本發明是有關於一種用於導電性樹脂膜的樹脂組成物，更詳細而言，是有關於用於拉伸伸長率、耐彎折性或柔軟性優異的導電性樹脂膜的樹脂組成物。The present invention relates to a resin composition for a conductive resin film, and more particularly to a resin composition for a conductive resin film excellent in tensile elongation, bending resistance, or flexibility.
近年來，作為代替石油等化石燃料或原子力的新的能量源，太陽光發電、風力發電及波浪發電等所謂的可再生能量受到關注。但是，這些可再生能量會強烈地受到天氣等的影響，因此輸出極不穩定。因此，為了將這些能量大量地連接至電力網，而例如需要並設大容量的蓄電池來進行輸出變動的平穩化等。In recent years, as a new energy source that replaces fossil fuels such as petroleum or atomic forces, so-called renewable energy such as solar power generation, wind power generation, and wave power generation has attracted attention. However, these renewable energies are strongly affected by the weather and the like, so the output is extremely unstable. Therefore, in order to connect these energies to the power grid in a large amount, for example, it is necessary to provide a large-capacity storage battery to smooth the output fluctuation.
大容量的蓄電池之一有氧化還原液流電池(redox flow cell)。氧化還原液流電池是藉由陽離子交換膜隔開2種離子溶液，在設置於兩種溶液中的電極上同時進行氧化反應與還原反應而進行充放電者。例如，在將釩的硫酸水溶液用於兩極的氧化還原液流電池中，在充電時，在正極將4價的釩氧化為5價，在負極將3價的釩還原為2價。在放電時，發生其逆反應。氧化還原液流電池具有設備的大型化容易的優點。另外，由於在室溫下運作、且不使用具有燃燒性或爆炸性的物質，並且亦不產生此種物質，因此與鈉-硫電池或鋰離子二次電池相比，安全性更優異。One of the large-capacity batteries is a redox flow cell. The redox flow battery is a charge and discharge device in which two kinds of ion solutions are separated by a cation exchange membrane, and an oxidation reaction and a reduction reaction are simultaneously performed on an electrode provided in the two solutions. For example, in a redox flow battery in which a vanadium sulfuric acid aqueous solution is used in a two-pole, a tetravalent vanadium is oxidized to a valence at the positive electrode and a trivalent vanadium is reduced to a valence at the negative electrode. When it is discharged, its reverse reaction occurs. The redox flow battery has the advantage that the size of the device is large. In addition, since it operates at room temperature and does not use substances that are flammable or explosive, and does not produce such substances,This is superior to sodium-sulfur batteries or lithium ion secondary batteries.
氧化還原液流電池的電極被浸漬於硫酸水溶液等電解液中，且於其中發生氧化還原反應，因此需要高的導電性及耐化學品性，而使用碳纖維集合體或鉑鍍金作為電極。但是，碳纖維集合體具有通液性，因此有碳纖維集合體與銅線的連接部被所輸送的硫酸水溶液等侵入的問題。另外，鉑鍍金是非常好的導體，且耐化學品性亦優異，但為貴金屬而有高價的難點。The electrode of the redox flow battery is immersed in an electrolytic solution such as a sulfuric acid aqueous solution, and a redox reaction occurs therein. Therefore, high conductivity and chemical resistance are required, and a carbon fiber assembly or platinum plating is used as an electrode. However, since the carbon fiber aggregate has liquid permeability, there is a problem in that the connection portion between the carbon fiber aggregate and the copper wire is invaded by the sulfuric acid aqueous solution or the like to be transported. In addition, platinum plating is a very good conductor and is excellent in chemical resistance, but it is expensive for precious metals.
因此進行：使用練入了科琴黑(Ketjen black)等導電性碳的導電性樹脂膜作為電極(例如專利文獻1~專利文獻4)，或者藉由上述導電性樹脂膜被覆碳纖維集合體或銅板等電極。但是，這些導電性樹脂膜若為了賦予充分高的導電性而練入大量的的導電性碳，則有拉伸伸長率、耐彎折性或柔軟性均不充分，且容易被物理性力破壞的問題。另外，若減少導電性碳的調配量而確保拉伸伸長率、耐彎折性及柔軟性，則體積電阻率超過10Ω．cm，將此種導電性膜用於電極或電極的被覆的氧化還原液流電池在內部電阻變大的方面無法滿足。Therefore, a conductive resin film in which conductive carbon such as Ketjen black or the like is used is used as an electrode (for example, Patent Documents 1 to 4), or a carbon fiber assembly or a copper plate is coated with the conductive resin film. Equal electrode. However, when these conductive resin films are trained in a large amount of conductive carbon in order to impart sufficiently high conductivity, tensile elongation, bending resistance, and flexibility are insufficient, and they are easily destroyed by physical force. The problem. In addition, if the amount of conductive carbon is reduced to ensure tensile elongation, bending resistance and flexibility, the volume resistivity exceeds 10 Ω. In the case where the conductive film is used for the coating of the electrode or the electrode, the redox flow battery cannot satisfy the internal resistance.
另外近年來，碳奈米管作為導電性碳而受到關注，並期待可解決上述問題(例如專利文獻5及非專利文獻1)。但是，碳奈米管難以解纖，因此有在樹脂中的分散非常難的問題。因此，為了獲得充分高的導電性，而與科琴黑同樣必須調配大量的碳奈米管，結果是導電性樹脂膜的拉伸伸長率、耐彎折性或柔軟性在實用上不充分。另外，為了使碳奈米管的解纖、分散狀態良好，若提高解纖、分散步驟中的剪應力(shearing stress)，則會導致碳奈米管破壞，結果為了獲得充分高的導電性，而需要大量地調配。In addition, in recent years, carbon nanotubes have been attracting attention as conductive carbon, and it is expected that the above problems can be solved (for example, Patent Document 5 and Non-Patent Document 1). However, since the carbon nanotubes are difficult to defibrate, there is a problem that dispersion in the resin is very difficult. Therefore, in order to obtain sufficiently high conductivity, a large number of carbon nanotubes must be prepared in the same manner as Ketjen black, and as a result, the tensile elongation, bending resistance, and flexibility of the conductive resin film are not practically sufficient. In addition, in order to make the carbon nanotubes defibrated and dispersed,If the shear stress in the defibration and dispersion steps is increased, the carbon nanotubes are destroyed, and as a result, a large amount of preparation is required in order to obtain sufficiently high conductivity.
另外提出包含以下組成物的導電性膜，該組成物是將碳黑或碳奈米管與丙烯-烯烴共聚物蠟混合而製成母料，並將其與有機聚合物混合而得(例如專利文獻6及專利文獻7)。上述母料可實現碳黑或碳奈米管的高填充，但所得的膜的導電性不充分。Further, a conductive film comprising a carbon black or a carbon nanotube and a propylene-olefin copolymer wax to form a master batch and mixing it with an organic polymer is proposed (for example, a patent) Document 6 and Patent Document 7). The above master batch can achieve high filling of carbon black or carbon nanotubes, but the conductivity of the obtained film is insufficient.
[專利文獻1]日本專利特開平1-149370號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 1-149370
[專利文獻2]日本專利特開平4-259754號公報[Patent Document 2] Japanese Patent Laid-Open No. Hei 4-259754
[專利文獻3]日本專利特開平7-053813號公報[Patent Document 3] Japanese Patent Laid-Open No. Hei 7-053813
[專利文獻4]日本專利特開2001-015144號公報[Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-015144
[專利文獻5]日本專利特開2006-111870號公報[Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-111870
[專利文獻6]日本專利特表2012-507586號公報[Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-507586
[專利文獻7]日本專利特表2012-507587號公報[Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-507587
[非專利文獻1]高瀬博文著、「碳奈米管的分散技術與評價」、成形加工第18卷第9號2006年、第646頁~第652頁[Non-Patent Document 1] Takahashi Bowen, "Dispersion Technology and Evaluation of Carbon Nanotubes", Forming and Processing, Vol. 18, No. 9 2006, pp. 646 - 652
本發明的目的是提供一種用於導電性樹脂膜的樹脂組成物，該導電性樹脂膜具有導電性，且拉伸伸長率、耐彎折性或柔軟性優異，並適合於電解液循環型二次電池、例如氧化還原液流電池、鋅-氯電池及鋅-溴電池等中的電極或電極的被覆保護。An object of the present invention is to provide a resin composition for a conductive resin film which has electrical conductivity and tensile elongation, bending resistance orIt is excellent in flexibility, and is suitable for coating protection of an electrode or an electrode in an electrolyte circulating secondary battery, for example, a redox flow battery, a zinc-chlorine battery, a zinc-bromine battery, or the like.
本發明者等人進行銳意研究，結果發現，藉由在熱塑性樹脂中添加碳奈米管與乙炔黑及/或石墨，而可達成上述課題。The inventors of the present invention conducted intensive studies and found that the above problems can be attained by adding a carbon nanotube and acetylene black and/or graphite to a thermoplastic resin.
即，本發明是一種樹脂組成物，其包含：100質量份的(A)熱塑性樹脂、1質量份~60質量份的(B)碳奈米管、及1質量份~100質量份的(C)選自由乙炔黑及石墨所組成的組群中的至少1種。That is, the present invention is a resin composition comprising: 100 parts by mass of (A) thermoplastic resin, 1 part by mass to 60 parts by mass of (B) carbon nanotube, and 1 part by mass to 100 parts by mass (C) And at least one selected from the group consisting of acetylene black and graphite.
包含本發明的樹脂組成物的膜具有高的導電性，且拉伸伸長率、耐彎折性及柔軟性優異，因此可適用於電解液循環型二次電池、例如氧化還原液流電池、鋅-氯電池及鋅-溴電池等中的電極或電極的被覆保護。The film containing the resin composition of the present invention has high conductivity and is excellent in tensile elongation, bending resistance, and flexibility, and thus is applicable to an electrolyte circulating secondary battery, such as a redox flow battery, and zinc. - Coating protection of electrodes or electrodes in chlorine batteries, zinc-bromine batteries, etc.
圖1是表示實施例及比較例的膜的體積電阻率ρ與拉伸伸長率E的關係的圖表。1 is a graph showing the relationship between the volume resistivity ρ and the tensile elongation E of the films of the examples and the comparative examples.
(A)熱塑性樹脂(A) thermoplastic resin
成分(A)接受作為碳填料的成分(B)~成分(D)，並對所得的膜賦予拉伸伸長率、耐彎折性或柔軟性等機械物性。作為此種熱塑性樹脂，例如可列舉：聚乙烯、聚丙烯、聚丁烯-1、聚4-甲基戊烯-1、氯化聚乙烯、乙烯-α-烯烴共聚物、乙烯-乙酸乙烯酯共聚物及乙烯-丙烯酸酯共聚物等聚烯烴系樹脂；聚氯乙烯-乙酸乙烯酯共聚物及氯乙烯-乙酸乙烯酯共聚物等聚氯乙烯系樹脂；尼龍11及尼龍12等聚醯胺系樹脂；聚胺基甲酸酯系樹脂：非晶性、低晶性或結晶性聚酯系樹脂；丙烯腈-丁二烯-苯乙烯共聚物((Acrylonitrile Butadiene Styrene，ABS)樹脂)；苯乙烯-共軛二烯共聚物的氫化物等氫化苯乙烯系彈性體；丙烯酸系樹脂；矽系樹脂；聚偏二氯乙烯系樹脂；氯丁二烯系樹脂等，可根據導電性樹脂膜的使用目的適當選擇而使用這些的1種或2種以上。The component (A) receives the component (B) to the component (D) as a carbon filler, and imparts mechanical properties such as tensile elongation, bending resistance, and flexibility to the obtained film. Examples of such a thermoplastic resin include polyethylene, polypropylene, polybutene-1, and poly 4-a polyolefin resin such as methylpentene-1, chlorinated polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer and ethylene-acrylate copolymer; polyvinyl chloride-vinyl acetate copolymer and Polyvinyl chloride resin such as vinyl chloride-vinyl acetate copolymer; polyamine resin such as nylon 11 and nylon 12; polyurethane resin: amorphous, low crystalline or crystalline polyester resin ; Acrylonitrile Butadiene Styrene (ABS) resin; hydrogenated styrene elastomer such as hydride of styrene-conjugated diene copolymer; acrylic resin; lanthanide resin A polyvinylidene chloride-based resin, a chloroprene-based resin, or the like may be used, and one or two or more kinds of these may be appropriately selected depending on the intended use of the conductive resin film.
例如在將所得的導電性樹脂膜用於氧化還原液流電池的電極或電極的被覆時，上述氧化還原液流電池是將釩的硫酸水溶液用於兩極，由於需要耐硫酸水溶液性，因此較佳為聚乙烯及氯化聚乙烯，更佳為氯含量為25質量%~45質量%的氯化聚乙烯。若考慮到壓延製膜性，則最佳為氯含量為25質量%~45質量%的結晶性氯化聚乙烯。另外，所謂結晶性氯化聚乙烯，是指使用日本TA儀器(TA Instruments Japan)股份有限公司的DSCQ1000型，於在190℃下保持5分鐘，以10℃/分鐘冷卻至-10℃，在-10℃下保持5分鐘，以10℃/分鐘升溫至190℃的測定程式中的第二熔解曲線(最後的升溫過程中所測定的熔解曲線)中，指示20J/g以上的熔解熱量(△H)者。作為此種結晶性氯化聚乙烯的市售例，可列舉：昭和電工股份有限公司的「Erasuren 404B(商品名)」、「Erasuren 303B(商品名)」等。For example, when the obtained conductive resin film is used for coating an electrode or an electrode of a redox flow battery, the redox flow battery is preferably used as a bisulfuric aqueous solution of vanadium, and is preferably a sulfuric acid-resistant aqueous solution. The polyethylene and the chlorinated polyethylene are more preferably a chlorinated polyethylene having a chlorine content of 25% by mass to 45% by mass. In view of the rolling film forming property, a crystalline chlorinated polyethylene having a chlorine content of 25% by mass to 45% by mass is preferable. In addition, the term "crystalline chlorinated polyethylene" refers to a DSCQ1000 type manufactured by TA Instruments Japan Co., Ltd., and is kept at 190 ° C for 5 minutes and at 10 ° C / minute to -10 ° C. Hold at 10 ° C for 5 minutes, and at a temperature of 10 ° C / min to 190 ° C in the second melting curve of the measurement program (melting curve measured during the final temperature rise), indicating the heat of fusion above 20 J / g (△H )By. As a commercially available example of such a crystalline chlorinated polyethylene, "Erasuren 404B (trade name)" and "Erasuren 303B (trade name)" of Showa Denko Co., Ltd., etc. are mentioned.
(B)碳奈米管(B) carbon nanotubes
碳奈米管是由碳構成的六員環的網狀結構(石墨烯(graphene)片)成為單層或多層的同軸管狀的直徑為1nm~250nm左右、長度為0.1μm~250μm左右的纖維狀物質，以導電性填料的方式發揮出對導電性樹脂膜賦予高的導電性的功能。因此，較佳為晶格缺陷少、且碳奈米管本身的導電性高者。另外，體積比重小者容易解纖，因此較佳。The carbon nanotube tube is a six-membered ring network structure (graphene sheet) made of carbon, which is a single-layer or multi-layered coaxial tubular fiber having a diameter of about 1 nm to 250 nm and a length of about 0.1 μm to 250 μm. The substance exhibits a function of imparting high conductivity to the conductive resin film in the form of a conductive filler. Therefore, it is preferable that the lattice defects are small and the conductivity of the carbon nanotube itself is high. Further, those having a small specific gravity are easily defibrated, and therefore are preferred.
作為此種碳奈米管的市售例，可列舉：納諾塞爾S.A.(NANOCYL S.A.)公司的「NANOCYL NC7000(商品名)」、昭和電工股份有限公司的「VGCF-X(商品名)」等。As a commercial example of such a carbon nanotube, "NANOCYL NC7000 (trade name)" of NANOCYL SA, "VGCF-X (brand name) of Showa Denko Co., Ltd." Wait.
相對於成分(A)100質量份，成分(B)的調配量為1質量份~60質量份、較佳為20質量份~50質量份。若成分(B)的調配量少於上述下限，則體積電阻率變得高於10Ω．cm，若成分(B)的調配量過多，則有拉伸伸長率、耐彎折性及柔軟性不充分的情況。The amount of the component (B) to be added is from 1 part by mass to 60 parts by mass, preferably from 20 parts by mass to 50 parts by mass, per 100 parts by mass of the component (A). If the compounding amount of the component (B) is less than the above lower limit, the volume resistivity becomes higher than 10 Ω. When the amount of the component (B) is too large, the tensile elongation, the bending resistance, and the flexibility may be insufficient.
(C)乙炔黑及石墨(C) acetylene black and graphite
成分(C)在樹脂組成物的製造(熔融混練)步驟及製膜步驟中，保持加工性，且有助於碳奈米管(B)及根據需要的碳纖維(D)的解纖、高分散化，其結果提高膜的導電性，並使拉伸伸長率等機械特性良好。另外，成分(C)由於其本身具有導電性，因此成分(C)本身亦發揮出提高膜的導電性的功能。The component (C) maintains workability in the production (melt kneading) step and the film forming step of the resin composition, and contributes to defibration and high dispersion of the carbon nanotube (B) and the carbon fiber (D) as needed. As a result, the conductivity of the film is improved, and mechanical properties such as tensile elongation are good. Further, since the component (C) itself has conductivity, the component (C) itself also functions to increase the conductivity of the film.
乙炔黑是藉由乙炔氣體的熱分解而製造的碳微粒子，是具有一部分經石墨化的結構的導電性碳黑。作為乙炔黑的市售例，可列舉：電氣化學工業股份有限公司的「Denka Black(商品名)」等。Acetylene black is a carbon microparticle produced by thermal decomposition of acetylene gas.Conductive carbon black having a portion of the graphitized structure. As a commercially available example of acetylene black, "Denka Black (trade name)" of Electric Chemical Industry Co., Ltd., etc. are mentioned.
作為導電性碳黑，除了乙炔黑外，已知有科琴黑。科琴黑具有高的導電性，但與乙炔黑不同，具有中空殼狀結構，因此將其與熱塑性樹脂及碳奈米管混練而得的組成物，在製膜時表現不出熔融延性，而無法製膜。As the conductive carbon black, in addition to acetylene black, Ketjen black is known. Ketjen black has high conductivity, but unlike acetylene black, it has a hollow shell structure. Therefore, the composition obtained by kneading it with a thermoplastic resin and a carbon nanotube does not exhibit melt ductility at the time of film formation. It is impossible to form a film.
石墨(graphite)亦被稱為黑鉛(black lead)，是包含碳的礦物，包括鱗狀石墨及土狀石墨等天然石墨、以及熱分解石墨等人造石墨。本發明中使用石墨的粉碎物。粉碎物較佳為平均粒徑為10μm以下者，更佳為5μm以下。若粒徑過大，則產生以下缺點：導電性樹脂膜開孔、或膜表面產生凸部、或膜的伸長率小等。上述平均粒徑是在使用日機裝股份有限公司的雷射繞射、散射式粒度分析計MT3200II(商品名)而測定的粒徑分布曲線中，自粒子小者起至累積為50質量%的粒徑。Graphite, also known as black lead, is a mineral containing carbon, including natural graphite such as scaly graphite and earthy graphite, and artificial graphite such as thermally decomposed graphite. A pulverized product of graphite is used in the present invention. The pulverized material preferably has an average particle diameter of 10 μm or less, more preferably 5 μm or less. If the particle diameter is too large, there are disadvantages in that the conductive resin film is opened, or a convex portion is formed on the surface of the film, or the elongation of the film is small. The average particle diameter is a particle size distribution curve measured by a laser diffraction or scattering particle size analyzer MT3200II (trade name) of Nikkiso Co., Ltd., from the small particle to the cumulative 50% by mass. Particle size.
相對於成分(A)100質量份，成分(C)的調配量為1質量份~100質量份、較佳為10質量份~60質量份、更佳為20質量份~50質量份。若成分(C)的調配量少於上述下限，則體積電阻率與拉伸伸長率的平衡降低，而無法滿足下述式(1)。若成分(C)的調配量過多，則有拉伸伸長率、耐彎折性及柔軟性不充分的情況。The compounding amount of the component (C) is from 1 part by mass to 100 parts by mass, preferably from 10 parts by mass to 60 parts by mass, more preferably from 20 parts by mass to 50 parts by mass, per 100 parts by mass of the component (A). When the compounding amount of the component (C) is less than the above lower limit, the balance between the volume resistivity and the tensile elongation is lowered, and the following formula (1) cannot be satisfied. When the amount of the component (C) is too large, the tensile elongation, the bending resistance, and the flexibility may be insufficient.
(D)碳纖維(D) carbon fiber
碳纖維是將有機纖維的前驅物(precursor)進行加熱碳化處理而得、以質量比計90%以上由碳構成的纖維。本發明中的成分(D)是為了對膜進一步賦予導電性而可添加的任意成分。The carbon fiber is a fiber obtained by subjecting a precursor of an organic fiber to a carbonization treatment by heating, and 90% or more by mass of carbon. The component (D) in the present invention is an optional component which can be added in order to further impart conductivity to the film.
碳纖維在其纖維配向方向可賦予高的導電性，但纖維配向方向與鉛垂方向的導電性低，因此有導電性的值因膜的測定位置或方向而大幅不同的問題。但是，令人驚訝的是，若將成分(D)與碳成分(B)及成分(C)一起加入至成分(A)中，則上述問題會大幅得到改良，而可提高膜的導電性。The carbon fiber can impart high conductivity in the fiber alignment direction, but the fiber alignment direction and the conductivity in the vertical direction are low. Therefore, the conductivity value greatly differs depending on the measurement position or direction of the film. However, surprisingly, when the component (D) is added to the component (A) together with the carbon component (B) and the component (C), the above problems are greatly improved, and the conductivity of the film can be improved.
作為成分(D)，較佳為其本身具有高的導電性者。另外，在樹脂組成物的製造步驟中，為了容易熔融混練，較佳為裁斷成纖維長為1mm~15mm左右者。作為此種碳纖維的市售例，可列舉：東麗(Toray)股份有限公司的碳纖維「TORAYCA CUTFIBER(商品名)」等。As the component (D), it is preferred that it has high conductivity itself. Further, in the production step of the resin composition, in order to facilitate the melt-kneading, it is preferable to cut into a fiber length of about 1 mm to 15 mm. As a commercial example of such a carbon fiber, the carbon fiber "TORAYCA CUTFIBER (trade name)" of Toray Co., Ltd., etc. are mentioned.
相對於成分(A)100質量份，成分(D)的調配量較佳為1質量份~60質量份，更佳為10質量份~30質量份。若成分(D)的調配量少於上述下限，則無法獲得調配成分(D)的效果，若成分(D)的調配量過多，則有拉伸伸長率、耐彎折性及柔軟性不充分的情況。The compounding amount of the component (D) is preferably from 1 part by mass to 60 parts by mass, more preferably from 10 parts by mass to 30 parts by mass, per 100 parts by mass of the component (A). When the blending amount of the component (D) is less than the above lower limit, the effect of blending the component (D) cannot be obtained, and if the blending amount of the component (D) is too large, the tensile elongation, the bending resistance, and the flexibility are insufficient. Case.
上述樹脂組成物中，在不脫離本發明的目的之限度內，可進一步含有公知的添加劑，例如潤滑劑、抗氧化劑、抗老化劑、光穩定劑或紫外線吸收劑等耐候性穩定劑、熱穩定劑、銅毒抑制劑、脫模劑、及界面活性劑等添加劑。上述添加劑的調配量相對於成分(A)100質量份為0.001質量份~5質量份左右。The resin composition may further contain a known additive such as a weathering stabilizer such as a lubricant, an antioxidant, an anti-aging agent, a light stabilizer or an ultraviolet absorber, and is thermally stable, without departing from the object of the present invention. Additives such as agents, copper poison inhibitors, mold release agents, and surfactants. The amount of the above additives is relatively100 parts by mass of the component (A) is about 0.001 parts by mass to 5 parts by mass.
另外，在不脫離本發明的目的之限度內，可進一步含有成分(B)~成分(D)以外的無機填充劑。作為上述無機填充劑，例如可列舉：輕質碳酸鈣、重質碳酸鈣、水合矽酸鎂及滑石等。上述無機填充劑的調配量相對於(A)熱塑性樹脂100質量份為1質量份~20質量份左右。Further, an inorganic filler other than the components (B) to (D) may be further contained within the limits of the object of the present invention. Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, hydrated magnesium citrate, and talc. The amount of the inorganic filler to be added is about 1 part by mass to 20 parts by mass based on 100 parts by mass of the (A) thermoplastic resin.
本發明的樹脂組成物藉由使用任意的熔融混練機將成分(A)~成分(C)及根據需要的成分(D)及其他任意成分進行熔融混練而得。作為熔融混練機，可列舉：加壓捏合機及混合機等批次混練機；同方向旋轉雙軸擠出機、異方向旋轉雙軸擠出機等擠出混練機；及壓延輥混練機等。可將這些進行任意組合而使用。所得的樹脂組成物藉由任意的方法顆粒化後，例如使用壓延加工機或使用擠出機與T模而可製膜。顆粒化可藉由熱切割、股線切割及水下切割等方法進行。或者亦可將經熔融混練的樹脂組成物直接送至壓延加工機或T模而製膜。壓延加工機可使用任意者，例如可列舉：直立型三輥、直立型四輥、L型四輥、反L型四輥及Z型輥等。擠出機可使用任意者，例如可列舉：單軸擠出機、同方向旋轉雙軸擠出機及異方向旋轉雙軸擠出機等。T模可使用任意者，例如可列舉：歧管模(manifold die)、魚尾式模(fishtail die)及衣架式模(coat hanger die)等。The resin composition of the present invention is obtained by melt-kneading the component (A) to the component (C) and the optional component (D) and other optional components by using an arbitrary melt kneader. Examples of the melt kneading machine include a batch kneading machine such as a pressure kneader and a mixer, an extrusion kneading machine such as a co-rotating twin-screw extruder and a counter-rotating twin-screw extruder, and a calender roll kneading machine. . These can be used in any combination. The obtained resin composition can be formed into a film by granulation by any method, for example, using a calendering machine or an extruder and a T die. Granulation can be carried out by methods such as thermal cutting, strand cutting and underwater cutting. Alternatively, the melt-kneaded resin composition may be directly sent to a calendering machine or a T-die to form a film. Any one of the calendering machines can be used, and examples thereof include an upright type three roll, an upright type four roll, an L type four roll, an inverse L type four roll, and a Z type roll. Any extruder may be used, and examples thereof include a single-shaft extruder, a co-rotating twin-screw extruder, and a counter-rotating twin-screw extruder. Any of the T modes may be used, and examples thereof include a manifold die, a fishtail die, and a coat hanger die.
如此而得的導電性樹脂膜為了提高其耐熱性或耐溶劑性，而可藉由公知的方法、例如電子束照射而交聯、硬化。The conductive resin film thus obtained can be crosslinked and cured by a known method such as electron beam irradiation in order to improve heat resistance and solvent resistance.
包含本發明的樹脂組成物的導電性膜，依據JIS K 7194而測定的體積電阻率ρ為10Ω．cm以下，且上述體積電阻率ρ與依據JIS K 7127而測定的拉伸伸長率E滿足式(1)。The conductive film containing the resin composition of the present invention has a volume resistivity ρ of 10 Ω measured in accordance with JIS K 7194. Below cm, the volume resistivity ρ and the tensile elongation E measured in accordance with JIS K 7127 satisfy the formula (1).
Logρ≦0.02E-1.4...式(1)Logρ≦0.02E-1.4...(1)
此處，ρ的單位為Ω．cm，E的單位為%。Here, the unit of ρ is Ω. Cm, the unit of E is %.
通常，為了將導電性樹脂膜用於氧化還原液流電池等中的電極或電極的被覆，而需要該膜的體積電阻率為10Ω．cm以下。該膜的體積電阻率較佳為1.0Ω．cm以下，更佳為0.1Ω．cm以下。體積電阻率越低越佳。Usually, in order to use a conductive resin film for coating of an electrode or an electrode in a redox flow battery or the like, the volume resistivity of the film is required to be 10 Ω. Below cm. The volume resistivity of the film is preferably 1.0 Ω. Below cm, more preferably 0.1Ω. Below cm. The lower the volume resistivity, the better.
另外，為了使包含導電性樹脂膜的電極或藉由導電性樹脂膜對電極進行的被覆不易藉由物理性力而破壞，導電性樹脂膜亦需要拉伸伸長率、耐彎折性及柔軟性等機械物性良好。因此，是體積電阻率越小，且拉伸伸長率等機械物性越大，則工業上實用性越高、且越有用的導電性膜。In addition, in order to prevent the electrode including the conductive resin film or the coating of the electrode by the conductive resin film from being broken by physical force, the conductive resin film also needs tensile elongation, bending resistance, and flexibility. The mechanical properties are good. Therefore, the smaller the volume resistivity and the higher the mechanical properties such as the tensile elongation, the higher the industrial applicability and the more useful the conductive film.
包含本發明的樹脂組成物的導電性樹脂膜由於體積電阻率ρ為10Ω．cm以下、且上述體積電阻率ρ與拉伸伸長率E滿足上述式(1)，因此可適用於氧化還原液流電池、鋅-氯電池及鋅-溴電池等中的電極或電極的被覆保護。The conductive resin film containing the resin composition of the present invention has a volume resistivity ρ of 10 Ω. Since the volume resistivity ρ and the tensile elongation E satisfy the above formula (1), it is applicable to coating protection of electrodes or electrodes in a redox flow battery, a zinc-chlorine battery, a zinc-bromine battery, or the like. .
滿足上述式(1)的膜表示體積電阻率ρ與拉伸伸長率E的平衡相較於不滿足式(1)的膜更良好。圖1是表示實施例(以○表示)與比較例(以◇表示)的膜的體積電阻率ρ與拉伸伸長率E的關係的半對數圖表(semilog graph)，縱軸為ρ、橫軸為E。直線(1)表示Logρ=0.02E-1.4，直線(2)表示Logρ=0.02E-1.6。膜的體積電阻率ρ的值越小，且拉伸伸長率E的值越大，則作為氧化還原液流電池等中的電極越佳，因此在圖1的圖表中，體積電阻率ρ越接近0、且拉伸伸長率E自0向右方向越偏離，則可以說兩者的平衡越良好。如圖1所見般，實施例的膜滿足式(1)，即在直線(1)上或較其下方繪圖，這表示與比較例的膜相比，上述平衡更良好。上述平衡越高越佳，更佳為滿足式(2)。The film satisfying the above formula (1) indicates that the balance of the volume resistivity ρ and the tensile elongation E is better than that of the film not satisfying the formula (1). Figure 1 is a diagram showing an embodiment (in○ shows a semilog graph of the relationship between the volume resistivity ρ and the tensile elongation E of the film of the comparative example (indicated by ◇), the vertical axis is ρ, and the horizontal axis is E. A straight line (1) indicates Logρ=0.02E-1.4, and a straight line (2) indicates Logρ=0.02E-1.6. The smaller the value of the volume resistivity ρ of the film is, and the larger the value of the tensile elongation E is, the better the electrode in the redox flow battery or the like is. Therefore, in the graph of Fig. 1, the volume resistivity ρ is closer. 0, and the tensile elongation E deviates from 0 to the right direction, it can be said that the balance between the two is better. As seen in Fig. 1, the film of the example satisfies the formula (1), i.e., plotted on or below the straight line (1), which indicates that the above balance is better than that of the film of the comparative example. The higher the above balance, the better, and it is better to satisfy the formula (2).
Logρ≦0.02E-1.6...式(2)Logρ≦0.02E-1.6...(2)
另外，本說明書中，體積電阻率ρ及拉伸伸長率E是藉由以下方法而確定的值。In the present specification, the volume resistivity ρ and the tensile elongation E are values determined by the following methods.
(a)體積電阻率ρ(a) Volume resistivity ρ
依據JIS K 7194，藉由4探針法(probe method)而測定。將在溫度為23℃±2℃及相對濕度為50%±5%的試驗室中進行了24小時以上狀態調節的膜，切出膜的縱方向(machine direction)80mm×膜的寬度方向50mm的大小，而作為試驗片。使用三菱化學分析技術(Mitsubishi Chemical Analytech)股份有限公司的電阻率計「Loresta GPMCP-T610型(商品名)」，使用在一直線上等間隔(探針間隔為5mm)排列的探針，對1片試驗片在5個測定位置進行測定。對3片試驗片進行該操作，將合計15個體積電阻率的值的平均值作為該膜的體積電阻率ρ。膜厚度是使用尾崎製作所股份有限公司的針盤式測厚儀(DIAL THICKNESS GAUGE)「H-1A(商品名)」，依據JIS K 7194所規定的試驗片的尺寸測定進行測定。另外，關於電阻率測定方法及其理論，可參照三菱化學分析技術股份有限公司的主頁(http：//www.mccat.co.jp/3seihin/genri/gh1up2.htm)等。It was measured by a probe method according to JIS K 7194. The film was adjusted in a test chamber having a temperature of 23 ° C ± 2 ° C and a relative humidity of 50% ± 5% for 24 hours or more, and the machine direction of the film was cut out to 80 mm × the width direction of the film was 50 mm. Size, and as a test piece. Using a resistivity meter "Loresta GPMCP-T610 type (trade name)" from Mitsubishi Chemical Analytech Co., Ltd., using a probe arranged at equal intervals (probe intervals of 5 mm) on a straight line, one piece is used. The test piece was taken at 5 measurement positions.Determination. This operation was performed on three test pieces, and the average value of the total of 15 volume resistivities was taken as the volume resistivity ρ of the film. The film thickness was measured using the DIAL THICKNESS GAUGE "H-1A (trade name)" of Ozaki Manufacturing Co., Ltd., and the measurement of the size of the test piece specified in JIS K 7194. In addition, the method of measuring the resistivity and the theory thereof can be referred to the homepage of Mitsubishi Chemical Analysis Technology Co., Ltd. (http://www.mccat.co.jp/3seihin/genri/gh1up2.htm).
(b)拉伸伸長率E(b) Tensile elongation E
依據JIS K 7127進行測定。對在溫度為23℃±2℃及相對濕度為50%±5%的試驗室中進行了24小時以上狀態調節的膜，使用島津製作所股份有限公司的拉伸試驗機「AUTOGRAPHAGS-1kNG(商品名)」，將膜的寬度方向設為拉伸方向，在試驗片類型為1號啞鈴、夾頭間的初始距離為120mm、標線間距離為50mm、拉伸速度為5mm/分鐘的條件下進行拉伸試驗，而求出斷裂時的伸長率的值。對5個試驗片進行該試驗，將這些的平均值作為該膜的拉伸伸長率E。膜厚度是使用尾崎製作所股份有限公司的針盤式測厚儀「H-1A(商品名)」，對試驗片的標線間進行測定(計10個部位)，並使用這些的平均值。The measurement was carried out in accordance with JIS K 7127. For the film which was adjusted for 24 hours or more in a laboratory having a temperature of 23 ° C ± 2 ° C and a relative humidity of 50% ± 5%, the tensile tester "AUTOGRAPHAGS-1kNG (product name) of Shimadzu Corporation was used. ), the width direction of the film is set to the stretching direction, and the test piece type is No. 1 dumbbell, the initial distance between the chucks is 120 mm, the distance between the lines is 50 mm, and the stretching speed is 5 mm/min. The tensile test was performed to determine the value of the elongation at the time of the fracture. This test was carried out on five test pieces, and the average value of these was taken as the tensile elongation E of the film. The thickness of the film was measured using a dial gauge "H-1A (trade name)" of Ozaki Co., Ltd., and the measurement lines of the test pieces were measured (10 parts), and the average value of these was used.
以下，藉由實施例對本發明進行說明，但本發明並不限定於此。Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto.
實施例1~實施例11及比較例1~比較例14Example 1 to Example 11 and Comparative Example 1 to Comparative Example 14
使用日本輥製造(Nippon Roll MFG)股份有限公司的5升強混合機(intensive mixer)，將表1所示的調配比的調配物進行熔融混練。此時，排出溫度設為190℃。接著，使用日本輥製造股份有限公司的輥直徑為200mm、輥寬度為700mm的反L字四個輥壓延機，而獲得厚度為300μm的膜(輥溫度按第一輥/第二輥/第三輥/第四輥的順序為205℃/205℃/185℃/175℃、拉伸速度為5m/分鐘)。對所得的膜，確定體積電阻率ρ及拉伸伸長率E，並且依據下述方法，進行耐彎折性及柔軟性的試驗。將結果表示於表1。The blending ratio of the formulation shown in Table 1 was melt-kneaded using a 5-liter intensive mixer manufactured by Nippon Roll MFG Co., Ltd. At this time, the discharge temperature was set to 190 °C. Next, a four-roll calender having a roll diameter of 200 mm and a roll width of 700 mm was used, and a film having a thickness of 300 μm was obtained (the roll temperature was the first roll/second roll/third The order of the rolls/fourth rolls was 205 ° C / 205 ° C / 185 ° C / 175 ° C, and the drawing speed was 5 m / min). The volume resistivity ρ and the tensile elongation E were determined for the obtained film, and tests for bending resistance and flexibility were carried out in accordance with the following methods. The results are shown in Table 1.
(c)耐彎折性(c) bending resistance
自在溫度為23℃±2℃及相對濕度為50%±5%的試驗室中進行了24小時以上狀態調節的膜，以膜的縱方向成為拉伸方向的方式，衝壓JIS K 7127的試驗片類型1B的試驗片，以試驗片的兩端的夾頭部的整體重疊的方式，彎折180°，用手指捋彎折位置後翻起。接著，將其向相反側同樣彎折180°，用手指捋彎折位置後翻起。將如此在相同的彎折位置，彎折翻起，並向相反側彎折翻起的操作設為1組，重複該操作，藉由以下基準進行判斷。A film which was adjusted in a state of 24 hours or more in a test chamber having a temperature of 23 ° C ± 2 ° C and a relative humidity of 50% ± 5%, and a test piece of JIS K 7127 was punched so that the longitudinal direction of the film became the stretching direction. The test piece of the type 1B was bent by 180° so that the entire head of the test piece was overlapped with each other, and the position was folded by the finger and then turned up. Next, the same side is bent 180° to the opposite side, and the finger is bent at the bent position and then turned up. The operation of bending up and down at the same bending position and bending up to the opposite side was set to one set, and the operation was repeated, and the judgment was made by the following criteria.
○：6組後膜亦未斷裂。○: The film was not broken after the 6 groups.
△：2組~6組後膜斷裂。△: Membrane rupture in group 2 to group 6.
×：1組後膜斷裂。×: After 1 group, the membrane was broken.
(d)柔軟性(d) softness
使用上述(b)的拉伸試驗中所得的應力應變曲線，將伸長率為5%時的模數值作為柔軟性指標而算出。該值小則表示柔軟性高。Using the stress-strain curve obtained in the tensile test of the above (b), the modulus value at an elongation of 5% was calculated as a softness index. Smaller value means softnesshigh.
所使用的材料如以下所述。The materials used are as follows.
成分(A)Ingredient (A)
(A-1)昭和電工股份有限公司的氯化聚乙烯「Erasuren 404B(商品名)」、氯含量為40質量%、熔融流動速率(180℃、211.8N)為25g/10分鐘、熔解熱量為29J/g(A-1) chlorinated polyethylene "Erasuren 404B (trade name)" of Showa Denko Co., Ltd., chlorine content of 40% by mass, melt flow rate (180 ° C, 211.8 N) of 25 g/10 min, and heat of fusion 29J/g
(A-2)昭和電工股份有限公司的氯化聚乙烯「Erasuren 303B(商品名)」、氯含量為32質量%、熔融流動速率(180℃、211.8N)為25g/10分鐘、熔融熱量為50J/g(A-2) chlorinated polyethylene "Erasuren 303B (trade name)" of Showa Denko Co., Ltd., chlorine content of 32% by mass, melt flow rate (180 ° C, 211.8 N) of 25 g/10 min, and heat of fusion 50J/g
(A-3)陶氏化學(Dow Chemical)公司的低密度聚乙烯「D9100.00(商品名)」、熔融流動速率(190℃、21.18N)為1g/10分鐘、密度為877Kg/m3(A-3) Low Density Polyethylene "D9100.00 (trade name)" of Dow Chemical Co., Ltd., melt flow rate (190 ° C, 21.18 N) of 1 g/10 min, density of 877 Kg/m3
成分(B)Ingredient (B)
(B-1)納諾塞爾S.A.公司的多層碳奈米管「NANOCYL NC7000(商品名)」、平均直徑為9.5nm、平均長度為1.5μm、體積比重為0.043g/cm3、純度為90質量%(B-1) Nanosoil SA's multilayer carbon nanotube "NANOCYL NC7000 (trade name)", with an average diameter of 9.5 nm, an average length of 1.5 μm, a bulk specific gravity of 0.043 g/cm3 , and a purity of 90 quality%
(B-2)昭和電工股份有限公司的多層碳奈米管「VGCF-X(商品名)」、平均直徑為15nm、平均長度為3μm、體積比重為0.08g/cm3、純度為93質量%(B-2) Multilayer carbon nanotube "VGCF-X (trade name)" of Showa Denko Co., Ltd., having an average diameter of 15 nm, an average length of 3 μm, a bulk specific gravity of 0.08 g/cm3 , and a purity of 93% by mass.
(B-3)阿科瑪(Arkema)公司的多層碳奈米管「C100(商品名)」、平均直徑為12nm、平均長度為1μm、體積比重為0.1g/cm3、純度為90質量%(B-3) Arkema's multilayer carbon nanotube "C100 (trade name)", having an average diameter of 12 nm, an average length of 1 μm, a bulk specific gravity of 0.1 g/cm3 , and a purity of 90% by mass.
成分(C)Ingredient (C)
(C-1)電氣化學工業股份有限公司的乙炔黑「Denka Black粒狀(商品名)」、一次粒子的平均粒徑為35nm(藉由電子顯微鏡(Transmission electron microscope，TEM)觀察而測定)、比表面積為69m2/g(C-1) acetylene black "Denka Black Granular (trade name)" of the Electrochemical Industry Co., Ltd., and the average particle diameter of the primary particles is 35 nm (measured by transmission electron microscope (TEM) observation), Specific surface area is 69m2 /g
(C-2)伊藤石墨工業股份有限公司的天然石墨粉碎物「Z-5F(商品名)」、鱗片狀、平均粒徑為4μm(C-2) Natural graphite pulverized material "Z-5F (trade name)" of Ito Graphite Industry Co., Ltd., scaly, average particle size 4 μm
比較成分(C)Comparative ingredient (C)
(C-3)獅王(LION)股份有限公司的科琴黑「KJ300(商品名)」(C-3) Keqin Black "KJ300 (trade name)" of Lion King (LION) Co., Ltd.
成分(D)Ingredient (D)
(D-1)東麗股份有限公司的碳纖維「TORAYCA CUTFIBER T008A-006(商品名)」、切割長度為6mm、纖維直徑為7μm(D-1) Toray Co., Ltd. carbon fiber "TORAYCA CUTFIBER T008A-006 (trade name)", cutting length of 6mm, fiber diameter of 7μm
任意成分Optional ingredient
日東化成工業股份有限公司的氯化聚乙烯用穩定劑「STANN JF-95B(商品名)」Nitto Chemical Industry Co., Ltd. Stabilizer "STANN JF-95B (trade name)" for chlorinated polyethylene
實施例1~實施例11的膜滿足式(1)，並具有低的體積電阻率與高的拉伸伸長率、耐彎折性及柔軟性。另一方面，比較例1~比較例12的膜不滿足式(1)，拉伸伸長率、耐彎折性、柔軟性的任一種均不充分，或導電性差。使用科琴黑代替成分(C)的比較例13及比較例14中，樹脂組成物在製膜時完全未顯現熔融延性，而無法獲得膜。The films of Examples 1 to 11 satisfy the formula (1) and have low volume resistivity and high tensile elongation, bending resistance and flexibility. On the other hand, in the film of Comparative Example 1 to Comparative Example 12, the formula (1) was not satisfied, and any of tensile elongation, bending resistance, and flexibility was insufficient, or conductivity was poor. In Comparative Example 13 and Comparative Example 14 in which Ketjen black was used instead of the component (C), the resin composition did not exhibit melt ductility at the time of film formation, and the film could not be obtained.
而且，對於實施例9的膜，亦測定拉伸試驗後的體積電阻率ρ。將膜的寬度方向設為長度方向，將切出100mm×25mm的大小的膜作為試驗片，在其中心點(兩對角線的交點)藉由標記油墨進行標記，在拉伸速度為5mm/分鐘的條件下進行拉伸，直至夾頭間的初始距離50mm變為100mm後，將上述標記位置1個部位作為測定位置，除此以外，以與上述(a)相同的方式，測定拉伸試驗後的體積電阻率ρ。拉伸試驗前的體積電阻率為2.5×10-1Ω．cm，相對於此，拉伸試驗後為3.6×100Ω．cm。即，即便進行100%的拉伸變形，體積電阻率的降低亦為1位數。這表示包含本發明的樹脂組成物的導電性樹脂膜，因變形所致的導電性的變化非常小。Further, with respect to the film of Example 9, the volume resistivity ρ after the tensile test was also measured. The width direction of the film was set to the longitudinal direction, and a film having a size of 100 mm × 25 mm was cut out as a test piece, and the center point (the intersection of the two diagonal lines) was marked with a marking ink at a stretching speed of 5 mm/ Tensile test was carried out in the same manner as in the above (a) except that the initial distance between the chucks was changed to 50 mm after the initial distance of 50 mm was changed to 100 mm. After the volume resistivity ρ. The volume resistivity before the tensile test was 2.5×10-1 Ω. Cm, in contrast, after the tensile test is 3.6 × 100 Ω. Cm. That is, even if 100% tensile deformation is performed, the volume resistivity is reduced by one digit. This indicates that the conductive resin film containing the resin composition of the present invention has a very small change in conductivity due to deformation.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW102119863ATWI585139B (en) | 2013-06-05 | 2013-06-05 | Resin composition and conductive resin film |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW102119863ATWI585139B (en) | 2013-06-05 | 2013-06-05 | Resin composition and conductive resin film |
| Publication Number | Publication Date |
|---|---|
| TW201446855A TW201446855A (en) | 2014-12-16 |
| TWI585139Btrue TWI585139B (en) | 2017-06-01 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102119863ATWI585139B (en) | 2013-06-05 | 2013-06-05 | Resin composition and conductive resin film |
| Country | Link |
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| TW (1) | TWI585139B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844926A (en)* | 2010-04-16 | 2012-12-26 | 住友电气工业株式会社 | Bipolar plate for redox flow battery |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844926A (en)* | 2010-04-16 | 2012-12-26 | 住友电气工业株式会社 | Bipolar plate for redox flow battery |
| Publication number | Publication date |
|---|---|
| TW201446855A (en) | 2014-12-16 |
| Publication | Publication Date | Title |
|---|---|---|
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