JP2005082438A - Yo-hen adorned pottery and its manufacturing method - Google Patents

Yo-hen adorned pottery and its manufacturing method Download PDF

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JP2005082438A
JP2005082438A JP2003315575A JP2003315575A JP2005082438A JP 2005082438 A JP2005082438 A JP 2005082438A JP 2003315575 A JP2003315575 A JP 2003315575A JP 2003315575 A JP2003315575 A JP 2003315575A JP 2005082438 A JP2005082438 A JP 2005082438A
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Osamu Ohira
修 大平
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of developing on purpose a yo-hen (best-quality) pattern, which naturally occurs at a high temperature furnace and can be called an accidental product, and being formed as a design. <P>SOLUTION: In this method, a yo-hen nucleating agent containing lead and silver is prepared and it is partly attached to the glaze surface of a temmoku glaze cup, and it is sintered in a reducing condition, then in the periphery of the part 1 where the yo-hen nucleating agent is coated and melted in glass-like black or gray dot, a gradation pattern 2 is developed dispersed in a color of sky blue to indigo. This gradation pattern 2 is in a color of gold or rainbow, and it is baked as a yo-hen pattern whose luster fluctuates by the direction of a light. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、曜変紋様によって加飾される陶磁器およびその製造法に関するものであって、特に、焼成時の加飾用元素の拡散蒸着現象を利用した陶磁器の加飾技術に関する。   The present invention relates to a ceramic decorated with a day variation pattern and a method for producing the same, and more particularly to a ceramic decorating technique using a diffusion vapor deposition phenomenon of a decorating element during firing.

従来、施釉した陶磁器の表面に絵柄や紋様を加飾する方法として上絵顔料による技法や、光彩を放つ加飾法としてラスタ−彩等があるが、それらは所要の色素顔料を塗布した釉薬表面部分にのみ色彩が発現するのが通例であった。一方、曜変釉、油滴天目釉あるいは一部の結晶釉等のように高火度で焼かれる釉薬では、焼成により出現する油滴紋や、大きく成長した結晶を加飾文様とするが、それは釉薬層内部から物理化学的反応として自然に湧き起こるものであって、特定の企画されたデザインに制御することは殆ど不可能であった。   Conventionally, there are two methods for decorating patterns and patterns on the surface of glazed ceramics, such as a technique using an upper picture pigment and a raster-coloring method for giving a glow, but these are glaze surfaces coated with the required pigments. It was customary that the color developed only in the part. On the other hand, in glazes that are baked at a high fire temperature, such as the day change, oil droplets, or some crystal glazes, oil droplets that appear by firing and large crystals are used as decorative patterns. It occurs naturally as a physicochemical reaction from the inside of the layer, and it was almost impossible to control to a specific designed design.

また、このような曜変釉の紋様を工業的に実現するものとして、プリント法が提案されている。（特許文献１を参照）
この方法では、素焼きタイル上にベース釉を焼付け、このベース釉に窯変調模様をプリントし、次いで、その上に複数の有色透明釉をスプレーした後、再度焼付けを行い、プリント模様をぼやかすことにより趣のある窯変調模様を形成する方法である。
特開平６−３２１６６７号公報：段落（００１２）（００１３） Also, a printing method has been proposed as an industrial implementation of such a day-changing pattern. (See Patent Document 1)
In this method, a base tile is baked on an unglazed tile, a kiln-modulated pattern is printed on the base tile, and then a plurality of colored transparent tiles are sprayed on it, and then baked again to blur the printed pattern. This is a method for forming a quaint kiln modulation pattern.
JP-A-6-321667: paragraphs (0012) (0013)

ところが、この方法で得られる模様は、同文献の段落（００２９）にあるように、基本的な色調や模様構成や質感などは殆ど等しいので、違和感のない均一なタイル施工面を形成できるものではあるが、所詮は、プリントされた窯変調模様を表現するに過ぎず、プリントされていない部分にまで自然の曜変釉にような複雑な虹彩紋様を発現するものではなかった。   However, the pattern obtained by this method, as described in paragraph (0029) of the same document, is almost the same in basic color tone, pattern configuration, texture, etc., so that it is not possible to form a uniform tile construction surface without a sense of incongruity. However, it was only a printed kiln modulation pattern, and it did not express a complex iris pattern like a natural day change to the unprinted part.

本発明は、上記の問題点を解決するためになされたものであり、高温の窯内において自然に発現する偶然の産物とも言える曜変紋様を、ある程度意図して発現させ、デザインとして形成することを可能とする曜変加飾陶磁器およびその製造法を提供するものである。かくして、同一デザインとして認識される曜変紋様の発現した陶磁器を工業的に製造可能とするものである。   The present invention has been made to solve the above-mentioned problems, and it is intended to form the design as a design by intentionally expressing to some extent a day variation pattern that can be said to be a natural product that naturally appears in a high-temperature kiln. The present invention provides a day-changing decorative ceramic and a manufacturing method thereof. In this way, it is possible to industrially manufacture ceramics that have the daily variation pattern recognized as the same design.

上記の問題は、第１発明であるところの、陶磁器の釉薬表面に焼き付けた鉛と銀とを含む曜変核形成剤の部分を核として、その周辺部位に複数の色調からなる虹彩を含む曜変紋様を発現させたことを特徴とする本発明の曜変加飾陶磁器によって解決することができる。   The above-mentioned problem is that the first aspect of the invention is the day variation pattern that includes an iris composed of a plurality of colors in the peripheral portion with the portion of the day variation nucleus forming agent containing lead and silver baked on the surface of the glaze of the ceramic. Can be solved by the day-decorated decorative ceramics according to the present invention.

また、上記の問題は、第２発明であるところの、鉛と銀とを含む曜変核形成剤を準備する工程と、この曜変核形成剤を陶磁器の釉薬表面に部分的に付着させる工程と、これを還元焼成することにより前記曜変核形成剤の部分を核として、その周辺部位に複数の色調からなる虹彩を含む曜変紋様を発現させる工程を含むことを特徴とする本発明の曜変加飾陶磁器の製造法によって解決することができる。   In addition, the above problem is the second invention, a step of preparing a day-of-day nucleation agent containing lead and silver, a step of partially attaching this day-of-day nucleation agent to the glaze surface of the ceramic, The present invention includes a step of developing a day variation pattern including an iris composed of a plurality of colors in the peripheral portion of the day variation nucleating agent as a nucleus by reducing and firing this, and the day variation decoration ceramic of the present invention It can be solved by the manufacturing method.

さらに、この曜変加飾陶磁器の製造法では、前記曜変核形成剤にアルカリ金属化合物が添加されたり、珪酸分が添加されるのが好ましく、また、これらの曜変加飾陶磁器の製造法における還元焼成が、最高温度６００〜８００℃においてＣＯ濃度１〜３％の還元雰囲気で焼成するのが特に好ましい。   Furthermore, in the method for producing the day-changing decorative ceramics, it is preferable that an alkali metal compound or a silicic acid component is added to the day-changing nucleating agent, and reduction baking in the method for producing these day-changing decorative ceramics. However, firing at a maximum temperature of 600 to 800 ° C. in a reducing atmosphere with a CO concentration of 1 to 3% is particularly preferable.

なお、曜変とは、本来、焼成雰囲気の変化や燃焼火炎の影響を受けて釉原料中の不純物の析出や燃料の灰分などが付着することにより、意図しなかった釉の発色が発現する現象をいうが、本発明において曜変紋様とは、特に希少価値のある曜変天目のような多色の複雑な虹彩で彩られたグラデーション模様、または油滴天目のような虹彩グラデーション模様で取り囲まれた多数の斑点状模様を含む用語として用いている。また、曜変は窯変とも記載されることがあるが、両者は同じ意味の用語であって、本発明では曜変の用語に統一して用いることとする。   In addition, the day change is a phenomenon in which unintended soot coloring appears due to the deposition of impurities in the soot raw material or the deposition of fuel ash due to the influence of the firing atmosphere or the combustion flame. However, in the present invention, the day variation pattern is a number of gradation patterns that are surrounded by a complex multi-colored iris, such as the rare day variation, or an iris gradation pattern, such as an oil drop celestial eye. It is used as a term including spotted patterns. Moreover, although a day change may be described as a kiln change, both are terms having the same meaning, and in the present invention, they are used in a unified manner.

本発明の加飾技術の要点は、鉛と銀との化合物に、必要に応じてナトリウムまたはカリウムなどのアルカリ化合物を添加した組成物を陶磁器の釉薬表面に付着させ、最高温度６００〜８００℃の還元焼成によって曜変紋様を発現させるための発生源として使用する点にある。この付着された組成物を中心核として、曜変紋様が形成されるので、本発明ではこれを曜変核形成剤ということとする。   The main point of the decorating technique of the present invention is that a composition in which an alkali compound such as sodium or potassium is added to a compound of lead and silver as necessary is attached to the glaze surface of a ceramic, and the maximum temperature is 600 to 800 ° C. It exists in the point used as a generation | occurrence | production source for expressing a day variation pattern by reduction baking. A day variation pattern is formed using the deposited composition as a central core, and in the present invention, this is referred to as a day variation nucleus forming agent.

本発明では、主に曜変核形成剤の付着部の外側周辺に多色の、例えば藍、水色、紺色、黄色、赤色、金色、緑色、虹のような虹彩を含むグラデーション模様からなる曜変紋様が対象釉の性質、曜変核形成剤の成分、焼付け条件などによって発現するのであるが、この加飾方法の原理は、特定の元素からなる１ミクロン以下の無機薄膜が釉面に拡散的に蒸着し、干渉色により虹彩を発現する加飾膜を構成する、すなわち特定の元素の拡散蒸着の現象に拠るものと思われる。この光彩の輝きはその陶磁器製品の美的価値を高めるのであるが、加飾膜は釉面に拡散融着したものであるから、一般的な陶磁器の用途において十分な耐久性を持つものである。   In the present invention, a daily variation pattern consisting of a multicolored gradation pattern including, for example, indigo, light blue, amber, yellow, red, gold, green, and an rainbow-like iris is mainly formed on the outer periphery of the adhesion portion of the daily variation nucleating agent. It depends on the nature of the target soot, the components of the day-changing nucleating agent, the baking conditions, etc. The principle of this decorating method is that an inorganic thin film of 1 micron or less consisting of a specific element is diffusely deposited on the face. It is considered that the decorative film that expresses the iris by the interference color is constituted, that is, depends on the phenomenon of diffusion deposition of a specific element. This glow of shine enhances the aesthetic value of the ceramic product, but the decorative film is diffused and fused to the surface, so that it has sufficient durability for general ceramic applications.

本発明において、曜変核形成剤中の銀成分は発色のための必須な有効成分であり、鉛成分は銀成分を釉面に拡散させ融着させる役割を持つと思われる必須成分である。また、アルカリ金属成分は前記鉛成分と銀成分の拡散を促進する拡散助剤として機能する。曜変核形成剤中にアルカリ成分を添加しない場合でも、下地の釉薬に通常含まれているアルカリが作用して曜変紋様が発現する場合もあるが、一般にその作用は薄弱なので別途曜変核形成剤中に添加するのが好ましい。   In the present invention, the silver component in the day-changing nucleating agent is an essential active component for color development, and the lead component is an essential component that seems to have a role of diffusing and fusing the silver component to the surface. The alkali metal component functions as a diffusion aid that promotes diffusion of the lead component and the silver component. Even if no alkali component is added to the day-changing nucleating agent, the alkali usually contained in the base glaze may act and the day-shaped pattern may appear. It is preferable to add to.

本発明の曜変加飾陶磁器およびその製造法は、このように、曜変紋様を発現させる曜変核形成剤として銀成分と鉛成分が有効成分であることを見出したことに基づくのであり、自然曜変と同様な不可思議で魅力的な虹彩を含む多彩なグラデーション模様で陶磁器の釉面を彩ることが可能となり、その商品価値を飛躍的に向上させることに大きく寄与するものである。   The day-changing decorative ceramic of the present invention and the manufacturing method thereof are based on the fact that the silver component and the lead component are found to be effective components as the day-varying nucleating agent for developing the day-changing pattern. It is possible to color the surface of ceramics with a variety of gradation patterns including the same mysterious and attractive iris, which greatly contributes to a dramatic improvement in the product value.

また、曜変紋様を上絵窯と同程度の最高温度６００〜８００℃で焼付け可能であり、しかも曜変核形成剤を意図したデザインに付着させることにより、意図したデザインに沿った形態の曜変模様が創作できるから、大量生産にも適しているという優れた効果がある。よって本発明は、従来の問題点を解消した曜変加飾陶磁器およびその製造法として、工業的、技術的価値はきわめて大なるものがある。   In addition, it is possible to bake the sun deformation pattern at a maximum temperature of 600 to 800 ° C., which is the same as that of the upper picture kiln, and by attaching the day deformation nucleating agent to the intended design, the shape of the sun deformation pattern according to the intended design Since it can be created, it has the excellent effect of being suitable for mass production. Therefore, the present invention has a very large industrial and technical value as a day-changing decorative ceramic and a method for manufacturing the same, which have solved the conventional problems.

次に、本発明の曜変加飾陶磁器およびその製造法に係る実施形態について、図１を参照しながら説明するが、先ず、第２発明である曜変加飾陶磁器の製造法から説明する。
本発明は、（１）鉛と銀とを含む曜変核形成剤を準備する工程、（２）この曜変核形成剤を陶磁器の釉薬表面に部分的に付着させる工程、（３）これを還元焼成することにより前記曜変核形成剤の部分を核として、その周辺部位に複数の色調からなる虹彩を含むグラデーション模様を発現させる工程、を含む。 Next, an embodiment according to a day-changing decorative ceramic of the present invention and a method for manufacturing the same will be described with reference to FIG. 1. First, a method for manufacturing a day-changing decorative ceramic according to the second invention will be described.
The present invention includes (1) a step of preparing a day-varying nucleating agent containing lead and silver, (2) a step of partially attaching the day-varying nucleating agent to the glaze surface of the ceramic, and (3) reduction firing. And a step of expressing a gradation pattern including an iris composed of a plurality of color tones in the peripheral portion with the portion of the day-changing nucleating agent as a nucleus.

（曜変核形成剤の準備）
本発明の曜変核形成剤は、鉛と銀を必須成分とし、アルカリを好ましい成分として、これらの機械的固形混合物、混合溶液、混合溶融固化物などの形態が利用できる。このうち、鉛成分としては金属鉛、酸化鉛の他、鉛化合物が適当であり、鉛白、密陀僧、鉛丹、白玉等、硝酸鉛が応用可能である。また、銀成分は、金属銀、酸化銀の他、銀化合物が適当であって、塩化銀、硝酸銀、炭酸銀が適用できる。アルカリ成分は、アルカリ金属塩として、塩化カリ、硝酸カリ、硝酸ソーダ、水ガラス、塩化ナトリウム等が用いられ得る。 (Preparation of day-changing agent)
The day-changing nucleating agent of the present invention may be in the form of a mechanical solid mixture, a mixed solution, a mixed molten solidified product, etc., with lead and silver as essential components and alkali as a preferred component. Among these, as lead components, lead compounds are suitable in addition to metallic lead and lead oxide, and lead nitrates such as white lead, dense nun, red lead, white ball, etc. are applicable. The silver component is suitably a silver compound in addition to silver metal and silver oxide, and silver chloride, silver nitrate and silver carbonate can be applied. As the alkali component, potassium chloride, potassium nitrate, sodium nitrate, water glass, sodium chloride, or the like can be used as an alkali metal salt.

混合溶液タイプの曜変核形成剤としては、例えば、可溶性の硝酸鉛と硝酸銀と硝酸カリの組み合わせを選択し、これに水アメを溶媒として混合し、水溶性の曜変核形成剤液とすることができる。この場合、適宜な水分で粘度を調整し、刷毛塗り、スプレー塗布など適宜な工法で陶磁器の釉薬面に付着させれば、焼成後、凹凸の少ない平滑な曜変紋様が得られる。   As the mixed solution type diurnal nucleating agent, for example, a combination of soluble lead nitrate, silver nitrate and potassium nitrate is selected and mixed with water candy as a solvent to form a water-soluble diurnal nucleating agent solution. it can. In this case, if the viscosity is adjusted with an appropriate amount of water and then adhered to the glaze surface of the ceramic by an appropriate method such as brushing or spraying, a smooth day-shaped pattern with few irregularities can be obtained after firing.

混合溶融固形物タイプの曜変核形成剤としては、例えば、鉛と銀の化合物にガラス形成剤として珪石を添加した混合物を加熱溶融して得た溶融物を冷却固化し、粉砕して粉末とし、これに適宜なバインダ、例えばＣＭＣや、アルカリ塩、水分を添加して、粘着性の曜変核形成剤ペーストとすることができる。この場合、ＣＭＣに代えて上絵用油性溶剤と混合し、インキとして上絵用転写紙に印刷すれば、陶磁器釉面に所定のデザインとして貼り付けるという慣用の転写技術が採用できるので、大量生産も可能となる利点がある。   As a mixed molten solid type diurnal nucleating agent, for example, a melt obtained by heating and melting a mixture of lead and silver compound added with silica as a glass forming agent is cooled and solidified, pulverized into a powder, An appropriate binder, for example, CMC, an alkali salt, and moisture can be added thereto to obtain an adhesive day-changing nucleator paste. In this case, mixing with oily solvent for overprint instead of CMC and printing on the transfer paper for overprint as ink can adopt the conventional transfer technology of pasting as a predetermined design on the ceramic surface, so mass production There are also advantages that are possible.

また、バインダとしては、ＣＭＣ、ふのり、蜂蜜、水あめ、バルサム、上絵用顔料溶剤、グリセリン、でんぷん、油、ＰＶＡ、アラビアゴム等があるが、ＣＭＣ、ＰＶＡは微量で粘着性に優れ効果が高いので推奨される。   In addition, examples of binders include CMC, funari, honey, starch candy, balsam, pigment solvent for painting, glycerin, starch, oil, PVA, gum arabic, etc. So recommended.

さらに付言すると、銀成分は発色源、鉛成分は焼成時の高温下において銀を釉面に拡散融着させる役割を持つもので、この必須成分の銀成分と鉛成分の好ましい配合比率は、金属換算で、鉛／銀＝５〜２０である。鉛成分の配合量が前記範囲より過小の場合は、核になる部分のガラス化が進まず剥離し易く、曜変紋様も拡散しにくい。また過大の場合は、発色源の銀成分が相対的に減少するので曜変紋様の発色が弱くなるので好ましくない。さらに、特に好ましい範囲は、鉛／銀＝５〜１０である。   In addition, the silver component is a color source and the lead component has the role of diffusing and fusing the silver to the surface at a high temperature during firing. The preferred mixing ratio of the essential silver component and lead component is a metal In conversion, it is lead / silver = 5-20. When the blending amount of the lead component is less than the above range, vitrification of the core portion does not proceed and it is easy to peel off, and the day variation pattern is difficult to diffuse. On the other hand, when the amount is too large, the silver component of the color source is relatively decreased, and the color change of the day variation pattern becomes weak. Furthermore, a particularly preferable range is lead / silver = 5-10.

また、アルカリ成分は、前記銀成分の拡散促進剤であり、釉薬層からアルカリが供給される場合もあるので、添加しなくても曜変紋様が発現する場合もあるが、意図して添加した方が得られる曜変紋様が安定するので、銀成分と鉛成分の合量に対して、少なくとも０．５％添加するのが好ましい。また、硝酸塩より塩化塩の方が紋を広げる効果は大きいが、時として異常に紋を広げすぎてしまうので硝酸塩の方が紋の形を制御し易く推奨される。アルカリ成分が過大となると紋様が荒れて汚れた感じになるので２０％までに抑えるのが好ましい。   The alkali component is a diffusion promoter for the silver component, and alkali may be supplied from the glaze layer. Therefore, it is preferable to add at least 0.5% with respect to the total amount of the silver component and the lead component. In addition, the effect of spreading chloride is greater than that of nitrate, but nitrate is recommended because it sometimes causes abnormally widening of the pattern, and nitrate is easier to control the shape of the pattern. If the alkali component is excessive, the pattern becomes rough and dirty, so it is preferable to keep it to 20%.

（曜変核形成剤の付着）
本発明による曜変紋様の加飾を施す母体たる陶磁器は、施釉焼成されたもので陶器と磁器の種類を問わない。また、その対象釉薬も、必ずしも鉄を発色剤として含む天目釉系の黒色釉に限るものではなく、通常の無色の長石系釉薬、銅を発色剤として含む織部調の緑釉、コバルトを発色剤とした瑠璃色釉など、各種の発色顔料で着色した多くの低火度釉および高火度釉が対象となり、本発明によれば、これらの釉薬の本来の発色を示す釉層上に本発明の曜変紋様が斑紋として重なり合って発現するので、それぞれの発色が混合した個性的な色紋様が得られるのである。 (Adherence of nucleating agent on day)
The ceramic that is the mother body decorated with the modified pattern of the day according to the present invention is glazed and fired regardless of the type of ceramic or porcelain. The target glaze is not necessarily limited to the Tenmoku-type black agate containing iron as a color former, but a normal colorless feldspar-type glaze, a woven green tone containing copper as a color former, and cobalt as a color former. Many low-fired and high-fired cocoons colored with various coloring pigments, such as the above-described amber-colored candy, are targeted, and according to the present invention, the present invention is provided on the glazing layer showing the original color of these glazes. Since the day variation pattern of No. 1 appears as an overlapping pattern, a unique color pattern in which each color is mixed is obtained.

適宜に選択した陶磁器に、前記のように得た曜変核形成剤を付着させるには、前記したところの、刷毛塗り、スプレー吹き付け、ゴム球に付けた細管から押し出すイッチン技法、転写紙転写の他、スクリーン印刷など従来から知られている工業的手法が採用できる。ただし、本発明では、曜変核形成剤の付着部分を核にして発色が拡散状に生じるので、デザインの意図に応じて曜変核形成剤を釉表面に０．５〜１０ｍｍ程度の斑点状もしくは線状に塗布するのが好ましい。   In order to adhere the day-changing nucleating agent obtained as described above to appropriately selected ceramics, in addition to the above-mentioned brush coating, spraying, itching technique for extruding from a thin tube attached to a rubber ball, transfer paper transfer, etc. Conventionally known industrial methods such as screen printing can be employed. However, in the present invention, the color development occurs in a diffused manner with the adhering portion of the day-changing nucleating agent as the nucleus, so that the day-changing nucleating agent has a spot-like shape or line of about 0.5 to 10 mm on the surface of the eyelid according to the design intention. It is preferable to apply in the shape of a film.

（焼付け）
かくして得られた素材は、焼き付けられるが、発現する曜変紋様の広がりと濃さは最高焼成温度、還元濃度および経過時間に影響される。好ましい焼成最高温度は、６００℃から８００℃までの温度であって、還元焼成する。この場合、還元濃度は、ＣＯ濃度で１％〜５％が適当であり、１％未満の弱い還元濃度では、発色が微弱すぎて好ましくなく、また５％を超えるＣＯ濃度のより強い還元雰囲気では、紋の彩度が低下し汚れた感じになり好ましくない。さらに過剰な還元をかけた場合、曜変核形成剤の付着部分に銀の析出と思われる顕著な変色が生じ、斑紋の広がりが大きくならず曜変紋様として貧弱なものとなる。 (printing)
The material thus obtained is baked, but the spread and density of the developed day variation pattern is affected by the maximum firing temperature, reduction concentration and elapsed time. A preferable firing maximum temperature is a temperature from 600 ° C. to 800 ° C., and reduction firing is performed. In this case, the reduction concentration is suitably 1% to 5% in terms of CO concentration. A weak reduction concentration of less than 1% is not preferable because color development is too weak, and in a reducing atmosphere with a CO concentration exceeding 5%. , It is not preferable because the saturation of the crest is lowered and it feels dirty. Further, when excessive reduction is applied, a noticeable discoloration that appears to be silver deposition occurs in the adhering portion of the day-changing nucleating agent, and the spread of the mottle is not increased, resulting in a poor day-like pattern.

最高焼成温度が高ければ、拡散蒸着効果は大きく、低ければ効果は小さい。しかし高い温度で長時間還元を保つと紋様の色が飛散して退色する。好ましい条件として、７００℃〜８００℃で、５〜１５分程度前記濃度の還元をかけて、以後６５０℃まで冷却するまで還元を継続する方法が推奨される。   If the maximum firing temperature is high, the diffusion deposition effect is large, and if it is low, the effect is small. However, if the reduction is maintained at a high temperature for a long time, the pattern color will scatter and fade. As a preferable condition, a method is recommended in which the reduction is performed at 700 to 800 ° C. for about 5 to 15 minutes, and then the reduction is continued until cooling to 650 ° C.

かくして、陶磁器の釉薬表面に焼き付けた鉛と銀とを含む曜変核形成剤の部分を核として、その周辺部位に複数の色調からなる虹彩を含む曜変紋様を発現させたことを特徴とする第１発明である曜変加飾陶磁器を得ることができる。
また、本発明では、鉄を含む天目釉を用いた場合、斑紋は紺・青・空色のように拡散蒸着の程度によりグラデーションをなす干渉色を発現したり、それが光の反射で金色や虹色に光って観察されることもある。また、釉薬中に銅成分を含んだり、曜変核形成剤に銅成分を含む場合のように、銅成分が存在する場合には、赤い発色が生じるときがある。これは銅と銀とが反応した結果と考えられる。 Thus, with the part of the day-changing nucleation agent containing lead and silver baked on the glaze surface of the ceramic as a nucleus, the day-shaped pattern containing the iris composed of a plurality of colors is developed in the peripheral part. It is possible to obtain a day-changing decorative ceramic that is an invention.
Further, in the present invention, when a Tenmoku kite containing iron is used, the mottles develop interference colors that form a gradation depending on the degree of diffusion deposition, such as kite, blue, and sky blue. It may be observed by shining in color. In addition, when a copper component is present, such as when the glaze contains a copper component or the day-changing nucleating agent contains a copper component, red coloring may occur. This is considered to be a result of the reaction between copper and silver.

従って、織部釉を対象に本発明を行った場合、赤銅光彩を発することが多い。また、高温で気化する銅は、窯の中に残留することがあるので、銅釉を焼いた窯で天目釉を対象として本発明を実施すると赤く発色する傾向が見られる。また、還元濃度の程度によっても、曜変紋様が赤銅光彩、黄金光彩を発する場合がある。   Therefore, when the present invention is applied to the weaving folds, a bronze glow is often emitted. Further, since copper that is vaporized at a high temperature may remain in the kiln, when the present invention is applied to the Tenmoku pot in a kiln that burns a copper pot, a tendency to develop a red color is observed. Also, depending on the degree of reduction concentration, the day variation pattern may emit a bronze glow or a golden glow.

以上説明した本発明の曜変核形成剤には、補助成分として珪素成分、例えば珪石粉末を３０％未満添加すると、焼成後の紋様の耐久性・耐酸性を向上させることができる。また、発色濃度や色調を変化させるために、銀以外の金属成分を１０％未満の範囲で添加することも可能である。この目的には、銅、ニッケル、コバルト、マンガン、チタニウムなどの金属、酸化物または塩類などが選択される。   When the silicon component, for example, silica powder, is added in an amount of less than 30% as an auxiliary component, the durability and acid resistance of the pattern after firing can be improved. In order to change the color density and color tone, it is also possible to add a metal component other than silver in a range of less than 10%. For this purpose, metals such as copper, nickel, cobalt, manganese, titanium, oxides or salts are selected.

対象とする陶磁器を次のように準備した。ゼーゲル式：（０．３２ＣａＯ，０．３５ＭｇＯ，０．２５Ｋ２Ｏ，０．０８Ｎａ２Ｏ）０．５６Ａｌ２Ｏ３−５．０ＳｉＯ２で表される基礎釉にＦｅ２Ｏ３を６％（外割）含む天目釉を、大平長石（ＳＳ−１５０）４５．３％、石灰６．６％、焼きタルク９．２％、珪石２６．６％、仮焼ニュージーランドカオリン７．３％、生ニュージーランドカオリン５％、紅柄６％（外割）によって調合し、磁器製茶碗に掛け、昇温時に１１５０までは酸化焼成を行いその温度で１時間保持した後、還元雰囲気にして１３００度Ｃまで昇温した。次いでそのまま１時間半保持し、その後９００度までは還元冷却する方法で全体が黒くなる天目釉茶碗を焼成した。 The target ceramics were prepared as follows. Zegeru formula: (0.32CaO, 0.35MgO, 0.25K 2 O, 0.08Na 2 O) to Fe 2 O 3 underlying glaze represented by 0.56Al 2 O 3 -5.0SiO 2 6% ( Tenmoku-an, which includes 45% Ohira feldspar (SS-150), 6.6% lime, 9.2% baked talc, 26.6% silica, 7.3% calcined New Zealand kaolin, raw New Zealand Prepared with 5% kaolin and 6% red pattern (spread), placed in a porcelain teacup, heated to 1150 when heated and kept at that temperature for 1 hour, then raised to 1300 ° C in reducing atmosphere Warm up. Next, it was held for one and a half hours, and then the Tenmoku tea bowl that became black as a whole was baked by reducing and cooling to 900 degrees.

曜変核形成剤を次ぎのように準備して天目釉茶碗に付着させた。前記鉛丹７５％、塩化銀１０％、珪石１５％の混合物をるつぼを用いて加熱、溶融してフリットを作り、微粉末に粉砕してから、２倍量のＣＭＣ３％糊剤溶液と混合し、さらに前記フリット量の１０％に当たる硝酸カリを加え、よく攪拌して曜変核形成剤からなる粘着性のペーストを得た。このペーストを上記天目釉の表面に１〜５ｍｍ径の多数の斑点状に塗布した。   The day-changing nucleating agent was prepared as follows and adhered to the Tenmoku Tea Bowl. The mixture of 75% lead red, 10% silver chloride and 15% silica is heated and melted in a crucible to make a frit, pulverized into fine powder, and then mixed with twice the amount of CMC 3% paste solution. Further, potassium nitrate corresponding to 10% of the frit amount was added and stirred well to obtain a sticky paste composed of a day-changing nucleating agent. This paste was applied to the surface of the above Tenmoku rice cake in a number of spots having a diameter of 1 to 5 mm.

このように準備した試料を、プロパンガスバーナを付設し還元焼成が可能な電気炉で、７５０℃まで酸化で昇温し、その温度においてＣＯ濃度が１．７％の還元焼成に切り換えて１０分間保持した。そして、６５０℃まで還元雰囲気のまま冷却し、以後常温まで通常に冷却して本発明の曜変加飾陶磁器である天目釉茶碗を得た。   The sample prepared in this way was heated to 750 ° C by oxidation in an electric furnace equipped with a propane gas burner and capable of reduction firing, and then switched to reduction firing with a CO concentration of 1.7% at that temperature and held for 10 minutes. did. And it cooled to 650 degreeC with a reducing atmosphere, and cooled normally to normal temperature after that, and the Tenmoku bowl which is a day change decoration ceramics of this invention was obtained.

得られた天目釉茶碗の表面には、図１に示すように、黒ないし灰色のガラス状に溶融した斑点状の曜変核形成剤の塗布部分１が核となって、その外周辺には、水色から紺色に発色したグラデーション模様２が拡散して発現していて、このグラデーション模様２は、金色あるいは虹色に彩られ、光の当たり具合によってそれら光彩が変化するところの曜変紋様として焼き付けられていた。なお、この核となる斑点部分１は、５μｍ程度の厚みを持つ部分であるが、グラデーション模様２は、厚さ０．１μｍ程度の層であって、銀と鉛を含む拡散層であることが確認された。   On the surface of the resulting Tenmoku bowl, as shown in FIG. 1, the application portion 1 of the spotted day-changing nucleating agent melted in a black or gray glass form serves as a nucleus, A gradation pattern 2 that is colored from light blue to amber is diffused and expressed, and this gradation pattern 2 is colored in gold or iridescent, and is baked as a day variation pattern in which these luminosity changes depending on how light strikes. It was. The spotted portion 1 serving as the core is a portion having a thickness of about 5 μm, but the gradation pattern 2 is a layer having a thickness of about 0.1 μm and is a diffusion layer containing silver and lead. confirmed.

下記表１に配合を示す曜変核形成剤を実施例１に準じて製作し、同様な対象陶磁器に施し、これを表１の最高温度、そのときの還元雰囲気（ＣＯ濃度）で焼き付けて曜変紋様の発現状態を観察した。
その結果は、鉛／銀配合比: ５〜２０、アルカリ量（Ｋ２Ｏ％）:銀成分と鉛成分の合量に対して０．５〜２０％、最高温度：６００〜８００℃、ＣＯ濃度：１〜３％、を満足する条件においてはいずれも好ましい曜変紋様が得られたが、この範囲外では、曜変紋様が極めて不十分であるか、または過剰な発色が生じるなど本発明の効果が得られないことが分った。なお、鉛／銀配合比: ５〜１０の範囲が最も好ましいことも分った。 A day-changing nucleating agent having the composition shown in Table 1 below is manufactured according to Example 1 and applied to the same target ceramics, which is then baked at the maximum temperature in Table 1 and the reducing atmosphere (CO concentration) at that time. The expression state of was observed.
The results are: Lead / silver blend ratio: 5-20, alkali amount (K 2 O%): 0.5-20% with respect to the total amount of silver component and lead component, maximum temperature: 600-800 ° C., CO In any of the conditions satisfying the density of 1 to 3%, a desirable day variation pattern was obtained. However, outside of this range, the day variation pattern was extremely insufficient or an effect of the present invention such as excessive color formation occurred. It was found that could not be obtained. It has also been found that the lead / silver blend ratio is most preferably in the range of 5-10.

焼成結果は、◎（試験結果中で最も好ましい色調、拡散程度が得られた）、○（曜変紋様として評価できる結果が得られた）で表示した。 The firing results are indicated by ◎ (the most preferable color tone and degree of diffusion were obtained among the test results), and ◯ (results that can be evaluated as a daily variation pattern were obtained).

実施例１の曜変紋様を示す写真。The photograph which shows the day variation pattern of Example 1.

符号の説明Explanation of symbols

１：塗布部分
２：グラデーション模様 1: Application part 2: Gradation pattern

Claims (5)

陶磁器の釉薬表面に焼き付けた鉛と銀とを含む曜変核形成剤の部分を核として、その周辺部位に複数の色調からなる虹彩を含む曜変紋様を発現させたことを特徴とする曜変加飾陶磁器。   Day-changing decorative ceramics characterized by the development of a day-shaped pattern containing irises consisting of multiple colors in the surrounding area with the day-shaped nucleating agent containing lead and silver baked on the glaze surface of the ceramic . 鉛と銀とを含む曜変核形成剤を準備する工程と、この曜変核形成剤を陶磁器の釉薬表面に部分的に付着させる工程と、これを還元焼成することにより前記曜変核形成剤の部分を核として、その周辺部位に複数の色調からなる虹彩を含む曜変紋様を発現させる工程を含むことを特徴とする曜変加飾陶磁器の製造法。   A step of preparing a day-varying nucleating agent containing lead and silver, a step of partially attaching the day-varying nucleating agent to the glaze surface of the ceramic, and reducing and firing the portion of the day-varying nucleating agent. A method for producing a day-changing decorative ceramic, comprising a step of developing a day-shaped pattern including an iris having a plurality of colors as a core. 前記曜変核形成剤にアルカリ金属化合物が添加されている請求項２に記載の曜変加飾陶磁器の製造法。   The method for producing a day-changing decorative ceramic according to claim 2, wherein an alkali metal compound is added to the day-changing nucleating agent. 前記曜変核形成剤に珪酸分が添加されている請求項２または３に記載の曜変加飾陶磁器の製造法。   The manufacturing method of the day change decoration ceramics of Claim 2 or 3 with which the silicic acid component is added to the said day change nucleus formation agent. 前記請求項２、３または４に記載の曜変加飾陶磁器の製造法における還元焼成が、最高温度６００〜８００℃においてＣＯ濃度１〜５％の還元雰囲気で焼成するものであることを特徴とする曜変加飾陶磁器の製造法。

The reduction firing in the method for producing a day-changing decorative ceramic according to claim 2, 3 or 4, wherein firing is carried out in a reducing atmosphere having a CO concentration of 1 to 5% at a maximum temperature of 600 to 800 ° C. Manufacturing method of the day-changing decorative ceramics.

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