JP2017114699A - Porous composite particle and production method thereof - Google Patents
Porous composite particle and production method thereof Download PDFInfo
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- JP2017114699A JP2017114699A JP2015248818A JP2015248818A JP2017114699A JP 2017114699 A JP2017114699 A JP 2017114699A JP 2015248818 A JP2015248818 A JP 2015248818A JP 2015248818 A JP2015248818 A JP 2015248818A JP 2017114699 A JP2017114699 A JP 2017114699A
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- porous composite
- friction material
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- 239000011246 composite particle Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000002783 friction material Substances 0.000 claims abstract description 72
- -1 titanate compound Chemical class 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 23
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 43
- 239000010936 titanium Substances 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 229920001187 thermosetting polymer Polymers 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 9
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-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 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 abstract description 10
- 230000016571 aggressive behavior Effects 0.000 abstract description 2
- 230000013011 mating Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 34
- 239000000835 fiber Substances 0.000 description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 238000000227 grinding Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000002904 solvent 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
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910006501 ZrSiO Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007908 dry granulation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 241000224489 Amoeba Species 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010425 asbestos 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
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000002301 combined effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000001914 filtration Methods 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
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000004570 mortar (masonry) Substances 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
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011342 resin composition 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
- 239000007787 solid 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
- 230000003746 surface roughness Effects 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
- 238000003856 thermoforming Methods 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
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Mechanical Operated Clutches (AREA)
- Braking Arrangements (AREA)
Abstract
Description
本発明は、多孔質複合粒子及びその製造方法に関する。 The present invention relates to a porous composite particle and a method for producing the same.
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（結合材）からなる樹脂組成物が摩擦材として使用されてきた。 Friction materials used in brake systems for various vehicles, industrial machines and the like are required to have a high coefficient of friction and be stable and to have excellent wear resistance. In order to satisfy these characteristics, a resin composition comprising a potassium titanate fiber, an inorganic filler, an organic filler, etc., and a thermosetting resin (binding material) such as a phenol resin that binds these is used as a friction material. It has been.
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。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（吸入性繊維とする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。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。 Potassium titanate fiber is not carcinogenic like asbestos and does not damage the rotor like metal fiber. However, many potassium titanate fibers have an average fiber diameter of 0.1 to 0.5 μm and an average fiber length of 10 to 20 μm, and are recommended by the World Health Organization (WHO) (WHO as an inhalable fiber). Fiber: other than a fibrous compound 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. In addition, the potassium titanate fiber does not have sufficient wear resistance at high temperatures. Therefore, Patent Document 1 proposes scaly magnesium potassium titanate, Patent Document 2 proposes scaly lithium potassium titanate, and Patent Document 3 proposes amoeba-like potassium titanate.
一方、摩擦材に銅を含有することで、低温での摩擦係数の安定化、高温での高い摩擦係数を維持することが知られている。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、海洋汚染等の原因となる可能性が示唆されている。また、摩擦材に含有される金属成分が脱落し摩擦材に食い込み、凝集して大きな金属塊となると、ローターを異常摩耗させることが知られている。 On the other hand, it is known that the friction material contains copper to stabilize the friction coefficient at a low temperature and maintain a high friction coefficient at a high temperature. However, it has been suggested that the friction material containing copper contains copper in the abrasion powder generated at the time of braking and may cause river, lake, marine pollution, and the like. It is also known that when the metal component contained in the friction material falls off and bites into the friction material and aggregates into a large metal lump, the rotor is abnormally worn.
そこで、特許文献４では、銅成分を含まない摩擦材であって、安定した摩擦特性を持ち、耐摩耗性に優れ、かつ相手材攻撃性が小さい摩擦材として、複数の凸部形状を有するチタン酸カリウム、モース硬度７以上の研削材、及びエラストマー変性フェノール樹脂を含有する摩擦材を提案している。 Therefore, in Patent Document 4, a friction material that does not contain a copper component, has a stable friction characteristic, is excellent in wear resistance, and has a plurality of convex shapes as a friction material that is less attacking by the counterpart material. A friction material containing potassium acid, a grinding material having a Mohs hardness of 7 or more, and an elastomer-modified phenol resin is proposed.
さらに、摩擦材は耐フェード性が優れていることが求められている。フェード現象は、摩擦材の高温化に伴って摩擦材中の有機成分がガス化し、ディスクとの摩擦界面に気層が形成されることに起因する現象である。摩擦界面の気層の形成を抑制することにより、耐フェード性を改善することができる。それには、摩擦材の気孔率を高めて摩擦界面からガスを逃し易くすることが有効である。 Furthermore, the friction material is required to have excellent fade resistance. The fade phenomenon is a phenomenon resulting from the formation of a gas layer at the frictional interface with the disk due to gasification of organic components in the friction material as the temperature of the friction material increases. By suppressing the formation of a gas layer at the friction interface, the fade resistance can be improved. For this purpose, it is effective to increase the porosity of the friction material so that gas can easily escape from the friction interface.
摩擦材の気孔率を高める方法として、原料混合物を結着成形する工程での成形圧力を低めに調節設定することが考えられるが、成形圧力を低くすると、摩擦材の強度や耐摩耗性が低下し、摩擦特性が得られなくなる。そこで、特許文献５では、棒状、柱状、円柱状、短冊状、粒状及び／又は板状の形状を有するチタン酸アルカリ粒子が結合した中空体からなるチタン酸アルカリの中空体粉末を提案している。 As a method of increasing the porosity of the friction material, it may be possible to adjust and set the molding pressure lower in the process of binding the raw material mixture. However, if the molding pressure is lowered, the strength and wear resistance of the friction material will decrease. As a result, friction characteristics cannot be obtained. Therefore, Patent Document 5 proposes a hollow body powder of alkali titanate composed of a hollow body in which alkali titanate particles having a rod-like, columnar, columnar, strip-like, granular and / or plate-like shape are combined. .
しかし、特許文献１〜５では、銅成分を含有することなく、耐フェード性に優れ、安定した摩擦特性をもち、かつ相手材攻撃性が小さい摩擦材を得ることが難しいという問題がある。 However, Patent Documents 1 to 5 have a problem that it is difficult to obtain a friction material that does not contain a copper component, has excellent fade resistance, has a stable friction characteristic, and has a small counterpart material attack.
本発明の目的は、摩擦材に用いた場合に、優れた耐フェード性、安定した摩擦特性、かつ相手材への低攻撃性を付与することができる多孔質複合粒子を提供することにある。 An object of the present invention is to provide porous composite particles that can impart excellent fade resistance, stable friction characteristics, and low attack to a counterpart material when used in a friction material.
本発明者らは、チタン酸塩化合物と研削材との単なる混合粉末を摩擦材に用いた場合における摩擦材マトリックス中での研削材の存在状態に着目し鋭意研究を重ねた。その結果、チタン酸塩化合物と研削材とを複合化した多孔質粒子が、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 inventors of the present invention have made extensive studies by paying attention to the state of presence of the abrasive in the friction material matrix when a simple powder mixture of the titanate compound and the abrasive is used as the friction material. As a result, the inventors have found that porous particles obtained by combining a titanate compound and an abrasive achieve the above object, and have completed the present invention.
すなわち、本発明は、以下の多孔質複合粒子、摩擦材組成物、摩擦材、摩擦部材、及び多孔質複合粒子の製造方法を提供する。 That is, the present invention provides the following porous composite particles, friction material composition, friction material, friction member, and method for producing porous composite particles.
項１ チタン酸塩化合物の結晶粒とモース硬度６以上の無機化合物粒とが結合した多孔質複合粒子であって、細孔直径０．０１〜１．０μｍの範囲の積算細孔容積が５％以上であることを特徴とする、多孔質複合粒子。 Item 1 A porous composite particle in which a crystal grain of a titanate compound and an inorganic compound grain having a Mohs hardness of 6 or more are combined, and an integrated pore volume within a pore diameter range of 0.01 to 1.0 μm is 5%. A porous composite particle characterized by the above.
項２ 前記無機化合物の含有量が、多孔質複合粒子１００質量％に対して１〜３０質量％であることを特徴とする、項１に記載の多孔質複合粒子。 Item 2 The porous composite particle according to Item 1, wherein the content of the inorganic compound is 1 to 30% by mass with respect to 100% by mass of the porous composite particle.
項３ 前記多孔質複合粒子の平均粒子径が、５〜５００μｍであることを特徴とする、項１又は２に記載の多孔質複合粒子。 Item 3. The porous composite particle according to Item 1 or 2, wherein the porous composite particle has an average particle diameter of 5 to 500 µm.
項４ 前記チタン酸塩化合物が、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］で表されることを特徴とする、項１〜３のいずれか一項に記載の多孔質複合粒子。 Item 4 The titanate compound is 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 porous composite particle according to any one of Items 1 to 3.
項５ 前記無機化合物が、珪酸ジルコニウム、酸化ジルコニウム、酸化ケイ素、酸化アルミニウム、シリコンカーバイド、酸化マグネシウム、酸化鉄（III）、及び酸化クロム（III）の少なくとも１種であることを特徴とする、項１〜４のいずれか一項に記載の多孔質複合粒子。 Item 5 The inorganic compound is at least one of zirconium silicate, zirconium oxide, silicon oxide, aluminum oxide, silicon carbide, magnesium oxide, iron (III) oxide, and chromium (III) oxide. The porous composite particle as described in any one of 1-4.
項６ 項１〜５のいずれか一項に記載の多孔質複合粒子と、熱硬化性樹脂とを含有していることを特徴とする、摩擦材組成物。 Item 6. A friction material composition comprising the porous composite particles according to any one of Items 1 to 5 and a thermosetting resin.
項７ 項６に記載の摩擦材組成物を成形してなる、摩擦材。 Item 7 A friction material obtained by molding the friction material composition according to Item 6.
項８ 項７に記載の摩擦材と基材とを用いて形成される、摩擦部材。 Item 8 A friction member formed using the friction material according to Item 7 and a base material.
項９ 項１〜５のいずれか一項に記載の多孔質複合粒子を製造する方法であって、チタン源とアルカリ金属塩とモース硬度６以上の無機化合物とをメカニカルに粉砕し、粉砕混合物を準備する工程と、前記粉砕混合物を乾式造粒し、造粒物を準備する工程と、前記造粒物を焼成する工程とを備えていることを特徴とする、多孔質複合粒子の製造方法。 Item 9 A method for producing the porous composite particles according to any one of Items 1 to 5, wherein a titanium source, an alkali metal salt, and an inorganic compound having a Mohs hardness of 6 or more are mechanically pulverized, and a pulverized mixture is obtained. A method for producing porous composite particles, comprising a step of preparing, a step of dry granulating the pulverized mixture to prepare a granulated product, and a step of firing the granulated product.
本発明の多孔質複合粒子は、摩擦材に用いた場合に、優れた耐フェード性、安定した摩擦特性、かつ相手材への低攻撃性を付与することができる。 When used for a friction material, the porous composite particles of the present invention can impart excellent fade resistance, stable friction characteristics, and low attack to a counterpart material.
さらに、チタン酸塩化合物と研削材とが一体化されていることから、摩擦材に配合する原料数を削減でき、摩擦材の製造工程を簡便にすることができる。 Furthermore, since the titanate compound and the abrasive are integrated, the number of raw materials blended in the friction material can be reduced, and the manufacturing process of the friction material can be simplified.
以下、好ましい実施形態について説明する。但し、以下の実施形態は単なる例示であり、本発明は以下の実施形態に限定されるものではない。 Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments.
＜多孔質複合粒子＞
本発明の多孔質複合粒子は、チタン酸塩化合物の結晶粒とモース硬度６以上の無機化合物粒とが結合した多孔質複合粒子であって、細孔直径０．０１〜１．０μｍの範囲の積算細孔容積が５％以上であることを特徴とし、チタン酸塩化合物の結晶粒間、チタン酸塩化合物の結晶粒とモース硬度６以上の無機化合物粒とが、焼結及び／又は融着等により強固に結合したものである。本発明によれば、銅成分を含有せずとも、摩擦材に用いて、優れた耐フェード性、安定した摩擦特性、かつ相手材への低攻撃性を付与することができる。
<Porous composite particles>
The porous composite particle of the present invention is a porous composite particle in which a crystal grain of a titanate compound and an inorganic compound particle having a Mohs hardness of 6 or more are combined, and has a pore diameter in the range of 0.01 to 1.0 μm. The accumulated pore volume is 5% or more, and between the crystal grains of the titanate compound, the crystal grains of the titanate compound and the inorganic compound grains having a Mohs hardness of 6 or more are sintered and / or fused. Etc., which are firmly bonded. According to the present invention, even if it does not contain a copper component, it can be used for a friction material to impart excellent fade resistance, stable friction characteristics, and low attack to a counterpart material.
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、さらに好ましくは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、さらに好ましくは３０％である。上記積算細孔容積が小さすぎると、摩擦材に用いた場合に、優れた耐フェード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、チタン酸塩化合物の結晶粒とモース硬度６以上の無機化合物粒と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。細孔分布の極大値は、０．０５〜０．３０μｍの範囲であることが好ましく、０．１０〜０．２５μｍの範囲であることがさらに好ましい。 In the present invention, the cumulative pore volume is preferably 10% or more, and more preferably 15% or more. A preferable upper limit of the cumulative pore volume is 40%, more preferably 30%. If the cumulative pore volume is too small, there may be cases where excellent fade resistance cannot be obtained when used for a friction material. If the cumulative pore volume is too large, the bonding between the titanate compound crystal grains and between the titanate compound crystal grains and the inorganic compound grains having a Mohs hardness of 6 or more becomes weak, and the porous structure cannot be maintained. There is a case. The integrated pore volume can be measured by a mercury intrusion method. The maximum value of the pore distribution is preferably in the range of 0.05 to 0.30 μm, and more preferably in the range of 0.10 to 0.25 μm.
本発明の多孔質複合粒子の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さらに好ましい。上記ＢＥＴ比表面積が小さすぎると、摩擦材に用いた場合に、優れた耐フェード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 composite particles of the present invention is preferably in the range of 1~13m 2 / g, and even more preferably within the range of 3~9m 2 / g. If the BET specific surface area is too small, excellent fade resistance may not be obtained when used as a friction material. If the BET specific surface area is too large, the chemical reaction in the firing step may not be completed.
本発明の多孔質複合粒子における上記無機化合物の含有量は、多孔質複合粒子１００質量％に対して１〜３０質量％であることが好ましい。１質量％より少ないと、チタン酸塩化合物との複合効果が十分に発現されない場合があり、３０質量％より多いと、多孔質構造が保てなくなったり、チタン酸化合物及びモース硬度６以上の無機化合物以外の化合物が生成する場合がある。 It is preferable that content of the said inorganic compound in the porous composite particle of this invention is 1-30 mass% with respect to 100 mass% of porous composite particles. If the amount is less than 1% by mass, the combined effect with the titanate compound may not be sufficiently exhibited. If the amount is more than 30% by mass, the porous structure cannot be maintained, or the titanate compound and an inorganic material having a Mohs hardness of 6 or more. A compound other than the compound may be formed.
本発明の多孔質複合粒子の粒子形状は、球状、不定形状等の粉末状であることが好ましく、非繊維状であることが好ましい。特に、球状であることが好ましい。 The particle shape of the porous composite particles of the present invention is preferably a powder shape such as a spherical shape or an indefinite shape, and is preferably non-fibrous. In particular, a spherical shape is preferable.
本発明の多孔質複合粒子の粒子サイズは特に制限されないが、摩擦材組成物中への分散性の点から、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 composite particles of the present invention is not particularly limited, but from the viewpoint of dispersibility in the friction material composition, the average particle diameter is preferably 5 to 500 μm, more preferably 10 to 300 μm. preferable. In the present invention, the average particle diameter means a particle diameter having an integrated value of 50% in the particle size distribution obtained by a laser diffraction / scattering method in which dispersion by ultrasonic waves is not performed. These various particle shapes and particle sizes can be arbitrarily controlled by production conditions, particularly raw material composition, firing conditions, pulverization conditions, and the like.
本発明の多孔質複合粒子は、分散性の向上、熱硬化性樹脂との密着性の向上等を目的として、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もよい。 The porous composite particles of the present invention are subjected to a surface treatment according to a conventional method with a silane coupling agent, a titanate coupling agent, etc. for the purpose of improving dispersibility and improving adhesion with a thermosetting resin. Also good.
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。 As titanate compounds, composition formula A 2 Ti n O (2n + 1) [wherein A is one or more selected from alkali metals, n = 2 to 8], M x A y Ti (2- y) O 4 [wherein M is an alkali metal excluding lithium, A is one or more selected from lithium, magnesium, zinc, nickel, copper, iron, aluminum, gallium, and manganese, 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. The titanate compound represented by 4 Ti 1.6 O 3.7-4 etc. can be mentioned.
上述のチタン酸塩化合物の中でも、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］で表されること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、この中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。 Among the titanate compounds described above, titanate represented by the composition formula A 2 Ti n O (2n + 1) [wherein A is one or more selected from alkali metals, n = 2 to 8]. it is preferably a compound, wherein, a is one or more selected from alkali metal] formula a 2 Ti 6 O 13 is more preferably a titanate compound be represented by. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium. Among these, lithium, sodium, and potassium are preferable from the economically advantageous point. 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.
本発明の多孔質複合粒子は、上述のように細孔直径が小さいことから、多孔質複合粒子内への熱硬化性樹脂が含浸するのを抑制できる。そのため、本発明の多孔質複合粒子を含有する摩擦材組成物を成形してなる摩擦材において、この多孔質複合粒子はフェードガスの抜け穴となる。このため、原料混合物を結着成形する工程での成形圧力を低めに調節設定しなくても、優れた耐フェード性が得られるものと考えられる。 Since the porous composite particles of the present invention have a small pore diameter as described above, it is possible to suppress impregnation of the thermosetting resin into the porous composite particles. Therefore, in the friction material formed by molding the friction material composition containing the porous composite particles of the present invention, the porous composite particles serve as a fad gas loophole. For this reason, it is considered that excellent fade resistance can be obtained without adjusting and setting the molding pressure in the step of binding and molding the raw material mixture.
また、上記無機化合物が研削材として作用し、チタン酸塩化合物と複合化していることで無機化合物が摩擦材から脱落しにくく安定して存在することができ、安定した摩擦特性、かつ相手材への低攻撃性を付与できるものと考ええられる。 In addition, the inorganic compound acts as an abrasive and is compounded with the titanate compound, so that the inorganic compound can be stably prevented from falling off from the friction material, and stable friction characteristics and to the counterpart material It can be considered that the low aggression property can be imparted.
無機化合物のモース硬度を６以上と限定したのは、チタン酸塩化合物より硬いものを用いることで、チタン酸塩化合物との複合効果を得られるからである。更に、本発明の多孔質複合粒子は、非繊維形状の多孔質体にすることができるので、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。 The reason why the Mohs hardness of the inorganic compound is limited to 6 or more is that a composite effect with the titanate compound can be obtained by using a harder one than the titanate compound. Furthermore, since the porous composite particle of the present invention can be made into a non-fibrous porous body, it is also expected as a friction modifier that does not contain WHO fibers.
本発明の多孔質複合粒子の製造方法は、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とモース硬度６以上の無機化合物と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 the porous composite particles of the present invention is not particularly limited as long as the above-described characteristics can be obtained. For example, the titanium source, the alkali metal salt, and an inorganic compound having a Mohs hardness of 6 or more are mechanically pulverized. Examples thereof include a method of dry granulating the obtained pulverized mixture and producing it by firing.
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。 Examples of the mechanical pulverization include a method of pulverizing while applying a physical impact. Specifically, pulverization by a vibration mill can be mentioned. By pulverizing with a vibration mill, the disorder of atomic arrangement and the decrease in interatomic distance occur simultaneously due to the shear stress due to the grinding of the mixed powder, resulting in atomic movement of the contact part of different particles, resulting in a metastable phase. Can be obtained. Thereby, a pulverized mixture having high reaction activity can be obtained, the firing temperature described later can be lowered, and unreacted substances can be reduced even if the pulverized mixture is granulated. The mechanical pulverization is preferably a dry treatment without using water or a solvent in order to efficiently apply shear stress to the raw material.
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 generally it is preferably in 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複合粒子が得られ、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 pulverized mixture is performed by dry granulation without using water and a solvent. Dry granulation can be performed by a known method, and examples thereof include rolling granulation, fluidized bed granulation, and stirring granulation. Wet granulation is preferable because in the drying process of the granulated product, porous composite particles having large cavities inside are obtained as a result of vaporization of the liquid material inside the granulated product, resulting in a decrease in powder strength. Absent. Moreover, heating is required to vaporize water and the 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 at which the granulated product is fired can be appropriately selected depending on the composition of the target titanate compound, but is preferably in the range of 650 to 1000 ° C and in the range of 800 to 950 ° C. Further preferred. The firing time is preferably 0.5 to 8 hours, and 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 that contains titanium element and does not hinder the formation of oxides by firing, and includes, for example, a compound that is led to titanium oxide by firing in air. Examples of such compounds include titanium oxide, rutile ore, titanium hydroxide wet cake, hydrous titania, and titanium oxide is preferable.
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。 Alkali metal salts include alkali metal carbonates, hydrogen carbonates, organic acid salts such as hydroxides and acetates, sulfates, nitrates, and the like, with carbonates being preferred.
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.
モース硬度６以上の無機化合物としては、摩擦材に含有された場合に相手材を研削し摩擦係数を向上させる目的として使用される無機化合物（研削材）であれば公知のものを使用することができる。具体的には、珪酸ジルコニウム（モース硬度７．５）、酸化ジルコニウム（モース硬度７．５）、酸化ケイ素（モース硬度７）、酸化アルミニウム（モース硬度９）、シリコンカーバイド（モース硬度９）、酸化マグネシウム（モース硬度６）、酸化鉄（III）（モース硬度６）、酸化クロム（III）（モース硬度６．５）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。 As an inorganic compound having a Mohs hardness of 6 or more, a known compound may be used as long as it is an inorganic compound (grinding material) that is used for the purpose of grinding the mating material and improving the friction coefficient when contained in the friction material. it can. Specifically, zirconium silicate (Mohs hardness 7.5), zirconium oxide (Mohs hardness 7.5), silicon oxide (Mohs hardness 7), aluminum oxide (Mohs hardness 9), silicon carbide (Mohs hardness 9), oxidation Examples thereof include magnesium (Mohs hardness 6), iron oxide (III) (Mohs hardness 6), chromium oxide (III) (Mohs hardness 6.5), etc., and one of these may be used alone or in combination of two or more. Can be used.
前述の無機化合物の中でもモース硬度６〜９であることが好ましく、高速・高負荷での制動で要求される高い摩擦係数が得られる点からモース硬度７〜９であることがより好ましい。また、均質な多孔質複合粒子を形成し、無機化合物との複合効果を十分に発現するためには、前述の無機化合物の平均粒子径は好ましくは１〜１０μｍの範囲、より好ましくは１〜５μｍの範囲のものが使用される。 Among the inorganic compounds described above, Mohs hardness of 6 to 9 is preferable, and Mohs hardness of 7 to 9 is more preferable from the viewpoint of obtaining a high friction coefficient required for braking at high speed and high load. Moreover, in order to form homogeneous porous composite particles and to fully exhibit the composite effect with the inorganic compound, the average particle diameter of the inorganic compound is preferably in the range of 1 to 10 μm, more preferably 1 to 5 μm. Those in the range are used.
＜摩擦材組成物＞
本発明の摩擦材組成物は、上記多孔質複合粒子と、熱硬化性樹脂とを含有することを特徴とする。本発明の摩擦材組成物は、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。以下に、本発明の摩擦材組成物の各構成成分について説明する。
<Friction material composition>
The friction material composition of the present invention contains the porous composite particles and a thermosetting resin. The friction material composition of the present invention can further contain other materials as required. Below, each structural component of the friction material composition of this invention is demonstrated.
（多孔質複合粒子）
多孔質複合粒子は、上述のも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。
(Porous composite particles)
The porous composite particles can be appropriately selected from the above-mentioned ones.
摩擦材組成物における多孔質複合粒子の含有量は、摩擦材組成物の合計量１００質量％に対して、３〜３０質量％であることが好ましい。多孔質複合粒子の含有量を３〜３０質量％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 composite particles in the friction material composition is preferably 3 to 30% by mass with respect to 100% by mass of the total amount of the friction material composition. By setting the content of the porous composite particles in the range of 3 to 30% by mass, excellent friction characteristics can be obtained.
（熱硬化性樹脂）
熱硬化性樹脂は、多孔質複合粒子等を一体化し、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。このなかでも良好な耐熱性、成形性、摩擦特性の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 binding material that integrates porous composite particles and the like to give strength, and arbitrarily selected from known thermosetting resins used as the binding material. be able to. For example, phenol resins; elastomer-dispersed phenol resins such as acrylic elastomer-dispersed phenol resins and silicone elastomer-dispersed phenol resins; modified phenol resins such as acrylic-modified phenol resins and silicone-modified phenol resins; formaldehyde resins; melamine resins; epoxy resins; Group polyester resin; urea resin; and the like. One of these may be used alone, or two or more thereof may be used in combination. Of these, phenol resins and modified phenol resins are preferred from the viewpoint of good heat resistance, moldability, and friction characteristics.
摩擦材組成物における熱硬化性樹脂の含有量は、摩擦材組成物の合計量１００質量％に対して、３〜２０質量％であることが好ましい。熱硬化性樹脂の含有量を３〜２０質量％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。 It is preferable that content of the thermosetting resin in a friction material composition is 3-20 mass% with respect to 100 mass% of total amounts of a friction material composition. By setting the content of the thermosetting resin in the range of 3 to 20% by mass, an appropriate amount of the binder is filled in the gaps of the blended material, and excellent friction characteristics can be obtained.
（その他材料）
本発明の摩擦材組成物は、上記の多孔質複合粒子、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 friction material composition of the present invention can contain other materials as needed in addition to the porous composite particles and the thermosetting resin. Examples of other materials include the following fiber base materials and friction modifiers.
繊維基材としては、アラミド繊維、アクリル繊維等の有機繊維；スチール繊維、銅繊維等の金属繊維；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；等が挙げられる。 Examples of fiber base materials include organic fibers such as aramid fibers and acrylic fibers; metal fibers such as steel fibers and copper fibers; glass fibers, rock wool, ceramic fibers, biodegradable fibers, biodissolvable fibers, wollastonite fibers, etc. Inorganic fiber; carbon fiber; and the like.
摩擦調整材としては、カシューダスト、レジンダスト等の有機粉末；合成又は天然黒鉛、カーボンブラック、硫化錫、二硫化モリブデン、三硫化アンチモン、硫酸バリウム、炭酸カルシウム、クレー、マイカ、タルク等の無機粉末；銅、アルミニウム、亜鉛、鉄等の金属粉末；本発明の多孔質複合粒子以外の球状、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；等が挙げられ、これらの１種を単独で、又は２種以上を組み合わせて使用することができる。 As friction modifier, organic powder such as cashew dust, resin dust; inorganic powder such as synthetic or natural graphite, carbon black, tin sulfide, molybdenum disulfide, antimony trisulfide, barium sulfate, calcium carbonate, clay, mica, talc Metal powders such as copper, aluminum, zinc, iron and the like; titanate compound powders having particle shapes such as spherical, layered, plate-like, columnar, block-like, and irregular shapes other than the porous composite particles of the present invention; These 1 type can be used individually or in combination of 2 or more types.
摩擦材組成物におけるその他材料の含有量は、摩擦材組成物の合計量１００質量％に対して、５０〜９４質量％であることが好ましい。 The content of other materials in the friction material composition is preferably 50 to 94% by mass with respect to 100% by mass of the total amount of the friction material composition.
（摩擦材組成物の製造方法）
本発明の摩擦材組成物は、（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 friction material composition)
The friction material composition of the present invention comprises (1) a method of mixing each component with a mixer (Laedge mixer, pressure kneader, Eirich mixer, etc.); (2) a granulated product of the desired component is prepared. If necessary, it can be produced by a method of mixing other components with a mixer (Laedge mixer, pressure kneader, Eirich mixer, etc.);
本発明の摩擦材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。 Content of each component of the friction material composition of this invention can be suitably selected with the desired friction characteristic and a softness | flexibility, and it can manufacture using said manufacturing method.
また、本発明の摩擦材組成物は、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。 The friction material composition of the present invention may be prepared by preparing a master batch containing a specific constituent component at a high concentration, and adding and mixing a thermosetting resin or the like to the master batch.
＜摩擦材及び摩擦部材＞
本発明の摩擦材は、本発明の摩擦材組成物を、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（１５０〜２２０℃、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 a temporary molding of the friction material composition of the present invention at room temperature, and the obtained temporary molding is heated and pressed (molding pressure 10 to 40 MPa, molding temperature 150 to 200 ° C.), If necessary, heat treatment (150 to 220 ° C., holding for 1 to 12 hours) is performed on the obtained molded body in a heating furnace, and then the molded body is subjected to machining and polishing to have a predetermined shape. A friction 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、摩擦面を本発明の摩擦材組成物からなる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 to be a friction surface. The friction member that can be formed using the friction material includes, for example, (1) a configuration of only the friction material, (2) a base material such as a back metal, and a friction surface provided on the base material. The structure etc. which have the friction material which consists of these friction material compositions are mentioned.
上記基材は、摩擦部材の機械的強度の向上の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 for improving the mechanical strength of the friction member, and as the material, metal, fiber reinforced resin, or the like can be used. For example, iron, stainless steel, glass fiber reinforced resin, carbon fiber resin, and the like can be given.
本発明の摩擦材は、各種車両や産業機械のブレーキパッド、ブレーキライニング、クラッチフェーシング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、自然環境への配慮の観点から、銅粉末、銅繊維等の銅を含有しなくても優れた摩擦特性を得ることができる。 The friction material of the present invention can be used for friction members such as brake pads, brake linings, and clutch facings of various vehicles and industrial machines. Moreover, the friction material of this invention can acquire the outstanding friction characteristic, even if it does not contain copper, such as copper powder and copper fiber, from a viewpoint of consideration to a natural environment.
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。 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 implemented with appropriate modifications without departing from the scope of the invention.
＜多孔質複合粒子の製造＞
（実施例１）
酸化チタン６７．５質量％、炭酸ナトリウム１４．９質量％、珪酸ジルコニウム（平均粒子径：１．１μｍ）１７．６質量％となるように秤量した、酸化チタン、炭酸ナトリウム及び珪酸ジルコニ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。
<Manufacture of porous composite particles>
Example 1
Titanium oxide, sodium carbonate and zirconium silicate were weighed so as to be 67.5% by mass of titanium oxide, 14.9% by mass of sodium carbonate, and 17.6% by mass of zirconium silicate (average particle size: 1.1 μm). And mixed for 10 minutes while grinding. The obtained pulverized mixture was dry-granulated with a high speed mixer and then baked 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、Ｕｌｔｉｍａ ＩＶ）により、Ｎａ２Ｔｉ６Ｏ１３とＺｒＳｉＯ４とからなる混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、ＳＡＬＤ−２１００）により測定した結果、３５．７μｍであった。 The obtained powder was confirmed to be a mixed phase composed of Na 2 Ti 6 O 13 and ZrSiO 4 using an X-ray diffraction measurement device (Rigaku Corporation, Ultimate IV). The average particle size was 35.7 μm as a result of measurement using a laser diffraction particle size distribution analyzer (SALD-2100, manufactured by Shimadzu Corporation).
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、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球状粒子であることが分かる。 The shape of the obtained powder was observed using a field emission scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation, S-4800). FIG. 1 shows an SEM photograph of the whole image of the particle, and FIG. 2 shows an SEM photograph of the internal structure of the particle. 1 and 2, it can be seen that the obtained powder is spherical particles having fine voids of less than 1 μm between 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、ポアマスター６０−ＧＴ）を用いて測定した。０．０１〜１．０μｍの細孔直径範囲にある積算細孔容積は２３．５％、細孔分布の極大値は０．２２μｍであった。 The pores of the obtained powder were measured using a mercury porosimeter (manufactured by Quanta Chrome, Poremaster 60-GT). The cumulative pore volume in the pore diameter range of 0.01 to 1.0 μm was 23.5%, and the maximum value of the pore distribution was 0.22 μm.
又、得られた粉末についてＢＥＴ比表面積を測定した結果、６．９ｍ２／ｇであった。 Moreover, as a result of measuring the BET specific surface area about the obtained powder, it was 6.9 m < 2 > / g.
（実施例２）
酸化チタン６３．９質量％、炭酸カリウム１８．４質量％、珪酸ジルコニウム（平均粒子径：１．１μｍ）１７．６質量％となるように秤量した、酸化チタン、炭酸カリウム及び珪酸ジルコニ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。
(Example 2)
Titanium oxide, potassium carbonate and zirconium silicate were weighed so as to be 63.9% by mass of titanium oxide, 18.4% by mass of potassium carbonate, and 17.6% by mass of zirconium silicate (average particle size: 1.1 μm). And mixed for 10 minutes while grinding. The obtained pulverized mixture was dry-granulated with a high speed mixer and then baked at 850 ° C. for 4 hours in an electric furnace to obtain a powder.
得られた粉末の評価は、実施例１と同様に行った。その結果、Ｋ２Ｔｉ６Ｏ１３とＺｒＳｉＯ４とからなる混相であり、平均粒子径は６６．２μｍ、０．０１〜１．０μｍの細孔直径範囲にある積算細孔容積は２１．２％、細孔分布の極大値は０．１１μｍの球状粒子であることを確認した。 Evaluation of the obtained powder was performed in the same manner as in Example 1. As a result, it is a mixed phase composed of K 2 Ti 6 O 13 and ZrSiO 4 , the average particle diameter is 66.2 μm, and the cumulative pore volume in the pore diameter range of 0.01 to 1.0 μm is 21.2%. It was confirmed that the maximum value of the pore distribution was 0.11 μm spherical particles.
又、得られた粉末についてＢＥＴ比表面積を測定した結果、６．０ｍ２／ｇであった。 Moreover, as a result of measuring the BET specific surface area about the obtained powder, it was 6.0 m < 2 > / g.
＜多孔質チタン酸塩化合物粒子の製造＞
（参考例１）
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。
<Production of porous titanate compound particles>
(Reference Example 1)
Titanium oxide and sodium carbonate weighed so that Ti: Na = 3: 1 (molar ratio) were mixed for 10 minutes while being pulverized with a vibration mill. The obtained pulverized mixture was dry-granulated with a high speed mixer and then baked at 850 ° C. for 4 hours in an electric furnace to obtain a powder.
得られた粉末の評価は、実施例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５６μｍ、０．０１〜１．０μｍの細孔直径範囲にある積算細孔容積は２０．３％、細孔分布の極大値は０．２４μｍの球状の多孔質チタン酸塩化合物粒子であることを確認した。 Evaluation of the obtained powder was performed in the same manner as in Example 1. As a result, it is a single phase of Na 2 Ti 6 O 13 , the average particle size is 56 μm, the cumulative pore volume in the pore diameter range of 0.01 to 1.0 μm is 20.3%, and the maximum pore distribution The value was confirmed to be 0.24 μm spherical porous titanate compound particles.
又、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。 Moreover, as a result of measuring a BET specific surface area about the obtained powder, it was 4.4 m < 2 > / g.
（参考例２）
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。
(Reference Example 2)
Titanium oxide and sodium carbonate weighed so that Ti: K = 3: 1 (molar ratio) were mixed for 10 minutes while being pulverized with a vibration mill. The obtained pulverized mixture was dry-granulated with a high speed mixer and then baked at 850 ° C. for 4 hours in an electric furnace to obtain a powder.
得られた粉末の評価は、実施例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１６９μｍ、０．０１〜１．０μｍの細孔直径範囲にある積算細孔容積は１９．８％、細孔分布の極大値は０．１３μｍの球状の多孔質チタン酸塩化合物粒子であることを確認した。 Evaluation of the obtained powder was performed in the same manner as in Example 1. As a result, it was a single phase of K 2 Ti 6 O 13 , the average particle diameter was 169 μm, the cumulative pore volume in the pore diameter range of 0.01 to 1.0 μm was 19.8%, and the maximum pore distribution The value was confirmed to be 0.13 μm spherical porous titanate compound particles.
又、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。 Moreover, as a result of measuring a BET specific surface area about the obtained powder, it was 5.9 m < 2 > / g.
＜比較のチタン酸塩化合物粒子の製造＞
（比較例１）
以下のようにして、上記特許文献５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。
<Production of comparative titanate compound particles>
(Comparative Example 1)
The hollow titanate compound particles disclosed in Patent Document 5 were produced 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 weighed so that Ti: K = 3: 1 (molar ratio) were mixed for 10 minutes while being pulverized with a vibration mill. The obtained pulverized mixture was baked at 1050 ° C. for 4 hours in an electric furnace, and the baked product was pulverized with a pulverizer. 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, an ethylcellulose-based binder, and a polycarboxylic acid ammonium salt, and the resulting 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、実施例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、１〜５μｍの空隙を多く持つ中空状球状粒子であることが分かる。 Evaluation of the obtained powder was performed in the same manner as in Example 1. As a result, it was a single phase of K 2 Ti 6 O 13 , the average particle size 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 The value was confirmed to be 1.9 μm spherical particles. FIG. 3 shows an SEM photograph of the whole image of the particle, and FIG. 4 shows an SEM photograph of the internal structure of the particle. 3 and 4, it can be seen that the hollow spherical particles have many voids of 1 to 5 μm.
又、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。 Moreover, as a result of measuring a BET specific surface area about the obtained powder, it was 0.6 m < 2 > / g.
（比較例２）
比較例１で得られた粉末を乳鉢で粉砕し、柱状粉末を得た。図５に粒子の全体像のＳＥＭ写真を示した。
(Comparative Example 2)
The powder obtained in Comparative Example 1 was pulverized in a mortar to obtain a columnar powder. FIG. 5 shows a SEM photograph of the entire particle.
（比較例３）
Ｔｉ：Ｋ＝１：１（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常法により混合し、原料混合物を振動ミルにて粉砕しながら３０分間混合した。得られた粉砕混合物を電気炉にて７８０℃で４時間焼成後、焼成物を粉砕することで、２チタン酸カリウム（Ｋ２Ｔｉ２Ｏ５）を得た。
(Comparative Example 3)
Titanium oxide and potassium carbonate weighed so that Ti: K = 1: 1 (molar ratio) were mixed by a conventional method, and the raw material mixture was mixed for 30 minutes while pulverizing with a vibration mill. The obtained pulverized mixture was baked at 780 ° C. for 4 hours in an electric furnace, and then the baked product was pulverized to obtain potassium dititanate (K 2 Ti 2 O 5 ).
得られた２チタン酸カリウムを水中に分散させ１５質量％スラリーを調製し、さらに酸を添加した。このスラリーの固形分を濾取し、乾燥した。乾燥後、電気炉にて６００℃で１時間焼成し、焼成物をハンマーミルにて解砕することで粉末を得た。 The obtained potassium dititanate was dispersed in water to prepare a 15% by mass slurry, and an acid was further added. The solid content of this slurry was collected by filtration and dried. After drying, it was fired at 600 ° C. for 1 hour in an electric furnace, and the fired product was crushed with a hammer mill to obtain a powder.
得られた粉末は、Ｘ線回折測定装置により７．９チタン酸カリウム（Ｋ２Ｔｉ７．９Ｏ１６．８）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により１１μｍであった。粉末の形状は、ＳＥＭを用いて不定形の形状を有し、不規則な方向に複数の突起が延びる形状（アメーバ形状）を有している粒子であることを確認した。 The obtained powder was confirmed to be 7.9 potassium titanate (K 2 Ti 7.9 O 16.8 ) using an X-ray diffractometer. The average particle diameter was 11 μm by a laser diffraction particle size distribution analyzer. The shape of the powder was confirmed to be particles having an irregular shape using an SEM and having a shape (amoeba shape) in which a plurality of protrusions extend in an irregular direction.
＜摩擦材の製造＞
表１に従う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、得られた混合物を仮成形（２５ＭＰａ）、熱成形（１５０℃、２０ＭＰａ）を行い、さらに２２０℃で熱処理を行った。得られた成形体を面積５．５ｃｍ２の扇形に加工して摩擦材を得た。
<Manufacture of friction material>
The materials were blended according to the blending ratio according to Table 1, mixed with a Laedige mixer, the resulting mixture was subjected to temporary molding (25 MPa), thermoforming (150 ° C., 20 MPa), and further heat-treated at 220 ° C. . The obtained molded body was processed into a sector shape having an area of 5.5 cm 2 to obtain a friction material.
＜摩擦材の評価＞
摩擦試験は、汎用のフルサイズダイナモ試験機を用いてＪＡＳＯ Ｃ−４０６に準拠して行い、「第１フェード試験における制動１０回中の最低摩擦係数」及び「平均摩擦係数」を測定した。対面損傷性は、フェード試験後の相手材(材種：ＦＣ２５０)の摩擦面を非接触式３Ｄ測定機（キーエンス社製、ＶＲ−３０００）にて平均粗さＲａを測定した。表面粗さＲａはＪＩＳ Ｂ０６０１で規格された算術平均粗さ（Ｒａ）を表している。摩擦材の気孔率は、ＪＩＳ Ｄ４４１８に準拠して、油中含浸により測定を行った。結果を表１に示した。
<Evaluation of friction material>
The friction test was performed in accordance with JASO C-406 using a general-purpose full-size dynamo testing machine, and the “minimum friction coefficient during 10 brakings in the first fade test” and the “average friction coefficient” were measured. For the face-to-face damage, the average roughness Ra of the friction surface of the counterpart material (material type: FC250) after the fade test was measured with a non-contact type 3D measuring machine (manufactured by Keyence Corporation, VR-3000). The surface roughness Ra represents the arithmetic average roughness (Ra) standardized by JIS B0601. The porosity of the friction material was measured by impregnation in oil according to JIS D4418. The results are shown in Table 1.
表１に示すように、本発明に従う実施例１及び２の多孔質複合粒子を用いた実施例３及び４は、比較例１〜３のチタン酸塩化合物粒子を用いた比較例８〜１０に比べ、最低摩擦係数及び平均摩擦係数が高く、対面損傷性が少なくなっていることが分かる。また、実施例３及び４と、参考例１及び２の多孔質チタン酸塩化合物粒子を用いた比較例４〜７との比較から、単にケイ酸ジルコニウムと多孔質チタン酸塩化合物粒子とを摩擦材組成物を調製する際に混合するのみでは、本発明の効果が得られないことが分かる。 As shown in Table 1, Examples 3 and 4 using the porous composite particles of Examples 1 and 2 according to the present invention correspond to Comparative Examples 8 to 10 using the titanate compound particles of Comparative Examples 1 to 3, respectively. In comparison, it can be seen that the minimum coefficient of friction and the average coefficient of friction are high, and the face-to-face damage is reduced. Further, from comparison between Examples 3 and 4 and Comparative Examples 4 to 7 using the porous titanate compound particles of Reference Examples 1 and 2, friction was simply caused between zirconium silicate and porous titanate compound particles. It turns out that the effect of this invention is not acquired only by mixing at the time of preparing a material composition.
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| JPH09328561A (en) * | 1996-06-12 | 1997-12-22 | Kubota Corp | Friction material |
| JP2010030812A (en) * | 2008-07-28 | 2010-02-12 | Toho Titanium Co Ltd | Method for producing alkali metal titanate composite particle |
| WO2010137582A1 (en) * | 2009-05-26 | 2010-12-02 | 石原産業株式会社 | Lithium titanate, process for production of same, and electrode active material and electricity storage device each comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09328561A (en) * | 1996-06-12 | 1997-12-22 | Kubota Corp | Friction material |
| JP2010030812A (en) * | 2008-07-28 | 2010-02-12 | Toho Titanium Co Ltd | Method for producing alkali metal titanate composite particle |
| WO2010137582A1 (en) * | 2009-05-26 | 2010-12-02 | 石原産業株式会社 | Lithium titanate, process for production of same, and electrode active material and electricity storage device each comprising same |
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