JP2020029490A - Friction material composition, friction material, and friction member - Google Patents

Abstract

To provide a friction material composition excellent in yield of heating molding even when a copper component is not contained, or content of the copper component is set low.SOLUTION: There is provided a friction composition including thermosetting resin composition containing a titanate compound and a thermosetting resin, and barium sulfate, in which volume-based cumulative 50% particle diameter (D) of the barium sulfate of 0.1 μm to 20 μm, and content of the copper component as a copper element of 0.5 mass% or less in 100 mass% of total amount of the friction material composition.SELECTED DRAWING: None

Description

  The present invention relates to a friction material composition containing a titanate compound, and a friction material and a friction member using the friction material composition.

  Friction members such as brake linings, disc pads, and clutch facings that constitute braking devices for various vehicles, industrial machines, etc. have a high friction coefficient, are stable, have excellent fade resistance, and have excellent wear resistance. In addition, low rotor (opposite material) aggressiveness is required.

  In order to satisfy these characteristics, a friction material formed from a resin composition containing a filler such as a fibrous potassium titanate and a thermosetting resin (a binder) such as a phenol resin that binds the filler. Friction members having the following have been used. The fibrous potassium titanate does not damage the rotor (counterpart) and has excellent friction characteristics, but the average fiber diameter is 0.1 μm to 0.5 μm and the average fiber length is 10 μm to 20 μm. Many contain WHO fibers (fibrous particles having a major axis of 5 μm or more, a minor axis of 3 μm or less, and an aspect ratio of 3 or more) specified by the World Health Organization (WHO). Therefore, as a substitute, non-fibrous (plate-like, column-like, shape having a plurality of convex portions, etc.) titanic acid which can achieve the required characteristics as a friction material while avoiding health and safety concerns. Salt compounds have been proposed and used.

  In the composition used for the friction material (friction material composition), copper fibers and copper powder are further compounded for improving abrasion resistance. This is because, when friction occurs between the friction material and the rotor (partner material), an adhesive film is formed on the rotor surface due to the ductility of copper, and this adhesive film acts as a protective film, thereby achieving a high friction coefficient at high temperatures. It is thought that it can maintain. However, copper-containing friction materials contain copper in wear powder generated during braking, and it has been suggested that this may cause rivers, lakes, marine pollution, etc. Was to be done. Therefore, in order to contain no copper component or to reduce the content of the copper component, a friction material composition containing lithium potassium titanate and graphite (Patent Document 1), two or more types of titanate compounds and ceramic fibers Material (Patent Document 2), a friction material composition containing a titanate compound having a tunnel-like crystal structure and a titanate compound having a layered crystal structure (Patent Document 3), a plurality of convex portions A friction material composition containing a titanate compound having the following formula and a biosoluble inorganic fiber has been proposed (Patent Document 4).

  On the other hand, as a conventional friction material manufacturing process, a method of heating and pressing a friction material composition obtained by dry-mixing a phenol resin, a filler, and a curing agent to obtain a cured body is performed. ing. However, the required characteristics of friction materials are becoming stricter every day. In order to improve the mechanical properties, moldability, friction characteristics, etc. of the friction materials, thermosetting properties in which fillers are dispersed in thermosetting resin It has been proposed to heat mold a friction material composition obtained using a resin composition. For example, Patent Document 5 discloses that the use of a phenol resin composition containing a filler, a phenol resin, and a curing agent improves wear resistance. Patent Document 6 discloses that use of a phenol resin composition containing potassium titanate, an uncrosslinked rubber, a phenol resin, and a curing agent improves mechanical properties at high temperatures. Patent Document 7 discloses that use of a phenol resin composition obtained by dispersing a titanate compound in a phenol resin containing no curing agent improves moldability and abrasion resistance. .

WO 2012/066968 pamphlet JP 2015-59143 A JP 2015-147913 A JP 2013-76058 A JP 2007-126600A JP 2011-105864 A JP 2014-189612 A

  However, when the friction material composition containing the thermosetting resin composition disclosed in Patent Documents 5 to 7 does not contain a copper component or has a low content of a copper component, the molded product swells or cracks after heat molding. (Cracks) are liable to occur, and the yield of heat molding is deteriorated.

  An object of the present invention is to provide a friction material composition having excellent heat molding yield even when the copper component is not contained or the content of the copper component is reduced, and a friction material using the friction material composition and It is to provide a friction member.

  The present inventors have conducted intensive studies and found that, even when no copper component is contained or the content of the copper component is reduced, a thermosetting resin composition containing a titanate compound and a thermosetting resin It has been found that the above problem can be solved by using a friction material composition containing barium sulfate having a specific particle diameter and the present invention, and the present invention has been completed.

  That is, the present invention provides the following friction material composition, friction material, and friction member.

Item 1. In a friction material composition comprising a thermosetting resin composition containing a titanate compound and a thermosetting resin, and barium sulfate, a volume-based cumulative 50% particle diameter (D ₅₀ ) of barium sulfate is used. Is 0.1 μm to 20 μm, and the content of a copper component is 0.5% by mass or less as a copper element in a total amount of 100% by mass of the friction material composition, wherein the friction material composition is .

Item 2 The friction material composition according to Item 1, wherein the barium sulfate has a volume-based cumulative 90% particle diameter (D ₉₀ ) of 0.1 μm to 20 μm.

  Item 3. The friction material composition according to Item 1 or 2, wherein the thermosetting resin is a phenol resin.

  Item 4 The friction material according to any one of Items 1 to 3, wherein the thermosetting resin composition is obtained by dispersing a titanate compound in a thermosetting resin before curing. Composition.

  Item 5. The friction material according to any one of Items 1 to 4, wherein the thermosetting resin composition is obtained by mixing a titanate compound with a liquid thermosetting resin. Composition.

  Item 6: The thermosetting resin composition according to any one of Items 1 to 4, wherein the thermosetting resin composition is obtained by mixing a titanate compound with a liquid thermosetting resin containing no curing agent. 3. The friction material composition according to item 1.

  Item 7 The friction material composition according to Item 5 or 6, wherein the titanate compound is non-fibrous particles.

Item 8 The friction material composition according to any one of Items 5 to 7, wherein the volume-based cumulative 50% particle diameter (D ₅₀ ) of the titanate compound is 0.1 μm to 150 μm. object.

Claim 9 wherein the titanate _{compound, A 2 Ti n O (2n} + 1) wherein, A is one or more alkali metals except Li, n is the number of 4 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 except Li, and M is Li, Mg, Zn, Ga , Ni, Cu, Fe, Al, Mn, z is an integer of 1 to 3 in the valence of the element M, 0.05 ≦ x ≦ 0.5, 0 ≦ y ≦ (4 -z) _{x], a x M y Ti (2} -y) O 4 wherein, a is one or more alkali metals except Li, M is Li, Mg, Zn, Ga, Ni, Cu , Fe, Al, 1 or 2 or more selected from Mn, x is 0.5 to 1.0, y is the number of 0.25 to _{1.0], a 0.5~0.7} Li _{0. 7} Ti _1.73 O _3.85~3.95 wherein, A is one or more alkali metals except _{Li], A} 0.2~0.7 _Mg 0.40 _{Ti 1.6} O _{3.7 to 3.95} wherein, a is one or more alkali metals except _{Li], a 0.5~0.7 Li (0.27-x} ) M y Ti (1.73 _{-Z )} O _{3.85 to 3.95} [where A is one or more of alkali metals except Li, and M is selected from Mg, Zn, Ga, Ni, Cu, Fe, Al and Mn. One or more kinds (however, in the case of two or more kinds, excluding combinations of ions having different valences), x and z are x = 2y / 3 and z = y / 3 when M is a divalent metal. , M is a trivalent metal, x = y / 3, z = 2y / 3, and y is 0.004 ≦ y ≦ 0.4]. And characterized in that the friction material composition according to any one of claim 1 to claim 8.

  Item 10: The content of Item 1 to Item 9, wherein the content of the titanate compound is 10% by mass to 90% by mass with respect to 100% by mass of the total amount of the thermosetting resin composition. The friction material composition according to any one of the preceding claims.

  Item 11: The content of Item 1 to Item 10, wherein the content of the thermosetting resin composition is 1% by mass to 50% by mass with respect to 100% by mass of the total amount of the friction material composition. The friction material composition according to any one of the preceding claims.

  Item 12 The content according to any one of Items 1 to 11, wherein the content of the barium sulfate is 1% by mass to 50% by mass with respect to 100% by mass of the total amount of the friction material composition. 3. The friction material composition according to item 1.

  Item 13 The friction material composition according to any one of Items 1 to 12, further comprising a curing agent.

  Item 14 A friction material, which is a molded article of the friction material composition according to any one of Items 1 to 13.

  Item 15 A friction member comprising the friction material according to Item 14.

  The friction material composition of the present invention has excellent heat molding yield even when the copper component is not contained or the content of the copper component is reduced.

  Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are merely examples. The present invention is not at all limited to the following embodiments.

<Friction material composition>
The friction material composition of the present invention comprises a thermosetting resin composition containing a titanate compound and a thermosetting resin, and barium sulfate. The particle size (D ₅₀ ) is 0.1 μm to 20 μm, and the content of copper component is 0.5% by mass or less as a copper element in the total amount of 100% by mass of the friction material composition. Other materials may be further contained according to the requirements.

  When the total amount of the friction material composition is 100% by mass, the content of the copper component is 0.5% by mass or less as a copper element, and preferably the copper component is not contained. Can be reduced. In the present invention, “containing no copper component” means that any of copper fiber, copper powder, copper-containing alloy (such as brass or bronze) and a compound is blended as a raw material of the friction material composition. Not that.

(Thermosetting resin composition)
The thermosetting resin composition used in the present invention is characterized by containing a titanate compound and a thermosetting resin, wherein the titanate compound is dispersed in the thermosetting resin before curing. preferable.

  It is preferable that the thermosetting resin before curing contains no curing agent. When a curing agent is contained, the thermosetting resin may be cured when the thermosetting resin is heated and melted to mix the titanate compound. However, the present invention is not limited to this, and the thermosetting resin before curing may include a curing agent.

  The thermosetting resin is a liquid, semi-solid or solid at room temperature, and is made of a substance having a relatively low molecular weight that exhibits fluidity at room temperature or under heating. This substance means a resin capable of causing a chemical reaction such as a curing reaction or a cross-linking reaction by the action of a curing agent or heat to form a network-like three-dimensional structure while increasing the molecular weight to become insoluble and infusible. In addition, in this specification, in order to distinguish from the thermosetting resin (cured body) after thermosetting, it may be called the thermosetting resin before hardening.

  The thermosetting resin composition can be obtained, for example, by mixing and dispersing a titanate compound in a liquid thermosetting resin, and adding a titanate compound to a liquid thermosetting resin containing no curing agent. Are preferably obtained by mixing and dispersing. The method of mixing and dispersing the titanate compound in the liquid thermosetting resin is not particularly limited. For example, (1) the thermosetting resin is heated and melted, and the molten thermosetting resin and titanium are mixed. (2) a method of polymerizing a thermosetting resin material monomer in the presence of a titanate compound, (3) a method of dissolving a thermosetting resin in a solvent, and adding a titanate compound to the solution. A method of mixing and the like can be mentioned. Among these, the method (1) is particularly preferable. Specifically, a method of adding and mixing a titanate compound to a molten thermosetting resin, a method of adding and mixing a molten thermosetting resin to a titanate compound, a method of mixing a thermosetting resin and titanic acid A method in which each of the crushed salt compounds is dry-mixed and then heated to melt the thermosetting resin.The thermosetting resin and the titanate compound are simultaneously crushed and dry-mixed, and then heated to form a thermosetting resin. For example, a method of melting can be exemplified. As the temperature for heating and melting the thermosetting resin, a temperature at which the thermosetting resin has fluidity can be appropriately selected. A known means for heating and melting the thermosetting resin can be appropriately selected, and for example, melt kneading can be used.

  As the thermosetting resin, any one of known thermosetting resins can be appropriately selected and used, for example, phenol resin, formaldehyde resin, melamine resin, epoxy resin, acrylic resin, aromatic polyester Resin, urea resin and the like can be mentioned. Of these, phenol resins are preferred.

  A phenolic resin can be obtained by reacting a phenolic compound with an aldehyde in the presence of a basic catalyst and a resol-type phenolic resin obtained by reacting a phenol with an aldehyde in the presence of an acidic catalyst. A novolak type phenol resin can be exemplified, but a novolak type phenol resin is preferable from the viewpoint of mechanical strength and heat resistance.

  Examples of phenols include monohydric phenols such as phenol, o-, m- or p-cresol, xylenol, p-tert-butylphenol, α-naphthol, β-naphthol, p-phenylphenol; catechol, resorcinol, Divalent phenols such as 4,4'-dihydroxydiphenylmethane (bisphenol F) and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A); trivalent or higher polyvalent such as trisphenol compounds and tetraphenol compounds Phenols; and the like. These can be used alone or in combination of two or more. Preferably, monohydric phenols can be used.

  Examples of the aldehydes include monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, caproaldehyde, benzaldehyde, phenylacetaldehyde, o-tolualdehyde, and dialdehydes such as glyoxal. These can be used alone or in combination of two or more. Preferably, monoaldehydes can be used.

  The reaction molar ratio [F / P] when reacting the phenol (P) and the aldehyde (F) is not particularly limited, but is preferably 0.5 to 0.9.

  By setting the reaction molar ratio [F / P] within the above range, a novolak-type phenol resin having a suitable molecular weight can be synthesized without gelling the resin during the reaction. If the reaction molar ratio [F / P] is less than the above lower limit, the amount of unreacted phenols contained in the resulting novolak-type phenol resin may increase. When the reaction molar ratio [F / P] exceeds the upper limit, the novolak-type phenol resin may gel depending on the reaction conditions.

  Examples of the acidic catalyst include, but are not particularly limited to, organic acids such as oxalic acid; mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; p-toluenesulfonic acid; The amount of the acidic catalyst used is not particularly limited, but the reaction molar ratio [A / P] when reacting the phenol (P) with the catalyst (A) is preferably 0.001 to 0.2. . More preferably, it is 0.005 to 0.1.

  In a curing reaction of a novolak phenol resin as an example of a thermosetting resin, for example, hexamethylenetetramine used as a curing agent is bonded to a hydroxyl group in the novolak phenol resin by opening a ring to initiate a curing reaction. However, at this time, if an alkali metal ion is present, an ion exchange reaction occurs with hydrogen ions in the hydroxyl group of the novolak type phenol resin, and the bond between hexamethylenetetramine (curing agent) and the novolak type phenol resin (thermosetting resin). (Hardening inhibition). Therefore, when a titanate compound having a high alkali metal ion elution rate is added to the friction material composition, the wear resistance can be increased, but the friction material may be deteriorated. However, when the titanate compound having a high alkali metal ion elution rate is dispersed in the thermosetting resin before curing, the deterioration of the friction material can be further suppressed.

  Further, when the alkali metal ion elution rate of the titanate compound is small, deterioration of the friction material can be further suppressed, but good wear resistance may not be obtained in some cases. However, when the titanate compound having a low alkali metal ion elution rate is dispersed in the thermosetting resin before curing, the wear resistance can be further improved.

  The alkali metal ion elution rate of the titanate compound is preferably 0.01% by mass to 4.5% by mass, more preferably 0.01% by mass to 4% by mass, and still more preferably 0.01% by mass to 3% by mass. % By mass.

  In the present invention, the alkali metal ion elution rate refers to a mass ratio of alkali metal ions eluted from water in a water at 80 ° C. from a titanate compound.

Examples of the titanate compound include titanate compounds of one or more elements selected from the group of alkali metals except Li (hereinafter, these are collectively abbreviated as “element A”). . Such a titanate compound has a crystal structure such as a layered structure in which TiO ₆ octahedron and TiO ₅ triangular bipyramid are linked while sharing a twill line, and a tunnel structure. The ions of the element A are coordinated between layers having a layered structure or in a tunnel having a tunnel structure. In addition to ions of the A element, ions of alkaline earth metals may be coordinated between layers having a layered structure or in a tunnel having a tunnel structure.

  Examples of the element A include Na, K, Rb, Cs, and Fr, and Na and K are preferable. Note that Li is not included in the A element because it has a property in which the ionic radius is small and different from other alkali metals. Examples of the alkaline earth metal include Ca, Sr, Ba, and Ra.

In the titanate compound, a part of the Ti site is one or more selected from Li, Mg, Zn, Ga, Ni, Cu, Fe, Al, and Mn (hereinafter, these are collectively referred to as “M element”). Abbreviated). The element M is preferably Li, Mg, Zn, Ga, Ni, Fe, Al, or Mn from the viewpoint of the environment. In addition, from the viewpoint of further increasing the friction characteristics, Li and Mg are more preferable. Since the ions of the M element have the same ionic radius as that of Ti ⁴⁺ , it is possible to replace Ti with the M element.

The titanate compounds, e.g., wherein, A is one or more alkali metals except Li, n is a number from 4 to 11] general formula _{A 2 Ti n O (2n +} 1), A ( _{2 + y)} Ti _(6-x) M _x O _{(13 + y / 2- (4-z) x / 2) wherein} A is one or more alkali metals except Li, M is Li, Mg, One or more selected from Zn, Ga, Ni, Cu, Fe, Al, and Mn, z is a valence of element M and is an integer of 1 to 3, 0.05 ≦ x ≦ 0.5, 0 ≦ y ≤ (4-z) x] and the like.

In general formula _{A x M y Ti (2-} y) O 4 wherein, A is one or more alkali metals except Li, M is Li, Mg, Zn, Ga, Ni, Cu, One or more selected from Fe, Al and Mn, x is 0.5 to 1.0, y is 0.25 to 1.0], A _{0.5 to 0.7} Li _0.27 Ti _1.73 O _{3.85 to 3.95} [where A is one or more alkali metals except Li], A _{0.2 to 0.7} Mg _0.40 Ti _1.6 O _{3 .7～3.95} wherein, a is one or more alkali metals except _{Li], a 0.5~0.7 Li (0.27-x} ) M y Ti (1.73- _z) O _{3.85 to 3.95} [where A is one or more of alkali metals except Li, and M is Mg, Zn, Ga, Ni, Cu, Fe, Al, Mn One or more selected types (excluding combinations of ions having different valences in the case of two or more types), x and z are x = 2y / 3 and z = y when M is a divalent metal. / 3, when M is a trivalent metal, x = y / 3, z = 2y / 3, and y is 0.004 ≦ y ≦ 0.4]. No.

It is preferable that the titanate compound has a composition not containing a copper element from the viewpoint of the environment. Such titanate compounds, for _{example, A 2 Ti n O (2n} + 1) wherein, A is one or more alkali metals except Li, n is the number of 4 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 except Li, M is Li, Mg, One or more selected from Zn, Ga, Ni, Fe, Al and Mn, z is a valence of element M and is an integer of 1 to 3, 0.05 ≦ x ≦ 0.5, 0 ≦ y ≦ ( 4-z) _{x], a x M y Ti (2} -y) O 4 wherein, a is one or more alkali metals except Li, M is Li, Mg, Zn, Ga, Ni, One or more selected from Fe, Al, and Mn, x is 0.5 to 1.0, y is 0.25 to 1.0], A _{0.5 to 0.7} Li _{0 .27} Ti _1.73 O _{3.85 to 3.95} wherein, A is one or more alkali metals except _{Li], A} 0.2~0.7 _Mg 0.40 _{Ti 1.6} O _{from 3.7 to 3.95} wherein, a is one or more alkali metals except _{Li], a 0.5~0.7 Li (0.27-x} ) M y Ti (1. _73-z) O _{3.85 to 3.95} [where A is one or more of alkali metals except Li, and M is 1 selected from Mg, Zn, Ga, Ni, Fe, Al and Mn. Species or two or more (however, in the case of two or more, combinations of ions having different valences are excluded), x and z are such that when M is a divalent metal, x = 2y / 3, z = y / 3, When M is a trivalent metal, it is preferable that x = y / 3, z = 2y / 3, and y is at least one selected from 0.004 ≦ y ≦ 0.4]. .

Specific examples of the titanate compound include K ₂ Ti _4.8 O _10.6 (4.8 potassium titanate), K ₂ Ti ₆ O ₁₃ (potassium hexatitanate), 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 (potassium octa titanate), K ₂ Ti _10.9 O _22.8 (10.9 potassium titanate), Na ₂ Ti ₆ O ₁₃ (sodium hexatitanate), Na ₂ Ti ₈ O ₁₇ (sodium _octa titanate), K _0.8 Li _0.27 Ti _1.73 O ₄ (lithium potassium titanate), K _2.15 Ti _5.85 Al _0.15 O _13.0 (potassium aluminum titanate), K _2.20 Ti _5.60 Al _0.40 O _12.9 (titanium Acid aluminum Um _{potassium), K 2.21 Ti 5.90 Li 0.10} O 12.9 ( lithium potassium _{titanate), K 0.8 Li 0.27 Ti 1.73} O 4 ( lithium potassium titanate), _{K 0 .7} Li _0.27 Ti _1.73 O _3.95 (potassium lithium _{titanate), K 0.8 Mg 0.4 Ti 1.6} O 4 ( magnesium potassium _titanate), K 0.7 _{Mg 0.4} Ti _1.6 O _3.95 (potassium magnesium _{titanate), K 0.7 Li 0.13 Mg 0.2} Ti 1.67 O 3.95 ( potassium lithium titanate _magnesium), K 0.7 _{Li 0. 24} Mg _0.04 Ti _1.72 O _3.95 (lithium magnesium potassium _{titanate), K 0.7 Li 0.13 Fe 0.4} Ti 1.47 O 3.95 ( titanate Lithium iron potassium), and the like.

  The crystal structure of the titanate compound is preferably a tunnel structure from the viewpoint of further lowering the alkali metal ion elution rate, and the crystal structure is a layer structure from the viewpoint of further increasing the wear resistance in a high temperature region. Is preferred.

  In the present invention, when the alkali metal ion elution rate is within the above range, one or more of the titanate compounds can be appropriately selected according to the characteristics of the intended friction material. Further, a titanate compound having a tunnel structure and a titanate compound having a layered structure may be used in combination.

  The titanate compound has a spherical shape (including a surface having some irregularities, but also having a substantially spherical shape such as an elliptical cross section), a columnar shape (a rod shape, a cylindrical shape, a prismatic shape, a strip shape, a substantially cylindrical shape, Non-standard shapes such as a generally rectangular shape, including a substantially columnar shape), a plate shape, a block shape, a shape having a plurality of convex portions (amoeba shape, boomerang shape, cruciform shape, confetti shape, etc.), an irregular shape, etc. Fibrous particles are preferable, and among these, particles having a columnar shape or a particle shape having a plurality of convex portions are preferable from the viewpoint of further increasing the friction material strength in a high temperature range. The titanate compound is a porous material such as a particle in which a plurality of columnar particles are irregularly oriented and integrated, and a particle in which crystal grains of the titanate compound are bonded by sintering and / or fusion. The particles may be shaped like particles. These various particle shapes can be arbitrarily controlled by production conditions, in particular, raw material composition, firing conditions, and the like. Further, the particle shape can be analyzed by, for example, observation with a scanning electron microscope (SEM).

  In the present invention, the term “non-fibrous particles” refers to the longest major axis L of the rectangular parallelepiped having the smallest volume (circumscribed rectangular parallelepiped) among the rectangular parallelepipeds circumscribed by the particles, the next longest side to the minor axis B, and the shortest side to the thickest side. As T (B> T), L / B refers to particles having a particle size of less than 5. Further, “having a plurality of convex portions” means that the projected shape on a plane can take a shape having convex portions in two or more directions unlike at least a normal polygon, circle, ellipse, or the like. Specifically, the convex portion refers to a portion corresponding to a portion protruding from a polygon (a circle, an ellipse, or the like (basic figure) applied to a photograph (projection diagram) by a scanning electron microscope (SEM). .

  The porous particles preferably have a cumulative pore volume of 5% or more, preferably 10% or more, more preferably 15% or more, with a pore diameter in the range of 0.01 μm to 1.0 μm. It is preferably at most 40%, more preferably at most 30%. The cumulative pore volume can be measured by a mercury porosimetry.

  As a method for producing the porous titanate compound particles, for example, the production methods described in WO2016 / 063688 and WO2017 / 051690 can be used. Further, the powder obtained from these production methods can be used after being pulverized.

The volume-based cumulative 50% particle diameter (D ₅₀ ) of the titanate compound is, for example, 0.1 μm to 150 μm, preferably 0.3 μm to 100 μm, and more preferably 0.5 μm to 50 μm. When the volume-based cumulative 50% particle diameter (D ₅₀ ) is within the above range, the friction characteristics of the friction material can be further enhanced. The titanate compounds include those forming secondary particles due to difficulty in monodispersed primary particles, and granulated products obtained by granulating the secondary particles.

The term “volume-based cumulative 50% particle size (D ₅₀ )” refers to the particle size at a volume-based cumulative 50% in the particle size distribution measured by a laser diffraction method. This D ₅₀ is obtained by calculating the particle size distribution on a volume basis, counting the number of particles from the smaller particle size in the cumulative curve with the total volume being 100%, and calculating the particle size at the point where the cumulative value becomes 50%. is there.

Similarly, the volume-based cumulative 10% particle size (D ₁₀ ) and the volume-based cumulative 90% particle size (D ₉₀ ) are calculated from the smaller particle size in the cumulative curve in which the total volume of the obtained particle size distribution is 100%. The number of particles is counted, and the particle diameter at the point where the accumulated value becomes 10% and 90%, respectively, is shown. Therefore, the ratio (D ₉₀ / D ₁₀ ) between D ₉₀ and D ₁₀ can be regarded as an index indicating the breadth of the particle size distribution. As the value of D ₉₀ / _{D 10} is large, it has a broad particle size distribution. Further, as the value of D ₉₀ / D ₁₀ is closer to 1, the particle size distribution is closer to monodispersion.

The volume-based cumulative 90% particle diameter (D ₉₀ ) of the titanate compound is preferably from 0.1 μm to 150 μm, more preferably from 0.3 μm to 100 μm, and preferably from 0.5 μm to 50 μm. More preferred. The D ₉₀ Within the above range, the friction characteristics of the friction material can be further enhanced.

Titanate _compounds, the value of D 90 _{/ D 10} is, for example, 30 or less, preferably in the range of 1 to 15. When the value of D ₉₀ / D ₁₀ is within the above range, the friction characteristics of the friction material can be further enhanced.

The specific surface area of the titanium salt compound ^is preferably 0.3m ² / g~10m 2 / ^g, more preferably ^{0.5m 2 / g~9m 2 / g,} 0.5m 2 / g More preferably, it is で³ m ² / g. The specific surface area can be measured according to JIS Z8830. If the specific surface area is too large, the wet area with the thermosetting resin may be too large, and the amount of the thermosetting resin that contributes to the strength of the entire friction material may be reduced.

  The titanate compound used in the present invention has a treatment layer comprising a surface treatment agent on the surface of the titanate compound for the purpose of further improving dispersibility and further improving adhesion with the thermosetting resin. It may be formed.

  Examples of the surface treatment agent include a silane coupling agent and a titanium coupling agent. Among these, a silane coupling agent is preferable, and an amino silane coupling agent, an epoxy silane coupling agent, and an alkyl silane coupling agent are more preferable. One of the above surface treatment agents may be used alone, or two or more thereof may be used in combination.

  Examples of the amino-based silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Methoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2 -Aminoethyl-3-aminopropyltrimethoxysilane and the like.

  Examples of the epoxy-based silane coupling agent include 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, triethoxy (3-glycidyloxypropyl) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

  Examples of the alkyl-based silane coupling agent include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane , N-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane and the like.

  As a method of forming a treatment layer comprising a surface treatment agent on the surface of the titanate compound, a known surface treatment method can be used. For example, a solvent that promotes hydrolysis (for example, water, alcohol, or a mixture thereof). A solution is prepared by dissolving the surface treating agent in a mixed solvent) and spraying the solution onto the titanate compound.

  The amount of the surface treatment agent when the surface treatment agent is treated on the surface of the titanate compound used in the present invention is not particularly limited, but in the case of a wet method, for example, based on 100 parts by mass of the titanate compound The solution of the surface treatment agent may be sprayed so that the surface treatment agent is 0.1 to 20 parts by mass.

  The content of the titanate compound in the thermosetting resin composition used in the present invention is preferably in the range of 10% by mass to 90% by mass with respect to 100% by mass of the total of the thermosetting resin composition. The upper limit of the titanate compound is preferably 90% by mass, more preferably 80% by mass, and even more preferably 70% by mass. The lower limit of the titanate compound is preferably 10% by mass, more preferably 20% by mass, and still more preferably 30% by mass.

  In the thermosetting resin composition used in the present invention, as long as the preferable physical properties are not impaired, conventionally, a friction material generally contains one or more additives such as a fiber base material and an additive used as a friction modifier. They can be combined and combined. These can be blended according to the friction characteristics required for the product, for example, the friction coefficient, abrasion resistance, vibration characteristics, squeal characteristics and the like.

As the fiber base material, aromatic polyamide (aramid) fiber, fibrillated aramid fiber, acrylic fiber (fiber of a homopolymer or copolymer whose main raw material is acrylonitrile), fibrillated acrylic fiber, cellulose fiber, fibrillated Organic fibers such as cellulose fibers and phenolic resin fibers; mainly metals such as aluminum, iron, zinc, tin, titanium, nickel, magnesium, silicon and other metals other than copper and copper alloys, or fibers in the form of alloys and cast iron fibers metal fibers of straight shape or curled shape and; glass fiber, rock wool, ceramic fibers, biodegradable ceramic fibers, biodegradable mineral fibers, (such as SiO ₂ -CaO-SrO-based fiber) biosoluble fibers, Warasuto Inorganic fibers other than titanate fibers such as knit fibers, silicate fibers, and mineral fibers; , PAN-based carbon fibers, pitch-based carbon fibers, carbon fibers such as activated carbon fiber; and the like. One of these may be used alone, or two or more may be used in combination.

  Non-vulcanized or vulcanized rubber powders such as tire rubber, acrylic rubber, isoprene rubber, NBR (nitrile butadiene rubber), SBR (styrene butadiene rubber), chlorinated butyl rubber, butyl rubber, silicone rubber; cashew dust; Organic fillers such as melamine dust; inorganic powders such as calcium carbonate, sodium carbonate, lithium carbonate, calcium hydroxide (hydrated lime), vermiculite, clay, mica, talc, dolomite, chromite, mullite; aluminum, zinc, iron, tin, etc. Inorganic fillers such as metal powders in the form of simple metals or alloys other than copper and copper alloys; silicon carbide (silicon carbide), titanium oxide, alumina (aluminum oxide), silica (silicon dioxide), magnesia (magnesium oxide), Zirconia (zirconium oxide Abrasives such as zirconium silicate, chromium oxide, iron oxide (triiron tetroxide), chromite, quartz, etc .; synthetic or natural graphite (graphite), phosphate-coated graphite, carbon black, coke, antimony trisulfide, And solid lubricants such as molybdenum sulfide, tin sulfide, iron sulfide, zinc sulfide, bismuth sulfide, tungsten disulfide, and polytetrafluoroethylene (PTFE).

  By curing the friction material composition containing the thermosetting resin composition used in the present invention, a friction material having excellent wear resistance can be obtained. Although the reason is not clear, the wear resistance is improved by dispersing the titanate compound more uniformly in the friction material than in the conventional method, and the metal titanate compound is present in the thermosetting resin. Thus, it is considered that the wear resistance is also improved while the curing inhibition of the thermosetting resin is suppressed.

  The content of the thermosetting resin composition in the friction material composition is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, based on 100% by mass of the total amount of the friction material composition. %, More preferably 4 to 30% by mass. By setting the content of the thermosetting resin composition within the above range, the gap between the compounding materials is filled with an appropriate amount of the binder, and more excellent friction characteristics can be obtained.

(Barium sulfate)
The barium sulfate used in the present invention has a volume-based cumulative 50% particle diameter (D ₅₀ ) of 0.1 μm to 20 μm, preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5 μm. , 0.5 μm to 3 μm. Barium sulfate also includes those forming secondary particles due to the difficulty of monodispersing the primary particles, and granulated products of the secondary particles.

In the friction material composition, if the copper component is not contained or the content of the copper component is small, swelling or cracking (crack) is likely to occur in the molded article after the heat molding, and the yield by the heat molding is deteriorated. This is considered to be due to the absence of copper having excellent thermal conductivity. However, contrary to expectation, the friction material composition of the present invention uses barium sulfate having a small volume-based cumulative 50% particle diameter (D ₅₀ ) without containing copper having excellent thermal conductivity. The yield rate of thermoforming of the friction material composition is superior to the case where copper is contained.

The volume-based cumulative 90% particle diameter (D ₉₀ ) of barium sulfate used in the present invention is preferably 0.1 μm to 20 μm, more preferably 0.1 μm to 10 μm, and more preferably 1 μm to 5 μm. More preferred. The amount of the D ₉₀ coarse particles in the barium sulfate by the above-mentioned range is reduced, further it is possible to further improve the yield by thermoforming.

The barium sulfate used in the present invention has a value of D ₉₀ / D ₁₀ of, for example, 20 or less, preferably 1 to 15, more preferably 1 to 10. When the value of D ₉₀ / D ₁₀ is within the above range, the friction characteristics of the friction material can be further improved.

  Barium sulfate includes barium sulfate (barite powder) obtained by pulverizing a mineral called barite, removing iron, washing and elutriation, and precipitated barium sulfate synthesized artificially. The size of the precipitated barium sulfate can be controlled by the conditions at the time of synthesis, and fine barium sulfate having a small content of the target coarse particles can be produced. From the viewpoint of further reducing impurities and making the particle size distribution of barium sulfate more uniform, it is preferable to use sedimentable barium sulfate.

  The content of barium sulfate is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, and more preferably 15% by mass, based on 100% by mass of the total amount of the friction material composition. The content is more preferably from 30 to 45% by mass, and particularly preferably from 30 to 45% by mass. By setting the content of barium sulfate within the above range, more excellent friction characteristics can be obtained.

  The mass ratio of barium sulfate to the thermosetting resin (barium sulfate / thermosetting resin) is preferably 30/70 or more, more preferably 50/50 or more, and 90/10 or less. Is preferred.

(Other materials)
In addition to the thermosetting resin composition and barium sulfate, a curing agent and other materials can be added to the friction material composition of the present invention, if necessary.

  As the curing agent, when the thermosetting resin contained in the thermosetting resin composition is a novolak-type phenol resin, hexamethylenetetramine can be used. The amount of hexamethylenetetramine used is not particularly limited, but is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the novolak-type phenol resin. By setting the use amount of hexamethylenetetramine in the above range, a cured product having more excellent mechanical strength and abrasion resistance can be obtained. Before obtaining the cured material, the particle size of the friction material composition of the present invention may be adjusted by pulverization, granulation, or the like according to the intended use.

  Examples of other materials include the following thermosetting resins, fiber base materials, friction modifiers, and the like.

  The thermosetting resin is used as a binder that integrates each component of the friction material composition and gives strength. Therefore, any one of known thermosetting resins used as a binder can be appropriately selected and used.

  Examples of the thermosetting resin include a phenol resin; an elastomer-dispersed phenol resin such as an acrylic elastomer-dispersed phenol resin and a silicone elastomer-dispersed phenol resin; a modified phenol resin such as an acrylic-modified phenol resin and a silicone-modified phenol resin; a formaldehyde resin; Epoxy resin; acrylic resin; aromatic polyester resin; urea resin; One of these can be used alone or in combination of two or more. Among them, a phenol resin (straight phenol resin) and a modified phenol resin are preferable because heat resistance, moldability, and friction characteristics can be further improved.

As the fiber base material, aromatic polyamide (aramid) fiber, fibrillated aramid fiber, acrylic fiber (fiber of a homopolymer or copolymer whose main raw material is acrylonitrile), fibrillated acrylic fiber, cellulose fiber, fibrillated Organic fibers such as cellulose fibers and phenolic resin fibers; mainly metals such as aluminum, iron, zinc, tin, titanium, nickel, magnesium, silicon and other metals other than copper and copper alloys, or fibers in the form of alloys and cast iron fibers metal fibers of straight shape or curled shape and; glass fiber, rock wool, ceramic fibers, biodegradable ceramic fibers, biodegradable mineral fibers, (such as SiO ₂ -CaO-SrO-based fiber) biosoluble fibers, Warasuto Inorganic fibers other than titanate fibers such as knit fibers, silicate fibers, and mineral fibers; , PAN-based carbon fibers, pitch-based carbon fibers, carbon fibers such as activated carbon fiber; and the like. One of these may be used alone, or two or more may be used in combination.

  Non-vulcanized or vulcanized rubber powders such as tire rubber, acrylic rubber, isoprene rubber, NBR (nitrile butadiene rubber), SBR (styrene butadiene rubber), chlorinated butyl rubber, butyl rubber, silicone rubber; cashew dust; Organic fillers such as melamine dust; titanate compounds such as potassium titanate, sodium titanate, lithium potassium titanate, magnesium potassium titanate, calcium carbonate, sodium carbonate, lithium carbonate, calcium hydroxide (hydrated lime), vermiculite, Inorganic powders such as clay, mica, talc, dolomite, chromite, and mullite; inorganic fillers such as metal powders in the form of simple metals or alloys other than copper and copper alloys such as aluminum, zinc, iron, and tin; silicon carbide (carbonized) Silicon), titanium oxide, Abrasives such as lumina (aluminum oxide), silica (silicon dioxide), magnesia (magnesium oxide), zirconia (zirconium oxide), zirconium silicate, chromium oxide, iron oxide (triiron tetroxide, etc.), chromite, quartz, etc .; Or natural graphite (graphite), phosphate-coated graphite, carbon black, coke, antimony trisulfide, molybdenum disulfide, tin sulfide, iron sulfide, zinc sulfide, bismuth sulfide, tungsten disulfide, polytetrafluoroethylene (PTFE), etc. Solid lubricant; and the like. One of these may be used alone, or two or more may be used in combination.

  The content of other materials in the friction material composition is preferably 20% by mass to 90% by mass with respect to 100% by mass of the total amount of the friction material composition.

(Method for producing friction material composition)
The friction material composition of the present invention is prepared by mixing the components with a mixer such as (1) a Reidige mixer (“Reidge” is a registered trademark), a pressure kneader, or an Eirich mixer (“Eirich” is a registered trademark). Method: (2) A method of preparing a granulated product of a desired component and mixing other components with a mixer such as a Reidige mixer, a pressure kneader, and an Erich mixer if necessary. it can.

  The content of each component of the friction material composition of the present invention can be appropriately selected depending on desired friction characteristics, and can be produced by the above production method.

  Further, the friction material composition of the present invention may be prepared by preparing a master batch containing a specific component at a high concentration, adding a thermosetting resin or the like to the master batch, and mixing.

<Friction materials and friction members>
In the present invention, the friction material composition is preliminarily molded at normal temperature (20 ° C.), and the obtained temporarily molded body is subjected to heat and pressure molding (molding pressure 10 MPa to 40 MPa, molding temperature 150 ° C. to 200 ° C.). If necessary, the obtained molded body is subjected to a heat treatment (maintained at 150 ° C. to 220 ° C. for 1 hour to 12 hours) in a heating furnace, and thereafter, the molded body is subjected to machining and polishing to obtain a predetermined A friction material having a shape can be manufactured.

  The friction material of the present invention is used as a friction member in which the friction material is formed as a friction surface. Examples of the friction member that can be formed by using a friction material include (1) a configuration including only a friction material, (2) a base material such as a backing metal, and a book provided on the base material and providing a friction surface. And the like having the friction material of the invention.

  The base material is used to further improve the mechanical strength of the friction member, and a metal or a fiber-reinforced resin or the like can be used as a material. For example, iron, stainless steel, glass fiber reinforced resin, carbon fiber reinforced resin and the like can be mentioned.

  Normally, a number of fine pores are formed inside the friction material, which serves as an escape route for decomposition products (gases and liquids) at high temperatures, preventing the deterioration of friction characteristics, and reducing the rigidity of the friction material and damping it The squealing is prevented by improving the performance. In a normal friction material, the composition of the materials and the molding conditions are controlled so that the porosity is 5% to 30%, preferably 15% to 30%. Conventional friction material compositions tend to have poor yields when heated and molded by setting the blending and molding conditions so that the porosity of the friction material is high, but the porosity can be reduced by using the friction material composition of the present invention. The yield of heat molding is excellent even if the

  Since the friction member of the present invention is constituted by the friction material composition of the present invention, even when the copper component is not contained or the content of the copper component is reduced, the friction coefficient is high, the fade rate and the wear resistance are high. Excellent in nature. Therefore, the friction member of the present invention can be suitably used for brake systems such as brake linings, disc pads, clutch facings, and the like that constitute braking devices for various vehicles, industrial machines, and the like.

  Hereinafter, the present invention will be described in more detail based on specific examples.

  The present invention is not limited to the following examples in any way, and can be implemented by appropriately changing the scope without changing the gist.

  Table 1 shows barium sulfates 1 and 2 used in Examples and Comparative Examples.

  The thermosetting resins and other additives used in Examples and Comparative Examples are as follows.

・ Phenolic resin: Novolak phenol resin powder containing hexamethylenetetramine ・ Cashew dust ・ Artificial graphite ・ Mica ・ Iron oxide ・ Zirconium silicate ・ Antimonium sulfide ・ Rock wool ・ Calcium hydroxide ・ Fibrillated aramid fiber ・ Copper fiber

(Production Example 1: Titanate compound A)
A porous titanate compound (composition: K ₂ Ti ₆ O ₁₃ , trade name: TERRACESS DP-A, manufactured by Otsuka Chemical Co., Ltd.) is dry-pulverized by a vibration mill, and the obtained pulverized material is classified by elutriation classification. Powder was obtained. It was confirmed that the particle shape of the titanate compound A thus produced was non-fibrous particles. Further, the alkali metal ion elution rate, the particle diameter, and the specific surface area were measured. Table 2 shows the results.

(Production Example 2: Composition A)
A reaction vessel equipped with a condenser and a stirrer was charged with 150 parts by mass of phenol, 71 parts by mass of 37% formalin, and then 2 parts by mass of oxalic acid dihydrate. After the temperature was gradually raised to reach 95 ° C., a reflux reaction was performed for 180 minutes. Subsequently, a dehydration reaction was performed under a reduced pressure of 30 Torr, and the mixture was heated to a temperature of 150 ° C. Thereafter, 152 parts by mass of the titanate compound A shown in Table 2 was added and the mixture was stirred in a uniform state. Subsequently, the mixture was discharged from the reaction vessel, solidified at room temperature, and pulverized in a mortar to obtain a thermosetting resin composition composed of 138 g of a novolak-type phenol resin and 152 g of a titanate compound A. To 290 parts by mass of the obtained thermosetting resin composition, 14 parts by mass of hexamethylenetetramine as a curing agent was added, and the mixture was pulverized again with a mortar to obtain composition A.

(Example 1, Comparative Examples 1 to 3)
Each material was blended according to the blending ratios shown in Table 3 and mixed for 3 minutes using an Erich mixer. The obtained mixture was pressurized at normal temperature (20 ° C.) at a pressure of 15 MPa for 5 seconds to prepare a temporary molded body. The above temporary molded body is fitted into the cavity of the heat molding mold heated to 150 ° C., and a back plate (material: steel) coated with an adhesive is placed on the temporary molded body under a pressure of 20 MPa. Pressurized for seconds. During 60 to 90 seconds measured from the start of pressurization, five gas removal processes were performed. The obtained member was placed in a constant temperature drier heated to 220 ° C., held for 2 hours, and completely cured to obtain a friction member.

<Evaluation of titanate compound and barium sulfate>
(Alkali metal ion elution rate)
The mass (X) of the test sample was measured, and the test sample was added to distilled water to prepare a 1% by mass slurry. After stirring at 80 ° C. for 4 hours, the solid content was removed with a membrane filter having a pore size of 0.2 μm. And an extract was obtained. The alkali metal (Y) of the obtained extract was measured with an ion chromatograph (manufactured by Dionex, product number “ICS-1100”). Next, using the values of the above (X) and (Y), the alkali metal ion elution rate (% by mass) was calculated based on the formula [(Y) / (X)] × 100.

(Particle shape)
The particle shape was observed with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, product number "S-4800").

(Particle size)
The particle size was measured by a laser diffraction type particle size distribution analyzer (manufactured by Shimadzu Corporation, product number “SALD-2100”).

Specifically, the particle diameter at a volume-based cumulative 50% in the particle size distribution measured by a laser diffraction type particle size distribution measuring apparatus, that is, D ₅₀ (median diameter) was determined.

Particle diameter when volume-reduced cumulative 10% in the particle size distribution measured by laser diffraction particle size distribution measuring apparatus, i.e. to determine the D _10.

The particle diameter at 90% by volume accumulation in the particle size distribution measured by a laser diffraction type particle size distribution measuring apparatus, that is, _D90 was determined.

_Further, from the ratio of the _{D 90} and _{D 10,} it was determined _D 90 _/ D _10.

(Specific surface area)
The specific surface area was measured by an automatic specific surface area measuring device (manufactured by micromeritics, product number “TriStarII3020”).

<Evaluation of friction members>
(Molding yield rate)
At the time of heat molding at 150 ° C., molding abnormalities due to swelling and cracking of the friction member after thermoforming were visually confirmed, and the ratio of the number of sheets that did not cause abnormal molding to the number of thermoformed sheets was defined as the molding yield rate.

(Porosity)
The porosity was measured according to the method of JIS D4421.

(Rockwell hardness)
Rockwell hardness was measured according to the method of JIS D4421. The hardness scale used was an S scale.

(Friction characteristics)
The surface (friction surface) of the friction member manufactured in Example 1 and Comparative Examples 1 to 3 was polished to 1.0 mm, and a brake efficiency test was performed based on JASO C406. The average friction coefficient and the first fade fade rate (%) , And the friction material wear amount and the rotor wear amount were determined. The rotor used was a cast iron rotor belonging to type A in the ASTM standard.

  First fade The fade rate was calculated by the following formula.

  First fade Fade rate (%) = (minimum friction coefficient / maximum friction coefficient) × 100

  The results are shown in Table 3 below.

Claims (15)

A thermosetting resin composition containing a titanate compound and a thermosetting resin, and a barium sulfate, in a friction material composition,
The barium sulfate has a volume-based cumulative 50% particle diameter (D ₅₀ ) of 0.1 μm to 20 μm,
A friction material composition characterized in that the content of a copper component is 0.5 mass% or less as a copper element in a total amount of 100 mass% of the friction material composition. The volume-reduced cumulative 90% particle diameter of the barium sulfate _{(D 90),} characterized in that a 0.1Myuemu～20myuemu, friction material composition according to claim 1.   The friction material composition according to claim 1, wherein the thermosetting resin is a phenol resin.   The friction material according to any one of claims 1 to 3, wherein the thermosetting resin composition is obtained by dispersing a titanate compound in a thermosetting resin before curing. Composition.   The friction material according to any one of claims 1 to 4, wherein the thermosetting resin composition is obtained by mixing a titanate compound with a liquid thermosetting resin. Composition.   The said thermosetting resin composition was obtained by mixing a titanate compound with the liquid thermosetting resin which does not contain a hardening | curing agent, The any one of Claims 1-4 characterized by the above-mentioned. 3. The friction material composition according to item 1.   The friction material composition according to claim 5, wherein the titanate compound is non-fibrous particles. Volume-based cumulative 50% particle diameter of the titanium salt compound _{(D 50),} characterized in that it is a 0.1Myuemu～150myuemu, friction material composition according to any one of claims 5 to 7 object. The titanate _{compound, A 2 Ti n O (2n} + 1) wherein, A is one or more alkali metals except Li, n is the number of 4 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 except Li, and M is Li, Mg, Zn, Ga, Ni , Cu, Fe, Al, or Mn, z is an integer of 1 to 3 in the valence of the element M, 0.05 ≦ x ≦ 0.5, 0 ≦ y ≦ (4-z ) _x], a _x M _{y Ti (in 2-y) O 4} [wherein, a is one or more alkali metals except Li, M is Li, Mg, Zn, Ga, Ni, Cu, Fe , Al, 1 or 2 or more selected from Mn, x is 0.5 to 1.0, y is the number of 0.25 to _{1.0], a 0.5 to 0.7} Li _0.27 i _1.73 O _{3.85 to 3.95} wherein, A is one or more alkali metals except _{Li], A 0.2~0.7 Mg 0.40 Ti 1.6 O} 3 _.7～3.95 wherein, a is one or more alkali metals except _{Li], a 0.5~0.7 Li (0.27-x} ) M y Ti (1.73- _z) O _{3.85 to 3.95} [where A is one or more alkali metals except Li, and M is 1 selected from Mg, Zn, Ga, Ni, Cu, Fe, Al and Mn. Species or two or more (however, in the case of two or more, excluding a combination of ions having different valences), x and z are such that when M is a divalent metal, x = 2y / 3, z = y / 3, When M is a trivalent metal, at least one compound selected from the group consisting of x = y / 3, z = 2y / 3, and y is 0.004 ≦ y ≦ 0.4] Characterized Rukoto, friction material composition according to any one of claims 1 to 8.   The content of the titanate compound is 10% by mass to 90% by mass with respect to 100% by mass of the total amount of the thermosetting resin composition. The friction material composition according to any one of the preceding claims.   The content of the thermosetting resin composition is 1% by mass to 50% by mass based on 100% by mass of the total amount of the friction material composition. The friction material composition according to any one of the preceding claims.   The content of the barium sulfate is 1% by mass to 50% by mass with respect to 100% by mass of the total amount of the friction material composition. 3. The friction material composition according to item 1.   The friction material composition according to any one of claims 1 to 12, further comprising a curing agent.   A friction material, which is a molded product of the friction material composition according to any one of claims 1 to 13.   A friction member comprising the friction material according to claim 14.