WO2023013396A1 - Composition de matériau de frottement, matériau de frottement et élément de frottement - Google Patents

Composition de matériau de frottement, matériau de frottement et élément de frottement Download PDF

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WO2023013396A1
WO2023013396A1 PCT/JP2022/028011 JP2022028011W WO2023013396A1 WO 2023013396 A1 WO2023013396 A1 WO 2023013396A1 JP 2022028011 W JP2022028011 W JP 2022028011W WO 2023013396 A1 WO2023013396 A1 WO 2023013396A1
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mass
friction material
material composition
titanate
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PCT/JP2022/028011
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Japanese (ja)
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恵美子 大門
靖仁 伊東
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大塚化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • 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—Composition of linings ; Methods of manufacturing

Definitions

  • the present invention relates to a friction material composition, and a friction material and a friction member using the friction material composition.
  • Friction materials used in brakes such as disc brakes and drum brakes that constitute braking devices for various vehicles and industrial machines must have a large and stable coefficient of friction, excellent wear resistance, and aggressiveness to mating materials. is required to be low.
  • Such a friction material includes a semi-metallic material containing steel fibers such as steel fibers and stainless steel fibers as a fiber base material at a rate of 30% by mass or more and less than 60% by mass; It is classified into three types: low steel materials containing less than mass %; and NAO (Non-Asbestos-Organic) materials containing no steel fibers. However, friction materials containing a small amount of steel fibers are also classified as NAO materials.
  • NAO material which has low aggressiveness to mating materials and excellent balance between squeal and wear resistance, is the mainstream.
  • Compositions used for friction materials generally contain copper fibers and copper powder.
  • a primary role of copper is to provide thermal conductivity. Copper has a high thermal conductivity, so by diffusing the heat generated during braking from the friction surface, it is possible to reduce wear of the friction material due to excessive temperature rise and suppress vibration during braking.
  • a second role of copper is to protect friction surfaces during high temperature braking. Due to the ductility of copper, it extends to form a coating on the friction material surface during braking. It also transfers to the surface of the mating material to form an adhesive film (hereinafter referred to as "transfer film”).
  • friction materials containing copper contain copper in the wear powder generated during braking, and it has been suggested that it may cause pollution of rivers, lakes, and oceans. From 2021 onwards, state laws will be enforced prohibiting the sale and installation of friction materials containing 5% by mass or more of copper in new vehicles, and from 2025 onwards, those containing 0.5% by mass or more of copper.
  • titanates such as potassium titanate, lithium potassium titanate, and magnesium potassium titanate are attracting attention as components other than copper that bear the transfer film.
  • a friction material composition containing lithium potassium titanate and graphite Patent Document 1
  • a friction material composition containing two or more titanates and ceramic fibers Patent Document 2
  • a tunnel crystal structure Patent Document 3
  • a titanate having a layered crystal structure Patent Document 3
  • low steel materials have a large coefficient of friction and good stability in effectiveness, but they are highly aggressive to the mating material, and the friction material and rotor (mating material) wear dust on the wheel (wheel) becomes a problem. ing. Therefore, it is required not only to reduce the content of the copper component in the friction material, but also to reduce the amount of abrasion dust during braking.
  • As a method for reducing abrasion dust it is conceivable to reduce the load on the friction brake.
  • the popularization of regenerative cooperative braking by EV (electric vehicle) and hybrid vehicles is being promoted.
  • EV vehicles are heavier than gasoline vehicles, and regenerative cooperative braking does not have a uniform level of regeneration depending on the vehicle type and driving conditions, so the effect of reducing abrasion dust is not sufficient.
  • brake emissions are scheduled to be regulated after 2025.
  • AGVES Advisory Group on Vehicle Emission Standards
  • PM particles substance 10
  • regulation values for PM2.5 and PN are also being discussed, and the particle size of abrasion dust is also emphasized.
  • the present invention has been made in view of the above circumstances. 10 ⁇ m or less particulate matter), PM2.5 (particulate matter with an aerodynamic diameter of 2.5 ⁇ m or less), etc.
  • a friction material composition that can form a low steel material that generates a small amount of fine abrasion dust.
  • An object of the present invention is to provide a product, and a friction material and a friction member using the friction material composition.
  • the present invention provides the following friction material composition, and a friction material and a friction member using the friction material composition.
  • Item 1 A friction material composition having a copper component content of less than 0.5% by mass as a copper element, containing a binder, steel fibers, and a titanate, wherein the content of the steel fibers is A friction material composition that is 10% by mass or more and less than 30% by mass with respect to 100% by mass of the total amount of the friction material composition.
  • Item 2 The friction material composition according to Item 1, wherein the content of the titanate is 5% by mass or more and 30% by mass or less with respect to 100% by mass of the total amount of the friction material composition.
  • Item 3 The friction material composition according to Item 1 or 2, wherein the mass ratio of the titanate to the steel fiber (titanate/steel fiber) is 0.1 or more and 3.0 or less.
  • Item 4 The friction material according to any one of Items 1 to 3, wherein the mass ratio of the titanate to the binder (titanate/binder) is 0.4 or more and 8.0 or less. Composition.
  • Item 5 The friction material composition according to any one of Items 1 to 4, wherein the titanate is at least one of a titanate having a tunnel crystal structure and a titanate having a layered crystal structure.
  • the titanate is A x M y Ti (2-y) O 4 [wherein A is one or more alkali metals excluding Li, M is Li, Mg, Zn, Ga, Ni , Cu, Fe, Al, one or more selected from Mn, x is 0.5 to 1.0, y is a number of 0.25 to 1.0], A 0.1 to 0.8 Li 0.2-0.4 Ti 1.6-1.8 O 3.65-3.95 [wherein A is one or more alkali metals excluding Li], A 0.2-0.
  • Item 7 The friction material composition according to any one of Items 1 to 6, wherein the alkali metal ion elution rate of the titanate is 0.01% by mass or more and 15% by mass or less.
  • the titanate is at least one non-fibrous particle selected from the group consisting of spherical particles, columnar particles, plate-like particles, block particles, particles having a plurality of convex shapes, and irregularly shaped particles. , the friction material composition according to any one of items 1 to 7.
  • Item 9 The friction material composition according to any one of Items 1 to 8, wherein the titanate has an average particle size of 0.1 ⁇ m or more and 200 ⁇ m or less.
  • Item 10 The friction material composition according to any one of Items 1 to 9, wherein the steel-based fibers have an average fiber length of 0.1 mm or more and 5 mm or less.
  • Item 11 The friction material composition according to any one of Items 1 to 10, wherein the steel-based fibers are curled fibers.
  • Item 12 The friction material composition according to any one of Items 1 to 11, wherein the content of the carbon-based solid lubricant is less than 10% by mass with respect to the total amount of 100% by mass of the friction material composition. thing.
  • Item 13 A friction material that is a molded body of the friction material composition according to any one of Items 1 to 12.
  • Item 14 A friction member comprising the friction material according to Item 13.
  • a friction material composition capable of forming a low steel material, and a friction material and a friction member using the friction material composition can be provided.
  • FIG. 1 is a photograph showing a cross section of the friction member obtained in Example 1 after the friction test.
  • FIG. 2 is a photograph showing a cross section of a friction member made of NAO material after a friction test.
  • Friction Material Composition has a copper component content of less than 0.5% by mass as a copper element with respect to the total amount of 100% by mass of the friction material composition, and It contains an acid salt, and the content of steel fibers is 10% by mass or more and less than 30% by mass with respect to 100% by mass of the total amount of the friction material composition. Moreover, the friction material composition of the present invention may further contain other materials as necessary. In this specification, the term “friction material composition” refers to a composition used for a friction material.
  • the content of the copper component is less than 0.5% by mass as a copper element with respect to the total amount of 100% by mass of the friction material composition, and preferably the copper component is not contained, so that the conventional friction material composition environmental load can be reduced compared to
  • "does not contain a copper component” means that any of copper fiber, copper powder, and copper-containing alloys (brass, bronze, etc.) and compounds are blended as raw materials of the friction material composition. It means that you have not.
  • the friction material composition of the present invention has the above configuration, it is possible to form a low steel material that generates a small amount of fine abrasion dust such as PM10 and PM2.5 during braking. This point will be described below with reference to FIGS. 1 and 2.
  • FIG. 1 shows a low steel material that generates a small amount of fine abrasion dust such as PM10 and PM2.5 during braking.
  • titanate is known as a component other than copper that plays a role in the transfer film.
  • a coating such as that shown in FIG. 2 is formed, which migrates to the mating material to form a transfer film.
  • conventional low steel materials are difficult to form a film, and the iron of the rotor and the iron of the steel fibers are fused due to friction, and the steel fibers are easily separated from the pad. As a result, unevenness is formed on the friction surface, which accelerates wear and increases the amount of dust.
  • the amount of minute abrasion dust such as PM10 and PM2.5 generated during braking can be reduced.
  • the amount of copper in the abrasion powder generated during braking is less, so the environmental load can be reduced.
  • FIG. 1 is a photograph showing a cross section of the friction member obtained in Example 1, which will be described later, after the friction test.
  • FIG. 2 is a photograph showing a cross section of a friction member made of NAO material after a friction test.
  • the binder unites the steel fibers, titanate, etc. contained in the friction material composition to provide strength.
  • the binder used in the friction material composition of the present invention is not particularly limited, and thermosetting resins commonly used as binders for friction materials can be used.
  • Thermosetting resins include, for example, phenolic resins; elastomer-dispersed phenolic resins such as acrylic elastomer-dispersed phenolic resins and silicone elastomer-dispersed phenolic resins; acrylic-modified phenolic resins, silicone-modified phenolic resins, cashew-modified phenolic resins, epoxy-modified phenolic resins, Modified phenol resins such as alkylbenzene-modified phenol resins; formaldehyde resins; melamine resins; epoxy resins; acrylic resins; aromatic polyester resins; One of these may be used alone, or two or more may be used in combination. Among these, phenolic resins (straight phenolic resins) and modified phenolic resins are preferred because they can further improve heat resistance, moldability, and frictional properties.
  • the content of the binder in the friction material composition is preferably 5% by mass or more, more preferably 6% by mass or more, and preferably 20% by mass or less with respect to 100% by mass of the total amount of the friction material composition. More preferably, it is 15% by mass or less.
  • steel fibers examples include steel fibers and stainless steel fibers, with steel fibers being preferred.
  • steel fibers examples include straight fibers obtained by chatter vibration cutting and curled fibers obtained by cutting long fibers.
  • a straight fiber is a linear fiber shape.
  • a curled fiber indicates a shape having a curved portion, and includes a simple circular arc shape, an undulating shape, a helically or spirally curved shape, and the like.
  • the steel fibers are preferably curled fibers from the viewpoint of less falling off from the friction material on the friction surface and more reliable retention of friction characteristics during high-temperature braking. Furthermore, it is more preferable that the curled fibers include a portion having a radius of curvature of 100 ⁇ m or less. In this case, the adhesion to the friction material becomes stronger, and the falling off of the friction material from the friction surface is further reduced.
  • the average fiber length of steel fibers is preferably 5 mm or less, more preferably 2.5 mm or less.
  • the thickness is preferably 0.1 mm or more, more preferably 0.5 mm or more, and still more preferably 1.1 mm or more. Taking these into consideration, the average fiber length of the steel-based fibers is preferably 0.1 mm to 5 mm, more preferably 0.5 mm to 2.5 mm, even more preferably 1.1 mm to 2.5 mm.
  • the average fiber diameter of the steel-based fibers is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, from the viewpoint of further suppressing brake vibration at high temperatures.
  • the thickness is preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more. Considering these, the average fiber diameter of the steel-based fiber is preferably 10 ⁇ m to 300 ⁇ m, more preferably 30 ⁇ m to 100 ⁇ m.
  • the average fiber length and average fiber diameter of steel fibers can be confirmed with a microscope. For example, it can be the average value of 30 steel fibers observed with a microscope.
  • the content of the steel-based fiber is 10% by mass or more, preferably 12% by mass or more, more preferably 15% by mass or more, and less than 30% by mass, preferably less than 30% by mass, with respect to 100% by mass of the total amount of the friction material composition is 28% by mass or less, more preferably 25% by mass or less.
  • a titanate has a crystal structure such as a tunnel structure and a layered structure, and at least one of a titanate with a tunnel crystal structure and a titanate with a layered crystal structure is preferable. From the viewpoint of further reducing abrasion dust, titanates having a layered crystal structure are preferred. From the viewpoint of further increasing the coefficient of friction, a titanate having a tunnel crystal structure is preferable. Therefore, a titanate having a tunnel crystal structure and a titanate having a layered crystal structure may be used in combination.
  • the titanate is preferably magnesium potassium titanate or lithium potassium titanate from the viewpoint of further reducing wear dust, and from the viewpoint of further increasing the coefficient of friction and further reducing wear dust, Magnesium potassium titanate with a layered crystal structure is more preferred.
  • Examples of the titanate having a layered crystal structure include A x M y Ti (2-y) O 4 [wherein A is one or more alkali metals excluding lithium (Li), M is Li, one or more selected from Mg, Zn, Ga, Ni, Cu, Fe, Al, and Mn, x is 0.5 to 1.0, y is a number of 0.25 to 1.0], A 0 .1 to 0.8 Li 0.2 to 0.4 Ti 1.6 to 1.8 O 3.65 to 3.95 [wherein A is one or more alkali metals excluding Li], A 0.2-0.8 Mg 0.3-0.5 Ti 1.5-1.7 O 3.7-3.95 [In the formula, A is one or more alkali metals excluding Li ], A 0.5-0.7 Li (0.27-x) M y Ti (1.73-z) O 3.85-3.95 [wherein A is an alkali metal other than Li or two or more, and M is one or two or more selected from Mg, Zn, Ga, Ni, Cu, Fe, Al,
  • a x M y Ti (2-y) O 4 [wherein A is one or more alkali metals excluding Li, M is Li, Mg, Zn, Ga, Ni, Cu, Fe, Al , Mn, x is 0.5 to 1.0, and y is a number of 0.25 to 1.0], A 0.5 to 0.7 Li 0.27 Ti 1. 73 O 3.85-3.95 [wherein A is one or more alkali metals excluding Li], and A 0.2-0.7 Mg 0.40 Ti 1.6 O 3.7 ⁇ 3.95 [In the formula, A is one or more alkali metals excluding Li].
  • alkali metals other than lithium (Li) include sodium, potassium, rubidium, cesium, and francium. Among them, sodium and potassium are preferable because they are economically advantageous.
  • titanates having a layered crystal structure include K 0.8 Li 0.27 Ti 1.73 O 4 (potassium lithium titanate) and K 0.7 Li 0.27 Ti 1.73 O 3.95. (potassium lithium titanate), K 0.6 Li 0.27 Ti 1.73 O 3.9 (potassium lithium titanate), K 0.4 Li 0.27 Ti 1.73 O 3.8 (lithium titanate potassium ) , K0.3Li0.27Ti1.73O3.7 (potassium lithium titanate) , K0.8Mg0.4Ti1.6O4 ( potassium magnesium titanate) , K0 .
  • titanates having a tunnel crystal structure examples include A 2 Ti n O (2n+1) [wherein A is one or more alkali metals excluding Li, n is a number from 2 to 11], A (2+y) Ti (6-x) M x O (13+y/2-(4-z)x/2) [Wherein, A is one or more alkali metals excluding Li, M is Li, Mg , one or more selected from Zn, Ga, Ni, Cu, Fe, Al, and Mn, z is the valence of the element M and an integer of 1 to 3, x is 0.05 ⁇ x ⁇ 0.5, y is 0 ⁇ y ⁇ (4 ⁇ z)x] and the like, preferably A 2 Ti n O (2n+1) [wherein A is one or more alkali metals excluding Li, n is 2 to 11], more preferably A 2 Ti n O (2n+1) [wherein A is one or more alkali metals excluding Li, and n is a number from 4 to 9], more preferably is at
  • titanates having a tunnel crystal structure include K 2 Ti 4.8 O 10.6 (potassium 4.8 titanate), K 2 Ti 6 O 13 (potassium 6 titanate), and K 2 Ti 6 .1 O 13.2 (6.1 potassium titanate), K 2 Ti 7.9 O 16.8 (7.9 potassium titanate), K 2 Ti 8 O 17 (8 potassium titanate), K 2 Ti 10.9O22.8 ( 10.9 potassium titanate) , Na2Ti6O13 (6 sodium titanate), Na2Ti8O17 ( 8 sodium titanate ) , K2.15 Ti5.85 Al 0.15 O 13.0 (potassium aluminum titanate), K 2.20 Ti 5.60 Al 0.40 O 12.9 (potassium aluminum titanate), K 2.20 Ti 5.90 Li 0.10 O 12.9 (lithium potassium titanate) and the like can be mentioned.
  • the titanate is preferably non-fibrous particles from the viewpoint of working environment.
  • the non-fibrous particles include, for example, spherical particles (including particles having slightly uneven surfaces and particles having a substantially spherical shape such as an elliptical cross section), columnar particles (rod-like, columnar, prismatic, strip-like, (Including those whose overall shape is almost columnar, such as a substantially cylindrical shape, a substantially rectangular shape, etc.), plate-like, block-like, shape with multiple protrusions (ameba-like, boomerang-like, cross-like, confetti-like, etc.), indeterminate Particle shapes such as shape can be mentioned, and these can also be used in combination.
  • tabular particles are preferred.
  • the titanate may be porous particles. These various particle shapes can be arbitrarily controlled by production conditions, particularly raw material composition, firing conditions, and the like. Also, the particle shape can be analyzed, for example, by scanning electron microscope (SEM) observation.
  • SEM scanning electron microscope
  • non-fibrous particles refers to a rectangular parallelepiped having the smallest volume among the rectangular parallelepipeds circumscribing the particle (circumscribing rectangular parallelepiped). is the thickness T (where B>T), and L/B is 5 or less.
  • “having a plurality of protrusions” means that the projected shape on a plane can take a shape having protrusions in at least two directions, unlike ordinary polygons, circles, ellipses, and the like. Specifically, this convex portion is a portion corresponding to a portion protruding from a polygon, circle, ellipse, etc. (basic figure) applied to a photograph (projection view) taken by a scanning electron microscope (SEM). say.
  • the average particle size of the titanate is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 80 ⁇ m or less, and particularly preferably 35 ⁇ m or less. . When the average particle size is within the above range, the amount of abrasion dust generated can be further reduced.
  • the average particle size refers to the particle size ( D50 ) at 50% volume-based accumulation in the particle size distribution measured by the laser diffraction method.
  • This D50 is the particle diameter at the point where the particle size distribution is obtained on a volume basis, the number of particles is counted from the smallest particle size on the cumulative curve with the total volume as 100%, and the cumulative value becomes 50%. be.
  • the specific surface area of the titanate is preferably 0.1 m 2 /g or more, more preferably 0.2 m 2 /g or more, still more preferably 0.5 m 2 /g or more, preferably 10 m 2 /g or less, It is more preferably 8 m 2 /g or less, still more preferably 6 m 2 /g or less, and particularly preferably 5 m 2 /g or less.
  • the specific surface area can be measured according to JIS Z8830.
  • the alkali metal ion elution rate of the titanate is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 15% by mass. % or less, more preferably 10 mass % or less, still more preferably 6 mass % or less, and particularly preferably 4 mass % or less.
  • hexamethylenetetramine as a curing accelerator is ring-opened to bond with hydroxyl groups in the novolac-type phenolic resin to cure.
  • a reaction is initiated.
  • alkali metal ions if alkali metal ions are present, an ion exchange reaction occurs with the hydrogen ions in the hydroxyl groups in the novolak-type phenolic resin, causing hexamethylenetetramine (hardening accelerator) and the novolac-type phenolic resin (thermosetting resin). It is thought to inhibit binding (hardening inhibition).
  • alkaline components derived from titanate are eluted on the friction surface due to wear and destruction of the friction material due to braking.
  • the alkali metal ion elution rate to the above upper limit or less, it is possible to prevent inhibition of curing of the thermosetting resin during heat and pressure molding, and as a result, crack resistance at high temperature and high load is further improved. can be improved. Further, by making the alkali metal ion elution rate equal to or higher than the above lower limit, rusting of the rotor can be suppressed even if the friction material of the present invention is left unused for a long period of time after braking. That is, by setting the alkali metal ion elution rate within the above range, both the crack resistance of the friction material and the suppression of rusting of the rotor can be achieved.
  • the alkali metal ion elution rate refers to the mass ratio of alkali metal ions eluted into water from a measurement sample such as titanate in water at 80°C.
  • a treatment layer made of a surface treatment agent may be formed on the surface of the titanate. good.
  • the surface treatment agent is not particularly limited, but includes silane coupling agents, titanium coupling agents, and the like. Among these, a silane coupling agent is preferable, and an amino-based silane coupling agent, an epoxy-based silane coupling agent, or an alkyl-based silane coupling agent is more preferable.
  • One of the surface treating agents may be used alone, or two or more thereof may be used in combination.
  • amino-based silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2 -aminoethyl-3-aminopropyltrimethoxysilane and the like.
  • epoxy-based silane coupling agents include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, triethoxy(3-glycidyloxypropyl)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like.
  • alkyl-based silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane. , n-hexyltrimethoxysilane, n-hexylriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane and the like.
  • a known surface treatment method can be used as a method for forming a treatment layer made of a surface treatment agent on the surface of the titanate.
  • the surface treatment agent is dissolved in a solvent that promotes hydrolysis (e.g., water, alcohol, or a mixed solvent thereof) to form a solution, and the solution is treated with titanic acid.
  • a solvent that promotes hydrolysis e.g., water, alcohol, or a mixed solvent thereof
  • examples include a wet method of spraying salt.
  • the amount of the surface treatment agent when the surface of the titanate is treated with the surface treatment agent is not particularly limited. .
  • the solution of the surface treatment agent may be sprayed so as to be 1 part by mass to 20 parts by mass.
  • the titanate used in the present invention can also be used by treating the titanate with the surface treatment agent and granulating it.
  • the average particle size of the granular titanate is preferably 100 ⁇ m or more and preferably 200 ⁇ m or less.
  • the titanate content is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 30% by mass with respect to 100% by mass of the total amount of the friction material composition. % by mass or less, more preferably 28% by mass or less, and even more preferably 25% by mass or less.
  • the mass ratio of titanate to steel fiber is preferably 0.1 or more, more preferably 0.6 or more, still more preferably 0.7 or more, and particularly preferably 0.8. or more, preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 1.5 or less.
  • the mass ratio of titanate to binder is preferably 0.4 or more, more preferably 0.6 or more, still more preferably 1.5 or more, and particularly preferably 1.7 or more. Yes, preferably 8.0 or less, more preferably 5.0 or less, still more preferably 3.0 or less.
  • the friction material composition of the present invention may optionally contain other materials (fiber base material, organic friction modifier, etc.) usually used in friction material compositions. materials, inorganic friction modifiers, lubricants, pH modifiers, fillers, etc.) can be blended.
  • the content of other materials in the friction material composition is preferably 20% by mass or more and preferably 80% by mass or less with respect to 100% by mass of the total amount of the friction material composition.
  • Fiber base material The fiber base material exhibits reinforcing properties in the friction material.
  • fiber base materials include inorganic fibers, metal fibers, organic fibers, and carbon-based fibers. One of these may be used alone, or two or more may be used in combination.
  • the content is preferably 0.1% by mass or more with respect to 100% by mass of the total amount of the friction material composition, preferably It is 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.
  • inorganic fibers include glass fiber, rock wool, ceramic fiber, biodegradable ceramic fiber, biodegradable mineral fiber, biosoluble fiber (SiO 2 —CaO—SrO fiber, etc.), wollastonite fiber, silicate fiber, Mineral fibers and the like can be mentioned, and among these, rock wool is preferable.
  • Metal fibers include straight-shaped or curled-shaped fibers mainly composed of metals such as aluminum, iron, zinc, tin, titanium, nickel, magnesium, silicon, etc., or alloy fibers (excluding steel fibers). Mention may be made of metal fibers.
  • Organic fibers include aromatic polyamide (aramid) fiber, fibrillated aramid fiber, acrylic fiber (homopolymer or copolymer fiber with acrylonitrile as the main raw material), fibrillated acrylic fiber, cellulose fiber, fibrillated cellulose Fibers, phenolic resin fibers and the like can be mentioned.
  • aromatic polyamide aramid
  • fibrillated aramid fiber acrylic fiber (homopolymer or copolymer fiber with acrylonitrile as the main raw material), fibrillated acrylic fiber, cellulose fiber, fibrillated cellulose Fibers, phenolic resin fibers and the like can be mentioned.
  • carbon-based fibers examples include carbon-based fibers such as flame-resistant fibers, PAN-based carbon fibers, pitch-based carbon fibers, and activated carbon fibers.
  • the fiber base material is preferably aramid fiber.
  • the fiber base material is preferably para-aramid fibers represented by poly-p-phenylene terephthalamide and the like.
  • the fiber base material is preferably fibrillated aramid fiber (also referred to as aramid pulp).
  • the specific surface area of the fibrillated aramid fibers is preferably 5 m 2 /g or more, preferably 25 m 2 /g or less, more preferably 15 m 2 /g or less.
  • the fibrillated aramid fiber preferably has a fiber length of 0.5 mm or more and preferably 1.2 mm or less.
  • the content is preferably 1% by mass or more, preferably 10% by mass or less, more preferably 10% by mass or less, with respect to 100% by mass of the total amount of the friction material composition It is 8% by mass or less, more preferably 6% by mass or less. If the content of fibrillated aramid fibers is at least the above lower limit, the crack resistance and wear resistance will be better, and if the content of fibrillated aramid fibers is below the above upper limit, fibrillated aramid fibers and other It is possible to prevent deterioration of crack resistance and wear resistance due to uneven distribution with the material.
  • rock wool When rock wool is contained in the friction material composition, its content is preferably 1% by mass or more, preferably 10% by mass or less, more preferably 9% by mass with respect to 100% by mass of the total amount of the friction material composition % or less. If the content of rock wool is within the above range, the coefficient of friction can be increased during high-load braking.
  • Organic friction modifier is a friction modifier that is blended for the purpose of further improving the noise and vibration performance, wear resistance, and the like of the friction material.
  • Organic friction modifiers include tire rubber, acrylic rubber, isoprene rubber, NBR (nitrile-butadiene rubber), SBR (styrene-butadiene rubber), unvulcanized or vulcanized rubber powder such as chlorinated butyl rubber, butyl rubber, and silicone rubber; dust; rubber-coated cashew dust; melamine dust and the like. One of these may be used alone, or two or more may be used in combination.
  • the content is preferably 0.1% by mass or more, preferably 30% by mass, with respect to 100% by mass of the total amount of the friction material composition. Below, it is more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 6% by mass or less.
  • Inorganic friction modifiers are friction modifiers added for the purpose of further improving the coefficient of friction in order to avoid deterioration of the heat resistance of the friction material, improve the wear resistance, or the like.
  • examples of inorganic friction modifiers include abrasives, metal powders, and other inorganic fillers.
  • the abrasive can be appropriately selected from those that act as an abrasive and improve the friction coefficient depending on the material of the rotor, which is the mating material, and can be selected based on the Mohs hardness of the mating material.
  • abrasives examples include silicon carbide (silicon carbide), titanium oxide, ⁇ -alumina, ⁇ -alumina, silica (silicon dioxide), magnesia (magnesium oxide), zirconia (zirconium oxide), zircon (zirconium silicate), oxide Chromium, iron oxide (triiron tetroxide, etc.), chromite, quartz, iron sulfide and the like can be mentioned.
  • an abrasive with a large average particle size and an abrasive with a small average particle size may be used together. Specifically, it is preferable to use an abrasive with an average particle size of 0.5 ⁇ m to 15 ⁇ m and an abrasive with an average particle size of 20 ⁇ m to 200 ⁇ m.
  • the mass ratio of the abrasive with a small average particle size to the abrasive with a large average particle size is preferable from the viewpoint of further reducing abrasion dust. is 0.1 or more, more preferably 2 or more, preferably 10 or less, more preferably 8 or less.
  • the content thereof is preferably 0.1% by mass or more, preferably 30% by mass or less, more preferably 30% by mass or less, with respect to 100% by mass of the total amount of the friction material composition It is 15% by mass or less.
  • Metal powders include single metals such as aluminum, zinc, iron, and tin, or powders in the form of alloys. One of these may be used alone, or two or more may be used in combination.
  • inorganic fillers include vermiculite, clay, mica, talc, dolomite, chromite, mullite, and calcium silicate. One of these may be used alone, or two or more may be used in combination.
  • the lubricant is preferably a solid lubricant, and examples thereof include carbon-based solid lubricants, metal sulfide-based solid lubricants, and polytetrafluoroethylene (PTFE). It may be used alone or in combination of two or more. Lubricants are preferably one or more selected from the group consisting of carbon-based solid lubricants and metal sulfide-based solid lubricants.
  • the content thereof is preferably 0.1% by mass or more, more preferably 1% by mass or more, with respect to 100% by mass of the total amount of the friction material composition, It is preferably 30% by mass or less, more preferably 20% by mass or less.
  • Examples of the carbon-based solid lubricant include synthetic or natural graphite (graphite), scale-like graphite, phosphate-coated graphite, carbon black, coke, activated carbon, elastic graphitized carbon, and the like. Synthetic graphite and natural graphite are preferred from the standpoint of further enhancement.
  • a carbon-based solid lubricant When a carbon-based solid lubricant is contained, its content is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass with respect to 100% by mass of the total amount of the friction material composition. % or more, preferably less than 15% by mass, more preferably less than 10% by mass, and even more preferably 8% by mass or less. If the content of the carbon-based solid lubricant is at least the above lower limit, friction material wear tends to be better at high temperatures. It tends to be easy to suppress the decrease in the coefficient.
  • sulfur-based solid lubricants include antimony trisulfide, molybdenum disulfide, tin sulfide, iron sulfide, zinc sulfide, bismuth sulfide, and tungsten disulfide. are tin sulfide and molybdenum disulfide.
  • a sulfur-based solid lubricant When a sulfur-based solid lubricant is contained, its content is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass with respect to 100% by mass of the total amount of the friction material composition. % or more, preferably less than 15% by mass, more preferably less than 10% by mass, and even more preferably 8% by mass or less.
  • the content of the sulfur-based solid lubricant is at least the above lower limit, there is a tendency to further suppress rotor wear, and if the content of the sulfur-based solid lubricant is at most the above upper limit, the decrease in the friction coefficient is suppressed tend to be easy.
  • pH adjusters include calcium hydroxide (slaked lime), sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, disodium hydrogen phosphate, and tripotassium phosphate. , dipotassium hydrogen phosphate and the like, and organic bases such as imidazole, histidine and hexamethylenediamine, and inorganic bases are preferred from the viewpoint of cost and hygroscopicity. One of these may be used alone, or two or more may be used in combination.
  • the pH adjusting material is sometimes used to prevent rust adhesion between the friction material and the mating material (rotor).
  • the content is preferably 0.1% by mass or more and preferably 8% by mass or less with respect to 100% by mass of the total amount of the friction material composition.
  • filler examples include barium sulfate and calcium carbonate, preferably barium sulfate. One of these may be used alone, or two or more may be used in combination.
  • Barium sulfate consists of elutriated barium sulfate (barite powder) obtained by pulverizing a mineral called barite, removing iron from it, washing it, and elutriating it, and artificially synthesized precipitated barium sulfate.
  • the particle size of precipitated barium sulfate can be controlled by the conditions during synthesis, and fine barium sulfate with a small content of coarse particles can be produced.
  • the friction material composition of the present invention is prepared by (1) mixing each component with a mixer such as a Loedige mixer (“Loedige” is a registered trademark), a pressure kneader, or an Eirich mixer (“Eirich” is a registered trademark). Method; (2) A method of preparing granules of desired components and, if necessary, mixing other components using a mixer such as a Loedige mixer, a pressure kneader, or an Eirich mixer. can.
  • a mixer such as a Loedige mixer (“Loedige” is a registered trademark), a pressure kneader, or an Eirich mixer (“Eirich” is a registered trademark).
  • the content of each component of the friction material composition of the present invention can be appropriately selected depending on the desired friction characteristics, and can be produced by the above production method.
  • the friction material composition of the present invention may be prepared by preparing a masterbatch containing a specific component at a high concentration, and adding a thermosetting resin or the like to this masterbatch and mixing.
  • Friction Material and Friction Member> the friction material composition is temporarily molded at room temperature (20° C.), and the obtained temporary molded body is heat-pressed (molding pressure: 10 MPa to 40 MPa, molding temperature: 150° C. to 200° C.). , If necessary, the obtained compact is subjected to heat treatment in a heating furnace (150° C. to 220° C., held for 1 hour to 12 hours), and then the compact is machined and polished. A friction material having a predetermined shape can be manufactured.
  • Friction members that can be formed using a friction material include, for example, (1) a structure consisting of only the friction material, (2) a base material such as a backing metal, and a book provided on the base material to provide a friction surface. A configuration including the friction material of the invention and the like can be mentioned.
  • the base material is used to further improve the mechanical strength of the friction member, and can be made of metal, fiber-reinforced resin, or the like.
  • metals or fiber reinforced resins include iron, stainless steel, glass fiber reinforced resins, carbon fiber reinforced resins, and the like.
  • Friction materials usually have a large number of fine pores inside, which act as an escape route for decomposition products (gases and liquids) at high temperatures, preventing deterioration in friction characteristics and reducing the rigidity of the friction material for damping. It prevents the occurrence of squeal by improving the durability.
  • the material composition and molding conditions are controlled so that the porosity is preferably 5% to 30%, more preferably 10% to 25%.
  • the friction member of the present invention is composed of the friction material composition of the present invention, fine wear such as PM10 and PM2.5 can be achieved even when the copper component is not contained or the copper component content is reduced. Low dust generation. Therefore, the friction member of the present invention can be suitably used in brake systems in general, such as disc pads, brake linings, and clutch facings, which constitute braking devices for various vehicles and industrial machines. It can be preferably used as.
  • the present invention is by no means limited to the following examples, and can be modified as appropriate within the scope of not changing the gist of the invention.
  • Phenolic resin novolac type phenolic resin (straight phenolic resin) powder containing hexamethylenetetramine
  • Table 3 shows the physical properties of the powder.
  • Tianate 4 403.1 g of titanium oxide, 377.2 g of potassium carbonate, and 3.8 g of lithium carbonate were mixed for 1 hour while pulverizing with a vibration mill. A crucible was filled with 500 g of the pulverized mixed powder obtained, and the mixture was fired in an electric furnace at 850° C. for 4 hours in an air atmosphere.
  • the obtained titanate 4 had a particle shape with a plurality of projections and a tunnel-like crystal structure of K 2.10 Ti 5.90 Li 0.10 O 12.9 .
  • Table 3 shows the physical properties of the powder.
  • Steel fiber 1 curled fiber, average fiber length (cut length) 1.5 mm, average fiber diameter 50 ⁇ m, trade name "Cut Wool BS-1V", manufactured by Bonstar Sales Co., Ltd.
  • Steel fiber 2 straight fiber, average fiber length (cut Length) 3 mm, average fiber diameter 60 ⁇ m, trade name “KC Metal Fiber”, manufactured by Nijieda Co., Ltd.
  • Aramid fiber fibrillated para-aramid fiber (aramid pulp), fiber length 0.89 mm, specific surface area 9.8 m 2 /g
  • Barium sulfate elutriation barium sulfate powder, average particle size 24 ⁇ m
  • Mica natural mica powder, average particle size 180 ⁇ m
  • Zircon Zirconium silicate powder, average particle size 1.5 ⁇ m
  • Alumina ⁇ -alumina powder, average particle size 57 ⁇ m
  • Tin sulfide Tin (II) sulfide powder, average particle size 7 ⁇ m
  • Graphite Synthetic graphite powder, average particle size 730 ⁇ m
  • Average particle size Measured with a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, product number “SALD-2100”), and the particle size at 50% cumulative volume basis in the obtained particle size distribution was defined as the average particle size.
  • the average particle size of graphite is the average value of 30 particles observed with a digital microscope (manufactured by Keyence, "VHX-1000"). Rogis Co., Ltd., product number "S-4800”) was observed, and the average value of 200 samples was taken.
  • [Alkali metal ion elution rate] Measure the mass (X) g of the sample, then add the sample to ultrapure water to prepare a 1% by mass slurry, stir at 80 ° C. for 4 hours, and remove the solid content with a membrane filter having a pore size of 0.2 ⁇ m. , to obtain an extract.
  • the mass (Y) g of alkali metal ions in the obtained extract was measured with an ion chromatograph (manufactured by Dionex, product number "ICS-1100").
  • the alkali metal ion elution rate (% by mass) was calculated based on the formula [(Y)/(X)] ⁇ 100 using the mass (X) g and (Y) g values.
  • the Rockwell hardness of the surface of the friction member was measured according to JIS D4421.
  • the hardness scale used was the S scale.
  • Example 12 in which the total amount of solid lubricant is the same as in Examples 1 to 11 and the blending ratio of graphite is increased, the amount of fine wear dust generated can be reduced, but the coefficient of friction is lowered. Recognize.
  • the reduction rate of wear dust in Tables 5 and 6 is calculated based on Comparative Example 1 in which the blending amount of steel fibers is the same.

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Abstract

L'invention concerne une composition de matériau de frottement à partir de laquelle il est possible de former un matériau à faible teneur en acier qui produit une quantité plus faible de poudre fine d'abrasion et de poussières, telles que PM10 et PM2.5, au cours du freinage, même lorsqu'elle ne contient pas de constituants de type cuivre ou les contient en une petite quantité inférieure à 0,5 % en masse ; et un matériau de frottement et un élément de frottement qui font appel à cette composition de matériau de frottement.　La composition de matériau de frottement de l'invention contient, en tant qu'éléments de type cuivre, moins de 0,5 % en masse de constituants de type cuivre. La composition de matériau de frottement contient un matériau liant, des fibres à base d'acier et un titanate. La quantité contenue des fibres à base d'acier n'est pas inférieure à 10 % en masse mais est inférieure à 30 % en masse pour 100 % en masse de la quantité totale de la composition de matériau de frottement.
PCT/JP2022/028011 2021-08-03 2022-07-19 Composition de matériau de frottement, matériau de frottement et élément de frottement WO2023013396A1 (fr)

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JP2014196445A (ja) * 2013-03-29 2014-10-16 曙ブレーキ工業株式会社 摩擦材
JP2016121243A (ja) * 2014-12-24 2016-07-07 日本ブレーキ工業株式会社 摩擦材組成物、摩擦材組成物を用いた摩擦材および摩擦部材
JP2017014369A (ja) * 2015-06-30 2017-01-19 株式会社アドヴィックス 摩擦材
JP2020029490A (ja) * 2018-08-21 2020-02-27 大塚化学株式会社 摩擦材組成物、摩擦材及び摩擦部材
JP2020094115A (ja) * 2018-12-12 2020-06-18 大塚化学株式会社 摩擦材組成物、摩擦材組成物を用いた摩擦材及び摩擦部材
JP2020203966A (ja) * 2019-06-14 2020-12-24 大塚化学株式会社 摩擦材組成物、摩擦材、及び摩擦部材

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005282738A (ja) * 2004-03-30 2005-10-13 Hitachi Ltd ブレーキ摩擦材
JP2014196445A (ja) * 2013-03-29 2014-10-16 曙ブレーキ工業株式会社 摩擦材
JP2016121243A (ja) * 2014-12-24 2016-07-07 日本ブレーキ工業株式会社 摩擦材組成物、摩擦材組成物を用いた摩擦材および摩擦部材
JP2017014369A (ja) * 2015-06-30 2017-01-19 株式会社アドヴィックス 摩擦材
JP2020029490A (ja) * 2018-08-21 2020-02-27 大塚化学株式会社 摩擦材組成物、摩擦材及び摩擦部材
JP2020094115A (ja) * 2018-12-12 2020-06-18 大塚化学株式会社 摩擦材組成物、摩擦材組成物を用いた摩擦材及び摩擦部材
JP2020203966A (ja) * 2019-06-14 2020-12-24 大塚化学株式会社 摩擦材組成物、摩擦材、及び摩擦部材

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