JP5102952B2 - Sliding member and method of manufacturing sliding member - Google Patents

Description

  The present invention relates to a sliding member used for sliding portions of various devices and a method for manufacturing the same.

  Polyamideimide resin is a resin material that has excellent heat resistance and mechanical strength and has self-lubricating properties. Therefore, it is often used for sliding members of various devices.

  For example, as disclosed in Patent Document 1, the sliding member includes a base material, and a sliding layer made of a solid lubricant and a polyamideimide resin that is a binder that holds the solid lubricant. Such a sliding layer is usually obtained by applying a coating composition in which a solid lubricant is mixed with a resin varnish to the sliding surface side of the substrate.

  There is also a member produced by injection molding from a molding material in which polyphenylene sulfide resin or polyarylene sulfide resin is blended with polyamideimide resin. For example, Patent Document 2 discloses a sliding ring made of a resin composition in which an organic clay complex obtained by treating a swellable layered silicate with an organic cation in a molding material made of a polyamideimide resin and a polyarylene sulfide resin. Are listed. However, injection molding is performed by injecting heat-melted material into a mold and molding, so there is no degree of freedom for the shape, and it is not compatible with sliding parts that require a thin sliding layer. It is difficult to ensure adhesion. Moreover, in the polymer blend system as described above, since the polymer to be blended is different from the polyamideimide resin as the matrix, the mechanical properties are deteriorated and the heat resistance is inferior due to the influence of the blended polymer.

And in recent years, in order to ensure the reliability more than before, the further improvement of the characteristic of a sliding member is calculated | required.
Japanese Patent Laid-Open No. 11-13638 JP 2001-302914 A

  In view of the above circumstances, an object of the present invention is to provide a novel sliding member having characteristics superior to those of the prior art and a manufacturing method thereof.

  As a result of intensive research and trial and error, the present inventors have further improved the characteristics of the sliding member by using, for the sliding layer, a resin composition in which an organic layered clay mineral is uniformly dispersed in a polyamide-imide resin. It has been found that it can be further improved.

That is, the sliding member of the present invention has a base material and a sliding layer, and the sliding layer is
Formed on at least the sliding surface side of the substrate,
A polyamide-imide resin, and an organic lamellar clay mineral was uniformly dispersed in the polyamide-imide resin a layered clay mineral that has been organized by the organic onium ion, and a resin composition comprising,
A solid lubricant retained in the resin composition;
And wherein the Tona Turkey.

Here, the “organized layered clay mineral” is a layered clay mineral organized by organic onium ions . Layered clay mineral is usually a large number of sheets has a laminated layer structure (interlayer distance d = 12 nm), the organic lamellar clay mineral, the interlayer is swollen by being organized. Since such an organized layered clay mineral has high compatibility with organic matter, the interlayer distance of each layer is increased in the polyamideimide resin, and in some cases, each layer is peeled off in the polyamideimide resin. As a result, the organically modified layered clay mineral can be uniformly dispersed in the polyamideimide resin.

Under the present circumstances, it is preferable that the average linear expansion coefficient in 100-200 degreeC of the resin composition which comprises the said sliding layer is 5 * 10 < ^-5 > / degrees C or less.

And the manufacturing method of the sliding member of this invention is a manufacturing method of the above-mentioned sliding member of this invention, Comprising: The resin solution which consists of a polyamideimide resin and the solvent which melt | dissolves this polyamideimide resin, and a solid lubricant And a coating composition application step of applying a coating composition comprising a mixture of the organic layered clay mineral, which is a layered clay mineral organized by organic onium ions, to at least the sliding surface side of the substrate, and the coating And a sliding layer forming step of forming a sliding layer by removing the solvent of the composition.

  According to the sliding member and the manufacturing method of the sliding member of the present invention, the organically layered clay mineral is uniformly dispersed in the polyamideimide resin. Since the layered clay mineral dispersed in the polyamideimide resin is an inorganic substance, the resin composition is excellent in wear resistance. As a result, since the wear resistance of the sliding layer is improved, a sliding member having excellent sliding characteristics can be obtained.

In particular, if the average linear expansion coefficient at 100 to 200 ° C. of the resin composition is 5 × 10 ⁻⁵ / ° C. or less, even if the temperature of the sliding layer rises due to sliding, the thermal expansion of the sliding layer Is small. Therefore, it is possible to prevent the peeling of the sliding layer that occurs during use at a high temperature.

  The sliding layer of the sliding member of the present invention is a sliding layer formed on a substrate, and is a paint obtained by mixing a solid lubricant and an organic layered clay mineral in a resin solution comprising a polyamideimide resin and a solvent. It is formed by applying the composition to a substrate. Therefore, it is different from the sliding member manufactured by injection molding, and as in Patent Document 2, it is not necessary to add polyphenylene sulfide resin or polyarylene sulfide resin to the polyamideimide resin. Moreover, even if it is a polyamide imide resin excellent in heat resistance, manufacture is easy.

  The best mode for carrying out the sliding member and the manufacturing method of the sliding member of the present invention will be described below.

[Sliding member]
The sliding member of the present invention mainly has a base material and a sliding layer.

  The substrate is not particularly limited as long as it is a sliding part of various devices, but is preferably made of metal. For example, iron, steel, aluminum, aluminum alloy containing Mg, Cu, Zn, Si, Mn and the like, copper, copper alloy containing Zn, Al, Sn, Mn and the like are preferable. And it is preferable that especially a base material is a sliding component of a compressor. That is, the sliding member of the present invention can be used as a sliding member for a compressor. For example, the sliding member of the present invention can be used for a swash plate of a swash plate compressor. The sliding member of the present invention can be used for a shoe of a compressor. In some cases, the swash plate and the shoe of the swash plate compressor slide relative to each other in a dry state where there is no lubricating oil. Even when sliding in such a very severe unlubricated state, it is desirable not to cause seizure or wear. By using the sliding member of the present invention for a swash plate, a shoe or the like of a swash plate compressor, the conditions required for the swash plate compressor can be sufficiently satisfied.

  In addition to the above, it can also be used for bearings that support the drive shaft of the compressor. In addition, it is pivotally supported integrally with the drive shaft of the piston compressor, and the drive shaft is rotatably supported by the housing of the piston compressor so as to rotate synchronously with the drive shaft so that the compression chamber and the suction pressure region are separated. It can also be used for a rotary valve that can open and close a gas passage between them, or a piston of a piston type compressor.

  The sliding layer is formed on at least the sliding surface side of the base material.

  The sliding layer is composed of a resin composition composed of a polyamideimide resin and an organically modified layered clay mineral uniformly dispersed in the polyamideimide resin, and a solid lubricant retained in the resin composition. That is, the resin composition serves as a binder that holds the solid lubricant.

  There is no particular limitation on the polyamide-imide resin that can be used in the resin composition, but it can be produced by a usual method such as a diisocyanate method or an acid chloride method. Of these, the diisocyanate method is preferred from the viewpoint of polymerizability and cost. In addition, the number average molecular weight of the polyamideimide resin is preferably 10,000 or more, more preferably 12,000 or more, and further preferably 14,000 or more. When the number average molecular weight is less than 10,000, flexibility and heat resistance tend to decrease. In the present invention, the higher the number average molecular weight of the polyamideimide resin, the better the sliding properties, but it is preferably 35,000 or less. When it becomes larger than 35,000, the viscosity of the coating composition for the sliding member finally obtained becomes high and the workability at the time of coating is inferior.

  Organic solvents used for polymerization include amide solvents such as n-methyl-2-pyrrolidone, dimethylacetamide and dimethylformamide, sulfur solvents such as dimethylsulfoxide and sulfolane, nitro solvents such as nitromethane and nitroethane, and diglyme. Ether solvents such as tetrahydrofuran, ketone solvents such as cyclohexanone and methyl ethyl ketone, nitrile solvents such as acetonitrile and propionitrile, and solvents having a relatively high dielectric constant such as γ-butyrolactone and tetramethylurea However, a solvent having a relatively low dielectric constant such as xylene or toluene may be mixed and used.

  The reaction temperature is usually preferably 50 to 200 ° C., and is carried out in the presence of tertiary amines, alkali metals, alkaline earth metals, metals such as cobalt, tin, and zinc, and metalloid compounds to promote the reaction. Also good.

  In order to obtain the polyamideimide resin of the present invention, trimellitic anhydride is used as an acid component monomer, but oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid are used to impart solubility and polymerizability to the solvent. , Pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and other aliphatic dicarboxylic acids, isophthalic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, terephthalic acid, Diphenylmethane 4,4′dicarboxylic acid, diphenylmethane 2,4′dicarboxylic acid, diphenylmethane 3,4′dicarboxylic acid, diphenylmethane 3,3′dicarboxylic acid, 1,2 diphenylethane 4,4′dicarboxylic acid, 1,2 diphenylethane 2 , 4 'dicarboxylic acid, 1,2 diphenylethane 3,4' dicarboxylic acid 1,2 diphenylethane 3,3′dicarboxylic acid, 2,2′bis (4carboxyphenyl) propane, 2- (2carboxyphenyl) 2- (4carboxyphenyl) propane, 2- (3carboxyphenyl) 2- (4 carboxyphenyl) propane, diphenyl ether 4,4 ′ dicarboxylic acid, diphenyl ether 2,4 dicarboxylic acid, diphenyl ether 3,4 dicarboxylic acid, diphenyl ether 3,3 ′ dicarboxylic acid, diphenyl sulfone 4,4 ′ dicarboxylic acid, diphenyl sulfone 2, 4 dicarboxylic acid, diphenyl sulfone 3,4 dicarboxylic acid, diphenyl sulfone 3,3 ′ dicarboxylic acid, benzophenone 4,4 ′ dicarboxylic acid, benzophenone 2,4 dicarboxylic acid, benzophenone 3,4 dicarboxylic acid, benzophenone 3,3 ′ di Aromatic dicarboxylic acids such as rubonic acid, pyridine 2,6 dicarboxylic acid, bis [(4 carboxy) phthalimide] 4,4 ′ diphenyl ether, bis [(4 carboxy) phthalimide] α, α ′ metaxylene, butane 1,2, 4-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid and anhydrides thereof, butane 1,2,3,4 tetracarboxylic acid, pyromellitic acid, benzophenone 3,3 ′, 4,4 ′ tetracarboxylic acid, diphenyl ether 3,3 ′, 4,4 ′ tetracarboxylic acid, biphenyl 3,3 ′, 4,4 ′ tetracarboxylic acid, biphenyl 2,2 ′, 3,3 ′ tetracarboxylic acid, naphthalene 2,3,6,7 tetra Carboxylic acid, naphthalene 1,2,4,5 tetracarboxylic acid, naphthalene 1,4,5,8 tetracarboxylic acid and their dianhydrides , Ethylene glycol bisanhydro trimellitate, propylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene glycol bis anhydro trimellitate, etc. Two or more mixtures can be copolymerized.

  On the other hand, as the amine component, m-phenylenediamine, p-phenylenediamine, oxydianiline, methylenedianiline, hexafluoroisopropylidenedianiline, diamino m-xylene, diamino p-xylene, 1,4 naphthalenediamine, 1, 5 naphthalenediamine, 2,6 naphthalenediamine, 2,7 naphthalenediamine, 2,2′bis (4aminophenyl) propane, 2,2′bis (aminophenyl) hexafluoropropane, 4,4′diaminodiphenylsulfone, 4 , 4 'diaminodiphenyl ether, 3,3' diaminodiphenyl sulfone, 3,4 diaminobiphenyl, 4,4 'diaminobenzophenone, hexamethylene diamine, tetramethylene diamine, isophorone diamine, 3,4 diamino diphenyl ether, Sopropylidenedianiline, 3,3′diaminobenzophenone, dicyclohexyl 4,4′diamine, 4,4′diaminodiphenylmethane, o-tolidine, 2,4tolylenediamine, 1,3-bis (3aminophenoxy) benzene, 1,3-bis (4aminophenoxy) benzene, 1,4-bis (4aminophenoxy) benzene, 2,2-bis [4- (4aminophenoxy) phenyl] propane, 2,2-bis [4- ( 4aminophenoxy) phenyl] sulfone, 4,4′bis (4aminophenoxy) biphenyl, 2,2-bis [4- (4aminophenoxy) phenyl] hexafluoropropane, 4,4′diaminodiphenyl sulfide, 3,3 'Diaminodiphenyl sulfide or one or more of these diisocyanates The compound can be copolymerized. Among these isocyanate components or amine components, diphenylmethane diisocyanate is most preferable from the viewpoints of reactivity, abrasion resistance, solubility, and price.

Although there is no limitation in particular in the organic layered clay mineral disperse | distributed in the said polyamidoimide resin, in this invention, the layered clay mineral organized by the organic onium ion is essential .

  Here, the layered clay mineral is a so-called layered phyllosilicate. For example, there are smectite layered clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, swellable mica, kaolinite and the like. These may be natural or synthesized. Therefore, the organically modified layered clay mineral is preferably sodium-type montmorillonite or sodium-type mica organized by organic onium ions. Sodium-type montmorillonite exists widely in nature, and sodium-type mica is stably supplied as a synthetic product and is easily available. Therefore, it is preferable as a raw material for organically layered clay minerals.

  The organic onium ion preferably has 6 or more carbon atoms, for example, an alkylonium ion is representative. If the number of carbon atoms is less than 6, it is difficult for the polyamideimide resin to enter (intercalate) between the layers, and each layer may be peeled off and cannot be dispersed. The organic onium ion further preferably has 10 or more carbon atoms. When the number of carbon atoms is 10 or more, the organic onium ions shield the hydrophilicity of the clay layer, so that compatibility with the polyamideimide resin is enhanced. The organic onium ion is more preferably one containing a polar group such as a hydroxyl group. When a polar group such as a hydroxyl group is contained, the interaction with the amide group or imide group of the polyamide-imide resin is enhanced, and the mechanical properties are improved due to the dispersion of the clay layer and the hydrogen bond with the amide group or imide group. It is to do.

  Examples of onium ions are quaternary ammonium ions such as hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, dodecyl trimethyl ammonium ion, lauryl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion. Ion, trioctylammonium ion, dioctadecyldimethylammonium ion, trioctylammonium ion, dioctadecyldimethylammonium ion (also known as distearyldimethylammonium ion), trioctadecylammonium ion, benzyldimethyloctadecylammonium ion, methyloctadecylbis-2-hydroxyl Ammonium ion, ammoni Or the like can be used Mudodekan acid.

  Further, phosphenium ions may be used. Examples of the phosphenium ion include tetraethylphosphenium ion, triethylbenzylphosphenium ion, tetra-n-butylphosphenium ion, tri-n-butylhexadecylphosphenium ion, tri-n-butylbenzylphosphenium ion, and the like. Can be used.

  Since the layered clay mineral is uniformly dispersed in the polyamide-imide resin in a state where the layers of each layer are sufficiently spread or in a state where each layer is separated, it is preferable that the layers are greatly swollen. The cation exchange capacity of the layered clay mineral is preferably 50 to 200 meq / 100 g, more preferably 70 to 150 meq / 100 g. If the cation exchange capacity is in the above range, the organic onium ion is sufficiently organically formed by ion exchange, and thus the organically layered clay mineral is well dispersed in the polyamideimide resin.

  When the cation exchange capacity exceeds 200 meq / 100 g, the number of bonds between the negative charge of the clay layer and the cations between the clay layers increases, so that the bond strength between the layered clay minerals becomes stronger, and organic Intervention between layers by ion exchange of onium ions becomes difficult, and as a result, swelling of the layered clay mineral may be insufficient.

  The resin composition may be 10 to 70% by weight, more preferably 20 to 60% by weight when the entire sliding layer is 100% by weight. The organic layered clay mineral is preferably added at least 1% by weight, more preferably at least 3 to 20% by weight, when the resin composition is 100% by weight. If it is less than 1% by weight, the performance may be insufficient, and if it is 20% by weight or more, dispersibility may deteriorate. If the organic layered clay mineral is added in the above range, the resin composition has a smaller coefficient of thermal expansion and a higher Young's modulus than the polyamide-imide resin to which no organic layered clay mineral is added.

  Solid lubricants retained in the resin composition include layered structures such as graphite and talc, soft metals such as Pb, Ag and Cu and compounds thereof, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), Usual solid lubricants such as fluorine compounds such as ethylene-tetrafluoroethylene copolymer (ETFE), perfluoroethylene-propene copolymer (FEP), polyvinylidene fluoride (PVDF), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc. Any material may be used as long as it is used, and it preferably contains at least one of fluororesin, molybdenum disulfide, and graphite. In particular, when the sliding member of the present invention is used in a non-lubricated state, it is preferable to use PTFE as a solid lubricant. The solid lubricant is preferably in the form of powder and dispersed in the resin composition, and a powder having an average primary particle size of 0.1 to 20 μm, preferably 0.1 to 10 μm is used.

  The solid lubricant is preferably held at 10 to 90% by weight, more preferably 20 to 70% by weight, when the entire sliding layer is 100% by weight.

And in the sliding member of the present invention having the above-mentioned configuration, the average linear expansion coefficient at 100 to 200 ° C. of the resin composition constituting the sliding layer is smaller than that of the polyamide-imide resin to which no organic layered clay mineral is added, It is preferably 5 × 10 ⁻⁵ / ° C. or less. If the thermal expansion coefficient of the resin composition is within the above range, even when the sliding member is used under high temperature conditions, or even when the temperature of the sliding layer rises due to sliding, the thermal expansion of the sliding layer It is possible to prevent the sliding layer from being peeled off.

  Further, the Young's modulus (tensile modulus) of the resin composition is larger than that of a single polyamideimide resin, and preferably 2500 MPa or more. If the Young's modulus of the resin composition is too low, the wear resistance tends to decrease. In addition, the sliding layer made of a resin composition having a high Young's modulus is easily deformed even when an impact is applied, and the area subjected to the impact can be increased by the deformation, thereby reducing the surface pressure. .

In addition, the sliding member of this invention is not limited to said embodiment, You may add another structure. For example, a substrate having a surface treatment on the surface on the sliding surface side or a substrate having an intermediate layer different from the sliding layer on the surface may be used, and further, titanium oxide, barium sulfate. Coloring of inorganic particles such as calcium carbonate, alumina, silicon oxide, iron oxide and chromium oxide, extreme pressure agents such as sulfur-containing metal compounds such as zinc sulfide (ZnS) and silver sulfide (Ag ₂ S), dyes and pigments Agents, surfactants, dispersants, antioxidants, flame retardants, antistatic agents, leveling agents, antifoaming agents, silane coupling agents and epoxy resins, phenol resins, melamine resins, polyfunctional isocyanates and other crosslinking agents The sliding layer may contain any or all of the additives.

[Sliding member manufacturing method]
The manufacturing method of the sliding member of this invention is a manufacturing method of the said sliding member, Comprising: A coating composition application | coating process and a sliding layer formation process are comprised.

  The coating composition application step is a step of applying the coating composition to at least the sliding surface side of the substrate. The coating composition is composed of a mixture of a resin solution, a solid lubricant, and an organized layered clay mineral. The resin solution is not particularly limited as long as it is a resin solution comprising a polyamideimide resin and a solvent for dissolving the polyamideimide resin. A so-called PAI resin varnish comprising the above-mentioned polyamideimide resin (PAI resin) and a solvent for dissolving the PAI resin is desirable. In this case, the solvent may be a polar solvent such as n-methyl-2-pyrrolidone or xylene in which the polyamideimide resin to be used and the organically modified layered clay mineral to be added are soluble. These solvents may be used alone or in a mixed solvent.

  When mixing the coating composition, the organic layered clay mineral may be added to the resin solution and mixed, and then the solid lubricant may be added and mixed again. Alternatively, the solid lubricant may be added to the resin solution. Alternatively, the organically modified layered clay mineral may be added all at once and mixed. What is necessary is just to mix using a general ball mill and a mixer, when mixing a coating composition. By putting at least the organic layered clay mineral into the resin solution and mixing it, the organic part of the layered clay mineral becomes compatible (compatible) with the polyamideimide resin. Spreads further, and in some cases, each layer is peeled off and dispersed, and is uniformly dispersed in the resin solution. As a result, a sliding layer is obtained in which the organic layered clay mineral is uniformly dispersed in the polyamideimide resin. Further, the solid lubricant is also uniformly dispersed in the resin solution.

  Also, there is no particular limitation on the method of applying the coating composition to the substrate, and the coating composition is applied to the target portion by a normal coating method such as coating method, flow coating method, spray coating method, spin coating method, roll coating method, etc. What is necessary is just to apply.

  In addition, you may perform surface treatments, such as a plating process, a thermal spraying process, an anodizing process, a chemical conversion process, or a rough surface formation process, to the sliding surface side of a base material. Moreover, you may form the intermediate | middle layer located between a base material and a sliding layer.

  A sliding layer formation process is a process of removing the solvent of the said coating composition, and forming a sliding layer. The sliding layer is obtained by drying (baking if necessary) and curing the coating composition applied to the substrate. At this time, the drying conditions and the like may be appropriately selected according to the type of solvent of the resin solution.

  Below, the Example of the manufacturing method of the sliding member and sliding member of this invention is described with a comparative example.

[Production of Organized Clay (Organized Layered Clay Mineral)]
As a layered clay mineral, sodium type montmorillonite (Kunimine Industries Co., Ltd. Kunipia F (Organized clay Cloisite30B manufactured by Southern Clay Products Co., No. 8 only)), sodium type mica (CO100 Chemical Co., Ltd. ME100) and organic onium salts are shown in Table 1. The described organic cation was prepared. These were stirred and mixed in water so that the cation exchange capacity was 110 meq / 100 g, and sodium ions of the layered clay mineral were ion exchanged with organic onium ions. 1 to 10 organoclays were prepared. In Table 1, no. 11 is sodium-type montmorillonite which is not organically formed.

[Production of sliding members]
HPC-5000 manufactured by Hitachi Chemical Co., Ltd. (number average molecular weight of PAI resin: 19000, solid content concentration: 37 wt%, solvent: n-methyl-2-pyrrolidone and xylene) was used as the PAI resin varnish. Organized clay was introduced into this PAI resin varnish, and the mixture was stirred for 3 minutes and then defoamed for 30 seconds with a mixer (manufactured by Shinky, Super-Turning Revolution Super Mixer Nertaro Awatori) to obtain a mixture. Solid lubricant powder was put into the obtained mixture and mixed for 3 hours using a ball mill to obtain a coating composition.

  The coating composition was applied to the sliding surface of a disk-shaped substrate (φ90 mm, thickness 5 mm) made of an aluminum alloy (A390), dried at 80 ° C. for 30 minutes, and then fired at 200 ° C. for 1 hour. Sliding members A to L having a sliding layer having the composition shown in FIG. A sliding member X4 was produced in the same manner except that sodium montmorillonite (No. 11) that was not organicized was used.

  Further, sliding members M, N and X5 were obtained in the same manner as in the above procedure except that the number average molecular weight of the PAI resin used was 12000 or 8000.

  In Table 2, the sliding members X1 to X3 are comparative examples containing no organoclay, and are obtained by adding solid lubricant powder to the PAI resin varnish and mixing for 3 hours using a ball mill. Other than using the paint composition, it was produced in the same manner as the sliding members A to L. At this time, in the sliding member X2, as a PAI resin varnish, HPC-4250 manufactured by Hitachi Chemical Co., Ltd. (number average molecular weight of PAI resin: 18000, solid content concentration: 37 wt%, solvent: n-methyl-2-pyrrolidone and xylene) ) Was used.

  In the sliding members A to N and X1 to X5, the thickness of the sliding layer formed on the sliding surface was 15 μm.

[Production of film specimen]
The PAI resin varnish (the PAI resin is HPC-5000 (number average molecular weight: 19000) or HPC-4250 (number average molecular weight: 18000)) and the organoclay, and the composition after removal of the solvent is as shown in Table 3. And kneaded with the mixer in the same manner to obtain a mixture. The obtained mixture was applied with a bar coater, dried at 80 ° C. for 30 minutes, and then fired at 200 ° C. for 1 hour to obtain film test pieces a to g. Among these, the film test pieces a to d were transparent, and it was confirmed visually that the organized clay was uniformly dispersed in the PAI resin. It was confirmed that the film test piece g had irregularities on the surface and was not uniformly dispersed.

  In addition, film test piece ag is binder resin (resin composition) holding the solid lubricant powder of a sliding layer.

[Evaluation]
(X-ray diffraction measurement)
In order to confirm the dispersion state of the organized clay in the PAI resin, X-ray diffraction measurement was performed on the film test pieces a and g. The diffraction chart at this time is shown in FIG. For the measurement, RAD-B manufactured by Rigaku Denki Co., Ltd. was used, and CuKα Using X-rays, tube voltage: 30 kV, tube current: 30 mA, slit width: DS: 0.17 mm, RS: 0.15 mm, SS: 0.17 mm, and the 2θ-θ method was used.

  As can be seen from FIG. 1, in the film test piece g in which the layered clay mineral is untreated (No. 11), a diffraction line (2θ = 6.7) due to the (001) plane of sodium-type montmorillonite is observed. . However, in the case of the film test piece a, the diffraction line resulting from the (001) plane was not seen. From this, the organic clay no. No. 8 is considered to be uniformly dispersed in the polyamide-imide resin because the layers are open and no longer have a layered structure.

(Viscoelasticity measurement)
In order to evaluate the mechanical properties, viscoelasticity measurements were performed on the film specimens a and e. The measurement results are shown in FIG. For measurement, DMS manufactured by Seiko Instruments Inc. was used, the distance between chucks was 20 mm, the measurement frequency was 1 Hz, the tensile load was 50 mN, and the temperature was increased from room temperature (25 ° C.) to 280 ° C. at 3 ° C./min. Moreover, the width | variety of the sample (film test piece) was 4 mm, and thickness was 50 micrometers.

  The difference between the film test piece a and the film test piece e is the presence or absence of addition of organic clay. From FIG. 2, it can be seen that the addition of organoclay to the PAI resin improves the elastic modulus by about 1.5 times in the range from room temperature to around 220 ° C.

[Evaluation of sliding members]
In order to evaluate the sliding member of the present invention, the sliding characteristics of the sliding members A to N and X1 to X5 were evaluated.

(Non-lubricated seizure test)
A non-lubricated seizure test was performed on each sliding member. Specifically, using the test apparatus shown in FIG. 3, each sliding member in which the rotating shaft 5 is fixed from the base material 1 side on the upper surface of the shoe 6 made of bearing steel (SUJ2) fixed to the pedestal 7 is used as the shaft. The sliding layer 2 and the upper surface of the shoe 6 were brought into sliding contact with each other by rotating around. Then, the sliding speed was 10 m / s and the load was 2000 N, and the time from the arrival of the load 2000 N to the occurrence of seizure was measured. The results are shown in Table 2 and FIG.

  In the sliding members A to L of the present example in which the number average molecular weight of the PAI resin was 19000, no seizure occurred even when the test time was 150 seconds or more. Therefore, the sliding layers of the sliding members A to L are excellent in seizure resistance, and the sliding members A to L are superior in sliding characteristics to the sliding members X1 and X2 to which no organic clay is added. In the sliding layer of the sliding member M and the sliding member X3, the amount of solid lubricant powder used was the same, but a low molecular weight (8000) PAI resin was used. From the seizure test results of the sliding member M and the sliding member X3, it was found that the seizure resistance was improved by the addition of the organic clay.

  That is, the addition of the organic clay improved the seizure resistance regardless of the molecular weight of the resin used. The effect was more remarkable when the molecular weight of the resin was large (10,000 or more).

  Moreover, even if sodium-type montmorillonite (No. 11), which is not organicized, was added as in the sliding members X4 and X5, the effect of improving the seizure resistance was not observed.

  As the solid lubricant powder, PTFE having a particularly large influence on the sliding characteristics was used so as to have the same ratio in each sliding member (Table 2). Therefore, there is almost no difference in sliding characteristics depending on the blending amount of the solid lubricant powder in each sliding member.

(Oil lubrication test)
An oil lubrication test was performed on the sliding member H and the sliding member X1. Using the test apparatus shown in FIG. 3, the friction coefficient was measured under lubrication with refrigeration oil at a sliding speed of 10 m / s and a load of 5000 N (reached in 3000 seconds). The measurement results are shown in FIG. The friction coefficient after the load reached 5000 N was 0.06 to 0.08 for the sliding member H and 0.13 to 0.15 for the sliding member X1.

  In the sliding member H of this example, no seizure occurred even when the test time exceeded 10,000 seconds, but in the sliding member X1, seizure occurred when it exceeded 6000 seconds. Further, the sliding member H of this embodiment has a smaller coefficient of friction than the sliding member X1, and is excellent in slidability.

[Evaluation of binder resin]
In the sliding member of the present invention, in order to evaluate the binder resin constituting the sliding layer, the mechanical properties of the film test pieces a to f were evaluated.

(Tensile test)
A tensile test was performed on the film test pieces a, c, e, and f. Each film test piece was measured with a width of 4 mm and a thickness of 50 μm, a distance between chucks: 20 mm, and a tensile speed of 10 mm / min. The measurement temperature was room temperature (25 ° C.). The measurement results are shown in FIG. 6 (tensile strength), FIG. 7 (tensile modulus), and Table 4.

  Although there was no big difference in the tensile strength of each film test piece from FIG. 6, as shown in FIG. 7, a change arises in a tensile elasticity modulus (longitudinal elastic modulus) with the addition amount of the organized clay dispersed in PAI resin. It was. By dispersing the organized clay in the PAI resin, the tensile elastic modulus becomes 2500 MPa or more (film test pieces a and c).

(Measurement of linear expansion coefficient)
The average linear expansion coefficient in 100-200 degreeC was measured with respect to the film test pieces af. Each film test piece was measured with a width of 2 mm and a thickness of 50 μm, and with a thermomechanical analyzer (TMA), the distance between chucks: 10 mm, the tensile load: 100 mN, and the heating rate: 10 ° C./min. The measurement results are shown in FIG.

In FIG. 8, the added amount of the organized clay decreases in the order of a, b... E on the horizontal axis (e is no addition). That is, the average linear expansion coefficient at 100 to 200 ° C. becomes 5 × 10 ⁻⁵ / ° C. or less by the addition of the organized clay, and the larger the amount of the organized clay dispersed in the PAI resin, the smaller the thermal expansion coefficient. .

(Coating film evaluation)
The coating film appearance was observed with respect to the film test pieces I-VI. Each film test piece of I to VI was prepared from PAI resin varnishes having different number average molecular weights of PAI resin and organic clay no. 8 was added, and the mixture was stirred for 3 minutes and then defoamed for 30 seconds with a mixer (manufactured by Shinky, rotation and revolution super mixer Awatori Netaro) to obtain a mixture. Solid lubricant powder was put into the obtained mixture and mixed for 3 hours using a ball mill to obtain a coating composition. The coating composition is PAI resin: 13 wt%, organic clay: 1 wt%, molybdenum sulfide: 10 wt%, graphite: 7 wt%, PTFE: 3 wt%, n-methyl-2-pyrrolidone: 57 wt%. The obtained coating composition was applied to a PET film with a bar coater in an environment of relative humidity of 40% and temperature of 25 ° C., and the appearance of the coating film after 30 minutes was observed. The results are shown in Table 5.

  When the number average molecular weight is 36000, the appearance is deteriorated, and it is considered that the paint stability and the coating workability are inferior.

It is a X-ray-diffraction measurement result of the film test pieces a and g which consist of PAI resin and organic clay which were used for preparation of a sliding member. It is a graph which shows the viscoelasticity measurement result of the film test pieces a and e which consist of PAI resin and organic clay which were used for preparation of a sliding member. It is a schematic diagram explaining the test apparatus used for evaluation of the sliding characteristic of a sliding member. It is a graph which shows the result of a non-lubricated seizure test about sliding member A-N and X1-X5. It is a graph which shows the result of an oil lubrication test about sliding member X1 and sliding member H. It is a graph which shows the tensile strength of binder resin about film test piece a, c, and e, f. It is a graph which shows the tensile elasticity modulus of binder resin about the film test piece a, c, and e, f. It is a graph which shows the thermal expansion coefficient of binder resin about film test piece ae.

Explanation of symbols

1: Base material 2: Sliding layer

Claims (19)

A substrate and a sliding layer , the sliding layer comprising :
Formed on at least the sliding surface side of the substrate,
A polyamide-imide resin, and an organic lamellar clay mineral was uniformly dispersed in the polyamide-imide resin a layered clay mineral that has been organized by the organic onium ion, and a resin composition comprising,
A solid lubricant retained in the resin composition;
Sliding member, wherein the Tona Turkey. The sliding member according to claim 1, wherein the resin composition has an average linear expansion coefficient at 100 to 200 ° C. of 5 × 10 ⁻⁵ / ° C. or less.   The sliding member according to claim 1, wherein the solid lubricant includes at least one of a fluororesin, molybdenum disulfide, and graphite.   The sliding member according to claim 1, wherein the solid lubricant contains at least polytetrafluoroethylene.   The sliding member according to claim 1, wherein the polyamideimide resin has a number average molecular weight of 10,000 to 35,000. Before SL layer-like clay minerals, the sliding member according to claim 1, wherein the sodium montmorillonite or sodium-type mica. The organic onium ion sliding member according to claim 1 containing a hydroxyl group.   The sliding member according to claim 1, wherein the base material is a sliding component of a compressor.   The sliding member according to claim 8, wherein the sliding component is a swash plate of a swash plate compressor.   The sliding member according to claim 8, wherein the sliding component is a shoe of a compressor.   The sliding member according to claim 8, wherein the sliding component is a drive shaft of a compressor or a bearing that supports the drive shaft.   The sliding member according to claim 8, wherein the sliding component is a piston of a piston compressor. Coating composition comprising a mixture of a polyamideimide resin and a resin solution comprising a solvent that dissolves the polyamideimide resin, a solid lubricant, and an organized layered clay mineral that is a layered clay mineral organized by organic onium ions A coating composition application step of applying an article to at least the sliding surface side of the substrate;
A sliding layer forming step of forming a sliding layer by removing the solvent of the coating composition;
The manufacturing method of the sliding member characterized by comprising.   The method for manufacturing a sliding member according to claim 13, wherein the solid lubricant of the coating composition contains at least one of fluororesin, molybdenum disulfide, and graphite.   The method for manufacturing a sliding member according to claim 13, wherein the solid lubricant of the coating composition contains at least polytetrafluoroethylene. Layer clay minerals of the coating composition, method for producing a sliding member according to claim 13, wherein a sodium-type mica or sodium montmorillonite. The organic onium ion production method of a sliding member according to claim 1 3, wherein the hydroxyl group-containing.   The method for manufacturing a sliding member according to claim 13, wherein the solvent of the resin solution contains at least one of n-methyl-2-pyrrolidone and xylene.   The method for producing a sliding member according to claim 13, wherein the polyamideimide resin has a number average molecular weight of 10,000 to 35,000.

Images