JP2012035536A - Method for manufacturing high surface hardness film containing diamond fine particles having silicon and/or fluorine - Google Patents
Method for manufacturing high surface hardness film containing diamond fine particles having silicon and/or fluorine Download PDFInfo
- Publication number
- JP2012035536A JP2012035536A JP2010178661A JP2010178661A JP2012035536A JP 2012035536 A JP2012035536 A JP 2012035536A JP 2010178661 A JP2010178661 A JP 2010178661A JP 2010178661 A JP2010178661 A JP 2010178661A JP 2012035536 A JP2012035536 A JP 2012035536A
- Authority
- JP
- Japan
- Prior art keywords
- surface hardness
- high surface
- fine particles
- film
- diamond fine
- 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.)
- Granted
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 138
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 138
- 239000010419 fine particle Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 76
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 57
- 239000011737 fluorine Substances 0.000 title claims abstract description 54
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 46
- 239000010703 silicon Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 73
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- 238000004898 kneading Methods 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 238000010030 laminating Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims description 79
- 239000002113 nanodiamond Substances 0.000 claims description 64
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- 238000004880 explosion Methods 0.000 claims description 18
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- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 5
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- 229910052902 vermiculite Inorganic materials 0.000 description 5
- 235000019354 vermiculite Nutrition 0.000 description 5
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 4
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
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- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 4
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- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 1
- LCNWHVJMIOOGTC-UHFFFAOYSA-N trimethylsilyl prop-2-ynoate Chemical compound C[Si](C)(C)OC(=O)C#C LCNWHVJMIOOGTC-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
Description
本発明は、耐擦傷性や耐摩耗性に優れるとともに、指紋が付着しにくく、また付着した指紋を容易に拭き取ることができる高表面硬度フィルムの製造方法に関し、さらに詳しくは、高硬度フィルム又は高硬度層を押出により形成する工程を含む高表面硬度フィルムの製造方法に関するものである。 The present invention relates to a method for producing a high surface hardness film that has excellent scratch resistance and abrasion resistance, is difficult to attach fingerprints, and can easily wipe off the attached fingerprints. The present invention relates to a method for producing a high surface hardness film including a step of forming a hardness layer by extrusion.
近年、市場が増大している携帯用の情報端末への入力装置として、ディスプレイ画面を直接指、ペン等で触れることによってデータを入力するタッチパネルが利用されている。タッチパネルには、耐擦傷性向上のため、通常、透明保護層及びハードコート層が形成されている。このハードコート層は、硬度や滑り性に優れるので、透明保護層表面の傷付き防止等に用いられる。このようなハードコート層は、透明保護層の表面に紫外線硬化型材料や熱硬化型樹脂からなる硬化材料液を塗布し、光照射又は加熱し、硬化させて形成する。 2. Description of the Related Art In recent years, a touch panel for inputting data by directly touching a display screen with a finger, a pen, or the like is used as an input device for a portable information terminal whose market is increasing. In order to improve the scratch resistance, a transparent protective layer and a hard coat layer are usually formed on the touch panel. Since this hard coat layer is excellent in hardness and slipperiness, it is used for preventing scratches on the surface of the transparent protective layer. Such a hard coat layer is formed by applying a curing material liquid made of an ultraviolet curable material or a thermosetting resin to the surface of the transparent protective layer, and irradiating with light or heating to cure.
特開2004-42653号（特許文献１）には、ハードコート層に雲母、合成雲母、シリカ、アルミナ、酸化カルシウム、チタニア、酸化ジルコニウム、酸化亜鉛、フッ化マグネシウム、スメクタイト、合成スメクタイト、バーミキュライト、ITO（酸化インジウム／酸化錫）、ATO（酸化アンチモン／酸化錫）、酸化錫、酸化インジウム、酸化カドミウム及び酸化アンチモン等の無機微粒子を添加する技術が開示されている。特許文献１は、これらの無機微粒子を添加することによりハードコートフィルムのブロッキングを防止できると記載している。 Japanese Patent Application Laid-Open No. 2004-42653 (Patent Document 1) discloses that a hard coat layer includes mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO. A technique of adding inorganic fine particles such as (indium oxide / tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, cadmium oxide and antimony oxide is disclosed. Patent Document 1 describes that blocking of the hard coat film can be prevented by adding these inorganic fine particles.
しかしながら、特許文献１に記載の無機微粒子は、耐擦傷性や耐摩耗性に対してある程度の効果があるものの、繰り返し使用したときに効果が低減し、また指紋の付着防止、指紋の拭き取り性向上にはほとんど効果がない。そのため耐擦傷性や耐摩耗性を改良するとともに、指紋の付着防止、指紋の拭き取り性向上に効果を発揮するフィラーの開発が望まれている。 However, the inorganic fine particles described in Patent Document 1 have a certain effect on the scratch resistance and abrasion resistance, but the effect is reduced when used repeatedly, prevention of fingerprint adhesion, and improvement of fingerprint wiping property. Has little effect. Therefore, it is desired to develop a filler that improves the scratch resistance and wear resistance, as well as prevents the adhesion of fingerprints and improves the wiping property of fingerprints.
防汚性や汚れ除去性を付与するために、ハードコート層にシリコーン系化合物やフッ素系化合物を含有させ、ハードコート層表面に撥水性を付与することが行われている。しかしながら、これらのシリコーン系化合物やフッ素系化合物は効果が長期にわたって持続しないという欠点があり、また付着した指紋を除去しようとして指やティッシュで擦ると、添加剤のシリコーン系化合物やフッ素系化合物と混ざり合って、拭き跡が残る場合がある。 In order to impart antifouling properties and stain removability, it has been practiced to include a silicone compound or a fluorine compound in the hard coat layer to impart water repellency to the hard coat layer surface. However, these silicone compounds and fluorine compounds have the disadvantage that the effects do not last for a long time, and when they are rubbed with a finger or tissue to remove the attached fingerprint, they are mixed with the additive silicone compound or fluorine compound. Accordingly, a wiping mark may remain.
特開2004-230562号（特許文献２）には、透明基材フィルムの少なくとも片面に、電離放射線感応型樹脂組成物の硬化物からなり、かつ表面の水の接触角が70°以下になるようにアルカリ性水溶液で表面処理されてなるハードコート層を設けたことを特徴とするハードコートフィルムが開示されており、耐擦傷性や耐摩耗性に優れるとともに、指紋が付着しにくく、また付着した指紋を容易に拭き取ることができると記載されている。特許文献２には、電離放射線感応型樹脂組成物とは、紫外線又は電子線などを照射することにより、架橋、硬化する樹脂組成物であり、光重合性プレポリマー及び／又は光重合性モノマーを用いることができ、アルカリ性水溶液としては、一般に水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物の中から選ばれる少なくとも１種を含む水溶液が用いられると記載されている。 Japanese Patent Application Laid-Open No. 2004-230562 (Patent Document 2) discloses that at least one surface of a transparent base film is made of a cured product of an ionizing radiation sensitive resin composition, and the contact angle of water on the surface is 70 ° or less. Discloses a hard coat film characterized by having a hard coat layer surface-treated with an alkaline aqueous solution, which is excellent in scratch resistance and wear resistance, and is difficult to attach a fingerprint, and also has an attached fingerprint. It can be easily wiped off. In Patent Document 2, an ionizing radiation-sensitive resin composition is a resin composition that crosslinks and cures when irradiated with ultraviolet rays or an electron beam, and includes a photopolymerizable prepolymer and / or a photopolymerizable monomer. It is described that an aqueous solution containing at least one selected from alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide is generally used as the alkaline aqueous solution.
しかしながら、特許文献２に記載のハードコートフィルムも、強く擦った場合に指紋付着を防止する効果がなくなる等、効果の持続性は十分に満足の行くものではない。 However, even the hard coat film described in Patent Document 2 is not sufficiently satisfactory in sustaining the effect, for example, when the effect of preventing adhesion of fingerprints is lost when rubbed strongly.
特開2002−192596号（特許文献３）には、樹脂と充填材とを溶融混練し、押出成形する工程により形成された高表面硬度フィルムが開示されており、前記樹脂材料としては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエチレンテレフタレートとポリエチレンナフタレートとの混合物、主としてエチレンテレフタレート単位とエチレンナフタレート単位とからなる共重合体等のポリエステル、ポリカーボネート、ノルボルネン系樹脂（環状オレフィン共重合体）、トリアセチルセルロース、ジアセチルセルロース等のセルロース樹脂、ポリアリレート、ポリメタクリル酸メチルエステルが挙げられており、前記充填材として、シリカ、アルミナ、チタニア、ジルコニア、雲母、タルク、炭酸カルシウム、硫酸バリウム、酸化亜鉛、酸化マグネシウム、硫酸カルシウム、カオリンのような無機微粒子、架橋ポリスチレンのような有機微粒子が挙げられている。 Japanese Patent Application Laid-Open No. 2002-192596 (Patent Document 3) discloses a high surface hardness film formed by a process of melt-kneading a resin and a filler and extrusion molding, and the resin material includes polyethylene terephthalate. , Polyethylene naphthalate, a mixture of polyethylene terephthalate and polyethylene naphthalate, polyester such as a copolymer mainly composed of ethylene terephthalate units and ethylene naphthalate units, polycarbonate, norbornene resin (cyclic olefin copolymer), triacetyl cellulose , Cellulose resin such as diacetylcellulose, polyarylate, polymethacrylic acid methyl ester, and as the filler, silica, alumina, titania, zirconia, mica, talc, calcium carbonate, barium sulfate, suboxide Examples include inorganic fine particles such as lead, magnesium oxide, calcium sulfate, and kaolin, and organic fine particles such as crosslinked polystyrene.
しかしながら、特許文献３に記載の高表面硬度フィルムは、例えばタッチパネル等の表面保護フィルムとしての使用を考えた場合、硬度が不十分であり、高表面硬度フィルムにさらにハードコート層を設ける必要があった。 However, the high surface hardness film described in Patent Document 3 is insufficient in hardness when considering use as a surface protective film such as a touch panel, for example, and it is necessary to further provide a hard coat layer on the high surface hardness film. It was.
従って、本発明の目的は、耐擦傷性や耐摩耗性に優れるとともに、指紋が付着しにくく、また付着した指紋を容易に拭き取ることができる、タッチパネル、各種ディスプレイ等の保護用に好適な高表面硬度フィルムを簡便に製造する方法を提供することである。 Accordingly, the object of the present invention is to provide a high surface suitable for protection of touch panels, various displays, etc., which has excellent scratch resistance and abrasion resistance, is difficult to attach fingerprints, and can easily wipe off attached fingerprints. It is providing the method of manufacturing a hardness film easily.
上記目的に鑑み鋭意研究の結果、本発明者らは、バインダー材料と、ケイ素及び／又はフッ素を有するダイヤモンド微粒子との混練物を押出成形することにより、簡便な方法で耐擦傷性、耐摩耗性が飛躍的に改良し、指紋が付着しにくい高表面硬度フィルムを製造することができることを見出し、本発明に想到した。 As a result of diligent research in view of the above-mentioned object, the present inventors have obtained a scratch resistance and wear resistance by a simple method by extruding a kneaded product of a binder material and diamond fine particles having silicon and / or fluorine. Has been found to be able to produce a high surface hardness film that is difficult to adhere to fingerprints, and has led to the present invention.
すなわち、高表面硬度フィルムを製造する本発明の方法は、(a)バインダー材料と、ケイ素を有するダイヤモンド微粒子及び／又はフッ素を有するダイヤモンド微粒子とを混練する工程、及び(b)その混練物を押出成形しフィルムを形成する工程を有することを特徴とする。 That is, the method of the present invention for producing a high surface hardness film comprises (a) a step of kneading a binder material with diamond fine particles having silicon and / or diamond fine particles having fluorine, and (b) extruding the kneaded product. It has the process of shape | molding and forming a film, It is characterized by the above-mentioned.
高表面硬度フィルムを製造する本発明のもう一つの方法は、(a)バインダー材料と、ケイ素及びフッ素を有するダイヤモンド微粒子とを混練する工程、及び(b)その混練物を押出成形しフィルムを形成する工程を有することを特徴とする。 Another method of the present invention for producing a high surface hardness film includes (a) a step of kneading a binder material and diamond fine particles having silicon and fluorine, and (b) forming the film by extruding the kneaded product. It has the process to perform.
前記押出成形により得られたフィルムを基材に積層する工程を有することにより、基材と高硬度層とが積層された高表面硬度フィルムを製造することができる。 By having the process of laminating the film obtained by the extrusion molding on the base material, a high surface hardness film in which the base material and the high hardness layer are laminated can be produced.
高表面硬度フィルムを製造する本発明の他の方法は、(a)バインダー材料と、ケイ素を有するダイヤモンド微粒子及び／又はフッ素を有するダイヤモンド微粒子とを混練する工程、及び(b)基材を形成する材料と、得られた混練物とを共押出成形により積層する工程を有することを特徴とする。 Another method of the present invention for producing a high surface hardness film includes (a) a step of kneading a binder material with diamond fine particles having silicon and / or diamond fine particles having fluorine, and (b) forming a substrate. It has the process of laminating | stacking material and the obtained kneaded material by coextrusion molding.
高表面硬度フィルムを製造する本発明のさらに他の方法は、(a)バインダー材料と、ケイ素及びフッ素を有するダイヤモンド微粒子とを混練する工程、及び(b)基材を形成する材料と、得られた混練物とを共押出成形により積層する工程を有することを特徴とする。 Still another method of the present invention for producing a high surface hardness film is obtained by (a) a step of kneading a binder material and diamond fine particles having silicon and fluorine, and (b) a material for forming a substrate. It has the process of laminating | stacking the kneaded material by co-extrusion molding.
前記ケイ素を有するダイヤモンド微粒子はケイ素化処理されたダイヤモンド微粒子であり、前記フッ素を有するダイヤモンド微粒子はフッ素化処理されたダイヤモンド微粒子であるのが好ましい。 Preferably, the silicon-containing diamond fine particles are siliconized diamond fine particles, and the fluorine-containing diamond fine particles are fluorinated diamond fine particles.
前記ケイ素及びフッ素を有するダイヤモンド微粒子が、ケイ素化処理及びフッ素化処理されたダイヤモンド微粒子であるのが好ましい。 The diamond fine particles having silicon and fluorine are preferably diamond fine particles that have been siliconized and fluorinated.
前記ケイ素化処理はシリル化処理であるのが好ましく、前記フッ素化処理はフルオロアルキル基含有オリゴマーによる処理であるのが好ましい。 The siliconization treatment is preferably silylation treatment, and the fluorination treatment is preferably treatment with a fluoroalkyl group-containing oligomer.
前記ダイヤモンド微粒子は***法で得られたナノダイヤモンドであるのが好ましい。 The diamond fine particles are preferably nanodiamonds obtained by an explosion method.
前記バインダー材料は、ポリエステル、アクリル樹脂、ポリオレフィン、ポリカーボネート、又はフッ素樹脂であるのが好ましい。 The binder material is preferably polyester, acrylic resin, polyolefin, polycarbonate, or fluororesin.
前記バインダー材料は、熱硬化型樹脂、紫外線硬化型材料、及び電子線硬化型材料からなる群から選ばれた少なくとも1種の硬化材料であるのが好ましい。 The binder material is preferably at least one curable material selected from the group consisting of thermosetting resins, ultraviolet curable materials, and electron beam curable materials.
前記基材は、ポリエステル、アクリル樹脂、ポリオレフィン、又はフッ素樹脂からなるのが好ましい。 The base material is preferably made of polyester, acrylic resin, polyolefin, or fluororesin.
前記高表面硬度フィルムは、タッチパネル用保護フィルムとして用いられるのが好ましい。 The high surface hardness film is preferably used as a protective film for a touch panel.
本発明の高表面硬度フィルムは、耐擦傷性、耐摩耗性に優れ、指紋が付着しにくく、また付着した指紋を容易に拭き取ることができるので、タッチパネル、各種ディスプレイ等の保護用に好適である。 The high surface hardness film of the present invention is suitable for protecting touch panels, various displays and the like because it has excellent scratch resistance and abrasion resistance, is difficult to adhere fingerprints, and can easily wipe off the attached fingerprints. .
１．高表面硬度フィルム
[1]構成
本発明の高表面硬度フィルムは、フィルムの表面がJIS K5600-5-4で示す鉛筆硬度試験で「4H」以上の硬度を示す高硬度表面を有するフィルムであり、バインダー材料と後述の修飾ダイヤモンド微粒子とを含む混練物を押出して形成されるフィルム、又はそのフィルムを基材に積層してなる積層フィルムである。
1. High surface hardness film
[1] Configuration The high surface hardness film of the present invention is a film having a high hardness surface in which the surface of the film exhibits a hardness of “4H” or higher in a pencil hardness test indicated by JIS K5600-5-4. A film formed by extruding a kneaded material containing the modified diamond fine particles, or a laminated film obtained by laminating the film on a substrate.
本発明の第1の高表面硬度フィルム10は、図１に示すように、修飾ダイヤモンド微粒子１が分散されたバインダー２からなるフィルムであり、バインダー材料と、前記修飾ダイヤモンド微粒子１とを混練し、その混練物を押出成形して形成する。前記修飾ダイヤモンド微粒子１は、(i)ケイ素を有するダイヤモンド微粒子、(ii)フッ素を有するダイヤモンド微粒子、(iii)ケイ素を有するダイヤモンド微粒子及びフッ素を有するダイヤモンド微粒子の混合物、又は(iv)ケイ素及びフッ素を有するダイヤモンド微粒子を含む。 As shown in FIG. 1, the first high surface hardness film 10 of the present invention is a film made of a binder 2 in which modified diamond fine particles 1 are dispersed. The binder material and the modified diamond fine particles 1 are kneaded, The kneaded product is formed by extrusion. The modified diamond fine particles 1 include (i) diamond fine particles having silicon, (ii) diamond fine particles having fluorine, (iii) a mixture of diamond fine particles having silicon and fluorine fine particles, or (iv) silicon and fluorine. Containing diamond fine particles.
本発明の第2の高硬度フィルム20は、図２に示すように、修飾ダイヤモンド微粒子１が分散されたバインダー２からなる高硬度層３と、基材４とからなるフィルムであり、バインダー材料と、前記修飾ダイヤモンド微粒子１とを混練し、その混練物を押出成形して形成してなるフィルム（高硬度層３）を、基材４に積層することによって得られる。基材４と前記修飾ダイヤモンド微粒子１を含むフィルムとの積層は、基材４と前記修飾ダイヤモンド微粒子１を含むフィルムとを別々に形成した後に積層しても良いし、基材を形成する材料５と、バインダー材料及び前記修飾ダイヤモンド微粒子１との混練物とを共押出成形により積層して形成しても良い。前記修飾ダイヤモンド微粒子１は、前記高表面硬度フィルム10で挙げたものと同じである。 As shown in FIG. 2, the second high-hardness film 20 of the present invention is a film comprising a high-hardness layer 3 made of a binder 2 in which modified diamond fine particles 1 are dispersed, and a base material 4. The modified diamond fine particles 1 are kneaded and a film (high hardness layer 3) formed by extruding the kneaded product is laminated on the substrate 4. The substrate 4 and the film containing the modified diamond fine particles 1 may be laminated after the substrate 4 and the film containing the modified diamond fine particles 1 are separately formed, or the material 5 for forming the substrate. And a binder material and a kneaded product of the modified diamond fine particles 1 may be laminated by coextrusion molding. The modified diamond fine particles 1 are the same as those mentioned for the high surface hardness film 10.
第1の高表面硬度フィルム10及び第2の高表面硬度フィルム20の高硬度層３は基本的に同じものであり、バインダー材料と、修飾ダイヤモンド微粒子とを混練し、その混練物を押出成形して形成する。ここで、第1の高表面硬度フィルム10ではこの押出成形したフィルムを積層しないで使用し、第2の高表面硬度フィルム20では、他の基材と積層して使用する。 The high hardness layer 3 of the first high surface hardness film 10 and the second high surface hardness film 20 is basically the same, and the binder material and the modified diamond fine particles are kneaded and the kneaded material is extruded. Form. Here, the first high surface hardness film 10 is used without being laminated, and the second high surface hardness film 20 is used by being laminated with another substrate.
前記修飾ダイヤモンド微粒子を含むフィルム中のケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、及びケイ素及びフッ素を有するダイヤモンド微粒子の含有量は特に限定されないが、バインダー材料に対して、合計で0.001〜10質量%であるのが好ましく、0.01〜5質量%であるのがより好ましく、0.1〜2質量%であるのが最も好ましい。 The content of silicon-containing diamond fine particles, fluorine-containing diamond fine particles, and silicon and fluorine-containing diamond fine particles in the film containing the modified diamond fine particles is not particularly limited, but is 0.001 to 10 mass in total with respect to the binder material. % Is preferable, 0.01 to 5% by mass is more preferable, and 0.1 to 2% by mass is most preferable.
第1の高表面硬度フィルム10及び第2の高表面硬度フィルム20の厚さは、50〜300μmが好ましく、80〜260μmがより好ましい。第2の高表面硬度フィルム20の高硬度層３の厚さは、0.1〜50μm程度であるのが好ましく、1〜30μmであるのがより好ましい。 The thickness of the first high surface hardness film 10 and the second high surface hardness film 20 is preferably 50 to 300 μm, and more preferably 80 to 260 μm. The thickness of the high hardness layer 3 of the second high surface hardness film 20 is preferably about 0.1 to 50 μm, and more preferably 1 to 30 μm.
ケイ素を有するダイヤモンド微粒子及びフッ素を有するダイヤモンド微粒子を混合して使用する場合は、それらの比率はどのような比率でも良いが、2:8〜9:1の範囲であるのが好ましく、3:7〜8:2の範囲であるのがより好ましい。 When diamond fine particles having silicon and diamond fine particles having fluorine are mixed and used, their ratio may be any ratio, but is preferably in the range of 2: 8 to 9: 1, and 3: 7 More preferably, it is in the range of ~ 8: 2.
[2]第1の高表面硬度フィルムの製造方法
(1)バインダー材料
高硬度フィルムを形成するバインダー材料としては、熱可塑性樹脂、熱硬化型樹脂、紫外線硬化型材料、電子線硬化型材料等が挙げられる。
[2] Manufacturing method of first high surface hardness film
(1) Binder material Examples of the binder material for forming the high hardness film include thermoplastic resins, thermosetting resins, ultraviolet curable materials, and electron beam curable materials.
熱可塑性樹脂としては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエチレンテレフタレートとポリエチレンナフタレートとの混合物、主としてエチレンテレフタレート単位とエチレンナフタレート単位とからなる共重合体等のポリエステル、ポリカーボネート、ポリスチレン、ポリプロピレン、ノルボルネン系樹脂（環状オレフィン共重合体）、アクリル樹脂、トリアセチルセルロース、ジアセチルセルロース等のセルロース樹脂、フッ素樹脂、ポリエチレン、ポリアリレート、ポリメタクリル酸メチルエステル等が好ましい。 Examples of thermoplastic resins include polyethylene terephthalate, polyethylene naphthalate, a mixture of polyethylene terephthalate and polyethylene naphthalate, and polyesters such as copolymers consisting mainly of ethylene terephthalate units and ethylene naphthalate units, polycarbonate, polystyrene, polypropylene, norbornene series Preferred are resins (cyclic olefin copolymers), acrylic resins, cellulose resins such as triacetyl cellulose and diacetyl cellulose, fluororesins, polyethylene, polyarylate, and polymethacrylic acid methyl ester.
これら熱可塑性樹脂のうち処理が比較的簡便でかつ良好な高硬度フィルム又は高硬度層が形成される、ポリエステル、アクリル樹脂、ポリオレフィン、ポリカーボネート、フッ素樹脂等が好ましい。 Of these thermoplastic resins, polyesters, acrylic resins, polyolefins, polycarbonates, fluororesins, etc., which are relatively easy to process and can form a good high hardness film or high hardness layer, are preferred.
熱硬化型樹脂とは、熱の作用を受けて分子間架橋による硬化反応を起こし、不溶不融性の三次元網目構造をとる樹脂であり、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、ケイ素樹脂、ポリウレタン樹脂、ジアリルフタレート樹脂等が挙げられる。 A thermosetting resin is a resin that undergoes a curing reaction due to intermolecular crosslinking under the action of heat and takes an insoluble and infusible three-dimensional network structure, such as a phenol resin, a urea resin, a melamine resin, and an unsaturated polyester resin. , Epoxy resin, silicon resin, polyurethane resin, diallyl phthalate resin and the like.
紫外線硬化型材料及び電子線硬化型材料としては、光重合性の官能基を2個以上、特に3〜6個有するモノマー又はオリゴマーが挙げられる。前記モノマー又はオリゴマーとしては、ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート、ポリエーテルアクリレート、アクリレートモノマー、シリコンアクリレート等が挙げられる。紫外線硬化型材料とは、前記モノマー又はオリゴマーのうち、紫外線照射により重合や架橋を起すものであり、電子線硬化型材料とは、前記モノマー又はオリゴマーのうち、電子線照射により重合や架橋を起すものである。前記モノマーやオリゴマーは一種類でもよいし、二種類以上を併用してもよい。 Examples of the ultraviolet curable material and the electron beam curable material include monomers or oligomers having two or more, particularly 3 to 6, photopolymerizable functional groups. Examples of the monomer or oligomer include urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, acrylate monomer, and silicon acrylate. The ultraviolet curable material is one that causes polymerization or cross-linking by ultraviolet irradiation among the monomers or oligomers, and the electron beam curable material causes polymerization or cross-linking by electron beam irradiation among the monomers or oligomers. Is. The monomer or oligomer may be one kind, or two or more kinds may be used in combination.
(2)ケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子
ケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子は、10〜500 nm程度のダイヤモンド微粒子を、ケイ素原子を含有する基及び／又はフッ素原子を含有する基で修飾したものである。すなわち、ケイ素のみを有するダイヤモンド微粒子であってもよいし、フッ素のみを有するダイヤモンド微粒子であってもよいし、ケイ素及びフッ素を有するダイヤモンド微粒子であってもよい。本発明において、これらのダイヤモンド微粒子を総称して修飾ダイヤモンド微粒子と呼ぶ。
(2) Diamond fine particles containing silicon, diamond fine particles containing fluorine, and diamond fine particles containing silicon and fluorine Diamond fine particles containing silicon, diamond fine particles containing fluorine, and diamond fine particles containing silicon and fluorine are about 10 to 500 nm. The diamond fine particles are modified with a group containing a silicon atom and / or a group containing a fluorine atom. That is, diamond fine particles having only silicon, diamond fine particles having only fluorine, or diamond fine particles having silicon and fluorine may be used. In the present invention, these diamond fine particles are collectively referred to as modified diamond fine particles.
ケイ素原子を含有する基及び／又はフッ素原子を含有する基を修飾するためのダイヤモンド微粒子としては、***法で得られたナノダイヤモンドを用いるのが好ましい。***法で得られた未精製のナノダイヤモンドは、ナノダイヤモンドの表面をグラファイト系炭素が覆ったコア/シェル構造を有しており黒く着色している。未精製のナノダイヤモンドをこのまま用いても良いが、より着色の少ない高表面硬度フィルムを得るためには、未精製のナノダイヤモンドを酸化処理し、グラファイト相の一部又はほぼ全部を除去して用いるのが好ましい。 As diamond fine particles for modifying a group containing a silicon atom and / or a group containing a fluorine atom, it is preferable to use nanodiamond obtained by an explosion method. The unpurified nanodiamond obtained by the blasting method has a core / shell structure in which the surface of the nanodiamond is covered with graphite-based carbon, and is colored black. Unpurified nanodiamonds may be used as they are, but in order to obtain a high surface hardness film with less coloring, the unpurified nanodiamonds are oxidized and used by removing part or almost all of the graphite phase. Is preferred.
酸化処理して得られたナノダイヤモンドは、2〜10 nm程度のダイヤモンドの一次粒子からなるメジアン径30〜250 nm(動的光散乱法)の二次粒子である。グラファイト相を除去することにより、着色成分はほとんどなくなるが、微量に残ったグラファイト系炭素の表面に-COOH、-OH等の親水性官能基が存在するため、水、アルコール等の親水的な溶剤への分散に優れている。 Nanodiamonds obtained by oxidation treatment are secondary particles having a median diameter of 30 to 250 nm (dynamic light scattering method) composed of diamond primary particles of about 2 to 10 nm. By removing the graphite phase, there is almost no coloring component, but because there are hydrophilic functional groups such as -COOH and -OH on the surface of the remaining graphite carbon, a hydrophilic solvent such as water and alcohol. Excellent dispersion.
ケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子は、前記***法で得られた未精製のナノダイヤモンド、又は前記酸化処理して得られたナノダイヤモンドを、ケイ素化処理及び／又はフッ素化処理することによって得られ、前記ナノダイヤモンド表面に存在する-COOH、-OH等の親水性官能基にケイ素原子を有する基、及び／又はフッ素原子を有する基が結合したものである。 Diamond fine particles having silicon, diamond fine particles having fluorine, and diamond fine particles having silicon and fluorine are obtained by converting unpurified nanodiamonds obtained by the above-described explosion method or nanodiamonds obtained by the above oxidation treatment into silicon. A group having a silicon atom and / or a group having a fluorine atom is bonded to a hydrophilic functional group such as —COOH or —OH obtained on the surface of the nanodiamond, which is obtained by fluorination treatment and / or fluorination treatment. Is.
ケイ素を有するダイヤモンド微粒子、又はケイ素及びフッ素を有するダイヤモンド微粒子中のケイ素原子の量は、特に限定されないが、ダイヤモンド微粒子に対して、0.1〜25質量%であるのが好ましく、0.2〜20質量%であるのがより好ましい。フッ素を有するダイヤモンド微粒子、又はケイ素及びフッ素を有するダイヤモンド微粒子中のフッ素原子の量は特に限定されないが、ダイヤモンド微粒子に対して、0.1〜20質量%であるのが好ましく、0.2〜15質量%であるのがより好ましい。 The amount of silicon atoms in the diamond fine particles having silicon or the diamond fine particles having silicon and fluorine is not particularly limited, but is preferably 0.1 to 25% by mass, and preferably 0.2 to 20% by mass with respect to the diamond fine particles. More preferably. The amount of fluorine atoms in the diamond fine particles having fluorine or the diamond fine particles having silicon and fluorine is not particularly limited, but is preferably 0.1 to 20% by mass, and preferably 0.2 to 15% by mass with respect to the diamond fine particles. Is more preferable.
(3)その他の添加物
第1の高表面硬度フィルムには、硬度をアップさせ傷付き耐性を高める目的で、修飾ダイヤモンド微粒子の他に無機微粒子を含んでもよい。前記無機微粒子としては、雲母、合成雲母、シリカ、アルミナ、酸化カルシウム、チタニア、酸化ジルコニウム、酸化亜鉛、フッ化マグネシウム、スメクタイト、合成スメクタイト、バーミキュライト、ITO(酸化インジウム/酸化錫)、ATO(酸化アンチモン/酸化錫)、酸化錫、酸化インジウム、酸化カドミウム、酸化アンチモン等が挙げられる。
(3) Other Additives The first high surface hardness film may contain inorganic fine particles in addition to the modified diamond fine particles for the purpose of increasing hardness and improving scratch resistance. Examples of the inorganic fine particles include mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO (antimony oxide). / Tin oxide), tin oxide, indium oxide, cadmium oxide, antimony oxide and the like.
中でも、雲母、合成雲母、シリカ、チタニア、酸化ジルコニウム、フッ化マグネシウム、スメクタイト、合成スメクタイト、ITO(酸化インジウム/酸化錫)、ATO(酸化アンチモン/酸化錫)、酸化錫、バーミキュライトが好ましく、雲母、合成雲母、スメクタイト、合成スメクタイト、バーミキュライトがより好ましい。前記無機微粒子は、一種類でもよいし、二種類以上を併用してもよい。 Among these, mica, synthetic mica, silica, titania, zirconium oxide, magnesium fluoride, smectite, synthetic smectite, ITO (indium oxide / tin oxide), ATO (antimony oxide / tin oxide), tin oxide, vermiculite are preferable, mica, Synthetic mica, smectite, synthetic smectite, and vermiculite are more preferable. One kind of inorganic fine particles may be used, or two or more kinds may be used in combination.
無機微粒子の平均粒子径は、10〜300 nmが好ましく、10〜200 nmがより好ましく、30〜150 nmが最も好ましい。平均粒子径が、10 nm以上の場合は、より小さい表面粗さを有する高硬度層を形成することができ、一方、前記平均粒子径が300 nm以下の場合は、より優れた光学特性を有する高表面硬度フィルムを形成できる。 The average particle size of the inorganic fine particles is preferably 10 to 300 nm, more preferably 10 to 200 nm, and most preferably 30 to 150 nm. When the average particle size is 10 nm or more, a high hardness layer having a smaller surface roughness can be formed. On the other hand, when the average particle size is 300 nm or less, it has better optical properties. High surface hardness film can be formed.
鱗片状及び/又は不規則薄片状の無機微粒子を使用することにより、より優れたブロッキング防止効果を有する高硬度層を形成できる。このような形状を有する無機微粒子としては、シリカ、チタニア、酸化ジルコニウム、ITO等を鱗片状に成形したもの、雲母、合成雲母、スメクタイト、合成スメクタイト、バーミキュライト等が挙げられる。 By using scale-like and / or irregular flaky inorganic fine particles, a high-hardness layer having a more excellent anti-blocking effect can be formed. Examples of the inorganic fine particles having such a shape include those obtained by molding silica, titania, zirconium oxide, ITO and the like into a scale, mica, synthetic mica, smectite, synthetic smectite, vermiculite and the like.
第1の高表面硬度フィルム中の無機微粒子の含有量は、0.01〜6重量％であるのか好ましく、0.01〜5.5重量％であるのがより好ましい。前記含有量が、0.01重量％以上であると、より優れたブロッキング防止効果を有する高表面硬度フィルムを形成することができ、6重量％以下であると、より優れた光学特性を有する高表面硬度フィルムを形成できる。 The content of inorganic fine particles in the first high surface hardness film is preferably 0.01 to 6% by weight, and more preferably 0.01 to 5.5% by weight. When the content is 0.01% by weight or more, a high surface hardness film having a better anti-blocking effect can be formed, and when the content is 6% by weight or less, high surface hardness having more excellent optical properties. A film can be formed.
第1の高表面硬度フィルムには、さらに必要に応じて、アニオン、カチオン性やノニオン性界面活性剤、光安定剤や紫外線吸収剤、触媒、熱・光重合開始剤、重合禁止剤、シリコーン消泡剤、レベリング剤、増粘剤、沈殿防止剤、垂れ防止剤、難燃剤、有機・無機顔料・染料の各種添加剤、添加助剤等を含むことができる。 For the first high surface hardness film, an anionic, cationic or nonionic surfactant, light stabilizer or ultraviolet absorber, catalyst, thermal / photopolymerization initiator, polymerization inhibitor, silicone Foaming agents, leveling agents, thickeners, suspending agents, anti-sagging agents, flame retardants, various organic / inorganic pigment / dye additives, additive aids, and the like can be included.
(4)高表面硬度フィルムの形成
バインダー材料、修飾ダイヤモンド微粒子、及び必要に応じてその他の添加物の混練は、既存の押出混練機を用いて行うことができる。混練温度、混練時間、剪断応力等の混練条件は、樹脂の種類、充填材の種類、これらの量、割合等により適宜決定される。一般的には、混練温度は、通常200℃〜450℃、好ましくは220℃〜400℃、さらに好ましくは240℃〜350℃であり、混練時間は通常1分〜200分以下、より好ましくは2分〜100分、さらに好ましくは3分〜30分である。
(4) Formation of High Surface Hardness Film Kneading of the binder material, the modified diamond fine particles, and other additives as necessary can be performed using an existing extrusion kneader. Kneading conditions such as kneading temperature, kneading time and shear stress are appropriately determined depending on the type of resin, the type of filler, the amount and ratio thereof. Generally, the kneading temperature is usually 200 ° C. to 450 ° C., preferably 220 ° C. to 400 ° C., more preferably 240 ° C. to 350 ° C., and the kneading time is usually 1 minute to 200 minutes or less, more preferably 2 Minutes to 100 minutes, more preferably 3 minutes to 30 minutes.
混練物は、公知の押出法により押出してフィルムを形成する。例えば、口金から回転する金属ロールなどに押出して急冷し、得られた未延伸フィルムを、必要に応じて連続製膜方向（MD方向）及び連続製膜方向に対して垂直な方向（TD方向）に延伸し、熱固定処理を施すことにより製造する。 The kneaded product is extruded by a known extrusion method to form a film. For example, extruding from a die to a rotating metal roll or the like and quenching, the obtained unstretched film is continuously formed (MD direction) and perpendicular to the continuous film forming direction (TD direction) as necessary. It is manufactured by being stretched and subjected to heat setting treatment.
[3]第2の高表面硬度フィルムの製造方法
第2の高表面硬度フィルムは、第1の高表面硬度フィルムと同じ構成の高硬度層を基材上に積層したものなので、前記高硬度層を形成するバインダー材料、修飾ダイヤモンド微粒子、及び必要に応じて使用するその他の添加物については第1の高表面硬度フィルムで説明したものと同様である。従って、これらの説明は省略し、基材及び高表面硬度フィルムの形成方法について詳しく説明する。
[3] Method for producing second high surface hardness film Since the second high surface hardness film is obtained by laminating a high hardness layer having the same configuration as the first high surface hardness film on the substrate, the high hardness layer The binder material, the modified diamond fine particles, and other additives used as necessary are the same as those described for the first high surface hardness film. Therefore, these descriptions are omitted, and the method for forming the base material and the high surface hardness film will be described in detail.
(1)基材
基材については特に制限はなく、光学用フィルムの基材として公知のプラスチックフィルムの中から適宜選択して用いることができる。このようなプラスチックフィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート等のポリエステル系フィルム、ポリメチルメタクリレート等のアクリル系フィルム、ポリエチレン、ポリプロピレン、ポリメチルペンテン、脂環式構造含有重合体等のポリオレフィン系フィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン-酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ポリアミドフィルム等を用いることができる。
(1) Substrate The substrate is not particularly limited, and can be appropriately selected from known plastic films as a substrate for optical films. Examples of such plastic films include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyester films such as polycarbonate, acrylic films such as polymethyl methacrylate, polyethylene, polypropylene, polymethylpentene, and alicyclic structure-containing polymers. Polyolefin films such as cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polysulfone Film, polyetheretherketone film, polyethersulfone film, polyether An imide film, a polyimide film, a fluororesin film, a polyamide film, or the like can be used.
これらの透明基材フィルムの中で、タッチパネル用や各種ディスプレイの表面保護用フィルム等の光学用フィルムの基材としては、性能及び経済性の面からポリエステル系フィルム、アクリル系フィルム及びポリオレフィン系フィルムが好適であり、特に耐熱性が要求される用途には、脂環式構造含有ポリオレフィン系フィルム、フッ素樹脂等が好ましく用いられる。 Among these transparent substrate films, polyester films, acrylic films, and polyolefin films are used as optical film substrates such as touch panel and various display surface protection films from the viewpoint of performance and economy. In applications where heat resistance is particularly required, alicyclic structure-containing polyolefin films, fluororesins, and the like are preferably used.
これらの基材フィルムは、透明、半透明のいずれであってもよく、着色されていてもよいし、無着色のものでもよく、用途に応じて適宜選択すればよい。液晶表示体の保護用として用いる場合には、無色透明のフィルムが好適である。 These base films may be either transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected depending on the application. When used for protecting a liquid crystal display, a colorless and transparent film is suitable.
これらの透明基材フィルムの厚さは特に制限はなく、状況に応じて適宜選定されるが、通常15〜300μm、好ましくは30〜250μmの範囲である。また、この透明基材フィルムは、その表面に設けられる層との密着性を向上させる目的で、所望により片面又は両面に、酸化法や凹凸化法などにより表面処理を施すことができる。上記酸化法としては、コロナ放電処理、クロム酸処理(湿式)、火炎処理、熱風処理、オゾン・紫外線照射処理等が挙げられ、また、凹凸化法としては、サンドブラスト法、溶剤処理法等が挙げられる。これらの表面処理法は透明基材フィルムの種類に応じて適宜選ばれるが、一般にはコロナ放電処理法が効果及び操作性等の面から、好ましく用いられる。 The thickness of these transparent substrate films is not particularly limited and is appropriately selected depending on the situation, but is usually in the range of 15 to 300 μm, preferably 30 to 250 μm. Moreover, this transparent base film can be surface-treated by an oxidation method, an uneven | corrugated method, etc. on one side or both sides as needed for the purpose of improving the adhesiveness with the layer provided in the surface. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include a sand blast method and a solvent treatment method. It is done. These surface treatment methods are appropriately selected according to the type of the transparent substrate film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.
(2) 高表面硬度フィルムの形成
(i) 基材と高硬度層とを別々に形成し積層する方法
第1の高表面硬度フィルムと同様にして、バインダー材料、修飾ダイヤモンド微粒子、及び必要に応じてその他の添加物を混練し、得られた混練物を公知の押出法により押出して高硬度フィルムを形成する。この高硬度フィルムを、別に形成した基材とドライラミネーション、熱ラミネーション等により貼り合わせ得て積層する。これらのフィルムを延伸する場合は、積層する前に個々の状態で延伸しても良く、また積層した後に延伸しても良い。
(2) Formation of high surface hardness film
(i) Method of separately forming and laminating the base material and the high hardness layer In the same manner as the first high surface hardness film, the binder material, the modified diamond fine particles, and other additives as necessary are kneaded, The obtained kneaded material is extruded by a known extrusion method to form a high hardness film. This high-hardness film is laminated with a separately formed substrate by dry lamination, thermal lamination, or the like. When these films are stretched, they may be stretched in individual states before being laminated, or may be stretched after being laminated.
(ii) 基材と高硬度層とを共押出により積層する方法
基材を形成する材料と、バインダー材料、修飾ダイヤモンド微粒子、及びその他の添加物からなる混練物とを共押出しにより積層する。生産性の点で、前記の別々にフィルムを形成した後に積層するよりも、共押出しにより積層する方が好ましい。さらに共押出成形の場合には、複雑な工程（乾燥工程や塗工工程）を経なくてもよいため、ゴミなどの外部異物の混入が少なく、優れた光学性能を発揮できる。
(ii) Method of Laminating Base Material and High Hardness Layer by Coextrusion A material for forming the base material and a kneaded material comprising a binder material, modified diamond fine particles, and other additives are laminated by coextrusion. In terms of productivity, it is preferable to laminate by coextrusion rather than laminating after forming the films separately. Furthermore, in the case of coextrusion molding, it is not necessary to go through a complicated process (drying process or coating process), so that there is little mixing of external foreign matters such as dust, and excellent optical performance can be exhibited.
[4]高表面硬度フィルムの特性
本発明の高表面硬度フィルムは、バインダー材料中に、修飾ダイヤモンド微粒子（ケイ素を有するダイヤモンド微粒子及び／又はフッ素を有するダイヤモンド微粒子、又はケイ素及びフッ素を有するダイヤモンド微粒子）を含有する高い表面硬度を有するフィルムである。修飾ダイヤモンド微粒子を含有させることで、優れた耐擦傷性と高い硬度をフィルムに持たせることができ、フィルムの鉛筆硬度が上がり、高表面硬度を実現することができるとともに、指紋が付着しにくく、また付着した指紋を容易に拭き取ることができるようになる。鉛筆硬度は、JIS K5600-5-4が規定する鉛筆硬度評価方法により求められる値であり、フィルムの表面硬度を量る指標となる。鉛筆硬度が4H以上であれば、フィルムとしては十分な表面硬度を有し、好ましくは5H以上である。
[4] Characteristics of High Surface Hardness Film The high surface hardness film of the present invention includes a modified diamond fine particle (diamond fine particle having silicon and / or diamond fine particle having fluorine, or diamond fine particle having silicon and fluorine) in a binder material. Is a film having a high surface hardness. By including modified diamond fine particles, the film can have excellent scratch resistance and high hardness, the pencil hardness of the film can be increased, high surface hardness can be realized, and fingerprints are difficult to adhere, In addition, the attached fingerprint can be easily wiped off. The pencil hardness is a value obtained by a pencil hardness evaluation method specified by JIS K5600-5-4, and is an index for measuring the surface hardness of the film. If the pencil hardness is 4H or more, the film has a sufficient surface hardness, preferably 5H or more.
[5]その他の層
(1)透明導電層
第1及び第2の高表面硬度フィルムには、必要に応じて１つの面に透明導電層を設けてもよい。第2の高表面硬度フィルムの場合、高硬度層３が形成された面とは反対の面に透明導電層を設けるのが好ましい。透明導電層としては、酸化錫(SnO2等)、酸化インジウム、酸化アンチモン、酸化亜鉛(ZnO)、酸化カドミウム、インジウム錫酸化物(ITO)等の金属酸化物、金、銀、銅、アルミニウム、錫、ニッケル等の金属膜が挙げられる。その中でも、金属酸化膜は、成長が速く、中でもZnO、SnO2等の単一金属からなる酸化物が化学量論比による制御が容易で高性能な薄膜が得られる点で好ましい。透明導電層の形成方法は特に限定されず、スパッタリング法、真空蒸着法、イオンプレーティング法、低圧プラズマ、塗工法、常圧プラズマCVD法等が挙げられる。透明導電層の厚さは、表面抵抗が発現し、透明性が保たれる厚みであることが好ましく、赤外線及び電磁波の低減性能が発現し、可視光透過率が60％以上であるためには、膜厚は30〜200 nmであるのが好ましい。
[5] Other layers
(1) Transparent conductive layer The first and second high surface hardness films may be provided with a transparent conductive layer on one surface as necessary. In the case of the second high surface hardness film, it is preferable to provide a transparent conductive layer on the surface opposite to the surface on which the high hardness layer 3 is formed. As the transparent conductive layer, metal oxides such as tin oxide (SnO 2 etc.), indium oxide, antimony oxide, zinc oxide (ZnO), cadmium oxide, indium tin oxide (ITO), gold, silver, copper, aluminum, Examples of the metal film include tin and nickel. Among them, the metal oxide film is preferable because it grows quickly, and oxides made of a single metal such as ZnO and SnO 2 are particularly easy to control by the stoichiometric ratio and provide a high-performance thin film. The method for forming the transparent conductive layer is not particularly limited, and examples thereof include a sputtering method, a vacuum deposition method, an ion plating method, a low pressure plasma, a coating method, and an atmospheric pressure plasma CVD method. The thickness of the transparent conductive layer is preferably a thickness where surface resistance is expressed and transparency is maintained. In order to exhibit infrared and electromagnetic wave reduction performance and a visible light transmittance of 60% or more, The film thickness is preferably 30 to 200 nm.
(2)反射防止層
第1及び第2の高表面硬度フィルムには、本発明の目的を阻害しない範囲で、フィルムの表面に反射防止層を設けることができる。反射防止層としては、TiO2、ZrO2、SiO2、MgF等が用いられる。高性能な反射防止機能を付与するには、TiO2層とSiO2層との積層体を用いるのが好ましい。このような積層体としては、第1の高表面硬度フィルム又は第2の高表面硬度フィルムの高硬度層上に屈折率の高いTiO2層(屈折率：約1.8〜2.1)を形成し、このTiO2層上に屈折率の低いSiO2層(屈折率：約1.4〜1.5)を形成してなる2層積層体、さらにこの2層積層体上に、TiO2層及びSiO2層をこの順に形成してなる4層積層体が好ましい。このような2層積層体又は4層積層体の反射防止層を設けることにより、特定波長の光の反射率を低くすることができる。
(2) Antireflection layer The first and second high surface hardness films can be provided with an antireflection layer on the surface of the film as long as the object of the present invention is not impaired. As the antireflection layer, TiO 2 , ZrO 2 , SiO 2 , MgF or the like is used. In order to provide a high-performance antireflection function, it is preferable to use a laminate of a TiO 2 layer and a SiO 2 layer. As such a laminate, a high refractive index TiO 2 layer (refractive index: about 1.8 to 2.1) is formed on the high hardness layer of the first high surface hardness film or the second high surface hardness film. lower SiO 2 layer having a refractive index in the TiO 2 layer on the (refractive index: about 1.4 to 1.5) 2-layer laminate obtained by forming a further two-layer laminate on the TiO 2 layer and the SiO 2 layer in this order A four-layer laminate formed is preferable. By providing such an antireflection layer of a two-layer laminate or a four-layer laminate, the reflectance of light having a specific wavelength can be lowered.
反射防止層の膜厚をd、屈折率をn、入射光の波長をλとしたとき、反射防止層の膜厚とその屈折率との間でnd＝λ/4なる関係式が成立するように反射防止層を設ける。反射防止層の屈折率が基材の屈折率より小さい場合は、上記関係式が成立する条件では反射率が最小となる。従って、得られる反射防止層の屈折率nが分かっていれば、膜厚dは反射防止層の製造における成膜速度とその処理時間で決定でき、特定の入射光の波長λ(単色光)に対して反射率を最小にすることができる。 When the thickness of the antireflection layer is d, the refractive index is n, and the wavelength of incident light is λ, the relational expression nd = λ / 4 holds between the thickness of the antireflection layer and its refractive index. Is provided with an antireflection layer. When the refractive index of the antireflection layer is smaller than the refractive index of the base material, the reflectance is minimized under the condition that the above relational expression is satisfied. Therefore, if the refractive index n of the obtained antireflection layer is known, the film thickness d can be determined by the film formation speed and the processing time in the production of the antireflection layer, and the wavelength λ (monochromatic light) of the specific incident light. On the other hand, the reflectance can be minimized.
2層以上の薄膜で反射防止層を形成する場合は、最上層(表面層)を低屈折率材料のλ/4膜近辺となるようにし、基材上から高屈折率材料と低屈折率が交互に配置するのが好ましい。ここで、表面から2層目以降の膜厚は、波長450〜650nmでの反射率が小さくなるように設定され、屈折率との兼ね合いになるが、一般にλ/2膜以下の厚さとなる。これにより、単層の反射防止層よりも低反射の波長領域を広げることができる。 When forming the antireflection layer with two or more thin films, the uppermost layer (surface layer) should be near the λ / 4 film of the low refractive index material, and the high refractive index material and low refractive index should be It is preferable to arrange them alternately. Here, the film thickness of the second and subsequent layers from the surface is set so that the reflectance at a wavelength of 450 to 650 nm is small, and it is in balance with the refractive index, but generally has a thickness of λ / 2 film or less. Thereby, the wavelength range of low reflection can be expanded compared with a single-layer antireflection layer.
上記反射防止層の積層方法は特に限定されず、スパッタリング、蒸着、低圧プラズマCVD、塗工等が挙げられる。好ましくは、常圧プラズマCVD法である。 The method for laminating the antireflection layer is not particularly limited, and examples thereof include sputtering, vapor deposition, low pressure plasma CVD, and coating. The atmospheric pressure plasma CVD method is preferable.
２．ケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子の製造方法
ケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子は、ダイヤモンド微粒子をケイ素化処理及び／又はフッ素化処理することにより得ることができる。ケイ素化処理は、フッ素化処理よりも先に行うのが好ましい。
2. Diamond fine particles containing silicon, diamond fine particles containing fluorine, and diamond fine particles containing silicon and fluorine. Diamond fine particles containing silicon, diamond fine particles containing fluorine, and diamond fine particles containing silicon and fluorine are siliconized diamond fine particles. It can be obtained by treatment and / or fluorination treatment. The siliconization treatment is preferably performed prior to the fluorination treatment.
[1]ダイヤモンド微粒子の製造方法
ダイヤモンド微粒子としては、***法により得られた未精製のナノダイヤモンド（BDと言うこともある。）、又はそれを酸化処理しグラファイト系炭素の一部又は全部を除去したナノダイヤモンドが好ましい。前記酸化処理して得られるナノダイヤモンドとしては、後述のグラファイト相の一部が除去されたナノダイヤモンド（グラファイト-ダイヤモンド粒子と呼ぶ）及びグラファイト相がほとんど除去された精製ナノダイヤモンド粒子が好ましい。
[1] Method for producing diamond fine particles As diamond fine particles, unpurified nanodiamond (sometimes referred to as BD) obtained by an explosion method, or a part or all of graphite-based carbon by oxidizing it. The removed nanodiamond is preferred. The nanodiamond obtained by the oxidation treatment is preferably nanodiamond from which a part of the graphite phase described later is removed (referred to as graphite-diamond particles) and purified nanodiamond particles from which the graphite phase is almost removed.
酸化処理したナノダイヤモンドの比重は、グラファイト系炭素（グラファイトの比重：2.25 g/cm3）の残存量が少なくなればなるほどダイヤモンドの比重（3.50 g/cm3）に近づく。従って、精製度が高くグラファイト系炭素の残存量が少ないほど比重が高くなる。本発明で用いるナノダイヤモンドの比重は2.55 g/cm3（ダイヤモンド24体積％）以上3.48 g/cm3（ダイヤモンド98体積％）以下であるのが好ましく、3.0 g/cm3（ダイヤモンド84体積％）以上3.46 g/cm3（ダイヤモンド97体積％）以下であるのがより好ましく、3.38 g/cm3（ダイヤモンド90体積％）以上3.45 g/cm3（ダイヤモンド96体積％）以下であるのが最も好ましい。なおナノダイヤモンド中のダイヤモンドの体積％は、前記ダイヤモンドの比重3.50 g/cm3及びグラファイトの比重2.25 g/cm3を用いて、ナノダイヤモンドの比重から算出した。 The specific gravity of the oxidized nanodiamond approaches the specific gravity of diamond (3.50 g / cm 3 ) as the residual amount of graphite-based carbon (graphite specific gravity: 2.25 g / cm 3 ) decreases. Therefore, the specific gravity increases as the degree of purification increases and the remaining amount of graphite carbon decreases. The specific gravity of the nano diamond used in the present invention is preferably 2.55 g / cm 3 (24% by volume of diamond) or more and 3.48 g / cm 3 (98% by volume of diamond) or less, 3.0 g / cm 3 (84% by volume of diamond). It is more preferably 3.46 g / cm 3 (diamond 97% by volume) or less, and most preferably 3.38 g / cm 3 (diamond 90% by volume) or more and 3.45 g / cm 3 (diamond 96% by volume). . The volume percentage of diamond in the nanodiamond was calculated from the specific gravity of the nanodiamond using the specific gravity of the diamond of 3.50 g / cm 3 and the specific gravity of graphite of 2.25 g / cm 3 .
未精製の粗ダイヤモンドの酸化処理方法としては、(a) 硝酸等の共存下で高温高圧処理する方法（酸化処理A）、(b)水及び／又はアルコールからなる超臨界流体中で処理する方法（酸化処理B）、(c)水及び／又はアルコールからなる溶媒に酸素を共存させて、前記溶媒の標準沸点以上の温度及び0.1 MPa（ゲージ圧）以上の圧力で処理する方法（酸化処理C）、又は(d)380〜450℃で酸素を含む気体により処理する方法（酸化処理D）が挙げられる。これらの酸化処理は、単独で行ってもよいし、組合せて行っても良い。酸化処理を組合せる場合は、***法で得られた未精製の粗ダイヤモンドにまず酸化処理Aを施し、さらに酸化処理B〜Cのいずれかを施すのが好ましい。 Oxidation treatment of unpurified crude diamond includes (a) high-temperature and high-pressure treatment in the presence of nitric acid (oxidation treatment A), and (b) treatment in a supercritical fluid composed of water and / or alcohol. (Oxidation treatment B), (c) A method in which oxygen is present in a solvent consisting of water and / or alcohol, and the treatment is performed at a temperature not lower than the normal boiling point of the solvent and at a pressure not lower than 0.1 MPa (gauge pressure) (oxidation treatment C). ) Or (d) a method (oxidation treatment D) in which treatment is performed with a gas containing oxygen at 380 to 450 ° C. These oxidation treatments may be performed alone or in combination. When combining the oxidation treatment, it is preferable to first subject the unpurified crude diamond obtained by the explosion method to oxidation treatment A, and then to any one of oxidation treatments B to C.
***法で得られた未精製の粗ダイヤモンドに酸化処理Aを施すことによりグラファイト相の一部が除去されたナノダイヤモンド（グラファイト-ダイヤモンド粒子）が得られ、このグラファイト-ダイヤモンド粒子に酸化処理B〜Cのいずれかの処理を施すことにより前記グラファイト相をさらに除去することができる。 By applying oxidation treatment A to the unpurified crude diamond obtained by the explosion method, nanodiamonds (graphite-diamond particles) from which a part of the graphite phase has been removed are obtained. The graphite phase can be further removed by performing any one of the processes of ~ C.
(1) ***法によるBDの合成
***法によるBDの合成は、例えば、水と多量の氷を満たした純チタン製の耐圧容器に、電気***を装着した爆薬［例えば、TNT(トリニトロトルエン)/HMX(シクロテトラメチレンテトラニトラミン)＝50/50］を胴内に収納させ、片面プラグ付き鋼鉄製パイプを水平に沈め、この鋼鉄製パイプに鋼鉄製のヘルメット状カバーを被覆して、前記爆薬を爆裂させることにより行うことができる。反応生成物としてのBDは容器中の水及び氷中から回収する。
(1) Synthesis of BD by explosion method BD synthesis by explosion method is, for example, explosives in which an electric detonator is mounted on a pressure vessel made of pure titanium filled with water and a large amount of ice [for example, TNT (trinitrotoluene ) / HMX (Cyclotetramethylenetetranitramine) = 50/50] is stored in the body, a steel pipe with a single-sided plug is submerged horizontally, and this steel pipe is covered with a steel helmet-like cover. This can be done by exploding the explosive. BD as a reaction product is recovered from water and ice in the container.
前記***法は、Science, Vol. 133, No.3467(1961), pp1821-1822、特開平1-234311号、特開平2-141414号、Bull. Soc. Chem. Fr. Vol. 134(1997), pp. 875-890、Diamond and Related materials Vol. 9(2000), pp861-865、Chemical Physics Letters, 222(1994), pp. 343-346、Carbon, Vol. 33, No. 12(1995), pp. 1663-1671、Physics of the Solid State, Vol. 42, No. 8 (2000), pp. 1575-1578、K. Xu. Z. Jin, F. Wei and T. Jiang, Energetic Materials, 1, 19(1993)、特開昭63-303806号、特開昭56-26711報、英国特許第1154633号、特開平3-271109号、特表平6-505694号(WO93/13016号)、炭素, 第22巻, No. 2, 189〜191頁(1984)、Van Thiei. M. & Rec., F. H., J. Appl. Phys. 62, pp. 1761〜1767 (1987)、特表平7-505831号 (WO94/18123号)、米国特許第5861349号及び特開2006-239511号等に記載の方法を用いることができる。 The above-mentioned explosion method is described in Science, Vol. 133, No. 3467 (1961), pp 1821-1822, JP-A No. 1-234311, JP-A No. 21-14414, Bull. Soc. Chem. Fr. Vol. 134 (1997). ), pp. 875-890, Diamond and Related materials Vol. 9 (2000), pp861-865, Chemical Physics Letters, 222 (1994), pp. 343-346, Carbon, Vol. 33, No. 12 (1995) , pp. 1663-1671, Physics of the Solid State, Vol. 42, No. 8 (2000), pp. 1575-1578, K. Xu. Z. Jin, F. Wei and T. Jiang, Energetic Materials, 1 , 19 (1993), JP-A-63-303806, JP-A-56-26711, British Patent No. 1154633, JP-A-3-271109, JP-A-6-505694 (WO93 / 13016), Carbon , Vol. 22, No. 2, 189-191 (1984), Van Thiei. M. & Rec., FH, J. Appl. Phys. 62, pp. 1761-1767 (1987), 7-1-1 No. 505831 (WO94 / 18123), US Pat. No. 5,861,349, JP-A-2006-239511, and the like can be used.
(2)酸化処理工程
(i)酸化処理A
***法で得られた未精製の粗ダイヤモンド(BD)は、まず酸化処理Aを施すのが好ましい。酸化処理Aを施すことによりグラファイト相の一部が除去されたグラファイト-ダイヤモンド粒子が得られる。酸化処理Aは、(a) ***法で得られたBDを、酸中で酸化性分解処理する工程、(b)酸化性分解処理したBDを、さらに厳しい条件で処理する酸化性エッチング処理工程、(c)酸化性エッチング処理後の液を中和する工程、(d)脱溶媒工程、及び(e)洗浄工程からなり、必要に応じてグラファイト-ダイヤモンド粒子分散液の(f)pH及び濃度を調製する工程、又は(g) 乾燥して微粉末とする工程からなる。
(2) Oxidation process
(i) Oxidation treatment A
The unpurified crude diamond (BD) obtained by the explosion method is preferably first subjected to oxidation treatment A. By performing the oxidation treatment A, graphite-diamond particles from which a part of the graphite phase has been removed can be obtained. Oxidation treatment A consists of (a) a process in which BD obtained by the explosion method is subjected to an oxidative decomposition process in an acid, and (b) an oxidative etching process in which the BD that has been subjected to an oxidative decomposition process is processed under more severe conditions , (C) a step of neutralizing the solution after the oxidative etching treatment, (d) a desolvation step, and (e) a washing step, and (f) pH and concentration of the graphite-diamond particle dispersion as necessary. Or (g) a step of drying into a fine powder.
(a) 酸化性分解処理工程
回収したBDを55〜56質量％の濃硝酸、又は濃硝酸と濃硫酸との混合物とともに、1.4 MPa程度の圧力及び150〜180℃程度の温度で10〜30分間処理し、電気***等の混入金属、炭素等の夾雑物等の不純物を分解する。
(a) Oxidative decomposition treatment process Collected BD together with 55-56 mass% concentrated nitric acid or a mixture of concentrated nitric acid and concentrated sulfuric acid at a pressure of about 1.4 MPa and a temperature of about 150-180 ° C for 10-30 minutes Process and decompose impurities such as mixed metal such as electric detonator, carbon and other impurities.
(b) 酸化性エッチング処理工程
酸化性分解処理したBDは、濃硝酸中で酸化性分解処理よりもさらに厳しい条件（例えば、1.4 MPa、200〜240℃）で行う。このような条件で10〜30分処理すると、BD表面を被覆する硬質炭素、すなわちグラファイトを大部分除去することができる。
(b) Oxidative Etching Process Step The BD subjected to the oxidative decomposition treatment is performed under concentrated conditions (for example, 1.4 MPa, 200 to 240 ° C.) in concentrated nitric acid. When treated for 10 to 30 minutes under such conditions, most of the hard carbon, ie, graphite, covering the BD surface can be removed.
(c) 中和工程
酸化性エッチング処理後のグラファイト-ダイヤモンド粒子を含む硝酸水溶液（pHが2〜6.95）に、それ自身又はその分解反応生成物が揮発性の塩基性物質を加えて中和反応させる。塩基性物質の添加によりpH7.05〜12に上昇する。前記塩基性物質を使用することにより、凝集したグラファイト-ダイヤモンド粒子内に浸透した塩基が、粒子内の硝酸と反応し、ガス化することにより凝集体を個々のグラファイト-ダイヤモンド粒子に解体するといった効果が得られる。この工程により、グラファイト-ダイヤモンド粒子の大きな比表面積及び孔部吸着空間が形成されるものと思われる。
(c) Neutralization process Neutralization reaction by adding a volatile basic substance itself or its decomposition product to an aqueous nitric acid solution (pH 2 to 6.95) containing graphite-diamond particles after oxidative etching. Let The pH rises to 7.05-12 by the addition of basic substances. By using the basic substance, the base that has penetrated into the agglomerated graphite-diamond particles reacts with nitric acid in the particles and gasifies to break up the agglomerates into individual graphite-diamond particles. Is obtained. This process seems to form a large specific surface area and pore adsorption space of graphite-diamond particles.
塩基性材料としては、アンモニア、ヒドラジン、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エタノールアミン、プロピルアミン、イソプロピルアミン、ジプロピルアミン、アリルアミン、アニリン、N,N-ジメチルアニリン、ジイソプロピルアミン、ジエチレントリアミンやテトラエチレンペンタミンのようなポリアルキレンポリアミン、2-エチルヘキシルアミン、シクロヘキシルアミン、ピペリジン、ホルムアミド、N,N-メチルホルムアミド、尿素等を挙げることができる。 Basic materials include ammonia, hydrazine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, propylamine, isopropylamine, dipropylamine, allylamine, aniline, N, N-dimethylaniline, diisopropylamine. And polyalkylene polyamines such as diethylenetriamine and tetraethylenepentamine, 2-ethylhexylamine, cyclohexylamine, piperidine, formamide, N, N-methylformamide, urea and the like.
(d) 脱溶媒工程
得られたグラファイト-ダイヤモンド粒子を含む液は、遠心分離、デカンテーション等により脱溶媒するのが好ましい。
(d) Desolvation step The obtained liquid containing graphite-diamond particles is preferably desolvated by centrifugation, decantation or the like.
(e) 水洗工程
脱溶媒したグラファイト-ダイヤモンド粒子はデカンテーション法により水洗するのが好ましい。洗浄操作は３回以上行うのが好ましい。水洗したグラファイト-ダイヤモンド粒子は、再度遠心分離し、脱水するのが好ましい。
(e) Water washing step The desolvated graphite-diamond particles are preferably washed by decantation. The washing operation is preferably performed three times or more. The graphite-diamond particles washed with water are preferably centrifuged again and dehydrated.
(f) pH及び濃度を調製する工程
グラファイト-ダイヤモンド粒子分散液は、pH 4〜10、好ましくはpH5〜8、より好ましくはpH6〜7.5に調節する。グラファイト-ダイヤモンド粒子濃度は0.05〜16％、好ましくは0.1〜12％、より好ましくは1〜5％に調製するのが好ましい。
(f) Step of adjusting pH and concentration The graphite-diamond particle dispersion is adjusted to pH 4 to 10, preferably pH 5 to 8, more preferably pH 6 to 7.5. The graphite-diamond particle concentration is preferably adjusted to 0.05 to 16%, preferably 0.1 to 12%, more preferably 1 to 5%.
グラファイト相を有するナノダイヤモンド（グラファイト-ダイヤモンド粒子）はさらに酸化処理B〜Dを施すことによりグラファイト層をさらに除去するのが好ましい。もちろんBDに直接酸化処理B〜Dを施しても良い。 It is preferable that the nanodiamond having graphite phase (graphite-diamond particles) is further subjected to oxidation treatments B to D to further remove the graphite layer. Of course, BD may be directly subjected to oxidation treatments B to D.
(ii)酸化処理B
酸化処理Bは、(a) グラファイト相を有するナノダイヤモンドと、酸化性化合物と、水及び／又はアルコールからなる溶媒とからなる混合物A（単に「混合物A」とよぶことがある）を調製し、(b) この混合物Aを、溶媒の臨界点以上の温度及び圧力にした状態でグラファイト相を有するナノダイヤモンドを処理し、(c) 得られた精製ダイヤモンド粒子を含む液を遠心分離して溶媒を除去する工程を有する。さらに、脱溶媒した精製ダイヤモンド粒子を(d)水洗及び遠心分離により脱水する工程を設けるのが好ましい。工程(c)と(d)の間に、必要に応じて、脱溶媒した精製ダイヤモンド粒子を(e)塩基性溶液で中和する工程、及び(f)弱酸で処理する工程を設けてもよい。工程(c)又は(d)で得られた精製ダイヤモンド粒子は乾燥して微粉末にする。
(ii) Oxidation treatment B
Oxidation treatment B prepares a mixture A (sometimes referred to simply as “mixture A”) comprising (a) a nanodiamond having a graphite phase, an oxidizing compound, and a solvent comprising water and / or alcohol; (b) Treating this mixture A with nanodiamond having a graphite phase in a state where the temperature and pressure are higher than the critical point of the solvent, and (c) centrifuging the resulting liquid containing purified diamond particles to remove the solvent. Removing. Furthermore, it is preferable to provide a step (d) of dewatering the purified diamond particles that have been desolvated by water washing and centrifugation. Between steps (c) and (d), if necessary, a step of neutralizing the desolvated purified diamond particles with (e) a basic solution and a step of (f) treating with a weak acid may be provided . The refined diamond particles obtained in step (c) or (d) are dried to a fine powder.
(a) 混合物Aの調製工程
混合物Aは、グラファイト相を有するナノダイヤモンドの粉末に、酸化性化合物、及び水及び／又はアルコールからなる溶媒を混合することにより調製する。又は、前記溶媒にあらかじめグラファイト相を有するナノダイヤモンドを分散した液に、前記酸化性化合物又はその溶液を添加して調製しても良い。混合物Aには、酸化性化合物による酸化反応を促進させるため、塩基性化合物又は酸化性化合物を添加しても良い。
(a) Preparation Step of Mixture A Mixture A is prepared by mixing nanodiamond powder having a graphite phase with an oxidizing compound and a solvent composed of water and / or alcohol. Alternatively, the oxidizing compound or a solution thereof may be added to a liquid in which nanodiamond having a graphite phase is dispersed in advance in the solvent. In order to promote the oxidation reaction by the oxidizing compound, a basic compound or an oxidizing compound may be added to the mixture A.
酸化性化合物としては、硝酸、過酸化水素、過炭酸ナトリウム、過炭酸カリウム、過ホウ酸ナトリウム、過ホウ酸カリウム、次亜塩素酸ナトリウム、次亜塩素酸カリウム、亜塩素酸ナトリウム、亜塩素酸カリウム、塩素酸リチウム、塩素酸ナトリウム、塩素酸カリウム、過塩素酸リチウム、過塩素酸ナトリウム、過塩素酸カリウム、過マンガン酸ナトリウム、過マンガン酸カリウム、マンガン酸ナトリウム、マンガン酸カリウム、過硫酸ナトリウム、過硫酸カリウム、重クロム酸カリウム、クロム酸カリウム等が挙げられ、硝酸及び過酸化水素が好ましい。特に酸化性化合物を単独で使用する場合は、過酸化水素を使用するのが最も好ましい。 Examples of oxidizing compounds include nitric acid, hydrogen peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium hypochlorite, potassium hypochlorite, sodium chlorite, chlorite Potassium, lithium chlorate, sodium chlorate, potassium chlorate, lithium perchlorate, sodium perchlorate, potassium perchlorate, sodium permanganate, potassium permanganate, sodium manganate, potassium manganate, sodium persulfate Potassium persulfate, potassium dichromate, potassium chromate and the like, and nitric acid and hydrogen peroxide are preferred. In particular, when an oxidizing compound is used alone, it is most preferable to use hydrogen peroxide.
酸性化合物としては、硝酸、硫酸、塩酸、リン酸、ホウ酸、フッ酸、臭化水素酸等の無機酸、及び蟻酸、酢酸、メタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸等の有機酸が挙げられ、無機酸が好ましく、硝酸がより好ましい。 Acidic compounds include inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, hydrofluoric acid, hydrobromic acid, and organic acids such as formic acid, acetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. An acid is mentioned, An inorganic acid is preferable and nitric acid is more preferable.
塩基性化合物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、四ホウ酸リチウム、四ホウ酸ナトリウム、四ホウ酸カリウム、アンモニア等が挙げられる。 Basic compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium tetraborate, sodium tetraborate, potassium tetraborate , Ammonia and the like.
酸化性化合物と酸性化合物とを組合せて使用する場合は、過酸化水素と硝酸との組合せが好ましく、酸化性化合物と塩基性化合物とを組合せて使用する場合は、過酸化水素とアンモニアとの組合せが好ましい。 A combination of hydrogen peroxide and nitric acid is preferable when using a combination of an oxidizing compound and an acidic compound, and a combination of hydrogen peroxide and ammonia is used when a combination of an oxidizing compound and a basic compound is used. Is preferred.
溶媒としては、水、アルコール又はこれらの混合液を用いる。アルコールとしては炭素数１〜３の低級アルコールが好ましい。低級アルコールの具体例として、メタノール、エタノール、n-プロパノール、イソプロパノール及びこれらの混合液が挙げられる。 As the solvent, water, alcohol or a mixture thereof is used. The alcohol is preferably a lower alcohol having 1 to 3 carbon atoms. Specific examples of the lower alcohol include methanol, ethanol, n-propanol, isopropanol, and a mixture thereof.
(b) 超臨界処理工程
混合物Aを溶媒の臨界点以上の温度及び圧力で処理する。処理温度は溶媒の臨界温度以上、600℃以下であるのが好ましく、550℃以下であるのがより好ましい。処理圧力は溶媒の臨界圧力以上、100 MPa以下であるのが好ましく、70 MPa以下であるのがより好ましく、50 MPa以下であるのが最も好ましい。処理時間は温度及び圧力により適宜設定すればよいが、１〜24時間が好ましい。
(b) Supercritical processing step Mixture A is processed at a temperature and pressure above the critical point of the solvent. The treatment temperature is preferably not lower than the critical temperature of the solvent and not higher than 600 ° C., more preferably not higher than 550 ° C. The treatment pressure is preferably not less than the critical pressure of the solvent and not more than 100 MPa, more preferably not more than 70 MPa, and most preferably not more than 50 MPa. The treatment time may be appropriately set depending on the temperature and pressure, but is preferably 1 to 24 hours.
(c) 脱溶媒工程
酸化処理Aと同様にして行う。
(c) Desolvation step Performed in the same manner as oxidation treatment A.
(d) 水洗工程
酸化処理Aと同様にして行う。
(d) Washing step Performed in the same manner as oxidation treatment A.
(e) 中和工程
工程(c)で脱溶媒した精製ダイヤモンド粒子を、水酸化ナトリウム、水酸化カリウム等の塩基で中和してもよい。塩基性溶液の濃度は0.01〜0.5 mol／Lが好ましい。脱溶媒した精製ダイヤモンド粒子に塩基性溶液を添加し、超音波処理するのが好ましい。
(e) Neutralization step The purified diamond particles removed in the step (c) may be neutralized with a base such as sodium hydroxide or potassium hydroxide. The concentration of the basic solution is preferably 0.01 to 0.5 mol / L. It is preferable to add a basic solution to the purified diamond particles from which the solvent has been removed, followed by ultrasonic treatment.
(f) 弱酸処理工程
工程(e)で中和した精製ダイヤモンド粒子を弱酸溶液で洗浄するのが好ましい。弱酸溶液の例として、0.01〜0.5 mol／Lの塩酸が挙げられる。中和した精製ダイヤモンド粒子に弱酸溶液を添加し、超音波処理するのが好ましい。
(f) Weak acid treatment step The purified diamond particles neutralized in step (e) are preferably washed with a weak acid solution. An example of a weak acid solution is 0.01 to 0.5 mol / L hydrochloric acid. It is preferable to add a weak acid solution to the neutralized purified diamond particles and sonicate.
(iii)酸化処理C
酸化処理Cは、(a) グラファイト相を有するナノダイヤモンドと、水及び／又はアルコールからなる溶媒とからなる混合物Bを調製し、(b) この混合物Bに酸素を共存させた状態で、処理溶媒の標準沸点以上の温度及び0.1 MPa（ゲージ圧）以上の圧力でグラファイト相を有するナノダイヤモンドを処理し、(c) 得られた精製ダイヤモンド粒子を含む液を遠心分離して溶媒を除去する工程を有する。さらに、脱処理溶媒した精製ダイヤモンド粒子を(d)水洗及び遠心分離により脱水する工程を設けるのが好ましい。工程(c)又は(d)で得られた精製ダイヤモンド粒子は乾燥して微粉末にする。
(iii) Oxidation treatment C
The oxidation treatment C comprises (a) preparing a mixture B composed of nanodiamond having a graphite phase and a solvent composed of water and / or alcohol, and (b) treating the solvent in a state where oxygen is present in the mixture B. (C) a step of removing the solvent by centrifuging the liquid containing the purified diamond particles and treating the nanodiamond having a graphite phase at a temperature higher than the normal boiling point and a pressure of 0.1 MPa (gauge pressure) or higher. Have. Further, it is preferable to provide (d) a step of dewatering the purified diamond particles that have been subjected to the detreatment solvent by water washing and centrifugation. The refined diamond particles obtained in step (c) or (d) are dried to a fine powder.
(a)混合物Bの調製工程
混合物Bは、グラファイト相を有するナノダイヤモンドと、水及び／又はアルコールからなる溶媒とを混合することにより調製する。混合物B中のグラファイト相を有するナノダイヤモンドの濃度は、0.05〜16質量％が好ましく、0.1〜12質量％がより好ましく、1〜10質量％が最も好ましい。この濃度が16質量％を超えると、精製が不十分となる恐れがある。一方0.05質量％未満であると、回収時のロスの割合が多くなり生産性が悪化する。
(a) Preparation Step of Mixture B The mixture B is prepared by mixing nanodiamond having a graphite phase and a solvent composed of water and / or alcohol. The concentration of the nanodiamond having a graphite phase in the mixture B is preferably 0.05 to 16% by mass, more preferably 0.1 to 12% by mass, and most preferably 1 to 10% by mass. If this concentration exceeds 16% by mass, purification may be insufficient. On the other hand, if it is less than 0.05% by mass, the ratio of loss at the time of recovery increases and productivity deteriorates.
溶媒としては、前記混合物Aの調製で用いることのできるものと同じものが使用できる。 As the solvent, the same solvents that can be used in the preparation of the mixture A can be used.
(b) 精製処理工程
混合物Bをオートクレーブに入れ、酸素を導入する。酸素の導入量は、グラファイト相を有するナノダイヤモンド中のグラファイト１ gに対して、0.1モル以上が好ましく、0.15モル以上がより好ましく、0.2モル以上が最も好ましい。この導入量の上限は特に制限されない。
(b) Purification treatment step Mixture B is placed in an autoclave and oxygen is introduced. The amount of oxygen introduced is preferably 0.1 mol or more, more preferably 0.15 mol or more, and most preferably 0.2 mol or more with respect to 1 g of graphite in the nanodiamond having a graphite phase. The upper limit of the introduction amount is not particularly limited.
処理溶媒の標準沸点Tb以上及び0.1 MPa（ゲージ圧）以上となるように、オートクレーブ内の温度及び圧力を調整する。処理溶媒のTb以上及び0.1 MPa（ゲージ圧）以上にする限り、処理溶媒を亜臨界状態［Tb以上の温度及び0.1 MPa（ゲージ圧）以上の圧力で、かつ臨界温度Tc未満及び／又は臨界圧力Pc未満の状態］にしてもよいし、超臨界状態にしてもよい。亜臨界又は超臨界状態の酸素及び処理溶媒により、グラファイト相を効率的に選択酸化することができる。 The temperature and pressure in the autoclave are adjusted so that the standard boiling point Tb and 0.1 MPa (gauge pressure) of the processing solvent will be exceeded. As long as the processing solvent is Tb or higher and 0.1 MPa (gauge pressure) or higher, the processing solvent is in a subcritical state [temperature of Tb or higher and pressure of 0.1 MPa (gauge pressure) or lower, and / or lower than the critical temperature Tc. It may be in a state less than Pc] or in a supercritical state. The graphite phase can be efficiently selectively oxidized by subcritical or supercritical oxygen and the processing solvent.
処理温度の下限は（処理溶媒の臨界温度Tc-150℃）が好ましく、（Tc−100℃）がより好ましい。処理温度の上限は800℃が好ましく、600℃がより好ましい。処理圧力の下限は、処理溶媒の臨界圧力Pcの30％が好ましく、Pcの50％がより好ましく、Pcの70％が最も好ましい。処理圧力の上限は70 MPaが好ましく、50 MPaがより好ましい。処理時間は温度及び圧力により適宜設定すればよいが、0.1〜24時間が好ましい。 The lower limit of the treatment temperature is preferably (critical temperature of treatment solvent Tc-150 ° C), more preferably (Tc-100 ° C). The upper limit of the treatment temperature is preferably 800 ° C, more preferably 600 ° C. The lower limit of the processing pressure is preferably 30% of the critical pressure Pc of the processing solvent, more preferably 50% of Pc, and most preferably 70% of Pc. The upper limit of the treatment pressure is preferably 70 MPa, more preferably 50 MPa. The treatment time may be appropriately set depending on the temperature and pressure, but is preferably 0.1 to 24 hours.
(c) 脱溶媒工程
酸化処理Aと同様にして行う。
(c) Desolvation step Performed in the same manner as oxidation treatment A.
(d) 水洗工程
酸化処理Aと同様にして行う。
(d) Washing step Performed in the same manner as oxidation treatment A.
(iv)酸化処理D
酸化処理Dは、前記グラファイト相を有するナノダイヤモンドを反応管に入れ、常圧下で酸素を含む気体を流しながら380〜450℃に加熱する工程を有する。加熱温度は400〜430℃であるのが好ましい。酸素を含む気体は、酸素ガス、空気等を使用できるが、簡便さから空気が好ましい。
(iv) Oxidation treatment D
The oxidation treatment D includes a step of putting nanodiamond having the graphite phase into a reaction tube and heating to 380 to 450 ° C. while flowing a gas containing oxygen under normal pressure. The heating temperature is preferably 400 to 430 ° C. As the gas containing oxygen, oxygen gas, air, or the like can be used, but air is preferable for simplicity.
(3)メディア分散処理
酸化処理を効率よく行い、着色の少ない精製ダイヤモンド粒子を得るために、酸化処理B〜Dの前にBD又はグラファイト-ダイヤモンド粒子をビーズミル等の公知のメディア分散法により粉砕するのが好ましい。ビーズミルによる分散は、ジルコニアビーズを使用するのが好ましい。BD又はグラファイト-ダイヤモンド粒子をメディア分散することにより、メジアン径を100 nm以下にするのが好ましく、50 nm以下にするのがより好ましく、30 nm以下にするのが最も好ましい。
(3) Media dispersion treatment BD or graphite-diamond particles are pulverized by a known media dispersion method such as a bead mill before oxidation treatment B to D in order to efficiently carry out oxidation treatment and obtain purified diamond particles with less coloring. Is preferred. For dispersion by a bead mill, zirconia beads are preferably used. By dispersing the media of BD or graphite-diamond particles, the median diameter is preferably 100 nm or less, more preferably 50 nm or less, and most preferably 30 nm or less.
[2]ケイ素化処理
前記***法で得られた未精製のナノダイヤモンド、又は前記酸化処理して得られたナノダイヤモンドに、シリル化剤、アルコキシシラン、シランカップリング剤等を反応させることによりナノダイヤモンドの表面にある水酸基等の親水性基を、ケイ素を含む有機基に置換することができる。ケイ素化処理は、シリル化剤を用いるのが好ましい。
[2] Siliconation treatment By reacting unpurified nanodiamond obtained by the above-mentioned explosion method or nanodiamond obtained by the above oxidation treatment with a silylating agent, alkoxysilane, silane coupling agent, or the like. A hydrophilic group such as a hydroxyl group on the surface of the nanodiamond can be substituted with an organic group containing silicon. In the siliconization treatment, a silylating agent is preferably used.
好ましいシリル化剤としては、トリエチルクロロシラン、トリメチルクロロシラン、ジエチルジクロロシラン、ジメチルジクロロシラン、アセトキシトリメチルシラン、アセトキシシラン、ジアセトキシジメチルシラン、メチルトリアセトキシシラン、フェニルトリアセトキシシラン、ジフェニルジアセトキシシラン、トリメチルエトキシシラン、トリメチルメトキシシラン、2-トリメチルシロキシペント-2-エン-4-オン、n-（トリメチルシリル）アセトアミド、2-（トリメチルシリル）酢酸、n-（トリメチルシリル）イミダゾール、トリメチルシリルプロピオレート、ノナメチルトリシラザン、ヘキサメチルジシラザン、ヘキサメチルジシロキサン、トリメチルシラノール、トリエチルシラノール、トリフェニルシラノール、t-ブチルジメチルシラノール、ジフェニルシランジオール等が挙げられる。本発明に用いられるシリル化剤は、これらの化合物に限定されない。 Preferred silylating agents include triethylchlorosilane, trimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, acetoxytrimethylsilane, acetoxysilane, diacetoxydimethylsilane, methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldiacetoxysilane, trimethylethoxy Silane, trimethylmethoxysilane, 2-trimethylsiloxypent-2-en-4-one, n- (trimethylsilyl) acetamide, 2- (trimethylsilyl) acetic acid, n- (trimethylsilyl) imidazole, trimethylsilylpropiolate, nonamethyltrisilazane , Hexamethyldisilazane, hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilane Examples include lanol and diphenylsilanediol. The silylating agent used in the present invention is not limited to these compounds.
シリル化剤溶液の溶媒はヘキサン、シクロヘキサン、ペンタン、ヘプタン等の炭化水素類、アセトン、メチルイソブチルケトン等のケトン類、ベンゼン、トルエン等の芳香族化合物が好ましい。 The solvent of the silylating agent solution is preferably a hydrocarbon such as hexane, cyclohexane, pentane or heptane, a ketone such as acetone or methyl isobutyl ketone, or an aromatic compound such as benzene or toluene.
シリル化剤の種類や濃度にもよるが、シリル化反応は10〜40℃で十分攪拌しながら進行させるのが好ましい。10℃未満では反応が進行しにくく、40℃超ではナノダイヤモンド表面に均一にシリル化されなくなる。例えば、トリエチルクロロシランのヘキサン溶液をシリル化剤として使用した場合、10〜40℃で10〜40時間程度攪拌しながら反応させると、ナノダイヤモンド表面の水酸基が十分にシリル修飾される。 Although depending on the type and concentration of the silylating agent, the silylation reaction is preferably allowed to proceed at 10 to 40 ° C. with sufficient stirring. If it is less than 10 ° C., the reaction hardly proceeds, and if it exceeds 40 ° C., it is not uniformly silylated on the nanodiamond surface. For example, when a hexane solution of triethylchlorosilane is used as a silylating agent, the hydroxyl group on the surface of the nanodiamond is sufficiently silyl modified by reacting at 10 to 40 ° C. with stirring for about 10 to 40 hours.
[3]フッ素化処理
前記***法で得られた未精製のナノダイヤモンド、又は前記酸化処理により得られたナノダイヤモンドは、フルオロアルキル基含有オリゴマーを使用した方法、フッ素ガスと直接反応させる方法、フッ素プラズマによる方法等により、その表面をフッ素又はフッ素を有する基で修飾することができる。
[3] Fluorination treatment The unpurified nanodiamond obtained by the explosion method or the nanodiamond obtained by the oxidation treatment is a method using a fluoroalkyl group-containing oligomer, a method of directly reacting with fluorine gas, The surface can be modified with fluorine or a fluorine-containing group by a method using fluorine plasma or the like.
(1)フルオロアルキル基含有オリゴマーを使用した方法
高分子主鎖の両末端にフルオロアルキル基が直接炭素−炭素結合により導入された高分子界面活性剤（含フッ素オリゴマー）は、水溶液中又は有機溶媒中において自己組織化したナノレベルの分子集合体を形成することが知られている。このフルオロアルキル基が末端に導入された含フッ素オリゴマーを用いることにより、フルオロアルキル基で修飾したナノダイヤモンドを形成することができる。
(1) Method using a fluoroalkyl group-containing oligomer A polymer surfactant (fluorinated oligomer) in which a fluoroalkyl group is directly introduced into both ends of a polymer main chain by a carbon-carbon bond is used in an aqueous solution or an organic solvent. It is known to form nano-level molecular assemblies that are self-assembled therein. By using this fluorine-containing oligomer having a fluoroalkyl group introduced at the terminal, nanodiamonds modified with a fluoroalkyl group can be formed.
フルオロアルキル基で修飾したナノダイヤモンドは、***法で得られた未精製のナノダイヤモンド、又は前記酸化処理により得られたナノダイヤモンドを、一般式(1)で表される含フッ素オリゴマーで処理することによって得ることができる。 For nanodiamonds modified with a fluoroalkyl group, unpurified nanodiamonds obtained by the explosion method or nanodiamonds obtained by the oxidation treatment are treated with a fluorine-containing oligomer represented by the general formula (1). Can be obtained.
ここで、RFはフルオロアルキル基であり、具体的には、-CF(CF3)OC3F7、-CF(C3F)OCF2CF(CF3)OC3F7等の基が好ましい。Rは置換基であり、-N(CH3)2、-OH、-NHC(CH3)2CH2C(=O)CH3、-Si(OCH3)3、-COOH等の基が好ましい。nは５〜2000であるのが好ましい。 Here, R F is a fluoroalkyl group, specifically, a group such as —CF (CF 3 ) OC 3 F 7 , —CF (C 3 F) OCF 2 CF (CF 3 ) OC 3 F 7, etc. preferable. R is a substituent, and groups such as —N (CH 3 ) 2 , —OH, —NHC (CH 3 ) 2 CH 2 C (═O) CH 3 , —Si (OCH 3 ) 3 , —COOH, etc. are preferred. . n is preferably 5 to 2000.
ナノダイヤモンドと一般式(1)で表される含フッ素オリゴマーとをメタノール、エタノール等のアルコール溶媒中で混合し、室温〜80℃で2〜48時間撹拌することによりナノダイヤモンド表面にフルオロアルキル基(RF)が修飾された複合粒子を高い収率で得ることができる。反応を促進させるために、アンモニア等の塩基を使用してもよい。 The nano-diamond and the fluorine-containing oligomer represented by the general formula (1) are mixed in an alcohol solvent such as methanol and ethanol, and stirred at room temperature to 80 ° C. for 2 to 48 hours to form a fluoroalkyl group ( Composite particles modified with R F ) can be obtained in high yield. To accelerate the reaction, a base such as ammonia may be used.
(2)フッ素ガスと直接反応させる方法
フッ素ガスと直接反応させる方法は、ナノダイヤモンドを入れた反応管（ニッケル製等）に、フッ素ガスとアルゴン等の不活性ガスとの混合ガスを300〜500℃で10〜500時間流すことにより行う。
(2) Method of reacting directly with fluorine gas The method of reacting directly with fluorine gas is to mix a mixed gas of fluorine gas and inert gas such as argon in a reaction tube (made of nickel, etc.) containing nano diamond. It is carried out by flowing at a temperature of 10 to 500 hours.
フッ素化ダイヤモンド微粒子のフッ素含有量は0.1〜20 wt％であるのが好ましく、0.2〜15 wt％であるのが好ましい。フッ素含有量が0.1 wt％未満であると、フッ素含有の高分子樹脂を用いたとき、樹脂との相溶性が低下する。フッ素含有量が20 wt％以上であると、非フッ素系の溶剤や添加剤との相溶性が低下する。 The fluorine content of the fluorinated diamond fine particles is preferably 0.1 to 20 wt%, and preferably 0.2 to 15 wt%. When the fluorine content is less than 0.1 wt%, compatibility with the resin is reduced when a fluorine-containing polymer resin is used. When the fluorine content is 20 wt% or more, the compatibility with non-fluorinated solvents and additives decreases.
本発明を実施例によりさらに詳細に説明するが、本発明はそれらに限定されるものではない。 The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
実施例1
(1)ナノダイヤモンドの作製
TNT(トリニトロトルエン)とRDX（シクロトリメチレントリニトロアミン）を60/40の比で含む0.65 kgの爆発物を３ m3の爆発チャンバー内で爆発させて生成するBDを保存するための雰囲気を形成した後、同様の条件で２回目の爆発を起こしBDを合成した。爆発生成物が膨張し熱平衡に達した後、15 mmの断面を有する超音速ラバルノズルを通して35秒間ガス混合物をチャンバーより流出させた。チャンバー壁との熱交換及びガスにより行われた仕事（断熱膨張及び気化）のため、生成物の冷却速度は280℃/分であった。サイクロンで捕獲した生成物（黒色の粉末、BD）の比重は2.55 g/cm3、メジアン径（動的光散乱法）は220 nmであった。このBDは比重から計算して、76体積％のグラファイト系炭素と24体積％のダイヤモンドからなっていると推定された。
Example 1
(1) Fabrication of nano diamond
An atmosphere for storing BD produced by detonating 0.65 kg of explosives containing TNT (trinitrotoluene) and RDX (cyclotrimethylenetrinitroamine) in a ratio of 60/40 in a 3 m 3 explosion chamber. After formation, BD was synthesized by causing a second explosion under the same conditions. After the explosion product expanded and reached thermal equilibrium, the gas mixture was allowed to flow out of the chamber for 35 seconds through a supersonic Laval nozzle with a 15 mm cross section. Due to the heat exchange with the chamber walls and the work done by the gas (adiabatic expansion and vaporization), the product cooling rate was 280 ° C./min. The product (black powder, BD) captured by the cyclone had a specific gravity of 2.55 g / cm 3 and a median diameter (dynamic light scattering method) of 220 nm. This BD was calculated from specific gravity, and was estimated to be composed of 76% by volume of graphite-based carbon and 24% by volume of diamond.
このBDを60質量％硝酸水溶液と混合し、160℃、14気圧、20分の条件で酸化性分解処理を行った後、130℃、13気圧、1時間で酸化性エッチング処理を行った。酸化性エッチング処理により、BDからグラファイトが一部除去された粒子が得られた。この粒子を、アンモニアを用いて、210℃、20気圧、20分還流し中和処理した後、自然沈降させデカンテーションにより35質量％硝酸での洗浄を行い、さらにデカンテーションにより３回水洗し、遠心分離により脱水し、120℃で加熱乾燥し、グラファイト相を有するナノダイヤモンドの粉末を得た。このナノダイヤモンドの粉末の比重は3.38 g/cm3であり、メジアン径は5.5μm（動的光散乱法）であった。比重から計算して、90体積％のダイヤモンドと10体積％のグラファイト系炭素からなっていると推定された。 This BD was mixed with a 60% by mass nitric acid aqueous solution, subjected to an oxidative decomposition treatment at 160 ° C. and 14 atm for 20 minutes, and then an oxidative etching treatment at 130 ° C. and 13 atm for 1 hour. Particles from which graphite was partially removed from BD were obtained by oxidizing etching treatment. The particles were refluxed with ammonia at 210 ° C., 20 atm for 20 minutes, neutralized, then naturally settled, washed with 35% by mass nitric acid by decantation, and further washed with water three times by decantation. The powder was dehydrated by centrifugation and dried by heating at 120 ° C. to obtain nanodiamond powder having a graphite phase. The specific gravity of the nanodiamond powder was 3.38 g / cm 3 and the median diameter was 5.5 μm (dynamic light scattering method). Calculated from the specific gravity, it was estimated to be composed of 90 vol% diamond and 10 vol% graphite carbon.
(2)ケイ素化処理
得られたナノダイヤモンドの粉末をメチルイソブチルケトンに３質量%の濃度で分散させ、トリメチルクロロシランのメチルイソブチルケトン溶液（濃度7.5質量％）を１：１の容量で加え、48時間撹拌してナノダイヤモンドをトリメチルシランで修飾した。得られた分散物をメチルイソブチルケトンで洗浄後、乾燥し、トリメチルシラン修飾ナノダイヤモンド粉末を得た。
(2) Siliconation treatment The obtained nanodiamond powder was dispersed in methyl isobutyl ketone at a concentration of 3% by mass, and a methyl isobutyl ketone solution of trimethylchlorosilane (concentration 7.5% by mass) was added at a volume of 1: 1. The nanodiamond was modified with trimethylsilane by stirring for a period of time. The obtained dispersion was washed with methyl isobutyl ketone and then dried to obtain trimethylsilane-modified nanodiamond powder.
(3)ポリエステル樹脂の合成
テレフタル酸ジメチルエステル80部、エチレングリコ-ル58部、酢酸マンガン4水和物0.029部、三酸化アンチモン0.028部を反応器に仕込み、撹拌しながら窒素雰囲気下で200℃に加熱した。副生するメタノ-ルを除去しつつ235℃まで昇温した。メタノ-ルの副生が終了後トリメチルリン酸0.03部を添加し、285℃に昇温しながら0.3 Torrに減圧し固有粘度0.62のPETを得た。なお、固有粘度は、ポリエステルをフェノール/1,1,2,2-テトラクロロエタン混合溶媒(質量比：60/40)に溶解した0.2g/dl、0.6g/dl、1.0g/dlの溶液を、ウベローデ粘度計を用いて20℃で測定し、濃度に対し粘度をプロットし、濃度＝0に外挿したときの値である。
(3) Synthesis of polyester resin 80 parts of dimethyl terephthalate, 58 parts of ethylene glycol, 0.029 part of manganese acetate tetrahydrate and 0.028 part of antimony trioxide were charged into a reactor and stirred at 200 ° C under a nitrogen atmosphere. Heated. The temperature was raised to 235 ° C. while removing by-product methanol. After completion of the by-production of methanol, 0.03 part of trimethyl phosphoric acid was added, and the pressure was reduced to 0.3 Torr while raising the temperature to 285 ° C. to obtain PET having an intrinsic viscosity of 0.62. The intrinsic viscosity is 0.2 g / dl, 0.6 g / dl, 1.0 g / dl in which polyester is dissolved in a phenol / 1,1,2,2-tetrachloroethane mixed solvent (mass ratio: 60/40). It is a value when measured at 20 ° C. using an Ubbelohde viscometer, the viscosity plotted against the concentration, and extrapolated to concentration = 0.
(4) 高表面硬度フィルムの作製
二軸押出混練機を用いて、得られたPETを100重量部と、コロイダルシリカ(東芝シリコーン社製、UVHC-1105)10重量部と、得られたトリメチルシラン修飾ナノダイヤモンド粉末5質量部とを280℃から320℃に昇温しながら、20分間溶融混練した。この混練物を、平均目開きが10μmのステンレス鋼細線フィルターでろ過し、3 mmのスリット状ダイを通して表面温度60℃の回転冷却ドラム上に押出し、急冷して未延伸フィルムを得た。
(4) Production of high surface hardness film Using a twin screw extrusion kneader, 100 parts by weight of the obtained PET, 10 parts by weight of colloidal silica (manufactured by Toshiba Silicone, UVHC-1105), and the obtained trimethylsilane 5 parts by mass of the modified nanodiamond powder was melt-kneaded for 20 minutes while raising the temperature from 280 ° C to 320 ° C. This kneaded product was filtered with a stainless steel fine wire filter having an average opening of 10 μm, extruded through a 3 mm slit die onto a rotary cooling drum having a surface temperature of 60 ° C., and rapidly cooled to obtain an unstretched film.
得られた未延伸フィルムを120℃にて予熱し、さらに低速及び高速のロール間でフィルム温度が140℃となるようにIRヒーターにて上下から加熱して、連続製膜方向(MD方向)に3.3倍に延伸した。続いてテンターに供給し、145℃にて連続製膜方向と垂直な方向(TD方向)に3.5倍に延伸した。得られた二軸配向フィルムを240℃の温度で熱固定し厚み100μmの高表面硬度フィルムを得た。 The obtained unstretched film is preheated at 120 ° C, and further heated from above and below with an IR heater so that the film temperature is 140 ° C between low and high speed rolls, in the continuous film forming direction (MD direction). Stretched 3.3 times. Subsequently, the film was supplied to a tenter and stretched 3.5 times in a direction (TD direction) perpendicular to the continuous film forming direction at 145 ° C. The obtained biaxially oriented film was heat-set at a temperature of 240 ° C. to obtain a high surface hardness film having a thickness of 100 μm.
実施例２
二軸押出混練機を用いて、実施例１で得られたPETを280℃から320℃に昇温しながら、20分間溶融させた。
Example 2
The PET obtained in Example 1 was melted for 20 minutes while the temperature was raised from 280 ° C. to 320 ° C. using a biaxial extrusion kneader.
一方で、別の二軸押出混練機を用いて、実施例１で得られたPETを100重量部と、コロイダルシリカ(東芝シリコーン社製、UVHC-1105)10重量部と、得られたトリメチルシラン修飾ナノダイヤモンド粉末5質量部とを280℃から320℃に昇温しながら、20分間溶融混練した。 On the other hand, using another biaxial extrusion kneader, 100 parts by weight of the PET obtained in Example 1, 10 parts by weight of colloidal silica (UVHC-1105, manufactured by Toshiba Silicone Co., Ltd.), and the obtained trimethylsilane 5 parts by mass of the modified nanodiamond powder was melt-kneaded for 20 minutes while raising the temperature from 280 ° C to 320 ° C.
得られたPET溶融物と、混練物とを、各二軸押出機から平均目開きが10μmのステンレス鋼細線フィルターを通し、二層用Tダイから、PET/混練物＝80/20となるように、表面温度60℃の回転冷却ドラム上に押出し、急冷して未延伸フィルムを得た。 The obtained PET melt and kneaded product are passed through a stainless steel fine wire filter having an average opening of 10 μm from each twin-screw extruder, and from a T-die for two layers, PET / kneaded product = 80/20 Then, it was extruded onto a rotary cooling drum having a surface temperature of 60 ° C. and rapidly cooled to obtain an unstretched film.
得られた未延伸フィルムを120℃にて予熱し、さらに低速及び高速のロール間でフィルム温度が140℃となるようにIRヒーターにて上下から加熱して、連続製膜方向(MD方向)に3.3倍に延伸した。続いてテンターに供給し、145℃にて連続製膜方向と垂直な方向(TD方向)に3.5倍に延伸した。得られた二軸配向フィルムを240℃の温度で熱固定し厚み100μmの高表面硬度フィルムを得た。この高表面硬度フィルムは、80μmのPET層（基材）と、20μmの高硬度層（PET＋コロイダルシリカ＋トリメチルシラン修飾ナノダイヤモンド）とが積層されたフィルムであった。 The obtained unstretched film is preheated at 120 ° C, and further heated from above and below with an IR heater so that the film temperature is 140 ° C between low and high speed rolls, in the continuous film forming direction (MD direction). Stretched 3.3 times. Subsequently, the film was supplied to a tenter and stretched 3.5 times in a direction (TD direction) perpendicular to the continuous film forming direction at 145 ° C. The obtained biaxially oriented film was heat-set at a temperature of 240 ° C. to obtain a high surface hardness film having a thickness of 100 μm. This high surface hardness film was a film in which an 80 μm PET layer (base material) and a 20 μm high hardness layer (PET + colloidal silica + trimethylsilane modified nanodiamond) were laminated.
実施例３
基材フィルムとして、ポリエチレンテレフタレートフィルム(東洋紡社製、O-PET、75μm)の表面にスパッタリングで100 nmのITO層を形成させたシートを上部電極として得た。この上部電極の表面固有抵抗は300Ω/cm2であった。
Example 3
As a base film, a sheet in which a 100 nm ITO layer was formed by sputtering on the surface of a polyethylene terephthalate film (Toyobo Co., Ltd., O-PET, 75 μm) was obtained as an upper electrode. The surface resistivity of the upper electrode was 300 Ω / cm 2 .
この基材フィルムに、厚みを20μmとした以外は実施例１と同様にして作製した高硬度フィルムを加熱法により積層し、高表面硬度フィルムを作製した。 A high-hardness film produced in the same manner as in Example 1 except that the thickness was 20 μm was laminated on this base film by a heating method to produce a high-surface hardness film.
実施例４〜６
(1)フッ素化処理
実施例１で作製したナノダイヤモンドの粉末を３質量%の濃度でメタノールに分散させ、下記式：
Examples 4-6
(1) Fluorination treatment The nanodiamond powder prepared in Example 1 was dispersed in methanol at a concentration of 3% by mass, and the following formula:
（RFは-CF(CF3)OC3F7基、Rは-OH基、nは約800である。）表される含フッ素オリゴマー、及び28質量%アンモニア水を、ナノダイヤモンド分散物100質量部に対してそれぞれ50質量部及び10質量部加え、80℃で20時間撹拌して反応させた。得られた分散物を中和、洗浄及び乾燥し、ナノダイヤモンド表面がフルオロアルキル基で修飾された複合粒子を得た。 (R F is —CF (CF 3 ) OC 3 F 7 group, R is —OH group, and n is about 800.) The fluorine-containing oligomer represented, and 28% by mass of ammonia water were added to the nanodiamond dispersion 100. 50 parts by mass and 10 parts by mass were added to each part by mass, and the mixture was stirred at 80 ° C. for 20 hours for reaction. The obtained dispersion was neutralized, washed and dried to obtain composite particles in which the nanodiamond surface was modified with a fluoroalkyl group.
(2) 高表面硬度フィルムの作製
トリメチルシラン修飾ナノダイヤモンド粉末の添加量の40質量%をフルオロアルキル基修飾ナノダイヤモンド粉末に置き換えた以外実施例１〜３と同様にして、高表面硬度フィルムを作製した。
(2) Production of high surface hardness film A high surface hardness film was produced in the same manner as in Examples 1 to 3 except that 40% by mass of the addition amount of trimethylsilane-modified nanodiamond powder was replaced with fluoroalkyl group-modified nanodiamond powder. did.
実施例７〜９
(1)ケイ素化及びフッ素化
実施例１で作製したトリメチルシラン修飾ナノダイヤモンド分散物を用いて、実施例２と同様にして、ナノダイヤモンド表面をフルオロアルキル基で修飾し、ナノダイヤモンド表面がトリメチルシラン及びフルオロアルキル基で修飾された複合粒子を得た。
Examples 7-9
(1) Siliconation and fluorination Using the trimethylsilane-modified nanodiamond dispersion prepared in Example 1, the nanodiamond surface was modified with a fluoroalkyl group in the same manner as in Example 2, and the nanodiamond surface was trimethylsilane. And composite particles modified with fluoroalkyl groups were obtained.
(2) 高表面硬度フィルムの作製
トリメチルシラン修飾ナノダイヤモンド粉末の代わりに、トリメチルシラン及びフルオロアルキル基修飾ナノダイヤモンド粉末を使用した以外実施例１〜３と同様にして、高表面硬度フィルムを作製した。
(2) Production of high surface hardness film A high surface hardness film was produced in the same manner as in Examples 1 to 3 except that trimethylsilane and fluoroalkyl group-modified nanodiamond powder were used instead of trimethylsilane-modified nanodiamond powder. .
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