JP2002105354A - Ultramarine composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultramarine composition having both high acid resistance and heat resistance. SOLUTION: This ultramarine composition is such that the surface of ultramarine particles is provided with a metal oxide coating layer capable of improving the acid resistance or heat resistance of the composition (particularly, a composite oxide such as silica-alumina, silica-zirconia, silica-titania or the like); wherein the amount of the coating layer to be provided is preferably 5-50 wt.%, especially 10-40 wt.%, based on the ultramarine particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultramarine composition comprising a surface of ultramarine blue particles coated with a metal oxide, and a method for producing the ultramarine blue composition.

[0002]

2. Description of the Related Art Ultramarine (ultramarine) is known as an inorganic pigment, and is used for paints, printing inks, detergents, etc., cosmetics, color filters of liquid crystal display devices, and the like. However, for example, it is known that when used as a colorant for plastics, the plastics may be acidified with time, and the ultramarine may fade and whiten. It is also known that, when used in cosmetics, ultramarines fade and become white when they become acidic due to sweating.
Further, it is also known that when exposed to a high temperature using a paint, a printing ink, a plastic, and the like, such as a color display device used in an atmosphere under a high temperature or under a high temperature under reduced pressure, the color is also faded and whitened.

[0003] For this reason, Japanese Patent Application Laid-Open (JP-A) No. 61-111366 discloses that ultrafine blue particles are coated with silica to suppress acid discoloration and to improve acid resistance or corrosion resistance. Further, Japanese Patent No. 2915627 (Japanese Patent Application Laid-Open No. 5-1235) discloses that active silica sol is deposited on the surface of ultramarine blue particles. However, even with such ultramarine particles coated with silica, it has been difficult to suppress the fading of the ultramarine particles when the particles are brought into contact with an acidic medium at a high temperature, or at a high temperature of 100 ° C. or more, or under a high-temperature reduced pressure.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and is an ultramarine having excellent acid resistance and heat resistance (maintaining a unique hue even at high temperatures and not fading with time). An object of the present invention is to provide a composition and a method for producing an ultramarine blue composition.

[0005]

Means for Solving the Problems The ultramarine blue composition of the present invention comprises:
IIIA group, IIIB group, IVA group, IVB group,
It is characterized by having at least one metal oxide coating layer of one or more elements selected from the group VA and the group VIB. The coating layer in contact with the ultramarine blue particle surface is preferably a composite oxide coating layer. The composite oxide is preferably any of silica-alumina, silica-zirconia, and silica-titania. Preferably, the coating layer is composed of two layers, and the outermost layer is a silica layer.

[0006] The method of producing the ultramarine blue composition according to the present invention is characterized by comprising the following steps (a) to (f). (A) Step of preparing a dispersion of ultramarine blue particles (b) Step of adjusting the pH of the dispersion to a range of 8 to 12 (c) Formation of a first layer by adding an aqueous solution of an inorganic compound salt to the dispersion (D) if necessary, a step of adding an aqueous solution of a component different from that of the first layer in the same manner as in step (c) to form the second and lower layers (e) washing as necessary Step (f) Step of hydrothermal treatment as necessary (g) Step of drying and firing

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Ultramarine (ultramarine) is one of synthetic blue pigments and has a general formula [Na _x Al _x Si _(12-x)
O ₂₄ · Na _y S _z ]. As is well known, ultramarine is stable to alkali but very weak to acid. In the ultramarine blue composition according to the present invention, the ultramarine blue particles preferably have an average particle diameter of 0.01 to 5 μm, particularly preferably 0.05 to 1 μm. When the average particle size is less than 0.01 μm, the blue color is insufficient, and the average particle size is 5 μm.
If it exceeds, it may become white due to scattering, and the original color of the ultramarine blue may be lost.

On the surface of the ultramarine blue particles of the present invention, Group IIIA, II
A metal oxide coating layer of one or more elements selected from the group IB, IVA, IVB, VA, and VIB is formed. As the above element, for example, as Group IIIA,
B, Al, III As group B, Ce, as group IVA, S
i, Sn, IVB group, Ti, Zr, Hf, VA group, P, Sb, VIB group, Mo, W and the like. Specific metal oxides include alumina, zirconia, titania, silica. Alumina, silica / zirconia, silica / titania and the like can be mentioned. The metal oxide coating layer improves the acid resistance and heat resistance of the ultramarine composition. This is because the metal oxide coating layer suppresses the tendency that NaS bonds in ultramarine blue are broken in an acidic atmosphere to release Na or S, and also suppresses the tendency of S to oxidize and discolor even at high temperatures. It is thought to be. Among the above-mentioned metal oxide coating layers, composite oxides such as silica-alumina, silica-zirconia, and silica-titania have a remarkable effect of improving heat resistance as well as acid resistance.

[0009] The amount of the metal oxide coating layer formed is preferably in the range of 5 to 50% by weight, particularly 10 to 40% by weight of the ultramarine blue particles. If the amount is less than 5% by weight, sufficient acid resistance and heat resistance cannot be obtained due to a small coating amount.
If it exceeds 50% by weight, the original coloration of ultramarine blue may be hindered, which is not preferred.

In the present invention, the metal oxide coating layer may be formed of two or more different types of metal oxide coating layers. By forming a plurality of metal oxide coating layers,
For example, when the first layer can improve the heat resistance but the improvement of the acid resistance is insufficient, the heat resistance and the heat resistance can be improved by forming a metal oxide coating layer capable of improving the acid resistance on the second layer. Acid resistance can be improved. When the first layer can improve the acid resistance but the heat resistance is not sufficiently improved, the heat resistance can be improved by forming a metal oxide coating layer capable of improving the heat resistance on the second layer. And acid resistance can be improved. It is preferable that the formation amount of the metal oxide coating layer as the second layer is such that the total amount with the first layer is in the range of 5 to 50% by weight of the ultramarine blue particles.

The metal oxide coating layer forming the second layer may be silica, alumina, titania, zirconia, or the like, or may be a composite oxide similar to that used for the first layer and different from the first layer. Things can be used. Normal,
A coating layer of a single component such as silica, titania, and zirconia tends to improve acid resistance, and a composite oxide coating layer tends to particularly improve heat resistance in addition to acid resistance. Silica single coating layer can coat ultramarine particles more densely than other metal oxide coating layers, and ultramarine particles can improve acid resistance without direct contact with acid, so two or more layers Is preferably used as the outermost layer of the coating layer. However, it is not appropriate to use the silica single coating layer as the first layer for the reason described in the section of the prior art.

Next, the method for producing the ultramarine blue composition of the present invention is described below.
The steps (a) to (f) will be described in order. Step (a) In step (a), an aqueous dispersion of ultramarine blue particles is prepared. At this time, the concentration of the ultramarine particles in the dispersion is preferably in the range of 1 to 20% by weight, particularly preferably 2 to 10% by weight. If the amount is less than 1% by weight, the metal oxide precursor cannot be efficiently deposited on the ultramarine blue particles due to the low concentration.
If it exceeds 20% by weight, the ultramarine blue particles tend to aggregate,
Monodisperse modified ultramarine particles may not be obtained.

Step (b) In step (b), the pH of the dispersion is adjusted in advance to a range of 8 to 12. By adjusting such pH,
A precursor (a hydrolyzate of an inorganic compound salt to be described later) of the metal oxide coating layer to be subsequently added can be uniformly and densely deposited on the ultramarine blue particle surface.

Step (c) In step (c), an aqueous solution of an inorganic compound salt or the like is added to the dispersion to form a first layer. As the inorganic compound salt or the like, specifically, Al, B, Ti, Zr, Si, Sn,
Examples include oxo acids of elements selected from Ce, P, Sb, Mo, W, and the like, and alkali metal or alkaline earth metals, ammonium salts, and quaternary ammonium salts of the oxo acids. More specifically, preferred are sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, sodium silicate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, sodium phosphate and the like.

When a composite oxide coating layer is formed as the metal oxide coating layer, the composite oxide is preferably a silica-based composite oxide containing at least silica. At this time, a silicate or an organic silicon compound of an alkali metal, ammonium or an organic base can be used as a silica source. Examples of the alkali metal silicate include sodium silicate (water glass) and potassium silicate. Further, a silicate solution obtained by removing alkali from sodium silicate can also be used. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline aqueous solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound, or the like to a silicate solution. Examples of the organosilicon compound include a compound represented by the general formula R _n Si (OR ′) _4-n [where R and R ′ are a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, and an acryl group; Or 3] can be used. In particular,
Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, ethyltriethoxysilane and the like can be mentioned.

When forming a silica-based composite oxide coating layer
The amount of each addition of _TwoExpressed as silica
MO of the inorganic salt outside_xWhen expressed as_x/
(SiO_Two+ MO_x) Weight ratio in the range of 0.05 to 0.6
And (SiO_Two+ MO_x) Is 5-50 weights of ultramarine particles
The amount is added so as to be in the range of%. MO_x/ (SiO_Two
+ MO_x) When the weight ratio is less than 0.05, the heat resistance is improved.
Is not enough, MO_x/ (SiO_Two+ MO_x) Weight ratio
Exceeds 0.6, the acid resistance may be insufficient.
In addition, inorganic compounds other than silicate and silica at this time
The rate of salt addition is determined by converting the silicate to SiO_TwoExpressed in other than silica
Inorganic compound salt of MO_xWhen represented by (SiO_Two+
MO_x) As 0.5 to 20% by weight / hour of ultramarine particles,
In particular, it is preferably in the range of 1 to 10% by weight / hour.
No. If the addition rate of the inorganic compound salt is within the above range, uniform
To form a uniformly laminated coating layer
Therefore, the ultramarine particles obtained are excellent in heat resistance and acid resistance.
You.

Step (d) Step (d) is optional, and an aqueous solution of a component different from that used for the first layer is added in the same manner as in step (c).
The second and lower layers are formed. As the silica source and the inorganic compound other than silica at this time, the same compounds as described above can be used. In particular, when a layer made of silica is formed using a silicate or a silicate solution as the second layer, the ultramarine blue particles on which the first layer has been formed can be densely covered, so that the acid resistance and heat resistance can be further improved. At this time, the addition amount and the addition rate are different from those of the first layer in the components, and MO _x / (Si
O ₂ + MO _x ) The same as the first layer except that the weight ratio is in the range of 0 to 0.6.

Step (e) Step (e) is also optional, and is a washing step following step (c) or step (d). A cation exchange resin, an anion exchange resin or both ion exchange resins are added to the dispersion prepared in the step (c) or the step (d), and the pH of the dispersion is in the range of 1 to 10, preferably 2 to 9. Adjust so that When the pH of the dispersion liquid is less than 1, in addition to the fact that NaS bonds in ultramarine blue particles are broken and the original color tone of ultramarine blue may be impaired, components other than silica forming the composite metal oxide are eluted. In some cases, the improvement in heat resistance may be insufficient. By removing cations and anions by ion exchange resin, the acid resistance, heat stability and dispersion stability of ultramarine blue particles are not impaired, and the effect of improving acid resistance and heat resistance by forming a metal oxide coating layer is sufficient. Can be expressed. The conductivity of the dispersion after removing cations and anions with an ion exchange resin is 2 m
S / cm or less, preferably 1 mS / cm or less, particularly preferably 0.5 mS / cm or less.

Step (f) Step (f) is also optional, and is a hydrothermal treatment step following the above step. In the step (f), the steps (c), (d),
After any one of the steps (e), the dispersion liquid is added in an amount of 50 to 2 depending on the type of the metal oxide layer, the coating amount, and the like.
It is preferable to perform a hydrothermal treatment in the range of 50 ° C. By performing the hydrothermal treatment, the coating layer can be more firmly bonded to the ultramarine blue particles, and can be further densified. Further, the composite can be promoted, so that the acid resistance and the heat resistance can be improved.

Step (g) In step (g), drying and, if necessary, firing are performed. After any of the steps of baking (c) to step (f), the ultramarine particles having the coating layer formed thereon are separated from the dispersion, dried, and dried.
Bake if necessary. The separation method is not particularly limited as long as the ultramarine blue particles having the coating layer formed thereon can be separated, and a conventionally known method can be employed. The drying method is not particularly limited, and a conventionally known method can be employed. The drying temperature is preferably about 60 to 200 ° C. The firing temperature in the firing step is preferably in the range of 300 to 800 ° C.
When the temperature is lower than 300 ° C., the densification of the coating layer does not easily proceed,
Therefore, the acid resistance may not be sufficiently improved. If the firing temperature exceeds 800 ° C., NaS in the ultramarine blue particles may be oxidized or decomposed and decolorized, which is not preferable.

[0021]

The modified ultramarine particles according to the present invention have excellent heat resistance in addition to acid resistance since a specific metal oxide layer or composite oxide coating layer is formed on the ultramarine particles. Therefore, even when used in paints, printing inks, detergents, etc., the hue unique to ultramarine blue does not change (fading / bleaching). Also, when used in cosmetics, ultramarines do not fade and whiten even when they become acidic due to sweating. When used in a color display device or the like, the ultramarine blue does not easily fade and become white even when exposed to a high temperature or under reduced pressure or vacuum.

[0022]

EXAMPLES Example 1 Ultramarine particles (COSMETIC ULTRAMARI manufactured by Daiichi Kasei Kogyo Co., Ltd.)
NE BLUE CB-80, particle diameter 1.6 μm, hereinafter referred to as raw material group blue particles. ) Was pulverized with a sand mill, 50 g of ultramarine blue particles (average particle size: 1.1 μm) were dispersed in 950 g of pure water, and the ultramarine blue particle dispersion was placed in a reactor equipped with a reflux device.
The pH of the dispersion was adjusted to 11 with a 1% by weight aqueous NaOH solution.
Then, the mixture was heated at 95 ° C. for 30 minutes with stirring. Subsequently, sodium silicate (SiO ₂ / Na ₂ O molar ratio: 3.1) 1250 having a concentration as SiO ₂ of 1.5% by weight was used.
g at a rate of 5 g / min, and at the same time, a sodium aluminate aqueous solution (Na) having a concentration of 0.5% by weight as Al ₂ O _3.
1250 g of a ₂ O / Al ₂ O ₃ molar ratio (1.2) was added at a rate of 5 g / min to obtain a dispersion of the ultramarine blue composition having a silica-alumina coating layer (Ad). A cation exchange resin was added to the dispersion (Ad) to perform ion exchange until the pH reached 3, and then the ultramarine composition was separated and removed, followed by drying.
An ultramarine blue composition (A) having a silica-alumina coating layer was obtained. The ultramarine composition (A) was evaluated for acid resistance and heat resistance, and the results are shown in Table 1.

Evaluation of Acid Resistance The ultramarine blue composition (A) was added to a 1% by weight aqueous hydrochloric acid solution so that the solid content concentration became 0.2% by weight, and the mixture was stirred at 25 ° C. for 1 hour. Separate and dry at 110 ° C. The ultramarine particles have a wavelength of 200 on a spectrophotometer.
The spectrum was measured in the range of ８００800 nm, and this was compared with the spectrum measured for the original ultramarine blue particles before forming the coating layer, and evaluated according to the following criteria. No change in spectrum: ◎ Small change in spectrum: ○ During change in spectrum: △ Large change in spectrum: ×

Evaluation of heat resistance The ultramarine composition (A) is baked at 450 ° C. for 1 hour and dispersed in ethylene glycol so that the solid content concentration becomes 0.2% by weight. The spectrum of this ultramarine blue particle was measured with a spectrophotometer in the wavelength range of 200 to 800 nm, and this was compared with the spectrum measured for the original ultramarine blue particle before forming the coating layer, and evaluated according to the following criteria. No change in spectrum: ◎ Small change in spectrum: ○ During change in spectrum: △ Large change in spectrum: ×

Example 2 50 g of ultramarine blue particles (average particle diameter: 1.1 μm) obtained by pulverizing raw ultramarine blue particles in a sand mill were dispersed in 950 g of pure water, and the ultramarine blue particle dispersion was charged into a reactor equipped with a reflux condenser. ,
The pH of the dispersion was adjusted to 11 with a 1% by weight aqueous NaOH solution.
Then, the mixture was heated at 95 ° C. for 30 minutes with stirring. Then, 1590 sodium silicate (SiO ₂ / Na ₂ O molar ratio 3.1) having a concentration of 1.5% by weight as SiO _2.
g at a rate of 5 g / min, and at the same time, a sodium aluminate aqueous solution (Na) having a concentration of 0.5% by weight as Al ₂ O _3.
1590 g of a ₂ O / Al ₂ O ₃ molar ratio of 1.2) was added at a rate of 5 g / min to obtain a dispersion of an ultramarine blue composition having a silica-alumina coating layer. Next, pure water was added until the pH of the dispersion reached 10 while maintaining the liquid level of the dispersion at an ultra-concentrator. This dispersion having a pH of 10 was heated to 80 ° C., and while stirring, the concentration as SiO ₂ was 3.1.
Weight percent sodium silicate (SiO ₂ / Na ₂ O molar ratio 3.
440 g of a silicate solution having a concentration of 3.0% by weight as SiO ₂ obtained by cation exchange of 1) was added at a rate of 1 g / min, and ultramarine having a silica coating layer on a silica-alumina coating layer was added. A dispersion (Bd) of the composition was obtained. Dispersion (Bd
), A cation exchange resin was added thereto, and the mixture was ion-exchanged until the pH reached 3. Then, the ultramarine composition was separated and removed, and then dried. The ultramarine composition having a silica coating layer on a silica-alumina coating layer ( B) was obtained. The same evaluation as in Example 1 was performed for the ultramarine blue composition (B).

Example 3 50 g of ultramarine blue particles (average particle diameter 1.1 μm) obtained by pulverizing raw ultramarine blue particles in a sand mill were dispersed in 950 g of pure water, and the ultramarine blue particle dispersion was charged into a reactor equipped with a reflux condenser. ,
The pH of the dispersion was adjusted to 11 with a 1% by weight aqueous NaOH solution.
Then, the mixture was heated at 95 ° C. for 30 minutes with stirring. Next, 335 g of sodium silicate (SiO ₂ / Na ₂ O molar ratio: 3.1) having a concentration of 1.5% by weight as SiO _2.
Was added at a rate of 5 g / min, and at the same time, sodium aluminate (Na ₂ O / A) having a concentration of 0.5% by weight as Al ₂ O _3.
335 g of l ₂ O ₃ molar ratio 1.2) was added at a rate of 5 g / min to obtain a dispersion liquid (Cd-1) of the ultramarine composition having a silica-alumina coating layer. Pure water was added to the dispersion (Cd-1) until the pH of the dispersion reached 10 while maintaining the level of the dispersion at an ultra-concentrator. This pH 10
The dispersion was heated to 80 ° C., with stirring, the concentration of the SiO ₂ 3. 1 wt% of sodium silicate (SiO ₂ / N
SiO ₂ obtained by cation exchange of a ₂ O molar ratio 3.1)
334 g of a 3.0% by weight silicic acid solution as
Per minute to obtain a dispersion (Cd-2) of an ultramarine blue composition having a silica coating layer on a silica-alumina coating layer. Add cation exchange resin to dispersion (Cd-2) and adjust pH
Was ion-exchanged to 3 and then the ultramarine composition was separated and removed, followed by drying to obtain an ultramarine blue composition (C) having a silica coating layer on a silica-alumina coating layer. The same evaluation as in Example 1 was performed for the ultramarine blue composition (C).

Example 4 50 g of ultramarine blue particles (average particle size: 1.1 μm) obtained by pulverizing raw ultramarine blue particles in a sand mill were dispersed in 950 g of pure water, and the ultramarine blue dispersion was placed in a reactor equipped with a reflux condenser. After adjusting the pH of the dispersion to 11 with a 1% by weight aqueous solution of NaOH, the dispersion was heated at 80 ° C. for 30 minutes with stirring.
Subsequently, 1250 g of sodium silicate (SiO ₂ / Na ₂ O molar ratio 3.1) having a concentration of 1.5% by weight as SiO ₂ was added at a rate of 5 g / min, and at the same time, the concentration as ZrO ₂ was 0.5. 1% by weight aqueous solution of zirconyl ammonium carbonate 1
250 g was added at a rate of 3 g / min to obtain a dispersion (Dd) of the ultramarine composition having a silica-zirconia coating layer. A cation exchange resin was added to the dispersion (Dd) to perform ion exchange until the pH reached 3, and then the ultramarine composition was separated and removed, and then dried to obtain an ultramarine composition (D) having a silica-zirconia coating layer. I got The same evaluation as in Example 1 was performed for the ultramarine blue composition (D).

Example 5 50 g of ultramarine blue particles (average particle size: 1.1 μm) obtained by pulverizing raw ultramarine blue particles in a sand mill were dispersed in 950 g of pure water, and the ultramarine blue dispersion was charged into a reactor equipped with a reflux condenser. After adjusting the pH of the dispersion to 11 with a 1% by weight aqueous solution of NaOH, the dispersion was heated at 80 ° C. for 30 minutes with stirring.
Next, 770 g of sodium silicate (SiO ₂ / Na ₂ O molar ratio 3.1) having a concentration of 1.5% by weight as SiO ₂ was added to 5
g / min, and at the same time, an aqueous solution of zirconyl ammonium carbonate 77 having a concentration of 0.5% by weight as ZrO _2.
0 g was added at a rate of 3 g / min to obtain a dispersion liquid of the ultramarine composition having a silica-zirconia coating layer. Next, pure water was added until the pH of the dispersion reached 10 while maintaining the liquid level of the dispersion at an ultra-concentrator. This dispersion having a pH of 10 was heated to 80 ° C., and while stirring, sodium silicate (SiO ₂ / Na) having a concentration of 3.1% by weight as SiO ₂ was used.
384 g of a silicate solution having a concentration of 3.0% by weight as SiO ₂ obtained by cation exchange of a ₂ O molar ratio of 3.1) was 1 g / g.
Min. To obtain a dispersion liquid (Ed) of the ultramarine composition having a silica coating layer on the silica-zirconia coating layer. A cation exchange resin is added to the dispersion (Ed) to conduct ion exchange until the pH becomes 3. Then, the ultramarine composition is separated and removed, and then dried to have a silica coating layer on the silica-zirconia coating layer. An ultramarine composition (E) was obtained. The same evaluation as in Example 1 was performed for the ultramarine blue composition (E).

Example 6 An ultramarine blue composition having a silica-alumina coating layer was prepared in the same manner as in Example 1 except that ultramarine blue particles (average particle diameter 0.4 μm) obtained by pulverizing raw ultramarine blue particles with a sand mill were used. After obtaining a dispersion (Fd) of the product, an ultramarine blue composition (F) having a silica-alumina coating layer was obtained. The same evaluation as in Example 1 was performed for the ultramarine blue composition (F).

Example 7 The procedure of Example 2 was repeated except that ultramarine blue particles (average particle diameter 0.4 μm) obtained by pulverizing the raw ultramarine blue particles with a sand mill were used to form a silica on the silica-alumina coating layer. An ultramarine blue composition (G) having a coating layer was obtained. The same evaluation as in Example 1 was performed for the ultramarine blue composition (G).

Example 8 50 g of ultramarine blue particles (average particle diameter: 1.1 μm) obtained by pulverizing raw ultramarine blue particles in a sand mill are dispersed in 950 g of pure water, and the ultramarine blue particle dispersion is put into a reactor equipped with a reflux condenser. ,
The pH of the dispersion was adjusted to 11 with a 1% by weight aqueous NaOH solution.
Then, the mixture was heated at 95 ° C. for 30 minutes with stirring. Next, 1400 g of an aqueous solution of zirconyl ammonium carbonate having a concentration of 0.5% by weight as ZrO ₂ was added at a rate of 3 g / min to prepare a dispersion of the ultramarine composition having a zirconia coating layer. Pure water was added until the pH of the dispersion reached 10 while keeping the level of the dispersion constant. This dispersion having a pH of 10 is heated to 80 ° C., and while stirring, sodium silicate having a concentration as SiO ₂ of 3.1% by weight (a molar ratio of SiO ₂ / Na ₂ O 3.1) is subjected to cation exchange to obtain the dispersion. 500 g of a silicic acid solution having a concentration of 3.0% by weight as SiO ₂ was added at a rate of 1 g / min, and a dispersion of ultramarine blue composition having a silica coating layer on a zirconia coating layer (I
d) Got it. A cation exchange resin was added to the dispersion (Id) and ion-exchanged until the pH reached 3. Then, the ultramarine composition was separated and removed, and then dried to form an ultramarine composition having a silica coating layer on a zirconia coating layer. The product (I) was obtained. The same evaluation as in Example 1 was performed for the ultramarine blue composition (I).

Example 9 50 g of ultramarine blue particles (average particle diameter: 1.1 μm) obtained by pulverizing raw ultramarine blue particles in a sand mill were dispersed in 950 g of pure water, and the ultramarine blue particle dispersion was charged into a reactor equipped with a reflux condenser. ,
The pH of the dispersion was adjusted to 11 with a 1% by weight aqueous NaOH solution.
Then, the mixture was heated at 95 ° C. for 30 minutes with stirring. Next, sodium aluminate having a concentration of 0.5% by weight as Al ₂ O ₃ (Na ₂ O / Al ₂ O ₃ molar ratio: 1.
2) A dispersion of the ultramarine composition having an alumina coating layer was prepared by adding 2000 g of an aqueous solution at a rate of 5 g / min, and the pH of the dispersion was adjusted while keeping the level of the dispersion constant with an ultraconcentrator. Pure water was added to reach 10. This dispersion having a pH of 10 is heated to 80 ° C., and while stirring, sodium silicate (SiO ₂ / Na ₂₎ having a concentration of 3.1% by weight as SiO ₂ is used.
500 g of a silicate solution having a concentration of 3.0% by weight as SiO ₂ obtained by cation exchange of an O mole ratio of 3.1) was added at a rate of 1 g / min, and a silica coating layer was formed on the alumina coating layer. A dispersion liquid (Jd) of the ultramarine blue composition having the following formula was obtained. Dispersion (J
d) A cation exchange resin was added to the mixture, and the mixture was ion-exchanged until the pH became 3. Then, the ultramarine composition was separated and removed and dried, and the ultramarine composition having a silica coating layer on an alumina coating layer (J). ) Got. The same evaluation as in Example 1 was performed for the ultramarine blue composition (J).

Example 10 To the dispersion (Cd-1) obtained in Example 3, pure water was added until the pH of the dispersion reached 10 while keeping the level of the dispersion at an ultra-concentrator. did. This dispersion of pH 10 is
C., and while stirring, 1400 aqueous solution of zirconyl ammonium carbonate having a concentration of 0.5% by weight as ZrO _2.
g at a rate of 3 g / min to obtain a dispersion (Kd) of the ultramarine blue composition having a zirconia coating layer on a silica-alumina coating layer. A cation exchange resin is added to the dispersion (Kd) to conduct ion exchange until the pH becomes 3, and then the ultramarine composition is separated and removed, and then dried to have a zirconia coating layer on the silica-alumina coating layer. An ultramarine composition (K) was obtained. The same evaluation as in Example 1 was performed for the ultramarine blue composition (K).

Comparative Example 1, Comparative Example 2 Ultramarine blue particles pulverized and used in Examples 1 and 6 were evaluated for acid resistance and heat resistance in the same manner as in Example 1.

Comparative Example 3 A dispersion of ultramarine blue particles, in which 50 g of ultramarine blue particles as raw materials were dispersed in 950 g of pure water, was placed in a reactor equipped with a reflux condenser, and the pH of the dispersion was adjusted to 10 with a 1% by weight aqueous NaOH solution. Then, the mixture was heated at 80 ° C. for 30 minutes with stirring. Then, the concentration of the concentration of 1.5 wt% of sodium silicate as SiO ₂ (SiO ₂ / Na ₂ O molar ratio 3.1) as SiO ₂ obtained by cation exchange of 1.5 wt% silicate Liquid 3
30 g was added at a rate of 1 g / min to obtain a dispersion (Hd) of the ultramarine composition having a silica coating layer. Dispersion (Hd
), A cation exchange resin was added thereto, and the mixture was ion-exchanged until the pH reached 3. Then, the ultramarine composition was separated and removed and dried to obtain an ultramarine composition (H) having a silica coating layer. The same evaluation as in Example 1 was performed for the ultramarine blue composition (H).

[0036]

[Table 1] Ultramarine blue particle coating material ( coating amount ) Acid resistance and heat resistance diameter ( μm ) First layer (wt% ) Second layer (wt% ) Example 1 1.1 SiO ₂ -Al ₂ O ₃ (33) --○ ◎ Example 2 1.1 SiO ₂ -Al ₂ O ₃ (33) SiO ₂ (14) ◎ ◎ Example 3 1.1 SiO ₂ -Al ₂ O ₃ (10) SiO ₂ (15) ◎ ◎ Example 4 1.1 SiO ₂ -ZrO ₂ (33)--◎ ◎ Example 5 1.1 SiO ₂ -ZrO ₂ (20) SiO ₂ (15) ◎ ◎ Example 6 0.4 SiO ₂ -Al ₂ O ₃ (33)--○ ◎ Example 7 0.4 SiO ₂ -Al ₂ O ₃ (33) SiO ₂ (14) ◎ ◎ Example 8 1.1 ZrO ₂ (10) SiO ₂ (21) ◎ ◎ Example 9 1.1 Al ₂ O ₃ (13) SiO ₂ ( 20) ◎ ◎ Example 10 1.1 SiO ₂ -Al ₂ O ₃ (10) ZrO ₂ (11) ◎ ◎ Comparative Example 1 1.1----× × Comparative Example 2 0.4----× × Comparative Example 3 1.6 SiO ₂ (9)--○ △

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Toshiro Komatsu 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Catalyst F-term in the Wakamatsu Plant (reference) 4J037 AA17 CA09 CA12 CA24 DD23 DD24 DD27 EE04 EE14 EE16 EE26 EE35 EE43 EE46 EE47 FF08 FF13 FF25

Claims (5)

[Claims] 1. A group IIIA group, a group IIIB group, and a group IV
An ultramarine blue composition comprising at least one metal oxide coating layer of one or more elements selected from Group A, IVB, VA, and VIB. 2. The coating layer in contact with the ultramarine blue particle surface,
The ultramarine blue composition according to claim 1, which is a coating layer of a composite oxide. 3. The ultramarine blue composition according to claim 2, wherein the composite oxide is one of silica-alumina, silica-zirconia, and silica-titania. 4. The ultramarine blue composition according to claim 1, wherein the coating layer comprises two layers, and the outermost layer is a silica layer. 5. The method for producing an ultramarine blue composition according to claim 1, comprising the following steps (a) to (f). (A) Step of preparing a dispersion of ultramarine blue particles (b) Step of adjusting the pH of the dispersion to a range of 8 to 12 (c) Formation of a first layer by adding an aqueous solution of an inorganic compound salt to the dispersion (D) if necessary, a step of adding an aqueous solution of a component different from that of the first layer in the same manner as in step (c) to form the second and lower layers (e) washing as necessary Step (f) Step of hydrothermal treatment as necessary (g) Step of drying and firing