JP2009173514A - Colored glass article for building and method for manufacturing the same - Google Patents
Colored glass article for building and method for manufacturing the same Download PDFInfo
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本発明は、建築用の着色ガラス物品及びその製造方法に関するものである。 The present invention relates to a colored glass article for construction and a method for producing the same.
ガラスレンガは、化学的耐久性、機械的強度等の特性に優れており、また石材、人工石材の人研、陶板、タイル、着色ガラス等とは異なる新しい独特の外観を呈するデザインを追及する各種の提案がなされている。 Glass bricks are excellent in chemical durability, mechanical strength and other properties, and are designed to pursue a new and unique design that is different from stones, artificial stones, ceramic plates, tiles, colored glass, etc. Proposals have been made.
耐火性容器内に複数個のガラス粒を充填し、熱処理して融着一体化する、いわゆる集積法によって作製された建築用のガラスレンガは、耐火性容器と接触する面が粗面となり、また、ガラスレンガの中に多くの気泡を含有し、透光不透視となるため、焼成クレーレンガや中空ガラスブロックとは異なった意匠性を有する。そのため、このガラスレンガは、その透光性を利用して床や壁の躯体に固定し、ガラスレンガと躯体との間に光源（照明）を設置して誘導灯、歩道灯、足元灯の面材として使用されてきた。 A glass brick for construction made by the so-called integration method, in which a plurality of glass particles are filled in a refractory container and fused and integrated by heat treatment, the surface in contact with the refractory container becomes rough, Since many bubbles are contained in the glass brick and it becomes non-translucent see-through, it has a design that is different from the fired clay brick and the hollow glass block. For this reason, this glass brick is fixed to the floor or wall frame using its translucency, and a light source (lighting) is installed between the glass brick and the frame to provide a surface material for guide lights, sidewalk lights, and foot lamps. Has been used as.
また、装飾性を向上させるため、従来の着色ガラスレンガは、複数個のガラス小体と着色剤及びバインダーを混合撹拌して複数個の着色剤付ガラス小体を作製し、耐火容器内に、複数個の着色剤付ガラス小体を集積し、耐火容器内の着色剤付ガラス小体を熱処理して互いに焼結させることで製造されている。 Moreover, in order to improve decorativeness, the conventional colored glass bricks are prepared by mixing and stirring a plurality of glass bodies, a colorant and a binder to produce a plurality of glass bodies with a colorant, It is manufactured by accumulating a plurality of glass bodies with a colorant, and heat-treating the glass bodies with a colorant in a refractory container and sintering them.
また、装飾性を向上させたガラス建材として、例えば、特許文献１〜４に、着色ガラスを使用した建築用着色ガラス物品等が提案されている。
しかしながら、図２に写真で示すように、従来の白色の着色剤で着色した建築用着色ガラスレンガ１は、複数個のガラス小体と着色剤及びバインダーを混合撹拌して複数個の着色剤付ガラス小体を作製する混合工程があるため、生産の効率が悪く、また、着色剤付ガラス小体の焼成時に着色剤が軟化したガラス小体の流動に影響してガラス小体の輪郭を浮き上がらせてガラスレンガ１の外観を見苦しくし、場合によっては焼成時にガラスの流動を阻害してガラスレンガ１の意匠面の平滑性が低下することがあった。また、ガラス小体に青色の着色剤を付着させて着色したガラスレンガ２は、着色剤により透光性が優れず、全体が濁ったような外観を呈するものである。 However, as shown in the photograph in FIG. 2, the architectural colored glass brick 1 colored with a conventional white colorant is mixed with a plurality of glass bodies, a colorant and a binder, and a plurality of colorants are attached. Since there is a mixing process to make the glass body, the production efficiency is poor, and when the glass body with colorant is baked, the outline of the glass body is raised by affecting the flow of the glass body with the softened colorant. In some cases, the appearance of the glass brick 1 is unsightly, and in some cases, the flow of the glass is inhibited during firing, and the smoothness of the design surface of the glass brick 1 may be lowered. Moreover, the glass brick 2 colored by attaching a blue colorant to a glass body exhibits an appearance that the whole color is not turbid due to the colorant and the whole is cloudy.
本発明は上記事情に着目し、ガラス原料を調合する際に金属酸化物を添加することで、あらかじめガラス生地が着色されたガラス小体を使用して焼成することにより成型することで、新たな外観を呈する建築用着色ガラス物品と、ガラス小体の焼成の際に軟化したガラスに流動性の問題が生じない建築用着色ガラス物品の製造方法を提供することにある。 The present invention pays attention to the above circumstances, and by adding a metal oxide when preparing a glass raw material, it is molded by firing by using a glass body in which a glass dough is colored in advance. An object of the present invention is to provide a method for producing an architectural colored glass article that exhibits an appearance and an architectural colored glass article that does not cause a fluidity problem in glass that has been softened during firing of the glass body.
本発明に係る本発明の建築用着色ガラス物品は、内部に、クリストバライトの結晶を生じて、多数の薄片状模様を形成してなることを特徴とする。 The colored glass article for building of the present invention according to the present invention is characterized in that a crystal of cristobalite is produced inside to form a large number of flaky patterns.
本発明で、内部にクリストバライトの結晶の薄片状模様を形成する結晶成長の核になる着色剤としては、ＮｉＯ、ＣｏＯ又はＣｕＯが使用可能である。 In the present invention, NiO, CoO, or CuO can be used as a colorant that becomes the nucleus of crystal growth that forms a flaky pattern of cristobalite crystals inside.
また、本発明の建築用着色ガラス物品は、ガラス生地がＮｉＯ、ＣｏＯ及びＣｕＯのうち一種以上の金属酸化物着色剤により着色された透光性の生地着色ガラス小体と、前記着色剤により着色しない未着色ガラス小体とを混合したガラス小体混合物が焼結一体化されたガラス焼結体よりなることを特徴とする。 Moreover, the colored glass article for building of the present invention is colored with a translucent fabric-colored glass body in which a glass fabric is colored with one or more metal oxide colorants among NiO, CoO and CuO, and the colorant. It is characterized by comprising a glass sintered body in which a glass body mixture obtained by mixing uncolored glass bodies that are not formed is sintered and integrated.
本発明では、ガラス生地がＮｉＯ、ＣｏＯ及びＣｕＯのうち一種以上の金属酸化物着色剤により着色された透光性の生地着色ガラス小体と、前記着色剤により着色しない未着色ガラス小体とを混合したガラス小体混合物を焼結一体化する熱処理工程においてＮｉＯ、ＣｏＯ又はＣｕＯを核としてクリストバライトの結晶が析出し、薄片状模様を形成してなるものである。また薄片状模様は、葉状、鱗片状、フレーク状、平らな花弁状とも表現できるものである。 In the present invention, the glass fabric is a translucent fabric-colored glass body colored with one or more metal oxide colorants of NiO, CoO, and CuO, and an uncolored glass body that is not colored by the colorant. In the heat treatment step of sintering and integrating the mixed glass body mixture, cristobalite crystals are precipitated with NiO, CoO or CuO as nuclei to form a flaky pattern. The flaky pattern can be expressed as a leaf shape, a scale shape, a flake shape, or a flat petal shape.
また、本発明の建築用着色ガラス物品は、金属酸化物着色剤として、ＮｉＯ、ＣｏＯ又はＣｕＯの添加量がガラス物品の質量比で０．０１％〜５％程度であることが、上記の色彩模様を呈し、かつガラス小体を焼成する際に軟化したガラスの良好な流動性を確保する上で好ましい。また、他の酸化物着色剤と組み合わせて用いると、多様な彩色が可能となる。 Moreover, the colored glass article for construction of the present invention has the above-described color that the addition amount of NiO, CoO or CuO as the metal oxide colorant is about 0.01% to 5% by mass ratio of the glass article. It is preferable for ensuring good fluidity of the glass that has a pattern and is softened when the glass body is fired. In addition, when used in combination with other oxide colorants, various colors can be achieved.
また、建築用着色ガラス物品を構成する透光性のガラス小体が、焼成後に、波長４００ｎｍ〜７００ｎｍの範囲において、肉厚７ｍｍで平均透過率が１５％より低いと、光源からの光がほとんど透過しないため、暗所における意匠面としては殆ど目立たないものとなり、例えば、誘導灯、歩道灯、又は足元灯等の機能を果たし難くなる。一方、平均透過率が８５％を超えると、施工した際、構造材が透けて見えるので、外観及びプライバシー保護性の点で好ましくなく、あるいは反対側の光源からの光が直接目に入り好ましくない。本発明の建築用着色ガラス物品としては、焼成後に、波長４００ｎｍ〜７００ｎｍの範囲において、肉厚７ｍｍで平均透過率が１５％〜８５％となる透光性のガラス小体を使用してガラス焼結体を作製することで、ガラス物品の内部で光が散乱し、意匠面からは目にやさしい散乱光が放射されることになり好ましい。 Moreover, when the light-transmitting glass body constituting the colored glass article for building has a thickness of 7 mm and an average transmittance lower than 15% in the wavelength range of 400 nm to 700 nm after firing, most of the light from the light source is present. Since it does not transmit, it becomes almost inconspicuous as a design surface in a dark place, and for example, it becomes difficult to perform functions such as a guide light, a sidewalk light, or a foot lamp. On the other hand, if the average transmittance exceeds 85%, the construction material can be seen through when constructed, which is not preferable in terms of appearance and privacy protection, or light from the light source on the opposite side is not directly in the eyes. . As the colored glass article for building of the present invention, after firing, glass baked using a translucent glass body having a thickness of 7 mm and an average transmittance of 15% to 85% in a wavelength range of 400 nm to 700 nm. By producing a bonded body, light is scattered inside the glass article, and scattered light that is kind to the eyes is emitted from the design surface.
また、本発明の建築用着色ガラス物品は、建築物の床面に使用する場合、意匠面が凹凸状であると、雨で濡れても滑りにくく、正反射率が２％以下であると、柔らかな光が放射され目にやさしいため好ましい。 Moreover, when the colored glass article for building of the present invention is used for a floor surface of a building, if the design surface is uneven, it is difficult to slip even when wet with rain, and the regular reflectance is 2% or less. Since soft light is emitted and is easy on the eyes, it is preferable.
また、本発明の建築用着色ガラス物品は、ガラスが、ソーダ石灰ガラス、ホウケイ酸ガラス（Ｂ2Ｏ3−ＳｉＯ2系ガラス）、アルミノケイ酸ガラス（Ａｌ2Ｏ3−ＳｉＯ2系ガラス）およびアルミノホウケイ酸ガラス（Ｂ2Ｏ3−Ａｌ2Ｏ3−ＳｉＯ2系ガラス）からなる群より選択される一種または二種以上のガラスからなるものであり、熱衝撃に強く、耐薬品性に優れているため、熱処理工程における冷却時の熱衝撃や、激しい気候変化による寒暖差に起因する熱衝撃でも破損することがなく、耐候性に優れている点でホウケイ酸ガラス、アルミノケイ酸ガラス、あるいはアルミノホウケイ酸ガラスからなることが好ましい。 In the colored glass article for building of the present invention, the glass is soda-lime glass, borosilicate glass (B 2 O 3 —SiO 2 glass), aluminosilicate glass (Al 2 O 3 —SiO 2 glass) and alumino. It is made of one or two or more kinds of glass selected from the group consisting of borosilicate glass (B 2 O 3 —Al 2 O 3 —SiO 2 glass), and is resistant to thermal shock and excellent in chemical resistance. Therefore, borosilicate glass, aluminosilicate glass, or aluminoborosilicate is not damaged by thermal shock during cooling in the heat treatment process or thermal shock caused by temperature difference due to severe climate change, and is excellent in weather resistance. It is preferable to consist of acid glass.
また、本発明の建築用着色ガラス物品は、ガラスに１０2〜１０12個／ｋｇの気泡を有していると、波長４００ｎｍ〜７００ｎｍの範囲において、肉厚７ｍｍで平均透過率が１５％〜８５％になるため好ましい。すなわち、ガラス物品内部の気泡が、光入射面からガラス物品に入射した光を反射あるいは散乱するため、気泡の量によって平均透過率を調整できるからである。また、本発明の建築用着色ガラス物品は、１ｋｇあたり１０2個〜１０12個の気泡を含有するものであると透光不透視となるため、透光性を有しながら人物や物体を明瞭に視認することができないという、いわゆるプライバシー保護性が得られやすいとともに、本発明の建築用着色ガラス物品からなるガラスレンガ構築体の背面側に光源を設置した場合、光源からの光がガラスレンガ中の気泡によって散乱されて、意匠面側からあたかもガラスレンガ自体が発光しているように見えるため意匠的に好ましい。気泡の数が１ｋｇあたり１００個よりも少ないガラスからなると上記した効果が得られにくく、１ｋｇあたり１０12個よりも多いガラスからなると、肉厚７ｍｍで可視光線の平均透過率が１５％よりも低くなりやすいとともに機械的強度が損なわれやすい。なお、気泡とは０．０１ｍｍ以上の直径を有するものを指す。 Moreover, when the colored glass article for construction of the present invention has 10 2 to 10 12 bubbles / kg in the glass, the average transmittance is 15% with a thickness of 7 mm in the wavelength range of 400 nm to 700 nm. It is preferable because it is 85%. That is, because the bubbles inside the glass article reflect or scatter light incident on the glass article from the light incident surface, the average transmittance can be adjusted by the amount of bubbles. Moreover, since the colored glass article for construction of the present invention contains 10 2 to 10 12 bubbles per 1 kg, it becomes transparent, so that a person or an object can be clearly seen while having translucency. When the light source is installed on the back side of the glass brick construction made of the colored glass article for building of the present invention, the light from the light source is contained in the glass brick. Since the glass brick itself appears to emit light from the design surface side, it is preferable in terms of design. The effect mentioned above is difficult to obtain if the number of bubbles is less than 100 per kg. If the glass is more than 10 12 per kg, the average visible light transmittance is less than 15% at a thickness of 7 mm. And mechanical strength is likely to be impaired. In addition, a bubble refers to what has a diameter of 0.01 mm or more.
また、本発明の建築用着色ガラス物品は、波長４００ｎｍ〜７００ｎｍの範囲において、肉厚７ｍｍで平均透過率が１５％〜８５％になればよい。なお、平均透過率の好ましい範囲は３０％〜８０％、さらに好ましくは４０％〜６５％である。 Moreover, the colored glass article for construction of this invention should just become an average transmittance | permeability 15%-85% by thickness 7mm in the wavelength range of 400 nm-700 nm. In addition, the preferable range of average transmittance is 30% to 80%, more preferably 40% to 65%.
また本発明の建築用着色ガラス物品は、ガラスの質量に対して０．１質量％から１０質量％の発光材を含有する部位を形成してなることを特徴とする。本発明で、発光材の含有量がガラスの質量に対して０．１質量％未満であると、発光現象を殆ど観察することができない。一方、発光材の含有量が１０質量％を超えると、熱処理工程においてガラス小体が十分に流動しないので、平滑な表面を得ることが困難になる。好ましくは、意匠面側に、ガラス質量に対して発光材の含有量が１質量％から５質量％の部位を設けてなることで、十分な発光性能を有する建築用着色ガラス物品を得ることができる。 Moreover, the colored glass article for construction of the present invention is characterized by forming a part containing 0.1 to 10% by mass of a light emitting material with respect to the mass of the glass. In the present invention, when the content of the luminescent material is less than 0.1% by mass with respect to the mass of the glass, almost no light emission phenomenon can be observed. On the other hand, if the content of the luminescent material exceeds 10% by mass, the glass bodies do not flow sufficiently in the heat treatment step, and it becomes difficult to obtain a smooth surface. Preferably, a colored glass article for construction having sufficient light emission performance can be obtained by providing a portion having a light emitting material content of 1% by mass to 5% by mass with respect to the glass mass on the design surface side. it can.
本発明で発光材としては、１０００℃前後の焼成温度でも発光性を失わなければ使用可能であり、ＳｒＡｌ2Ｏ4にＥｕ2+、Ｄｙ3+をドープした蓄光材やＺｎＳにＣｕ+、Ａｌ3+をドープした蛍光材などが適している。 As the light emitting material in the present invention, it can be used as long as the light emitting property is not lost even at a firing temperature of about 1000 ° C., and is a phosphorescent material doped with Eu 2+ and Dy 3+ in SrAl 2 O 4 or Cu + , Al in ZnS. A fluorescent material doped with 3+ is suitable.
また、本発明の建築用着色ガラス物品は、発光材が蓄光材を含むものであることを特徴とする。現在、入手可能な蓄光材は、焼成時に外気により酸化すると発光能力が経時的に低下し、かつ、焼成後においても外気との酸化や水分との接触により、発光能力が低下する。そこで、本発明では、予め蓄光材を透光性ガラスで覆って酸化を抑制した、すなわち蓄光材をガラス封止したガラス小体を使用すると、焼成後の建築用着色ガラス物品で半永久的に安定した発光が可能となる。この蓄光材を封じたガラス小体とは、蓄光材とガラス片とが焼結された後、破砕されるなどして発光材が融着されたガラス小体内に密封されたもの、または蓄光材が融着されたガラス小体に付着して部分的に埋設されもの等のガラス小体を意味している。このような蓄光材を封じたガラス小体を使用した場合には、ガラス小体に発光性物質を直接分散させて作製したものとは外観が異なり、建築用着色ガラス物品の意匠面に奥行き感を有する模様が観察される状態となる。また、優れた耐候性により、ガラス焼結体の外面に、蓄光材をガラス封止したガラス小体を配置しても、蓄光材を建築用着色ガラス物品内部に均一に分散した従来のものに比べて遜色のない表面の発光能力を得ることができる。 Moreover, the colored glass article for construction of the present invention is characterized in that the luminescent material includes a phosphorescent material. Currently available phosphorescent materials, when oxidized by the outside air at the time of firing, the light emitting ability decreases with time, and even after firing, the light emitting ability is lowered by oxidation with the outside air and contact with moisture. Therefore, in the present invention, the phosphorescent material is previously covered with translucent glass to prevent oxidation, that is, when a glass body in which the phosphorescent material is glass-sealed is used, it is semi-permanently stable in the architectural colored glass article after firing. Light emission is possible. The glass body in which the phosphorescent material is sealed is one in which the phosphorescent material and the glass piece are sintered and then sealed, for example, in a glass body in which the light emitting material is fused, or the phosphorescent material. Means a glass body such as one that is attached and partially embedded in the fused glass body. When a glass body with such a phosphorescent material is used, the appearance is different from that produced by directly dispersing a luminescent material in the glass body, and the design surface of colored glass articles for construction has a sense of depth. A pattern having a mark is observed. In addition, due to excellent weather resistance, even if a glass body that is glass-sealed with a phosphorescent material is placed on the outer surface of the sintered glass body, the phosphorescent material is uniformly dispersed inside the colored glass article for construction. Compared with the surface, it is possible to obtain a light emitting ability that is comparable to that of the surface.
また、本発明の建築用着色ガラス物品の蓄光材を含む部位の発光性能としては、１０００ルクスの光を２０分間照射した直後の初期発光強度が２００〜４０００ｍｃｄ／ｍ2であり、照射停止１０分後の発光強度が、初期発光強度の１０％以上であることが好ましい。 Moreover, as a light emission performance of the site | part containing the phosphorescent material of the colored glass article for construction of this invention, the initial light emission intensity immediately after irradiating 1000 lux light for 20 minutes is 200-4000 mcd / m < 2 >, and irradiation stop for 10 minutes The subsequent emission intensity is preferably 10% or more of the initial emission intensity.
本発明に係る建築用着色ガラス物品の製造方法は、ＮｉＯ、ＣｏＯ及びＣｕＯのうち一種以上の金属酸化物着色剤を添加したガラス原料を溶融し、得られたガラス固化体を粉砕して透光性の生地着色ガラス小体を得る着色ガラス小体形成工程と、前記着色剤が無添加のガラス原料を溶融し、得られたガラス固化体を粉砕して透光性の未着色ガラス小体を得る未着色ガラス小体形成工程と、複数個の生地着色ガラス小体と未着色ガラス小体とを混合してガラス小体混合物を得る混合工程と、該ガラス小体混合物を耐火容器内に集積してガラス集積層を形成する集積工程と、該ガラス集積層を焼成することによりガラス焼結体を得る焼成工程とを有することを特徴とする。 According to the present invention, there is provided a method for manufacturing a colored glass article for building, wherein a glass raw material to which at least one metal oxide colorant is added among NiO, CoO, and CuO is melted, and the obtained glass solidified material is pulverized to transmit light. A colored glass body forming step for obtaining a dough-colored colored glass body, melting a glass raw material to which the colorant is not added, pulverizing the obtained glass solidified body, and translucent uncolored glass body An uncolored glass body forming step to be obtained, a mixing step of mixing a plurality of dough-colored glass bodies and uncolored glass bodies to obtain a glass body mixture, and collecting the glass body mixture in a fireproof container And an accumulation step for forming a glass accumulation layer, and a firing step for obtaining a glass sintered body by firing the glass accumulation layer.
本発明の建築用着色ガラス物品の製造方法で、着色ガラス小体形成工程は、ＮｉＯ、ＣｏＯ及びＣｕＯ等の金属酸化物よりなる着色剤のうち一種以上をガラス原料に添加し、そのガラス原料を加熱・溶融することで溶融ガラスとし、この溶融ガラスを適宜の形状寸法に固化させ、水砕その他の粉砕手段により粉砕して、粒状または鱗片状等の所望する形状とし、必要ならば篩いで分級して透光性の生地着色ガラス小体を得るものである。また、未着色ガラス小体形成工程は、前記着色剤が無添加のガラス原料を使用し、３０℃〜３８０℃における平均線膨張係数が７０×１０-7／Ｋ以下で、ガラス焼結体が波長４００ｎｍ〜７００ｎｍの範囲において、肉厚７ｍｍで平均透過率が１５％〜８５％になる未着色ガラス小体が得られるものであればよい。 In the manufacturing method of colored glass articles for building of the present invention, the colored glass body forming step includes adding one or more colorants made of metal oxides such as NiO, CoO and CuO to the glass raw material, Heat and melt to form molten glass, solidify the molten glass into an appropriate shape and size, and crush it with water or other pulverizing means to obtain the desired shape such as granular or scale-like, and classify with a sieve if necessary. Thus, a light-transmitting dough-colored glass body is obtained. In the uncolored glass body forming step, a glass raw material to which the colorant is not added is used, the average linear expansion coefficient at 30 ° C. to 380 ° C. is 70 × 10 −7 / K or less, and the glass sintered body is Any uncolored glass body having a thickness of 7 mm and an average transmittance of 15% to 85% in the wavelength range of 400 nm to 700 nm may be used.
本発明の建築用着色ガラス物品の製造方法で、透光ガラス集積層を形成するための耐火容器としては、１２００℃以下の温度で軟化変形しない材質が好ましく、ムライト、コージエライト、アルミナセラミックス製等の耐火性容器が好適である。また、耐火性セラミックスシートを使用する場合、ガラスレンガと耐火性容器との離型材として作用するものであれば何ら制限なく使用できるが、特にシリカ、ムライト、アルミナ等のファイバーシートが好ましく、単独あるいは組み合わせて用いてもよい。また、耐火性セラミックスシートを耐火性容器内に施す方法は、シートを箱型にする方法、シートを分割して容器の内壁に設置する方法があるが、前もって容器の内壁にアルミナ等の微粉末をエアースプレー塗装、刷毛塗装、浸漬塗装等の方法による塗布することが、融着を防止する上で好適である。 In the manufacturing method of colored glass articles for building of the present invention, as a refractory container for forming a translucent glass integrated layer, a material that is not softened and deformed at a temperature of 1200 ° C. or less is preferable, such as mullite, cordierite, and alumina ceramics. A refractory container is preferred. In addition, when using a refractory ceramic sheet, it can be used without any limitation as long as it acts as a release material between the glass brick and the refractory container, but fiber sheets such as silica, mullite, alumina, etc. are particularly preferable, alone or You may use it in combination. In addition, the method of applying the refractory ceramic sheet in the refractory container includes a method of making the sheet into a box shape and a method of dividing the sheet and installing it on the inner wall of the container. It is preferable to apply the coating by a method such as air spray coating, brush coating, or dip coating in order to prevent fusion.
本発明の建築用着色ガラス物品の製造方法では、７００℃〜１１００℃、好ましくは８００℃〜１０００℃で熱処理することがよい。熱処理温度が７００℃より低いと、ガラスの軟化流動が充分に行われず、機械的強度が低くなり、１１００℃を超えると、ガラス焼結体の気泡が少なくなり、可視光の透過率が高くなって、施工時に構造材が透けて見え、また、ガラス小体と離型材との反応性が高くなり、ガラス小体と耐火性容器とが融着しやすくなるため好ましくない。 In the manufacturing method of the colored glass article for building of the present invention, heat treatment is preferably performed at 700 ° C to 1100 ° C, preferably 800 ° C to 1000 ° C. When the heat treatment temperature is lower than 700 ° C., the glass does not sufficiently soften and flow, and the mechanical strength is lowered. When the heat treatment temperature exceeds 1100 ° C., bubbles in the glass sintered body are reduced and the visible light transmittance is increased. In addition, the structural material can be seen through at the time of construction, and the reactivity between the glass body and the release material is increased, and the glass body and the refractory container are easily fused, which is not preferable.
また、本発明の建築用着色ガラス物品の製造方法は、ガラスがリボイルする温度範囲内で熱処理すると、ガラス小体の間隙が残存することによって生じる気泡に加えて、リボイルによりガラス焼結体の内部に新たに気泡が生成されるため好ましい。ガラス内部に溶存していたガスが気泡となってリボイルの現れ始める温度は、ガラスの軟化点よりも約５０℃高い温度である。熱処理温度をさらに上昇させると、それに伴い、ガラス内部での気泡の生成がさらに活発になるが、ガラスの粘度も低下するため、生成した気泡は、次第に大きくなり、浮上してガラスの外部に放出されてしまう。ここでは、ガラスがリボイルする温度範囲とは、ガラス内部に溶存していたガスが気泡となって現れ始めてからガラスの外部に放出されてしまうまでの温度範囲を指し、例えば、Ｂ2Ｏ3−ＳｉＯ2系ガラスでは、約８００℃〜１０００℃となる。 In addition, in the method for producing a colored glass article for building of the present invention, when heat treatment is performed within a temperature range in which the glass is reboiled, in addition to bubbles generated by the gaps in the glass bodies remaining, It is preferable because bubbles are newly generated. The temperature at which the gas dissolved in the glass becomes bubbles and the reboil begins to appear is about 50 ° C. higher than the softening point of the glass. When the heat treatment temperature is further increased, bubbles are generated more actively inside the glass, but the viscosity of the glass also decreases, so the generated bubbles gradually increase, float and release to the outside of the glass. Will be. Here, the temperature range in which the glass reboils refers to the temperature range from when gas dissolved in the glass starts to appear as bubbles until it is released to the outside of the glass. For example, B 2 O 3 − the SiO 2 -based glass is about 800 ° C. to 1000 ° C..
本発明の建築用着色ガラス物品は、内部にクリストバライトの結晶を生じて多数の薄片状模様を形成してなるので、着色された透光性ガラスの内部に多数の薄片状模様が分散配置された過去にない独特の新た意匠を有するガラス建材を提供することができる。 The architectural colored glass article of the present invention is formed by forming cristobalite crystals inside to form a large number of flaky patterns, so that a large number of flaky patterns are dispersedly arranged inside the colored translucent glass. A glass building material having a unique new design that has never existed in the past can be provided.
また、本発明のガラス生地がＮｉＯ、ＣｏＯ及びＣｕＯのうち一種以上の金属酸化物着色剤により着色された透光性の生地着色ガラス小体と、前記着色剤により着色しない未着色ガラス小体とを混合したガラス小体混合物が焼結一体化されたガラス焼結体よりなる建築用着色ガラス物品によれば、着色剤に、ＮｉＯ、ＣｏＯ又はＣｕＯの金属酸化物を使用することで、褐色、青色又は黒色のガラス生地中に白みがかった薄片状模様を呈する建築用着色ガラス物品を得ることができる。 Further, the glass fabric of the present invention is a translucent fabric-colored glass body colored with one or more metal oxide colorants of NiO, CoO, and CuO, and an uncolored glass body that is not colored with the colorant. According to the architectural colored glass article comprising a glass sintered body in which a glass body mixture obtained by mixing is sintered and integrated, by using a metal oxide of NiO, CoO or CuO as a colorant, brown, It is possible to obtain an architectural colored glass article that exhibits a whited flaky pattern in a blue or black glass fabric.
また、本発明の建築用着色ガラス物品は、ガラスの質量に対して０．１質量％から１０質量％の発光材を含有する部位を形成してなるので、暗所において従来に無い奥行き感と色調を備えた発光模様の外観を有する意匠性に富んだ建築用着色ガラス物品を提供することができる。また、発光材が、蓄光材を含むものであると、光源がなくても光る点、光の演出の自由度が広がる点及び発光効率の点で優れた建築用着色ガラス物品となる。 Moreover, since the colored glass article for construction of the present invention forms a part containing 0.1 to 10% by mass of a light emitting material with respect to the mass of the glass, it has an unprecedented depth feeling in a dark place. It is possible to provide an architectural colored glass article having a good design with an appearance of a light emitting pattern having a color tone. In addition, if the light emitting material includes a phosphorescent material, the colored glass article for construction is excellent in that it emits light without a light source, the degree of freedom of light production is widened, and the light emission efficiency.
本発明の建築用着色ガラス物品の製造方法は、ＮｉＯ、ＣｏＯ及びＣｕＯのうち一種以上の金属酸化物着色剤を添加したガラス原料を溶融し、固化体を粉砕して透光性の生地着色ガラス小体を得る着色ガラス小体形成工程と、前記着色剤を添加しないガラス原料を溶融し、固化体を粉砕して透光性の未着色ガラス小体を得る未着色ガラス小体形成工程と、複数個の生地着色ガラス小体と未着色ガラス小体とを混合してガラス小体混合物を得る混合工程と、該ガラス小体混合物を耐火容器内に集積してガラス集積層を形成する集積工程と、該ガラス集積層を焼成することによりガラス焼結体を得る焼成工程とを有するので、独特の新た意匠を有する上記本発明の建築用着色ガラス物品を製造することができる。また、ガラス小体の焼成時に着色剤がガラスの流動に悪影響を及ぼすこともないので、ガラス焼結体を構成するガラス小体の輪郭を浮き上がらせて外観を見苦しくすることがなく、またガラスの流動を阻害しないので、平滑性に優れた建築用着色ガラス物品を効率よく製造することが可能になる。 The method for producing a colored glass article for building according to the present invention includes a glass raw material to which one or more metal oxide colorants of NiO, CoO, and CuO are added, and a solidified body is pulverized to obtain a translucent dough-colored glass. A colored glass body forming step for obtaining a small body, an uncolored glass body forming step for obtaining a translucent uncolored glass body by melting a glass raw material to which the colorant is not added, and crushing the solidified body; A mixing step of mixing a plurality of dough-colored glass bodies and uncolored glass bodies to obtain a glass body mixture, and an accumulation step of accumulating the glass body mixture in a refractory container to form a glass accumulation layer. And a firing step of obtaining a glass sintered body by firing the glass integrated layer, the colored glass article for building of the present invention having a unique new design can be produced. In addition, since the colorant does not adversely affect the flow of the glass when the glass body is fired, the outline of the glass body constituting the glass sintered body is not lifted and the appearance of the glass body is not obscure. Since the flow is not hindered, it is possible to efficiently produce an architectural colored glass article having excellent smoothness.
以下、実施例及び比較例に基づいて本発明の実施形態を説明する。 Hereinafter, embodiments of the present invention will be described based on examples and comparative examples.
本実施例に係る建築用着色ガラス物品として、模様入り着色ガラスレンガ１０は、図１の写真に示すように、２００ｍｍ×１００ｍｍ×１５０ｍｍの寸法を有し、黒色に着色された透光性ガラスの内部にクリストバライトの結晶析出による失透が局所的に現れて多数の薄片状模様１１が分散して配置された従来に無い独特の外観を呈する建築用着色ガラス物品である。模様入り着色ガラスレンガ１０は、質量％表示で、ＳｉＯ2 ７０．２％、Ａｌ2Ｏ3 ５．４％、Ｂ2Ｏ3 １３．５％、ＣａＯ ０．５％、ＢａＯ １．５％、Ｎａ2Ｏ ６．７％、Ｋ2Ｏ ２．２％の組成を有するように調合したガラス原料に対して、質量比でＮｉＯを１．０％、ＣｏＯを０．１５％添加して溶融し、得られた生地着色ガラス小体と、ＮｉＯ及びＣｏＯを添加しない未着色ガラス小体とを混合したガラス小体混合体が焼結一体化されたガラス焼結体よりなるものである。 As a colored glass article for building according to the present example, a colored glass brick 10 with a pattern has a size of 200 mm × 100 mm × 150 mm and is a transparent glass colored black as shown in the photograph of FIG. This is a colored glass article for construction that exhibits an unprecedented unique appearance in which devitrification due to crystal precipitation of cristobalite appears locally and a large number of flaky patterns 11 are dispersed. The patterned colored glass brick 10 is expressed in terms of mass%, SiO 2 70.2%, Al 2 O 3 5.4%, B 2 O 3 13.5%, CaO 0.5%, BaO 1.5%, A glass raw material prepared to have a composition of Na 2 O 6.7% and K 2 O 2.2% was melted by adding 1.0% NiO and 0.15% CoO by mass ratio. The glass body mixture obtained by mixing the obtained dough-colored glass body and the uncolored glass body to which NiO and CoO are not added is formed by sintering and integrating the glass body.
また、模様入り着色ガラスレンガ１０は内部に気泡を約５×１０4個／ｋｇの割合で有しているため、肉厚が７ｍｍで波長４００〜７００ｎｍの範囲における平均透過率が３０％のガラス焼結体からなり、図１に示すような外観を呈するものである。また、模様入り着色ガラスレンガ１０は、３０℃〜３８０℃における平均線膨張係数が５５×１０-7／Ｋであり、熱衝撃に強く、かつ耐薬品性に優れているものでもある。また、厚さ１００ｍｍ前後の実際の模様入り着色ガラスレンガ１０での平均透過率は数％程度になるので、構造材が透けて見えることがなく、プライバシー保護性にも優れ意匠的に好ましい。 Further, the patterned colored glass brick 10 has bubbles inside at a rate of about 5 × 10 4 / kg, so that the glass has a thickness of 7 mm and an average transmittance of 30% in the wavelength range of 400 to 700 nm. It consists of a sintered body and exhibits an appearance as shown in FIG. The patterned colored glass brick 10 has an average coefficient of linear expansion of 55 × 10 −7 / K at 30 ° C. to 380 ° C., is strong against thermal shock, and has excellent chemical resistance. In addition, since the average transmittance of the actual patterned colored glass brick 10 having a thickness of about 100 mm is about several percent, the structural material is not seen through, and it is excellent in privacy protection and is preferable in design.
これに対して、比較例として、透光性のガラス小体に、後から珪酸ジルコニウム及びバインダーを添加して混合撹拌して複数個の着色剤付ガラス小体を作製し、耐火容器内に、複数個の着色剤付ガラス小体を集積して焼結一体化した図２に示す建築用ガラスレンガ１は、焼成時にガラスの一部に流動不足を生じた痕跡がある外観を呈している。 On the other hand, as a comparative example, to the light-transmitting glass body, after adding zirconium silicate and a binder and mixing and stirring to produce a plurality of glass bodies with colorants, in a refractory container, The building glass brick 1 shown in FIG. 2 in which a plurality of glass bodies with colorants are integrated and integrated by sintering has an appearance with traces of insufficient flow in a part of the glass during firing.
次に、本発明の模様入り着色ガラスレンガ１０を製造する方法を説明する。 Next, a method for producing the patterned colored glass brick 10 of the present invention will be described.
上記本発明の模様入り着色ガラスレンガ１０を製造する場合、まず、質量％で、ＳｉＯ2 ７０．２％、Ａｌ2Ｏ3 ５．４％、Ｂ2Ｏ3 １３．５％、ＣａＯ ０．５％、ＢａＯ １．５％、Ｎａ2Ｏ ６．７％、Ｋ2Ｏ ２．２％の組成を有するようにガラス原料を調合し、着色剤としてガラス質量に対し質量比でＮｉＯを１．０％、ＣｏＯを０．１５％となるように添加してガラス原料とし、加熱溶融した溶融ガラスを板状に成形した後、粉砕、分級等により最大３０ｍｍで薄片状の透光性の生地着色ガラス小体を作製する。また、ＳｉＯ2 ７０．２％、Ａｌ2Ｏ3 ５．４％、Ｂ2Ｏ3 １３．５％、ＣａＯ ０．５％、ＢａＯ １．５％、Ｎａ2Ｏ ６．７％、Ｋ2Ｏ ２．２％の組成を有するようにガラス原料を調合し、加熱溶融した溶融ガラスを板状に成形した後、粉砕、分級等により最大３０ｍｍで薄片状の透光性の未着色ガラス小体を作製する。次に、生地着色ガラス小体と未着色ガラス小体とを混合してガラス小体混合体を作製する。次に内寸が２００ｍｍ×１００ｍｍ×１５０ｍｍのコージエライト製容器の内壁に、アルミナのスラリーを刷毛で塗布し、放置乾燥させた後、ＳｉＯ2 ５２質量％、Ａｌ2Ｏ3 ４２質量％、有機バインダー ６質量％のセラミックファイバーシートを容器の寸法に加工し、容器の内壁面に載置した。次いで、その耐火性容器内に、ガラス小体混合体を積層してガラス集積層とし、９５０℃で５時間熱処理して、１９７ｍｍ×９７ｍｍ×６０ｍｍのブロック状のガラス焼結体からなる模様入り着色ガラスレンガ１０を得た。 When the patterned colored glass brick 10 according to the present invention is manufactured, first, by mass%, SiO 2 70.2%, Al 2 O 3 5.4%, B 2 O 3 13.5%, CaO 0.5 %, BaO 1.5%, Na 2 O 6.7%, K 2 O 2.2%, and a glass raw material is prepared. %, CoO is added to 0.15% to form a glass raw material, and the molten glass melted by heating is formed into a plate shape, and then crushed, classified, etc. to obtain a flaky translucent dough-colored glass having a maximum thickness of 30 mm Create a body. Further, SiO 2 70.2%, Al 2 O 3 5.4%, B 2 O 3 13.5%, CaO 0.5%, BaO 1.5%, Na 2 O 6.7%, K 2 O A glass raw material is prepared so as to have a composition of 2.2%, and molten glass that has been heated and melted is formed into a plate shape. Make it. Next, the dough-colored glass body and the uncolored glass body are mixed to produce a glass body mixture. Next, an alumina slurry was applied to the inner wall of a cordierite container having an inner size of 200 mm × 100 mm × 150 mm with a brush, allowed to dry, and then SiO 2 52 mass%, Al 2 O 3 42 mass%, organic binder 6 A ceramic fiber sheet of mass% was processed into the dimensions of the container and placed on the inner wall surface of the container. Next, a glass body mixture is laminated in the refractory container to form a glass accumulation layer, which is heat-treated at 950 ° C. for 5 hours and patterned with a block-like glass sintered body of 197 mm × 97 mm × 60 mm. Glass brick 10 was obtained.
得られた模様入り着色ガラスレンガ１０は、図１に示すように、黒色のガラス生地の内部に分散状態で一部白色の薄片状模様１１を呈し、かつ光沢のある独特の意匠面１０ａを有する建築用着色ガラス物品となった。なお、裏面１０ｂ及び側面１０ｃは、セラミックファイバーシートとの接触により梨子地面になっている。 The obtained colored glass brick 10 with a pattern, as shown in FIG. 1, exhibits a partially white flaky pattern 11 in a dispersed state inside a black glass fabric, and has a unique design surface 10 a that is glossy. It became a colored glass article for construction. In addition, the back surface 10b and the side surface 10c are pear ground by contact with the ceramic fiber sheet.
次ぎに、実施例２の模様入り着色ガラスレンガについて説明する。まず実施例２の模様入り着色ガラスレンガを作製する場合、模様入り着色ガラスレンガ１０と同様のガラス原料を調合し、着色剤としてガラス質量に対し質量比でＮｉＯを１．０％、ＣｏＯを０．１５％となるように添加してガラス原料とし、加熱溶融した溶融ガラスを板状に成形した後、粉砕、分級等により最大３０ｍｍで薄片状の透光性の生地着色ガラス小体を作製する。また、模様入り着色ガラスレンガ１０と同様の組成を有するようにガラス原料を調合し、加熱溶融した溶融ガラスを板状に成形した後、粉砕、分級等により最大３０ｍｍで薄片状の透光性の未着色ガラス小体を作製する。次に、生地着色ガラス小体と未着色ガラス小体と混合してガラス小体混合体を作製する。これとは別に生地着色ガラス小体と、未着色ガラス小体と、ガラスの質量に対して蓄光材を２．５質量％含む量の発光材として無機質蓄光材（商品名：α‐ＦＬＡＳＨ ＰＧ５００ ＬＴＩ社製）と、バインダーとを混合し、発光材付きガラス小体混合体を作製する。この際、予め蓄光材とガラス片と焼結させた後、破砕して融着されたガラス小体内に蓄光材をガラス封止して密封した発光材付きガラス小体を作製し、使用することが好ましい。次にコージエライト製容器の内壁に、アルミナのスラリーを刷毛で塗布し、放置乾燥させた後、セラミックファイバーシートを容器の寸法に加工し、容器の内壁面に載置した。次いで、その耐火性容器内に、ガラス小体混合体を積層してガラス集積層とし、その上に、発光材付きガラス小体混合体を積層し、さらにその上を該ガラス小体混合体で覆うように充填する。その後、９５０℃で５時間熱処理して、１９７×９７×６０ｍｍのブロック状の内部に発光材も封入された模様入り着色ガラスレンガを得た。この模様入り着色ガラスレンガの意匠面側の内部には、ガラスの質量に対して２．５質量％の蓄光材を含む発光部位が形成されている。 Next, the patterned colored glass brick of Example 2 will be described. First, when preparing the patterned colored glass brick of Example 2, the same glass raw material as the patterned colored glass brick 10 is prepared, and NiO is 1.0% and CoO is 0 by mass ratio with respect to the glass mass as a coloring agent. Add to 15% to make a glass raw material, heat-melted molten glass into a plate shape, then pulverize, classify, etc. to produce a flaky translucent dough-colored glass body with a maximum of 30 mm . Moreover, after preparing a glass raw material so that it may have the same composition as the colored glass brick 10 with a pattern, and shape | molding the molten glass heated and melted in plate shape, it is a translucent of a flaky shape at a maximum of 30 mm by grinding | pulverization, classification, etc. An uncolored glass body is produced. Next, the dough-colored glass body and the uncolored glass body are mixed to produce a glass body mixture. Apart from this, as a luminescent material containing 2.5% by mass of the phosphorescent material relative to the mass of the glass, an inorganic phosphorescent material (trade name: α-FLASH PG500 LTI) A glass body mixture with a luminescent material. At this time, after preliminarily sintering the phosphorescent material and the glass piece, producing and using a glass body with a light emitting material in which the phosphorescent material is sealed in a glass body that has been crushed and fused. Is preferred. Next, the alumina slurry was applied to the inner wall of the cordierite container with a brush and allowed to dry, and then the ceramic fiber sheet was processed into the dimensions of the container and placed on the inner wall surface of the container. Next, a glass body mixture is laminated in the refractory container to form a glass accumulation layer, and a glass body mixture with a light emitting material is laminated thereon, and further on the glass body mixture. Fill to cover. Then, it heat-processed at 950 degreeC for 5 hours, and obtained the colored glass brick with a pattern by which the luminescent material was also enclosed inside the block shape of 197x97x60 mm. A light emitting portion containing 2.5% by mass of a phosphorescent material with respect to the mass of the glass is formed inside the design surface side of the patterned colored glass brick.
本実施例２の模様入り着色ガラスレンガ２は、厚さ１０ｍｍにおいて、透光率が数％であり、１０００ルクスの光を２０分間照射した直後の初期発光強度が５００ｍｃｄ／ｍ2であり、照射停止１０分後の発光強度が、初期発光強度の１０％以上であった。なお、透光率は、５０×５０×１０ｍｍの大きさに切断し両面を光学研磨した板状の試料を作製し、光源である蛍光灯から照度計に直接照射された光が１０００ルクスの照度となるように調整し、蛍光灯と照度計の間に試料を挿置したときの照度（ルクス）を１０回測定し、その平均値を１０００ルクスで除し、１００を乗じた値を指す。 The patterned colored glass brick 2 of Example 2 has a transmissivity of several percent at a thickness of 10 mm, an initial emission intensity immediately after irradiation of 1000 lux of light for 20 minutes, and 500 mcd / m 2. The emission intensity after 10 minutes from the stop was 10% or more of the initial emission intensity. The light transmittance is obtained by preparing a plate-like sample cut to a size of 50 × 50 × 10 mm and optically polished on both sides, and the light directly irradiated from the fluorescent lamp as the light source to the illuminometer is 1000 lux. The illuminance (lux) when the sample is inserted between the fluorescent lamp and the illuminometer is measured 10 times, the average value is divided by 1000 lux, and multiplied by 100.
なお、上記の気泡量は、作製した模様入り着色ガラスレンガ１０を約３０ｍｍ×３０ｍｍ×１０ｍｍに切断し、その質量を測定し、次いで、その中に存在する気泡数をカウントし、単位質量当たりの個数に換算して求めた。 In addition, said bubble amount cuts the produced colored glass brick 10 with a pattern into about 30 mm x 30 mm x 10 mm, measures the mass, then counts the number of bubbles which exist in it, per unit mass It was calculated in terms of number.
また、３０℃〜３８０℃における平均線膨張係数は、ブルカー・エイエックスエス株式会社製の熱機械分析装置 ディラトメータにて測定した。波長４００ｎｍ〜７００ｎｍの範囲における、肉厚７ｍｍでの平均透過率は、光学研磨された２０ｍｍ×２０ｍｍ×７ｍｍの試料を作製し、株式会社島津製作所製の分光光度計 ＵＶ２５００ＰＣで測定した。 Moreover, the average linear expansion coefficient in 30 degreeC-380 degreeC was measured with the thermomechanical analyzer dilatometer made from Bruker AXS. The average transmittance at a thickness of 7 mm in the wavelength range of 400 nm to 700 nm was measured with a spectrophotometer UV2500PC manufactured by Shimadzu Corporation, which was an optically polished 20 mm × 20 mm × 7 mm sample.
本発明によれば、着色ガラス小体と未着色ガラス小体とが焼結一体化された建築用着色ガラス物品を提供することができる。 According to the present invention, it is possible to provide an architectural colored glass article in which a colored glass body and an uncolored glass body are integrated by sintering.
１、２ 従来のガラスレンガ
１０ 模様入り着色ガラスレンガ（建築用着色ガラス物品）
１０ａ 意匠面
１０ｂ 裏面
１０ｃ 側面
１１ 薄片状模様
1, 2 Conventional glass bricks 10 Colored glass bricks with patterns (colored glass articles for construction)
10a Design surface 10b Back surface 10c Side surface 11 Flaky pattern
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| JP2009173514A true JP2009173514A (en) | 2009-08-06 |
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