JP2963487B2 - Glaze and glazed articles - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a glaze comprising a metal powder in a frit glaze and a glazed article glazed with the glaze.

The glaze product glazed with the glaze according to the present invention is a surface-coated acid-resistant product having a metallic luster, and is useful as a tile, various building materials, and the like.

[Prior art] As is well known, glazed articles make the surface of a base material beautiful and give durability at the same time. Therefore, as typified by tiles, it is indispensable for today's daily life. Has become.

Many of the glazed articles used as industrial products are glazed with frit glaze. Therefore, the surface of the glazed article whose surface is decorated has a coloring color obtained by adding various pigments and the like to the frit glaze.

By the way, as a conventional example of using metal powder as a frit glaze, for example, Yoichi Motoki, “Glasses and Their Pigments” 73
On page 8 (October 15, 1968, published by Gihodo Co., Ltd.), it is described that ceramics are coated with a metal by glazing.

[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 imparting 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 that if the glaze contains a metal powder and is glazed, the metal powder often becomes oxidized or reacts with the glaze during firing, and the metal powder cannot be stored stably. This is because the glazed article after firing almost loses the metallic luster and cannot be obtained.

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

In view of the problems described above, the inventors of the present invention have conducted intensive studies on glazes that impart a beautiful metallic glossy surface, and when using glazes containing flaky metal powder in specific frit glazes, With the knowledge that a glazed article having a certain metallic luster and having acid resistance can be obtained,
The present invention has been completed.

[Means for Solving the Problems] That is, the present invention relates to a glaze characterized by comprising a flaky metal powder in a mixed frit glaze of a borosilicate frit glaze and a lead-containing frit glaze. .

Further, the present invention has a metallic luster obtained by applying a glaze containing a flake-like metal powder to a mixed frit glaze of the above borosilicate frit glaze and a lead-containing frit glaze on the surface of the inorganic molded body. Pertains to glazed articles.

 Hereinafter, the present invention will be described in detail.

In the glaze according to the present invention, a mixed frit glaze is used, and a mixture of a borosilicate frit glaze and a lead-containing frit glaze is used as the mixed frit glaze.

The borosilicate frit glaze, one of the components contained in the mixed frit glaze, is preferably a lead-free glaze, and its chemical composition is determined by the glaze method, the flake-like metal powder to be blended, the use of the substrate or the glaze article, and the like. Although it is not uniform, for example, SiO ₂ 45 to 55 wt% in oxide representation, B ₂ O ₃ 15 to 25 w
t%, Al ₂ O _{3 5 to} 15 wt%, MO _{5 to} 15 wt% (M is Ca, Mg or Ba
5) to 20% by weight of R ₂ O (R represents Li, K or Na), and others having a composition in the range of 0 to 15% by weight.

Further, the chemical composition of the lead-containing frit glaze of the other component is not uniform according to the glaze method, the flake-like metal powder to be blended, the substrate, or the use of the glaze article, for example, as described above. SiO ₂ 30~55wt% oxide view, B ₂ O
_{30 to} 15 wt%, Al ₂ O _{3 5 to} 15 wt%, MO 0 to 10 wt% (M is Ca, M
represents g or _{Ba), R 2 O 0~10wt%} (R represents Li, K or Na), PbO 15~55wt%, those having a composition in the range of other 0-5 wt% preferred.

The mixing ratio of the borosilicate frit glaze and the lead-containing frit glaze contained in the mixed frit glaze is 0.1 to 5 parts by weight of the lead-containing frit glaze per 1 part by weight of the borosilicate frit glaze. Preferably, the range of 0.5 to 2 parts by weight is desirable, and if it is less than 0.1 part by weight, the glaze surface is weak in gloss,
If the color tone becomes dark, foaming is likely to occur, and if it exceeds 5 parts by weight, the glazed surface is rough, the gloss is weak, and the acid resistance is undesirably low. Needless to say, such a state of the glaze surface is not limited to the above-mentioned mixing ratio, and it is needless to say that the state changes subtly depending on not only the chemical composition of each glaze, but also the heating temperature, the type of the metal powder and the amount thereof. Thus, in the present invention, by using a mixed frit glaze in which the borosilicate frit glaze and the lead-containing frit glaze are mixed in the above ratio, the flake-like metal powder is stabilized in a uniformly dispersed state. It is possible to obtain a glaze having little gloss on the surface of the glaze, little gloss during baking, gloss and acid resistance.

The composition of the mixed frit glaze is composed of a mixture of the above-described borosilicate frit glaze and a lead-containing frit glaze. In particular, PbO, alkali components, B ₂ O ₃
The content of PbO is 15 to 45 wt%, R2O is _{2 to} 10 wt% (R is Li,
K or Na), and B ₂ O ₃ is preferably in the range of _{3 to} 15 wt%. If the composition deviates from this range, it may be difficult for the flake-shaped metal powder to be present in the frit in a substantially stable state during heating and firing in relation to the flake-shaped metal powder to be blended. For example, in order to add flake-like metal powder to a mixed frit glaze to give a metal-specific luster, the content of alkali components such as Na ₂ O, K ₂ O, Li ₂ O and B ₂ O ₃ must be Those having a composition within the above range are preferred. However, in the case of a frit containing a small amount of these components, the melting temperature of the glaze increases, and the high temperature during firing causes the flake-like metal powder to exceed its heat resistance limit, discoloring and leaving no gloss.

As described above, the melting temperature of the glaze is important in terms of the stability of the metal powder and is closely related to the chemical composition.However, the mixed frit can be glazed in the temperature range of 650 to 1000 ° C. is important. The reason for this is that if the temperature is low, the acid resistance of the glazed surface is poor, while if it is too high, the metal powder discolors or melts and cannot be stably present in the glaze vehicle. Therefore, the temperature is preferably in the range of 750 to 900 ° C.

In addition, leaded glazes generally have a tendency to lack acid resistance, but using a mixed frit glaze combining the above-mentioned leaded glaze and lead-free glaze of the present invention can provide a glaze excellent in acid resistance. it can. If necessary, Al ₂ O ₃ or ZrO ₂
Can be included to improve acid resistance.

Next, examples of the flake-like metal powder to be mixed with the mixed frit glaze include stainless steel powder, powder of a metal such as copper, iron, aluminum, nickel, titanium or zinc, and alloy powder such as bronze powder. Among them, stainless powder is particularly preferable.
Note that these flake-like metal powders may be colored by an interference film obtained by baking and thinly oxidizing the surface.

The flaky metal powder preferably has an average particle diameter of at least 30 μm or more in order to obtain a powder having good color tone, glossiness and dispersibility, and particularly preferably in the range of 30 to 200 μm. If the average particle size is less than 30 μm,
Since the particles become fine particles, the reactivity to the glaze is improved by heating, so that the color becomes darker and the glossiness is weaker.
The average particle size indicates the size of the flake surface of the particles measured by the wet sieving method.

In the present invention, the flake shape is not particularly strictly specified, but refers to a flake shape or a plate shape observed with the naked eye or a microscope. The shape of the flake surface may be any of an irregular shape and a regular shape such as a hexagonal plate shape. In many cases, the aspect ratio is in the range of 1:10 to 1: 100.

The mixing ratio of the flaky metal powder to the mixed frit glaze is not uniform depending on the type of the flaky metal powder to be blended, the metal or the use of the glazed article, etc. The amount of the metal powder is preferably 0.1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight. If the amount is less than 0.1 part by weight, the amount of flake-like metal powder is so small that a metallic glossy surface cannot be obtained on the surface of the glazed article, and if it exceeds 10 parts by weight, the metal powder comes out on the glazed surface and the surface becomes rough. State, the firing temperature rises,
Conditions such as extension of the firing time are required, which is economically disadvantageous and not preferable.

The glaze according to the present invention is basically composed of the above-mentioned mixed frit glaze and flake-like metal powder. However, when glazing the base material surface, various kinds of surfactants and viscosity adjustments are required as required. A mixture of an auxiliary agent, an organic or inorganic dispersant, a colorant, and the like as an auxiliary is usually used in a state of slurry 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, a glazed article having various colors and having a metallic luster can be obtained. As a coloring agent,
Organic or inorganic pigments commonly used for colorless and transparent frit glazes can be used.

Further, the amount of the colorant added is not uniform depending on the type of the colorant and the flake-like metal powder, the use of the substrate or the glazed article, etc., but usually 1 to 5 parts by weight based on 100 parts by weight of the mixed frit glaze. And particularly preferably in the range of 1 to 3 parts by weight.

The substrate on which the glaze according to the present invention is applied is not particularly limited as long as it is an inorganic molded body, but in many cases, a heat-resistant molded body such as ceramics is preferred. In addition, as long as the strength does not substantially deteriorate at the heating temperature, it may be a special cement molded product.

Next, the method for glazing the glaze according to the present invention is to immerse the inorganic molded body of the base material in a slurry of the glaze, or spray or glaze the slurry of the glaze, and perform glaze by a desired means such as printing. , Dry if necessary, then
Heating is performed at a firing temperature of 1000 ° C. or lower, preferably 750 to 900 ° C., and heat treatment is performed at the firing temperature for 5 to 30 minutes.

Further, as an operation of applying a glaze to the surface of the base material, from the other side, for example, a glaze method in the following mode can be adopted.

As a first method, the glaze according to the present invention is applied to the base material once by glazing, and as a second method, the glaze is glazed, and then the mixed frit glaze constituting the glaze is glazed thereon. As a third method, there is a third method in which a single glazing is applied, a flake-like metal powder is applied, and a mixed frit glaze is applied thereon.

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 5 and Comparative Examples 1 to 5 The borosilicate frit glazes A, B, and C and the lead-containing frit glazes X and Y having the compositions shown in Table 1 below are shown in Table 2 100 parts by weight of the mixed frit glaze blended with the above, and a glaze consisting of 5 parts by weight of stainless flake (produced by Kawatetsu Techno Research Co., Ltd.) having an average particle diameter of 150 μm as a flake-like metal powder, and a surfactant (Emulgen: manufactured by Kao Corporation) 0.15 parts by weight, dispersant (CMC: manufactured by Shikoku Chemicals) 2
It was added to 100 parts by weight of an aqueous solution containing parts by weight to prepare a uniform slurry-like glaze.

Then, this slurry was sprayed with a spray gun to 100 × 1
After glazing on a 00x3mm inorganic molded plate (tile base), 110
C. for about 30 minutes and then fired to obtain a glazed article.
Table 2 shows the results.

Also, as comparative examples, each plain frit glaze A, B, C,
Each glazed article was obtained using X and Y in the same manner as described above. The results are shown in Table 2.

(Note 1) The gloss was evaluated by visually observing the appearance of the glaze surface. (The same shall apply hereinafter.) Excellent: The glaze surface is uniform and has excellent metallic luster.

Good: The glaze surface is uniform, but lacks some metallic luster.

Inferior… The glaze surface is discolored and has no metallic luster.

(Note 2) Acid resistance is as follows: hydrochloric acid solution (10W / V%)
Was dropped and left for a whole day and night, and the degree of discoloration of the glaze surface was visually observed and evaluated.

Excellent: The glaze surface is in a state that hardly discolors to hydrochloric acid.

 Good: Some discoloration is recognized.

 Bad: Discoloration is remarkable.

The glazed articles obtained using the borosilicate frit glazes of Comparative Examples 1 to 3 retain glossiness but react with the glaze to have many portions where the color tone turns blackish. Glazes A and B foamed when the glazed film was thickly applied. Glaze C showed roughness on the glazed surface.

Glazed articles obtained using the lead-containing frit glazes of Comparative Examples 4 and 5 are slightly inferior in acid resistance but excellent in glossiness.
Glaze X had low hardness, and glaze Y had a large golden luster with roughness on the glazed surface.

Examples 6 to 9 and Comparative Examples 6, 7 The same stainless steel flakes as in Example 1 were used as the flake-like metal powder, and a test was conducted to examine the change in the state of the glazed surface due to the change in the mixing ratio of the glaze.

Example 1 was obtained by using a mixed frit glaze in which borosilicate frit glaze A and lead-containing frit glaze Y having the compositions shown in Table 1 were mixed at various ratios shown in Table 3.
Each glazed article was obtained in the same manner as described above. Table 3 shows the results.

From the results shown in Table 3, the mixed frit glaze was found to be glaze A: Y
In the case of having a composition of = 1: 1, the best results were obtained in consideration of the glossiness, the state of the glaze surface, and the hardness.

Examples 10 to 12 In the blended components of the mixed frit glazes D, E, and F of Examples 1 to 3, a colored pigment was further added at 2% by weight based on the glaze. An inorganic molded plate having various colors and a metallic luster was obtained.

 Table 4 shows the results.

By adding a colored pigment, it was possible to obtain a glaze surface having various colors and a metallic luster.

Example 13 The glaze E of Example 2 was used for the mixed frit glaze, the stainless flakes were used for the flaky metal powder, and the metallic luster was obtained in the same manner as in Example 2 except that the firing temperature was variously changed. An inorganic molded plate was obtained.

 Table 6 shows the results.

Example 14 The same method as in Example 2 was carried out except that the glaze E of Example 2 was used as the mixed frit glaze, stainless flake was used as the flake-like metal powder, and the amount of stainless flake was varied. A glossy inorganic molded plate was obtained.

 Table 7 shows the results.

From the results shown in Table 7, when the flake-form metal powder is added in an amount of 8% by weight or more with respect to the glaze, roughness is observed on the glaze surface. This is because the metal powder appears on the surface of the glaze as the amount added increases. When the addition amount becomes 16% by weight, the glaze surface becomes considerably rough.

Example 15 An inorganic molded plate having a metallic luster was obtained in the same manner as in Example 2, except that stainless flakes colored by the following firing were used instead of the stainless flakes of the flaky metal powder used in Example 2. . Table 8 shows the results.

From the results shown in Table 8, the formation of the oxide film on the surface of the metal powder by firing at 300 ° C. or less did not show a significant difference from the solid product.

Discoloration of the surface of the metal powder is observed from the baked product at 400 ° C. or higher, and the color tone changes as the calcination temperature increases in the order of gold-blue-black. The gloss after firing the glaze is good, and the color shifts from silver to gold as the product becomes hotter.

The products baked at 600 ° C and 700 ° C do not show strong glossiness in appearance, but glossiness remains on the glaze surface after firing. This is because the discolored part of the metal surface reacts easily with the glaze, and the undiscolored part is difficult to react, so glossiness remains, which also requires a certain size of the particle size. It may be 30 μm or more.

[Effects of the Invention] As described above, if the mixed frit glaze of the borosilicate-based frit glaze and the lead-containing frit glaze of the present invention and the glaze containing the flake-shaped metal powder are used, the flakes are obtained by firing after glazing. The metallic powder does not react with the mixed frit glaze, and a glazed article having a metallic luster and having acid resistance can be obtained.

The glazed article of the present invention is a valuable product having a metallic luster and whose surface is decorated, and is extremely useful as a tile, various building materials, and the like.

Continuing from the front page (72) Inventor Hiroaki Kamio 3-2-43 Fukumachi, Nishiyodogawa-ku, Osaka-shi, Osaka Japan Chemical Industry Co., Ltd. Nishiyodogawa Plant (72) Inventor Yasushi Nakayama 2-5-1 Minamisuna, Koto-ku, Tokyo (72) Inventor: Yoshikazu Yokoi, 3221 Kasahara-cho, Toki-gun, Gifu Prefecture (58) Field surveyed (Int.Cl. ⁶ , DB name) C03C 8/00-8/24 C03C 14 / 00

Claims (4)

(57) [Claims] 1. A glaze characterized in that a flaky metal powder is contained in a mixed frit glaze of a borosilicate frit glaze and a lead-containing frit glaze. 2. The glaze according to claim 1, wherein the mixed frit glaze can be glazed at a temperature of 650 to 1000 ° C. 3. The glaze according to claim 1, wherein the flake-like metal powder is a stainless steel powder having an average particle diameter of at least 30 μm. 4. A glazed article having a metallic luster obtained by glazing the surface of an inorganic molded article with the glaze according to claim 1.