JPS60245671A - Lower titanium oxide pigment - Google Patents

Abstract

PURPOSE:To provide a lower titanium oxide pigment having excellent physical properties such as gloss, light resistance, dispersibility, storage stability, etc., by providing a coating layer of an oxide or a hydroxide of a metal such as Al, Ti or Si on the surface of the pigment. CONSTITUTION:A lower titanium oxide pigment is obtd. by coating the surface of a lower titanium oxide of the formula TiOx (wherein x is 1.5-1.9) (having an average particle size of 0.1-1mu and obtd. by heat-treating a mixture of titanium dioxide and metallic titanium in a non-oxidizing atmosphere with 0.1-8wt% metal oxide (selected from among oxides of Al, Ti, Si, Zr, Sn, Sb and Ce). The pigment is excellent in pigment characteristics, harmless to the human, highly safe against the skin, and suitable for use as a pigment for food packaging materials, cosmetics, etc.

Description

Detailed Description of the Invention Titanium dioxide is a low-order oxide that is produced by irradiating it with ultraviolet rays or heating it at high temperatures in a reducing atmosphere, and since this substance has conductivity, it can be used as a conductive agent. It is proposed to use On the other hand, lower titanium oxide has a gray to black hue depending on its degree of reduction and is harmless to humans, so its use as a black pigment has also been proposed.

This low-order titanium oxide has favorable properties as a pigment even as it is, and can be incorporated into various coloring compositions.

In other words, compared to carbon black and iron oxide, which have traditionally been used as black pigments, lower titanium oxide has better miscibility with the vehicle of a coloring composition, and can also be used in combination with other general-purpose pigments such as titanium dioxide. In this case, they are highly miscible because their physical and chemical properties are similar.

However, when lower titanium oxide is used as it is as a black pigment, it cannot be said to have sufficient physical properties such as dispersibility, storage stability, gloss, and weather resistance compared to titanium dioxide pigments.

The present invention particularly relates to a low titanium oxide pigment with improved pigment physical properties such as gloss and weather resistance.

That is, the present invention provides general formula Ti0x(X;1.!5-1
．． 9) on the surface of the lower titanium oxide particles represented by AQ
The present invention is a low-order titanium oxide pigment containing a coating layer of a hydrous oxide or oxide of at least one metal selected from the group consisting of Si, Zr, Sn, Sl), and Ce.

In the present invention, the general formula Ti0x (X; 1.5-1.9
), the ratio of 〇 to T is 1.
It has a composition of 5-1.0, preferably 1.6-1.8, particularly preferably 1.6-1.7. Examples of low-order titanium oxide with such a composition include TiO, Ti, and O.
,,1″+305, T1407, TI, 09, T160
1 T17017, Ti8015, Ti90.9, T1
A compound such as 1oO1 exists in a substantially single phase within the range of oxidation degree X of the above general formula, or a compound in which a plurality of phases coexist.

That is, the general formula of the present invention expresses the composition of the lower titanium oxide particles as an average value. The average particle diameter of the lower titanium oxide in the present invention is usually 1 to 1μ, preferably 2 to 0.7μ, particularly preferably 2 to 0.7μ.
It is 0.5μ.

These low-order titanium oxides are obtained by heating a mixture of titanium dioxide and metallic titanium in a vacuum, an inert gas, or a reducing atmosphere, and titanium dioxide is heated in a reducing gas atmosphere such as ammonia gas or hydrogen gas. Any of those obtained by heating and reducing in a solvent can be used.

In the present invention, the metal component of the hydrated metal oxide or oxide present on the surface of the low-order titanium oxide is A(!,
These include Ti, Sl, Zr, Sn, Sb, and Ce. In the present invention, a coating layer of a water-conserving oxide or oxide of at least one of these metals is contained on the surface of the low-order titanium oxide particles. The coating amount is 0.1 to 8%, preferably 0.2 to 6%, particularly preferably +i+,5=5%, based on the weight of Tiox as metal oxide.

When the coating amount is less than the above range, the desired weather resistance of the present invention is achieved.
It is not desirable to obtain a glossy effect, and too much is not only disadvantageous in terms of medicine, but also reduces dispersibility, gloss, etc., and tends to cause foaming in plastics. do not have.

Among the coating metal compounds in the present invention, AQ, Ti, S
i is preferable, and A0 is especially preferable from the viewpoint of weather resistance.
Coating with AQ and Ti, or a combination of AQ, I and Sl is desirable. These coating layers may be present in the form of two continuous films of the low-order titanium oxide particles or in the form of discontinuous films.

In the present invention, if necessary, an organic compound such as polyhydric alcohol, alcamelamine, organosilicon, etc. may be coated as long as the basic characteristics of the present invention are not impaired.

The low titanium oxide pigment of the present invention has excellent pigment properties such as weather resistance, gloss, dispersibility, and storage stability, and is used as a coloring agent in various fields such as paints, inks, plastics, and cosmetics. useful. In particular, the low-order titanium oxide pigment of the present invention is suitable for use in food packaging materials and cosmetics because it is harmless to humans and highly safe to the skin.

To produce the pigment of the present invention, first, lower titanium oxide is made into an aqueous slurry, and AO11'i, Si, Z
A soluble compound of at least one metal selected from the group consisting of R, Sn, St), and Ce is added and neutralized with an acid or alkali to form a hydrous oxide of the metal on the surface of the lower titanium oxide particles. It is precipitated to form a covering layer. The pigment concentration of low titanium oxide aqueous slurry is usually 100-800.
g/θ is preferably 200 to 4.008/ρ, and the temperature is desirably maintained at 50 to 90°C, preferably 60 to 80°C. Examples of soluble compounds of metals added to this aqueous slurry include alkali aluminate, aluminum chloride, aluminum sulfate, titanium chloride, titanium sulfate, alkali silicate, tin chloride, tin sulfate, tin oxychloride, and potassium sulfate. , rukonium chloride, ruphnium sulfate, rukonium acetate, antimony chloride, HE cerium, and the like can be used. When coating two or more metal compounds, the soluble compounds may be added simultaneously or sequentially. In order to precipitate the coating material added to the aqueous low-order titanium oxide slurry as a hydrated oxide on the surface of the low-order titanium oxide, if the slurry is alkaline, add an acidic compound such as sulfuric acid or hydrochloric acid. If the slurry is acidic, an alkaline compound is added to neutralize it and adjust the pH of the slurry to 6-8. The neutralized slurry is aged at a temperature of 40 to 90°C for a certain period of time, usually 10 to 60 minutes, filtered and washed to remove soluble salts, dried, and then subjected to a conventional pulverization treatment to reduce the lower oxidation. It is a titanium pigment product.

Examples include lower titanium oxide (X value: 1.65, average particle size 0.3μ) obtained by heating a mixture of titanium oxide powder and metal titanium powder in an inert atmosphere of nitrogen gas flow. 3. After heating the aqueous slurry (concentration 40 (11, /θ) to 50″C, add sodium aluminate solution to AQ203.
Added 0%. Thereafter, after stirring for 20 minutes, sulfuric acid was added to adjust the 111-I of the slurry to 7 to precipitate aluminum water oxide. After that, it was aged for 60 minutes, filtered, washed, heated for 5 days and night, then heated to 80%
The mixture was dried at °C for 1 hour and pulverized using ultra-pulverized rock to obtain the low-order titanium oxide pigment of the present invention. (Pigment A) Example 2 In Example 1, except that before adding the sodium aluminate solution to the aqueous slurry at 50°C, 0.8% titanium tetrachloride solution as TlO2 was first added, and then stirred for 10 minutes. was treated in the same manner to form the lower titanium oxide pigment of the present invention. (Pigment B) Example 3 In Example 1, before adding the sodium aluminate solution to the aqueous slurry at 50°C, a titanium tetrachloride solution of 0.8% as TlO2 was first added, and then stirred for 10 minutes. Next, add 1.0% sodium silicate solution as SiO2, stir for 20 minutes, and then hydroxide). A lower titanium oxide pigment of the present invention was obtained by the same treatment. (Pigment C) Comparative Example Addition of sodium aluminate, solution and sulfuric acid to the aqueous slurry at 50°C in Example 1, without subsequent aging, directly filtering after adjusting the slurry to p+-+s with sulfuric acid, Washed, dried at 1'C for a day and night, and crushed in an ordinary crusher to obtain a low titanium oxide pigment. (Pigment D) Test Example Low titanium oxide pigments A-D of the above Examples and Comparative Examples The performance was tested and the results shown in Tables 1, 2 and 3 were obtained.

As is clear from these results, it can be seen that the low titanium oxide pigment of the present invention has excellent performance in both gloss and weather resistance.

Table 1 Actual A 84 68 43 88 (-, + 1+') Implementation B
83 694.6 940 1+'1 The evaluation in Table 1 was performed as follows.

(1) Preparation of test plate Dissolve the low-order titanium oxide pigment in coconut oil-modified short oil alkyd 414 fat/butylated melamine resin (7/3 weight ratio) varnish, mix, and use a paint shaker (Lenddevil Co., Ltd. well 5i).
io) to form a paint, this material was applied to a zinc phosphate-treated steel plate (7 cm x 35 cm) to a thickness of approximately 60 μm (as a dry coating), and baked for 30 minutes at "130" (:) for a black test. Created a board.

(2) Measurement of specular gloss initial gloss of black test plate (20°-20° and 6t)'
-60° specular gloss) was measured using a gloss meter (Model GM-26D manufactured by Toshigami Color Research Institute).

(3) Weather resistance evaluation Gloss retention is based on Carbon Arc type Sunshine Weather.
Meter device (manufactured by Suga Test Instruments KK, WE-8UN-DC
.

A black test panel was exposed to accelerated exposure (12 minutes of precipitation during 60 minutes of irradiation, black panel temperature was 63±3°C) in a mold) and was evaluated by measuring 60°-60° specular gloss at regular intervals. In addition, chalking resistance was measured according to the chalking start time and the paint film evaluation standards of the Japan Paint Inspection Association.
indicates that no chalking has occurred, and the smaller the value, the greater the degree of chalking.

Table 2 Actual A 53 82 Application B 51 81 The evaluation in Table 2 was performed by applying the melamine alkyd black paint obtained in (1) above to a glass plate to a thickness of approximately 45 μm (as a dry coating film), and achieving gloss (2 (1 ”-2 (1° and 60'-60°
The mirror gloss) was measured using the gloss meter described in (2) above.

Table 3 Actual A 0.56.39.610.411.5 +, 2.
7th B 1.06; [310,111,712,843
, 8 Evaluation method of Table 3; Pigment concentration 2 of 1 grade titanium oxide pigment in vinyl chloride resin powder containing lead-based stabilizer
, 51] HR, kneaded thoroughly using two 6-inch rolls, and then press-molded to create a vinyl chloride sheet. This vinyl chloride sheet was acceleratedly exposed using the carbon arc type sunshine weather meter device described in (3) above, and the color of the sheet was checked at regular intervals using a color difference meter (manufactured by Nippon Heavy Industries, Model N1-101D). -a・1〕
Measure the value and calculate the color difference △ from the initial color based on the value.
E (L+ L,)' + (+)l 112)2+(
a1a2)2) was calculated.

Patent applicant: Ishihara Sangyo Co., Ltd.

Claims (1)

[Claims] On the surface of the lower titanium oxide particles represented by the general formula Ti0x (X; 1.5 to 1.9),
A low-order titanium oxide pigment containing a coating layer of a hydrated oxide or oxide of at least one metal selected from the group consisting of: r, Sn, St), and Ce.