JP5229828B2 - Copper red glass - Google Patents
Copper red glass Download PDFInfo
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- JP5229828B2 JP5229828B2 JP2009526976A JP2009526976A JP5229828B2 JP 5229828 B2 JP5229828 B2 JP 5229828B2 JP 2009526976 A JP2009526976 A JP 2009526976A JP 2009526976 A JP2009526976 A JP 2009526976A JP 5229828 B2 JP5229828 B2 JP 5229828B2
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- 239000010949 copper Substances 0.000 title claims description 62
- 229910052802 copper Inorganic materials 0.000 title claims description 34
- 239000011521 glass Substances 0.000 title claims description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000005361 soda-lime glass Substances 0.000 claims description 5
- 238000003303 reheating Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
本発明は、ガラスびん、食器、花器、板ガラスなどとして広く使用することができる赤色に発色させたソーダ石灰ガラスに関する。 The present invention relates to red soda-lime glass that can be widely used as glass bottles, tableware, vases, plate glass, and the like.
下記特許文献１には、清澄剤である芒硝を０〜０．３ｋｇ/砂１００ｋｇに制限し、ガラス中の硫黄成分を極力少なくすることで、還元状態におけるアンバー色を抑え、再加熱処理を行うことなく、赤色に発色させる技術が開示されている。
In
前記特許文献１に開示されている技術は、再加熱処理を行うことなく赤色ガラスを得ることは可能であるが、赤色の発色が不安定で、ときとして赤色が薄くなったり、茶色がかったりする場合があった。
本発明は、再加熱処理を行うことなく良好な赤色（いわゆる銅赤）に安定して発色する赤色ガラスを開発することを課題とするものである。The technique disclosed in
An object of the present invention is to develop a red glass that stably develops a good red color (so-called copper red) without performing reheating treatment.
本発明は、ＣｕをＣｕ２Ｏ換算で０．０２５〜０．０８５ｍｏｌ％、ＳをＳＯ３換算値で０．０２３〜０．０７8ｍｏｌ％含み、かつ、ＣｕとＳの量の比がＣｕ２Ｏ換算モル値／ＳＯ３換算モル値で１．５０〜０．７０のソーダ石灰ガラスでなることを特徴とする銅赤ガラスである。
ガラス中の銅、硫黄の量をこのように構成することで、主波長（λｄ）が５９３〜６２０ｎｍの良好な赤色を呈する銅赤ガラスを、再加熱処理を行うことなく、優れた再現性をもって製造できる。
The present invention includes 0.025 to 0.085 mol% of Cu in terms of Cu 2 O, 0.023 to 0.078 mol% of S in terms of SO 3 , and the ratio of the amount of Cu and S is Cu 2 O. It is copper red glass characterized by consisting of 1.50 to 0.70 soda-lime glass in terms of converted molar value / SO 3 converted molar value.
By configuring the amount of copper and sulfur in the glass in this way, the copper red glass exhibiting a good red color having a dominant wavelength (λd) of 593 to 620 nm can be reproducibly performed without reheating. Can be manufactured.
また本発明は、ＣｕをＣｕ２Ｏ換算で０．０３４〜０．０６５ｍｏｌ％、ＳをＳＯ３換算値で０．０２９〜０．０６ｍｏｌ％含み、かつ、ＣｕとＳの量の比がＣｕ２Ｏ換算モル値／ＳＯ３換算モル値で１．４５〜０．７８のソーダ石灰ガラスでなることを特徴とする銅赤ガラスである。
ガラス中の銅、硫黄の量をこのように構成することで、主波長（λｄ）が６００〜６２０ｎｍのさらに良好な赤色を呈する銅赤ガラスを、再加熱処理を行うことなく、優れた再現性をもって製造できる。
Further, the present invention includes 0.034 to 0.065 mol% Cu in terms of Cu 2 O, 0.029 to 0.06 mol% in terms of SO 3 , and the ratio of the amount of Cu and S is Cu 2. It is copper red glass characterized by consisting of 1.45 to 0.78 soda-lime glass in terms of O converted molar value / SO 3 converted molar value.
By configuring the amount of copper and sulfur in the glass in this manner, excellent reproducibility without reheating the copper red glass exhibiting a better red color having a dominant wavelength (λd) of 600 to 620 nm. Can be manufactured.
本発明において、ガラス中のＣｕ２Ｏの量はＣｕ２Ｏ換算で０．０２５〜０．０８５ｍｏｌ％が好ましく、さらに好ましくはＣｕ２Ｏ換算で０．０３４〜０．０６５ｍｏｌ％である。Ｃｕ２Ｏの量が少なすぎると、着色成分である銅コロイドが減り発色に至らない。多すぎるとコスト高になる。
本発明において、銅赤ガラスに使用する量は従来よりもきわめて少量でよい。例えば、前記特許文献１における銅の量（Ｃｕ２Ｏ換算）は０．５〜０．９mass％（ｍｏｌ換算すると０．３５〜０．６３ｍｏｌ％）程度である。In the present invention, the amount of Cu 2 O in the glass is preferably 0.025～0.085Mol% in Cu 2 O in terms of, even more preferably 0.034～0.065Mol% in Cu 2 O conversion. If the amount of
In the present invention, the amount used for the copper red glass may be much smaller than the conventional amount. For example, the amount of copper (in terms of Cu 2 O) in
ガラス中のＳの量（ＳＯ３換算値）は０．０２３〜０．０７８ｍｏｌ％が好ましく、さらに好ましくは０．０２９〜０．０６ｍｏｌ％である。Ｓ成分の原料は芒硝の他、硫化亜鉛、硫化鉄等の硫化物の形で添加してもよい。ガラス中のＳ（ＳＯ３換算値）の量が少なすぎると、核である硫化物の生成量が減り、銅コロイドが析出しなくなり、再加熱処理が必要になる。多すぎると、ＣｕＳやＦｅＳなどの硫化物の生成量が多くなりアンバー発色してしまう。The amount of S in the glass (SO 3 equivalent value) is preferably 0.023 to 0.078 mol%, more preferably 0.029 to 0.06 mol%. The raw material of the S component may be added in the form of sulfides such as zinc sulfide and iron sulfide in addition to sodium sulfate. If the amount of S (SO 3 equivalent value) in the glass is too small, the amount of sulfides that are nuclei will be reduced, copper colloid will not precipitate, and reheating will be necessary. If the amount is too large, the amount of sulfides such as CuS and FeS increases, resulting in amber coloration.
本発明は、ガラス中のＣｕとＳの量の比がＣｕ２Ｏ換算モル値／ＳＯ３換算モル値で１．５０〜０．７０であることを特徴とする。さらに好ましくは１．４５〜０．７８である。本発明において、再加熱処理を行うことなく良好な赤色を安定して得るためには、ＣｕとＳの量の比が重要であることが発見されたのである。The present invention is characterized in that the ratio of the amount of Cu and S in the glass is 1.50 to 0.70 in terms of Cu 2 O equivalent molar value / SO 3 equivalent molar value. More preferably, it is 1.45 to 0.78. In the present invention, it has been discovered that the ratio of the amount of Cu and S is important in order to stably obtain a good red color without performing reheating treatment.
表１は、ガラス中のＣｕの量を固定し、Ｓの量の比を変化させた場合の色の変化を調べた結果である。ＣｕとＳの量は、それぞれＣｕ２Ｏ換算モル％、ＳＯ３換算モル％で表している。
また、図１は表１をグラフにしたものである。
FIG. 1 is a graph of Table 1.
表１及び図１から明らかなように、Ｃｕに対してＳが少なすぎるとガラスの色は青色になり、多すぎると茶色になる。
図１において、主波長（λd）５９３〜６２０ｎｍの良好な赤色（銅赤）となるとためのＣｕ２Ｏ換算ｍｏｌ値／ＳＯ３換算モル値は１．５０〜０．７０である。また、主波長（λd）６００〜６２０ｎｍのさらに良好な赤色（銅赤）となるためのＣｕ２Ｏ換算ｍｏｌ値／ＳＯ３換算モル値は１．４５〜０．７８である。
したがって、ＣｕとＳの量の比をこの範囲とすることで、良好な銅赤ガラスを安定して得ることができる。As apparent from Table 1 and FIG. 1, when the amount of S is too small with respect to Cu, the color of the glass is blue, and when it is too large, the color is brown.
In FIG. 1, the Cu 2 O equivalent mol value / SO 3 equivalent mol value for a good red (copper red) having a dominant wavelength (λd) of 593 to 620 nm is 1.50 to 0.70. Also, dominant wavelength (.lambda.d) better red Cu 2 O in terms mol value for a (Doaka) / SO 3 conversion mole value of 600~620nm is 1.45 to 0.78.
Therefore, a favorable copper red glass can be stably obtained by setting the ratio of the amount of Cu and S in this range.
その理由として、ガラスが赤色に発色する原因となる銅コロイドは、核となる物質の周りに金属銅が析出して成長すると考えられ、ガラス中のＣｕとＳの量の比が適度であれば、核となるＣｕＳやＦｅＳの量が適度となり、銅コロイドが順調に生成されて良好な赤色に発色するが、Ｃｕに対してＳの量が少なすぎると、核になる物質が少なくなって銅コロイドの生成が不十分となり、赤色が薄くなったり赤色に発色せずに青色となったりし、Ｃｕに対してＳの量が多すぎるとガラス中のＣｕＳの量が多くなりすぎ、茶色系の色となってしまうと考えられる。 The reason for this is that the copper colloid that causes the glass to develop a red color is thought to grow by depositing copper metal around the core material, and if the ratio of the amount of Cu and S in the glass is moderate The amount of CuS and FeS serving as nuclei becomes moderate, and copper colloids are generated smoothly and develop a good red color. However, if the amount of S relative to Cu is too small, the amount of nuclei becomes less and copper Colloid formation is insufficient, red color becomes thin or blue color does not develop red, and if the amount of S relative to Cu is too large, the amount of CuS in the glass becomes too large, It is thought that it becomes a color.
本発明の銅赤ガラスは、再加熱処理を行うことなく安定して銅赤色に発色するので、歩留まりよく製造することができる。また、使用する銅の量が少なくてよいので、従来よりも低コストとなる。 Since the copper red glass of the present invention stably develops a copper red color without reheating, it can be manufactured with a high yield. Moreover, since the amount of copper to be used may be small, the cost is lower than in the past.
〔実施例〕
表２のガラス組成となるように原料を調合し、１４５０℃の電気炉で１時間溶融し、攪拌を行った後に、さらに1時間溶融した。できたガラスは６００℃の徐冷炉に投入後、常温になるまで自然放冷を行って比較例及び、硫黄成分を芒硝で添加した実施例１、硫黄成分を硫化亜鉛で添加した実施例２のガラスを作成した。
The raw materials were prepared so as to have the glass composition of Table 2, melted in an electric furnace at 1450 ° C. for 1 hour, stirred, and further melted for 1 hour. The resulting glass was placed in a slow cooling furnace at 600 ° C. and then allowed to cool to room temperature, and then the glass of Comparative Example, Example 1 in which the sulfur component was added with sodium sulfate, and Example 2 in which the sulfur component was added with zinc sulfide. It was created.
比較例の光透過率曲線を図２に示す。
比較例は、Ｃｕ２Ｏ／ＳＯ３換算モル比が所定の範囲より大きく、ガラス中のＳの量がＣｕの量に対して不足しているため、核になる物質が少なくなって銅コロイドの生成が不十分となり赤色に発色しなかった。The light transmittance curve of the comparative example is shown in FIG.
In the comparative example, the Cu 2 O / SO 3 conversion molar ratio is larger than the predetermined range, and the amount of S in the glass is insufficient with respect to the amount of Cu. Formation was insufficient and the color did not develop red.
実施例１の光透過率曲線を図３に、実施例２の透過率曲線を図４に示す。
実施例１、２は、共に、Ｃｕ２Ｏ／ＳＯ３換算モル比が所定の範囲であるので、良好な銅赤ガラスとなっている。
The light transmittance curve of Example 1 is shown in FIG. 3, and the transmittance curve of Example 2 is shown in FIG.
In both Examples 1 and 2, the Cu 2 O / SO 3 equivalent molar ratio is within a predetermined range, and therefore, it is a good copper red glass.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2009/055128 WO2010106634A1 (en) | 2009-03-17 | 2009-03-17 | Copper ruby glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2010106634A1 JPWO2010106634A1 (en) | 2012-09-20 |
| JP5229828B2 true JP5229828B2 (en) | 2013-07-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009526976A Active JP5229828B2 (en) | 2009-03-17 | 2009-03-17 | Copper red glass |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5229828B2 (en) |
| TW (1) | TW201034994A (en) |
| WO (1) | WO2010106634A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5388947B2 (en) * | 2010-05-19 | 2014-01-15 | 東洋ガラス株式会社 | Copper red glass |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316450A (en) * | 1997-05-14 | 1998-12-02 | Yamamura Glass Co Ltd | Batch composition for producing soda lime silica-based copper red glass and production of the glass |
| JP2000044280A (en) * | 1998-07-30 | 2000-02-15 | Toyo Glass Co Ltd | Red glass and its production |
| JP2000233940A (en) * | 1998-12-14 | 2000-08-29 | Toyo Glass Co Ltd | Deep-colored amber glass and glass bottle |
-
2009
- 2009-03-17 WO PCT/JP2009/055128 patent/WO2010106634A1/en active Application Filing
- 2009-03-17 JP JP2009526976A patent/JP5229828B2/en active Active
-
2010
- 2010-03-16 TW TW099107639A patent/TW201034994A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316450A (en) * | 1997-05-14 | 1998-12-02 | Yamamura Glass Co Ltd | Batch composition for producing soda lime silica-based copper red glass and production of the glass |
| JP2000044280A (en) * | 1998-07-30 | 2000-02-15 | Toyo Glass Co Ltd | Red glass and its production |
| JP2000233940A (en) * | 1998-12-14 | 2000-08-29 | Toyo Glass Co Ltd | Deep-colored amber glass and glass bottle |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201034994A (en) | 2010-10-01 |
| TWI430973B (en) | 2014-03-21 |
| WO2010106634A1 (en) | 2010-09-23 |
| JPWO2010106634A1 (en) | 2012-09-20 |
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