JP2009155699A - Method of forming lubricant coating of fluorine resin on surface of base - Google Patents
Method of forming lubricant coating of fluorine resin on surface of base Download PDFInfo
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- JP2009155699A JP2009155699A JP2007336600A JP2007336600A JP2009155699A JP 2009155699 A JP2009155699 A JP 2009155699A JP 2007336600 A JP2007336600 A JP 2007336600A JP 2007336600 A JP2007336600 A JP 2007336600A JP 2009155699 A JP2009155699 A JP 2009155699A
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title abstract description 29
- 239000011248 coating agent Substances 0.000 title abstract description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000011737 fluorine Substances 0.000 title abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 21
- 239000000314 lubricant Substances 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 title abstract description 6
- 239000011347 resin Substances 0.000 title abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 54
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 230000001050 lubricating effect Effects 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 11
- 230000003746 surface roughness Effects 0.000 claims description 11
- 238000005422 blasting Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000002048 anodisation reaction Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 15
- 238000005299 abrasion Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 38
- 239000000463 material Substances 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000007743 anodising Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000013011 mating Effects 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
- 238000010422 painting Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Lubricants (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本発明は、金属基材の表面に、潤滑性および耐摩耗のフッ素樹脂皮膜を形成する方法に関する。 The present invention relates to a method for forming a fluororesin film having lubricity and wear resistance on the surface of a metal substrate.
ポリテトラフルオロエチレン（ＰＴＦＥ）に代表されるフッ素樹脂は、耐熱性で低粘着性であり、固体潤滑剤として使用し得る程の低い摩擦抵抗を持っている。これらの特性を利用して、フッ素樹脂は台所用調理器具や加熱装置に付着した汚染物の除去を容易にする耐汚染性コーティングに使用されている。また低摩擦抵抗（潤滑性）を利用し、相対的に摺動する金属の二面間に膜を形成し、摩擦、摩耗を減少させる固体潤滑剤として使用される。 A fluororesin represented by polytetrafluoroethylene (PTFE) has heat resistance and low adhesiveness, and has low frictional resistance that can be used as a solid lubricant. Taking advantage of these properties, fluororesins are used in antifouling coatings that facilitate the removal of contaminants attached to kitchen utensils and heating equipment. In addition, a low friction resistance (lubricity) is used to form a film between two surfaces of a relatively sliding metal, and it is used as a solid lubricant that reduces friction and wear.
二硫化モリブデン、二硫化タングステン、黒鉛などを含めて、摺動するに面間に固体潤滑剤の薄膜を形成する方法には、単に粉末を擦り込む方法、結合剤で付着させる方法、スパッタリング法、イオンプレーティング法などがあるが、ＰＴＦＥに適用可能で多用されているのは結合剤で付着させる方法である。この方法はポリサルホン、ポリイミドアミドなどの結合剤を含む塗料にＰＴＦＥ粉末を分散し、この塗料の塗膜を表面に形成し、乾燥後塗膜を焼付けることよりなる（特許文献１および２参照）。 The method of forming a thin film of solid lubricant between sliding surfaces, including molybdenum disulfide, tungsten disulfide, graphite, etc., is simply a method of rubbing powder, a method of attaching with a binder, a sputtering method, There are ion plating methods and the like, but what is applicable to PTFE and frequently used is a method of attaching with a binder. This method comprises dispersing PTFE powder in a paint containing a binder such as polysulfone or polyimide amide, forming a paint film on the surface, and baking the paint film after drying (see Patent Documents 1 and 2). .
固体潤滑剤は、荷重が加えられた時接触する二面間で低いせん断力により自らが変形して下地材料を保護することが求められる。ところが結合剤にはせん断などにより自ら変形する能力が乏しいので、結合剤を使用して付着させた膜は、ＰＴＦＥ１００％の膜に比較して固体潤滑剤としての性能が低下する。 The solid lubricant is required to be deformed by a low shear force between the two surfaces in contact with each other when a load is applied to protect the base material. However, since the binder does not have the ability to deform itself due to shearing or the like, the film attached using the binder has a lower performance as a solid lubricant than the film of 100% PTFE.
ＰＴＦＥは非粘着性であり、溶剤にも溶けず、融点以上に加熱しても流動しないため、結合剤を使用せざるを得ず、これまでＰＴＦＥ１００％の固体潤滑膜をうまく形成する方法は知られていなかった。
そこで本発明は、結合剤などを用いず、簡単な方法で、金属基材の表面などにＰＴＦＥ１００％の固体潤滑皮膜を形成する方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method of forming a solid lubricating film of 100% PTFE on the surface of a metal substrate by a simple method without using a binder or the like.
本発明者らは、ＰＴＦＥを金属基材の表面に固着および被覆する方法としてボールミルを用いた機械的コーティング方法に着目し、添加するＰＴＦＥの性状、被覆される金属基材の性状およびボールミルの処理条件などについて鋭意検討を重ねた結果、以下に述べるようなＰＴＦＥ１００％の固体潤滑皮膜を形成する新しい方法を発明した。 The present inventors paid attention to a mechanical coating method using a ball mill as a method for fixing and coating PTFE on the surface of a metal substrate, the properties of PTFE to be added, the properties of the metal substrate to be coated, and the treatment of the ball mill. As a result of intensive studies on the conditions, etc., a new method for forming a solid lubricating film of 100% PTFE as described below was invented.
本発明は、平均表面粗さＲａが０．６μｍ以上の粗面仕上げした表面を有する金属基材と、ＰＴＦＥの粉末と、粉砕媒体のボールを回転するボールミル内で流動させ、落下するボールの衝撃力により金属表面に密着したＰＴＦＥ皮膜が形成されるまでボールミルの回転を継続することを特徴とする金属基材の表面にフッ素樹脂潤滑皮膜を形成する方法に存する。 The present invention relates to a metal base material having a roughened surface with an average surface roughness Ra of 0.6 μm or more, PTFE powder, and impact of a ball that is caused to fall in a ball mill that rotates a ball of grinding media and falls. The present invention resides in a method of forming a fluororesin lubricating film on the surface of a metal substrate, wherein the rotation of the ball mill is continued until a PTFE film adhered to the metal surface by force is formed.
皮膜の下地素材への高い密着性が望まれる場合は、皮膜をＰＴＦＥの融点以上の温度へ加熱し、焼成することができる。 When high adhesion of the film to the base material is desired, the film can be heated to a temperature equal to or higher than the melting point of PTFE and fired.
金属基材の平均表面粗さＲａが０．６μｍ以上の粗面仕上げは、ブラスト処理、エッチング、化成処理、そしてアルミニウムの場合はプラズマ電解陽極酸化処理、および硫酸浴陽極酸化処理と組合せたブラスト処理などで達成される。 Roughing of metal substrates with an average surface roughness Ra of 0.6 μm or more is blasting, etching, chemical conversion, and in the case of aluminum, plasma electrolytic anodizing, and blasting combined with sulfuric acid bath anodizing And so on.
本発明の方法は、粉砕媒体であるボールの落下衝撃によって固体ＰＴＦＥへせん断力を加え、基材表面へ薄い膜として展延することを原理とするので、ＰＴＦＥの展性、ボールの落下衝撃力が重要である。ＰＴＦＥの展性はその分子量に関係し、平均分子量１×１０４〜１×１０５の範囲が好ましいことがわかった。ボールの落下衝撃力はボールの重量、従って比重に関係し、比重の大きいセラミックス製または金属製のボールを使用し、表面の平滑な仕上がり状態および処理物の形状に追随した仕上げを可能とするため、直径３ｍｍφ以下の大きさのボールが平滑な薄い膜の形成に適していることがわかった。 The method of the present invention is based on the principle that a shear force is applied to the solid PTFE by a drop impact of a ball as a grinding medium and spreads as a thin film on the surface of the base material. is important. It has been found that the malleability of PTFE is related to its molecular weight, and an average molecular weight in the range of 1 × 10 4 to 1 × 10 5 is preferable. The ball drop impact force is related to the weight of the ball, and therefore the specific gravity, so that a ceramic or metal ball with a large specific gravity can be used to achieve a smooth finish on the surface and a finish that follows the shape of the processed material. It was found that a ball having a diameter of 3 mmφ or less is suitable for forming a smooth thin film.
固体潤滑剤は、一般に油やグリースが使用不可能な又は望ましくない環境において使用される。ＰＴＦＥはこれまで知られた固体潤滑剤のうち最も低い摩擦係数を有するので、結合剤を使用することなく１００％ＰＴＦＥ潤滑膜の形成を可能とする本発明は、最も低い摩擦係数を有する固体潤滑膜の形成を可能とするものである。 Solid lubricants are generally used in environments where oils and greases are not available or desirable. Since PTFE has the lowest coefficient of friction among the solid lubricants known so far, the present invention, which enables the formation of a 100% PTFE lubricating film without using a binder, is a solid lubricant having the lowest coefficient of friction. The film can be formed.
下記に示す表１を参照して理解されるように、ボールミルを使用したＰＴＦＥ皮膜の形成は、素材表面粗さＲａに関係し、Ｒａが０．６μｍ以上ないと所望の機能が発揮される皮膜が形成されない。粗面仕上げは、機械的なブラスト処理および化学的なエッチング、リン酸化合物による化成処理などがある。アルミニウムの場合は、単独でプラズマ電解陽極酸化処理を行うか、または硫酸浴陽極酸化処理後、ブラスト処理を組み合わせて実施することにより、より耐磨耗性の高い皮膜を得ることができる。いずれにしても本発明の処理において平均表面粗さＲａが０．６μｍ以上になると、ＰＴＦＥ粉末の付着により、摩擦係数の低減若しくは耐磨耗性の向上に対して効果的なＰＴＦＥ皮膜が形成される。 As will be understood with reference to Table 1 below, the formation of a PTFE film using a ball mill is related to the material surface roughness Ra, and a film that exhibits a desired function unless Ra is 0.6 μm or more. Is not formed. The rough surface finish includes mechanical blasting and chemical etching, and chemical conversion treatment with a phosphoric acid compound. In the case of aluminum, a film with higher wear resistance can be obtained by performing plasma electrolytic anodizing treatment alone or by performing blast treatment in combination after sulfuric acid bath anodizing treatment. In any case, when the average surface roughness Ra becomes 0.6 μm or more in the treatment of the present invention, the PTFE film effective for reducing the friction coefficient or improving the wear resistance is formed by the adhesion of the PTFE powder. The
先に述べたとおり、ＰＴＦＥの分子量は皮膜の品質に影響する。平滑な表面を有する皮膜を形成するためには、平均分子量（数平均分子量）が１×１０４〜１×１０５の範囲にあるもの、例えば２〜５万のものが好ましい。分子量が過大であると形成される皮膜の表面粗さが大きくなり易く、またＰＴＦＥの付着性も悪化するため良好なフッ素皮膜を形成し難くなる。反対に過小の場合は基材表面に付着し易く、薄膜にコントロールするのが困難になる。 As mentioned earlier, the molecular weight of PTFE affects the quality of the coating. In order to form a film having a smooth surface, those having an average molecular weight (number average molecular weight) in the range of 1 × 10 4 to 1 × 10 5 , for example, 2 to 50,000 are preferable. When the molecular weight is excessive, the surface roughness of the formed film tends to increase, and the adhesion of PTFE deteriorates, so that it is difficult to form a good fluorine film. On the other hand, if it is too small, it tends to adhere to the surface of the substrate, making it difficult to control it to a thin film.
ボールの重量は、その落下衝撃力によって基材表面でＰＴＦＥへせん断力を加え、展延させるのに過不足ない重量であることが理想的であるが、ボールの材質がアルミナのようなセラミックス製の場合、ボールの直径は３ｍｍφ以下であることが適当である。匹敵する比重を有する他のセラミックス製または金属製のボールについても同様である。このボール直径は、円筒面のような曲面に皮膜を形成する場合にも適応する。これは、フッ素粉末はボール表面に一旦付着し、各ボールに付着したフッ素が製品表面に叩き付けられるため、より均一に製品表面にフッ素が付着する効果があるからであり、このためＰＴＦＥの粒子径はそれ程重要ではなく、１〜２０μｍの範囲のものであればよい。 Ideally, the ball should be made of a ceramic material such as alumina, although the ball should have a weight that is sufficient to apply a shear force to PTFE on the surface of the base material due to its drop impact force and spread it. In this case, it is appropriate that the diameter of the ball is 3 mmφ or less. The same applies to other ceramic or metal balls having comparable specific gravity. This ball diameter is also applicable when a film is formed on a curved surface such as a cylindrical surface. This is because the fluorine powder once adheres to the ball surface, and the fluorine adhering to each ball is struck against the product surface, so that the fluorine adheres more uniformly to the product surface. Therefore, the particle size of PTFE Is not so important and may be in the range of 1 to 20 μm.
ボールミルへのＰＴＦＥとボールの合計仕込量およびボールミルの回転数は、ボールの落下距離が最大になるように制御される。ボールの落下衝撃はＰＴＦＥが過剰に付着するのを妨げるようにも作用するので、本発明の方法によって形成されるＰＴＦＥ皮膜の厚みは適切にセルフコントロールされる。下記の表２より、セルフコントロールにより膜が一定の厚みに達するまでには、上に述べた適切な条件が満たされれば通常１時間で十分である。 The total amount of PTFE and balls fed to the ball mill and the number of rotations of the ball mill are controlled so that the ball drop distance is maximized. Since the ball drop impact also acts to prevent excessive PTFE adhesion, the thickness of the PTFE coating formed by the method of the present invention is appropriately self-controlled. From Table 2 below, one hour is usually sufficient as long as the appropriate conditions described above are satisfied until the film reaches a certain thickness by self-control.
このようにして形成された薄い皮膜は、単にＰＴＦＥ粉末を擦り込んだものと異なり、通常下地基材への十分な密着性を発揮する。しかしながら高い荷重が加わる場合のように、基材への一層高い密着性が求められる場合には、皮膜をＰＴＦＥの融点（３２７℃）以上の温度で焼成することが有用である。高分子量のＰＴＦＥは融点に達しても流動しないが、本発明のように分子量が１×１０４〜１×１０５の範囲にある場合、分子量１０万以上のＰＴＦＥと比べ流動し易い傾向を示す。また焼成は、皮膜の動摩擦係数を有意に低下させる効果がある。 The thin film formed in this way usually exhibits sufficient adhesion to the underlying substrate, unlike the case of simply rubbing PTFE powder. However, when higher adhesion to the substrate is required, such as when a high load is applied, it is useful to fire the coating at a temperature equal to or higher than the melting point (327 ° C.) of PTFE. High molecular weight PTFE does not flow even when reaching the melting point, but when the molecular weight is in the range of 1 × 10 4 to 1 × 10 5 as in the present invention, it tends to flow more easily than PTFE having a molecular weight of 100,000 or more. . Firing also has the effect of significantly reducing the dynamic friction coefficient of the coating.
以下、本発明を実施例により説明する。なお、本発明は以下に示される実施例に限定されるものではなく、本発明の技術的思想を逸脱しない範囲内で各種の変更が可能である。 Hereinafter, the present invention will be described with reference to examples. In addition, this invention is not limited to the Example shown below, A various change is possible within the range which does not deviate from the technical idea of this invention.
皮膜形成方法
本発明によるフッ素樹脂潤滑皮膜の形成方法として、平均分子量１×１０４〜１×１０５のポリテトラフルオロエチレン粉末（粒子径：１〜２０μｍ）と、セラミックス製または金属製メディアと、表面に微細な凹凸を形成した製品をボールミルのポット内に収納し、ポットごと回転させることにより発生する機械的エネルギーを利用して製品表面にフッ素樹脂のコーティング皮膜を形成した。
Film Forming Method As a method for forming a fluororesin lubricating film according to the present invention, polytetrafluoroethylene powder having an average molecular weight of 1 × 10 4 to 1 × 10 5 (particle diameter: 1 to 20 μm), ceramic or metal media, A product with fine irregularities formed on the surface was stored in a pot of a ball mill, and a fluororesin coating film was formed on the surface of the product using mechanical energy generated by rotating the pot together.
本発明によるフッ素処理条件
本発明によるフッ素処理条件として、ボールミルに仕込んだボールとＰＴＦＥの重量比は、ボール／ＰＴＦＥ＝４０／１〜１２０／１の範囲が処理可能な範囲であり、下記に述べる実施例においては全てボール／ＰＴＦＥ＝５０／１の重量比でボールミルを用いたフッ素コーティングを実施した。また、本発明の実施例２〜１４においてフッ素樹脂潤滑皮膜の形成に用いたコーティング材は、全て分子量２万のＰＴＦＥを使用した。
Fluorine treatment conditions according to the present invention As the fluorine treatment conditions according to the present invention, the ball / PTFE weight ratio in the range of ball / PTFE = 40/1 to 120/1 can be treated as described below. In all the examples, fluorine coating using a ball mill was performed at a weight ratio of ball / PTFE = 50/1. Moreover, the coating materials used for forming the fluororesin lubricating film in Examples 2 to 14 of the present invention were all PTFE having a molecular weight of 20,000.
摩擦係数及び耐摩耗性の評価方法
・ 評価機器：新東科学製表面性測定機 トライボギア１４ＦＷ
・ 相手材：５mmφ鋼球
・ 荷重：１Ｋｇ
・ 摩耗速度：２４００mm／ｍｉｎ
・ 摩耗距離：１０mm 往復摩耗
・ 環境：室温ドライ雰囲気
本発明の実施例（フッ素樹脂潤滑皮膜）およびその比較例については、上記の試験条件および試験機で各サンプルの摩擦係数及び耐摩耗性について測定を行い評価した。摩擦係数については、静摩擦係数：μｓと動摩擦係数：μｋとを測定した。また、耐摩耗性は、摩耗時摩擦力が急激に上昇し始める摩耗回数によって判定した（したがって、摩耗回数が大きいほど耐摩耗性が良いことを示している）。
以下に、本発明の実施例（フッ素樹脂潤滑皮膜）およびその比較例のサンプル作製条件を示す。
Friction coefficient and abrasion resistance evaluation method and evaluation equipment: Shinto Kagaku surface quality measuring machine Tribogear 14FW
・ Mating material: 5mmφ steel ball ・ Load: 1Kg
・ Wear rate: 2400mm / min
・ Wear distance: 10mm reciprocating wear
-Environment: room temperature dry atmosphere For the examples of the present invention (fluororesin lubricating film) and comparative examples thereof, the friction coefficient and wear resistance of each sample were measured and evaluated with the above test conditions and tester. As for the friction coefficient, a static friction coefficient: μs and a dynamic friction coefficient: μk were measured. Further, the wear resistance was determined by the number of wears at which the frictional force during wear began to increase rapidly (thus, the greater the number of wears, the better the wear resistance).
The sample preparation conditions for the examples of the present invention (fluororesin lubricating film) and comparative examples thereof are shown below.
実施例１
実施例１では、処理原料となるフッ素樹脂（四フッ化エチレン樹脂，ＰＴＦＥ）粉末の分子量を変化させたものを使用し、ブラスト処理したＳＰＣＣ（冷延鋼板）板をボールミルポットにて１時間処理した場合の、フッ素コーティング皮膜の表面粗さＲａ，摩擦係数，耐摩耗性について上述された評価方法にて評価を行った。
Example 1
In Example 1, using a fluororesin (tetrafluoroethylene resin, PTFE) powder having a changed molecular weight as a processing raw material, a blasted SPCC (cold rolled steel sheet) plate was treated in a ball mill pot for 1 hour. In this case, the surface roughness Ra, the friction coefficient, and the wear resistance of the fluorine coating film were evaluated by the evaluation methods described above.
表３は、フッ素樹脂粉末の変化させた分子量および各分子量における表面粗さＲａなどの測定結果である。表３から、原料であるＰＴＦＥ粉末の分子量が２０〜３０万ぐらいになると、処理後のテストピース表面粗さが粗くなる傾向が認められるとともに、ポット内においてフッ素粉末の凝集が生じやすい傾向があることがわかった。したがって、皮膜の耐摩耗性、仕上げ表面状態、連続コーティング処理性を考慮すると、ＰＴＦＥの平均分子量は１×１０４〜１×１０５の範囲にあることが好ましい。 Table 3 shows the measurement results such as the changed molecular weight of the fluororesin powder and the surface roughness Ra at each molecular weight. From Table 3, when the molecular weight of the PTFE powder as a raw material is about 200,000 to 300,000, the test piece surface roughness after the treatment tends to be coarse and the fluorine powder tends to aggregate in the pot. I understood it. Therefore, in consideration of the abrasion resistance of the film, the finished surface state, and the continuous coating processability, the average molecular weight of PTFE is preferably in the range of 1 × 10 4 to 1 × 10 5 .
比較例１
比較例１は、溶剤系潤滑塗料を使用した皮膜の形成例であって、ポリエーテルサルフォン樹脂をバインダーとしたフッ素樹脂タイプの塗料（ＰＴＦＥ／バインダーの重量比＝６４／３６）をブラスト処理したＳＰＣＣ板に塗装後、３８０℃×２０分焼付けを実施して作製したものである。
Comparative Example 1
Comparative Example 1 is an example of forming a film using a solvent-based lubricating paint, and a fluorinated resin type paint (polyether sulfone resin as a binder) (PTFE / binder weight ratio = 64/36) was blasted. After coating on the SPCC plate, it was produced by baking at 380 ° C. for 20 minutes.
比較例２
比較例２は、溶剤系潤滑塗料を使用した皮膜の形成例であって、エポキシ樹脂をバインダーとしたフッ素樹脂タイプの塗料（ＰＴＦＥ／バインダーの重量比＝３８／６２）をブラスト処理したＳＰＣＣ板に塗装後、１８０℃×２０分焼付けを実施して作製したものである。
Comparative Example 2
Comparative Example 2 is an example of forming a film using a solvent-based lubricating paint on a SPCC plate blasted with a fluororesin type paint (PTFE / binder weight ratio = 38/62) using an epoxy resin as a binder. After painting, it is produced by baking at 180 ° C. for 20 minutes.
比較例３
比較例３は、溶剤系潤滑塗料を使用した皮膜の形成例であって、ポリアミドイミド樹脂をバインダーとしたフッ素樹脂タイプの塗料（ＰＴＦＥ／バインダーの重量比＝１／１）をブラスト処理したＳＰＣＣ板に塗装後、２３０℃×２０分焼付けを実施して作製したものである。
Comparative Example 3
Comparative Example 3 is an example of forming a film using a solvent-based lubricating paint, and an SPCC plate blasted with a fluororesin type paint (PTFE / binder weight ratio = 1/1) using a polyamide-imide resin as a binder After coating, it was produced by baking at 230 ° C. for 20 minutes.
比較例４
比較例４は、ブラスト処理していないＳＰＣＣ板のブランク材である。
Comparative Example 4
Comparative Example 4 is a blank material of an SPCC plate that has not been blasted.
実施例２
実施例２は、ブラスト処理したＳＰＣＣ板に分子量２万のＰＴＦＥ粉末を用い、実施例１と同条件で処理した後、３８０℃×１０分焼付けを実施して作製したものである。
Example 2
Example 2 was prepared by using PTFE powder having a molecular weight of 20,000 on a blasted SPCC plate and treating it under the same conditions as in Example 1, followed by baking at 380 ° C. for 10 minutes.
比較例５
比較例５は、ブラスト処理していないＳＰＣＣ板のブランク材に実施例２と同条件でフッ素コーティングを実施した後、３８０℃×１０分焼付けを実施して作製したものである。
Comparative Example 5
Comparative Example 5 was prepared by performing fluorine coating on a blank material of an SPCC plate not subjected to blasting under the same conditions as in Example 2 and baking at 380 ° C. for 10 minutes.
実施例３
実施例３は、ブラスト処理したＳＰＣＣ板に実施例２と同条件でフッ素コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 3
In Example 3, the SPCC plate subjected to blasting was subjected to fluorine coating under the same conditions as in Example 2, and then produced without baking.
比較例６
比較例６は、ブラスト処理していないＳＰＣＣ板のブランク材に実施例２と同条件でフッ素コーティングを実施した後、焼付けを実施せずに作製したものである。
Comparative Example 6
The comparative example 6 is produced without performing baking after performing fluorine coating on the blank material of the SPCC board which has not been blasted on the same conditions as Example 2. FIG.
比較例７
比較例７は、ブラスト処理していないＳＵＳ４３０板のブランク材である。
Comparative Example 7
Comparative Example 7 is a blank material of SUS430 plate that has not been blasted.
実施例４
実施例４は、ブラスト処理したＳＵＳ４３０板を実施例２と同条件でフッ素コーティングを実施した後、３８０℃×１０分焼付けを実施して作製したものである。
Example 4
In Example 4, the blasted SUS430 plate was subjected to fluorine coating under the same conditions as in Example 2, and then baked at 380 ° C. for 10 minutes.
比較例８
比較例８は、ブラスト処理していない純アルミニウム板（１１００）のブランク材である。
Comparative Example 8
Comparative Example 8 is a blank material of a pure aluminum plate (1100) that has not been blasted.
実施例５
実施例５は、ブラスト処理した純アルミニウム板（１１００）を実施例２と同条件でフッ素コーティングを実施した後、３８０℃×１０分焼付けを実施して作製したものである。
Example 5
In Example 5, a blasted pure aluminum plate (1100) was subjected to fluorine coating under the same conditions as in Example 2, and then baked at 380 ° C. for 10 minutes.
実施例６
実施例６は、ブラスト処理した純アルミニウム板（１１００）を実施例２と同条件でフッ素コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 6
In Example 6, a blasted pure aluminum plate (1100) was prepared by performing fluorine coating under the same conditions as in Example 2 and then without baking.
実施例７
実施例７は、３０％ＮａＯＨ，４０℃×１０分のエッチング処理を実施したアルミニウム板を実施例２と同条件でフッ素コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 7
In Example 7, an aluminum plate subjected to an etching treatment of 30% NaOH and 40 ° C. × 10 minutes was prepared by performing fluorine coating under the same conditions as in Example 2 and then without baking.
比較例９
比較例９は、アルミニウム板（５０５２）にプラズマ電解陽極酸化処理（プラズマ電解陽極酸化処理，２０℃×４０分，膜厚２５μｍ）を実施して作製したものである。
Comparative Example 9
Comparative Example 9 was produced by performing plasma electrolytic anodizing treatment (plasma electrolytic anodizing treatment, 20 ° C. × 40 minutes, film thickness 25 μm) on an aluminum plate (5052).
実施例８
実施例８は、比較例９と同条件でプラズマ電解陽極酸化処理したアルミニウム板（５０５２）を、実施例２と同条件でフッ素樹脂コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 8
In Example 8, an aluminum plate (5052) subjected to plasma electrolytic anodization treatment under the same conditions as in Comparative Example 9 was prepared without performing baking after performing fluororesin coating under the same conditions as in Example 2. is there.
実施例９
実施例９は、比較例９と同条件でプラズマ電解陽極酸化処理したアルミニウム板（５０５２）を、実施例２と同条件でフッ素樹脂コーティングを実施した後、３８０℃×１０分焼付けを実施して作製したものである。
Example 9
In Example 9, an aluminum plate (5052) that was plasma electrolytically anodized under the same conditions as in Comparative Example 9 was coated with a fluororesin under the same conditions as in Example 2, followed by baking at 380 ° C. for 10 minutes. It was produced.
比較例１０
比較例１０は、アルミニウム板（５０５２）に硫酸浴陽極酸化処理（１５％Ｈ２ＳＯ４，１８℃，１．５Ａ／ｄｍ２，３０分，膜厚１０μｍ）を実施して作製したものである。
Comparative Example 10
Comparative Example 10 was prepared by subjecting an aluminum plate (5052) to sulfuric acid bath anodization treatment (15% H 2 SO 4 , 18 ° C., 1.5 A / dm 2 , 30 minutes, film thickness 10 μm). .
実施例１０
実施例１０は、比較例１０と同条件で硫酸浴陽極酸化処理したアルミニウム陽極酸化皮膜面上をブラスト処理し、実施例２と同条件でフッ素コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 10
In Example 10, the surface of the aluminum anodic oxide film that had been subjected to sulfuric acid bath anodization under the same conditions as in Comparative Example 10 was blasted, and after fluorine coating was performed under the same conditions as in Example 2, baking was not performed. It is what.
比較例１１
比較例１１は、アルミニウム板（５０５２）に硬質陽極酸化処理（２０％Ｈ２ＳＯ４ ，３Ａ／ｄｍ２，５℃，３０分，膜厚２０μｍ）を実施して作製したものである。
Comparative Example 11
In Comparative Example 11, a hard anodizing treatment (20% H 2 SO 4 , 3 A / dm 2 , 5 ° C., 30 minutes, film thickness 20 μm) was performed on an aluminum plate (5052).
実施例１１
実施例１１は、比較例１１と同条件で硬質陽極酸化処理したアルミニウム陽極酸化皮膜面上をブラスト処理し、実施例２と同条件でフッ素コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 11
In Example 11, the aluminum anodized film surface hard-anodized under the same conditions as in Comparative Example 11 was blasted, and after fluorine coating was carried out under the same conditions as in Example 2, it was produced without baking. Is.
比較例１２
比較例１２は、ＳＰＣＣ板に燐酸マンガン処理を施して作製したものである。
Comparative Example 12
Comparative Example 12 was prepared by applying a manganese phosphate treatment to an SPCC plate.
実施例１２
実施例１２は、比較例１２と同条件で燐酸マンガン処理したＳＰＣＣ板を、実施例２と同条件でフッ素コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 12
In Example 12, an SPCC plate treated with manganese phosphate under the same conditions as in Comparative Example 12 was prepared without applying baking after performing fluorine coating under the same conditions as in Example 2.
比較例１３
比較例１３は、ＳＰＣＣ板に燐酸亜鉛処理を実施して作製したものである。
Comparative Example 13
In Comparative Example 13, the SPCC plate was prepared by performing zinc phosphate treatment.
実施例１３
実施例１３は、比較例１３と同条件で燐酸亜鉛処理したＳＰＣＣ板を、実施例２と同条件でフッ素樹脂コーティングを実施した後、焼付けを実施せずに作製したものである。
Example 13
In Example 13, an SPCC plate treated with zinc phosphate under the same conditions as in Comparative Example 13 was prepared without performing baking after performing fluororesin coating under the same conditions as in Example 2.
実施例１４
実施例１４は、ブラスト処理することにより表面粗さＲａが１．８５μｍとなったポリフェニレンサルファイド（ＰＰＳ）成形体にフッ素樹脂コーティングを実施して作製したものである。
Example 14
In Example 14, a polyphenylene sulfide (PPS) molded body having a surface roughness Ra of 1.85 μm by blasting was coated with a fluororesin.
比較例１４
比較例１４は、無処理のＰＰＳ成形体である。
Comparative Example 14
Comparative Example 14 is an untreated PPS molded body.
上述された実施例２〜１４および比較例１〜１４のサンプルについて、被表面処理素材の表面処理条件などを変化させた場合の摩擦係数および耐磨耗性等についての測定結果を表４に示す。 Table 4 shows the measurement results of the coefficient of friction, the wear resistance, and the like when the surface treatment conditions of the surface-treated material are changed for the samples of Examples 2 to 14 and Comparative Examples 1 to 14 described above. .
表１に示されるＰＴＦＥ皮膜の付着量確保の観点からの他、表４に示されるＰＴＦＥ皮膜の摩擦係数の低減および耐摩耗性向上の観点からも、ボールミルを使用したＰＴＦＥ皮膜の形成は少なくとも表面粗さＲａが０．６μｍ以上の素材に適用されることが好ましいことが確認された。 From the viewpoint of securing the adhesion amount of the PTFE film shown in Table 1, and also from the viewpoint of reducing the friction coefficient and improving the wear resistance of the PTFE film shown in Table 4, the formation of the PTFE film using a ball mill is at least the surface It was confirmed that the material is preferably applied to a material having a roughness Ra of 0.6 μm or more.
また、本発明によるＰＴＦＥ皮膜の形成に適した粗面仕上げは、実施例２〜４で示されるような機械的なブラスト処理の他、実施例１２，１３で示されるような化学的なエッチングおよびリン酸化合物による化成処理などを使用することも有効である。また、被処理材がアルミニウムの場合は、単独でプラズマ電解陽極酸化処理を行うか、または硫酸浴陽極酸化処理後、ブラスト処理を組み合わせて実施することにより、より耐磨耗性の高い皮膜を得ることができる。（実施例５〜１１及び比較例８〜１１参照）。さらに、素材がポリフェニレンサルファイド（ＰＰＳ）のような素材であっても、本発明によるフッ素樹脂固体潤滑皮膜の形成方法を有効に適用できることがわかった。 In addition, the rough surface finish suitable for the formation of the PTFE film according to the present invention includes chemical blasting as shown in Examples 12 and 13 as well as mechanical blasting as shown in Examples 2 to 4. It is also effective to use a chemical conversion treatment with a phosphoric acid compound. In addition, when the material to be treated is aluminum, plasma electrolytic anodizing treatment is performed alone, or after a sulfuric acid bath anodizing treatment, a blast treatment is performed in combination to obtain a film with higher wear resistance. be able to. (See Examples 5 to 11 and Comparative Examples 8 to 11). Furthermore, it has been found that the method for forming a fluororesin solid lubricating film according to the present invention can be effectively applied even if the material is a material such as polyphenylene sulfide (PPS).
また、ボールミル処理により形成したフッ素樹脂固体潤滑皮膜の焼付け・焼成は、皮膜の動摩擦係数を有意に低下させる効果があることがわかった。このため、被処理材への皮膜のより高い密着性および高い耐磨耗性を望む場合は、形成されたフッ素樹脂固体潤滑皮膜をＰＴＦＥの融点（３２７℃）以上の温度で焼成することが効果的である。 It was also found that baking and baking of a fluororesin solid lubricating film formed by ball milling has the effect of significantly reducing the dynamic friction coefficient of the film. For this reason, when higher adhesion of the film to the material to be treated and higher wear resistance are desired, it is effective to fire the formed fluororesin solid lubricating film at a temperature equal to or higher than the melting point (327 ° C.) of PTFE. Is.
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| JP2001220686A (en) * | 2000-02-02 | 2001-08-14 | Daido Steel Co Ltd | Method for producing member coated with lubricated layer and member coated with lubricated layer |
| JP2003145039A (en) * | 2001-11-16 | 2003-05-20 | Fuji Kihan:Kk | Method of forming fluororesin coating film |
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| JPH06159373A (en) * | 1992-11-12 | 1994-06-07 | Nippon Seiko Kk | Self-lubricant coating roller bearing |
| JP2000312858A (en) * | 1999-04-28 | 2000-11-14 | Fuji Seisakusho:Kk | Method for forming thin film of fluoroplastic or copolymer resin with fluoroplastic |
| JP2001049461A (en) * | 1999-08-09 | 2001-02-20 | Rubutekku:Kk | Method for formation of solid lubricating film |
| JP2001220686A (en) * | 2000-02-02 | 2001-08-14 | Daido Steel Co Ltd | Method for producing member coated with lubricated layer and member coated with lubricated layer |
| JP2003145039A (en) * | 2001-11-16 | 2003-05-20 | Fuji Kihan:Kk | Method of forming fluororesin coating film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011208215A (en) * | 2010-03-30 | 2011-10-20 | Dowa Thermotech Kk | Member coated with sulfurized layer and method for manufacturing the same |
| JP2016199794A (en) * | 2015-04-13 | 2016-12-01 | Ｊｆｅスチール株式会社 | Steel sheet and method for manufacturing the same |
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| JP4977599B2 (en) | 2012-07-18 |
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