JP6753649B2 - Friction materials and members - Google Patents
Friction materials and members Download PDFInfo
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- JP6753649B2 JP6753649B2 JP2015022169A JP2015022169A JP6753649B2 JP 6753649 B2 JP6753649 B2 JP 6753649B2 JP 2015022169 A JP2015022169 A JP 2015022169A JP 2015022169 A JP2015022169 A JP 2015022169A JP 6753649 B2 JP6753649 B2 JP 6753649B2
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- friction material
- friction
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- rust
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- 239000002783 friction material Substances 0.000 title claims description 152
- 239000000835 fiber Substances 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000011256 inorganic filler Substances 0.000 claims description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 19
- 229920006231 aramid fiber Polymers 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 11
- 239000012766 organic filler Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 65
- 238000000465 moulding Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 239000005011 phenolic resin Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000004760 aramid Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000012784 inorganic fiber Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 5
- 244000226021 Anacardium occidentale Species 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000010425 asbestos Substances 0.000 description 4
- 235000020226 cashew nut Nutrition 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052895 riebeckite Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 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
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000002557 mineral fiber Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 241001255854 Teras Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide 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
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001449 anionic compounds Chemical group 0.000 description 1
- 238000007743 anodising Methods 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 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
- 238000013329 compounding Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HZZOEADXZLYIHG-UHFFFAOYSA-N magnesiomagnesium Chemical compound [Mg][Mg] HZZOEADXZLYIHG-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 210000002268 wool Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- 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)
Description
本発明は、自動車等の制動に用いられるディスクブレーキパッド等の摩擦材に関し、特にアスベストを含まないノンアスベスト摩擦材に関する。また、該摩擦材と裏金を組み合わせて形成した摩擦部材に関する。 The present invention relates to a friction material such as a disc brake pad used for braking an automobile or the like, and more particularly to a non-asbestos friction material containing no asbestos. Further, the present invention relates to a friction member formed by combining the friction material and a back metal.
自動車等には、その制動のためにディスクブレーキパッド、ブレーキライニング等の摩擦材が使用されている。摩擦材は、ディスクローター、ブレーキドラム等の対面材と摩擦することにより、制動の役割を果たしている。そのため、摩擦材には、良好な摩擦係数、耐摩耗性（摩擦材の寿命が長いこと）、強度、音振性（ブレーキ鳴きや異音が発生しにくいこと）等が要求される。摩擦係数は車速、減速度やブレーキ温度によらず安定であることが要求される。また、摩擦界面で発生した錆によって摩擦材が摩擦対面材と固着し、発車時の異音発生や摩擦材の表面剥離（錆剥離）などの問題が生じる場合がある。錆固着性能を改善するために、犠牲陽極として作用する亜鉛やｐＨを上げるアルカリ金属塩を添加するなどの摩擦材組成が提案されている。（特許文献１〜２） Friction materials such as disc brake pads and brake linings are used for braking in automobiles and the like. The friction material plays a role of braking by rubbing against a facing material such as a disc rotor and a brake drum. Therefore, the friction material is required to have a good friction coefficient, wear resistance (long life of the friction material), strength, sound vibration property (less likely to generate brake squeal or abnormal noise), and the like. The coefficient of friction is required to be stable regardless of vehicle speed, deceleration and braking temperature. In addition, the rust generated at the friction interface may cause the friction material to adhere to the friction facing material, causing problems such as generation of abnormal noise at the time of departure and surface peeling (rust peeling) of the friction material. In order to improve the rust fixing performance, a friction material composition such as adding zinc acting as a sacrificial anode or an alkali metal salt for raising pH has been proposed. (Patent Documents 1 and 2)
摩擦材には、結合材、繊維基材、無機充填材および有機充填材等を含む摩擦材組成物が用いられ、前記特性を発現させるために、一般的に、各成分を１種または２種以上を組合せた摩擦材組成物が用いられる。中でも銅は繊維や粉末の形態で摩擦材に配合され、高温での制動条件下での摩擦係数の保持（耐フェード性）や高温での耐摩耗性改善、摩擦材の強度向上に有効な成分である。しかし、銅を含有する摩擦材は、制動時に生成する摩耗粉に銅を含み、河川、湖や海洋汚染等の原因となる可能性が示唆されているため、使用を制限する動きが高まっている。 As the friction material, a friction material composition containing a binder, a fiber base material, an inorganic filler, an organic filler and the like is used, and in order to exhibit the above-mentioned characteristics, generally one or two kinds of each component are used. A friction material composition combining the above is used. Among them, copper is blended in the friction material in the form of fiber or powder, and is an effective component for maintaining the coefficient of friction (fade resistance) under braking conditions at high temperature, improving wear resistance at high temperature, and improving the strength of the friction material. Is. However, copper-containing friction materials contain copper in the abrasion powder generated during braking, and it has been suggested that it may cause pollution of rivers, lakes, oceans, etc., so there is a growing movement to limit its use. ..
このような銅の使用量を制限する動きの中、特許文献３には、銅を含有しない組成における強度、耐摩耗性を改善する手法として、複数の凸形状を有するチタン酸カリウムと生体溶解性無機繊維とを含有させることを特徴とする摩擦材が提案されている。 In such a movement to limit the amount of copper used, Patent Document 3 describes potassium titanate having a plurality of convex shapes and biosolubility as a method for improving strength and abrasion resistance in a composition containing no copper. A friction material characterized by containing an inorganic fiber has been proposed.
環境有害性の高い銅を含まない摩擦材は材料強度が低く、錆剥離が問題となる。特許文献１〜２で提案されている防錆効果や、特許文献３で提案されている銅を含有しない組成における摩擦材強度向上では、銅を含有しない摩擦材の錆剥離の改善効果は充分ではなかった。 Friction materials that do not contain copper, which are highly harmful to the environment, have low material strength, and rust peeling becomes a problem. In the rust preventive effect proposed in Patent Documents 1 and 2 and the improvement of the friction material strength in the copper-free composition proposed in Patent Document 3, the effect of improving the rust peeling of the friction material not containing copper is sufficient. There wasn't.
本発明では、上記事情を鑑みなされたもので、環境負荷の高い銅を含有しない、または銅の含有量が０．５質量％以下の摩擦材において、錆固着力、錆剥離の少ない摩擦材を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and in a friction material which does not contain copper having a high environmental load or has a copper content of 0.5% by mass or less, a friction material having less rust adhesion and rust peeling is provided. It is intended to be provided.
本発明者らは、銅を含有せず、摩擦材の材料強度を向上するためにフィブリル化アラミド繊維を含有する組成において、摩擦材の強度と錆の抑制効果、および錆と摩擦材の相互作用の観点で錆固着力と錆剥離の低減を鋭意検討し、油含浸法で測定される気孔率が１５％以下であって、イオンクロマトグラフで測定される硫酸イオン濃度が１０００ｐｐｍ以下とすることが効果的であることを見出した。すなわち、フィブリル化アラミド繊維を含有し、かつ気孔率を１５％以下とすることで摩擦材の強度が十分高くなり、錆剥離しにくいだけでなく、気孔率が小さいことで摩擦材の気孔への錆の侵入が少なくなることを見出した。また、フィブリル化アラミド繊維を含有するとともに気孔率を１５％以下とした上で、さらに、硫酸イオンを低減すると、上記効果に加えて防食作用が向上し、銅を含有しない摩擦材においても錆固着力、錆剥離を大幅に低減することが可能であることを見出した。 In a composition that does not contain copper and contains fibrillated aramid fibers in order to improve the material strength of the friction material, the strength of the friction material and the effect of suppressing rust, and the interaction between rust and the friction material From this point of view, the reduction of rust adhesion and rust peeling is diligently examined, and the pore ratio measured by the oil impregnation method is 15% or less, and the sulfate ion concentration measured by the ion chromatograph is 1000 ppm or less. Found to be effective. That is, by containing fibrillated aramid fibers and having a porosity of 15% or less, the strength of the friction material is sufficiently high, and not only is it difficult for rust to peel off, but also the porosity is small, so that the friction material has pores. We found that the invasion of rust was reduced. Further, if the porosity is 15% or less while containing the fibrillated aramid fiber and the sulfate ion is further reduced, the anticorrosion effect is improved in addition to the above effect, and the friction material containing no copper is rusted. It was found that it is possible to significantly reduce the adhesive force and rust peeling.
上記のフィブリル化アラミド繊維を含有するとともに気孔率を１５％以下とした上で硫酸イオンを低減した摩擦材においては、犠牲陽極として防錆作用を示す亜鉛粉末や、摩擦材のｐＨを効果的に向上せしめる水酸化カルシウムまたは／および炭酸ナトリウムを特定量含有させることで、上記の摩擦材における錆固着力、錆剥離の改善効果を更に向上させることができることを見出した。また、摩擦材強度を向上せしめかつ発錆量が少なくなる特定量のスチール繊維の添加や、同じく摩擦材強度を向上せしめる複数の凸部形状を有するチタン酸カリウムを添加することにより、上記の摩擦材における錆固着力、錆剥離の改善効果を更に向上させることができることを見出した。さらに、摩擦材のｐＨを１２〜１３とすることで、上記の摩擦材における錆固着力、錆剥離の改善効果を更に向上させることができることを見出した。 In the friction material containing the above-mentioned fibrillated aramid fiber and having a pore ratio of 15% or less and reducing sulfate ions, zinc powder showing a rust preventive action as a sacrificial anode and the pH of the friction material are effectively used. It has been found that by containing a specific amount of calcium hydroxide and / or sodium carbonate to be improved, the effect of improving the rust adhesion and rust peeling in the above-mentioned friction material can be further improved. Further, by adding a specific amount of steel fiber that improves the friction material strength and reduces the amount of rust, or by adding potassium titanate having a plurality of convex shapes that also improves the friction material strength, the above friction It has been found that the effect of improving rust adhesion and rust peeling in the material can be further improved. Furthermore, it has been found that by setting the pH of the friction material to 12 to 13, the effect of improving the rust adhesion and rust peeling in the above-mentioned friction material can be further improved.
本発明はこれらの知見に基づくものであり、本発明の摩擦材は、具体的に、結合剤、有機充填材、無機充填材および繊維基材を含む摩擦材であって、該摩擦材中に元素としての銅を含まない、または銅の含有量が０．５質量％以下であり、前記繊維基材としてフィブリル化アラミド繊維を含有し、油含浸法で測定される気孔率が１５％以下であって、イオンクロマトグラフで測定される硫酸イオン濃度が１０００ｐｐｍ以下であることを特徴とする。 The present invention is based on these findings, and the friction material of the present invention is specifically a friction material containing a binder, an organic filler, an inorganic filler and a fiber base material, and the friction material contains the friction material. It does not contain copper as an element, or the content of copper is 0.5% by mass or less, it contains fibrillated aramid fiber as the fiber base material, and the pore ratio measured by the oil impregnation method is 15% or less. It is characterized in that the sulfate ion concentration measured by an ion chromatograph is 1000 ppm or less.
本発明の摩擦材においては、前記無機充填剤として亜鉛粉末を含有することが好ましく、前記無機充填剤として水酸化カルシウムを２．５〜１０質量％または／および炭酸ナトリウムを０．２〜２質量％で含有することが好ましい。また、本発明の摩擦材においては、前記繊維基材としてスチール繊維を２〜８質量％で含有することが好ましく、前記無機充填材として、複数の凸部形状を有するチタン酸カリウムを含有することが好ましい。さらに、本発明の摩擦材においては、摩擦材のｐＨは１２〜１３であることが好ましい。 The friction material of the present invention preferably contains zinc powder as the inorganic filler, and 2.5 to 10% by mass of calcium hydroxide and / or 0.2 to 2% by mass of sodium carbonate as the inorganic filler. It is preferably contained in%. Further, the friction material of the present invention preferably contains 2 to 8% by mass of steel fiber as the fiber base material, and contains potassium titanate having a plurality of convex shapes as the inorganic filler. Is preferable. Further, in the friction material of the present invention, the pH of the friction material is preferably 12 to 13.
また、本発明の摩擦部材は、上記の本発明の摩擦材摩擦材と裏金とを用いて形成されることを特徴とするものである。 Further, the friction member of the present invention is characterized in that it is formed by using the friction material friction material of the present invention and a back metal.
本発明によれば、自動車用ディスクブレーキパッド等の摩擦材に用いた際に、環境負荷の高い銅を用いなくとも、錆固着力が小さく錆剥離の少ない摩擦材および摩擦部材を提供することができる。 According to the present invention, when used as a friction material for an automobile disc brake pad or the like, it is possible to provide a friction material and a friction member having a small rust adhesion force and less rust peeling without using copper having a high environmental load. it can.
以下、本発明の摩擦材および摩擦部材について詳述する。なお、本発明の摩擦材は、アスベストを含まない、いわゆるノンアスベスト摩擦材である。
［摩擦材］
Hereinafter, the friction material and the friction member of the present invention will be described in detail. The friction material of the present invention is a so-called non-asbestos friction material that does not contain asbestos.
[Friction material]
本実施形態の摩擦材は、銅を含有しない、もしくは銅を含有する場合において銅の含有量が０．５質量％以下であることを特徴とする摩擦材である。すなわち、環境有害性の高い銅および銅合金を実質的に含有せず、元素としての銅の含有量が０．５重量％以下であり、好ましくは含有量０質量％の摩擦材である。このため、制動時に摩耗粉が生成しても、河川、湖や海洋汚染の原因とならない。 The friction material of the present embodiment is a friction material that does not contain copper or that contains copper and has a copper content of 0.5% by mass or less. That is, it is a friction material that does not substantially contain copper and a copper alloy having high environmental hazards, and has a copper content of 0.5% by weight or less as an element, preferably a content of 0% by mass. Therefore, even if wear debris is generated during braking, it does not cause pollution of rivers, lakes and the ocean.
（フィブリル化アラミド繊維）
本発明の摩擦材は、フィブリル化アラミド繊維を含む。フィブリル化アラミド繊維は、複数の枝分かれを有し、ＢＥＴ比表面積が５〜１５ｍ２／ｇであることが特徴であり、帝人株式会社製Ｔｗａｒｏｎ１０９９、１０９５、３０９１、東レ・デュポン株式会社製ケブラー１Ｆ５３８、１Ｆ１７１０などが挙げられる。これらのフィブリル化アラミド繊維は、繊維強度が高く多数の枝分かれを有するため、銅を含有しない組成においても効果的に摩擦材強度を向上させるため、摩擦材の繊維基材として好適なものである。
(Fibrilized aramid fiber)
The friction material of the present invention contains fibrillated aramid fibers. The fibrillated aramid fiber has a plurality of branches and is characterized by having a BET specific surface area of 5 to 15 m 2 / g. 1F1710 and the like can be mentioned. Since these fibrillated aramid fibers have high fiber strength and have a large number of branches, they effectively improve the friction material strength even in a composition that does not contain copper, and are therefore suitable as fiber base materials for friction materials.
（気孔率）
本発明の摩擦材においては、油含浸法で測定される気孔率を１５％以下とする。ここでいう油含浸法で測定される気孔率とは、ＪＩＳ Ｄ４４１８に準じて測定される気孔率であり、閉気孔を含まない開気孔率のことをいう。本発明の摩擦材は、気孔率を小さくすることで、銅を含有しない組成においても摩擦材の強度を十分なものとするとともに、気孔を通じての摩擦材への錆の取り込みを少なくして、錆固着力を小さくすることで錆剥離を防止する。摩擦材の気孔率は、製造工程で調整が可能であり、特に成形工程における成形圧力、成形温度、成形時間による調整が容易である。具体的には、成形圧力、成形温度を高くし、成形時間を長くすることで気孔率を低減することができる。
(Porosity)
In the friction material of the present invention, the porosity measured by the oil impregnation method is 15% or less. The porosity measured by the oil impregnation method referred to here is a porosity measured according to JIS D4418, and means an open porosity that does not include closed pores. By reducing the porosity, the friction material of the present invention makes the friction material strong enough even in a composition that does not contain copper, and reduces the uptake of rust into the friction material through the pores to reduce rust. Prevents rust peeling by reducing the adhesive force. The porosity of the friction material can be adjusted in the manufacturing process, and in particular, it is easy to adjust by the molding pressure, the molding temperature, and the molding time in the molding process. Specifically, the porosity can be reduced by increasing the molding pressure and the molding temperature and lengthening the molding time.
（硫酸イオン）
摩擦材の硫酸イオン濃度が高くなると、その分、摩擦材に錆が発生しやすくなる。このため、本発明の摩擦材は、イオンクロマトグラフで測定される硫酸イオン濃度が１０００ｐｐｍ以下とする。また、イオンクロマトグラフで測定される硫酸イオン濃度を５００ｐｐｍ以下とすると、より錆が発生しにくくなるため好ましい。摩擦材中の硫酸イオン濃度の低減は、通常の摩擦材に用いられる素材のうち、製造工程で硫酸を使用することがあるチタン酸塩やカシューダストなどについて、硫酸イオンの少ない銘柄を使用することで可能である。例えば、硫酸イオンの少ないチタン酸塩としては、具体的に東邦マテリアル株式会社製ＴＯＦＩＸなどが挙げられる。また、硫酸イオンの少ないチタン酸塩としては、東北化工株式会社製ＦＦ１７００などが挙げられる。
(Sulfate ion)
The higher the sulfate ion concentration of the friction material, the more likely it is that rust will occur on the friction material. Therefore, the friction material of the present invention has a sulfate ion concentration of 1000 ppm or less as measured by an ion chromatograph. Further, it is preferable that the sulfate ion concentration measured by the ion chromatograph is 500 ppm or less because rust is less likely to occur. To reduce the concentration of sulfate ions in the friction material, use a brand with a small amount of sulfate ions for titanate, cashew dust, etc., which may use sulfuric acid in the manufacturing process, among the materials used for ordinary friction materials. It is possible with. For example, as a titanate having a small amount of sulfate ions, TOFIX manufactured by Toho Material Co., Ltd. can be specifically mentioned. Further, examples of the titanate having a small amount of sulfate ions include FF1700 manufactured by Tohoku Kako Co., Ltd.
なお、摩擦材の硫酸イオン濃度は、次の手順で測定することができる。摩擦材３．０ｇに純水２０ｇを加え、１３０℃で３時間加熱抽出する。放冷後、抽出液をろ過し、更に固層抽出を行い適宜希釈することで試料溶液とする。この試料溶液について、硫酸イオン標準液による検量線法で、イオンクロマトグラフを用いて硫酸イオンを定量測定する。 The sulfate ion concentration of the friction material can be measured by the following procedure. 20 g of pure water is added to 3.0 g of the friction material, and heat extraction is performed at 130 ° C. for 3 hours. After allowing to cool, the extract is filtered, and a solid layer is extracted and diluted appropriately to obtain a sample solution. For this sample solution, sulfate ions are quantitatively measured using an ion chromatograph by a calibration curve method using a sulfate ion standard solution.
以下に、イオンクロマトグラフの測定条件の一例を例示する。
検 出 器：電気伝導度検出器
カ ラ ム：無機陰イオン交換カラム（ダイオネクス製IonPac AS12Aなど）
溶 離 液：２．７ｍｍｏｌ／ｌ Ｎａ２ＣＯ３＋０．３ｍｍｏｌ／ｌ ＮａＨＣＯ３
流 速：１．３３ｍｌ／ｍｉｎ
注 入 量：２５μｌ
定量方法：硫酸イオン標準液のイオンクロマトグラムと保持時間の一致するピークについて、検量線法により検出量を計測する。
An example of the measurement conditions of the ion chromatograph will be illustrated below.
Detector: Electrical conductivity detector Format: Inorganic anion exchange column (Dionex IonPac AS12A, etc.)
Leached solution: 2.7 mmol / l Na 2 CO 3 + 0.3 mmol / l NaHCO 3
Flow speed: 1.33 ml / min
Injection amount: 25 μl
Quantification method: For peaks that have the same retention time as the ion chromatogram of the sulfate ion standard solution, measure the amount detected by the calibration curve method.
（亜鉛粉末）
上記のフィブリル化アラミド繊維を含有するとともに気孔率を１５％以下とした上で硫酸イオンを低減した本発明の摩擦材においては、亜鉛粉末を含有させることが好ましい。粉末状の亜鉛は、制動により摩擦材の摩擦界面に延展して摩擦界面を被覆する状態となるが、亜鉛は酸化しやすいことから摩擦界面を被覆した亜鉛が、犠牲陽極作用により選択的に酸化されることで、摩擦材中の他の成分の酸化すなわち発錆を防止して摩擦界面全体の防錆を行う。このため、摩擦材中に亜鉛粉末を含有させると、錆固着力がよりいっそう低減するとともに、錆剥離を抑制する効果がより大きくなる。粉末状の亜鉛としては、アトマイズなどで製造される通常摩擦材に用いられる粉末状の亜鉛を用いることができるが、摩擦材表面での延展による防錆効果の観点で粒径は細かいほどよく、１０〜５００μｍが好ましく、１０〜１００μｍがより好ましい。また、亜鉛の添加量は、防錆効果の観点で１質量％以上が好ましく、２質量％がより好ましい。しかしながら、亜鉛の過剰添加は、高温使用時における摩擦材の耐摩耗性の悪化を引き起こすため、１０質量％以下の添加量で用いることが好ましく、８質量％がより好ましい。
(Zinc powder)
In the friction material of the present invention containing the above-mentioned fibrillated aramid fiber and having a porosity of 15% or less and reduced sulfate ions, it is preferable to contain zinc powder. Powdered zinc spreads to the friction interface of the friction material by braking and covers the friction interface, but since zinc is easily oxidized, the zinc covering the friction interface is selectively oxidized by the sacrificial anodizing action. By doing so, oxidation of other components in the friction material, that is, rusting is prevented, and the entire friction interface is prevented from rusting. For this reason, when zinc powder is contained in the friction material, the rust fixing force is further reduced and the effect of suppressing rust peeling is further increased. As the powdered zinc, powdered zinc usually used for friction materials manufactured by atomization or the like can be used, but the finer the particle size, the better from the viewpoint of the rust preventive effect due to the spread on the friction material surface. 10 to 500 μm is preferable, and 10 to 100 μm is more preferable. The amount of zinc added is preferably 1% by mass or more, more preferably 2% by mass, from the viewpoint of rust preventive effect. However, excessive addition of zinc causes deterioration of wear resistance of the friction material when used at a high temperature, so it is preferable to use it in an amount of 10% by mass or less, and more preferably 8% by mass.
（水酸化カルシウムおよび／または炭酸ナトリウム）
本発明の摩擦材においては、無機充填材として、水酸化カルシウムおよび／または炭酸ナトリウムを含有させることが好ましい。水酸化カルシウムや炭酸ナトリウムは、通常の摩擦材に用いられる粉末状の水酸化カルシウムおよび炭酸ナトリウムを用いることができるが、水溶性の観点で、粒径の細かいもの、特に１００μｍ以下の粉末が好ましい。水酸化カルシウムおよび炭酸ナトリウムは摩擦対面材の防錆効果があるだけでなく摩擦材の成形時にフェノール樹脂の硬化触媒として作用し、摩擦材強度を向上させる。しかし、過度に添加しすぎるとフィブリル化アラミド繊維の強度を低下させる。そのため、本発明の摩擦材においては水酸化カルシウムの含有量は２．５〜１０質量％が好ましく、炭酸ナトリウムの含有量は０．２〜２質量％が好ましい。このような水酸化カルシウムおよび炭酸ナトリウムは、上記の摩擦材に一方のみを添加しても良く、両方を同時に添加しても良い。
(Calcium hydroxide and / or sodium carbonate)
In the friction material of the present invention, it is preferable to contain calcium hydroxide and / or sodium carbonate as the inorganic filler. As the calcium hydroxide and sodium carbonate, powdered calcium hydroxide and sodium carbonate used for ordinary friction materials can be used, but from the viewpoint of water solubility, those having a fine particle size, particularly powders having a particle size of 100 μm or less are preferable. .. Calcium hydroxide and sodium carbonate not only have a rust preventive effect on the friction facing material, but also act as a curing catalyst for the phenol resin during molding of the friction material, improving the strength of the friction material. However, too much addition reduces the strength of the fibrillated aramid fibers. Therefore, in the friction material of the present invention, the content of calcium hydroxide is preferably 2.5 to 10% by mass, and the content of sodium carbonate is preferably 0.2 to 2% by mass. Only one of such calcium hydroxide and sodium carbonate may be added to the above friction material, or both may be added at the same time.
（スチール繊維）
本発明の摩擦材においては、繊維基材として、スチール繊維を含有させることが好ましい。スチール繊維は、びびり振動切削法などで得られるストレート繊維と、長繊維のカットなどで得られるカール状繊維がある。ストレート繊維が直線状の繊維形状なのに対し、カール状繊維は繊維が曲がった形状をしている。カール状繊維のほうが摩擦界面において摩擦材からの脱落が少なく、高温制動における摩擦特性保持の観点で好ましい。カール状のスチール繊維は、日本スチールウール株式会社製カットウールなど、市販されているものを使用することができる。スチール繊維は、摩擦材の強度を向上させ錆剥離を抑制するが、スチール繊維自体が錆びることで、多量の添加により錆固着力を増加させてしまう。スチール繊維の含有量を２〜８質量％とすることで、本発明の摩擦材において、錆固着力と錆剥離を両立して抑制することができる。スチール繊維の繊維径は、高温における耐摩耗性の観点で１００μｍ以下が好ましい。スチール繊維の繊維長は、高温における耐摩耗性の観点で２５００μｍ以下が好ましい。
(Steel fiber)
In the friction material of the present invention, it is preferable to contain steel fibers as the fiber base material. Steel fibers include straight fibers obtained by chatter vibration cutting and the like, and curled fibers obtained by cutting long fibers. While straight fibers have a linear fiber shape, curled fibers have a bent fiber shape. The curled fiber is preferable from the viewpoint of maintaining the frictional characteristics at high temperature braking because it is less likely to fall off from the friction material at the friction interface. As the curled steel fiber, commercially available one such as cut wool manufactured by Nippon Steel Wool Co., Ltd. can be used. Steel fiber improves the strength of the friction material and suppresses rust peeling, but when the steel fiber itself rusts, the rust adhesion is increased by adding a large amount. By setting the content of the steel fiber to 2 to 8% by mass, the friction material of the present invention can suppress both the rust fixing force and the rust peeling at the same time. The fiber diameter of the steel fiber is preferably 100 μm or less from the viewpoint of wear resistance at high temperatures. The fiber length of the steel fiber is preferably 2500 μm or less from the viewpoint of wear resistance at high temperatures.
（複数の凸形状を有するチタン酸カリウム）
本発明の摩擦材においては、無機充填材として、複数の凸形状を有するチタン酸カリウムを含有させることが好ましい。複数の凸形状を有するチタン酸カリウムとは、不規則な方向に複数の凸部が延びる形状を有する不定形のチタン酸カリウムのことで、摩擦調整剤として用いることができることが知られている（特許文献３）。例えば、大塚化学株式会社製「テラセスＪＰ」が挙げられる。このような不規則な方向に複数の凸部が延びる形状を有する不定形のチタン酸カリウムは、凸部が摩擦材の強度向上に効果的であり、特に本発明の摩擦材の錆剥離の抑制に効果的である。本発明の摩擦材中における複数の凸形状を有するチタン酸カリウムの含有量は、錆剥離抑制の観点で１〜３０質量％が好ましく、１〜２０質量％であることがより好ましい。
(Potassium titanate with multiple convex shapes)
In the friction material of the present invention, it is preferable to contain potassium titanate having a plurality of convex shapes as the inorganic filler. Potassium titanate having a plurality of convex shapes is an amorphous potassium titanate having a shape in which a plurality of convex portions extend in irregular directions, and is known to be usable as a friction modifier (). Patent Document 3). For example, "Terases JP" manufactured by Otsuka Chemical Co., Ltd. can be mentioned. The amorphous potassium titanate having a shape in which a plurality of convex portions extend in such irregular directions is effective in improving the strength of the friction material, and particularly suppresses rust peeling of the friction material of the present invention. It is effective for. The content of potassium titanate having a plurality of convex shapes in the friction material of the present invention is preferably 1 to 30% by mass, more preferably 1 to 20% by mass from the viewpoint of suppressing rust peeling.
（摩擦材のｐＨ）
本発明の摩擦材においては、摩擦材のｐＨを高くすると、錆固着力をより低減できるとともに、錆剥離をより抑制できるため、摩擦材のｐＨを１２以上とすることが好ましい。摩擦材のｐＨは、水酸化カルシウム、水酸化ナトリウム、炭酸ナトリウムなど、水溶時にアルカリ性を示す成分を含有させることで容易に増加させることができる。ただし、上記のフィブリル化アラミド繊維は、高いｐＨの水溶液に長時間曝露することで、加水分解により強度が低下するため、摩擦材のｐＨは１３以下とすることが好ましい。摩擦材のｐＨは、ＪＡＳＯ Ｃ４５８−８６に準拠して測定することができる。
(PH of friction material)
In the friction material of the present invention, when the pH of the friction material is increased, the rust fixing force can be further reduced and the rust peeling can be further suppressed. Therefore, the pH of the friction material is preferably 12 or more. The pH of the friction material can be easily increased by containing a component that is alkaline when water is water, such as calcium hydroxide, sodium hydroxide, and sodium carbonate. However, since the strength of the above-mentioned fibrillated aramid fiber is lowered by hydrolysis when exposed to an aqueous solution having a high pH for a long time, the pH of the friction material is preferably 13 or less. The pH of the friction material can be measured according to JASO C458-86.
（結合材）
結合剤は、摩擦材に含まれる有機充填材、無機充填材および繊維基材などを一体化し、強度を与えるものである。本発明の摩擦材に含まれる結合材としては特に制限は無く、通常、摩擦材の結合材として用いられる熱硬化性樹脂を用いることができる。
(Binder)
The binder integrates the organic filler, the inorganic filler, the fiber base material, and the like contained in the friction material to give strength. The binder contained in the friction material of the present invention is not particularly limited, and a thermosetting resin usually used as a binder of the friction material can be used.
上記熱硬化性樹脂としては、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およびシリコーンエラストマー分散フェノール樹脂などの各種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、カシュー変性フェノール樹脂、エポキシ変性フェノール樹脂およびアルキルベンゼン変性フェノール樹脂などの各種変性フェノール樹脂などが挙げられ、これらを単独でまたは２種類以上を組み合わせて使用することができる。特に、良好な耐熱性、成形性および摩擦係数を与えることから、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、アルキルベンゼン変性フェノール樹脂を用いることが好ましい。 Examples of the thermosetting resin include phenolic resins; various elastomer-dispersed phenolic resins such as acrylic elastomer-dispersed phenolic resins and silicone elastomer-dispersed phenolic resins; acrylic-modified phenolic resins, silicone-modified phenolic resins, cashew-modified phenolic resins, and epoxy-modified phenolic resins. Examples thereof include resins and various modified phenolic resins such as alkylbenzene-modified phenolic resins, and these can be used alone or in combination of two or more. In particular, it is preferable to use a phenol resin, an acrylic-modified phenol resin, a silicone-modified phenol resin, or an alkylbenzene-modified phenol resin because it provides good heat resistance, moldability, and a coefficient of friction.
本発明の摩擦材組成物中における、結合材の含有量は、５〜２０質量％であることが好ましく、５〜１０質量％であることがより好ましい。結合材の含有量を５〜２０質量％の範囲とすることで、摩擦材の強度低下をより抑制でき、また、摩擦材の弾性率が高くなることによる鳴きなどの音振性能悪化をより抑制できる。 The content of the binder in the friction material composition of the present invention is preferably 5 to 20% by mass, and more preferably 5 to 10% by mass. By setting the content of the binder in the range of 5 to 20% by mass, it is possible to further suppress the decrease in the strength of the friction material, and further suppress the deterioration of sound vibration performance such as squeal due to the high elastic modulus of the friction material. it can.
（有機充填剤）
有機充填材は、摩擦材の音振性能や耐摩耗性などを向上させるための摩擦調整剤として含まれるものである。本発明の摩擦材に含まれる有機充填材としては、上記性能を発揮できるものであれば特に制限はなく、通常、有機充填材として用いられる、カシューダストやゴム成分などを用いることができる。
(Organic filler)
The organic filler is contained as a friction modifier for improving the sound vibration performance and wear resistance of the friction material. The organic filler contained in the friction material of the present invention is not particularly limited as long as it can exhibit the above performance, and cashew dust, a rubber component, or the like, which is usually used as an organic filler, can be used.
上記カシューダストは、カシューナッツシェルオイルを硬化させたものを粉砕して得られる、通常、摩擦材に用いられるものであればよい。 The cashew dust may be any one usually used as a friction material, which is obtained by crushing a hardened cashew nut shell oil.
上記ゴム成分としては、例えば、タイヤゴム、アクリルゴム、イソプレンゴム、ＮＢＲ（ニトリルブタジエンゴム）、ＳＢＲ（スチレンブタジエンゴム）、塩素化ブチルゴム、ブチルゴム、シリコーンゴム、などが挙げられ、これらを単独でまたは２種類以上を組み合わせて使用される。 Examples of the rubber component include tire rubber, acrylic rubber, isoprene rubber, NBR (nitrile butadiene rubber), SBR (styrene butadiene rubber), chlorinated butyl rubber, butyl rubber, silicone rubber, etc., and these may be used alone or 2 Used in combination of more than one type.
本発明の摩擦材中における、有機充填材の含有量は、１〜２０質量％であることが好ましく、１〜１０質量％であることがより好ましく、３〜８質量％であることが特に好ましい。有機充填材の含有量を１〜２０質量％の範囲とすることで、摩擦材の弾性率が高くなること、鳴きなどの音振性能の悪化を避けることができ、また耐熱性の悪化、熱履歴による強度低下を避けることができる。 The content of the organic filler in the friction material of the present invention is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 3 to 8% by mass. .. By setting the content of the organic filler in the range of 1 to 20% by mass, the elastic modulus of the friction material becomes high, deterioration of sound vibration performance such as squeal can be avoided, and deterioration of heat resistance and heat can be avoided. It is possible to avoid a decrease in strength due to history.
（無機充填材）
無機充填材は、摩擦材の耐熱性の悪化を避けるためや、耐摩耗性を向上させるため、摩擦係数を向上する目的で添加される摩擦調整剤として含まれるものである。本発明の摩擦材は、通常、摩擦材に用いられる無機充填剤であれば特に制限はない。
(Inorganic filler)
The inorganic filler is contained as a friction modifier added for the purpose of improving the friction coefficient in order to avoid deterioration of the heat resistance of the friction material and to improve the wear resistance. The friction material of the present invention is not particularly limited as long as it is an inorganic filler usually used for the friction material.
上記無機充填材としては、例えば、マイカ、硫化錫、二硫化モリブデン、硫化鉄、三硫化アンチモン、硫化ビスマス、硫化亜鉛、酸化カルシウム、硫酸バリウム、コークス、黒鉛、マイカ、バーミキュライト、硫酸カルシウム、タルク、クレー、ゼオライト、ムライト、クロマイト、酸化チタン、酸化マグネシウム、シリカ、ドロマイト、炭酸カルシウム、炭酸マグネシウム、γアルミナ、珪酸ジルコニウム、二酸化マンガン、酸化亜鉛、酸化セリウム、ジルコニア、酸化鉄などを用いることができ、これらを単独でまたは２種類以上を組み合わせて使用することができる。また、前記複数の凸形状を有するチタン酸カリウムの他に粒状または板状のチタン酸塩を組合わせて用いることができる。粒状または板状のチタン酸塩としては、６チタン酸カリウム、８チタン酸カリウム、チタン酸リチウムカリウム、チタン酸マグネシウムカリウム、チタン酸ナトリウムなどを用いることができる。 Examples of the inorganic filler include mica, tin sulfide, molybdenum disulfide, iron sulfide, antimony trisulfide, bismuth sulfide, zinc sulfide, calcium oxide, barium sulfate, coke, graphite, mica, vermiculite, calcium sulfate, talc, and the like. Clay, zeolite, mullite, chromate, titanium oxide, magnesium oxide, silica, dolomite, calcium carbonate, magnesium carbonate, γ alumina, zirconium silicate, manganese dioxide, zinc oxide, cerium oxide, zirconia, iron oxide, etc. can be used. These can be used alone or in combination of two or more. Further, in addition to the above-mentioned potassium titanate having a plurality of convex shapes, granular or plate-shaped titanate can be used in combination. As the granular or plate-shaped titanate, potassium hexatitanate, potassium octatate, lithium titanate, magnesium magnesium titanate, sodium titanate and the like can be used.
本発明の摩擦材中における、無機充填材の含有量は、３０〜８０質量％であることが好ましく、４０〜７０質量％であることがより好ましく、５０〜６０質量％であることが特に好ましい。無機充填材の含有量を３０〜８０質量％の範囲とすることで、耐熱性の悪化を避けることができ、摩擦材のその他成分の含有量バランスの点でも好ましい。 The content of the inorganic filler in the friction material of the present invention is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and particularly preferably 50 to 60% by mass. .. By setting the content of the inorganic filler in the range of 30 to 80% by mass, deterioration of heat resistance can be avoided, and it is also preferable in terms of the content balance of other components of the friction material.
（繊維基材）
繊維基材は、摩擦材において補強作用を示すものである。
(Fiber base material)
The fiber base material exhibits a reinforcing action in the friction material.
本発明の摩擦材は、通常、繊維基材として用いられる、無機繊維、金属繊維、有機繊維、炭素系繊維などを用いることができ、これらを単独でまたは二種類以上を組み合わせて使用することができる。 As the friction material of the present invention, inorganic fibers, metal fibers, organic fibers, carbon-based fibers and the like, which are usually used as a fiber base material, can be used, and these can be used alone or in combination of two or more. it can.
上記無機繊維としては、セラミック繊維、生分解性セラミック繊維、鉱物繊維、ガラス繊維、シリケート繊維などを用いることができ、１種または２種以上を組み合わせて用いることができる。これら、無機繊維の中では、ＳｉＯ２、Ａｌ２Ｏ３、ＣａＯ、ＭｇＯ、ＦｅＯ、Ｎａ２Ｏなどを任意の組み合わせで含有した生分解性鉱物繊維が好ましく、市販品としてはLAPINUS FIBERS B.V製のＲｏｘｕｌシリーズなどが挙げられる。 As the inorganic fiber, ceramic fiber, biodegradable ceramic fiber, mineral fiber, glass fiber, silicate fiber and the like can be used, and one kind or a combination of two or more kinds can be used. Among these inorganic fibers, biodegradable mineral fibers containing SiO 2 , Al 2 O 3 , CaO, MgO, FeO, Na 2 O, etc. in any combination are preferable, and commercially available products are manufactured by LAPINUS FIBERS BV. Examples include the Roxul series.
上記金属繊維としては、通常、摩擦材に用いられるものであれば特に制限はないが、例えば、前記亜鉛粉末以外に、アルミ、鉄、錫、チタン、ニッケル、マグネシウム、シリコンなどの銅および銅合金以外の金属単体または合金形態の繊維や、鋳鉄繊維などの金属を主成分とする繊維が挙げられる。 The metal fiber is not particularly limited as long as it is usually used as a friction material. For example, in addition to the zinc powder, copper and copper alloys such as aluminum, iron, tin, titanium, nickel, magnesium and silicon are used. Examples thereof include fibers in the form of simple substances or alloys other than metals, and fibers containing a metal as a main component, such as cast iron fibers.
上記有機繊維としては、前記フィブリル化アラミド繊維以外に、チョップドアラミド繊維などの枝分かれを持たないアラミド繊維、セルロース繊維、アクリル繊維、フェノール樹脂繊維などを用いることができ、これらを単独でまたは２種類以上を組み合わせて使用することができる。 As the organic fiber, in addition to the fibrillated aramid fiber, aramid fiber having no branching such as chopped aramid fiber, cellulose fiber, acrylic fiber, phenol resin fiber and the like can be used, and these may be used alone or in combination of two or more. Can be used in combination.
上記炭素系繊維としては、耐炎化繊維、ピッチ系炭素繊維、ＰＡＮ系炭素繊維、活性炭繊維などを用いることができ、これらを単独でまたは２種類以上を組み合わせて使用することができる。 As the carbon-based fiber, flame-resistant fiber, pitch-based carbon fiber, PAN-based carbon fiber, activated carbon fiber and the like can be used, and these can be used alone or in combination of two or more.
本発明の摩擦材における、繊維基材の含有量は、摩擦材において５〜４０質量％であることが好ましく、５〜２０質量％であることがより好ましく、５〜１５質量％であることが特に好ましい。繊維基材の含有量を５〜４０質量％の範囲とすることで、摩擦材としての最適な気孔率が得られ、鳴き防止ができ、適正な材料強度が得られ、耐摩耗性を発現し、成形性をよくすることができる。 The content of the fiber base material in the friction material of the present invention is preferably 5 to 40% by mass, more preferably 5 to 20% by mass, and preferably 5 to 15% by mass in the friction material. Especially preferable. By setting the content of the fiber base material in the range of 5 to 40% by mass, the optimum porosity as a friction material can be obtained, squeal can be prevented, appropriate material strength can be obtained, and wear resistance is exhibited. , The moldability can be improved.
［摩擦材］
本発明の摩擦材は、上記の結合剤、有機充填材、無機充填材および繊維基材からなる摩擦材の組成物を一般に使用されている方法で成形して製造することができ、好ましくは加熱加圧成形して製造される。詳細には、例えば、レーディゲミキサー（「レーディゲ」は登録商標）、加圧ニーダー、アイリッヒミキサー（「アイリッヒ」は登録商標）等の混合機を用いて均一に混合し、この混合物を成形金型にて予備成形し、得られた予備成形物を成形温度１３０〜１６０℃、成形圧力２０〜５０ＭＰａ、成形時間２〜１０分間の条件で成形し、得られた成形物を１５０〜２５０℃で２〜１０時間熱処理することで製造される。また更に、必要に応じて塗装、スコーチ処理、研磨処理を行うことで製造される。
[Friction material]
The friction material of the present invention can be produced by molding a composition of a friction material composed of the above-mentioned binder, organic filler, inorganic filler and fiber base material by a commonly used method, and is preferably heated. Manufactured by pressure molding. Specifically, for example, the mixture is uniformly mixed using a mixer such as a Reedige mixer (“Reidigue” is a registered trademark), a pressurized kneader, and an Erich mixer (“Eirich” is a registered trademark) to form this mixture. Pre-molded with a mold, the obtained pre-molded product was molded under the conditions of a molding temperature of 130 to 160 ° C., a molding pressure of 20 to 50 MPa, and a molding time of 2 to 10 minutes, and the obtained molded product was molded at 150 to 250 ° C. It is manufactured by heat treatment for 2 to 10 hours. Furthermore, it is manufactured by performing painting, scorch treatment, and polishing treatment as necessary.
［摩擦部材］
本実施形態の摩擦部材は、上記の本実施形態の摩擦材を摩擦面となる摩擦材として用いてなる。上記摩擦部材としては、例えば、下記の構成が挙げられる。
（１）摩擦材のみの構成。
（２）裏金と、該裏金の上に摩擦面となる本発明の摩擦材とを有する構成。
（３）上記（２）の構成において、裏金と摩擦材との間に、裏金の接着効果を高めるための表面改質を目的としたプライマー層、および、裏金と摩擦材との接着を目的とした接着層を更に介在させた構成。
[Friction member]
The friction member of the present embodiment uses the above-mentioned friction material of the present embodiment as a friction material serving as a friction surface. Examples of the friction member include the following configurations.
(1) Consists of only friction material.
(2) A configuration having a back metal and a friction material of the present invention serving as a friction surface on the back metal.
(3) In the configuration of (2) above, the purpose is to bond a primer layer between the back metal and the friction material for the purpose of surface modification to enhance the adhesive effect of the back metal, and to bond the back metal and the friction material. A structure in which the adhesive layer is further interposed.
上記裏金は、摩擦部材の機械的強度の向上のために、通常、摩擦部材として用いるものであり、材質としては、金属または繊維強化プラスチック等、具体的には、鉄、ステンレス、無機繊維強化プラスチック、炭素繊維強化プラスチック等が挙げられる。プライマー層および接着層は、通常、ブレーキシュー等の摩擦部材に用いられるものであればよい。 The back metal is usually used as a friction member in order to improve the mechanical strength of the friction member, and the material is metal, fiber reinforced plastic, or the like, specifically, iron, stainless steel, or inorganic fiber reinforced plastic. , Carbon fiber reinforced plastic and the like. The primer layer and the adhesive layer may be those usually used for friction members such as brake shoes.
本実施形態の摩擦材は、錆固着力が小さく、錆剥離が少ないため、自動車等のディスクブレーキパッドやブレーキライニング等の上張り材として特に有用であるが、摩擦部材の下張り材として成形して用いることもできる。なお、「上張り材」とは、摩擦部材の摩擦面となる摩擦材であり、「下張り材」とは、摩擦部材の摩擦面となる摩擦材と裏金との間に介在する、摩擦材と裏金との接着部付近のせん断強度、耐クラック性向上等を目的とした層のことである。 The friction material of the present embodiment has a small rust adhesion force and less rust peeling, and is therefore particularly useful as an upholstery material for disc brake pads and brake linings of automobiles, etc., but is molded as an underlay material for friction members. It can also be used. The "upholstery material" is a friction material that serves as a friction surface of the friction member, and the "underlay material" is a friction material that is interposed between the friction material that is the friction surface of the friction member and the back metal. It is a layer for the purpose of improving shear strength and crack resistance in the vicinity of the adhesive portion with the back metal.
以下、本発明の摩擦材および摩擦部材について、実施例および比較例を用いて更に詳細に説明するが、本発明は何らこれらに制限されるものではない。 Hereinafter, the friction material and the friction member of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
［実施例１〜９および比較例１〜４］（ディスクブレーキパッドの作製）
表１に示す配合比率に従って材料を配合し、実施例１〜９および比較例１〜４の摩擦材の組成物を得た。表中の配合比率は質量％である。
[Examples 1 to 9 and Comparative Examples 1 to 4] (Preparation of disc brake pads)
The materials were blended according to the blending ratios shown in Table 1 to obtain the friction material compositions of Examples 1 to 9 and Comparative Examples 1 to 4. The compounding ratio in the table is mass%.
この摩擦材組成物をレーディゲミキサー（株式会社マツボー製、商品名：レーディゲミキサーＭ２０）で混合し、得られた混合物を成形プレス（王子機械工業株式会社製）で予備成形した。得られた予備成形物を成形温度１４０〜１６０℃、成形圧力１５〜４５ＭＰａ、成形時間３〜１０分間の条件で、成形プレス（三起精工株式会社製）を用いて鉄製の裏金（日立オートモティブシステムズ株式会社製）と共に加熱加圧成形した。得られた成形品を２００℃で４．５時間熱処理し、ロータリー研磨機を用いて研磨し、必要に応じてスコーチ処理を行うことで実施例１〜９および比較例１〜４のディスクブレーキパッドを得た。なお、実施例および比較例では、裏金の厚さ６ｍｍ、摩擦材の厚さ１１ｍｍ、摩擦材投影面積５２ｃｍ２のディスクブレーキパッドを作製した。 This friction material composition was mixed with a Ladyge mixer (manufactured by Matsubo Co., Ltd., trade name: Ladyge mixer M20), and the obtained mixture was premolded with a molding press (manufactured by Oji Machinery Co., Ltd.). The obtained premolded product was subjected to an iron backing (Hitachi Automotive Systems) using a molding press (manufactured by Sanki Seiko Co., Ltd.) under the conditions of a molding temperature of 140 to 160 ° C., a molding pressure of 15 to 45 MPa, and a molding time of 3 to 10 minutes. Heat and pressure molding together with (manufactured by Co., Ltd.). The obtained molded product is heat-treated at 200 ° C. for 4.5 hours, polished using a rotary polishing machine, and scorch-treated as necessary to perform disc brake pads of Examples 1 to 9 and Comparative Examples 1 to 4. Got In the examples and comparative examples, disc brake pads having a back metal thickness of 6 mm, a friction material thickness of 11 mm, and a friction material projection area of 52 cm 2 were produced.
（錆固着力および錆剥離の評価）
ＪＩＳ Ｄ４４１４「さび固着試験方法」に準拠し、錆固着試験を行い、錆固着力を下記基準にて評価を行い、錆固着力５０Ｎ未満のものを「◎」、錆固着力５０Ｎ以上かつ１００Ｎ未満のものを「○」、錆固着力１００Ｎ以上のものを「×」として評価し、表１および表２に併せて記載した。
(Evaluation of rust adhesion and rust peeling)
In accordance with JIS D4414 "Rust adhesion test method", a rust adhesion test is conducted, the rust adhesion is evaluated according to the following criteria, and those with a rust adhesion of less than 50N are "◎", and those with a rust adhesion of 50N or more and less than 100N. Those having a rust adhesion of 100 N or more were evaluated as "○", and those having a rust adhesion of 100 N or more were evaluated as "x", and are described together with Tables 1 and 2.
また、上記錆固着試験後、摩擦材の表面が剥離してロータ表面に転移しているかどうかを確認し、錆剥離として評価し、錆剥離が生じていないものを「○」、錆剥離が生じているものを「×」として評価し、この評価結果を表１および表２に併せて記載した。 In addition, after the above rust adhesion test, it is confirmed whether the surface of the friction material is peeled off and transferred to the rotor surface, evaluated as rust peeling, and those without rust peeling are marked with "○", and rust peeling occurs. The rust was evaluated as "x", and the evaluation results are shown in Tables 1 and 2.
本発明の実施例１〜９は、銅を含有する比較例２と同様、錆剥離は発生せず、小さい錆固着力を示した。また、銅を含有せず、フィブリル化アラミド繊維を含有するものの気孔率と硫酸イオン量が本発明の範囲を満足しない比較例１、３、４に対し、実施例１〜９は錆固着力、錆剥離が少ないことは明らかである。 In Examples 1 to 9 of the present invention, similar to Comparative Example 2 containing copper, rust peeling did not occur and a small rust fixing force was exhibited. Further, in contrast to Comparative Examples 1, 3 and 4 which did not contain copper and contained fibrillated aramid fibers but whose porosity and sulfate ion amount did not satisfy the scope of the present invention, Examples 1 to 9 had rust adhesion. It is clear that there is little rust peeling.
本発明の摩擦材組成物は、従来品と比較して、環境負荷の高い銅を用いなくとも、錆固着力が小さく、錆剥離も起こしにくいため、該摩擦材組成物は乗用車用ブレーキパッド等の摩擦材および摩擦部材に好適である。 Compared with conventional products, the friction material composition of the present invention has a small rust adhesion force and is less likely to cause rust peeling even if copper, which has a high environmental load, is not used. Therefore, the friction material composition is used for passenger vehicle brake pads and the like. Suitable for friction materials and friction members.
Claims (9)
該摩擦材中に元素としての銅を含まない、または銅の含有量が０．５質量％以下であり、
前記繊維基材としてフィブリル化アラミド繊維を含有し、
油含浸法で測定される気孔率が１５％以下であって、
イオンクロマトグラフで測定される硫酸イオン濃度が１０００ｐｐｍ以下である摩擦材。 A friction material containing a binder, an organic filler, an inorganic filler and a fiber base material.
The friction material does not contain copper as an element, or the copper content is 0.5% by mass or less.
It contains fibrillated aramid fiber as the fiber base material and contains
The porosity measured by the oil impregnation method is 15% or less,
Sulfate ion concentration measured by ion chromatograph Ru der less 1000ppm friction Kosuzai.
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| KR101878055B1 (en) * | 2016-09-01 | 2018-07-16 | 현대자동차주식회사 | Metallic friction material for brake pad |
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| JPH02186135A (en) * | 1989-01-13 | 1990-07-20 | Nisshinbo Ind Inc | Friction material |
| JPH02186134A (en) * | 1989-01-13 | 1990-07-20 | Nisshinbo Ind Inc | Friction material |
| JPH04249629A (en) * | 1990-12-28 | 1992-09-04 | Toyota Motor Corp | Frictional member |
| JPH04275386A (en) * | 1991-03-02 | 1992-09-30 | Nisshinbo Ind Inc | Non-asbestos friction material |
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| JP5790175B2 (en) * | 2011-06-07 | 2015-10-07 | 日立化成株式会社 | Non-asbestos friction material composition |
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