JPS58157867A - White paint for oil painting - Google Patents

Abstract

PURPOSE:The titled paint, containing zirconium oxide powder having a specific particle diameter in the dispersed state in a drying oil as a vehicle, and having a deep elegant hue without causing the toxicity nor cracking in the coating films. CONSTITUTION:A white or gray oil paint obtained by incorporating a zirconium oxide powder having 40-1,200nm particle diameter or a mixture consisting essentially of the zirconium oxide powder and another pigment in the dispersed state in a drying oil, e.g. safflower oil or poppy oil, as a vehicle. The zirconium oxide powder is the monoclinic or tetragonal system, and obtained by adding an alkaline aqueous solution, e.g., aqueous ammonia, to an aqueous solution of zirconium sulfate, forming a gelatinous white precipitate ZrO2.xH2O, washing the precipitate with water, drying and dehydrating the dried precipitate. EFFECT:The mixing with another paint is freely carried out, and no discoloration will be caused later by the mixing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel paint for oil paintings whose main coloring component is zirconium oxide powder having a particle size in the range of 4Q nm to 1,200 nm. The purpose is to provide non-toxic, 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 pigments.

Oil paints contain pigments as coloring materials, a color vehicle mainly composed of drying oil, and auxiliary agents to maintain shape.

It is manufactured by mixing together with a drying accelerator, etc. the current,
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. Demand for white oil paint accounts for approximately 40% of all oil paints.

, 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 been recognized by people in the industry and artists, and there are many reports regarding this phenomenon. Recent examples include Makishima, Toyota, Okamura 0 Shikizai, 44, 156 (197
1) is reported in detail in . As described above, the coating film formed with zinc white has defects, and although there are many problems in drawing, 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 component, basic lead carbonate,
It is famous for causing lead poisoning when it was once used as a cosmetic. The use of such poisonous substances poses a risk of pollution, and is therefore undesirable for oil paints. Also, if this silver white is mixed with oil paints that use sulfide pigments such as ultramarine, vermilion, and cadmium yellow, it will darken later. Furthermore, it turns black when exposed to hydrogen sulfide gas, so it cannot be used for paintings of industrial or volcanic areas.

The cause of the black discoloration is based on the formation of black lead sulfide. Such matters are described in detail in Kuwabara and Ando, [Pigments and Colors J, 195, Kyoritsu Shuppan (1972).

Titanium white paint, which uses titanium white, does not react with drying oils, 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 excessive coloring power and hiding power as an oil paint, so it is rather incompatible as an oil paint. In drawing, when mixing colors or painting in many layers, it significantly subtracts other colors and lowers 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, and its usage is small.

The present invention has developed high-quality white and gray oil paints suitable for oil paintings, which eliminate the various drawbacks associated with white oil paints as described above. That is, by employing zirconium oxide powder with an average particle diameter in the range of 401 m to 1.200 nm as a pigment for oil paint,
We have succeeded in preparing a new white oil paint that eliminates cracks in the paint film, reduces color reduction and deterioration of saturation due to color mixing, and has a deep and elegant tone.

In general, the color of a pigment varies depending on the absorption, refractive index, particle morphology, etc. based on the crystal structure of the compound. For 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 hiding power of covering the base layer becomes large. However, there is a certain limit.
As the particles become smaller, the hiding power increases, but when the particle size becomes less than the wavelength of visible light, the particles become transparent due to complex optical phenomena such as scattering and diffraction, and rapidly decrease. In other words, the maximum value of covert particles appears with respect to the particle size. This value is also influenced by the refractive index and the type of vehicle. The refractive index is the particle size at which the hiding power of a white pigment reaches its maximum value. It is shown in Table 1 along with the specific gravity. These things are explained by Kubota, [Powder J p, 90B, Maruzen (1972).
(Published) and Kuwabara, Ando, [Pigments and Paints JP, 82゜Kyoritsu Shuppan (1972).

Table 1 *9 Edited by the Chemical Society of Japan, “Chemical Handbook, Basic Edition 1” Maruzen (19
80).

Table 1 summarizes the physical properties of known white pigments and compares them with zirconium oxide powder. By comparing and considering these values, the optimum particle diameter X value and hiding power when using zirconium oxide powder as a pigment can be estimated. The inventors conducted the following experiments based on ideas based on such reasoning, and came to invent a new white oil paint.

Next, zirconium oxide (m, -name zirco=7.Zr
O will be explained. A highly polished product is produced by heating and dehydrating zirconium hydrated oxide or oxyacid. At approximately 1.000"C, the crystal transitions from monoclinic (low temperature type) to tetragonal (high and low type). Zirconia.

ZrO□ is a hard, high melting point, and extremely stable compound. It has been used as a refractory material since ancient times, but
After the war, its uses expanded as special porcelain and electromagnetic ware.

The powder used in the present invention is a monoclinic (low-temperature type) fine powder with a particle size of 4° to 1,2001 m. An example of a manufacturing method for this is zirconium sulfate Zr (804
) Add an alkaline aqueous solution such as ammonia water to the 2 aqueous solution to form gel-like white precipitates Zr01 and ra2o, which are washed with water, dried, and dehydrated to obtain a fine powder. At this time, ZrO2 having various particle sizes can be produced by adjusting the conditions such as the concentration and temperature of the aqueous solution used for the precipitation reaction.

Next, the research results will be explained. The zirconium oxide powders having different particle sizes used in the experiment were prepared in four different ways by adjusting the production conditions of the hydrous zirconium oxide Zr0)+ and H2O.

That is, sample A (average particle diameter 5Q nm), sample B
(Same 10100n, Sample C (Same 2001m), Sample D
(500 nm), sample E (1.000 nm)
It is. The coloring power and hiding power of this paste were measured, and the ratio t = river was calculated. Commercially available zinc white, lead white and titanium white were used as a control sample and hiding power, and the test results for each were compared. It is listed in Table 2. The coloring power and hiding power were measured according to the method of JIS K5101-5 to 6, and the coloring power of titanium white was set as 100, and the coloring power and hiding power of other pigments were converted. This is what was shown.

As seen in Table 1 and Table 2, titanium white has excellent coloring power and hiding power, and particularly high hiding power. Because these are too excessive, if you mix the paint using titanium white with other paints or apply multiple coats, the other colors will be diminished.
It also reduces saturation. When titanium white is diluted with a transparent pigment such as finely powdered silicic acid, the tinting power and hiding power decrease at the same time, but the relative value of the two cannot be changed. Therefore, it is impossible to maintain coloring power and reduce hiding power in paints using titanium white.

Based on the opinions of many painters and the long experience of oil paint manufacturing engineers, adaptability as a white oil paint requires a balance between coloring power and hiding power, which is shown numerically in Table 2.
From the results, colored crabs ranged from 10 to 80. t: 1.0~
It was determined that a range of 8.0 is preferable. The zirconium oxide powders A', B, C, D, and E with a particle size of 40 to 1.200 nm according to the present invention have a coloring power of 11
~26. t: 1.2 to 7.0, which is a suitable range for white oil paint. It is clear that the values are similar to those of zinc white and lead white.

Therefore, if white and gray oil paints are manufactured using this, high-quality oil paints that have elegant color tones like zinc white and silver white, which have been used for a long time, and are not toxic or cause cracks in the paint film, can be produced. The zirconium oxide powder that can be produced as a raw material for the oil paint of the present invention has a particle size in the range of 4Q nm to 1,200 nm,
The crystal system may be monoclinic (low temperature type) or tetragonal (high temperature type). Alternatively, the surfaces of these particles may be modified by coating them with alumina, silica, stearic acid, or the like. Particles having a particle size within the above range exhibit pigment properties suitable for oil paints and exhibit deep and elegant aesthetic effects. Note that saffron oil, poppy seed oil, oil-modified alkyd resin, and the like are used as the color vehicle.

Next, an example will be explained.

Example 1 Fine particle zircon oxide powder A, average particle size 5Qnmioo
,oo part poppy oil 80.00
Part: Calcium stearate: 0.90 Part: Calcium naphthenate: o, oa parts The mixture with the above weight composition was kneaded with a ceramic roll mill,
An oil paint with good dispersion was prepared. If the results are shown in the same comparative value as the test results in Table 2 above, colored crab 15.0
, the hidden pay crab was 1.6 and the ratio t: 8.8.
As a white oil paint, it has a slightly transparent color tone that gives a sense of depth.

Example 2 Zircon oxide powder C0 average particle diameter 2001 m100, (
0 parts poppy oil 25.00
0.75 parts calcium stearate 0.75 parts calcium naphthenate O, OA parts The above mixture was kneaded in the same manner as in Example 1 to prepare an oil paint.
The results are shown using the same comparative values as in Table 2, and the colored crabs are 25.
Hidden pay crab 14.5 The ratio t: was 1.7.

This was an excellent white oil paint that had somewhat high tinting power, but also moderately reduced the color of the other color when mixed.

Example 3 Zircon oxide powder E, average particle size 1.000 nm 100
．． 00 parts poppy oil 20.00
Part: Calcium stearate: 0.60 Part: Calcium naphthenate: 0.02 part The above mixture was kneaded in the same manner as in Example 1 to prepare an oil paint.
The results are shown using the same comparative values as in Table 2. Colored crab 1B
, 4 , Hidden Paykani 11.0. The ratio t: 1.2. Met.

This is a sticky oil paint with slightly low tinting strength and transparency.

Example 4 Zircon oxide powder C0 average particle diameter 200 nm 100
．． 00 parts benzidine yellow 7.50 parts safflower oil ao, oo parts calcium stearate 0.90 parts cobalt naphthenate 0
．． 08 parts The above mixture was kneaded in the same manner as in Example 1 to prepare a lemon yellow oil paint, generally referred to as so-called gray oil paint, in which benzidine yellow 10G was diluted with fine zirconium oxide.

As a result, the color display according to JI828901 showed a chromaticity of x: 0°426, y: 0.460, and Y (tonia) 5° (Company).

This paint has a color difference △E of 0.4 and NBS compared to the one prepared with conventional zinc white instead of zircon oxide powder.
There was only a slight perceptible color difference in each unit. This coating film is stable and will not crack later due to deterioration.

The characteristics of the white and gray oil paints of the present invention are summarized as follows.

+1+ Does not contain toxic ingredients such as lead compounds.

(2) The formed coating has long-term stability and is not weakened by oral changes.

(3) The coating film does not crack due to oral changes.

(4) Colors can be mixed freely with other paints, and there is no risk of discoloration later.

(5) It is a high-quality oil paint with a deep and elegant color tone.

Claims (1)

[Claims] l. A drying oil is used as a color vehicle, and a particle size of 40 nm to 1.
．． A paint for oil painting characterized by containing zirconium oxide powder in a dispersed state in a range of 200 nm. 2. Japanese-French paint according to item 1, characterized in that zirconium oxide powder is used as the main Tp1, and pigments of other components are mixed and dispersed therein.