JP2013014459A - Surface treatment liquid for producing anti-glare surface of glass substrate - Google Patents
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本発明は、ソーダガラス基板、無アルカリガラス基板、又はアルミノケイ酸ガラス基板の表面を防眩化（アンチグレア化）するための表面処理液及び当該表面処理液を用いた防眩化ガラス基板の製造方法に関する。本発明の表面処理液は、特にタッチパネル用の前記ガラス基板の表面を防眩化するために好適に用いられる。 The present invention relates to a surface treatment liquid for anti-glare (anti-glare) the surface of a soda glass substrate, an alkali-free glass substrate, or an aluminosilicate glass substrate, and a method for producing an anti-glare glass substrate using the surface treatment liquid About. The surface treatment liquid of the present invention is suitably used particularly for antiglare the surface of the glass substrate for a touch panel.
液晶テレビに代表される薄型テレビ及びパーソナルコンピュータのモニタなどの画像表示装置には、外光や屋内照明による反射の影響で視認性が低下することを防止するために反射防止膜が設けられている。 An image display device such as a flat-screen television represented by a liquid crystal television and a monitor of a personal computer is provided with an antireflection film in order to prevent the visibility from being deteriorated due to the influence of reflection by external light or indoor lighting. .
また近年、高機能携帯電話（スマートフォン）やタブレット型携帯端末に代表されるタッチパネルを搭載した電子デバイスがめざましい勢いで普及している。これらの携帯端末は、屋外での使用頻度が高いなどの理由により、反射防止性に優れることが求められる。 In recent years, electronic devices equipped with a touch panel typified by a high-function mobile phone (smart phone) and a tablet-type mobile terminal have been rapidly spreading. These portable terminals are required to have excellent antireflection properties for the reason that they are frequently used outdoors.
従来、ガラス基板表面の反射率を下げて、かつ光透過率を向上させる方法としては、ガラス基板表面にガラスよりも低い屈折率を有する反射防止膜を設ける方法が採用されている。しかし、タッチパネルを搭載した電子デバイスの場合、頻繁に指やペンでディスプレイ表面に触れるため、反射防止膜の劣化や剥がれが起こりやすいという問題があった。 Conventionally, as a method of reducing the reflectance of the glass substrate surface and improving the light transmittance, a method of providing an antireflection film having a refractive index lower than that of glass on the glass substrate surface has been adopted. However, in the case of an electronic device equipped with a touch panel, since the display surface is frequently touched with a finger or a pen, there is a problem that the antireflection film is likely to be deteriorated or peeled off.
ガラスの光反射を防止することを目的として、特許文献１では、弗化水素酸溶液に腐蝕されない物質の薄層で板ガラス片面を被覆し、該板ガラスを弗化水素酸と酢酸アンモニウムの混合溶液に常温で浸漬し、次に弗化水素酸の単独溶液または弗化水素酸の溶液と硫酸との混合溶液に常温で浸漬することを特徴とする透明性良好な無反射性ガラスの製造方法が提案されている。 In order to prevent light reflection of the glass, in Patent Document 1, one side of the plate glass is covered with a thin layer of a material that is not corroded by the hydrofluoric acid solution, and the plate glass is made into a mixed solution of hydrofluoric acid and ammonium acetate. Proposal of a method for producing non-reflective glass with good transparency, characterized by dipping at room temperature and then dipping in hydrofluoric acid alone or a mixture of hydrofluoric acid and sulfuric acid at room temperature Has been.
しかし、当該製造方法は２回の処理工程が必要であるため製造効率に劣る。また、２段階目の処理において、弗化水素酸の単独溶液を用いるとガラス成分に起因するカルシウムやアルミニウムの弗化物がガラス表面に堆積し、均一性が損なわれる。また、弗化水素酸と硫酸の混合溶液を用いた場合には、弗化物の発生は少ないが、ガラス表面に大きなうねりが生じることがある。 However, the manufacturing method is inferior in manufacturing efficiency because it requires two processing steps. In addition, if a single hydrofluoric acid solution is used in the second stage treatment, fluorides of calcium and aluminum resulting from the glass components are deposited on the glass surface and the uniformity is impaired. In addition, when a mixed solution of hydrofluoric acid and sulfuric acid is used, the generation of fluoride is small, but a large undulation may occur on the glass surface.
また、特許文献２では、二酸化珪素を過飽和状態とした珪弗化水素酸溶液よりなる処理液に基板を接触させて、該基板表面に二酸化珪素被膜を成膜することにより、基板表面に反射防止層を形成して低反射基板を製造する方法において、該二酸化珪素被膜の成膜速度を２０〜１００ｎｍ／時とすることにより該二酸化珪素被膜中の弗素含有量を調整し、屈折率１．４３５以下の反射防止層を形成することを特徴とする低反射基板の製造方法が提案されている。 Further, in Patent Document 2, the substrate is brought into contact with a treatment liquid made of a hydrosilicofluoric acid solution in which silicon dioxide is supersaturated, and a silicon dioxide film is formed on the substrate surface, thereby preventing reflection on the substrate surface. In the method for producing a low-reflection substrate by forming a layer, the fluorine content in the silicon dioxide film is adjusted by adjusting the film formation rate of the silicon dioxide film to 20 to 100 nm / hour, and the refractive index is 1.435. There has been proposed a method for manufacturing a low-reflection substrate characterized by forming the following antireflection layer.
しかし、上記で述べたように、当該低反射基板をタッチパネルに用いると、反射防止層の劣化や剥がれが起こりやすくなる。 However, as described above, when the low reflective substrate is used for a touch panel, the antireflection layer is likely to be deteriorated or peeled off.
また、非特許文献１には、ガラス基板のアンチグレア化（防眩化）処理は、フッ化水素とフッ化アンモニウムの混合液を用いて実施されることが記載されている。しかし、当該混合液を用いた場合には、処理後のガラス基板表面に白色のフッ化物結晶が残存したり、均一性が損なわれるという問題がある。 Non-Patent Document 1 describes that the antiglare (antiglare) treatment of the glass substrate is performed using a mixed liquid of hydrogen fluoride and ammonium fluoride. However, when the mixed solution is used, there is a problem that white fluoride crystals remain on the surface of the glass substrate after processing or the uniformity is impaired.
本発明は、ソーダガラス基板、無アルカリガラス基板、又はアルミノケイ酸ガラス基板の表面を防眩化（アンチグレア化）するための表面処理液及び当該表面処理液を用いた防眩化ガラス基板の製造方法を提供することを目的とする。 The present invention relates to a surface treatment liquid for anti-glare (anti-glare) the surface of a soda glass substrate, an alkali-free glass substrate, or an aluminosilicate glass substrate, and a method for producing an anti-glare glass substrate using the surface treatment liquid The purpose is to provide.
本発明者らは、前記従来の問題点を解決すべく表面処理液について検討した。その結果、ＨＦとＨ２ＳＯ４とを特定濃度で含有する混合溶液を用いることにより、前記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have studied surface treatment solutions to solve the conventional problems. As a result, it has been found that the above problem can be solved by using a mixed solution containing HF and H 2 SO 4 at a specific concentration, and the present invention has been completed.
すなわち本発明は、ガラス基板の表面を防眩化するための表面処理液において、
前記ガラス基板は、ソーダガラス基板、無アルカリガラス基板、又はアルミノケイ酸ガラス基板であり、
前記表面処理液は、下記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合でＨＦとＨ２ＳＯ４とを含有することを特徴とする表面処理液、に関する。
（ａ）Ｘ＝０．５
（ｂ）Ｘ＝１２
（ｃ）Ｙ＝７５
（ｄ）Ｙ＝２Ｘ＋８７
上記式（ａ）〜（ｄ）において、ＸはＨＦの濃度（重量％）であり、ＹはＨ２ＳＯ４の濃度（重量％）である。ただし、上記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合のうち、Ｘ＋Ｙ≧１００となる濃度割合を除く。
That is, the present invention provides a surface treatment liquid for antiglare the surface of a glass substrate.
The glass substrate is a soda glass substrate, an alkali-free glass substrate, or an aluminosilicate glass substrate,
It said surface treatment liquid, the surface treatment solution is characterized by containing HF and H 2 SO 4 at a concentration ratio surrounded by a straight line represented by the following formula (a) ~ (d), relates.
(A) X = 0.5
(B) X = 12
(C) Y = 75
(D) Y = 2X + 87
In the above formulas (a) to (d), X is the concentration (wt%) of HF, and Y is the concentration (wt%) of H 2 SO 4 . However, the density ratio satisfying X + Y ≧ 100 is excluded from the density ratio surrounded by the straight lines represented by the above formulas (a) to (d).
表面処理液中に硫酸を加えることにより、ガラスに含まれるカルシウム、アルミニウムなどの金属のフッ化物が溶液中に溶けやすくなり、前記ガラス基板上にフッ化物結晶が残存し難くなるため、均一なエッチングが可能になる。 By adding sulfuric acid to the surface treatment solution, fluorides of metals such as calcium and aluminum contained in the glass are easily dissolved in the solution, and fluoride crystals are difficult to remain on the glass substrate. Is possible.
また、本発明者らは、上記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合でＨＦとＨ２ＳＯ４とを含有する表面処理液を用いることにより、エッチング時に前記ガラス基板表面から気泡が発生し、この気泡がエッチングを一部阻害するマスク代わりとなり、前記ガラス基板表面に均一な凹凸が形成されることを見出した。 Moreover, the present inventors use the surface treatment liquid containing HF and H 2 SO 4 at a concentration ratio surrounded by the straight lines represented by the above formulas (a) to (d), so that the glass substrate is etched. It has been found that bubbles are generated from the surface, the bubbles serve as a mask that partially inhibits etching, and uniform irregularities are formed on the glass substrate surface.
表面処理液中のＨＦとＨ２ＳＯ４との濃度割合が、上記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合の範囲外の場合には、前記ガラス基板表面から気泡が発生せず、エッチングが均一に進行するため凹凸が十分に形成されない。そのため、前記ガラス基板に防眩性を付与することができない。 When the concentration ratio between HF and H 2 SO 4 in the surface treatment liquid is outside the concentration ratio range surrounded by the straight lines represented by the above formulas (a) to (d), bubbles are generated from the glass substrate surface. It does not occur, and the etching proceeds uniformly, so that the unevenness is not sufficiently formed. Therefore, antiglare property cannot be imparted to the glass substrate.
ガラス基板は、ソーダガラス基板、無アルカリガラス基板、又はアルミノケイ酸ガラス基板であることが必要である。ＳｉＯ２成分以外の元素が多く含まれるガラス基板を用いることにより、エッチング時に気泡が多く発生し、均一な微細凹凸が形成され、ガラス基板に十分な防眩性を付与することができる。石英ガラスのようにＳｉＯ２成分しか含まないガラス基板、又はホウケイ酸ガラスのようにＳｉＯ２成分の比率が高いガラス基板を用いると、エッチング時に気泡が発生し難くなるため、エッチングが均一に進行して凹凸が形成され難くなる。そのため、ガラス基板に防眩性を付与することができない。 The glass substrate needs to be a soda glass substrate, an alkali-free glass substrate, or an aluminosilicate glass substrate. By using a glass substrate containing a large amount of elements other than the SiO 2 component, many bubbles are generated during etching, uniform fine irregularities are formed, and sufficient antiglare properties can be imparted to the glass substrate. When a glass substrate containing only SiO 2 component such as quartz glass or a glass substrate having a high SiO 2 component ratio such as borosilicate glass is used, bubbles are less likely to be generated during etching, so that etching proceeds uniformly. As a result, it becomes difficult to form irregularities. Therefore, antiglare property cannot be imparted to the glass substrate.
また本発明は、前記表面処理液をソーダガラス基板、無アルカリガラス基板、又はアルミノケイ酸ガラス基板の表面に接触させて、当該表面を防眩処理する工程を含む防眩化ガラス基板の製造方法、に関する。 Further, the present invention provides a method for producing an antiglare glass substrate comprising a step of bringing the surface treatment liquid into contact with the surface of a soda glass substrate, an alkali-free glass substrate, or an aluminosilicate glass substrate, and subjecting the surface to an antiglare treatment, About.
本発明によれば、画像表示装置用の特定のガラス基板に簡易な方法で効果的に防眩処理を施すことができ、反射による景色の映り込み等を抑制することでディスプレイの視認性を向上させることができる。また、本発明の防眩化ガラス基板は、ガラス基板上に反射防止膜を設けておらず、ガラス基板に直接防眩処理を施しているため、タッチパネル用途に好適に用いられる。 According to the present invention, a specific glass substrate for an image display device can be effectively subjected to an antiglare treatment by a simple method, and the visibility of a display is improved by suppressing reflection of a landscape due to reflection. Can be made. Moreover, since the anti-glare glass substrate of this invention does not provide the anti-reflective film on the glass substrate and has performed the glare-proof process directly on the glass substrate, it is used suitably for a touch-panel use.
本発明に係る表面処理液の実施の形態について、以下に説明する。 Embodiments of the surface treatment liquid according to the present invention will be described below.
本発明の表面処理液は、下記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合でＨＦとＨ２ＳＯ４とを含有する。
（ａ）Ｘ＝０．５
（ｂ）Ｘ＝１２
（ｃ）Ｙ＝７５
（ｄ）Ｙ＝２Ｘ＋８７
上記式（ａ）〜（ｄ）において、ＸはＨＦの濃度（重量％）であり、ＹはＨ２ＳＯ４の濃度（重量％）である。ただし、上記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合のうち、Ｘ＋Ｙ≧１００となる濃度割合を除く。好ましくはＸ＋Ｙ＞９９となる濃度割合を除く。より好ましくはＸ＋Ｙ＞９７となる濃度割合を除く。特に好ましくはＸ＋Ｙ＞９５となる濃度割合を除く。
The surface treatment liquid of the present invention contains HF and H 2 SO 4 at a concentration ratio surrounded by straight lines represented by the following formulas (a) to (d).
(A) X = 0.5
(B) X = 12
(C) Y = 75
(D) Y = 2X + 87
In the above formulas (a) to (d), X is the concentration (wt%) of HF, and Y is the concentration (wt%) of H 2 SO 4 . However, the density ratio satisfying X + Y ≧ 100 is excluded from the density ratio surrounded by the straight lines represented by the above formulas (a) to (d). Preferably, the concentration ratio where X + Y> 99 is excluded. More preferably, the concentration ratio that satisfies X + Y> 97 is excluded. Particularly preferably, the concentration ratio in which X + Y> 95 is excluded.
前記表面処理液を調製する際には、通常６０％フッ化水素酸と９８％硫酸とが用いられるが、他の濃度のフッ化水素酸と硫酸とを混合して調製してもよい。 In preparing the surface treatment liquid, 60% hydrofluoric acid and 98% sulfuric acid are usually used, but other concentrations of hydrofluoric acid and sulfuric acid may be mixed and prepared.
前記表面処理液は、ＨＦを３〜６重量％、かつＨ２ＳＯ４を８４〜８７重量％含むことが好ましい。それにより、ガラス基板表面により均一な微細凹凸を形成でき、防眩性をより向上させることができる。 The surface treatment liquid preferably contains 3 to 6% by weight of HF and 84 to 87% by weight of H 2 SO 4 . Thereby, a uniform fine unevenness | corrugation can be formed on the glass substrate surface, and anti-glare property can be improved more.
前記表面処理液は、必須成分であるＨＦ及びＨ２ＳＯ４以外に任意成分を含んでいてもよい。任意成分としては、例えば、界面活性剤、過酸化水素、キレート剤などが挙げられる。 The surface treatment liquid may contain an optional component in addition to HF and H 2 SO 4 which are essential components. Examples of the optional component include a surfactant, hydrogen peroxide, and a chelating agent.
界面活性剤は特に制限されないが、強酸性水溶液中でも安定なポリエチレングリコールアルキルエーテル、ポリエチレングリコールアルキルフェニルエーテル、及びポリエチレングリコール脂肪酸エステル等の非イオン系界面活性剤が好ましい。 The surfactant is not particularly limited, but nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, and polyethylene glycol fatty acid ester that are stable even in a strongly acidic aqueous solution are preferable.
界面活性剤の含有量は、表面処理液中に０．００１〜０．１重量％であることが好ましく、０．００３〜０．０５重量％であることがより好ましい。界面活性剤を添加することにより、エッチング時にガラス基板表面から発生する気泡の大きさをコントロールしやすくなる。界面活性剤の含有量が０．００１重量％未満の場合には、気泡の大きさをコントロールし難くなり、一方０．１重量％を超えると気泡が消えやすくなる。 The surfactant content in the surface treatment liquid is preferably 0.001 to 0.1% by weight, and more preferably 0.003 to 0.05% by weight. By adding a surfactant, it becomes easy to control the size of bubbles generated from the glass substrate surface during etching. When the content of the surfactant is less than 0.001% by weight, it is difficult to control the size of the bubbles. On the other hand, when the content exceeds 0.1% by weight, the bubbles easily disappear.
以下、前記表面処理液を用いた防眩化ガラス基板の製造方法にについて説明する。 Hereinafter, the manufacturing method of the glare-proof glass substrate using the said surface treatment liquid is demonstrated.
ガラス基板としては、ソーダガラス基板、無アルカリガラス基板、又はアルミノケイ酸ガラス基板を用いる。 As the glass substrate, a soda glass substrate, a non-alkali glass substrate, or an aluminosilicate glass substrate is used.
前記ガラス基板の防眩処理（エッチング処理）としては、種々のウエットエッチング法が採用でき、具体的には前記表面処理液をガラス基板の表面に接触させることにより行う。エッチング処理はガラス基板の全面に行ってもよく、一部分のみに行ってもよい。また、ガラス基板の一方の面のみをエッチング処理するために、他面に保護シートを設けておいてもよい。 As the antiglare treatment (etching treatment) of the glass substrate, various wet etching methods can be employed. Specifically, the surface treatment liquid is brought into contact with the surface of the glass substrate. The etching process may be performed on the entire surface of the glass substrate, or may be performed on only a part of the glass substrate. Moreover, in order to etch only one side of the glass substrate, a protective sheet may be provided on the other side.
前記表面処理液をガラス基板の表面に接触させる方法は特に制限されず、例えば、浸漬式、塗布式、及びスプレー式などが挙げられる。浸漬式は、エッチング時にガラス基板表面から発生する気泡を安定化させることができるため好適である。浸漬式の場合、表面処理液の循環を行ったり、ガラス基板を揺動させながらエッチング処理を行ってもよい。 A method for bringing the surface treatment liquid into contact with the surface of the glass substrate is not particularly limited, and examples thereof include an immersion method, a coating method, and a spray method. The dipping method is preferable because bubbles generated from the glass substrate surface during etching can be stabilized. In the case of the immersion type, the etching treatment may be performed while circulating the surface treatment liquid or swinging the glass substrate.
前記表面処理液の温度は特に制限されないが、１０〜４０℃であることが好ましく、より好ましくは２０〜３０℃である。前記温度範囲の場合、表面処理液中の成分の蒸発を抑制することができ、組成変化を防止することができる。温度が高すぎると表面処理液中の成分の蒸発により処理時間の制御が困難になり、温度が低すぎるとガラス基板の溶解によって生成するフッ化物が結晶化しやすくなる。 The temperature of the surface treatment liquid is not particularly limited, but is preferably 10 to 40 ° C, more preferably 20 to 30 ° C. In the case of the above temperature range, evaporation of components in the surface treatment liquid can be suppressed, and a change in composition can be prevented. If the temperature is too high, it becomes difficult to control the treatment time due to evaporation of the components in the surface treatment liquid, and if the temperature is too low, the fluoride produced by dissolution of the glass substrate tends to crystallize.
エッチング時間は、使用するガラス基板の種類等に応じて適宜調整する必要があるが、通常１０秒〜１０分程度であり、好ましくは３０秒〜２分である。 Although it is necessary to adjust etching time suitably according to the kind etc. of glass substrate to be used, it is about 10 second-about 10 minutes normally, Preferably it is 30 second-2 minutes.
以下、本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
［測定、評価方法］
（反射率の測定）
エッチング処理したガラス基板の反射率は、光干渉式膜厚測定装置（ナノメトリクス社製、Ｎａｎｏｓｐｅｃ６１００ＵＶ）を用いて測定した。なお、測定波長は５５０ｎｍ、入射角は０度として正反射率を測定した。
[Measurement and evaluation methods]
(Measurement of reflectance)
The reflectance of the etched glass substrate was measured using an optical interference film thickness measuring device (Nanometric 6100UV, manufactured by Nanometrics). The regular reflectance was measured at a measurement wavelength of 550 nm and an incident angle of 0 degree.
（透過率の測定方法）
エッチング処理したガラス基板の透過率は、分光光度計（日立ハイテク社製、Ｕ−２０００）を用いて測定した。なお、測定波長は５５０ｎｍ、入射角は０度として正透過率を測定した。
(Measurement method of transmittance)
The transmittance of the etched glass substrate was measured using a spectrophotometer (manufactured by Hitachi High-Tech, U-2000). The regular transmittance was measured with a measurement wavelength of 550 nm and an incident angle of 0 degree.
（防眩化状態の評価方法）
ガラス基板の防眩化状態を目視にて観察し、下記基準で評価した。
◎：約２ｍ上方にある蛍光灯をガラス基板に映した時、蛍光灯の輪郭がぼやけ、かつガラス基板を通して１０ｃｍ先の文字が読み取れる。
○：約２ｍ上方にある蛍光灯をガラス基板に映した時、蛍光灯の輪郭がぼやけ、かつガラス基板を通して１０ｃｍ先の文字が読み取れるが、ガラス基板表面の凹凸が不均一である。
×：約２ｍ上方にある蛍光灯をガラス基板に映した時、蛍光灯の輪郭がはっきり視認でき、かつガラス基板を通して１０ｃｍ先の文字が読み取れる。あるいは、約２ｍ上方にある蛍光灯をガラス基板に映した時、蛍光灯の輪郭がぼやけ、かつガラス基板を通して１０ｃｍ先の文字が読み取れない。
(Evaluation method of anti-glare state)
The antiglare state of the glass substrate was visually observed and evaluated according to the following criteria.
A: When a fluorescent lamp approximately 2 m above is projected on a glass substrate, the outline of the fluorescent lamp is blurred and a character 10 cm ahead can be read through the glass substrate.
○: When a fluorescent lamp approximately 2 m above is projected on a glass substrate, the outline of the fluorescent lamp is blurred and characters 10 cm ahead can be read through the glass substrate, but the unevenness of the glass substrate surface is uneven.
X: When a fluorescent lamp approximately 2 m above is projected on a glass substrate, the outline of the fluorescent lamp can be clearly seen, and a character 10 cm ahead can be read through the glass substrate. Alternatively, when a fluorescent lamp located approximately 2 m above is projected on a glass substrate, the outline of the fluorescent lamp is blurred and characters 10 cm ahead cannot be read through the glass substrate.
実施例１
（ガラス基板の前処理）
ソーダガラス基板（厚さ０．５５ｍｍ）を４０ｍｍ×４０ｍｍにカットし、その片面に耐酸性テープを貼付した。基板表面の汚染を除去するために、０．５％のフッ化水素酸で３０秒間エッチング処理し、その後、超純水で５分間リンスを行い、窒素ブローにて乾燥させた。
Example 1
(Pretreatment of glass substrate)
A soda glass substrate (thickness 0.55 mm) was cut into 40 mm × 40 mm, and acid-resistant tape was stuck on one side thereof. In order to remove the contamination on the substrate surface, the substrate was etched with 0.5% hydrofluoric acid for 30 seconds, rinsed with ultrapure water for 5 minutes, and dried by nitrogen blowing.
（表面処理液の調製）
容器にフッ化水素酸（ステラケミファ（株）製、濃度６０重量％）１７重量部、及び超純水１６７重量部を加えて混合し、さらに硫酸（三菱化学（株）製、濃度９８重量％）８１６重量部を加えて混合した。その後、当該容器を２５℃に設定した高温槽に浸漬して１時間放置し、ＨＦを１重量％及びＨ２ＳＯ４を８０重量％含む表面処理液を調製した。図１のグラフ中に当該表面処理液のＨＦ濃度及びＨ２ＳＯ４濃度を示す。
(Preparation of surface treatment solution)
In a container, 17 parts by weight of hydrofluoric acid (manufactured by Stella Chemifa Co., Ltd., concentration 60% by weight) and 167 parts by weight of ultrapure water were added and mixed, and further sulfuric acid (manufactured by Mitsubishi Chemical Corporation, concentration 98% by weight). ) 816 parts by weight were added and mixed. Thereafter, the vessel was allowed to stand for 1 hour by immersion in hot bath set to 25 ° C., to prepare the surface treatment liquid HF 1 wt% and the H 2 SO 4 and containing 80% by weight. The HF concentration and H 2 SO 4 concentration of the surface treatment liquid are shown in the graph of FIG.
（ガラス基板のエッチング処理）
前処理したソーダガラス基板を前記表面処理液に１０分間浸漬した後、超純水で５分間リンスを行い、窒素ブローにて乾燥させた。なお、エッチング処理時には、ソーダガラス基板の表面から気泡が多く発生していた。片面の耐酸性テープを剥離し、ガラス面に残存したテープの粘着剤残渣を除去するため、０．５％のフッ化水素酸で３０秒間エッチング処理し、その後、超純水で５分間リンスを行い、窒素ブローにて乾燥させた。
(Glass substrate etching process)
The pretreated soda glass substrate was immersed in the surface treatment solution for 10 minutes, rinsed with ultrapure water for 5 minutes, and dried by nitrogen blowing. During the etching process, many bubbles were generated from the surface of the soda glass substrate. In order to remove the acid-resistant tape on one side and remove the adhesive residue of the tape remaining on the glass surface, it was etched with 0.5% hydrofluoric acid for 30 seconds, and then rinsed with ultrapure water for 5 minutes. And dried with nitrogen blow.
実施例２〜１０、比較例１〜５
表１に示す表面処理液を用い、エッチング時間を変更した以外は実施例１と同様の方法でソーダガラス基板をエッチング処理した。図１のグラフ中にこれら表面処理液のＨＦ濃度及びＨ２ＳＯ４濃度を示す。
Examples 2-10, Comparative Examples 1-5
The soda glass substrate was etched by the same method as in Example 1 except that the surface treatment liquid shown in Table 1 was used and the etching time was changed. The HF concentration and H 2 SO 4 concentration of these surface treatment solutions are shown in the graph of FIG.
表１及び図１からわかるように、（ａ）Ｘ＝０．５、（ｂ）Ｘ＝１２、（ｃ）Ｙ＝７５、及び（ｄ）Ｙ＝２Ｘ＋８７で示される直線によって囲まれる濃度割合でＨＦとＨ２ＳＯ４とを含有する表面処理液を用いた実施例１〜１０においては、エッチング処理中にガラス基板表面から気泡が発生することで均一な凹凸が形成されており、適度な防眩化処理ができている。一方、ＨＦとＨ２ＳＯ４との濃度割合が、前記直線（ａ）〜（ｄ）によって囲まれる濃度割合の範囲外である表面処理液を用いた比較例１〜５においては、エッチング処理中にガラス基板表面から気泡が発生せず、ガラス基板表面が均一にエッチングされたため凹凸が形成されなかった。そのため、防眩化表面を得ることはできなかった。 As can be seen from Table 1 and FIG. 1, (a) X = 0.5, (b) X = 12, (c) Y = 75, and (d) Y = 2X + 87. In Examples 1 to 10 using the surface treatment liquid containing HF and H 2 SO 4 , uniform irregularities are formed by generating bubbles from the surface of the glass substrate during the etching treatment, and appropriate protection Dazzling treatment has been completed. On the other hand, in Comparative Examples 1 to 5 using the surface treatment liquid in which the concentration ratio of HF and H 2 SO 4 is outside the range of the concentration ratio surrounded by the straight lines (a) to (d), the etching process is in progress. No air bubbles were generated from the surface of the glass substrate, and the glass substrate surface was uniformly etched, so that no irregularities were formed. Therefore, an antiglare surface could not be obtained.
実施例１１〜１４、比較例６〜９
表２に示すガラス基板及び表面処理液を用い、エッチング時間を変更した以外は実施例１と同様の方法でガラス基板をエッチング処理した。
Examples 11-14, Comparative Examples 6-9
The glass substrate was etched by the same method as in Example 1 except that the etching time was changed using the glass substrate and the surface treatment liquid shown in Table 2.
表２からわかるように、無アルカリガラス基板又はアルミノケイ酸ガラス基板を用いた実施例１１〜１４においては、エッチング処理中にガラス基板表面から気泡が発生することで均一な凹凸が形成されており、適度な防眩化処理ができている。一方、石英ガラス基板又はホウケイ酸ガラス基板を用いた比較例６〜９においては、エッチング処理中にガラス基板表面から気泡がほとんど発生せず、ガラス基板表面が均一にエッチングされたため凹凸がほとんど形成されなかった。そのため、防眩化表面を得ることはできなかった。 As can be seen from Table 2, in Examples 11 to 14 using an alkali-free glass substrate or an aluminosilicate glass substrate, uniform irregularities are formed by generating bubbles from the glass substrate surface during the etching process, Appropriate anti-glare treatment has been achieved. On the other hand, in Comparative Examples 6 to 9 using a quartz glass substrate or a borosilicate glass substrate, almost no bubbles are generated from the glass substrate surface during the etching process, and the glass substrate surface is etched uniformly, so that most irregularities are formed. There wasn't. Therefore, an antiglare surface could not be obtained.
本発明の表面処理液は、画像表示装置用のガラス基板の表面を防眩化（アンチグレア化）するために用いられる。本発明の表面処理液は、特にタッチパネル用のガラス基板の表面を防眩化するために好適に用いられる。 The surface treatment liquid of the present invention is used for anti-glare (anti-glare) the surface of a glass substrate for an image display device. The surface treatment liquid of the present invention is suitably used particularly for antiglare the surface of a glass substrate for a touch panel.
Claims (2)
前記ガラス基板は、ソーダガラス基板、無アルカリガラス基板、又はアルミノケイ酸ガラス基板であり、
前記表面処理液は、下記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合でＨＦとＨ２ＳＯ４とを含有することを特徴とする表面処理液。
（ａ）Ｘ＝０．５
（ｂ）Ｘ＝１２
（ｃ）Ｙ＝７５
（ｄ）Ｙ＝２Ｘ＋８７
上記式（ａ）〜（ｄ）において、ＸはＨＦの濃度（重量％）であり、ＹはＨ２ＳＯ４の濃度（重量％）である。ただし、上記式（ａ）〜（ｄ）で示される直線によって囲まれる濃度割合のうち、Ｘ＋Ｙ≧１００となる濃度割合を除く。 In the surface treatment liquid for anti-glare the surface of the glass substrate,
The glass substrate is a soda glass substrate, an alkali-free glass substrate, or an aluminosilicate glass substrate,
Said surface treatment liquid, the surface treatment solution is characterized by containing HF and H 2 SO 4 at a concentration ratio surrounded by a straight line represented by the following formula (a) ~ (d).
(A) X = 0.5
(B) X = 12
(C) Y = 75
(D) Y = 2X + 87
In the above formulas (a) to (d), X is the concentration (wt%) of HF, and Y is the concentration (wt%) of H 2 SO 4 . However, the density ratio satisfying X + Y ≧ 100 is excluded from the density ratio surrounded by the straight lines represented by the above formulas (a) to (d).
A method for producing an antiglare glass substrate, comprising the step of bringing the surface treatment liquid according to claim 1 into contact with the surface of a soda glass substrate, an alkali-free glass substrate, or an aluminosilicate glass substrate, and subjecting the surface to antiglare treatment.
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| JP2015521151A (en) * | 2012-05-10 | 2015-07-27 | コーニング インコーポレイテッド | Glass etching medium and method |
| CN105152542A (en) * | 2015-10-19 | 2015-12-16 | 上海光和光学制造股份有限公司 | Preparation method of anti-dazzle glass |
| WO2017038075A1 (en) * | 2015-08-31 | 2017-03-09 | 日本板硝子株式会社 | Method for producing glass with fine structure |
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