JP2005097375A - Nano-diamond nonaqueous dispersion and its preparing method - Google Patents

Nano-diamond nonaqueous dispersion and its preparing method Download PDF

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JP2005097375A
JP2005097375A JP2003330923A JP2003330923A JP2005097375A JP 2005097375 A JP2005097375 A JP 2005097375A JP 2003330923 A JP2003330923 A JP 2003330923A JP 2003330923 A JP2003330923 A JP 2003330923A JP 2005097375 A JP2005097375 A JP 2005097375A
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diamond
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Tsutomu Yamada
山田　　勉
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Okamoto Machine Tool Works Ltd
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<P>PROBLEM TO BE SOLVED: To provide a nano-diamond nonaqueous dispersion superior in storage properties, in which a primary particle of the nano-diamond is uniformly dispersed in a nonaqueous liquid dispersion medium. <P>SOLUTION: This preparing method comprises a step of putting a slurry liquid, which is obtained by previously mixing a cluster diamond aggregation 2 with a nonaqueous liquid medium 3 by using a homogenizer, into a premixing vessel 4, a step of conducting the slurry into a vessel 7 of a wet bead mill machine 6 by using a pump 5 and pulverizing the cluster diamond aggregation in a wet process by turning effort among a ceramic bead 8 and a rotor 9, a step of returning the slurry 10 obtained by pulverizing in the wet process into the above premixing vessel 4 via a tube 11, a step of circulating it again to the bead mill machine 6 by using the pump 5, and a step of opening a change valve 12 after termination of dispersion and conducting a prepared nano-diamond nonaqueous dispersion 14 into a product tank 13. This nano-diamond nonaqueous dispersion is useful for a modifier of lubricity, gloss and hardness of a coating. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、自動車や金属工作機械の精密加工剤（研磨剤）、エンジンオイルの添加剤、塗料、爪ペイント、印刷インクの添加剤、等として有用なナノダイヤモンド非水分散液およびその調製方法に関する。   The present invention relates to a nano-diamond non-aqueous dispersion useful as a precision processing agent (abrasive) for automobiles and metal machine tools, an additive for engine oil, a paint, a nail paint, an additive for printing ink, and the like, and a method for preparing the same. .

トリニトロトルエン（ＴＮＴ）、ヘキソ−ゲン等の酸素欠乏型爆薬を爆発させて得られた炭素質煤を回収し、異物を分離し、硝酸や硫酸、過マンガン酸カリウム等での化学的酸化処理し、精製を行うことにより粒子径が５０〜７５００ナノメ−トル（ｎｍ）の二次、三次凝集ダイヤモンド凝集体（いわゆるクラスタ−ダイヤモンド）が製造されることは公知である。このクラスタ−ダイヤモンドは、一次粒子径が３〜２０ｎｍ、好ましくは、３〜５ｎｍのナノダイヤモンド微粒子表面の黒鉛質皮膜が融着・二次あるいは三次凝集したものである（例えば、特許文献１、特許文献２、特許文献３、非特許文献１参照。）。   Collect carbonaceous soot obtained by exploding oxygen-deficient explosives such as trinitrotoluene (TNT) and hexogen, separate foreign matter, and perform chemical oxidation treatment with nitric acid, sulfuric acid, potassium permanganate, etc. It is known that secondary and tertiary agglomerated diamond aggregates (so-called cluster diamond) having a particle diameter of 50 to 7500 nanometers (nm) are produced by purification. The cluster-diamond is obtained by fusing, secondary or tertiary aggregation of a graphite film on the surface of nanodiamond fine particles having a primary particle diameter of 3 to 20 nm, preferably 3 to 5 nm (for example, Patent Document 1, Patent). (Ref. Literature 2, Patent Literature 3, and Non-Patent Literature 1).

このクラスタ−ダイヤモンドを０．１重量％配合した潤滑油Ｉ−４０は、滑り軸受の摩擦係数を１．５〜１．８のファクタ−まで低下させることができる（例えば、特許文献１参照。）。また、灯油、軽油、スピンドル油、石油オイル、エチレングリコ−ル、グリ−ス、エチレングリコ−ル等の溶媒に０．１〜２重量％含有させた精密加工剤は貯蔵安定性に優れることも知られている（例えば、特許文献４参照。）。   Lubricating oil I-40 containing 0.1% by weight of the cluster diamond can reduce the friction coefficient of the sliding bearing to a factor of 1.5 to 1.8 (see, for example, Patent Document 1). . Precision processing agents containing 0.1 to 2% by weight in solvents such as kerosene, light oil, spindle oil, petroleum oil, ethylene glycol, grease, and ethylene glycol may have excellent storage stability. It is known (for example, refer to Patent Document 4).

さらに、粒子径が４〜８ｎｍのナノダイヤモンド粒子を水に超音波分散させたナノダイヤモンド水分散液が耐磨耗性の優れた膜を与えることも知られている（例えば、特許文献５参照。）。
特許第２７９９３３７号公報 中国特許第１４０００４１号明細書 中国特許第１３８２５２０号明細書 特開平５−１５６２３９号公報 独国特許出願公開第１０１２５２８９号明細書 砥粒加工学会誌 Vol.47 No.8 2003年 418-421頁 Furthermore, it is also known that a nanodiamond aqueous dispersion obtained by ultrasonically dispersing nanodiamond particles having a particle diameter of 4 to 8 nm in water gives a film having excellent wear resistance (see, for example, Patent Document 5). ).
Japanese Patent No. 2799337 Chinese Patent No. 1400041 Chinese Patent No. 1382520 Specification JP-A-5-156239 German Patent Application Publication No. 10125289 Journal of the Japan Society for Abrasive Technology Vol.47 No.8 2003 418-421

前記特許文献５に記載される超音波を用いて水に分散させたナノダイヤモンド水分散液は、貯蔵安定性が悪く、調製したら比較的速やかに用いる必要がある。また、水が分散媒であるため、水分を嫌う用途、例えば油性塗料、印刷インク、油性ワニス、潤滑油には使用できない。   The nanodiamond aqueous dispersion dispersed in water using ultrasonic waves described in Patent Document 5 has poor storage stability and needs to be used relatively quickly after preparation. Moreover, since water is a dispersion medium, it cannot be used for applications that dislike moisture, such as oil paints, printing inks, oil varnishes, and lubricating oils.

また、前記特許文献１および特許文献４に記載されるクラスタ−ダイヤモンド非水分散液は、分散しているクラスタ−ダイヤモンド凝集体の粒子径が５０〜７５００ｎｍと巨大であるとともに、不揃い（粒度分布が広い）である。本発明者は、この非水分散媒に分散している粒子が一次粒子であれば、平均粒径も３〜２０ｎｍ、好ましくは、３〜５ｎｍと粒度分布も狭くなり、このナノダイヤモンド非水分散液を油性塗料に用いたときは金属や木材等の基材への皮膜の密着性が向上するとともに、また、膜厚分布も不揃いとなるため、得られる皮膜の光沢、硬度も向上し、摩擦係数も低くなることに着目し、貯蔵安定性に優れるナノダイヤモンド非水分散液の調製方法の提供を目的とするものである。   In addition, the cluster-diamond non-aqueous dispersions described in Patent Document 1 and Patent Document 4 have a large cluster-diamond aggregate particle size of 50 to 7500 nm and are irregular (particle size distribution is Wide). The present inventor, if the particles dispersed in the non-aqueous dispersion medium are primary particles, the average particle size is also 3 to 20 nm, preferably 3 to 5 nm, the particle size distribution becomes narrow, this nanodiamond non-aqueous dispersion When the liquid is used for oil-based paints, the adhesion of the film to a substrate such as metal or wood is improved, and the film thickness distribution is not uniform. The purpose is to provide a method for preparing a nanodiamond non-aqueous dispersion excellent in storage stability, paying attention to a low coefficient.

請求項１の発明は、沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下の非水系液状媒体に、平均粒子径が３〜２０ナノメ−トルのナノダイヤモンド粒子 ０．１〜１５重量％を均一に分散してなる、ナノダイヤモンド非水分散液を提供するものである。   The invention according to claim 1 is a non-aqueous liquid medium having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less, and nanodiamond particles having an average particle diameter of 3 to 20 nanometers. % Is uniformly dispersed, and a nanodiamond non-aqueous dispersion is provided.

請求項２の発明は、前記ナノダイヤモンド非水分散液において、非水系液状媒体が、灯油、軽油、テレビン油、モ−タ−オイル、潤滑油、炭素数１０〜２０のα−オレフィン、エチレングリコ−ル、エチルアルコ−ル、ポリビニルアルコ−ル、エナメル、油性ワニスより選ばれたものであることを特徴とする。   The invention according to claim 2 is the nanodiamond non-aqueous dispersion, wherein the non-aqueous liquid medium is kerosene, light oil, turpentine oil, motor oil, lubricating oil, α-olefin having 10 to 20 carbon atoms, ethylene glycol It is characterized by being selected from ru, ethyl alcohol, polyvinyl alcohol, enamel and oily varnish.

請求項３の発明は、酸素欠乏型爆薬を爆発させて製造したクラスタ−ダイヤモンド凝集体と、沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下の非水系液状媒体との混合物を、ビ−ズミル機に導き、直径３０〜５００μｍのセラミックビ−ズを用いてクラスタ−ダイヤモンド凝集体を湿式微粉砕して沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下の非水系液状媒体に、平均粒子径が３〜２０ナノメ−トルのナノダイヤモンド粒子 ０．１〜１５重量％を均一に分散してなる、ナノダイヤモンド非水分散液を調製する方法を提供するものである。   The invention of claim 3 comprises a mixture of a cluster-diamond aggregate produced by detonating an oxygen-deficient explosive and a non-aqueous liquid medium having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less, A non-aqueous liquid having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less by wet pulverization of cluster diamond agglomerates using a ceramic bead with a diameter of 30 to 500 μm. The present invention provides a method for preparing a nanodiamond non-aqueous dispersion in which 0.1 to 15% by weight of nanodiamond particles having an average particle diameter of 3 to 20 nanometers are uniformly dispersed in a medium.

分散されたナノダイヤモンド粒子が一次粒子で、凝集していないので基材への皮膜の密着性が向上するとともに、皮膜の光沢、硬度も向上し、摩擦係数も低くなる。また、分散媒が非水系分散媒であるので、水を嫌う用途、例えば、エンジンの潤滑油、印刷インク、油性塗料、爪エナメルにも使用できる。   Since the dispersed nanodiamond particles are primary particles and are not agglomerated, the adhesion of the film to the substrate is improved, the gloss and hardness of the film are improved, and the coefficient of friction is lowered. Further, since the dispersion medium is a non-aqueous dispersion medium, it can be used for applications that dislike water, such as engine lubricating oil, printing ink, oil-based paint, and nail enamel.

酸素欠乏型爆薬を爆発させて製造した５０〜７５００ナノメ−トルの凝集粒子径を有するクラスタ−ダイヤモンド凝集体を非水系液状分散体中でビ−ズミル粉砕して得られるナノダイヤモンド非水分散液中の分散粒子である一次粒子のナノダイヤモンド(粒子径３〜５０ｎｍ)は、比表面積が極端に大きく、かつ、水酸基、カルボキシル基、アミノ基、カルボニル基等の各種官能基を有するので、分散姓に優れ、貯蔵安定性がよい。   In a nanodiamond non-aqueous dispersion obtained by bead milling a cluster-diamond aggregate having an aggregated particle size of 50-7500 nanometers produced by detonating an oxygen-deficient explosive in a non-aqueous liquid dispersion The primary particle nanodiamond (particle diameter 3-50 nm), which is a dispersed particle, has an extremely large specific surface area and has various functional groups such as a hydroxyl group, a carboxyl group, an amino group, and a carbonyl group. Excellent and storage stability is good.

以下、図１を用いて本発明を詳述する。図１は、ナノダイヤモンド非水分散液液の調製機の正面図である。
ナノダイヤモンド非水分散液液を調製するには、図１に示す調製機１を用い、クラスタ−ダイヤモンド凝集体２と、沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下の非水系液状媒体３とを予めホモジナイザ−で混合して得たスラリ−液をプレ混合槽４内に仕込み、このスラリ−液を、ポンプ５で湿式ビ−ズミル機６のベッセル７内に導き、ジルコニアやアルミナ等の直径３０〜５００μｍのセラミックビ−ズ８とロ−タ９の回転力を用いてクラスタ−ダイヤモンド凝集体を湿式微粉砕し、この湿式微粉砕したスラリ−液１０を管１１を経由して前記プレ混合槽４に戻し、再び、前記ポンプ５でビ−ズミル機６に循環させ、分散作業が終了したら切換弁１２を開き、調製されたナノダイヤモンド非水分散液１４を製品タンク１３内へと導く。 Hereinafter, the present invention will be described in detail with reference to FIG. FIG. 1 is a front view of a nanodiamond non-aqueous dispersion liquid preparation machine.
In order to prepare a nanodiamond non-aqueous dispersion, a preparation machine 1 shown in FIG. 1 is used, and a cluster-diamond aggregate 2 and a non-aqueous system having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less. A slurry liquid obtained by previously mixing the liquid medium 3 with a homogenizer is charged into a premixing tank 4, and this slurry liquid is guided into a vessel 7 of a wet bead mill 6 by a pump 5, and zirconia or Cluster diamond agglomerates are wet pulverized using the rotational force of ceramic beads 8 and rotor 9 having a diameter of 30 to 500 μm, such as alumina, and this wet pulverized slurry liquid 10 is passed through tube 11. Then, it is returned to the pre-mixing tank 4 and is circulated again to the bead mill 6 by the pump 5. When the dispersing operation is completed, the switching valve 12 is opened, and the prepared nanodiamond non-aqueous dispersion 14 is produced. Leading to the link 13.

ロ−タ９の回転速度は、５〜２０ｍ／秒で、粉砕・分散時間は、２〜６時間が好ましい。
製品タンク１３内のナノダイヤモンド非水分散液１４は、沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下の非水系液状媒体に、平均粒子径が３〜２０ナノメ−トルのナノダイヤモンド粒子 ０．１〜１５重量％を均一に分散してなる非水分散液である。 The rotation speed of the rotor 9 is preferably 5 to 20 m / second, and the pulverization / dispersion time is preferably 2 to 6 hours.
The nanodiamond non-aqueous dispersion 14 in the product tank 13 is a nanodiamond having an average particle size of 3 to 20 nanometers in a nonaqueous liquid medium having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less. This is a non-aqueous dispersion obtained by uniformly dispersing 0.1 to 15% by weight of particles.

酸素欠如爆発方法によるクラスタ−ダイヤモンド２の製造方法は、前記特許文献１、特許文献２、特許文献３に記載されている。粒子径が５０〜７５００ｎｍのクラスタ−ダイヤモンドは中国の凌雲納米材料有限公司よりダイヤモンド ナノパウダ−（Diamond Nanopowder）の商品名で、ロシアのアルタイケミカル社（ＡＬＴＡＩ Ｃｈｅｍｉｃａｌ）よりUltra Fine Water Dispersed Diamond の商品名で入手できる。   The method for producing cluster diamond 2 by the oxygen deficient explosion method is described in Patent Document 1, Patent Document 2, and Patent Document 3. Clusters with a particle size of 50-7500 nm are named Diamond Nanopowder from China's Ling Yun Material Co., Ltd., and Ultra Fine Water Dispersed Diamond from ALTAI Chemical, Russia. Available.

沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下、好ましくは０．８〜４センチポイズの非水系液状媒体３としては、軽油、灯油、テレビン油、モ−タ−オイル、潤滑油、炭素数１０〜２０のα−オレフィン、エナメル、油性ワニス、エチルアルコ−ル、エチレングリコ−ル、アクリル化ポリビニルアルコ−ル等が挙げられる。炭素数１０〜２０のα−オレフィンは、例えば三菱化学株式会社よりダイヤレン（登録商標）の商品名で入手できる。例えば、テトラドデセンはダイヤレン−１４の商品名で購入できる。湿式ビ−ズミル機６は、例えば、アシザワ・ファインテック株式会社よりアジテ−タミル ＬＭＺやラブスタ−の商品名で市販されている。油性ワニスとしては、ウレタン系樹脂、アクリル系樹脂、油性アルキッド樹脂、弗素系樹脂、エポキシ系樹脂、不飽和脂肪油等を有機溶剤で溶解したものが挙げられる。非水系液状媒体は、引火点が６０℃以上であるものが取り扱い易い。   Non-aqueous liquid medium 3 having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less, preferably 0.8 to 4 centipoise includes light oil, kerosene, turpentine oil, motor oil, lubricating oil, carbon Examples include α-olefins of several 10 to 20, enamel, oily varnish, ethyl alcohol, ethylene glycol, acrylated polyvinyl alcohol, and the like. The α-olefin having 10 to 20 carbon atoms can be obtained, for example, from Mitsubishi Chemical Corporation under the trade name of Dialen (registered trademark). For example, tetradodecene can be purchased under the trade name Dialen-14. The wet bead mill 6 is commercially available, for example, from Ashizawa Finetech Co., Ltd. under the trade names of Agitator Mill LMZ and Labstar. Examples of the oil varnish include urethane resin, acrylic resin, oil alkyd resin, fluorine resin, epoxy resin, unsaturated fatty oil and the like dissolved in an organic solvent. A non-aqueous liquid medium having a flash point of 60 ° C. or higher is easy to handle.

ナノダイヤモンド非水分散液液を調製する際に、界面活性剤を混合物に配合してナノダイヤモンド粒子の分散をより向上させてもよい。界面活性剤としては、ラウリルアルコ−ルポリオキシエチレンエ−テル、トリデシルポリオキシエチレンエ−テル、モノステアリン酸ポリエチレングリコ−ル等のノニオン系界面活性剤が好ましい。界面活性剤は、クラスタ−ダイヤモンドに対し０．５〜２重量％の割合で用いられる。また、シリコンオイル等の消泡剤をクラスタ−ダイヤモンドに対し１〜１０重量％の割合で配合してもよい。   When preparing the nanodiamond non-aqueous dispersion, a surfactant may be added to the mixture to further improve the dispersion of the nanodiamond particles. As the surfactant, nonionic surfactants such as lauryl alcohol polyoxyethylene ether, tridecyl polyoxyethylene ether, and polyethylene glycol monostearate are preferable. The surfactant is used in a proportion of 0.5 to 2% by weight based on the cluster diamond. Moreover, you may mix | blend antifoamers, such as a silicone oil, in the ratio of 1 to 10 weight% with respect to a cluster diamond.

また、ナノダイヤモンド非水分散液を調製する際に最終目的物の組成（分散液中のナノダイヤモンドの濃度は０．１〜１５重量％）となるよう、極圧油や顔料、チキソトロピック剤等の添加剤をクラスタ−ダイヤモンドと非水媒体との混合物に配合してもよいし、非水分散液中のナノダイヤモンド濃度が５〜１５重量％のナノダイヤモンド非水分散液をマスタ−バッチとしてこれを市販のエンジンオイルや油性塗料、精密加工油に配合してもよい。   Moreover, extreme pressure oils, pigments, thixotropic agents, etc. so that the final target composition (concentration of nanodiamond in the dispersion is 0.1 to 15% by weight) when the nanodiamond non-aqueous dispersion is prepared May be added to a mixture of cluster-diamond and non-aqueous medium, or a nano-diamond non-aqueous dispersion having a nano-diamond concentration in the non-aqueous dispersion of 5 to 15% by weight as a master batch. May be blended into commercially available engine oils, oil-based paints, and precision processing oils.

実施例１
クラスタ−ダイヤモンドとして、中国の凌雲納米材料有限公司より入手した次ぎの粒度分布（日機装株式会社製マイクロトラック ＵＰＡ型機器で測定）のダイヤモンド ナノパウダ−（純度９５％以上、比重３．０５〜３．１２、比表面積（Caluculated Surface Area） ２８０〜３３０ｍ２／ｇ）を用いた。
粒度分布： Ｄ１０ １０９．９ｎｍ、Ｄ５０ ２３７．７ｎｍ、Ｄ９０ ７８９．５ｎｍ
最小粒子径 ８５．９ｎｍ、最大粒子径 ２３１２．５ｎｍ
なお、ここで、Ｄ１０、Ｄ５０およびＤ９０の意味は、重量基準でサイズ別累積曲線から全粒子重量の１０％のサイズがＤ１０、全粒子重量の５０％のサイズがＤ５０、全粒子重量の９０％のサイズがＤ９０である。 Example 1
Diamond nanopowder (purity 95% or more, specific gravity 3.05 to 3.12) with the following particle size distribution (measured with Nikkiso Co., Ltd., Microtrac UPA type equipment) obtained from Lingyun Ningyo Material Co., Ltd. in China as cluster diamond Specific surface area (280-330 m 2 / g) was used.
Particle size distribution: D 10 109.9 nm, D 50 237.7 nm, D 90 789.5 nm
Minimum particle size 85.9 nm, maximum particle size 2312.5 nm
Here, the meanings of D 10 , D 50, and D 90 are, based on the weight-based cumulative curve by size, 10% of the total particle weight is D 10 , 50% of the total particle weight is D 50 , 90% of the size of the particles by weight are D 90.

非水液状媒体として、三菱化学株式会社のα−オレフィン（Ｃ14）のダイヤレン−１４（商品名）（引火点１１０℃以上、沸点２５０〜２５３℃、２０℃でのブルックフィ−ルド粘度１．９４ｃｐｓ、比重０．７７２）を用いた。 As a non-aqueous liquid medium, an α-olefin (C 14 ) dialen-14 (trade name) of Mitsubishi Chemical Co., Ltd. (Brookfield viscosity at a flash point of 110 ° C. or higher, a boiling point of 250 to 253 ° C., and 20 ° C. 94 cps, specific gravity 0.772) was used.

特殊機化工業株式会社のホモジナイザ−ＲＯＢＯＭＩＸ（商品名）の容量６リットルの混合槽内に、上記ダイヤレン−１４を３リットル、クラスタ−ダイヤモンドを１４０ｇ、分散助剤としてラウリルアルコ−ルポリオキシエチレンエ−テル１０ｇを入れ、攪拌軸回転数８０００ｒｐｍの条件下で１０分混合し、混合スラリ−液を調製した。このスラリ−液中のクラスタ−ダイヤモンド濃度は約６重量％であった。   In a 6 liter mixing tank of homogenizer-ROBOMIX (trade name) manufactured by Tokushu Kika Kogyo Co., Ltd., 3 liters of dialen-14, 140 g of cluster diamond, and lauryl alcohol polyoxyethylene ester as a dispersion aid. -10 g of tellurium was added and mixed for 10 minutes under the condition of a stirring shaft speed of 8000 rpm to prepare a mixed slurry liquid. The cluster diamond concentration in the slurry was about 6% by weight.

上記混合スラリ−液を、図１に示すアシザワ・ファインテック株式会社の微粉砕・分散機 ＬＡＢＳＴＡＲ（商品名）の混合槽４に仕込み、このスラリ−液をポンプ５で湿式ボ−ルミル機６のベッセル７内に導き、粒子直径５０μｍのジルコニアセラミックビ−ズ８とロ−タ９の回転力を用いてクラスタ−ダイヤモンド凝集体を湿式微粉砕し、この湿式微粉砕したスラリ−液１０を前記プレ混合槽４内に管１１を経由して戻し、再び、前記ポンプ５でビ−ズミル機６に循環させ、この２時間３０分の分散作業が終了したら切換弁１２を開き、調製されたナノダイヤモンド非水分散液１４を製品タンク１３内へと導いた。   The above mixed slurry liquid is charged into a mixing tank 4 of a fine pulverizer / disperser LABSTAR (trade name) of Ashizawa Finetech Co., Ltd. shown in FIG. 1, and this slurry liquid is pumped by a wet ball mill 6. The cluster diamond agglomerate is wet-pulverized by using the rotational force of the zirconia ceramic beads 8 and the rotor 9 having a particle diameter of 50 μm, guided into the vessel 7, and the wet-pulverized slurry liquid 10 is added to the pre-pressed slurry. The mixture is returned to the mixing tank 4 via the pipe 11 and is circulated again to the bead mill 6 by the pump 5. When the dispersion work is completed for 2 hours and 30 minutes, the switching valve 12 is opened and the prepared nanodiamond The non-aqueous dispersion 14 was introduced into the product tank 13.

各々の分散作業時間におけるダイヤモンド粒子の粒度分布と、最小粒子径および最大粒子径を表１に示す。なお、１５０分要して分散化させたナノダイヤモンド非水分散液は、６０日経過した時点でも二次凝集は見られず、貯蔵性は安定していた。
表１

Figure 2005097375
Table 1 shows the particle size distribution, minimum particle size, and maximum particle size of the diamond particles in each dispersion operation time. The nanodiamond non-aqueous dispersion dispersed for 150 minutes did not show secondary aggregation even after 60 days, and the storage stability was stable.
Table 1
Figure 2005097375

実施例２
実施例１において、非水系液状媒体のダイヤレン−１４の使用量を３リットル、界面活性剤の使用量を１０ｇ、クラスタ−ダイヤモンドの使用量を３３０ｇ、ビ−ズとして直径５００μｍのジルコニアセラミックビ−ズを、および分散作業時間を１８０分とする他は同様にしてスラリ−中のクラスタ−ダイヤモンド濃度が約１０重量％のスラリ−液を調製し、および実施例１と同様にして湿式ビ−ズミル粉砕を行って次表２に示すダイヤモンド粒子の粒度分布と、最小粒子径および最大粒子径を有するナノダイヤモンド比水分散液を調製した。なお、１８０分要して分散化させたナノダイヤモンド非水分散液は、６０日経過した時点でも二次凝集は見られず、貯蔵性は安定していた。 Example 2
In Example 1, a zirconia ceramic bead having a diameter of 500 μm was used as a non-aqueous liquid medium, dialen-14, 3 liters, a surfactant, 10 g, a cluster diamond, 330 g, and beads. And a slurry solution having a cluster diamond concentration of about 10 wt% in the slurry was prepared in the same manner except that the dispersion time was 180 minutes, and wet bead milling was carried out in the same manner as in Example 1. Then, a nanodiamond specific aqueous dispersion having a particle size distribution of diamond particles and a minimum particle size and a maximum particle size shown in Table 2 below was prepared. The nanodiamond non-aqueous dispersion dispersed for 180 minutes did not show secondary aggregation even after 60 days, and the storage stability was stable.

表２

Figure 2005097375
Table 2
Figure 2005097375

応用例１
実施例１で得たナノダイヤモンド非水分散液１５重量部を市販のアクリル系油性塗料８５重量部に混合し、この塗料を脱脂処理したステンレス鋼板の表面に膜厚が２０μｍとなるように塗布し、乾燥させた。塗膜の鉛筆硬度は、乾燥時３Ｈ、湿潤時２Ｈであり、光沢（７５度測定ＧＵＲＯＳＵ）は９２％であった。塗膜の動摩擦係数は０．１３７であった。 Application example 1
15 parts by weight of the nanodiamond non-aqueous dispersion obtained in Example 1 was mixed with 85 parts by weight of a commercially available acrylic oil-based paint, and this paint was applied to the surface of a stainless steel plate subjected to degreasing treatment so that the film thickness was 20 μm. , Dried. The pencil hardness of the coating film was 3H when dried, 2H when wet, and the gloss (75-degree GROSU) was 92%. The dynamic friction coefficient of the coating film was 0.137.

比較応用例１
市販のアクリル系油性塗料９９重量部に、実施例１で用いたクラスタ−ダイヤモンドを乳鉢で粉砕化したもの１重量部を混合し、この塗料を脱脂処理したステンレス鋼板の表面に膜厚が２０μｍとなるように塗布し、乾燥させた。塗膜の鉛筆硬度は、乾燥時３Ｈ、湿潤時２Ｈであり、光沢は８７％であった。塗膜の動摩擦係数は０．１５６であった。 Comparative application example 1
99 parts by weight of a commercially available acrylic oil-based paint is mixed with 1 part by weight of the crushed cluster-diamond used in Example 1, and the film thickness is 20 μm on the surface of a stainless steel plate obtained by degreasing the paint. It was applied and dried. The pencil hardness of the coating film was 3H when dried, 2H when wet, and the gloss was 87%. The dynamic friction coefficient of the coating film was 0.156.

本発明のビ−ズミル機を用いてクラスタ−ダイヤモンドを湿式微粉砕して調製されたナノダイヤモンド非水分散液は、潤滑性と光沢性の優れた皮膜を与える。   The nanodiamond non-aqueous dispersion prepared by wet pulverization of cluster diamond using the bead mill of the present invention gives a film having excellent lubricity and gloss.

ナノダイヤモンド非水分散液を調製する調製機の正面図である。It is a front view of the preparation machine which prepares a nano diamond non-aqueous dispersion.

符号の説明Explanation of symbols

１ 調製機（微粉砕・分散機）
２ クラスタ−ダイヤモンド凝集体
３ 非水系液状媒体
４ プレ混合槽
６ 湿式ビ−ズミル機
１３ 製品タンク
１４ ナノダイヤモンド非水分散液 1 Preparation machine (fine grinding / dispersing machine)
2 Cluster-diamond aggregate 3 Non-aqueous liquid medium 4 Pre-mixing tank 6 Wet bead mill 13 Product tank 14 Nano diamond non-aqueous dispersion

Claims (3)

沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下の非水系液状媒体に、平均粒子径が３〜２０ナノメ−トルのナノダイヤモンド粒子 ０．１〜１５重量％を均一に分散してなる、ナノダイヤモンド非水分散液。   In a non-aqueous liquid medium having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less, 0.1 to 15% by weight of nanodiamond particles having an average particle diameter of 3 to 20 nanometers are uniformly dispersed. Nano-diamond non-aqueous dispersion. 非水系液状媒体が、灯油、軽油、テレビン油、モ−タ−オイル、潤滑油、炭素数１０〜２０のα−オレフィン、エチレングリコ−ル、エチルアルコ−ル、ポリビニルアルコ−ル、エナメル、ワニスより選ばれたものであることを特徴とする、請求項１に記載のナノダイヤモンド非水分散液。   Non-aqueous liquid medium is selected from kerosene, light oil, turpentine oil, motor oil, lubricating oil, α-olefin having 10 to 20 carbon atoms, ethylene glycol, ethyl alcohol, polyvinyl alcohol, enamel and varnish. The nanodiamond non-aqueous dispersion according to claim 1, wherein 酸素欠乏型爆薬を爆発させて製造したクラスタ−ダイヤモンド凝集体と、沸点が５０〜３００℃、ブルックフィ−ルド粘度が１０センチポイズ以下の非水系液状媒体の混合物を、ビ−ズミル機に導き、直径３０〜５００μｍのセラミックビ−ズを用いてクラスタ−ダイヤモンド凝集体を湿式微粉砕して請求項１に記載のナノダイヤモンド非水分散液を調製する方法。   A mixture of a cluster-diamond aggregate produced by detonating an oxygen-deficient explosive and a non-aqueous liquid medium having a boiling point of 50 to 300 ° C. and a Brookfield viscosity of 10 centipoise or less is led to a bead mill. The method for preparing a nanodiamond non-aqueous dispersion according to claim 1, wherein the cluster-diamond aggregate is wet-pulverized using a ceramic bead of 30 to 500 μm.
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