JPH0269572A - Titanium dioxide pigment - Google Patents
Titanium dioxide pigmentInfo
- Publication number
- JPH0269572A JPH0269572A JP22198988A JP22198988A JPH0269572A JP H0269572 A JPH0269572 A JP H0269572A JP 22198988 A JP22198988 A JP 22198988A JP 22198988 A JP22198988 A JP 22198988A JP H0269572 A JPH0269572 A JP H0269572A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- metal particles
- base material
- pigment
- color
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 239000000049 pigment Substances 0.000 title claims abstract description 26
- 239000002923 metal particle Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 abstract description 26
- 238000000149 argon plasma sintering Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 235000019646 color tone Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 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 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は二酸化チタン系の新規な顔料に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a novel pigment based on titanium dioxide.
〔従来の技術］
従来より、塗料、絵の具などの白色顔料として一酸化チ
タンが多用されている。この二酸化チタンは低価格であ
り、高屈折率であるという特徴を有しているが、白色顔
料としての用途以外には殆んど利用されていないのが現
状である。[Prior Art] Titanium monoxide has been widely used as a white pigment in paints, paints, and the like. Although titanium dioxide is characterized by being low in price and having a high refractive index, it is currently hardly used for purposes other than as a white pigment.
また近年、雲母表面に二酸化チタン層を形成した真珠光
沢を有する顔料が開発されている。さらに特開昭６０−
６０１６３号公報にみられるように、雲母表面にチタン
の酸化度合が二酸化チタンより低い低次酸化チタンを被
覆し、さらに二酸化チタンで被覆した顔料も開示されて
いる。これらの顔料は再表層の二酸化チタン層における
光干渉による干渉光を強く発色させるものであるが、基
材としては雲母を用いており二酸化チタンの使用品は僅
かである。Furthermore, in recent years, pearlescent pigments with a titanium dioxide layer formed on the mica surface have been developed. Furthermore, JP-A-60-
As seen in Japanese Patent No. 60163, a pigment in which the mica surface is coated with lower titanium oxide whose degree of oxidation is lower than that of titanium dioxide, and further coated with titanium dioxide is also disclosed. These pigments strongly color the interference light caused by light interference in the titanium dioxide layer on the surface, but since mica is used as the base material, only a few products use titanium dioxide.
このように二酸化チタンを原料とした顔料としての例は
、上記以外には報告されていない。In this way, no other examples of pigments using titanium dioxide as a raw material have been reported.
［発明が解決しようとする課題］
本発明は二酸化チタンを出発原料とし、新規な発色原理
に基づいて従来にない新規な色を拡大、開発することを
技術的課題とするものである。[Problems to be Solved by the Invention] The technical problem of the present invention is to use titanium dioxide as a starting material and to expand and develop new colors that have never existed before based on a new coloring principle.
［課題を解決するための手段］
本発明者等は金属微粒子の光散乱による発色の応用を試
み、種々検討を重ねたが、金属自体の微粒子を製造しよ
うとしても凝集が生じ、散乱光を発するような微粒子と
することは現時点では困難である。そこで他物質を介在
させ、その物質表面に金属粒子を形成することを案出し
、種々検討を重ねた結果二酸化チタン粉末に金属粒子を
形成すると、金属粒子の凝集が防止されることを発見し
本発明を完成したしのである。[Means for Solving the Problems] The present inventors have attempted to apply coloring by light scattering of fine metal particles, and have conducted various studies, but even when attempting to produce fine particles of the metal itself, agglomeration occurs and scattering light is emitted. At present, it is difficult to produce such fine particles. Therefore, we came up with the idea of interposing other substances and forming metal particles on the surface of the substance, and as a result of various studies, we discovered that forming metal particles in titanium dioxide powder would prevent the metal particles from agglomerating. This is the person who completed the invention.
すなわち本発明の顔料は、二酸化チタンよりなる基材と
、基材表面に島状に点在して付着した金属粒子と、から
なり、主として金属粒子の散乱光により発色する構成と
したことを特徴とする。That is, the pigment of the present invention is characterized by being composed of a base material made of titanium dioxide and metal particles scattered and attached to the surface of the base material in the form of islands, and colored mainly by scattered light from the metal particles. shall be.
基材としては二酸化チタンが用いられる。アナターゼ型
、ルプル型のいずれも用いることができる。この二酸化
チタンの粒径は、０．１〜１μｍの範囲であることが好
ましい。粒径が０．１μｍより小さくなると金属粒子を
島状に付着させても散乱光が弱く、また粒径が１μｍよ
り大きくなると塗料化して塗装しても平滑な塗膜が得に
くく、塗料用顔料としてあまり好ましくない。Titanium dioxide is used as the base material. Both anatase type and lupul type can be used. The particle size of this titanium dioxide is preferably in the range of 0.1 to 1 μm. If the particle size is smaller than 0.1 μm, the scattered light will be weak even if metal particles are attached in the form of islands, and if the particle size is larger than 1 μm, it will be difficult to obtain a smooth coating even if it is made into a paint. I don't like it very much.
基材表面には金属粒子が°島状に点在して付着している
。この金属粒子の粒径は少なくとも散乱光を発する粒径
のものを含む必要があり、例えば金属が銀である場合に
は１ｎｍ〜５００ｎｍが好ましい。この金属粒子の粒径
により散乱光の色調が種々変化することがわかっている
。なお、凝集などにより粒径の大きな金属粒子を含む場
合には、散乱光のみならず金属自体の反射光も加味され
た発色が得られる。また金属粒子の付着していない部分
からは、二酸化チタンによる白色光が発色する場合もあ
る。従って本発明の顔料では、これらの発色が混合され
た発色となり、従来にない新規な意匠を具現することが
できる。Metal particles are scattered and attached to the surface of the base material in the form of islands. The particle size of the metal particles must include at least a particle size that emits scattered light, and for example, when the metal is silver, it is preferably 1 nm to 500 nm. It is known that the color tone of scattered light varies depending on the particle size of the metal particles. In addition, when metal particles having a large particle size due to agglomeration or the like are included, color development is obtained that takes into account not only the scattered light but also the reflected light from the metal itself. Furthermore, white light due to titanium dioxide may be emitted from areas to which metal particles are not attached. Therefore, the pigment of the present invention produces a color that is a mixture of these colors, making it possible to realize a novel design that has never existed before.
金属粒子の二酸化チタン表面を覆う割合は、酸化チタン
全表面積に対して０．０５〜０．９５％とするの・が望
ましい。金属粒子の付着面積が０゜０５％より少ないと
二酸化チタンの白色が強く表出し、所望の発色効果が得
られない場合がある。The proportion of the metal particles covering the surface of titanium dioxide is preferably 0.05 to 0.95% of the total surface area of titanium oxide. If the adhesion area of the metal particles is less than 0.05%, the white color of titanium dioxide will appear strongly, and the desired coloring effect may not be obtained.
また９５％より多くなると金属自体の色が強く表出し、
同様に所望の発色効果が得られない場合がある。Also, when it exceeds 95%, the color of the metal itself becomes more pronounced,
Similarly, the desired coloring effect may not be obtained.
この金属粒子の材質としては金属、合金など特に制限さ
れず、銀、ニッケル、パラジウムなどを用いることがで
きる。The material of the metal particles is not particularly limited to metals, alloys, etc., and silver, nickel, palladium, etc. can be used.
［発明の作用及び効果］
本発明の顔料は、二酸化チタンよりなる基材表面に金属
粒子が島状に点在し、その金属粒子の散乱光により発色
する構成である。すなわち金属粒子はほぼコロイド状粒
子であるために、特有の光散乱現象が生ずる。一方、金
属粒子により光の吸収も生じるが、吸収の波長依存性は
粒径によって異なるため、外部より児える余色も金属粒
子の粒径によって異なる。すなわち金属粒子の粒径によ
り種々の散乱色が発色する。[Operations and Effects of the Invention] The pigment of the present invention has a structure in which metal particles are scattered in the form of islands on the surface of a base material made of titanium dioxide, and color is developed by scattered light from the metal particles. That is, since metal particles are almost colloidal particles, a unique light scattering phenomenon occurs. On the other hand, metal particles also absorb light, but the wavelength dependence of absorption differs depending on the particle size, so the extra color produced from the outside also differs depending on the particle size of the metal particles. That is, various scattering colors develop depending on the particle size of the metal particles.
すなわち本発明の顔料によれば、主として金属粒子の光
散乱による発色が見え、従来の二酸化チタン系顔料では
得られなかった種々の色調の発色が得られる。また金属
粒子の粒径を変更するだけで種々の色調とすることがで
きる。そして明度、彩度などの色調に優れ、かつ安全性
、耐候性、耐薬品性、耐熱性などの諸性能に優れること
はその構成からも明らかである。That is, according to the pigment of the present invention, color development is mainly visible due to light scattering of metal particles, and various color tones that cannot be obtained with conventional titanium dioxide pigments can be obtained. Moreover, various color tones can be obtained simply by changing the particle size of the metal particles. It is clear from its structure that it has excellent color tones such as brightness and chroma, as well as various properties such as safety, weather resistance, chemical resistance, and heat resistance.
さらに光散乱に基づ（発色であるため、ゆ料などに適用
した場合、バインダの屈折率により色調が異なり、新規
な意匠を具現することが可能である。Furthermore, since it is based on light scattering (color development), when applied to food materials, the color tone varies depending on the refractive index of the binder, making it possible to realize new designs.
［実施例］ 以下、実施例により具体的に説明する。[Example] Hereinafter, this will be explained in detail using examples.
（実施例１）
第１図に本発明の１実施例の顔料の模式的拡大断面図を
示す。この顔料は、二酸化チタンよりなる基材１と、基
材１表面に島状に点在して付着するコロイド状の銀粒子
２と、より構成される。(Example 1) FIG. 1 shows a schematic enlarged sectional view of a pigment according to an example of the present invention. This pigment is composed of a base material 1 made of titanium dioxide and colloidal silver particles 2 attached to the surface of the base material 1 in a dotted manner.
以下、上記顔料の製造方法を説明しながらその構造の詳
細を説明する。Hereinafter, details of the structure of the pigment will be explained while explaining the method for producing the pigment.
二酸化チタン（アナターゼ型１級試薬、牛丼化学（株）
製、粒径０．１２〜０．３０μｍ）６Ｃ１を水１８０ｍ
Ｎと混合して懸濁させ、その中に硝酸銀溶液（硝酸銀５
００が２８％アンモニア水５０ｍＩに溶解した溶液を水
で希釈して１ｊにしたもの）を１２ｍＪｌ添加する。そ
して５分間撹拌後、ホルマリン液（３５％ホルマリン液
４５ｍ」を水で希釈して２００ｍｊｌにしたもの）８ｍ
ｌｌを滴下し、６０分後にろ別して１００℃で乾燥して
本実第 １
表
て、１′３つ、アクリル・メラミン系樹脂塗料中に１０
ｆｌｕｆｆｉ％となるように配合、分散して塗料化し、
塗膜としたときの塗色を色差計（スガ試験機（株）￥Ｊ
）で測色した。結果を第１表に示す。Titanium dioxide (anatase type 1st class reagent, Gyudon Kagaku Co., Ltd.)
Particle size: 0.12-0.30 μm) 6C1 in 180 m of water
Mix with N and suspend, add silver nitrate solution (silver nitrate 5
Add 12 mJl of a solution of 00 dissolved in 50 ml of 28% ammonia water diluted with water to make 1j. After stirring for 5 minutes, add 8 m of formalin solution (45 m of 35% formalin solution diluted with water to make 200 mjl).
After 60 minutes, filtrate and dry at 100°C.
Blended and dispersed to make a paint with fluffi%,
Measure the color of the paint film using a color difference meter (Suga Test Instruments Co., Ltd.) ￥J
). The results are shown in Table 1.
また得られた顔料を透過型電子顕微鏡で観察し、その写
真を第２図に示す。第２図より二酸化チタンよりなる基
材１（写真の白っぽい粒子）表面にｆｙｌ細な銀粒子２
（写真の黒っぽい粒子）が島状に点在して付着している
ことが認められる。この銀粒子は殆んど２０ｎｍ以下の
粒度を示していた。The obtained pigment was also observed with a transmission electron microscope, and a photograph thereof is shown in FIG. From Figure 2, the surface of the base material 1 made of titanium dioxide (whitish particles in the photo) is covered with fine silver particles 2.
It is observed that (dark particles in the photo) are scattered and attached in the form of islands. Most of the silver particles had a particle size of 20 nm or less.
また銀粒子の付１ｆｆｉは基材１に対して６．４重量％
であり、面積比では約０．１１％である。In addition, 1ffi of silver particles is 6.4% by weight based on base material 1.
The area ratio is approximately 0.11%.
（実施例２）
一酸化チタンとして９９．９９％特級グレードの二酸化
チタン（ルチル型、レアメタリック（株）製、粒径０．
２５〜０．３５μｍ）を用い、実施例１と同様にして顔
料を得た。この顔料は青色を呈しており、実施例１と同
様にして塗料化し塗色を測色した結果を第１表に示す。(Example 2) 99.99% special grade titanium dioxide as titanium monoxide (rutile type, manufactured by Rare Metallic Co., Ltd., particle size 0.
25 to 0.35 μm), a pigment was obtained in the same manner as in Example 1. This pigment has a blue color, and it was made into a paint in the same manner as in Example 1, and the color of the paint was measured, and the results are shown in Table 1.
また実施例１と同様に透過型電子顕微鏡の写真を第３図
に示す。Similarly to Example 1, a transmission electron microscope photograph is shown in FIG.
第３図よりルチル型の二酸化チタンの場合には、実施例
１のアナターゼ型の場合に比べて比較的大きな４０〜５
Ｑｎｍ程度の銀粒子が存在している。Figure 3 shows that in the case of rutile type titanium dioxide, the 40 to 5
Silver particles of about Qnm are present.
（実施例３）
二酸化ブタンとして塗料用ルチル型酸化チタン顔料（ｒ
ＣＲ−９０Ｊデュポン社製、粒径０．２０〜０．３５μ
ｍ）を用いたこと以外は実施例１と同様にして顔料を製
造した。この顔料は茶色を呈しており、実施例１と同様
にして塗料化し、塗色を測色した結果を第１表に示す。(Example 3) Rutile type titanium oxide pigment (r
CR-90J DuPont, particle size 0.20-0.35μ
A pigment was produced in the same manner as in Example 1 except that m) was used. This pigment exhibits a brown color, and was made into a paint in the same manner as in Example 1, and the results of color measurement of the paint color are shown in Table 1.
すなわち、これらの実施例より二酸化チタンを基材とし
て種々の色調に発色させることができることが明らかで
ある。That is, it is clear from these Examples that various colors can be developed using titanium dioxide as a base material.
第１図は本発明の一実施例の顔料の構成を示す説明断面
図である。第２図及び第３図はそれぞれ実施例で得られ
た本発明の顔料の粒子構造を示す電子顕微鏡写真である
。
１・・・基材（二酸化チタン）
２・・・銀粒子
第１２
特許出願人 トヨタ自動車株式会社FIG. 1 is an explanatory sectional view showing the structure of a pigment according to an embodiment of the present invention. FIGS. 2 and 3 are electron micrographs showing the particle structures of the pigments of the present invention obtained in Examples, respectively. 1... Base material (titanium dioxide) 2... Silver particles No. 12 Patent applicant Toyota Motor Corporation
Claims (1)
なり、 主として該金属粒子の散乱光により発色する構成とした
ことを特徴とする二酸化チタン系顔料。(1) It consists of a base material made of titanium dioxide and metal particles scattered and attached to the surface of the base material in the form of islands, and is characterized by a structure in which color is generated mainly by scattered light from the metal particles. Titanium dioxide pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22198988A JPH0269572A (en) | 1988-09-05 | 1988-09-05 | Titanium dioxide pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22198988A JPH0269572A (en) | 1988-09-05 | 1988-09-05 | Titanium dioxide pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0269572A true JPH0269572A (en) | 1990-03-08 |
Family
ID=16775336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22198988A Pending JPH0269572A (en) | 1988-09-05 | 1988-09-05 | Titanium dioxide pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0269572A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997018268A1 (en) * | 1995-11-13 | 1997-05-22 | E.I. Du Pont De Nemours And Company | TiO2 PIGMENT COATED WITH SMALL INORGANIC PARTICLES |
| JP2003261828A (en) * | 2002-03-07 | 2003-09-19 | Sk Kaken Co Ltd | Coating composition |
| JP2004323555A (en) * | 2003-04-21 | 2004-11-18 | Nippon Paint Co Ltd | Metal colloid luster material and its manufacturing method |
| US11118061B2 (en) * | 2018-12-17 | 2021-09-14 | Viavi Solutions Inc. | Article including at least one metal portion |
| US11740532B2 (en) | 2018-12-17 | 2023-08-29 | Viavi Solutions Inc. | Article including light valves |
-
1988
- 1988-09-05 JP JP22198988A patent/JPH0269572A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997018268A1 (en) * | 1995-11-13 | 1997-05-22 | E.I. Du Pont De Nemours And Company | TiO2 PIGMENT COATED WITH SMALL INORGANIC PARTICLES |
| JP2003261828A (en) * | 2002-03-07 | 2003-09-19 | Sk Kaken Co Ltd | Coating composition |
| JP2004323555A (en) * | 2003-04-21 | 2004-11-18 | Nippon Paint Co Ltd | Metal colloid luster material and its manufacturing method |
| US11118061B2 (en) * | 2018-12-17 | 2021-09-14 | Viavi Solutions Inc. | Article including at least one metal portion |
| US11740532B2 (en) | 2018-12-17 | 2023-08-29 | Viavi Solutions Inc. | Article including light valves |
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