JP2017007299A - Laminate and method for manufacturing the same - Google Patents
Laminate and method for manufacturing the same Download PDFInfo
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- JP2017007299A JP2017007299A JP2015128274A JP2015128274A JP2017007299A JP 2017007299 A JP2017007299 A JP 2017007299A JP 2015128274 A JP2015128274 A JP 2015128274A JP 2015128274 A JP2015128274 A JP 2015128274A JP 2017007299 A JP2017007299 A JP 2017007299A
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- carbon nanotube
- laminate
- carbon
- resin
- molding
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Abstract
Description
本発明は、カーボンナノチューブと樹脂とを含んでなるカーボンナノチューブ含有層を有する積層体およびその製造方法に関する。 The present invention relates to a laminate having a carbon nanotube-containing layer comprising a carbon nanotube and a resin, and a method for producing the same.
直径が数ナノメートルから数十ナノメートルの筒状炭素材料であるカーボンナノチューブは、高い導電性、機械的強度を有することから、燃料電池、電極、電磁波シールド材、導電性樹脂、電界放出ディスプレー（ＦＥＤ）用部材、水素を始めとする各種ガスの吸蔵材料などの機能性材料として、エレクトロニクス、エネルギー分野等の幅広い分野への利用が期待されている。 Carbon nanotubes, which are cylindrical carbon materials with a diameter of several nanometers to several tens of nanometers, have high electrical conductivity and mechanical strength. Therefore, fuel cells, electrodes, electromagnetic wave shielding materials, conductive resins, field emission displays ( It is expected to be used in a wide range of fields such as electronics and energy as functional materials such as FED) members and various gas storage materials such as hydrogen.
その中でも、カーボンナノチューブを用いた導電性透明フィルムの検討が多く行われている。例えば、透明基材の片面上にカーボンナノチューブ導電膜と透明保護膜を積層させたものが提案されている。（例えば、特許文献１参照） Among them, many studies have been conducted on conductive transparent films using carbon nanotubes. For example, what laminated | stacked the carbon nanotube electrically conductive film and the transparent protective film on the single side | surface of a transparent base material is proposed. (For example, see Patent Document 1)
また、カーボンナノチューブ分散体を基材表面に塗工し、乾燥させた後、樹脂溶液を塗工する導電性透明フィルムの製造方法も提案されている。（特許文献２参照） There has also been proposed a method for producing a conductive transparent film in which a carbon nanotube dispersion is coated on a substrate surface, dried, and then coated with a resin solution. (See Patent Document 2)
一方、カーボンナノチューブを色材として使用した例は少なく、漆黒性の樹脂塗工物、フィルム、成形物を得るためにはカーボンブラックを樹脂溶液や固形樹脂に均一に分散させたものを使用してきた。（特許文献３、４参照）しかし、当該手段においては、明度（Ｌ*）が高い（灰色・白）方向にあり、色度（a*、b*）がプラス方向（＋a*:赤、＋b*:黄）となり、いわゆる「ピアノブラック」や「カラスの濡れ羽色」といった漆黒性を表現することが困難であった。 On the other hand, there are few examples of using carbon nanotubes as a color material, and in order to obtain jet-black resin coatings, films, and moldings, carbon blacks uniformly dispersed in resin solutions and solid resins have been used. . However, in this means, the lightness (L * ) is in the high (gray / white) direction, and the chromaticity (a *, b *) is in the positive direction (+ a *: red, + b *: Yellow), and it was difficult to express jetness such as so-called “piano black” and “wet crow feathers”.
また、カーボンブラックを使用した成形物の色調はカーボンブラックの一次粒子径により異なる傾向にある。具体的には、一次粒子径が小さなカーボンブラックを使用すると、青味はあるが黒度が低下する。このように、黒色の着色は黒度と青味はトレードオフの関係にあるため、青味があって、かつ黒度が高い漆黒の色調を再現することは困難であった。 Further, the color tone of a molded product using carbon black tends to vary depending on the primary particle diameter of carbon black. Specifically, when carbon black having a small primary particle size is used, the blackness is lowered although it is bluish. Thus, since black coloration has a trade-off relationship between blackness and blueness, it has been difficult to reproduce a jet-black color tone that is bluish and has high blackness.
そこで、カーボンブラックの粒径や凝集粒サイズなどのコロイダル特性を変えたり、オゾン酸化、硝酸酸化といった表面処理をカーボンブラックに施し、分散体中での分散状態を変えるなどして、黒度の調製を行ってきた。（特許文献５、６、７参照）また、黒色に加えて青味をだすために、さらにフタロシアニンブルーなどの有機顔料を添加する方法もある。しかし、有機顔料の添加に伴い黒度が低下し、成形体を直射日光下で観察すると赤味が浮いて観察される、いわゆるブロンズ現象が発生する問題があった。 Therefore, the blackness is adjusted by changing the colloidal properties such as the particle size and aggregate particle size of the carbon black, or by applying surface treatment such as ozone oxidation and nitric acid oxidation to the carbon black and changing the dispersion state in the dispersion. I went. (See Patent Documents 5, 6, and 7) There is also a method of adding an organic pigment such as phthalocyanine blue in order to produce a bluish color in addition to black. However, there is a problem in that the blackness decreases with the addition of the organic pigment, and a so-called bronze phenomenon occurs in which a reddish color is observed when the molded body is observed under direct sunlight.
本発明は、上記従来の問題を解決するものであり、青味があり、かつ黒度の高い漆黒性に優れた積層体を提供することにある。 This invention solves the said conventional problem, and is providing the laminated body excellent in jetness with a bluishness and high blackness.
本発明者らは、上記課題を解決すべく鋭意検討した結果、カーボンナノチューブと樹脂を含む樹脂組成物を積層することにより、漆黒性に優れた樹脂組成物の積層体を得ることができることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a laminate of a resin composition having excellent jetness can be obtained by laminating a resin composition containing carbon nanotubes and a resin. The present invention has been reached.
すなわち、本発明は、カーボンナノチューブと樹脂とを含んでなるカーボンナノチューブ含有層と、クリア層とを有する積層体であって、クリア層の面方向から測定した積層体のＬ*が２６以下かつｂ*が−１０以上０．３以下であり、カーボンナノチューブ含有層が塗布以外の方法で形成されてなり、クリア層が透明樹脂またはガラスであることを特徴とする積層体に関する。
（ただし、Ｌ*およびｂ*は、ＪＩＳ Ｚ８７２９で規定されるＬ*ａ*ｂ*表色系における値を表わす。）
That is, the present invention is a laminate having a carbon nanotube-containing layer comprising a carbon nanotube and a resin, and a clear layer, wherein the laminate has an L * of 26 or less and b measured from the surface direction of the clear layer. The present invention relates to a laminate in which * is -10 or more and 0.3 or less, the carbon nanotube-containing layer is formed by a method other than coating, and the clear layer is a transparent resin or glass.
(However, L * and b * represent values in the L * a * b * color system defined by JIS Z8729.)
また、本発明は、塗布以外の方法が、押出成形、射出成形、ブロー成形、圧縮成形、トランスファー成形、インフレーション成形、またはカレンダー成形のいずれかの方法である前記積層体に関する。 The present invention also relates to the laminate, wherein the method other than coating is any one of extrusion molding, injection molding, blow molding, compression molding, transfer molding, inflation molding, or calendar molding.
また、本発明は、カーボンナノチューブの繊維径が、８〜２５ｎｍである前記積層体に関する。 The present invention also relates to the laminate, wherein the carbon nanotube has a fiber diameter of 8 to 25 nm.
本発明は、カーボンナノチューブ含有層中のカーボンナノチューブの量が、０．１〜１０質量％である前記積層体に関する。 The present invention relates to the laminate, wherein the amount of carbon nanotubes in the carbon nanotube-containing layer is 0.1 to 10% by mass.
また、本発明は、カーボンナノチューブ含有層の膜厚が、５０μｍ〜５ｍｍである前記積層体に関する。 Moreover, this invention relates to the said laminated body whose film thickness of a carbon nanotube content layer is 50 micrometers-5 mm.
本発明は、クリア層の膜厚が、５μｍ〜４０μｍである前記積層体に関する。 This invention relates to the said laminated body whose film thickness of a clear layer is 5 micrometers-40 micrometers.
また、本発明は、クリア層の面方向から測定した積層体の波長３８０〜７８０ｎｍにおける平均反射率が、１０％以下である前記積層体に関する。 Moreover, this invention relates to the said laminated body whose average reflectance in wavelength 380-780 nm of the laminated body measured from the surface direction of the clear layer is 10% or less.
本発明は、カーボンナノチューブと樹脂とを含んでなるカーボンナノチューブ含有層と、クリア層とを有する積層体の製造方法であって、クリア層の面方向から測定した積層体のＬ*が２６以下かつｂ*が−１０以上０．３以下であり、クリア層が透明樹脂またはガラスであり、カーボンナノチューブ含有層が塗布以外の方法により形成される前記積層体の製造方法に関する。 The present invention relates to a method for producing a laminate having a carbon nanotube-containing layer comprising carbon nanotubes and a resin, and a clear layer, wherein the L * of the laminate measured from the plane direction of the clear layer is 26 or less and It is related with the manufacturing method of the said laminated body by which b * is -10 or more and 0.3 or less, a clear layer is transparent resin or glass, and a carbon nanotube content layer is formed by methods other than application | coating.
また、本発明は、塗布以外の方法が、押出成形、射出成形、ブロー成形、圧縮成形、トランスファー成形、インフレーション成形、またはカレンダー成形のいずれかの方法である前記積層体の製造方法に関する。 The present invention also relates to a method for producing the laminate, wherein the method other than coating is any one of extrusion molding, injection molding, blow molding, compression molding, transfer molding, inflation molding, or calendar molding.
本発明の積層体を使用することにより、漆黒性に優れた積層体が得られる。よって、高い漆黒性が必要とされる様々な用途分野において、本発明で得られる積層体を使用することが可能である。 By using the laminate of the present invention, a laminate excellent in jetness can be obtained. Therefore, it is possible to use the laminate obtained by the present invention in various application fields where high jetness is required.
以下、本発明の積層体（ａ）について詳しく説明する。
本発明の積層体（ａ）は、カーボンナノチューブと樹脂とを含んでなるカーボンナノチューブ含有層と、クリア層とを有する積層体であって、クリア層の面方向から測定した積層体のＬ*が２６以下かつｂ*が−１０以上０．３以下であり、カーボンナノチューブ含有層が塗布以外の方法で形成されてなり、クリア層が透明樹脂またはガラスであることを特徴とする積層体である。
Hereinafter, the laminate (a) of the present invention will be described in detail.
The laminate (a) of the present invention is a laminate having a carbon nanotube-containing layer comprising carbon nanotubes and a resin, and a clear layer, and the L * of the laminate measured from the plane direction of the clear layer is 26 or less, b * is −10 or more and 0.3 or less, the carbon nanotube-containing layer is formed by a method other than coating, and the clear layer is a transparent resin or glass.
更に、前記積層体（ａ）のクリア層の面方向から測定した積層体のａ*が、−２以上６以下であることが好ましく、このようなＬ*、ａ*およびｂ*を示す積層体の場合、漆黒性に優れた積層体（ａ）となる。 Furthermore, it is preferable that a * of the laminate measured from the plane direction of the clear layer of the laminate (a) is −2 or more and 6 or less, and such a laminate showing L * , a * and b *. In this case, the laminate (a) is excellent in jetness.
ここで、Ｌ*、ａ*およびｂ*は、ＪＩＳ Ｚ８７２９で規定されるＬ*ａ*ｂ*表色系における値を表わし、前記積層体（ａ）のクリア層の面方向から、色差計（ＮＩＰＰＯＮＤＥＮＳＨＯＫＵ社製、ＳｐｅｃｔｒｏＣｏｌｏｒＭｅｔｅｒＳＥ２０００）を用いて測定することによって得られる。 Here, L * , a * and b * represent values in the L * a * b * color system defined by JIS Z8729. From the surface direction of the clear layer of the laminate (a), a color difference meter ( It is obtained by measuring using NIPPONDENSHOKU, SpectroColorMeterSE2000).
本発明の積層体は、カーボンナノチューブ含有層とクリア層とが、密着して積層されていなくても構わないが、これらの層が密着して積層されている方が、より漆黒性に優れた積層体（ａ）が得られる。 In the laminate of the present invention, the carbon nanotube-containing layer and the clear layer may not be laminated in close contact with each other, but it is more excellent in jetness when these layers are adhered and laminated. A laminate (a) is obtained.
一般的に、Ｌ*が小さい程、黒度が高い（明度が低い）ことを示す。a*とｂ*はゼロ（０）に近い値である程、黒い色相であるといえる。また、ｂ*がマイナスである程、青味（青色）が強い色相であるといえる。したがって、漆黒性という観点では、若干青味（青色）を有する黒色である場合が、漆黒性が高いと考えられるため、上記の数値範囲が好ましいと考えられる。 Generally, the smaller L * is, the higher the blackness (the lightness is low). It can be said that the closer the value of a * and b * is to zero (0), the darker the hue. Further, it can be said that the more b * is negative, the stronger the bluish (blue) hue. Therefore, from the viewpoint of jetness, since the case where the color is slightly bluish (blue) is considered to be high jetness, the above numerical range is considered preferable.
クリア層（ｅ）から測定した積層体の波長３８０〜７８０nmにおける平均反射率は１０％以下であることが好ましく、５％未満であることがさらに好ましい。特に斯かる範囲であれば、漆黒性に優れた積層体が得られる。 The average reflectance of the laminate measured from the clear layer (e) at a wavelength of 380 to 780 nm is preferably 10% or less, and more preferably less than 5%. If it is especially in such a range, the laminated body excellent in jetness will be obtained.
本発明のカーボンナノチューブ含有層（ｂ）について詳しく説明する。
本発明のカーボンナノチューブ含有層（ｂ）は、少なくともカーボンナノチューブ（ｃ）と樹脂（ｄ）とを含んでなるカーボンナノチューブ含有層（ｂ）であり、カーボンナノチューブ含有樹脂組成物（ｂ’）を塗布以外の方法で形成されてなることを特徴とする。
好ましい方法として、具体的には、押出成形、射出成形、ブロー成形、圧縮成形、トランスファー成形、Ｔ−ダイ成形やインフレーション成形のようなフィルム成形、カレンダー成形等を挙げることができる。
たとえば射出成形の場合、カーボンナノチューブ含有樹脂組成物（ｂ’）を溶融混練後、金型に射出することで、任意の形状のカーボンナノチューブ含有層（ｂ）を形成することができる。
The carbon nanotube-containing layer (b) of the present invention will be described in detail.
The carbon nanotube-containing layer (b) of the present invention is a carbon nanotube-containing layer (b) comprising at least the carbon nanotube (c) and the resin (d), and the carbon nanotube-containing resin composition (b ′) is applied. It is formed by methods other than.
Specific examples of preferable methods include extrusion molding, injection molding, blow molding, compression molding, transfer molding, film molding such as T-die molding and inflation molding, and calendar molding.
For example, in the case of injection molding, the carbon nanotube-containing layer (b) having an arbitrary shape can be formed by melting and kneading the carbon nanotube-containing resin composition (b ′) and then injecting it into a mold.
カーボンナノチューブ含有層（ｂ）の膜厚は５０μｍ〜５ｍｍであることが好ましく、１００μｍ〜３ｍｍであることがさらに好ましい。 The film thickness of the carbon nanotube-containing layer (b) is preferably 50 μm to 5 mm, and more preferably 100 μm to 3 mm.
本発明のカーボンナノチューブ含有層（ｂ）に用いられるカーボンナノチューブ（ｃ）について説明する。
カーボンナノチューブ（ｃ）は、グラファイトの１枚面を巻いて円筒状にした形状を有しており、そのグラファイト層が１層で巻いた構造を持つ単層カーボンナノチューブ、２層またはそれ以上で巻いた多層カーボンナノチューブでも、これらが混在するものであっても良いが、コスト面や着色効果の面から多層カーボンナノチューブであることが好ましい。また、カーボンナノチューブ（ｃ）の側壁がグラファイト構造ではなく、アモルファス構造をもったカーボンナノチューブ（ｃ）を用いることもできる。
The carbon nanotube (c) used for the carbon nanotube content layer (b) of this invention is demonstrated.
The carbon nanotube (c) has a shape in which one surface of graphite is wound into a cylindrical shape, and the single-walled carbon nanotube having a structure in which the graphite layer is wound in one layer is wound in two layers or more. These multi-walled carbon nanotubes may be mixed, but multi-walled carbon nanotubes are preferable from the viewpoint of cost and coloring effect. Further, carbon nanotubes (c) having an amorphous structure on the side wall of the carbon nanotubes (c) may be used instead of the graphite structure.
カーボンナノチューブ（ｃ）の形状は、針状、円筒チューブ状、魚骨状（フィッシュボーン、カップ積層型）、トランプ状（プレートレット）、コイル状の形態などいずれの形態を有するものであってもよい。具体的には、例えばグラファイトウィスカー、フィラメンタスカーボン、グラファイトファイバー、極細炭素チューブ、カーボンチューブ、カーボンフィブリル、カーボンマイクロチューブ、カーボンナノファイバーなどを挙げることができる。これらの形態として１種または２種以上を組み合わせた形態において使用することができる。本発明は魚骨状（フィッシュボーン、カップ積層型）、トランプ状（プレートレット）、コイル状以外の形態であることが好ましい。魚骨状、トランプ状の場合は、樹脂組成物・成形体の製造時に発生するせん断応力によりカップ・トランプ状グラファイトシートの積層面（ｘ−ｙ面）よりカーボンナノチューブ（ｂ）の切断が起こり、樹脂中に十分なネットワーク構造を形成できず、光閉じ込め効果が減少して黒度の低下に繋がる恐れがある。コイル状の場合も同様に、製造時にその３次元構造が破壊されやすく、着色効果が低下する可能性がある。 The shape of the carbon nanotube (c) may be any shape such as a needle shape, a cylindrical tube shape, a fish bone shape (fishbone, cup laminated type), a trump shape (platelet), and a coil shape. Good. Specific examples include graphite whiskers, filamentous carbon, graphite fibers, ultrafine carbon tubes, carbon tubes, carbon fibrils, carbon microtubes, and carbon nanofibers. These forms can be used in the form of one or a combination of two or more. The present invention is preferably in a form other than a fishbone shape (fishbone, cup laminate type), a trump shape (platelet), and a coil shape. In the case of a fish bone shape or a trump shape, the carbon nanotubes (b) are cut from the laminated surface (xy plane) of the cup / trump graphite sheet due to the shear stress generated during the production of the resin composition / molded body, A sufficient network structure cannot be formed in the resin, and the light confinement effect may decrease, leading to a decrease in blackness. Similarly, in the case of a coil shape, the three-dimensional structure is easily destroyed during manufacturing, and the coloring effect may be reduced.
本発明のカーボンナノチューブ（ｃ）は、一般にレーザーアブレーション法、アーク放電法、熱ＣＶＤ法、プラズマＣＶＤ法、燃焼法などで製造できるが、どのような方法で製造したカーボンナノチューブ（ｂ）でも構わない。例えば、触媒を用いて、酸素濃度が１体積％以下の雰囲気中、５００〜１０００℃にて、炭素源として炭化水素および／またはアルコールとを接触反応させてカーボンナノチューブ（ｃ）を製造することができる。 The carbon nanotube (c) of the present invention can be generally produced by a laser ablation method, an arc discharge method, a thermal CVD method, a plasma CVD method, a combustion method, etc., but the carbon nanotube (b) produced by any method may be used. . For example, a carbon nanotube (c) can be produced by catalytically reacting a hydrocarbon and / or alcohol as a carbon source at 500 to 1000 ° C. in an atmosphere having an oxygen concentration of 1% by volume or less using a catalyst. it can.
カーボンナノチューブ（ｃ）の炭素源としての原料ガスは、従来公知の任意のものを使用でき、例えば、炭素を含むガスとしてメタン、エチレン、プロパン、ブタンやアセチレン等の炭化水素や一酸化炭素、アルコールなどを用いることができるが、特に使いやすさの理由により、炭化水素やアルコールを用いることが望ましい。 As the raw material gas as the carbon source of the carbon nanotube (c), any conventionally known gas can be used. For example, as the gas containing carbon, hydrocarbons such as methane, ethylene, propane, butane and acetylene, carbon monoxide, alcohol However, it is desirable to use hydrocarbons or alcohols for reasons of ease of use.
触媒は、必要に応じて、還元性ガス雰囲気下で活性化した後、又は還元性ガスと共に、酸素濃度１体積％以下の雰囲気中、炭素源としての原料ガスと接触反応させて製造することが好ましい。酸素濃度１体積％以下の雰囲気は特に制限はないが、アルゴンガスのような希ガスや窒素ガス等の不活性ガスの雰囲気が好ましい。活性化に使用する還元性ガスとしては、水素、アンモニア等を用いることができるが、特に水素が好ましい。 If necessary, the catalyst may be produced after being activated in a reducing gas atmosphere, or together with the reducing gas, by contact reaction with a source gas as a carbon source in an atmosphere having an oxygen concentration of 1% by volume or less. preferable. The atmosphere with an oxygen concentration of 1% by volume or less is not particularly limited, but an atmosphere of an inert gas such as a rare gas such as argon gas or nitrogen gas is preferable. As the reducing gas used for the activation, hydrogen, ammonia or the like can be used, and hydrogen is particularly preferable.
触媒としては、従来公知の様々な金属酸化物を使用することができる。例えば、コバルト、ニッケルや鉄等の活性成分を含む金属とマグネシウム、アルミニウム等の担持成分を含む金属を組み合わせた触媒が挙げられる。 Various conventionally known metal oxides can be used as the catalyst. For example, a catalyst in which a metal containing an active component such as cobalt, nickel, or iron and a metal containing a supporting component such as magnesium or aluminum are combined.
カーボンナノチューブ（ｃ）の繊維径は、分散の容易さや色相の観点から、１〜５００ｎｍが好ましく、８〜２５ｎｍがより好ましい。 The fiber diameter of the carbon nanotube (c) is preferably 1 to 500 nm, more preferably 8 to 25 nm, from the viewpoint of ease of dispersion and hue.
カーボンナノチューブ（ｃ）の繊維径は、走査透過電子顕微鏡によって、カーボンナノチューブ（ｃ）を観測し、観測写真において、任意の１００個のカーボンナノチューブ（ｃ）を選び、それぞれの外径を計測し、その数平均値を求めることにより、カーボンナノチューブ（ｃ）の平均粒径（ｎｍ）を算出することにより測定できる。 The fiber diameter of the carbon nanotube (c) is observed with a scanning transmission electron microscope, the carbon nanotube (c) is observed, an arbitrary 100 carbon nanotubes (c) are selected in the observation photograph, and the outer diameter of each is measured, By obtaining the number average value, it can be measured by calculating the average particle diameter (nm) of the carbon nanotubes (c).
カーボンナノチューブ（ｃ）の繊維長は、分散の容易さや色相の観点から、０．１〜１５０μｍが好ましく、１〜１０μｍがより好ましい。 The fiber length of the carbon nanotube (c) is preferably 0.1 to 150 μm and more preferably 1 to 10 μm from the viewpoint of ease of dispersion and hue.
カーボンナノチューブ（ｃ）の炭素純度は、カーボンナノチューブ（ｃ）１００質量％中、８５質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上がさらに好ましい。 The carbon purity of the carbon nanotube (c) is preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more in 100% by mass of the carbon nanotube (c).
本発明でカーボンナノチューブ（ｃ）は、一般的に二次粒子として存在している。この二次粒子形状は、例えば一般的な一次粒子であるカーボンナノチューブ（ｃ）が複雑に絡み合っている状態でもよく、ほぐれ易くカーボンナノチューブ（ｃ）を直線状にしたものの集合体であっても良い。直線状のカーボンナノチューブ（ｃ）の集合体である二次粒子は絡み合っているものと比べると分散性が良いので好ましい。 In the present invention, the carbon nanotube (c) generally exists as secondary particles. The secondary particle shape may be, for example, a state where carbon nanotubes (c), which are general primary particles, are intricately intertwined, or may be an aggregate of carbon nanotubes (c) that are easily loosened and linear. . Secondary particles, which are aggregates of linear carbon nanotubes (c), are preferable because they have better dispersibility than those intertwined.
カーボンナノチューブ（ｃ）は、表面処理を行ったものや、カルボキシル基などの官能基を付与させたカーボンナノチューブ誘導体であってもよい。また、有機化合物や金属原子、フラーレン等を内包させたカーボンナノナノチューブ（ｃ）等も用いることができる。 The carbon nanotube (c) may be a surface-treated carbon nanotube derivative or a carbon nanotube derivative provided with a functional group such as a carboxyl group. In addition, carbon nano-nanotubes (c) encapsulating organic compounds, metal atoms, fullerenes, and the like can also be used.
カーボンナノチューブ含有層（ｂ）中のカーボンナノチューブ（ｃ）の量は、用途に応じて適宜選択すればよいが、好ましくは０．０１〜３０質量％、より好ましくは０．０５〜２０質量％、更に好ましくは０．１〜１０質量％の範囲である。特に斯かる範囲であれば、漆黒性に優れた積層体が得られる。 The amount of the carbon nanotube (c) in the carbon nanotube-containing layer (b) may be appropriately selected depending on the use, but is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, More preferably, it is the range of 0.1-10 mass%. If it is especially in such a range, the laminated body excellent in jetness will be obtained.
カーボンナノチューブ含有層（ｂ）には、本発明の目的を阻害しない範囲であれば、カーボンナノチューブ（ｃ）とカーボンブラックとを併用することができる。カーボンブラックの具体例としては、ケッチェンブラック、アセチレンブラック、ファーネスブラック、チャンネルブラック並びにナフサなどの炭化水素を水素及び酸素の存在下で部分酸化して、水素及び一酸化炭素を含む合成ガスを製造する際に副生するカーボンブラック、あるいはこれを酸化または還元処理したカーボンブラックなどが挙げられる。これらのカーボンブラックは、単独でも２種類以上併用しても良い。また、黒度を向上する視点から、カーボンブラックは平均粒径が２０ｎｍ以下で、かつ、ＤＢＰ吸油量が８０ｍｌ／１００ｇ以下のものが好ましく使用される。また、本発明においてＤＢＰ吸油量とは、カーボンブラック粒子間の化学的ないし物理的結合による複雑な凝集形態（ストラクチャー）の尺度で、カーボンブラック１００ｇ当りに包含することのできるジブチルフタレート（ＤＢＰ）の量（ｍｌ）を表す。 Carbon nanotubes (c) and carbon black can be used in combination in the carbon nanotube-containing layer (b) as long as the object of the present invention is not impaired. As specific examples of carbon black, hydrocarbons such as ketjen black, acetylene black, furnace black, channel black and naphtha are partially oxidized in the presence of hydrogen and oxygen to produce synthesis gas containing hydrogen and carbon monoxide. And carbon black produced as a by-product during oxidation, or carbon black obtained by oxidizing or reducing it. These carbon blacks may be used alone or in combination of two or more. From the viewpoint of improving blackness, carbon black having an average particle diameter of 20 nm or less and a DBP oil absorption of 80 ml / 100 g or less is preferably used. Further, in the present invention, the DBP oil absorption is a measure of a complex agglomeration form (structure) due to chemical or physical bonding between carbon black particles, and the dibutyl phthalate (DBP) that can be included per 100 g of carbon black. Represents volume (ml).
カーボンブラックの平均粒径は、カーボンナノチューブ（ｃ）の繊維径と同様の方法で求められる。具体的には、走査透過電子顕微鏡によって、カーボンブラックを観測し、観測写真において、任意の１００個のカーボンブラックを選び、それぞれの外径を計測し、その数平均値を求めることにより、カーボンブラックの平均粒径を算出することができる。 The average particle diameter of carbon black is determined by the same method as the fiber diameter of the carbon nanotube (c). Specifically, carbon black was observed with a scanning transmission electron microscope, and arbitrary 100 carbon blacks were selected in the observation photograph, each outer diameter was measured, and the number average value thereof was obtained. The average particle diameter can be calculated.
カーボンブラックの使用量は、カーボンナノチューブ（ｃ）１００重量部に対して、１〜１００重量部が好ましく、１〜５０重量部がより好ましく、１〜２５重量部がさらに好ましい。一方、１００重量部を超えると、成形体の黒度と青味が低下する可能性がある。青味が低下し、赤味が増すと、漆黒性に優れた積層体が得られにくい。 The amount of carbon black used is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and still more preferably 1 to 25 parts by weight with respect to 100 parts by weight of the carbon nanotube (c). On the other hand, if it exceeds 100 parts by weight, the blackness and bluishness of the molded product may be lowered. When blueness falls and redness increases, it is difficult to obtain a laminate having excellent jetness.
本発明のカーボンナノチューブ含有層（ｂ）に用いられる樹脂（ｄ）について説明する。
本発明に用いられる樹脂（ｄ）は、カーボンナノチューブ（ｃ）を分散安定化し、固定化させるバインダーとしての役割を担う。
The resin (d) used for the carbon nanotube-containing layer (b) of the present invention will be described.
The resin (d) used in the present invention plays a role as a binder for dispersing and stabilizing the carbon nanotube (c).
本発明に用いられる樹脂（ｄ）は、カーボンナノチューブを分散安定化する納涼があり、成形可能なものであれば特に制限されるものではないが、加熱溶融により成形可能な熱可塑性樹脂であることが好ましい。熱可塑性樹脂は、例えば、ポリエチレン（ＰＥ）樹脂、ポリプロピレン（ＰＰ）樹脂などのポリオレフィン系樹脂、ポリスチレン系樹脂、ポリフェニレンエーテル系樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリアセタール樹脂、ポリエステル系樹脂、ポリ塩化ビニル樹脂、アクリル樹脂、ポリエーテルイミド樹脂等が挙げられる。熱可塑性樹脂（Ａ）は、単独または２種類以上を併用できる。 The resin (d) used in the present invention is not particularly limited as long as it has a cooling effect to stabilize the dispersion of carbon nanotubes and can be molded, but is a thermoplastic resin that can be molded by heating and melting. Is preferred. Examples of the thermoplastic resin include polyolefin resins such as polyethylene (PE) resin and polypropylene (PP) resin, polystyrene resins, polyphenylene ether resins, polyethylene terephthalate (PET) resins, acrylonitrile-butadiene-styrene copolymer resins, Examples thereof include polycarbonate resin, polyamide resin, polyacetal resin, polyester resin, polyvinyl chloride resin, acrylic resin, and polyetherimide resin. The thermoplastic resin (A) can be used alone or in combination of two or more.
本発明のカーボンナノチューブ（ｃ）と樹脂（ｄ）からカーボンナノチューブ含有樹脂組成物（ｂ’）を作る方法としては、特に限定されるものではないが、一般的な高速せん断型混合機であるヘンシェルミキサーまたはスーパーミキサー等に投入し混合した後、二本ロール、三本ロール、加圧ニーダー、バンバリーミキサー、単軸混練押出し機または二軸混練押出し機等を用いて溶融混練を行いペレット状に押出し成形して得ることができる。
また、必要に応じて、例えば紫外線吸収剤、酸化防止剤、架橋剤、分散剤、などの添加剤を本発明の目的を阻害しない範囲で適宜配合することができる。
The method for producing the carbon nanotube-containing resin composition (b ′) from the carbon nanotube (c) and the resin (d) of the present invention is not particularly limited, but Henschel is a general high-speed shear mixer. After mixing and mixing in a mixer or super mixer, etc., it is melt-kneaded using a two-roll, three-roll, pressure kneader, Banbury mixer, single-screw kneading extruder or twin-screw kneading extruder, and extruded into pellets It can be obtained by molding.
Further, if necessary, additives such as an ultraviolet absorber, an antioxidant, a crosslinking agent, and a dispersing agent can be appropriately blended within a range that does not impair the object of the present invention.
本発明のクリア層（ｅ）について詳しく説明する。
本発明のクリア層（ｅ）はカーボンナノチューブ層（ｂ）を視認できる程度の透明性を有するものである。具体的には透明樹脂、ガラス等をあげることができる。透明樹脂としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）などのポリエステル、ポリイミド、ポリフェニレンスルフィド、アラミド、ポリプロピレン、ポリエチレン、ポリ乳酸、ポリ塩化ビニル、ポリカーボネート、ポリメタクリル酸メチル、脂環式アクリル樹脂、シクロオレフィン樹脂、トリアセチルセルロース、エポキシ樹脂、フェノール樹脂、アルキッド樹脂、石油樹脂、ビニル系樹脂、オレフィン樹脂、合成ゴム、ポリアミド樹脂、アクリル樹脂、スチレン樹脂、メラミン樹脂、ウレタン樹脂、アミノ樹脂、フッ素系樹脂、フッ化ビニリデン樹脂、塩化ビニル樹脂、ＡＢＳ樹脂、シリコーン系樹、ニトロセルロース、ロジン変性フェノール樹脂、ロジン変性ポリアミド樹脂、天然ゴム、ゼラチン、ロジン、セラック、多糖類、ギルソナイト等を挙げることができる。ガラスとしては、通常のソーダガラスを用いることができる。これらの複数の基材を組み合わせて用いることもできる。また、カーボンナノチューブ層（ｂ）を視認できる程度のカーボンブラックやカーボンナノチューブ（ｃ）が含まれても良い。
The clear layer (e) of the present invention will be described in detail.
The clear layer (e) of the present invention is transparent enough to visually recognize the carbon nanotube layer (b). Specific examples include transparent resin and glass. Transparent resins include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, and alicyclic acrylic. Resin, cycloolefin resin, triacetyl cellulose, epoxy resin, phenol resin, alkyd resin, petroleum resin, vinyl resin, olefin resin, synthetic rubber, polyamide resin, acrylic resin, styrene resin, melamine resin, urethane resin, amino resin, Fluorine resin, vinylidene fluoride resin, vinyl chloride resin, ABS resin, silicone resin, nitrocellulose, rosin modified phenolic resin, rosin modified polyamide resin, natural rubber, gela Down, rosin, mention may be made of shellac, polysaccharides, Gilsonite and the like. As the glass, ordinary soda glass can be used. A combination of these substrates can also be used. Carbon black and carbon nanotubes (c) that can visually recognize the carbon nanotube layer (b) may also be included.
クリア層（ｅ）を形成する方法としては、形成する物質により最適な方法を選択すれば良く、真空蒸着、EB蒸着、スパッタ蒸着などのドライ法、キャスト、スピンコート、ディップコート、バーコート、スプレー、ブレードコート、スリットダイコート、グラビアコート、リバースコート、スクリーン印刷、鋳型塗布、印刷転写、インクジェットなどのウエットコート法等、一般的な方法を挙げることができる。また、クリア層（ｅ）は製膜されたものをラミネートしても良い。 As a method for forming the clear layer (e), an optimum method may be selected depending on the material to be formed, and dry methods such as vacuum deposition, EB deposition, and sputter deposition, casting, spin coating, dip coating, bar coating, and spraying. General methods such as wet coating methods such as blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, print transfer, and inkjet can be used. The clear layer (e) may be laminated.
クリア層（ｅ）の膜厚は５〜４０μｍ、好ましくは２５〜３５μｍの範囲内であることが好ましい。特に斯かる範囲であれば、漆黒性に優れた積層体が得られる。 The film thickness of the clear layer (e) is 5 to 40 μm, preferably 25 to 35 μm. If it is especially in such a range, the laminated body excellent in jetness will be obtained.
以下に実施例を挙げて、本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。例中、特に断わりのない限り、「部」とは「質量部」、「％」とは「質量％」をそれぞれ意味する。また、「カーボンナノチューブ」を「ＣＮＴ」、「カーボンブラック」を「ＣＢ」と略記することがある。 EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified. Further, “carbon nanotube” may be abbreviated as “CNT”, and “carbon black” may be abbreviated as “CB”.
＜物性の測定方法＞
後述の各実施例及び比較例において使用された積層体の物性は、以下の方法により測定した。
<Method of measuring physical properties>
The physical properties of the laminates used in Examples and Comparative Examples described later were measured by the following methods.
＜膜厚＞
積層体中のカーボンナノチューブ含有層、クリア層の膜厚は膜厚計（ＮＩＫＯＮ社製、ＤＩＧＩＭＩＣＲＯ ＭＨ−１５Ｍ）を用いて、３点を測定し、その平均値を膜厚とした。
<Film thickness>
The film thickness of the carbon nanotube-containing layer and the clear layer in the laminate was measured at three points using a film thickness meter (manufactured by NIKON, DIGIMICRO MH-15M), and the average value was taken as the film thickness.
＜Ｌ*ａ*b*＞
積層体のクリア層の面方向から、色差計（ＮＩＰＰＯＮＤＥＮＳＨＯＫＵ社製、ＳｐｅｃｔｒｏＣｏｌｏｒＭｅｔｅｒＳＥ２０００）を用いてＪＩＳ Ｚ８７２９で規定されるＬ*ａ*ｂ*表色系における明度（Ｌ*）および色度（a*、b*）を測定した。
<L * a * b * >
From the surface direction of the clear layer of the laminate, L * a * b * color values (L * ) and chromaticity (a *, chromaticity) defined by JIS Z8729 using a color difference meter (manufactured by NIPPONDENSHOKU, SpectroColorMeterSE2000) b *) was measured.
＜平均反射率＞
紫外可視近赤外分光光度計（日立製作所社製、ＵＶ−３５００、積分球使用）を用い、積層体のクリア層の面方向から波長３００〜１５００ｎｍにおける絶対反射スペクトルを５ｎｍの範囲で測定し、波長３８０ｎｍ〜７８０ｎｍの各反射率の加重平均値を求め、これを平均反射率とした。
<Average reflectance>
Using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., UV-3500, using an integrating sphere), the absolute reflection spectrum at a wavelength of 300 to 1500 nm from the plane direction of the clear layer of the laminate is measured in the range of 5 nm. A weighted average value of each reflectance at wavelengths of 380 nm to 780 nm was determined, and this was used as the average reflectance.
＜カーボンナノチューブの繊維径＞
走査透過電子顕微鏡（日本電子株式会社製ＪＥＭ−６７００Ｍ）によって、得られたカーボンナノチューブを観測した。観測写真において、任意の１００個のカーボンナノチューブを選び、それぞれの外径を計測し、その数平均値を求めることによりカーボンナノチューブの繊維径（ｎｍ）を算出した。
<Carbon nanotube fiber diameter>
The obtained carbon nanotubes were observed with a scanning transmission electron microscope (JEM-6700M manufactured by JEOL Ltd.). In the observation photograph, arbitrary 100 carbon nanotubes were selected, each outer diameter was measured, and the number average value thereof was obtained to calculate the fiber diameter (nm) of the carbon nanotubes.
＜カーボンブラックの平均粒径＞
走査透過電子顕微鏡（日本電子株式会社製ＪＥＭ−６７００Ｍ）によって、カーボンブラックを観測した。観測写真において、任意の１００個のカーボンブラックを選び、それぞれの外径を計測し、その数平均値を求めることにより、カーボンブラックの平均粒径（ｎｍ）を算出した。
<Average particle size of carbon black>
Carbon black was observed with a scanning transmission electron microscope (JEM-6700M manufactured by JEOL Ltd.). In the observation photograph, arbitrary 100 carbon blacks were selected, each outer diameter was measured, and the number average value thereof was obtained to calculate the average particle diameter (nm) of the carbon black.
＜カーボンナノチューブ合成用触媒およびカーボンナノチューブの製造例＞
後述の各実施例及び比較例において使用されたカーボンナノチューブ合成用触媒およびアーボンナノチューブは以下の方法により作製した。
<Examples of carbon nanotube synthesis catalyst and carbon nanotube production>
Catalysts for carbon nanotube synthesis and Arbon nanotubes used in Examples and Comparative Examples described later were prepared by the following method.
＜カーボンナノチューブ合成用触媒（Ａ）の作製＞
酢酸コバルト・四水和物２００ｇおよび担持成分としての酢酸マグネシウム・四水和物１７２ｇをビーカーに秤取り、均一になるまで撹拌した。耐熱性容器に移し替え、電気オーブンを用いて、１９０±５℃の温度で３０分乾燥させ水分を蒸発させた後、乳鉢で粉砕してカーボンナノチューブ合成用触媒(Ａ)の前駆体を得た。得られたカーボンナノチューブ合成用触媒触媒(Ａ)の前駆体１００ｇを耐熱容器に秤取り、マッフル炉にて、空気中５００℃±５℃雰囲気下で３０分焼成した後、乳鉢で粉砕して触媒（Ａ）を得た。
<Preparation of carbon nanotube synthesis catalyst (A)>
200 g of cobalt acetate tetrahydrate and 172 g of magnesium acetate tetrahydrate as a supporting component were weighed in a beaker and stirred until uniform. It was transferred to a heat-resistant container, and dried for 30 minutes at a temperature of 190 ± 5 ° C. using an electric oven to evaporate the water, and then pulverized in a mortar to obtain a precursor of the carbon nanotube synthesis catalyst (A). . 100 g of the precursor of the catalyst catalyst (A) for carbon nanotube synthesis obtained was weighed in a heat-resistant container, calcined in a muffle furnace in an atmosphere of 500 ° C. ± 5 ° C. for 30 minutes, and then pulverized in a mortar. (A) was obtained.
＜カーボンナノチューブ合成用触媒（Ｂ）の作製＞
水酸化コバルト７４ｇおよび担持成分としての酢酸マグネシウム・四水和物１７２ｇをビーカーに秤取り、均一になるまで撹拌した。耐熱性容器に移し替え、電気オーブンを用いて、１９０±５℃の温度で３０分乾燥させ水分を蒸発させた後、乳鉢で粉砕してカーボンナノチューブ合成用触媒(Ｂ)の前駆体を得た。得られたカーボンナノチューブ合成用触媒触媒(Ｂ)の前駆体１００ｇを耐熱容器に秤取り、マッフル炉にて、空気中５００℃±５℃雰囲気下で３０分焼成した後、乳鉢で粉砕して触媒（Ｂ）を得た。
<Preparation of carbon nanotube synthesis catalyst (B)>
74 g of cobalt hydroxide and 172 g of magnesium acetate tetrahydrate as a supporting component were weighed in a beaker and stirred until uniform. It was transferred to a heat-resistant container, and dried for 30 minutes at a temperature of 190 ± 5 ° C. using an electric oven to evaporate the water, and then pulverized in a mortar to obtain a precursor of carbon nanotube synthesis catalyst (B). . 100 g of the precursor of the catalyst catalyst (B) for synthesizing the carbon nanotube thus obtained was weighed in a heat-resistant container, calcined in a muffle furnace in an atmosphere of 500 ° C. ± 5 ° C. for 30 minutes, and then pulverized in a mortar. (B) was obtained.
＜カーボンナノチューブ（Ａ１）の作製＞
加圧可能で、外部ヒーターで加熱可能な、内容積が１０リットルの横型反応管の中央部に、カーボンナノチューブ合成用触媒(Ａ)１．０ｇを散布した石英ガラス製耐熱皿を設置した。アルゴンガスを注入しながら排気を行い、反応管内の空気をアルゴンガスで置換し、横型反応管中の雰囲気を酸素濃度１体積％以下とした。次いで、外部ヒーターにて加熱し、横型反応管内の中心部温度が７００℃になるまで加熱した。７００℃に到達した後、毎分０．１リットルの流速で１分間、水素ガスを反応管内に導入し、触媒を活性化処理した。その後、炭素源としてエチレンガスを毎分１リットルの流速で反応管内に導入し、１時間接触反応させた。反応終了後、反応管内のガスをアルゴンガスで置換し、反応管内の温度を１００℃以下になるまで冷却し、得られたカーボンナノチューブを採取した。得られたカーボンナノチューブは、８０メッシュの金網で粉砕ろ過した。
<Production of carbon nanotube (A1)>
A quartz glass heat-resistant dish in which 1.0 g of the carbon nanotube synthesis catalyst (A) was dispersed was installed in the center of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 liters. Exhaust was performed while injecting argon gas, the air in the reaction tube was replaced with argon gas, and the atmosphere in the horizontal reaction tube was adjusted to an oxygen concentration of 1% by volume or less. Subsequently, it heated with the external heater and it heated until the center part temperature in a horizontal type reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute to activate the catalyst. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute, and contact reaction was performed for 1 hour. After completion of the reaction, the gas in the reaction tube was replaced with argon gas, the reaction tube was cooled to a temperature of 100 ° C. or less, and the resulting carbon nanotubes were collected. The obtained carbon nanotubes were pulverized and filtered with an 80 mesh wire mesh.
＜カーボンナノチューブ（Ａ２）の作製＞
加圧可能で、外部ヒーターで加熱可能な、内容積が１０リットルの横型反応管の中央部に、カーボンナノチューブ合成用触媒(Ａ)１．０ｇを散布した石英ガラス製耐熱皿を設置した。アルゴンガスを注入しながら排気を行い、反応管内の空気をアルゴンガスで置換し、横型反応管中の雰囲気を酸素濃度１体積％以下とした。次いで、外部ヒーターにて加熱し、横型反応管内の中心部温度が７００℃になるまで加熱した。７００℃に到達した後、毎分０．１リットルの流速で１分間、水素ガスを反応管内に導入し、触媒を活性化処理した。その後、炭素源としてエチレンガスを毎分１リットルの流速で反応管内に導入し、２時間接触反応させた。反応終了後、反応管内のガスをアルゴンガスで置換し、反応管内の温度を１００℃以下になるまで冷却し、得られたカーボンナノチューブを採取した。得られたカーボンナノチューブは、８０メッシュの金網で粉砕ろ過した。
<Production of carbon nanotube (A2)>
A quartz glass heat-resistant dish in which 1.0 g of the carbon nanotube synthesis catalyst (A) was dispersed was installed in the center of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 liters. Exhaust was performed while injecting argon gas, the air in the reaction tube was replaced with argon gas, and the atmosphere in the horizontal reaction tube was adjusted to an oxygen concentration of 1% by volume or less. Subsequently, it heated with the external heater and it heated until the center part temperature in a horizontal type reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute to activate the catalyst. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute, and contact reaction was performed for 2 hours. After completion of the reaction, the gas in the reaction tube was replaced with argon gas, the reaction tube was cooled to a temperature of 100 ° C. or less, and the resulting carbon nanotubes were collected. The obtained carbon nanotubes were pulverized and filtered with an 80 mesh wire mesh.
＜カーボンナノチューブ（Ｂ１）の作製＞
加圧可能で、外部ヒーターで加熱可能な、内容積が１０リットルの横型反応管の中央部に、カーボンナノチューブ合成用触媒(Ｂ)１．０ｇを散布した石英ガラス製耐熱皿を設置した。アルゴンガスを注入しながら排気を行い、反応管内の空気をアルゴンガスで置換し、横型反応管中の雰囲気を酸素濃度１体積％以下とした。次いで、外部ヒーターにて加熱し、横型反応管内の中心部温度が７００℃になるまで加熱した。７００℃に到達した後、毎分０．１リットルの流速で１分間、水素ガスを反応管内に導入し、触媒を活性化処理した。その後、炭素源としてエチレンガスを毎分１リットルの流速で反応管内に導入し、１時間接触反応させた。反応終了後、反応管内のガスをアルゴンガスで置換し、反応管内の温度を１００℃以下になるまで冷却し、得られたカーボンナノチューブを採取した。得られたカーボンナノチューブは、８０メッシュの金網で粉砕ろ過した。
<Production of carbon nanotube (B1)>
A quartz glass heat-resistant dish in which 1.0 g of the carbon nanotube synthesis catalyst (B) was dispersed was installed in the center of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 liters. Exhaust was performed while injecting argon gas, the air in the reaction tube was replaced with argon gas, and the atmosphere in the horizontal reaction tube was adjusted to an oxygen concentration of 1% by volume or less. Subsequently, it heated with the external heater and it heated until the center part temperature in a horizontal type reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute to activate the catalyst. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute, and contact reaction was performed for 1 hour. After completion of the reaction, the gas in the reaction tube was replaced with argon gas, the reaction tube was cooled to a temperature of 100 ° C. or less, and the resulting carbon nanotubes were collected. The obtained carbon nanotubes were pulverized and filtered with an 80 mesh wire mesh.
＜カーボンナノチューブ（Ｂ２）の作製＞
加圧可能で、外部ヒーターで加熱可能な、内容積が１０リットルの横型反応管の中央部に、カーボンナノチューブ合成用触媒(Ｂ)１．０ｇを散布した石英ガラス製耐熱皿を設置した。アルゴンガスを注入しながら排気を行い、反応管内の空気をアルゴンガスで置換し、横型反応管中の雰囲気を酸素濃度１体積％以下とした。次いで、外部ヒーターにて加熱し、横型反応管内の中心部温度が７００℃になるまで加熱した。７００℃に到達した後、毎分０．１リットルの流速で１分間、水素ガスを反応管内に導入し、触媒を活性化処理した。その後、炭素源としてエチレンガスを毎分１リットルの流速で反応管内に導入し、２時間接触反応させた。反応終了後、反応管内のガスをアルゴンガスで置換し、反応管内の温度を１００℃以下になるまで冷却し、得られたカーボンナノチューブを採取した。得られたカーボンナノチューブは、８０メッシュの金網で粉砕ろ過した。
<Production of carbon nanotube (B2)>
A quartz glass heat-resistant dish in which 1.0 g of the carbon nanotube synthesis catalyst (B) was dispersed was installed in the center of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 liters. Exhaust was performed while injecting argon gas, the air in the reaction tube was replaced with argon gas, and the atmosphere in the horizontal reaction tube was adjusted to an oxygen concentration of 1% by volume or less. Subsequently, it heated with the external heater and it heated until the center part temperature in a horizontal type reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute to activate the catalyst. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute, and contact reaction was performed for 2 hours. After completion of the reaction, the gas in the reaction tube was replaced with argon gas, the reaction tube was cooled to a temperature of 100 ° C. or less, and the resulting carbon nanotubes were collected. The obtained carbon nanotubes were pulverized and filtered with an 80 mesh wire mesh.
＜ＣＮＴ含有樹脂組成物の製造＞
まず、実施例に先立って、ＣＮＴ含有樹脂組成物の作製方法を以下に示す。
<Manufacture of CNT-containing resin composition>
First, prior to Examples, a method for producing a CNT-containing resin composition is shown below.
＜ＣＮＴ含有樹脂組成物１の製造＞
カーボンナノチューブ（Ａ１）０．５部、およびＰＥＴ樹脂（エチレングリコール−テレフタル酸共重合体、ＭＡ−２１０１、ユニチカ社製）９９．５部をスーパーミキサー（カワタ社製）に投入し、２５℃にて３分間撹拌して混合物を得た。次いで前記混合物を二軸押出し機(日本プラコン社製)に投入し、２６０℃で押し出し、ペレタイザーでカットすることでＣＮＴ含有樹脂組成物１を得た。
<Production of CNT-containing resin composition 1>
Charge carbon nanotube (A1) 0.5 part and PET resin (ethylene glycol-terephthalic acid copolymer, MA-2101, manufactured by Unitika Co., Ltd.) 99.5 parts into a super mixer (produced by Kawata Co., Ltd.) at 25 ° C. And stirred for 3 minutes to obtain a mixture. Next, the mixture was put into a twin screw extruder (manufactured by Nippon Placon Co., Ltd.), extruded at 260 ° C., and cut with a pelletizer to obtain a CNT-containing resin composition 1.
＜ＣＮＴ含有樹脂組成物２〜１４の製造＞
表１に掲載した樹脂の種類、カーボンナノチューブの種類とカーボンナノチューブの添加量に変更した以外は、ＣＮＴ含有樹脂組成物１の製造方法と同様の方法により、それぞれＣＮＴ含有樹脂組成物２〜１４を得た。
<Manufacture of CNT-containing resin compositions 2-14>
The CNT-containing resin compositions 2 to 14 were prepared in the same manner as in the production method of the CNT-containing resin composition 1 except that the resin type, the carbon nanotube type and the carbon nanotube addition amount listed in Table 1 were changed. Obtained.
＜カーボンブラック含有樹脂組成物１の作製＞
カーボンブラック（ファーネスブラック粉、ニテロン♯１０、平均粒径４０ｎｍ、新日化カーボン社製）５部、およびＰＥＴ樹脂（エチレングリコール−テレフタル酸共重合体、ＭＡ−２１０１、ユニチカ社製）９５部をスーパーミキサー（カワタ社製）に投入し、２５℃にて３分間撹拌して混合物を得た。次いで前記混合物を二軸押出し機(日本プラコン社製)に投入し、２６０℃で押し出し、ペレタイザーでカットすることでカーボンブラック含有樹脂組成物１を得た。
<Preparation of carbon black-containing resin composition 1>
5 parts of carbon black (furnace black powder, Niteron # 10, average particle size 40 nm, manufactured by Nisshin Carbon) and 95 parts of PET resin (ethylene glycol-terephthalic acid copolymer, MA-2101, manufactured by Unitika) The mixture was put into a super mixer (manufactured by Kawata) and stirred at 25 ° C. for 3 minutes to obtain a mixture. Subsequently, the said mixture was thrown into the twin-screw extruder (made by Nippon Placon Co., Ltd.), it extruded at 260 degreeC, and the carbon black containing resin composition 1 was obtained by cutting with a pelletizer.
＜クリア塗料の調製＞
クリア層の形成に用いるクリア塗料は丸底フラスコ中に、有機溶剤（トルエン／キシレン／酢酸エチル／酢酸ブチル＝７０部／１５部／１０部／５部からなる混合液）を入れ、メラミン焼き付け用アクリル樹脂（ＤＩＣ株式会社製、ＡＣＲＹＤＩＣ Ａ４０５）を添加し、１時間撹拌することにより調製した。
<Preparation of clear paint>
The clear paint used to form the clear layer is used for baking melamine with an organic solvent (mixed solution of toluene / xylene / ethyl acetate / butyl acetate = 70 parts / 15 parts / 10 parts / 5 parts) in a round bottom flask. An acrylic resin (manufactured by DIC Corporation, ACRYDIC A405) was added and the mixture was stirred for 1 hour.
（実施例１）
＜ＣＮＴ含有層１の作成＞
ＣＮＴ含有樹脂組成物１を、Ｔ−ダイ押出機で２８０℃にて押出成形し、厚さ１００μｍのＣＮＴ含有フィルムを作成し、ＣＮＴ含有層１とした。
＜積層体１の作成＞
ＣＮＴ含有層１を基材として、クリア塗料を乾燥後の膜厚が１０μｍとなるようにバーコーターを用いて塗工後、電気オーブン中で１５０±５℃にて２０分間乾燥させ、クリア層を形成することにより積層体１を作製した。得られた積層体について、Ｌ*ａ*ｂ*および平均反射率を測定した。
Example 1
<Creation of CNT-containing layer 1>
The CNT-containing resin composition 1 was extruded at 280 ° C. with a T-die extruder to prepare a CNT-containing film having a thickness of 100 μm.
<Creation of laminated body 1>
Using the CNT-containing layer 1 as a base material, the clear coating is applied using a bar coater so that the film thickness after drying is 10 μm, and then dried in an electric oven at 150 ± 5 ° C. for 20 minutes to form a clear layer. The laminated body 1 was produced by forming. About the obtained laminated body, L * a * b * and average reflectance were measured.
（実施例２〜１９）
実施例１で使用したＣＮＴ含有樹脂組成物１の替わりに、表２に掲載したＣＮＴ含有樹脂組成物とＣＮＴ含有層及びクリア層の種類または膜厚を変更した以外は、実施例１と同様な方法により、積層体２〜１２を作製した。得られた積層体について、Ｌ*ａ*ｂ*及び平均反射率を測定した。
(Examples 2 to 19)
Instead of the CNT-containing resin composition 1 used in Example 1, the same as in Example 1 except that the types or film thicknesses of the CNT-containing resin composition, the CNT-containing layer, and the clear layer listed in Table 2 were changed. Laminates 2 to 12 were produced by the method. About the obtained laminated body, L * a * b * and average reflectance were measured.
表２に実施例１〜１９で作製した積層体の作製条件と評価結果を示す。
漆黒性の評価基準は、以下を基準とした。
◎ Ｌ*が２４未満かつｂ*が０．３以下の両方を満たす場合（極めて良好）
〇 Ｌ*が２４〜２６かつｂ*が０．３以下の両方を満たす場合（良好）
× Ｌ*が２６を超える、またはｂ*が０．３以下を超える（不良）
Table 2 shows the production conditions and evaluation results of the laminates produced in Examples 1 to 19.
The evaluation criteria for jetness were based on the following.
◎ When both L * is less than 24 and b * is 0.3 or less (very good)
〇 When both L * is 24-26 and b * is 0.3 or less (good)
× L * exceeds 26, or b * exceeds 0.3 or less (defect)
（比較例１）
＜カーボンブラック含有層の作製＞
カーボンブラック含有樹脂組成物１を、Ｔ−ダイ押出機で２８０℃にて押出成形し、厚さ１００μｍのカーボンブラック含有フィルムを作成し、カーボンブラック含有層とした。次いで、ＣＮＴ含有層１の代わりにカーボンブラック含有層を用いること以外は、積層体１と同様にして、積層体２０を作成し、Ｌ*ａ*ｂ*を測定した。
(Comparative Example 1)
<Preparation of carbon black-containing layer>
The carbon black-containing resin composition 1 was extruded at 280 ° C. with a T-die extruder to prepare a carbon black-containing film having a thickness of 100 μm, which was used as a carbon black-containing layer. Next, a laminate 20 was prepared in the same manner as the laminate 1 except that a carbon black-containing layer was used instead of the CNT-containing layer 1, and L * a * b * was measured.
（比較例２）
実施例１でクリア層を形成しないＣＮＴ含有層1のみのものについて、Ｌ*ａ*ｂ*および平均反射率を測定した。
(Comparative Example 2)
L * a * b * and average reflectance were measured for only the CNT-containing layer 1 that did not form a clear layer in Example 1.
表３に比較例１〜２で作製した積層体の作製条件と評価結果を示す。 Table 3 shows the production conditions and evaluation results of the laminates produced in Comparative Examples 1 and 2.
（実施例２１）
＜ＣＮＴ含有層２１の作成＞
ＣＮＴ含有樹脂組成物１を、射出成形機（東芝機械社製ＩＳ−１００Ｆ型）を用いて射出成形を行い、縦１００ｍｍ×横１００ｍｍ×厚さ３ｍｍのＣＮＴ含有プレートを作成し、ＣＮＴ含有層２１とした。
(Example 21)
<Creation of CNT-containing layer 21>
The CNT-containing resin composition 1 is injection-molded using an injection molding machine (IS-100F type manufactured by Toshiba Machine Co., Ltd.) to produce a CNT-containing plate having a length of 100 mm × width of 100 mm × thickness of 3 mm. It was.
＜積層体２１の作成＞
ＣＮＴ含有層２１を基材として、クリア塗料を乾燥後の膜厚が１０μｍとなるようにバーコーターを用いて塗工後、電気オーブン中で１５０±５℃にて２０分間乾燥させ、クリア層を形成することにより積層体２１を作製した。得られた積層体について、Ｌ*ａ*ｂ*および平均反射率を測定した。
<Creation of laminated body 21>
Using the CNT-containing layer 21 as a base material, the clear coating is applied using a bar coater so that the film thickness after drying is 10 μm, and then dried in an electric oven at 150 ± 5 ° C. for 20 minutes to form a clear layer. The laminated body 21 was produced by forming. About the obtained laminated body, L * a * b * and average reflectance were measured.
（実施例２２〜２８）
実施例２１で使用したＣＮＴ含有樹脂組成物１の替わりに、表４に掲載したＣＮＴ含有樹脂組成物とＣＮＴ含有層及びクリア層の種類または膜厚を変更した以外は、実施例２１と同様な方法により、積層体２２〜２８を作製した。得られた積層体について、Ｌ*ａ*ｂ*及び平均反射率を測定した。
(Examples 22 to 28)
Instead of the CNT-containing resin composition 1 used in Example 21, the same as in Example 21 except that the types or film thicknesses of the CNT-containing resin composition, the CNT-containing layer, and the clear layer listed in Table 4 were changed. Laminates 22 to 28 were produced by the method. About the obtained laminated body, L * a * b * and average reflectance were measured.
（比較例３）
＜カーボンブラック含有層の作製＞
カーボンブラック含有樹脂組成物１を、射出成形機（東芝機械社製ＩＳ−１００Ｆ型）を用いて射出成形を行い、縦１００ｍｍ×横１００ｍｍ×厚さ３ｍｍのＣB含有プレートを作成し、カーボンブラック含有層とした。次いで、ＣＮＴ含有層１の代わりにカーボンブラック含有層を用いること以外は、積層体２１と同様にして、積層体２９を作成し、Ｌ*ａ*ｂ*を測定した。
(Comparative Example 3)
<Preparation of carbon black-containing layer>
The carbon black-containing resin composition 1 is injection-molded using an injection molding machine (IS-100F type manufactured by Toshiba Machine Co., Ltd.) to create a CB-containing plate measuring 100 mm in length, 100 mm in width, and 3 mm in thickness. Layered. Next, a laminate 29 was prepared in the same manner as the laminate 21 except that a carbon black-containing layer was used instead of the CNT-containing layer 1, and L * a * b * was measured.
（比較例４）
実施例２１でクリア層を形成しないＣＮＴ含有層２１のみのものについて、Ｌ*ａ*ｂ*および平均反射率を測定した。
(Comparative Example 4)
L * a * b * and average reflectance were measured for only the CNT-containing layer 21 that did not form a clear layer in Example 21.
表５に比較例３〜４で作製した積層体の作製条件と評価結果を示す。 Table 5 shows the production conditions and evaluation results of the laminates produced in Comparative Examples 3 to 4.
（実施例３１）
＜ＣＮＴ含有層３１の作成＞
ＣＮＴ含有樹脂組成物１０を、小型インフレーション成形機（サーモ・プラスティックス工業社製）を用いてインフレーション成形を行い、厚さ５０μｍの筒状のインフレーション成形ＣＮＴフィルムを作成し、ＣＮＴ含有層３１とした。
(Example 31)
<Creation of CNT-containing layer 31>
The CNT-containing resin composition 10 was subjected to inflation molding using a small inflation molding machine (manufactured by Thermo Plastics Industry Co., Ltd.) to produce a tubular inflation-molded CNT film having a thickness of 50 μm. .
＜積層体３１の作成＞
ＣＮＴ含有層３１を基材として、クリア塗料を乾燥後の膜厚が１０μｍとなるようにバーコーターを用いて塗工後、電気オーブン中で１２０±５℃にて２０分間乾燥させ、クリア層を形成することにより積層体３１を作製した。得られた積層体について、Ｌ*ａ*ｂ*および平均反射率を測定した。
<Creation of laminated body 31>
Using the CNT-containing layer 31 as a base material, the clear coating is applied using a bar coater so that the film thickness after drying is 10 μm, and then dried in an electric oven at 120 ± 5 ° C. for 20 minutes to form a clear layer. By forming, the laminated body 31 was produced. About the obtained laminated body, L * a * b * and average reflectance were measured.
（実施例３２〜３６）
実施例３１で使用したＣＮＴ含有樹脂組成物１０の替わりに、表６に掲載したＣＮＴ含有樹脂組成物とＣＮＴ含有層の種類または膜厚、及びクリア層の膜厚を変更した以外は、実施例３１と同様な方法により、積層体３２〜３６を作製した。得られた積層体について、Ｌ*ａ*ｂ*及び平均反射率を測定した。
(Examples 32-36)
Instead of the CNT-containing resin composition 10 used in Example 31, the examples except that the CNT-containing resin composition listed in Table 6 and the type or film thickness of the CNT-containing layer and the film thickness of the clear layer were changed. By the same method as 31, laminates 32 to 36 were produced. About the obtained laminated body, L * a * b * and average reflectance were measured.
（比較例５）
＜カーボンブラック含有層の作製＞
カーボンブラック含有樹脂組成物１を、小型インフレーション成形機（サーモ・プラスティックス工業社製）を用いてインフレーション成形を行い、厚さ５０μｍの筒状のインフレーション成形ＣＢフィルムを作成した。次いで、ＣＮＴ含有層３１の代わりにカーボンブラック含有層を用いること以外は、積層体３１と同様にして、積層体３７を作成し、Ｌ*ａ*ｂ*を測定した。
(Comparative Example 5)
<Preparation of carbon black-containing layer>
The carbon black-containing resin composition 1 was subjected to inflation molding using a small inflation molding machine (manufactured by Thermo Plastics Industries Co., Ltd.) to produce a tubular inflation molded CB film having a thickness of 50 μm. Next, a laminate 37 was prepared in the same manner as the laminate 31 except that a carbon black-containing layer was used instead of the CNT-containing layer 31, and L * a * b * was measured.
（比較例６）
実施例３１でクリア層を形成しないＣＮＴ含有層３１のみのものについて、Ｌ*ａ*ｂ*および平均反射率を測定した。
(Comparative Example 6)
L * a * b * and average reflectance were measured for only the CNT-containing layer 31 that did not form a clear layer in Example 31.
表７に比較例５〜６で作製した積層体の作製条件と評価結果を示す。 Table 7 shows the production conditions and evaluation results of the laminates produced in Comparative Examples 5-6.
上記結果から、本発明のカーボンナノチューブと樹脂を含む積層体を用いた場合、比較例で使用したカーボンブラックを使用した積層体やクリア層がない場合よりも、漆黒性の高い積層体が得られることが明らかとなった。 From the above results, when the laminate including the carbon nanotubes and the resin of the present invention is used, a laminate having a high jetness can be obtained as compared with the case where there is no laminate using the carbon black used in the comparative example and no clear layer. It became clear.
Claims (9)
（ただし、Ｌ*およびｂ*は、ＪＩＳ Ｚ８７２９で規定されるＬ*ａ*ｂ*表色系における値を表わす。） A laminate having a carbon nanotube-containing layer comprising carbon nanotubes and a resin, and a clear layer, wherein the laminate has an L * of 26 or less and a b * of -10 or more and 0 as measured from the plane direction of the clear layer 3 or less, the carbon nanotube-containing layer is formed by a method other than coating, and the clear layer is a transparent resin or glass.
(However, L * and b * represent values in the L * a * b * color system defined by JIS Z8729.)
（ただし、Ｌ*、ａ*およびｂ*は、ＪＩＳ Ｚ８７２９で規定されるＬ*ａ*ｂ*表色系における値を表わす。） A method for producing a laminate having a carbon nanotube-containing layer comprising a carbon nanotube and a resin, and a clear layer, wherein the laminate has an L * of 26 or less and b * of − as measured from the plane direction of the clear layer. 10 or more and 0.3 or less, the clear layer is transparent resin or glass, and the carbon nanotube-containing layer is formed by a method other than coating.
(However, L * , a * and b * represent values in the L * a * b * color system defined by JIS Z8729.)
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| JP2011201961A (en) * | 2010-03-24 | 2011-10-13 | Nagase & Co Ltd | Resin colorant and resin composition |
| JP2012066580A (en) * | 2010-08-18 | 2012-04-05 | Toray Ind Inc | Transparent conductive laminate |
| JP2013028053A (en) * | 2011-07-28 | 2013-02-07 | Techno Polymer Co Ltd | Black decorative sheet |
| JP2013209494A (en) * | 2012-03-30 | 2013-10-10 | Toyo Ink Sc Holdings Co Ltd | Resin composition |
| JP2014015037A (en) * | 2012-06-11 | 2014-01-30 | Kobe Steel Ltd | Metal sheet coated with black thin film |
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| JP2011201961A (en) * | 2010-03-24 | 2011-10-13 | Nagase & Co Ltd | Resin colorant and resin composition |
| JP2012066580A (en) * | 2010-08-18 | 2012-04-05 | Toray Ind Inc | Transparent conductive laminate |
| JP2013028053A (en) * | 2011-07-28 | 2013-02-07 | Techno Polymer Co Ltd | Black decorative sheet |
| JP2013209494A (en) * | 2012-03-30 | 2013-10-10 | Toyo Ink Sc Holdings Co Ltd | Resin composition |
| JP2014015037A (en) * | 2012-06-11 | 2014-01-30 | Kobe Steel Ltd | Metal sheet coated with black thin film |
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