JPS623044A - Ink for pottery and glass - Google Patents
Ink for pottery and glassInfo
- Publication number
- JPS623044A JPS623044A JP14045785A JP14045785A JPS623044A JP S623044 A JPS623044 A JP S623044A JP 14045785 A JP14045785 A JP 14045785A JP 14045785 A JP14045785 A JP 14045785A JP S623044 A JPS623044 A JP S623044A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- glass
- black pigment
- pigment
- ceramics
- 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.)
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Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は陶磁器・ガラス用インキに関し、更に詳しくは
複合酸化物系黒色顔料を着色剤とする耐変色性良好な陶
磁器・ガラス用黒色インキに関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an ink for ceramics and glass, and more particularly to a black ink for ceramics and glass that uses a complex oxide black pigment as a coloring agent and has good discoloration resistance. .
（従来の技術）
従来、陶磁器やカラス製品に印刷を施す１つの手段とし
て、低融点フリットと顔料からなる陶磁器・ガラス用イ
ンキを使用して陶磁器やガラス製品の表面に印刷を施し
、これを５００〜７００ ”（！の温度で焼付ける方法
が行われている。このような陶磁器・ガラス用インキ用
の顔料としては、高い耐熱性を有する顔料が要求される
ため、通常は各種の無機顔料が使用されている。(Prior art) Conventionally, one way to print on ceramics and glass products is to print on the surface of ceramics and glass products using a ceramic and glass ink consisting of a low melting point frit and a pigment. A method of baking at a temperature of ~700" (!) is used. Pigments for such ceramic and glass inks require pigments with high heat resistance, so various inorganic pigments are usually used. It is used.
（発明が解決しようとしている問題点）上記無機顔料の
うちで黒色の顔料については複合酸化物系黒色顔料が各
種性能に優れているため、陶磁器・ガラス用インキ用顔
料として広く使用されているが、その中でも特に銅を含
む複合酸化物系黒色顔料は、漆黒性、隠蔽力、着色力、
耐薬品性及び耐熱性に優れている。(Problem to be solved by the invention) Among the above-mentioned inorganic pigments, complex oxide black pigments are widely used as ink pigments for ceramics and glass because they have excellent various performances. Among them, complex oxide black pigments containing copper have jet blackness, hiding power, coloring power,
Excellent chemical resistance and heat resistance.
しかしながら、銅を含む複合酸化物系黒色顔料を含有し
た陶磁器−ガラス用インキを使用して陶磁器やガラス製
品の表面に印刷を施し、これを焼付焼成した場合、焼付
焼成時の雰囲気が還元性雰囲気であると、顔料中の銅の
一部が還元されて赤く発色し、漆黒性が損われるという
欠点があり、焼付焼成時に煩雑な条件設定等の必要を生
じる。However, if the surface of ceramic or glass products is printed using a ceramic-glass ink containing a complex oxide black pigment containing copper and then baked, the atmosphere at the time of baking is a reducing atmosphere. In this case, a part of the copper in the pigment is reduced and the pigment develops a red color, resulting in a loss of jet blackness, which requires complicated setting of conditions during baking.
このため、焼付焼成時に変色を生じない複合酸化物系黒
色顔料の開発が要望されている。For this reason, there is a demand for the development of a complex oxide black pigment that does not cause discoloration during baking.
（問題点を解決するための手段）
本発明者は上記の如き従来技術の要望に応えるべく鋭意
研究の結果、陶磁器Φガラス用インキ用の複合酸化物系
黒色顔料に特定の処理を施すことによって、どのような
雰囲気下で焼付焼成しても変色を生じない複合酸化物系
黒色顔料が得られることを知見して本発明を完成した。(Means for Solving the Problems) As a result of intensive research in order to meet the demands of the prior art as described above, the present inventor has developed a method by applying a specific treatment to a complex oxide black pigment for ink for ceramic Φ glass. The present invention was completed based on the finding that a composite oxide black pigment that does not change color even when baked in any atmosphere can be obtained.
すなわち、本発明は低融点フリットおよび顔料からなる
陶磁器令ガラス用インキにおいて、顔料が粒子表面にシ
リカ被膜を有する複合酸化物系黒色顔料であることを特
徴とする陶磁器・ガラス用インキである。That is, the present invention is an ink for ceramics and glass comprising a low melting point frit and a pigment, characterized in that the pigment is a composite oxide black pigment having a silica coating on the particle surface.
本発明を更に詳細に説明すると、本発明において使用し
本発明を主として特徴づけるシリカ被膜を有する複合酸
化物系黒色顔料１は、従来公知のいずれの技術によって
も得ることができるが、特に好ｔ Ｌ、い方法は、複合
酸化物系黒色顔料を水または希薄なケ”イ酸塩水溶液中
に均一に分散させ、この分散液を均一に撹拌しながら、
この中にケイ酸塩水溶液と中和剤である酸を、同時にか
つ徐々に添加することにより、複合酸化物系黒色顔料表
面にシリカ被膜を沈着形成する方法である。To explain the present invention in more detail, the composite oxide black pigment 1 having a silica film used in the present invention and which mainly characterizes the present invention can be obtained by any conventionally known technique, but is particularly preferred. L. The second method involves uniformly dispersing a complex oxide black pigment in water or a dilute aqueous silicate solution, and stirring the dispersion uniformly.
In this method, a silicate aqueous solution and an acid as a neutralizing agent are simultaneously and gradually added to the mixture, thereby depositing and forming a silica film on the surface of the composite oxide black pigment.
例えば、分散液を８０℃以上好ましくは８５〜９５℃に
加熱し、１〜６重量％のケイ酸塩水溶液と０．５〜３重
量％の酸の水溶液を撹拌しながら、同時にかつ徐々に添
加し、この間の溶液のｐ）１を約９．０〜９．５にａ１
節することにより、最良のシリカ被膜を有する複合酸化
物系黒色顔料得ることがでさる。For example, the dispersion is heated to 80°C or higher, preferably 85 to 95°C, and 1 to 6% by weight silicate aqueous solution and 0.5 to 3% by weight acid aqueous solution are simultaneously and gradually added while stirring. During this time, the p)1 of the solution was adjusted to about 9.0 to 9.5.
By controlling the amount of silica, it is possible to obtain a composite oxide black pigment having the best silica coating.
複合酸化物系黒色顔料を水またはケイ酸塩水溶液中に分
散させる方法は、従来公知の顔料の分散方法はいずれも
使用でき、例えばガラスピーズをメディアとしたサンド
ミル等の分散機ケ用いることができる。To disperse the complex oxide black pigment in water or an aqueous silicate solution, any conventional pigment dispersion method can be used, for example, a dispersion machine such as a sand mill using glass beads as a media can be used. .
複合酸化物系黒色顔料の分散濃度は特に限定されないが
、経済性および製品の均一性を考慮すれば、約５〜１５
重量％程度が好ましい。The dispersion concentration of the complex oxide black pigment is not particularly limited, but considering economic efficiency and product uniformity, it is about 5 to 15
It is preferably about % by weight.
上記において、ケイ酸塩水溶液と酸の水溶液との添加に
要する時間は製造スケールにより異なるが、あまり長時
間であると不経済であるので、一般的には約１〜５時間
程度が好ましい。In the above, the time required for adding the silicate aqueous solution and the acid aqueous solution varies depending on the manufacturing scale, but if it takes too long, it is uneconomical, so it is generally preferred to be about 1 to 5 hours.
本発明において使用するケイ酸塩とは、従来公知の水溶
性のケイ酸塩はいずれも使用でき、またケイ酸塩以外に
ジルコン酸塩、チタン酸塩、その他の金属塩を少量含有
するものであってもよい。The silicates used in the present invention may be any conventionally known water-soluble silicates, and may contain small amounts of zirconates, titanates, and other metal salts in addition to silicates. There may be.
本発明において最も好ましいものは、ケイ酸アルカリ金
属塩、特に３号ケイ酸ナトリウムである。Most preferred in the present invention are alkali metal silicate salts, particularly No. 3 sodium silicate.
また中和剤として使用する酸としては、いずれの無機酸
あるいは有！！１＃でもよいが、最も好ましいものは、
濃度０．５〜３重量％程度の硫酸である。In addition, as the acid used as a neutralizing agent, any inorganic acid or organic acid can be used. ! 1# is acceptable, but the most preferable one is
It is sulfuric acid with a concentration of about 0.5 to 3% by weight.
本発明の陶磁器・ガラス用インキは上記の如きシリカ被
膜を有する複合酸化物系黒色顔料を使用することを主た
る特徴としており、それ以外の成分、例えば低融点フリ
ットおよびベヒクル等はいずれも従来公知のものがその
まま使用できる。The main feature of the ink for ceramics and glass of the present invention is that it uses a complex oxide black pigment having a silica coating as described above, and other components such as a low melting point frit and a vehicle are all conventionally known. Things can be used as is.
例えば低融点フリットとしては、酸化鉛を主成分として
、その他、アルミナ、シリカ、酸化カルシウム、酸化チ
タン、酸化ナトリウム、酸化カリウム、酸化ジルコニウ
ム、耐化亜鉛、酸化ホウ素等から形成されるものであり
、酸化鉛のモル比を調節してその融点を５５０’Ｃ〜６
２０’０程度に調節したものが好ましい、このような低
融点フリー２トはいずれも市場から容易に入手すること
ができる。For example, a low melting point frit is formed from lead oxide as a main component, as well as alumina, silica, calcium oxide, titanium oxide, sodium oxide, potassium oxide, zirconium oxide, zinc oxide, boron oxide, etc. Adjust the molar ratio of lead oxide to increase its melting point from 550'C to 6.
Preferably, the melting point is adjusted to about 20'0, and any such low melting point free 2 can be easily obtained from the market.
またベヒクルとしては、従来陶磁器・ガラス用インキに
用いられているスキージオイルが好ましく使用される。As the vehicle, squeegee oil, which is conventionally used in inks for ceramics and glass, is preferably used.
本発明の陶磁器−ガラス用インキは上記の三成分を必須
成分とするが、その他各種の無機顔料等の如〈従来公知
の添加剤はいずれも必要に応じて併用し得るものである
。The ink for ceramics and glass of the present invention has the above-mentioned three components as essential components, but any conventionally known additives such as various inorganic pigments may be used in combination as necessary.
以上の如き好ましい方法または他の方法で得られるシリ
カ被１漠を有する複合酸化物系黒色顔料は、その全量の
うち約２〜１０重量％がシリカ被膜であるのが好適であ
り、約２重量％未満の量では、得られる複合酸化物系黒
色顔料の耐変色性が不十分であり、また約１０重量％を
越える量では得られる複合酸化物系黒色顔料の着色力、
Ｗｌｌ方力その他の顔料としての性質が低下するので好
ましくない。In the composite oxide black pigment having a silica coating obtained by the above-mentioned preferred method or other methods, it is preferable that the silica coating accounts for about 2 to 10% by weight of the total amount, and about 2% by weight of the silica coating. If the amount is less than about 10% by weight, the color fastness of the obtained complex oxide black pigment will be insufficient, and if the amount exceeds about 10% by weight, the coloring power of the obtained complex oxide black pigment will be insufficient.
This is not preferable because the WII polarity and other properties as a pigment deteriorate.
上記方法で使用する複合酸化物系黒色顔料としては従来
公知の複合酸化物系黒色顔料はいずれも使用でき、例え
ば銅およびクロムの酸化物から成るもの、銅、鉄、クロ
ムの酸化物から成るもの、銅、クロム、マンガンの酸化
物から成るもの等が挙げられる。As the complex oxide black pigment used in the above method, any conventionally known complex oxide black pigment can be used, such as those consisting of copper and chromium oxides, and those consisting of copper, iron, and chromium oxides. , copper, chromium, manganese oxides, etc.
本発明の陶磁器−ガラス用インキにおいては、前記のシ
リカ被膜を有する複合酸化物系黒色顔料は、インキ中に
おいて約４〜８重量％を占める割合で使用するのが好ま
しく、また低融点フリットはインキ中で約６０〜７０重
量％を占める割合で使用するのが好ましく、またベヒク
ルはインキ中で約２５〜３０重量％を占める割合で使用
するのが好ましい。In the ink for ceramics and glass of the present invention, the composite oxide black pigment having a silica coating is preferably used in an amount of about 4 to 8% by weight in the ink, and the low melting point frit is preferably used in the ink. Preferably, the vehicle is used in an amount of about 60 to 70% by weight in the ink, and the vehicle is preferably used in an amount of about 25 to 30% by weight in the ink.
本発明の陶磁器・ガラス用インキを製造する方法自体は
従来公知の方法１例えば３本ロール等を用いて配合物を
十分に混合・磨砕−練肉することによって得ることがで
きる。The ink for ceramics and glass of the present invention can be produced by a conventionally known method 1, for example, by thoroughly mixing, grinding, and kneading the mixture using a three-roller or the like.
（作用・効果）
以上の如き本発明の陶磁器・ガラス用インキは、各種の
陶磁器、ガラス器、ホーロー製品等の表面に各種の文字
５図形等の絵柄を付与するインキとして有用であり１例
えば不発明力陶磁器・ガラス用インキをシルクスクリー
ン印刷やその他の各種の曲面印刷技術によって任意の絵
柄を印刷し、これを約５００〜７００℃の温度で焼付焼
成することにより黒色の諸堅牢性に優れた絵柄を付与す
ることができる。(Function/Effect) The ink for ceramics and glass of the present invention as described above is useful as an ink for imparting patterns such as various letters and figures to the surfaces of various ceramics, glassware, enamel products, etc. Inventiveness By printing any pattern using ink for ceramics and glass using silk screen printing or other various curved surface printing techniques, and baking this at a temperature of about 500 to 700 degrees Celsius, we have created a black color with excellent solidity. A pattern can be added.
本発明の陶磁器−ガラス用インキの最大の特徴は、従来
の複合酸化物系黒色顔料を着色成分とする陶磁器・ガラ
ス用インキにおいては、その焼成焼付時の雰囲気が還元
性であると、顔料中の銅の一部が還元され赤く発色し、
複合酸化物系黒色顔料の漆黒性が失われるため５１％ｌ
化性雰囲気としなければならなかったのに対して、本発
明の陶磁器・ガラス用インキは酸化−ａ元いずれの雰囲
気下で焼付焼成しても、インキ中の複合酸化物系黒色顔
料が何ら変色することなく優れた着色性を有する絵柄を
与えることができる点である。The most important feature of the ink for ceramics and glass of the present invention is that in conventional inks for ceramics and glass that use a complex oxide black pigment as a coloring component, if the atmosphere during baking is reducing, the pigment Some of the copper is reduced and develops a red color,
51% because the jet blackness of the complex oxide black pigment is lost.
In contrast, the ink for ceramics and glass of the present invention does not cause any discoloration of the complex oxide black pigment in the ink even if it is baked in either an oxidizing or oxidizing atmosphere. The point is that it is possible to provide a pattern with excellent coloring properties without the need for coloring.
従って本発明の陶磁器・ガラス用インキを使用すること
によって、簡単な設備で優れた着色陶磁器、着色ガラス
器、着色ホーロー製品等を安価に提供することができる
。Therefore, by using the ink for ceramics and glass of the present invention, excellent colored ceramics, colored glassware, colored enamel products, etc. can be provided at low cost with simple equipment.
次に実施例を挙げて本発明を更に具体的に説明する。な
お、文中％とあるのは重量基準である。Next, the present invention will be explained in more detail with reference to Examples. Note that % in the text is based on weight.
実施例１
複合酸化物系黒色赤色顔料（Ｃｕ−Ｃｒの酸化物系から
成る黒色顔料）２００ｇを水２文中に十分に分散させ、
８５℃に加熱後、この温度に保ちながらスラリー中に、
３号ケイ酸ソーダ（Ｎ ａ２０／５ｉ０２＝局、３０％
水溶液）３４ｇを水４００ＩＩｎ見に加え稀釈した水溶
液と、稀硫酸とを同時にかつ徐々に撹拌しながら３時間
を要して添加する。その１１Ｊ１のスラリーのｐＨは９
．２〜９，５に調節する。Example 1 200 g of a complex oxide-based black red pigment (a black pigment consisting of a Cu-Cr oxide system) was sufficiently dispersed in 2 cups of water,
After heating to 85°C, while maintaining this temperature, in the slurry,
No. 3 Sodium Silicate (N a20/5i02= Bureau, 30%
An aqueous solution prepared by adding 34 g of aqueous solution to 400 IIn of water and diluted with diluted sulfuric acid are added simultaneously and gradually with stirring over a period of 3 hours. The pH of the 11J1 slurry is 9
．． Adjust to 2-9.5.
滴下終了後、撹拌を止めそのままの状態で約１時間熟成
し、その後希硫酸で中和しスラリーのｐＨを７に調節し
、シリカ被膜を完成させる。After the dropwise addition is completed, the stirring is stopped and the slurry is aged for about 1 hour, and then neutralized with dilute sulfuric acid to adjust the pH of the slurry to 7 to complete the silica coating.
次いで常法により濾過、水洗および乾燥して、シリカ被
膜を有する複合酸化物系黒色顔料２１０ｇを得た。この
顔料中のシリカ被膜は、顔料の５ｆｆｉｆｆｉ％を占め
るものであった。The mixture was then filtered, washed with water, and dried in a conventional manner to obtain 210 g of a composite oxide black pigment having a silica coating. The silica film in this pigment accounted for 5ffiffi% of the pigment.
実施例２
複合酸化物系黒色顔料（Ｃｕ−Ｃｒ−Ｍｎの酸化物系か
ら成る黒色顔料）を使用し、他は実施例１と同様にして
シリカ被膜（５重量％）を有する複合酸化物系黒色顔料
を得た。Example 2 A complex oxide black pigment (a black pigment consisting of a Cu-Cr-Mn oxide system) was used, except that a complex oxide system with a silica coating (5% by weight) was prepared in the same manner as in Example 1. A black pigment was obtained.
実施例３
複合酸化物系黒色顔料（Ｃｕ−Ｆｅ−Ｃｒの酸化物系か
ら成る黒色顔料）を使用し、他は実施例ｌと同様にして
シリカ被膜（５重量％）を有する複合酸化物系黒色顔料
を得た。Example 3 A complex oxide black pigment (a black pigment consisting of a Cu-Fe-Cr oxide system) was used, except that a complex oxide system with a silica coating (5% by weight) was prepared in the same manner as in Example 1. A black pigment was obtained.
実施例４
実施例１〜３で得られたシリカ被膜を有する複合酸化物
系黒色顔料０．５ｇ、低融点フリット５ｇおよびスキー
ジオイル２ｇをセラミック用３木ロールで混合分散して
本発明の陶磁器・ガラス用インキＡ（実施例１）、Ｂ（
実施例２）およびＣ（実施例３）を得た。一方実施例１
〜３に対応するシリカ被ｎりを有さない複合酸化物系黒
色顔料をそれぞれ用いて同様にして比較用の陶磁器・ガ
ラス用インキＡ′（実施例１に対応する顔料）、Ｂ′
（実施例２に対応する顔料）およびＣ′ （実施例３に
対応する顔料）を得た。Example 4 0.5 g of the composite oxide black pigment having a silica coating obtained in Examples 1 to 3, 5 g of low melting point frit, and 2 g of squeegee oil were mixed and dispersed using a 3-wooden roll for ceramics to produce the ceramic of the present invention. Glass ink A (Example 1), B (
Example 2) and C (Example 3) were obtained. On the other hand, Example 1
Comparative ceramic/glass inks A' (pigment corresponding to Example 1) and B' were prepared in the same manner using complex oxide-based black pigments without silica coating corresponding to No. 3 to 3, respectively.
(pigment corresponding to Example 2) and C' (pigment corresponding to Example 3) were obtained.
上記の本発明の陶磁器・ガラス用インキＡ−Ｃおよび比
較用の陶磁器・ガラス用インキＡ′〜Ｃ′をガラス容器
にスクリーン印刷し、次いで還元雰囲気下で６２０℃で
２０分間焼付焼成したところ、本発明の陶磁器・ガラス
用インキＡ−Ｃを用いたものはそれぞれ漆黒性ある発色
を示したが、比較用の陶磁器・ガラス用インキＡ′〜Ｃ
′を用いたものはいずれも色調が赤味をおび、漆黒性に
劣るものであった。The above inks for ceramics and glass of the present invention A-C and comparative inks for ceramics and glass A' to C' were screen printed on a glass container, and then baked at 620°C for 20 minutes in a reducing atmosphere. Inks using inks A-C for ceramics and glass of the present invention exhibited jet-black coloring, but comparative inks A' to C for ceramics and glass showed jet-black coloring.
All of the products using `` had a reddish tone and were inferior in jet blackness.
特許出願人 大日精化工業株式会社（他１名）Patent applicant: Dainichiseika Kagyo Co., Ltd. (1 other person)
Claims (4)
ス用インキにおいて、顔料が粒子表面にシリカ被膜を有
する複合酸化物系黒色顔料であることを特徴とする陶磁
器・ガラス用インキ。(1) An ink for ceramics and glass comprising a low melting point frit and a pigment, characterized in that the pigment is a composite oxide black pigment having a silica coating on the particle surface.
を占める特許請求の範囲第（１）項に記載の陶磁器・ガ
ラス用インキ。(2) The amount of silica film is 2 to 10% by weight in the entire pigment
The ink for ceramics and glass according to claim (1), which occupies the following.
る特許請求の範囲第（１）項に記載の陶磁器・ガラス用
インキ。(3) The ink for ceramics and glass according to claim (1), wherein the low melting point frit is a lead oxide based low melting point frit.
範囲第（１）項に記載の陶磁器・ガラス用インキ。(4) The ink for ceramics and glass according to claim (1), wherein the complex oxide black pigment contains copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14045785A JPS623044A (en) | 1985-06-28 | 1985-06-28 | Ink for pottery and glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14045785A JPS623044A (en) | 1985-06-28 | 1985-06-28 | Ink for pottery and glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS623044A true JPS623044A (en) | 1987-01-09 |
| JPH0210103B2 JPH0210103B2 (en) | 1990-03-06 |
Family
ID=15269051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14045785A Granted JPS623044A (en) | 1985-06-28 | 1985-06-28 | Ink for pottery and glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS623044A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996041773A1 (en) * | 1995-06-08 | 1996-12-27 | Saint-Gobain Vitrage | Curable squeegee paste for printing on glass surfaces, and method for making same |
| CN104098271A (en) * | 2013-04-04 | 2014-10-15 | Tdk株式会社 | Black marker composition and an electronic component using these |
-
1985
- 1985-06-28 JP JP14045785A patent/JPS623044A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996041773A1 (en) * | 1995-06-08 | 1996-12-27 | Saint-Gobain Vitrage | Curable squeegee paste for printing on glass surfaces, and method for making same |
| CN104098271A (en) * | 2013-04-04 | 2014-10-15 | Tdk株式会社 | Black marker composition and an electronic component using these |
| JP2014201484A (en) * | 2013-04-04 | 2014-10-27 | Tdk株式会社 | Black marking composition and electronic component using the same |
| CN104098271B (en) * | 2013-04-04 | 2017-05-10 | Tdk株式会社 | Black marker composition and an electronic component using these |
| US9966342B2 (en) | 2013-04-04 | 2018-05-08 | Tdk Corporation | Black marker composition and an electronic component using these |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0210103B2 (en) | 1990-03-06 |
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