JP2003155422A - Composite film pigment and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite film pigment which exhibits a deep, unique sheen color tone, and to provide a production method therefor. SOLUTION: The composite film pigment is composed of a scaly inorganic pigment coated with titanium dioxide and a metallic film layer with which the surface of the pigment is coated in the form of islands, and the metallic film layer is composed of islands of 1×10<10> -10<15> /m<2> in number per specific surface area of the pigment and, simultaneously, its attached amount, in terms of metal weight, of 0.00001-0.050 g/m<2> . The above scaly inorganic pigment contains at least one kind selected from the group consisting of a mica flake, a silica flake, an alumina flake, an aluminum flake, and a mica-like iron oxide. The method for producing the composite film pigment comprises forming a metallic film layer in an amount, in terms of metal weight, of 0.00001-0.050 g/m<2> on the surface of the scaly inorganic pigment coated with the titanium dioxide in the form of islands of 1×10<10> -10<15> /m<2> in the number per specific surface area of the pigment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite film pigment and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, titanium dioxide pigments and pigments coated with titanium dioxide have been favorably used in various paints, cosmetics, plastic moldings and the like. The presence of interference light due to the high refractive index of titanium dioxide enhances the sharpness and glossiness of the coating film appearance, and imparts a uniquely high design property to the appearance of the coating film and cosmetics mixed with it.

Conventionally, scale-like inorganic pigments coated with titanium dioxide (that is, pigments obtained by coating scale-like inorganic pigments with titanium dioxide) are known, and various scale-like inorganic pigments such as mica and aluminum thin films are known. Is used.
However, in recent years, in order to obtain even higher designability, a method of thinly coating the surface of the scale-like inorganic pigment coated with titanium dioxide with a metal or a metal oxide (JP-A-57-16105).
No. 5, JP-A-1-108267, and JP-A-4-108267.
268380). These coating treatments aim to develop the interference light of titanium dioxide more beautifully.

By the way, when the surface of the scale-like inorganic pigment coated with titanium dioxide is thinly coated with a metal or a metal oxide, the interference light of titanium dioxide may develop a more beautiful color, but the principle of the color development is still not always true. Not clarified. Incidentally, among the above-mentioned patent publications, Japanese Unexamined Patent Publication No. 4-2
In Japanese Patent No. 68380, when interference of reflected light is absorbed by a light absorbing portion, interference light is colored beautifully, but most of the patent publications do not clearly describe the coloring principle. The coloring principle is unknown.

Further, when the scale-like inorganic pigment coated with titanium dioxide is coated with a metal or a metal oxide by using the method of the invention proposed above, the interference light of titanium dioxide is slightly increased in any case. Although it stands out at all, at the same time, it had a drawback that it was colored a little black gray and the brightness was lowered, and the color tone was drastically reduced as compared with the scale-like pigment coated with titanium dioxide.

The action of the color tone produced when the scale-like inorganic pigment coated with titanium dioxide is coated with a metal or a metal oxide can be considered as the following three types. Reduction of interference light due to reduction of total area of titanium dioxide Increase of interference light due to absorption of transmitted light Effect of imparting metallic luster by metal coating and coloring with metal oxide That is, coating titanium dioxide with metal or metal oxide Then, as the adhesion area (covering area) increases, the substantial surface area of titanium dioxide that produces interference light decreases, which reduces interference light and reduces saturation. However, the coating of metal or metal oxide also has the function of absorbing transmitted light depending on the adhesion conditions, so if the absorption of transmitted light can be performed efficiently, the effect of The interference light will increase. However, the lightness of the color tone decreases as the amount of light decreases. Further, due to the effect of, the added value can be further added to the color tone of the interference light as the base.

In Japanese Patent Laid-Open No. 57-161055, since the scale-like pigment coated with titanium dioxide is almost completely covered with a metal, the effect of completely covering the titanium dioxide cannot be expected. In JP-A-1-108267,
Although it is said that there are variations in color tone depending on how metal is adhered, the saturation and lightness are dull because the effects of are not taken into consideration. JP-A-4-268 in which mica is coated with a metal layer through a low-order oxide layer of titanium
In the metallic pigment according to Japanese Patent No. 380, the lower oxide of titanium is formed in the lower layer of the metal-deposited portion, which is thought to maintain a little balance with the result, but since it does not consider Both the degree and the brightness are slightly dark and dull.

Further, when a scale-like inorganic pigment coated with titanium dioxide is overlaid with a metal or a metal oxide, a slight difference in conditions has a delicate influence on the color tone of the pigment. It is an essential condition in industrial production to be able to control the variation in color tone for each lot, and these controls can only be achieved by accurately grasping. However, since the above-mentioned (1) to (3) have not been taken into consideration, the existing technology has not been able to find a condition for exhibiting the color tone with the highest added value, and has not been able to fully control the variation in the color tone.

In the first place, when a scale-like inorganic pigment coated with titanium dioxide is mixed in a paint and used for coating, it is not necessary to coat the scale-like inorganic pigment coated with titanium dioxide with a metal or a metal oxide. If a black coating is applied to the base, the transmitted light can be easily absorbed, and the interference light can be emphasized without making the color tone dull. Therefore, because the scale-like inorganic pigment coated with titanium dioxide is purposely subjected to a coating treatment with a metal or a metal oxide, the reduction in saturation and brightness is not reduced as much as possible, and the merits of the color tone due to the coating treatment of the metal or the metal oxide are reduced. Is required. Furthermore, it is extremely costly to coat a scale-like inorganic pigment coated with titanium dioxide with metal or a metal oxide, so if it is not added enough product value to compensate for it, it will be an extremely commercial product. It cannot be sold.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art with respect to a composite film pigment in which the surface of a scale-like inorganic pigment coated with titanium dioxide is thinly coated with a metal or a metal oxide, An object of the present invention is to provide a composite film pigment exhibiting a unique luster color tone with a depth that is unprecedented and to provide a method for producing the same.

[0011]

Means for Solving the Problems The inventors of the present invention have made earnest studies on means for solving the above problems, and as a result, formed an island-shaped metal film on the surface of the scale-like inorganic pigment coated with titanium dioxide. It was found that a composite film pigment can be obtained by the above. Furthermore, in order to develop the interference light of titanium dioxide more beautifully and with good reproducibility, it was found that it is necessary to coat the metal film layer to be formed with a smaller amount of metal, more finely and uniformly with an island distribution, and the present invention Has been completed.

That is, the present invention comprises a scale-like inorganic pigment coated with titanium dioxide, and a metal coating layer in which the surface of the pigment is coated in an island shape, and the metal coating layer is 1 × per specific surface area of the pigment. Island-shaped consisting of 10 ¹⁰ to 10 ¹⁵ pieces / m ² and 0.00001 to 0.050 g in terms of metal weight
It is a composite film pigment having an adhesion amount of / m ² . The scale-like inorganic pigment is preferably at least one selected from the group consisting of mica flakes, silica flakes, alumina flakes, aluminum flakes and mica-like iron oxide. In addition, the present invention provides the surface of a scale-like inorganic pigment coated with titanium dioxide on a surface of 1 × 10 ¹⁰ to 1 × 10 ¹⁰ per specific surface area of the pigment.
A method for producing a composite coated pigment is characterized in that a metal coating layer of 0.00001 to 0.050 g / m ^{2 in} terms of weight of metal coated in an island shape consisting of 10 ¹⁵ pieces / m ² is formed.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The contents of the present invention will be described in detail below. The flaky inorganic pigment in the present invention is a mica flakes,
Examples include silica flakes, alumina flakes, aluminum flakes, and mica-like iron oxide. In the present invention, the “flake inorganic pigment coated with titanium dioxide” means a pigment obtained by coating the above flake inorganic pigment with titanium dioxide. The method of coating the scale-like inorganic pigment with titanium dioxide is not particularly limited. For example, a method of boiling a sulfuric acid acid titanium oxysulfate solution to hydrolyze it (eg, JP-B-43-256).
No. 44) or a method of hydrolyzing titanium tetrachloride (for example, Japanese Examined Patent Publication No. 46-3824) can be used.

The metal coating layer formed on the surface of the scale-like inorganic pigment coated with titanium dioxide in the present invention and coating the surface of the pigment in an island shape will be described. The scale-like inorganic pigment coated with titanium dioxide exhibits a highly saturated color due to interference light when the transmitted light is efficiently absorbed. This is a phenomenon that can be easily observed by, for example, placing a scale-like inorganic pigment coated with titanium dioxide on black colored paper. The wavelength of the interference light is determined by the film thickness of titanium dioxide,
Therefore, the color developed can be controlled by the film thickness of titanium dioxide.

Even if another substance is attached to the surface of the scale-like inorganic pigment coated with titanium dioxide, the same phenomenon may occur. Although it does not necessarily develop color in all cases of adhesion, the substance to be adhered in the case of color development does not need to be a black substance that is particularly easy to absorb light, and if it can be firmly adhered to the surface of the pigment, Regardless of the material or appearance color tone of the material, it exhibits the base color tone due to interference light according to the film thickness of titanium dioxide.

However, in this case, even if the scale-like inorganic pigment coated with titanium dioxide is the same blue pigment, the color tone is dull dark blue to vivid blue, metallic blue or white. The present inventors have found that it depends to a large extent on the substance such as blue color that is attached to the surface and the form of attachment. When this adhered substance (herein referred to as an adhered substance) is covered with a film thickness of more than 10 nm and completely covers the entire surface of the scale-like inorganic pigment coated with titanium dioxide without any defects, the color tone of the interference light due to the thin film of titanium dioxide is improved. I hardly get it. Therefore, in order to obtain the color tone of the interference light, it is necessary to coat the adhering substance in a state with an appropriate coating defect. In the present invention, a metal is used as the adhering substance.

For the scale-like inorganic pigment coated with titanium dioxide
On the other hand, using the same amount of metal per unit area as the adhered substance
When coated, it was coated in more finely dispersed islands
A better interference color due to titanium dioxide can be obtained. That
Therefore, even if the same amount of metal is attached,
In this case, we have found that there are the following general rules. sand
That is, a very small amount of metal adhesion (metal adhesion amount = 0.0000
1 to 0.010 g / m ²), The amount of metal adhered is fixed
When it does, it increases the degree of dispersion of metal on the surface and
Titanium dioxide was coated as it became finely island-shaped.
The color tone of the scale-like inorganic pigment is “white” → “light blue” →
"Slightly bright blue" → "Metallic feeling due to adhered metal"
There is a slight dark blue color. Well
In addition, a slightly large amount of metal deposition (metal deposition amount = 0.010
~ 0.050 g / m²), Fix the metal adhesion amount.
In the case of metal, increase the degree of adhesion and dispersion of metal on the surface and
Scales coated with titanium dioxide
The color tone of the flake inorganic pigment is “white” → “light blue” → “ya”
"Bright blue" → "Dark dark blue" → "Black-gray wear
Color or only metallic luster color due to adhered metal "
I found that

As described above, by coating the metal finer and smoother, the transmitted light can be effectively absorbed with a small coating amount, and the interference light due to the titanium dioxide coating can be highlighted, and the unevenness of the coated metal surface can be enhanced. Is small, a vivid deep blue appearance color tone "having a slight metallic feeling due to the adhered metal" can be obtained. The absorption of transmitted light by this metal occurs even when a metal having a low reducing property, that is, platinum or gold is attached, but in this case, the lower oxide of titanium due to the reduction of the underlying titanium dioxide does not occur. Therefore, the coloring system in the present invention is different from the one described in the above-mentioned Japanese Patent Laid-Open No. 4-268380 in which the light absorbing portion made of the titanium low order oxide is provided.

The principle that the interference light due to the titanium dioxide coating can be highlighted by coating the scale-like inorganic pigment coated with titanium dioxide with a metal (using a metal as an adhering substance) is speculated as follows. To be done. That is, as described above, the action of the metal when the metal is used as the adhering substance is divided into the following three. Reduction of interference light due to reduction of total area of titanium dioxide Increase of interference light due to absorption of transmitted light Giving metallic luster by metal coating When metal deposition is performed on titanium dioxide, titanium dioxide that produces interference light increases with increase of metal area of adhesion. The real surface area is reduced and the interference light is reduced. However, if the absorption of transmitted light is further caused by metal adhesion,
The effect of and is canceled out, and the substantial interference light increases. Further, when the amount of the adhered metal is constant, it is more effective to coat the finer islands, but the finer islands substantially increase the metal surface area and reduce the light reflection area. Since it increases, the effect of imparting metallic luster is enhanced. In addition, coating the surface of titanium dioxide with the smallest possible amount of the adhered metal does not impair the smoothness of the surface of the scaly pigment, and therefore does not impair the distribution characteristics when used as a mixture in the paint. There are advantages.

The amount of metal adhering to the surface of the scale-like inorganic pigment coated with titanium dioxide (the scale-like inorganic pigment coated with titanium dioxide) is 0.00001 to 0 per specific surface area of the pigment in terms of metal weight. 0.050 g / m ² , more preferably 0.0001 to 0.010 g / m ^2.
Is. When the amount of deposited metal is less than 0.00001 g / m ² , no interference color of titanium dioxide can be obtained no matter how the number of islands per specific surface area of the pigment is controlled.
After the treatment, the pigment remains white, which is the color of the pigment, or milky white. When the metal deposition amount exceeds 0.050 g / m ² , the interference color of titanium dioxide may be obtained by controlling the number of islands per specific surface area of the above pigment, but after the treatment, The color of the pigment is dull and blue, which is close to black, and the commercial value as a design pigment cannot be expected at all. Also, in terms of cost, it is disadvantageous to use excess metal.

Metal adhesion amount is 0.0001 to 0.010 g
For / m ^2, a condition exhibiting "light blue" - "slightly brilliant blue" - "vivid dark blue metallic effect due to adhesion metal is in the slightly" as described above, per specific surface area of the scale-like inorganic pigment It is necessary to attach the metal in an island shape composed of 1 × 10 ¹⁰ to 10 ¹⁵ pieces / m ² . Then, as a condition for exhibiting "a bright dark blue color with a slight metallic feeling due to the adhered metal", the metal is adhered in an island shape composed of 1 × 10 ¹¹ to 10 ¹⁴ particles / m ² per specific surface area of the scaly inorganic pigment. It is preferable. In addition, the metal adhesion amount is a value in terms of metal weight. In the present invention, coating (adhesion)
A metal is used as the metal. For example, when the metal becomes a metal oxide, it is converted into the metal weight.

Among the pigments obtained in the present invention, the color tone obtained by mixing a pigment exhibiting "a vivid deep blue color with a slight metallic feeling due to an adhering metal" with a resin is the same as that of existing conventional blue paints. It has no similar color and has a very high design quality. The tone of this "bright dark blue with a slight metallic feel due to the adhered metal" is
It is achieved only by controlling the amount of metal deposition and the number of islands thereof within the above range. Further, in producing a pigment having a desired color tone during industrial production, control of these two numerical values is also an essential condition for producing a pigment product having good color tone reproducibility.

The conditions for coating the surface of the scale-like inorganic pigment with the adhering substance in the form of islands have been described above by taking the core body of blue interference color as an example. However, the conditions of gold interference color, green interference color or red interference color are described. In the case of using a core body, the above-mentioned color-developing conditions by the island-shaped coating are exactly the same.

In the present invention, a metal is used as the adhering substance. In the present invention, in order to obtain a deep interference color while having a metallic tone of the metal, it is necessary to coat in a fine island-like distribution with a smaller coating amount, and a metal having a brighter feeling. Need to use. In particular, when the corrosive environment using the pigment is not a problem, the metal to be attached can be any metal having a bright feeling.
Such metals include platinum, gold, palladium,
Mention may be made of silver, chromium, nickel, aluminum, iron, titanium, zinc, cobalt, magnesium, tin or copper. Further, an alloy such as stainless steel can also be used. However, the surface activity is high due to the amount of metal adhering on a minute diameter of nm unit, and there is a possibility that the absorption of transmitted light due to adhesion to the titanium dioxide surface may be lost by slight corrosion, so it is more corrosion resistant depending on the environment used. It is necessary to use a certain metal. Examples of such a metal having corrosion resistance include platinum, gold, palladium, or silver having inert corrosion resistance, or chromium, nickel, stainless steel, or aluminum having corrosion resistance by forming an oxide film or a hydroxide film on the surface. , Or copper can be used. More preferably, platinum, gold, palladium or silver having an inert type corrosion resistance is used.

The method for coating the metal film may be any method, and well-known means such as a dry process method by vacuum deposition or sputtering or a wet process method such as electroless plating can be used. Further, in many cases, the scale-like inorganic pigment coated with titanium dioxide by using these methods contains 0.00001 to 0.
When coating is performed with an adhesion amount of 050 g / m ² , inevitably a suitable coating defect occurs and it becomes possible to coat in an island shape.
However, as described above, it is necessary to control the number of islands in order to obtain color tone reproducibility, so no matter which treatment method is used to coat the metal film layer, management that affects the number of islands Keep items tight. For example,
When the metal is coated by electroless plating after the pretreatment of Sn-Pd by the two-liquid method, the number of attached Pd, which is the nucleus for plating, affects the number of islands, so Sn-Pd depending on the situation Appropriate pretreatment and management are required.

The composite film pigment having a durable luster thus obtained can be used by mixing it into various paints, cosmetics, plastic molded products, etc. by a known method. The composite film pigment of the present invention exhibits excellent dispersibility in these resins and paints. In addition, the appearance has a vivid interference color due to the titanium dioxide thin film while having a metallic tone.

[0027]

EXAMPLES In order to explain the present invention in more detail, examples will be specifically described along with comparative examples, but the scope of the present invention is not limited by these examples.

Example 1 The surface of a mica flakes having an average particle size of 18.4 μm was coated with 7.5% by mass of titanium dioxide based on the mica flakes. In this case, mica was dispersed in a titanium tetrachloride solution and the pH was adjusted to coat titanium hydroxide first, and this was baked at 1000 ° C. for 1 hour to obtain titanium dioxide having a rutile crystal structure. It was found that the titanium dioxide-coated mica thus obtained was coated with titanium dioxide in such a thickness that a bright blue color was produced on black carbon paper and the interference light became blue. The specific surface area of the titanium dioxide-coated mica flakes was 10 m ² / g. Next, the titanium dioxide-coated mica flakes were subjected to Ag plating by electroless plating. First, the activation treatment was performed by the known Sn-Pd two-liquid method. 100 g of titanium dioxide coated mica flakes,
Sensitizing treatment was carried out in a 0.001 mol / liter SnCl ₂ hydrochloric acid 1 liter solution, and then it was thoroughly washed with pure water until the specific electric conductivity of the wash water became 50 μS / cm or less. Next, 0.056 mol / liter of PdCl
_{2 The} activation treatment was performed in a 1 liter solution of hydrochloric acid. Similarly to the sensitizing treatment, the washing after the activating treatment was also performed with pure water until the concentration became 50 μS / cm or less. The Pd precipitation efficiency by the activating treatment was 100%. The activated titanium dioxide-coated mica flakes thus obtained were Ag-plated. The electroless plating was carried out under the condition that Ag was coated at 0.002 g / m ² . After plating, the specific electric conductivity is 50 μS /
It was thoroughly washed with pure water until it became cm or less. Finally, it was collected with filter paper and dried at 120 ° C. for 3 hours. The solid thus obtained was easily micronized by lightly applying vibration.

Example 2 Titanium dioxide-coated mica flakes obtained by the same treatment as in Example 1 were used. In this titanium dioxide coated mica flakes,
Ag plating was performed by electroless plating. First, Sn-P
The activation treatment was performed by the two-liquid method of d. 100 g of titanium dioxide-coated mica flakes are mixed with 0.008 mol / liter of S
Sensitizing treatment was carried out in a 1 liter solution of nCl ₂ hydrochloric acid, and then the resultant was thoroughly washed with pure water until the specific electric conductivity of the washing water became 50 μS / cm or less. Next, activating treatment was carried out in a 1 liter solution of 0.056 mol / liter PdCl ₂ hydrochloric acid. As with the sensitizing process, the washing after the activating process is 50μ with pure water.
It carried out until it became below S / cm. The activated titanium dioxide-coated mica flakes thus obtained were Ag-plated. The electroless plating was carried out under the condition that Ag was coated at 0.01 g / m ² . After plating, the specific electric conductivity is 50
It was thoroughly washed with pure water until it became below μS / cm. last,
It was collected with filter paper and dried at 120 ° C. for 3 hours.

Example 3 The surface of silica flakes having an average particle size of 25.4 μm was coated with 14.9% by mass of titanium dioxide. After dispersing the pigment in an aqueous solution of titanium coupling agent,
The pigment was filtered, collected, and calcined at 1100 ° C. to coat titanium dioxide having a rutile type crystal structure. The titanium dioxide-coated silica flakes thus obtained developed a vivid green color on black carbon paper. The specific surface area of the titanium dioxide-coated silica flakes was 10 m ² / g. next,
Au was vapor-deposited on the titanium dioxide-coated silica flakes by a sputtering method. During vapor deposition, the titanium dioxide-coated silica flakes were kept in a state of being constantly agitated by a rotary vibration tray of a pigment receiver. Au deposition is 0.001 g / m
^It was carried out under the condition of being coated with ² .

Example 4 A titanium dioxide-coated silica flake obtained by the same treatment as in Example 3 was used. Cr was vapor-deposited on the titanium dioxide-coated silica flakes by a sputtering method. During vapor deposition, the titanium dioxide-coated silica flakes were kept in a state of being constantly agitated by a rotary vibration tray of a pigment receiver. The vapor deposition of Cr was carried out under the condition of coating with 0.002 g / m ² .

Example 5 Titanium dioxide-coated silica flakes obtained by the same treatment as in Example 3 were used. Fe was vapor-deposited on the titanium dioxide-coated silica flakes by a sputtering method. At the time of vapor deposition, the titanium oxide-coated silica flakes were kept in a state of being constantly stirred by the rotary vibration tray of the pigment receiver. The vapor deposition of Fe was carried out under the condition of coating with 0.002 g / m ² .

Comparative Example 1 Titanium dioxide-coated mica flakes obtained by the same treatment as in Example 1 were used. In this titanium dioxide coated mica flakes,
Ag plating was performed by electroless plating. First, Sn-P
The activation treatment was performed by the two-liquid method of d. 100 g of titanium dioxide-coated mica flakes are mixed with 0.008 mol / liter of S
Sensitizing treatment was carried out in a 1 liter solution of nCl ₂ hydrochloric acid, and then the resultant was thoroughly washed with pure water until the specific electric conductivity of the washing water became 50 μS / cm or less. Then 0.0056
The activating treatment was carried out in a 1 liter solution of PdCl ₂ hydrochloric acid at mol / liter. As with the sensitizing treatment, the washing after the activating treatment is performed with pure water.
The process was repeated until it became μS / cm or less. The activated titanium dioxide-coated mica flakes thus obtained were Ag-plated. The conditions from Ag plating to drying and recovery were exactly the same as in Example 1.

Comparative Example 2 Titanium dioxide-coated mica flakes obtained by the same treatment as in Example 1 were used. In this titanium dioxide coated mica flakes,
Ag plating was performed by electroless plating. First, Sn-P
The activation treatment was performed by the two-liquid method of d. 100 g of titanium dioxide-coated mica flakes are mixed with 0.008 mol / liter of S
Sensitizing treatment was carried out in a 1 liter solution of nCl ₂ hydrochloric acid, and then the resultant was thoroughly washed with pure water until the specific electric conductivity of the washing water became 50 μS / cm or less. Then 0.0003
The activating treatment was carried out in a 1 liter solution of PdCl ₂ hydrochloric acid at mol / liter. As with the sensitizing treatment, the washing after the activating treatment is performed with pure water.
The process was repeated until it became μS / cm or less. The activated titanium dioxide-coated mica flakes thus obtained were Ag-plated. The conditions from Ag plating to drying and recovery are as in Example 1.
And exactly the same.

Comparative Example 3 Titanium dioxide-coated mica flakes obtained by the same treatment as in Example 1 were used. Further, the activation treatment conditions before electroless plating were exactly the same as in Example 1. Electroless plating is
It was carried out under the condition that Ag was coated at 0.10 g / m ² .
After plating, the plate was thoroughly washed with pure water until the specific electric conductivity was 50 μS / cm or less. The flow up to the subsequent drying and recovery was exactly the same as in Example 1.

Comparative Example 4 A titanium dioxide-coated mica flake obtained by the same treatment as in Example 1 was used. Further, the activation treatment conditions before electroless plating were exactly the same as in Example 1. Electroless plating is
It was carried out under the condition that Ag was coated at 0.00005 g / m ² . After plating, the plate was thoroughly washed with pure water until the specific electric conductivity was 50 μS / cm or less. The flow up to the subsequent drying and recovery was exactly the same as in Example 1.

Comparative Example 5 A was prepared under the same conditions as in Example 1 except that the mica flakes used in Example 1 were used without being coated with titanium dioxide.
g plating, drying, and recovery.

Comparative Example 6 The surface of an almost spherical barium sulfate powder having an average particle size of 5 μm was coated with 1.0% by mass of titanium dioxide based on the powder. The titanium dioxide coating method was exactly the same as in Example 1. The specific surface area of the barium sulfate powder after coating with titanium dioxide was 0.8 m ² / g. This titanium dioxide-coated barium sulfate powder was plated with Ag. The conditions from Ag plating to drying and recovery were exactly the same as in Example 1.

For each of the above examples and comparative examples,
The kind of adhered metal and the amount of adhered metal (g / m ²) And metal islands
Number (pieces / m²) Are collectively shown in Table 1. Also each
The color tones are also shown in Table 1. The number of metal islands in the table is E
The number of adhesion was measured by elemental mapping of PMA. color
The evaluation of the tone is excellent = ⊚> ∘> Δ> × = poor.

[0040]

[Table 1]

As is clear from the results in Table 1, Examples 1 to 5, which are within the scope of the present invention, showed a good color tone appearance. In Comparative Examples 1 to 6, which are outside the scope of the present invention, good color tone appearance was not obtained.

[0042]

Industrial Applicability The composite film pigment of the present invention has a novel design property that has never existed before, and when it is mixed with various paints, cosmetics, plastic moldings, etc., it has a high added value in its appearance. It can be given. Further, the production method of the present invention makes it possible to efficiently produce a composite pigment.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takumi Ozaki             1-15-1 Nihonbashi, Chuo-ku, Tokyo Japan Par             Within Colorizing Co., Ltd. (72) Inventor Koji Kondo             1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto             Car Co., Ltd. (72) Inventor Shin Umemura             1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto             Car Co., Ltd. (72) Inventor Hiroshi Hosono             1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto             Car Co., Ltd. F term (reference) 4G072 AA41 BB09 GG02 GG03 HH14                       JJ26 NN11 QQ09 TT05 UU30                 4G073 BA20 BD30 CM22 CN09 UB36                 4J037 AA22 CA03 CA09 CA24 EE04

Claims (3)

[Claims] 1. A scale-like inorganic pigment coated with titanium dioxide, and a metal coating layer in which the surface of the pigment is coated in an island shape, the metal coating layer being 1 × 10 ¹⁰ per specific surface area of the pigment.
10 is ¹⁵ / m ² islands consisting of a composite film pigment, characterized in that and a amount of adhering 0.00001～0.050G / m ² by metal weight basis. 2. The composite film pigment according to claim 1, wherein the scale-like inorganic pigment is at least one selected from the group consisting of mica flakes, silica flakes, alumina flakes, aluminum flakes and mica-like iron oxide. 3. A scale-like inorganic pigment coated with titanium dioxide is coated on the surface thereof in an island shape of 1 × 10 ¹⁰ to 10 ¹⁵ pieces / m ² per specific surface area of the pigment and converted into a metal weight of 0.0.
A method for producing a composite coating pigment, which comprises forming a metal coating layer of 0001 to 0.050 g / m ² .