JP3603764B2 - How to clean glass - Google Patents
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- JP3603764B2 JP3603764B2 JP2000260416A JP2000260416A JP3603764B2 JP 3603764 B2 JP3603764 B2 JP 3603764B2 JP 2000260416 A JP2000260416 A JP 2000260416A JP 2000260416 A JP2000260416 A JP 2000260416A JP 3603764 B2 JP3603764 B2 JP 3603764B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、ガラスの洗浄方法に関するものである。
【０００２】
【従来の技術】
例えば一般照明用管球やブラウン管等に用いられているガラス製の部材は、通常、製造工程での前処理として、表面に付着した異物（例えばダスト等）を除去するために洗浄されている。
【０００３】
従来、ガラスの洗浄方法としては、ガラスの洗浄溶液として、適当な濃度のフッ化水素酸水溶液が一般的に用いられていた。
【０００４】
また、ガラスの洗浄方法に用いられる別の洗浄溶液としては、洗浄速度や洗浄能力を向上させるために、フッ化水素酸や酸性フッ化アンモニウムの水溶液に塩酸や硝酸等の液体の無機酸を添加したものが知られている（特開平８−１７３４８号公報）。
【０００５】
【発明が解決しようとする課題】
しかしながら、上記従来のガラスの洗浄方法では、フッ化水素酸水溶液が用いられているため、人体への安全性や環境保護の観点からフッ化水素酸水溶液そのものを使用することは適切でないという問題があった。
【０００６】
また、フッ化水素酸水溶液そのものは使用していないが、酸性フッ化アンモニウムの水溶液に塩酸や硝酸等の液体の無機酸を添加した洗浄溶液を用いた場合でも、酸性フッ化アンモニウムと塩酸や硝酸との反応によってフッ化水素酸が多量に生成されるため、結果として、人体への安全性や環境保護の観点から不適切であるという問題があった。
【０００７】
さらに、塩酸や硝酸等は酸の刺激臭が強いので、これらの無機酸を用いることは作業上での環境面から見ても好ましくないという問題があった。
【０００８】
本発明は、上記問題を解決するためになされたもので、十分なガラスの清浄効果を得つつ、人体への安全性が高く、作業上での環境も含めた環境全体への配慮がなされたガラスの洗浄方法を提供することを目的とするものである。
【０００９】
【課題を解決するための手段】
本発明のガラスの洗浄方法は、水と、フッ化アンモニウムと、硫酸水素アンモニウム、硫酸水素ナトリウム、硫酸水素カリウム、亜硫酸水素アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、リン酸二水素アンモニウム、リン酸二水素ナトリウム、リン酸二水素カリウム、および亜リン酸の中から選ばれる少なくとも１種からなる固体性の無機酸とを含む洗浄溶液によってガラスを洗浄する方法を用いている。
【００１０】
この方法によれば、十分なガラスの洗浄効果を得つつ、前記固体性の無機酸が弱酸性であるために、フッ化アンモニウムと固体性の無機酸との化学反応が小さく、よってフッ化水素酸の生成量を少量に抑えることができるので、人体への安全性が高く、かつ環境面に配慮がなされたガラスの洗浄方法を実現することができ、また塩酸や硝酸等の液体の無機酸を用いていないために、つまり固体性の無機酸を用いているために、強い酸の刺激臭が発生せず、作業上での環境をも改善することができる。
【００１１】
【発明の実施の形態】
本発明の実施の形態であるガラスの洗浄方法では、水と、フッ化アンモニウムと、固体性の無機酸とを含む洗浄溶液が用いられる。
【００１２】
この洗浄溶液には、水１ｌ当たりに対してフッ化アンモニウムが１ｍｏｌ〜６ｍｏｌ、無機酸が１ｍｏｌ〜３ｍｏｌ含まれていることが好ましい。
【００１３】
無機酸は、硫酸水素アンモニウム、硫酸水素ナトリウム、硫酸水素カリウム、亜硫酸水素アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、リン酸二水素アンモニウム、リン酸二水素ナトリウム、リン酸二水素カリウム、および亜リン酸の中から選ばれる少なくとも１種からなる。
【００１４】
次に、本発明の実施の形態にかかるガラスの洗浄方法の概略を説明する。
【００１５】
まず、被洗浄物であるガラス（石英ガラス、ソーダライムガラス、または鉛ガラス等からなる管球用ガラスやブラウン管用ガラス）を上記洗浄溶液中に浸漬して、ガラスの表面層を溶解することにより、ガラス表面に付着している異物を剥離させる（洗浄工程）。ガラスの表面層は、フッ化アンモニウムと固体性の無機酸との化学反応によって生成された少量のフッ化水素酸により溶解される。洗浄溶液中において、フッ化水素酸はガラスの溶解によって消費（分解）されると、その消費分程度が同じくフッ化アンモニウムと固体性の無機酸との化学反応によって新たに生成される。つまり、洗浄溶液中には、常に一定のフッ化水素酸が存在している。
【００１６】
なお、フッ化水素酸とガラス（例えば石英ガラス（ＳｉＯ２））との化学反応式を次式に示す。
【００１７】
６ＨＦ＋ＳｉＯ２ → Ｈ２ＳｉＦ６＋２Ｈ２Ｏ
また、洗浄工程において、ガラスの洗浄効果を高めるために、洗浄溶液の温度を１０℃以上に設定することが好ましい。しかし、洗浄溶液の温度が高すぎると、洗浄溶液中の水分が蒸発し、洗浄溶液の濃度が高くなりすぎる恐れがあるため、実用上、洗浄溶液の温度は８０℃以下が好ましい。
【００１８】
洗浄工程後、洗浄したガラスを純水に浸漬し、ガラスに付着した洗浄溶液とともに、剥離した異物を洗い落とす（水洗工程）。この水洗工程は数回繰り返される。
【００１９】
その後、水洗したガラスに温風を吹きかけ、乾燥させる（乾燥工程）。
【００２０】
以上のように水と、フッ化アンモニウムと、硫酸水素アンモニウム、硫酸水素ナトリウム、硫酸水素カリウム、亜硫酸水素アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、リン酸二水素アンモニウム、リン酸二水素ナトリウム、リン酸二水素カリウム、および亜リン酸の中から選ばれる少なくとも１種からなる固体性の無機酸とを含む洗浄溶液によってガラスを洗浄する方法を用いることにより、十分なガラスの洗浄効果を得つつ、固体性の無機酸が弱酸性であるために、フッ化アンモニウムと固体性の無機酸との化学反応が小さく、よってフッ化水素酸の生成量を少量に抑えることができるので、人体への安全性が高く、かつ環境面に配慮がなされたガラスの洗浄方法を実現することができ、また塩酸や硝酸等の液体の無機酸を用いていないために、つまり固体性の無機酸を用いているために、強い酸の刺激臭が発生せず、作業上での環境をも改善することができる。
【００２１】
ここで、洗浄溶液には水１ｌ当たりに対してフッ化アンモニウムが１ｍｏｌ〜６ｍｏｌ、無機酸が１ｍｏｌ〜３ｍｏｌ含まれていることが好ましい理由について説明する。
【００２２】
被洗浄物として、管外径１８ｍｍ（管内径１５ｍｍ）、管長３５ｍｍのメタルハライドランプの発光管用の石英ガラス管を用いた。
【００２３】
この石英ガラス管を、表１に示すように組成が種々異なる洗浄溶液を用いて洗浄し、洗浄力の評価を行った。
【００２４】
なお、本発明における洗浄力の評価は、被洗浄物の洗浄前後の重量を比較し、その重量差が大きいほど、洗浄力が高いと評価した。表１中、「◎」は「非常に洗浄力が高い」を、「○」は「洗浄力が高い」を、「×」は「洗浄力が低い」をそれぞれ示す。
【００２５】
また、上記評価において、固体性の無機酸として、硫酸水素アンモニウム単体を用いた。また、洗浄工程における洗浄溶液の浸漬時間を１５分、洗浄溶液の温度を３０℃とした。
【００２６】
【表１】
表１から明らかなように、水１ｌ当たりに対してフッ化アンモニウムが１ｍｏｌ〜６ｍｏｌ、無機酸が１ｍｏｌ〜３ｍｏｌ含まれる洗浄溶液では、ガラスの表面層の溶解量が多く、高い洗浄力が得られることがわかった。
【００２８】
また、特に、水１ｌ当たりに対してフッ化アンモニウムが３．５ｍｏｌ〜５ｍｏｌ、無機酸が２．７ｍｏｌ〜３ｍｏｌ含まれる洗浄溶液では、ガラスの表面層の溶解量が一層多く、非常に高い洗浄力が得られることがわかった。このように非常に高い洗浄力が得られれば、洗浄溶液への浸漬時間を短くすることができるので、洗浄の作業効率を向上させることができる。
【００２９】
一方、実施例１ないし実施例５のように水１ｌ当たりのフッ化アンモニウムの含有量が１ｍｏｌ未満では、洗浄力が低いことがわかった。これは、無機酸との化学反応によって生成されるフッ化水素酸量が著しく少なくなるためであると考えられる。また、実施例３１ないし実施例３５のように水１ｌ当たりのフッ化アンモニウムの含有量が６ｍｏｌを越える場合でも、洗浄力が低いことがわかった。これは、フッ化アンモニウムの含有量が多すぎ、洗浄溶液が飽和濃度に近づいたためであると考えられる。
【００３０】
また、水１ｌ当たりに対するフッ化アンモニウムの含有量が最適な量（１ｍｏｌ〜６ｍｏｌ）の場合であっても、実施例６、実施例１１、実施例１６、実施例２１、および実施例２６のように水１ｌ当たりの硫酸水素アンモニウムの含有量が１ｍｏｌ未満では、洗浄力が低いことがわかった。これは、フッ化アンモニウムとの化学反応が十分に進まず、よって生成されるフッ化水素酸量が著しく減少するためであると考えられる。また、実施例１０、実施例１５、実施例２０、実施例２５、および実施例３０のように水１ｌ当たりの硫酸水素アンモニウムの含有量が３ｍｏｌを越える場合でも、洗浄力が低いことがわかった。これは、硫酸水素アンモニウムが飽和により水に溶解しなくなるためであると考えられる。
【００３１】
したがって、洗浄溶液には水１ｌ当たりに対してフッ化アンモニウムが１ｍｏｌ〜６ｍｏｌ、無機酸が１ｍｏｌ〜３ｍｏｌ含まれることにより、高い洗浄力を得ることができる。
【００３２】
なお、上記実施の形態では、洗浄工程において、洗浄溶液中にガラスを浸漬する方法を用いた場合について説明したが、ガラスに洗浄溶液を噴射することによりガラスの表面層の溶解を行っても上記と同様の効果を得ることができる。
【００３３】
また、上記実施の形態では、固体性の無機酸として、硫酸水素アンモニウム単体のみを用いた場合について説明したが、固体性の無機酸として、硫酸水素アンモニウム、硫酸水素ナトリウム、硫酸水素カリウム、亜硫酸水素アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、リン酸二水素アンモニウム、リン酸二水素ナトリウム、リン酸二水素カリウム、亜リン酸の中から選ばれる少なくとも１種からなるものを用いた場合でも上記と同様の効果を得ることができる。
【００３４】
【発明の効果】
以上説明したように、本発明は、十分なガラスの洗浄効果を得つつ、人体への安全性が高く、作業上での環境も含めた環境全体への配慮がなされたガラスの洗浄方法を提供することができるものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for cleaning glass.
[0002]
[Prior art]
For example, a glass member used for a general lighting tube, a cathode ray tube, or the like is usually washed as a pretreatment in a manufacturing process to remove foreign substances (for example, dust) attached to the surface.
[0003]
Conventionally, as a method of cleaning glass, an aqueous solution of hydrofluoric acid having an appropriate concentration has been generally used as a glass cleaning solution.
[0004]
As another cleaning solution used in the glass cleaning method, a liquid inorganic acid such as hydrochloric acid or nitric acid is added to an aqueous solution of hydrofluoric acid or ammonium acid fluoride in order to improve the cleaning speed and cleaning performance. The known one is known (JP-A-8-17348).
[0005]
[Problems to be solved by the invention]
However, in the above-mentioned conventional glass cleaning method, since a hydrofluoric acid aqueous solution is used, there is a problem that it is not appropriate to use the hydrofluoric acid aqueous solution itself from the viewpoint of safety to human bodies and environmental protection. there were.
[0006]
Further, although the aqueous solution of hydrofluoric acid itself is not used, even when a cleaning solution obtained by adding a liquid inorganic acid such as hydrochloric acid or nitric acid to the aqueous solution of ammonium ammonium fluoride is used, the acid fluoride ammonium and the hydrochloric acid or nitric acid are used. As a result, a large amount of hydrofluoric acid is generated by the reaction, and as a result, there is a problem that the hydrofluoric acid is inappropriate from the viewpoint of safety to human bodies and environmental protection.
[0007]
Furthermore, since hydrochloric acid, nitric acid and the like have a strong irritating odor of acid, there is a problem that using these inorganic acids is not preferable from the viewpoint of working environment.
[0008]
The present invention has been made in order to solve the above-mentioned problems, and while obtaining a sufficient glass cleaning effect, safety to the human body is high, and consideration has been given to the entire environment including the working environment. It is an object of the present invention to provide a method for cleaning glass.
[0009]
[Means for Solving the Problems]
The glass cleaning method of the present invention includes water, ammonium fluoride, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium dihydrogen phosphate, and dihydrogen phosphate. A method is used in which the glass is washed with a washing solution containing at least one solid inorganic acid selected from sodium hydrogen, potassium dihydrogen phosphate, and phosphorous acid .
[0010]
According to this method, while obtaining a cleaning effect sufficient glass for the solid inorganic acid is weakly acidic, low chemical reaction between ammonium fluoride and a solid inorganic acid, thus hydrogen fluoride Since the amount of acid generated can be reduced to a small amount, it is possible to realize a method for cleaning glass that is highly safe for the human body and environmentally friendly, and can also be used for liquid inorganic acids such as hydrochloric acid and nitric acid. Since no inorganic acid is used, that is, since a solid inorganic acid is used, strong irritating odor of the acid is not generated, and the working environment can be improved.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
In the glass cleaning method according to the embodiment of the present invention, a cleaning solution containing water, ammonium fluoride, and a solid inorganic acid is used.
[0012]
This washing solution preferably contains 1 mol to 6 mol of ammonium fluoride and 1 mol to 3 mol of inorganic acid per liter of water.
[0013]
Inorganic acids include ammonium bisulfate, sodium bisulfate, potassium bisulfate, ammonium bisulfite, sodium bisulfite, potassium bisulfite, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and phosphorous acid And at least one member selected from the group consisting of:
[0014]
Next, an outline of the glass cleaning method according to the embodiment of the present invention will be described.
[0015]
First, by immersing the glass to be cleaned (glass for a bulb made of quartz glass, soda lime glass, or lead glass, or glass for a cathode ray tube) into the above-described cleaning solution, and dissolving the surface layer of the glass. Then, the foreign matter adhering to the glass surface is peeled off (cleaning step). The glass surface layer is dissolved by a small amount of hydrofluoric acid generated by a chemical reaction between ammonium fluoride and a solid inorganic acid. In the cleaning solution, when hydrofluoric acid is consumed (decomposed) by melting glass, the consumed amount is newly generated by a chemical reaction between ammonium fluoride and a solid inorganic acid. That is, a certain amount of hydrofluoric acid is always present in the cleaning solution.
[0016]
The chemical reaction formula between hydrofluoric acid and glass (for example, quartz glass (SiO 2 )) is shown below.
[0017]
6HF + SiO 2 → H 2 SiF 6 + 2H 2 O
In the cleaning step, it is preferable to set the temperature of the cleaning solution to 10 ° C. or higher in order to enhance the cleaning effect of the glass. However, if the temperature of the cleaning solution is too high, the water in the cleaning solution will evaporate, and the concentration of the cleaning solution may become too high.
[0018]
After the washing step, the washed glass is immersed in pure water, and the peeled foreign substances are washed away together with the washing solution attached to the glass (water washing step). This washing step is repeated several times.
[0019]
Thereafter, hot air is blown onto the water-washed glass to dry it (drying step).
[0020]
As described above, water, ammonium fluoride, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium bisulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid By using a method for washing glass with a washing solution containing potassium dihydrogen and a solid inorganic acid composed of at least one selected from phosphorous acid , a solid washing effect is obtained while obtaining a sufficient glass washing effect. Since the inorganic acid is weakly acidic, the chemical reaction between ammonium fluoride and the solid inorganic acid is small, and the amount of hydrofluoric acid generated can be suppressed to a small amount, which is safe for the human body. It is possible to realize a glass cleaning method that is highly cost-effective and environmentally friendly. To not used, that is due to the use of solid inorganic acids, without irritating smell strong acid generator can also improve the environment on the work.
[0021]
Here, the reason why the cleaning solution preferably contains 1 mol to 6 mol of ammonium fluoride and 1 mol to 3 mol of inorganic acid per 1 liter of water will be described.
[0022]
As an object to be cleaned, a quartz glass tube for an arc tube of a metal halide lamp having a tube outer diameter of 18 mm (tube inner diameter of 15 mm) and a tube length of 35 mm was used.
[0023]
The quartz glass tube was cleaned using cleaning solutions having various compositions as shown in Table 1, and the cleaning power was evaluated.
[0024]
In the evaluation of the detergency in the present invention, the weight of the object to be cleaned before and after cleaning was compared, and the larger the difference in weight, the higher the detergency was evaluated. In Table 1, “◎” indicates “very high detergency”, “○” indicates “high detergency”, and “×” indicates “low detergency”.
[0025]
In the above evaluation, ammonium hydrogen sulfate alone was used as the solid inorganic acid. Further, the immersion time of the cleaning solution in the cleaning step was 15 minutes, and the temperature of the cleaning solution was 30 ° C.
[0026]
[Table 1]
As is clear from Table 1, in a cleaning solution containing 1 mol to 6 mol of ammonium fluoride and 1 mol to 3 mol of inorganic acid per liter of water, a large amount of glass surface layer is dissolved, and high cleaning power is obtained. I understand.
[0028]
Particularly, in a cleaning solution containing 3.5 mol to 5 mol of ammonium fluoride and 2.7 mol to 3 mol of inorganic acid per 1 liter of water, the amount of the surface layer of glass dissolved is much larger, and the cleaning power is very high. Was obtained. If a very high cleaning power is obtained as described above, the immersion time in the cleaning solution can be shortened, so that the cleaning operation efficiency can be improved.
[0029]
On the other hand, it was found that when the content of ammonium fluoride per liter of water was less than 1 mol as in Examples 1 to 5, the detergency was low. This is considered to be because the amount of hydrofluoric acid generated by the chemical reaction with the inorganic acid is significantly reduced. It was also found that the detergency was low even when the content of ammonium fluoride per liter of water exceeded 6 mol as in Examples 31 to 35. This is considered to be because the content of ammonium fluoride was too large, and the cleaning solution approached the saturation concentration.
[0030]
Further, even when the content of ammonium fluoride per 1 liter of water is an optimal amount (1 mol to 6 mol), as in Examples 6, 11, 11, 16, 21, and 26. When the content of ammonium hydrogen sulfate per liter of water was less than 1 mol, the detergency was found to be low. This is presumably because the chemical reaction with ammonium fluoride did not proceed sufficiently, and the amount of hydrofluoric acid produced was significantly reduced. In addition, even when the content of ammonium hydrogen sulfate per liter of water exceeds 3 mol as in Examples 10, 15, 20, 25, and 30, it was found that the detergency was low. . It is considered that this is because ammonium hydrogen sulfate is not dissolved in water due to saturation.
[0031]
Therefore, high cleaning power can be obtained by the cleaning solution containing 1 mol to 6 mol of ammonium fluoride and 1 mol to 3 mol of inorganic acid per 1 liter of water.
[0032]
Note that, in the above embodiment, the case where the method of dipping glass in the cleaning solution was used in the cleaning step was described. The same effect as described above can be obtained.
[0033]
Further, in the above embodiment, the case where only ammonium hydrogen sulfate alone was used as the solid inorganic acid was described. However, as the solid inorganic acid, ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, and hydrogen sulfite were used. Ammonium, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and the same as above even when at least one selected from the group consisting of phosphorous and phosphorous is used. The effect of can be obtained.
[0034]
【The invention's effect】
As described above, the present invention provides a method for cleaning glass, which has a sufficient effect of cleaning glass, is highly safe for the human body, and takes into consideration the entire environment including the environment during work. Is what you can do.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000260416A JP3603764B2 (en) | 2000-08-30 | 2000-08-30 | How to clean glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000260416A JP3603764B2 (en) | 2000-08-30 | 2000-08-30 | How to clean glass |
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| JP2002069493A JP2002069493A (en) | 2002-03-08 |
| JP3603764B2 true JP3603764B2 (en) | 2004-12-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2857042B2 (en) * | 1993-10-19 | 1999-02-10 | 新日本製鐵株式会社 | Cleaning liquid for silicon semiconductor and silicon oxide |
| JPH0817348A (en) * | 1994-06-30 | 1996-01-19 | Toshiba Corp | Manufacture of cathode-ray tube |
| JP3046208B2 (en) * | 1994-08-05 | 2000-05-29 | 新日本製鐵株式会社 | Cleaning liquid for silicon wafer and silicon oxide |
| JP2000117208A (en) * | 1998-10-13 | 2000-04-25 | Kurita Water Ind Ltd | Electronic material washing method |
| JP3313333B2 (en) * | 1998-11-12 | 2002-08-12 | ジョンソン・プロフェッショナル株式会社 | Aqueous composition for removing contamination on the surface of existing exterior glass |
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