JP5400306B2 - White conductive powder and its use - Google Patents
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- 239000000843 powder Substances 0.000 title claims description 110
- 229910052787 antimony Inorganic materials 0.000 claims description 44
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 44
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 40
- 229910001887 tin oxide Inorganic materials 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 150000003606 tin compounds Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000009503 electrostatic coating Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は、優れた導電性と色調を有する白色導電粉末とその用途に関する。より詳しくは、本発明は、白色無機粉末を基材とし、その表面に導電性および色調に優れた導電層を設けた白色導電粉末とその用途に関する。
The present invention relates to a white conductive powder having excellent conductivity and color tone and its use . More specifically, the present invention relates to a white conductive powder in which a white inorganic powder is used as a base material and a conductive layer excellent in conductivity and color tone is provided on the surface thereof and to its use.
導電粉末は帯電防止・帯電制御・静電防止・防塵等の用途に現在広く用いられている。従来、導電性を高めるために、アンチモン等をドープした導電粉末が使用されている。具体的には、白色導電粉末として、例えば、酸化アルミニウムをドープした酸化亜鉛、二酸化チタン粉末等の表面に酸化アンチモンをドープした酸化スズ膜を形成した白色導電粉末が知られている（特許文献１、特許文献２、特許文献３）。 Conductive powders are currently widely used in applications such as antistatic, charge control, antistatic, and dustproof. Conventionally, conductive powder doped with antimony or the like has been used to increase conductivity. Specifically, as the white conductive powder, for example, white conductive powder in which a tin oxide film doped with antimony oxide is formed on the surface of zinc oxide doped with aluminum oxide, titanium dioxide powder or the like (Patent Document 1) is known. Patent Document 2, Patent Document 3).
また、アンチモン成分を含有する酸化スズからなる導電被膜をチタン酸カリウム繊維に形成した白色導電繊維が知られている（特許文献４、特許文献５）。さらに、二酸化チタン粒子表面に酸化スズおよびリンを含む導電層を形成した白色導電性二酸化チタン粉末が知られている（特許文献６）。一方、これらのドープ成分を含有しない表面改質した透明導電性酸化スズ粉末などが知られている（特許文献７）。 Moreover, the white conductive fiber which formed the conductive film which consists of tin oxide containing an antimony component in the potassium titanate fiber is known (patent documents 4 and patent documents 5). Furthermore, white conductive titanium dioxide powder in which a conductive layer containing tin oxide and phosphorus is formed on the surface of titanium dioxide particles is known (Patent Document 6). On the other hand, a surface-modified transparent conductive tin oxide powder that does not contain these dope components is known (Patent Document 7).
しかし、酸化アンチモンをドープした酸化スズ膜を有する白色導電粉末は導電性が安定しているが、従来の粉末は白色性に劣り、具体的には青色や灰色の強い色調を示すので、白色環境を要求される用途には適さないと云う問題がある。 However, the white conductive powder having a tin oxide film doped with antimony oxide is stable in conductivity, but the conventional powder is inferior in whiteness, and specifically shows a strong color tone of blue or gray. Therefore, there is a problem that it is not suitable for a use requiring the above.
一方、リンをドープした酸化スズ膜を有する酸化チタンは、導電性が不安定であり、またリンの偏在性の問題があった。さらに、表面改質されたノンドープ酸化スズからなる透明導電性酸化スズ粉末はカーボン残存等の問題がある。
本発明は、従来の白色導電粉末における上記問題を解決したものであり、アンチモン含有酸化スズ層を有する白色導電粉末について、アンチモンを含有するものの、青色や灰色の色調を示さず、優れた白色性を有する白色導電粉末とその用途を提供する。
The present invention solves the above-mentioned problems in the conventional white conductive powder, and the white conductive powder having an antimony-containing tin oxide layer contains antimony, but does not show blue or gray color tone, and has excellent whiteness And a use thereof.
本発明は、以下の構成によって上記課題を解決した白色導電粉末に関する。
〔１〕白色無機粉末表面にアンチモンを含む酸化スズ層を有し、Ｌａｂ表色系においてＬ＝８０以上、ａ＝(−２)〜(＋２)、ｂ＝(−４)〜(＋４)の色調を有する白色導電粉末であり、ＢＥＴ比表面積が１５〜３０ｍ 2 /ｇであって、酸化スズ層のアンチモン含有量が１.０〜１０.０質量％であり、該粉末におけるアンチモン含有酸化スズ層の割合が２０〜４０質量％であり、該粉末を固形分７０質量％含有する膜厚２μｍの塗膜において該塗膜の表面抵抗が１.０×１０ 10 Ω/□以下であることを特徴とする白色導電粉末。
The present invention relates to a white conductive powder that has solved the above-described problems by the following configuration.
[1] It has a tin oxide layer containing antimony on the surface of the white inorganic powder, and in the Lab color system, L = 80 or more, a = (− 2) to (+2), b = (− 4) to (+4) A white conductive powder having a color tone, a BET specific surface area of 15 to 30 m 2 / g, and an antimony content of the tin oxide layer is 1.0 to 10.0% by mass, and the antimony-containing tin oxide in the powder The surface resistance of the coating film is 1.0 × 10 10 Ω / □ or less in a coating film having a film thickness of 2 μm containing 20 to 40% by mass of the powder and containing 70% by mass of the solid content of the powder. Characteristic white conductive powder.
本発明の白色導電性粉末は以下の態様を含み、以下の用途に用いることができる。
〔２〕白色無機粉末が酸化チタンである上記[１]に記載する白色導電粉末。
〔３〕アンチモン含有酸化スズ層が、白色無機粉末表面に湿式処理によってアンチモン含有スズ化合物を形成し、これを熟成し、熱処理したものである上記[１]または上記[２]の何れかに記載する白色導電粉末。
〔４〕上記[１]〜上記[３]の何れかに記載する白色導電粉末を溶媒に分散してなる分散液。
〔５〕上記[１]〜上記[３]の何れかに記載する白色導電粉末を含有する導電膜。
〔６〕白色導電粉末を固形分７０質量％含有し、膜厚２μｍにおいて表面抵抗が１.０×１０10Ω/□以下である上記[５]に記載する導電膜。
The white conductive powder of the present invention includes the following modes and can be used for the following applications.
[2] The white conductive powder according to [1], wherein the white inorganic powder is titanium oxide.
[3] The antimony-containing tin oxide layer is formed by forming an antimony-containing tin compound on the surface of the white inorganic powder by wet treatment, aging and heat-treating the antimony-containing tin oxide layer, White conductive powder.
[4] A dispersion obtained by dispersing the white conductive powder according to any one of [1] to [3] above in a solvent.
[5] A conductive film containing the white conductive powder according to any one of [1] to [3].
[6] a white conductive powder containing solid content of 70 wt%, the conductive film surface resistivity in the thickness 2μm is that described in [5] is 1.0 × 10 10 Ω / □ or less.
本発明の白色導電粉末は、粉末表面の酸化スズ層のアンチモン含有量を制御することによって、高い導電性を維持しながら優れた白色性を有するようにしたものであり、具体的には、Ｌａｂ表色系においてＬ＝８０以上、ａ＝(−２)〜(＋２)、ｂ＝(−４)〜(＋４)の色調を有し、アンチモンを含有するものの、青色や灰色の色調を帯びず、かつ白色度の高い導電粉末である。 The white conductive powder of the present invention has excellent whiteness while maintaining high conductivity by controlling the antimony content of the tin oxide layer on the powder surface. Specifically, Lab In the color system, L = 80 or more, a = (− 2) to (+2), b = (− 4) to (+4), and contains antimony, but has no blue or gray color tone In addition, the conductive powder has high whiteness.
本発明の白色導電粉末は、ＢＥＴ比表面積１５〜３０ｍ2/ｇの粉末について固形分７０質量％になるように該粉末を添加して膜厚２μｍの塗膜を形成したときに、該塗膜の表面抵抗が１.０×１０10Ω/□以下になる白色導電性粉末であり、優れた白色性と共に高い導電性を有する。
White conductive powder of the present invention, when forming a coating film having a thickness of 2μm was added to the powder so that the solid content of 70 wt% for a powder having a BET specific surface area of 15 to 30 m 2 / g, the coating film Is a white conductive powder having a surface resistance of 1.0 × 10 10 Ω / □ or less, and has high conductivity as well as excellent whiteness.
本発明の白色導電粉末は、酸化スズ層のアンチモン含有量１.０〜１０.０質量％、粉末のアンチモン含有酸化スズ層の割合が２０〜４０質量％であり、該粉末を添加した塗膜を形成したときに、優れた導電性と共に白色による隠蔽性を有する。
The white conductive powder of the present invention has an antimony content of the tin oxide layer of 1.0 to 10.0% by mass, a ratio of the antimony-containing tin oxide layer of the powder of 20 to 40% by mass, and the coating film to which the powder is added When formed, it has a concealing property due to white as well as excellent conductivity.
本発明の白色導電粉末は、表面の導電層（アンチモン含有酸化スズ層）を湿式処理によって形成することができるので気相処理に比べて容易に製造することできる。 Since the conductive layer (antimony-containing tin oxide layer) on the surface can be formed by wet processing, the white conductive powder of the present invention can be easily manufactured as compared with gas phase processing.
本発明の粉末は導電性と共に白色性に優れるので、外観や機能面から白色環境が求められる用途、例えば、自動車用静電塗装プライマー、半導体製造クリーンルームやコンピュータルーム、病院等の内装材ないしカーペットなどにおける導電材料として好適である。また、白色性のみならず、隠蔽性も高く、様々に着色可能で、従来のものと比べ格段に性能が向上している。 Since the powder of the present invention is excellent in whiteness as well as conductivity, it is used in applications where a white environment is required in terms of appearance and function, such as an electrostatic coating primer for automobiles, interior materials or carpets for semiconductor manufacturing clean rooms, computer rooms, hospitals, etc. It is suitable as a conductive material. Moreover, not only whiteness but also concealability is high, it can be colored in various ways, and the performance is remarkably improved as compared with the conventional one.
また、本発明の白色導電粉末は、安定で高い導電性を有するので、機能的な導電材料として各種の機器に広く用いることができる。具体的には、例えば、静電塗装プライマー、帯電防止効果を有する樹脂やタイル、導電性塗料、静電記録材料、複写機関連の帯電ローラー、感光ドラム、トナー、静電ブラシなどにおける導電材料として好適である。 Further, since the white conductive powder of the present invention has a stable and high conductivity, it can be widely used in various devices as a functional conductive material. Specifically, for example, as conductive materials in electrostatic coating primers, resins and tiles having antistatic effects, conductive paints, electrostatic recording materials, copier-related charging rollers, photosensitive drums, toners, electrostatic brushes, etc. Is preferred.
さらに、本発明の白色導電粉末は、酸化スズ層にリンやインジウムを含まないので低コストである。また、本発明の白色導電粉末は水等の溶媒にも分散可能であるので、水性塗料等の導電材料として用いることができる。 Furthermore, the white conductive powder of the present invention is low in cost because the tin oxide layer does not contain phosphorus or indium. Further, since the white conductive powder of the present invention can be dispersed in a solvent such as water, it can be used as a conductive material such as an aqueous paint.
以下、本発明を実施形態に基づいて具体的に説明する。なお、％は特に示さない限り、また数値固有の場合を除いて質量％である。 Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise indicated, “%” means “% by mass” unless otherwise specified.
〔白色導電粉末〕
本発明に係る導電粉末は、白色無機粉末表面にアンチモンを含む酸化スズ層を有し、Ｌａｂ表色系においてＬ＝８０以上、ａ＝(−２)〜(＋２)、ｂ＝(−４)〜(＋４)の色調を有する白色導電粉末であり、ＢＥＴ比表面積が１５〜３０ｍ 2 /ｇであって、酸化スズ層のアンチモン含有量が１.０〜１０.０質量％であり、該粉末におけるアンチモン含有酸化スズ層の割合が２０〜４０質量％であり、該粉末を固形分７０質量％含有する膜厚２μｍの塗膜において該塗膜の表面抵抗が１.０×１０ 10 Ω/□以下であることを特徴とする白色導電粉末である。
[White conductive powder]
The conductive powder according to the present invention has a tin oxide layer containing antimony on the surface of the white inorganic powder. In the Lab color system, L = 80 or more, a = (− 2) to (+2), b = (− 4) A white conductive powder having a color tone of (+4), a BET specific surface area of 15 to 30 m 2 / g, and a tin oxide layer having an antimony content of 1.0 to 10.0% by mass, The ratio of the antimony-containing tin oxide layer is 20 to 40% by mass, and the surface resistance of the coating film is 1.0 × 10 10 Ω / □ in a 2 μm-thick coating film containing 70% by mass of the solid content of the powder. The white conductive powder is characterized by the following .
本発明の白色導電粉末は、その基材として白色無機粉末である酸化チタン用いることができる。酸化チタンはルチル型、アナターゼ型の何れでもよい。なお、ルチル型酸化チタンはアナターゼ型酸化チタンを用いたときよりも少量の酸化スズ量で同等の導電性が得られるので好ましい。 In the white conductive powder of the present invention, titanium oxide, which is a white inorganic powder, can be used as the base material. Titanium oxide may be either a rutile type or an anatase type. In addition, rutile type titanium oxide is preferable since equivalent conductivity can be obtained with a small amount of tin oxide than when anatase type titanium oxide is used.
上記酸化チタン粉末は、溶液や樹脂などに分散したときに、良好な分散性を得るには平均粒径０.０１〜１μmであって球状のものが好ましい。また、酸化チタン粉末表面にアンチモン含有酸化スズ層を有する白色導電粉末は１５〜３０ｍ2/ｇのＢＥＴ比表面積を有するものが好ましい。この場合、上記平均粒径を有する粉末の表面が僅かな凹凸を有するようになり、光の反射などによって白色度が高くなるので好ましい。 The titanium oxide powder preferably has a mean particle size of 0.01 to 1 [mu] m and is spherical to obtain good dispersibility when dispersed in a solution or resin. The white conductive powder having an antimony-containing tin oxide layer on the surface of the titanium oxide powder preferably has a BET specific surface area of 15 to 30 m 2 / g. In this case, it is preferable because the surface of the powder having the average particle diameter has slight irregularities, and the whiteness is increased by light reflection or the like.
本発明の白色導電粉末において、粉末のアンチモン含有酸化スズ層の割合は２０〜４０％が適当であり、２５〜３５％が好ましい。この量が２０％未満では所望の導電性が得るのが難しい。また、この量が４０％より多いと低抵抗にはなるものの、凝集の問題が生じるので好ましくない。 In the white conductive powder of the present invention, the proportion of the antimony-containing tin oxide layer in the powder is suitably 20 to 40%, preferably 25 to 35%. If this amount is less than 20%, it is difficult to obtain desired conductivity. On the other hand, if the amount is more than 40%, the resistance becomes low, but the problem of aggregation occurs, which is not preferable.
アンチモン含有酸化スズ層において、酸化スズ層中のアンチモン含有量は１.０〜１０.０％が好ましい。アンチモン量が１.０％未満では表面抵抗が低下しない。一方、アンチモン量が１０.０％より多いと青色や灰色の色調が強くなり、白色性に問題を生じる。上記アンチモン含有量において、Ｌａｂ表色系のＬ＝８０以上、ａ＝(−２)〜(＋２)、ｂ＝(−４)〜(＋４)の色調を有することができる。Ｌａｂの値が上記範囲を外れるものは白色性に関与する色調が損なわれるので好ましくない。本発明の白色導電粉末はＬａｂの各値が上記範囲内であり、濁りのない良好な白色を有する。 In the antimony-containing tin oxide layer, the antimony content in the tin oxide layer is preferably 1.0 to 10.0%. When the amount of antimony is less than 1.0%, the surface resistance does not decrease. On the other hand, when the amount of antimony is more than 10.0%, the color tone of blue or gray becomes strong, causing a problem in whiteness. The antimony content may have a color tone of L = 80 or more in the Lab color system, a = (− 2) to (+2), and b = (− 4) to (+4). A Lab value outside the above range is not preferred because the color tone related to whiteness is impaired. The white conductive powder of the present invention has each value of Lab within the above range, and has a good white color without turbidity.
本発明の白色導電粉末は、上記含有量の酸化スズ層を有し、酸化スズ層のアンチモン含有量が上記範囲であるものは、固形分７０質量％になるように該粉末を添加して膜厚２μｍの塗膜を形成したときに、該塗膜の表面抵抗が１.０×１０10Ω/□以下の導電性を有することができる。
The white conductive powder of the present invention has a tin oxide layer having the above-mentioned content. When the antimony content of the tin oxide layer is in the above range, the powder is added so that the solid content is 70% by mass. When a coating film having a thickness of 2 μm is formed, the surface resistance of the coating film can have a conductivity of 1.0 × 10 10 Ω / □ or less.
〔製造方法〕
本発明の白色導電粉末について、アンチモンを含有する酸化スズ層を有するものは、白色無機粉末の表面に湿式処理によってアンチモン含有スズ化合物を形成し、これを熱処理してアンチモンを含有する酸化スズ層を形成することによって製造することができる。
〔Production method〕
The white conductive powder of the present invention having an antimony-containing tin oxide layer is formed by forming an antimony-containing tin compound on the surface of the white inorganic powder by wet treatment, and heat-treating this to form a tin oxide layer containing antimony. It can be manufactured by forming.
好ましくは、基材の白色無機粉末を水に分散させ、これにアンチモンを含有するスズ源を加え、低ｐＨ下、例えばｐＨ２以下で加水分解して基材粉末表面にアンチモン含有スズ化合物を析出させ、乾燥後、酸素雰囲気下で熱処理して基材粉末表面に上記酸化スズ層を形成する。 Preferably, the white inorganic powder of the base material is dispersed in water, and a tin source containing antimony is added thereto, and hydrolyzed at a low pH, for example, at pH 2 or lower, to deposit an antimony-containing tin compound on the surface of the base powder. After drying, heat treatment is performed in an oxygen atmosphere to form the tin oxide layer on the surface of the substrate powder.
基材の白色無機粉末としては酸化チタン粉末が用いられる。該基材粉末を水に分散させて４０〜１００℃に加温し、これにアンチモンを含有させたスズ源を加え、これを加水分解して基材粉末表面にスズ化合物を析出・熟成させる。スズ源としては塩化スズ、硝酸スズ、酢酸スズ、その他の可溶性スズ塩を用いることができる。 Titanium oxide powder is used as the white inorganic powder of the substrate. The base powder is dispersed in water, heated to 40 to 100 ° C., a tin source containing antimony is added thereto, and this is hydrolyzed to precipitate and age a tin compound on the surface of the base powder. As the tin source, tin chloride, tin nitrate, tin acetate, and other soluble tin salts can be used.
基材粉末表面にアンチモン含有スズ化合物を析出させた後に、デカンテーションにより残留塩分を除去して乾燥する。なお、スズ源として塩化スズを用いる場合には、塩酸水溶液を加え、ｐＨ４以下でスズ化合物を析出させ、その後の洗浄は塩酸が僅かに残留する程度に止めるのが良い。 After depositing an antimony-containing tin compound on the surface of the substrate powder, the residual salt is removed by decantation and dried. When tin chloride is used as the tin source, an aqueous hydrochloric acid solution is added to precipitate a tin compound at a pH of 4 or lower, and the subsequent washing should be stopped to the extent that hydrochloric acid remains slightly.
本発明の白色導電粉末は、上記湿式処理の後に乾燥し、熱処理を行ってアンチモン含有酸化スズ層を形成する。熱処理温度は４００℃以上〜８００℃以下が好ましい。熱処理温度が４００℃より低いと十分な導電性が得られず、また８００℃より高いと粉末の焼結が始まるので好ましくない。上記熱処理において、白色性をより向上させるには、例えば熱処理を空気中で行うのが好ましい。 The white conductive powder of the present invention is dried after the wet treatment and heat-treated to form an antimony-containing tin oxide layer. The heat treatment temperature is preferably 400 ° C. or higher and 800 ° C. or lower. If the heat treatment temperature is lower than 400 ° C., sufficient conductivity cannot be obtained, and if it is higher than 800 ° C., powder sintering starts, which is not preferable. In the heat treatment, in order to further improve the whiteness, for example, the heat treatment is preferably performed in air.
本発明の白色導電粉末は多様な形態で利用することができる。例えば、該白色導電粉末を溶媒に分散した分散液として利用することができる。また、該白色導電粉末を塗料に添加し、これを塗布して成膜することによって導電膜を形成することができる。具体的には、例えば、本発明の白色導電粉末を固形分７０質量％になるように塗料に加え、膜厚２μｍに成膜し、表面抵抗１.０×１０10Ω/□以下の導電膜を得ることができる。 The white conductive powder of the present invention can be used in various forms. For example, it can be used as a dispersion in which the white conductive powder is dispersed in a solvent. In addition, the conductive film can be formed by adding the white conductive powder to the coating material and applying it to form a film. Specifically, for example, the white conductive powder of the present invention is added to the paint so as to have a solid content of 70% by mass, and the film is formed to a thickness of 2 μm, and the conductive film having a surface resistance of 1.0 × 10 10 Ω / □ or less. Can be obtained.
以下に本発明の実施例を比較例と共に示す。実施例および比較例において、粉末体積抵抗は試料粉末を圧力容器に入れて１００kgf/cm2で圧縮し、この圧粉をデジタルマルチメーター（横河電機製品：型式7561-02）によって測定した。粉体のＬ値、ａ値、ｂ値はスガ試験機社製装置（SM-7-IS-2B）を用いて測定した。塗布膜の表面抵抗は白色導電粉末を含む膜厚約１００μmの薄膜について表面抵抗計（ハイレスタ：三菱油化製品：型式HT-210、供給電圧１００Ｖ）を用いて測定した。ＢＥＴ比表面積は窒素吸着法（柴田化学製品：SA1100型）によって測定した。 Examples of the present invention are shown below together with comparative examples. In Examples and Comparative Examples, the powder volume resistance was measured with a digital multimeter (Yokogawa Electric product: Model 7561-02) after putting the sample powder into a pressure vessel and compressing the powder at 100 kgf / cm 2 . The L value, a value, and b value of the powder were measured using an apparatus (SM-7-IS-2B) manufactured by Suga Test Instruments. The surface resistance of the coating film was measured using a surface resistance meter (Hiresta: Mitsubishi Yuka product: model HT-210, supply voltage 100 V) for a thin film having a thickness of about 100 μm containing white conductive powder. The BET specific surface area was measured by a nitrogen adsorption method (Shibata Chemical product: SA1100 type).
〔実施例１〕
酸化チタン粉末（ルチル型）５０ｇを水３００ccに分散させ、９５℃に加温した。この分散液に、粉体中の酸化スズ含有量が表１の値になるようにアンチモン含有塩化スズを加え、塩酸水溶液を４０分〜６０分かけて添加してｐＨ１〜２に調整した。この湿式処理した粉末を取り出して洗浄し乾燥した。上記湿式処理で加えたアンチモン含有塩化スズは実質的に全量が加水分解され、粉末表面にアンチモン含有スズ化合物が析出した。この乾燥粉末２０ｇを石英管状炉に入れ、表１に示す温度で熱処理した。処理した粉末を取り出して圧粉し、粉末体積抵抗を測定した。また、ＢＥＴ比表面積およびＬａｂ表色系の値を測定した。この結果を表１に示した。
[Example 1]
50 g of titanium oxide powder (rutile type) was dispersed in 300 cc of water and heated to 95 ° C. Antimony-containing tin chloride was added to this dispersion so that the tin oxide content in the powder would be the value shown in Table 1, and an aqueous hydrochloric acid solution was added over 40 to 60 minutes to adjust the pH to 1-2. The wet-processed powder was taken out, washed and dried. The antimony-containing tin chloride added by the wet treatment was substantially entirely hydrolyzed, and an antimony-containing tin compound was deposited on the powder surface. 20 g of this dry powder was placed in a quartz tube furnace and heat-treated at the temperature shown in Table 1. The treated powder was taken out and compacted, and the powder volume resistance was measured. Further, the BET specific surface area and the value of the Lab color system were measured. The results are shown in Table 1.
〔比較例１〕
酸化スズ含有量、熱処理温度を表１に示す条件にした以外は実施例１と同様にして白色導電粉末を製造した。この粉末について粉末体積抵抗、ＢＥＴ比表面積およびＬａｂ表色系の値を測定した。この結果を表１に示した。
[Comparative Example 1]
A white conductive powder was produced in the same manner as in Example 1 except that the tin oxide content and the heat treatment temperature were changed to the conditions shown in Table 1 . The powder volume resistance, BET specific surface area, and Lab color system were measured for this powder. The results are shown in Table 1.
〔実施例２・比較例２〕
実施例１および比較例１において製造した白色導電微粉末２３.０ｇを、市販のアクリル塗料（樹脂含有量10％）１００ｇに加え、ビーズを入れたペイントシェーカーで３０分攪拌した。この塗料をアプリケータでＰＥＴフィルムに乾燥後の膜厚が約２μmになるように塗布し、乾燥後の表面抵抗を表面抵抗計にて測定した。また、塗膜の性状（凝集体によるブツの有無）を目視にて確認した。この結果を表１に示した。
[Example 2 and Comparative Example 2]
23.0 g of the white conductive fine powder produced in Example 1 and Comparative Example 1 was added to 100 g of a commercially available acrylic paint (resin content: 10%) and stirred for 30 minutes with a paint shaker containing beads. This paint was applied to a PET film with an applicator so that the film thickness after drying was about 2 μm, and the surface resistance after drying was measured with a surface resistance meter. In addition, the properties of the coating film (the presence or absence of irregularities due to aggregates) were visually confirmed. The results are shown in Table 1.
表１に示すように、本発明試料Ａ１〜Ａ５は何れもＬ値が８０以上で白色度が高く、表面抵抗が１.０×１０10Ω/□以下であり、導電性が高い。一方、比較試料Ｂ１は塗膜の表面抵抗は低いが、Ｌ値が低く、白色度の高い粉末を得ることができず、しかもｂ値が−５.０であり青色の強い粉末である。また、Ｂ２は表面抵抗が各段に高く、導電性に優れた粉末を得ることができない。
As shown in Table 1, all of the inventive samples A1 to A5 have an L value of 80 or more, high whiteness, a surface resistance of 1.0 × 10 10 Ω / □ or less, and high conductivity. On the other hand, comparative sample B1 has a low surface resistance of the coating film, but has a low L value, a powder with high whiteness cannot be obtained, and has a b value of −5.0 and is a strong blue powder. Further, B2 has a high surface resistance at each stage, and a powder having excellent conductivity cannot be obtained.
また、本発明試料Ａ１〜Ａ２は、酸化スズ層のアンチモン量が少ないので粉体の体積抵抗はＡ３〜Ａ５に比べて高いが、塗膜を形成したときの表面抵抗は格段に低くなり、Ａ３〜Ａ５に近い表面抵抗になる利点がある。 In addition, since the present invention samples A1 to A2 have a small volume of antimony in the tin oxide layer, the volume resistance of the powder is higher than that of A3 to A5, but the surface resistance when the coating film is formed is remarkably low. There is an advantage of surface resistance close to ~ A5.
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