TWI617522B - Glass product with protective film and manufacturing method thereof - Google Patents
Glass product with protective film and manufacturing method thereof Download PDFInfo
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- TWI617522B TWI617522B TW103112007A TW103112007A TWI617522B TW I617522 B TWI617522 B TW I617522B TW 103112007 A TW103112007 A TW 103112007A TW 103112007 A TW103112007 A TW 103112007A TW I617522 B TWI617522 B TW I617522B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/76—Hydrophobic and oleophobic coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
- G02F2201/501—Blocking layers, e.g. against migration of ions
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Abstract
本發明之課題在於提供一種保護膜之形成較容易、其去除亦可利用簡便之操作容易地進行，且可有效賦予污染之防止效果之新穎的附有保護膜之玻璃製品。 The object of the present invention is to provide a novel glass product with a protective film, which is relatively easy to form a protective film, can be easily removed by simple operations, and can effectively provide a pollution prevention effect.
本發明之附有保護膜之玻璃製品1於玻璃製品2之表面具有保護膜3，該保護膜3包含：含有具有碳數為8以上之疏水性基之吡啶鎓鹽之陽離子界面活性劑或平均分子量為500~1000萬之陽離子聚合物。該保護膜3為單層結構，製造操作較為簡便，且可顯著提高污染之防止效果，並且可藉由清洗而容易地去除。 The glass product 1 with a protective film of the present invention has a protective film 3 on the surface of the glass product 2. The protective film 3 includes: a cationic surfactant containing a pyridinium salt having a hydrophobic group with a carbon number of 8 or more, or an average Cationic polymer with a molecular weight of 5-10 million. The protective film 3 has a single-layer structure, which is simple in manufacturing operation, can significantly improve the effect of preventing pollution, and can be easily removed by washing.
Description
本發明係關於一種附有保護膜之玻璃製品及其製造方法。 The invention relates to a glass product with a protective film and a manufacturing method thereof.
玻璃製品之表面易被污染，若暴露於外部環境中，則環境中所含之灰塵或有機物等附著，即刻被污染。尤其是用於平板顯示器(FPD，Flat Panel Display)等精密設備之玻璃製品為了不產生由灰塵或有機物等導致之污染，必須於清潔之狀態下處理其表面。因此，其製造係藉由無塵室等進行。 The surface of glass products is easy to be contaminated. If exposed to the external environment, dust or organic substances contained in the environment are attached and immediately contaminated. In particular, glass products used in precision devices such as flat panel displays (FPD, Flat Panel Display) must be cleaned in order to prevent contamination caused by dust or organic matter. Therefore, the manufacturing is performed by a clean room or the like.
但例如於FPD用之玻璃基板之情形時，於製造此種玻璃基板後，加工為顯示器用之製品時，會將該玻璃基板運輸至顯示器製造工廠並保管等。此時，即便於玻璃基板製造時製造為非常清潔之表面，於其使用時(製造顯示器時)，亦多會產生某些污染。作為其原因之一，可想到為了不使玻璃基板彼此接觸，而常於基板間預先隔著間隔紙，可能被源自該間隔紙之TiO2微粒子或矽酮顆粒污染。 However, for example, in the case of a glass substrate for FPD, when the glass substrate is manufactured and processed into a display product, the glass substrate is transported to a display manufacturing factory and stored. At this time, even when the glass substrate is manufactured as a very clean surface, some pollution may occur during its use (when manufacturing a display). As one of the reasons, it is conceivable that a spacer paper is often interposed between the substrates in order to prevent the glass substrates from contacting each other, and may be contaminated by TiO 2 fine particles or silicone particles derived from the spacer paper.
又，此種表面污染之問題長期存在，此前亦研究各種防止玻璃製品之表面之污染的方法。例如，已知如下方法：為了自剛製造玻璃製品後起即將其保護，而將該方法併入玻璃製品之製造製程中，保護玻璃製品之表面。該方法係於溫度高於175℃之熱玻璃製品上，藉由至少一種界面活性劑於表面形成疏水性塗層，實施玻璃製品之切斷、粗磨、研磨的玻璃之處理方法(參照專利文獻1)。 In addition, such a problem of surface contamination has existed for a long time, and various methods for preventing the surface contamination of glass products have been studied before. For example, a method is known in which the method is incorporated into a glass product manufacturing process to protect the surface of the glass product in order to protect it immediately after the glass product is manufactured. This method is a hot glass product with a temperature higher than 175 ° C. A hydrophobic coating is formed on the surface by at least one surfactant, and the glass product is cut, roughed, and polished. (See Patent Literature 1).
進而，亦已知有包含陰離子性界面活性劑之水溶性保護膜(參照 專利文獻2)、使親水基之一部分向與親水性構件之表面相反之側配向之水溶性塗層(參照專利文獻3)、具有羥基、羧基等作為親水性基之長鏈有機材料(參照專利文獻4)等保護膜。 Furthermore, a water-soluble protective film containing an anionic surfactant is also known (see Patent Document 2), a water-soluble coating that aligns a part of the hydrophilic group to the side opposite to the surface of the hydrophilic member (refer to Patent Document 3), a long-chain organic material having a hydrophilic group such as a hydroxyl group and a carboxyl group (see Patent Reference 4) and other protective films.
[專利文獻1]日本專利特開2000-319038號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2000-319038
[專利文獻2]日本專利特開2000-211947號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2000-211947
[專利文獻3]日本專利特開2002-46225號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2002-46225
[專利文獻4]日本專利特開2012-116748號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2012-116748
然而，專利文獻1中將保護膜之形成併入玻璃製品之製造製程中，無法應用於製造玻璃製品後實施研磨步驟之情形。又，認為專利文獻2~4所記載之保護膜由於與玻璃製品表面之矽烷醇基之相互作用較弱，其形成須費工夫，且保護膜相對不穩定。 However, in Patent Document 1, the formation of the protective film is incorporated into the manufacturing process of the glass product, and cannot be applied to the case where the polishing step is performed after the glass product is manufactured. In addition, it is considered that the protective films described in Patent Documents 2 to 4 have weak interactions with silanol groups on the surface of glass products, and it takes time to form the protective films, and the protective films are relatively unstable.
因此，本發明之目的在於提供一種可利用簡便之操作容易地進行保護膜之形成、去除，保護膜相對穩定，且可有效地賦予污染之防止效果之新穎之保護膜。 Therefore, an object of the present invention is to provide a novel protective film that can be easily formed and removed with a simple operation, the protective film is relatively stable, and can effectively impart a pollution prevention effect.
本發明之附有保護膜之玻璃製品之特徵在於：其於玻璃製品之表面具有包含含有具有碳數為8以上之疏水性基之吡啶鎓鹽之陽離子界面活性劑或平均分子量為500~1000萬之陽離子聚合物之保護膜。 The protective glass product of the present invention is characterized in that it has a cationic surfactant containing a pyridinium salt having a hydrophobic group having a carbon number of 8 or more on the surface of the glass product or an average molecular weight of 5-10 million Protective film of cationic polymer.
又，本發明之附有保護膜之玻璃製品之製造方法之特徵在於具有如下步驟：使包含含有具有碳數為8以上之疏水性基之吡啶鎓鹽之陽離子界面活性劑或平均分子量為500~1000萬之陽離子聚合物之溶液與玻璃製品之表面接觸並加以乾燥，而形成包含上述陽離子界面活 性劑或上述陽離子聚合物之保護膜。 In addition, the method for manufacturing a glass product with a protective film of the present invention is characterized by having the following steps: a cationic surfactant containing a pyridinium salt containing a hydrophobic group having a carbon number of 8 or more or an average molecular weight of 500 to A solution of 10 million cationic polymers is brought into contact with the surface of a glass product and dried to form the above-mentioned cationic interface Protective film of anionic or cationic polymer.
根據本發明之附有保護膜之玻璃製品及其製造方法，於玻璃製品之表面設置保護膜，可防止於玻璃製品之製造至使用前之期間異物附著等之污染。又，於使用玻璃製品前，該保護膜可藉由水洗或鹼洗等簡便之操作而容易地去除。 According to the glass product with a protective film of the present invention and a method for manufacturing the same, a protective film is provided on the surface of the glass product to prevent contamination from foreign matter and the like from the time when the glass product is manufactured to before use. Moreover, before using a glass product, this protective film can be easily removed by simple operations, such as water washing and alkali washing.
1‧‧‧附有保護膜之玻璃製品 1‧‧‧ Glass products with protective film
2‧‧‧玻璃製品 2‧‧‧ glass products
3‧‧‧保護膜 3‧‧‧ protective film
圖1係表示本發明之附有保護膜之玻璃製品之概略構成的剖面圖。 FIG. 1 is a cross-sectional view showing a schematic configuration of a glass product with a protective film according to the present invention.
圖2係表示實施例及比較例之TiO2微粒子之殘留量的圖。 FIG. 2 is a graph showing the residual amount of TiO 2 fine particles in Examples and Comparative Examples.
圖3係表示實施例及比較例之與純水之接觸角的圖。 FIG. 3 is a view showing contact angles with pure water in Examples and Comparative Examples.
以下，一面參照圖式一面說明本發明之附有保護膜之玻璃製品。再者，圖1係表示本發明之附有保護膜之玻璃製品之概略構成的剖面圖，本發明之附有保護膜之玻璃製品1包含玻璃製品2、及形成於其表面之保護膜3。 Hereinafter, the glass product with a protective film of this invention is demonstrated, referring drawings. In addition, FIG. 1 is a cross-sectional view showing a schematic configuration of the glass product with a protective film of the present invention. The glass product 1 with a protective film of the present invention includes a glass product 2 and a protective film 3 formed on a surface thereof.
此處所使用之玻璃製品2只要為於其表面露出玻璃之玻璃製品，則可無特別限定地列舉。再者，尤佳為應用於與要求將玻璃製品之表面保持為清潔之半導體製品之製造相關而使用之玻璃製品，例如平板顯示器(FPD)用玻璃基板、光學多層膜基板等。 The glass product 2 used here is not specifically limited as long as it is a glass product whose glass is exposed on the surface. Furthermore, it is particularly preferably applied to glass products used in connection with the manufacture of semiconductor products that require the surface of glass products to be kept clean, such as glass substrates for flat panel displays (FPDs), optical multilayer film substrates, and the like.
本發明所使用之保護膜3係設置於玻璃製品2之表面之單層結構之膜。此處，保護膜3係如下膜，其包含：含有具有碳數為8以上之疏水性基之吡啶鎓鹽之陽離子界面活性劑或平均分子量為500~1000萬之陽離子聚合物。 The protective film 3 used in the present invention is a film having a single-layer structure provided on the surface of the glass product 2. Here, the protective film 3 is a film including a cationic surfactant containing a pyridinium salt having a hydrophobic group having a carbon number of 8 or more, or a cationic polymer having an average molecular weight of 5 to 10 million.
作為此處所使用之陽離子界面活性劑，只要為具有碳數為8以上之疏水性基之吡啶鎓鹽，則可無特別限定地使用。若其疏水性基之碳 數增大，則玻璃表面之被覆性增高，防污性提高，因此較佳為疏水性基之碳數為12以上。作為此種疏水性基，典型而言可列舉碳數為8~18之烷基，尤佳為碳數為16~18之烷基。例如可列舉：氯化辛基吡啶鎓、氯化癸基吡啶鎓、氯化十二烷基吡啶鎓、氯化十四烷基吡啶鎓、氯化十六烷基吡啶鎓、氯化十八烷基吡啶鎓等吡啶鎓鹽等。該吡啶鎓鹽可提高玻璃製品之撥水性，尤其是氯化十六烷基吡啶鎓(別名：氯化鯨蠟基吡啶鎓)就可大量生產、易於廉價地獲得之方面而言較佳。 The cationic surfactant used herein can be used without particular limitation as long as it is a pyridinium salt having a hydrophobic group having a carbon number of 8 or more. If the carbon of its hydrophobic group When the number is increased, the coverability of the glass surface is increased, and the antifouling property is improved. Therefore, the number of carbons of the hydrophobic group is preferably 12 or more. Examples of such a hydrophobic group include an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 16 to 18 carbon atoms is particularly preferred. Examples include octylpyridinium chloride, decylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium chloride, and octadecyl chloride Pyridinium salts and the like. The pyridinium salt can improve the water repellency of glass products. In particular, hexadecylpyridinium chloride (alias: cetylpyridinium chloride) is preferable in terms of mass production and easy and inexpensive acquisition.
又，作為此處所使用之陽離子聚合物，只要為平均分子量為500~1000萬且分子中具有陽離子性基之聚合物即可。再者，於本說明書中，平均分子量係指重量平均分子量。陽離子性基係溶解於水等溶劑中時成為陽離子之基，例如可列舉胺基、四級銨基等。此時，胺基係自氨、一級胺、二級胺中去除氫之一價官能基，分別形成一級胺、二級胺、三級胺。又，四級銨基形成四級銨陽離子。 The cationic polymer used herein may be a polymer having an average molecular weight of 5 to 10 million and a cationic group in the molecule. In addition, in this specification, an average molecular weight means a weight average molecular weight. The cationic group is a group which becomes a cation when dissolved in a solvent such as water, and examples thereof include an amine group and a quaternary ammonium group. At this time, the amine group removes the monovalent functional group of hydrogen from ammonia, primary amine, and secondary amine to form primary amine, secondary amine, and tertiary amine, respectively. The quaternary ammonium group forms a quaternary ammonium cation.
作為此處所使用之陽離子聚合物，例如可列舉：聚氯化二烯丙基二甲基銨(PDAC或PDADMAC(poly(diallyldimethyl ammonium chloride)))、聚(丙烯酸二甲胺基乙酯氯甲烷四級鹽)、聚(甲基丙烯酸二甲胺基乙酯氯甲烷四級鹽)、三甲基銨烷基丙烯醯胺聚合物鹽、二甲基胺表氯醇縮合物鹽、聚烯丙胺、聚伸乙基亞胺等。 Examples of the cationic polymer used herein include polydiallyl dimethyl ammonium chloride (PDAC or PDADMAC (poly (diallyl dimethyl ammonium chloride))), and poly (dimethylaminoethyl acrylate, methyl chloride, tetrachloromethane). Grade salt), poly (dimethylaminoethyl methacrylate quaternary salt), trimethylammonium alkylpropeneamine polymer salt, dimethylamine epichlorohydrin condensate salt, polyallylamine, Polyethyleneimine and so on.
作為陽離子聚合物，較佳為陽離子性基之個數於分子量每1000具有4~25個。 As the cationic polymer, the number of cationic groups per molecular weight is preferably 4 to 25.
上述保護膜3為單層結構之保護膜，其製造操作簡便，並且可提高污染之防止效果。又，此處所形成之保護膜包含界面活性劑，與玻璃製品之表面藉由靜電結合而結合，可藉由使用純水或陰離子性洗劑之清洗而容易地去除。 The protective film 3 is a protective film with a single-layer structure, which is simple in manufacturing operation and can improve the effect of preventing pollution. In addition, the protective film formed here contains a surfactant, which is combined with the surface of the glass product by electrostatic bonding, and can be easily removed by washing with pure water or an anionic detergent.
繼而，對附有保護膜之玻璃製品之製造方法進行說明。 Next, the manufacturing method of the glass product with a protective film is demonstrated.
作為形成本發明之保護膜之方法，使包含含有具有碳數為8以上 之疏水性基之吡啶鎓鹽之陽離子界面活性劑或平均分子量為500~1000萬之陽離子聚合物之溶液與玻璃製品之表面接觸並加以乾燥，形成包含陽離子界面活性劑或陽離子聚合物之保護膜即可。 As a method for forming the protective film of the present invention, A cationic surfactant of a pyridinium salt of a hydrophobic group or a solution of a cationic polymer having an average molecular weight of 5-10 million is brought into contact with the surface of a glass product and dried to form a protective film containing a cationic surfactant or a cationic polymer Just fine.
此時，陽離子界面活性劑或陽離子聚合物係使用純水或乙醇等水溶性有機溶劑之水溶液作為溶劑，溶解於其中而製成溶液。此時，陽離子界面活性劑之溶液濃度較佳為0.01mmol/L~100mmol/L，為了適當地覆蓋玻璃製品表面且不過量，更佳為0.1~10mmol/L。又，於使用陽離子聚合物之情形時，較佳為使其溶液中之陽離子性基之濃度(當量)成為0.01meq/L~100meq/L之範圍，為了適當地覆蓋玻璃製品之表面且不過量，更佳為0.1meq/L~10meq/L。此外，於1L溶液中含有1mol陽離子性基之情形時，將其濃度設為1當量，表示為1eq/L。又，溶液之pH值為酸性~鹼性(例如，pH值4~12左右)時可使用，但就藉由促進玻璃製品表面之矽烷醇基之電離，使其帶負電，可使靜電結合力更堅固，且增加附著量之方面而言，溶液之pH值較佳為8~12，更佳為10~11。 At this time, a cationic surfactant or a cationic polymer is dissolved in an aqueous solution of a water-soluble organic solvent such as pure water or ethanol as a solvent to prepare a solution. At this time, the solution concentration of the cationic surfactant is preferably 0.01 mmol / L to 100 mmol / L. In order to properly cover the surface of the glass product without excessive amount, it is more preferably 0.1 to 10 mmol / L. When a cationic polymer is used, the concentration (equivalent) of the cationic group in the solution is preferably in a range of 0.01 meq / L to 100 meq / L. In order to properly cover the surface of the glass product and not excessively, , More preferably 0.1meq / L ~ 10meq / L. When 1 mol of a cationic group is contained in a 1 L solution, the concentration is set to 1 equivalent and expressed as 1 eq / L. In addition, the solution can be used when the pH value is acidic to alkaline (for example, pH value is about 4 to 12), but by promoting the ionization of the silanol groups on the surface of the glass product to make it negatively charged, the electrostatic binding force can be made. In terms of being stronger and increasing the amount of adhesion, the pH of the solution is preferably from 8 to 12, more preferably from 10 to 11.
使以上述方式獲得之溶液接觸並塗佈於欲形成保護膜之玻璃製品之表面。此時，塗佈方法可列舉浸漬塗佈、噴塗、利用海綿等之塗佈等公知之膜形成方法所使用之塗佈方法。又，該步驟中，溶液中所含之陽離子界面活性劑或陽離子聚合物僅藉由接觸，而使陽離子界面活性劑之親水性基或陽離子聚合物之陽離子部分朝向玻璃基板之表面側排列，使陽離子界面活性劑之疏水性基或陽離子聚合物之連接陽離子部分之聚合物之主鏈部分朝向作為其相反側之環境中排列。其原因在於，由於存在於玻璃製品之表面之矽烷醇基(-Si-OH)容易帶-電荷，因此僅藉由接觸，帶+電荷之陽離子界面活性劑之親水性基或陽離子聚合物之陽離子部分被靜電吸引向玻璃製品之表面側。 The solution obtained in the above manner is brought into contact with and coated on the surface of a glass article to be formed into a protective film. In this case, examples of the coating method include coating methods used in known film forming methods such as dip coating, spray coating, and coating with a sponge. In addition, in this step, the cationic surfactant or cationic polymer contained in the solution is aligned with the hydrophilic group of the cationic surfactant or the cationic part of the cationic polymer toward the surface side of the glass substrate only by contact. The hydrophobic group of the cationic surfactant or the main chain portion of the polymer of the cationic polymer connected to the cationic portion is aligned in the environment as its opposite side. The reason is that, because the silanol group (-Si-OH) existing on the surface of the glass product is easy to be -charged, only by contacting the hydrophilic group of the cationic surfactant with a charge or the cation of the cationic polymer A part is attracted to the surface side of the glass product by static electricity.
若於以上述方式使陽離子界面活性劑或陽離子聚合物排列之狀 態下，藉由加熱或鼓風等去除溶劑，則可容易地形成均質之第1膜。此時，加熱乾燥中，較佳為加熱至50~80℃，鼓風中，較佳為吹送15~30℃之空氣。 If the cationic surfactant or cationic polymer is arranged in the above manner In a state, the first film can be easily formed by removing the solvent by heating, blowing, or the like. At this time, it is preferable to heat to 50 to 80 ° C during heating and drying, and it is preferable to blow air at 15 to 30 ° C during blowing.
又，於形成該保護膜之情形時，可藉由於室溫下塗佈溶液之簡便之操作而達成，進而，可達成亦不會違反排水限制、不會增大環境負荷之玻璃製品之表面保護。 In addition, in the case of forming the protective film, it can be achieved by the simple operation of coating the solution at room temperature, and further, the surface protection of glass products that do not violate drainage restrictions and increase environmental load can be achieved. .
以下，基於實施例及比較例，進一步對本發明進行詳細說明。 Hereinafter, the present invention will be described in more detail based on examples and comparative examples.
以作為陽離子性界面活性劑之氯化鯨蠟基吡啶鎓(CPC，cetylpyridinium chloride)成為1mmol/L及氨成為10mmol/L之濃度之方式，將各成分溶解於純水中，製備保護膜形成用之溶液。該溶液之pH值約為10.5。 Cetylpyridinium chloride (CPC) as a cationic surfactant was used at a concentration of 1 mmol / L and ammonia at a concentration of 10 mmol / L. The components were dissolved in pure water to prepare a protective film. Its solution. The pH of this solution is about 10.5.
以作為陽離子聚合物之聚氯化二烯丙基二甲基銨(PDAC或PDADMAC；和光純藥工業公司製造之膠體滴定用標準液，分子量6萬~11萬)成為1meq/L及氨成為10mmol/L之濃度之方式，將各成分溶解於純水中，製備保護膜形成用之溶液。該溶液之pH值約為10.5。 As a cationic polymer, polydiallyldimethylammonium chloride (PDAC or PDADMAC; a standard solution for colloidal titration manufactured by Wako Pure Chemical Industries, Inc., molecular weight 60,000 to 110,000) becomes 1 meq / L and ammonia becomes 10 mmol / L concentration method, each component was dissolved in pure water to prepare a solution for forming a protective film. The pH of this solution is about 10.5.
以作為陽離子聚合物之聚伸乙基亞胺(PEI(polyethyleneimine)；日本觸媒公司製造之Epomin SP-006(分子量約600))成為1meq/L之濃度之方式，將其溶解於純水中，製備保護膜形成用之溶液3。該溶液之pH值約為10.5。 Polyethyleneimine (PEI (polyethyleneimine) as a cationic polymer; Epimin SP-006 (molecular weight of about 600) manufactured by Nippon Catalytic Corporation) was dissolved in pure water so that the concentration became 1 meq / L. To prepare a solution 3 for forming a protective film. The pH of this solution is about 10.5.
以作為陽離子聚合物之聚伸乙基亞胺(PEI；日本觸媒公司製造之 Epomin SP-200(分子量約10000))成為1meq/L之濃度之方式，將其溶解於純水中，製備保護膜形成用之溶液。該溶液之pH值約為10.5。 Polyethylenimine (PEI as a cationic polymer; Epomin SP-200 (molecular weight: about 10,000)) was prepared in a concentration of 1 meq / L. The solution was dissolved in pure water to prepare a solution for forming a protective film. The pH of this solution is about 10.5.
將經表面研磨之長50mm×寬50mm×厚0.7mm之無鹼硼矽酸鹽玻璃製之玻璃板於上述保護膜形成用之溶液1中浸漬10秒而取出後，利用鼓風乾燥表面之溶液，藉由如上之浸漬塗佈法，於玻璃板之表面形成保護膜，製成附有保護膜之玻璃製品。 After the surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm was immersed in the above-mentioned solution 1 for forming a protective film for 10 seconds and taken out, the solution on the surface was dried by blasting By the above dip coating method, a protective film is formed on the surface of the glass plate to make a glass product with a protective film.
將經表面研磨之長50mm×寬50mm×厚0.7mm之無鹼硼矽酸鹽玻璃製之玻璃板於上述保護膜形成用之溶液2中浸漬10秒而取出後，利用鼓風乾燥表面之溶液，藉由如上之浸漬塗佈法，於玻璃板之表面形成保護膜，製成附有保護膜之玻璃製品。 After the surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm was immersed in the above-mentioned solution 2 for forming a protective film for 10 seconds and taken out, the solution on the surface was dried by blasting By the above dip coating method, a protective film is formed on the surface of the glass plate to make a glass product with a protective film.
將經表面研磨之長50mm×寬50mm×厚0.7mm之無鹼硼矽酸鹽玻璃製之玻璃板於上述保護膜形成用之溶液3中浸漬10秒而取出後，利用鼓風乾燥表面之溶液，藉由如上之浸漬塗佈法，於玻璃板之表面形成保護膜，製成附有保護膜之玻璃製品。 After the surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm was immersed in the above-mentioned solution 3 for forming a protective film for 10 seconds and taken out, the solution on the surface was dried by blast By the above dip coating method, a protective film is formed on the surface of the glass plate to make a glass product with a protective film.
將經表面研磨之長50mm×寬50mm×厚0.7mm之無鹼硼矽酸鹽玻璃製之玻璃板於上述保護膜形成用之溶液4中浸漬10秒而取出後，利用鼓風乾燥表面之溶液，藉由如上之浸漬塗佈法，於玻璃板之表面形成保護膜，製成附有保護膜之玻璃製品。 After the surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm was immersed in the above-mentioned solution 4 for forming a protective film for 10 seconds, and then taken out, the surface solution was dried by blasting By the above dip coating method, a protective film is formed on the surface of the glass plate to make a glass product with a protective film.
利用純水清洗經表面研磨之長50mm×寬50mm×厚0.7mm之無鹼硼矽酸鹽玻璃製之玻璃板。該玻璃板為表面經研磨後之狀態，未設有保護膜等。 The purely water-washed glass plate made of alkali-free borosilicate glass with a length of 50 mm × width 50 mm × thickness 0.7 mm was cleaned. The glass plate is in a state where the surface is polished, and is not provided with a protective film or the like.
將經表面研磨之長50mm×寬50mm×厚0.7mm之無鹼硼矽酸鹽玻璃製之玻璃板於將作為陰離子性界面活性劑之磺基丁二酸二辛酯鈉以成為1mmol/L之濃度之方式溶解於純水中而成之陰離子性界面活性劑溶液中浸漬10秒而取出後，利用鼓風乾燥表面之溶液，藉由如上之浸漬塗佈法，於玻璃板之表面形成陰離子性界面活性劑之膜。 Surface-milled a glass plate made of alkali-free borosilicate glass having a length of 50 mm × width 50 mm × thickness 0.7 mm to a sodium dioctyl sulfosuccinate as an anionic surfactant to be 1 mmol / L. Anionic surfactant solution prepared by dissolving in pure water in a concentration method, immersed in the solution for 10 seconds, and then taken out. The solution on the surface was dried by blasting, and anionic was formed on the surface of the glass plate by the above dipping coating method Surfactant film.
將塗有製紙添加用TiO2微粒子顏料之間隔紙壓抵於實施例及比較例之玻璃製品之表面，而轉印TiO2微粒子。對該玻璃製品進行吹送30秒約25℃之空氣之鼓風，其後於25℃之純水中進行30秒100kHz下之超音波清洗，進而，於將市售之鹼性洗劑原液(Parker Corporation公司製造，商品名：PK-LCG211)稀釋100倍而成之鹼洗液中進行30秒28kHz下之超音波清洗。利用螢光X射線法，對鼓風後、純水清洗後、鹼性洗劑清洗後之各處理後之玻璃製品之表面監控TiO2微粒子之殘留狀況，將其結果示於圖2。關於與鼓風後相比之鹼洗後之TiO2微粒子之去除率，實施例1為59%，實施例2為48%，實施例3為55%，實施例4為50%，比較例1為35%，比較例2為34%。 The spacer paper coated with the TiO 2 fine particle pigment for papermaking was pressed against the surface of the glass products of the examples and comparative examples, and the TiO 2 fine particles were transferred. This glass product was blown with air at about 25 ° C for 30 seconds, and then ultrasonically cleaned at 100kHz for 30 seconds in pure water at 25 ° C. Furthermore, a commercially available alkaline lotion stock solution (Parker Corporation, trade name: PK-LCG211) was diluted 100-fold in an alkaline washing solution and subjected to ultrasonic cleaning at 28 kHz for 30 seconds. Fluorescence X-ray method was used to monitor the residual state of TiO 2 fine particles on the surface of each processed glass product after blowing, pure water cleaning, and alkaline detergent cleaning, and the results are shown in FIG. 2. Regarding the removal rate of TiO 2 fine particles after alkali washing compared with that after blowing, Example 1 was 59%, Example 2 was 48%, Example 3 was 55%, Example 4 was 50%, and Comparative Example 1 It was 35% and Comparative Example 2 was 34%.
根據該結果，實施例1之污染之防止效果最高，實施例3次之。比較例1及2中TiO2微粒子之殘留量較多，污染之防止效果較低。於比較例2之使用陰離子性界面活性劑之情形時，推測於利用鼓風進行之乾燥步驟中，由於陰離子性界面活性劑與玻璃製品之表面無相互作用，因此於將水去除之同時，其大部分被去除，成為與未設保護膜之比較例1同等之結果。 From this result, the pollution prevention effect of Example 1 was the highest, and Example 3 was the next. In Comparative Examples 1 and 2, the residual amount of TiO 2 fine particles was large, and the effect of preventing pollution was low. In the case of using an anionic surfactant in Comparative Example 2, it is presumed that during the drying step using a blast, the anionic surfactant does not interact with the surface of the glass product. Therefore, while removing water, the Most of them were removed, and the result was equivalent to that of Comparative Example 1 without a protective film.
以成為100μg/ml之方式將聚矽氧油(聚二甲基矽氧烷：分子量約4200)溶解於丙酮中，使該溶液含浸於間隔紙並乾燥，製備為4μg/cm2 之附著量。使該含浸有聚矽氧油之間隔紙與實施例及比較例之玻璃製品交替相隔，將整體用彈簧夾夾持而製成試樣束。將其於50℃、濕度80%之環境下保持20小時，使聚矽氧油轉印至玻璃製品之表面。於將市售之鹼性洗劑原液(Parker Corporation公司製造，商品名：PK-LCG211)稀釋100倍而成之鹼洗液中進行30秒28kHz下之超音波清洗，進而使用聚乙烯醇製海綿，利用相同之鹼洗液手工擦洗3分鐘、約200次。於剛轉印後、超音波清洗後、手工擦洗後測定接觸角，將其結果示於圖3。雖然接觸角並非定量表示聚矽氧油之附著量者，但大小關係可定性評價附著量。關於與剛轉印後相比之手工擦洗後之接觸角之變化率，實施例1為39%，實施例2為68%，實施例3為35%，實施例4為31%，比較例1為91%，比較例2為89%。 Polysiloxane oil (polydimethylsiloxane: molecular weight of about 4200) was dissolved in acetone so that the solution was impregnated with spacer paper and dried to obtain an adhesion amount of 4 μg / cm 2 . The spacer paper impregnated with the silicone oil was alternately separated from the glass products of Examples and Comparative Examples, and the whole was clamped with a spring clip to form a sample bundle. Keep it at 50 ° C and 80% humidity for 20 hours to transfer the silicone oil to the surface of the glass product. Ultrasonic cleaning was performed at 28 kHz for 30 seconds in an alkaline lotion obtained by diluting a commercially available alkaline lotion stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) 100 times, and then using a polyvinyl alcohol sponge Use the same alkaline lotion to scrub by hand for 3 minutes, about 200 times. The contact angle was measured immediately after transfer, after ultrasonic cleaning, and after manual scrubbing, and the results are shown in FIG. 3. Although the contact angle does not quantitatively indicate the adhesion amount of silicone oil, the magnitude relationship can qualitatively evaluate the adhesion amount. Regarding the change rate of the contact angle after manual scrubbing compared with immediately after the transfer, Example 1 was 39%, Example 2 was 68%, Example 3 was 35%, Example 4 was 31%, and Comparative Example 1 It was 91% and Comparative Example 2 was 89%.
於測定對象之玻璃基板之表面滴1滴純水，基於自基板側面拍攝其表面之水滴而得之資料，將5點之測定結果平均而算出各基板與純水之接觸角。 One drop of pure water was dropped on the surface of the glass substrate to be measured, and based on data obtained by photographing water droplets on the surface of the substrate from the side of the substrate, the measurement results at five points were averaged to calculate the contact angle between each substrate and the pure water.
根據該結果，實施例4之污染之防止效果最高，實施例3次之。比較例1及2中聚矽氧油之殘留量較多，污染之防止效果較低。於比較例2之使用陰離子性界面活性劑之情形時，認為於利用鼓風進行之乾燥步驟中，由於陰離子性界面活性劑與玻璃製品之表面無相互作用，因此於去除水之同時，其大部分被去除。因此，推測成為與未設保護膜之比較例1同等之結果。 From this result, the pollution prevention effect of Example 4 was the highest, and Example 3 was the next. In Comparative Examples 1 and 2, the residual amount of the silicone oil was large, and the effect of preventing pollution was low. In the case of using an anionic surfactant in Comparative Example 2, it is considered that, in the drying step using a blast, there is no interaction between the anionic surfactant and the surface of the glass product. Partially removed. Therefore, it is estimated that it is a result equivalent to the comparative example 1 in which a protective film was not provided.
本發明之附有保護膜之玻璃製品及其製造方法可廣泛應用於玻璃製品中，可有效防止玻璃製品表面之污染，尤其是對用於平板顯示器(FPD)等液晶顯示器之製造等之玻璃基板而言較佳。 The glass product with a protective film of the present invention and the manufacturing method thereof can be widely used in glass products, which can effectively prevent the surface of the glass product from being polluted, especially for glass substrates used in the manufacture of liquid crystal displays such as flat panel displays (FPD). It ’s better.
1‧‧‧附有保護膜之玻璃製品 1‧‧‧ Glass products with protective film
2‧‧‧玻璃製品 2‧‧‧ glass products
3‧‧‧保護膜 3‧‧‧ protective film
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW593187B (en) * | 1999-10-25 | 2004-06-21 | Nippon Sheet Glass Co Ltd | Method for preparing article covered with light absorption pattern film and article covered with light absorption pattern film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5432521A (en) * | 1977-08-17 | 1979-03-09 | Asahi Denka Kogyo Kk | Method of protecting glass |
| GB2028165A (en) * | 1978-08-17 | 1980-03-05 | Pilkington Brothers Ltd | Treatment of flat glass |
| JPS5567542A (en) * | 1978-11-10 | 1980-05-21 | Nippon Oil & Fats Co Ltd | Lubrication treating method for glass container |
| US6379746B1 (en) * | 1999-02-02 | 2002-04-30 | Corning Incorporated | Method for temporarily protecting glass articles |
| JP5465184B2 (en) * | 2008-01-24 | 2014-04-09 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for preparing superhydrophilic layer |
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2014
- 2014-03-31 KR KR1020157025585A patent/KR20150138192A/en not_active Application Discontinuation
- 2014-03-31 JP JP2015510073A patent/JP6132013B2/en not_active Expired - Fee Related
- 2014-03-31 WO PCT/JP2014/059411 patent/WO2014163034A1/en active Application Filing
- 2014-03-31 TW TW103112007A patent/TWI617522B/en not_active IP Right Cessation
- 2014-03-31 CN CN201480018971.7A patent/CN105102391B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW593187B (en) * | 1999-10-25 | 2004-06-21 | Nippon Sheet Glass Co Ltd | Method for preparing article covered with light absorption pattern film and article covered with light absorption pattern film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2014163034A1 (en) | 2017-02-16 |
| KR20150138192A (en) | 2015-12-09 |
| WO2014163034A1 (en) | 2014-10-09 |
| JP6132013B2 (en) | 2017-05-24 |
| TW201446687A (en) | 2014-12-16 |
| CN105102391B (en) | 2017-12-12 |
| CN105102391A (en) | 2015-11-25 |
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| Date | Code | Title | Description |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |