JP2000160500A - Electroconductive polymer complex paper and its production - Google Patents
Electroconductive polymer complex paper and its productionInfo
- Publication number
- JP2000160500A JP2000160500A JP10342089A JP34208998A JP2000160500A JP 2000160500 A JP2000160500 A JP 2000160500A JP 10342089 A JP10342089 A JP 10342089A JP 34208998 A JP34208998 A JP 34208998A JP 2000160500 A JP2000160500 A JP 2000160500A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- conductive polymer
- pulp
- polymer
- composite paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この出願の発明は、導電性高
分子複合紙とその製造方法に関するものである。さらに
詳しくは、この出願の発明は、紙ベースの電子部材、計
測部材等として有用な、高付加価値紙製品の展開を可能
とする、新しい導電性複合紙とその製造方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive polymer composite paper and a method for producing the same. More specifically, the invention of this application relates to a new conductive composite paper, which is useful as a paper-based electronic member, a measuring member, and the like, and enables the development of high value-added paper products, and a method of manufacturing the same.
【０００２】[0002]
【従来の技術とその課題】従来より、古い歴史を有する
紙製品については、その用途の多様化とともに各種の機
能が付与されたものが開発されてきている。しかしなが
ら、古来からの紙パルプを主として抄造される紙製品に
ついては、たとえば電子・光機能等の先端的な機能が付
与されたものは数が少く、実際的には、技術革新の時代
に即応した高付加価値品の展開はあまり進んでいないの
が実情である。2. Description of the Related Art Conventionally, paper products having an old history have been developed with various functions and various functions. However, for paper products mainly made of paper pulp from ancient times, few of them are provided with advanced functions such as electronic and optical functions, and in reality, they responded quickly to the era of technological innovation. The fact is that the development of high value-added products has not progressed much.
【０００３】そこで、この出願の発明は、以上のような
状況に鑑みて、紙パルプを主とする抄造製品について、
その用途の多様化と高付加価値化を図ることができる、
新しい導電性複合紙を提供することを課題としている。[0003] In view of the above situation, the invention of this application relates to a papermaking product mainly comprising paper pulp.
It is possible to diversify its uses and add value.
It is an object to provide a new conductive composite paper.
【０００４】[0004]
【課題を解決するための手段】この出願の発明は、上記
の課題を解決するものとして、まず第１には、紙パルプ
に導電性高分子が内添されて抄紙されていることを特徴
とする導電性高分子複合紙を提供する。またこの出願
は、第２には、導電性高分子がポリアニリン系高分子、
ポリピロール系高分子、またはポリチオフェン系高分子
である前記複合紙を、第３には、エメラルデインベース
として、紙パルプとの合計量に対して５〜２５重量％の
割合で内添されている複合紙を、第４には、電気伝導度
が１Ｓ／ｃｍ以上である複合紙をも提供する。Means for Solving the Problems According to the invention of the present application, first of all, the invention is characterized in that paper pulp is paper-made by adding a conductive polymer to paper pulp. To provide a conductive polymer composite paper. Also, this application is based on the following problem: the conductive polymer is a polyaniline polymer;
Third, the composite paper, which is a polypyrrole-based polymer or a polythiophene-based polymer, is internally added as an emeraldine base at a ratio of 5 to 25% by weight based on the total amount of the paper pulp. Paper is also provided, fourthly, a composite paper having an electrical conductivity of 1 S / cm or more.
【０００５】そして、この出願の発明は、第５には前記
の第１ないし第４のいずれかの複合紙の製造方法であっ
て、紙パルプにエメラルデインベースの導電性高分子を
内添し、抄紙した後に酸処理することことを特徴とする
導電性高分子複合紙の製造方法を、第６には、紙パルプ
にエメラルデインソルト状態の導電性高分子を内添し、
抄紙することを特徴とする導電性高分子複合紙の製造方
法を提供する。Fifth, the invention of this application is the method for producing a composite paper according to any one of the first to fourth aspects, wherein an emeraldine-based conductive polymer is internally added to the paper pulp. A method for producing a conductive polymer composite paper, which is characterized by performing an acid treatment after papermaking; sixth, internally adding a conductive polymer in an emeraldine salt state to paper pulp;
Provided is a method for producing a conductive polymer composite paper characterized by papermaking.
【０００６】以上のとおりのこの出願の発明の導電性高
分子複合紙は、その製造において、混合抄紙によって安
価に作成できる上に、作成されたものは劇的な電気伝導
度と色調の変化、および水素イオンセンシング機能を有
する等から、たとえば静電防止梱包紙、コンデンサー電
極、酸性度の検出素子等の用途への展開に有用なものと
なる。[0006] As described above, the conductive polymer composite paper of the invention of this application can be produced at low cost by mixed papermaking in the production thereof, and the produced one has a dramatic change in electric conductivity and color tone. In addition, since it has a hydrogen ion sensing function, it is useful for developing applications such as antistatic wrapping paper, condenser electrodes, and acidity detecting elements.
【０００７】[0007]
【発明の実施の形態】この出願の発明の実施の形態につ
いて以下に説明する。まず、この発明の導電性高分子複
合紙については、前記のとおり、紙パルプを主として、
これに導電性高分子が内添されて抄紙されたものである
ことを本質的な特徴としている。Embodiments of the present invention will be described below. First, as described above, the conductive polymer composite paper of the present invention mainly includes paper pulp,
An essential feature is that the paper is made by internally adding a conductive polymer thereto.
【０００８】この場合の紙パルプは、従来より使用され
ているものをはじめとして各種のものであってよい。製
紙用として使用することができる、針葉樹や広葉樹の木
材パルプをはじめ、非木材系のリンターパルプ等であっ
てよく、製造法としての区分では、メカニカルパルプ、
ケミカルパルプ、セミケミカルパルプのうちの各種のも
の、あるいはそれらの混合であってよい。[0008] The paper pulp in this case may be of various types including those conventionally used. It can be used for papermaking, including coniferous and hardwood wood pulp, non-wood linter pulp, and the like.
Various kinds of chemical pulp and semi-chemical pulp, or a mixture thereof may be used.
【０００９】一方、内添される導電性高分子も各種のも
のでよく、たとえば代表例としては、ポリアニリン系高
分子、ポリピロール系高分子、ポリチオフェン系高分子
等が挙げられる。ここで、たとえば、ポリアニリン系高
分子と表現する場合の「系」については、高分子の基本
主鎖構造がポリアニリンであって、これに各種の化学修
飾が行われているもので、導電性を示すことのできる各
種のものが含まれることを意味している。つまり、ポニ
アニリンとその修飾体としての導電性高分子が意味され
ている。他の場合についても同様である。On the other hand, the conductive polymer to be added may be of various types, and typical examples thereof include polyaniline-based polymers, polypyrrole-based polymers, and polythiophene-based polymers. Here, for example, the “system” when expressed as a polyaniline-based polymer is a polymer in which the basic main chain structure of the polymer is polyaniline, which has been subjected to various chemical modifications, and thus has a conductivity. It means that various things that can be shown are included. That is, ponianiline and a conductive polymer as its modified product are meant. The same applies to other cases.
【００１０】これらの導電性高分子は、この発明におい
ては、いわゆる脱ドープされている非酸化状態のエメラ
ルデインベースとして、あるいは酸化状態にあるエメラ
ルデインソルトとして添加混合することができる。たと
えばポニアニリンのエメラルデインベース状態のものを
使用する場合について説明すると、エメラルデインベー
スとは、前記のとおり、脱ドープした状態のポニアニリ
ンをさす。このため、この状態では導電性は生じないが
塩酸などで酸処理してｐＨを下げ、いわゆるドーピング
処理を行うことにより、酸化状態にするとエメラルデイ
ンソルトという導電性状態に変化する。紙に内添したポ
リアニリンも同様に絶縁性状態から導電性状態に変化す
る。それとともに色が深い青からエメラルドグリーンに
変化する。この状態でこの導電性高分子複合紙の導電性
が生ずる。また酸化状態のエメラルデインソルトと紙パ
ルプより、最初から導電性を有する状態で抄紙すること
も可能であり、酸による上記のドーピング処理を行うこ
と無しに導電性の紙が作製できる。In the present invention, these conductive polymers can be added and mixed as a so-called undoped non-oxidized emeraldine base or as an oxidized emeraldine salt. For example, a case where ponianiline in an emeraldine base state is used will be described. The emeraldine base refers to de-doped ponianiline as described above. For this reason, in this state, conductivity does not occur, but by performing an acid treatment with hydrochloric acid or the like to lower the pH and performing a so-called doping treatment, when the state is oxidized, the state changes to a conductive state called emeraldine salt. Similarly, polyaniline internally added to paper changes from an insulating state to a conductive state. At the same time, the color changes from deep blue to emerald green. In this state, conductivity of the conductive polymer composite paper occurs. It is also possible to make paper from an oxidized state of emeraldine salt and paper pulp in a state having conductivity from the beginning, and a conductive paper can be produced without performing the above doping treatment with an acid.
【００１１】いずれの場合も、複合紙は紙パルプと混合
抄紙することで作製できるので極めて製法が容易であ
る。電気伝導度や色の変化は内添するポリアニリンの量
を変化させることにより調節できる。また、前記例示の
他の導電性高分子であるポリピロールやポリチオフェン
でも同様な複合紙を作製でき、同様な性能を得ることが
できる。In any case, since the composite paper can be produced by mixing paper pulp and making paper, the production method is extremely easy. The change in electric conductivity and color can be adjusted by changing the amount of polyaniline added. Further, the same composite paper can be produced with other conductive polymers such as polypyrrole and polythiophene, and the same performance can be obtained.
【００１２】なお、エメラルデインソルトの状態（導電
性状態）にしてからアンモニアなどのアルカリに、気相
ないしは液相で接触させると絶縁体に変化することか
ら、この発明の導電性複合紙はアルカリセンサーとして
も用いることができる。紙パルプへの導電性高分子の配
合割合については特に限定はなく、使用する導電性高分
子の種類、所望の電気伝導度のレベル等により適宜に調
整される。一般的には、エメラルデインベースとして、
紙パルプとの合計量に対して１〜４０重量％、さらには
５〜２５重量％程度が適当な目安となる。The conductive composite paper of the present invention is converted into an insulator when it is brought into an emeraldine salt state (conductive state) and then brought into contact with an alkali such as ammonia in a gas phase or a liquid phase. It can also be used as a sensor. The mixing ratio of the conductive polymer to the paper pulp is not particularly limited, and is appropriately adjusted according to the type of the conductive polymer used, the desired level of electric conductivity, and the like. Generally, as an emeraldine base,
A suitable standard is 1 to 40% by weight, more preferably about 5 to 25% by weight, based on the total amount of the paper pulp.
【００１３】そして、この発明においては、より具体的
には、電気伝導度が１Ｓ／ｃｍ以上である導電性高分子
複合紙が提供されることになる。もちろん、この発明の
複合紙においては、所望により他の配合成分が適宜に添
加されてもよいことは言うまでもない。また、抄紙につ
いては、従来同様の方法、そして装置が適宜に使用でき
ることになる。According to the present invention, more specifically, a conductive polymer composite paper having an electric conductivity of 1 S / cm or more is provided. Of course, it goes without saying that in the composite paper of the present invention, other components may be appropriately added as desired. For papermaking, the same method and apparatus can be used as appropriate.
【００１４】また、エメラルデインベースで内添した後
の酸処理には、塩酸が最も簡便に使用できるが、これに
限定されることはなく、ｐＨを下げ、酸化状態とするこ
とのできる鉱酸あるいは有機酸のうちの各種のものであ
ってよい。塩酸を用いる場合には、常温、常圧で、空気
中で蒸発するＨＣｌによるドープとして行うことができ
る。たとえば塩酸以外には、硫酸、ギ酸等も例示され
る。また、酸処理は導電性を賦活するためのドープとし
て行われるものであるが、この賦活のためのドープは、
ヨウ素やヒ素（ＡｓＦ5 等による）で行ってもよい。In addition, hydrochloric acid can be used most easily for acid treatment after internal addition based on emeraldine, but is not limited to this. Mineral acid capable of lowering pH and bringing it into an oxidized state can be used. Alternatively, various kinds of organic acids may be used. In the case of using hydrochloric acid, the doping can be performed at room temperature and normal pressure by HCl evaporating in the air. For example, in addition to hydrochloric acid, sulfuric acid, formic acid and the like are also exemplified. Further, the acid treatment is performed as a dope for activating conductivity, the dope for this activation,
It may be performed with iodine or arsenic (by AsF 5 or the like).
【００１５】そこで以下に実施例を示し、さらに詳しく
この発明について説明する。もちろん、この発明は以下
の例に限定されるものではない。The present invention will be described in more detail with reference to the following examples. Of course, the present invention is not limited to the following examples.
【００１６】[0016]
【実施例】紙パルプ：ＮＢＫＰ（針葉樹パルプ）／ＬＢ
ＫＰ（広葉樹パルプ）（重量比）＝７０／３０にポリア
ニリンエメラルデインベースを１３．５重量％内添し、
抄紙装置により複合紙を作製した。この場合、坪量は１
９５ｇ／ｍ2 であった。これを常温、常圧で塩酸蒸気に
さらすことにより最高１．９５Ｓ／ｃｍの電気伝導度が
発生することが確認された。添付の図１に示したよう
に、塩酸蒸気にさらす前は絶縁体の領域であったが塩酸
蒸気に接触させるとほぼ同時に導体の領域に電気伝導度
が向上した。その上昇率は一億倍であった。[Example] Paper pulp: NBKP (softwood pulp) / LB
13.5% by weight of polyaniline emeraldine base was internally added to KP (hardwood pulp) (weight ratio) = 70/30,
Composite paper was produced by a papermaking machine. In this case, the grammage is 1
It was 95 g / m 2 . It was confirmed that an electric conductivity of up to 1.95 S / cm was generated by exposing this to hydrochloric acid vapor at normal temperature and normal pressure. As shown in the attached FIG. 1, before the exposure to the hydrochloric acid vapor, the region was the insulator, but almost immediately upon contact with the hydrochloric acid vapor, the electric conductivity was improved in the conductor region. The rate of increase was 100 million times.
【００１７】[0017]
【発明の効果】以上詳しく説明したとおり、この出願の
発明によって、混合抄紙という簡単な手段で、紙パルプ
を主とする導電性複合紙を提供することができる。この
複合紙は、製法が容易であるだけでなく、電気伝導度や
色の変化は内添するポリアニリンの量を変化させること
により調節でき、また、水素イオンセンシング機能を有
し、色および電気伝導度の劇的な変化から酸性度のチェ
ック、および静電防止梱包剤等に用いることができる。
さらにはアルカリセンサーとしても使用することができ
る。またポリアニリン等の導電性高分子の単体にはな
い、紙特有の柔らかさ、安価性、しなやかさ、強靱性を
有するため、製紙業界の電子分野における新たな分野の
開拓に繋がる。As described above in detail, according to the invention of this application, it is possible to provide a conductive composite paper mainly composed of paper pulp by a simple means called mixed papermaking. Not only is this composite paper easy to manufacture, but it can be adjusted by changing the amount of polyaniline to be added, and it has a hydrogen ion sensing function. It can be used for acidity check, antistatic packing, etc. from dramatic change in degree.
Furthermore, it can be used as an alkaline sensor. In addition, since it has the softness, low cost, flexibility, and toughness unique to paper, which is not found in simple conductive polymers such as polyaniline, it leads to the development of new fields in the electronics field of the papermaking industry.
【図１】エメラルデインベースのポリアニリンの内添の
紙についての塩酸処理にともなう電気伝導度の変化を例
示した図である。BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram illustrating a change in electric conductivity of emeraldine-based polyaniline internally treated paper with hydrochloric acid treatment.
Claims (6)
紙されていることを特徴とする導電性高分子複合紙。1. A conductive polymer composite paper, wherein a conductive polymer is internally added to paper pulp to make paper.
ポリピロール系高分子、またはポリチオフェン系高分子
である請求項１の複合紙。2. The conductive polymer is a polyaniline polymer,
The composite paper according to claim 1, which is a polypyrrole-based polymer or a polythiophene-based polymer.
との合計量に対して５〜２５重量％の割合で内添されて
いる請求項１または２の複合紙。3. The composite paper according to claim 1, wherein the emeraldine base is internally added at a ratio of 5 to 25% by weight based on the total amount of the paper pulp.
項１ないし３のいずれかの複合紙。4. The composite paper according to claim 1, which has an electric conductivity of 1 S / cm or more.
製造方法であって、紙パルプにエメラルデインベースの
導電性高分子を内添し、抄紙した後に酸処理することを
特徴とする導電性高分子複合紙の製造方法。5. The method for producing composite paper according to claim 1, wherein an emeraldine-based conductive polymer is internally added to the paper pulp, and the paper is subjected to acid treatment after papermaking. A method for producing a conductive polymer composite paper.
製造方法であって、紙パルプにエメラルデインソルト状
態の導電性高分子を内添し、抄紙することを特徴とする
導電性高分子複合紙の製造方法。6. The method for producing composite paper according to claim 1, wherein a conductive polymer in an emeraldine salt state is internally added to the paper pulp, and the paper is made. Manufacturing method of molecular composite paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34208998A JP3705709B2 (en) | 1998-12-01 | 1998-12-01 | Method for producing conductive polymer composite paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34208998A JP3705709B2 (en) | 1998-12-01 | 1998-12-01 | Method for producing conductive polymer composite paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000160500A true JP2000160500A (en) | 2000-06-13 |
| JP3705709B2 JP3705709B2 (en) | 2005-10-12 |
Family
ID=18351081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34208998A Expired - Fee Related JP3705709B2 (en) | 1998-12-01 | 1998-12-01 | Method for producing conductive polymer composite paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3705709B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004523670A (en) * | 2001-03-05 | 2004-08-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conductive para-aramid pulp |
| WO2011118407A1 (en) | 2010-03-25 | 2011-09-29 | 凸版印刷株式会社 | Conductive film and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5271558B2 (en) * | 2008-02-06 | 2013-08-21 | 国立大学法人 筑波大学 | Method for producing pulp / polyaniline composite |
-
1998
- 1998-12-01 JP JP34208998A patent/JP3705709B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004523670A (en) * | 2001-03-05 | 2004-08-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conductive para-aramid pulp |
| WO2011118407A1 (en) | 2010-03-25 | 2011-09-29 | 凸版印刷株式会社 | Conductive film and manufacturing method thereof |
| US9243073B2 (en) | 2010-03-25 | 2016-01-26 | Toppan Printing Co., Ltd. | Conductive film and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3705709B2 (en) | 2005-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | High‐fidelity bioelectronic muscular actuator based on graphene‐mediated and TEMPO‐oxidized bacterial cellulose | |
| You et al. | Crab chitin‐based 2D soft nanomaterials for fully biobased electric devices | |
| Wan et al. | Formation mechanism of polyaniline microtubules synthesized by a template‐free method | |
| Jalili et al. | One‐step wet‐spinning process of poly (3, 4‐ethylenedioxythiophene): poly (styrenesulfonate) fibers and the origin of higher electrical conductivity | |
| JP4519679B2 (en) | Conductive polymer composition and solid electrolytic capacitor using the same | |
| JP5660595B2 (en) | Conductive paper and manufacturing method thereof, conductive cellulose composition and manufacturing method thereof, article, electronic device | |
| Long et al. | Electrical conductivity of an individual polyaniline nanotube synthesized by a self‐assembly method | |
| Latypova et al. | Synthesis and physicochemical properties of poly [2‐(2‐chloro‐1‐methylbut‐2‐en‐1‐yl) aniline] obtained with various dopants | |
| JP6580436B2 (en) | Conductive polymer composition and use thereof | |
| TW200949878A (en) | Capacitor and production method thereof | |
| Kar et al. | Electrical and dielectric properties of polyaniline doped with carboxyl‐functionalized multiwalled carbon nanotube | |
| JPH01503242A (en) | conductive plastic composite | |
| Ruiz et al. | Improving the processability of conductive polymers: The case of polyaniline | |
| US4519873A (en) | Process for producing fibrous sheet | |
| Gomez et al. | Analysis of crosslinking in polypyrrole particles synthesized by plasma | |
| Richardson et al. | Electronic properties of intrinsically conducting polymer-cellulose based composites | |
| JP2000160500A (en) | Electroconductive polymer complex paper and its production | |
| Zhang et al. | Synthesis of conductive polyaniline nanofibers in one step by protonic acid and iodine doping | |
| Dubey et al. | Surfactant assisted synthesis of pH responsive polyaniline-cellulose biocomposite for sensor applications | |
| US11515058B2 (en) | Conductive film, production method thereof, and display apparatus | |
| Oh et al. | Electrical property and stability of electrochemically synthesized polypyrrole films | |
| Minisy et al. | Frozen‐State Polymerization as a Tool in Conductivity Enhancement of Polypyrrole | |
| Aggas et al. | Chemiresistive and Chemicapacitive Devices Formed via Morphology Control of Electroconductive Bio‐nanocomposites | |
| Branzoi et al. | Fabrication and characterisation of conducting composite films based on conducting polymers and functionalised carbon nanotubes | |
| Corona-Rivera et al. | Morphology and conductivity tuning of polyaniline using short-chain alcohols by heterophase polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20031210 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20041130 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041207 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050202 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050412 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050608 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050705 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050726 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |