JP6179519B2 - Friction material composition, friction material using friction material composition, and friction member - Google Patents
Friction material composition, friction material using friction material composition, and friction member Download PDFInfo
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- JP6179519B2 JP6179519B2 JP2014533123A JP2014533123A JP6179519B2 JP 6179519 B2 JP6179519 B2 JP 6179519B2 JP 2014533123 A JP2014533123 A JP 2014533123A JP 2014533123 A JP2014533123 A JP 2014533123A JP 6179519 B2 JP6179519 B2 JP 6179519B2
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- 239000002783 friction material Substances 0.000 title claims description 154
- 239000000203 mixture Substances 0.000 title claims description 89
- 239000002245 particle Substances 0.000 claims description 73
- 239000000835 fiber Substances 0.000 claims description 52
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 44
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 25
- 239000011256 inorganic filler Substances 0.000 claims description 22
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 22
- 244000226021 Anacardium occidentale Species 0.000 claims description 19
- 235000020226 cashew nut Nutrition 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000000428 dust Substances 0.000 claims description 17
- 239000012766 organic filler Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
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- 229920001971 elastomer Polymers 0.000 claims description 10
- 239000005060 rubber Substances 0.000 claims description 10
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical group [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 6
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 claims description 3
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 claims description 3
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- 238000000034 method Methods 0.000 description 9
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- -1 resins, acrylic modified phenol Chemical class 0.000 description 6
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- 239000012784 inorganic fiber Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
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- 229940007424 antimony trisulfide Drugs 0.000 description 3
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 3
- 229920006231 aramid fiber Polymers 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
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- 231100000260 carcinogenicity Toxicity 0.000 description 3
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
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- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
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- 229910052726 zirconium Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 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 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000000241 respiratory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000005748 tumor development Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
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- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
- F16D69/02—Compositions of linings; Methods of manufacturing
- F16D69/025—Compositions based on an organic binder
- F16D69/026—Compositions based on an organic binder containing fibres
Description
本発明は、自動車等の制動に用いられるディスクブレーキパッド、ブレーキライニング等の摩擦材に適した摩擦材組成物、該摩擦材組成物を用いた摩擦材及び摩擦部材に関する。 The present invention relates to a friction material composition suitable for friction materials such as disc brake pads and brake linings used for braking of automobiles, etc., and a friction material and a friction member using the friction material composition.
自動車等には、その制動のためにディスクブレーキパッドやブレーキライニング等の摩擦材が使用されている。ディスクブレーキパッドやブレーキライニング等の摩擦材は、相手材となるディスクローターやブレーキドラム等と摩擦することによって制動の役割を果たす。そのため摩擦材には、使用条件に応じた適切な摩擦係数及び摩擦係数の安定性（効き特性）が求められるだけでなく、鳴きが発生しにくいこと（鳴き特性）、摩擦材の寿命が長いこと（耐摩耗性）等が要求される。 In automobiles and the like, friction materials such as disc brake pads and brake linings are used for braking. Friction materials such as a disc brake pad and a brake lining play a role of braking by friction with a disc rotor, a brake drum, or the like as a counterpart material. For this reason, the friction material is required not only to have an appropriate friction coefficient and stability of the friction coefficient (effect characteristics) depending on the use conditions, but also to make it difficult for squeal (squeal characteristics) and to have a long life of the friction material. (Abrasion resistance) is required.
効き特性として、摩擦材には、運転時の安全性及びドライバーの快適性の観点から、様々な制動条件で摩擦係数の変化率が少ないこと、つまり摩擦係数が安定していることが求められている。摩擦材は、自動車の運動エネルギーを制動時に発生する熱エネルギーに変換することで減速、停止を可能とする。従って摩擦材には、常温から約８００℃に至る高温まで幅広い熱負荷がかかるため、常に安定した摩擦係数を発現することは難しい。例えば、高速条件からの急制動（以下、高負荷制動時という）を行うことで、摩擦材を構成する樹脂マトリックス（摩擦材組成物中の硬化した樹脂）が一気に熱分解し、摩擦係数が低下するフェード現象を挙げることができる。さらに、前記フェード現象等の熱的損傷は一時的なものではなく、摩擦材に熱履歴として残り、その熱履歴後の通常制動の摩擦係数（以下、熱履歴後の摩擦係数という）も低下してしまう傾向がある。 In terms of effectiveness, friction materials are required to have a low rate of change in friction coefficient under various braking conditions, that is, from the viewpoint of driving safety and driver comfort. Yes. The friction material can be decelerated and stopped by converting the kinetic energy of the automobile into thermal energy generated during braking. Therefore, since the friction material is subjected to a wide heat load from room temperature to about 800 ° C., it is difficult to always express a stable friction coefficient. For example, sudden braking from high speed conditions (hereinafter referred to as “high load braking”) causes the resin matrix (cured resin in the friction material composition) constituting the friction material to be thermally decomposed at once and the friction coefficient to decrease. A fading phenomenon can be given. Furthermore, the thermal damage such as the fade phenomenon is not temporary and remains in the friction material as a heat history, and the friction coefficient of normal braking after the heat history (hereinafter referred to as the friction coefficient after the heat history) also decreases. There is a tendency to end up.
摩擦係数を安定化するために、摩擦材に銅繊維又は針状チタン酸塩を含有させる方法が一般的に知られている（例えば、特許文献１参照）。銅繊維、針状チタン酸塩は、繊維形状であるため補強材として摩擦材の機械的強度を向上し、摩擦係数を安定化させる。特に銅は、制動後に摩擦材表面と対面材との間で延び、摩擦材及び対面材に金属皮膜を形成することで摩擦係数の安定化に大きく寄与している。そのため、現在多くの摩擦材に銅繊維が使用されている。 In order to stabilize a friction coefficient, the method of making a friction material contain a copper fiber or acicular titanate is generally known (for example, refer patent document 1). Since copper fiber and acicular titanate have a fiber shape, they improve the mechanical strength of the friction material as a reinforcing material and stabilize the friction coefficient. In particular, copper extends between the friction material surface and the facing material after braking, and contributes greatly to the stabilization of the friction coefficient by forming a metal film on the friction material and the facing material. For this reason, copper fibers are currently used in many friction materials.
しかし、銅及び銅合金を含む銅繊維等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、河川汚染、海洋汚染等の原因となる可能性が示唆されているため、使用を制限する動きが高まっている。また、針状チタン酸塩は発癌性の観点から摩擦材に含有しないことが望まれている。例えば、銅及び銅合金を含まずに、摩擦係数、耐摩耗性、及び耐相手材攻撃性が良好な摩擦材を提供するために、酸化マグネシウムと黒鉛を摩擦材中に４５〜８０体積％含有し、酸化マグネシウムと黒鉛の比を１/１〜４/１とする方法が提案されている（特許文献２参照）。 However, it is suggested that friction materials containing copper fibers including copper and copper alloys contain copper in the wear powder generated during braking, which may cause river pollution, marine pollution, etc. There is a growing movement to limit. Further, it is desired that acicular titanate is not contained in the friction material from the viewpoint of carcinogenicity. For example, in order to provide a friction material that does not contain copper and copper alloy and has a good coefficient of friction, wear resistance, and attack resistance against the counterpart material, magnesium oxide and graphite are contained in the friction material in an amount of 45 to 80% by volume. However, a method has been proposed in which the ratio of magnesium oxide to graphite is 1/1 to 4/1 (see Patent Document 2).
一方で、摩擦材には、高負荷制動時、熱履歴後、また通常の制動時だけではなく、低温及び高湿度条件下で放置後の摩擦係数（以下、低温放置後の摩擦係数という）の安定性も求められている。一般的に、低温及び高湿度条件下で放置した後の摩擦材の摩擦係数は上昇してしまい、それに伴い鳴き発生率が上昇する。例えば冬場の朝、一晩放置してあった自動車を発進し、一回目の制動を行った時に、ブレーキ鳴きが発生しやすい。特に上記一回目の制動は低速及び低減速度で行われることが多いが、この場合、自動車の駆動系機関の静粛性が極めて高い。そのため、僅かなブレーキ鳴きであっても容易に知覚されてしまう。上記の理由から、低温放置後の摩擦係数の上昇を抑制することも求められている。 On the other hand, the friction material has a friction coefficient after being left under low temperature and high humidity conditions (hereinafter referred to as a friction coefficient after being left at low temperature) as well as during high load braking, after thermal history, and during normal braking. There is also a need for stability. In general, the coefficient of friction of the friction material after being left under low temperature and high humidity conditions increases, and the squeal rate increases accordingly. For example, when a car that has been left overnight is started in the morning in winter and the first braking is performed, a brake squeal is likely to occur. In particular, the first braking is often performed at a low speed and a reduced speed, but in this case, the quietness of the driveline engine of the automobile is extremely high. Therefore, even a slight brake squeal is easily perceived. For the above reasons, it is also required to suppress an increase in the coefficient of friction after being left at a low temperature.
しかしながら、銅を含まない摩擦材（例えば、特許文献２の摩擦材）で、高負荷制動時、熱履歴後の摩擦係数の低下を抑制しつつ、低温放置後の摩擦係数の上昇を抑制することは困難であった。 However, a friction material that does not contain copper (for example, the friction material of Patent Document 2) suppresses a decrease in the coefficient of friction after thermal history and suppresses an increase in the coefficient of friction after being left at a low temperature during high load braking. Was difficult.
そこで本発明は、銅の含有量が少ない摩擦材であり、高負荷制動時及び熱履歴後の摩擦係数の低下を抑制し、かつ低温放置後の摩擦係数の上昇を抑制できる摩擦材を与える摩擦材組成物を提供することを目的とする。また、該摩擦材組成物を用いた摩擦材及び摩擦部材を提供することを目的とする。 Accordingly, the present invention is a friction material that has a low copper content, and that provides a friction material that can suppress a decrease in the friction coefficient during high-load braking and after a thermal history and can suppress an increase in the friction coefficient after being left at a low temperature. An object is to provide a material composition. Another object of the present invention is to provide a friction material and a friction member using the friction material composition.
本発明者等は、結合材、有機充填材、無機充填材、及び繊維基材を含有する摩擦材組成物であり、該摩擦材組成物中の銅の含有量が銅元素として５質量％以下であり、特定の平均粒子径を有する酸化ジルコニウム、及びカシューダストを特定量含有する摩擦材組成物とすることで、銅が少ない摩擦材であっても、高負荷制動時及び熱履歴後の摩擦係数の低下を抑制し、かつ低温放置後の摩擦係数の上昇を抑制できることを見出した。 The present inventors are a friction material composition containing a binder, an organic filler, an inorganic filler, and a fiber substrate, and the copper content in the friction material composition is 5% by mass or less as a copper element. By using a friction material composition containing a specific amount of zirconium oxide and cashew dust having a specific average particle size, even when the friction material is low in copper, the friction during high-load braking and after thermal history It has been found that the decrease in the coefficient can be suppressed and the increase in the friction coefficient after being left at low temperature can be suppressed.
すなわち、本発明は次の事項に関する。
＜１＞結合材、有機充填材、無機充填材、及び繊維基材を含有する摩擦材組成物であり、上記摩擦材組成物中の銅の含有量が銅元素として５質量％以下であり、上記無機充填材として平均粒子径（Ｄ５０）が０．１〜４μｍである酸化ジルコニウムを３〜２０質量％含有し、上記有機充填材としてカシューダストを２〜８質量％含有する摩擦材組成物。
＜２＞粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含有しない、前記摩擦材組成物。
＜３＞さらに、無機充填材として黒鉛を含有する、前記摩擦材組成物。
＜４＞前記黒鉛の平均粒子径（Ｄ５０）が１〜１００μｍである、前記摩擦材組成物。
＜５＞さらに、無機充填材としてチタン酸塩を含有する、前記摩擦材組成物。
＜６＞前記チタン酸塩が、チタン酸カリウム、チタン酸リチウムカリウム又はチタン酸マグネシウムカリウムである、前記摩擦材組成物。
＜７＞前記チタン酸塩の含有量が１０〜２０質量％である、前記摩擦材組成物。
＜８＞前記チタン酸塩が、柱状、板状、粒子状又は燐片状である、前記摩擦材組成物。
＜９＞前記摩擦材組成物を成形してなる摩擦材。
＜１０＞前記摩擦材組成物を成形してなる摩擦材と裏金とを用いて形成される摩擦部材。That is, the present invention relates to the following matters.
<1> A friction material composition containing a binder, an organic filler, an inorganic filler, and a fiber base material, wherein the copper content in the friction material composition is 5% by mass or less as a copper element, A friction material composition containing 3 to 20% by mass of zirconium oxide having an average particle diameter (D50) of 0.1 to 4 μm as the inorganic filler and 2 to 8% by mass of cashew dust as the organic filler.
<2> The friction material composition substantially containing no zirconium oxide having a particle size of 30 μm or more.
<3> The friction material composition further comprising graphite as an inorganic filler.
<4> The friction material composition, wherein the graphite has an average particle diameter (D50) of 1 to 100 μm.
<5> The friction material composition further comprising titanate as an inorganic filler.
<6> The friction material composition, wherein the titanate is potassium titanate, lithium potassium titanate, or magnesium potassium titanate.
<7> The friction material composition, wherein the titanate content is 10 to 20% by mass.
<8> The friction material composition, wherein the titanate has a columnar shape, a plate shape, a particle shape, or a flake shape.
<9> A friction material formed by molding the friction material composition.
<10> A friction member formed by using a friction material obtained by molding the friction material composition and a back metal.
本発明によれば、銅の含有量が少ない摩擦材であっても、高負荷制動時及び熱履歴後の摩擦係数の低下を抑制し、かつ低温放置後の摩擦係数の上昇を抑制できる摩擦材を与える摩擦材組成物を提供することができる。また、該摩擦材組成物を用いた摩擦材及び摩擦部材を提供することができる。 According to the present invention, even if the friction material has a small copper content, the friction material can suppress a decrease in the friction coefficient during high load braking and after a thermal history, and can suppress an increase in the friction coefficient after being left at a low temperature. The friction material composition which provides can be provided. Moreover, the friction material and friction member using this friction material composition can be provided.
以下、本発明の摩擦材組成物、これを用いた摩擦材及び摩擦部材について詳述する。なお、本発明の摩擦材組成物は、ノンアスベスト摩擦材組成物である。 Hereinafter, the friction material composition of the present invention, the friction material using the same, and the friction member will be described in detail. The friction material composition of the present invention is a non-asbestos friction material composition.
＜摩擦材組成物＞
本発明の摩擦材組成物は、結合材、有機充填材、無機充填材、及び繊維基材を含有する摩擦材組成物であり、上記摩擦材組成物中の銅の含有量が銅元素として５質量％以下であり、上記無機充填材として平均粒子径（Ｄ５０）が０．１〜４μｍである酸化ジルコニウムを３〜２０質量％含有し、上記有機充填材としてカシューダストを２〜８質量％含有する摩擦材組成物である。上記構成により、本発明の摩擦材組成物を用いた摩擦材及び摩擦部材は、従来品と比較して制動時に生成する摩耗粉中の銅が少ないことから環境に優しく、かつ安定した摩擦係数を発現する。また上記構成により、良好な耐摩耗性、及び鳴き特性を発現することもできる。<Friction material composition>
The friction material composition of the present invention is a friction material composition containing a binder, an organic filler, an inorganic filler, and a fiber substrate, and the copper content in the friction material composition is 5 as a copper element. 3 to 20% by mass of zirconium oxide having an average particle size (D50) of 0.1 to 4 μm as the inorganic filler, and 2 to 8% by mass of cashew dust as the organic filler. The friction material composition. With the above configuration, the friction material and the friction member using the friction material composition of the present invention have an environment-friendly and stable friction coefficient because there is less copper in the wear powder generated during braking compared to the conventional product. To express. In addition, the above configuration can also exhibit good wear resistance and squeal characteristics.
［結合材］
本発明の摩擦材組成物は結合材を含有する。結合材は、摩擦材組成物に含まれる有機充填材及び繊維基材等を一体化して、強度を与えるものである。本発明の摩擦材組成物に含まれる結合材は、通常、摩擦材に用いられる熱硬化性樹脂を用いることができる。
熱硬化性樹脂としては、例えば、フェノール樹脂や、アクリル変性フェノール樹脂、シリコーン変性フェノール樹脂、カシュー変性フェノール樹脂、エポキシ変性フェノール樹脂、アルキルベンゼン変性フェノール樹脂等の各種変性フェノール樹脂等が挙げられ、これらを単独で又は２種類以上を組み合わせて使用することができる。良好な耐熱性、成形性及び摩擦係数を与えることから、フェノール樹脂、アクリル変性フェノール樹脂、シリコーン変性フェノール樹脂、アルキルベンゼン変性フェノール樹脂を用いることが好ましい。[Binder]
The friction material composition of the present invention contains a binder. The binding material provides strength by integrating the organic filler and the fiber base material included in the friction material composition. As the binder contained in the friction material composition of the present invention, a thermosetting resin usually used for a friction material can be used.
Examples of the thermosetting resin include phenol resins, acrylic modified phenol resins, silicone modified phenol resins, cashew modified phenol resins, epoxy modified phenol resins, various modified phenol resins such as alkylbenzene modified phenol resins, and the like. It can be used alone or in combination of two or more. In order to give good heat resistance, moldability and friction coefficient, it is preferable to use a phenol resin, an acrylic modified phenol resin, a silicone modified phenol resin, or an alkylbenzene modified phenol resin.
本発明の摩擦材組成物における、結合材の含有量は、５〜２０質量％であることが好ましく、５〜１５質量％であることがより好ましく、５〜１０質量％であることがさらに好ましい。結合材の含有量を５〜２０質量％の範囲とすることで、摩擦材の強度低下をより抑制でき、また、摩擦材の気孔率が減少し、弾性率が高くなることによる鳴き等の音振性能悪化をより抑制できる。 The content of the binder in the friction material composition of the present invention is preferably 5 to 20% by mass, more preferably 5 to 15% by mass, and further preferably 5 to 10% by mass. . By setting the content of the binder in the range of 5 to 20% by mass, it is possible to further suppress the strength reduction of the friction material, reduce the porosity of the friction material, and increase the elastic modulus. Vibration performance deterioration can be further suppressed.
［有機充填材］
本発明の摩擦材組成物は有機充填材を含有する。有機充填材は、摩擦材の音振性能や耐摩耗性等を向上させるための摩擦調整材として含まれるものである。本発明の摩擦材組成物に含まれる有機充填材としてはカシューダストが挙げられ、さらにゴム成分等を含ませることができる。
上記カシューダストは、カシューナッツシェルオイルを硬化させたものを粉砕して得られる、通常、摩擦材に用いられるものであればよい。
上記カシューダストの含有量は、２〜８質量％であり、２〜７質量％であることが好ましく、３〜７質量％であることがより好ましい。カシューダストの含有量が２〜８質量％の範囲外であると、摩擦材の弾性率が高くなることによる鳴き等の音振性能が悪化し、また耐熱性が悪化し、熱履歴により強度が低下する。[Organic filler]
The friction material composition of the present invention contains an organic filler. The organic filler is included as a friction modifier for improving the sound vibration performance and wear resistance of the friction material. The organic filler contained in the friction material composition of the present invention includes cashew dust, and can further contain a rubber component and the like.
The cashew dust is not particularly limited as long as it is obtained by pulverizing a hardened cashew nut shell oil and is usually used for a friction material.
Content of the said cashew dust is 2-8 mass%, it is preferable that it is 2-7 mass%, and it is more preferable that it is 3-7 mass%. When the content of cashew dust is outside the range of 2 to 8% by mass, the vibration performance such as squeal due to the increase in the elastic modulus of the friction material is deteriorated, the heat resistance is deteriorated, and the strength is increased by the heat history. descend.
上記ゴム成分としては、例えば、タイヤゴム、アクリルゴム、イソプレンゴム、ＮＢＲ（ニトリルブタジエンゴム）、ＳＢＲ（スチレンブタジエンゴム）等が挙げられ、これらを単独で又は２種類以上を組み合わせて使用される。
また、カシューダストとゴム成分とを併用してもよく、カシューダストをゴム成分で被覆したものを用いてもよいが、音振性能の観点から、カシューダストとゴム成分とを併用することが好ましい。
カシューダストとゴム成分とを併用する場合、カシューダストとゴム成分とは、質量比で１：４〜１０：１の割合であることが好ましく、１：３〜９：１であることがより好ましく、１：２〜８：１であることがさらに好ましい。Examples of the rubber component include tire rubber, acrylic rubber, isoprene rubber, NBR (nitrile butadiene rubber), SBR (styrene butadiene rubber) and the like, and these are used alone or in combination of two or more.
In addition, cashew dust and a rubber component may be used in combination, or cashew dust coated with a rubber component may be used, but from the viewpoint of sound vibration performance, it is preferable to use cashew dust and a rubber component in combination. .
When cashew dust and a rubber component are used in combination, the cashew dust and the rubber component are preferably in a mass ratio of 1: 4 to 10: 1, more preferably 1: 3 to 9: 1. 1 to 2: 1 is more preferable.
本発明の摩擦材組成物中における、有機充填材の含有量は、１〜２０質量％であることが好ましく、１〜１５質量％であることがより好ましく、２〜１０質量％であることがさらに好ましい。有機充填材の含有量を１〜２０質量％の範囲とすることで、摩擦材の弾性率が高くなることによる鳴き等の音振性能の悪化を避けることができ、また耐熱性の悪化、熱履歴による強度低下を避けることができる。 The content of the organic filler in the friction material composition of the present invention is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and 2 to 10% by mass. Further preferred. By setting the content of the organic filler in the range of 1 to 20% by mass, it is possible to avoid deterioration of sound vibration performance such as squeal due to an increase in the elastic modulus of the friction material, deterioration of heat resistance, heat It is possible to avoid a decrease in strength due to history.
［無機充填材］
本発明の摩擦材組成物は無機充填材を含有する。無機充填材は、摩擦材の耐熱性の悪化を抑制するために摩擦調整材として含まれるものである。
本発明の摩擦材組成物は、無機充填材として平均粒子径（Ｄ５０）が０．１〜４μｍである酸化ジルコニウムを３〜２０質量％含有する。[Inorganic filler]
The friction material composition of the present invention contains an inorganic filler. The inorganic filler is included as a friction modifier in order to suppress deterioration of the heat resistance of the friction material.
The friction material composition of this invention contains 3-20 mass% of zirconium oxide whose average particle diameter (D50) is 0.1-4 micrometers as an inorganic filler.
上記酸化ジルコニウムの含有量が３質量％未満であると、摩擦係数、特に高負荷制動時の摩擦係数の低下を抑制することができず、また耐摩耗性を発現することができない。酸化ジルコニウムの含有量が２０質量％を超えると、摩擦係数の安定性が悪くなり、耐摩耗性を発現することができない。酸化ジルコニウムの含有量は３〜１９質量％であることが好ましく、５〜１９質量％であることがより好ましく、７〜１７質量％であることがさらに好ましい。 When the content of the zirconium oxide is less than 3% by mass, it is not possible to suppress a decrease in the friction coefficient, particularly a friction coefficient during high load braking, and it is impossible to develop wear resistance. When the content of zirconium oxide exceeds 20% by mass, the stability of the friction coefficient is deteriorated and the wear resistance cannot be expressed. The content of zirconium oxide is preferably 3 to 19% by mass, more preferably 5 to 19% by mass, and further preferably 7 to 17% by mass.
また上記酸化ジルコニウムの平均粒子径（Ｄ５０）が０．１μｍ未満であると、摩擦係数の安定性が悪くなり、耐摩耗性を発現することができない。また、酸化ジルコニウムの平均粒子径（Ｄ５０）が４μｍを超えると、耐摩耗性が悪化する。
酸化ジルコニウムの平均粒子径（Ｄ５０）は、０．１〜３μｍであることが好ましく、０．１〜２．５μｍであることがより好ましく、０．１〜２μｍであることがさらに好ましい。なお、酸化ジルコニウムの平均粒子径（Ｄ５０）は、レーザー回折粒度分布測定等の方法を用いて、粒子径分布を測定することで求めることができる。
具体的には、粒子径分布積算曲線を描いた時に粒子径の最も小さい粒子から順次積算して全体の５０％に達するところの粒子径を、平均粒子径（Ｄ５０）とする。体積分布は、例えば、レーザー回折／散乱式粒子径分布測定装置 ＬＡ・９２０（（株）堀場製作所製）で測定することができる。When the average particle diameter (D50) of the zirconium oxide is less than 0.1 μm, the stability of the friction coefficient is deteriorated and the wear resistance cannot be expressed. Further, when the average particle diameter (D50) of zirconium oxide exceeds 4 μm, the wear resistance is deteriorated.
The average particle diameter (D50) of zirconium oxide is preferably 0.1 to 3 μm, more preferably 0.1 to 2.5 μm, and further preferably 0.1 to 2 μm. In addition, the average particle diameter (D50) of a zirconium oxide can be calculated | required by measuring particle diameter distribution using methods, such as a laser diffraction particle size distribution measurement.
Specifically, the average particle size (D50) is the particle size at which 50% of the total particle size is accumulated from the smallest particle size when the particle size distribution integration curve is drawn. The volume distribution can be measured, for example, with a laser diffraction / scattering particle size distribution measuring apparatus LA.920 (manufactured by Horiba, Ltd.).
また、摩擦材組成物は粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含有しないことが好ましい。粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含有しないことで、良好な摩擦係数が発現し、耐摩耗性の悪化を避けることができる。さらに、粒子径が２０μｍ以上の酸化ジルコニウムを実質的に含有しないことがより好ましく、粒子径が１０μｍ以上の酸化ジルコニウムを実質的に含有しないことがさらに好ましい。
上記「実質的に含有しない」とは、本発明の摩擦材組成物に含有される酸化ジルコニウムのうち、その含有量が１．０質量％以下であることをいい、好ましくは０．５質量％以下であることをいう。特に好ましくは３０μｍを超える酸化ジルコニウムを含有しないことである。Further, it is preferable that the friction material composition does not substantially contain zirconium oxide having a particle size of 30 μm or more. By substantially not containing zirconium oxide having a particle size of 30 μm or more, a good coefficient of friction is exhibited, and deterioration of wear resistance can be avoided. Furthermore, it is more preferable that zirconium oxide having a particle diameter of 20 μm or more is substantially not contained, and it is further preferable that zirconium oxide having a particle diameter of 10 μm or more is not substantially contained.
The “substantially not containing” means that the content of zirconium oxide contained in the friction material composition of the present invention is 1.0% by mass or less, preferably 0.5% by mass. It means the following. Particularly preferably, it does not contain zirconium oxide exceeding 30 μm.
なお、粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含有するかどうかは、レーザー回折粒度分布測定等の方法を用いて、粒子径の分布を測定することで求めることができる。具体的には、粒子径分布積算曲線を描いた時に粒子径の最も小さい粒子から順次積算して全体の９９.９％に達するところの粒子径が３０μｍより小さければ、粒子径が３０μｍ以上の酸化ジルコニウムを含有しないといえる。
粒子径分布は例えば、レーザー回折／散乱式粒子径分布測定装置 ＬＡ・９２０（（株）堀場製作所製）で測定することができる。Whether or not zirconium oxide having a particle size of 30 μm or more is substantially contained can be determined by measuring the particle size distribution using a method such as laser diffraction particle size distribution measurement. Specifically, when the particle diameter distribution integration curve is drawn, if the particle diameter at which 99.9% of the total particles are integrated from the smallest particle diameter is smaller than 30 μm, the oxidation with a particle diameter of 30 μm or more. It can be said that it does not contain zirconium.
The particle size distribution can be measured, for example, with a laser diffraction / scattering particle size distribution measuring apparatus LA.920 (manufactured by Horiba, Ltd.).
本発明の摩擦材組成物は、さらに、無機充填材として黒鉛を含有することが好ましい。黒鉛を含有することで、対面材への攻撃性を低下することができる。また黒鉛の平均粒子径（Ｄ５０）は、１〜１００μｍであることが好ましい。黒鉛の平均粒子径を１μｍ以上とすることでより良好な摩擦係数、耐摩耗性が発現し、１００μｍ以下とすることで、摩擦材の熱伝導率の低下をより避けることができる。黒鉛の平均粒子径は１〜５０μｍであることがより好ましく、１〜３０μｍであることがさらに好ましい。
なお、平均粒子径（Ｄ５０）は、上記酸化ジルコニウムの平均粒子径（Ｄ５０）と同様の方法で求めることができる。The friction material composition of the present invention preferably further contains graphite as an inorganic filler. By containing graphite, the aggressiveness to the facing material can be reduced. Moreover, it is preferable that the average particle diameter (D50) of graphite is 1-100 micrometers. By setting the average particle diameter of graphite to 1 μm or more, a better friction coefficient and wear resistance are exhibited. By setting the average particle diameter to 100 μm or less, a decrease in the thermal conductivity of the friction material can be avoided. The average particle diameter of graphite is more preferably 1 to 50 μm, and further preferably 1 to 30 μm.
In addition, an average particle diameter (D50) can be calculated | required by the method similar to the average particle diameter (D50) of the said zirconium oxide.
本発明の摩擦材組成物は、さらに無機充填材としてチタン酸塩を含有することが好ましい。チタン酸塩を含有することで摩擦係数の安定性を向上することができる。
なお、本発明において、チタン酸塩を含有する場合、針状のチタン酸塩は発癌性の観点から摩擦材に実質的に含有しないこと（例えば、５質量%以下、好ましくは含まないこと）が望まれている。チタン酸塩を含有する場合、チタン酸塩の形状は、柱状、板状、粒子状又は鱗片状のもの等を用いることができ、これらを単独で又は２種類以上を組み合わせて使用することができる。
チタン酸塩の形状は、例えば走査型電子顕微鏡（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ；ＳＥＭ）観察から解析することができる。The friction material composition of the present invention preferably further contains titanate as an inorganic filler. By containing titanate, the stability of the friction coefficient can be improved.
In the present invention, when titanate is contained, acicular titanate is not substantially contained in the friction material from the viewpoint of carcinogenicity (for example, 5% by mass or less, preferably not contained). It is desired. When the titanate is contained, the shape of the titanate can be columnar, plate-like, particulate or scale-like, and these can be used alone or in combination of two or more. .
The shape of the titanate can be analyzed, for example, by observation with a scanning electron microscope (SEM).
ここで、チタン酸塩の形状についての定義の一例を記載する。チタン酸塩に外接する直方体のうち最小の体積をもつ直方体（外接直方体）の最も長い辺を長径Ｌ、次に長い辺を短径Ｂ、最も短い辺を厚さＴとして（Ｂ＞Ｔとする）、チタン酸塩の形状をアスペクト比（Ｌ／Ｔ、Ｌ／Ｂ）で定義する。
針状のチタン酸塩とは、Ｌ／Ｔが１０よりも大きく、Ｌ／Ｂが１０よりも大きいチタン酸塩である。例えば、ティスモＤ、ティスモＮ（いずれも、大塚化学（株）製）等が挙げられる。
柱状のチタン酸塩とは、Ｌ／Ｔ＝２〜１０、Ｌ／Ｂ＝２〜１０であるチタン酸塩である。ＴＯＦＩＸ−Ｓ（東邦マテリアル（株）製）等が挙げられる。
板状のチタン酸塩とは、Ｌ／Ｔが１０よりも大きく、Ｌ／Ｂが１０よりも小さいチタン酸塩である。例えば、ＴＸＡＸ−Ａ、ＴＸＡＸ−ＭＡ、ＴＸＡＸ−ＫＡ、ＴＸＡＸ−ＣＴ（いずれも、（株）クボタ製）等が挙げられる。Here, an example of the definition about the shape of titanate will be described. Of the rectangular parallelepipeds circumscribing the titanate, the longest side of the rectangular parallelepiped having the smallest volume (the circumscribed rectangular parallelepiped) is the major axis L, the next longest side is the minor axis B, and the shortest side is the thickness T (B> T) ), And the shape of titanate is defined by the aspect ratio (L / T, L / B).
An acicular titanate is a titanate having an L / T greater than 10 and an L / B greater than 10. For example, Tismo D, Tismo N (both manufactured by Otsuka Chemical Co., Ltd.) and the like can be mentioned.
The columnar titanate is a titanate having L / T = 2 to 10 and L / B = 2 to 10. And TOFIX-S (manufactured by Toho Material Co., Ltd.).
The plate-like titanate is a titanate having L / T larger than 10 and L / B smaller than 10. For example, TXAX-A, TXAX-MA, TXAX-KA, TXAX-CT (all manufactured by Kubota Corporation) and the like can be mentioned.
粒子状のチタン酸塩とは、Ｌ／Ｔが１０よりも小さく、Ｌ／Ｂが２よりも小さいチタン酸塩である。例えば、ＴＯＦＩＸ−ＳＧＬ（東邦マテリアル（株）製）、ＧＴＸ−Ｃ（（株）クボタ製）等が挙げられる。
また、粒子状のチタン酸塩のうち、鱗のような薄板状の形状のものを鱗片状のチタン酸塩といい、例えば、テラセスＰＳ、テラセスＰＭ、テラセスＬ、テラセスＴＦ−Ｓ（いずれも、大塚化学（株）製）等が挙げられる。
また、粒子状のチタン酸塩の平均粒子径が１〜５０μｍ、比表面積が０．５〜１０ｍ2／ｇのものが好ましい。なお、平均粒子径はメジアン径で表され、メジアン径とは、レーザー回折法の体積分布から求めた５０％径をいう。また、比表面積は吸着ガスとして窒素ガスを用いたＢＥＴ法等により求めることができる。
上記の様な柱状、板状、粒子状又は鱗片状等のチタン酸塩を用いることで、高い環境適合性と摩擦係数の安定性を両立することができる。The particulate titanate is a titanate having an L / T smaller than 10 and an L / B smaller than 2. For example, TOFIX-SGL (manufactured by Toho Material Co., Ltd.), GTX-C (manufactured by Kubota Co., Ltd.) and the like can be mentioned.
Further, among the particulate titanates, those having a thin plate shape such as a scale are referred to as scaly titanates. For example, Terraces PS, Terraces PM, Terraces L, Terraces TF-S (both are Otsuka Chemical Co., Ltd.).
Further, it is preferable that the particulate titanate has an average particle diameter of 1 to 50 μm and a specific surface area of 0.5 to 10 m 2 / g. In addition, an average particle diameter is represented by a median diameter, and a median diameter means the 50% diameter calculated | required from the volume distribution of the laser diffraction method. The specific surface area can be determined by a BET method using nitrogen gas as an adsorption gas.
By using such a columnar, plate-like, particle-like, or scale-like titanate, both high environmental compatibility and stability of the friction coefficient can be achieved.
本発明において好適に用いられるチタン酸塩としては、具体的には、柱状、板状、粒子状又は鱗片状のチタン酸カリウム、チタン酸リチウムカリウム及びチタン酸マグネシウムカリウムが挙げられる。
またチタン酸塩を含有する場合、チタン酸塩の含有量は、摩擦材組成物中に１０〜２０質量％であることが好ましい。Specific examples of titanates that are preferably used in the present invention include columnar, plate-like, particulate or scale-like potassium titanate, lithium potassium titanate, and magnesium potassium titanate.
Moreover, when it contains a titanate, it is preferable that content of a titanate is 10-20 mass% in a friction material composition.
また、本発明の効果を損なわない程度であれば、本発明の摩擦材組成物に、上記酸化ジルコニウム、黒鉛及びチタン酸塩以外の、通常、摩擦材に用いられる無機充填材を組み合わせて用いることができる。
上記酸化ジルコニウム、黒鉛及びチタン酸塩以外の無機充填材としては、例えば、三硫化アンチモン、硫化スズ、二硫化モリブデン、硫化鉄、硫化ビスマス、硫化亜鉛、水酸化カルシウム、酸化カルシウム、炭酸ナトリウム、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、ドロマイト、コークス、黒鉛、マイカ、酸化鉄、バーミキュライト、硫酸カルシウム、タルク、クレー、ゼオライト、珪酸ジルコニウム、ムライト、クロマイト、酸化チタン、酸化マグネシウム、シリカ、γ−アルミナ等の活性アルミナ等を用いることができ、これらを単独で又は２種類以上を組み合わせて使用することができる。本発明において、無機充填材としては、対面材への攻撃性低下の観点から、硫酸バリウム、三硫化アンチモン、水酸化カルシウム、ゼオライト、珪酸ジルコニウム及びアルミナから選ばれる１種類又は２種類以上を含有することが好ましい。Moreover, as long as the effect of the present invention is not impaired, the friction material composition of the present invention is used in combination with inorganic fillers that are usually used for friction materials other than the zirconium oxide, graphite, and titanate. Can do.
Examples of inorganic fillers other than the zirconium oxide, graphite, and titanate include, for example, antimony trisulfide, tin sulfide, molybdenum disulfide, iron sulfide, bismuth sulfide, zinc sulfide, calcium hydroxide, calcium oxide, sodium carbonate, and carbonic acid. Calcium, magnesium carbonate, barium sulfate, dolomite, coke, graphite, mica, iron oxide, vermiculite, calcium sulfate, talc, clay, zeolite, zirconium silicate, mullite, chromite, titanium oxide, magnesium oxide, silica, γ-alumina, etc. Activated alumina or the like can be used, and these can be used alone or in combination of two or more. In the present invention, the inorganic filler contains one or more kinds selected from barium sulfate, antimony trisulfide, calcium hydroxide, zeolite, zirconium silicate and alumina from the viewpoint of reducing the aggressiveness to the facing material. It is preferable.
無機充填材の総含有量は、酸化ジルコニウムを含め、摩擦材組成物において２０〜８０質量％であることが好ましく、３０〜７０質量％であることがより好ましく４０〜７０質量％であることがさらに好ましい。無機充填材の含有量を２０〜８０質量％とすると、耐熱性の悪化を避けることができる。 The total content of the inorganic filler, including zirconium oxide, is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 40 to 70% by mass in the friction material composition. Further preferred. When content of an inorganic filler shall be 20-80 mass%, a heat resistant deterioration can be avoided.
[繊維基材]
本発明の摩擦材組成物は繊維基材を含有する。繊維基材は摩擦材において補強作用を示すものである。繊維基材としては、有機繊維、金属繊維、無機繊維等が挙げられる。[Fiber base]
The friction material composition of the present invention contains a fiber base material. The fiber base material exhibits a reinforcing action in the friction material. Examples of the fiber base material include organic fibers, metal fibers, and inorganic fibers.
本発明の摩擦材組成物は有機繊維としてアラミド繊維、アクリル繊維、セルロース繊維、フェノール樹脂繊維等を用いることができ、これらを単独で又は２種類以上を組み合わせて使用することができる。この中でも、耐熱性、補強効果の観点から、アラミド繊維を用いることが好ましい。 In the friction material composition of the present invention, an aramid fiber, an acrylic fiber, a cellulose fiber, a phenol resin fiber or the like can be used as an organic fiber, and these can be used alone or in combination of two or more. Among these, it is preferable to use an aramid fiber from the viewpoint of heat resistance and a reinforcing effect.
金属繊維としては銅繊維、黄銅繊維、青銅繊維、鉄繊維、チタン繊維、亜鉛繊維、アルミ繊維等を用いることができ、１種又は２種類以上を組み合わせて用いることができる。この中でも、熱伝導率、融点、延性、引っ張り強度等の観点からは、銅繊維を用いることが好ましいが、環境への優しさの観点から、本発明では摩擦材組成物中、銅の含有量が銅元素として５質量％以下であること（銅繊維は実質的に含有しないこと）を要する。
本発明の摩擦材組成物は、銅繊維を実質的に含有しない場合でも、良好な摩擦係数の安定性を示し、また、良好な耐摩耗性、鳴き特性を発現することができる。As the metal fiber, copper fiber, brass fiber, bronze fiber, iron fiber, titanium fiber, zinc fiber, aluminum fiber, or the like can be used, and one or a combination of two or more can be used. Among these, from the viewpoint of thermal conductivity, melting point, ductility, tensile strength, etc., it is preferable to use copper fiber, but from the viewpoint of environmental friendliness, in the friction material composition in the present invention, the content of copper Is 5 mass% or less as a copper element (copper fiber is not substantially contained).
The friction material composition of the present invention exhibits good friction coefficient stability and can exhibit good wear resistance and squeal characteristics even when it contains substantially no copper fiber.
無機繊維としては、セラミック繊維、生分解性セラミック繊維、鉱物繊維、炭素繊維、ガラス繊維、チタン酸カリウム繊維、アルミノシリケート繊維等を用いることができ、これらを単独で又は２種類以上を組み合わせて使用することができる。これらの中でも、耐摩耗性の観点から、鉱物繊維を用いることが好ましい。一方、環境への優しさ及び人体への影響の観点から、吸引性のチタン酸カリウム繊維等を含有しないことが好ましい。 As inorganic fiber, ceramic fiber, biodegradable ceramic fiber, mineral fiber, carbon fiber, glass fiber, potassium titanate fiber, aluminosilicate fiber, etc. can be used, and these are used alone or in combination of two or more. can do. Among these, it is preferable to use mineral fibers from the viewpoint of wear resistance. On the other hand, from the viewpoint of environmental friendliness and influence on the human body, it is preferable not to contain attractive potassium titanate fibers or the like.
なお、ここでいう鉱物繊維とは、スラグウール等の高炉スラグ、バサルトファイバー等の玄武岩、その他の天然岩石等を主成分として溶融紡糸した人造無機繊維であり、Ａｌ元素を含む天然鉱物であることがより好ましい。具体的には、ＳｉＯ2、Ａｌ2Ｏ3、ＣａＯ、ＭｇＯ、ＦｅＯ、Ｎａ2Ｏ等が含まれるもの、又はこれら化合物が１種又は２種以上含有されるものを用いることができ、より好ましくはこれらのうちＡｌ元素を含むものが、鉱物繊維として用いることができる。摩擦材組成物中に含まれる鉱物繊維全体の平均繊維長が大きくなるほど摩擦材組成物中の各成分との接着強度が低下する傾向があるため、鉱物繊維全体の平均繊維長は５００μｍ以下が好ましく、より好ましくは１００〜４００μｍである。ここで、平均繊維長とは、該当する全ての繊維の長さの平均値を示した数平均繊維長のことをいう。例えば２００μｍの平均繊維長とは、摩擦材組成物原料として用いる鉱物繊維を無作為に５０個選択し、光学顕微鏡で繊維長を測定し、その平均値が２００μｍであることを示す。The mineral fiber referred to here is a man-made inorganic fiber melt-spun mainly composed of blast furnace slag such as slag wool, basalt such as basalt fiber, and other natural rocks, and is a natural mineral containing Al element. Is more preferable. Specifically, those containing SiO 2 , Al 2 O 3 , CaO, MgO, FeO, Na 2 O, etc., or those containing one or more of these compounds can be used, more preferably. Of these, those containing Al element can be used as mineral fibers. Since the adhesive strength with each component in the friction material composition tends to decrease as the average fiber length of the entire mineral fiber contained in the friction material composition increases, the average fiber length of the entire mineral fiber is preferably 500 μm or less. More preferably, it is 100-400 micrometers. Here, the average fiber length refers to a number average fiber length indicating an average value of the lengths of all corresponding fibers. For example, the average fiber length of 200 μm indicates that 50 mineral fibers used as a friction material composition raw material are randomly selected, the fiber length is measured with an optical microscope, and the average value is 200 μm.
本発明で用いられる鉱物繊維は、人体有害性の観点で生体溶解性であることが好ましい。ここでいう生体溶解性の鉱物繊維とは、人体内に取り込まれた場合でも短時間で一部分解され体外に排出される特徴を有する鉱物繊維である。具体的には、化学組成がアルカリ酸化物、アルカリ土類酸化物総量（ナトリウム、カリウム、カルシウム、マグネシウム、バリウムの酸化物の総量）が１８質量％以上で、かつ呼吸による短期バイオ永続試験で、２０μｍ以上の繊維の質量半減期が４０日以内又は腹膜内試験で過度の発癌性の証拠がないか又は長期呼吸試験で関連の病原性や腫瘍発生がないことを満たす繊維を示す（ＥＵ指令９７／６９／ＥＣのＮｏｔａ Ｑ（発癌性適用除外））。このような生体分解性鉱物繊維としては、ＳｉＯ2−Ａｌ2Ｏ3−ＣａＯ−ＭｇＯ−ＦｅＯ−Ｎａ2Ｏ系繊維等が挙げられ、ＳｉＯ2、Ａｌ2Ｏ3、ＣａＯ、ＭｇＯ、ＦｅＯ、Ｎａ2Ｏ等を任意の組み合わせで含有した繊維が挙げられる。市販品としてはＬＡＰＩＮＵＳ ＦＩＢＥＲＳ Ｂ．Ｖ製のＲｏｘｕｌシリーズ等が挙げられる。「Ｒｏｘｕｌ」は、ＳｉＯ2、Ａｌ2Ｏ3、ＣａＯ、ＭｇＯ、ＦｅＯ、Ｎａ2Ｏ等が含まれる。The mineral fiber used in the present invention is preferably biosoluble from the viewpoint of human harm. The term “biosoluble mineral fiber” as used herein refers to a mineral fiber having a characteristic that even if it is taken into the human body, it is partially decomposed and discharged outside the body in a short time. Specifically, the chemical composition is alkali oxide, alkaline earth oxide total amount (total amount of oxides of sodium, potassium, calcium, magnesium, barium) is 18% by mass or more, and in a short-term biopermanent test by respiration, A fiber that has a mass half-life of 20 μm or more within 40 days or no evidence of excessive carcinogenicity in an intraperitoneal test or that has no associated pathogenicity or tumor development in a long-term respiratory test (EU Directive 97 / 69 / EC Nota Q (carcinogenic exclusion)). Examples of such biodegradable mineral fibers include SiO 2 —Al 2 O 3 —CaO—MgO—FeO—Na 2 O fibers and the like, and include SiO 2 , Al 2 O 3 , CaO, MgO, FeO, Na. Examples thereof include fibers containing 2 O or the like in any combination. As a commercial item, LAPINUS FIBERS B.M. Examples include V Roxul series. “Roxul” includes SiO 2 , Al 2 O 3 , CaO, MgO, FeO, Na 2 O and the like.
本発明の摩擦材組成物における繊維基材の含有量は、５〜４０質量％であることが好ましく、５〜２０質量％であることがより好ましく、５〜１８質量％であることがさらに好ましい。繊維基材の含有量を５〜４０質量％とすると、効き特性の著しい低下等の弊害を与えることなく、適度な補強効果を摩擦材に付与することができる。 The content of the fiber base material in the friction material composition of the present invention is preferably 5 to 40% by mass, more preferably 5 to 20% by mass, and further preferably 5 to 18% by mass. . When the content of the fiber base is 5 to 40% by mass, an appropriate reinforcing effect can be imparted to the friction material without causing adverse effects such as a significant decrease in effectiveness characteristics.
［その他の成分］
また、本発明の摩擦材組成物は、前記の材料以外に、必要に応じてその他の材料を配合することができ、例えば、銅粉、黄銅粉、亜鉛粉等の金属粉末等を配合することができ、これらの中では亜鉛粉が好ましい。
銅を含有する場合は、環境への優しさの観点から、摩擦材組成物中の銅の含有量を銅元素として５質量％以下とする必要がある。また、銅を多量に含有すると、金属皮膜による寄与が過剰となり、逆に熱履歴後の摩擦係数が上昇することで、効きの安定性が損なわれる傾向があるため、銅の含有量は上記含有量としている。[Other ingredients]
Moreover, the friction material composition of this invention can mix | blend other materials as needed other than the said material, for example, metal powders, such as copper powder, brass powder, zinc powder, etc. Among these, zinc powder is preferable.
When it contains copper, it is necessary to make content of copper in a friction material composition into 5 mass% or less as a copper element from a viewpoint of the kindness to an environment. In addition, if copper is contained in a large amount, the contribution due to the metal film becomes excessive, and conversely, the coefficient of friction tends to deteriorate the stability of the effect by increasing the coefficient of friction after the heat history. Amount.
＜摩擦材及び摩擦部材＞
本発明の摩擦材組成物は、これを成形することにより、自動車等のディスクブレーキパッドやブレーキライニング等の摩擦材として使用することができる。また本発明の摩擦材組成物を目的形状に成形、加工、貼り付け等の工程を施すことによりクラッチフェーシング、電磁ブレーキ、保持ブレーキ等の摩擦材としても使用することができる。本発明の摩擦材は摩擦係数の安定性に優れているため、制動時に負荷の大きいディスクブレーキパッドの摩擦材に好適である。
さらに、上記摩擦材を用いることにより、該摩擦材を摩擦面となるように形成した摩擦部材を得ることができる。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、下記の構成等が挙げられる。
（１）摩擦部材のみの構成
（２）裏金と、該裏金の上に形成させ、摩擦面となる本発明の摩擦材組成物からなる摩擦部材とを有する構成
（３）上記（２）の構成において、裏金と摩擦部材との間に、裏金の接着効果を高めるための表面改質を目的としたプライマー層、裏金と摩擦部材の接着を目的とした接着層をさらに介在させた構成、等が挙げられる。
上記裏金は、摩擦部材の機械的強度の向上のために、通常、摩擦部材として用いるものであり、材質としては、金属又は繊維強化プラスチック等を用いることができ、例えば、鉄、ステンレス、無機繊維強化プラスチック、炭素繊維強化プラスチック等が挙げられる。プライマー層及び接着層としては、通常、ブレーキシュー等の摩擦部材に用いられるものであればよい。<Friction material and friction member>
By molding the friction material composition of the present invention, it can be used as a friction material for disc brake pads and brake linings of automobiles and the like. In addition, the friction material composition of the present invention can be used as a friction material for clutch facing, electromagnetic brake, holding brake, etc. by subjecting the friction material composition of the present invention to steps such as molding, processing, and pasting. Since the friction material of the present invention is excellent in the stability of the friction coefficient, it is suitable as a friction material for a disc brake pad having a large load during braking.
Furthermore, by using the friction material, it is possible to obtain a friction member in which the friction material is formed to be a friction surface. Examples of the friction member that can be formed using the friction material include the following configurations.
(1) Configuration of only friction member (2) Configuration having a back metal and a friction member formed on the back metal and made of the friction material composition of the present invention to be a friction surface (3) Configuration of (2) above In the structure, a primer layer for the purpose of surface modification for enhancing the adhesion effect of the back metal between the back metal and the friction member, a configuration in which an adhesive layer for the purpose of bonding the back metal and the friction member is further interposed, etc. Can be mentioned.
The backing metal is usually used as a friction member in order to improve the mechanical strength of the friction member. As the material, metal or fiber reinforced plastic can be used, for example, iron, stainless steel, inorganic fiber, etc. Examples thereof include reinforced plastic and carbon fiber reinforced plastic. The primer layer and the adhesive layer may be those used for friction members such as brake shoes.
本発明の摩擦材は、一般に使用されている方法を用いて製造することができ、本発明の摩擦材組成物を加熱加圧成形等して製造することができる。
詳細には、例えば、本発明の摩擦材組成物をレディーゲミキサー、加圧ニーダー、アイリッヒミキサー等の混合機を用いて均一に混合し、この混合物を成形金型にて予備成形し、得られた予備成形物を成形温度１３０〜１６０℃、成形圧力２０〜５０ＭＰａの条件で２〜１０分間成形し、得られた成形物を１５０〜２５０℃で２〜１０時間熱処理することにより本発明の摩擦材を得ることができる。なお、必要に応じて塗装、スコーチ処理、研磨処理等を行ってもよい。The friction material of the present invention can be produced by a generally used method, and can be produced by subjecting the friction material composition of the present invention to heat-pressure molding or the like.
Specifically, for example, the friction material composition of the present invention is uniformly mixed using a mixer such as a Readyge mixer, a pressure kneader, or an Eirich mixer, and this mixture is preformed in a molding die to obtain a mixture. The obtained preform is molded for 2 to 10 minutes under the conditions of a molding temperature of 130 to 160 ° C. and a molding pressure of 20 to 50 MPa, and the obtained molded product is heat-treated at 150 to 250 ° C. for 2 to 10 hours. A friction material can be obtained. In addition, you may perform a coating, a scorch process, a grinding | polishing process, etc. as needed.
本発明の摩擦材組成物は、高負荷制動時及び熱履歴後の摩擦係数の低下を抑制し、かつ低温放置後の摩擦係数の上昇を抑制できる摩擦材を与えることから、ディスクブレーキパッドやブレーキライニング等の摩擦部材の「上張り材」として有用であり、さらに摩擦部材の「下張り材」として成形して用いることもできる。
なお、「上張り材」とは、摩擦部材の摩擦面となる摩擦材であり、「下張り材」とは、摩擦部材の摩擦面となる摩擦材と裏金との間に介在する、摩擦材と裏金との接着部付近の剪断強度、耐クラック性向上を目的とした層のことである。The friction material composition of the present invention provides a friction material that suppresses a decrease in the coefficient of friction during high load braking and after a thermal history, and can suppress an increase in the coefficient of friction after being left at a low temperature. It is useful as a “upper material” of a friction member such as a lining, and can also be used after being molded as a “lower material” of a friction member.
The “upper material” is a friction material that becomes the friction surface of the friction member, and the “underlay material” is a friction material that is interposed between the friction material that becomes the friction surface of the friction member and the back metal. It is a layer for the purpose of improving the shear strength and crack resistance in the vicinity of the adhesion part with the back metal.
本発明によれば、自動車用ディスクブレーキパッドやブレーキライニング等の摩擦材に用いた際に、高負荷制動時、熱履歴後の摩擦係数の低下を抑制し、かつ低温放置後の摩擦係数の上昇を抑制する、つまり様々な制動条件で安定した摩擦係数を発現することができる。また、本発明の摩擦材組成物は、耐摩耗性にも優れ、さらに鳴き特性も優れる。また、本発明によれば、上記特性を有する摩擦材及び摩擦部材を提供することができる。 According to the present invention, when used in a friction material such as an automotive disc brake pad or brake lining, a decrease in the friction coefficient after thermal history is suppressed during high load braking, and an increase in the friction coefficient after being left at low temperature. In other words, a stable friction coefficient can be expressed under various braking conditions. Further, the friction material composition of the present invention is excellent in wear resistance and also in squeal characteristics. Moreover, according to this invention, the friction material and friction member which have the said characteristic can be provided.
以下、実施例により本発明をさらに詳細に説明する。本発明は何らこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these.
＜実施例１〜６及び比較例１〜８＞
［ディスクブレーキパッドの作製］
表１及び２に示す配合量に従って材料を混合し、実施例１〜６及び比較例１〜８の摩擦材組成物を得た。なお、表１及び２の各成分の配合量の単位は、摩擦材組成物中の質量％である。<Examples 1-6 and Comparative Examples 1-8>
[Production of disc brake pads]
The materials were mixed according to the blending amounts shown in Tables 1 and 2, and the friction material compositions of Examples 1 to 6 and Comparative Examples 1 to 8 were obtained. In addition, the unit of the compounding quantity of each component of Table 1 and 2 is the mass% in a friction material composition.
この摩擦材組成物をレディーゲミキサー（（株）マツボー社製、商品名：レディーゲミキサーＭ２０）で混合し、この混合物を成形プレス（王子機械工業（株）製）で予備成形し、得られた予備成形物を成形温度１４５℃、成形圧力３５ＭＰａの条件で５分間成形プレス（三起精工（株）社製）を用いて、日立オートモティブシステムズ（株）製の裏金と共に加熱加圧成形し、得られた成形品を２００℃で４．５時間熱処理し、ロータリー研磨機を用いて研磨し、５００℃のスコーチ処理を行って、ディスクブレーキパッド（摩擦材の厚さ９．５ｍｍ、摩擦材投影面積５２ｃｍ2）を得た。This friction material composition is mixed with a ladyge mixer (manufactured by Matsubo Co., Ltd., trade name: ladyge mixer M20), and this mixture is preformed with a molding press (manufactured by Oji Machinery Co., Ltd.). The pre-molded product was heated and pressure-molded with a backing metal manufactured by Hitachi Automotive Systems, Ltd. using a molding press (manufactured by Sanki Seiko Co., Ltd.) for 5 minutes under conditions of a molding temperature of 145 ° C. and a molding pressure of 35 MPa, The resulting molded product was heat treated at 200 ° C. for 4.5 hours, polished using a rotary polishing machine, subjected to scorch treatment at 500 ° C., and a disc brake pad (friction material thickness 9.5 mm, friction material projection). An area of 52 cm 2 ) was obtained.
なお、実施例及び比較例において使用した各種材料は次のとおりである。
（結合材）
・フェノール樹脂：日立化成（株）製（商品名：ＨＰ４９１ＵＰ）
（有機充填材）
・カシューダスト：東北化工（株）製（商品名：ＦＦ−１０５６）
・ＳＢＲ粉：ミサワ東洋（株）製（商品名：粉末ＴＰＡ）
（無機充填材）
・黒鉛：ＴＩＭＣＡＬ社製（商品名：ＫＳ１５）;平均粒子径（Ｄ５０）＝８．５μｍ
・チタン酸カリウム：大塚化学（株）製（商品名：テラセスＴＦ−Ｓ、鱗片状）
・硫酸バリウム：堺化学（株）製（商品名：ＢＡ）
・アルミナ：昭和電工（株）製（商品名：Ａ−４３−Ｍ）
・珪酸ジルコニウム：第１稀元素化学工業（株）製（商品名：ＭＺ１０００Ｂ）
・三硫化アンチモン：Ｃｈｅｍｔａｌｌ Ｇｅｓ．ｍ．ｂ．Ｈ製（商品名：FRICSTAR）
・水酸化カルシウム：秩父石炭工業（株）製（商品名：ＳＡ１４９）
・ゼオライト：水澤化学工業（株）製（商品名：シルトンＢ）
・酸化ジルコニウムＡ：第一稀元素化学工業（株）製（商品名：ＢＲ３ＱＺ）;平均粒子径（Ｄ５０）＝２．５μｍ
・酸化ジルコニウムＢ：第一稀元素化学工業（株）製（商品名：ＢＲＱＺ）;平均粒子径（Ｄ５０）＝５．７μｍ
・酸化ジルコニウムＣ：第一稀元素化学工業（株）製（商品名：ＢＲ１２ＱＺ）;平均粒子径（Ｄ５０）＝６．７μｍ
・酸化ジルコニウムＤ：ユニバーサルアメリカ製（商品名：Ｚ９９ ２−２．６）;平均粒子径（Ｄ５０）＝１．４μｍ
・酸化ジルコニウムＥ：ユニバーサルアメリカ製（商品名：Ｚ９９ ２−３．５）;平均粒子径（Ｄ５０）=２．９μｍ
・酸化ジルコニウムＦ:ユニバーサルアメリカ製（商品名：Ｚ９９ ３−５）;平均粒子径（Ｄ５０）=４．１μｍThe various materials used in the examples and comparative examples are as follows.
(Binder)
・ Phenolic resin: manufactured by Hitachi Chemical Co., Ltd. (trade name: HP491UP)
(Organic filler)
・ Cashew dust: Tohoku Kako Co., Ltd. (trade name: FF-1056)
・ SBR powder: manufactured by Misawa Toyo Co., Ltd. (trade name: powder TPA)
(Inorganic filler)
Graphite: manufactured by TIMCAL (trade name: KS15); average particle diameter (D50) = 8.5 μm
Potassium titanate: Otsuka Chemical Co., Ltd. (trade name: Terrases TF-S, scale-like)
-Barium sulfate: manufactured by Sakai Chemical Co., Ltd. (trade name: BA)
・ Alumina: Showa Denko Co., Ltd. (trade name: A-43-M)
・ Zirconium silicate: manufactured by 1st Rare Element Chemical Industry Co., Ltd. (trade name: MZ1000B)
Antimony trisulfide: Chemtall Ges. m. b. Made by H (trade name: FRICSTAR)
・ Calcium hydroxide: manufactured by Chichibu Coal Industry Co., Ltd. (trade name: SA149)
・ Zeolite: Made by Mizusawa Chemical Co., Ltd. (trade name: Shilton B)
Zirconium oxide A: manufactured by Daiichi Rare Element Chemical Co., Ltd. (trade name: BR3QZ); average particle diameter (D50) = 2.5 μm
Zirconium oxide B: manufactured by Daiichi Rare Element Chemical Industries, Ltd. (trade name: BRQZ); average particle diameter (D50) = 5.7 μm
Zirconium oxide C: manufactured by Daiichi Rare Element Chemical Industries, Ltd. (trade name: BR12QZ); average particle diameter (D50) = 6.7 μm
Zirconium oxide D: made by Universal America (trade name: Z99 2-2.6); average particle diameter (D50) = 1.4 μm
Zirconium oxide E: manufactured by Universal America (trade name: Z99 2-3.5); average particle diameter (D50) = 2.9 μm
Zirconium oxide F: manufactured by Universal America (trade name: Z99 3-5); average particle diameter (D50) = 4.1 μm
なお、酸化ジルコニウムＣは、粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含み、酸化ジルコニウムＢ、Ｆは、粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含まず、酸化ジルコニウムＥは粒子径が２０μｍ以上の酸化ジルコニウムを実質的に含まず、酸化ジルコニウムＡ、Ｄは粒子径が１０μｍ以上の酸化ジルコニウムを実質的に含まない。
なお、粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含有するかどうかは、レーザー回折粒度分布測定等の方法を用いて、粒子径の分布を測定することで求めた。具体的には、粒子径分布積算曲線を描いた時に粒子径の最も小さい粒子から順次積算して全体の９９.９％に達するところの粒子径が３０μより小さければ、粒子径が３０μｍ以上の酸化ジルコニウムを実質的に含有しないといえる。２０、１０μm以上の酸化ジルコニウムを実質的に含有するかどうかについても同様の手法で求めることができる。粒子径分布は、レーザー回折／散乱式粒子径分布測定装置 ＬＡ・９２０（（株）堀場製作所製）で測定した。
また、酸化ジルコニウムの平均粒子径（Ｄ５０）は、粒子径分布積算曲線を描いた時に粒子径の最も小さい粒子から順次積算して全体の５０％に達するところの粒子径を、平均粒子径（Ｄ５０）とした。粒子径分布は、レーザー回折／散乱式粒子径分布測定装置 ＬＡ・９２０（（株）堀場製作所製）で測定した。Zirconium oxide C substantially contains zirconium oxide having a particle diameter of 30 μm or more, zirconium oxides B and F substantially do not contain zirconium oxide having a particle diameter of 30 μm or more, and zirconium oxide E has a particle diameter. Zirconium oxide having a particle diameter of 10 μm or more is substantially free of zirconium oxide A and D.
Whether or not zirconium oxide having a particle size of 30 μm or more was substantially contained was determined by measuring the particle size distribution using a method such as laser diffraction particle size distribution measurement. Specifically, when the particle diameter distribution cumulative curve is drawn, the particles having the smallest particle diameter are accumulated sequentially to reach 99.9% of the whole. It can be said that zirconium is not substantially contained. Whether it substantially contains 20, 10 μm or more of zirconium oxide can also be determined by the same method. The particle size distribution was measured with a laser diffraction / scattering particle size distribution measuring apparatus LA.920 (manufactured by Horiba, Ltd.).
In addition, the average particle diameter (D50) of zirconium oxide is the average particle diameter (D50) obtained by sequentially integrating the particles having the smallest particle diameter from the smallest particle diameter when drawing the particle size distribution integration curve and reaching 50% of the total particle diameter. ). The particle size distribution was measured with a laser diffraction / scattering particle size distribution measuring apparatus LA.920 (manufactured by Horiba, Ltd.).
（繊維基材）
・アラミド繊維（有機繊維）：東レ・デュポン（株）製（商品名：１Ｆ５３８）
・銅繊維（金属繊維）：Ｓｕｎｎｙ Ｍｅｔａｌ製（商品名：ＳＣＡ−１０７０）
・鉱物繊維（無機繊維）：ＬＡＰＩＮＵＳ ＦＩＢＥＲＳ Ｂ．Ｖ製（商品名：ＲＢ２４０ Ｒｏｘｕｌ １０００）
（亜鉛粉）
・亜鉛粉：福田金属箔粉工業（株）製（商品名：Ｚｎ−Ａｔ−２００）(Fiber base)
・ Aramid fiber (organic fiber): manufactured by Toray DuPont Co., Ltd. (trade name: 1F538)
・ Copper fiber (metal fiber): manufactured by Sunny Metal (trade name: SCA-1070)
Mineral fiber (inorganic fiber): LAPINUS FIBERS B. Product made in V (Brand name: RB240 Roxul 1000)
(Zinc powder)
・ Zinc powder: Fukuda Metal Foil Powder Industry Co., Ltd. (trade name: Zn-At-200)
［性能評価］
前記の方法で形成した実施例１〜６及び比較例１〜８のディスクブレーキパッドを、ブレーキダイナモ試験機（新日本特機（株）製）を用いて次に示す各種性能の評価を行った。実験には、一般的なピンスライド式のコレット型キャリパー及びキリウ社製ベンチレーテッドディスクローター（ＦＣ２５０）を用い、日産自動車（株）製スカイラインＶ３５の慣性モーメントで評価を行った。評価結果を表１及び２に示した。[Performance evaluation]
The disk brake pads of Examples 1 to 6 and Comparative Examples 1 to 8 formed by the above method were evaluated for various performances shown below using a brake dynamo tester (manufactured by Shin Nippon Toki Co., Ltd.). . In the experiment, a general pin-slide type collet caliper and a ventilated disc rotor (FC250) manufactured by Kiriu Corporation were used, and evaluation was performed with the moment of inertia of the Skyline V35 manufactured by Nissan Motor Co., Ltd. The evaluation results are shown in Tables 1 and 2.
（鳴き特性の評価）
ブレーキ鳴きを顕著に発生させるため、ディスクブレーキパッドには、一般的に鳴き防止のために装着される減衰シムを用いずに鳴き試験を行った。これにより、条件間の鳴き特性を効果的に比較評価できる。
低温鳴き特性の評価に関して説明する。最初に、ＪＡＳＯ Ｃ４２７に準拠したすり合わせ（初速度５０ｋｍ／ｈ、減速度０．３Ｇ、制動前ブレーキ温度１００℃、制動回数２００回）を行った。その後、温度−５℃、湿度４０％ＲＨの環境で２時間放置し、１２０秒のインターバルで車速１０ｋｍ／ｈ、ブレーキ液圧０．５ＭＰａの制動を１０回繰り返した。上記の１０回制動を１サイクルとし、各サイクル間で３０分放置をはさんで計５サイクル実施した。計５０回制動の内、７０ｄＢ以上の音圧で計測されたブレーキ鳴きの発生率を、実施例１〜６及び比較例１〜８のディスクブレーキパッドについてそれぞれ評価し、低温鳴き性能とした。
低温鳴き発生率＝（（７０ｄＢ以上の音圧が発生した回数）÷５０）×１００（％）(Evaluation of squeal characteristics)
In order to generate the brake squeeze significantly, the squeal test was conducted without using a damping shim generally attached to the disc brake pad to prevent the squeal. This makes it possible to effectively compare and evaluate the squeal characteristics between conditions.
The evaluation of the low temperature squeal characteristics will be described. First, the sizing according to JASO C427 (initial speed 50 km / h, deceleration 0.3 G, brake temperature before braking 100 ° C., number of times of braking 200 times) was performed. After that, it was left for 2 hours in an environment of temperature -5 ° C. and humidity 40% RH, and braking at a vehicle speed of 10 km / h and a brake hydraulic pressure of 0.5 MPa was repeated 10 times at an interval of 120 seconds. The 10 times of braking described above was taken as one cycle, and a total of 5 cycles were carried out with 30 minutes left between each cycle. The occurrence rate of brake squeal measured at a sound pressure of 70 dB or more out of a total of 50 brakings was evaluated for each of the disc brake pads of Examples 1 to 6 and Comparative Examples 1 to 8, and was defined as low temperature squeal performance.
Low-temperature squeak occurrence rate = ((number of occurrences of sound pressure of 70 dB or more) ÷ 50) × 100 (%)
（耐摩耗性（摩耗特性）の評価）
試験はＪＡＳＯ Ｃ４２７に準拠し、制動前ブレーキ温度が１００、２００、３００、４００℃におけるディスクパッドの摩耗量をそれぞれ計測し、耐摩耗性として評価した。(Evaluation of wear resistance (wear characteristics))
The test was based on JASO C427, and the amount of wear of the disk pad at brake temperatures before braking of 100, 200, 300, and 400 ° C. was measured and evaluated as wear resistance.
（効き特性の評価）
摩擦係数：
摩擦係数は、自動車技術会規格ＪＡＳＯ Ｃ４０６に準拠し、第２効力試験（通常制動時）、第２フェード試験（高負荷制動時）及び第３効力試験（熱履歴後）を行なった。
第２効力試験及び第３効力試験における、摩擦係数の平均値をそれぞれ算出した。また、第２フェード試験における摩擦係数のｍｉｎ−ｍｉｎμ値（制動開始時から車両停止０．５秒前までの摩擦係数の最低値）を高負荷制動時の摩擦係数として評価した。
摩擦係数の変化率：
第２効力試験及び第３効力試験の間にフェード試験を実施するため、第２効力試験の摩擦係数及び第３効力試験の摩擦係数結果を比較することで、熱履歴前後での摩擦係数の変動を評価できる。第２効力試験の摩擦係数と比較した第３効力試験の摩擦係数の変化率は、熱履歴前後での摩擦係数安定性の観点から、９５〜１０５％であることが望ましい。
さらに、上記の鳴き特性評価試験の−５℃条件における摩擦係数を低温時効力（低温時の摩擦係数）とした。この低温時効力と、上記の第２効力試験の摩擦係数とを比較することで、低温条件における摩擦係数の変動を評価できる。第２効力試験の摩擦係数と比較した低温時効力の変化率は、低温時の摩擦係数安定性、及び鳴き特性の観点から、１００〜１２０％であることが望ましい。(Evaluation of efficacy characteristics)
Coefficient of friction:
The friction coefficient was in accordance with the Japan Society of Automotive Engineers Standard JASO C406, and a second efficacy test (during normal braking), a second fade test (during high load braking), and a third efficacy test (after thermal history) were performed.
The average value of the friction coefficient in the second efficacy test and the third efficacy test was calculated. Further, the min-minμ value of the friction coefficient in the second fade test (the minimum value of the friction coefficient from the start of braking to 0.5 seconds before the vehicle stop) was evaluated as the friction coefficient during high load braking.
Friction coefficient change rate:
In order to perform a fade test between the second efficacy test and the third efficacy test, by comparing the friction coefficient results of the second efficacy test and the friction coefficient result of the third efficacy test, the variation of the friction coefficient before and after the thermal history Can be evaluated. The rate of change of the coefficient of friction of the third efficacy test compared to the coefficient of friction of the second efficacy test is desirably 95 to 105% from the viewpoint of friction coefficient stability before and after the thermal history.
Furthermore, the coefficient of friction in the above squeal property evaluation test at −5 ° C. was defined as the effect at low temperature (friction coefficient at low temperature). By comparing this low temperature effect with the friction coefficient of the second efficacy test described above, it is possible to evaluate the variation of the friction coefficient under low temperature conditions. It is desirable that the rate of change in the efficacy at low temperature compared to the friction coefficient in the second efficacy test is 100 to 120% from the viewpoint of the friction coefficient stability at low temperature and the squeal characteristics.
実施例１〜６は、元素としての銅を５質量％を超えて含有する比較例８と同水準の耐摩耗性を有しており、さらに低温時や熱履歴後における摩擦係数の安定性は比較例８より良好であった。また、メジアン半径が４μｍを超える酸化ジルコニウムを含む比較例１〜３、酸化ジルコニウムの含有量が２０質量％を超える比較例４、酸化ジルコニウムの含有量が３質量％未満である比較例５、カシューダストを８質量％より多く含有する比較例６、カシューダストを３質量％より少なく含有する比較例７と比較して、実施例１〜６は低温時鳴き発生率が低く、耐摩耗性も良好で、高負荷制動（フェード）時の摩擦係数が高く、低温時や熱履歴後でも摩擦係数安定性に優れることは明らかである。 Examples 1 to 6 have the same level of wear resistance as Comparative Example 8 containing more than 5% by mass of copper as an element, and the stability of the coefficient of friction at low temperatures and after thermal history is It was better than Comparative Example 8. Comparative Examples 1 to 3 containing zirconium oxide having a median radius exceeding 4 μm, Comparative Example 4 having a zirconium oxide content of more than 20% by mass, Comparative Example 5 having a zirconium oxide content of less than 3% by mass, Cashew Compared to Comparative Example 6 containing more than 8% by mass of dust and Comparative Example 7 containing less than 3% by mass of cashew dust, Examples 1 to 6 have a low squeaking rate at low temperatures and good wear resistance. Thus, it is clear that the friction coefficient at the time of high load braking (fade) is high, and that the friction coefficient stability is excellent even at a low temperature or after a thermal history.
本発明の摩擦材組成物、これを用いた摩擦材及び摩擦部材は、従来品と比較して制動時に生成する摩耗粉中の銅が少ないことから環境に優しく、かつ良好な摩擦係数の安定性、耐摩耗性、及び低温時の鳴き特性の発現が可能であり、乗用車用ブレーキパッド等の摩擦材及び摩擦部材に好適である。 The friction material composition of the present invention, the friction material using the friction material, and the friction member are environmentally friendly and have a good coefficient of friction because the amount of copper in the wear powder generated during braking is less than that of conventional products. It is possible to exhibit wear resistance and squeal characteristics at low temperatures, and is suitable for friction materials and friction members such as brake pads for passenger cars.
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| JP2016011404A (en) * | 2014-06-30 | 2016-01-21 | 日立オートモティブシステムズ株式会社 | Brake friction material |
| JP5963814B2 (en) * | 2014-08-01 | 2016-08-03 | 日清紡ブレーキ株式会社 | Friction material |
| JP6490942B2 (en) * | 2014-10-14 | 2019-03-27 | 日本ブレーキ工業株式会社 | Friction material composition, friction material and friction member |
| JP6570167B2 (en) * | 2015-01-20 | 2019-09-04 | 日本ブレーキ工業株式会社 | Friction material composition, and friction material and friction member using the same |
| WO2016121748A1 (en) * | 2015-01-29 | 2016-08-04 | 日本ブレーキ工業株式会社 | Friction material composition, and friction material and friction member using friction material composition |
| JP6559964B2 (en) * | 2015-01-29 | 2019-08-14 | 日本ブレーキ工業株式会社 | Friction material composition, friction material and friction member |
| JP6799364B2 (en) * | 2015-01-29 | 2020-12-16 | 日本ブレーキ工業株式会社 | Friction material composition, friction material and friction member |
| JP6592976B2 (en) * | 2015-06-10 | 2019-10-23 | 日立化成株式会社 | Friction material composition, friction material using friction material composition, and friction member |
| JP6610014B2 (en) * | 2015-06-10 | 2019-11-27 | 日立化成株式会社 | Friction material composition, friction material using friction material composition, and friction member |
| KR20190017068A (en) | 2016-04-21 | 2019-02-19 | 히타치가세이가부시끼가이샤 | Friction material composition, friction material using same and friction member |
| JP6795035B2 (en) * | 2016-07-26 | 2020-12-02 | 昭和電工マテリアルズ株式会社 | Resin molded body and resin gear |
| WO2019150504A1 (en) * | 2018-01-31 | 2019-08-08 | 日立化成株式会社 | Friction material, friction material composition and friction member |
| JPWO2019150502A1 (en) * | 2018-01-31 | 2021-02-25 | 昭和電工マテリアルズ株式会社 | Friction material, friction material composition and friction member |
| JPWO2019150501A1 (en) * | 2018-01-31 | 2021-02-04 | 昭和電工マテリアルズ株式会社 | Friction material, friction material composition and friction member |
| JP2020073635A (en) * | 2019-09-18 | 2020-05-14 | 日本ブレーキ工業株式会社 | Friction material composition, friction material and friction member |
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