JP7367334B2 - Method for producing nanodiamond composition - Google Patents
Method for producing nanodiamond composition Download PDFInfo
- Publication number
- JP7367334B2 JP7367334B2 JP2019083346A JP2019083346A JP7367334B2 JP 7367334 B2 JP7367334 B2 JP 7367334B2 JP 2019083346 A JP2019083346 A JP 2019083346A JP 2019083346 A JP2019083346 A JP 2019083346A JP 7367334 B2 JP7367334 B2 JP 7367334B2
- Authority
- JP
- Japan
- Prior art keywords
- dispersion
- composition
- nanodiamond
- base oil
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Carbon And Carbon Compounds (AREA)
Description
本発明はナノダイヤモンド（以下、「ＮＤ」と言うことがある。）組成物とその製造法に関する。このＮＤ組成物は、潤滑油添加剤、ＣＭＰ（Chemical Mechanical Polishing ：化学機械研磨）向け研磨剤、燃料電池向け耐腐食性電極メッキ材料、切削工具などの高硬度表面コ－ティング層形成材料、高耐電圧材料、高耐熱・高熱伝導材料など、工学応用分野で利用できる。 The present invention relates to a nanodiamond (hereinafter sometimes referred to as "ND") composition and a method for producing the same. This ND composition is used as lubricating oil additives, abrasives for CMP (Chemical Mechanical Polishing), corrosion-resistant electrode plating materials for fuel cells, materials for forming high-hardness surface coating layers on cutting tools, etc. It can be used in engineering applications, such as voltage-resistant materials, high heat resistance, and high heat conduction materials.
ＮＤは、爆轟法や高温高圧法によって製造される。爆轟法は、トリニトロトルエン及びヘキソーゲンを爆轟させることにより、ナノサイズのダイヤモンドを得る方法である。この方法で得られるＮＤは、水や極性有機溶媒への溶解性は高いが、油や低極性有機溶媒への溶解性が低いという問題がある。そのため、ＮＤの用途開発はさほど進んでいない。
このため、水や有機溶媒に対する溶解性を向上させる目的で、ＮＤの表面を化学修飾する試みがなされている。
特許文献１では、ポリエチレングリコール構造を含む分子でＮＤ表面を修飾することで、水や極性有機溶媒への溶解性が向上することが報告されている
特許文献２では、カチオン極性基を含む分子でＮＤ表面を修飾することで、ＮＤ粒子同士が静電反発により分離し凝集しにくくなることが報告されている。
ND is manufactured by a detonation method or a high temperature/high pressure method. The detonation method is a method for obtaining nano-sized diamonds by detonating trinitrotoluene and hexogen. The ND obtained by this method has a problem of high solubility in water and polar organic solvents, but low solubility in oil and low polar organic solvents. Therefore, the development of applications for ND has not progressed very much.
For this reason, attempts have been made to chemically modify the surface of NDs in order to improve their solubility in water and organic solvents.
Patent Document 1 reports that the solubility in water and polar organic solvents is improved by modifying the ND surface with a molecule containing a polyethylene glycol structure. It has been reported that by modifying the ND surface, ND particles are separated from each other due to electrostatic repulsion and become less likely to aggregate.
しかしながら、特許文献１や特許文献２に記載された方法では、導入される結合基が極性を有するために、例えば、鉱油のような非水系の低極性な液体への溶解性は十分ではなかった。そのためＮＤは潤滑剤として用いられるが、液体への溶解性が不十分であると粗粒が含まれるため、ＮＤを添加することによって却って潤滑性が低下することがあった。また、ＮＤを有機合成によって修飾する場合、ＮＤを修飾する化合物は有機合成に適用できる官能基含有化合物に限定され、またその官能基を有する化合物を合成しなければならないという問題があった。 However, in the methods described in Patent Document 1 and Patent Document 2, because the bonding group introduced has polarity, the solubility in non-aqueous low polarity liquids such as mineral oil was not sufficient. . Therefore, ND is used as a lubricant, but if its solubility in liquid is insufficient, it will contain coarse particles, so adding ND may actually reduce the lubricity. Furthermore, when modifying NDs by organic synthesis, the compounds that modify the NDs are limited to functional group-containing compounds that can be applied to organic synthesis, and there is a problem in that a compound having the functional group must be synthesized.
本発明は、上記事情に鑑みてなされたものであって、事前に修飾する化合物を合成することなく極性及び低極性いずれの基油に対しても溶解性に優れた高溶解性のＮＤ組成物と、その製造法を提供し、その結果得られたＮＤ組成物の耐摩耗性を向上させることを目的とする。 The present invention has been made in view of the above circumstances, and provides a highly soluble ND composition with excellent solubility in both polar and low polar base oils without the need to synthesize a modifying compound in advance. The present invention aims to provide a method for producing the same, and to improve the wear resistance of the resulting ND composition.
［１］基油とナノダイヤモンドとを混合し、前記基油と前記ナノダイヤモンドを含むナノダイヤモンド分散体を得る分散工程と、前記ナノダイヤモンド分散体への加熱及び放射線照射の少なくとも一方を行う変性工程と、を含むナノダイヤモンド組成物の製造方法。
［２］前記ナノダイヤモンド分散体を得る分散工程において、反応性成分を混合する［１］に記載のナノダイヤモンド組成物の製造方法。
［３］前記ナノダイヤモンド分散体の変性工程において、加熱と放射線照射を同時に行う［１］または［２］に記載のナノダイヤモンド組成物の製造方法。
［４］前記ナノダイヤモンド分散体の変性工程において、前記ナノダイヤモンド分散体中の酸素分子濃度を１０質量ｐｐｍ以下とする［１］～［３］に記載のナノダイヤモンド組成物の製造方法。
［５］前記ナノダイヤモンド分散体の変性工程で、前記ナノダイヤモンド分散体の加熱を、６０℃以上２００℃以下で行う［１］～［４］のいずれかに記載のナノダイヤモンド組成物の製造方法。
［６］前記ナノダイヤモンド分散体の変性工程で、前記ナノダイヤモンド分散体の放射線照射を、ナノダイヤモンド分散体１ｍＬあたりに照射するエネルギー量が、１～１００Ｊで行う［１］～［５］のいずれかに記載のナノダイヤモンド組成物の製造方法。
［７］前記ナノダイヤモンド分散体を得る分散工程と、前記ナノダイヤモンド分散体の変性工程の間に、前記ナノダイヤモンドの解砕工程を含む、［１］～［６］のいずれかに記載のナノダイヤモンド組成物の製造方法。
［８］前記ナノダイヤモンド分散体を得る分散工程及び前記ナノダイヤモンド分散体の変性工程の少なくとも一方の工程を、前記ナノダイヤモンドを解砕しながら行う［１］～［７］のいずれか１項に記載のナノダイヤモンド組成物の製造方法。
［９］前記ナノダイヤモンド分散体及び前記ナノダイヤモンド組成物の少なくとも一方から、粗粒成分を除去する工程を含む［１］～［８］のいずれかに記載のナノダイヤモンド組成物の製造方法。
［１０］前記ナノダイヤモンド組成物から、前記反応性成分を除去する工程を含む［２］～［９］のいずれかに記載のナノダイヤモンド組成物の製造方法。
［１１］基油、ナノダイヤモンド、ナノダイヤモンド付加体、を含むナノダイヤモンド組成物。
[1] A dispersion step of mixing base oil and nanodiamonds to obtain a nanodiamond dispersion containing the base oil and the nanodiamonds, and a modification step of performing at least one of heating and irradiating the nanodiamond dispersion. and a method for producing a nanodiamond composition.
[2] The method for producing a nanodiamond composition according to [1], wherein a reactive component is mixed in the dispersion step for obtaining the nanodiamond dispersion.
[3] The method for producing a nanodiamond composition according to [1] or [2], wherein heating and radiation irradiation are performed simultaneously in the modification step of the nanodiamond dispersion.
[4] The method for producing a nanodiamond composition according to [1] to [3], wherein in the modification step of the nanodiamond dispersion, the concentration of oxygen molecules in the nanodiamond dispersion is 10 mass ppm or less.
[5] The method for producing a nanodiamond composition according to any one of [1] to [4], wherein in the modification step of the nanodiamond dispersion, the nanodiamond dispersion is heated at a temperature of 60° C. or higher and 200° C. or lower. .
[6] Any one of [1] to [5] in which the nanodiamond dispersion is irradiated with radiation at an energy amount of 1 to 100 J per 1 mL of the nanodiamond dispersion in the modification step of the nanodiamond dispersion. A method for producing a nanodiamond composition according to claim 1.
[7] The nanodiamond dispersion according to any one of [1] to [6], including a step of crushing the nanodiamonds between the dispersion step of obtaining the nanodiamond dispersion and the modification step of the nanodiamond dispersion. Method for producing a diamond composition.
[8] According to any one of [1] to [7], at least one of the dispersion step of obtaining the nanodiamond dispersion and the modification step of the nanodiamond dispersion is performed while crushing the nanodiamonds. A method of manufacturing the described nanodiamond composition.
[9] The method for producing a nanodiamond composition according to any one of [1] to [8], which includes a step of removing coarse grain components from at least one of the nanodiamond dispersion and the nanodiamond composition.
[10] The method for producing a nanodiamond composition according to any one of [2] to [9], which includes a step of removing the reactive component from the nanodiamond composition.
[11] A nanodiamond composition containing a base oil, a nanodiamond, and a nanodiamond adduct.
本発明によれば、基油への溶解性に優れた高溶解性のＮＤ組成物と、その製造法を提供し、その結果得られたＮＤ組成物の耐摩耗性を向上させることができる。ＮＤを基油に溶解させる場合、事前にＮＤを修飾する化合物を合成した上で、ＮＤに反応させる工程が不要になり、溶解させたい基油にＮＤを混合し、熱処理及び放射線照射の少なくとも一方を行うだけで、十分に溶解させることができる。 According to the present invention, it is possible to provide a highly soluble ND composition with excellent solubility in base oil and a method for producing the same, and to improve the wear resistance of the resulting ND composition. When dissolving NDs in base oil, it is no longer necessary to synthesize a compound that modifies NDs in advance and react with NDs. Instead, it is necessary to mix NDs into the base oil to be dissolved, and then perform at least one of heat treatment and radiation irradiation. It can be sufficiently dissolved by simply doing the following.
以下、本発明を適用したＮＤ組成物及びその製造方法の実施の形態について説明する。
なお、本実施の形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
Hereinafter, embodiments of an ND composition and a method for manufacturing the same to which the present invention is applied will be described.
It should be noted that the present embodiment is specifically explained in order to better understand the gist of the invention, and is not intended to limit the invention unless otherwise specified.
［ＮＤ組成物］
本実施形態のＮＤ組成物は、基油と、ＮＤと、を含み、後述する本実施形態のＮＤ組成物の製造方法において、少なくとも基油と、ＮＤとを含む混合物（「ＮＤ分散体」という）を熱処理及び放射線照射の少なくとも一方を行うことで得られる。ＮＤ分散体は、さらに反応性成分を含んでもよい。
なお、本明細書において、「分散」とは、溶液中でチンダル現象（溶液に光を通したときに、光の入射方向より斜めより見ると光の通路が見える現象）が確認できる状態を指す。この状態では、目視で液体は濁って見え、ＮＤの粒子が凝集し、光の波長（３００ナノメートル）以上の大きさで、溶液中に存在していると考えられる。
一方「溶解」とは、溶液中でチンダル現象は確認できない状態を指す。溶液は目視で濁りがなく見える。この状態では、ＮＤは３００ナノメートル未満の大きさで、溶液中に存在していると考えられる。
[ND composition]
The ND composition of this embodiment contains a base oil and ND, and in the method for producing an ND composition of this embodiment described later, a mixture (referred to as "ND dispersion") containing at least base oil and ND is used. ) can be obtained by performing at least one of heat treatment and radiation irradiation. The ND dispersion may further contain a reactive component.
In this specification, "dispersion" refers to a state in which the Tyndall phenomenon (a phenomenon in which when light passes through a solution, the path of light is visible when viewed from an angle from the direction of incidence of the light) can be observed. . In this state, the liquid appears cloudy to the naked eye, and it is thought that the ND particles aggregate and exist in the solution with a size larger than the wavelength of light (300 nanometers).
On the other hand, "dissolution" refers to a state in which the Tyndall phenomenon cannot be observed in a solution. The solution does not appear cloudy to the naked eye. In this state, the NDs are considered to be less than 300 nanometers in size and present in solution.
（基油）
本実施形態のＮＤ組成物に含まれる基油とは、通常、潤滑油において添加剤などを混入する前の油のことであり、特に限定されるものではない。潤滑油の基油として広く使用されている鉱油及び合成油が好適に用いられる。
潤滑油として用いられる鉱油は、一般的に、内部に含まれる炭素―炭素二重結合を水素添加により飽和して、飽和炭化水素に変換したものである。このような鉱油としては、パラフィン系基油、ナフテン系基油等が挙げられる。
合成油としては、合成炭化水素油、エーテル油、エステル油等が挙げられる。具体的には、ポリα－オレフィン、ジエステル、ポリアルキレングリコール、ポリアルファオレフィン、ポリアルキルビニールエーテル、ポリブテン、イソパラフィン、オレフィンコポリマー、アルキルベンゼン、アルキルナフタレン、ジイソデシルアジペート、モノエステル、二塩基酸エステル、三塩基酸エステル、ポリオールエステル（トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール２－エチルヘキサノエート、ペンタエリスリトールペラルゴネート等）、ジアルキルジフェニルエーテル、アルキルジフェニルサルファイド、ポリフェニルエーテル、シリコーン潤滑油（ジメチルシリコーン等）、パーフルオロポリエーテル、１，２，４－トリメチルベンゼン等が好適に用いられる。これらの中でも、ポリα－オレフィン、ジエステル、ポリオールエステル、ポリアルキレングリコール、ポリアルキルビニールエーテル、１，２，４－トリメチルベンゼンがより好適に用いられる。
これらの鉱油や合成油は、１種を単独で用いてもよく、これらの中から選ばれる２種以上を任意の割合で混合して用いてもよい。
基油は、後述する変性工程において、変性処理を行うことにより、基油を構成する分子の化学結合が開裂（以下、“結合開裂”）し、その結果、化学反応性に富むラジカルが発生し、このラジカルがＮＤに付加反応して、ＮＤ付加体を形成すると考えられる。基油は、変性処理によって、炭素－炭素結合やシリコーンのケイ素－酸素結合が切れたり、水酸基から水素が引き抜かれることによって、ラジカルが発生する。すなわちＮＤ分散体の変性処理を行うことにより、ＮＤより、基油への親和性の高いＮＤ付加体となる。ＮＤ付加体とは、変性処理することにより基油や後述する反応性成分由来の基がＮＤに付加した化合物を指す。ＮＤは凝集しやすく、通常は、基油との親和性が低いため基油に混合しても凝集したままか、あるいは更に大きな凝集粒子になるが、変性処理することで基油への親和性が向上したＮＤ付加体が形成され、ＮＤの基油への分散性が向上すると考えられる。そのためＮＤ組成物は、ＮＤの凝集体ではなく、ＮＤ付加体を高分散させ、溶解した状態で含んでいるため、基油の耐摩耗性や低摩擦性を向上することができる。
(base oil)
The base oil contained in the ND composition of the present embodiment is usually a lubricating oil before adding additives and the like, and is not particularly limited. Mineral oils and synthetic oils that are widely used as base oils for lubricating oils are preferably used.
Mineral oil used as a lubricating oil is generally one in which the carbon-carbon double bonds contained therein are saturated by hydrogenation to convert them into saturated hydrocarbons. Examples of such mineral oils include paraffinic base oils, naphthenic base oils, and the like.
Examples of synthetic oils include synthetic hydrocarbon oils, ether oils, ester oils, and the like. Specifically, polyα-olefins, diesters, polyalkylene glycols, polyalphaolefins, polyalkyl vinyl ethers, polybutenes, isoparaffins, olefin copolymers, alkylbenzenes, alkylnaphthalenes, diisodecyl adipates, monoesters, dibasic acid esters, and tribasic acid esters. Acid esters, polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), dialkyl diphenyl ethers, alkyldiphenyl sulfides, polyphenyl ethers, silicone lubricating oils (dimethyl silicone, etc.), perfluoropolyether, 1,2,4-trimethylbenzene, etc. are preferably used. Among these, polyα-olefins, diesters, polyol esters, polyalkylene glycols, polyalkyl vinyl ethers, and 1,2,4-trimethylbenzene are more preferably used.
These mineral oils and synthetic oils may be used alone or in a mixture of two or more selected from them in any proportion.
When base oil is modified in the modification process described below, the chemical bonds of the molecules that make up the base oil are cleaved (hereinafter referred to as "bond cleavage"), and as a result, highly chemically reactive radicals are generated. It is thought that this radical undergoes an addition reaction with ND to form an ND adduct. Radicals are generated in base oils by breaking carbon-carbon bonds and silicon-oxygen bonds in silicone or extracting hydrogen from hydroxyl groups through modification treatment. That is, by modifying the ND dispersion, it becomes an ND adduct that has a higher affinity for base oil than ND. The ND adduct refers to a compound in which a group derived from a base oil or a reactive component described below is added to ND through modification treatment. ND tends to aggregate and usually has low affinity with base oil, so even when mixed with base oil, it remains aggregated or becomes even larger aggregated particles, but by modifying it, it can improve its affinity for base oil. It is thought that an ND adduct with improved ND adduct is formed, and the dispersibility of ND in the base oil is improved. Therefore, since the ND composition contains the ND adduct in a highly dispersed and dissolved state rather than an aggregate of ND, the wear resistance and low friction properties of the base oil can be improved.
（ナノダイヤモンド：ＮＤ）
ナノダイヤモンドとは、ナノマテリアルの一種で粒子状のダイヤモンドである。ナノダイヤモンドは一次粒子の粒径が２ナノメートル以上、２０ナノメートル以下であることが好ましく、４ナノメートル以上、１５ナノメートル以下であることがより好ましい。ＮＤは、例えば、爆轟法により製造したナノダイヤモンドを用いることができる。爆轟法は、ＴＮＴ（トリニトロトルエン）とトリメチレントリニトロアミンとを密閉容器内で反応（爆発）させる方法である。ここで、ナノダイヤモンドの一次粒子の数平均粒径は、固体であれば、粒子の大きさに応じて透過型電子顕微鏡（ＴＥＭ）あるいは走査型電子顕微鏡（ＳＥＭ）を用いて観察した画像を解析することによって求められる。またナノダイヤモンドが液体中に分散している場合は、動的レーザー散乱法を用いて重量粒度分布から重量平均粒子径を測定する。液体中に分散していても、乾燥させて固体のナノダイヤモンドにしてから、ＴＥＭやＳＥＭで測定しても良い。
ＮＤは、水や極性有機溶媒への溶解性を高めるために、例えば、特許文献１で開示されるＮＤのように表面にアミン結合（－ＮＨ－）、エーテル結合（－Ｏ－）、カルボキシル結合（－ＣＯＯ－）、フェニル基（－ＰＨ）、チオエーテル結合（－Ｓ－）などを介して、ポリグリセリル基などを導入したＮＤを用いてもよい。これらの表面修飾したＮＤを、本実施形態におけるＮＤ組成物とすることで、基油への溶解性が向上し、耐摩耗性及び低摩擦性を向上することができる。
(Nano diamond: ND)
Nanodiamond is a type of nanomaterial and is a particulate diamond. The primary particle size of nanodiamonds is preferably 2 nanometers or more and 20 nanometers or less, more preferably 4 nanometers or more and 15 nanometers or less. For example, nanodiamonds manufactured by a detonation method can be used as the ND. The detonation method is a method in which TNT (trinitrotoluene) and trimethylene trinitramine are reacted (exploded) in a closed container. Here, the number average particle size of the primary particles of nanodiamonds can be determined by analyzing images observed using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) depending on the size of the particles if they are solid. required by doing. In addition, when nanodiamonds are dispersed in a liquid, the weight average particle diameter is measured from the weight particle size distribution using a dynamic laser scattering method. Even if they are dispersed in a liquid, they may be dried to form solid nanodiamonds and then measured using a TEM or SEM.
In order to increase the solubility in water and polar organic solvents, NDs have amine bonds (-NH-), ether bonds (-O-), and carboxyl bonds on the surface, as in the ND disclosed in Patent Document 1, for example. An ND into which a polyglyceryl group or the like is introduced via a (-COO-), phenyl group (-PH), thioether bond (-S-), etc. may also be used. By using these surface-modified NDs as the ND composition in this embodiment, solubility in base oil can be improved, and wear resistance and low friction properties can be improved.
（反応性成分）
ＮＤ分散体には、またＮＤの溶解性を向上させる目的で反応性成分を添加してもよい。ＮＤの基油への親和性が高くない場合、後述する第一工程でＮＤが凝集するのを防ぐ目的で、反応性成分を添加し、反応性成分中にＮＤを分散させることができる、その結果基油中にＮＤが凝集せず分散させることができるため、その後の工程を効率よく進めることができる。反応性成分は、ＮＤの溶解性を向上させるために、ＮＤとの親和性が高く、更に基油とも親和性が高いものが好ましい。また更に後述する変性処理で、ラジカルを発生させＮＤに付加する化合物であることが好ましい。ＮＤは基油だけでなく反応性成分とも化学結合することにより、更にＮＤの基油への溶解性が向上する。
反応性成分は、ラジカル発生しやすい化合物で、かつ基油への溶解性の点で基油と親和性が高い化合物であることが好ましく、また、約２００℃以下でＮＤに化学結合する化合物であることが好ましい。
また反応性成分として、用途に適した別の種類の基油を用いても構わない。
(reactive component)
A reactive component may also be added to the ND dispersion for the purpose of improving the solubility of ND. If the affinity of the NDs to the base oil is not high, a reactive component can be added to disperse the NDs in the reactive component in order to prevent the NDs from agglomerating in the first step described below. As a result, the NDs can be dispersed in the base oil without agglomerating, so that subsequent steps can be carried out efficiently. In order to improve the solubility of ND, the reactive component preferably has high affinity with ND and also has high affinity with base oil. Furthermore, it is preferable that the compound is a compound that generates radicals and adds them to NDs in the modification treatment described later. By chemically bonding the ND with not only the base oil but also the reactive component, the solubility of the ND in the base oil is further improved.
The reactive component is preferably a compound that easily generates radicals and has high affinity with the base oil in terms of solubility in the base oil, and is also a compound that chemically bonds to the ND at temperatures below about 200°C. It is preferable that there be.
Furthermore, other types of base oil suitable for the application may be used as the reactive component.
反応性成分としては、例えば、基油に該当しない、パラフィン、オレフィン、ナフテン、芳香族等の炭化水素、アルコール、ポリエーテル、ポリエステル等の骨格を有する化合物が好ましい。
また、反応性成分は、約２００℃以下でＮＤに化学結合させるという点では、例えば、側鎖や環を有する飽和炭化水素、ジエン、芳香族等の不飽和炭化水素、環を複数有する芳香族、アルキル側鎖を有する芳香族、エーテル結合を有する化合物、エステル結合を有する化合物、リン酸エステル結合を有する化合物、ジスルフィド結合を有する化合物、フェノール水酸を有する化合物及びシリコーンが好ましい。
The reactive component is preferably a compound having a skeleton such as paraffin, olefin, naphthene, aromatic hydrocarbon, alcohol, polyether, or polyester, which is not a base oil.
In addition, in terms of chemically bonding the reactive component to the ND at temperatures below about 200°C, for example, saturated hydrocarbons having side chains or rings, dienes, unsaturated hydrocarbons such as aromatics, aromatic compounds having multiple rings, etc. , aromatics having an alkyl side chain, compounds having an ether bond, compounds having an ester bond, compounds having a phosphate ester bond, compounds having a disulfide bond, compounds having a phenolic hydroxyl, and silicones are preferable.
このような反応性成分としては、具体的には、直鎖または分岐した炭化水素（例えば、ヘキサン、デカン、シクロヘキサン、イソブタン、デカリン等）、不飽和２重結合を有する炭化水素（例えば、ヘキサセン、ペンタセン、シクロヘキセン、デセン、テレピン油、テルペン誘導体、α－オレフィン等）、アルキルを有する芳香族炭化水素（例えば、ドデシルベンゼン、ヘキサベンゼン、エチルベンゼン、トリメチルベンゼン、テトラメチルベンゼン、クメン、メチルナフタレン、アントラセン、ブタセン、ヘキサセンなどの多環芳香環の炭化水素等）、アルコール（例えば、エタノール、ブタノール、ヘキサノール、デカノール）、エーテル結合を有する化合物（例えば、プロピレングリコール、ポリプロピレングリコール、ポリエチレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、トリプロピレングリコール、ジプロピレングリコール、トリエチレングリコール、テトラヒロドフラン等）、エステル基を有する化合物（例えば、酢酸エチル、酢酸オクチル等）、γ－ブチロラクトンや脂肪（脂肪酸グリセリンエステル）、リン酸エステル結合を有する化合物（例えば、リン酸トリクレジル（ＴＣＰ）、リン酸トリフェニル（ＴＰＰ）、２，６－ジ－ｔｅｒｔ－ブチルフェノール（ＤＴＰ）等）、ジスルフィド結合を有する化合物（例えば、ジベンジルジサルファイド（ＤＢＤＳ）、ジ－ｐ－トリルジスルフィド（ＤＴＤＳ）等）、フェノール水酸を有する化合物（例えば、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン（ＢＨＴ）、ブチルヒドロキシアニソール（ＢＨＡ）、２，６－ブチルフェノール（ＤＴＰ）、ビス(３、５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル)メタン（ＢＤＢＡ）、２，４，６－トリブチルフェノール（ＴＢＰ）等）、ジアゾ化合物、シリコーン、等が挙げられ、さらに、これらの組み合わせが挙げられる。
上記のうち、特にアルコール、ポリエーテル、グリコールは、ＮＤの溶解性が高いため、好ましい。
反応性成分を混合する場合、ＮＤの質量に対して、１０～１００００倍量の反応性成分混合することが好ましく、３０～５０００倍量混合することがより好ましく、更に５０～１０００倍量混合することがより好ましい。
Specifically, such reactive components include straight-chain or branched hydrocarbons (e.g., hexane, decane, cyclohexane, isobutane, decalin, etc.), hydrocarbons having unsaturated double bonds (e.g., hexacene, pentacene, cyclohexene, decene, turpentine oil, terpene derivatives, α-olefin, etc.), aromatic hydrocarbons having alkyl (e.g. dodecylbenzene, hexabenzene, ethylbenzene, trimethylbenzene, tetramethylbenzene, cumene, methylnaphthalene, anthracene, polycyclic aromatic hydrocarbons such as butacene and hexacene), alcohols (e.g. ethanol, butanol, hexanol, decanol), compounds with ether bonds (e.g. propylene glycol, polypropylene glycol, polyethylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tripropylene glycol, dipropylene glycol, triethylene glycol, tetrahydrofuran, etc.), compounds with ester groups (e.g. ethyl acetate, octyl acetate, etc.), γ-butyrolactone and fats (fatty acid glycerin esters) ), compounds having a phosphate ester bond (e.g., tricresyl phosphate (TCP), triphenyl phosphate (TPP), 2,6-di-tert-butylphenol (DTP), etc.), compounds having a disulfide bond (e.g., dibenzyl disulfide (DBDS), di-p-tolyl disulfide (DTDS), etc.), compounds containing phenolic hydroxyl (e.g., 3,5-di-tert-butyl-4-hydroxytoluene (BHT), butylhydroxyanisole) (BHA), 2,6-butylphenol (DTP), bis(3,5-di-tert-butyl-4-hydroxyphenyl)methane (BDBA), 2,4,6-tributylphenol (TBP), etc.), diazo compounds, silicones, etc., and combinations thereof.
Among the above, alcohol, polyether, and glycol are particularly preferable because they have high solubility for ND.
When mixing reactive components, it is preferable to mix the reactive components in an amount of 10 to 10,000 times, more preferably 30 to 5,000 times, and further 50 to 1,000 times the mass of the ND. It is more preferable.
これらの反応性成分がＮＤに付加する場合は、上述した基油と同様、後述する変性処理を行うことにより、反応性成分を構成する分子の化学結合が開裂（以下、“結合開裂”）し、その結果、化学反応性に富むラジカルが発生し、このラジカルがＮＤに付加反応して、ＮＤ付加体を形成すると考えられる。
ＮＤ分散体の変性処理を行うことにより、ＮＤより基油への親和性の高いＮＤ付加体となり、その結果、基油への溶解性が向上すると考えられる。
反応性成分がＮＤに付加したＮＤ付加体では、ＮＤの表面に上記の反応性成分の分子（基）が存在する。したがって、ＮＤ付加体は、その表面に存在する反応性成分より得られる基により、基油との親和性に優れる。よって、ＮＤ組成物がＮＤ付加体を含むことにより、基油の耐摩耗性及び低摩擦性を向上することができる。
When these reactive components are added to ND, the chemical bonds of the molecules constituting the reactive components are cleaved (hereinafter referred to as "bond cleavage") by performing the modification treatment described below, similar to the base oil described above. As a result, highly chemically reactive radicals are generated, and this radical is thought to undergo an addition reaction with ND to form an ND adduct.
It is thought that by modifying the ND dispersion, it becomes an ND adduct that has a higher affinity for base oil than ND, and as a result, its solubility in base oil improves.
In an ND adduct in which a reactive component is added to an ND, molecules (groups) of the above-mentioned reactive component are present on the surface of the ND. Therefore, the ND adduct has excellent affinity with the base oil due to the groups obtained from the reactive components present on its surface. Therefore, by including the ND adduct in the ND composition, the wear resistance and low friction properties of the base oil can be improved.
本実施形態のＮＤ組成物は、後述するＮＤ組成物の製造方法により製造されるＮＤ組成物である。 The ND composition of this embodiment is an ND composition manufactured by a method for manufacturing an ND composition described below.
本実施形態のＮＤ組成物は、潤滑油、潤滑グリース、作動油、加工油等の各種用途に使用することができる。 The ND composition of the present embodiment can be used in various applications such as lubricating oil, lubricating grease, hydraulic oil, and processing oil.
［ＮＤ組成物の製造方法］
本実施形態のＮＤ組成物の製造方法は、基油とＮＤとを混合し、ＮＤの溶解成分を基油中に溶解し、基油とＮＤの混合物を得る分散工程（以下、「第一工程」ともいう。）と、ＮＤ分散体への熱処理及び放射線照射の少なくとも一方を行う変性工程（以下、「第二工程」ともいう。）と、を含む。
さらに、本実施形態のＮＤ組成物の製造方法は、第一工程以降に、混合物に含まれる粗粒成分を除去する工程（以下、「第三工程」ともいう。）を含んでもよい。第一工程にて、ＮＤと基油の混合物であるＮＤ分散体を得る。第一工程後のＮＤ分散体は、第二工程を経て、ＮＤ付加体を形成し、このＮＤ付加体を含んだＮＤ組成物を得る。
さらに、本実施形態のＮＤ組成物の製造方法は、第二工程の後に、ＮＤ組成物に残存した反応性物質を除去する工程（以下、「第四工程」ともいう。）を含んでもよい。
[Method for manufacturing ND composition]
The method for producing an ND composition of the present embodiment includes a dispersion step (hereinafter referred to as "first step") in which base oil and ND are mixed, dissolved components of ND are dissolved in the base oil, and a mixture of base oil and ND is obtained. ), and a modification step (hereinafter also referred to as "second step") in which the ND dispersion is subjected to at least one of heat treatment and radiation irradiation.
Furthermore, the method for producing an ND composition of the present embodiment may include, after the first step, a step of removing coarse particles contained in the mixture (hereinafter also referred to as "third step"). In the first step, an ND dispersion, which is a mixture of ND and base oil, is obtained. The ND dispersion after the first step passes through the second step to form an ND adduct, and an ND composition containing this ND adduct is obtained.
Furthermore, the method for producing an ND composition of the present embodiment may include, after the second step, a step of removing the reactive substance remaining in the ND composition (hereinafter also referred to as "fourth step").
以下、本実施形態のＮＤ組成物の製造方法を詳細に説明する。
（第一工程）
原料のＮＤと基油を混合させる。必要に応じて、反応性成分の混合も行う。反応性成分は、ＮＤと混合してから基油に混合しても良く、ＮＤと基油を混合したものに加えても良く、ＮＤと基油と同時に加えても良い。これらのうち、反応性成分はＮＤと混合してから基油に添加するのが好ましい。
原料のＮＤの仕込み量は、例えば、最終的に調製したいＮＤ組成物のＮＤ濃度を考慮して、計算上、基油に対して所望のＮＤの濃度が得られるＮＤ量の１．０倍～１００倍、より好ましくは１．０倍～２０倍とする。１．０倍以上であれば、所望のＮＤの濃度を満たすことができる。また１００倍以下であれば、粗粒成分を除去する第三工程において、例えばろ過の途中で濾過速度の低下が生じにくく、実施時間を比較的短くできる。さらに、過剰量のＮＤを添加することが避けられるため、ＮＤの原料コスト上昇を抑制できる。
Hereinafter, the method for manufacturing the ND composition of this embodiment will be described in detail.
(First step)
The raw material ND and base oil are mixed. If necessary, reactive components are also mixed. The reactive component may be mixed with the ND and then mixed with the base oil, added to a mixture of the ND and the base oil, or added at the same time as the ND and the base oil. Among these, it is preferable that the reactive component is mixed with the ND and then added to the base oil.
The amount of ND to be charged as a raw material is, for example, 1.0 times to 1.0 times the amount of ND that will give the desired ND concentration to the base oil, calculated considering the ND concentration of the ND composition that you want to finally prepare. 100 times, more preferably 1.0 times to 20 times. If it is 1.0 times or more, the desired ND concentration can be achieved. Moreover, if it is 100 times or less, in the third step of removing coarse particle components, the filtration rate is less likely to decrease, for example, during filtration, and the implementation time can be relatively shortened. Furthermore, since it is possible to avoid adding an excessive amount of ND, an increase in the cost of raw materials for ND can be suppressed.
前記ＮＤ分散体は、ＮＤの濃度が１質量ｐｐｍ（０．０００１質量％）以上１００００質量ｐｐｍ（１．０質量％）であることが好ましく、１質量ｐｐｍ（０．０００５質量％）以上１０００質量ｐｐｍ（０．１質量％）であることがより好ましく、１質量ｐｐｍ（０．００１質量％）以上１００質量ｐｐｍ（０．００１質量％）であることがさらに好ましい。ＮＤの濃度が上記範囲であれば、ＮＤの添加による、効果を長期間維持することができる。また、ＮＤ組成物の使用時におけるＮＤの劣化等による、ＮＤの濃度の低下を補うことができる。 The ND dispersion preferably has an ND concentration of 1 mass ppm (0.0001 mass %) or more and 10000 mass ppm (1.0 mass %), and 1 mass ppm (0.0005 mass %) or more and 1000 mass ppm or more. ppm (0.1% by mass), more preferably 1 ppm (0.001% by mass) or more and 100 ppm (0.001% by mass). If the concentration of ND is within the above range, the effect of adding ND can be maintained for a long period of time. Further, it is possible to compensate for a decrease in the concentration of ND due to deterioration of ND during use of the ND composition.
原料のＮＤと、必要に応じて反応性成分を基油に投入したら、必要に応じて攪拌機等の分散手段を用いて、室温付近で１時間～４８時間の分散処理を施す。このときの分散処理は、ＮＤを基油中にできるだけ分散させるのが目的である。 After the raw material ND and, if necessary, reactive components are added to the base oil, a dispersion treatment is performed at around room temperature for 1 to 48 hours using a dispersion means such as a stirrer, if necessary. The purpose of the dispersion treatment at this time is to disperse the ND in the base oil as much as possible.
原料ＮＤは、その表面層が、配位的に不飽和な原子の割合が大きいので、隣接粒子の表面原子間で作用し得るファンデルワールス力の総和が大きくて凝集しやすい。通常、数百ナノナノメートルから数ミクロンの大きさに凝集している。第一工程で得られたＮＤ分散体を、第二工程で効率よく変性処理するために、ＮＤの凝集体を解砕することが好ましい。この解砕処理は、第一工程の前から第二工程を実施するまでの間のいずれの段階で行っても良く、複数の工程で複数回行っても良い。第一工程の前や第二工程の前に解砕処理を行うと、第二工程での変性処理効果が得やすいという利点がある。また第一工程及び／または第二工程実施時に同時に行うと、上述した効果とともに、工程数を減らせる利点がある。
ＮＤを解砕するための解砕手段としては、例えば、超音波分散装置、ホモジナイザー、ボールミル、ビーズミル、三本ロール、ニーダー等が挙げられる。特に、凝集体を解砕する能力を備えるミクロビーズ法が好ましい。ビーズミルを用いることで、原料ＮＤは、１００ナノメートル以下の凝集体にまで解砕することができる。
Since the raw material ND has a large proportion of coordinately unsaturated atoms in its surface layer, the sum of van der Waals forces that can act between the surface atoms of adjacent particles is large and tends to aggregate. Usually, they are aggregated to a size of several hundred nanometers to several micrometers. In order to efficiently modify the ND dispersion obtained in the first step in the second step, it is preferable to disintegrate the ND aggregates. This crushing treatment may be performed at any stage from before the first step until the second step is performed, or may be performed multiple times in a plurality of steps. If the crushing treatment is performed before the first step or the second step, there is an advantage that the effect of the modification treatment in the second step can be easily obtained. Moreover, if the first step and/or the second step are performed simultaneously, there is an advantage that the number of steps can be reduced in addition to the above-mentioned effects.
Examples of the crushing means for crushing the NDs include an ultrasonic dispersion device, a homogenizer, a ball mill, a bead mill, a triple roll, a kneader, and the like. In particular, the microbead method, which has the ability to break up aggregates, is preferred. By using a bead mill, the raw ND can be crushed into aggregates of 100 nanometers or less.
（第二工程）
第一工程で得たＮＤ分散体を第二工程の変性工程で変性処理し、ＮＤ組成物を得る。
第二工程では、ＮＤ分散体を変性処理することにより、基油及び／または反応性成分を開裂させ、ＮＤに化学結合させて、ＮＤ付加体を形成する。そのため、変性処理後に得られるＮＤ組成物におけるＮＤの濃度は、変性処理前のＮＤ分散体におけるＮＤの濃度よりも低くなる。言い換えれば、変性処理後により、ＮＤ付加体が形成されるので、ＮＤは消費され、その濃度は、変性処理前よりも低くなる。
(Second process)
The ND dispersion obtained in the first step is modified in the second modification step to obtain an ND composition.
In the second step, the ND dispersion is subjected to a modification treatment to cleave the base oil and/or the reactive component and chemically bond it to the ND to form an ND adduct. Therefore, the concentration of ND in the ND composition obtained after the modification treatment is lower than the concentration of ND in the ND dispersion before the modification treatment. In other words, as more ND adducts are formed after the denaturation treatment, NDs are consumed and their concentration becomes lower than before the denaturation treatment.
第二工程では、変性処理としては、ＮＤ分散体を加熱する、放射線照射する、あるいは加熱と放射線照射を同時に行う方法が挙げられる。加熱は、ＮＤ分散体を収納した容器を加熱することで行うことができる。放射線照射は、放射線を発する光源を、ＮＤ分散体を収納した容器の内部に配置、あるいは容器の外部に配置し、それぞれ放射線をＮＤ分散体に照射させることで行うことができる。後者の場合は、容器は放射線が透過する材質である必要がある。また、放射線照射の際に、容器を加熱することで、熱と放射性照射を同時に行うことができる。 In the second step, examples of the modification treatment include heating the ND dispersion, irradiating it with radiation, or simultaneously performing heating and irradiation with radiation. Heating can be performed by heating a container containing the ND dispersion. Radiation irradiation can be performed by placing a light source that emits radiation inside or outside the container containing the ND dispersion, and respectively irradiating the ND dispersion with radiation. In the latter case, the container must be made of a material that is transparent to radiation. Moreover, by heating the container during radiation irradiation, heat and radioactive irradiation can be performed simultaneously.
変性処理を加熱で行う場合、ＮＤ分散体の加熱温度は、基油や反応性成分が蒸発してＮＤ分散体の重量が減少しすぎない温度が好ましい。ただし、この温度を超えても、蒸発成分を冷却管等で回収し、基油に戻す操作を行う場合、あるいは、圧力容器内で圧力をかけて蒸発を抑えた状態で熱処理する場合には、ＮＤ分散体の加熱温度をＮＤ分散体や反応性成分が蒸発する温度よりも高くすることができる。ＮＤ分散体の加熱温度が高い程、ＮＤ分散体に含まれる基油や反応性成分の結合開裂が速く進行するために、加熱時間を短くすることができる。
またＮＤ分散体の変性は、加熱温度を６０℃以上にすると、より効果的に結合開裂が進行するため好ましい。工業的にＮＤ組成物を製造する場合には、ＮＤ分散体の加熱温度は、１００℃以上であることがより好ましく、１２０℃以上であることがさらに好ましい。具体的には混合物の加熱温度は、６０℃以上２００℃以下であることが好ましく、８０℃以上１８０℃以下であることがより好ましく、１００℃以上１５０℃以下であることがさらに好ましい。この温度範囲であれば、加熱温度が高温で、ＮＤ分散体の成分が蒸発したり、ＮＤ分散体の結合開裂する基油以外の基油成分が熱分解することで、基油が劣化・変質することを抑制し、更に変性処理も短時間で行うことができる。
また、ＮＤ分散体が室温で固体の場合は、加熱により溶融状態とすることが好ましく、加熱温度は溶融温度より高くすることが好ましい。
When the modification treatment is performed by heating, the heating temperature of the ND dispersion is preferably a temperature at which the base oil and reactive components do not evaporate and the weight of the ND dispersion does not decrease too much. However, even if this temperature is exceeded, if the evaporated components are recovered using a cooling pipe etc. and returned to the base oil, or if heat treatment is performed in a pressure vessel to suppress evaporation, The heating temperature of the ND dispersion can be made higher than the temperature at which the ND dispersion and the reactive components evaporate. The higher the heating temperature of the ND dispersion, the faster the bond cleavage of the base oil and reactive components contained in the ND dispersion proceeds, so the heating time can be shortened.
Further, when modifying the ND dispersion, it is preferable to set the heating temperature to 60° C. or higher because bond cleavage proceeds more effectively. When producing an ND composition industrially, the heating temperature of the ND dispersion is more preferably 100°C or higher, and even more preferably 120°C or higher. Specifically, the heating temperature of the mixture is preferably 60°C or more and 200°C or less, more preferably 80°C or more and 180°C or less, and even more preferably 100°C or more and 150°C or less. In this temperature range, the heating temperature is high enough to cause evaporation of the components of the ND dispersion or thermal decomposition of base oil components other than the base oil that cleaves bonds in the ND dispersion, resulting in deterioration and deterioration of the base oil. Furthermore, the modification treatment can be carried out in a short time.
Further, when the ND dispersion is solid at room temperature, it is preferable to bring it into a molten state by heating, and the heating temperature is preferably higher than the melting temperature.
変性処理は、ＮＤ分散体に放射線を照射することによっても行うことができる。放射線照射で用いる放射線は、その波長に相当するエネルギー（光子エネルギー）が、基油を基油や反応性成分の結合開裂に要するエネルギーよりも大きいことが好ましい。つまり、宇宙線（光波長１ｐｍ未満）、ガンマ線（光波長１ｐｍ以上１００pｍ未満）、レントゲン線（光波長１００ｐｍ以上１０ｎｍ未満）、紫外線（光波長１０ｎｍ以上４００ｎｍ未満）が好ましい。
放射線照射の光子エネルギーは、結合開裂のエネルギーを極度に超え、結合開裂が過剰に進行し、ＮＤ付加体以外の成分も生成する可能性が低いことが好ましい。このため放射線照射は一定の範囲の光波長（光子エネルギー）を含んでいるのが良い。具体的には、紫外線（光波長１００ｎｍ以上４５０ｎｍ未満）が好ましく、より好ましくは、４５０ナノメートル以下１９０ナノメートル以上、さらにより好ましく、４１０ナノメートル以下２４０ナノメートル以上である。
紫外線照射に用いる光源としては、通常の低圧水銀ランプ、ＵＶオゾンランプ、紫外ＬＥＤ、エキシマランプ、キセノンランプなど用いることができる。
放射線照射の波長は、結合開裂を適度に引き起こし、かつ結合開裂の過剰な進行を抑制するために、適正な範囲で行うことが好ましい。
The modification treatment can also be performed by irradiating the ND dispersion with radiation. It is preferable that the energy (photon energy) corresponding to the wavelength of the radiation used for radiation irradiation is larger than the energy required for bond cleavage between the base oil and the reactive component. That is, cosmic rays (light wavelength less than 1 pm), gamma rays (light wavelength 1 pm or more and less than 100 pm), Roentgen rays (light wavelength 100 pm or more and less than 10 nm), and ultraviolet rays (light wavelength 10 nm or more and less than 400 nm) are preferable.
It is preferable that the photon energy of radiation irradiation extremely exceeds the energy of bond cleavage, so that bond cleavage proceeds excessively and there is a low possibility that components other than the ND adduct will be produced. For this reason, radiation irradiation preferably includes a certain range of light wavelengths (photon energy). Specifically, ultraviolet light (light wavelength of 100 nm or more and less than 450 nm) is preferred, more preferably 450 nm or less and 190 nm or more, and even more preferably 410 nm or less and 240 nm or more.
As a light source used for ultraviolet irradiation, an ordinary low-pressure mercury lamp, UV ozone lamp, ultraviolet LED, excimer lamp, xenon lamp, etc. can be used.
The wavelength of radiation irradiation is preferably carried out within an appropriate range in order to appropriately cause bond cleavage and to suppress excessive progress of bond cleavage.
放射線照射の線源照射量は、照射エネルギーとしても規定できる。つまり、あらかじめ光度計を用いて、放射線照射の照射光のエネルギー密度（ｍＷ／ｃｍ２）を測定しておき、次に照射時間（秒）を規定することにより、照射する放射線照射の光照射エネルギー（Ｊ／ｃｍ２）を決定する。
具体的なエネルギー量は、ＮＤ分散体１ｍＬあたりに照射するエネルギー量は、１～１００Ｊが好ましく、１～５０Ｊがより好ましく、更に２～２０Ｊがより好ましい。
The source dose of radiation irradiation can also be defined as irradiation energy. In other words, by measuring the energy density (mW/cm2) of the irradiation light for radiation irradiation in advance using a photometer and then specifying the irradiation time (seconds), the light irradiation energy (mW/cm2) of the radiation irradiation to be irradiated ( J/cm2).
The specific amount of energy irradiated per mL of the ND dispersion is preferably 1 to 100 J, more preferably 1 to 50 J, and even more preferably 2 to 20 J.
上記、加熱と放射照射とは同時に行うこともできる。それぞれ加熱と放射線照射とを独立で行う場合と比較して、処理時間の短縮や、照射エネルギーの低減、あるいは加熱温度を低下させることができる。 The above heating and radiation irradiation can also be performed simultaneously. Compared to the case where heating and radiation irradiation are performed independently, it is possible to shorten processing time, reduce irradiation energy, or lower heating temperature.
第一工程で得られたＮＤ分散体は、通常第一工程で大気に曝されるため、内部の酸素分子濃度が大気中の酸素と平衡状態になっている。そのため、第二工程は、変性処理を行う際に、ＮＤ分散体中の酸素分子濃度を、大気中に放置した状態よりも低下させる操作を含むことが好ましい。酸素分子濃度を低下させることにより、ＮＤ付加体が効率よく生成することができる。
混合物中の酸素分子濃度は、１０質量ｐｐｍ以下が好ましく、５質量ｐｐｍ以下がより好ましく、１質量ｐｐｍ以下がさらに好ましい。その後、酸素分子濃度を低下させたＮＤ分散体を、再び大気に触れさせることなく、熱処理すると良い。
The ND dispersion obtained in the first step is usually exposed to the atmosphere in the first step, so that the concentration of oxygen molecules inside is in equilibrium with the oxygen in the atmosphere. Therefore, it is preferable that the second step includes an operation in which the concentration of oxygen molecules in the ND dispersion is lowered than when it is left in the atmosphere when performing the modification treatment. By lowering the oxygen molecule concentration, the ND adduct can be efficiently produced.
The oxygen molecule concentration in the mixture is preferably 10 mass ppm or less, more preferably 5 mass ppm or less, and even more preferably 1 mass ppm or less. Thereafter, it is preferable to heat-treat the ND dispersion whose oxygen molecule concentration has been reduced without exposing it to the atmosphere again.
酸素分子濃度を低下させた状態で変性処理を行う好ましい方法としては、例えば、下記の３つ方法が挙げられる。
第一の方法を説明する。
気密可能なステンレス等の金属製容器、あるいはガラス等の光透過性のある容器の内部に、第一工程で得られたＮＤ分散体を収容する。
次いで、窒素ガスやアルゴンガス等の不活性ガスで容器内を置換するか、あるいは、さらに容器内のＮＤ分散体を不活性ガスでバブリングすることにより、ＮＤ分散体を不活性ガスと平衡状態にする。
次いで、容器を密閉する。その後、容器を加熱、容器内部に放射線照射、あるいは加熱と放射線照射とを同時に行うことにより、ＮＤ分散体を変性処理することができる。
第一の方法では、ＮＤ分散体と不活性ガスの平衡状態を保ったまま容器を加熱、放射線照射、あるいは加熱と放射線照射を同時に行うことにより、ＮＤ分散体の変性処理を、低酸素雰囲気下で行うことができる。
Preferred methods for carrying out the modification treatment in a state where the concentration of oxygen molecules is reduced include, for example, the following three methods.
The first method will be explained.
The ND dispersion obtained in the first step is placed inside an airtight metal container such as stainless steel or a light-transmissive container such as glass.
Next, by purging the inside of the container with an inert gas such as nitrogen gas or argon gas, or by bubbling the ND dispersion in the container with an inert gas, the ND dispersion is brought into equilibrium with the inert gas. do.
The container is then sealed. Thereafter, the ND dispersion can be modified by heating the container, irradiating the inside of the container with radiation, or simultaneously heating and irradiating radiation.
In the first method, the ND dispersion is modified in a low oxygen atmosphere by heating the container, irradiating the container, or simultaneously heating and irradiating the ND dispersion while maintaining an equilibrium state between the ND dispersion and the inert gas. It can be done with
第二の方法を説明する。
気密可能なステンレス等の金属製容器、あるいはガラス等の光透過性のある容器の内部に、第一工程で得たＮＤ分散体を収容した後、容器を密閉する。
次いで、容器を減圧して、ＮＤ分散体中の酸素分子濃度を低下させる。
次いで、ＮＤ分散体中の酸素分子濃度を低下させた状態を保ったまま容器を加熱、容器内部に放射線照射、あるいは加熱と放射線照射とを同時に行うことにより、ＮＤ分散体を変性処理することができる。
第二の方法では、ＮＤ分散体中の酸素分子濃度を低下させた状態を保ったまま、減圧下で容器を加熱、容器内部に放射線照射、あるいは加熱と放射線照射とを同時に行うことにより、ＮＤ分散体の変性処理を、低酸素雰囲気下で行う。
The second method will be explained.
After the ND dispersion obtained in the first step is placed inside an airtight metal container such as stainless steel or a light-transmissive container such as glass, the container is sealed.
Next, the pressure in the container is reduced to reduce the concentration of oxygen molecules in the ND dispersion.
Next, the ND dispersion can be modified by heating the container while keeping the concentration of oxygen molecules in the ND dispersion in a reduced state, irradiating the inside of the container with radiation, or performing heating and irradiation simultaneously. can.
In the second method, the ND dispersion is heated by heating the container under reduced pressure, irradiating the inside of the container with radiation, or simultaneously heating and irradiating the ND dispersion while keeping the concentration of oxygen molecules in the ND dispersion in a reduced state. The modification treatment of the dispersion is carried out under a low oxygen atmosphere.
第三の方法を説明する。
気密可能なステンレス等の金属製容器、あるいはガラス等の光透過性のある容器の内部に、第一工程で得たＮＤ分散体を収容した後、容器を密閉する。
次いで、容器を減圧して、ＮＤ分散体中の酸素分子濃度を低下させる。
次いで、窒素ガス等の不活性ガスで容器内を置換するか、あるいは、さらに容器内のＮＤ分散体を不活性ガスでバブリングすることにより、ＮＤ分散体を不活性ガスと平衡状態にする。
次いで、ＮＤ分散体と不活性ガスの平衡状態を保ったまま容器を加熱、容器内部に放射線照射、あるいは加熱と放射線照射とを同時に行うことにより、ＮＤ分散体を変性処理することができる。
第三の方法では、ＮＤ分散体と不活性ガスの平衡状態を保ったまま容器を加熱、容器内部に放射線照射、あるいは加熱と放射線照射とを同時に行うことにより、ＮＤ分散体の変性処理を低酸素雰囲気下で行う。
The third method will be explained.
After the ND dispersion obtained in the first step is placed inside an airtight metal container such as stainless steel or a light-transmissive container such as glass, the container is sealed.
Next, the pressure in the container is reduced to reduce the concentration of oxygen molecules in the ND dispersion.
Next, the interior of the container is replaced with an inert gas such as nitrogen gas, or the ND dispersion in the container is further bubbled with an inert gas to bring the ND dispersion into an equilibrium state with the inert gas.
Next, the ND dispersion can be modified by heating the container while maintaining an equilibrium state between the ND dispersion and the inert gas, irradiating the inside of the container with radiation, or heating and irradiating the container simultaneously.
In the third method, the denaturation treatment of the ND dispersion is reduced by heating the container while maintaining an equilibrium state between the ND dispersion and the inert gas, irradiating the inside of the container with radiation, or performing heating and irradiation simultaneously. Perform under oxygen atmosphere.
ＮＤ分散体中の酸素分子濃度を低くすると、変性処理を行った場合、結合開裂で生成するラジカルが酸素と反応して過酸化物となることを抑制でき、ＮＤ分散体の変性処理を効率よく進行させることができる。また、この結果、発生する過酸化物が少なければ、ＮＤ分散体が、着色したり、基油の粘度が上昇あるいは低下したり、揮発成分が増えて揮発性が増すなどして、最終的に得られるＮＤ組成物の特性を低下させることも抑制できるため好ましい。 By lowering the concentration of oxygen molecules in the ND dispersion, it is possible to suppress the radicals generated by bond cleavage from reacting with oxygen to form peroxides during modification treatment, making the modification treatment of the ND dispersion more efficient. It can be advanced. As a result, if less peroxide is generated, the ND dispersion may become colored, the viscosity of the base oil may increase or decrease, the volatile components may increase, and volatility may increase, resulting in This is preferable because deterioration of the properties of the obtained ND composition can also be suppressed.
なお、ＮＤ分散体が１０分以上大気に触れると、ＮＤ分散体中の酸素分子濃度が、大気との平衡状態の濃度に近くなる。このようなＮＤ分散体から酸素を低減させた状態で、第二工程の変性処理をすると、ＮＤ分散体の構成成分の酸化に起因する劣化が生じにくく、ＮＤ組成物の耐熱性が低下する可能性も低くなる。すなわち、ＮＤ分散体中の酸素分子濃度が低い程、基油の熱劣化が抑制され、ＮＤ組成物の耐熱性が低下しない。ＮＤ分散体中の酸素の濃度は、大気中の酸素分子濃度よりも低いことが好ましく、大気中の酸素分子濃度の１０分の１以下であることがより好ましい。具体的には、ＮＤ分散体中の酸素分子濃度を、１０質量ｐｐｍ以下とすることが好ましく、５質量ｐｐｍ以下とすることがより好ましく、１質量ｐｐｍ以下とすることがさらに好ましい。
ＮＤ分散体中の酸素分子濃度は、溶存酸素計を用いて測定することができる。なお、酸素分子濃度が低い場合には、工業的には、酸素分子濃度を正確に測定することが難しいため、製造条件を調整することにより、ＮＤ分散体中の酸素分子濃度を所定の範囲とする。
変性処理は分散処理を併用することが好ましい。例えば、撹拌機、超音波分散装置、ホモジナイザー、ボールミル、ビーズミル等が挙げられる。
（第三工程）
第一工程や第二工程で得られたＮＤ分散体やＮＤ組成物には、粗粒成分として、原料のＮＤ由来の不純物、ＮＤの凝集物、未溶解のＮＤ、基油の不純物、製造過程で混入した粒子（コンタミネーション等）等が含まれる場合がある。そのため、これらの粗粒成分が含まれたＮＤ組成物をそのまま用いると、一定以上の大きさのものは、ＮＤ組成物と接触している摺動部等が摩耗する等の不具合が生じることがある。そこで、第一工程や第二工程の後に、粗粒成分を除去する第三工程を設けることができる。具体的には、第一工程で得たＮＤ分散体あるいは第二工程で得たＮＤ組成物をろ過する第三工程を行ってもよい。一定以上の大きさは用途によって異なるが、通常０．１μｍ以上の大きさの粒子は除去することが好ましい。その場合、例えば０．１μｍの濾紙を使用することで除去することができる。
第三工程としては、例えば、（１）メンブランフィルターを用いた除去工程、（２）遠心分離器を用いた除去工程、（３）メンブランフィルターと遠心分離器を組み合わせて用いる除去工程等が挙げられる。これらの除去工程の中でも、濾過時間の点から、少量のＮＤ組成物を得る場合は（１）メンブランフィルターを用いた除去工程が好ましく、大量のＮＤ組成物を得る場合は（２）遠心分離器を用いた除去工程が好ましい。
Note that when the ND dispersion is exposed to the atmosphere for 10 minutes or more, the concentration of oxygen molecules in the ND dispersion approaches the concentration in equilibrium with the atmosphere. If such a ND dispersion is subjected to the second modification treatment in a state in which oxygen is reduced, deterioration due to oxidation of the constituent components of the ND dispersion is unlikely to occur, and the heat resistance of the ND composition may decrease. Sexuality also decreases. That is, the lower the concentration of oxygen molecules in the ND dispersion, the more the thermal deterioration of the base oil is suppressed, and the heat resistance of the ND composition does not deteriorate. The concentration of oxygen in the ND dispersion is preferably lower than the concentration of oxygen molecules in the atmosphere, and more preferably one-tenth or less of the concentration of oxygen molecules in the atmosphere. Specifically, the concentration of oxygen molecules in the ND dispersion is preferably 10 mass ppm or less, more preferably 5 mass ppm or less, and even more preferably 1 mass ppm or less.
The concentration of oxygen molecules in the ND dispersion can be measured using a dissolved oxygen meter. Note that when the oxygen molecule concentration is low, it is difficult to accurately measure the oxygen molecule concentration industrially, so by adjusting the manufacturing conditions, the oxygen molecule concentration in the ND dispersion can be kept within a predetermined range. do.
It is preferable to use dispersion treatment together with the modification treatment. Examples include a stirrer, an ultrasonic dispersion device, a homogenizer, a ball mill, a bead mill, and the like.
(Third step)
The ND dispersion and ND composition obtained in the first and second steps contain impurities derived from the raw ND, ND aggregates, undissolved ND, base oil impurities, and impurities from the manufacturing process. It may contain particles mixed in (contamination, etc.). Therefore, if an ND composition containing these coarse particles is used as is, if the size exceeds a certain level, problems such as abrasion of the sliding parts etc. that are in contact with the ND composition may occur. be. Therefore, a third step for removing coarse grain components can be provided after the first step and the second step. Specifically, a third step may be performed in which the ND dispersion obtained in the first step or the ND composition obtained in the second step is filtered. Although the size of particles larger than a certain value varies depending on the use, it is usually preferable to remove particles with a size of 0.1 μm or larger. In that case, it can be removed by using, for example, a 0.1 μm filter paper.
Examples of the third step include (1) a removal step using a membrane filter, (2) a removal step using a centrifuge, and (3) a removal step using a combination of a membrane filter and a centrifuge. . Among these removal steps, from the viewpoint of filtration time, (1) removal step using a membrane filter is preferable when obtaining a small amount of ND composition, and (2) removal step using a centrifugal separator is preferable when obtaining a large amount of ND composition. A removal step using is preferred.
（第四工程）
第四工程は、ＮＤ組成物に含まれる反応性成分を除去する工程である。第三工程の後に、第一工程で混合した反応性成分を除去するのが主な目的になる。反応性成分を除去する方法としては、例えば、加熱または減圧下で加熱して反応性成分を蒸発させる方法等が挙げられる。
第四工程は、第三工程に連続して行うことができる。例えば、第三工程の第一～第三方法では、変性処理を終えた後に、真空ポンプ等を用いて、容器の圧力を減圧することで、ＮＤ組成物に含まれる反応性成分を除去することができる。
このとき、ＮＤ組成物中の揮発性成分も除去することができる。
(Fourth step)
The fourth step is a step of removing reactive components contained in the ND composition. After the third step, the main purpose is to remove the reactive components mixed in the first step. Examples of the method for removing the reactive components include a method of evaporating the reactive components by heating or heating under reduced pressure.
The fourth step can be performed consecutively to the third step. For example, in the first to third methods of the third step, after finishing the denaturation treatment, the pressure in the container is reduced using a vacuum pump or the like to remove reactive components contained in the ND composition. I can do it.
At this time, volatile components in the ND composition can also be removed.
［ＮＤ組成物］
ＮＤ組成物を潤滑油として使用する場合、例えば、鉱油系潤滑油、ＰＡＯ系潤滑油、ＰＶＥ系潤滑油、ＰＯＥ系潤滑油、シリコン系潤滑油、フッ素系潤滑油の用途で使用することができる。ＮＤ組成物をそのままあるいは、一般的に用いられる添加剤を加えて使用できる。また、本実施形態の方法で作製したＮＤ組成物を、ＮＤ組成物で用いた基油と同じ、あるいは他の種類の基油、あるいは潤滑油組成物に配合することができる。後者は、前者に比べて少量のＮＤ組成物を、通常用いている基油や潤滑油に添加して用いることができるため、簡易な製造方法となり好ましい。これらの得られた潤滑油は、耐摩耗性及び低摩擦性を向上することができる。
[ND composition]
When the ND composition is used as a lubricating oil, it can be used, for example, as a mineral oil-based lubricating oil, a PAO-based lubricating oil, a PVE-based lubricating oil, a POE-based lubricating oil, a silicone-based lubricating oil, or a fluorine-based lubricating oil. . The ND composition can be used as it is or with commonly used additives added thereto. Further, the ND composition produced by the method of the present embodiment can be blended with the same base oil as the base oil used in the ND composition, or with a different type of base oil, or with a lubricating oil composition. The latter method is preferable because it allows a smaller amount of the ND composition to be added to commonly used base oils or lubricating oils than the former method, resulting in a simpler manufacturing method. These obtained lubricating oils can have improved wear resistance and low friction properties.
本実施形態の潤滑油組成物の製造方法によれば、耐摩耗性及び低摩擦性に優れる潤滑油組成物が得られる。 According to the method for producing a lubricating oil composition of the present embodiment, a lubricating oil composition having excellent wear resistance and low friction properties can be obtained.
以上、本発明の好ましい実施の形態について詳述したが、本発明は特定の実施の形態に限定されるものではなく、特許請求の範囲内に記載された本発明の要旨の範囲内において、種々の変形・変更が可能である。 Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the specific embodiments, and various modifications may be made within the scope of the gist of the present invention described within the scope of the claims. It is possible to transform and change.
［実施例１］
（ＮＤ組成物の調製）
＜第一工程＞
基油として、鉱油（出光興産製、ダイアナフレシアＮ２８）１００ｇ、反応性成分としてヘキサノール（東京化成製）４０ｇ、ＮＤとして、ＮＤ３０（トーメイダイヤ株式会社製、体積平均粒子径３０ｎｍのナノダイヤモンド）０．０５ｇとを樹脂製の２５０ｍｌサンプル容器に入れ、さらに、これに解砕ボールとして、３０ミクロンのジルコニアビーズを１００ｇ加えて、サンプル容器を毎分６０回転で２４時間ボールミル解砕を行った。次にジルコニアビーズを取り除いて、ＮＤ分散体を得た。
[Example 1]
(Preparation of ND composition)
<First step>
As the base oil, 100 g of mineral oil (manufactured by Idemitsu Kosan, Diana Fresia N28), as a reactive component, 40 g of hexanol (manufactured by Tokyo Kasei), as the ND, 0. 05 g was placed in a 250 ml resin sample container, and 100 g of 30 micron zirconia beads were added thereto as a crushing ball, and the sample container was crushed in a ball mill at 60 revolutions per minute for 24 hours. Next, the zirconia beads were removed to obtain an ND dispersion.
＜第二工程＞
前記ＮＤ分散体１４ｇを蓋の部分に２つのガス注入口を取り付けた容量２５ｍｌの石英ガラス製の容器内に移し、容器の内部を、ガス注入口の一方から窒素ガスを流し、もう一方から容器内のガスを排気するようにして、３０分間放置した後に、窒素ガス注入を中止して、密栓した。この状態で、容器を１４０℃のオイルバスにつけて８時間放置して加熱した。
ここで、ＮＤ分散体に溶存する酸素分子濃度を次の手順で測定した。まず、あらかじめ、ｎ－ドデカン（和光純薬工業株式会社製）１００ｍＬを２５０ｍＬビーカーに取り出し、ここに１０分間空気でバブリングした。
次に、溶存酸素計（製品名：Ｂ－５０６、飯島電子工業株式会社製）を用いてこの溶液の酸素分子濃度を基準（飽和度１００％）に設定した。
次に、上記第二工程で窒素ガスを流通させる前と後のＮＤ分散体の酸素分子濃度を各々測定した。その結果、窒素ガスを流す前は、酸素分子濃度は１１０％、流した後は７％であった。
次に、ｎ－ドデカンの空気中での飽和酸素分子濃度を７３質量ｐｐｍとし、この数値と先のＮＤ分散体の測定結果の１１０％及び７％とから、ＮＤ分散体の溶存酸素分子濃度を８０質量ｐｐｍと５ｐｐｍとそれぞれ算出した。
<Second process>
Transfer 14 g of the ND dispersion into a 25 ml quartz glass container with two gas inlets attached to the lid, flow nitrogen gas through one of the gas inlets, and fill the container with nitrogen gas from the other. After allowing the gas inside to be evacuated and leaving it for 30 minutes, the injection of nitrogen gas was stopped and the container was tightly stoppered. In this state, the container was placed in a 140° C. oil bath and left to heat for 8 hours.
Here, the concentration of oxygen molecules dissolved in the ND dispersion was measured according to the following procedure. First, 100 mL of n-dodecane (manufactured by Wako Pure Chemical Industries, Ltd.) was taken into a 250 mL beaker and bubbled with air for 10 minutes.
Next, using a dissolved oxygen meter (product name: B-506, manufactured by Iijima Electronics Co., Ltd.), the oxygen molecule concentration of this solution was set as a standard (saturation level: 100%).
Next, the oxygen molecule concentration of the ND dispersion was measured before and after flowing nitrogen gas in the second step. As a result, the oxygen molecule concentration was 110% before flowing nitrogen gas, and 7% after flowing nitrogen gas.
Next, the saturated oxygen molecule concentration of n-dodecane in the air is set to 73 mass ppm, and from this value and the previous measurement results of ND dispersion of 110% and 7%, the dissolved oxygen molecule concentration of the ND dispersion is calculated. They were calculated to be 80 mass ppm and 5 ppm, respectively.
＜第四工程＞
オイルバスで８時間放置した後、容器を室温まで冷却し、その後第四工程として、容器のガス注入口の一方に真空ポンプを接続して、容器内部を減圧状態にした。この状態で１時間放置し、容器内部のヘキサノールを除去した。容器内部から高粘性の液体を取り出し、ＮＤ組成物を得ることができた。得られたＮＤ組成物の質量は、１０ｇであり、未反応のヘキサノールが除去された、基油およびＮＤやＮＤ付加体が残存した状態であった。
得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなく、透明であった。すなわちＮＤが溶解したと言える。
<Fourth step>
After being left in an oil bath for 8 hours, the container was cooled to room temperature, and then, in the fourth step, a vacuum pump was connected to one of the gas injection ports of the container to reduce the pressure inside the container. The container was left in this state for 1 hour, and the hexanol inside the container was removed. A highly viscous liquid was taken out from inside the container and an ND composition could be obtained. The mass of the obtained ND composition was 10 g, and unreacted hexanol was removed, but the base oil, ND, and ND adduct remained.
In the obtained ND composition, no Tyndall phenomenon was observed, and there was no turbidity when visually observed, and the composition was transparent. In other words, it can be said that the ND was dissolved.
（耐摩耗性及び摩擦性の測定）
第四工程で得られたＮＤ組成物について、摩擦摩耗試験機（Ａｎｔｏｎ Ｐａａｒ社製、製品名「ボールオンディスクトライボメーター」）を用いて、耐摩耗性を評価した。
摩擦摩耗試験機を構成する基板及びボールの材質を、高炭素クロム軸受鋼鋼材であるＳＵＪ２とした。なお、ボールは直径が６ｍｍ、基板は１５ｃｍ角を用いた。
まず、基板の一主面に得られたＮＤ組成物約１ｇを塗布した。
次に、ＮＤ組成物を介して、基板の一主面上にて、ボールが同心円状の軌道（直径約１０ｃｍの円状）を描くように、ボールを摺動させた。基板の一主面上におけるボールの速度を１０ｍｍ／秒、ボールによる基板の一主面に対する荷重を３０Ｎとした。基板の一主面上におけるボールの摺動距離が積算１００ｍに到達した時点で、ボールを装置より取り出し、ボールの基板との接触面を、光学顕微鏡で観察し、表面のすり減りを、すり減り面の円の最大直径をＤ（μｍ）とした。ここで最大直径Ｄを摩耗係数と定義した。つまり、最大直径Ｄの数字が小さいほど、摩耗が抑制されており、組成物の特性として好ましい状態である。通常、円形にすり減るが、楕円を帯びる場合がある。その場合は、最大径になる部分を最大直径Ｄとした。なお、この測定は２５±２℃の環境下で行った。
得られたＮＤ組成物の摩耗係数を表１に示した。
(Measurement of wear resistance and friction properties)
The wear resistance of the ND composition obtained in the fourth step was evaluated using a friction and wear tester (manufactured by Anton Paar, product name: "Ball-on-Disc Tribometer").
The material of the substrate and balls constituting the friction and wear tester was SUJ2, which is a high carbon chromium bearing steel material. Note that the ball used had a diameter of 6 mm, and the substrate used had a square size of 15 cm.
First, about 1 g of the obtained ND composition was applied to one main surface of the substrate.
Next, the ball was slid on one main surface of the substrate through the ND composition so that the ball traced a concentric trajectory (a circle with a diameter of about 10 cm). The speed of the ball on one main surface of the substrate was 10 mm/sec, and the load exerted by the ball on one main surface of the substrate was 30 N. When the sliding distance of the ball on one principal surface of the substrate reaches a total of 100 m, the ball is removed from the device and the contact surface of the ball with the substrate is observed with an optical microscope. The maximum diameter of the circle was defined as D (μm). Here, the maximum diameter D was defined as the wear coefficient. In other words, the smaller the maximum diameter D, the more suppressed the wear, which is a preferable state as a characteristic of the composition. It usually wears in a circular shape, but may take on an oval shape. In that case, the portion having the maximum diameter was defined as the maximum diameter D. Note that this measurement was performed in an environment of 25±2°C.
Table 1 shows the wear coefficient of the obtained ND composition.
［実施例２］
実施例１で、ＮＤ分散体を熱処理する工程で、窒素ガスの代わりに、体積濃度２％酸素ガスを含む窒素ガスを用いたこと以外は、実施例１の操作でＮＤ組成物を得た。ガス置換後のＮＤ分散体の酸素分子濃度は１０％（実施例１と同様に換算した溶存酸素分子濃度は、９質量ｐｐｍ）であった。また、得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなく、透明な液体であった。
得られたＮＤ組成物の耐摩耗性を表１に示す。
[Example 2]
An ND composition was obtained by the operation of Example 1, except that in the step of heat-treating the ND dispersion, nitrogen gas containing 2% oxygen gas by volume was used instead of nitrogen gas. The oxygen molecule concentration of the ND dispersion after gas replacement was 10% (the dissolved oxygen molecule concentration calculated in the same manner as in Example 1 was 9 mass ppm). Further, the obtained ND composition had no Tyndall phenomenon observed, was not visually turbid, and was a transparent liquid.
Table 1 shows the wear resistance of the obtained ND composition.
［実施例３］
実施例１で、ＮＤ分散体を熱処理する工程で、窒素ガスの代わりに空気を用いたこと以外は、実施例１と同様の手順でＮＤ組成物を得た。空気流通後のＮＤ分散体の酸素分子濃度は８０％であった。また、得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなく、透明な液体であった。得られたＮＤ組成物の耐摩耗性を表１に示す。
[Example 3]
An ND composition was obtained in the same manner as in Example 1, except that air was used instead of nitrogen gas in the step of heat-treating the ND dispersion. The oxygen molecule concentration of the ND dispersion after air circulation was 80%. Further, the obtained ND composition had no Tyndall phenomenon observed, was not visually turbid, and was a transparent liquid. Table 1 shows the wear resistance of the obtained ND composition.
［比較例１］
比較として、ＮＤ分散体にＮＤを添加しなかったこと、加熱工程を省いたこと以外は実施例１と同様の手順でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
ＮＤ組成物の耐摩耗性を表１に示す。
[Comparative example 1]
For comparison, an ND composition was obtained in the same manner as in Example 1 except that ND was not added to the ND dispersion and the heating step was omitted. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
Table 1 shows the wear resistance of the ND composition.
［比較例２］
比較として、ＮＤ分散体にＮＤを添加しなかったこと以外は実施例１の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
ＮＤ組成物の耐摩耗性を表１に示す。
[Comparative example 2]
For comparison, an ND composition was obtained by the procedure of Example 1 except that no ND was added to the ND dispersion. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
Table 1 shows the wear resistance of the ND composition.
［比較例３］
比較として、ＮＤ分散体の加熱を省いたこと以外は実施例１の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象が観察され、また目視で僅かに濁りがあった。
ＮＤ組成物の耐摩耗性を表１に示す。
[Comparative example 3]
For comparison, an ND composition was obtained by the procedure of Example 1 except that heating of the ND dispersion was omitted. Tyndall phenomenon was observed in the obtained ND composition, and it was visually observed to be slightly cloudy.
Table 1 shows the wear resistance of the ND composition.
実施例１～３と、比較例１及び比較例３とを比較すると、耐摩耗性では前者が後者を上回った。つまり、ＮＤ分散体に加熱を行ったことにより、得られたＮＤ組成物の耐摩耗性が改善された。
実施例３、実施例２、実施例１を比較すると、この順序で耐摩耗性が向上している。つまり、熱処理を行う際の、ＮＤ分散体の酸素分子濃度を低下させるほど、得られたＮＤ組成物の耐摩耗性が改善された。
比較例３と実施例１とを比較すると、比較例３では、ＮＤが基油である鉱油と親和性が悪く、分散性が低いために、得られたＮＤ組成物でチンダル現象が観察され、また濁りが見られた。ＮＤが凝集していることが原因と考えられる。また耐摩耗性もＮＤ無添加の比較例１に対してほとんど向上が見られなかった。これに対して、実施例１では、ＮＤは加熱により、ＮＤと鉱油との親和性が向上し、このために、得られたＮＤ組成物では、ＮＤが鉱油に分散し、濁りが確認されなかった。また耐摩耗性も向上し、ＮＤを添加した効果が確認された。
比較例２と実施例１を比較すると、ＮＤを添加しなかった比較例２に対し、ＮＤを添加した実施例１は、耐摩耗性が向上し、本発明の方法でＮＤを添加した効果を確認することができた。
When Examples 1 to 3 were compared with Comparative Examples 1 and 3, the former exceeded the latter in terms of wear resistance. That is, by heating the ND dispersion, the wear resistance of the obtained ND composition was improved.
Comparing Example 3, Example 2, and Example 1, the wear resistance improves in this order. In other words, the lower the oxygen molecule concentration of the ND dispersion during heat treatment, the more the wear resistance of the obtained ND composition was improved.
Comparing Comparative Example 3 and Example 1, in Comparative Example 3, the Tyndall phenomenon was observed in the obtained ND composition because the ND had poor affinity with mineral oil as the base oil and had low dispersibility. Cloudiness was also seen. This is thought to be caused by aggregation of ND. In addition, almost no improvement in wear resistance was observed compared to Comparative Example 1 in which no ND was added. On the other hand, in Example 1, the affinity between the NDs and mineral oil was improved by heating the NDs, and therefore, in the obtained ND composition, the NDs were dispersed in the mineral oil, and no turbidity was observed. Ta. The wear resistance was also improved, confirming the effect of adding ND.
Comparing Comparative Example 2 and Example 1, compared to Comparative Example 2 in which ND was not added, Example 1 in which ND was added had improved wear resistance, and the effect of adding ND using the method of the present invention was improved. I was able to confirm.
［実施例４］
実施例１で、第二工程で加熱を行う代わりに、石英ガラス容器外部より放射線照射として紫外線照射を２回行ったことを除いては、実施例１の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
紫外線照射は、紫外照射装置（サンエイテック製、オムニキュアＳ２０００）を用い、フィルターを２５０－４５０ｎｍとし、照射範囲２ｃｍ２、出力を１Ｗ／ｃｍ２に設定し、照射タイマーを５０秒に設定し、１回の照射で１００Ｊのエネルギーを照射することができる。つまり、２回の照射により、ＮＤ分散体に２００Jの紫外線を照射した。
ＮＤ組成物の耐摩耗性を表１に示す。
[Example 4]
An ND composition was obtained in the same manner as in Example 1, except that instead of heating in the second step, ultraviolet irradiation was performed twice from outside the quartz glass container as radiation irradiation. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
For ultraviolet irradiation, an ultraviolet irradiation device (manufactured by Sanei Tech, Omnicure S2000) was used, the filter was set to 250-450 nm, the irradiation range was set to 2 cm 2 , the output was set to 1 W/cm 2 , and the irradiation timer was set to 50 seconds. It is possible to irradiate energy of 100 J in one irradiation. That is, the ND dispersion was irradiated with 200 J of ultraviolet rays through two irradiations.
Table 1 shows the wear resistance of the ND composition.
［実施例５］
実施例４で、紫外線照射を４回行ったことを除いては、実施例４と同様の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
ＮＤ組成物の耐摩耗性を表１に示す。
[Example 5]
In Example 4, an ND composition was obtained in the same manner as in Example 4, except that the ultraviolet irradiation was performed four times. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
Table 1 shows the wear resistance of the ND composition.
［実施例６］
実施例４で、紫外線照射を８回行ったことを除いては、実施例４の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
ＮＤ組成物の耐摩耗性を表１に示す。
[Example 6]
An ND composition was obtained by the procedure of Example 4 , except that the ultraviolet irradiation was performed eight times. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
Table 1 shows the wear resistance of the ND composition.
実施例４～６と、比較例３とを比較すると、耐摩耗性では前者が後者を上回った。つまり、ＮＤ分散体に放射線を照射したことにより、得られたＮＤ組成物の耐摩耗性が改善された。実施例４～６では、ＮＤが放射線照射により、ＮＤと鉱油との親和性が向上し、その結果得られたＮＤ組成物では、ＮＤが鉱油に分散し、濁りが確認されなかったため、耐摩耗性が向上したと考えられる。 Comparing Examples 4 to 6 and Comparative Example 3, the former exceeded the latter in terms of wear resistance. That is, by irradiating the ND dispersion with radiation, the wear resistance of the obtained ND composition was improved. In Examples 4 to 6, the affinity between the ND and mineral oil was improved by irradiation of the ND, and the resulting ND composition had good wear resistance because the ND was dispersed in the mineral oil and no turbidity was observed. It is thought that the performance has improved.
［実施例７］
実施例１で、加熱しながら、実施例５と同様にして紫外線照射を４回行ったことを除いては、実施例１の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
ＮＤ組成物の耐摩耗性を表１に示す。
実施例７と、実施例１と７とを比較すると、耐摩耗性では前者が後者を上回った。つまり、ＮＤ分散体に加熱と放射線照射とを同時に行うことにより、加熱と放射線照射のいずれか一方を行った場合よりも、得られたＮＤ組成物の耐摩耗性がやや改善された。
[Example 7]
In Example 1, an ND composition was obtained by the same procedure as in Example 1, except that while heating, ultraviolet irradiation was performed four times in the same manner as in Example 5. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
Table 1 shows the wear resistance of the ND composition.
When Example 7 was compared with Examples 1 and 7, the former exceeded the latter in terms of wear resistance. That is, by simultaneously heating and irradiating the ND dispersion, the wear resistance of the resulting ND composition was slightly improved compared to when either heating or irradiation was performed.
［実施例８～１２］
実施例１で、容器をステンレス製の耐圧容器としたこと、加熱温度を表1に記載の６０℃～２００℃としたこと、を除いては、実施例１の操作でＮＤ組成物を得た。得られたＮＤ組成物は、各実施例においてチンダル現象は観察されず、また目視で濁りはなかった。
ＮＤ組成物の耐摩耗性を表１に示す。
[Examples 8 to 12]
An ND composition was obtained by the operation of Example 1, except that the container was a stainless steel pressure-resistant container and the heating temperature was 60 ° C. to 200 ° C. as shown in Table 1. . In the obtained ND compositions, no Tyndall phenomenon was observed in each of the Examples, and no turbidity was observed visually.
Table 1 shows the wear resistance of the ND composition.
実施例８～１２と比較例３とを比較すると、６０℃から２００℃の範囲の加熱により、耐摩耗性が改善された。
実施例８～１２、および実施例１から、加熱温度１００℃と１４０℃のＮＤ組成物で最も耐摩耗性が改善された。次いで、加熱温度８０℃と１８０℃のＮＤ組成物で耐摩耗性が改善された。次いで、加熱温度６０℃と２００℃のＮＤ組成物で耐摩耗性が改善された。
Comparing Examples 8 to 12 and Comparative Example 3, the wear resistance was improved by heating in the range of 60°C to 200°C.
From Examples 8 to 12 and Example 1, the wear resistance was improved the most with the ND compositions heated at temperatures of 100°C and 140°C. Next, wear resistance was improved in the ND compositions heated at temperatures of 80°C and 180°C. Next, the wear resistance was improved in the ND compositions heated at 60°C and 200°C.
［実施例１３］
実施例１で、得られたＮＤ組成物１０ｇを、ＰＡＯ（ポリ－α－オレフィン、製品名：ＳｐｅｃｔｒａＳｙｎ（登録商標）、ＥＸＸＯＮＭＯＢＩＬ社製））４０ｇに撹拌子を用いて攪拌しながら添加して、希釈ＮＤ組成物を得た。得られた希釈ＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
希釈ＮＤ組成物の耐摩耗性を表１に示す。
[Example 13]
10 g of the ND composition obtained in Example 1 was added to 40 g of PAO (poly-α-olefin, product name: SpectraSyn (registered trademark), manufactured by EXXONMOBIL) while stirring using a stir bar, A diluted ND composition was obtained. In the obtained diluted ND composition, no Tyndall phenomenon was observed, and no turbidity was observed with the naked eye.
Table 1 shows the wear resistance of the diluted ND composition.
［比較例４］
比較として、実施例１のＮＤ分散体の加熱を省いた比較例３で得られたＮＤ組成物を使用したこと以外は実施例１３と同様の操作で希釈ＮＤ組成物を得た。得られた希釈ＮＤ組成物は、チンダル現象が観察され、また目視で僅かに濁りがあった。
希釈ＮＤ組成物の耐摩耗性を表１に示す。
実施例１３と、比較例４とを比較すると、基油を鉱油としたＮＤ組成物をＰＡＯに添加して希釈ＮＤ組成物を得た場合においても、加熱を行うことによって得られた希釈ＮＤ組成物の耐摩耗性が改善されることが確認された。
[Comparative example 4]
For comparison, a diluted ND composition was obtained in the same manner as in Example 13, except that the ND composition obtained in Comparative Example 3, in which heating of the ND dispersion of Example 1 was omitted, was used. Tyndall phenomenon was observed in the obtained diluted ND composition, and it was visually observed to be slightly cloudy.
Table 1 shows the wear resistance of the diluted ND composition.
Comparing Example 13 and Comparative Example 4, even when a diluted ND composition was obtained by adding the ND composition using mineral oil as the base oil to PAO, the diluted ND composition obtained by heating It was confirmed that the wear resistance of objects was improved.
［実施例１４］
実施例１で、基油としてＰＯＥ（ポリオールエステル型）であるポリオールエステル（ＰＯＥ－Ａ、ユニスター（登録商標）Ｈ－３３４Ｒ、日油株式会社製）を１００ｇとし、反応性成分としてジエチレングリコール（東京化成製）を４０ｇとしたことを除いては、実施例１の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
第四工程を経て、得られたＮＤ組成物の質量は、１０ｇであり、溶剤が除去された、基油およびＮＤが残存した状態であった。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
[Example 14]
In Example 1, 100 g of POE (polyol ester type) polyol ester (POE-A, Unistar (registered trademark) H-334R, manufactured by NOF Corporation) was used as the base oil, and diethylene glycol (Tokyo) was used as the reactive component. An ND composition was obtained in the same manner as in Example 1, except that 40 g of the ND composition (manufactured by Kasei Co., Ltd.) was used. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
The mass of the ND composition obtained through the fourth step was 10 g, with the solvent removed and the base oil and ND remaining.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
［実施例１５］
実施例１４で、加熱の代わりに、実施例５で行った紫外線照射を４回行ったことを除いては、実施例１４と同様の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象は観察されず、また目視で濁りはなかった。
第四工程を経て、得られたＮＤ組成物の質量は、１０ｇであり、溶剤が除去された、基油およびＮＤが残存した状態であった。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
[Example 15]
In Example 14, an ND composition was obtained in the same manner as in Example 14, except that instead of heating, the ultraviolet irradiation performed in Example 5 was performed four times. The Tyndall phenomenon was not observed in the obtained ND composition, and no turbidity was observed visually.
The mass of the ND composition obtained through the fourth step was 10 g, with the solvent removed and the base oil and ND remaining.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
［比較例５］
比較として、ＮＤ分散体の加熱を省いたこと以外は実施例１４の操作でＮＤ組成物を得た。得られたＮＤ組成物は、チンダル現象が観察され、また目視で僅かに濁りがあった。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
実施例１４と１５と、比較例５とを比較すると、ポリオールエステル型を基油とするＮＤ分散体においても、加熱あるいは放射線を照射したことにより、得られたＮＤ組成物の耐摩耗性が改善された。
[Comparative example 5]
For comparison, an ND composition was obtained by the procedure of Example 14 except that heating of the ND dispersion was omitted. Tyndall phenomenon was observed in the obtained ND composition, and it was visually observed to be slightly cloudy.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
Comparing Examples 14 and 15 and Comparative Example 5, it was found that even in the ND dispersion using a polyol ester base oil, the wear resistance of the obtained ND composition was improved by heating or irradiating with radiation. It was done.
［実施例１６］
実施例１で、ＮＤ分散体の作製で反応性成分を用いなかったことと、ボールミル解砕を行わなかったこと、および窒素による酸素除去を行わず大気雰囲気でＮＤ分散体の加熱を行ったこと、を除いては、実施例１の操作と同様にしたＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
[Example 16]
In Example 1, no reactive component was used in the preparation of the ND dispersion, no ball mill disintegration was performed, and the ND dispersion was heated in an atmospheric atmosphere without removing oxygen with nitrogen. An ND composition was obtained in the same manner as in Example 1 except for the following.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
［実施例１７］
実施例４で、ＮＤ分散体の作製で反応性成分を用いなかったこと、解砕ボールを用いたボールミル解砕を行わなかったこと、窒素による酸素除去を行わず大気雰囲気でＮＤ分散体の加熱を行ったこと、を除いては、実施例４と同様の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
[Example 17]
In Example 4, no reactive component was used in the preparation of the ND dispersion, no ball mill disintegration using a disintegration ball was performed, and the ND dispersion was heated in an atmospheric atmosphere without removing oxygen with nitrogen. An ND composition was obtained in the same manner as in Example 4, except that.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
［比較例６］
比較として、ＮＤ分散体の加熱を省いたこと以外は実施例１６の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
実施例１６及び実施例１７と比較例６とを比較すると、加熱や放射線照射をしたことにより、得られたＮＤ組成物の耐摩耗性が改善されることが確認された。
[Comparative example 6]
For comparison, an ND composition was obtained by the procedure of Example 16 except that heating of the ND dispersion was omitted.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
Comparing Examples 16 and 17 with Comparative Example 6, it was confirmed that heating and radiation irradiation improved the wear resistance of the obtained ND compositions.
［実施例１８］
実施例１で、ＮＤ分散体の作製で解砕ボールを用いたボールミル解砕を行わなかったこと、窒素ガスによる酸素除去を行わず大気雰囲気でＮＤ分散体の加熱を行ったこと、を除いては、実施例１の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す
[Example 18]
In Example 1, except that ball mill disintegration using a disintegration ball was not performed in the production of the ND dispersion, and the ND dispersion was heated in an atmospheric atmosphere without removing oxygen with nitrogen gas. An ND composition was obtained by the operation of Example 1.
Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition are shown in Table 1.
［比較例７］
比較として、ＮＤ分散体の加熱を省いたこと以外は実施例１８の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
[Comparative Example 7]
For comparison, an ND composition was obtained by the procedure of Example 18 except that heating of the ND dispersion was omitted.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
実施例１８と比較例７とを比較すると、加熱をしたことにより、得られたＮＤ組成物の耐摩耗性が改善された。 A comparison between Example 18 and Comparative Example 7 shows that the wear resistance of the obtained ND composition was improved by heating.
［実施例１９］
実施例１で、ＮＤ分散体の作製で反応性成分を用いなかったこと、窒素ガスによる酸素除去を行わず大気雰囲気でＮＤ分散体の加熱を行ったこと、を除いては、実施例１の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す
[Example 19]
Example 1 was performed in the same manner as in Example 1, except that no reactive component was used in the preparation of the ND dispersion, and the ND dispersion was heated in an atmospheric atmosphere without removing oxygen with nitrogen gas. An ND composition was obtained by the operation.
Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition are shown in Table 1.
［比較例８］
比較として、ＮＤ分散体の加熱を省いたこと以外は実施例１９の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す。
[Comparative example 8]
For comparison, an ND composition was obtained by the procedure of Example 19 except that heating of the ND dispersion was omitted.
Table 1 shows the Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition.
実施例１９と比較例８とを比較すると、加熱をしたことにより、得られたＮＤ組成物の耐摩耗性が改善された。 Comparing Example 19 and Comparative Example 8, heating improved the abrasion resistance of the resulting ND composition.
［実施例２０］
実施例１７で、第一工程において、解砕処理を行わず鉱油を攪拌子で約２００ｒｐｍで攪拌しながらＮＤを添加し、その後実施例１と同様のボールミルによる解砕処理を行ったことを除いては、実施例１７の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す
実施例１７と実施例２０の結果から、解砕処理を第一工程の後行っても耐摩耗性が向上することが確認された。
[Example 20]
In Example 17, in the first step, ND was added while stirring the mineral oil at about 200 rpm with a stirrer without performing the crushing process, and then the same crushing process as in Example 1 was performed using a ball mill. Then, an ND composition was obtained by the operation of Example 17.
The Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition are shown in Table 1. From the results of Examples 17 and 20, it was confirmed that the abrasion resistance was improved even if the crushing treatment was performed after the first step. Ta.
［実施例２１］
実施例１で、第二工程と第四工程との間に、第三工程として、０．１ミクロンのメンブランフィルターでろ過し、ＮＤ組成物を得たことを除いては、実施例１の操作でＮＤ組成物を得た。
ＮＤ組成物のチンダル現象と濁り及び耐摩耗性を表１に示す
実施例２１と実施例１の結果から、第三工程を設けることで、耐摩耗性が向上することが確認された。
[Example 21]
The procedure of Example 1 was repeated, except that the ND composition was obtained by filtering with a 0.1 micron membrane filter as a third step between the second and fourth steps. An ND composition was obtained.
The Tyndall phenomenon, turbidity, and abrasion resistance of the ND composition are shown in Table 1. From the results of Example 21 and Example 1, it was confirmed that the abrasion resistance was improved by providing the third step.
Claims (9)
前記ナノダイヤモンド分散体への加熱及び放射線照射の少なくとも一方を行う変性工程と、
を含み、
前記変性工程において、前記ナノダイヤモンド分散体の加熱を、８０℃以上２００℃以下で行うナノダイヤモンド組成物の製造方法。 a dispersion step of mixing base oil and nanodiamonds to obtain a nanodiamond dispersion containing the base oil and the nanodiamonds;
a modification step of performing at least one of heating and irradiating the nanodiamond dispersion;
including;
A method for producing a nanodiamond composition, in which, in the modification step, the nanodiamond dispersion is heated at a temperature of 80°C or higher and 200°C or lower.
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| JP2008179738A (en) | 2007-01-26 | 2008-08-07 | Nissan Motor Co Ltd | Lubricant composition |
| US20100029518A1 (en) | 2008-07-02 | 2010-02-04 | Nanotech Lubricants, LLC | Lubricant with nanodiamonds and method of making the same |
| CN102086421A (en) | 2009-12-04 | 2011-06-08 | 中泰恒森(北京)科技有限公司 | Polycrystalline nanodiamond lubricating oil additive |
| US20110172132A1 (en) | 2010-01-12 | 2011-07-14 | Branson Blake T | Materials comprising deaggregated diamond nanoparticles |
| JP2017128482A (en) | 2016-01-21 | 2017-07-27 | 株式会社ダイセル | Surface-modified nanodiamond and nanodiamond dispersion |
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| JP2008179738A (en) | 2007-01-26 | 2008-08-07 | Nissan Motor Co Ltd | Lubricant composition |
| US20100029518A1 (en) | 2008-07-02 | 2010-02-04 | Nanotech Lubricants, LLC | Lubricant with nanodiamonds and method of making the same |
| CN102086421A (en) | 2009-12-04 | 2011-06-08 | 中泰恒森(北京)科技有限公司 | Polycrystalline nanodiamond lubricating oil additive |
| US20110172132A1 (en) | 2010-01-12 | 2011-07-14 | Branson Blake T | Materials comprising deaggregated diamond nanoparticles |
| JP2017128482A (en) | 2016-01-21 | 2017-07-27 | 株式会社ダイセル | Surface-modified nanodiamond and nanodiamond dispersion |
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