JP3697016B2 - Acicular conductive antimony-containing tin oxide powder aqueous dispersion and conductive paint - Google Patents
Acicular conductive antimony-containing tin oxide powder aqueous dispersion and conductive paint Download PDFInfo
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- tin oxide
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Description
【０００１】
【発明の属する技術分野】
本発明は、新規な針状導電性アンチモン含有酸化錫粉末の水性分散体及びこれを用いた水性系の導電性塗料に関するものである。
【０００２】
【従来の技術】
透明導電材として、特にテレビ、ブラウン管、ＯＨＰやレントゲンフィルム等の透明シート、透明性の要求される包装材等の高度の透明性と帯電防止能が要求される分野で微粒子の球状或いは針状のアンチモン含有酸化錫粉末が用いられている。
【０００３】
これらのアンチモン含有酸化錫粉末を水性系導電性塗料に適用する場合には、該酸化錫粉末もしくは該酸化錫粉末の製造工程から得られる可溶性塩類を除去処理した後の処理ケーキを、水性媒体に分散させてなる水性分散体を調製し、該水性分散体と水溶性樹脂等とを混合して塗料化する。該塗料や紙やゴム、高分子フィルムなどの絶縁性基体に塗布することにより、該基体上に導電性塗膜を形成させることができる。
【０００４】
しかしながら、針状のアンチモン含有酸化錫粉末を配合した水性分散体や導電性塗料には、球状のアンチモン含有酸化錫粉末を配合した場合に比べて、粉末粒子の分散が困難であるという問題点があった。そのために、針状のアンチモン含有酸化錫粉末を用いた場合は、高い導電性を有し、しかも透明性も優れた塗膜を得ることが難しかった。
【０００５】
【発明が解決しようとする課題】
本発明は、針状アンチモン含有酸化錫粉末を含む水性分散体や導電性塗料の上記問題点を解消し、高い導電性を有し透明性も優れた塗膜を得ることを可能とする新規な水性分散体及び水性系の導電性塗料を提供するためになされたものである。
【０００６】
【課題を解決するための手段】
本発明者らは、上記目的を達成するために、鋭意研究を重ねた結果、リン酸イオンを存在させた針状アンチモン含有酸化錫粉末を含む水性分散体や導電性塗料がこの目的に適合することを見出し、この知見に基づいて本発明を完成するに至った。
【０００７】
すなわち、本発明は、分散媒としての水性媒体、針状導電性アンチモン含有酸化錫粉末及びリン酸イオンを含んでなり、リン酸イオンがＰ２Ｏ５として針状導電性アンチモン含有酸化錫粉末の重量基準で０．３〜３％であり、針状導電性アンチモン含有酸化錫粉末が１０〜５０重量％である水性分散体並びに該水性分散体と水溶性樹脂やポリアルコキシシロキサンとを混合させてなる導電性塗料である。
【０００８】
本発明の針状導電性アンチモン含有酸化錫粉末は、SnO2/Sb2O3/SiO2/NaClを焼成する方法（特開平8-231222）或いは、基体粒子としての針状酸化錫粒子の表面に含水酸化アンチモンを沈着した後、焼成することにより得ることができる。
【０００９】
本発明の針状導電性アンチモン含有酸化錫粉末は、短軸平均粒子径が０．００５〜０．０５μｍ、好ましくは０．００５〜０．０２μｍであり、長軸平均粒子径が０．１〜３μｍ、好ましくは０．２〜３μｍであって、軸比が５〜６００であるものが好ましい。
【００１０】
なお、本発明において「針状」とは、上記軸比の範囲における針状のものの他、繊維状、柱状、棒状、その他類似形状のものも包含する。
【００１１】
本発明の水性分散体における針状導電性アンチモン含有酸化錫粉末の含有量は、１０〜５０重量％、好ましくは１５〜５０重量％で、ｐＨは４〜１１、好ましくは５〜９である。この含有率は高い方が良いが高きに過ぎると、工業的に良好な水性分散体を得るのが難しく、また、低きに過ぎると、導電性塗料として濃度を上げられないなど、使用上問題となる。
【００１２】
本発明において使用するリン酸イオンを供与する化合物としては、例えば、オルソリン酸、メタリン酸、ヘキサメタリン酸、ピロリン酸、トリポリリン酸、テトラポリリン酸、亜リン酸、次亜リン酸などやこれらのアルカリ金属塩が挙げられる。リン酸イオンは、P2O5として針状導電性アンチモン含有酸化錫粉末の重量基準で０．０１〜１０％、好ましくは０．３〜３％配合することによって、分散性、粘度、安定性などの点で良好な水性分散体が得られる。この配合量を必要以上に多くしても更なる分散性の改良にはならず、経済的でないばかりか導電性の悪化を来すことになり望ましくない。また、その配合量が少なきに過ぎると十分な安定性が得られない。リン酸、リン酸塩は１種のものに限定する必要はなく、２種以上のものを組み合わせて使用してもよい。
【００１３】
本発明の水性分散体は、リン酸・リン酸塩、水性媒液及び針状導電性アンチモン含有酸化錫粉末を、種々の方法によって分散させることによって得られるが、例えば、羽根型攪拌機、ディスパー、ホモミキサー等を用いて予備混合したのち、サンドミル、ディスクミル、ボールミル等の粉砕機を用いて針状導電性アンチモン含有酸化錫粉末を分散させることによって調製することができる。更に分級を施し、粗粒を除去することもできる。上記の予備混合法としては、先ず水性媒液にリン酸イオンを存在させ、次いで針状導電性アンチモン含有酸化錫粉末を投入し、混合する方法、或いは、予め水性媒液に針状導電性アンチモン含有酸化錫粉末を投入、混合し、次いでこの分散液にリン酸・リン酸塩を添加する方法などを適宜選択できる。
【００１４】
本発明の導電性塗料は、本発明の水性分散体と水溶性樹脂とを混合させることによって得られる。水溶性樹脂としては、例えば、ポリビニルアルコール樹脂、アクリル樹脂、アルキッド樹脂、ゼラチン、ヒドロキシセルロースなどを用いることができる。針状導電性アンチモン含有酸化錫粉末の水溶性樹脂への配合量は、水溶性樹脂１００重量部（固形分基準）に対して２５〜４００重量部、好ましくは３３〜１８５重量部である。この配合量が多きに過ぎると十分な透明性が得られず、塗膜と基材の密着性が低下する。また、配合量が少なきに過ぎると十分な導電性が得られない。
【００１５】
本発明の導電性塗料は、本発明の水性分散体とポリアルコキシシロキサンとを混合させることによっても得ることができる。ポリアルコキシシロキサンとしては、例えばメチルシリケート、エチルシリケートなどのアルキルシリケート及び／又はこれらの加水分解によって得られた重合物、更には、これらをメタノール、エタノール、プロパノールなどのアルコール類で希釈したものなどから任意に選択することができる。
【００１６】
針状導電性アンチモン含有酸化錫粉末のポリアルコキシシロキサンへの配合量は、ポリアルコキシシロキサン１００重量部（固形分基準）に対して２５〜４００重量部、好ましくは３３〜１８５重量部である。この配合量が多きに過ぎると十分な透明性が得られず、塗膜と基材の密着性が低下する。また、配合量が少なきに過ぎると十分な導電性が得られない。
【００１７】
【実施例】
次に実施例、比較例によってこの発明をさらに詳細に説明する。
実施例１
９０℃の純水５リットル中に塩化第二錫５水塩５００ｇ及び三塩化アンチモン３．３６ｇを３Ｎ塩酸水溶液５００ｍｌに溶解した溶液と、ケイ酸ナトリウム水溶液（SiO2として３００ｇ／ｌ）１７．９ｍｌと水酸化ナトリウムとを系のｐＨを７．０〜７．５に維持するように２０分間にわたって並行添加して共沈物を生成させた。次に、ここへ塩酸を加えて系のｐＨを３に調整した後、該沈澱物を濾過し、その後、濾液の比抵抗が15,000Ωｃｍになるまで水洗した。得られたケーキを１１０℃で１２時間乾燥して乾燥物（Ａ）を得た。
この乾燥物（Ａ）１００重量部に対して２０重量部の割合の塩化ナトリウムを加え、両者を均一に混合粉砕した。この混合物を電気炉で８００℃にて１時間焼成した。しかる後、得られた焼成物をフッ化水素酸水溶液に浸漬して可溶性塩類を除去した後、乾燥・粉砕を行って針状導電性アンチモン含有酸化錫粉末を得た（Ｂ）。
得られた針状導電性アンチモン含有酸化錫粉末４００ｇを水１リットル中に入れ、ヘキサメタリン酸ナトリウムをP2O5として４ｇ添加し、水酸化ナトリウム水溶液を加えてスラリーのｐＨを９．０に調整した。この混合液をサンドミルで１時間粉砕して本発明の針状導電性アンチモン含有酸化錫の水性分散体を得た。
【００１８】
実施例２
実施例１のヘキサメタリン酸ナトリウムをピロリン酸ナトリウムに代え、同様の操作をして本発明の針状導電性アンチモン含有酸化錫の水性分散体を得た。
【００１９】
実施例３
実施例１のヘキサメタリン酸ナトリウムをリン酸水素二ナトリウムに代え、同様の操作をして本発明の針状導電性アンチモン含有酸化錫の水性分散体を得た。
【００２０】
比較例１
実施例１のヘキサメタリン酸ナトリウムを添加しないこと以外は同様の操作をして針状導電性アンチモン含有酸化錫の水性分散体を得た。
【００２１】
比較例２
実施例１で得た乾燥物を電気炉で焼成し、比表面積７５m2/gの球状の導電性アンチモン含有酸化錫を得た（Ａ）。この焼成物を粉砕し、実施例１と同様の操作を行ない、球状導電性アンチモン含有酸化錫の水性分散体を得た。
【００２２】
試験例１
得られた各水性分散体の固形分濃度を２０％に調整し、１６．７ｇを秤取り、純水を４０．５ｇ加えた後、２０％水溶性樹脂溶液１１．１ｇを加え、攪拌混合して各水性塗料を得た。
ＰＥＴフィルム上にバーコーター＃５にて塗布後、自然乾燥して試験用塗膜を得た（ＰＷＣ：６０％，ＳＶＣ：４．５％，乾燥膜厚：０．３μｍ）。
得られた塗膜の表面抵抗をアドバンテスト社製TR-8601 にて計測した。また、ヘイズを日本電色社製ヘイズメーターNDH-300Aにて計測した。
以上の試験結果を表１に示す。
【００２３】
【表１】
【発明の効果】
本発明の針状導電性アンチモン含有酸化錫粉末水性分散体は、導電性に優れた針状のアンチモン含有酸化錫を非常に良く分散した状態で含有する。そのため、該水性分散体を水溶性樹脂やポリアルコキシシロキサンに配合して導電性塗料を得、このものを紙、ゴム、高分子フィルム、ガラス板などの絶縁性基体に塗布すると、高い導電性を有し、しかも透明性にも優れた塗膜の形成が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel aqueous dispersion of acicular antimony-containing tin oxide powder and an aqueous conductive coating using the same.
[0002]
[Prior art]
As a transparent conductive material, in particular in the field where high transparency and antistatic ability are required such as television, cathode ray tube, transparent sheet such as OHP and X-ray film, packaging material requiring transparency, etc. Antimony-containing tin oxide powder is used.
[0003]
When these antimony-containing tin oxide powders are applied to aqueous conductive coatings, the treated cake after removing the tin oxide powder or soluble salts obtained from the production process of the tin oxide powder is used as an aqueous medium. An aqueous dispersion formed by dispersion is prepared, and the aqueous dispersion and a water-soluble resin are mixed to form a paint. By applying to an insulating substrate such as the paint, paper, rubber or polymer film, a conductive coating film can be formed on the substrate.
[0004]
However, aqueous dispersions and conductive coatings containing needle-shaped antimony-containing tin oxide powder have a problem that it is difficult to disperse powder particles compared to the case where spherical antimony-containing tin oxide powder is added. there were. Therefore, when acicular antimony-containing tin oxide powder is used, it is difficult to obtain a coating film having high conductivity and excellent transparency.
[0005]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems of aqueous dispersions and conductive paints containing acicular antimony-containing tin oxide powder, and makes it possible to obtain a coating film having high conductivity and excellent transparency. The invention has been made to provide an aqueous dispersion and an aqueous conductive paint.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that an aqueous dispersion or conductive paint containing acicular antimony-containing tin oxide powder in the presence of phosphate ions meets this purpose. Based on this finding, the present invention has been completed.
[0007]
That is, the present invention comprises an aqueous medium as a dispersion medium, acicular conductive antimony-containing tin oxide powder and phosphate ions, and the phosphate ion is P 2 O 5 and the acicular conductive antimony-containing tin oxide powder. Ri 0.3 to 3% der by weight, mixing the acicular conductive antimony-containing tin oxide powder is Ru 10 to 50 wt% der aqueous dispersion and aqueous dispersion and a water-soluble resin or polyalkoxysiloxane It is the conductive paint made to do.
[0008]
The acicular conductive antimony-containing tin oxide powder of the present invention is obtained by firing SnO 2 / Sb 2 O 3 / SiO 2 / NaCl (Japanese Patent Laid-Open No. 8-231222) or the surface of acicular tin oxide particles as base particles It can be obtained by depositing hydrous antimony oxide on and baking it.
[0009]
The acicular antimony-containing tin oxide powder of the present invention has a minor axis average particle size of 0.005 to 0.05 μm, preferably 0.005 to 0.02 μm, and a major axis average particle size of 0.1 to 0.05 μm. It is preferably 3 μm, preferably 0.2 to 3 μm, and an axial ratio of 5 to 600.
[0010]
In the present invention, the term “needle” includes not only needles in the above axial ratio range but also fibers, columns, rods, and other similar shapes.
[0011]
The content of the acicular antimony-containing tin oxide powder in the aqueous dispersion of the present invention is 10 to 50% by weight, preferably 15 to 50% by weight, and the pH is 4 to 11, preferably 5 to 9. If this content is higher, it is better, but if it is too high, it is difficult to obtain an industrially good aqueous dispersion, and if it is too low, the concentration as a conductive paint cannot be increased. It becomes.
[0012]
Examples of compounds that donate phosphate ions used in the present invention include orthophosphoric acid, metaphosphoric acid, hexametaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, phosphorous acid, hypophosphorous acid, and alkali metals thereof. Salt. Phosphate ions, 0.01% to 10% by weight of the acicular conductive antimony-containing tin oxide powder as P 2 O 5, preferably by from 0.3 to 3% formulation, dispersibility, viscosity, stability A favorable aqueous dispersion is obtained in terms of the above. Increasing the blending amount more than necessary does not further improve dispersibility, and is not economical, and it is undesirable because it deteriorates conductivity. In addition, if the blending amount is too small, sufficient stability cannot be obtained. Phosphoric acid and phosphate need not be limited to one type, and two or more types may be used in combination.
[0013]
The aqueous dispersion of the present invention can be obtained by dispersing phosphoric acid / phosphate, aqueous medium and acicular conductive antimony-containing tin oxide powder by various methods. For example, a blade-type stirrer, a disper, After premixing using a homomixer or the like, it can be prepared by dispersing the acicular antimony-containing tin oxide powder using a pulverizer such as a sand mill, a disk mill, or a ball mill. Further, classification can be performed to remove coarse particles. As the above premixing method, first, phosphate ions are present in an aqueous medium, and then acicular conductive antimony-containing tin oxide powder is added and mixed. Alternatively, acicular conductive antimony is previously added to an aqueous medium. A method of adding and mixing the tin oxide powder and then adding phosphoric acid / phosphate to the dispersion can be selected as appropriate.
[0014]
The conductive paint of the present invention can be obtained by mixing the aqueous dispersion of the present invention and a water-soluble resin. As the water-soluble resin, for example, polyvinyl alcohol resin, acrylic resin, alkyd resin, gelatin, hydroxycellulose and the like can be used. The blending amount of the acicular conductive antimony-containing tin oxide powder in the water-soluble resin is 25 to 400 parts by weight, preferably 33 to 185 parts by weight with respect to 100 parts by weight of the water-soluble resin (solid content basis). If the amount is too large, sufficient transparency cannot be obtained, and the adhesion between the coating film and the substrate is lowered. Moreover, when there are too few compounding quantities, sufficient electroconductivity will not be obtained.
[0015]
The conductive paint of the present invention can also be obtained by mixing the aqueous dispersion of the present invention and polyalkoxysiloxane. Examples of the polyalkoxysiloxane include alkyl silicates such as methyl silicate and ethyl silicate and / or polymers obtained by hydrolysis thereof, and those diluted with alcohols such as methanol, ethanol and propanol. Can be arbitrarily selected.
[0016]
The compounding amount of the acicular conductive antimony-containing tin oxide powder in the polyalkoxysiloxane is 25 to 400 parts by weight, preferably 33 to 185 parts by weight, based on 100 parts by weight of the polyalkoxysiloxane (solid content basis). If the amount is too large, sufficient transparency cannot be obtained, and the adhesion between the coating film and the substrate is lowered. Moreover, when there are too few compounding quantities, sufficient electroconductivity will not be obtained.
[0017]
【Example】
Next, the present invention will be described in more detail with reference to examples and comparative examples.
Example 1
A solution of 500 g of stannic chloride pentahydrate and 3.36 g of antimony trichloride in 500 ml of 3N hydrochloric acid solution in 5 liters of pure water at 90 ° C., and 17.9 ml of sodium silicate aqueous solution (300 g / l as SiO 2 ) And sodium hydroxide were added in parallel over 20 minutes to maintain the pH of the system at 7.0-7.5 to produce a coprecipitate. Next, hydrochloric acid was added thereto to adjust the pH of the system to 3, and then the precipitate was filtered, and then washed with water until the specific resistance of the filtrate reached 15,000 Ωcm. The obtained cake was dried at 110 ° C. for 12 hours to obtain a dried product (A).
20 parts by weight of sodium chloride was added to 100 parts by weight of the dried product (A), and both were uniformly mixed and ground. This mixture was baked in an electric furnace at 800 ° C. for 1 hour. Thereafter, the fired product obtained was immersed in an aqueous hydrofluoric acid solution to remove soluble salts, and then dried and ground to obtain acicular antimony-containing tin oxide powder (B).
400 g of the obtained needle-like conductive antimony-containing tin oxide powder is put into 1 liter of water, 4 g of sodium hexametaphosphate is added as P 2 O 5 , and the pH of the slurry is adjusted to 9.0 by adding an aqueous sodium hydroxide solution. did. This mixed liquid was pulverized with a sand mill for 1 hour to obtain an aqueous dispersion of tin oxide containing acicular conductive antimony of the present invention.
[0018]
Example 2
The same procedure was followed to replace the sodium hexametaphosphate of Example 1 with sodium pyrophosphate to obtain an aqueous dispersion of acicular antimony-containing tin oxide of the present invention.
[0019]
Example 3
An aqueous dispersion of acicular conductive antimony-containing tin oxide of the present invention was obtained by replacing sodium hexametaphosphate of Example 1 with disodium hydrogen phosphate and performing the same operation.
[0020]
Comparative Example 1
An aqueous dispersion of acicular antimony-containing tin oxide was obtained in the same manner as in Example 1 except that sodium hexametaphosphate was not added.
[0021]
Comparative Example 2
The dried product obtained in Example 1 was fired in an electric furnace to obtain spherical conductive antimony-containing tin oxide having a specific surface area of 75 m 2 / g (A). The fired product was pulverized and the same operation as in Example 1 was performed to obtain an aqueous dispersion of spherical conductive antimony-containing tin oxide.
[0022]
Test example 1
The solid content concentration of each aqueous dispersion obtained was adjusted to 20%, 16.7 g was weighed, 40.5 g of pure water was added, 11.1 g of 20% water-soluble resin solution was added, and the mixture was stirred and mixed. Thus, each water-based paint was obtained.
After coating on a PET film with a bar coater # 5, it was naturally dried to obtain a test coating film (PWC: 60%, SVC: 4.5%, dry film thickness: 0.3 μm).
The surface resistance of the obtained coating film was measured with TR-8601 manufactured by Advantest Corporation. Further, the haze was measured with a Nippon Denshoku haze meter NDH-300A.
The test results are shown in Table 1.
[0023]
[Table 1]
【The invention's effect】
The needle-shaped conductive antimony-containing tin oxide powder aqueous dispersion of the present invention contains needle-shaped antimony-containing tin oxide excellent in conductivity in a very well dispersed state. Therefore, when the aqueous dispersion is mixed with a water-soluble resin or polyalkoxysiloxane to obtain a conductive paint, and this is applied to an insulating substrate such as paper, rubber, polymer film, glass plate, etc., high conductivity is obtained. In addition, it is possible to form a coating film having excellent transparency.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07897697A JP3697016B2 (en) | 1997-03-12 | 1997-03-12 | Acicular conductive antimony-containing tin oxide powder aqueous dispersion and conductive paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07897697A JP3697016B2 (en) | 1997-03-12 | 1997-03-12 | Acicular conductive antimony-containing tin oxide powder aqueous dispersion and conductive paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10255548A JPH10255548A (en) | 1998-09-25 |
| JP3697016B2 true JP3697016B2 (en) | 2005-09-21 |
Family
ID=13676939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07897697A Expired - Lifetime JP3697016B2 (en) | 1997-03-12 | 1997-03-12 | Acicular conductive antimony-containing tin oxide powder aqueous dispersion and conductive paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3697016B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5674354B2 (en) * | 2009-06-30 | 2015-02-25 | 三菱マテリアル株式会社 | Conductive acicular antimony tin oxide fine powder and method for producing the same |
| CN103298902B (en) * | 2012-01-11 | 2014-12-10 | 三菱综合材料株式会社 | Infrared cut material, infrared cut material dispersion liquid, composition for forming infrared cut film, and infrared cut film |
-
1997
- 1997-03-12 JP JP07897697A patent/JP3697016B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10255548A (en) | 1998-09-25 |
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