CN107265844B - External protective cover glass, manufacturing method thereof, glass substrate and protective cover glass - Google Patents

External protective cover glass, manufacturing method thereof, glass substrate and protective cover glass Download PDF

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Publication number
CN107265844B
CN107265844B CN201710363113.1A CN201710363113A CN107265844B CN 107265844 B CN107265844 B CN 107265844B CN 201710363113 A CN201710363113 A CN 201710363113A CN 107265844 B CN107265844 B CN 107265844B
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China
Prior art keywords
glass substrate
glass
cover glass
electronic equipment
main surface
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CN201710363113.1A
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CN107265844A (en
Inventor
下川贡一
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Hoya Corp
Hoya Glass Disk Philippines Inc
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Hoya Corp
Hoya Glass Disk Philippines Inc
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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
    • 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
    • B32B17/10—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 synthetic resin
    • B32B17/10005—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 synthetic resin laminated safety glass or glazing
    • B32B17/10009—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 synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—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 synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C03C15/02—Surface treatment of glass, not in the form of fibres or filaments, by etching for making a smooth surface
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2571/00—Protective equipment
    • 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

Abstract

The invention relates to an external protective cover glass, a manufacturing method thereof, a glass substrate and a protective cover glass. The external protective cover glass for electronic equipment can exert both the smoothness and the durability of the antifouling coating.

Description

External protective cover glass, manufacturing method thereof, glass substrate and protective cover glass
The application is a divisional application, the international application number of the original application is PCT/JP2013/075667, the Chinese national application number of the original application is 201380044280.X, the application date is 2013, 09 and 24 days, and the invention name is cover glass for electronic equipment and a manufacturing method thereof.
Technical Field
The present invention relates to cover glass (cover glass) for electronic devices used for protecting display screens of portable devices such as mobile phones, portable game devices, PDAs (Personal Digital assistants), Digital cameras, video cameras, tablet PCs (Personal computers), and the like, and a method for manufacturing the cover glass.
Background
Conventionally, in order to protect a display screen of a portable device such as a mobile phone, an acrylic resin sheet having excellent transparency and light weight has been generally used. In recent years, touch panel type mobile devices have become mainstream, and in order to cope with the touch panel function, it is required to improve the strength of a display screen, and a thin and high-strength glass material is often used instead of a conventional acrylic resin material. Further, glass materials are superior to conventional acrylic resin materials in terms of mechanical strength (scratch resistance, impact resistance), surface smoothness, protection (weather resistance, stain resistance), appearance, and high-grade appearance.
In a touch panel type portable device, since a finger is directly touched on a display screen to perform an operation, dirt such as a fingerprint or sebum is likely to adhere to a cover glass that protects the display screen. Therefore, it is desired to prevent or suppress adhesion of dirt such as fingerprints to the cover glass or to facilitate wiping even if dirt such as fingerprints is adhered. Therefore, an antifouling coating is usually formed on the surface of the cover glass.
Patent document 1 describes that a fluorine-based surface layer is provided as an antifouling coating on the surface of cover glass. As the coating material, alkoxysilyl perfluoropolyether is exemplified. Patent document 1 describes a coating process in which a material is coated by dipping, vapor deposition, spraying, and coating using a roller, and then the material is hardened, and then the unbound coating layer is removed by rinsing with a solvent. Patent document 1 describes that by providing a fluorine-based surface layer, cover glass having antifouling properties (water repellency and oil repellency, collectively referred to as "double repellency") and scratch resistance can be formed.
Documents of the prior art
Patent document
Patent document 1: japanese Kohyo publication 2011-510904
Disclosure of Invention
Problems to be solved by the invention
However, since a user rubs his or her finger on the cover glass for electronic devices of the touch panel system for handling, smoothness when touched with a finger is required for the antifouling coating layer.
In addition, in portable devices such as smartphones which have become widespread in recent years, the software product life (service life) is longer than that of conventional touch-panel type portable devices such as PDAs because of the function of updating software such as the OS. Accordingly, the portable device is required to have improved durability even in a long-term use in terms of hardware. In particular, since cover glass for electronic equipment is incorporated into electronic equipment in a state where the surface is exposed, durability that is resistant to friction with the fingers of a user and contact with various objects and that exerts antifouling property and smoothness for a long period of time is required for an antifouling coating.
That is, the antifouling coating layer of the cover glass for electronic devices is required to have both smoothness and durability.
Patent document 1 discloses the antifouling property and scratch resistance of the antifouling coating layer, but does not consider the slipperiness and does not disclose a structure satisfying both the slipperiness and the durability. Therefore, only by the technique disclosed in patent document 1, desired characteristics as an antifouling coating cannot be achieved.
Accordingly, an object of the present invention is to provide a cover glass for an electronic device, which can exhibit both of the smoothness and durability of an antifouling coating layer, and a method for producing the same.
Means for solving the problems
In order to solve the above problems, the inventors have made intensive studies and focused on the following techniques: inside the antifouling coating layer of the cover glass for electronic devices, there are an adhesion region that adheres to the glass surface and affects durability, and a flow region that contributes to smoothness. Then, the present inventors have conceived of developing both of the smoothness and the durability by appropriately forming these regions, and have completed the present invention.
That is, a typical configuration of a cover glass for electronic equipment according to the present invention is characterized in that the cover glass for electronic equipment includes: a glass substrate; and an antifouling coating layer formed on a surface of the glass substrate, the antifouling coating layer having: an attachment region attached to a surface of the glass substrate; and a flow region disposed on a surface of the attachment region.
According to the above configuration, both smoothness and durability can be exhibited. The adhesion region is a region remaining when impregnated with a solvent (for example, by immersion in HFE for 1 minute), and the flow region is a region dissolved when immersed in a solvent.
The ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer is preferably 20% to 80%, more preferably 40% to 70%. This is because if the ratio of the thickness of the adhesion region is less than 20%, durability cannot be exhibited. If the thickness ratio of the adhesion region is higher than 80%, smoothness cannot be exhibited.
The thickness of the antifouling coating is preferably, for example, 3nm to 30 nm. This is because if the thickness of the antifouling coating layer is less than 3nm, durability cannot be exhibited. Further, if the thickness of the antifouling coating is larger than 30nm, the thickness uniformity cannot be ensured and the transparency is lowered, so that the requirement of the portable device cannot be satisfied.
Preferably, the surface of the flow region has a static friction coefficient of 0.2 to 0.4, a dynamic friction coefficient of 0.1 to 0.3, and a contact angle of water of 100 to 120 degrees. Within the above range, the smoothness and stain resistance can be suitably achieved.
The antifouling coating preferably contains a perfluoropolyether compound having a hydroxyl group at the terminal group. This strongly bonds to a functional group such as a hydroxyl group or a carboxyl group on the surface of the glass substrate, and can exhibit high durability.
In addition, a typical configuration of a method for manufacturing a cover glass for an electronic device according to the present invention is characterized in that the method for manufacturing a cover glass for an electronic device includes: a glass substrate manufacturing process; and an antifouling coating layer forming step of applying a coating layer having antifouling properties to the glass substrate, wherein in the antifouling coating layer forming step, an adhesion region and a flow region are formed, the adhesion region adhering to the surface of the glass substrate, and the flow region being disposed on the surface of the adhesion region.
Preferably, the antifouling coating layer forming step is followed by a zone thickness adjusting step of adjusting the ratio of the thickness of the adhesion zone to the thickness of the antifouling coating layer by adjusting the thickness of the flow zone. This makes it possible to set the thickness of the adhesion region to a desired ratio. Preferably, the ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer in the region thickness adjusting step is 20% to 80%, and more preferably 40% to 70%.
Preferably, in the region thickness adjusting step, the thickness of the flow region is adjusted by baking (bake) treatment, ultraviolet irradiation treatment, and vacuum degree adjusting treatment by reduced pressure.
Preferably, in the antifouling coating layer forming step, the thickness of the antifouling coating layer is 3nm to 30 nm.
Another typical configuration of the cover glass for electronic devices according to the present invention is characterized in that a surface of a glass substrate is coated with a coating material containing a perfluoropolyether compound having a hydroxyl group at an end group to form an antifouling coating layer having 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 cover glass for electronic equipment is an external cover glass for electronic equipment that is detachably attached to cover a part of a housing of the electronic equipment, and includes: 1 st main surface; a 2 nd main surface, the 2 nd main surface being a back surface opposite to the 1 st main surface, for being disposed toward a housing of the electronic apparatus; and an end surface connecting the 1 st main surface and the 2 nd main surface, a recessed portion being provided in at least a part of an outer periphery of the 2 nd main surface, the recessed portion being recessed from the end surface toward an inside in a plane direction of the 2 nd main surface.
According to the above configuration, when the cover glass for electronic equipment is attached to the electronic equipment, a gap is generated between the cover glass for electronic equipment and the electronic equipment by the concave portion. Since the cover glass for electronic equipment can be peeled off by the user by hooking a nail or the like in the gap, the cover glass for electronic equipment can be made of glass which exhibits smoothness and durability and has excellent peelability.
The glass substrate may have the above-described 1 st main surface, 2 nd main surface, and an end surface, and the bonded portion may be provided along the 2 nd main surface, and at least a part of an outer peripheral end of the bonded portion may be disposed at an interval inward in a surface direction of the 2 nd main surface from the end surface to form the recessed portion. According to the above configuration, at least a part of the outer peripheral end of the bonded portion is disposed at an interval inward in the surface direction of the 2 nd main surface from the end surface to form the recessed portion. Therefore, the recessed portion can be formed easily.
The depth of the recessed portion from the end surface is in the range of 0.1mm to 0.3 mm. According to the above structure, both peelability and beauty can be achieved. That is, when the depth from the end face is 0.1mm or more, the peelability can be further exhibited. If the depth from the end face exceeds 0.3mm, dust or the like remains in the recessed portion with the passage of time, which may result in a loss of appearance.
The glass substrate may include a glass substrate having the 1 st main surface, the 2 nd main surface, and an end surface, and an intermediate surface that becomes at least a part of the recessed portion may be formed between the end surface and the 2 nd main surface. According to the above configuration, a part of the recessed portion can be formed by the configuration of the glass substrate. With this configuration, the user can easily catch a nail or the like in the gap, and thus the peelability of the cover glass for an electronic device can be improved.
The end face may be an inclined face which is inclined so as to taper from the 2 nd main surface side toward the 1 st main surface side end and which is linear or curved in a sectional view. According to the above structure, the user's finger or the like can be prevented from being caught on the edge of the glass substrate. Therefore, the present invention is particularly effective in the case of a smartphone or the like having a touch panel display.
The cover glass for electronic equipment may be attached to and detached from the case cover glass so as to cover a main surface of the case cover glass which is a part of a case of the electronic equipment. According to the above configuration, the cover glass of the electronic device can be prevented from being damaged or contaminated.
Preferably, the glass surface modification treatment comprising two treatments, a planar plasma treatment and a concurrent plasma treatment, is performed before the antifouling coating layer forming step. Therefore, the adhesion stability of the antifouling coating material to the glass substrate is improved, and the durability of the surface of the antifouling coating material can be obviously improved.
Effects of the invention
According to the cover glass for electronic equipment and the method for manufacturing the same of the present invention, both the smoothness and the durability of the antifouling coating layer can be exhibited.
Drawings
Fig. 1 is a schematic cross-sectional view showing one embodiment of a cover glass for an electronic device of the present invention.
Fig. 2 is a flowchart of a method for manufacturing a cover glass for an electronic device according to the present invention.
Fig. 3 is a plan view showing an example of the shape of the cover glass substrate.
Fig. 4 is a schematic cross-sectional view showing a method for manufacturing a cover glass for an electronic device according to the present invention in order of steps.
Fig. 5 is a diagram showing a state in which the cover glass for an electronic device of embodiment 2 is attached to the electronic device.
Fig. 6 is a schematic cross-sectional view of the electronic device of fig. 5 after the cover glass is attached to the electronic device.
Fig. 7 is an enlarged view of the range X of fig. 6.
Fig. 8 is a diagram showing a layer structure of the cover glass for electronic device of fig. 5.
Fig. 9 is a diagram showing a step of forming the cover glass for electronic device of fig. 5.
Fig. 10 is an explanatory diagram about a range where the depression portion of fig. 7 is formed.
Fig. 11 is a diagram showing an outer peripheral portion of a cover glass for electronic equipment according to embodiment 3.
Fig. 12 is a diagram showing another example of the cover glass for electronic equipment according to embodiment 3.
Fig. 13 is a view illustrating a method of processing an outer peripheral portion of the glass substrate shown in fig. 11 and 12.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Dimensions, materials, and other specific numerical values and the like shown in the embodiments are merely examples for easy understanding of the invention, and are not intended to limit the invention unless otherwise specified. In the present specification and the drawings, elements having substantially the same function and configuration are denoted by the same reference numerals, so that overlapping description is omitted, and elements not directly related to the present invention are omitted.
[ embodiment 1]
In embodiment 1, a cover glass assembled to a case so as to be a part of a housing of an electronic device will be described as an example of the cover glass for an electronic device.
Fig. 1 is a schematic cross-sectional view showing one embodiment of a cover glass for an electronic device of the present invention, and only a part of the vicinity of the surface is shown in an enlarged manner. The cover glass 1 for electronic equipment of the present embodiment includes a flat plate-like glass substrate 10. The antifouling coating 20 is formed on the main surface 12 of the glass substrate 10. As described later, the antifouling coating layer 20 has: an attachment region 22, the attachment region 22 being attached to the surface of the glass substrate 10; and a flow region 24, the flow region 24 being disposed on a surface of the attachment region 22.
The adhesion region 22 is a region where molecules of the coating material are strongly bonded to functional groups such as hydroxyl groups or carboxyl groups at the surface of the glass substrate. The flow region 24 is a region where molecular chains of the coating materials maintain a polymerized state with each other. The composition of the adhesion region 22 and the flow region 24 is the same, and there is no difference in appearance based on a photomicrograph or the like. However, the flow region 24 is easily dissolved in the solvent, and the adhesion region 22 is not easily dissolved in the solvent. Thus, the identification can be performed as follows: the attachment region 22 is a region that remains when immersed in a solvent (for example, immersed in HFE for 1 minute), and the flow region 24 is a region that dissolves when immersed in a solvent.
The material of the antifouling coating layer 20 will be explained. In the case of a touch panel operation type portable device, a user directly touches the display screen with a finger to perform an operation, and therefore dirt such as a fingerprint is likely to adhere to the display screen. Therefore, it is desired to prevent or suppress adhesion of dirt such as fingerprints to the display screen or to easily wipe off even if dirt such as fingerprints is adhered. Therefore, as the material of the antifouling coating layer 20, a material having the following antifouling property is preferably selected: even if the finger is directly touched (pressed), adhesion of dirt such as a fingerprint is prevented or suppressed, or even if the dirt such as a fingerprint is adhered, the dirt is easily wiped off. Further, it is important to have excellent transparency. In the present invention, as a material having good antifouling property and excellent transparency, for example, a material having a reduced surface energy such as a fluorine-based resin material (for example, a perfluoropolyether compound) is preferable.
Preferably, the contact angle of water on the surface (surface on the side opposite to the glass substrate 10) of the antifouling coating layer 20 is 100 to 120 degrees, and the contact angle of oil such as hexadecane is 60 to 70 degrees. The contact angle is a value measured in an environment of 22. + -. 2 ℃.
By setting the contact angle to water or oil within the above range, the following excellent antifouling property is exhibited: even if a finger is directly touched (pressed), adhesion of dirt such as a fingerprint is prevented or suppressed, or even if dirt such as a fingerprint is adhered, the dirt is easily wiped off. Although the contact angle is the initial contact angle after the antifouling coating layer is formed, the contact angle is less decreased even if the steel wool sliding durability test described in the examples below is performed, and good antifouling property can be maintained.
In the cover glass 1 for electronic equipment of the present invention, it is preferable that the coefficient of static friction on the surface of the antifouling coating layer 20 formed on the main surface 12 of the glass substrate is 0.2 to 0.4 and the coefficient of dynamic friction is 0.1 to 0.3. By making the coefficient of static friction or the coefficient of dynamic friction of the surface of the antifouling coating layer 20 within the above range, the smoothness of the antifouling coating layer surface is good and the tactile sensation of the hand when touched with a finger is good, so that in a portable device provided with the cover glass of the present invention, the operability of the user on, for example, a touch panel is good.
The glass constituting the glass substrate 10 is preferably amorphous aluminosilicate glass. The glass substrate made of such aluminosilicate glass has high strength after chemical strengthening, and is suitable for cover glass for electronic devices. As such aluminosilicate glass, for example, aluminosilicate glass containing as main components: SiO 2258 to 75 wt.% of Al2O34 to 20% by weight of Li20 to 10% by weight of O and Na2O accounts for 4 to 20 wt%.
From the viewpoint of responding to recent market demand for weight reduction of portable devices, the thickness of the glass substrate 10 is preferably in the range of, for example, 0.3mm to 1.5mm, and more preferably in the range of 0.5mm to 0.7 mm.
Next, the method for manufacturing a cover glass for an electronic device of the present invention described above will be described. Fig. 2 is a flowchart of a method for manufacturing a cover glass for an electronic device according to the present invention, fig. 3 is a plan view showing an example of the shape of a glass substrate, and fig. 4 is a schematic sectional view showing the method for manufacturing the cover glass for an electronic device according to the present invention in order of steps.
[ production of glass substrate (step S100) ]
First, a large-sized glass plate is cut (diced) into a predetermined size by machining or the like, and a glass substrate 10 for cover glass is manufactured.
For example, a plurality of glass plates (for example, about several tens of glass plates) having a thickness of, for example, about 0.5mm, which are manufactured by a down-draw method, a float method, or the like, are stacked (laminated), and cut into small pieces having a predetermined size using a glass cutter. In this way, when the glass plate in the stacked state is cut at a time, the shape of the small pieces in the stacked state can be processed at a time in the next shape processing step, which is advantageous for production. The size of the chip is determined by considering the size obtained by adding the margin required for the outline shape processing to the size of the cover glass of the product.
Here, the outer shape processing may be performed on the sheet-like glass material sheet by sheet instead of the cutting processing in the laminated state. In addition, for the outline processing, etching may be used as a means other than machining.
Next, the glass substrate 10 processed into small pieces of the predetermined size is subjected to necessary drilling processing, peripheral shape processing, and the like by machining or etching processing. In the example shown in fig. 3, the glass substrate 10 is formed with an outer peripheral end face 10a, a notch 10b, an ear hole 10c, and a key operation hole 10 d. Such drilling and peripheral shape processing may be performed by mechanical processing such as sandblasting, or by collectively processing these by etching. For particularly complicated shape processing, etching processing is advantageous. Further, a combination of machining and etching may be used depending on the shape to be processed. Further, the sheet-like glass material may be formed into small pieces by appropriately setting the dissolution pattern in the etching process, and the small pieces may be formed into the shape of the glass substrate 10 shown in fig. 3 in the same step of forming the small pieces.
Next, the glass substrate 10 having been subjected to the shape processing is subjected to a chemical strengthening treatment. As a method of the chemical strengthening treatment, for example, a low-temperature ion exchange method in which ion exchange is performed at a temperature not higher than the glass transition point, for example, at a temperature of 300 to 500 ℃. The chemical strengthening treatment is a treatment in which: by bringing the molten chemical strengthening salt into contact with the glass substrate, the alkali metal element having a relatively large ionic radius in the chemical strengthening salt and the alkali metal element having a relatively small atomic radius in the glass substrate are ion-exchanged, whereby the alkali metal element having a large ionic radius penetrates the surface layer of the glass substrate, and a compressive stress is generated on the surface of the glass substrate. As the chemical strengthening salt, an alkali metal nitrate such as potassium nitrate or sodium nitrate can be preferably used. Since the glass substrate subjected to the chemical strengthening treatment has high strength and excellent impact resistance, it is suitable for cover glass used in portable devices that require high strength when subjected to impact or pressure.
[ glass substrate modification treatment (step S102) ]
Next, the glass substrate 10 produced as described above is subjected to a glass surface modification treatment. In general, since the printed surface side formed on the surface of the glass substrate 10 is mounted facing the inside of the mobile device, the main surface 12 opposite to the printed surface, that is, exposed to the outside of the mobile device is subjected to glass surface modifying treatment.
The planar plasma processing is as follows: the plasma processing apparatus has 2 discharge electrodes at a certain interval, and a substrate to be processed is mounted in the interval, and plasma is generated to perform processing. In this case, as the gas used for plasma generation, He, Ar, or N is used, for example2And the like. A voltage necessary for generating plasma is applied between 2 electrodes, and ions ionized in the plasma space are accelerated in the space and collide with the surface of the substrate to be processed. Thus, the surface of the glass substrate is modified so that the skewness (Rsk: skew) of the profile curve of the surface of the glass substrate approaches 0, and the variation of the uneven shape of the surface of the glass substrate is reduced. Here, Rsk is preferably in the range of 0 ± 0.3, and more preferably in the range of 0 ± 0.15.
In addition, the so-called downstream (down stream) plasma processing is a type in which a voltage necessary for generating plasma is applied between 2 electrodes arranged facing each other through a supply path for supplying a gas to a substrate to be processed, and the substrate is irradiated with the gas formed by plasma supply to perform processing. The surface of the substrate is modified by irradiating the surface of the substrate with an excited gas to form a functional group such as a hydroxyl group or a carboxyl group on the surface of the substrate. Further, the method can be used for removing organic contaminants on the surface of the substrate. As the gas used in this case, for example, N is used2And O2Or a mixed gas of air, etc.
In the present embodiment, it is important to perform both the planar plasma treatment and the downstream plasma treatment as the glass surface modification treatment. By performing the glass surface modification treatment, for example, as compared with an antifouling coating formed by a conventional dipping method without particularly performing a surface treatment or the like on a glass substrate, the adhesion stability of an antifouling coating material to a glass substrate is improved, and the durability of the surface of the antifouling coating can be remarkably improved. As the antifouling coating material to be applied to the glass surface, a fluorine-based resin material is preferably used. However, when the fluorine-based resin material is applied to a glass substrate by an immersion method, the adhesion stability to the glass substrate is particularly poor. Therefore, even when such a fluorine-based resin material is used as an antifouling coating material and applied to a glass substrate by an immersion method, the adhesion stability to the glass substrate is improved, and the durability of the surface of the antifouling coating layer can be significantly improved.
In the case of the above planar plasma treatment, the reaction gas used is preferably He, Ar or N2More preferably He. The power used varies depending on the kind of the reaction gas used, but is preferably in the range of 200 to 500W, more preferably 300 to 400W. The treatment time is preferably 10 to 250 seconds, and more preferably 30 to 90 seconds. On the other hand, in the case of the concurrent plasma treatment described above, the reaction gases used are preferably an inert gas and air or O2More preferably N2And air. The power used varies somewhat depending on the kind of the reaction gas used, but is preferably in the range of 400 to 1200W, more preferably 600 to 1000W. The treatment time is preferably 5 to 60 seconds, and more preferably 10 to 15 seconds.
As the order of the planar plasma processing and the downstream plasma processing, the planar plasma processing is performed first, and then the downstream plasma processing is performed. This is preferable because the shape of the glass surface is changed and then functional groups are generated on the glass surface.
[ formation of antifouling coating layer (step S104) ]
Next, the antifouling coating 20 is formed on the main surface 12. As a result, the state where only the glass substrate 10 is present as shown in fig. 4(a) changes to the state where the antifouling coating 20 is formed as shown in fig. 4 (b). The coating material is preferably a perfluoropolyether compound (fluorine-based resin) having a hydroxyl group at the terminal group. This strongly bonds to a functional group such as a hydroxyl group or a carboxyl group on the surface of the glass substrate, and can exhibit high durability.
The antifouling coating layer 20 can be formed by, for example, dipping. The impregnation process is carried out as follows: the entire glass substrate 10 is immersed in a coating liquid containing a coating material in an appropriate solvent, taken out, and dried. By this immersion method, the antifouling coating layer 20 having a uniform thickness can be formed on the entire surface of the glass substrate 10 without using a vacuum deposition apparatus. The film forming method is not limited to the dipping method, and there are spin coating methods in which a film is formed by a centrifugal force, spray coating methods in which a target substance is sprayed with a spray gun, vapor deposition methods, and the like, and the film forming of the lubricating layer 128 can be performed by these methods.
The coating film thickness of the antifouling coating layer 20 is not particularly limited, but is preferably in the range of, for example, 3nm to 30 nm. If the film thickness is less than 3nm, the durability is insufficient, and the antifouling function may not be sufficiently exhibited in long-term use. On the other hand, if the film thickness exceeds 30nm, the thickness uniformity of the antifouling coating layer 20 cannot be ensured, and the transparency is lowered, so that the requirement of the portable device cannot be satisfied.
By providing the antifouling coating layer, when an external force is applied to the cover glass, the impact on the surface of the glass substrate is alleviated by the antifouling coating layer, and cracks are less likely to occur in the glass substrate, which are factors that reduce the strength of the glass that is a brittle material, so that the mechanical strength of the cover glass can be improved. That is, the mechanical strength as a cover glass can be further improved by forming an antifouling coating layer on a chemically strengthened glass substrate.
[ Regulation of regional thickness (step S106) ]
The antifouling coating 20 formed as described above forms the adhesion region 22 and the flow region 24 in the inside thereof with hardening (solvent evaporation). The adhesion region 22 is a region that adheres to the main surface 12 and affects durability. The flow area 24 is an area that contributes to smoothness. Therefore, in the present invention, the partial thickness adjusting step is performed to adjust the ratio of the thickness of the adhesion region 22 to the thickness of the antifouling coating layer 20.
In the zone thickness adjusting step, the evaporation rate of the solvent is adjusted to volatilize the molecules having a small molecular weight, thereby reducing the thickness of the flow zone 24 and adjusting the thickness as shown in fig. 4 (c). That is, the region thickness adjusting step is a step of indirectly adjusting the ratio of the thickness of the adhesion region 22 to the thickness of the antifouling coating layer 20. In the zone thickness adjusting step, no significant thickness reduction is observed in the adhesion zone 22 as compared with the flow zone 24. This is considered to be because molecules of the coating material constituting the adhesion region 22 are strongly bonded to functional groups such as hydroxyl groups or carboxyl groups at the surface of the glass substrate.
The ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer is preferably 20% to 80%, and more preferably 40% to 70%. This is because if the ratio of the thickness of the adhesion region is less than 20%, durability cannot be exhibited. Further, if the thickness ratio of the adhesion region is higher than 80%, smoothness cannot be exhibited. Further, if the content is 40% to 70%, the durability and the smoothness can be more favorably exhibited.
As the region thickness adjusting step, specifically, baking treatment, ultraviolet irradiation treatment, and vacuum degree adjusting treatment by reduced pressure may be performed.
In the baking treatment, the antifouling coating layer 20 can be dried by heating in a constant temperature oven at a temperature equal to or higher than the evaporation temperature of the solvent. The heating temperature is preferably 120 to 180 ℃. The heating time is preferably 30 minutes to 1 hour. Here, the higher the heating temperature is, and the longer the heating time is, the more the thickness of the flow region 24 can be reduced. At the same time, the molecules of the coating material constituting the adhesion region 22 are promoted to bond with the surface of the glass substrate by heat, and the adhesion region 22 can be enlarged.
In the ultraviolet irradiation treatment, as the ultraviolet ray, an ultraviolet ray having a wavelength of 150 to 400 nm is preferable. As the light source of ultraviolet rays, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or the like can be used. The illuminance of the ultraviolet light source may be 300[ cmW/cm ]2]Left and right. The higher the illuminance of the ultraviolet rays and the longer the irradiation time, the more the thickness of the flow field 24 can be reduced.In addition, the heating treatment may be performed while adjusting the ambient temperature in the ultraviolet irradiation treatment. This can enlarge the attachment region 22.
In the vacuum degree adjustment process, the solvent can be evaporated by adjusting the vacuum degree so that the pressure becomes lower than the vapor pressure of the solvent. The higher the degree of vacuum (lower the gas pressure), and the longer the treatment time, the more the thickness of the flow region 24 can be reduced. In the vacuum degree adjustment process, the heating process may be performed while adjusting the ambient temperature. This can enlarge the attachment region 22.
Further, after printing is performed as necessary to form transparent electrodes for a touch panel, the cover glass is assembled to a mobile device.
[ examples ]
The cover glass for electronic equipment and the method for manufacturing the same according to the present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples.
(1) Process for producing glass substrate
First, a glass substrate for cover glass is produced by cutting a glass plate having a thickness of 0.5mm, which is made of aluminosilicate glass produced by a down-draw method or a float method, into a predetermined size. As the aluminosilicate glass, a glass for chemical strengthening containing: SiO 2258 to 75 wt.% of Al2O34 to 20% by weight of Li23-10% by weight of O and Na2O accounts for 4 to 13 wt%.
Next, a hole is formed in the glass substrate using a grindstone (for small diameter machining) or the like, and the outer peripheral end face is shaped as shown in fig. 3, for example, as described above. The glass substrate having been subjected to shape processing is subjected to chemical strengthening, and then immersed in respective cleaning tanks of sulfuric acid, a neutral cleaning agent, pure water, IPA, and IPA (vapor drying) in this order, and then subjected to ultrasonic cleaning and dried. Thus, a glass substrate was produced.
(2) Antifouling coating layer Forming Process
An antifouling coating layer made of a fluorine-based resin was applied to the entire surface of a glass substrate by dipping using a coating liquid (liquid temperature 25 ℃) obtained by adjusting the concentration of a fluorine-based resin (product name, KY100 series, manufactured by shin-Etsu chemical Co., Ltd.) to an appropriate concentration with a solvent. The coating thickness of the antifouling coating was 10 nm.
(3) Region thickness adjusting step
Next, as a zone thickness adjusting step, hot air drying was performed for 30 minutes. Here, as shown in table 1, a plurality of samples were prepared with different drying temperatures. Then, after the thickness of the dried antifouling coating layer 20 was measured, the flow region 24 was removed by immersing in HFE as a solvent for 1 minute, and the thickness of the adhesion region 22 was measured. Table 1 shows the ratio of the thickness of the adhesion region 22 to the thickness of the antifouling coating layer 20 thus obtained. The film thickness was measured by ellipsometer MARY-102 manufactured by FiveLab corporation.
[ Table 1]
Figure BDA0001300868460000121
The steel wool (#0000) was slid on the antifouling coating surface of each sample with a load of 1kg, and variations in the static friction coefficient, the dynamic friction coefficient, and the contact angle to water on the antifouling coating surface were examined. The measurement results are shown in tables 2 to 4. The initial values of the static friction coefficient and the dynamic friction coefficient were 0.35 for the static friction coefficient and 0.21 for the dynamic friction coefficient. The conditions for measuring the friction coefficient used were a sliding contact having a load of 50gf, a sliding speed of 50 mm/sec, a sliding distance of 50mm, a surface material of the end of polyethylene and a curved shape of the end. The initial value of the contact angle of water is 115 degrees. The contact angle of water was measured according to JIS R3257 using a contact angle meter DM-501 manufactured by Kyowa Kagaku K.K.
In table 2, the evaluation was made based on whether or not the static friction coefficient of the surface of the flow region was 0.2 to 0.4. In Table 3, the evaluation was made based on whether or not the coefficient of kinetic friction was 0.1 to 0.3. In table 4, the evaluation was performed based on whether or not the contact angle of water was 100 to 120 degrees.
[ Table 2]
Figure BDA0001300868460000122
Figure BDA0001300868460000131
[ Table 3]
Figure BDA0001300868460000132
[ Table 4]
Figure BDA0001300868460000133
In tables 2 and 3, referring to samples 1 and 2, it is seen that the coefficient of friction greatly increases as the steel wool is slid 1000 times and 2000 times. Also in table 4, referring to samples 1 and 2, the contact angle of water is greatly reduced. This is considered to be: the flow region 24 is easily removed by the sliding of the steel wool, and the adhesion region 22 is also removed due to the thinness, so that the glass substrate is exposed. From this, it is found that if the ratio of the thickness of the adhesion region is less than 20%, the durability cannot be exhibited.
As is clear from reference to sample 9 in tables 2 and 3, the friction coefficient is increased unlike samples 1 and 2. This is considered to be because: the molecular chains of the coating material are finely divided by the baking treatment at 200 ℃, the fluidity of the molecules in the fluidized layer is further improved, and the durability of the fluidized layer itself is significantly reduced. From this, it is found that, if the thickness ratio of the adhesion region is higher than 80%, smoothness after the durability test cannot be exhibited.
Therefore, the thickness of the adhesion region is preferably 20% to 80%. Further, the friction coefficient of samples 4 to 7 in tables 2 and 3 hardly changed even after 2000 times of sliding. From this, it is found that the ratio of the thickness of the adhesion region is more preferably 40% to 70%.
In addition, referring to sample 9 in table 4, the contact angle of water hardly decreases. This is considered to be because the adhesion region 22 remained after 2000 slips, and the contact angle of water was maintained. Summarizing the above results, it can be seen that: it is assumed that in the case where only the adhesion regions 22 are formed as the coating layer, the antifouling property (which can be evaluated by a contact angle) has durability, but the lubricity (which can be evaluated by a friction coefficient) does not have durability. Furthermore, it can be seen that: by setting the ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer to 20% to 80% as shown in the present invention, both the smoothness and the durability of the antifouling coating layer can be exhibited.
[ 2 nd embodiment ]
Embodiment 2 of the cover glass for electronic equipment of the present invention will be explained. In this embodiment, an external cover glass will be described as an example of the cover glass for an electronic device, and the cover glass is detachably attached so as to cover a part of a housing of the electronic device.
Fig. 5 is a diagram showing a state in which the cover glass for electronic equipment (hereinafter, cover glass 100) according to embodiment 2 is attached to an electronic equipment. As shown in fig. 5, the cover glass 100 is an external cover glass that is detachably attached so as to cover a part of the housing of the electronic device. In embodiment 2, the smartphone 300 is shown as an example of an electronic device, but the electronic device is not limited to this, and may be another mobile phone, a portable game machine, a PDA (Personal digital Assistant), a digital camera, a video camera, a tablet PC (Personal Computer), or the like.
The smartphone 300 includes a touch panel display 302 and a cover glass for housing (cover glass for electronic device) 304 that covers the surface of the touch panel display 302. Cover glass 304 for the case is attached to the inside of a bezel (bezel) of case 306 so as to be a part of the case of smartphone 300.
The cover glass 100 includes a glass substrate 102. In order to protect cover glass 304 for a housing, cover glass 100 is attached to a user of smartphone 300 so as to cover the outer main surface of cover glass 304 for a housing.
Fig. 6 is a schematic cross-sectional view after the cover glass 100 of fig. 5 is attached to an electronic device (smartphone 300). In fig. 6, a cover glass 304 for a housing is shown for the smartphone 300, and components other than the cover glass 304 for the housing are schematically shown as a smartphone main body 300A.
As shown in fig. 6, the cover glass 100 includes: a glass substrate 102, the glass substrate 102 for protecting an electronic device (e.g., a smartphone 300); and a bonding portion (bonding layer) 104 provided on the back surface side of the glass substrate 102, the bonding portion 104 being used for detachably bonding the glass substrate 102 to the electronic device (smartphone 300). The glass substrate 102 includes: surface 102B (1 st major surface); a back surface 102C (2 nd main surface) that is arranged to face a housing of the electronic apparatus 102C; and an end face 102A, the end face 102A connecting the surface 102B and the back face 102C. The thickness of the glass substrate 102 is 0.2 to 0.5 mm. As shown in fig. 5, an opening is formed in the glass substrate 102 so as to correspond to a position of a microphone, a speaker, a button, or the like of the electronic device. The bonding portion 104 is formed over the entire surface of the back surface 102C of the glass substrate 102 excluding the opening portion and the outer peripheral portion in a plan view.
Fig. 7 is an enlarged view of the range X of fig. 6. As shown in fig. 7, the cover glass 100 has, as an integral structure, a recessed portion 106 recessed inward in the plane direction on the back side of the outer peripheral portion thereof. In embodiment 2, the outer peripheral edge 104A of the bonded portion 104 is disposed at a distance inward in the surface direction (the left-right direction in fig. 7) from the end surface 102A of the glass substrate 102, and the recessed portion 106 is formed as a space surrounded by the outer peripheral portion of the back surface 102C, the outer peripheral edge 104A of the bonded portion, and the cover glass 304 for the housing.
By forming the recess 106 as described above, when the cover glass 100 is attached to the smartphone 300, a gap is generated between the cover glass 100 and the smartphone 300 by the recess 106. Therefore, the user can hook a nail or the like in the gap and peel the cover glass 100. Therefore, the cover glass 100 made of glass having good peelability can be realized.
In particular, by forming the recessed portion 106 by disposing the outer peripheral end 104A of the bonded portion 104 at a position spaced apart from the end surface 102A, the recessed portion 106 can be formed easily without processing glass having high hardness.
Fig. 8 is a diagram showing a layer structure of the cover glass 100 of fig. 5, and fig. 9 is a diagram showing a step of forming the cover glass 100 of fig. 5. As shown in fig. 9, the cover glass 100 is manufactured through (1) a glass substrate forming step S400, (2) a chemical strengthening step S402, (4) a glass surface modification treatment S404, (4) an antifouling coating layer forming step S406, and (5) a bonded portion forming step S410.
In the glass substrate forming step S400, the glass substrate 102 having a desired shape is formed by machining and etching. For the glass substrate 102, aluminosilicate glass containing: SiO 2258 to 75 wt.% of Al2O34 to 20% by weight of Li23-10% by weight of O and Na2O is 4 to 13% by weight, but not limited thereto, soda lime glass (soda glass) or the like may be used.
In the chemical strengthening step S402, the glass substrate 102 obtained in step S400 is subjected to chemical strengthening treatment. The chemical strengthening treatment is a treatment in which a molten chemical strengthening salt is brought into contact with the glass substrate 102 to cause ion exchange between alkali metal ions having a relatively large atomic radius in the chemical strengthening salt and alkali metal ions having a relatively small atomic radius in the glass substrate 102, thereby causing the alkali metal ions having a large ionic radius to permeate into the surface layer of the glass substrate 102, thereby generating a compressive stress.
As the chemical strengthening salt, an alkali metal nitrate such as potassium nitrate or sodium nitrate is preferably used. Further, as a method of the chemical strengthening treatment, a low-temperature ion exchange method is preferable, in which ion exchange is performed at a temperature not higher than the glass transition point, for example, at a temperature of 300 to 500 ℃. Since the glass substrate 102 subjected to the chemical strengthening treatment has high strength and excellent impact resistance, the glass substrate 102 for the cover glass 100 can sufficiently exhibit the effect as a cover glass even if the thickness is, for example, about 0.3 mm.
In the glass surface modification treatment S404, the surface of the glass substrate 102 is subjected to a glass surface modification treatment composed of two treatments, i.e., a planar plasma treatment and a downstream plasma treatment. This sufficiently improves the adhesion stability of the antifouling coating layer to the glass substrate, and can improve the durability of the surface of the antifouling coating material. The details of the glass surface modification treatment S404 are the same as those of step S102 described in embodiment 1.
In the antifouling coating forming step S406, the antifouling coating 110 is formed on the glass substrate 102 chemically strengthened in step S402. The anti-fouling coating layer 110 is formed on the surface of the glass substrate 102 by, for example, spraying, dipping, vapor deposition, or brushing. The coating material is preferably a perfluoropolyether compound (fluorine-based resin) having a hydroxyl group at the terminal group. This strongly bonds to a functional group such as a hydroxyl group or a carboxyl group on the surface of the glass substrate 102, and can exhibit high smoothness and durability. Further, by forming the stain-proofing coating layer 110, adhesion of stains such as fingerprints is suppressed, and even if stains such as fingerprints adhere, they can be easily wiped off.
The antifouling coating 110 forms the adhesion region 110a and the flow region 110b in its interior accompanied by hardening (solvent evaporation). In the zone thickness adjusting step S408, the evaporation rate of the solvent is adjusted to volatilize the molecules having a small molecular weight, thereby reducing the thickness of the flow zone 110 b. The ratio of the thickness of the adhesion region 110a to the thickness of the antifouling coating layer 110 is 20% to 80%, and more specifically 40% to 70%. As the zone thickness adjusting step, baking treatment, ultraviolet irradiation treatment, and vacuum degree adjusting treatment by reduced pressure are specifically performed.
In the bonded portion forming step S410, the bonded portion 104 is formed on the glass substrate 102. The adhesion portion 104 is formed of a silicon adhesive. Here, the attachment portion 104 may have the following structure: a reinforcing film for reinforcing the glass substrate 102; a 1 st adhesive layer for adhering the back surface 102C and the reinforcing film; and a 2 nd adhesive layer formed of a silicon-based adhesive for bonding the reinforcing film to the cover glass 304 for a housing (each layer is not shown). By providing such a reinforcing film, the glass substrate 102 can be reinforced from the back side. In addition, from the viewpoint of achieving both the release property and the thinning of the cover glass 100, the thickness of the bonded portion 104 is preferably in the range of 0.02 to 0.2mm, and more preferably in the range of 0.05 to 0.1 mm.
Reference is again made to fig. 7. As shown in fig. 7, the length L1 of the recess 106 recessed inward (depth of the recess 106 from the end face 102A) may be in the range of 0.1mm to 0.3mm from the end face 102A of the glass substrate 102. This can achieve both peelability and a good appearance. That is, when the length L1 is 0.1mm or more, the peelability can be further exhibited. In the case where the length L1 exceeds 0.3mm, dust, sebum, and the like remain in the recess 106 with the passage of time, possibly detracting from the aesthetic appearance of the smartphone 300. In particular, in a mobile electronic device such as a mobile phone including the smartphone 300, since the device is often put in a pocket of clothes of a user, fibers of clothes and the like tend to be easily left in the recess 106 as dust.
Fig. 10 is an explanatory diagram about a range where the depression 106 of fig. 7 is formed. Fig. 10(a) is a view showing a 1 st example, and fig. 10(b) is a view showing a 2 nd example. In fig. 10(a) and (b), the range of the recess 106 is indicated by a broken line.
As shown in fig. 10(a), a recessed portion 106 may be provided on the entire periphery of the back surface side of the outer peripheral portion of the cover glass 100. As shown in fig. 10(b), the recessed portion 106 may be provided only on a part of the rear surface side of the outer peripheral portion of the cover glass 100. In fig. 10b, the recessed portion 106 is provided on one side (the upper side in fig. 10 b) of the pair of short sides of the smartphone 300, but the recessed portion 106 is not limited thereto, and a recessed portion having an arc shape in a plan view may be provided on a part of the side, or a recessed portion may be provided on a corner portion of the cover glass 100 in a plan view, and the recessed portion 106 may be provided on at least a part of an outer peripheral portion of the cover glass 100.
[ embodiment 3]
In embodiment 2 described above, the recessed portion 106 is formed by the position of the outer peripheral end 104A of the bonded portion 104, but the cover glass 200 of embodiment 3 is different from the cover glass 100 of embodiment 2 in that: the back surface side of the outer peripheral portion of the glass substrate 202 is recessed inward, forming a part of the recessed portion 106.
Fig. 11 is a diagram showing an outer peripheral portion of a cover glass 200 of embodiment 3, and fig. 12 is a diagram showing another example of embodiment 3. Fig. 11 and 12 correspond to fig. 7 of embodiment 2.
In the cover glass 200 shown in fig. 11, an intermediate surface 202D inclined inward from the end surface 202A (inward in the surface direction of the rear surface 202C) is formed between the end surface 202A and the rear surface 202C of the glass substrate 202. The intermediate surface 202D may be formed on the entire periphery of the outer periphery of the glass substrate 202, or may be formed only on a partial side of the outer periphery, or a part of the outer periphery, or a corner portion of the glass substrate 202 in a plan view. The intermediate surface 202D constitutes a part of the contour of the recess 106.
With such a configuration, the gap generated between cover glass 200 and smartphone 300 can be made larger than the thickness of attachment portion 104. Therefore, the user more easily hooks the nail or the like in the gap of the depression 106. Therefore, the peelability of the cover glass 200 can be improved as compared with embodiment 2.
In the cover glass 210 shown in fig. 12, a glass substrate 212 includes: surface (1 st major surface) 212B; back surface (2 nd main surface) 212C; an end surface 212E as an inclined surface curved in a sectional view; and an intermediate surface 212D between the back surface 212C and the end surface 212E. The end surface 212E is inclined in such a manner as to taper from the back surface 212C side toward the surface 212B side. Also, a boundary portion 212F between the surface 212B and the end face 212E of the glass substrate 212 is formed in a rounded shape. Moreover, a boundary portion 212A between the end surface 212E and the intermediate surface 212D (the outermost peripheral portion of the end surface 212E) is also formed in a rounded shape.
In addition, the height of the end surface 212E is preferably higher than the height of the intermediate surface 212D in terms of the height of the glass substrate 212 in the thickness direction. This is because: in normal use (after the end of the attaching work), smoothness at the time of contact is more important than ease of hooking.
As described above, the end face 212E is inclined so as to taper from the back face 212C side toward the front face 212B side, and therefore, when the user operates the electronic apparatus, hooking of a finger or the like of the user can be prevented. Further, by forming the boundary portion 212A of the surface 212B and the end face 212E of the glass substrate 212 to be rounded, the tactile sensation when the user touches the boundary portion with a finger can be made smoother. Therefore, it is particularly effective in the case of the smartphone 300 having the touch panel display 302.
Fig. 13 is a view illustrating a method of processing the outer peripheral portion of the glass substrates 202 and 212 shown in fig. 11 and 12.
Fig. 13(a) is a diagram of processing the glass substrate 202 by machining. When the intermediate surface 202D having a linear cross-sectional shape is formed as in the glass substrate 202 of fig. 11, the machining (for example, machining using the rotary grinder 308) illustrated in fig. 13(a) is effective.
Fig. 13(b) is a diagram of processing the glass substrate 212 by etching. When the intermediate surface 212D having a curved cross-sectional shape is formed as in the glass substrate 212 of fig. 12, the etching process illustrated in fig. 13(b) is effective. Further, even when the end surface 212E is formed in addition to the intermediate surface 212D and the boundary portion 212F is formed to have a rounded shape, etching is advantageous because etching can be performed at once if etching is performed. Specifically, the shapes of the intermediate surface 212D, the end surface 212E, and the boundary portions 212A and 212F in fig. 12 can be appropriately produced by masking the region of the glass substrate 212 other than the region to be etched with the resist material 310 and etching the front surface side more than the back surface side.
In the above embodiments, the structure in which the cover glasses 100, 200, and 210 are attached to the cover glass 304 for the case of the smartphone 300 is described. However, the present invention is not limited to this, and may be configured to be attached to the back surface side of the case 306 of the smartphone 300, for example.
[ examples ]
As an example, as shown in fig. 7 of embodiment 2, a test and evaluation were performed by forming a recessed portion 106 by disposing only an outer peripheral end 104A of a bonded portion 104 with a space from an end surface 102A, and changing a length L1 of the recessed portion 106. The thickness of the glass substrate 102 is 0.3mm, and the height of the recess 106 is 0.1 mm.
The cover glasses 100 having the length L1 of the recessed portion 106 of the samples 101 to 110 described in table 5 were prepared, and the following tests were performed. That is, the respective cover glasses of the samples 101 to 110 were actually stuck to the smartphone 300, and how many times the subject could peel the cover glasses with the finger was tested. The evaluation criteria are as follows.
◎ success 1 time, ○ success 2-3 times, △ success 4-5 times, and more than 6 times
Further, in order to investigate the productivity of each cover glass of the samples 101 to 110, after each cover glass was attached to the smartphone 300, the state after 30 days of use was investigated. In this embodiment, a smartphone 300 in which the outer periphery of the cover glass 304 for the housing is black-painted is used.
[ Table 5]
Figure BDA0001300868460000191
[ results ]
As is clear from table 5, the length L1 of the recessed portion 106 (depth of the recessed portion 106 from the end face 102A) may be in the range of 0.1mm to 0.3 mm.
While the preferred embodiments of the present invention have been described above with reference to the drawings, it is needless to say that the present invention is not limited to the examples. It is obvious to those skilled in the art that various modifications and variations can be made within the scope of the claims and that these modifications and variations also fall within the technical scope of the present invention.
In particular, in embodiments 2 and 3, the description has been given mainly on the configuration in which the outer peripheral end of the bonded portion is disposed at an interval from the end face of the glass substrate to the inner side in the surface direction of the back face of the glass substrate. However, a notch-like structure may be provided between the 2 nd main surface and the end surface of the glass substrate, and only the notch structure may be used as the recessed portion. For example, in this case, the following configuration may be adopted: in the cross-sectional view, the position of the outer peripheral end of the bonded portion and the position of the end face of the glass substrate are aligned, and the outer peripheral portion of the bonded portion is aligned with the inner surface of the notch structure of the glass substrate. Thus, a gap can be formed between the outer peripheral portion of the attachment portion and the housing of the electronic device, and the gap can be made a recessed portion. In such a configuration, a process of reducing the adhesiveness of the outer peripheral portion of the attachment portion may be performed in advance.
Industrial applicability
The present invention is applicable to cover glasses for electronic devices used for protecting display screens of portable devices such as mobile phones, portable game machines, PDAs (Personal digital assistants), digital cameras, video cameras, and tablet PCs (Personal computers), and a method for manufacturing the cover glasses.
Description of the reference symbols
1: cover glass for electronic equipment; 10: a glass substrate; 10 a: an outer peripheral end surface; 10 b: a notch; 10 c: an ear hole; 10 d: a key operation hole; 12: a major surface; 20: an antifouling coating; 22: an attachment region; 24: a flow region; 100. 200, 210: a protective cover glass; 102. 202, 212: a glass substrate; 102A, 202A: an end face; 102B, 202B, 212B: surface (1 st major surface); 102C, 202C, 212C: a back side (2 nd major surface); 202D, 212D: a middle surface; 212E: an end face; 212A, 212F: a boundary portion; 104: a sticking part; 104A: an outer peripheral end; 106: a recessed portion; 110: an antifouling coating; 300: a smart phone; 300A: a smartphone body portion; 302: a touch panel display; 304: a cover glass for the housing; 306: a housing; 308: rotating the grinding tool; 310: a corrosion resistant material.

Claims (15)

1. An external cover glass for electronic equipment, which can be attached to and detached from an electronic equipment case so as to cover a part of the electronic equipment case,
this external safety cover glass possesses:
a glass substrate having: 1 st main surface; a 2 nd main surface which is a rear surface opposite to the 1 st main surface and is disposed facing a housing of the electronic device; and an end face connecting the 1 st main surface and the 2 nd main surface, an
A bonding unit for attaching and detaching the glass substrate to and from a housing of the electronic device;
an intermediate surface is formed between the end surface of the glass substrate and the 2 nd main surface,
a gap is provided between the housing of the electronic device and the intermediate surface by a recess portion formed by the intermediate surface and at least a part of the outer peripheral end of the attachment portion.
2. The external cover glass for electronic equipment according to claim 1, wherein the adhesive portion is adhered to a cover glass for housing which is a part of a housing of the electronic equipment.
3. The externally-attached cover glass for electronic equipment as claimed in claim 2, wherein said attachment portion is formed of a silicon-based adhesive.
4. The external protective cover glass for electronic equipment according to claim 3,
the sticking portion has:
a reinforcing film for reinforcing the glass substrate;
a 1 st adhesive layer for bonding the 2 nd main surface and the reinforcing film; and
and a 2 nd bonding device formed of the silicon-based adhesive and configured to bond the reinforcing film to the cover glass for a housing.
5. The external protective cover glass for electronic equipment according to any one of claims 1 to 4, wherein the thickness of said adhesion portion is in the range of 0.02mm to 0.2 mm.
6. The external protective cover glass for electronic equipment according to any one of claims 1 to 4, wherein a depth of the recessed portion from the end surface is in a range of 0.1mm to 0.3 mm.
7. The externally-mounted protective cover glass for electronic equipment as defined in any one of claims 1 to 4, wherein said end surface is inclined so as to taper from said 2 nd main surface side toward said 1 st main surface side, and is an inclined surface which is linear or curved in a sectional view.
8. The externally-mounted protective cover glass for electronic equipment as set forth in any one of claims 1 to 4, which is detachably attached so as to cover a main surface of a cover glass for housing which is a part of a housing of the electronic equipment.
9. The externally mounted protective cover glass for electronic equipment as claimed in claim 1, wherein said glass substrate is chemically strengthened and has a compressive stress layer.
10. The externally-mounted protective cover glass for electronic equipment as claimed in claim 1, wherein an antifouling coating containing a perfluoropolyether compound is provided on the surface of said glass substrate.
11. A method for manufacturing external protective cover glass for electronic equipment is characterized in that,
the manufacturing method comprises the following steps:
a glass substrate production step of producing a glass substrate having: 1 st main surface; a 2 nd main surface which is a rear surface opposite to the 1 st main surface and is disposed facing a housing of the electronic device; and an end face connecting the 1 st main surface and the 2 nd main surface, an
A bonded portion forming step of forming a bonded portion for detachably attaching the glass substrate to a housing of the electronic device, in such a manner that: the bonded portion is arranged along the 2 nd main surface of the glass substrate with a gap from the end surface to the inside in the surface direction of the 2 nd main surface, and at least a part of the outer peripheral end of the bonded portion is arranged to form a recessed portion.
12. The method for manufacturing an external protective cover glass for electronic equipment according to claim 11, wherein in the step of forming the bonded portion, the thickness of the bonded portion is set to 0.02mm to 0.2 mm.
13. The method for manufacturing an external protective cover glass for electronic equipment according to claim 11 or 12, wherein in the step of forming the bonded portion, the depth of the recessed portion from the end surface is set to 0.1mm to 0.3 mm.
14. A glass substrate which is chemically strengthened,
the surface of the chemically strengthened glass substrate has an antifouling coating,
the antifouling coating layer contains a perfluoropolyether compound having a hydroxyl group at the terminal group, and has an adhesion region that adheres to the surface of the chemically strengthened glass substrate and remains when immersed in a solvent comprising HFE for 1 minute, and a flow region that is disposed on the surface of the adhesion region and dissolves when immersed in the solvent for 1 minute; the thickness of the antifouling coating layer is 3nm to 30nm, and the ratio of the thickness of the adhesion region to the thickness of the antifouling coating layer is in the range of 20% to 80%,
the glass constituting the glass substrate is amorphous aluminosilicate glass.
15. A cover glass having a chemically strengthened glass substrate and a detachably bonded portion, characterized in that,
the surface of the chemically strengthened glass substrate has an antifouling coating,
the antifouling coating layer contains a perfluoropolyether compound having a hydroxyl group at the terminal group, has an adhesion region and a flow region,
the adhesion region is a region which adheres to the surface of the chemically strengthened glass substrate and remains when immersed in a solvent comprising HFE for 1 minute,
the flow region is disposed on the surface of the adhesion region and is dissolved when immersed in the solvent for 1 minute,
the sticking portion has: a reinforcing film; a 1 st adhesive layer for bonding the glass substrate and the reinforcing film; and a 2 nd adhesive layer made of an adhesive for detachably adhering the glass substrate,
the glass constituting the glass substrate is amorphous aluminosilicate glass.
CN201710363113.1A 2012-09-28 2013-09-24 External protective cover glass, manufacturing method thereof, glass substrate and protective cover glass Active CN107265844B (en)

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