JPH08199096A - Conductive film-forming composition and production of glass plate covered with transparent conductive film - Google Patents
Conductive film-forming composition and production of glass plate covered with transparent conductive filmInfo
- Publication number
- JPH08199096A JPH08199096A JP1098395A JP1098395A JPH08199096A JP H08199096 A JPH08199096 A JP H08199096A JP 1098395 A JP1098395 A JP 1098395A JP 1098395 A JP1098395 A JP 1098395A JP H08199096 A JPH08199096 A JP H08199096A
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- conductive film
- coupling agent
- glass plate
- weight
- metal compound
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、透明電極、帯電防止
膜、熱線反射膜、電磁波シールド膜、面発熱体、タッチ
パネル等の分野に利用できる導電膜形成用組成物と、そ
の導電膜形成用組成物から形成された透明導電膜被覆ガ
ラスに関するものである。FIELD OF THE INVENTION The present invention relates to a conductive film-forming composition which can be used in the fields of transparent electrodes, antistatic films, heat ray reflective films, electromagnetic wave shield films, surface heating elements, touch panels, and the like. The present invention relates to a transparent conductive film-coated glass formed from the composition.
【０００２】[0002]
【従来の技術】透明導電膜の形成法は、ＣＶＤ、スパッ
タリング法等を含む気相法と、塗布法とに大別される。
気相法は、従来より最も広く用いれらている膜形成方法
であり、高性能の透明導電膜を形成できるが、装置が高
価であって、生産性や歩留まりが悪く、大面積の成膜に
は不向きである。2. Description of the Related Art Methods for forming a transparent conductive film are roughly classified into a vapor phase method including a CVD method, a sputtering method and the like, and a coating method.
The vapor phase method is the most widely used film forming method in the past, and can form high-performance transparent conductive films, but the equipment is expensive, productivity and yield are poor, and large-area film formation is possible. Is not suitable for.
【０００３】一方、導電性微粒子をバインダー溶液 (バ
インダーと溶媒からなる溶液) 中に分散させて塗料化
し、得られた導電性塗料を基板に塗布して乾燥、硬化さ
せ、透明導電膜を形成する塗布法は、導電膜を形成する
基板の寸法や形成の制限が少なく、設備が簡単で生産性
に優れており、簡便に透明導電膜を形成することができ
る。塗布法でヘーズ (曇度) の低い透明性に優れた導電
膜を得るには、塗料化の段階でバインダー溶液中に導電
性微粒子を一次粒子に近い状態までほぼ完全に分散させ
ることが重要である。即ち、バインダーは、ＩＴＯ粉末
を分散させる作用と、ＩＴＯ粉末を結合させる作用を果
たす必要がある。On the other hand, conductive fine particles are dispersed in a binder solution (solution consisting of a binder and a solvent) to form a paint, and the obtained conductive paint is applied to a substrate, dried and cured to form a transparent conductive film. In the coating method, there are few restrictions on the size and formation of the substrate on which the conductive film is formed, the equipment is simple and the productivity is excellent, and the transparent conductive film can be easily formed. In order to obtain a transparent conductive film with low haze (cloudiness) by the coating method, it is important to disperse the conductive fine particles in the binder solution almost completely to the state of primary particles at the stage of coating. is there. That is, the binder needs to have a function of dispersing the ITO powder and a function of binding the ITO powder.
【０００４】バインダーとしては、アクリル樹脂、ポリ
エステル樹脂、ポリカーボネート樹脂等の透明性に優れ
た樹脂が一般的であるが、エチルシリケートやその縮合
物などの金属アルコキシドを使用する場合もある。導電
性微粒子としては、ドープ原子としてAlまたは他の金属
を含有する酸化亜鉛、アンチモンを含有する酸化錫等も
使用できるが、代表例は、特に低抵抗の膜を得ることが
知られている、錫を含有する酸化インジウム (以下、Ｉ
ＴＯともいう) である。As the binder, a resin having excellent transparency such as an acrylic resin, a polyester resin or a polycarbonate resin is generally used, but a metal alkoxide such as ethyl silicate or a condensate thereof may be used in some cases. As the conductive fine particles, zinc oxide containing Al or another metal as a doping atom, tin oxide containing antimony, etc. can be used, but a typical example is known to obtain a film having particularly low resistance, Indium oxide containing tin (hereinafter, I
(Also called TO).
【０００５】[0005]
【発明が解決しようとする課題】近年、液晶ディスプレ
イ、タッチパネル、プラズマディスプレイ、エレクトロ
ルミネッセンスディスプレイあるいは蛍光ディスプレイ
等の高性能化は目ざましく、これらに用いられる透明電
極や帯電防止膜は、より一層の光学特性と導電性の向上
が求められるようになってきた。しかし、塗布法により
形成される導電膜は、導電性微粒子としてＩＴＯ粉末を
使用しても、気相法により得られたものに比べ、ヘーズ
や導電性の点で劣っており、上記の要請には満足に対応
することができなかった。In recent years, liquid crystal displays, touch panels, plasma displays, electroluminescent displays, fluorescent displays, and the like have been remarkably improved in performance, and transparent electrodes and antistatic films used in these have improved optical performance. There has been a demand for improvement in characteristics and conductivity. However, the conductive film formed by the coating method is inferior to that obtained by the vapor phase method in terms of haze and conductivity even when ITO powder is used as the conductive fine particles. Was unable to respond satisfactorily.
【０００６】本発明の目的は、導電膜を容易に形成でき
る塗布法を用いて、ヘーズ、導電性、密着性および膜硬
度に優れた導電膜を形成しうる導電膜形成用組成物とそ
の透明導電膜形成用組成物から形成された透明導電膜被
覆ガラスを提供することである。An object of the present invention is to provide a conductive film-forming composition capable of forming a conductive film excellent in haze, conductivity, adhesion and film hardness by using a coating method capable of easily forming a conductive film, and a transparent composition thereof. It is intended to provide a transparent conductive film-coated glass formed from a composition for forming a conductive film.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく検討を重ねた。その結果、ＩＴＯ粉末、溶
媒およびバインダーからなる、塗布法に用いる従来の導
電塗料では、ヘーズ低下のために行うＩＴＯ粉末の分散
処理工程で、ＩＴＯ粉末の表面が絶縁性のバインダーで
被覆されてしまい、バインダーが乾燥または焼付後の塗
膜中にも残留するため、塗膜内のＩＴＯ粉末はバインダ
ーにより被覆されたままであり、粉末間の直接接触が必
要な電子移動が阻害されて、導電性の向上 (抵抗値の低
下) を妨げることがわかった。Means for Solving the Problems The present inventors have made extensive studies to achieve the above object. As a result, in the conventional conductive coating material used for the coating method, which is composed of the ITO powder, the solvent and the binder, the surface of the ITO powder is covered with the insulating binder in the step of dispersing the ITO powder to reduce the haze. Since the binder remains in the coating film after drying or baking, the ITO powder in the coating film remains covered with the binder, and the electron transfer that requires direct contact between the powders is hindered, resulting in a conductive property. It was found that the improvement (reduction of resistance value) was hindered.
【０００８】従って、バインダーを使用した従来の導電
塗料では、ヘーズ低下を優先させるために十分なＩＴＯ
粉末の分散を行うと、膜の抵抗値が増大する。逆に、抵
抗値の低下を優先させると、ＩＴＯ粉末の分散が犠牲と
なりヘーズが高くなる。そのため、ヘーズと導電性とを
同時に改善することが困難である。Therefore, in the conventional conductive paint using the binder, sufficient ITO is added to give priority to the haze reduction.
When the powder is dispersed, the resistance value of the film increases. On the contrary, if priority is given to the reduction of the resistance value, the dispersion of the ITO powder is sacrificed and the haze becomes high. Therefore, it is difficult to improve haze and conductivity at the same time.
【０００９】このような知見に基づいてさらに研究を続
けた結果、バインダーの代わりに焼成時に分解するカッ
プリング剤を用いても、ＩＴＯ粉末を塗料中に十分に分
散させることができることを見出した。しかし、カップ
リング剤だけではＩＴＯ粉末の結合力が不足し、焼成後
に得られる透明導電膜の密着性や膜硬度が低下し、ヘー
ズや導電性もまだ不十分である。この点は、焼結助剤と
して金属の有機酸塩または無機酸塩等の金属化合物を使
用し、この金属化合物を予め塗料中にカップリング剤と
一緒に配合しておくか、或いはＩＴＯ粉末とカップリン
グ剤から得られた塗膜に、この金属化合物の溶液を含浸
させることで解決でき、上記目的を達成することができ
ることが判明した。As a result of further research based on these findings, it was found that the ITO powder can be sufficiently dispersed in the paint even if a coupling agent that decomposes during firing is used instead of the binder. However, the coupling agent alone lacks the binding force of the ITO powder, reduces the adhesion and film hardness of the transparent conductive film obtained after firing, and has insufficient haze and conductivity. In this respect, a metal compound such as an organic acid salt or an inorganic acid salt of a metal is used as a sintering aid, and this metal compound is preliminarily compounded in a coating material together with a coupling agent, or is mixed with an ITO powder. It was found that the problem can be solved by impregnating the coating film obtained from the coupling agent with the solution of the metal compound, and the above object can be achieved.
【００１０】本発明の導電膜形成用組成物は、下記の
１液型組成物と、下記の２液型組成物のいずれの形態
でもよい。 錫を含有する酸化インジウム粉末 (＝ＩＴＯ粉末) 、
溶媒、カップリング剤、ならびに金属の有機酸塩および
無機酸塩より選ばれた金属化合物、からなる導電膜形成
用組成物であって、前記酸化インジウム粉末100 重量部
に対して前記カップリング剤を 0.1〜５重量部、前記金
属化合物を 0.2〜15重量部の割合で含有することを特徴
とする無バインダーの導電膜形成用組成物。The conductive film-forming composition of the present invention may be in any form of the following one-pack type composition and the following two-pack type composition. Indium oxide powder containing tin (= ITO powder),
A composition for forming a conductive film comprising a solvent, a coupling agent, and a metal compound selected from organic acid salts and inorganic acid salts of metals, wherein the coupling agent is added to 100 parts by weight of the indium oxide powder. A binder-free conductive film-forming composition comprising 0.1 to 5 parts by weight and the metal compound in an amount of 0.2 to 15 parts by weight.
【００１１】ＩＴＯ粉末、溶媒、ならびに前記粉末10
0 重量部に対して 0.1〜５重量部の量のカップリング剤
からなるＡ液と、金属の有機酸塩および無機酸塩より選
ばれた金属化合物と溶媒とからなるＢ液とから構成され
る、無バインダーの２液型の導電膜形成用組成物。ただ
し、Ａ液は、上記金属化合物を前記粉末100 重量部に対
して15重量部より少ない量でさらに含有していてもよ
い。即ち、上記金属化合物の一部はＡ液中に存在させて
もよい。ITO powder, solvent, and said powder 10
It is composed of solution A consisting of a coupling agent in an amount of 0.1 to 5 parts by weight relative to 0 part by weight, and solution B consisting of a metal compound selected from organic acid salts and inorganic acid salts of metals and a solvent. A binder-free two-component conductive film-forming composition. However, the liquid A may further contain the metal compound in an amount of less than 15 parts by weight with respect to 100 parts by weight of the powder. That is, part of the metal compound may be present in the liquid A.
【００１２】好適態様にあっては、前記カップリング剤
はシラン系カップリング剤、チタネート系カップリング
剤、およびアルミネート系カップリング剤より選ばれ、
前記金属化合物はCo、Ni、Pb、In、Zn、Al、Fe、Ti、Sn
およびSbより選ばれた金属の化合物である。In a preferred embodiment, the coupling agent is selected from silane coupling agents, titanate coupling agents, and aluminate coupling agents,
The metal compound is Co, Ni, Pb, In, Zn, Al, Fe, Ti, Sn
And a compound of a metal selected from Sb.
【００１３】上記の１液型の導電膜形成用組成物は、
これをガラス板に塗布し、300 ℃以上の不活性または還
元性雰囲気中で焼成することにより、ガラス板上に透明
導電膜を形成することができる。The above-mentioned one-component type conductive film forming composition is
A transparent conductive film can be formed on a glass plate by applying this to a glass plate and baking it in an inert or reducing atmosphere at 300 ° C. or higher.
【００１４】上記の２液型の導電膜形成用組成物は、
そのＡ液をガラス板に塗布した後、得られた塗膜に、前
記粉末100 重量部に対して 0.2〜15重量部の量の前記金
属化合物を含有するＢ液を含浸させ、300 ℃以上の不活
性または還元性雰囲気中で焼成することにより、ガラス
板上に透明導電膜を形成することができる。なお、Ａ液
が既に前記金属化合物を含有している場合には、Ｂ液の
含浸量は、含浸後の塗膜中の前記金属化合物の割合が、
前記粉末100 重量部に対して 0.2〜15重量部となるよう
にする。The above-mentioned two-component type conductive film forming composition is
After applying the solution A to a glass plate, the obtained coating film is impregnated with solution B containing the metal compound in an amount of 0.2 to 15 parts by weight with respect to 100 parts by weight of the powder, and the temperature is 300 ° C or more. The transparent conductive film can be formed on the glass plate by baking in an inert or reducing atmosphere. When the liquid A already contains the metal compound, the impregnation amount of the liquid B is determined by the ratio of the metal compound in the coating film after the impregnation.
The amount is 0.2 to 15 parts by weight based on 100 parts by weight of the powder.
【００１５】なお、２液型の導電膜形成用組成物は、塗
布前にＡ液とＢ液とを混合し、上記１液型の導電膜形成
用組成物と同様に塗布および焼成して、ガラス板上に透
明導電膜を形成することもできる。The two-component type conductive film forming composition is prepared by mixing the liquid A and the liquid B before coating and applying and baking the same as the one-component type conductive film forming composition. A transparent conductive film can also be formed on the glass plate.
【００１６】いずれの方法により得られた透明導電膜
も、ＩＴＯ粉末が、カップリング剤および焼結助剤とし
て用いた金属化合物の分解により生成した金属酸化物な
どの無機金属化合物によって焼結された構造を有する。In each of the transparent conductive films obtained by any of the methods, the ITO powder was sintered with an inorganic metal compound such as a metal oxide produced by decomposition of the metal compound used as a coupling agent and a sintering aid. Have a structure.
【００１７】[0017]
【作用】本発明で用いるＩＴＯ粉末は、市販品を利用し
てもよく、あるいは公知の方法(例えば、錫とインジウ
ムの塩化物の酸性水溶液をアルカリで中和して、錫／イ
ンジウム水酸化物を共沈させ、この共沈物を焼成する)
で製造することもできる。ＩＴＯ粉末は、 (In＋Sn) の
合計量に対するSnの含有量が１〜15原子％の範囲のもの
が、特に低抵抗であるので好ましい。Sn含有量がこの範
囲を外れると、ＩＴＯ粉末自体の抵抗 (体積抵抗値) が
高くなる傾向がある。また、ＩＴＯ粉末の平均一次粒子
径は、形成された膜の透明性を阻害しないように、0.5
μｍ以下、特に0.2 μｍ以下であることが好ましい。The ITO powder used in the present invention may be a commercially available product, or a known method (for example, tin / indium hydroxide prepared by neutralizing an acidic aqueous solution of tin and indium chloride with an alkali). Co-precipitate and calcine this co-precipitate)
It can also be manufactured in. It is preferable that the ITO powder has a Sn content in the range of 1 to 15 atomic% with respect to the total amount of (In + Sn), since it has a particularly low resistance. If the Sn content deviates from this range, the resistance (volume resistance value) of the ITO powder itself tends to increase. The average primary particle diameter of the ITO powder is 0.5 so as not to impair the transparency of the formed film.
It is preferably not more than μm, particularly preferably not more than 0.2 μm.
【００１８】ＩＴＯ粉末の表面にはＯＨ基などの極性基
が存在し、しかも非常に微細な粒子からなるため、表面
活性が高い。従って、ＩＴＯ粉末は非常に凝集し易く、
溶媒中で分散させるために、分散剤や界面活性剤ではＩ
ＴＯ粉末を完全に分散させることは難しく、たとえ分散
できたとしても、焼成時に導電性に悪影響を及ぼす熱分
解物が生じることが判明した。The surface of the ITO powder has a polar group such as an OH group and is composed of very fine particles, so that the surface activity is high. Therefore, ITO powder is very likely to aggregate,
In order to disperse in a solvent, I
It has been found that it is difficult to completely disperse the TO powder, and even if the TO powder can be dispersed, a thermal decomposition product that adversely affects the conductivity is generated during firing.
【００１９】本発明では、カップリング剤を用いてＩＴ
Ｏ粉末を溶媒中に分散させる。本発明で使用可能なカッ
プリング剤としては、シラン系カップリング剤、チタネ
ート系カップリング剤、およびアルミネート系カップリ
ング剤から選ばれた１種もしくは２種以上を使用するこ
とが好ましい。これらのカップリング剤の例としては、
炭素数１〜８のアルキル基もしくはフェニル基を有する
シラン系カップリング剤、炭素数１〜18のアルキレート
基を有するチタネート系カップリング剤、アルキルホス
ファイト基もしくはアルキルパイロホスフェート基を有
するチタネート系カップリング剤、ならびにアセトアル
コキシ基を有するアルミネート系カップリング剤が代表
的なものとして挙げられる。In the present invention, IT is obtained by using a coupling agent.
Disperse O powder in solvent. As the coupling agent that can be used in the present invention, it is preferable to use one or more selected from silane coupling agents, titanate coupling agents, and aluminate coupling agents. Examples of these coupling agents include:
A silane coupling agent having a C1-8 alkyl group or a phenyl group, a titanate coupling agent having a C1-18 alkylate group, a titanate cup having an alkylphosphite group or an alkylpyrophosphate group. Representative examples include ring agents and aluminate-based coupling agents having an acetoalkoxy group.
【００２０】本発明で使用できるカップリング剤の具体
例としては、メチルトリエトキシシラン、ｎ−プロピル
トリメトキシシラン、イソブチルトリメトキシシラン、
オクチルトリエトキシシラン等の炭素数１〜８のアルキ
ル基を有するシラン系カップリング剤；フェニルトリメ
トキシシラン、フェニルトリエトキシシラン、ジフェニ
ルジエトキシシラン等のフェニル基を有するシラン系カ
ップリング剤；イソプロピルトリイソステアロイルチタ
ネート、イソプロピルトリオクチロイルチタネート等の
炭素数１〜18のアルキレート基を有するチタネート系カ
ップリング剤；テトライソプロピルビス (ジオクチルホ
スファイト) チタネート、テトラオクチルビス (ジドデ
シルホスファイト) チタネート等のアルキルホスファイ
ト基を有するチタネート系カップリング剤；ビス (ジオ
クチルパイロホスフェート) オキシアセテートチタネー
ト、イソプロピルトリス (ジオクチルパイロホスフェー
ト) チタネート等のアルキルパイロホスフェート基を有
するチタネート系カップリング剤；アセトエチルアルミ
ニウムジイソプロピレート、アセトオクチルアルミニウ
ムジイソプロピレート等のアセトアルコキシ基を有する
アルミネート系アルミニウム系カップリング剤が挙げら
れる。Specific examples of the coupling agent usable in the present invention include methyltriethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane,
Silane coupling agents having an alkyl group having 1 to 8 carbon atoms such as octyltriethoxysilane; silane coupling agents having a phenyl group such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane; isopropyltri Titanate coupling agents having an alkylate group having 1 to 18 carbon atoms such as isostearoyl titanate and isopropyl trioctyloyl titanate; tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (didodecyl phosphite) titanate Titanate coupling agents having an alkyl phosphite group; bis (dioctyl pyrophosphate) oxyacetate titanate, isopropyl tris (dioctyl pyrophosphate) titanate, etc. Titanate coupling agent having an Le pyrophosphate group; acetoethyl aluminum diisopropylate, aluminate aluminum coupling agent having a acetoalkoxy groups such as aceto-octyl aluminum diisopropylate and the like.
【００２１】これらのカップリング剤は、ＩＴＯ粉末に
対する親和性の高い極性基 (例、アルコキシ基) と、溶
媒に対する親和性の高い基 (例、アルキル基、フェニル
基)とを有している。カップリング剤の極性基がＩＴＯ
粉末表面の極性基と結合して、粉末表面にカップリング
剤が適度に吸着される結果、粉末の凝集が制御され、同
時にカップリング剤の別の基が溶媒に対して親和性を示
すことにより、ＩＴＯ粉末の溶媒中での分散性が向上す
るものと推測される。また、カップリング剤は有機金属
化合物であるから、焼成中に熱分解して無機金属化合物
に変化し、ＩＴＯ粉末の焼結にも寄与する。しかし、前
述したように、カップリング剤単独では、ＩＴＯ粉末の
粒子間およびこの粒子と基体のガラス間の結合は十分で
はないので、別に後述する焼結助剤も併用する。These coupling agents have a polar group having a high affinity for the ITO powder (eg, an alkoxy group) and a group having a high affinity for the solvent (eg, an alkyl group, a phenyl group). The polar group of the coupling agent is ITO
By coupling with the polar group on the powder surface and moderately adsorbing the coupling agent on the powder surface, the aggregation of the powder is controlled, and at the same time, another group of the coupling agent has an affinity for the solvent. It is presumed that the dispersibility of the ITO powder in the solvent is improved. Further, since the coupling agent is an organic metal compound, it is thermally decomposed during firing to be converted into an inorganic metal compound, which also contributes to the sintering of the ITO powder. However, as described above, the coupling agent alone does not sufficiently bond between the particles of the ITO powder and between the particles and the glass of the substrate. Therefore, a sintering aid to be described later is also used in combination.
【００２２】カップリング剤の使用量は、ＩＴＯ粉末10
0 重量部に対する量で 0.1〜５重量部、好ましくは 0.5
〜３重量部の範囲である。カップリング剤の量が0.1 重
量部未満であると、ＩＴＯ粉末の分散が不十分となり、
ヘーズなどの光学特性が低下する。また、カップリング
剤の量が５重量部を越えるとＩＴＯ粉末への被覆が多く
なり、導電性が悪くなる。The amount of coupling agent used is 10 parts by weight of ITO powder.
0.1-5 parts by weight, preferably 0.5, based on 0 parts by weight
Is in the range of 3 parts by weight. If the amount of the coupling agent is less than 0.1 part by weight, the ITO powder will not be sufficiently dispersed,
Optical characteristics such as haze are deteriorated. On the other hand, if the amount of the coupling agent exceeds 5 parts by weight, the coating on the ITO powder increases and the conductivity deteriorates.
【００２３】本発明で焼結助剤として用いる金属化合物
は、金属の有機酸塩および無機酸塩から選ばれ、これら
の１種または２種以上を使用することができる。これら
の金属化合物は焼成により無機金属化合物に変化して、
ＩＴＯ粉末の粒子間およびこの粒子と基体のガラス間を
結合させ、密着性が良好で高硬度の透明導電膜の形成に
寄与する。The metal compound used as the sintering aid in the present invention is selected from organic acid salts and inorganic acid salts of metals, and one or more of these can be used. These metal compounds are converted to inorganic metal compounds by firing,
The particles of the ITO powder and the particles of the ITO powder are bonded to each other to contribute to the formation of a transparent conductive film having good adhesion and high hardness.
【００２４】この金属化合物としては、無機酸化物に転
換した後の透明性に優れ、膜のヘーズを妨害しない金属
が好ましく、具体的にはCo、Ni、Pb、In、Zn、Al、Fe、
Ti、SnおよびSbから選ばれた金属の化合物を用いること
が好ましい。The metal compound is preferably a metal which is excellent in transparency after being converted into an inorganic oxide and does not interfere with the haze of the film, specifically, Co, Ni, Pb, In, Zn, Al, Fe,
It is preferable to use a compound of a metal selected from Ti, Sn and Sb.
【００２５】焼結助剤として有用な金属化合物の例とし
ては、金属の炭素数１〜20の脂肪族、脂環式、および芳
香族カルボン酸塩 (例えば、オクチル酸インジウム、オ
クチル酸亜鉛、酪酸錫、ナフテン酸コバルト、安息香酸
鉛等) 、ならびに硝酸塩、硫酸塩、リン酸塩などの無機
酸塩 (例えば、硝酸インジウム、硝酸コバルト、硝酸鉛
等) などが代表的なものとして挙げられる。Examples of metal compounds useful as sintering aids include aliphatic, alicyclic, and aromatic carboxylic acid salts of metals having from 1 to 20 carbon atoms (eg, indium octylate, zinc octylate, butyric acid). Representative examples thereof include tin, cobalt naphthenate, lead benzoate, etc.), and inorganic acid salts such as nitrates, sulfates, phosphates (eg, indium nitrate, cobalt nitrate, lead nitrate, etc.).
【００２６】焼結助剤の金属化合物の量は、ＩＴＯ粉末
100 重量部に対する量で、 0.2〜15重量部、好ましくは
0.5〜10重量部の範囲である。この金属化合物の量が0.
2 重量部未満であると、焼成時のＩＴＯ粉末の焼結性が
不十分となり、導電性、密着性等の膜特性が低下する。
一方、この金属化合物の量が15重量部を越えると、焼成
後の塗膜に金属が出現し、ヘーズが高くなり、密着性が
低下する。The amount of the metal compound of the sintering aid is ITO powder.
0.2 to 15 parts by weight, preferably 100 to 100 parts by weight, preferably
It is in the range of 0.5 to 10 parts by weight. The amount of this metal compound is 0.
If the amount is less than 2 parts by weight, the sinterability of the ITO powder during firing becomes insufficient, and the film properties such as conductivity and adhesiveness deteriorate.
On the other hand, when the amount of the metal compound exceeds 15 parts by weight, the metal appears in the coating film after firing, the haze increases, and the adhesion decreases.
【００２７】ＩＴＯ粉末を分散させる溶媒としては、メ
タノール、エタノール、イソプロパノール、ブタノール
などのアルコール類、アセトン、メチルエチルケトン、
ジアセトンアルコール、シクロヘキサノン、イソホロン
等のケトン類、トルエン、キシレン、ヘキサン、シクロ
ヘキサン等の炭化水素類、N,N-ジメチルホルムアミド、
N,N-ジメチルアセトアミド等のアミド類ならびに水など
が挙げられる。溶媒は、使用するカップリング剤が溶解
し、かつ焼結助剤の金属化合物が溶解もしくは安定に分
散するように、これらの種類に応じて、１種もしくは２
種以上を選択して用いる。溶媒の量は特に制限されず、
塗布に適した粘度の組成物が得られるような量であれば
よい。通常は、組成物の固形分が５〜60重量％の範囲と
なるような使用量が適当である。As a solvent for dispersing the ITO powder, alcohols such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone,
Ketones such as diacetone alcohol, cyclohexanone and isophorone, hydrocarbons such as toluene, xylene, hexane and cyclohexane, N, N-dimethylformamide,
Examples thereof include amides such as N, N-dimethylacetamide and water. The solvent may be 1 type or 2 types depending on these types so that the coupling agent used is dissolved and the metal compound of the sintering aid is dissolved or stably dispersed.
Select and use at least one species. The amount of solvent is not particularly limited,
The amount may be such that a composition having a viscosity suitable for coating is obtained. Usually, the amount used is such that the solid content of the composition is in the range of 5 to 60% by weight.
【００２８】上記のＩＴＯ粉末、溶媒、カップリング
剤、および焼結助剤の金属化合物を用いて導電膜形成用
組成物を調製するのであるが、本発明においては、１液
型と２液型の２種類の形態の導電膜形成用組成物が可能
である。A conductive film forming composition is prepared by using the above-mentioned ITO powder, a solvent, a coupling agent, and a metal compound of a sintering aid. In the present invention, the one-pack type and the two-pack type are used. The following two types of compositions for forming a conductive film are possible.
【００２９】１液型の本発明の導電膜形成用組成物は、
カップリング剤と焼結助剤の金属化合物が溶解あるいは
分散した溶液中にＩＴＯ粉末を分散させることにより調
製できる。各成分とも１種もしくは２種以上を使用でき
る。混合は、従来より塗料の調製に利用されてきた任意
の手段により実施できる。所望により、上記以外の任意
添加成分をこの組成物にさらに含有させることもでき
る。このような添加成分の例には、界面活性剤、レベリ
ング剤等が挙げられるが、これらを多量に添加すること
は好ましくなく、通常は導電膜形成用組成物の固形分の
５重量％以下が望ましい。The one-component type conductive film-forming composition of the present invention is
It can be prepared by dispersing ITO powder in a solution in which a coupling agent and a metal compound of a sintering aid are dissolved or dispersed. Each component may be used alone or in combination of two or more. Mixing can be carried out by any means conventionally used in the preparation of paints. If desired, optional components other than the above may be further contained in the composition. Examples of such an additive component include a surfactant and a leveling agent, but it is not preferable to add a large amount of these, and usually 5% by weight or less of the solid content of the conductive film-forming composition is used. desirable.
【００３０】得られた導電膜形成用組成物を、基板のガ
ラス板、好ましくは無アルカリガラス板に塗布し、300
℃以上、好ましくは 350〜550 ℃の不活性または還元性
雰囲気中で焼成すると、透明導電膜が形成される。塗布
方法は、スピンコート、ロールコート、スプレーコー
ト、フローコートなどの常法により実施すればよい。焼
成雰囲気の例は、窒素、アルゴン等の不活性ガス雰囲
気、またはこの不活性ガスと水素との混合ガスからなる
還元性ガス雰囲気である。焼成時間は特に制限されない
が、通常は 0.5〜２時間の範囲である。塗布厚みは乾燥
膜厚で0.05〜5.0 μｍの範囲が好ましい。The obtained conductive film-forming composition is applied to a glass plate of a substrate, preferably a non-alkali glass plate,
A transparent conductive film is formed by baking in an inert or reducing atmosphere at a temperature of not less than ℃, preferably 350 to 550 ℃. The coating method may be a conventional method such as spin coating, roll coating, spray coating, or flow coating. Examples of the firing atmosphere are an inert gas atmosphere such as nitrogen and argon, or a reducing gas atmosphere composed of a mixed gas of this inert gas and hydrogen. The firing time is not particularly limited, but is usually in the range of 0.5 to 2 hours. The coating thickness is preferably a dry film thickness in the range of 0.05 to 5.0 μm.
【００３１】２液型の本発明の導電膜形成用組成物で
は、ＩＴＯ粉末、溶媒、およびカップリング剤を混合し
たＡ液 (カップリング剤が溶解した溶媒中にＩＴＯ粉末
が分散した分散液) と、焼結助剤の金属化合物と溶媒を
混合したＢ液 (溶媒中に金属化合物が溶解ないし分散し
た液) とを調製する。In the two-pack type composition for forming a conductive film of the present invention, a liquid A in which ITO powder, a solvent, and a coupling agent are mixed (a dispersion liquid in which the ITO powder is dispersed in a solvent in which the coupling agent is dissolved) And a solution B (a solution in which the metal compound is dissolved or dispersed in the solvent) prepared by mixing the metal compound of the sintering aid with the solvent.
【００３２】前述したように、所望により、焼結助剤の
金属化合物の一部をＡ液中に配合してもよい。したがっ
て、金属化合物の含有量が比較的少ない上記１液型の本
発明の導電膜形成用組成物をＡ液として使用することも
できる。As mentioned above, if desired, a part of the metal compound of the sintering aid may be mixed in the liquid A. Therefore, the one-pack type conductive film-forming composition of the present invention having a relatively small content of the metal compound can also be used as the liquid A.
【００３３】このＡ液を、基板のガラス板上に塗布し、
必要に応じ乾燥させる。その後、得られた塗膜にＢ液を
含浸させる。この含浸は、Ｂ液を塗布するか、或いはＡ
液を塗布したガラス板をＢ液中に浸漬することにより実
施できる。塗布法は上記と同様でよい。塗膜へのＢ液の
含浸量は、１液型の場合と同様に、塗膜中のＩＴＯ粉末
100 重量部に対するＢ液中の金属化合物の量が、 0.2〜
15重量部、好ましくは0.5〜10重量部となる量である。
Ｂ液の含浸後は、上記と同様の条件で焼成を行う。This solution A is applied on the glass plate of the substrate,
Dry if necessary. Then, the obtained coating film is impregnated with the liquid B. For this impregnation, the solution B is applied or the solution A
It can be carried out by immersing the glass plate coated with the liquid in the liquid B. The coating method may be the same as above. The amount of the liquid B impregnated into the coating film is the same as in the case of the one-pack type ITO powder in the coating film.
The amount of the metal compound in the liquid B is 0.2 to 100 parts by weight.
The amount is 15 parts by weight, preferably 0.5 to 10 parts by weight.
After impregnation with the liquid B, firing is performed under the same conditions as above.
【００３４】前述したように、２液型の導電膜形成用組
成物のＡ液とＢ液とを塗布前に混合して使用することも
できる。その場合、Ａ液とＢ液との混合比率は、混合後
のＩＴＯ粉末100 重量部に対する金属化合物の量が 0.2
〜15重量部の範囲内となるような比率とする。この混合
により、前述した１液型の導電膜形成用組成物が得られ
るので、これを１液型の導電膜形成用組成物と同様に塗
布し、焼成する。As described above, the liquid A and the liquid B of the two-component type conductive film forming composition may be mixed and used before coating. In that case, the mixing ratio of the liquid A and the liquid B was such that the amount of the metal compound was 0.2 per 100 parts by weight of the ITO powder after mixing.
The ratio should be within the range of up to 15 parts by weight. By this mixing, the above-described one-component type conductive film-forming composition is obtained. Therefore, this is applied and baked in the same manner as the one-component type conductive film-forming composition.
【００３５】１液型と２液型のいずれの導電膜形成用組
成物を使用した場合にも、焼成前の塗膜においては、カ
ップリング剤がＩＴＯ粉末表面に吸着することによっ
て、ＩＴＯ粉末が低ヘーズ化に十分な程度まで分散し、
この分散したＩＴＯ粉末間の間隙に焼結助剤の金属化合
物が存在している。そして、焼成によって、カップリン
グ剤と焼結助剤は分解し、これらの化合物の分解により
生成した無機金属化合物を介してＩＴＯ粉末同士が融着
し、ＩＴＯ粉末の焼結が行われる。すなわち、カップリ
ング剤と焼結助剤の分解生成物である無機金属化合物に
よってＩＴＯ粉末の粒子間およびＩＴＯ粉末とガラス基
体との間が結合することによって、基体に密着し、かつ
一体化した透明導電膜がガラス板上に形成される。な
お、分解により生成した無機金属化合物には、導電性を
著しく低下させない範囲で有機物が多少残存していても
よい。In both cases of using the one-component type or the two-component type conductive film forming composition, in the coating film before firing, the coupling agent adsorbs on the surface of the ITO powder, whereby the ITO powder is removed. Disperse to a degree sufficient for low haze,
A metal compound as a sintering aid is present in the gaps between the dispersed ITO powders. Then, the firing decomposes the coupling agent and the sintering aid, and the ITO powders are fused to each other through the inorganic metal compound generated by the decomposition of these compounds, whereby the ITO powders are sintered. That is, the inorganic metal compound, which is a decomposition product of the coupling agent and the sintering aid, bonds between the particles of the ITO powder and between the ITO powder and the glass substrate, thereby adhering to the substrate and integrating the transparent material. A conductive film is formed on the glass plate. It should be noted that some organic substances may remain in the inorganic metal compound generated by decomposition so long as the conductivity is not significantly reduced.
【００３６】焼成温度を300 ℃以上とすることにより、
特に粒界における酸素原子の移動拡散が促進され、それ
に伴う結晶成長を利用してＩＴＯ粉末間の結合を強固に
することができる。そのため、ヘーズを低く保ったま
ま、導電性、密着性および膜硬度が著しく向上した透明
導電膜被覆ガラス板が得られる。By setting the firing temperature to 300 ° C. or higher,
In particular, the migration and diffusion of oxygen atoms at the grain boundaries are promoted, and the crystal growth associated therewith can be utilized to strengthen the bonds between the ITO powders. Therefore, it is possible to obtain a transparent conductive film-covered glass plate having significantly improved conductivity, adhesion and film hardness while keeping the haze low.
【００３７】[0037]
【実施例】次に本発明を実施例により具体的に説明す
る。なお、実施例で使用したＩＴＯ粉末は、いずれも
(In＋Sn) の合計量に対するSn含有量が５原子％、平均
一次粒子径0.05μｍの粉末である。EXAMPLES Next, the present invention will be specifically described by way of examples. The ITO powders used in the examples are all
This is a powder having a Sn content of 5 atomic% with respect to the total amount of (In + Sn) and an average primary particle diameter of 0.05 μm.
【００３８】(実施例１)本実施例は、本発明にかかる１
液型の導電膜形成用組成物を用いた透明導電膜被覆ガラ
ス板の製造を例示する。(Embodiment 1) This embodiment relates to the present invention 1
The production of a transparent conductive film-coated glass plate using a liquid type conductive film forming composition will be illustrated.
【００３９】ＩＴＯ粉末を表１に示す種類および割合の
溶媒、カップリング剤、および焼結助剤の金属化合物と
ともに (以上の成分の合計量＝100 ｇ) 250 ccの容器に
入れ、直径 0.3〜0.6 mmのジルコニアビーズ (ミクロハ
イカ、昭和シェル石油製)100ｇを加え、ペイントシェー
カーで３時間混合してＩＴＯ粉末を分散させることによ
り、１液型の導電膜形成用組成物を得た。ビーズを除去
した後、組成物のＩＴＯ粉末の分散状態を目視観察によ
り評価した。The ITO powder was put in a 250 cc container together with the solvent, the coupling agent, and the metal compound of the sintering aid in the types and ratios shown in Table 1 (the total amount of the above components = 100 g), and the diameter of 0.3 to 0.6 g of zirconia beads (Micro-Hika, Showa Shell Sekiyu KK) (100 g) was added, and the mixture was mixed for 3 hours with a paint shaker to disperse the ITO powder to obtain a one-pack type conductive film-forming composition. After removing the beads, the dispersion state of the ITO powder of the composition was evaluated by visual observation.
【００４０】こうして調製した各導電膜形成用組成物を
傾斜させたガラス板 (厚さ２mm、ヘーズ0.0 ％) にフロ
ーコート法により塗布し、表１に記載した温度および雰
囲気で１時間焼成して、ガラス板上に透明導電膜を形成
した。焼成前の塗膜中のＩＴＯ粉末100 重量部に対する
カップリング剤と金属化合物の量も表１に示す。Each of the conductive film-forming compositions thus prepared was applied to a tilted glass plate (thickness: 2 mm, haze: 0.0%) by a flow coating method, and baked at the temperature and atmosphere shown in Table 1 for 1 hour. A transparent conductive film was formed on the glass plate. Table 1 also shows the amounts of the coupling agent and the metal compound with respect to 100 parts by weight of the ITO powder in the coating film before baking.
【００４１】得られた透明導電膜の表面抵抗値を四探針
法 (ロレスタAP: 三菱油化) により、ヘーズをヘーズメ
ーター(HGM−3D：スガ試験機) により測定した。また、
膜厚をＳＥＭ断面写真より、密着性を１mm/mm 基盤目ク
ロスカット・セロファンテープ剥離法 (升目数100)よ
り、膜硬度を鉛筆硬度法により求めた。これらの測定結
果も表１に示す。The surface resistance of the obtained transparent conductive film was measured by the four-point probe method (Loresta AP: Mitsubishi Yuka), and the haze was measured by a haze meter (HGM-3D: Suga Tester). Also,
The film thickness was determined from the SEM cross-sectional photograph, and the adhesiveness was determined by the 1 mm / mm substrate cross-cut cellophane tape peeling method (100 squares), and the film hardness was determined by the pencil hardness method. The results of these measurements are also shown in Table 1.
【００４２】比較のために、導電膜形成用組成物の組成
が本発明の範囲外であるか、焼成条件が本発明の範囲外
である比較例の実験も行った。その試験条件および試験
結果も表１に併せて示す。For comparison, an experiment of a comparative example in which the composition of the conductive film-forming composition was outside the scope of the present invention or the firing conditions were outside the scope of the present invention was also conducted. The test conditions and test results are also shown in Table 1.
【００４３】なお、表１で使用した溶媒、カップリング
剤、有機金属化合物および無機金属化合物の記号の意味
は次の通りであり、カッコ内の比率は重量比である。 １）溶媒 Ａ：キシレン Ｂ：キシレン／ジアセトンアルコール (70/30) Ｃ：キシレン／ジアセトンアルコール／アセチルアセト
ン (65/30/5) ２）カップリング剤 Ｄ：ビス (ジオクチルパイロホスフェート) オキシアセ
テートチタネート Ｅ：テトラオクチルビス (ジトリデシルホスファイト)
チタネート Ｆ：イソプロピルトリイソステアロイルチタネート Ｇ：アセトステアリルアルミニウムジイソプロピレート Ｈ：オクチルトリメトキシシラン Ｉ：ジフェニルジメトキシシラン Ｊ：Ｄ＋Ｅ (50/50) ３）有機金属化合物 Ｋ：オクチル酸In／ナフテン酸Fe (95/5) Ｌ：オクチル酸In／オクチル酸Sn (95/5) Ｍ：オクチル酸In／オクチル酸Sb (95/5) Ｎ：オクチル酸In／オクチル酸Al／オクチル酸Ti (95/3
/2) ４) 無機金属化合物 Ｐ：硝酸In／硝酸Co (80/20) ５) バインダー樹脂 三菱レーヨン製アクリル樹脂LR 980 (樹脂固形分38wt
％) 。The symbols of the solvent, coupling agent, organic metal compound and inorganic metal compound used in Table 1 have the following meanings, and the ratios in parentheses are weight ratios. 1) Solvent A: Xylene B: Xylene / Diacetone Alcohol (70/30) C: Xylene / Diacetone Alcohol / Acetylacetone (65/30/5) 2) Coupling Agent D: Bis (dioctyl pyrophosphate) Oxyacetate titanate E: Tetraoctyl bis (ditridecyl phosphite)
Titanate F: Isopropyltriisostearoyl titanate G: Acetostearyl aluminum diisopropylate H: Octyltrimethoxysilane I: Diphenyldimethoxysilane J: D + E (50/50) 3) Organometallic compound K: Inoctyl acid In / naphthenic acid Fe ( 95/5) L: In octyl acid / Sn octyl acid (95/5) M: In octyl acid / Sb (95/5) N: In octyl acid / Al octyl acid / Ti octyl acid (95/3)
/ 2) 4) Inorganic metal compound P: In nitrate nitrate / Co nitrate (80/20) 5) Binder resin Mitsubishi Rayon acrylic resin LR 980 (resin solid content 38wt)
%).
【００４４】[0044]
【表１】 [Table 1]
【００４５】表１に示すように、本発明に従って実施例
では、ヘーズ１％以下、表面抵抗値101〜102 Ω／□
(ほとんどは101 Ω／□台) 、密着性 100/100、鉛筆硬
度４Ｈ以上という低ヘーズ、低抵抗で密着性、硬度に優
れた導電膜を形成することができた。これに対し、焼成
温度が300 ℃未満であるか、カップリング剤または焼結
助剤の量が範囲外である比較例では、透明性 (ヘーズ)
、導電性、密着性、膜硬度がいずれも低下した。ま
た、従来法によりバインダー樹脂を用いて得た透明導電
膜も、ヘーズ、導電性、密着性がすべて劣っていた。As shown in Table 1, in the examples according to the present invention, the haze was 1% or less, and the surface resistance value was 10 1 to 10 2 Ω / □.
(Mostly 10 1 Ω / □ platform), adhesion 100/100, low haze as more pencil hardness 4H, adhesion at low resistance, it was possible to form an excellent conductive film hardness. On the other hand, in Comparative Examples in which the firing temperature is less than 300 ° C or the amount of the coupling agent or the sintering aid is out of the range, the transparency (haze)
, Conductivity, adhesion, and film hardness were all decreased. Also, the transparent conductive film obtained by using the binder resin by the conventional method was inferior in all of haze, conductivity and adhesion.
【００４６】(実施例２)本実施例では、本発明にかかる
２液型の導電膜形成用組成物と、この組成物を用いた透
明導電膜被覆ガラス板の製造を例示する。(Example 2) In this example, the two-component type conductive film forming composition of the present invention and the production of a transparent conductive film-coated glass plate using this composition are illustrated.
【００４７】ＩＴＯ粉末を、表２のＡ液の欄に示す種類
および割合の溶媒およびカップリング剤とともに (以上
の成分の合計量＝100 ｇ) 250 ccの容器に入れ、直径0.
3 〜0.6 mmのジルコニアビーズ (ミクロハイカ、昭和シ
ェル石油製) 100 ｇを加えペイントシェーカーで３時間
混合してＩＴＯ粉末を分散させることにより、塗布用Ｉ
ＴＯ粉末分散液 (Ａ液) を得た。また、実施例１の試験
No.4で得たＩＴＯ分散液もＡ液として使用した。ビーズ
を除去した後、このＡ液のＩＴＯ粉末の分散状態は目視
で評価した。The ITO powder was placed in a 250 cc container together with the solvent and the coupling agent of the types and proportions shown in the column of liquid A in Table 2 (total amount of the above components = 100 g), and the diameter was adjusted to 0.
By adding 100 g of 3 to 0.6 mm zirconia beads (Micro-Hika, Showa Shell Sekiyu) and mixing with a paint shaker for 3 hours to disperse the ITO powder, coating I
A TO powder dispersion (Liquid A) was obtained. Also, the test of Example 1
The ITO dispersion liquid obtained in No. 4 was also used as the A liquid. After removing the beads, the dispersion state of the ITO powder of this liquid A was visually evaluated.
【００４８】別に、表２のＢ液の欄に示す種類および割
合で焼結助剤の有機および／または無機金属化合物を溶
媒に溶解あるいは分散させることにより、含浸用組成物
(Ｂ液) を調製した。Separately, the impregnating composition was prepared by dissolving or dispersing the organic and / or inorganic metal compound of the sintering aid in the solvent in the types and proportions shown in the column of liquid B in Table 2.
(Solution B) was prepared.
【００４９】上記の各Ａ液を傾斜させたガラス板 (厚さ
２mm、ヘーズ0.0 ％) にフローコート法により塗布し、
風乾により塗膜を乾燥させた後、得られた塗膜上にＢ液
を再度フローコート法により塗布して塗膜に含浸させ、
乾燥させた。含浸後の乾燥塗膜中のＩＴＯ粉末100 重量
部に対するカップリング剤と金属化合物の量を表２に示
す。その後、表２に記載した温度および雰囲気で１時間
焼成して、ガラス板上に透明導電膜を形成した。得られ
た導電膜の表面抵抗値、ヘーズ、膜厚、密着性および硬
度を実施例１と同様に測定した結果も表２に併せて示
す。Each of the above liquids A was applied to a tilted glass plate (thickness 2 mm, haze 0.0%) by a flow coating method,
After the coating film is dried by air drying, the solution B is applied again to the obtained coating film by the flow coating method to impregnate the coating film,
Dried. Table 2 shows the amounts of the coupling agent and the metal compound with respect to 100 parts by weight of the ITO powder in the dried coating film after the impregnation. Then, the transparent conductive film was formed on the glass plate by firing at the temperature and atmosphere shown in Table 2 for 1 hour. Table 2 also shows the results of measuring the surface resistance value, haze, film thickness, adhesion and hardness of the obtained conductive film in the same manner as in Example 1.
【００５０】[0050]
【表２】 [Table 2]
【００５１】表２からわかるように、本発明に従った実
施例では、２液型の導電膜形成用組成物とし、ＩＴＯ粉
末とカップリング剤成分を含有するＡ液から得られた塗
膜に、焼結助剤の金属化合物を含むＢ液を含浸させて焼
成するという膜形成方法でも、実施例１の１液型組成物
の場合に匹敵する性能を備えた、導電性、密着性、透明
性および硬度のいずれにも優れた透明導電膜を得ること
ができた。As can be seen from Table 2, in the examples according to the present invention, a two-pack type conductive film forming composition was used, and a coating film obtained from the liquid A containing the ITO powder and the coupling agent component was used. Even in the film forming method of impregnating and baking the liquid B containing a metal compound as a sintering aid, the film has a performance comparable to that of the one-pack composition of Example 1, and has conductivity, adhesion, and transparency. It was possible to obtain a transparent conductive film having excellent properties and hardness.
【００５２】[0052]
【発明の効果】本発明の導電膜形成用組成物は、バイン
ダーを用いた従来の導電膜形成用組成物 (導電塗料) に
比べて、透明性、導電性、密着性、および塗膜硬度のい
ずれにも優れた、ガラス質の透明導電膜を形成すること
ができる。その結果、塗布法という簡便かつ効率的な方
法により、0.05〜5.0 μｍの膜厚で、表面抵抗値が 101
〜103 Ω／□台、好ましくは 101〜102 Ω／□台、さら
に好ましくは101 Ω／□台、ヘーズが２％以下、好まし
くは１％以下、密着性 (１mm/mm 基盤目クロスカットセ
ロテープ剥離) が95/100以上、好ましくは100/100 、鉛
筆硬度が４Ｈ以上という優れた特性を示す透明導電膜被
覆ガラス板を製造することができる。EFFECTS OF THE INVENTION The conductive film-forming composition of the present invention has higher transparency, conductivity, adhesiveness, and coating film hardness than the conventional conductive film-forming composition using a binder (conductive paint). It is possible to form a vitreous transparent conductive film which is excellent in both cases. As a result, a simple and efficient coating method was used to obtain a surface resistance value of 10 1 at a film thickness of 0.05 to 5.0 μm.
To 10 3 Ω / □, preferably 10 1 to 10 2 Ω / □, more preferably 10 1 Ω / □, haze 2% or less, preferably 1% or less, adhesion (1 mm / mm substrate It is possible to produce a transparent conductive film-coated glass plate having excellent characteristics such as a cross-cut cellophane tape peeling ratio) of 95/100 or more, preferably 100/100, and a pencil hardness of 4H or more.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西原 明 埼玉県大宮市北袋町１丁目297番地 三菱 マテリアル株式会社中央研究所内 (72)発明者 石原 真興 栃木県宇都宮市富士見ヶ丘２−９−16 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akira Nishihara 1-297 Kitabukuro-cho, Omiya City, Saitama Mitsubishi Materials Corporation Central Research Laboratory (72) Inventor Maoki Ishihara 2-9-16 Fujimigaoka, Utsunomiya City, Tochigi Prefecture
Claims (7)
媒、カップリング剤、ならびに金属の有機酸塩および無
機酸塩より選ばれた金属化合物、からなる無バインダー
の導電膜形成用組成物であって、前記酸化インジウム粉
末100 重量部に対して前記カップリング剤を 0.1〜５重
量部、前記金属化合物を 0.2〜15重量部の割合で含有す
ることを特徴とする導電膜形成用組成物。1. A binder-free composition for forming a conductive film, comprising indium oxide powder containing tin, a solvent, a coupling agent, and a metal compound selected from organic acid salts and inorganic acid salts of metals. A composition for forming a conductive film, which comprises 0.1 to 5 parts by weight of the coupling agent and 0.2 to 15 parts by weight of the metal compound with respect to 100 parts by weight of the indium oxide powder.
媒、ならびに前記粉末100 重量部に対して 0.1〜５重量
部の量のカップリング剤からなるＡ液と、金属の有機酸
塩および無機酸塩より選ばれた金属化合物と溶媒とから
なるＢ液とから構成される、無バインダーの２液型の導
電膜形成用組成物。2. Liquid A comprising tin-containing indium oxide powder, a solvent, and a coupling agent in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the powder, and organic and inorganic acid salts of metals. A binder-free two-component conductive film-forming composition composed of a liquid B selected from a metal compound selected from the above and a solvent.
酸塩より選ばれた金属化合物を前記粉末100 重量部に対
して15重量部より少ない量でさらに含有している、請求
項２記載の導電膜形成用組成物。3. The liquid A further contains a metal compound selected from an organic acid salt and an inorganic acid salt of a metal in an amount of less than 15 parts by weight based on 100 parts by weight of the powder. The composition for forming a conductive film as described above.
ング剤、チタネート系カップリング剤、およびアルミネ
ート系カップリング剤より選ばれ、前記金属化合物がC
o、Ni、Pb、In、Zn、Al、Fe、Ti、SnおよびSbより選ば
れた金属の化合物である、請求項１、２または３記載の
導電膜形成用組成物。4. The coupling agent is selected from a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, and the metal compound is C
The composition for forming a conductive film according to claim 1, 2 or 3, which is a compound of a metal selected from o, Ni, Pb, In, Zn, Al, Fe, Ti, Sn and Sb.
成物をガラス板に塗布し、300 ℃以上の不活性または還
元性雰囲気中で焼成することからなる、透明導電膜被覆
ガラス板の製造方法。5. A transparent conductive film-coated glass plate, which comprises applying the composition for forming a conductive film according to claim 1 or 4 to a glass plate and baking the composition in an inert or reducing atmosphere at 300 ° C. or higher. Production method.
用組成物のＡ液をガラス板に塗布した後、得られた塗膜
に、この導電膜形成用組成物のＢ液を、含浸後の塗膜中
の前記金属化合物の量が前記粉末100 重量部に対して
0.2〜15重量部となるように含浸させ、300 ℃以上の不
活性または還元性雰囲気中で焼成することからなる、透
明導電膜被覆ガラス板の製造方法。6. A solution of the conductive film-forming composition according to claim 2, 3 or 4 is applied to a glass plate, and then the solution B of the conductive film-forming composition is added to the obtained coating film. The amount of the metal compound in the coating film after impregnation is 100 parts by weight of the powder.
A process for producing a transparent conductive film-coated glass plate, which comprises impregnating the glass plate with 0.2 to 15 parts by weight and baking in an inert or reducing atmosphere at 300 ° C or higher.
ング剤、チタネート系カップリング剤、およびアルミネ
ート系カップリング剤より選ばれ、前記金属化合物がC
o、Ni、Pb、In、Zn、Al、Fe、Ti、SnおよびSbより選ば
れた金属の化合物である、請求項５または６記載の透明
導電膜被覆ガラス板の製造方法。7. The coupling agent is selected from a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, and the metal compound is C
7. The method for producing a transparent conductive film-coated glass plate according to claim 5, which is a compound of a metal selected from o, Ni, Pb, In, Zn, Al, Fe, Ti, Sn and Sb.
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|---|---|---|---|
| JP01098395A JP3473146B2 (en) | 1995-01-26 | 1995-01-26 | Composition for forming conductive film and method for producing transparent conductive film-coated glass plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01098395A JP3473146B2 (en) | 1995-01-26 | 1995-01-26 | Composition for forming conductive film and method for producing transparent conductive film-coated glass plate |
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|---|---|
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| JP3473146B2 JP3473146B2 (en) | 2003-12-02 |
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ID=11765394
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