JPH04173955A - Production of colored nacreous mica rigment - Google Patents
Production of colored nacreous mica rigmentInfo
- Publication number
- JPH04173955A JPH04173955A JP29552490A JP29552490A JPH04173955A JP H04173955 A JPH04173955 A JP H04173955A JP 29552490 A JP29552490 A JP 29552490A JP 29552490 A JP29552490 A JP 29552490A JP H04173955 A JPH04173955 A JP H04173955A
- Authority
- JP
- Japan
- Prior art keywords
- mica
- sputtering
- coated
- titanium
- titanium dioxide
- 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.)
- Granted
Links
- 239000010445 mica Substances 0.000 title claims abstract description 97
- 229910052618 mica group Inorganic materials 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000049 pigment Substances 0.000 claims abstract description 61
- 238000004544 sputter deposition Methods 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000012530 fluid Substances 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 15
- 239000003086 colorant Substances 0.000 abstract description 8
- 239000011164 primary particle Substances 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 2
- 235000019646 color tone Nutrition 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000009467 reduction Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- -1 inorganic acid salt Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、雲母粒子表面が膜厚方向にチタンと酸素の成
分比が変化する特殊な酸化チタン皮膜で被覆された、干
渉色を有する有色の着色真珠光沢雲母顔料の製造方法に
関する。Detailed Description of the Invention [Industrial Field of Application] The present invention provides colored mica particles having an interference color, in which the surface of mica particles is coated with a special titanium oxide film in which the composition ratio of titanium and oxygen changes in the film thickness direction. The present invention relates to a method for producing a colored pearlescent mica pigment.
既知の真珠光沢顔料の一つは、微細な薄片状雲母の表面
に二酸化チタン層を形成させたもので、真珠光沢を有し
、種々の干渉色を呈する。その製法としては特公昭４３
−２５６４４に見られるようなチタンの無機酸塩（たと
えば硫酸チタニル）の水溶液を雲母の存在下で加水分解
し、雲母表面に含水二酸化チタンを析出させたのち加熱
する方法が一般的である。使用する雲母ばあらかしめ水
粉枠し、フルイを用いて粒子径を５μｍ〜２００μｍの
範囲にそろえた透明な白雲母系雲母を用いることが多い
。One of the known pearlescent pigments is one in which a titanium dioxide layer is formed on the surface of fine flaky mica, which has pearlescent luster and exhibits various interference colors. The manufacturing method is
A common method is to hydrolyze an aqueous solution of an inorganic acid salt of titanium (for example, titanyl sulfate) such as that seen in No. 25644 in the presence of mica, precipitate hydrated titanium dioxide on the mica surface, and then heat it. The mica used is often transparent muscovite-based mica, which has been sieved with water powder and the particle size is adjusted to a range of 5 μm to 200 μm using a sieve.
生成した真珠光沢顔料は雲母粒子表面の二酸化チタン被
覆層の厚さによって様々な干渉色を呈する。The produced pearlescent pigment exhibits various interference colors depending on the thickness of the titanium dioxide coating layer on the mica particle surface.
干渉色は二酸化チタンの量が生成物の２６〜４０％では
金色、４０〜５０％の範囲では二酸化チタン層の増加の
方向に、赤色、青色、緑色へと変化し、さらに５０〜６
０％では高いオーダーの干渉色が得られる。The interference color is golden when the amount of titanium dioxide is 26-40% of the product, and in the range of 40-50% it changes to red, blue, green in the direction of increasing titanium dioxide layer, and further in the range of 50-60%.
At 0%, high order interference colors are obtained.
こうした真珠光沢雲母顔料は真珠光沢と種々の干渉色を
有するものの、外観は常に白色に近く、鮮やかな外観色
を呈するものは得られていなかった。Although these pearlescent mica pigments have pearlescent luster and various interference colors, their appearance is always close to white, and no one with a bright external color has been obtained.
そこで従来は、様々な外観色を出すために真珠光沢雲母
顔料に酸化鉄、紺青、酸化クロム、カーボンブラック、
カーボンなどの有色顔料を添加していた。しかし、この
ような複数の顔料を混合して使用すると、真珠光沢雲母
顔料が本来有している光沢性や干渉色がそこなわれるた
めに、意匠性に劣るとされていた。Conventionally, in order to create a variety of external colors, pearlescent mica pigments were mixed with iron oxide, deep blue, chromium oxide, and carbon black.
Colored pigments such as carbon were added. However, when such a plurality of pigments are mixed and used, the luster and interference color inherent to the pearlescent mica pigment are impaired, and it has been considered that the design is inferior.
そこで、さらに意匠性の優れた真珠光沢雲母顔料の改良
研究がなされ、以下に示す３つの代表的な方法が報告さ
れている。Therefore, research has been carried out to improve pearlescent mica pigments with better design properties, and the following three representative methods have been reported.
１）二酸化チタン被覆雲母を水中に分散させ、この分散
液に塩基を加えてｐＨを調整し、これと同時に酸化剤と
鉄（ＩＩ）塩とを有する水溶液を徐々に加え、二酸化チ
タン被覆雲母粒子の表面にさらに四三酸化鉄（Ｆｅ３０
４）の沈澱を生じさせて被覆する黒色系の着色真珠光沢
雲母顔料の製造法およびこの黒色系の顔料をさらに大気
中で５００〜１０００℃の範囲で熱処理した赤色系の着
色真珠光沢雲母顔料の製造法（特開昭６ｌ−１９６６６
）。1) Disperse titanium dioxide-coated mica in water, add a base to this dispersion to adjust the pH, and at the same time gradually add an aqueous solution containing an oxidizing agent and iron (II) salt to form titanium dioxide-coated mica particles. Furthermore, triiron tetroxide (Fe30
4) A method for producing a black colored pearlescent mica pigment which is coated by precipitation, and a red colored pearlescent mica pigment obtained by further heat-treating this black pigment in the air at a temperature in the range of 500 to 1000°C. Manufacturing method (JP-A-6L-19666
).
２）二酸化チタン（水和物も含む）もしくは二酸化チタ
ンと金属酸化物の複合体（水和物も含む）で被覆された
薄片状雲母をアンモニアＮＨ，気流中６００〜９５０℃
の温度で加熱処理を行って、二酸化チタンを一酸化チタ
ンへ還元することを特徴とする暗色真珠光沢雲母顔料の
製造法（特開昭５８−１６４６５３）。2) Flaky mica coated with titanium dioxide (including hydrates) or a composite of titanium dioxide and metal oxide (including hydrates) is heated with ammonia NH at 600 to 950°C in an air stream.
1. A method for producing a dark pearlescent mica pigment, which comprises reducing titanium dioxide to titanium monoxide by heat treatment at a temperature of (Japanese Patent Laid-Open No. 164653/1983).
３）雲母粒子表面が二酸化チタンと低次酸化チタン、ま
たは低次酸化チタンで被覆されている有色顔料を造る方
法としては、例えば市販の真珠光沢雲母顔料を５００〜
１０００℃、好ましくは７００〜９００℃の温度で水素
ガスおよびアンモニアガスなどの還元力を有するガスと
ヘリウムガス、アルゴンガス、窒素ガスなどの不活性ガ
スとの混合ガスによって加熱還元する方法、市販の真珠
光沢雲母顔料に二酸化チタンを混合し、該混合物を上記
の方法によって加熱還元する方法、または市販の真珠光
沢雲母顔料に金属チタンを混合し、該混合物を真空下で
５００〜１０００℃、好ましくは７００〜９００″Ｃの
加熱還元するなどの方法を挙げることができる。さらに
は特公昭４３−２５６４４に見られるようなチタンの無
機塩（たとえば硫酸チタニル）の水溶液を前述した雲母
の存在下で加水分解し、雲母粒子表面に含水二酸化チタ
ンを析出させ、これを５００〜１０００℃、好ましくは
７００〜９００℃の温度で水素ガスおよびアンモニアガ
スなどの還元力を有するガスとヘリウムガス、アルゴン
ガス、窒素ガスなどの不活性ガスとの混合ガスによって
加熱還元するか、あるいは雲母粒子表面に含水二酸化チ
タンを析出させたのち加熱して酸化チタン被覆雲母を生
成させ、これを上記市販の真珠光沢雲母顔料の製造と同
様な方法で還元してもよい。また、還元の方法は上述の
水素ガスやアンモニアガスのような還元ガスを用いる方
法に限定されるものではなく、酸化チタン被覆雲母を水
素などの還元炎を用いて還元する方法や、雲母粒子をハ
ロゲン化チタン、例えば四塩化チタンの溶液に懸濁させ
、この懸濁液を空気と水素の混合ガスの炎中で酸化分解
させる方法をとることもできる（特開昭５９−２１２４
２２）。3) As a method for producing a colored pigment in which the surface of mica particles is coated with titanium dioxide, lower titanium oxide, or lower titanium oxide, for example, a commercially available pearlescent mica pigment is
A method of thermal reduction using a mixed gas of a gas having reducing power such as hydrogen gas and ammonia gas and an inert gas such as helium gas, argon gas, or nitrogen gas at a temperature of 1000°C, preferably 700 to 900°C, commercially available A method in which a pearlescent mica pigment is mixed with titanium dioxide and the mixture is heated and reduced by the above method, or a commercially available pearlescent mica pigment is mixed with metallic titanium and the mixture is heated under vacuum at 500 to 1000°C, preferably Examples include methods such as thermal reduction at 700 to 900"C.Furthermore, as shown in Japanese Patent Publication No. 43-25644, an aqueous solution of an inorganic titanium salt (for example, titanyl sulfate) is hydrated in the presence of the above-mentioned mica. Decomposed to precipitate hydrated titanium dioxide on the surface of mica particles, which is then heated at a temperature of 500 to 1000°C, preferably 700 to 900°C, with a gas having reducing power such as hydrogen gas and ammonia gas, helium gas, argon gas, and nitrogen gas. Either by heating reduction with a mixed gas with an inert gas such as gas, or by precipitating hydrated titanium dioxide on the surface of mica particles and then heating to produce titanium oxide-coated mica, this is mixed with the above-mentioned commercially available pearlescent mica pigment. The reduction may be carried out in the same manner as in production.The reduction method is not limited to the above-mentioned method using a reducing gas such as hydrogen gas or ammonia gas; titanium oxide-coated mica may be reduced by hydrogen or other It is also possible to use a method of reduction using a flame, or a method of suspending mica particles in a solution of titanium halide, such as titanium tetrachloride, and oxidizing and decomposing this suspension in a flame of a mixed gas of air and hydrogen. It can be done (Japanese Patent Application Laid-Open No. 59-2124
22).
上記の１）の方法では赤色および黒色系のものしか得ら
れず、２）の方法では青色、青黒色、黒色および茶黒色
系のものしか製造できないという欠点が各々にあった。Each method had the drawback that the method 1) could only produce red and black products, and the method 2) could only produce blue, blue-black, black, and brown-black products.
一方、３）の方法では青色、緑色、金色および赤紫色な
どの着色が可能であるが、二酸化チタンで被覆した真珠
光沢雲母顔料を水素ガス雰囲気下で５００〜１０００℃
の高温度で加熱還元する必要があり、二酸化チタンの膜
厚が非常に小さいので５００〜１０００℃の高温で還元
を行うと二酸化チタン皮膜全体が還元されるおそれがあ
り１粒径方向のチタンと酸素の成分比の変化の制御がむ
つかしい。さらに、この温度では二酸化チタン被覆雲母
粒子どうしが焼結し凝集固化して単分散の微細な粉末顔
料が得られず、粉末状態を保つには特別の装置が必要と
なる。On the other hand, method 3) allows coloring such as blue, green, gold, and reddish-purple, but pearlescent mica pigment coated with titanium dioxide is heated at 500 to 1000°C in a hydrogen gas atmosphere.
Since the film thickness of titanium dioxide is very small, if reduction is carried out at a high temperature of 500 to 1000°C, there is a risk that the entire titanium dioxide film will be reduced. It is difficult to control changes in the oxygen component ratio. Furthermore, at this temperature, the titanium dioxide-coated mica particles sinter and coagulate together, making it impossible to obtain a monodisperse fine powder pigment, and a special device is required to maintain the powder state.
雲母粒子自体に、酸素ガス気流中で（減圧下に）チタン
をスパッタしてチタン酸化物の皮膜を形成する方法も考
えられるが、チタンターゲットと酸素が反応してターゲ
ットが酸化し、さらに酸素ガスによるスパッタ率はアル
ゴンガスやヘリウムガスによるそれに比べて、著しく小
さいので実用的でない。また粒径方向のチタンと酸素の
成分比の変化の制御も極めてむづかしい。It is also possible to form a titanium oxide film on the mica particles themselves by sputtering titanium in an oxygen gas stream (under reduced pressure), but the titanium target and oxygen react and the target is oxidized, and further oxygen gas The sputtering rate is significantly lower than that using argon gas or helium gas, so it is not practical. Furthermore, it is extremely difficult to control changes in the component ratio of titanium and oxygen in the grain size direction.
〔発明が解決しようとしている問題点〕本発明者らは前
記従来の着色真珠光沢雲母顔料およびその製造法が抱え
る問題点を解決すべく鋭意研究したところ、真空条件下
で二酸化チタン被覆雲母の表面をスパッタリング法によ
って金属チタンで被覆すると、二酸化チタン皮膜が低次
酸化物に還元される現象を発見した。この方法によると
水素ガス中で５００〜１０００℃に加熱還元する必要が
ない。その上、金色、銀色、赤色、青色および緑色など
の多種類の着色が可能になるうえ、干渉色も兼備するこ
とから、従来具られなかった新しい意匠性を有する着色
真珠光沢雲母顔料を製造できることを見出した。[Problems to be Solved by the Invention] The present inventors conducted extensive research to solve the problems faced by the conventional colored pearlescent mica pigments and their production methods, and found that the surface of titanium dioxide-coated mica under vacuum conditions We discovered that when titanium dioxide is coated with metallic titanium by sputtering, the titanium dioxide film is reduced to a lower oxide. According to this method, there is no need for heating reduction to 500 to 1000°C in hydrogen gas. Furthermore, it is possible to produce a variety of colored pearlescent mica pigments such as gold, silver, red, blue, and green, as well as interference colors, making it possible to produce colored pearlescent mica pigments with new design properties that have not been available in the past. I found out.
二酸化チタン被覆雲母の表面にさらに金属チタンを被覆
する方法としては、前記のスパッタリング法以外にも真
空蒸着法、イオンブレーティング法、ＣＶＤ法などの公
知の方法を適用することが考えられるが、コーティング
の対象が粉末であるために、装置の構造や操作に関して
なお問題がある。As a method for further coating the surface of titanium dioxide-coated mica with metallic titanium, in addition to the sputtering method described above, it is possible to apply known methods such as vacuum evaporation method, ion blating method, and CVD method. Since the target is powder, there are still problems with the structure and operation of the device.
〔問題点を解決するための手段・発明の構成〕本発明は
、二酸化チタンで被覆した雲母からなる真珠光沢雲母顔
料の表面を、さらにスパッタリング法によって金属チタ
ンで被覆処理し、それにより該二酸化チタン皮膜を低次
酸化物に還元することからなる着色真珠光沢雲母顔料の
製造法を提供する。[Means for Solving the Problems/Structure of the Invention] In the present invention, the surface of a pearlescent mica pigment made of mica coated with titanium dioxide is further coated with metallic titanium by a sputtering method, whereby the titanium dioxide is A method for producing colored pearlescent mica pigments is provided, which comprises reducing a film to a lower oxide.
本発明はまた、粉体減圧熱処理帯域と、流動床スパッリ
ング帯域と、流体ミル粉体分散処理帯域とを設け、二酸
化チタン被覆雲母からなる真珠光沢雲母顔料をこの三帯
域の間を循環させて、スパッタリングによる金属チタン
被覆処理を反復して行う着色真珠光沢雲母顔料の製造法
を提供する。The present invention also includes a powder vacuum heat treatment zone, a fluidized bed sparring zone, and a fluid mill powder dispersion treatment zone, and a pearlescent mica pigment made of titanium dioxide coated mica is circulated between these three zones. , provides a method for producing a colored pearlescent mica pigment in which a metallic titanium coating treatment by sputtering is repeated.
スパッタリングは、好ましくは２００℃以下の温度で行
う。２００℃を超えると、真珠光沢雲母顔料の凝集が激
しくなり、塊化が起こり、均一なチタン被覆が困難とな
るからである。Sputtering is preferably performed at a temperature of 200°C or lower. This is because if the temperature exceeds 200° C., the pearlescent mica pigment will agglomerate violently, resulting in agglomeration, making it difficult to uniformly coat titanium.
その製品は原料の二酸化チタン被覆雲母からなる真珠光
沢雲母顔料の干渉色の色調と本発明による着色真珠光沢
雲母顔料の色調とが同一系統であることおよび低次酸化
物皮膜中のチタンと酸素の成分比が膜厚方向で変化して
いることを特徴とする。The product is characterized in that the interference color tone of the pearlescent mica pigment made of mica coated with titanium dioxide as a raw material is the same as that of the colored pearlescent mica pigment according to the present invention, and that It is characterized in that the component ratio changes in the film thickness direction.
二酸化チタン被覆雲母の真珠光沢雲母顔料としては、粒
径が５μｍ〜２００μｍの範囲の雲母の表面に例えば、
特公昭４３−２５６４４に見られるようなチタンの無機
酸塩（たとえば硫酸チタニル）の水溶液を雲母の存在下
で加水分解し、雲母の表面に含水二酸化チタンを析出さ
せたのち加熱する方法によって製造したものを使用する
ことができる。二酸化チタンの含有率は１０ｗｔ％〜６
０ｗｔ％の範囲で、膜厚によって銀色、青色、緑色、赤
色、赤紫色および金色などの干渉色が付与される。As a pearlescent mica pigment of titanium dioxide-coated mica, for example,
It was produced by a method of hydrolyzing an aqueous solution of an inorganic acid salt of titanium (for example, titanyl sulfate) in the presence of mica, precipitating hydrated titanium dioxide on the surface of the mica, and then heating it, as shown in Japanese Patent Publication No. 43-25644. things can be used. The content of titanium dioxide is 10wt%~6
In the range of 0 wt%, interference colors such as silver, blue, green, red, magenta, and gold are imparted depending on the film thickness.
二酸化チタン被覆雲母の真珠光沢雲母顔料への金属チタ
ンのスパッタリング法による被覆は実開平２−１４３６
０または特願平１−７４７７０に開示された技術によっ
て実施できる。これらの技術は、金属、セラミックスま
たはプラスチックの微粉末を、（イ）不活性雰囲気中で
気流ジェットミル処理して一次粒子に分散し、
（ロ）該分散処理して得た微粉末を不活性雰囲気中で減
圧加熱処理し、
（ハ）該加熱処理した微粉末をスパッタリング源を納め
た回転容器に仕込み、該容器を回転させて微粉末の流動
層を形成し、容器を回転した状態で流動微粉末にスパッ
タリングすることにより被覆することからなる微粉末を
被覆する方法であり、（１）連続しない別々の回転軸に
支持される回転可能で真空排気可能のバレルであって、
その内部に第１の回転軸に支持されるスパッタ源が設け
られ、第２の回転軸が被覆されるべき微粉未導入路およ
び排気路としての機能を有し、かつその内部に真空排気
および不活性ガス導入の管路を備えているものからなる
スパッタリング室と；（２）該スパッタリング室の第２
の回転軸の微粉末排出路に弁を有する連通路によって連
通ずるジェットミル手段と：
（３）該ジェットミルに弁を有する連通路（導管）によ
って連通ずる真空排気可能の加熱攪拌容器と；（４）該
攪拌容器と前記第１の回転軸に連通ずる、弁を有する微
粉末導管と；
とからなる連続微粉末被覆装置である。Coating of titanium dioxide-coated mica onto pearlescent mica pigment by sputtering method of metallic titanium is disclosed in Utility Model Application Publication No. 2-1436.
0 or Japanese Patent Application No. 1-74770. These techniques involve (a) dispersing fine powders of metals, ceramics, or plastics into primary particles through air jet milling in an inert atmosphere, and (b) dispersing the fine powders obtained through the dispersion treatment into inert particles. (c) The heat-treated fine powder is charged into a rotating container containing a sputtering source, the container is rotated to form a fluidized bed of fine powder, and the fine powder is fluidized while the container is rotated. A method of coating a fine powder comprising coating the fine powder by sputtering, the method comprising: (1) a rotatable and evacuable barrel supported on separate, discontinuous rotating shafts;
A sputtering source supported by a first rotating shaft is provided inside the sputtering shaft, and the second rotating shaft has functions as a passage for introducing fine powder to be coated and an exhaust passage. a sputtering chamber comprising a conduit for introducing active gas; (2) a second sputtering chamber;
(3) A heating stirring vessel that can be evacuated and communicated with the jet mill through a communication passage (conduit) having a valve; 4) A continuous fine powder coating device comprising: a fine powder conduit having a valve and communicating with the stirring vessel and the first rotating shaft.
上記の発明において、雲母に種々の金属、例えば鉄、銅
、銀、金、錫、白金、ニッケル、チタン、コバルト、ク
ロム、アルミニウム、亜鉛、タングステンおよびこれら
の合金を被覆することが可能であることはすでに開示さ
れているが、本発明は原材料として二酸化チタン被覆雲
母である真珠光沢雲母顔料を使用し、これをさらにスパ
ッタリング法によって金属チタンで被覆する際に二酸化
チタンが還元されて低次酸化物の皮膜になる新しく発見
された現象に基づいている。In the above invention, it is possible to coat mica with various metals, such as iron, copper, silver, gold, tin, platinum, nickel, titanium, cobalt, chromium, aluminum, zinc, tungsten, and alloys thereof. has already been disclosed, but the present invention uses a pearlescent mica pigment, which is titanium dioxide-coated mica, as a raw material, and when this is further coated with metallic titanium by a sputtering method, the titanium dioxide is reduced to form a lower oxide. It is based on a newly discovered phenomenon in which the film of
本発明の方法は種々の装置で実施することができるが、
前述の装置を使用して連続的に実施するのが好都合であ
る。Although the method of the present invention can be carried out in a variety of devices,
Conveniently, it is carried out continuously using the apparatus described above.
第１図は本発明方法に使用する装置の一例の構造を示す
１側面から眺めて適宜断面で示す概念図であり、第２図
は第１図に示す装置を第１図と直角の方向から眺めた大
体において第１図の■−■線にそった断面を示す同様の
図面である。FIG. 1 is a conceptual diagram showing the structure of an example of the device used in the method of the present invention, viewed from one side and showing appropriate cross sections, and FIG. 2 is a conceptual diagram showing the device shown in FIG. 1 from a direction perpendicular to FIG. This is a similar drawing showing a cross section generally taken along the line ■--■ of FIG. 1 when viewed.
装置の主要部は、減圧加熱処理室１、回転バレル型スパ
ッタリング室２、流体ジェットミル３および粉末フィル
ター４からなる。The main parts of the apparatus consist of a reduced pressure heat treatment chamber 1, a rotating barrel type sputtering chamber 2, a fluid jet mill 3, and a powder filter 4.
減圧加熱処理室１は、電気抵抗加熱される容器であって
フィルター５を介して主排気系６および高度排気系７に
連通ずる。主排気系は機械的真空ポンプであり、高度排
気系はクライオソープションポンプ、ターボ分子ポンプ
またはメカニカルブースターポンプ等と冷却トラップの
組合せである。The reduced pressure heat treatment chamber 1 is a container heated by electrical resistance and communicates with a main exhaust system 6 and an advanced exhaust system 7 via a filter 5 . The main evacuation system is a mechanical vacuum pump, and the advanced evacuation system is a combination of a cryosorption pump, turbomolecular pump, or mechanical booster pump, etc., and a cooling trap.
減圧加熱処理室１は減圧加熱処理した微粉末８を回転バ
レル型スパッタリング室２に送入する導管ｌＯへ落下さ
せるためのスクリューフィーダー９とこれを回転するモ
ーター４０を備えている。The reduced pressure heat treatment chamber 1 is equipped with a screw feeder 9 for dropping the fine powder 8 subjected to the reduced pressure heat treatment into a conduit lO for feeding into the rotating barrel type sputtering chamber 2, and a motor 40 for rotating the screw feeder 9.
バレル型スパッタリング室（以下単にバレルと称するこ
とがある）２は第２図に示されるようにボールミルのよ
うな構造の回転円筒体であって。The barrel-type sputtering chamber (hereinafter sometimes simply referred to as barrel) 2 is a rotating cylindrical body having a ball mill-like structure, as shown in FIG.
減圧加熱処理室１と、同じ導管１０に連通ずる排気系６
．７に連通ずる。そしてその一方の側壁は、前記の導管
１０が下方に延び、その後に緩やかに直角方向に湾曲す
る水平部分を回転軸として支持される。この軸とバレル
２の側壁の間には気密を保つために軸受として磁気シー
ル３０が使用される。An exhaust system 6 communicating with the reduced pressure heat treatment chamber 1 and the same conduit 10
．． It connects to 7. One side wall is supported with a horizontal portion as a rotation axis where the conduit 10 extends downward and then gently curves at right angles. A magnetic seal 30 is used as a bearing between this shaft and the side wall of the barrel 2 to maintain airtightness.
このバレルの反対側の側壁からは同様の軸受機構３０′
を介してバレル２の回転軸として機能するシャフトが
挿入され、その先端にスパッタリング装置５０が対峙し
て保持される。その姿勢は垂直ではなく後に説明するバ
レル２の回転によって生ずる粉末床の位置によって決定
される傾きを有する。From the opposite side wall of this barrel is a similar bearing mechanism 30'.
A shaft functioning as a rotating shaft of the barrel 2 is inserted through the shaft, and the sputtering device 50 is held at the tip thereof facing each other. Its position is not vertical but has an inclination determined by the position of the powder bed caused by the rotation of the barrel 2, which will be explained later.
このスパッタ源は、バレルの回転中心軸を経て供給され
る図示されていない電源よりの高周波電流によって作動
される。This sputtering source is operated by a high frequency current from a power supply (not shown) supplied through the central axis of rotation of the barrel.
スパッタリング室２は減圧加熱処理室１と流体ジェット
ミル３を介して連結するが、その導管１０と１１には弁
１２１および１２２を備えている。導管１０は前記のよ
うに水平に湾曲してバレル２の中に進入してから再び下
方に湾曲してバレルの底部近くに到達する。この場合そ
の湾曲は垂直に下方に向かうのではなく、バレルの回転
によって生ずる微粉末の流動床の生成する位置に向けら
れている。The sputtering chamber 2 is connected to the reduced pressure heat treatment chamber 1 via a fluid jet mill 3, the conduits 10 and 11 of which are equipped with valves 121 and 122. The conduit 10 curves horizontally into the barrel 2 as described above and then curves downward again until it reaches near the bottom of the barrel. In this case, the curvature is not directed vertically downwards, but towards the point at which a fluidized bed of fine powder is created by the rotation of the barrel.
スパッタリング室の他方の側壁は別の軸１２によってお
なじく磁気シール３０によって回転可能に支持される。The other side wall of the sputtering chamber is rotatably supported by another shaft 12, also by a magnetic seal 30.
スパッタリング室は、支持ロール１３と回転モーター１
４とプーリー１５によって回転させらされたまま制御さ
れる。なお、スパッタリング室２の内部の微粉末搬送導
管１０および搬出導管１１および真空排気系に連通する
細径のパイプ１９はいずれもスパッタリングによって被
覆されにくい黒鉛製のものを用いた。The sputtering chamber includes a support roll 13 and a rotating motor 1.
4 and pulley 15 to keep it rotating. The fine powder conveying conduit 10 and the discharge conduit 11 inside the sputtering chamber 2 and the small diameter pipe 19 communicating with the evacuation system were all made of graphite, which is difficult to be coated by sputtering.
スパッタ源５０、例えば二極マグネトロンは、前記の軸
１２の延長上に支持され、図示されていないが、高さ調
整ネジによって微粉末の流動層１８との距離が調節でき
る構造となっている。勿論この操作は作業の休止中に、
バレルの側壁を除去した状態で実施される。A sputtering source 50, for example a bipolar magnetron, is supported on an extension of the shaft 12, and has a structure in which the distance from the fine powder fluidized bed 18 can be adjusted by a height adjustment screw (not shown). Of course, this operation can be performed while work is paused.
It is carried out with the side wall of the barrel removed.
スパッタリングによって被覆された微粉末は減圧熱処理
室１を減圧しておき、弁１２１を閉じ、弁１２２を解放
して、減圧加熱処理室１とスパッタリング室２との連絡
を遮断し、不活性ガス送入パイプ１９より不活性ガスを
少しずつ送入することによって流体ジェットミル３に搬
送できる。流体ジェットミル３はモーター２０によって
高速回転するプロペラ２１に不活性ガス流に乗せた微粉
末を衝突させる構造のものである。言うまでもなく、軸
１２の内部にはスパッタ源に電気を供給する導線が納め
られている。The fine powder coated by sputtering is removed by reducing the pressure in the reduced pressure heat treatment chamber 1, closing the valve 121 and opening the valve 122 to cut off communication between the reduced pressure heat treatment chamber 1 and the sputtering chamber 2, and inert gas supply. The inert gas can be conveyed to the fluid jet mill 3 by introducing the inert gas little by little from the inlet pipe 19. The fluid jet mill 3 has a structure in which fine powder carried by an inert gas flow collides with a propeller 21 rotated at high speed by a motor 20. Needless to say, inside the shaft 12 is housed a conductor for supplying electricity to the sputtering source.
ジェットミル３の排出側は弁２２を備えた微粉末１ｉ環
パイプ２３に連通し、さらに減圧熱処理室１に連通ずる
。この微粉末循環パイプ２３の弁２２の下部から弁２４
を備えた分岐管により粉末フィルター４に連通ずる。こ
の粉末フィルター４は円筒形フィルター２５を介して排
気系２６に連なるトラップである。The discharge side of the jet mill 3 communicates with a fine powder 1i ring pipe 23 equipped with a valve 22, and further communicates with the reduced pressure heat treatment chamber 1. From the bottom of the valve 22 of this fine powder circulation pipe 23 to the valve 24
It communicates with the powder filter 4 through a branch pipe equipped with a. This powder filter 4 is a trap connected to an exhaust system 26 via a cylindrical filter 25.
この装置は、本発明者らの一部の者の設計に基づき（株
）三栄理研によって製作され、概路次の寸法を有する。This device was manufactured by Sanei Riken Co., Ltd. based on a design by some of the inventors, and has the following general dimensions.
減圧加熱処理室の直径３００ｍｍ、高さ１５０ｍｍ、回
転式バレル型スパッタリング室の直径５００ｍｍ、厚さ
３００ｍｍ、なお使用されたスパッタリング源は東京ハ
イパワー社製のｒ１５００ＤＪであり、使用されたジェ
ットミルは三協電業（株）製のｒＤＡ−３４であった。The reduced pressure heat treatment chamber has a diameter of 300 mm and a height of 150 mm, and the rotating barrel type sputtering chamber has a diameter of 500 mm and a thickness of 300 mm.The sputtering source used was R1500DJ manufactured by Tokyo High Power Co., Ltd., and the jet mill used was It was rDA-34 manufactured by Kyodo Gyo Co., Ltd.
着色真珠光沢雲母顔料の色は原料の二酸化チタン被覆雲
母からなる真珠光沢雲母顔料の色調と同一系統であり、
金属チタンのスパッタリングの量が少いほど明色になり
、多いほど暗色となる傾向がある。なお、金属チタンの
スパッタリングの量は二酸化チタン被覆雲母からなる真
珠光沢雲母顔料に対して、１νｔ％〜３０ｗｔ％が好ま
しい。１ｗｔ％未満ではほとんど着色効果は認められず
、３０ｔｚｔ％を超えると有彩色ではない灰色のメタリ
ック調となるので好ましくない。The color of the colored pearlescent mica pigment is the same as that of the pearlescent mica pigment made of titanium dioxide-coated mica as a raw material,
The smaller the amount of sputtered titanium metal, the brighter the color, and the larger the amount, the darker the color. The amount of sputtering of metallic titanium is preferably 1vt% to 30wt% with respect to the pearlescent mica pigment made of titanium dioxide-coated mica. If it is less than 1 wt%, almost no coloring effect is observed, and if it exceeds 30 tzt%, it becomes a gray metallic tone that is not a chromatic color, which is not preferable.
次ぎに本発明を実施例によって例示する。The invention will now be illustrated by examples.
実施例１
雲母フレーク（径１０〜２０μ、厚さ０．５μ程度）５
０ｇをイオン交換水５００＋ａＱに添加して十分に攪拌
し均一に分散させた。得られた分散液に濃度４０重量％
の硫酸チタニル水溶液１５８．２ｍｆｌを加えて、攪拌
しながら加熱し６時間沸騰させた。放冷後、ろ過水法し
９００℃で焼成して、表面が二酸化チタンで被覆された
赤色の干渉色を有する真珠光沢雲母顔料９０ｇを得た。Example 1 Mica flakes (diameter 10-20μ, thickness approximately 0.5μ) 5
0g was added to 500+aQ of ion-exchanged water and thoroughly stirred to uniformly disperse it. The resulting dispersion had a concentration of 40% by weight.
158.2 mfl of an aqueous titanyl sulfate solution was added thereto, and the mixture was heated while stirring and boiled for 6 hours. After cooling, it was fired at 900° C. using the filtered water method to obtain 90 g of a pearlescent mica pigment whose surface was coated with titanium dioxide and had a red interference color.
次に、第１図および第２図に示す粉末スパッタリング装
置を用いて１０ｗｔ％量の金属チタンのスパッタリング
を行なった。すなわち、前述の９０ｇの二酸化チタン被
覆雲母顔料を回転式バレル型スパッタリング室に側壁を
外して装入し、次いで減圧加熱処理室を２ Ｘ １０−
’Ｔｏｒｒに減圧した後、アルゴンガスを不活性ガス送
入パイプより徐々に送り込むと同時に流体ジェットミル
を使用して一次粒子に分散した後、減圧加熱処理室に捕
集した。捕集した二酸化チタン被覆雲母顔料を２×１Ｏ
−２Ｔｏｒｒに減圧しツツ、ヒーターで１００℃に加熱
して、乾燥および脱ガスを３０分間行なった。次に、あ
らかじめアルゴンガスで置換されたスパッタリング室に
二酸化チタン被覆雲母顔料を移送した。移送後、スパッ
タリング室を回転数５ ｒｐ＋＊で回転しつつ、２ Ｘ
１Ｏ−２Ｔｏｒｒの減圧下で二極方式マグネトロンに
よるスパッタリング（電力０．２ｋＶＸ２個、周波数１
３．５６ＭＨｚ）を開始した。二酸化チタン被覆雲母顔
料の温度は２００ ’Ｃ以下であった。１時間で約０，
２ｗｔ％量の金属チタン被覆が形成された。この工程を
５回繰り返して、合計１，０ｗｔ％量の金属チタン被覆
が生じた。Next, 10 wt % of titanium metal was sputtered using the powder sputtering apparatus shown in FIGS. 1 and 2. That is, 90 g of the titanium dioxide-coated mica pigment described above was charged into a rotating barrel-type sputtering chamber with the side wall removed, and then the vacuum heat treatment chamber was heated to 2×10 −
After the pressure was reduced to 'Torr, argon gas was gradually fed through an inert gas inlet pipe and at the same time dispersed into primary particles using a fluid jet mill, the particles were collected in a reduced pressure heat treatment chamber. The collected titanium dioxide-coated mica pigment was
The pressure was reduced to -2 Torr, and the mixture was heated to 100°C using a heater to perform drying and degassing for 30 minutes. Next, the titanium dioxide-coated mica pigment was transferred to a sputtering chamber that had been previously purged with argon gas. After the transfer, while rotating the sputtering chamber at a rotation speed of 5 rp+*,
Sputtering using a two-pole magnetron under reduced pressure of 1O-2Torr (power 0.2kV x 2, frequency 1
3.56 MHz). The temperature of the titanium dioxide coated mica pigment was below 200'C. Approximately 0 in 1 hour,
A 2 wt% amount of titanium metal coating was formed. This process was repeated 5 times, resulting in a total amount of 1.0 wt% titanium metal coating.
スパッタリングによる被覆作業終了後は不活性ガス送入
パイプを通してスパッタリング室にアルゴンガスを導入
しつつ、雲母顔料を含むアルゴンガス流を粉末フィルタ
ーに送り込んで赤色真珠光沢雲母顔料を得た。After the sputtering coating was completed, argon gas was introduced into the sputtering chamber through an inert gas supply pipe, and a flow of argon gas containing the mica pigment was sent to the powder filter to obtain a red pearlescent mica pigment.
本実施例によって得られた赤色真珠光沢雲母顔料はｗｔ
察の結果、雲母表面が第３図のオージェ分析結果で示す
ような、膜厚方向でチタンと酸素の成分比が変化してい
る約２ 、９００人厚０チタン低次酸化物の皮膜によっ
ておおわれていることが判明した。The red pearlescent mica pigment obtained in this example was wt
As a result of our investigation, we found that the mica surface was covered with a film of lower titanium oxide with a thickness of approximately 2,900 mm and a composition ratio of titanium and oxygen varying in the film thickness direction, as shown in the Auger analysis results in Figure 3. It turned out that
実施例２
実施例１で用いたものと同じ雲母フレーク５０ｇをイオ
ン交換水５００ｍＱに添加して十分に攪拌し均一に分散
させた。得られた分散液に濃度４０重量％の硫酸チタニ
ル水溶液３１２５．５ｍＱを加えて、撹拌しながら加熱
し６時間沸騰させた。放冷後、ろ過水法し９００℃で焼
成して、表面が二酸化チタンで被覆された緑色の干渉色
を有する真珠光沢雲母顔料１００ｇを得た。次に、前述
の第１図および第２図に示す粉末スパッタリング装置を
用いて３０％ｉｔ％量の金属チタンのスパッタリングを
行なった。すなわち、前述の１００ｇの真珠光沢雲母顔
料を回転式バレル型スパッタリング室に投入し、次いで
減圧加熱処理室を２ Ｘ １０−”Ｔｏｒｒに減圧した
後、アルゴンガスを不活性ガス送入パイプより徐々に送
り込むと同時に流体ジェットミルを使用して一次粒子に
分散した後、減圧加熱処理室に捕集した。捕集した雲母
顔料を２ Ｘ １０−”Ｔｏｒｒに減圧しつつ、ヒータ
ーで１００℃に加熱して、乾燥および脱ガス３０分間行
なった。次に、あらかじめアルゴンガスで置換されたス
パッタリング室に雲母顔料を移送した。移送後、スパッ
タリング室を回転数５ｒρｍで回転しつつ、 ２ Ｘ
１Ｏ−２Ｔｏｒｒの減圧下で二極方式マグネトロン方式
によるスパッタリング（電力３．０１ＷＸ２個、周波数
１３．５６ＭＨｚ）を開始した。雲母顔料の温度は２０
０℃以下であった。１時間で約３ｗｔ％量の金属チタン
が付着した。この工程を１０回繰り返して合計３０ｔｙ
ｔ％量の金属チタン被覆を施した。Example 2 50 g of the same mica flakes used in Example 1 were added to 500 mQ of ion-exchanged water and thoroughly stirred to uniformly disperse the mixture. 3125.5 mQ of titanyl sulfate aqueous solution having a concentration of 40% by weight was added to the obtained dispersion, and the mixture was heated with stirring and boiled for 6 hours. After cooling, the mixture was fired at 900° C. using a filtered water method to obtain 100 g of a pearlescent mica pigment having a green interference color and whose surface was coated with titanium dioxide. Next, titanium metal was sputtered in an amount of 30% it% using the powder sputtering apparatus shown in FIGS. 1 and 2 described above. That is, 100 g of the above-mentioned pearlescent mica pigment was put into a rotating barrel-type sputtering chamber, and then, after reducing the pressure in the reduced-pressure heat treatment chamber to 2 x 10-'' Torr, argon gas was gradually introduced from an inert gas supply pipe. At the same time as feeding, it was dispersed into primary particles using a fluid jet mill, and then collected in a vacuum heat treatment chamber.The collected mica pigment was heated to 100°C with a heater while reducing the pressure to 2 x 10-'' Torr. Then, drying and degassing were performed for 30 minutes. Next, the mica pigment was transferred to a sputtering chamber that had been previously purged with argon gas. After the transfer, while rotating the sputtering chamber at a rotation speed of 5 rpm,
Sputtering using a bipolar magnetron method (power: 3.01 W x 2, frequency: 13.56 MHz) was started under a reduced pressure of 1 O -2 Torr. The temperature of mica pigment is 20
The temperature was below 0°C. Approximately 3 wt% of metallic titanium was deposited in 1 hour. Repeat this process 10 times for a total of 30ty
A metallic titanium coating was applied in an amount of t%.
スパッタリングによる被覆作業終了後は不活性ガス送入
パイプを通してスパッタリング室にアルゴンガスを導入
しつつ、雲母顔料を含むアルゴンガス流を粉末フィルタ
ーに送り込んで緑色真珠光沢雲母顔料を得た。After the sputtering coating was completed, argon gas was introduced into the sputtering chamber through an inert gas supply pipe, and a stream of argon gas containing the mica pigment was sent to the powder filter to obtain a green pearlescent mica pigment.
本実施例によって得られた緑色真珠光沢雲母顔料は観察
の結果、雲母粒子の表面が第４図のオージェ分析結果で
示すような、膜厚方向でチタンと酸素の成分比が変化し
ている約６ 、６００人厚０チタンの低次酸化物の皮膜
によっておおわれていることが判明した。As a result of observation, the green pearlescent mica pigment obtained in this example has a surface of mica particles with a composition ratio of titanium and oxygen that changes in the film thickness direction, as shown in the Auger analysis results in Figure 4. It was found that the surface was covered with a low-order oxide film of titanium with a thickness of 0.6 and 600.
これらの着色真珠光沢雲母顔料は、塗料やプラスチック
の新しい着色顔料として外装建材、内装建材、家電製品
、自動車、船舶などの用途に使用することができる。These colored pearlescent mica pigments can be used as new coloring pigments for paints and plastics in applications such as exterior building materials, interior building materials, home appliances, automobiles, and ships.
第１図は本発明の方法を実施するための装置の概念を示
す一側面の断面図、第２図は第１図の■−■線にそった
断面図で示す第１図と直角方向の概念的断面図である。
第３図および第４図は各々本発明の製品である赤色およ
び緑色の真珠光沢顔料の直径方向のオージェ分析結果を
示すグラフである。第１．２図において、
１・・・減圧加熱処理室
２・・・回転バレル型スパッタリング室３・・・流体ジ
ェットミル
４・・・粉末フィルター
５・・・フィルター
６・・・主排気系
７・・・高度排気系
８・・・減圧加熱した粉末
９・・・スクリューフィーダー
１０、１１・・・導管
１２１、１２２・・・弁
１３・・・支持ロール
１４、２０・・・モーター
１５・・・プーリー
１８・・・微粉末の流動層
１９・・・不活性ガス送入パイプ
２１・・・プロペラ
２２、２４・・・弁
２３・・・微粉末循環パイプ
２５・・・円筒形フィルター
２６・・・排気系
２７・・・モーター
２８・・・スパッタリング源FIG. 1 is a cross-sectional view of one side showing the concept of an apparatus for carrying out the method of the present invention, and FIG. 2 is a cross-sectional view taken along the line ■-■ in FIG. It is a conceptual cross-sectional view. Figures 3 and 4 are graphs showing the results of diametrical Auger analysis of red and green pearlescent pigments, respectively, products of the present invention. In Fig. 1.2, 1...Reduced pressure heat treatment chamber 2...Rotating barrel type sputtering chamber 3...Fluid jet mill 4...Powder filter 5...Filter 6...Main exhaust system 7 ... Advanced exhaust system 8 ... Powder heated under reduced pressure 9 ... Screw feeders 10, 11 ... Conduits 121, 122 ... Valve 13 ... Support rolls 14, 20 ... Motor 15 ...・Pulley 18...Fine powder fluidized bed 19...Inert gas feed pipe 21...Propeller 22, 24...Valve 23...Fine powder circulation pipe 25...Cylindrical filter 26... ...Exhaust system 27...Motor 28...Sputtering source
Claims (3)
顔料の表面を、さらにスパッタリング法によって金属チ
タン被覆処理し、それにより二酸化チタンを低次酸化チ
タンに還元することからなる着色真珠光沢雲母顔料の製
造方法。1. A method for producing a colored pearlescent mica pigment, which comprises further treating the surface of a pearlescent mica pigment made of mica coated with titanium dioxide with metallic titanium by a sputtering method, thereby reducing the titanium dioxide to lower titanium oxide.
１に記載の方法。2. 2. A method according to claim 1, wherein the sputtering is carried out at a temperature below 200<0>C.
と、流体ミル粉体分散処理帯域とを設け、二酸化チタン
被覆雲母からなる真珠光沢雲母顔料をこの三帯域の間を
循環させて、スパッタリングによる金属チタン被覆処理
を反復して行う請求項１に記載の方法。3. A powder vacuum heat treatment zone, a fluidized bed sputtering zone, and a fluid mill powder dispersion treatment zone are provided, and a pearlescent mica pigment made of titanium dioxide-coated mica is circulated between these three zones to coat titanium metal by sputtering. 2. The method of claim 1, wherein the process is performed iteratively.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29552490A JP2883441B2 (en) | 1990-11-02 | 1990-11-02 | Method for producing colored pearlescent mica pigment |
| EP91309988A EP0484108B1 (en) | 1990-11-02 | 1991-10-29 | Pigment and process for producing the same |
| DE69111375T DE69111375T2 (en) | 1990-11-02 | 1991-10-29 | Pigment and manufacturing process. |
| US07/785,328 US5238492A (en) | 1990-11-02 | 1991-11-01 | Pigment and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29552490A JP2883441B2 (en) | 1990-11-02 | 1990-11-02 | Method for producing colored pearlescent mica pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04173955A true JPH04173955A (en) | 1992-06-22 |
| JP2883441B2 JP2883441B2 (en) | 1999-04-19 |
Family
ID=17821742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29552490A Expired - Lifetime JP2883441B2 (en) | 1990-11-02 | 1990-11-02 | Method for producing colored pearlescent mica pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2883441B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807939A (en) * | 2015-11-27 | 2017-06-09 | 上海朗亿功能材料有限公司 | One type of metal flakelike powder |
| CN116478560A (en) * | 2023-03-24 | 2023-07-25 | 瑞彩科技股份有限公司 | Black pearlescent pigment and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108051569B (en) * | 2017-12-26 | 2021-03-05 | 奇瑞商用车（安徽）有限公司 | Gradient board and experiment method based on gradient board paint covering power |
-
1990
- 1990-11-02 JP JP29552490A patent/JP2883441B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807939A (en) * | 2015-11-27 | 2017-06-09 | 上海朗亿功能材料有限公司 | One type of metal flakelike powder |
| CN116478560A (en) * | 2023-03-24 | 2023-07-25 | 瑞彩科技股份有限公司 | Black pearlescent pigment and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2883441B2 (en) | 1999-04-19 |
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