JPH03279237A - Glaze and glazed article - Google Patents
Glaze and glazed articleInfo
- Publication number
- JPH03279237A JPH03279237A JP7681190A JP7681190A JPH03279237A JP H03279237 A JPH03279237 A JP H03279237A JP 7681190 A JP7681190 A JP 7681190A JP 7681190 A JP7681190 A JP 7681190A JP H03279237 A JPH03279237 A JP H03279237A
- Authority
- JP
- Japan
- Prior art keywords
- glaze
- glazed
- frit
- metal powder
- mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000002932 luster Substances 0.000 claims abstract description 26
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 239000002253 acid Substances 0.000 abstract description 11
- 230000003796 beauty Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 238000010304 firing Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000003086 colorant Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000049 pigment Substances 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- -1 titanium or zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、フリット釉薬に金属粉末を含有してなる釉薬
及びこの釉薬で施釉した施釉物品に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a glaze comprising a frit glaze containing metal powder and a glazed article glazed with this glaze.
本発明に係る釉薬で施釉した釉薬物品は、金属光沢を有
する表面化粧された耐酸性の製品であり、タイルや各種
の建築材料等として有用である。A glazed product coated with the glaze according to the present invention is an acid-resistant product with a surface decorated with metallic luster, and is useful as tiles and various building materials.
［従来の技術］
周知の様に、施釉物品は基材表面を化粧して美感と同時
に耐久性を与えることから、タイルなどで代表されるよ
うに、今日の日常生活に欠くことができないものとなっ
ている。[Prior Art] As is well known, glazed articles are indispensable in today's daily life, as exemplified by tiles, because they decorate the surface of the base material and give it both beauty and durability. It has become.
そして、工業製品として用いられている施釉物品の多く
は、フリット釉薬によって施釉されたものが使用されて
いる。したがって、表面化粧された施釉物品は、その表
面はフリット釉薬に各種の顔料等を含有させることによ
り着色された彩色を有するものである。Many of the glazed articles used as industrial products are glazed with a frit glaze. Therefore, the surface of a glazed article is colored by incorporating various pigments into the frit glaze.
ところで、フリット釉薬として金属粉末を使用する従来
の例としては、例えば素木洋−著「釉とその顔料」７３
８頁（昭和４３年１０月１５日、■技報堂発行）に、セ
ラミックスに施釉により金属被覆することが記載されて
いる。By the way, as a conventional example of using metal powder as a frit glaze, for example, Hiroshi Motoki, "Glaze and Its Pigments" 73
On page 8 (October 15, 1963, published by ■Gihodo), it is described that ceramics are coated with metal by glazing.
［発明が解決しようとする課題］
しかしながら、上記の金属被覆はセラミックスの表面を
彩飾する目的ではな（、導電性などの金属がもつ機能を
セラミックスの表面に付与させることにある。[Problems to be Solved by the Invention] However, the purpose of the above-mentioned metal coating is not to decorate the surface of the ceramic (but to impart functions that metal has, such as conductivity, to the surface of the ceramic).
また、今日、市販されている多様な釉薬を調べてみても
、基材表面に金属特有の光沢と美感を付与させるものは
殆んど実用化されていない現状である。この理由として
は、釉薬に金属粉末を含有させて施釉すると、焼成の際
、多（の場合、金属粉末が酸化したり、あるいは釉薬と
反応したりして金属粉末を安定に保存することができず
、焼成後の施釉物品は殆んど金属光沢を失ったものきり
得られないからである。Furthermore, even if we examine the various glazes that are commercially available today, there are hardly any glazes that can give the surface of a base material the luster and beauty that are unique to metals and have been put to practical use. The reason for this is that if the glaze contains metal powder and is applied, the metal powder may oxidize or react with the glaze during firing, making it difficult to store the metal powder stably. First, the glazed article after firing has almost no metallic luster and cannot be obtained.
この様な現状において、金属光沢を有する施釉が可能と
なれば、施釉物品の意匠性が多様になり、その用途は多
大であることは明らかである。Under these current circumstances, it is clear that if it were possible to apply a glaze with metallic luster, the designs of glazed articles would be diverse and their uses would be wide-ranging.
本発明者らは叙上の問題点を鑑み、美感のある金属光沢
面を付与する釉薬について鋭意研究したところ、特定の
フリット釉薬にフレーク状の金属粉末を含有させた釉薬
を使用すると、美感のある金属光沢を有し、かつ耐酸性
を有する施釉物品を得ることができることを知見し、本
発明を完成した。In view of the above-mentioned problems, the present inventors conducted intensive research on glazes that give an aesthetically pleasing metallic luster surface, and found that when a glaze containing flaky metal powder is used in a specific frit glaze, the aesthetic appearance is improved. The present invention was completed based on the discovery that it is possible to obtain a glazed article having a certain metallic luster and acid resistance.
［課題を解決するための手段］
すなわち、本発明は、ホウ珪酸塩系フリット釉薬と台船
系フリット釉薬との混合フリット釉薬にフレーク状金属
粉末を含有してなることを特徴とする釉薬に係る。[Means for Solving the Problems] That is, the present invention relates to a glaze characterized by containing flaky metal powder in a mixed frit glaze of a borosilicate-based frit glaze and a barge-based frit glaze. .
更に、本発明は、無機質成形体の表面に、上記のホウ珪
酸塩系フリット釉薬と台船系フリット釉薬との混合フリ
ット釉薬にフレーク状金属粉末を含有する釉薬を施釉し
てなる金属光沢を有する施釉物品に係る。Furthermore, the present invention provides a metallic luster obtained by applying a glaze containing flaky metal powder to a mixed frit glaze of the above-mentioned borosilicate-based frit glaze and barge-based frit glaze on the surface of the inorganic molded body. Pertains to glazed articles.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に係る釉薬においては混合フリット釉薬が用いら
れ、該混合フリット釉薬にはホウ珪酸塩系フリット釉薬
と台船系フリット釉薬との混合物が使用される。In the glaze according to the present invention, a mixed frit glaze is used, and the mixed frit glaze is a mixture of a borosilicate-based frit glaze and a barge-based frit glaze.
この混合フリット釉薬に含有される一方の成分のホウ珪
酸塩系フリット釉薬は、無鉛のものが好ましく、その化
学組成は、施釉方法や配合されるフレーク状金属粉末、
基材あるいは施釉物品の用途等により一様ではないが、
例えば酸化物表示でＳｉｎｇ ４５〜５５ｗｔ％、Ｂｚ
Ｏｉ１５〜２５ｗｔ％、ＡＩ！″２０３５〜１５ｗｔ％
、ＭＯ５〜１５ｗｔ％ （ＭはＣａ、 Ｍｇ又はＢａを
表わす）、Ｒ２Ｏ５〜２０ｗｔ％（ＲはＬｉ、 Ｋ又は
Ｎａを表わす）、その他０”−１５ｗｔ％の範囲にある
組成を有するものが好ましい。The borosilicate frit glaze, which is one of the components contained in this mixed frit glaze, is preferably lead-free, and its chemical composition is determined by the glazing method, the flaky metal powder mixed,
Although it varies depending on the base material or the use of the glazed article,
For example, Sing 45-55wt% in oxide display, Bz
Oi15-25wt%, AI! ″2035~15wt%
, MO5 to 15 wt% (M represents Ca, Mg, or Ba), R2O5 to 20 wt% (R represents Li, K, or Na), and others having a composition in the range of 0'' to 15 wt%.
また、他方の成分の台船系フリット釉薬は、その化学組
成は、上記と同様に、施釉方法や配合されるフレーク状
金属粉末、基材あるいは施釉物品の用途等により一様で
はないが、例えば酸化物表示でＳｉ０□３０〜５５ｗｔ
％、ＢｚＯａ Ｏ〜１５ｗｔ％、ＡｆｚＯｓ５〜１５ｗ
ｔ％、ＭＯＯ〜１０ｗｔ％ （ＭはＣａ、 Ｍｇ又は
Ｂａを表わす）、Ｒ２００〜１０ｗｔ％（ＲはＬｉ、
Ｋ又はＮａを表わす） 、Ｐｂ０１５〜５５ｗｔ％、そ
の他Ｏ〜５ｗｔ％の範囲にある組成を有するものが好ま
しい。The chemical composition of the other component, the barge-based frit glaze, varies depending on the glazing method, the flake metal powder mixed, the base material, or the use of the glazed article, etc., as described above, but, for example, Si0□30~55wt in oxide display
%, BzOa O~15wt%, AfzOs5~15w
t%, MOO~10wt% (M represents Ca, Mg or Ba), R200~10wt% (R is Li,
(representing K or Na), Pb015 to 55 wt%, and others preferably having a composition in the range of O to 5 wt%.
また、混合フリット釉薬に含有されるホウ珪酸塩系フリ
ット釉薬と台船系フリット釉薬との混合割合は、ホウ珪
酸塩系フリット釉薬１重量部に対して台船系フリット釉
薬０．１〜５重量部、好ましくは０．５〜２重量部の範
囲が望ましく、０．１重量部未満では施釉表面の光沢が
弱（、色調が黒っぽ（なり、発泡が起こりやす（、また
５重量部を越えると施釉表面がザラツキ、光沢が・弱（
、耐酸性が低（なり好ましくない。尤も、このような施
釉表面の状態は、上記の混合比に限らず、各釉薬の化学
組成は勿論、加熱温度、金属粉末の種類とその配合量等
によって微妙に変化することは言うまでもない。このよ
うに、本発明においては、ホウ珪酸塩系フリット釉薬と
台船系フリット釉薬とを上記の割合に混合した混合フリ
ット釉薬を用いることにより、フレーク状金属粉末を均
一に分散した状態で安定させ、焼成時の発泡がほとんど
なく、施釉表面のザラツキも少な（、光沢および耐酸性
を有する釉薬を得ることができる。In addition, the mixing ratio of the borosilicate frit glaze and the barge frit glaze contained in the mixed frit glaze is 0.1 to 5 parts by weight of the barge frit glaze to 1 part by weight of the borosilicate frit glaze. If the amount is less than 0.1 part by weight, the glazed surface will have a weak luster, the color tone will be dark, and foaming will occur easily. If it exceeds the limit, the glazed surface will be rough and the gloss will be weak (
However, the condition of the glazed surface is not limited to the above mixing ratio, but also depends on the chemical composition of each glaze, as well as the heating temperature, the type and amount of metal powder mixed, etc. Needless to say, there will be slight changes.As described above, in the present invention, by using a mixed frit glaze in which a borosilicate-based frit glaze and a barge-based frit glaze are mixed in the above ratio, flaky metal powder It is possible to obtain a glaze that is stable in a uniformly dispersed state, has almost no foaming during firing, and has less roughness on the glazed surface (and has gloss and acid resistance).
また、混合フリット釉薬の組成は、上記のホウ珪酸塩系
フリット釉薬と台船系フリット釉薬との混合組成からな
るが、特にこの混合組成中のｐｂｏ 、アルカリ成分、
Ｂ２Ｏ３の含有量は、ＰｂＯ１５〜４５ｗｔ％、Ｒ２
０２〜１０ｗｔ％（ＲはＬｉ、 Ｋ又はＮａを表わす）
、８２０．３〜１５ｗｔ％の範囲にあることが好まし
い。この範囲の組成からはずれると、配合されるフレー
ク状金属粉末との関係で、加熱焼成の際、フレーク状金
属粉末がフリット中に実質的に安定な状態で存在するこ
とが難しくなる場合が生ずる。例えば、フレーク状金属
粉末を混合フリット釉薬に添加して金属特有の光沢を出
そうとするには、Ｎａ２１． Ｒ２０，ＬｉｚＯ等のア
ルカリ成分およびＢ２Ｏ３の含有量は上記の範囲内の組
成のものが好ましい。しかし、これらの成分が少ないフ
リットの場合、釉薬の溶融温度が高くなり、焼成時の高
熱によりフレーク状金属粉末が耐熱の限度をこえるため
変色し光沢を残さな（なる。The composition of the mixed frit glaze is a mixture of the above-mentioned borosilicate-based frit glaze and barge-based frit glaze, and in particular, pbo, alkali components,
The content of B2O3 is PbO15-45wt%, R2
02-10wt% (R represents Li, K or Na)
, preferably in the range of 820.3 to 15 wt%. If the composition deviates from this range, it may become difficult for the flaky metal powder to exist in a substantially stable state in the frit during heating and firing due to the relationship with the flaky metal powder blended. For example, if you want to add flaky metal powder to a mixed frit glaze to give it a metallic luster, Na21. The content of alkaline components such as R20 and LizO and B2O3 is preferably within the above range. However, in the case of a frit containing few of these components, the melting temperature of the glaze becomes high, and the flaky metal powder exceeds its heat resistance limit due to the high heat during firing, resulting in discoloration and loss of luster.
この様に釉薬の溶融温度は、金属粉末の安定性に関し、
化学組成と密接な相関のもとに重要なことであるが、混
合フリットが６５０〜１０００℃の温度範囲で施釉でき
るものであることが重要である。In this way, the melting temperature of the glaze is related to the stability of the metal powder.
Closely related to the chemical composition, it is important that the mixed frit can be glazed in the temperature range of 650 to 1000C.
この理由は、その温度が低いと施釉面の耐酸性に欠け、
一方高すぎると金属粉末が変色ないし溶けて釉ビヒクル
中に安定して存在できな（なるからである。従って、好
ましくは７５０〜９００℃の範囲がよい。The reason for this is that when the temperature is low, the glazed surface lacks acid resistance.
On the other hand, if the temperature is too high, the metal powder will discolor or melt and cannot stably exist in the glaze vehicle. Therefore, the temperature is preferably in the range of 750 to 900°C.
さらに、−船釣には有鉛釉薬は耐酸性に欠ける傾向にあ
るが、本発明の前記の有鉛釉薬と無鉛釉薬を組み合わせ
た混合フリット釉薬を用いると、耐酸性に優れた釉薬を
得ることができる。なお、必要に応じ、Ａｊ！ｇｏｓや
ＺｒＯ２の成分を含有させて耐酸性を改善させることも
できる。Furthermore, for boat fishing, leaded glazes tend to lack acid resistance, but by using the mixed frit glaze of the present invention, which is a combination of the leaded glaze and lead-free glaze, a glaze with excellent acid resistance can be obtained. I can do it. In addition, if necessary, Aj! Acid resistance can also be improved by incorporating components such as gos and ZrO2.
次に、かかる混合フリット釉薬に配合されるフレーク状
金属粉末としては、例えばステンレス粉、その他に銅、
鉄、アルミニウム、ニッケル。Next, the flaky metal powder to be added to the mixed frit glaze includes, for example, stainless steel powder, copper,
iron, aluminum, nickel.
チタン又は亜鉛等の金属の粉末、ブロンズパウダー等の
合金粉末などが挙げられるが、それらの中で特にステン
レス粉が好ましい。なお、これらのフレーク状金属粉末
は、焼成により、その表面を薄く酸化して得られる干渉
膜により着色されたものであってもよい。Examples include powders of metals such as titanium or zinc, and alloy powders such as bronze powders, among which stainless steel powders are particularly preferred. Note that these flaky metal powders may be colored with an interference film obtained by thinly oxidizing the surface of the powder by firing.
また、フレーク状金属粉末は、その粒径は平均粒子径が
少なくとも３０ｐｍ以上のものが、色調、光沢性１分散
性のよいものを得るのに好ましく、特に３０〜２００ｐ
ｍの範囲のものが好ましい。平均粒子径が３０ｐｍ未満
では、微粒子となるために加熱により釉薬に対しての反
応性がよくなるため黒っぽい色調となり、光沢性も弱（
なる。なお、平均粒子径は湿式篩法で測定した粒子のフ
レーク面の大きさを示す。In addition, the flaky metal powder preferably has an average particle size of at least 30 pm or more in order to obtain good color tone, gloss, and dispersibility, particularly 30 to 200 pm.
A range of m is preferred. If the average particle size is less than 30 pm, the particles become fine and have good reactivity with the glaze when heated, resulting in a dark tone and poor gloss (
Become. Note that the average particle diameter indicates the size of the flake surface of particles measured by a wet sieving method.
なお、本発明でフレーク状とは、特に特定する程の厳密
なものではなく、肉眼又は顕微鏡でフレーク状又は板状
に観察されるものをいう。フレーク面の形状は不定形又
は六角板状などの定形のいずれであってもよい。多くの
場合、アスペクト比１：１０〜１：１００の範囲のもの
である。Incidentally, in the present invention, the term "flake-like" is not strictly specified, but refers to something that is observed as a flake-like or plate-like shape with the naked eye or under a microscope. The shape of the flake surface may be either irregular or regular, such as a hexagonal plate shape. In many cases, the aspect ratio is in the range of 1:10 to 1:100.
混合フリット釉薬に対するフレーク状金属粉末の配合割
合は、配合されるフレーク状金属粉末の種類、基材ある
いは施釉物品の用途等により一様ではないが、通常は混
合フリット釉薬１００重量部に対してフレーク状金属粉
末を０．１〜１０重量部、特に１〜５重量部の範囲が好
ましい。０．１重量部未満ではフレーク状金属粉末が少
ないためにそれに基づき施釉物品の表面に金属光沢面が
得られず、また１０重量部を越えてると施釉表面に金属
粉末が出てくるためにザラついた状態となり、焼成温度
の上昇、焼成時間の延長等の条件が必要となるので経済
的に不利となり好ましくない。The blending ratio of flaky metal powder to the mixed frit glaze varies depending on the type of flaky metal powder mixed, the base material, the use of the glazed article, etc., but it is usually a proportion of flakes to 100 parts by weight of the mixed frit glaze. The amount of the metal powder is preferably 0.1 to 10 parts by weight, particularly 1 to 5 parts by weight. If it is less than 0.1 part by weight, the amount of flaky metal powder will be small and the surface of the glazed product will not have a metallic luster, and if it exceeds 10 parts by weight, the metal powder will come out on the glazed surface and it will be rough. This is not preferable because it is economically disadvantageous because conditions such as raising the firing temperature and extending the firing time are required.
本発明に係る釉薬は、上記の混合フリット釉薬とフレー
ク状金属粉末とにより基本的に構成されるものであるが
、基材表面に施釉するに当り、必要に応じ各種の界面活
性剤、粘度調整剤、有機又は無機系の分散剤１着色剤等
を助剤として配合したものを、通常は水でスラリー化し
た状態で使用する。The glaze according to the present invention is basically composed of the above mixed frit glaze and flaky metal powder, but when applying the glaze to the surface of the base material, various surfactants and viscosity adjustment may be used as necessary. A dispersant, an organic or inorganic dispersant 1, a coloring agent, etc. are blended as auxiliary agents, and are usually used in the form of a slurry with water.
特に、本発明の釉薬の配合成分の中に、着色剤を添加し
て施釉すると、種々の着色を呈すると共に金属光沢を有
する施釉物品を得ることができる。着色剤としては、無
色透明フリット釉薬に通常使用されている有機又は無機
系の顔料を用いることができる。In particular, when a coloring agent is added to the ingredients of the glaze of the present invention for glazing, glazed articles exhibiting various colors and having metallic luster can be obtained. As the colorant, organic or inorganic pigments commonly used in colorless transparent frit glazes can be used.
また、着色剤の添加量は、着色剤およびフレーり状金属
粉末の種類、基材あるいは施釉物品の用途等により一様
ではないが、通常は混合フリット釉薬１００重量部に対
して１〜５重量部、特に１〜３重量部の範囲が好ましい
。The amount of colorant added varies depending on the type of colorant and flaky metal powder, the use of the base material or the glazed article, etc., but it is usually 1 to 5 parts by weight per 100 parts by weight of the mixed frit glaze. parts, especially in the range from 1 to 3 parts by weight.
本発明に係る釉薬を施釉する基材は無機質成形体であれ
ば、特に限定することはないが、多くの場合セラミック
スなどの耐熱成形体が好ましい。また、加熱温度で強度
劣化が実質的に生じないようなものであれば、特殊セメ
ント成形品であって差支えない。The base material to 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 most cases, heat-resistant molded bodies such as ceramics are preferred. In addition, any special cement molded product may be used as long as it does not substantially deteriorate in strength at heating temperatures.
次に、本発明に係る釉薬を施釉する方法は、基材の無機
質成形体を釉薬のスラリーに浸漬させるか、釉薬のスラ
リーをスプレー掛は或いははけ塗り、印刷などの所望の
手段で施釉した後、必要に応じて乾燥を施し、次いで１
０００℃以下、好ましくは７５０〜９００℃の焼成温度
で加熱し、その焼成温度で５〜３０分間加熱処理する。Next, the method of applying the glaze according to the present invention is to immerse the inorganic molded body of the base material in a glaze slurry, or apply the glaze slurry by a desired method such as spraying, brushing, printing, etc. After that, dry as necessary, then 1
000°C or less, preferably at a firing temperature of 750 to 900°C, and heat-treated at that firing temperature for 5 to 30 minutes.
また、基材の表面に釉薬を施こす操作としては、他面か
ら見れば、例えば、次のような態様の施釉方法を採るこ
とができる。From another perspective, the following glazing method can be used to apply the glaze to the surface of the base material.
第１の方法としては、本発明に係る釉薬を基材に一度掛
けにより施釉する方法、第２の方法としては、釉薬を施
釉後その上に該釉薬を構成する混合フリット釉薬単味を
施釉する二度掛けによる方法、第３の方法としては単味
を施釉後、フレーク状金属粉末単味を掛け、更にその上
に混合フリット釉薬単味を施釉する三度掛けによる方法
等が挙げられる。The first method is to apply the glaze according to the present invention to the base material once, and the second method is to apply the glaze and then apply a mixed frit glaze component constituting the glaze on top of the glaze. A third method is to apply a single layer of glaze, then apply a flaky metal powder layer, and then glaze a mixed frit glaze layer three times.
上記の施釉方法を適当に選択することにより、また施釉
された釉薬の厚さにより、施釉面の金属光沢の状態を適
宜変化させることができる。By appropriately selecting the above-mentioned glazing method and by changing the thickness of the applied glaze, the state of the metallic luster on the glazed surface can be changed as appropriate.
［実施例］ 以下、実施例を示し本発明をさらに具体的に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１〜５および比較例１〜５
下記の第１表に示す組成を有するホウ珪酸塩系フリット
釉薬Ａ、Ｂ、Ｃと台船系フリット釉薬Ｘ、Ｙとを、第２
表に示す割合で配合した混合フリット釉薬１００重量部
と、フレーク状金属粉末として平均粒子径１５０１ｉｍ
のステンレスフレーク（川鉄テクノリサーチ株式会社製
）５重量部よりなる釉薬を、界面活性剤（エマルゲン：
花王株式％式％：
株式会社製）２重量部を含有する水溶液１００重量部に
添加して均一なスラリー状の釉薬を調製した。Examples 1 to 5 and Comparative Examples 1 to 5 Borosilicate-based frit glazes A, B, and C having the compositions shown in Table 1 below and barge-based frit glazes X and Y were mixed into a second
100 parts by weight of mixed frit glaze mixed in the ratio shown in the table and an average particle size of 1501 mm as flaky metal powder.
A glaze consisting of 5 parts by weight of stainless steel flakes (manufactured by Kawatetsu Techno Research Co., Ltd.) was mixed with a surfactant (Emulgen:
A uniform slurry-like glaze was prepared by adding it to 100 parts by weight of an aqueous solution containing 2 parts by weight of Kao Stock (% formula %: manufactured by Kao Corporation).
次いで、このスラリーをスプレーガンにより、１００Ｘ
１００Ｘ ３ ｍｍの無機成形板（タイル素地）に
施釉した後、１１０℃で約３０分間乾燥し、次いで焼成
して施釉物品を得た。その結果を第２表に示す。Next, this slurry was sprayed at 100X using a spray gun.
After glazing a 100×3 mm inorganic shaped board (tile base), it was dried at 110° C. for about 30 minutes and then fired to obtain a glazed article. The results are shown in Table 2.
また、比較例として各々の単味のフリット釉薬Ａ、Ｂ、
Ｃ，Ｘ、Ｙを用いて、上記と同様の方法により各々の施
釉物品を得た。その結果を第２表に併記する。In addition, as comparative examples, each plain frit glaze A, B,
Using C, X, and Y, each glazed article was obtained in the same manner as above. The results are also listed in Table 2.
（注１）光沢性は施釉表面の外観を目視により観察して
評価した。（以下同様とする）
優・・・施釉表面が均一で優れた金属光沢を有した状態
にあるもの。(Note 1) Glossiness was evaluated by visually observing the appearance of the glazed surface. (The same shall apply hereinafter) Excellent: The glazed surface is uniform and has an excellent metallic luster.
良・・・施釉表面が均一であるが、やや金属光沢性を欠
く状態にあるもの。Good: The glazed surface is uniform, but it lacks metallic luster.
不良・・・施釉表面が変色し、金属光沢を有していない
状態にあるもの。Defective: The glazed surface is discolored and does not have metallic luster.
（注２）耐酸性は、施釉焼成品に塩酸溶液（１０■ハ％
）を滴下し、−昼夜放置し、その施釉表面の変色度合い
を目視により観察して評価した。(Note 2) Acid resistance is based on hydrochloric acid solution (10%) applied to glazed fired products.
) was dropped and left to stand day and night, and the degree of discoloration of the glazed surface was visually observed and evaluated.
優・・・施釉表面が塩酸に対して殆ど変色しない状態に
あるもの。Excellent: The glazed surface hardly changes color when exposed to hydrochloric acid.
良・・・やや変色が認められるもの。Good: Slight discoloration is observed.
不良・・・変色が著しいもの。Defective: Items with significant discoloration.
比較例１〜３のホウ珪酸塩系フリット釉薬を用いて得ら
れた施釉物品は、光沢性は残るが釉薬と反応して色調は
黒っぽく変色する部分が多（なる。また、釉薬Ａ、Ｂは
施釉膜を厚（掛けると発泡した。釉薬Ｃは施釉表面にザ
ラツキが表れた。The glazed articles obtained using the borosilicate frit glazes of Comparative Examples 1 to 3 remain glossy, but there are many parts where the color changes to black due to reaction with the glaze. When the glazed film was applied thickly, it foamed.Glaze C showed roughness on the glazed surface.
比較例４，５の台船系フリット釉薬を用いて得られた施
釉物品は、耐酸性に若干劣るが、光沢性は優れている。The glazed articles obtained using the barge-type frit glazes of Comparative Examples 4 and 5 were slightly inferior in acid resistance, but excellent in gloss.
また、釉薬Ｘは硬度が弱く、釉薬Ｙは施釉表面にザラツ
キが表れた金色系の光沢が多（なった。Furthermore, glaze X had low hardness, and glaze Y had a golden luster with roughness on the glazed surface.
実施例６〜９および比較例６，７
フレーク状金属粉末には実施例１と同様のステンレスフ
レークを用いて、釉薬の混合割合の変化による施釉表面
の状態の変化を調べる試験を行なった。Examples 6 to 9 and Comparative Examples 6 and 7 Using the same stainless steel flakes as in Example 1 as the flaky metal powder, a test was conducted to examine changes in the state of the glazed surface due to changes in the mixing ratio of the glaze.
前記第１表に示す組成を有するホウ珪酸塩系フリット釉
薬Ａと台船系フリット釉薬Ｙとを、第３表に示す各種の
割合で配合した混合フリット釉薬を用いて、実施例１と
同様の方法により各々の施釉物品を得た。その結果を第
３表に示す。Using a mixed frit glaze in which borosilicate-based frit glaze A and barge-based frit glaze Y having the compositions shown in Table 1 were mixed in various proportions shown in Table 3, the same process as in Example 1 was carried out. Each glazed article was obtained by the method. The results are shown in Table 3.
第
３
表
第３表に示す結果から、混合フリット釉薬が釉薬Ａ：Ｙ
＝１：１の組成を有する場合が、光沢性、施釉面の状態
および硬度を加味すると最も優れた結果が得られた。Table 3 From the results shown in Table 3, the mixed frit glaze is glaze A:Y.
When the composition was 1:1, the best results were obtained when considering gloss, glazed surface condition, and hardness.
実施例１０〜１２
実施例１〜３の混合フリット釉薬り、Ｅ、Ｆの配合成分
の中に、さらに有色顔料を釉薬に対し２重量％添加し、
実施例１〜３と同様の方法により、種々の着色を呈する
と共に金属光沢を有する無機成形板を得た。Examples 10 to 12 A colored pigment was further added in an amount of 2% by weight based on the glaze to the mixed frit glazes of Examples 1 to 3, and the ingredients of E and F.
Inorganic molded plates exhibiting various colors and having metallic luster were obtained by the same method as in Examples 1 to 3.
その結果を第４表に示す。The results are shown in Table 4.
第４表 （注） 有色顔料は、 下記の第５表に示す日脚産業 株式会社製の有色顔料を使用した。Table 4 (note) Colored pigments are Japanese leg industry shown in Table 5 below Colored pigments manufactured by Co., Ltd. were used.
第５表
有色顔料を添加することにより、種々の着色を呈すると
共に、金属光沢を有する施釉表面を得ることができた。Table 5 By adding colored pigments, it was possible to obtain glazed surfaces exhibiting various colors and having metallic luster.
実施例１３
混合フリット釉薬には実施例２の釉薬Ｅを用いて、フレ
ーク状金属粉末にはステンレスフレークを用いて、焼成
温度を種々に変える以外は実施例２と同様の方法で金属
光沢を有する無機成形板を得た。Example 13 A product with metallic luster was produced in the same manner as in Example 2 except that glaze E of Example 2 was used for the mixed frit glaze, stainless steel flakes were used for the flaky metal powder, and the firing temperature was varied. An inorganic molded plate was obtained.
その結果を第６表に示す。The results are shown in Table 6.
第 ６ 表 （注）＊は比較例を示す。No. 6 table (Note) * indicates a comparative example.
実施例１４
混合フリット釉薬には実施例２の釉薬Ｅを用いて、フレ
ーク状金属粉末にはステンレスフレークを用いて、ステ
ンレスフレークの添加量を種々に変える以外は実施例２
と同様の方法で金属光沢を有する無機成形板を得た。Example 14 Example 2 except that glaze E of Example 2 was used for the mixed frit glaze, stainless steel flakes were used for the flaky metal powder, and the amount of stainless flakes added was varied.
An inorganic molded plate with metallic luster was obtained in the same manner as above.
その結果を第７表に示す。The results are shown in Table 7.
第
表
（注１）添加量は釉薬に対するステンレスフレークの添
加量を示す。The amount added in Table (Note 1) indicates the amount of stainless steel flakes added to the glaze.
（注２）＊は比較例を示す。(Note 2) * indicates a comparative example.
第７表に示す結果から、フレーク状金属粉末は釉薬に対
して８重量％以上の添加量になると施釉表面にザラつき
が見られる。これは添加量が多くなるにしたがって釉薬
の表面に金属粉末が出るためである。添加量カ月６重量
％になると施釉表面はかなりザラついた状態とななる。From the results shown in Table 7, when the amount of flaky metal powder added to the glaze is 8% by weight or more, roughness is observed on the glazed surface. This is because metal powder appears on the surface of the glaze as the amount added increases. When the amount added is 6% by weight, the glazed surface becomes quite rough.
実施例１５
実施例２で使用したフレーク状金属粉末のステンレスフ
レークの代わりに、下記焼成により着色させたステンレ
スフレークを使用し、実施例２と同様の方法により金属
光沢を有する無機成形板を得た。その結果を第８表に示
す。Example 15 Instead of the stainless steel flakes of flaky metal powder used in Example 2, stainless steel flakes colored by the following firing were used, and an inorganic molded plate with metallic luster was obtained in the same manner as in Example 2. . The results are shown in Table 8.
第
表
第８表に示す結果がら、３００ ”Ｃ以下での焼成によ
る金属粉末表面の酸化皮膜の形成では、有姿品との間に
は大きな違いは見られなかった。From the results shown in Table 8, there was no significant difference between the solid product and the solid product in the formation of an oxide film on the surface of the metal powder by firing at 300''C or less.
４００℃以上の焼成品から金属粉末表面の変色が見られ
、金色−青色−黒色の順で焼成温度が高くなるにつれ色
調が変化する。施釉焼成後の光沢は良好であり、高温焼
成品になるほど色調はシルバー系からゴールド系へと移
行してゆく。Discoloration of the surface of the metal powder is observed in products fired at 400° C. or higher, and the color tone changes in the order of gold, blue, and black as the firing temperature increases. The gloss after glazing and firing is good, and the color tone shifts from silver to gold as the product is fired at higher temperatures.
６００℃及び７００℃での焼成品は、外観に強い光沢性
は見られないものの、施釉焼成後の施釉表面に光沢性が
残る。これは金属表面の変色した部分が釉薬と反応しや
すく、未変色部分は反応しにくいために光沢性が残るた
めで、このことからも粒径はある程度の大きさが必要で
あり、多（の場合３０ルｍ以上であればよい。Products fired at 600° C. and 700° C. do not have strong gloss in appearance, but gloss remains on the glazed surface after glazing and firing. This is because the discolored parts of the metal surface are more likely to react with the glaze, while the undiscolored parts are less likely to react and remain glossy.For this reason, the particle size needs to be a certain size, and In this case, it is sufficient if the distance is 30 lm or more.
［発明の効果］
以上説明した様に、本発明のホウ珪酸塩系フリット釉薬
と台船系フリット釉薬との混合フリット釉薬とフレーク
状金属粉末を含有する釉薬を用いれば、施釉後の焼成に
よりフレーク状金属粉末は混合フリット釉薬と反応する
ことはなく、金属光沢を有し、かつ耐酸性を有する施釉
物品を得ることができる。[Effects of the Invention] As explained above, if the mixed frit glaze of the present invention containing a borosilicate-based frit glaze and a barge-based frit glaze and a glaze containing flaky metal powder are used, flakes will be produced by firing after glazing. The shaped metal powder does not react with the mixed frit glaze, and it is possible to obtain a glazed article having metallic luster and acid resistance.
また、本発明の施釉物品は金属光沢を有する表面化粧さ
れた珍重な製品であり、タイルや各種の建築材料等とし
て極めて有用である。Furthermore, the glazed article of the present invention is a rare product with a surface decorated with metallic luster, and is extremely useful as tiles and various building materials.
Claims (4)
との混合フリット釉薬にフレーク状金属粉末を含有して
なることを特徴とする釉薬。(1) A glaze characterized by containing flaky metal powder in a mixed frit glaze of a borosilicate frit glaze and a lead-containing frit glaze.
施釉できるものである請求項１記載の釉薬。(2) The glaze according to claim 1, wherein the mixed frit glaze can be glazed at a temperature of 650 to 1000°C.
０μｍ以上のステンレス粉である請求項１記載の釉薬。(3) The flaky metal powder has an average particle size of at least 3
The glaze according to claim 1, which is stainless steel powder with a diameter of 0 μm or more.
釉してなる金属光沢を有する施釉物品。(4) A glazed article having metallic luster, which is obtained by applying the glaze according to claim 1 to the surface of an inorganic molded body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7681190A JP2963487B2 (en) | 1990-03-28 | 1990-03-28 | Glaze and glazed articles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7681190A JP2963487B2 (en) | 1990-03-28 | 1990-03-28 | Glaze and glazed articles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03279237A true JPH03279237A (en) | 1991-12-10 |
| JP2963487B2 JP2963487B2 (en) | 1999-10-18 |
Family
ID=13616054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7681190A Expired - Fee Related JP2963487B2 (en) | 1990-03-28 | 1990-03-28 | Glaze and glazed articles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2963487B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100478583B1 (en) * | 2001-11-16 | 2005-03-28 | 주식회사 서울세라믹스 | Glaze composition for metallic tile using thereof and Preparing method |
| US6881690B2 (en) * | 2002-02-19 | 2005-04-19 | Noritake Co., Ltd. | Compositions for the decoration of ceramic materials |
| JP2019127404A (en) * | 2018-01-23 | 2019-08-01 | Ａｇｃ株式会社 | Glass, method for producing glass, conductive paste, and solar cell |
| KR20210037866A (en) * | 2019-09-30 | 2021-04-07 | 한국세라믹기술원 | Glaze composition for forming glaze layer having high contact angle and anti-stain properties and manufacturing method of ceramic tile using the composition |
| KR20220065246A (en) * | 2020-11-13 | 2022-05-20 | 대동산업 주식회사 | Glaze composition having high stability of dispersion and manufacturing method of ceramic tile using the composition |
| KR20220083041A (en) * | 2020-12-11 | 2022-06-20 | 한국세라믹기술원 | Antibacterial glaze composition and manufacturing method of ceramic tile using the composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102352357B1 (en) * | 2019-11-04 | 2022-01-17 | 한국세라믹기술원 | Manufacturing method of ceramic tile using the glaze composition for forming glaze layer having high contact angle and excellent hardness properties |
-
1990
- 1990-03-28 JP JP7681190A patent/JP2963487B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100478583B1 (en) * | 2001-11-16 | 2005-03-28 | 주식회사 서울세라믹스 | Glaze composition for metallic tile using thereof and Preparing method |
| US6881690B2 (en) * | 2002-02-19 | 2005-04-19 | Noritake Co., Ltd. | Compositions for the decoration of ceramic materials |
| JP2019127404A (en) * | 2018-01-23 | 2019-08-01 | Ａｇｃ株式会社 | Glass, method for producing glass, conductive paste, and solar cell |
| KR20210037866A (en) * | 2019-09-30 | 2021-04-07 | 한국세라믹기술원 | Glaze composition for forming glaze layer having high contact angle and anti-stain properties and manufacturing method of ceramic tile using the composition |
| KR20220065246A (en) * | 2020-11-13 | 2022-05-20 | 대동산업 주식회사 | Glaze composition having high stability of dispersion and manufacturing method of ceramic tile using the composition |
| KR20220083041A (en) * | 2020-12-11 | 2022-06-20 | 한국세라믹기술원 | Antibacterial glaze composition and manufacturing method of ceramic tile using the composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2963487B2 (en) | 1999-10-18 |
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