JPH05186718A - Conductive coating composition and production of conductive coating film - Google Patents
Conductive coating composition and production of conductive coating filmInfo
- Publication number
- JPH05186718A JPH05186718A JP155692A JP155692A JPH05186718A JP H05186718 A JPH05186718 A JP H05186718A JP 155692 A JP155692 A JP 155692A JP 155692 A JP155692 A JP 155692A JP H05186718 A JPH05186718 A JP H05186718A
- Authority
- JP
- Japan
- Prior art keywords
- conductive coating
- coating film
- solvent
- tin oxide
- coupling agent
- 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
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は導電性塗料組成物に関
し、さらに詳しくはガラス、セラミックスなどの基材面
上に透明性に優れた導電膜を形成するのに好適な導電塗
料組成物およびこれを用いた導電塗膜の製造法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive coating composition, and more particularly to a conductive coating composition suitable for forming a conductive film having excellent transparency on the surface of a substrate such as glass or ceramics. Relates to a method for producing a conductive coating film.
【０００２】[0002]
【従来の技術】近年、帯電防止を目的として、テレビの
ブラウン管や各種のＯＡ機器のディスプレーのガラス面
上に導電性の塗膜が形成されている。この方法には、水
酸基含有ポリマー、高級アルコール、界面活性剤などの
有機物を塗布する方法があるが、この方法では耐溶剤性
および耐擦傷性が劣るため、帯電防止効果の寿命が短く
実用的でない。またその他の方法として、無機系材料を
用いた帯電防止膜の形成が試みられている。例えば特開
昭６２−１８７１８８号公報には、加水分解可能なスズ
化合物やアンチモンドープスズ化合物を加水分解して微
粒子を得た後、水を除去し、エタノール中に分散し焼成
する方法が開示されている。しかし、この方法ではバイ
ンダーを含まないため耐擦傷性に劣るという欠点があ
る。特開昭６２−２５２４８１号公報には、導電性粉
末、バインダー、溶剤から成る組成物が開示されている
が、バインダーが有機系のため耐擦傷性に限界がある。
特開平１−２９９８８７号公報には、酸化スズ微粒子、
シリカゾル、有機溶剤からなる帯電防止処理液が開示さ
れているが、本液は加熱硬化タイプのため、ブラウン管
表面の薄い帯電防止膜を完全硬化するにはブラウン管全
体を加熱しなければならず、エネルギー効率上望ましく
なく、かつ、加熱、冷却に多大な時間を要する。2. Description of the Related Art In recent years, a conductive coating film has been formed on a glass surface of a cathode ray tube of a television or a display of various OA devices for the purpose of preventing static electricity. This method includes a method of applying an organic substance such as a hydroxyl group-containing polymer, a higher alcohol, and a surfactant, but this method has poor solvent resistance and scratch resistance, and therefore has a short life of antistatic effect and is not practical. . As another method, formation of an antistatic film using an inorganic material has been attempted. For example, JP-A-62-187188 discloses a method in which a hydrolyzable tin compound or antimony-doped tin compound is hydrolyzed to obtain fine particles, water is removed, and the particles are dispersed in ethanol and baked. ing. However, this method has a drawback that it is inferior in scratch resistance because it does not contain a binder. Japanese Unexamined Patent Publication (Kokai) No. 62-252481 discloses a composition comprising a conductive powder, a binder and a solvent, but the binder is an organic type, so that the scratch resistance is limited.
Japanese Unexamined Patent Application Publication No. 1-29887 discloses tin oxide fine particles,
An antistatic treatment liquid consisting of silica sol and an organic solvent is disclosed, but since this liquid is a heat-curing type, it is necessary to heat the entire CRT in order to completely cure the thin antistatic film on the surface of the CRT. It is not desirable in efficiency, and it takes a lot of time for heating and cooling.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記従来技
術の問題点を解決し、導電性、透明性、耐溶剤性および
耐擦傷性に優れた導電塗膜を生成する導電塗料組成物及
び導電塗膜の製造法を提供するものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a conductive coating composition which produces a conductive coating film excellent in conductivity, transparency, solvent resistance and scratch resistance, and A method for producing a conductive coating film is provided.
【０００４】[0004]
【課題を解決するための手段】本発明は、（Ａ）下記一
般式（Ｉ）で示されるケイ酸、（Ｂ）アンチモンがドー
プされた粒径が０．２μｍ以下の酸化スズ粉末をシラン
カップリング剤で分散して得られる混合物、（Ｃ）光増
感剤および（Ｄ）溶剤を含有してなる導電塗料組成物並
びに本組成物を基材面上に塗装し、紫外線を照射し硬化
する導電塗膜の製造法に関する。The present invention is directed to (A) silicic acid represented by the following general formula (I), and (B) antimony-doped tin oxide powder having a particle size of 0.2 μm or less. A mixture obtained by dispersing with a ring agent, a conductive coating composition containing (C) a photosensitizer and (D) a solvent, and this composition are coated on the surface of a base material and cured by irradiation with ultraviolet rays. The present invention relates to a method for producing a conductive coating film.
【化２】 （式中、ｎは３〜６の整数である）[Chemical 2] (In the formula, n is an integer of 3 to 6)
【０００５】本発明の（Ａ）成分であるケイ酸は、日本
化学会誌、１９８１、１１５２〜１１５８頁に報告され
ている方法によって容易に得られる。例えば、水ガラ
ス、メタケイ酸ソーダ、ケイ酸アンモニウム等の可溶性
ケイ酸塩の水溶液を酸によって中和処理することによ
り、あるいは陽イオン交換樹脂で処理することにより、
ケイ酸塩類からケイ酸水溶液が得られる。この溶液をテ
トラヒドロフラン、アルコールあるいはケトンで抽出す
ることにより、これらのケイ酸の有機溶剤溶液を調製で
きる。通常は、最も抽出率の高いテトラヒドロフランが
用いられる。The silicic acid which is the component (A) of the present invention can be easily obtained by the method reported in Journal of Chemical Society of Japan, 1981, pp. 1152-1158. For example, water glass, sodium metasilicate, by neutralizing an aqueous solution of a soluble silicate such as ammonium silicate with an acid, or by treating with a cation exchange resin,
A silicic acid aqueous solution is obtained from silicates. An organic solvent solution of these silicic acids can be prepared by extracting this solution with tetrahydrofuran, alcohol or ketone. Tetrahydrofuran, which has the highest extraction rate, is usually used.
【０００６】（Ｂ）成分のアンチモンがドープされた酸
化スズ粉末（以下アンチモンドープ酸化スズ粉末と記
す）は、例えば塩酸の水溶液、アルコール溶液又はこれ
らの混合溶液に塩化スズと塩化アンチモンとを溶解させ
て得られる溶液を、加熱水中に加えて沈殿物を析出さ
せ、これを濾別洗浄したあと、焼成、粉砕することによ
って製造できる。この粉末の粒径は０．２μｍ以下の物
が使用可能であるが、０．０５μｍ以下のものがより好
ましい。粒径が０．２μｍを越えると、薄膜形成が出来
ずかつ透明性が低下し、沈降が生じ易い。アンチモンド
ープ酸化スズ粉末の好適な例としては、三菱金属（株）
製Ｔ−１などがある。The component (B) tin oxide powder doped with antimony (hereinafter referred to as antimony-doped tin oxide powder) is prepared by dissolving tin chloride and antimony chloride in an aqueous solution of hydrochloric acid, an alcohol solution or a mixed solution thereof. The solution thus obtained is added to heated water to precipitate a precipitate, which is filtered and washed, followed by firing and pulverization. Particles having a particle size of 0.2 μm or less can be used, but those having a particle size of 0.05 μm or less are more preferable. If the particle size exceeds 0.2 μm, a thin film cannot be formed, the transparency decreases, and sedimentation easily occurs. Suitable examples of the antimony-doped tin oxide powder include Mitsubishi Metal Co., Ltd.
Manufactured by T-1 and the like.
【０００７】（Ｂ）成分の製造に用いられるシランカッ
プリング剤の例としては、γ−メタクリルオキシプロピ
ルトリメトキシシラン、ビニルトリエトキシシラン、γ
−グリシドキシプロピルトリメトキシシラン等があげら
れる。Examples of the silane coupling agent used for producing the component (B) include γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and γ.
-Glycidoxypropyltrimethoxysilane and the like.
【０００８】酸化スズ粉末を上記一般式（ＩＩ）で示さ
れるシランカップリング剤で分散し、混合物を得る方法
としは、酸化スズ粉末がヘンシェルミキサー、スーパー
ミキサーなどでよく撹拌されている中へシランカップリ
ング剤を噴霧あるいは点滴により添加する乾式法、酸化
スズ粉末を溶剤の存在下にシランカップリング剤と共に
高速撹拌する湿式法、高温状態の酸化スズ粉末にシラン
カップリング剤をスプレーにより噴霧添加するスプレー
法等があるが、粒子全体を均一に処理することができる
湿式法が好ましい。湿式法による分散装置としては、ボ
ールミル、サンドミル、３本ロールなどが用いられる。The tin oxide powder is dispersed with the silane coupling agent represented by the above general formula (II) to obtain a mixture. The tin oxide powder is well stirred in a Henschel mixer, a super mixer or the like. Dry method of adding coupling agent by spraying or drip, Wet method of stirring tin oxide powder with silane coupling agent at high speed in the presence of solvent, Spray addition of silane coupling agent to tin oxide powder in high temperature state Although there is a spray method or the like, a wet method that can uniformly treat the entire particle is preferable. A ball mill, a sand mill, a triple roll, or the like is used as a dispersing device by the wet method.
【０００９】（Ｃ）成分の光増感剤としては、ベンジル
ジメチルケタール、ベンゾフェノン、アセトフェノン
（誘導体）、ベンゾイン（誘導体）など常用の光増感剤
が使用できる。As the photosensitizer of the component (C), a conventional photosensitizer such as benzyl dimethyl ketal, benzophenone, acetophenone (derivative) or benzoin (derivative) can be used.
【００１０】（Ｄ）成分の溶剤としては、アセトン、メ
チルエチルケトンなどのケトン系溶剤、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、ジア
セトンアルコールなどのアルコール系溶剤、酢酸エチ
ル、酢酸ブチルなどのエステル系溶剤、塩化メチレン、
１，１，１−トリクロロエタンなどの塩素系溶剤が使用
可能であるが成膜性の点からメチルエチルケトンを主成
分とすることが好ましい。Examples of the solvent of the component (D) include ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol and diacetone alcohol, ester solvents such as ethyl acetate and butyl acetate, Methylene chloride,
A chlorine-based solvent such as 1,1,1-trichloroethane can be used, but it is preferable to use methyl ethyl ketone as a main component from the viewpoint of film forming property.
【００１１】本発明の導電塗料組成物の固形分は０．１
〜１０重量％の範囲であることが好ましい。０．１重量
％未満では、低抵抗化が不十分で、１０重量％を超える
と耐擦傷性が低下する傾向がある。前記（Ｄ）成分の溶
剤は組成物の固型分が０．１〜１０重量％になるように
配合されることが好ましい。（Ｃ）成分の光増感剤は
（Ｂ）成分のシランカップリング剤１００重量部に対し
０．１〜１０重量部の範囲で使用することが好ましい。
０．１重量部未満では光硬化性が低下し、１０重量部を
超えると耐擦傷性が低下する傾向がある。（Ｂ）成分の
アンチモンドープ酸化スズ粉末をシランカップリング剤
で分散する時の配合比は、シランカップリング剤１００
重量部に対し、アンチモンドープ酸化スズが５０〜２０
００重量部の範囲が好ましい。この範囲以外では、ロー
ル分散が困難である。次に、（Ａ）成分のケイ酸と
（Ｂ）成分のアンチモンドープ酸スズ粉末及びシランカ
ップリング剤の配合比について述べる。ケイ酸１００重
量部に対し、アンチモンドープ酸化スズ粉末は１０〜４
００重量部の範囲で使用することが好ましい。１０重量
部未満では低抵抗化が不十分であり、４００重量部を超
えると耐擦傷性が低下する傾向がある。また、シランカ
ップリング剤の配合比は、ケイ酸とアンチモンドープ酸
スズ粉末の合計１００重量部に対し、０．１〜２００重
量部の範囲が好ましい。０．１重量部未満では、硬化性
が低下し、２００重量部を超えると耐擦傷性が低下する
傾向がある。アンチモンドープ酸化スズ粉末のシランカ
ップリング剤による分散はせん断力の強いロール分散が
好ましいが、サンドグラインダーなどのビーズミルによ
る分散も可能である。アンチモンドープ酸化スズ粉末と
シランカップリング剤の分散液をケイ酸および溶剤に分
散させる場合はビーズミル、超音波分散など通常の分散
法が適用できる。The conductive coating composition of the present invention has a solid content of 0.1.
It is preferably in the range of 10% by weight. If it is less than 0.1% by weight, the resistance reduction is insufficient, and if it exceeds 10% by weight, the scratch resistance tends to be lowered. The solvent of the component (D) is preferably blended so that the solid content of the composition is 0.1 to 10% by weight. The photosensitizer as the component (C) is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the silane coupling agent as the component (B).
If it is less than 0.1 part by weight, the photocurability tends to be low, and if it exceeds 10 parts by weight, the scratch resistance tends to be low. When the antimony-doped tin oxide powder as the component (B) is dispersed with a silane coupling agent, the compounding ratio is 100 silane coupling agent.
Antimony-doped tin oxide is 50 to 20 parts by weight.
A range of 00 parts by weight is preferred. Outside of this range, roll dispersion is difficult. Next, the compounding ratio of the silicic acid as the component (A), the antimony-doped tin acid powder as the component (B), and the silane coupling agent will be described. Antimony-doped tin oxide powder is 10-4 with respect to 100 parts by weight of silicic acid.
It is preferably used in the range of 00 parts by weight. If it is less than 10 parts by weight, the resistance reduction is insufficient, and if it exceeds 400 parts by weight, the scratch resistance tends to decrease. The compounding ratio of the silane coupling agent is preferably in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the total of silicic acid and antimony-doped tin acid powder. If it is less than 0.1 part by weight, the curability tends to decrease, and if it exceeds 200 parts by weight, the scratch resistance tends to decrease. Dispersion of the antimony-doped tin oxide powder with a silane coupling agent is preferably roll dispersion with a strong shearing force, but dispersion with a bead mill such as a sand grinder is also possible. When a dispersion liquid of antimony-doped tin oxide powder and a silane coupling agent is dispersed in silicic acid and a solvent, a usual dispersion method such as bead milling or ultrasonic dispersion can be applied.
【００１２】本発明の導電塗料組成物は、スピンコー
ト、スプレーコート、ロールコート、ディップコートな
どの一般的な塗装方法でガラス、セラミックなどの基材
面上に塗装し、高圧水銀灯、超高圧水銀灯、メタルハラ
イドランプなど一般的な紫外線照射装置で紫外線を照射
し硬化して導電塗膜とされる。加熱硬化も可能であるが
紫外線硬化の方が低温・短時間処理が可能である。処理
膜厚は、耐クラック性の点から、４０μｍ以下とするの
が好ましい。The conductive coating composition of the present invention is applied on the surface of a substrate such as glass or ceramic by a general coating method such as spin coating, spray coating, roll coating or dip coating to obtain a high pressure mercury lamp or an ultra high pressure mercury lamp. A conductive coating film is obtained by irradiating ultraviolet rays with a general ultraviolet ray irradiating device such as a metal halide lamp and curing. It can be cured by heating, but UV curing can be performed at low temperature for a short time. The treated film thickness is preferably 40 μm or less from the viewpoint of crack resistance.
【００１３】[0013]
【実施例】次に実施例を説明する。実施例、比較例の中
で部、％とあるのは重量基準である。 ケイ酸溶液Ａの合成 １ｌのガラス製の４つ口フラスコに、塩酸２０ｇ、水１
２０ｇを仕込み５℃で撹拌しながら、メタケイ酸ナトリ
ウム６０ｇを水１２０ｇに溶解したメタケイ酸ナトリウ
ム水溶液を１時間かけて滴下した。次にテトラヒドロフ
ラン２５０ｇを１時間かけて滴下した。この溶液に塩化
ナトリウム５０ｇを加えた後、テトラヒドロフラン層を
分取して、ケイ酸溶液Ａを得た。この不揮発分を測定し
た結果、８％であった。EXAMPLES Next, examples will be described. In Examples and Comparative Examples, parts and% are based on weight. Synthesis of silicic acid solution A In a 1-liter glass four-necked flask, 20 g of hydrochloric acid and 1 part of water were added.
20 g was charged and an aqueous solution of sodium metasilicate in which 60 g of sodium metasilicate was dissolved in 120 g of water was added dropwise over 1 hour while stirring at 5 ° C. Next, 250 g of tetrahydrofuran was added dropwise over 1 hour. After adding 50 g of sodium chloride to this solution, the tetrahydrofuran layer was separated to obtain a silicic acid solution A. As a result of measuring the nonvolatile content, it was 8%.
【００１４】実施例１ Ｔ−１（三菱マテリアル（株）製アンチモンドープ酸化
スズ粉末の商品名、アンチモンドープ量１０％、一次粒
子の粒径約０．０５μｍ）５０部、ジアセトンアルコー
ル２５部およびγ−メタアクリロキシプロピルトリメト
キシシラン２５部の混合物を３本ロールに３回通し分散
混合物を得た。この混合物１部ケイ酸溶液Ａ３０部、ベ
ンジルジメチルケタール０．００３部、メチルエチルケ
トン６９部をビーズミル（ジルコニアビーズ０．５ｍｍ
φ）で混合撹拌して組成物Ａを得た。これをガラス基板
上に３００ｒｐｍで３０秒スピンコートし、その後超高
圧水銀灯で３０ｍＷ／ｃｍ2の露光照度で１５分照射し
硬化させ導電塗膜を得た。 実施例２ γ−メタアクリロキシトリメトキシシランをビニルトリ
エトキシシランに変えた以外は実施例１と全く同じ方法
で導電塗膜を得た。 比較例１ 組成物Ａからベンジルジメチルケタールを除いた組成物
を実施例１と同様にスピンコートし、その後１６０℃で
３０分間硬化させ導電塗膜を得た。 比較例２ ケイ酸溶液Ａ３０部、Ｔ−１を０．７部、メチルエチル
ケトン６９部をビーズミル（ジルコニアビーズ０．５ｍ
ｍφ）で混合撹拌して組成物Ｂを得た。これより実施例
１と全く同じ硬化方法で導電塗膜を得た。得られた導電
塗膜について、表面抵抗、５５０ｎｍでの透過率、鉛筆
硬度および耐エチルアルコール性を評価した。表１に結
果を示す。Example 1 50 parts of T-1 (trade name of antimony-doped tin oxide powder manufactured by Mitsubishi Materials Corp., antimony doping amount of 10%, primary particle size of about 0.05 μm), 25 parts of diacetone alcohol, and A mixture of 25 parts of γ-methacryloxypropyltrimethoxysilane was passed through a triple roll three times to obtain a dispersion mixture. 1 part of this mixture, 30 parts of silicic acid solution A, 0.003 parts of benzyl dimethyl ketal, 69 parts of methyl ethyl ketone were added to a bead mill (zirconia beads 0.5 mm
φ) was mixed and stirred to obtain a composition A. This was spin-coated on a glass substrate at 300 rpm for 30 seconds and then irradiated with an ultrahigh pressure mercury lamp at an exposure illuminance of 30 mW / cm 2 for 15 minutes to be cured to obtain a conductive coating film. Example 2 A conductive coating film was obtained by the same method as in Example 1 except that γ-methacryloxytrimethoxysilane was changed to vinyltriethoxysilane. Comparative Example 1 A composition obtained by removing benzyl dimethyl ketal from Composition A was spin-coated in the same manner as in Example 1 and then cured at 160 ° C. for 30 minutes to obtain a conductive coating film. Comparative Example 2 30 parts of silicic acid solution A, 0.7 parts of T-1 and 69 parts of methyl ethyl ketone were bead milled (zirconia beads 0.5 m
Composition B was obtained by mixing and stirring with mφ). From this, a conductive coating film was obtained by the same curing method as in Example 1. The obtained conductive coating film was evaluated for surface resistance, transmittance at 550 nm, pencil hardness and ethyl alcohol resistance. The results are shown in Table 1.
【００１５】[0015]
【表１】 [Table 1]
【００１６】＊１、東京電子株式会社製高抵抗計スタッ
クＴＲ−３で測定した。 ＊２、ＵＶ分光光度計で５５０ｎｍの吸光度を測定し
た。 ＊３、ＪＩＳ Ｃ３００３に準じて行った。 ＊４、エチルアルコール中に室温で２４時間浸漬し、外
観の変化を目視で確認した。 ＊５、導電塗膜の外観を肉眼で観察した。 表１から本発明の導電塗料組成物により得られる導電塗
膜は、表面抵抗が低く高透明でかつ鉛筆硬度が硬いため
耐擦傷性に優れまた耐溶剤性に優れていることが示され
る。* 1, measured with a high resistance meter stack TR-3 manufactured by Tokyo Electronics Co., Ltd. * 2, the absorbance at 550 nm was measured with a UV spectrophotometer. * 3, performed according to JIS C3003. * 4: Immersed in ethyl alcohol at room temperature for 24 hours, and visually confirmed changes in appearance. * 5, The appearance of the conductive coating film was visually observed. Table 1 shows that the conductive coating film obtained from the conductive coating composition of the present invention has low surface resistance, high transparency, and high pencil hardness, and thus has excellent scratch resistance and solvent resistance.
【０００１７】[00017]
【発明の効果】本発明の導電塗料組成物を紫外線硬化し
て、導電性、透明性、耐溶剤性、耐擦傷性、鉛筆硬度に
優れた塗膜とすることができる。The conductive coating composition of the present invention can be UV-cured to form a coating film having excellent conductivity, transparency, solvent resistance, scratch resistance and pencil hardness.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年５月１５日[Submission date] May 15, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】（Ｂ）成分の製造に用いられるシランカッ
プリング剤の例としては、γ−メタアクリロキシプロピ
ルトリメトキシシラン、ビニルトリエトキシシラン、γ
−グリシドキシプロピルトリメトキシシラン等があげら
れる。Examples of the silane coupling agent used for producing the component (B) include γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and γ.
-Glycidoxypropyltrimethoxysilane and the like.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】酸化スズ粉末をシランカップリング剤で分
散し、混合物を得る方法としは、酸化スズ粉末がヘンシ
ェルミキサー、スーパーミキサーなどでよく撹拌されて
いる中へシランカップリング剤を噴霧あるいは点滴によ
り添加する乾式法、酸化スズ粉末を溶剤の存在下にシラ
ンカップリング剤と共に高速撹拌する湿式法、高温状態
の酸化スズ粉末にシランカップリング剤をスプレーによ
り噴霧添加するスプレー法等があるが、粒子全体を均一
に処理することができる湿式法が好ましい。湿式法によ
る分散装置としては、ボールミル、サンドミル、３本ロ
ールなどが用いられる。A method for obtaining a mixture by dispersing tin oxide powder with a silane coupling agent is to add the silane coupling agent by spraying or drip in while tin oxide powder is well agitated by a Henschel mixer, a super mixer or the like. There are a dry method, a wet method in which tin oxide powder is rapidly stirred with a silane coupling agent in the presence of a solvent, and a spray method in which a silane coupling agent is spray-added to tin oxide powder in a high temperature state. Is preferably a wet method capable of uniformly treating A ball mill, a sand mill, a triple roll, or the like is used as a dispersing device by the wet method.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】実施例１ Ｔ−１（三菱マテリアル（株）製アンチモンドープ酸化
スズ粉末の商品名、アンチモンドープ量１０％、一次粒
子の粒径約０．０５μｍ）５０部、ジアセトンアルコー
ル２５部およびγ−メタアクリロキシプロピルトリメト
キシシラン２５部の混合物を３本ロールに３回通し分散
混合物を得た。この混合物１部ケイ酸溶液Ａ３０部、ベ
ンジルジメチルケタール０．００３部、メチルエチルケ
トン６９部をビーズミル（ジルコニアビーズ０．５ｍｍ
φ）で混合撹拌して組成物Ａを得た。これをガラス基板
上に３００ｒｐｍで３０秒スピンコートし、その後超高
圧水銀灯で３０ｍＷ／ｃｍ2の露光照度で１５分照射し
硬化させ導電塗膜を得た。 実施例２ γ−メタアクリロキシプロピルトリメトキシシランをビ
ニルトリエトキシシランに変えた以外は実施例１と全く
同じ方法で導電塗膜を得た。 比較例１ 組成物Ａからベンジルジメチルケタールを除いた組成物
を実施例１と同様にスピンコートし、その後１６０℃で
３０分間硬化させ導電塗膜を得た。 比較例２ ケイ酸溶液Ａ３０部、Ｔ−１を０．７部、メチルエチル
ケトン６９部をビーズミル（ジルコニアビーズ０．５ｍ
ｍφ）で混合撹拌して組成物Ｂを得た。これより実施例
１と全く同じ硬化方法で導電塗膜を得た。得られた導電
塗膜について、表面抵抗、５５０ｎｍでの透過率、鉛筆
硬度および耐エチルアルコール性を評価した。表１に結
果を示す。Example 1 50 parts of T-1 (trade name of antimony-doped tin oxide powder manufactured by Mitsubishi Materials Corp., antimony doping amount of 10%, primary particle size of about 0.05 μm), 25 parts of diacetone alcohol, and A mixture of 25 parts of γ-methacryloxypropyltrimethoxysilane was passed through a triple roll three times to obtain a dispersion mixture. 1 part of this mixture, 30 parts of silicic acid solution A, 0.003 parts of benzyl dimethyl ketal, 69 parts of methyl ethyl ketone were added to a bead mill (zirconia beads 0.5 mm
φ) was mixed and stirred to obtain a composition A. This was spin-coated on a glass substrate at 300 rpm for 30 seconds and then irradiated with an ultrahigh pressure mercury lamp at an exposure illuminance of 30 mW / cm 2 for 15 minutes to be cured to obtain a conductive coating film. Example 2 A conductive coating film was obtained in the same manner as in Example 1 except that γ-methacryloxypropyltrimethoxysilane was changed to vinyltriethoxysilane. Comparative Example 1 A composition obtained by removing benzyl dimethyl ketal from Composition A was spin-coated in the same manner as in Example 1 and then cured at 160 ° C. for 30 minutes to obtain a conductive coating film. Comparative Example 2 30 parts of silicic acid solution A, 0.7 parts of T-1 and 69 parts of methyl ethyl ketone were bead milled (zirconia beads 0.5 m
Composition B was obtained by mixing and stirring with mφ). From this, a conductive coating film was obtained by the same curing method as in Example 1. The obtained conductive coating film was evaluated for surface resistance, transmittance at 550 nm, pencil hardness and ethyl alcohol resistance. The results are shown in Table 1.
Claims (2)
酸、（Ｂ）アンチモンがドープされた粒径が０．２μｍ
以下の酸化スズ粉末をシランカップリング剤で分散して
得られる混合物、（Ｃ）光増感剤および（Ｄ）溶剤を含
有してなる導電塗料組成物。 【化１】 （式中、ｎは３〜６の整数である）1. A particle size of 0.2 μm doped with (A) silicic acid represented by the following general formula (I) and (B) antimony:
A conductive coating composition comprising a mixture obtained by dispersing the following tin oxide powder with a silane coupling agent, (C) a photosensitizer and (D) a solvent. [Chemical 1] (In the formula, n is an integer of 3 to 6)
上に塗装し、紫外線を照射し硬化する導電塗膜の製造
法。2. A method for producing a conductive coating film, which comprises coating the conductive coating composition according to claim 1 on the surface of a substrate and irradiating it with ultraviolet rays to cure it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP155692A JPH05186718A (en) | 1992-01-08 | 1992-01-08 | Conductive coating composition and production of conductive coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP155692A JPH05186718A (en) | 1992-01-08 | 1992-01-08 | Conductive coating composition and production of conductive coating film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05186718A true JPH05186718A (en) | 1993-07-27 |
Family
ID=11504802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP155692A Pending JPH05186718A (en) | 1992-01-08 | 1992-01-08 | Conductive coating composition and production of conductive coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05186718A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674625A (en) * | 1993-11-10 | 1997-10-07 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| KR100383086B1 (en) * | 1998-09-08 | 2003-08-21 | 주식회사 엘지화학 | UV-curable coating composition with excellent antistatic properties and adhesion to the conductor |
| JP2009197217A (en) * | 2008-01-21 | 2009-09-03 | Canon Inc | Resin composition and optical element, diffractive optical element and laminated diffractive optical element molded by the same |
-
1992
- 1992-01-08 JP JP155692A patent/JPH05186718A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674625A (en) * | 1993-11-10 | 1997-10-07 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| US5856016A (en) * | 1993-11-10 | 1999-01-05 | Central Glass Company Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| KR100383086B1 (en) * | 1998-09-08 | 2003-08-21 | 주식회사 엘지화학 | UV-curable coating composition with excellent antistatic properties and adhesion to the conductor |
| JP2009197217A (en) * | 2008-01-21 | 2009-09-03 | Canon Inc | Resin composition and optical element, diffractive optical element and laminated diffractive optical element molded by the same |
| US8124324B2 (en) * | 2008-01-21 | 2012-02-28 | Canon Kabushiki Kaisha | Laminated diffractive optical element and resin composition therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3302186B2 (en) | Substrate with transparent conductive film, method for producing the same, and display device provided with the substrate | |
| JP5427093B2 (en) | Uniformly dispersible photocatalyst coating liquid, method for producing the same, and photocatalytically active composite material obtained using the same | |
| JP5057199B2 (en) | Method for producing hollow SiO2 fine particle dispersion, coating composition, and substrate with antireflection coating | |
| JPH06322317A (en) | Coating composition for absorption of ultraviolet ray and its production | |
| WO2017169819A1 (en) | Black photosensitive resin composition | |
| JP5096666B2 (en) | Method for producing chain conductive oxide fine particles, chain conductive oxide fine particles, transparent conductive film-forming coating material, and substrate with transparent conductive film | |
| WO2007058016A1 (en) | Process for producing base material for forming heat shielding film | |
| JP7141885B2 (en) | Surface-treated zirconium nitride powder and its surface treatment method | |
| JP3619724B2 (en) | Molded product having transparent super water-repellent surface and method for producing the same | |
| JP2004204175A (en) | Coating containing colored pigment particle and substrate with visible light-shading film | |
| JP2011132343A (en) | Antistatic hard coating material and optical member | |
| JPH05186718A (en) | Conductive coating composition and production of conductive coating film | |
| JPH06184470A (en) | Production of electrically conductive coating composition and electrically conductive film | |
| JP5284632B2 (en) | Conductive fibrous hollow silica fine particle dispersoid and process for producing the same | |
| JPH06166834A (en) | Conductive coating composition and production of conductive coating film | |
| JPH05239409A (en) | Conductive coating composition and production of conductive coating film | |
| JPH06264009A (en) | Conductive coating composition and production of conductive coating film | |
| JP2002249678A (en) | Resin coated carbon black and color filter | |
| JP2007136362A (en) | Compound coating film structure and coated exterior material | |
| JP7212471B2 (en) | Manufacturing method of zirconium nitride film | |
| JP2637793B2 (en) | Composition for coating | |
| JP4415953B2 (en) | Selective permeable membrane coating solution, selective permeable membrane and selective permeable multilayer membrane | |
| JP2012168377A (en) | Ultraviolet shielding particle, resin composition for ultraviolet shielding hard coat, ultraviolet shielding hard coat film, plastic head lens cover for vehicle | |
| JP2001207079A (en) | Highly resistant carbon black and color filter | |
| KR100268727B1 (en) | Transparent conductive film, manufacturing method thereof and cathode ray tube including the transparent conductive film |