JP7488508B2 - Glass articles - Google Patents
Glass articles Download PDFInfo
- Publication number
- JP7488508B2 JP7488508B2 JP2020057265A JP2020057265A JP7488508B2 JP 7488508 B2 JP7488508 B2 JP 7488508B2 JP 2020057265 A JP2020057265 A JP 2020057265A JP 2020057265 A JP2020057265 A JP 2020057265A JP 7488508 B2 JP7488508 B2 JP 7488508B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- glass article
- content
- refractive index
- coloring
- 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.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims description 55
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000010437 gem Substances 0.000 claims description 4
- 229910001751 gemstone Inorganic materials 0.000 claims description 4
- 238000004040 coloring Methods 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000004017 vitrification Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 235000019646 color tone Nutrition 0.000 description 8
- 239000003086 colorant Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000006103 coloring component Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Adornments (AREA)
- Glass Compositions (AREA)
Description
本発明は、装飾用として好適なガラス物品に関する。 The present invention relates to glass articles suitable for decorative purposes.
従来、ガラス中に着色剤を添加することにより、ガラスに種々の色調を付与する技術が提案されている。例えば、イオンによる着色、コロイド粒子による着色等が古くから行われており、様々な発色が実現されている。例えば、赤系の色調を呈するガラスを得るための着色方法としては、酸化物系ガラスにおいては、Ｃｄ－Ｓｅによる着色、Ａｕコロイドによる着色、Ｃｕコロイドによる着色が知られている。また、着色剤として酸化銅と酸化ネオジム、還元剤として酸化スズ、安定剤として酸化アンチモンを組み合わせる着色方法も提案されている（例えば特許文献１参照）。 Conventionally, techniques have been proposed for imparting various color tones to glass by adding colorants to the glass. For example, coloring with ions and coloring with colloidal particles have been used for a long time, and various colors have been achieved. For example, coloring with Cd-Se, coloring with Au colloid, and coloring with Cu colloid are known as coloring methods for obtaining glass with a reddish color tone in oxide-based glass. In addition, a coloring method has been proposed that combines copper oxide and neodymium oxide as colorants, tin oxide as a reducing agent, and antimony oxide as a stabilizer (see, for example, Patent Document 1).
Ｃｄ－Ｓｅのような着色剤は鮮明な赤色を与えるが、毒性成分であるために好ましくない。またＡｕコロイドによる着色は青みを帯びた鮮やかな赤になり、Ｃｕコロイドによる着色は少し暗みを帯びた雰囲気のある赤色が得られるが、いずれも酸化／還元の雰囲気や、温度制御が難しいという問題があり、さらに熱処理により結晶化しやすい不安定なガラスには適応しにくいという問題もある。酸化銅と酸化ネオジムに対し、還元剤及び安定剤を組み合わせた着色方法も、着色の制御が複雑であり、安定した色調の赤色ガラスを得ることは困難である。 Colorants such as Cd-Se give a vivid red color, but are undesirable because they are toxic components. Coloring with Au colloids produces a vivid red with a bluish tinge, while coloring with Cu colloids produces a red color with a slightly darker atmosphere, but both have problems with the oxidation/reduction atmosphere and difficulty in controlling the temperature, and there is also the problem that they are difficult to apply to unstable glass that easily crystallizes due to heat treatment. Coloring methods that combine copper oxide and neodymium oxide with reducing agents and stabilizers also require complex color control, making it difficult to obtain red glass with a stable color tone.
以上に鑑み、本発明は、毒性成分を含有しなくても鮮やかな赤色を発色し、色再現性が高い、装飾用として好適であるガラス物品を提供することを目的とする。 In view of the above, the present invention aims to provide a glass article that produces a vivid red color without containing any toxic components, has high color reproducibility, and is suitable for decorative purposes.
本発明者等が鋭意検討した結果、ＴｉＯ２を必須成分として含有する特定組成のガラス中に、着色剤であるＣｅＯ２を添加することで、上記課題を達成できることを見出した。 As a result of intensive research, the present inventors have found that the above object can be achieved by adding CeO2 , which is a colorant, to glass having a specific composition containing TiO2 as an essential component.
即ち、本発明のガラス物品は、モル％で、ＴｉＯ２ ２０～８５％、Ｂ２Ｏ３ ０～４０％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５＋Ｔａ２Ｏ５＋Ｇｄ２Ｏ３＋ＺｒＯ２ ０．１～８０％未満、及び、ＣｅＯ２ ０超～１０％を含有することを特徴とする。ガラス組成をこのような範囲に規定することにより、色再現性の高い鮮やかな色調の赤系着色ガラス部物品を得ることができる。 That is, the glass article of the present invention is characterized by containing, in mol %, 20 to 85% TiO 2 , 0 to 40% B 2 O 3 , 0.1 to less than 80% La 2 O 3 + Nb 2 O 5 + Ta 2 O 5 + Gd 2 O 3 + ZrO 2 , and more than 0 to 10% CeO 2. By defining the glass composition within such ranges, it is possible to obtain a red-colored glass article with a vivid color tone and high color reproducibility.
本発明のガラス物品は、屈折率（ｎｄ）が２．０以上であることが好ましい。このようにすれば、ガラス物品の内部と外部（大気）との屈折率差が大きくなり、ガラス物品内部で光が反射しやすくなる。その結果、輝きが強くなり装飾用のガラス物品として好適となる。 The glass article of the present invention preferably has a refractive index (nd) of 2.0 or more. This increases the difference in refractive index between the inside and outside (atmosphere) of the glass article, making it easier for light to be reflected inside the glass article. As a result, the glass article has a stronger shine and is suitable as a decorative glass article.
本発明のガラス物品は、面取り加工が施されていることが好ましい。このようにすれば、ガラス物品内部で光が反射しやすくなり、輝きを高めることが可能となる。 It is preferable that the glass article of the present invention is chamfered. This makes it easier for light to be reflected inside the glass article, enhancing its brilliance.
本発明のガラス物品は、疑似宝石であることが好ましい。 The glass article of the present invention is preferably a pseudo-gemstone.
本発明の装飾品は、上記のガラス物品を備えることを特徴とする。 The decorative article of the present invention is characterized by comprising the above-mentioned glass article.
本発明によれば、毒性成分を含有しなくても鮮やかな赤色を発色し、色再現性が高い、装飾用として好適であるガラス物品を提供することができる。 The present invention provides a glass article that is suitable for decorative purposes, has a vivid red color and high color reproducibility, even without containing toxic components.
本発明のガラス物品は、モル％で、ＴｉＯ２ ２０～８５％、Ｂ２Ｏ３ ０～４０％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５＋Ｔａ２Ｏ５＋Ｇｄ２Ｏ３＋ＺｒＯ２ ０．１～８０％未満、及び、ＣｅＯ２ ０超～１０％を含有することを特徴とする。ガラス組成をこのように限定した理由を以下に説明する。なお、以下の各成分の含有量に関する説明において、特に断りのない限り「％」は「モル％」を意味する。 The glass article of the present invention is characterized by containing, in mole percent, 20-85% TiO 2 , 0-40% B 2 O 3 , 0.1-less than 80% La 2 O 3 +Nb 2 O 5 +Ta 2 O 5 +Gd 2 O 3 +ZrO 2 , and more than 0-10% CeO 2 . The reason for limiting the glass composition in this way will be explained below. In the following explanation of the content of each component, "%" means "mol %" unless otherwise specified.
ＴｉＯ２は吸収端を長波長へシフトさせる成分であり、赤系着色を得るために重要な成分である。また、屈折率を高める効果が大きい成分であり、化学的耐久性を高める効果もある。またアッベ数を低下させ高分散にする効果もある。ガラスが高分散となると、「ファイア」と呼ばれる虹色の輝きが発現しやすくなる。ＴｉＯ２の含有量は２０～８５％、２１～８４％、２３～８４％、２４～８４％、特に２５～８４％であることが好ましい。ＴｉＯ２の含有量が少なすぎると、鮮やかな赤系発色が得られにくくなる。一方、ＴｉＯ２の含有量が多すぎると、ガラス化しにくくなる。 TiO2 is a component that shifts the absorption edge to longer wavelengths, and is an important component for obtaining red coloring. It is also a component that has a large effect of increasing the refractive index, and also has the effect of increasing chemical durability. It also has the effect of lowering the Abbe number and making it highly dispersive. When glass has a high dispersion, it is easy to develop the rainbow-colored shine called "fire". The content of TiO2 is preferably 20-85%, 21-84%, 23-84%, 24-84%, and especially 25-84%. If the content of TiO2 is too low, it is difficult to obtain a vivid red color. On the other hand, if the content of TiO2 is too high, it is difficult to vitrify.
Ｂ２Ｏ３はガラス骨格となり、ガラス化範囲を広げる成分である。ただし、Ｂ２Ｏ３の含有量が多すぎると、屈折率が低下して所望の光学特性が得にくくなる。従って、Ｂ２Ｏ３の含有量は０～４０％、０．１～４０％、１～３０％、２～２５％、特に３～２０％であることが好ましい。 B 2 O 3 is a component that forms a glass skeleton and expands the vitrification range. However, if the content of B 2 O 3 is too high, the refractive index decreases and it becomes difficult to obtain the desired optical characteristics. Therefore, the content of B 2 O 3 is preferably 0 to 40%, 0.1 to 40%, 1 to 30%, 2 to 25%, and particularly preferably 3 to 20%.
Ｌａ２Ｏ３＋Ｎｂ２Ｏ５＋Ｔａ２Ｏ５＋Ｇｄ２Ｏ３＋ＺｒＯ２の含有量は０．１～８０％未満であり、好ましくは１０～７７％、より好ましくは２０～７５％である。Ｌａ２Ｏ３＋Ｎｂ２Ｏ５＋Ｔａ２Ｏ５＋Ｇｄ２Ｏ３＋ＺｒＯ２が少なすぎると、ガラス化しにくくなり、また所望の屈折率が得られにくくなる。一方、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５＋Ｔａ２Ｏ５＋Ｇｄ２Ｏ３＋ＺｒＯ２が多すぎると、かえってガラス化しにくくなる。またＴｉＯ２の含有量が少なくなって、所望の赤色着色が得にくくなる。なお本明細書において、「○＋○＋・・・」は各成分の合量を意味する。 The content of La 2 O 3 + Nb 2 O 5 + Ta 2 O 5 + Gd 2 O 3 + ZrO 2 is 0.1 to less than 80%, preferably 10 to 77%, more preferably 20 to 75%. If the amount of La 2 O 3 + Nb 2 O 5 + Ta 2 O 5 + Gd 2 O 3 + ZrO 2 is too small, it becomes difficult to vitrify and it becomes difficult to obtain the desired refractive index. On the other hand, if the amount of La 2 O 3 + Nb 2 O 5 + Ta 2 O 5 + Gd 2 O 3 + ZrO 2 is too large, it becomes difficult to vitrify. In addition, the content of TiO 2 becomes small, and it becomes difficult to obtain the desired red coloring. In this specification, "○ + ○ + ..." means the total amount of each component.
以下、Ｌａ２Ｏ３、Ｎｂ２Ｏ５、Ｔａ２Ｏ５、Ｇｄ２Ｏ３及びＺｒＯ２の各成分について説明する。 Hereinafter , each of the components La2O3 , Nb2O5 , Ta2O5 , Gd2O3 and ZrO2 will be described.
Ｌａ２Ｏ３はガラス骨格を形成する成分であり、光透過率を低下させることなく屈折率を高める成分である。また、ガラス化の安定性を高める成分でもある。Ｌａ２Ｏ３の含有量は０～６０％、１～４５％、５～４３％、特に８～４０％であることが好ましい。Ｌａ２Ｏ３の含有量が多すぎると、かえってガラス化しにくくなる。 La 2 O 3 is a component that forms a glass skeleton and increases the refractive index without decreasing the light transmittance. It is also a component that increases the stability of vitrification. The content of La 2 O 3 is preferably 0 to 60%, 1 to 45%, 5 to 43%, and particularly preferably 8 to 40%. If the content of La 2 O 3 is too high, vitrification becomes difficult.
Ｎｂ２Ｏ５は屈折率を高める効果が大きい成分であり、アッベ数を低下させ高分散にする成分である。またガラス化範囲を広げる効果もある。Ｎｂ２Ｏ５の含有量は０～７０％、１～６０％、２～５０％、３～４８％、特に４～４５％であることが好ましい。Ｎｂ２Ｏ５の含有量が多すぎると、かえってガラス化しにくくなる。 Nb 2 O 5 is a component that has a large effect of increasing the refractive index, and is a component that reduces the Abbe number and provides high dispersion. It also has the effect of widening the vitrification range. The content of Nb 2 O 5 is preferably 0 to 70%, 1 to 60%, 2 to 50%, 3 to 48%, and particularly preferably 4 to 45%. If the content of Nb 2 O 5 is too high, vitrification becomes more difficult.
Ｔａ２Ｏ５は屈折率を高める効果が大きい成分である。ただし、Ｔａ２Ｏ５の含有量が多すぎると、ガラス化しにくくなり、また原料コストが高くなる傾向がある。従って、Ｔａ２Ｏ５の含有量は０～６０％、０．１～６０％、１～５０％、２～４５％、特に３～４０％であることが好ましい。 Ta 2 O 5 is a component that has a large effect of increasing the refractive index. However, if the content of Ta 2 O 5 is too high, vitrification becomes difficult and the raw material cost tends to increase. Therefore, the content of Ta 2 O 5 is preferably 0 to 60%, 0.1 to 60%, 1 to 50%, 2 to 45%, and particularly preferably 3 to 40%.
Ｇｄ２Ｏ３は屈折率を高める成分である。また、耐候性を向上させる効果もある。ただし、Ｇｄ２Ｏ３の含有量が多すぎると、ガラス化しにくくなる。従って、Ｇｄ２Ｏ３の含有量は０～４０％、０．１～４０％、１～３０％、特に２～２０％であることが好ましい。 Gd 2 O 3 is a component that increases the refractive index. It also has the effect of improving weather resistance. However, if the Gd 2 O 3 content is too high, it becomes difficult to vitrify. Therefore, the Gd 2 O 3 content is preferably 0 to 40%, 0.1 to 40%, 1 to 30%, and particularly preferably 2 to 20%.
ＺｒＯ２は屈折率を高める成分である。また、ガラス化範囲を広げる効果がある。ただし、ＺｒＯ２の含有量が多すぎると、かえってガラス化しにくくなり、また溶融温度が高くなりすぎる。従って、ＺｒＯ２の含有量は０～４０％、０．１～４０％、１～３０％、２～２５％、特に３～２０％であることが好ましい。 ZrO2 is a component that increases the refractive index. It also has the effect of widening the vitrification range. However, if the ZrO2 content is too high, vitrification becomes difficult and the melting temperature becomes too high. Therefore, the ZrO2 content is preferably 0 to 40%, 0.1 to 40%, 1 to 30%, 2 to 25%, and particularly preferably 3 to 20%.
ＣｅＯ２は赤系着色成分であり、ＴｉＯ２による吸収端の長波長側へのシフトの効果と相まって、ガラスに鮮やかな赤色の色調を付与する。ただし、ＣｅＯ２の含有量が多すぎると、着色が濃くなりすぎ、鮮やかな赤色が得られにくくなる。従って、ＣｅＯ２の含有量は０超～１０％、０．１～５％、０．２～４％、特に０．３～３％であることが好ましい。 CeO2 is a red-based coloring component, and in combination with the effect of shifting the absorption edge to the long wavelength side by TiO2 , it gives the glass a vivid red color tone. However, if the CeO2 content is too high, the coloring becomes too dark and it becomes difficult to obtain a vivid red color. Therefore, the CeO2 content is preferably more than 0 to 10%, 0.1 to 5%, 0.2 to 4%, and particularly 0.3 to 3%.
本発明のガラス物品には、上記成分以外にも、ガラス化範囲を広げるためＳｉＯ２、Ａｌ２Ｏ３、ＺｎＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ等を各々１０％以下の範囲で、Ｙ２Ｏ３を２０％以下の範囲で含有させてもよい。 In addition to the above components, the glass article of the present invention may contain SiO2 , Al2O3 , ZnO , MgO, CaO, SrO, BaO, etc., each in an amount of 10% or less, and Y2O3 in an amount of 20% or less, in order to expand the vitrification range.
本発明のガラス物品には、所望の色調に調整するため、ＣｅＯ２以外の遷移金属酸化物や希土類酸化物といった着色成分を含有させてもよい。具体的には、遷移金属酸化物としては、Ｃｒ２Ｏ３、ＭｎＯ２、Ｆｅ２Ｏ３、ＣｏＯ、ＮｉＯ、ＣｕＯ、Ｖ２Ｏ５、ＭｏＯ３、ＲｕＯ２等が挙げられる。なお、ＣｅＯ２による着色は若干橙色寄りの赤色となる傾向があるが、ＣｅＯ２に加えてＣｒ２Ｏ３またはＦｅ２Ｏ３を含有させることにより、より鮮明な赤色を呈するガラス物品を得ることが可能となる。希土類酸化物としては、Ｎｄ２Ｏ３、Ｅｕ２Ｏ３、Ｔｂ２Ｏ３、Ｄｙ２Ｏ３、Ｅｒ２Ｏ３等が挙げられる。これらの遷移金属酸化物及び希土類酸化物は単独で含有させてもよく、２種以上を含有させてもよい。これらの遷移金属酸化物及び希土類酸化物の含有量（２種以上含有させる場合は合量）は、０～５％、０．０００１～３％、０．００１～３％、０．０１～２％、０．０２～１％、特に０．０２～０．１％であることが好ましい。なお、含有させる成分によっては着色が強くなりすぎて、可視域透過率が低下し、所望の輝きが得られない場合がある。その場合は、上記の遷移金属酸化物及び希土類酸化物の含有量を１％未満、０．５％以下、０．１％以下、さらには０．０１％以下としてもよい。 The glass article of the present invention may contain coloring components such as transition metal oxides and rare earth oxides other than CeO 2 in order to adjust the color tone to a desired tone. Specifically, examples of transition metal oxides include Cr 2 O 3 , MnO 2 , Fe 2 O 3 , CoO, NiO, CuO, V 2 O 5 , MoO 3 , and RuO 2. Note that coloring by CeO 2 tends to be a red color slightly closer to orange, but by adding Cr 2 O 3 or Fe 2 O 3 in addition to CeO 2 , it is possible to obtain a glass article that exhibits a brighter red color. Examples of rare earth oxides include Nd 2 O 3 , Eu 2 O 3 , Tb 2 O 3 , Dy 2 O 3 , and Er 2 O 3. These transition metal oxides and rare earth oxides may be contained alone or in combination of two or more. The content of these transition metal oxides and rare earth oxides (total amount when two or more kinds are contained) is preferably 0 to 5%, 0.0001 to 3%, 0.001 to 3%, 0.01 to 2%, 0.02 to 1%, and particularly preferably 0.02 to 0.1%. Note that, depending on the components contained, the coloring may be too strong, the visible transmittance may decrease, and the desired brightness may not be obtained. In such cases, the content of the above transition metal oxides and rare earth oxides may be less than 1%, 0.5% or less, 0.1% or less, or even 0.01% or less.
本発明のガラス物品は、Ｌａ２Ｏ３、Ｎｂ２Ｏ５、Ｂ２Ｏ３等のガラス化範囲を広げる成分を積極的に含有させることにより、ガラス作製時における不当な結晶化を抑制し、ガラス物品のサイズを大きくする（例えば、直径２ｍｍ以上、３ｍｍ以上、４ｍｍ以上、特に５ｍｍ以上）ことが容易になる。 The glass article of the present invention actively contains components that expand the vitrification range, such as La2O3 , Nb2O5 , and B2O3 , which suppresses inappropriate crystallization during glass production and makes it easy to increase the size of the glass article (for example, a diameter of 2 mm or more, 3 mm or more, 4 mm or more, and particularly 5 mm or more).
本発明のガラス物品は、屈折率（ｎｄ）が２．０以上、２．１以上、２．２以上、特に２．２５以上であることが好ましい。このようにすれば、ガラス物品の内部と外部（大気）との屈折率差が大きくなり、ガラス物品内部で光が反射しやすくなる。その結果、輝きが強くなり装飾用のガラス物品として好適となる。なお、屈折率の上限は特に限定されないが、大きすぎるとガラス化が不安定になるため、２．６以下、２．５以下、特に２．４以下であることが好ましい。 The glass article of the present invention preferably has a refractive index (nd) of 2.0 or more, 2.1 or more, 2.2 or more, and particularly preferably 2.25 or more. This increases the difference in refractive index between the inside and outside (atmosphere) of the glass article, making it easier for light to be reflected inside the glass article. As a result, the glass article has a stronger shine and is suitable as a decorative glass article. There is no particular upper limit to the refractive index, but if it is too high, vitrification becomes unstable, so it is preferably 2.6 or less, 2.5 or less, and particularly preferably 2.4 or less.
本発明のガラス物品のアッベ数（νｄ）は５０以下、４０以下、３０以下、特に２５以下であることが好ましい。このようにすれば、ガラス物品が高分散となり、ファイアが発現しやすくなる。なお、アッベ数の下限は特に限定されないが、小さすぎるとガラス化が不安定になるため、５以上、特に１０以上であることが好ましい。 The Abbe number (νd) of the glass article of the present invention is preferably 50 or less, 40 or less, 30 or less, and particularly 25 or less. In this way, the glass article becomes highly dispersed and fire is more likely to occur. There is no particular lower limit to the Abbe number, but if it is too small, vitrification becomes unstable, so it is preferably 5 or more, and particularly 10 or more.
本発明のガラス物品は、宝飾品、芸術品、食器等の装飾品用途に使用することができる。例えば、指輪、ペンダント、イヤリング、ブレスレット等の装飾品（宝飾品）に疑似宝石として取り付けて使用することができる。ガラス物品の形状は特に限定されず球形、楕球形、多面体等が挙げられる。 The glass article of the present invention can be used for decorative purposes such as jewelry, art, and tableware. For example, it can be attached to decorative items (jewelry) such as rings, pendants, earrings, and bracelets as a pseudo-gemstone. The shape of the glass article is not particularly limited, and examples include a sphere, an ellipse, and a polyhedron.
本発明のガラス物品は、いわゆるブリリアントカット、ステップカットやミックスカット等の面取り加工が施されていることが好ましい。このようにすれば、ガラス物品内部で光が反射しやすくなり、輝きを高めることが可能となり、特に疑似宝石として好適となる。 The glass article of the present invention is preferably subjected to chamfering such as brilliant cut, step cut, or mixed cut. This makes it easier for light to be reflected inside the glass article, enhancing its brilliance, making it particularly suitable as a pseudo-gemstone.
以下、本発明のガラス物品について、実施例を用いて詳細に説明するが、本発明は以下の実施例に限定されるものではない。 The glass article of the present invention will be described in detail below using examples, but the present invention is not limited to the following examples.
表１～３は、本発明の実施例（Ｎｏ．１～２２）及び比較例（Ｎｏ．２３～２４）を示す。 Tables 1 to 3 show examples of the present invention (Nos. 1 to 22) and comparative examples (Nos. 23 to 24).
まず表に示す各ガラス組成となるように原料を調合して原料バッチを作製し、均質になるまで溶融した。溶融温度は、試料Ｎｏ．１～２３は１５００～２０００℃、試料Ｎｏ．２４は１４００～１５００℃とした。溶融ガラスを急冷固化させた後、ガラス転移温度付近（４５０～８００℃）でアニールすることによりガラス試料を得た。得られたガラス試料について、下記の方法により屈折率（ｎｄ）及び色調を評価した。 First, raw materials were mixed to prepare raw material batches for each glass composition shown in the table, and melted until homogeneous. The melting temperatures were 1500-2000°C for samples No. 1-23, and 1400-1500°C for sample No. 24. The molten glass was rapidly cooled and solidified, and then annealed near the glass transition temperature (450-800°C) to obtain glass samples. The refractive index (nd) and color tone of the obtained glass samples were evaluated using the following method.
屈折率（ｎｄ）は、ガラス試料に対して直角研磨を行い、ＫＰＲ－２０００（島津製作所製）を用いて測定した。屈折率（ｎｄ）はヘリウムランプｄ線（５８７．６ｎｍ）に対する測定値で評価した。 The refractive index (nd) was measured using a KPR-2000 (Shimadzu Corporation) after polishing the glass sample at a right angle. The refractive index (nd) was evaluated using the measured value for the helium lamp d line (587.6 nm).
色調は、各試料を蛍光灯光源下で目視にて観察することにより評価した。なお、Ｎｏ．１３、Ｎｏ．２３、Ｎｏ．２４の試料の写真を図１に示す（Ｎｏ．１３、Ｎｏ．２３の試料についてはブリリアントカット加工を施している）。 The color tone was evaluated by visually observing each sample under a fluorescent light source. Photographs of samples No. 13, No. 23, and No. 24 are shown in Figure 1 (samples No. 13 and No. 23 were subjected to brilliant cut processing).
表１～３及び図１から明らかなように、実施例であるＮｏ．１～２２の試料は色調が赤色であり、屈折率が２．２３０以上と高かった。なお、Ｎｏ．１～３、５～９、１１、１２～１６、１８、１９、２１、２２の試料は若干橙色寄りの赤色を呈していたのに対し、Ｎｏ．４、１０、１７、２０の試料は鮮明な赤色を呈していた。一方、比較例であるＮｏ．２３の試料は色調が橙色であった。また、Ｎｏ．２４の試料は淡黄色であり、屈折率が１．５１６と低かった。 As is clear from Tables 1 to 3 and Figure 1, the samples No. 1 to 22, which are examples, were red in color and had a high refractive index of 2.230 or more. Samples No. 1 to 3, 5 to 9, 11, 12 to 16, 18, 19, 21, and 22 were red with a slight orange tint, while samples No. 4, 10, 17, and 20 were bright red. On the other hand, sample No. 23, which is a comparative example, was orange in color. Sample No. 24 was pale yellow and had a low refractive index of 1.516.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019131845 | 2019-07-17 | ||
| JP2019131845 | 2019-07-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021017393A JP2021017393A (en) | 2021-02-15 |
| JP7488508B2 true JP7488508B2 (en) | 2024-05-22 |
Family
ID=74563997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020057265A Active JP7488508B2 (en) | 2019-07-17 | 2020-03-27 | Glass articles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7488508B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011093769A (en) | 2009-10-31 | 2011-05-12 | Ohara Inc | Glass ceramic and method for manufacturing the same |
| JP2013123790A (en) | 2011-12-16 | 2013-06-24 | Asahi Glass Co Ltd | Polishing brush, polishing method of end face of glass substrate, and method for manufacturing glass substrate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA919195A (en) * | 1963-02-14 | 1973-01-16 | Fang Tung Chi | High index glass elements |
| JPS59164650A (en) * | 1983-03-10 | 1984-09-17 | Toshiba Glass Co Ltd | Glass bead having high refractive index |
| JPH04106806A (en) * | 1990-08-27 | 1992-04-08 | Matsushita Electric Works Ltd | Complex dielectric |
| CZ307684B6 (en) * | 2016-12-23 | 2019-02-13 | Preciosa, A.S. | A material for the production of costume jewellery and jewellery stones with a high index of refraction and high heat resistance |
-
2020
- 2020-03-27 JP JP2020057265A patent/JP7488508B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011093769A (en) | 2009-10-31 | 2011-05-12 | Ohara Inc | Glass ceramic and method for manufacturing the same |
| JP2013123790A (en) | 2011-12-16 | 2013-06-24 | Asahi Glass Co Ltd | Polishing brush, polishing method of end face of glass substrate, and method for manufacturing glass substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021017393A (en) | 2021-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10150694B2 (en) | Opaque colored glass-ceramics comprising nepheline crystal phases | |
| TWI316929B (en) | Optical glass | |
| US7297645B2 (en) | Opalescent glass-ceramic product | |
| TW201311601A (en) | Glass to be chemically reinforced and glass housing | |
| WO1997014661A1 (en) | High-index glasses that absorb uv radiation | |
| JP2014031305A (en) | Glass for chemical strengthening and chemically strengthened glass | |
| JPH08109039A (en) | Photochromic glass and lens for glasses consisting of it | |
| EP1015394A1 (en) | Improved photochromic glasses | |
| TW201638039A (en) | Glass article and light guide | |
| JP7488508B2 (en) | Glass articles | |
| US5387558A (en) | Colored glass-ceramic articles | |
| JP2006327882A (en) | Crystallized glass, crystallized glass building material, and manufacture method of crystallized glass article | |
| JP2020502026A (en) | Holmium-based contrast-enhancing UV-blocking glass composition | |
| CN105923991B (en) | Optical glass, its preparation method and application | |
| JP7445195B2 (en) | glass articles | |
| CN111517643A (en) | Glass composition and method for producing the same | |
| WO2015118964A1 (en) | Near-infrared absorbing/high-contrast glass lens | |
| WO2021095622A1 (en) | Glass article | |
| WO2020203673A1 (en) | Decorative glass article | |
| WO2020203309A1 (en) | Decorative glass article | |
| WO2014007222A1 (en) | Glass production method and chemically strengthened glass | |
| JP2020172427A (en) | Decorative glass article | |
| US4687751A (en) | Opal glass exhibiting a creamy-white tint | |
| JP2021066654A (en) | Glass article | |
| JP7507332B1 (en) | Dental porcelain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230208 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230710 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230803 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230921 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231207 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240122 |
|
| 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: 20240410 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240423 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7488508 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |