JP5072156B2 - Manufacturing method of UV blocking glass container - Google Patents
Manufacturing method of UV blocking glass container Download PDFInfo
- Publication number
- JP5072156B2 JP5072156B2 JP2001292724A JP2001292724A JP5072156B2 JP 5072156 B2 JP5072156 B2 JP 5072156B2 JP 2001292724 A JP2001292724 A JP 2001292724A JP 2001292724 A JP2001292724 A JP 2001292724A JP 5072156 B2 JP5072156 B2 JP 5072156B2
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- glass
- cerium oxide
- blocking effect
- vanadium oxide
- 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.)
- Expired - Fee Related
Links
- 230000000903 blocking effect Effects 0.000 title claims description 27
- 239000011521 glass Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000005361 soda-lime glass Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 22
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 19
- 229910001935 vanadium oxide Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000006121 base glass Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 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
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
Landscapes
- 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
【０００１】
【発明の属する技術分野】
本発明は、ソーダ石灰ガラスの無色透明性を有しながら、紫外線を有効に遮断する紫外線遮断ガラス容器の製造方法に関する。
【０００２】
【従来の技術】
透明性を有する紫外線遮断ガラスとしては、特開平２−３８３３９に酸化セリウムを含有するもの、特開平２−４８４２７に酸化バナジウムを含有するものが開示されている。
【０００３】
【発明が解決しようとする課題】
従来の酸化セリウム（ＣｅＯ２）又は酸化バナジウム（Ｖ２Ｏ５）を含有する紫外線遮断ガラスは、酸化セリウム又は酸化バナジウムを多量に使用しなければならず、コスト高になっていた。本発明は、製造コストが安く、紫外線遮断効果の高いガラス及びガラス容器を開発することを課題としてなされたものである。
【０００４】
【課題を解決するための手段】
本発明は、ソーダ石灰ガラスであって、重量％で０．００１〜０．００９％のＶ２Ｏ５と、０．００１〜０．０５％のＣｅＯ２を、Ｖ２Ｏ５／ＣｅＯ２の比が０．０２〜９．０の割合で含む無色透明性を有する紫外線遮断ガラスを成形後、使用に先立って、屋外での紫外線暴露期間２週間相当以上紫外線に暴露させることを特徴とする無色透明性を有する紫外線遮断ガラス容器の製造方法である。
【０００５】
本願の発明者は、酸化セリウムと酸化バナジウムの双方を含むガラスは、相乗的な紫外線遮断効果を生み出すことを発見した。これは、ガラス中に酸化セリウムと酸化バナジウムの双方が存在すると、
Ｃｅ３＋ ＋ Ｖ３＋ → Ｃｅ４＋ ＋ Ｖ２＋
の反応が起こり、Ｃｅ４＋が非常に増大し、Ｃｅ４＋はＣｅ３＋に比べて紫外線遮断効果が大きいので、ガラスの紫外線遮断効果が増大するものと推定できる。また、ガラスが紫外線に暴露されると、上記の反応式が促進されてＣｅ４＋がさらに増加し、紫外線遮断効果がさらに向上することも発見した。野外での紫外線暴露期間２週間相当以上の暴露量で十分な紫外線遮断効果の向上が見込める。
【０００６】
また、酸化バナジウムはベースガラスが酸化側であるほど紫外部の吸収（紫外線遮断効果）は増し、可視部の吸収は減る（着色しにくくなる）が、酸化セリウムが加わるとベースガラスが酸化側に寄り、紫外線遮断効果と無色透明性が増大する。さらに、酸化セリウムと酸化バナジウムでは良く吸収する波長が異なり（酸化セリウムはより短い波長側、酸化バナジウムはより長い波長側の吸収が良い）、双方を含有させることで紫外線がむらなく吸収される。
【０００７】
酸化バナジウムの添加量は０．００１〜０．００９％が好適である。０．００１％よりも少ないと相乗的な紫外線遮断効果が不足し、０．００９％よりも多いと着色が多くなる。酸化セリウムの添加量は０．００１〜０．０５％が好適である。０．００１％よりも少ないと相乗的な紫外線遮断効果が不足し、０．０５％よりも多いと着色が多くなる。酸化バナジウム／酸化セリウムの比が０．０２〜９．０の割合が好適である。この範囲から外れると相乗的な紫外線遮断効果が減少する。
【０００８】
【発明の実施の形態】
次の実施例１〜３のガラス板（厚さ１０ｍｍ）を製作した。実施例１〜３のガラス板はいずれも十分な無色透明性を有していた。
実施例１：
酸化セリウム０．０３６％、酸化バナジウム０．００３％を添加したソーダ石灰ガラス
実施例２：
酸化セリウム０．０３６％、酸化バナジウム０．００５％を添加したソーダ石灰ガラス
実施例３：
酸化セリウム０．０３６％、酸化バナジウム０．００７％を添加したソーダ石灰ガラス
【０００９】
また、実施例の効果を比較、確認するため、次の比較例１〜３のガラス板（厚さ１０ｍｍ）を製作した。
比較例１：
酸化セリウム及び酸化バナジウムを含まない無色透明な通常のソーダ石灰ガラス
比較例２：
酸化セリウム０．０３６％を添加したソーダ石灰ガラス
比較例３：
酸化バナジウム０．００７％を添加したソーダ石灰ガラス
比較例４：
酸化セリウム０．０６２％を添加したソーダ石灰ガラス
【００１０】
図１は実施例３及び比較例１〜３の紫外域における透過率を示している。同図から明らかなように、実施例３は、紫外線吸収剤が酸化セリウムのみの比較例２や酸化バナジウムのみの比較例３に比べて優れた紫外線遮断効果を有している。これにより、酸化セリウムと酸化バナジウムの相乗効果によって紫外線遮断効果が増大することが確認できる。
【００１１】
図２は実施例１〜３と比較例１、４の紫外域における透過率を示している。実施例１〜３は、酸化セリウムを大量に含む比較例４よりも優れた紫外線遮断効果を有している。これにより、酸化セリウムに少量の酸化バナジウムが加わることによって、紫外線遮断効果が大幅に増大することが確認できる。
【００１２】
図３は実施例１の紫外線暴露による透過率の変化を示している。紫外線の暴露は、ＪＩＳＢ７７５３（サンシャインカーボンアーク灯式耐光性及び耐候性試験機）に準じている試験機で、放射照度２５５Ｗ／ｍ２で行った。この場合、１５０時間の照射時間で野外暴露１２カ月に相当する。同図に示すように、野外暴露２週間相当（２週）は、暴露しないもの（０週）よりもかなり紫外線遮断効果が増大している。例えば波長３６０ｎｍで見ると、透過率６７％だったものが４９％に減少しており、これは紫外線遮断効果が５０％以上向上していることになる。その後、野外暴露４週間相当（４週）から６週間相当（６週）と暴露量が多くなるにつれて少しずつ紫外線遮断効果が向上することが確認できる。
【００１３】
図４は実施例２の、図５は実施例３の紫外線暴露による透過率の変化を示している。実施例２、３においても実施例１と同様に、２週暴露によって大きく紫外線遮断効果が増大し、その後少しずつ効果が向上することが確認できる。
【００１４】
【発明の効果】
本発明は、紫外線吸収剤として、酸化セリウム又は酸化バナジウムを単独で使用する場合に比べて、同程度の紫外線遮断効果を得るために、酸化セリウム又は酸化バナジウムの添加量を少なくすることができるので、コストダウンを実現できる。さらに、ガラス又はガラス容器が紫外線暴露されることで一層紫外線遮断効果が増大し、ガラス容器の内容物の変質を防止することができる。同様に充填後でもガラス容器は紫外線暴露されることにより紫外線遮断効果が増大するため、内容物を紫外線から保護することができる。
【図面の簡単な説明】
【図１】実施例３及び比較例１〜３の紫外域における透過率の説明図である。
【図２】実施例１〜３と比較例１、４の紫外域における透過率の説明図である。
【図３】実施例１の紫外線暴露による紫外域における透過率の変化の説明図である。
【図４】実施例２の紫外線暴露による紫外域における透過率の変化の説明図である。
【図５】実施例３の紫外線暴露による紫外域における透過率の変化の説明図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an ultraviolet blocking glass container that effectively blocks ultraviolet rays while having colorless transparency of soda-lime glass.
[0002]
[Prior art]
As the ultraviolet blocking glass having transparency, JP-A-2-38339 discloses a glass containing cerium oxide, and JP-A-2-48427 discloses a glass containing vanadium oxide.
[0003]
[Problems to be solved by the invention]
Conventional ultraviolet blocking glass containing cerium oxide (CeO 2 ) or vanadium oxide (V 2 O 5 ) has to use a large amount of cerium oxide or vanadium oxide, which increases the cost. An object of the present invention is to develop a glass and a glass container having a low production cost and a high ultraviolet blocking effect.
[0004]
[Means for Solving the Problems]
The present invention provides a soda-lime glass, and from 0.001 to 0.009% of V 2 O 5 in wt% 0.001 to 0.05% of the CeO 2, of V 2 O 5 / CeO 2 after molding the ultraviolet blocking glass having a colorless transparent containing ratio at a rate of 0.02 to 9.0, prior to use, characterized in that Ru is exposed to ultraviolet
[0005]
The inventors of the present application have discovered that glasses containing both cerium oxide and vanadium oxide produce a synergistic UV blocking effect. This is because when both cerium oxide and vanadium oxide are present in the glass,
Ce 3+ + V 3+ → Ce 4+ + V 2+
It is estimated that Ce 4+ is greatly increased and Ce 4+ has a larger ultraviolet blocking effect than Ce 3+ , so that the ultraviolet blocking effect of the glass is increased. It was also discovered that when glass is exposed to ultraviolet light, the above reaction formula is promoted, Ce 4+ is further increased, and the ultraviolet blocking effect is further improved. Sufficient UV blocking effect can be expected with an exposure amount equivalent to 2 weeks or more in the outdoor UV exposure period.
[0006]
Also, vanadium oxide increases the absorption in the ultraviolet part (ultraviolet ray blocking effect) and decreases the absorption in the visible part (it becomes difficult to be colored) as the base glass is on the oxidation side, but when cerium oxide is added, the base glass moves to the oxidation side. Nearly, the UV blocking effect and colorless transparency increase. Furthermore, cerium oxide and vanadium oxide have different absorption wavelengths (cerium oxide has better absorption on the shorter wavelength side and vanadium oxide has better absorption on the longer wavelength side), and by containing both, ultraviolet rays are absorbed evenly.
[0007]
The amount of vanadium oxide added is preferably 0.001 to 0.009%. If it is less than 0.001%, the synergistic ultraviolet blocking effect is insufficient, and if it is more than 0.009%, coloring is increased. The amount of cerium oxide added is preferably 0.001 to 0.05%. If it is less than 0.001%, the synergistic ultraviolet blocking effect is insufficient, and if it is more than 0.05%, coloring is increased. A ratio of vanadium oxide / cerium oxide ratio of 0.02 to 9.0 is preferred. Outside this range, the synergistic UV blocking effect is reduced.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The glass plates (
Example 1:
Soda lime glass added with 0.036% cerium oxide and 0.003% vanadium oxide Example 2:
Soda lime glass added with 0.036% cerium oxide and 0.005% vanadium oxide Example 3:
Soda lime glass added with 0.036% cerium oxide and 0.007% vanadium oxide
Moreover, in order to compare and confirm the effects of the examples, glass plates (
Comparative Example 1:
Colorless transparent ordinary soda-lime glass containing no cerium oxide and vanadium oxide Comparative Example 2:
Soda lime glass added with 0.036% cerium oxide Comparative Example 3:
Soda lime glass added with 0.007% vanadium oxide Comparative Example 4:
Soda lime glass added with 0.062% cerium oxide
FIG. 1 shows the transmittance in the ultraviolet region of Example 3 and Comparative Examples 1-3. As can be seen from the figure, Example 3 has an excellent ultraviolet blocking effect compared to Comparative Example 2 in which the ultraviolet absorber is only cerium oxide and Comparative Example 3 in which only vanadium oxide is used. Thereby, it can be confirmed that the ultraviolet blocking effect is increased by the synergistic effect of cerium oxide and vanadium oxide.
[0011]
FIG. 2 shows the transmittance in Examples 1 to 3 and Comparative Examples 1 and 4 in the ultraviolet region. Examples 1 to 3 have an ultraviolet blocking effect superior to that of Comparative Example 4 containing a large amount of cerium oxide. Thereby, it can be confirmed that the ultraviolet blocking effect is greatly increased by adding a small amount of vanadium oxide to cerium oxide.
[0012]
FIG. 3 shows the change in transmittance due to exposure to ultraviolet light in Example 1. The exposure to ultraviolet rays was carried out at an irradiance of 255 W / m 2 using a tester according to JISB7753 (Sunshine carbon arc lamp type light resistance and weather resistance tester). In this case, it corresponds to 12 months of field exposure with an irradiation time of 150 hours. As shown in the figure, the UV blocking effect is significantly increased in the field exposure for 2 weeks (2 weeks) than in the case of no exposure (week 0). For example, when viewed at a wavelength of 360 nm, the transmittance of 67% is reduced to 49%, which means that the ultraviolet blocking effect is improved by 50% or more. Thereafter, it can be confirmed that the UV blocking effect is gradually improved as the amount of exposure increases from 4 weeks (4 weeks) to 6 weeks (6 weeks).
[0013]
FIG. 4 shows the change in transmittance of Example 2 and FIG. In Examples 2 and 3, as in Example 1, it can be confirmed that the ultraviolet blocking effect is greatly increased by exposure for 2 weeks, and thereafter the effect is gradually improved.
[0014]
【Effect of the invention】
In the present invention, the amount of cerium oxide or vanadium oxide added can be reduced in order to obtain the same level of ultraviolet blocking effect as when using cerium oxide or vanadium oxide alone as an ultraviolet absorber. Cost reduction can be realized. Furthermore, when the glass or the glass container is exposed to ultraviolet rays, the ultraviolet blocking effect is further increased, and the contents of the glass container can be prevented from being altered. Similarly, the glass container is protected from ultraviolet rays by being exposed to ultraviolet rays after filling, so that the contents can be protected from the ultraviolet rays.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of transmittance in the ultraviolet region of Example 3 and Comparative Examples 1 to 3. FIG.
FIG. 2 is an explanatory diagram of transmittance in Examples 1 to 3 and Comparative Examples 1 and 4 in the ultraviolet region.
3 is an explanatory diagram of a change in transmittance in the ultraviolet region due to exposure to ultraviolet light in Example 1. FIG.
4 is an explanatory diagram of a change in transmittance in the ultraviolet region due to exposure to ultraviolet light in Example 2. FIG.
5 is an explanatory diagram of a change in transmittance in the ultraviolet region due to exposure to ultraviolet light in Example 3. FIG.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001292724A JP5072156B2 (en) | 2001-09-26 | 2001-09-26 | Manufacturing method of UV blocking glass container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001292724A JP5072156B2 (en) | 2001-09-26 | 2001-09-26 | Manufacturing method of UV blocking glass container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003095696A JP2003095696A (en) | 2003-04-03 |
| JP5072156B2 true JP5072156B2 (en) | 2012-11-14 |
Family
ID=19114634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001292724A Expired - Fee Related JP5072156B2 (en) | 2001-09-26 | 2001-09-26 | Manufacturing method of UV blocking glass container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5072156B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012219614B3 (en) * | 2012-10-26 | 2013-12-19 | Schott Ag | Borosilicate glass, used to prepare glass tubes or manufacture lamps, includes e.g. silicon dioxide, boron trioxide, aluminum oxide, lithium oxide, sodium oxide, potassium oxide, barium oxide, calcium oxide, magnesium oxide, and zinc oxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0238339A (en) * | 1988-07-27 | 1990-02-07 | Ishizuka Glass Co Ltd | Glass container that blocks UV rays |
| JPH0656467A (en) * | 1992-08-07 | 1994-03-01 | Nippon Electric Glass Co Ltd | Ultraviolet light absorbing glass |
-
2001
- 2001-09-26 JP JP2001292724A patent/JP5072156B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003095696A (en) | 2003-04-03 |
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