JPH03218989A - Glaze and glazed article - Google Patents
Glaze and glazed articleInfo
- Publication number
- JPH03218989A JPH03218989A JP4260990A JP4260990A JPH03218989A JP H03218989 A JPH03218989 A JP H03218989A JP 4260990 A JP4260990 A JP 4260990A JP 4260990 A JP4260990 A JP 4260990A JP H03218989 A JPH03218989 A JP H03218989A
- Authority
- JP
- Japan
- Prior art keywords
- glaze
- metal powder
- frit
- powder
- glazed
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 claims abstract description 59
- 239000002932 luster Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 53
- 239000000155 melt Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 239000003086 colorant Substances 0.000 abstract description 8
- 239000010935 stainless steel Substances 0.000 abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- -1 0-70% Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002002 slurry Substances 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
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000010410 layer Substances 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 101100348017 Drosophila melanogaster Nazo gene Proteins 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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000001354 calcination Methods 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
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 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
- 235000013372 meat Nutrition 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
- 238000007873 sieving Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution 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
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、フリット釉薬に金属粉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《ことができないものとなっ
ている。[Prior Art] As is well known, glazed articles are essential to 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 becomes.
そして、工業製品として用いられている施釉物品の多《
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。There are many glazed items used as industrial products.
The ones used are those glazed with 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、例えば素木洋一著「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, "Glaze and Its Pigments" 73 by Yoichi Motoki
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コ
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く、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 provide the surface of the ceramic with functions possessed by metal, such as conductivity.
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、１０００℃以下で溶融するフリッ
ト釉薬とフレーク状金属粉を含有す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 a frit glaze that melts at 1000° C. or lower and flaky metal powder.
更に、本発明は、無機質成形体の表面に、１０００℃以
下で溶融するフリット釉薬とフレーク状金属粉を含有す
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 relates to a glazed article having metallic luster, which is obtained by applying a frit glaze that melts at 1000° C. or lower and a glaze containing flaky metal powder to the surface of an inorganic molded body.
以下、本発明について詳述する。The present invention will be explained in detail below.
本発明に係る釉薬において、フリット釉薬は金属粉末に
対し可及的に不活性なビヒクルとしての釉薬であれば特
に限定するものではないが、例えばホウ珪酸塩系フリッ
ト釉薬等が挙げられる。In the glaze according to the present invention, the frit glaze is not particularly limited as long as it is a glaze that serves as a vehicle that is as inert as possible to the metal powder, and examples thereof include borosilicate-based frit glazes.
このホウ珪酸塩系フリット釉薬は、含鉛又は無鉛のいず
れでも用いることができる。This borosilicate-based frit glaze can be used either lead-containing or lead-free.
かかるフリット釉薬は、１０００℃以下、好まし《は７
５０〜８５０℃の加熱温度で溶融されるものであるが、
耐酸性を特に要求しない場合は、約４００℃までの低融
点フリット釉薬でも適用できる。また、１０００℃を越
えて加熱溶融すると、後述するフレーク状の金属粉末と
の関係で加熱の際、フレーク状金属粉がフリット中に実
質的に安定な状態で存在することが難しいためである。Such a frit glaze has a temperature of 1000°C or less, preferably <<7
It is melted at a heating temperature of 50 to 850°C,
If acid resistance is not particularly required, a frit glaze with a low melting point of up to about 400° C. can also be used. Further, if the frit is heated and melted at a temperature exceeding 1000° C., it is difficult for the flaky metal powder to exist in a substantially stable state in the frit during heating due to the relationship with the flaky metal powder described below.
また、フリット釉薬の化学組成は、加熱温度や配合され
るフレーク状金属粉、基材あるいは施釉物品の用途等に
より一様ではないが、酸化物表示で、Ｓｉ０２１０ 〜
７５ｗｔ％、ＢｚＯａ ５ 〜３０ｗｔ％、Ａｉｌｌ２
０３０〜１５ｗｔ％、ＰｂＯ Ｏ 〜７０ｗｔ％、 Ｍ
ＯＯ〜１５ｗｔ％（ＭはＣａ， Ｍｇ， Ｚｎ又はＢａ
を表わす）、Ｒ２００〜２０ｗｔ％（ＲはＬｉ， Ｋ又
はＮａを表わす）、その他０〜１ ５ｗｔ％の範囲にあ
る組成を有するものが好ましい。この範囲の組成からは
ずれると、前記と同様に配合されるフレーク状金属粉と
の関係で、加熱の際、フレーク状金属粉がフリット釉薬
中に実質的に安定な状態で存在することが難し《なるた
めである。特に、Ｂ２０３およびＲ２０の組成が上記の
範囲よりも多くなると、フレーク状金属粉と反応しやす
《なり、フレーク状金属粉が変色又は溶解するために低
融点焼成しなければならない。そのた？に、フレーク状
金属粉を釉薬に添加して金属特有ノ光沢を出そうとする
には、ＮａｚＯ． ＫｚＯ， ＬｉｚＯ等のアルカリ成
分およびＢ２０３の含有量の少ないものがフレーク状金
属粉との反応を抑制するので、このようなフリットを可
及的に高温加熱することが好ましい。しかし、金属フレ
ークの耐熱性を損う程の高溶融点フリットは焼成時の高
熱によりフレーク状金属粉が変色し光沢を残さな《なる
ために避けるべきである。In addition, the chemical composition of the frit glaze varies depending on the heating temperature, the flake metal powder mixed, the base material, the use of the glazed article, etc., but in terms of oxides, Si0210 ~
75wt%, BzOa 5 ~ 30wt%, Aill2
030~15wt%, PbO~70wt%, M
OO~15wt% (M is Ca, Mg, Zn or Ba
), R200 to 20 wt% (R represents Li, K or Na), and others having a composition in the range of 0 to 15 wt%. If the composition deviates from this range, it is difficult for the flaky metal powder to exist in a substantially stable state in the frit glaze during heating due to the relationship with the flaky metal powder mixed in the same way as above. To become. In particular, when the composition of B203 and R20 exceeds the above range, they tend to react with the flaky metal powder, and the flaky metal powder must be fired at a low melting point in order to discolor or dissolve. Besides? In addition, in order to add flaky metal powder to the glaze to create a luster unique to metals, NazO. Since alkaline components such as KzO and LizO and those with a low content of B203 suppress the reaction with the flaky metal powder, it is preferable to heat such a frit as high as possible. However, a frit with a high melting point that impairs the heat resistance of the metal flakes should be avoided because the flaky metal powder will discolor due to the high heat during firing and will not retain its luster.
なお、施釉の化粧面の耐酸性は可及的に高溶融点フリッ
トを用いればよいが、化学組成的には周知のようにＡＮ
ｚｏｓやＺｒＯ ２成分を含有するものを用いることに
よっても得ることができる。In addition, for the acid resistance of the glazed decorative surface, it is best to use a frit with a high melting point as much as possible, but in terms of chemical composition, as is well known, AN
It can also be obtained by using a material containing two components of zos and ZrO.
従って、金属粉末を含有する釉薬においては、施釉表面
に係る金属粉末の安定性および金属光沢性と耐酸性など
の耐久性とは施釉条件が矛盾する。Therefore, in a glaze containing metal powder, the stability of the metal powder on the glazed surface, the metallic luster, and the durability such as acid resistance are inconsistent with the glazing conditions.
しかしながら、本発明に係る釉薬において、金属光沢性
と耐酸性の優れたものは、多くの場合、無鉛釉薬では、
ＳｉＯ■４５〜５５ｗｔ％、Ｂ２０３ １５〜２５？ｔ
％、ＡＰ２０３ ５〜１５ｗｔ％、ＭＯ５ 〜１５ｗｔ
％、Ｒ２０ ５〜２０ｗｔ％、その他Ｏ〜５Ｗｔ％（但
し、Ｍ， Ｒは前記と同義である）の化学組成の範囲を
有し、また、有鉛釉薬の場合は． ＳｉＯ■３０〜５５
ｗｔ％、Ｂ２０３０〜１５ｗｔ％、ＡｊｈＯｉ ５〜１
５Ｗｔ％、ＭＯＯ〜１０ｗｔ％、Ｒ．００〜ｌＯｗｔ％
、Ｐｂ０１５〜５５Ｗｔ％、その他Ｏ〜５Ｗｔ％（但し
、Ｍ， Ｒは前記と同義である）の化学組成を有してい
る。これら釉薬においては、特にＲ２０２〜１０ｗｔ％
、Ｂ２０３ ３ 〜１５ｗｔ％、有鉛の場合は、ｐｂｏ
１５〜４５ｗｔ％の範囲が好ましい。However, in the glaze according to the present invention, in many cases, the glaze with excellent metallic luster and acid resistance is not lead-free.
SiO■45~55wt%, B203 15~25? t
%, AP203 5~15wt%, MO5 ~15wt
%, R20 5 to 20 wt%, others O to 5 wt% (however, M and R have the same meanings as above), and in the case of leaded glaze. SiO■30~55
wt%, B2030~15wt%, AjhOi 5~1
5wt%, MOO~10wt%, R. 00～lOwt%
, Pb015 to 55 Wt%, and others O to 5 Wt% (where M and R have the same meanings as above). In these glazes, especially R202~10wt%
, B203 3 ~ 15wt%, in the case of leaded, pbo
A range of 15 to 45 wt% is preferred.
また、上記の化学組成の範囲に入るフリット釉薬は単独
でそのまま使用することができるが、範囲に入らないフ
リット釉薬は２種以上を調合して上記の範囲の組成に調
製して用いることができる。Additionally, frit glazes that fall within the chemical composition range above can be used alone as is, but frit glazes that do not fall within the range can be used by mixing two or more types to have a composition within the above range. .
次に、かかるフリット釉薬に配合されるフレーク状金属
粉としては、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，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。Next, examples of the flaky metal powder to be added to the frit glaze include stainless steel powder, other metal powders such as copper, iron, aluminum, nickel, titanium, or zinc, and alloy powders such as bronze powder. but,
Among them, stainless steel powder is particularly preferred.
さらに、フレーク状金属粉としては、上記の粉末の他に
、金属メッキ品粉末も使用することができ、例えばマイ
力やその他の芯材をコア材とする無電解メッキ粉末が挙
げられる。なお、これらのフレーク状金属粉は、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。Further, as the flaky metal powder, in addition to the above-mentioned powders, metal plated product powders can also be used, such as electroless plating powders having a core material such as Myroku or other core materials. Note that these flaky metal powders may be colored by an interference film obtained by thinly oxidizing the surface by firing.
また、フレーク状金属粉は、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，分散性
のよいものを得るのに好ましく、特に３０〜２００＃Ｌ
ｍの範囲のものが好ましい。平均粒子径が３０μｍ未満
では、微粒子となるために加熱により釉薬に対して反応
し易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, it is preferable that the flaky metal powder has an average particle size of at least 30 pm or more in order to obtain good color tone, gloss, and dispersibility, especially 30 to 200 #L.
A range of m is preferred. If the average particle diameter is less than 30 μm, the particles become fine and easily react with the glaze when heated, resulting in a dark tone and poor gloss. 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［１！又は顕微鏡でフレーク状又は
扱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。In addition, in the present invention, the term "flake-like" is not strictly specified, but rather refers to the shape of meat [1! Or something that can be observed under a microscope in the form of flakes or flakes. 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.
フリット釉薬に対するフレーク状金属粉の配合割合は、
配合されるフレーク状金属粉の種類、基材あるいは施釉
物品の用途等により一様ではないが、通常はフリット釉
薬１００重量部に対してフレーク状金属粉を０．１〜１
０重量部、特に１〜３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が少ないためにそれに
基づき施釉物品の表面に光沢面が得られず、またｌＯ重
量部を越えてると施釉表面にフレーク状金属粉が出て《
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 frit glaze is
Although it varies depending on the type of flaky metal powder to be mixed, the use of the base material or the glazed article, etc., it is usually 0.1 to 1 part by weight of flaky metal powder per 100 parts by weight of the frit glaze.
A range of 0 parts by weight, particularly 1 to 3 parts by weight, is preferred. 0.1
If it is less than 1 part by weight, the amount of flaky metal powder will be small and the surface of the glazed article will not have a glossy surface, and if it exceeds 10 parts by weight, flaky metal powder will appear on the glazed surface.
This is not preferable because it is economically disadvantageous because it becomes rough and requires conditions such as raising the firing temperature and extending the firing time.
本発明に係る釉薬は、上記のフリット釉薬とフレーク状
金属粉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，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-mentioned frit glaze and flaky metal powder, but when applying the glaze to the surface of the base material, various surfactants may be added as necessary.
A viscosity modifier, an organic or inorganic dispersant, a coloring agent, etc. are blended as auxiliary agents, which 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ク状金属
粉の種類、基材あるいは施釉物品の用途等により一様で
はないが、通常はフリット釉薬１００重量部に対して１
〜５重量部、特に２〜３重量部の範囲が好ましい。The amount of the 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 part by weight per 100 parts by weight of the frit glaze.
A range of 5 parts by weight, especially 2 to 3 parts by weight is preferred.
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、施釉温度で強度
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. Moreover, it may be a special cement molded product as long as it does not substantially deteriorate in strength at the glazing temperature.
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
リーをスプレー掛け或いははけ塗り、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４
００〜１０００℃、好ましくは７５０〜９００℃の焼成
温度まで昇温し、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. , dry as necessary, then 4
The temperature is raised to a firing temperature of 00 to 1000°C, preferably 750 to 900°C, and heat treatment is performed 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、フレーク状金属粉単味を掛け、更にその上にフリ
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 single frit glaze constituting the glaze. A third method is a three-layer method in which a single layer of glaze is applied, a flake metal powder layer is applied, and then a frit glaze layer is applied on top of that.
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１〜７
下記の組成を有する各種のフリット釉薬１２０重量部と
、フレーク状金属粉として平均粒子径３０μｍのステン
レスフレーク（川鉄テクノリサーチ株式会社製）３重量
部よりなる釉薬を、界面活性剤（エマルゲン：花王株式
会社製） ０．１５重量部、分散剤（ビスマール：日本
化学工業株式会社製）０．２０重量部を含有する水溶液
１２０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 7 A glaze consisting of 120 parts by weight of various frit glazes having the following compositions and 3 parts by weight of stainless steel flakes (manufactured by Kawatetsu Techno Research Co., Ltd.) with an average particle diameter of 30 μm as flaky metal powder was mixed with a surfactant. A uniform slurry-like glaze was prepared by adding it to 120 parts by weight of an aqueous solution containing 0.15 parts by weight of Emulgen (manufactured by Kao Corporation) and 0.20 parts by weight of a dispersant (Bismal: manufactured by Nihon Kagaku Kogyo Co., Ltd.). did.
次いで、このスラリーをスプレーガンにより、１００Ｘ
５０Ｘ １０ｍｍ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、次いで焼成した
。Next, this slurry was sprayed at 100X using a spray gun.
A 50×10 mm inorganic molded board (tile base) was glazed, dried at 110° C. for about 30 minutes, and then fired.
その結果を第１表に示す。The results are shown in Table 1.
（注１）光沢性は施釉面の外観を肉眼観察して評価する
。（以下同様とする）
優・・・施釉面が均一に金属光沢を有し、意匠性の優れ
た状態にあるもの。(Note 1) Glossiness is evaluated by visually observing the appearance of the glazed surface. (The same shall apply hereinafter) Excellent: The glazed surface has a uniform metallic luster and is in an excellent state of design.
良・・・均一性はあるが、やや金属光沢性を欠《状態に
あるもの。Good: Uniform, but somewhat lacking in metallic luster.
不良・・・施釉面が変色し、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 a metallic luster.
実施例８〜ｌ３
実施例１および４で用いたフリット釉薬ＡとＤの２種に
対し、ステンレスフレーク，アルミニウム粉末，無電解
Ｎｉめっき雲母粉末のフレーク状金属粉を混合した釉薬
を、実施例１と同様の条件でタイル素地に施釉して美感
のある施釉タイルを得た。Examples 8 to 13 A glaze obtained by mixing flaky metal powder of stainless steel flakes, aluminum powder, and electroless Ni-plated mica powder was used in Example 1 for the two types of frit glazes A and D used in Examples 1 and 4. A beautiful glazed tile was obtained by glazing the tile base under the same conditions as above.
その結果を第２表に示す。The results are shown in Table 2.
（注）
■・・・アルミニウム粉末（キシダ化学■製品、平均粒
子径４５終ｍ
■・・・Ｎｉめっき雲母（ブライト、日本化学工業■製
品、平均粒子径６５＃Ｌｍ
実施例１４〜１７
実施例１で使用したフレーク状金属粉の代わりに、下記
焼成により着色させたフレーク状金属粉を使用し、実施
例１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３表に示す。(Note) ■... Aluminum powder (Kishida Chemical ■ product, average particle size 45 #Lm ■... Ni-plated mica (Bright, Nippon Chemical Industry ■ product, average particle size 65 #Lm) Examples 14 to 17 Examples In place of the flaky metal powder used in Example 1, flaky metal powder colored by the following firing process was used to obtain an inorganic molded plate with metallic luster in the same manner as in Example 1.The results were reported in Example 3. Shown in the table.
第
３
表
丈
（注）
（１）焼成ステンレスフレーク
実施例１と同じステンレスフレークを５００℃で３０分
間焼成したフレーク状金属粉。Table 3 Length (Note) (1) Fired stainless steel flakes A flaky metal powder obtained by firing the same stainless steel flakes as in Example 1 at 500°C for 30 minutes.
（２）焼成Ｎｉめっき雲母粉末
前記■のＮｉめっき雲母粉末を３００℃で３０分間焼成
したフレーク状金属粉。(2) Calcined Ni-plated mica powder A flaky metal powder obtained by calcining the Ni-plated mica powder of (1) above at 300°C for 30 minutes.
実施例１８〜２１
実施例１４〜１７の釉薬の配合成分の中に、さらに有色
顔料をフリットに対し２重量部添加し、実施例１４〜１
７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 18 to 21 2 parts by weight of a colored pigment was further added to the frit to the ingredients of the glazes of Examples 14 to 17.
Inorganic molded plates exhibiting various colors and having metallic luster were obtained by the same method as in Example 7.
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
ブルー色（日陶産業■製品、Ｍ−９２３）栗茶色（日陶
産業■製品、Ｍ−１０ ）黄色（日陶産業■製品、 Ｚ
−５８０ ）赤茶色（日陶産業側製品、Ｌ−９６ ）実
施例２２〜２８
下記の第５表に示す組成を有する各種のフリット釉薬１
００重量部と、フレーク状金属粉として平均粒子径１５
０ｐｍ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：花王株式会社製）０．１５重量部、分散剤（ＣＭ
Ｃ ：四国化成株式会社製）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。Table 4 (Note) ■Colored pigment blue color (Nissto Sangyo ■product, M-923) Chestnut brown (Nissto Sangyo ■product, M-10) Yellow (Nissto Sangyo ■product, Z
-580) Reddish brown (Nichito Sangyo product, L-96) Examples 22 to 28 Various frit glazes 1 having the compositions shown in Table 5 below
00 parts by weight and an average particle size of 15 as flaky metal powder.
A glaze consisting of 5 parts by weight of 0pm stainless steel flakes (manufactured by Kawatetsu Techno Research Co., Ltd.), 0.15 parts by weight of a surfactant (Emulgen, manufactured by Kao Corporation), and a dispersant (CM
C: manufactured by Shikoku Kasei Co., Ltd.) to 100 parts by weight of an aqueous solution containing 2 parts by weight to prepare a uniform slurry-like glaze.
次いで、このスラリーをスプレーガンにより、１００Ｘ
ＩＯＯＸ ３ ｍｍの無機成形板（タイル素地）に
施釉した後、１１０’Ｃで約３０分間乾燥し、次いで焼
成して施釉物品を得た。Next, this slurry was sprayed at 100X using a spray gun.
After applying the glaze to an inorganic molded board (tile base) of IOOX 3 mm, it was dried at 110'C for about 30 minutes and then fired to obtain a glazed article.
（注２）耐酸性は、施釉焼成品に塩酸溶液（１０Ｗ／Ｖ
％）を滴下し、一昼夜放置し、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 (10W/V) applied to glazed fired products.
%) was dropped and allowed to stand overnight, 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.
［発明の効果］
以上説明した様に、本発明のフリット釉薬とフレーク状
金属粉を含有する釉薬を用いれば、施釉後の焼成により
フレーク状金属粉はフリット釉薬と反応することはな《
、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 frit glaze of the present invention and the glaze containing flaky metal powder are used, the flaky metal powder will not react with the frit glaze during firing after glazing.
A glazed article having metallic luster and acid resistance can be obtained.
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 (3)
ク状金属粉を含有することを特徴とする釉薬。(1) A glaze characterized by containing a frit glaze that melts at 1000°C or lower and flaky metal powder.
μｍ以上である請求項１記載の釉薬。(2) The flaky metal powder has an average particle size of at least 30
The glaze according to claim 1, which has a diameter of μm or more.
るフリット釉薬とフレーク状金属粉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。(3) A glazed article having metallic luster, which is obtained by applying a frit glaze that melts at 1000° C. or lower and a glaze containing flaky metal powder to the surface of an inorganic molded body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4260990A JPH03218989A (en) | 1989-02-27 | 1990-02-26 | Glaze and glazed article |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4323089 | 1989-02-27 | ||
| JP1-43230 | 1989-02-27 | ||
| JP4260990A JPH03218989A (en) | 1989-02-27 | 1990-02-26 | Glaze and glazed article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03218989A true JPH03218989A (en) | 1991-09-26 |
Family
ID=26382330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4260990A Pending JPH03218989A (en) | 1989-02-27 | 1990-02-26 | Glaze and glazed article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03218989A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006136610A2 (en) * | 2005-06-23 | 2006-12-28 | Colorobbia Italia S.P.A. | Materials for coating ceramic bodies, processes for the preparation thereof, use thereof and ceramic articles including these materials |
| CN110304828A (en) * | 2019-07-31 | 2019-10-08 | 佛山欧神诺陶瓷有限公司 | A kind of preparation method and ceramic tile without overglaze ceramic tile with concave-convex discoloration metal effect |
-
1990
- 1990-02-26 JP JP4260990A patent/JPH03218989A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006136610A2 (en) * | 2005-06-23 | 2006-12-28 | Colorobbia Italia S.P.A. | Materials for coating ceramic bodies, processes for the preparation thereof, use thereof and ceramic articles including these materials |
| WO2006136610A3 (en) * | 2005-06-23 | 2007-07-12 | Colorobbia Italiana Spa | Materials for coating ceramic bodies, processes for the preparation thereof, use thereof and ceramic articles including these materials |
| CN110304828A (en) * | 2019-07-31 | 2019-10-08 | 佛山欧神诺陶瓷有限公司 | A kind of preparation method and ceramic tile without overglaze ceramic tile with concave-convex discoloration metal effect |
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