JP2011195408A - Composite sheet and method for production thereof - Google Patents
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本発明は、複合シート及びその製造方法 The present invention relates to a composite sheet and a method for producing the same
近年、炭素骨格を有し且つ形状異方性の高い物質として、黒鉛をその層面間で剥離し、層面（グラフェン）の重なりが数十層以下になるまで薄片化した薄片化黒鉛が注目されており、薄片化黒鉛は非常に大きな表面積を有するため、薄片化黒鉛の添加で各種機能が発現すると期待されている。 In recent years, exfoliated graphite, which has a carbon skeleton and has high shape anisotropy, has been attracted attention by exfoliating graphite between its layer surfaces and exfoliating until the layer surface (graphene) overlaps to several tens of layers or less. Since exfoliated graphite has a very large surface area, the addition of exfoliated graphite is expected to exhibit various functions.
又、従来から、高度なバリア性を有するバリア材が所望されており、種々検討がなされている。例えば、特許文献１には、プラスチック基材（Ｉ）上に、コーティング膜層（II）を設けた構成のガスバリア性フィルムにおいて、コーティング膜層（II）が、少なくとも下記の非水溶性樹脂微粒子（Ａ）、金属酸化物（Ｂ）を含有し、コーティング膜層（II）が（Ｂ）金属酸化物を主とするマトリックスに、成分（Ａ）が分散した構造となっているガスバリア性フィルムが開示されている。 Conventionally, a barrier material having a high barrier property has been desired, and various studies have been made. For example, Patent Document 1 discloses that in a gas barrier film having a coating film layer (II) provided on a plastic substrate (I), the coating film layer (II) has at least the following water-insoluble resin fine particles ( A) A gas barrier film containing a metal oxide (B) and having a structure in which the component (A) is dispersed in a matrix mainly composed of the metal oxide (B) in the coating film layer (II) is disclosed. Has been.
しかしながら、上記ガスバリア性フィルムは、コーティング膜によるものであり、ピンホールやクラックなどの欠陥が避けられず、そのためにガスバリア性が低下するという問題点を有している。 However, the gas barrier film is a coating film, and defects such as pinholes and cracks are unavoidable, so that the gas barrier property is lowered.
更に、特許文献２には、粘土のみ又は粘土と添加剤からなる膜を製造する方法であって、粘土が液体に分散した所定の固液比の粘土ペーストを作製し、この粘土ペーストを物体の表面に塗布し、これを乾燥し、剥離する粘土膜の製造方法が開示されている。 Furthermore, Patent Document 2 discloses a method for producing a film made of only clay or a clay and an additive, and a clay paste having a predetermined solid-liquid ratio in which clay is dispersed in a liquid is prepared. A method for producing a clay film that is applied to a surface, dried, and peeled is disclosed.
しかしながら、得られた粘度膜は、水素や酸素についてバリア性に優れているものの、水蒸気バリア性が低いという問題点を有する。 However, although the obtained viscosity film is excellent in barrier properties with respect to hydrogen and oxygen, it has a problem of low water vapor barrier properties.
本発明は、優れたガスバリア性及び水蒸気バリア性を有する複合シート及びその製造方法を提供する。 The present invention provides a composite sheet having excellent gas barrier properties and water vapor barrier properties and a method for producing the same.
本発明の複合シートは、黒鉛化合物を薄片化してなる薄片化黒鉛と層状珪酸塩とを含有しており、上記薄片化黒鉛と上記層状珪酸塩とが不規則に重なり合っていることを特徴とする。 The composite sheet of the present invention contains exfoliated graphite obtained by exfoliating a graphite compound and a layered silicate, and the exfoliated graphite and the layered silicate are irregularly overlapped. .
本発明において用いられる黒鉛化合物としては、黒鉛、黒鉛層間化合物の何れであってもよい。なお、黒鉛に官能基が化学的に結合してしても、或いは、黒鉛に官能基が弱い相互作用により疑似的に結合していてもよい。 The graphite compound used in the present invention may be any of graphite and graphite intercalation compounds. Note that a functional group may be chemically bonded to graphite, or a functional group may be artificially bonded to graphite due to weak interaction.
黒鉛としては、粒子全体で単一の多層構造を有する黒鉛が好ましく、例えば、天然黒鉛、キッシュ黒鉛、高配向性熱分解黒鉛などが挙げられる。天然黒鉛とキッシュ黒鉛は、各層面（基本層）が略単一の方位を有する単独の結晶であり、高配向性熱分解黒鉛の各層面（基本層）は異なる方位を有する多数の小さな化粧の集合体である。 As the graphite, graphite having a single multilayer structure as a whole is preferable, and examples thereof include natural graphite, quiche graphite, and highly oriented pyrolytic graphite. Natural graphite and quiche graphite are single crystals in which each layer surface (basic layer) has a substantially single orientation, and each layer surface (basic layer) of highly oriented pyrolytic graphite has a number of small makeups having different orientations. It is an aggregate.
黒鉛層間化合物は、上記黒鉛の層面間にインターカレーターを挿入することによって形成されている。黒鉛層間化合物における黒鉛の層面間に挿入されるインターカレーターとしては、特に限定されず、例えば、酸、酸化剤、金属、金属塩、気体、ハロゲン化合物などが挙げられ、高圧条件を用いることなく黒鉛層間化合物を生成することができるので、酸と酸化剤との混合物が好ましい。インターカレーターは単独で用いられても二種以上が併用されてもよい。 The graphite intercalation compound is formed by inserting an intercalator between the graphite layer surfaces. The intercalator inserted between the graphite layer surfaces in the graphite intercalation compound is not particularly limited, and examples thereof include acids, oxidants, metals, metal salts, gases, halogen compounds, and the like, without using high-pressure conditions. Since an intercalation compound can be formed, a mixture of an acid and an oxidizing agent is preferred. An intercalator may be used independently or 2 or more types may be used together.
酸としては、例えば、硝酸、塩酸、硫酸、カルボン酸、クロム酸、リン酸、ヨウ素酸などが挙げられる。酸化剤としては、例えば、硝酸カリウム、硝酸セリウムアンモニウム、過塩素酸、過マンガン酸塩などが挙げられる。金属としては、例えば、カリウム、ナトリウムなどが挙げられる。金属塩としては、例えば、塩化ナトリウム、塩化カリウム、硫酸銅、酢酸ナトリウムなどが挙げられる。気体としては、例えば、水素などが挙げられる。ハロゲン化合物としては、例えば、塩化ヨウ素、塩化臭素、臭化ヨウ素、フッ化ヨウ素、フッ化臭素、フッ化塩素、フッ素、塩素、塩化アルミニウムなどが挙げられる。 Examples of the acid include nitric acid, hydrochloric acid, sulfuric acid, carboxylic acid, chromic acid, phosphoric acid, iodic acid and the like. Examples of the oxidizing agent include potassium nitrate, cerium ammonium nitrate, perchloric acid, permanganate and the like. Examples of the metal include potassium and sodium. Examples of the metal salt include sodium chloride, potassium chloride, copper sulfate, sodium acetate and the like. Examples of the gas include hydrogen. Examples of the halogen compound include iodine chloride, bromine chloride, iodine bromide, iodine fluoride, bromine fluoride, chlorine fluoride, fluorine, chlorine, and aluminum chloride.
黒鉛の層面間にインターカレーターを挿入して黒鉛層間化合物を製造する方法としては、公知の方法を採用することができ、例えば、黒鉛をインターカレーターの溶液に分散させて、分散液中において黒鉛とインターカレーターとを反応させて黒鉛層間化合物を製造する方法、黒鉛と気体状のインターカレーターとを高圧下にて反応させて黒鉛層間化合物を製造する方法、酸化剤を用いてＨｕｍｍｅｒｓ−Ｏｆｆｅｍａｎ法によって黒鉛層間化合物を製造する方法などが挙げられ、酸化剤を用いてＨｕｍｍｅｒｓ−Ｏｆｆｅｍａｎ法によって黒鉛層間化合物を製造する方法が好ましい。 As a method for producing a graphite intercalation compound by inserting an intercalator between graphite layer surfaces, a known method can be adopted. For example, graphite is dispersed in an intercalator solution, and graphite and A method for producing a graphite intercalation compound by reacting with an intercalator, a method for producing a graphite intercalation compound by reacting graphite and a gaseous intercalator under high pressure, and a graphite by a Hummers-Offeman method using an oxidizing agent. The method of manufacturing an intercalation compound etc. are mentioned, The method of manufacturing a graphite intercalation compound by the Hummers-Offeman method using an oxidizing agent is preferred.
上述の要領で製造された黒鉛層間化合物に薄層化処理を施して原料黒鉛よりも薄層化させておくことが好ましい。黒鉛層間化合物に施す薄層化処理としては、例えば、黒鉛層間化合物にマイクロ波又は超音波を照射する方法、黒鉛層間化合物に物理的に応力を加えて黒鉛層間化合物を粉砕する方法などが挙げられる。 It is preferable to apply a thinning treatment to the graphite intercalation compound produced as described above to make it thinner than the raw material graphite. Examples of the thinning treatment applied to the graphite intercalation compound include a method of irradiating the graphite intercalation compound with microwaves or ultrasonic waves, and a method of physically applying stress to the graphite intercalation compound to pulverize the graphite intercalation compound. .
黒鉛化合物において、レーザー光回折法により粒度分布を測定した場合に５０％体積平均径として得られる値は、小さいと、黒鉛化合物を薄片化して得られる薄片化黒鉛において異方性が得られないことがあり、大きいと、黒鉛化合物の層面間に五員環を含有する環状化合物が侵入しにくくなり、黒鉛化合物の薄片化が進行しにくいことがあるので、０．１〜５０μｍが好ましい。 In graphite compounds, when the particle size distribution is measured by the laser diffraction method, the value obtained as the 50% volume average diameter is small, and anisotropy cannot be obtained in exfoliated graphite obtained by exfoliating graphite compounds. If it is large, a cyclic compound containing a five-membered ring does not easily enter between the layer surfaces of the graphite compound, and the flaking of the graphite compound may not easily proceed, so 0.1 to 50 μm is preferable.
なお、レーザー光回折法により粒度分布を測定した場合に５０％体積平均径として得られる値が２０μｍ未満である黒鉛化合物は、例えば、ＳＥＣカーボン社から商品名「ＳＮＯ−１５」などのＳＮＯシリーズにて、中越黒鉛工業所から商品名「ＣＸ−３０００」にて、伊藤黒鉛社からＣＮＰ−シリーズにて、ＸＧＳｉｅｎｃｅ社から商品名「ＸＧｎＰ−５」にて市販されている。 In addition, when the particle size distribution is measured by a laser light diffraction method, a graphite compound having a value obtained as a 50% volume average diameter of less than 20 μm is, for example, an SNO series such as a trade name “SNO-15” from SEC Carbon. These products are commercially available from Chuetsu Graphite Industries Co., Ltd. under the trade name “CX-3000”, from Ito Graphite Co. in the CNP-series, and from XGSience Corporation under the trade name “XGnP-5”.
次に、黒鉛化合物を薄片化する方法としては、黒鉛化合物を構成している層面を剥離させて薄片化黒鉛とすることができれば、特に限定されず、例えば、（１）黒鉛化合物と、一級アミン、ヒドラジン及びアンモニアからなる群から選ばれた少なくとも一種の窒素化合物と、水とを混合してｐＨが１０〜１４である混合液とし、上記黒鉛化合物を薄片化する薄片化黒鉛の製造方法、（２）黒鉛化合物と五員環を含有する環状化合物とを含む被処理液を振とうさせて、上記黒鉛化合物を薄片化する薄片化黒鉛の製造方法、（３）黒鉛化合物とアルカリ金属の水酸化物と水とを混合してｐＨが７〜１０である混合液とし、上記黒鉛化合物を薄片化する薄片化黒鉛の製造方法などが挙げられる。 Next, the method of exfoliating the graphite compound is not particularly limited as long as the layer surface constituting the graphite compound can be peeled to obtain exfoliated graphite. For example, (1) a graphite compound and a primary amine , A method for producing exfoliated graphite, wherein at least one nitrogen compound selected from the group consisting of hydrazine and ammonia and water are mixed to form a mixed solution having a pH of 10 to 14, and the graphite compound is exfoliated, 2) A method for producing exfoliated graphite in which a liquid to be treated containing a graphite compound and a cyclic compound containing a five-membered ring is shaken to exfoliate the graphite compound, and (3) hydroxylation of the graphite compound and alkali metal. Examples include a method for producing exfoliated graphite, in which a product and water are mixed to obtain a mixed solution having a pH of 7 to 10, and the graphite compound is exfoliated.
上記（１）の薄片化黒鉛の製造方法を説明する。窒素化合物としては、一級アミン、ヒドラジン及びアンモニアからなる群から選ばれた少なくとも一種の窒素化合物が用いられる。一級アミンとしては、例えば、メチルアミン、エタノールアミンなどが挙げられる。なお、窒素化合物は、単独で用いられても二種以上が併用されてもよい。 The method for producing exfoliated graphite (1) above will be described. As the nitrogen compound, at least one nitrogen compound selected from the group consisting of primary amine, hydrazine and ammonia is used. Examples of the primary amine include methylamine and ethanolamine. In addition, a nitrogen compound may be used independently or 2 or more types may be used together.
黒鉛化合物と窒素化合物と水とを混合して混合液を作製する方法としては、特に限定されず、例えば、黒鉛化合物を水に分散させて黒鉛化合物分散液を作製すると共に、窒素化合物を水に溶解させて窒素化合物水溶液を作製し、黒鉛化合物分散液と窒素化合物水溶液とを均一に混合して混合液を作製する方法、窒素化合物を水に溶解させて窒素化合物水溶液を作製し、この窒素化合物水溶液に黒鉛化合物を添加して均一に混合して混合液を作製する方法などが挙げられる。 A method for preparing a mixed liquid by mixing a graphite compound, a nitrogen compound, and water is not particularly limited. For example, a graphite compound is dispersed in water to prepare a graphite compound dispersion, and the nitrogen compound is mixed in water. A method of dissolving a nitrogen compound aqueous solution to prepare a mixed liquid by uniformly mixing a graphite compound dispersion and a nitrogen compound aqueous solution, and dissolving the nitrogen compound in water to prepare a nitrogen compound aqueous solution. Examples thereof include a method in which a graphite compound is added to an aqueous solution and mixed uniformly to prepare a mixed solution.
黒鉛化合物と窒素化合物と水とを混合させて混合液を作製するにあたって、得られる混合液のｐＨが１０〜１４となるように黒鉛化合物と窒素化合物と水の混合割合を調整する必要がある。 In preparing a mixed solution by mixing a graphite compound, a nitrogen compound, and water, it is necessary to adjust the mixing ratio of the graphite compound, the nitrogen compound, and water so that the pH of the obtained mixed solution becomes 10-14.
混合液をｐＨ１０〜１４に調整する理由は明確には解明されていないが、黒鉛化合物の層面間に窒素化合物を挿入させることによって、窒素化合物の有する非共有電子対間の静電反発力によって黒鉛化合物の対向する層面を互いが離間する方向に変位させることにより黒鉛化合物の層面間の間隔が拡がり、黒鉛化合物における層面間の剥離の進行を促進し黒鉛化合物を薄片化して薄片化黒鉛の製造を効率的に行うことができると考えている。そして、混合液をｐＨが１０〜１４となるように調整することによって、黒鉛化合物の層面間への窒素化合物の進入が容易となり、その結果、上述の作用によって黒鉛化合物の層面間における剥離が円滑に行われて黒鉛化合物を薄片化して薄片化黒鉛を効率良く製造できると考えられる。 The reason for adjusting the mixed solution to pH 10 to 14 is not clearly clarified, but by inserting a nitrogen compound between the layer surfaces of the graphite compound, the graphite repulsive force between the unshared electron pairs of the nitrogen compound is reduced. Displacement of the opposing layer surfaces of the compound in the direction away from each other widens the spacing between the layer surfaces of the graphite compound, promotes the progress of delamination between the layer surfaces of the graphite compound, and exfoliates the graphite compound to produce exfoliated graphite. I think it can be done efficiently. Then, by adjusting the mixed solution so that the pH is 10 to 14, the nitrogen compound can easily enter between the layer surfaces of the graphite compound, and as a result, the peeling between the layer surfaces of the graphite compound is smooth due to the above-described action. It is considered that the exfoliated graphite can be efficiently produced by flaking the graphite compound.
上述のように、黒鉛化合物と窒素化合物と水とを混合させてｐＨが１０〜１４の混合液を製造した後、この混合液を静置することによって黒鉛化合物の層面間における剥離を進行させ、黒鉛化合物を薄片化させて得られる薄片化黒鉛が水中に安定的に分散してなる薄片化黒鉛分散液を得ることができる。 As described above, a graphite compound, a nitrogen compound, and water are mixed to produce a mixed solution having a pH of 10 to 14, and then the separation between the layer surfaces of the graphite compound proceeds by allowing the mixed solution to stand, An exfoliated graphite dispersion liquid in which exfoliated graphite obtained by exfoliating a graphite compound is stably dispersed in water can be obtained.
次に、上記（２）の薄片化黒鉛の製造方法を説明する。先ず、上記黒鉛化合物と五員環を含有する環状化合物とを含有する被処理液を用意する。五員環を含有する環状化合物としては、特に限定されず、例えば、テトラヒドロフラン、Ｎ−メチルピロリドン、ピロール、チオフェン、イミダゾール、ピラゾール、チアゾール又はこれらの誘導体が挙げられ、テトラヒドロフラン、Ｎ−メチルピロリドンが好ましい。なお、五員環を含有する環状化合物は単独で用いられても二種以上が併用されてもよい。 Next, the manufacturing method of the exfoliated graphite of said (2) is demonstrated. First, a liquid to be treated containing the graphite compound and a cyclic compound containing a five-membered ring is prepared. The cyclic compound containing a five-membered ring is not particularly limited, and examples thereof include tetrahydrofuran, N-methylpyrrolidone, pyrrole, thiophene, imidazole, pyrazole, thiazole or derivatives thereof, and tetrahydrofuran and N-methylpyrrolidone are preferable. . In addition, the cyclic compound containing a 5-membered ring may be used independently, or 2 or more types may be used together.
五員環を含有する環状化合物が官能基を有している場合、官能基の炭素数は、大きいと、黒鉛化合物の層面間に五員環を含有する環状化合物が進入しにくくなり、黒鉛化合物の薄片化が進みにくくなることがあるので、４以下が好ましい。 When the cyclic compound containing a five-membered ring has a functional group, if the carbon number of the functional group is large, the cyclic compound containing the five-membered ring is difficult to enter between the layer surfaces of the graphite compound, and the graphite compound Is preferably 4 or less, because it may be difficult to proceed with thinning.
被処理液中における黒鉛化合物と五員環を有する環式化合物との含有割合は、黒鉛化合物が少ないと、黒鉛化合物に対して多量の溶媒を使用することとなり、環境負荷が大きくなることがあり、黒鉛化合物が多いと、黒鉛化合物の層面間に五員環を有する環式化合物が進入しにくくなることがあるので、黒鉛化合物１００重量部に対して五員環を含有する環状化合物１００〜１００万重量部が好ましく、１０００〜１０万重量部がより好ましい。 The content ratio of the graphite compound and the cyclic compound having a five-membered ring in the liquid to be treated is such that if the graphite compound is small, a large amount of solvent is used for the graphite compound, which may increase the environmental load. If the graphite compound is large, a cyclic compound having a five-membered ring may not easily enter between the graphite compound layer surfaces. Therefore, the cyclic compounds 100 to 100 containing a five-membered ring with respect to 100 parts by weight of the graphite compound. 10,000 parts by weight is preferable, and 1,000 to 100,000 parts by weight is more preferable.
黒鉛化合物と五員環を含有する環状化合物とを含有する被処理液を作製する方法としては、特に限定されず、例えば、黒鉛化合物を入れた容器内に五員環を含有する環状化合物を供給してもよいし、五員環を含有する環状化合物中に黒鉛化合物を供給してもよい。 A method for preparing a liquid to be treated containing a graphite compound and a cyclic compound containing a five-membered ring is not particularly limited. For example, a cyclic compound containing a five-membered ring is supplied into a container containing the graphite compound. Alternatively, the graphite compound may be supplied into a cyclic compound containing a five-membered ring.
そして、被処理液を振とうさせて黒鉛化合物を薄片化して、薄片化黒鉛が五員環を含有する環状化合物中に分散してなる薄片化黒鉛分散液を製造することができる。被処理液の振とう方法としては、特に限定されず、例えば、被処理液を入れた容器を手で上下方向又は左右方向に振ることによって容器内の被処理液を振とうする方法、被処理液を入れた容器を振とう装置に配設して容器を振とうさせて容器内の被処理液を振とうする方法などが挙げられる。 And a to-be-processed liquid is shaken, and a graphite compound is exfoliated, The exfoliated graphite dispersion liquid in which exfoliated graphite disperse | distributes in the cyclic compound containing a 5-membered ring can be manufactured. The method for shaking the liquid to be treated is not particularly limited. For example, a method for shaking the liquid to be treated in the container by shaking the container containing the liquid to be treated in the vertical direction or the left-right direction by hand. Examples include a method in which a container containing a liquid is disposed in a shaking device and the container is shaken to shake the liquid to be treated in the container.
このように、被処理液を振とうすることによって黒鉛化合物が薄片化されて、薄片化黒鉛が五員環を含有する環状化合物中に分散してなる薄片化黒鉛分散液が得られる理由は明確には解明されていないが、黒鉛化合物が黒鉛である場合には以下のように推察される。五員環を有する環式化合物は、黒鉛化合物と分子構造が類似しているため、黒鉛化合物の層面間に進入し易く、五員環を含有する環状化合物が黒鉛の層面間に進入することによって、互いに隣接する層面間に働いているファンデルワールス結合を切断することができ、その結果、黒鉛の層面間同士の剥離を容易にし、黒鉛の薄片化を進行させているものと考えられる。 Thus, it is clear why the exfoliated graphite dispersion liquid is obtained by exfoliating the graphite compound by shaking the liquid to be treated and dispersing the exfoliated graphite in a cyclic compound containing a five-membered ring. However, when the graphite compound is graphite, it is presumed as follows. Since a cyclic compound having a five-membered ring has a molecular structure similar to that of a graphite compound, it easily enters between the layer surfaces of the graphite compound, and a cyclic compound containing a five-membered ring enters between the layer surfaces of the graphite. It is considered that van der Waals bonds acting between adjacent layer surfaces can be cut, and as a result, the graphite layer surfaces can be easily separated from each other, and the graphite thinning is promoted.
又、黒鉛化合物が黒鉛層間化合物又は官能基を有する黒鉛である場合にも、インターカレーターが挿入されていない層面間や、官能基を有していない層面間において、上述の現象が生じる結果、黒鉛化合物の薄片化をより効率良く行うことができるものと考えられる。 Further, when the graphite compound is a graphite intercalation compound or a graphite having a functional group, the above phenomenon occurs as a result of the above phenomenon occurring between the layer surfaces in which no intercalator is inserted or between the layer surfaces having no functional group. It is considered that the compound can be thinned more efficiently.
続いて、上記（３）の薄片化黒鉛の製造方法を説明する。アルカリ金属の水酸化物としては、特に限定されず、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウムなどが挙げられ、水酸化ナトリウム、水酸化カリウムが好ましい。なお、アルカリ金属の水酸化物は、単独で用いられても二種以上が併用されてもよい。 Then, the manufacturing method of the exfoliated graphite of said (3) is demonstrated. The alkali metal hydroxide is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, and lithium hydroxide, and sodium hydroxide and potassium hydroxide are preferable. The alkali metal hydroxides may be used alone or in combination of two or more.
黒鉛化合物とアルカリ金属の水酸化物と水とを混合して混合液を作製する方法としては、特に限定されず、例えば、黒鉛化合物を水に分散させて黒鉛化合物分散液を作製すると共に、アルカリ金属の水酸化物を水に溶解させてアルカリ金属の水酸化物水溶液を作製し、黒鉛化合物分散液とアルカリ金属の水酸化物水溶液とを均一に混合して混合液を作製する方法、アルカリ金属の水酸化物を水に溶解させてアルカリ金属の水酸化物水溶液を作製し、このアルカリ金属の水酸化物水溶液に黒鉛化合物を添加して均一に混合して混合液を作製する方法などが挙げられる。 A method of preparing a mixed liquid by mixing a graphite compound, an alkali metal hydroxide, and water is not particularly limited. For example, a graphite compound dispersion is prepared by dispersing a graphite compound in water, and an alkali is used. A method in which a metal hydroxide is dissolved in water to prepare an alkali metal hydroxide aqueous solution, and a graphite compound dispersion and an alkali metal hydroxide aqueous solution are uniformly mixed to prepare a mixed solution, alkali metal A method of preparing an aqueous solution of an alkali metal hydroxide by dissolving the hydroxide of water in water, adding a graphite compound to the aqueous solution of the alkali metal hydroxide and uniformly mixing the solution, etc. It is done.
黒鉛化合物とアルカリ金属の水酸化物と水とを混合させて混合液を作製するにあたって、得られる混合液のｐＨが７〜１０となるように黒鉛化合物とアルカリ金属の水酸化物と水の混合割合を調整する。黒鉛化合物が黒鉛（黒鉛が官能基を有する場合を含む）である場合には、混合液のｐＨを８〜１０に調整することが好ましい。 When preparing a mixed solution by mixing a graphite compound, an alkali metal hydroxide and water, mixing the graphite compound, the alkali metal hydroxide and water so that the pH of the resulting mixed solution is 7 to 10 Adjust the percentage. When the graphite compound is graphite (including the case where the graphite has a functional group), it is preferable to adjust the pH of the mixed solution to 8 to 10.
混合液をｐＨ７〜１０に調整する理由は明確には解明されていないが、アルカリ金属の水酸化物由来のアルカリ金属イオンが黒鉛化合物の層面間に進入し、アルカリ金属イオンの有する正電荷同士の反発力によって、黒鉛化合物の対向する層面を互いが離間する方向に変位させることにより黒鉛化合物の層面間の間隔が拡がり、黒鉛化合物における層面間の剥離の進行を促進し黒鉛化合物を薄片化して薄片化黒鉛の製造を効率的に行うことができると考えている。そして、分散液をｐＨが７〜１０に調整することによって、黒鉛化合物の層面間へのアルカリ金属の水酸化物由来のアルカリ金属イオンの進入が容易となり、その結果、上述の作用によって黒鉛化合物の層面間における剥離が円滑に行われて黒鉛化合物を薄片化して薄片化黒鉛を効率良く製造できると考えられる。 The reason for adjusting the mixed solution to pH 7 to 10 is not clearly understood, but alkali metal ions derived from alkali metal hydroxide enter between the layer surfaces of the graphite compound, and the positive charges of the alkali metal ions are between each other. By repelling, the opposing layer surfaces of the graphite compound are displaced in a direction away from each other, thereby widening the spacing between the layer surfaces of the graphite compound, promoting the progress of delamination between the layer surfaces in the graphite compound, and flaking the graphite compound We believe that it is possible to efficiently produce graphite oxide. Then, by adjusting the pH of the dispersion to 7 to 10, it becomes easy for alkali metal ions derived from alkali metal hydroxide to enter between the layer surfaces of the graphite compound. It is considered that exfoliation between the layer surfaces is smoothly performed, and the graphite compound is exfoliated to efficiently produce exfoliated graphite.
上述のように、黒鉛化合物とアルカリ金属の水酸化物と水とを混合させてｐＨが７〜１０の混合液を製造した後、この混合液を静置することによって黒鉛化合物の層面間における剥離を進行させ、黒鉛化合物を薄片化させて得られる薄片化黒鉛が水中に安定的に分散してなる薄片化黒鉛分散液を得ることができる。 As described above, a graphite compound, an alkali metal hydroxide, and water are mixed to produce a mixed liquid having a pH of 7 to 10, and then the mixed liquid is allowed to stand to peel off the graphite compound between the layer surfaces. To obtain a exfoliated graphite dispersion in which exfoliated graphite obtained by exfoliating a graphite compound is stably dispersed in water.
上述の（１）〜（３）のようにして薄片化黒鉛が作製される。これらの薄片化黒鉛と後述する層状珪酸塩とから混合物分散液が作製される。薄片化黒鉛は分散液から遠心分離法や吸引濾過などの汎用の要領で分離されてもよい。更に、薄片化黒鉛は、洗浄され乾燥されてもよい。薄片化黒鉛分散液をそのまま後述する混合物分散液の作製に用いてもよいし、別の溶媒に置換されてもよい。 Exfoliated graphite is produced as described in (1) to (3) above. A mixture dispersion is prepared from these exfoliated graphite and a layered silicate described later. The exfoliated graphite may be separated from the dispersion by a general method such as centrifugal separation or suction filtration. Further, the exfoliated graphite may be washed and dried. The exfoliated graphite dispersion may be used as it is for preparing a mixture dispersion described later, or may be replaced with another solvent.
得られた薄片化黒鉛の層面の面方向に沿った大きさは、０．０１〜１０００μｍが好ましい。薄片化黒鉛の厚みは、１００ｎｍ以下が好ましい。薄片化黒鉛のアスペクト比は、１０〜５００が好ましい。 As for the magnitude | size along the surface direction of the layer surface of the obtained exfoliated graphite, 0.01-1000 micrometers is preferable. The thickness of exfoliated graphite is preferably 100 nm or less. The aspect ratio of exfoliated graphite is preferably 10 to 500.
薄片化黒鉛の層面の面方向に沿った大きさとは、薄片化黒鉛の面積が最も大きくなる方向から見た時に、薄片化黒鉛を包囲し得る最小径の真円の直径をいう。 The size along the surface direction of the layer surface of exfoliated graphite refers to the diameter of a perfect circle having the smallest diameter that can surround exfoliated graphite when viewed from the direction in which the area of exfoliated graphite is the largest.
薄片化黒鉛の厚みとは、薄片化黒鉛の面積が最も大きくなる方向から見た時の薄片化黒鉛の表面に対して直交する方向の薄片化黒鉛の最大寸法をいう。 The thickness of exfoliated graphite refers to the maximum dimension of exfoliated graphite in the direction orthogonal to the surface of exfoliated graphite when viewed from the direction in which the area of exfoliated graphite is the largest.
薄片化黒鉛のアスペクト比とは、薄片化黒鉛の長さとなる方向に対して層面に沿い且つ直交する方向において最大の寸法を薄片化黒鉛の幅とした時に、薄片化黒鉛の長さを薄片化黒鉛の幅で除した値をいう。 The aspect ratio of exfoliated graphite is the exfoliated graphite length when the maximum dimension in the direction along the layer surface and perpendicular to the direction of the exfoliated graphite length is the width of exfoliated graphite. The value divided by the width of graphite.
なお、薄片化黒鉛の長さ、厚み及びアスペクト比は、ＦＥ−ＳＥＭ又はＡＦＭによって測定することができる。 In addition, the length, thickness, and aspect ratio of exfoliated graphite can be measured by FE-SEM or AFM.
一方、複合シートを構成している層状珪酸塩としては、天然物であっても合成物であってもよく、例えば、モンモリロナイト、サポナイト、ヘクトライト、バイデライト、スティブンサイト、ノントロナイトなどのスメクタイト系粘土鉱物や、バーミキュライト、ハロイサイト、膨潤性マイカなどが挙げられ、モンモリロナイト、膨潤性マイカが好ましい。なお、層状珪酸塩は、単独で用いられても二種以上が併用されてもよい。又、層状珪酸塩として、表面が有機官能基で修飾された有機化クレイが用いられてもよい。 On the other hand, the layered silicate constituting the composite sheet may be a natural product or a synthetic product, for example, smectite such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite. Clay minerals, vermiculite, halloysite, swellable mica and the like, and montmorillonite and swellable mica are preferred. In addition, a layered silicate may be used independently or 2 or more types may be used together. Further, as the layered silicate, an organized clay whose surface is modified with an organic functional group may be used.
層状珪酸塩の形状は、平均長さが０．０１〜１０００μｍ、厚みが１００ｎｍ以下、アスペクト比が１０〜５００である層状珪酸塩が好ましく、平均長さが０．１〜１０μｍ、厚みが２０ｎｍ以下、アスペクト比が５０〜２００である層状珪酸塩がより好ましい。 The shape of the layered silicate is preferably a layered silicate having an average length of 0.01 to 1000 μm, a thickness of 100 nm or less, and an aspect ratio of 10 to 500, an average length of 0.1 to 10 μm, and a thickness of 20 nm or less. A layered silicate having an aspect ratio of 50 to 200 is more preferable.
層状珪酸塩の長さとは、層状珪酸塩の面積が最も大きくなる方向から見た時に、層状珪酸塩を包囲し得る最小径の真円の直径をいう。層状珪酸塩の平均長さとは、各層状珪酸塩の長さを相加平均した値をいう。 The length of the layered silicate refers to the diameter of the smallest perfect circle that can surround the layered silicate when viewed from the direction in which the area of the layered silicate becomes the largest. The average length of the layered silicate refers to a value obtained by arithmetically averaging the length of each layered silicate.
層状珪酸塩の厚みとは、層状珪酸塩の面積が最も大きくなる方向から見た時の層状珪酸塩の表面に対して直交する方向の層状珪酸塩の最大寸法をいう。層状珪酸塩の平均長さとは、各層状珪酸塩の長さを相加平均した値をいう。 The thickness of the layered silicate refers to the maximum dimension of the layered silicate in the direction orthogonal to the surface of the layered silicate when viewed from the direction in which the area of the layered silicate becomes the largest. The average length of the layered silicate refers to a value obtained by arithmetically averaging the length of each layered silicate.
層状珪酸塩のアスペクト比とは、層状珪酸塩の長さとなる方向に対して層状珪酸塩の表面に沿い且つ直交する方向において最大の寸法を層状珪酸塩の幅とした時に、層状珪酸塩の長さを層状珪酸塩の幅で除した値をいう。 The aspect ratio of the layered silicate is the length of the layered silicate when the maximum dimension in the direction along the surface of the layered silicate and perpendicular to the direction of the length of the layered silicate is the width of the layered silicate. The value obtained by dividing the thickness by the width of the layered silicate.
なお、層状珪酸塩の長さ、厚み及びアスペクト比は、ＦＥ−ＳＥＭ又はＡＦＭによって測定することができる。 The length, thickness and aspect ratio of the layered silicate can be measured by FE-SEM or AFM.
次に、薄片化黒鉛と層状珪酸塩とを分散媒体中に分散させた混合物分散液を作製する。薄片化黒鉛分散液から分離した薄片化黒鉛を用いる場合には、薄片化黒鉛と層状珪酸塩とを分散媒体中に分散させて混合物分散液を製造する。なお、分散媒体としては、薄片化黒鉛と層状珪酸塩とを分散させることができれば、特に限定されず、例えば、水、エチルアルコール、メチルアルコールなどのアルコール、酢酸エチル、トルエン、ジエチルケトン、ジエチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジメチルホルムアミド（ＤＭＦ）などの汎用の媒体が挙げられ、水、アルコール、テトラヒドロフランが好ましい。なお、分散媒体は、単独で用いられても二種以上が併用されてもよい。 Next, a mixture dispersion in which exfoliated graphite and layered silicate are dispersed in a dispersion medium is prepared. When exfoliated graphite separated from exfoliated graphite dispersion is used, exfoliated graphite and layered silicate are dispersed in a dispersion medium to produce a mixture dispersion. The dispersion medium is not particularly limited as long as exfoliated graphite and layered silicate can be dispersed. Examples thereof include water, alcohols such as ethyl alcohol and methyl alcohol, ethyl acetate, toluene, diethyl ketone, and diethyl ether. , Tetrahydrofuran (THF), dimethylformamide (DMF) and the like, and water, alcohol, and tetrahydrofuran are preferable. In addition, a dispersion medium may be used independently or 2 or more types may be used together.
混合物分散液の作製方法は、特に限定されず、例えば、薄片化黒鉛を分散媒体中に分散させてなる薄片化黒鉛分散液と、層状珪酸塩を分散媒体中に分散させてなる層状珪酸塩分散液とを混合することによって混合物分散液を製造する方法などが挙げられる。なお、混合物分散液中には、必要に応じてバンダーポリマー、分散助剤が含有されてもよい。 The method of preparing the mixture dispersion is not particularly limited. For example, exfoliated graphite dispersion obtained by dispersing exfoliated graphite in a dispersion medium, and layered silicate dispersion obtained by dispersing layered silicate in a dispersion medium. Examples thereof include a method of producing a mixture dispersion by mixing a liquid. The mixture dispersion may contain a bander polymer and a dispersion aid as necessary.
又、薄片化黒鉛分散液をそのまま用いる場合には、薄片化黒鉛分散液中に層状珪酸塩を供給して薄片化黒鉛と層状珪酸塩とを水中に分散させて混合物分散液を作製すればよい。 When the exfoliated graphite dispersion is used as it is, a layered silicate is supplied into the exfoliated graphite dispersion and the exfoliated graphite and the layered silicate are dispersed in water to prepare a mixture dispersion. .
混合物分散液中における薄片化黒鉛の含有量は、少ないと、得られる複合シートの水蒸気バリア性が低下し、多いと、相対的に層状珪酸塩の含有量が少なくなり、得られる複合シートの強度や成形性が低下するので、層状珪酸塩１００重量部に対して５〜５００重量部が好ましい。 If the content of exfoliated graphite in the mixture dispersion is small, the water vapor barrier property of the resulting composite sheet is lowered, and if it is large, the content of the layered silicate is relatively reduced, and the strength of the resulting composite sheet is reduced. And the moldability is reduced, so 5 to 500 parts by weight is preferable with respect to 100 parts by weight of the layered silicate.
更に、混合物分散液中における分散媒体の量は、少ないと、混合物分散液からの複合シートの製造が困難となることがあり、多いと、複合シートの強度が低下することがあるので、混合物分散液中、２０〜９８重量％が好ましい。 Furthermore, if the amount of the dispersion medium in the mixture dispersion is small, it may be difficult to produce a composite sheet from the mixture dispersion, and if it is large, the strength of the composite sheet may be reduced. 20 to 98 weight% is preferable in a liquid.
そして、上記混合物分散液から分散媒体を除去して、薄片化黒鉛及び層状珪酸塩を含む混合物をシート状に成形することによって複合シートを製造することができる。混合物分散液から分散媒体を除去して複合シートを製造する方法としては、特に限定されず、例えば、混合物分散液から遠心分離、濾過などの汎用の方法を用いて分散媒体を低減した上で、薄片化黒鉛及び層状珪酸塩を含む混合物を支持体上にシート状に成形し、この状態で混合物中に含まれている分散媒体を除去して乾燥させて、薄片化黒鉛と層状珪酸塩とを含有してなる複合シートを製造する方法、混合物分散液を支持体上に塗布した後、薄片化黒鉛及び層状珪酸塩を含む混合物中に含まれている分散媒体を除去して乾燥させて、薄片化黒鉛と層状珪酸塩とを含有してなる複合シートを製造する方法などが挙げられる。 And a composite sheet can be manufactured by removing a dispersion medium from the said mixture dispersion liquid, and shape | molding the mixture containing exfoliated graphite and a layered silicate in a sheet form. The method for producing the composite sheet by removing the dispersion medium from the mixture dispersion is not particularly limited.For example, after reducing the dispersion medium using a general-purpose method such as centrifugation or filtration from the mixture dispersion, A mixture containing exfoliated graphite and layered silicate is formed into a sheet on a support, and in this state, the dispersion medium contained in the mixture is removed and dried to obtain exfoliated graphite and layered silicate. A method for producing a composite sheet containing the composition, after applying a mixture dispersion on a support, removing the dispersion medium contained in the mixture containing exfoliated graphite and layered silicate, and drying, Examples thereof include a method for producing a composite sheet containing graphite oxide and layered silicate.
薄片化黒鉛及び層状珪酸塩を含む混合物中に含まれている分散媒体を除去する方法としては、特に限定されず、例えば、混合物を真空中に配設し、混合物中に含まれている分散媒体を減圧下にて蒸発、除去する方法、混合物を加熱して分散媒体を蒸発、除去する方法などが挙げられる。 The method for removing the dispersion medium contained in the mixture containing exfoliated graphite and layered silicate is not particularly limited. For example, the dispersion medium is disposed in a vacuum and the mixture is contained in the mixture. And a method of evaporating and removing the dispersion medium under reduced pressure and a method of evaporating and removing the dispersion medium by heating the mixture.
このようにして得られた複合シートは、薄片化黒鉛と層状珪酸塩とが不規則に且つ互いに重なり合った状態に形成されている。そして、薄片化黒鉛は、疎水性であって水蒸気バリア性に優れている一方、層状珪酸塩は、水蒸気バリア性に若干劣るものの、酸素、水素
などのガスバリア性に優れている。
The composite sheet thus obtained is formed such that exfoliated graphite and layered silicate are irregularly overlapped with each other. And exfoliated graphite is hydrophobic and excellent in water vapor barrier properties, while layered silicate is excellent in gas barrier properties such as oxygen and hydrogen, although it is slightly inferior in water vapor barrier properties.
従って、複合シートは、上述のように、薄片化黒鉛と層状珪酸塩とが不規則に重なり合っていることから、薄片化黒鉛及び層状珪酸塩は、それぞれが有する優れたバリア性を発揮しつつ、互いの欠点を補完し合い、よって、複合シートは、薄片化黒鉛及び層状珪酸塩のそれぞれが有する優れたバリア性、即ち、優れたガスバリア性及び水蒸気バリア性の双方を備えている。 Therefore, as described above, since the exfoliated graphite and the layered silicate are irregularly overlapped as described above, the exfoliated graphite and the layered silicate exhibit excellent barrier properties that each has, Complementing each other's drawbacks, the composite sheet thus has both excellent barrier properties possessed by exfoliated graphite and layered silicate, that is, both excellent gas barrier properties and water vapor barrier properties.
本発明の複合シートは、黒鉛化合物を薄片化してなる薄片化黒鉛と層状珪酸塩とを含有しており、上記薄片化黒鉛と上記層状珪酸塩とが不規則に重なり合っているので、優れたガスバリア性及び水蒸気バリア性の双方を備えている。 The composite sheet of the present invention contains exfoliated graphite obtained by exfoliating a graphite compound and layered silicate, and the exfoliated graphite and the layered silicate are irregularly overlapped with each other, so that an excellent gas barrier is provided. And both water vapor barrier properties.
本発明の複合シートの製造方法は、黒鉛化合物を薄片化してなる薄片化黒鉛と層状珪酸塩とを分散媒体中に分散させてなる混合物分散液から水を除去してシート状に成形することを特徴とするので、優れたガスバリア性及び水蒸気バリア性を有する複合シートを容易に製造することができる。 The method for producing a composite sheet according to the present invention comprises forming a sheet by removing water from a mixture dispersion obtained by dispersing exfoliated graphite obtained by flaking a graphite compound and layered silicate in a dispersion medium. Since it is the characteristic, the composite sheet which has the outstanding gas barrier property and water vapor | steam barrier property can be manufactured easily.
次に本発明の実施例を説明するが、本発明は下記実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to the following examples.
（実施例１）
黒鉛化合物（ＳＥＣカーボン社製 商品名「ＳＮＯ−１５」、レーザー光回折法により粒度分布を測定した場合に５０％径として得られる値：１５μｍ）を用意した。
Example 1
A graphite compound (trade name “SNO-15” manufactured by SEC Carbon Co., Ltd., a value obtained as a 50% diameter when the particle size distribution was measured by a laser diffraction method: 15 μm) was prepared.
次に、ｐＨが１０のアンモニア水溶液を用意し、このアンモニア水溶液１８ｇに上記黒鉛化合物０．０５ｇを供給して均一に混合してｐＨ１０の混合液を製造し、この混合液を２５℃にて６０分間に亘って静置して黒鉛化合物をその層面間から剥離し薄片化して薄片化黒鉛を生成し、この薄片化黒鉛が水中に分散してなる薄片化黒鉛分散液を得た。なお、薄片化黒鉛は、その層面の面方向に沿った大きさは、７．４μｍであった。薄片化黒鉛の厚みは、２４ｎｍであった。 Next, an aqueous ammonia solution having a pH of 10 is prepared, 0.05 g of the graphite compound is supplied to 18 g of the aqueous ammonia solution and uniformly mixed to produce a mixed solution of pH 10, and the mixed solution is heated at 25 ° C. at 60 ° C. The graphite compound was exfoliated from between the layer surfaces by being allowed to stand for a minute and exfoliated to produce exfoliated graphite, and an exfoliated graphite dispersion liquid in which the exfoliated graphite was dispersed in water was obtained. The exfoliated graphite had a size along the surface direction of the layer surface of 7.4 μm. The thickness of exfoliated graphite was 24 nm.
なお、薄片化黒鉛分散液中には、黒鉛化合物と推定される沈殿物が残っていたので沈殿物のない上方部分を採取し、薄片化黒鉛分散液とした。薄片化黒鉛分散液は目視にて略無色透明であった。薄片化黒鉛分散液に波長５３２ｎｍのレーザー光を照射したところ、散乱光が確認できたため、薄片化黒鉛分散液中には高度に薄片化された薄片化黒鉛が分散していると推定された。 In addition, in the exfoliated graphite dispersion liquid, a precipitate presumed to be a graphite compound remained. Therefore, an upper part without the precipitate was collected to obtain an exfoliated graphite dispersion liquid. The exfoliated graphite dispersion was substantially colorless and transparent by visual observation. When the exfoliated graphite dispersion was irradiated with a laser beam having a wavelength of 532 nm, scattered light could be confirmed. Therefore, it was presumed that exfoliated graphite highly exfoliated was dispersed in the exfoliated graphite dispersion.
薄片化黒鉛分散液の上方部分から試験液を３ｃｍ3採取し、この試験液を２５℃にて２４時間に亘って静置したが沈殿物は生成しなかった。 3 cm 3 of the test solution was sampled from the upper part of the exfoliated graphite dispersion, and this test solution was allowed to stand at 25 ° C. for 24 hours, but no precipitate was produced.
得られた薄片化黒鉛分散液を濾過し薄片化黒鉛を分離して薄片化黒鉛を蒸留水で洗浄した後、薄片化黒鉛を蒸留水に分散させて薄片化黒鉛分散液を作製した。なお、薄片化黒鉛分散液中における薄片化黒鉛の含有量は３重量％であった。 The obtained exfoliated graphite dispersion was filtered to separate exfoliated graphite, and the exfoliated graphite was washed with distilled water, and then exfoliated graphite was dispersed in distilled water to prepare an exfoliated graphite dispersion. The content of exfoliated graphite in the exfoliated graphite dispersion was 3% by weight.
天然モンモリオナイトである層状珪酸塩（クニミネ工業社製 商品名「クニピアＰ」、平均長さ：０．８６μｍ、平均厚み：１．４ｎｍ）を蒸留水に分散させて層状珪酸塩分散液を作製した。なお、層状珪酸塩分散液中における層状珪酸塩の含有量は３重量％であった。 A layered silicate dispersion (manufactured by Kunimine Kogyo Co., Ltd., trade name “Kunipia P”, average length: 0.86 μm, average thickness: 1.4 nm) is dispersed in distilled water to produce a layered silicate dispersion. did. The content of layered silicate in the layered silicate dispersion was 3% by weight.
上記薄片化黒鉛分散液と上記層状珪酸塩分散液とを重量比で１：１となるように混合して混合物分散液を作製した。 The exfoliated graphite dispersion and the layered silicate dispersion were mixed at a weight ratio of 1: 1 to prepare a mixture dispersion.
次に、混合物分散液を濾過して薄片化黒鉛及び層状珪酸塩の混合物を分離した後、この混合物を表面が平滑面に形成された合成樹脂板上に均一な厚みとなるように層状に塗布し、混合物を６０℃に加熱することによって乾燥させた。更に、混合物を大気雰囲気中において２００℃にて２時間に亘って熱処理した後に窒素雰囲気中において８００℃にて２時間に亘って熱処理することによって厚みが０．４ｍｍの複合シートを得た。 Next, the mixture dispersion is filtered to separate a mixture of exfoliated graphite and layered silicate, and then this mixture is applied in layers so that the surface has a uniform thickness on a synthetic resin plate having a smooth surface. And the mixture was dried by heating to 60 ° C. Furthermore, the mixture was heat-treated at 200 ° C. for 2 hours in an air atmosphere and then heat-treated at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a composite sheet having a thickness of 0.4 mm.
（実施例２）
黒鉛化合物（ＳＥＣカーボン社製 商品名「ＳＮＯ−１５」、レーザー光回折法により粒度分布を測定した場合に５０％径として得られる値：１５μｍ）を用意した。
(Example 2)
A graphite compound (trade name “SNO-15” manufactured by SEC Carbon Co., Ltd., a value obtained as a 50% diameter when the particle size distribution was measured by a laser diffraction method: 15 μm) was prepared.
次に、テトラヒドロフランを用意し、このテトラヒドロフラン１８ｇに上記黒鉛化合物０．１ｇを供給して混合して被処理液を作製した。この被処理液を入れた容器を手で把持して上下方向に振ることによって容器内の被処理液を振とうさせて黒鉛化合物をその層面間から剥離し薄片化して薄片化黒鉛を生成し、この薄片化黒鉛がテトラヒドロフラン中に分散してなる薄片化黒鉛分散液を製造した。なお、薄片化黒鉛は、その層面の面方向に沿った大きさは、１１．４μｍであった。薄片化黒鉛の厚みは１．６ｎｍであった。 Next, tetrahydrofuran was prepared, and 0.1 g of the graphite compound was supplied to 18 g of tetrahydrofuran and mixed to prepare a liquid to be treated. The container containing the liquid to be treated is manually grasped and shaken in the vertical direction to shake the liquid to be treated in the container, and the graphite compound is exfoliated between the layer surfaces to produce exfoliated graphite. A exfoliated graphite dispersion was prepared by dispersing the exfoliated graphite in tetrahydrofuran. The exfoliated graphite had a size along the surface direction of the layer surface of 11.4 μm. The thickness of exfoliated graphite was 1.6 nm.
なお、薄片化黒鉛分散液中には、黒鉛化合物と推定される沈殿物が残っていたので沈殿物のない上方部分を採取し、薄片化黒鉛分散液とした。薄片化黒鉛分散液は目視にて透明度の高い黒銀色であり、薄片化黒鉛分散液中には高度に薄片化された薄片化黒鉛が分散していると推定された。 In addition, in the exfoliated graphite dispersion liquid, a precipitate presumed to be a graphite compound remained. Therefore, an upper part without the precipitate was collected to obtain an exfoliated graphite dispersion liquid. The exfoliated graphite dispersion was visually black and black with high transparency, and it was presumed that exfoliated graphite highly exfoliated was dispersed in the exfoliated graphite dispersion.
薄片化黒鉛分散液の上方部分から試験液を３ｃｍ3採取し、この試験液を２５℃にて２４時間に亘って静置したが沈殿物は生成しなかった。 3 cm 3 of the test solution was sampled from the upper part of the exfoliated graphite dispersion, and this test solution was allowed to stand at 25 ° C. for 24 hours, but no precipitate was produced.
得られた薄片化黒鉛分散液を濾過して薄片化黒鉛を分離し、薄片化黒鉛をメタノールで洗浄した後、薄片化黒鉛をメタノールに分散させて薄片化黒鉛分散液を作製した。なお、薄片化黒鉛分散液中における薄片化黒鉛の含有量は３重量％であった。 The obtained exfoliated graphite dispersion was filtered to separate exfoliated graphite, and the exfoliated graphite was washed with methanol, and then exfoliated graphite was dispersed in methanol to prepare an exfoliated graphite dispersion. The content of exfoliated graphite in the exfoliated graphite dispersion was 3% by weight.
表面処理が有機官能基で修飾された有機化クレイである層状珪酸塩（ホージュン社製 商品名「エスベンＥ」、平均長さ：０．３５μｍ、平均厚み：１．７ｎｍ）をメタノールに分散させて層状珪酸塩分散液を作製した。なお、層状珪酸塩分散液中における層状珪酸塩の含有量は３重量％であった。 A layered silicate (trade name “Esven E” manufactured by Hojun Co., Ltd., average length: 0.35 μm, average thickness: 1.7 nm), an organic clay modified with an organic functional group, is dispersed in methanol. A layered silicate dispersion was prepared. The content of layered silicate in the layered silicate dispersion was 3% by weight.
上記薄片化黒鉛分散液と上記層状珪酸塩分散液とを重量比で１：１となるように混合すると共にこの混合液にポリビニルピロリドン（日本触媒社製 商品名「Ｋ−３０」）を添加して均一に攪拌して混合物分散液を作製した。なお、混合物分散液中におけるポリビニルピロリドンの含有量は１．５重量％であった。上記混合物分散液を用いたこと以外は実施例１と同様にして厚みが０．３ｍｍの複合シートを得た。 The exfoliated graphite dispersion and the layered silicate dispersion were mixed at a weight ratio of 1: 1, and polyvinylpyrrolidone (trade name “K-30” manufactured by Nippon Shokubai Co., Ltd.) was added to the mixture. The mixture dispersion was prepared by stirring uniformly. The polyvinyl pyrrolidone content in the mixture dispersion was 1.5% by weight. A composite sheet having a thickness of 0.3 mm was obtained in the same manner as in Example 1 except that the above mixture dispersion was used.
（実施例３）
黒鉛化合物（ＸＧＳｉｅｎｃｅ社製 商品名「ＸＧｎＰ−５」、レーザー光回折法により粒度分布を測定した場合に５０％径として得られる値：５μｍ）を用意した。
(Example 3)
A graphite compound (trade name “XGnP-5” manufactured by XGSense, Inc., a value obtained as a 50% diameter when the particle size distribution is measured by a laser diffraction method: 5 μm) was prepared.
次に、ｐＨが９の水酸化ナトリウム水溶液を用意し、この水酸化ナトリウム水溶液１８ｇに上記黒鉛化合物０．０５ｇを供給して均一に混合してｐＨ９の混合液を製造し、この混合液を２５℃にて６０分間に亘って静置して黒鉛化合物をその層面間から剥離し薄片化して、薄片化黒鉛が水中に分散してなる薄片化黒鉛分散液を得た。薄片化黒鉛分散液中には沈殿物は生じていなかった。なお、薄片化黒鉛は、その層面の面方向に沿った大きさは９．２μｍであった。薄片化黒鉛の厚みは１．５ｎｍであった。 Next, a sodium hydroxide aqueous solution having a pH of 9 is prepared, and 0.05 g of the graphite compound is supplied to 18 g of the sodium hydroxide aqueous solution and mixed uniformly to produce a mixed solution of pH 9. The graphite compound was peeled from the surface of the layers by being allowed to stand at 60 ° C. for 60 minutes and exfoliated to obtain an exfoliated graphite dispersion in which exfoliated graphite was dispersed in water. No precipitate was formed in the exfoliated graphite dispersion. The exfoliated graphite had a size along the surface direction of the layer surface of 9.2 μm. The thickness of exfoliated graphite was 1.5 nm.
薄片化黒鉛分散液から試験液を３ｃｍ3採取し、この試験液を２５℃にて２４時間に亘って静置したが沈殿物は生成しなかった。 3 cm 3 of the test solution was sampled from the exfoliated graphite dispersion, and this test solution was allowed to stand at 25 ° C. for 24 hours, but no precipitate was produced.
得られた薄片化黒鉛分散液を濾過して薄片化黒鉛を分離し、薄片化黒鉛を蒸留水で洗浄した後、薄片化黒鉛を蒸留水に分散させて薄片化黒鉛分散液を作製した。なお、薄片化黒鉛分散液中における薄片化黒鉛の含有量は３重量％であった。この薄片化黒鉛分散液を用いたこと以外は実施例１と同様の要領で厚みが０．４ｍｍの複合シートを得た。 The obtained exfoliated graphite dispersion was filtered to separate exfoliated graphite, and the exfoliated graphite was washed with distilled water, and then exfoliated graphite was dispersed in distilled water to prepare an exfoliated graphite dispersion. The content of exfoliated graphite in the exfoliated graphite dispersion was 3% by weight. A composite sheet having a thickness of 0.4 mm was obtained in the same manner as in Example 1 except that this exfoliated graphite dispersion was used.
（比較例１）
天然モンモリロナイトである層状珪酸塩（クニミネ工業社 商品名「クニピアＰ」）１ｇを蒸留水６０ｇに供給し攪拌して層状珪酸塩が水中に分散してなる分散液を得た。この分散液をトレイ上に供給した上で、このトレイをオーブン内に供給して５０℃にて５時間に亘って乾燥させた後、１０００℃にて２４時間に亘って熱処理を行い、厚さが約０．３ｍｍの層状珪酸塩のみからなる層状珪酸塩シートを得た。
(Comparative Example 1)
1 g of layered silicate (Kunimine Kogyo Co., Ltd., trade name “Kunipia P”), which is natural montmorillonite, was supplied to 60 g of distilled water and stirred to obtain a dispersion in which the layered silicate was dispersed in water. After supplying this dispersion onto the tray, this tray was supplied into the oven and dried at 50 ° C. for 5 hours, and then heat treated at 1000 ° C. for 24 hours to obtain a thickness. Obtained a layered silicate sheet consisting only of a layered silicate of about 0.3 mm.
得られた複合シート及び層状珪酸塩シートの酸素透過性及び水蒸気透過性を下記の要領で測定し、その結果を表１に示した。 The oxygen permeability and water vapor permeability of the obtained composite sheet and layered silicate sheet were measured in the following manner, and the results are shown in Table 1.
（酸素透過性及び水蒸気透過性）
複合シート及び層状珪酸塩シートの酸素透過性及び水蒸気透過性を測定装置（ＧＴＲ−テック社製 商品名「ＧＴＲ−ＷＶ」）を用いて測定した。
(Oxygen permeability and water vapor permeability)
The oxygen permeability and water vapor permeability of the composite sheet and the layered silicate sheet were measured using a measuring device (trade name “GTR-WV” manufactured by GTR-Tech).
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