JP2013166815A - Rubber composition for tire and pneumatic tire - Google Patents
Rubber composition for tire and pneumatic tire Download PDFInfo
- Publication number
- JP2013166815A JP2013166815A JP2012029457A JP2012029457A JP2013166815A JP 2013166815 A JP2013166815 A JP 2013166815A JP 2012029457 A JP2012029457 A JP 2012029457A JP 2012029457 A JP2012029457 A JP 2012029457A JP 2013166815 A JP2013166815 A JP 2013166815A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- tire
- mass
- rubber composition
- cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- 239000005060 rubber Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 11
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 11
- 229920001194 natural rubber Polymers 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- -1 alkaline earth metal salt Chemical class 0.000 claims description 22
- 229920003244 diene elastomer Polymers 0.000 claims description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000001993 dienes Chemical class 0.000 abstract 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229920002678 cellulose Polymers 0.000 description 32
- 235000010980 cellulose Nutrition 0.000 description 32
- 239000001913 cellulose Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 238000002156 mixing Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000008186 active pharmaceutical agent Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000006266 etherification reaction Methods 0.000 description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 7
- 229920003043 Cellulose fiber Polymers 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000004181 carboxyalkyl group Chemical group 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 229960000869 magnesium oxide Drugs 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000984084 Helianthemum nummularium subsp. grandiflorum Species 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 241000723267 Diospyros Species 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 241000758791 Juglandaceae Species 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- DIXGJWCZQHXZNR-UHFFFAOYSA-L magnesium citrate Chemical compound [Mg+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O DIXGJWCZQHXZNR-UHFFFAOYSA-L 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 229960000816 magnesium hydroxide Drugs 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000021018 plums Nutrition 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、タイヤに用いられるゴム組成物に関するものであり、より詳細には、例としてスタッドレスタイヤやスノータイヤなどの冬用タイヤ（ウインタータイヤ）のトレッドに好適に用いることのできるゴム組成物、及びそれを用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition used for a tire, and more specifically, a rubber composition that can be suitably used for a tread of a winter tire (winter tire) such as a studless tire or a snow tire, as an example, And a pneumatic tire using the same.
スタッドレスタイヤのトレッドゴムは、氷上路面での接地性を高めるために種々の工夫がなされており、例えば、０℃前後またはそれ以下の低温でゴム硬度が低くなるように調整されている。また、氷上摩擦力を高めるため、発泡ゴム、中空粒子、ガラス繊維、クルミ殻粉などのリグノセルロース材料の粒状体等の硬質材料を配合して、氷表面の引っかき効果を得たり、摩耗の進行により硬質材料が脱落したときに生じる脱落孔の凹凸を利用したりする等の手法が提案されている。 The tread rubber of the studless tire has been devised in various ways to improve the contact property on the road surface on ice. For example, the tread rubber is adjusted so that the rubber hardness becomes low at a low temperature of around 0 ° C. or lower. In addition, in order to increase the frictional force on ice, hard materials such as foamed rubber, hollow particles, glass fibers, and granular materials of lignocellulosic materials such as walnut shell powder are blended to obtain a scratching effect on the ice surface and the progress of wear. For example, a technique has been proposed in which the unevenness of the dropout hole that occurs when the hard material falls off is used.
また、湿潤路面（ウェット路面）におけるグリップ性能を改良するために、充填剤とオイルの配合量を増やす手法も用いられているが、この方法では、タイヤの転がり抵抗性能（低発熱性能）や耐摩耗性能が低下してしまうという問題が生じる。 In order to improve grip performance on wet road surfaces (wet road surfaces), a method of increasing the blending amount of filler and oil is also used, but in this method, tire rolling resistance performance (low heat generation performance) and resistance There arises a problem that the wear performance is lowered.
下記特許文献１には、ジエン系ゴムに、グラスファイバー等の短繊維と、古紙と、シリカを配合するとともに、もみ殻等のリグノセルロース系またはセルロース系物質を含む粉体加工品を配合し、短繊維や粉体加工品が脱落して生じる脱落孔により水膜除去効果を得ることについて提案されている。しかし、この方法では、優れたウェット・氷上制動性能が安定的に維持され難く、また、これらの短繊維や粉体加工品の分散性が低いため、ゴムの補強性が低下するという問題も生じる。 In the following Patent Document 1, a diene rubber is blended with short fibers such as glass fiber, waste paper, and silica, and a powder processed product containing lignocellulosic or cellulosic material such as rice husk, It has been proposed that a water film removing effect is obtained by a drop hole formed by dropping a short fiber or a processed powder product. However, with this method, it is difficult to stably maintain excellent wet / ice braking performance, and the dispersibility of these short fibers and powder processed products is low, resulting in a problem that the rubber reinforcing property is lowered. .
一方、下記特許文献２には、ゴム成分中に変性セルロース繊維を混合することが開示されている。該変性セルロース繊維としては、イソシアネート基とビニル基とを有する化合物を用いて、セルロース繊維の水酸基にイソシアネート基を反応結合させたものが用いられている。この文献では、セルロース繊維をゴム補強材として用いる場合に、セルロース繊維が親水性ではゴム成分に対する親和性が低いことから、セルロース繊維にビニル基を導入し、ビニル基を介してゴム成分との間で架橋関係を生じさせ、これにより、耐久性及び剛性を発揮するものであり、氷上路面や湿潤路面での接地性や制動性能については開示されていない。 On the other hand, Patent Document 2 below discloses mixing modified cellulose fibers in a rubber component. As the modified cellulose fiber, a compound in which an isocyanate group is reactively bonded to a hydroxyl group of a cellulose fiber using a compound having an isocyanate group and a vinyl group is used. In this document, when cellulose fiber is used as a rubber reinforcing material, if the cellulose fiber is hydrophilic, the affinity for the rubber component is low. Therefore, a vinyl group is introduced into the cellulose fiber and the rubber component is interposed between the vinyl group and the rubber component. In this way, a cross-linking relationship is produced, thereby exhibiting durability and rigidity, and the ground contact property and braking performance on an icy road surface or a wet road surface are not disclosed.
本発明は、タイヤの耐摩耗性能や転がり抵抗性能の低下を抑えながら、湿潤路面や氷上路面での接地性や制動性能が向上したタイヤが得られるタイヤ用ゴム組成物、及びそれを用いた空気入りタイヤを提供することを目的とする。 The present invention relates to a rubber composition for a tire from which a tire having improved grounding property and braking performance on a wet road surface or an ice surface can be obtained while suppressing a decrease in wear resistance performance and rolling resistance performance of the tire, and an air using the same. An object is to provide a tire entering.
本発明に係るタイヤ用ゴム組成物は、天然ゴム及び／又は他のジエン系ゴムからなるジエン系ゴム成分１００質量部に対して、親水性の変性セルロースの粉末を０．１〜３０質量部と、アルカリ土類金属塩を０．１〜１０質量部配合したものである。 The rubber composition for a tire according to the present invention comprises 0.1 to 30 parts by mass of hydrophilic modified cellulose powder with respect to 100 parts by mass of a diene rubber component composed of natural rubber and / or other diene rubber. And 0.1 to 10 parts by mass of an alkaline earth metal salt.
本発明に係る空気入りタイヤは、該ゴム組成物を用いてなるトレッドを備えたものである。 The pneumatic tire according to the present invention includes a tread made using the rubber composition.
本発明に係るゴム組成物より得られるタイヤであると、湿潤路面や氷上路面の水膜を効果的に除去することができるものとなり、タイヤの耐摩耗性能や転がり抵抗性能の低下を抑えながら、湿潤路面や氷上路面での制動性能を向上させることが可能となる。 When the tire is obtained from the rubber composition according to the present invention, the water film on the wet road surface and the road surface on ice can be effectively removed, while suppressing the decrease in the wear resistance performance and rolling resistance performance of the tire, It becomes possible to improve the braking performance on wet road surfaces and on-ice road surfaces.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本実施形態に係るタイヤ用ゴム組成物において、ゴム成分として用いられるジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）などの各種ジエン系ゴムが挙げられる。これらジエン系ゴムは、いずれか１種単独で、又は２種以上ブレンドして用いることができる。 In the rubber composition for tires according to the present embodiment, examples of the diene rubber used as the rubber component include natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), and styrene butadiene rubber (SBR). And various diene rubbers. These diene rubbers can be used alone or in a blend of two or more.
ジエン系ゴム成分として、好ましくは、天然ゴムと他のジエン系ゴムとのブレンドを用いることであり、特に好ましくは、天然ゴム（ＮＲ）とポリブタジエンゴム（ＢＲ）とのブレンドゴムを用いることである。その場合、ＢＲの比率が少なすぎるとゴム組成物の低温特性が得難くなり、逆に多くなりすぎると加工性の悪化や耐引き裂き抵抗性が低下する傾向になるので、ＮＲ／ＢＲの比率は、質量比で３０／７０〜８０／２０、更には４０／６０〜７０／３０程度であることが好ましい。 As the diene rubber component, a blend of natural rubber and another diene rubber is preferably used, and a blend rubber of natural rubber (NR) and polybutadiene rubber (BR) is particularly preferably used. . In that case, if the ratio of BR is too small, it is difficult to obtain low temperature characteristics of the rubber composition. Conversely, if the ratio is too large, the processability tends to deteriorate and the tear resistance tends to decrease, so the ratio of NR / BR is The mass ratio is preferably about 30/70 to 80/20, more preferably about 40/60 to 70/30.
本実施形態に係るゴム組成物において使用する親水性の変性セルロースの粉末とは、セルロース分子の水酸基の水素原子を適度に他の基に置換した化学修飾セルロースの粉末であり、特には、エーテル変性することにより、その水酸基同士の水素結合が起こらないようにしたセルロースエーテルの粉末である。すなわち、セルロースは多くの水酸基を有するため、分子間でその水酸基同士が強い水素結合を形成して凝集するが、水酸基同士の水素結合を抑制することによりセルロース分子同士が凝集し難くなり、よって分散性のよいパウダー状のセルロースが得られる。このようなパウダー状の変性セルロースはゴムとの親和性も良好であり、ゴム中での分散性に優れると考えられる。 The hydrophilic modified cellulose powder used in the rubber composition according to the present embodiment is a chemically modified cellulose powder in which hydrogen atoms of hydroxyl groups of cellulose molecules are appropriately substituted with other groups, and in particular, ether-modified This is a cellulose ether powder in which hydrogen bonding between the hydroxyl groups does not occur. In other words, since cellulose has many hydroxyl groups, the hydroxyl groups form a strong hydrogen bond between molecules and aggregate, but by suppressing the hydrogen bond between hydroxyl groups, the cellulose molecules become difficult to aggregate and thus dispersed. A good powdery cellulose is obtained. Such powdery modified cellulose has good affinity with rubber and is considered to be excellent in dispersibility in rubber.
セルロース分子の水酸基の水素原子を置換する置換基の例としては、メチル基等のアルキル基；ヒドロキシエチル基、ヒドロキシプロピル基等のヒドロキシアルキル基；カルボキシメチル基、カルボキシエチル基等のカルボキシアルキル基等が挙げられる。また、メチルヒドロキシエチルセルロースといった、複数種のエーテル基を導入したものであっても良い。これらの中でも、好ましくは、セルロースの水酸基をカルボキシアルキルエーテルに変換したものであり、すなわち、変性セルロースとしては、カルボキシメチルセルロースや、カルボキシエチルセルロースなどのカルボキシアルキルセルロースが好適に用いられる。特に好ましくはカルボキシメチルセルロースである。 Examples of substituents for substituting hydrogen atoms of hydroxyl groups of cellulose molecules include alkyl groups such as methyl groups; hydroxyalkyl groups such as hydroxyethyl groups and hydroxypropyl groups; carboxyalkyl groups such as carboxymethyl groups and carboxyethyl groups Is mentioned. Moreover, what introduce | transduced multiple types of ether groups, such as methylhydroxyethylcellulose, may be used. Among these, Preferably, the hydroxyl group of cellulose is converted to carboxyalkyl ether, that is, carboxyalkyl cellulose such as carboxymethyl cellulose and carboxyethyl cellulose is preferably used as the modified cellulose. Particularly preferred is carboxymethylcellulose.
上記変性セルロースのエーテル化度（置換度ＤＳ）は０．１〜３．０の範囲、通常は０．１〜２．５である。好ましくは、エーテル化度は、０．２〜１．５の範囲であり、０．２〜１．０の範囲であることがさらに好ましく、０．２〜０．９の範囲、特には０．２〜０．８または０．２〜０．７であることがより好ましい。エーテル化度が０．１より低いと分散性及び親水性が不十分となりやすく、１．５より大きいと、セルロース原料（通常、木材パルプからの溶解パルプ、または精製したリンター）の繊維形状が失われて行き、塊状の粒子となって行くことから、分散性及び実際上の吸水性が小さくなり、路面の水膜を除去する効果が得られ難くなる。エーテル化度とは、無水グルコース１単位当たりのエーテル置換基数である。 The etherification degree (substitution degree DS) of the modified cellulose is in the range of 0.1 to 3.0, usually 0.1 to 2.5. Preferably, the degree of etherification is in the range of 0.2 to 1.5, more preferably in the range of 0.2 to 1.0, more preferably in the range of 0.2 to 0.9, in particular 0. It is more preferable that it is 2-0.8 or 0.2-0.7. If the degree of etherification is less than 0.1, dispersibility and hydrophilicity tend to be insufficient, and if it is greater than 1.5, the fiber shape of the cellulose raw material (usually dissolved pulp from wood pulp or refined linter) is lost. Since the particles are broken and become agglomerated particles, the dispersibility and the actual water absorption are reduced, and it is difficult to obtain the effect of removing the water film on the road surface. The degree of etherification is the number of ether substituents per unit of anhydrous glucose.
エーテル化度の測定は、例えばメチルセルロースなどの場合、置換されていない水酸基についてメトキシアセチル化などを施した後、ＮＭＲにより測定することができる。また、カルボキシメチルセルロースのナトリウム塩などの場合、灰化した後、中和滴定を行うことにより、容易に測定を行うことができる。親水性のセルロースエーテルは、一般的な工業的製法によると、木材由来の溶解パルプ、または、精製コットンリンターなどといった繊維状のセルロース原料に、粉砕後、アルカリを加え、含水有機溶媒中でエーテル化剤（メチルクロリド、モノクロロ酢酸など）を反応させて、中和、脱塩、乾燥及び粉砕・分級などを行うことで製造される。したがって、セルロースのエーテル化は、不均一に進行し、エーテル化度が比較的低い製品、特に０．５以下の製品にあっては、粉末粒子の表面に近い部分で、粉末粒子の芯の部分より置換度が高いと考えられる。なお、親水性のセルロースエーテル製品は、吸湿性を有し、通常１０質量％以下、通常２〜８質量％の含水率を有する。本願における配合量の記載は、絶乾（例えば１０５℃で４時間乾燥）質量に基づいている。 For example, in the case of methyl cellulose, the degree of etherification can be measured by NMR after performing methoxyacetylation on an unsubstituted hydroxyl group. Moreover, in the case of sodium salt of carboxymethylcellulose, etc., it can be easily measured by performing neutralization titration after ashing. According to a general industrial production method, hydrophilic cellulose ether is ground into fibrous cellulose raw material such as wood-derived dissolving pulp or refined cotton linter, added with alkali, and then etherified in a hydrous organic solvent. It is produced by reacting an agent (methyl chloride, monochloroacetic acid, etc.), neutralizing, desalting, drying, pulverizing / classifying and the like. Therefore, the etherification of cellulose proceeds in a non-uniform manner, and in products having a relatively low degree of etherification, particularly in products of 0.5 or less, the portion close to the surface of the powder particles, the core portion of the powder particles It is considered that the degree of substitution is higher. The hydrophilic cellulose ether product has a hygroscopic property and usually has a water content of 10% by mass or less, and usually 2 to 8% by mass. The description of the blending amount in the present application is based on the absolute dry mass (for example, drying at 105 ° C. for 4 hours).
上記の親水性変性セルロースの１質量％水溶液の粘度は、好ましくは５〜１０００ｍPa・sec、より好ましくは１０〜３５０ｍPa・sec、さらに好ましくは１０〜２００ｍPa・secである。粘度は、ＢＭ型粘度計を用い、２５℃にて、ローターの回転開始から６０秒後の数値を読むことにより測定できる。 The viscosity of the 1% by mass aqueous solution of the above hydrophilic modified cellulose is preferably 5 to 1000 mPa · sec, more preferably 10 to 350 mPa · sec, still more preferably 10 to 200 mPa · sec. The viscosity can be measured by reading a numerical value after 60 seconds from the start of rotation of the rotor at 25 ° C. using a BM viscometer.
カルボキシメチルセルロースの一般的な工業製品はナトリウム塩であるが、カリウム塩やアンモニウム塩であってもよい。カルボキシメチルセルロース製品としては、例えば、日本製紙ケミカル（株）のサンローズＦ０１ＭＣ（ＤＳ：０．７、１％粘度：１０ｍPa・sec）、Ｆ１０ＭＣ（ＤＳ：０．７、１％粘度：１００ｍPa・sec）、Ｆ３０ＭＣ（ＤＳ：０．７、１％粘度：３００ｍPa・sec）、Ｆ０１ＬＣ（ＤＳ：０．６、１％粘度：１０ｍPa・sec）、Ｆ１０ＬＣ（ＤＳ：０．６、１％粘度：１００ｍPa・sec）、Ｆ２０ＬＣ（ＤＳ：０．６、１％粘度：２００ｍPa・sec）、ＳＬＤ（ＤＳ：０．２〜０．３、１％粘度：１００ｍPa・sec）などを好ましいものとして挙げることができる。また、メチル化セルロース製品としては、例えば、信越化学工業(株)のメトローズＳＲシリーズの各製品を用いることができる。 A common industrial product of carboxymethyl cellulose is a sodium salt, but may be a potassium salt or an ammonium salt. Examples of carboxymethylcellulose products include Sunrose F01MC (DS: 0.7, 1% viscosity: 10 mPa · sec), F10MC (DS: 0.7, 1% viscosity: 100 mPa · sec) from Nippon Paper Chemicals Co., Ltd. , F30MC (DS: 0.7, 1% viscosity: 300 mPa · sec), F01LC (DS: 0.6, 1% viscosity: 10 mPa · sec), F10LC (DS: 0.6, 1% viscosity: 100 mPa · sec) ), F20LC (DS: 0.6, 1% viscosity: 200 mPa · sec), SLD (DS: 0.2 to 0.3, 1% viscosity: 100 mPa · sec) and the like can be mentioned as preferable examples. In addition, as the methylated cellulose product, for example, each product of Metroze SR series of Shin-Etsu Chemical Co., Ltd. can be used.
また、上記変性セルロースは、平均粒径（質量平均粒径）が２０〜１００μｍの範囲であるパウダー状であることが好ましい。平均粒径が２０μｍより小さいと分散性が不十分となり易く、１００μｍより大きいとゴムとの親和性が小さくなりタイヤの耐摩耗性能が低下し易い。なお、本明細書でいう平均粒径は篩にて分級することにより算出したものとする。 Moreover, it is preferable that the said modified cellulose is a powder form whose average particle diameter (mass average particle diameter) is the range of 20-100 micrometers. If the average particle size is less than 20 μm, the dispersibility tends to be insufficient, and if it is more than 100 μm, the affinity with rubber is reduced and the wear resistance of the tire tends to be reduced. In addition, the average particle diameter as used in this specification shall be computed by classifying with a sieve.
上記のようにセルロース分子中の水酸基を適度に他の基に置換した変性セルロースを使用した場合、これらの変性セルロースは、ゴム中での分散性が良好であることから、ゴムの補強性や耐摩耗性能の向上または維持に寄与するとともに、親水性が高く湿潤路面や氷上路面の水膜を吸水および除水することにより、優れた制動性能が発現されると考えられる。また、この変性セルロース、とりわけカルボキシアルキルセルロースは、シリカ等のフィラーと共に使用した場合、これらのフィラーの分散剤としても機能すると考えられる。 When modified cellulose in which the hydroxyl group in the cellulose molecule is appropriately substituted with other groups as described above is used, these modified celluloses have good dispersibility in rubber, so that the reinforcing properties and resistance of rubber are reduced. It contributes to the improvement or maintenance of the wear performance, and it is considered that excellent braking performance is expressed by absorbing and removing water film having high hydrophilicity and wet road surface and on-ice road surface. Moreover, when this modified cellulose, especially carboxyalkyl cellulose are used with fillers, such as a silica, it is thought that it functions also as a dispersing agent of these fillers.
本実施形態のゴム組成物においては、ジエン系ゴム成分１００質量部に対して、上記親水性の変性セルロースの粉末を０．１〜３０質量部配合するものとし、好ましくは１〜２５質量部、より好ましくは２〜２５質量部、さらに好ましくは、２〜１５質量部、一層好ましくは５〜１５質量部配合するものとする。その配合量が０．１質量部より少ないと水膜除去効果が得られず、３０質量部より大きいと耐摩耗性能が著しく低下する。 In the rubber composition of this embodiment, 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass of the hydrophilic modified cellulose powder is added to 100 parts by mass of the diene rubber component. More preferably 2 to 25 parts by mass, still more preferably 2 to 15 parts by mass, and still more preferably 5 to 15 parts by mass. If the blending amount is less than 0.1 parts by mass, the effect of removing the water film cannot be obtained.
本実施形態に係るゴム組成物において使用するアルカリ土類金属塩とは、べリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、ラジウムの塩化合物があり、アルカリ土類金属の酸化物、水酸化物、水素化物、塩化物、炭酸塩、硫酸塩、リン酸塩、硝酸塩、シュウ酸塩、酢酸塩等が挙げられる。 The alkaline earth metal salt used in the rubber composition according to the present embodiment includes a salt compound of beryllium, magnesium, calcium, strontium, barium, radium, an alkaline earth metal oxide, hydroxide, hydrogen Compound, chloride, carbonate, sulfate, phosphate, nitrate, oxalate, acetate and the like.
アルカリ土類金属塩として、具体的には、水酸化マグネシウム、酸化マグネシウム、炭酸マグネシウム、クエン酸マグネシウム、クエン酸水素マグネシウム、酢酸マグネシウム、リン酸マグネシウムなどのマグネシウム塩化合物；水酸化カルシウム、酸化カルシウム、炭酸カルシウム、クエン酸カルシウム、リン酸カルシウム、リン酸水素カルシウム、酢酸カルシウム、塩化カルシウム、水素化カルシウムなどのカルシウム塩化合物；炭酸ストロンチウム、酢酸ストロンチウム、シュウ酸ストロンチウム、水酸化ストロンチウム、酸化ストロンチウムなどのストロンチウム塩化合物；水酸化バリウムなどのバリウム塩化合物などが挙げられる。これらのアルカリ土類金属塩は、１種のみを用いてもよく、２種以上を併用してもよい。これらの中でも、カルシウム塩及び／又はマグネシウム塩が好ましく用いられ、より好ましくは、炭酸カルシウム、水酸化カルシウム、酸化カルシウム、酸化マグネシウム、水酸化マグネシウムよりなる群から選択された少なくとも１種であり、更に好ましくは炭酸カルシウム及び／又は酸化マグネシウムである。 Specific examples of the alkaline earth metal salt include magnesium hydroxide compounds such as magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium citrate, magnesium hydrogen citrate, magnesium acetate, and magnesium phosphate; calcium hydroxide, calcium oxide, Calcium salt compounds such as calcium carbonate, calcium citrate, calcium phosphate, calcium hydrogen phosphate, calcium acetate, calcium chloride, calcium hydride; strontium salt compounds such as strontium carbonate, strontium acetate, strontium oxalate, strontium hydroxide, strontium oxide A barium salt compound such as barium hydroxide; These alkaline earth metal salts may be used alone or in combination of two or more. Among these, calcium salt and / or magnesium salt is preferably used, more preferably at least one selected from the group consisting of calcium carbonate, calcium hydroxide, calcium oxide, magnesium oxide, magnesium hydroxide, Preferred is calcium carbonate and / or magnesium oxide.
上記変性セルロース粉末とともに、これらのアルカリ土類金属塩を配合することにより、路面の水膜を除去する効果を高めて、湿潤路面や氷上路面での制動性能をより一層向上させることができる。特に、変性セルロースとしてカルボキシル基を持つカルボキシアルキルセルロースを用いた場合、二価の金属カチオンであるアルカリ土類金属イオンを介して変性セルロース分子が三次元網目構造を形成し、親水性の空洞を生成するものと考えられる。すなわち、変性セルロース分子のカルボキシル基の陰イオンがアルカリ土類金属イオンと錯体を形成することで、変性セルロース分子同士がアルカリ土類金属イオンを介して架橋構造を形成し、これにより親水性の空洞が生成されるので、より効果的に吸水、除水効果が発揮されて、優れた湿潤・氷上制動性能が得られるものと考えられる。 By blending these alkaline earth metal salts with the modified cellulose powder, the effect of removing the water film on the road surface can be enhanced, and the braking performance on wet road surfaces and on-ice road surfaces can be further improved. In particular, when carboxyalkyl cellulose having a carboxyl group is used as the modified cellulose, the modified cellulose molecules form a three-dimensional network structure via alkaline earth metal ions, which are divalent metal cations, to generate hydrophilic cavities. It is thought to do. That is, the anion of the carboxyl group of the modified cellulose molecule forms a complex with the alkaline earth metal ion, so that the modified cellulose molecules form a crosslinked structure via the alkaline earth metal ion, thereby forming a hydrophilic cavity. Therefore, it is considered that water absorption and dewatering effects are more effectively exhibited and excellent wet / ice braking performance is obtained.
本実施形態のゴム組成物においては、ジエン系ゴム成分１００質量部に対して、上記アルカリ土類金属塩を０．１〜１０質量部配合するものとし、好ましくは０．５〜８質量部、より好ましくは１〜５質量部配合することである。アルカリ土類金属塩の配合量が０．１質量部より少ないとその添加効果が十分とはいえず、逆に１０質量部を超えて配合しても更なる水膜除去効果の向上効果は得られない。 In the rubber composition of the present embodiment, 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass of the alkaline earth metal salt is added to 100 parts by mass of the diene rubber component. More preferably, 1 to 5 parts by mass is blended. If the blending amount of the alkaline earth metal salt is less than 0.1 parts by mass, the effect of addition cannot be said to be sufficient. I can't.
本実施形態に係るゴム組成物には、フィラー（補強性充填剤）として、カーボンブラック及び／又はシリカを配合することができる。フィラーの配合量は、特に限定されず、例えば、上記ジエン系ゴム成分１００質量部に対し２５〜１２５質量部であることが好ましく、より好ましくは３０〜８０質量部である。 In the rubber composition according to the present embodiment, carbon black and / or silica can be blended as a filler (reinforcing filler). The compounding quantity of a filler is not specifically limited, For example, it is preferable that it is 25-125 mass parts with respect to 100 mass parts of said diene rubber components, More preferably, it is 30-80 mass parts.
カーボンブラックとしては、スタッドレスタイヤのトレッド部に用いる場合、ゴム組成物の低温性能、耐摩耗性能やゴムの補強性などの観点から、窒素吸着比表面積（Ｎ２ＳＡ）（ＪＩＳ Ｋ６２１７−２）が７０〜１５０ｍ２／ｇであり、かつＤＢＰ吸油量（ＪＩＳ Ｋ６２１７−４）が１００〜１５０ｍｌ／１００ｇであるものが好ましく用いられる。具体的にはＳＡＦ，ＩＳＡＦ，ＨＡＦ級のカーボンブラックが例示され、配合量としてはジエン系ゴム成分１００質量部に対して１０〜８０質量部程度の範囲で使用されることが好ましく、より好ましくは１５〜５０質量部である。 As carbon black, when used in a tread portion of a studless tire, a nitrogen adsorption specific surface area (N 2 SA) (JIS K6217-2) is used from the viewpoint of low temperature performance, wear resistance performance, rubber reinforcement and the like of the rubber composition. 70~150m a 2 / g, and DBP oil absorption (JIS K6217-4) is preferably used is 100 to 150 ml / 100 g. Specifically, SAF, ISAF, HAF grade carbon black is exemplified, and the blending amount is preferably used in the range of about 10 to 80 parts by mass, more preferably about 100 parts by mass of the diene rubber component. 15 to 50 parts by mass.
シリカとしては、例えば、湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）、或いは表面処理シリカなどが使用され、配合量はゴムのｔａｎδのバランスや補強性などの観点からジエン系ゴム成分１００質量部に対して１０〜５０質量部であることが好ましく、より好ましくは１５〜５０質量部である。 As silica, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), surface-treated silica, or the like is used, and the blending amount is a diene rubber component from the viewpoint of the balance of tan δ of rubber and reinforcing properties. It is preferable that it is 10-50 mass parts with respect to 100 mass parts, More preferably, it is 15-50 mass parts.
シリカを配合する場合、スルフィドシラン、メルカプトシランなどのシランカップリング剤を併用することが好ましく、その配合量はシリカ配合量に対して２〜２０質量％であることが好ましい。 When silica is blended, a silane coupling agent such as sulfide silane or mercaptosilane is preferably used in combination, and the blending amount is preferably 2 to 20% by mass with respect to the silica blending amount.
本実施形態に係るゴム組成物には、上記した各成分に加え、通常のゴム工業で使用されているプロセスオイル、亜鉛華、ステアリン酸、軟化剤、可塑剤、ワックス、老化防止剤（アミン−ケトン系、芳香族第２アミン系、フェノール系、イミダゾール系等）、加硫剤、加硫促進剤（グアニジン系、チアゾール系、スルフェンアミド系、チウラム系等）などの配合薬品類を通常の範囲内で適宜配合することができる。 In addition to the above-described components, the rubber composition according to the present embodiment includes process oil, zinc white, stearic acid, softener, plasticizer, wax, anti-aging agent (amine-amine) used in the normal rubber industry. Ketones, aromatic secondary amines, phenols, imidazoles, etc.), vulcanizing agents, vulcanization accelerators (guanidines, thiazoles, sulfenamides, thiurams, etc.) It can mix | blend suitably within the range.
加硫剤としては、硫黄、硫黄含有化合物等が挙げられ、特に限定するものではないが、その配合量は上記ジエン系ゴム成分１００質量部に対して０．１〜１０質量部であることが好ましく、より好ましくは０．５〜５質量部である。また、加硫促進剤の配合量としては、上記ジエン系ゴム成分１００質量部に対して０．１〜７質量部であることが好ましく、より好ましくは０．５〜５質量部である。 Examples of the vulcanizing agent include sulfur and sulfur-containing compounds, and are not particularly limited. However, the amount of the vulcanizing agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber component. Preferably, it is 0.5-5 mass parts. Moreover, as a compounding quantity of a vulcanization accelerator, it is preferable that it is 0.1-7 mass parts with respect to 100 mass parts of said diene rubber components, More preferably, it is 0.5-5 mass parts.
本実施形態に係るゴム組成物には、また、氷上性能を更に向上するために、種子の殻又は果実の核を粉砕してなる植物性粒状体や、植物の多孔質性炭化物の粉砕物を配合してもよい。植物性粒状体としては、胡桃（クルミ）、椿などの種子の殻、あるいは桃、梅などの果実の核を公知の方法で粉砕してなる粉砕品を用いることができる。多孔質性炭化物粉砕物としては、木、竹などの植物を材料として炭化して得られる炭素を主成分とする固体生成物からなる多孔質性物質を粉砕してなるものであり、中でも竹炭の粉砕物（竹炭粉砕物）が好適に用いられる。 In order to further improve the performance on ice, the rubber composition according to the present embodiment includes a plant granule obtained by pulverizing a seed shell or a fruit core, or a pulverized product of a porous carbide of a plant. You may mix | blend. As the plant granules, pulverized products obtained by pulverizing seed husks such as walnuts and persimmons or fruit nuclei such as peaches and plums by a known method can be used. The porous carbide pulverized product is obtained by pulverizing a porous substance composed of a solid product mainly composed of carbon obtained by carbonizing a plant such as wood or bamboo. A pulverized product (bamboo charcoal pulverized product) is preferably used.
本実施形態に係るゴム組成物は、通常のバンバリーミキサーやニーダー、ロール等の混合機を用いて、常法に従い混練し作製することができる。すなわち、第一混合段階で、ゴム成分に対し、変性セルロース粉末及びアルカリ土類金属塩とともに、加硫剤及び加硫促進剤を除く他の添加剤を添加混合し、次いで、得られた混合物に、最終混合段階で加硫剤及び加硫促進剤を添加混合することによりゴム組成物を調製することができる。 The rubber composition according to the present embodiment can be prepared by kneading according to a conventional method using a mixer such as a normal Banbury mixer, a kneader, or a roll. That is, in the first mixing stage, the rubber component is added and mixed with the modified cellulose powder and the alkaline earth metal salt together with other additives excluding the vulcanizing agent and the vulcanization accelerator, and then the resulting mixture is mixed. The rubber composition can be prepared by adding and mixing the vulcanizing agent and the vulcanization accelerator in the final mixing stage.
このようにして得られるゴム組成物は、空気入りタイヤの接地面を構成するトレッドゴムに好適に用いられ、より好ましくは、スタッドレスタイヤ、スノータイヤなどの冬用タイヤ（ウインタータイヤ）のトレッド部のためのゴム組成物として好適に用いられ、常法に従い、例えば１４０〜１８０℃で加硫成形することにより、該トレッド部を形成することができる。空気入りタイヤのトレッド部には、キャップゴムとベースゴムとの２層構造からなるものと、両者が一体の単層構造のものがあるが、接地面を構成するゴムに用いられるので、単層構造のものであれば、当該トレッドゴムが上記ゴム組成物からなり、２層構造のものであれば、キャップゴムが上記ゴム組成物からなる。 The rubber composition thus obtained is preferably used for a tread rubber constituting a ground contact surface of a pneumatic tire, and more preferably a tread portion of a winter tire (winter tire) such as a studless tire or a snow tire. For example, the tread portion can be formed by vulcanization molding at 140 to 180 ° C. according to a conventional method. There are two types of pneumatic tire tread parts, one with a cap rubber and one base rubber structure, and the other with a single-layer structure. In the case of a structure, the tread rubber is composed of the rubber composition, and in the case of a two-layer structure, the cap rubber is composed of the rubber composition.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
バンバリーミキサーを使用し、下記表１に示す配合（質量部）に従い、まず、第一混合段階で、硫黄と加硫促進剤を除く成分を添加混合し、次いで、得られた混合物に、最終混合段階で硫黄と加硫促進剤を添加混合して、タイヤトレッド用ゴム組成物を調製した。表１中の各成分の詳細は以下の通りである。 Using a Banbury mixer, according to the composition (parts by mass) shown in Table 1 below, first, in the first mixing stage, components other than sulfur and vulcanization accelerator are added and mixed, and then the resulting mixture is finally mixed. In the step, sulfur and a vulcanization accelerator were added and mixed to prepare a rubber composition for a tire tread. The details of each component in Table 1 are as follows.
・ＮＲ：天然ゴム（ＲＳＳ＃３）
・ＢＲ：ＪＳＲ（株）製「ＢＲ０１」(ハイシスＢＲ，シス１，４結合含量９５％)
・カーボンブラック：東海カーボン（株）製「シーストＫＨ（Ｎ３３９）」（Ｎ２ＳＡ＝９３ｍ２／ｇ、ＤＢＰ＝１１９ｍｌ／１００ｇ）
・シリカ：東ソー・シリカ株式会社製「ニップシールＡＱ」
・シランカップリング剤：デグサ社製「Ｓｉ７５」
・パラフィンオイル：ＪＯＭＯサンエナジー（株）製「プロセスＰ２００」
・未変性セルロース：日本製紙ケミカル（株）製「ＫＣフロックＷ−５０」（平均粒径：５０μｍ）
・変性セルロース：日本製紙ケミカル（株）製「サンローズＦ１０ＭＣ」（カルボキシメチルセルロース、エーテル化度：０．７０、平均粒径：５０μｍ、１％水溶液粘度：約１００ｍPa・sec）
・炭酸カルシウム:日東粉化工業 (株) 製「ノーベライト３Ｔ」
・酸化マグネシウム：協和化学工業（株）製「キョーワマグ１５０」
・ステアリン酸：日本油脂（株）製「ステアリン酸」
・亜鉛華：三井金属鉱業（株）製「亜鉛華１種」
・老化防止剤：住友化学工業（株）製「アンチゲン６Ｃ」
・ワックス：日本精蝋株式会社製「ＯＺＯＡＣＥ０３５５」
・加硫促進剤：住友化学工業（株）製「ソクシノールＣＺ」
・硫黄：鶴見化学工業（株）製「粉末硫黄」
・ NR: Natural rubber (RSS # 3)
-BR: "BR01" manufactured by JSR Corporation (high cis BR, cis 1,4 bond content 95%)
Carbon black: “Seast KH (N339)” manufactured by Tokai Carbon Co., Ltd. (N 2 SA = 93 m 2 / g, DBP = 119 ml / 100 g)
・ Silica: “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd.
Silane coupling agent: “Si75” manufactured by Degussa
Paraffin oil: “Process P200” manufactured by JOMO Sun Energy Co., Ltd.
Unmodified cellulose: “KC Flock W-50” manufactured by Nippon Paper Chemicals Co., Ltd. (average particle size: 50 μm)
Modified cellulose: “Sunrose F10MC” manufactured by Nippon Paper Chemical Co., Ltd. (carboxymethylcellulose, degree of etherification: 0.70, average particle size: 50 μm, 1% aqueous solution viscosity: about 100 mPa · sec)
・ Calcium carbonate: “Nobelite 3T” manufactured by Nitto Flour Industry Co., Ltd.
Magnesium oxide: “Kyowa Mug 150” manufactured by Kyowa Chemical Industry Co., Ltd.
・ Stearic acid: “Stearic acid” manufactured by NOF Corporation
・ Zinc flower: “Zinc flower 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
Anti-aging agent: “Antigen 6C” manufactured by Sumitomo Chemical Co., Ltd.
・ Wax: Nippon Seiwa Co., Ltd. “OZOACE0355”
・ Vulcanization accelerator: “Soxinol CZ” manufactured by Sumitomo Chemical Co., Ltd.
・ Sulfur: “Powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
得られた各ゴム組成物について、硬度を測定した。また、各ゴム組成物を用いてスタッドレスタイヤを作製した。タイヤサイズは１９５／６５Ｒ１５として、そのトレッドに各ゴム組成物を適用し、常法に従い加硫成形することによりタイヤを製造した。得られた各タイヤについて、耐摩耗性能、氷上制動性能、湿潤制動性能、転がり抵抗性能を評価した（使用リムは１５×５．５ＪＪ）。各測定、評価方法は次の通りである。 The hardness of each rubber composition obtained was measured. Also, studless tires were produced using each rubber composition. The tire size was 195 / 65R15, and each rubber composition was applied to the tread, and a tire was manufactured by vulcanization molding according to a conventional method. Each of the obtained tires was evaluated for wear resistance performance, on-ice braking performance, wet braking performance, and rolling resistance performance (the rim used was 15 × 5.5 JJ). Each measurement and evaluation method is as follows.
・硬度：ＪＩＳ Ｋ６２５３に準拠したデュロメータ タイプＡにより、１５０℃×３０分で加硫したサンプル（厚みが１２ｍｍ以上のもの）について、２３℃及び−５℃での硬度を測定した。 Hardness: The hardness at 23 ° C. and −5 ° C. was measured for a sample (thickness of 12 mm or more) vulcanized at 150 ° C. × 30 minutes by durometer type A according to JIS K6253.
・耐摩耗性能：上記タイヤを２０００ｃｃの４ＷＤ車に装着し、２５００ｋｍ毎に左右ローテーションさせながら１００００ｋｍ走行させて、走行後の残溝の深さを測定した。残溝は４本の平均値である。比較例１の値を１００とした指数で表示し、指数が大きいほど耐摩耗性能が良好であることを示す。 Wear resistance performance: The tire was mounted on a 2000 cc 4WD vehicle and traveled 10,000 km while rotating left and right every 2500 km, and the depth of the remaining groove after traveling was measured. The remaining groove is an average value of four. The value of Comparative Example 1 is expressed as an index, and the larger the index, the better the wear resistance.
・氷上制動性能：上記タイヤを２０００ｃｃのＦＦ車に装着し、氷盤路（気温−３±３℃）上で４０ｋｍ／ｈ走行からＡＢＳ作動させて制動距離を測定し（ｎ＝１０の平均値）、制動距離の逆数について比較例１の値を１００とした指数で表示した。指数が大きいほど制動距離が短く、氷上路面での制動性能に優れることを示す。 ・ Ice braking performance: The above tires are mounted on a 2000cc FF vehicle, and the braking distance is measured by running ABS from 40km / h on an icy road (temperature -3 ± 3 ℃) (average value of n = 10) ), The reciprocal of the braking distance is expressed as an index with the value of Comparative Example 1 being 100. The larger the index, the shorter the braking distance and the better the braking performance on the road surface on ice.
・湿潤制動性能：上記タイヤを２０００ｃｃのＦＦ車に装着し、湿潤路面上で９０ｋｍ／ｈ走行からＡＢＳ作動させ、２０ｋｍ／ｈまで減速時の制動距離を測定し（ｎ＝１０の平均値）、制動距離の逆数について比較例１の値を１００とした指数で表示した。指数が大きいほど制動距離が短く、湿潤路面での制動性能に優れることを示す。 -Wet braking performance: The above tire is mounted on a 2000 cc FF vehicle, ABS is operated from 90 km / h running on a wet road surface, and the braking distance during deceleration to 20 km / h is measured (average value of n = 10). The reciprocal of the braking distance was expressed as an index with the value of Comparative Example 1 as 100. The larger the index, the shorter the braking distance and the better the braking performance on wet road surfaces.
・転がり抵抗性能：空気圧２３０ｋＰａ、荷重４．４ｋＮ、室温２３℃、８０ｋｍ／ｈの条件下で、ＲＲ測定ドラムを使用して転がり抵抗を測定し、転がり抵抗の逆数について比較例１の値を１００とした指数で表示した。指数が大きいほど転がり抵抗が小さく、良好であることを示す。 Rolling resistance performance: rolling resistance was measured using an RR measuring drum under conditions of air pressure 230 kPa, load 4.4 kN, room temperature 23 ° C., 80 km / h, and the value of Comparative Example 1 was set to 100 for the reciprocal of rolling resistance. It was expressed as an index. The larger the index, the smaller the rolling resistance and the better.
結果は、表１に示す通りであり、実施例のゴム組成物から得られたタイヤであると、コントロールである比較例１に対し、耐摩耗性能と転がり抵抗性能の低下を抑えながら、氷上路面及び湿潤路面での制動性能が大幅に向上していた。 The results are as shown in Table 1. In the case of a tire obtained from the rubber composition of the example, the road surface on ice is controlled against the control of Comparative Example 1 while suppressing a decrease in wear resistance and rolling resistance performance. In addition, braking performance on wet roads was greatly improved.
詳細には、比較例２に示されたように、未変性のセルロースを配合した場合、氷上制動性能及び湿潤制動性能の向上は見られず、耐摩耗性が悪化していた。比較例３に示されたように、未変性セルロースに炭酸カルシウムを配合した場合も、同様であった。比較例６に示されたように、炭酸カルシウムの単独添加でも同様であった。 Specifically, as shown in Comparative Example 2, when unmodified cellulose was blended, no improvement was observed in ice braking performance and wet braking performance, and the wear resistance was deteriorated. As shown in Comparative Example 3, the same was true when calcium carbonate was blended with unmodified cellulose. As shown in Comparative Example 6, it was the same even when calcium carbonate was added alone.
一方、比較例４及び５に示されたように、変性セルロース粉末を配合した場合、コントロールである比較例１に対して、耐摩耗性能と転がり抵抗性能の低下を抑えながら、氷上路面及び湿潤路面での制動性能を向上することができた。変性セルロースを配合した場合、発泡剤を使用しなくても、平均孔径が２０〜８０μｍ、より詳細には４０〜５０μｍ程度の均一できめ細かな気泡を有するミクロボイド構造をゴム中に形成するのが認められた。そのため、変性セルロース自体の親水性による吸水及び除水効果とともに、このミクロボイド構造もタイヤを形成した際に吸水、除水及びエッジ効果等を発揮し、優れた湿潤制動性能・氷上制動性能の維持に寄与していると考えられる。ミクロボイド構造が形成されるメカニズムは明らかではないが、タイヤ組成物の混合中等に発生する水分や揮発成分が、カルボキシメチルセルロース分子の存在によって、分散した状態で捕捉されると推測される。すなわち、カルボキシメチルセルロースは、吸湿性が高いため、混練工程中に粉末粒子内部の水分が抜け切らず、加硫成形の工程中まで一部の水分が残存するものと推測される。 On the other hand, as shown in Comparative Examples 4 and 5, when the modified cellulose powder was blended, the surface on ice and the wet road surface were suppressed with respect to Comparative Example 1 as a control while suppressing a decrease in wear resistance performance and rolling resistance performance. The braking performance in the car could be improved. When modified cellulose is blended, it is recognized that even if no foaming agent is used, a microvoid structure having uniform fine bubbles with an average pore diameter of 20 to 80 μm, more specifically about 40 to 50 μm, is formed in the rubber. It was. Therefore, in addition to the water absorption and water removal effects due to the hydrophilicity of the modified cellulose itself, this microvoid structure also exhibits water absorption, water removal and edge effects when forming tires, and maintains excellent wet braking performance and on-ice braking performance. It is thought that it has contributed. Although the mechanism by which the microvoid structure is formed is not clear, it is presumed that moisture and volatile components generated during mixing of the tire composition are captured in a dispersed state due to the presence of carboxymethylcellulose molecules. That is, since carboxymethyl cellulose has high hygroscopicity, it is presumed that the moisture inside the powder particles is not completely removed during the kneading process, and that some moisture remains until the vulcanization molding process.
このように変性セルロース粉末単独でも、氷上制動性能及び湿潤制動性能の向上はみられたが、変性セルロース粉末に炭酸カルシウムや酸化マグネシウムを併用することにより、実施例１〜３に示されたように、氷上制動性能及び湿潤制動性能において更なる改善効果が認められた。これは、上述したように、カルボキシアルキルセルロース分子がカルシウムイオンやマグネシウムイオンを介して三次元網目構造を形成し、親水性の空洞を生成するものと考えられる。すなわち、変性セルロース粉末自体による上記ミクロボイド構造とともに、アルカリ土類金属イオンを配合することにより形成される複合構造による親水性の空洞（ミクロボイド）により、より一層効果的に吸水、除水効果が発揮されて、湿潤制動性能及び氷上制動性能の更なる改善が図られるものと考えられる。その一方で、これら実施例１〜３では、耐摩耗性能と転がり抵抗性能については、比較例４及び５に対して同等以上であり、これらの性能の低下を伴うものではなかった。 Thus, even with the modified cellulose powder alone, improvement in braking performance on ice and wet braking performance was observed, but by using calcium carbonate and magnesium oxide in combination with the modified cellulose powder, as shown in Examples 1 to 3 Further improvements in ice braking performance and wet braking performance were observed. As described above, this is considered that the carboxyalkyl cellulose molecule forms a three-dimensional network structure via calcium ions or magnesium ions, thereby generating a hydrophilic cavity. In other words, the water absorption and dewatering effects are more effectively exhibited by the hydrophilic voids (microvoids) formed by compounding alkaline earth metal ions together with the microvoid structures formed by the modified cellulose powder itself. Therefore, it is considered that the wet braking performance and the braking performance on ice are further improved. On the other hand, in Examples 1 to 3, the wear resistance performance and the rolling resistance performance were equal to or greater than those of Comparative Examples 4 and 5, and these performances were not deteriorated.
本発明のゴム組成物は、乗用車、ライトトラック、トラック・バス等の各種タイヤに用いることができる。 The rubber composition of the present invention can be used for various tires such as passenger cars, light trucks, trucks and buses.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012029457A JP5918560B2 (en) | 2012-02-14 | 2012-02-14 | Rubber composition for tire and pneumatic tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012029457A JP5918560B2 (en) | 2012-02-14 | 2012-02-14 | Rubber composition for tire and pneumatic tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013166815A true JP2013166815A (en) | 2013-08-29 |
| JP5918560B2 JP5918560B2 (en) | 2016-05-18 |
Family
ID=49177487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012029457A Active JP5918560B2 (en) | 2012-02-14 | 2012-02-14 | Rubber composition for tire and pneumatic tire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5918560B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013237810A (en) * | 2012-05-16 | 2013-11-28 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread, and pneumatic tire |
| JP2017008207A (en) * | 2015-06-22 | 2017-01-12 | 株式会社ブリヂストン | Rubber composition, laminate, and conveyor belt |
| JP2017222848A (en) * | 2016-05-25 | 2017-12-21 | ライプニッツ−インスティチュート フュア ポリマーフォルシュング ドレスデン エーファウＬｅｉｂｎｉｚ−Ｉｎｓｔｉｔｕｔ ｆｕｅｒ Ｐｏｌｙｍｅｒｆｏｒｓｃｈｕｎｇ Ｄｒｅｓｄｅｎ ｅ．Ｖ． | Elastomer composition and method for producing the composition |
| WO2019031144A1 (en) * | 2017-08-10 | 2019-02-14 | 株式会社ブリヂストン | Rubber composition, production method therefor, and tire |
| JP2020015815A (en) * | 2018-07-25 | 2020-01-30 | 住友ゴム工業株式会社 | Rubber composition, pneumatic tire and vulcanization bladder |
| JP2020180253A (en) * | 2019-04-26 | 2020-11-05 | 横浜ゴム株式会社 | Rubber composition for studless tire and studless tire |
| JP2020203983A (en) * | 2019-06-17 | 2020-12-24 | 株式会社ブリヂストン | Rubber composition, tire rubber composition, crawler rubber composition, tire and rubber crawler |
| JP2020203982A (en) * | 2019-06-17 | 2020-12-24 | 株式会社ブリヂストン | Vulcanized rubber, tire and rubber crawler |
| WO2021049122A1 (en) | 2019-09-13 | 2021-03-18 | 株式会社Ｔｂｍ | Biodegradable rubber composition, method for producing biodegradable rubber composition, and biodegradable molded rubber article |
| KR20220010680A (en) * | 2020-07-17 | 2022-01-26 | 한국생산기술연구원 | Silica-rubber composite composition containing cellulose derivative dispersant and method for producing the same |
| WO2022176825A1 (en) * | 2021-02-19 | 2022-08-25 | 株式会社ダイセル | Cellulose acylate composition and production method therefor |
| WO2023079949A1 (en) * | 2021-11-05 | 2023-05-11 | 株式会社ブリヂストン | Rubber composition for tire, rubber member for tire, and tire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03159803A (en) * | 1989-11-17 | 1991-07-09 | Sumitomo Rubber Ind Ltd | Studless tire |
| JP2010059248A (en) * | 2008-09-01 | 2010-03-18 | Sumitomo Rubber Ind Ltd | Rubber composition for studless tire and studless tire |
| WO2011073188A1 (en) * | 2009-12-18 | 2011-06-23 | Societe De Technologie Michelin | Winter tyre with improved grip on ice |
-
2012
- 2012-02-14 JP JP2012029457A patent/JP5918560B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03159803A (en) * | 1989-11-17 | 1991-07-09 | Sumitomo Rubber Ind Ltd | Studless tire |
| JP2010059248A (en) * | 2008-09-01 | 2010-03-18 | Sumitomo Rubber Ind Ltd | Rubber composition for studless tire and studless tire |
| WO2011073188A1 (en) * | 2009-12-18 | 2011-06-23 | Societe De Technologie Michelin | Winter tyre with improved grip on ice |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013237810A (en) * | 2012-05-16 | 2013-11-28 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread, and pneumatic tire |
| JP2017008207A (en) * | 2015-06-22 | 2017-01-12 | 株式会社ブリヂストン | Rubber composition, laminate, and conveyor belt |
| JP2017222848A (en) * | 2016-05-25 | 2017-12-21 | ライプニッツ−インスティチュート フュア ポリマーフォルシュング ドレスデン エーファウＬｅｉｂｎｉｚ−Ｉｎｓｔｉｔｕｔ ｆｕｅｒ Ｐｏｌｙｍｅｒｆｏｒｓｃｈｕｎｇ Ｄｒｅｓｄｅｎ ｅ．Ｖ． | Elastomer composition and method for producing the composition |
| WO2019031144A1 (en) * | 2017-08-10 | 2019-02-14 | 株式会社ブリヂストン | Rubber composition, production method therefor, and tire |
| JP7201596B2 (en) | 2017-08-10 | 2023-01-10 | 株式会社ブリヂストン | Rubber composition, manufacturing method thereof, and tire |
| JPWO2019031144A1 (en) * | 2017-08-10 | 2020-08-27 | 株式会社ブリヂストン | Rubber composition, method for producing the same, and tire |
| JP7151243B2 (en) | 2018-07-25 | 2022-10-12 | 住友ゴム工業株式会社 | Rubber composition, pneumatic tire and vulcanized bladder |
| JP2020015815A (en) * | 2018-07-25 | 2020-01-30 | 住友ゴム工業株式会社 | Rubber composition, pneumatic tire and vulcanization bladder |
| JP2020180253A (en) * | 2019-04-26 | 2020-11-05 | 横浜ゴム株式会社 | Rubber composition for studless tire and studless tire |
| JP7381835B2 (en) | 2019-04-26 | 2023-11-16 | 横浜ゴム株式会社 | Rubber composition for studless tires and studless tires |
| JP2020203982A (en) * | 2019-06-17 | 2020-12-24 | 株式会社ブリヂストン | Vulcanized rubber, tire and rubber crawler |
| JP2020203983A (en) * | 2019-06-17 | 2020-12-24 | 株式会社ブリヂストン | Rubber composition, tire rubber composition, crawler rubber composition, tire and rubber crawler |
| JP7333208B2 (en) | 2019-06-17 | 2023-08-24 | 株式会社ブリヂストン | Rubber composition, rubber composition for tire, rubber composition for crawler, tire and rubber crawler |
| JP7204588B2 (en) | 2019-06-17 | 2023-01-16 | 株式会社ブリヂストン | Vulcanized rubber, tires and rubber crawlers |
| JP2021042347A (en) * | 2019-09-13 | 2021-03-18 | 株式会社Ｔｂｍ | Biodegradable rubber composition, method for producing biodegradable rubber composition, and biodegradable molded rubber article |
| KR20220043224A (en) | 2019-09-13 | 2022-04-05 | 가부시키가이샤 티비엠 | Biodegradable rubber composition, manufacturing method of biodegradable rubber composition, and biodegradable rubber molded article |
| WO2021049122A1 (en) | 2019-09-13 | 2021-03-18 | 株式会社Ｔｂｍ | Biodegradable rubber composition, method for producing biodegradable rubber composition, and biodegradable molded rubber article |
| KR102389823B1 (en) | 2020-07-17 | 2022-04-26 | 한국생산기술연구원 | Silica-rubber composite composition containing cellulose derivative dispersant and method for producing the same |
| KR20220010680A (en) * | 2020-07-17 | 2022-01-26 | 한국생산기술연구원 | Silica-rubber composite composition containing cellulose derivative dispersant and method for producing the same |
| WO2022176825A1 (en) * | 2021-02-19 | 2022-08-25 | 株式会社ダイセル | Cellulose acylate composition and production method therefor |
| WO2023079949A1 (en) * | 2021-11-05 | 2023-05-11 | 株式会社ブリヂストン | Rubber composition for tire, rubber member for tire, and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5918560B2 (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5918560B2 (en) | Rubber composition for tire and pneumatic tire | |
| JP5694010B2 (en) | Rubber composition for tire | |
| JP5436953B2 (en) | Rubber composition and pneumatic tire | |
| JP5301338B2 (en) | Heavy duty tire tread rubber composition and heavy duty pneumatic tire | |
| CN110382613B (en) | Tread rubber composition for studless tire | |
| JP6094614B2 (en) | Rubber composition for tire, method for producing thermally expandable microcapsule composite, and pneumatic tire using the composition | |
| JP5851763B2 (en) | COMPOSITE MANUFACTURING METHOD, RUBBER COMPOSITION, AND PNEUMATIC TIRE | |
| US20170088699A1 (en) | Rubber composition for tire tread and method for producing the same | |
| CN104448411B (en) | Rubber composition for tire tread and pneumatic tire | |
| EP3112412B1 (en) | Rubber composition for studless winter tires, and studless winter tire | |
| JP7357841B2 (en) | Rubber composition for tires, pneumatic tires using the same, and studless tires | |
| JP2005029708A (en) | Studless tire rubber composition | |
| JP6437391B2 (en) | Rubber composition for tire, tire and method for producing the same | |
| CN107936313B (en) | Rubber composition for studless tire and studless tire | |
| JP5730705B2 (en) | Rubber composition for tire tread and pneumatic tire | |
| JP6420206B2 (en) | Rubber composition for tire tread | |
| JP6617011B2 (en) | Rubber composition for studless tire | |
| JP2009029992A (en) | Rubber composition for tire tread | |
| JP6129673B2 (en) | Rubber composition and tire manufacturing method | |
| JP6113419B2 (en) | Rubber composition for tire tread and pneumatic tire | |
| JP2018090669A (en) | Rubber composition for studless tire, and studless tire | |
| JP2017222817A (en) | Rubber composition | |
| KR101571049B1 (en) | Rubber composition for racing tire tread and manufacturing method of the same | |
| JP2011168717A (en) | Rubber composition for tire | |
| JP2011168719A (en) | Rubber composition for tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150129 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150812 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150901 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151023 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160322 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160408 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5918560 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |