JPS6319045B2 - - Google Patents
Info
- Publication number
- JPS6319045B2 JPS6319045B2 JP13173881A JP13173881A JPS6319045B2 JP S6319045 B2 JPS6319045 B2 JP S6319045B2 JP 13173881 A JP13173881 A JP 13173881A JP 13173881 A JP13173881 A JP 13173881A JP S6319045 B2 JPS6319045 B2 JP S6319045B2
- Authority
- JP
- Japan
- Prior art keywords
- paste
- transparent conductive
- film
- conductive film
- forming
- 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.)
- Expired
Links
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- -1 phenylazo Chemical group 0.000 claims description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 238000007650 screen-printing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000000020 Nitrocellulose Substances 0.000 description 6
- 229920001220 nitrocellulos Polymers 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 229940007550 benzyl acetate Drugs 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Conductive Materials (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、スクリーン印刷と焼成により、ガラ
ス、セラミツク等の絶縁基板上に、基板との密着
性が優れた金属酸化物よりなる透明導電性被膜を
所望の形状に形成するための透明導電性被膜形成
用ペーストに関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a method of producing a transparent conductive material made of a metal oxide with excellent adhesion to the substrate on an insulating substrate such as glass or ceramic by screen printing and baking. The present invention relates to a paste for forming a transparent conductive film for forming a film into a desired shape.
ガラス、セラミツク等の絶縁基板上に形成した
In，Sn，Sb，Cd等の酸化物被膜は、透過率が高
く良好な導電性を示すことはよく知られており半
導体素子、液晶表示装置等に使用したり、或は、
窓ガラス等の氷結防止用導電膜として利用された
りして近年益々その応用範囲が拡大してきてい
る。この様な金属酸化物透明導電性被膜の形成方
法としては、化学スプレー法、真空蒸着法、スク
リーン印刷法等がある。
Formed on an insulating substrate such as glass or ceramic
It is well known that oxide films such as In, Sn, Sb, and Cd have high transmittance and good conductivity, and are used in semiconductor devices, liquid crystal display devices, etc.
In recent years, its range of applications has been expanding, including as a conductive film for preventing icing on window glass and the like. Methods for forming such a metal oxide transparent conductive film include chemical spraying, vacuum evaporation, and screen printing.
化学スプレー法は、比較的大面積の形状の被膜
を得るには、有利であるが、微細で複雑な形状の
ものを得るには、エツチング等の余分な工程が必
要となり経済的ではない。真空蒸着法は、最近マ
スク蒸着法が発達し、エツチング処理は必要でな
くなつたが、バツチ式である為、量産向きとは言
えない。スクリーン印刷法では、係る問題がなく
目的形状のものを、印刷焼成により得ることがで
き、エツチング処理にともなう廃液処理の必要も
ないという利点がある。 The chemical spray method is advantageous for obtaining a film with a relatively large area, but is not economical because it requires extra steps such as etching to obtain a film with a fine and complex shape. The vacuum evaporation method has recently developed into a mask evaporation method and no longer requires etching, but since it is a batch method, it cannot be said to be suitable for mass production. The screen printing method has the advantage that it does not have such problems and can obtain the desired shape by printing and firing, and there is no need for waste liquid treatment accompanying the etching process.
しかし、従来のスクリーン印刷法では、透明導
電性被膜形成用ペースト自体の安定性や印刷性が
良くないため、スクリーン印刷時の作業性も悪く
且つ、形成された被膜の抵抗値のバラツキもあつ
たので歩留も低いという欠点を持つていた。
However, in the conventional screen printing method, the stability and printability of the paste itself for forming a transparent conductive film are not good, resulting in poor workability during screen printing and variations in the resistance value of the formed film. Therefore, it had the disadvantage of low yield.
従来、この種のペーストにおいては、オクチル
酸インジウム（（C7H13CO2）3In）等のイオン結合
の強い有機酸インジウムを主成分として用いてい
たが、有機酸インジウムは加水分解し易く、又、
ペーストとなした場合、ペーストのゲル化を促進
する等、比較的容易に化学変化するという欠点を
持つていた為、ペースト自体の寿命を短かくし、
スクリーン印刷時の作業性を悪くする原因となつ
ていた。 Conventionally, this type of paste has used indium organic acids with strong ionic bonds, such as indium octylate ((C 7 H 13 CO 2 ) 3 In), as the main ingredient, but indium organic acids are easily hydrolyzed. ,or,
When made into a paste, it had the disadvantage of being relatively easily chemically changed, such as promoting gelation of the paste, which shortened the lifespan of the paste itself.
This was a cause of poor workability during screen printing.
又、バインダーにエチルセルローズを用いてい
たが、その熱安定性（500℃で完全燃焼しないこ
ともある）の故に、比較的高抵抗で被膜強度の弱
い被膜しか得られなかつた。本発明者等は、これ
らの欠点をなくす為、前出願（特公昭62―17324
号）に示す如く、焼成により金属酸化物被膜を与
える化合物として、例えば、アセチルアセトン
（Hacac）の配位したトリスアセチルアセトナー
トインジウム（）（In（acac）3）等の有機インジ
ウム錯体を使用したり、抵抗値調整用スズ化合物
として、例えば、ジメチルスズアセトープ
（（CH3）2Sn（acac）2）等の有機スズ錯体を用いて
ペーストの安定性を高め好結果を得ている。更
に、粘性剤として使用するセルローズ化合物に、
ニトロセルローズを用いることで、密着強度大
で、低抵抗な被膜が得られることをつきとめてい
る。 Furthermore, although ethyl cellulose was used as a binder, due to its thermal stability (it may not burn completely at 500°C), only a film with relatively high resistance and low film strength could be obtained. In order to eliminate these drawbacks, the present inventors have filed a previous application (Japanese Patent Publication No. 62-17324).
As shown in No. 1), for example, an organic indium complex such as trisacetylacetonatoindium (In(acac) 3 ) coordinated with acetylacetone (Hacac) is used as a compound that forms a metal oxide film by firing. For example, organic tin complexes such as dimethyltin acetope ((CH 3 ) 2 Sn(acac) 2 ) have been used as tin compounds for adjusting the resistance value to improve the stability of the paste and good results have been obtained. Furthermore, cellulose compounds used as viscosity agents,
It has been found that by using nitrocellulose, a film with high adhesion strength and low resistance can be obtained.
しかし、ニトロセルローズを用いた場合、エチ
ルセルローズを用いた場合と比較して、ペースト
自体の寿命が短く、スクリーン印刷時の作業性も
悪いという欠点を持つていた。そこで本発明者ら
は、前出願で、脱酸処理したニトロセルローズを
用いることで特性改善がなされることを見出した
が、スクリーン印刷時にペーストの粘度上昇や、
にじみがあり、作業性がまだ十分とは言えなかつ
た。 However, when nitrocellulose is used, the life of the paste itself is shorter than when ethylcellulose is used, and the workability during screen printing is also poor. Therefore, in a previous application, the present inventors found that the characteristics were improved by using deoxidized nitrocellulose, but the viscosity of the paste increased during screen printing,
There was some smearing, and the workability was still not satisfactory.
本発明は、叙上の欠点を解消し、ペースト寿命
の長い、印刷作業性の良い、かつ従来通りの被膜
特性、すなわち低抵抗で透明度及び密着強度の良
好さを与える透明導電性被膜形成用ペーストを提
供する目的でなされたものである。 The present invention solves the above-mentioned drawbacks, and provides a paste for forming a transparent conductive film that has a long paste life, good printing workability, and has the same film characteristics as before, namely, low resistance, good transparency, and adhesion strength. It was made for the purpose of providing.
本発明は前述の目的を達成するため、焼成によ
つて透明導電性金属酸化物となる有機金属化合物
と、有機溶剤と、粘性剤とを含有する透明導電性
被膜形成用ペーストを対象とするものである。
In order to achieve the above-mentioned object, the present invention is directed to a paste for forming a transparent conductive film containing an organic metal compound that becomes a transparent conductive metal oxide upon firing, an organic solvent, and a viscous agent. It is.
そして、このペースト組成物に、500℃で残渣
がほとんどなく、分子構造中に金属原子やＦ，
Cl，Ｓなどを含まない下記の分子構造式を有する
1.フエニルアゾ―2.ナフトールを添加したことを
特徴とするものである。 This paste composition has almost no residue at 500℃ and has metal atoms, F,
It has the following molecular structure that does not contain Cl, S, etc.
It is characterized by the addition of 1. Phenylazo and 2. Naphthol.
分子構造式
〔実施例〕
即ち、ニトロセルローズを用いたペーストの寿
命が短く、スクリーン印刷時にも、印刷シヨツト
数が多くなるにつれペーストの粘度が高くなると
共に、にじみも激しくなるなどの作業性が悪くな
るという点に注目し、ペーストに油溶性有機色素
の１つである1.フエニルアゾ―2.ナフトール（例
えば和光純薬社製 商品名スダン）を添加する
ことにより、スクリーン印刷性を著しく改善する
ことができた。 molecular structure formula [Example] That is, the life of the paste using nitrocellulose is short, and even during screen printing, as the number of printing shots increases, the viscosity of the paste increases and the smearing becomes more severe, resulting in poor workability. By focusing on this, we were able to significantly improve screen printability by adding 1. Phenylazo-2. Naphthol (for example, Wako Pure Chemical Industries, Ltd., product name Sudan), which is an oil-soluble organic pigment, to the paste. .
ペースト化に必要な有機溶媒としては、ベンジ
ルアルコール、ジプロピレングリコール、などの
高沸点アルコール類、ベンジルアセテート、カル
ビトールアセテート等の高沸点エステル類、ブチ
ルセロソルブ等の高沸点エーテル類などの高沸点
有機溶媒が適用できる。 Organic solvents required for pasting include high-boiling point alcohols such as benzyl alcohol and dipropylene glycol, high-boiling point esters such as benzyl acetate and carbitol acetate, and high-boiling point organic solvents such as high-boiling point ethers such as butyl cellosolve. is applicable.
以下、実施例をもとに、更に詳しく本発明を説
明する。 Hereinafter, the present invention will be explained in more detail based on Examples.
実施例 １
トリスアセチルアセトナートインジウム（）
2.69重量部とジメチルスズアセトープ0.31重量部
を正確に秤量し、次にブチルカルビトール32.8重
量部とブチルセロソルブ16.4重量部とベンジルア
セテート16.4重量部とジブチルカルビトール16.4
重量部の各溶媒を添加し、120〜150℃で約３時間
加熱濃縮する。濃縮が終了した後、常温までに冷
却し、油溶性有機色素として、和光純薬社製商品
名スダン0.2重量部を混合し、数分間撹拌後、
ニトロセルローズ15.8重量部を混合し、撹拌機で
８時間撹拌して、ニトロセルローズを完全に溶解
させて、透明導電性被膜形成用ペーストを得た。Example 1 Trisacetylacetonatoindium ()
Accurately weigh 2.69 parts by weight and 0.31 parts by weight of dimethyltin acetope, then 32.8 parts by weight of butyl carbitol, 16.4 parts by weight of butyl cellosolve, 16.4 parts by weight of benzyl acetate, and 16.4 parts by weight of dibutyl carbitol.
Parts by weight of each solvent are added and concentrated by heating at 120 to 150°C for about 3 hours. After the concentration was completed, it was cooled to room temperature, and 0.2 parts by weight of Sudan (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed as an oil-soluble organic pigment, and after stirring for several minutes,
15.8 parts by weight of nitrocellulose was mixed and stirred for 8 hours using a stirrer to completely dissolve the nitrocellulose to obtain a paste for forming a transparent conductive film.
このようにして得られたペーストは、チクソト
ロピー性（ペーストを基板等の上に印刷した後で
も、印刷したペーストが流れない性質）が最適で
あり、スクリーン印刷に極めて適したものであつ
た。
The paste thus obtained had optimal thixotropy (the property that the printed paste does not flow even after printing on a substrate, etc.) and was extremely suitable for screen printing.
なお、本発明ペーストをソーダガラス基板に所
望形状に、スクリーン印刷し、150℃、20分間予
備乾燥後、500℃30分間焼成して得られた透明導
電性被膜の面積抵抗値は３〜4KΩ／cm2で、密着
強度等の被膜特性は、従来と比較して何ら変るこ
とのない優秀なものであることは勿論である。 The paste of the present invention was screen printed on a soda glass substrate in the desired shape, pre-dried at 150°C for 20 minutes, and then baked at 500°C for 30 minutes. The area resistance value of the transparent conductive film obtained was 3 to 4 KΩ/ cm 2 , it goes without saying that the film properties such as adhesion strength are excellent, with no change in comparison with conventional products.
Claims (1)
機金属化合物と、有機溶剤と、粘性剤とを含有す
る透明導電性被膜形成用ペーストにおいて、 該ペーストに、1.フエニルアゾー2.ナフトール
が添加されていることを特徴とする透明導電性被
膜形成用ペースト。[Scope of Claims] 1. A paste for forming a transparent conductive film containing an organometallic compound that becomes a transparent conductive metal oxide upon firing, an organic solvent, and a viscous agent, wherein the paste contains 1. phenylazo. 2. A paste for forming a transparent conductive film characterized by the addition of naphthol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13173881A JPS5834505A (en) | 1981-08-22 | 1981-08-22 | Paste for forming transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13173881A JPS5834505A (en) | 1981-08-22 | 1981-08-22 | Paste for forming transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5834505A JPS5834505A (en) | 1983-03-01 |
| JPS6319045B2 true JPS6319045B2 (en) | 1988-04-21 |
Family
ID=15065031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13173881A Granted JPS5834505A (en) | 1981-08-22 | 1981-08-22 | Paste for forming transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5834505A (en) |
-
1981
- 1981-08-22 JP JP13173881A patent/JPS5834505A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5834505A (en) | 1983-03-01 |
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