JP2016130183A - Lepidochrocite-type titanate, method for producing the same, and inorganic composite material, resin composition and friction material containing the same - Google Patents
Lepidochrocite-type titanate, method for producing the same, and inorganic composite material, resin composition and friction material containing the same Download PDFInfo
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- JP2016130183A JP2016130183A JP2015004162A JP2015004162A JP2016130183A JP 2016130183 A JP2016130183 A JP 2016130183A JP 2015004162 A JP2015004162 A JP 2015004162A JP 2015004162 A JP2015004162 A JP 2015004162A JP 2016130183 A JP2016130183 A JP 2016130183A
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- lipidocrocite
- titanate
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011342 resin composition Substances 0.000 title claims abstract description 23
- 239000002783 friction material Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910003471 inorganic composite material Inorganic materials 0.000 title claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 24
- 150000002736 metal compounds Chemical class 0.000 claims description 23
- 238000010304 firing Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 24
- 239000002002 slurry Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000007580 dry-mixing Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline earth metals Titanate Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 2
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000224489 Amoeba Species 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 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
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 239000011229 interlayer Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 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
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 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
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、レピドクロサイト型チタン酸塩及びその製造方法、それを含有する無機複合材、樹脂組成物並びに摩擦材に関する。 The present invention relates to a lipidocrocite-type titanate and a production method thereof, an inorganic composite material containing the same, a resin composition, and a friction material.
各種車両や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、ローター攻撃性が低い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、アスベスト、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。しかし、アスベストは発癌性が確認されており、かつ粉塵化し易いため、作業時の吸入による環境衛生上の問題からその使用が自粛されたことから、代替品としてチタン酸カリウム繊維、金属繊維等が使用されてきた。 Friction materials used in brake systems for various vehicles and industrial machines are required to have high and stable friction coefficients, excellent wear resistance, and low rotor attack. In order to satisfy these characteristics, resin compositions comprising asbestos, inorganic fillers, organic fillers, etc., and thermosetting resins (binders) such as phenol resins that bind them have been used as friction materials. . However, since asbestos has been confirmed to be carcinogenic and is easily dusted, its use has been refrained from environmental hygiene problems due to inhalation during work. As an alternative, potassium titanate fiber, metal fiber, etc. Have been used.
チタン酸カリウム繊維は、ローターを傷付けないという利点を有している。しかし、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、摩擦調整材として鱗片状のチタン酸マグネシウムカリウム（Ｋ０．２〜０．７Ｍｇ０．４Ｔｉ１．６Ｏ３．７〜４）を使用することが提案されている。また、特許文献２では、摩擦調整材として鱗片状のチタン酸リチウムカリウム（Ｋ０．５〜０．７Ｌｉ０．２７Ｔｉ１．７３Ｏ３．８５〜３．９５）を使用することが提案されている。
Potassium titanate fibers have the advantage of not damaging the rotor. However, the wear resistance at high temperatures is not sufficient. Therefore, in
金属繊維としては、摩擦材の強度補強、放熱効率の向上、耐摩耗性の向上のために、ローター攻撃性が低い銅繊維が使用されている。さらに耐摩耗性を向上させるために銅粉末も多量に用いられている。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、湖や海洋汚染などの原因となる可能性が示唆されていることから、北米において銅の使用量が規制されることになった。そこで、特許文献３では、チタン酸リチウムカリウム及び黒鉛を含有する樹脂組成物を摩擦材として使用することが提案されている。 As the metal fibers, copper fibers having low rotor attack are used for reinforcing the strength of the friction material, improving the heat dissipation efficiency, and improving the wear resistance. Further, a large amount of copper powder is also used to improve wear resistance. However, it is suggested that friction materials containing copper contain copper in the abrasion powder generated during braking, which may cause river, lake and marine pollution. It was to be done. Therefore, Patent Document 3 proposes the use of a resin composition containing lithium potassium titanate and graphite as a friction material.
しかし、特許文献１〜３で用いられるチタン酸塩は、結晶構造が層状構造であり、樹脂組成物の成形時に層状構造の層間に配位しているアルカリ成分が溶出し、樹脂組成物のマトリックスを構成する熱硬化性樹脂の硬化阻害を起こす問題がある。このことにより、成形温度を高くしたり、成形時間を長くしたりする必要があり、また得られる樹脂組成物が劣化することもある。
However, the titanate used in
本発明の目的は、熱硬化性樹脂の硬化阻害を抑制することができるレピドクロサイト型チタン酸塩、その製造方法及び無機複合材並びに優れた耐摩耗性を有する樹脂組成物及び摩擦材を提供することにある。 An object of the present invention is to provide a lipidcrocite-type titanate capable of suppressing the inhibition of curing of a thermosetting resin, a production method thereof, an inorganic composite material, a resin composition having excellent wear resistance, and a friction material. There is to do.
本発明は、以下のレピドクロサイト型チタン酸塩、及びその製造方法、それを含有する無機複合材、樹脂組成物並びに摩擦材を提供する。 The present invention provides the following lipidocrosite-type titanate, a method for producing the same, an inorganic composite material containing the same, a resin composition, and a friction material.
項１ ＴｉＯ６八面体の連鎖により形成される層状構造を有し、Ｔｉ席の一部がＬｉ，Ｍｇ，Ｚｎ，Ｎｉ，Ｃｕ，Ｆｅ，Ａｌ，Ｇａ，Ｍｎから選ばれる少なくとも１種のＭ金属イオンで置換され、層間にＬｉを除くアルカリ金属から選ばれる少なくとも１種のＡ金属イオンと、アルカリ土類金属から選ばれる少なくとも１種のＢ金属イオンとを有することを特徴とするレピドクロサイト型チタン酸塩。 Item 1: At least one M metal having a layered structure formed by a chain of TiO 6 octahedrons, part of which is selected from Li, Mg, Zn, Ni, Cu, Fe, Al, Ga, and Mn Repidocrosite type, characterized by having at least one A metal ion selected from alkali metals excluding Li and intercalated with ions, and at least one B metal ion selected from alkaline earth metals Titanate.
項２ Ｔｉ席の１０〜４０モル％が、前記Ｍ金属イオンで置換されていることを特徴とする、項１に記載のレピドクロサイト型チタン酸塩。
Item 2 10. The lipidocrocite-type titanate according to
項３ 層間の前記Ａ金属イオンと前記Ｂ金属イオンとのモル比（Ａ金属イオン：Ｂ金属イオン）が、（５０：５０）〜（９９：１）の範囲であることを特徴とする、項１又は２に記載のレピドクロサイト型チタン酸塩。 Item 3 The molar ratio of the A metal ion and the B metal ion between the layers (A metal ion: B metal ion) is in the range of (50:50) to (99: 1), The lepidochrosite titanate according to 1 or 2.
項４ 組成式：Ａ（０．２〜０．７）−ｘＢｘ／２Ｍｇ０．４Ｔｉ１．６Ｏ３．７〜４［式中、Ａはリチウムを除くアルカリ金属、Ｂはアルカリ土類金属から選ばれる少なくとも１種、ｘは０．００２≦ｘ≦０．３５］で表わ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レピドクロサイト型チタン酸塩。
Item 4 Composition formula: A (0.2 to 0.7) -x B x / 2 Mg 0.4 Ti 1.6 O 3.7 to 4 [In the formula, A is an alkali metal excluding lithium, and B is an alkali. Item 4. A lipidocrocite-type titanate according to any one of
項５ 組成式：Ａ（０．５〜０．７）−ｘＢｘ／２Ｌｉ０．２７Ｔｉ１．７３Ｏ３．８５〜３．９５［式中、Ａはリチウムを除くアルカリ金属、Ｂはアルカリ土類金属から選ばれる少なくとも１種、ｘは０．００５≦ｘ≦０．３５］で表わ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レピドクロサイト型チタン酸塩。 Item 5 Composition formula: A (0.5 to 0.7) -x B x / 2 Li 0.27 Ti 1.73 O 3.85 to 3.95 [wherein A is an alkali metal excluding lithium, B Item 4 is at least one selected from alkaline earth metals, and x is expressed by 0.005 ≦ x ≦ 0.35]. Acid salt.
項６ 項１〜５のいずれか一項に記載のレピドクロサイト型チタン酸塩とＢ金属化合物とを含むことを特徴とする無機複合材。
Item 6 An inorganic composite material comprising the lipidocrosite type titanate according to any one of
項７ 項１〜５のいずれか一項に記載のレピドクロサイト型チタン酸塩又は項６に記載の無機複合材と熱硬化性樹脂とを含有していることを特徴とする樹脂組成物。
Item 7 A resin composition comprising the lipidocrocite-type titanate according to any one of
項８ 項７に記載の樹脂組成物を含有していることを特徴とする摩擦材。 Item 8 A friction material comprising the resin composition according to Item 7.
項９ 項１〜５のいずれか一項に記載のレピドクロサイト型チタン酸塩を製造する方法であって、チタン化合物とＡ金属化合物とＭ金属化合物との混合物を焼成して焼成物を準備する工程と、前記焼成物を酸洗浄して酸洗浄物を準備する工程と、Ｂ金属化合物と前記酸洗浄物との混合物を焼成する工程とを備えることを特徴とするレピドクロサイト型チタン酸塩の製造方法。
Item 9 A method for producing a lipidocrocite-type titanate according to any one of
本発明のレピドクロサイト型チタン酸塩及び無機複合材は、熱硬化性樹脂の硬化阻害を抑制することができる。本発明の樹脂組成物は、硬化阻害を受けることなく、硬化させることができる。本発明の樹脂組成物及び摩擦材は、優れた耐摩耗性を有している。本発明の製造方法によれば、上記本発明のレピドクロサイト型チタン酸塩を効率良く製造することができる。 The lipidocrosite type titanate and the inorganic composite material of the present invention can suppress the inhibition of curing of the thermosetting resin. The resin composition of the present invention can be cured without being inhibited by curing. The resin composition and friction material of the present invention have excellent wear resistance. According to the production method of the present invention, the above-described lipidocrocite-type titanate of the present invention can be efficiently produced.
以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は単なる例示である。本発明は、下記の実施形態に何ら限定されない。 Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.
本発明のチタン酸塩は、レピドクロサイト型チタン酸塩であり、ＴｉＯ６八面体の連鎖により形成される層状構造を有し、その層間に金属イオンを有する結晶である。この層は本来電気的に中性であるが、４価のＴｉ席の一部を１価〜３価の金属イオンで置換されることで負に帯電している。これらを層間の金属イオンが補償する形になっている。 The titanate of the present invention is a lipid docrosite type titanate, which is a crystal having a layered structure formed by a chain of TiO 6 octahedrons and having metal ions between the layers. This layer is inherently electrically neutral, but is negatively charged by replacing a part of the tetravalent Ti site with a monovalent to trivalent metal ion. These are compensated by metal ions between the layers.
Ｔｉ席の一部を置換する金属イオンは、Ｔｉ４＋と同程度のイオン半径を有しているＬｉ、Ｍｇ、Ｚｎ、Ｎｉ、Ｃｕ、Ｆｅ、Ａｌ、Ｇａ、Ｍｎから選ばれる少なくとも１種の金属（これらを総称して「Ｍ金属」と略記する）のイオン（Ｍ金属イオン）であり、好ましくはＴｉ席の１０〜４０モル％が上記Ｍ金属イオンで置換されていることがよく、より好ましくはＴｉ席の１０〜３０モル％が上記Ｍ金属イオンで置換されていることがよい。 The metal ion that replaces a part of the Ti site is at least one metal selected from Li, Mg, Zn, Ni, Cu, Fe, Al, Ga, and Mn having an ion radius comparable to that of Ti 4+ (M metal ions are generally referred to as "M metal"), and preferably 10 to 40 mol% of the Ti site is substituted with the M metal ion, more preferably It is preferable that 10 to 30 mol% of the Ti seat is substituted with the M metal ion.
層間の金属イオンは、イオン半径が小さいＬｉを除くアルカリ金属から選ばれる少なくとも１種の金属（これらを総称して「Ａ金属」と略記する）のイオン（Ａ金属イオン）と、アルカリ土類金属から選ばれる少なくとも１種の金属（これらを総称して「Ｂ金属」と略記する）のイオン（Ｂ金属イオン）である。 The metal ions between the layers include ions (A metal ions) of at least one metal selected from alkali metals excluding Li having a small ionic radius (these are collectively abbreviated as “A metal”), and alkaline earth metals. An ion (B metal ion) of at least one metal selected from the above (collectively abbreviated as “B metal”).
Ａ金属としてはＮａ、Ｋ、Ｒｂ、Ｃｓ等を例示することができ、好ましくはＫがよい。Ｂ金属としては、Ｃａ、Ｓｒ、Ｂａ、Ｒａ等を例示することができ、好ましくはＣａ、Ｂａがよい。また、結晶全体を電気的に中性にできる量の金属イオンを層間に有していることが好ましく、層間のＡ金属イオンとＢ金属イオンとのモル比（Ａ金属イオン：Ｂ金属イオン）が、（５０：５０）〜（９９：１）の範囲であることがより好ましい。 Examples of the A metal include Na, K, Rb, and Cs. K is preferable. Examples of the B metal include Ca, Sr, Ba, Ra and the like, and Ca and Ba are preferable. Further, it is preferable to have an amount of metal ions that can neutralize the entire crystal between layers, and the molar ratio of A metal ions to B metal ions between the layers (A metal ions: B metal ions) , (50:50) to (99: 1) is more preferable.
本発明のチタン酸塩は、層間にＡ金属イオンとＢ金属イオンとを有することで、熱硬化性樹脂の硬化阻害を抑制することができる。熱硬化性樹脂の硬化阻害を抑制することができる理由について、詳細は明らかではないが、層間のアルカリ成分の溶出を防ぎ、熱硬化性樹脂の硬化阻害を抑制することができるものと考えられる。 The titanate of this invention can suppress hardening inhibition of a thermosetting resin by having A metal ion and B metal ion between layers. Although it is not clear about the reason why the inhibition of curing of the thermosetting resin can be suppressed, it is considered that the elution of alkali components between layers can be prevented and the inhibition of curing of the thermosetting resin can be suppressed.
本発明のチタン酸塩は、球状、粒状、板状、柱状、ブロック状、不定形状、複数の凸部を有する形状（アメーバ形状）等の粉末状の非繊維状粒子である。これらの各種粒子形態および粒子サイズは、製造条件、特に原料組成、焼成条件、焼成処理後の粉砕処理条件などにより任意に制御することができる。 The titanate of the present invention is powdery non-fibrous particles such as a spherical shape, a granular shape, a plate shape, a column shape, a block shape, an indefinite shape, and a shape having a plurality of convex portions (amoeba shape). These various particle forms and particle sizes can be arbitrarily controlled by production conditions, particularly raw material composition, firing conditions, pulverization conditions after firing, and the like.
樹脂組成物に配合されるチタン酸塩は、上記各種の粒子形態を有するものを適宜使用することができる。 As the titanate blended in the resin composition, those having the above-mentioned various particle forms can be appropriately used.
本発明のチタン酸塩は、例えば、組成式：Ａ（０．２〜０．７）−ｘＢｘ／２Ｍｇ０．４Ｔｉ１．６Ｏ３．７〜４［式中、Ａはリチウムを除くアルカリ金属、Ｂはアルカリ土類金属から選ばれる少なくとも１種、ｘは０．００２≦ｘ≦０．３５］、組成式：Ａ（０．５〜０．７）−ｘＢｘ／２Ｌｉ０．２７Ｔｉ１．７３Ｏ３．８５〜３．９５［式中、Ａはリチウムを除くアルカリ金属、Ｂはアルカリ土類金属から選ばれる少なくとも１種、ｘは０．００５≦ｘ≦０．３５］等で表される化合物を例示することができ、そのなかでも式：Ｋ（０．２〜０．７）−ｘＢａｘ／２Ｍｇ０．４Ｔｉ１．６Ｏ３．７〜４［式中、ｘは０．００２≦ｘ≦０．３５］、式：Ｋ（０．５〜０．７）−ｘＢａｘ／２Ｌｉ０．２７Ｔｉ１．７３Ｏ３．８５〜３．９５［式中、ｘは０．００５≦ｘ≦０．３５］等で表される化合物が好ましい。 Titanate of the present invention, for example, the composition formula: A (0.2 to 0.7) in -x B x / 2 Mg 0.4 Ti 1.6 O 3.7~4 [ wherein, A is lithium And B is at least one selected from alkaline earth metals, x is 0.002 ≦ x ≦ 0.35], composition formula: A (0.5 to 0.7) −x B x / 2 Li 0.27 Ti 1.73 O 3.85 to 3.95 [wherein A is an alkali metal excluding lithium, B is at least one selected from alkaline earth metals, and x is 0.005 ≦ x ≦ 0. .35] and the like, among which the formula: K (0.2-0.7) -x Ba x / 2 Mg 0.4 Ti 1.6 O 3.7- 4 [wherein x is 0.002 ≦ x ≦ 0.35], formula: K (0.5 to 0.7) −x Ba x / 2 Li 0.27 Ti 1 .73 O 3.85 to 3.95 [wherein x is preferably 0.005 ≦ x ≦ 0.35] or the like.
本発明のチタン酸塩の製造方法は特に限定されるものではないが、例えば、酸化チタン又は加熱により酸化チタンを生成する化合物（これらを総称して「チタン化合物」と略記する）と、Ａ金属の酸化物、加熱によりＡ金属の酸化物を生成する化合物又はＡ金属の塩（これらを総称して「Ａ金属化合物」と略記する）と、Ｍ金属の酸化物、加熱によりＭ金属の酸化物を生成する化合物又はＭ金属の塩（これらを総称して「Ｍ金属化合物」と略記する）と、フラックスとを混合した混合物を焼成（１次焼成）して焼成物（１次焼成物）を準備し、得られた焼成物を酸洗浄して酸洗浄物を準備し、さらにＢ金属の酸化物、加熱によりＢ金属の酸化物を生成する化合物又はＢ金属の塩（これらを総称して「Ｂ金属化合物」と略記する）と得られた酸洗浄物との混合物を焼成（２次焼成）することにより得ることができる。なお、上記フラックスは混合しなくともよい。上記フラックスを混合した場合、反応をより一層均一化することができ、また結晶をより一層成長させることができるため好ましい。 The method for producing the titanate of the present invention is not particularly limited. For example, titanium oxide or a compound that generates titanium oxide by heating (generically abbreviated as “titanium compound”) and A metal Oxides, compounds that produce A metal oxides upon heating or A metal salts (collectively abbreviated as “A metal compounds”), M metal oxides, M metal oxides upon heating Or a mixture of M metal salt (collectively abbreviated as “M metal compound”) and a flux, and firing (primary firing) to obtain a fired product (primary fired product). The resulting fired product is acid washed to prepare an acid washed product, and further a B metal oxide, a compound that forms a B metal oxide by heating, or a B metal salt (collectively referred to as “ Abbreviated as “B metal compound”) and the resulting acid. A mixture of Kiyoshibutsu can be obtained by firing (secondary firing). The flux does not have to be mixed. When the flux is mixed, the reaction can be made more uniform and crystals can be further grown, which is preferable.
原料の混合割合は、目的とするチタン酸塩の組成式により適宜調整することができるが、Ｂ金属化合物の混合割合は、好ましくはモル比で１次焼成物：Ｂ金属化合物＝９：１〜１：３、より好ましくは２：１〜１：２とするのがよい。 The mixing ratio of the raw materials can be appropriately adjusted according to the compositional formula of the target titanate, but the mixing ratio of the B metal compound is preferably a primary firing product: B metal compound = 9: 1 to 1 in a molar ratio. 1: 3, more preferably 2: 1 to 1: 2.
２次焼成後に残存しているＢ金属化合物は、水洗等の公知方法で除去することができるが、本発明のチタン酸塩を摩擦材の摩擦調整材として用いる場合は、Ｂ金属化合物が摩擦調整材としても寄与するものと考えられることから、チタン酸塩とＢ金属化合物との混合物として用いてもよい。 The B metal compound remaining after the secondary firing can be removed by a known method such as washing with water. However, when the titanate of the present invention is used as a friction modifier for a friction material, the B metal compound is used for friction adjustment. Since it is thought that it contributes also as a material, you may use as a mixture of a titanate and a B metal compound.
本発明のチタン酸塩の製造方法は、Ａ金属化合物とＢ金属化合物とを別々に混合して焼成することで、層間にＡ金属イオンとＢ金属イオンとを有することができる。また、前述のように乾式法で製造することで原料の水等の溶媒への溶解性を考慮することなく製造することができる。 The titanate production method of the present invention can have A metal ions and B metal ions between the layers by separately mixing and firing the A metal compound and the B metal compound. Moreover, it can manufacture without considering the solubility to solvents, such as water, of a raw material by manufacturing by a dry method as mentioned above.
チタン化合物としては、低次酸化チタンや、酸化チタンの含水物、酸化チタンの水和物、水酸化チタン等を使用できる。Ａ金属化合物としては、Ａ金属の炭酸塩、水酸化物、硝酸塩、硫酸塩等が使用できるが、これらのなかでもＡ金属の炭酸塩、水酸化物が好ましい。Ｂ金属化合物としては、Ｂ金属の炭酸塩、水酸化物、硝酸塩、硫酸塩等が使用できるが、これらのなかでもＢ金属の硫酸塩、硝酸塩が好ましい。Ｍ金属化合物としては、Ｍ金属の炭酸塩、水酸化物、酸化物、硝酸塩、硫酸塩等が使用できるが、これらのなかでもＭ金属の炭酸塩、水酸化物が好ましい。 As the titanium compound, low-order titanium oxide, hydrated titanium oxide, hydrated titanium oxide, titanium hydroxide, or the like can be used. As the A metal compound, carbonates, hydroxides, nitrates, sulfates and the like of A metal can be used, and among these, carbonates and hydroxides of A metal are preferable. B metal carbonates, hydroxides, nitrates, sulfates, and the like can be used as the B metal compound. Among these, B metal sulfates and nitrates are preferable. As the M metal compound, M metal carbonates, hydroxides, oxides, nitrates, sulfates and the like can be used. Of these, M metal carbonates and hydroxides are preferable.
フラックスとしては、塩化カリウム、フッ化カリウム、モリブデン酸カリウム、タングステン酸カリウム等を例示でき、これらのなかでも塩化カリウムが好ましい。フラックスの添加割合は、上記原料とのモル比（原料：フラックス）で３：１〜３：１５、好ましくは３：３．５〜３：１０の割合とするのがよい。 Examples of the flux include potassium chloride, potassium fluoride, potassium molybdate, potassium tungstate, and the like. Among these, potassium chloride is preferable. The addition ratio of the flux is 3: 1 to 3:15, preferably 3: 3.5 to 3:10, in terms of a molar ratio with the above raw material (raw material: flux).
１次焼成は、電気炉等を用いて行われ、８００〜１１００℃の温度範囲で、１〜２４時間保持することで焼成反応を完結することができる。 The primary firing is performed using an electric furnace or the like, and the firing reaction can be completed by holding in a temperature range of 800 to 1100 ° C. for 1 to 24 hours.
酸洗浄は、１次焼成物を適宜サイズに粉砕処理し、得られた粉砕物を水中に分散させて水性スラリーとし、水性スラリーに酸を添加して攪拌することにより行うことができる。水性スラリーの濃度は特に制限はなく、広い範囲から適宜選択できるが、作業性等を考慮すると、１〜３０質量％程度、好ましくは２〜２０質量％程度とすればよい。 Acid washing can be performed by pulverizing the primary baked product to an appropriate size, dispersing the obtained pulverized product in water to form an aqueous slurry, adding an acid to the aqueous slurry, and stirring. The concentration of the aqueous slurry is not particularly limited and can be appropriately selected from a wide range, but considering workability and the like, it may be about 1 to 30% by mass, preferably about 2 to 20% by mass.
酸としては、例えば、硫酸、塩酸、硝酸等の無機酸、酢酸等の有機酸を例示することができる。酸は必要に応じて２種以上を併用してもよい。水性スラリーに対する酸の添加量は、水性スラリーのｐＨが７〜１１、好ましくは７〜９になる量とすればよい。なお、水性スラリーのｐＨの測定は、酸を添加し、１〜５時間程度攪拌した後に行う。酸は通常水溶液（酸水溶液）の形態で使用される。酸水溶液の濃度は特に制限はなく広い範囲から適宜選択できるが、通常１〜９８質量％程度とすればよい。 Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid. Two or more acids may be used in combination as required. The amount of acid added to the aqueous slurry may be such that the pH of the aqueous slurry is 7 to 11, preferably 7 to 9. The pH of the aqueous slurry is measured after adding an acid and stirring for about 1 to 5 hours. The acid is usually used in the form of an aqueous solution (acid aqueous solution). The concentration of the acid aqueous solution is not particularly limited and can be appropriately selected from a wide range, but it may be usually about 1 to 98% by mass.
水性スラリーのｐＨを上記所定範囲に調整した後、濾過、遠心分離などにより固形分を該スラリーから分離する。分離された固形分は、必要に応じて、水洗、乾燥することができる。 After adjusting the pH of the aqueous slurry to the predetermined range, the solid content is separated from the slurry by filtration, centrifugation, or the like. The separated solid content can be washed with water and dried as necessary.
２次焼成は、電気炉等を用いて行われ、６００〜８５０℃の温度範囲で、１〜２４時間保持することで焼成反応を完結することができる。２次焼成後、得られる粉体を所望のサイズに粉砕したり、篩に通してほぐしてもよい。以上のようにして、本発明のチタン酸塩を得ることができる。 The secondary firing is performed using an electric furnace or the like, and the firing reaction can be completed by holding in a temperature range of 600 to 850 ° C. for 1 to 24 hours. After the secondary firing, the obtained powder may be pulverized to a desired size or passed through a sieve. As described above, the titanate of the present invention can be obtained.
本発明の無機複合材は、本発明に従って構成されるレピドクロサイト型チタン酸塩と、上記Ｂ金属化合物とを含むことを特徴とする。無機複合材は、上記２次焼成後に残存しているＢ金属化合物と、上記レピドクロサイト型チタン酸塩との混合物であってもよいし、上記レピドクロサイト型チタン酸塩に別途Ｂ金属化合物を混合したものでもよい。 The inorganic composite material of the present invention is characterized by comprising a lipidocrosite type titanate constituted according to the present invention and the B metal compound. The inorganic composite material may be a mixture of the B metal compound remaining after the secondary firing and the lipidocrocite-type titanate, or may be separately added to the lipidocrocite-type titanate. May be mixed.
本発明の樹脂組成物は、上記チタン酸塩と熱硬化性樹脂、又は上記無機複合材と熱硬化性樹脂とを含有していることを特徴とする。熱硬化性樹脂としては、公知の熱硬化性樹脂のなか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、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使用することができる。このなかでもフェノール樹脂が好ましい。本発明のチタン酸塩は、分散性、熱硬化性樹脂との密着性向上などを目的として、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使用されてもよい。樹脂組成物における本発明のチタン酸塩の含有量は、特に制限されるものではないが、樹脂組成物全体の３〜３０体積％であることが好ましい。 The resin composition of the present invention is characterized by containing the titanate and a thermosetting resin, or the inorganic composite material and a thermosetting resin. As the thermosetting resin, any one of known thermosetting resins can be appropriately selected and used. For example, a phenol resin, a formaldehyde resin, a melamine resin, an epoxy resin, an acrylic resin, an aromatic polyester resin, a urea resin, and the like can be given. One of these can be used alone, or two or more can be used in combination. Among these, a phenol resin is preferable. The titanate of the present invention may be used after being 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 adhesion with a thermosetting resin. Good. The content of the titanate of the present invention in the resin composition is not particularly limited, but is preferably 3 to 30% by volume of the entire resin composition.
本発明の樹脂組成物は、耐摩耗性を必要とする製品に使用することができ、特に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材に好適に用いることができる。また、本発明の樹脂組成物は、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耐摩耗性を得ることができる。 The resin composition of the present invention can be used for products that require wear resistance, and can be particularly suitably used for friction materials such as brake pads, brake linings, and clutch facings of various vehicles and industrial machines. Moreover, the resin composition of this invention can obtain the outstanding abrasion resistance, even if it does not contain copper, such as copper powder and copper fiber, from a viewpoint of consideration to a natural environment.
本発明の樹脂組成物を摩擦材として用いる場合は、必要とする特性に応じて、公知の繊維基材、摩擦調整材等を適宜配合し、常温にて所定圧力で成形し、次いで所定温度にて熱成形し、熱処理及び仕上げ処理することにより摩擦材の成形体に仕上げることができる。 When the resin composition of the present invention is used as a friction material, a known fiber base material, friction modifier, etc. are appropriately blended according to required properties, molded at a predetermined pressure at room temperature, and then at a predetermined temperature. The molded body of the friction material can be finished by thermoforming, heat treatment and finishing.
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；等があり、これらの１種を単独又は２種以上を組み合わせて使用することができる。 Examples of 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; etc., and one of these can be used alone or two or more of them can be used in combination.
摩擦調整材としては、加硫又は未加硫の天然又は合成ゴム、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；アルミナ、シリカ、マグネシア、ジルコニア（酸化ジルコニウム）、酸化クロム、二酸化モリブデン、ケイ酸ジルコニウム、酸化チタン、酸化鉄等の酸化物粉末；等があり、これらの１種を単独又は２種以上を組み合わせて使用することができる。 Examples of friction modifiers include organic powders such as vulcanized or unvulcanized natural or synthetic rubber, cashew dust, and resin dust; synthetic or natural graphite, carbon black, tin sulfide, molybdenum disulfide, antimony trisulfide, barium sulfate, Inorganic powder such as calcium carbonate, clay, mica and talc; metal powder such as copper, aluminum, zinc and iron; alumina, silica, magnesia, zirconia (zirconium oxide), chromium oxide, molybdenum dioxide, zirconium silicate, titanium oxide, These may be used alone or in combination of two or more.
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.
粒子形状は電界放出型走査電子顕微鏡（日立ハイテクノロジーズ社製、Ｓ−４８００）により確認し、結晶構造はＸ線回折測定装置（リガク社製、ＵｌｔｉｍａIV）により確認した。 The particle shape was confirmed with a field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), and the crystal structure was confirmed with an X-ray diffractometer (manufactured by Rigaku Corporation, Ultimate IV).
＜チタン酸塩の製造＞
（実施例１）
酸化チタン４９２．９ｇ、炭酸カリウム２１３．２ｇ、水酸化マグネシウム８９．９ｇを振動ミルにて粉砕しながら１時間混合した。粉砕混合粉５００ｇをルツボに充填し、電気炉にて１０５０℃で４時間焼成し、焼成物をハンマーミルにて粉砕した。
<Manufacture of titanate>
Example 1
492.9 g of titanium oxide, 213.2 g of potassium carbonate, and 89.9 g of magnesium hydroxide were mixed for 1 hour while being pulverized with a vibration mill. 500 g of the pulverized mixed powder was filled in a crucible, fired at 1050 ° C. for 4 hours in an electric furnace, and the fired product was pulverized by a hammer mill.
得られた粉砕物２００ｇを脱イオン水８００ｇに分散し２時間攪拌することでスラリーを調製した。これに９８％硫酸５．２ｇを添加して２時間攪拌しｐＨを９に調整した。このスラリーの固形分を濾別、乾燥した。乾燥物１００ｇと硫酸バリウム１００ｇとをハイスピードミキサーにて乾式混合した。乾式混合により得られた混合物を、ルツボに充填し、電気炉にて８００℃で１時間焼成した。 200 g of the obtained pulverized product was dispersed in 800 g of deionized water and stirred for 2 hours to prepare a slurry. To this, 5.2 g of 98% sulfuric acid was added and stirred for 2 hours to adjust the pH to 9. The solid content of this slurry was filtered and dried. 100 g of the dried product and 100 g of barium sulfate were dry mixed with a high speed mixer. The mixture obtained by dry mixing was filled in a crucible and baked at 800 ° C. for 1 hour in an electric furnace.
なお、Ｘ線回折測定により、得られた粉末が板状のレピドクロサイト型層状結晶のＫ０．４Ｂａ０．１５Ｍｇ０．４Ｔｉ１．６Ｏ３．９５と硫酸バリウム（ＢａＳＯ４）との混合物であることを確認した。 Note that, by X-ray diffraction measurement, the obtained powder was a plate-shaped lepidochrosite-type layered crystal of K 0.4 Ba 0.15 Mg 0.4 Ti 1.6 O 3.95 and barium sulfate (BaSO 4 ). It was confirmed that the mixture was.
（実施例２）
酸化チタン４９２．９ｇ、炭酸カリウム２１３．２ｇ、水酸化マグネシウム８９．９ｇを振動ミルにて粉砕しながら１時間混合した。粉砕混合粉５００ｇをルツボに充填し、電気炉にて１０５０℃で４時間焼成し、焼成物をハンマーミルにて粉砕した。
(Example 2)
492.9 g of titanium oxide, 213.2 g of potassium carbonate, and 89.9 g of magnesium hydroxide were mixed for 1 hour while being pulverized with a vibration mill. 500 g of the pulverized mixed powder was filled in a crucible, fired at 1050 ° C. for 4 hours in an electric furnace, and the fired product was pulverized by a hammer mill.
得られた粉砕物２００ｇを脱イオン水８００ｇに分散し２時間攪拌することでスラリーを調製した。これに９８％硫酸５．２ｇを添加して２時間攪拌しｐＨを９に調整した。このスラリーの固形分を濾別、乾燥した。乾燥物１００ｇと硫酸ストロンチウム７８．６ｇとをハイスピードミキサーにて乾式混合した。乾式混合により得られた混合物を、ルツボに充填し、電気炉にて８００℃で１時間焼成した。 200 g of the obtained pulverized product was dispersed in 800 g of deionized water and stirred for 2 hours to prepare a slurry. To this, 5.2 g of 98% sulfuric acid was added and stirred for 2 hours to adjust the pH to 9. The solid content of this slurry was filtered and dried. 100 g of the dried product and 78.6 g of strontium sulfate were dry mixed with a high speed mixer. The mixture obtained by dry mixing was filled in a crucible and baked at 800 ° C. for 1 hour in an electric furnace.
なお、Ｘ線回折測定により、得られた粉末が板状のレピドクロサイト型層状結晶のＫ０．４Ｓｒ０．１５Ｍｇ０．４Ｔｉ１．６Ｏ３．９５と硫酸ストロンチウム（ＳｒＳＯ４）との混合物であることを確認した。 In addition, it was confirmed by X-ray diffraction measurement that the obtained powder was a plate-shaped lepidocrocite-type layered crystal K 0.4 Sr 0.15 Mg 0.4 Ti 1.6 O 3.95 and strontium sulfate (SrSO 4 ) It was confirmed that the mixture was.
（実施例３）
酸化チタン４９２．９ｇ、炭酸カリウム２１３．２ｇ、水酸化マグネシウム８９．９ｇを振動ミルにて粉砕しながら１時間混合した。粉砕混合粉５００ｇをルツボに充填し、電気炉にて１０５０℃で４時間焼成し、焼成物をハンマーミルにて粉砕した。
Example 3
492.9 g of titanium oxide, 213.2 g of potassium carbonate, and 89.9 g of magnesium hydroxide were mixed for 1 hour while being pulverized with a vibration mill. 500 g of the pulverized mixed powder was filled in a crucible, fired at 1050 ° C. for 4 hours in an electric furnace, and the fired product was pulverized by a hammer mill.
得られた粉砕物２００ｇを脱イオン水８００ｇに分散し２時間攪拌することでスラリーを調製した。これに９８％硫酸５．２ｇを添加して２時間攪拌しｐＨを９に調整した。このスラリーの固形分を濾別、乾燥した。乾燥物１００ｇと硫酸カルシウム６２．２ｇとをハイスピードミキサーにて乾式混合した。乾式混合により得られた混合物を、ルツボに充填し、電気炉にて８００℃で１時間焼成した。 200 g of the obtained pulverized product was dispersed in 800 g of deionized water and stirred for 2 hours to prepare a slurry. To this, 5.2 g of 98% sulfuric acid was added and stirred for 2 hours to adjust the pH to 9. The solid content of this slurry was filtered and dried. 100 g of the dried product and 62.2 g of calcium sulfate were dry mixed with a high speed mixer. The mixture obtained by dry mixing was filled in a crucible and baked at 800 ° C. for 1 hour in an electric furnace.
なお、Ｘ線回折測定により、得られた粉末が板状のレピドクロサイト型層状結晶のＫ０．４Ｃａ０．１５Ｍｇ０．４Ｔｉ１．６Ｏ３．９５と硫酸カルシウム（ＣａＳＯ４）との混合物であることを確認した。 Note that, by X-ray diffraction measurement, the obtained powder was a plate-shaped lepidocrocite-type layered crystal of K 0.4 Ca 0.15 Mg 0.4 Ti 1.6 O 3.95 and calcium sulfate (CaSO 4 ). It was confirmed that the mixture was.
（実施例４）
酸化チタン５４０．９ｇ、炭酸カリウム２１６．１ｇ、炭酸リチウム３９．０ｇを振動ミルにて粉砕しながら１時間混合した。粉砕混合粉５００ｇをルツボに充填し、電気炉にて９００℃で４時間焼成し、焼成物をハンマーミルにて粉砕した。
Example 4
540.9 g of titanium oxide, 216.1 g of potassium carbonate, and 39.0 g of lithium carbonate were mixed for 1 hour while being pulverized by a vibration mill. 500 g of the pulverized mixed powder was filled in a crucible, fired at 900 ° C. for 4 hours in an electric furnace, and the fired product was pulverized by a hammer mill.
得られた粉砕物２００ｇを脱イオン水８００ｇに分散し２時間攪拌することでスラリーを調製した。これに９８％硫酸５．２ｇを添加して２時間攪拌しｐＨを９に調整した。このスラリーの固形分を濾別、乾燥した。乾燥物１００ｇと硫酸バリウム１００ｇとをハイスピードミキサーにて乾式混合した。乾式混合により得られた混合物を、ルツボに充填し、電気炉にて８００℃で１時間焼成した。 200 g of the obtained pulverized product was dispersed in 800 g of deionized water and stirred for 2 hours to prepare a slurry. To this, 5.2 g of 98% sulfuric acid was added and stirred for 2 hours to adjust the pH to 9. The solid content of this slurry was filtered and dried. 100 g of the dried product and 100 g of barium sulfate were dry mixed with a high speed mixer. The mixture obtained by dry mixing was filled in a crucible and baked at 800 ° C. for 1 hour in an electric furnace.
なお、Ｘ線回折測定により、得られた粉末が板状のレピドクロサイト型層状結晶のＫ０．４Ｂａ０．１５Ｌｉ０．２７Ｔｉ１．７３Ｏ３．９５と硫酸バリウム（ＢａＳＯ４）との混合物であることを確認した。 Note that, by X-ray diffraction measurement, the obtained powder was a plate-like lepidocrotite-type layered crystal of K 0.4 Ba 0.15 Li 0.27 Ti 1.73 O 3.95 and barium sulfate (BaSO 4 ). It was confirmed that the mixture was.
（比較例１）
酸化チタン４９２．９ｇ、炭酸カリウム２１３．２ｇ、水酸化マグネシウム８９．９ｇを振動ミルにて粉砕しながら１時間混合した。粉砕混合粉５００ｇをルツボに充填し、電気炉にて１０００℃で４時間焼成し、焼成物をハンマーミルにて粉砕した。
(Comparative Example 1)
492.9 g of titanium oxide, 213.2 g of potassium carbonate, and 89.9 g of magnesium hydroxide were mixed for 1 hour while being pulverized with a vibration mill. 500 g of the pulverized mixed powder was filled in a crucible, fired at 1000 ° C. for 4 hours in an electric furnace, and the fired product was pulverized by a hammer mill.
得られた粉砕物２００ｇを脱イオン水８００ｇに分散し２時間攪拌することでスラリーを調製した。これに９８％硫酸５．２ｇを添加して２時間攪拌しｐＨを９に調整した。このスラリーの固形分を濾別、乾燥した。乾燥後、ルツボに充填し、電気炉にて５００℃で１時間焼成した。 200 g of the obtained pulverized product was dispersed in 800 g of deionized water and stirred for 2 hours to prepare a slurry. To this, 5.2 g of 98% sulfuric acid was added and stirred for 2 hours to adjust the pH to 9. The solid content of this slurry was filtered and dried. After drying, the crucible was filled and baked in an electric furnace at 500 ° C. for 1 hour.
なお、Ｘ線回折測定により、得られた粉末が板状のレピドクロサイト型層状結晶のＫ０．７Ｍｇ０．４Ｔｉ１．６Ｏ３．９５であることを確認した。 In addition, it was confirmed by X-ray diffraction measurement that the obtained powder was K 0.7 Mg 0.4 Ti 1.6 O 3.95 which is a plate-like lepidocrotite-type layered crystal.
（比較例２）
酸化チタン５４０．９ｇ、炭酸カリウム２１６．１ｇ、炭酸リチウム３９．０ｇを振動ミルにて粉砕しながら１時間混合した。粉砕混合粉５００ｇをルツボに充填し、電気炉にて９００℃で４時間焼成し、焼成物をハンマーミルにて粉砕した。
(Comparative Example 2)
540.9 g of titanium oxide, 216.1 g of potassium carbonate, and 39.0 g of lithium carbonate were mixed for 1 hour while being pulverized by a vibration mill. 500 g of the pulverized mixed powder was filled in a crucible, fired at 900 ° C. for 4 hours in an electric furnace, and the fired product was pulverized by a hammer mill.
得られた粉砕物２００ｇを脱イオン水８００ｇに分散し２時間攪拌することでスラリーを調製した。これに９８％硫酸５．２ｇを添加して２時間攪拌しｐＨを９に調整した。このスラリーの固形分を濾別、乾燥した。乾燥後、ルツボに充填し、電気炉にて５００℃で１時間焼成した。 200 g of the obtained pulverized product was dispersed in 800 g of deionized water and stirred for 2 hours to prepare a slurry. To this, 5.2 g of 98% sulfuric acid was added and stirred for 2 hours to adjust the pH to 9. The solid content of this slurry was filtered and dried. After drying, the crucible was filled and baked in an electric furnace at 500 ° C. for 1 hour.
なお、Ｘ線回折測定により、得られた粉末が板状のレピドクロサイト型層状結晶のＫ０．７Ｌｉ０．２７Ｔｉ１．７３Ｏ３．９５であることを確認した。 In addition, it was confirmed by X-ray diffraction measurement that the obtained powder was K 0.7 Li 0.27 Ti 1.73 O 3.95 which is a plate-like lepidocrotite-type layered crystal.
＜Ｘ線回折測定＞
図１は、実施例１で得られた粉末及び比較例１で得られた粉末とＢａＳＯ４との混合物（比較例１で得られた粉末：ＢａＳＯ４＝１：１）のＸ線回折チャートを示す図である。図１に示すように、実施例１では、２次焼成することによって、１次焼成で得られるチタン酸カリウムマグネシウムのレピドクロサイト型層状結晶の一部のピーク強度が低下していることがわかる（図１の点線部分）。
<X-ray diffraction measurement>
FIG. 1 shows an X-ray diffraction chart of the powder obtained in Example 1 and a mixture of the powder obtained in Comparative Example 1 and BaSO 4 (powder obtained in Comparative Example 1: BaSO 4 = 1: 1). FIG. As shown in FIG. 1, in Example 1, it is understood that the peak intensity of a part of the lipidic crocite-type layered crystal of potassium magnesium titanate obtained by the primary baking is reduced by the secondary baking. (Dotted line portion in FIG. 1).
このことから、実施例１では、ＴｉＯ６八面体の連鎖により形成される層状構造を維持しながら、層間カリウムイオンの一部がバリウムイオンに置換されていることがわかる。すなわち、レピドクロサイト型チタン酸塩の層間に、カリウムイオン（Ａ金属イオン）及びバリウム（Ｂ金属イオン）が存在することがわかる。なお、実施例２〜４においても同様に、レピドクロサイト型チタン酸塩の層間に、Ａ金属イオン及びＢ金属イオンが存在することを確認している。 Therefore, in Example 1, while maintaining the layered structure formed by TiO 6 octahedrons chain, it can be seen that part of the interlayer potassium ions are replaced by barium ions. That is, it can be seen that potassium ions (A metal ions) and barium (B metal ions) exist between the layers of the lipidocrosite type titanate. Similarly, in Examples 2 to 4, it was confirmed that A metal ions and B metal ions exist between the layers of the lipidocrocite-type titanate.
＜硬化発熱ピーク温度の測定＞
（試験例１〜１０）
表１に記載の粉末１５０ｍｇとフェノール樹脂（住友ベークライト社製、スミライトレジンＰＲ−５００６４）５０ｍｇをメノウ乳鉢で混合した。得られた混合粉体を、示差走査熱量計（エスアイアイ・ナノテクノロジーズ社製、ＥＸＳＴＡＲ６０００ ＤＳＣ６２２０）を用い、窒素気流下（５０ｍｌ／ｍｉｎ）で、昇温温度２℃／ｍｉｎで測定を行った。示差走査熱量計のデータから、ＪＩＳ Ｋ６９１０−２００７の方法に準じて硬化発熱ピーク温度を算出した。結果を表１に示した。
<Measurement of curing exothermic peak temperature>
(Test Examples 1 to 10)
150 mg of the powder described in Table 1 and 50 mg of phenol resin (Sumitite Resin PR-50064, manufactured by Sumitomo Bakelite Co., Ltd.) were mixed in an agate mortar. The obtained mixed powder was measured at a temperature elevation temperature of 2 ° C./min under a nitrogen stream (50 ml / min) using a differential scanning calorimeter (EXSTAR DSC6220, manufactured by SII Nano Technologies). From the data of the differential scanning calorimeter, the curing exothermic peak temperature was calculated according to the method of JIS K6910-2007. The results are shown in Table 1.
表１の結果より、試験例１〜４は、試験例５〜１０と比べ、硬化発熱ピーク温度が低いことから、本発明のチタン酸塩が熱硬化性樹脂の硬化阻害を抑制しており、従来のチタン酸塩では、本発明の効果が得られないことが分かる。 From the results in Table 1, since Test Examples 1 to 4 have a lower curing exothermic peak temperature than Test Examples 5 to 10, the titanate of the present invention suppresses the inhibition of curing of the thermosetting resin, It can be seen that the effect of the present invention cannot be obtained with conventional titanates.
＜摩擦材の製造＞
（実施例５）
実施例１で得られた粉末３０質量部に、フェノール樹脂（住友ベークライト社製、スミライトレジンＰＲ−５００６４）１２質量部、アラミドパルプとフリクションダストの混合物８質量部、硫酸バリウム１３質量部、無機充填材２６質量部、黒鉛６質量部を配合し、レーディゲミキサーにて混合後、得られた混合物を仮成型（２５ＭＰａ）、熱成型（１５０℃，２０ＭＰａ）し、さらに熱処理（１６０〜２１０℃）を行い、ディスクブブレーキ用パッドを製造した。ディスクブレーキ用パッドとは、ＪＩＳ Ｄ０１０７の図２０−１５２（番号１５２−４）に記載されている形状のものであり、ディスクブレーキシステムで使用される摩擦材である。
<Manufacture of friction material>
(Example 5)
30 parts by mass of the powder obtained in Example 1, 12 parts by mass of a phenol resin (Sumilite Resin PR-50064, manufactured by Sumitomo Bakelite Co., Ltd.), 8 parts by mass of a mixture of aramid pulp and friction dust, 13 parts by mass of barium sulfate, inorganic After blending 26 parts by mass of filler and 6 parts by mass of graphite and mixing with a Laedige mixer, the resulting mixture was temporarily molded (25 MPa), thermoformed (150 ° C., 20 MPa), and further heat treated (160-210). The disc brake pad was manufactured. The disc brake pad has a shape described in FIG. 20-152 (number 152-4) of JIS D0107, and is a friction material used in the disc brake system.
（実施例６）
実施例１で得られた粉末に代えて、実施例４で得られた粉末を使用する以外は実施例５と同様にして、ディスクブレーキ用パッドを製造した。
(Example 6)
A disc brake pad was manufactured in the same manner as in Example 5 except that the powder obtained in Example 4 was used instead of the powder obtained in Example 1.
（比較例３）
実施例１で得られた粉末に代えて、比較例１の粉末と硫酸バリウムとの１：１混合物（質量比）を使用する以外は実施例５と同様にして、ディスクブレーキ用パッドを製造した。
(Comparative Example 3)
A disc brake pad was produced in the same manner as in Example 5 except that a 1: 1 mixture (mass ratio) of the powder of Comparative Example 1 and barium sulfate was used instead of the powder obtained in Example 1. .
（比較例４）
実施例１で得られた粉末に代えて、比較例２の粉末と硫酸バリウムとの１：１混合物（質量比）を使用する以外は実施例５と同様にして、ディスクブレーキ用パッドを製造した。
(Comparative Example 4)
A disc brake pad was manufactured in the same manner as in Example 5 except that a 1: 1 mixture (mass ratio) of the powder of Comparative Example 2 and barium sulfate was used instead of the powder obtained in Example 1. .
＜摩擦材の評価＞
摩擦材の気孔率はＪＩＳ Ｄ４４１８に基づき測定した。摩擦材の摩耗量は、ＪＡＳＯ Ｃ４２７に準拠し、ダイナモメーターにより測定した。摩擦後の摩擦材の外観は、実施例６より得られた摩擦材の摩擦面を基準に○とし、クラックの程度や白化した程度を比較し、状態の良いものから◎、○、×で表記した。結果を表２に示した。
<Evaluation of friction material>
The porosity of the friction material was measured based on JIS D4418. The amount of wear of the friction material was measured with a dynamometer in accordance with JASO C427. Appearance of the friction material after friction is marked with ◯, ○, × from the one with the best condition, comparing the degree of cracking and whitening with the friction surface of the friction material obtained from Example 6 as a reference. did. The results are shown in Table 2.
表２の結果より、従来のチタン酸塩を用いた比較例３及び４では、摩擦後の外観が悪くなっている。これに対し、本発明のチタン酸塩を用いた実施例５及び６では、摩耗量は同程度であるが、摩擦後の外観が改善されている。表１のように本発明のチタン酸塩を用いると熱硬化性樹脂の硬化阻害が抑制されるため、３次元架橋の度合い、マトリックス強度が向上し、摩擦後の摩擦材の外観が改善するものと考えられる。 From the results in Table 2, in Comparative Examples 3 and 4 using conventional titanates, the appearance after friction is poor. In contrast, in Examples 5 and 6 using the titanate of the present invention, the amount of wear is similar, but the appearance after friction is improved. When the titanate of the present invention is used as shown in Table 1, inhibition of curing of the thermosetting resin is suppressed, so that the degree of three-dimensional crosslinking and matrix strength are improved, and the appearance of the friction material after friction is improved. it is conceivable that.
Claims (9)
チタン化合物とＡ金属化合物とＭ金属化合物との混合物を焼成して焼成物を準備する工程と、
前記焼成物を酸洗浄して酸洗浄物を準備する工程と、
Ｂ金属化合物と前記酸洗浄物との混合物を焼成する工程とを備えることを特徴とするレピドクロサイト型チタン酸塩の製造方法。 A method for producing the lipidocrocite-type titanate according to any one of claims 1 to 5,
Firing a mixture of a titanium compound, an A metal compound, and an M metal compound to prepare a fired product;
A step of acid-washing the fired product to prepare an acid-washed product;
And a step of firing a mixture of the B metal compound and the acid-washed product.
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