WO2010050444A1 - Ptfe系摺動材料、軸受及びptfe系摺動材料の製造方法 - Google Patents
Ptfe系摺動材料、軸受及びptfe系摺動材料の製造方法 Download PDFInfo
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- WO2010050444A1 WO2010050444A1 PCT/JP2009/068355 JP2009068355W WO2010050444A1 WO 2010050444 A1 WO2010050444 A1 WO 2010050444A1 JP 2009068355 W JP2009068355 W JP 2009068355W WO 2010050444 A1 WO2010050444 A1 WO 2010050444A1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/20—Sliding surface consisting mainly of plastics
- F16C33/201—Composition of the plastic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
- F05C2225/00—Synthetic polymers, e.g. plastics; Rubber
- F05C2225/04—PTFE [PolyTetraFluorEthylene]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12042—Porous component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/249955—Void-containing component partially impregnated with adjacent component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249958—Void-containing component is synthetic resin or natural rubbers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/249962—Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
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- Y10T428/31678—Of metal
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- Y10T428/31699—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a PTFE sliding material, a bearing, in particular a bearing for a car cooler compressor, and a method for manufacturing a PTFE sliding material.
- PTFE polytetrafluoroethylene
- B Melting point: Research has been published that the melting point is constant or has a width of 327 ° C.
- Melt viscosity Melt viscosity is very high at 10 11 to 10 12 Poise at 327 ° C., and commercially available PTFE hardly flows even above the melting point. For this reason, voids are likely to remain after firing.
- C Crystallinity: Classified as crystalline resin, with high molecular weight.
- Patent Document 1 Japanese Patent Application Laid-Open No. 1-108413 proposes to impregnate and coat a porous layer of a back metal with an aromatic polyether ketone, PTFE and a metal fluoride.
- Patent Document 2 Japanese Patent Laid-Open No. 8-41484 discloses a PTFE sliding material to which the following components A, B, and C are added.
- PTFE and petroleum solvent are impregnated into the porous layer of the backing metal plate, the solvent is evaporated at 200 ° C., then the roller is pressed, heated at 370 ° C. for 10 minutes, and the roller is pressed again. Is going.
- Patent Document 3 Japanese Patent Application Laid-Open No. 2002-20568 discloses barium sulfate, molybdenum disulfide, graphite and the like as countermeasures thereof. Is proposed to be added to PTFE.
- an additive such as barium sulfate and PTFE resin (a spherical colloid hydrophobic resin obtained by emulsion polymerization) are mixed, and the mixture is roll-impregnated into a porous layer of a backing metal, and 370 to 420 ° C. It is fired at.
- Patent Document 4 Japanese Patent Application Laid-Open No. 2007-09216 discloses a countermeasure for the problem that the PTFE resin is not satisfied under severe conditions such as a main bearing for a compressor in terms of wear resistance and seizure resistance. It is proposed to eliminate the boundary layer and strengthen PTFE by firing twice.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2008-69196, which does not belong to any of the above two categories, contains a small amount of perfluorooctanoic acid as an auxiliary during production and is dispersed with an acrylic resin dispersant.
- a method is described in which PTFE dispersion is impregnated into a porous layer of a backing metal and fired at 380 to 430 ° C.
- the carboxyl group contained in the acrylic resin dispersant adversely affects the bearing performance.
- the complete decomposition of the acrylic resin takes several hours to several tens of hours. Therefore, it is impossible to completely decompose the acrylic resin. It is regulated to 0.5% or less for PTFE.
- the main bearings and needle thrust bearings for car cooler compressors are PTFE systems in which a porous copper alloy sintered layer is impregnated on the back metal and impregnated with a mixture of fluorine resin and a solid lubricant such as Pb, Zn, barium sulfate, graphite, etc. Many sliding materials are used.
- JP-A-1-108413 Japanese Patent Laid-Open No. 8-41484 Japanese Patent Laid-Open No. 2002-20568 JP 2007-9216 A JP 2008-69196 A
- a bearing for a car cooler compressor in which the PTFE-based sliding material of the present invention is used is general.
- Such a bearing is designed so that a single load is applied, and a porous copper alloy sintered layer impregnated with a PTFE bearing material receives a local load and is slid by a PTFE resin layer.
- PTFE bearing materials utilize the friction reduction effect of PTFE transfer.
- an object of the present invention is to improve the characteristics of PTFE resin used for parts that are subjected to a single load and are susceptible to uneven wear.
- the present invention has a problem of increased torque due to increased friction starting from the worn part because it receives a single load due to its structure, and if used continuously as it is, it is used for a compressor main bearing of a car air conditioner that eventually gets seized.
- the purpose is to improve the performance of PTFE sliding materials.
- the present inventors conducted extensive research on PTFE reinforcing materials, and removed oxygen, hydrogen, nitrogen, etc. other than carbon from organic materials such as surfactants in the vicinity of the firing temperature of PTFE with oxygen blocked as much as possible.
- organic materials such as surfactants
- the carbonized substance is entangled with the PTFE fiber, and the carbide is finely dispersed more significantly than the material fired by adding carbide or graphite particles to the PTFE dispersion. It has been found that the PTFE coating is reinforced, resulting in improved wear resistance. This is also attributed to the fact that the oligomer or polymer used in the present invention has hydrophilic groups and is uniformly dispersed in the PTFE dispersion.
- reference numeral 1 denotes fibrous PTFE, which is a string-like shape caused by mixing of PTFE dispersions.
- 2 is a substance obtained by carbonizing an oligomer or polymer having a hydrophilic group (hereinafter referred to as “carbide”). That is, when focusing on the fibrous PTFE 1 and looking at the carbide 2, 1 sandwiches 2 at the curved portion, or 2 exists in the vicinity of 1. Looking at the carbide 2 and looking at the fibrous PTFE, 1 exists so as to surround 2. As a whole, carbides 2 are mixed between the intertwined PTFE fibers 1.
- the PTFE-based sliding material according to the present invention is formed by impregnating and firing a porous sintered layer on the back metal surface, and optionally impregnating either or both of a solid lubricant and an antiwear additive.
- the PTFE-based sliding material thus obtained is characterized in that carbon in which the oligomer or polymer is carbonized is mixed in the entangled structure of the fibrous PTFE, and the production of the PTFE-based sliding material according to the present invention
- the hydrophilic group is obtained by firing in a non-oxidizing atmosphere.
- One or two of oligomers and polymers having carbon are carbonized and left as a reinforcing component.
- PTFE dispersion contains PTFE fine particles and an activator (surfactant) as basic components, and is added in many cases with polymer solids. Depending on the case, barium sulfate, graphite, iron phosphorus compounds, etc. Is added.
- PTFE dispersion is impregnated into the porous layer on the back metal surface and baked in the vicinity of the melting point of PTFE, water and surfactant are evaporated.
- the polymer solids and the surfactant present in the PTFE dispersion are substantially free of substances other than carbon such as oxygen, hydrogen, and nitrogen during the firing. It turns out that it becomes only carbon and is carbonized.
- the volatile components become tar-like on the surface of the impregnated PTFE layer, and further, if the firing is continued, the tar-like substance is removed, and the surfactant is substantially converted to carbon in the entire sintered material. Become.
- the material thus formed is a carbide.
- the carbide in the present invention will be described. According to X-ray diffraction, the structure does not have a crystal structure such as graphite but is an amorphous structure. After the volatile matter in the oligomer molecule is lost, the carbon is agglomerated with each other, and these fine particles are not covered with PTFE fibers, but are sandwiched between the entangled structure of thicker PTFE fibers. And are attached to or close to the surface of the fiber. That is, since it is mixed in such an entangled structure, it is considered that the carbide particles make the PTFE fibers difficult to move and reinforce, and further, each of the PTFE fibers and the carbonized fine particles slides with the counterpart material.
- the oligomer used in the present invention is preferably a surfactant having a nonionic (nonionic) hydrophilic group.
- a surfactant having a nonionic (nonionic) hydrophilic group Specifically, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester Fatty acid alkanolamides and other fatty acid types, polyoxyethylene alkyl ethers, higher alcohols such as alkyl glycosides, and polyphenols such as polyoxyethylene alkylphenyl ethers. More preferred are higher alcohols and alkylphenols.
- an alkylamine oxide can also be used as an amphoteric surfactant.
- polymers such as polyvinyl alcohol and polyacrylic acid are preferably used. These oligomers and polymers are preferably water-soluble substances that dissolve in water in PTFE dispersion and do not impair the dispersion stability.
- the surfactant contained in the commercially available polymer dispersion is only carbonized, it is effective, but even if the above-mentioned surface activity is additionally added to the commercially available polymer dispersion, firing and carbide formation are simultaneously performed in a normal firing time. be able to. It is preferable that the amount of the surfactant added after the reaction is large because the amount of carbide increases and the strength of the film is increased. However, if too much hydrophilic organic substance is added, the viscosity of the PTFE dispersion becomes high and the impregnation property into the porous sintered layer is deteriorated. Therefore, it is necessary to adjust the addition amount.
- the thickness of the back metal, porous sintered layer, impregnated layer and the like are known, and those described in Patent Document 4 (paragraph number 0007) can be appropriately employed.
- the PTFE-based sliding material of the present invention is preferably a solid lubricant that is at least one selected from MoS 2 , graphite, BaSO 4 , Zn, and Pb, and preferably Al 2 O 3 , BN, iron-phosphorus compounds , SiO 2 and aromatic polyester, or at least one selected from anti-wear additives, or both.
- the back metal is preferably a steel plate
- the porous sintered layer is preferably a copper alloy.
- the PTFE-based sliding material according to the present invention can be preferably used for a main bearing of an automobile or a domestic compressor.
- the PTFE-based sliding material according to the present invention can prevent uneven wear due to a single load is that (i) dispersion uniformity of carbide, (b) fine particle form, (c) dispersion in an entangled structure, D) It is thought to be due to strengthening by carbides. That is, the carbide resulting from the carbonization of the surfactant of the present invention is a substance in which most of the components of the liquid surfactant uniformly dispersed in the dispersion are volatilized and remain in a finely dispersed form after impregnation. ing. Further, carbides are dispersed in the entangled structure of the PTFE fibers, and when sliding, the fibers are made difficult to move to strengthen the entire material.
- the carbide of the present invention is entangled with PTFE fibers, not only does it not interfere with the contact state where PTFE comes into contact with the mating material, but also makes the PTFE fibers difficult to move during sliding.
- the present invention will be described in more detail with reference to examples.
- Example A phosphor bronze sintered layer was laminated to a thickness of 0.3 mm on a low carbon steel (S15C) backing metal having a thickness of 0.85 mm.
- the following materials were used as the components of the sliding material.
- PTFE (Daikin Kogyo Co., Ltd .: trade name Polyflon Dispersion D1E, 100 parts by weight of nonionic surfactant (manufactured by NOF HS, Nonion HS-204.5) 3 parts by weight as a carbonized reinforcing material thing).
- the PTFE dispersion was not separated from water and others.
- Comparative Example 1 in the table is an example in which the nonionic surfactant is not added, the firing atmosphere is air, and carbonization is not strengthened.
- MoS 2 Average particle size .1.0 ⁇ m (manufactured by Sumiko Lubricant: trade name PA powder)
- Graphite average particle size 1.0 ⁇ m (Nippon Graphite Co., Ltd .: trade name CSSP)
- BaSO 4 average particle size 10 ⁇ m (manufactured by Sakai Chemical Co., Ltd .: trade name BMH-100)
- Al 2 O 3 Average particle size 0.5 ⁇ m (Wako Pure Chemical Industries, Ltd .: Trade name M60G-B)
- BN Average particle size 1 ⁇ m (Denki Kagaku Kogyo Co., Ltd .: Trade name SP-1)
- the above sliding material components were blended and mixed so as to have the composition shown in Table 1, and then the PTFE fiberized paste was gently kneaded so that PTFE did not agglomerate, and the copper alloy powder was sintered on the backing metal.
- the impregnated porous layer was impregnated and dried at about 100 ° C., and then the examples were baked in a nitrogen gas atmosphere at 380 ° C. for 5 minutes.
- carbides were mixed in the entangled structure of fibrous PTFE as shown in FIG. 1, while only the entangled structure of fibrous PTFE was observed in the comparative example. . From this result, it was found that all the surfactants originally added in the PTFE dispersion were decomposed and volatilized.
- the thin plate specimen 3 and the cylindrical counterpart material 4 were arranged to measure the amount of wear.
- the test conditions were as follows. Speed -0.3m / s Load: 5M Pa Test time: 3 hours Temperature: Room temperature Counterpart material: JIS SCM415 Lubrication: None Table 1 shows the test results.
- the PTFE sliding material of the present invention is particularly suitable as a bearing for a compressor for a car air conditioner that receives a single load.
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Sliding-Contact Bearings (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
(イ)融点:融点は327℃の一定である、あるいは幅をもつなどの研究が発表されている。
(ロ)溶融粘度:溶融粘度は327℃で1011~1012Poise(ポイズ)と非常に高く、市販のPTFEは融点以上でもほとんど流動しない。このため焼成後にボイドが残り易い。
(ハ)結晶性:結晶性樹脂に分類されており、分子量が大きい。
(ニ)処理法:PTFEの微粒子、界面活性剤及び水等からなるPTFEディパージョンが多孔質焼結層に含浸され、焼成されて、軸受として使用されている。
(ホ)組織:焼成前のPTFEはせん断を与えると簡単に繊維化(フィブリル化)する。繊維組織は焼成後に一部は消失したように見えるが、精度を上げて観察すると残存している。したがって、上記(ニ)のように処理されるPTFE摺動材料は繊維状結晶の形態を呈している。
まず、添加剤により耐摩耗性を向上する従来技術を挙げる。
特許文献1:特開平1-108413号公報は、裏金の多孔質層に,芳香族ポリエーテルケトン、PTFE及びフッ化金属を含浸被覆することを提案している。
特許文献4:特開2007-09216号公報は、PTFE系樹脂の耐摩耗性、耐焼付性の点でコンプレッサー用主軸受けのような片荷重になるような厳しい条件では満足しないという問題点の対策として2度焼成を行うことにより、境界層をなくしPTFEを強化することを提案している。
本発明のPTFE系摺動材料が使用される、カークーラーコンプレッサー用軸受の構造は一般的なものである。かかる軸受は構造上片荷重が加わる設計となっており、PTFE系軸受材料を含浸している多孔質銅合金焼結層が局部荷重を受け、PTFE系樹脂層で摺動させる構造となっている。PTFE系軸受材料は、PTFEの移着による摩擦低減効果を利用する。コンプレッサーでの使用環境の場合、境界潤滑となり、PTFEの移着効果が弱く、またPTFEと硬質樹脂もしくは耐摩耗性添加材料の界面の結合力が弱いために、耐摩耗性が期待できない。従って、多孔質焼結層上の樹脂皮膜の強化により摺動性能を向上させる必要がある。
特許文献4が提案する2度焼成法はかかる要請に応えるものであるが、コストの増大をもたらすという問題がある。
ポリマーとしては、ポリビニルアルコール、ポリアクリル酸などのポリマーが好ましく使用されている。これらオリゴマー、ポリマーは水溶性でありPTFEディスパージョンの中の水に溶解し、分散安定性を損なわない物質が好ましい。
さらに、裏金が鋼板であり、かつ多孔質焼結層は銅合金であることが好ましい。
また、本発明に係るPTFE系摺動材料は自動車または家庭用コンプッレッサーの主軸受に好ましく使用することができる。
即ち、本発明の界面活性剤の炭化による炭化物はディスパージョン中に均一分散している液状の界面活性剤のほとんどの成分が揮発して残った物質であり、含浸後も微細分散形態を維持している。さらに、炭化物がPTFE繊維の絡み合い構造中に分散しており、摺動の際、該繊維を動き難くして材料全体を強化している。このためにPTFEの移着が期待できない状況でも、十分な耐摩耗性を発揮する。これに対して、硫酸バリウム及び黒鉛は、その物性により耐摩耗性を向上させる作用はもっているが、粉末状体の添加混合であるためPTFEを均一分散させる機能はもっていないから、この性質に起因する上記(イ)~(ニ)のすべてを欠いている。
次に、平均15μm程度の本末の芳香族ポリエステルは、全体がPTFEと混合されたような状態になるから、(ロ)、(ハ)、(ニ)が実現されない。これに対して、本発明の炭化物はPTFE繊維を絡んで存在するから、PTFEが相手材と接触する接触状態を妨げないのみならず、摺動の際にPTFE繊維を動き難くしている。
以下、実施例により本発明をより詳しく説明する。
厚さが0.85mmの低炭素鋼(S15C)裏金上にリン青銅焼結層を厚さ0.3mmに積層した。摺動材料の成分としては次のものを使用した。
PTFE(ダイキン工業社製:商品名ポリフロンディスパージョンD1E,100重量部に対してノニオン系界面活性剤(日油化学社製品、ノニオンHS-204.5)を炭化強化材として3重量部配合したもの)。なお、PTFEディスパージョンが水とその他と分離しないようにした。また、表中の比較例1は、上記ノニオン系界面活性剤を添加せず、焼成雰囲気を空気とし、炭化強化しない例である。
MoS2:平均粒径.1.0μm(住鉱潤滑剤社製:商品名PAパウダー)
黒鉛:平均粒径1.0μm(日本黒鉛社製:商品名CSSP)
BaSO4:平均粒径10μm(堺化学社製:商品名BMH-100)
Al2O3:平均粒径0.5μm(和光純薬社製:商品名M60G-B)
BN:平均粒径 1μm( 電気化学工業社製:商品名SP-1 )
速度-0.3m/s
荷重: 5M Pa
試験時間:3時間
温度:室温
相手材:JIS SCM415
潤滑:なし
試験の結果を表1に示す。
2 炭化物
3 供試材
4 相手材
Claims (8)
- 裏金表面の多孔質焼結層にPTFEが含浸されかつ焼成されてなり、繊維状PTFE、及び場合によりさらに固体潤滑剤及び耐摩耗添加剤の何れか又は両者が含浸されてなるPTFE系摺動材料において、前記繊維状PTFEの絡合い構造中にオリゴマー又はポリマーの炭化物が混在していることを特徴とするPTFE系摺動材料。
- 前記固体潤滑剤はMoS2,黒鉛、BaSO4, Zn及びPbから選択された少なくとも1種である請求項1に記載のPTFE系摺動材料。
- 前記耐摩耗添加剤はAl2O3, BN, 鉄リン系化合物,SiO2及び芳香族ポリエステルら選択された少なくとも1種である請求項1又は2に記載のPTFE系摺動材料。
- 前記ポリマーはポリビニルアルコール又はポリアクリル酸である請求項1から3までの何れか1項に記載のPTFE系摺動材料。
- 前記オリゴマーは非イオン系界面活性剤である請求項1から4までの何れか1項に記載のPTFE系摺動材料。
- 裏金が鋼板であり、かつ前記多孔質焼結層が銅合金である請求項1から5までの何れか1項に記載のPTFE系摺動材料。
- 請求項1から6までの何れか1項に記載のPTFE系摺動材料を使用した自動車又は家庭用コンプッレッサー用軸受。
- 親水基を有するオリゴマー及びポリマーの1種又は2種を含んでなるPTFEディスパージョンを焼成するPTFE系摺動材料の製造方法において、前記焼成雰囲気を非酸化性雰囲気とすることにより、前記親水基を有するオリゴマー及びポリマーの1種又は2種を炭化させ、強化成分として残存させることを特徴とするPTFE系摺動材料の製造方法。
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US12/937,722 US8962143B2 (en) | 2008-10-27 | 2009-10-26 | PTFE-based sliding material, bearing, and method for producing PTFE-based sliding material |
JP2010535785A JP5432173B2 (ja) | 2008-10-27 | 2009-10-26 | Ptfe系摺動材料、軸受及びptfe系摺動材料の製造方法 |
EP09823554.2A EP2341258B1 (en) | 2008-10-27 | 2009-10-26 | Ptfe series sliding material, bearing, and ptfe series sliding material manufacturing method |
CN200980142466.2A CN102216633B (zh) | 2008-10-27 | 2009-10-26 | Ptfe系滑动材料、轴承和ptfe系滑动材料的制备方法 |
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Families Citing this family (8)
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EP3127944A4 (en) * | 2014-03-31 | 2018-03-07 | Nichias Corporation | Molded body and method for producing same |
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KR102149751B1 (ko) * | 2018-11-30 | 2020-08-31 | 이원석 | 전기방사를 이용한 베어링/부싱용 슬라이딩 재료 및 그 제조방법 |
CN114264596B (zh) * | 2021-12-23 | 2023-12-19 | 杭州电子科技大学 | Ptfe材料与金属生成转移膜润滑性测试装置及方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01108413A (ja) | 1987-10-20 | 1989-04-25 | Daido Metal Co Ltd | 複層摺動部材 |
JPH03119095A (ja) * | 1989-10-02 | 1991-05-21 | Central Glass Co Ltd | フッ素樹脂含浸多孔質材料 |
JPH0841484A (ja) | 1994-05-23 | 1996-02-13 | Oiles Ind Co Ltd | 摺動部材用樹脂組成物およびこれを使用した摺動部材 |
JPH10219270A (ja) * | 1997-02-10 | 1998-08-18 | Nhk Spring Co Ltd | ポリテトラフルオロエチレン含有潤滑シート及びその製造方法 |
JPH10246231A (ja) * | 1997-03-06 | 1998-09-14 | Hitachi Constr Mach Co Ltd | すべり軸受組立体 |
JP2002020568A (ja) | 2000-07-07 | 2002-01-23 | Taiho Kogyo Co Ltd | 摺動材料 |
JP2002030166A (ja) * | 2000-07-19 | 2002-01-31 | Japan Atom Energy Res Inst | 改質フッ素樹脂成形体を製造する方法 |
JP2007009216A (ja) | 2006-07-25 | 2007-01-18 | Shin Etsu Chem Co Ltd | 被膜形成用組成物用フロロオルガノポリシロキサン樹脂の製造方法 |
JP2008069196A (ja) | 2006-09-12 | 2008-03-27 | Daido Metal Co Ltd | 摺動部材 |
Family Cites Families (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB796610A (en) * | 1954-09-24 | 1958-06-18 | Du Pont | Improvements in or relating to sealing materials for use as gaskets, packings, and similar sealing devices |
GB1006190A (en) | 1961-05-19 | 1965-09-29 | Du Pont | Shaped articles |
CA980038A (en) * | 1969-04-23 | 1975-12-16 | Dexter Worden | Flexible, non-woven compositions and process for producing same |
GB1313651A (en) | 1969-06-25 | 1973-04-18 | Nat Res Dev | Bearing component |
US4277118A (en) * | 1978-05-15 | 1981-07-07 | Incom International Inc. | Bearings with felted teflon liners |
JPS6013991A (ja) | 1983-07-06 | 1985-01-24 | Taiho Kogyo Co Ltd | 斜板式コンプレツサ |
JPS6072952A (ja) | 1983-09-30 | 1985-04-25 | Taiho Kogyo Co Ltd | 摺動部材 |
US4615854A (en) * | 1984-04-30 | 1986-10-07 | Federal-Mogul Corporation | Method of making a PTFE based tape suitable for impregnation into a porous metal matrix |
US4923737A (en) | 1988-10-20 | 1990-05-08 | Northrop Corporation | Surface modified plastic and composite articles and method |
JPH0721318B2 (ja) | 1990-05-16 | 1995-03-08 | 日本ピラー工業株式会社 | 高分子複合材料 |
JP2962843B2 (ja) | 1990-06-07 | 1999-10-12 | キヤノン株式会社 | クリーニングブレード及びこれを用いた装置 |
US5415791A (en) * | 1990-08-02 | 1995-05-16 | Oiles Corporation | Lubricating composition and a sliding member comprising the composition |
US5272186A (en) * | 1992-05-01 | 1993-12-21 | E. I. Du Pont De Nemours And Company | Concentration of fluoropolymer dispersions using acrylic polymers of high acid content |
GB2279998B (en) * | 1993-07-14 | 1997-04-09 | T & N Technology Ltd | Plain bearing |
JP3017626B2 (ja) | 1993-08-03 | 2000-03-13 | トヨタ自動車株式会社 | 摺動用樹脂組成物 |
US5486299A (en) | 1993-11-02 | 1996-01-23 | Dow Corning Asia, Ltd | Wear-resistant lubricant composition |
DE69514994T3 (de) | 1994-03-16 | 2008-07-03 | Taiho Kogyo Co., Ltd., Toyota | Taumelscheibe für taumelscheibenverdichter |
US5405923A (en) * | 1994-05-02 | 1995-04-11 | E. I Du Pont De Nemours And Company | Suspension polymerization of TFE |
DE69500545T2 (de) | 1994-05-23 | 1998-01-29 | Oiles Industry Co Ltd | Harzzusammensetzung für Gleitelement und Gleitelement daraus |
IT1275972B1 (it) * | 1995-03-24 | 1997-10-24 | Ausimont Spa | Dispersioni di politetrafluoroetilene in un solvente organico ed agenti disperdenti ivi impiegati |
JP3519243B2 (ja) * | 1997-06-02 | 2004-04-12 | カネボウ株式会社 | 球状炭素材 |
JP4023872B2 (ja) | 1997-06-26 | 2007-12-19 | 大豊工業株式会社 | 斜板式コンプレッサー用斜板 |
JP2000136397A (ja) | 1998-10-30 | 2000-05-16 | Taiho Kogyo Co Ltd | 固体潤滑皮膜材料及びそれを用いた摺動材料 |
JP2000169697A (ja) | 1998-12-08 | 2000-06-20 | Daido Metal Co Ltd | 複層軸受 |
JP4614213B2 (ja) * | 1999-03-08 | 2011-01-19 | オイレス工業株式会社 | 摺動部材用樹脂組成物及びこれを使用した摺動部材 |
JP4001257B2 (ja) | 1999-03-17 | 2007-10-31 | 株式会社豊田自動織機 | 圧縮機 |
DE60024579T2 (de) * | 2000-03-08 | 2006-08-03 | Oiles Corp. | Harzzusammensetzung für Gleitelement und daraus hergestelltes Gleitelement |
JP2002005013A (ja) | 2000-06-27 | 2002-01-09 | Toyota Industries Corp | 斜板式圧縮機 |
JP2002039062A (ja) | 2000-07-26 | 2002-02-06 | Toyota Industries Corp | 圧縮機 |
JP2002089437A (ja) | 2000-09-13 | 2002-03-27 | Toyota Industries Corp | 圧縮機における潤滑用皮膜形成対象部品 |
JP2002180961A (ja) | 2000-10-03 | 2002-06-26 | Toyota Industries Corp | 斜板式圧縮機における斜板 |
WO2003010237A1 (en) | 2001-07-26 | 2003-02-06 | Solvay Advanced Polymers, Llc | Improved polyamide-imide molding resins and methods for their preparation |
JP3918516B2 (ja) | 2001-11-07 | 2007-05-23 | 株式会社豊田自動織機 | 斜板式圧縮機 |
JP2003183685A (ja) * | 2001-12-20 | 2003-07-03 | Toyota Industries Corp | 摺動部材 |
KR20030063566A (ko) | 2002-01-22 | 2003-07-31 | (주) 진성 티앤티 | 내 마모성 용융 화합물 |
DE10322182A1 (de) * | 2003-05-16 | 2004-12-02 | Blue Membranes Gmbh | Verfahren zur Herstellung von porösem, kohlenstoffbasiertem Material |
JP3973619B2 (ja) * | 2003-12-04 | 2007-09-12 | 大同メタル工業株式会社 | 複層摺動部材 |
DE102004008772A1 (de) | 2004-02-23 | 2005-09-08 | Institut für Neue Materialien Gemeinnützige GmbH | Abriebbeständige und alkalibeständige Beschichtungen oder Formkörper mit Niedrigenergieoberfläche |
JP5113982B2 (ja) * | 2004-04-23 | 2013-01-09 | トヨタ自動車株式会社 | 金属炭化物粒子が分散した炭素複合材料の製造方法 |
JP4584101B2 (ja) | 2005-09-29 | 2010-11-17 | 大豊工業株式会社 | 樹脂系摺動部材及びその製造方法 |
JP5050442B2 (ja) * | 2006-07-12 | 2012-10-17 | 旭硝子株式会社 | ポリテトラフルオロエチレン水性分散液 |
-
2009
- 2009-10-26 US US12/937,722 patent/US8962143B2/en active Active
- 2009-10-26 EP EP09823554.2A patent/EP2341258B1/en not_active Not-in-force
- 2009-10-26 CN CN200980142466.2A patent/CN102216633B/zh active Active
- 2009-10-26 KR KR1020107023752A patent/KR101261110B1/ko active IP Right Grant
- 2009-10-26 JP JP2010535785A patent/JP5432173B2/ja active Active
- 2009-10-26 WO PCT/JP2009/068355 patent/WO2010050444A1/ja active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01108413A (ja) | 1987-10-20 | 1989-04-25 | Daido Metal Co Ltd | 複層摺動部材 |
JPH03119095A (ja) * | 1989-10-02 | 1991-05-21 | Central Glass Co Ltd | フッ素樹脂含浸多孔質材料 |
JPH0841484A (ja) | 1994-05-23 | 1996-02-13 | Oiles Ind Co Ltd | 摺動部材用樹脂組成物およびこれを使用した摺動部材 |
JPH10219270A (ja) * | 1997-02-10 | 1998-08-18 | Nhk Spring Co Ltd | ポリテトラフルオロエチレン含有潤滑シート及びその製造方法 |
JPH10246231A (ja) * | 1997-03-06 | 1998-09-14 | Hitachi Constr Mach Co Ltd | すべり軸受組立体 |
JP2002020568A (ja) | 2000-07-07 | 2002-01-23 | Taiho Kogyo Co Ltd | 摺動材料 |
JP2002030166A (ja) * | 2000-07-19 | 2002-01-31 | Japan Atom Energy Res Inst | 改質フッ素樹脂成形体を製造する方法 |
JP2007009216A (ja) | 2006-07-25 | 2007-01-18 | Shin Etsu Chem Co Ltd | 被膜形成用組成物用フロロオルガノポリシロキサン樹脂の製造方法 |
JP2008069196A (ja) | 2006-09-12 | 2008-03-27 | Daido Metal Co Ltd | 摺動部材 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2341258A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023238798A1 (ja) * | 2022-06-08 | 2023-12-14 | Agc株式会社 | 組成物 |
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WO2010050444A9 (ja) | 2010-09-02 |
CN102216633B (zh) | 2015-06-03 |
KR20100124840A (ko) | 2010-11-29 |
JP5432173B2 (ja) | 2014-03-05 |
EP2341258A4 (en) | 2012-10-03 |
US20110097593A1 (en) | 2011-04-28 |
CN102216633A (zh) | 2011-10-12 |
KR101261110B1 (ko) | 2013-05-06 |
EP2341258B1 (en) | 2015-12-23 |
EP2341258A1 (en) | 2011-07-06 |
US8962143B2 (en) | 2015-02-24 |
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