JP2023175418A - Friction material-forming composition, friction material, friction member, and automotive disc brake pad - Google Patents
Friction material-forming composition, friction material, friction member, and automotive disc brake pad Download PDFInfo
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- 239000002783 friction material Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 28
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 239000003607 modifier Substances 0.000 description 6
- 230000001629 suppression Effects 0.000 description 5
- 239000003082 abrasive agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- 239000000945 filler Substances 0.000 description 3
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- 239000005011 phenolic resin Substances 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 229920000058 polyacrylate Polymers 0.000 description 2
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019492 Cashew oil Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
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- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
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Abstract
Description
本開示は、摩擦材形成用組成物、摩擦材、摩擦部材及び自動車用ディスクブレーキパッドに関する。 The present disclosure relates to a composition for forming a friction material, a friction material, a friction member, and an automobile disc brake pad.
従来、乗用車の制動装置としてディスクブレーキが使用されており、その摩擦部材として金属製のベース部材に摩擦材が貼り付けられたディスクブレーキパッドが使用されている。繊維基材、摩擦調整材、結合材等を配合した摩擦材組成物を用い、予備成形、熱成形、仕上げ等の工程からなる製造プロセスによって摩擦材は製造される。 Conventionally, a disc brake has been used as a braking device for a passenger car, and a disc brake pad in which a friction material is attached to a metal base member is used as the friction member. A friction material is manufactured using a friction material composition containing a fiber base material, a friction modifier, a binder, etc., through a manufacturing process including steps such as preforming, thermoforming, and finishing.
自動車用ディスクブレーキパッドに用いられる摩擦材組成物としては、例えば、繊維基材、結合材及び摩擦調整材を含み、該摩擦材組成物中の銅の含有量が０．５質量％以下であり、平均粒子径が０．５～８μｍのフッ素系ポリマー粒子を含有することを特徴とする摩擦材組成物が提案されている（例えば、特許文献１参照）。 The friction material composition used for automobile disc brake pads includes, for example, a fiber base material, a binder, and a friction modifier, and the content of copper in the friction material composition is 0.5% by mass or less. , a friction material composition characterized by containing fluoropolymer particles having an average particle diameter of 0.5 to 8 μm has been proposed (see, for example, Patent Document 1).
自動車用ディスクブレーキパッド（以下、「ブレーキパッド」ともいう。）に使用される摩擦材としては、ブレーキパッドの摩耗、使用環境による摩擦特性の変化、使用時のブレーキ鳴き、ブレーキパッドと接触するローターの摩耗等を抑制可能であることが望ましい。 Friction materials used in automobile disc brake pads (hereinafter also referred to as "brake pads") include wear of the brake pads, changes in friction characteristics due to usage environment, brake squeal during use, and rotors that come into contact with the brake pads. It is desirable to be able to suppress wear, etc.
例えば、ブレーキパッドの使用環境による摩擦特性の変化としては、高湿条件下等に放置する前後の摩擦係数（μ）の変化率（例えば、高湿条件下に放置する前の摩擦係数に対する高湿条件下に放置した後の摩擦係数の比、以下、「放置後μ比」ともいう。）によって評価することが可能である。例えば、放置後μ比が１よりも大きくなる場合、高湿条件によって摩擦係数が増加することで、使用時のブレーキの鳴きが発生しやすくなる。そのため、放置後μ比の上昇を抑制可能であることが望ましい。 For example, changes in the friction characteristics of brake pads due to the environment in which they are used include the rate of change in the coefficient of friction (μ) before and after leaving the brake pads in high humidity conditions (for example, It is possible to evaluate by the ratio of friction coefficients after being left under certain conditions (hereinafter also referred to as "μ ratio after being left"). For example, if the μ ratio becomes larger than 1 after being left unused, the friction coefficient increases due to high humidity conditions, making the brakes more likely to squeal during use. Therefore, it is desirable to be able to suppress the increase in μ ratio after standing.
放置後μ比の上昇を抑制する手法としては、摩擦材組成物に含まれる繊維基材、摩擦調整材、研削材等の各成分を調整することが考えられる。しかし、ブレーキパッドに求められる所望の摩擦係数を維持しながら、各成分の組成を調整して放置後μ比の上昇を抑制することを試みた場合、ブレーキパッドと接触するローターの摩耗が発生しやすくなる。そのため、低い放置後μ比と、ローター摩耗の抑制とはトレードオフの関係にあり、両立させることが難しい。 As a method for suppressing the increase in μ ratio after standing, it is possible to adjust each component contained in the friction material composition, such as a fiber base material, a friction modifier, and an abrasive material. However, if an attempt is made to suppress the increase in μ ratio after storage by adjusting the composition of each component while maintaining the desired coefficient of friction required for a brake pad, wear of the rotor that comes into contact with the brake pad will occur. It becomes easier. Therefore, there is a trade-off relationship between a low μ ratio after standing and suppression of rotor wear, and it is difficult to achieve both.
本開示は上記事情に鑑みてなされたのであり、低い放置後μ比及びローター摩耗の抑制を両立可能な摩擦材を作製可能な摩擦材形成用組成物、これを成形して得られる摩擦材、並びに当該摩擦材を備える摩擦部材及び自動車用ディスクブレーキパッドを提供することを目的とする。 The present disclosure has been made in view of the above circumstances, and includes a composition for forming a friction material that can produce a friction material that can achieve both a low μ ratio after standing and suppression of rotor wear, a friction material obtained by molding the composition, Another object of the present invention is to provide a friction member and a disc brake pad for automobiles that include the friction material.
上記課題を解決するための手段には、以下の実施態様が含まれる。
＜１＞ チタン酸塩と、ポリテトラフルオロエチレンと、酸化ジルコニウムとを含み、
銅を含まないか、あるいは、銅の含有率が元素基準にて０質量％を超えて０．５質量％以下であり、
前記チタン酸塩の含有率が２０質量％以上３５質量％未満であり、
前記ポリテトラフルオロエチレンの含有率が０．５質量％以上５質量％未満であり、
前記酸化ジルコニウムの体積平均粒径が８．０μｍよりも大きい摩擦材形成用組成物。
＜２＞ 金属硫化物を含まない＜１＞に記載の摩擦材形成用組成物。
＜３＞ 鉄に対して犠牲防食作用を有する金属粉末をさらに含む＜１＞又は＜２＞に記載の摩擦材形成用組成物。
＜４＞ 前記酸化ジルコニウムが脱珪ジルコニアを含む＜１＞～＜３＞のいずれか１つに記載の摩擦材形成用組成物。
＜５＞ 前記ポリテトラフルオロエチレンの体積平均粒径が０．５μｍ～８．０μｍである＜１＞～＜４＞のいずれか１つに記載の摩擦材形成用組成物。
＜６＞ ＜１＞～＜５＞のいずれか１つに記載の摩擦材形成用組成物を成形して得られる摩擦材。
＜７＞ ＜６＞に記載の摩擦材と、裏金とを備える摩擦部材。
＜８＞ ＜６＞に記載の摩擦材を備える自動車用ディスクブレーキパッド。
Means for solving the above problems include the following embodiments.
<1> Contains titanate, polytetrafluoroethylene, and zirconium oxide,
Does not contain copper, or has a copper content of more than 0% by mass and 0.5% by mass or less on an elemental basis,
The content of the titanate is 20% by mass or more and less than 35% by mass,
The content of the polytetrafluoroethylene is 0.5% by mass or more and less than 5% by mass,
A composition for forming a friction material, wherein the volume average particle size of the zirconium oxide is larger than 8.0 μm.
<2> The composition for forming a friction material according to <1>, which does not contain metal sulfides.
<3> The composition for forming a friction material according to <1> or <2>, further comprising a metal powder having a sacrificial anticorrosion effect on iron.
<4> The composition for forming a friction material according to any one of <1> to <3>, wherein the zirconium oxide contains desiliconized zirconia.
<5> The composition for forming a friction material according to any one of <1> to <4>, wherein the polytetrafluoroethylene has a volume average particle diameter of 0.5 μm to 8.0 μm.
<6> A friction material obtained by molding the composition for forming a friction material according to any one of <1> to <5>.
<7> A friction member comprising the friction material according to <6> and a back metal.
<8> An automobile disc brake pad comprising the friction material according to <6>.
本開示によれば、低い放置後μ比及びローター摩耗の抑制を両立可能な摩擦材を作製可能な摩擦材形成用組成物、これを成形して得られる摩擦材、並びに当該摩擦材を備える摩擦部材及び自動車用ディスクブレーキパッドが提供される。 According to the present disclosure, a composition for forming a friction material that can produce a friction material that can achieve both a low μ ratio after standing and suppression of rotor wear, a friction material obtained by molding the composition, and a friction material comprising the friction material A component and an automotive disc brake pad are provided.
以下、本開示を実施するための形態について詳細に説明する。但し、本開示は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本開示を制限するものではない。 Hereinafter, embodiments for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including elemental steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and they do not limit the present disclosure.
本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を１種のみ含んでいてもよく、複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率を意味する。
In the present disclosure, numerical ranges indicated using "~" include the numerical values written before and after "~" as minimum and maximum values, respectively.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In the present disclosure, each component may contain only one type of the relevant substance, or may contain multiple types of the relevant substance. When a plurality of substances corresponding to each component are present in the composition, the content of each component means the total content of the plurality of substances present in the composition, unless otherwise specified.
＜摩擦材形成用組成物＞
本開示の摩擦材形成用組成物は、チタン酸塩と、ポリテトラフルオロエチレンと、酸化ジルコニウムとを含み、銅を含まないか、あるいは、銅の含有率が元素基準にて０質量％を超えて０．５質量％以下であり、前記チタン酸塩の含有率が２０質量％以上３５質量％未満であり、前記ポリテトラフルオロエチレンの含有率が０．５質量％以上５質量％未満であり、前記酸化ジルコニウムの体積平均粒径が８．０μｍよりも大きい組成物である。本開示の摩擦材形成用組成物では、各成分の組成を調整することで低い放置後μ比及びローター摩耗の抑制を両立可能な摩擦材を作製可能である。
<Composition for forming friction material>
The composition for forming a friction material of the present disclosure includes a titanate, polytetrafluoroethylene, and zirconium oxide, and either does not contain copper or has a copper content of more than 0% by mass on an elemental basis. and the content of the titanate is 20% by mass or more and less than 35% by mass, and the content of the polytetrafluoroethylene is 0.5% by mass or more and less than 5% by mass. , a composition in which the volume average particle size of the zirconium oxide is larger than 8.0 μm. In the composition for forming a friction material of the present disclosure, by adjusting the composition of each component, it is possible to produce a friction material that can achieve both a low μ ratio after standing and suppression of rotor wear.
本開示の摩擦材形成用組成物は、チタン酸塩と、ポリテトラフルオロエチレン（ＰＴＦＥ）と、酸化ジルコニウムとを含み、必要に応じて他の成分を含んでいてもよい。以下、本開示の摩擦材形成用組成物に含まれ得る各成分について具体的に説明する。 The composition for forming a friction material of the present disclosure contains a titanate, polytetrafluoroethylene (PTFE), and zirconium oxide, and may contain other components as necessary. Each component that can be included in the composition for forming a friction material of the present disclosure will be specifically described below.
（チタン酸塩）
摩擦材形成用組成物に含まれるチタン酸塩としては、６チタン酸カリウム、８チタン酸カリウム、チタン酸リチウムカリウム、チタン酸マグネシウムカリウム等のチタン及びカリウムを含む塩が挙げられる。中でも、摩擦材のμレベルを高める観点から、６チタン酸カリウムを含むことが好ましい。
６チタン酸カリウムの含有率は、μレベルを所望の範囲に調整しやすい観点から、チタン酸塩全量に対して、５０質量％～１００質量％であってもよく、８０質量％～１００質量％であってもよい。
(titanate)
Examples of the titanate included in the composition for forming a friction material include salts containing titanium and potassium, such as potassium hexatitanate, potassium octitanate, potassium lithium titanate, and potassium magnesium titanate. Among these, from the viewpoint of increasing the μ level of the friction material, it is preferable to include potassium hexatitanate.
The content of potassium hexatitanate may be 50% by mass to 100% by mass, or 80% by mass to 100% by mass, based on the total amount of titanate, from the viewpoint of easily adjusting the μ level to a desired range. It may be.
チタン酸塩（好ましくは６チタン酸カリウム）の含有率は、摩擦材形成用組成物全量に対して、２０質量％以上３５質量％未満であり、放置後μ比をより低下させ、かつパッド摩耗を抑制する観点から、２３質量％以上３０質量％であってもよく、２５質量％～３０質量％であってもよい。 The content of the titanate (preferably potassium hexatitanate) is 20% by mass or more and less than 35% by mass based on the total amount of the friction material forming composition, which further reduces the μ ratio after standing and reduces pad wear. From the viewpoint of suppressing this, the content may be 23% by mass or more and 30% by mass, or may be 25% by mass to 30% by mass.
（ポリテトラフルオロエチレン（ＰＴＦＥ））
ポリテトラフルオロエチレンの体積平均粒径は、０．５μｍ～８．０μｍであってもよく、１．０μｍ～７．０μｍであってもよく、２．０μｍ～６．０μｍであってもよい。摩擦材形成用組成物に含まれるポリテトラフルオロエチレンは、一次粒子が凝縮した二次粒子の状態であってもよい。前述のポリテトラフルオロエチレンの体積平均粒径は、二次粒子の体積平均粒径であってもよい。
(Polytetrafluoroethylene (PTFE))
The volume average particle size of polytetrafluoroethylene may be 0.5 μm to 8.0 μm, 1.0 μm to 7.0 μm, or 2.0 μm to 6.0 μm. The polytetrafluoroethylene contained in the composition for forming a friction material may be in the form of secondary particles in which primary particles are condensed. The volume average particle size of the polytetrafluoroethylene mentioned above may be the volume average particle size of secondary particles.
ポリテトラフルオロエチレンの一次粒子の体積平均粒径は、１００ｎｍ～２００ｎｍであってもよく、１００ｎｍ～１５０ｎｍであってもよい。ポリテトラフルオロエチレンの一次粒径を小さくする観点から、直接重合法により製造されたポリテトラフルオロエチレンを用いることが好ましい。 The volume average particle size of the primary particles of polytetrafluoroethylene may be 100 nm to 200 nm, or 100 nm to 150 nm. From the viewpoint of reducing the primary particle size of polytetrafluoroethylene, it is preferable to use polytetrafluoroethylene produced by a direct polymerization method.
本開示において、粒子の体積平均粒径は、レーザー回折式粒度分布測定装置で測定される体積基準の粒度分布において、小径側からの積算が５０％となるときの値（メジアン径（Ｄ５０））を意味する。 In the present disclosure, the volume average particle diameter of particles is the value when the integration from the small diameter side is 50% (median diameter (D50)) in the volume-based particle size distribution measured by a laser diffraction particle size distribution measuring device. means.
ポリテトラフルオロエチレンの含有率は、摩擦材形成用組成物全量に対して、０．５質量％以上５質量％未満であり、低い放置後μ比及びローター摩耗の抑制の両立の観点から、０．７質量％以上３質量％以下であってもよく、０．８質量％以上２質量％以下であってもよい。 The content of polytetrafluoroethylene is 0.5% by mass or more and less than 5% by mass based on the total amount of the friction material forming composition, and from the viewpoint of achieving both a low μ ratio after standing and suppression of rotor wear, The content may be .7% by mass or more and 3% by mass or less, or 0.8% by mass or more and 2% by mass or less.
（酸化ジルコニウム）
酸化ジルコニウムの体積平均粒径は、８．０μｍよりも大きく、フェード時のトルク振動の抑制、低い放置後μ比及びローター摩耗の抑制の両立の観点から、８．０μｍ以上２０μｍ以下であってもよく、８．５μｍ以上１５μｍ以下であってもよく、９．０μｍ以上１３μｍ以下であってもよい。
(zirconium oxide)
The volume average particle diameter of zirconium oxide is larger than 8.0 μm, and even if it is 8.0 μm or more and 20 μm or less, from the viewpoint of suppressing torque vibration during fade, achieving a low μ ratio after standing, and suppressing rotor wear. It may be 8.5 μm or more and 15 μm or less, or 9.0 μm or more and 13 μm or less.
摩擦材形成用組成物に含まれる酸化ジルコニウムは、μレベルを所望の範囲に調整しやすい観点から、脱珪ジルコニアを含むことが好ましい。脱珪ジルコニアは、珪素濃度が低く、酸化ジルコニウムの純度が高いものであればよく、例えば、ＳｉＯ２量が粒子全体に対して、５質量％以下であることが好ましく、０．５質量％以下であることがより好ましい。 The zirconium oxide contained in the composition for forming a friction material preferably contains desiliconized zirconia from the viewpoint of easily adjusting the μ level to a desired range. The desiliconized zirconia may have a low silicon concentration and a high purity zirconium oxide. For example, the amount of SiO2 is preferably 5% by mass or less, and 0.5% by mass or less based on the entire particle. It is more preferable that
脱珪ジルコニアの含有率は、μレベルを所望の範囲に調整しやすい観点から、酸化ジルコニウム全量に対して、５０質量％～１００質量％であってもよく、８０質量％～１００質量％であってもよい。 The content of desiliconized zirconia may be 50% by mass to 100% by mass, or 80% by mass to 100% by mass, based on the total amount of zirconium oxide, from the viewpoint of easily adjusting the μ level to a desired range. You can.
摩擦材形成用組成物では、酸化ジルコニウムの含有率は、摩擦材形成用組成物全量に対して、１０質量％以上３０質量％以下であってもよく、１３質量％以上２５質量％以下であってもよく、１５質量％以上２３質量％以下であってもよい。 In the friction material forming composition, the content of zirconium oxide may be 10% by mass or more and 30% by mass or less, and 13% by mass or more and 25% by mass or less, based on the total amount of the friction material forming composition. It may be 15% by mass or more and 23% by mass or less.
（銅）
摩擦材形成用組成物は、銅を含まないか、あるいは、銅の含有率が元素基準にて０質量％を超えて０．５質量％以下である。これにより、摩擦材からの銅の流出を防止あるいは抑制することができる。
(copper)
The composition for forming a friction material does not contain copper, or has a copper content of more than 0% by mass and 0.5% by mass or less on an elemental basis. Thereby, the outflow of copper from the friction material can be prevented or suppressed.
（金属硫化物）
摩擦材形成用組成物は、金属硫化物を含まないことが好ましい。これにより、温度変化による金属酸化物の発生、金属酸化物による摩擦係数（μ）の変動等を抑制でき、さらに、メタルピックアップと呼ばれるブレーキパッド表面における鉄成分の発生、ローター摩耗の増大等の使用中の特性変化を抑制できる。
(metal sulfide)
The composition for forming a friction material preferably does not contain metal sulfides. This can suppress the generation of metal oxides due to temperature changes and fluctuations in the coefficient of friction (μ) due to metal oxides, and can also suppress the generation of iron components on the brake pad surface called metal pickup and increase rotor wear. Changes in characteristics inside can be suppressed.
（特定の金属粉末）
摩擦材形成用組成物は、鉄に対して犠牲防食作用を有する金属粉末（以下、特定の金属粉末とも称する。）をさらに含むことが好ましい。これにより、摩擦材のさび抑制が可能となる。特定の金属粉末は、鉄よりもイオン化傾向が高い金属の粉末であることが好ましい。特定の金属粉末の具体例としては、亜鉛粉末が好ましい。
(Specific metal powder)
It is preferable that the composition for forming a friction material further contains a metal powder (hereinafter also referred to as a specific metal powder) having a sacrificial anticorrosion effect on iron. This makes it possible to suppress rust on the friction material. Preferably, the particular metal powder is a powder of a metal that has a higher ionization tendency than iron. As a specific example of the specific metal powder, zinc powder is preferred.
（他の成分）
摩擦材形成用組成物は、本発明の効果を奏する範囲において、他の成分を含んでいてもよい。他の成分としては、結合材、結着材等の樹脂、摩擦調整材、研削材、繊維基材、ｐＨ調整剤、充填材などが挙げられる。
(other ingredients)
The composition for forming a friction material may contain other components as long as the effects of the present invention are achieved. Other components include binders, resins such as binders, friction modifiers, abrasives, fiber base materials, pH adjusters, fillers, and the like.
結合材、結着材等の樹脂としては、ストレートフェノール樹脂、カシューオイル変性フェノール樹脂、アクリルゴム変性フェノール樹脂、シリコーンゴム変性フェノール樹脂、ニトリルゴム（ＮＢＲ）変性フェノール樹脂、フェノール・アラルキル樹脂、フルオロポリマー分散フェノール樹脂、シリコーンゴム分散フェノール樹脂等が挙げられる。 Resins such as binding materials and binding materials include straight phenolic resin, cashew oil modified phenolic resin, acrylic rubber modified phenolic resin, silicone rubber modified phenolic resin, nitrile rubber (NBR) modified phenolic resin, phenol/aralkyl resin, and fluoropolymer. Examples include dispersed phenolic resin, silicone rubber dispersed phenolic resin, and the like.
摩擦材形成用組成物では、樹脂の含有率は、摩擦材形成用組成物全量に対して、５質量％～２０質量％であってもよく、６質量％～１５質量％であってもよく、８質量％～１２質量％であってもよい。 In the composition for forming a friction material, the content of the resin may be 5% by mass to 20% by mass, or 6% by mass to 15% by mass, based on the total amount of the composition for forming a friction material. , 8% to 12% by mass.
摩擦調整材、研削材等（但し、チタン酸塩、ポリテトラフルオロエチレン（ＰＴＦＥ）、及び酸化ジルコニウムを除く）としては、タイヤトレッドゴム、ニトリルゴム、アクリルゴム、シリコーンゴム、ブチルゴム等のゴム、フリクションダスト、黒鉛、バーミキュライト、金雲母、白雲母、四三酸化鉄、ケイ酸カルシウム、酸化マグネシウム、ケイ酸ジルコニウム、ジルコン、γアルミナ、αアルミナ、炭化ケイ素、ウォラストナイト、セピオライト等が挙げられる。 Friction modifiers, abrasives, etc. (excluding titanate, polytetrafluoroethylene (PTFE), and zirconium oxide) include tire tread rubber, nitrile rubber, acrylic rubber, silicone rubber, butyl rubber, and other rubbers, friction Examples include dust, graphite, vermiculite, phlogopite, muscovite, triiron tetroxide, calcium silicate, magnesium oxide, zirconium silicate, zircon, γ alumina, α alumina, silicon carbide, wollastonite, sepiolite, and the like.
摩擦材形成用組成物では、摩擦調整材及び研削材（但し、チタン酸塩、ポリテトラフルオロエチレン（ＰＴＦＥ）、及び酸化ジルコニウムを除く）の合計含有率は、摩擦材形成用組成物全量に対して、１０質量％～５０質量％であってもよく、１５質量％～４０質量％であってもよく、２０質量％～３５質量％であってもよい。 In the composition for forming a friction material, the total content of friction modifiers and abrasives (excluding titanate, polytetrafluoroethylene (PTFE), and zirconium oxide) is based on the total amount of the composition for forming a friction material. The content may be 10% by mass to 50% by mass, 15% by mass to 40% by mass, or 20% by mass to 35% by mass.
繊維基材としては、バサルト繊維、ガラス繊維、アラミド繊維、セルロース繊維、ポリパラフェニレンベンゾビスオキサゾール繊維、アクリル繊維、ロックウール等が挙げられる。 Examples of the fiber base material include basalt fiber, glass fiber, aramid fiber, cellulose fiber, polyparaphenylenebenzobisoxazole fiber, acrylic fiber, and rock wool.
摩擦材形成用組成物では、繊維基材の含有率は、摩擦材形成用組成物全量に対して、５質量％～２０質量％であってもよく、６質量％～１５質量％であってもよく、８質量％～１２質量％であってもよい。 In the composition for forming a friction material, the content of the fiber base material may be 5% by mass to 20% by mass, or 6% to 15% by mass, based on the total amount of the composition for forming a friction material. It may be 8% by mass to 12% by mass.
ｐＨ調整剤としては、水酸化カルシウム、水酸化マグネシウム等が挙げられる。 Examples of the pH adjuster include calcium hydroxide, magnesium hydroxide, and the like.
摩擦材形成用組成物では、ｐＨ調整剤の含有率は、摩擦材形成用組成物全量に対して、１質量％～１０質量％であってもよく、２質量％～８質量％であってもよく、３質量％～６質量％であってもよい。 In the composition for forming a friction material, the content of the pH adjuster may be 1% by mass to 10% by mass, or 2% to 8% by mass, based on the total amount of the composition for forming a friction material. It may be 3% by mass to 6% by mass.
充填材としては、硫酸バリウム、硫酸カルシウム、炭酸カルシウム等が挙げられる。 Examples of the filler include barium sulfate, calcium sulfate, calcium carbonate, and the like.
摩擦材形成用組成物では、充填材の含有率は、摩擦材形成用組成物全量に対して、５質量％～２０質量％であってもよく、６質量％～１５質量％であってもよく、８質量％～１２質量％であってもよい。 In the composition for forming a friction material, the content of the filler may be from 5% by mass to 20% by mass, or from 6% by mass to 15% by mass, based on the total amount of the composition for forming a friction material. It may be 8% to 12% by weight.
＜摩擦材＞
本開示の摩擦材は、前述の本開示の摩擦材形成用組成物を成形して得られる。摩擦材は、摩擦材形成用組成物を従来公知の方法で成形することで得られる。例えば、チタン酸塩と、ポリテトラフルオロエチレンと、酸化ジルコニウムと、必要に応じて前述のその他の成分と、を混合して摩擦材形成用組成物を調製し、調製した摩擦材形成用組成物を加熱成形することで摩擦材を作製できる。摩擦材形成用組成物の調製に結合材、結着材等の樹脂を用いる場合には、結合材、結着材等の樹脂を熱硬化させてもよい。
<Friction material>
The friction material of the present disclosure is obtained by molding the aforementioned composition for forming a friction material of the present disclosure. The friction material can be obtained by molding a composition for forming a friction material by a conventionally known method. For example, a composition for forming a friction material is prepared by mixing titanate, polytetrafluoroethylene, zirconium oxide, and other components mentioned above as necessary. A friction material can be produced by heating and molding. When a binder, a binder, or other resin is used to prepare a composition for forming a friction material, the binder, binder, or other resin may be thermally cured.
摩擦材形成用組成物を加熱成形する際、他の部材（例えば、後述の裏金）とともに摩擦材形成用組成物を加熱成形してもよい。摩擦材形成用組成物を加熱成形して摩擦材を作製した後に、必要に応じて摩擦材の表面を研磨してもよい。 When heat-molding the friction material-forming composition, the friction material-forming composition may be heat-molded together with other members (for example, a back metal as described below). After the friction material is produced by heat-molding the composition for forming a friction material, the surface of the friction material may be polished if necessary.
＜摩擦材の用途＞
本開示の摩擦材の用途としては、摩擦部材、自動車用ディスクブレーキパッド等が挙げられる。摩擦部材は、本開示の摩擦材と、裏金とを備える構成が挙げられる。摩擦材形成用組成物を用いて摩擦部材、自動車用ディスクブレーキパッド等を作製する方法としては、従来公知の方法が挙げられる。
<Uses of friction materials>
Applications of the friction material of the present disclosure include friction members, automobile disc brake pads, and the like. The friction member may have a configuration including the friction material of the present disclosure and a back metal. Conventionally known methods can be used for producing friction members, automobile disc brake pads, etc. using the composition for forming a friction material.
以下、上記実施形態を実施例により具体的に説明するが、上記実施形態はこれらの実施例に限定されるものではない。 Hereinafter, the above-mentioned embodiment will be specifically explained using examples, but the above-mentioned embodiment is not limited to these examples.
［ディスクブレーキパッドの作製］
＜実施例１～３及び比較例１～７＞
表１に示す配合比率（質量％）に従って各材料を配合し、各摩擦材形成用組成物を得た。表１中の空欄は、未配合を意味する。なお、樹脂、酸化ジルコニウム、チタン酸塩及びＰＴＦＥとしては以下の成分を用いた。
－各材料－
・樹脂（シリコーンゴム変性フェノール樹脂）
・酸化ジルコニウム１（体積平均粒径３．４μｍの脱珪ジルコニア）
・酸化ジルコニウム２（体積平均粒径６．１μｍの脱珪ジルコニア）
・酸化ジルコニウム３（体積平均粒径８．２μｍの脱珪ジルコニア）
・酸化ジルコニウム４（体積平均粒径１０．２μｍの脱珪ジルコニア）
・酸化ジルコニウム５（体積平均粒径１２．２μｍの脱珪ジルコニア）
・チタン酸塩（６チタン酸カリウム）
・ＰＴＦＥ（体積平均粒径（二次粒子）４．０μｍ±２．０μｍ）
[Production of disc brake pad]
<Examples 1 to 3 and Comparative Examples 1 to 7>
Each material was blended according to the blending ratio (mass %) shown in Table 1 to obtain each composition for forming a friction material. A blank column in Table 1 means that it is not blended. Note that the following components were used as the resin, zirconium oxide, titanate, and PTFE.
-Each material-
・Resin (silicone rubber modified phenolic resin)
・Zirconium oxide 1 (desiliconized zirconia with a volume average particle size of 3.4 μm)
・Zirconium oxide 2 (desiliconized zirconia with a volume average particle size of 6.1 μm)
・Zirconium oxide 3 (desiliconized zirconia with a volume average particle size of 8.2 μm)
・Zirconium oxide 4 (desiliconized zirconia with a volume average particle diameter of 10.2 μm)
・Zirconium oxide 5 (desiliconized zirconia with a volume average particle size of 12.2 μm)
・Titanate (potassium hexatitanate)
・PTFE (volume average particle diameter (secondary particles) 4.0 μm ± 2.0 μm)
摩擦材形成用組成物をレーディゲミキサー（株式会社マツボー製、商品名：レーディゲ（登録商標）ミキサーＭ２０）で撹拌混合し、得られた混合物を、成形プレス（株式会社テクノマルシチ製）を用いて鉄製の裏金（厚さ６ｍｍ）と共に加熱加圧成形した。得られた成形品を、２００℃で３．５時間熱処理し、ロータリー研磨機を用いて研磨した。次いで、成形品に対して５００℃で３分間のスコーチ処理を行い、厚さ１０ｍｍ、投影面積６０ｃｍ２の摩擦材を備えるディスクブレーキパッドを作製した。 The friction material forming composition was stirred and mixed with a Loedige mixer (manufactured by Matsubo Co., Ltd., product name: Loedige (registered trademark) mixer M20), and the resulting mixture was mixed using a molding press (manufactured by Techno Marushichi Co., Ltd.). Then, it was molded under heat and pressure together with an iron backing metal (thickness: 6 mm). The obtained molded article was heat treated at 200° C. for 3.5 hours and polished using a rotary polisher. Next, the molded product was subjected to a scorch treatment at 500° C. for 3 minutes to produce a disc brake pad with a friction material having a thickness of 10 mm and a projected area of 60 cm 2 .
（放置後μ比、フェード時トルク振動、パッド摩耗及びローター摩耗）
各実施例及び各比較例にて作製したディスクブレーキパッドを用い、表２の試験条件に準拠して実施した試験によって放置後μ比、フェード時トルク振動、パッド摩耗及びローター摩耗を求めた。放置後μ比は、Ｎｏ．６及びＮｏ．９の１制動目平均μ比（［Ｎｏ．９でのμ（放置後μ ２回目 ０．５ＭＰａ５ｋｍ／ｈ）／Ｎｏ．６でのμ（放置後μ １回目 ０．５ＭＰａ５ｋｍ／ｈ）］×１００）より算出した。フェード時トルク振動は、Ｎｏ．１４及びＮｏ．１８における１制動中トルク変動の最大値をフェード時トルク振動とした。パッド摩耗は試験前と試験後のブレーキパッドの厚み差より算出し、ローター摩耗は試験前と試験後のローターの厚み差より算出した。
表２中の初速度の単位はｋｍ／ｈ、減速度の単位はｍ／ｓ２、液圧の単位はＭＰａである。
(μ ratio after storage, torque vibration during fade, pad wear and rotor wear)
Using the disc brake pads produced in each example and each comparative example, the μ ratio after standing, torque vibration during fade, pad wear, and rotor wear were determined by tests conducted in accordance with the test conditions shown in Table 2. The μ ratio after standing was No. 6 and no. 9's first braking average μ ratio ([μ at No. 9 (μ after leaving for the second time 0.5 MPa 5 km/h) / μ at No. 6 (μ after leaving for the first time 0.5 MPa 5 km/h)] × 100 ). Torque vibration during fade is No. 14 and no. The maximum value of the torque fluctuation during one braking in No. 18 was taken as the torque vibration during fade. Pad wear was calculated from the difference in brake pad thickness before and after the test, and rotor wear was calculated from the difference in rotor thickness before and after the test.
In Table 2, the unit of initial velocity is km/h, the unit of deceleration is m/s 2 , and the unit of hydraulic pressure is MPa.
放置後μ比、フェード時トルク振動、パッド摩耗及びローター摩耗の結果を表１に示す。これらの各項目の評価基準は以下の通りである。それぞれの項目について評価Ｂ以上であれば、結果は良好である。
－放置後μ比の評価基準－
Ａ：１２０％未満
Ｂ：１２０％以上１３０％未満
Ｃ：１３０％以上
－フェード時トルク振動の評価基準－
Ａ：４００Ｎｍ未満
Ｂ：４００Ｎｍ以上６００Ｎｍ未満
Ｃ：６００Ｎｍ以上
－パッド摩耗の評価基準－
Ａ：２．２０ｍｍ未満
Ｂ：２．２０ｍｍ以上２．８０ｍｍ未満
Ｃ：２．８０ｍｍ以上
－ローター摩耗の評価基準－
Ａ：０．０２０未満
Ｂ：０．０２０以上０．０２５未満
Ｃ：０．０２５以上
Table 1 shows the results of μ ratio after standing, torque vibration during fade, pad wear, and rotor wear. The evaluation criteria for each of these items are as follows. If each item is evaluated as B or higher, the result is good.
-Evaluation criteria for μ ratio after standing-
A: Less than 120% B: 120% or more and less than 130% C: 130% or more - Evaluation criteria for torque vibration during fade -
A: Less than 400Nm B: 400Nm or more and less than 600Nm C: 600Nm or more - Evaluation criteria for pad wear -
A: Less than 2.20 mm B: 2.20 mm or more and less than 2.80 mm C: 2.80 mm or more - Evaluation criteria for rotor wear -
A: Less than 0.020 B: 0.020 or more and less than 0.025 C: 0.025 or more
表１に示すように、各実施例では、放置後μ比、フェード時トルク振動、パッド摩耗及びローター摩耗の評価結果がいずれもＢ以上であった。
一方、各比較例では、放置後μ比、フェード時トルク振動、パッド摩耗及びローター摩耗の評価結果の少なくともいずれか１つがＣであった。より詳細には、各比較例では、放置後μ比及びローター摩耗の評価結果の少なくとも一方がＣであった。
As shown in Table 1, in each Example, the evaluation results of μ ratio after standing, torque vibration during fade, pad wear, and rotor wear were all B or higher.
On the other hand, in each comparative example, at least one of the evaluation results of μ ratio after standing, torque vibration during fade, pad wear, and rotor wear was C. More specifically, in each comparative example, at least one of the evaluation results of μ ratio and rotor wear after standing was C.
Claims (8)
銅を含まないか、あるいは、銅の含有率が元素基準にて０質量％を超えて０．５質量％以下であり、
前記チタン酸塩の含有率が２０質量％以上３５質量％未満であり、
前記ポリテトラフルオロエチレンの含有率が０．５質量％以上５質量％未満であり、
前記酸化ジルコニウムの体積平均粒径が８．０μｍよりも大きい摩擦材形成用組成物。 Contains titanate, polytetrafluoroethylene, and zirconium oxide,
Does not contain copper, or has a copper content of more than 0% by mass and 0.5% by mass or less on an elemental basis,
The content of the titanate is 20% by mass or more and less than 35% by mass,
The content of the polytetrafluoroethylene is 0.5% by mass or more and less than 5% by mass,
A composition for forming a friction material, wherein the volume average particle size of the zirconium oxide is larger than 8.0 μm.
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