WO2005118730A1 - Aqueous coating material for sliding member and sliding member - Google Patents

Abstract

Disclosed is a sliding member obtained by a simple working process which exhibits excellent sliding durability at high temperatures and does not abrade the object material even when the object material is a soft metal. Also disclosed is a coating material used for such a sliding member. Specifically disclosed is an aqueous coating material for sliding members which contains a heat-resistant resin (A), at least one lubricant component (B) selected from the group consisting of molybdenum disulfide, boron nitride, graphites, polytetrafluoroethylenes, waxes and fatty acid salts, a copolymer (C) of fluoroolefin and a vinyl compound having a hydrophilic group or hydrophilic chain, and water. In this connection, the components (A)-(C) are dissolved or dispersed in water.

Description

 Specification

 Water-based paint for sliding members and sliding members

 Technical field

 The present invention relates to a water-based paint for a sliding member and a sliding member.

 Background art

 [0002] Conventionally, thermoplastic resins having excellent wear resistance, such as polyamide resins and polyacetal resins, have been widely used for sliding members. Also, special engineering plastics such as polyimide resin and polyamideimide resin are used for sliding parts that require heat resistance.

Thermosetting resins such as phenolic resins are used.

 In general, these resins do not exhibit lubricity and cannot be used unless they are lubricated or otherwise lubricated.

[0003] To improve this point, sliding in which a solid lubricant such as disulfide molybdenum, boron nitride, graphite, polytetrafluoroethylene, or the like is blended with an abrasion-resistant resin is used. A resin composition for members has been proposed.

 However, when a solid lubricant is used, the compounding amount must be increased in order to obtain good lubrication performance, and a molded article of such a resin composition has a problem that the mechanical strength is extremely poor. There is.

 [0004] On the other hand, Patent Document 1 proposes a polytetrafluoroethylene resin composition filled with carbon fibers and the like, but the one containing carbon fibers has improved mechanical strength, , It was difficult to obtain sufficient sliding characteristics.

 [0005] On the other hand, among the heat-resistant resins, a composition using phenolic resin uses a soft metal such as aluminum as a mating material of a sliding member because the surface of a molded article obtained is relatively hard. Then, there is a problem that the partner material is worn.

[0006] On the other hand, Patent Document 2 proposes a fluorine resin composition that is suitably used for a soft metal mating member and a sliding component member or the like in which self-abrasion is reduced. Powder filling or melt mixing is performed in the preparation of the product, and a firing process at 360 to 390 ° C. is required to obtain a molding material, which has a problem that the processing temperature is high. Since such a composition for a sliding member is based on a powder or a solvent, it needs to be fired or volatilize the solvent.

 Patent Document 1: JP-A-2002-317089

 Patent Document 2: JP-A-6-25499

 Disclosure of the invention

 Problems to be solved by the invention

[0008] Therefore, the present invention provides a sliding member that exhibits excellent sliding resistance even at high temperatures, does not wear a mating material even when a soft metal is used as a partner material, and has a simple working process. And a paint used for the same.

 Means for solving the problem

 The present inventors have conducted intensive studies to achieve the above object, and as a result, by adding a specific fluorine-containing copolymer to a water-based paint containing a heat-resistant resin and a lubricant component. The present inventors have found that a sliding member having a coating film on its surface exhibits excellent sliding resistance even at high temperatures and suppresses abrasion of a mating material, thereby completing the present invention. Further, the present inventor has further found that the addition of urethane resin results in excellent toughness of a coating film and excellent adhesion to a substrate.

 [0010] The present invention provides the following water-based paints for sliding members (1) to (8) and the sliding members of (9) and (10).

 (1) heat-resistant resin (A),

 Molybdenum disulfide, boron nitride, graphite, polytetrafluoroethylene, wax and at least one kind of lubricant component (B) selected from a group consisting of a fatty acid salt and

 A copolymer of fluorofluorin and a vinyl compound having a hydrophilic group or a hydrophilic chain (C),

 Containing water and

 An aqueous paint for a sliding member, wherein the components (A) to (C) are dissolved or dispersed in the water.

(2) The ratio of the copolymer (C) to the heat-resistant resin (A) is (C) / (A) = 0.01 to 0.8 in terms of solid content mass ratio (1). 3. The water-based paint for a sliding member according to 1. (3) The ratio of the lubricant component (B) to the heat-resistant resin (A) is (B) / (A) = 0.02 to 0.8 in terms of solid content mass ratio, wherein (1) or Water-based paint for sliding members according to (2)

(4) The water-based paint for a sliding member according to any one of (1) to (3), further comprising a urethane resin (D).

 (5) The ratio of the urethane resin (D) to the heat resistant resin (A) is (D) Z (A) = 0.01 or more: L5 in terms of solid content mass ratio (4). 3. The water-based paint for a sliding member according to 1.

 (6) The water-based paint for a sliding member according to any one of the above (1) to (5), wherein the heat-resistant resin (A) is a phenol resin.

 (7) The aqueous paint for a sliding member according to the above (6), wherein the phenol resin is a water-soluble resol type phenol resin.

 (8) The water-based paint for a sliding member according to the above (6), wherein the phenol resin is a water-soluble resole type phenol resin mainly having mononuclear and Z or dinuclear properties.

 (9) A sliding member having on its surface a coating film formed from the water-based paint for a sliding member according to any one of the above (1) to (8).

 (10) The sliding member according to (9), wherein the amount of the copolymer (C) in the coating film is larger on the outside than on the inside.

 The invention's effect

 [0011] The sliding member using the water-based paint for a sliding member of the present invention exhibits excellent sliding resistance even at a high temperature, and suppresses abrasion of a mating material.

 In addition, the water-based paint for sliding members of the present invention has a simple work process, and has a good work environment in consideration of global environmental conservation.

 Therefore, the water-based paint for a sliding member of the present invention and the sliding member using the same have extremely high industrial utility value.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the water-based paint for a sliding member and the sliding member of the present invention will be described in detail.

 First, the water-based paint for a sliding member of the present invention will be described.

The water-based paint for a sliding member of the present invention comprises a heat-resistant resin (A), molybdenum disulfide, At least one lubricant component (B) selected from the group consisting of nitrogen, graphite, polytetrafluoroethylene, wax and a salt of a fatty acid, fluorofluorin, and vinyl having a hydrophilic group or a hydrophilic chain. A water-based paint for a sliding member, comprising a copolymer (C) with a compound and water, and wherein the components (A) to (C) are dissolved or dispersed in the water. .

[0014] The heat-resistant resin (A) used in the present invention is not particularly limited as long as it dissolves or disperses in water. Examples thereof include phenol resin, polyamideimide resin, silicone resin, and silicone resin. And epoxy resin.

 Among them, phenolic resin is preferred because the coating film becomes hard and can be obtained at low cost. The type and structure of the phenol resin are not particularly limited, but need to be dissolved or dispersed in water.

 As such a phenolic resin, a water-soluble resol type phenolic resin is preferably exemplified. As a water-soluble resol type phenol resin, it is possible to stabilize water solubility and to make the sliding resistance of the coating film particularly excellent. Or those that also have two nuclear strength are preferred.

 The heat-resistant resin (A) may be used alone or in combination of two or more.

[0015] The lubricant component (B) used in the present invention imparts lubricity, and has a group strength of molybdenum disulfide, boron nitride, graphite, polytetrafluoroethylene, wax and a fatty acid salt. At least one selected.

 In particular, when heat resistance is required, it is preferable to use at least one of molybdenum disulfide, boron nitride, graphite, and a group force including polytetrafluoroethylene force.

 [0016] In particular, polytetrafluoroethylene having excellent continuous heat-resistant temperature characteristics and exhibiting the lowest friction coefficient among these solid lubricants is preferable. The particle size of polytetrafluoroethylene is not particularly limited, but it is preferable to use particles having an average particle size of 0.1 to 5 / ζπι, and the average particle size is 0.1. It is more preferable to use particles having a particle size of about 1 / ζπι.

The polytetrafluoroethylene is preferably present in the aqueous coating composition for a sliding member of the present invention in a form of being stably dispersed. Use a known surfactant for stable dispersion be able to. In this case, an aqueous dispersion in which polytetrafluoroethylene particles are dispersed in the presence of an anionic or nonionic surfactant can be used.

[0017] The wax is not particularly limited in structure, type and the like, but a synthetic wax is preferably exemplified in that it has an effect of extremely reducing the friction coefficient of a coating film.

 Among them, those that are stable in water and have excellent mechanical strength of the coating film are preferable. Specific examples include microcrystalline wax, polyethylene wax, polypropylene wax, and carnauba wax. It is preferable that these are mixed with other components in the form of a disposable material and then incorporated into the water-based paint for sliding members of the present invention.

 The type of the fatty acid salt is not specified, but, for example, at least one selected from the group consisting of a fatty acid having 12 to 26 carbon atoms and zinc, calcium, norium, aluminum, magnesium, sodium and lithium. Those obtained by reacting with a metal are preferred. Among them, stearates are preferred.

 In the water-based paint for sliding members of the present invention, (B) / (A) = 0.02-0 in terms of the ratio of the ratio of the lubricant component (B) to the heat-resistant resin (A) and the solid content mass ratio. 8 is preferred 0.1 to 0.3 is more preferred. (B) When Z (A) is 0.02 or more, the lubrication performance becomes more excellent. ) When the value of (8) is 0.8 or less, the mechanical strength becomes more excellent, so that a better sliding resistance can be obtained. Further, the properties of the copolymer (C) described later can be obtained. And functions appear more effectively.

 [0020] The copolymer (C) used in the present invention is a copolymer of fluorofluorin and a vinyl compound having a hydrophilic group or a hydrophilic chain.

 Fluoroolefin is a compound in which at least one hydrogen atom of olefin is substituted with a fluorine atom, and one or more hydrogen atoms may be substituted with a chlorine atom. For example, compounds having 2 to 4 carbon atoms such as tetrafluoroethylene, chlorofluoroethylene, trifluoroethylene, bi-lidene fluoride, hexafluoropropylene, pentafluoropropylene, etc. Preferred examples are given. These may be used alone or in combination of two or more.

As a Birui dani product, for example, hydroxy group, carboxy group, sulfo group, salts thereof A hydrophilic group such as a group of (for example, an alkali metal salt) or a belief conjugate having a hydrophilic chain such as polyethylene oxide, hydroxyalkyl butyl ether, hydroxyalkyl butyl ester, etc. These may be used alone or in combination of two or more.

[0021] the proportion of units based on the full O Roo Lev-in in the copolymer (C) is preferably Ru 30-70 mole _^0/0 der. Within the above range, the balance between the sliding performance and flexibility of the coating film and the water solubility or water dispersibility becomes excellent.

 The copolymer (C) may be any of an alternating copolymer, a block copolymer, and a random copolymer, but is preferably an alternating copolymer.

 The copolymer (C) preferably has a number average molecular weight of about 1,000 to 5,000,000, more preferably a power of about 3,000 to 2,000,000! / ヽ.

This copolymer (C) is known to exhibit excellent heat resistance due to a strong bonding force between a fluorine atom and a carbon atom, and to impart low frictional properties due to its low polarizability. .

 However, the inventor of the present invention has come up with a surprising result during his research and development. That is, by blending a copolymer (C) with an aqueous paint containing a heat-resistant resin (A) and a lubricant component (B), the toughness and flexibility of the coating film are increased, and the coating film is broken against external force.を We found that it was possible to express its stiffness. In particular, it has been found that when a phenolic resin having poor toughness is used as the heat-resistant resin (A), the effect is large.

 In addition, the present inventor can freely control the surface hardness of the coating film without impairing the adhesion between the coating film and the substrate by adjusting the blending amount of the copolymer (C), As a result, they found that when the mating material is a soft metal such as aluminum, it is possible to significantly reduce the wear of the mating material.

 None of these findings were known. The present inventors have completed the present invention based on these findings.

[0023] In contrast, according to the research of the present inventors, even if the same fluorine-containing polymer, polytetrafluoroethylene, is similarly mixed, the surface hardness of the coating film can be freely controlled. It is difficult. [0024] The mechanism by which the water-based paint for sliding members of the present invention achieves both the adhesion and flexibility of the coating film is not clear, but the inference of the present inventors is as follows.

 The present inventors performed cross-sectional analysis using an electron probe microanalyzer (EPMA: Electron Probe Microanalyser) in order to examine how the copolymer (C) was distributed in the coating film. As a result, a large amount of the copolymer (C) was detected in the surface layer of the coating film, and was hardly detected in the deep layer.

 From this result, the present inventor concluded that the copolymer (C) was present in a large amount on the surface layer of the coating film, so that it was possible to control the surface hardness with a relatively small amount of the copolymer, while the It was thought that, since there was not much in the vicinity, even if it was mixed in a large amount, there was little risk of impairing the adhesion to the base material.

 [0025] In the water-based paint for sliding members of the present invention, the ratio of the copolymer (C) to the heat-resistant resin (A) and the solid content mass ratio, (C) / (A) = It is preferably from 0.01 to 0.8, and more preferably from 0.1 to 0.3. (C) When Z (A) is 0.01 or more, the coating film becomes more tough and the sliding resistance becomes more excellent. In addition, the aqueous liquid paint for sliding members of the present invention has more excellent temporal stability. (If the value of 7 (8) is 0.8 or less, the flexibility of the coating film becomes appropriate and the sliding resistance becomes more excellent.

 The water-based paint for a sliding member of the present invention contains water in addition to the components (A) to (C) described above, and the components (A) to (C) are dissolved or dispersed in the water. hand! /

 As described above, the water-based paint for a sliding member of the present invention is a water-based paint in which components are dissolved or dispersed in water. The sintering at a high temperature as described above is not required, and the volatilization of the solvent as in the case of using a solvent is unnecessary. Therefore, the work process is simple, and the global environment is considered, and the work environment is good.

 [0027] The water-based paint for sliding members of the present invention preferably further contains a urethane resin (D) in addition to the above-mentioned components (A) to (C) and water. When the water-based paint for a sliding member of the present invention contains the urethane resin (D), the toughness of the coating film and the adhesion to the base material are further improved.

The urethane resin (D) used in the present invention may be any one dissolved or dispersed in water. There is no particular limitation on the structure, type, and the like. For example, a reaction product of a polyol, such as a polyester polyol, a polyether polyol, or a polycarbonate polyol, and a polyisocyanate, such as an aliphatic polyisocyanate or an aromatic polyisocyanate, may be used.

 When the urethane resin (D) is contained, a coating film having excellent adhesion to various substrates is obtained. Among them, urethane resins having a hydrophilic component, for example, a hydrophilic group such as a carboxy group or a sulfo group or a salt thereof in the main chain, are oriented to a polar substrate and have excellent adhesion to the substrate. A coating is obtained. In particular, it is possible to obtain a coating film having excellent adhesion to aluminum and a substrate having an alloying power thereof.

 The urethane resin (D) preferably has a high glass transition point and a high melting temperature in that the sliding resistance of the coating film is particularly excellent at high temperatures. Specifically, the melting temperature of the urethane resin is preferably 200 ° C. or higher.

 [0029] In the water-based paint for a sliding member of the present invention, the urethane resin for the heat-resistant resin (A) is used.

 (D) Ratio power (D) / (A) = 0.01 to 1.5, preferably 0.1 to 1.0, more preferably 0.1 to 1.0. (D) When Z (A) is 0.01 or more, the adhesiveness to the substrate is excellent. (D) If Z (A) is 1.5 or less, better sliding resistance can be obtained.

 [0030] The water-based coating composition for a sliding member of the present invention may contain various components in addition to the components (A) to (C) and water and optionally the component (D) as long as the object of the present invention is not impaired. Additives can be included. For example, fillers are included for the purpose of mechanical properties (tensile strength, wear resistance, lubricity, toughness, etc.), thermal properties (heat resistance, thermal shock resistance, etc.), thickening of coating films, etc. be able to. Further, a surfactant, a thickener, and the like can be contained for the purpose of improving the leveling property, suppressing cissing, preventing dripping, and the like. Further, a pigment may be included for coloring purposes. Further, an organic solvent such as alcohol can be contained within a range not to impair the object of the present invention.

[0031] Examples of the filler include titanium oxide, zinc oxide, aluminum oxide, iron oxide, tin oxide, fumed silica, colloidal silica, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and calcium carbonate. , Magnesium carbonate, zinc carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum nitride, silicon nitride, talc, my force, carbohydrate Black and white.

 These can be used alone or in combination of two or more.

[0032] Examples of the surfactant include a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant.

 The nonionic surfactant is not particularly limited, and includes, for example, polyoxyethylene alkyl ether, alkylphenol ether, and polyethylene glycol.

 The anionic surfactant is not particularly limited, and includes, for example, sulfates, sulfonates, and phosphates.

 The amphoteric surfactant is not particularly limited, and examples thereof include an alkylamino fatty acid salt and an alkyl amine oxide.

 The cationic surfactant is not particularly limited, and includes, for example, fatty acid amine salts and quaternary ammonium salts.

 These can be used alone or in combination of two or more.

[0033] Examples of the thickener include an inorganic thickener and an organic thickener.

 The inorganic thickener is not particularly limited, and examples thereof include finely divided silica. Examples of the fine silica include montmorillonite, paiderite, nontronite, sabonite, and hectorite.

 The organic thickener is not particularly limited, and includes, for example, hydroxyethyl cellulose, carboxylmethyl cellulose, polyacrylamide, sodium polyacrylate, and polybutyl alcohol.

 These can be used alone or in combination of two or more.

[0034] The pigment is not particularly limited, and examples thereof include zinc oxide, titanium oxide, antimony oxide, carbon black, graphite, cyanine black, iron oxide, iron oxide, ultramarine blue, and phthalocyanine green.

 These can be used alone or in combination of two or more.

[0035] The water-based paint for sliding members of the present invention has a coating film that exhibits excellent sliding resistance even at high temperatures, and does not cause abrasion of the mating material even when a soft metal is used as the mating material.

Further, since the water-based paint for a sliding member of the present invention is a water-based paint, the working process is simple. is there. Furthermore, considering the global environment conservation, the working environment is good.

 Therefore, the water-based paint for sliding members of the present invention is suitably used for various sliding members.

 [0036] The sliding member of the present invention is a sliding member having on its surface a coating film formed of the water-based paint for a sliding member of the present invention.

 As described above, according to the analysis of the present inventors, the amount of the copolymer (C) is large in the surface layer of the coating film and small in the deep layer. As a result, it is considered that a moderate surface hardness and excellent adhesion to the base material and the coating film are obtained. Therefore, in the sliding member of the present invention, it is preferable that the amount of the copolymer (C) in the coating film is very large inside and outside of the coating. That is, it is preferable that the film is an inclined coating film.

 [0037] In the sliding member of the present invention, the thickness of the coating film is not particularly limited, but is preferably 1 to 150 m, more preferably 10 to 100 m. When the thickness of the coating film is 1 μm or more, the sliding resistance becomes more excellent. When the thickness of the coating film is 150 m or less, V, a good coating appearance without so-called rough surface can be easily obtained.

 [0038] As a material of a base material for forming a coating film, a metal material or a resin material can be suitably used. For example, aluminum, aluminum alloys, copper, copper alloys, magnesium, magnesium alloys, steel, steel alloys (eg, stainless steel), titanium, titanium alloys; plated products of these (eg, plated steel); Is mentioned. Among them, soft metal materials such as aluminum, aluminum alloy, copper, and copper alloy are preferable.

 The substrate is preferably formed into a coating film after the cleaning treatment. The cleaning treatment can improve the adhesion between the substrate and the coating film. The method of the cleaning treatment is not particularly limited, and examples thereof include shot blasting, alkali cleaning, and acid cleaning. These can be performed by a known method.

 The manufacturing method of the sliding member of the present invention is not particularly limited, and it can be obtained by forming a coating film of the water-based coating material for a sliding member of the present invention on the surface of a substrate by a conventionally known method. . For example, a preferred method is to apply the water-based coating material for a sliding member of the present invention to the surface of the substrate after the cleaning treatment and then to dry the film to form a coating film on the surface of the substrate.

The application method is not particularly limited. For example, spray coating, dip coating, flow coating And bar coat. When applying the water-based paint for a sliding member of the present invention, it is preferable to appropriately adjust the concentration so as to obtain a desired film thickness.

 The drying method is not particularly limited, but hot air drying is generally used. As the drying conditions, for example, a method in which preliminary drying is 120 to 130, main drying is 150 to 200 ° C., and each is 30 to 90 minutes, is preferably mentioned.

 In addition, a method in which the temperature is gradually increased to perform drying without performing preliminary drying is also preferably used.

 [0040] The sliding member of the present invention is not particularly limited in use, and is suitable for, for example, sliding parts of pneumatic equipment, machine tools, office equipment, automobiles, motorcycles, aircraft, ships, railways, home appliances, and the like. Used for Among them, rotors, cylinders, gears, bearings, and pumps for machine tools, which are sliding parts that require heat resistance; pistons, transmissions, and camshafts for automobile-related parts; suitable for scrolling home appliances such as refrigerators and air conditioners Used for

 [0041] Since the sliding member of the present invention has a coating film formed of the water-based paint for a sliding member of the present invention, it exhibits excellent sliding resistance even at high temperatures, and uses soft metal as a mating material. Even when used, it does not wear the mating material.

 Example

 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

1. Manufacture of sliding members

 (Example 1)

Water-soluble resole type phenol resin consisting mainly of mono- and di-nucleated methyl syrup with methylol (component (A)) 100 parts by mass (solid content), water-dispersible PTFE (component (B), average particles Diameter 0.2 m) 20 parts by mass (solid content) and a water-dispersed copolymer (component (C)), a compound having a hydrophilic chain of tetrafluoroethylene, cyclotrifluoroethylene, and hydroxybutyl ether a copolymer of things, full O Roo reflex and in-units and Bulle ether units have alternating copolymer, a copolymer proportion of units based on full O Roo reflex in is 50 mole _^0/0 A number-average molecular weight of 1,000,000, a particle diameter of 0.1 to 0.2 m) and 20 parts by mass (solid content) to prepare a water-based paint for a sliding member.

Aluminum alloy (A4032) plate 70 x 150 mm in size and 1.5 mm in thickness Was prepared, and after washing, the aqueous coating material for a sliding member obtained above was bar-coated.

 Then, pre-drying is performed at 130 ° C for 30 minutes, and then main drying is performed at 180 ° C for 30 minutes to form a 30-m-thick coating film on the surface of the specimen to obtain a sliding member. Was.

(Examples 2 to 6)

 A sliding member was obtained in the same manner as in Example 1 except that the mass ratio of each component was as shown in Table 1.

(Example 7)

 Instead of 20 parts by mass (solid content) of water-dispersible PTFE ((B) component, average particle size 0.2; Δη), 20 parts by mass (solid component) of water-dispersible polypropylene wax ((B) component, average particle size 0.5 m) A sliding member was obtained in the same manner as in Example 1 except that (i) was used.

(Example 8)

 Instead of 20 parts by mass (solid content) of water-dispersed PTFE ((B) component, average particle size 0.2; ζΐη), 20 parts by mass of barium stearate powder ((Β) component, average particle size 5 μm) was used. A sliding member was obtained in the same manner as in Example 1 except for using the sliding member.

(Example 9)

 Instead of 20 parts by mass (solid content) of water-dispersed PTFE ((B) component, average particle size 0.2; ζΐη), use 20 parts by mass of boron nitride powder ((Β) component, average particle size 6 μm) A sliding member was obtained in the same manner as in Example 1 except for the above.

(Example 10)

 Instead of 20 parts by mass (solid content) of water-dispersed PTFE ((B) component, average particle size 0.2; Δη), 20 parts by mass of graphite powder ((B) component, average particle size 2 m) was used. Except for the above, a sliding member was obtained in the same manner as in Example 1.

(Example 11)

 Instead of 20 parts by mass (solid content) of water-dispersed PTFE ((B) component, average particle size 0.2; ζΐη), 20 mass parts of powder of disulfide molybdenum ((Β) component, average particle size 1 μm) 20 mass A sliding member was obtained in the same manner as in Example 1 except that the part was used.

(Example 12)

Water-soluble resol type phenol resin (component (A)) Instead of 100 parts by mass (solid content), A water-soluble novolak-type phenol resin into which ethanolamine was introduced ((A) component, number average molecular weight: 3,000) Except that 100 parts by mass (solid content) was used, the same method as in Example 1 was used. A moving member was obtained.

 (Example 13)

 Instead of 100 parts by mass (solid content) of a water-soluble resol type phenol resin (component (A)), 100 parts by mass of bisphenol A type epoxy resin (component (A), epoxy equivalent 1,800) A sliding member was obtained in the same manner as in Example 1 except that (i) was used.

 (Example 14)

 The procedure was carried out except that 100 parts by mass (solid content) of a polyamide imide resin (component (A)) was used instead of 100 parts by mass (solid content) of the water-soluble resol type phenol resin (component (A)). A sliding member was obtained in the same manner as in Example 1.

 (Example 15)

Water-soluble resole type phenol resin consisting mainly of mono- and di-nucleated methyl syrup with methylol (component (A)) 100 parts by mass (solid content), water-dispersible PTFE (component (B), average particles Diameter 0.2 m) 20 parts by mass (solid content) and water-dispersed copolymer (component (C), a compound having a hydrophilic chain of tetrafluoroethylene, chlorofluoroethylene and hydroxybutyl ether) a copolymer of things, full O Roo reflex and in-units and Bulle ether units have alternating copolymer, a copolymer proportion of units based on full O Roo reflex in is 50 mole _^0/0 , Number average molecular weight: 1,000,000, particle size: 0.1 to 0.2 m) 20 parts by mass (solid content) and an ionic water-based polyurethane resin ((D) component, polyether polyol aliphatic) Polyisocyanate type, number average molecular weight 1,000,000, average particle size 0.09 m) 30 parts by mass (solid content) , To prepare an aqueous paint sliding member.

 Using this water-based paint for a sliding member, a sliding member was obtained in the same manner as in Example 1.

 (Example 16)

 Water-dispersible PTFE ((B) component, average particle size 0.2; ΐ ΐη) Instead of 20 parts by mass (solid content), water-dispersible polypropylene wax ((B) component, average particle size 0.5 m) A sliding member was obtained in the same manner as in Example 15 except that 20 parts by mass (solid content) was used.

(Example 17) Instead of 20 parts by mass (solid content) of water-dispersed PTFE ((B) component, average particle size 0.2; ζΐη), barium stearate powder ((B) component, average particle size 5 μm) 20 mass A sliding member was obtained in the same manner as in Example 15 except that the part was used.

(Example 18)

 Instead of water-dispersed PTFE ((B) component, average particle size 0.2; Δη) 20 parts by mass (solid content), boron nitride powder ((B) component, average particle size 6 μm) 20 parts by mass A sliding member was obtained in the same manner as in Example 15, except for using.

(Example 19)

 Instead of 20 parts by mass (solid content) of water-dispersed PTFE ((B) component, average particle size 0.2; Δη), 20 parts by mass of graphite powder ((B) component, average particle size 2 m) A sliding member was obtained in the same manner as in Example 15 except that the sliding member was used.

(Example 20)

 Instead of water-dispersed PTFE ((B) component, average particle size 0.2; 20η) 20 parts by mass (solid content), powder of disulfide molybdenum ((B) component, average particle size 1 μm) A sliding member was obtained in the same manner as in Example 15 except that 20 parts by mass was used.

(Examples 21 to 23)

 A sliding member was obtained in the same manner as in Example 15 except that the mass ratio of each component was as shown in Table 1.

(Comparative Example 1)

 A water-dispersed copolymer ((C) component, number average molecular weight: 1,000,000, particle size: 0.1 to 0.2 μm) Example 1 was repeated except that 20 parts by mass (solid content) was used. A sliding member was obtained in the same manner as described above.

(Comparative Example 2)

 A sliding member was obtained in the same manner as in Example 1, except that 20 parts by mass (solid content) of water-dispersed PTFE (component (B), average particle size 0.2 m) was not used.

(Comparative Example 3)

Water-dispersed PTFE ((B) component, average particle size 0.2 m) 20 parts by mass (solid content) and water-dispersed copolymer ((C) component, number average molecular weight 1, 000, 000, particle size 0) .1 ~ 0.2μ20 A sliding member was obtained in the same manner as in Example 1 except that a force using parts by mass (solid content) was not used.

 [0063] 2. Analysis of coating film

 Example 8-: The coating film of each sliding member obtained in L1 was subjected to an accelerating voltage of 15 kV, a sample current of 0.05 μm, and a beam diameter of 1 μm using an EPMA (Electron Beam Probe Microscope Analyzer). Under the condition of φ, mapping analysis of the cross section of the coating film was performed using fluorine as a marker.

 As a result, in each case, it was confirmed that the fluorine strength was higher on the surface side than on the substrate side of the coating film.

[0064] 3. Various evaluation tests

 Various evaluation tests were performed on the water-based paints for sliding members and the sliding members obtained above as follows.

 (1) Liquid stability

 24 hours after the preparation of the water-based paint for the sliding member, the liquid stability was evaluated by visual observation after 24 hours.

 The results are shown in Table 1. In the table, those with no occurrence of aggregates are indicated by “〇”, and those with occurrence of aggregates are indicated by “X”.

[0065] (2) Pencil hardness

 Regarding the coating film of the sliding member, the pencil hardness was measured in accordance with the provisions of JIS 5600-5: 4: 1999 "Pull hardness (pencil method)".

 The results are shown in Table 1.

(3) Coating adhesion

 The adhesion of the coating film of the sliding member was evaluated by the following two methods. A cross-cut method was applied to the coating film of the sliding member according to JIS 5600 5-6: 1999 "Adhesion (cross-cut method)" to evaluate the coating film adhesion.

 The results are shown in Table 1. In the table, 〇 indicates the force that did not cause peeling, and も の indicates the force that caused peeling.

In addition, the weight of the coating film of the sliding member shall be in accordance with the “DuPont type” of JIS 5600-5: 3: 1999 “Water resistance to falling”, weight: 500g, shooting type: radius 6.35mm, Table: An impact deformation test was performed on a flat surface with a weight height of 100 mm or 500 mm to evaluate the adhesion of the coating film.

 The results are shown in Table 1. In the table, ◎ indicates a force that did not cause peeling at a weight height of 500 mm, Δ indicates a force that did not cause peeling at a weight height of 100 mm, and X indicates a force that caused peeling at a weight height of 100 mm.

(4) Sliding performance

 The coating film of the sliding member was subjected to a sliding test using a surface property measuring device (Tribogear) under the following conditions, and the sliding performance was evaluated by the number of times of sliding until the scratch reached the base material of the specimen.

 The results are shown in Table 1.

<Sliding test conditions>

 Load: 9.8N

 Indenter: ball (diameter 5. Omm)

 Indenter material: SUJ— 2

 Sliding width: 10mm

 Sliding speed: 2400mmZmin

 Test piece temperature: 130 ° C

[0069] (5) Roughness of sliding marks

 A sliding test was performed under the same conditions as above, and the sliding marks of the specimen after sliding 1000 times were measured for roughness using a three-dimensional surface roughness measuring device.

 The results are shown in Table 1. In Comparative Examples 2 and 3, the sliding test was terminated at that time because the coating film reached the base material of the specimen when slid several times.

[0070] (6) Scratch property of the indenter

 A sliding test was performed under the same conditions as above except that a ball made of pure aluminum was used as the indenter.The appearance of the indenter after sliding 2000 times was visually observed and observed with a metallographic microscope, and the indenter's scratch resistance was checked. evaluated.

The results are shown in Table 1. In the table, 力 indicates that a scratch was not observed, and X indicates that a scratch was observed. In Comparative Examples 2 and 3, when slid several times, Since the specimen reached the base material of the specimen, the sliding test was stopped.

 [0071] (7) Comprehensive judgment

 A comprehensive judgment was made based on the results of (1) and (6) above. The results are shown in Table 1.

[Table 1]

[Table 2]

O o O o O O o O O O

 o 0 0 0 O o 0 0 o o

 o 0 0 0 Θ Θ

O 0 0 0 O o 0 0 o O

 0 0 0 Θ Θ

[Table 3]

As is clear from Table 1, the water-based paint for sliding members of the present invention (Example 123) is excellent in liquid stability, coating film adhesion and sliding performance at high temperatures, and is excellent at high temperatures. The soft metal indenter did not hurt. Above all, when urethane resin (D) is contained (Example 15 To 23) were particularly excellent in coating film adhesion (impact deformation resistance).

 On the other hand, when the specific copolymer (C) was not contained (Comparative Example 1), the liquid stability was poor, a normal continuous coating film was not obtained, and the coating film was hard and damaged the indenter. Was. When the lubricant component (B) was not contained (Comparative Example 2), the friction coefficient of the coating film surface was high (that is, the sliding performance was poor), and the surface of the specimen was exposed immediately after the start of the sliding test. Further, when the lubricant component (B) and the specific copolymer (C) were not contained (Comparative Example 3), the friction coefficient of the coating film surface was high (that is, the sliding performance was poor), and The surface of the specimen was exposed immediately after the start of the sliding test in which the coating film was brittle.

Claims

The scope of the claims  [1] heat-resistant resin (A),  Molybdenum disulfide, boron nitride, graphite, polytetrafluoroethylene, wax and at least one kind of lubricant component (B) selected from a group consisting of a fatty acid salt and  A copolymer of fluorofluorin and a vinyl compound having a hydrophilic group or a hydrophilic chain (C),  Containing water and  An aqueous paint for a sliding member, wherein the components (A) to (C) are dissolved or dispersed in the water.  [2] The ratio according to claim 1, wherein the ratio of the copolymer (C) to the heat-resistant resin (A) is (C) / (A) = 0.01 to 0.8 in terms of a solid content mass ratio. A water-based paint for a sliding member according to the above.  [3] The ratio of the lubricant component (B) to the heat-resistant resin (A) is (B) / (A) = 0.02 to 0.8 in terms of solid mass ratio. 3. The water-based paint for a sliding member according to 1.  [4] The water-based paint for a sliding member according to any one of claims 1 to 3, further comprising a urethane resin (D).  [5] The ratio of the urethane resin (D) to the heat-resistant resin (A) is a solid content mass ratio,  5. The water-based paint for a sliding member according to claim 4, wherein (D) / (A) = 0.01 or more: L5.  6. The water-based paint for a sliding member according to claim 1, wherein the heat-resistant resin (A) is a phenol resin.  7. The water-based paint for a sliding member according to claim 6, wherein the phenol resin is a water-soluble resol type phenol resin.  [8] The water-based paint for a sliding member according to claim 6, wherein the phenol resin is a water-soluble resol type phenol resin mainly having mononuclear and Z or dinuclear properties.  [9] A sliding member having on its surface a coating film formed from the water-based paint for a sliding member according to any one of claims 1 to 8.  10. The sliding member according to claim 9, wherein the amount of the copolymer (C) in the coating film is larger on the outside than on the inside.