JP2012020922A - Natural marble-like crystallized glass, natural marble-like crystallized glass article and production method therefor - Google Patents
Natural marble-like crystallized glass, natural marble-like crystallized glass article and production method therefor Download PDFInfo
- Publication number
- JP2012020922A JP2012020922A JP2011104805A JP2011104805A JP2012020922A JP 2012020922 A JP2012020922 A JP 2012020922A JP 2011104805 A JP2011104805 A JP 2011104805A JP 2011104805 A JP2011104805 A JP 2011104805A JP 2012020922 A JP2012020922 A JP 2012020922A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- glass
- natural marble
- crystallized glass
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
- Glass Compositions (AREA)
Abstract
Description
本発明は、天然大理石様結晶化ガラス（天然大理石の代替として使用される結晶化ガラス）、天然大理石様結晶化ガラス物品及びその製造方法に関し、特に建築物の内装材や外装材に使用される天然大理石様結晶化ガラス、天然大理石様結晶化ガラス物品及びその製造方法に関する。 The present invention relates to a natural marble-like crystallized glass (crystallized glass used as a substitute for natural marble), a natural marble-like crystallized glass article, and a method for producing the same, and particularly to interior materials and exterior materials for buildings. The present invention relates to a natural marble-like crystallized glass, a natural marble-like crystallized glass article, and a method for producing the same.
従来、天然大理石模様を呈する結晶化ガラスは、化学的耐久性、機械的強度等の特性に優れているため、主に天然大理石の代替として使用されてきたが、現在では、色調と肌理の自由度が高く、自然には存在しない美しい外観を呈するため、デザイン性を追求する建築物の内装材や外装材に使用されている。 Conventionally, crystallized glass with a natural marble pattern has been used mainly as a substitute for natural marble because of its excellent chemical durability and mechanical strength, but now it is free of color and texture. Because it has a high degree of appearance and a beautiful appearance that does not exist in nature, it is used for interior and exterior materials in buildings that pursue design.
この種の結晶化ガラスとして、結晶性ガラスを焼成することにより、主結晶としてβ−ウォラストナイト結晶（ＣａＯ・ＳｉＯ２）を析出させた天然大理石様結晶化ガラスが提案されている。 As this kind of crystallized glass, natural marble-like crystallized glass in which β-wollastonite crystal (CaO · SiO 2 ) is precipitated as a main crystal by firing crystalline glass has been proposed.
例えば、特許文献１には、質量％で、ＳｉＯ２ ５０〜６５％、Ａｌ２Ｏ３ ３〜１３％、ＣａＯ １５〜２５％、ＺｎＯ ２〜１０％を必須成分とする調合原料を溶融し、成形した後、再加熱して得られる主として、β−ウォラストナイト結晶からなる天然大理石様結晶化ガラスが開示されている。 For example, in Patent Document 1, a raw material containing 50% to 65% SiO 2 , 3 % to 13% Al 2 O 3 , 15% to 25% CaO, and 2% to 10% ZnO is melted in mass%, A natural marble-like crystallized glass mainly composed of β-wollastonite crystals obtained by reheating after molding is disclosed.
さらに、特許文献２には、質量％で本質的にＳｉＯ２ ４８〜６８％、ＣａＯ ６〜２２％、Ｒ２Ｏ ５〜２２％、Ａｌ２Ｏ３ ０．５〜１７％、ＭｇＯ ０．２〜８％、Ｂ２Ｏ３ ０〜６％、ＺｎＯ ０〜９％、ＢａＯ ０〜８％、但しＺｎＯ＋ＢａＯ＜１５％、着色酸化物０〜１０％からなるガラスを熱処理して、主結晶としてβ−ウォラストナイト結晶を析出させる結晶化ガラスの製造方法が開示されている。 Further, Patent Document 2, essentially SiO 2 48 to 68% by mass%, CaO 6~22%, R 2 O 5~22%, Al 2 O 3 0.5~17%, MgO 0.2 ~ 8%, B 2 O 3 0-6%, ZnO 0-9%, BaO 0-8%, but ZnO + BaO <15%, colored oxide 0-10% is heat treated to produce β as the main crystal -A method for producing crystallized glass for precipitating wollastonite crystals is disclosed.
近年、建築物の低価格化の要求に伴い、天然大理石様結晶化ガラスの低価格化も要求されている。天然大理石様結晶化ガラスの低価格化の方法として、原料コストや溶融コストの低下、焼成温度の低温化、表面粗さや平坦度の向上が効果的である。具体的に言えば、結晶性ガラスのガラス原料として、窓板ガラス、ビンガラス、ディスプレイ用ガラス等の異種ガラスカレット、つまり廉価な異種ガラスカレットの使用比率を高めると、原料コストと溶融コストを低下することができる。また、結晶性ガラスの焼成温度を１１００℃以下にすれば、燃料費を抑制できると共に、耐火性容器を長寿命化することができる。また、焼成工程で結晶性ガラスから微細な結晶を析出させると、表面粗さや平坦度が向上し、研磨効率を高めることができる。 In recent years, with the demand for lower prices for buildings, there has been a demand for lower prices for natural marble-like crystallized glass. As a method for reducing the cost of natural marble-like crystallized glass, it is effective to lower raw material costs and melting costs, lower firing temperatures, and improve surface roughness and flatness. Specifically, as the glass raw material for crystalline glass, increasing the usage ratio of different types of glass cullet, such as window glass, bottle glass, display glass, etc. Can do. Moreover, if the baking temperature of crystalline glass shall be 1100 degrees C or less, while being able to suppress a fuel cost, a refractory container can be extended in life. Further, when fine crystals are precipitated from the crystalline glass in the firing step, the surface roughness and flatness are improved, and the polishing efficiency can be increased.
しかし、特許文献１に記載の天然大理石様結晶化ガラスは、焼成温度が高いため、低価格化が困難である。また、特許文献１に記載の天然大理石様結晶化ガラスは、添加可能な成分が限られているため、ガラス原料として、異種ガラスカレットの使用比率を高めることが困難であり、結果として、低価格化が困難である。 However, since the natural marble-like crystallized glass described in Patent Document 1 has a high firing temperature, it is difficult to reduce the price. Moreover, since the natural marble-like crystallized glass described in Patent Document 1 has limited components that can be added, it is difficult to increase the use ratio of different glass cullet as a glass raw material. Is difficult.
また、特許文献２に記載の天然大理石様結晶化ガラスは、低温で焼成可能であるが、異種結晶が析出し易く、また表面の結晶が粗大化し易いため、低価格化が困難である。 Further, the natural marble-like crystallized glass described in Patent Document 2 can be fired at a low temperature, but it is difficult to reduce the price because different types of crystals are likely to precipitate and the surface crystals are likely to be coarse.
そこで、本発明は、原料コストや溶融コストを低下できると共に、低温で焼成可能であり、しかも焼成後の表面精度を向上し得る天然大理石様結晶化ガラスの製造方法を創案することにより、安価な天然大理石様結晶化ガラス及び天然大理石様結晶化ガラス物品を得ることを技術的課題とする。 Therefore, the present invention can reduce the raw material cost and the melting cost, and can be fired at a low temperature, and can be inexpensively created by creating a method for producing natural marble-like crystallized glass that can improve the surface accuracy after firing. It is a technical object to obtain natural marble-like crystallized glass and natural marble-like crystallized glass articles.
本発明者は、種々の検討を行った結果、ＳｉＯ２、ＣａＯ、ＺｎＯ、Ｌｉ２Ｏ、ＭｇＯ、ＳｒＯ及びＺｒＯ２の含有量を所定範囲に規制することにより、上記技術的課題を解決できることを見出し、本発明として、提案するものである。すなわち、本発明の天然大理石様結晶化ガラスは、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２（ＭｇＯ、ＳｒＯ、ＺｒＯ２の合量）を０．１質量％以上含み、主結晶としてβ−ウォラストナイト結晶が析出していることを特徴とする。 As a result of various studies, the present inventor has found that the above technical problem can be solved by regulating the contents of SiO 2 , CaO, ZnO, Li 2 O, MgO, SrO and ZrO 2 within a predetermined range. It is proposed as a heading and the present invention. That is, the natural marble-like crystallized glass of the present invention has a composition of SiO 2 of 45 mass% or more, CaO of 7.5 mass% or more, ZnO of 0.05 mass% or more, MgO + SrO + ZrO 2 (MgO, SrO, ZrO 2 ) in an amount of 0.1% by mass or more, and β-wollastonite crystals are precipitated as main crystals.
組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上添加すると、結晶性ガラスの流動性が向上し、具体的には１１００℃以下で焼成し易くなり、また微細なβ−ウォラストナイト結晶が析出し易くなる。また、本発明の天然大理石様結晶化ガラスは、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含むため、結晶性ガラスの溶解性や流動性が良好であり、具体的には１１００℃以下で焼成し易くなり、また化学的耐久性が良好である。また、このようにすれば、窓板ガラス、ビンガラス、ディスプレイ用ガラス等の異種ガラスカレット、つまり廉価な異種ガラスカレットの使用比率を高めることが可能になり、原料コストと溶融コストを低下することができる。なお、ガラスカレットの使用比率が高い程、ガラスバッチの溶解性が向上して、溶融コストが低下する。したがって、本発明の天然大理石様結晶化ガラスは、上記のように成分組成が規制されているため、低価格化の要請を満たすことができる。 Addition of 45% by mass or more of SiO 2 , 7.5% by mass or more of CaO and 0.05% by mass or more of ZnO as the composition improves the fluidity of the crystalline glass, specifically, firing at 1100 ° C. or less. And fine β-wollastonite crystals are likely to precipitate. In addition, the natural marble-like crystallized glass of the present invention contains MgO + SrO + ZrO 2 in an amount of 0.1% by mass or more, so that the solubility and fluidity of the crystalline glass are good, and specifically, it is easy to fire at 1100 ° C. or less. In addition, the chemical durability is good. In addition, this makes it possible to increase the usage ratio of different types of glass cullet, such as window glass, bottle glass, and display glass, that is, low-cost different types of glass cullet, thereby reducing raw material costs and melting costs. . In addition, the higher the usage ratio of the glass cullet, the better the solubility of the glass batch and the lower the melting cost. Therefore, the natural marble-like crystallized glass of the present invention can satisfy the demand for cost reduction because the component composition is regulated as described above.
第二に、本発明の天然大理石様結晶化ガラスは、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、Ｌｉ２Ｏを０．０５質量％以上１質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含み、主結晶としてβ−ウォラストナイト結晶が析出していることを特徴とする。 Second, the natural marble-like crystallized glass of the present invention has a composition of SiO 2 of 45% by mass or more, CaO of 7.5% by mass or more, ZnO of 0.05% by mass or more, and Li 2 O of 0.000. It is characterized by containing 0.5 mass% or more and less than 1 mass%, MgO + SrO + ZrO 2 by 0.1 mass% or more, and β-wollastonite crystals are precipitated as main crystals.
第三に、本発明の天然大理石様結晶化ガラスは、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上６質量％未満、Ｎａ２Ｏ＋Ｋ２Ｏ（Ｎａ２ＯとＫ２Ｏの合量）を３．８質量％以上１０質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含み、主結晶としてβ−ウォラストナイト結晶が析出していることを特徴とする。 Third, the natural marble-like crystallized glass of the present invention has a composition of SiO 2 of 45 mass% or more, CaO of 7.5 mass% or more, ZnO of 0.05 mass% or more and less than 6 mass%, Na 2. O + K 2 O (total amount of Na 2 O and K 2 O) is 3.8% by mass to less than 10% by mass, MgO + SrO + ZrO 2 is 0.1% by mass or more, and β-wollastonite crystal is precipitated as the main crystal. It is characterized by.
第四に、本発明の天然大理石様結晶化ガラスは、ＣａＯ＋ＺｎＯ＋Ｌｉ２Ｏ（ＣａＯ、ＺｎＯ、及びＬｉ２Ｏの合量）の含有量が２１〜３１質量％であることが好ましい。 Fourth, the natural marble-like crystallized glass of the present invention preferably has a content of CaO + ZnO + Li 2 O (total amount of CaO, ZnO, and Li 2 O) of 21 to 31% by mass.
第五に、本発明の天然大理石様結晶化ガラスは、質量％で、ＳｉＯ２ ４５〜７５％、Ａｌ２Ｏ３ １〜２５％、ＣａＯ ５〜２５％、ＺｎＯ ０．０５〜１０％、ＢａＯ １〜１５％、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２ ０．１〜９％、Ｌｉ２Ｏ ０〜０．９９％、Ｎａ２Ｏ １〜１５％、Ｋ２Ｏ ０〜７％、Ｂ２Ｏ３ ０〜５％、ＣｅＯ２ ０〜０．５％、ＳＯ３ ０〜０．５％、Ｓｂ２Ｏ３ ０〜１％ Ａｓ２Ｏ３ ０〜１％を含有することが好ましい。 Fifth, natural marble-like crystallized glass of the present invention, in mass%, SiO 2 45~75%, Al 2 O 3 1~25%, CaO 5~25%, ZnO 0.05~10%, BaO 1~15%, MgO + SrO + ZrO 2 0.1~9%, Li 2 O 0~0.99%, Na 2 O 1~15%, K 2 O 0~7%, B 2 O 3 0~5%, CeO 2 0~0.5%, SO 3 0~0.5% , preferably contains Sb 2 O 3 0~1% As 2 O 3 0~1%.
第六に、本発明の天然大理石様結晶化ガラスは、ＳｉＯ２＋Ａｌ２Ｏ３＋ＣａＯ＋ＺｎＯ＋Ｌｉ２Ｏ＋ＢａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｂ２Ｏ３＋Ｓｂ２Ｏ３＋ＣｅＯ２＋ＳＯ３＋Ｆｅ２Ｏ３＋ＮｉＯ＋ＣｏＯ（ＳｉＯ２、Ａｌ２Ｏ３、ＣａＯ、ＺｎＯ、Ｌｉ２Ｏ、ＢａＯ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｂ２Ｏ３、Ｓｂ２Ｏ３、ＣｅＯ２、ＳＯ３、Ｆｅ２Ｏ３、ＮｉＯ、及びＣｏＯの合量）の含有量が９０〜９９．８質量％未満であることが好ましい。 Sixth, the natural marble-like crystallized glass of the present invention is SiO 2 + Al 2 O 3 + CaO + ZnO + Li 2 O + BaO + Na 2 O + K 2 O + B 2 O 3 + Sb 2 O 3 + CeO 2 + SO 3 + Fe 2 O 3 + NiO + CoO (SiO 2 , Al 2 O 3 , CaO, ZnO, Li 2 O, BaO, Na 2 O, K 2 O, B 2 O 3 , Sb 2 O 3 , CeO 2 , SO 3 , Fe 2 O 3 , NiO, and CoO) The content of is preferably 90 to less than 99.8% by mass.
第七に、本発明の天然大理石様結晶化ガラスは、Ｆｅ２Ｏ３の含有量が２０００ｐｐｍ以下であることが好ましい。 Seventh, the natural marble-like crystallized glass of the present invention preferably has an Fe 2 O 3 content of 2000 ppm or less.
第八に、本発明の天然大理石様結晶化ガラス物品は、表面から内部に向かって針状のβ−ウォラストナイト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なる天然大理石様結晶化ガラス物品であって、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含むことを特徴とする。このようにすれば、天然大理石様結晶化ガラス物品の低価格化の要請を満たすことができる。 Eighth, the natural marble-like crystallized glass article of the present invention is a natural marble formed by fusing together a plurality of crystallized glass small regions in which acicular β-wollastonite crystals are precipitated from the surface toward the inside. A crystallized glass article having a composition containing SiO 2 of 45% by mass or more, CaO of 7.5% by mass or more, ZnO of 0.05% by mass or more, and MgO + SrO + ZrO 2 of 0.1% by mass or more. Features. If it does in this way, the request | requirement of the price reduction of a natural marble-like crystallized glass article can be satisfy | filled.
第九に、本発明の天然大理石様結晶化ガラス物品は、表面から内部に向かって針状のβ−ウォラストナイト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なる天然大理石様結晶化ガラス物品であって、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、Ｌｉ２Ｏを０．０５質量％以上１質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含むことを特徴とする。 Ninth, the natural marble-like crystallized glass article of the present invention is a natural marble formed by fusing together a plurality of crystallized glass small regions in which acicular β-wollastonite crystals are precipitated from the surface toward the inside. A crystallized glass article having a composition of SiO 2 of 45% by mass or more, CaO of 7.5% by mass or more, ZnO of 0.05% by mass or more, and Li 2 O of 0.05% by mass or more of 1% by mass. %, MgO + SrO + ZrO 2 is contained in an amount of 0.1% by mass or more.
第十に、本発明の天然大理石様結晶化ガラス物品は、表面から内部に向かって針状のβ−ウォラストナイト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なる天然大理石様結晶化ガラス物品であって、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上６質量％未満、Ｎａ２Ｏ＋Ｋ２Ｏを３．８質量％以上１０質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含むことを特徴とする。 Tenth, the natural marble-like crystallized glass article of the present invention is a natural marble formed by fusing together a plurality of crystallized glass small regions in which acicular β-wollastonite crystals are precipitated from the surface toward the inside. A crystallized glass article having a composition of SiO 2 of 45 mass% or more, CaO of 7.5 mass% or more, ZnO of 0.05 mass% or more and less than 6 mass%, and Na 2 O + K 2 O of 3. It is characterized by containing 8% by mass or more and less than 10% by mass and containing 0.1% by mass or more of MgO + SrO + ZrO 2 .
第十一に、本発明の天然大理石様結晶化ガラス物品は、表面のβ−ウォラストナイト結晶の最大粒径が８００μｍ以下であることが好ましい。なお、表面のβ−ウォラストナイト結晶の最大粒径は、ＳＥＭ等で測定可能である。 Eleventh, the natural marble-like crystallized glass article of the present invention preferably has a maximum particle size of β-wollastonite crystals of 800 μm or less. The maximum particle size of the surface β-wollastonite crystal can be measured by SEM or the like.
第十二に、本発明の天然大理石様結晶化ガラス物品の製造方法は、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含む複数の結晶性ガラス小体を耐火性容器内に収容した後、結晶性ガラス小体の軟化点より高い温度で熱処理することにより、結晶性ガラス小体の表面から主結晶として針状のβ−ウォラストナイト結晶を析出させながら、複数の結晶性ガラス小体を軟化変形させて互いに融着させることが好ましい。このようにすれば、天然大理石様結晶化ガラス物品を安価に作製することができる。 Twelfth, the method for producing a natural marble-like crystallized glass article according to the present invention has a composition of SiO 2 of 45 mass% or more, CaO of 7.5 mass% or more, ZnO of 0.05 mass% or more, MgO + SrO + ZrO. The surface of the crystalline glass body is heat treated at a temperature higher than the softening point of the crystalline glass body after accommodating a plurality of crystalline glass bodies containing 2 in an amount of 0.1% by mass or more in a refractory container. From the above, it is preferable to soften and deform a plurality of crystalline glass bodies and fuse them together while precipitating acicular β-wollastonite crystals as main crystals. In this way, a natural marble-like crystallized glass article can be produced at a low cost.
第十三に、本発明の天然大理石様結晶化ガラス物品の製造方法は、自由表面の表面粗さＲａが１μｍ以下になるように、複数の結晶性ガラス小体を軟化変形させて互いに融着させることが好ましい。ここで、「表面粗さＲａ」は、ＪＩＳ Ｂ０６０１：２００１に準拠した方法で測定した値を指す。 Thirteenth, according to the method for producing a natural marble-like crystallized glass article of the present invention, a plurality of crystalline glass bodies are softened and fused together so that the surface roughness Ra of the free surface is 1 μm or less. It is preferable to make it. Here, “surface roughness Ra” refers to a value measured by a method based on JIS B0601: 2001.
第十四に、本発明の天然大理石様結晶化ガラス物品の製造方法は、結晶性ガラス小体のガラス原料として、ＭｇＯ、ＳｒＯ、ＺｒＯ２のいずれかを含むガラスカレットを用いることが好ましい。なお、ガラスカレットとして、ＭｇＯ、ＳｒＯ、ＺｒＯ２のいずれかを含む限り、種々のガラスカレットが使用可能である。 Fourteenth, in the method for producing a natural marble-like crystallized glass article of the present invention, it is preferable to use a glass cullet containing any of MgO, SrO, and ZrO 2 as a glass raw material for the crystalline glass body. As the glass cullet, various glass cullets can be used as long as any of MgO, SrO, and ZrO 2 is included.
第十五に、本発明の天然大理石様結晶化ガラス物品の製造方法は、ガラスカレットとして、窓板ガラスのガラスカレット、ビンガラスのガラスカレット、ディスプレイ用ガラスのガラスカレットのいずれかを含むことが好ましい。 Fifteenth, the method for producing a natural marble-like crystallized glass article of the present invention preferably includes any one of a glass cullet of window glass, a glass cullet of bottle glass, and a glass cullet of glass for display.
第十六に、本発明の天然大理石様結晶化ガラス物品の製造方法は、１０４．０Ｐａ・ｓにおけるガラスカレットの温度をＴ１、１０４．０Ｐａ・ｓにおける結晶性ガラスの温度をＴ２としたとき、｜Ｔ１−Ｔ２｜≦２００℃の関係を満たすガラスカレットを用いることが好ましい。ここで、Ｔ２は、ガラスカレットを用いず、固体結晶原料のみで結晶性ガラスを作製した場合、つまりオールバッチで結晶性ガラスを作製した場合に得られる値である（以下同様）。また、「１０４．０Ｐａ・ｓにおける温度」は、白金球引き上げ法等で測定可能である。 Sixteenth, manufacturing method of natural marble-like crystallized glass article of the present invention, the temperature of the crystallizable glass temperature of the glass cullet in 10 4.0 Pa · s at T 1, 10 4.0 Pa · s When T 2 is used, it is preferable to use glass cullet that satisfies the relationship of | T 1 −T 2 | ≦ 200 ° C. Here, T 2 does not use a glass cullet, if produced only crystalline glass solid crystalline material, i.e. a value obtained when producing a crystallizable glass in all batches, and so forth. The “temperature at 10 4.0 Pa · s” can be measured by a platinum ball pulling method or the like.
本発明の天然大理石様結晶化ガラスは、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含み、主結晶としてβ−ウォラストナイト結晶が析出していることを特徴とする。上記のように、各成分の含有量を限定した理由を下記に示す。 Natural marble-like crystallized glass of the present invention, a composition, a SiO 2 45% by mass or more, CaO 7.5 wt% or more, ZnO 0.05% by mass or more, includes a MgO + SrO + ZrO 2 0.1 wt% The β-wollastonite crystal is precipitated as the main crystal. The reason for limiting the content of each component as described above is shown below.
本発明の天然大理石様結晶化ガラスにおいて、ＳｉＯ２は、β−ウォラストナイト結晶を構成する成分であり、その含有量は４５％以上、４５〜７５％、特に５０〜７０％が好ましい。ＳｉＯ２の含有量が４５％より少ないと、成形時に結晶性ガラスが失透し易くなる。 In the natural marble-like crystallized glass of the present invention, SiO 2 is a component constituting β-wollastonite crystal, and the content thereof is preferably 45% or more, 45 to 75%, particularly preferably 50 to 70%. If the content of SiO 2 is less than 45%, the crystalline glass tends to be devitrified during molding.
本発明の天然大理石様結晶化ガラスにおいて、ＣａＯは、β−ウォラストナイト結晶を構成する成分であり、その含有量は７．５％以上、７．５〜２５％、１０〜２３％、１５〜２０％、特に１６〜１９％が好ましい。ＣａＯの含有量が７．５％より少ないと、β−ウォラストナイト結晶の析出量が少なくなり過ぎて、機械的強度が低下し、建材に使用する場合、耐久性が低下し易くなり、また粗大な結晶が析出して、表面精度が低下し易くなる。 In the natural marble-like crystallized glass of the present invention, CaO is a component constituting β-wollastonite crystal, and its content is 7.5% or more, 7.5 to 25%, 10 to 23%, 15 -20%, especially 16-19% is preferred. When the content of CaO is less than 7.5%, the amount of β-wollastonite crystals precipitated becomes too small, the mechanical strength decreases, and when used for building materials, the durability tends to decrease, Coarse crystals are precipitated, and the surface accuracy tends to be lowered.
本発明の天然大理石様結晶化ガラスにおいて、ＺｎＯは、結晶化特性を変化させずに結晶性ガラスの流動性を高める成分であり、その含有量は０．０５％以上、０．０５〜１０％、２〜８％、特に４〜８％が好ましい。ＺｎＯの含有量が０．０５％より少ないと、上記効果を享受し難くなる。 In the natural marble-like crystallized glass of the present invention, ZnO is a component that improves the fluidity of the crystalline glass without changing the crystallization characteristics, and its content is 0.05% or more and 0.05 to 10% 2 to 8%, particularly 4 to 8% is preferable. If the ZnO content is less than 0.05%, it is difficult to receive the above effects.
本発明の天然大理石様結晶化ガラスにおいて、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２は、結晶性ガラスの溶解性や流動性を高める成分であり、また化学的耐久性を高める成分であり、その含有量は０．１％以上、０．１〜９％、０．３〜５％、特に０．５〜２％が好ましい。ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量が０．１％より少ないと、上記効果を享受し難くなる。さらに、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量が０．１％より少ないと、異種ガラスカレットの使用比率を高めることが困難になり、結果として、原料コストと溶融コストの高騰を招く。なお、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量が９％より多いと、焼成時に異種結晶又は粗大結晶が析出して、結晶性ガラスの流動性が低下し易くなり、また所望の表面精度を確保し難くなる。 In the natural marble-like crystallized glass of the present invention, MgO + SrO + ZrO 2 is a component that enhances the solubility and fluidity of the crystalline glass, and is a component that enhances chemical durability, and its content is 0.1% or more. 0.1 to 9%, 0.3 to 5%, particularly 0.5 to 2% is preferable. When the content of MgO + SrO + ZrO 2 is less than 0.1%, it is difficult to receive the above effect. Furthermore, if the content of MgO + SrO + ZrO 2 is less than 0.1%, it is difficult to increase the usage ratio of the different glass cullet, resulting in a rise in raw material costs and melting costs. When the content of MgO + SrO + ZrO 2 is more than 9%, different crystals or coarse crystals are precipitated during firing, and the flowability of the crystalline glass is likely to be lowered, and it is difficult to ensure the desired surface accuracy.
本発明の天然大理石様結晶化ガラスは、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、Ｌｉ２Ｏを０．０５質量％以上１質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含み、主結晶としてβ−ウォラストナイト結晶が析出していることを特徴とする。 The natural marble-like crystallized glass of the present invention has a composition of SiO 2 of 45 mass% or more, CaO of 7.5 mass% or more, ZnO of 0.05 mass% or more, and Li 2 O of 0.05 mass% or more. It is characterized by containing less than 1% by mass, 0.1% by mass or more of MgO + SrO + ZrO 2, and β-wollastonite crystals are precipitated as main crystals.
ＳｉＯ２、ＣａＯ、ＺｎＯ、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量を限定した理由は、上記の通りである。Ｌｉ２Ｏは、焼成工程で結晶化速度を速める成分であり、また結晶性ガラスの流動性を高める成分であり、その含有量は０．０５〜０．９９％、０．１〜０．９５％、特に０．２〜０．９％が好ましい。Ｌｉ２Ｏの含有量が０．０５％より少ないと、上記効果を享受し難くなる。一方、Ｌｉ２Ｏの含有量が１％以上であると、熱膨張係数が不当に高くなり、また化学的耐久性が低下し易くなり、更には粘性が不当に低下するおそれがある。なお、粘性が低下し過ぎると、結晶性ガラスの流動性が向上するが、焼成工程後の結晶化ガラスに泡が残留し易くなる。 The reason for limiting the content of SiO 2 , CaO, ZnO, MgO + SrO + ZrO 2 is as described above. Li 2 O is a component that accelerates the crystallization speed in the firing step, and is a component that improves the fluidity of the crystalline glass, and its content is 0.05 to 0.99%, 0.1 to 0.95. %, Particularly 0.2 to 0.9% is preferable. When the content of Li 2 O is less than 0.05%, it is difficult to receive the above effect. On the other hand, when the content of Li 2 O is 1% or more, the thermal expansion coefficient is unduly high, the chemical durability tends to be lowered, and the viscosity may be unduly lowered. If the viscosity is too low, the flowability of the crystalline glass is improved, but bubbles are likely to remain in the crystallized glass after the firing step.
本発明の天然大理石様結晶化ガラスは、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上６質量％未満、Ｎａ２Ｏ＋Ｋ２Ｏを３．８質量％以上１０質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含み、主結晶としてβ−ウォラストナイト結晶が析出していることを特徴とする。 The natural marble-like crystallized glass of the present invention has a composition of SiO 2 of 45 mass% or more, CaO of 7.5 mass% or more, ZnO of 0.05 mass% or more and less than 6 mass%, Na 2 O + K 2 O. 3.8% by mass or more and less than 10% by mass, MgO + SrO + ZrO 2 is contained by 0.1% by mass or more, and β-wollastonite crystals are precipitated as main crystals.
ＳｉＯ２、ＣａＯ、ＺｎＯ、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量を限定した理由は、上記の通りである。Ｎａ２Ｏ＋Ｋ２Ｏは、焼成工程で結晶化速度を速める成分であり、また結晶性ガラスの流動性を高める成分であり、その含有量は３．８〜１０％未満、４〜８％、特に４．１〜６％が好ましい。Ｎａ２Ｏ＋Ｋ２Ｏの含有量が３．８％より少ないと、結晶性ガラスの溶融温度が上昇すると共に、粘度が上昇して、結晶性ガラスの流動性が低下し易くなる。一方、Ｎａ２Ｏ＋Ｋ２Ｏの含有量が１０％以上であると、熱膨張係数が不当に高くなり、建材用途に使用し難くなる。 The reason for limiting the content of SiO 2 , CaO, ZnO, MgO + SrO + ZrO 2 is as described above. Na 2 O + K 2 O is a component that accelerates the crystallization rate in the firing step, and is a component that improves the fluidity of the crystalline glass, and its content is less than 3.8-10%, especially 4-8%, 4.1 to 6% is preferable. When the content of Na 2 O + K 2 O is less than 3.8%, the melting temperature of the crystalline glass rises, the viscosity rises, and the fluidity of the crystalline glass tends to be lowered. On the other hand, if the content of Na 2 O + K 2 O is 10% or more, the thermal expansion coefficient becomes unreasonably high and it is difficult to use it for building materials.
本発明の天然大理石様結晶化ガラスは、質量％で、ＳｉＯ２ ４５〜７５％、Ａｌ２Ｏ３ １〜２５％、ＣａＯ ７．５〜２５％、ＺｎＯ ０．０５〜１０％、Ｌｉ２Ｏ ０〜０．９９％、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２ ０．１〜９％、ＢａＯ １〜１５％、Ｎａ２Ｏ １〜１５％、Ｋ２Ｏ ０〜７％、Ｂ２Ｏ３ ０〜５％、ＣｅＯ２ ０〜０．５％、ＳＯ３ ０〜０．５％、Ｓｂ２Ｏ３ ０〜１％ Ａｓ２Ｏ３ ０〜１％を含有することが好ましい。本発明の天然大理石様結晶化ガラスにおいて、上記のように各成分の含有量を限定した理由を以下に説明する。 Natural marble-like crystallized glass of the present invention, in mass%, SiO 2 45~75%, Al 2 O 3 1~25%, CaO 7.5~25%, ZnO 0.05~10%, Li 2 O 0-0.99%, MgO + SrO + ZrO 2 0.1-9%, BaO 1-15%, Na 2 O 1-15%, K 2 O 0-7%, B 2 O 3 0-5%, CeO 2 0 ~0.5%, SO 3 0~0.5%, preferably contains Sb 2 O 3 0~1% As 2 O 3 0~1%. The reason why the content of each component is limited as described above in the natural marble-like crystallized glass of the present invention will be described below.
ＳｉＯ２は、β−ウォラストナイト結晶を構成する成分であり、その含有量は４５〜７５％、特に５０〜７０％が好ましい。ＳｉＯ２の含有量が４５％より少ないと、成形時に結晶性ガラスが失透し易くなる。一方、ＳｉＯ２の含有量が７５％より多いと、結晶性ガラスの溶融温度が上昇すると共に、粘度が上昇して結晶性ガラスの流動性が低下し易くなる。 SiO 2 is a component constituting β-wollastonite crystal, and its content is preferably 45 to 75%, particularly preferably 50 to 70%. If the content of SiO 2 is less than 45%, the crystalline glass tends to be devitrified during molding. On the other hand, when the content of SiO 2 is more than 75%, the melting temperature of the crystalline glass rises, the viscosity rises, and the fluidity of the crystalline glass tends to decrease.
Ａｌ２Ｏ３は、失透を抑制する成分であり、その含有量は１〜２５％、特に３〜１５％が好ましい。Ａｌ２Ｏ３の含有量が１％より少ないと、耐失透性が低下し易くなり、化学的耐久性も低下し易くなる。一方、Ａｌ２Ｏ３の含有量が２５％より多いと、結晶性ガラスの溶解性が低下し易くなり、また異種結晶（アノーサイト）が析出して、結晶性ガラスの流動性が低下し易くなる。 Al 2 O 3 is a component that suppresses devitrification, and its content is preferably 1 to 25%, particularly preferably 3 to 15%. When the content of Al 2 O 3 is less than 1%, the devitrification resistance is liable to be lowered, and the chemical durability is also liable to be lowered. On the other hand, when the content of Al 2 O 3 is more than 25%, the solubility of the crystalline glass is likely to be lowered, and different crystals (anocite) are precipitated, so that the fluidity of the crystalline glass is likely to be lowered. Become.
ＣａＯは、β−ウォラストナイト結晶を構成する成分であり、その含有量は７．５〜２５％、１０〜２３％、１５〜２０％、特に１６〜１９％が好ましい。ＣａＯの含有量が７．５％より少ないと、β−ウォラストナイト結晶の析出量が少なくなり過ぎて、機械的強度が低下し、建材に使用する場合、耐久性が低下し易くなり、また粗大な結晶が析出して、表面精度が低下し易くなる。一方、ＣａＯの含有量が２５％より多いと、耐失透性が低下し易くなるため、結晶性ガラスの成形が困難になり、またβ−ウォラストナイト結晶の析出量が多くなり過ぎて、表面精度が低下し易くなる。 CaO is a component constituting β-wollastonite crystals, and the content thereof is preferably 7.5 to 25%, 10 to 23%, 15 to 20%, and particularly preferably 16 to 19%. When the content of CaO is less than 7.5%, the amount of β-wollastonite crystals precipitated becomes too small, the mechanical strength decreases, and when used for building materials, the durability tends to decrease, Coarse crystals are precipitated, and the surface accuracy tends to be lowered. On the other hand, if the content of CaO is more than 25%, the devitrification resistance tends to be lowered, so that it becomes difficult to form crystalline glass, and the amount of β-wollastonite crystals precipitated becomes too large. Surface accuracy is likely to decrease.
ＺｎＯは、結晶化特性を変化させずに結晶性ガラスの流動性を高める成分であり、その含有量は０．０５〜１０％、２〜８％、特に４〜８％が好ましい。ＺｎＯの含有量が０．０５％より少ないと、上記効果を享受し難くなる。一方、ＺｎＯの含有量が１０％より多いと、β−ウォラストナイト結晶が析出し難くなる。なお、ＺｎＯは、Ｌｉ２Ｏと同様の効果を有する成分である。 ZnO is a component that enhances the fluidity of the crystalline glass without changing the crystallization characteristics, and its content is preferably 0.05 to 10%, 2 to 8%, particularly 4 to 8%. If the ZnO content is less than 0.05%, it is difficult to receive the above effects. On the other hand, if the ZnO content is more than 10%, β-wollastonite crystals are difficult to precipitate. ZnO is a component having the same effect as Li 2 O.
Ｌｉ２Ｏは、焼成工程で結晶化速度を速める成分であり、また結晶性ガラスの流動性を高める成分であり、その含有量は０〜０．９９％、０．０５〜０．９９％、０．１〜０．９５％、特に０．２〜０．９％が好ましい。Ｌｉ２Ｏの含有量が１％以上であると、熱膨張係数が不当に高くなり、また化学的耐久性が低下し易くなり、更には粘性が不当に低下するおそれがある。なお、粘性が低下し過ぎると、結晶性ガラスの流動性が向上するが、焼成工程後の結晶化ガラスに泡が残留し易くなる。また、Ｌｉ２Ｏの含有量が０．０５％より少ないと、上記効果を享受し難くなる。 Li 2 O is a component that increases the crystallization speed in the firing step, and is a component that improves the fluidity of the crystalline glass, and its content is 0 to 0.99%, 0.05 to 0.99%, It is preferably 0.1 to 0.95%, particularly preferably 0.2 to 0.9%. When the Li 2 O content is 1% or more, the thermal expansion coefficient is unduly high, the chemical durability tends to be lowered, and the viscosity may be unduly lowered. If the viscosity is too low, the flowability of the crystalline glass is improved, but bubbles are likely to remain in the crystallized glass after the firing step. Further, when the content of Li 2 O is less than 0.05%, it is difficult to receive the above effect.
ＣａＯ＋ＺｎＯ＋Ｌｉ２Ｏの含有量は２１〜３１％、２１．５〜２８％、特に２２〜２７％が好ましい。ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量が多い場合、結晶成長を阻害する粗大結晶が析出し易くなるが、ＣａＯ＋ＺｎＯ＋Ｌｉ２Ｏを上記範囲に規制すれば、このような事態を防止し易くなる。なお、質量比（ＣａＯ＋ＺｎＯ＋Ｌｉ２Ｏ）／（ＭｇＯ＋ＳｒＯ＋ＺｒＯ２）の値は３．０〜１００、５〜５０、特に８〜３０が好ましい。この値が小さ過ぎると、焼成時に異種結晶又は粗大結晶が析出して、結晶性ガラスの流動性が低下し易くなり、また所望の表面精度を確保し難くなる。一方、この値が大き過ぎると、異種ガラスカレットの使用比率を高めることが困難になり、結果として、原料コストと溶融コストの高騰を招く。 The content of CaO + ZnO + Li 2 O is preferably 21 to 31%, 21.5 to 28%, particularly preferably 22 to 27%. When the content of MgO + SrO + ZrO 2 is large, coarse crystals that inhibit crystal growth are likely to precipitate. However, if CaO + ZnO + Li 2 O is regulated within the above range, such a situation can be easily prevented. The value of the mass ratio (CaO + ZnO + Li 2 O ) / (MgO + SrO + ZrO 2) is 3.0～100,5～50, particularly 8 to 30 are preferred. If this value is too small, different crystals or coarse crystals are precipitated during firing, the fluidity of the crystalline glass tends to be lowered, and it is difficult to ensure the desired surface accuracy. On the other hand, if this value is too large, it will be difficult to increase the usage ratio of the different glass cullet, resulting in an increase in raw material costs and melting costs.
ＭｇＯ＋ＳｒＯ＋ＺｒＯ２は、結晶性ガラスの溶解性や流動性を高める成分であり、また化学的耐久性を高める成分であり、その含有量は０．１〜９％、０．３〜５％、特に０．５〜２％が好ましい。ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量が０．１％より少ないと、上記効果を享受し難くなる。さらに、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量が０．１％より少ないと、異種ガラスカレットの使用比率を高めることが困難になり、結果として、原料コストと溶融コストの高騰を招く。一方、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２の含有量が９％より多いと、焼成時に異種結晶又は粗大結晶が析出して、結晶性ガラスの流動性が低下し易くなり、また所望の表面精度を確保し難くなる。 MgO + SrO + ZrO 2 is a component that enhances the solubility and fluidity of the crystalline glass, and is a component that enhances chemical durability, and its content is 0.1 to 9%, 0.3 to 5%, particularly 0. 0.5 to 2% is preferable. When the content of MgO + SrO + ZrO 2 is less than 0.1%, it is difficult to receive the above effect. Furthermore, if the content of MgO + SrO + ZrO 2 is less than 0.1%, it is difficult to increase the usage ratio of the different glass cullet, resulting in a rise in raw material costs and melting costs. On the other hand, if the content of MgO + SrO + ZrO 2 is more than 9%, different crystals or coarse crystals are precipitated during firing, and the fluidity of the crystalline glass tends to be lowered, and it is difficult to ensure the desired surface accuracy.
ＭｇＯは、結晶性ガラスの溶解性や流動性を高める成分であり、その含有量は０〜２％、特に０．１〜１．５％が好ましい。ＭｇＯの含有量が２％より多いと、焼成時にＭｇ系の異種結晶が析出して、結晶性ガラスの流動性が低下し易くなり、また所望の表面精度を確保し難くなる。なお、ＭｇＯは、窓板ガラス、ビンガラス、液晶ディスプレイ用ガラス等に含まれる成分である。このため、ＭｇＯの含有量が０．１％以上であると、ガラス原料として、窓板ガラス、ビンガラス、液晶ディスプレイ用ガラス等のガラスカレットを使用し易くなる。 MgO is a component that enhances the solubility and fluidity of the crystalline glass, and its content is preferably 0 to 2%, particularly preferably 0.1 to 1.5%. When the content of MgO is more than 2%, Mg-based heterogeneous crystals are precipitated during firing, and the fluidity of the crystalline glass tends to be lowered, and it is difficult to ensure desired surface accuracy. MgO is a component contained in window glass, bottle glass, liquid crystal display glass, and the like. For this reason, when the content of MgO is 0.1% or more, it becomes easy to use glass cullet such as window glass, bottle glass, and liquid crystal display glass as a glass raw material.
ＳｒＯは、結晶性ガラスの溶解性や流動性を高める成分であり、その含有量は０〜５％、特に０．１〜２．５％が好ましい。ＳｒＯの含有量が５％より多いと、焼成時にＳｒ系の異種結晶が析出して、結晶性ガラスの流動性が低下し、また所望の表面精度を確保し難くなる。なお、ＳｒＯは、液晶ディスプレイ用ガラス、プラズマディスプレイ用ガラス等に含まれる成分である。このため、ＳｒＯの含有量が０．１％以上であると、ガラス原料として、液晶ディスプレイ用ガラス、プラズマディスプレイ用ガラス等のガラスカレットを使用し易くなる。 SrO is a component that enhances the solubility and fluidity of the crystalline glass, and its content is preferably 0 to 5%, particularly preferably 0.1 to 2.5%. If the SrO content is more than 5%, Sr-based heterogeneous crystals are precipitated during firing, the fluidity of the crystalline glass is lowered, and it is difficult to ensure the desired surface accuracy. SrO is a component contained in liquid crystal display glass, plasma display glass, and the like. For this reason, it becomes easy to use glass cullet, such as glass for liquid crystal displays and glass for plasma displays, as a glass raw material as content of SrO is 0.1% or more.
ＺｒＯ２は、化学耐久性を高める成分であり、その含有量は０〜２％、特に０．１〜１％が好ましい。ＺｒＯ２の含有量が２％より多いと、結晶成長を阻害する粗大結晶が析出し易くなるため、結晶性ガラスの流動性が低下したり、所望の表面精度を確保し難くなったり、曲げ加工し難くなる。なお、ＺｒＯ２は、プラズマディスプレイ用ガラス等に含まれる成分である。このため、ＺｒＯ２の含有量が０．１％以上であると、ガラス原料として、プラズマディスプレイ用ガラス等のガラスカレットを使用し易くなる。 ZrO 2 is a component that enhances chemical durability, and its content is preferably 0 to 2%, particularly preferably 0.1 to 1%. If the content of ZrO 2 is more than 2%, coarse crystals that hinder crystal growth tend to precipitate, so that the fluidity of the crystalline glass is lowered, it is difficult to ensure the desired surface accuracy, or bending processing is performed. It becomes difficult to do. ZrO 2 is a component contained in plasma display glass and the like. Therefore, the content of ZrO 2 is 0.1% or more, as a glass raw material, tends to use a glass cullet, such as glass for a plasma display.
ＢａＯは、結晶性ガラスの流動性を高める成分であり、その含有量は０〜１５％、２〜１５％、特に３〜１４％が好ましい。ＢａＯの含有量が２０％より多いと、β−ウォラストナイト結晶が析出し難くなる。なお、ＢａＯの含有量を１％以上添加すれば、粘性が低下して、所望の表面平滑性を確保し易くなる。 BaO is a component that enhances the fluidity of the crystalline glass, and its content is preferably 0 to 15%, 2 to 15%, and particularly preferably 3 to 14%. When the content of BaO is more than 20%, β-wollastonite crystals are difficult to precipitate. If the BaO content is 1% or more, the viscosity is lowered and it becomes easy to ensure the desired surface smoothness.
Ｎａ２Ｏは、粘性を低下させる成分であり、その含有量は１〜１５％、特に１〜１０％が好ましい。Ｎａ２Ｏの含有量が１％より少ないと、粘性が増大して結晶性ガラスの溶解性や流動性が低下し易くなると共に、板ガラス、ビンガラス等の異種ガラスカレットを使用し難くなる。一方、Ｎａ２Ｏの含有量が１５％より多いと、化学的耐久性が低下し易くなり、また熱膨張係数が不当に高くなるため、建材用途に使用し難くなる。 Na 2 O is a component that lowers the viscosity, and its content is preferably 1 to 15%, particularly preferably 1 to 10%. When the content of Na 2 O is less than 1%, the viscosity increases and the solubility and fluidity of the crystalline glass are likely to be lowered, and it is difficult to use dissimilar glass cullet such as plate glass and bottle glass. On the other hand, when the content of Na 2 O is more than 15%, the chemical durability tends to be lowered, and the thermal expansion coefficient is unduly increased, which makes it difficult to use for building materials.
Ｋ２Ｏは、粘性を低下させる成分であり、その含有量は０〜７％、０〜５％、特に０〜１．９％が好ましい。Ｋ２Ｏの含有量が７％より多いと、化学的耐久性が低下し易くなり、またβ−ウォラストナイト結晶が粗大化し易くなり、所望の表面精度を確保し難くなる。 K 2 O is a component that lowers the viscosity, and its content is preferably 0 to 7%, 0 to 5%, particularly preferably 0 to 1.9%. When the content of K 2 O is more than 7%, chemical durability tends to be lowered, and β-wollastonite crystals are likely to be coarsened, making it difficult to ensure desired surface accuracy.
Ｎａ２Ｏ＋Ｋ２Ｏの含有量は３．８〜１０％、４〜８％、特に４．１〜６％が好ましい。Ｎａ２Ｏ＋Ｋ２Ｏの含有量が３．８％より少ないと、結晶性ガラスの溶融温度が上昇すると共に、粘度が上昇して、結晶性ガラスの流動性が低下し易くなる。一方、Ｎａ２Ｏ＋Ｋ２Ｏの含有量が１０％より多いと、熱膨張係数が不当に高くなり、建材用途に使用し難くなる。なお、組成中にＬｉ２Ｏを０．０５％以上含む場合は、Ｎａ２Ｏ＋Ｋ２Ｏの含有量の下限範囲を２％以上とすることができる。 The content of Na 2 O + K 2 O is preferably 3.8 to 10%, 4 to 8%, particularly 4.1 to 6%. When the content of Na 2 O + K 2 O is less than 3.8%, the melting temperature of the crystalline glass rises, the viscosity rises, and the fluidity of the crystalline glass tends to be lowered. On the other hand, if the content of Na 2 O + K 2 O is more than 10%, the coefficient of thermal expansion becomes unreasonably high, making it difficult to use for building materials. In the case where in the composition containing Li 2 O 0.05% or more, the lower limit range of the content of Na 2 O + K 2 O can be 2% or more.
ガラスバッチ中のガラスカレットの比率が高い場合、質量比Ｋ２Ｏ／Ｎａ２Ｏの値は小さいことが好ましく、具体的には５．０以下、３．０以下、特に１．０以下が好ましい。 When the ratio of glass cullet in the glass batch is high, the value of the mass ratio K 2 O / Na 2 O is preferably small, specifically 5.0 or less, 3.0 or less, particularly 1.0 or less. .
Ｂ２Ｏ３は、結晶化前後で熱膨張係数を変化させずに結晶性ガラスの流動性を高める成分であり、その含有量は０〜５％、０〜３％、特に０〜１％が好ましい。Ｂ２Ｏ３の含有量が５％より多いと、焼成時にホウ酸系の異種結晶が析出して、結晶性ガラスの流動性が低下し易くなる。 B 2 O 3 is a component that increases the fluidity of the crystalline glass without changing the thermal expansion coefficient before and after crystallization, and its content is 0 to 5%, 0 to 3%, particularly 0 to 1%. preferable. When the content of B 2 O 3 is more than 5%, a boric acid-based heterogeneous crystal is precipitated at the time of firing, and the fluidity of the crystalline glass tends to be lowered.
Ａｓ２Ｏ３は、清澄剤として機能する成分であると共に、Ｆｅ２＋による青色着色を抑制する成分であり、その含有量は０〜１％、特に０〜０．５％が好ましい。Ａｓ２Ｏ３の含有量が１％より多いと、環境負荷が大きくなる。 As 2 O 3 is a component that functions as a fining agent and a component that suppresses blue coloring by Fe 2+ , and its content is preferably 0 to 1%, particularly preferably 0 to 0.5%. When the content of As 2 O 3 is more than 1%, the environmental load increases.
Ｓｂ２Ｏ３は、清澄剤として機能する成分であると共に、Ｆｅ２＋による青色着色を抑制する成分であり、その含有量は０〜１％、特に０〜０．５％が好ましい。Ｓｂ２Ｏ３の含有量が１％より多いと、環境負荷が大きくなる。 Sb 2 O 3 is a component that functions as a fining agent and a component that suppresses blue coloring by Fe 2+ , and its content is preferably 0 to 1%, particularly preferably 0 to 0.5%. When the content of Sb 2 O 3 is more than 1%, the environmental load increases.
なお、Ａｓ２Ｏ３＋Ｓｂ２Ｏ３（Ａｓ２Ｏ３とＳｂ２Ｏ３の合量）の含有量は０〜１％、特に０〜０．５％が好ましい。Ａｓ２Ｏ３＋Ｓｂ２Ｏ３の含有量が１％より多いと、環境負荷が大きくなる。 In addition, the content of As 2 O 3 + Sb 2 O 3 (the total amount of As 2 O 3 and Sb 2 O 3 ) is 0 to 1%, and particularly preferably 0 to 0.5%. When the content of As 2 O 3 + Sb 2 O 3 is more than 1%, the environmental load increases.
ＣｅＯ２は、清澄剤であるＡｓ２Ｏ３＋Ｓｂ２Ｏ３の含有量が０．１％以下の場合に、結晶化ガラスの白色度の低下を抑制する成分である。また、ＣｅＯ２は、還元雰囲気の溶融において、Ｆｅ２Ｏ３中のＦｅ２＋による青色着色を抑制する成分であり、特にＳＯ３（芒硝）と共存する場合にＦｅ２＋による青色着色を顕著に抑制する成分である。ＣｅＯ２の含有量は０〜０．５％、特に０．０５〜０．３％が好ましい。なお、組成中にＣｅＯ２を含む場合、ガラス原料として研磨スラッジを使用し易くなる。 CeO 2 is a component that suppresses a decrease in whiteness of the crystallized glass when the content of As 2 O 3 + Sb 2 O 3 as a fining agent is 0.1% or less. CeO 2 is a component that suppresses blue coloring due to Fe 2+ in Fe 2 O 3 in melting in a reducing atmosphere, and particularly suppresses blue coloring due to Fe 2+ when coexisting with SO 3 (sodium salt). It is an ingredient to do. The CeO 2 content is preferably 0 to 0.5%, particularly preferably 0.05 to 0.3%. In the case where in the composition containing CeO 2, easily use abrasive sludge as glass raw materials.
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％、特に０．０５〜０．３％が好ましい。ＳＯ３の含有量が０．５％より多いと、溶融ガラス中に気泡が発生し過ぎて、結晶化ガラス中に気泡が残留し易くなることに加えて、焼成時に硫化物系の異種結晶が析出して、結晶性ガラスの流動性が低下し易くなる。 SO 3 is a component that functions as a fining agent, and its content is preferably 0 to 0.5%, particularly preferably 0.05 to 0.3%. When the content of SO 3 is more than 0.5%, bubbles are generated too much in the molten glass, and the bubbles are likely to remain in the crystallized glass. It precipitates and the fluidity of the crystalline glass tends to decrease.
上記成分以外にも、例えば以下の成分を添加してもよい。 In addition to the above components, for example, the following components may be added.
Ｆｅ２Ｏ３は、着色成分であり、また不純物として混入する成分であり、その含有量は２０００ｐｐｍ以下、１０００ｐｐｍ以下、８００ｐｐｍ以下、特に５００ｐｐｍ以下が好ましい。Ｆｅ２Ｏ３の含有量が２０００ｐｐｍより多いと、結晶化ガラスの白色度が低下して、結晶化ガラスの拡散反射率が低下し易くなる。 Fe 2 O 3 is a coloring component and a component mixed as an impurity, and its content is preferably 2000 ppm or less, 1000 ppm or less, 800 ppm or less, and particularly preferably 500 ppm or less. When the content of Fe 2 O 3 is more than 2000 ppm, and reduced whiteness of the crystallized glass, diffuse reflectance of the crystallized glass is liable to decrease.
ＮｉＯは、着色成分であり、その含有量は１０００ｐｐｍ以下、８００ｐｐｍ以下、特に５００ｐｐｍ以下が好ましい。ＮｉＯの含有量が１０００ｐｐｍより多いと、結晶化ガラスの白色度が低下して、結晶化ガラスの拡散反射率が低下し易くなる。 NiO is a coloring component, and its content is preferably 1000 ppm or less, 800 ppm or less, and particularly preferably 500 ppm or less. When the content of NiO is more than 1000 ppm, the whiteness of the crystallized glass decreases, and the diffuse reflectance of the crystallized glass tends to decrease.
ＣｏＯは、着色成分であり、その含有量は１０００ｐｐｍ以下、８００ｐｐｍ以下、特に５００ｐｐｍ以下が好ましい。ＣｏＯの含有量が１０００ｐｐｍより多いと、結晶化ガラスの白色度が低下して、結晶化ガラスの拡散反射率が低下し易くなる。 CoO is a coloring component, and its content is preferably 1000 ppm or less, 800 ppm or less, and particularly preferably 500 ppm or less. When there is more content of CoO than 1000 ppm, the whiteness of crystallized glass will fall and the diffuse reflectance of crystallized glass will fall easily.
ＳｉＯ２＋Ａｌ２Ｏ３＋ＣａＯ＋Ｌｉ２Ｏ＋ＺｎＯ＋Ｂ２Ｏ３＋ＢａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｓｂ２Ｏ３＋ＣｅＯ２＋ＳＯ３＋Ｆｅ２Ｏ３＋ＮｉＯ＋ＣｏＯの含有量は９０〜９９．８％未満、特に９３〜９９％が好ましい。ＳｉＯ２＋Ａｌ２Ｏ３＋ＣａＯ＋Ｌｉ２Ｏ＋ＺｎＯ＋Ｂ２Ｏ３＋ＢａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｓｂ２Ｏ３＋ＣｅＯ２＋ＳＯ３＋Ｆｅ２Ｏ３＋ＮｉＯ＋ＣｏＯの含有量が９０％より少ないと、β−ウォラストナイト結晶が析出し難くなったり、表面のβ−ウォラストナイト結晶が粗大化し易くなる。一方、ＳｉＯ２＋Ａｌ２Ｏ３＋ＣａＯ＋Ｌｉ２Ｏ＋ＺｎＯ＋Ｂ２Ｏ３＋ＢａＯ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｓｂ２Ｏ３＋ＣｅＯ２＋ＳＯ３＋Ｆｅ２Ｏ３＋ＮｉＯ＋ＣｏＯの含有量が９９．８％以上であると、ガラス原料として、異種ガラスカレットを使用し難くなる。 The content of SiO 2 + Al 2 O 3 + CaO + Li 2 O + ZnO + B 2 O 3 + BaO + Na 2 O + K 2 O + Sb 2 O 3 + CeO 2 + SO 3 + Fe 2 O 3 + NiO + CoO is preferably 90 to 99.8%, particularly preferably 93 to 99%. When the content of SiO 2 + Al 2 O 3 + CaO + Li 2 O + ZnO + B 2 O 3 + BaO + Na 2 O + K 2 O + Sb 2 O 3 + CeO 2 + SO 3 + Fe 2 O 3 + NiO + CoO is less than 90%, β-wollastonite crystals are difficult to precipitate. Or β-wollastonite crystals on the surface are likely to be coarsened. On the other hand, if the content of SiO 2 + Al 2 O 3 + CaO + Li 2 O + ZnO + B 2 O 3 + BaO + Na 2 O + K 2 O + Sb 2 O 3 + CeO 2 + SO 3 + Fe 2 O 3 + NiO + CoO is 99.8% or more, different glass It becomes difficult to use cullet.
次に本発明の天然大理石様結晶化ガラス物品について説明する。なお、本発明の天然大理石様結晶化ガラス物品の成分組成は、本発明の天然大理石様結晶化ガラスの成分組成と同様である。ここでは、便宜上、成分組成に関する説明を省略する。 Next, the natural marble-like crystallized glass article of the present invention will be described. The component composition of the natural marble-like crystallized glass article of the present invention is the same as the component composition of the natural marble-like crystallized glass of the present invention. Here, for convenience, the description regarding the component composition is omitted.
本発明の天然大理石様結晶化ガラス物品において、表面のβ−ウォラストナイト結晶の最大粒径は８００μｍ以下、特に５００μｍ以下が好ましい。表面のβ−ウォラストナイト結晶の最大粒径が８００μｍより大きいと、結晶性ガラスの流動性が阻害されると共に、平滑な自由表面になり難いため、研磨効率を高め難くなる。結果として、表面のβ−ウォラストナイト結晶の最大粒径が８００μｍより大きいと、結晶化ガラス物品の製造コストが高騰し易くなる。 In the natural marble-like crystallized glass article of the present invention, the maximum particle size of β-wollastonite crystals on the surface is preferably 800 μm or less, particularly preferably 500 μm or less. When the maximum particle diameter of the β-wollastonite crystal on the surface is larger than 800 μm, the flowability of the crystalline glass is inhibited and it is difficult to obtain a smooth free surface, so that it is difficult to increase the polishing efficiency. As a result, when the maximum particle size of the surface β-wollastonite crystal is larger than 800 μm, the manufacturing cost of the crystallized glass article is likely to increase.
次に本発明の天然大理石様結晶化ガラス物品の製造方法について説明する。本発明の天然大理石様結晶化ガラス物品の製造方法は、組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含む複数の結晶性ガラス小体を耐火性容器内に収容した後、結晶性ガラス小体の軟化点より高い温度で熱処理することにより、結晶性ガラス小体の表面から主結晶として針状のβ−ウォラストナイト結晶を析出させながら、複数の結晶性ガラス小体を軟化変形させて互いに融着させることを特徴とする。なお、本発明の天然大理石様結晶化ガラス物品の製造方法における結晶性ガラス小体の成分組成は、本発明の天然大理石様結晶化ガラスの成分組成と同様である。ここでは、便宜上、成分組成に関する説明を省略する。 Next, the method for producing the natural marble-like crystallized glass article of the present invention will be described. The method for producing a natural marble-like crystallized glass article of the present invention has a composition of SiO 2 of 45 mass% or more, CaO of 7.5 mass% or more, ZnO of 0.05 mass% or more, and MgO + SrO + ZrO 2 of 0.1%. A plurality of crystalline glass bodies containing at least mass% are accommodated in a refractory container, and then subjected to heat treatment at a temperature higher than the softening point of the crystalline glass bodies, so that the needles from the surface of the crystalline glass bodies as main crystals. A plurality of crystalline glass bodies are softened and deformed and fused together while precipitating β-wollastonite crystals. The component composition of the crystalline glass body in the method for producing a natural marble-like crystallized glass article of the present invention is the same as the component composition of the natural marble-like crystallized glass of the present invention. Here, for convenience, the description regarding the component composition is omitted.
以下のようにして、結晶性ガラス小体を作製することができる。まず上記の組成になるようにガラス原料を調合し、ガラスバッチを作製する。次に、ガラスバッチを溶融炉に投入し、ガラスバッチを溶融する。続いて、得られた溶融ガラスを水砕等することにより、結晶性ガラス小体を作製する。なお、ガラス原料として、例えば珪砂、長石、スポジュメン、ガラスカレットを使用することができる。 A crystalline glass body can be produced as follows. First, glass raw materials are prepared so as to have the above composition, and a glass batch is prepared. Next, the glass batch is put into a melting furnace to melt the glass batch. Subsequently, the obtained molten glass is subjected to water granulation or the like to produce a crystalline glass body. In addition, as a glass raw material, for example, silica sand, feldspar, spodumene, and glass cullet can be used.
さらに、複数の結晶性ガラス小体を耐火性容器（型枠）内に集積した後、結晶性ガラス小体の軟化点より高い温度で熱処理すると、各結晶性ガラス小体の表面から内部に向かって針状のβ−ウォラストナイトが析出すると共に、各結晶性ガラス小体が融着一体化して、天然大理石様結晶化ガラス物品を得ることができる。 Furthermore, after a plurality of crystalline glass bodies are accumulated in a refractory container (form), heat treatment is performed at a temperature higher than the softening point of the crystalline glass bodies. Thus, acicular β-wollastonite precipitates and the crystalline glass bodies are fused and integrated to obtain a natural marble-like crystallized glass article.
本発明の天然大理石様結晶化ガラス物品の製造方法において、自由表面の表面粗さＲａが１μｍ以下、特に０．８μｍ以下になるように、複数の結晶性ガラス小体を軟化変形させて互いに融着させることが好ましい。天然大理石様結晶化ガラス物品は、通常、研磨、サンドブラスト、エッチング等により表面処理されている。特に、結晶化ガラスの表面を鏡面研磨する場合、自由表面の表面粗さＲａが重要になり、自由表面の表面粗さＲａが１μｍより大きいと、研磨効率が低下し易くなり、結晶化ガラス物品の製造コストが高騰し易くなる。 In the method for producing a natural marble-like crystallized glass article according to the present invention, a plurality of crystalline glass particles are softened and deformed so that the surface roughness Ra of the free surface is 1 μm or less, particularly 0.8 μm or less. It is preferable to wear. Natural marble-like crystallized glass articles are usually surface treated by polishing, sandblasting, etching or the like. In particular, when the surface of the crystallized glass is mirror-polished, the surface roughness Ra of the free surface is important. If the surface roughness Ra of the free surface is greater than 1 μm, the polishing efficiency tends to decrease, and the crystallized glass article The manufacturing cost is likely to rise.
本発明の天然大理石様結晶化ガラス物品の製造方法において、焼成時に結晶性ガラス小体中の非晶質ガラスの含有量が５０〜９５質量％になるように調整することが好ましい。このようにすれば、結晶性ガラス小体の表面から主結晶として針状のβ−ウォラストナイト結晶を析出させながら、結晶性ガラス小体を軟化変形させ易くなる。非晶質ガラスの含有量が５０質量％より少ないと、流動に寄与しない結晶成分の量が多くなり、流動不足が発生し易くなる。一方、非晶質ガラスの含有量が９５質量％より多いと、β−ウォラストナイト結晶の析出量が少なくなり、焼成時に粒界に存在する泡が上昇して、結晶化ガラス物品中に泡が残存し易くなる。 In the method for producing a natural marble-like crystallized glass article of the present invention, it is preferable to adjust so that the amorphous glass content in the crystalline glass body is 50 to 95% by mass during firing. This makes it easier to soften and deform the crystalline glass body while precipitating acicular β-wollastonite crystals as main crystals from the surface of the crystalline glass body. When the content of the amorphous glass is less than 50% by mass, the amount of the crystal component that does not contribute to the flow increases and the flow shortage tends to occur. On the other hand, if the content of the amorphous glass is more than 95% by mass, the amount of β-wollastonite crystals precipitated decreases, and the bubbles present at the grain boundaries rise during firing, and bubbles are formed in the crystallized glass article. Tends to remain.
本発明の天然大理石様結晶化ガラス物品の製造方法において、結晶性ガラス小体のガラス原料として、ＭｇＯ、ＳｒＯ、ＺｒＯ２のいずれかを含むガラスカレットを用いることが好ましい。ガラス原料として、ＭｇＯ、ＳｒＯ、ＺｒＯ２のいずれかを含むガラスカレットを使用すれば、原料コストと溶融コストを低下することができる。但し、ガラスカレット中のＭｇＯ、ＳｒＯ、ＺｒＯ２の含有量は、カレットの種類により変化する。 In the method for producing a natural marble-like crystallized glass article of the present invention, it is preferable to use a glass cullet containing any of MgO, SrO, and ZrO 2 as a glass raw material of the crystalline glass body. If a glass cullet containing any of MgO, SrO, and ZrO 2 is used as the glass raw material, the raw material cost and the melting cost can be reduced. However, the contents of MgO, SrO, and ZrO 2 in the glass cullet vary depending on the type of cullet.
本発明の天然大理石様結晶化ガラス物品の製造方法において、ガラスカレットとして、窓板ガラスのガラスカレット、ビンガラスのガラスカレット、ディスプレイ用ガラスのガラスカレットのいずれかを含むことが好ましい。これらのガラスカレットは、流通量が多いため、価格が安く、またリサイクルの必要性が高い。 In the method for producing a natural marble-like crystallized glass article of the present invention, the glass cullet preferably contains any of glass cullet of window glass, glass cullet of bottle glass, and glass cullet of display glass. Since these glass cullet has a large distribution volume, the price is low and the necessity for recycling is high.
窓板ガラスのガラスカレットの組成は、一般的に、質量％で、ＳｉＯ２ ７１％、Ａｌ２Ｏ３ ２％、ＣａＯ ９％、ＭｇＯ ４％、Ｎａ２Ｏ １３％、Ｋ２Ｏ １％である。 The composition of the glass cullet of the window glass is generally SiO 2 71%, Al 2 O 3 2%, CaO 9%, MgO 4%, Na 2 O 13%, K 2 O 1% by mass%. .
ビンガラスのガラスカレットの組成は、一般的に、質量％で、ＳｉＯ２ ７２％、Ａｌ２Ｏ３ ２％、ＣａＯ １１％、ＭｇＯ １％、Ｎａ２Ｏ １３％、Ｋ２Ｏ １％である。 The composition of the glass cullet of Bingarasu typically, in mass%, SiO 2 72%, Al 2 O 3 2%, CaO 11%, MgO 1%, Na 2 O 13%, a K 2 O 1%.
液晶ディスプレイ用ガラスのガラスカレットの組成は、一般的に、質量％で、ＳｉＯ２ ５０％以上、Ａｌ２Ｏ３ １０〜２０％、Ｂ２Ｏ３ ５〜２０％、ＭｇＯ＋ＳｒＯ＋ＣａＯ＋ＢａＯ＋ＺｎＯ ５〜２０％、ＺｒＯ２ ０〜３％であり、実質的にアルカリ金属酸化物を含有していない。 The composition of the glass cullet of LCD glass, typically, in mass%, SiO 2 50% or more, Al 2 O 3 10~20%, B 2 O 3 5~20%, MgO + SrO + CaO + BaO + 5~20% ZnO, ZrO It is 20 to 3% and does not substantially contain an alkali metal oxide.
プラズマディスプレイ用ガラスのガラスカレットの組成は、一般的に、質量％で、ＳｉＯ２ ５０％以上、Ａｌ２Ｏ３ １０〜２０％、Ｂ２Ｏ３ ５〜２０％、ＭｇＯ＋ＳｒＯ＋ＣａＯ＋ＢａＯ ５〜２０％、ＺｒＯ２ ０〜３％である。 The composition of the glass cullet of glass for plasma display, typically, in mass%, SiO 2 50% or more, Al 2 O 3 10~20%, B 2 O 3 5~20%, MgO + SrO + CaO + BaO 5~20%, ZrO it is a 2 0-3%.
本発明の天然大理石様結晶化ガラス物品の製造方法において、１０４．０Ｐａ・ｓにおけるガラスカレットの温度をＴ１、１０４．０Ｐａ・ｓにおける結晶性ガラスの温度をＴ２としたとき、｜Ｔ１−Ｔ２｜≦２００℃、特に｜Ｔ１−Ｔ２｜≦１５０℃の関係を満たすガラスカレットを用いることが好ましい。｜Ｔ１−Ｔ２｜＞２００℃であると、溶融分離が生じ易くなる。 The method of manufacturing a natural marble-like crystallized glass article of the present invention, when the temperature of the crystallizable glass temperature of the glass cullet in 10 4.0 Pa · s at T 1, 10 4.0 Pa · s was T 2 , | T 1 −T 2 | ≦ 200 ° C., in particular, glass cullet satisfying the relationship of | T 1 −T 2 | ≦ 150 ° C. is preferably used. If | T 1 −T 2 |> 200 ° C., melt separation tends to occur.
本発明の天然大理石様結晶化ガラス物品の製造方法において、ガラスカレットの平均粒径は５０ｍｍ以下、特に３０ｍｍ以下が好ましい。また、｜Ｔ１−Ｔ２｜＞２００℃の関係を満たす場合、ガラスカレットの平均粒径は１０ｍｍ以下、特に５ｍｍ以下が好ましい。このようにすれば、溶融分離を防止し易くなる。 In the method for producing a natural marble-like crystallized glass article of the present invention, the average particle size of the glass cullet is preferably 50 mm or less, particularly preferably 30 mm or less. Moreover, | T 1 -T 2 |> 200 if it meets ℃ relations, the average particle size of the glass cullet 10mm or less, especially 5mm or less. This makes it easy to prevent melt separation.
以下、実施例に基づいて、本発明を説明する。なお、以下の実施例は単なる例示である。本発明は、これらの実施例に何ら限定されない。 Hereinafter, the present invention will be described based on examples. The following examples are merely illustrative. The present invention is not limited to these examples.
表１〜３は、本発明の実施例（試料Ｎｏ．１〜２６）及び比較例（試料Ｎｏ．２７、２８）を示している。 Tables 1 to 3 show examples of the present invention (sample Nos. 1 to 26) and comparative examples (samples No. 27 and 28).
次のようにして、試料Ｎｏ．１〜２８を調製した。まず表中の組成になるように珪砂、長石、酸化アルミ又は水酸化アルミニウム、炭酸カルシウム、炭酸バリウム、ソーダ灰、炭酸カリウム、スポジュメン又は炭酸リチウム、硝酸ソーダ、酸化アンチモン、及び各種ガラスカレットを調合し、ガラスバッチを作製した（但し、ガラスカレットの含有量を同一とした）。次に、ガラスバッチを白金坩堝に投入し、１５５０℃で５時間溶融した。続いて、得られた溶融ガラスを水砕し、乾燥、分級して粒径１〜５ｍｍの結晶性ガラス小体を得た。さらに、複数の結晶性ガラス小体を、内壁にアルミナ粉が塗布された耐火性容器内に集積し、これを電気炉内に投入した後、１２０℃／Ｈｒの速度で昇温し、表中の焼成温度で１時間保持することにより、各結晶性ガラス小体を軟化変形させて互いに融着させると共に、結晶化させた。なお、各試料間で融着状態が同一になるように、焼成温度を調整した。 Sample no. 1-28 were prepared. First, silica sand, feldspar, aluminum oxide or aluminum hydroxide, calcium carbonate, barium carbonate, soda ash, potassium carbonate, spodumene or lithium carbonate, sodium nitrate, antimony oxide, and various glass cullet are prepared so as to have the composition in the table. A glass batch was prepared (however, the glass cullet content was the same). Next, the glass batch was put into a platinum crucible and melted at 1550 ° C. for 5 hours. Subsequently, the obtained molten glass was crushed, dried and classified to obtain a crystalline glass body having a particle diameter of 1 to 5 mm. Further, a plurality of crystalline glass bodies are accumulated in a refractory container whose inner wall is coated with alumina powder, and this is put into an electric furnace, and then heated at a rate of 120 ° C./Hr. The crystalline glass bodies were softened and deformed to be fused with each other and crystallized by holding at the firing temperature of 1 hour. The firing temperature was adjusted so that the fused state was the same between the samples.
各試料につき、主結晶、表面粗さＲａ、最大粒径、色調Ｌ＊を評価した。その結果を表１、２に示す。 For each sample, the main crystal, surface roughness Ra, maximum particle size, and color tone L * were evaluated. The results are shown in Tables 1 and 2.
Ｘ線回折装置により主結晶を同定した。なお、表中においてβ−ウォラストナイト結晶を「β−Ｗ」と表記した。 The main crystal was identified by an X-ray diffractometer. In the table, β-wollastonite crystal was expressed as “β-W”.
表面粗さＲａは、表面粗さ計（東京精密株式会社製）で測定した値である。 The surface roughness Ra is a value measured with a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.).
最大粒径は、各試料の表面をＳＥＭで測定した値である。 The maximum particle size is a value obtained by measuring the surface of each sample with an SEM.
色調Ｌ＊は、色差計（ジューキ株式会社製ＪＰ−７２００）により、反射による色調Ｌ＊値を測定したものである。 The color tone L * is obtained by measuring the color tone L * value by reflection with a color difference meter (JP-7200 manufactured by Juki Corporation).
表１〜３から明らかなように、試料Ｎｏ．１〜２６は、ＳｉＯ２、ＣａＯ、ＺｎＯ、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を所定量含んでいるため、焼成温度が１１００℃以下、表面粗さＲａが０．８μｍ以下、色調Ｌ＊が８４以上であった。 As is apparent from Tables 1 to 3, sample No. 1 to 26 contained SiO 2 , CaO, ZnO, MgO + SrO + ZrO 2 in predetermined amounts, so that the firing temperature was 1100 ° C. or less, the surface roughness Ra was 0.8 μm or less, and the color tone L * was 84 or more.
一方、表３から明らかなように、試料Ｎｏ．２７、２８は、焼成温度が高く、表面粗さＲａや最大粒径が大きかった。なお、試料Ｎｏ．２７、２８は、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を含んでいないため、ガラス原料として、窓板ガラス等の異種ガラスカレットを使用し難いと考えられる。 On the other hand, as apparent from Table 3, the sample No. In Nos. 27 and 28, the firing temperature was high, and the surface roughness Ra and the maximum particle size were large. Sample No. Since 27 and 28 do not contain MgO + SrO + ZrO 2 , it is considered difficult to use dissimilar glass cullet such as window glass as a glass raw material.
表１の試料Ｎｏ．１の組成になるように珪砂、長石、酸化アルミ又は水酸化アルミニウム、炭酸カルシウム、炭酸バリウム、ソーダ灰、炭酸カリウム、スポジュメン又は炭酸リチウム、硝酸ソーダ、酸化アンチモン、窓板ガラス又は液晶ディスプレイ用ガラスのガラスカレットを調合し、ガラスバッチを作製した。１０４．０Ｐａ・ｓにおけるガラスカレットの温度をＴ１、１０４．０Ｐａ・ｓにおける結晶性ガラスの温度をＴ２としたとき、｜Ｔ１−Ｔ２｜＝１００℃、２５０℃の関係を満たすガラスカレットを使用した。なお、ガラスバッチ中のガラスカレットの比率を１０質量％とした。次に、得られたガラスバッチを白金製三角坩堝に投入し、１５５０℃で１時間溶融した後、急冷して、得られた結晶性ガラスを白金製三角坩堝から除去した。 Sample No. in Table 1 Silica sand, feldspar, aluminum oxide or aluminum hydroxide, calcium carbonate, barium carbonate, soda ash, potassium carbonate, spodumene or lithium carbonate, sodium nitrate, antimony oxide, window glass or glass for liquid crystal display A cullet was prepared to prepare a glass batch. When the temperature of the glass cullet at 10 4.0 Pa · s is T 1 and the temperature of the crystalline glass at 10 4.0 Pa · s is T 2 , | T 1 −T 2 | = 100 ° C., 250 ° C. A glass cullet that satisfies the relationship was used. In addition, the ratio of the glass cullet in a glass batch was 10 mass%. Next, the obtained glass batch was put into a platinum triangular crucible, melted at 1550 ° C. for 1 hour, and then rapidly cooled to remove the obtained crystalline glass from the platinum triangular crucible.
得られた結晶性ガラスの上部（溶融ガラスの液面上部に相当する部分）を切り出し、アルキメデス法で密度を測定すると共に、断面状態を観察した。 The upper part of the obtained crystalline glass (the part corresponding to the liquid surface upper part of the molten glass) was cut out, the density was measured by the Archimedes method, and the cross-sectional state was observed.
｜Ｔ１−Ｔ２｜＝１００℃の関係を満たすガラスカレットを用いた場合、固体結晶原料のみで作製した結晶性ガラスの密度と同様であった。しかし、｜Ｔ１−Ｔ２｜＝２５０℃の関係を満たすガラスカレットを用いた場合、固体結晶原料のみで作製した結晶性ガラスの密度より約０．１５ｇ／ｃｍ３低かった。 When the glass cullet satisfying the relationship of | T 1 −T 2 | = 100 ° C. was used, the density was the same as the density of the crystalline glass produced using only the solid crystal raw material. However, when glass cullet satisfying the relationship of | T 1 −T 2 | = 250 ° C. was used, the density was about 0.15 g / cm 3 lower than the density of the crystalline glass produced only from the solid crystal raw material.
図１（Ａ）、（Ｂ）から明らかなように、｜Ｔ１−Ｔ２｜＝１００℃の関係を満たすガラスカレットを用いた場合、相分離は認められなかったが、｜Ｔ１−Ｔ２｜＝２５０℃の関係を満たすガラスカレットを用いた場合、ガラスカレットが上方に偏在していた。 As is clear from FIGS. 1A and 1B, when glass cullet satisfying the relationship of | T 1 −T 2 | = 100 ° C. was used, phase separation was not observed, but | T 1 −T When the glass cullet satisfying the relationship of 2 | = 250 ° C. was used, the glass cullet was unevenly distributed upward.
本発明の天然大理石様結晶化ガラス及び天然大理石様結晶化ガラス物品は、建築物の内装材や外装材以外にも、厨房・テーブルトップの内装材や外装材にも使用可能である。 The natural marble-like crystallized glass and natural marble-like crystallized glass article of the present invention can be used for interior materials and exterior materials for kitchens and tabletops in addition to interior materials and exterior materials for buildings.
Claims (16)
組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含むことを特徴とする天然大理石様結晶化ガラス物品。 A natural marble-like crystallized glass article formed by fusing together a plurality of crystallized glass subregions in which acicular β-wollastonite crystals are precipitated from the surface toward the inside,
Natural marble-like crystallized glass comprising, as a composition, SiO 2 of 45% by mass or more, CaO of 7.5% by mass or more, ZnO of 0.05% by mass or more, and MgO + SrO + ZrO 2 of 0.1% by mass or more. Goods.
組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上、Ｌｉ２Ｏを０．０５質量％以上１質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含むことを特徴とする天然大理石様結晶化ガラス物品。 A natural marble-like crystallized glass article formed by fusing together a plurality of crystallized glass subregions in which acicular β-wollastonite crystals are precipitated from the surface toward the inside,
As a composition, SiO 2 is 45 mass% or more, CaO is 7.5 mass% or more, ZnO is 0.05 mass% or more, Li 2 O is 0.05 mass% or more and less than 1 mass%, MgO + SrO + ZrO 2 is 0.1 mass%. A natural marble-like crystallized glass article characterized by containing at least mass%.
組成として、ＳｉＯ２を４５質量％以上、ＣａＯを７．５質量％以上、ＺｎＯを０．０５質量％以上６質量％未満、Ｎａ２Ｏ＋Ｋ２Ｏを３．８質量％以上１０質量％未満、ＭｇＯ＋ＳｒＯ＋ＺｒＯ２を０．１質量％以上含むことを特徴とする天然大理石様結晶化ガラス物品。 A natural marble-like crystallized glass article formed by fusing together a plurality of crystallized glass subregions in which acicular β-wollastonite crystals are precipitated from the surface toward the inside,
A composition, a SiO 2 45% by mass or more, CaO 7.5 wt% or more, ZnO less than 0.05 mass% to 6 mass%, Na 2 O + K 2 O less than 3.8 wt% to 10 wt%, A natural marble-like crystallized glass article comprising 0.1% by mass or more of MgO + SrO + ZrO 2 .
｜Ｔ１−Ｔ２｜≦２００℃の関係を満たすガラスカレットを用いることを特徴とする請求項１４又は１５に記載の天然大理石様結晶化ガラス物品の製造方法。 When the temperature of the glass cullet at 10 4.0 Pa · s is T 1 and the temperature of the crystalline glass at 10 4.0 Pa · s is T 2 ,
The method for producing a natural marble-like crystallized glass article according to claim 14 or 15, wherein a glass cullet satisfying a relationship of | T 1 -T 2 | ≦ 200 ° C. is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011104805A JP5737620B2 (en) | 2010-06-17 | 2011-05-10 | Natural marble-like crystallized glass, natural marble-like crystallized glass article and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010138549 | 2010-06-17 | ||
| JP2010138549 | 2010-06-17 | ||
| JP2011104805A JP5737620B2 (en) | 2010-06-17 | 2011-05-10 | Natural marble-like crystallized glass, natural marble-like crystallized glass article and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012020922A true JP2012020922A (en) | 2012-02-02 |
| JP5737620B2 JP5737620B2 (en) | 2015-06-17 |
Family
ID=45775500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011104805A Active JP5737620B2 (en) | 2010-06-17 | 2011-05-10 | Natural marble-like crystallized glass, natural marble-like crystallized glass article and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5737620B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115959830A (en) * | 2021-10-08 | 2023-04-14 | 湖州大享玻璃制品有限公司 | SiO (silicon dioxide) 2 Crystallized glass of-CaO system and method for producing same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03164446A (en) * | 1989-11-24 | 1991-07-16 | Asahi Glass Co Ltd | Production of crystallized glass |
| JPH04154645A (en) * | 1990-10-16 | 1992-05-27 | Asahi Glass Co Ltd | Production of crystallized glass |
| JPH06247744A (en) * | 1992-05-11 | 1994-09-06 | Nippon Electric Glass Co Ltd | Marble-like crystallized glass |
| JPH09132429A (en) * | 1995-11-02 | 1997-05-20 | Nippon Electric Glass Co Ltd | Crystallized glass article and its production |
| JPH1025133A (en) * | 1996-07-09 | 1998-01-27 | Nippon Electric Glass Co Ltd | Sintered and crystallized glass article and its production |
| JPH10297930A (en) * | 1997-04-24 | 1998-11-10 | Nippon Electric Glass Co Ltd | Finishing material of crystallized glass for building |
| JP2009073726A (en) * | 2007-08-28 | 2009-04-09 | Nippon Electric Glass Co Ltd | Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and its manufacturing method |
-
2011
- 2011-05-10 JP JP2011104805A patent/JP5737620B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03164446A (en) * | 1989-11-24 | 1991-07-16 | Asahi Glass Co Ltd | Production of crystallized glass |
| JPH04154645A (en) * | 1990-10-16 | 1992-05-27 | Asahi Glass Co Ltd | Production of crystallized glass |
| JPH06247744A (en) * | 1992-05-11 | 1994-09-06 | Nippon Electric Glass Co Ltd | Marble-like crystallized glass |
| JPH09132429A (en) * | 1995-11-02 | 1997-05-20 | Nippon Electric Glass Co Ltd | Crystallized glass article and its production |
| JPH1025133A (en) * | 1996-07-09 | 1998-01-27 | Nippon Electric Glass Co Ltd | Sintered and crystallized glass article and its production |
| JPH10297930A (en) * | 1997-04-24 | 1998-11-10 | Nippon Electric Glass Co Ltd | Finishing material of crystallized glass for building |
| JP2009073726A (en) * | 2007-08-28 | 2009-04-09 | Nippon Electric Glass Co Ltd | Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and its manufacturing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115959830A (en) * | 2021-10-08 | 2023-04-14 | 湖州大享玻璃制品有限公司 | SiO (silicon dioxide) 2 Crystallized glass of-CaO system and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5737620B2 (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5779296B2 (en) | Glass composition, glass composition for chemical strengthening, tempered glass article, and cover glass for display | |
| CN103249688B (en) | The not general glass of boracic | |
| KR101343767B1 (en) | Boron-free glass | |
| KR101153751B1 (en) | Method for production of non-alkaline glass | |
| JP5267464B2 (en) | Method for producing alkali-free glass | |
| JP7421171B2 (en) | glass | |
| JP2001048573A (en) | Non-alkali aluminoborosilicate glass, its use and its production | |
| WO2016017558A1 (en) | High-transparency glass | |
| JP2013193887A (en) | Glass composition, glass composition for chemical strengthening, strengtheneded glass product, cover glass for display and method for producing strengthened glass product | |
| CN102781864A (en) | Process for production of LAS-system crystalline glass | |
| JP2021063010A (en) | Glass | |
| CN1944300B (en) | Low expansion coefficient micro crystal glass and its heat processing method | |
| JP2013063870A (en) | Method for producing silicate glass | |
| CN102515524A (en) | Boroaluminosilicate glass substrate and preparation method thereof | |
| JP2016074598A (en) | Manufacturing method of silicate glass | |
| JP5737620B2 (en) | Natural marble-like crystallized glass, natural marble-like crystallized glass article and method for producing the same | |
| WO2011158616A1 (en) | Natural marble-like crystallised glass, natural marble-like crystallised glass products and production method therefor | |
| JPWO2017110927A1 (en) | Mixed raw material for silicate glass and method for producing tube glass using the same | |
| JP2013107801A (en) | Method for producing glass substrate | |
| JP3269416B2 (en) | Crystallized glass and method for producing the same | |
| JP2009073726A (en) | Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and its manufacturing method | |
| JP5943502B2 (en) | Method for producing natural marble-like crystallized glass | |
| WO2021117360A1 (en) | Method for producing alkaline earth aluminoborosilicate glass | |
| JP2007077001A (en) | Natural marble-like crystallized glass and process for production thereof | |
| JP6562240B2 (en) | Manufacturing method of silicate glass and silica raw material for silicate glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140401 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140827 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140828 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141017 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150327 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150409 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5737620 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |