JPH1160269A - Ultraviolet-absorbing colorless transparent glass - Google Patents

Ultraviolet-absorbing colorless transparent glass

Info

Publication number
JPH1160269A
JPH1160269A JP22296497A JP22296497A JPH1160269A JP H1160269 A JPH1160269 A JP H1160269A JP 22296497 A JP22296497 A JP 22296497A JP 22296497 A JP22296497 A JP 22296497A JP H1160269 A JPH1160269 A JP H1160269A
Authority
JP
Japan
Prior art keywords
oxide
glass
cerium oxide
color
ultraviolet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP22296497A
Other languages
Japanese (ja)
Other versions
JP3079506B2 (en
Inventor
Hidetoshi Komiya
秀利 小宮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Glass Co Ltd
Original Assignee
Toyo Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyo Glass Co Ltd filed Critical Toyo Glass Co Ltd
Priority to JP09222964A priority Critical patent/JP3079506B2/en
Publication of JPH1160269A publication Critical patent/JPH1160269A/en
Application granted granted Critical
Publication of JP3079506B2 publication Critical patent/JP3079506B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/08Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass

Abstract

PROBLEM TO BE SOLVED: To obtain the subject glass at lower cost more easily and more colorlessly than conventional ones. SOLUTION: This glass is obtained by incorporating 0.02-0.07 wt.% of erbium oxide as color fading agent in a soda-lime glass containing 0.3-0.6 wt.% of cerium oxide and <=0.05 wt.% of iron oxide. Incorporation of the cerium oxide affords this glass with ultraviolet light absorption effect. Yellowish color due to the iron oxide and cerium oxide can be corrected owing to the pale pinky color of the erbium oxide, getting virtually colorless. The color development of the erbium oxide is highly stable, being hard to be influenced by atmospheric change or an oxidizing agent such as the cerium oxide, thereby easily affording desired effects.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、特にガラスびんと
して用いて好適な紫外線吸収無色透明ガラスに関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV-absorbing colorless and transparent glass particularly suitable for use as a glass bottle.

【0002】[0002]

【従来の技術】ガラスびんにおいては、内容物の変質を
防ぐために紫外線を吸収し、しかも、内容物の様子を正
確に確認することのできる無色透明性を有するものが望
まれている。従来、このような用途のガラスは、特公昭
45−17794号、特公平5−354号などて提案さ
れている。前者のものは、ソーダライムガラスにセリウ
ム酸化物を0.2〜0.5重量%、ネオジウム酸化物を
0.05〜0.3重量%加えるというもので、セリウム
酸化物を加えることで紫外線を吸収し、それによって黄
色味をおびる色を消色剤であるネオジウム酸化物を加え
ることで無色に近くなるよに補正しようというものであ
る。後者のものは、容器の最大長を250mm以下と
し、重量%で0.04〜0.1%の酸化セリウムと、
0.065%以下の酸化鉄を含有させたソーダライムガ
ラスのびんである。やはり、酸化セリウムを添加するこ
とで紫外線を吸収し、黄色味を助長させる酸化鉄の含有
量を抑えると共にびんの最大長さを制限することでガラ
スが黄色に見えることを極力抑えようというものであ
る。
2. Description of the Related Art In glass bottles, those which absorb ultraviolet rays in order to prevent alteration of the contents and have a colorless and transparent property capable of accurately confirming the state of the contents are desired. Conventionally, glass for such a use has been proposed in Japanese Patent Publication No. 45-17794 and Japanese Patent Publication No. 5-354. The former is to add 0.2 to 0.5% by weight of cerium oxide and 0.05 to 0.3% by weight of neodymium oxide to soda lime glass. It is intended to correct the yellowish color by absorbing neodymium oxide, which is a decolorizing agent, so that the color becomes almost colorless. In the latter, the maximum length of the container is 250 mm or less, and 0.04 to 0.1% by weight of cerium oxide,
This is a soda lime glass bottle containing iron oxide of 0.065% or less. After all, adding cerium oxide absorbs ultraviolet rays, suppresses the content of iron oxide that promotes yellowishness, and limits the maximum length of the bottle to minimize the appearance of glass as yellow. is there.

【0003】[0003]

【発明が解決しようとする課題】上記の従来技術の前者
のものは、青紫色を付けるネオジウム酸化物を加えるこ
とで、酸化セリウムの黄色若しくは黄緑色を消して無色
に近づけようとするものであるが、ネオジウム酸化物が
高価であるうえに、添加する分量が難しく、少なすぎる
とガラスは黄色ないしは黄緑色を呈し、多すぎると青色
を呈してしまうという課題がある。
The former of the above-mentioned prior art is intended to eliminate the yellow or yellowish green color of cerium oxide by adding neodymium oxide which gives bluish purple to make it closer to colorless. However, neodymium oxide is expensive, and the amount to be added is difficult. If the amount is too small, the glass exhibits yellow or yellow-green, and if the amount is too large, the glass exhibits blue.

【0004】上記の従来技術の後者のものは、大型のび
んが作れない上に、セリウムの添加量が少ないから十分
な紫外線吸収効果を期待できず、また、セリウム酸化物
による黄色味を消すことができないから、結局ガラスの
色は無色とすることができず、黄色味をおびたガラスと
なってしまう。
[0004] In the latter conventional technique, a large-sized bottle cannot be produced, and a sufficient amount of cerium is not added, so that a sufficient ultraviolet absorbing effect cannot be expected. Therefore, the color of the glass cannot be colorless, and the glass becomes yellowish.

【0005】本発明は、このような課題を解決するもの
で、より安価で、より容易に、より無色に近い紫外線吸
収無色透明ガラスを得ることができるものである。
SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and it is possible to obtain an ultraviolet-absorbing colorless transparent glass that is less expensive, more easily, and more nearly colorless.

【0006】[0006]

【課題を解決するための手段】本発明は、重量%で酸化
セリウム0.3〜0.6%、酸化鉄0.05%以下を含
むソーダライムガラスで、消色剤として酸化エルビウム
0.02〜0.07%を添加したことを特徴とする紫外
線吸収無色透明ガラスである。
The present invention relates to a soda-lime glass containing 0.3 to 0.6% of cerium oxide and 0.05% or less of iron oxide by weight, and 0.02% of erbium oxide as a decolorizing agent. It is an ultraviolet-absorbing colorless and transparent glass characterized by adding about 0.07%.

【0007】本発明においては、酸化セリウムを加える
ことで紫外線吸収効果を得る。酸化セリウムの添加量
は、少なすぎては紫外線吸収作用が弱く、多すぎてはガ
ラスが強く発色し無色透明とすることができず、0.3
〜0.6%の量が双方の要素のバランスが良く、好適で
ある。表1に酸化セリウムの添加率と紫外線吸収率の関
係を示す。この表は、紫外線吸収率を該当波長範囲での
平均吸収率と定義し算出した。すなわち、10nm毎の
透過率を100から引いて、その平均値を求めている。
このように、酸化セリウムの添加量を増やすと、紫外線
吸収率が向上する。0.3〜0.6%とすれば、実用的
な紫外線吸収率を得ることができる。なお、表1におけ
るガラスの厚みは3mmである。
In the present invention, an ultraviolet absorbing effect is obtained by adding cerium oxide. If the amount of cerium oxide added is too small, the ultraviolet absorbing effect is weak, and if it is too large, the glass develops a strong color and cannot be colorless and transparent.
An amount of about 0.6% is preferable because the two elements are well-balanced. Table 1 shows the relationship between the cerium oxide addition rate and the ultraviolet absorption rate. In this table, the ultraviolet absorption was defined and calculated as the average absorption in the corresponding wavelength range. That is, the average value is obtained by subtracting the transmittance for each 10 nm from 100.
As described above, when the added amount of cerium oxide is increased, the ultraviolet absorption rate is improved. When the content is 0.3 to 0.6%, a practical ultraviolet absorptivity can be obtained. In addition, the thickness of the glass in Table 1 is 3 mm.

【表1】 [Table 1]

【0008】酸化セリウムを加えることで、ガラス中に
不純物として存在している鉄を酸化する。そのため、2
価の鉄イオンの緑色着色が少なくなり、3価の鉄イオン
の黄色が多くなる。これにより、明度Yが大きくなり、
主波長λdは長波長側へシフトし、ガラスの色が黄色味
がかる。不純物である酸化鉄の含有量を0.05%以下
に抑えることで、ガラスの黄色ないし黄緑色の発色を最
小限に抑制する。なお、酸化鉄の含有量を0.05%以
下に抑えることは、当業者にとって容易になし得ること
である。
By adding cerium oxide, iron present as an impurity in the glass is oxidized. Therefore, 2
The green coloring of the trivalent iron ion decreases, and the yellow color of the trivalent iron ion increases. This increases the brightness Y,
The main wavelength λd shifts to the longer wavelength side, and the color of the glass becomes yellowish. By suppressing the content of iron oxide, which is an impurity, to 0.05% or less, yellow or yellow-green coloring of the glass is minimized. In addition, it can be easily performed by those skilled in the art to reduce the content of iron oxide to 0.05% or less.

【0009】酸化鉄の含有量を抑えるだけではガラスを
無色にすることはできない。そこで、本発明において
は、消色剤として酸化エルビウム0.02〜0.07%
を添加する。酸化セリウムで黄色味がかった色は酸化エ
ルビウムの淡いピンク色で補正されて無色に近くなる。
酸化エルビウムの発色はきわめて安定していて、雰囲気
の変化や酸化セリウムのような酸化剤の影響を受けにく
く、所望の効果を容易に得ることができる。
The glass cannot be made colorless only by reducing the content of iron oxide. Therefore, in the present invention, 0.02 to 0.07% of erbium oxide is used as a decolorizing agent.
Is added. The yellowish color of cerium oxide is corrected to the pale pink color of erbium oxide and becomes almost colorless.
The color development of erbium oxide is extremely stable, hardly affected by changes in the atmosphere or an oxidizing agent such as cerium oxide, and a desired effect can be easily obtained.

【0010】[0010]

【実施例】本発明の実施例を表2に示す。酸化セリウム
を0.3%、0.4%又は0.6%添加し、それぞれに
ついて消色剤を添加したもの(実施例)と添加しないも
の(比較例)を試料として作成し、三刺激値を測定し
た。いずれの試料においてもガラスの厚みは10mm、
酸化鉄の含有量は0.038%である。三刺激値は、明
度Yが85%以上、主波長λdが565〜575nm、
刺激純度Peが1.5%以下の範囲の値となれば、ほぼ
良好な無色透明性を有すると判断できるが、主波長につ
いては568〜572nmの範囲となることが最も好ま
しい。消色剤として酸化エルビウムを添加した実施例
は、いずれも三刺激値がこの最も好ましい範囲にあり、
良好な無色透明性を有すると判断できる。また、視覚検
査においても、いずれの実施例も比較例に対して無色透
明性が向上しており、良好な無色透明ガラスとなってい
ることが確認された。
EXAMPLES Examples of the present invention are shown in Table 2. 0.3%, 0.4% or 0.6% of cerium oxide was added, and a sample having a decolorizing agent added thereto (Example) and a sample not containing the decoloring agent (Comparative Example) were prepared as tristimulus values. Was measured. The thickness of the glass in each sample was 10 mm,
The content of iron oxide is 0.038%. The tristimulus values are such that the brightness Y is 85% or more, the main wavelength λd is 565 to 575 nm,
When the stimulus purity Pe is in the range of 1.5% or less, it can be determined that the color filter has substantially good colorless transparency. However, the main wavelength is most preferably in the range of 568 to 572 nm. In all of the examples in which erbium oxide was added as a decolorizing agent, the tristimulus values were within this most preferred range,
It can be determined that it has good colorless transparency. Visual inspection also confirmed that all of the examples had improved colorless and transparent properties as compared with the comparative examples, and were good colorless and transparent glasses.

【表2】 [Table 2]

【0011】[0011]

【発明の効果】本発明は、酸化セリウムを添加すること
で紫外線を吸収し、消色剤として酸化エルビウムを用い
たので、安価かつ容易に無色透明性の高いガラスを得る
ことができる。
According to the present invention, since cerium oxide is added to absorb ultraviolet rays and erbium oxide is used as a decolorizing agent, glass having high colorless and transparent can be obtained easily at low cost.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 重量%で酸化セリウム0.3〜0.6
%、酸化鉄0.05%以下を含むソーダライムガラス
で、消色剤として酸化エルビウム0.02〜0.07%
を添加したことを特徴とする紫外線吸収無色透明ガラス
1. Cerium oxide 0.3 to 0.6% by weight
%, Soda lime glass containing iron oxide 0.05% or less, erbium oxide 0.02 to 0.07% as a decolorizing agent
UV-absorbing colorless transparent glass characterized by the addition of
JP09222964A 1997-08-06 1997-08-06 UV absorbing colorless transparent glass Expired - Fee Related JP3079506B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP09222964A JP3079506B2 (en) 1997-08-06 1997-08-06 UV absorbing colorless transparent glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP09222964A JP3079506B2 (en) 1997-08-06 1997-08-06 UV absorbing colorless transparent glass

Publications (2)

Publication Number Publication Date
JPH1160269A true JPH1160269A (en) 1999-03-02
JP3079506B2 JP3079506B2 (en) 2000-08-21

Family

ID=16790651

Family Applications (1)

Application Number Title Priority Date Filing Date
JP09222964A Expired - Fee Related JP3079506B2 (en) 1997-08-06 1997-08-06 UV absorbing colorless transparent glass

Country Status (1)

Country Link
JP (1) JP3079506B2 (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001322829A (en) * 2000-05-12 2001-11-20 Toyo Glass Co Ltd Glass having high transparency, method for manufacturing glass having high transparency and frit for glass having high transparency
WO2003064342A1 (en) * 2002-01-28 2003-08-07 Guardian Industries Corp. Clear glass composition
US6962887B2 (en) * 2003-05-14 2005-11-08 Ppg Industries Ohio, Inc. Transparent glass having blue edge color
US7037869B2 (en) 2002-01-28 2006-05-02 Guardian Industries Corp. Clear glass composition
US7151065B2 (en) 2003-07-21 2006-12-19 Guardian Industries Corp. Grey glass composition
US7169722B2 (en) 2002-01-28 2007-01-30 Guardian Industries Corp. Clear glass composition with high visible transmittance
US7557053B2 (en) 2006-03-13 2009-07-07 Guardian Industries Corp. Low iron high transmission float glass for solar cell applications and method of making same
US7560402B2 (en) 2006-10-06 2009-07-14 Guardian Industries Corp. Clear glass composition
US7560403B2 (en) 2006-10-17 2009-07-14 Guardian Industries Corp. Clear glass composition with erbium oxide
US7562538B2 (en) 2005-05-27 2009-07-21 Guardian Industries Corp. Method of making clear glass composition
US7601660B2 (en) 2004-03-01 2009-10-13 Guardian Industries Corp. Clear glass composition
US7700869B2 (en) 2005-02-03 2010-04-20 Guardian Industries Corp. Solar cell low iron patterned glass and method of making same
US7700870B2 (en) 2005-05-05 2010-04-20 Guardian Industries Corp. Solar cell using low iron high transmission glass with antimony and corresponding method
US7767253B2 (en) 2007-03-09 2010-08-03 Guardian Industries Corp. Method of making a photovoltaic device with antireflective coating
US20110000260A1 (en) * 2008-03-03 2011-01-06 Doctors Optics Gmbh Method for producing an optical glass part, particularly of a motor vehicle headlight lens
US8153282B2 (en) 2005-11-22 2012-04-10 Guardian Industries Corp. Solar cell with antireflective coating with graded layer including mixture of titanium oxide and silicon oxide
US8237047B2 (en) 2007-05-01 2012-08-07 Guardian Industries Corp. Method of making a photovoltaic device or front substrate for use in same with scratch-resistant coating and resulting product
US8319095B2 (en) 2007-11-27 2012-11-27 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
US8445774B2 (en) 2007-07-26 2013-05-21 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
US8450594B2 (en) 2007-07-26 2013-05-28 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product and photovoltaic device comprising same
US8617641B2 (en) 2009-11-12 2013-12-31 Guardian Industries Corp. Coated article comprising colloidal silica inclusive anti-reflective coating, and method of making the same
US8637762B2 (en) 2006-11-17 2014-01-28 Guardian Industries Corp. High transmission glass ground at edge portion(s) thereof for use in electronic device such as photovoltaic applications and corresponding method
US8648252B2 (en) 2006-03-13 2014-02-11 Guardian Industries Corp. Solar cell using low iron high transmission glass and corresponding method
US8668961B2 (en) 2008-07-31 2014-03-11 Guardian Industries Corp. Titania coating and method of making same
US9272949B2 (en) 2010-07-09 2016-03-01 Guardian Industries Corp. Coated glass substrate with heat treatable ultraviolet blocking characteristics

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001322829A (en) * 2000-05-12 2001-11-20 Toyo Glass Co Ltd Glass having high transparency, method for manufacturing glass having high transparency and frit for glass having high transparency
US7482295B2 (en) 2002-01-28 2009-01-27 Guardian Industries Corp. Clear glass composition with high visible transmittance
WO2003064342A1 (en) * 2002-01-28 2003-08-07 Guardian Industries Corp. Clear glass composition
US6949484B2 (en) * 2002-01-28 2005-09-27 Guardian Industries Corp. Clear glass composition
US7683000B2 (en) 2002-01-28 2010-03-23 Guardian Industries Corp. Clear glass composition with high visible transmittance
US7030047B2 (en) 2002-01-28 2006-04-18 Guardian Industries Corp. Clear glass composition
US7037869B2 (en) 2002-01-28 2006-05-02 Guardian Industries Corp. Clear glass composition
US7858545B2 (en) 2002-01-28 2010-12-28 Guardian Industries Corp. Clear glass composition with high visible transmittance
US7169722B2 (en) 2002-01-28 2007-01-30 Guardian Industries Corp. Clear glass composition with high visible transmittance
US6962887B2 (en) * 2003-05-14 2005-11-08 Ppg Industries Ohio, Inc. Transparent glass having blue edge color
US7151065B2 (en) 2003-07-21 2006-12-19 Guardian Industries Corp. Grey glass composition
WO2005082799A3 (en) * 2004-02-25 2006-05-26 Guardian Industries Clear glass composition
US7601660B2 (en) 2004-03-01 2009-10-13 Guardian Industries Corp. Clear glass composition
US7700869B2 (en) 2005-02-03 2010-04-20 Guardian Industries Corp. Solar cell low iron patterned glass and method of making same
US7700870B2 (en) 2005-05-05 2010-04-20 Guardian Industries Corp. Solar cell using low iron high transmission glass with antimony and corresponding method
US8802216B2 (en) 2005-05-05 2014-08-12 Guardian Industries Corp. Solar cell using low iron high transmission glass with antimony and corresponding method
US7562538B2 (en) 2005-05-27 2009-07-21 Guardian Industries Corp. Method of making clear glass composition
US8153282B2 (en) 2005-11-22 2012-04-10 Guardian Industries Corp. Solar cell with antireflective coating with graded layer including mixture of titanium oxide and silicon oxide
US7557053B2 (en) 2006-03-13 2009-07-07 Guardian Industries Corp. Low iron high transmission float glass for solar cell applications and method of making same
US8648252B2 (en) 2006-03-13 2014-02-11 Guardian Industries Corp. Solar cell using low iron high transmission glass and corresponding method
US7893350B2 (en) 2006-03-13 2011-02-22 Guardian Industries Corp. Low iron transmission float glass for solar cell applications and method of making same
US7560402B2 (en) 2006-10-06 2009-07-14 Guardian Industries Corp. Clear glass composition
US7560403B2 (en) 2006-10-17 2009-07-14 Guardian Industries Corp. Clear glass composition with erbium oxide
US8637762B2 (en) 2006-11-17 2014-01-28 Guardian Industries Corp. High transmission glass ground at edge portion(s) thereof for use in electronic device such as photovoltaic applications and corresponding method
US8450600B2 (en) 2007-03-09 2013-05-28 Guardian Industries Corp. Photovoltaic device with scratch-resistant coating
US7767253B2 (en) 2007-03-09 2010-08-03 Guardian Industries Corp. Method of making a photovoltaic device with antireflective coating
US8237047B2 (en) 2007-05-01 2012-08-07 Guardian Industries Corp. Method of making a photovoltaic device or front substrate for use in same with scratch-resistant coating and resulting product
US8445774B2 (en) 2007-07-26 2013-05-21 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
US8450594B2 (en) 2007-07-26 2013-05-28 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product and photovoltaic device comprising same
US8319095B2 (en) 2007-11-27 2012-11-27 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
US20110000260A1 (en) * 2008-03-03 2011-01-06 Doctors Optics Gmbh Method for producing an optical glass part, particularly of a motor vehicle headlight lens
US8668961B2 (en) 2008-07-31 2014-03-11 Guardian Industries Corp. Titania coating and method of making same
US8617641B2 (en) 2009-11-12 2013-12-31 Guardian Industries Corp. Coated article comprising colloidal silica inclusive anti-reflective coating, and method of making the same
US9272949B2 (en) 2010-07-09 2016-03-01 Guardian Industries Corp. Coated glass substrate with heat treatable ultraviolet blocking characteristics

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