JPWO2014080917A1 - Glass substrate cleaning method - Google Patents
Glass substrate cleaning method Download PDFInfo
- Publication number
- JPWO2014080917A1 JPWO2014080917A1 JP2014548586A JP2014548586A JPWO2014080917A1 JP WO2014080917 A1 JPWO2014080917 A1 JP WO2014080917A1 JP 2014548586 A JP2014548586 A JP 2014548586A JP 2014548586 A JP2014548586 A JP 2014548586A JP WO2014080917 A1 JPWO2014080917 A1 JP WO2014080917A1
- Authority
- JP
- Japan
- Prior art keywords
- glass substrate
- cleaning
- acid
- mass
- cleaning liquid
- 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.)
- Pending
Links
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Images
Classifications
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/044—Hydroxides or bases
-
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Abstract
研磨後のガラス基板の洗浄方法において、洗浄されたガラス基板表面に形成される樹脂ＢＭ膜の密着性低下を抑制して、樹脂ＢＭ膜の剥れを防止する。酸化セリウム粒子を含有する研磨剤により研磨されたガラス基板を、有機酸を含む酸性の水系洗浄液により洗浄し、次いで塩基を含むアルカリ性の水系洗浄液により洗浄することを特徴とするガラス基板の洗浄方法である。In the glass substrate cleaning method after polishing, the resin BM film formed on the surface of the cleaned glass substrate is prevented from being lowered in adhesion, thereby preventing the resin BM film from peeling off. A method of cleaning a glass substrate, characterized in that a glass substrate polished with an abrasive containing cerium oxide particles is washed with an acidic aqueous cleaning solution containing an organic acid, and then washed with an alkaline aqueous cleaning solution containing a base. is there.
Description
本発明は、酸化セリウム粒子を含有する研磨剤で研磨されたガラス基板を洗浄するための洗浄方法に係り、特に、液晶表示装置用等のガラス基板を洗浄するための洗浄方法に関する。 The present invention relates to a cleaning method for cleaning a glass substrate polished with an abrasive containing cerium oxide particles, and more particularly to a cleaning method for cleaning a glass substrate for a liquid crystal display device or the like.
液晶表示装置（ＬＣＤ）等のＦＰＤ（Flat Panel Display）用として用いられるガラス基板は、例えば、溶融ガラスから板状に成形されたガラス基板を、自転および公転する研磨具で研磨して表面の微小な凹凸やうねりを除去することによって、ＦＰＤ用ガラス基板に要求される平坦度を満足させた、所定の厚さ（例えば、０．４〜１．１ｍｍ）の薄板状に形成される。 A glass substrate used for an FPD (Flat Panel Display) such as a liquid crystal display device (LCD), for example, a glass substrate formed into a plate shape from molten glass is polished by a rotating and revolving polishing tool to obtain a fine surface. By removing irregularities and undulations, a thin plate having a predetermined thickness (for example, 0.4 to 1.1 mm) that satisfies the flatness required for the glass substrate for FPD is formed.
このようなガラス基板の研磨には、砥粒として酸化セリウム粒子を含有する研磨剤（スラリー）が使用されており、研磨後は、ガラス基板表面に付着している研磨剤（砥粒等）を、洗浄液により洗浄し除去することが行われている（例えば、特許文献１参照）。 For polishing such a glass substrate, an abrasive (slurry) containing cerium oxide particles is used as abrasive grains, and after polishing, abrasives (abrasive grains, etc.) adhering to the glass substrate surface are used. Cleaning with a cleaning solution is performed (see, for example, Patent Document 1).
そして、このような酸化セリウム粒子を砥粒とする研磨剤の残留に対しては、例えば、無機または有機のアルカリ成分と界面活性剤とを含むアルカリ性の洗浄液では、洗浄性が不十分であり、粒径がサブミクロンオーダーの砥粒残渣を十分に除去することができなかった。 And with respect to the residue of the abrasive with such cerium oxide particles as an abrasive, for example, an alkaline cleaning liquid containing an inorganic or organic alkali component and a surfactant has insufficient cleaning properties, Abrasive grain residues having a particle size of submicron order could not be sufficiently removed.
前記アルカリ洗浄における問題点の解決策として、本発明者らは、有機ホスホン酸のような有機酸を含む酸性の洗浄液を使用し、酸化セリウムを溶かす等の方法で、ガラス基板上の砥粒の残渣を除去する方法を提案した（特願２０１１−１１５３５３号参照）。 As a solution to the problems in the alkali cleaning, the present inventors use an acidic cleaning liquid containing an organic acid such as organic phosphonic acid, and dissolve abrasive grains on the glass substrate by a method such as dissolving cerium oxide. A method for removing the residue was proposed (see Japanese Patent Application No. 2011-115353).
しかしながら、ＬＣＤ用等のアルミノケイ酸ガラスからなる基板を、前記した酸性の洗浄液で洗浄した場合、リーチング（leaching、浸出）作用により、ガラス基板の表面（表層）のＡｌイオン等のＡｌ成分が抜け出す結果、ガラス基板の表面に、ＯＨ基が過剰な親水性の高い層（以下、ＯＨリッチ親水層という。）が形成される。 However, when a substrate made of aluminosilicate glass for LCD or the like is washed with the above-described acidic cleaning solution, Al components such as Al ions on the surface (surface layer) of the glass substrate escape due to the leaching action. On the surface of the glass substrate, a highly hydrophilic layer containing excess OH groups (hereinafter referred to as OH-rich hydrophilic layer) is formed.
そのため、洗浄後のガラス基板の上に、カーボンブラックのような黒色顔料を含有する樹脂組成物を用いてカラーフィルター用のブラックマトリクス（ＢＭ）を形成する工程で、ガラス基板表面のＯＨリッチ親水層と樹脂系のブラックマトリクス膜との界面から現像液が浸入し、膜剥れを引き起こすという問題があった。 Therefore, in the process of forming a black matrix (BM) for a color filter using a resin composition containing a black pigment such as carbon black on a glass substrate after washing, an OH-rich hydrophilic layer on the surface of the glass substrate There is a problem that the developer enters from the interface between the resin and the black matrix film of the resin and causes film peeling.
本発明は上記問題を解決するためになされたもので、ガラス基板の平坦性を損なうことなく、その表面に残留・付着した研磨砥粒を分散して除去することができ、かつ洗浄後のガラス基板表面に形成される樹脂系ブラックマトリクス膜（以下、樹脂ＢＭ膜ともいう。）の密着性低下を抑制して、樹脂ＢＭ膜の剥れを防止することができる、ガラス基板の洗浄方法を提供することを目的としている。 The present invention has been made to solve the above problems, and can remove and remove abrasive grains remaining on and adhered to the surface of the glass substrate without deteriorating the flatness of the glass substrate. Provided is a glass substrate cleaning method capable of preventing a resin BM film from peeling off by suppressing a decrease in adhesion of a resin black matrix film (hereinafter also referred to as a resin BM film) formed on a substrate surface. The purpose is to do.
本発明のガラス基板の洗浄方法は、酸化セリウム粒子を含有する研磨剤により研磨されたガラス基板を、有機酸を含む酸性の水系洗浄液により洗浄し、次いで塩基を含むアルカリ性の水系洗浄液により洗浄することを特徴とする。 In the glass substrate cleaning method of the present invention, a glass substrate polished with an abrasive containing cerium oxide particles is washed with an acidic aqueous cleaning solution containing an organic acid, and then washed with an alkaline aqueous cleaning solution containing a base. It is characterized by.
本発明のガラス基板の洗浄方法において、前記酸性の水系洗浄液は、ｐＨ５以下であることが好ましい。また、前記酸性の水系洗浄液は、（Ａ）有機ホスホン酸と、（Ｂ）ポリカルボン酸塩と、（Ｃ）芳香族スルホン酸と、（Ｄ）アミン−アルキレンオキサイド付加物とを含有する水系洗浄液であることが好ましい。また、前記酸性の水系洗浄液は、前記（Ａ）〜（Ｄ）の各成分の含有割合が、（Ａ）〜（Ｄ）の合計量１００質量％に対して、（Ａ）有機ホスホン酸が０．０１〜５０質量％、（Ｂ）ポリカルボン酸塩が０．０１〜１０質量％、（Ｃ）芳香族スルホン酸が０．０１〜５０質量％、および（Ｄ）アミン−アルキレンオキサイド付加物が０．０２〜１０質量％であることが好ましい。さらに、前記アルカリ性の水系洗浄液は、ｐＨ１０以上の水系洗浄液であることが好ましい。また、前記アルカリ性の水系洗浄液は、塩基とキレート剤と界面活性剤とを含有する水系洗浄液であることが好ましい。さらに前記アルカリ性の水系洗浄液は、前記塩基と前記キレート剤と前記界面活性剤との質量含有比率である、（塩基）：（キレート剤）：（界面活性剤）が、（１〜１０）：（１〜１０）：（１〜１０）であることが好ましい。
さらにまた、前記ガラス基板は、アルミノケイ酸ガラスからなるガラス基板であることが好ましい。そして、前記アルミノケイ酸ガラスは、アルカリ金属成分を実質的に含有しないアルミノホウケイ酸ガラスであることが好ましい。さらに、前記ガラス基板は、その上に樹脂系ブラックマトリックス膜が形成される液晶表示装置用のガラス基板であることが好ましい。In the glass substrate cleaning method of the present invention, the acidic aqueous cleaning solution preferably has a pH of 5 or less. The acidic aqueous cleaning liquid is an aqueous cleaning liquid containing (A) an organic phosphonic acid, (B) a polycarboxylic acid salt, (C) an aromatic sulfonic acid, and (D) an amine-alkylene oxide adduct. It is preferable that Further, in the acidic aqueous cleaning liquid, the content ratio of the components (A) to (D) is (A) the organic phosphonic acid is 0 with respect to the total amount of 100% by mass of (A) to (D). 0.01-50 mass%, (B) 0.01-10 mass% polycarboxylate, (C) 0.01-50 mass% aromatic sulfonic acid, and (D) amine-alkylene oxide adduct. It is preferable that it is 0.02-10 mass%. Furthermore, the alkaline aqueous cleaning liquid is preferably an aqueous cleaning liquid having a pH of 10 or more. The alkaline aqueous cleaning liquid is preferably an aqueous cleaning liquid containing a base, a chelating agent, and a surfactant. Further, the alkaline aqueous cleaning liquid has a mass content ratio of the base, the chelating agent, and the surfactant, and (base) :( chelating agent) :( surfactant) is (1-10) :( 1-10): (1-10) is preferable.
Furthermore, it is preferable that the glass substrate is a glass substrate made of aluminosilicate glass. The aluminosilicate glass is preferably an aluminoborosilicate glass that does not substantially contain an alkali metal component. Further, the glass substrate is preferably a glass substrate for a liquid crystal display device on which a resin black matrix film is formed.
本発明の洗浄方法によれば、酸化セリウム粒子を含有する研磨剤で研磨されたガラス基板を、表面の平坦性を損なうことなく効率的に洗浄して、表面に残留・付着した酸化セリウム粒子等の砥粒を除去することができ、かつ洗浄後のガラス基板表面に形成される樹脂ＢＭ膜の密着性低下を抑制して、樹脂ＢＭ膜の剥れを防止することができる。 According to the cleaning method of the present invention, a glass substrate polished with an abrasive containing cerium oxide particles is efficiently cleaned without impairing the flatness of the surface, and the cerium oxide particles remaining on and adhered to the surface, etc. The abrasive grains can be removed, and the decrease in the adhesion of the resin BM film formed on the surface of the glass substrate after washing can be suppressed to prevent the resin BM film from peeling off.
すなわち、本発明の洗浄方法において、前記研磨剤で研磨されたガラス基板は、まず有機酸を含む酸性の水系洗浄液により洗浄され、ガラス基板の表面に残留・付着した酸化セリウム粒子等の砥粒が効率的に除去された後、この酸洗浄により生じたガラス基板表面のＯＨリッチ親水層が、塩基を含むアルカリ性の水系洗浄液により除去される。このようにガラス基板表面のＯＨリッチ親水層が除去される結果、ガラス基板上に樹脂ＢＭ膜が形成される際に、ガラス基板とＢＭ用樹脂組成物膜との界面からの現像液の浸入が抑えられ、樹脂ＢＭ膜の密着性が向上し膜剥れが防止される。 That is, in the cleaning method of the present invention, the glass substrate polished with the abrasive is first cleaned with an acidic aqueous cleaning solution containing an organic acid, and abrasive grains such as cerium oxide particles remaining and adhered to the surface of the glass substrate are present. After being removed efficiently, the OH-rich hydrophilic layer on the surface of the glass substrate generated by this acid cleaning is removed with an alkaline aqueous cleaning solution containing a base. As a result of removing the OH-rich hydrophilic layer on the surface of the glass substrate in this way, when the resin BM film is formed on the glass substrate, the intrusion of the developer from the interface between the glass substrate and the BM resin composition film is caused. The adhesion of the resin BM film is improved and film peeling is prevented.
以下、本発明を、ＬＣＤ等のＦＰＤ用として使用されるガラス基板を洗浄するための洗浄方法を例にして説明する。本発明はこの実施形態に限定されるものではなく、本発明の趣旨に合致する限り、他の実施の形態も本発明の範疇に属し得る。 Hereinafter, the present invention will be described with reference to a cleaning method for cleaning a glass substrate used for FPD such as LCD. The present invention is not limited to this embodiment, and other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.
本発明に係るガラス基板の洗浄方法は、酸化セリウム粒子を含有する研磨剤により研磨されたガラス基板を、有機酸を含む酸性の水系洗浄液（以下、酸性洗浄液ともいう。）により洗浄し、次いで塩基を含むアルカリ性の水性洗浄液（以下、アルカリ性洗浄液ともいう。）により洗浄することを特徴とする。なお、以下、酸性洗浄液による洗浄を酸洗浄、アルカリ性洗浄液による洗浄をアルカリ洗浄ともいう。
また、本発明の洗浄方法において、酸洗浄とアルカリ洗浄との間に乾燥を行ってもよい。さらに、アルカリ洗浄の後に乾燥を行ってもよい。乾燥方法としては、温風を吹き付ける方法や、圧縮した空気を吹き付ける方法等が挙げられる。In the method for cleaning a glass substrate according to the present invention, a glass substrate polished with an abrasive containing cerium oxide particles is washed with an acidic aqueous cleaning solution containing an organic acid (hereinafter also referred to as an acidic cleaning solution), and then a base. It wash | cleans by the alkaline aqueous washing | cleaning liquid (henceforth an alkaline washing | cleaning liquid) containing this. Hereinafter, cleaning with an acidic cleaning liquid is also referred to as acid cleaning, and cleaning with an alkaline cleaning liquid is also referred to as alkaline cleaning.
In the cleaning method of the present invention, drying may be performed between the acid cleaning and the alkali cleaning. Furthermore, you may dry after alkali washing. Examples of the drying method include a method of blowing warm air, a method of blowing compressed air, and the like.
＜ガラス基板＞
本発明において、洗浄対象物であるガラス基板は、ＬＣＤのようなＦＰＤ用のガラス基板であり、酸化セリウム粒子を含有する研磨剤で研磨された後、表面の研磨剤等の残さを除去するために洗浄される。このガラス基板を構成するガラスは、ＳｉＯ２とＡｌ２Ｏ３とＢ２Ｏ３およびアルカリ土類金属の酸化物を含む組成を有するアルミノケイ酸ガラスが好ましく、ガラス組成にアルカリ金属成分を実質的に含まない、いわゆる無アルカリのアルミノホウケイ酸ガラスがより好ましい。なお、アルカリ金属成分を実質的に含まないとは、ガラス組成中におけるアルカリ金属酸化物の含有量が１質量％以下であることをいう。<Glass substrate>
In the present invention, the glass substrate that is an object to be cleaned is a glass substrate for FPD such as LCD, and after polishing with an abrasive containing cerium oxide particles, the residue such as abrasive on the surface is removed. To be washed. The glass constituting the glass substrate is preferably an aluminosilicate glass having a composition containing SiO 2 , Al 2 O 3 , B 2 O 3 and an oxide of an alkaline earth metal, and an alkali metal component is substantially added to the glass composition. A so-called alkali-free aluminoborosilicate glass that does not contain is more preferable. In addition, that an alkali metal component is not included substantially means that content of the alkali metal oxide in a glass composition is 1 mass% or less.
洗浄前の研磨では、このようなガラス基板の表面を、例えば、研磨パッドを使用し、砥粒として酸化セリウム粒子を含む研磨剤（スラリー）により研磨する。砥粒の平均粒径は、例えば０．８〜１．０μｍの範囲が好ましい。 In polishing before cleaning, the surface of such a glass substrate is polished with a polishing agent (slurry) containing cerium oxide particles as abrasive grains, for example, using a polishing pad. The average grain size of the abrasive grains is preferably in the range of 0.8 to 1.0 μm, for example.
＜酸性の水系洗浄液＞
本発明においては、前記研磨剤により研磨されたガラス基板を、有機酸を含む酸性の洗浄液によって洗浄する（以下、この洗浄工程を酸洗浄工程という。）。酸性洗浄液のｐＨは、６以下が好ましく、５以下がより好ましく、３．５以下が特に好ましい。また、酸性洗浄液のｐＨは、１以上が好ましく、１．５以上がより好ましく、２以上が特に好ましい。酸性洗浄液に含有される有機酸としては、例えば、アスコルビン酸、クエン酸のような有機カルボン酸や、有機ホスホン酸等が挙げられるが、これらに限定されない。これらの有機酸とともに、無機酸（例えば、硫酸、リン酸、硝酸、フッ酸、塩酸など）を加えることができる。また、ｐＨの変動を抑制するために、前記無機酸とともにこれらの酸の塩を加えることも可能である。<Acid aqueous cleaning solution>
In the present invention, the glass substrate polished with the abrasive is washed with an acidic washing solution containing an organic acid (hereinafter, this washing step is referred to as an acid washing step). The pH of the acidic cleaning solution is preferably 6 or less, more preferably 5 or less, and particularly preferably 3.5 or less. Further, the pH of the acidic cleaning solution is preferably 1 or more, more preferably 1.5 or more, and particularly preferably 2 or more. Examples of the organic acid contained in the acidic cleaning liquid include, but are not limited to, organic carboxylic acids such as ascorbic acid and citric acid, and organic phosphonic acids. An inorganic acid (for example, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, hydrochloric acid, etc.) can be added together with these organic acids. Moreover, in order to suppress the fluctuation | variation of pH, it is also possible to add the salt of these acids with the said inorganic acid.
研磨後のガラス基板の表面に残留・付着した酸化セリウムの除去性、および洗浄排液中の砥粒残渣の凝集防止の観点から、酸性洗浄液として、（Ａ）有機ホスホン酸と（Ｂ）ポリカルボン酸塩と（Ｃ）芳香族スルホン酸と（Ｄ）アミン−アルキレンオキサイド付加物とを含む洗浄液の使用が好ましい。 From the viewpoint of removing cerium oxide remaining and adhered to the surface of the polished glass substrate and preventing aggregation of abrasive residue in the cleaning waste liquid, (A) organic phosphonic acid and (B) polycarboxylic acid are used as acidic cleaning liquid. It is preferable to use a cleaning solution containing an acid salt, (C) an aromatic sulfonic acid, and (D) an amine-alkylene oxide adduct.
この酸性洗浄液において、（Ａ）成分である有機ホスホン酸は、酸化セリウムに対するキレート剤として作用し、ガラス基板の表面に付着・残留する酸化セリウム等からなる砥粒の分散を促し、ガラス基板表面から引き剥がし除去する働きをする。 In this acidic cleaning solution, the organic phosphonic acid which is component (A) acts as a chelating agent for cerium oxide, promotes the dispersion of abrasive grains made of cerium oxide and the like adhering to and remaining on the surface of the glass substrate, and from the surface of the glass substrate. It works to peel off and remove.
ここで、有機ホスホン酸とは、式：−Ｐ（＝Ｏ）（ＯＨ）２で表わされるホスホン酸基が炭素原子に結合した構造を有する有機化合物をいう。有機ホスホン酸１分子あたりのホスホン酸基の数は２以上が好ましく、２〜８がより好ましく、２〜４が特に好ましい。Here, the organic phosphonic acid refers to an organic compound having a structure in which a phosphonic acid group represented by the formula: —P (═O) (OH) 2 is bonded to a carbon atom. The number of phosphonic acid groups per molecule of the organic phosphonic acid is preferably 2 or more, more preferably 2 to 8, and particularly preferably 2 to 4.
有機ホスホン酸としては、置換基を有していてもよい炭化水素類の炭素に結合した水素原子を、ホスホン酸基に置換した構造を有する化合物、または、アンモニアやアミン類の窒素原子に結合した水素原子を、−ＣＨ２−Ｐ（＝Ｏ）（ＯＨ）２で表わされるメチレンホスホン酸基に置換した構造を有する化合物が好ましい。The organic phosphonic acid is a compound having a structure in which a hydrogen atom bonded to carbon of hydrocarbons which may have a substituent is substituted with a phosphonic acid group, or bonded to a nitrogen atom of ammonia or amines. A compound having a structure in which a hydrogen atom is substituted with a methylenephosphonic acid group represented by —CH 2 —P (═O) (OH) 2 is preferable.
上記前者の構造の有機ホスホン酸において、置換基を有していてもよい炭化水素類としては、脂肪族炭化水素または水酸基含有脂肪族炭化水素が好ましい。これら脂肪族炭化水素等において、その炭素数は１〜６が好ましく、水酸基数は２以下が好ましい。この構造を有する有機ホスホン酸としては、具体的には、例えば、メチルジホスホン酸、および１−ヒドロキシエタン−１，１−ジホスホン酸等を挙げることができる。
下記メチレンホスホン酸基を有する構造の有機ホスホン酸も含めて、本発明における有機ホスホン酸としては、水酸基含有脂肪族炭化水素の炭素に結合した水素原子をホスホン酸基に置換した構造を有する化合物が特に好ましく、具体的には、１−ヒドロキシエタン−１，１−ジホスホン酸が最も好ましい。In the organic phosphonic acid having the former structure, the hydrocarbons which may have a substituent are preferably aliphatic hydrocarbons or hydroxyl group-containing aliphatic hydrocarbons. In these aliphatic hydrocarbons, the number of carbon atoms is preferably 1 to 6, and the number of hydroxyl groups is preferably 2 or less. Specific examples of the organic phosphonic acid having this structure include methyl diphosphonic acid and 1-hydroxyethane-1,1-diphosphonic acid.
The organic phosphonic acid in the present invention, including the organic phosphonic acid having a structure having the following methylenephosphonic acid group, includes a compound having a structure in which a hydrogen atom bonded to carbon of a hydroxyl group-containing aliphatic hydrocarbon is substituted with a phosphonic acid group. Particularly preferred is 1-hydroxyethane-1,1-diphosphonic acid.
前記後者の構造の有機ホスホン酸としては、アンモニアや脂肪族アミンの窒素原子に結合した水素原子の全てが、メチレンホスホン酸基に置換した構造を有する化合物が好ましい。ただし、アミン類窒素原子に結合した水素原子の一部は、アルキル基等の有機基に置換されていてもよい。脂肪族アミンとしては、アルキレンジアミンやその多量体であるポリアルキレンポリアミンが好ましい。アルキレンジアミンの炭素数は２〜４が好ましい。これらアミン類の窒素原子に結合した水素原子（メチレンホスホン酸基に置換される水素原子）の数は２〜８が好ましく、２〜４がより好ましい。 As the organic phosphonic acid having the latter structure, a compound having a structure in which all hydrogen atoms bonded to nitrogen atoms of ammonia or aliphatic amines are substituted with methylenephosphonic acid groups is preferable. However, a part of hydrogen atoms bonded to amine nitrogen atoms may be substituted with an organic group such as an alkyl group. As the aliphatic amine, an alkylene diamine or a polyalkylene polyamine which is a multimer thereof is preferable. As for carbon number of alkylenediamine, 2-4 are preferable. 2-8 are preferable and, as for the number of the hydrogen atoms (hydrogen atom substituted by a methylene phosphonic acid group) couple | bonded with the nitrogen atom of these amines, 2-4 are more preferable.
この構造を有する有機ホスホン酸としては、具体的には、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、ヘキサメチレンジアミンテトラ（メチレンホスホン酸）、プロピレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、トリエチレンテトラミンヘキサ（メチレンホスホン酸）、トリス（２−アミノエチル）アミンヘキサ（メチレンホスホン酸）、トランス−１、２−シクロヘキサンジアミンテトラ（メチレンホスホン酸）、グリコールエーテルジアミンテトラ（メチレンホスホン酸）、およびテトラエチレンペンタミンヘプタ（メチレンホスホン酸）等を挙げることができる。 Specific examples of organic phosphonic acids having this structure include aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), propylenediaminetetra (methylenephosphonic acid), and diethylenetriamine. Penta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), tris (2-aminoethyl) aminehexa (methylenephosphonic acid), trans-1,2-cyclohexanediaminetetra (methylenephosphonic acid), glycol etherdiaminetetra (Methylene phosphonic acid), and tetraethylene pentamine hepta (methylene phosphonic acid).
（Ｂ）成分であるポリカルボン酸塩と（Ｃ）成分である芳香族スルホン酸とは、前記（Ａ）有機ホスホン酸による研磨砥粒の分散・除去性を向上させるとともに、砥粒の再付着を防止する働きをする。（Ｂ）成分であるポリカルボン酸塩としては、ポリ（メタ）アクリル酸塩、（メタ）アクリル酸−マレイン酸共重合体の塩等を例示することができる。
ここで、（メタ）アクリル酸という表記は、アクリル酸とメタクリル酸の両方を意味する。ポリカルボン酸の重量平均分子量（以下、Ｍｗと略記。）は、砥粒の再付着防止および低泡性の観点から、２，０００〜５０，０００の範囲であることが好ましい。なお、Ｍｗは、ゲルパーミエーションクロマトグラフィー（以下、ＧＰＣと略記。）によって、測定された値である。The (B) component polycarboxylate and the (C) component aromatic sulfonic acid improve the dispersion / removability of the abrasive grains by the (A) organic phosphonic acid and reattach the abrasive grains. It works to prevent. Examples of the polycarboxylic acid salt as component (B) include poly (meth) acrylates, salts of (meth) acrylic acid-maleic acid copolymers, and the like.
Here, the notation (meth) acrylic acid means both acrylic acid and methacrylic acid. The weight average molecular weight (hereinafter abbreviated as Mw) of the polycarboxylic acid is preferably in the range of 2,000 to 50,000 from the viewpoint of preventing reattachment of abrasive grains and low foaming properties. Mw is a value measured by gel permeation chromatography (hereinafter abbreviated as GPC).
ポリカルボン酸塩において、塩を形成する対イオンは特に限定されないが、アルカリ金属（ナトリウムおよびカリウム）塩、アンモニウム塩、１級アミン（例えば、メチルアミン、エチルアミンおよびブチルアミン等のアルキルアミン）の塩、２級アミン（例えば、ジメチルアミン、ジエチルアミンおよびジブチルアミン等のジアルキルアミン、ならびにジエタノールアミン等のジアルカノールアミン）の塩、３級アミン（例えば、トリメチルアミン、トリエチルアミンおよびトリブチルアミン等のトリアルキルアミン、トリエタノールアミン等のトリアルカノールアミン、Ｎ−メチルジエタノールアミン等のＮ−アルキルジアルカノールアミン、ならびに１，８−ジアザビシクロ［５．４．０］−７−ウンデセン、１，５−ジアザビシクロ［４．３．０］−５−ノネン、１，４−ジアザビシクロ［２．２．２］オクタン、１Ｈイミダゾール、２−メチル−１Ｈ−イミダゾール、２−エチル−１Ｈ−イミダゾール、４，５−ジヒドロ−１Ｈイミダゾール、２−メチル−４，５−ジヒドロ−１Ｈイミダゾール、１，４，５，６−テトラヒドロ−ピリミジン、１，６（４）−ジヒドロピリミジン等の含窒素複素環状の３級アミン）の塩、または第４級アンモニウム塩（テトラアルキルアンモニウム塩等）が好ましい。パーティクルの再付着防止の観点から、これらの中で好ましいものは、アルカリ金属（ナトリウムおよびカリウム）塩、アンモニウム塩、１級アミン塩、２級アミン塩、３級アミン塩または第４級アンモニウム塩であり、特に好ましいものは、アルカリ金属（ナトリウムおよびカリウム）塩、またはアンモニウム塩である。 In the polycarboxylate, the counter ion that forms the salt is not particularly limited, but salts of alkali metals (sodium and potassium), ammonium salts, primary amines (for example, alkylamines such as methylamine, ethylamine, and butylamine), Salts of secondary amines (eg, dialkylamines such as dimethylamine, diethylamine and dibutylamine, and dialkanolamines such as diethanolamine), tertiary amines (eg, trialkylamines such as trimethylamine, triethylamine and tributylamine, triethanolamine) N-alkyl dialkanolamines such as N-methyldiethanolamine, and 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo 4.3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] octane, 1H imidazole, 2-methyl-1H-imidazole, 2-ethyl-1H-imidazole, 4,5-dihydro- 1H imidazole, 2-methyl-4,5-dihydro-1H imidazole, 1,4,5,6-tetrahydro-pyrimidine, nitrogen-containing heterocyclic tertiary amines such as 1,6 (4) -dihydropyrimidine) Or a quaternary ammonium salt (such as a tetraalkylammonium salt) is preferred. From the viewpoint of preventing re-adhesion of particles, preferred among these are alkali metal (sodium and potassium) salts, ammonium salts, primary amine salts, secondary amine salts, tertiary amine salts, or quaternary ammonium salts. Particularly preferred are alkali metal (sodium and potassium) salts or ammonium salts.
（Ｃ）成分である芳香族スルホン酸としては、炭素数８〜１４のアルキル基を有するアルキルベンゼンスルホン酸、石油スルホネート、トルエンスルホン酸、キシレンスルホン酸（別名：ジメチルベンゼンスルホン酸）、およびクメンスルホン酸等が挙げられる。特に、メタキシレンスルホン酸（別名：２，４−ジメチルベンゼンスルホン酸）の使用が好ましい。 The aromatic sulfonic acid as component (C) includes alkylbenzene sulfonic acid having 8 to 14 carbon atoms, petroleum sulfonate, toluene sulfonic acid, xylene sulfonic acid (also known as dimethylbenzene sulfonic acid), and cumene sulfonic acid. Etc. In particular, the use of metaxylene sulfonic acid (also known as 2,4-dimethylbenzene sulfonic acid) is preferable.
（Ｄ）成分であるアミン−アルキレンオキサイド付加物は、砥粒とガラス基板との界面への前記（Ａ）有機ホスホン酸の浸透を促進する働きをする。アミン−アルキレンオキサイド付加物としては、アルキレンオキサイド付加型のノニオン系界面活性剤として知られている化合物が好ましい。アルキレンオキサイドとしては、エチレンオキサイド（以下、ＥＯともいう。）またはプロピレンオキサイド（以下、ＰＯともいう。）が好ましく、それらの一方のみを付加した構造の化合物であってもよく、それらの両方を付加した構造の化合物であってもよい。ＥＯとＰＯの両者を付加した化合物においては、ＥＯの単位（すなわち、オキシエチレン基）とＰＯの単位（すなわち、オキシプロピレン基）はブロック状に存在していてもよく、ランダム状に存在していてもよい。前者はアミンにＥＯとＰＯを別々に順次付加して得られ、後者はアミンにＥＯとＰＯの混合物を付加して得られる。ＰＯ−ＥＯ付加物とは、それら付加方法のいずれかで得られる付加物をいう。 The amine-alkylene oxide adduct as component (D) functions to promote penetration of the organic phosphonic acid (A) into the interface between the abrasive grains and the glass substrate. As the amine-alkylene oxide adduct, a compound known as an alkylene oxide addition type nonionic surfactant is preferable. The alkylene oxide is preferably ethylene oxide (hereinafter also referred to as EO) or propylene oxide (hereinafter also referred to as PO), and may be a compound having a structure in which only one of them is added, or both of them are added. It may be a compound having the above structure. In a compound in which both EO and PO are added, the EO unit (that is, oxyethylene group) and the PO unit (that is, oxypropylene group) may exist in a block form or in a random form. May be. The former is obtained by sequentially adding EO and PO separately to the amine, and the latter is obtained by adding a mixture of EO and PO to the amine. The PO-EO adduct refers to an adduct obtained by any of these addition methods.
アルキレンオキサイドが付加されるアミン類としては、窒素原子に結合した水素原子の数が２〜８であり、アミノ基の数が１〜４のアミン類が好ましい。また、アミン類の炭素数は１６以下が好ましく、１０以下がより好ましい。このようなアミン類としては、例えば、脂肪族のモノアミンやポリアミン、脂環族のモノアミンやポリアミン、芳香族のモノアミンやポリアミンを挙げることができる。より具体的は、アルキルモノアミン、アルキレンジアミンやその多量体であるポリアルキレンポリアミン、脂環に結合したアミノ基やアミノアルキル基を１個以上有する脂環族のモノアミンやポリアミン、芳香環に結合したアミノ基やアミノアルキル基を１個以上有する芳香族のモノアミンやポリアミンなどが好ましい。 As amines to which alkylene oxide is added, amines having 2 to 8 hydrogen atoms bonded to nitrogen atoms and 1 to 4 amino groups are preferred. Moreover, 16 or less are preferable and, as for carbon number of amines, 10 or less are more preferable. Examples of such amines include aliphatic monoamines and polyamines, alicyclic monoamines and polyamines, and aromatic monoamines and polyamines. More specifically, alkyl monoamines, alkylene diamines and polyalkylene polyamines that are multimers thereof, alicyclic monoamines and polyamines having at least one amino group or aminoalkyl group bonded to an alicyclic ring, and amino groups bonded to an aromatic ring. Aromatic monoamines and polyamines having at least one group or aminoalkyl group are preferred.
（Ｄ）成分であるアミン−アルキレンオキサイド付加物としては、その少なくとも一部がアルキレンジアミンのＰＯ−ＥＯ付加物であることが好ましい。アルキレンジアミンとしては、炭素数２〜４のアルキレンジアミンが好ましく、エチレンジアミンが特に好ましい。エチレンジアミンのＰＯ−ＥＯ付加物としては、例えばエチレンジアミンの窒素原子に結合した４個の水素原子にＰＯとＥＯが付加した化合物を挙げることができる。また、（Ｄ）アミン−アルキレンオキサイド付加物として、前記エチレンジアミンのＰＯ−ＥＯ付加物とともに、芳香族アミンのＰＯ付加物を併用することも好ましい。芳香族アミンのＰＯ付加物としては、例えばメタキシリレンジアミンのＰＯ付加物が挙げられる。（Ｄ）アミン−アルキレンオキサイド付加物として、エチレンジアミンのＰＯ−ＥＯ付加物と芳香族アミンのＰＯ付加物を併用した場合には、洗浄液の洗浄・除去能力の安定性がよりいっそう向上する。 The amine-alkylene oxide adduct as the component (D) is preferably at least partly an alkylenediamine PO-EO adduct. As alkylene diamine, C2-C4 alkylenediamine is preferable and ethylenediamine is especially preferable. Examples of the PO—EO adduct of ethylenediamine include a compound in which PO and EO are added to four hydrogen atoms bonded to the nitrogen atom of ethylenediamine. It is also preferable to use an aromatic amine PO adduct in combination with the ethylenediamine PO-EO adduct as the (D) amine-alkylene oxide adduct. Examples of the PO adducts of aromatic amines include metaxylylenediamine PO adducts. (D) When an ethylenediamine PO-EO adduct and an aromatic amine PO adduct are used in combination as the amine-alkylene oxide adduct, the stability of the washing liquid cleaning / removing ability is further improved.
（Ａ）〜（Ｄ）の各成分の含有割合は、（Ａ）〜（Ｄ）の合計量に対して、（Ａ）有機ホスホン酸は０．０１〜５０質量％、（Ｂ）ポリカルボン酸塩は０．０１〜１０質量％、（Ｃ）芳香族スルホン酸は０．０１〜５０質量％、および（Ｄ）アミン−アルキレンオキサイド付加物は０．０２〜１０質量％であることが好ましい。また、（Ｂ）ポリカルボン酸塩と（Ｃ）芳香族スルホン酸の合計の割合は０．０３〜６０質量％であることが好ましい。（Ｄ）アミン−アルキレンオキサイド付加物として、アルキレンジアミンのＰＯ−ＥＯ付加物と芳香族アミンのＰＯ付加物を併用する場合は、アルキレンジアミンのＰＯ−ＥＯ付加物０．０１〜５質量％と芳香族アミンのＰＯ付加物０．０１〜５質量％であって、その合計の割合は上記０．０２〜１０質量％であることが好ましい。 The content ratio of each component of (A) to (D) is 0.01 to 50% by mass of (A) organic phosphonic acid and (B) polycarboxylic acid with respect to the total amount of (A) to (D). It is preferable that the salt is 0.01 to 10% by mass, (C) the aromatic sulfonic acid is 0.01 to 50% by mass, and (D) the amine-alkylene oxide adduct is 0.02 to 10% by mass. Moreover, it is preferable that the ratio of the sum total of (B) polycarboxylate and (C) aromatic sulfonic acid is 0.03-60 mass%. (D) When an amine-alkylene oxide adduct is used in combination with an alkylenediamine PO-EO adduct and an aromatic amine PO adduct, 0.01 to 5% by mass of an alkylenediamine PO-EO adduct It is preferable that it is 0.01-5 mass% of PO adducts of group amines, and the total ratio is 0.02-10 mass%.
本発明で使用される好ましい酸性洗浄液は、前記（Ａ）〜（Ｄ）の各成分を、水に溶解させてなる水系洗浄液である。水としては、脱イオン水、超純水、電荷イオン水、水素水およびオゾン水などを使用することができる。なお、水は洗浄液の流動性を制御する機能を有するので、その含有量は、洗浄速度等の目標とする洗浄特性に合わせて適宜設定することができる。通常は、前記（Ａ）〜（Ｄ）の各成分を比較的高濃度で含む水溶液（以下、酸性洗浄剤原液という。）を使用前に水で希釈して酸性洗浄液とし、それをガラス基板の洗浄に使用する。（Ａ）〜（Ｄ）の各成分を前記範囲で含有する酸性洗浄剤原液において、水の含有割合は、５５〜９８質量％とすることができる。また、この酸性洗浄剤原液には、上記（Ａ）〜（Ｄ）の各成分以外に、分散剤、水溶性有機溶剤、酸化防止剤、防錆剤、ｐＨ調整剤、緩衝剤、消泡剤、防腐剤、ハイドロトロープ剤等の添加剤を水に配合することができる。 A preferable acidic cleaning liquid used in the present invention is an aqueous cleaning liquid obtained by dissolving the components (A) to (D) in water. As water, deionized water, ultrapure water, charged ion water, hydrogen water, ozone water, or the like can be used. Since water has a function of controlling the fluidity of the cleaning liquid, its content can be appropriately set according to the target cleaning characteristics such as the cleaning speed. Usually, an aqueous solution containing the components (A) to (D) at a relatively high concentration (hereinafter referred to as an acidic cleaning agent stock solution) is diluted with water before use to form an acidic cleaning solution. Used for cleaning. In the acidic detergent stock solution containing the components (A) to (D) in the above range, the content ratio of water can be 55 to 98% by mass. In addition to the components (A) to (D), the acidic detergent stock solution includes a dispersant, a water-soluble organic solvent, an antioxidant, a rust inhibitor, a pH adjuster, a buffer, and an antifoaming agent. Additives such as preservatives and hydrotropes can be added to the water.
このような酸性洗浄剤原液を洗浄に使用するに当たっては、酸性洗浄剤原液の含有割合（濃度）が０．５〜２．５質量％となるように水で希釈して使用することが好ましい。このように水で希釈して使用することで、ガラス基板表面を荒らすことなく、残留・付着した酸化セリウム等からなる砥粒を良好に除去することができる。 When using such an acidic detergent stock solution for washing, it is preferable to dilute with water so that the content ratio (concentration) of the acidic detergent stock solution is 0.5 to 2.5% by mass. By diluting with water in this way, it is possible to satisfactorily remove abrasive grains composed of residual and attached cerium oxide or the like without roughening the surface of the glass substrate.
＜酸洗浄工程＞
本発明の酸洗浄においては、前記酸性洗浄剤原液を水で希釈した希釈液（酸性洗浄液）を使用して、研磨後のガラス基板の表面を洗浄する。枚葉方式で洗浄することが好ましい。洗浄液をガラス基板の表面に直接接触させて洗浄する方法であれは、洗浄方法は特に限定されない。スクラブ洗浄、シャワー洗浄（噴射洗浄）、ディップ（浸漬）洗浄等を用いることができる。洗浄液の温度は特に限定されることはなく、室温（１５℃）〜９５℃で使用される。９５℃を超える場合には、水が沸騰するおそれがあり、洗浄操作上不便であり好ましくない。酸洗浄時間は、１．５秒〜１時間が好ましく、１．５秒〜１分がさらに好ましく、１．５秒〜１５秒が特に好ましい。<Acid cleaning process>
In the acid cleaning of the present invention, the surface of the polished glass substrate is cleaned using a diluted solution (acid cleaning solution) obtained by diluting the acidic cleaning agent stock solution with water. It is preferable to wash by a single wafer method. The cleaning method is not particularly limited as long as the cleaning liquid is brought into direct contact with the surface of the glass substrate for cleaning. Scrub cleaning, shower cleaning (jet cleaning), dip (immersion) cleaning, and the like can be used. The temperature of the cleaning liquid is not particularly limited, and is used at room temperature (15 ° C.) to 95 ° C. If it exceeds 95 ° C., water may boil, which is inconvenient in the washing operation and is not preferable. The acid washing time is preferably 1.5 seconds to 1 hour, more preferably 1.5 seconds to 1 minute, and particularly preferably 1.5 seconds to 15 seconds.
酸洗浄工程では、例えば、図１に示すように、搬送ロール１等の機構により洗浄室２内を水平方向に連続的に搬送されるガラス基板３の上下両面に、洗浄ノズル４から噴射された酸性洗浄液５を吹き付けながら、両面側に配置された回転ブラシ６でスクラブする（擦る）方法を採ることができる。
In the acid cleaning step, for example, as shown in FIG. 1, the cleaning nozzle 4 sprays the upper and lower surfaces of the glass substrate 3 which are continuously transported in the
ここで、洗浄用の回転ブラシ６としては、ＰＶＡ（ポリビニルアルコール）スポンジ（発泡体）製などで外径７０〜１００ｍｍの円柱形状のものを複数個使用する。そして、これらのブラシを、回転軸がガラス基板３の被洗浄面に対して垂直になるように、かつ先端部がガラス基板３の被洗浄面と接触するか、２ｍｍ未満の間隔となるように配置する。回転ブラシ６の回転速度は、１００〜５００ｒｐｍとすることが好ましい。
Here, as the rotating
酸性洗浄液５としては、前記した酸性洗浄剤原液を所望の濃度になるように水で希釈したものを使用し、希釈された洗浄液の流量（噴射量）は、１５〜４０リットル／分とすることが好ましい。また、スクラブ時間は１．５秒以上とすることが好ましい。さらに、スクラブ時間は１５秒以下とすることが好ましい。 As the acidic cleaning solution 5, a solution obtained by diluting the above-mentioned acidic cleaning agent stock solution with water to a desired concentration is used, and the flow rate (injection amount) of the diluted cleaning solution is 15 to 40 liters / minute. Is preferred. The scrub time is preferably 1.5 seconds or longer. Furthermore, the scrub time is preferably 15 seconds or less.
＜アルカリ性の水系洗浄液＞
本発明においては、前記酸洗浄工程で酸性洗浄液により洗浄されたガラス基板を、次いで、アルカリ性洗浄液（すなわち、塩基を含むアルカリ性の水系洗浄液）により洗浄する（以下、この洗浄工程をアルカリ洗浄工程という。）。アルカリ性洗浄液のｐＨは、８以上が好ましく、１０以上がより好ましく、１２以上が特に好ましい。また、アルカリ性洗浄液のｐＨは、１４以下が好ましい。また、このアルカリ性洗浄液は、塩基以外にキレート剤や界面活性剤を含有することができる。特に、キレート剤と界面活性剤を併用することが好ましい。<Alkaline aqueous cleaning solution>
In the present invention, the glass substrate cleaned with the acidic cleaning solution in the acid cleaning step is then cleaned with an alkaline cleaning solution (that is, an alkaline aqueous cleaning solution containing a base) (hereinafter, this cleaning step is referred to as an alkali cleaning step). ). The pH of the alkaline cleaning liquid is preferably 8 or more, more preferably 10 or more, and particularly preferably 12 or more. Further, the pH of the alkaline cleaning liquid is preferably 14 or less. The alkaline cleaning liquid can contain a chelating agent and a surfactant in addition to the base. In particular, it is preferable to use a chelating agent and a surfactant in combination.
アルカリ性洗浄液に含有される塩基としては、アルカリ金属水酸化物やアルカリ金属炭酸塩などのアルカリ金属化合物、アミン類や水酸化第４級アンモニウムなどが挙げられる。塩基としては、水酸化カリウムや水酸化ナトリウム等のアルカリ金属水酸化物が好ましい。キレート剤としては、エチレンジアミン四酢酸系キレート剤、グルコン酸系キレート剤、ニトリロ三酢酸系キレート剤、イミノコハク酸系キレート剤などを挙げることができる。特にエチレンジアミン四酢酸系キレート剤が好ましい。界面活性剤としては、ノニオン性界面活性剤が好ましい。ノニオン性界面活性剤としては、前記酸性洗浄剤の（Ｄ）成分であるアミン−アルキレンオキサイド付加物、ポリオキシエチレンドデシルエーテル等のポリオキシアルキレンエーテル系のノニオン性界面活性剤、ポリオキシエチレンソルビタン脂肪酸エステル等のポリオキシアルキレンエーテルエステル系のノニオン性界面活性剤、グリセリン脂肪酸エステル等のエステル系のノニオン性界面活性剤を挙げることができる。 Examples of the base contained in the alkaline cleaning liquid include alkali metal compounds such as alkali metal hydroxides and alkali metal carbonates, amines, and quaternary ammonium hydroxide. As the base, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are preferable. Examples of chelating agents include ethylenediaminetetraacetic acid chelating agents, gluconic acid chelating agents, nitrilotriacetic acid chelating agents, and iminosuccinic acid chelating agents. In particular, an ethylenediaminetetraacetic acid chelating agent is preferred. As the surfactant, a nonionic surfactant is preferable. Nonionic surfactants include amine-alkylene oxide adducts that are component (D) of the acidic detergent, polyoxyalkylene ether-based nonionic surfactants such as polyoxyethylene dodecyl ether, and polyoxyethylene sorbitan fatty acids. Examples thereof include polyoxyalkylene ether ester-based nonionic surfactants such as esters and ester-based nonionic surfactants such as glycerin fatty acid esters.
本発明で使用されるアルカリ性洗浄液は、上記塩基等を水に溶解させてなる水系洗浄液である。水としては、脱イオン水、超純水、電荷イオン水、水素水およびオゾン水などを使用することができる。なお、水は洗浄液の流動性を制御する機能を有するので、その含有量は、洗浄速度等の目標とする洗浄特性に合わせて適宜設定することができる。通常は、上記塩基等を比較的高濃度で含む水溶液（以下、アルカリ性洗浄剤原液という。）を使用前に水で希釈してアルカリ性洗浄液とし、それを洗浄に使用する。アルカリ性洗浄剤原液において、水の含有割合は、５５〜９８質量％とすることができる。また、このアルカリ性洗浄剤原液には、上記塩基、キレート剤、および界面活性剤の各成分以外に、分散剤、水溶性有機溶剤、酸化防止剤、防錆剤、ｐＨ調整剤、緩衝剤、消泡剤、防腐剤、ハイドロトロープ剤等の添加剤を水に配合することができる。 The alkaline cleaning liquid used in the present invention is an aqueous cleaning liquid obtained by dissolving the above-described base or the like in water. As water, deionized water, ultrapure water, charged ion water, hydrogen water, ozone water, or the like can be used. Since water has a function of controlling the fluidity of the cleaning liquid, its content can be appropriately set according to the target cleaning characteristics such as the cleaning speed. Usually, an aqueous solution containing the above-mentioned base or the like at a relatively high concentration (hereinafter referred to as an alkaline detergent stock solution) is diluted with water before use to obtain an alkaline cleaning solution, which is used for washing. In the alkaline detergent stock solution, the content ratio of water can be 55 to 98% by mass. In addition to the base, chelating agent, and surfactant components, the alkaline detergent stock solution includes a dispersant, a water-soluble organic solvent, an antioxidant, a rust inhibitor, a pH adjuster, a buffer, Additives such as foaming agents, preservatives, hydrotropes and the like can be incorporated into the water.
アルカリ性洗浄剤原液における前記各成分の含有割合は、塩基、キレート剤、およびノニオン性界面活性剤がいずれも１〜１０質量％であり、残部が水であることが好ましい。 The content ratio of each component in the alkaline detergent stock solution is preferably 1 to 10% by mass for the base, the chelating agent, and the nonionic surfactant, and the balance is preferably water.
アルカリ洗浄工程においては、各成分を前記範囲で含有するアルカリ性洗浄剤原液を、原液の含有割合（濃度）が１〜５質量％となるように水で希釈してアルカリ性洗浄液とし、このアルカリ性洗浄液を使用することが好ましい。このように水で希釈して使用することで、ガラス基板表面を過度に荒らすことなく、酸洗浄工程でガラス基板の表面に生じたＯＨリッチ親水層のみを除去し、密着性の高い樹脂ＢＭ膜を形成し得るガラス基板表面を得ることができる。 In the alkaline cleaning step, an alkaline detergent stock solution containing each component in the above range is diluted with water so that the content ratio (concentration) of the stock solution is 1 to 5% by mass to obtain an alkaline cleaning solution. It is preferable to use it. By diluting with water in this way, only the OH-rich hydrophilic layer generated on the surface of the glass substrate in the acid cleaning step is removed without excessively roughening the surface of the glass substrate, and a highly adhesive resin BM film It is possible to obtain a glass substrate surface capable of forming
＜アルカリ洗浄工程＞
アルカリ洗浄工程においては、酸洗浄工程で酸性洗浄液により洗浄されたガラス基板を、前記アルカリ性洗浄剤原液を水で希釈したアルカリ性洗浄液により洗浄する。枚葉方式で洗浄することが好ましい。アルカリ性洗浄液をガラス基板の表面に直接接触させて洗浄する方法であれは、洗浄方法は特に限定されない。前記した酸性洗浄液による洗浄と同様に、スクラブ洗浄、シャワー洗浄（噴射洗浄）、ディップ（浸漬）洗浄等を用いることができる。また、アルカリ性洗浄液の温度も、前記酸性洗浄液と同様に特に限定されることはなく、室温（１５℃）〜９５℃で使用される。９５℃を超える場合には、水が沸騰するおそれがあり、洗浄操作上不便であり好ましくない。アルカリ洗浄時間は、１．５秒〜１時間が好ましく、１．５秒〜１分がさらに好ましく、１．５秒〜１５秒が特に好ましい。<Alkali cleaning process>
In the alkaline cleaning step, the glass substrate cleaned with the acidic cleaning solution in the acid cleaning step is cleaned with an alkaline cleaning solution obtained by diluting the alkaline cleaning agent stock solution with water. It is preferable to wash by a single wafer method. The cleaning method is not particularly limited as long as it is a method in which the alkaline cleaning liquid is cleaned by directly contacting the surface of the glass substrate. Similar to the cleaning with the acidic cleaning liquid described above, scrub cleaning, shower cleaning (jet cleaning), dip (immersion) cleaning, and the like can be used. Further, the temperature of the alkaline cleaning liquid is not particularly limited as in the case of the acidic cleaning liquid, and is used at room temperature (15 ° C.) to 95 ° C. If it exceeds 95 ° C., water may boil, which is inconvenient in the washing operation and is not preferable. The alkali cleaning time is preferably 1.5 seconds to 1 hour, more preferably 1.5 seconds to 1 minute, and particularly preferably 1.5 seconds to 15 seconds.
アルカリ洗浄工程においても、前記した酸洗浄工程と同様に、図１に示す洗浄装置を使用して洗浄を行うことができる。図１に示すように、酸洗浄が終了したガラス基板をさらに搬送ロール１等の機構により洗浄室２内を水平方向に連続的に搬送し、酸洗浄工程の下流側でガラス基板３の上下両面に、洗浄ノズル４から噴射されたアルカリ性洗浄液７を吹き付けながら、両面側に配置された回転ブラシ６でガラス基板の両面をスクラブする方法を採ることができる。そして、洗浄液７としては、前記したアルカリ性洗浄剤原液を所望の濃度になるように水で希釈して得られたアルカリ性洗浄液を使用し、アルカリ性洗浄液の流量（噴射量）は、１５〜４０リットル／分とすることが好ましい。また、スクラブ時間は、１．５秒以上とすることが好ましい。さらに、スクラブ時間は１５秒以下とすることが好ましい。
In the alkali cleaning step, similarly to the acid cleaning step described above, cleaning can be performed using the cleaning apparatus shown in FIG. As shown in FIG. 1, the glass substrate after the acid cleaning is further transported continuously in the
本発明の洗浄方法において、酸化セリウム粒子を含有する研磨剤で研磨されたガラス基板は、まず酸洗浄工程で、有機酸を含む酸性洗浄液により洗浄され、その表面に残留・付着した酸化セリウム粒子等の砥粒が効率的に除去された後、アルカリ洗浄工程で塩基を含むアルカリ性洗浄液により洗浄されることで、前記酸洗浄で生じたガラス基板の表面のＯＨリッチ親水層が除去される。その結果、樹脂ＢＭ膜の形成工程で、ガラス基板表面とＢＭ用樹脂組成物膜との界面からの現像液の浸入が抑えられ、樹脂ＢＭ膜の密着性が向上する。したがって、樹脂ＢＭ膜の密着性が良好で膜剥れが防止されたガラス基板を得ることができる。 In the cleaning method of the present invention, a glass substrate polished with an abrasive containing cerium oxide particles is first cleaned with an acidic cleaning solution containing an organic acid in an acid cleaning step, and the cerium oxide particles remaining on and adhered to the surface thereof. After the abrasive grains are efficiently removed, the OH-rich hydrophilic layer on the surface of the glass substrate generated by the acid cleaning is removed by cleaning with an alkaline cleaning liquid containing a base in an alkaline cleaning step. As a result, in the process of forming the resin BM film, the intrusion of the developer from the interface between the glass substrate surface and the BM resin composition film is suppressed, and the adhesion of the resin BM film is improved. Therefore, it is possible to obtain a glass substrate in which the adhesion of the resin BM film is good and film peeling is prevented.
以下、本発明の実施例について具体的に説明するが、本発明はこれらの実施例に限定されるものではない。以下の例において、特に断らない限り、「％」は質量％を意味し、「部」は質量部を意味する。 Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, “%” means mass%, and “part” means mass part.
実施例１，２、比較例１、比較例２
図１に示す洗浄装置を使用し、以下に示すようにして、表面を研磨されたガラス基板の洗浄を行った。Examples 1 and 2, Comparative Example 1 and Comparative Example 2
Using the cleaning apparatus shown in FIG. 1, the glass substrate whose surface was polished was cleaned as follows.
ガラス基板としては、アルミノケイ酸ガラスからなるＬＣＤ用ガラス基板（旭硝子社製、商品名；ＡＮ１００）を使用し、このガラス基板の表面を、研磨パッドを用い、粒径０．８〜１．０μｍの酸化セリウム粒子を含む研磨剤スラリー（昭和電工（株）製、商品名；ＳＨＯＲＯＸ Ａ１０）を使用して研磨した。 As the glass substrate, a glass substrate for LCD (made by Asahi Glass Co., Ltd., trade name: AN100) made of aluminosilicate glass is used, and the surface of this glass substrate is used with a polishing pad and has a particle size of 0.8 to 1.0 μm. Polishing was performed using an abrasive slurry containing cerium oxide particles (manufactured by Showa Denko KK, trade name: SHOROX A10).
実施例１および２では、研磨後のガラス基板の表面に、組成を１００部としたとき、有機ホスホン酸９．０部、ポリカルボン酸塩１．０部、芳香族スルホン酸１０．０部およびアミン−アルキレンオキサイド１．０部、残りが水を含有する酸性洗浄剤原液（パーカーコーポレーション社製、商品名；ＰＫ−ＬＣＧ４９１Ａ）を、原液（水を含む）の濃度が０．５％になるように水で希釈した酸性洗浄液（ｐＨ２．３〜２．８）を、１分間に２５Ｌの流量（以下、洗浄液流量と示す。）で吹き付けながら、回転するＰＶＡ製のブラシでスクラブして酸洗浄を行った後、アルカリ洗浄を行った。アルカリ洗浄は、酸洗浄後のガラス基板の表面に、アルカリ性洗浄剤原液（パーカーコーポレーション社製、商品名；ＰＫ−ＬＣＧ２１１）を原液（水を含む）の濃度が１．５％になるように水で希釈したアルカリ性洗浄液（ｐＨ１１〜１２）を、１分間に２５Ｌの流量で吹き付けながらスクラブして行った。なお、酸洗浄およびアルカリ洗浄における各洗浄液の温度は、実施例１では２５℃とし、実施例２では３５℃とした。また、酸洗浄工程およびアルカリ洗浄工程におけるスクラブ時間の平均は、それぞれ２．９４秒であった。実施例１，２の洗浄後のガラス基板には、砥粒の残存が認められていない。 In Examples 1 and 2, when the composition is 100 parts on the surface of the polished glass substrate, 9.0 parts of organic phosphonic acid, 1.0 part of polycarboxylate, 10.0 parts of aromatic sulfonic acid, and An acidic detergent stock solution (trade name; PK-LCG491A, manufactured by Parker Corporation) containing 1.0 part of an amine-alkylene oxide and water so that the concentration of the stock solution (including water) is 0.5%. The acid cleaning solution diluted with water (pH 2.3 to 2.8) was scrubbed with a rotating PVA brush while spraying at a flow rate of 25 L per minute (hereinafter referred to as the cleaning solution flow rate) for acid cleaning. After the cleaning, alkali cleaning was performed. Alkaline cleaning is performed by applying an alkaline detergent stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) to the surface of the glass substrate after acid cleaning so that the concentration of the stock solution (including water) is 1.5%. The alkaline cleaning solution (pH 11 to 12) diluted with 1 was scrubbed while sprayed at a flow rate of 25 L per minute. The temperature of each cleaning solution in acid cleaning and alkali cleaning was 25 ° C. in Example 1 and 35 ° C. in Example 2. The average scrub time in the acid cleaning step and the alkali cleaning step was 2.94 seconds. No residual abrasive grains are observed on the glass substrates after cleaning in Examples 1 and 2.
比較例１では、研磨後のガラス基板の表面にアルカリ洗浄のみを行った。アルカリ洗浄は、ガラス基板の表面に、アルカリ性洗浄剤原液（パーカーコーポレーション社製、商品名；ＰＫ−ＬＣＧ２１１）を原液の濃度が１．５％になるように水で希釈した２５℃のアルカリ性洗浄液を、１分間に２５Ｌの流量で吹き付けながら、回転するＰＶＡ製のブラシでスクラブして洗浄した。スクラブ時間の平均は、２．９４秒であった。比較例１の洗浄後のガラス基板には、砥粒の残存が認められた。 In Comparative Example 1, only the alkali cleaning was performed on the surface of the polished glass substrate. Alkaline cleaning is performed by applying an alkaline cleaning solution at 25 ° C., which is obtained by diluting an alkaline detergent stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) with water so that the concentration of the stock solution becomes 1.5% on the surface of the glass substrate. While spraying at a flow rate of 25 L per minute, scrubbing with a rotating PVA brush was performed. The average scrub time was 2.94 seconds. Remaining abrasive grains were observed on the glass substrate after cleaning in Comparative Example 1.
比較例２では、研磨後のガラス基板の表面に酸洗浄のみを行った。酸洗浄は、前記した酸性洗浄剤原液であるＰＫ−ＬＣＧ４９１Ａの原液を０．５％に希釈した２５℃の酸性洗浄液を、１分間に２５Ｌの流量で吹き付けながら、回転するＰＶＡ製のブラシでスクラブして洗浄した。スクラブ時間の平均は３．９２秒であった。比較例２の洗浄後のガラス基板には、砥粒の残存が認められていない。 In Comparative Example 2, only the acid cleaning was performed on the surface of the polished glass substrate. The acid cleaning is performed by scrubbing with a rotating PVA brush while spraying an acidic cleaning solution at 25 ° C. obtained by diluting the stock solution of PK-LCG491A, which is the above-mentioned acidic cleaning agent stock solution, to 0.5% at a flow rate of 25 L per minute. And washed. The average scrub time was 3.92 seconds. No abrasive grains are observed on the glass substrate after the cleaning in Comparative Example 2.
こうして洗浄されたガラス基板の表面について、以下に示す方法で、樹脂ＢＭ膜の密着性を評価した。また、ガラス基板表面のＡｌ濃度（Ａｌ／Ｓｉ比）および接触角の測定を行った。 With respect to the surface of the glass substrate thus cleaned, the adhesion of the resin BM film was evaluated by the following method. Further, the Al concentration (Al / Si ratio) and contact angle of the glass substrate surface were measured.
＜樹脂ＢＭ膜の密着性の評価＞
まず、以下に示す各成分を以下の組成で配合し、均一に混合して、固形分濃度１５％の感光性ＢＭ形成用樹脂組成物を調製した。
［ＢＭ形成用樹脂組成物の組成］
・バインダ樹脂（日本化薬社製、商品名；ＺＣＲ１５６９Ｈ）２８．４部
・光活性剤（光重合開始剤）
（チバ・スペシャルティ・ケミカル社製、商品名；イルガキュアＯＸＥ０２）６．１部
・コロイダルシリカ微粒子（日産化学社製、商品名；ＰＭＡＳＴ）２０．３部
・カーボンブラック３２．５部
・界面活性剤（ビックケミー・ジャパン社製、商品名；ＢＹＫ３０６）０．３部
・架橋剤（日本化薬社製、商品名；ＵＸ５００２Ｄ）６．１部
（日本化薬社製、商品名；ＮＣ３０００Ｈ）３．０部
・シランカップリング剤（信越化学社製、商品名；ＫＢＭ４０３）３．０部
・リン酸化合物（リン酸とモノメタクリロイルオキシエチルフォスフェート、ジメタクリロイルオキシエチルフォスフェートの２：１（質量比）混合物）０．３部<Evaluation of adhesion of resin BM film>
First, each component shown below was blended in the following composition and uniformly mixed to prepare a photosensitive BM-forming resin composition having a solid content concentration of 15%.
[Composition of resin composition for BM formation]
Binder resin (Nippon Kayaku Co., Ltd., trade name: ZCR1569H) 28.4 parts Photoactive agent (photopolymerization initiator)
(Ciba Specialty Chemicals, trade name: Irgacure OXE02) 6.1 parts Colloidal silica fine particles (Nissan Chemicals, trade name: PMAST) 20.3 parts Carbon black 32.5 parts Surfactant BYK Chemie Japan Co., Ltd., trade name: BYK306) 0.3 parts Crosslinking agent (Nippon Kayaku Co., Ltd., trade name: UX5002D) 6.1 parts (Nippon Kayaku Co., Ltd., trade name: NC3000H) 3.0 parts Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM403) 3.0 parts Phosphoric acid compound (2: 1 (mass ratio) mixture of phosphoric acid and monomethacryloyloxyethyl phosphate, dimethacryloyloxyethyl phosphate) ) 0.3 parts
次いで、このＢＭ形成用樹脂組成物を、洗浄後のガラス基板の表面に、スピンコート装置（ミカサ社製、装置名；ＭＳ−Ａ１００）を使用し、２００ｒｐｍで１０秒間塗布（スピンコート）した後、ホットプレート（アズワン社製、装置名；ＨＩ−１０００）を使用し、９０℃で６０秒間加熱・乾燥して塗膜を形成した。その後、露光装置（大日本科研製、装置名；ＭＡ−１２００）を使用し、フォトマスクを介して露光（照度：３０ｍＷ／ｃｍ２、露光量：３０ｍＪ／ｃｍ２、露光ＧＡＰ：５０μｍ）した後、現像装置（アクテス社製、装置名；ＡＤＥ−３０００Ｓ）を使用し、０．０４５％ＫＯＨ水溶液を用いて１５秒間現像した。続いて、純水洗浄することにより、ガラス基板の表面に樹脂ＢＭ膜のパターンを形成した。Next, this BM-forming resin composition was applied (spin coated) at 200 rpm for 10 seconds on the surface of the cleaned glass substrate using a spin coater (manufactured by Mikasa Co., Ltd., device name: MS-A100). Using a hot plate (manufactured by AS ONE, apparatus name: HI-1000), the coating film was formed by heating and drying at 90 ° C. for 60 seconds. Then, after exposing using a photomask (exposure intensity: 30 mW / cm 2 , exposure amount: 30 mJ / cm 2 , exposure GAP: 50 μm) using an exposure apparatus (manufactured by Dainippon Institute of Science, apparatus name: MA-1200). Using a developing device (manufactured by Actes, device name: ADE-3000S), development was performed for 15 seconds using a 0.045% KOH aqueous solution. Subsequently, a pattern of a resin BM film was formed on the surface of the glass substrate by washing with pure water.
フォトマスクは、以下に示すＬ１〜Ｌ４の４種類のパターン形状を有し、かつ各種類ごとに線幅を１μｍづつ変化させた計１１０種類のパターンとした。
Ｌ１………パターン間隔１００μｍで１ブロック（２８３５μｍ×２０００μｍ）に２５本の線状パターン（線幅は１〜２５μｍの範囲で可変）
Ｌ２………パターン間隔５０μｍで１ブロック（２９５２．６μｍ×２０００μｍ）に３０本の線状パターン（線幅は１〜３０μｍの範囲で可変）
Ｌ３………パターン間隔２００μｍで１ブロック（２６８２．５μｍ×２０００μｍ）に２５本の線状パターン（線幅は１〜２５μｍの範囲で可変）
Ｌ４………パターン間隔２００μｍで１ブロック（２６８２．５μｍ×２０００μｍ）に２５本の短い線状パターン（線幅は１〜２５μｍの範囲で可変）The photomask had four types of pattern shapes L1 to L4 shown below, and a total of 110 types of patterns in which the line width was changed by 1 μm for each type.
L1 ......... 25 linear patterns in one block (2835 μm × 2000 μm) with a pattern spacing of 100 μm (the line width is variable in the range of 1 to 25 μm)
L2 ......... 30 linear patterns in one block (2952.6 μm × 2000 μm) with a pattern spacing of 50 μm (the line width is variable in the range of 1-30 μm)
L3 ......... 25 linear patterns in one block (2682.5 μm × 2000 μm) with a pattern spacing of 200 μm (the line width is variable in the range of 1 to 25 μm)
L4 ......... 25 short linear patterns in one block (2682.5 μm × 2000 μm) with a pattern spacing of 200 μm (the line width is variable in the range of 1 to 25 μm)
現像後のガラス基板をレーザー顕微鏡（キーエンス社製、装置名；ＶＫ−９５１０）により観測し、ガラス基板上に樹脂ＢＭ膜のパターンが残るマスクの線幅を、Ｌ１〜Ｌ４の４種類のパターン形状それぞれについて調べた。そして、線幅が最大のものの線幅値（以下、残し解像度最大値と示す。）と最小のものの線幅値（以下、残し解像度最小値と示す。）、および平均値（以下、残し解像度平均値と示す。）を求めた。これらの結果を、表１および図２のグラフに示す。残し解像度とは、現像後に残るマスクの線幅（Ｌｉｎｅ ｗｉｄｔｈ ｏｆ ｔｈｅ ｍａｓｋ ｗｈｉｃｈ ｒｅｍａｉｎｓ ａｆｔｅｒ ｄｅｖｅｌｏｐｉｎｇ）のことである。
なお、残し解像度最大値、残し解像度最小値および残し解像度平均値は、いずれも小さいほど、洗浄後のガラス基板上に形成された樹脂ＢＭ膜の密着性が高いことを示している。The developed glass substrate is observed with a laser microscope (manufactured by Keyence Corporation, apparatus name: VK-9510), and the line width of the mask in which the pattern of the resin BM film remains on the glass substrate is represented by four types of pattern shapes L1 to L4. Each was examined. The line width value with the largest line width (hereinafter referred to as the maximum remaining resolution value), the line width value with the minimum line width (hereinafter referred to as the minimum remaining resolution value), and the average value (hereinafter referred to as the average remaining resolution). Value). These results are shown in Table 1 and the graph of FIG. The remaining resolution refers to the line width of the mask remaining after development (Line width of the mask why remains after developing).
In addition, it has shown that the adhesiveness of the resin BM film | membrane formed on the glass substrate after washing | cleaning is so high that all of the residual resolution maximum value, the residual resolution minimum value, and the residual resolution average value are small.
＜表面Ａｌ濃度（Ａｌ／Ｓｉ比）の測定＞
洗浄後のガラス基板表面のＡｌ濃度およびＳｉ濃度を、Ｘ線光電子分光法を用いて測定し、Ａｌ濃度とＳｉ濃度の比（Ａｌ／Ｓｉ比）を求めた。ＥＳＣＡ（Electron Spectroscopy for Chemical Analysis）の測定には、アルバック・ファイ社製のＥＳＣＡ５５００を使用し、Ｓｉ（２ｐ）およびＡｌ（２ｐ）のピークを用い、パスエネルギー１１７．４ｅＶ、エネルギーステップ０．５ｅＶ／ｓｔｅｐ、取り出し角（試料表面と検出器のなす角度）１５°の条件で測定を行った。スペクトルの解析には、解析ソフトＭｕｌｔｉＰａｋ Ｖｅｒ．８．２を使用した。得られた結果を、表１に示す。
なお、表面Ａｌ濃度およびＡｌ／Ｓｉ比は、基板表面の濡れ性（親水性）の指標の一つとすることができる。すなわち、表面Ａｌ濃度およびＡｌ／Ｓｉ比が高いほど、ガラス基板表面（表層）のＡｌ成分の浸出が少ないことを意味し、ガラス基板表面のＯＨリッチ親水層に起因する親水性（濡れ性）が低いことを示している。<Measurement of surface Al concentration (Al / Si ratio)>
The Al concentration and Si concentration on the surface of the glass substrate after cleaning were measured using X-ray photoelectron spectroscopy, and the ratio of Al concentration to Si concentration (Al / Si ratio) was determined. ESCA (Electron Spectroscopy for Chemical Analysis) is measured using ESCA5500 manufactured by ULVAC-PHI, using Si (2p) and Al (2p) peaks, a path energy of 117.4 eV, an energy step of 0.5 eV / Measurement was carried out under the conditions of step and take-off angle (angle formed by the sample surface and the detector) of 15 °. For analysis of the spectrum, analysis software MultiPak Ver. 8.2 was used. The obtained results are shown in Table 1.
The surface Al concentration and the Al / Si ratio can be one of the indicators of the wettability (hydrophilicity) of the substrate surface. That is, the higher the surface Al concentration and the Al / Si ratio, the less leaching of the Al component on the glass substrate surface (surface layer), and the hydrophilicity (wetting property) caused by the OH-rich hydrophilic layer on the glass substrate surface. It is low.
表１から、研磨後のガラス基板表面を酸性洗浄液により洗浄（酸洗浄）した後、アルカリ性洗浄液により洗浄（アルカリ洗浄）した実施例１および実施例２では、樹脂ＢＭ膜の残し解像度最大値、残し解像度最小値および残し解像度平均値が、酸洗浄のみを行った比較例に比べて小さく、アルカリ洗浄のみを行った比較例１と同程度となっており、ガラス基板表面への樹脂ＢＭ膜の密着性が良好であることがわかった。 From Table 1, in Example 1 and Example 2 in which the polished glass substrate surface was cleaned with an acidic cleaning solution (acid cleaning) and then cleaned with an alkaline cleaning solution (alkali cleaning), the maximum resolution value of the remaining resin BM film was left. The minimum resolution value and the average remaining resolution value are smaller than those of the comparative example in which only the acid cleaning is performed, and are similar to those in the comparative example 1 in which only the alkali cleaning is performed. The properties were found to be good.
また、酸洗浄およびアルカリ洗浄における洗浄液の温度を３５℃とした実施例２では、酸洗浄およびアルカリ洗浄を２５℃の洗浄液を用いて行った実施例１と比べて、残し解像度最大値と残し解像度最小値との差が小さくなっており、洗浄液の温度を上げることで、樹脂ＢＭ膜の密着性のばらつきが減少することがわかった。 Further, in Example 2 in which the temperature of the cleaning liquid in acid cleaning and alkaline cleaning was 35 ° C., the maximum remaining resolution and the remaining resolution were compared with Example 1 in which acid cleaning and alkaline cleaning were performed using a cleaning liquid of 25 ° C. It was found that the difference from the minimum value was small, and that the variation in the adhesion of the resin BM film was reduced by raising the temperature of the cleaning solution.
さらに、実施例１および実施例２では、Ａｌ／Ｓｉ比が、比較例２に比べて高く、比較例１と同程度となっており、酸性洗浄液により洗浄した後にアルカリ性洗浄液により洗浄することで、ガラス基板表面の親水性（濡れ性）は、酸洗浄を行わずにアルカリ洗浄のみを行った比較例１と同程度に低いものとなり、樹脂ＢＭ膜の密着性が良好なガラス基板表面が得られることがわかった。 Further, in Example 1 and Example 2, the Al / Si ratio is higher than that in Comparative Example 2 and is about the same as that in Comparative Example 1, and after washing with an acidic washing liquid, washing with an alkaline washing liquid, The hydrophilicity (wettability) of the glass substrate surface is as low as that of Comparative Example 1 in which only alkali cleaning is performed without acid cleaning, and a glass substrate surface with good adhesion of the resin BM film is obtained. I understood it.
＜接触角の測定＞
洗浄直後のガラス基板の表面に、約１μＬの純水の水滴を着滴させ、接触角計（ＦＡＣＥ社製、装置名；ＣＡ−Ｘ）を用いて、水に対する接触角を測定した。また、洗浄から７日、１４日、２１日および２８日経過後において、ガラス基板の表面の水に対する接触角を、前記と同様にして測定した。測定結果を、表２および図３のグラフに示す。
なお、水に対する接触角も、基板表面の濡れ性（親水性）の指標の一つとすることができる。ガラス基板表面の水に対する接触角が大きいほど、親水性（濡れ性）が低いことを示している。<Measurement of contact angle>
About 1 μL of pure water droplets were deposited on the surface of the glass substrate immediately after washing, and the contact angle with water was measured using a contact angle meter (manufactured by FACE, apparatus name: CA-X). Further, after 7 days, 14 days, 21 days and 28 days from the cleaning, the contact angle of the glass substrate surface with water was measured in the same manner as described above. The measurement results are shown in Table 2 and the graph of FIG.
Note that the contact angle with water can also be one of the indicators of the wettability (hydrophilicity) of the substrate surface. The larger the contact angle of the glass substrate surface with water, the lower the hydrophilicity (wetting property).
表２から以下のことがわかった。すなわち、洗浄直後の接触角については、実施例１と比較例１および比較例２の間でほとんど差異がないが、基板を１週間以上暴露した後の接触角は、実施例１では、比較例１よりも低いが比較例２に比べて大幅に高くなっていた。このことから、酸性の洗浄液により洗浄した後にアルカリ洗浄することで、酸洗浄のみを行った比較例２と比べて、ガラス基板を１週間以上暴露した後の実施例１では、接触角が高く、親水性（濡れ性）が低下し、樹脂ＢＭ膜の密着性が良好なガラス基板表面が得られることがわかった。 Table 2 shows the following. That is, there is almost no difference between Example 1 and Comparative Example 1 and Comparative Example 2 in the contact angle immediately after cleaning, but the contact angle after exposing the substrate for one week or more is in Comparative Example 1 in Example 1. Although it was lower than 1, it was significantly higher than Comparative Example 2. From this, the contact angle is higher in Example 1 after exposing the glass substrate for one week or more than in Comparative Example 2 in which only the acid cleaning was performed by cleaning with an acidic cleaning solution and then with alkali cleaning. It was found that the hydrophilicity (wetting property) was lowered and a glass substrate surface with good adhesion of the resin BM film was obtained.
本発明の洗浄方法によれば、酸化セリウムを含有する研磨剤による研磨後のガラス基板を、表面の平坦性を損なうことなく効率的に洗浄して、表面に残留・付着した砥粒を除去することができ、かつ洗浄後のガラス基板表面に形成される樹脂ＢＭ膜の密着性低下を抑制して、樹脂ＢＭ膜の剥れを防止することができる。したがって、本発明の洗浄方法は、ＬＣＤのようなＦＰＤ用に使用されるガラス基板の洗浄に有効に適用することができる。 According to the cleaning method of the present invention, the glass substrate after being polished with the abrasive containing cerium oxide is efficiently cleaned without impairing the flatness of the surface, and the abrasive grains remaining on and adhered to the surface are removed. In addition, it is possible to prevent the resin BM film from peeling off by suppressing the decrease in the adhesion of the resin BM film formed on the surface of the glass substrate after washing. Therefore, the cleaning method of the present invention can be effectively applied to cleaning glass substrates used for FPDs such as LCDs.
なお、２０１２年１１月２２日に出願された日本特許出願２０１２−２５６７１４号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2012-256714 filed on November 22, 2012 is cited herein as the disclosure of the specification of the present invention. Incorporated.
１…搬送ロール、２…洗浄室、３…ガラス基板、４…洗浄ノズル、５…酸性洗浄液、６…回転ブラシ、７…アルカリ性洗浄液。 DESCRIPTION OF SYMBOLS 1 ... Conveyance roll, 2 ... Cleaning chamber, 3 ... Glass substrate, 4 ... Cleaning nozzle, 5 ... Acidic cleaning liquid, 6 ... Rotary brush, 7 ... Alkaline cleaning liquid.
Claims (10)
請求項３に記載のガラス基板の洗浄方法。The content ratio of the components (A) to (D) in the acidic aqueous cleaning solution is 0.01% of (A) organic phosphonic acid with respect to 100% by mass of the total amount of (A) to (D). -50 mass%, (B) 0.01-10 mass% of polycarboxylic acid salt, (C) 0.01-50 mass% of aromatic sulfonic acid, and (D) amine-alkylene oxide adduct is 0.00. It is 02-10 mass%, The cleaning method of the glass substrate of Claim 3.
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| JP2012256714 | 2012-11-22 | ||
| JP2012256714 | 2012-11-22 | ||
| PCT/JP2013/081203 WO2014080917A1 (en) | 2012-11-22 | 2013-11-19 | Glass substrate cleaning method |
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| KR (1) | KR20150087224A (en) |
| CN (1) | CN104781204A (en) |
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| KR20160144406A (en) | 2014-04-04 | 2016-12-16 | 코닝 인코포레이티드 | Treatment of glass surfaces for improved adhesion |
| JP2017100933A (en) * | 2015-11-20 | 2017-06-08 | 旭硝子株式会社 | Glass substrate and glass plate packaging body |
| JP6670104B2 (en) * | 2015-12-28 | 2020-03-18 | ＡｖａｎＳｔｒａｔｅ株式会社 | Cleaning solution for glass substrate for color filter and method for cleaning glass substrate for color filter |
| CN109517676B (en) * | 2017-09-20 | 2021-04-09 | 蓝思科技（长沙）有限公司 | Cleaning agent for cleaning glass antireflection film and cleaning process of glass antireflection film |
| US20200399173A1 (en) * | 2018-03-09 | 2020-12-24 | Corning Incorporated | Method for minimizing dent defects in chemically strengthened glass |
| JP6837032B2 (en) * | 2018-05-30 | 2021-03-03 | 双葉電子工業株式会社 | Method of manufacturing polymer substrate and method of manufacturing electronic device |
| CN109536293B (en) * | 2018-11-30 | 2021-04-09 | 蓝思科技（长沙）有限公司 | Acidic lotion for cleaning arc-edge milled powder of 3D glass and cleaning process |
| KR102604565B1 (en) * | 2019-01-10 | 2023-11-23 | 삼성디스플레이 주식회사 | Window and method of manufacturing the same |
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| JP7316112B2 (en) | 2019-06-25 | 2023-07-27 | 花王株式会社 | Substrate cleaning method |
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| CN110767534B (en) * | 2019-10-28 | 2021-12-28 | 江苏晶杰光电科技有限公司 | Wafer cleaning method |
| CN111073767A (en) * | 2019-12-25 | 2020-04-28 | 东莞市晶博光电有限公司 | Glass cover plate cleaning agent and cleaning method thereof |
| KR20220157931A (en) * | 2020-03-25 | 2022-11-29 | 니폰 덴키 가라스 가부시키가이샤 | Manufacturing method of glass plate |
| CN111498797A (en) * | 2020-03-31 | 2020-08-07 | 北京航天控制仪器研究所 | Manufacturing method of wafer-level glass cavity |
| CN113717799A (en) * | 2021-10-08 | 2021-11-30 | 台州星星光电科技有限公司 | Method for cleaning polished sapphire glass |
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| KR20150087224A (en) | 2015-07-29 |
| CN104781204A (en) | 2015-07-15 |
| WO2014080917A1 (en) | 2014-05-30 |
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