JP2011168476A - Patterned crystallized glass article and method of producing the same - Google Patents
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本発明は、建築物の内外装材及び装飾材に好適な模様入り結晶化ガラス物品と、その製造方法に関するものである。 The present invention relates to a crystallized glass article with a pattern suitable for an interior / exterior material of a building and a decoration material, and a method for producing the same.
近年のガラスの建材の動向として、柔らかい光を透過させる建材が流行りである。従来の結晶化ガラス建材は、壁材としての使用例が多く、光を透過させることを目的としていなかったため、結晶化ガラスのみで構成した結晶化ガラス建材が主流であった。 As a trend of glass building materials in recent years, building materials that transmit soft light are in fashion. Since conventional crystallized glass building materials have many examples of use as wall materials and are not intended to transmit light, crystallized glass building materials composed only of crystallized glass have been mainstream.
透光部を有する結晶化ガラス建材としては、例えば、特許文献１には、非結晶性のガラス小片を埋め込んだ結晶化ガラス物品とその製造方法が開示されている。 As a crystallized glass building material having a translucent part, for example, Patent Document 1 discloses a crystallized glass article in which an amorphous glass piece is embedded and a method for manufacturing the same.
また、特許文献２には、透明部分と不透明部分が混在する模様付き結晶化ガラスとその製造方法が開示されている。 Patent Document 2 discloses a crystallized glass with a pattern in which a transparent part and an opaque part are mixed, and a manufacturing method thereof.
さらに、本出願人による特許文献３〜５には、同時に熱処理すると結晶析出量が異なる２種類の結晶化ガラスを用いて結晶析出量が少ない透明部分と結晶析出量が多い不透明部分が混在する模様付き結晶化ガラスと、その製造方法が開示されている。 Further, in Patent Documents 3 to 5 by the present applicant, a transparent portion with a small amount of crystal precipitation and an opaque portion with a large amount of crystal precipitation are mixed using two types of crystallized glass having different amounts of crystal precipitation when heat-treated simultaneously. A crystallized glass and a method for producing the same are disclosed.
特許文献１に記載の従来の結晶化ガラス物品では、非結晶性のガラス小片と結晶化ガラスとの膨張係数が考慮されておらず、破損する問題があった。 In the conventional crystallized glass article described in Patent Document 1, the expansion coefficient between the non-crystalline glass piece and the crystallized glass is not taken into consideration, and there is a problem of breakage.
また、特許文献２に記載の模様付き結晶化ガラスでは、普通ガラスと結晶化ガラスとの線膨張係数の差を、両者の中間の線膨張係数を有する薄層をガラス粒・粉状体に被覆する開示があるが、製造コストが著しく高額となり、また介在する薄層の滑り現象により強度が不足するという問題があった。 Moreover, in the crystallized glass with a pattern described in Patent Document 2, the difference in linear expansion coefficient between ordinary glass and crystallized glass is covered with a thin layer having a linear expansion coefficient intermediate between the two, on a glass particle / powder body. However, there is a problem that the manufacturing cost is remarkably high and the strength is insufficient due to the slip phenomenon of the intervening thin layer.
また、特許文献３〜５に記載の模様付き結晶化ガラスでは、透光性の結晶化ガラス部位は乳白色となり可視光透過率が低く、特に透過照明を用いた際には模様があまり明確に現れないという問題があった。 In addition, in the crystallized glass with a pattern described in Patent Documents 3 to 5, the translucent crystallized glass part is milky white and has low visible light transmittance, and the pattern appears very clearly particularly when using transmitted illumination. There was no problem.
本発明の課題は、内外装建材としての装飾性、間接照明等に好適な適度な透光性と実用強度とを兼ね備えた模様入り結晶化ガラス物品及びその製造方法を提供することである。 An object of the present invention is to provide a patterned crystallized glass article having a suitable translucency and practical strength suitable for decorative and indirect lighting as an interior / exterior building material and a method for producing the same.
上記技術的課題を解決するためになされた本発明に係る模様入り結晶化ガラス物品は、表面から内部に向かって針状の結晶が析出した複数の結晶化ガラス小領域が互いに融着している成形体中に、透光性の非晶質ガラスよりなる複数の透光領域が埋設された模様入り結晶化ガラス物品であって、前記結晶化ガラスの粘度が１０４Ｐａ・ｓとなる温度と、前記非晶質ガラスが前記粘度と同一となる温度との温度差が１００℃以内であり、かつ前記透光領域の厚さ１ｍｍにおける可視光平均透過率が１０％以上であることを特徴とする。 In the patterned crystallized glass article according to the present invention made to solve the above technical problem, a plurality of crystallized glass small regions in which needle-like crystals are precipitated from the surface toward the inside are fused to each other. A patterned crystallized glass article in which a plurality of translucent regions made of translucent amorphous glass are embedded in a molded body, wherein the crystallized glass has a viscosity of 10 4 Pa · s; The temperature difference between the amorphous glass and the temperature at which the amorphous glass becomes the same as the viscosity is within 100 ° C., and the average visible light transmittance at a thickness of 1 mm of the light transmitting region is 10% or more. To do.
また、本発明に係る模様入り結晶化ガラス物品の製造方法は、結晶性ガラス小体と、該結晶性ガラス小体が結晶化した後の結晶化ガラスとの３０〜３８０℃における線膨張係数差が１０×１０−７／Ｋ以下であり、かつ、粘度が１０４Ｐａ・ｓとなる前記結晶化ガラスの温度との温度差が１００℃以内である透光性の非晶質ガラス体とを、耐火性容器に充填して加熱して、互いに融着させつつ、結晶性ガラス小体の表面から内部に向けて針状結晶を析出させることを特徴とする。 In addition, the method for producing a patterned crystallized glass article according to the present invention includes a difference in linear expansion coefficient at 30 to 380 ° C. between the crystalline glass body and the crystallized glass after the crystalline glass body is crystallized. A translucent amorphous glass body having a temperature difference of not more than 10 × 10 −7 / K and a temperature difference of 100 ° C. or less with respect to the temperature of the crystallized glass having a viscosity of 10 4 Pa · s. It is characterized in that acicular crystals are deposited from the surface of the crystalline glass body toward the inside while being filled in a refractory container and heated to be fused together.
上記本発明の模様入り結晶化ガラス物品は、結晶化ガラスの粘度が１０４Ｐａ・ｓとなる温度と、非晶質ガラスが前記粘度と同一となる温度との温度差が１００℃以内であり、透光領域の厚さ１ｍｍにおける可視光平均透過率が１０％以上であるので、内外装建材としての装飾性、間接照明等に好適な適度な透光性と実用強度とを兼ね備えた新たな結晶化ガラス建材を提供することができる。 In the patterned crystallized glass article of the present invention, the temperature difference between the temperature at which the crystallized glass has a viscosity of 10 4 Pa · s and the temperature at which the amorphous glass has the same viscosity is within 100 ° C. Since the average visible light transmittance at a thickness of 1 mm of the light-transmitting region is 10% or more, a new combination of suitable translucency suitable for interior and exterior building materials, indirect lighting, etc., and practical strength. A crystallized glass building material can be provided.
本発明の模様入り結晶化ガラス物品の製造方法は、結晶性ガラス小体と、この結晶性ガラス小体が結晶化した後の結晶化ガラスとの３０〜３８０℃における線膨張係数差が１０×１０−７／Ｋ以下であり、かつ、粘度が１０４Ｐａ・ｓとなる前記結晶化ガラスの温度との温度差が１００℃以内である透光性の非晶質ガラス体とを、耐火性容器に充填して加熱して、互いに融着させつつ、結晶性ガラス小体の表面から内部に向けて針状結晶を析出させるので、上記本発明の新たな模様入り結晶化ガラス物品を効率よく製造することができる。 In the method for producing a patterned crystallized glass article according to the present invention, the difference in linear expansion coefficient at 30 to 380 ° C. between the crystalline glass body and the crystallized glass after the crystalline glass body is crystallized is 10 ×. A translucent amorphous glass body having a temperature difference of not more than 10 −7 / K and a viscosity of 10 4 Pa · s with respect to the temperature of the crystallized glass within 100 ° C. Since the needle-like crystals are deposited from the surface of the crystalline glass body toward the inside while being fused and heated by filling the container, the above-described new patterned crystallized glass article of the present invention can be efficiently used. Can be manufactured.
以下に、表面から内部に向かって針状の結晶が析出した複数の結晶化ガラス小領域が互いに融着している成形体中に、透光性の非晶質ガラスよりなる複数の透光領域が埋設され、その結晶化ガラスの粘度が１０４Ｐａ・ｓとなる温度と、非晶質ガラスの粘度が１０４Ｐａ・ｓとなる温度との温度差が１００℃以内であり、かつ前記透光領域の厚さ１ｍｍにおける可視光平均透過率が１０％以上である本発明の模様入り結晶化ガラス物品の実施形態について説明する。 In the following, a plurality of light-transmitting regions made of light-transmitting amorphous glass are formed in a molded body in which a plurality of crystallized glass small regions in which needle-like crystals are precipitated from the surface toward the inside. The temperature difference between the temperature at which the crystallized glass has a viscosity of 10 4 Pa · s and the temperature at which the amorphous glass has a viscosity of 10 4 Pa · s is within 100 ° C., and An embodiment of the patterned crystallized glass article of the present invention having an average visible light transmittance of 10% or more at a thickness of 1 mm in the light region will be described.
模様入り結晶化ガラス物品で、成形体を形成する結晶化ガラスの粘度が１０４Ｐａ・ｓとなる温度と、非晶質ガラスの粘度が１０４Ｐａ・ｓとなる温度との温度差が１００℃を超えると、模様入り結晶化ガラス物品の意匠面に、突起又は発泡を生じて外観が損なわれる。本発明の模様入り結晶化ガラス物品を構成する結晶化ガラス及び非晶質ガラスとしては、結晶化ガラスと非晶質ガラスの粘度が１０４Ｐａ・ｓとなる温度の温度差が１００℃以内であることが重要である。 In a patterned crystallized glass article, the temperature difference between the temperature at which the crystallized glass forming the molded body has a viscosity of 10 4 Pa · s and the temperature at which the amorphous glass has a viscosity of 10 4 Pa · s is 100. When it exceeds ° C., protrusions or foaming occurs on the design surface of the patterned crystallized glass article, and the appearance is impaired. As the crystallized glass and the amorphous glass constituting the patterned crystallized glass article of the present invention, the temperature difference between the temperatures at which the viscosity of the crystallized glass and the amorphous glass is 10 4 Pa · s is within 100 ° C. It is important to be.
本発明の模様入り結晶化ガラス物品で、結晶化ガラスよりなる成形体中に埋設された透光性の非晶質ガラスよりなる複数の透光領域としては、アルミノ珪酸塩ガラス、ホウ珪酸ガラス等のうち３０〜３８０℃における線膨張係数が、比較的結晶化ガラスの線膨張係数に近い非晶質ガラスからなり、結晶化ガラスよりも十分に透明なものであれば使用可能である。また、透光領域の厚さ１ｍｍにおける可視光平均透過率が１０％未満であると、光が十分に透過せず、自然光や照明を用いた壁面等の演出が不十分なものになる。 In the patterned crystallized glass article of the present invention, the plurality of translucent regions made of translucent amorphous glass embedded in a molded body made of crystallized glass include aluminosilicate glass, borosilicate glass, etc. Of these, any glass can be used as long as it has a linear expansion coefficient at 30 to 380 ° C. made of amorphous glass that is relatively close to that of crystallized glass, and is sufficiently transparent than crystallized glass. In addition, when the visible light average transmittance at a thickness of 1 mm in the translucent region is less than 10%, light is not sufficiently transmitted, and effects such as a wall surface using natural light or illumination become insufficient.
本発明の模様入り結晶化ガラス物品は、ＡＳＴＭ Ｃ１５８−２００７に基づいた４点支持曲げ試験において、寸法５０ｍｍ×２５０ｍｍ×厚さ１５ｍｍの試験体における曲げ強度が２００Ｋｇ／ｃｍ２以上であることが好ましい。なお、単位Ｋｇ／ｃｍ２はｋｇｆ／ｃｍ２と同じ意味である。 The crystallized glass article with a pattern of the present invention preferably has a bending strength of 200 kg / cm 2 or more in a test body having dimensions of 50 mm × 250 mm × thickness of 15 mm in a four-point support bending test based on ASTM C158-2007. . The unit Kg / cm 2 has the same meaning as kgf / cm 2 .
模様入り結晶化ガラス物品の曲げ強度が２００Ｋｇ／ｃｍ２未満であると、施工後に負荷がかかった場合に破損する虞があるため、施工面積を小さくする必要が生じて商品価値がなくなる。 If the bending strength of the patterned crystallized glass article is less than 200 kg / cm 2 , it may be damaged when a load is applied after the construction, so the construction area needs to be reduced and the commercial value is lost.
また、本発明の模様入り結晶化ガラス物品は、前記結晶化ガラスと前記非晶質ガラスとの３０〜３８０℃における線膨張係数の差が、１０×１０−７／Ｋ以下であることが好ましい。 In the patterned crystallized glass article of the present invention, the difference in linear expansion coefficient at 30 to 380 ° C. between the crystallized glass and the amorphous glass is preferably 10 × 10 −7 / K or less. .
結晶化ガラスと非晶質ガラスとの線膨張係数の差が１０×１０−７／Ｋを超えると、結晶化ガラスと非晶質ガラスとの界面に、クラックが生じて強度が不足する。また、模様入り結晶化ガラス物品の温度が変化した際に、結晶化ガラスと非晶質ガラスとの境目からクラックが進行し、やがて破損に至ることになる。 When the difference in linear expansion coefficient between the crystallized glass and the amorphous glass exceeds 10 × 10 −7 / K, cracks are generated at the interface between the crystallized glass and the amorphous glass and the strength is insufficient. In addition, when the temperature of the patterned crystallized glass article changes, a crack progresses from the boundary between the crystallized glass and the amorphous glass, and eventually breaks.
また、本発明の模様入り結晶化ガラス物品は、前記非晶質ガラスの質量割合が、１０〜６０％であることが好ましい。 In the patterned crystallized glass article of the present invention, the mass ratio of the amorphous glass is preferably 10 to 60%.
非晶質ガラスの質量割合が１０％未満であると、透光性及び装飾性に乏しいものとなる。一方、非晶質ガラスの質量割合が６０％を超えると、非晶質ガラスよりなる複数の小領域が繋がって、結晶化ガラスの連続領域が分断され、模様入り結晶化ガラス物品の強度が低下する。 When the mass ratio of the amorphous glass is less than 10%, the light transmitting property and the decorative property are poor. On the other hand, when the mass ratio of the amorphous glass exceeds 60%, a plurality of small regions made of the amorphous glass are connected, the continuous region of the crystallized glass is divided, and the strength of the patterned crystallized glass article is lowered. To do.
また、本発明の模様入り結晶化ガラス物品は、前記非晶質ガラスが、質量百分率表示でＳｉＯ２ ６５〜８０％、Ａｌ２Ｏ３ ２〜８％、Ｂ２Ｏ３ １０〜１５％、ＣａＯ ０〜３％、ＢａＯ ０〜５％、ＺｎＯ ０〜２％、Ｎａ２Ｏ ０〜７％ Ｋ２Ｏ ０〜３％の組成を含有するＢ２Ｏ３−ＳｉＯ２系ガラスからなることが高い化学的耐久性を実現することができるので、好ましい。さらに上記の結晶化ガラスとの膨張係数差を調整するにも好ましく、軟化したガラスの粘性的にも調整しやすいために所望の模様も得やすい。 Further, with patterns crystallized glass article of the present invention, the amorphous glass, SiO 2 65-80% by mass percentage, Al 2 O 3 2~8%, B 2 O 3 10~15%, CaO Highly composed of B 2 O 3 —SiO 2 glass containing a composition of 0 to 3%, BaO 0 to 5%, ZnO 0 to 2%, Na 2 O 0 to 7% K 2 O 0 to 3% This is preferable because chemical durability can be realized. Furthermore, it is also preferable for adjusting the difference in expansion coefficient from the above-mentioned crystallized glass, and since it is easy to adjust the viscosity of the softened glass, it is easy to obtain a desired pattern.
本発明において、非晶質ガラスの各成分の含有量を限定した理由を以下に述べる。 The reason for limiting the content of each component of the amorphous glass in the present invention will be described below.
ＳｉＯ２はガラスのネットワークを形成する成分であり、その含有量が８０％より多いとガラスの溶融温度が高くなるとともに、粘度が増大して熱処理時の流動性が悪くなる。一方、６５％より少ないとアルカリ溶出量が多くなるとともに、耐薬品性や耐熱性が低くなって耐熱性が悪化する。本発明ではＳｉＯ２の含有量は７０〜７３％がさらに好適である。 SiO 2 is a component that forms a network of glass. If its content is more than 80%, the melting temperature of the glass increases, and the viscosity increases, resulting in poor fluidity during heat treatment. On the other hand, if the amount is less than 65%, the amount of alkali elution increases, and the chemical resistance and heat resistance are lowered to deteriorate the heat resistance. In the present invention, the content of SiO 2 is more preferably 70 to 73%.
Ａｌ２Ｏ３はガラスの耐熱性、耐失透性を高める成分であり、その含有量が８％より多いとガラスの溶解性が悪くなり、２％より少ないと失透温度が著しく上昇して溶融ガラス中に失透が生じ易くなり、またガラスのアルカリ溶出量が多くなり化学的耐久性も低下する。本発明ではＡｌ２Ｏ３の含有量は５〜７％がさらに好適である。 Al 2 O 3 is a component that enhances the heat resistance and devitrification resistance of the glass. If its content is more than 8%, the solubility of the glass deteriorates. If it is less than 2%, the devitrification temperature increases remarkably. Devitrification is likely to occur in the molten glass, and the amount of alkali elution of the glass increases and the chemical durability also decreases. In the present invention, the content of Al 2 O 3 is more preferably 5 to 7%.
Ｂ２Ｏ３はガラスの線膨張係数を変化させずに溶融ガラスの粘性を低下させる成分であり、その含有量が１５％より多いと耐酸性や耐熱性が悪化する。一方、１０％より少ないと融剤としての効果が不十分となる。本発明ではＢ２Ｏ３の含有量は１１〜１４％がさらに好適である。 B 2 O 3 is a component that lowers the viscosity of the molten glass without changing the linear expansion coefficient of the glass. If its content exceeds 15%, the acid resistance and heat resistance deteriorate. On the other hand, if it is less than 10%, the effect as a flux becomes insufficient. In the present invention, the content of B 2 O 3 is more preferably 11 to 14%.
ＣａＯ、ＢａＯ及びＺｎＯはともに高温域の粘度を下げてガラスの溶融を容易にする成分であり、ＣａＯが３％、ＢａＯが５％、ＺｎＯが２％よりも多いと高温粘度が低下しすぎて相対的に液相粘度が低くなるため結晶が析出し易くなり、成型温度が著しく制限される。本発明ではＣａＯの含有量は０．５〜１％、ＢａＯは１〜２％がさらに好適である。 CaO, BaO, and ZnO are components that lower the viscosity in the high temperature range to facilitate melting of the glass. If CaO is 3%, BaO is 5%, and ZnO is more than 2%, the high temperature viscosity is too low. Since the liquid phase viscosity is relatively low, crystals are likely to precipitate, and the molding temperature is significantly limited. In the present invention, the CaO content is more preferably 0.5 to 1%, and the BaO content is more preferably 1 to 2%.
Ｎａ２Ｏは溶融ガラスの粘性を低下させるアルカリ成分であり、その含有量が７％よりも多いと化学的耐久性が悪くなり、線膨張係数が高くなる傾向になるために建材として好ましくない。一方、５％より少ないと溶融ガラスの粘性が増大して溶解性や流動性が悪くなる傾向になるので、本発明ではＮａ２Ｏの含有量は５〜７％がさらに好適である。 Na 2 O is an alkaline component that lowers the viscosity of the molten glass. If its content is more than 7%, the chemical durability tends to deteriorate and the linear expansion coefficient tends to increase, which is not preferable as a building material. On the other hand, if the content is less than 5%, the viscosity of the molten glass tends to increase and the solubility and fluidity tend to deteriorate. Therefore, in the present invention, the content of Na 2 O is more preferably 5 to 7%.
Ｋ２Ｏは溶融ガラスの粘性を低下させるアルカリ成分であり、その含有量が３％より多いとガラスのアルカリ溶出量が多くなり化学的耐久性が低下する傾向になる。一方、１％より少ないとガラスの溶融性が悪くなる傾向になるので、本発明ではＫ２Ｏの含有量は１〜３％がさらに好適である。 K 2 O is an alkaline component that lowers the viscosity of the molten glass. If its content is more than 3%, the amount of alkali elution of the glass increases and the chemical durability tends to decrease. On the other hand, when the content is less than 1%, the melting property of the glass tends to deteriorate, and therefore, in the present invention, the content of K 2 O is more preferably 1 to 3%.
清澄剤として機能するＳｂ２Ｏ３を使用する場合、０．０１％未満では清澄効果が低下するので、０．０１〜０．０５％が適量である。また、１％を超える使用は環境上好ましくない。 When Sb 2 O 3 that functions as a fining agent is used, the fining effect is reduced at less than 0.01%, so 0.01 to 0.05% is an appropriate amount. Moreover, use exceeding 1% is not preferable environmentally.
また、本発明の模様入り結晶化ガラス物品は、前記結晶化ガラスが、質量百分率表示でＳｉＯ２ ４５〜７５％、Ａｌ２Ｏ３ １〜２５％、ＣａＯ ２〜２５％、ＺｎＯ ０〜１８％、ＢａＯ ０〜２０％、ＭｇＯ ０〜１．５％、ＳｒＯ ０〜１．５％、Ｎａ２Ｏ １〜２５％ Ｋ２Ｏ ０〜７％、Ｌｉ２Ｏ ０〜５％、Ｂ２Ｏ３ ０〜１．５％、ＣｅＯ２ ０〜０．５％、ＳＯ３ ０〜０．５％、Ａｓ２０３ ０〜１％、Ｓｂ２Ｏ３ ０〜１％、着色酸化物０〜３％の組成を含有し、主結晶としてβ−ウォラストナイトの針状結晶を析出してなるものであることが好ましい。また、この組成を有する結晶性ガラス小体に、着色酸化物として３％未満の無機着色剤等を添加することも可能である。 Further, with patterns crystallized glass article of the present invention, the crystallized glass, SiO 2 45 to 75% by mass percentage, Al 2 O 3 1~25%, CaO 2~25%, ZnO 0~18% , BaO 0~20%, MgO 0~1.5% , SrO 0~1.5%, Na 2 O 1~25% K 2 O 0~7%, Li 2 O 0~5%, B 2 O 3 0~1.5%, CeO 2 0~0.5%, SO 3 0~0.5%, As 2 0 3 0~1%, Sb 2 O 3 0~1%, coloring oxides 0-3% It is preferable that it is formed by precipitating β-wollastonite needle crystals as main crystals. Moreover, it is also possible to add an inorganic colorant of less than 3% as a colored oxide to the crystalline glass body having this composition.
本発明において、結晶化ガラスの各成分の含有量を限定した理由を以下に述べる。 The reason for limiting the content of each component of the crystallized glass in the present invention will be described below.
ＳｉＯ２はβ−ウォラストナイトの成分であり、その含有量が７５％より多いとガラスの溶融温度が高くなるとともに、粘度が増大して熱処理時の流動性が悪くなる。一方、４５％より少ないと成型時の失透性が強くなる。また、本発明ではＳｉＯ２の含有量は５９〜６３％がさらに好適である。 SiO 2 is a component of β-wollastonite, and if its content is more than 75%, the melting temperature of the glass is increased, the viscosity is increased, and the fluidity during heat treatment is deteriorated. On the other hand, if it is less than 45%, devitrification at the time of molding becomes strong. In the present invention, the content of SiO 2 is more preferably 59 to 63%.
Ａｌ２Ｏ３は失透を抑制する成分であり、その含有量が２５％より多いとガラスの溶解性が悪くなるとともに異種結晶（アノーサイト）が析出し熱処理時の流動性が悪くなる。一方、１％より少ないと失透性が強くなり化学的耐久性も低下する。また、本発明ではＡｌ２Ｏ３の含有量は６〜７％がさらに好適である。 Al 2 O 3 is a component that suppresses devitrification, and if its content is more than 25%, the solubility of the glass deteriorates, and dissimilar crystals (anosites) precipitate, resulting in poor fluidity during heat treatment. On the other hand, if it is less than 1%, the devitrification becomes strong and the chemical durability is also lowered. In the present invention, the content of Al 2 O 3 is more preferably 6 to 7%.
ＣａＯはβ−ウォラストナイトの成分であり、その含有量が２５％よりも多いと失透性が強くなり成形が困難となり、又β−ウォラストナイトの析出量が多くなり過ぎて所望の表面平滑性が得難くなる。一方、２％より少ないとβ−ウォラストナイトの析出量が少なくなり過ぎて機械的強度が低下する。また、本発明ではＣａＯの含有量は１４〜１８％がさらに好適である。 CaO is a component of β-wollastonite, and if its content is more than 25%, devitrification becomes strong and molding becomes difficult, and the amount of β-wollastonite is excessively increased, resulting in a desired surface. Smoothness becomes difficult to obtain. On the other hand, if it is less than 2%, the precipitation amount of β-wollastonite becomes too small and the mechanical strength is lowered. In the present invention, the CaO content is more preferably 14 to 18%.
ＺｎＯは結晶化時のガラスの流動性を促進するために添加する成分であり、その含有量が１８％より多いと、β−ウォラストナイトが析出し難くなって所望の特性が得られなくなる。また、本発明ではＺｎＯを使用する場合には、その含有量は５〜７％がさらに好適である。 ZnO is a component added to promote the fluidity of the glass during crystallization. If the content is more than 18%, β-wollastonite is difficult to precipitate and desired characteristics cannot be obtained. In the present invention, when ZnO is used, the content is more preferably 5 to 7%.
ＢａＯも結晶化時のガラスの流動性を促進するために添加する成分であり、含有量が２０％より多いとβ−ウォラストナイトの析出量が少なくなる。また、本発明ではＢａＯの含有量は４〜５％がさらに好適である。 BaO is also a component added to promote the fluidity of the glass during crystallization. If the content is more than 20%, the amount of β-wollastonite decreases. In the present invention, the BaO content is more preferably 4 to 5%.
ＭｇＯはガラスの溶解性や流動性を促進させる成分であるが、３％より多くなると異種結晶を析出するため、流動性を阻害し、特性上も好ましくない。 MgO is a component that promotes the solubility and fluidity of the glass. However, if it exceeds 3%, different crystals are precipitated, which hinders fluidity and is not preferable in terms of properties.
ＳｒＯはガラスの溶解性や流動性を促進させる成分であり、５％より多くなると異種結晶を析出するため、流動性を阻害し、特性上も好ましくない。 SrO is a component that promotes the solubility and fluidity of the glass, and when it exceeds 5%, different crystals are precipitated, which hinders fluidity and is not preferable in terms of characteristics.
Ｎａ２Ｏは溶融ガラスの粘性を低下させるアルカリ成分であり、その含有量が２５％よりも多いと化学的耐久性が悪くなり、膨張係数が高くなるために建材として好ましくない。１％より少ないとガラスの粘性が増大して溶解性や流動性が悪くなる。また、本発明ではＮａ２Ｏの含有量は３〜４％がさらに好適である。 Na 2 O is an alkaline component that lowers the viscosity of the molten glass. If its content is more than 25%, the chemical durability deteriorates and the expansion coefficient becomes high, which is not preferable as a building material. If it is less than 1%, the viscosity of the glass increases and the solubility and fluidity deteriorate. In the present invention, the content of Na 2 O is more preferably 3 to 4%.
Ｋ２Ｏは溶融ガラスの粘性を低下させるアルカリ成分であり、その含有量が７％より多いと化学的耐久性が低下する。また、本発明ではＫ２Ｏの含有量は２〜３％がさらに好適である。 K 2 O is an alkaline component that lowers the viscosity of the molten glass, and if its content is more than 7%, the chemical durability is lowered. In the present invention, the content of K 2 O is more preferably 2 to 3%.
Ｌｉ２Ｏは結晶化速度を速める効果と流動性を促進する効果がある成分であり、その含有量が５％より多いと、線膨張係数が大きくなり、化学的耐久性が低下し、粘性も低下する。ＺｎＯを使用しない場合には、Ｌｉ２Ｏ粘性の低下は熱処理工程において発泡を生じやすくなる。本発明ではＬｉ２Ｏを使用する場合には、その含有量は０．１〜３％がさらに好適である。 Li 2 O is a component that has the effect of accelerating the crystallization rate and the effect of promoting fluidity. If its content is more than 5%, the coefficient of linear expansion increases, the chemical durability decreases, and the viscosity also increases. descend. When ZnO is not used, the decrease in Li 2 O viscosity tends to cause foaming in the heat treatment step. In the present invention, when Li 2 O is used, its content is more preferably 0.1 to 3%.
Ｂ２Ｏ３はガラスの線膨張係数を変化させずに溶融ガラスの粘性を低下させる成分であり、その含有量が１．５％より多いと異種結晶が析出し、所望の特性が得られなくなる。また、本発明ではＢ２Ｏ３の含有量は０．３〜１．０％がさらに好適である。 B 2 O 3 is a component that lowers the viscosity of the molten glass without changing the linear expansion coefficient of the glass. When the content is more than 1.5%, different crystals are precipitated and desired characteristics cannot be obtained. . In the present invention, the content of B 2 O 3 is more preferably 0.3 to 1.0%.
ＣｅＯ２は清澄剤としてのＡｓ２Ｏ３又はＳｂ２Ｏ３の添加が環境上好ましくないことから、Ａｓ２Ｏ３又はＳｂ２Ｏ３の何れかあるいはそれらの合量としての含有量が０．１％以下の場合における結晶化ガラスの白色度の急減を抑制するために使用する成分であり、ＣｅＯ２の含有量は０〜０．５％、好ましくは０．０５〜０．３％である。さらにＣｅＯ２は、還元雰囲気溶融において不純物として含有するＦｅ２Ｏ３によるＦｅ２＋の発色を抑制し、特にＳＯ３（三酸化硫黄）と共存する場合には発色抑制効果が顕著に現れる。ＣｅＯ２が０．５％より多いとＣｅ４＋による褐色の着色が強く現れるようになる。 CeO 2 has an environmentally unfavorable addition of As 2 O 3 or Sb 2 O 3 as a clarifier, and therefore, the content of either As 2 O 3 or Sb 2 O 3 or the total amount thereof is 0. It is a component used for suppressing the rapid decrease in whiteness of crystallized glass in the case of 1% or less, and the content of CeO 2 is 0 to 0.5%, preferably 0.05 to 0.3%. . Further, CeO 2 suppresses the color development of Fe 2+ due to Fe 2 O 3 contained as an impurity in melting in a reducing atmosphere, and particularly when it coexists with SO 3 (sulfur trioxide), the color development suppressing effect appears remarkably. When CeO 2 is more than 0.5%, brown coloring due to Ce 4+ appears strongly.
ＳＯ３は清澄剤として機能する成分であり、その含有量は０〜０．５％、好ましくは０．０２〜０．３％である。ＳＯ３が０．５％より多いと異種結晶が析出する。 SO 3 is a component that functions as a fining agent, and its content is 0 to 0.5%, preferably 0.02 to 0.3%. When SO 3 is more than 0.5%, different crystals are precipitated.
清澄剤として機能するＡｓ２Ｏ３またはＳｂ２Ｏ３を使用する場合、０．１％未満では清澄効果が低下するので、０．２〜０．４％が適量ではあるが、１％を超える使用は環境上好ましくない。 When As 2 O 3 or Sb 2 O 3 that functions as a fining agent is used, the fining effect is reduced at less than 0.1%, so 0.2 to 0.4% is an appropriate amount, but it exceeds 1%. Use is environmentally undesirable.
また、本発明の模様入り結晶化ガラス物品は、前記非晶質ガラスの透光領域の少なくとも一部が、外接円直径が３０〜１００ｍｍであることが好ましい。このような大きさの非晶質ガラスによる透光領域としては、模様として認識される形状であればよいが、外接円直径が３０ｍｍ未満では建材等の明確な大柄模様として認識し難い。一方、外接円直径が１００ｍｍを超えると、融着不足による曲げ強度低下等の問題が生じる虞がある。また上記の曲げ強度を確保する上で、３０〜１００ｍｍの透光領域は、成形体を貫通しない薄板状であることが好ましく、各透光領域が互いに連通していないことがさらに好ましい。 In the patterned crystallized glass article of the present invention, it is preferable that at least a part of the translucent region of the amorphous glass has a circumscribed circle diameter of 30 to 100 mm. The light-transmitting region of amorphous glass having such a size may have any shape that can be recognized as a pattern, but if the circumscribed circle diameter is less than 30 mm, it is difficult to recognize as a clear large pattern such as a building material. On the other hand, if the circumscribed circle diameter exceeds 100 mm, problems such as a decrease in bending strength due to insufficient fusion may occur. Moreover, when ensuring said bending strength, it is preferable that the 30-100 mm translucent area | region is a thin-plate shape which does not penetrate a molded object, and it is still more preferable that each translucent area | region does not mutually communicate.
このような外接円直径が３０〜１００ｍｍである透光領域が形成された模様入り結晶化ガラス物品によれば、任意の大柄な透光模様による光の演出が可能となる。 According to the crystallized glass article with a pattern in which a translucent region having a circumscribed circle diameter of 30 to 100 mm is formed, it is possible to produce light with an arbitrary large translucent pattern.
次に、結晶性ガラス小体と、該結晶性ガラス小体が結晶化した後の結晶化ガラスとの３０〜３８０℃における線膨張係数差が１０×１０−７／Ｋ以下であり、かつ、粘度が１０４Ｐａ・ｓとなる前記結晶化ガラスの温度との温度差が１００℃以内である透光性の非晶質ガラス体とを、耐火性容器に充填して加熱して、互いに融着させつつ、結晶性ガラス小体の表面から内部に向けて針状結晶を析出させる本発明の模様入り結晶化ガラス物品の製造方法について、以下に説明する。 Next, the difference in coefficient of linear expansion at 30 to 380 ° C. between the crystalline glass body and the crystallized glass after the crystalline glass body has crystallized is 10 × 10 −7 / K or less, and A translucent amorphous glass body having a temperature difference of 100 ° C. or less with respect to the temperature of the crystallized glass having a viscosity of 10 4 Pa · s is filled in a refractory container and heated to melt each other. A method for producing a patterned crystallized glass article of the present invention in which acicular crystals are precipitated from the surface of the crystalline glass body toward the inside while being worn will be described below.
結晶性ガラス小体が結晶化した後の結晶化ガラスと透光性の非晶質ガラスとの３０〜３８０℃における線膨張係数差が１０×１０−７／Ｋを超えると、模様入り結晶化ガラス物品に、望まないひび割れ等を生じる。結晶化ガラスと透光性非晶質ガラスとの線膨張係数差が１０×１０−７／Ｋ以内であることが重要であり、５×１０−７／Ｋ以内であることが好ましい。 When the difference in linear expansion coefficient at 30 to 380 ° C. between the crystallized glass after crystallizing the crystalline glass body and the translucent amorphous glass exceeds 10 × 10 −7 / K, patterned crystallization Undesired cracks and the like occur in the glass article. It is important that the difference in coefficient of linear expansion between the crystallized glass and the translucent amorphous glass is within 10 × 10 −7 / K, and preferably within 5 × 10 −7 / K.
また、熱処理の際の粘度が１０４Ｐａ・ｓとなる結晶性ガラス小体の温度及び透光性非晶質ガラス体の温度との温度差ΔＴが１００℃を超えると、模様入り結晶化ガラス物品の意匠面に突起又は発泡を生じて外観が損なわれる。本発明の模様入り結晶化ガラス物品の製造方法は、結晶化ガラスと透光性の非晶質ガラスとを１０４Ｐａ・ｓとなる温度で熱処理することで、意匠面に結晶性ガラス小体及び透光性非晶質ガラス体の形状による突起を生じることが無く、且つ粘性の低下による発泡も無い模様入り結晶化ガラス物品を得ることができる。 When the temperature difference ΔT between the temperature of the crystalline glass body and the temperature of the translucent amorphous glass body at which the viscosity during heat treatment is 10 4 Pa · s exceeds 100 ° C., the patterned crystallized glass Protrusion or foaming occurs on the design surface of the article and the appearance is impaired. In the method for producing a patterned crystallized glass article according to the present invention, a crystallized glass body is formed on the design surface by heat-treating the crystallized glass and the light-transmitting amorphous glass at a temperature of 10 4 Pa · s. And the crystallized glass article with a pattern which does not produce the protrusion by the shape of a translucent amorphous glass body, and does not foam by the viscosity fall can be obtained.
また、本発明の模様入り結晶化ガラス物品の製造方法は、前記結晶性ガラス小体と形状の異なる形状の透光性の非晶質ガラス体を使用することが好ましい。結晶性ガラス小体と、透光性の非晶質ガラス体の形状としては、球形状、粉末形状、管形状、板形状、棒形状やこれらを破砕した形状等を使用するものである。 Moreover, it is preferable that the manufacturing method of the crystallized glass article with a pattern of this invention uses the translucent amorphous glass body of a shape different from the said crystalline glass body. As a shape of the crystalline glass body and the light-transmitting amorphous glass body, a spherical shape, a powder shape, a tube shape, a plate shape, a rod shape, a shape obtained by crushing these, or the like is used.
このように製造方法において、結晶性ガラス小体と異なる形状を有する透光性非晶質ガラス体を使用することで、透光部分の形状にバラエティーを持たせ、光の散乱状体による演出が可能な本発明の模様入り結晶化ガラス物品を製造することができる。 In this way, in the manufacturing method, by using a light-transmitting amorphous glass body having a shape different from that of the crystalline glass body, the shape of the light-transmitting part is varied, and the production by the light scattering-like body is achieved. Possible patterned crystallized glass articles of the invention can be produced.
また、本発明の模様入り結晶化ガラス物品の製造方法は、前記非晶質ガラス体が小体であり、前記結晶性ガラス小体と非晶質ガラス小体とを９０：１０〜４０：６０の質量割合で混合し、耐火性容器に充填して加熱して、互いに融着させつつ、結晶性ガラス小体の表面から内部に向けて針状結晶を析出させることが好ましい。 In the method for producing a patterned crystallized glass article according to the present invention, the amorphous glass body is a small body, and the crystalline glass body and the amorphous glass body are 90:10 to 40:60. It is preferable that the acicular crystals are precipitated from the surface of the crystalline glass body toward the inside while being mixed and heated in a refractory container, heated and fused together.
また、結晶性ガラス小体の質量割合が９０％を超える場合、すなわち透光性の非晶質ガラス小体の質量割合が１０％未満のものであると、透光性に乏しい結晶化ガラスの相対面積が大きくなり模様入り結晶化ガラス物品が透光性及び装飾性に乏しいものとなる。一方、結晶性ガラス小体の質量割合が４０％未満の場合、すなわち非晶質ガラスの質量割合が６０％を超えるものであると、非晶質ガラスよりなる複数の小領域が繋がって、強度が高い結晶化ガラスが連続した領域が分断され、模様入り結晶化ガラス物品の強度が低下する。 Moreover, when the mass ratio of the crystalline glass body is more than 90%, that is, when the mass ratio of the translucent amorphous glass body is less than 10%, the crystallized glass having poor translucency is used. The relative area becomes large, and the patterned crystallized glass article has poor translucency and decorativeness. On the other hand, when the mass ratio of the crystalline glass body is less than 40%, that is, when the mass ratio of the amorphous glass is more than 60%, a plurality of small regions made of amorphous glass are connected, and the strength is increased. The region where the high crystallized glass is continuous is divided, and the strength of the patterned crystallized glass article is lowered.
このように結晶性ガラス小体と非晶質ガラス小体とを９０：１０〜４０：６０の質量割合で混合し、耐火性容器に充填することで、非晶質ガラスの透光領域が全体にほぼ均等に分散埋設された模様入り結晶化ガラス物品を得ることができる。 In this way, the crystalline glass body and the amorphous glass body are mixed at a mass ratio of 90:10 to 40:60 and filled in a refractory container, so that the entire transparent region of the amorphous glass is obtained. It is possible to obtain a patterned crystallized glass article dispersed and embedded almost uniformly.
また、本発明の模様入り結晶化ガラス物品の製造方法は、耐火性容器に、外接円直径が３０〜１００ｍｍの透光性ガラスの薄板（フレーク）を配設することが好ましい。この、透光領域を形成する非晶質ガラスの薄板としては、模様として認識される平面形状であればよく、成形体を貫通しない薄板状であることが重要であり、具体的には、成形体の厚さ１０〜１５ｍｍに対して、２０〜３０％となる厚さが３〜５ｍｍの範囲であると、大柄な透光模様として認識されやすくなり好ましい。また、外接円直径が３０〜１００ｍｍの透光性ガラスの薄板を結晶性ガラス小体の意匠面側又は集積体内部に配設することが、透光模様を形成する上で好ましい。 In the method for producing a patterned crystallized glass article of the present invention, it is preferable to dispose a thin plate (flakes) of translucent glass having a circumscribed circle diameter of 30 to 100 mm in a refractory container. The thin plate of amorphous glass forming the light-transmitting region may be a flat shape recognized as a pattern, and it is important that the thin plate does not penetrate the molded body. A thickness of 20 to 30% with respect to the body thickness of 10 to 15 mm is preferably in the range of 3 to 5 mm because it is easily recognized as a large translucent pattern. In addition, it is preferable to dispose a thin plate of translucent glass having a circumscribed circle diameter of 30 to 100 mm on the design surface side of the crystalline glass body or inside the integrated body in order to form a translucent pattern.
ガラス模様入り結晶化ガラス物品の装飾効果を向上させるために、無機物である遷移元素酸化物の着色材等の添加、あるいは、着色酸化物で着色された結晶性ガラス小体の採用等を行ってもよい。 In order to improve the decorative effect of crystallized glass articles with glass patterns, add colorants such as inorganic transition element oxides or adopt crystalline glass bodies colored with colored oxides. Also good.
以下、本発明の模様入り結晶化ガラス物品及びその製造方法の実施例について、図１を参照して説明する。 Hereinafter, an example of a patterned crystallized glass article and a manufacturing method thereof according to the present invention will be described with reference to FIG.
本発明の模様入り結晶化ガラス物品１０は、図１（ａ）に示すように、針状のβ−ウォラストナイトを主結晶として析出して線膨張係数が６０×１０−７／Ｋの結晶化ガラス部位１０ａに、線膨張係数が５１×１０−７／Ｋの硼珪酸ガラスからなる透光性領域１０ｂが分散して埋設され、断面の透明ガラスの配置などの従来にない特徴を有するものである。また、図１（ｂ）に示すように、裏面側中央に照明を置いて照明光をあてると、透光性領域１０ｂから比較的高い強度の透過光が出て、その周囲の結晶化ガラス部位１０ａからは柔らかい透過光が出て独特の意匠表現が可能となっている。また、光源から離れるにつれて、徐々に光が減衰して光源の形状を反映した柔らかな模様を形成することができる。本実施例１の模様入り結晶化ガラス物品１０は、透光領域１０ｂの厚さ１ｍｍにおける可視光平均透過率が１５％である。 The patterned crystallized glass article 10 of the present invention is a crystal having a linear expansion coefficient of 60 × 10 −7 / K by depositing acicular β-wollastonite as a main crystal as shown in FIG. A translucent region 10b made of borosilicate glass having a linear expansion coefficient of 51 × 10 −7 / K is dispersed and embedded in the vitrified glass portion 10a, and has characteristics not found in the past such as the arrangement of transparent glass in a cross section It is. Moreover, as shown in FIG. 1B, when illumination is applied to the center of the back side and illumination light is applied, a relatively high intensity transmitted light is emitted from the translucent region 10b, and the surrounding crystallized glass region. From 10a, soft transmitted light is emitted, and a unique design expression is possible. Further, as the distance from the light source increases, the light gradually attenuates, and a soft pattern reflecting the shape of the light source can be formed. The patterned crystallized glass article 10 of Example 1 has an average visible light transmittance of 15% when the light-transmitting region 10b has a thickness of 1 mm.
次に、模様入り結晶化ガラス物品１０の製造方法について説明する。 Next, the manufacturing method of the crystallized glass article 10 with a pattern is demonstrated.
まず、質量％でＳｉＯ２ ５９％、Ａｌ２Ｏ３ ６．５％、ＣａＯ ２０．６％、ＺｎＯ ４．６％、ＢａＯ ５％、Ｎａ２Ｏ ４％、Ｋ２Ｏ ０．１％、Ｓｂ２Ｏ３ ０．２％の組成となるように調合したガラス原料混合物を１４００〜１５００℃で１６時間溶融した。次いで、この溶融ガラスを水中に投下して水砕した後、得られた水砕物を乾燥後、分級して直径１〜５ｍｍの結晶性ガラス小体Ａを作製した。この結晶性ガラス小体Ａは、軟化点（約８００℃）より高い温度で熱処理すると、軟化変形しながらβ−ウォラストナイトを主結晶として析出して線膨張係数が６０×１０−７／Ｋの結晶化ガラスとなるものである。この結晶性ガラス小体Ａは球形状や棒形状を破砕した形状を有している。 First, in terms of mass%, SiO 2 59%, Al 2 O 3 6.5%, CaO 20.6%, ZnO 4.6%, BaO 5%, Na 2 O 4%, K 2 O 0.1%, Sb A glass raw material mixture prepared so as to have a composition of 2 O 3 0.2% was melted at 1400 to 1500 ° C. for 16 hours. Next, this molten glass was dropped into water and crushed, and then the obtained crushed product was dried and classified to produce a crystalline glass body A having a diameter of 1 to 5 mm. When this crystalline glass body A is heat-treated at a temperature higher than the softening point (about 800 ° C.), β-wollastonite precipitates as a main crystal while softening and deforming, and the linear expansion coefficient is 60 × 10 −7 / K. This is a crystallized glass. The crystalline glass body A has a shape obtained by crushing a spherical shape or a rod shape.
次いで、質量％でＳｉＯ２ ７２．８％、Ａｌ２Ｏ３ ６．５％、Ｂ２Ｏ３ １１％、ＣａＯ ０．７％、ＢａＯ １．２％、Ｎａ２Ｏ ５．９％、Ｋ２Ｏ １．８％、Ｓｂ２Ｏ３ ０．１％の組成となるように調合したガラス原料混合物を１４００〜１５００℃で１６時間溶融した。次いでこの溶融ガラスを肉厚が１ｍｍの管状に成形し、ロールクラッシャーにて粉砕し、分級して、２ｍｍ〜７ｍｍの硼珪酸ガラスからなり、線膨張係数が結晶化ガラスよりも９×１０−７／Ｋ小さい５１×１０−７／Ｋの透光性ガラス小体Ｂを作製した。この透光性ガラス小体Ｂは管ガラスを破砕した曲面部位がある形状を有している。 Next, SiO 2 72.8%, Al 2 O 3 6.5%, B 2 O 3 11%, CaO 0.7%, BaO 1.2%, Na 2 O 5.9%, K 2 by mass%. A glass raw material mixture prepared so as to have a composition of 1.8% O and 0.1% Sb 2 O 3 was melted at 1400 to 1500 ° C. for 16 hours. Next, this molten glass was formed into a tube having a thickness of 1 mm, crushed by a roll crusher, classified, and made of borosilicate glass of 2 mm to 7 mm. The linear expansion coefficient was 9 × 10 −7 than that of crystallized glass. A translucent glass body B having a small / K of 51 × 10 −7 / K was produced. The translucent glass body B has a shape with a curved surface portion obtained by crushing the tube glass.
次に、結晶性ガラス小体Ａと透光性ガラス小体Ｂを、質量比で結晶性ガラス小体Ａ：透光性ガラス小体Ｂ＝８０：２０で混合し、かつ焼結後の厚さが１５ｍｍになるように質量を秤量し、図２に示すように、アルミナ粉が塗布されたムライト製の型枠１１内に集積した後、１１４０℃で２時間熱処理したところ、各ガラス小体が互いに軟化融着し、図１に示すような結晶化ガラス部位１０ａの白色部分と透光領域１０ｂの透明部分との表面模様を有する平滑な板状の模様入り結晶化ガラス物品１０が得られた。 Next, the crystalline glass body A and the translucent glass body B are mixed at a mass ratio of crystalline glass body A: translucent glass body B = 80: 20, and the thickness after sintering is mixed. As shown in FIG. 2, the mass was weighed so as to be 15 mm and accumulated in a mold 11 made of mullite coated with alumina powder, followed by heat treatment at 1140 ° C. for 2 hours. Are softened and fused to each other to obtain a smooth plate-like patterned crystallized glass article 10 having a surface pattern of the white portion of the crystallized glass portion 10a and the transparent portion of the light-transmitting region 10b as shown in FIG. It was.
模様入り結晶化ガラス物品１０を構成する結晶化ガラスの粘度が１０４Ｐａ・ｓとなる温度と、非晶質ガラスの粘度が１０４Ｐａ・ｓとなる温度は、それぞれ１１６０℃と１１００℃であり、温度差ΔＴは６０℃であった。 The temperature at which the viscosity of the crystallized glass constituting the patterned crystallized glass article 10 is 10 4 Pa · s and the temperature at which the viscosity of the amorphous glass is 10 4 Pa · s are 1160 ° C. and 1100 ° C., respectively. The temperature difference ΔT was 60 ° C.
本実施例２の模様入り結晶化ガラス物品の製造方法では、結晶性ガラス小体Ａ：透光性ガラス小体Ｂ＝５０：５０で混合し、かつ焼結後の厚さが１５ｍｍになるように質量を秤量し、アルミナ粉が塗布されたムライト製の型枠内に集積した後、１１４０℃で２時間熱処理したところ、各ガラス小体が互いに軟化融着し、表面模様が白色部分と透明部分を有する平滑な板状物品を得た。本実施例２の模様入り結晶化ガラス物品は、２種類の形状の異なるガラス小体を融着させることで従来に無い意匠性を有すものである。この模様入り結晶化ガラス物品の透光性領域の厚さ１ｍｍにおける可視光平均透過率は１８％である。 In the method for producing a patterned crystallized glass article of Example 2, the crystalline glass body A: translucent glass body B = 50: 50 are mixed, and the thickness after sintering is 15 mm. After weighed and collected in a mullite mold coated with alumina powder and heat treated at 1140 ° C. for 2 hours, the glass bodies softened and fused together, and the surface pattern was transparent with the white part. A smooth plate-like article having a part was obtained. The patterned crystallized glass article of Example 2 has an unprecedented design by fusing two kinds of glass bodies having different shapes. The average visible light transmittance at a thickness of 1 mm of the translucent region of this patterned crystallized glass article is 18%.
比較例１として結晶性ガラス小体Ａのみ、比較例２として透光性ガラス小体Ｂのみ焼結後の厚さが１５ｍｍになるように質量を秤量し、アルミナ粉が塗布されたムライト製の型枠内に集積した後、同様に１１４０℃で２時間熱処理した。比較例１の結晶性ガラス小体Ａのみでは、従来の不透光性結晶化ガラス板が得られた。また、比較例２の透光性ガラス小体Ｂのみでは、従来の透光性の焼結ガラス物品が得られた。 As comparative example 1, only crystalline glass body A, and as comparative example 2, only translucent glass body B was weighed so that the thickness after sintering was 15 mm, and made of mullite coated with alumina powder. After accumulating in the mold, it was similarly heat treated at 1140 ° C. for 2 hours. With only the crystalline glass body A of Comparative Example 1, a conventional opaque glass crystallized glass plate was obtained. Moreover, only the translucent glass body B of Comparative Example 2 yielded a conventional translucent sintered glass article.
本実施例による試験体寸法５０ｍｍ×２５０ｍｍ×厚さ１５ｍｍにおける各試料のＡＳＴＭ Ｃ１５８−２００７に基づいた４点単純曲げ強度は、装飾材としては全く問題のないものであった。各試料における４点単純曲げ強度は、下記の通りであった。 The four-point simple bending strength based on ASTM C158-2007 of each sample in the specimen size of 50 mm × 250 mm × thickness 15 mm according to this example was not a problem as a decoration material. The 4-point simple bending strength in each sample was as follows.
それに対して比較例１の結晶性ガラス小体Ａのみを使用した従来の不透光性結晶化ガラス板は、４点支持曲げ強度は高いものの、意匠性に乏しいものであった。また、比較例２の透光性ガラス小体Ｂのみを使用した焼結ガラス物品では、全体が透光性で意匠性に乏しく、かつ建築用途の板状体としては強度が不足するものであった。 On the other hand, the conventional non-transparent crystallized glass plate using only the crystalline glass body A of Comparative Example 1 was poor in design, although the four-point support bending strength was high. Moreover, in the sintered glass article using only the translucent glass body B of Comparative Example 2, the whole is translucent and has poor design, and the strength is insufficient as a plate for architectural use. It was.
本発明の模様入り結晶化ガラス物品２０は、図３に示すように、針状のβ−ウォラストナイトを主結晶として析出して線膨張係数が６０×１０−７／Ｋの結晶化ガラス部位２０ａに、線膨張係数が５１×１０−７／Ｋの硼珪酸ガラスからなる透光性領域２０ｂが分散して埋設され、断面方向の透明ガラスの配置などに従来にない特徴を有するものである。裏面側から照明を置いて照明光をあてると、外接円直径ｄが３０〜１００ｍｍの多様な形状の透光性領域２０ｂから比較的高い強度の透過光による深みのある大柄模様が現れ、その周囲の結晶化ガラス部位２０ａからは仄かな柔らかい透過光が出る。 As shown in FIG. 3, the patterned crystallized glass article 20 according to the present invention precipitates acicular β-wollastonite as a main crystal and has a linear expansion coefficient of 60 × 10 −7 / K. In 20a, a translucent region 20b made of borosilicate glass having a linear expansion coefficient of 51 × 10 −7 / K is dispersed and embedded, and has an unprecedented feature in the arrangement of transparent glass in the cross-sectional direction. . When the illumination light is applied from the back side, a large pattern with a depth due to a relatively high intensity of transmitted light appears from various shapes of the translucent region 20b having a circumscribed circle diameter d of 30 to 100 mm. A faint soft transmitted light is emitted from the crystallized glass portion 20a.
次に、模様入り結晶化ガラス物品２０の製造方法について説明する。 Next, a method for manufacturing the patterned crystallized glass article 20 will be described.
まず、結晶化ガラスとの３０〜３８０℃における線膨張係数の差が、１０×１０−7／Ｋ 以下である非晶質ガラスをアルミナ質のロールクラッシャーにて２〜７ｍｍに粉砕し、ガラス小体Ｂを得た。 First, an amorphous glass having a difference in linear expansion coefficient at 30 to 380 ° C. with crystallized glass of 10 × 10 −7 / K or less is pulverized to 2 to 7 mm with an alumina roll crusher, Body B was obtained.
次に、このガラス小体Ｂを厚みで３〜５ｍｍになるように重量を秤量し、アルミナペーパーが設置されたムライト製の型枠１１内に集積した後、９３０〜９５０℃で焼成し、板状の非晶質ガラスを作った。それをハンマーにて粉砕して外接円直径ｄが約３０〜１００ｍｍの透光性ガラスのフレークＣを作った。 Next, the glass body B is weighed so as to have a thickness of 3 to 5 mm, and is accumulated in the mullite mold 11 provided with alumina paper, and then fired at 930 to 950 ° C. Amorphous glass was made. This was pulverized with a hammer to make a translucent glass flake C having a circumscribed circle diameter d of about 30 to 100 mm.
次に、質量でＳｉＯ２ ６１．４％、Ａｌ２Ｏ３ ６．４％、ＣａＯ １６．４％、ＺｎＯ ５．７％、 ＢａＯ ４％、Ｎａ２Ｏ ３．３％、Ｋ２Ｏ １．９％、Ｓｂ２Ｏ３ ０．１％からなり、直径１〜５ｍｍの結晶性ガラス小体Ａを、図４（ａ）に示すように、その焼成後の厚さが１５ｍｍになるように秤量し、ムライト製の型枠１１内に集積し、表面を平にした。 Next, SiO 2 61.4% by weight, Al 2 O 3 6.4%, CaO 16.4%, 5.7% ZnO, BaO 4%, Na 2 O 3.3%, K 2 O 1. 9% and Sb 2 O 3 0.1%, and the crystalline glass body A having a diameter of 1 to 5 mm is weighed so that the thickness after firing is 15 mm as shown in FIG. Then, they were accumulated in a mold 11 made of mullite and the surface was flattened.
次に、集積された結晶性ガラス小体Ａの上に、非晶質ガラスのフレークＣを意匠面となる表面と平行に分散設置して１０９０℃で２時間熱処理した。 Next, the amorphous glass flakes C were dispersed and placed on the collected crystalline glass bodies A in parallel with the surface to be the design surface, and heat-treated at 1090 ° C. for 2 hours.
その結果、結晶性ガラス及び非晶質ガラスのそれぞれが互いに軟化融着し、部分的に深みのある大柄な模様の結晶化ガラス物品２０が得られた。 As a result, each of the crystalline glass and the amorphous glass was softened and fused to each other, and a crystallized glass article 20 having a large pattern with a partial depth was obtained.
その他の実施例として、図４（ｂ）に示すように、集積された結晶性ガラス小体Ａの内部に、非晶質ガラスのフレークＣを意匠面となる表面と平行に分散設置してもよく、また、図４（ｃ）に示すように、曲げ強度が低下しない範囲で、結晶性ガラス小体Ａと透光性ガラス小体Ｂの混合物の上に、フレークＣを平行に分散設置して大柄模様の結晶化ガラス物品を作製してもよい。 As another example, as shown in FIG. 4 (b), the amorphous glass flakes C may be distributed in parallel with the surface to be the design surface inside the collected crystalline glass bodies A. Well, as shown in FIG. 4 (c), the flakes C are distributed in parallel on the mixture of the crystalline glass body A and the translucent glass body B as long as the bending strength does not decrease. A crystallized glass article having a large pattern may be produced.
上記の平均線膨張係数はブルカー・エイエックスエス株式会社製 ディラトメータにて測定を行った。模様入り結晶化ガラス物品の結晶化ガラスと透光性非晶質ガラスの粘度が１０４Ｐａ・ｓとなる温度は、結晶化ガラス物品を粉砕して結晶化ガラスの破片と透光部の破片に分別し、直径８ｍｍφ×厚さ６ｍｍの円板形状に加工した各試料を作製し、モトヤマ製の平行板式粘度計にて試料の上に１ｍｍφの白金球を置き、１００ｇの荷重をかけて測定した。また、製造工程管理上、結晶性ガラス小体と透光性ガラス小体を使用して各試料を作製し、粘度が１０４Ｐａ・ｓとなる温度を測定した。透光領域の波長３８０〜７８０ｎｍの範囲における可視光の平均透過率は、透光領域を中心にして光学研磨された２０×２０×１ｍｍの試料を作製し、株式会社島津製作所製 分光光度計 ＵＶ２５００ＰＣで測定した。４点支持曲げ強度は、ＡＳＴＭ Ｃ１５８−２００７に基づき島津製作所社製オートグラフにより測定した。 The average linear expansion coefficient was measured with a dilatometer manufactured by Bruker AXS. The temperature at which the crystallized glass and the translucent amorphous glass of the patterned crystallized glass article have a viscosity of 10 4 Pa · s is obtained by crushing the crystallized glass article to break the crystallized glass and the translucent part. Each sample was processed into a disk shape with a diameter of 8 mmφ x thickness of 6 mm, and a 1 mmφ platinum ball was placed on the sample with a parallel plate viscometer made by Motoyama, and a load of 100 g was measured. did. For manufacturing process control, each sample was prepared using a crystalline glass body and a light-transmitting glass body, and the temperature at which the viscosity was 10 4 Pa · s was measured. The average transmittance of visible light in the wavelength range of 380 to 780 nm of the translucent region is a 20 × 20 × 1 mm sample optically polished around the translucent region, and a spectrophotometer UV2500PC manufactured by Shimadzu Corporation. Measured with The 4-point support bending strength was measured by an autograph manufactured by Shimadzu Corporation based on ASTM C158-2007.
本発明によれば、従来よりも透光性に富み、かつ実用強度、外観として高級感のある新規な模様入り結晶化ガラス物品とその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the crystallized glass article with a new pattern which is rich in translucency compared with the past, and has a high-grade feeling as practical strength and an external appearance, and its manufacturing method can be provided.
１０、２０ 模様入り結晶化ガラス物品
１０ａ、２０ａ 結晶化ガラス部位
１０ｂ、２０ｂ 透光性領域
１１ 型枠（耐火性容器）
Ａ 結晶性ガラス小体
Ｂ 非晶質ガラスのガラス小体
Ｃ 非晶質ガラスのフレーク
ｄ 透光領域の外接円直径
10, 20 Patterned crystallized glass articles 10a, 20a Crystallized glass parts 10b, 20b Translucent region 11 Formwork (fireproof container)
A Crystalline glass body B Glass body of amorphous glass C Flakes of amorphous glass d Diameter of circumscribed circle of translucent region
Claims (11)
前記結晶化ガラスの粘度が１０４Ｐａ・ｓとなる温度と、前記非晶質ガラスが前記粘度と同一となる温度との温度差が１００℃以内であり、かつ前記透光領域の厚さ１ｍｍにおける可視光平均透過率が１０％以上であることを特徴とする模様入り結晶化ガラス物品。 A plurality of translucent regions made of translucent amorphous glass are embedded in a molded body in which a plurality of crystallized glass subregions with acicular crystals deposited from the surface toward the inside are fused together. A crystallized glass article with a pattern,
The temperature difference between the temperature at which the crystallized glass has a viscosity of 10 4 Pa · s and the temperature at which the amorphous glass becomes the same as the viscosity is within 100 ° C., and the thickness of the translucent region is 1 mm. A patterned crystallized glass article characterized by having an average visible light transmittance of 10% or more.
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