JP7460947B2 - Crystallized glass, crystallized glass, and method for producing crystallized glass - Google Patents
Crystallized glass, crystallized glass, and method for producing crystallized glass Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims description 182
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002932 luster Substances 0.000 claims description 43
- 239000013078 crystal Substances 0.000 claims description 27
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910000500 β-quartz Inorganic materials 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000005354 aluminosilicate glass Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 24
- 229910052723 transition metal Inorganic materials 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 9
- 239000006121 base glass Substances 0.000 description 7
- 238000013461 design Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052644 β-spodumene Inorganic materials 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- -1 and in particular Substances 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000006018 Li-aluminosilicate Substances 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003426 chemical strengthening reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
- Glass Compositions (AREA)
Description
本発明は、結晶化ガラス、特に表面に金属光沢を有する結晶化ガラスに関する。 The present invention relates to crystallized glass, particularly crystallized glass having a metallic luster on the surface.
従来、金属光沢などの意匠性を有するガラス物品を得る方法としては、例えば、特許文献１及び２に記載のように、スパッタを用いてガラスに金属膜を被覆する方法が知られている。 BACKGROUND ART Conventionally, as a method of obtaining a glass article having a design such as metallic luster, a method of coating glass with a metal film using sputtering is known, for example, as described in Patent Documents 1 and 2.
しかし、大面積のガラス板にスパッタ方式で金属膜を被覆する場合は、ムラや膜剥がれなどが生じやすい。また、スパッタのための大型装置が必要となり製造コストが高くなりやすいという問題がある。 However, when a large-area glass plate is coated with a metal film by sputtering, unevenness and film peeling are likely to occur. Another problem is that a large sputtering device is required, which tends to increase manufacturing costs.
本発明は、金属膜を被覆させずとも金属光沢を有し、優れた意匠性を有する結晶化ガラスを提供することを目的とする。 An object of the present invention is to provide crystallized glass that has metallic luster and excellent design without being coated with a metal film.
本発明者は、鋭意検討した結果、結晶化ガラスに第一遷移金属酸化物を所定量含有させ、更に、結晶化度を規制することにより、結晶化ガラスの表面に金属光沢を発現させることができることを突き止め、本発明を提案するに至った。 As a result of extensive studies, the present inventor has discovered that it is possible to develop metallic luster on the surface of crystallized glass by containing a predetermined amount of a first transition metal oxide in crystallized glass and further regulating the degree of crystallinity. We have discovered what is possible and have proposed the present invention.
本発明者が見出した機構は以下の通りである。第一遷移金属酸化物を所定量含んだ結晶性ガラスを、一定結晶化度以上に結晶化させると、結晶化ガラス中の結晶に固溶しにくい第一遷移金属イオンは、結晶化ガラス中のガラスマトリックス中に濃縮されると考えられる。そして、濃縮された第一遷移金属イオンは、ガラスマトリックスとともに結晶化ガラスの表面に移行し、その結果、金属リッチな表面層が形成され、結晶化ガラスの表面に金属光沢が発現すると考えられる。 The mechanism discovered by the present inventor is as follows. When a crystalline glass containing a predetermined amount of a first transition metal oxide is crystallized to a certain degree of crystallinity or higher, the first transition metal ions, which are difficult to dissolve in the crystals in the crystallized glass, are dissolved in the crystallized glass. It is believed to be concentrated in the glass matrix. It is thought that the concentrated first transition metal ions migrate to the surface of the crystallized glass together with the glass matrix, and as a result, a metal-rich surface layer is formed and a metallic luster appears on the surface of the crystallized glass.
なお、一般的に遷移金属元素とは、周期表で第３～１１族元素の間に存在する元素の総称のことであり、第４周期に存在する遷移金属元素を第一遷移金属元素という。また遷移金属元素の中でも第４族元素については、結晶に固溶したりして表面の金属光沢に寄与しにくい。そのため、本発明では、遷移金属元素として、これらの元素（具体的には、Ｔｉ、Ｚｒ、Ｈｆ、Ｒｆ）を除いた元素を対象とする。 In general, transition metal elements are a general term for elements that exist between Groups 3 and 11 in the periodic table, and transition metal elements that exist in the fourth period are called first transition metal elements. Among transition metal elements, Group 4 elements are less likely to contribute to the metallic luster of the surface by forming solid solutions in crystals. For this reason, the present invention targets transition metal elements excluding these elements (specifically, Ti, Zr, Hf, and Rf).
すなわち、本発明の結晶化ガラスは、外掛けの質量％で、第４族を除く第一遷移金属酸化物を１超～１０％含有し、結晶化度が７０％以上であることを特徴とする。 In other words, the crystallized glass of the present invention is characterized by containing, in terms of mass percent by weight, more than 1 to 10% of a first transition metal oxide excluding Group 4, and having a degree of crystallinity of 70% or more.
また、本発明の結晶化ガラスは、アルミノシリケートガラスであることが好ましい。 The crystallized glass of the present invention is preferably an aluminosilicate glass.
また、本発明の結晶化ガラスは、質量％で、ＳｉＯ２ ５０～８０％、Ａｌ２Ｏ３ １０～２５％、Ｌｉ２Ｏ ０．１～２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～１０％であることが好ましい。 The crystallized glass of the present invention preferably contains, in mass %, SiO 2 50-80%, Al 2 O 3 10-25%, Li 2 O 0.1-20%, and MgO+CaO+SrO+BaO+ZnO 0-10%.
更に、本発明の結晶化ガラスは、質量％で、ＴｉＯ２ ０．１～５％、ＺｒＯ２ ０．１～５％含有することが好ましい。 Further, the crystallized glass of the present invention preferably contains TiO 2 0.1 to 5% and ZrO 2 0.1 to 5% in mass %.
また、本発明の結晶化ガラスは、前記第一遷移金属酸化物が、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯから選択される一種類以上であることが好ましい。 In the crystallized glass of the present invention, the first transition metal oxide is preferably one or more selected from the group consisting of Fe 2 O 3 , CoO, NiO and CuO.
このようにすれば、金属光沢を有する結晶化ガラスを得やすくなる。 This makes it easier to obtain crystallized glass with metallic luster.
また、本発明の結晶化ガラスは、主結晶が、βクォーツであることが好ましい。 In addition, it is preferable that the main crystal of the crystallized glass of the present invention is β-quartz.
このようにすれば、結晶化ガラス本体に透光性を付与することができる。その結果、金属光沢を有し且つガラスの透光性を併せ持つ意匠性の高いガラス物品を得ることが可能になる。 In this way, translucency can be imparted to the crystallized glass body. As a result, it becomes possible to obtain a highly designed glass article that has metallic luster and the translucency of glass.
また、本発明の結晶化ガラスは、金属光沢を有することが好ましい。 The crystallized glass of the present invention preferably has a metallic luster.
また、本発明の結晶化ガラスは、表面抵抗率が、８Ω・ｃｍ以下であることが好ましい。 The crystallized glass of the present invention preferably has a surface resistivity of 8 Ω·cm or less.
このようにすれば、膜抵抗器として使用することができる。 In this way, it can be used as a film resistor.
本発明の結晶化ガラスは、結晶化ガラスが、ガラス本体とその表面に形成された金属光沢層を有し、金属光沢層の表面抵抗率が、ガラス本体の表面抵抗率と異なることが好ましい。なお、本発明においてガラス本体とは、少なくとも金属光沢層を完全に取り除いたガラスのことを指し、より具体的には、研磨等により表面から５００μｍ（０．５ｍｍ）以上の厚みの層を除去したガラスを指す。 The crystallized glass of the present invention preferably has a glass body and a metallic gloss layer formed on its surface, and the surface resistivity of the metallic gloss layer is different from the surface resistivity of the glass body. In the present invention, the glass body refers to glass from which at least the metallic gloss layer has been completely removed, and more specifically, refers to glass from which a layer of 500 μm (0.5 mm) or more in thickness has been removed from the surface by polishing or the like.
本発明の結晶化ガラスは、金属光沢層の表面抵抗率が、ガラス本体の表面抵抗率に比べて０．５Ω・ｃｍ以上低いことが好ましい。 In the crystallized glass of the present invention, it is preferable that the surface resistivity of the metallic luster layer is at least 0.5 Ω·cm lower than the surface resistivity of the glass body.
本発明の結晶性ガラスは、前記結晶化ガラスの前駆体であって、外掛けの質量％で、第４族を除く第一遷移金属酸化物を１超～１０％含有することが好ましい。 The crystallizable glass of the present invention is a precursor of the crystallized glass, and preferably contains, in terms of mass percent by weight, more than 1 to 10% of a first transition metal oxide excluding Group 4.
本発明の結晶化ガラスの製造方法は、前記結晶性ガラスを７００～１０００℃の熱処理に供することにより結晶化させることを特徴とする。 The method for producing crystallized glass of the present invention is characterized in that the crystallized glass is crystallized by subjecting it to heat treatment at 700 to 1000°C.
本発明によれば、スパッタ方式等で金属膜を被覆させずとも金属光沢を有し、優れた意匠性を有する結晶化ガラスを得ることが可能になる。また、スパッタ方式を用いないので、ムラや膜剥がれなどが生じにくい。更に、スパッタのために大型装置が必要ないため、製造コストや手間を低減できる。 According to the present invention, it is possible to obtain crystallized glass that has a metallic luster and excellent design properties without coating it with a metal film using a sputtering method or the like. In addition, since no sputtering method is used, unevenness and film peeling are unlikely to occur. Furthermore, since no large equipment is required for sputtering, manufacturing costs and labor can be reduced.
本発明の結晶化ガラスは、第４族を除く第一遷移金属酸化物を含有する。本発明において、第４族、すなわちＴｉＯ２を除く第一遷移金属酸化物（以降、第一遷移金属酸化物と称する）の含有量は、ベースガラスに対して、外掛けの質量％で、１超～１０％であり、１．２～９％、１．４～８．５％、１．６～８％、１．８～７．５％、１．９～７％、２～６％、特に２．２～５％が好ましい。第一遷移金属酸化物の含有量が少なすぎると、結晶化ガラスの表面に金属光沢を発現させにくくなる。一方、第一遷移金属酸化物の含有量が多すぎると、結晶化ガラスの前駆体である結晶性ガラスが不均質になったり、ガラス化が困難になったりして、生産性が低下する虞がある。 The crystallized glass of the present invention contains a first transition metal oxide excluding a group 4 metal oxide. In the present invention, the content of Group 4, that is, the first transition metal oxide excluding TiO2 (hereinafter referred to as the first transition metal oxide) is 1% by mass relative to the base glass. >10%, 1.2-9%, 1.4-8.5%, 1.6-8%, 1.8-7.5%, 1.9-7%, 2-6% , particularly preferably 2.2 to 5%. If the content of the first transition metal oxide is too small, it will be difficult to develop metallic luster on the surface of the crystallized glass. On the other hand, if the content of the first transition metal oxide is too high, the crystalline glass, which is the precursor of crystallized glass, may become inhomogeneous or difficult to vitrify, which may reduce productivity. There is.
ところで、本発明の結晶化ガラスにおいて、第二～四遷移金属元素は表面の金属光沢に影響しにくいため、第４族を除く第二～四遷移金属酸化物（以降、第二～四遷移金属酸化物と称する）の含有量は限定されない。ただし、遷移金属元素はガラスを着色し易い成分であるため、ガラスの着色を低減する観点では、第二～四遷移金属酸化物の含有量を規制してもよい。その場合、第二～四遷移金属酸化物の含有量は、ベースガラスに対して、外掛けの質量％で、好ましくは０～１０％であり、好ましくは０．１～８％、より好ましくは０．５～５％である。 In the crystallized glass of the present invention, the content of the oxides of the second to fourth transition metals excluding group 4 (hereinafter referred to as the second to fourth transition metal oxides) is not limited because the second to fourth transition metal elements do not easily affect the metallic luster of the surface. However, because the transition metal elements are components that tend to color the glass, the content of the oxides of the second to fourth transition metals may be regulated from the viewpoint of reducing the coloration of the glass. In this case, the content of the oxides of the second to fourth transition metals is preferably 0 to 10%, preferably 0.1 to 8%, and more preferably 0.5 to 5%, in terms of mass % of the outer percentage of the base glass.
また、本発明に係る第一遷移金属酸化物は、Ｖ２Ｏ５、Ｃｒ２Ｏ３、ＭｎＯ、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯから選択される一種類以上であることが好ましい。またこの場合、Ｖ２Ｏ５、Ｃｒ２Ｏ３、ＭｎＯ、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯの含有量の合量は、好ましくは１超～１０％であり、１．２～９％、１．４～８．５％、１．６～８％、１．８～７．５％、１．９～７％、２～６％、特に２．２％～５％が好ましい。このようにすると、更に本発明の効果を得やすい。 The first transition metal oxide according to the present invention is preferably one or more selected from V 2 O 5 , Cr 2 O 3 , MnO, Fe 2 O 3 , CoO, NiO, and CuO. In this case, the total content of V 2 O 5 , Cr 2 O 3 , MnO, Fe 2 O 3 , CoO, NiO, and CuO is preferably more than 1 to 10%, more preferably 1.2 to 9%, 1.4 to 8.5%, 1.6 to 8%, 1.8 to 7.5%, 1.9 to 7%, 2 to 6%, and particularly preferably 2.2 to 5%. In this way, the effects of the present invention are more easily obtained.
また、本発明に係る第一遷移金属酸化物は、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯから選択される一種類以上であることがより好ましい。これらを第一遷移金属酸化物として用いると、本発明の効果を得やすい。またこの場合、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯの含有量の合量は、好ましくは１超～１０％であり、１．２～９％、１．４～８．５％、１．６～８％、１．８～７．５％、１．９～７％、２～６％、特に２．２～５％が好ましい。このようにすると、特に本発明の効果を得やすい。 Moreover, the first transition metal oxide according to the present invention is more preferably one or more selected from Fe 2 O 3 , CoO, NiO, and CuO. Using these as the first transition metal oxide makes it easier to obtain the effects of the present invention. In this case, the total content of Fe 2 O 3 , CoO, NiO, and CuO is preferably more than 1% and up to 10%, and is preferably 1.2 to 9%, 1.4 to 8.5%, 1.6 to 8%, 1.8 to 7.5%, 1.9 to 7%, 2 to 6%, and particularly preferably 2.2 to 5%. In this way, it is especially easy to obtain the effects of the present invention.
また、Ｖ２Ｏ５、Ｃｒ２Ｏ３、ＭｎＯ、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯの各々の含有量は、好ましくは０～１０％であり、０超～１０％、０．１～９．６％、０．１超～９．４％、０．２～９％、０．５～８.６％、０．８～８．４％、１～７．８％、１．２～７．５％、１．４～７％、１．７～６．５％、１．８～６％、１．９～５．５％、特に２～５％が好ましい。なお、上記した第一遷移金属酸化物は、それぞれ単独で使用しても良いし、任意の割合で混合して使用してもよい。なお、環境負荷や毒性の観点からは、ＣｏＯの含有量は、好ましくは０．０４％以下であり、０．０３５％以下、０．０３％以下、０．０２％以下、０．０１％以下、特に含有しないことが好ましい。 Further, the content of each of V 2 O 5 , Cr 2 O 3 , MnO, Fe 2 O 3 , CoO, NiO, and CuO is preferably 0 to 10%, more than 0 to 10%, and 0.1 to 10%. 9.6%, more than 0.1 to 9.4%, 0.2 to 9%, 0.5 to 8.6%, 0.8 to 8.4%, 1 to 7.8%, 1.2 -7.5%, 1.4-7%, 1.7-6.5%, 1.8-6%, 1.9-5.5%, particularly 2-5% are preferred. Note that the above-described first transition metal oxides may be used alone, or may be used in combination in any proportion. In addition, from the viewpoint of environmental load and toxicity, the content of CoO is preferably 0.04% or less, 0.035% or less, 0.03% or less, 0.02% or less, 0.01% or less. , it is particularly preferable not to contain it.
また、上記したように、遷移金属酸化物は、一般的に結晶化ガラスにおいて着色を強める成分であるが、Ｎｄ２Ｏ３については、ガラスの透明度を低下させる一方、着色を低減する効果を有する成分でもある。そのため、Ｎｄ２Ｏ３の含有量としては、好ましくは０～０．２％、より好ましくは０～０．１％、特に実質的に含有しない（具体的には、１００ｐｐｍ以下）ことが好ましいが、透明感の高さよりも着色の少なさを優先させる場合には、例えばＮｄ２Ｏ３を５００ｐｐｍ程度添加しても構わない。 Furthermore, as mentioned above, transition metal oxides are generally components that strengthen coloring in crystallized glass, but Nd 2 O 3 has the effect of reducing coloring while reducing the transparency of glass. It is also an ingredient. Therefore, the content of Nd 2 O 3 is preferably 0 to 0.2%, more preferably 0 to 0.1%, and particularly preferably substantially not contained (specifically, 100 ppm or less). If less coloring is given priority over higher transparency, for example, about 500 ppm of Nd 2 O 3 may be added.
また、本発明に係る遷移金属元素は、上記したとおり第４族を除いた、すなわち第３及び第５～１１族の遷移金属元素のことを指すが、遷移金属元素は、好ましくは第５～１１族、より好ましくは第６～１１族、更に好ましくは第７～１１族、特に好ましくは第８～１１族である。このようにすれば、遷移金属元素がイオン化しやすくなるため、金属光沢を有する結晶化ガラスを得やすくできる。 As described above, the transition metal element according to the present invention refers to a transition metal element of Group 3 and Groups 5 to 11 excluding Group 4, but the transition metal element is preferably a transition metal element of Groups 5 to 11, more preferably a transition metal element of Groups 6 to 11, even more preferably a transition metal element of Groups 7 to 11, and particularly preferably a transition metal element of Groups 8 to 11. In this way, the transition metal element is easily ionized, making it easier to obtain crystallized glass with metallic luster.
本発明の結晶化ガラスは、結晶化度が７０％以上であり、より好ましくは７２％以上、更に好ましくは７３％以上、７５％以上、７７％以上、特に好ましくは７９％以上である。結晶化度が低すぎると、結晶化ガラス中のガラスマトリックスに遷移金属イオンが濃縮しにくくなるため、結晶化ガラスの表面に金属光沢を発現させにくくなる。一方、結晶化度の上限は特に限定されず、１００％であっても良いが、現実的には、９９％以下、９５％以下、９０％以下、特に８９％以下が好ましい。 The crystallinity of the crystallized glass of the present invention is 70% or more, more preferably 72% or more, still more preferably 73% or more, 75% or more, 77% or more, particularly preferably 79% or more. If the crystallinity is too low, transition metal ions will be difficult to concentrate in the glass matrix in the crystallized glass, making it difficult to develop metallic luster on the surface of the crystallized glass. On the other hand, the upper limit of the degree of crystallinity is not particularly limited and may be 100%, but in reality, it is preferably 99% or less, 95% or less, 90% or less, particularly 89% or less.
本発明の結晶化ガラスは、第一遷移金属酸化物を所定量含有し且つ結晶化度が７０％以上のものであれば、ガラス組成を問わない。結晶化ガラスのガラス組成としては、例えば、アルミノシリケートガラスであることが好ましく、特にリチウムアルミノシリケートガラスであることが好ましい。 The crystallized glass of the present invention may have any glass composition as long as it contains a specified amount of first transition metal oxide and has a crystallinity of 70% or more. The glass composition of the crystallized glass is preferably, for example, aluminosilicate glass, and in particular, lithium aluminosilicate glass.
本発明の結晶化ガラスは、結晶としてβクォーツ、βスポジュメンから選択される一種類以上を含むことが好ましく、特に、主結晶がβクォーツであることが好ましい。特に、主結晶がβクォーツの固溶体を含む結晶化ガラスは、透光性を有する。そのため、主結晶がβクォーツの固溶体を含む結晶性ガラスに第一遷移金属酸化物を所定量含有させると、金属光沢を有し且つガラスの透光性を併せ持つ意匠性の高いガラス物品を得ることができる。 The crystallized glass of the present invention preferably contains one or more types of crystals selected from β-quartz and β-spodumene, and in particular, it is preferable that the main crystal is β-quartz. In particular, crystallized glass containing a solid solution of β-quartz as the main crystal has translucency. Therefore, by adding a predetermined amount of first transition metal oxide to crystallized glass containing a solid solution of β-quartz as the main crystal, it is possible to obtain a highly designable glass article that has metallic luster and the translucency of glass.
本発明の結晶化ガラスは、表面抵抗率（ｌｏｇρ）が、好ましくは８Ω・ｃｍ以下であり、より好ましくは７．５Ω・ｃｍ以下、更に好ましくは７Ω・ｃｍ以下である。このようにすると、電荷移動速度を大きくでき、導電性を向上させやすくできる。 The crystallized glass of the present invention preferably has a surface resistivity (log ρ) of 8 Ω·cm or less, more preferably 7.5 Ω·cm or less, and even more preferably 7 Ω·cm or less. This makes it possible to increase the charge transfer rate and to easily improve the electrical conductivity.
また、本発明の結晶化ガラスは、ガラス本体とその表面に形成された金属光沢層を有し、金属光沢層の表面抵抗率が、ガラス本体の表面抵抗率と異なることが好ましい。また、金属光沢層の表面抵抗率が、ガラス本体の表面抵抗率よりも低いことが好ましい。更に、金属光沢層の表面抵抗率が、ガラス本体の表面抵抗率に比べて、好ましくは０．５Ω・ｃｍ以上低く、より好ましくは１Ω・ｃｍ以上低く、更に好ましくは１．５Ω・ｃｍ以上低いことが好ましい。金属光沢層の表面抵抗率とガラス本体の表面抵抗率の差が大きいほど、膜抵抗器として用いた際に性能が高くなる。 Moreover, the crystallized glass of the present invention preferably has a glass body and a metallic luster layer formed on the surface thereof, and the surface resistivity of the metallic luster layer is different from the surface resistivity of the glass body. Moreover, it is preferable that the surface resistivity of the metallic luster layer is lower than the surface resistivity of the glass body. Furthermore, the surface resistivity of the metallic luster layer is preferably lower than the surface resistivity of the glass body by 0.5 Ω·cm or more, more preferably 1 Ω·cm or more lower, and even more preferably 1.5 Ω·cm or more lower. It is preferable. The larger the difference between the surface resistivity of the metallic luster layer and the surface resistivity of the glass body, the higher the performance when used as a film resistor.
また、本発明の結晶化ガラスにおいて、金属光沢層の厚みは、好ましくは１０～５００μｍであり、３０～３００μｍ、５０～１００μｍである。金属光沢層の厚みが薄いほど、精密な部品を作製しやすい。一方、金属光沢層の厚みが厚いほど、膜抵抗器として用いた際に性能が安定しやすい。 In addition, in the crystallized glass of the present invention, the thickness of the metallic luster layer is preferably 10 to 500 μm, 30 to 300 μm, or 50 to 100 μm. The thinner the metallic luster layer, the easier it is to manufacture precision parts. On the other hand, the thicker the metallic luster layer, the more stable the performance when used as a film resistor.
以下に、本発明の結晶化ガラスのベースガラスのガラス組成について詳述する。以下の説明において、特段の断りがない限り、「％」は質量％を示す。また、「含有する」という用語に関し、「０～」と規定された成分については、「０％」、すなわち、全く含まない場合もあり得ることを意味する。 Below, the glass composition of the base glass of the crystallized glass of the present invention will be explained in detail. In the following description, "%" indicates mass % unless otherwise specified. Furthermore, regarding the term "contains", a component defined as "0~" means that it may be "0%", that is, it may not be contained at all.
本発明の結晶化ガラスは、上述したとおりガラス組成を問わないが、例えば、質量％で、ＳｉＯ２ ５０～８０％、Ａｌ２Ｏ３ １０～２５％、Ｌｉ２Ｏ ０．１～２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～１０％を含有することが好ましい。このようにすると、結晶化ガラスを容易に得ることができる。本発明の結晶化ガラスは、結晶化工程において、結晶化ガラス中のガラスマトリックスに遷移金属イオンが濃縮することで金属光沢が発現すると考えられる。そのため、前駆体である結晶性ガラスを容易に結晶化ガラスにできることが重要である。 As described above, the crystallized glass of the present invention can have any glass composition, but it is preferable that the crystallized glass contains, for example, SiO 2 50-80%, Al 2 O 3 10-25%, Li 2 O 0.1-20%, and MgO+CaO+SrO+BaO+ZnO 0-10% by mass. In this way, the crystallized glass of the present invention can be easily obtained. It is considered that the crystallized glass of the present invention exhibits metallic luster by concentrating transition metal ions in the glass matrix in the crystallized glass in the crystallization process. Therefore, it is important that the precursor crystallizable glass can be easily made into the crystallized glass.
ＳｉＯ２はガラスの骨格成分であり、結晶化ガラス中の結晶を構成する成分である。ＳｉＯ２の含有量は、好ましくは５０～８０％であり、より好ましくは５５～７３％、更に好ましくは６３～７０％である。ＳｉＯ２の含有量が少なすぎると、結晶析出量が少なくなり、金属光沢を有する結晶化ガラスを得にくくなる。一方、多すぎるとガラスの溶融性が低下したり、成形が困難になったりする。 SiO2 is a glass framework component, and is a component that constitutes the crystals in crystallized glass. The content of SiO2 is preferably 50-80%, more preferably 55-73%, and even more preferably 63-70%. If the content of SiO2 is too small, the amount of crystal precipitation is small, and it is difficult to obtain crystallized glass with metallic luster. On the other hand, if the content is too large, the melting property of glass is reduced, and molding becomes difficult.
Ａｌ２Ｏ３はガラスの骨格成分であり、結晶化ガラス中の結晶を構成する成分でもある。Ａｌ２Ｏ３の含有量は、好ましくは１０～２５％であり、より好ましくは１７～２４％、更に好ましくは１８～２２．５％である。Ａｌ２Ｏ３の含有量が少なすぎると、結晶析出量が少なくなり、金属光沢を有する結晶化ガラスを得にくくなる。一方、多すぎるとガラスの溶融性が低下したり、成形が困難になったりする。 Al 2 O 3 is a skeletal component of glass, and is also a component constituting crystals in crystallized glass. The content of Al 2 O 3 is preferably 10 to 25%, more preferably 17 to 24%, even more preferably 18 to 22.5%. If the content of Al 2 O 3 is too small, the amount of crystal precipitation will be small, making it difficult to obtain crystallized glass with metallic luster. On the other hand, if the amount is too high, the melting properties of the glass will decrease or molding will become difficult.
Ｌｉ２Ｏはガラスの結晶性に大きな影響を与える。Ｌｉ２Ｏは、結晶化ガラスの結晶を構成する成分である。Ｌｉ２Ｏの含有量は、好ましくは０．１～２０％であり、より好ましくは２～１０％、更に好ましくは３～５％である。Ｌｉ２Ｏの含有量が少なすぎると結晶析出量が少なくなり、金属光沢を有する結晶化ガラスを得にくくなる。一方、多すぎると結晶性が過剰に強くなり、ガラスの成形が困難になりやすい。 Li 2 O has a large effect on the crystallinity of glass. Li 2 O is a component that constitutes the crystals of crystallized glass. The content of Li 2 O is preferably 0.1-20%, more preferably 2-10%, and even more preferably 3-5%. If the content of Li 2 O is too small, the amount of crystal precipitation is small, and it is difficult to obtain crystallized glass with metallic luster. On the other hand, if the content is too large, the crystallinity becomes excessively strong, and it is easy to make it difficult to mold the glass.
ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯは、Ｌｉ２Ｏの替わりにβクォーツに固溶する成分である。また、ガラスの粘性を低下させて溶融性及び成形性を向上させる成分でもある。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量は、好ましくは０～１０％であり、より好ましくは０～５％、更に好ましくは０．１～２％である。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量が多すぎると結晶性が過剰に強くなり失透する傾向にあり、ガラスの成形が困難になりやすい。また、ガラスが破損しやすくなる。なお、「ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ」とは、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの含有量の合量を指す。 MgO, CaO, SrO, BaO, and ZnO are components that are dissolved in β-quartz instead of Li 2 O. It is also a component that reduces the viscosity of glass and improves its meltability and moldability. The content of MgO+CaO+SrO+BaO+ZnO is preferably 0 to 10%, more preferably 0 to 5%, and still more preferably 0.1 to 2%. If the content of MgO+CaO+SrO+BaO+ZnO is too large, the crystallinity tends to become excessively strong and devitrification tends to occur, making it difficult to mold the glass. Moreover, the glass becomes easily damaged. Note that "MgO+CaO+SrO+BaO+ZnO" refers to the total content of MgO, CaO, SrO, BaO, and ZnO.
また、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの各々の含有量は、好ましくは０～２％であり、より好ましくは０～１．５％、更に好ましくは０．１～１．２％である。ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの各々の含有量が多すぎると結晶性が過剰に強くなり失透する傾向にあり、ガラスの成形が困難になりやすい。また、ガラスが破損しやすくなる。 The content of each of MgO, CaO, SrO, BaO and ZnO is preferably 0-2%, more preferably 0-1.5%, and even more preferably 0.1-1.2%. If the content of each of MgO, CaO, SrO, BaO and ZnO is too high, the crystallinity becomes excessively strong and tends to devitrify, making it difficult to mold the glass. In addition, the glass becomes more susceptible to breakage.
また、上記成分以外にも、ベースガラスの成分として、ＴｉＯ２、ＺｒＯ２を含有させることができる。 Moreover, in addition to the above-mentioned components, TiO 2 and ZrO 2 can be included as components of the base glass.
ＴｉＯ２は結晶化工程で結晶を析出させるための核形成成分である。ＴｉＯ２の含有量は、好ましくは０．１～５％であり、より好ましくは０．１～４％、０．２～３．５％、０．５～３％、０．８～２．８％、１～２．６％、１超～２．５％、特に好ましくは１．２～２．３％である。ＴｉＯ２の含有量が多すぎると、ガラスが失透する傾向にあり、破損しやすくなる。一方、少なすぎると、結晶核が十分に形成されず、粗大な結晶が析出して破損するおそれがある。 TiO 2 is a nucleation component for precipitating crystals in the crystallization process. The content of TiO 2 is preferably 0.1-5%, more preferably 0.1-4%, 0.2-3.5%, 0.5-3%, 0.8-2. 8%, 1 to 2.6%, more than 1 to 2.5%, particularly preferably 1.2 to 2.3%. If the content of TiO 2 is too large, the glass tends to devitrify, making it easy to break. On the other hand, if the amount is too small, crystal nuclei will not be sufficiently formed, and coarse crystals may precipitate and be damaged.
ＺｒＯ２はＴｉＯ２と同様に、結晶化工程で結晶を析出させるための結晶核を構成する成分である。ＺｒＯ２の含有量は、好ましくは０．１～５％であり、より好ましくは０．１～４％、更に好ましくは０．５～３％である。ＺｒＯ２の含有量が多すぎると、ガラスを溶融する際に失透する傾向にあり、ガラスの成形が困難になりやすい。一方、少なすぎると、結晶核が十分に形成されず、粗大な結晶が析出して破損するおそれがある。 ZrO2 , like TiO2 , is a component that constitutes the crystal nucleus for precipitating crystals in the crystallization process. The content of ZrO2 is preferably 0.1 to 5%, more preferably 0.1 to 4%, and even more preferably 0.5 to 3%. If the content of ZrO2 is too high, the glass tends to devitrify when melted, making it difficult to mold the glass. On the other hand, if the content is too low, the crystal nucleus is not sufficiently formed, and coarse crystals may precipitate and break.
さらに、上記成分以外にも要求される特性を損なわない範囲で種々の成分を添加することができる。 Furthermore, in addition to the above-mentioned components, various components can be added within a range that does not impair the required properties.
Ｐ２Ｏ５はガラスの分相を促進し、結晶核を形成しやすくする成分である。Ｐ２Ｏ５の含有量は、好ましくは０～５％であり、より好ましくは０～３％、更に好ましくは０．１～２％である。Ｐ２Ｏ５の含有量が多すぎると、溶融工程においてガラスが過剰に分相し、所望の組成を有するガラスが得にくくなるとともに、不透明となる傾向がある。 P 2 O 5 is a component that promotes phase separation of glass and makes it easier to form crystal nuclei. The content of P 2 O 5 is preferably 0 to 5%, more preferably 0 to 3%, and further preferably 0.1 to 2%. If the content of P 2 O 5 is too high, the glass undergoes excessive phase separation in the melting step, making it difficult to obtain glass having the desired composition and tending to become opaque.
Ｎａ２ＯやＫ２Ｏはガラスの粘性を低下させて、ガラスの溶融及び成形性を向上させる成分である。Ｎａ２Ｏの含有量は、好ましくは０～３％であり、より好ましくは０～２％、更に好ましくは０．３～０．７％である。また、Ｋ２Ｏの含有量は、好ましくは０～３％であり、より好ましくは０～２％、更に好ましくは０．３～０．７％である。Ｎａ２ＯやＫ２Ｏの含有量が多すぎると、ガラスが失透しやすくなる。 Na 2 O and K 2 O are components that reduce the viscosity of glass and improve the melting and formability of glass. The content of Na 2 O is preferably 0 to 3%, more preferably 0 to 2%, and even more preferably 0.3 to 0.7%. The content of K 2 O is preferably 0 to 3%, more preferably 0 to 2%, and even more preferably 0.3 to 0.7%. If the content of Na 2 O or K 2 O is too high, the glass is likely to devitrify.
Ｂ２Ｏ３はβ－スポジュメンの析出を抑制する効果がある成分である。また、ガラス溶融工程においてＳｉＯ２原料の溶解を促進する効果もある。Ｂ２Ｏ３の含有量は、好ましくは０．０５～１．５％であり、より好ましくは０．１～１％である。Ｂ２Ｏ３の含有量が少なすぎると、前述した効果が得にくくなる。一方、Ｂ２Ｏ３の含有量が多すぎると、ガラスが白濁しやすくなり、透明感の高いガラスが得にくくなる。また、Ｂ２Ｏ３は結晶化により残存ガラス相に濃縮され、残存ガラス相の粘性を低下させる。そのため、結晶化ガラスを高温で使用した際に軟化変形しやすくなる。 B 2 O 3 is a component that has the effect of suppressing the precipitation of β-spodumene. It also has the effect of promoting the dissolution of the SiO 2 raw material in the glass melting process. The content of B 2 O 3 is preferably 0.05 to 1.5%, more preferably 0.1 to 1%. If the content of B 2 O 3 is too small, it is difficult to obtain the above-mentioned effects. On the other hand, if the content of B 2 O 3 is too large, the glass tends to become cloudy, making it difficult to obtain glass with high transparency. In addition, B 2 O 3 is concentrated in the remaining glass phase by crystallization, reducing the viscosity of the remaining glass phase. Therefore, when the crystallized glass is used at high temperatures, it is easy to soften and deform.
ＳｎＯ２はガラスを清澄し、均質なガラスを得るために有効な成分である。ＳｎＯ２の含有量は、好ましくは０．１～２％であり、より好ましくは０．１～１％、さらに好ましくは０．２～０．８％である。ＳｎＯ２の含有量が少なすぎると、清澄剤としての効果が得にくくなる。一方、ＳｎＯ２の含有量が多すぎると、結晶化ガラスが黄色味を帯びやすくなる。また、メカニズムの詳細は不明であるが、ＳｎＯ２はβ－スポジュメンの失透速度を上げる働きがあるため、添加量が多すぎると失透が生じやすくなる。 SnO2 is an effective component for refining glass and obtaining homogeneous glass. The content of SnO 2 is preferably 0.1 to 2%, more preferably 0.1 to 1%, even more preferably 0.2 to 0.8%. If the content of SnO 2 is too low, it will be difficult to obtain the effect as a clarifying agent. On the other hand, if the content of SnO 2 is too large, the crystallized glass tends to take on a yellowish tinge. Further, although the details of the mechanism are unknown, SnO 2 has the effect of increasing the devitrification rate of β-spodumene, so if the amount added is too large, devitrification tends to occur.
また、清澄剤として、ＳＯ２やＣｌを必要に応じて単独で又は組み合わせて添加してもよい。これらの成分の合量は０．５％以下とすることが望ましい。なおＳｂ２Ｏ３も清澄成分であり、含有させることができるが、環境負荷が大きく含有しないことが好ましい。 Further, as a clarifying agent, SO 2 or Cl may be added alone or in combination as necessary. The total amount of these components is desirably 0.5% or less. Incidentally, Sb 2 O 3 is also a clarifying component and can be contained, but it is preferable not to contain it because it causes a large environmental load.
また、本発明においては、環境負荷が大きい酸化ヒ素、酸化鉛を実質的に含まないことが好ましい。なお、本発明において、「実質的に含まない」とは、意図的にガラスに添加しないという意味であり、不可避不純物まで完全に排除するものではない。より客観的には、不純物を含めた含有量が０．０１％以下であるということを意味する。 Further, in the present invention, it is preferable that arsenic oxide and lead oxide, which have a large environmental impact, are substantially not included. In the present invention, "substantially free" means that it is not intentionally added to the glass, and does not mean completely eliminating inevitable impurities. More objectively, it means that the content including impurities is 0.01% or less.
また、本発明の結晶性ガラスは、上記した結晶化ガラスの前駆体、すなわち結晶化前のガラスであることが好ましい。なお、結晶性ガラスのガラス組成等については、上記した結晶化ガラスと同じであり、具体的な好ましい範囲については、説明を割愛する。 Further, the crystalline glass of the present invention is preferably a precursor of the above-mentioned crystallized glass, that is, a glass before crystallization. Note that the glass composition of the crystalline glass is the same as that of the above-mentioned crystallized glass, and a description of the specific preferred range will be omitted.
本発明の結晶化ガラスの製造方法は、前記した結晶性ガラスを結晶化させることにより製造することができる。例えば、前述した結晶性ガラスを７００～１０００℃の熱処理に供することにより結晶化させることが好ましい。熱処理温度の下限を上記の通り規制すると、結晶化度が７０％以上であり金属光沢を有する結晶化ガラスを得やすくなる。一方、熱処理温度の上限を上記の通り規制すると、βクォーツ及び／又はβスポジュメン結晶のみを析出させることができる。 The method for producing crystallized glass of the present invention can be produced by crystallizing the above-described crystalline glass. For example, it is preferable to crystallize the above-mentioned crystalline glass by subjecting it to heat treatment at 700 to 1000°C. When the lower limit of the heat treatment temperature is regulated as described above, it becomes easier to obtain crystallized glass having a crystallinity of 70% or more and a metallic luster. On the other hand, if the upper limit of the heat treatment temperature is regulated as described above, only β-quartz and/or β-spodumene crystals can be precipitated.
なお、結晶化方法の一例としては、成形した結晶性ガラスを、例えば６００～８００℃で１～５時間熱処理して結晶核を形成した後、更に７００～１０００℃で数分～数時間熱処理を行い、主結晶としてβクォーツ及び／又はβスポジュメン結晶を析出させる方法が挙げられる。 One example of a crystallization method is to heat treat the molded crystalline glass at, for example, 600 to 800°C for 1 to 5 hours to form crystal nuclei, and then further heat treat it at 700 to 1000°C for several minutes to several hours to precipitate β-quartz and/or β-spodumene crystals as the main crystals.
本発明の結晶化ガラスは、内部（ガラス本体）において、ＣＩＥ規格のＬ＊ａ＊ｂ＊表示のＬ＊値が、４ｍｍ厚で、好ましくは４５以上、５０以上、５５以上、特に６０以上であることが好ましい。このようにすると外観が明るくなり、意匠性の高い結晶化ガラスを得ることができる。また、本発明の結晶化ガラスは、ＣＩＥ規格のＬ＊ａ＊ｂ＊表示のｂ＊値が、４ｍｍ厚で、好ましくは４．５以下、４以下、３以下、２以下、特に１．４以下であることが好ましい。このようにすると、黄色着色が少なくなり、意匠性に優れる。また、４３０ｎｍの透過率が、４ｍｍ厚で、好ましくは７％以上、１０％以上、１５％以上、２０％以上、３０％以上、４０％以上、５０％以上、６０％以上、７０％以上、８０％以上、８２．５％以上、特に８３％以上であることが好ましい。このようにすると、結晶化ガラスが透光性を有するため、意匠性の高い結晶化ガラスを得ることができる。 The crystallized glass of the present invention has an L* value of L*a*b* according to the CIE standard in the interior (glass body) at a thickness of 4 mm, preferably 45 or more, 50 or more, 55 or more, especially 60 or more. It is preferable that there be. By doing so, it is possible to obtain a crystallized glass with a bright appearance and a high design quality. Further, the crystallized glass of the present invention has a b* value of L*a*b* according to the CIE standard at a thickness of 4 mm, preferably 4.5 or less, 4 or less, 3 or less, 2 or less, particularly 1.4. It is preferable that it is below. In this way, yellowing is reduced and the design is excellent. Further, the transmittance at 430 nm is preferably 7% or more, 10% or more, 15% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, with a thickness of 4mm. It is preferably 80% or more, 82.5% or more, particularly 83% or more. In this way, since the crystallized glass has translucency, it is possible to obtain a crystallized glass with a high design quality.
また、本発明の結晶化ガラスは、３０～３８０℃の温度範囲での熱膨張係数が、好ましくは－２．５×１０－７～２．５×１０－７／℃であり、より好ましくは－１．５×１０－７／℃～１．５×１０－７／℃である。熱膨張係数が小さくなりすぎる又は大きくなりすぎると、破損のリスクが高くなりやすい。 The crystallized glass of the present invention preferably has a thermal expansion coefficient of −2.5×10 −7 to 2.5×10 −7 /° C., more preferably −1.5×10 −7 /° C. to 1.5×10 −7 /° C., in the temperature range of 30 to 380 ° C. If the thermal expansion coefficient is too small or too large, the risk of breakage tends to increase.
本発明の結晶化ガラスは、切断、研磨、曲げ加工、強化等の加工を施してもよい。但し、金属光沢面が必要な部分には研磨を行わないことが好ましい。また、金属光沢が損なわれる虞がある場合には、熱強化や化学強化等の強化処理を行わないことが好ましい。 The crystallized glass of the present invention may be subjected to processing such as cutting, polishing, bending, and strengthening. However, it is preferable not to polish areas where a metallic shiny surface is required. Furthermore, if there is a risk that the metallic luster may be impaired, it is preferable not to perform a strengthening treatment such as thermal strengthening or chemical strengthening.
以下、実施例に基づいて実施例を用いて本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではないことは明らかである。 EXAMPLES Hereinafter, the present invention will be explained in detail based on Examples, but it is clear that the present invention is not limited to these Examples.
表１及び表２は、ベースガラスと、本発明の実施例（Ｎｏ．１～８）及び比較例（Ｎｏ．９～１３）を示している。 Tables 1 and 2 show the base glass, examples of the present invention (Nos. 1 to 8), and comparative examples (Nos. 9 to 13).
各試料は次のようにして調整した。まず、表１に記載の組成となるように、ベースガラスバッチを作製した。更に、表２の割合になるように、外掛けの質量％で、表２に記載の遷移金属酸化物をベースガラスバッチに添加して、各バッチを作製した。次いで白金坩堝を用いて各バッチを１５５０～１６５０℃で２０時間溶融し、カーボン板の上に５ｍｍ厚の２本のスペーサーを載置し、スペーサーの間に溶融ガラスを流し出すとともにローラーにて均一の厚みの板状に成形した。更に、板状試料を６５０～７５０℃に保持した電気炉に投入して、３０分保持後に３００℃まで約６時間かけて徐冷し、その後室温まで放冷して結晶性ガラスを作製した。 Each sample was prepared as follows. First, a base glass batch was prepared so as to have the composition shown in Table 1. Then, the transition metal oxides shown in Table 2 were added to the base glass batch in the mass percentage of the outer percentage so as to obtain the ratio shown in Table 2, to prepare each batch. Next, each batch was melted at 1550-1650°C for 20 hours using a platinum crucible, and two spacers with a thickness of 5 mm were placed on a carbon plate, and the molten glass was poured out between the spacers and formed into a plate of uniform thickness using a roller. Furthermore, the plate-shaped sample was placed in an electric furnace maintained at 650-750°C, and after holding for 30 minutes, it was slowly cooled to 300°C over approximately 6 hours, and then allowed to cool to room temperature to produce a crystalline glass.
その後、得られた結晶性ガラスを約３０×３０ｍｍの板に切断し、研磨加工して鏡面研磨面を得た。 Thereafter, the obtained crystalline glass was cut into plates of about 30 x 30 mm and polished to obtain mirror-polished surfaces.
次いで、約３０×３０ｍｍの結晶性ガラスを電気炉で下記ＳＴＥＰ通り熱処理することによって結晶化ガラスを得た。
ＳＴＥＰ１： 室温から６６０～７００℃の温度に昇温、２０分～５時間保持
ＳＴＥＰ２： ６６０～７００℃から８７０～９１０℃に昇温、１０分～２時間保持
ＳＴＥＰ３： ８７０～９１０℃から室温まで約１０時間かけて室温まで降温
Next, a crystallized glass of approximately 30×30 mm was heat-treated in an electric furnace according to the following STEP to obtain a crystallized glass.
STEP 1: Raise the temperature from room temperature to 660-700°C and hold for 20 minutes to 5 hours STEP 2: Raise the temperature from 660-700°C to 870-910°C and hold for 10 minutes to 2 hours STEP 3: Raise the temperature from 870-910°C to room temperature Cool down to room temperature over about 10 hours
上記のようにして得た各試料について、外観観察、ＸＲＤにより、結晶化ガラス中の結晶の同定及び結晶化度の測定を行った。 For each sample obtained as described above, the crystals in the crystallized glass were identified and the degree of crystallinity was measured by visual observation and XRD.
また、金属光沢層の有無は目視で判断し、金属光沢層の構成元素の同定はＥＤＸ(日立製Ｓ－３４００Ｎ)で行った。 The presence or absence of a metallic gloss layer was determined visually, and the constituent elements of the metallic gloss layer were identified using EDX (Hitachi S-3400N).
更に、ガラスの表面抵抗率（Ｓｕｒｆａｃｅ ｒｅｓｉｓｔｉｖｉｔｙ）は、ＪＩＳ６９１１（１９９５）に従い、内部電極直径５０ｍｍ、外部電極直径５７．２ｍｍの二重リング法で、印加電圧１０００Ｖ、抵抗補正係数１００、測定温度２５℃、測定湿度３５％の大気雰囲気下にて計測を行った。計測は５回行い、その算術平均値を採用した。また金属光沢層の抵抗を測定した後に表面から５００～１０００μｍ研磨して金属光沢層を完全に除去して結晶化ガラス本体を表面に露出させ、ガラス本体表面の表面抵抗率を測定した。なお、金属光沢層が形成されなかったガラスについては、研磨前のガラスの表面抵抗率と、研磨後のガラスの表面抵抗率をそれぞれ測定した。 Furthermore, the surface resistivity of the glass was measured according to JIS6911 (1995) using the double ring method with an inner electrode diameter of 50 mm and an outer electrode diameter of 57.2 mm, an applied voltage of 1000 V, a resistance correction coefficient of 100, and a measurement temperature of 25°C. The measurement was carried out in an atmospheric atmosphere with a measurement humidity of 35%. Measurement was performed five times, and the arithmetic mean value was used. After measuring the resistance of the metallic luster layer, the metallic lustrous layer was completely removed by polishing from the surface by 500 to 1000 μm to expose the crystallized glass body to the surface, and the surface resistivity of the glass body surface was measured. In addition, regarding the glass on which the metallic luster layer was not formed, the surface resistivity of the glass before polishing and the surface resistivity of the glass after polishing were measured, respectively.
図１に、試料Ｎｏ．４の結晶化ガラスの外観写真を示し、図２に結晶化前の結晶性ガラスの外観写真を示す。図２より、結晶化前の結晶性ガラスは全体的に透光性を有していることが分かる。また、図１より、結晶化後の結晶化ガラス表面は金属光沢層を有していることが分かる。更に、図１の結晶化ガラスについて、金属光沢層を研磨除去して結晶化ガラス本体を確認したところ、ガラス本体は透光性を有していた。 In FIG. 1, sample No. A photograph of the appearance of the crystallized glass of No. 4 is shown, and FIG. 2 shows a photograph of the appearance of the crystallized glass before crystallization. From FIG. 2, it can be seen that the crystalline glass before crystallization has translucency as a whole. Further, from FIG. 1, it can be seen that the surface of the crystallized glass after crystallization has a metallic luster layer. Further, regarding the crystallized glass shown in FIG. 1, when the metallic luster layer was removed by polishing and the crystallized glass main body was confirmed, the glass main body had translucency.
また、表２から明らかなように、実施例である試料Ｎｏ．１～８は結晶化ガラスの表面層に金属光沢を有していた。更に、試料Ｎｏ．２において、金属光沢層の表面抵抗率は、金属光沢層を除去した結晶化ガラス本体の表面抵抗率よりも低くなっていた。 As is clear from Table 2, the surface layer of the crystallized glass in the examples of Samples No. 1 to 8 had a metallic luster. Furthermore, in Sample No. 2, the surface resistivity of the metallic luster layer was lower than the surface resistivity of the crystallized glass body from which the metallic luster layer had been removed.
本発明の結晶化ガラスは、光学部品のミラーや、意匠性に優れた調理器用のトッププレートとして使用可能である。また、本発明の結晶化ガラスの金属光沢層の表面抵抗率は、金属光沢層を除去した結晶化ガラス内部の表面抵抗率より低いことから、本発明の結晶化ガラスは、膜抵抗器としても利用可能である。 The crystallized glass of the present invention can be used as a mirror for an optical component or a top plate for a cooker with excellent design. Furthermore, since the surface resistivity of the metallic luster layer of the crystallized glass of the present invention is lower than the surface resistivity of the interior of the crystallized glass from which the metallic luster layer has been removed, the crystallized glass of the present invention can also be used as a film resistor. Available.
Claims (9)
外掛けの質量％で、第４族を除く第一遷移金属酸化物を１超～１０％含有し、
前記第一遷移金属酸化物が、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯから選択される一種類以上であり、結晶化度が７０％以上であることを特徴とする結晶化ガラス。 In mass %, SiO 2 50-80%, Al 2 O 3 10-25%, Li 2 O 0.1-20%, MgO + CaO + SrO + BaO + ZnO 0-10%, TiO 2 0.1-5%, ZrO 2 0.1 Contains ~5%,
Contains more than 1 to 10% of a first transition metal oxide excluding Group 4 in terms of external mass %,
A crystallized glass, wherein the first transition metal oxide is one or more selected from Fe 2 O 3 , CoO, NiO, and CuO, and has a crystallinity of 70% or more.
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| US3926602A (en) * | 1974-06-19 | 1975-12-16 | Corning Glass Works | Glass-ceramic articles with reflective surfaces |
| US4414281A (en) * | 1982-02-16 | 1983-11-08 | Corning Glass Works | Glass-ceramic articles having metallic surfaces |
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| JP2011073935A (en) | 2009-09-30 | 2011-04-14 | Ohara Inc | Crystallized glass |
| WO2016042985A1 (en) | 2014-09-16 | 2016-03-24 | 日本電気硝子株式会社 | Li2o-al2o3-sio2-based crystallized glass and production method therefor |
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