TWI763082B - Paper recycling and remaking conductive paper and its making method - Google Patents

Paper recycling and remaking conductive paper and its making method Download PDF

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TWI763082B
TWI763082B TW109136068A TW109136068A TWI763082B TW I763082 B TWI763082 B TW I763082B TW 109136068 A TW109136068 A TW 109136068A TW 109136068 A TW109136068 A TW 109136068A TW I763082 B TWI763082 B TW I763082B
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paper
conductive
conductive paper
recycling
expanded graphite
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TW202217114A (en
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石燕鳳
楊佳欣
陳政廷
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朝陽科技大學
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A paper recycling and remaking conductive paper and its making method, the conductive paper is made by wet papermaking and consists of recycled pulp, expanded graphite, dispersant and interfacial active agent, the recycled pulp is made of waste paper, the expanded graphite is a modified carbon material with chemically modified grafted epoxy group, hydroxyl group, carbonyl group or its combination active functional group, by adding the modified expanded graphite, the conductive paper has the advantages of conductivity, low cost, resistance to combustion and recycling, moreover, by using the waste paper as the main source of pulp material, the conductive paper can reuse the filler of the waste paper itself or the material printed on it to achieve the purpose of not adding a large amount of interfacial active agents and conductive materials.

Description

紙張回收再製導電紙及其製法Conductive paper made from paper recycling and its production method

本發明有關於導電紙，特別是指利用紙張回收再製成的導電紙及其製法。The present invention relates to conductive paper, in particular to conductive paper made by recycling paper and its production method.

導電紙是一種具有良好導電性能的紙，其導電性對外界環境的濕度變化不敏感，具有較高的抗張和撕裂強度。導電紙主要使用化學木漿抄造，透過在紙漿中加入一些導電物質，如導電炭黑（conductive carbon black）或乙炔炭黑（acetylene black）或碳纖維，也可以加入少量導電性能良好的金屬粉末或金屬化纖維，或者在原紙表面噴塗金屬、金屬氧化物等。目前，導電紙主要用作熱電照相紙、電敏紙和電印刷紙等，近年來更發展在可撓曲顯示器和可穿戴設備之應用。Conductive paper is a kind of paper with good electrical conductivity, its electrical conductivity is not sensitive to the humidity change of the external environment, and has high tensile and tear strength. Conductive paper is mainly made of chemical wood pulp. By adding some conductive substances to the pulp, such as conductive carbon black or acetylene black or carbon fiber, a small amount of metal powder or metal with good conductivity can also be added. Chemical fiber, or spray metal, metal oxide, etc. on the surface of the base paper. At present, conductive paper is mainly used as thermoelectrophotographic paper, electrosensitive paper and electroprinting paper, etc. In recent years, it has been further developed in flexible displays and wearable devices.

其中，碳纖維導電紙是將碳纖維與木質紙漿、合成纖維紙漿，采用濕法造紙技術，經科學方法將其均勻的分散在一起，使其達到具有導電均勻、抗靜電、防屏蔽等功能。碳纖維導電紙是將碳纖維和其他纖維或者粉末材料在溶劑中充分分散，抄成紙張烘乾而得到。為了使纖維之間交織得更充分，通常要加入有機化合物，例如聚乙烯醇、聚亞酰胺等黏合劑和陽離子補強劑，以增加纖維之間的結合力；同時碳纖維的含量也可以在很寬的範圍內調節。Among them, carbon fiber conductive paper is made of carbon fiber, wood pulp and synthetic fiber pulp, using wet papermaking technology, and dispersing them evenly by scientific methods, so that it has the functions of uniform conductivity, antistatic, and anti-shielding. Carbon fiber conductive paper is obtained by fully dispersing carbon fiber and other fibers or powder materials in a solvent, and drying it into paper. In order to make the fibers more fully intertwined, organic compounds, such as polyvinyl alcohol, polyimide and other adhesives and cationic reinforcing agents are usually added to increase the bonding force between fibers; at the same time, the content of carbon fibers can also be very wide. adjustment within the range.

值得注意的是，在碳材料中，石墨烯因具有優異的導電及導熱性而被廣泛應用在半導體、高分子複合材料中，但石墨烯高昂的價格經常是開發與研究上的一大阻力。此外，奈米碳管也是被廣泛地用於複合材料之中，利用奈米碳管的性質可以製作出很多性能優異的複合材料；例如，使用奈米碳管材料增強的塑料力學性能優良、導電性好等優點，但研究發現，奈米碳管疑似為致癌物質，並且長時間接觸之後，對肺臟可能有類似石棉的影響，因此，奈米碳管的大量使用及普及化仍然是需要受到更多考驗的；再者，奈米碳管不易均勻分散於紙漿中，因而導致目前以奈米碳管製成的導電紙存在生產及製作成本高的技術問題。It is worth noting that among carbon materials, graphene is widely used in semiconductor and polymer composite materials due to its excellent electrical and thermal conductivity, but the high price of graphene is often a major obstacle to development and research. In addition, carbon nanotubes are also widely used in composite materials, and many composite materials with excellent performance can be made by using the properties of carbon nanotubes; for example, plastics reinforced with carbon nanotubes have excellent mechanical properties and electrical conductivity. However, studies have found that carbon nanotubes are suspected to be carcinogens, and after prolonged exposure, they may have asbestos-like effects on the lungs. Therefore, the extensive use and popularization of carbon nanotubes still needs to be more In addition, the carbon nanotubes are not easy to be uniformly dispersed in the pulp, which leads to the technical problem of high production and production cost of the conductive paper made of carbon nanotubes at present.

為克服上述技術問題，本發明之目的在於提供一種紙張回收再製導電紙及其製法，本發明導電紙係經濕法造紙技術製成，且該導電紙的組成包括回收紙漿、膨脹石墨、分散劑以及界面活性劑，其中，該回收紙漿係由廢棄紙張製成之紙漿，該膨脹石墨係經化學改質接枝環氧基（-CH(O)CH-）、羥基（-OH）、羰基（-C=O）或其組合之活性官能基的改質碳材料。藉此，本發明導電紙透過添加改質膨脹石墨不僅增加導電性能，並能有效改善一般紙張遇火即燃的特性，兼具導電、低成本、耐燃與循環再利用等優勢；此外，本發明導電紙透過使用廢棄紙張作為主要的紙漿材料來源，能夠再利用廢棄紙張本身的填料或其上印製的材料（例如影印紙的碳粉），達到不需要添加大量界面活性劑（填料）及導電材（碳粉）之目的。In order to overcome the above-mentioned technical problems, the purpose of the present invention is to provide a kind of paper recycling and remanufacturing conductive paper and its preparation method, the conductive paper of the present invention is made by wet papermaking technology, and the composition of the conductive paper includes recycled pulp, expanded graphite, dispersant And a surfactant, wherein, the recycled pulp is pulp made from waste paper, and the expanded graphite is chemically modified to graft epoxy (-CH(O)CH-), hydroxyl (-OH), carbonyl (- -C=O) or the modified carbon material of the active functional group of its combination. Thereby, the conductive paper of the present invention not only increases the electrical conductivity by adding modified expanded graphite, but also can effectively improve the characteristics of ordinary paper that it ignites when exposed to fire, and has the advantages of electrical conductivity, low cost, flame resistance, and recycling. By using waste paper as the main source of pulp material, conductive paper can reuse the filler of waste paper itself or the materials printed on it (such as carbon powder for photocopying paper), so that it does not need to add a lot of surfactants (fillers) and conduct electricity. material (toner).

為達上述目的，本發明所提供一種紙張回收再製導電紙，係經濕法造紙技術製成，該導電紙以其總重量百分比（wt%）計算的組成配比包括：回收紙漿，佔55wt%至90wt%；膨脹石墨（EG），佔10wt%至40wt%；分散劑，佔0.1wt%至0.5wt%；界面活性劑，佔0.02wt%至0.2wt%；其中，該膨脹石墨係經化學改質接枝環氧基（-CH(O)CH-）、羥基（-OH）、羰基（-C=O）或其組合之活性官能基的改質碳材料。In order to achieve the above-mentioned purpose, the present invention provides a kind of paper recycling and remanufacturing conductive paper, which is made by wet papermaking technology. The composition ratio of the conductive paper calculated by its total weight percentage (wt%) includes: recycled pulp, accounting for 55wt% to 90wt%; expanded graphite (EG), accounting for 10wt% to 40wt%; dispersant, accounting for 0.1wt% to 0.5wt%; surfactant, accounting for 0.02wt% to 0.2wt%; Modified carbon material with active functional groups of modified grafted epoxy group (-CH(O)CH-), hydroxyl group (-OH), carbonyl group (-C=O) or their combination.

於本發明紙張回收再製導電紙的實施例中，該回收紙漿係選自印製碳粉之影印紙張、書籍紙張、印刷紙張或其組合。In the embodiment of the present invention in which the paper is recycled into conductive paper, the recycled pulp is selected from photocopying paper, book paper, printing paper or a combination thereof for printing toner.

於本發明紙張回收再製導電紙的實施例中，該分散劑係選自聚乙烯醇、聚醋酸乙烯酯、羧甲基纖維素或羧乙基纖維素。In the embodiment of the present invention in which the paper is recycled to make conductive paper, the dispersant is selected from polyvinyl alcohol, polyvinyl acetate, carboxymethyl cellulose or carboxyethyl cellulose.

於本發明紙張回收再製導電紙的實施例中，以導電紙總重量百分比（wt%）計算，該界面活性劑包括：第一界面活性劑，佔0.01wt%至0.1wt%，該第一界面活性劑，係選自陰離子界面性活性劑，較佳選自含10至18個碳之磺酸鹽；第二界面活性劑，佔0.01wt%至0.1wt%；該第二界面活性劑，係選自非離子界面活性劑，較佳選自吐溫-60（Tween 60）、吐溫-80（Tween 80）、斯盤-60（Span 60）或斯盤-80（Span 80）。In the embodiment of the present invention in which the paper is recycled into conductive paper, calculated in terms of the total weight percentage (wt%) of the conductive paper, the surfactant includes: a first surfactant, accounting for 0.01wt% to 0.1wt%, the first interface The active agent is selected from anionic surfactants, preferably selected from sulfonates containing 10 to 18 carbons; the second surfactant accounts for 0.01wt% to 0.1wt%; the second surfactant is It is selected from non-ionic surfactants, preferably selected from Tween-60 (Tween 60), Tween-80 (Tween 80), Span-60 (Span 60) or Span-80 (Span 80).

於本發明紙張回收再製導電紙的實施例中，該膨脹石墨透過氧化劑氧化表面以接枝環氧基（-CH(O)CH-）、羥基（-OH）及/或羰基（-C=O）。如下列化學結構式，顯示本發明同時接枝環氧基、羥基及羰基的改質膨脹石墨：In the embodiment of the present invention in which the paper is recycled into conductive paper, the expanded graphite oxidizes the surface through an oxidizing agent to graft epoxy groups (-CH(O)CH-), hydroxyl groups (-OH) and/or carbonyl groups (-C=O ). The following chemical structural formula shows the modified expanded graphite grafted with epoxy group, hydroxyl group and carbonyl group of the present invention at the same time:

Figure 02_image001
其中，(A)為環氧基（-CH(O)CH-），(B)為羥基（-OH）、(C)為羰基（-C=O）。
Figure 02_image001
Among them, (A) is an epoxy group (-CH(O)CH-), (B) is a hydroxyl group (-OH), and (C) is a carbonyl group (-C=O).

於本發明紙張回收再製導電紙的實施例中，該氧化劑係選自酸或高錳酸鉀，較佳地，酸係選自鹽酸、硝酸或硫酸。In the embodiment of the present invention, the oxidizing agent is selected from acid or potassium permanganate, preferably, the acid is selected from hydrochloric acid, nitric acid or sulfuric acid.

本發明另提供一種紙張回收再製導電紙之製法，該製法步驟包括：The present invention further provides a method for producing conductive paper by recycling paper, the steps of the method comprising:

取材步驟：提供如前所述之導電紙之組成成分及配比；Material acquisition steps: provide the composition and proportion of the conductive paper as described above;

濕法造紙步驟：將前述導電紙之組成成分按配比混合後，採用濕法造紙技術製成導電紙。Wet papermaking step: After mixing the above-mentioned components of the conductive paper according to the proportions, the conductive paper is made by wet papermaking technology.

於本發明紙張回收再製導電紙之製法的實施例中，前述導電紙之組成成分係於室溫下攪拌混合。In the embodiment of the method for producing conductive paper from paper recycling of the present invention, the components of the conductive paper are stirred and mixed at room temperature.

於本發明紙張回收再製導電紙之製法的實施例中，前述導電紙之組成成分係於每分鐘80至120轉之攪拌速度持續攪拌5至10分鐘，以獲得混合均勻的複合紙漿。In the embodiment of the method for producing conductive paper from paper recycling of the present invention, the components of the conductive paper are continuously stirred at a stirring speed of 80 to 120 rpm for 5 to 10 minutes to obtain a uniformly mixed composite pulp.

於本發明紙張回收再製導電紙之製法的實施例中，該複合紙漿倒入篩網至均勻瀝乾水分後，取下含水紙張；該含水紙張經熱壓機壓平後再烘乾，製得該導電紙。In the embodiment of the method for producing conductive paper from paper recycling of the present invention, the composite pulp is poured into a screen until the water is evenly drained, and then the water-containing paper is removed; the water-containing paper is flattened by a hot press and then dried to obtain a The conductive paper.

有關於本發明為達成上述目的，所採用之技術、手段及其他功效，茲舉較佳可行實施例並配合圖式詳細說明如後。Regarding the techniques, means and other effects adopted by the present invention to achieve the above-mentioned objects, preferred feasible embodiments are given and described in detail in conjunction with the drawings as follows.

為利於對本發明的瞭解，以下結合實施例進行說明。In order to facilitate the understanding of the present invention, the following description is given in conjunction with the embodiments.

本發明特徵與優點的一些實施例將在以下說明中詳細敘述。應理解的是本發明能夠在不同的態樣上具有各種的變化，然其皆不脫離本發明的範圍，且其中的說明及圖式在本質上係當作說明之用，而非用於限制本發明。Some embodiments of the features and advantages of the present invention are set forth in detail in the following description. It should be understood that the present invention can have various changes in different aspects without departing from the scope of the present invention, and the descriptions and drawings therein are essentially used for illustration rather than limitation this invention.

本發明導電紙係經濕法造紙技術製成，該導電紙是一種利用廢棄紙張作為紙漿來源，配合添加界面活性劑、分散劑以及接枝有環氧基（-CH(O)CH-）、羥基（-OH）、羰基（-C=O）或其組合等官能基進行化學改質之膨脹石墨（EG），以令膨脹石墨更均勻地分散於紙漿中並提高膨脹石墨與紙漿之親和性。The conductive paper of the present invention is made by wet papermaking technology. The conductive paper is a kind of paper using waste paper as a pulp source, and adding a surfactant, a dispersant and grafted epoxy groups (-CH(O)CH-), Expanded graphite (EG) chemically modified with functional groups such as hydroxyl (-OH), carbonyl (-C=O) or their combination to make the expanded graphite more uniformly dispersed in the pulp and improve the affinity between the expanded graphite and the pulp .

具體地，本發明之導電紙以其總重量百分比（wt%）計算，該導電紙的組成配比包括：佔整體55wt%至90wt%的回收紙漿、佔整體10wt%至40wt%的膨脹石墨（EG）、佔整體0.1wt%至0.5wt%的分散劑以及佔整體0.02wt%至0.2wt%的界面活性劑；其中，該膨脹石墨係經化學改質接枝環氧基（-CH(O)CH-）、羥基（-OH）、羰基（-C=O）或其組合之活性官能基的改質碳材料。Specifically, the conductive paper of the present invention is calculated based on its total weight percentage (wt%), and the composition ratio of the conductive paper includes: 55wt% to 90wt% of recycled pulp, 10wt% to 40wt% of expanded graphite ( EG), a dispersant accounting for 0.1wt% to 0.5wt% of the whole, and a surfactant accounting for 0.02wt% to 0.2wt% of the whole; wherein, the expanded graphite is a chemically modified grafted epoxy group (-CH(O )CH-), hydroxyl (-OH), carbonyl (-C=O) or the modified carbon material of the active functional group of the combination.

本發明導電紙中的回收紙漿是指由廢棄紙張回收再製之紙漿；其中，所述廢棄紙張可選自印有碳粉之影印紙、書籍紙張、印刷紙張或其組合。較佳地，該廢棄紙張係經過影印而附著有影印機碳粉之影印紙；藉此，利用影印紙製做時添加的填料，達到降低界面活性劑在導電紙材料中的添加量，並利用廢棄影印紙上的碳粉做為導電材，從而製備出導電性能優異的導電紙，並能改善一般紙張遇火即燃的特性。The recycled pulp in the conductive paper of the present invention refers to pulp recovered from waste paper; wherein, the waste paper can be selected from photocopying paper, book paper, printing paper or a combination thereof printed with carbon powder. Preferably, the waste paper is photocopying paper with photocopier toner attached to it by photocopying; thereby, the filler added when the photocopying paper is made is used to reduce the amount of surfactant added in the conductive paper material, and use The carbon powder on the waste photocopying paper is used as a conductive material, so as to prepare conductive paper with excellent electrical conductivity, and can improve the characteristics of ordinary paper that it ignites when exposed to fire.

於本發明實施例中，該回收紙漿的預處理方法步驟包括：In the embodiment of the present invention, the pretreatment method steps of the recycled pulp include:

步驟1：將廢棄紙張放到水中，水的體積為廢棄紙張的2至3倍；Step 1: Put the waste paper into water, the volume of water is 2 to 3 times that of the waste paper;

步驟2：將步驟1的紙張與水混合液加熱到60至80℃，並持續攪拌至形成所需要的紙漿。Step 2: Heat the mixed solution of paper and water in Step 1 to 60 to 80°C, and continue stirring until the desired pulp is formed.

本發明導電紙中的分散劑和界面活性劑主要用於增加膨脹石墨在本發明導電紙複合材料中的分散性，使膨脹石墨均勻地分散於複合材料中。其中，該分散劑可選自聚乙烯醇、聚醋酸乙烯酯、羧甲基纖維素或羧乙基纖維素；較佳地，本發明導電紙中的分散劑為聚乙烯醇（簡稱PVA，分子式為(C 2H 4O) x）。其中，該界面活性劑包括佔該導電紙整體重量百分比0.01wt%至0.1wt%的第一界面活性劑以及佔整體0.01wt%至0.1wt%的第二界面活性劑。更具體地，該第一界面活性劑可選自陰離子界面活性劑，較佳選自含10至18個碳之磺酸鹽；該第二界面活性劑可選自非離子界面活性劑，較佳選自吐溫-60（Tween 60）、吐溫-80（Tween 80）、斯盤-60（Span 60）或斯盤-80（Span 80）。較佳地，於本發明實施例中，該第一界面活性劑較佳為十二烷基磺酸鈉，該第二界面活性劑較佳為吐溫-80（Tween 80）。 The dispersant and the surfactant in the conductive paper of the present invention are mainly used to increase the dispersibility of the expanded graphite in the conductive paper composite material of the present invention, so that the expanded graphite is uniformly dispersed in the composite material. Wherein, the dispersant can be selected from polyvinyl alcohol, polyvinyl acetate, carboxymethyl cellulose or carboxyethyl cellulose; preferably, the dispersant in the conductive paper of the present invention is polyvinyl alcohol (PVA for short, molecular formula is (C 2 H 4 O) x ). Wherein, the surfactant includes a first surfactant in an amount of 0.01wt% to 0.1wt% of the entire conductive paper and a second surfactant in an overall amount of 0.01wt% to 0.1wt%. More specifically, the first surfactant can be selected from anionic surfactants, preferably selected from sulfonates containing 10 to 18 carbons; the second surfactant can be selected from nonionic surfactants, preferably Select from Tween 60, Tween 80, Span 60 or Span 80. Preferably, in the embodiment of the present invention, the first surfactant is preferably sodium dodecyl sulfonate, and the second surfactant is preferably Tween-80 (Tween 80).

於本發明實施例中，本發明導電紙中的膨脹石墨是透過氧化劑氧化表面並接枝環氧基（-CH(O)CH-）、羥基（-OH）及/或羰基（-C=O）等官能基，從而達到化學改質膨脹石墨以增加其和紙漿之間親和性之目的。具體地，該氧化劑係選自酸或高錳酸鉀，其中，該酸較佳係選自鹽酸、硝酸或硫酸。In the embodiment of the present invention, the expanded graphite in the conductive paper of the present invention oxidizes the surface through an oxidizing agent and grafts epoxy groups (-CH(O)CH-), hydroxyl groups (-OH) and/or carbonyl groups (-C=O ) and other functional groups, so as to achieve the purpose of chemically modifying expanded graphite to increase the affinity between it and pulp. Specifically, the oxidizing agent is selected from acid or potassium permanganate, wherein, the acid is preferably selected from hydrochloric acid, nitric acid or sulfuric acid.

本發明膨脹石墨（EG）之化學改質方法步驟包括：The chemical modification method steps of the expanded graphite (EG) of the present invention include:

步驟1：提供氧化劑及膨脹石墨，以每公克膨脹石墨添加1莫耳氧化劑的比例均勻分散在水中；Step 1: Provide oxidant and expanded graphite, and evenly disperse in water at the ratio of adding 1 mole of oxidant per gram of expanded graphite;

步驟2：將步驟1的混合液加熱到120℃，以每分鐘300轉至400轉的攪拌速率攪拌4小時；Step 2: Heat the mixed solution of Step 1 to 120°C, and stir at a stirring rate of 300 to 400 rpm for 4 hours;

步驟3：使攪拌後的混合液冷卻，再過濾出其中的膨脹石墨，以水沖洗該膨脹石墨以去除氧化劑，將水洗後的膨脹石墨放置烘箱至乾燥，製得改質膨脹石墨。Step 3: cooling the stirred mixture, filtering out the expanded graphite therein, washing the expanded graphite with water to remove the oxidant, and placing the washed expanded graphite in an oven to dry to obtain modified expanded graphite.

藉此，膨脹石墨透過前述步驟與氧化劑反應後達到改質目的，使膨脹石墨表面氧化並接枝有環氧基（-CH(O)CH-）、羥基（-OH）及/或羰基（-C=O）等官能基。Thereby, the expanded graphite reacts with the oxidant through the aforementioned steps to achieve the purpose of modification, so that the surface of the expanded graphite is oxidized and grafted with epoxy groups (-CH(O)CH-), hydroxyl groups (-OH) and/or carbonyl groups (- C=O) and other functional groups.

以上說明本發明紙張回收再製導電紙的組成配比，以下說明前述導電紙的製法步驟。The composition ratio of the conductive paper made from the paper recycling of the present invention is described above, and the steps of the manufacturing method of the conductive paper are described below.

本發明紙張回收再製導電紙之製法步驟包括：The manufacturing method steps of the paper recycling and remanufacturing conductive paper of the present invention include:

取材步驟：以導電紙總重量百分比（wt%）計算，提供60wt%至90wt%的回收紙漿，10wt%至40wt%的膨脹石墨（EG），0.1wt%至0.5wt%的分散劑，0.02wt%至0.2wt%的界面活性劑；其中，該膨脹石墨係經化學改質接枝羥基（-OH）、羰基（-C=O）或其組合之活性官能基的改質碳材料；Material sampling steps: Calculated on the basis of the total weight percentage (wt%) of the conductive paper, provide 60wt% to 90wt% recycled pulp, 10wt% to 40wt% expanded graphite (EG), 0.1wt% to 0.5wt% dispersant, 0.02wt% % to 0.2wt% of a surfactant; wherein, the expanded graphite is a modified carbon material that has been chemically modified and grafted with active functional groups of hydroxyl (-OH), carbonyl (-C=O) or a combination thereof;

濕法造紙步驟：將前述導電紙之組成成分按配比混合後，採用濕法造紙技術製成導電紙。Wet papermaking step: After mixing the above-mentioned components of the conductive paper according to the proportions, the conductive paper is made by wet papermaking technology.

於本發明實施例中，該濕法造紙步驟還包括：In the embodiment of the present invention, the wet papermaking step further includes:

步驟1：按前述取材步驟的配比提供導電紙之組成材料。Step 1: Provide the constituent materials of the conductive paper according to the ratio of the above-mentioned steps of obtaining materials.

步驟2：將導電紙組成材料於室溫下加入水中，水體積為所有材料的2至3倍，經攪拌動作充分混合，製得複合紙漿。其中，該攪拌動作較佳以每分鐘80轉至120轉的攪拌速率為持續攪拌5至10分鐘。Step 2: Add the conductive paper constituent materials into water at room temperature, the water volume is 2 to 3 times that of all the materials, and fully mix through stirring to obtain composite pulp. Wherein, the stirring action is preferably continuous stirring for 5 to 10 minutes at a stirring speed of 80 to 120 revolutions per minute.

步驟3：將該複合紙漿倒入篩網至均勻瀝乾水分後形成含水紙張。Step 3: Pour the composite pulp into the screen until the water is evenly drained to form a water-containing paper.

步驟4：取下該含水紙張，並以熱壓機壓平後進行乾燥，製得紙張回收再製導電紙成品。其中，於本步驟中，該熱壓機係不開加溫之條件下壓平該含水紙張，目的在於壓平擠出多餘水分，再將半乾之含水紙張進行最後乾燥處理，以製得導電紙成品。Step 4: Remove the water-containing paper, flatten it with a hot press, and then dry it to obtain a finished paper recycled and remanufactured conductive paper. Wherein, in this step, the hot press is used to flatten the water-containing paper under the condition of no heating, the purpose is to flatten and squeeze out excess water, and then the semi-dry water-containing paper is finally dried to obtain conductive Finished paper.

請配合參閱圖1、圖2及表1、表2、表3，說明本發明經前述組成配比及製法製得之導電紙的性能表現。Please refer to FIG. 1, FIG. 2 and Table 1, Table 2, and Table 3 to illustrate the performance of the conductive paper prepared by the above-mentioned composition ratio and preparation method of the present invention.

表1顯示本發明導電紙的組成配比實施例，表2顯示表1之實施例於表面電阻測試之數據，表3顯示表1之實施例於拉伸強度測試之數據。其中，表1實施例中，回收紙漿的廢棄紙張來源為經影印附著有碳粉之廢棄影印紙，分散劑為聚乙烯醇，第一界面活性劑為十二烷基磺酸鈉，第二界面活性劑為吐溫-80。Table 1 shows the composition ratio examples of the conductive paper of the present invention, Table 2 shows the data of the examples in Table 1 in the surface resistance test, and Table 3 shows the data of the examples in Table 1 in the tensile strength test. Wherein, in the embodiment of Table 1, the source of waste paper of recycled pulp is waste photocopying paper with carbon powder attached to it by photocopying, the dispersant is polyvinyl alcohol, the first surfactant is sodium dodecyl sulfonate, the second interface is The active agent is Tween-80.

[表1]：各樣品之組成配比實施例。 樣品 紙漿 (wt%) 改質 膨脹石墨 (wt%) 聚乙烯醇 (wt%) 十二烷基 磺酸鈉 (wt%) Tween 80 (wt%) P 99.7 0 0.3 0 0 P/EG-10 89.64 10 0.3 0.03 0.03 P/EG-17 82.58 17 0.3 0.06 0.06 P/EG-23 76.52 23 0.3 0.09 0.09 RP 99.7 0 0.3 0 0 RP/EG-10 89.64 10 0.3 0.03 0.03 RP/EG-17 82.58 17 0.3 0.06 0.06 RP/EG-20 79.55 20 0.3 0.075 0.075 RP/EG-23 76.52 23 0.3 0.09 0.09 〔縮寫說明〕 P：Paper，未經使用的空白影印紙。 RP：Recycled Paper，經影印附著有超過紙張面積1/2之碳粉的廢棄影印紙。 EG：Expanded Graphite，膨脹石墨；實際添加為化學改質膨脹石墨。 P/EG-10、P/EG-17、P/EG-23：依序指化學改質膨脹石墨在空白影印紙紙漿中的添加量為10wt%、17wt%、23wt%。 RP/EG-10、RP/EG-17、RP/EG-20、RP/EG-23：依序指化學改質膨脹石墨在廢棄影印紙紙漿中的添加量為10wt%、17wt%、20wt%、23wt%。 [Table 1]: Example of composition ratio of each sample. sample Pulp (wt%) Modified expanded graphite (wt%) Polyvinyl alcohol (wt%) Sodium dodecyl sulfonate (wt%) Tween 80 (wt%) P 99.7 0 0.3 0 0 P/EG-10 89.64 10 0.3 0.03 0.03 P/EG-17 82.58 17 0.3 0.06 0.06 P/EG-23 76.52 twenty three 0.3 0.09 0.09 RP 99.7 0 0.3 0 0 RP/EG-10 89.64 10 0.3 0.03 0.03 RP/EG-17 82.58 17 0.3 0.06 0.06 RP/EG-20 79.55 20 0.3 0.075 0.075 RP/EG-23 76.52 twenty three 0.3 0.09 0.09 [Description of Abbreviations] P: Paper, unused blank photocopying paper. RP: Recycled Paper, waste photocopying paper with toner that exceeds 1/2 of the paper area after photocopying. EG: Expanded Graphite, expanded graphite; the actual addition is chemically modified expanded graphite. P/EG-10, P/EG-17, P/EG-23: The additions of chemically modified expanded graphite in blank photocopying paper pulp are 10wt%, 17wt%, and 23wt% in order. RP/EG-10, RP/EG-17, RP/EG-20, RP/EG-23: The addition of chemically modified expanded graphite in waste photocopying paper pulp is 10wt%, 17wt%, 20wt% in order , 23wt%.

[表2]：導電紙複合材料之表面電阻數據。 樣品 電阻 (Ω/sq) P 4181333.00 P/EG-10 1439.49 P/EG-17 1112.26 P/EG-23 0.00035 RP 1163620.00 RP/EG-10 1072.88 RP/EG-17 884.58 RP/EG-23 0.00014 〔縮寫說明〕請參閱表1說明。 [Table 2]: Surface resistance data of conductive paper composites. sample Resistance (Ω/sq) P 4181333.00 P/EG-10 1439.49 P/EG-17 1112.26 P/EG-23 0.00035 RP 1163620.00 RP/EG-10 1072.88 RP/EG-17 884.58 RP/EG-23 0.00014 [Abbreviation description] Please refer to Table 1 for description.

[表3]導電紙複合材料之拉伸強度。 樣品 拉伸強度 (MPa) RP 5.62 RP/EG-17 6.34 RP/EG-20 9.77 RP/EG-23 7.16 〔縮寫說明〕請參閱表1說明。 [Table 3] Tensile strength of conductive paper composite material. sample Tensile strength (MPa) RP 5.62 RP/EG-17 6.34 RP/EG-20 9.77 RP/EG-23 7.16 [Abbreviation description] Please refer to Table 1 for description.

由表2的實驗結果可知，本發明導電紙複合材料僅添加10wt%改質膨脹石墨時，其表面電阻有顯著下降，改質膨脹石墨添加至23wt%時其電阻由純料之電阻1163620.00(Ω/sq)降至0.00014(Ω/sq)。在機械性能方面，隨改質膨脹石墨（EG）添加量增加時，其拉伸強度由純料之5.62(MPa)上升至23wt%之7.16(MPa) ，由表1至表3之實施例證實本發明採用影印回收紙及改質膨脹石墨可達到低電阻又提升其機械強度，同時降低成本及符合環保趨勢。It can be seen from the experimental results in Table 2 that when only 10wt% of modified expanded graphite is added to the conductive paper composite material of the present invention, its surface resistance is significantly reduced. When the modified expanded graphite is added to 23wt%, its resistance is changed from the resistance of pure material to 1163620.00 (Ω). /sq) to 0.00014(Ω/sq). In terms of mechanical properties, as the amount of modified expanded graphite (EG) added increases, its tensile strength increases from 5.62 (MPa) of pure material to 7.16 (MPa) of 23wt%, which is confirmed by the examples in Table 1 to Table 3. By adopting photocopying recycled paper and modified expanded graphite, the present invention can achieve low resistance and improve its mechanical strength, while reducing cost and conforming to the trend of environmental protection.

如圖1所示，將本發明之導電紙11連接燈泡12、電池13、電線14，可以看到本發明之導電紙11能夠成功使燈泡12發亮，顯示其導電性能優異。如圖2所示，顯示本發明之導電紙15進行耐燃分析而被燃燒時，可發現導電紙11幾乎不會燃燒，具備良好的耐燃性。As shown in FIG. 1, the conductive paper 11 of the present invention is connected to the light bulb 12, the battery 13, and the wire 14. It can be seen that the conductive paper 11 of the present invention can successfully make the light bulb 12 light up, showing its excellent electrical conductivity. As shown in FIG. 2 , when the conductive paper 15 of the present invention is subjected to flame resistance analysis and burned, it can be found that the conductive paper 11 hardly burns and has good flame resistance.

綜上所述，本發明利用廢棄紙張回收再製之導電紙具有以下技術功效：To sum up, the conductive paper recycled from waste paper in the present invention has the following technical effects:

（1）廢棄紙張再利用，符合環保趨勢。(1) The reuse of waste paper is in line with the trend of environmental protection.

（2）特別是經過影印而印上碳粉的廢棄影印紙，透過印製碳粉以及影印紙本身的填料，使得採用廢棄影印紙製備導電紙時不再需要添加大量界面活性劑（填料）及導電材（碳粉）。(2) Especially the waste photocopying paper that has been printed with toner after photocopying, through the printing toner and the filler of the photocopying paper itself, it is no longer necessary to add a large amount of surfactant (filler) and Conductive material (carbon powder).

（3）本發明導電紙透過添加化學改質接枝環氧基（-CH(O)CH-）、羥基（-OH）及/或羰基（-C=O）的膨脹石墨，有效改善碳纖維材料與紙漿的親和性，並配合加入分散劑使膨脹石墨能均勻分散於構成導電紙的複合材料中。(3) The conductive paper of the present invention can effectively improve the carbon fiber material by adding chemically modified expanded graphite with grafted epoxy group (-CH(O)CH-), hydroxyl group (-OH) and/or carbonyl group (-C=O). The affinity with pulp and the addition of dispersant can make the expanded graphite evenly dispersed in the composite material constituting the conductive paper.

（4）本發明導電紙採用改質膨脹石墨作為導電紙的主要導電材料，相較於石墨烯、奈米碳管，膨脹石墨的價格低、具有耐燃性且對肺部無不良健康影響，是以，本發明導電紙透過添加改質膨脹石墨不僅增加導電性能，並能有效改善一般紙張遇火即燃的特性，兼具導電、低成本、耐燃與循環再利用等優勢。(4) The conductive paper of the present invention uses modified expanded graphite as the main conductive material of the conductive paper. Compared with graphene and carbon nanotubes, expanded graphite has low price, flame resistance and no adverse health effects on the lungs. Therefore, by adding modified expanded graphite, the conductive paper of the present invention not only increases the electrical conductivity, but also can effectively improve the characteristics of ordinary paper that it ignites when exposed to fire, and has the advantages of electrical conductivity, low cost, flame resistance and recycling.

（5）由於導電紙在可撓曲顯示器和可穿戴設備之應用，已被視為將成為塑膠基板的替代品。而當紙張具有導電性時，在電子產品應用中變得更加有價值。(5) Due to the application of conductive paper in flexible displays and wearable devices, it has been regarded as a substitute for plastic substrates. And when paper is conductive, it becomes even more valuable in electronics applications.

11、15…導電紙 12…燈泡 13…電池 14…電線 11, 15...Conductive paper 12…Bulbs 13…Battery 14…Wire

圖1是本發明製得之導電紙成品及其用於電燈導電分析之示意圖； 圖2是本發明製得之導電紙成品於耐燃分析中被燃燒後之示意圖。 Fig. 1 is the schematic diagram of the conductive paper finished product obtained by the present invention and its use in electric light conduction analysis; Fig. 2 is a schematic diagram of the finished conductive paper produced by the present invention after being burned in the flame resistance analysis.

Figure 01_image001
Figure 01_image001

Claims (7)

一種紙張回收再製導電紙，係經濕法造紙技術製成，該導電紙以其總重量百分比(wt%)計算的組成配比包括：回收紙漿，佔55wt%至90wt%；膨脹石墨(EG)，佔10wt%至40wt%；分散劑，佔0.1wt%至0.5wt%；界面活性劑，佔0.02wt%至0.2wt%；其中，該回收紙漿係選自印製碳粉之影印紙張、書籍紙張、印刷紙張或其組合，該膨脹石墨係經氧化劑氧化表面以接枝環氧基(-CH(O)CH-)、羥基(-OH)、羰基(-C=O)或其組合之活性官能基的改質碳材料，該氧化劑係選自酸或高錳酸鉀。 A kind of paper recycling and remanufacturing conductive paper, which is made by wet papermaking technology. The composition ratio of the conductive paper calculated by its total weight percentage (wt%) includes: recycled pulp, accounting for 55wt% to 90wt%; expanded graphite (EG) , accounting for 10wt% to 40wt%; dispersant, accounting for 0.1wt% to 0.5wt%; surfactant, accounting for 0.02wt% to 0.2wt%; wherein, the recycled pulp is selected from photocopying paper, books for printing toner Paper, printing paper, or combinations thereof, the expanded graphite having the activity of oxidizing the surface with an oxidizing agent to graft epoxy groups (-CH(O)CH-), hydroxyl groups (-OH), carbonyl groups (-C=O), or combinations thereof Functional group modified carbon material, the oxidant is selected from acid or potassium permanganate. 如申請專利範圍第1項所述之紙張回收再製導電紙，其中，該分散劑係選自聚乙烯醇、聚醋酸乙烯酯、羧甲基纖維素或羧乙基纖維素。 The conductive paper made from paper recycling as described in item 1 of the patent application scope, wherein the dispersant is selected from polyvinyl alcohol, polyvinyl acetate, carboxymethyl cellulose or carboxyethyl cellulose. 如申請專利範圍第1項所述之紙張回收再製導電紙，其中，以導電紙總重量百分比(wt%)計算，該界面活性劑包括：第一界面活性劑，係陰離子界面活性劑，其佔0.01wt%至0.1wt%；第二界面活性劑，係非離子界面活性劑，其佔0.01wt%至0.1wt%。 The conductive paper made from paper recycling according to item 1 of the patent application scope, wherein, calculated on the basis of the total weight percentage (wt%) of the conductive paper, the surfactant includes: a first surfactant, which is an anionic surfactant, which accounts for 0.01wt% to 0.1wt%; the second surfactant is a nonionic surfactant, which accounts for 0.01wt% to 0.1wt%. 一種紙張回收再製導電紙之製法，該製法步驟包括：取材步驟：提供如申請專利範圍第1至3中任一項所述之導電紙之組成成分及配比；濕法造紙步驟：將前述導電紙之組成成分按配比混合後，採用濕法造紙技術製成導電紙。 A method for producing conductive paper from paper recycling, the production method steps include: a material sampling step: providing the composition and proportion of the conductive paper described in any one of the first to third patent application scopes; wet papermaking step: mixing the aforementioned conductive paper After the components of the paper are mixed according to the proportions, the conductive paper is made by wet papermaking technology. 如申請專利範圍第4項所述之紙張回收再製導電紙之製法，其中，前述導電紙之組成成分係於室溫下加入水中攪拌混合，該水的體積為所有材料的2至3倍。 According to the method for producing conductive paper from paper recycling as described in item 4 of the scope of the patent application, the components of the conductive paper are added to water at room temperature and stirred and mixed, and the volume of the water is 2 to 3 times that of all the materials. 如申請專利範圍第5項所述之紙張回收再製導電紙之製法，其中，前述導電紙之組成成分係於每分鐘80至120轉之攪拌速度持續攪拌5至10分鐘，以獲得混合均勻的複合紙漿。 The method for producing conductive paper from paper recycling as described in item 5 of the scope of the patent application, wherein the components of the conductive paper are continuously stirred for 5 to 10 minutes at a stirring speed of 80 to 120 revolutions per minute to obtain a uniformly mixed composite pulp. 如申請專利範圍第6項所述之紙張回收再製導電紙之製法，其中，該複合紙漿倒入篩網至均勻瀝乾水分後，取下含水紙張；該含水紙張經熱壓機壓平後再烘乾，製得該導電紙。 The method for producing conductive paper from paper recycling as described in item 6 of the patent application scope, wherein the composite pulp is poured into a screen to drain the water evenly, and then the water-containing paper is removed; the water-containing paper is flattened by a hot press and then After drying, the conductive paper was prepared.
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* Cited by examiner, † Cited by third party
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CN102575423A (en) * 2009-10-26 2012-07-11 巴斯夫欧洲公司 Method for recycling paper products glued and/or coated with biodegradable polymers
TW201602440A (en) * 2014-07-03 2016-01-16 Peng-Yi Guo Paper production method using recycled article as material
CN106219525A (en) * 2016-07-11 2016-12-14 武汉大学 A kind of preparation method of expanded graphite paper
CN106495696A (en) * 2016-10-24 2017-03-15 黑龙江奥星能源科技有限公司 Graphite cake, the leftover bits recoverying and utilizing method of paper
CN110373954A (en) * 2019-07-22 2019-10-25 陕西科技大学 It is a kind of to suppress extraordinary conductive paper waterproof paper and preparation method thereof using polysaccharide fibre thin layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102575423A (en) * 2009-10-26 2012-07-11 巴斯夫欧洲公司 Method for recycling paper products glued and/or coated with biodegradable polymers
TW201602440A (en) * 2014-07-03 2016-01-16 Peng-Yi Guo Paper production method using recycled article as material
CN106219525A (en) * 2016-07-11 2016-12-14 武汉大学 A kind of preparation method of expanded graphite paper
CN106495696A (en) * 2016-10-24 2017-03-15 黑龙江奥星能源科技有限公司 Graphite cake, the leftover bits recoverying and utilizing method of paper
CN110373954A (en) * 2019-07-22 2019-10-25 陕西科技大学 It is a kind of to suppress extraordinary conductive paper waterproof paper and preparation method thereof using polysaccharide fibre thin layer

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