JP4241004B2 - Multilayer interference pigment - Google Patents

Description

表１に示した判定結果の基準は、◎印が良好、○印が普通、△印が劣ることを示している。
【００７７】
（用途例４）化粧料粉末固形ファンデーション
下記１〜８を秤取りヘンシェルミキサーで混合し、これに９〜１３を加熱溶解混合したものを添加混合後、パルベライザーで粉砕した。該混合粉砕品を中皿に成型し、所望する粉末固形ファンデーションを得た。

この用途例の粉末固形ファンデーションは、伸びが軽く、顔料色と本発明の多層干渉性顔料から生じる赤色干渉色との作用により、肌色を美しく改善する効果が認められた。
【００７８】
（用途例５）印刷用インキ組成物
下記成分を混合し、サンドミルで混練して印刷用インキ組成物を得た。

この用途例の印刷用インキ組成物を用いて、塗膜厚（乾燥後）５０μｍで白紙上に印刷を行ったところ、塗装体は青色の鮮やかな光沢のある干渉色を有していた。
【００７９】
（用途例６）印刷用インキ組成物
用途例５と同様の配合割合で、本発明の製造例３の緑色の多層干渉性顔料を配合し印刷用インキ組成物を得た。
【００８０】
この用途例の印刷用インキ組成物を用いて、塗膜厚（乾燥後）５０μｍで白紙上に印刷を行ったところ、塗装体は緑色鮮やかな光沢のある干渉色を有していた。
【００８１】
【発明の効果】
本発明は、上記の通り、低屈折率を有する金属酸化物及び高屈折率を有する金属酸化物の交互層で被覆されている鮮やかな干渉色を発色した多層干渉性顔料に関するものであり、具体的には、薄片状の基質表面にチタン組成物を被覆し、更に、この被覆チタン組成物を剥離し、剥離したチタン組成物を基質として、この表面に低屈折率を有する金属酸化物と高屈折率を有する金属酸化物とを交互層で被覆した新規な多層干渉性顔料を提供することを可能とした。更に、塗料、化粧品、インキ、プラスチック等に配合することにより鮮やかに干渉色で発色した光輝感と色の鮮明度を発現し、しかも余色が濁らない非常に優れた商品を提供することができる。
【図面の簡単な説明】
【図１】本発明の原理作用の説明
【図２】本発明の多層干渉性顔料の断面図
【図３】本発明の多層干渉材の図２Ａの部分の拡大図
【図４】本発明の多層干渉性顔料の製造方法を示す概念図
【図５】本発明のコアとなる高屈折率金属酸化物の製造工程の概念図
【図６】本発明のコアとなる高屈折率金属酸化物の剥離工程の概念図
【図７】本発明の製造例１で製造したコア粉体のＸ線回折パターン
【図８】本発明の製造例１で製造したコア粉体の走査型電子顕微鏡の写真
【図９】本発明の製造例１で製造したコア粉体の測色反射率曲線
【符号の説明】
１ 高屈折率層
２ 低屈折率層
３ 薄片状担体材料
４ 高屈折率金属酸化物層
４ａ 高屈折率金[0001]
[Industrial application fields]
The present invention relates to a multilayer interference pigment which is coated with alternating layers of a metal oxide having a low refractive index and a metal oxide having a high refractive index, and which develops a bright interference color. The surface of the substrate is coated with a titanium composition, and then the coated titanium composition is peeled off. Using the peeled titanium composition as a substrate, a metal oxide having a low refractive index and a metal oxide having a high refractive index are coated on the surface. The present invention relates to a novel multilayer interference pigment coated with alternating layers and a method for producing the same. More specifically, the present invention relates to a multilayer interference pigment useful as an optical functional material such as paint, cosmetics, ink, and plastic.
[0002]
[Prior art]
First, the present inventors previously formed a coating layer of a titanium composition having a thickness of 0.05 to 0.6 μm on the surface of a flaky substrate having a size of 50 to 800 μm, and from the coating composition to titanium. The release composition formed by peeling the coating layer of the composition is high-iris titanium dioxide, and the high-irradiation titanium oxide is 70 to 95% by weight of titanium dioxide or titanium hydroxide. Has invented.
[0003]
The above-mentioned high-iris color titanium oxide has a new and excellent radiance and color sharpness that can be recognized by interference colors, and has the characteristics that the extra color does not become cloudy.
[0004]
On the other hand, an interference pigment is known in which metal oxides having different refractive indexes are alternately laminated. For example, in Japanese Patent Publication No. 7-759, in order to obtain a lustrous appearance of chromatic color against a pigment that cannot obtain an interference color such as metal foil powder, a flat fine powder having a metallic luster on its surface. A chromatic-colored glittering powder is disclosed in which two or more layers of six layers of transparent and smooth silicon dioxide thin films are alternately laminated on the surface.
[0005]
In JP-A-7-246366, glass flakes are used as a base material in order to develop a color alone without using a pigment, and titanium dioxide is used as a high refractive index material and silicon dioxide is used as a low refractive index material. A light interference material and a coating material containing the same are disclosed by alternately laminating titanium and silicon dioxide. Furthermore, in Japanese translations of PCT publication No. 2000-501774 and JP-T 2000-517374, a low-refractive-index metal oxide layer comprising a transparent carrier material coated with alternating layers of low-refractive index and high-refractive index metal oxides. Are disclosed which are optically inert multilayer interference pigments.
[0006]
However, in the case of the above-mentioned pigment, for example, “The film thickness of each layer is prepared according to the desired brightness color. In principle, each film thickness is the refractive index of the film × the geometric thickness = the chromatic color to be obtained. The thickness of the metal oxide having a high refractive index is an integral multiple of the optical thickness required for the desired interference color. Although the thickness of the low refractive index is 1 to 20 nm, etc., there is a flat fine powder as a core, or glass flake for a transparent carrier material, mica for a mica carrier material, etc. A thick film such as phyllosilicate and flaky silicon dioxide and a material with low transmittance are used. Therefore, a clear interference color can be obtained due to the edge effect as a whole of the multilayer pigment. There was no problem.
[0007]
By the way, the color is originally a very important color tone that gives humans a physiological and psychological sense of cleanliness, refreshment and security. In fact, it is a technique to create a safe and efficient working environment and a healthy and comfortable living environment by utilizing the physiological and psychological effects that color can have on humans. Obtaining a body is very significant in various industrial fields.
[0008]
Usually, various coloring pigments are used to impart color to a substance. This colored pigment gives a desired color by utilizing phenomena such as light absorption and scattering, but the color pigment alone cannot meet the demands of various sensitivities and designs for recent colors. In addition to this colored pigment, a pearlescent pigment represented by titanium dioxide-coated mica, which is a pigment that utilizes the interference phenomenon of light, has been provided. A major feature of this pearl pigment is that it can provide a so-called flip-flop effect in which the color tone changes slightly depending on the angle.
[0009]
This type of pearlescent pigment is used in various fields such as cosmetics, paints, adhesives, printing inks, and resin kneading, but the following drawbacks have been pointed out. For example, a pearl luster pigment has flaky or plate-like particles such as natural mica, synthetic mica, alumina, silica, silicate glass, borate glass, etc. as a core, and this is coated with titanium dioxide. By controlling the amount, it exhibits a pearly luster with various interference colors. For this reason, when such a pearlescent pigment is used as a pigment for an external composition in cosmetics, paints, printing inks, pressure-sensitive adhesives, resin kneadings, etc., the film becomes an ultra-thin film because the particles are thick. There are disadvantages such as inability to control the thickness and lack of design effect due to the flip-flop effect because of light scattering at the particle edge.
[0010]
On the other hand, for interference pigments in which metal oxides having different refractive indexes are alternately laminated, for example, in the above Japanese Patent Publication No. 7-759, the interference pigments such as metal foil powder that cannot obtain interference colors are countered. In order to obtain a lustrous lustrous appearance of chromatic color, a transparent and smooth silicon dioxide thin film as well as a transparent and smooth titanium dioxide thin film are alternately applied to the surface of a flat fine powder having a metallic luster on the surface. A chromatic luster powder formed by laminating two or more layers is disclosed. Specifically, a glass flake having a thickness of 5 μm and a particle size of 60 to 120 μm is nickel-plated with a thickness of 0.15 μm. The nickel-plated silver glitter powder is used as a base powder, and the powder is dispersed in isopropyl alcohol. Tetraethoxysilane is added to the powder, and water is added. Ete was heated to 60 ° C., after stirring was continued for 60 min, and powder was dried by filtration, washed 120 ° C. SiO₂It is said. Then, in order to form a titanium oxide film on the surface of the powder, tetraisopropoxy titanium is added, water is further added and heated to 60 ° C., stirred for 60 minutes, and then the powder is filtered and washed. After heat treatment at 200 ° C. for 80 minutes, the obtained powder was SiO 2 in the same manner.₂And heat-treated at 200 ° C. to form SiO 2 on the surface of the base powder.₂/ TiO₂/ SiO₂The three-layer film is formed. In addition, using the base powder and tetraethoxysilane and tetraisopropoxytitanium in the same manner as described above,₂/ TiO₂/ SiO₂/ TiO₂/ SiO₂The film is formed in the order of.
[0011]
However, in the specification, although there is a description such as “the powder obtained in this way had a bright blue color”, the edge of the substrate powder (core) was actually too thick. Due to the effect, there is a problem that a clear interference color cannot be obtained, and because the powder is thick, the usage is limited.
[0012]
Further, as another example, the pigment of JP-A-7-246366 is a hydrated titanium oxide produced by hydrolyzing a glass flake as a base material by dispersing it in water and adding a titanium salt and a tin salt. An object is deposited on the surface of the glass flakes.
[0013]
This pigment is washed with water, dried, calcined at 800-1000 ° C. to form titanium oxide, and glass flakes on which titanium oxide is deposited are dispersed in water. Tetraethoxysilane, hydrochloric acid, and ethanol are added to this. In addition, it is hydrolyzed.
[0014]
In this case, the present invention utilizes the fact that a hydrate is formed and then a polycondensation reaction takes place and silica is deposited on the flake surface. TiO₂/ SiO₂/ TiO₂/ SiO₂/ TiO₂The optical interference material can be obtained by controlling the thickness of the deposited film at an odd multiple of about 1/4 wavelength, but the substrate is made of glass flakes. There is a problem that the thickness of the interference material becomes thick and the edge effect has an effect, so that a clear interference color cannot be obtained.
[0015]
Furthermore, as another example, in Japanese translations of PCT publication Nos. 2000-501774 and 2000-517374, a mica, various phyllosilicates, flaky glass, or a water glass solution is solidified on a continuous belt by the technique described in WO93 / 08237. Using flaky silicon dioxide or the like prepared by hydrolysis as a transparent carrier material, for example, an aqueous hydrochloric acid solution is added to adjust the pH to 1.8, and the suspension is heated to 75 ° C. with stirring. Then, tin oxide solution and caustic soda solution are added to coat tin oxide.
[0016]
This pigment is further added with a titanium tetrachloride solution and an aqueous caustic soda solution to coat titanium oxide. When the green interference color is reached, the coating is interrupted, and the aqueous caustic soda solution is added to adjust the pH to 8.0. To this, a water glass solution is added to coat silicon dioxide, and then an aqueous hydrochloric acid solution is added to adjust the pH to 1.8, and a titanium tetrachloride solution and a caustic soda solution are added to coat the second titanium oxide layer. When the green interference color is reached, the coating is interrupted, washed with water, filtered, dried and baked at 850 ° C. for 30 minutes.
[0017]
Although the pigment thus obtained has a description of “having a strong green interference color”, since the transparent carrier material is used, the thickness of the light interference material is increased, and the edge effect influences the clearness. There are problems such as that it is impossible to obtain a satisfactory interference color, and that the use is limited because it is thick.
[0018]
Moreover, in Japanese translations of PCT publication No. 2000-515828, an aqueous solution of a thermally hydrolyzable titanium compound is applied on a continuous belt with an applicator, then hydrolyzed, the resulting coating film is peeled off, and the resulting titanium oxide is used as a carrier material. In addition, by alternately coating silicon oxide and titanium oxide in the same manner as the above-mentioned special table 2000-501774, TiO₂/ SiO₂/ TiO₂/ SiO₂/ TiO₂A five-layer system consisting of
[0019]
However, although there is a description of “having yellow interference color or blue interference color”, the thickness of titanium oxide as a carrier material cannot be controlled by an applicator. Therefore, the particle thickness is as thick as 100 nm, and control within 10 nm cannot be performed. For this reason, the interference color of the carrier material cannot be controlled, and since the thickness of the particles is large, the edge effect is influenced and a clear interference color cannot be obtained. Furthermore, there are many problems such as poor productivity due to the manufacture by the belt.
[0020]
[Problems to be solved by the invention]
In view of the above problems, the present invention provides a multilayer interference pigment having a clearer color tone, a high saturation of interference color, and capable of smooth color development without graininess.
[0021]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have made a transparent carrier material coated with alternately laminated metal oxides having a high refractive index and metal oxides having a low refractive index. Thus, a novel multilayer interference pigment was obtained that eliminates this problem because the metal oxide having a high refractive index as a core is a thin film peeled off after being coated with a flaky carrier material.
[0022]
More specifically, the multilayer interference pigment of the present invention comprises a transparent carrier material that is coated by alternately laminating a metal oxide having a high refractive index and a metal oxide having a low refractive index.
Of these, at least the core metal oxide is coated on a flaky carrier material selected from natural mica, synthetic mica, various phyllosilicates, flaky glass, basic lead carbonate, bismuth oxychloride, or flaky silica. The thin film is peeled off after having a high refractive index of 2.0 to 2.7 and a thickness of 0.05 to 0.7 μm.
On the other hand, a metal oxide having a low refractive index is SiO.₂, Al2O₃, AlOOH, BaO, BaSO₄Or a mixture thereof, wherein the difference in refractive index between the metal oxide having a high refractive index and the metal oxide having a low refractive index is at least 0.3 to 1.2, and the transmittance of the multilayer pigment is 40%. Laminated below.
[0023]
As shown in FIG. 1, when the high refractive index layer (refractive index n1) and the low refractive index (refractive index n2) are alternately laminated in a sparse, dense, sparse, dense, and sparse manner, the light is dense. The light phase does not change for light a and c reflected when going sparse, but the phase of the light changes by half wavelength for light b reflected when light goes from sparse to dense. Therefore, if these phases are aligned, the lights a and b interfere, for example. Here, considering the phase shift between the light beams a and b, if the thickness of the low refractive index n2 is χ, the optical distance of b is 2χ · n2, but the light b is reflected. Since the phase of the wavelength (λ) is changed by a half wavelength, in practice, it becomes (2t + (1/2) λ) · n2. On the other hand, since the phase of the light part a is not changed, the light of b is (2t + (1/2) λ) · n2 2 mλ (m = 1, 2, 3,...) , A strengthening with the light of a. Solving for t, t = (2m−1) λ / c4n2) (m = 1, 2, 3,...), And b light is a low refractive index layer (refractive index n2). Is intensified with the light a when the thickness is an odd multiple of λ / (4n2).
The present invention applies such an interference principle.
[0024]
FIG. 2 shows a cross-sectional view of the multilayer interference material of the present invention. FIG. 2 is an enlarged view of the portion A. As can be seen from FIG. 2, the low refractive index material layer 2 and the high refractive index material layer 1 are alternately laminated on the flaky high refractive index substrate layer 1 so that the transmittance is 40% or less. For example, in the case of the five layers shown in FIG. 3, the light a reflected from the high refractive index base layer 1 and the interface immediately below the incident light, and the interface between the low refractive index material layer 2 and the high refractive index base layer 1 Interference with light b reflected by the light, and light c reflected at the interface between the high refractive index material layer 1 and the low refractive index material layer 2 and the interface between the low refractive index material layer 2 and the high refractive index material layer 1 Interference with the light d reflected by the light, light e reflected at the interface between the high refractive index material layer 1 and the low refractive index material layer 2 and light 5 reflected at the interface between the air and the high refractive index material layer 1 Interference action occurs. With such a laminated structure, the overall light reflectance can be effectively increased with a simple structure, and dark interference light can be developed. Further, by controlling the thickness of the high refractive index material layer 1, the color tone of the colored light can be changed to interference light. That is, a vivid color can be obtained in which colors other than the target color tone are not mixed by controlling the layer thickness and the number of layers.
The reflectance R of the laminated body varies depending on the number of film layers to be laminated 2p + 1 (p = 1, 2,...) And is expressed by the following equation.
(Equation 1)
R = [{1- (nh / ne)^2pnh} / {1+ (nh / ne)^2pnh}]²
nh: Refractive index of the high refractive index material layer
ne: Refractive index of the low refractive index agent layer
Number of layers of multilayer film: 2p + 1 (p = 1, 2,...)
[0025]
For example, when nh is 2.5 and ne is 1.5 and the layers are laminated, R = about 88%, and when nine layers are laminated, R = about 98%.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0027]
(Core high refractive index)
The metal oxide having a high refractive index according to the present invention can provide a glossy coating layer containing a metal oxide and / or metal hydroxide based on anatase or rutile titanium oxide on the surface of a flaky substrate. A composition coated to a specific thickness of 0.05 to 0.6 μm is formed.
[0028]
The flaky substrate is rich in smoothness, and the particle diameter of the particles is preferably in the range of 50 to 800 μm in terms of laser diameter. If the particle diameter is 50 μm or less, the particle diameter of the peeled titanium oxide or titanium hydroxide is too small, and even if the interference gloss can be sufficiently exhibited, the titanium oxide or titanium hydroxide is hardly peeled off. Further, when the particle diameter of the particles is 800 μm or more, the interference gloss of titanium oxide or titanium hydroxide can be sufficiently exerted, but the use is limited because the mechanical strength of the separated particles is weak.
[0029]
Most preferably, it is in the range of 100 to 700 μm. When a substrate of 100 μm or less is used, the particles of the peeling composition described later are too fine, and the coloration of the high iris interference color becomes weak. On the other hand, when the particle diameter of the substrate is larger than 700 μm, the coloring of the high iris interference color by the particles of the peeling composition becomes strong, but it is not preferable because the particles feel rough. Further, when the thickness is 100 to 300 μm, the gloss is strong and peeling is easy.
[0030]
Specifically, FIG. 5 and FIG. 6 show conceptual diagrams of processes for manufacturing the core. Examples of the exfoliated substrate 3 that easily falls within the particle diameter range include natural mica, synthetic mica, glass flake, silica flake, alumina flake, and barium sulfate. Silica flake is relatively easy to control its shape and the degree of smoothness of the surface, and it is also compared that a uniform coating layer 4 is coated on the surface to a specific thickness that gives gloss. This is a preferable material for selection as the flaky substrate 3 in that it is easy.
[0031]
The thickness of the particles of the flaky substrate is not particularly defined, but is preferably in the range of 0.1 to 10 μm. When the thickness of the particles is 0.1 μm or less, the periphery of the substrate curls round, and the interference gloss of the coated titanium oxide or titanium hydroxide cannot be sufficiently exhibited. Further, when the thickness of the particle is 10 μm or more, the interference color of the titanium oxide or titanium hydroxide peeled off in the plane and thickness direction of the coated titanium oxide or titanium hydroxide differs in the plane and thickness direction. Therefore, the overall interference gloss is insufficient.
[0032]
The coating layer is a layer containing a titanium oxide or a titanium hydroxide composition, and is coated to a specific thickness at which gloss is obtained. This is preferably obtained by hydrolysis of a soluble aqueous solution of titanyl sulfate or titanium tetrachloride or titanium alcoholate. Moreover, the coating layer 4 can improve the light resistance and the crushing strength of the peeling composition by including a reinforcing agent of silica and / or metal oxide such as alumina, Zr, Ce, or Zn.
[0033]
When the thickness of the titanium oxide or titanium hydroxide composition layer that is the coating layer is 0.05 μm or less, the particles of the release composition are too fine and the interference color is poor and there is no glitter, and the thickness is 0.6 μm or more. Then, the thickness of the particles of the peeling composition is too thick, so that light scattering by the edge increases, resulting in poor interference color and poor glitter. Therefore, the thickness of the metal oxide serving as the core is preferably 0.1 to 0.5 μm.
[0034]
The size of the coated particles is 0.01-0.05 μm, preferably 0.02-0.04 μm aggregate, but 0.02 μm of titanium oxide or titanium hydroxide when the size of the substrate particles is 300 μm The composition is most easily peeled off. When the particle size of the substrate is 800 μm, the particles of the coating layer can be peeled even with a particle size as small as 0.01 μm. However, when the particle size of the substrate 3 is 100 μm or less, the particle size of the coating layer is also 0. It cannot be peeled off unless the size is 05 μm. That is, the particle diameter of the substrate and the particle diameter of the coating layer 4 are in an inversely proportional relationship.
[0035]
In the present invention, first, a coating composition is formed as described above, and then the coating layer is peeled from the coating composition, thereby finally obtaining the peeling composition. That is, the metal oxide having a high refractive index according to the present invention is a stripping composition formed by stripping a metal oxide or metal hydroxide, which is a coating layer of this coating composition, from the surface of a flaky substrate. .
[0036]
As the exfoliated substrate, commercially available flaky powder can be used, but natural mica, synthetic mica, barium sulfate, silica flake, alumina flake and the like are preferable. For example, Indian chip-like natural mica can be fired in the atmosphere, and the fired chip-like natural mica can be crushed and classified to obtain it.
[0037]
In addition, the surface is further coated with silica or an alumina compound in advance using water glass, organic silica, soluble aluminum salt or the like before peeling, and then the coating composition is peeled off, so that the light resistance is good and the curl is not curled. A composition can be obtained. As described above, first, the coating composition 4 is formed by coating the surface of the flaky substrate with a titanium oxide or a titanium hydroxide composition to a specific thickness at which gloss is obtained. This is preferably obtained by hydrolysis of a soluble aqueous solution of titanyl sulfate or titanium tetrachloride or titanium alcoholate.
[0038]
In obtaining the stripping composition, the coating composition is calcined in advance at 300 to 800 ° C., and the coating layer is peeled off from the flaky substrate in an alkali to obtain a stripping composition having no curling and excellent smoothness. Obtainable.
[0039]
This improves the gloss and interference color of the release composition. When the firing temperature is lower than 300 ° C., the particles of the release composition curl, and when higher than 800 ° C., the titanium oxide of the release composition aggregates, resulting in poor gloss and interference color after release.
[0040]
The stripping composition is filtered, washed with water, dried and then fired to maintain gloss and prevent curling. In addition, as post-treatment after peeling, various types of coatings with iron oxide, cobalt, nickel, lithium, sodium, potassium, colored inorganic compounds, and coating with organic pigments to make organic pigments are various. It can be realized by publicly known according to the application and embodiment.
The high refractive index metal oxide, which is the release composition thus obtained, has a thickness of 0.05 to 0.6 μm. This can be explained by the relationship between the geometric film thickness exhibiting the iris color and the optical film thickness (film thickness x refractive index). In general, the geometric thickness is 0.05 to 0.5 μm, and the optical thickness is This indicates that it is preferable to select a thickness in the range of 0.1 to 0.9 μm.
[0041]
If the composition is too thin, it is difficult to produce the desired interference color, which is not preferable. On the contrary, if the composition is too thick, the interference color intensity is not preferable because the interference intensity decreases due to scattering of the thickness.
[0042]
Next, the high refractive index material layer formed as described above is used as a core, and this is coated with SiO.₂, Al2O₃, AlOOH, BaO, BaSO₄Alternatively, a metal oxide having a low refractive index composed of the mixture is coated.
[0043]
FIG. 4 shows a conceptual diagram of the manufacturing method. In this method, first, a metal oxide having a high refractive index as a core is coated on a flaky carrier material, for example, with titanium oxide, and then peeled off.
[0044]
Next, the peeled titanium oxide is coated with a metal oxide having a low refractive index. When the low refractive index is silica, the exfoliated titanium oxide is dispersed in water, the pH is adjusted to 8.8 with caustic soda, and this dispersion is heated to 80 ° C. with stirring, hydrolyzed, and hydrated. To coat. Subsequently, a polycondensation reaction occurs, and the silica coats the surface of the titanium oxide. The product was washed with filtered water. Further, this is coated with titanium oxide. Titanium oxide is hydrolyzed by adding a tin salt to an aqueous solution of titanium tetrachloride, and the resulting titanium oxide hydrate is coated on the silica surface. The film thickness to be coated is controlled by the amount of titanium tetrachloride. The product is filtered, washed with water and dried. The dried powder is fired at 700 to 1000 ° C. to obtain titanium oxide. As for the powder produced | generated here, the laminated body by which the core was coat | covered with the titanium oxide and the surface was coat | covered with the silica layer and the titanium oxide layer is obtained. Next, this laminate is coated with silica by the same production method as described above. Further, this is coated with titanium oxide by the same production method as described above. The cross-sectional view of the multilayer interference pigment shown in FIG. 2 was generated in this way.
[0045]
As described above, by controlling the number of layers of the high refractive material layer 1 and the low refractive material layer 2 that are alternately laminated and the thickness of the layer film, the transmittance (reflectance) of the specific color of the laminated pigment is developed. Is determined.
[0046]
Hereinafter, specific production examples will be described. The technical scope of the present invention is not limited by these production examples.
[0047]
(Production Example 1)
The manufacturing method of the peeling thin film layer of the high refractive index metal oxide used as a core is explained in full detail. 1 kg of glass flake (RCF140 manufactured by Nippon Sheet Glass Co., Ltd.) having a laser diameter of 50 to 200 μm and an average diameter of 140 μm is put in a 40 liter pulling container, 18 liters of 10% titanyl sulfate aqueous solution, and 0.06 mol / liter sulfuric acid aqueous solution 5 10 liters of urea and 10 liters of clean water were added to the liter, and the mixture was heated with propeller stirring and hydrolyzed at a temperature of 90 ° C. or higher for 6 hours. After allowing to cool, decantation was repeated and washed with water. After washing with water, a 10% caustic soda aqueous solution and 30 liters of clean water were added, the pH of the liquid was adjusted to 8.8, and the mixture was heated to 80 ° C. with propeller stirring. While maintaining the pH and temperature, 0.85 liter of a 1 mol / liter water glass aqueous solution and a 1N hydrochloric acid aqueous solution were added at a flow rate of 0.014 liter per minute for 1 hour. Thereafter, it was further aged for 3 hours. After allowing to cool, a 1 mol / liter sodium carbonate aqueous solution was added to the dispersion to adjust the pH to 12, and the mixture was allowed to stand for 4 days. After standing, the mixture was dispersed for 10 minutes with propeller stirring. Stirring was stopped and the mixture was allowed to stand, and the white powder in the supernatant was separated by decantation. This operation was repeated to recover the powder in the supernatant. The collected powder was washed with water, filtered and dried at 150 ° C. After drying, it was further calcined at 600 ° C. for 2 hours in the air to obtain 730 g of a white powder having a blue interference color. The obtained powder was prepared with an X-ray diffractometer miniflex manufactured by Rigaku Corporation.
[0048]
The X-ray diffraction pattern was a broad peak as shown in FIG. 7, but was an anatase type of titanium oxide. Moreover, it observed at 2000 times and 20000 times with the scanning electron microscope S-2100B type (SEM) made by Hitachi. As a result, as shown in FIG. 8, the flaky particles had an average plate diameter of 8 μm and a particle thickness of 0.30 μm. To further check the color tone, 1 part of this powder was mixed with 30 parts of acrylic clear lacquer made by Musashi Paint Co., Ltd. and applied to a black and white concealment rate test paper, JIS-K5400 with a 4 mil applicator. The reflectance of black paper was measured with a Minolta colorimeter CM-1000. The results are shown in FIG. As can be seen from FIG. 9, a reflectance curve centered on 480 nm is shown, and it can be seen that the color is blue.
[0049]
Titanium oxide flake powder with blue interference color produced as described above is used as a core, and this is coated with metal oxide with low refractive index and metal oxide with high refractive index alternately. To produce a multilayer interference pigment.
[0050]
Weigh 100 g of titanium oxide flake powder with blue interference color into a 5 liter flask, add 2 liters of clean water and 10% caustic soda to pH 8.8, and heat with stirring with a propeller. While maintaining the pH and temperature, a 12.5% aqueous water glass solution and a 1N aqueous hydrochloric acid solution were added at a flow rate of 0.017 liters per minute for 2 hours. Thereafter, it was aged for 3 hours. After standing to cool, it was filtered, washed with water and dried to obtain 230 g of silica-coated titanium oxide having a blue interference color.
[0051]
Put 230 g of silica-coated titanium oxide in a 10-liter container, and put 6.2 liters of 10% titanyl sulfate aqueous solution, 1.8 liters of 0.06 mol / liter sulfuric acid aqueous solution, 35 g of urea and 1 liter of clean water. In addition, the mixture was heated with propeller stirring and hydrolyzed at a temperature of 90 ° C. or more for 5 hours. After standing to cool, it was washed with filtered water and dried at 150 ° C. The dried powder was fired at 600 ° C. in the atmosphere for 2 hours. 450 g of powder having a blue interference color was obtained. The obtained powder is a titanium oxide powder coated with titanium oxide and silica.
[0052]
450 g of titanium oxide powder coated with titanium oxide and silica was placed in a 50-liter pulling container, and 30 liters of clean water and 10% aqueous caustic soda were added to adjust the pH to 8.8. Heat to 80 ° C. with propeller stirring. While maintaining the pH and temperature, 0.02 liter of 12.5% water glass aqueous solution and 1N aqueous hydrochloric acid solution were added for 2 hours. Furthermore, it was aged for 3 hours in that state. After standing to cool, it was washed with filtered water and dried at 150 ° C. 595 g of powder having a blue interference color was obtained. The obtained powder is a titanium oxide powder coated with silica-titanium oxide-silica.
[0053]
595 g of titanium oxide powder coated with silica-titanium oxide-silica is placed in a 10 liter pulling container, 6.8 liter of 10% titanyl sulfate aqueous solution, 2.0 liter of 0.06 mol / liter sulfuric acid aqueous solution, 38 g of urea, and water 1 The mixture was heated with propeller stirring and hydrolyzed at a temperature of 90 ° C. or higher for 5 hours. After standing to cool, it was washed with filtered water and dried at 150 ° C. The dried powder was fired at 600 ° C. in the atmosphere for 2 hours. 845 g of a powder having a bright blue interference color was obtained. The obtained powder is a titanium oxide powder coated with titanium oxide-silica-titanium oxide-silica.
[0054]
(Production Example 2)
The manufacturing method of the peeling thin film layer of the high-refractive-index metal oxide used as a core similarly to the manufacture example 1 is explained in full detail. 1 kg of natural mica pulverized and classified product having a laser diameter of 150 to 500 μm and an average diameter of 250 μm is put in a 40 liter pulling container, 14.4 liters of 10% titanyl sulfate aqueous solution and 5.2 liters of 0.06 mol / liter sulfuric acid aqueous solution. Then, 100 g of urea and 15 liters of clean water were added thereto, and the mixture was heated and hydrolyzed at a temperature of 90 ° C. or more for 6 hours while stirring with a propeller. After allowing to cool, decantation was repeated and washed with water. After washing with water, a 10% caustic soda aqueous solution and 30 liters of clean water were added, the pH of the liquid was adjusted to 8.8, and the mixture was heated to 80 ° C. with propeller stirring. While maintaining pH and temperature, 0.68 liter of 1 mol / liter aqueous water glass solution and 1N aqueous hydrochloric acid solution were added at a flow rate of 0.014 liter per minute for 50 minutes. Thereafter, it was further aged for 3 hours. After the statute, 1 mol / liter sodium carbonate aqueous solution was added to the dispersion to adjust the pH to 12, and left for 4 days. After standing, the mixture was dispersed for 10 minutes with propeller stirring. Stirring was stopped and the mixture was allowed to stand, and the white powder in the supernatant was separated by decantation. This operation was repeated to recover the powder in the supernatant. The collected powder was washed with water, filtered and dried at 150 ° C. After drying, it was further calcined at 600 ° C. for 2 hours in the air to obtain 580 g of white powder having a red interference color.
[0055]
The obtained powder was measured with an X-ray diffractometer miniflex manufactured by Rigaku Corporation. Although the X-ray diffraction pattern was a broad peak, it was an anatase type of titanium oxide. Moreover, it observed at 2000 times and 20000 times with the scanning electron microscope S-2100B type (SEM) made by Hitachi. The results were flaky particles with an average plate diameter of 8 μm and a particle thickness of 0.25 μm. To further check the color tone, 1 part of this powder was mixed with 30 parts of acrylic clear lacquer made by Musashi Paint Co., Ltd., and applied to a black and white concealment rate test paper JIS-K5400 with a 4 mil applicator. The reflectance was measured with a Minolta colorimeter CM-1000. As a result, the reflectance at a wavelength of 650 nm or more was high and the interference color was red.
[0056]
Titanium oxide flake powder with red interference color produced as described above is used as a core, and this is coated with metal oxide with low refractive index and metal oxide with high refractive index alternately. To produce a multilayer interference pigment.
[0057]
100 g of titanium oxide flake powder having a red interference color is weighed into a 5 liter flask, and 2 liters of tap water and 10% caustic soda are added to adjust the pH to 8.8. While maintaining the pH and temperature, 12.5% aqueous water glass solution and 1N aqueous hydrochloric acid solution were added at a flow rate of 0.02 liters per minute for 2 hours. Thereafter, it was aged for 3 hours. The mixture was allowed to cool, filtered, washed with water, and dried to obtain 270 g of silica-coated titanium oxide having a red interference color.
[0058]
Put 270 g of silica-coated titanium oxide in a 10-liter container, add 7.3 liters of 10% titanyl sulfate aqueous solution, 1.8 liters of 0.06 mol / liter sulfuric acid aqueous solution, and 35 g of urea, and stir with a propeller. The mixture was then heated and hydrolyzed for 5 hours at a temperature of 90 ° C. After standing to cool, it was washed with filtered water and dried at 150 ° C. The dried powder was fired at 600 ° C. in the atmosphere for 2 hours. 530 g of powder having a red interference color was obtained. The obtained powder was a titanium oxide powder coated with titanium oxide and silica.
[0059]
530 g of titanium oxide powder coated with titanium oxide and silica was placed in a 50-liter container, and 30 liters of clean water and 10% aqueous sodium hydroxide solution were added to adjust the pH to 8.8. Heat to 80 ° C. with propeller stirring. While maintaining the pH and temperature, 0.024 liter of 12.5% water glass aqueous solution and 1N aqueous hydrochloric acid solution were added for 2 hours. Furthermore, it was aged for 3 hours in that state. After standing to cool, it was washed with filtered water and dried at 150 ° C. 700 g of powder having a red interference color was obtained. The obtained powder was a titanium oxide powder coated with silica-titanium oxide-silica.
[0060]
700 g of titanium oxide powder coated with silica-titanium oxide-silica is put in a 15 liter pulling container, 8.1 liters of 10% titanyl sulfate aqueous solution, 2.0 liters of 0.06 mol / liter sulfuric acid aqueous solution and 38 g of urea. In addition, the mixture was heated with propeller stirring and hydrolyzed at a temperature of 90 ° C. or more for 5 hours. After standing to cool, it was washed with filtered water and dried at 150 ° C. The dried powder was fired at 600 ° C. in the atmosphere for 2 hours. 980 g of a powder having a bright red interference color was obtained. The obtained powder was a titanium oxide powder coated with titanium oxide-silica-titanium oxide-silica.
[0061]
(Production Example 3)
The manufacturing method of the peeling thin film layer of the high refractive index metal oxide used as a core is demonstrated in full detail similarly to the manufacture example 1 and the manufacture example 2. FIG. Put 2 kg of natural mica pulverized and classified product with a laser diameter of 500-800 μm and an average diameter of 650 μm in a 40 liter pulling container, 6 liters of 10% titanyl sulfate aqueous solution, and 5 liters of 0.06 mol / liter sulfuric acid aqueous solution. 110 g of urea and 15 liters of clean water were added, heated with propeller stirring, and hydrolyzed at a temperature of 90 ° C. or higher for 6 hours. After allowing to cool, decantation was repeated and washed with water. After washing with water, 10% caustic soda aqueous solution and 30 liters of clean water were added to adjust the pH of the solution to 9.0, and the mixture was heated to 80 ° C. with propeller stirring. While maintaining the pH and temperature, 0.37 liter of 1 mol / liter aqueous water glass solution and 1N aqueous hydrochloric acid solution were added at a flow rate of 0.014 liter per minute for 1 hour. Thereafter, it was further aged for 3 hours. After allowing to cool, a 1 mol / liter sodium carbonate aqueous solution was added to the dispersion to adjust the pH to 11, and the mixture was allowed to stand for 3 days. After standing, the mixture was dispersed for 10 minutes with propeller stirring. Stirring was stopped and the mixture was left standing, and the white powder in the supernatant was separated by decantation. This operation was repeated to recover the powder in the supernatant. The collected powder was washed with water, filtered and dried at 150 ° C. After drying, it was further calcined at 650 ° C. for 2 hours in the air to obtain 310 g of a white powder having a green interference color.
[0062]
The obtained powder was measured with an X-ray diffractometer miniflex manufactured by Rigaku Corporation. Although the X-ray diffraction pattern was a broad peak, it was an anatase type of titanium oxide. Moreover, it observed at 2000 times and 20000 times with the scanning electron microscope S-2100B type (SEM) made by Hitachi. As a result, the flaky particles had an average plate diameter of 10 μm and a particle thickness of 0.35 μm. In order to further check the color tone, 1 part of this powder was mixed with 30 parts of acrylic clear lacquer made by Musashi Paint Co., Ltd., and applied to a black and white concealment rate test paper, JIS-K5400 with a 4 mil applicator. The reflectance of black paper was measured with a Minolta colorimeter CM-1000. The result shows a reflectance curve centered on 520 nm, which is green.
[0063]
Titanium oxide flake powder with green interference color produced as described above is used as a core, and this is coated with metal oxide with low refractive index and metal oxide with high refractive index alternately. To produce a multilayer interference pigment.
[0064]
100 g of titanium oxide flake powder having a green interference color is weighed in a 5 liter flask, and 2 liters of tap water and 10% aqueous caustic soda solution are added to adjust the pH to 9.0. While maintaining pH and temperature, 12.5% aqueous water glass solution and 1N aqueous hydrochloric acid solution were added at a flow rate of 0.015 liters per minute for 2 hours. Thereafter, it was aged for 3 hours. After allowing to cool, filtration, washing with water and drying were performed to obtain 200 g of silica-coated titanium oxide having a green interference color.
[0065]
200 g of silica-coated titanium oxide is put in a 10-liter container, and 5.4 liters of a 10% titanyl sulfate aqueous solution, 1.8 liters of a 0.06 mol / liter sulfuric acid aqueous solution, 35 g of urea, and 1 liter of clean water. In addition, the mixture was heated with propeller stirring and hydrolyzed at a temperature of 90 ° C. or more for 5 hours. After standing to cool, it was washed with filtered water and dried at 150 ° C. The dried powder was fired at 600 ° C. in the atmosphere for 2 hours. 390 g of a powder having a green interference color was obtained. The obtained powder is a titanium oxide powder coated with titanium oxide and silica.
[0066]
390 g of titanium oxide powder coated with titanium oxide and silica was placed in a 50-liter container, and 30 liters of clean water and a 10% aqueous sodium hydroxide solution were added to adjust the pH to 9.0. Heat to 80 ° C. with propeller stirring. While maintaining the pH and temperature, 0.017 liter of 12.5% water glass aqueous solution and 1N aqueous hydrochloric acid solution were added for 2 hours. Furthermore, it was aged for 3 hours in that state. After standing to cool, it was washed with filtered water and dried at 150 ° C. A powder 515 having a green interference color was obtained. The obtained powder is a titanium oxide powder coated with silica-titanium oxide-silica.
[0067]
515 g of titanium oxide powder coated with silica-titanium oxide-silica is placed in a 10 liter pulling container, 6.0 liter of 10% titanyl sulfate aqueous solution, 2.0 liter of 0.06 mol / liter sulfuric acid aqueous solution and 38 g of urea. In addition, the mixture was heated with propeller stirring and hydrolyzed at a temperature of 90 ° C. or more for 5 hours. After standing to cool, it was washed with filtered water and dried at 150 ° C. The dried powder was fired at 600 ° C. in the atmosphere for 2 hours. 730 g of powder having a bright green interference color was obtained. The obtained powder is a titanium oxide powder coated with titanium oxide-silica-titanium oxide-silica.
[0068]
In each of Production Examples 1, 2, and 3, the core is made of titanium oxide having a high refractive index, which is alternately coated with silica having a low refractive index and titanium oxide having a high refractive index. All the laminates had a reflectance of 98% or more.
[0069]
In the present invention, the multilayer interference pigment produced as described above is used as the above-mentioned application, and typical examples of the application will be described below. However, the technical scope of the present invention is not limited by these uses.
[0070]
(Application 1) Automotive paint
A steel sheet having an intermediate coating film formed on the electrodeposition coating film was prepared, and after applying a color base coating, it was baked and dried at 140 ° C. for 30 minutes. Next, a base paint containing 5% by weight of a multilayer interference color pigment having a blue interference color obtained in Production Example 1 in a resin liquid composed of an acrylic resin and a melamine resin is prepared, and a film thickness is formed on the surface of the color base coating film. Spray coating was performed to a thickness of 15 μm. Then, the acrylic-melamine clear coating was further spray-coated with a wet-on-wet so as to keep the film thickness of 40 μm, and baked at 140 ° C. for 30 minutes to integrally cure the base coating film and the clear coating film.
[0071]
(Application example 2) Automotive paint
A multilayer interference color pigment having a red interference color obtained in Production Example 2 was blended in the same manner as in Application Example 1. The type of paint and the coating thickness were applied under the same conditions as in Application Example 1.
[0072]
(Application 3) Automotive paint
A multilayer interference color pigment having a green interference color obtained in Production Example 3 was blended in the same manner as in Application Example 1. The type of paint and the coating thickness were applied under the same conditions as in Application Example 1.
[0073]
(Comparative Example 1) Automotive paint
In the same manner as in Application Example 1, the flaky powder of titanium oxide having the blue interference color used as the core in Production Example 1 was blended. The type of paint and the coating thickness were applied under the same conditions as in Application Example 1.
[0074]
(Comparative Example 2) Automotive paint
In the same manner as in Application Example 1, commercially available interference titanium oxide-coated mica (Iriodin 225 manufactured by Merck) was blended. The type of paint and the coating thickness were applied under the same conditions as in Application Example 1.
[0075]
About the coated steel plate obtained in the above, the degree of the design property which takes brightness, a saturation, and a color tone was judged relatively by visual observation of the judgment expert. The results are shown in Table 1.
[0076]
[Table 1]

The criteria for the determination results shown in Table 1 indicate that ◎ is good, ○ is normal, and Δ is inferior.
[0077]
(Application example 4) Cosmetic powder solid foundation
The following 1 to 8 were weighed and mixed with a Henschel mixer, and after 9 to 13 was dissolved by heating and mixed with this, the mixture was added and mixed, and then pulverized with a pulverizer. The mixed pulverized product was molded into an intermediate dish to obtain a desired powder solid foundation.

The powder solid foundation of this application example has a light elongation, and the effect of beautifully improving the skin color was recognized by the action of the pigment color and the red interference color generated from the multilayer interference pigment of the present invention.
[0078]
(Application example 5) Ink composition for printing
The following components were mixed and kneaded with a sand mill to obtain a printing ink composition.

When printing was performed on a white paper with a coating thickness (after drying) of 50 μm using the printing ink composition of this application example, the coated body had a blue, bright and glossy interference color.
[0079]
(Application example 6) Ink composition for printing
A green multilayer interference pigment of Production Example 3 of the present invention was blended at the same blending ratio as in Application Example 5 to obtain a printing ink composition.
[0080]
When printing was performed on a white paper with a coating thickness (after drying) of 50 μm using the printing ink composition of this application example, the coated body had a bright green glossy interference color.
[0081]
【The invention's effect】
As described above, the present invention relates to a multilayer interference pigment that develops a bright interference color and is coated with alternating layers of a metal oxide having a low refractive index and a metal oxide having a high refractive index. Specifically, the surface of a flaky substrate is coated with a titanium composition, the coated titanium composition is further peeled off, and the peeled titanium composition is used as a substrate to form a metal oxide having a low refractive index and a high surface. It has become possible to provide a novel multilayer interference pigment in which a metal oxide having a refractive index is coated with alternating layers. Furthermore, by blending with paints, cosmetics, inks, plastics, etc., it is possible to provide a very excellent product that expresses the brilliant color and the vividness of colors that are vividly colored with interference colors and that does not turbidity. .
[Brief description of the drawings]
FIG. 1 illustrates the principle and operation of the present invention.
FIG. 2 is a cross-sectional view of the multilayer interference pigment of the present invention.
3 is an enlarged view of the portion of FIG. 2A of the multilayer interference material of the present invention.
FIG. 4 is a conceptual diagram showing a method for producing a multilayer interference pigment of the present invention.
FIG. 5 is a conceptual diagram of a manufacturing process of a high refractive index metal oxide which is a core of the present invention.
FIG. 6 is a conceptual diagram of a peeling process of a high refractive index metal oxide serving as a core of the present invention.
7 is an X-ray diffraction pattern of the core powder produced in Production Example 1 of the present invention. FIG.
8 is a scanning electron microscope photograph of the core powder produced in Production Example 1 of the present invention. FIG.
FIG. 9 is a colorimetric reflectance curve of the core powder produced in Production Example 1 of the present invention.
[Explanation of symbols]
1 High refractive index layer
2 Low refractive index layer
3 Flaky carrier material
4 High refractive index metal oxide layer
4a high refractive index gold

Claims (6)

It consists of a transparent carrier material that is coated by alternately laminating a metal oxide having a high refractive index and a metal oxide having a low refractive index, and the core metal oxide having a high refractive index is natural mica or synthetic mica. Metal oxides that are at least the core of a thin film that has been peeled off after being coated with a flaky carrier material selected from various phyllosilicates, flaky glass, basic lead carbonate, bismuth oxychloride, or flaky silica A multilayer interference pigment having a refractive index of 2.0 to 2.7 and a thickness of 0.05 to 0.6 μm. The multilayer interference pigment according to claim 1, wherein a difference in refractive index between the metal oxide having a high refractive index and the metal oxide having a low refractive index is at least 0.3 to 1.2. The multilayer interference pigment according to claim 2, wherein the multilayer interference pigment is laminated with a transmittance of 40% or less. The oxide having the high refractive index is TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , Fe ₃ O ₄ , Cr ₂ O ₃ , or ZnO, or a mixture of these oxides, or iron titanate, hydrated iron 2. The multilayer interference pigment according to claim 1, wherein the multilayer interference pigment is an oxide, a low-order titanium oxide, or a mixture of these compounds. The metal oxide having a low refractive _{index, SiO 2, Al 2 O 3} , AlOOH, BaO, multilayer interference pigment according to claim 1, characterized in that the BaSO ₄ or mixtures thereof. 5. The multilayer interference pigment according to claim 1, wherein the multilayer interference pigment is used in colored paints, printing inks, plastics, cosmetics, ceramics, and glass bottles.

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