JPH05140475A - Colored pearlescent pigment excellent in weatherability - Google Patents

Abstract

PURPOSE:To improve the weatherability by providing two specified layers of zirconium hydroxide in addition in a colored pearlescent pigment obtained by forming an interference layer made of TiO2 on a scaly base material and then forming light absorbing parts and bright parts thereon. CONSTITUTION:A transparent or translucent scaly base material (e.g. mica) 100 is covered with an interference layer 101 composed mainly of rutile titanium dioxide. On the whole or a part of the surface of the layer 101, a first zirconium hydroxide layer 102 is formed. Light absorbing parts 103 made of a lower titanium oxide are formed in dots also on the surface of the layer 101, and bright parts 104 made of metallic titanium are formed in dots on the layer 101 or 102. A second zirconium hydroxide layer 105 is then formed so as to cover the surfaces of the layers 101, 103 and 104, thus producing a colored pearlescent pigment excellent in weatherability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel pigment used as a colorant for paints and plastics.

[0002]

2. Description of the Related Art Pearl mica pigments are known as pigments used in paints for automobiles. This pearl mica pigment has titanium dioxide (hereinafter referred to as TiO _{2) on} the surface of mica particles.
) Is coated, and is used for coating using the interference color due to the high refractive index of TiO ₂ .

By the way, paints particularly suitable for coating external metal surfaces such as automobile paints have excellent weather resistance that does not change their appearance for several years even when exposed to various weather conditions. Sex is required. This weather resistance is not only the weather resistance of the resin component as the matrix,
The weather resistance of the contained pigment itself has a great influence. Therefore, in order to improve the weather resistance of the paint, it is important to improve the weather resistance of the pigment itself. For example, for a typical TiO ₂ pigment as a white pigment, various methods have been proposed to improve weather resistance.

For example, in US Pat. No. 2,242,320, chromium naphthenate is used as a surface coating material for TiO ₂ pigments. In US Pat. No. 2,346,322 0.5% chromium in oxide form on calcined TiO ₂ , in order to improve resistance to chalking and discoloration, 2.
A combination of 0% zirconium silicate and 1.0% alumina is colored. U.S. Patent Publication No. 2,226,142
U.S. Pat. No. 2,045,836, a chromium compound is added to a TiO ₂ pigment before calcination.
The publication discloses precipitating TiO _{2 in} the presence of chromic acid to form a TiO ₂ pigment containing chromate ions. Also, in US Pat. No. 2,231,268, calcined TiO ₂ containing a small amount of aluminum hydroxide (0.25% to 2% as Al ₂ O ₃ ) and chromium (0.01 to 2% as Cr ₂ O ₃ ) was prepared and then A method of preparing a dried pigment is disclosed.

However from the viewpoint of the stability of the paint that is exposed to various weather conditions, pearl mica pigment composed of mica particles coated with TiO ₂ is much more complex matter than mere TiO ₂ pigment. Therefore, Ti
The methods and techniques used to stabilize O ₂ pigments are either ineffective or inadequate as a means of imparting stability to pearl mica pigments. The reason is that a reaction occurs at the interface between mica and TiO ₂ , and the TiO ₂ layer itself also reacts.

Therefore, in West German Laid-Open Patent No. 1,467,468 and West German Laid-Open Patent No. 2,852,585, a chromium hydroxide thin film layer is further formed on mica particles coated with anatase type or rutile type TiO _2. , It is disclosed that the stability against light can be improved. Further, Japanese Patent Laid-Open Nos. 63-130673 and 1-292067 disclose
In the presence of hypophosphite, the surface of metal oxide-coated mica pigments such as rutile-type titanium oxide-coated mica, iron oxide-coated mica having a titanium oxide layer, and iron oxide-coated mica, which are conventional pearl mica, is used. A method of hydrolyzing zirconium oxychloride or a mixed salt of zirconium oxychloride and cobalt chloride with a sodium solution to form and deposit zirconium hydroxide or a mixture of zirconium hydroxide and cobalt hydroxide is disclosed. It is reported that the oxide-coated mica pigment has improved water resistance and weather resistance. The metal oxide means Japanese Patent Publication No. 49-3824, Japanese Patent Publication No. 49-94714 and Japanese Patent Publication No. 51-179.
Titanium oxide, iron oxide, tin oxide, chromium oxide, zirconium oxide and the like as described in JP-A No. 10 and JP-A-53-230 and the like are shown.

[0007]

[Problems to be Solved by the Invention] Pearl mica pigment is
There is a problem that the hiding power and metallic luster are poor. Therefore, the inventors of the present application have proposed a colored pearlescent pigment having an excellent design effect in Japanese Patent Application No. 3-50834. This pigment is a transparent or translucent scale-like substrate, an interference layer made of TiO ₂ coated on the entire surface of the substrate, and titanium low-order oxidation formed on the surface of the interference layer in a scattered manner. It is composed of a light absorbing part made of a material and a bright part having a metallic luster formed on the surface of the interference layer in a scattered manner. Further, it has three optical functions of reflection / scattering action of metal, interference action by the interference layer, and coloring action by partial reduction of the interference layer, and has an excellent colored pearl luster.

The most significant feature of the above-mentioned pigment is that it has a light absorption part formed by low-order titanium oxide and a bright part formed by metal titanium, which are formed in a scattered manner on the surface of the interference layer. Low-order titanium oxide has a reflection / absorption characteristic unlike a colorless and transparent interference layer. Therefore, it has an object color of blue to brown to black, and various colors can be obtained by combining with the interference color of the interference layer. This light absorbing portion can be formed by locally reducing the interference layer with metallic titanium.

However, the above-mentioned pigments cannot be put to practical use as they are even if they are mixed in various paints and plastics because of insufficient weather resistance. The object of the present invention is to improve the weather resistance of this colored pearlescent pigment.

[0010]

SUMMARY OF THE INVENTION The inventors of the present invention have made zirconium hydroxide on the outermost surface of the obtained pigment according to the prior arts such as the above-mentioned JP-A-63-130,673 and JP-A-1-292,067. Although treated, the weather resistance was not improved. on the other hand,
The surface of pearl mica pigment treated with zirconium hydroxide was coated with low-order titanium oxide and metallic titanium in a spot-like manner by the same method as those of the prior art, but the weather resistance was not improved.

However, the surface of the pearl mica pigment treated with zirconium hydroxide was coated with the low-order titanium oxide and the titanium metal in a scattered manner by the sputtering method, and then the zirconium hydroxide treatment was repeated.
The present invention has been found to exhibit extremely excellent weather resistance. The colored pearlescent pigment having excellent weather resistance of the present invention is a transparent or translucent scaly base material, an interference layer containing rutile titanium dioxide as a main component coated on the surface of the base material, and the interference layer. A first zirconium hydroxide layer coated on the surface, a light absorption part made of low-order titanium oxide formed in a dotted pattern on the surface of the interference layer, and a scattered point on the first zirconium hydroxide layer or the interference layer And a second zirconium hydroxide layer coated on the surface of the first zirconium hydroxide layer, the light absorbing part and the bright part.

The scale-like base material used in the present invention is a base material of a pigment, and a transparent or translucent scale-like material such as mica, glass foil, molybdenum disulfide, MIO and the like is used. Mica, which naturally occurs as scaly crystals, is particularly preferred. The mica particles usually have a length of 1 to 75 μm, preferably 5 to 40 μm and a thickness of 0.03 to 0.3 μm, preferably 0.10 to 1.0 μm. The surface area of these mica is BE
Measured at T method 1 ~10m ² / g, preferably from ² ~6m 2 / g. Hereinafter, mica is selected as the scale-like base material for description.
Other scale-like substrates can also be used according to this.

The surface of the mica is covered with an interference layer made of rutile type TiO ₂ . The preparation of pearl mica pigments consisting of rutile TiO ₂ coated mica is described in US Pat. No. 4,038,099. In order to ensure that rutile crystalline TiO ₂ is ensured in the final calcined product, one must start with the coating of the tin compound. This can be easily done by treating the aqueous mica slurry with a solution of stannic chloride or stannic sulfate. Generally, the concentration of mica in this slurry is 1 ~
It is in the range of 25% by weight, preferably 5 to 15%.

TiO ₂ can be coated by adding an acidic titanyl sulfate solution into an aqueous mica slurry which has been previously treated with a tin compound. Titanyl sulfate solution as an ordinary TiO ₂ has a 2-12% concentration, including its preferred range is from 3.0 to 6.0 percent addition of 10-30% sulfuric acid. The system is heated to 70-110 ° C to effectively effect the hydrolysis of titanyl sulfate, so that the mica particles are coated with hydrous amorphous titanium hydroxide. The titanium hydroxide coated mica particles are then separated from the reaction solution by filtration, washed with distilled water and then in an oven at 80-130 ° C.
And dried for 1 to 6 hours to obtain TiO ₂ -coated mica. This coating with TiO ₂ can also be done with TiCl ₄ , or other soluble titanium compounds or complex compounds. Generally, this TiO ₂ film has a thickness of 20 to
It has a thickness of 350 μm.

The calcination for converting the hydroxide into a crystalline oxide needs to be carried out at a high temperature for a long time in order to give the maximum weather resistance. Calcination at least 950 ° C
Must be done in 30 minutes. Actual temperature is 900-1000
C or higher. The higher the temperature, the less time is required to perform the minimum amount of calcination. For example, 90
Calcination at 0 ° C for 90 minutes is substantially equivalent to calcination at 925 ° C for 50 minutes, 950 ° C for 30 minutes, and 1000 ° C for 15 minutes.

A first zirconium hydroxide layer is formed on the surface of the interference layer. It may be formed on the entire surface of the interference layer or may be formed partially. This first zirconium hydroxide layer is formed as follows.
That is, a dilute solution of a soluble zirconium salt such as chloride or sulfate is hydrolyzed with a sodium hydroxide solution in the presence of hypophosphite at a temperature of 50 ° C. or higher to form a thin film of zirconium hydroxide on the surface of mica particles. To form. Dilute solution is 0.5-5%. It preferably contains 2-3% metallic zirconium. As the soluble zirconium hydroxide _{salt, ZrCl 4, Zr (NO 3} ) 4 · 5H 2 O, Zr (SO 4) 2 · 4H 2 O, ZrOCl 2 ·
8H ₂ O, ZrO (NO ₂ ) ₂ / 2H ₂ O, ZrSO ₄ / 4H ₂ O, etc.

Light-absorbing portions made of low-order titanium oxide are formed in a scattered manner on the surface of the interference layer, and bright portions made of metallic titanium are formed in a scattered manner in the first zirconium hydroxide layer or the interference layer. Has been formed. The light absorbing part and the bright part are
It is desirable that the total projected area on the interference layer is in the range of 0.05 to 95% with respect to the total surface area of the interference layer. If it is less than 0.05%, the hiding power is reduced, and if it is more than 95%, the interference color is weakened.

The light absorbing portion and the bright portion should be formed separately.
However, it is also possible to use the method disclosed in JP-A-1-108267
Or, according to Japanese Patent Application No. 3-50834, sputtering,
By physical methods such as evaporation or ion plating
Titanium metal ₂When attached to a layer, the metal
At the same time as titanium deposition, TiO₂The reduction of the layers occurs,
Low-order titanium oxide can be formed in scattered dots
The absorbing part and the bright part can be formed at the same time.

In the pigment of the present invention, a second zirconium hydroxide layer is further formed. This second zirconium hydroxide layer can be formed by the same method as the first zirconium hydroxide layer, but it is preferable that the second zirconium hydroxide layer be repeatedly processed so that it can be formed on the entire surface. This significantly improves the weather resistance. When the pigment of the present invention is used in a paint or the like, it is desirable to treat it with a coupling agent before use. This can significantly improve the dispersibility in the paint. This coupling treatment can be performed continuously after the formation of the second zirconium hydroxide layer. As the coupling agent, γ- (2-aminoethyl) aminopropyltrimethoxylane, aminosilane, γ-glycidoxypropropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane and the like can be used.

[0020]

The greatest optical feature of the pigment of the present invention is that it has a light absorbing portion formed by low-order titanium oxide and a bright portion formed by metallic titanium, which are formed in a scattered manner on the surface of the interference layer. Low-order titanium oxide has a reflection / absorption characteristic unlike a colorless and transparent interference layer. Therefore, it has an object color of blue to brown to black, and various colors can be obtained by combining with the interference color of the interference layer.

In the pigment of the present invention, as shown in FIG.
Transparent TiO with high refractive index ₂Layer 101 surface reflection
Light A and TiO₂Reflected at the interface between layer 101 and mica particle 100
The reflected light B interferes with each other, and TiO₂Layer thickness x T
iO₂It produces an interference color determined by the refractive index of the layer. Low order
In the light absorption part 103 made of titanium oxide, part of the reflected light is
Is absorbed, and the reflected light C emits the object color of the light absorbing portion 103.
To color. In addition, in the bright part 105 made of metal titanium,
The reflected light D emitted gives a metallic luster. Because
A unique and deep combination of these colors
A metallic color tone can be obtained. In addition, this
Such as metal titanium and low order titanium oxide and rutile type
Has novel optical properties consisting of three components of titanium oxide
The effect of zirconium hydroxide treatment on mica
Are the above-mentioned JP-A-63-130673 and JP-A-1-292067.
Is not mentioned at all.

Here, the hiding power of the pigment generally decreases as more light passes through the pigment. In the pigment of the present invention, part of the light F that has passed through the mica particle 100 is part of the light absorbing portion 10 on the opposite side.
Since it is absorbed by 3, the amount of transmitted light is less than that of the conventional pearl mica pigment, and the hiding power is improved. Further, when viewed in the shade, due to the action of the light by the light absorbing portion 103, irregular reflection is reduced and vivid color is produced, so that the contrast with the case when viewed from the front is large and a good flip-flop property is exhibited.

The reflected light E which is transmitted through the pigment, reflected on the base or the surface of another pigment, is incident on the pigment again and is transmitted, is recombined with the reflected light A and the reflected light B to weaken the interference light. However, in the pigment of the present invention, a part of the light that has passed through the mica particles is absorbed by the light absorbing portion 103 on the opposite side, and the light that passes through the pigment and is reflected by the base or other pigment surface is incident on the pigment again. Since part of the light is absorbed by the light absorbing portion 103, the amount of the reflected light E is reduced as compared with the conventional pearl mica pigment. This prevents the interference light from being weakened, and produces a strong interference color.

Therefore, the pigment of the present invention provides a metallic luster, strong interference color, and color development by the object color of the light absorbing portion, and has a large hiding power, and is therefore extremely useful as a coating material for automobiles. Incidentally, sufficient weather resistance could not be obtained only by the so-called primary zirconium hydroxide treatment before the formation of the light absorbing portion and the bright portion, because a part of the zirconium hydroxide film was formed by the plasma of titanium in the high energy state. It is presumed that this is due to destruction.

On the other hand, the reason why the so-called secondary zirconium hydroxide treatment after the sputtering treatment alone does not sufficiently improve the weather resistance is that the conventional techniques are not limited to rutile type Ti or the like.
A post-treatment method intended for a simple one-component coating made of O ₂ and for a complicated coating made of TiO ₂ and low-order titanium oxide and metallic titanium as in the present invention. That's not the point. For this, this 3
It is highly probable that it was difficult to apply the uniform zirconium hydroxide treatment to the entire surface of the coating film composed of the components in a single treatment, and the weather resistance was not improved because some untreated portions remained.

However, if the second zirconium hydroxide treatment is repeatedly performed after forming the first zirconium hydroxide layer and forming the light absorbing portion and the bright portion, the titanium zirconium oxide layer is destroyed by the high energy plasma of titanium during sputtering. The zirconium hydroxide film can also be coated with zirconium hydroxide again, and since a considerable part of the TiO ₂ layer has been previously coated with zirconium hydroxide, low-order oxidation formed in a spot-like shape is possible. It is presumed that zirconium hydroxide treatment can be efficiently performed on titanium and metal titanium.

[0027]

INDUSTRIAL APPLICABILITY The pigment of the present invention is remarkably excellent in weather resistance as compared with the pigments produced by the prior art. The pigments of the invention can then be used in the same applications as they currently exist, that is to say for example in plastics, inks, paints and cosmetics. Since the pigment of the present invention has excellent weather resistance,
It is preferable as a paint for automobiles which is exposed to various environments.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples. [Example 1] FIGS. 1 and 2 are schematic cross-sectional views of a pigment according to an example of the present invention. This pigment is an interference layer composed of mica particles 100 and TiO ₂ coated on the surface of the mica particles 100.
101, a first zirconium hydroxide layer 102 coated on the surface of the interference layer 101, a light absorption portion 103 made of low-order titanium oxide formed on the surface of the interference layer 101 in a scattered manner, and a light absorption portion 103 of the light absorption portion 103. A bright portion 104 made of titanium metal formed on the surface, a second zirconium hydroxide layer 105 further covering the entire surface, and a second zirconium hydroxide layer.
105 and the coupling layer 106 formed on the surface.

With this pigment, as shown in FIG. 2, for example, the reflected light A reflected on the surface of the transparent interference layer 101 having a high refractive index and the reflected light B reflected on the interface between the interference layer 101 and the mica particles 100. Interfere with each other to produce an interference color determined by the thickness of the interference layer x the refractive index of the interference layer. In addition, a part of the incident light is absorbed by the light absorption portion 103 made of low-order titanium oxide,
The reflected light C develops the object color of the light absorbing portion 103. Further, a metallic luster can be obtained by the reflected light D reflected by the bright portion 104 made of metallic titanium. Therefore, it is possible to obtain a deep and unique colored metallic tone color, which is a combination of the reflected light, the interference light, the absorbed light and the metallic luster. The first zirconium hydroxide layer 102
Although the second zirconium hydroxide layer 105 has no optical design effect, the weather resistance is remarkably improved by the presence of such a two-layer structure.

The method for producing this pigment will be described below. (Production of pearl mica) Mica particles (diameter 10 to 20 μm, thickness
50 g (0.5 μm) was added to 500 ml of ion-exchanged water, and the mixture was thoroughly stirred and uniformly dispersed. The resulting dispersion has a concentration of 40
158.2 ml of a wt% titanyl sulfate aqueous solution was added, and the mixture was heated with stirring and boiled for 6 hours. After cooling, it was filtered, washed with water, and baked at 900 ° C. to obtain 90 g of red pearl mica pigment having the surface coated with TiO ₂ . (Primary zirconium hydroxide treatment) 90 g of the obtained red pearl mica pigment was made into a slurry with 1500 ml of distilled water,
The pH was adjusted to 1.5 by dropwise addition of 3.5 wt% dilute hydrochloric acid. Then 45 ml of 10 wt% zirconium oxychloride solution
After adding, the mixture was heated to 75 ° C. and heated. Further, 360 ml of a 1 wt% sodium hypophosphite solution was added to the stirring suspension over 30 minutes, and the stirring was continued for 30 minutes. 5 wt% zirconium hydroxide solution at a rate of 4 ml / min
Was added dropwise to raise the pH to 7. Filtration by centrifugal separation of the slurry and washing with water were repeated until the electric conductivity of the washing water reached 20 μS / cm or less, and then dried by heating in a vacuum dryer at 120 ° C. for about 3 hours. (Explanation of powder sputtering apparatus) Next, referring to FIG. 3 and FIG.
Sputtering of metallic titanium was performed on the pearl mica pigment using the sputtering apparatus shown in FIG. This powder sputtering apparatus comprises a reduced pressure heat treatment chamber 1, a rotary barrel type sputtering chamber 2, a fluid jet mill 3 and a powder filter 4.

The reduced pressure heat treatment chamber 1 is a container that is electrically resistance-heated, and communicates with a main exhaust system 6 and an advanced exhaust system 7 via a filter 5. The main exhaust system 6 is a mechanical vacuum pump, and the advanced exhaust system 7 is a combination of a clion sorption pump, a turbo molecular pump or a mechanical booster pump, and a cooling trap. The reduced-pressure heat treatment chamber 1 is equipped with a screw feeder 9 and a motor 40 for rotating the screw feeder 9, and is configured to drop the reduced-pressure heat-treated fine powder 8 into a conduit 10 which is fed into the rotary barrel type sputtering chamber 2. There is.

The rotary barrel type sputtering chamber 2 (hereinafter simply referred to as a barrel) is a rotary cylinder having a structure like a ball mill as shown in FIG. 4, and one side wall of the rotary barrel type sputtering chamber 2 serves as a shaft which also serves as the conduit 10. It is rotatably supported by a magnetic seal 30 as a bearing. The other side wall is pivotally supported by a shaft 12 functioning as a rotary shaft via a magnetic seal 30. At the tip of the shaft 12, a pair of sputtering devices
50 are held facing each other. The attitude is not vertical and has a tilt determined by the position of the powder bed caused by the rotation of the barrel 2 as will be explained later. The sputtering apparatus 50 is operated by a high frequency current supplied from a power source (not shown) supplied via the shaft 12.

The conduit 10 is connected to the vacuum heat treatment chamber 1 via the valve 121.
Is in communication with. This conduit 10 reaches near the bottom of the barrel 2. In this case, the curvature is not directed vertically downwards, but rather at the position where the starting bed of fine powder produced by the rotation of the barrel 2 is produced. Inside this conduit 10, a pipe 19 is provided which communicates with the main exhaust system 6, the advanced exhaust system 7 and the inert gas supply source 31. Further, the conduit 10 is in rotary communication with the conduit 11 for supplying the fine powder to the fluid jet mill 3 and the valve 122.

The barrel 2 is supported by a support roll 13. The support roll 13 is connected to the rotary shaft of the motor 14 via a belt 15 and drives the barrel 2 to rotate by the rotation of the motor 14. The fluid jet mill 3 has a propeller 21 which is rotated at a high speed by a motor 20, and is configured so that the fine powder conveyed from the conduit 11 collides with the propeller 21. The discharge side of the fluid jet mill 3 communicates with a circulation pipe 23 having a valve 22, and the circulation pipe 23 further communicates with the reduced pressure heat treatment chamber 1. The powder filter 4 having a valve 24 is connected to the lower portion of the valve 22 of the circulation pipe 23. The powder filter 4 is a trap that communicates with the exhaust system 26 via the cylindrical filter 25. (Formation of light absorbing portion and bright portion) The pearl mica pigment described above.
93.6 g is put into the barrel 2 of the powder sputtering apparatus, and the reduced pressure heat treatment chamber 1 is reduced in pressure to 2 × 10 ⁻⁴ Torr. Then, argon gas is gradually supplied from the pipe 31 to supply the pigment to the fluid jet mill 3, collide with the propeller 21 to disperse the primary particles, and then the pigment is collected in the reduced pressure heat treatment chamber 1. Reduced pressure heat treatment chamber 1 to 2 × 10 ^-2 Torr,
The collected material was dried and degassed for 30 minutes by heating to 100 ° C. with a heater.

Next, the pigment was transferred into the barrel 2 that had been previously replaced with argon gas, and while the barrel 2 was rotating at 5 rpm, sputtering with a bipolar magnetron was started under a reduced pressure of 2 × 10 ^-2 Torr. .. The conditions are that the target is titanium, the electric power is 0.2 KW × 2, the frequency is 13.5 MHz, and the temperature of the pigment is 200 ° C. or less. Then, about 0.05% (2.0% by weight) of the entire surface was coated with titanium in 1 hour. This process was repeated 10 times to coat a total of 20 wt% titanium.

After the coating treatment, argon gas was supplied from the pipe 31 into the barrel 2 and the obtained pigment was mixed with the powder filter 4.
Caught inside. (Second treatment with zirconium hydroxide) 117 g of the obtained pearl mica pigment was made into a slurry with 2000 ml of distilled water, and the pH was adjusted to 1.5 by dropping 3.5% by weight of dilute hydrochloric acid. Then, 60 ml of a 10 wt% zirconium oxychloride solution was added, and then the temperature was raised to 75 ° C. Further, 470 ml of a 1% by weight sodium hypophosphite solution was added to the stirring suspension.
After adding over a period of 1 minute, stirring was continued for 30 minutes. A 5 wt% sodium hydroxide solution was added dropwise at a rate of 4 ml / min to adjust the pH.
Of the silane coupling agent (SH6040 manufactured by Toray Silicone Co., Ltd.) of 200 wt.
1 was added and well stirred for 30 minutes. Filtration by centrifugal separation of the slurry and washing with water were repeated until the electric conductivity of the washing water was 20 μS / cm or less, and then the mixture was heated and dried at 120 ° C. for about 3 hours in a vacuum dryer. This coats the pearl mica pigment with a thin layer of zirconium hydroxide in an amount of 3% by weight. The obtained pigment has an off-white metallic tone and a red intermediate color.

The resulting pigment was mixed in an acrylic melamine clear paint so that the pwc was 10%, and was coated on a steel plate undercoated with a 5 μm epoxy resin-based paint using a 25 mil bar coater. Then, it was baked and dried at 140 ° C. for 30 minutes to form a coated plate. Then, a 1000-hour QUV test was performed. The results are shown in Table 1. The amounts of the components of the film in the table are calculated by calculating the amounts of each of the pigments that have been subjected to the final treatment. [Example 2] Example 1 except that the coating amount of titanium by sputtering was 2.0% by weight and the treatment amount of primary and secondary zirconium hydroxide was 0.2% by weight, respectively.
A pigment of this example was obtained in the same manner as in. Then, Table 1 shows the results of coating and evaluation in the same manner as in Example 1. This color is intermediate between red and silver, which is close to aluminum metallic. [Comparative Example 1] A pigment prepared in the same manner as in Example 1 except that the first and second zirconium hydroxide treatments were not carried out was used as the pigment of Comparative Example 1. Then, Table 1 shows the results of evaluation in the same manner as in Example 1 to make a coating. [Comparative Example 2] A pigment formed in the same manner as in Example 1 except that the first zirconium hydroxide treatment was not performed was used as a pigment in Comparative Example 2. Then, Table 1 shows the results of evaluation in the same manner as in Example 1 to make a coating. [Comparative Example 3] A pigment formed in the same manner as in Example 1 except that the second zirconium hydroxide treatment was not performed was used as a pigment of Comparative Example 3. Then, Table 1 shows the results of evaluation by coating in the same manner as in Example 1. [Comparative Example 4] A pigment formed in the same manner as in Example 1 except that the primary zirconium hydroxide treatment was not performed was used as a pigment of Comparative Example 4. However, 120 ml of a 10 wt% zirconium oxychloride solution and 940 ml of a 1 wt% sodium hypophosphite solution were used so that the amount of the second zirconium hydroxide layer formed was doubled to 3% by weight. .. Then, Table 1 shows the results of evaluation in the same manner as in Example 1 to make a coating.

[0038]

[Table 1]

[Evaluation] As shown in Table 1, the pigments of Examples 1 and 2 of the present invention, which were subjected to the primary and secondary zirconium hydroxide treatments, were discolored after 1000 hours of QUV test. It was found that there was not much deterioration in gloss and gloss, and that it had excellent weather resistance. On the other hand, Comparative Example 1 in which no zirconium hydroxide treatment was performed at all, Comparative Example 2 in which only the secondary zirconium hydroxide treatment was performed, and Comparative Example 3 in which only the primary zirconium hydroxide treatment was performed were QUV tests.
Great discoloration and loss of gloss after 1000 hours. In particular, the deterioration was extremely remarkable in Comparative Example 1 in which the zirconium hydroxide treatment was not performed at all. It is understood that the primary zirconium hydroxide treatment is slightly larger than the secondary zirconium hydroxide treatment as an effect of improving the weather resistance.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a pigment of the present invention.

FIG. 2 is an explanatory view showing an optical action of the pigment of the present invention.

FIG. 3 is a front view of the powder sputtering apparatus.

FIG. 4 is a side view of the powder sputtering apparatus.

[Explanation of symbols]

100: Mica particles 101: Interference layer (Ti
O ₂ layer) 102: first zirconium hydroxide layer 103: light absorbing part (low order titanium oxide) 104: bright part (titanium metal) 105: second zirconium hydroxide layer 106: coupling layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Shirokura 7-1 Takatani Shinmachi, Ichikawa City, Chiba Nisshin Steel Co., Ltd. New Materials Research Center (72) Inventor Hiroshi Ito 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto Car Co., Ltd. (72) Inventor Noriyuki Suzuki 1 Toyota Town, Toyota City, Aichi Toyota Motor Co., Ltd.

Claims (1)

[Claims] 1. A transparent or translucent scaly substrate, an interference layer containing rutile-type titanium dioxide as a main component coated on the surface of the substrate, and a first hydroxide coated on the surface of the interference layer. A zirconium layer, a light absorbing part formed on the surface of the interference layer in a scattered manner and made of low-order titanium oxide, and a brilliance made of a metal titanium formed in a scattered manner on the first zirconium hydroxide layer or the interference layer. And a second zirconium hydroxide layer coated on the surfaces of the first zirconium hydroxide layer, the light absorbing part and the bright part, and a colored pearlescent pigment having excellent weather resistance.