JP3294705B2 - High-temperature firing conductive paste and translucent conductive film - Google Patents
High-temperature firing conductive paste and translucent conductive filmInfo
- Publication number
- JP3294705B2 JP3294705B2 JP5116694A JP5116694A JP3294705B2 JP 3294705 B2 JP3294705 B2 JP 3294705B2 JP 5116694 A JP5116694 A JP 5116694A JP 5116694 A JP5116694 A JP 5116694A JP 3294705 B2 JP3294705 B2 JP 3294705B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive film
- film
- light
- powder
- acicular
- 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 - Fee Related
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Landscapes
- Glass Compositions (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Description
【0001】[0001]
【産業上の利用分野】この発明は、エレクトロルミネッ
センス(EL)発光素子等の透光性電極の形成に用いる
導電ペーストおよび透光性導電膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive paste and a light-transmitting conductive film used for forming a light-transmitting electrode such as an electroluminescence (EL) light-emitting device.
【0002】[0002]
【従来の技術】エレクトロルミネッセンス(EL)発光
素子は、蛍光体に高い電界を印加し発光させるものであ
り、その中で5〜30μm程度の蛍光体を用い、適当な
バインダーと混合し、成膜するタイプのものは、分散型
ELと呼ばれている。分散型ELとしては、樹脂やプラ
スチックをバインダー等に用い、100〜200℃程度
の比較的低温で製造されるタイプのものが広く用いられ
ているが、一部ではガラス等の無機バインダーを用い、
500〜600℃の高温プロセスを通して製造されるタ
イプのELもある。2. Description of the Related Art An electroluminescent (EL) light-emitting device emits light by applying a high electric field to a phosphor, and uses a phosphor of about 5 to 30 .mu.m and mixes it with an appropriate binder to form a film. This type is called a distributed EL. As the dispersion type EL, a type which uses a resin or a plastic as a binder and is manufactured at a relatively low temperature of about 100 to 200 ° C. is widely used.
Some types of EL are manufactured through a high temperature process of 500-600 ° C.
【0003】前者のタイプの分散型EL素子の透光性電
極には、プラスチックフィルム上にスパッタリング等に
よりITO(インジウムー錫酸化物)膜を形成したもの
や、導電性フィラーを樹脂を溶解した溶剤中に分散させ
た導電ペーストにより形成したものが用いられている。The light-transmitting electrodes of the former type of dispersion type EL element are formed by forming an ITO (indium-tin oxide) film on a plastic film by sputtering or the like, or a conductive filler in a solvent in which a resin is dissolved. What is formed of a conductive paste dispersed in a conductive paste is used.
【0004】後者のタイプの分散型EL素子は、例えば
低炭素鋼板の上にBaTiO3やTiO等の白色ホーロ
ー層を焼付け、その上に低融点で高誘電率の透明ガラス
と蛍光体粉末の混合物を用い蛍光体層を焼付けるもの
で、透光性電極としては、塩化物のCVD法等によるネ
サ膜が用いられている。In the latter type of dispersion type EL device, for example, a white enamel layer such as BaTiO 3 or TiO is baked on a low carbon steel plate, and a mixture of a transparent glass having a low melting point and a high dielectric constant and a phosphor powder is formed thereon. Is used to bake the phosphor layer. As the translucent electrode, a Nesa film formed by a chloride CVD method or the like is used.
【0005】しかしながら、ネサ膜を用いる場合、次の
ような欠点がある。 (1)CVD法により成膜するために、全面に導電膜が
形成され、パターンニングが困難である。 (2)白色ホーロー層、蛍光体層、透明性保護層(透光
性導電膜上に形成される)は、すべてスクリーン印刷等
の印刷法により形成されるが、ネサ膜だけがCVD法で
あり、工程の簡略化にとって不都合である。However, the use of the Nesa film has the following disadvantages. (1) Since a film is formed by the CVD method, a conductive film is formed on the entire surface, and patterning is difficult. (2) The white enamel layer, the phosphor layer, and the transparent protective layer (formed on the light-transmitting conductive film) are all formed by a printing method such as screen printing, but only the nesa film is a CVD method. This is inconvenient for simplifying the process.
【0006】[0006]
【発明が解決しようとする課題】この発明は、従来のこ
のような実情に鑑み、スクリーン印刷等の印刷法を用
い、高温焼成により透光性導電膜を形成できる導電ペー
ストおよび透光性導電膜を提案しようとするものであ
る。SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a conductive paste and a light-transmitting conductive film that can form a light-transmitting conductive film by high-temperature firing using a printing method such as screen printing. It is intended to propose.
【0007】[0007]
【課題を解決するための手段】この発明に係る導電ペー
ストは、透明ガラスフリット、溶剤および、長径5μm
以上で短径に対する長径の比が5以上の針状インジウム
ー錫酸化物微粉末を含有することを特徴とし、またこの
導電ペーストは、針状インジウムー錫酸化物微粉末:透
明ガラスフリットの体積の比が10:90〜50:50
であることを特徴とする。また、この発明に係る透光性
導電膜は、針状インジウムー錫酸化物微粉末とガラスと
からなり、膜の比抵抗が5.0Ω・cm以下であること
を特徴とする。The conductive paste according to the present invention comprises a transparent glass frit, a solvent, and a long diameter of 5 μm.
It is characterized in that it contains acicular indium-tin oxide fine powder having a ratio of a major axis to a minor axis of 5 or more, and this conductive paste has a volume ratio of acicular indium-tin oxide fine powder: transparent glass frit. Is 10:90 to 50:50
It is characterized by being. In addition, the light-transmitting conductive film according to the present invention is made of acicular indium-tin oxide fine powder and glass, and has a specific resistance of 5.0 Ω · cm or less.
【0008】[0008]
【作用】この発明で用いる針状インジウムー錫酸化物微
粉末は、針状で5以上の高アスペクト比を有し、抵抗値
が低いという特徴を有するもので、その製法としては、
以下に示す方法が知られている。The acicular indium-tin oxide fine powder used in the present invention is acicular and has a characteristic of having a high aspect ratio of 5 or more and a low resistance value.
The following methods are known.
【0009】(A)インジウムイオンと、硝酸イオン
と、仮焼によりSnO2となる錫化合物とを含有する水
溶液を、加熱濃縮して高粘度スラリーを生成せしめ、該
スラリーから針状粉末第一中間体を分離し、この針状粉
末第一中間体を仮焼する方法。(A) An aqueous solution containing indium ions, nitrate ions, and a tin compound that becomes SnO 2 by calcination is heated and concentrated to form a high-viscosity slurry. A method of separating the body and calcining the needle-like powder first intermediate.
【0010】(B)インジウムイオンと、硝酸イオン
と、水酸化インジウムおよび/または酸化インジウム
と、仮焼によりSnO2となる錫化合物とを含有する水
溶液を、加熱濃縮して高粘度スラリーを生成せしめ、該
スラリーから針状粉末第一中間体を分離し、この針状粉
末第一中間体を仮焼する方法。(B) An aqueous solution containing indium ions, nitrate ions, indium hydroxide and / or indium oxide, and a tin compound which becomes SnO 2 by calcination is heated and concentrated to form a high viscosity slurry. Separating the acicular powder first intermediate from the slurry and calcining the acicular powder first intermediate.
【0011】(C)インジウムイオンと、硝酸イオン
と、インジウムー錫水酸化物とを含有する水溶液を、加
熱濃縮して高粘度スラリーを生成せしめ、該スラリーか
ら針状粉末第一中間体を分離し、この針状粉末第一中間
体を仮焼する方法。(C) An aqueous solution containing indium ions, nitrate ions, and indium-tin hydroxide is heated and concentrated to form a high-viscosity slurry, and a needle-like powder first intermediate is separated from the slurry. And calcining the first intermediate of the acicular powder.
【0012】(D)インジウムイオンと、硝酸イオンと
を含有する水溶液を、加熱濃縮して高粘度スラリーを生
成せしめ、該スラリーから針状粉末第一中間体を分離
し、この針状粉末第一中間体に仮焼により二酸化錫とな
る錫化合物を被覆して仮焼する方法。(D) An aqueous solution containing indium ions and nitrate ions is concentrated by heating to form a high-viscosity slurry, and the first intermediate powder of the acicular powder is separated from the slurry. A method in which the intermediate is coated with a tin compound which becomes tin dioxide by calcination and calcined.
【0013】(E)インジウムイオンと、硝酸イオン
と、水酸化インジウムおよび/または酸化インジウムと
を含有する水溶液を、加熱濃縮して高粘度スラリーを生
成せしめ、該スラリーから針状粉末第一中間体を分離
し、この針状粉末第一中間体に仮焼により二酸化錫とな
る錫化合物を被覆して仮焼する方法。(E) An aqueous solution containing indium ions, nitrate ions, indium hydroxide and / or indium oxide is heated and concentrated to form a high-viscosity slurry, and the needle-like powder first intermediate is produced from the slurry. And calcinating the first intermediate of the acicular powder by coating with a tin compound which becomes tin dioxide by calcination.
【0014】前記の各製法において、加熱濃縮して生成
させた高粘度スラリーから針状粉末第一中間体を分離す
る方法としては、スラリーに多量の水を加えて濾過する
方法が用いられる。濾過によって得た針状粉末は洗浄、
乾燥した後、700〜1200℃程度で数十分仮焼す
る。In each of the above-mentioned production methods, as a method for separating the acicular powder first intermediate from the high-viscosity slurry produced by heat concentration, a method of adding a large amount of water to the slurry and filtering the slurry is used. The needle powder obtained by filtration is washed,
After drying, it is calcined at about 700 to 1200 ° C. for several tens minutes.
【0015】また、前記の各製法おいては、針状粉末第
一中間体をアルカリ水溶液と反応させて針状粉末第二中
間体を得、この針状粉末第二中間体を仮焼する方法をと
ってもよい。In each of the above-mentioned production methods, a method for reacting the first intermediate acicular powder with an aqueous alkali solution to obtain a second intermediate acicular powder, and calcining the second intermediate acicular powder. May be taken.
【0016】前記の各製法によれば、長径5μm以上、
アスペクト比5以上で、添加する錫化合物、濃縮条件に
よりアスペクト比が30程度のものまで得られる。この
粉末を100kgf/cm2の圧力を加えてペレット状
にしたときの比抵抗(以下、圧粉抵抗という)は0.0
3Ω・cm程度である。なお、アスペクト比を5以上と
するのは、ガラスに対し少量の使用で導電性が得られる
ようにするためである。アスペクト比が5未満では、膜
の比抵抗を5.0Ω・cm以下にすることが達成できな
いからである。アスペクト比は高い方がよく、好ましく
は10以上がよい。According to each of the above manufacturing methods, the major axis is 5 μm or more,
With an aspect ratio of 5 or more, an aspect ratio of about 30 can be obtained depending on the tin compound to be added and the concentration conditions. The specific resistance (hereinafter referred to as the powder resistance) when the powder is formed into a pellet by applying a pressure of 100 kgf / cm 2 is 0.0
It is about 3Ω · cm. The aspect ratio is set to 5 or more so that conductivity can be obtained by using a small amount of glass. If the aspect ratio is less than 5, the specific resistance of the film cannot be reduced to 5.0 Ω · cm or less. The aspect ratio is preferably higher, more preferably 10 or more.
【0017】また、使用する針状インジウムー錫酸化物
微粉末の長径を5μm以上とするのは、長径が大きいほ
ど粒子どうしの接点の数が少なくて低抵抗の膜が得られ
ることと、例えば分散型ELに用いる場合、塗布面の蛍
光体層は5〜30μm径の硫化亜鉛粒子を用いているた
め、その表面に数μm程度の凹凸があるが、長径が5μ
m以上あるとこのような凹凸があっても、針状粒子どう
しの接触が保たれ、必要な導電性が得られるからであ
る。ただし、長径が100μm以上となると、スクリー
ン印刷時にスクリーンの網目を通りにくくなり、印刷に
支障をきたすおそれがあるため、一般的には100μm
以下の長径のものが好ましい。ただ100メッシュ以下
の粗い目のスクリーンを用いる場合は、この限りではな
い。この発明の導電ペーストでは、比較的に大きなフィ
ラーを用いているが、200μm程度の幅の線をスクリ
ーン印刷することは可能である。Further, the major axis of the acicular indium-tin oxide fine powder to be used is set to 5 μm or more because the larger the major axis, the smaller the number of contact points between the particles and a lower resistance film is obtained. When used for a mold EL, since the phosphor layer on the coating surface uses zinc sulfide particles having a diameter of 5 to 30 μm, the surface has irregularities of about several μm, but the long diameter is 5 μm.
This is because if the number is not less than m, the contact between the acicular particles is maintained and the necessary conductivity can be obtained even if such irregularities are present. However, if the major axis is 100 μm or more, it is difficult to pass through the screen mesh at the time of screen printing, which may hinder printing.
The following major diameter is preferred. However, this does not apply when a coarse screen having a mesh size of 100 mesh or less is used. In the conductive paste of the present invention, a relatively large filler is used, but a line having a width of about 200 μm can be screen-printed.
【0018】この発明に用いるガラスフリットとして
は、300〜500メッシュの篩を通過したものを用い
ることができる。また、種類としては特に制限はない
が、焼成する温度により選定される。500〜600℃
の焼成温度では、例えば比較的低融点であるPbO−B
2O3−SiO2系のガラスを用いることができる。た
だし、EL素子の蛍光体上に形成する場合は、蛍光体の
硫化亜鉛(ZnS)と反応しないガラスを選定する必要
がある。PbO−B2O3−SiO2系ガラスは、Pb
OがZnSと反応するため、この場合は好ましくない。
EL素子に用いる場合は、PbOを含まない例えばNa
2O−B2O3−ZnO系のガラスを用いることができ
る。As the glass frit used in the present invention, a glass frit that has passed through a sieve of 300 to 500 mesh can be used. The type is not particularly limited, but is selected according to the firing temperature. 500-600 ° C
Is, for example, PbO-B having a relatively low melting point.
2 O 3 —SiO 2 glass can be used. However, when formed on the phosphor of the EL element, it is necessary to select a glass that does not react with zinc sulfide (ZnS) of the phosphor. PbO-B 2 O 3 -SiO 2 based glass, Pb
This is not preferred because O reacts with ZnS.
When used for an EL element, for example, Na containing no PbO
2 O-B 2 O 3 -ZnO based glass can be used.
【0019】また、この発明において、ペースト中の針
状インジウムー錫酸化物微粉末とガラスフリットとの体
積比を10:90〜50:50に限定したのは、10:
90よりガラスが多いと透光性導電膜の抵抗が高くなり
すぎ、50:50よりガラスが少ないと透光性導電膜の
強度が低下すると同時に抵抗も高くなるからである。In the present invention, the volume ratio of the acicular indium-tin oxide fine powder in the paste to the glass frit is limited to 10:90 to 50:50.
If the amount of glass is more than 90, the resistance of the light-transmitting conductive film becomes too high, and if the amount of glass is less than 50:50, the strength of the light-transmitting conductive film is reduced and the resistance is also increased.
【0020】ここで、針状インジウムー錫酸化物微粉末
とガラスフリットの比率として体積比を用いたのは、ガ
ラスフリットの比重が、用いるフリットにより2〜6と
大きく異なるためである。例えば、バインダーに樹脂を
用いた場合は、樹脂の比重は通常1.1〜1.3である
ため、重量比、体積比のどちらを用いても大きな問題と
はならない。The reason why the volume ratio is used as the ratio between the acicular indium-tin oxide fine powder and the glass frit is that the specific gravity of the glass frit varies greatly from 2 to 6 depending on the frit used. For example, when a resin is used as the binder, the specific gravity of the resin is usually 1.1 to 1.3, so that using either the weight ratio or the volume ratio does not cause a serious problem.
【0021】一方、ペーストは、通常スクリーン印刷に
より印刷するため増粘剤を用いて適度な粘度に調整され
る。増粘剤としては、メチルセルロース、エチルセルロ
ース等のセルロース系のものや、アクリル等の樹脂を用
いることができる。これらは、焼成過程で燃焼除去され
るものであればよく、上記以外でも同様の効果を示すも
のであれば用いることができる。On the other hand, the paste is usually adjusted to an appropriate viscosity by using a thickener for printing by screen printing. As the thickener, a cellulose-based material such as methylcellulose or ethylcellulose, or a resin such as acryl can be used. Any of these may be used as long as they are burned and removed during the firing process.
【0022】ペーストに用いる溶剤は、一般の塗料・ペ
ーストに用いられる有機溶剤または水を用いることがで
きる。例えば、有機溶剤としては、シクロヘキサノン、
イソホロン、ジアセトンアルコール等のケトン系溶剤、
メチルアルコール、エチルアルコール、イソプロピルア
ルコール等のアルコール系溶剤、酢酸エチル、酢酸ブチ
ル等のエステル系溶剤、セロソルブ、ブチルセロソル
ブ、ブチルカルビトール、N.Nージメチルホルムアミ
ド等があげられるが、これらに限定されるものではな
い。As the solvent used for the paste, an organic solvent or water used for general paints and pastes can be used. For example, as the organic solvent, cyclohexanone,
Ketone solvents such as isophorone and diacetone alcohol;
Alcohol solvents such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ester solvents such as ethyl acetate and butyl acetate; cellosolve, butyl cellosolve, butyl carbitol; Examples include, but are not limited to, N-dimethylformamide.
【0023】塗膜の焼成温度は、用いるガラスフリット
の軟化点以上であることが好ましい。軟化点以下である
と、バインダーであるガラスフリットの流動が不十分で
十分な強度を有する膜が得られない。The baking temperature of the coating film is preferably higher than the softening point of the glass frit used. If it is lower than the softening point, the flow of the glass frit as a binder is insufficient and a film having sufficient strength cannot be obtained.
【0024】塗膜の焼成は大気中で行うことができる。
なお、不活性ガスまたは弱還元性雰囲気中で行うことも
できるが、この場合、ITO粒子中に空孔が導入される
ため、大気中で焼成するのに比べ抵抗を低下することが
可能である。しかし、通常用いる増粘剤成分であるセル
ロース類、樹脂類の燃焼には酸素が必要であり、これら
増粘剤成分の燃焼終了後に不活性ガス雰囲気または弱還
元性雰囲気にする必要がある。The firing of the coating film can be performed in the air.
In addition, although it can also be performed in an inert gas or weakly reducing atmosphere, in this case, since holes are introduced into the ITO particles, the resistance can be reduced as compared with firing in the air. . However, combustion of celluloses and resins, which are commonly used thickener components, requires oxygen, and after completion of combustion of these thickener components, an inert gas atmosphere or a weak reducing atmosphere is required.
【0025】[0025]
実施例1 インジウムメタルを硝酸に溶解した溶液に四塩化錫含水
塩を加え、撹拌しながら加熱濃縮し、液温130〜15
0℃まで濃縮して濃厚なスラリーを生成せしめ、このス
ラリーに多量の水を加えて濾過し、濾過によって得た針
状粉末を洗浄、乾燥し、1200℃程度で30分間仮焼
して得られた、長径が5μm以上でアスペクト比が5以
上、圧粉抵抗0.02Ω・cm、錫含有量2.5重量%
の図1に示す針状インジウムー錫酸化物微粉末(以下、
ITO粉末という)と、ガラスフリットを表1のペース
ト1の組成に配合して混合しよく撹拌した後、200メ
ッシュステンレス金網で濾過し、得られた導電ペースト
を75×75×1.1mmのソーダライムガラス板に2
00メッシュのスクリーン版で、4×5cmの大きさに
スクリーン印刷し、120℃で20分間乾燥後、大気中
540℃で10分間焼成して得られた透光性導電膜の2
000倍顕微鏡写真を図2に、膜厚、表面抵抗、全光線
透過率(380〜780mm)、ヘーズ値、比抵抗を表
2にそれぞれ示す。Example 1 Tin tetrachloride hydrate was added to a solution in which indium metal was dissolved in nitric acid, and the mixture was heated and concentrated with stirring, and the solution temperature was 130 to 15%.
The solution is concentrated to 0 ° C. to form a thick slurry, a large amount of water is added to the slurry, and the slurry is filtered. The acicular powder obtained by the filtration is washed, dried, and calcined at about 1200 ° C. for 30 minutes. In addition, the major axis is 5 μm or more, the aspect ratio is 5 or more, the dust resistance is 0.02Ω · cm, and the tin content is 2.5% by weight.
Needle-like indium-tin oxide fine powder shown in FIG.
An ITO powder) and a glass frit were blended into the composition of paste 1 in Table 1, mixed and stirred well, filtered through a 200-mesh stainless steel wire mesh, and the obtained conductive paste was soaked in 75 × 75 × 1.1 mm soda. 2 on lime glass plate
A screen printing plate having a size of 4 × 5 cm was printed on a 00 mesh screen plate, dried at 120 ° C. for 20 minutes, and then baked at 540 ° C. in the air for 10 minutes.
FIG. 2 shows a 000-fold micrograph, and Table 2 shows the film thickness, surface resistance, total light transmittance (380 to 780 mm), haze value, and specific resistance.
【0026】膜厚は、東京精密社製の表面粗さ測定機
(商品名:サーフコム900A)により測定した。その
際、膜の表面に凹凸があるため測定チャートから0.5
μm単位で読取った。表面抵抗は、三菱油化社製のロー
レスタMCPーT400(商品名)により測定した。全
光線透過率、ヘーズ値は、基板のガラス板と一緒にスガ
試験機械社製の直読ヘーズコンピュータHGMーZDP
(商品名)により測定した。膜の比抵抗は下記式により
求めた。 膜の比抵抗(Ω・cm)=表面抵抗(kΩ/□)×膜厚
(10−4cm)The film thickness was measured with a surface roughness measuring device (trade name: Surfcom 900A) manufactured by Tokyo Seimitsu Co., Ltd. At this time, the measurement chart shows 0.5
Read in μm units. The surface resistance was measured with a LORESTA MCP-T400 (trade name) manufactured by Mitsubishi Yuka Corporation. The total light transmittance and the haze value were measured using the HGM-ZDP direct reading haze computer manufactured by Suga Test Machine Co., Ltd.
(Trade name). The specific resistance of the film was determined by the following equation. Specific resistance of the film (Ω · cm) = surface resistance (kΩ / □) × film thickness (10 −4 cm)
【0027】実施例2 ペーストの組成が表1のペースト2である以外は、実施
例1と同じITO粉末を用い実施例1と同様にして導電
ペーストおよび透光性導電膜を得た。得られた透光性導
電膜の2000倍の顕微鏡写真を図3に、実施例1と同
様の手段で求めた膜厚、表面抵抗、全光線透過率(38
0〜780mm)、ヘーズ値、比抵抗を表2にそれぞれ
示す。Example 2 A conductive paste and a light-transmitting conductive film were obtained in the same manner as in Example 1 except that the composition of the paste was Paste 2 shown in Table 1. FIG. 3 is a photomicrograph (magnification: 2000) of the obtained light-transmitting conductive film. FIG. 3 shows the film thickness, surface resistance, and total light transmittance (38
Table 2 shows the haze value and the specific resistance.
【0028】実施例3 スクリーン印刷のスクリーン版が150メッシュである
以外は、実施例2と同様にして導電ペーストおよび透光
性導電膜を得た。得られた透光性導電膜の、実施例1と
同様の手段で求めた膜厚、表面抵抗、全光線透過率(3
80〜780mm)、ヘーズ値、比抵抗を表2に示す。Example 3 A conductive paste and a light-transmitting conductive film were obtained in the same manner as in Example 2, except that the screen plate used for screen printing was 150 mesh. The thickness, surface resistance, and total light transmittance (3%) of the obtained translucent conductive film obtained by the same means as in Example 1.
Table 2 shows the haze value and the specific resistance.
【0029】実施例4 ペーストの組成が表1のペースト3で、焼成を大気中5
60℃で10分間行った以外は、実施例1と同じITO
粉末を用い、実施例1と同様にして導電ペーストおよび
透光性導電膜を得た。得られた透光性導電膜の、実施例
1と同様の手段で求めた膜厚、表面抵抗、全光線透過率
(380〜780mm)、ヘーズ値、比抵抗を表2に示
す。Example 4 The composition of the paste was the paste 3 shown in Table 1, and the baking was performed in the atmosphere 5
The same ITO as in Example 1 except that it was performed at 60 ° C. for 10 minutes.
A conductive paste and a light-transmitting conductive film were obtained in the same manner as in Example 1 using the powder. Table 2 shows the film thickness, surface resistance, total light transmittance (380 to 780 mm), haze value, and specific resistance of the obtained translucent conductive film obtained by the same means as in Example 1.
【0030】実施例5 スクリーン印刷のスクリーン版が150メッシュである
以外は、実施例4と同様にして導電ペーストおよび透光
性導電膜を得た。得られた透光性導電膜の、実施例1と
同様の手段で求めた膜厚、表面抵抗、全光線透過率(3
80〜780mm)、ヘーズ値、比抵抗を表2に示す。Example 5 A conductive paste and a light-transmitting conductive film were obtained in the same manner as in Example 4, except that the screen plate used for screen printing was 150 mesh. The thickness, surface resistance, and total light transmittance (3%) of the obtained translucent conductive film obtained by the same means as in Example 1.
Table 2 shows the haze value and the specific resistance.
【0031】実施例6 基板に75×75×1.1mmの低アルカリガラスを用
い、焼成を大気中600℃で10分間行った以外は、実
施例5と同様にして導電ペーストおよび透光性導電膜を
得た。得られた透光性導電膜の、実施例1と同様の手段
で求めた膜厚、表面抵抗、全光線透過率(380〜78
0mm)、ヘーズ値、比抵抗を表2に示す。Example 6 A conductive paste and a light-transmitting conductive material were prepared in the same manner as in Example 5, except that a low alkali glass of 75 × 75 × 1.1 mm was used for the substrate and sintering was performed at 600 ° C. in the air for 10 minutes. A membrane was obtained. The film thickness, surface resistance, and total light transmittance (380 to 78) of the obtained light-transmitting conductive film obtained by the same means as in Example 1.
0 mm), haze value, and specific resistance are shown in Table 2.
【0032】[0032]
【比較例】ペーストの組成が表1のペースト4である以
外は、実施例1と同じITO粉末を用い、実施例1と同
様にして導電ペーストおよび透光性導電膜を得た。得ら
れた透光性導電膜の、実施例1と同様の手段で求めた膜
厚、表面抵抗、全光線透過率(380〜780mm)、
ヘーズ値、比抵抗を表2に示す。Comparative Example A conductive paste and a light-transmitting conductive film were obtained in the same manner as in Example 1 except that the composition of the paste was Paste 4 shown in Table 1 and the same ITO powder was used. The film thickness, surface resistance, total light transmittance (380 to 780 mm) of the obtained translucent conductive film obtained by the same means as in Example 1,
Table 2 shows the haze value and the specific resistance.
【0033】[0033]
【表1】 [Table 1]
【0034】[0034]
【表2】 [Table 2]
【0035】[0035]
【発明の効果】以上説明したごとく、この発明の導電ペ
ーストおよび透光性導電膜は、十分な導電性と光線透過
性が得られ、エレクトロルミネッセンス(EL)発光素
子等の透光性電極の形成に大きく寄与する。As described above, the conductive paste and the light-transmitting conductive film of the present invention have sufficient conductivity and light transmittance, and can form a light-transmitting electrode such as an electroluminescent (EL) light-emitting element. Greatly contributes to
【図1】この発明の実施例1において使用した針状イン
ジウムー錫酸化物微粉末の結晶構造を示す顕微鏡写真で
ある。FIG. 1 is a micrograph showing a crystal structure of a fine acicular indium-tin oxide powder used in Example 1 of the present invention.
【図2】同上の実施例2で得られた透光性導電膜の顕微
鏡写真である。FIG. 2 is a micrograph of a light-transmitting conductive film obtained in Example 2 of the above.
【図3】同上の実施例3で得られた透光性導電膜の顕微
鏡写真である。FIG. 3 is a micrograph of a light-transmitting conductive film obtained in Example 3 of the above.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平3−80591(JP,A) 特開 平3−24188(JP,A) 特開 平3−62433(JP,A) (58)調査した分野(Int.Cl.7,DB名) H01B 1/16 H01B 1/00 H01B 5/14 C01G 19/00 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-80591 (JP, A) JP-A-3-24188 (JP, A) JP-A-3-62433 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01B 1/16 H01B 1/00 H01B 5/14 C01G 19/00
Claims (3)
5μm以上で短径に対する長径の比が5以上の針状イン
ジウムー錫酸化物微粉末を含有する高温焼成用導電ペー
スト。1. A conductive paste for high-temperature firing containing a transparent glass frit, a solvent, and a fine powder of acicular indium-tin oxide having a major axis of 5 μm or more and a ratio of the major axis to the minor axis of 5 or more.
ガラスフリットの体積の比が10:90〜50:50で
あることを特徴とする請求項1記載の導電ペースト。2. The conductive paste according to claim 1, wherein the volume ratio of the acicular indium-tin oxide fine powder to the transparent glass frit is from 10:90 to 50:50.
スとからなる透光性導電膜であって、膜の比抵抗が5.
0Ω・cm以下であることを特徴とする透光性導電膜。3. A light-transmitting conductive film comprising acicular indium-tin oxide fine powder and glass, wherein the specific resistance of the film is 5.
A light-transmitting conductive film having a resistivity of 0 Ω · cm or less.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5116694A JP3294705B2 (en) | 1994-02-24 | 1994-02-24 | High-temperature firing conductive paste and translucent conductive film |
US08/659,821 US5833941A (en) | 1993-04-05 | 1996-06-07 | Raw material for producing powder of indium-tin oxide aciculae and method of producing the raw material, powder of indium-tin oxide aciculae and method of producing the powder, electroconductive paste and light-transmitting electroconductive film |
US08/662,150 US5849221A (en) | 1993-04-05 | 1996-06-12 | Raw material for producing powder of indium-tin oxide aciculae and method of producing the raw material, powder of indium-tin oxide aciculae and method of producing the powder, electroconductive paste and light-transmitting electroconductive film |
US08/662,145 US5820843A (en) | 1993-04-05 | 1996-06-12 | Raw material for producing powder of indium-tin oxide aciculae and method of producing the raw material, powder of indium-tin oxide aciculae and method of producing the powder, electroconductive paste and light-transmitting electroconductive film |
US09/199,443 US6511614B1 (en) | 1993-04-05 | 1999-02-19 | Raw material for producing powder of indium-tin oxide aciculae and method of producing the raw material, powder of indium-tin oxide aciculae and method of producing the powder, electroconductive paste and light-transmitting electroconductive film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5116694A JP3294705B2 (en) | 1994-02-24 | 1994-02-24 | High-temperature firing conductive paste and translucent conductive film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07235214A JPH07235214A (en) | 1995-09-05 |
JP3294705B2 true JP3294705B2 (en) | 2002-06-24 |
Family
ID=12879245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5116694A Expired - Fee Related JP3294705B2 (en) | 1993-04-05 | 1994-02-24 | High-temperature firing conductive paste and translucent conductive film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3294705B2 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7763189B2 (en) | 2001-05-16 | 2010-07-27 | E. I. Du Pont De Nemours And Company | Dielectric composition with reduced resistance |
US6908574B2 (en) | 2001-08-13 | 2005-06-21 | Dowa Mining Co., Ltd. | Tin-containing indium oxides, a process for producing them, a coating solution using them and electrically conductive coatings formed of them |
US20070023765A1 (en) * | 2005-07-29 | 2007-02-01 | Thomas Alan C | Acicular ITO for LED array |
JP5068298B2 (en) * | 2009-10-08 | 2012-11-07 | 日揮触媒化成株式会社 | Transparent conductive film-forming coating liquid, transparent conductive film-coated substrate, and display device |
KR102041269B1 (en) * | 2019-05-20 | 2019-11-06 | 유한회사 대동 | Transparent heat generating body for protect eyes and the producing method thereof |
-
1994
- 1994-02-24 JP JP5116694A patent/JP3294705B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH07235214A (en) | 1995-09-05 |
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