FRICTION MATERIAL

Abstract

[Object] This invention relates to a friction material used for a disc brake pad, which is manufactured by forming a non-asbestos-organic (NAO) friction material composition that contains a binder, a fiber base material, a friction modifier, a lubricant, a pH adjuster, and a filler, which satisfies requirements for the required braking effectiveness, crack resistance, and fade resistance.

[Means to Resolve] The friction material, which is made from the NAO friction material composition, which includes the binder, the fiber base material, the friction modifier, the lubricant, the pH adjuster, and the filler, where the friction modifier contains 5-30 mass % of a magnesium potassium titanate, which has the alkali elution rate of 0.1-2.5 mass %, relative to the total amount of the friction material composition. Preferably, in the friction material, the titanate is a magnesium potassium titanate, and as the friction modifier, 5-25 mass % of a zirconium oxide relative to the total amount of the friction material composition and 1-5 mass % of a fibrillated organic fiber as the fiber base material relative to the total amount of the friction material composition are contained.

Claims

1. A friction material used for a disc brake pad, which is manufactured by forming a non-asbestos-organic (NAO) friction material composition that contains a binder, a fiber base material, a friction modifier, a lubricant, a pH adjuster, and a filler, wherein said friction material composition contains 5-30 mass % of a magnesium potassium titanate, as the friction modifier, relative to the total amount of the friction material composition, where said magnesium potassium titanate has 0.1 or more mass % but 2.5 or less mass % of alkali elution rate that is a mass rate of the alkali metal and the alkali-earth metal eluted from the titanate compound in water at 80 centigrade.

2. The friction material according to claim 1, wherein alkali elution rate of said layer crystal structure magnesium potassium titanate is 0.5 mass % or more but 1.5 mass % or less.

3. The friction material according to claim 1, wherein said friction material composition contains 5-25 mass % of a zirconium oxide relative to the total amount of the friction material composition, as the friction modifier and 1-5 mass % of a fibrillated organic fiber relative to the total amount of the friction material composition, as the fiber base material.

4. The friction material according to claim 2, wherein said friction material composition contains 5-25 mass % of a zirconium oxide relative to the total amount of the friction material composition, as the friction modifier and 1-5 mass % of a fibrillated organic fiber relative to the total amount of the friction material composition, as the fiber base material.

Description

EMBODIMENTS OF THE INVENTION

[0025] In this invention, the friction material composition is used for the friction material for the disc brake pad, and the friction material is made from the non-asbestos (NAO) friction material composition, which includes the binder, the fiber base material, the friction modifier, the lubricant, the pH adjuster, and the filler, where 5-30 mass % of the layer crystal structure titanate with the alkali elution rate of 0.1 mass % or more but 2.5 mass % or less, relative to the total amount of the friction material composition.

[0026] The layer crystal structure titanate tends to form a stable film on a sliding surface of the mating member comparing with the tunnel crystal structure titanate. By adding 5-30 mass % of such layer crystal structure titanate, relative to the total amount of the friction material composition, the braking effectiveness can be improved to satisfy the required performance.

[0027] Also, using the layer crystal structure titanate with the alkali elution rate of 0.1 mass % or more but 2.5 mass % or less helps not to hinder an curing reaction of a thermosetting resin as the binder during the heat press forming, and as a result, the mechanical strength of the friction material increases and the crack resistance during the high temperature and high load braking can be improved.

More preferably the layer crystal structure titanate with the alkali elution rate of 0.5 mass % or more but 1.5 mass % or less.

[0028] As the layer crystal structure titanate, one type or a combination of two types selected from the magnesium potassium titanate and lithium potassium titanate may be used. In order to improve the fade resistance, the use of magnesium potassium titanate with high heat-resisting property alone is preferred.

[0029] Furthermore, by adding 5-25 mass % of the zirconium oxide, relative to the total amount of the friction material composition, as the friction modifier, and 1-5 mass % of the fibrillated organic fiber, relative to the total amount of the friction material composition, as the fiber base material, the fade resistance can be improved.

[0030] The zirconium oxide is characterized to cause volumetric shrinkage at high temperature and to make tetragonal phase transition.

Therefore, during the high temperature and high load braking, the zirconium oxide makes phase transition to shrink the volume, thereby tending to displace the same from the matrix.
The displaced zirconium oxide is supplied onto the friction surface, and by the grinding effect of the zirconium oxide, the frictional destruction of the layer crystal structure titanate progresses and the alkali component is released from the titanate.

[0031] Also, by adding the fibrillated organic fiber, the friction material obtains appropriate water absorbency, and atmospheric moisture tends to be absorbed inside the friction material.

The atmospheric moisture absorbed inside the friction material tends to release the alkali component of the layer crystal structure titanate.

[0032] When the layer crystal structure titanate with relatively lower alkali elution rate is used, a multiplier effect of the above-described effect, during the high temperature and high load braking, allows to supply sufficient alkali component onto the friction surface, thereby promoting the decomposition of the organic substance. As a result, the fade resistance is improved.

[0033] Using the zirconium oxide with the average particle diameter of 1.0-3.0 μm improves the frictional resistance and reduces the aggressiveness against the mating surface.

Also, the average particle diameter, measured by the laser diffraction size analyzing method, is 50% particle diameter.

[0034] As the fibrillated organic fiber, one type or any combination of two or more types of fibers selected from the aramid fiber, the cellulose fiber, and the polyacrylonitrile fiber can be used. In order to improve the crack resistance, it is preferable to use the aramid fiber alone which has a higher reinforcing effect.

[0035] The friction material of this invention includes the binder, the fiber base material, the friction modifier, the lubricant, the pH adjuster, and the filler that are generally used for the friction material in addition to the above-described layer crystal structure titanate, the zirconium oxide and the fibrillated organic fiber.

[0036] The binder may be binders that are generally used for the friction material such as a straight phenolic resin, the resin as a result of modifying the phenolic resin by a cashew oil, various elastomers such as an acryl rubber and a silicone rubber, an aralkyl modified phenolic resin obtained by reacting the phenol compound, aralkyl ethyl compound and an aldehyde compound, and a thermosetting resin obtained by dispersing such as various elastomers or fluoropolymer in the phenolic resin, one type or any combination of two or more types may be used.

[0037] The amount of the binder, for the purpose of securing the mechanical strength and wear resistance, is preferably 7-15 mass % relative to the total amount of the friction material composition but more preferably 8-12 mass % relative to the total amount of the friction material composition.

[0038] The fiber base material, in addition to the above-described fibrillated organic fiber, may be metal fibers such as a copper fiber, a bronze fiber, a brass fiber, an aluminum fiber and an aluminum alloy fiber, and one type or any combination of two or more types may be used.

[0039] When the metal fiber is used, the content of the fiber base material together with the above-described fibrillated organic fiber is 2-20 mass % relative to the total amount of the friction material composition but more preferably 3-15 mass % relative to the total amount of the friction material composition.

[0040] The inorganic friction modifier, in addition to the above-described layer crystal structure titanate and the zirconium oxide, may be a particle inorganic modifier such as the stabilized zirconium oxide, a zirconium silicate, a magnesium oxide, an α-alumina, a γ-alumina, a talc, a mica, a vermiculite, a zinc particle, a copper particle, a brass particle, an aluminum particle, an aluminum alloy particle, and a tunnel crystal structure titanate and a fiber inorganic friction modifier such as a wollastonite, a sepiolite, a basalt fiber, a grass fiber, a biosoluble ceramic fiber, and a rock wool. In this invention, one type or any combination of two or more types of the above-inorganic friction modifier may be used.

[0041] The amount of the inorganic friction modifier together with the above-described layer crystal structure titanate and the zirconium oxide is preferably 30-70 mass % relative to the total amount of the friction material composition but more preferably 40-60 mass % relative to the total amount of the friction material composition.

[0042] The organic friction modifier may be a cashew dust, a pulverized powder of a tire tread rubber, or a vulcanized rubber powder or an unvulcanized rubber powder of a nitrile rubber, an acrylic rubber, a butyl rubber, a silicone rubber and so on. In this invention, one type or any combination of two or more types of the above-organic friction modifier may be used.

[0043] The amount of the organic friction modifier contained in the friction material composition is preferably 3-8 mass % relative to the total amount of the friction material composition but more preferably 4-7 mass % relative to the total amount of the friction material composition.

[0044] The lubricant may be such as metal sulfide type lubricants such as a zinc sulfide, a molybdenum disulfide, a tin sulfide, an iron sulfide, and a composite metal sulfide and carbon type lubricants such as a synthetic graphite, a natural graphite, an exfoliated graphite, a petroleum coke, a resilient graphitic carbon, and a polyacrylonitrile oxidized fiber pulverized powder, which are normally used in the friction material. In this invention, one type or any combination of two or more types of the above-lubricants may be used.

[0045] The amount of lubricant is preferably 3-8 mass % relative to the total amount of the friction material composition but more preferably 4-6 mass % relative to the total amount of the friction material composition.

[0046] The pH adjuster, such as a calcium hydroxide, which normally used for the friction material may be used.

The amount of pH adjuster is preferably 2-6 mass % relative to the total amount of the friction material composition but more preferably 2-3 mass % relative to the total amount of the friction material composition.

[0047] The filler may be such as a barium sulfate and a calcium carbonate.

[0048] Also, with respect to the copper component contained in the friction material, California State (CA) and Washington State (WA) of the United States of America passed a bill to prohibit the sales of the friction member using the friction material containing 5.0 mass % or more of the copper component relative to the total amount of the friction material composition and an act of assembling the subject friction member in a new car from the year of 2021, and to prohibit the sales of the friction member using the friction material containing 0.5 mass % or more of the copper component relative to the total amount of the friction material composition and an act of assembling the subject friction member in a new car from the year of 2025. Accordingly, preferably, the copper component such as the fiber and particles containing copper is added to the friction material composition so as to conform to the regulations but more preferably the copper component is not added to the friction material composition.

[0049] The friction material of this invention is manufactured through a mixing step for mixing the predetermined amount of the friction material composition uniformly using a mixer so as to obtain a raw friction material mixture, a heat press forming step for heat press forming the raw friction material mixture superposed on a back plate which is pre-washed, surface-treated, and adhesive coated to obtain a molded article, a heat treatment step for completing the curing effect of the binder by heating the molded article to obtain heated article, a coating step for coating the heated article with such as splay coating and electrostatic powder coating to obtain coated article, a coating baking step for baking the coating on the coated article to obtain a backed article, and grinding step for grinding the backed article by the rotating grinding stone.

[0050] Yet, after the heat press forming step, the coating step, the heat treatment step doubling the coating baking step and the grinding step may be allowed.

As necessary, prior to the heat press forming step, a granulating step for granulating the raw friction material mixture, a kneading step for kneading the raw friction material mixture, and a preforming step for forming an intermediate preformed product by molding the raw friction material mixture, the granulated friction material composition obtained through the granulating step or the kneaded friction material composition obtained through the kneading step in the preforming die, may be performed, and a scorch step may be performed after the heat press forming step.

EMBODIMENTS

[0051] In the following sections, the embodiments and the comparative examples are shown to give more specific explanations of this invention; however, this invention is not limited to what is described in the following embodiments and comparative examples.

[0052] [Manufacturing Method for the Friction Material Embodiments 1-19 and Comparative Examples 1-4]

The friction material composition shown in TABLE 2, TABLE 3, and TABLE 4 is mixed for 5 minutes with the Loedige mixer and is pressed in the forming die for 10 seconds under 30 MPa for form the intermediate preformed product. This intermediate preformed product is superposed on the steel back plate that is pre-washed, pre-surface treated, and pre-adhesive coated, formed in the heat forming die at 150 degrees centigrade of the forming temperature under 40 MPa of the forming pressure for 10 minutes. After that, heat-treated (cured) at 200 degrees centigrade for 5 hours, and grinded to form the friction surface in order to manufacture the disc brake pad for a passenger car. (See Embodiments 1-19 and Comparative Examples 1-4)
Here, the magnesium potassium titanate in Tables 2 to 4 is a lepidocrosite type magnesium potassium titanate having a layer crystal structure

TABLE-US-00002 TABLE 2 Embodiments 1 2 3 4 5 6 7 8 9 10 Binder straight phenolic 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 resin Fiber fibrillated aramid 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Base fiber Material fibrillated 3.0 cellulose fiber fibrillated polyacrylonitrile fiber Lubricant molybdenum 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 disulfide graphite 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Inorganic magnesium Friction potassium Modifier titanate (alkali elution rate = 3.0%) magnesium 20.0 potassium titanate (alkali elution rate = 2.5%) magnesium 20.0 potassium titanate (alkali elution rate = 1.5%) magnesium 20.0 10.0 5.0 30.0 20.0 potassium titanate (alkali elution rate = 1.0%) magnesium 20.0 potassium titanate (alkali elution rate = 0.5%) magnesium 20.0 potassium titanate (alkali elution rate = 0.1%) magnesium potassium titanate (alkali elution rate = 0.05%) lithium 20.0 10.0 potassium titanate (alkali elution rate = 1.0%) zirconium oxide 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 (average particle diameter = 2.0 μm) zirconium silicate 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 mica 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Organic cashew dust 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Friction pulverized 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Modifier powder of tire tread rubber pH calcium 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Adjuster hydroxide Filler barium sulfate 27.0 27.0 27.0 27.0 27.0 27.0 27.0 42.0 17.0 27.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

TABLE-US-00003 TABLE 3 Embodiments 11 12 13 14 15 16 17 18 19 Binder straight 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 phenolic resin Fiber fibrillated 1.5 1.0 2.0 4.0 5.0 3.0 3.0 3.0 3.0 Base aramid fiber Material fibrillated cellulose fiber fibrillated 1.5 polyacrylonitrile fiber Lubricant molybdenum 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 disulfide graphite 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Inorganic magnesium Friction potassium Modifier titanate (alkali elution rate = 3.0%) magnesium potassium titanate (alkali elution rate = 2.5%) magnesium potassium titanate (alkali elution rate = 1.5%) magnesium 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 potassium titanate (alkali elution rate = 1.0%) magnesium potassium titanate (alkali elution rate = 0.5%) magnesium potassium titanate (alkali elution rate = 0.1%) magnesium potassium titanate (alkali elution rate = 0.05%) lithium potassium titanate (alkali elution rate = 1.0%) zirconium oxide 20.0 20.0 20.0 20.0 20.0 4.0 5.0 25.0 26.0 (average particle diameter = 2.0 μm) zirconium 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 silicate mica 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Organic cashew dust 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Friction pulverized 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Modifier powder of tire tread rubber pH calcium 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Adjuster hydroxide Filler barium sulfate 27.0 29.0 28.0 26.0 25.0 43.0 42.0 22.0 21.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

TABLE-US-00004 TABLE 4 Comparative Examples 1 2 3 4 Binder straight phenolic resin 8.0 8.0 8.0 8.0 Fiber Base fibrillated aramid fiber 3.0 3.0 3.0 3.0 Material fibrillated cellulose fiber fibrillated polyacrylonitrile fiber Lubricant molybdenum disulfide 1.0 1.0 1.0 1.0 graphite 3.0 3.0 3.0 3.0 Inorganic magnesium potassium titanate 20.0 Friction (alkali elution rate = 3.0%) Modifier magnesium potassium titanate (alkali elution rate = 2.5%) magnesium potassium titanate (alkali elution rate = 1.5%) magnesium potassium titanate 4.0 31.0 (alkali elution rate = 1.0%) magnesium potassium titanate (alkali elution rate = 0.5%) magnesium potassium titanate (alkali elution rate = 0.1%) magnesium potassium titanate 20.0 (alkali elution rate = 0.05%) lithium potassium titanate (alkali elution rate = 1.0%) zirconium oxide (average 20.0 20.0 20.0 20.0 particle diameter = 2.0 μm) zirconium silicate 3.0 3.0 3.0 3.0 mica 5.0 5.0 5.0 5.0 Organic cashew dust 5.0 5.0 5.0 5.0 Friction pulverized powder of tire tread 2.0 2.0 2.0 2.0 Modifier rubber pH Adjuster calcium hydroxide 3.0 3.0 3.0 3.0 Filler barium sulfate 27.0 27.0 43.0 16.0 Total 100.0 100.0 100.0 100.0

[0053] The braking effectiveness, the crack resistance, and the fade resistance of these disc brake pads are evaluation based on the conditions shown in TABLE 5. The evaluation standard is shown in TABLE 5, and the evaluation results are shown in TABLE 6, TABLE 7, and TABLE 8.

TABLE-US-00005 TABLE 5 Braking Fade Brake Effectiveness Crack Resistance Resistance Noise Based on Based on JASO C427 Based on Based on JASO C406 Wear test on JASO JASO 2nd individual temperature C406 1st C404 Effectiveness Pre-braking Fade Test Brake Test temperature: 400 Minimum noise Average degrees centigrade friction occurrence friction Repeat braking until coefficient rate coefficient thickness of the friction material becomes half Excellent 0.45 or more No visible crack and 0.32 or less than (EX) fissure on the friction more 1.0% material surface after testing Good 0.42 or more Slight cracking on the 0.30 or 1.0% or (GD) but less than friction material more but more but 0.45 surface after testing less than less than (Unable to insert 0.32 1.5% 0.1 mm thickness gage) Average 0.39 or more Small cracking on the 0.28 or 1.5% or (AV) but less than friction material more but more but 0.42 surface after testing less than less than (Able to insert 0.1 mm 0.30 2.0% thickness gage but unable to insert 0.5 mm thickness gage) Bad less than 0.39 Large cracking on the less than 2.0% or (BD) friction material 0.28 more surface after testing (Able to insert 0.5 mm thickness gage)

TABLE-US-00006 TABLE 6 Embodiments 1 2 3 4 5 6 7 8 9 10 Evaluation Braking GD EX EX EX EX GD EX AV AV EX Result Effectiveness Crack GD EX EX EX EX EX EX EX GD AV Resistance Fade GD EX EX EX GD GD GD AV AV EX Resistance Brake Noise EX EX EX EX EX EX EX EX EX EX Mixture No No No No No No No No No No Condition (Fiber Ball Existence) EX = Excellent, GD = Good, AV = Average

TABLE-US-00007 TABLE 7 Embodiments 11 12 13 14 15 16 17 18 19 Evaluation Braking EX EX EX EX EX EX EX EX EX Result Effectiveness Crack GD EX EX EX EX EX EX EX EX Resistance Fade EX AV GD EX EX AV GD EX EX Resistance Brake Noise EX EX EX EX EX EX EX GD AV Mixture No No No No Exist No No No No Condition (Fiber Ball Existence)

TABLE-US-00008 TABLE 8 Comparative Examples 1 2 3 4 Evaluation Braking Effectiveness BD GD BD BD Result Crack Resistance GD EX EX GD Fade Resistance BD BD BD AV Brake Noise EX EX EX EX Mixture Condition No No No No (Fiber Ball Existence)

[0054] From the respective TABLES, the friction materials satisfying the conditions described in this invention show excellent braking effectiveness, crack resistance, and fade resistance.

INDUSTRIAL APPLICABILITY

[0055] According to this invention, the friction material for the disc brake pad, which is manufactured by forming NAO friction material composition, can satisfy the legal requirement with respect to the minimum amount of the copper component and can satisfy the required performance with respect to the braking effectiveness, the crack resistance, and the fade resistance, thereby offering highly practical and valuable product.