JP2005325182A - Solid lubricant and sliding member - Google Patents
Solid lubricant and sliding member Download PDFInfo
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- JP2005325182A JP2005325182A JP2004142962A JP2004142962A JP2005325182A JP 2005325182 A JP2005325182 A JP 2005325182A JP 2004142962 A JP2004142962 A JP 2004142962A JP 2004142962 A JP2004142962 A JP 2004142962A JP 2005325182 A JP2005325182 A JP 2005325182A
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- 239000007787 solid Substances 0.000 title claims abstract description 56
- 239000000314 lubricant Substances 0.000 title claims abstract description 54
- 229920002545 silicone oil Polymers 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- -1 polysiloxane Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 27
- 239000004810 polytetrafluoroethylene Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 24
- 239000001993 wax Substances 0.000 description 16
- 238000000465 moulding Methods 0.000 description 11
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920006358 Fluon Polymers 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229920006310 Asahi-Kasei Polymers 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229920006361 Polyflon Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
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- 239000010409 thin film Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Lubricants (AREA)
Abstract
Description
本発明は、固体潤滑剤及び摺動部材に関し、詳しくは、摺動部材基体の摺動面に形成された孔又は溝に埋め込まれる固体潤滑剤及び摺動部材に関する。 The present invention relates to a solid lubricant and a sliding member, and more particularly to a solid lubricant and a sliding member embedded in a hole or groove formed in a sliding surface of a sliding member base.
従来、この種の固体潤滑剤としては、層状構造を持つもの、中でもとくに黒鉛を主成分とするものが賞用されている。黒鉛はその組織が層状構造のため荷重方向に対しては大きい抵抗力を示すが、すべり方向に対しては抵抗力が小さく、しかも軟質であり、さらに常温からかなりの高温まで潤滑性能を保つことができるという利点を有している。軸受など摺動部材の摺動面に埋め込まれて使用されるこのような固体潤滑剤は、摺動面に適当な薄膜として形成されてはじめて有用なものであり、被膜形成の巧拙が摩擦摩耗特性及び被膜の寿命に大きな影響を及ぼす。 Conventionally, as this type of solid lubricant, those having a layered structure, in particular, those mainly composed of graphite have been awarded. Graphite shows a large resistance to the load direction due to its lamellar structure, but it has a low resistance to the sliding direction and is soft, and also maintains lubrication performance from room temperature to a fairly high temperature. Has the advantage of being able to Such a solid lubricant embedded in the sliding surface of a sliding member such as a bearing is useful only when it is formed as a suitable thin film on the sliding surface. And greatly affects the life of the coating.
しかしながら、前述の黒鉛を主成分とした固体潤滑剤は、被膜の形成能がやや不足するとともに、繰り返し摩擦に対する被膜の寿命の点で充分でない。そのため、低速度、高荷重用途には不向きである。 However, the above-described solid lubricant containing graphite as a main component has a slightly insufficient ability to form a film and is not sufficient in terms of the life of the film against repeated friction. Therefore, it is not suitable for low speed and high load applications.
他方、高荷重用途に使用される固体潤滑剤としては、四ふっ化エチレン樹脂と、インジウム、鉛、錫などの軟質金属と、炭化水素系ワックスなどのワックスとが配合された固体潤滑剤がある（特許文献１参照）。この固体潤滑剤は、高荷重条件下において摩擦係数がきわめて低く、また被膜の形成能に優れ、該被膜の寿命も長く、さらに被膜の自己補修性にも優れているという利点を有しているものである。 On the other hand, solid lubricants used for high-load applications include solid lubricants in which ethylene tetrafluoride resin, soft metals such as indium, lead, and tin are mixed with waxes such as hydrocarbon waxes. (See Patent Document 1). This solid lubricant has the advantage that it has a very low coefficient of friction under high load conditions, is excellent in the ability to form a film, has a long life, and is excellent in self-repairability of the film. Is.
しかしながら、近年の機械装置の大型化、高性能化に伴い、このような固体潤滑剤を埋め込んだ摺動部材には、さらなる負荷能力、摩擦摩耗特性の向上などが要求されている。また、別の観点では、近年、材料開発の動向は環境問題への配慮から環境負荷物質である鉛を含有しない方向に進んでおり、この開発動向は上記固体潤滑剤においても例外ではない。しかしながら、固体潤滑剤において、摩擦摩耗等の摺動特性を満足させる上で鉛は重要な構成成分である。とくに、軸受などの摺動部材の摺動面に形成された孔又は溝に埋め込んで高荷重条件下で使用する場合は、被膜形成能の点からも鉛は重要である。 However, with the recent increase in size and performance of mechanical devices, sliding members embedded with such solid lubricants are required to have further improved load capacity and frictional wear characteristics. Further, from another viewpoint, in recent years, the trend of material development has progressed in a direction not containing lead, which is an environmentally hazardous substance, in consideration of environmental problems, and this development trend is no exception in the solid lubricant. However, in a solid lubricant, lead is an important component for satisfying sliding characteristics such as frictional wear. In particular, lead is important from the viewpoint of film forming ability when it is used in a high load condition by being embedded in a hole or groove formed on a sliding surface of a sliding member such as a bearing.
鉛を含有しない摺動部材として、メラミンとイソシアヌル酸との付加物を含有する樹脂を成形してなる摺動部材が例示されている（特許文献２参照）。しかしながら、このメラミンとイソシアヌル酸との付加物を含有する樹脂を成形してなる摺動部材組成物を固体潤滑剤として使用した場合、高荷重条件下における摩擦係数が充分とは言えない。このため、上記した環境問題を解決することができ、かつ鉛を含有することなく高荷重条件下で充分な摩擦摩耗等の摺動特性を発揮する固体潤滑剤の提供が望まれている。 As a sliding member not containing lead, a sliding member formed by molding a resin containing an adduct of melamine and isocyanuric acid is exemplified (see Patent Document 2). However, when a sliding member composition formed by molding a resin containing an adduct of melamine and isocyanuric acid is used as a solid lubricant, it cannot be said that the coefficient of friction under high load conditions is sufficient. Therefore, it is desired to provide a solid lubricant that can solve the environmental problems described above and that exhibits sufficient sliding characteristics such as frictional wear under high load conditions without containing lead.
本発明は前記諸点に鑑みてなされたもので、その目的とするところは、高荷重条件下での使用においても、鉛を用いなくても従来の鉛を含有する固体潤滑剤よりも優れた摺動特性を発揮し得る固体潤滑剤及び該固体潤滑剤を埋め込んだ摺動部材を提供することにある。 The present invention has been made in view of the above-mentioned points. The object of the present invention is to provide a sliding material superior to conventional solid lubricants containing lead, even when used under high load conditions, without using lead. An object of the present invention is to provide a solid lubricant capable of exhibiting dynamic characteristics and a sliding member embedded with the solid lubricant.
本発明の第一の要旨は、摺動部材基体の摺動面に形成された孔又は溝に埋め込まれる固体潤滑剤であって、シリコーン油５〜３０重量％とシリコーンワックス２０〜４０重量％とメラミンシアヌレート２０〜４０重量％と四ふっ化エチレン樹脂２０〜５０重量％とから成ることを特徴とする固体潤滑剤に存する。 The first gist of the present invention is a solid lubricant embedded in a hole or groove formed in a sliding surface of a sliding member base, and includes 5 to 30% by weight of silicone oil and 20 to 40% by weight of silicone wax. A solid lubricant comprising 20 to 40% by weight of melamine cyanurate and 20 to 50% by weight of ethylene tetrafluoride resin.
本発明の第二の要旨は、摺動部基体の摺動面に形成された孔又は溝に、上記固体潤滑剤を埋め込んで成る摺動部材に存する。 The second gist of the present invention resides in a sliding member formed by embedding the solid lubricant in a hole or groove formed in the sliding surface of the sliding portion base.
本発明によれば、環境負荷物質である鉛を用いなくてもよい固体潤滑剤であって、高荷重条件下で当該鉛を含有する固体潤滑剤よりも優れた摺動特性を発揮し、しかも摺動部材基体の摺動面に形成された孔又は溝に埋め込んで使用されるのに好適な固体潤滑剤が提供される。 According to the present invention, it is a solid lubricant that does not require the use of lead, which is an environmentally hazardous substance, and exhibits superior sliding characteristics than a solid lubricant containing lead under high load conditions. A solid lubricant suitable for use by being embedded in a hole or groove formed in a sliding surface of a sliding member base is provided.
以下、本発明を説明する。先ず、固体潤滑剤について述べる。シリコーンワックスは、主として摩擦係数を低減する作用を発揮するとともに、後述するシリコーン油を吸収保持する担体としての役割を果たす。シリコーンワックスとしては、ジメチルポリシロキサン、メチルフェニルポリシロキサン、長鎖アルキル変性ポリシロキサン、トリフルオロプロピルメチルシロキサンなどを好ましい例として挙げることができる。具体的には、例えば旭化成ワッカーシリコーン社製の「シリコーンワックスＷ２３（商品名）」が挙げられる。このシリコーンワックスの配合割合は、２０〜４０重量％、好ましくは２５〜３０重量％である。配合割合が２０重量％未満の場合は、所望の低摩擦特性が得られず、また、４０重量％を超えた場合は、成形性が悪くなるとともに、成形体（固体潤滑剤）の強度が低下する。 The present invention will be described below. First, the solid lubricant will be described. Silicone wax mainly exerts an effect of reducing the friction coefficient and plays a role as a carrier for absorbing and holding silicone oil described later. Preferred examples of the silicone wax include dimethylpolysiloxane, methylphenylpolysiloxane, long chain alkyl-modified polysiloxane, trifluoropropylmethylsiloxane, and the like. Specific examples include “silicone wax W23 (trade name)” manufactured by Asahi Kasei Wacker Silicone. The blending ratio of the silicone wax is 20 to 40% by weight, preferably 25 to 30% by weight. When the blending ratio is less than 20% by weight, desired low friction characteristics cannot be obtained. When the blending ratio exceeds 40% by weight, the moldability deteriorates and the strength of the molded body (solid lubricant) decreases. To do.
シリコーン油は、とくに高荷重条件下での使用において、上記シリコーンワックスと協働して低摩擦性を向上させる。シリコーン油は、ジメチルシリコーン油又はジメチルポリシロキサンのメチル基の一部をポリエーテル基、フェニル基、アルキル基、アラルキル基若しくはふっ素化アルキル基等で置換したシリコーン油が好ましく、粘度（２５℃）が１００〜５００００ｃＳｔ、好ましくは５００〜１００００ｃＳｔのものが使用されて好適である。具体的には、信越化学工業社製のジメチルシリコーン油「ＫＦ９６Ｈ（商品名）」、旭化成ワッカーシリコーン社製のジメチルシリコーン油「ＡＫシリーズ（商品名）」を挙げることができる。このシリコーン油は、前述したシリコーンワックスと混合されることにより、そのほとんどが該ワックスに吸収保持されるので、比較的多量の配合が可能である。そして、シリコーン油の配合割合は、５〜３０重量％、好ましくは１０〜２５重量％である。配合割合が５重量％未満の場合は、高荷重条件下での使用において、摺動面への供給量が少なく低摩擦性の向上に充分効果が発揮されず、また３０重量％を超えた場合は、成形時に流出（ブリードアウト）するとともに、成形体の保形性を低下させる虞がある。 Silicone oils work with the silicone wax to improve low friction, especially when used under high load conditions. The silicone oil is preferably a dimethyl silicone oil or a silicone oil in which a part of the methyl group of dimethylpolysiloxane is substituted with a polyether group, a phenyl group, an alkyl group, an aralkyl group or a fluorinated alkyl group, and has a viscosity (25 ° C.). 100 to 50000 cSt, preferably 500 to 10000 cSt, is preferably used. Specific examples include dimethyl silicone oil “KF96H (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd. and dimethyl silicone oil “AK series (trade name)” manufactured by Asahi Kasei Wacker Silicone. Since most of this silicone oil is absorbed and retained by the above-mentioned silicone wax, a relatively large amount of the silicone oil can be blended. And the compounding ratio of a silicone oil is 5 to 30 weight%, Preferably it is 10 to 25 weight%. When the blending ratio is less than 5% by weight, when used under high load conditions, the amount supplied to the sliding surface is small and the effect of improving the low friction property is not sufficiently exerted, and when it exceeds 30% by weight May flow out (bleed out) during molding, and may reduce the shape retention of the molded body.
メラミンシアヌレートは、メラミンとシアヌル酸又はイソシアヌル酸との付加化合物であり、６員環構造のメラミン分子とシアヌル酸（イソシアヌル酸）分子が水素結合により平面状に配列し、その平面が弱い結合力で層状に重なり合っており、二硫化モリブデンやグラファイトのような劈開性を有するものである。このメラミンシアヌレートは、固体潤滑剤の低摩擦性及び耐摩耗性を向上させる作用を有する。その配合割合は、通常２０〜４０重量％、好ましくは２５〜３５重量％である。配合割合が２０重量％未満では、低摩擦性及び耐摩耗性を向上させる作用が充分発揮されず、また４０重量％を超えた場合は、却って耐摩耗性を低下させる虞がある。 Melamine cyanurate is an addition compound of melamine and cyanuric acid or isocyanuric acid. A 6-membered ring melamine molecule and cyanuric acid (isocyanuric acid) molecule are arranged in a plane by hydrogen bonds, and the plane has weak bonding strength. The layers overlap each other and have cleavage properties such as molybdenum disulfide and graphite. This melamine cyanurate has the effect | action which improves the low friction property and abrasion resistance of a solid lubricant. The blending ratio is usually 20 to 40% by weight, preferably 25 to 35% by weight. When the blending ratio is less than 20% by weight, the effect of improving the low friction property and the wear resistance is not sufficiently exhibited, and when it exceeds 40% by weight, the wear resistance may be lowered.
四ふっ化エチレン樹脂（以下、「ＰＴＦＥ」と略称する。）は、主として低摩擦性を付与する作用を発揮する。本発明で使用されるＰＴＦＥは、モールディングパウダー又はファインパウダーとして主に成形用に使用されるＰＴＦＥ（以下、「高分子量ＰＴＦＥ」と略称する。）と、放射線照射などにより高分子量ＰＴＦＥを分解又はＰＴＦＥの重合時に分子量を調節して、高分子量ＰＴＦＥに比べて分子量を低下させた、粉砕し易く、また分散性がよい、主に添加材料として使用されるＰＴＦＥ（以下、「低分子量ＰＴＦＥ」と略称する。）とに大別される。ＰＴＦＥとしては、高分子量ＰＴＦＥ単独又は高分子量ＰＴＦＥと低分子量ＰＴＦＥとの混合物を使用することができる。混合物としての高分子量ＰＴＦＥと低分子量ＰＴＦＥとの配合割合（重量）は、通常１：１〜３：１である。 Tetrafluoroethylene resin (hereinafter abbreviated as “PTFE”) mainly exhibits an effect of imparting low friction. The PTFE used in the present invention is PTFE mainly used for molding as molding powder or fine powder (hereinafter abbreviated as “high molecular weight PTFE”), and the high molecular weight PTFE is decomposed or irradiated by radiation. PTFE used as an additive material (hereinafter abbreviated as “low molecular weight PTFE”), which has a molecular weight lower than that of high molecular weight PTFE, is easy to grind, and has good dispersibility. ). As PTFE, high molecular weight PTFE alone or a mixture of high molecular weight PTFE and low molecular weight PTFE can be used. The blending ratio (weight) of the high molecular weight PTFE and the low molecular weight PTFE as a mixture is usually 1: 1 to 3: 1.
モールディングパウダー用高分子量ＰＴＦＥとしては、三井・デュポンフロロケミカル社製の「テフロン（登録商標）７−Ｊ（商品名）」、「テフロン（登録商標）７Ａ−Ｊ（商品名）」、「テフロン（登録商標）７０−Ｊ（商品名）」等、ダイキン工業社製の「ポリフロンＭ−１２（商品名）」等、旭硝子社製の「フルオンＧ１６３（商品名）」、「フルオンＧ１９０（商品名）」等が挙げられる。ファインパウダー用高分子量ＰＴＦＥとしては、三井・デュポンフロロケミカル社製の「テフロン（登録商標）６ＣＪ（商品名）」等、ダイキン工業社製の「ポリフロンＦ２０１（商品名）」等、旭硝子社製の「フルオンＣＤ０７６（商品名）」、「フルオンＣＤ０９０（商品名）」等が挙げられる。 As high molecular weight PTFE for molding powder, “Teflon (registered trademark) 7-J (trade name)”, “Teflon (registered trademark) 7A-J (trade name)”, “Teflon (manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.)” "Registered trademark" 70-J (trade name) "," Polyflon M-12 (trade name) "manufactured by Daikin Industries, Ltd.," Fluon G163 (trade name) "," Fluon G190 (trade name) "manufactured by Asahi Glass Or the like. As high molecular weight PTFE for fine powder, “Teflon (registered trademark) 6CJ (trade name)” manufactured by Mitsui / Dupont Fluoro Chemical Co., Ltd., “Polyflon F201 (trade name)” manufactured by Daikin Industries, Ltd., etc., manufactured by Asahi Glass Co., Ltd. “Full-on CD076 (product name)”, “Full-on CD090 (product name)”, and the like.
また、高分子量ＰＴＦＥとしては、上記高分子量ＰＴＦＥ以外に、高分子量ＰＴＦＥをスチレン系、アクリル酸エステル系、メタクリル酸エステル系、アクリロニトリル系重合体などで変性したものも使用でき、具体的には、三菱レイヨン社製の「メタブレンＡ−３０００（商品名）」等が挙げられる。低分子量ＰＴＦＥとしては、三井・デュポンフロロケミカル社製の「ＴＬＰ−１０Ｆ（商品名）」等、ダイキン工業社製の「ルブロンＬ−５（商品名）」等、旭硝子社製の「フルオンＬ１６９Ｊ（商品名）」等、喜多村社製の「ＫＴＬ−８Ｎ（商品名）」等が挙げられる。 Further, as the high molecular weight PTFE, in addition to the above high molecular weight PTFE, those obtained by modifying the high molecular weight PTFE with a styrene-based, acrylate-based, methacrylic ester-based, acrylonitrile-based polymer, etc. can be used. Examples thereof include “Metablene A-3000 (trade name)” manufactured by Mitsubishi Rayon Co., Ltd. Low molecular weight PTFE includes “TLP-10F (trade name)” manufactured by Mitsui DuPont Fluoro Chemical Co., “Lublon L-5 (trade name)” manufactured by Daikin Industries, Ltd., and “Fullon L169J (trade name) manufactured by Asahi Glass Co., Ltd. Product name) "and" KTL-8N (product name) "manufactured by Kitamura.
ＰＴＦＥの配合割合は、２０〜５０重量％、好ましくは２５〜４０重量％である。配合割合が２０重量％未満の場合は、所望の低摩擦性が得られず、また５０重量％を超えた場合は、耐摩耗性を悪化させるとともに、成形体としての保形性が悪化し、成形体の強度低下を来すことになる。 The blending ratio of PTFE is 20 to 50% by weight, preferably 25 to 40% by weight. When the blending ratio is less than 20% by weight, the desired low friction property cannot be obtained, and when it exceeds 50% by weight, the wear resistance is deteriorated and the shape retention as a molded body is deteriorated, The strength of the molded body will be reduced.
本発明の固体潤滑剤及び摺動部材は、つぎのようにして形成される。ヘンシェルミキサー、スーパーミキサー、ボールミル、タンブラー等の混合機によって上述の各成分の所定量を混合し、得られた混合物を成分中のワックスが溶融する温度で溶融混練したのち、この混練物を孔又は溝が形成された摺動部材基体に供給する。ついで、所定の圧力で圧縮して該混練物を摺動部材基体の孔又は溝に充填するとともに該基体の表面に薄膜として形成したのち所定時間放置することにより、固体潤滑剤を埋め込んだ摺動部材が形成される。 The solid lubricant and the sliding member of the present invention are formed as follows. A predetermined amount of each of the above-mentioned components is mixed by a mixer such as a Henschel mixer, a super mixer, a ball mill, or a tumbler, and the obtained mixture is melt-kneaded at a temperature at which the wax in the components melts. It supplies to the sliding member base | substrate with which the groove | channel was formed. Next, the slide is filled with a solid lubricant by compressing at a predetermined pressure to fill the kneaded material into the holes or grooves of the sliding member base, and forming a thin film on the surface of the base and leaving it for a predetermined time. A member is formed.
摺動部材基体としては、高力黄銅などの銅合金又は繊維織布強化熱硬化性合成樹脂の積層材が使用される。摺動部材基体に設けられる孔又は溝の開口面積の摺動面に占める割合は通常２０〜３５％が適当である。 As the sliding member base, a laminated material of a copper alloy such as high-strength brass or a fiber woven cloth reinforced thermosetting synthetic resin is used. The ratio of the opening area of the hole or groove provided in the sliding member base to the sliding surface is usually 20 to 35%.
以下、実施例により本発明を詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded.
〔相手材の作製〕
相手材：Ｉ
幅６２ｍｍ、長さ１７８ｍｍのステンレス鋼板（ＳＵＳ３０４）を使用し、これを相手材Ｉとした。
[Production of mating material]
Opponent material: I
A stainless steel plate (SUS304) having a width of 62 mm and a length of 178 mm was used as a counterpart material I.
相手材：ＩＩ
幅６２ｍｍ、長さ１７８ｍｍのステンレス鋼板（ＳＵＳ３０４）を準備し、この鋼板の一方の表面をショットブラストにより粗面化すると共に脱脂処理を施した。四ふっ化エチレン樹脂粉末として、ダイキン工業社製の「ルブロンＬ５（商品名）」を３５重量％含有するポリアミドイミド樹脂粉末を有機溶剤に溶かして得た固形分が３０重量％の溶液を、上記鋼板の粗面化した面に吹付け手段により塗膜を形成し、熱風乾燥炉で３０分間予備乾燥を行って溶剤を逸散除去させたのち、２３０℃の温度で３０分間過熱焼成を行い、厚さ２３μｍの被複層を形成し、これを相手材ＩＩとした。
Opponent material: II
A stainless steel plate (SUS304) having a width of 62 mm and a length of 178 mm was prepared, and one surface of the steel plate was roughened by shot blasting and degreased. As a tetrafluoroethylene resin powder, a solution having a solid content of 30% by weight obtained by dissolving a polyamideimide resin powder containing 35% by weight of “Lublon L5 (trade name)” manufactured by Daikin Industries, Ltd. in an organic solvent, A coating film is formed by spraying means on the roughened surface of the steel sheet, preliminarily dried in a hot air drying furnace for 30 minutes to dissipate and remove the solvent, and then heated at 230 ° C. for 30 minutes, A multi-layer having a thickness of 23 μm was formed, and this was used as a counterpart material II.
〔摺動部材基体の作製〕
摺動部材基体Ｉ
高力黄銅鋳物４種（ＪＩＳ Ｈ ５１２０）を準備し、機械加工により直径６０ｍｍ、厚さ１０．５ｍｍの円板に形成したのち、一方の表面に直径８ｍｍ、深さ３ｍｍの円形凹部を１２個形成（円板の表面の面積に占める凹部の開口部面積の割合は２１％）し、これを摺動部材基体Ｉとした。
[Production of sliding member base]
Sliding member base I
Four types of high-strength brass castings (JIS H 5120) were prepared and formed into a disk with a diameter of 60 mm and a thickness of 10.5 mm by machining, followed by 12 circular recesses with a diameter of 8 mm and a depth of 3 mm on one surface. This was formed (the ratio of the opening area of the recess to the surface area of the disk was 21%), and this was used as the sliding member base I.
摺動部材基体ＩＩ
強化繊維布として平織綿布を準備し、該綿布を送りローラにて、樹脂固形分６４．５重量％のフェノール樹脂ワニスを貯えた容器内を通過させて、該綿布の表面に樹脂ワニスを塗工し、圧縮ロールによって綿布の表面に塗工された樹脂ワニスを繊維組織間隙にまで含浸せしめたのち、乾燥炉内で溶剤を飛ばすと同時に樹脂の反応を進めプリプレグ（樹脂加工綿布）を得た。このプリプレグを直径６０ｍｍの円形状に切断し、これを８枚重ね合わせた。８枚重ね合わせたプリプレグに、厚さ方向に成形圧力７０ｋｇ／ｃｍ２、成形温度１６０℃、成形時間１０分間の条件で圧縮成形し、積層体（積層体の厚さ１０．５ｍｍ）を得た。
Sliding member base II
A plain woven cotton cloth is prepared as a reinforcing fiber cloth, and the cotton cloth is passed by a feed roller through a container storing a phenol resin varnish having a resin solid content of 64.5% by weight, and the resin varnish is applied to the surface of the cotton cloth. Then, after impregnating the resin varnish coated on the surface of the cotton cloth with a compression roll into the gap between the fiber structures, the solvent was blown in the drying furnace and the reaction of the resin proceeded to obtain a prepreg (resin-processed cotton cloth). This prepreg was cut into a circular shape having a diameter of 60 mm, and eight sheets thereof were overlapped. Eight sheets of prepregs were compression molded in the thickness direction at a molding pressure of 70 kg / cm 2 , a molding temperature of 160 ° C., and a molding time of 10 minutes to obtain a laminate (laminate thickness 10.5 mm). .
この積層体の一方の表面に直径８ｍｍ、深さ３ｍｍの円形凹部を１２個形成（積層体の表面の面積に占める凹部の開口部面積の割合は２１％）し、これを摺動部材基体ＩＩとした。 Twelve circular recesses having a diameter of 8 mm and a depth of 3 mm were formed on one surface of the laminate (the ratio of the opening area of the recess to the surface area of the laminate was 21%). It was.
〔固体潤滑剤Ｉの作製〕
シリコーン油としてジメチルシリコーン油〔信越化学工業社製の「ＫＦ９６Ｈ（商品名）」〕１０〜２５重量％と、シリコーンワックスとして５０℃での粘度が３００ｃＳｔを呈する旭化成ワッカーシリコーン社製の「シリコーンワックスＷ２３（商品名）」２５〜３０重量％と、メラミンシアヌレートとして三菱化学社製の「ＭＣＡ（商品名）」２５重量％と、ＰＴＦＥとして高分子量ＰＴＦＥ〔旭硝子社製の「フルオンＧ１６３（商品名）」〕２５〜４０重量％とをヘンシェルミキサーに投入して混合物を作製した。得られた混合物を成分中のシリコーンワックスの融点以上の８０℃の温度に加熱し、溶融混練して固体潤滑剤混練物を作製した。
[Preparation of solid lubricant I]
10% to 25% by weight of dimethyl silicone oil (“KF96H (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone oil and “silicone wax W23 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. having a viscosity at 50 ° C. of 300 cSt. (Trade name) "25-30% by weight," MCA (trade name) "25% by weight made by Mitsubishi Chemical as melamine cyanurate, and high molecular weight PTFE [Fluon G163 (trade name) made by Asahi Glass Co., Ltd. ]] 25-40 wt% was charged into a Henschel mixer to prepare a mixture. The obtained mixture was heated to a temperature of 80 ° C. above the melting point of the silicone wax in the component, and melt kneaded to prepare a solid lubricant kneaded product.
〔固体潤滑剤ＩＩの作製〕
シリコーン油としてジメチルシリコーン油（上記と同じ）１０〜２５重量％と、シリコーンワックス（上記と同じ）２５重量％と、メラミンシアヌレート（上記と同じ）２５重量％と、ＰＴＦＥとして高分子量ＰＴＦＥ（上記と同じ）１２．５〜２０重量％と低分子量ＰＴＦＥ〔旭硝子社製の「フルオンＬ１６９Ｊ（商品名）」〕１０〜２０重量％とをヘンシェルミキサーに投入して混合物を作製した。得られた混合物を成分中のシリコーンワックスの融点以上の８０℃の温度に加熱し、溶融混練して固体潤滑剤混練物を作製した。
[Preparation of Solid Lubricant II]
10 to 25% by weight of dimethyl silicone oil (same as above) as silicone oil, 25% by weight of silicone wax (same as above), 25% by weight of melamine cyanurate (same as above), high molecular weight PTFE (same as above) 12.5-20% by weight and low molecular weight PTFE ["Fluon L169J (trade name)" manufactured by Asahi Glass Co., Ltd.) 10-20% by weight were charged into a Henschel mixer to prepare a mixture. The obtained mixture was heated to a temperature of 80 ° C. above the melting point of the silicone wax in the component, and melt kneaded to prepare a solid lubricant kneaded product.
実施例１〜４
上記摺動部材基体Ｉ及び摺動部材基体ＩＩの一方の表面に固体潤滑剤Ｉの混練物の所定量を供給したのち、摺動部材基体Ｉ及び摺動部材基体ＩＩと該摺動部材基体Ｉ及び摺動部材基体ＩＩの凹部を含む表面に供給した固体潤滑剤混練物とを、８０℃の温度で１分間圧縮成形し、該摺動部材基体Ｉ及び摺動部材基体ＩＩの凹部に該混練物を充填すると共に該摺動部材基体Ｉ及び摺動部材基体ＩＩの表面に該混練物の被覆層を形成し、これらを摺動部材とした。
Examples 1-4
After supplying a predetermined amount of the kneaded material of the solid lubricant I to one surface of the sliding member base I and the sliding member base II, the sliding member base I and the sliding member base II and the sliding member base I are supplied. And the solid lubricant kneaded material supplied to the surface including the concave portion of the sliding member base II is compression-molded at a temperature of 80 ° C. for 1 minute, and the kneading is performed in the concave portions of the sliding member base I and the sliding member base II. In addition, a coating layer of the kneaded material was formed on the surfaces of the sliding member base I and the sliding member base II, and these were used as sliding members.
実施例５〜７
上記摺動部材基体Ｉ及び摺動部材基体ＩＩの一方の表面に固体潤滑剤ＩＩの混練物の所定量を供給したのち、摺動部材基体Ｉ及び摺動部材基体ＩＩと該摺動部材基体Ｉ及び摺動部材基体ＩＩの凹部を含む表面に供給した固体潤滑剤混練物とを、８０℃の温度で１分間圧縮成形し、該摺動部材基体Ｉ及び摺動部材基体ＩＩの凹部に該混練物を充填すると共に該摺動部材基体Ｉ及び摺動部材基体ＩＩの表面に該混練物の被覆層を形成し、これらを摺動部材とした。
Examples 5-7
After supplying a predetermined amount of the kneaded material of the solid lubricant II to one surface of the sliding member base I and the sliding member base II, the sliding member base I and the sliding member base II and the sliding member base I are supplied. And the solid lubricant kneaded material supplied to the surface including the concave portion of the sliding member base II is compression-molded at a temperature of 80 ° C. for 1 minute, and the kneading is performed in the concave portions of the sliding member base I and the sliding member base II. In addition, a coating layer of the kneaded material was formed on the surfaces of the sliding member base I and the sliding member base II, and these were used as sliding members.
比較例
四ふっ化エチレン樹脂粉末（三井・デュポンフロロケミカル社製の「テフロン（登録商標）７Ａ−Ｊ（商品名）」）５０体積％と、アトマイズ鉛粉末４０体積％とを混合撹拌して混合物を得た。この混合物をプレス成形機により加圧成形し、直径８ｍｍ、長さ３ｍｍの円柱状固体潤滑剤を作成した。ついで、この円柱状固体潤滑剤を潤滑油（モービル社製の「ＤＴＥエキストラヘビーオイル（商品名）」）の入った油槽に浸漬し、１０体積％の潤滑油を含浸させた（重量換算で四ふっ化エチレン樹脂１８．８重量％、鉛７９．６重量％、潤滑油１．６重量％）。この固体潤滑剤を前記と同様の積層体からなる摺動部材基体の表面に形成された孔に充填し、これを摺動部材とした。
Comparative Example 50% by volume of ethylene tetrafluoride resin powder (“Teflon (registered trademark) 7A-J (trade name)” manufactured by Mitsui DuPont Fluorochemicals) and 40% by volume of atomized lead powder were mixed and stirred. Got. This mixture was subjected to pressure molding with a press molding machine to prepare a cylindrical solid lubricant having a diameter of 8 mm and a length of 3 mm. Next, this cylindrical solid lubricant was immersed in an oil tank containing lubricating oil (“DTE Extra Heavy Oil (trade name)” manufactured by Mobil Corporation) and impregnated with 10% by volume of lubricating oil (four by weight). Ethylene fluoride resin 18.8 wt%, lead 79.6 wt%, lubricating oil 1.6 wt%). This solid lubricant was filled in holes formed on the surface of a sliding member base made of the same laminate as described above, and this was used as a sliding member.
つぎに、上記実施例１〜７の摺動部材及び比較例からなる摺動部材について、スラスト試験にて摩擦性能を試験した。試験条件を表１に示す。 Next, the sliding performance of the sliding members of Examples 1 to 7 and the comparative example was tested for friction performance by a thrust test. Table 1 shows the test conditions.
（表１）
面 圧： １７Ｎ／ｍｍ２ （１７３ｋｇｆ／ｃｍ２）
速 度： ２００ｍｍ／ｓｅｃ
相手材： 上記相手材Ｉ 相手材ＩＩ
摺動距離：４００ｍ
潤 滑： 無潤滑
試験方法：二軸試験機の台上に相手材を固定し、該相手材に摺動部材の被覆層を摺動自
在に接触させると共に、該摺動部材に面圧が１７Ｎ／ｍｍ２となるように荷
重を加え、相手材側に加振（±１００ｍｍ）を行った。
摩擦係数の測定：摺動距離８０ｍ、１６０ｍ、２４０ｍ、３２０ｍ、４００ｍにそれぞ
れ達した時点の摩擦係数を測定した。
(Table 1)
Surface pressure: 17 N / mm 2 (173 kgf / cm 2 )
Speed: 200mm / sec
Mating material: Mating material I Mating material II
Sliding distance: 400m
Lubrication: Unlubricated Test method: Fix the mating material on the base of the biaxial testing machine, and slide the coating layer of the sliding member on the mating material
Load the sliding member so that the surface pressure is 17 N / mm 2.
Heavy weight was applied, and vibration (± 100 mm) was performed on the counterpart material side.
Coefficient of friction measurement: sliding distances of 80m, 160m, 240m, 320m and 400m respectively
The coefficient of friction at the time of reaching was measured.
上記試験条件で行った実施例１〜７及び比較例からなる摺動部材の試験結果を表２、表３及び表４に示す。なお、表２及び表３中、摺動部材Ａは摺動部材基体Ｉの摺動部材を、摺動部材Ｂは摺動部材基体ＩＩの摺動部材を示す。
Tables 2, 3 and 4 show the test results of the sliding members made of Examples 1 to 7 and Comparative Examples, which were performed under the above test conditions. In Tables 2 and 3, the sliding member A represents the sliding member of the sliding member base I, and the sliding member B represents the sliding member of the sliding member base II.
（表２）
実施例 １ ２ ３ ４
固体潤滑剤（重量％）
シリコーン油（ジメチルシリコーン油） １０ １０ ２０ ２５
シリコーンワックス ２５ ３０ ３０ ２５
メラミンシアヌレート ２５ ２５ ２５ ２５
ＰＴＦＥ（高分子量） ４０ ３５ ２５ ２５
摺動部材 Ａ Ｂ Ａ Ｂ
相手材 Ｉ ＩＩ ＩＩ ＩＩ
摩擦係数（ ８０ｍ到達時） 0.062 0.048 0.042 0.040
（１６０ｍ到達時） 0.064 0.046 0.040 0.038
（２４０ｍ到達時） 0.064 0.046 0.040 0.038
（３２０ｍ到達時） 0.064 0.046 0.040 0.038
（４００ｍ到達時） 0.064 0.046 0.040 0.038
(Table 2)
Example 1 2 3 4
Solid lubricant (wt%)
Silicone oil (dimethyl silicone oil) 10 10 20 25
Silicone wax 25 30 30 25
Melamine cyanurate 25 25 25 25
PTFE (high molecular weight) 40 35 25 25
Sliding member A B A B
Mating material I II II II
Coefficient of friction (when reaching 80m) 0.062 0.048 0.042 0.040
(When reaching 160m) 0.064 0.046 0.040 0.038
(When reaching 240m) 0.064 0.046 0.040 0.038
(When reaching 320m) 0.064 0.046 0.040 0.038
(When reaching 400m) 0.064 0.046 0.040 0.038
（表３）
実施例 ５ ６ ７
固体潤滑剤（重量％）
シリコーン油（ジメチルシリコーン油） １０ ２０ ２５
シリコーンワックス ２５ ２５ ２５
メラミンシアヌレート ２５ ２５ ２５
ＰＴＦＥ（高分子量） ２０ ２０ １２．５
ＰＴＦＥ（低分子量） ２０ １０ １２．５
摺動部材 Ｂ Ａ Ｂ
相手材 Ｉ ＩＩ ＩＩ
摩擦係数（ ８０ｍ到達時） 0.060 0.040 0.040
（１６０ｍ到達時） 0.056 0.036 0.034
（２４０ｍ到達時） 0.056 0.036 0.034
（３２０ｍ到達時） 0.056 0.036 0.034
（４００ｍ到達時） 0.056 0.036 0.034
(Table 3)
Examples 5 6 7
Solid lubricant (wt%)
Silicone oil (dimethyl silicone oil) 10 20 25
Silicone wax 25 25 25
Melamine cyanurate 25 25 25
PTFE (high molecular weight) 20 20 12.5
PTFE (low molecular weight) 20 10 12.5
Sliding member B A B
Opponent material I II II
Coefficient of friction (when reaching 80m) 0.060 0.040 0.040
(When reaching 160m) 0.056 0.036 0.034
(When reaching 240m) 0.056 0.036 0.034
(When reaching 320m) 0.056 0.036 0.034
(When reaching 400m) 0.056 0.036 0.034
（表４）
比較例
相手材 Ｉ ＩＩ
摩擦係数（ ８０ｍ到達時） 0.086 0.082
（１６０ｍ到達時） 0.092 0.086
（２４０ｍ到達時） 0.100 0.094
（３２０ｍ到達時） 0.112 0.100
（４００ｍ到達時） 0.120 0.116
(Table 4)
Comparative example Counterpart material I II
Coefficient of friction (when reaching 80m) 0.086 0.082
(When reaching 160m) 0.092 0.086
(When reaching 240m) 0.100 0.094
(When reaching 320m) 0.112 0.100
(When reaching 400m) 0.120 0.116
以上の試験結果から明らかなように、本発明の固体潤滑剤を埋め込んで成る摺動部材は、低速度・高荷重条件下において、比較例に示す鉛を含有する固体潤滑剤を埋め込んで成る摺動部材に比して低い摩擦係数を示した。 As is clear from the above test results, the sliding member embedded with the solid lubricant of the present invention is a sliding member embedded with the solid lubricant containing lead shown in the comparative example under low speed and high load conditions. The coefficient of friction was lower than that of the moving member.
Claims (6)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007153919A (en) * | 2005-11-30 | 2007-06-21 | Ricoh Co Ltd | Lubricant molding, method for producing the same, lubricant coater and image forming apparatus |
| JP2011111524A (en) * | 2009-11-26 | 2011-06-09 | Momentive Performance Materials Inc | Silicone lubricant composition |
| EP2821443A4 (en) * | 2012-05-07 | 2016-05-25 | Nok Klueber Co Ltd | Composition for sliding member |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216193A (en) * | 1988-07-04 | 1990-01-19 | Kyodo Yushi Kk | Silicone greaser composition having excellent lubricity |
| JPH0489890A (en) * | 1990-08-02 | 1992-03-24 | Oiles Ind Co Ltd | Solid lubricant and sliding member with the solid lubricant embedded therein |
| JPH0489891A (en) * | 1990-08-02 | 1992-03-24 | Oiles Ind Co Ltd | Solid lubricant and sliding member with the solid lubricant embedded therein |
| JPH069979A (en) * | 1991-10-25 | 1994-01-18 | Oiles Ind Co Ltd | Lubricating composition and sliding member |
-
2004
- 2004-05-12 JP JP2004142962A patent/JP4543742B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216193A (en) * | 1988-07-04 | 1990-01-19 | Kyodo Yushi Kk | Silicone greaser composition having excellent lubricity |
| JPH0489890A (en) * | 1990-08-02 | 1992-03-24 | Oiles Ind Co Ltd | Solid lubricant and sliding member with the solid lubricant embedded therein |
| JPH0489891A (en) * | 1990-08-02 | 1992-03-24 | Oiles Ind Co Ltd | Solid lubricant and sliding member with the solid lubricant embedded therein |
| JPH069979A (en) * | 1991-10-25 | 1994-01-18 | Oiles Ind Co Ltd | Lubricating composition and sliding member |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007153919A (en) * | 2005-11-30 | 2007-06-21 | Ricoh Co Ltd | Lubricant molding, method for producing the same, lubricant coater and image forming apparatus |
| JP2011111524A (en) * | 2009-11-26 | 2011-06-09 | Momentive Performance Materials Inc | Silicone lubricant composition |
| EP2821443A4 (en) * | 2012-05-07 | 2016-05-25 | Nok Klueber Co Ltd | Composition for sliding member |
| US9777241B2 (en) | 2012-05-07 | 2017-10-03 | Nok Klueber Co., Ltd. | Composition for sliding member |
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| JP4543742B2 (en) | 2010-09-15 |
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