JP6540344B2 - LAMINATE AND METHOD FOR MANUFACTURING THE SAME - Google Patents
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- JP6540344B2 JP6540344B2 JP2015154256A JP2015154256A JP6540344B2 JP 6540344 B2 JP6540344 B2 JP 6540344B2 JP 2015154256 A JP2015154256 A JP 2015154256A JP 2015154256 A JP2015154256 A JP 2015154256A JP 6540344 B2 JP6540344 B2 JP 6540344B2
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Description
本発明は、積層体およびその製造方法に関する。 The present invention relates to a laminate and a method of manufacturing 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 conductivity and mechanical strength, so fuel cells, electrodes, electromagnetic shielding materials, conductive resins, field emission displays ( As functional materials such as members for FEDs and storage materials of various gases including hydrogen, their application to a wide range of fields such as electronics and energy fields is expected.
例えば、特許文献１〜３では、カーボンナノチューブを含む多層フィルムが提案されている。しかし、これらはいずれもカーボンナノチューブの有する高い導電性を生かした透明性の導電性フィルムとしての使用を目的としたものであり、カーボンナノチューブを色材として使用するものではなかった。
透明性、経済性等に優れた、導電性樹脂組成物を提供することを目的とする
For example, Patent Documents 1 to 3 propose multilayer films containing carbon nanotubes. However, these were all intended for use as a transparent conductive film utilizing the high conductivity of carbon nanotubes, and carbon nanotubes were not used as a coloring material.
An object of the present invention is to provide a conductive resin composition excellent in transparency, economy and the like.
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、例えば、塗料分野において漆黒性の高い塗膜を得るためには、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４、５参照）。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 in which carbon nanotubes are used as a coloring material. For example, in order to obtain a paint film having high jet-blackness in the paint field, carbon black uniformly dispersed in a resin solution or solid resin has been used. (See Patent Documents 4 and 5). However, in the means, the lightness (L * ) is in the high (grey / white) direction, and the chromaticity (a *, b *) is in the positive direction (+ a *: red, + b *: yellow). It was difficult to express jet-blackness such as "Piano Black" and "wet feather color of crow".
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。 In addition, the color tone of a molded article using carbon black tends to be different depending on the primary particle diameter of carbon black. Specifically, when carbon black having a small primary particle diameter is used, it has bluish but blackness decreases. As described above, 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 a high degree of blackness.
本発明は、上記従来の問題を解決するものであり、高い漆黒性に優れた積層体を提供することにある。 The present invention solves the above-mentioned conventional problems, and provides a laminate excellent in high jetness.
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。 MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discover that the laminated body of the resin composition excellent in jet-blackness can be obtained by laminating | stacking the resin composition containing a carbon nanotube and resin. The present invention has been achieved.
すなわち、本発明は、少なくとも第一層および第二層の二層を有する積層体であって、下記（１）〜（３）の条件を満たすことを特徴とする積層体に関する。
（１）第一層は、顔料と樹脂とを含む。
（２）第二層は、カーボンナノチューブと樹脂とを含む。
（３）第一層および第二層に含まれる樹脂は、それぞれ独立に、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン―酢酸ビニル共重合体樹脂、塩化ビニリデン樹脂、ポリカーボネード樹脂およびポリエステル樹脂からなる群より選ばれる少なくとも１種を含む。
That is, the present invention relates to a laminate having at least two layers of a first layer and a second layer, and satisfying the following conditions (1) to (3).
(1) The first layer contains a pigment and a resin.
(2) The second layer contains carbon nanotubes and a resin.
(3) The resins contained in the first layer and the second layer are each independently selected from the group consisting of polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, vinylidene chloride resin, polycarbonate resin and polyester resin It contains at least one kind.
また、本発明は、第二層に含まれるカーボンナノチューブの含有量が、第二層全体に対して、０．００５質量％以上０．１質量％以下である上記積層体に関する。 The present invention also relates to the above-mentioned laminate, wherein the content of carbon nanotubes contained in the second layer is 0.005% by mass or more and 0.1% by mass or less with respect to the entire second layer.
また、本発明は、第一層に含まれる顔料が、カーボンブラックを含む上記積層体に関する。 The present invention also relates to the above-mentioned laminate, wherein the pigment contained in the first layer contains carbon black.
また、本発明は、第二層表面の、Ｌ*が２６以下、かつｂ*が−１０以上０．３以下である上記積層体に関する。（但し、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す。） Further, the present invention relates to the above-mentioned laminate having L * of 26 or less and b * of −10 or more and 0.3 or less on the surface of the second layer. (However, L * and b * represent values in the L * a * b * color system specified in JIS Z8729.)
また、本発明は、第二層の波長３８０〜７８０ｎｍにおける平均透過率が、５％以上８０％以下である上記積層体に関する。 Moreover, this invention relates to the said laminated body whose average transmittance | permeability in wavelength 380-780 nm of 2nd layer is 5% or more and 80% or less.
また、本発明は、第一層の膜厚が、１０μｍ以上３ｍｍ以下である上記積層体に関する。 Moreover, this invention relates to the said laminated body whose film thickness of a 1st layer is 10 micrometers or more and 3 mm or less.
また、本発明は、第二層の膜厚が、５０μｍ以上１ｍｍ以下である上記積層体に関する。 Moreover, this invention relates to the said laminated body whose film thickness of a 2nd layer is 50 micrometers or more and 1 mm or less.
また、本発明は、少なくとも第一層および第二層の二層を有する積層体の製造方法であって、下記（１）〜（３）の条件を満たし、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により製造することを特徴とする積層体の製造方法に関する。
（１）第一層は、顔料と樹脂とを含む。
（２）第二層は、カーボンナノチューブと樹脂とを含む。
（３）第一層および第二層に含まれる樹脂は、それぞれ独立に、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン―酢酸ビニル共重合体樹脂、塩化ビニリデン樹脂、ポリカーボネード樹脂およびポリエステル樹脂からなる群より選ばれる少なくとも１種を含む。
Further, the present invention is a method for producing a laminate having at least two layers of a first layer and a second layer, which satisfy the following conditions (1) to (3), extrusion molding, injection molding, blow molding, The present invention relates to a method for producing a laminate characterized by being produced by any method of compression molding, transfer molding, inflation molding or calendar molding.
(1) The first layer contains a pigment and a resin.
(2) The second layer contains carbon nanotubes and a resin.
(3) The resins contained in the first layer and the second layer are each independently selected from the group consisting of polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, vinylidene chloride resin, polycarbonate resin and polyester resin It contains at least one kind.
本発明により、高い漆黒性が必要とされる様々な用途分野において、漆黒性の高い積層体を使用することが可能となった。 According to the present invention, it has become possible to use highly jet-fast laminates in various application fields where high jet-fastness is required.
以下、本発明について詳しく説明する。
本発明の積層体は、少なくとも第一層（ａ）および第二層（ｂ）の二層を有する積層体であって、下記（１）〜（３）の条件を満たすことを特徴とする積層体である。
（１）第一層（ａ）は、顔料と樹脂とを含む。
（２）第二層（ｂ）は、カーボンナノチューブと樹脂とを含む。
（３）第一層（ａ）および第二層（ｂ）に含まれる樹脂は、それぞれ独立に、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン―酢酸ビニル共重合体樹脂、塩化ビニリデン樹脂、ポリカーボネード樹脂およびポリエステル樹脂からなる群より選ばれる少なくとも１種を含む。
Hereinafter, the present invention will be described in detail.
The laminate of the present invention is a laminate having at least two layers of a first layer (a) and a second layer (b), and is characterized by satisfying the following conditions (1) to (3): It is a body.
(1) The first layer (a) contains a pigment and a resin.
(2) The second layer (b) contains carbon nanotubes and a resin.
(3) The resins contained in the first layer (a) and the second layer (b) are each independently polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, vinylidene chloride resin, polycarbonate resin and polyester resin And at least one selected from the group consisting of
＜第一層（ａ）＞
第一層（ａ）は、顔料と樹脂とを含む第一層形成用樹脂組成物（ａ´）からなる層である。第一層形成用樹脂組成物（ａ´）を得る方法は、特に制限はないが、例えば、顔料と樹脂と、更に必要に応じて他の添加剤とを混合し、樹脂の軟化点以上の温度で、二軸押出し機等の混練機を用いて溶融混練することで容易に得ることができる。
<First layer (a)>
The first layer (a) is a layer formed of a resin composition for forming a first layer (a ′) containing a pigment and a resin. The method for obtaining the first layer-forming resin composition (a ′) is not particularly limited, but, for example, a pigment and a resin, and, if necessary, other additives are mixed to obtain a resin composition having a softening point or more. It can be easily obtained by melt-kneading using a kneader such as a twin-screw extruder at a temperature.
顔料としては、無機顔料および有機顔料が挙げられ、これらは一種のみ使用しても二種以上併用しても構わない。漆黒性の高い積層体を得るためには、第一層は黒色であることが好ましく、黒色の層を得るためには、複数種の有色顔料を併用して加法混色により黒色を得る方法と、黒色顔料を使用して黒色を得る方法が考えられるが、黒色顔料を使用して黒色を得る方法が好ましい。 Examples of the pigment include inorganic pigments and organic pigments, which may be used alone or in combination of two or more. In order to obtain a laminate having high jet-blackness, the first layer is preferably black, and in order to obtain a black layer, a method of obtaining black by additive color mixing using a plurality of colored pigments in combination, Although methods of obtaining black using black pigments are conceivable, methods of obtaining black using black pigments are preferred.
黒色顔料としては、無機系黒色顔料および有機系黒色顔料が挙げられる。無機系黒色顔料としては、カーボンブラック（Ｃ．Ｉ．ピグメントブラック７）、黒鉛、チタンブラック、ビスマス複合酸化物、鉄酸化物（マグネタイト型四酸化三鉄）、銅−クロム複合酸化物、銅−クロム−亜鉛複合酸化物、Ｃ.Ｉ.ピグメントブラック２７、等が挙げられる。有機系黒色顔料としては、アニリンブラック（Ｃ．Ｉ．ピグメントブラック１）、ペリレンブラック、Ｃ．Ｉ．ピグメントブラック３１、Ｃ．Ｉ．ピグメントブラック３２等が挙げられる。これら顔料の内、カーボンブラックが好ましい。尚、「Ｃ．Ｉ．」とは、カラーインデックスを表す。 Examples of black pigments include inorganic black pigments and organic black pigments. As the inorganic black pigment, carbon black (CI pigment black 7), graphite, titanium black, bismuth complex oxide, iron oxide (magnetite type triiron tetraoxide), copper-chromium complex oxide, copper- Chromium-zinc composite oxide, CI pigment black 27, etc. may be mentioned. Organic black pigments include aniline black (C.I. pigment black 1), perylene black, C.I. I. Pigment black 31, C.I. I. Pigment black 32 and the like. Among these pigments, carbon black is preferred. "CI" indicates a color index.
カーボンブラックとしては、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、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、あるいはこれら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。 As carbon black, a hydrocarbon such as ketjen black, acetylene black, furnace black, channel black and naphtha is partially oxidized in the presence of hydrogen and oxygen to produce a synthesis gas containing hydrogen and carbon monoxide. Examples thereof include carbon black to be produced, and carbon black obtained by oxidizing or reducing these.
第一層（ａ）に含まれる顔料の含有量は、特に制限はないが、０．０１質量％以上５０質量％以下が好ましく、０．１質量％以上２０質量％以下がより好ましく、０．５質量％以上２０質量％以下が更に好ましい。 The content of the pigment contained in the first layer (a) is not particularly limited, but is preferably 0.01% by mass to 50% by mass and more preferably 0.1% by mass to 20% by mass, and more preferably 0. 5 mass% or more and 20 mass% or less are more preferable.
尚、黒色顔料を使用する場合、用途に応じて、本発明の効果を損なわない範囲で、光輝性顔料等の黒色顔料以外の顔料を併用しても構わない。 In addition, when using a black pigment, you may use together pigments other than black pigments, such as a luster pigment, in the range which does not impair the effect of this invention according to a use.
第一層（ａ）に含まれる樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン―酢酸ビニル共重合体樹脂、塩化ビニリデン樹脂、ポリカーボネード樹脂およびポリエステル樹脂が挙げられ、これらの樹脂は１種類のみ使用しても２種類以上併用しても構わない。 Examples of the resin contained in the first layer (a) include polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, vinylidene chloride resin, polycarbonate resin and polyester resin, and only one of these resins is used Even two or more types may be used in combination.
尚、用途に応じて、本発明の効果を損なわない範囲で、上記以外の天然樹脂や合成樹脂を併用しても構わない。天然樹脂としては、天然ゴム、ゼラチン、ロジン、セラック、多糖類、ギルソナイト等が挙げられる。また、合成樹脂としては、フェノール樹脂、アルキッド樹脂、石油樹脂、ビニル系樹脂、合成ゴム、ポリアミド樹脂、アクリル樹脂、スチレン樹脂、エポキシ樹脂、メラミン樹脂、ウレタン樹脂、アミノ樹脂、アミド樹脂、イミド樹脂、フッ素系樹脂、フッ化ビニリデン樹脂、ＡＢＳ樹脂、シリコーン系樹脂、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等が挙げられる。 In addition, according to a use, you may use together natural resin and synthetic resin other than the above in the range which does not impair the effect of this invention. Natural resins include natural rubber, gelatin, rosin, shellac, polysaccharides, gilsonite and the like. Further, as the synthetic resin, phenol resin, alkyd resin, petroleum resin, vinyl resin, synthetic rubber, polyamide resin, acrylic resin, styrene resin, epoxy resin, melamine resin, urethane resin, amino resin, amide resin, imide resin, A fluorine resin, a vinylidene fluoride resin, an ABS resin, a silicone resin, nitrocellulose, a rosin modified phenol resin, a rosin modified polyamide resin etc. are mentioned.
また、第一層形成用樹脂組成物（ａ´）は、必要に応じて、紫外線吸収剤、酸化防止剤、架橋剤、分散剤、防カビ剤、離型剤、滑剤、ワックス等の他の添加剤を含んでも良い。 In addition, the resin composition for forming the first layer (a ′) may be any of UV absorber, antioxidant, crosslinking agent, dispersing agent, antifungal agent, mold release agent, lubricant, wax and the like, as necessary. An additive may be included.
＜第二層（ｂ）＞
第二層（ｂ）は、カーボンナノチューブと樹脂とを含む第二層形成用樹脂組成物（ｂ´）からなる層である。第二層形成用樹脂組成物（ｂ´）を得る方法は、特に制限はないが、例えば、カーボンナノチューブと樹脂とを混合し、第一層形成用樹脂組成物（ａ´）を得る方法と同様にして得ることができる。
<Second layer (b)>
The second layer (b) is a layer formed of a resin composition for forming a second layer (b ′) containing carbon nanotubes and a resin. The method for obtaining the second layer forming resin composition (b ′) is not particularly limited, but, for example, a method for mixing the carbon nanotube and the resin to obtain the first layer forming resin composition (a ′) It can be obtained similarly.
カーボンナノチューブは、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（ＳＷＣＮＴ）、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（ＭＷＣＮＴ）でも、これらが混在するものであっても良いが、多層カーボンナノチューブ（ＭＷＣＮＴ）であることが好ましい。また、カーボンナノチューブ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を用いることもできる。 A carbon nanotube has a cylindrical shape obtained by winding one surface of graphite, and the single-layer carbon nanotube (SWCNT) having a structure in which the graphite layer is wound in one layer is wound with two or more layers. The multi-walled carbon nanotubes (MWCNT) may be mixed, but they may be mixed, but multi-walled carbon nanotubes (MWCNT) are preferable. In addition, carbon nanotubes in which the sidewall of the carbon nanotube does not have a graphite structure but an amorphous structure can also be used.
カーボンナノチューブの形状は、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）、コイル状などいずれの形状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。本発明で使用するカーボンナノチューブは、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）、コイル状以外の形状であることが好ましい。 The shape of the carbon nanotube may be any shape such as needle shape, cylindrical tube shape, fish bone shape (fish bone, cup laminated type), card shape (platelet), coil shape and the like. Specifically, for example, graphite whiskers, filamentous carbon, graphite fibers, ultrafine carbon tubes, carbon tubes, carbon fibrils, carbon microtubes, carbon nanofibers and the like can be mentioned. The carbon nanotube used in the present invention is preferably in a shape other than a fish bone shape (fish bone, cup stacked type), a card shape (platelet), or a coil shape.
カーボンナノチューブの繊維径は、１〜５００ｎｍが好ましく、５〜５０ｎｍがより好ましい。また、カーボンナノチューブの繊維長は、０．１〜１５０μｍが好ましく、１〜５０μｍがより好ましい。更に、カーボンナノチューブの炭素純度は、カーボンナノチューブ１００質量％中、８０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 fiber diameter of the carbon nanotube is preferably 1 to 500 nm, and more preferably 5 to 50 nm. Moreover, 0.1-150 micrometers is preferable and, as for the fiber length of a carbon nanotube, 1-50 micrometers is more preferable. Furthermore, 80 mass% or more is preferable in 100 mass% of carbon nanotubes, as for the carbon purity of a carbon nanotube, 90 mass% or more is more preferable, and 95 mass% or more is more preferable.
カーボンナノチューブは、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等も用いることができる。 The carbon nanotube may be one which has been subjected to surface treatment or a carbon nanotube derivative to which a functional group such as a carboxyl group is imparted. In addition, carbon nano nanotubes etc. in which an organic compound, a metal atom, fullerene or the like is contained can also be used.
第二層（ｂ）に含まれる樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン―酢酸ビニル共重合体樹脂、塩化ビニリデン樹脂、ポリカーボネード樹脂およびポリエステル樹脂が挙げられ、これらの樹脂は１種類のみ使用しても２種類以上併用しても構わない。尚、用途に応じて、本発明の効果を損なわない範囲で、上記以外の天然樹脂や合成樹脂を併用しても構わない。また、第二層形成用樹脂組成物（ｂ´）は、必要に応じて、紫外線吸収剤、酸化防止剤、架橋剤、分散剤等の添加剤を含んでも良い。 Examples of the resin contained in the second layer (b) include polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, vinylidene chloride resin, polycarbonate resin and polyester resin, and only one of these resins is used Even two or more types may be used in combination. In addition, according to a use, you may use together natural resin and synthetic resin other than the above in the range which does not impair the effect of this invention. Moreover, the resin composition (b ') for 2nd layer formation may also contain additives, such as a ultraviolet absorber, an antioxidant, a crosslinking agent, a dispersing agent, as needed.
第二層に含まれるカーボンナノチューブの含有量は、特に制限はないが、第二層全体に対して、０．００５質量％以上０．１質量％以下であることが好ましい。 The content of carbon nanotubes contained in the second layer is not particularly limited, but is preferably 0.005% by mass or more and 0.1% by mass or less with respect to the entire second layer.
＜積層体の製造方法＞
本発明の積層体は、第一層形成用樹脂組成物（ａ´）と第二層形成用樹脂組成物（ｂ´）とを、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により積層することによって製造することができる。
<Method of manufacturing laminate>
The laminate of the present invention is formed by extrusion molding, injection molding, blow molding, compression molding, transfer molding, and the first layer forming resin composition (a ') and the second layer forming resin composition (b'). It can be produced by laminating by either inflation molding or calendar molding.
＜積層体＞
本発明の積層体は、第二層表面のＬ*が２６以下、かつｂ*が−１０以上０．３以下であることが好ましく、第一層のＬ*が３０以下であることがより好ましい。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、第二層の表面方向から、色差計（ＮＩＰＰＯＮＤＥＮＳＨＯＫＵ社製、ＳｐｅｃｔｒｏＣｏｌｏｒＭｅｔｅｒＳＥ２０００）を用いて測定して得られた値である。
<Laminate>
In the laminate of the present invention, L * of the second layer surface is preferably 26 or less, and b * is preferably -10 or more and 0.3 or less, and more preferably L * of the first layer is 30 or less . Here, L * , a * and b * represent values in the L * a * b * color system specified in JIS Z8729, and from the surface direction of the second layer, a color difference meter (manufactured by NIPPON DENSHOKU Co., Ltd., SpectroColorMeter SE2000) It is a value obtained by measuring using.
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 lower the lightness). The closer a * and b * are to zero (0), the blacker the hue. Also, it can be said that bluish (blue) has a stronger hue as b * is more negative. Therefore, from the viewpoint of jet blackness, it is considered that jet blackness is high when it is black having a slight bluish color (blue color), so the above numerical range is considered to be preferable.
本発明の積層体は、第一層と第二層とが、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が得られる。 In the laminate of the present invention, the first layer and the second layer may not be laminated in close contact with each other, but when these layers are laminated in close contact with each other, the jet blackness is more excellent. A laminate is obtained.
第二層の波長３８０〜７８０ｎｍにおける平均透過率が、５％以上８０％以下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であるといえる。本明細書における平均透過率とは、第二層（ｂ）を、紫外可視近赤外分光光度計（日立製作所社製、ＵＶ−３５００）を用いて、波長３００〜１５００ｎｍにおける透過スペクトルを５ｎｍの範囲で測定し、波長３８０ｎｍ〜７８０ｎｍの各波長での透過率の加重平均値である。 The average transmittance of the second layer at a wavelength of 380 to 780 nm is preferably 5% to 80%. If it is such a range in particular, it can be said that it is a layered product excellent in jet blackness. The average transmittance in the present specification means that the second layer (b) has a transmission spectrum at a wavelength of 300 to 1,500 nm of 5 nm using an ultraviolet-visible near-infrared spectrophotometer (UV-3500 manufactured by Hitachi, Ltd.). It is measured in the range, and is a weighted average value of the transmittance at each wavelength of 380 nm to 780 nm.
第一層（ａ）の膜厚は、１０μｍ以上３ｍｍ以下であることが好ましい。また、第二層（ｂ）の膜厚は５０μｍ以上１ｍｍ以下であることが好ましい。斯かる範囲であれば、より漆黒性に優れた積層体が得られる。 The film thickness of the first layer (a) is preferably 10 μm or more and 3 mm or less. Moreover, it is preferable that the film thickness of 2nd layer (b) is 50 micrometers or more and 1 mm or less. Within such a range, a laminate having more excellent jettackiness can be obtained.
本発明のカーボンナノチューブと樹脂から第二層形成用樹脂組成物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。 The method for producing the resin composition for forming the second layer from the carbon nanotube of the present invention and the resin is not particularly limited, but it is introduced into a general high speed shear mixer such as a Henschel mixer or a super mixer. After mixing, it can be obtained by melt-kneading using a two-roll, three-roll, pressure kneader, Banbury mixer, single-screw kneader or twin-screw kneader, etc. and extrusion molded into pellets.
第二層（ｂ）を第一層（ａ）上に形成する方法としては、第二層形成用樹脂組成物（ｂ´）を塗布以外の方法で形成されてなることを特徴とし、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、任意の形状の第一層を形成することができる。
また、第二層（ｂ）は製膜されたものをラミネートしても良く、必ずしもこれらの層が密着していなくても良い。
As a method of forming the second layer (b) on the first layer (a), the method is characterized in that the resin composition (b ') for forming the second layer is formed by a method other than coating, and a preferred method Specific examples thereof include film molding such as extrusion molding, injection molding, blow molding, compression molding, transfer molding, T-die molding and inflation molding, and calendar molding.
For example, in the case of injection molding, the first layer of any shape can be formed by melt-kneading the carbon nanotube-containing resin composition (b ′) and injecting it into a mold.
The second layer (b) may be formed by laminating a film, and these layers do not necessarily have to be in close contact with each other.
また、積層体（ｃ）は基材の上に第一層（ａ）と第二層（ｂ）が共押出し成形で成形されることが好ましい。 The laminate (c) is preferably formed by coextrusion of the first layer (a) and the second layer (b) on the substrate.
積層体（ｃ）のＪＩＳ Ｚ８７２９に基づいたＬ*,a*,ｂ*表色系におけるＬ*は２６以下であることが好ましく、２４．０以下であることがさらに好ましい。また、a*は−２．０以上２．０以下であることが好ましく、ｂ*は−１０．０以上０．３以下であることが好ましく、−３．０以上０以下であることがより好ましい。特に斯かる範囲であれば、漆黒性に優れた積層体（ｃ）が得られる。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。 Based on JIS Z8729 of the laminate (c) L *, a *, preferably b * L in colorimetric system * is 26 or less, still more preferably 24.0 or less. Further, a * is preferably -2.0 or more and 2.0 or less, b * is preferably -10.0 or more and 0.3 or less, and more preferably -3.0 or more and 0 or less. preferable. If it is such a range in particular, a laminate (c) excellent in jet-blackness can be obtained. The smaller L * is, the higher the degree of blackness (the lower the lightness). The closer a * and b * are to zero (0), the blacker the hue. Also, it can be said that bluish (blue) has a stronger hue as b * is more negative. Therefore, from the viewpoint of jet blackness, it is considered that jet blackness is high when it is black having a slight bluish color (blue color), so the above numerical range is considered to be preferable.
グロスメーターＧＭ−２６Ｄ（村上色彩研究所製）の６０°グロスにおいて、グロス値は８０以上であることが好ましく、８５以上であることがさらに好ましい。特に斯かる範囲であれば、光沢によりＬ*を小さくできるため、漆黒性に優れた積層体（ｃ）が得られる。 The 60 ° gloss of the gloss meter GM-26D (manufactured by Murakami Color Research Laboratory) preferably has a gloss value of 80 or more, more preferably 85 or more. In such a range in particular, L * can be reduced by the gloss, so that a laminate (c) excellent in jet blackness can be obtained.
以下本発明について実施例を掲げて更に詳しく説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、本実施例中で単に「％」と記載した場合は「質量％」を指すものとする。また、「カーボンブラック」を「ＣＢ」、「カーボンナノチューブ」を「ＣＮＴ」と略記することがある。 EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, when only describing as "%" in a present Example, "mass%" shall be pointed out. In addition, "carbon black" may be abbreviated as "CB", and "carbon nanotube" may be abbreviated as "CNT".
＜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>
Physical properties of the laminate used in each of the following Examples and Comparative Examples were measured by the following methods.
＜膜厚＞
積層体中の第一層、第二層の膜厚は膜厚計（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 first layer and the second 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*＞
積層体の第二層の表面方向から、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 second layer of the laminate, brightness (L * ) and chromaticity (a *) in the L * a * b * color specification system defined by JIS Z8729 using a color difference meter (SpectroColorMeter SE2000 manufactured by NIPPON DENSHOKU Co., Ltd.) , 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、積層体の第二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>
Measure the absolute reflection spectrum at a wavelength of 300 to 1500 nm in the range of 5 nm from the surface direction of the second layer of the laminate using an ultraviolet visible near infrared spectrophotometer (manufactured by Hitachi, Ltd., UV-3500, using integrating sphere) The weighted average value of each reflectance of wavelength 380 nm-780 nm was calculated | required, and this was made into 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。
Fiber diameter of carbon nanotubes
The obtained carbon nanotubes were observed by a scanning transmission electron microscope (JEM-6700M manufactured by JEOL Ltd.). In the observation photograph, arbitrary 100 carbon nanotubes were selected, the outer diameter of each was measured, and the fiber diameter (nm) of the carbon nanotubes was calculated by calculating the number average value.
＜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>
The carbon black was observed by a scanning transmission electron microscope (JEM-6700M manufactured by Nippon Denshi Co., Ltd.). In the observation photograph, 100 arbitrary carbon blacks were selected, the outer diameter of each was measured, and the average particle diameter (nm) of carbon black was calculated by calculating the number average value.
＜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。
<Example of catalyst for carbon nanotube synthesis and production of carbon nanotubes>
The catalyst for carbon nanotube synthesis and the carbon nanotube used in each of the following Examples and Comparative Examples were produced 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 Catalyst (A) for Carbon Nanotube Synthesis>
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. After transferring to a heat resistant container and drying for 30 minutes at a temperature of 190 ± 5 ° C. using an electric oven to evaporate water, it was ground in a mortar to obtain a precursor of a catalyst for carbon nanotube synthesis (A) . 100 g of the obtained precursor of the catalyst for carbon nanotube synthesis (A) is weighed in a heat resistant container, calcined in an atmosphere of 500 ° C. ± 5 ° C. in air for 30 minutes in a muffle furnace, and then crushed in a mortar I got (A).
＜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 catalyst (B) for carbon nanotube synthesis>
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 water, and then ground in a mortar to obtain a precursor of a catalyst (B) for carbon nanotube synthesis . 100 g of the obtained precursor of the catalyst for carbon nanotube synthesis (B) is weighed in a heat resistant container, calcined in an atmosphere of 500 ° C. ± 5 ° C. in air for 30 minutes in a muffle furnace, and then pulverized in a mortar I got (B).
＜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)>
In a central portion of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an inner volume of 10 liters, a quartz glass heat-resistant dish, in which 1.0 g of a catalyst for carbon nanotube synthesis (A) was dispersed, was installed. The 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 an external heater and heated until the center temperature in a horizontal reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube for 1 minute at a flow rate of 0.1 liter per 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 temperature in the reaction tube was cooled to 100 ° C. or less, and the obtained carbon nanotubes were collected. The obtained carbon nanotubes were crushed and filtered through a 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)>
In a central portion of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an inner volume of 10 liters, a quartz glass heat-resistant dish, in which 1.0 g of a catalyst for carbon nanotube synthesis (A) was dispersed, was installed. The 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 an external heater and heated until the center temperature in a horizontal reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube for 1 minute at a flow rate of 0.1 liter per 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 temperature in the reaction tube was cooled to 100 ° C. or less, and the obtained carbon nanotubes were collected. The obtained carbon nanotubes were crushed and filtered through a 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)>
In a central portion of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an inner volume of 10 liters, a quartz glass heat-resistant dish in which 1.0 g of a catalyst (B) for carbon nanotube synthesis was dispersed was installed. The 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 an external heater and heated until the center temperature in a horizontal reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube for 1 minute at a flow rate of 0.1 liter per 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 temperature in the reaction tube was cooled to 100 ° C. or less, and the obtained carbon nanotubes were collected. The obtained carbon nanotubes were crushed and filtered through a 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)>
In a central portion of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an inner volume of 10 liters, a quartz glass heat-resistant dish in which 1.0 g of a catalyst (B) for carbon nanotube synthesis was dispersed was installed. The 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 an external heater and heated until the center temperature in a horizontal reaction tube became 700 degreeC. After reaching 700 ° C., hydrogen gas was introduced into the reaction tube for 1 minute at a flow rate of 0.1 liter per 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 temperature in the reaction tube was cooled to 100 ° C. or less, and the obtained carbon nanotubes were collected. The obtained carbon nanotubes were crushed and filtered through a 80 mesh wire mesh.
＜第一層形成用樹脂組成物の製造＞
まず、実施例に先立って、第一層形成用樹脂組成物の作製方法を以下に示す。
<Production of resin composition for forming first layer>
First, prior to Examples, a method for producing a resin composition for forming a first layer is shown below.
＜第一層形成用樹脂組成物１の製造＞
顔料としてカーボンブラック１（ファーネスブラック粉、ニテロン♯１０ＭＡＦ、平均粒径４０ｎｍ、新日化カーボン社製）０．５部、樹脂としてＨＤＰＥ樹脂（高密度ポリエチレン樹脂、ハイゼックス６００８B、日本ポリエチレン社製）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、２２０℃で押し出し、ペレタイザーでカットすることで第一層形成用樹脂組成物１を得た。
<Production of Resin Composition 1 for Forming First Layer>
0.5 parts of carbon black 1 (furness black powder, NITERON # 10 MAF, average particle diameter 40 nm, manufactured by Nippon Steel Carbon Co., Ltd.) as a pigment, HDPE resin as resin (high density polyethylene resin, Hyzex 6008 B, manufactured by Nippon Polyethylene Co., Ltd.) 99 .5 parts were put into a super mixer (manufactured by Kawata Co., Ltd.) and stirred at 25 ° C for 3 minutes to obtain a mixture. Subsequently, the mixture was put into a twin-screw extruder (manufactured by Nippon Placon Co., Ltd.), extruded at 220 ° C., and cut by a pelletizer to obtain a resin composition 1 for forming a first layer.
＜第一層形成用樹脂組成物２〜８の製造＞
表１に挙げた樹脂の種類、顔料の添加量に、それぞれ変更した以外は、第一層形成用樹脂組成物１の製造方法と同様の方法により、それぞれ第一層形成用樹脂組成物２〜８を得た。
<Production of Resin Composition 2 to 8 for Forming First Layer>
Resin composition for forming the first layer 2-2 respectively by the same method as the method for producing the resin composition for forming the first layer 1 except that the kind of resin and the addition amount of the pigment listed in Table 1 are changed respectively. I got eight.
＜第二層形成用樹脂組成物の製造＞
続いて、第二層形成用樹脂組成物の作製方法を以下に示す。
<Production of Resin Composition for Forming Second Layer>
Then, the preparation methods of the resin composition for 2nd layer formation are shown below.
＜第二層形成用樹脂組成物１の製造＞
カーボンナノチューブとしてカーボンナノチューブ（Ａ１）０．０５部、樹脂としてＰＰ樹脂（ポリプロピレン樹脂、プライムポリプロＦ３２７、プライムポリマー社製）９９．９５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、２４０℃で押し出し、ペレタイザーでカットすることで第二層形成用樹脂組成物１を得た。
<Production of Resin Composition 1 for Forming Second Layer>
0.05 parts of carbon nanotubes (A1) as carbon nanotubes and 99.95 parts of PP resin (polypropylene resin, Prime Polypro F327, made by Prime Polymer Co., Ltd.) as a resin are put into a super mixer (made by Kawata Co., Ltd.) Stir for 3 minutes to obtain a mixture. Next, the mixture was charged into a twin-screw extruder (manufactured by Nippon Placon Co., Ltd.), extruded at 240 ° C., and cut with a pelletizer to obtain a resin composition 1 for forming a second layer.
＜第二層形成用樹脂組成物２〜７の製造＞
表２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、第一層形成用樹脂組成物１の製造方法と同様の方法により、それぞれ第一層形成用樹脂組成物２〜７を得た。
<Production of Resin Compositions 2 to 7 for Forming Second Layer>
Resin for forming the first layer by the same method as the method for producing the resin composition for forming the first layer 1 except that the type of the resin, the type of the carbon nanotube, and the addition amount of the carbon nanotube listed in Table 2 were changed The compositions 2 to 7 were obtained.
＜第二層形成用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）０．０５部、およびＰＰ樹脂（ポリプロピレン、プライムポリプロＦ３２７、プライムポリマー社製）９９．９５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、２４０℃で押し出し、ペレタイザーでカットすることで第二層形成用カーボンブラック含有樹脂組成物１の作製を得た。
<Production of Carbon Black-Containing Resin Composition 1 for Forming Second Layer>
Super mixer with 0.05 parts of carbon black (furness black powder, Niteron # 10, average particle diameter 40 nm, manufactured by Nippon Steel Carbon Co., Ltd.), and 99.95 parts of PP resin (polypropylene, Prime Polypro F327, manufactured by Prime Polymer Co.) The mixture was poured into (Kawata Co., Ltd.) and stirred at 25 ° C. for 3 minutes to obtain a mixture. Subsequently, the mixture was introduced into a twin-screw extruder (manufactured by Nippon Placon Co., Ltd.), extruded at 240 ° C., and cut with a pelletizer to obtain a carbon black-containing resin composition 1 for forming a second layer.
（実施例１）
＜積層体１の作成＞
多層ブロー成形機（株式会社プラコー製）を用いて、第一層形成用樹脂組成物１と第二層形成用樹脂組成物１を用いて、内側に第一層（膜厚１．８ｍｍ）、外側に第二層（膜厚０．２ｍｍ）を形成した積層体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
<Creating a Laminate 1>
A first layer (film thickness 1.8 mm) on the inner side using a resin composition 1 for forming a first layer and a resin composition 1 for forming a second layer using a multilayer blow molding machine (manufactured by Placo Co., Ltd.), The layered product 1 which produced the 2nd layer (film thickness 0.2 mm) outside was produced. L * a * b * and average reflectance were measured about the obtained laminated body.
（実施例２〜１７）
実施例１で使用した第一層形成用樹脂組成物１または第二層形成用樹脂組成物１の替わりに、表３に掲載した第一層形成用樹脂組成物または第二層形成用樹脂組成物を用いて、第一層または第二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２〜１７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 17)
The resin composition for forming the first layer or the resin composition for forming the second layer listed in Table 3 instead of the resin composition for forming the first layer or the resin composition for forming the second layer 1 used in Example 1 Laminates 2 to 17 were produced in the same manner as in Example 1 except that the type or thickness of the first layer or the second layer was changed using a metal. L * a * b * and average reflectance were measured about the obtained laminated body.
表３に実施例１〜１７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 3 shows preparation conditions and evaluation results of the laminates manufactured in Examples 1 to 17.
Evaluation criteria for jet blackness were as follows.
場合 L * less than 24 and b * less than 0.3 (very good)
○ If L * satisfies both 24 and 26 and b * is 0.3 or less (good)
× L * exceeds 26 or b * exceeds 0.3 or less (defect)
（比較例１）
＜積層体１８の作製＞
実施例１で使用した第二層形成用樹脂組成物１の代わりに第二層形成用カーボンブラック含有樹脂組成物１を用いて、内側に第一層（膜厚１．８ｍｍ）、外側に第二層（膜厚０．２ｍｍ）を形成した積層体１８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。
(Comparative example 1)
<Production of Laminate 18>
A carbon black-containing resin composition 1 for forming a second layer is used in place of the resin composition 1 for forming a second layer used in Example 1, and a first layer (film thickness 1.8 mm) is formed on the inner side, The laminated body 18 in which two layers (film thickness 0.2 mm) were formed was produced. L * a * b * and average reflectance were measured about the obtained laminated body.
（比較例２）
実施例１で第二層を形成しない第１層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)
The L * a * b * and the average reflectance were measured for only the first layer in which the second layer was not formed in Example 1.
表４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 4 shows preparation conditions and evaluation results of the laminates manufactured in Comparative Examples 1 and 2.
上記結果から、本発明のカーボンナノチューブを含む積層体は、カーボンナノチューブを含まない積層体よりも、漆黒性の高い積層体であることが明らかとなった。 From the above results, it has become clear that the laminate containing the carbon nanotube of the present invention is a laminate having a higher jet-black than the laminate containing no carbon nanotube.
押出し成形や射出成形についても、共押出成形や共射出成形することで、同様に積層体を製造し、漆黒性の高い積層体が得られることを確認した。 Also for extrusion molding and injection molding, it was confirmed that a laminate was similarly produced by co-extrusion molding and co-injection molding, and a laminate having high jet-blackness could be obtained.
Claims (6)
（１）第一層は、顔料と樹脂とを含む。
（２）第二層は、カーボンナノチューブと樹脂とを含む。
（３）第一層および第二層に含まれる樹脂は、それぞれ独立に、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン―酢酸ビニル共重合体樹脂、塩化ビニリデン樹脂、ポリカーボネード樹脂およびポリエステル樹脂からなる群より選ばれる少なくとも１種を含む。
（４）第二層に含まれるカーボンナノチューブの含有量が、第二層全体に対して、０．００５質量％以上０．１質量％以下である。 A laminate comprising at least two layers of a first layer and a second layer, wherein the laminate satisfies the following conditions (1) to (4) .
(1) The first layer contains a pigment and a resin.
(2) The second layer contains carbon nanotubes and a resin.
(3) The resins contained in the first layer and the second layer are each independently selected from the group consisting of polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, vinylidene chloride resin, polycarbonate resin and polyester resin It contains at least one kind.
(4) The content of carbon nanotubes contained in the second layer is 0.005% by mass or more and 0.1% by mass or less with respect to the entire second layer.
（１）第一層は、顔料と樹脂とを含む。
（２）第二層は、カーボンナノチューブと樹脂とを含む。
（３）第一層および第二層に含まれる樹脂は、それぞれ独立に、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン―酢酸ビニル共重合体樹脂、塩化ビニリデン樹脂、ポリカーボネード樹脂およびポリエステル樹脂からなる群より選ばれる少なくとも１種を含む。
（４）第二層に含まれるカーボンナノチューブの含有量が、第二層全体に対して、０．００５質量％以上０．１質量％以下である。 A method for producing a laminate having at least two layers of a first layer and a second layer, wherein the following conditions (1) to (4) are satisfied, and extrusion molding, injection molding, blow molding, compression molding, transfer molding, A method for producing a laminate, which is produced by any method of inflation molding or calendar molding.
(1) The first layer contains a pigment and a resin.
(2) The second layer contains carbon nanotubes and a resin.
(3) The resins contained in the first layer and the second layer are each independently selected from the group consisting of polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, vinylidene chloride resin, polycarbonate resin and polyester resin It contains at least one kind.
(4) The content of carbon nanotubes contained in the second layer is 0.005% by mass or more and 0.1% by mass or less with respect to the entire second layer.
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