JPH10167756A - Lead-free overglaze color for pottery - Google Patents
Lead-free overglaze color for potteryInfo
- Publication number
- JPH10167756A JPH10167756A JP32057696A JP32057696A JPH10167756A JP H10167756 A JPH10167756 A JP H10167756A JP 32057696 A JP32057696 A JP 32057696A JP 32057696 A JP32057696 A JP 32057696A JP H10167756 A JPH10167756 A JP H10167756A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- oxide
- weight
- free
- paint
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、陶磁器加飾用上絵
具に関し、特に鉛を含まない陶磁器用無鉛上絵具に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic decorative paint, and more particularly to a lead-free ceramic lead-free paint.
【０００２】[0002]
【従来の技術】古来（中国宗時代に始まる）から現代の
伝統的な東洋陶磁には、陶磁器表面に一定の厚さ（２０
〜８００μｍ程度）を有するガラス質層により特徴のあ
る多色の加飾が施されている。これらを日本では、盛り
絵具又は和絵具と称される陶磁器加飾用上絵具により加
飾されている。陶磁器加飾用上絵具としては、多くの場
合、鉛を含有する上絵具が使用されている。2. Description of the Related Art Traditional oriental ceramics from ancient times (beginning in the Chinese sect era) have a certain thickness (20
Characteristic multicolor decoration is performed by a glassy layer having a thickness of about 800 μm. In Japan, these are decorated with a ceramic decorative paint, which is called a prime paint or a Japanese paint. In many cases, lead paint containing lead is used as a decorative paint for ceramics.
【０００３】しかし、昭和４５（１９７０）年以来、米
国を始めとして世界各国で鉛に対する安全規制が実施さ
れ、米国食品医薬品局（ＦＤＡ）の規制が制定され、平
行して我が国における食品衛生法で、有害重金属の規制
値の強化があり、鉛、カドミウムの安全使用に関わる技
術対策の研究が進められてきた。However, since 1970, safety regulations for lead have been implemented in the United States and other countries around the world, and regulations of the US Food and Drug Administration (FDA) have been enacted. In addition, regulations on toxic heavy metals have been strengthened, and research on technical measures related to the safe use of lead and cadmium has been promoted.
【０００４】また、近年では国際標準化機構（ＩＳＯ）
の規制値の低下と追い討ち的にカリフォルニヤ州のプロ
ポジション６５により、食器からの鉛溶出への規制はま
すます厳しいものになっている。In recent years, the International Organization for Standardization (ISO)
In tandem with the lowering of regulatory values, California's Proposition 65 has placed increasingly stringent restrictions on lead elution from tableware.
【０００５】さらに、有鉛上絵具は食酢や食器自動洗浄
器の熱アルカリ溶液に侵され、また、多少の衝撃、摩
擦、磨耗により変色、絵落ち、剥離、傷による艶落ち等
がみられるばかりか、陶磁器の上絵付け作業従事者の身
体への悪影響の恐れや絵筆や容器その他の洗浄の際に排
出される鉛・カドミウム含有廃液による河川等の汚染は
深刻な環境問題となっている。[0005] Furthermore, leaded paints are attacked by vinegar and hot alkaline solutions of automatic dishwashers, and are discolored by slight impact, friction and abrasion, and are easily discolored, peeled off, and delustered by scratches. On the other hand, there is a serious environmental problem due to the danger of adverse effects on the bodywork of the painter, and the pollution of rivers and the like by the waste liquid containing lead and cadmium discharged when washing paintbrushes, containers and the like.
【０００６】そのため、食器からの鉛・カドミウム溶出
規制に関してこれまで様々な溶出抑制方法が提案されて
きた。例えば、珪酸−鉛系フリットに微量の酸化ジルコ
ニウムを添加して耐酸性を向上させたり、焼成工程にお
いて窯詰めを工夫したり、さらには炉内温度の均一化を
図ったり、焼成中に水蒸気を吹き込む工法やガス抜きを
促進させるなどの試みがなされた。しかしながら、従来
から使用されている有鉛上絵具は珪酸−鉛系フリットか
らなるため、これらの方法ではわずかな焼成条件の変化
を受け易く、鉛成分の溶出を完全に抑制することは不可
能であり、鉛を含有する陶磁器用上絵具を使用する限り
においては、鉛成分の溶出を完全に抑制を完全に解決す
る方法は見出されていない。[0006] For this reason, various elution control methods have been proposed so far with respect to the regulation of lead and cadmium elution from tableware. For example, a small amount of zirconium oxide is added to a silicic acid-lead frit to improve acid resistance, a method of packing in a kiln in the baking process, a uniform temperature in the furnace, and a method of generating water vapor during baking. Attempts were made to promote the blowing method and degassing. However, since the leaded paints conventionally used are made of silicate-lead frit, these methods are susceptible to slight changes in firing conditions, and it is impossible to completely suppress the elution of lead components. However, as long as a lead-containing ceramic paint is used, no method has been found to completely suppress the elution of the lead component.
【０００７】そこで、無鉛上絵具の開発が進められ、陶
磁器に８００°Ｃ前後で焼き付き、剥離も無く、種々の
呈色を表す無鉛上絵具が提案された（特公平５−５３７
３５号公報）。[0007] Therefore, lead-free paints have been developed, and lead-free paints exhibiting various colors without burning or peeling at about 800 ° C on ceramics have been proposed (Japanese Patent Publication No. 5-537).
No. 35).
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、前記の
無鉛上絵具は、伝統的な有鉛上絵具と対比すれば、有鉛
上絵具の醸し出す独特の色艶と明らかに相違するため、
市場に受け入れられ難く、その普及率は低いのが現状で
ある。また、市販の無鉛フリットを用いた上絵具や「交
趾」と称する加飾剤があるが、特に耐酸性が低く食酢等
に侵され易く実用するには問題がある。However, since the above-mentioned lead-free upper paint is clearly different from the traditional color and luster produced by the lead-free upper paint when compared with the traditional lead-like upper paint,
At present, it is hardly accepted by the market and its penetration rate is low. In addition, there are commercially available overpaints using lead-free frit and decorative agents called "toes". However, they are particularly low in acid resistance and are easily susceptible to vinegar and the like, which poses a problem in practical use.
【０００９】本発明は、従来から使用されてきた有鉛上
絵具の醸し出す独特の色艶に非常に近似し、さらに、耐
食性に優れた陶磁器用無鉛上絵具を提供するものであ
る。[0009] The present invention provides a lead-free paint for ceramics which is very similar to the unique color and luster produced by the conventionally used leaded paints and has excellent corrosion resistance.
【００１０】[0010]
【課題を解決するための手段】本発明の陶磁器用無鉛上
絵具は、酸化珪素３０〜６０重量％、酸化硼素１０〜４
０重量％、アルカリ金属酸化物５〜２０重量％、酸化亜
鉛０．５〜６重量％、酸化ジルコニウム２〜１０重量
％、酸化アルミニウム１〜６重量％、酸化ニオブ又は酸
化タンタルの１種又は２種０．５〜１５重量％からなる
フリットに着色剤を含有させる。さらに、アルカリ土類
金属酸化物を０．５〜１０重量％含有させてもよい。The lead-free paint for ceramics according to the present invention comprises 30 to 60% by weight of silicon oxide and 10 to 4% of boron oxide.
0% by weight, 5 to 20% by weight of alkali metal oxide, 0.5 to 6% by weight of zinc oxide, 2 to 10% by weight of zirconium oxide, 1 to 6% by weight of aluminum oxide, one or two of niobium oxide or tantalum oxide A colorant is included in a frit consisting of 0.5 to 15% by weight of the seed. Further, an alkaline earth metal oxide may be contained in an amount of 0.5 to 10% by weight.
【００１１】[0011]
【発明の実施の形態】有鉛上絵具の醸し出す独特の色艶
を発現する無鉛上絵具について、両者の光学的特性を比
較した結果は、次のとおりであった。BEST MODE FOR CARRYING OUT THE INVENTION The results of comparing the optical properties of lead-free paints, which exhibit the unique color and luster produced by the lead paints, are as follows.
【００１２】（１） 従来の有鉛上絵具の屈折率１．６
〜１．７に対し、従来の無鉛上絵具の屈折率は１．４〜
１．５である。(1) Refractive index 1.6 of conventional leaded paint
The refractive index of the conventional lead-free paint is 1.4 to 1.7.
1.5.
【００１３】（２） ４００ｎｍ付近の吸収スベクトル
は従来の有鉛フリットで０．４Ａｂｓに対し、従来の無
鉛上絵具のそれは０．０５Ａｂｓであった。さらに、各
種「有鉛フリット」はわずかに黄味を帯びている。(2) The absorption spectrum near 400 nm was 0.4 Abs for the conventional leaded frit, whereas that of the conventional lead-free top paint was 0.05 Abs. In addition, various "leaded frit" are slightly yellowish.
【００１４】この点に着目し、屈折率及び吸収スペクト
ルは、それぞれ単独に又は相互作用によって上絵具の色
艶の差となって現れ、有鉛上絵具の持つ特有の色艶は鉛
ガラスのもつ光学的特性に影響されるものであり、無鉛
上絵具、つまりアルカリガラスとは屈折率、吸収スペク
トルの相対強度及び色に差があることになる。したがっ
て、無鉛フリットの吸収スペクトルの相対強度を１．５
５〜１．７に近付けるとともに、屈折率を０．４Ａｂｓ
に近付けかつ有鉛フリットに近い黄色味を付与するた
め、屈折率及び吸収スペクトルを制御することにより有
鉛上絵具に近似した無鉛上絵具とすることを知見した。Paying attention to this point, the refractive index and the absorption spectrum appear as a difference in the color and luster of the upper paint alone or by interaction, and the characteristic color and luster of the leaded upper paint is that of lead glass. It is affected by the optical characteristics, and has a difference in the refractive index, the relative intensity of the absorption spectrum, and the color from the lead-free paint, that is, the alkali glass. Therefore, the relative intensity of the absorption spectrum of the lead-free frit is set to 1.5.
5 to 1.7 and refractive index of 0.4 Abs
It has been found that a lead-free paint similar to a lead-free paint is obtained by controlling a refractive index and an absorption spectrum to give a yellow tint close to that of a lead frit.
【００１５】そこで、ガラス組成のなかで屈折率および
色について鉛ガラスと近似した光学的特性を無鉛上絵具
に付与するため、ガラスにおける屈折率を向上させかつ
可視光線の吸収を左右する元素としてタンタル、ニオブ
の一種又は二種をガラス組成の中に組み込む。Therefore, in order to impart, to the lead-free paint, optical properties similar to those of lead glass in terms of refractive index and color in the glass composition, tantalum is used as an element that improves the refractive index of glass and affects the absorption of visible light. One or two of niobium are incorporated into the glass composition.
【００１６】本発明の陶磁器用無鉛上絵具において、酸
化珪素は、上絵具フリットにおける主成分で３０〜６０
重量％含有させ、３０重量％未満であると化学的耐久性
が劣化し、６０重量％を超えると溶融温度が高くなると
いう問題が生じる。In the lead-free top paint for ceramics of the present invention, silicon oxide is a main component in the top paint frit and is 30 to 60%.
If the content is less than 30% by weight, the chemical durability deteriorates, and if it exceeds 60% by weight, the melting temperature becomes high.
【００１７】酸化硼素は、上絵具フリットの溶融温度を
低下させる目的で含有させ、１０重量％未満であると溶
融温度低下の効果が少なく、４０重量％を超えると耐酸
性が悪くなるので、１０〜４０重量％含有させる。Boron oxide is contained for the purpose of lowering the melting temperature of the upper paint frit. If the content is less than 10% by weight, the effect of lowering the melting temperature is small, and if it exceeds 40% by weight, the acid resistance deteriorates. -40% by weight.
【００１８】アルカリ金属酸化物は、１種又は２種以上
を溶融温度を低下させる目的で５〜２０重量％含有さ
せ、５重量％未満であると溶融温度低下の効果が少な
く、２０重量％を超えると耐酸性がなくなり、貫入が発
生しやすくなる。アルカリ金属酸化物は、焼成により酸
化物となるものものであればよく、例えば、炭酸塩の形
で添加すればよい。One or more alkali metal oxides are contained in an amount of 5 to 20% by weight for the purpose of lowering the melting temperature. When the content is less than 5% by weight, the effect of lowering the melting temperature is small, and 20% by weight is used. If it exceeds, acid resistance is lost, and penetration easily occurs. The alkali metal oxide may be any as long as it becomes an oxide upon firing, and for example, may be added in the form of a carbonate.
【００１９】酸化亜鉛は、上絵具の溶化温度調整剤とし
て使用し、特に着画面の平滑性を発揮させるために、
０．５〜６重量％含有させ、０．５％未満では平滑性が
なく筆跡が残りムラが生じ、また、６重量％を超えると
溶化温度が高くなるため、表面に気泡跡が目立ち美観を
損なう。Zinc oxide is used as a solubilizing temperature adjusting agent for overcolor paints.
If it is contained in an amount of from 0.5 to 6% by weight, if it is less than 0.5%, there is no smoothness and the handwriting remains and unevenness occurs. If it exceeds 6% by weight, the solubilizing temperature becomes high, so that the air bubble mark is conspicuous on the surface and the appearance is beautiful. Spoil.
【００２０】酸化ジルコニウムは熱膨張調整剤として、
また、色調調整剤として２〜１０重量％含有させ、２重
量％未満であると剥離しやすく、１０重量％を超えると
乳濁し、透明感が損なわれる。Zirconium oxide is used as a thermal expansion regulator.
Further, 2 to 10% by weight is contained as a color tone adjusting agent, and if it is less than 2% by weight, it is easy to peel off, and if it exceeds 10% by weight, it becomes milky and the transparency is impaired.
【００２１】酸化アルミニウムは、絵具の安定剤が溶け
て流れ落ちるのを防止するための粘調剤として、１〜６
重量％含有させ、１重量％未満であると、適正焼成温度
幅が著しく狭くなり、６重量％を超えると透明感が損な
われ、また、溶け難くなる。本発明の陶磁器用無鉛上絵
具は、前記の各組成成分のほかに、さらにＶＡ族の酸化
ニオブ及び／又は酸化タンタルを０．５〜１５重量％含
有させる。酸化ニオブ及び酸化タンタルは、化学的耐久
性を向上させるとともに、熱膨張調整剤として作用し、
０．５重量％未満であると化学的耐久性が劣化し、釉薬
から剥奪する。また、１５重量％を超えると溶融温度が
上がり、溶け不足により失透する。Aluminum oxide is used as a thickening agent for preventing a paint stabilizer from melting and falling off.
If the content is less than 1% by weight, the appropriate firing temperature range becomes extremely narrow, and if it exceeds 6% by weight, the transparency is impaired and it becomes difficult to melt. The lead-free top paint for ceramics of the present invention further contains 0.5 to 15% by weight of VA group niobium oxide and / or tantalum oxide in addition to the above-mentioned respective components. Niobium oxide and tantalum oxide improve chemical durability and act as a thermal expansion regulator,
If it is less than 0.5% by weight, the chemical durability deteriorates, and it is stripped from the glaze. On the other hand, if the content exceeds 15% by weight, the melting temperature rises and devitrification occurs due to insufficient melting.
【００２２】本発明の陶磁器用無鉛上絵具は、さらに、
アルカリ土類金属酸化物を０．５〜１０重量％含有させ
てもよい。アルカリ土類金属酸化物は、酸化珪素の溶化
を促進する作用があるが、０．５重量％未満ではその効
果がなく、また、１０重量％を超えると乳濁し、また、
上絵具に平滑性がなくなる。The lead-free paint for ceramics of the present invention further comprises:
The alkaline earth metal oxide may be contained in an amount of 0.5 to 10% by weight. Alkaline earth metal oxides have the effect of accelerating the solubilization of silicon oxide. However, when the content is less than 0.5% by weight, the effect is not obtained.
The upper paint loses smoothness.
【００２３】したがって、溶融温度と熱膨張係数はＳｉ
Ｏ2／Ｋ2Ｏ＋Ｎａ2Ｏ＋Ｂ2Ｏ3とＴａ2Ｏ3＋Ｎｂ2Ｏ5の
比で材料設計を行う。また、屈折率及びガラスの黄色味
はニオブ及びタン夕ルの酸化物をガラス組成へ加えるこ
とで鉛ガラスに近似した無鉛上絵具用フリットが得られ
る。Therefore, the melting temperature and the coefficient of thermal expansion are
The material is designed based on the ratio of O 2 / K 2 O + Na 2 O + B 2 O 3 to Ta 2 O 3 + Nb 2 O 5 . Also, by adding oxides of niobium and tansol to the glass composition with respect to the refractive index and the yellow tint of the glass, it is possible to obtain a frit for a lead-free upper paint similar to lead glass.
【００２４】本発明の陶磁器用無鉛上絵具の好ましいフ
リットの配合割合は、酸化珪素４５．３重量％、酸化硼
素２５．５重量％、酸化ナトリウム３．０重量％、酸化
カリウム８．８重量％、酸化亜鉛４．９重量％、酸化ジ
ルコニウム４．７重量％、酸化アルミニウム２．９重量
％、酸化バリウム５．０重量％の混合物に酸化ニオブ
８．０重量％又は酸化タンタル４．０重量％である。The preferred proportion of the frit in the lead-free paint for ceramics of the present invention is 45.3% by weight of silicon oxide, 25.5% by weight of boron oxide, 3.0% by weight of sodium oxide and 8.8% by weight of potassium oxide. 4.9% by weight of zinc oxide, 4.7% by weight of zirconium oxide, 2.9% by weight of aluminum oxide and 5.0% by weight of barium oxide in a mixture of 8.0% by weight of niobium oxide or 4.0% by weight of tantalum oxide. It is.
【００２５】着色剤としては、銅、クロム、コバルト、
ニッケル、マンガン、鉄、アンチモン等の酸化物及び炭
酸塩やスピネル型、インクルージョン型等の顔料を添加
する。As the coloring agent, copper, chromium, cobalt,
Oxides and carbonates such as nickel, manganese, iron and antimony, and pigments such as spinel type and inclusion type are added.
【００２６】[0026]
フリットの製造方法 天然原料として珪石、カオリンを使用し、これに珪酸ジ
ルコニウム、酸化硼素、酸化バリウム、酸化亜鉛、酸化
ナトリウム、酸化カリウムを表１及び表２に示す組成割
合に合わせ調整し、１バッチ、１ｋｇとし、１時間をか
けて乾式で粉砕混合した。Production method of frit Silica and kaolin are used as natural raw materials, and zirconium silicate, boron oxide, barium oxide, zinc oxide, sodium oxide, and potassium oxide are adjusted to the composition ratios shown in Tables 1 and 2, and one batch. 1 kg, and pulverized and mixed in a dry manner over 1 hour.
【００２７】[0027]
【表１】 次いで、混合物を坩堝に移し、電気炉で１２８０°Ｃで
２時間溶融熟成した後、水中にその溶融物を落下させ、
急冷し、最大粒径５ｍｍφ程度のフリットとした。さら
に、このフリットを乾式微粉砕機で微粉末化した。その
際の容器はジルコニア製ポット（内容積：５００ｍｌ）
で、粉砕メディアはジルコニア製ボール（１ｃｍφ）と
ジルコニア製ビーズ（０．５ｃｍφ）の二段階に変えて
数ミクロン程度のフリット粉末に調整した。[Table 1] Next, the mixture was transferred to a crucible, melt-aged in an electric furnace at 1280 ° C. for 2 hours, and then the melt was dropped into water.
It was rapidly cooled to obtain a frit having a maximum particle size of about 5 mmφ. Further, the frit was pulverized with a dry pulverizer. The container at that time is a zirconia pot (internal volume: 500 ml)
The pulverization medium was changed to two stages of a zirconia ball (1 cmφ) and a zirconia bead (0.5 cmφ) to prepare a frit powder of about several microns.
【００２８】各種フリットの屈折率及び吸収スペクトル
（４００ｎｍ）の相対強度は表３に示すとおりである。The refractive index and the relative intensity of the absorption spectrum (400 nm) of the various frit are as shown in Table 3.
【００２９】[0029]
【表２】 本発明の実施例からも明らかなとおり、本発明は光学特
性において、屈折率は、従来の無鉛上絵具（比較例３及
び４）と同等あるいはそれ以上の値を示し、吸収スペク
トルは無鉛上絵具（比較例３及び４）と同等あるいはそ
れ以上の差があり無鉛上絵具の基礎となるフリットと同
様な黄色味を呈しているため、実施例１〜９では、有鉛
上絵具と同等の色艶が得られた。中でも、実施例６で
は、有鉛上絵具（比較例１及び２）と近似した屈折率及
び吸収スペクトルが得られた。[Table 2] As is clear from the examples of the present invention, in the present invention, in the optical characteristics, the refractive index shows a value equal to or higher than that of the conventional lead-free paint (Comparative Examples 3 and 4), and the absorption spectrum shows the lead-free paint. (Comparative Examples 3 and 4) There is a difference equal to or greater than that of Comparative Examples 3 and 4, and it has the same yellow tint as the frit that is the basis of the lead-free upper paint. A luster was obtained. Above all, in Example 6, a refractive index and an absorption spectrum similar to those of the leaded paint (Comparative Examples 1 and 2) were obtained.
【００３０】本発明の実施例のフリットに顔料を添加し
た陶磁器用無鉛上絵具は、７５０〜１０５０°Ｃの範囲
で溶融することにより陶磁器表面にガラス層として焼き
付けることがてき、わずかに黄色味を帯び、また、熱膨
張係数が５．２〜７．５×１０6／°Ｃの範囲で陶磁器
のそれとあまり差がないため、陶磁器への親和性も良か
った。さらに、本発明の無鉛上絵具は、従来の無鉛上絵
具（比較例３及び４）に比較して、明らかに色艶が優
れ、有鉛上絵具の色艶と同等であった。The lead-free paint for porcelain obtained by adding a pigment to the frit according to the embodiment of the present invention can be baked as a glass layer on the porcelain surface by melting at a temperature in the range of 750 to 1050 ° C. In addition, since there was little difference from that of the ceramic in the range of 5.2 to 7.5 × 10 6 / ° C., the affinity for the ceramic was good. Furthermore, the lead-free upper paint of the present invention was clearly superior in color and luster to the conventional lead-free upper paint (Comparative Examples 3 and 4), and was equivalent to the color and luster of the leaded upper paint.
【００３１】また、耐酸・耐アルカリ性は３％塩酸水溶
液、３％苛性ソーダ水溶液にそれぞれ８時間浸漬（陶磁
器質タイルＪＩＳＡ５２０９による）試験でも外観上変
化せず、各種各色の無鉛上絵具からは有害元素の溶出は
全く検出されず、しかも外観上も曇り等の変化も生じな
いものである。また、４％酢酸水溶液１日浸漬試験でも
同様であった。In addition, the acid and alkali resistance does not change in appearance even in a 3% hydrochloric acid aqueous solution and a 3% caustic soda aqueous solution for 8 hours (according to JIS A5209 for ceramic tile). No elution is detected, and no change in appearance such as cloudiness occurs. The same applies to a 1% immersion test in a 4% acetic acid aqueous solution.
【００３２】さらに、本発明の無鉛上絵具は、機械的強
度、表面硬度及び密着性に優れ、多少の衝撃、摩擦によ
っても絵落ち、剥離、傷による艶落ち等がみられなかっ
た。以上の結果より、本発明の無鉛上絵具は、屈折率お
よび色合いを制御することによって、従来から使用され
ている有鉛上絵具と同等の質感を発現することが可能で
あることがわかる。Furthermore, the lead-free top paint of the present invention is excellent in mechanical strength, surface hardness, and adhesion, and does not show picture dropping, peeling, or glazing due to scratches even with some impact or friction. From the above results, it can be seen that the lead-free upper paint of the present invention can exhibit the same texture as the conventionally used lead-like upper paint by controlling the refractive index and the color.
【００３３】[0033]
（１） 本発明の無鉛上絵具は、鉛を用いないので、陶
磁器からの鉛溶出が全くないため、有害物資による陶磁
器の使用者及び上絵付作業従事者の身体への悪影響がな
く、また、有害物質による環境汚染がない。(1) Since the lead-free paint of the present invention does not use lead, there is no lead elution from the ceramic, so there is no adverse effect on the body of the user of the ceramic and the worker engaged in overpainting due to harmful substances. No environmental pollution by harmful substances.
【００３４】（２） 本発明の無鉛上絵具は、熱膨張係
数が陶磁器のそれとあまり差がないため、陶磁器への親
和力が高く、剥離が起こらない。(2) The lead-free paint of the present invention has a high coefficient of thermal expansion, which is not so different from that of porcelain, so that it has a high affinity for porcelain and does not peel off.
【００３５】（３） 本発明の無鉛上絵具は、耐酸・耐
アルカリ性に優れ、外観の変化がない。(3) The lead-free top paint of the present invention is excellent in acid resistance and alkali resistance and has no change in appearance.
【００３６】（４） 本発明の無鉛上絵具は、機械的強
度、表面硬度及び密着性に優れ、多少の衝撃、摩擦によ
って剥離、傷による艶落ち等がみられない。(4) The lead-free top paint of the present invention is excellent in mechanical strength, surface hardness, and adhesion, and does not show any peeling due to some impact or friction, and no glazing due to scratches.
Claims (2)
０〜４０重量％、アルカリ金属酸化物５〜２０重量％、
酸化亜鉛０．５〜６重量％、酸化ジルコニウム２〜１０
重量％、酸化アルミニウム１〜６重量％、酸化ニオブ又
は酸化タンタルの１種又は２種０．５〜１５重量％から
なるフリットに着色剤を含有させた陶磁器用無鉛上絵
具。1. Silicon oxide 30 to 60% by weight, boron oxide 1
0 to 40% by weight, 5 to 20% by weight of an alkali metal oxide,
0.5 to 6% by weight of zinc oxide, 2 to 10 of zirconium oxide
A lead-free paint for ceramics, comprising a frit comprising 0.5% to 15% by weight of one or two kinds of niobium oxide or tantalum oxide in an amount of 0.5 to 15% by weight.
重量％含有させたことを特徴とする請求項１記載の陶磁
器用無鉛上絵具。2. An alkaline earth metal oxide having a content of 0.5 to 10
The lead-free paint for ceramics according to claim 1, wherein the paint is contained by weight%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8320576A JP2975318B2 (en) | 1996-11-29 | 1996-11-29 | Lead-free paint for ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8320576A JP2975318B2 (en) | 1996-11-29 | 1996-11-29 | Lead-free paint for ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10167756A true JPH10167756A (en) | 1998-06-23 |
| JP2975318B2 JP2975318B2 (en) | 1999-11-10 |
Family
ID=18122977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8320576A Expired - Fee Related JP2975318B2 (en) | 1996-11-29 | 1996-11-29 | Lead-free paint for ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2975318B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492289B1 (en) | 1999-05-24 | 2002-12-10 | Denso Corporation | Lead-free glaze and spark plug |
| US6881690B2 (en) | 2002-02-19 | 2005-04-19 | Noritake Co., Ltd. | Compositions for the decoration of ceramic materials |
| US6924246B2 (en) | 2002-08-07 | 2005-08-02 | Noritake Co., Limited | Lead-free glass compositions for decorating ceramic materials |
| WO2019142426A1 (en) * | 2018-01-19 | 2019-07-25 | 佐賀県 | Overglaze decoration material, ceramic product and method for manufacturing ceramic product |
| WO2019202759A1 (en) * | 2018-04-19 | 2019-10-24 | 佐賀県 | Glass material for enamel, enamel product, and method for producing enamel product |
| JP2019202902A (en) * | 2018-05-22 | 2019-11-28 | 日本電気硝子株式会社 | Glass, glass filler, and resin mixture |
| CN115108723A (en) * | 2022-07-12 | 2022-09-27 | 福建省丰永顺陶瓷花纸有限公司 | Irregular-shape ceramic glazing process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101141262B1 (en) | 2010-02-05 | 2012-05-04 | 경기도 | Multi-color and marbling frit glaze and method of ceramic ware using the same |
-
1996
- 1996-11-29 JP JP8320576A patent/JP2975318B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492289B1 (en) | 1999-05-24 | 2002-12-10 | Denso Corporation | Lead-free glaze and spark plug |
| US6881690B2 (en) | 2002-02-19 | 2005-04-19 | Noritake Co., Ltd. | Compositions for the decoration of ceramic materials |
| US6924246B2 (en) | 2002-08-07 | 2005-08-02 | Noritake Co., Limited | Lead-free glass compositions for decorating ceramic materials |
| WO2019142426A1 (en) * | 2018-01-19 | 2019-07-25 | 佐賀県 | Overglaze decoration material, ceramic product and method for manufacturing ceramic product |
| JP2019123655A (en) * | 2018-01-19 | 2019-07-25 | 佐賀県 | Overglaze decorative material, pottery product, and method for producing pottery product |
| CN111788166A (en) * | 2018-01-19 | 2020-10-16 | 佐贺县 | Over-glaze decoration material, ceramic ware product and method for manufacturing ceramic ware product |
| US11479514B2 (en) | 2018-01-19 | 2022-10-25 | Saga Prefecture | Overglaze decoration material |
| WO2019202759A1 (en) * | 2018-04-19 | 2019-10-24 | 佐賀県 | Glass material for enamel, enamel product, and method for producing enamel product |
| JP2019189477A (en) * | 2018-04-19 | 2019-10-31 | 佐賀県 | Glass material for enamel, enamel product, production method of enamel product |
| JP2019202902A (en) * | 2018-05-22 | 2019-11-28 | 日本電気硝子株式会社 | Glass, glass filler, and resin mixture |
| CN115108723A (en) * | 2022-07-12 | 2022-09-27 | 福建省丰永顺陶瓷花纸有限公司 | Irregular-shape ceramic glazing process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2975318B2 (en) | 1999-11-10 |
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