JP2974251B2 - Glazed articles - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a glaze containing mica-like iron oxide and a glazed article having a metallic luster obtained by glazing the surface of an inorganic molded article with the glaze.

Articles glazed with the glaze according to the present invention are useful as tiles and various building materials.

[Conventional technology]

As is well known, a glazed article makes the surface of a base material beautiful and gives durability at the same time, so that it is indispensable to today's daily life as represented by tiles and the like.

Many of the glazed articles used as industrial products are glazed with frit glaze. Therefore, the surface of the glazed article whose surface was decorated had a color obtained by coloring the frit glaze with various pigments or the like.

Examples of using metal powder as a frit glaze include:
Yoichi Aoki, Glazes and Their Pigments, p. 738 (October 15, 1968
(Published by Gihodo Co., Ltd.) describes that ceramics are coated with metal by glaze.

[Problems to be solved by the invention]

However, the above-mentioned metal coating is not for the purpose of decorating the surface of the ceramic, but for giving the function of the metal such as conductivity to the surface of the ceramic.

In addition, even if a variety of glazes that are commercially available are examined today, the one that imparts the luster and aesthetics peculiar to a metal to the surface of a base material has hardly been put to practical use. The reason for this is
When glaze is made by adding metal powder to the glaze,
This is because the metal powder is not oxidized or reacts with the glaze, so that the metal powder cannot be stably present, and the glazed article obtained after glazing can be obtained only with almost no metal luster.

Under such circumstances, if glaze having metallic luster becomes possible, the design of the glaze article will be diversified, and it is clear that its use is enormous.

By the way, synthetic mica-like iron oxides having a large particle size have a metallic luster, so their use as a special pigment as a coloring material for paints and plastics is being planned, but their use as glaze materials is not known at all. .

In view of the above problems, the present inventors have conducted intensive studies on glazes that impart a beautiful metallic glossy surface, and when glazed with frit glaze containing synthetic mica-like iron oxide having metallic luster, The present inventors have found that the glazed article has an excellent design with metallic luster scattered by dispersed iron oxide particles, and completed the present invention.

[Means and actions for solving the problem]

That is, a glazed article provided by the present invention is a glazed article in which a frit glaze containing mica-like iron oxide is glazed directly on the surface of clay-based ceramics, porcelain ceramics, or interior or exterior tiles. It is characterized in that iron oxide is dispersed and has a metallic luster.

 Hereinafter, the present invention will be described in detail.

In the glaze according to the present invention, the frit glaze is not particularly limited, and typically includes a borosilicate frit glaze, and may be either lead-containing or lead-free.

However, since the frit must be a vehicle in which MIO is present as particles with metallic luster as much as possible when heated and glazed, and the stability of the glazed surface is required, its melting point is important for practical use. Yes, often 700-1
Those in the range of 100 ° C, preferably 750 to 1000 ° C are good.

Further, when viewed from the frit chemical composition, since the alkali component tends such as loss of trends or discolored by metallic luster melting reacting the boron component is too large and MIO or MIO, the alkali component M ₂ Preferably, O (M represents Li, Na or K) is in the range of at most 10 wt%, and the boron component is in the range of at most 20 wt% as B ₂ O ₃ .

Next, MIO to be blended with frit glaze is often
It is a synthetic MIO having a hexagonal plate-like metallic luster, and preferably has an average particle size (size of plate surface) of 30 μm or more, particularly 50 to 15 μm.
Large single crystal particles having a size in the range of 0 μm are preferred.

The larger the single crystal, the better the metallic luster is, and the color tone is brown, purple or silver, and the smaller it is, the more reddish brown it is.

The mixing ratio of MIO with respect to the frit is not uniform due to the physical properties of MIO, particularly the particle size, the base material, the physical properties of the frit, or the design and use of the glazed article, but is usually 0.5 to 15 parts per 100 parts by weight of the frit. Parts, preferably 1 to 10 parts by weight.

If the compounding ratio is less than 0.6 parts by weight, the characteristic scattered metallic glossy surface cannot be obtained on the glaze surface due to a small amount of MIO.
If the amount exceeds 15 parts by weight, the glaze surface tends to be rough, and the design property tends to be impaired.

The glaze according to the present invention is basically constituted by including the MIO having a metallic luster in the frit glaze as described above. An appropriate amount of an activator, a viscosity modifier, a dispersant, and the like, as an auxiliary, is usually used in a slurry state with water.

In particular, when a glaze is added to the components of the glaze of the present invention and a coloring agent is added, metallic glossy surfaces having various slightly different colors can be obtained.

As the colorant, a pigment usually used for a colorless and transparent frit glaze can be used.

The substrate on which the glaze according to the present invention is glazed is not particularly limited as long as it is a heat-resistant inorganic molded body, but is usually a clay-based ceramic or porcelain ceramic, and is special as long as the heat resistance permits. It may be a cement molded product.

The shape of the substrate is not particularly limited, but is often a tile or other plate-like article for an inner bag or an outer bag.

The method of glazing the glaze according to the present invention comprises immersing the inorganic molded body of the base material in a slurry of the glaze, or spraying or brushing the slurry of the glaze, glazing by a desired means such as printing, and then drying as desired. And then 700-110
Heat treatment is performed at 0 ° C., preferably 750 to 1000 ° C. for 5 to 60 minutes.

In addition, as an operation of applying a glaze to the surface of the base material, for example, a glaze method in the following manner can be adopted from various aspects.

As a first method, the glaze according to the present invention is applied to the substrate once by glazing, and as a second method, the glaze is glazed, and then a low melting point frit unit constituting the glaze is applied thereon. As a third method, a third method is to apply a single layer of glaze, then apply a single layer of metal powder, and further apply a single layer of low melting point frit thereon to glaze.

The state of the metallic luster on the glazed surface can be appropriately changed by appropriately selecting the above glaze method and by the thickness of the glazed glaze.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples.

Examples 1 to 3 Hexagonal plate-shaped MIO (average particle size 126.3 μm) 5 having silver metallic luster in 100 parts by weight of frit glaze having the following composition
Parts by weight were blended. Then, 0.15 parts by weight of this glaze as a surfactant (Emulgen: Kao Corporation) and CM as a dispersant
Aqueous solution 10 containing 2.0 parts by weight of C (manufactured by Shikoku Chemicals Co., Ltd.)
It was added to 0 parts by weight to prepare a uniform slurry glaze.

This slurry is sprayed with a spray gun to 100 × 30 × 100mm
After drying at 110 ° C. glazed on an inorganic molded plate (tile base) for about 30 minutes, it was fired.

 Table 1 shows the results.

Examples 4-6, Comparative Examples 1-2 leaded frit glaze _{(SiO 2: 42.2wt%, B} 2 O 3: 11.1wt%,
(A ₂ O ₃ : 8.5 wt%, PbO: 27.2 wt%, Na ₂ O: 2.5 wt%) 100 parts by weight were mixed with a predetermined amount of the same MIO as used in Example 1.
Next, the same glazing plate as in Example 1 was prepared by heating each of the glazes at 850 ° C. for 30 minutes. The results shown in Table 2 were obtained.

Examples 7 to 8 The same MIO as in Example 1 was added to 100 parts by weight of the glaze used in Example 3.
5 parts by weight and 2 parts by weight of a colored pigment were blended. Next, the glaze was fired and fired under the same conditions as in Example 3 to produce a glaze molded plate. The results shown in Table 3 were obtained.

[Effect of the Invention] According to the glaze according to the present invention, a glaze having a metallic luster containing a nonmetallic substance called MIO instead of metal powder having low heat resistance can be provided.

When glaze is applied to the surface of the substrate using this glaze, the decorative surface of the glaze has hexagonal plate-like MIO with metallic luster substantially stably existing in the glaze matrix even after the glaze. In addition, it has a unique metallic luster. Such a glazed article has never been known before, and it can be convinced that its design is extremely high.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroaki Kamio 2-4-243 Fukumachi, Nishiyodogawa-ku, Osaka-shi, Nippon Kagaku Kogyo Co., Ltd. Nishiyodogawa Plant (56) References JP-A-1-149975 (JP, A) JP-A-59-232923 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C03C 8/14

Claims (1)

(57) [Claims] 1. A glazed article in which a frit glaze containing mica-like iron oxide is directly glazed on the surface of clay-based ceramics, porcelain ceramics or interior or exterior tiles,
A glazed article characterized in that mica-like iron oxide is dispersed and has a metallic luster.