JPH0214300B2 - - Google Patents
Info
- Publication number
- JPH0214300B2 JPH0214300B2 JP57083528A JP8352882A JPH0214300B2 JP H0214300 B2 JPH0214300 B2 JP H0214300B2 JP 57083528 A JP57083528 A JP 57083528A JP 8352882 A JP8352882 A JP 8352882A JP H0214300 B2 JPH0214300 B2 JP H0214300B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- treatment
- refractive index
- silica
- added
- 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 - Lifetime
Links
- 238000011282 treatment Methods 0.000 claims description 54
- 239000011521 glass Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 44
- 238000002834 transmittance Methods 0.000 description 26
- 235000003270 potassium fluoride Nutrition 0.000 description 22
- 239000011698 potassium fluoride Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 239000006059 cover glass Substances 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Landscapes
- Surface Treatment Of Glass (AREA)
- Chemically Coating (AREA)
Description
【発明の詳細な説明】
本発明は、ガラスの反射率を低下させ、透過率
を増大させるために、ガラス表面にポーラスでシ
リカリツチな層を均一に形成させる製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a manufacturing method for uniformly forming a porous and siliceous layer on a glass surface in order to reduce the reflectance and increase the transmittance of the glass.
更に詳細には、ガラスを珪弗化水素酸のシリカ
過飽和水溶液に浸漬などで接触させることによ
り、ガラス表面のシリカ以外の成分を選択的に溶
出除去してシリカの骨格層を残すようにした化学
的エツチング方法において、ガラス表面に生成す
るシリカ骨格層の屈折率を処理途中で知ることに
より、処理工程を制御することを特徴とする反射
防止ガラスの製造方法に関する。 More specifically, it is a chemical method in which components other than silica on the glass surface are selectively eluted and removed, leaving behind a silica skeleton layer, by contacting glass with a silica supersaturated aqueous solution of hydrofluorosilicic acid, such as by immersing it. The present invention relates to a method for manufacturing antireflection glass, characterized in that in a target etching method, the processing steps are controlled by knowing the refractive index of a silica skeleton layer formed on the glass surface during the processing.
近年、省エネルギー政策のため、太陽熱を利用
する研究が盛んに行われ、集熱効率を向上させた
種々の太陽熱集熱器が開発されている。この太陽
熱集熱器は一般的には、その集熱部を太陽に臨む
べく、外部へ露出させるため集熱部或いは集光部
に損傷を与えないように、透過性のすぐれたガラ
スの板、パイプ等でカバーされている。 In recent years, research into utilizing solar heat has been actively conducted due to energy conservation policies, and various solar heat collectors with improved heat collection efficiency have been developed. This solar heat collector generally exposes the heat collecting part to the outside to face the sun, so in order to avoid damaging the heat collecting part or the light collecting part, a glass plate with excellent transparency is used. Covered with pipes, etc.
該ガラスは、カバーとして機能するとともに太
陽熱集熱器の本来の目的を達成すべく、大量の光
エネルギーを通過させ、更には集熱器に吸収され
た熱エネルギーを外部に放散することなく、確保
するという機能を有さなければならない。集熱器
のカバー用ガラスが上記の如き機能を果すことに
よつて、太陽熱集熱器の集熱効率を一層向上せし
めることができるのである。実際には、集熱器が
吸収した熱エネルギーを確保するために、カバー
用ガラスを二層にして設けるのが一般的である。 The glass functions as a cover and allows a large amount of light energy to pass through in order to achieve the original purpose of the solar collector, and it also secures the heat energy absorbed by the collector without dissipating it to the outside. It must have the function of By having the cover glass of the heat collector perform the above-mentioned functions, the heat collection efficiency of the solar heat collector can be further improved. In practice, in order to secure the thermal energy absorbed by the heat collector, it is common to provide two layers of cover glass.
一方、カバー用ガラスにおいてより多くの光エ
ネルギーを通過せしめるために、ガラス自体の反
射率を低下させる必要がある。特にカバー用ガラ
スによる太陽光の反射損失は、ガラス一枚で集熱
器に照射される全エネルギーの７〜８％、従つて
二層のガラスでは12〜14％に達するため、ガラス
の反射による損失を低下せしめ、透過率を増大さ
せることは、集熱器の集熱効率の向上に大きく寄
与する。 On the other hand, in order to allow more light energy to pass through the cover glass, it is necessary to reduce the reflectance of the glass itself. In particular, the reflection loss of sunlight due to cover glass is 7 to 8% of the total energy irradiated to the collector with a single glass layer, and 12 to 14% with two layers of glass. Reducing loss and increasing transmittance greatly contributes to improving the heat collection efficiency of the heat collector.
従来、ガラスの反射率を低下せしめる方法とし
て、ガラスの表面に真空蒸着法によつて弗化マグ
ネシウム等の低屈折率薄膜をコーテイングする方
法があるが、この方法は主に、レンズ・フイルタ
ー等の小型の精密光学部品に使用されるもので、
装置の構造上、及びコスト的に太陽熱集熱器のカ
バーガラスの如き大型のものに使用することは困
難である。 Conventionally, there is a method of reducing the reflectance of glass by coating the surface of the glass with a thin film of low refractive index such as magnesium fluoride by vacuum evaporation, but this method is mainly used to reduce the reflectance of lenses, filters, etc. It is used for small precision optical parts.
Due to the structure and cost of the device, it is difficult to use it for large items such as cover glasses for solar heat collectors.
大型のガラスの反射率を低減し、透過率を増大
せしめる方法として、ニコルらによる米国特許第
2486431号、トムセンによる米国特許第2990662号
に開示された珪弗化水素酸のシリカ過飽和水溶液
を利用するエツチング方法がある。 A method for reducing the reflectance and increasing the transmittance of large glass glasses is described in U.S. Pat.
No. 2,486,431 and US Pat. No. 2,990,662 to Thomsen disclose an etching method that utilizes a supersaturated aqueous solution of silica in hydrofluorosilicic acid.
この方法によれば、ガラスを上記水溶液中に浸
漬し、ガラス成分であるアルカリ及びアルカリ土
類金属酸化物をガラス表面から取り除き、シリカ
成分のみを選択的に残すことによつて多孔質のシ
リカスケルトンからなる厚みが0.1μ前後の極めて
薄い層をガラス表面に形成することにより反射率
が低減された反射防止ガラスが得られる。 According to this method, a porous silica skeleton is formed by immersing glass in the above aqueous solution, removing alkali and alkaline earth metal oxides, which are glass components, from the glass surface and selectively leaving only the silica component. By forming an extremely thin layer of approximately 0.1 μm in thickness on the glass surface, antireflection glass with reduced reflectance can be obtained.
ところで上述の公知のエツチング方法による処
理では、処理液は珪弗化水素酸のシリカ過飽和水
溶液であるが、処理する時には、これに微量のホ
ウ酸又はフツ化カリウムを添加して液の状態を調
整する。ホウ酸は処理液中に存在するフツ素イオ
ンを減少させ、フツ化カリウムは逆に増加させる
と考えられる。液の状態が処理に適している時、
処理後のガラスは未処理ガラスと比較して、太陽
光透過率が約５％増加するが、このような液の状
態は、ホウ酸又はフツ化カリウムの添加量のある
せまい範囲でのみ達成される。さらにフツ素イオ
ン濃度が測定できないので液の状態が処理に適し
ているか否かを処理する前に知ることはできず、
処理後のガラスの太陽光透過率を測定して初めて
処理の可否を判定できる。太陽光透過率の測定を
行うには、ガラスを取り出して洗浄・乾燥する時
間が必要である。したがつて、連続的に処理を繰
り返す工程では、処理されたガラスの太陽光透過
率を測定して次の処理におけるフツ化カリウムの
添加量を判断し、次の処理を行うとすると、透過
率測定に要する時間は、次回の処理が行えず、見
かけの一回の処理時間が長くなり製造効率が低く
なる。また処理されたガラスの太陽光透過率の測
定結果がでる前に、透過率測定によつて経験的に
得られている一定量のフツ化カリウムを添加して
続けて処理を行つていくと、透過率測定結果のフ
イードバツクは次次回の処理時でなければ反映さ
れないことになる。従つて透過率の測定の結果、
一定量の添加量に補正を加える必要がある場合は
次回の処理時には補正がなされず、次に処理した
ガラスは所定の反射防止層が得られず、品質規格
からはずれたものとなり、歩留の低下となる。 By the way, in the treatment by the above-mentioned known etching method, the treatment liquid is a silica supersaturated aqueous solution of hydrosilicofluoric acid, but at the time of treatment, a trace amount of boric acid or potassium fluoride is added to this to adjust the condition of the liquid. do. It is believed that boric acid reduces fluorine ions present in the treatment solution, while potassium fluoride increases them. When the liquid condition is suitable for processing,
The treated glass has an approximately 5% increase in solar transmittance compared to the untreated glass, but this liquid state is only achieved within a certain narrow range of boric acid or potassium fluoride additions. Ru. Furthermore, since the fluorine ion concentration cannot be measured, it is not possible to know before processing whether the state of the liquid is suitable for treatment.
Only after measuring the sunlight transmittance of the glass after treatment can it be determined whether or not the treatment is appropriate. To measure sunlight transmittance, it is necessary to take out the glass, wash it, and dry it. Therefore, in a process where treatments are repeated continuously, the sunlight transmittance of the treated glass is measured to determine the amount of potassium fluoride added in the next treatment. The time required for measurement makes it impossible to carry out the next process, which increases the apparent time required for one process and reduces manufacturing efficiency. Furthermore, before the measurement results of the solar transmittance of the treated glass are obtained, if a certain amount of potassium fluoride, which has been empirically obtained from transmittance measurements, is added and the treatment is continued, The feedback of the transmittance measurement results will not be reflected until the next processing. Therefore, the result of transmittance measurement is
If it is necessary to make a correction to a certain amount of addition, the correction will not be made during the next processing, and the next processed glass will not have the specified anti-reflection layer and will deviate from the quality standard, resulting in a reduction in yield. This results in a decrease.
そこで処理が終了する前に次回処理のために処
理液に添加すべきフツ化カリウムの量が簡単に判
断できる方法の開発が望まれていた。 Therefore, it has been desired to develop a method that can easily determine the amount of potassium fluoride to be added to the treatment solution for the next treatment before the treatment is completed.
本発明者らは、この問題を解決すべく種々の検
討を行つた結果、処理の途中でガラス表面に生成
しつつある反射防止層の屈折率を測定することに
より、処理の成否を正確に予測し、次の処理にお
けるフツ化カリウムの最適添加量を決定する製造
方法を発明した。 As a result of various studies to solve this problem, the inventors of the present invention were able to accurately predict the success or failure of the treatment by measuring the refractive index of the antireflection layer that is forming on the glass surface during the treatment. We have invented a production method that determines the optimal amount of potassium fluoride to be added in the next treatment.
新しく調製した1.25mol／の珪弗化水素酸の
シリカ過飽和水溶液に一定量のホウ酸を添加し、
さらにフツ化カリウムを添加して調整した処理液
に、85.8％の太陽光透過率を有する３mm厚の普通
板ガラスを処理液１当り表面積300cm2で浸漬し、
処理時間を変えて取り出し、太陽光透過率を測定
した結果を第１図に示した。Ａ、Ｂ、Ｃはホウ酸
を処理液１当り、60×10-4mol添加し、さらに
フツ化カリウムを処理液１当り、それぞれ10×
10-4mol、16×10-4mol、22×10-4mol添加した処
理液で処理したガラスの太陽光透過率を示す。図
のようにＡ，Ｂ，Ｃのカーブは140分後に最大に
達し、太陽光透過率はそれぞれ90.2、91.0、90.0
％を示した。Ｂでは処理液の状態が処理して適し
ていたと判断できる。これに対してＡではフツ化
カリウムの添加量が不足し、Ｃでは過剰であつた
と考えられる。 A certain amount of boric acid was added to a freshly prepared 1.25 mol/hydrosilicic acid supersaturated aqueous solution of silica,
Furthermore, a 3 mm thick ordinary plate glass with a solar transmittance of 85.8% was immersed in a treatment solution prepared by adding potassium fluoride, with a surface area of 300 cm 2 per treatment solution.
Figure 1 shows the results of measuring the sunlight transmittance after taking out the samples at different treatment times. For A, B, and C, 60×10 -4 mol of boric acid was added per 1 treatment solution, and 10× potassium fluoride was added per 1 treatment solution.
It shows the sunlight transmittance of glass treated with treatment solutions containing 10 -4 mol, 16 x 10 -4 mol, and 22 x 10 -4 mol. As shown in the figure, curves A, B, and C reach their maximum after 140 minutes, and the sunlight transmittance is 90.2, 91.0, and 90.0, respectively.
%showed that. In case B, it can be determined that the condition of the processing liquid was suitable for processing. On the other hand, it is thought that in A, the amount of potassium fluoride added was insufficient, and in C, it was in excess.
同じガラスについて、表面に生成したシリカ多
孔層の屈折率（ｎ）、膜厚(d)を偏光解析装置（エ
リプソメーター）で測定し、第２図、第３図に示
した。140分処理後、Ａではｎ＝1.328、ｄ＝930
Å、Ｂではｎ＝1.269、ｄ＝1070Å、Ｃではｎ＝
1.224、ｄ＝1140Åであつた。また、80分処理後
ではＡでｎ＝1.249、ｄ＝410Å、Ｂでｎ＝1.154、
ｄ＝550Å、Ｃでｎ＝1.126、ｄ＝580Åであつた。
第２図からわかるように、処理液の状態によつて
生成する膜の屈折率が異なつており80分の処理時
間で十分に差を把握することができることがわか
つた。 Regarding the same glass, the refractive index (n) and film thickness (d) of the silica porous layer formed on the surface were measured using an ellipsometer (ellipsometer) and are shown in FIGS. 2 and 3. After 140 minutes of processing, n = 1.328, d = 930 for A
Å, for B n=1.269, d=1070Å, for C n=
1.224, d=1140 Å. In addition, after 80 minutes of treatment, n = 1.249, d = 410 Å in A, n = 1.154 in B,
d=550 Å, n=1.126 for C, and d=580 Å.
As can be seen from FIG. 2, the refractive index of the produced film differs depending on the state of the processing solution, and it was found that the processing time of 80 minutes was sufficient to determine the difference.
また第４図に実験で求めた80分処理時における
反射防止層の屈折率と次回処理時に添加すべきフ
ツ化カリウム添加量との関係を示す。 Furthermore, FIG. 4 shows the relationship between the refractive index of the antireflection layer after 80 minutes of treatment, determined by experiment, and the amount of potassium fluoride to be added in the next treatment.
上記フツ化カリウム添加量は、添加後の処理液
中へガラスを140分間浸漬したときに最高の太陽
光透過率が得られるような添加量である。 The amount of potassium fluoride added is such that the highest sunlight transmittance can be obtained when the glass is immersed in the treatment solution for 140 minutes after addition.
例えば、新規な処理液中にガラス板を80分間浸
漬した後取り出してその屈折率を測定して屈折率
が1.154であつたとすれば、同一の処理液を用い
て次回の処理を行なうに先立つてフツ化カリウム
を処理液１当り７×10-4molだけ添加すれば処
理液が最適条件に維持されて次回の処理時も140
分間の浸漬処理で最高の太陽光透過率が得られる
ことがわかる。以上のようにして反射防止層を生
成する最適処理時間の少くとも1/2の処理時間以
上処理したガラスの屈折率および必要に応じて膜
厚を測定することにより、処理液の状態を把握
し、最適状態からのずれから、次の処理における
フツ化カリウムの添加量を決めることができる。
太陽光透過率をもとに判断する場合第１図のよう
に、液の状態が異つていても、80分の値の差が小
さく処理途中で処理の成否を正確に推測すること
はできない。 For example, if a glass plate is immersed in a new treatment solution for 80 minutes and then taken out and its refractive index is measured and the refractive index is 1.154, then the refractive index is 1.154. By adding 7×10 -4 mol of potassium fluoride per treatment solution, the treatment solution can be maintained at optimal conditions and the next treatment will also have a
It can be seen that the highest sunlight transmittance can be obtained with a minute immersion treatment. By measuring the refractive index and, if necessary, the film thickness of the glass treated for at least 1/2 of the optimal treatment time to generate the antireflection layer as described above, the condition of the treatment solution can be ascertained. , the amount of potassium fluoride added in the next treatment can be determined based on the deviation from the optimum state.
When making judgments based on sunlight transmittance, as shown in Figure 1, even if the state of the liquid is different, the difference in the values at 80 minutes is small and it is not possible to accurately estimate the success or failure of processing during the process. .
以下に実施例を述べる。 Examples will be described below.
実施例
新しく調製した濃度1.25mol／の珪弗化水素
酸のシリカ過飽和水溶液からなる処理液に１当
り60×10-4molの割合でホウ酸を添加し、さらに
フツ化カリウムを１当り16×10-4molの割合で
添加して液の状態を調整した。これに、85.5％の
太陽光透過率を有する３mm厚の普通板ガラスを浸
漬して140分間放置した。ガラスを取り出して洗
浄、乾燥した後、太陽光透過率を測定した。太陽
光透過率は91.0％であり、未処理のガラスより
5.2％増加した。したがつて液の状態が処理に適
していたことがわかつた。連続して処理を行う場
合、処理ごとに処理液１当り、７×10-4molの
割合でフツ化カリウムを添加すると、次回の処理
でも太陽光透過率が約５％増加したガラスが得ら
れることが経験によつてわかつているので、この
割合でフツ化カリウムを添加した。これに３mm厚
の普通板ガラスを二枚浸漬し、一枚を80分後に取
り出した。これを洗浄、乾燥して表面に生成した
膜の屈折率と膜厚を偏光解析装置で測定したとこ
ろｎ＝1.154、ｄ＝550Åであつた。この値は、第
２図、第３図におけるＢの値と一致した。残りの
一枚を140分後にとり出して洗浄、乾燥した後、
太陽光透過率を測定したところ、91.0％であり、
未処理より5.2％増加した。Example: Boric acid was added at a rate of 60×10 -4 mol/unit to a newly prepared treatment solution consisting of a silica supersaturated aqueous solution of hydrosilicofluoric acid at a concentration of 1.25 mol/unit, and potassium fluoride was further added at a rate of 16×/unit/unit. The liquid condition was adjusted by adding it at a rate of 10 -4 mol. A 3 mm thick ordinary plate glass with a solar transmittance of 85.5% was immersed in this solution and left for 140 minutes. After the glass was taken out, washed, and dried, the sunlight transmittance was measured. Solar transmittance is 91.0%, better than untreated glass
It increased by 5.2%. Therefore, it was found that the condition of the liquid was suitable for treatment. When performing continuous treatments, adding potassium fluoride at a rate of 7 x 10 -4 mol per treatment solution for each treatment will result in glass with approximately 5% increased solar transmittance in the next treatment. Since this was known from experience, potassium fluoride was added at this rate. Two sheets of ordinary plate glass with a thickness of 3 mm were immersed in this solution, and one sheet was taken out after 80 minutes. This was washed and dried, and the refractive index and film thickness of the film formed on the surface were measured using an ellipsometer, and found that n=1.154 and d=550 Å. This value coincided with the value of B in FIGS. 2 and 3. The remaining piece was taken out after 140 minutes, washed and dried,
When we measured the sunlight transmittance, it was 91.0%.
Increased by 5.2% from untreated.
次にこの処理液に、処理液１当り１×
10-4molの割合でフツ化カリウムを添加し、３mm
厚の普通板ガラスを二枚浸漬した。一枚を80分後
にとり出し、洗浄、乾燥した後、表面に生成した
膜の屈折率と膜厚を偏光解析装置で測定したとこ
ろｎ＝1.249、ｄ＝410Åであつた。この値は第２
図、第３図のＡの値に一致した。残りの一枚を
140分後に取り出し、洗浄、乾燥した後、太陽光
透過率を測定したところ、90.2％であり、未処理
より4.4％しか増加しなかつた。 Next, add 1× to this treatment solution per treatment solution.
Potassium fluoride was added at a ratio of 10 -4 mol, and 3 mm
Two sheets of thick ordinary plate glass were immersed. One sheet was taken out after 80 minutes, washed and dried, and the refractive index and film thickness of the film formed on the surface were measured using an ellipsometer, and found that n = 1.249 and d = 410 Å. This value is the second
It matched the value of A in Figure 3. the remaining one
After being taken out after 140 minutes, washed and dried, the solar transmittance was measured to be 90.2%, an increase of only 4.4% over the untreated sample.
次いで、この処理液に処理液１当り、前回の
不足分を考慮して13×10-4molの割合でフツ化カ
リウムを添加し、３mm厚の普通板ガラスを二枚浸
漬した。一枚を80分後に取り出し、洗浄、乾燥し
て表面に生成した膜の屈折率と膜厚を偏光解析装
置で測定したところｎ＝1.154、ｄ＝550Åであつ
た。この値は第２図、第３図におけるＢの値と一
致した。残りの一枚を140分後に取り出し洗浄、
乾燥した後、太陽光透過率を測定したところ、
91.0％であり、未処理より5.2％増加した。屈折
率から判断したフツ化カリウムの添加量で処理液
の状態は回復した。 Next, potassium fluoride was added to this treatment solution at a rate of 13×10 −4 mol per treatment solution, taking into account the shortage from the previous treatment, and two sheets of ordinary plate glass with a thickness of 3 mm were immersed. One sheet was taken out after 80 minutes, washed and dried, and the refractive index and film thickness of the film formed on the surface were measured using an ellipsometer; n=1.154 and d=550 Å. This value coincided with the value of B in FIGS. 2 and 3. Remove the remaining piece after 140 minutes and wash it.
After drying, the sunlight transmittance was measured.
It was 91.0%, an increase of 5.2% from the untreated state. The condition of the treatment liquid was restored by adding the amount of potassium fluoride determined from the refractive index.
本実施例では、膜の屈折率膜厚の測定に偏光解
析装置を使用したが、他の方法でもよい。 In this example, an ellipsometer was used to measure the refractive index film thickness of the film, but other methods may be used.
第１図は珪弗化水素酸のシリカ過飽和水溶液に
フツ化カリウムを分量を変えて添加した処理液に
ガラスを浸漬した場合における処理時間と処理後
のガラスの太陽光透過率との関係を示すグラフ、
第２図は上記処理液への浸漬時間と得られるガラ
ス表面の反射防止層の屈折率との関係を示すグラ
フ、第３図は上記処理液への浸漬時間と得られる
ガラス表面の反射防止層の膜厚との関係を示すグ
ラフ、第４図は80分浸漬処理後の反射防止層の屈
折率と次回の処理時に液に添加すべきフツ化カリ
ウムの量との関係の一例を示すグラフである。
Figure 1 shows the relationship between the treatment time and the sunlight transmittance of the glass after treatment when glass is immersed in a treatment solution in which potassium fluoride is added in varying amounts to a silica supersaturated aqueous solution of hydrofluorosilicic acid. graph,
Figure 2 is a graph showing the relationship between the immersion time in the above treatment liquid and the refractive index of the resulting antireflection layer on the glass surface, and Figure 3 is a graph showing the relationship between the immersion time in the treatment liquid and the resulting antireflection layer on the glass surface. Figure 4 is a graph showing an example of the relationship between the refractive index of the antireflection layer after 80-minute immersion treatment and the amount of potassium fluoride that should be added to the solution during the next treatment. be.
Claims (1)
に接触させることによりガラス表面のシリカ以外
の成分を選択的に除去してシリカを主体とする多
孔層からなる反射防止層を形成する方法におい
て、前記処理の途中でガラス表面に生成したシリ
カ多孔層の屈折率を測定し、この屈折率と処理液
への添加剤の最適添加量との関係を予め求めてお
き、処理途中での屈折率測定から求めた所定量の
添加剤を次回処理時に加えて処理液を調整するこ
とを特徴とする反射防止ガラスの製造方法。1. In the method of forming an antireflection layer consisting of a porous layer mainly composed of silica by selectively removing components other than silica on the glass surface by bringing the glass into contact with a silica supersaturated aqueous solution of hydrofluorosilicic acid, The refractive index of the silica porous layer formed on the glass surface during the processing is measured, and the relationship between this refractive index and the optimal amount of additives to be added to the processing solution is determined in advance, and from the refractive index measurement during the processing. A method for producing antireflection glass, characterized by adjusting a treatment liquid by adding a determined amount of the additive in the next treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57083528A JPS58199744A (en) | 1982-05-18 | 1982-05-18 | Manufacture of antireflection glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57083528A JPS58199744A (en) | 1982-05-18 | 1982-05-18 | Manufacture of antireflection glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58199744A JPS58199744A (en) | 1983-11-21 |
| JPH0214300B2 true JPH0214300B2 (en) | 1990-04-06 |
Family
ID=13804983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57083528A Granted JPS58199744A (en) | 1982-05-18 | 1982-05-18 | Manufacture of antireflection glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58199744A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05260799A (en) * | 1992-01-27 | 1993-10-08 | Ind Technol Res Inst | Power factor controller for induction type methane gas generator |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60235745A (en) * | 1984-05-07 | 1985-11-22 | Hoya Corp | Porous antireflection film and its manufacture |
| LU86925A1 (en) * | 1987-06-19 | 1989-03-08 | Glaverbel | GLASS ARTICLE TRANSMITTING LIGHT AND HAVING LOW SPECULAR REFLECTION |
| CN102674704B (en) * | 2011-03-11 | 2014-07-09 | 北京市太阳能研究所有限公司 | Preparation method of porous nano silicon dioxide antireflection film |
| US9670088B2 (en) * | 2014-05-20 | 2017-06-06 | Corning Incorporated | Scratch resistant glass and method of making |
-
1982
- 1982-05-18 JP JP57083528A patent/JPS58199744A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05260799A (en) * | 1992-01-27 | 1993-10-08 | Ind Technol Res Inst | Power factor controller for induction type methane gas generator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58199744A (en) | 1983-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4019884A (en) | Method for providing porous broad-band antireflective surface layers on chemically-durable borosilicate glasses | |
| US4510344A (en) | Thin film solar cell substrate | |
| US2490662A (en) | Skeletonizing glass | |
| CN104347756A (en) | One-sided polishing method for monocrystalline silicon wafer for solar battery | |
| CN101599514A (en) | A kind of textured mono-crystalline silicon solar battery and preparation method thereof and preparation system | |
| AU529399B2 (en) | Black coatings on substrates | |
| CN102491649A (en) | Preparation method for anti-reflective glass | |
| US4693910A (en) | Process for producing porous antireflective coatings | |
| JP2012526719A (en) | Method for manufacturing reflection-reducing window glass | |
| US8445309B2 (en) | Anti-reflective photovoltaic module | |
| CN108048803A (en) | A kind of lens coating method | |
| CN101441330B (en) | Light-induced anti-fouling, anti-fog, self-cleaning resin lens and preparation method thereof | |
| JPH0214300B2 (en) | ||
| CA1148037A (en) | Process for preparing improved silvered glass mirrors | |
| CN105866976A (en) | Ultraviolet-proof lens structure and preparation method thereof | |
| NO760690L (en) | ||
| TW201813118A (en) | Solar cell manufacturing method | |
| CN106219992A (en) | A chemical etching preparation process for anti-glare glass | |
| JPS5845135A (en) | How to prevent deterioration of anti-reflective glass | |
| US3864194A (en) | Optical shielding element having low reflecting power and method for producing | |
| CN201327536Y (en) | Light-induction antifouling and anti-fog self-cleaning resin lens | |
| CN107099779A (en) | It is a kind of to improve optics laser damage threshold and the IAD plating methods of face shape | |
| CN112553585A (en) | Polymethyl methacrylate substrate medium antireflection film and preparation method thereof | |
| CN118206111A (en) | Carbon-based array structure for photothermal water evaporation system and preparation method thereof | |
| JPS6033775B2 (en) | Method of manufacturing anti-reflective glass |