JP2020164595A - Film formation method and surface protection oil - Google Patents

Film formation method and surface protection oil Download PDF

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JP2020164595A
JP2020164595A JP2019064617A JP2019064617A JP2020164595A JP 2020164595 A JP2020164595 A JP 2020164595A JP 2019064617 A JP2019064617 A JP 2019064617A JP 2019064617 A JP2019064617 A JP 2019064617A JP 2020164595 A JP2020164595 A JP 2020164595A
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film
silane compound
surface protective
oil
protective oil
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JP7312591B2 (en
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矢野　昭彦
Akihiko Yano
昭彦 矢野
藍 礒橋
Ai ISOHASHI
藍 礒橋
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Mitsubishi Heavy Industries Ltd
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Abstract

To provide the film formation method and the surface protection oil, that can suppress damage to members.SOLUTION: The surface protection oil for forming a film M on a surface A1 of a member A comprises a silane compound which is tetraethoxysilane and a lubricating oil, wherein the silane compound is contained in an amount of 2 wt.% or more to 50 wt.% by or less. Further, the film formation method for forming the film M on the surface A1 of the member A comprises a contact step of bringing the surface protection oil into contact with the surface A1 of the member A, and a film forming step of forming the film M containing Si and O on the surface A1 of the member A by hydrolyzing the silane compound and dehydrating and condensing the silane compound.SELECTED DRAWING: Figure 5

Description

本発明は、被膜形成方法及び表面保護油に関する。 The present invention relates to a film forming method and a surface protective oil.

転がり軸受などの部材は、摺動により繰り返し応力を受ける。このような部材は、疲労限を超えた面圧条件下では、有限の疲労寿命を有することとなり、この疲労寿命は、安全率などを考慮して設定される。しかし、例えば、部材の潤滑状態が不適切であったり、異物で部材の表面に傷が形成されたり、錆が発生したり、想定より高い負荷が加わった場合などにおいては、設定された疲労寿命より短い時間で損傷が発生するおそれがあり、このように損傷が生じた場合、動作不良を起こしたり、損傷の進展により部材が破損したりするおそれもある。従って、例えば特許文献１には、損傷した摺動面を修復するための摩耗修復剤が記載されており、摺動面を修復することにより、部材の破損などを抑制する旨が記載されている。 Members such as rolling bearings are repeatedly stressed by sliding. Such a member has a finite fatigue life under a surface pressure condition exceeding the fatigue limit, and this fatigue life is set in consideration of a safety factor and the like. However, for example, when the lubrication state of the member is improper, the surface of the member is scratched by foreign matter, rust is generated, or a load higher than expected is applied, the set fatigue life is set. Damage may occur in a shorter period of time, and if such damage occurs, malfunction may occur or the member may be damaged due to the progress of damage. Therefore, for example, Patent Document 1 describes a wear repairing agent for repairing a damaged sliding surface, and describes that repairing the sliding surface suppresses damage to members. ..

特許第６２３６５９３号公報Japanese Patent No. 6236593

しかし、部材の破損を抑制する点については、改善の余地がある。 However, there is room for improvement in suppressing damage to the members.

本発明は、上述した課題を解決するものであり、部材の破損を抑制可能な被膜形成方法及び表面保護油を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a film forming method and a surface protective oil capable of suppressing damage to members.

上述した課題を解決し、目的を達成するために、本開示に係る表面保護油は、部材の表面に被膜を形成するための表面保護油であって、テトラエトキシシランであるシラン化合物と、潤滑油とを含み、前記シラン化合物が、２重量％以上５０重量％以下含まれている。 In order to solve the above-mentioned problems and achieve the object, the surface protective oil according to the present disclosure is a surface protective oil for forming a film on the surface of a member, and is lubricated with a silane compound which is tetraethoxysilane. The silane compound is contained in an amount of 2% by weight or more and 50% by weight or less, including oil.

この表面保護油を用いると、表面保護油のシラン化合物を反応させることで、部材の表面に、シラン化合物の反応による被膜を形成することができる。従って、被膜で部材の損傷箇所を覆うことが可能となり、部材の破損を抑制することができる。 When this surface protective oil is used, a film formed by the reaction of the silane compound can be formed on the surface of the member by reacting the silane compound of the surface protective oil. Therefore, it is possible to cover the damaged portion of the member with the coating film, and it is possible to suppress the damage of the member.

前記表面保護油は、さらに、ＳｉＯ２の粒子であるシリカ粒子を含むことが好ましい。この表面保護油によると、部材の表面上に、シリカを含む被膜を形成することが可能となり、被膜により部材の破損を抑制することができる。 The surface protective oil preferably further contains silica particles which are particles of SiO 2 . According to this surface protective oil, a film containing silica can be formed on the surface of the member, and the film can suppress damage to the member.

前記シリカ粒子の平均粒径は、２μｍ以下であることが好ましい。シリカ粒子の粒径をこの範囲とすることで、軸受面にシリカ粒子を入り込ませて被膜を好適に形成させつつ、シリカ粒子の噛み込みによる焼き付きを抑制することができる。 The average particle size of the silica particles is preferably 2 μm or less. By setting the particle size of the silica particles in this range, it is possible to suppress the seizure due to the biting of the silica particles while allowing the silica particles to enter the bearing surface to preferably form a coating film.

前記シリカ粒子が、２重量％以下含まれていることが好ましい。シリカ粒子をこの量とすることで、被膜の硬度を高く保ちつつ、シリカの研磨作用によって被膜の形成が阻害されることを抑制できる。 It is preferable that the silica particles are contained in an amount of 2% by weight or less. By setting the amount of silica particles to this amount, it is possible to prevent the formation of the film from being hindered by the polishing action of silica while keeping the hardness of the film high.

上述した課題を解決し、目的を達成するために、本開示に係る被膜形成方法は、部材の表面に被膜を形成する被膜形成方法であって、前記表面保護油を、前記部材の表面に接触させる接触ステップと、前記シラン化合物を加水分解して脱水縮合させることで、ＳｉとＯとを含む被膜を前記部材の表面に形成する被膜形成ステップと、を有する。この被膜形成方法によると、部材の表面に表面保護油を接触させて、表面保護油のシラン化合物を反応させることで、表面に被膜を形成する。従って、被膜によって、表面の損傷箇所を覆うことが可能となり、部材の破損を抑制することができる。 In order to solve the above-mentioned problems and achieve the object, the film forming method according to the present disclosure is a film forming method for forming a film on the surface of a member, and the surface protective oil is brought into contact with the surface of the member. It has a contact step for forming a coating film containing Si and O on the surface of the member by hydrolyzing and dehydrating and condensing the silane compound. According to this film forming method, a surface protective oil is brought into contact with the surface of the member and a silane compound of the surface protective oil is reacted to form a film on the surface. Therefore, the coating makes it possible to cover the damaged portion on the surface and suppress the damage of the member.

前記被膜形成ステップを開始してから所定時間経過後に、前記表面保護油に、前記被膜の形成を停止させる反応停止物を添加する反応停止ステップをさらに有することが好ましい。 It is preferable to further have a reaction termination step of adding a reaction terminator for stopping the formation of the coating to the surface protective oil after a lapse of a predetermined time from the start of the coating formation step.

前記反応停止物は、アルキル基を含むシラン化合物であることが好ましい。 The reaction terminator is preferably a silane compound containing an alkyl group.

本発明によれば、部材の損傷を抑制することができる。 According to the present invention, damage to the member can be suppressed.

図１は、第１実施形態に係る部材を示す模式図である。FIG. 1 is a schematic view showing a member according to the first embodiment. 図２は、第１実施形態に係る被膜形成方法を説明するフローチャートである。FIG. 2 is a flowchart illustrating a film forming method according to the first embodiment. 図３は、部材に被膜が形成される反応を説明する模式図である。FIG. 3 is a schematic view illustrating a reaction in which a film is formed on a member. 図４は、部材に被膜が形成される反応を説明する模式図である。FIG. 4 is a schematic view illustrating a reaction in which a film is formed on a member. 図５は、部材に被膜が形成される反応を説明する模式図である。FIG. 5 is a schematic view illustrating a reaction in which a film is formed on a member. 図６は、部材に被膜が形成される反応を説明する模式図である。FIG. 6 is a schematic view illustrating a reaction in which a film is formed on a member. 図７は、部材に被膜が形成される反応を説明する模式図である。FIG. 7 is a schematic view illustrating a reaction in which a film is formed on a member. 図８は、実施例２の疲労強度試験の結果を示すグラフである。FIG. 8 is a graph showing the results of the fatigue strength test of Example 2.

以下に添付図面を参照して、本発明の好適な実施形態を詳細に説明する。なお、この実施形態により本発明が限定されるものではなく、また、実施形態が複数ある場合には、各実施形態を組み合わせて構成するものも含むものである。 Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The present invention is not limited to this embodiment, and when there are a plurality of embodiments, the present invention also includes a combination of the respective embodiments.

（第１実施形態）
最初に、第１実施形態について説明する。図１は、第１実施形態に係る部材を示す模式図である。部材Ａは、潤滑油が充填された環境下で別の部材Ｂの表面Ｂ１と対向しており、部材Ｂから繰り返し荷重を受ける。すなわち、部材Ａと部材Ｂとが収納される収納室Ｃには、潤滑油が充填されており、収納室Ｃ内において、部材Ａが部材Ｂから繰り返し荷重を受ける。本実施形態では、収納室Ｃ内において、部材Ａは、部材Ａの表面Ａ１上で部材Ｂが摺動することで、部材Ｂから繰り返し荷重を受ける。言い換えれば、表面Ａ１は摺動面である。部材Ａは、転がり軸受などの軸受であり、例えば、風車の主軸受や翼旋回輪の軸受に用いられる。ただし、部材Ａは、風車に用いられることに限られず、任意の装置に用いられてよい。また、部材Ａは、軸受であることに限られず、例えばギアなど、任意の部材であってよい。また、図１における部材Ａ、Ｂの形状は模式的に示したものであり、実際の形状は図１で示したものに限られない。 (First Embodiment)
First, the first embodiment will be described. FIG. 1 is a schematic view showing a member according to the first embodiment. The member A faces the surface B1 of another member B in an environment filled with lubricating oil, and repeatedly receives a load from the member B. That is, the storage chamber C in which the member A and the member B are stored is filled with lubricating oil, and the member A is repeatedly loaded by the member B in the storage chamber C. In the present embodiment, in the storage chamber C, the member A repeatedly receives a load from the member B by sliding the member B on the surface A1 of the member A. In other words, the surface A1 is a sliding surface. The member A is a bearing such as a rolling bearing, and is used, for example, as a main bearing of a wind turbine or a bearing of a wing swivel wheel. However, the member A is not limited to being used for a wind turbine, and may be used for any device. Further, the member A is not limited to a bearing, and may be any member such as a gear. Further, the shapes of the members A and B in FIG. 1 are schematically shown, and the actual shapes are not limited to those shown in FIG.

部材Ａは、金属製の部材であり、本実施形態では、軸受鋼ＳＵＪ２など、Ｆｅを含む部材である。ただし、部材Ａの材料は任意であってよい。ただし、部材Ａは、表面において、ＯＨ基が終端となる部材であることが好ましい。 The member A is a metal member, and in the present embodiment, it is a member containing Fe such as bearing steel SUJ2. However, the material of the member A may be arbitrary. However, the member A is preferably a member whose surface is terminated by an OH group.

図２は、第１実施形態に係る被膜形成方法を説明するフローチャートである。図３から図５は、部材に被膜が形成される反応を説明する模式図である。図１に示すように、第１実施形態に係る被膜形成方法は、表面保護油１により、部材Ａの表面Ａ１に被膜Ｍを形成する。図２に示すように、第１実施形態に係る被膜形成方法においては、最初に、接触ステップを実行する（ステップＳ１０）。接触ステップにおいては、表面保護油１を、部材Ａに接触させる。具体的には、接触ステップにおいては、部材Ａと部材Ｂとが収納される収納室Ｃに、表面保護油１が充填される。これにより、収納室Ｃ内において、部材Ａの表面Ａ１に表面保護油１が接触する。 FIG. 2 is a flowchart illustrating a film forming method according to the first embodiment. 3 to 5 are schematic views illustrating a reaction in which a film is formed on a member. As shown in FIG. 1, in the film forming method according to the first embodiment, the film M is formed on the surface A1 of the member A by the surface protective oil 1. As shown in FIG. 2, in the film forming method according to the first embodiment, the contact step is first executed (step S10). In the contact step, the surface protective oil 1 is brought into contact with the member A. Specifically, in the contact step, the surface protective oil 1 is filled in the storage chamber C in which the member A and the member B are stored. As a result, the surface protective oil 1 comes into contact with the surface A1 of the member A in the storage chamber C.

第１実施形態における表面保護油１は、シラン化合物１０と、潤滑油１２とを含む。シラン化合物１０は、シランを含む化合物であり、本実施形態では、アルコキシシランである。シラン化合物１０は、シランカップリング剤であるともいえる。シラン化合物１０としては、例えば、テトラエトキシシラン（（Ｃ２Ｈ５Ｏ）４Ｓｉ）、又はテトラメトキシシラン（（ＣＨ３Ｏ）４Ｓｉ）が挙げられ、テトラエトキシシランとテトラメトキシシランとの両方を含んでいてもよい。さらに言えば、シラン化合物１０は、テトラエトキシシランであることが好ましく、また、テトラエトキシシランの重合体であってもよい。テトラエトキシシランの重合体は、例えば、テトラエトキシシランのオリゴマーである。テトラエトキシシランの重合体は、粘度が高いため、これを用いることで、表面保護油１の粘度の低下を抑制して、表面保護油１を収納室Ｃに充填した場合の、油膜形成能力の低下や部材Ａの耐摩耗性の低下を抑制できる。 The surface protection oil 1 in the first embodiment contains the silane compound 10 and the lubricating oil 12. The silane compound 10 is a compound containing silane, and in this embodiment, it is an alkoxysilane. It can be said that the silane compound 10 is a silane coupling agent. Examples of the silane compound 10 include tetraethoxysilane ((C 2 H 5 O) 4 Si) and tetramethoxysilane ((CH 3 O) 4 Si), and both tetraethoxysilane and tetramethoxysilane. May include. Furthermore, the silane compound 10 is preferably tetraethoxysilane, and may be a polymer of tetraethoxysilane. The polymer of tetraethoxysilane is, for example, an oligomer of tetraethoxysilane. Since the polymer of tetraethoxysilane has a high viscosity, by using this, it is possible to suppress a decrease in the viscosity of the surface protective oil 1 and to have an oil film forming ability when the surface protective oil 1 is filled in the storage chamber C. It is possible to suppress the decrease and the decrease in the wear resistance of the member A.

潤滑油１２は、油であり、例えば、鉱油、ポリアルフォオレフィン、ポリオールエステルなどが挙げられる。潤滑油１２は、粘度グレードがＶＧ３２以上ＶＧ６８０以下であることが好ましい。 The lubricating oil 12 is an oil, and examples thereof include mineral oil, polyalphaolefin, and polyol ester. The lubricating oil 12 preferably has a viscosity grade of VG32 or more and VG680 or less.

表面保護油１は、シラン化合物１０が、５重量％以上５０重量％以下含まれることが好ましい。より詳しくは、表面保護油１は、シラン化合物１０と潤滑油１２との合計の重量に対し、シラン化合物１０が、２重量％以上５０重量％以下含まれることが好ましく、５重量％以上１０重量％以下含まれることがより好ましい。従って、表面保護油１は、シラン化合物１０と潤滑油１２との合計の重量に対し、潤滑油１２が、５０重量％以上９８重量％以下含まれることが好ましく、９０重量％以上９５重量％以下含まれることがより好ましい。また、表面保護油１は、４０℃における動粘度が２７ｃＳｔ以上２０７ｃＳＴ以下であることが好ましい。 The surface protection oil 1 preferably contains the silane compound 10 in an amount of 5% by weight or more and 50% by weight or less. More specifically, the surface protective oil 1 preferably contains 2% by weight or more and 50% by weight or less of the silane compound 10 with respect to the total weight of the silane compound 10 and the lubricating oil 12, and 5% by weight or more and 10% by weight or less. It is more preferable that it is contained in% or less. Therefore, the surface protection oil 1 preferably contains 50% by weight or more and 98% by weight or less of the lubricating oil 12 with respect to the total weight of the silane compound 10 and the lubricating oil 12, and is 90% by weight or more and 95% by weight or less. It is more preferable to be included. Further, the surface protective oil 1 preferably has a kinematic viscosity at 40 ° C. of 27 cSt or more and 207 cST or less.

表面保護油１は、シラン化合物１０が潤滑油１２に添加されることで生成される。表面保護油１において、シラン化合物１０は、潤滑油１２に油溶した状態となっている。なお、表面保護油１は、潤滑油１２にシラン化合物１０が添加された状態、すなわちシラン化合物１０が油溶した状態で、収納室Ｃ内に注入されてもよい。また、シラン化合物１０を含まない潤滑油１２を収納室Ｃ内に充填し、収納室Ｃ内の潤滑油１２に、シラン化合物１０を添加することで、表面保護油１を生成してもよい。 The surface protective oil 1 is produced by adding the silane compound 10 to the lubricating oil 12. In the surface protection oil 1, the silane compound 10 is in a state of being oil-dissolved in the lubricating oil 12. The surface protection oil 1 may be injected into the storage chamber C in a state where the silane compound 10 is added to the lubricating oil 12, that is, in a state where the silane compound 10 is oil-dissolved. Further, the surface protective oil 1 may be produced by filling the storage chamber C with the lubricating oil 12 containing no silane compound 10 and adding the silane compound 10 to the lubricating oil 12 in the storage chamber C.

なお、表面保護油１は、シラン化合物１０及び潤滑油１２に加え、さらに、硬化触媒と水とを含んでもよい。また、表面保護油１は、以上説明した成分以外にも、不可避的不純物を含んでもよい。硬化触媒は、シラン化合物１０の加水分解及び縮合反応を促進させる触媒であり、例えば、チタンを含む物質である。硬化触媒は、表面保護油１に添加されなくてもよい。水は、シラン化合物１０の加水分解に用いられるが、潤滑油１２に水が含まれている場合は、表面保護油１に添加されなくてもよい。すなわち、ここでの水とは、潤滑油１２に含まれず、潤滑油１２に対し不純物となる水を指す。硬化触媒は、表面保護油１の全体の重量に対し、０重量％より高く、０．１重量％以下含まれていることが好ましい。また、水は、表面保護油１の全体の重量に対し、０重量％より高く、０．１重量％以下含まれていることが好ましい。なお、表面保護油１が硬化触媒と水（不純物としての水）とを含む場合、潤滑油１２にシラン化合物１０と硬化触媒と水とが添加された状態で、収納室Ｃ内に注入されてもよい。また、潤滑油１２が収納室Ｃ内に充填されており、収納室Ｃ内の潤滑油１２に、シラン化合物１０と硬化触媒と水とを添加することで、表面保護油１としてもよい。 The surface protection oil 1 may further contain a curing catalyst and water in addition to the silane compound 10 and the lubricating oil 12. Further, the surface protective oil 1 may contain unavoidable impurities in addition to the components described above. The curing catalyst is a catalyst that promotes the hydrolysis and condensation reaction of the silane compound 10, and is, for example, a substance containing titanium. The curing catalyst does not have to be added to the surface protection oil 1. Water is used for hydrolysis of the silane compound 10, but when the lubricating oil 12 contains water, it does not have to be added to the surface protection oil 1. That is, the water here refers to water that is not contained in the lubricating oil 12 and is an impurity with respect to the lubricating oil 12. The curing catalyst is preferably contained in an amount of more than 0% by weight and 0.1% by weight or less based on the total weight of the surface protective oil 1. Further, the water is preferably contained in an amount of 0.1% by weight or less, which is higher than 0% by weight, based on the total weight of the surface protective oil 1. When the surface protection oil 1 contains a curing catalyst and water (water as an impurity), the surface protective oil 1 is injected into the storage chamber C in a state where the silane compound 10 and the curing catalyst and water are added to the lubricating oil 12. May be good. Further, the lubricating oil 12 is filled in the storage chamber C, and the surface protective oil 1 may be obtained by adding the silane compound 10, the curing catalyst, and water to the lubricating oil 12 in the storage chamber C.

図２に示すように、接触ステップを実行したら、被膜形成ステップを実行する（ステップＳ１２）。被膜形成ステップにおいては、表面保護油１を部材Ａに接触させた状態で、すなわち表面保護油１を収納室Ｃ内に充填させた状態で、表面保護油１に含まれるシラン化合物１０を加水分解して縮合させることで、部材Ａの表面Ａ１に、被膜Ｍを形成する。図３に示すように、表面保護油１は、シラン化合物１０（ここでは（Ｃ２Ｈ５Ｏ）４Ｓｉ）と、水（Ｈ２Ｏ）とを含む。ここでの水は、潤滑油１２に含まれる水、又は、不純物として添加された水である。シラン化合物１０は、水と反応して加水分解する。図４に示すように、シラン化合物１０は、加水分解により、第１物質１０Ａと第２物質１０Ｂとに分解する。第１物質１０Ａは、ＳｉとＯＨとを含み、Ｓｉ基とＯＨ基とが結合した物質である。第１物質１０Ａは、本実施形態では、テトラシラノール（Ｓｉ（ＯＨ）４）である。第２物質１０Ｂは、シラン化合物１０及び水から第１物質１０Ａが除去された物質（有機物）であり、本実施形態では、エタノール（Ｃ２Ｈ５ＯＨ）である。なお、図３及び図４では、説明の便宜上、シラン化合物１０及び水を、それぞれ１つだけ記載しているが、実際には複数存在する。 As shown in FIG. 2, after the contact step is executed, the film forming step is executed (step S12). In the film forming step, the silane compound 10 contained in the surface protective oil 1 is hydrolyzed in a state where the surface protective oil 1 is in contact with the member A, that is, in a state where the surface protective oil 1 is filled in the storage chamber C. A coating film M is formed on the surface A1 of the member A. As shown in FIG. 3, the surface protective oil 1 contains a silane compound 10 (here, (C 2 H 5 O) 4 Si) and water (H 2 O). The water here is water contained in the lubricating oil 12 or water added as an impurity. The silane compound 10 reacts with water and hydrolyzes. As shown in FIG. 4, the silane compound 10 is decomposed into the first substance 10A and the second substance 10B by hydrolysis. The first substance 10A contains Si and OH, and is a substance in which a Si group and an OH group are bonded. The first substance 10A is tetrasilanol (Si (OH) 4 ) in this embodiment. The second substance 10B is a substance (organic substance) from which the first substance 10A has been removed from the silane compound 10 and water, and is ethanol (C 2 H 5 OH) in this embodiment. Although only one silane compound 10 and one water are shown in FIGS. 3 and 4 for convenience of explanation, there are actually a plurality of each.

ここで、図３及び図４に示すように、部材Ａは、ＯＨ基で終端されている。すなわち、部材Ａは、表面Ａ１が金属酸化物（ここでば、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４などの酸化鉄）となっているため、ＯＨ基で終端されている。言い換えれば、部材Ａの表面Ａ１には、ＯＨ基が存在する。第１物質１０Ａ、ここではテトラシラノールは、不安定な物質であり、反応し易い。従って、第１物質１０Ａは、表面Ａ１のＯＨ基と反応して、縮合、ここでは脱水縮合して、図５に示すように、シロキサン結合（Ｓｉ基とＯ基との結合）を生じる。すなわち、第１物質１０Ａに含まれているＳｉ基に結合しているＯＨ基が脱水縮合して、Ｓｉ基が、Ｏ基を介して、部材ＡのＦｅと結合する。従って、部材Ａの表面Ａ１には、ＳｉとＯとを含む被膜Ｍが形成される。また、第１物質１０Ａは、他の第１物質１０Ａとも脱水縮合する。言い換えれば、加水分解したシラン化合物１０同士も、脱水縮合する。すなわち、第１物質１０ＡのＳｉ基は、Ｏ基を介して、他の第１物質１０ＡのＳｉ基とも結合する。従って、被膜Ｍは、Ｓｉ基とＯ基との結合を複数含むように形成され、Ｓｉ基がＯ基を介して部材ＡのＦｅと結合し、かつ、Ｓｉ基同士がＯ基を介して結合した構成となる。従って、被膜Ｍを、厚い膜として形成することができる。なお、図５における被膜Ｍの構成（化学組成）は、一例であり、例えば、さらにＳｉ基が結合してもよい。 Here, as shown in FIGS. 3 and 4, the member A is terminated with an OH group. That is, since the surface A1 of the member A is a metal oxide (here, iron oxides such as Fe 2 O 3 and Fe 3 O 4 ), the member A is terminated by an OH group. In other words, an OH group is present on the surface A1 of the member A. The first substance 10A, here tetrasilanol, is an unstable substance and easily reacts. Therefore, the first substance 10A reacts with the OH group on the surface A1 to be condensed, here dehydrated and condensed to form a siloxane bond (bonding of Si group and O group) as shown in FIG. That is, the OH group bonded to the Si group contained in the first substance 10A is dehydrated and condensed, and the Si group is bonded to Fe of the member A via the O group. Therefore, a coating film M containing Si and O is formed on the surface A1 of the member A. Further, the first substance 10A is also dehydrated and condensed with the other first substance 10A. In other words, the hydrolyzed silane compounds 10 are also dehydrated and condensed. That is, the Si group of the first substance 10A also bonds with the Si group of another first substance 10A via the O group. Therefore, the coating film M is formed so as to include a plurality of bonds between the Si group and the O group, the Si group is bonded to Fe of the member A via the O group, and the Si groups are bonded to each other via the O group. The configuration is as follows. Therefore, the film M can be formed as a thick film. The composition (chemical composition) of the coating film M in FIG. 5 is an example, and for example, a Si group may be further bonded.

なお、被膜形成ステップは、表面保護油１を部材Ａに接触させたら、すなわち表面保護油１を収納室Ｃに充填させたら、開始する。すなわち、被膜形成ステップにおいては、表面保護油１を部材Ａに接触させる以外の処理（表面保護油１を収納室Ｃ内に充填させる以外の処理）は、不要である。ただし、被膜形成ステップにおいて、被膜Ｍの形成促進のため、表面保護油１を部材Ａに接触させる以外の処理を行ってもよい。例えば、被膜形成ステップにおいて、部材Ａと部材Ｂとを有する装置を駆動することで部材Ｂを部材Ａ上で摺動させて、部材Ｂにより部材Ａに繰り返し荷重を負荷してもよい。また、被膜形成ステップにおいて、収納室Ｃを６０℃以上９０℃以下の温度で加熱してもよい。 The film forming step is started when the surface protective oil 1 is brought into contact with the member A, that is, when the surface protective oil 1 is filled in the storage chamber C. That is, in the film forming step, a treatment other than bringing the surface protective oil 1 into contact with the member A (a treatment other than filling the storage chamber C with the surface protective oil 1) is unnecessary. However, in the film forming step, in order to promote the formation of the film M, a process other than bringing the surface protective oil 1 into contact with the member A may be performed. For example, in the film forming step, the member B may be slid on the member A by driving a device having the member A and the member B, and the member B may repeatedly apply a load to the member A. Further, in the film forming step, the storage chamber C may be heated at a temperature of 60 ° C. or higher and 90 ° C. or lower.

図２に示すように、被膜形成ステップを実行したら、反応停止ステップを実行する（ステップＳ１４）。反応停止ステップは、被膜形成ステップを開始してから所定時間経過後に実行される。ここで、被膜形成ステップは、表面保護油１を部材Ａに接触させたタイミング、すなわち表面保護油１を収納室Ｃに充填させたタイミングで開始する。従って、反応停止ステップは、表面保護油１を部材Ａに接触させたタイミングから所定時間経過後に実行されると言ってもよい。反応停止ステップにおいては、収納室Ｃに充填された表面保護油１に、被膜Ｍの形成を停止させる反応停止物を添加する。反応停止物は、本実施形態では、アルキル基を含むシラン化合物である。反応停止物としては、例えば、エトキンシラン（（Ｃ２Ｈ５Ｏ）Ｓｉ（ＣＨ３）３）、ジエトキンシラン（（Ｃ２Ｈ５Ｏ）２Ｓｉ（ＣＨ３）２）、トリエトキンシラン（（Ｃ２Ｈ５Ｏ）３Ｓｉ（ＣＨ３））などが挙げられ、これらの複数を含んでもよい。ＯＨ基の脱水反応、すなわち脱水縮合によるシロキサン結合は、反応停止物に含まれるアルキル基で停止するため、被膜Ｍを形成する脱水縮合が停止して、被膜Ｍの形成が停止される。なお、反応停止物に含まれるアルキル基は、例えばメチル基（ＣＨ３）であるが、それに限られず、エチル基（Ｃ２Ｈ５）などであってもよい。 As shown in FIG. 2, after the film formation step is executed, the reaction stop step is executed (step S14). The reaction stop step is executed after a predetermined time has elapsed from the start of the film formation step. Here, the film forming step starts at the timing when the surface protective oil 1 is brought into contact with the member A, that is, when the surface protective oil 1 is filled in the storage chamber C. Therefore, it can be said that the reaction stop step is executed after a predetermined time has elapsed from the timing when the surface protective oil 1 is brought into contact with the member A. In the reaction stop step, a reaction stop product for stopping the formation of the coating film M is added to the surface protective oil 1 filled in the storage chamber C. The reaction terminator is, in this embodiment, a silane compound containing an alkyl group. Examples of the reaction terminator include ettkinsilane ((C 2 H 5 O) Si (CH 3 ) 3 ), dietkin silane ((C 2 H 5 O) 2 Si (CH 3 ) 2 ), and trietkin silane ((C 2 )). H 5 O) 3 Si (CH 3 )) and the like, and a plurality of these may be included. Since the dehydration reaction of the OH group, that is, the siloxane bond due to the dehydration condensation is stopped at the alkyl group contained in the reaction terminator, the dehydration condensation forming the film M is stopped, and the formation of the film M is stopped. The alkyl group contained in the reaction terminator is, for example, a methyl group (CH 3 ), but is not limited to this, and may be an ethyl group (C 2 H 5 ) or the like.

なお、図２の例では、このように、被膜形成ステップの後に反応停止ステップを実行するが、反応停止ステップを実行しなくてもよい。また、収納室Ｃ内には、部材Ｂも設けられる。従って、部材Ｂの表面Ｂ１にも、被膜Ｍが形成されてもよい。 In the example of FIG. 2, the reaction stop step is executed after the film formation step in this way, but the reaction stop step may not be executed. A member B is also provided in the storage chamber C. Therefore, the coating film M may be formed on the surface B1 of the member B as well.

本実施形態においては、表面Ａ１上に形成される被膜Ｍの厚みは、０．０１μｍ以上１μｍ以下であることが好ましい。 In the present embodiment, the thickness of the coating film M formed on the surface A1 is preferably 0.01 μm or more and 1 μm or less.

以上説明したように、本実施形態に係る被膜形成方法は、表面保護油１を部材Ａの表面Ａ１に接触させる接触ステップＳ１０と、表面保護油１のシラン化合物１０を加水分解して脱水縮合させることで、ＳｉとＯとを含む被膜Ｍを部材Ａの表面Ａ１に形成する被膜形成ステップＳ１２とを有する。表面保護油１は、部材Ａの表面Ａ１に被膜Ｍを形成するためのものであり、シラン化合物１０と潤滑油１２とを含む。 As described above, in the film forming method according to the present embodiment, the contact step S10 in which the surface protective oil 1 is brought into contact with the surface A1 of the member A and the silane compound 10 of the surface protective oil 1 are hydrolyzed and dehydrated and condensed. This includes a film forming step S12 for forming a film M containing Si and O on the surface A1 of the member A. The surface protective oil 1 is for forming a coating film M on the surface A1 of the member A, and contains a silane compound 10 and a lubricating oil 12.

部材Ａは、部材Ｂから繰り返し荷重を受けるため、表面Ａ１に損傷が発生するおそれがある。表面Ａ１に損傷が発生すると、損傷が伸展することで部材Ａが破損するおそれがある。それに対し、本実施形態においては、部材Ａの表面Ａ１に表面保護油１を接触させて、表面保護油１のシラン化合物１０を反応させることで、表面Ａ１に被膜Ｍを形成する。従って、被膜Ｍによって、表面Ａ１の損傷箇所を覆うことが可能となり、損傷の進展が抑制され、部材Ａの破損を抑制することができる。また、損傷が発生する前に、すなわち損傷が発生していない箇所に、被膜Ｍを形成することで、損傷自体が起こることを抑制することもできる。また、被膜Ｍは、シラン化合物１０の反応により形成されるため、損傷箇所が微小なクラックなどであっても、そのクラックに被膜Ｍを充填することが可能となり、クラックを起点とする破損を好適に抑制できる。また、被膜Ｍは、ＳｉとＯとを含むシロキサン結合により形成されるため、例えばシリカ（ＳｉＯ２）などのように硬度が高くなり、部材Ａの破損を好適に抑制できる。また、表面保護油１は、潤滑油１２を含むため、被膜Ｍを形成した後も、部材Ａと部材Ｂとの潤滑油としてそのまま用いることができる。この場合、シラン化合物１０を追加で添加することにより、被膜Ｍを一度形成した後に、さらに被膜Ｍを形成することもできる。 Since the member A repeatedly receives a load from the member B, the surface A1 may be damaged. If the surface A1 is damaged, the damage may be extended and the member A may be damaged. On the other hand, in the present embodiment, the surface protective oil 1 is brought into contact with the surface A1 of the member A and the silane compound 10 of the surface protective oil 1 is reacted to form a film M on the surface A1. Therefore, the coating film M makes it possible to cover the damaged portion of the surface A1, suppress the progress of the damage, and suppress the damage of the member A. Further, by forming the coating film M before the damage occurs, that is, at the place where the damage has not occurred, it is possible to suppress the damage itself from occurring. Further, since the coating film M is formed by the reaction of the silane compound 10, even if the damaged portion is a minute crack or the like, the coating film M can be filled in the crack, and the damage starting from the crack is suitable. Can be suppressed. Further, since the coating film M is formed by a siloxane bond containing Si and O, the hardness becomes high like, for example, silica (SiO2), and damage to the member A can be suitably suppressed. Further, since the surface protective oil 1 contains the lubricating oil 12, it can be used as it is as the lubricating oil between the member A and the member B even after the coating M is formed. In this case, by additionally adding the silane compound 10, the film M can be formed once and then the film M can be further formed.

また、シラン化合物１０は、テトラエトキシシランである。本実施形態に係る被膜形成方法は、シラン化合物１０としてテトラエトキシシランを用いることで、加水分解により生成した第１物質１０Ａを、テトラシラノール（Ｓｉ（ＯＨ）４）とすることが可能となり、シロキサン結合の被膜Ｍを好適に形成することができる。 Further, the silane compound 10 is tetraethoxysilane. In the film forming method according to the present embodiment, by using tetraethoxysilane as the silane compound 10, the first substance 10A produced by hydrolysis can be converted to tetrasilanol (Si (OH) 4 ), and siloxane. The bonding film M can be preferably formed.

また、表面保護油１は、シラン化合物１０が、２重量％以上５０重量％以下含まれている。本実施形態に係る被膜形成方法は、この量のシラン化合物１０を表面保護油１に含ませることで、シロキサン結合の被膜Ｍを好適に生成することができる。すなわち、例えばシラン化合物１０が２重量％より少ないと、被膜Ｍの厚みＤ２が薄くなって被膜Ｍの強度が十分に保てないおそれがある。また、シラン化合物１０が５０重量％より多いと、被膜Ｍの厚みＤ２が厚くなり過ぎて部材Ａと部材Ｂとが適切に摺動されなくなったり、表面保護油１の粘度が低くなり過ぎて潤滑性能が低下したりするおそれがある。 Further, the surface protective oil 1 contains 2% by weight or more and 50% by weight or less of the silane compound 10. In the film forming method according to the present embodiment, a siloxane-bonded film M can be suitably formed by including this amount of the silane compound 10 in the surface protective oil 1. That is, for example, if the amount of the silane compound 10 is less than 2% by weight, the thickness D2 of the coating film M may become thin and the strength of the coating film M may not be sufficiently maintained. Further, when the amount of the silane compound 10 is more than 50% by weight, the thickness D2 of the coating film M becomes too thick and the member A and the member B do not slide properly, or the viscosity of the surface protective oil 1 becomes too low to lubricate. Performance may deteriorate.

また、本実施形態に係る被膜形成方法は、被膜形成ステップＳ１２を開始してから所定時間経過後に、表面保護油１に、被膜Ｍの形成を停止させる反応停止物を添加する反応停止ステップＳ１４をさらに有してもよい。反応停止ステップＳ１４を行うことで、被膜Ｍが厚くなり過ぎることを抑制して、部材Ａと部材Ｂとが適切なクリアランスを保持して摺動されなくなることを抑制できる。また、反応停止物は、アルキル基を含むシラン化合物であることが好ましい。アルキル基を含むシラン化合物を用いることで、脱水縮合によるシロキサン結合を停止させて、被膜Ｍの形成を好適に停止できる。 Further, the film forming method according to the present embodiment includes a reaction stopping step S14 in which a reaction terminator for stopping the formation of the film M is added to the surface protective oil 1 after a lapse of a predetermined time from the start of the film forming step S12. You may also have more. By performing the reaction stop step S14, it is possible to prevent the coating film M from becoming too thick and to prevent the member A and the member B from sliding while maintaining an appropriate clearance. The reaction terminator is preferably a silane compound containing an alkyl group. By using a silane compound containing an alkyl group, the siloxane bond due to dehydration condensation can be stopped, and the formation of the film M can be preferably stopped.

（第２実施形態）
次に、第２実施形態について説明する。第２実施形態においては、表面保護油１ａに、シリカ粒子１４が含まれる点で、第１実施形態とは異なる。第２実施形態において、第１実施形態と構成が共通する箇所は、説明を省略する。 (Second Embodiment)
Next, the second embodiment will be described. The second embodiment is different from the first embodiment in that the surface protective oil 1a contains silica particles 14. In the second embodiment, the description of the parts having the same configuration as that of the first embodiment will be omitted.

第２実施形態に係る表面保護油１ａは、シラン化合物１０及び潤滑油１２に加え、シリカ粒子１４を含む。シリカ粒子１４は、シリカ（ＳｉＯ２）の粒子であり、表面保護油１ａに複数個添加される。シリカ粒子１４は、表面保護油１ａの全体の重量に対し、０重量％より高く、２重量％以下含まれていることが好ましい。シリカ粒子１４をこの量とすることで、被膜の硬度を高く保ちつつ、シリカの研磨作用によって被膜の形成が阻害されることを抑制できる。また、シリカ粒子１４の平均粒径は、０．２μｍ以上２μｍ以下であることが好ましい。また、シリカ粒子１４の平均粒径は、部材Ａの表面Ａ１と部材Ｂの表面Ｂ１との間の距離Ｄ１に対し、１％以上１０％以下の大きさであることが好ましい。シリカ粒子１４の粒径をこの範囲とすることで、軸受面、すなわち表面Ａ１とＢ１との間にシリカ粒子１４を入り込ませて被膜を好適に形成させつつ、シリカ粒子１４の噛み込みによる焼き付きを抑制することができる。また、このようにシリカ粒子１４の径をある程度大きくすることで、例えば、表面Ａ１に圧痕など比較的面積や深さが大きい損傷が発生した場合に、シリカ粒子１４でその圧痕を埋めることが可能となるため、大きな損傷起点の破損も抑制できる。なお、表面保護油１ａは、第１実施形態の表面保護油１と同様に、さらに、硬化触媒と水とを含んでもよい。 The surface protection oil 1a according to the second embodiment contains silica particles 14 in addition to the silane compound 10 and the lubricating oil 12. The silica particles 14 are silica (SiO 2 ) particles, and a plurality of silica particles 14 are added to the surface protective oil 1a. The silica particles 14 are preferably contained in an amount of more than 0% by weight and 2% by weight or less based on the total weight of the surface protective oil 1a. By setting the amount of the silica particles 14 to this amount, it is possible to prevent the formation of the coating film from being hindered by the polishing action of silica while maintaining the hardness of the coating film high. The average particle size of the silica particles 14 is preferably 0.2 μm or more and 2 μm or less. The average particle size of the silica particles 14 is preferably 1% or more and 10% or less with respect to the distance D1 between the surface A1 of the member A and the surface B1 of the member B. By setting the particle size of the silica particles 14 in this range, the silica particles 14 are allowed to enter the bearing surface, that is, between the surfaces A1 and B1 to preferably form a film, and the silica particles 14 are seized by biting. It can be suppressed. Further, by increasing the diameter of the silica particles 14 to some extent in this way, for example, when damage having a relatively large area or depth such as an indentation occurs on the surface A1, the indentation can be filled with the silica particle 14. Therefore, damage at the origin of large damage can be suppressed. The surface protection oil 1a may further contain a curing catalyst and water, as in the surface protection oil 1 of the first embodiment.

なお、本実施形態におけるシリカ粒子１４の粒径の測定方法は任意であるが、例えば、レーザ回折・散乱法によって求められた粒度分布に基づき求められた粒径である。粒度分布として、体積分布を用いてもよいし個数分布を用いてもよい。この場合、シリカ粒子１４の平均粒径は、例えば、レーザ回折・散乱法によって求められた粒度分布の平均値である。 The method for measuring the particle size of the silica particles 14 in the present embodiment is arbitrary, but is, for example, the particle size obtained based on the particle size distribution obtained by the laser diffraction / scattering method. As the particle size distribution, a volume distribution may be used or a number distribution may be used. In this case, the average particle size of the silica particles 14 is, for example, the average value of the particle size distribution obtained by the laser diffraction / scattering method.

図６及び図７は、部材に被膜が形成される反応を説明する模式図である。第２実施形態における被膜形成方法も、第１実施形態と同様に、接触ステップＳ１０と被膜形成ステップＳ１２とを実行する。また、必要に応じて反応停止ステップＳ１４を実行してもよい。図６に示すように、第２実施形態においては、被膜形成ステップＳ１２において、シラン化合物１０は、加水分解により、第１物質１０Ａと第２物質１０Ｂとに分解する。ここで、シリカ粒子１４は、部材Ａの表面Ａ１と同様に、ＯＨ基で終端されている。すなわち、シリカ粒子１４の表面には、ＯＨ基が存在する。従って、第１物質１０Ａは、部材Ａの表面Ａ１のＯＨ基と反応すると共に、シリカ粒子１４の表面のＯＨ基とも反応する。すなわち、第１物質１０Ａは、図７に示すように、脱水縮合してシロキサン結合を生じて、Ｓｉ基がＯ基を介して、部材ＡのＦｅと結合する。また、第１物質１０Ａは、脱水縮合して、Ｓｉ基が、Ｏ基を介して、シリカ粒子１４とも結合する。従って、第２実施形態においては、部材ＡのＦｅとシリカ粒子１４とが、第１物質１０ＡのＳｉ基及びＯ基を介して、結合する。また、シリカ粒子１４同士も、第１物質１０ＡのＳｉ基及びＯ基を介して、互いに結合する。従って、第２実施形態においては、部材Ａの表面Ａ１に、Ｓｉ及びＯと、シリカ粒子１４とが含まれる被膜Ｍが形成される。言い換えれば、第２実施形態における被膜Ｍは、部材ＡのＦｅとシリカ粒子１４とが、Ｓｉ基及びＯ基を介して結合し（シロキサン結合で結合し）、シリカ粒子１４同士が、Ｓｉ基及びＯ基を介して結合した（シロキサン結合で結合した）構成となる。なお、図７における被膜Ｍの構成（化学組成）は、一例であり、例えば、さらにＳｉ基やシリカ粒子１４などが結合してもよい。 6 and 7 are schematic views illustrating a reaction in which a film is formed on a member. As for the film forming method in the second embodiment, the contact step S10 and the film forming step S12 are executed in the same manner as in the first embodiment. Further, the reaction stop step S14 may be executed if necessary. As shown in FIG. 6, in the second embodiment, in the film forming step S12, the silane compound 10 is decomposed into the first substance 10A and the second substance 10B by hydrolysis. Here, the silica particles 14 are terminated with OH groups, similarly to the surface A1 of the member A. That is, an OH group is present on the surface of the silica particles 14. Therefore, the first substance 10A reacts with the OH groups on the surface A1 of the member A and also reacts with the OH groups on the surface of the silica particles 14. That is, as shown in FIG. 7, the first substance 10A is dehydrated and condensed to form a siloxane bond, and the Si group is bonded to Fe of the member A via the O group. In addition, the first substance 10A is dehydrated and condensed, and the Si group is also bonded to the silica particles 14 via the O group. Therefore, in the second embodiment, the Fe of the member A and the silica particles 14 are bonded to each other via the Si group and the O group of the first substance 10A. Further, the silica particles 14 are also bonded to each other via the Si group and the O group of the first substance 10A. Therefore, in the second embodiment, a coating film M containing Si and O and silica particles 14 is formed on the surface A1 of the member A. In other words, in the coating film M in the second embodiment, Fe of the member A and the silica particles 14 are bonded via a Si group and an O group (bonded by a siloxane bond), and the silica particles 14 are bonded to each other via a Si group and an O group. It has a structure in which it is bonded via an O group (bonded by a siloxane bond). The composition (chemical composition) of the coating film M in FIG. 7 is an example, and for example, a Si group or silica particles 14 may be further bonded.

このように、第２実施形態に係る表面保護油１ａは、ＳｉＯ２の粒子であるシリカ粒子１４を含む。従って、第２実施形態によると、部材Ａの表面Ａ１上に、シリカを含む被膜Ｍを形成することが可能となり、被膜Ｍにより部材Ａの破損を抑制することができる。言い換えれば、第２実施形態においては、加水分解したシラン化合物１０同士（第１物質１０Ａ同士）を脱水縮合し、加水分解したシラン化合物１０と部材Ａとを接合し、加水分解したシラン化合物とシリカ粒子１４とを結合して、被膜Ｍを形成する。 As described above, the surface protection oil 1a according to the second embodiment contains silica particles 14 which are particles of SiO 2 . Therefore, according to the second embodiment, it is possible to form a coating film M containing silica on the surface A1 of the member A, and the coating film M can suppress damage to the member A. In other words, in the second embodiment, the hydrolyzed silane compounds 10 (first substances 10A) are dehydrated and condensed, the hydrolyzed silane compound 10 and the member A are joined, and the hydrolyzed silane compound and silica are bonded. It combines with the particles 14 to form a coating M.

また、シリカ粒子１４の平均粒径は、２μｍ以下であることが好ましい。シリカ粒子１４の粒径をこの範囲とすることで、軸受面にシリカ粒子１４を侵入させて被膜を好適に形成させつつ、シリカ粒子１４の噛み込みによる焼き付きを抑制することができる。 The average particle size of the silica particles 14 is preferably 2 μm or less. By setting the particle size of the silica particles 14 in this range, it is possible to prevent the silica particles 14 from being seized due to the biting of the silica particles 14 while allowing the silica particles 14 to penetrate into the bearing surface to form a suitable film.

また、表面保護油１は、シリカ粒子１４が２重量％以下含まれていることが好ましい。シリカ粒子１４をこの量とすることで、被膜Ｍの硬度を高く保ちつつ、シリカの研磨作用によって被膜Ｍの形成が阻害されることを抑制できる。 Further, the surface protective oil 1 preferably contains 2% by weight or less of silica particles 14. By setting the amount of the silica particles 14 to this amount, it is possible to prevent the formation of the coating film M from being hindered by the polishing action of silica while maintaining the hardness of the coating film M high.

（実施例１）
次に、実施例について説明する。実施例１においては、部材Ａとして、円錐ころ軸受に対し、表面保護油１に被膜Ｍが形成されるかを確認した。実施例１においては、シラン化合物１０を５０重量％として潤滑油を５０重量％とした表面保護油１を用いた場合に、部材Ａの表面Ａ１に厚みＤ２が５μｍとなる被膜Ｍが形成されることが確認された。また、シラン化合物１０を５重量％として潤滑油を９５重量％とした表面保護油１を用いた場合に、部材Ａの表面Ａ１に厚みＤ２が０．３μｍとなる被膜Ｍが形成されることが確認された。このように、表面保護油１を用いることで、適切に被膜Ｍが形成されることが分かる。 (Example 1)
Next, an embodiment will be described. In the first embodiment, it was confirmed whether or not the coating M was formed on the surface protective oil 1 on the conical roller bearing as the member A. In Example 1, when the surface protective oil 1 in which the silane compound 10 is 50% by weight and the lubricating oil is 50% by weight is used, a coating film M having a thickness D2 of 5 μm is formed on the surface A1 of the member A. It was confirmed that. Further, when the surface protective oil 1 in which the silane compound 10 is 5% by weight and the lubricating oil is 95% by weight is used, a coating film M having a thickness D2 of 0.3 μm may be formed on the surface A1 of the member A. confirmed. As described above, it can be seen that the film M is appropriately formed by using the surface protective oil 1.

（実施例２）
実施例２においては、部材Ａに被膜Ｍを形成した上で、疲労強度試験を行った。図８は、実施例２の疲労強度試験の結果を示すグラフである。実施例２においては、内輪内径が２５ｍｍの円すいころ軸受を使用し、疲労寿命を求める試験を行った。試験を加速するため、軸受の外輪部にはブラスト処理によって疵を設けた。また、軸受に加える面圧は、２．６ＧＰａとし、回転数は３５００ｒｐｍとした。実施例２に係る表面保護油１は、潤滑油１２の粘度グレードをＶＧ３２とし、シラン化合物１０として、テトラエトキシシランのオリゴマーを５重量％とし、チタン系の硬化触媒を０．１重量％、水を０．１重量％添加した。また、比較例としては、実施例２と同じ潤滑油１２を使用したが、シラン化合物１０、硬化触媒及び水を加えなかった。図８は、実施例２と比較例との疲労試験の結果を示している。図８のデータＴ１が実施例２の結果で、データＴ２が比較例の結果である。図８に示すように、シラン化合物１０を添加剤として加えた場合、加えない場合と比較して、軸受の寿命が延びる傾向にあることが分かり、延命効果は、少なくとも約２倍であることが分かる。 (Example 2)
In Example 2, a fatigue strength test was conducted after forming a coating film M on the member A. FIG. 8 is a graph showing the results of the fatigue strength test of Example 2. In Example 2, a tapered roller bearing having an inner ring inner diameter of 25 mm was used, and a test was conducted to determine the fatigue life. In order to accelerate the test, the outer ring of the bearing was blasted with flaws. The surface pressure applied to the bearing was 2.6 GPa, and the rotation speed was 3500 rpm. In the surface protection oil 1 according to Example 2, the viscosity grade of the lubricating oil 12 is VG32, the silane compound 10 is 5% by weight of the tetraethoxysilane oligomer, the titanium-based curing catalyst is 0.1% by weight, and water. Was added in an amount of 0.1% by weight. Further, as a comparative example, the same lubricating oil 12 as in Example 2 was used, but the silane compound 10, the curing catalyst and water were not added. FIG. 8 shows the results of the fatigue test between Example 2 and Comparative Example. Data T1 in FIG. 8 is the result of Example 2, and data T2 is the result of Comparative Example. As shown in FIG. 8, it was found that when the silane compound 10 was added as an additive, the life of the bearing tended to be extended as compared with the case where the silane compound 10 was not added, and the life extension effect was at least about twice. I understand.

以上、本発明の実施形態を説明したが、この実施形態の内容により実施形態が限定されるものではない。また、前述した構成要素には、当業者が容易に想定できるもの、実質的に同一のもの、いわゆる均等の範囲のものが含まれる。さらに、前述した構成要素は適宜組み合わせることが可能である。さらに、前述した実施形態の要旨を逸脱しない範囲で構成要素の種々の省略、置換又は変更を行うことができる。 Although the embodiments of the present invention have been described above, the embodiments are not limited by the contents of the embodiments. Further, the above-mentioned components include those that can be easily assumed by those skilled in the art, those that are substantially the same, that is, those in a so-called equal range. Further, the above-mentioned components can be combined as appropriate. Further, various omissions, replacements or changes of the components can be made without departing from the gist of the above-described embodiment.

１ 表面保護油
１０ シラン化合物
１０Ａ 第１物質
１２ 潤滑油
１４ シリカ粒子
Ａ 部材 1 Surface protection oil 10 Silane compound 10A First substance 12 Lubricating oil 14 Silica particles A member

Claims (7)

部材の表面に被膜を形成するための表面保護油であって、
テトラエトキシシランであるシラン化合物と、潤滑油とを含み、
前記シラン化合物が、２重量％以上５０重量％以下含まれている、表面保護油。 A surface protective oil for forming a film on the surface of a member.
It contains a silane compound that is tetraethoxysilane and a lubricating oil.
A surface protective oil containing 2% by weight or more and 50% by weight or less of the silane compound. さらに、ＳｉＯ２の粒子であるシリカ粒子を含む、請求項１に記載の表面保護油。 The surface protective oil according to claim 1, further comprising silica particles which are particles of SiO 2 . 前記シリカ粒子の平均粒径は、２μｍ以下である、請求項２に記載の表面保護油。 The surface protective oil according to claim 2, wherein the silica particles have an average particle size of 2 μm or less. 前記シリカ粒子が、２重量％以下含まれている、請求項２又は請求項３に記載の表面保護油。 The surface protective oil according to claim 2 or 3, wherein the silica particles are contained in an amount of 2% by weight or less. 部材の表面に被膜を形成する被膜形成方法であって、
請求項１から請求項４のいずれか１項に記載の表面保護油を、前記部材の表面に接触させる接触ステップと、
前記シラン化合物を加水分解して脱水縮合させることで、ＳｉとＯとを含む被膜を前記部材の表面に形成する被膜形成ステップと、
を有する、被膜形成方法。 A film forming method for forming a film on the surface of a member.
A contact step in which the surface protective oil according to any one of claims 1 to 4 is brought into contact with the surface of the member.
A film forming step of forming a film containing Si and O on the surface of the member by hydrolyzing and dehydrating and condensing the silane compound.
A film forming method having. 前記被膜形成ステップを開始してから所定時間経過後に、前記表面保護油に、前記被膜の形成を停止させる反応停止物を添加する反応停止ステップをさらに有する、請求項５に記載の被膜形成方法。 The film forming method according to claim 5, further comprising a reaction termination step of adding a reaction terminator for stopping the film formation to the surface protective oil after a lapse of a predetermined time from the start of the film forming step. 前記反応停止物は、アルキル基を含むシラン化合物である、請求項６に記載の被膜形成方法。 The film-forming method according to claim 6, wherein the reaction terminator is a silane compound containing an alkyl group.
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JP2005048808A (en) * 2003-07-30 2005-02-24 Nsk Ltd Rolling device
JP2008056930A (en) * 2006-08-31 2008-03-13 Chevron Oronite Co Llc Method for forming tetraoxy-silane derived antiwear film and lubricating oil composition therefor
JP2016030777A (en) * 2014-07-28 2016-03-07 奥野製薬工業株式会社 Process liquid for siliceous film formation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005048808A (en) * 2003-07-30 2005-02-24 Nsk Ltd Rolling device
JP2008056930A (en) * 2006-08-31 2008-03-13 Chevron Oronite Co Llc Method for forming tetraoxy-silane derived antiwear film and lubricating oil composition therefor
JP2016030777A (en) * 2014-07-28 2016-03-07 奥野製薬工業株式会社 Process liquid for siliceous film formation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023037928A1 (en) * 2021-09-07 2023-03-16 三菱重工業株式会社 Method for forming coating film and lubricating oil composition

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