JP6330994B2 - Low thermal expansion ceramic products - Google Patents
Low thermal expansion ceramic products Download PDFInfo
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- JP6330994B2 JP6330994B2 JP2013217556A JP2013217556A JP6330994B2 JP 6330994 B2 JP6330994 B2 JP 6330994B2 JP 2013217556 A JP2013217556 A JP 2013217556A JP 2013217556 A JP2013217556 A JP 2013217556A JP 6330994 B2 JP6330994 B2 JP 6330994B2
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- 239000000919 ceramic Substances 0.000 title claims description 14
- 229910052878 cordierite Inorganic materials 0.000 claims description 56
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000013078 crystal Substances 0.000 claims description 43
- 229910052573 porcelain Inorganic materials 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 20
- 238000010304 firing Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 230000035939 shock Effects 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000035515 penetration Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052670 petalite Inorganic materials 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 229910052845 zircon Inorganic materials 0.000 description 6
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910018068 Li 2 O Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000010433 feldspar Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 235000021186 dishes Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は、陶磁器製品に用いられる釉薬に関するもので、特に、耐熱衝撃性の高い低熱膨張の陶磁器製品に用いられる釉薬に関する。 The present invention relates to a glaze used for ceramic products, and more particularly to a glaze used for ceramic products with high thermal shock resistance and low thermal expansion.
従来より、コーディエライト（2MgO・2Al2O3・5SiO2）を用いた低膨張のセラミックス焼結体、特に磁器食器が存在する。コーディエライトは、吸水率0.1%以下の磁器質であるとともに、熱膨張係数が小さいことから耐熱衝撃性に優れていることが知られている。そのため、その素材に関し、種々のものが報告されている。例えば、特開２０１３−１８６９４号（特許文献１）には、タルク、アルミナ、カオリンなどに、Li含有材料をLi2Oとして0.12〜1.0％相当量をあらかじめ素地中に含有せしめ、さらにNa2O+K2Oが1.1重量%〜2.8重量%とした低熱膨張磁器が開示されている。また、特開２００３−２３８２３８号（特許文献２）には、タルク、カオリン、アルミナ、Li含有材料と共に、合成コーディエライトとジルコンを素地原料とすると共に、Li含有材料とジルコンを釉薬原料に用いた低熱膨張磁器が開示されている。さらに、特開昭５７−０２７９４５号（特許文献３）には、釉薬組成に関しSiO2、Al2O3、MgO、B2O3、KNaO、ZnO、ZrO2量を一定範囲とすることで、焼成時に素地との反応によりコーディエライト結晶と少量のコランダム、スピネルからなる釉薬の生成が開示されている。 Conventionally, there is a low-expansion ceramic sintered body using cordierite (2MgO · 2Al 2 O 3 · 5SiO 2 ), especially porcelain tableware. Cordierite is known to have excellent thermal shock resistance due to its porcelain with a water absorption of 0.1% or less and a low coefficient of thermal expansion. For this reason, various materials have been reported. For example, in JP 2013-18694 (Patent Document 1), a tantalum, alumina, kaolin, or the like contains a Li-containing material of Li 2 O in an amount of 0.12 to 1.0% in advance, and further contains Na 2 O. A low thermal expansion porcelain with + K 2 O of 1.1 wt% to 2.8 wt% is disclosed. JP 2003-238238 (Patent Document 2) uses synthetic cordierite and zircon as a raw material together with talc, kaolin, alumina, and a Li-containing material, and uses a Li-containing material and zircon as a glaze raw material. A low thermal expansion porcelain was disclosed. Furthermore, JP-A-57-027945 (Patent Document 3) discloses that the amount of SiO 2 , Al 2 O 3 , MgO, B 2 O 3 , KNaO, ZnO, and ZrO 2 is within a certain range with respect to the glaze composition. The production of a glaze composed of cordierite crystals and a small amount of corundum and spinel is disclosed by reaction with the substrate during firing.
しかし特許文献１に関しては、コーディエライト質の素地に対してＬｉ系釉を施釉した場合、たとえ素地中にLi含有材料をLi2Oとして0.12〜1.0％相当量をあらかじめ含有せしめ、さらにNa2O+K2Oが1.1重量%〜2.8重量%としても、さらに焼成時に充分時間をかけて冷却温度をコントロールしなければ貫入が発生してしまう。つまり、焼成時の冷却段階において、釉薬層にβ-石英とユークリプタイトとの固溶体といわれているシリカ-O系の結晶が生成する温度域、1000℃〜900℃間を4時間以上かけて冷却し、シリカ-O系の結晶を充分生成・成長させる必要がある。
しかしこれでは、貫入の発生を抑制することはできるが、一定期間内に焼成できる回数、つまり生産数量が減少することで、生産効率が悪いだけでなく、冷却工程において急冷を抑えるため余分な燃料が必要となり、更なるコストアップとなる。
また、特許文献２に関して、合成コーディエライトは素地の原料の一つに用いられているが、釉薬には用いられておらず、釉薬には熱膨張の大きなジルコンが結晶生成核用材料として使用されている。ジルコンはシリカ-O系などの結晶生成用の核にはなるが、熱膨張を下げるまで結晶が成長するには、どうしても焼成時の冷却時間を充分に遅くする必要があるため、その効果はわずかなものである。しかもジルコンは、コーディエライトに比べて熱膨張が大きいため、シリカ-O系の結晶成長が充分でなければ、逆に釉薬の熱膨張を上げてしまう。
さらに、特許文献３に関して、合成コーディエライトではなく、焼成時の反応によりコーディエライト結晶を析出させている。しかも釉薬原料だけの反応ではコーディエライト結晶が生成しないため、素地と釉薬による界面での反応によるものと記載されている。このように焼成時の反応による結晶生成では、冷却速度の影響を受けやすく、しかも素地を含めた反応でもあるため、素地の組成もＬｉ2Ｏを存在させてはならないと記載されているように、限定されたものとなる。
よって、コーディエライト質の素地に対し、釉薬を施釉した従来のものはいずれも、焼成時の冷却にかなり長時間を必要するため、一般の陶磁器製造に比べ、時間やコストが大幅に掛かってしまう。さらに、反応による結晶生成のため、釉薬だけでなく素地の組成も厳密に管理することが必要となる。このような理由から、コーディエライト素地だけであれば工業部品などとして使用されているが、コーディエライト素地に釉薬を施した磁器質の耐熱製品は、製造が困難なことから、耐熱製品といえば製造の容易なペタライト質のものに限られている。
However, with respect to Patent Document 1, when Li-based soot is applied to a cordierite base, an equivalent amount of 0.12 to 1.0% is preliminarily contained in the base as a Li-containing material as Li 2 O, and Na 2 is further added. Even if O + K 2 O is 1.1% to 2.8% by weight, penetration occurs if the cooling temperature is not controlled over a sufficient period of time during firing. In other words, in the cooling stage at the time of firing, a temperature range where silica-O-based crystals, which are said to be a solid solution of β-quartz and eucryptite, are generated in the glaze layer, between 1000 ° C and 900 ° C over 4 hours. It is necessary to cool and to sufficiently generate and grow silica-O-based crystals.
However, this can suppress the occurrence of penetration, but the number of times that firing can be performed within a certain period, that is, the production quantity is reduced, so that not only the production efficiency is bad, but also excess fuel is added to suppress rapid cooling in the cooling process. Is required, which further increases costs.
Regarding Patent Document 2, synthetic cordierite is used as one of the raw materials of the substrate, but it is not used in glazes. Zircon, which has a large thermal expansion, is used as glaze nucleation material in glazes. Has been. Zircon is a nucleus for crystal formation such as silica-O system, but it is necessary to slow down the cooling time at the time of firing sufficiently for the crystal to grow until the thermal expansion is lowered. It is a thing. Moreover, since zircon has a larger thermal expansion than cordierite, if the silica-O-based crystal growth is not sufficient, the thermal expansion of the glaze is increased.
Furthermore, with respect to Patent Document 3, cordierite crystals are precipitated not by synthetic cordierite but by a reaction during firing. Moreover, since cordierite crystals are not formed by the reaction of only the glaze raw material, it is described that it is due to the reaction at the interface between the substrate and the glaze. As described above, it is described that the crystal formation by the reaction at the time of firing is easily influenced by the cooling rate and also includes the substrate, so that the composition of the substrate should not contain Li 2 O. It will be limited.
Therefore, all of the conventional ones with glaze applied to the cordierite base require a considerable amount of time for cooling during firing, which is significantly more time consuming and costly than general ceramic production. End up. Furthermore, in order to produce crystals by reaction, it is necessary to strictly control not only the glaze but also the composition of the substrate. For this reason, cordierite substrates are used as industrial parts only, but porcelain heat-resistant products with glaze applied to cordierite substrates are difficult to manufacture. For example, it is limited to a petalite material that is easy to manufacture.
そこで本発明は、素地と釉薬からなる低膨張で耐熱衝撃性に優れたコーディエライト質の陶磁器製品を提供するとともに、特に焼成時の冷却時間が短時間でも貫入の発生しない耐熱衝撃性に優れた陶磁器製品を提供することを目的とするものである。 Accordingly, the present invention provides a cordierite-type ceramic product having a low expansion and excellent thermal shock resistance composed of a base material and a glaze, and is particularly excellent in thermal shock resistance that does not cause penetration even when the cooling time during firing is short. The purpose is to provide ceramic products.
本発明は上記問題点を解決するために創作されたものであって、発明１は、素地層と釉薬層を有する陶磁器製品において、前記素地層には低熱膨張のコーディエライト結晶が形成され、前記釉薬層には非晶質のガラス相と共に、低熱膨張の結晶体としてシリカ-O系の結晶体とコーディエライトの結晶体から成ることを特徴とする。このようにコーディエライト素地の表面に、少なくともシリカ-O系の結晶体とコーディエライト結晶体の２つの低熱膨張結晶が安定して形成された釉薬層を施すことで、釉薬の熱膨張が素地の熱膨張に比べて充分に小さくなり、耐熱衝撃性の高い磁器焼結体を得ることができる。また、発明２は、これまでは焼成時に充分時間をかけて冷却することで、釉薬層にシリカ-O系の結晶体を析出させる必要があった。しかし、合成コーディエライトをあらかじめ釉薬に添加することで、冷却速度に関係なく、素地と同じで、しかも高純度のため熱膨張の小さいコーディエライト結晶体が、釉中に安定して残存していることで、シリカ-O系の析出量が少なくても釉薬の熱膨張は素地よりも充分低い値となる。このように、釉薬原料に合成コーディエライトを添加することで、コーディエライトが焼成後も熔融・消失することなく釉薬層に安定して存在することを見出したことが本発明の特徴である。このことにより、これまで長時間を要していたコーディエライト磁器製品の焼成が、普通磁器と同じ冷却速度でも焼成可能となった。
発明３は、特許文献１にあるように、これまではコーディエライト質の素地に対してLi系釉を施釉する場合、焼成時の貫入を抑制するため素地中にLi含有材料をLi2Oとして0.12〜1.0％相当量をあらかじめ含有しておく必要があった。それに対し本発明では、釉薬層のコーディエライト結晶は、素地の組成に影響を受けにくく非常に安定して残存するため、あらかじめコーディエライト質の素地にLi含有材料を添加しなくても貫入が発生しないことを見出したことも本発明の新しい点である。このように、素地中に高価なＬｉ含有材料を添加する必要がなくなることで、原料コストの低下と、Li含有材料に代えて粘土分を多くできることで、成形性が大幅に改善し歩留まりが向上した。勿論、特許文献３とは異なり、釉薬層のコーディエライト結晶は焼成時の反応により生成するものではないため、素地中にLi含有材料があったとしても問題はない。
発明４は、釉薬層におけるシリカ-O系の結晶体は、釉薬原料として配合した６０重量％〜９５重量％の珪石、アルミナ、ドロマイト、長石、ペタライト、仮焼タルクが焼成時に反応して生成されたものであり、この時、シリカ-O系の結晶体と共に非晶質のガラスも生成する。この非晶質のガラスの生成により、釉薬として表面の光沢が発現することを特徴とする。釉薬原料として配合した珪石、アルミナ、ドロマイト、長石、ペタライト、仮焼タルクが６０重量％未満になると、ガラスの生成量が少ないため表面の平滑性や光沢が低下する。一方、９５重量％を超えると、合成コーディエライトの添加量が５重量％未満となるため、貫入が発生しやすくなり好ましくない。さらに貫入の防止と表面状態を考慮すると、珪石、アルミナ、ドロマイト、長石、ペタライト、仮焼タルクは６５重量％〜７５重量％がより好ましい。
The present invention was created to solve the above problems, and the invention 1 is a ceramic product having a base layer and a glaze layer, wherein the base layer is formed with cordierite crystals having low thermal expansion, The glaze layer is characterized by comprising an amorphous glass phase and silica-O based crystals and cordierite crystals as low thermal expansion crystals. By applying a glaze layer in which at least two low thermal expansion crystals, at least silica-O-based crystals and cordierite crystals, are stably formed on the surface of the cordierite substrate, the thermal expansion of the glaze is improved. A ceramic sintered body that is sufficiently smaller than the thermal expansion of the substrate and has high thermal shock resistance can be obtained. Further, in the invention 2, it has been necessary to deposit a silica-O-based crystal in the glaze layer by cooling for a sufficient time during firing so far. However, by adding synthetic cordierite to the glaze in advance, cordierite crystals that are the same as the base material and have low thermal expansion due to high purity, regardless of the cooling rate, remain stably in the glaze. As a result, the thermal expansion of the glaze is sufficiently lower than that of the substrate even if the amount of precipitated silica-O is small. Thus, by adding synthetic cordierite to the glaze material, it has been found that cordierite is stably present in the glaze layer without melting or disappearing even after firing. . As a result, cordierite porcelain products, which have taken a long time, can be fired at the same cooling rate as ordinary porcelain.
Invention 3, as described in Patent Document 1, heretofore if the glazed a Li-based glaze against green body of cordierite, the Li-containing material in the matrix to inhibit the penetration during sintering Li 2 O As an amount equivalent to 0.12 to 1.0%. In contrast, in the present invention, the cordierite crystal of the glaze layer is not affected by the composition of the substrate and remains extremely stable, so that it does not penetrate into the cordierite substrate without adding a Li-containing material in advance. It is also a new point of the present invention that it has been found that this does not occur. In this way, it is not necessary to add expensive Li-containing materials to the substrate, reducing raw material costs and increasing the amount of clay instead of Li-containing materials, greatly improving moldability and improving yield. did. Of course, unlike Patent Document 3, cordierite crystals in the glaze layer are not produced by a reaction during firing, so there is no problem even if there is a Li-containing material in the substrate.
In the invention 4, the silica-O-based crystal in the glaze layer is produced by reacting 60 wt% to 95 wt% of silica, alumina, dolomite, feldspar, petalite, calcined talc blended as a glaze raw material. At this time, amorphous glass is also produced together with the silica-O-based crystal. Due to the generation of this amorphous glass, the surface gloss is manifested as a glaze. When the silica, alumina, dolomite, feldspar, petalite, and calcined talc blended as the glaze raw material is less than 60% by weight, the smoothness and gloss of the surface are lowered because the amount of glass produced is small. On the other hand, if it exceeds 95% by weight, the amount of synthetic cordierite added is less than 5% by weight, which is not preferable because penetration tends to occur. Further, when considering prevention of penetration and surface condition, the content of silica, alumina, dolomite, feldspar, petalite and calcined talc is more preferably 65% by weight to 75% by weight.
上記構成としたことにより、コーディエライト素地に低熱膨張の結晶を含有・生成する釉薬を施すことで、普通磁器と同様の焼成時の冷却時間でも貫入が発生することなく、耐熱衝撃性の高い磁器質の耐熱製品を安定して製造することが可能となる。本発明の耐熱製品は、熱膨張係数が３．８×１０-6以下の製品であるため、２８０℃の温度差にも耐えうる高い耐熱衝撃性を有する。そのため、電子レンジは勿論、オーブンレンジにも充分使用可能である。また、原料価格の高いペタライトを素地の原料として使用せず、比較的価格の安いタルクを主原料とすることで、原料費を抑えた低熱膨張磁器が得られる。更に、従来のペタライト質の耐熱衝撃性の食器は吸水性があるため、使用するたびに食品を含む水分を吸収・蓄積し、シミとなって残存する。そのため、シミが目立たぬよう、黒や茶色の釉薬を施した食器しか製品化できないといった問題があった。それに対し、本発明品は低熱膨張で、耐熱衝撃性に優れることは勿論、吸水性のない磁器製品であることも大きな特徴とする。そのため、これまでの耐熱製品では作りたくても作れなかった、外観が一般食器同様の白磁の食器や、白磁に下絵を施したものも耐熱製品として商品化が可能になった。つまり、調理後の料理を盛りつけた状態で、そのままフリーザー、オーブン、スチームオーブン、電子レンジのいずれにも使用することが可能である上、例えば、調理後に該焼結体に盛りつけた料理をそのままフリーザーで保管し、食事の前にスチームオーブンや電子レンジで加熱して、食卓にそのまま供することができる。 By adopting the above configuration, by applying a glaze that contains and generates crystals with low thermal expansion to the cordierite substrate, penetration does not occur even during the firing time similar to ordinary porcelain, and high thermal shock resistance It becomes possible to stably manufacture a heat-resistant product made of porcelain. Since the heat-resistant product of the present invention is a product having a thermal expansion coefficient of 3.8 × 10 −6 or less, it has high thermal shock resistance that can withstand a temperature difference of 280 ° C. Therefore, it can be sufficiently used not only for microwave ovens but also for microwave ovens. Moreover, a low thermal expansion porcelain with reduced raw material costs can be obtained by using talc, which is relatively inexpensive, as the main raw material without using petalite having a high raw material price as a raw material. Furthermore, since conventional petalite-type thermal shock resistant tableware absorbs water, it absorbs and accumulates water containing food every time it is used, and remains as a stain. Therefore, there was a problem that only the tableware with black or brown glaze could be commercialized so that the spots were not noticeable. In contrast, the product of the present invention is characterized by low thermal expansion and excellent thermal shock resistance, as well as a porcelain product having no water absorption. For this reason, white porcelain dishes with the same appearance as general tableware, or white porcelain with a background, which could not be made with conventional heat-resistant products, can now be commercialized as heat-resistant products. In other words, it can be used in any of a freezer, an oven, a steam oven, and a microwave oven as it is after cooking the dishes. It can be stored in the oven, heated in a steam oven or microwave before meals, and served directly on the table.
以下、本発明の実施の形態を表１〜表２、及び、図１に基づいて説明する Hereinafter, embodiments of the present invention will be described with reference to Tables 1 and 2 and FIG.
先ず、素地層に用いる原料には、カオリン（Al2O3・２SiO2・２H2O）と、タルク（３MgO・４SiO2・H2O）と、アルミナ（Al2O3）と長石粉末を、コーディエライト組成になるよう秤量し、湿式ボールミルで混合・粉砕した。微粉砕の後、通常の陶磁器製品の製造方法と同様、フィルタープレスにより脱水処理を行い、粘度調整の後、圧力鋳込み成形により、直径180mmで高さ30mmの皿を成形した。その後、乾燥したものを電気炉により900℃で素焼きを行った。
一方、釉薬原料は、表1に示すように合成コーディエライト無添加の従来釉薬と、合成コーディエライトの添加量が5%のA-1、25%のA-2、40%のA-3と、45%配合の比較例について、それぞれボールミルに投入し、同量の水を入れ、平均粒径が4μｍ以下になるまで充分に微粉砕した。
First, the raw materials used for the base layer are kaolin (Al 2 O 3 .2SiO 2 .2H 2 O), talc (3MgO.4SiO 2 .H 2 O), alumina (Al 2 O 3 ) and feldspar powder. The cordierite composition was weighed and mixed and pulverized by a wet ball mill. After the fine pulverization, a dehydration process was performed by a filter press in the same manner as in a general method for producing ceramic products. After adjusting the viscosity, a plate having a diameter of 180 mm and a height of 30 mm was formed by pressure casting. Thereafter, the dried product was baked at 900 ° C. in an electric furnace.
On the other hand, as shown in Table 1, the glaze raw materials include conventional glazes without synthetic cordierite added, synthetic cordierite addition amount of 5% A-1, 25% A-2, 40% A- For Comparative Examples 3 and 45%, each was put into a ball mill, the same amount of water was added, and the mixture was sufficiently pulverized until the average particle size was 4 μm or less.
各釉薬をそれぞれ少量乾燥した後、るつぼに入れ電気炉で1300℃焼成を行い、1300℃から−600℃／Hrの速度で炉冷した。室温まで冷却した後、直径5mm×長さ20mmに切り出し、熱膨張測定を行った結果、表１に記載の通り、合成コーディエライト添加量の増加に伴い、熱膨張係数が小さくなることが確認された。
更に、焼成後のA-2配合の釉薬について微粉砕の後、X線回折測定を行った結果を図1に示す。図1に図示する如く、釉薬中には、結晶相としてシリカ-O系とコーディエライトの結晶の存在が認められた。また、表１中には、釉薬のX線回折測定による結晶相を示している。その結果、比較例1の従来釉薬は焼成時に生成したシリカ-O系の結晶だけであるが、それ以外の本発明品と比較例２は、シリカ-O系とコーディエライト結晶を含むことが分かった。更に、そのピーク強度であるが、表1中に示した2θが26°にあるシリカ-O系のメインピークの強度は、合成コーディエライトの添加量の増加に伴い減少した。一方、2θが6°にあるコーディエライト結晶のメインピーク強度は、合成コーディエライト無添加の比較例（従来釉薬）には認められず、その他の釉薬からは合成コーディエライト添加量の増加に伴い強度も増加することが確かめられた。このことから、釉薬層のコーディエライト結晶は、合成コーディエライトが焼成後も残存したものであると考えられ、それを確かめるため、釉薬に添加する前の合成コーディエライト粉末についてX線回折測定を行った結果、釉薬添加後のコーディエライトのピークとすべて一致した。次に、コーディエライト結晶とシリカ-O系結晶の強度から、その強度比を算出した。コーディエライト結晶／シリカ-O系結晶の強度比の値は、比較例1（従来釉薬）が０、本発明品（A-1）が0.053、本発明品（A-2）が0.628、本発明品（A-3）が3.421、比較例２が9.846となる。このことから、コーディエライト結晶とシリカ-O系結晶の強度比は0.053以上、9.846未満であればよく、より好ましくは0.628以上、3.421以下の範囲である。
次に、素焼きした皿形状の素地に、比較例１の従来釉薬とA-1〜A-3釉薬、比較例２の釉薬をそれぞれ施釉した後、電気炉で1300℃焼成し、最高温度1300℃から−600℃／Hrの速度で炉冷した。室温まで冷却した後、焼結体を取り出し、貫入の発生有無と表面状態について確認した結果を表２に示す。
Each glaze was dried in a small amount and then placed in a crucible and fired at 1300 ° C. in an electric furnace and cooled at a rate of 1300 ° C. to −600 ° C./Hr. After cooling to room temperature, cut into 5mm diameter x 20mm length and measured thermal expansion. As shown in Table 1, it was confirmed that the coefficient of thermal expansion decreased as the amount of synthetic cordierite added increased. It was done.
Further, FIG. 1 shows the result of X-ray diffraction measurement after fine pulverization of the glaze containing A-2 after firing. As shown in FIG. 1, the presence of silica-O-based and cordierite crystals as crystal phases was observed in the glaze. Moreover, in Table 1, the crystal phase by the X-ray diffraction measurement of the glaze is shown. As a result, the conventional glaze of Comparative Example 1 is only silica-O-based crystals produced during firing, but the other products of the present invention and Comparative Example 2 contain silica-O-based and cordierite crystals. I understood. Furthermore, as for the peak intensity, the intensity of the main peak of the silica-O system having 2θ of 26 ° shown in Table 1 decreased as the amount of synthetic cordierite added increased. On the other hand, the main peak intensity of cordierite crystals with 2θ of 6 ° is not observed in the comparative example with no added synthetic cordierite (conventional glaze), and the amount of synthetic cordierite added from other glazes is increased. It was confirmed that the strength increased with this. From this, it is considered that the cordierite crystals in the glaze layer are those in which the synthetic cordierite remains after firing. To confirm this, X-ray diffraction was performed on the synthetic cordierite powder before being added to the glaze. As a result of the measurement, all the cordierite peaks after the glaze addition were in agreement. Next, the strength ratio was calculated from the strength of the cordierite crystal and the silica-O-based crystal. The value of the strength ratio of cordierite crystal / silica-O-based crystal is 0 for Comparative Example 1 (conventional glaze), 0.053 for the product of the present invention (A-1), and 0.628 for the product of the present invention (A-2). Invention (A-3) is 3.421, and Comparative Example 2 is 9.846. Therefore, the strength ratio of cordierite crystal and silica-O-based crystal may be 0.053 or more and less than 9.846, and more preferably 0.628 or more and 3.421 or less.
Next, after applying the conventional glaze of Comparative Example 1, the A-1 to A-3 glaze, and the glaze of Comparative Example 2 to the unglazed dish-shaped substrate, each was fired at 1300 ° C. in an electric furnace, and the maximum temperature was 1300 ° C. To furnace cooling at a rate of −600 ° C./Hr. After cooling to room temperature, the sintered body was taken out, and the results of confirming the occurrence of penetration and the surface state are shown in Table 2.
表２より、合成コーディエライト無添加の従来釉薬は貫入の発生が認められたが、合成コーディエライトを添加したものはすべて貫入の発生は認められず、さらに熱衝撃試験においても、２８０℃の温度差にも耐える高い耐熱衝撃性をもつことが確認された。ただ、合成コーディエライトの添加量が最も多い比較例の釉薬は、ガラス生成量が少ないため、表面の平滑性が低下し凹凸が若干認められるようになった。一方、素地の部分を切り出し、X線回折測定を行った結果、コーディエライト結晶とガラス相からなることが確認され、700℃での熱膨張係数も測定の結果、２．９×１０-6と低熱膨張であった。上述のように、これまで吸水性のない磁器焼結体で、しかも亀裂の発生しない製品を、歩留まり良く製造することが困難であった低熱膨張のコーディエライト磁器製品を、本発明によれば、普通磁器と同じ焼成条件でも安定して製造することが可能となった。そのため、現在、主流となっている原料価格は高いが、歩留まり良く、製造が容易なペタライト質の耐熱衝撃性の食器に代わり、原料価格の安いコーディエライト質の耐熱衝撃性の食器の製造が主流になるものと考えられる。また、ペタライト質の耐熱衝撃性の食器は吸水性があるため、使用するたびに食品を含む水分を吸収・蓄積し、シミとなって残存する。そのため、シミが目立たぬよう、黒や茶色の釉薬を施した食器しか製品化できないのに対し、本発明品は低熱膨張で、耐熱衝撃性に優れ、しかも吸水性のない磁器製品であり、白磁の食器として製品化が可能である。更に、釉薬中に残存するコーディエライト結晶は、光の屈折率の値が1.54と、ガラスの値1.51に近いため、引用文献２に示されている屈折率1.92のジルコンでは、不透明なマット釉となるため困難な、白磁に下絵を施す加飾も、本発明品では製品化することが可能である。 From Table 2, the occurrence of penetration was observed in the conventional glazes with no synthetic cordierite added, but no penetration was observed in any of the synthetic cordierite added, and also in the thermal shock test at 280 ° C. It was confirmed that it has high thermal shock resistance that can withstand the temperature difference. However, the glaze of the comparative example having the largest added amount of synthetic cordierite has a small glass production amount, so that the smoothness of the surface is lowered and some irregularities are recognized. On the other hand, as a result of cutting out the base material and performing X-ray diffraction measurement, it was confirmed that it was composed of cordierite crystal and a glass phase, and the coefficient of thermal expansion at 700 ° C. was measured to be 2.9 × 10 −6. And low thermal expansion. As described above, according to the present invention, a cordierite porcelain product having low thermal expansion, which has been difficult to produce a ceramic sintered body having no water absorption and crack-free products with high yield, It became possible to manufacture stably even under the same firing conditions as ordinary porcelain. For this reason, although the price of raw materials, which is currently the mainstream, is high, the production of cordierite-type thermal shock-resistant tableware, which is cheaper in raw material price, is being used instead of petalite-type thermal shock-resistant tableware that is easy to manufacture. It is considered to become mainstream. In addition, since the petalitic thermal shock resistant tableware absorbs water, it absorbs and accumulates water containing food every time it is used, and remains as a stain. For this reason, only tableware with black and brown glazes can be commercialized so that stains are not noticeable, while the product of the present invention is a porcelain product with low thermal expansion, excellent thermal shock resistance, and no water absorption. It can be commercialized as a tableware. Furthermore, since the cordierite crystal remaining in the glaze has a light refractive index value of 1.54, which is close to the glass value of 1.51, zircon having a refractive index of 1.92 shown in the cited reference 2 has an opaque matte wrinkle. Therefore, it is difficult to decorate the white porcelain with a sketch, and the product of the present invention can be commercialized.
そのため、従来のペタライト製品の場合、製品の上で食品を加熱した後、白色の一般食器に移し替えて食卓に供していたが、その移し替えの手間を省くことが可能となる。つまり、調理後の料理を盛りつけた状態でそのままフリーザー、オーブン、スチームオーブン、電子レンジのいずれにも使用することが可能である上、例えば、調理後に該焼結体に盛りつけた料理をそのままフリーザーで保管し、食事の前にスチームオーブンや電子レンジで加熱して、食卓にそのまま供することができる。加えて、食事後には、焼結体を自動洗浄機で洗浄し、熱風乾燥機で乾燥することも可能である。なお、上記焼結体は、皿状を呈する食器であるとして説明したが、皿状以外の形状を呈する食器でもよく、更に、食器以外の加熱調理器などであってもよい。また、原料に関しても、これまでは素地層の原料に、リチウム元素を有する原料を含むことが貫入防止のために必要条件であったが、本発明の釉薬においては、その制約が不要であるため、粘性原料への置き換えにより、原料コストの低下と、製造歩留まりの向上が可能となる。 For this reason, in the case of the conventional petalite product, the food is heated on the product, and then transferred to white general tableware for use on the table. However, it is possible to save the time and effort of the transfer. In other words, it can be used in any of a freezer, an oven, a steam oven, and a microwave oven in a state where the cooked food is served. It can be stored and heated in a steam oven or microwave oven before meals and served directly on the table. In addition, after the meal, the sintered body can be washed with an automatic washing machine and dried with a hot air drier. In addition, although demonstrated that the said sintered compact was tableware which exhibits a dish shape, the tableware which exhibits shapes other than a dish shape may be sufficient, and also heating cookers other than a tableware may be sufficient. In addition, regarding raw materials, it has been a necessary condition for preventing intrusion to include a raw material having lithium element in the raw material of the base layer so far, but the glaze of the present invention does not require that restriction. By replacing with a viscous raw material, the raw material cost can be reduced and the production yield can be improved.
本発明で得られた低熱膨張磁器は、食器以外にもさまざまな用途に使用できる可能性を有する。例えば、現在、金属製のものが使用されているオーブンレンジやスチームオーブン、ガスオーブン用のトレイ、あるいはオーブントースター用のトレイなどとしても充分使用可能である。更には、炊飯器用の内釜、あるいは炊いたご飯を保存するおひつなどにも利用できる可能性がある。 The low thermal expansion porcelain obtained by the present invention has a possibility of being used for various purposes other than tableware. For example, it can be sufficiently used as a microwave oven, a steam oven, a gas oven tray, an oven toaster tray, or the like that is currently made of metal. Furthermore, there is a possibility that it can be used for an inner pot for a rice cooker or a diaper for storing cooked rice.
Ｓ シリカ-O系
Ｃ コーディエライト
S Silica-O C Cordierite
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