WO2016122059A1 - Structure en verre comportant une couche de dureté élevée et résistant aux empreintes, et son procédé de revêtement - Google Patents

Structure en verre comportant une couche de dureté élevée et résistant aux empreintes, et son procédé de revêtement Download PDF

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Publication number
WO2016122059A1
WO2016122059A1 PCT/KR2015/006984 KR2015006984W WO2016122059A1 WO 2016122059 A1 WO2016122059 A1 WO 2016122059A1 KR 2015006984 W KR2015006984 W KR 2015006984W WO 2016122059 A1 WO2016122059 A1 WO 2016122059A1
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WIPO (PCT)
Prior art keywords
layer
glass
fingerprint
high hardness
glass structure
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PCT/KR2015/006984
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English (en)
Korean (ko)
Inventor
김영수
Original Assignee
주식회사 맥스젠테크놀로지
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Publication of WO2016122059A1 publication Critical patent/WO2016122059A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions

Definitions

  • the present invention relates to a high hardness glass structure and a coating method having an anti-fingerprint layer, and more particularly to a coating method for a glass structure and a glass structure having a high hardness and anti-fingerprint layer to be implemented in a touch screen panel.
  • Conventional glass structures use non-tempered glass, chemically tempered glass or ordinary tempered glass.
  • Chemical tempered glass is a glass tempered in a high temperature KNO 3 tempered liquid of about 400 to about 600 degrees for 2 to 12 hours.
  • general tempered glass hardens the surface by quenching the glass at a high temperature of about 400 to 600 degrees.
  • Such glass structures are widely applied to touch screen panels of mobile devices such as mobile phones, smart phones, tablets, and terminals of information processors such as ATMs, kiosks, monitors, and TVs.
  • the glass structure has been applied to display surfaces such as LCD, PDP, OLED, QHD, including a touch screen panel.
  • the surface of the glass structure of the touch screen panel is coated with an anti-fingerprint material to prevent scratches or fingerprints from forming.
  • the glass structure applied to the touch screen panel is required to have high strength and anti-fingerprint.
  • the anti-fingerprint layer of the conventional glass structure may be coated with a fluorine resin or a silicone resin by a wet or dry method on the surface of the glass.
  • a fingerprint layer is formed by coating a deposition layer made of silica (SiO 2 ) and a fluorine resin or a silicone resin on the deposition layer.
  • coating the anti-fingerprint layer on the glass has an anti-fingerprint function as well as a slip function, thereby improving scratch resistance somewhat. Nevertheless, scratches occur on the display surface having the anti-fingerprint layer or to which tempered glass is applied, and are easily broken by an impact. Accordingly, unreinforced glass or tempered glass having stronger scratch resistance properties is required.
  • conventional non-reinforced glass and tempered glass is low in hardness, there is a limit to preventing scratches.
  • FIG. 1 is a flow chart showing a method of manufacturing a non-tempered glass or tempered glass with a conventional fingerprint layer. At this time, non-tempered glass or tempered glass is collectively called glass.
  • a glass-mounted jig is charged into an evaporator (S1).
  • foreign matter such as dust adhering to the surface of the glass is removed.
  • vacuum deposition forms a silica layer (SiO 2 layer) on the surface of the glass (S2).
  • deposition conditions such as chamber location, deposition thickness, and the like, are preset and supplement the chemicals required for the chamber.
  • the anti-fingerprint layer is formed on the silica layer by vacuum deposition (S3).
  • an electron beam deposition method is generally used. Specifically, after silica (SiO 2 ) is deposited on the glass, an anti-fingerprint layer is formed on the deposition surface by ECC (Easy Cleaning Coating). However, if there is no silica layer in the glass structure, the bonding strength between the glass and the anti-fingerprint layer is not strong and durability is poor. If the bonding force is low, the hardness decreases, and a sharp material may cause scratches on the surface of the glass structure.
  • ECC Electronic Cleaning Coating
  • the problem to be solved by the present invention is a strong bond between the high hardness layer and the fingerprint layer, the hardness of the high hardness layer is relatively high compared to the conventional non-reinforced glass or tempered glass or silica layer, fingerprints to prevent the occurrence of scratches It is to provide a high hardness glass structure having a protective layer and a coating method for the same.
  • the high hardness glass structure having an anti-fingerprint layer for solving the problems of the present invention includes an unreinforced glass or tempered glass and a base layer in which an alumina layer, a lower silica layer, a silicon carbide layer, and a zirconium layer are sequentially positioned on the glass. do.
  • it comprises a top silica layer located on the base layer and the anti-fingerprint layer located on the top silica layer.
  • the thickness of the base layer is preferably 100 kPa to 1,000 kPa, and preferably 350 kPa to 650 kPa.
  • the silicon carbide layer and the zirconium layer may be repeatedly formed.
  • zirconium carbide may be formed at an interface between the silicon carbide layer and the zirconium layer.
  • the thickness ratio of the alumina layer, the lower silica layer, the silicon carbide layer and the zirconium layer is preferably 40 to 60:10 to 30:10 to 25:10 to 25.
  • the upper silica layer may have a thickness of 50 kPa to 200 kPa.
  • the method of manufacturing a high hardness glass structure having an anti-fingerprint layer for solving other problems of the present invention first removes foreign substances on the glass surface. Thereafter, a base layer on which the alumina layer, the lower silica layer, the silicon carbide layer, and the zirconium layer are sequentially deposited is deposited on the surface of the glass from which the foreign matter is removed. A top silica layer is deposited on the base layer. Depositing an anti-fingerprint layer on the upper silica layer.
  • the foreign matter can be removed by the ion gun.
  • the base layer and the upper silica layer may be deposited by an electron beam method.
  • the anti-fingerprint layer may be deposited with a coating material including a fluorine series or a silicon series.
  • the bonding strength of the high hardness layer and the anti-fingerprint layer is increased. It is solid and the hardness of the high hardness layer is relatively high. In addition, by increasing the hardness, it is possible to prevent the occurrence of scratches by sharp materials.
  • 1 is a flowchart illustrating a method of manufacturing a tempered glass including a conventional anti-fingerprint layer.
  • FIG. 2 is a cross-sectional view showing a high hardness glass structure having an anti-fingerprint layer according to the present invention.
  • FIG. 3 is a flow chart for explaining a method of manufacturing a high hardness glass structure having an anti-fingerprint layer according to the present invention.
  • Embodiment of the present invention by applying a high hardness layer laminated a silica layer on a base layer including a silicon carbide layer and a zirconium layer, the bonding strength of the high hardness layer and the fingerprint layer is firm, the hardness of the high hardness layer is relatively High hardness glass structures and coating methods are presented. To this end, the structure of the base layer and the high hardness layer will be described in detail. In addition, the hardness of the glass structure in which the fingerprint layer is formed on the high hardness layer will be described in detail. Glass in the embodiment of the present invention includes unreinforced glass and tempered glass. Tempered glass is divided into chemical tempered glass and general tempered glass.
  • the high hardness glass structure of the present invention may be applied to windows and window protection films attached to a touch screen or a display.
  • the present invention may be applied to a display window, a touch surface of a touch screen panel, a window of a touch screen panel, a display for protection, or a window of a touch screen.
  • it can be applied to a table, a dining table, a blackboard, a glass wall, a building structure, a decoration, and the like with a touch screen or a display.
  • the glass structure of the high hardness of the present invention can be used in a touch screen or a vehicle glass with a display, household appliances glass and the like.
  • the glass structure of the present invention may serve as a protective film attached to the window on the touch screen.
  • FIG. 2 is a cross-sectional view showing a high hardness glass structure having an anti-fingerprint layer according to an embodiment of the present invention.
  • a cross-sectional view of a strict meaning is not represented, and there may be elements that may not appear on the cross-section for convenience of description.
  • a high hardness layer 40 and an anti-fingerprint layer 50 composed of a base layer 20 and an upper silica layer 30 are sequentially stacked on a transparent glass 10.
  • the base layer 20 increases adhesion to the glass 10, improves abrasion resistance, and maintains high hardness.
  • the base layer 20 consists of an alumina layer 21, a lower silica layer 22, a silicon carbide layer 23, and a zirconium layer 24.
  • the alumina layer 21 enhances the adhesion with the glass 10 and maintains high hardness.
  • Alumina is a high hardness material with a Mohs hardness of nine.
  • the lower silica layer 22 serves as a crosslinking agent for adhesion between the alumina layer 21 and the silicon carbide layer 23.
  • the silicon carbide layer 23 has a very high hardness of Mohs hardness of 9 to 9.5, has good abrasion resistance and low thermal expansion rate, thereby increasing the bonding force with the lower silica layer 22 and stabilizing the deposition of the zirconium layer 24.
  • Zirconium carbide (ZrC) is formed at the interface between the silicon carbide layer 23 and the zirconium layer 24.
  • Zirconium carbide (ZrC) is made by covalent bonding of zirconium and carbon (C), has a Mohs hardness of 8-9.
  • Zirconium carbide (ZrC) improves the interfacial stability of the silicon carbide layer 23 and the zirconium layer 24 on both sides. In other words, zirconium carbide increases the bonding force between the silicon carbide layer 23 and the zirconium layer 24 and stabilizes the deposited zirconium layer 24.
  • the thickness ratio of the alumina layer 21, the lower silica layer 22, the silicon carbide layer 23, and the zirconium layer 24 is 40 to 60:10 to 30:10 to 25:10. It is good to be -25. Such a thickness ratio is an optimal value considering the function of each layer and the wear resistance of the high hardness layer 40.
  • the thickness of the base layer 20 constituting the high hardness layer 40 is preferably 100 kPa to 1,000 kPa, more preferably 350 kPa to 650 kPa. If the thickness of the base layer 20 is less than 100 kPa, the effect of increasing the hardness is difficult to implement.
  • the thickness of the base layer 20 is greater than 1,000 mm, the distance from the surface of the glass structure is too far, the touch may not be properly recognized. In addition, if the thickness becomes too thick, when the glass structure is bent, the structure of the base layer 20 may be broken.
  • the silicon carbide layer 23 and the zirconium layer 24 according to the embodiment of the present invention may be repeatedly formed. That is, the wear resistance of the glass structure can be further improved by repeating the silicon carbide layer 23 and the zirconium layer 24.
  • the production of zirconium carbide a multilayer silicon carbide layer 23 and a zirconium layer 24 having stable interfaces can be obtained.
  • the number of repeating layers can be set in consideration of the use and environment in which the glass structure of the present invention is used.
  • the upper silica layer 30 is a layer for improving the bonding strength between the base layer 20 and the anti-fingerprint layer 50, and to increase the hardness of the glass structure of the present invention. 50 kPa to 200 kPa of the upper silica layer 30 is preferable. If the thickness of the upper silica layer 30 is less than 50 ⁇ , it is difficult to implement the effect of increasing the hardness and improve the adhesion. If the thickness of the upper silica layer 30 is larger than 200 mm 3, the thickness of the glass structure becomes too large. If the thickness is too large, it may cause an error in the operation of the touch panel.
  • the anti-fingerprint layer 50 has anti-fingerprint and antifouling properties, and mainly consists of fluorine or silicon. The anti-fingerprint layer 50 helps slip and scratch prevention. The thickness of the anti-fingerprint layer 50 is preferably 100 to 200 kPa.
  • FIG. 3 is a flowchart illustrating a method of manufacturing a high hardness glass structure having an anti-fingerprint layer according to an embodiment of the present invention.
  • the structure of the glass structure will be referred to FIG. 2.
  • the glass structure of the present invention in order to manufacture the glass structure of the present invention, first, foreign substances adhering to the surface of the glass 10 are removed (S10). That is, the glass 10 is placed on a jig to fix the glass 10. In the state where the glass 10 is fixed, a foreign substance or moisture adhering to the surface of the glass 10 is sufficiently removed using, for example, an ion gun. In addition, the ion gun activates the surface of the glass 10 so that the deposition in the deposition step described later is performed well.
  • the ion beam generated by the ion gun refers to a flow of ions that make a gas in a neutral state mixed with a positive charge and a negative charge, and extracts it by creating an external environment such as a potential difference or a pressure difference. At this time, the energy of the ion gun is set so that the surface etching of the glass 10 does not occur to an undesired degree.
  • the base layer 20 is deposited on the glass 10 using an electron beam method or a plasma method (S20). Specifically, when the glass 10 and the deposition material are mounted inside the vacuum chamber, and the vacuum evaporator is operated under the deposition conditions including the deposition thickness, the deposition source is vaporized while the electron beam strikes alumina, which is the deposition source. At this time, in the vaporized deposition source, the alumina layer 21, the lower silica layer 22, the silicon carbide layer 23, and the zirconium layer 24 are sequentially formed. Next, the upper silica layer 30 is deposited on the base layer 20 (S30). In this way, the high hardness layer 40 is formed in the glass 10.
  • the anti-fingerprint layer 50 is formed on the high hardness layer 40 by using a coating material containing fluorine-based or silicon-based (S40).
  • the anti-fingerprint layer 50 uses a water repellent principle that the water contact angle is about 110 to 116 °. This is to use a principle similar to antifouling processing so that fingerprints and contaminants, etc. are less burying the surface of the glass structure of the present invention.
  • the anti-fingerprint deposition as in the embodiment of the present invention the anti-fingerprint effect is significantly improved compared to the conventional anti-fingerprint coating or super water-repellent coating.
  • the high hardness glass structure having the anti-fingerprint layer 50 is inspected for reliability and appearance, such as a contact angle measurement test.
  • the glass structure that passed the inspection is attached to the protective film through a laminating process on the surface of the fingerprint layer (S50).
  • High hardness glass structure having an anti-fingerprint layer is a high hardness layer 40 composed of a base layer 20 and the upper silica layer 30 between the glass 10 and the anti-fingerprint layer 50. Deposit. This improves the durability, reliability and corrosion resistance of the anti-fingerprint layer 20 by a series of processes called deposition. In addition, since both the high hardness layer 40 and the anti-fingerprint layer 50 are formed by vapor deposition, the process can be simplified. Thereby, the yield in production of the glass structure of this invention can be improved.
  • Table 1 represents the hardness measurement results according to the thickness of the base layer according to the conventional and embodiments of the present invention.
  • the high hardness layer of the present invention was formed by vacuum deposition at a deposition temperature of 150 °C.
  • Comparative Example 1 was a chemically strengthened glass structure without a conventional high hardness layer
  • Comparative Example 2 was a chemically strengthened glass structure formed with a conventional anti-fingerprint layer and a silica layer
  • the embodiment has an anti-fingerprint layer and a high hardness layer of the present invention It was a chemically strengthened glass structure.
  • Hardness was processed by carbon steel (SM45C) into a pencil shape, and confirmed by scratching the glass structure by the same method as the pencil hardness measurement method.
  • the glass sample is a chemically toughened glass from Corning, USA.
  • (circle) is a state without a scratch at all
  • x represents the state in which a scratch exists.
  • the deposition thickness when the deposition thickness was 200 kPa and 300 kPa, the scratch occurred when the carbon steel measurement hardness was larger than 600 g.
  • the deposition thickness was 400 kPa to 600 kPa, no scratch occurred even when the carbon steel measurement hardness was 1,000 g. That is, it was found that the deposition thickness has the highest hardness at 350 kPa to 650 kPa.
  • the deposition thickness of 700 kPa and 800 kPa no scratch was observed even though the carbon steels measured hardness were 900 g and 800 g, respectively.
  • the deposition thickness of 900 ⁇ was similar to that of 200 ⁇ and 300 ⁇ .
  • the deposition thickness by the Example of this invention deviated from 350 kPa-650 kPa, it had hardness higher than the comparative examples 1 and 2 of the conventional. Accordingly, even if the deposition thickness of the embodiment of the present invention is 100 kPa to 1,000 kPa, since it has a higher hardness than the conventional one, it can be used as a glass structure. More preferably, it was a glass structure with optimum hardness when it was 350 kPa-650 kPa.
  • the glass structure according to the embodiment of the present invention increases adhesion to glass with an alumina layer, improves abrasion resistance with a silicon carbide layer and a zirconium layer, and enhances bonding strength with an anti-fingerprint layer with a silica layer. Accordingly, the bonding force between the high hardness layer and the fingerprint prevention layer is robust.
  • a zirconium layer it is possible to increase the hardness of the non-tempered glass or tempered glass compared with the conventional.
  • the manufacturing process is simple because it is produced continuously by vapor deposition.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une structure en verre comportant une couche de dureté élevée et résistant aux empreintes, et son procédé de revêtement, dans laquelle une couche de dureté élevée et une couche résistant aux empreintes sont solidement liées, la couche de dureté élevée ayant une dureté supérieure comparativement à une couche classique. La structure et le procédé comprennent : une couche de base comprenant une couche d'alumine, une couche de silice inférieure, une couche de carbure de silicium et une couche de zirconium stratifiées dans cet ordre sur un verre non trempé ou un verre trempé ; une couche de silice supérieure agencée sur la couche de base ; et une couche résistant aux empreintes agencée sur la couche de silice supérieure, la couche de base et la couche de silice supérieure formant une couche de dureté élevée, et la couche de base, la couche de silice supérieure et la couche résistant aux empreintes étant formées par dépôt.
PCT/KR2015/006984 2015-01-26 2015-07-07 Structure en verre comportant une couche de dureté élevée et résistant aux empreintes, et son procédé de revêtement WO2016122059A1 (fr)

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KR10-2015-0011812 2015-01-26
KR1020150011812A KR101630450B1 (ko) 2015-01-26 2015-01-26 지문방지층을 가진 고경도의 유리 구조체 및 이를 위한 코팅방법

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Cited By (4)

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CN109280887A (zh) * 2017-07-20 2019-01-29 深圳市诺真空科技有限公司 一种防指纹膜的镀膜方法
CN109279917A (zh) * 2017-07-20 2019-01-29 深圳市诺真空科技有限公司 一种陶瓷表面的镀膜方法
CN113862611A (zh) * 2021-09-30 2021-12-31 台州星星光电科技有限公司 一种抗强碱的蓝宝石玻璃面板表面的镀膜方法
CN115678447A (zh) * 2022-10-09 2023-02-03 箭牌家居集团股份有限公司 易洁卷材及其制备方法

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KR101932359B1 (ko) 2017-11-30 2018-12-24 유흥상 블루라이트 차폐 코팅층이 형성되는 스마트폰 보호필름 및 그 형성방법
WO2019107995A1 (fr) * 2017-11-30 2019-06-06 유흥상 Verre protecteur et film protecteur pour smartphone avec couche de revêtement bloquant la lumière bleue formée sur celui-ci, et son procédé de formation

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN109280887A (zh) * 2017-07-20 2019-01-29 深圳市诺真空科技有限公司 一种防指纹膜的镀膜方法
CN109279917A (zh) * 2017-07-20 2019-01-29 深圳市诺真空科技有限公司 一种陶瓷表面的镀膜方法
CN113862611A (zh) * 2021-09-30 2021-12-31 台州星星光电科技有限公司 一种抗强碱的蓝宝石玻璃面板表面的镀膜方法
CN115678447A (zh) * 2022-10-09 2023-02-03 箭牌家居集团股份有限公司 易洁卷材及其制备方法
CN115678447B (zh) * 2022-10-09 2023-09-05 箭牌家居集团股份有限公司 易洁卷材及其制备方法

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