JPS5943406B2 - yellow pigment - Google Patents

Description

Detailed Description of the Invention The present invention provides (2n+m)ZnO, nTiO22mFe2
This invention relates to a novel yellow pigment made of composite oxide powder containing O3 zinc, titanium, and iron as main components.

Conventionally, yellow pigments made of inorganic substances include, for example, yellow lead,
Cadmium yellow is well known, but these pigments contain toxic lead, chromium, cadmium, etc. as main raw materials, and in recent years, from the perspective of preventing pollution during the production or use of pigments, There is a strong desire for a non-polluting yellow pigment to replace the above pigments.

The present inventor has been researching yellow pigments made of inorganic substances for many years, producing composite oxide powders of various metals, and examining their color tone. Zinc, titanium oxide, and iron oxide are blended in various ratios and fired to produce composite oxides with various composition ratios, and various studies have been conducted on the color tone of the composite oxide powder and the structure of the substance itself.

As a result, it was confirmed that if a spinel single phase diffraction result was obtained in the X1 diffraction of the resulting composite oxide, the color tone of the composite oxide powder would be a clear yellowish color.

When the X-ray diffraction result of spinel single phase is obtained, the composition of the composite oxide is (2n+m)ZnO, nTiO2,
mFe203 (However, the present inventors believe that the obtained composite oxide is (ZnO), a composite oxide of .TiO2 and a complex oxide of ZoO.Fe
I thought that it would depend on the total solid solution with the complex oxide 2O3.

By the way, (ZnO)2・TiO2 and znO-Fe2
It is well known that both 03 and 03 are spinel type compounds.

Therefore, the obtained composite oxide is (ZnO)2 ・T'i
On the other hand, it is conceivable that it is a mixture of Zn()Fe203 and Zn()Fe203.

Therefore, the present inventor developed (ZnO)2・TiO2 powder and Z
nO Fe2O3 powder is produced separately, and this is converted into n[(Z
nO)2・TiO2].

Intense mixing was performed at a ratio of m (ZnO.Fe203).

However, the color tone of the above mixture is different from that of composite oxides with the same composition ratio, that is, ZnO*T i02 and Fe
(2n-+-m)ZnO obtained by mixing 2O3 and firing
.

Compared to composite oxides with compositions of nTiO2 and mFe2O3, the sharpness was noticeably lacking.

Accordingly, the present inventors believe that the obtained composite oxide is (ZnO)2
- It was concluded that it was not a mixture of TiO2 and ZnO-Fe2O3, but that these were mutually solid dissolved (total solid solution) to form a new solid solution.

The present invention was completed based on the above findings.

That is, the present invention provides a yellow pigment consisting of (2n+m)ZnO,nTiO2° pinel-type composite oxide powder of zinc, titanium, and iron.

Next, details of the yellow pigment of the present invention will be explained.

The composite oxide powder in the present invention can be produced, for example, by the following methods.

That is, the composition ratio already mentioned, (2n+m)ZnO, nT
iO2, mFe2O3 (however, tan and iron oxide (Fe20
g, Fe3O4, etc.) and calcined within a temperature range of about 800 to 1100℃, the particle size suitable as a pigment (
For example, it can be ground to a specific surface area of about 4 to 6 g/g by the BET method.

At this time, the composition ratios n and m may have arbitrary values;
Standard color chart (JISZ8721) J hue 4YR~l0Y
R, brightness 5-8, saturation 6-approximate to 0, 4YR5/
The color tone is close to 11.

The ratio of zinc oxide, titanium oxide, and iron oxide is (2n+m)Z
When nO, nTiO2, mFe2O3 are removed, the composite oxide does not become a spinel single phase in X-ray diffraction, but ZnO,
In the case of TiO□, the peak of Fe2O3 appears as a different phase.

As mentioned above, when a different phase appears (not a single spinel phase), the color tone loses its clarity.

The yellow pigment of the present invention described above is a pollution-free pigment that exhibits a clear yellow tone that conventional pigments made of inorganic substances do not have. It is possible to obtain any color tone from 4YR5/11 to 9YR8/8.

At the same time, the yellow pigment of the present invention is also a pigment with excellent heat resistance, weather resistance, and the like.

Next, the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 Zinc oxide 3551, titanium oxide 1231 and iron oxide (Fe
2O3) 233F and ZnO: 60 mol%,
Tie□: 20 mol%, Fe2O3: 20 mol% raw material blend.

Next, this raw material mixture was heated in an electric furnace at a temperature of 900°C for 2 hours.
A composite oxide was obtained by firing for a period of time.

The obtained composite oxide was pulverized with a vibration mill to obtain a yellow pigment as a powder having a specific surface area of 5.571 f/P by BET method.

When the obtained yellow pigment was subjected to X-ray diffraction, only the spinel phase was obtained.

FIG. 1 shows the Xa diffraction pattern.

Next, the obtained yellow pigment 0.52 and castor oil 0.5
1 was kneaded with a Tuba set muller to make a paste, clear lacquer 4.51 was added to this, kneaded to form a paint, applied onto mirror coated paper using a 5mm applicator, and dried to obtain a coating film. [Standard color chart (JIS Z8721)
It exhibited a color tone corresponding to J's 60 Y R6,2/10.6.

Comparative Example 1 472 ft of zinc oxide and 245 g of titanium oxide were mixed to produce ZnO: 66.6 mol%, TiO2: 33.3 mol%.
A raw material mixture of

This is referred to as raw material mixture A.

On the other hand, 237 g of zinc oxide and 465 g of iron oxide (Fe203)
ZnO: 50 mol%, Fe2O3:
The raw material mixture was 50 mol%.

This is referred to as raw material mixture B.

. Raw material mixtures A and B were heated to 900°C in an electric furnace.
After firing at a temperature of 100 ml for a time to obtain a composite oxide, both composite oxides were mixed and further ground to obtain a powder of 5.3 g/g.

A coating film obtained using the obtained powder in the same manner as in Example 1 was 4.
．． 6 YB2.7/L O,1.

Example 2 Using the same mixture as raw material mixtures A and B of Comparative Example 1,
Both raw material mixture A: 30 molar ratio, raw material mixture B near 0
The mixture was mixed according to the molar ratio, and the mixture was fired at a temperature of 850° C. for 2 hours to obtain a composite oxide, and then 6. Or
It was ground into If/P to obtain a yellow pigment.

The obtained yellow pigment was subjected to X-ray diffraction, and the same diffraction results as in Example 1 were obtained for only the spinel phase.

Moreover, the paint obtained in the same manner as in Example 1 was 4.5YR5.4.
/10.7.

- 0.21% of the obtained yellow pigment was placed in 40% of low density polyethylene (Ube Industries, Ltd. E-019) at a temperature of 120°C.
A heat-resistant test piece was prepared by kneading it to a thickness of 1.5 mm using a hot roll.
Heated for minutes.

The L a and b values of the test piece before and after heating were measured using a color difference meter to determine the color change rate ΔE due to heating. However, ΔL
- (b value before heating) - (b value after heating), Δa - (a value before heating) - (a value after heating), Δb = (b value before heating) = (b value after heating) value).

Example 3 Using the same mixture as raw material mixtures A and B of Comparative Example 1,
Both were mixed at a ratio of raw material mixture A: 5 moles and raw material mixture B: 95 moles, and the mixture was fired at a temperature of 950° C. for 2 hours to form a composite oxide, and then in a vibration mill for 5.2 mols.
It was ground to 7If/P to obtain a yellow pigment.

The obtained yellow pigment was subjected to X-ray diffraction, and the same diffraction results as in Example 1 were obtained for only the spinel phase.

Further, the paint obtained in the same manner as in Example 1 was 40YR5,1/
It exhibited a color tone of about 11.0.

Example 4 Using the same mixture as raw material mixtures A and B of Comparative Example 1,
Both raw material mixture A: 5 mol ratio, raw material mixture B: 25 mol.
Mix in molar proportions and heat the mixture at a temperature of 900°C.
5. Calcinate for a time to form a composite oxide, then use a vibration mill.
5d/′? It was ground into yellow pigment.

The obtained yellow pigment was subjected to X-ray diffraction, and the same diffraction results as in Example 1 were obtained for only the spinel phase.

Further, the coating film obtained in the same manner as in Example 1 was 8.8YR7,4
/ It exhibited a color tone of about 8.0.

Comparative Example 2 ZnO:5 by mixing 284.6P of zinc oxide, 147.9P of titanium oxide, and 288.99P of iron oxide (Fe203)
A raw material mixture containing 0 mol of TiO2 and 25 mol of Fe2O3 was prepared.

Next, the raw material mixture was fired in an electric furnace at a temperature of 900°C for 2 hours, and then heated to 5.4rrf/? in a vibration mill. It was ground into powder.

When the obtained powder was subjected to X-ray diffraction, spinel phase and Ti
An O2 peak was observed.

Figure 2 shows an X-ray diffraction diagram.

[Brief explanation of drawings]

The drawings are all X-ray diffraction diagrams; Figure 1 is an X-ray diffraction diagram of the yellow pigment obtained in Example 1, and Figure 2 is an X-ray diffraction diagram of the powder obtained in Comparative Example 2. .

Claims (1)

[Claims] 1 (2n+m)ZnO, nTiO2, mFe203
(However, it is a yellow pigment made of composite oxide powder of titanium and iron.