JP3875282B2 - Conductive thin plate barium sulfate filler and method for producing the same - Google Patents
Conductive thin plate barium sulfate filler and method for producing the same Download PDFInfo
- Publication number
- JP3875282B2 JP3875282B2 JP28219993A JP28219993A JP3875282B2 JP 3875282 B2 JP3875282 B2 JP 3875282B2 JP 28219993 A JP28219993 A JP 28219993A JP 28219993 A JP28219993 A JP 28219993A JP 3875282 B2 JP3875282 B2 JP 3875282B2
- Authority
- JP
- Japan
- Prior art keywords
- barium sulfate
- thin plate
- conductive
- filler
- indium
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/027—Barium sulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/066—Treatment or coating resulting in a free metal containing surface-region
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inorganic Fibers (AREA)
- Conductive Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は導電性薄板状硫酸バリウムフィラー及びその製造方法に関し、更に詳しくは、プラスチック、ゴム、樹脂、塗料、繊維、紙等に混入してそれらに導電性を付与するための、比電気抵抗値が低く且つ単位重量当たりの導電性付与効果が著しく優れている導電性薄板状硫酸バリウムフィラー及びその製造方法に関する。
【０００２】
【従来の技術】
ドイツ特許第４０１７０４４号明細書には、酸化アンチモンをドープした酸化錫層で被覆されている硫酸バリウム粒子からなる導電性硫酸バリウムフィラーが開示されている。
【０００３】
周知のごとく、プラスチックや塗料等に良好な導電性を付与するためには、混入した導電性フィラー同志が接触する必要があり、それ故に導電性フィラーが球状の場合には多量の添加が必要である。導電性フィラーが高価な場合には、そのような導電性フィラーを多量に混入して得た製品はコスト面でその用途が限定される。これを改善する目的で球状よりもアスペクト比が格段に大きく、比較的少量の添加でも導電性フィラー間の接触の機会が多い形状である繊維状導電性フィラーが提案されている。
【０００４】
例えば、特開昭５９−１０２８２０号公報、特開昭６２−５９５２８号公報には、一般式Ｍ2 Ｏ・ｎＴｉＯ2 ・ｍＨ2 Ｏで表されるチタン酸アルカリ金属繊維が酸化アンチモンをドープした酸化錫層で被覆されている導電性チタン酸アルカリ金属繊維からなるフィラーが開示されている。しかし、アスベスト等の繊維状フィラーにおいては発ガン性が指摘され、その使用が規制されているように、上記ウィスカー、セラミックファイバー等の歴史は新しく、長期毒性については不明な部分が多く、国際がん研究機関（ＩＡＲＣ）の発ガン性のランクはこれら人造鉱物繊維は第２群Ｂ（証拠は十分ではないが、ヒトに対して発ガンの可能性があると考えられる）に位置づけられており、その安全性について問題がある。
【０００５】
【発明が解決しようとする課題】
かかる事情に鑑み、本発明者等は上記のような欠点のない導電性薄板状硫酸バリウムフィラー、即ち、
（１）導電性薄板状硫酸バリウムフィラー自体の白色度が優れていて、その様なフィラーを紙、繊維、プラスチック、ゴム、樹脂、塗料等の基材に添加した場合にそれらの基材が導電性薄板状硫酸バリウムフィラーに起因して着色されることがなく、白色あるいは透明のままであり、それで着色剤を添加することによって任意の所望色調が得られ、
（２）繊維状導電性フィラーのような労働安全衛生上の問題もなく、
（３）安価に製造でき、
（４）樹脂、塗料等中への高い分散性を有し、
（５）球状粒子が点接触であるに対して、薄板状であるため面接触もしくは線接触となり、少量添加で高い導電性付与効果を有し、
（６）導電性薄板状硫酸バリウムフィラーを紙、繊維、プラスチック、ゴム、樹脂、塗料等の基材に添加する際に、導電性薄板状硫酸バリウムフィラーの表面に被覆されている導電性被膜が剥離して導電性の損失を生じることがない、
導電性薄板状硫酸バリウムフィラーを提供することを目的として種々検討を重ねて、本発明を完成した。
【０００６】
【課題を解決するための手段】
即ち、本発明の導電性薄板状硫酸バリウムフィラーは、薄板状硫酸バリウムからなる芯材と、その表面を被覆している導電性物質の層とからなり、該芯材が未被覆状態で０．１〜３０ｍ2 ／ｇの比表面積を有しており、該導電性物質の層がインジウム−錫複合酸化物からなる層であることを特徴とする。
【０００７】
本発明の導電性薄板状硫酸バリウムフィラーにおいては、芯材として使用する硫酸バリウム粒子の比表面積は未被覆状態で０．１〜３０ｍ2 ／ｇである。その比表面積が０．１ｍ2 ／ｇ未満の場合には、それを用いて得た導電性薄板状硫酸バリウムフィラーの単位重量当たりの導電率は小さく、従ってそのようなフィラーを例えば樹脂マトリックス中に混入しても満足な帯電防止効果は得られない。また、その比表面積が未被覆状態で３０ｍ2 ／ｇを超える場合には所望の導電性を達成するのに必要な被膜物質の量が多くなりコスト高になると同時に比重が大きくなり、所望の帯電防止効果を得るためには例えば樹脂マトリックス中への添加量を多くしなければならない。なお、本発明で芯材として使用する硫酸バリウム粒子は一般的には長径が３〜３００μｍ、厚みが０．１〜３μｍの薄板状のものである。硫酸バリウム粒子の比表面積が未被覆状態で０．１〜３０ｍ2 ／ｇである場合には、それを用いて得た導電性薄板状硫酸バリウムフィラーは透明であり、そのような粒子は塗料用に使用することが望ましく、そしてその塗料は導電性となる。またこの導電性薄板状硫酸バリウムフィラーの添加によっても添加顔料の隠蔽力が悪影響されることはない。なお、本発明で芯材として用いる硫酸バリウムは随伴不純物である硫化亜鉛を含んでいてもよい。
【０００８】
本発明の導電性薄板状硫酸バリウムフィラーにおいては、薄板状硫酸バリウムからなる芯材の表面を被覆している導電性物質の層はインジウム−錫複合酸化物からなる層である。本発明においては、インジウム元素と錫元素との重量比は特には限定されないが、酸化インジウム及び酸化錫として計算して一般的にはＩｎ2 Ｏ3 ：ＳｎＯ2 ＝１０００：１〜１：１である。
【０００９】
本発明の導電性薄板状硫酸バリウムフィラーにおいては、被膜の厚さは好ましくは２〜８０ｎｍである。被膜の厚さが２ｎｍ未満の場合にはその被覆された硫酸バリウムの導電性が不十分であり、従ってそのような粒子を例えば樹脂マトリックス中に混入しても満足な帯電防止効果は得られない。また、被膜の厚さが８０ｎｍを超えても、増加するコストに見合った帯電防止効果は達成されず、コスト高になってしまう。被膜が２〜８０ｎｍの厚さを有する場合、酸化錫からなる被膜と硫酸バリウム粒子との間の結合力は比較的強くなり、本発明による導電性薄板状硫酸バリウムフィラーが樹脂中へ混練される際にも、被膜は硫酸バリウム粒子から剥離することはない。
【００１４】
インジウム−錫複合酸化物からなる被覆層を有する導電性薄板状硫酸バリウムフィラーは本発明に従って下記の諸工程からなる製造方法によって得られる：
（ａ）比表面積が０．１〜３０ｍ2 ／ｇである薄板状硫酸バリウムを１０〜１０００ｇ／ｌの濃度で含有するスラリーと、３価のインジウム化合物及び４価の錫化合物を含有する酸溶液とを混合してｐＨ２以下の混合液を調製する工程、
（ｂ）その混合液にアルカリ溶液を添加してｐＨを４〜８とし該薄板状硫酸バリウムの表面上に酸化インジウム−酸化錫の水和物からなる被覆層を形成する工程、
（ｃ）その懸濁液の攪拌を続けて、被膜を熟成する工程、
（ｄ）それにより得られた固形物を固液分離し、水洗して可溶性塩を除去し、乾燥する工程、
（ｅ）空気中３００〜１０００℃あるいは不活性雰囲気下または還元性雰囲気下１５０〜６００℃で焼成する工程。
【００１５】
上記の（ａ）工程で用いる３価のインジウム化合物及び４価の錫化合物を含有する酸溶液においてはインジウム元素と錫元素との重量比は特には限定されないが、酸化インジウム及び酸化錫として計算して一般的にはＩｎ2 Ｏ3 ：ＳｎＯ2 ＝１０００：１〜１：１となるような割合で３価のインジウム化合物及び４価の錫化合物を含有する酸溶液を用いる。
【００１６】
本発明の製造方法は、薄板状硫酸バリウムがインジウム−錫複合酸化物からなる被覆層により完全に被覆されるという利点を与え、短時間で容易に実施することができ、また製造された導電性薄板状硫酸バリウムフィラーは樹脂中での高い分散性を示す。
【００１７】
本発明の導電性薄板状硫酸バリウムフィラーは芯材として薄板状硫酸バリウム粒子を使用し、その表面に２〜８０ｎｍの厚みを有する導電性物質の薄膜を形成しているので、透明性を有し且つ芯材の硫酸バリウムの屈折率も樹脂の屈折率に近似しているのでこの導電性薄板状硫酸バリウムフィラーを塗料、樹脂、プラスチック等に混入してもそれらの透明性を損なうことが少なく、ましてや着色することもなく、それで本導電性薄板状硫酸バリウムフィラーと共に着色剤を添加することによって所望の任意の色調が得られる。その上繊維状フィラーのような労働安全衛生上の問題もなく、分散性に優れ、球状粒子が点接触であるに対して、面接触もしくは線接触となるため少量添加で高い導電性付与効果を有する導電性薄板状硫酸バリウムフィラーである。
【００１８】
本発明の導電性薄板状硫酸バリウムフィラーは紙、繊維、プラスチック、ゴム、樹脂、塗料等に混入してそれらに導電性を付与することができ、それで、例えば、自動車静電塗装プライマー、精密電子機器の静電気障害防止、静電気災害の発生防止、防塵等のためのハウジング、建材、繊維、機械部品等の用途に用いることができる。更に、本発明の導電性薄板状硫酸バリウムフィラーは複写機関連で荷電調製剤として導電性ローラー、感光ドラム、トナーに、また電極改質剤として電池等にも用いることができる。更に、形状効果により透明で放射線遮蔽効果も大きい。
【００１９】
特に自動車用などの樹脂製部品などの非導電性材料の静電塗装用導電プライマーとして使用した場合は、その表面を導電化することにより、次の静電塗装の付着効率を著しく向上させるという本来の効果以外に、板状のフィラーが表面に平行に配向することにより、素地・塗幕界面に水分などが浸透することを抑制するので、塗膜の密着性、耐食性を向上させる効果も見られる。
【００２０】
【実施例】
以下、本発明を実施例により更に詳細に説明するが、本発明はかかる実施例によって限定されるものではない。
【００２２】
実施例１
比表面積が１．５ｍ2 ／ｇであり、マイクロトラック粒度分布測定装置で測定した平均粒子径が５．５μｍであり、アスペクト比（長径／厚み）が２０である薄板状硫酸バリウム粒子２００ｇを水１０００ｍｌ中に分散させ、この分散スラリーを４０℃まで加熱した。その後、その分散スラリーに、硝酸インジウム溶液（Ｉｎ：１ｍｏｌ／ｌ）２４２ｍｌとＳｎＣｌ4 溶液（９８％）３．１ｇとを混合した酸溶液を添加して、分散スラリーのｐＨを１．８に調整し、これに５％アンモニア溶液を９０分間かけて添加しｐＨが５になるまで中和して薄板状硫酸バリウム粒子の表面上に酸化インジウム−酸化錫の水和物からなる被覆層を形成させた。その後、ろ過し、洗浄し、乾燥し、マッフル炉中６００℃で２時間焼成して、本発明のインジウム−錫複合酸化物からなる被覆層を有する導電性薄板状硫酸バリウムフィラーを得た。この導電性薄板状硫酸バリウムフィラーの比電気抵抗値は１Ω・ｃｍであった。
【００２４】
実施例２
実施例１の方法において、硫酸バリウムの比表面積、被覆導電性物質の被覆率及び層厚、焼成雰囲気及び焼成温度を表１に示すように変更して実施例１と同様にして本発明の導電性薄板状硫酸バリウムフィラーを得た。その導電性薄板状硫酸バリウムフィラーの比電気抵抗率は表１に示す通りであった。なお、表１には実施例１の条件、結果も示す。
【００２５】
【表１】
【発明の効果】
本発明の導電性薄板状硫酸バリウムフィラーは、
（１）導電性薄板状硫酸バリウムフィラー自体の白色度が優れていて、その様なフィラーを紙、繊維、プラスチック、ゴム、樹脂、塗料等の基材に添加した場合にそれらの基材が導電性薄板状硫酸バリウムフィラーに起因して着色されることがなく、白色あるいは透明のままであり、それで着色剤を添加することによって任意の所望色調が得られ、
（２）繊維状導電性フィラーのような労働安全衛生上の問題もなく、
（３）安価に製造でき、
（４）樹脂、塗料等中への高い分散性を有し、
（５）球状粒子が点接触であるに対して、薄板状であるため面接触もしくは線接触となり、少量添加で高い導電性付与効果を有し、
（６）導電性薄板状硫酸バリウムフィラーを紙、繊維、プラスチック、ゴム、樹脂、塗料等の基材に添加する際に、導電性薄板状硫酸バリウムフィラーの表面に被覆されている導電性被膜が剥離して導電性の損失を生じることがない。[0001]
[Industrial application fields]
TECHNICAL FIELD The present invention relates to a conductive thin plate-like barium sulfate filler and a method for producing the same, and more specifically, specific electric resistance value for adding conductivity to plastic, rubber, resin, paint, fiber, paper, etc. The present invention relates to a conductive thin plate-like barium sulfate filler that has a low conductivity and has an extremely excellent conductivity imparting effect per unit weight, and a method for producing the same.
[0002]
[Prior art]
German Patent No. 4017044 discloses a conductive barium sulfate filler consisting of barium sulfate particles coated with a tin oxide layer doped with antimony oxide.
[0003]
As is well known, in order to give good conductivity to plastics and paints, it is necessary for the mixed conductive fillers to come into contact with each other. Therefore, when the conductive filler is spherical, a large amount of addition is necessary. is there. When the conductive filler is expensive, the use of a product obtained by mixing a large amount of such a conductive filler is limited in terms of cost. In order to improve this, there has been proposed a fibrous conductive filler having a shape that has a significantly larger aspect ratio than that of a sphere and has a large number of opportunities for contact between conductive fillers even when added in a relatively small amount.
[0004]
For example, in Japanese Patent Laid-Open Nos. 59-102820 and 62-59528, an oxidation in which an alkali metal titanate fiber represented by the general formula M 2 O.nTiO 2 .mH 2 O is doped with antimony oxide is disclosed. A filler made of conductive alkali metal titanate fibers coated with a tin layer is disclosed. However, as fibrous fillers such as asbestos have been pointed out to be carcinogenic and their use is regulated, the history of the above whiskers, ceramic fibers, etc. is new, and there are many unknown parts regarding long-term toxicity. The ranks of carcinogenicity of cancer research institutes (IARC) are placed in Group 2 B (though there is not enough evidence, it is thought that there is a possibility of carcinogenesis in humans). There is a problem with its safety.
[0005]
[Problems to be solved by the invention]
In view of such circumstances, the present inventors have a conductive thin plate-like barium sulfate filler that does not have the above disadvantages, that is,
(1) The whiteness of the conductive thin plate-like barium sulfate filler itself is excellent, and when such filler is added to a substrate such as paper, fiber, plastic, rubber, resin, paint, etc., the substrate becomes conductive. Is not colored due to the conductive lamellar barium sulfate filler, remains white or transparent, so that any desired color tone can be obtained by adding a colorant,
(2) Occupational safety and health problems like fibrous conductive fillers,
(3) Can be manufactured at low cost,
(4) High dispersibility in resin, paint, etc.
(5) Spherical particles are point contacts, but because they are thin plates, they become surface contacts or line contacts, and have a high conductivity imparting effect when added in a small amount.
(6) When a conductive thin plate-like barium sulfate filler is added to a substrate such as paper, fiber, plastic, rubber, resin, paint, etc., the conductive coating coated on the surface of the conductive thin plate-like barium sulfate filler Does not peel and cause loss of conductivity,
Various studies were repeated for the purpose of providing a conductive sheet-like barium sulfate filler, and the present invention was completed.
[0006]
[Means for Solving the Problems]
That is, the conductive thin plate-like barium sulfate filler of the present invention comprises a core material made of thin plate-like barium sulfate and a layer of a conductive material covering the surface thereof. It has a specific surface area of 1-30 m 2 / g, a layer Guy indium of the conductive material - is characterized in that a layer made of tin oxide.
[0007]
In the conductive thin plate-like barium sulfate filler of the present invention, the specific surface area of the barium sulfate particles used as the core material is 0.1 to 30 m 2 / g in an uncoated state. When the specific surface area is less than 0.1 m 2 / g, the conductivity per unit weight of the conductive lamellar barium sulfate filler obtained using the same is small, so that such filler is contained in, for example, a resin matrix. Even if mixed, a satisfactory antistatic effect cannot be obtained. Further, when the specific surface area exceeds 30 m 2 / g in the uncoated state, the amount of the coating material necessary to achieve the desired conductivity increases, the cost increases and the specific gravity increases, and the desired charge is increased. In order to obtain the prevention effect, for example, the amount added to the resin matrix must be increased. The barium sulfate particles used as the core material in the present invention are generally in the form of a thin plate having a major axis of 3 to 300 μm and a thickness of 0.1 to 3 μm. When the specific surface area of the barium sulfate particles is 0.1 to 30 m 2 / g in an uncoated state, the conductive thin plate-like barium sulfate filler obtained using the particles is transparent, and such particles are used for coatings. And the paint becomes conductive. Further, the hiding power of the added pigment is not adversely affected by the addition of the conductive lamellar barium sulfate filler. In addition, the barium sulfate used as a core material in the present invention may contain zinc sulfide which is an accompanying impurity.
[0008]
In the conductive thin plate barium sulfate filler of the present invention, the layer of conductive material covering the surface of the core material made of a thin plate barium sulfate Lee indium - is a layer made of tin oxide. In the present invention, i the weight ratio of indium element and tin element is not particularly limited, generally, calculated as indium oxide and tin oxide In 2 O 3: SnO 2 = 1000: 1~1: 1 It is.
[0009]
In the conductive thin plate-like barium sulfate filler of the present invention, the thickness of the coating is preferably 2 to 80 nm. When the thickness of the coating is less than 2 nm, the conductivity of the coated barium sulfate is insufficient, so that even if such particles are mixed into a resin matrix, for example, a satisfactory antistatic effect cannot be obtained. . Moreover, even if the thickness of the coating exceeds 80 nm, the antistatic effect commensurate with the increasing cost is not achieved and the cost increases. When the coating has a thickness of 2 to 80 nm, the bonding force between the coating made of tin oxide and the barium sulfate particles becomes relatively strong, and the conductive thin plate-like barium sulfate filler according to the present invention is kneaded into the resin. In particular, the coating does not peel from the barium sulfate particles.
[0014]
A conductive thin plate-like barium sulfate filler having a coating layer made of indium-tin composite oxide is obtained according to the present invention by a production method comprising the following steps:
(A) A slurry containing lamellar barium sulfate having a specific surface area of 0.1 to 30 m 2 / g at a concentration of 10 to 1000 g / l, an acid solution containing a trivalent indium compound and a tetravalent tin compound A step of preparing a liquid mixture having a pH of 2 or less by mixing
(B) adding an alkaline solution to the mixed solution to adjust the pH to 4 to 8 and forming a coating layer made of indium oxide-tin oxide hydrate on the surface of the thin plate-like barium sulfate;
(C) continuing the stirring of the suspension and aging the film;
(D) solid-liquid separation of the resulting solid, washing with water to remove soluble salts and drying;
(E) A step of baking in air at 300 to 1000 ° C. or in an inert atmosphere or a reducing atmosphere at 150 to 600 ° C.
[0015]
In the acid solution containing the trivalent indium compound and the tetravalent tin compound used in the step (a), the weight ratio of the indium element to the tin element is not particularly limited, but calculated as indium oxide and tin oxide. In general, an acid solution containing a trivalent indium compound and a tetravalent tin compound at a ratio of In 2 O 3 : SnO 2 = 1000: 1 to 1: 1 is used.
[0016]
Production method of the present invention, the thin plate barium sulfate Guy indium - gives the advantage of being completely covered with a covering layer made of tin oxide, can be readily implemented in a short time, also conductive produced Porous barium sulfate filler exhibits high dispersibility in the resin.
[0017]
The conductive thin plate-like barium sulfate filler of the present invention uses thin plate-like barium sulfate particles as a core material, and has a thin film of a conductive material having a thickness of 2 to 80 nm on its surface, so that it has transparency. And since the refractive index of barium sulfate of the core material approximates the refractive index of the resin, even if this conductive thin plate-like barium sulfate filler is mixed in paint, resin, plastic, etc., their transparency is less likely to be lost. Without any coloration, any desired color tone can be obtained by adding a colorant together with the present conductive lamellar barium sulfate filler. In addition, there are no problems with occupational safety and health like fibrous fillers, excellent dispersibility, and spherical particles are in point contact, whereas surface contact or line contact, so high conductivity imparting effect can be achieved by adding a small amount. It is a conductive thin plate-like barium sulfate filler.
[0018]
The conductive thin plate-like barium sulfate filler of the present invention can be mixed with paper, fiber, plastic, rubber, resin, paint, etc. to give them conductivity, so that, for example, automotive electrostatic coating primer, precision electronics It can be used for applications such as housing, building materials, textiles, machine parts, etc. for preventing static electricity failure of equipment, preventing occurrence of static electricity disasters, and dust prevention. Further, the conductive thin plate-like barium sulfate filler of the present invention can be used for a conductive roller, a photosensitive drum, and a toner as a charge adjusting agent in connection with a copying machine, and in a battery or the like as an electrode modifier. Further, it is transparent due to the shape effect and has a large radiation shielding effect.
[0019]
In particular, when used as a conductive primer for electrostatic coating of non-conductive materials such as plastic parts for automobiles, etc., it is essential to significantly improve the adhesion efficiency of the next electrostatic coating by making the surface conductive. In addition to the above effect, the plate-like filler is oriented parallel to the surface to prevent moisture and the like from penetrating into the substrate / coating interface, so the effect of improving the adhesion and corrosion resistance of the coating film is also seen. .
[0020]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this Example.
[0022]
Example 1
200 g of thin plate-like barium sulfate particles having a specific surface area of 1.5 m 2 / g, an average particle diameter of 5.5 μm and an aspect ratio (major axis / thickness) of 20 as measured with a Microtrac particle size distribution measuring device are water. Dispersed in 1000 ml, the dispersion slurry was heated to 40 ° C. Thereafter, an acid solution obtained by mixing 242 ml of indium nitrate solution (In: 1 mol / l) and 3.1 g of SnCl 4 solution (98%) is added to the dispersion slurry to adjust the pH of the dispersion slurry to 1.8. Then, a 5% ammonia solution was added to this over 90 minutes and neutralized until the pH reached 5 to form a coating layer made of indium oxide-tin oxide hydrate on the surface of the thin plate-like barium sulfate particles. It was. Then, it filtered, wash | cleaned, dried, and baked at 600 degreeC for 2 hours in the muffle furnace, and obtained the electroconductive sheet-like barium sulfate filler which has a coating layer which consists of an indium-tin composite oxide of this invention. The specific electric resistance value of the conductive thin plate-like barium sulfate filler was 1 Ω · cm.
[0024]
Example 2
In the method of Example 1, the specific surface area of barium sulfate, the coating rate and layer thickness of the coated conductive material, the firing atmosphere and the firing temperature were changed as shown in Table 1, and the conductivity of the present invention was the same as in Example 1. Thin plate-like barium sulfate filler was obtained. The specific electrical resistivity of the conductive thin plate-like barium sulfate filler was as shown in Table 1. Table 1 also shows the conditions and results of Example 1 .
[0025]
[Table 1]
【The invention's effect】
The conductive thin plate-like barium sulfate filler of the present invention is
(1) The whiteness of the conductive thin plate-like barium sulfate filler itself is excellent, and when such filler is added to a substrate such as paper, fiber, plastic, rubber, resin, paint, etc., the substrate becomes conductive. Is not colored due to the conductive lamellar barium sulfate filler, it remains white or transparent, so any desired color tone can be obtained by adding a colorant,
(2) Occupational safety and health problems like fibrous conductive fillers,
(3) Can be manufactured at low cost,
(4) High dispersibility in resin, paint, etc.
(5) Since the spherical particles are point contacts, they are in the form of thin plates, so they are surface contact or line contact, and have a high conductivity imparting effect with a small amount of addition,
(6) When a conductive thin plate-like barium sulfate filler is added to a substrate such as paper, fiber, plastic, rubber, resin, paint, etc., the conductive coating coated on the surface of the conductive thin plate-like barium sulfate filler It does not peel and cause loss of conductivity.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28219993A JP3875282B2 (en) | 1993-11-11 | 1993-11-11 | Conductive thin plate barium sulfate filler and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28219993A JP3875282B2 (en) | 1993-11-11 | 1993-11-11 | Conductive thin plate barium sulfate filler and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07133374A JPH07133374A (en) | 1995-05-23 |
| JP3875282B2 true JP3875282B2 (en) | 2007-01-31 |
Family
ID=17649364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28219993A Expired - Fee Related JP3875282B2 (en) | 1993-11-11 | 1993-11-11 | Conductive thin plate barium sulfate filler and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3875282B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5876633A (en) * | 1995-12-26 | 1999-03-02 | Monsanto Company | Electrochromic metal oxides |
| DE69628198D1 (en) * | 1995-12-26 | 2003-06-18 | Pharmacia Corp N D Ges D Staat | ELECTROCHROMIC TIN OXIDE |
| JP4718111B2 (en) * | 2003-09-30 | 2011-07-06 | 三井金属鉱業株式会社 | Conductive powder and method for producing the same |
| JP5285725B2 (en) * | 2011-02-18 | 2013-09-11 | 三井金属鉱業株式会社 | Conductive powder |
| JP6454974B2 (en) * | 2013-03-29 | 2019-01-23 | 株式会社リコー | Metal oxide film forming coating solution, metal oxide film manufacturing method, and field effect transistor manufacturing method |
| CN114426780A (en) * | 2021-12-29 | 2022-05-03 | 浙江凯色丽科技发展有限公司 | Preparation method of barium sulfate-based conductive composite pearlescent pigment |
-
1993
- 1993-11-11 JP JP28219993A patent/JP3875282B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07133374A (en) | 1995-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100394889B1 (en) | Needle-shaped electrically conductive tin oxide fine particles and preparation method thereof | |
| US5919518A (en) | Electrically conductive barium sulfate filler and method for preparing same | |
| JPH0714430A (en) | White conductive resin composition | |
| JP3346584B2 (en) | Fibrous conductive filler and method for producing the same | |
| JP5400307B2 (en) | White conductive powder and its use | |
| JP3875282B2 (en) | Conductive thin plate barium sulfate filler and method for producing the same | |
| JPH0640719A (en) | Electrically conductive barium sulfate and preparation thereof | |
| US6409815B1 (en) | Surface-modified conductive pigment | |
| JP5400306B2 (en) | White conductive powder and its use | |
| JP3609159B2 (en) | Acicular conductive antimony-containing tin oxide fine powder and method for producing the same | |
| DE10148055B4 (en) | Electrically conductive pigment | |
| JP3195072B2 (en) | Fibrous conductive filler and method for producing the same | |
| JPS61141616A (en) | Electrically conductive titanium dioxide fine powder, and production thereof | |
| CN1132885C (en) | Process for preparing conducting light colour flaky pigment | |
| JP3140576B2 (en) | Conductive barium sulfate filler and method for producing the same | |
| JP3647929B2 (en) | Method for producing conductive antimony-containing tin oxide fine powder | |
| JP5674354B2 (en) | Conductive acicular antimony tin oxide fine powder and method for producing the same | |
| JP3394556B2 (en) | Conductive barium sulfate filler and method for producing the same | |
| JPH0832561B2 (en) | Composite conductive powder and method for producing the same | |
| JP3557688B2 (en) | Strip-shaped conductive powder, its production method and use | |
| WO1999050179A1 (en) | Conductive powder ad transparent conductive composition | |
| JPS6333435A (en) | Electrically conductive filler | |
| JPH10316429A (en) | Electroconductive titanium oxide, production thereof, and plastic composition containing the same | |
| JPS61136532A (en) | Fibrous white electroconductive substance | |
| JPH05246710A (en) | Electroconductive powder and production therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20060816 Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060816 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20060816 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060921 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20061026 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091102 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101102 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111102 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121102 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131102 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |