JP6713392B2 - Resin composition, friction material using the same, friction member, and brake shoe for drum brake - Google Patents
Resin composition, friction material using the same, friction member, and brake shoe for drum brake Download PDFInfo
- Publication number
- JP6713392B2 JP6713392B2 JP2016189846A JP2016189846A JP6713392B2 JP 6713392 B2 JP6713392 B2 JP 6713392B2 JP 2016189846 A JP2016189846 A JP 2016189846A JP 2016189846 A JP2016189846 A JP 2016189846A JP 6713392 B2 JP6713392 B2 JP 6713392B2
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- JP
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- Prior art keywords
- resin composition
- rubber
- friction
- titanate compound
- friction material
- 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.)
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- 239000002783 friction material Substances 0.000 title claims description 62
- 239000011342 resin composition Substances 0.000 title claims description 54
- -1 titanate compound Chemical class 0.000 claims description 70
- 239000002245 particle Substances 0.000 claims description 66
- 229920001971 elastomer Polymers 0.000 claims description 35
- 239000005060 rubber Substances 0.000 claims description 35
- 239000011148 porous material Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 23
- 229920001187 thermosetting polymer Polymers 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 239000005011 phenolic resin Substances 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 229920003049 isoprene rubber Polymers 0.000 claims description 6
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 6
- 239000004636 vulcanized rubber Substances 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 25
- 239000000835 fiber Substances 0.000 description 25
- 239000010936 titanium Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 230000001186 cumulative effect Effects 0.000 description 10
- 238000010304 firing Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000007908 dry granulation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940007424 antimony trisulfide Drugs 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000005550 wet granulation Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Braking Arrangements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、樹脂組成物、これを用いた摩擦材、摩擦部材、及びドラムブレーキ用ブレーキシューに関する。 The present invention relates to a resin composition, a friction material using the same, a friction member, and a brake shoe for a drum brake.
各種車両、産業機械等のブレーキシステムに用いられる摩擦材は、摩擦係数が高く安定していること、耐摩耗性が優れていることが求められている。これらの特性を満足させるために、チタン酸カリウム繊維、無機充填材、有機充填材等と、これらを結合するフェノール樹脂等の熱硬化性樹脂からなる樹脂組成物が摩擦材として用いられてきた。チタン酸カリウム繊維は、アスベストのような発癌性を有さず、金属繊維のようにローターを傷付けない。 Friction materials used in brake systems for various vehicles and industrial machines are required to have a high coefficient of friction and stability and excellent wear resistance. In order to satisfy these characteristics, a resin composition composed of potassium titanate fiber, an inorganic filler, an organic filler and the like and a thermosetting resin such as a phenol resin which binds these fibers has been used as a friction material. Potassium titanate fibers are not carcinogenic like asbestos and do not scratch the rotor like metal fibers.
しかし、チタン酸カリウム繊維は平均繊維径が０．１〜０．５μｍ、平均繊維長が１０〜２０μｍのものが多く、世界保健機関（ＷＨＯ）で推奨されている範囲（吸入繊維とするＷＨＯファイバー：平均短径が３μｍ以下、平均繊維長が５μｍ以上及びアスペクト比が３以上の繊維状化合物以外）には含まれていない。 However, potassium titanate fibers often have an average fiber diameter of 0.1 to 0.5 μm and an average fiber length of 10 to 20 μm, and are in a range recommended by the World Health Organization (WHO) (WHO fiber to be inhaled fiber). : Other than fibrous compounds having an average minor axis of 3 μm or less, an average fiber length of 5 μm or more and an aspect ratio of 3 or more).
また、チタン酸カリウム繊維は高温域での耐摩耗性が十分ではない。そこで、特許文献１では鱗片状のチタン酸マグネシウムカリウム、特許文献２では鱗片状のチタン酸リチウムカリウム、特許文献３ではアメーバ状のチタン酸カリウムが提案されている。また、非特許文献１〜３では、チタン酸塩化合物を含有したフェノール樹脂を摩擦材として用いることで、凝着性の高いフェノール樹脂熱分解物の生成が抑制され、摩擦係数が安定化することが示唆されている。 Further, the potassium titanate fiber does not have sufficient wear resistance in a high temperature range. Therefore, Patent Document 1 proposes scaly magnesium potassium titanate, Patent Document 2 proposes scaly lithium potassium titanate, and Patent Document 3 proposes amoebic potassium titanate. Further, in Non-Patent Documents 1 to 3, by using a phenol resin containing a titanate compound as a friction material, generation of a highly adhesive phenol resin thermal decomposition product is suppressed and the friction coefficient is stabilized. Is suggested.
さらに、摩擦材は制動時に発生するブレーキノイズ（鳴き）の低減も求められている。鳴きは、摩擦材とローターとが触れたことによって発生する微小な摩擦振動が、ローター本体により増幅されて音となったものである。特にドラムブレーキの場合、ドラムがスピーカーとなるため音が大きくなり非常に不快なものとなる。そこで、特許文献４では鳴きの発生要因となる振動を減衰させるためにゴムを含有した樹脂組成物を摩擦材として用いることが提案されている。 Further, the friction material is also required to reduce brake noise (squeaking) generated during braking. The squeal is a sound in which a minute frictional vibration generated by the contact between the friction material and the rotor is amplified by the rotor body. Especially in the case of a drum brake, the sound becomes loud because the drum serves as a speaker, which is very uncomfortable. Therefore, in Patent Document 4, it is proposed to use a resin composition containing rubber as a friction material in order to damp vibrations that cause squeal.
一方で、ドラムブレーキは、半円弧状のブレーキシューの表面において摩擦材が貼られていることから、ディスクブレーキに用いられる摩擦材よりも柔軟であることが求められている。そのため、ゴムを含有した樹脂組成物が摩擦材として多く用いられている。 On the other hand, the drum brake is required to be more flexible than the friction material used for the disc brake, because the friction material is attached to the surface of the semicircular brake shoe. Therefore, a resin composition containing rubber is often used as a friction material.
摩擦材として、より摩擦摩耗特性が優れているもの、柔軟なものが求められている。しかし、チタン酸塩化合物とゴムとを含有した樹脂組成物を摩擦材として用いた場合、チタン酸塩化合物を含有しない樹脂組成物を摩擦材として用いた場合と比較して摩擦特性が低下することがある。 As the friction material, a material having more excellent friction and wear characteristics and a soft material are required. However, when a resin composition containing a titanate compound and rubber is used as a friction material, friction characteristics are deteriorated as compared with the case where a resin composition containing no titanate compound is used as a friction material. There is.
本発明の目的は、優れた摩擦特性と柔軟性とを与えることができる樹脂組成物、該樹脂組成物を用いた摩擦材、摩擦部材、及びドラムブレーキ用ブレーキシューを提供することにある。 An object of the present invention is to provide a resin composition that can provide excellent friction characteristics and flexibility, a friction material using the resin composition, a friction member, and a brake shoe for a drum brake.
本発明者は、上記のように摩擦特性が低下する理由として、摩擦界面の組成に着目し鋭意研究を重ねた。その結果、ローター温度が上昇しない低負荷条件の摩擦における未加硫ゴム由来の被膜形成が大きく寄与していると考えられ、チタン酸塩化合物の結晶粒が結合してなる多孔質チタン酸塩化合物粒子と、未加硫ゴムとを含有する樹脂組成物が、上記目的を達成することを見出し、本発明を完成するに至った。 The present inventor has conducted extensive studies focusing on the composition of the friction interface as the reason for the deterioration of the frictional characteristics as described above. As a result, it is considered that the formation of a film derived from unvulcanized rubber in friction under a low load condition in which the rotor temperature does not increase largely contributes to the formation of a porous titanate compound in which crystal grains of the titanate compound are bonded. It has been found that a resin composition containing particles and an unvulcanized rubber achieves the above object, and has completed the present invention.
すなわち、本発明は、以下の樹脂組成物、摩擦材、摩擦部材及びドラムブレーキ用ブレーキシューを提供する。 That is, the present invention provides the following resin composition, friction material, friction member, and brake shoe for a drum brake.
項１ 細孔直径０．０１〜１．０μｍの範囲の積算細孔容積が５％以上であり、チタン酸塩化合物の結晶粒が結合してなる多孔質チタン酸塩化合物粒子と、未加硫ゴムと、熱硬化性樹脂とを含有する、樹脂組成物。 Item 1 Porous titanate compound particles having an integrated pore volume of 5% or more in the range of pore diameters of 0.01 to 1.0 μm, in which crystal grains of titanate compounds are bonded, and unvulcanized A resin composition containing rubber and a thermosetting resin.
項２ 前記多孔質チタン酸塩化合物粒子の平均粒子径が、５〜５００μｍである、項１に記載の樹脂組成物。 Item 2. The resin composition according to Item 1, wherein the porous titanate compound particles have an average particle diameter of 5 to 500 μm.
項３ 前記多孔質チタン酸塩化合物粒子が、組成式Ａ２ＴｉｎＯ（２ｎ＋１）〔式中、Ａはアルカリ金属から選ばれる１種又は２種以上、ｎ＝２〜８〕で表される、項１又は２に記載の樹脂組成物。 Item 3 The porous titanate compound particles are represented by a composition formula A 2 Ti n O (2n+1) [wherein, A is one or more selected from alkali metals, n=2 to 8]. The resin composition according to item 1 or 2.
項４ 前記未加硫ゴムが、天然ゴム、スチレン・ブタジエンゴム、ブタジエンゴム、イソプレンゴム、ニトリルゴム、クロロプレンゴム、ブチルゴム、及びエチレン・プロピレンゴムから選ばれる少なくとも１種である、項１〜３のいずれか一項に記載の樹脂組成物。 Item 4 The items 1 to 3, wherein the unvulcanized rubber is at least one selected from natural rubber, styrene/butadiene rubber, butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, butyl rubber, and ethylene/propylene rubber. The resin composition according to any one of claims.
項５ 前記熱硬化性樹脂がフェノール樹脂である、項１〜４のいずれか一項に記載の樹脂組成物。 Item 5 The resin composition according to any one of Items 1 to 4, wherein the thermosetting resin is a phenol resin.
項６ 前記多孔質チタン酸塩化合物粒子の含有量が１〜３０体積％であり、前記未加硫ゴムの含有量が０．１〜３０体積％であり、前記熱硬化性樹脂の含有量が１〜５０体積％である、項１〜５のいずれか一項に記載の樹脂組成物。 Item 6 The content of the porous titanate compound particles is 1 to 30% by volume, the content of the unvulcanized rubber is 0.1 to 30% by volume, and the content of the thermosetting resin is Item 6. The resin composition according to any one of items 1 to 5, which is 1 to 50% by volume.
項７ 摩擦材用である、項１〜６のいずれか一項に記載の樹脂組成物。 Item 7. The resin composition according to any one of Items 1 to 6, which is for a friction material.
項８ 項１〜７のいずれか一項に記載の樹脂組成物の成形体である、摩擦材。 Item 8. A friction material, which is a molded product of the resin composition according to any one of Items 1 to 7.
項９ ＪＩＳ Ｄ４４２１に準拠して測定されたロックウェル硬度が、６０〜７０ＨＲＳである、項８に記載の摩擦材。 Item 9 The friction material according to item 8, wherein the Rockwell hardness measured according to JIS D4421 is 60 to 70 HRS.
項１０ 項８又は９に記載の摩擦材を備える、摩擦部材。 Item 10 A friction member comprising the friction material according to item 8 or 9.
項１１ シュー基材と、項８又は９に記載の摩擦材からなるライニングとを備える、ドラムブレーキ用ブレーキシュー。 Item 11 A brake shoe for a drum brake, comprising a shoe base material and a lining made of the friction material according to Item 8 or 9.
本発明の樹脂組成物を摩擦材として用いた場合、優れた摩擦特性と柔軟性とを付与することができる。本発明の樹脂組成物を用いることにより、優れた摩擦特性と柔軟性を有する摩擦材、摩擦部材、及びドラムブレーキ用ブレーキシューを提供することができる。 When the resin composition of the present invention is used as a friction material, excellent friction characteristics and flexibility can be imparted. By using the resin composition of the present invention, a friction material having excellent friction characteristics and flexibility, a friction member, and a brake shoe for a drum brake can be provided.
本発明の摩擦材、摩擦部材、及びドラムブレーキ用ブレーキシューは、優れた摩擦特性と柔軟性を有する。 The friction material, the friction member, and the brake shoe for the drum brake of the present invention have excellent friction characteristics and flexibility.
以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は単なる例示である。本発明は、下記の実施形態に何ら限定されない。 Hereinafter, an example of a preferable mode for carrying out the present invention will be described. However, the following embodiments are merely examples. The present invention is not limited to the embodiments described below.
＜樹脂組成物＞
本発明の樹脂組成物は、チタン酸塩化合物の結晶粒が結合してなる多孔質チタン酸塩化合物粒子と、未加硫ゴムと、熱硬化性樹脂とを含有する摩擦材用樹脂組成物であることを特徴とする。上記多孔質チタン酸塩化合物粒子における細孔直径０．０１〜１．０μｍの範囲の積算細孔容積は、５％以上である。本発明の樹脂組成物は、必要に応じて、その他材料をさらに含有することができる。
<Resin composition>
The resin composition of the present invention is a resin composition for a friction material containing porous titanate compound particles in which crystal grains of a titanate compound are bonded, unvulcanized rubber, and a thermosetting resin. It is characterized by The cumulative pore volume of the porous titanate compound particles in the pore diameter range of 0.01 to 1.0 μm is 5% or more. The resin composition of the present invention may further contain other materials, if necessary.
以下に、本発明の樹脂組成物の各構成成分について説明する。 Below, each component of the resin composition of this invention is demonstrated.
（多孔質チタン酸塩化合物粒子）
本発明で使用する多孔質チタン酸塩化合物粒子は、細孔直径０．０１〜１．０μｍの範囲の積算細孔容積が５％以上であり、チタン酸塩化合物の結晶粒が焼結及び／又は融着等により結合してなる多孔質チタン酸塩化合物粒子である。すなわち、上記多孔質チタン酸塩化合物粒子は、チタン酸塩化合物の結晶粒の結合体である。
(Porous titanate compound particles)
The porous titanate compound particles used in the present invention have an integrated pore volume of 5% or more in the pore diameter range of 0.01 to 1.0 μm, and the crystal grains of the titanate compound are sintered and/or Alternatively, it is a porous titanate compound particle formed by bonding by fusion or the like. That is, the porous titanate compound particles are a combination of crystal particles of the titanate compound.
本発明において、上記積算細孔容積は、好ましくは１０％以上であり、より好ましくは１５％以上である。上記積算細孔容積の好ましい上限値は４０％であり、より好ましくは３０％である。上記積算細孔容積が小さすぎると、優れた摩擦特性が得られない場合がある。上記積算細孔容積が大きすぎると、チタン酸塩化合物の結晶粒間の結合部分が弱くなり、多孔質構造が保てなくなる場合がある。上記積算細孔容積は、水銀圧入法により測定することができる。 In the present invention, the cumulative pore volume is preferably 10% or more, more preferably 15% or more. The preferable upper limit of the cumulative pore volume is 40%, more preferably 30%. If the cumulative pore volume is too small, excellent friction characteristics may not be obtained. If the cumulative pore volume is too large, the bonded portion between the crystal grains of the titanate compound may be weakened and the porous structure may not be maintained. The cumulative pore volume can be measured by the mercury penetration method.
本発明で使用する多孔質チタン酸塩化合物粒子のＢＥＴ比表面積は、１〜１３ｍ２／ｇの範囲内であることが好ましく、３〜９ｍ２／ｇの範囲内であることがより好ましい。上記ＢＥＴ比表面積が小さすぎると、優れた摩擦特性が得られない場合がある。上記ＢＥＴ比表面積が大きすぎると、焼成工程における化学反応が完結していない場合がある。 BET specific surface area of the porous titanate compound particles used in the present invention is preferably in the range of 1~13m 2 / g, more preferably in the range of 3~9m 2 / g. If the BET specific surface area is too small, excellent friction characteristics may not be obtained. If the BET specific surface area is too large, the chemical reaction in the firing step may not be completed.
本発明で使用する多孔質チタン酸塩化合物粒子の粒子形状は、球状、不定形状等の粉末状であることが好ましく、また非繊維状であることが好ましい。特に、球状であることがより好ましい。 The particle shape of the porous titanate compound particles used in the present invention is preferably in the form of powder such as sphere and irregular shape, and is preferably non-fibrous. In particular, the spherical shape is more preferable.
本発明で使用する多孔質チタン酸塩化合物粒子の粒子サイズは特に制限されないが、平均粒子径が５〜５００μｍであることが好ましく、１０〜３００μｍであることがより好ましく、２０〜１５０μｍであることがさらに好ましい。本発明において平均粒子径は、超音波による分散を行わないレーザー回折・散乱法によって求めた粒度分布における積算値５０％の粒子径を意味する。これらの各種粒子形状及び粒子サイズは、製造条件、特に原料組成、焼成条件、粉砕処理条件等により任意に制御することができる。 The particle size of the porous titanate compound particles used in the present invention is not particularly limited, but the average particle size is preferably 5 to 500 μm, more preferably 10 to 300 μm, and further preferably 20 to 150 μm. Is more preferable. In the present invention, the average particle size means a particle size with an integrated value of 50% in a particle size distribution obtained by a laser diffraction/scattering method without dispersion by ultrasonic waves. These various particle shapes and particle sizes can be arbitrarily controlled by the production conditions, particularly the raw material composition, the firing conditions, the pulverization processing conditions and the like.
多孔質チタン酸塩化合物粒子を構成するチタン酸塩化合物としては、組成式Ａ２ＴｉｎＯ（２ｎ＋１）［式中、Ａはアルカリ金属から選ばれる１種又は２種以上、ｎ＝２〜８］、ＭｘＡｙＴｉ（２−ｙ）Ｏ４［式中、Ｍはリチウムを除くアルカリ金属、Ａはリチウム、マグネシウム、亜鉛、ニッケル、銅、鉄、アルミニウム、ガリウム、マンガンより選ばれる１種又は２種以上、ｘ＝０．５〜１．０、ｙ＝０．２５〜１．０］、Ｋ０．５〜０．８Ｌｉ０．２７Ｔｉ１．７３Ｏ３．８５〜４、Ｋ０．２〜０．８Ｍｇ０．４Ｔｉ１．６Ｏ３．７〜４等で表されるチタン酸塩化合物を挙げることができる。 The titanate compound constituting the porous titanate compound particles has a composition formula A 2 Ti n O (2n+1) [wherein A is one or more selected from alkali metals, and n=2 to 8]. ], M x a y Ti in (2-y) O 4 [wherein, M is an alkali metal except lithium, a is lithium, magnesium, zinc, nickel, copper, iron, aluminum, gallium, one selected from manganese or two or more, x = 0.5~1.0, y = 0.25~1.0 ], K 0.5~0.8 Li 0.27 Ti 1.73 O 3.85~4, K 0.2~0.8 Mg 0.4 Ti 1.6 O titanate compound represented by like 3.7 to 4 can be exemplified.
チタン酸塩化合物はアルカリ成分が多く、結晶構造が化学的に不安定であると、樹脂組成物の成形時にアルカリ成分が溶出して、マトリックスを構成する熱硬化性樹脂の劣化を起こすことがある。これは溶出したアルカリ成分により熱硬化性樹脂の硬化阻害を起こすためと考えられる。上述のチタン酸塩化合物のなかでも、結晶構造がトンネル構造でありアルカリの溶出を抑えることできる点で、組成式Ａ２ＴｉｎＯ（２ｎ＋１）［式中、Ａはアルカリ金属から選ばれる１種又は２種以上、ｎ＝２〜８］で表されるチタン酸塩化合物であることが好ましく、組成式Ａ２Ｔｉ６Ｏ１３［式中、Ａはアルカリ金属から選ばれる１種又は２種以上］で表されるチタン酸塩化合物であることがより好ましい。アルカリ金属としてはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、フランシウムがあり、このなかでも経済的に有利な点からリチウム、ナトリウム、カリウムが好ましい。より具体的には、Ｌｉ２Ｔｉ６Ｏ１３、Ｋ２Ｔｉ６Ｏ１３、Ｎａ２Ｔｉ６Ｏ１３等を例示することができる。 If the titanate compound has a large amount of alkali component and its crystal structure is chemically unstable, the alkali component may elute during the molding of the resin composition, which may cause deterioration of the thermosetting resin constituting the matrix. .. It is considered that this is because the eluted alkali component causes the curing inhibition of the thermosetting resin. Among the above-mentioned titanate compounds, the crystal structure is a tunnel structure and the elution of alkali can be suppressed, so that the composition formula A 2 Ti n O (2n+1) [wherein A is one selected from alkali metals] Alternatively, the titanate compound represented by two or more kinds, n=2 to 8] is preferable, and the composition formula A 2 Ti 6 O 13 [wherein, A is one or more kinds selected from an alkali metal]. ] It is more preferable that it is a titanate compound represented by these. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium, and among these, lithium, sodium, and potassium are preferable because they are economically advantageous. More specifically, there can be mentioned Li 2 Ti 6 O 13, K 2 Ti 6 O 13, Na 2 Ti 6 O 13 and the like.
本発明の多孔質チタン酸塩化合物粒子の製造方法は、上述の特性を得ることができれば特に制限されないが、例えば、チタン源とアルカリ金属塩をメカニカルに粉砕をすることで得られる粉砕混合物を、乾式造粒し、焼成して製造する方法等を例示することができる。 The method for producing porous titanate compound particles of the present invention is not particularly limited as long as the above-mentioned properties can be obtained, for example, a pulverized mixture obtained by mechanically pulverizing a titanium source and an alkali metal salt, A method of producing by dry granulation and firing can be exemplified.
メカニカルな粉砕としては、物理的な衝撃を与えながら粉砕する方法が挙げられる。具体的には、振動ミルによる粉砕が挙げられる。振動ミルによる粉砕処理を行うことにより、混合粉体の摩砕によるせん断応力により、原子配列の乱れと原子間距離の減少が同時に起こり、異種粒子の接点部分の原子移動が起こる結果、準安定相が得られると考えられる。これにより、反応活性の高い粉砕混合物が得られ、後述の焼成温度を低くでき、粉砕混合物を造粒しても未反応物を低減することができる。メカニカルな粉砕は、原料に効率良くせん断応力を与えるため、水や溶剤を用いない乾式処理が好ましい。 Mechanical crushing includes a method of crushing while giving a physical impact. Specifically, pulverization with a vibration mill can be mentioned. By performing the pulverization process with the vibration mill, the shear stress due to the grinding of the mixed powder causes the disorder of the atomic arrangement and the decrease of the interatomic distance at the same time, resulting in the atom migration at the contact point of different particles, resulting in the metastable phase. Is believed to be obtained. As a result, a pulverized mixture having high reaction activity can be obtained, the firing temperature described below can be lowered, and unreacted substances can be reduced even if the pulverized mixture is granulated. Mechanical pulverization efficiently gives a shearing stress to the raw material, and thus a dry treatment that does not use water or a solvent is preferable.
メカニカルな粉砕による処理時間は、特に制限されるものではないが、一般に０．１〜２時間の範囲内であることが好ましい。 The treatment time by mechanical pulverization is not particularly limited, but it is generally preferably within the range of 0.1 to 2 hours.
粉砕混合物の造粒は、水及び溶剤を用いない乾式造粒で行われる。乾式造粒は、公知の方法で行うことができ、例えば転動造粒、流動層造粒、攪拌造粒等を例示することができる。湿式造粒は、造粒物の乾燥工程において、造粒物内部での液状物の気化に伴い、結果として内部に大きな空洞を有する多孔質粒子が得られ、粉体強度が低下するため好ましくない。また、水及び溶媒を気化させるために加熱が必要となり、量産性も悪い。 Granulation of the milled mixture is performed by dry granulation without water and solvent. The dry granulation can be carried out by a known method, and examples thereof include rolling granulation, fluidized bed granulation and stirring granulation. Wet granulation is not preferable because in the drying step of the granulated product, vaporization of the liquid material inside the granulated product results in the production of porous particles having large voids inside, which lowers the powder strength. .. Further, heating is required to vaporize water and a solvent, and mass productivity is poor.
造粒物を焼成する温度としては、目的とするチタン酸塩化合物の組成により適宜選択することができるが、６５０〜１０００℃の範囲であることが好ましく、８００〜９５０℃の範囲であることがさらに好ましい。焼成時間は、０．５〜８時間であることが好ましく、２〜６時間であることがさらに好ましい。 The temperature for firing the granulated product can be appropriately selected depending on the composition of the target titanate compound, but it is preferably in the range of 650 to 1000°C, and in the range of 800 to 950°C. More preferable. The firing time is preferably 0.5 to 8 hours, more preferably 2 to 6 hours.
チタン源としては、チタン元素を含有して焼成による酸化物の生成を阻害しない原材料であれば特に限定されないが、例えば空気中で焼成することにより酸化チタンに導かれる化合物等がある。かかる化合物としては、例えば酸化チタン、ルチル鉱石、水酸化チタンウェットケーキ、含水チタニア等が挙げられ、酸化チタンが好ましい。 The titanium source is not particularly limited as long as it is a raw material containing a titanium element and does not hinder the production of oxides by firing, and examples thereof include compounds that are converted into titanium oxide by firing in air. Examples of such compounds include titanium oxide, rutile ore, titanium hydroxide wet cake, hydrous titania, etc., with titanium oxide being preferred.
アルカリ金属塩としては、アルカリ金属の炭酸塩、炭酸水素塩、水酸化物、酢酸塩等の有機酸塩、硫酸塩、硝酸塩等があるが、炭酸塩が好ましい。 Examples of the alkali metal salt include alkali metal carbonates, hydrogen carbonates, hydroxides, organic acid salts such as acetates, sulfates and nitrates, and the carbonates are preferable.
チタン源とアルカリ金属塩の混合比は、目的とするチタン酸塩化合物の組成により適宜選択することができる。 The mixing ratio of the titanium source and the alkali metal salt can be appropriately selected depending on the composition of the target titanate compound.
本発明で使用する多孔質チタン酸塩化合物粒子は、上述のように細孔直径が小さいことから、多孔質粒子内への熱硬化性樹脂が含浸するのを抑制することができ、多孔質粒子内に多量の酸素を取り込んでいるものと考えられる。そのため、樹脂組成物を摩擦材として用いたとき、摩擦界面において上記多孔質チタン酸塩化合物粒子から放出された酸素が、摩擦時に生じる温度でゴムの不飽和構造に作用し、摩擦界面での未加硫ゴム由来の潤滑性被膜の形成を抑制するものと考えられる。従って、本発明の樹脂組成物は、酸化剤を併用しなくても優れた摩擦特性を得ることができる。さらに、本発明で使用する多孔質チタン酸塩化合物粒子は、摩擦特性を向上させるだけでなく、非繊維形状の多孔質体であることから、ＷＨＯファイバーが含まれない摩擦調整材としても期待される。 Porous titanate compound particles used in the present invention, since the pore diameter is small as described above, it is possible to suppress the thermosetting resin impregnation into the porous particles, the porous particles It is considered that a large amount of oxygen is taken in. Therefore, when the resin composition is used as a friction material, the oxygen released from the porous titanate compound particles at the friction interface acts on the unsaturated structure of the rubber at a temperature generated during friction, resulting in unreacted friction at the friction interface. It is considered to suppress the formation of a lubricating coating derived from vulcanized rubber. Therefore, the resin composition of the present invention can obtain excellent friction characteristics without using an oxidizing agent together. Furthermore, since the porous titanate compound particles used in the present invention not only improve friction characteristics but also are non-fibrous porous bodies, they are expected as friction modifiers that do not contain WHO fibers. It
本発明で使用する多孔質チタン酸塩化合物粒子は、分散性、熱硬化性樹脂との密着性向上等の目的として、シランカップリング剤、チタネート系カップリング剤等により表面処理を常法に従って施されていてもよい。 The porous titanate compound particles used in the present invention are subjected to a surface treatment by a conventional method with a silane coupling agent, a titanate coupling agent or the like for the purpose of improving dispersibility, adhesion with a thermosetting resin, or the like. It may have been done.
樹脂組成物における多孔質チタン酸塩化合物粒子の含有量は、樹脂組成物の合計量１００体積％に対して、１〜３０体積％であることが好ましく、１〜２０体積％であることがより好ましく、４〜１０体積％であることがさらに好ましい。チタン酸塩化合物の含有量を１〜３０体積％の範囲とすることで、優れた摩擦特性を得ることができる。 The content of the porous titanate compound particles in the resin composition is preferably 1 to 30% by volume, and more preferably 1 to 20% by volume with respect to 100% by volume of the total amount of the resin composition. It is more preferably 4 to 10% by volume. By setting the content of the titanate compound in the range of 1 to 30% by volume, excellent friction characteristics can be obtained.
（未加硫ゴム）
本発明で用いる未加硫ゴムとしては、室温（２０℃）で固体形状を有するものであれば特に制限なく用いることができ、例えば、天然ゴム（ＮＲ）、スチレン・ブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、イソプレンゴム（ＩＲ）、ニトリルゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）、エチレン・プロピレンゴム（ＥＰＤＭ）等が挙げられ、これらの１種を単独又は２種以上を組み合わせて用いることができる。これらのなかでも高不飽和ゴムであるスチレン・ブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、イソプレンゴム（ＩＲ）、ニトリルゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）が好ましい。
(Unvulcanized rubber)
The unvulcanized rubber used in the present invention can be used without particular limitation as long as it has a solid shape at room temperature (20° C.), and examples thereof include natural rubber (NR), styrene-butadiene rubber (SBR), and butadiene. Examples thereof include rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene rubber (EPDM), etc. One of these may be used alone or in combination of two or more. Can be used in combination. Of these, styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), and chloroprene rubber (CR), which are highly unsaturated rubbers, are preferable.
ゴムは、通常、摩擦材の剛性を低下させ振動の減衰性を向上させるために用いられているが、加硫ゴムは弾性が強いため、摩擦材の気孔率が大きくなる傾向がある。このため、加硫ゴムを用いた場合に摩擦材の気孔率を小さく制御しようと成形圧力を高くすると、摩擦材の剛性が大きくなる。しかし、未加硫ゴムは、成形時に一部が塑性変形するものと考えられることから、摩擦材の剛性と気孔率を制御しやすいという利点がある。 Rubber is usually used to reduce the rigidity of the friction material and improve the vibration damping property, but since vulcanized rubber has a strong elasticity, the porosity of the friction material tends to increase. Therefore, when vulcanized rubber is used, the rigidity of the friction material increases when the molding pressure is increased to control the porosity of the friction material to be small. However, unvulcanized rubber has a merit that it is easy to control the rigidity and the porosity of the friction material because it is considered that a part of the unvulcanized rubber is plastically deformed during molding.
本発明で用いる未加硫ゴムは、分散性の観点から粒子状であることが好ましい。平均粒子径が１〜３００μｍのものが好ましく、２０〜２００μｍのものがより好ましく、１００〜１５０μｍのものがさらに好ましい。 The unvulcanized rubber used in the present invention is preferably particulate from the viewpoint of dispersibility. The average particle size is preferably 1 to 300 μm, more preferably 20 to 200 μm, still more preferably 100 to 150 μm.
樹脂組成物における未加硫ゴムの含有量は、樹脂組成物の合計量１００体積％に対して、０．１〜３０体積％であることが好ましく、１〜２０体積％であることがより好ましく、５〜１５体積％であることがさらに好ましい。未加硫ゴムの含有量を０．１〜３０体積％の範囲とすることで、優れた柔軟性と摩擦特性を両立することができる。 The content of unvulcanized rubber in the resin composition is preferably 0.1 to 30% by volume, more preferably 1 to 20% by volume, based on 100% by volume of the total amount of the resin composition. , 5 to 15% by volume is more preferable. By setting the content of the unvulcanized rubber in the range of 0.1 to 30% by volume, excellent flexibility and frictional properties can both be achieved.
（熱硬化性樹脂）
熱硬化性樹脂は、多孔質チタン酸塩化合物粒子、未加硫ゴム等を一体化し、強度を与える結合材として用いられるものであり、結合材として用いられる公知の熱硬化性樹脂の中から任意のものを適宜選択して用いることができる。例えばフェノール樹脂；アクリルエラストマー分散フェノール樹脂、シリコーンエラストマー分散フェノール樹脂等のエラストマー分散フェノール樹脂；アクリル変性フェノール樹脂、シリコーン変性フェノール樹脂等の変性フェノール樹脂；ホルムアルデヒド樹脂；メラミン樹脂；エポキシ樹脂；アクリル樹脂；芳香族ポリエステル樹脂；ユリア樹脂；等を挙げることができ、これらの１種を単独又は２種以上を組み合わせて用いることができる。このなかでも耐熱性、成形性、摩擦特性をより一層向上できる点から、フェノール樹脂、変性フェノール樹脂が好ましい。
(Thermosetting resin)
The thermosetting resin is used as a binder that integrates porous titanate compound particles, unvulcanized rubber and the like to give strength, and can be selected from known thermosetting resins used as a binder. Those can be appropriately selected and used. For example, phenol resin; elastomer-dispersed phenol resin such as acrylic elastomer-dispersed phenol resin and silicone elastomer-dispersed phenol resin; modified phenol resin such as acrylic-modified phenol resin and silicone-modified phenol resin; formaldehyde resin; melamine resin; epoxy resin; acrylic resin; Group polyester resin; urea resin, etc. can be mentioned, and these 1 type can be used individually or in combination of 2 or more types. Of these, phenolic resins and modified phenolic resins are preferable because they can further improve heat resistance, moldability, and friction characteristics.
樹脂組成物における熱硬化性樹脂の含有量は、樹脂組成物の合計量１００体積％に対して、１〜５０体積％であることが好ましく、５〜４０体積％であることがより好ましく、１０〜３０体積％であることがさらに好ましい。熱硬化性樹脂の含有量を１〜５０体積％の範囲とすることで配合材料の隙間に適切な量の結合材が充填され、優れた摩擦特性を得ることができる。 The content of the thermosetting resin in the resin composition is preferably 1 to 50% by volume, more preferably 5 to 40% by volume, based on 100% by volume of the total amount of the resin composition. More preferably, it is -30% by volume. By setting the content of the thermosetting resin in the range of 1 to 50% by volume, an appropriate amount of the binder is filled in the gaps of the compounded material, and excellent friction characteristics can be obtained.
（その他材料）
本発明の摩擦材用樹脂組成物は、上記の多孔質チタン酸塩化合物粒子、未加硫ゴム、熱硬化性樹脂の材料以外に、必要に応じてその他材料を配合することができる。その他材料としては、例えば、以下の繊維基材、摩擦調整材等を挙げることができる。
(Other materials)
The resin composition for a friction material of the present invention may contain other materials, if necessary, in addition to the materials of the above-described porous titanate compound particles, unvulcanized rubber, and thermosetting resin. Examples of other materials include the following fibrous base materials and friction modifiers.
繊維基材としては、芳香族ポリアミド（アラミド）繊維、アクリル繊維、セルロース繊維、フェノール樹脂繊維等の有機繊維、スチール繊維、銅繊維、アルミナ繊維、亜鉛繊維等の金属繊維；ガラス繊維、ロックウール、セラミック繊維、生分解性繊維、生体溶解性繊維、ワラストナイト繊維等の無機繊維；炭素繊維等が挙げられ、これらの１種単独又は２種以上を組み合わせて使用することができる。 Examples of the fiber base material include organic fibers such as aromatic polyamide (aramid) fibers, acrylic fibers, cellulose fibers, and phenol resin fibers, metal fibers such as steel fibers, copper fibers, alumina fibers, and zinc fibers; glass fibers, rock wool, Inorganic fibers such as ceramic fibers, biodegradable fibers, biosoluble fibers, wollastonite fibers; carbon fibers and the like can be mentioned, and these can be used alone or in combination of two or more.
摩擦調整材としては、各種加硫ゴム粉末（タイヤ粉末等）、カシューダスト、メラミンダスト等の有機充填材；硫酸バリウム、炭酸カルシウム、炭酸リチウム、水酸化カルシウム、バーミキュライト、クレー、マイカ、タルク等の無機粉末、銅、青銅、アルミニウム、亜鉛、鉄、錫等の金属粉末、本発明で用いる多孔質チタン酸塩化合物粒子以外の球状、層状、板状、柱状、ブロック状、不定形状等の粒子形状のチタン酸塩化合物粉末等の無機充填材；シリコンカーバイト（炭化ケイ素）、酸化チタン、アルミナ（酸化アルミニウム）、シリカ（二酸化ケイ素）、マグネシア（酸化マグネシウム）、ジルコニア（酸化ジルコニウム）、ケイ酸ジルコニウム、酸化クロム、酸化鉄、クロマイト、石英等の研削材；合成又は天然黒鉛（グラファイト）、リン酸塩被覆黒鉛、カーボンブラック、コークス、三硫化アンチモン、二硫化モリブデン、硫化スズ、硫化鉄、硫化亜鉛、二硫化タングステン、ポリテトラフルオロエチレン（ＰＴＥＦ）等の固体潤滑材等が挙げられ、これらの１種単独又は２種以上を組み合わせて使用することができる。 Friction modifiers include various vulcanized rubber powders (tire powders, etc.), organic fillers such as cashew dust, melamine dust; barium sulfate, calcium carbonate, lithium carbonate, calcium hydroxide, vermiculite, clay, mica, talc, etc. Inorganic powder, metal powder such as copper, bronze, aluminum, zinc, iron, tin, etc., and particle shapes other than the porous titanate compound particles used in the present invention such as spherical, layered, plate-like, columnar, block-like, and irregular shape Inorganic filler such as titanate compound powder; silicon carbide (silicon carbide), titanium oxide, alumina (aluminum oxide), silica (silicon dioxide), magnesia (magnesium oxide), zirconia (zirconium oxide), zirconium silicate Abrasive materials such as chromium oxide, iron oxide, chromite, and quartz; synthetic or natural graphite (graphite), phosphate-coated graphite, carbon black, coke, antimony trisulfide, molybdenum disulfide, tin sulfide, iron sulfide, zinc sulfide Examples of the solid lubricants include tungsten disulfide, polytetrafluoroethylene (PTEF), and the like, and these can be used alone or in combination of two or more.
樹脂組成物におけるその他材料の含有量は、樹脂組成物の合計量１００体積％に対して、１０〜９０体積％であることが好ましく、２０〜９０体積％であることがより好ましく、４０〜８０体積％であることがさらに好ましい。 The content of the other material in the resin composition is preferably 10 to 90% by volume, more preferably 20 to 90% by volume, and 40 to 80% with respect to 100% by volume of the total amount of the resin composition. More preferably, it is the volume%.
（樹脂組成物の製造方法）
本発明の樹脂組成物は、（１）混合機（レーディゲミキサー、加圧ニーダー、アイリッヒミキサー等）で各成分を混合する方法；（２）所望する成分の造粒物を調製し、必要により他の成分を混合機（レーディゲミキサー、加圧ニーダー、アイリッヒミキサー等）で混合する方法等により製造することができる。
(Method for producing resin composition)
The resin composition of the present invention is (1) a method of mixing each component with a mixer (Ledige mixer, pressure kneader, Erich mixer, etc.); (2) preparing a granulated product of the desired component, If necessary, it can be produced by a method of mixing other components with a mixer (Ledige mixer, pressure kneader, Erich mixer, etc.).
本発明の樹脂組成物の各成分の含有量は、所望する摩擦特性、柔軟性により適宜選択することができ、上記の製造方法を用いて製造することができる。 The content of each component of the resin composition of the present invention can be appropriately selected according to desired frictional characteristics and flexibility, and can be produced using the above production method.
また、本発明の樹脂組成物は、特定の構成成分を高い濃度で含むマスターバッチを作製し、このマスターバッチに熱硬化性樹脂等を添加し混合することにより調製してもよい。 Further, the resin composition of the present invention may be prepared by preparing a masterbatch containing a specific constituent component in a high concentration, and adding a thermosetting resin or the like to the masterbatch and mixing them.
＜摩擦材及び摩擦部材＞
本発明の摩擦材は、本発明の樹脂組成物を、常温にて仮成形し、得られた仮成形物を加熱加圧成形（成形圧力１０〜４０ＭＰａ、成形温度１５０〜２００℃）し、必要に応じて、得られた成形体に加熱炉内で熱処理（１５０〜２００℃、１〜１２時間保持）を施し、しかる後その成形体に機械加工、研磨加工を加えて所定の形状を有する摩擦材を製造することができる。
<Friction material and friction member>
The friction material of the present invention is obtained by temporarily molding the resin composition of the present invention at room temperature and subjecting the obtained temporary molded product to heat and pressure molding (molding pressure 10 to 40 MPa, molding temperature 150 to 200°C). According to the above, heat treatment (150 to 200° C., holding for 1 to 12 hours) is performed on the obtained molded body, and then, the molded body is subjected to mechanical processing and polishing processing to obtain a friction having a predetermined shape. The material can be manufactured.
本発明の摩擦材は、該摩擦材を摩擦面となるように形成した摩擦部材として用いられる。摩擦材を用いて形成することができる摩擦部材としては、例えば、（１）摩擦材のみの構成、（２）裏金等の基材と、該基材の上に設けられ、摩擦面を与える本発明の摩擦材とを有する構成等が挙げられる。 The friction material of the present invention is used as a friction member in which the friction material is formed into a friction surface. Examples of the friction member that can be formed by using the friction material include (1) a structure of only the friction material, (2) a base material such as a backing metal, and a book provided on the base material to provide a friction surface. Examples include a configuration including the friction material of the invention.
上記基材は、摩擦部材の機械的強度をより一層向上させるために用いるものであり、材質としては、金属又は繊維強化樹脂等を用いることができる。例えば、鉄、ステンレス、ガラス繊維強化樹脂、炭素繊維樹脂等が挙げられる。 The base material is used to further improve the mechanical strength of the friction member, and as the material, metal or fiber reinforced resin can be used. Examples thereof include iron, stainless steel, glass fiber reinforced resin, carbon fiber resin and the like.
摩擦材には、通常、内部に微細な気孔が多数形成されており、高温時の分解生成物（ガスや液状物）の逃げ道となり摩擦特性の低下防止を図るとともに、摩擦材の剛性を下げ減衰性を向上させることで鳴きの発生を防止している。通常の摩擦材においては、気孔率が１０〜１４％になるように、材料の配合、成形条件を管理している。 Normally, many fine pores are formed inside the friction material, which serves as an escape route for decomposition products (gas and liquids) at high temperatures to prevent the deterioration of friction characteristics and reduce the rigidity of the friction material. Singing is prevented by improving the sound quality. In a normal friction material, material mixing and molding conditions are controlled so that the porosity is 10 to 14%.
本発明の摩擦材は、各種車両や産業機械のディスクブレーキ、ドラムブレーキ等の摩擦部材に用いることができる。また、本発明の摩擦材は、優れた摩擦特性と、柔軟性を有していることから、ドラムブレーキの摩擦部材に好適である。摩擦材を、ドラムブレーキの摩擦部材として用いる場合、摩擦材のロックウェル硬度を６０〜７０ＨＲＳになるように、材料の配合、成形条件を管理することが好ましい。 The friction material of the present invention can be used for friction members such as disc brakes and drum brakes of various vehicles and industrial machines. Further, the friction material of the present invention has excellent friction characteristics and flexibility, and thus is suitable for a friction member of a drum brake. When the friction material is used as a friction member of a drum brake, it is preferable to manage the material composition and molding conditions so that the Rockwell hardness of the friction material is 60 to 70 HRS.
＜ドラムブレーキ用ブレーキシュー＞
本発明のドラムブレーキ用ブレーキシューは、シュー基材と、上記摩擦材からなるライニングとを備える。従って、本発明のドラムブレーキ用ブレーキシューは、優れた摩擦特性と、柔軟性を有しており、ドラムブレーキに好適に用いることができる。
<Brake shoes for drum brakes>
A brake shoe for a drum brake of the present invention includes a shoe base material and a lining made of the friction material. Therefore, the brake shoe for a drum brake of the present invention has excellent friction characteristics and flexibility, and can be suitably used for a drum brake.
以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明する。本発明は、以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能である。なお、実施例及び比較例に用いたチタン酸塩化合物、未加硫ゴム及び熱硬化性樹脂は以下の通りである。 Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented within the scope of the invention. The titanate compound, unvulcanized rubber and thermosetting resin used in Examples and Comparative Examples are as follows.
（チタン酸塩化合物）
チタン酸塩化合物１〜６の組成式、粒子形状、平均粒子径、ＢＥＴ比表面積、細孔直径０．０１〜１．０μｍの範囲の積算細孔容積、及び細孔分布の極大値を下記の表１に示した。なお、チタン酸塩化合物１〜３は以下の通り製造した。
(Titanate compound)
The composition formula, particle shape, average particle diameter, BET specific surface area, cumulative pore volume in the range of 0.01 to 1.0 μm of pore diameter, and the maximum value of pore distribution of the titanate compounds 1 to 6 are shown below. The results are shown in Table 1. The titanate compounds 1 to 3 were manufactured as follows.
・チタン酸塩化合物１
Ｔｉ：Ｋ＝３：１（モル比）となるように秤量した酸化チタン及び炭酸カリウムを振動ミルにて粉砕しながら１０分間混合した。得られた粉砕混合物をハイスピードミキサーにて乾式造粒した後、電気炉にて８５０℃で４時間焼成することで粉末を得た。
・Titanate compound 1
Titanium oxide and potassium carbonate, which were weighed so that Ti:K=3:1 (molar ratio), were mixed for 10 minutes while being crushed by a vibration mill. The obtained pulverized mixture was dry-granulated with a high speed mixer and then fired at 850° C. for 4 hours in an electric furnace to obtain a powder.
得られた粉末は、Ｘ線回折測定装置（リガク社製、型番「Ｕｌｔｉｍａ ＩＶ」）により、Ｋ２Ｔｉ６Ｏ１３の単相であることを確認した。平均粒子径はレーザー回折式粒度分布測定装置（島津製作所製、型番「ＳＡＬＤ−２１００」）により９４μｍであった。 The obtained powder was confirmed to be a single phase of K 2 Ti 6 O 13 by means of an X-ray diffractometer (Rigaku Corporation, model number “Ultima IV”). The average particle diameter was 94 μm measured by a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model number “SALD-2100”).
得られた粉末の形状は、電界放出型走査電子顕微鏡（ＳＥＭ）（日立ハイテクノロジーズ社製、型番「Ｓ−４８００」）を用いて観察した。図１に粒子の全体像のＳＥＭ写真、図２に粒子の内部構造のＳＥＭ写真を示した。図１及び図２より、得られた粉末が、微粒子間に１μｍに満たない微細な空隙を有する多孔質の球状粒子であることがわかる。 The shape of the obtained powder was observed using a field emission scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation, model number "S-4800"). FIG. 1 shows an SEM photograph of the entire image of the particle, and FIG. 2 shows an SEM photograph of the internal structure of the particle. 1 and 2 that the obtained powder is a porous spherical particle having fine voids of less than 1 μm among the fine particles.
得られた粉末の細孔は、水銀ポロシメーター（Ｑｕａｎｔａ Ｃｈｒｏｍｅ社製、型番「ポアマスター６０−ＧＴ」）を用いて測定し、０．０１〜１．０μｍの細孔直径範囲にある積算細孔容積は２１．１％、細孔分布の極大値は０．１１μｍであった。また、得られた粉末についてＢＥＴ比表面積を測定した結果、５．９ｍ２／ｇであった。 The pores of the obtained powder were measured using a mercury porosimeter (manufactured by Quanta Chrome, model number "Poremaster 60-GT"), and the cumulative pore volume in the pore diameter range of 0.01 to 1.0 μm. Was 21.1%, and the maximum value of the pore distribution was 0.11 μm. The BET specific surface area of the obtained powder was measured and found to be 5.9 m 2 /g.
・チタン酸塩化合物２
Ｔｉ：Ｎａ＝３：１（モル比）となるように秤量した酸化チタン及び炭酸ナトリウムを振動ミルにて粉砕しながら１０分間混合した。得られた粉砕混合物をハイスピードミキサーにて乾式造粒した後、電気炉にて８５０℃で４時間焼成することで粉末を得た。
・Titanate compound 2
Titanium oxide and sodium carbonate, which were weighed so that Ti:Na=3:1 (molar ratio), were mixed for 10 minutes while being crushed by a vibration mill. The obtained pulverized mixture was dry-granulated with a high speed mixer and then fired at 850° C. for 4 hours in an electric furnace to obtain a powder.
得られた粉末の評価は、チタン酸塩化合物１と同様に行った。その結果、Ｎａ２Ｔｉ６Ｏ１３の単相であり、平均粒子径は２５μｍ、０．０１〜１．０μｍの細孔直径範囲にある積算細孔容積は２４．０％、細孔分布の極大値は０．３４μｍの球状粒子であることを確認した。 The obtained powder was evaluated in the same manner as the titanate compound 1. As a result, it was a single phase of Na 2 Ti 6 O 13 , the average particle size was 25 μm, the cumulative pore volume in the pore diameter range of 0.01 to 1.0 μm was 24.0%, and the maximum pore distribution was obtained. It was confirmed that the values were spherical particles having a size of 0.34 μm.
図３に粒子の全体像のＳＥＭ写真、図４に粒子の内部構造のＳＥＭ写真を示した。図３及び図４より、得られた粉末が、微細な空隙を有する多孔質の球状粒子であることがわかる。また、得られた粉末についてＢＥＴ比表面積を測定した結果、４．４ｍ２／ｇであった。 FIG. 3 shows an SEM photograph of the entire image of the particle, and FIG. 4 shows an SEM photograph of the internal structure of the particle. From FIG. 3 and FIG. 4, it can be seen that the obtained powder is porous spherical particles having fine voids. The BET specific surface area of the obtained powder was measured and found to be 4.4 m 2 /g.
・チタン酸塩化合物３
以下のようにして、特開２００９−１１４５０５号公報に開示された中空状のチタン酸塩化合物粒子を製造した。
・Titanate compound 3
The hollow titanate compound particles disclosed in JP 2009-114505 A were manufactured as follows.
Ｔｉ：Ｋ＝３：１（モル比）となるように秤量した酸化チタン及び炭酸カリウムを振動ミルにて粉砕しながら１０分間混合した。得られた粉砕混合物を、電気炉にて１０５０℃で４時間焼成し、焼成物を粉砕機にて粉砕し、平均短径１．９μｍ、平均長径３．１μｍ、平均アスペクト比１．７の柱状粉末を得た。 Titanium oxide and potassium carbonate, which were weighed so that Ti:K=3:1 (molar ratio), were mixed for 10 minutes while being crushed by a vibration mill. The obtained pulverized mixture was fired at 1050° C. for 4 hours in an electric furnace, and the fired product was pulverized by a pulverizer to obtain a columnar shape having an average minor axis of 1.9 μm, an average major axis of 3.1 μm, and an average aspect ratio of 1.7. A powder was obtained.
得られた柱状粉末、エチルセルロース系バインダー、ポリカルボン酸アンモニウム塩を用いてスラリーを製造し、得られたスラリーを噴霧乾燥した。次に噴霧乾燥して得られた粉末を９００℃で２時間熱処理を行った。 A slurry was produced using the obtained columnar powder, ethylcellulose-based binder, and polycarboxylic acid ammonium salt, and the obtained slurry was spray-dried. Next, the powder obtained by spray drying was heat-treated at 900° C. for 2 hours.
得られた粉末の評価は、チタン酸塩化合物１と同様に行った。その結果、Ｋ２Ｔｉ６Ｏ１３の単相であり、平均粒子径は１４１μｍ、０．０１〜１．０μｍの細孔直径範囲にある積算細孔容積は２．８％、細孔分布の極大値は１．９μｍの球状粒子であることを確認した。図５に粒子の全体像のＳＥＭ写真、図６に粒子の内部構造のＳＥＭ写真を示した。図５及び図６より、１．０〜５．０μｍの空隙を多く持つ中空状球状粒子であることがわかる。また、得られた粉末についてＢＥＴ比表面積を測定した結果、０．６ｍ２／ｇであった。 The obtained powder was evaluated in the same manner as the titanate compound 1. As a result, it was a single phase of K 2 Ti 6 O 13 , the average particle diameter was 141 μm, the cumulative pore volume in the pore diameter range of 0.01 to 1.0 μm was 2.8%, and the maximum pore distribution was obtained. It was confirmed that the particles were spherical particles having a value of 1.9 μm. FIG. 5 shows an SEM photograph of the entire image of the particle, and FIG. 6 shows an SEM photograph of the internal structure of the particle. From FIGS. 5 and 6, it can be seen that the particles are hollow spherical particles having many voids of 1.0 to 5.0 μm. The BET specific surface area of the obtained powder was measured and found to be 0.6 m 2 /g.
チタン酸塩化合物４〜６は、以下の市販品を用いた。 The following commercially available products were used as the titanate compounds 4 to 6.
・チタン酸塩化合物４
チタン酸塩化合物４としては、板状のチタン酸マグネシウムカリウム（大塚化学社製、商品名「テラセスＰＳ」）を用いた。なお、チタン酸塩化合物４の平均粒子径及びＢＥＴ比表面積は、下記表１に示す通りである。
・Titanate compound 4
As the titanate compound 4, plate-like magnesium potassium titanate (manufactured by Otsuka Chemical Co., Ltd., trade name “Teraces PS”) was used. The average particle diameter and BET specific surface area of the titanate compound 4 are as shown in Table 1 below.
・チタン酸塩化合物５
チタン酸塩化合物５としては、板状のチタン酸リチウムカリウム（大塚化学社製、商品名「テラセスＬ」）を用いた。なお、チタン酸塩化合物５の平均粒子径及びＢＥＴ比表面積は、下記表１に示す通りである。
・Titanate compound 5
As the titanate compound 5, plate-shaped lithium potassium titanate (manufactured by Otsuka Chemical Co., Ltd., trade name “Teraces L”) was used. The average particle diameter and BET specific surface area of the titanate compound 5 are as shown in Table 1 below.
・チタン酸塩化合物６
チタン酸塩化合物６としては、板状のチタン酸カリウム（大塚化学社製、商品名「テラセスＴＦ−Ｌ」）を用いた。なお、チタン酸塩化合物６の平均粒子径及びＢＥＴ比表面積は、下記表１に示す通りである。
・Titanate compound 6
As the titanate compound 6, plate-like potassium titanate (manufactured by Otsuka Chemical Co., Ltd., trade name “Teraces TF-L”) was used. The average particle size and BET specific surface area of the titanate compound 6 are as shown in Table 1 below.
（未加硫ゴム）
・ＮＢＲ（非繊維状粒子、平均粒子径１２０μｍ）
(Unvulcanized rubber)
・NBR (non-fibrous particles, average particle size 120 μm)
（熱硬化性樹脂）
・フェノール樹脂
(Thermosetting resin)
・Phenolic resin
＜実施例１〜２及び比較例１〜７＞
表２の配合比率に従って材料を配合し、レーディゲミキサーにて混合後、実施例及び比較例の樹脂組成物を得た。なお、表２における各成分の配合量の単位は、樹脂組成物中の体積％である。得られた樹脂組成物を仮成形し、加熱加圧成形（成形圧力１５ＭＰａ、成形温度１５０℃）し、さらに熱処理（１８０℃）を行った。得られた成形体を面積５．５ｃｍ２の扇型に加工して摩擦材を得た。
<Examples 1-2 and Comparative Examples 1-7>
The materials were blended in accordance with the blending ratio shown in Table 2, and after mixing with a Loedige mixer, resin compositions of Examples and Comparative Examples were obtained. The unit of the blending amount of each component in Table 2 is volume% in the resin composition. The obtained resin composition was temporarily molded, heated and pressed (molding pressure 15 MPa, molding temperature 150° C.), and further heat-treated (180° C.). The obtained molded body was processed into a fan shape having an area of 5.5 cm 2 to obtain a friction material.
＜評価＞
（ロックウェル硬度）
上記の方法で作製した実施例及び比較例の摩擦材のロックウェル硬度をＪＩＳ Ｄ４４２１に従い測定し、結果を表２に示した。硬さのスケールはＳスケールを使用した。
<Evaluation>
(Rockwell hardness)
The Rockwell hardness of the friction materials of Examples and Comparative Examples manufactured by the above method was measured according to JIS D4421, and the results are shown in Table 2. The S scale was used as the hardness scale.
（気孔率の測定）
上記の方法で作製した実施例及び比較例の摩擦材の気孔率をＪＩＳ Ｄ４４１８に従い測定し、結果を表２に示した。
(Measurement of porosity)
The porosities of the friction materials of Examples and Comparative Examples produced by the above method were measured according to JIS D4418, and the results are shown in Table 2.
（摩擦特性）
上記の方法で作製した実施例及び比較例の摩擦材について、スケールダイナモメーターを用いて摺り合わせ試験を行った。ローターはφ１１０ｍｍの鋳鉄（炭素含有量３．３％）を用い、１制動は初速度４０ｋｍ／ｈ、制動前ブレーキ温度９０℃以下、及び負荷荷重０．５ＭＰａの条件でブレーキを作動させ、停止するまでとし、同条件で３０００回制動を実施し、その間の摩擦係数を計測した。摩擦係数の計測は、制動を開始し負荷荷重が安定してから０．０１秒毎に実施した。
(Friction characteristics)
The friction materials of Examples and Comparative Examples produced by the above method were subjected to a sliding test using a scale dynamometer. The rotor uses cast iron of φ110 mm (carbon content 3.3%), and for 1 braking, the brake is operated and stopped under the conditions of an initial speed of 40 km/h, a braking temperature before braking of 90°C or less, and a load load of 0.5 MPa. Up to 3,000 times, braking was performed under the same conditions, and the friction coefficient during that period was measured. The measurement of the friction coefficient was performed every 0.01 seconds after the braking was started and the applied load was stabilized.
本発明において摩擦係数の振れ率とは、制動３０００回目における摩擦係数の振れ率とし、下式に基づき算出した。振れ率が２．０％以下のものを「◎」、２．０％を超え、２．５％以下のものを「○」、２．５％を超え、３．０％以下のものを「△」とし、３．０％を超えるものを「×」とし、表２に結果を示した。 In the present invention, the deflection rate of the friction coefficient is the deflection rate of the friction coefficient at the 3000th braking, and is calculated based on the following equation. "○" when the deflection rate is 2.0% or less, "○" when it exceeds 2.0% and 2.5% or less, and "O" when it exceeds 2.5% and 3.0% or less. The results are shown in Table 2 with “Δ” and those with more than 3.0% as “x”.
μi：制動３０００回目において、計測を開始してからｉ番目に計測した摩擦係数
μappi：計測した摩擦係数の関数μiを、最小二乗法により時間ｔに関する２次の多項式に近似し、得られた近似式より算出した時間tの値
μave3000：制動３０００回目の平均摩擦係数
ｎ:制動停止するまでに計測した摩擦係数の計測個数
μ i : At the 3000th braking, the friction coefficient measured i-th after the start of measurement μ appi : The function μ i of the measured friction coefficient is approximated to a quadratic polynomial with respect to time t by the least square method, and obtained. The value of the time t calculated from the approximate expression μ ave3000 : The average friction coefficient at the 3000th braking n: The number of friction coefficients measured until braking is stopped
本発明において平均摩擦係数の変化率とは、制動１０００回目の平均摩擦係数と制動３０００回目の平均摩擦係数との変化率とし、下式に基づき算出した。変化率が０％を超え、３．０％以下のものを「◎」、３．０％を超え、７．０％以下のものを「○」、７．０％を超える又は０％以下のものを「×」とし、表２に結果を示した。 In the present invention, the rate of change of the average friction coefficient is the rate of change between the average friction coefficient at 1000th braking and the average friction coefficient at 3000th braking, and was calculated based on the following equation. A rate of change of more than 0% and 3.0% or less is "A", a rate of more than 3.0% and 7.0% or less is "○", a rate of more than 7.0% or 0% or less. The result was shown in Table 2 with "x".
変化率（％）＝｜μave1000−μave3000｜÷μave1000×１００ Change rate (%) = |μ ave1000 −μ ave3000 ｜÷μ ave1000 ×100
μave1000：制動１０００回目の平均摩擦係数 μ ave1000 : Average friction coefficient at 1000th braking
摩擦係数の振れ率は、瞬間的に生じる摩擦係数の変化を示しており、摩擦材とローターとが触れたことによって発生する微小な摩擦振動と相関していると考えられる。本発明に従う実施例１〜２は、チタン酸塩化合物が添加されていない比較例５〜６と比べて振れ率が優れていることから、摩擦材は制動時に発生するブレーキノイズ（鳴き）の低減が期待できる。 The fluctuation rate of the friction coefficient indicates a momentary change in the friction coefficient, and is considered to correlate with a minute frictional vibration generated by the contact between the friction material and the rotor. In Examples 1 and 2 according to the present invention, since the runout rate is superior to Comparative Examples 5 and 6 in which the titanate compound is not added, the friction material reduces brake noise (squeaking) generated during braking. Can be expected.
平均摩擦係数の変化率は、従来の摩擦特性の評価方法である。未加硫ゴムを配合した比較例５にさらにチタン酸塩化合物３〜６を添加した比較例１〜４は、比較例５より変化率が悪くなっており、単にチタン酸塩化合物と未加硫ゴムとを組み合わせただけでは、本発明の効果が得られないことがわかる。これは、チタン酸塩化合物の添加により、熱硬化性樹脂からの凝着性の高い熱分解物の生成は抑制されるが、チタン酸塩化合物は未加硫ゴムに対して作用しないため、ローターの温度が上昇しない低負荷条件では、未加硫ゴム由来の潤滑性被膜が摩擦界面に形成されることが原因であると推測される。 The change rate of the average friction coefficient is a conventional evaluation method of friction characteristics. Comparative Examples 1 to 4 in which the titanate compounds 3 to 6 were further added to Comparative Example 5 containing unvulcanized rubber had a lower change rate than Comparative Example 5, and the titanate compound and the unvulcanized compound were simply added. It is understood that the effect of the present invention cannot be obtained only by combining with rubber. This is because the addition of the titanate compound suppresses the formation of highly cohesive thermal decomposition products from the thermosetting resin, but the titanate compound does not act on the unvulcanized rubber, so the rotor It is presumed that this is caused by the formation of a lubricious coating derived from unvulcanized rubber at the friction interface under the low load condition in which the temperature does not rise.
本発明の摩擦材は、特定形状を有するチタン酸塩化合物により未加硫ゴム由来の潤滑性被膜の形成が抑制され、単にチタン酸塩化合物と未加硫ゴムとを組み合わせるだけでは得られない予期せぬ効果が得られるものと推測される。 In the friction material of the present invention, the formation of the lubricating coating derived from the unvulcanized rubber is suppressed by the titanate compound having a specific shape, and it is expected that it cannot be obtained simply by combining the titanate compound and the unvulcanized rubber. It is presumed that the effect not obtained can be obtained.
比較例５と比較例６から、加硫ゴムだけでは摩擦材の気孔率が大きくなりすぎることがわかる。摩擦材の気孔率を小さく制御しようと成形圧力を強くすると摩擦材の硬度が大きくなるため好ましくない。 From Comparative Example 5 and Comparative Example 6, it is understood that the porosity of the friction material becomes too large only with the vulcanized rubber. If the molding pressure is increased to control the porosity of the friction material to be small, the hardness of the friction material increases, which is not preferable.
表２に示すように、本発明に従う実施例１〜２は、ロックウェル硬度が低く、柔軟性に優れており、かつ摩擦特性に優れていることがわかる。また、本発明に従う実施例１〜２は、多孔質チタン酸塩化合物粒子を用いていることから、銅の有無にかかわらず優れた耐フェード性が得られることも期待できる。 As shown in Table 2, Examples 1 and 2 according to the present invention have low Rockwell hardness, excellent flexibility, and excellent friction characteristics. Further, since Examples 1 and 2 according to the present invention use the porous titanate compound particles, it can be expected that excellent fade resistance can be obtained regardless of the presence or absence of copper.
Claims (11)
前記未加硫ゴムが、天然ゴム、スチレン・ブタジエンゴム、ブタジエンゴム、イソプレンゴム、ニトリルゴム、クロロプレンゴム、ブチルゴム、及びエチレン・プロピレンゴムから選ばれる少なくとも１種である、樹脂組成物。 Porous titanate compound particles having an accumulated pore volume of 5% or more in the range of pore diameters of 0.01 to 1.0 μm and formed by bonding crystal grains of a titanate compound, and unvulcanized rubber. , Containing a thermosetting resin ,
The resin composition, wherein the unvulcanized rubber is at least one selected from natural rubber, styrene/butadiene rubber, butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, butyl rubber, and ethylene/propylene rubber .
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