JP2012082122A - Method of manufacturing microwave heating pottery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pottery for microwave heating and a method for manufacturing the same since a usual pottery has a low heating effect in a microwave oven, therefore, it is unsuitable to cooking which roasts fish and meat, however, when a cooking utensil itself is heated strongly, cooking which roasts fish and meat by gas fire or charcoal fire can be performed, moreover, boiled rice can be attached with scorch, or is inserted into two flat plates and can be burned to be a rice cracker.SOLUTION: Thermal shock resistance of a green body must be high in order to highly efficiently heat a pottery vessel for food cooking by a microwave oven. Therefore, a green body composition is made such that a cordierite quality and β spodumene of a low thermal expansion property deposit in a raw material blending. For a material for raising heating efficiency, the calcination synthesis of stannic acid antimony (SbO-SnO) and transition element compound oxides, such as FeO, and CrO, MnO, CoO, and CuO is carried out, and synthesized products are added to a green body and a glaze, thereby the pottery vessel which efficiently heats is manufactured.

Description

発明の詳細な説明Detailed Description of the Invention

一般の家庭用電子レンジは電力をマグネトロンによって２４５０ＭＨｚのマイクロ波に変換し、主に食品に含まれる水分の加熱を促して調理する器具であるが、魚や肉を焼く、あるいは焚いたご飯に焦げ目を付ける、煎餅を焼くなどの調理には、用いる「器」が効率よく加熱しなければならない。そのような目的を叶えるため、マイクロ波吸収効率が高く、しかも熱衝撃に強い陶磁器製容器の開発が嘱望されている。  A general household microwave oven is an appliance that cooks by converting the electric power into microwaves of 2450 MHz with a magnetron and mainly promoting the heating of moisture contained in food, but it burns fish and meat, or burns rice For cooking such as attaching or baking rice crackers, the “vessel” used must be heated efficiently. In order to achieve such a purpose, development of a ceramic container having high microwave absorption efficiency and high resistance to thermal shock is desired.

一般に用いられる陶磁器製の食器、鍋などは２４５０ＭＨｚのマイクロ波による加熱性が低く、熱衝撃にも弱い。それを克服するためにコージライト質およびペタライトを母体とした陶磁器を用いて低熱膨張性であって熱衝撃にも強い素地を開発し、そのような素地素材および、それに適合する釉素材にマイクロ波吸収効率の高い添加物を配合に加えて電子レンジで強く加熱される陶磁器を製造することに成功した。  Commonly used ceramic tableware, pans, etc. have low heatability by 2450 MHz microwaves and are vulnerable to thermal shock. To overcome this problem, we developed a low thermal expansion and strong material against heat shock using ceramics based on cordierite and petalite. We have succeeded in manufacturing ceramics that are strongly heated in a microwave oven by adding additives with high absorption efficiency.

コージライト質陶器素地は、通常タルク（３ＭｇＯ・４ＳｉＯ_２・Ｈ_２Ｏ）と粘土（Ａｌ_２Ｏ_３・２ＳｉＯ_２・２Ｈ_２Ｏ）およびアルミナ（Ａｌ_２Ｏ_３）の混合物を１３５０℃から１４００℃の高温でコージライトクリンカー（２ＭｇＯ・２Ａｌ_２Ｏ_３・５ＳｉＯ_２）を作り、その粉体に成形を可能にする可視性粘土を加えて素地坏土を調整している。本発明ではタルク、可塑性粘土、長石、アルミナによる配合物に高効率マイクロ波吸収材を加えた生配合で素地坏土を作った。焼成温度は１１００℃〜１１５０℃である。Cordierite earthenware is usually made from a mixture of talc (3MgO · 4SiO ₂ · H ₂ O), clay (Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O) and alumina (Al ₂ O ₃ ) at 1350 ° C to 1400 ° C. Cordierite clinker (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ) is made at a high temperature, and visible clay that enables molding is added to the powder to adjust the base clay. In the present invention, a green clay was made with a raw blend obtained by adding a high-efficiency microwave absorber to a blend of talc, plastic clay, feldspar, and alumina. The firing temperature is 1100 ° C to 1150 ° C.

ペタライト（Ｌｉ_２Ｏ・Ａｌ_２Ｏ_３・８ＳｉＯ_２）を用いてβスポジューメン（Ｌｉ_２Ｏ・Ａｌ_２Ｏ_３・４ＳｉＯ_２）を析出させる陶磁器の素地はペタライトに可塑性粘土を成形に必要な量を加えて坏土とすればよい。Petalite an amount necessary to mold the β-spodumene ceramic green body plasticity clay petalite precipitating _{(Li 2 O · Al 2 O} 3 · 4SiO 2) using _{(Li 2 O · Al 2 O} 3 · 8SiO 2) In addition, it should be dredged.

このようなペタライトと可塑性粘土による陶磁器素地の焼成温度は１２００℃程度が適当であるが、低すぎると燒結性が悪く、多孔質であって機械的強度が弱い。またβスポジューメンの生成が不充分で低熱膨張にならない。また高すぎると素地そのものが軟化して変形する。  The firing temperature of the ceramic body made of such petalite and plastic clay is suitably about 1200 ° C., but if it is too low, the sintering property is poor, porous and the mechanical strength is weak. In addition, β-spodumene is not sufficiently produced and does not result in low thermal expansion. If it is too high, the substrate itself softens and deforms.

このようにして作るコージライト質やβスポジューメン析出耐熱衝撃性素地に用いる釉の熱膨張は、素地のそれと同等か幾分低めにすることである。素地と釉との間の適合性を図るには釉を低熱膨張にするコことが必要で、それにはペタライト用いた組成で作り易い。焼成適正温度を１１００℃から１２００℃に調整できる釉組成はペタライト長石、珪石、石灰石あるいはドロマイト、それに硼酸分を含む天然鉱物のウレキサイトあるいはコレマナイト、または硼珪酸塩フリットを釉配合に加えればよい。  The thermal expansion of the soot used for the cordierite and β-spodumene precipitation thermal shock resistant base material thus produced is to be the same as or somewhat lower than that of the base material. In order to achieve compatibility between the substrate and the kite, it is necessary to make the kite have a low thermal expansion, which is easy to make with a composition using petalite. The soot composition capable of adjusting the proper firing temperature from 1100 ° C. to 1200 ° C. may include petalite feldspar, silica stone, limestone or dolomite, and natural mineral urexite or colemanite containing boric acid, or borosilicate frit.

このようにして作られるマイクロ波加熱性を向上させるために付与する効果的な添加材が錫酸アンチモニー仮焼物（Ｓｂ_２Ｏ_５−ＳｎＯ_２）である。それは酸化アンチモニー（Ｓｂ_２Ｏ_３またはＳｂ_２Ｏ_３）と酸化錫（ＳｎＯ_２）を粉体混合して約１０００℃で焼成して得られる青鼠色の仮焼粉体である。
また酸化鉄、２酸化マンガン、酸化コバルト、酸化銅、酸化クロームなどの粉体を混合して約１２００℃で焼成して得られる黒色の複合遷移元素酸化物の仮焼粉体もマイクロは吸収性を向上させる素材になる。An effective additive imparted in order to improve the microwave heating property thus produced is antimony stannate calcined product (Sb ₂ O ₅ —SnO ₂ ). It is a blue-blue calcined powder obtained by powder mixing antimony oxide (Sb ₂ O ₃ or Sb ₂ O ₃ ) and tin oxide (SnO ₂ ) and firing at about 1000 ° C.
In addition, micro-absorbent powders of black composite transition element oxides obtained by mixing powders of iron oxide, manganese oxide, cobalt oxide, copper oxide, chrome oxide, etc. and firing at about 1200 ° C. It becomes a material to improve.

製造手順は、先ず素地配合物をボ−ルミルなどで湿式粉砕する。その泥漿は直接鋳込み成形ができる。またフィイルタープレスなどで脱水して練り土とすれば轆轤成形、「型起こし」などの成形に供することができる。釉も同様な粉砕方法で泥漿にする。
成形した素地を、よく乾燥すれば施釉できるが、８００℃程度で素焼きすれば容易に、かつ安全に施釉できる。In the manufacturing procedure, first, the base material mixture is wet-ground by a ball mill or the like. The slurry can be cast directly. Moreover, if it dehydrates and kneads with a filter press etc., it can use for shaping | molding, such as dredging molding and "mold raising". The cocoon is also crushed by the same grinding method.
The formed substrate can be glazed if it is thoroughly dried, but can be easily and safely glazed if it is unglazed at about 800 ° C.

１． コージライト質素地を用いたマイクロ波加熱用陶磁器
１．１．コージライト質素地はタルク、粘土、アルミナによる配合物を高温焼成でクリンカーとし、粉砕に可塑性粘土を加えて作るのが普通であるが、本実施例は焼結を低温度化するため珪・長石の砂婆を配合の中に加えた。また本発明に用いる加熱効果向上材もコージライト生成に効果がある。

上の原料を用いて素地坏土を作るが、本実施例の組成は以下の通りである。

この組成で素地坏土を作る。この素地の焼成適温度は１１５０℃である。
１．２．釉は器物が熱衝撃によって破壊されるのを防ぐため１１００℃〜１２００℃で熔融し、しかも熱膨張を素地のそれに適合させるため、ペタライトとウレキサイトを釉組成配合に加えた。ウレキサイトを用いた釉を同じゼーゲル式の釉に窯業計算をしてコレマナイトに代えることができる。

上の原料を用いて釉泥漿を作るが、本実施例の組成は以下の通りである。

この組成を釉とする。
１．３．（Ｓｂ_２Ｏ_５−ＳｎＯ_２系添加材）加熱効果向上添加剤は３酸化アンチモニー（Ｓｂ_２Ｏ_３）１０重量％をメタ錫酸（Ｈ_２ＳｎＯ_３）に加えて湿式粉砕して乾燥した粉体を１０００℃で仮焼して合成する。この添加材は青鼠色の電気伝導性物質であって電子レンジ加熱効果が高く、また全赤外線域での放射率がリニアーに高いので、これを加えた陶磁器は高効率赤外線放射体となる。
１．４．（複合遷移元素酸化物系添加材）２酸化マンガン（ＭｎＯ_２）６０重量％、酸化鉄（Ｆｅ_２Ｏ_３）２０重量％、酸化コバルト（ＣｏＯ）１０重量％、酸化銅（ＣｕＯ）１０重量％を混合し、湿式粉砕して乾燥した粉体を１２００℃で仮焼して合成する。黒色の全赤外線域で放射率がリニアーに高いので、これを加えた陶磁器は高効率赤外線放射体となる。
これらの陶磁器は１１００℃〜１１５０℃で焼成する。
このようにして作られた陶磁器素地の線熱膨張係数は約３〜４×１０^−６／℃であって、ガスコンロで３００℃程度に加熱し、直ちに水中に投じて急冷しても破壊しない耐熱衝撃性を有している。電子レンジ加熱でも、同様に耐熱衝撃性が高い。
１．５．素地配合にＳｂ_２Ｏ_５−ＳｎＯ_２系添加材を１０重量％加えてボールミル等で湿式粉砕し、鋳込み成型用の泥漿にする。また、それをフイルタープレスで脱水し、練り土用の坏土とする。釉は配合物を湿式粉砕して泥漿にする。
成形した素地を、よく乾燥するか８００℃で素焼きして施釉する。釉はマイクロ波向上添加物の無添加でも１０％添加しても良い。
ガス窯を用いて１１３０℃酸化焔で焼成したが、電気窯焼成でもよい。1. Ceramics for microwave heating using cordierite substrate 1.1. The cordierite substrate is usually made by mixing talc, clay, and alumina with clinker by high-temperature firing, and adding plastic clay to the pulverization, but this example uses silica and feldspar in order to lower the sintering temperature. Was added to the recipe. Moreover, the heating effect improving material used in the present invention is also effective in producing cordierite.

The base material is made using the above raw materials, and the composition of this example is as follows.

Make a base clay with this composition. The appropriate firing temperature of this substrate is 1150 ° C.
1.2. The soot was melted at 1100 ° C. to 1200 ° C. to prevent the vessel from being destroyed by thermal shock, and petalite and urexite were added to the soot composition formulation to match the thermal expansion to that of the substrate. The firewood using urexite can be converted to colemanite by performing ceramics calculation on the same Zegel type firewood.

The above raw material is used to make the sludge, and the composition of this example is as follows.

Let this composition be the cocoon.
1.3. (Sb ₂ O ₅ —SnO ₂ -based additive) The heating effect improving additive is a powder obtained by adding 10% by weight of antimony trioxide (Sb ₂ O ₃ ) to metastannic acid (H ₂ SnO ₃ ) and then wet-grinding and drying. The body is calcined at 1000 ° C. and synthesized. This additive is a blue-blue electroconductive substance, has a high microwave heating effect, and has a linearly high emissivity in the entire infrared region, so that ceramics to which this is added become a high-efficiency infrared radiator.
1.4. (Composite transition element oxide-based additive) Manganese dioxide (MnO ₂ ) 60% by weight, iron oxide (Fe ₂ O ₃ ) 20% by weight, cobalt oxide (CoO) 10% by weight, copper oxide (CuO) 10% by weight Are mixed, wet pulverized and dried, and calcined at 1200 ° C. to synthesize. Since the emissivity is linearly high in the black all-infrared region, ceramics with this addition become a high-efficiency infrared radiator.
These ceramics are fired at 1100 ° C to 1150 ° C.
The coefficient of linear thermal expansion of the ceramic body made in this way is about 3-4 × 10 ⁻⁶ / ° C., heat resistant to about 300 ° C. using a gas stove, and immediately destroyed by cooling it in water and rapidly cooling. Has impact. The heat shock resistance is also high in microwave oven heating.
1.5. 10% by weight of Sb ₂ O ₅ —SnO ₂ based additive is added to the base composition and wet pulverized with a ball mill or the like to obtain a slurry for casting. Moreover, it is dehydrated with a filter press and used as a clay for kneaded soil. The koji is wet milled into a slurry.
The formed substrate is dried well or baked at 800 ° C. The soot may be added without adding the microwave improving additive or 10%.
Although it baked with 1130 degreeC oxidation soot using a gas kiln, an electric kiln baking may be sufficient.

２． ペタライトを用いた低熱膨張性マイクロ波加熱用陶磁器
２．１．ペタライトを用いた陶磁器素地は低熱膨張であって、電子レンジ加熱の器に適する。素地組成を以下に示す。

この組成で素地坏土を作る。
ペタライトに成形可能な程度の可塑性粘土を加えて坏土とした素地は１１３０℃で燒結する。このような素地は焼成によってβスポジューメン（Ｌｉ_２Ｏ・Ａｌ_２Ｏ_３・４ＳｉＯ_２）が析出した低熱膨張性の素地となって耐熱衝撃性は極めて高い。
２．２．釉は器物が熱衝撃によって破壊されるのを防ぐため１２００℃で熔融し、しかも熱膨張を素地の、それに適合させるためペタライト主体の組成配合にした。

上の原料を用いて釉泥漿を作るが、本実施例の組成は以下の通りである。

この組成を釉とする。
２．３．素地配合にＳｂ_２Ｏ_５−ＳｎＯ_２系添加材を１０重量％加えてボールミル等で湿式粉砕し、鋳込み成型用の泥漿にする。また、それをフイルタープレスで脱水し、練り土用坏土とする。釉は配合物を湿式粉砕して泥漿にする。
成形した素地を、よく乾燥すれば、そのままで施釉できるが、８００℃で素焼きしておけば容易に安全に施釉できる。釉はマイクロ波向上添加物の無添加でも１０％添加しても良い。
焼成はガス窯を用いて１２００℃酸化焔で焼成したが、電気窯焼成でもよい。2. Ceramics for low thermal expansion microwave heating using petalite 2.1. A ceramic body using petalite has low thermal expansion and is suitable for a microwave oven. The substrate composition is shown below.

Make a base clay with this composition.
The base material made into a clay by adding plastic clay of a moldable degree to petalite is sintered at 1130 ° C. Such a base becomes a low thermal expansion base on which β-spodumene (Li ₂ O.Al ₂ O ₃ .4SiO ₂ ) is precipitated by firing, and has a very high thermal shock resistance.
2.2. Soot was melted at 1200 ° C. in order to prevent the container from being destroyed by thermal shock, and the composition was mainly composed of petalite in order to adapt the thermal expansion to the base material.

The above raw material is used to make the sludge, and the composition of this example is as follows.

Let this composition be the cocoon.
2.3. 10% by weight of Sb ₂ O ₅ —SnO ₂ based additive is added to the base composition and wet pulverized with a ball mill or the like to obtain a slurry for casting. Moreover, it is dehydrated with a filter press and used as a clay for kneading soil. The koji is wet milled into a slurry.
If the formed substrate is thoroughly dried, it can be glazed as it is, but if it is baked at 800 ° C., it can be easily and safely glazed. The soot may be added without adding the microwave improving additive or 10%.
Firing was performed using an oxygen furnace at 1200 ° C. using a gas kiln, but may be performed using an electric kiln.

発明の効果The invention's effect

加熱用マイクロ波は９１５ＭＨｚと２４５０ＭＨｚが用いられるが、大きな固形物を均一に加熱するには浸透力の高い９１５ＭＨｚが有利である。家庭用デンシレンジは水の加熱に効果の高い２４５０ＭＨｚが用いられているが、本発明の陶磁器は９１５ＭＨｚでも２４５０ＭＨＺでも加熱効果が高い。  As the microwave for heating, 915 MHz and 2450 MHz are used, but 915 MHz having a high osmotic force is advantageous for uniformly heating a large solid. The household densic range uses 2450 MHz, which is highly effective for heating water, but the ceramic of the present invention has a high heating effect at both 915 MHz and 2450 MHZ.

電子レンジは食品を均一に加熱できるように、それ自身は加熱し難い陶磁器製、あるいはガラス製のタンテーブルを用いる。また容器は陶磁器、あるいは耐熱性プラスチックが用いられることが普通である。  The microwave oven uses a ceramic or glass tongue table that is difficult to heat itself so that the food can be heated uniformly. The container is usually made of ceramic or heat-resistant plastic.

しかし容器自身が強く加熱すれば特徴ある調理ができる。また、容器の熱容量を大ききできることから冷め難くなる。そのことは通常の容器では出来ない、電子レンジによって魚や肉を焼く、ご飯に焦げ目を付ける、板状容器に挟んで煎餅を約焼くなどの特徴的な調理法が可能である。そのような目的のために開発したのが本発明のマイクロ波加熱陶磁器の製造法である。  However, if the container itself is heated strongly, cooking can be performed characteristically. Moreover, it becomes difficult to cool the container because the heat capacity of the container can be increased. This is not possible with ordinary containers, but it is possible to perform characteristic cooking methods such as grilling fish and meat with a microwave oven, scorching rice, or sandwiching rice crackers between plate-like containers. The microwave heating ceramic manufacturing method of the present invention has been developed for such a purpose.

Claims (3)

電子レンジはマイクロ波領域の電磁波を用いて水分を効果的に加熱し、それによって食品調理を行う器具であるが、魚や肉などを焼く調理には器そのものの加熱が必要である。しかし通常の陶磁器製器はマイクロ波の吸収が弱く加熱され難い。また、耐熱衝撃性も低い。したがって器、自身が電子レンジによって効率よく加熱し、熱衝撃で破壊しない特徴を有する陶磁器製容器が求められる。本発明は熱衝撃に強い陶磁器素地および釉にマイクロ波吸収率の高いセラミック粉末を添加して効率よく加熱する耐熱衝撃性陶磁器の製造法である。  A microwave oven is an instrument that effectively heats moisture using electromagnetic waves in the microwave region and thereby cooks food. However, cooking of grilling fish or meat requires heating of the vessel itself. However, ordinary ceramic ware is weak in microwave absorption and is not easily heated. Also, the thermal shock resistance is low. Therefore, there is a need for a ceramic container that has the characteristics that it is efficiently heated by a microwave oven and is not destroyed by thermal shock. The present invention is a method for producing a heat-resistant shock-resistant ceramic that is efficiently heated by adding ceramic powder having a high microwave absorption rate to a ceramic substrate that is resistant to thermal shock and a bowl. （素地と釉の熱的物性） 基礎素地は低熱膨張性で熱衝撃に強いコージライト質素地および酸化リチュウムを含むペタライト鉱物を主原料とし、焼成時にβスポジュウメンが析出して低熱膨張性となる素地組成であること。釉は、素地に適合する熱膨張に調整して釉貫入や器物のシバリング破壊を生じない釉であること。(Thermal physical properties of the substrate and cocoons) The basic substrate is a cordierite substrate that is low in thermal expansion and resistant to thermal shock, and a petalite mineral that contains lithium oxide. Be composition. The kite should be adjusted to the thermal expansion suitable for the substrate so that the kite does not penetrate and the shivering destruction of the equipment does not occur. （高効率マイクロ波吸収材） マイクロ波吸収率の高い錫酸アンチモニー仮焼物（Ｓｂ_２Ｏ_５−ＳｎＯ_２）および酸化鉄（Ｆｅ_２Ｏ_３）、２酸化マンガン（ＭｎＯ_２）、酸化コバルト（Ｃｏ（））、酸化銅（ＣｕＯ）、酸化クローム（Ｃｒ_２Ｏ_３）などの遷移元素による仮焼複合酸化物の粉末を素地および釉に添加したものを器物製造の素材にすること。コージライト質陶磁器素地やペタライト使用陶磁器素地に高効率マイクロ波吸収材を加えると焼結性が向上し１１００℃から１２００℃を適応焼成温度にすることができる。(High-efficiency microwave absorber) Antimony stannate calcined material (Sb ₂ O ₅ —SnO ₂ ), iron oxide (Fe ₂ O ₃ ), manganese dioxide (MnO ₂ ), cobalt oxide (Co ()), Calcined composite oxide powders made of transition elements such as copper oxide (CuO), chromium oxide (Cr ₂ O ₃ ), etc. are added to the substrate and the soot as a raw material for the production of equipment. When a high-efficiency microwave absorber is added to a cordierite ceramic body or a ceramic body using petalite, the sinterability is improved, and an adaptive firing temperature can be set from 1100 ° C to 1200 ° C.