WO2023112698A1 - Oxyde lithium potassium titane et procédé de production associé, modificateur de frottement, composition de matériau de frottement, matériau de frottement et élément de frottement - Google Patents

Oxyde lithium potassium titane et procédé de production associé, modificateur de frottement, composition de matériau de frottement, matériau de frottement et élément de frottement Download PDF

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WO2023112698A1
WO2023112698A1 PCT/JP2022/044381 JP2022044381W WO2023112698A1 WO 2023112698 A1 WO2023112698 A1 WO 2023112698A1 JP 2022044381 W JP2022044381 W JP 2022044381W WO 2023112698 A1 WO2023112698 A1 WO 2023112698A1
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potassium titanate
friction
lithium potassium
friction material
mass
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PCT/JP2022/044381
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Japanese (ja)
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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

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  • the present invention relates to lithium potassium titanate, a method for producing the lithium potassium titanate, and a friction modifier, friction material composition, friction material, and friction member using the lithium potassium titanate.
  • 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. Also, in Europe, low steel materials have been used from the viewpoint of maintaining the coefficient of friction during high-speed braking.
  • 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 interface, 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 the friction interface 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 abrasion powder generated during braking, and it has been suggested that it may cause pollution of rivers, lakes, and oceans.
  • a state law prohibiting the sale of friction materials containing 5% by mass or more of copper, and from 2025 onwards, prohibiting the sale and installation of friction materials in new vehicles.
  • Titanates include titanates with a tunnel crystal structure (e.g., potassium hexatitanate) and titanates with a layered crystal structure (e.g., lithium potassium titanate, magnesium potassium titanate). Each is used alone or in combination as appropriate.
  • a friction material composition containing titanate and barium sulfate having an average particle size of 0.1 ⁇ m to 20 ⁇ m has been proposed (Patent Document 1).
  • Potassium hexatitanate which has a thermally stable crystal structure, is an effective titanate that provides a coefficient of friction in the high-load range. and fibrous particles with an aspect ratio of 3 or more), their use is being refrained mainly in Europe.
  • lithium potassium titanate is known as a titanate that does not contain WHO fibers, but although it has excellent wear resistance, it has a problem of friction coefficient in a high load range.
  • An object of the present invention is to provide a lithium potassium titanate and a lithium potassium titanate that can increase the coefficient of friction in a high load range and improve the stability of the coefficient of friction when used as a friction material. and a friction modifier, a friction material composition, a friction material, and a friction member using the lithium potassium titanate.
  • the present invention provides the following lithium potassium titanate, a method for producing the lithium potassium titanate, and a friction modifier, friction material composition, friction material, and friction member using the lithium potassium titanate.
  • Item 2 The lithium potassium titanate according to Item 1, wherein the lithium potassium titanate is plate-like particles.
  • Item 3 The lithium potassium titanate according to Item 1 or 2, wherein the lithium potassium titanate has an average particle size of 0.1 ⁇ m or more and 100 ⁇ m or less.
  • Item 4 The lithium potassium titanate according to any one of items 1 to 3, wherein the lithium potassium titanate has a specific surface area of 0.1 m 2 /g or more and 10 m 2 /g or less.
  • Item 5 The lithium potassium titanate according to any one of items 1 to 4, wherein the lithium potassium titanate has an alkali metal ion elution rate of 0.01% by mass or more and 15% by mass or less.
  • Item 6 The method for producing lithium potassium titanate according to any one of items 1 to 5, comprising the steps of preparing a raw material lithium potassium titanate, and eluting a portion of potassium from the raw material lithium potassium titanate. and adjusting the molar ratio of titanium to potassium (TiO 2 /K 2 O) in terms of oxide to potassium to 8 to 35, followed by firing.
  • Item 7 A friction modifier comprising the lithium potassium titanate according to any one of Items 1 to 5.
  • Item 8 A friction material composition containing lithium potassium titanate according to any one of items 1 to 5 and a binder, and having a copper component content of less than 0.5% by mass as copper element.
  • Item 9 The friction material composition according to Item 8, wherein the content of the lithium potassium titanate is 1% by mass or more and 40% by mass or less with respect to 100% by mass of the total amount of the friction material composition.
  • Item 10 The friction material according to Item 8 or 9, characterized in that the mass ratio of the lithium potassium titanate to the binder (lithium potassium titanate/binder) is 0.1 or more and 8 or less. Composition.
  • Item 11 The friction material composition according to any one of Items 8 to 10, wherein the content of steel-based fibers is less than 10% by mass with respect to the total amount of 100% by mass of the friction material composition.
  • Item 12 A friction material that is a molded body of the friction material composition according to any one of Items 8 to 11.
  • Item 13 A friction member comprising the friction material according to Item 12.
  • lithium potassium titanate and lithium potassium titanate which can increase the friction coefficient in a high load region and improve the stability of the friction coefficient when used as a friction material. and a friction modifier, a friction material composition, a friction material, and a friction member using the lithium potassium titanate.
  • FIG. 1 is a diagram showing the relationship between the number of times of braking and the coefficient of friction during fading in the fading test of the friction members obtained in Examples 1 and 2 and Comparative Example 1.
  • FIG. 1 is a diagram showing the relationship between the number of times of braking and the coefficient of friction during fading in the fading test of the friction members obtained in Examples 1 and 2 and Comparative Example 1.
  • Lithium potassium titanate >
  • the present inventors have found that in lithium potassium titanate represented by the composition formula K 0.10 to 0.44 Li 0.27 Ti 1.73 O 3.65 to 3.82 , the X-ray diffraction of the lithium potassium titanate By setting the half width of the peak in the measurement to 0.20° or more, it is possible to increase the friction coefficient in a high load region when used as a friction material, and to improve the stability of the friction coefficient. I found
  • the lithium potassium titanate of the present invention is a low-crystalline compound, unlike conventional ones.
  • the term "low crystallinity" means that, in X-ray diffraction measurement, unlike an amorphous compound that does not have a specific peak, and unlike a crystalline compound that has a sharp peak, it shows an intermediate peak. It refers to things.
  • the term "amorphous" in X-ray diffraction measurement refers to, for example, a peak having a half-value width of 5.0° or more, and a broad halo being observed with almost no peak being observed.
  • the half width of the peak in lithium potassium titanate is preferably 0.25° or more, preferably 1.0° or less, and more preferably 0.8° or less.
  • the half width means the width of the diffraction angle at the half height of the peak obtained by X-ray diffraction measurement.
  • the half width of the peak in potassium lithium titanate can be adjusted, for example, by the molar ratio of titanium to potassium in terms of oxide (TiO 2 /K 2 O) in the manufacturing method described later.
  • the X-ray diffraction measurement can be performed by a wide-angle X-ray diffraction method, and CuK ⁇ rays (wavelength 1.5418 ⁇ ) can be used.
  • the X-ray diffraction measurement device for example, Rigaku's product number "Ultima IV" can be used.
  • the lithium potassium titanate is preferably non-fibrous particles from the viewpoint of working environment.
  • the non-fibrous particles include, for example, spherical particles (including those 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 shape such as shape can be mentioned.
  • the lithium potassium titanate is preferably tabular particles. Further, the lithium potassium titanate may be porous particles.
  • 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 lithium potassium titanate is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 3 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and more preferably 50 ⁇ m or less. It is preferably 30 ⁇ m or less.
  • the friction characteristics can be further improved when the friction material is produced.
  • the average particle size refers to the particle size at 50% cumulative volume based on the particle size distribution measured by 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 lithium potassium titanate is preferably 0.1 m 2 /g or more, more preferably 0.3 m 2 /g or more, still more preferably 0.5 m 2 /g or more, and preferably It is 10 m 2 /g or less, more preferably 6 m 2 /g or less, still more preferably 4 m 2 /g or less.
  • the specific surface area can be measured according to JIS Z8830.
  • the alkali metal ion elution rate of lithium potassium titanate is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and preferably 15% by mass. or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
  • a novolak-type phenolic resin which is an example of a thermosetting resin used in a friction material composition
  • a curing agent such as hexamethylenetetramine
  • the hardening reaction is initiated by bonding with the hydroxyl groups inside.
  • alkali metal ions are present at this time, an ion exchange reaction occurs with the hydrogen ions in the hydroxyl groups in the novolac-type phenolic resin, resulting in hexamethylenetetramine (curing agent (or curing accelerator)) and novolak-type phenolic resin (thermosetting).
  • the alkali metal ion elution rate to the above upper limit or less, it is possible to prevent the curing inhibition of the thermosetting resin during heat and pressure molding, and as a result, the crack resistance at high temperature and high load is further improved.
  • the alkali metal ion elution rate to the above lower limit or more, rusting of the rotor can be suppressed even if the friction material using the lithium potassium titanate 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 rust prevention of the rotor can be achieved at a higher level.
  • the alkali metal ion elution rate refers to the mass ratio of alkali metal ions eluted into water from a measurement sample such as lithium potassium titanate in water at 80°C.
  • a treated layer made of a surface treatment agent may be formed on the surface of the lithium potassium titanate from the viewpoint of further improving the adhesion with the binder used in the friction material composition.
  • surface treatment agents include silane coupling agents and titanium coupling agents. Among these, silane coupling agents are preferably used, and amino-based silane coupling agents, epoxy-based silane coupling agents, and alkyl-based silane coupling agents are more preferably used.
  • 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 lithium potassium titanate.
  • a wet method of dissolving the surface treatment agent in a mixed solvent) to form a solution and spraying the solution onto lithium potassium titanate can be used.
  • the amount of the surface treatment agent when the surface of the lithium potassium titanate is treated with the surface treatment agent is not particularly limited. is 0.1 parts by mass or more and 20 parts by mass or less.
  • the lithium potassium titanate used in the present invention can be granulated by treating the lithium potassium titanate with the surface treatment agent or the binder described below.
  • the average particle size of the granular lithium potassium titanate is preferably 100 ⁇ m or more and preferably 200 ⁇ m or less.
  • the method for producing lithium potassium titanate of the present invention is not particularly limited, it can be produced, for example, by the following method.
  • raw material lithium potassium titanate hereinafter referred to as “raw material KTLO”
  • part of the potassium is eluted from the raw material KTLO to adjust the molar ratio of titanium to potassium (TiO 2 /K 2 O) in terms of oxides to 8 or more and 35 or less (8 to 35), followed by firing.
  • the molar ratio of titanium to potassium in terms of oxide (TiO 2 /K 2 O) is preferably 20 or less, more preferably 16 or less, still more preferably 10 or less.
  • Lithium potassium titanate having a layered crystal structure of site type can be used.
  • raw material KTLO includes, for example, titanium oxide or a compound that generates titanium oxide by heating (these are collectively abbreviated as "titanium compound”), potassium oxide or a compound that generates potassium oxide by heating (these are collectively abbreviated as “potassium compound”), lithium oxide or a compound that generates lithium oxide by heating (these are collectively abbreviated as “lithium compound”), and, if necessary, a mixture of flux. , can be obtained by firing.
  • titanium compound low order titanium oxide, hydrous titanium oxide, hydrate of titanium oxide, titanium hydroxide, etc. can be used.
  • a titanium compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Potassium compounds include potassium oxide, potassium carbonate, potassium hydroxide, potassium nitrate, and the like. Among them, potassium carbonate or potassium hydroxide can be preferably used as the potassium compound.
  • a potassium compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Lithium compounds include lithium oxide, lithium hydroxide, and lithium carbonate.
  • As the lithium compound lithium hydroxide or lithium carbonate can be preferably used.
  • a lithium compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the mixing ratio of the titanium compound, the potassium compound, and the lithium compound can be appropriately adjusted according to the composition formula of the target raw material KTLO.
  • the purpose of the flux is to form crystals at a temperature lower than the melting point, and as the crystal grows, it has an idiomorphic shape surrounded by flat crystal planes that reflect the crystal structure, making it easy to specify the crystal orientation.
  • Potassium chloride, potassium fluoride, potassium molybdate, potassium tungstate, and the like can be suitably used as the material.
  • Firing in the production of the raw material KTLO can be performed using an electric furnace or the like. Further, the firing reaction can be completed by maintaining the temperature in the range of 800° C. to 1100° C. for 1 hour to 24 hours. After firing, the resulting powder may be pulverized to a desired size or passed through a sieve to loosen it.
  • the elution of potassium from the raw material KTLO can be performed by mixing an acid with an aqueous slurry in which the raw material KTLO is dispersed in water.
  • the concentration of the aqueous slurry is not particularly limited and can be appropriately selected from a wide range.
  • the concentration of the aqueous slurry may be about 1% by mass to 30% by mass in consideration of workability and the like.
  • solids are separated from the slurry by filtration, centrifugation, or the like. The separated solid content can be washed with water and dried as necessary.
  • the acid used here is not particularly limited, and known acids can be used.
  • acids include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid. Two or more acids may be used in combination as necessary.
  • the amount of acid added to the aqueous slurry can be appropriately adjusted depending on the desired molar ratio of titanium to potassium in terms of oxide (TiO 2 /K 2 O). Lithium potassium titanate can be made to have low crystallinity by the potassium elution.
  • Firing after elution of potassium can be performed using an electric furnace or the like. Further, the temperature is maintained in the range of 100° C. to 600° C., preferably 400° C. to 600° C. for 1 hour to 12 hours, more preferably 1 hour to 10 hours.
  • the elution amount of alkali metal ions in lithium potassium titanate can be adjusted by the firing temperature and firing time.
  • Lithium potassium titanate of the present invention can be obtained as described above.
  • Friction Material Composition contains the lithium potassium titanate of the present invention and a binder, and the content of the copper component in terms of copper element is 0.00% with respect to 100% by mass of the total amount of the friction material composition. It is characterized by being less than 5% by mass.
  • the lithium potassium titanate of the present invention can be used as a friction modifier.
  • the friction material composition of the present invention may further contain other materials as necessary.
  • the term "friction material composition” refers to a composition used for a friction material.
  • the friction material composition of the present invention contains the lithium potassium titanate of the present invention as a friction modifier, it is possible to increase the coefficient of friction in the high-load region of the friction material and to increase the stability of the coefficient of friction. be able to.
  • 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. environmental load can be reduced.
  • the phrase "does not contain a copper component” means that copper fiber, copper powder, and copper-containing alloys (brass, bronze, etc.) and compounds are blended as raw materials for the friction material composition. It means that you have not.
  • the friction material composition of the present invention excellent friction characteristics can be obtained even when the copper component is not contained or the copper component content is reduced.
  • the friction material composition of the present invention is an NAO material in which the content of steel fibers such as steel fibers and stainless steel fibers is less than 10% by mass with respect to 100% by mass of the total amount of the friction material composition. is preferred. In this case, it is easy to form a transfer film on the surface of the mating material, and excellent friction and wear characteristics can be obtained.
  • the binding material integrates the friction modifier such as lithium potassium titanate contained in the friction material composition and imparts 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.
  • phenol resins straight phenol resins
  • modified phenol resins are preferred as thermosetting resins from the viewpoint of further improving heat resistance, moldability, and friction characteristics.
  • the phenolic resin either a resol-type phenolic resin or a novolak-type phenolic resin can be used, but the novolac-type phenolic resin is preferable from the viewpoint of production stability and cost.
  • the novolak-type phenol resin may contain additives such as a curing agent and a curing accelerator (for example, hexamethylenetetramine, etc.) as necessary.
  • the content of the binder in the friction material composition is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 30% by mass or less with respect to 100% by mass of the total amount of the friction material composition. More preferably, it is 20% by mass or less.
  • the lithium potassium titanate used in the friction material composition of the present invention is the aforementioned lithium potassium titanate of the present invention.
  • the content of lithium potassium titanate in the friction material composition is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more with respect to 100% by mass of the total amount of the friction material composition. , preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.
  • the mass ratio of lithium potassium titanate to the binder is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.1 or more, preferably 8 or less, and more It is preferably 6 or less, more preferably 4 or less.
  • friction material composition of the present invention in addition to the binder and lithium potassium titanate of the present invention, other materials usually used in friction material compositions (fiber base material, organic friction modifier, Inorganic friction modifiers, lubricants, pH modifiers, fillers, etc.) can be blended.
  • the content of other materials in the friction material composition is preferably 30% by mass or more and preferably 94% 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.
  • 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.
  • 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 7% 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.
  • Metal fibers include single metals such as aluminum, iron, zinc, tin, titanium, nickel, magnesium, and silicon, fibers in the form of alloys (steel fibers, stainless steel fibers, etc.), and straight-shaped fibers mainly composed of metals such as cast iron fibers. Alternatively, curled metal fibers can be used.
  • Organic fibers include aromatic polyamide (aramid) fiber, fibrillated aramid fiber (aramid pulp), acrylic fiber (homopolymer or copolymer fiber with acrylonitrile as the main raw material), fibrillated acrylic fiber, and cellulose fiber. , fibrillated cellulose fibers, phenolic resin fibers, and the like.
  • the fibers are aramid fibers.
  • the organic fiber 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 the fibrillated aramid fiber is at least the above lower limit, the crack resistance and wear resistance will be better. Further, if the content of the fibrillated aramid fibers is equal to or less than the above upper limit, deterioration of crack resistance and wear resistance due to uneven distribution of the fibrillated aramid fibers and other materials can be more reliably prevented.
  • 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.
  • 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 (excluding lithium potassium titanate) are used for the purpose of avoiding deterioration of the heat resistance of the friction material, or for the purpose of further improving the coefficient of friction in order to improve the wear resistance. It is a friction modifier to be blended.
  • 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 coefficient of friction 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.
  • the Mohs hardness of the abrasive is preferably 6 or more, and preferably 8 or less, from the viewpoint of more effectively expressing the coefficient of friction of the abrasive.
  • 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.
  • zirconia (zirconium oxide) and zircon (zirconium silicate) are preferred.
  • the average particle size of zirconia (zirconium oxide) is preferably 1 ⁇ m to 14 ⁇ m.
  • the average particle size of zircon (zirconium silicate) is preferably 0.2 ⁇ m to 2 ⁇ m.
  • the content thereof is preferably 0.1% by mass or more, more preferably 5% 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 25% by mass or less, and even more preferably 18% 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, calcium silicate, and titanates other than the above lithium potassium titanate (hereinafter referred to as "other titanates").
  • other titanates include vermiculite, clay, mica, talc, dolomite, chromite, mullite, calcium silicate, and titanates other than the above lithium potassium titanate (hereinafter referred to as "other titanates”).
  • One of these may be used alone, or two or more may be used in combination.
  • titanates include Otsuka Chemical's TERRACESS JSL, TERRACESS JSL-R, TERRACESS DP-R, TERRACESS DP-A, TERRACESS DP-AS, Kubota's TXAX-MA, TXAX-A, and Toho Titanium.
  • Potassium hexatitanate such as TOFIX-S and TOFIX-SNR manufactured by Otsuka Chemical
  • Sodium hexatitanate such as TERRACESS DSR manufactured by Otsuka Chemical
  • Potassium octatitanate such as TERRACE JP
  • Potassium magnesium titanate such as TERRACE PM and TERRACE PS PS manufactured by Otsuka Chemical
  • Lithium potassium titanate such as TERRACE L, TERRACE L-SS, TERRACE JSM-M manufactured by Otsuka Chemical, etc.
  • Other titanates are preferably sodium hexatitanate, potassium octatitanate, potassium magnesium titanate, and potassium lithium titanate.
  • the mass ratio of the other titanate to the lithium potassium titanate of the present invention is the friction in the high load region From the viewpoint of the coefficient, it is preferably 0.1 or more and preferably 3 or less.
  • the lubricant is preferably a solid lubricant, and examples thereof include carbon-based lubricants, metal sulfide-based lubricants, and polytetrafluoroethylene (PTFE). It may be used, or two or more may be used in combination. Lubricants are preferably one or more selected from the group consisting of carbon-based lubricants and metal sulfide-based 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 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
  • Examples of the carbon-based 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 viewpoint that they can be imparted to.
  • Examples of the metal sulfide-based solid lubricant include antimony trisulfide, molybdenum disulfide, tin sulfide, iron sulfide, zinc sulfide, bismuth sulfide, tungsten disulfide, etc., and are less harmful to the human body. tin sulfide and molybdenum disulfide are preferred. One of these may be used alone, or two or more may be used in combination.
  • 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. From the viewpoint of cost and hygroscopicity, the pH adjuster is preferably an inorganic base. 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.
  • fillers examples include barium sulfate and calcium carbonate. Barium sulfate can preferably be used as the filler. 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 low content of coarse particles can be produced. From the viewpoint of further reducing impurities and making the particle size distribution of the barium sulfate particles more uniform, it is preferable to use precipitated barium sulfate.
  • the friction material composition of the present invention is produced by (1) mixing each component with a mixer such as a Loedige mixer (“Loedige” is a registered trademark), a pressure kneader, an Eirich mixer (“Eirich” is a registered trademark), or the like. 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.
  • 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, adding a thermosetting resin or the like to this masterbatch, and mixing.
  • 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 (150° C. to 220° C., held for 1 hour to 12 hours) in a heating furnace, 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.
  • Materials for the substrate include metals, fiber-reinforced resins, and 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, and these pores serve as escape routes for decomposition products (gases and liquids) at high temperatures. Squealing is prevented by lowering the rigidity and improving damping performance.
  • the composition of materials 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, excellent friction characteristics can be obtained even when the copper component is not contained or the copper component content is reduced. 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.
  • compositional formula The crystal structure was confirmed by an X-ray diffraction measurement device (manufactured by Rigaku, product number “Ultima IV”). In addition, the compositional formula was confirmed by an ICP-AES analyzer (manufactured by SII Nanotechnology Co., Ltd., product number "SPS5100").
  • Average particle size Measured with a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, product number “SALD-2300”), and the particle size at 50% cumulative volume basis in the obtained particle size distribution was defined as the average particle size.
  • 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.
  • Phenolic resin Novolac-type phenolic resin powder containing hexamethylenetetramine
  • Barium sulfate average particle size 1.6 ⁇ m Natural mica: average particle size 180 ⁇ m Cashew dust: average particle size 200 ⁇ m Iron oxide: average particle size 0.3 ⁇ m, Mohs hardness 6 Zirconium silicate: average particle size 1.1 ⁇ m, Mohs hardness 7.5 Antimony trisulfide: average particle size 1.5 ⁇ m Synthetic graphite: average particle size 730 ⁇ m Aramid fiber: fibrillated para-aramid fiber (aramid pulp), fiber length 0.89 mm, specific surface area 9.8 m 2 /g Slaked lime: average particle size 0.2 ⁇ m Rock wool: average fiber length 125 ⁇ m, maximum shot content (125 ⁇ m or more) 5.0%
  • the surface (friction surface) of the friction member was polished by 1.0 mm, and a brake efficacy test was conducted based on JASO C406. However, the first fade test conditions were changed to a speed of 160 km/h assuming a high load, and the braking effectiveness test was conducted.
  • the rotor used was a cast iron rotor belonging to standard number A48/A48M in ASTM standards.
  • FIG. 1 is a diagram showing the relationship between the number of times of braking and the coefficient of friction during fading in the fading test of the friction members obtained in Examples 1 and 2 and Comparative Example 1.

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Abstract

L'invention concerne un oxyde de lithium potassium titane qui peut augmenter un coefficient de frottement dans une région de charge élevée et qui peut améliorer la stabilité d'un coefficient de frottement lorsqu'il est utilisé dans un matériau de frottement.　L'oxyde de lithium potassium titane est représenté par la formule de composition : K0,10 à 0,44Li0,27Ti1,73O3,65-3,82, dans laquelle la demi-largeur d'un pic observé dans une plage d'angles de diffraction 2θ de 10,9° à 11,6° dans une mesure de diffraction de rayons X de l'oxyde de lithium potassium titane est de 0,20° ou plus.
PCT/JP2022/044381 2021-12-13 2022-12-01 Oxyde lithium potassium titane et procédé de production associé, modificateur de frottement, composition de matériau de frottement, matériau de frottement et élément de frottement WO2023112698A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000265157A (ja) * 1999-03-16 2000-09-26 Otsuka Chem Co Ltd 摩擦材
WO2014156654A1 (fr) * 2013-03-27 2014-10-02 大塚化学株式会社 Composition de résine, matériau de friction et procédé pour les produire
WO2017183155A1 (fr) * 2016-04-21 2017-10-26 日立化成株式会社 Composition de matériau de friction, matériau de friction et élément de friction obtenus à partir de ladite composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000265157A (ja) * 1999-03-16 2000-09-26 Otsuka Chem Co Ltd 摩擦材
WO2014156654A1 (fr) * 2013-03-27 2014-10-02 大塚化学株式会社 Composition de résine, matériau de friction et procédé pour les produire
WO2017183155A1 (fr) * 2016-04-21 2017-10-26 日立化成株式会社 Composition de matériau de friction, matériau de friction et élément de friction obtenus à partir de ladite composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUSE, Y. ET AL.: "Composition-Dependent Ion-Exchange Reactivity of Potassium Lithium Titanates", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 81, no. 6, 11 June 2008 (2008-06-11), pages 767 - 772, XP009546907, DOI: 10.1246/bcsj.81.767 *

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