WO2013089178A1 - 電子機器用カバーガラス及びその製造方法、並びにタッチセンサモジュールの製造方法 - Google Patents

電子機器用カバーガラス及びその製造方法、並びにタッチセンサモジュールの製造方法 Download PDF

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Publication number
WO2013089178A1
WO2013089178A1 PCT/JP2012/082321 JP2012082321W WO2013089178A1 WO 2013089178 A1 WO2013089178 A1 WO 2013089178A1 JP 2012082321 W JP2012082321 W JP 2012082321W WO 2013089178 A1 WO2013089178 A1 WO 2013089178A1
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Prior art keywords
glass
glass substrate
antifouling coating
coating layer
layer
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PCT/JP2012/082321
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English (en)
French (fr)
Japanese (ja)
Inventor
下川　貢一
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Hoya株式会社
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Application filed by Hoya株式会社 filed Critical Hoya株式会社
Priority to CN201280060645.3A priority Critical patent/CN103974919B/zh
Priority to JP2013506389A priority patent/JP5270810B1/ja
Publication of WO2013089178A1 publication Critical patent/WO2013089178A1/ja

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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
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/006—Other surface treatment of glass not in the form of fibres or filaments by irradiation by plasma or corona discharge

Definitions

  • the present invention provides a protection device for a display screen of a mobile device such as a mobile phone, a portable game machine, a PDA (Personal Digital Assistant), a digital still camera, a video camera, or a slate PC (Personal Computer), or a protective member for a display screen.
  • a mobile device such as a mobile phone, a portable game machine, a PDA (Personal Digital Assistant), a digital still camera, a video camera, or a slate PC (Personal Computer), or a protective member for a display screen.
  • the present invention relates to a cover glass for an electronic device that is provided in a laminated manner and is used as a further protective member, a method for manufacturing the same, and a method for manufacturing a touch sensor module.
  • a cover glass made of such a glass material is generally manufactured by the following process.
  • the glass material formed into a sheet is cut into a predetermined size by machining (cutting) or etching, and a glass substrate for cover glass is produced.
  • necessary drilling or outer peripheral shape processing is performed on the glass substrate by machining or etching.
  • This chemical strengthening treatment is a treatment method in which sodium Na + in glass is exchanged with potassium K + having a large ionic radius to form a compressive stress layer on the glass surface.
  • the cover glass is required to have high strength because of impact and pressure.
  • desired printing or the like is performed on the surface of the glass substrate subjected to the above chemical strengthening treatment.
  • the cover glass thus completed is incorporated into a portable device.
  • the display screen is directly touched and operated, so that dirt such as fingerprints tends to adhere to the cover glass that protects the display screen. Therefore, it is desirable to prevent or suppress the dirt such as fingerprints from adhering to the cover glass, or to easily wipe off even if dirt such as fingerprints adheres. Therefore, the surface of the cover glass is usually subjected to an antifouling coating treatment.
  • Patent Document 1 discloses such antifouling coating treatment.
  • Patent Document 1 discloses that the antifouling coating treatment is performed by a vapor deposition method or an immersion method.
  • the antifouling coating treatment is performed by the vapor deposition method or the dipping method, the adhesion between the glass substrate and the antifouling coating material is insufficient depending on the surface roughness of the surface of the glass substrate, and the antifouling coating layer. In some cases, the desired durability could not be obtained.
  • Patent Document 1 discloses an antifouling coating treatment by a dip method (dipping method).
  • the antifouling coating surface formed by the dip method is inferior in durability to the antifouling coating surface formed by the vapor deposition method. It turned out that there was a problem.
  • the present invention has been made to solve such a conventional problem, and an object of the present invention is to provide a cover glass for an electronic device that can remarkably improve the durability as compared with a conventional antifouling coating surface by a dip method. And a method of manufacturing the same. Another object is to provide an electronic device cover glass and a method for manufacturing the same, which can improve productivity as compared with an antifouling coating treatment by a vapor deposition method. Furthermore, another object is to provide a method for manufacturing a touch sensor module including a glass substrate with improved durability of the antifouling coating surface and improved adhesion stability of a transparent conductive layer or the like.
  • the present inventor has intensively studied to solve the above problems, and as a result, the following contents have been found regarding the durability of the antifouling coating surface.
  • the surface properties of the glass substrate subjected to the antifouling coating treatment when the skewness (Rsk: skewness) of the contour curve of the glass substrate surface is relatively far from 0, the unevenness of the unevenness of the glass substrate surface is large.
  • the adhesion stability of the antifouling coating layer applied to the glass substrate to the glass substrate was low. And it became clear that this adhesion stability has influenced the durability of the antifouling coating surface.
  • the glass substrate surface is modified so that the skewness (Rsk: skewness) of the contour curve of the glass substrate surface approaches zero by performing a planar plasma treatment on the glass substrate. It was confirmed that the unevenness of the uneven shape on the surface of the glass substrate was reduced. As a result, it was confirmed that the adhesion stability of the antifouling coating layer to the glass substrate was increased.
  • the present inventor sufficiently adheres the antifouling coating layer to the glass substrate by performing the glass surface modification treatment for performing the planar plasma processing and the downstream plasma processing in that order on the glass substrate. I found that it can be enhanced. And the inventor found that the durability of the antifouling coating surface can be improved by sufficiently increasing the adhesion stability of the antifouling coating layer to the glass substrate, that is, the above problem can be solved, and the present invention It came to complete. Moreover, even when a highly productive dip method is used for the coating method, the adhesion stability of the antifouling coating layer to the glass substrate can be sufficiently increased, and the durability of the antifouling coating surface can be improved. I found a possible point.
  • the present invention has the following configuration.
  • (Configuration 1) A method of manufacturing a cover glass for an electronic device comprising a glass substrate having a pair of main surfaces and an end surface adjacent to the pair of main surfaces, wherein one main surface of the pair of main surfaces of the glass substrate A glass surface modification treatment for performing a planar plasma treatment and a downstream plasma treatment in that order to form a glass treated surface, and a step of forming the glass treated surface, And a step of forming an antifouling coating layer on the treated surface.
  • the antifouling coating layer is formed on the entire outer surface of the glass substrate including the glass treated surface by immersing the entire glass substrate in an antifouling coating material. It is a manufacturing method of the cover glass for electronic devices of the structure 1. (Configuration 3) The antifouling coat layer formed on the other main surface of the pair of main surfaces is subjected to an antifouling coat surface modification treatment that reduces the contact angle of water on the surface, and the antifouling coat modification is performed. It is a manufacturing method of the cover glass for electronic devices of the structure 1 or 2 characterized by including the process of forming a layer.
  • a cover glass for an electronic device comprising a glass substrate having a pair of main surfaces and an end surface adjacent to the pair of main surfaces, wherein Rsk of one main surface of the pair of main surfaces is 0 ⁇ 0. 3 and an antifouling coating layer is formed on the one main surface, and # 0000 steel wool is slid 2000 times at a surface pressure of 1 kg / cm 2 on the surface of the antifouling coating layer.
  • a cover glass for electronic equipment, wherein when contacted, the contact angle of water on the surface of the antifouling coating layer is 105 degrees or more.
  • the antifouling coating layer is a cover glass for an electronic device according to Configuration 7, wherein the antifouling coating layer has an adhesion region attached to the surface of the glass substrate and a flow region disposed on the surface of the adhesion region. .
  • (Configuration 9) 9. The cover glass for an electronic device according to Configuration 8, wherein a ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer is 40% to 70%.
  • the contact angle of hexadecane on the surface opposite to the glass substrate of the antifouling coating layer formed on the one main surface is in the range of 60 degrees to 70 degrees, and is formed on the other main surface.
  • the cover glass for electronic equipment according to constitution 10 wherein the contact angle of hexadecane on the surface opposite to the glass substrate of the antifouling coating modified layer is in the range of 10 to 20 degrees. It is.
  • the dynamic friction coefficient on the surface opposite to the glass substrate of the antifouling coating layer formed on the one main surface is in the range of 0.1 to 0.3. It is the cover glass for electronic devices in any one of. (Configuration 13) 13.
  • (Configuration 14) 14 The cover glass for electronic equipment according to any one of Structures 7 to 13, wherein the antifouling coating layer is made of a fluorine resin material having a weight average molecular weight of 2000 to 5000.
  • the glass substrate is a cover glass for an electronic device according to any one of Structures 7 to 14, wherein the glass substrate is made of chemically strengthened aluminosilicate glass.
  • a method for manufacturing a touch sensor module comprising a glass substrate having a pair of main surfaces and end faces adjacent to the pair of main surfaces, wherein the operation of the touch sensor module is detected.
  • One of the main surfaces is formed with a glass surface to be treated by performing a glass surface modification treatment in the order of a planar plasma treatment and a downstream plasma treatment, and the glass includes the glass treated surface.
  • the glass substrate having an antifouling coating layer formed on the entire outer surface of the substrate a contact angle of water on the surface of the antifouling coating layer is reduced on the other main surface of the pair of main surfaces.
  • the cover glass for electronic devices which can improve durability remarkably compared with the antifouling coating surface by the conventional dip method, and its manufacturing method can be provided. Moreover, according to this invention, the cover glass for electronic devices which can improve productivity compared with the antifouling coating process by a vapor deposition method, and its manufacturing method can be provided. Furthermore, according to this invention, the manufacturing method of a touch sensor module provided with the glass substrate which improved durability of the antifouling coating surface and improved adhesion stability, such as a transparent conductive layer, can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a cover glass for portable equipment which is an embodiment of the cover glass for electronic equipment according to the present invention.
  • a cover glass 10 for a portable device according to the present invention includes a flat glass substrate 1.
  • the glass substrate 1 has a pair of front and back main surfaces 1A and 1B and an end face 1C adjacent to the pair of main surfaces.
  • a glass surface to be processed is formed by performing glass surface modification treatment.
  • the antifouling coating layer 3 is formed in the said glass to-be-processed surface and the said end surface 1C.
  • One of the characteristic configurations in the present invention is that a glass processing surface is formed on the one main surface 1A, and the glass processing surface is subjected to planar plasma processing and downstream plasma processing in this order. It is formed by performing the glass surface modification process to be performed.
  • the antifouling coating layer 3 is formed on the one main surface 1A on which the glass surface modification treatment is performed and the glass treated surface is formed. Yes.
  • the adhesion stability of the antifouling coating material to the glass substrate is improved as compared with a conventional antifouling coating layer formed by the dip method without performing surface treatment or the like on the glass substrate, for example. Durability is significantly improved.
  • a fluorine-based resin material is preferably used as the antifouling coating material. However, when this fluororesin material is applied to a glass substrate by a dip method, the adhesion stability to the glass substrate is particularly bad.
  • the adhesion stability to the glass substrate is improved and the durability of the antifouling coating surface is remarkably improved.
  • the present invention which can be made is particularly suitable. The details of the glass surface modification treatment in which the planar plasma treatment and the downstream plasma treatment are performed in this order will be described later.
  • the material of the antifouling coating layer 3 will be described.
  • the display screen is directly touched with a finger to operate, and thus a fingerprint or the like is likely to adhere to the display screen. Therefore, it is desirable to prevent or suppress the fingerprints and the like from adhering to the display screen, or to easily wipe off even if the fingerprints and the like are attached.
  • a material of the antifouling coating layer 3 even if it is directly touched (pressed) with a finger, it prevents or suppresses dirt such as fingerprints from being attached or easily wipes off even if dirt such as fingerprints adheres. It is preferable to select a material having antifouling properties. It is also important to have excellent transparency.
  • the surface energy of a fluorine resin material (for example, a perfluoropolyether compound having a hydroxyl group at a terminal group) is used as a material having good antifouling properties and excellent transparency.
  • a material for lowering is preferred.
  • the other main surface 1B of the pair of main surfaces in the glass substrate 1 is subjected to an antifouling coat surface modification process which is a process for reducing the contact angle of the surface with water on the antifouling coat layer 3.
  • the antifouling coat modified layer 3a is formed by applying.
  • An antifouling coating layer 3 is formed on one main surface 1A and the end surface 1C on which the glass treated surface is formed.
  • the entire glass substrate is immersed in the antifouling coating material by dipping.
  • the anti-staining coating layer is also formed on the other main surface 1B.
  • the cover glass 10 for a portable device in FIG. 1 the main surface 1A side of the glass substrate 1 whose durability of the antifouling coating surface is improved is usually outside the portable device, and the other main surface 1B of the glass substrate 1 is used. It is assembled with the side facing the inside of the mobile device.
  • a transparent conductive layer is formed on the main surface 1B side of the glass substrate 1 (via an insulating layer if necessary), and a signal corresponding to the user's operation is provided by the glass substrate 1 and the transparent conductive layer.
  • the antifouling coating layer 3 made of, for example, a fluorine resin material is formed on the main surface 1B side of the glass substrate 1, the insulating layer or the transparent conductive layer is formed on the outer surface of the antifouling coating layer 3.
  • the adhesion stability of is poor. For this reason, it is difficult to form the insulating layer and the transparent conductive layer on the outer surface of the antifouling coating layer 3, and a touch sensor module cannot be formed.
  • the other main surface 1B of the glass substrate 1 is subjected to the antifouling coat surface modification treatment, which is a treatment for reducing the contact angle of the surface with water, on the antifouling coating layer 3.
  • the antifouling coat surface modification treatment is a treatment for reducing the contact angle of the surface with water, on the antifouling coating layer 3.
  • the antifouling coating surface modification treatment include methods such as a helium (He) plasma exposure treatment or an ultraviolet irradiation treatment by a planar method.
  • the cover glass 10 for a portable device water contact on the surface of the antifouling coating layer 3 formed on one main surface 1A of the glass substrate 1 (the surface opposite to the glass substrate 1).
  • the angle is preferably in the range of 110 to 120 degrees, and the contact angle of the oil, such as hexadecane, is preferably in the range of 60 to 70 degrees.
  • the contact angle is an initial contact angle after the antifouling coating layer is formed.
  • the durability of the antifouling coating layer 3 formed on the main surface 1A of the glass substrate 1 is improved. For example, even if a durability test by sliding steel wool described in the examples described later is performed, the contact angle is hardly lowered and good antifouling property can be maintained.
  • the contact angle of water is 20 degrees or less, and the contact angle of oil such as hexadecane is preferably in the range of 10 to 20 degrees.
  • the contact angle with respect to water or oil is within the above range, adhesion stability when the above-described insulating layer or transparent conductive layer is formed on the outer surface of the antifouling coating modified layer 3a can be improved.
  • the contact angle is a value measured in an atmosphere of 22 ⁇ 2 ° C.
  • the dynamic friction coefficient in the surface (surface on the opposite side to the glass substrate 1) of the said antifouling coating layer 3 formed in one main surface 1A of the said glass substrate 1 is demonstrated. Is preferably in the range of 0.1 to 0.3, or the static friction coefficient is preferably in the range of 0.2 to 0.4. Since the surface of the antifouling coating layer 3 has a dynamic friction coefficient or a static friction coefficient within the above range, the antifouling coating surface is slippery and has a good feeling when touched with a finger. In a portable device provided with glass, the operability of a touch panel, for example, by a user is good.
  • the glass constituting the glass substrate 1 is preferably amorphous aluminosilicate glass.
  • a glass substrate made of such an aluminosilicate glass has a high strength after chemical strengthening and is suitable for a cover glass for portable devices.
  • As such an aluminosilicate glass for example, SiO 2 is 58 to 75 wt%, Al 2 O 3 is 4 to 20 wt%, Li 2 O is 0 to 10 wt%, and Na 2 O is 4 to 20 wt%.
  • An aluminosilicate glass containing as a main component can be used.
  • the thickness of the glass substrate 1 is preferably in the range of, for example, about 0.3 mm to 1.5 mm, more preferably from 0.5 mm to 1.5 mm, from the viewpoint of meeting the recent market needs for thinner and lighter portable devices.
  • the range is about 0.7 mm.
  • FIG. 2 is a flowchart of a method for manufacturing a cover glass for a portable device according to the present invention
  • FIG. 3 is a schematic cross-sectional view showing the method for manufacturing the cover glass for a portable device according to the present invention in the order of steps.
  • the cover glass for portable devices according to the present invention is manufactured by a process as described below.
  • a large glass plate is cut into a predetermined size by machining or the like to produce a glass substrate 1 for a cover glass.
  • a large number for example, about several tens
  • the laminated state is cut at a time, the laminated pieces can be shaped at the same time in the next shape processing step, which is advantageous in production.
  • the size of the small piece is determined in consideration of the size of the cover glass of the product plus the margin necessary for processing the outer peripheral shape.
  • the sheet-like glass material may be processed one by one.
  • an etching method may be applied to the outer shape processing as a means other than machining.
  • the glass composition of the glass substrate 1 is as described above.
  • the thickness of the glass substrate 1 is preferably in the range of, for example, about 0.3 mm to 1.5 mm, more preferably from the viewpoint of meeting the recent market needs for thinner and lighter portable devices. Is in the range of about 0.5 mm to 0.7 mm.
  • FIG. 4 is a plan view showing an example of the shape of the glass substrate.
  • the glass substrate 1 has an outer peripheral end face 1a, a notch 1b, an ear hole 1c, and a key operation hole 1d.
  • Such drilling and outer peripheral shape processing may be machined by sandblasting or the like, or these drilling processing and outer peripheral shape processing may be collectively performed by etching.
  • etching is advantageous for complex shape processing.
  • you may use together machining and an etching process according to a process shape.
  • the sheet-like glass material may be made into small pieces by appropriately setting the dissolution pattern during the etching process, and in the same process as this small piece, the small pieces may have the shape of the glass substrate 1 shown in FIG. .
  • a chemical strengthening process is performed on the glass substrate 1 that has undergone the shape processing.
  • a method of chemical strengthening treatment for example, a low temperature ion exchange method in which ion exchange is performed in a temperature range that does not exceed the temperature of the glass transition point, for example, a temperature of 300 ° C. to 500 ° C. is preferable.
  • the chemical strengthening treatment is a process in which a molten chemical strengthening salt is brought into contact with a glass substrate, whereby an alkali metal element having a relatively large atomic radius in the chemical strengthening salt and a relatively small atomic radius in the glass substrate.
  • alkali metal nitric acid such as potassium nitrate or sodium nitrate can be preferably used.
  • a chemically strengthened glass substrate is improved in strength and excellent in impact resistance, and thus is suitable for a cover glass used for a portable device that requires impact and pressure and requires high strength.
  • a cover glass for a mobile phone there are at least two layers such as a company name or a product name logo, an icon such as a touch panel, various sensor windows, a border around the screen, and a pressing pattern on the back surface.
  • a multi-color multilayer structure such as an eight-layer structure is required.
  • One example of the cover glass printing method is screen printing.
  • an antifouling coat is previously provided as a printing region protective layer. You may give it. Further, in this printing process, the operation of loading the glass substrate into the jig of the printing machine and removing it from the jig is repeated according to the number of times of printing. An antifouling coat may be applied in advance as a contact protective layer for preventing the glass substrate 1 from being damaged due to repeated contact. However, to prevent printing, the antifouling coating layer on the printing surface side is removed during the printing process, or a modification treatment is performed to reduce the contact angle of water on the surface of the antifouling coating layer. Is desirable.
  • Glass surface modification treatment (step S1)] Next, a glass surface modification treatment is performed on the glass substrate 1 (see FIG. 3A) produced as described above. Usually, since the printing surface formed on the surface of the glass substrate 1 is mounted toward the inside of the portable device, the surface opposite to the printing surface, that is, the glass substrate surface exposed toward the outside of the portable device. Glass surface modification treatment. In FIG. 2 and FIG. 3, although the description of the printing layer is omitted, for example, the printing layer is formed on the other main surface 1B side of the glass substrate 1, and the glass surface to be treated is provided on the one main surface 1A. 2 is formed (see FIG. 3B). The glass surface 2 is formed by performing a glass surface modification process in which a planar plasma process and a downstream plasma process are performed in this order.
  • the planar plasma processing is a mode in which two discharge electrodes are provided at a certain interval, a substrate to be processed is mounted within the interval, and plasma is generated to perform the processing.
  • a gas used for plasma generation for example, He, Ar, N 2 or the like is used as a gas used for plasma generation.
  • a voltage necessary for plasma generation is applied between the two electrodes, and ions ionized in the plasma space are accelerated in this space and collide with the surface of the substrate to be processed.
  • the glass substrate surface is modified so that the skewness (Rsk: skewness) of the contour curve on the glass substrate surface approaches 0, and the unevenness of the uneven shape on the glass substrate surface is reduced.
  • Rsk is preferably in the range of 0 ⁇ 0.3, more preferably in the range of 0 ⁇ 0.15.
  • the downstream type plasma processing means that a voltage required for plasma generation is applied between two electrodes arranged opposite to each other so as to sandwich a gas supply path to a substrate to be processed, and the plasmaized gas is processed.
  • the substrate is irradiated and supplied for processing.
  • a functional group such as a hydroxyl group or a carboxyl group is formed on the substrate surface, and the substrate surface is modified. It can also be used to remove organic contaminants on the substrate surface.
  • a gas used in this case for example, a mixed gas of N 2 and O 2 or air is used.
  • the adhesion stability of the antifouling coating material to the glass substrate is higher than that of a conventional antifouling coating layer formed by the dip method without particularly performing a surface treatment or the like on the glass substrate.
  • the durability of the antifouling coating surface can be remarkably improved.
  • a fluorine resin material is preferably used as the antifouling coating material applied to the glass surface. However, when this fluororesin material is applied to a glass substrate by a dip method, the adhesion stability to the glass substrate is particularly bad.
  • the reaction gas used in the case of the planar plasma treatment, is preferably He, Ar or N 2 , and more preferably He.
  • the power used is preferably in the range of 200 to 500 W, more preferably 300 to 400 W.
  • the treatment time is preferably in the range of 10 to 250 seconds, more preferably 30 to 90 seconds.
  • the reaction gas used in the case of the downstream plasma treatment, is preferably a mixed gas of an inert gas and air or O 2, and more preferably a mixed gas of N 2 and air.
  • the electric power used varies slightly depending on the type of reaction gas used, the power used is preferably in the range of 400 to 1200 W, more preferably in the range of 600 to 1000 W.
  • the processing time is preferably 5 to 60 seconds, and more preferably 10 to 15 seconds.
  • both the planar plasma treatment and the downstream plasma treatment are performed.
  • the planar plasma treatment is first performed as described above.
  • the downstream plasma treatment is then performed.
  • the glass surface shape is changed, and further, a functional group is generated on the glass surface, and the effects of the present invention are exhibited, which is preferable.
  • the glass surface modification treatment is performed on one main surface 1A, and the antifouling coating layer 3 is formed on the glass substrate 1 on which the glass treated surface is formed (FIG. 3C). reference).
  • the antifouling coating layer 3 is preferably formed by coating, for example, by a dip method.
  • the dip method is performed by immersing the entire glass substrate 1 in a coating solution containing, for example, the fluororesin as a main component in an appropriate solvent as an antifouling coating material, and taking it out and drying it.
  • the antifouling coating layer 3 having a uniform film thickness can be formed on the entire surface of the glass substrate 1 without using a vacuum film forming apparatus.
  • the coating thickness of the antifouling coating layer 3 is not particularly limited, but is preferably in the range of 0.3 nm to 30 nm, for example.
  • the film thickness is less than 0.3 nm, the durability is insufficient and the antifouling function may not be sufficiently exhibited.
  • the film thickness exceeds 30 nm, the transparency is lowered, so that it does not comply with the demand for portable devices.
  • the main surface 1A of the glass substrate 1 exposed on the front side of the portable device when incorporated in the display panel of the portable device is formed with a surface to be treated by the glass surface modification treatment of the present invention. Since the adhesion stability of the antifouling coating layer 3 formed by the dip method is improved, the durability can be remarkably improved as compared with the antifouling coating surface by the conventional dip method.
  • the antifouling coating layer alleviates the impact on the glass substrate surface, causing cracks in the glass substrate that cause a reduction in the strength of the brittle material glass. Since it becomes difficult, the mechanical strength of the cover glass can be improved. That is, the mechanical strength as the cover glass can be further improved by forming the antifouling coating layer on the chemically strengthened glass substrate.
  • the antifouling coating layer has an adhesion region that adheres to the surface of the glass substrate and a flow region that is disposed on the surface of the adhesion region.
  • the adhesion region is a region where molecules of the coating material are firmly bonded to a functional group such as a hydroxyl group or a carboxyl group on the surface of the glass substrate.
  • the flow region is a region where the molecular chains of the coating materials are intertwined to maintain the state.
  • the adhesion region and the flow region have the same composition, and there is no difference in appearance by a micrograph or the like. However, the flow region is easily dissolved in the solvent, and the adhesion region is not easily dissolved in the solvent.
  • the adhesion region is a region that remains when immersed in a solvent (for example, immersed in HFE for 1 minute), and the flow region can be identified as a region that dissolves when immersed in a solvent.
  • the film thickness of the adhesion region and the flow region can be measured by, for example, an ellipsometer MARY-102 manufactured by FiveLab.
  • the ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer is preferably 40% to 70%. This is because if the thickness ratio of the adhesion region is less than 40%, the durability cannot be exhibited. Further, if the ratio of the thickness of the adhesion region is more than 70%, the slipperiness cannot be exhibited. Furthermore, if it is 40% to 70%, durability and slipperiness can be exhibited better. Further, in order to better exhibit durability and slipperiness by setting the ratio of the thickness of the adhesion region to 40% to 70%, it is more preferable to use a fluorine resin material having a weight average molecular weight of 2000 to 5000 as a coating material. . In order to adjust the thickness of the adhesion region, specifically, a baking process, an ultraviolet irradiation process, a vacuum degree adjusting process using a reduced pressure, or the like can be performed.
  • the antifouling coating layer can be dried by heating at a temperature equal to or higher than the evaporation temperature of the solvent in a thermostatic oven.
  • the heating temperature is preferably 120 ° C to 180 ° C.
  • the heating time is preferably 30 minutes to 1 hour.
  • the higher the heating temperature and the longer the heating time the more the thickness of the flow region can be reduced.
  • the bonding between the molecules of the coating material constituting the adhesion region and the surface of the glass substrate is promoted by heat, and the adhesion region can be enlarged.
  • ultraviolet rays having a wavelength of 150 to 400 nanometers are preferable.
  • the ultraviolet light source for example, a low-pressure mercury lamp, a high-pressure mercury lamp, or an ultrahigh-pressure mercury lamp can be used.
  • the illuminance of the ultraviolet light source can be about 300 [cmW / cm 2 ]. The higher the illuminance of the ultraviolet light and the longer the irradiation time, the more the thickness of the flow region can be reduced.
  • the atmospheric temperature may be adjusted and the heat treatment may be performed simultaneously. Thereby, an adhesion area
  • the solvent can be evaporated by adjusting the degree of vacuum so that the pressure is lower than the vapor pressure of the solvent.
  • the atmospheric temperature may be adjusted and the heat treatment may be performed simultaneously. Thereby, an adhesion area
  • step S3 Next, the antifouling coat layer 3 formed on the other main surface 1B of the glass substrate 1 is subjected to an antifouling coat surface modification process which is a process for reducing the contact angle of water on the surface, thereby improving the antifouling coat.
  • a quality layer 3a is formed (see FIG. 3D).
  • An antifouling coating layer 3 is formed on one main surface 1A and the end surface 1C on which the glass treated surface is formed. For example, the entire glass substrate is immersed in the antifouling coating material by dipping. In the case of forming the dirty coating layer 3, the anti-staining coating layer is also formed on the other main surface 1B.
  • the anti-staining coating layer is also formed on the other main surface 1B.
  • at least one of an insulating layer and a transparent conductive layer is formed on the main surface 1B side of the glass substrate 1 incorporated toward the inside of the mobile device, and the operation of the user of the mobile device is detected.
  • a touch sensor module may be used.
  • the antifouling coating surface modification treatment is a treatment for reducing the contact angle of water on the surface of the antifouling coating layer 3 formed on the other main surface 1B of the glass substrate 1.
  • an antifouling coating surface modification treatment for example, a method such as a helium (He) plasma exposure treatment or an ultraviolet irradiation treatment by a planar method is preferably exemplified.
  • conditions such as irradiation energy and irradiation amount (irradiation time) when performing ultraviolet irradiation, and conditions such as plasma energy and processing time when performing plasma exposure treatment, preferable conditions can be selected as appropriate. It is possible to adjust the thickness in the depth direction of the antifouling coat modified layer 3a formed on the antifouling coat layer 3 by these ultraviolet irradiation conditions or plasma exposure treatment conditions.
  • the said transparent conductive layer is formed with predetermined thickness along the outer surface of the antifouling coat modification layer 3a formed in the main surface 1B of the glass substrate 1.
  • the “predetermined thickness” of the transparent conductive layer is, for example, 100 nm or less when formed by a sputtering method, and includes a transparent resin serving as a binder when formed by a printing method. 1000 nm or less.
  • a transparent conductive layer for example, an ITO (Indium Tin Oxide) film is formed on the outer surface of the antifouling coating modified layer 3a using a sputtering method or the like, and photolithography technology or YAG (Yttrium Aluminum Garnet) These are formed by processing the transparent conductive layer into a desired pattern shape using a laser patterning technique using a fundamental wave or a CO 2 laser.
  • the connection part (metal wiring) is formed by forming a metal conductive material on the surface of the printing region of the glass substrate by using a sputtering method or the like, and using a photolithography technique or the like to form the metal film. Is formed into a desired pattern shape.
  • an insulating layer may be provided between the surface of the antifouling coat modified layer 3a and the transparent conductive layer, and between the surface of the antifouling coat modified layer 3a and the connection portion (metal wiring), as necessary. Is formed.
  • This insulating layer is preferably formed using an insulating material having transparency, for example, an inorganic material such as SiO 2 .
  • the insulating layer is preferably formed to a thickness of about 50 to 1000 mm using, for example, a sputtering method.
  • the cover glass 10 for a mobile device according to the present embodiment is manufactured and incorporated into the mobile device.
  • the present invention also provides a method for manufacturing a touch sensor module. That is, a touch sensor module manufacturing method for detecting a user's operation, comprising a glass substrate having a pair of main surfaces and end faces adjacent to the pair of main surfaces, One main surface of the main surfaces is formed with a glass-treated surface by performing a glass surface modification treatment, and the glass-treated surface has an antifouling coating layer formed on the glass substrate. An antifouling coat reforming layer is formed on the other main surface of the pair of main surfaces by subjecting the antifouling coating layer to an antifouling coating surface modification treatment that reduces the contact angle of water on the surface. And a step of forming at least one of an insulating layer and a transparent conductive layer on the outer surface of the antifouling coating modified layer.
  • a touch sensor module including a glass substrate with improved durability of an antifouling coating surface and improved adhesion stability of a transparent conductive layer or the like can be obtained.
  • the antifouling coating treatment method is not limited to the dipping method, and for example, a spin coating method or a spray method. It can also be applied to vapor deposition, brush coating, and the like.
  • Example 1 The portable device of the present embodiment is subjected to the following (1) glass substrate manufacturing step, (2) glass surface modification treatment step, (3) antifouling coating layer forming step, and (4) antifouling coating surface modification treatment step. A cover glass was manufactured.
  • a glass substrate for cover glass was produced by cutting into a predetermined size from 0.5 mm thick plate glass made of aluminosilicate glass produced by the downdraw method or the float method.
  • aluminosilicate glass a chemical containing SiO 2 : 58 to 75 wt%, Al 2 O 3 : 4 to 20 wt%, Li 2 O: 3 to 10 wt%, Na 2 O: 4 to 13 wt% Tempered glass was used.
  • a hole was made in the glass substrate using a grindstone (for small opening diameter processing) or the like, and shape processing of the outer peripheral end face as shown in FIG. 4 was performed, for example.
  • chemical strengthening was performed on the glass substrate after the above-described shape processing.
  • a chemical strengthening solution in which potassium nitrate and sodium nitrate are mixed is prepared, this chemical strengthening solution is heated to 380 ° C., and the cleaned and dried glass substrate after the above shape processing is immersed for about 4 hours.
  • the glass substrate after chemical strengthening was sequentially immersed in each of washing tanks of sulfuric acid, neutral detergent, pure water, pure water, IPA, and IPA (steam drying), ultrasonically cleaned, and dried.
  • the printing process was implemented on the other main surface with respect to the glass substrate which performed the said chemical strengthening process. That is, a predetermined printing layer (ink layer) was formed by screen printing. Thus, a glass substrate was produced.
  • Antifouling coating layer forming step The above-mentioned coating solution (liquid temperature: 25 ° C.) prepared by adjusting the fluororesin (manufactured by Shin-Etsu Chemical Co., Ltd. (trade name) KY100 series) to an appropriate concentration with a solvent by the dipping method
  • the antifouling coating layer made of the fluororesin was applied to the entire surface of the glass substrate after the glass surface modification treatment, and dried with hot air at 100 ° C.
  • the coating thickness of the antifouling coating layer was 10 nm.
  • the film thickness of the antifouling coating layer is a value measured by an ellipsometer MARY-102 manufactured by FiveLab.
  • the contact angle (initial contact angle) with respect to water on the surface of the antifouling coating layer formed on the main surface of the glass substrate subjected to the glass surface modification treatment was 115 degrees.
  • the contact angle was measured according to JIS R3257 using a contact angle meter DM-501 manufactured by Kyowa Interface Science.
  • Antifouling coating surface modification treatment step The antifouling coating layer formed on the printed surface side of the glass substrate was subjected to plasma treatment by a planar method under the following conditions. ⁇ Reaction gas: He ⁇ Applied voltage: 300W Treatment time: 5 seconds Although the contact angle with water on the surface of the antifouling coating layer before the plasma treatment was 115 degrees, the contact angle immediately after the plasma treatment was lowered to 20 degrees or less.
  • the cover glass of this example was completed.
  • the static friction coefficient and dynamic friction coefficient of the antifouling coating layer surface were measured, the static friction coefficient was 0.35 and the dynamic friction coefficient was 0.21.
  • a load having a load of 50 gf, a sliding speed of 50 mm / second, a sliding distance of 50 mm, a tip surface material of polyethylene, and a tip having a curved shape was used.
  • the surface roughness Ra, Rq, the skewness Rsk, and the kurtosis Rku of the main surface were measured for the obtained cover glass.
  • These parameters are parameters defined by JIS B0601: 2001.
  • these parameters are measured with a scanning probe microscope (Atomic Force Microscope; AFM) nanoscope manufactured by Japan Veeco, and the surface roughness Ra can be calculated by a method defined in JIS R1683: 2007.
  • AFM Automatic Force Microscope
  • a value measured at a resolution of 512 ⁇ 128 pixels in a measurement area of 1 ⁇ m ⁇ 1 ⁇ m square can be used.
  • the measurement results are shown in Table 1.
  • the planar method is described as P method
  • the downstream method is described as D method.
  • steel wool (# 0000) is applied to the surface of the antifouling coat layer of the obtained cover glass, that is, the surface of the antifouling coat layer formed on the glass substrate main surface subjected to the glass surface modification treatment, with a load of 1 kg.
  • the surface was slid at (surface pressure 1 kg / cm 2 ), and the change in contact angle with water on the surface of the antifouling coating layer was examined.
  • the measurement results are shown in Table 2.
  • the contact angle after sliding 2000 times is ensured to be 110 degrees or more, the decrease from the initial contact angle (115 degrees) is small, and the durability of the antifouling coated surface can be remarkably improved.
  • the durability of the antifouling coated surface can be remarkably improved.
  • Example 2 A cover glass was manufactured in the same manner as in Example 1 except that in the (2) glass surface modification treatment step of Example 1, the planar plasma treatment time was set to 60 seconds.
  • parameters such as surface roughness and contact angle were measured in the same manner as in Example 1. These results are shown in Tables 1 and 2.
  • the contact angle after sliding 2000 times was ensured to be 105 degrees or more, and it was confirmed that the durability of the antifouling coating surface can be improved also in this example.
  • Example 3 A cover glass was produced in the same manner as in Example 1 except that in the (2) glass surface modification treatment step of Example 1, the planar plasma treatment time was 30 seconds.
  • parameters such as surface roughness and contact angle were measured in the same manner as in Example 1. These results are shown in Tables 1 and 2.
  • the contact angle after sliding 2000 times was ensured to be 105 degrees or more, and it was confirmed that the durability of the antifouling coating surface can be improved also in this example.
  • Example 1 A cover glass was produced in the same manner as in Example 1 except that (2) the glass surface modification treatment step in Example 1 was omitted.
  • the contact angle was measured in the same manner as in Example 1 on the surface of the antifouling coating layer of the obtained cover glass. The results are shown in Table 2.
  • the contact angle after sliding 1000 times was reduced to 100 degrees or less. That is, it was confirmed that the durability of the antifouling coating surface could not be sufficiently obtained even if the antifouling coating layer was formed without performing the glass surface modification treatment of the present invention.
  • Example 2 A cover glass was produced in the same manner as in Example 1 except that the downstream plasma treatment in the (2) glass surface modification treatment step of Example 1 was omitted.
  • the contact angle was measured in the same manner as in Example 1 on the surface of the antifouling coating layer of the obtained cover glass. The results are shown in Table 2.
  • the contact angle after 1000 times of sliding decreased to 105 degrees or less, and the contact angle after 2000 times of sliding decreased to 100 degrees or less. That is, it was confirmed that the durability of the antifouling coating surface could not be sufficiently obtained even if the antifouling coating layer was formed without performing the glass surface modification treatment of the present invention.
  • Example 3 A cover glass was produced in the same manner as in Example 1 except that the planar plasma treatment in the (2) glass surface modification treatment step of Example 1 was omitted.
  • parameters such as surface roughness and contact angle were measured in the same manner as in Example 1. These results are shown in Tables 1 and 2.
  • the contact angle after sliding 1000 times was reduced to 100 degrees or less. That is, it was confirmed that the durability of the antifouling coating surface could not be sufficiently obtained even if the antifouling coating layer was formed without performing the glass surface modification treatment of the present invention.
  • the glass substrate surface is modified so that the Rsk of the contour curve on the glass substrate surface approaches 0 and the Rku of the contour curve on the glass substrate surface decreases. It was confirmed that the unevenness of the uneven shape on the surface of the glass substrate was reduced.
  • the adhesion stability of the antifouling coating layer applied by the dip method to the glass substrate is further enhanced. It was confirmed that the durability of the antifouling coating surface could be improved compared to the case where the two-type plasma treatment was not performed (Comparative Examples 1 to 3). Further, when the ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer in Examples 1 to 3 was measured by the above method, it was in the range of 40% to 70%.
  • Example 4 an insulating layer mainly composed of SiO 2 was formed on the antifouling coating layer modified surface of the glass substrate produced in Example 1 by a sputtering method.
  • a transparent electrode film was formed on the surface of the insulating layer.
  • the transparent electrode film was formed by forming an ITO (Indium Tin Oxide) film by a sputtering method and processing the transparent electrode film into a desired pattern shape using a photolithography technique.
  • a conductive material was formed into a metal wiring by a sputtering method, and the conductive material film was processed into a desired pattern shape by a photolithography technique to manufacture a touch sensor module.
  • the touch sensor module of this example had good adhesion between the insulating layer and the transparent electrode film and the cover glass surface, and fulfilled a desired function as a touch sensor module.
  • Example 4 (Comparative Example 4)
  • the antifouling coating layer on the surface opposite to the surface subjected to the glass surface modification treatment was not subjected to plasma treatment ((4) antifouling coating surface modification treatment) by the planar method, but Example 4 Attempts were made to manufacture a touch sensor module in the same manner.
  • the adhesion between the insulating layer and the transparent electrode film and the cover glass surface is poor, and a part of the insulating layer and the transparent electrode film cannot be deposited without adhering to the cover glass surface.

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WO2014050798A1 (ja) * 2012-09-28 2014-04-03 Hoya株式会社 電子機器用カバーガラス及びその製造方法
JP2015141693A (ja) * 2014-01-30 2015-08-03 大日本印刷株式会社 表示装置用の電極付き前面保護板および表示装置用前面保護板の製造に用いられる基板
WO2015151592A1 (ja) * 2014-03-31 2015-10-08 株式会社ダイセル ペン入力デバイス用透明積層フィルム及びその製造方法
WO2016080432A1 (ja) * 2014-11-20 2016-05-26 旭硝子株式会社 透明板、タッチパッド、およびタッチパネル
WO2017026318A1 (ja) * 2015-08-10 2017-02-16 旭硝子株式会社 防汚層付きガラス板
US20190377386A1 (en) * 2018-06-12 2019-12-12 Samsung Display Co., Ltd. Window and display device comprising the same
JP2019215542A (ja) * 2018-06-12 2019-12-19 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． ウィンドウおよびこれを含む表示装置
JP2020140211A (ja) * 2016-01-12 2020-09-03 Ａｇｃ株式会社 防汚層付きガラス基体の製造方法
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CN204270266U (zh) 2014-02-28 2015-04-15 宸鸿科技(厦门)有限公司 一种复合基板结构及具有复合基板结构的触控面板
KR102648216B1 (ko) * 2016-07-06 2024-03-15 삼성디스플레이 주식회사 윈도우, 이를 포함하는 표시 장치, 및 윈도우 제조 방법
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WO2014050798A1 (ja) * 2012-09-28 2014-04-03 Hoya株式会社 電子機器用カバーガラス及びその製造方法
JP2015141693A (ja) * 2014-01-30 2015-08-03 大日本印刷株式会社 表示装置用の電極付き前面保護板および表示装置用前面保護板の製造に用いられる基板
WO2015151592A1 (ja) * 2014-03-31 2015-10-08 株式会社ダイセル ペン入力デバイス用透明積層フィルム及びその製造方法
JP2015194921A (ja) * 2014-03-31 2015-11-05 株式会社ダイセル ペン入力デバイス用透明積層フィルム及びその製造方法
US10719176B2 (en) 2014-03-31 2020-07-21 Daicel Corporation Transparent laminated film for pen input device and manufacturing method thereof
US10474283B2 (en) 2014-11-20 2019-11-12 AGC Inc. Transparent plate, touch pad, and touch panel
WO2016080432A1 (ja) * 2014-11-20 2016-05-26 旭硝子株式会社 透明板、タッチパッド、およびタッチパネル
JPWO2017026318A1 (ja) * 2015-08-10 2018-07-05 旭硝子株式会社 防汚層付きガラス板
JP7160155B2 (ja) 2015-08-10 2022-10-25 Ａｇｃ株式会社 防汚層付きガラス板
US11274063B2 (en) 2015-08-10 2022-03-15 AGC Inc. Glass plate with antifouling layer
CN113716879A (zh) * 2015-08-10 2021-11-30 Ａｇｃ株式会社 带防污层的玻璃板
JP2021185413A (ja) * 2015-08-10 2021-12-09 Ａｇｃ株式会社 防汚層付きガラス板
WO2017026318A1 (ja) * 2015-08-10 2017-02-16 旭硝子株式会社 防汚層付きガラス板
EP3718977A1 (en) * 2016-01-12 2020-10-07 Agc Inc. Glass substrate with antifouling layer and front plate for display
JP2020140211A (ja) * 2016-01-12 2020-09-03 Ａｇｃ株式会社 防汚層付きガラス基体の製造方法
JP2019215542A (ja) * 2018-06-12 2019-12-19 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． ウィンドウおよびこれを含む表示装置
US20190377386A1 (en) * 2018-06-12 2019-12-12 Samsung Display Co., Ltd. Window and display device comprising the same
US11500422B2 (en) * 2018-06-12 2022-11-15 Samsung Display Co., Ltd. Window and display device comprising the same
JP7377485B2 (ja) 2018-06-12 2023-11-10 三星ディスプレイ株式會社 ウィンドウおよびこれを含む表示装置

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