JPH0258578A - Production of pigment - Google Patents
Production of pigmentInfo
- Publication number
- JPH0258578A JPH0258578A JP21117588A JP21117588A JPH0258578A JP H0258578 A JPH0258578 A JP H0258578A JP 21117588 A JP21117588 A JP 21117588A JP 21117588 A JP21117588 A JP 21117588A JP H0258578 A JPH0258578 A JP H0258578A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- dioxide layer
- pigment
- chromium
- color tone
- 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
- 239000000049 pigment Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 29
- 239000011651 chromium Substances 0.000 claims abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000000149 argon plasma sintering Methods 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 239000010445 mica Substances 0.000 description 15
- 229910052618 mica group Inorganic materials 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 15
- 239000004332 silver Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- ACVSDIKGGNSZDR-UHFFFAOYSA-N [P].[W].[Ni] Chemical compound [P].[W].[Ni] ACVSDIKGGNSZDR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 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
- SQWDWSANCUIJGW-UHFFFAOYSA-N cobalt silver Chemical compound [Co].[Ag] SQWDWSANCUIJGW-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明は光干渉および光散乱により発色する新規なＭ料
の製造方法に関する。本発明の製造方法によれば、この
新規顔料を安定した色調で製造することができる。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing a novel M material that develops color by light interference and light scattering. According to the production method of the present invention, this new pigment can be produced with stable color tone.
［従来の技術１
従来より、雲母表面に二酸化チタンが被覆されたバール
マイカ顔料が知られている。このバールマイカ顔料は光
干渉により真珠のような光沢を発色し、二酸化チタン層
の厚さを変化させることにより種々の干渉色を（９るこ
とができる。また待間昭５９−７８２６５号、特公昭６
０−３３４５号などの公報には、バールマイカｍ 料の
二酸化チタン層の表面にさらにクロム化合物を析出させ
て耐候性を改良したｐｎ料も開示されている。[Prior Art 1] Burr mica pigments in which the surface of mica is coated with titanium dioxide have been known. This Burmica pigment develops a pearl-like luster through optical interference, and by changing the thickness of the titanium dioxide layer, various interference colors can be produced. 6
Publications such as No. 0-3345 also disclose a pn material in which weather resistance is improved by further precipitating a chromium compound on the surface of the titanium dioxide layer of the var mica material.
［発明が解決しようとイる課題１
しかしバールマイカ顔料を用いた４７（ｆ’Ｊより形成
された塗膜では、金属の光ｉｌｌ感が得られずメタリッ
ク！ｌ！！装としては不十分である。またアルミニウム
粉末を含有するメタリック塗膜に比べて、正面から見た
時の明度と斜め方向から見た時の明度との差が小さく、
いわゆるフリップフロップ性に劣るという不具合がある
。そこで本発明者らは、バールマイカ顔料またはクロム
化合物が析出されたバールマイカ顔料表面に、銀などの
金属または合金よりなり全表面積の０．０５〜９５％の
表面を占めるように島状に点在する光輝部をｂつ新規な
顔料を出願している（特願昭６２−２６５７９５号、本
発明の出願時未公開）。この顔料により形成されたメタ
リック塗膜は、金属による光輝感と光干渉による干渉色
および反射、散乱による散乱色を有し、フリップ７０ツ
ブ性にも優れている。[Problem to be solved by the invention 1 However, the coating film formed from 47(f'J) using Burl Mica pigment does not provide the metallic shine and is insufficient as a metallic!l!! Also, compared to metallic coatings containing aluminum powder, the difference between the brightness when viewed from the front and the brightness when viewed from an oblique direction is small.
There is a problem that the so-called flip-flop property is inferior. Therefore, the present inventors have discovered that the surface of Burl Mica pigment or Burl Mica pigment on which a chromium compound is precipitated is dotted with islands made of a metal such as silver or an alloy and occupying 0.05 to 95% of the total surface area. An application has been filed for a new pigment with b brightening parts (Japanese Patent Application No. 62-265795, unpublished at the time of filing of the present invention). The metallic coating film formed from this pigment has a metallic glitter, an interference color due to light interference, and a scattering color due to reflection and scattering, and also has excellent flip 70 flatness.
本発明者らはこの新規顔料について検討を重ねるうちに
、製造される顔料の発色にばらつきが生じることを発見
した。また、このばらつきは島状に点在する光１ｒｌｌ
ｒＡの占有面積の合計が小さい場合に顕著であることも
明らかとなった。そして顕微鏡観察などにＪ：りその原
因を追及した結果、光輝部を島状に点在させる時に、そ
の分布および粒径に偏りが生じて反射、散乱に影響し散
乱光がばらつくためであることが明らかとなった。As the inventors of the present invention continued to study this new pigment, they discovered that there were variations in the color development of the produced pigment. In addition, this variation is caused by the light 1rll scattered in an island shape.
It has also become clear that this effect is significant when the total area occupied by rA is small. After investigating the cause of this phenomenon, we found that it is because when bright areas are scattered in an island pattern, their distribution and particle size become uneven, which affects reflection and scattering and causes scattered light to vary. became clear.
本発明は、上記新規顔料において島状に点在する光輝部
の分布および粒径を均一にすることを技術的課題とする
ものである。The technical object of the present invention is to make uniform the distribution and particle size of the shiny parts scattered like islands in the above-mentioned novel pigment.
［課題を解決するための手段］
本発明の顔料の製造方法は、セラミック製鱗片状の基材
全表面に二酸化チタン層を形成する第１工程と、二酸化
チタン層の表面にり［］ム化合物を金属クロムに換算し
て０．０５〜０．２８重量％の聞で析出させる第２工程
と、主として二酸化チタン層表面に二酸化チタン層の全
表面積に対して０．０５〜９５％となるように島状に点
在する金属質の光輝部を形成する第３工程と、を行なう
ことを特徴とする。[Means for Solving the Problems] The method for producing a pigment of the present invention includes a first step of forming a titanium dioxide layer on the entire surface of a ceramic scale-like base material, and a step of forming a titanium dioxide layer on the surface of the titanium dioxide layer. A second step in which chromium is precipitated in an amount of 0.05 to 0.28% by weight calculated as metallic chromium, and a second step in which chromium is precipitated mainly on the surface of the titanium dioxide layer so that the amount is 0.05 to 95% of the total surface area of the titanium dioxide layer. A third step of forming metallic shiny parts dotted in the form of islands is performed.
セラミック性鱗片状の基材としては、雲母、二硫化モリ
ブデンなどを用いることができる。ロ面１〜而などから
雲母が待に推奨され、白雲母、黒雲母また（よ金雲母な
どの天然雲母、あるいは合成雲母を用いることができる
。、塗料用顔料とする場合は、厚さが５００〜１０００
人程度、長さが３〜５０μｍ＋￥度の粒度のものを用い
ることが好ましい。As the ceramic scale-like base material, mica, molybdenum disulfide, etc. can be used. Mica is highly recommended for reasons such as 1 and 2, and natural mica such as muscovite, biotite, phlogopite, or synthetic mica can be used.When used as a pigment for paint, the thickness is 500-1000
It is preferable to use particles with a length of 3 to 50 μm + ¥ degree, about the size of a human body.
第゛１工程は、上記基材表面に二酸化チタン層を形成す
る工程である。この工程は例えば米国特許第４０３８０
９９号公報に記載されでいるような硫酸チタニル法で行
なうことができる。この硫酸チタニル法では、予めスズ
化合物で処理された基Ｈの水性スラリー中に酸性のＦｉ
Ａ酸チタニル溶液を添加する。そして７０〜１１０℃に
加熱すると、硫酸チタニルは加水分解して塞材表面には
含水無定形水酸化チタンが被覆される。これをろ過し焼
成することにより、基材表面に二酸化チタン層が形成さ
れる。なお、この二酸化チタン層は水和物であってもよ
い。基Ｈに雲母を用いるのであれば、数多く市販されて
いるパールマイカを用いることにより第１工程を省略す
ることができる。The first step is a step of forming a titanium dioxide layer on the surface of the base material. This process is described in US Pat. No. 40380, for example.
This can be carried out by the titanyl sulfate method as described in Japanese Patent No. 99. In this titanyl sulfate method, acidic Fi is added to an aqueous slurry of group H that has been previously treated with a tin compound.
Add titanyl A acid solution. When heated to 70 to 110°C, the titanyl sulfate is hydrolyzed and the surface of the plugging material is coated with hydrous amorphous titanium hydroxide. By filtering and baking this, a titanium dioxide layer is formed on the surface of the base material. Note that this titanium dioxide layer may be a hydrate. If mica is used as the group H, the first step can be omitted by using pearl mica, which is commercially available in large numbers.
第２工程は第１■程で形成された二酸化チタン層表面に
クロム化合物を析出させる工程である。The second step is a step in which a chromium compound is deposited on the surface of the titanium dioxide layer formed in step 1.
この工程は、例えば特公昭６０−３３４５号公報に見ら
れるように、塩化物または硫酸塩などの可溶性クロム塩
の溶液を加水分解することにより水酸化クロムを析出さ
せる方法、あるいは特開昭５９−７８２６５号公報に見
られるように、鉄またはマンガンのイオンおよびクロム
イオンを含む溶液から、クロムを水酸化物、炭酸塩、リ
ン酸塩あるいはメクアクリレート銘体として沈澱させる
方法などを利用できる。This step is carried out by a method in which chromium hydroxide is precipitated by hydrolyzing a solution of soluble chromium salts such as chlorides or sulfates, as seen in Japanese Patent Publication No. 60-3345, or in Japanese Patent Publication No. 59-3345. As seen in Japanese Patent No. 78265, a method can be used in which chromium is precipitated as a hydroxide, carbonate, phosphate, or mechaacrylate from a solution containing iron or manganese ions and chromium ions.
本発明の最大の特徴は、全体を１００重邑％とじた場合
に、二酸化チタン層に析出するクロム化合物の析出間を
金属クロムに換算して０．０５〜０．２８重量％となる
ようにしたところにある。The greatest feature of the present invention is that when the whole is closed at 100% by weight, the amount of chromium compound precipitated in the titanium dioxide layer is 0.05 to 0.28% by weight in terms of metallic chromium. It's right there.
金属クロムに換算したクロム化合物の析出間がＯＯ５巾
間％より少ないと、最終的に得られる顔料の色調が、析
出間が０．０５重ｈ１％より多い場合に１ｒＩられる顔
料の色調と異なるようになる。その色調で安定して製造
できればよいが、クロム化合物の析出間を０．０５重量
％以下という狭い範囲で一定させることは困難である。If the precipitation interval of the chromium compound converted to metallic chromium is less than OO5 width%, the color tone of the pigment finally obtained will be different from the color tone of the pigment obtained when the precipitation interval is more than 0.05w/h1%. become. It would be fine if it could be produced stably with that color tone, but it is difficult to keep the amount of chromium compound precipitation constant within a narrow range of 0.05% by weight or less.
また０、２８重量％より多くなると、１ｑられる顔料の
発色の色調にばらつきが生じるようになり、安定した色
調で製造することは回能である。If the amount exceeds 0.28% by weight, the color tone of the pigment produced by 1q will vary, and it is difficult to produce with a stable color tone.
第３工程は、クロム化合物が析出した二酸化チタン層表
面に、金Ｈ質の光Ｖ＠部を島状に点在させて形成する工
程である。この光輝部を構成する金属としては、金、銀
、銅、パラジウム、コバルトなどの金属、あるいはニッ
ケルーリン、ニッケルーホウ素、ニッケルーコバルト−
リン、ニッケルータングステン−リン、銀−金、コバル
ト−銀などの合金を用いることができる。そしてこれら
の金属のイオンを含有する溶液から、例えば無電解めっ
き法などを利用して光輝部を形成することができる。The third step is a step in which optical V@ parts of H-gold are scattered in the form of islands on the surface of the titanium dioxide layer on which the chromium compound has been deposited. The metals that make up this bright part include metals such as gold, silver, copper, palladium, and cobalt, or nickel-phosphorus, nickel-boron, and nickel-cobalt.
Alloys such as phosphorus, nickel-tungsten-phosphorus, silver-gold, and cobalt-silver can be used. The bright portion can be formed from a solution containing ions of these metals by, for example, electroless plating.
この光ＩＦ１部は、その占有面積の合計が二酸化チタン
層の面積に対して０．０５〜９５％となるように形成さ
れる。合計面積が０．０５％より少ないと光輝部を形成
した効果が認められず、バールマイカ４１どと差異がな
くなる。また９５％を超えると、金属をほとんど全面に
ｍ覆したのと同様となり、透明感が乏しく真珠光沢が消
失して平凡な色調となる。なお、３０％〜９５％の範囲
では、光輝部の分布や粒径に偏りが生じても（ｑられる
色調には大きな影響がなく、色調のばらつきが小さい。This optical IF 1 portion is formed so that the total occupied area thereof is 0.05 to 95% of the area of the titanium dioxide layer. If the total area is less than 0.05%, the effect of forming the bright portion will not be recognized, and there will be no difference from Burl Mica 41 or the like. If it exceeds 95%, the result will be the same as if the metal was covered over almost the entire surface, and the transparency would be poor, the pearlescent luster would disappear, and the color tone would be ordinary. In addition, in the range of 30% to 95%, even if the distribution of bright parts or particle size is biased (q), it does not have a large effect on the color tone, and the variation in color tone is small.
従って、本発明は光輝部の占有面積の合計を０．０５〜
３０％の範囲とする場合に特に有用である。Therefore, in the present invention, the total occupied area of the bright parts is 0.05~
Particularly useful in the 30% range.
［発明の作用および効果〕
本発明の顔料の製造方法では、第２工程で二酸化チタン
層表面に金属りＯムに換算して０．０５〜０．２８重１
％のクロム化合物が析出される。[Operations and Effects of the Invention] In the method for producing a pigment of the present invention, in the second step, 0.05 to 0.28 weight 1 of the titanium dioxide layer is coated on the surface of the titanium dioxide layer.
% of chromium compounds are precipitated.
そして次に金属質の光輝部が島状に形成される。Then, metallic bright parts are formed in the form of islands.
ここでクロム化合物は光輝部を構成する金属の析出を抑
υｊする機能をもつ。従って光輝部の占有面積の合計を
一定とすると、クロム化合物の析出ωが０．０５重最％
より少ない場合には、第３工程を実行した直後に二酸化
チタン層のばば全面に多数の核が発生してそれぞれが成
長するため、光輝部の粒径は小さくなる。そのため光輝
部の粒径が大きい場合に比べて光散乱による発色の色調
が大きく異なるようになる。Here, the chromium compound has the function of suppressing the precipitation of the metal constituting the bright part. Therefore, assuming that the total area occupied by the bright parts is constant, the precipitation ω of the chromium compound is 0.05%
If the number is smaller, a large number of nuclei will be generated over the entire surface of the titanium dioxide layer immediately after the third step and each will grow, so that the particle size of the bright portion will become smaller. Therefore, compared to the case where the particle size of the bright portion is large, the color tone produced by light scattering becomes significantly different.
またクロム化合物の析出量が０．２８重ｆｆｉ％より多
くなると、表出する二酸化チタン層の面積が小さくなる
ため金属の核の発生が遅れ、−旦発生した核は凝集しや
すい。これにより光輝部の粒径の分布が広くなり、従っ
て発色の色調にばらつきが生じやすくなる。析出ｍが０
．０５〜０．２８重量％の範囲にあれば、金属の核は第
３工程を実行した直接に発生して成長し、凝集しにくく
均一な粒径の光ｒｉ部が形成される。従って安定した色
調の顔料を製造することができる。Furthermore, when the amount of precipitated chromium compound exceeds 0.28% by weight, the area of the exposed titanium dioxide layer becomes smaller, so that the generation of metal nuclei is delayed, and once generated, the nuclei tend to aggregate. This widens the distribution of particle sizes in the bright areas, and therefore tends to cause variations in color tone. Precipitation m is 0
．． If the amount is in the range of 0.05 to 0.28% by weight, metal nuclei will be generated and grown directly after the third step is performed, and a light ri portion with a uniform particle size that is difficult to agglomerate will be formed. Therefore, pigments with stable color tone can be produced.
［実施例］ 以下、実施例により本発明を具体的に説明する。[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.
（第１工程）
雲母表面にルチル型二酸化チタンが被覆されたバールマ
イカ（「イリオジン１０３」メルク社製）を用意した。(First step) Burl mica ("Iriodin 103" manufactured by Merck & Co., Ltd.) whose mica surface was coated with rutile titanium dioxide was prepared.
従って第１工程は省略された。なお、このバールマイカ
では、***国公開特許第２５２２５２７＠公報の例２の
製造方法に従って雲母に二酸化チタンが被覆されている
。Therefore, the first step was omitted. In this burr mica, mica is coated with titanium dioxide according to the manufacturing method of Example 2 of West German Published Patent Application No. 2,522,527@.
（第２工程）
次に上記バールマイカの表面に、全体を１００重量％と
した場合に、金属クロムに換算して０゜０１〜１０重量
％の範囲で１５水準選択してクロム化合物を析出させた
。析出方法としては、以下に説明する２つの方法を採用
した。(Second step) Next, a chromium compound was precipitated on the surface of the burr mica by selecting 15 levels in the range of 0.01 to 10% by weight in terms of metallic chromium, when the whole is 100% by weight. . As the precipitation method, two methods explained below were adopted.
第１の方法 ＦｅＳＯ４・７日ｔＯを９２ＱとＫＣｒ （Ｓ。First method FeSO4 7 days tO with 92Q and KCr (S.
４）ｙ−１２ＨｚＯを１７ａ含有する水溶液１０ｏｍｚ
、およびＮａＨｔＰＯ＊ ・２ｆ−１ｔＯを１゜５９含
有する水溶液１０ｏｍｉを、バールマイカ粉末１００ｇ
がＭ溜水１９．中に混合された懸濁液に、１−１４．５
．５０℃で１時間にわたって加える。この間、２％水酸
化ナトリウム溶液の同時添加により、上記ｐＨを一°定
に保持する。添加柊了侵ｐＨを５．０に上げ、さらにｌ
Ｐｒ間攪拌後、ろ過、水洗して１３０℃で乾燥させる。4) 10 omz aqueous solution containing 17a of y-12HzO
, and 10 omi of an aqueous solution containing 1°59 of NaHtPO* 2f-1tO and 100 g of burr mica powder.
19. 1-14.5 to the suspension mixed in
．． Add over 1 hour at 50°C. During this time, the pH is kept constant by simultaneous addition of 2% sodium hydroxide solution. Raise the pH of the addition to 5.0 and further add l
After stirring for a while, it is filtered, washed with water, and dried at 130°C.
この場合クロム化合物はリンＭ塩として析出する。なＪ
３、クロム化合物の析出量は、懸濁液に添加される２１
類の水溶液の出および添加時間を変更することにより行
なった。In this case, the chromium compound is precipitated as a phosphorus M salt. NaJ
3. The amount of chromium compound precipitated is determined by the amount of chromium compound added to the suspension.
This was done by changing the release and addition time of the same aqueous solution.
第２の方法
バールマイカ２００Ｑを３４００ｍλの蒸溜水でスラリ
ーとし、ｐＨを２Ｎの硫酸水溶液で６゜０に調製した。Second Method Burmica 200Q was made into a slurry with 3400 mλ of distilled water, and the pH was adjusted to 6°0 with a 2N aqueous sulfuric acid solution.
次に５％のＣｒＣｌ３水溶液６４ｒｒＢを２００ｍＲの
蒸溜水で稀釈し、この溶液を一定のｖ１合で約３０分間
で上記スラリーに添加する。この添加の間、１０％の水
酸化ナトリウム溶液を加えてそのｐ＋を絶えず６．０に
保持する。A 5% CrCl3 aqueous solution 64rrB is then diluted with 200 mR of distilled water and this solution is added to the slurry at a constant volume of about 30 minutes. During this addition, the p+ is constantly maintained at 6.0 by adding 10% sodium hydroxide solution.
その後スラリーをろ過、水洗して１１０〜１２０℃で１
時間乾燥する。この場合クロム化合物は水酸化クロムと
して析出する。なお、クロム化合物の析出量は、スラリ
ーに添加されるＣｒ’Ｃ１３水溶液の憬および添加時間
を変更することにより行なった。After that, the slurry was filtered, washed with water and heated to 110-120°C.
Dry for an hour. In this case, the chromium compound is precipitated as chromium hydroxide. The amount of chromium compound precipitated was determined by changing the volume and addition time of the Cr'C13 aqueous solution added to the slurry.
（第３王稈）
上記により得られたクロム化合物が析出したバールマイ
カを、それぞれ３０ｇ採取し、それぞれ蒸溜水９００ｍ
Ｒに懸濁させて攪拌する。そして硝酸銀５０Ｑ／ｉおよ
び２８％アンモニア水５０ｍ交／λを含有する銀波６０
ｍλをそれぞれのスラリーに添加し、さらに還元剤とし
てホルマリン（ホルムアルデヒド３５％含有＞１０ｍλ
を添加する。そして６０分間攪拌を続け、ろ過、水洗し
て８０”Ｃで３時１ｆｆｉ吃燥して、それぞれの顔料を
得た。得られた顔料には、それぞれ銀からなる島状の光
輝部が合計重量で５，９７重量％、占有面積の合計が１
．５％の割合で形成きれていた。(Third king culm) Collect 30g of each of the burr mica on which the chromium compound obtained above was precipitated, and add 900ml of distilled water to each of them.
Suspend in R and stir. and silver wave 60 containing silver nitrate 50Q/i and 28% ammonia water 50m/λ
mλ was added to each slurry, and formalin (>10 mλ containing 35% formaldehyde) was added as a reducing agent.
Add. Then, stirring was continued for 60 minutes, followed by filtration, washing with water, and drying at 80"C for 3 hours and 1ffi to obtain each pigment. Each of the obtained pigments had a total weight of island-shaped bright parts made of silver. 5.97% by weight, the total occupied area is 1
．． It was completely formed at a rate of 5%.
（色調の調査）
得られたそれぞれの顔料５．３ｇをアクリル−メラミン
系樹脂（固形分５３％）１００ｇに分散して塗料を調製
し、試験板に乾燥膜厚５００μｍどなるように塗装後、
１３０℃で２０分間加熱して焼付は乾燥した。そして形
成されたそれぞれの塗膜の色調を色差ｇｆ （スガ試験
機（株）製）にて測色し、その結果をハンターのＬａｂ
にお番プるｂ値で第１図に示す。(Investigation of color tone) A paint was prepared by dispersing 5.3 g of each of the obtained pigments in 100 g of acrylic-melamine resin (solid content 53%), and after coating it on a test plate to a dry film thickness of 500 μm,
The baking was dried by heating at 130° C. for 20 minutes. Then, the color tone of each coating film formed was measured using a color difference gf (manufactured by Suga Test Instruments Co., Ltd.), and the results were measured using Hunter's Lab.
Figure 1 shows the b-values that vary.
第１図より、クロム化合物の析出量が金属クロムに換陣
して０．０５〜０，２８重量％の範囲ある時に、ｂ １
６は一５近傍で安定してｄ３り色調のばらつきのない安
定した＾味の顔料が４！、７られることがわかる。この
時、銀粒子の粒径は１００〜２０Ｑ ｎ ｍ Ｆ安定し
て形成されている。From Figure 1, when the amount of precipitated chromium compound converted to metallic chromium is in the range of 0.05 to 0.28% by weight, b 1
6 is stable around 15 and is d3. 4 is a pigment with a stable taste with no variation in color tone! , 7 can be seen. At this time, the silver particles are stably formed with a particle size of 100 to 20 Q nm F.
クロム化合物の析出量が０．０５重ｆｆｉ％より少ない
と、ｂ値は＋２程度となり、肖味の顔料は得られない。If the amount of precipitated chromium compound is less than 0.05% by weight, the b value will be about +2, and a pigment with a portrait texture will not be obtained.
この場合は、銀粒子の粒径は１０〜５Ｑｎｍと小さくな
っている。In this case, the particle size of the silver particles is as small as 10 to 5 Qnm.
また０、２８重ω％より多くなると、ｂ ｈ＆は大きく
変動し色調のばらつきが大きいことがわかる。It can also be seen that when the amount exceeds 0.28 ω%, b h& changes greatly and the variation in color tone becomes large.
この場合は、銀粒子は５０〜８０ｍｍのらのが多く、一
部に凝集した１００〜５００ｎｍのものが形成されてい
る。In this case, most of the silver particles are 50 to 80 mm in size, and agglomerated particles of 100 to 500 nm are formed in some parts.
なお、クロム化合物の析出量が金属クロムに換陣して０
．３重Ｍ％の場合と０．２８重邑％の場合に６１ブるｌ
とｂＩＩｉの分布を第２図に示す。０゜２８重山％の場
合はＬ ｍとｂ値のばらつきは極めて小さいが、０．３
重間％になるとＬ値もｂ値も大きく変動し、特にｂ値の
ばらつきが大きいことが明らかである。In addition, the amount of precipitated chromium compounds is converted to metallic chromium and becomes 0.
．． 61 burl in case of 3-fold M% and 0.28-fold M%
The distribution of and bIIi is shown in FIG. In the case of 0°28 Juyama%, the variation in L m and b value is extremely small, but 0.3
It is clear that both the L value and the b value vary greatly when it comes to the weight percentage, and the variation in the b value is particularly large.
（光ｖｌ／ｉｌ＋の付着層と色調のばらつきとのｒＭ係
）上記したように、クロム化合物の析出間が金属クロム
に換算して０．２８重量％と０．３重Ｍ％とで色調のば
らつきが大きく異なることが明らかとなった。そこでこ
の２種類の析出量でそれぞれクロム化合物を析出させ、
銀の付着口を占有面積の合計で０．０３〜５０％の間で
６水＊Ｘ択して顔料を製造した。なお、銀の付ｉｔ面の
制御は銀波の添加昂を増減して行なった。そしてそれぞ
れの水準の顔料は２５０ツト￥Ｊ造し、それぞれ＃Ｊ紀
と同様に塗料化、塗装、測色して結果を第３図に示す。(rM relationship between adhesion layer of light vl/il+ and variation in color tone) As mentioned above, the difference in color tone is due to the difference between the precipitation of the chromium compound being 0.28% by weight and 0.3% by weight in terms of metallic chromium. It became clear that the dispersion was significantly different. Therefore, we precipitated chromium compounds with these two types of precipitation amounts,
A pigment was manufactured by selecting 6 water*X silver adhesion ports in a total area of 0.03 to 50%. Note that the adhesion of silver on the IT surface was controlled by increasing or decreasing the amount of silver waves added. Then, 250 yen of pigment was prepared for each level, and each was made into paint, painted, and measured in the same manner as #J, and the results are shown in Figure 3.
第３図より、クロム化合物の析出間が０．３Φ吊％のＪ
Ｊａ合は、銀の付衿Ｍが３０％より少なくなるとＬ値も
ｂ値もばらつきが大きくなっている。From Figure 3, J
In the case of Ja, when the silver collar M is less than 30%, the variation in both the L value and the b value becomes large.
特にｂ値のばらつきが大きい。しかし銀の付着端が３０
％を超えるとｂ値のばらつきが小さくなり、クロム化合
物の析出間が多い場合の色調のばらつきが緩和または解
消されていることがわかる。In particular, the variation in b value is large. However, the silver attached end is 30
%, the variation in the b value becomes smaller, and it can be seen that the variation in color tone that occurs when there are many chromium compound precipitations is alleviated or eliminated.
一方クロム化合物の析出量が０．２８重量％の場合は、
銀の付着量が０．０３％の場合を除いて銀の付ｅｌ！に
かかわらず安定した色調を示している。On the other hand, when the amount of chromium compound precipitated is 0.28% by weight,
Silver attachment el! except when the silver attachment amount is 0.03%! It shows a stable color tone regardless of the conditions.
第１図はクロム化合物の析出Ｍとｂ値との関係を示すグ
ラフ、第２図は２種類のクロム化合物析出間のし値とｂ
値の分布を示すグラフ、第３図は銀の付着室がＬ ｌａ
とｂ Ｉａの分布におよぼす影−を説明するグラフであ
る。Figure 1 is a graph showing the relationship between precipitation M of chromium compounds and b value, and Figure 2 is a graph showing the relationship between precipitation M of chromium compounds and b value.
A graph showing the distribution of values, Figure 3 shows that the silver deposition chamber is L la
It is a graph explaining the influence on the distribution of and b Ia.
Claims (1)
層を形成する第１工程と、 該二酸化チタン層の表面にクロム化合物を金属クロムに
換算して０．０５〜０．２８重量％の量で析出させる第
２工程と、 主として該二酸化チタン層表面に該二酸化チタン層の全
表面積に対して０．０５〜９５％となるように島状に点
在する金属質の光輝部を形成する第３工程と、を行なう
ことを特徴とする顔料の製造方法。(1) A first step of forming a titanium dioxide layer on the entire surface of a ceramic scale-like base material, and adding a chromium compound to the surface of the titanium dioxide layer in an amount of 0.05 to 0.28% by weight in terms of metallic chromium. a second step of precipitating the titanium dioxide layer in an amount, and forming metallic bright parts scattered in island shapes mainly on the surface of the titanium dioxide layer so as to account for 0.05 to 95% of the total surface area of the titanium dioxide layer. A method for producing a pigment, the method comprising: a third step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21117588A JP2504129B2 (en) | 1988-08-25 | 1988-08-25 | Pigment manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21117588A JP2504129B2 (en) | 1988-08-25 | 1988-08-25 | Pigment manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0258578A true JPH0258578A (en) | 1990-02-27 |
| JP2504129B2 JP2504129B2 (en) | 1996-06-05 |
Family
ID=16601652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21117588A Expired - Fee Related JP2504129B2 (en) | 1988-08-25 | 1988-08-25 | Pigment manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2504129B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03287670A (en) * | 1990-04-05 | 1991-12-18 | Toyota Motor Corp | Manufacture of pigment |
| US5308394A (en) * | 1990-04-05 | 1994-05-03 | Toyota Jidosha Kabushiki Kaisha | Pigment and process for producing the same |
-
1988
- 1988-08-25 JP JP21117588A patent/JP2504129B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03287670A (en) * | 1990-04-05 | 1991-12-18 | Toyota Motor Corp | Manufacture of pigment |
| US5308394A (en) * | 1990-04-05 | 1994-05-03 | Toyota Jidosha Kabushiki Kaisha | Pigment and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2504129B2 (en) | 1996-06-05 |
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