JPS6321713A - Manufacture of transparent conductive film - Google Patents
Manufacture of transparent conductive filmInfo
- Publication number
- JPS6321713A JPS6321713A JP61165163A JP16516386A JPS6321713A JP S6321713 A JPS6321713 A JP S6321713A JP 61165163 A JP61165163 A JP 61165163A JP 16516386 A JP16516386 A JP 16516386A JP S6321713 A JPS6321713 A JP S6321713A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- vapor
- gas
- pyrrole
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 53
- 239000012159 carrier gas Substances 0.000 claims description 14
- 229920000128 polypyrrole Polymers 0.000 claims description 12
- 239000012808 vapor phase Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- 229910001882 dioxygen Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000012685 gas phase polymerization Methods 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 101150095688 maf gene Proteins 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
「産業上の利用分野」
この発明は、気相重合法による透明導電性フィルムの製
造方法に係り、特に透明性や導電性の向上を図ることの
できる透明導電性フィルムの製造方法に関する。Detailed Description of the Invention "Industrial Application Field" The present invention relates to a method for producing a transparent conductive film using a gas phase polymerization method, and in particular to a method for producing a transparent conductive film that can improve transparency and conductivity. Relating to a manufacturing method.
１−従来技術とその問題点」
透明導電性フィルムを製造する方法として、例えばピロ
ールを気相重合法により透明な絶縁フィルム上にポリピ
ロールからなる透明導電層を形成する方法（高分子可能
性講座、講演要旨束５ｇ＜１９８５〉）が提案されてい
る。1-Prior art and its problems" As a method of manufacturing a transparent conductive film, for example, a method of forming a transparent conductive layer made of polypyrrole on a transparent insulating film by vapor phase polymerization of pyrrole (Polymer Possibility Course, A collection of lecture abstracts 5g <1985>) has been proposed.
この方法は、例えばポリエチレンテレフタレート（ＰＥ
Ｔ）などからなる透明絶縁フィルムを基板として、この
フィルム上にＦｅＣＬなどの重合開始剤（酸化剤）を含
む透明性のポリビニルアルコール（ＰＶＡ）層を設け、
次いてこのＰＶ、Ａ層表面に空気をキャリアガスとして
ピロール蒸気を流して、上記のＰＶＡ層上にピロール蒸
気を気相重合してポリピロールからなる透明導電層を形
成する方法である。このような方法によれば、非常に簡
便にかつ安価に透明導電性フィルムを製造できることか
ら、多用される傾向にある。This method uses, for example, polyethylene terephthalate (PE
A transparent insulating film made of T) or the like is used as a substrate, and a transparent polyvinyl alcohol (PVA) layer containing a polymerization initiator (oxidizing agent) such as FeCL is provided on this film,
Next, pyrrole vapor is flowed over the surface of the PV layer A using air as a carrier gas, and the pyrrole vapor is vapor-phase polymerized on the PVA layer to form a transparent conductive layer made of polypyrrole. According to such a method, a transparent conductive film can be produced very easily and inexpensively, and therefore it tends to be used frequently.
ところが、このような方法にあっては、良好な透明性や
導電性を有し、かつ実用に供することのできる透明導電
性フィルムを得ることができない不都合があった。However, such a method has the disadvantage that it is not possible to obtain a transparent conductive film that has good transparency and conductivity and can be put to practical use.
「問題点を解決するための手段！・
そこで、発明者らは、上記の事情に鑑み、鋭意検討を重
ねた結果、従来の方法において、ピロール蒸気のキャリ
アガスとして用いた空気中の酸素ガスが、ピロール蒸気
の気相重合を阻害し、最終的に得られる透明導電性フィ
ルムの導電性や透明性を大きく損なうことを見出だした
。すなわち、この発明の特徴は、気相１合に用いら几る
ピロール蒸気を不活性ガスでキャリアしてピロール蒸気
を絶縁フィルム上に流し、この絶縁フィルム上にピロー
ル蒸気を気相重合してポリピロールからなる透明導電層
を形成することにある。``Means for solving the problem!- Therefore, in view of the above circumstances, the inventors have made extensive studies and found that in the conventional method, oxygen gas in the air used as a carrier gas for pyrrole vapor is It was discovered that the vapor phase polymerization of pyrrole vapor is inhibited, and the conductivity and transparency of the finally obtained transparent conductive film are greatly impaired. The purpose is to carry the cooling pyrrole vapor with an inert gas, to flow the pyrrole vapor onto an insulating film, and to form a transparent conductive layer made of polypyrrole on the insulating film by vapor phase polymerization of the pyrrole vapor.
以下、図面を参照してこの発明の詳細な説明する。Hereinafter, the present invention will be described in detail with reference to the drawings.
図面は、この発明の透明導電性フィルムの製造方法によ
って得られた透明導電性フィルムの一例を示すものであ
る。まず、図中符号１は、透明でかつ電気絶縁性を有す
る絶縁フィルムであって、この絶縁フィルムｌを形成す
る材料と、しては、例えば前述したＰＥＴやポリイミド
など絶縁性に優れた合成樹脂ｈ（好適に用いられるが、
これに：限定されるもので１よｔい。The drawings show an example of a transparent conductive film obtained by the method for manufacturing a transparent conductive film of the present invention. First, reference numeral 1 in the figure is an insulating film that is transparent and has electrical insulation properties, and the material for forming this insulating film 1 is, for example, a synthetic resin with excellent insulating properties such as the aforementioned PET or polyimide. h (preferably used,
This: It's limited and it's better than 1.
次いで、この絶縁フィルム１上に、酸化剤を添加しｆこ
合成樹脂混合物を塗布し、硬化させて透明樹脂層２を積
層する。ここで、上記の酸化剤としては、後述のピロー
ルの気相重合の開始剤として働くものが選ばれ、具体的
には、塩化第二鉄（ＦｅＣ（！３）、ベルオクソニ硫酸
アンモニウムｃＪ Ｈ４）２８２０８などが好適に用い
られる。また、上記の合成樹脂には、透明性を有しかつ
後述のポリピロールからなる透明導電層の特性を安定化
させるものが選ばれ、具体的には水溶性のポリビニルア
ルコール（ＰＶＡ）が好適に用いられる。そして、上記
の合成樹脂に対する酸化剤の添加量は、合成樹脂や重合
開始剤の種類、後述のピロール蒸気雰囲気、ポリピロー
ル導電層の膜厚などに応じて適宜決められるが、ＰＶＡ
と塩化第二鉄の場合、７・３〜９：１程度の範囲とされ
、好ましくは８：２程度とされる。Next, on this insulating film 1, an oxidizing agent is added and a synthetic resin mixture is applied and cured to laminate the transparent resin layer 2. Here, as the above-mentioned oxidizing agent, one is selected that acts as an initiator for the gas phase polymerization of pyrrole, which will be described later. is preferably used. In addition, as the above-mentioned synthetic resin, one is selected that has transparency and stabilizes the characteristics of the transparent conductive layer made of polypyrrole, which will be described later. Specifically, water-soluble polyvinyl alcohol (PVA) is preferably used. It will be done. The amount of the oxidizing agent added to the above synthetic resin is determined as appropriate depending on the type of synthetic resin and polymerization initiator, the pyrrole vapor atmosphere described below, the thickness of the polypyrrole conductive layer, etc.
and ferric chloride, the ratio is about 7.3 to 9:1, preferably about 8:2.
次に、透明樹脂層２の表面に、不活性ガスをキャリアガ
スとしてピロール蒸気を送り、透明樹脂層２上に、ピロ
ール蒸気を気相重合してポリピロール導電層３を積層し
て、目的の透明導電性フィルム４を得る。ここで、この
透明導電性フィルム４の導電性や透明性を良好にするた
めには、上記のキャリアガス中の酸素ガスの気相重合温
度におけるガス分率が空気中の酸素ガス分率の２０％未
満とされ、好ましくは酸素ガスが皆無であることが望ま
しい。この酸素ガス分率が２０％以上では、酸素ガスが
多過ぎてピロール蒸気の気相重合が阻害されて、良好な
導電性や透明性を有する透明導電性フィルム４が得られ
ない。そして、上記のキャリアガスとして用いられる不
活性ガスとしては、通常のＨｅガス、Ｎｅガス、Ａｒガ
ス、Ｎ２ガスやこれらのガスの混合ガスなどが好適に用
いられる。また、上記のピロール蒸気の気相重合によっ
て得られたポリピロール導電層３の膜厚は、この導電層
３の透明性や得られる透明導電性フィルム４に要求され
る諸特性などに応じて適宜決められる。Next, pyrrole vapor is sent to the surface of the transparent resin layer 2 using an inert gas as a carrier gas, and a polypyrrole conductive layer 3 is laminated on the transparent resin layer 2 by vapor phase polymerization of the pyrrole vapor to obtain the desired transparent A conductive film 4 is obtained. Here, in order to improve the conductivity and transparency of the transparent conductive film 4, it is necessary that the gas fraction of oxygen gas in the carrier gas at the gas phase polymerization temperature be 20% of the oxygen gas fraction in air. %, preferably no oxygen gas at all. If the oxygen gas fraction is 20% or more, there is too much oxygen gas and gas phase polymerization of pyrrole vapor is inhibited, making it impossible to obtain a transparent conductive film 4 having good conductivity and transparency. As the inert gas used as the carrier gas, ordinary He gas, Ne gas, Ar gas, N2 gas, or a mixed gas of these gases is suitably used. Further, the film thickness of the polypyrrole conductive layer 3 obtained by the vapor phase polymerization of the above-mentioned pyrrole vapor is determined as appropriate depending on the transparency of the conductive layer 3 and various properties required of the transparent conductive film 4 obtained. It will be done.
また、上記のポリピロール導電層３には、導電性を高め
るために適当量のドーパントが添加されている。このド
ーパントとしては、塩素イオン（Ｃ１）や四フッ化ホウ
素（ＢＦ、）などが好適に用いられる。Furthermore, an appropriate amount of dopant is added to the polypyrrole conductive layer 3 in order to improve conductivity. As this dopant, chlorine ion (C1), boron tetrafluoride (BF, ), etc. are preferably used.
この方法によれば、ピロール蒸気のキャリアガスとして
不活性ガスを用いるようにしたので、良好な透明性や導
電性を有する透明導電性フィルムを製造することができ
る。According to this method, since an inert gas is used as a carrier gas for pyrrole vapor, a transparent conductive film having good transparency and conductivity can be produced.
以下、実験例を示す。Experimental examples are shown below.
（実験例）
絶縁フィルムとして板厚約１００μ屑程度のＰＥＴ製フ
ィルムを用意した。次いて、このＰＥＴ製フィルム上に
、ＰＶＡと重合開始剤の ＰｅＣｌ２３との混合割合が
８：２とした樹脂混合物を塗布し、硬化せしめて膜厚
約２μ肩程度の透明樹脂層を形成した。(Experimental Example) A PET film with a thickness of approximately 100 μm was prepared as an insulating film. Next, a resin mixture having a mixing ratio of PVA and PeCl23 as a polymerization initiator of 8:2 was applied onto this PET film and cured to form a transparent resin layer with a thickness of approximately 2 μm.
次に、この透明樹脂層表面に、アルゴンガスをキャリア
ガスとしてピロール蒸気を送り、上記のｄ明樹脂層表面
上に、ピロール蒸気を気相重合して膜厚約１μ肩程度の
ポリピロール導電層を形成して目的の透明導電性フィル
ムを作製した。なお、このピロール蒸気の気相重合時の
相対湿度を９０％とした。まｆ二、重合１変を２０°Ｃ
としたものを実施便ｊｌｌ、３．５とし、−１５℃とし
たものを実施例２．４．６とした。そして、これらの実
施例１〜６については第１表に、また比較例１．２につ
いては第２表にそれぞれ、ピロール蒸気のキャリアガス
中○駿素ガス分率を示すとともに、得られた週明１電性
フイルムのｄ過半（可視波長５５０ｎｍに対する光透過
性の割合）や表面電気抵抗値の結果を示した。Next, pyrrole vapor is sent to the surface of this transparent resin layer using argon gas as a carrier gas, and the pyrrole vapor is vapor-phase polymerized to form a polypyrrole conductive layer with a film thickness of about 1 μm on the surface of the d-light resin layer. The desired transparent conductive film was produced. Note that the relative humidity during the gas phase polymerization of this pyrrole vapor was 90%. Maf2, polymerization 1 at 20°C
The temperature at −15° C. was designated as Example 2.4.6. Table 1 shows Examples 1 to 6, and Table 2 shows Comparative Examples 1 and 2, respectively. The results of the d-majority (percentage of light transmittance for visible wavelengths of 550 nm) and surface electrical resistance values of the photovoltaic film are shown.
第１表
第１表から明らかなように、ピロール蒸気のキャリアガ
ス中の酸素ガス分率が２０％未満とした実施例１〜６は
、いずれら光透過率が高くなり、１０２〜１０３オーダ
ー程度まで表面電気抵抗値か低下して導電性が同上して
いることがわかる。Table 1 As is clear from Table 1, in Examples 1 to 6 in which the oxygen gas fraction in the carrier gas of pyrrole vapor was less than 20%, the light transmittance was high, on the order of 102 to 103. It can be seen that the surface electrical resistance value decreased to 100% and the conductivity increased.
第２表
第２表から明らかなように、ピロール蒸気のキャリアガ
ス中の酸素ガス分率が２０％以上とした比較例Ｉおよび
２は、どちらら光透過率が低く、表面電気抵抗値が低下
せず、良好な透過率や導電率を有する透明導電性フィル
ムが得られないことがわかる。Table 2 As is clear from Table 2, both Comparative Examples I and 2, in which the oxygen gas fraction in the carrier gas of pyrrole vapor was 20% or more, had low light transmittance and a decrease in surface electrical resistance. It can be seen that a transparent conductive film having good transmittance and conductivity cannot be obtained without the above.
すなわち、これら第１表および第２表から明らかなよう
に、ピロール蒸気のキャリアガス中の酸素ガス分率が２
０％未満の実施例１〜６は、いずれも酸素ガス分率が２
０％以上の比較例Ｉおよび２に比べて、実用に供するこ
とのできる即度に表面電気抵抗値が小さくかつ光透過率
が高い透明導電性フィルムが得られることがわかる。That is, as is clear from these Tables 1 and 2, the oxygen gas fraction in the carrier gas of pyrrole vapor is 2.
In Examples 1 to 6, the oxygen gas fraction was less than 0%.
It can be seen that compared to Comparative Examples I and 2 in which the film was 0% or more, a transparent conductive film with a small surface electrical resistance value and a high light transmittance that can be put to practical use immediately can be obtained.
「発明の効果」
以上説明したように、この発明は、絶縁フィルム表面に
、キャリアガスとともにピロール蒸気を流し、上記絶縁
フィルム表面上にピロール蒸気を気相重合してポリピロ
ールからなる導電層を形成する透明導電性フィルムの製
造方法において、上記ピロール蒸気のキャリアガスとし
て不活性ガスを用いるようにしたので、優れた透明性お
よび導電性を宵する透明導電性フィルムを製造すること
ができる。"Effects of the Invention" As explained above, the present invention involves flowing pyrrole vapor together with a carrier gas onto the surface of an insulating film, and vapor-phase polymerizing the pyrrole vapor onto the surface of the insulating film to form a conductive layer made of polypyrrole. In the method for producing a transparent conductive film, since an inert gas is used as a carrier gas for the pyrrole vapor, a transparent conductive film having excellent transparency and conductivity can be produced.
図面は、この発明の透明導電性フィルムの製造方法によ
って得られる透明導電性フィルムの一例を示す概略断面
図である。
■・・・絶縁フィルム、２・・透明樹脂層、３・・・ポ
リピロール導電層、４・・透明導電性フィルム。The drawing is a schematic cross-sectional view showing an example of a transparent conductive film obtained by the method for manufacturing a transparent conductive film of the present invention. ■...Insulating film, 2...Transparent resin layer, 3...Polypyrrole conductive layer, 4...Transparent conductive film.
Claims (1)
蒸気を流し、上記絶縁フィルム表面上にピロール蒸気を
気相重合してポリピロールからなる導電層を形成する透
明導電性フィルムの製造方法において、 上記ピロール蒸気のキャリアガスとして不活性ガスを用
いることを特徴とする透明導電性フィルムの製造方法。[Claims] A method for producing a transparent conductive film, which comprises flowing pyrrole vapor together with a carrier gas onto the surface of the insulating film, and vapor-phase polymerizing the pyrrole vapor onto the surface of the insulating film to form a conductive layer made of polypyrrole, A method for producing a transparent conductive film, characterized in that an inert gas is used as a carrier gas for the pyrrole vapor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61165163A JPS6321713A (en) | 1986-07-14 | 1986-07-14 | Manufacture of transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61165163A JPS6321713A (en) | 1986-07-14 | 1986-07-14 | Manufacture of transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6321713A true JPS6321713A (en) | 1988-01-29 |
Family
ID=15807062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61165163A Pending JPS6321713A (en) | 1986-07-14 | 1986-07-14 | Manufacture of transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6321713A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006035475A1 (en) * | 2004-09-27 | 2006-04-06 | Jsr Corporation | Laminated body and manufacturing method thereof |
-
1986
- 1986-07-14 JP JP61165163A patent/JPS6321713A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006035475A1 (en) * | 2004-09-27 | 2006-04-06 | Jsr Corporation | Laminated body and manufacturing method thereof |
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