JPS63199275A - White paint for painting - Google Patents

Abstract

PURPOSE:To provide the titled nontoxic paint giving elegant color tone such as of zinc white, causing no fissure of the coating film therefrom, comprising the vehicle and, as the coloring chief component, composite oxide powder derived from Zr and one or more kinds of metals with a specified particle size selected from Ti, Ba and Sr. CONSTITUTION:The objective paint comprising, in a dispersed state, (A) drying oil (e.g., safflower oil) as the vehicle and (B) as the white pigment, composite oxide powder derived from Zr and at least one kind of metal with an average particle size 0.03-2mum (pref., of spherical type) selected from Ti, Ba and Sr.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention is directed to the use of one or more metals selected from titanium, barium, and strontium having an average particle diameter in the range of 0.0'3 to 2 μm. The present invention relates to a new oil paint whose main coloring component is powder of a complex oxide consisting of zirconium, and I! # Concerning non-toxic and stable high quality white and gray oil paints. Here, the gray oil paint is a general term for paints having a color tone other than white, which are mainly composed of white pigment and contain other components.

"Prior Art and its Problems" Oil paints contain pigments as coloring materials, color vehicles mainly composed of drying oil, auxiliary agents for maintaining shape, and drying accelerators.
*b Manufactured together. Currently, as white oil paints, zinc white, which has zinc white as its main component, and silver white, which has lead white as its main component, are popular.

The demand for white oil paint is about 4 (1') of all oil paints.
occupies . Zinc white is the most widely used oil paint. However, its main component, zinc white, reacts with the drying oil of the color vehicle to form zinc soap, which accelerates the deterioration of the paint film, making it brittle and causing numerous cracks. This phenomenon has long been recognized by people in the industry and artists, and there are many reports regarding this phenomenon. For example, a recent example is Makishima, Toyoda, Domura, “Color Material J 44.156 (197
1) is reported in detail. As described above, although there are many defects and drawing problems in the paint film formed with Sync White, no suitable improvement method has yet been found.

Silver white has been widely used as an oil paint since ancient times because it has a bright white color and forms a strong film with drying oil. However, its main ingredient, basic lead carbonate, is also famous for causing lead poisoning when it was once used in cosmetics. The use of such poisonous substances poses a risk of pollution, and is therefore undesirable for oil paints. Additionally, this silvery white color gradually darkens when mixed with oil paints containing sulfide pigments such as ultramarine, permillion, and cadmium yellow. It also turns black due to hydrogen sulfide gas, so it cannot be used in industrial areas or volcanic areas due to its harmful effects. The cause of the black discoloration is mainly due to black lead sulfide. These matters are explained in detail in Kuwabara and Ando, ``Pigments and Colors JP 195, Kyoritsu Shuppan (1972).

Titanium white paint using titanium white does not react with drying oil, is non-toxic, and has no defects on the paint film. Incidentally, oil paints require different properties from paints whose main purpose is coating. Titanium white has too much coloring and opacity as an oil paint, so it is actually not suitable as an oil paint. In drawing, when this is used to mix colors and paint in multiple layers, it significantly reduces other colors and reduces the saturation to create a dark tone.

These drawbacks cannot be improved simply by adjusting the content of titanium white in the color vehicle because the balance between coloring power and hiding power cannot be achieved. Furthermore, it is impossible to maintain coloring power and suppress excessive hiding power. For this reason, titanium white has poor adaptability as an oil paint.
Its usage is small.

In addition, the color of a pigment generally varies depending on the original absorption, refractive index, particle morphology, etc. based on the crystal structure of the compound. In the case of the same compound, the finer the particles, the larger the surface area of the particles, which increases the amount of light reflected from the surface. Therefore, the hidden power of covering the base layer becomes greater. However, up to a certain limit, the hidden power increases as the particles become smaller, but when the particle size becomes less than the wavelength A of visible light, the particles become transparent due to complex optical phenomena such as scattering and diffraction, and rapidly decrease. Tsumashi,
The maximum value of covertness appears with respect to particle size.

This value is also influenced by the refractive index and the type of vehicle. The particle size at which the hiding power of the white pigment exhibits the maximum value is shown in Table 1 along with the refractive index and specific gravity.

These things are described in Kubo et al., “Powder JP 903 Maruzen (
(published in 1972) and Kuwabara and Ando, "Pigments and Colors," P32 Kyoritsu Shuppan, (published in 1972).

Table 1 In view of the problems of the prior art, the inventors of the present invention have conducted repeated research and have previously developed zirconium oxide powder (Japanese Patent Publication No. 60-353).
No. 84) and zirconium silicate powder (Special Publication No. 1984-
We proposed a white paint for oil paintings using No. 35385.) as a white pigment. Although this paint is of high quality and has solved the conventional problems, difficulties have arisen in the production technology of white pigment. This is because the primary particles of zirconium oxide powder have a high degree of agglomeration, which requires long milling times when using ordinary dispersers and mixers.Also, due to the wide particle size distribution, the pigment properties vary from manufacturing loft to manufacturing loft. It is difficult to maintain a constant value.

``Problems to be Solved by the Invention'' The purpose of the present invention is to solve the various drawbacks associated with the white oil paint, which can be sufficiently dispersed in a vehicle for oil painting, and has appropriate coloring power and hiding power. To provide high-quality white and gray oil paints suitable for oil paintings using the pigments shown.

As a result of intensive study, the present inventors discovered that titanium, barium,
By using a powder with controlled particle size of a composite oxide consisting of one or more metals selected from strontium and zirconium in oil paint pigments, cracks in the paint film can be eliminated, and color reduction and saturation due to color mixing can be prevented. The present invention has been achieved by successfully preparing a new white oil paint that has a deep and elegant color tone with less deterioration in color.

``Means for Solving the Problems'' That is, the present invention is characterized by the use of di/I/ : It is a white pigment made of powder of a complex oxide consisting of 1nium.

Furthermore, the present invention uses a drying oil as a color vehicle, and also contains titanium, j4lium, and a powder having an average particle size in the range of 0.03 to 2 μm.
This invention relates to a white thread paint for oil paintings, characterized in that it contains a composite oxide of one or more metals selected from strontium and zirconium in a dispersed state as a powder pigment.

The present invention will be explained in detail below.

Titanium and barium are raw materials for the oil paint of the present invention.

The composite oxide powder consisting of one or more metals selected from strontium and zirconium has an average particle size in the range of 0.03 to 2 cm, and is preferably close to spherical. By controlling the average particle size within the above range, the composite oxide powder exhibits coloring power and hiding power suitable for use as oil paint. Furthermore, the particle surface can be coated with alumina, silica, stearic acid, etc. to modify the surface.

As a color vehicle, a drying oil such as safflower oil, poppy oil, or oil-modified alkyd resin is used.

In the present invention, the composite oxide powder consisting of one or more metals selected from titanium, barium, and strontium and zirconium is prepared by mixing the entire compound solution or slurry of each of the constituent metals. It is obtained by forming a precipitate and then heat-treating the precipitate.

The composition of this composite oxide is titanium, nocurium,
The atomic ratio of one or more metals selected from strontium and zirconium is 5:95 to 80:20. Particularly preferred is a range of 10:90 to 50:50. If it is outside this range, the dispersibility will be poor and the desired pigment properties will not be obtained.

As a compound of each metal that is a component of the composite oxide, titanium tetrachloride is used as a titanium compound.

Titanium colloids (titanium hydroxide), titanium alkoxides, barium and strontium compounds such as their carbonates, nitrates, chlorides, hydroxides, etc. Zirconium compounds such as zirconium chloride, zirconium nitrate, etc. can be used.

In addition to these water-soluble compounds, it is also possible to use fine particles of 1 μm or less of oxides of the respective metals that are easily disposed of in suspension.

By adding caustic alkali, aqueous ammonia, carbonates, oxalates, amines, etc. to a solution or slurry containing compounds of metals of each of the constituent components of the composite oxide, a precipitate containing the constituent components can be obtained. is formed. In forming the precipitate, each constituent component may be precipitated simultaneously, or each constituent component may be precipitated one after another in stages.

The heat treatment temperature for the precipitate is preferably 500 to 1300°C.

If the temperature is too low, the dehydration and decomposition of the precipitate may be insufficient;
Moreover, if the temperature is too high, the powder will become coarse.

The paint according to the present invention is produced by mixing the above-described composite oxide powder and drying oil and kneading the mixture using a ceramic roll mill or the like.

The paint according to the present invention may be mixed with other components such as benzidine yellow G, if necessary.

"Examples" The present invention will now be described in more detail with reference to Examples and Comparative Examples.

Example 1 Titanium tetrachloride (TiO24) and zirconium oxychloride (zrOC22.8H20) were weighed out at a molar ratio of 1:9, and which one was added to water. Add 6N- to the solution dissolved in F.
Aqueous ammonia was added to completely form a precipitate.

Next, the precipitate was washed, passed through the mouth, and dried, and then the precipitate t-9
A Zr02-TIO2 composite oxide powder was obtained by heat treatment at 00°C. As shown in the transmission electron micrograph (TEM) of Fig. 1, the obtained powder has a K and an average particle size of 0.15 μm.
The particles were uniform.

100 parts by weight of the above powder, 40 parts by weight of poppy seed oil, 1.20 parts by weight of calcium stearate and 0.04 parts by weight of cobalt naphthenate were kneaded in a ceramic roll mill for 1 hour to develop an oil paint. The coloring power and hidden power of the obtained oil paint were measured, and the ratio was calculated as 1 coloring power/hidden power. The results are shown in the second column. In addition, commercially available zinc white, lead white and titanium white were used as control samples, and the test results for each are shown in Table 2. In addition, the color strength and hidden pigment measurements are conducted by JI.
It was determined by the method of SK 5101-5 and 6 and converted into titanium white coloring power t-100.

Comparative Example 1 ZrO2 powder was obtained in the same manner as in Example 1 except that titanium tetrachloride was not used and only zirconium oxychloride was used.

A TEM photograph of the obtained powder is shown in FIG. Further, oil paint was prepared in the same manner as in Example 1 using this powder. The results are shown in Table 2. For zirconium oxide only,
An hour of crosstalk did not show sufficient concealment power.

Example 2 Barium nitrate [: B a (Nos) 2 ] and zirconium oxychloride (zrocz2-8a20) were weighed out at a molar ratio of 1:1, and ammonium carbonate ( A solution of (NH4)2Co, ) was added to form a complete precipitate.

After washing, filtering and drying the precipitate, the precipitate t90
A BaO-ZrO2-based composite oxide powder was obtained by heat treatment at 0°C. As a result of TEM observation, the obtained powder had a nearly spherical shape with an average particle diameter of 0.25 μm and was well-organized.

100 parts by weight of the above powder, 35 parts by weight of poppy seed oil, 1.05 parts by weight of calcium stearate and 0.04 parts by weight of cobalt naphthenate were kneaded for 1 hour in a ceramic roll mill to prepare an oil paint. The results are shown in Table 2.

Example 3 The barium nitrate of Example 2 was converted into strontium nitrate [5r(
A SrO-ZrO□-based composite oxide powder was obtained in the same manner as in Example 2, except that the powder was changed to NO5)2 ].

The average particle diameter of the obtained powder was 0.32 μm.

Using this powder, oil paint was prepared in the same manner as in Example 2. The results are shown in Table 2.

Example 4 100 parts by weight of ZrO□-TiO2-based composite oxide powder obtained in Example 1, Benzidine Yellow 10G 7.5
0 parts by weight, 45 parts by weight of sour 7-rawa oil, 1.05 parts by weight of calcium stearate, and 0.0 parts by weight of copal naphthenate)
6 parts by weight were kneaded in a ceramic roll mill for 1 hour to prepare a lemon yellow oil paint, generally referred to as so-called gray oil paint, diluted with benzidine yellow 10G t-ZrO□-Tto2 powder. As a result, JIS 2890
1 x: 0.427, y: 0
．． 470°Y(4): It showed a chromaticity of 5aoo. This paint has a color difference ΔE- compared to that prepared with conventional zinc white.
It was 3.3. Color differences of this magnitude are hardly perceived visually. This oil paint film was stable and did not develop any cracks later on.

"Effects of the Invention" Pigment properties of the composite oxide powder of the present invention comprising one or more metals selected from titanium, barium, and strontium and zirconium and having an average particle diameter in the range of 0.03 to 2 μm. Coloring power = 10-20, t: 1
．． 8 to 2.5, which is comparable to that of zinc white and lead white, which are in the range suitable for white oil paint.

Therefore, by producing white and gray oil paints using this composite oxide powder, we can produce white and gray oil paints that have an elegant color vI4ft like the zinc white and silver white that have been used for a long time, but also have toxicity and no paint film. It is possible to obtain high-quality oil paints that do not cause cracks.

Moreover, the composite oxide powder of the present invention has a narrow particle size distribution,
It has the advantage that it is uniform, more easily dispersed in a color vehicle than zirconium oxide alone, and that it takes less time to cross-wire.

In addition, the oil paint of the present invention is less likely to lose color or decrease in saturation due to color mixing, and will not cause discoloration later.

[Brief explanation of the drawing]

FIGS. 1 and 2 are transmission electron micrographs (at a magnification of 10,000 times) as an alternative to FIG. 1, showing the particle shapes of the pigment powders obtained in Example 1 and J Comparative Example 1, respectively.

Claims (3)

[Claims] (1) A white pigment made of powder of a composite oxide made of zirconium and one or more metals selected from titanium, barium, and strontium and having an average particle size in the range of 0.03 to 2 μm. (2) Drying oil is used as a color vehicle and the average particle size is 0.0.
A white system for oil paintings characterized by containing powder of a composite oxide consisting of one or more metals selected from titanium, barium, and strontium and zirconium in the range of 3 to 2 μm as a pigment in a dispersed state. Paint. (3) A patent claim characterized in that the main component is a composite oxide powder consisting of zirconium and one or more metals selected from titanium, barium, and strontium, and other pigments are mixed and dispersed therein. A white paint for oil painting according to item 2.