JP3486438B2 - Glaze composition and inorganic substrate provided with the composition - Google Patents
Glaze composition and inorganic substrate provided with the compositionInfo
- Publication number
- JP3486438B2 JP3486438B2 JP31398293A JP31398293A JP3486438B2 JP 3486438 B2 JP3486438 B2 JP 3486438B2 JP 31398293 A JP31398293 A JP 31398293A JP 31398293 A JP31398293 A JP 31398293A JP 3486438 B2 JP3486438 B2 JP 3486438B2
- Authority
- JP
- Japan
- Prior art keywords
- glaze
- composition
- base material
- inorganic base
- plating
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は釉組成物、特に任意の無
機質基材に金属メッキを可能とする釉組成物及び該組成
物を施した無機質基材に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glaze composition, and more particularly to a glaze composition which enables metal plating on an arbitrary inorganic substrate and an inorganic substrate provided with the composition.
【0002】[0002]
【従来の技術】無機質材料よりなる基材(以下、無機質
基材という)の表面に金属化膜を形成することは、金属
的な外観付与のほか、耐摩耗性、機械的強度、導電性、
化学的性質等、無機質基材単独では有しない諸性質を付
与できるので、装飾品、日用品、電子基板材料等広範囲
の分野に利用される。2. Description of the Related Art Forming a metallized film on the surface of a substrate made of an inorganic material (hereinafter referred to as "inorganic substrate") not only gives a metallic appearance but also wear resistance, mechanical strength, conductivity,
It can be used in a wide range of fields such as ornaments, daily necessities, electronic substrate materials, etc., because it can impart various properties such as chemical properties that are not possessed by an inorganic substrate alone.
【0003】無機質基材に対するメタライジング(金属
化膜を形成する)方法は種々の方法が知られている。例
えば、イオンプレーティング法、スパッタ法、CVD法
等の固相−気相系では、高価な設備、装置等を要し、装
置、プロセス上、コスト高になってしまうと共に大型品
のメタライジングは困難である。Various methods are known for metalizing (forming a metallized film) on an inorganic substrate. For example, a solid phase-gas phase system such as an ion plating method, a sputtering method, or a CVD method requires expensive equipment, equipment, etc., which increases the cost in terms of equipment and process, and metalizing of large products is not possible. Have difficulty.
【0004】また、有機接着剤を用いる方法は、簡便、
低価格であるが、耐熱性、耐候性が悪いという短所があ
り、接合操作の加熱時に水分が抜けて出て硬化し、その
微細な穴のため完全には気密性になり難いことが欠点で
ある。The method using an organic adhesive is simple and easy.
Although it is low in price, it has the disadvantage of poor heat resistance and weather resistance, and it has the drawback that it is hard to become completely airtight due to its minute holes, which hardens due to the loss of water during heating during bonding operation. is there.
【0005】その他の方法として、高融点金属法、圧着
法、直流電圧印加法、還元法などがあるが、いずれも基
材の変化、寸法精度の低下、また残留応力が大きくなる
ことなどに伴う接合強度の低下をきたしたり、コスト高
となるなどの欠点がある。Other methods include a refractory metal method, a pressure bonding method, a DC voltage application method, and a reduction method, all of which are accompanied by a change in the base material, a decrease in dimensional accuracy, and an increase in residual stress. There are drawbacks such as a decrease in bonding strength and an increase in cost.
【0006】[0006]
【発明が解決しようとする課題】このような中で、無機
質基材へのメッキを施すことは、ほぼ室温下での簡便な
低価格なプロセスであること、複雑な形状基材へのまわ
り込みが可能であること、などの点で有利である。しか
し、無機質基材をメッキ可能な表面(粗化面)とするこ
とは難しく、特殊な技術を要する。サンドブラスト、タ
ンブラ磨き等の硬質の無機質基材に合理的な機械的エッ
チングを行うことは困難であり、多くの場合、基材の表
面平滑性が損なわれ、均一な状態でメッキを施すことは
困難である。また、無機質基材は、わずかな表面の傷の
影響で応力集中を受けやすく、構造材料としての信頼性
を低下させる原因ともなりかねない。Under these circumstances, plating an inorganic base material is a simple and low-priced process at about room temperature, and it is necessary to cover a base material with a complicated shape. Is possible, and so on. However, it is difficult to form the surface of the inorganic base material that can be plated (roughened surface), and a special technique is required. It is difficult to perform rational mechanical etching on a hard inorganic substrate such as sandblast and tumbler polishing, and in many cases, the surface smoothness of the substrate is impaired and it is difficult to plate in a uniform state. Is. In addition, the inorganic base material is likely to be subjected to stress concentration due to the influence of a slight surface scratch, which may cause a decrease in reliability as a structural material.
【0007】化学的なエッチングの場合でも、粗化面と
することは難しい。それは、無機質基材は、一般に耐薬
品性の高い材料であり、仮にエッチングが可能な薬品で
あっても無機質基材の材質により制限される。いずれに
しても、エッチング条件により、メッキ膜が敏感に対応
するため、硬質で耐薬品性の高い種々の無機質基材に、
再現性良く粗化面を得ることは容易でないため、量産は
難しい。しかも、無機質基材に部分的なメッキを施すこ
とは、エッチングに特殊なマスキングを要するため生産
性が低くコスト高になる。本発明の目的は、無機質基材
の材質に制約されることなくエッチング操作も不要で、
密着強度が高いメッキを低コストで施すことができると
共に、繊細なデザイン付与も容易にできる釉組成物を提
供するにある。Even in the case of chemical etching, it is difficult to form a roughened surface. That is, the inorganic base material is generally a material having high chemical resistance, and even if it is a chemical that can be etched, it is limited by the material of the inorganic base material. In any case, since the plating film is sensitive to the etching conditions, it can be applied to various inorganic base materials that are hard and have high chemical resistance.
Mass production is difficult because it is not easy to obtain a roughened surface with good reproducibility. Moreover, the partial plating of the inorganic base material requires a special masking for etching, resulting in low productivity and high cost. The purpose of the present invention is not limited to the material of the inorganic substrate, and the etching operation is not required,
It is an object of the present invention to provide a glaze composition that can be plated at high adhesion strength at low cost and can be easily given a delicate design.
【0008】[0008]
【課題を解決するための手段】上記の目的を達成するた
め、本発明はなされたもので、釉薬成分中にチタン酸ア
ルカリを5〜95重量%配合したことを特徴とする釉組
成物である。また、上記の釉組成物を施して焼成し、チ
タン酸アルカリを表面に固結せしめたことを特徴とする
無機質基材である。さらに、上記の無機質基材に金属メ
ッキを施したことを特徴とする金属メッキ層を有する無
機質基材である。 In order to achieve the above object, the present invention has been made, and is a glaze composition characterized by containing 5 to 95% by weight of alkali titanate in a glaze component. . In addition, after applying the above glaze composition and baking,
Characterized by the solidification of alkali titanate on the surface
It is an inorganic base material. In addition, the above-mentioned inorganic substrate is
With a metal plating layer characterized by being applied
It is an organic base material.
【0009】 チタン酸アルカリが配合されるベース釉
薬としては、対象の無機質基材の材質に適応した釉薬を
選択することができ、チタン酸アルカリを変質させない
低火度釉が好ましい。例えば、アルカリ釉、ホウ酸釉、
フリット釉、鉛釉等が挙げられる。そして、焼成によ
り、ガラスボンドの接合でチタン酸アルカリが無機質基
材に固結する。また、チタン酸アルカリの配合量は、5
〜95重量%、好ましくは30〜70重量%の範囲であ
る。5重量パーセント未満ではチタン酸アルカリの効果
が充分でなく、95重量パーセントを超えると釉成分の
作用が減少し、無機質基材に対する固着性が低下するの
で、上記の範囲から選択することが肝要である。As the base glaze to which the alkali titanate is mixed, a glaze suitable for the material of the target inorganic base material can be selected, and a low-grade glaze that does not deteriorate the alkali titanate is preferable. For example, alkaline glaze, boric acid glaze,
Examples include frit glaze and lead glaze. Then, by firing, the alkali titanate is solidified on the inorganic base material by the bonding of the glass bond. The amount of alkali titanate compounded is 5
The range is from 95 to 95% by weight, preferably from 30 to 70% by weight. If it is less than 5% by weight, the effect of alkali titanate is not sufficient, and if it exceeds 95% by weight, the effect of the glaze component is reduced and the adhesion to the inorganic base material is lowered. Therefore, it is important to select from the above range. is there.
【0010】本発明が適用できる無機質基材は、ガラ
ス、陶磁器、タイル、ニューセラミックス、マトリック
スを無機材料とする複合材料等が挙げられる。Examples of the inorganic base material to which the present invention can be applied include glass, ceramics, tiles, new ceramics, and composite materials using a matrix as an inorganic material.
【0011】本発明に用いられるチタン酸アルカリは、
M2 O(Mはアルカリ金属)とTiO2 との複合酸化
物、及びその水和物で、TiO6 八面体、あるいはTi
O5 三角両錘体の連鎖様式よりなる結晶構造をもつ特徴
があるものを表す。粉体であるチタン酸アルカリの形状
は、繊維状、板状、球状、不定形などで形状的な制約を
受けるものではないが、繊細なデザインに対応するに
は、細い粒度のチタン酸アルカリが適する。The alkali titanate used in the present invention is
A complex oxide of M 2 O (M is an alkali metal) and TiO 2 and its hydrate, which are TiO 6 octahedron or Ti
O 5 has a characteristic of having a crystal structure consisting of a triangular bipyramidal chain. The shape of the powdered alkali titanate is not restricted by the shape such as fibrous, plate-like, spherical, and amorphous, but in order to support delicate designs, fine-grained alkali titanate should be used. Suitable.
【0012】本発明の釉組成物を無機質基材の表面に付
与する手段としては、転写法、スクリーン印刷法、噴霧
法、その他刷毛塗り等公知の手段を採用することがで
き、特に限定されるものではない。所要の手段で付与し
た後、通常、100〜200℃で乾燥し、釉の種類に応
じた温度で焼成して無機質基材に固結させ、任意のデザ
インを形成することができる。固結後メッキを施す場合
は、従来のメッキ設備を変更することなく公知の方法で
行うことができる。すなわち、脱脂、洗浄、センシタイ
ジング、アクチベーティングを経た後、無電解メッキを
行う。必要があれば、更に無電解メッキ、又は電解メッ
キ又はろう付け等を施す。As a means for applying the glaze composition of the present invention to the surface of the inorganic base material, a known method such as a transfer method, a screen printing method, a spraying method, or a brush coating method can be adopted, and it is particularly limited. Not a thing. After being applied by the required means, it is usually dried at 100 to 200 ° C. and baked at a temperature depending on the type of glaze to be solidified on the inorganic base material, whereby an arbitrary design can be formed. When the plating is performed after the solidification, the known method can be used without changing the conventional plating equipment. That is, after degreasing, cleaning, sensitizing, and activating, electroless plating is performed. If necessary, electroless plating, or electrolytic plating or brazing is further performed.
【0013】[0013]
【作用】本発明の釉組成物は、含有するチタン酸アルカ
リが無機質基材表面に固結することで、密着強度にすぐ
れたメッキを行うことができる。金属との高い密着強
度、気密性は、チタン酸アルカリのTiO6 八面体、あ
るいはTiO5 三角両錘体の連鎖様式よりなる前述した
結晶構造に起因し、形成されるトンネルあるいは層側、
あるいは稜を共有して作るジグザグ状の連結部分が重要
な役割を演じ、そのミクロな凹部が強力なアンカー効果
(投錨効果)をもたらす。なお、チタン酸アルカリの表
面露出量を増大させる目的で、前処理として化学的また
は機械的エッチングを行うことも可能であるが、釉の種
類とチタン酸アルカリの配合量の関係で、このエッチン
グ操作は不要となる。In the glaze composition of the present invention, the contained alkali titanate is solidified on the surface of the inorganic base material, so that plating having excellent adhesion strength can be performed. The high adhesion strength and airtightness with the metal are due to the above-mentioned crystal structure consisting of the chain pattern of the TiO 6 octahedron of the alkali titanate or the TiO 5 triangular bipyramid, and the formed tunnel or layer side,
Alternatively, the zigzag-shaped connecting part that shares the ridge plays an important role, and the micro concave part provides a strong anchor effect (anchor effect). For the purpose of increasing the surface exposure amount of alkali titanate, chemical or mechanical etching can be performed as a pretreatment, but this etching operation is performed depending on the type of glaze and the blending amount of alkali titanate. Is unnecessary.
【0014】[0014]
【実施例1〜3】表1に示すようにチタン酸アルカリ粉
末とベース釉粉とを調合し、各調合に混ぜ、絵付け方法
に応じて適量の補助材料を加えて絵付けを行った後、乾
燥、焼成し、各無機質基材に釉組成物を固結した。次い
で、表面を界面活性剤で脱脂後、常法に従い、無電解メ
ッキを施した。各実施例において、絵付け部分に選択的
にメッキ層が得られ密着強度も高いものであった。[Examples 1 to 3] As shown in Table 1, alkali titanate powder and base glaze powder were blended, mixed into each blend, and an appropriate amount of auxiliary material was added according to the painting method, and after painting After drying and firing, the glaze composition was solidified on each inorganic substrate. Then, after degreasing the surface with a surfactant, electroless plating was performed according to a conventional method. In each of the examples, a plating layer was selectively obtained on the painted portion and the adhesion strength was high.
【0015】[0015]
【表1】 [Table 1]
【0016】[0016]
【実施例4〜8】フリット釉粉末とK2 O・6TiO2
粉末を表2に示すように調合し、適量の補助材料を加
え、アルミナ基板にスプレー噴霧し、乾燥後1050℃
で固結し、3%水酸化カリウム溶液で脱脂後、常法に従
い無電解銅メッキと、更に無電解ニッケルメッキ層を得
た。得られた膜の密着強度試験を行った結果を表2に示
す。なお、比較例2では、1050℃の焼成温度ではK
2 O・6TiO2 が固結しなかったため、メッキ層を得
ることができなかった。比較例3では、焼成温度を13
10℃とすることでアルミナ基板上にK2 O・6TiO
2 が固結されたため、メッキ層を得ることはできたが、
実施例に比べ密着強度の低いものであった。[Examples 4 to 8] Frit glaze powder and K 2 O · 6TiO 2
The powder was prepared as shown in Table 2, an appropriate amount of auxiliary material was added, and the mixture was sprayed onto an alumina substrate and dried at 1050 ° C.
After solidifying with, and degreasing with a 3% potassium hydroxide solution, electroless copper plating and an electroless nickel plating layer were obtained according to a conventional method. The results of the adhesion strength test of the obtained film are shown in Table 2. Incidentally, in Comparative Example 2, at a firing temperature of 1050 ° C., K
Since 2 O · 6 TiO 2 did not solidify, a plating layer could not be obtained. In Comparative Example 3, the firing temperature was 13
By setting the temperature to 10 ° C., K 2 O.6TiO was formed on the alumina substrate.
Since 2 was solidified, a plating layer could be obtained,
The adhesion strength was lower than in the examples.
【0017】[0017]
【表2】 [Table 2]
【0018】なお、前記実施例において補助材料は、無
機質基材に対する粘着性、接着性、乾燥性の調節のた
め、絵付け方法に適した液体すなわち水、水溶性溶剤又
は油性の液体など、及びそれに対応した公知の糊剤が用
いられ、いずれも焼成により消失する材料である。また
絵付け方法は、繊細なデザインに対応し、絵付け箇所に
選択的にメッキ膜を得る際、塗布厚さが一定で均一なチ
タン酸アルカリ組成物を無機質基材表面に形成するため
に転写法、スクリーン法が適する。また、3次曲面など
複雑な曲面には、転写法・刷毛塗りなどが適し、絵付け
方法はデザイン形状に応じて適宜選択することができ
る。このような方法が採用できることも本発明の利点で
ある。In the above-mentioned embodiment, the auxiliary material is a liquid suitable for the painting method, such as water, a water-soluble solvent or an oily liquid, in order to control the tackiness, adhesiveness and drying property of the inorganic substrate, and Known sizing agents corresponding thereto are used, and all are materials that disappear by firing. In addition, the painting method corresponds to a delicate design, and when the plating film is selectively obtained at the painting place, transfer is performed in order to form a uniform alkali titanate composition with a constant coating thickness on the surface of the inorganic substrate. Method and screen method are suitable. Further, for complicated curved surfaces such as a cubic curved surface, a transfer method or brush coating is suitable, and the painting method can be appropriately selected according to the design shape. It is also an advantage of the present invention that such a method can be adopted.
【0019】[0019]
【発明の効果】以上説明したように、本発明の釉組成物
は、無機質基材に対し、任意の絵付け手段により、密着
強度の高い金属膜が、通常のメッキ方法により形成でき
ると共に繊細なデザインにも対応できるので、無機質基
材単独では有しない諸性質を必要に応じて容易に付与す
ることができる。したがって、日用品はもとより、各種
電子基材等広い分野に利用し得るので、その効果は頗る
大きい。As described above, in the glaze composition of the present invention, a metal film having high adhesion strength can be formed on an inorganic base material by an arbitrary painting means by a usual plating method and is delicate. Since it can also be designed, various properties not possessed by the inorganic base material alone can be easily imparted as necessary. Therefore, it can be used not only in daily necessities but also in a wide range of fields such as various electronic base materials, and its effect is extremely large.
Claims (3)
5重量%配合したことを特徴とする釉組成物。1. A glaze component containing 5 to 9 alkali titanates.
A glaze composition characterized by containing 5% by weight .
し、チタン酸アルカリを表面に固結せしめたことを特徴
とする無機質基材。2. An inorganic base material, characterized in that the glaze composition according to claim 1 is applied and baked to solidify alkali titanate on the surface.
を施したことを特徴とする金属メッキ層を有する無機質
基材。3. An inorganic base material having a metal plating layer, characterized in that the inorganic base material according to claim 2 is plated with a metal.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31398293A JP3486438B2 (en) | 1993-11-22 | 1993-11-22 | Glaze composition and inorganic substrate provided with the composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31398293A JP3486438B2 (en) | 1993-11-22 | 1993-11-22 | Glaze composition and inorganic substrate provided with the composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07144980A JPH07144980A (en) | 1995-06-06 |
JP3486438B2 true JP3486438B2 (en) | 2004-01-13 |
Family
ID=18047815
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31398293A Expired - Fee Related JP3486438B2 (en) | 1993-11-22 | 1993-11-22 | Glaze composition and inorganic substrate provided with the composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3486438B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111470883A (en) * | 2020-04-07 | 2020-07-31 | 陕西科技大学 | SiO (silicon dioxide)2Photonic crystal structure color coating and preparation process thereof |
CN113061016B (en) * | 2021-03-09 | 2022-07-15 | 江西金唯冠建材有限公司 | Preparation method of integral metal stair ceramic tile with original groove |
-
1993
- 1993-11-22 JP JP31398293A patent/JP3486438B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH07144980A (en) | 1995-06-06 |
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