JP2005305395A - Method for coating aluminium based substrate and coated material of aluminium based substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for coating an aluminium based substrate and a coated material of the aluminium based substrate which can realize the improvement of adhesion between the substrate and a resin coating film without using environment load substances such as chromium(VI). <P>SOLUTION: In the method for coating the surface of the aluminium based substrate, which comprises a chemical treatment process chemically treating the surface of the aluminium based substrate consisting of an aluminium substrate and an aluminium alloy substrate, and a coating process for coating the chemically treated surface of the aluminium based substrate, the chemical treatment is, for example, carried out in such a away that the substrate is immersed into a chemically treating solution adjusted by pure water so as to become 16 wt% H<SB>2</SB>SO<SB>4</SB>(purity 98%), 16 wt% hydrogen peroxide water (purity 34%) and 4 wt% CuSO<SB>4</SB>-H<SB>2</SB>O. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for coating an aluminum-based substrate and a coated product thereof.

  When a resin film is applied to a metal substrate such as aluminum, if the resin film is directly applied to the surface of the substrate, the resin film may peel off due to poor adhesion. Then, in order to improve the adhesiveness of a base material and a resin film, as a coating method of an aluminum-type base material, it is disclosed by patent document 1 and 2 etc., for example.

Patent Document 1 discloses a method of manufacturing an aluminum alloy bearing in which an aluminum bearing alloy is brought into contact with an etching solution to be roughened, and an overlay is applied to the roughened surface. After the roughening treatment, phosphoric acid and chromic acid are used. And the use of a desmutting solution comprising a mineral acid other than hydrofluoric acid. Further, Patent Document 2 describes that, when coating is performed on an aluminum alloy base material, a coating base treatment for improving adhesion with a resin film is performed using a processing liquid not containing chromium. That is, the aluminum alloy base material is treated with an acidic solution containing ferric ions and sulfuric acid, then subjected to an acidic film forming treatment containing zirconium ions, titanium ions, phosphate ions, and fluorine ions, and then coated.
Japanese Patent No. 3383058 JP 2000-282251 A

  However, even the coating method disclosed above cannot yet be said to have sufficient adhesion, and further improvement in adhesion is desired. In addition, the use of hexavalent chromium, which is an environmentally hazardous substance, has been limited.

  The present invention has been made in view of such circumstances, and an aluminum-based substrate capable of improving the adhesion between a substrate and a resin film without using an environmentally hazardous substance such as hexavalent chromium. An object of the present invention is to provide a method for coating a material and a coated aluminum-based substrate.

  Therefore, the present inventor has intensively studied to solve this problem, and as a result of repeated trial and error, the surface roughening treatment of the base material and the formation of the metal film are simultaneously performed in the chemical conversion treatment as the base treatment of the coating. The inventors have come up with a method that makes it possible to complete the present invention.

(1) The coating method of the aluminum-type base material of this invention That is, the coating method of the aluminum-type base material of this invention is a chemical conversion treatment process which chemically converts the surface of the aluminum-type base material which consists of an aluminum base material or an aluminum alloy base material. And a coating step of coating a resin film on the surface of the chemical conversion-treated aluminum base material, wherein the chemical conversion treatment involves etching the aluminum base material with an etching solution and a water-soluble solution. It is characterized by being immersed in a chemical conversion treatment solution containing a functional metal salt.

  In the chemical conversion treatment, the metal constituting the water-soluble metal salt forms a metal film on the surface of the aluminum base material almost simultaneously with the roughening treatment on the surface of the aluminum base material by the etching solution. become. That is, a roughened metal film is present on the surface side of the semi-finished product after the chemical conversion treatment. Specifically, the surface of the aluminum base material itself is roughened, and a thin metal film is formed on the roughened surface side of the roughened aluminum base material.

(2) Aluminum-based substrate coated product of the present invention The aluminum-based substrate coated product of the present invention is a coated product produced by the above-described method for coating an aluminum-based substrate of the present invention. .

(1) Effect of the coating method of the aluminum-based substrate of the present invention According to the coating method of the aluminum-based substrate of the present invention, the surface side of the semi-finished product generated by the chemical conversion treatment, that is, the surface side of the metal film is roughened. Thus, the adhesion between the resin film coated on the surface and the aluminum-based substrate is improved. Thereby, peeling of the resin film can be suppressed.

  Furthermore, exposure of the aluminum base material itself is suppressed by forming a metal film on the surface side of the aluminum base material. For example, when a painted aluminum-based substrate coating is used as a sliding member, the aluminum-based substrate can be protected by a metal film in addition to the resin film. Moreover, when the metal film is partially deposited on the surface of the substrate at 1 μm or less by the chemical conversion treatment to form unevenness of micron or less, the adhesion between the aluminum-based substrate and the resin film can be improved. Conceivable. Since this will be described in detail in an example described later, this will be briefly described here. For example, when an aluminum-based substrate produced by the coating method of the present invention that forms a metal film and the coating method that does not form a metal film is used as a sliding member, the method using the coating method that does not form a metal film is a resin film. Although seizure occurred in a relatively short time due to peeling, the direction of the coating method for forming the metal film of the present invention does not cause peeling of the resin film even when a relatively long time has elapsed. There was no seizure. From this, it is considered that the metal film affected the strengthening of the adhesion between the aluminum-based substrate and the resin film.

  That is, according to the present invention, as described above, the aluminum-based substrate produced by the coating method of the aluminum-based substrate of the present invention by improving the adhesion between the aluminum-based substrate and the resin film and protecting the metal film. The seizure resistance and wear resistance of the coated material can be improved. That is, the produced aluminum-based base material can be effectively used for a sliding member or the like.

  Furthermore, according to the method for coating an aluminum-based substrate of the present invention, the surface roughening treatment and the metal film forming treatment can be performed almost simultaneously in the chemical conversion treatment, so that the manufacturing cost can be reduced. In addition, according to the present invention, since hexavalent chromium which is an environmentally hazardous substance is not used, it is not affected by restrictions on the use of hexavalent chromium.

(2) Effect of the aluminum-based substrate coated product of the present invention According to the aluminum-based substrate coated product of the present invention, the same effect as the effect in the method for coating an aluminum-based substrate of the present invention can be achieved.

  Next, the present invention will be described in more detail with reference to embodiments.

(1) Method for coating aluminum-based substrate The water-soluble metal salt used for the chemical conversion treatment in the above-described method for coating an aluminum-based substrate may be any one selected from sulfates and nitrates. In particular, sulfate is preferable. By using these water-soluble metal salts, a metal film can be reliably formed.

  The metal composing the water-soluble metal salt may be any one selected from copper, tin, nickel, and silver. The metal constituting the water-soluble metal salt may be any one metal selected from the above metals, or may be a plurality of metals selected from the above metals or all metals. In particular, the metal constituting the water-soluble metal salt is preferably copper. That is, the metal composing the water-soluble metal salt becomes the metal composing the metal film described above. By forming a metal film with this metal, it is possible to protect the above-described aluminum-based substrate and improve the adhesion between the aluminum-based substrate and the resin film. In particular, by using copper as the metal, it is possible to improve the slidability in addition to further improving the protection and adhesion of the aluminum-based substrate. That is, when a coated material generated by the coating method of the aluminum-based substrate is used for the sliding member, good sliding properties are required, and this requirement can be satisfied.

  Moreover, it is good for the said chemical conversion treatment solution to contain the said water-soluble metal salt below the mass which can be melt | dissolved by 1 wt% or more. If it is 1 wt% or more which is the lower limit of the water-soluble metal salt, the above-described effect of the metal film can be surely obtained. That is, when the chemical conversion solution contains 1 wt% or more of a water-soluble metal salt, a metal film having a film thickness that can achieve the above-described effect can be formed. Furthermore, a suitable chemical conversion treatment solution can be produced | generated by making the upper limit of water-soluble metal salt into below the mass which can be melt | dissolved. Here, the chemical conversion treatment solution preferably contains 3 wt% or more, more preferably 10 wt% or more of a water-soluble metal salt. Thereby, the metal film mentioned above can be formed more reliably. Furthermore, a metal film can be formed by a shorter chemical conversion treatment step. Further, the chemical conversion solution preferably contains 45 wt% or less, more preferably 30 wt% or less of a water-soluble metal salt. Moreover, the said chemical conversion treatment is good to immerse the said aluminum-type base material in the said chemical conversion treatment solution for 30 seconds-15 minutes. It is preferable to immerse for 1 to 10 minutes. By immersing for this time, the effect of the metal film can be maximized.

  Moreover, the said chemical conversion solution is good to set it as the liquid temperature of 15 degreeC or more. The liquid temperature is preferably 30 ° C. or higher. Thereby, a metal film can be formed reliably. Further, the liquid temperature is preferably 70 ° C. or lower. More preferably, the liquid temperature is 65 ° C. or lower. Thereby, it is possible to ensure good safety in painting.

  The etching solution may include one of sulfuric acid and nitric acid and hydrogen peroxide. Thereby, the roughening process of an aluminum-type base material can be performed reliably. In addition, it is good for the said chemical conversion treatment solution that either one of the sulfuric acid and nitric acid which comprise the said etching liquid, and hydrogen peroxide water are the range of 10-60 wt%, respectively. However, it is necessary to select the respective masses in a range where the total of either one of sulfuric acid and nitric acid and hydrogen peroxide does not exceed 100 wt%. In addition, Preferably it is good to set it as the range of 10-30 wt%. Further, the mass% of any one of sulfuric acid and nitric acid and the mass% of hydrogen peroxide solution may be substantially the same, or different ratios as long as they are within the above range. However, in the case of the same ratio, the mass% of both needs to be 50 wt% or less. When either one of sulfuric acid and nitric acid is 60 wt%, the hydrogen peroxide solution is 40 wt% or less.

  The resin film may be a solid lubricant surface layer made of a mixture obtained by mixing a solid lubricant and a heat resistant resin on the surface side of the aluminum base. Furthermore, the resin film is formed by mixing a resin intermediate layer made of a heat resistant resin for an intermediate layer on the surface side of the aluminum base material, and a solid lubricant and a heat resistant resin for a surface layer on the surface side of the resin intermediate layer. You may make it consist of a solid lubricant surface layer which consists of a mixture.

  Here, the intermediate layer heat-resistant resin constituting the latter resin film may be any one of polyamide-imide resin, polyimide resin, epoxy resin, and phenol resin. The heat-resistant resin as the former resin film and the heat-resistant resin for the surface layer constituting the latter resin film (hereinafter referred to as heat-resistant resin for the surface layer) are also similarly polyamideimide resin, polyimide resin, epoxy. It may be either resin or phenol resin. In the case of the heat-resistant resin for the surface layer, the polyamide-imide resin is optimal in consideration of the characteristics as the binder resin. This heat resistant resin for the surface layer is 20 to 80% by volume, preferably 40 to 65% by volume, based on the solid lubricant surface layer. Moreover, the said resin intermediate | middle layer is good in a film thickness being 0.1-20 micrometers. More preferably, the film thickness of the resin intermediate layer is 0.1 to 5 μm. Thereby, seizure resistance and wear resistance can be improved reliably.

  Moreover, the said resin intermediate | middle layer which comprises the latter resin film may be dried or baked in the temperature range of 80-200 degreeC. For example, in both cases, when the resin intermediate layer is dried at a temperature of 80 ° C. or when the resin intermediate layer is baked at 200 ° C., the seizure resistance and the wear resistance are improved. Can do. Thereby, for example, when the solid lubricant surface layer forming process, which is a subsequent process, is performed at 200 ° C., the production line for the solid lubricant surface layer can be used. That is, the drying temperature or the firing temperature can be set according to other manufacturing processes.

  The solid lubricant constituting the former and latter resin films may include at least one selected from molybdenum disulfide, graphite, and fluorine compounds. The fluorine compound is, for example, polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene (ETFE), tetrafluoroethylene hexafluoropropylene copolymer (FEP), or the like. In addition, in order to improve wear resistance, molybdenum disulfide should have an average primary particle size of 0.1 to 40 μm, preferably 1 to 10 μm. In order to improve the adhesion within the layer, graphite having an average primary particle size of 0.1 to 10 μm, preferably 1 to 5 μm is preferably used. A fluorine compound having an average primary particle size of 0.1 to 5 μm, preferably 1 to 3 μm is preferably used.

  The solid lubricant surface layer that is the former resin film and the solid lubricant surface layer that constitutes the latter resin film are further composed of hard particles, extreme pressure agent, surfactant, silane coupling agent, processing stability. Any or all of the additives for the surface layer may be contained. The resin intermediate layer in the latter coating method is for any or all of the intermediate layers of hard particles, extreme pressure materials, surfactants, silane coupling agents, processing stabilizers, antioxidants, solid lubricants. Containing an additive, and the content ratio of the intermediate layer additive in the resin intermediate layer is within a range not exceeding the content ratio of the solid lubricant and the surface layer additive in the solid lubricant surface layer. Good. Further, the resin intermediate layer may not contain any of hard particles, extreme pressure material, surfactant, silane coupling agent, processing stabilizer, antioxidant, and solid lubricant. Thereby, the seizure resistance and wear resistance of the sliding member can be further improved.

Here, the hard particles are, for example, alumina, silica, silicon carbide, silicon nitride and the like. The extreme pressure agent is, for example, a sulfur-containing metal compound such as zinc sulfide (ZnS) or silver sulfide (Ag ₂ S). Examples of the surfactant include a fluorine-based surfactant and a silicon-based surfactant. Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycid. Xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-amino Nopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-ureidopropyltri With ethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. That.

  The processing stabilizer is, for example, a bifunctional processing stabilizer, a single agent-added processing stabilizer, or the like. As the bifunctional processing stabilizer, the product name “Sumilizer GM” (chemical name: 2-tert-Butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzoyl) -4-methylphenyl manufactured by Sumitomo Chemical Co., Ltd. acrylate), a product name “Sumilizer GS (F)” manufactured by Sumitomo Chemical Co., Ltd. (chemical name: 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert -Pentylphenyl acrylate) and the like. As a single agent addition type (SA-System) processing stabilizer, a product name “Sumilizer GP” manufactured by Sumitomo Chemical Co., Ltd. (chemical name: 6- [3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propoxy) ] -2,4,8,10-tetra-t-butyldibenz [d, f] [1, 3, 2]).

  Examples of the antioxidant include a phenol-based primary antioxidant, an organic sulfur-based secondary antioxidant, an amine-based primary antioxidant, and a phosphite-based antioxidant. As phenolic primary antioxidants, the product name “Sumilizer MDP-S2” (chemical name: 2′-methylenebis (6-tert-butyl-4-methylphenol) manufactured by Sumitomo Chemical Co., Ltd., the product name “Sumizer BBM” manufactured by Sumitomo Chemical Industries, Ltd. -S "(chemical name: 4,4'-Butylidenebis (6-tert-butyl-3-methylphenol), product name" Sumilizer WX-R WX-RA WX-RC "manufactured by Sumitomo Chemical Co., Ltd. (chemical name: 4,4 '-Thiobis (6-tert-butyl-3-methylphenol)), product name “Sumilizer NW (N)” manufactured by Sumitomo Chemical Co., Ltd. (Scientific name: Alkylated bisphenol), product name “Sumilizer” manufactured by Sumitomo Chemical Industry GA-80 "(chemical name: 3,9-Bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl]]-1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5,5] undekane) etc. Examples of organic sulfur secondary antioxidants include the product name “Sumilizer MB” (chemical name: 2-Mercaptobenzimidazole) manufactured by Sumitomo Chemical Co., Ltd. Amine-based primary. Examples of the antioxidant include a product name “Sumilizer 9A” (chemical name: Alkylated diphenylamine) manufactured by Sumitomo Chemical Co., Ltd. As a phosphite antioxidant, a product name “ADK STAB PEP-36” manufactured by Asahi Denka Kogyo Co., Ltd. is there.

  The range in which the content ratio of the intermediate layer additive in the resin intermediate layer does not exceed the content ratio of the solid lubricant and the surface layer additive in the solid lubricant surface layer is, for example, the following cases. For example, when the solid lubricant surface layer has a solid lubricant content of 50% by volume and a surface layer additive content of 5% by volume, the solid lubricant and the surface layer in the solid lubricant surface layer The content ratio of the additive is 55% by volume. And the content rate of the additive for intermediate | middle layers in a resin intermediate | middle layer shall be less than 55 volume%.

(2) Aluminum-based substrate coated product The aluminum-based coated product of the present invention may be a sliding member. Although described in the above-described method for coating an aluminum-based substrate according to the present invention, the coated object according to the present invention can satisfy the seizure resistance and the wear resistance required for the sliding member. Furthermore, when forming a metal film made of copper, the slidability can be further improved, so that it is more suitable as a sliding member.

  For example, the sliding member to which the paint is applied includes a swash plate of a swash plate compressor, a shoe of the compressor, a slide bearing that supports a drive shaft of the compressor, a piston of a piston compressor, and a piston compressor. A gas passage between the compression chamber and the suction pressure region is pivotally supported integrally with the drive shaft and is rotatably supported by the housing of the piston compressor so as to rotate in synchronization with the drive shaft. There is at least one of the rotary valves that can be opened and closed.

  Next, an Example is given and this invention is demonstrated more concretely. In this embodiment, a case will be described in which an aluminum-based substrate coated product produced by the aluminum-based substrate coating method of the present invention is applied to a sliding surface of a swash plate of a swash plate compressor.

(1) Configuration of Swash Plate Type Compressor First, the configuration of the swash plate type compressor will be described with reference to FIG. FIG. 1 is a cross-sectional view showing a configuration of a swash plate compressor. As shown in FIG. 1, the swash plate compressor includes a drive shaft 1, a cylinder block 2, a front housing 3, a bore 5, a piston 6, a rotor 7, a swash plate 8, and a shoe 9. Is done. The drive shaft 1 is accommodated in a swash plate chamber 4 formed by a cylinder block 2 and a front housing 3, and is rotatably supported by a radial bearing. A plurality of bores 5 are disposed in the cylinder block 2 at positions surrounding the drive shaft 1. A single-headed piston 6 is fitted in each bore 5 so as to reciprocate. In the swash plate chamber 4, a rotor 7 is coupled to the drive shaft 1, and a swash plate 8 is fitted behind the rotor 7. In particular, in the variable capacity single-head swash plate compressor, the swash plate 8 can be tilted around a fulcrum, and the balance of gas pressure acting on both end faces of the piston 6 based on the pressure change in the swash plate chamber 4 The inclination displacement of the swash plate 8 is controlled. Further, the swash plate 8 is formed with a smooth sliding contact surface (sliding surface) 8a on the outer peripheral side of both end surfaces, and a shoe 9 is in contact with the sliding contact surface 8a. These shoes 9 are engaged with the hemispherical seat of the piston 6. When the piston 6 is linked to the swash plate 8 through the shoe 9, the rotational motion of the swash plate 8 is converted into the linear motion of the piston 6 and the medium is compressed.

(2) Coating method of sliding contact surface 8a of swash plate 8 Next, the coating method of Examples 1-7 when the present invention is applied to the sliding contact surface 8a of the swash plate 8 and the effect of the present invention are confirmed. A plurality of comparative methods 1 to 8 will be described. Here, FIG. 2 shows a schematic configuration of the sliding contact surface 8a of the swash plate 8 generated by the coating method of the example and the comparative example. As shown in FIG. 2, aluminum alloy A390 is used for the aluminum alloy base material of the swash plate 8. As shown in FIG. And the different chemical conversion treatment is given to the surface side (sliding surface side) of an aluminum alloy base material in each of an Example and a comparative example. Table 1 shows the chemical conversion treatment in each example and each comparative example. Further, a solid lubricant surface layer is formed on the surface side (sliding surface side) of the aluminum alloy base material subjected to the chemical conversion treatment.

(2-1) Example 1
First, the coating method of Example 1 will be described. This coating method includes a chemical conversion treatment process and a coating process. The chemical conversion treatment step is a step of chemical conversion treatment of the surface of the aluminum alloy base material to form a chemical conversion treatment surface, and the coating step is a step of coating the surface of the chemical conversion treatment aluminum alloy base material to form a resin film. .

(2-1-1) Chemical conversion treatment step In the chemical conversion treatment step in Example 1, first, a disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Example 1 of Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Example 1 is H ₂ SO ₄ (purity 98%) 16 wt%, hydrogen peroxide solution (purity 34%) 16 wt%, CuSO ₄ .5H ₂ O 4 wt%. It is generated by adjusting with pure water. And the produced chemical conversion treatment solution is kept at a liquid temperature of 65 ° C. Subsequently, the aluminum alloy substrate is immersed for 3 minutes in a chemical conversion treatment solution maintained at a liquid temperature of 65 ° C. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, H ₂ SO ₄ and hydrogen peroxide solution in the chemical conversion treatment solution correspond to the etching solution in the present invention, and CuSO ₄ .5H ₂ O corresponds to the water-soluble metal salt in the present invention.

  Here, the surface roughness of the aluminum alloy substrate was Rz 0.929 to 1.022 μm before the chemical conversion treatment, and Rz 0.379 to 0.49 μm after the chemical conversion treatment. That is, it can be seen that the surface of the aluminum base material is roughened by this chemical conversion treatment.

  In addition, a copper (Cu) -based metal film is formed on the surface of the aluminum-based substrate by the chemical conversion treatment. Hereinafter, a nickel (Ni) system or a tin (Sn) system may be used.

(2-1-2) Coating step Next, after the chemical conversion treatment step described above, a resin that is a solid lubricant surface layer on the surface side (sliding surface side) of the aluminum alloy base material generated by the chemical conversion treatment. A coating process for forming a film is performed. This coating process is carried out by first comprising a PAI resin varnish comprising 30% by mass of PAI resin, 70% by mass of a solvent (56% by mass of n-methyl-2-pyrrolidone, 14% by mass of xylene), and molybdenum disulfide having an average primary particle size of 1 μm. And graphite having an average primary particle size of 5 μm and PTFE having an average primary particle size of 0.3 μm are prepared. The solid lubricant surface layer is prepared by mixing the PAI resin varnish with molybdenum disulfide (MoS ₂ ), graphite, and PTFE, which are solid lubricants, in a predetermined ratio and stirring well, and then passing the solid lubricant surface layer through a three-roll mill. A coating composition was prepared. The composition of the solid lubricant surface layer was 50% by volume of PAI, 20% by volume of molybdenum disulfide, 20% by volume of graphite, and 10% by volume of PTFE. This coating composition is optionally diluted with a solvent n-methyl-2-pyrrolidone, xylene or a mixed solvent thereof depending on the type of coating method (spray coating, roll coating, etc.). The material thus obtained is coated on the resin intermediate layer (sliding surface side) by air spraying and then fired at 205 ° C. for about 1 hour to form a solid lubricant surface layer. did. In addition, the film thickness of this solid lubricant surface layer shall be 15-20 micrometers.

(2-2) Examples 2 to 7 and Comparative Examples 1 to 8
Next, the coating method of Examples 2-7 and Comparative Examples 1-8 is demonstrated. In addition, since the coating process of these coating methods is the same as the coating process in the said Example 1, only each chemical conversion treatment process is demonstrated below.

(2-2-1) Example 2
In the chemical conversion treatment step in Example 2, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Example 2 of Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion solution of Example 2 is such that HNO ₃ (purity 60%) is 16 wt%, hydrogen peroxide solution (purity 34%) is 16 wt%, and CuSO ₄ .5H ₂ O is 4 wt%. It is produced by adjusting with pure water. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Subsequently, the aluminum alloy base material is immersed in a chemical conversion treatment solution maintained at a liquid temperature of 25 ° C. for 3 minutes. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, HNO ₃ and hydrogen peroxide solution in the chemical conversion solution correspond to the etching solution in the present invention, and CuSO ₄ .5H ₂ O corresponds to the water-soluble metal salt in the present invention.

  Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1. In addition, a copper (Cu) -based metal film is formed on the surface of the aluminum-based substrate by the chemical conversion treatment.

(2-2-2) Example 3
In the chemical conversion treatment step in Example 3, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Example 3 of Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion solution of Example 3 is 16 wt% for H ₂ SO ₄ (purity 98%), 16 wt% for hydrogen peroxide (purity 34%), and 10 wt% for CuSO ₄ .5H ₂ O. It is generated by adjusting with pure water. And the produced chemical conversion treatment solution is kept at a liquid temperature of 65 ° C. Subsequently, the aluminum alloy substrate is immersed for 3 minutes in a chemical conversion treatment solution maintained at a liquid temperature of 65 ° C. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, H ₂ SO ₄ and hydrogen peroxide solution in the chemical conversion treatment solution correspond to the etching solution in the present invention, and CuSO ₄ .5H ₂ O corresponds to the water-soluble metal salt in the present invention.

  Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1. In addition, a copper (Cu) -based metal film is formed on the surface of the aluminum-based substrate by the chemical conversion treatment.

(2-2-3) Example 4
In the chemical conversion treatment step in Example 4, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Example 4 of Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Example 4 is 16 wt% for H ₂ SO ₄ (purity 98%), 16 wt% for hydrogen peroxide (purity 34%), and 4 wt% for NiSO ₄ .6H ₂ O. It is generated by adjusting with pure water. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Subsequently, the aluminum alloy base material is immersed in a chemical conversion treatment solution maintained at a liquid temperature of 25 ° C. for 3 minutes. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, H ₂ SO ₄ and hydrogen peroxide solution in the chemical conversion treatment solution correspond to the etching solution in the present invention, and NiSO ₄ .6H ₂ O corresponds to the water-soluble metal salt in the present invention.

  Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1. Further, a nickel (Ni) -based metal film is formed on the surface of the aluminum-based substrate by the chemical conversion treatment.

(2-2-4) Example 5
In the chemical conversion treatment step in Example 5, first, the disc-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Example 5 of Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Example 5 is 16 wt% for H ₂ SO ₄ (purity 98%), 16 wt% for hydrogen peroxide (purity 34%), and 10 wt% for NiSO ₄ .6H ₂ O. It is generated by adjusting with pure water. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Subsequently, the aluminum alloy base material is immersed in a chemical conversion treatment solution maintained at a liquid temperature of 25 ° C. for 3 minutes. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, H ₂ SO ₄ and hydrogen peroxide solution in the chemical conversion treatment solution correspond to the etching solution in the present invention, and NiSO ₄ .6H ₂ O corresponds to the water-soluble metal salt in the present invention.

  Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1. Further, a nickel (Ni) -based metal film is formed on the surface of the aluminum-based substrate by the chemical conversion treatment.

(2-2-5) Example 6
In the chemical conversion treatment step in Example 6, first, the disc-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Example 6 of Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Example 6 is pure so that H ₂ SO ₄ (purity 98%) is 16 wt%, hydrogen peroxide water (purity 34%) is 16 wt%, and SnSO ₄ is 4 wt%. Produced by adjusting with water. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Subsequently, the aluminum alloy base material is immersed in a chemical conversion treatment solution maintained at a liquid temperature of 25 ° C. for 3 minutes. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, H ₂ SO ₄ and hydrogen peroxide solution in the chemical conversion treatment solution correspond to the etching solution in the present invention, and SnSO ₄ corresponds to the water-soluble metal salt in the present invention.

  Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1. In addition, a tin (Sn) -based metal film is formed on the surface of the aluminum-based substrate by the chemical conversion treatment.

(2-2-6) Example 7
In the chemical conversion treatment step in Example 7, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Example 7 of Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Example 7 is H ₂ SO ₄ (purity 98%) 16 wt%, hydrogen peroxide (purity 34%) 16 wt%, SnSO ₄ .5H ₂ O 10 wt%. It is generated by adjusting with pure water. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Subsequently, the aluminum alloy base material is immersed in a chemical conversion treatment solution maintained at a liquid temperature of 25 ° C. for 3 minutes. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, H ₂ SO ₄ and hydrogen peroxide solution in the chemical conversion treatment solution correspond to the etching solution in the present invention, and SnSO ₄ corresponds to the water-soluble metal salt in the present invention.

  Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1. In addition, a tin (Sn) -based metal film is formed on the surface of the aluminum-based substrate by the chemical conversion treatment.

(2-2-7) Comparative Example 1
In the chemical conversion treatment step in Comparative Example 1, first, the disc-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 1 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Comparative Example 1 is produced by adjusting with pure water so that H ₂ SO ₄ (purity 98%) is 16 wt% and hydrogen peroxide water (purity 34%) is 16 wt%. Is done. And the produced chemical conversion treatment solution is kept at a liquid temperature of 65 ° C. Subsequently, the aluminum alloy substrate is immersed for 3 minutes in a chemical conversion treatment solution maintained at a liquid temperature of 65 ° C. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(2-2-8) Comparative Example 2
In the chemical conversion treatment step in Comparative Example 2, first, the disc-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 2 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Comparative Example 2 is produced by adjusting with pure water so that HNO ₃ (purity 60%) is 50 wt%. And the produced | generated chemical conversion treatment solution is hold | maintained at 60 degreeC liquid temperature. Then, an aluminum alloy base material is immersed for 1 minute in the chemical conversion treatment solution hold | maintained at 60 degreeC liquid temperature. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(2-2-9) Comparative Example 3
In the chemical conversion treatment step in Comparative Example 3, first, the disc-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 3 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Comparative Example 3 is produced by adjusting with pure water so that NaOH becomes 9 wt%. And the produced | generated chemical conversion treatment solution is hold | maintained at 60 degreeC liquid temperature. Then, an aluminum alloy base material is immersed for 1 minute in the chemical conversion treatment solution hold | maintained at 60 degreeC liquid temperature. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(2-2-10) Comparative Example 4
In the chemical conversion treatment step in Comparative Example 4, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 4 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Comparative Example 4 was 9 wt% H ₂ SO ₄ (purity 98%), 9 wt% hydrogen peroxide (purity 34%), and 0.5 wt% CuSO ₄ .5H ₂ O. It is generated by adjusting with pure water so as to be%. And the produced | generated chemical conversion treatment solution is hold | maintained at 60 degreeC liquid temperature. Then, an aluminum alloy base material is immersed for 1 minute in the chemical conversion treatment solution hold | maintained at 60 degreeC liquid temperature. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(2-2-11) Comparative Example 5
In the chemical conversion treatment step in Comparative Example 5, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 5 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion solution of Comparative Example 5 is produced by adjusting with pure water so that AgNO ₃ is 1 wt%. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Then, an aluminum alloy base material is immersed for 1 minute in the chemical conversion treatment solution hold | maintained at the liquid temperature of 25 degreeC. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(2-2-12) Comparative Example 6
In the chemical conversion treatment step in Comparative Example 6, first, the disc-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 6 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Comparative Example 6 is produced by adjusting with pure water so that hydrazine is 5 wt%. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Then, an aluminum alloy base material is immersed for 1 minute in the chemical conversion treatment solution hold | maintained at the liquid temperature of 25 degreeC. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(2-2-13) Comparative Example 7
In the chemical conversion treatment step in Comparative Example 7, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 7 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Comparative Example 7 is produced by adjusting with pure water so that Al (OH) ₃ becomes 1 wt%. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Then, an aluminum alloy base material is immersed for 1 minute in the chemical conversion treatment solution hold | maintained at the liquid temperature of 25 degreeC. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(2-2-14) Comparative Example 8
In the chemical conversion treatment step in Comparative Example 8, first, the disk-shaped aluminum alloy base material is degreased and then washed with water. Subsequently, 400 ml of the chemical conversion solution shown in Comparative Example 8 in Table 1 is prepared in a 500 ml beaker. Specifically, the chemical conversion treatment solution of Comparative Example 8 is produced by adjusting with pure water so that sodium borohydride is 1 wt%. And the produced | generated chemical conversion treatment solution is hold | maintained at the liquid temperature of 25 degreeC. Then, an aluminum alloy base material is immersed for 1 minute in the chemical conversion treatment solution hold | maintained at the liquid temperature of 25 degreeC. Then, after washing with water, drying is performed at about 80 ° C. for about 30 minutes. Here, the surface roughness of the aluminum alloy base material is substantially the same both before and after the chemical conversion treatment in Example 1.

(3) Test for measuring seizure time of swash plate 8 Next, effects such as seizure resistance in the case of using the aluminum base material produced by the aluminum base material coating method of the present invention as a sliding member were confirmed. In order to do this, a seizure time measurement test of the swash plate 8 was performed. Specifically, as shown in FIG. 3, the swash plate 8 is rotated around the vertical axis on the upper surface of the shoe 9 so that the sliding contact surface 8 a of the swash plate 8 is in sliding contact with the upper surface of the fixed shoe 9. Was done. The test conditions at this time were under refrigeration oil lubrication and rotated at a speed of 6 m / sec while applying a load of 5000 N. And the time until seizure was measured. The results of this seizure time measurement test are shown in FIG. FIG. 4 is a diagram showing the time until seizure for each of Examples 1 to 7 and Comparative Examples 1 to 8 in the seizure time measurement test.

  As shown in FIG. 4, the coated products produced by the coating methods of Examples 1 to 3 did not cause seizure even after 7000 seconds from the start of the test. The coated products produced by the coating methods of Examples 4 to 7 were seized approximately 6000 seconds after the start of the test. On the other hand, the coated products produced by the coating methods of Comparative Example 1 and Comparative Examples 3 to 7 were seized before 1000 seconds passed from the start of the test. The coated products produced by the coating methods of Comparative Example 2 and Comparative Example 8 were seized around 3000 seconds and 4000 seconds from the start of the test, respectively. That is, it can be seen that all of Examples 1 to 7 have a longer time until seizure than all of Comparative Examples 1 to 8.

In particular, when Example 1 and Comparative Example 1 are compared, the difference is whether or not CuSO ₄ .5H ₂ O is contained in the chemical conversion solution. From both test results, it can be seen that Example 1 containing CuSO ₄ .5H ₂ O has a significantly longer time to seizure than Comparative Example 1. That is, it can be seen that the seizure resistance is greatly improved by forming the Cu film on the aluminum-based substrate. Furthermore, when Example 1 and Comparative Example 4 are compared, both show that the amount of CuSO ₄ .5H ₂ O contained in the chemical conversion solution is smaller than that of Comparative Example 4 compared to Example 1, and the immersion time. However, Comparative Example 4 is different from Example 1 in that the time is shorter. And from both test results, it can be seen that Example 1 has a longer time to seizure than Comparative Example 4. That is, the seizure resistance is improved by increasing the proportion of the water-soluble metal salt as in Example 1. Furthermore, seizure resistance is improved by increasing the immersion time as in Example 1.

Further, according to Examples 4 and 6, even when instead of CuSO ₄ · 5H ₂ O in Example 1 as a water-soluble metal salt and NiSO ₄ · 6H ₂ O or SnSO _4, with good seizure It can be seen that sex can be obtained. However, as a kind of water-soluble metal salt, the seizure resistance is best when the CuSO ₄ .5H ₂ O of Example 1 is used. Furthermore, it can be seen that when the proportion of the water-soluble metal salt is increased as in Examples 3, 5, and 7, compared with Examples 1, 4, and 6, the time until seizure is extended. That is, it can be seen that the seizure resistance is improved by increasing the proportion of the water-soluble metal salt. Furthermore, according to Examples 1-7, even if the liquid temperature of a chemical conversion treatment solution is 65 degreeC, even if it is a case where it is 25 degreeC, it turns out that there exists the same effect. Moreover, it turns out that the same effect is produced even when nitric acid is used instead of sulfuric acid as an etching solution as in Example 2.

(4) Others In the above embodiment, only the solid lubricant surface layer is formed in the coating process, but the present invention is not limited to this. For example, as described above, the resin intermediate layer described above may be formed on the surface side of the aluminum-based substrate, and the solid lubricant surface layer may be formed on the surface side. In this case, the seizure resistance is further improved as compared with the case of the above embodiment.

It is sectional drawing which shows the structure of a swash plate type compressor. It is a schematic block diagram which shows the sliding contact surface 8a of the swash plate 8 produced | generated by the coating method of an Example and a comparative example. It is a figure explaining the burning time measurement test of the swash plate. It is a figure which shows the time until seizure for each of Examples 1 to 7 and Comparative Examples 1 to 8 in the seizure time measurement test.

Explanation of symbols

1: Drive shaft 2: Cylinder block 3: Front housing 4: Swash plate chamber 5: Bore 6: Piston 7: Rotor 8: Swash plate 8a: Sliding contact surface 9: Shoe

Claims (14)

A chemical conversion treatment step for chemical conversion treatment of the surface of an aluminum-based substrate comprising an aluminum substrate or an aluminum alloy substrate;
A painting step of painting a resin film on the surface of the aluminum base material subjected to the chemical conversion treatment;
In the coating method of an aluminum-based substrate comprising:
The chemical conversion treatment is performed by immersing the aluminum base material in a chemical conversion treatment solution containing an etching solution and a water-soluble metal salt.   In the chemical conversion treatment, the metal constituting the water-soluble metal salt forms a metal film on the surface of the aluminum base material substantially simultaneously with the roughening treatment on the surface of the aluminum base material by the etching solution. Item 2. A method for coating an aluminum-based substrate according to Item 1.   The method for coating an aluminum-based substrate according to any one of claims 1 and 2, wherein the water-soluble metal salt is any one selected from sulfates and nitrates.   The metal which comprises the said water-soluble metal salt consists of any one selected from copper, tin, nickel, and silver, The coating method of the aluminum-type base material as described in any one of Claims 1-3.   The said chemical conversion treatment solution is a coating method of the aluminum-type base material as described in any one of Claim 1 and 2 containing the said water-soluble metal salt below the mass which can be melt | dissolved by 1 wt% or more.   The said chemical conversion treatment is the coating method of the aluminum type base material as described in any one of Claims 1, 2, and 5 which immerses the said aluminum type base material in the said chemical conversion treatment solution for 30 seconds-15 minutes.   The said chemical conversion treatment solution is a liquid temperature of 15 degreeC or more, The coating method of the aluminum-type base material as described in any one of Claims 1, 2, 5, and 6.   The method for coating an aluminum-based substrate according to claim 1, wherein the etching solution contains one of sulfuric acid and nitric acid and a hydrogen peroxide solution.   9. The method for coating an aluminum-based substrate according to claim 8, wherein the chemical conversion treatment solution contains 10 to 60 wt% of either sulfuric acid or nitric acid constituting the etching solution and hydrogen peroxide.   10. The aluminum system according to claim 1, wherein the resin film is a solid lubricant surface layer made of a mixture obtained by mixing a solid lubricant and a heat-resistant resin on the surface side of the aluminum-based substrate. Substrate coating method. The resin film is
A resin intermediate layer comprising a heat-resistant resin for an intermediate layer on the surface side of the aluminum-based substrate;
A solid lubricant surface layer composed of a mixture of a solid lubricant and a heat-resistant resin for the surface layer mixed on the surface side of the resin intermediate layer;
The coating method of the aluminum-type base material as described in any one of Claims 1-9 which consists of.   An aluminum-based substrate coated product produced by the aluminum-based substrate coating method according to any one of claims 1 to 11.   The aluminum-based substrate coated product according to claim 12, wherein the aluminum-based substrate coated product is a sliding member.   The aluminum-based base material is integrated with the swash plate of the swash plate compressor, the shoe of the compressor, the slide bearing that supports the drive shaft of the compressor, the piston of the piston compressor, and the drive shaft of the piston compressor. The drive shaft is pivotally supported by the housing of the piston compressor and is rotated in synchronization with the drive shaft so that the gas passage between the compression chamber and the suction pressure region can be opened and closed. The aluminum-based substrate coated product according to claim 13, which is at least one of rotary valves.

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