JPH082917A - Superfine particulate brown pigment and its production - Google Patents

Abstract

PURPOSE:To produce the superfine particulate brown pigment imparting a flip-flop effect to metallic coatings, preventing the color separation and the irregular coloration of the coatings, and improving the weather resistance and heat resistance of the coatings by compounding the superfine particles of titanium, antimony and manganese oxides with each other. CONSTITUTION:A rutile type crystal structure fine titania sol having an average crystal diameter of 50-120Angstrom and obtained by neutralizing a titanium tetrachloride aqueous solution with an ammonia water to a pH of 7-8 and subsequently aging the produced colloidal amorphous water-containing titanium dioxide, etc., is used as a titanium source. An antimony source such as antimony trioxide or antimony pentoxide and a manganese source such as manganese (II) dichloride or manganese sulfate are added to the superfine particulate titanium hydroxide aqueous dispersion slurry in amounts of 10-40 pts.wt. and 3-15 pts.wt., respectively, per 100 pts.wt. of TiO2, and subsequently neutralized with an acid or alkali to deposit the components to the surfaces of the titanium hydroxide fine particles. The raw material mixture is calcined at 700-1100 deg.C and subsequently ground with a dry grinder to obtain the brown pigment having an average diameter of 0.01-0.1mum.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ultrafine particle brown pigment exhibiting excellent designability, durability and dispersibility, and a method for producing the same. The ultrafine particle brown pigment of the present invention comprises:
It is used as a color pigment for paints, inks, plastics and the like, and is particularly useful for high-grade industrial paints such as automobile paints.

[0002]

2. Description of the Related Art In recent years, ultrafine particles of titanium dioxide having an average particle diameter of 0.01 to 0.1 μm have been blended in a resin medium together with a metal flake pigment such as aluminum flakes or a metallic luster pigment such as titanium mica to obtain a so-called excellent flip. -High-quality metallic paint finish with a flop effect and excellent design has been noticed and put to practical use.

[0003]

By the way, in recent years, there has been an increasing demand for diversification of color design and high quality in automobiles and high-quality paint-finished furnishings. There is a strong demand for coating compositions for metallic paint finishes that exhibit a designable flip-flop effect. Therefore, for example, although it has been attempted to prepare a metallic coating composition by blending a white fine powder such as the ultrafine titanium dioxide and various organic pigments, color separation and color unevenness occur. There are many problems that still need improvement, such as being easy and having insufficient weather resistance and heat resistance.

[0004]

Means for Solving the Problems The present inventors have long focused on the excellent light-scattering ability of titanium oxide-based colored pigments, and by controlling it selectively, a wide variety of metallic paint finish systems can be obtained. Various studies were conducted in order to add a flip-flop effect to enrich the color design and to solve the above problems. As a result, the ultrafine particle colored pigment of the specific coloring system, which is composed of titanium as the main component and shares the specific component, has an excellent flip-flop effect that is rich in the coloring design in the metallic coating system. The present invention can be provided as a novel ultrafine particle brown pigment, which uses an ultrafine particle hydrous titanium oxide as a titanium source, in particular, a rutile crystal fine titania sol, and further uses silicon or aluminum for the hydrous titanium oxide. By treating the compound of
The present invention has been completed based on the finding that an ultrafine particle brown pigment having desired desired characteristics can be industrially advantageously produced.

That is, the present invention is as follows: 1. Ultrafine brown pigments having an average particle size of 0.01 to 0.15 µm, which are composed of oxides of titanium, antimony and manganese. The ultrafine brown powder according to 1 above, containing 10 to 40 parts by weight of an oxide of antimony as Sb ₂ O ₃ , _{3 to} 15 parts by weight of an oxide of manganese as MnO, and the remainder being substantially an oxide of titanium. Pigments, 3. 3. The ultrafine brown pigment according to claim 1, which has a coating of a hydrous oxide or oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin and antimony on the surface of the particle. 4. The ultrafine brown pigment according to the above 1, 2 or 3, wherein the particle surface has a coating of at least one organic compound selected from the group of polyhydric alcohols, alkanolamines and organosilicones. 5. A method for producing an ultrafine particle brown pigment, which comprises mixing ultrafine titanium oxide hydroxide, an antimony source and a manganese source and firing the mixture at 700 to 1100 ° C. An aqueous dispersion of ultrafine titanium oxide hydroxide is added with an antimony source and a manganese source, and then the treated product is treated.
6. The method for producing the ultrafine brown pigment according to the above item 5, which comprises firing at 700 to 1100 ° C. 7. The method for producing an ultrafine brown pigment according to the above 5, wherein the antimony source is antimony oxide and the manganese source is a sulfate thereof. In addition to the ultrafine titanium oxide hydroxide, antimony and manganese sources, aluminum and / or silica compounds are added in an amount of 1 to 10% by weight based on TiO _{2 of the} titanium oxide hydroxide and calcined at 700 to 1100 ° C. 8. The method for producing an ultrafine particle brown pigment according to the above item 5, 9. The method for producing an ultrafine brown pigment according to the above 5, 6, or 8, wherein the ultrafine titanium oxide hydroxide is a neutralized hydrolyzate of an aqueous titanium tetrachloride solution and is substantially a rutile crystal. , Ten. Aluminum in an aqueous dispersion of ultrafine brown pigment,
After adding a water-soluble salt of at least one element selected from the group consisting of silicon, titanium, zirconium, tin and antimony, an acid or an alkali is added to neutralize and precipitate on the surface of the brown pigment and fractionated. 10. The method for producing an ultrafine brown pigment according to the above 5, which is characterized by comprising: It is a metallic or pearl paint containing 1 to 20% by weight of an ultrafine brown pigment.

The ultrafine brown pigment of the present invention is titanium,
It is composed of oxides of antimony and manganese and has an average single particle diameter of 0.01 to 0.15 μm, preferably 0.03 to 0.1 μm, as determined by electron microscopy. If the average single particle diameter is smaller than the above range, the desired flip-flop effect is not brought about, and if it is larger than the above range, a coating film having a solid feeling which does not exhibit the desired flip-flop effect is easily obtained. Normally, antimony oxide is added to Sb ₂ O ₃
10 to 40 parts by weight, preferably 15 to 35 parts by weight, manganese oxide as MnO 3 to 15 parts by weight, preferably 4 to 12 parts by weight, and the remainder substantially consisting of titanium oxide, In addition, if necessary, a very small amount of oxides of lithium, sodium, phosphorus, calcium and the like may be contained. Such ultrafine brown pigments show a deep reddish brown to purple brown color, and are compounded with a metal flake pigment such as aluminum flakes or a metallic luster pigment such as mica titanium in a resin medium to give a unique color. A coating composition such as a metallic coating or a pearl coating exhibiting a flip-flop effect and excellent in designability can be obtained.

The ultrafine brown pigment of the present invention is further coated on its surface with a hydrous oxide or oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin and antimony, and a polyhydric alcohol. , An alkanolamine and an organosilicon, and may have a coating of at least one organic compound selected from the group of: The ultrafine brown pigment having such a coating is excellent in dispersibility and durability in a resin medium, and is more preferable in the above coating composition.
Can exhibit the flop effect. The coating amount is 1 to 30% by weight of aluminum as Al ₂ O ₃ , 1 to 20% by weight of silicon as SiO ₂ , and oxides (TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ ) 0.3
-15% by weight is suitable. Also, in the case of coating with an organic compound, as a solid content of the brown pigment of the core,
0.3-5% by weight is suitable.

In the manufacturing method of the present invention, a titanium source,
Mix the base components of the antimony source and the manganese source, and add 700
A brown pigment can be obtained by firing at a temperature of ~ 1100 ° C. The present invention is particularly characterized in that ultrafine particles of hydrous titanium oxide are used as the titanium source.
This is a fine titania sol having a rutile type crystal structure, a sol of fine hydrous titanium oxide showing a peak of a rutile type crystal when measured by an X-ray diffraction method, and its average crystallite diameter is usually 50 to 120 Å belongs to. This one is
For example, a colloidal amorphous hydrous titanium oxide obtained by neutralizing an aqueous solution of titanium tetrachloride with ammonia water at a pH of 7 to 8 is aged, or an amorphous hydrous titanium oxide such as metatitanic acid or orthotitanic acid is hydrous. It can be obtained by heating in an aqueous solution of sodium oxide and then in a hydrochloric acid solution, or by heating an aqueous solution of titanium tetrachloride for hydrolysis. In the present invention, such a fine titania sol having a rutile-type crystal structure can be used as it is or after being dried and pulverized as finely as possible.

Various substances can be used as the antimony source and the manganese source as the base component. For example, the antimony source includes antimony trioxide, antimony pentaoxide, antimony pentachloride, antimony trichloride, antimony soda, etc. As the manganese source, manganese (II) chloride, manganese sulfate, manganese carbonate, etc. can be used.

The raw materials for the respective components of the base can be mixed by various methods. For example, when powders are used as the raw materials, they may be simply mixed. When using a compound solution of a base component of an antimony source or a manganese source, for example, a solution of these base components is added to and mixed with ultrafine particulate hydrous titanium oxide, or dried, or ultrafine particulate hydrous oxide is used. A compound solution of each component is added to an aqueous dispersion slurry of titanium, and each component is precipitated on the surface of the hydrous titanium oxide by neutralizing with an acid or an alkali, or used as an aqueous dispersion of an antimony source and a manganese source. When this is done, the aqueous dispersion is added to the slurry of ultrafine titanium oxide hydroxide and mixed and filtered,
It can be performed by washing.

The mixing ratio of each component is 10 to 40 parts by weight, preferably 15 to 35 parts by weight, of Sb ₂ O ₃ as antimony and _{3 to 3} parts by weight of MnO based on 100 parts by weight of TiO _{2 of} ultrafine titanium oxide hydroxide. -15 parts by weight, preferably 4-1
2 parts by weight. In addition to these base components, various auxiliary components can be used, for example, a very small amount of a compound such as lithium, sodium, phosphorus or calcium can be mixed.

The raw material mixture obtained by mixing as described above is calcined at a temperature of 700 to 1100 ° C, preferably 800 to 1050 ° C. The raw material mixture may be in the form of slurry, cake or dry powder. Upon firing, each component undergoes a solid phase reaction to develop a color, and the brown pigment of the present invention is obtained. In the present invention, since ultrafine particles of hydrous titanium oxide are used as the titanium source, the calcined product is easily pulverized by a dry pulverizer such as a micronizer, a jet mill, a roller mill, a bantam mill, and a sample mill to easily obtain an average single particle. Particle size is 0.
It can be an ultrafine brown pigment of 01 to 0.1 µm. It should be noted that the ultrafine particles of hydrous titanium oxide used as the titanium source in the present invention are likely to cause particle growth or sintering during firing, and in order to suppress it, a silicon compound and / or an aluminum compound is subjected to a firing treatment. It is desirable to be present and baked as an auxiliary agent. In this case, the auxiliary agent may be added to the component raw material, pre-mixed with the hydrous titanium oxide and the auxiliary agent, or pre-coated with the auxiliary agent on the surface of the hydrous titanium oxide to be present. However, a coating method is more desirable. The amount of the auxiliary agent used cannot be specified unconditionally because it varies depending on the mixing ratios of the component raw materials and the firing conditions, but in terms of oxide of the auxiliary agent, it is 1 to 10% by weight based on TiO _{2 in} the hydrous titanium oxide. ,
It is preferably 3 to 8% by weight. Specific examples of the calcination treatment aid used include, for example, inorganic silicon compounds such as water-soluble silicates such as colloidal silica or sodium silicate, and organic silicon compounds such as silicone oil and silane coupling agents. Examples of the aluminum compound include water-soluble aluminum salts such as aluminum sulfate, aluminum nitrate, aluminum chloride and sodium aluminate.

The calcination can be carried out by various methods, for example, a static furnace such as an electric furnace, a tunnel kiln or an internal combustion type or an external combustion type rotary kiln.

In the present invention, the particle surface of the thus obtained ultrafine brown pigment is further selected from at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin and antimony. Of the above-mentioned and / or at least one organic compound selected from the group of polyhydric alcohols, alkanolamines and organosilicones, and in such a case, a resin medium. It is possible to further improve the dispersibility and durability. The ultrafine brown pigment thus obtained can exhibit a more preferable flip-flop effect in coating compositions such as metallic paints and pearl paints. The coating amount of aluminum is 1 to 30% by weight as Al ₂ O ₃ , 1 to 20% by weight as silicon SiO ₂ , and the other compounds are oxides (Ti
_{O 2, ZrO 2, SnO 2} , Sb 2 O 3) as a 0.3 to 15 wt% is appropriate. Further, in the case of coating with the organic compound, 0.3 to 5% by weight is suitable as the solid content of the brown pigment of the core.

The ultrafine brown pigment of the present invention is suitable not only for paints but also for various uses such as inks and plastics. However, it is a metallic that can exhibit an excellent flip-flop effect with a rich color design. It is particularly suitable for use in a coating composition. The metallic coating composition may be prepared by various methods. For example, the ultrafine brown pigments and various metallic flaky pigments such as scaly metallic pigments and pearl pigments may be used in a ratio of 0.1 to 10: 1. It can be carried out by blending them in a weight ratio and dispersing them in various thermosetting or thermoplastic resins. These resins are usually blended in a proportion of 10 to 50% by weight of the coating composition.

[0016]

【Example】

Example 1 500 ml of an aqueous titanium tetrachloride solution having a concentration of 200 g / l as TiO ₂
An aqueous sodium hydroxide solution having a concentration of 100 g / l as Na ₂ O,
The system was added in parallel to water so as to maintain the pH at 5-9, and aged for a predetermined time. The ultrafine particles of hydrous titanium dioxide precipitate obtained were filtered and washed, then dispersed again in water, and TiO ₂
As a water-containing titanium dioxide slurry having a concentration of 100 g / l. To this slurry was added 40 g of Sb ₂ O ₃ powder, then Mn
200 g / l manganese sulphate aqueous solution (MnSO ₄ 5H ₂ O
(Dissolved in a sulfuric acid solution of 50%), and a 20% aqueous ammonia solution was added to adjust the pH to 7 to form a precipitate of a manganese component. The hydrous titanium dioxide slurry thus treated was thoroughly stirred with a homomixer and then placed in an electric furnace.
It was calcined at 800 ° C. for 5 hours, allowed to cool, and dry-ground to obtain the ultrafine brown pigment of the present invention. This was a rutile type crystal with an average single particle size (electron microscopy) of 0.03 μm.

Example 2 Ultrafine brown pigment powder obtained by the same method as in Example 1 was dispersed in water to obtain a slurry having a solid content concentration of 100 g / l, wet pulverized and heated to 70 ° C. did. 1 wt% stannous chloride aqueous solution was added as SnO ₂ to the solid content of the slurry, then 2 wt% zirconium sulfate aqueous solution was added as ZrO ₂ , and then sodium hydroxide aqueous solution was added to adjust the pH to 7. After adjustment, the pH of the system was further adjusted to 7 to 10% by weight with an aqueous solution of sodium aluminate as Al ₂ O ₃ and sulfuric acid.
In order to maintain the temperature at 1, the hydrous oxides of tin, zirconium and aluminum were precipitated. After that, filtration, washing, drying and dry pulverization were carried out to obtain the ultrafine brown pigment of the present invention. This was a rutile type crystal with an average single particle size of 0.06 μm.

Example 3 An ultrafine brown pigment of the present invention was obtained by the same procedure as in Example 2 except that the firing temperature was 950 ° C. This was a rutile type crystal with an average single particle diameter of 0.08 μm.

Example 4 100 g of TiO ₂ obtained by the same method as in Example 1
/ l in the ultra-fine particles hydrous titanium dioxide slurry at a concentration of, SiO ₂
As a solution, 10 ml of a sodium silicate aqueous solution having a concentration of 100 g / l was added, and then sulfuric acid was added to adjust the pH to 7, followed by filtration and washing, and ultrafine particle hydrous dioxide coated with 1% by weight of a silicon compound as SiO _2. Titanium was obtained. Then, this was again made into an aqueous slurry, and the slurry was treated with Sb ₂ O ₃ and MnO in the same manner as in Example 1 below, after which 95
It was baked at 0 ° C. for 5 hours to obtain the ultrafine brown pigment of the present invention. This is a rutile type crystal with an average single particle size of 0.04.
μm.

Example 5 With respect to the ultrafine brown pigment obtained in the same manner as in Example 4, SnO ₂ was added in the same manner as in Example 2 below.
And Al ₂ O ₃ were treated to obtain the ultrafine brown pigment of the present invention. This is a rutile type crystal with an average single particle size of 0.04.
μm.

Example 6 An ultrafine brown pigment of the present invention was obtained in the same manner as in Example 5 except that the firing temperature was 1050 ° C. This was a rutile type crystal with an average single particle diameter of 0.08 μm.

Comparative Example A titanium sulfate aqueous solution having a concentration of 200 g / l as TiO ₂ was hydrolyzed by heating at 110 ° C. to obtain a hydrous titanium dioxide precipitate, which was filtered and washed, and then the same procedure as in Example 1 was performed. By the way
It was treated with Sb ₂ O ₃ and MnO, and then calcined at 1200 ° C. for 5 hours to obtain a brown pigment having an average single particle diameter of rutile crystals of 0.3 μm.

Test Example The performances of the ultrafine brown pigments of the above-mentioned examples and the brown pigment of the comparative example were tested, and the results shown in Table 1 were obtained.
The performance evaluation in Table 1 was performed as follows. 1. Preparation of paint 7.5g sample is acrylic resin / butylated melamine resin = 8 /
2 (weight ratio) 56.1 g (nonvolatile content 53%) of mixed varnish was mixed, and paint shaker (Red Devil Co., # 51
After dispersing in 10) to make a paint, aluminum paste was added (weight ratio sample / Al = 1/1) and mixed well to give a metallic paint. 2. Enamel coating color measurement Enamel paint without the addition of aluminum paste was applied on a white plate to a dry film thickness of 60 μm and baked at 105 ° C for 30 minutes, then the L value, a value and b value were measured with a color difference meter. It was measured. 3. Metallic paint film discoloration colorimetry This coating composition is applied on a steel plate so that the dry film thickness is 18 μm, and after setting for 30 minutes, acrylic clear is applied so that the dry film thickness is 12 μm. After 30 settings, It was baked at 130 ° C for 30 minutes. This coating plate is a gonio colorimeter
Using GCMS-3 (Murakami Color Research Laboratory), incident angle 45 °, measurement angle 40
The color was measured at ° (face color) and -20 ° (flop color), and ΔL, Δa and Δb were calculated by the following formulas. 3. ΔL = L (40 °) −L (−20 °) Δa = a (40 °) −a (−20 °) Δb = b (40 °) −b (−20 °) Comprehensive Evaluation Based on the color measurement results of 2 and 3, the color design was comprehensively evaluated. ⊚: Coloring and flip-flop effects are the best. ◯: Coloring property and flip-flop effect are both excellent. X: Those that do not exhibit the flip-flop effect.

[0024]

[Table 1]

[0025]

The ultrafine brown pigment of the present invention is a paint,
It is suitable as a coloring pigment for various uses such as ink and plastics, and is especially suitable for metallic paint systems that are desired to have an excellent flip-flop effect that is rich in colored design, such as color separation and color unevenness. It is also useful for high-grade paint finishing because it has excellent weather resistance and heat resistance. In addition, the production method of the present invention can be produced more industrially by using a microtitania sol of rutile crystals as the titanium source, or by adding a silicon compound or an aluminum compound and performing a firing treatment. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masanori Iida 1 Ishihara-cho, Yokkaichi-shi, Mie Ishihara Sangyo Co., Ltd. Yokkaichi Operations

Claims (11)

[Claims] 1. An ultrafine brown pigment comprising an oxide of titanium, antimony and manganese and having an average particle diameter of 0.01 to 0.15 μm. 2. An antimony oxide of 10 as Sb ₂ O _3.
~ 40 parts by weight, manganese oxide as MnO 3 ~ 15
The ultrafine brown pigment according to claim 1, which is contained in an amount of 1 part by weight and the balance is substantially an oxide of titanium. 3. The ultrafine brown pigment according to claim 1, wherein the particle surface has a coating of a hydrous oxide or oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin and antimony. 4. The ultrafine brown pigment according to claim 1, 2 or 3, wherein the surface of the particle is coated with at least one organic compound selected from the group consisting of polyhydric alcohols, alkanolamines and organosilicones. 5. A method for producing an ultrafine brown pigment, which comprises mixing ultrafine titanium oxide hydroxide, an antimony source and a manganese source and firing the mixture at a temperature of 700 to 1100 ° C. 6. An aqueous dispersion of ultrafine titanium oxide hydroxide,
The method for producing an ultrafine brown pigment according to claim 5, wherein an antimony source and a manganese source are added and treated, and then the treated product is calcined at 700 to 1100 ° C. 7. The antimony source is antimony oxide,
The method for producing an ultrafine particle brown pigment according to claim 5, wherein the manganese source is a sulfate thereof. 8. In addition to ultrafine titanium oxide hydroxide, antimony and manganese source, aluminum and / or silica compound is added in an amount of 1 to 10% by weight based on TiO _{2 of the} titanium oxide hydroxide in an amount of 700 to 700. The method for producing an ultrafine particle brown pigment according to claim 5, wherein the method is firing at 1100 ° C. 9. The ultrafine brown powder according to claim 5, wherein the ultrafine titanium oxide hydroxide is a neutralized hydrolyzate of an aqueous titanium tetrachloride solution and is substantially a rutile crystal. Method for producing a base pigment. 10. An aqueous dispersion of an ultrafine brown pigment is added with a water-soluble salt of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium, tin and antimony, and then an acid or alkali is added. Neutralize, precipitate on the surface of the brown pigment, fractionate, dry,
The method for producing an ultrafine brown pigment according to claim 5, wherein the method is pulverization. 11. 1 to 20% by weight of ultrafine brown pigment
Blended metallic or pearl paint.