JP2020132498A - Glass base material with anti-fouling layer and method for manufacturing same - Google Patents

Abstract

To improve wear resistance of a glass base material with an anti-fouling layer.SOLUTION: A glass base material with an anti-fouling layer includes a glass base material having a pair of main surfaces opposed to each other, an adhesive layer formed on at least one of the main surfaces of the glass base material, and the anti-fouling layer formed on the surface of the adhesive layer. Vickers hardness of the adhesive layer, which is measured by instrumentation indentation test in the international standard ISO14577 is 7.5 HV or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a glass substrate with an antifouling layer and a method for producing a glass substrate with an antifouling layer.

Conventionally, a cover glass has been used as a front plate of a touch panel or a display panel used in a display device of a smartphone, a tablet PC, a car navigation device, or the like. Since these touch panels and display panels are touched by human fingers during use, stains such as fingerprints, sebum, and sweat are likely to adhere. When these stains are attached, they are difficult to remove, and they are conspicuous due to the difference in light scattering and reflection between the portion where the stain is attached and the portion where the stain is not attached, which causes a problem of impairing visibility and aesthetics. Therefore, as these cover glasses, there is known a method of using a glass substrate having an antifouling layer made of a fluorine-containing organic compound formed on a portion touched by a human finger or the like (Patent Document 1). The antifouling layer is required to have high water repellency and oil repellency in order to suppress the adhesion of dirt, and is also required to have abrasion resistance against repeated wiping of the attached dirt.

Japanese Unexamined Patent Publication No. 2000-144097

However, the wear resistance of the antifouling layer is insufficient with the conventional cover glass.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a glass substrate with an antifouling layer having excellent wear resistance of the antifouling layer and a method for producing the same.

The present invention comprises a glass substrate having a pair of main surfaces facing each other.
With the adhesion layer formed on at least one main surface of the glass substrate,
A glass substrate with an antifouling layer provided with an antifouling layer formed on the surface of the adhesive layer.
Provided is a glass substrate with an antifouling layer having a Vickers hardness of 7.5 HV or more measured by an instrumentation indentation test (international standard ISO14577) of the adhesive layer.

According to the present invention, it is possible to provide a glass substrate with an antifouling layer having excellent wear resistance of the antifouling layer.

FIG. 1 is a schematic cross-sectional view of the glass substrate with an antifouling layer of the present invention according to the first embodiment. FIG. 2 is a schematic cross-sectional view of a modified example of the glass substrate with an antifouling layer of the present invention. FIG. 3 is a manufacturing flow according to the first embodiment of the method for manufacturing a glass substrate with an antifouling layer of the present invention.

The glass substrate with an antifouling layer of the present invention has an adhesion layer. The Vickers hardness of the adhesion layer of the glass substrate with an antifouling layer of the present invention is 7.5 HV or more. The Vickers hardness is preferably 8.0 HV or higher, more preferably 8.5 HV or higher, and even more preferably 9.1 HV or higher. The present invention has been made based on the finding that the abrasion resistance of the antifouling layer formed on the adhesion layer can be improved by increasing the Vickers hardness.

Here, if the hardness of the adhesion layer is high, it is difficult for the adhesion layer to peel off in a minute region, so that it is considered that the abrasion resistance of the antifouling layer is improved.

Further, it was found that the hardness of the outermost surface of the adhesion layer in the present invention is higher than the surface hardness of the glass substrate itself.
The thickness of the adhesion layer is preferably 20 nm or less, more preferably 15 nm or less, and further preferably 10 nm or less. When the thickness of the adhesive layer of the present invention is within the above range, the hardness of the adhesive layer can be increased and the wear resistance of the antifouling layer can be improved.
It is considered that when the adhesion layer of the present invention becomes thin, it is affected by the unevenness on the surface of the glass substrate, and the distribution of the adhesion layer is microscopically biased on the surface of the glass substrate. As a result, it is considered that a part of the adhesion layer is aggregated to increase the density and the hardness. The principle that the hardness increases due to the thin adhesion layer is not limited to this. On the other hand, the thickness of the adhesion layer is preferably 5 nm or more, which tends to be higher than the surface hardness of the glass substrate itself.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(Embodiment 1 of a glass substrate with an antifouling layer)
FIG. 1 is a schematic view of a glass substrate with an antifouling layer according to the first embodiment of the present invention. As shown in FIG. 1, the glass substrate 100 with an antifouling layer according to the first embodiment has a glass substrate 101, an adhesion layer 102, and an antifouling layer 103.

The glass substrate 101 has a first main surface 101a and a second main surface 101b that face each other. The adhesion layer 102 is formed on the first main surface 101a. The adhesion layer 102 has a first surface 102a far from the glass substrate 101 and a second surface 102b close to the glass substrate 101. An antifouling layer 103 is formed on the first surface 102a of the adhesion layer. The antifouling layer 103 has a first surface 103a far from the glass substrate 101 and a second surface 103b close to the glass substrate 101. The adhesion layer 102 and the antifouling layer 103 may be formed on the side of the second main surface 101b, or may be formed on both sides of the glass substrate (first main surface 101a, second main surface 101b). good.
Hereinafter, each configuration of the glass substrate 100 with an antifouling layer will be described in detail.

(Glass substrate)
The glass substrate 101 used in the present embodiment is not particularly limited, and general glass containing silicon dioxide as a main component, for example, soda lime silicate glass, aluminosilicate glass, borosilicate glass, non-alkali glass, quartz glass, etc. A glass substrate can be used.

The glass substrate 100 with an antifouling layer of the present invention is used as a cover glass for a touch panel or a display panel used in, for example, a display device of a smartphone, a tablet PC, a car navigation device, or the like. In this case, it is preferable that the glass substrate 101 is strengthened. The strengthening treatment is physical strengthening or chemical strengthening, and it is particularly preferable that the chemical strengthening treatment is performed.

Therefore, the composition of the glass substrate 101 used in the present embodiment is preferably a composition that can be strengthened by a chemical strengthening treatment, and preferably contains an alkali metal having a small ionic radius such as sodium and lithium. Examples of such glass include aluminosilicate glass, soda-lime silicate glass, borosilicate glass, lead glass, alkaline barium glass, aluminoborosilicate glass and the like.

Here, in the present specification, the glass after being chemically strengthened is referred to as "chemically strengthened glass". The mother composition of the chemically strengthened glass is the same as that of the glass before the chemically strengthened glass, and the mother composition of the chemically strengthened glass is the composition inside the glass excluding the ion-exchanged layer on the glass surface.

As a specific glass composition (that is, a mother composition in chemically strengthened glass), for example, the following glass composition is likely to form a preferable stress profile by the chemically strengthening treatment.
(1) In the oxide-based mass percentage display, SiO ₂ is 50 to 80%, Al ₂ O ₃ is 10 to 25%, B ₂ O ₃ is 0 to 10%, Li ₂ O is 2 to 10%, and Na. the ₂ O 0 to 11%, 0-10% of _{K 2} O, containing, MgO, CaO, SrO, the sum MgO + CaO + SrO + BaO is 0 to 10% of BaO content, the total of ZrO ₂ and TiO ₂ content It is preferable that ZrO ₂ + TiO ₂ is 0 to 5%.
(2) In the oxide-based mass percentage display, SiO ₂ is 55 to 80%, Al ₂ O ₃ is 10 to 28%, B ₂ O ₃ is 0 to 10%, Li ₂ O is 2 to 10%, and Na. the ₂ O containing 0-10% of 0.5 to 11% and _{K 2 O, MgO, CaO,} SrO, containing a total of BaO content (MgO + CaO + SrO + BaO ) is 0-10% and ZrO ₂ and TiO ₂ It is more preferable that the total amount (ZrO ₂ + TiO ₂ ) is 0 to 5%.
(3) In terms of oxide-based mass percentage display, SiO ₂ is 55 to 75%, Al ₂ O ₃ is 10 to 25%, B ₂ O ₃ is 0 to 10%, Li ₂ O is 2 to 10%, and Na ₂ It is more preferable that O is 1 to 11%, K ₂ O is 0.5 to 10%, (MgO + CaO + SrO + BaO) is 0 to 10%, and (ZrO ₂ + TiO ₂ ) is 0 to 5%.
Hereinafter, each component of the glass composition will be described in detail. In the following,% notation means mass percentage unless otherwise specified.

SiO ₂ is a component constituting the skeleton of glass. In addition, it is a component that increases chemical durability and reduces the occurrence of cracks when the glass surface is scratched. The content of SiO ₂ is preferably 50% or more, more preferably 55% or more, still more preferably 58% or more.
Further, in order to increase the meltability of the glass, the content of SiO ₂ is preferably 80% or less, more preferably 75% or less, still more preferably 70% or less.

Al ₂ O ₃ is an effective component for improving the ion exchange property during chemical strengthening and increasing the surface compressive stress after strengthening, and is a component that raises the glass transition temperature (Tg) and raises Young's modulus. Therefore, 10% or more is preferable, 13% or more is more preferable, and 15% or more is further preferable.
The content of Al ₂ O ₃ is preferably 28% or less, more preferably 26% or less, still more preferably 25% or less in order to increase the meltability.

B ₂ O ₃ is not essential, but can be added to improve the meltability during glass production and the like. When B ₂ O ₃ is contained, the content is preferably 0.5% or more, more preferably 1% or more, still more preferably 2% or more.
The content of B ₂ O ₃ is preferably 10% or less, more preferably 8% or less, still more preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. As a result, it is possible to prevent the occurrence of veins during melting and deterioration of the quality of the chemically strengthened glass. In order to increase the acid resistance, it is preferable that B ₂ O ₃ is not substantially contained.

Li ₂ O is a component that forms surface compressive stress by ion exchange. The content of Li ₂ O is preferably 2% or more, more preferably 3% or more, still more preferably 4% or more in order to increase the compressive stress layer depth DOL.
Further, in order to increase the chemical durability of the glass, the content of Li ₂ O is preferably 10% or less, more preferably 8% or less, still more preferably 7% or less. When Li ₂ O is in this range, the chemical durability is good and the acid treatment can be performed.

Na ₂ O Although not essential, Na ₂ O is a component that forms a surface compressive stress layer by ion exchange using a molten salt containing potassium, and is a component that improves the meltability of glass. The content of Na ₂ O is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more.
The Na ₂ O content is preferably 11% or less, more preferably 10% or less, still more preferably 8% or less, and particularly preferably 6% or less.

K ₂ O is not essential, but may be included to improve the meltability of the glass and suppress devitrification. The K ₂ O content is preferably 0.5% or more, more preferably 1% or more.
Further, the content of K 2 _O in order to increase the compressive stress value by ion exchange, preferably 10% or less, more preferably 9% or less, more preferably not more than 8%.

Alkali metal oxides such as Li ₂ O, Na ₂ O and K ₂ O are all components that lower the melting temperature of glass, and are the total contents of Li ₂ O, Na ₂ O and K ₂ O (Li). ₂ O + Na ₂ O + K ₂ O) is preferably 2% or more, more preferably 5% or more, further preferably 7% or more, still more preferably 8% or more.
(Li ₂ O + Na ₂ O + K ₂ O) is preferably 20% or less, more preferably 18% or less in order to maintain the strength of the glass.

Alkaline earth metal oxides such as MgO, CaO, SrO, and BaO are all components that increase the meltability of glass, but tend to reduce the ion exchange performance.
Therefore, the total content of MgO, CaO, SrO, and BaO (MgO + CaO + SrO + BaO) is preferably 10% or less, and more preferably 5% or less.

When any one of MgO, CaO, SrO and BaO is contained, it is preferable to contain MgO in order to increase the strength of the chemically strengthened glass.
When MgO is contained, the content is preferably 0.1% or more, more preferably 0.5% or more.
Further, in order to improve the ion exchange performance, 10% or less is preferable, and 5% or less is more preferable.

When CaO is contained, the content is preferably 0.5% or more, more preferably 1% or more. In order to improve the ion exchange performance, it is preferably 5% or less, more preferably 1% or less, and further preferably substantially not contained.

When SrO is contained, the content is preferably 0.5% or more, more preferably 1% or more. In order to improve the ion exchange performance, it is preferably 5% or less, more preferably 1% or less, and further preferably substantially not contained.

When BaO is contained, the content is preferably 0.5% or more, and more preferably 1% or more. In order to improve the ion exchange performance, it is preferably 5% or less, more preferably 1% or less, and further preferably substantially not contained.

ZnO is a component that improves the meltability of glass and may be contained. When ZnO is contained, the content is preferably 0.2% or more, more preferably 0.5% or more. In order to increase the weather resistance of the glass, the ZnO content is preferably 5% or less, more preferably 1% or less, and further preferably substantially not contained.

TiO ₂ is a component that improves the crushability of chemically strengthened glass, and may be contained. When TiO ₂ is contained, the content is preferably 0.1% or more. The content of TiO ₂ is preferably 5% or less, more preferably 1% or less, and even more preferably substantially absent, in order to suppress devitrification during melting.

ZrO ₂ is a component that increases the surface compressive stress due to ion exchange, and may be contained. When ZrO ₂ is contained, the content is preferably 0.5% or more, more preferably 1% or more. Further, in order to suppress devitrification at the time of melting, 5% or less is preferable, and 3% or less is more preferable.

Further, the content of TiO ₂ and ZrO ₂ (TiO ₂ + ZrO ₂ ) is preferably 5% or less, more preferably 3% or less.

Y ₂ O ₃ , La ₂ O ₃ , and Nb ₂ O ₅ are components that improve the crushability of chemically strengthened glass, and may be contained. When these components are contained, the content of each is preferably 0.5% or more, more preferably 1% or more, further preferably 1.5% or more, particularly preferably 2% or more, most preferably. It is preferably 2.5% or more.

The total content of Y ₂ O ₃ , La ₂ O ₃ , and Nb ₂ O ₅ is preferably 9% or less, more preferably 8% or less. Within such a range, the glass is less likely to be devitrified during melting, and it is possible to prevent the quality of the chemically strengthened glass from deteriorating. The contents of Y ₂ O ₃ , La ₂ O ₃ , and Nb ₂ O ₅ are preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, and particularly preferably 0.7%. It is less than or equal to, and most preferably 0.3% or less.

Ta ₂ O ₅ and Gd ₂ O ₃ may be contained in a small amount in order to improve the crushability of the chemically strengthened glass, but since the refractive index and the reflectance are increased, each is preferably 1% or less, preferably 0.5%. The following are more preferable, and it is further preferable that they are not substantially contained.

P ₂ O ₅ may be contained in order to improve the ion exchange performance. When P ₂ O ₅ is contained, the content is preferably 0.5% or more, and more preferably 1% or more. In order to increase the chemical durability, the content of P ₂ O ₅ is preferably 2% or less, and more preferably substantially not contained.

When the glass is colored and used, a coloring component may be added within a range that does not hinder the achievement of the desired chemical strengthening properties. Examples of the coloring component include Co ₃ O ₄ , MnO ₂ , Fe ₂ O ₃ , NiO, CuO, Cr ₂ O ₃ , V ₂ O ₅ , Bi ₂ O ₃ , SeO ₂ , TIO ₂ , CeO ₂ , Er _2. O ₃ , Nd ₂ O ₃ are mentioned as suitable ones. These may be used alone or in combination.

The total content of the coloring components is preferably 7% or less. As a result, devitrification of the glass can be suppressed. The content of the coloring component is more preferably 5% or less, further preferably 3% or less, and particularly preferably 1% or less. If it is desired to increase the visible light transmittance of the glass, it is preferable that these components are not substantially contained.

Further, SO ₃ , chloride, fluoride and the like may be appropriately contained as a fining agent at the time of glass melting. It is preferable that As ₂ O ₃ is substantially not contained. When Sb ₂ O ₃ is contained, it is preferably 0.3% or less, more preferably 0.1% or less, and most preferably substantially not contained.

Next, the properties of the glass substrate 101 will be described.

The shape of the glass substrate 101 is not limited to the flat shape as shown in FIG. 1, but may be a curved surface shape having one or more bent portions. Further, examples of the front view include a rectangle, a trapezoid, a circle, and an ellipse.

The thickness of the glass substrate 101 is not particularly limited. For example, in the case of a cover glass for a mobile device, it is preferably 0.1 mm to 2.5 mm, more preferably 0.2 mm to 1.5 mm, and further preferably 0.5 mm to 1 mm. For example, in the case of an image display device such as a display device, a car navigation system, a console panel, or an instrument panel, the thickness of the glass substrate 101 is preferably 0.1 mm to 2.1 mm. The thickness of the above glass means the thickness of a single piece of glass before being bonded when a plurality of glasses are bonded by a method such as a laminating material or an adhesive.

The Vickers hardness of the glass substrate 101 is preferably 5.5 HV or more, and more preferably 6.0 HV or more. On the other hand, it is preferably 7.5 HV or less, and more preferably 7.0 HV or less.
Further, as described above, when the adhesion layer 102 is thin, the Vickers hardness of the glass substrate 101 is preferably smaller than the Vickers hardness of the adhesion layer 102.
The method for measuring Vickers hardness will be described later.
(Adhesion layer)
The adhesion layer 102 is formed on the first main surface 101a of the glass substrate 101. The composition of the adhesion layer 102 is not particularly limited, and examples thereof include silicon dioxide and alumina. Preferably, it is composed mainly of silicon dioxide.

The Vickers hardness of the adhesion layer 102 is 7.5 HV or more. The Vickers hardness is preferably 8.0 HV or higher, more preferably 8.5 HV or higher, and even more preferably 9.1 HV or higher. When the Vickers hardness of the adhesion layer 102 is within this range, the wear resistance of the antifouling layer 103 formed on the adhesion layer 102 can be improved. On the other hand, the Vickers hardness of the adhesion layer 102 is, for example, 13.5 HV or less from the viewpoint of film forming technology.
In the present invention, the Vickers hardness is measured by the international standard ISO14577 instrumentation indentation test.

The thickness of the adhesion layer 102 is preferably 20 nm or less, more preferably 15 nm or less, and further preferably 10 nm or less. When the thickness of the adhesion layer is within the above range in the present invention, the hardness of the adhesion layer can be increased and the wear resistance of the antifouling layer can be improved. On the other hand, the thickness of the adhesion layer is preferably 5 nm or more because it tends to be higher than the surface hardness of the glass substrate itself.

(Anti-fouling layer)
The antifouling layer 103 contains a fluorine-containing organic compound. The fluorine-containing organic compound is not particularly limited as long as it has any one or more of antifouling property, water repellency, oil repellency, hydrophilicity and lipophilicity. The antifouling layer 103 may have functions such as suppressing adhesion of various stains such as sweat and dust as well as fingerprint traces, making it easier to wipe off the stains, and making the stains less noticeable.

Examples of the fluorine-containing organic compound include a perfluoroalkyl group-containing compound and a perfluoropolyether group-containing compound, and a silane compound having a perfluoropolyether group is preferably used.

Examples of the silane compound having a perfluoropolyether group include a material represented by the following formula A and / or a material containing a partially hydrolyzed condensate thereof.
Rf ^3- Rf ^2- Z ^{1 set} A
In formula A, Rf ³ is a group: C _m F _{2 m + 1} (where m is an integer of 1 to 6).
Rf ² is based on: -O- (C _a F _2a O) _n- (where a is an integer of 1 to 6, n is an integer of 1 or more, and n is 2 or more. , Each -C _a F _2a O- unit may be the same or different.)
Z ¹ is a group: -Q ^2- {CH ₂ CH (SiR ² _q X ² _3-q )} _r- H (where Q ² is-(CH ₂ ) _s- (where s is It is an integer of 0 to 12) or is − (CH ₂ ) _s − and −CH ₂ containing at least one selected from an ester bond, an ether bond, an amide bond, a urethane bond and a phenylene group. Part or all of the − units may be replaced by −CF ₂ − units and / or −CF (CF ₃ ) − units, where R ² is a hydrogen atom or a monovalent with 1 to 6 carbon atoms. The hydrocarbon group may contain a substituent, X ² is independently a hydroxyl group or a hydrolyzable group, and q is an integer of 0 to 2. Yes, r is an integer of 1 to 20).
Examples of the hydrolyzable group in X ² include an alkoxy group, an asyloxy group, a ketooxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, a halogen atom and the like. Among these, an alkoxy group, an isocyanate group and a halogen atom (particularly a chlorine atom) are preferable from the viewpoint of the balance between stability and ease of hydrolysis. As the alkoxy group, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.

Examples of materials that can form the antifouling layer 103 include commercially available "Afluid (registered trademark) S-550" (trade name, manufactured by Asahi Glass Co., Ltd.) and "KP-801" (trade name, Shin-Etsu Chemical Co., Ltd.). (Product name, manufactured by Shin-Etsu Chemical Co., Ltd.), "X-71" (product name, manufactured by Shin-Etsu Chemical Co., Ltd.), "KY-130" (product name, manufactured by Shin-Etsu Chemical Co., Ltd.), "KY-178" (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) "KY-185" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), "KY-195" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), "Optur (registered trademark) DSX (trade name)" , Daikin Kogyo Co., Ltd.), etc. Further, a commercially available product to which an oil added, an antistatic agent, etc. is added can also be used.

The thickness of the antifouling layer 103 is not particularly limited, but is preferably 8 nm or more, more preferably 10 nm or more, and further preferably 12 nm or more. On the other hand, the thickness of the antifouling layer 103 is preferably 30 nm or less, more preferably 20 nm or less, and further preferably 19 nm or less. When the thickness of the antifouling layer 103 is 8 nm or more, the layer in contact with the second surface 103b of the antifouling layer 103 can be uniformly covered, and the wear resistance is improved. Further, when the thickness of the antifouling layer 103 is 30 nm or less, the optical characteristics such as the visual reflectance and the haze value in the state where the antifouling layer 103 is laminated are good.

(Modification example)
Next, a modified example of the glass substrate with an antifouling layer in the present invention will be described. Hereinafter, the antireflection layer and the antiglare treatment will be described as modification examples, but the glass substrate with the antifouling layer in the present invention is not limited to this, and has other functions on the first main surface 101a of the glass substrate. A layer may be formed, and the first main surface 101a itself known as glass may be subjected to other treatments.

(Anti-reflective layer)
As shown in FIG. 2, the glass substrate 100 with an antifouling layer may have an antireflection layer 104 between the glass substrate 101 and the adhesion layer 102. The antireflection layer 104 may function as the adhesion layer 102 by lowering the packing density of the outermost layer or a part of the outermost layer. The antireflection layer 104 is, for example, a layer in which high refractive index layers and low refractive index layers are alternately laminated to suppress reflection by external light and improve the display quality of a display image.

The configuration of the antireflection layer 104 is not particularly limited as long as it can suppress the reflection of light within a predetermined range. For example, it is formed by alternately stacking a high refractive index layer of light having a wavelength of 550 nm having a refractive index of more than 1.6 and a low refractive index layer of light having a wavelength of 550 nm having a refractive index of 1.6 or less. ..

The antireflection layer 104 may include a high refractive index layer and a low refractive index layer one by one, and preferably includes two or more layers each. It more preferably contains 2 to 15 layers each, more preferably 4 to 13 layers each, and even more preferably 4 to 10 layers each. As a result, good antireflection characteristics can be obtained.

The materials constituting the high refractive index layer and the low refractive index layer are not particularly limited and can be arbitrarily selected in consideration of the required degree of antireflection and productivity. Examples of the material constituting the high refractive index layer include niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), and aluminum oxide (Al ₂ ). One or more of O ₃ ) and silicon nitride (SiN) may be used. Materials constituting the low refractive index layer include silicon oxide (particularly silicon dioxide SiO ₂ ), a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, and Si and Al. One or more of the materials containing the mixed oxide of the above may be selected and used.

When the thickness of the antireflection layer 104 is preferably 150 nm or more, the reflection of external light can be effectively suppressed. It is more preferably 250 nm or more, and further preferably 350 nm or more. On the other hand, the thickness of the antireflection layer 104 is preferably 1500 nm or less, preferably 1000 nm or less, still more preferably 800 nm or less, in order to secure the rubbing resistance of the steel wool of the film.

(Anti-glare processing)
The first main surface 101a of the glass substrate 101 may have an uneven shape in order to impart antiglare properties. The antiglare-processed first main surface 101a preferably has a root mean square roughness (RMS) of 10 to 1500 nm, more preferably 15 nm to 1000 nm, further preferably 10 nm to 500 nm, and 10 nm. It is particularly preferably ~ 200 nm. When the RMS is within the above range, the haze value of the first main surface 2 having an uneven shape can be adjusted to 3 to 30%, and as a result, the obtained glass substrate 1 with an antifouling layer has excellent antiglare properties. Can be granted.

The root mean square roughness (RMS) can be measured according to the method specified in JIS B 0601: (2001). The haze value is a value measured according to JIS K 7136.

Further, when the first main surface 101a having an uneven shape is observed from above, a circular hole is observed. The size of the circular hole observed in this way (diameter in terms of a perfect circle) is preferably 5 μm to 50 μm. Within such a range, it is possible to achieve both anti-glare and anti-glare properties of the glass substrate 100 with an antifouling layer.

(Embodiment 1 of the manufacturing method of the present invention)
Next, the first embodiment in the manufacturing method of the present invention will be described. FIG. 3 shows the flow in the first embodiment of the manufacturing method.

As shown in FIG. 3, in the first manufacturing method of the glass substrate with an antifouling layer of the present invention,
(Step S401) A step of preparing a glass substrate having a pair of main surfaces facing each other, and (a glass substrate preparation step).
(Step S402) A step of forming an adhesive layer on the main surface of the glass substrate and a (adhesive layer forming step).
(Step S403) A step of forming an antifouling layer on the adhesive layer and a step of forming an antifouling layer (step of forming an antifouling layer).
Have.
The details of each step will be described below with reference to FIGS. 1 and 3.

(Step S401)
First, a glass substrate 101 having a first main surface 101a and a second main surface 101b facing each other is prepared. The surface of the glass substrate 101 may be optionally subjected to treatments such as polishing, cleaning, and chemical strengthening.

(Chemical strengthening treatment)
The glass substrate 101 can be chemically strengthened by immersing it in a molten salt and subjecting the surfaces of the first main surface 101a and the second main surface 101b to an ion exchange treatment. In the ion exchange treatment, metal ions having a small ionic radius (typically Li ions or Na ions) existing near the main surface of the glass substrate 101 are converted into ions having a larger ionic radius (typically Li ions). On the other hand, it is Na ion or K ion, and for Na ion, it is replaced with K ion). The molten salt is not particularly limited, but for example, a salt containing K ions is selected.

As the temperature of the molten salt, a temperature below the glass transition point is selected. Although it depends on the composition of the glass and the molten salt, a temperature of 350 ° C. or higher and 500 ° C. or lower is specifically selected.

The immersion time is not particularly limited, but is usually 10 minutes or more and 24 hours or less.

By performing such a chemical strengthening treatment, the surface hardness of the glass substrate 101 can be improved, and when applied to a cover glass or the like, cracking due to impact can be prevented, which is preferable.

(Alkaline treatment)
By immersing the glass substrate 101 in an alkaline solution, organic substances adhering to the surfaces of the first main surface 101a and the second main surface 101b of the glass substrate can be removed.

(Plasma cleaning)
By irradiating the first main surface 101a of the glass substrate with plasma in the atmosphere, the organic matter adhering to the first main surface 101a can be removed. This is preferable because the adhesion to the layer formed on the first main surface 101a is enhanced and the durability is improved.

(Step S402)
Next, the adhesion layer 102 is formed on the first main surface 101a of the glass substrate. The method for forming the adhesion layer is not particularly limited, but it can be formed by, for example, a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method. Examples of the physical vapor deposition method include a vacuum vapor deposition method, an ion-assisted sputtering method (IAD method), a sputtering method, a post-oxidation sputtering method, an ion-assisted sputtering method, an ion beam sputtering method, and an ion-assisted ion beam method. A sputtering method, a post-oxidation sputtering method, or an ion-assisted vapor deposition method is preferable because the hardness of the adhesion layer 102 can be increased relatively easily.

The pressure in the chamber during vacuum deposition is preferably 0.15 Pa or less because the hardness of the adhesion layer 102 can be increased. It is preferably 0.01 Pa or less, more preferably 0.8 Pa or less. On the other hand, when the pressure is 0.03 Pa or more, the plasma discharge can be stably maintained, which is preferable.

Silicon dioxide (SiO ₂ ) is preferable as the sample for vacuum deposition. The sample is placed in a heating container, evaporated by being heated under a low vacuum, and formed on the first main surface 101a of the glass substrate placed facing the heating container.

When the sputtering method is used, the discharge power at the time of film formation is preferably 5000 W or more, and more preferably 7,000 W or more because the hardness of the film can be increased. On the other hand, the discharge power of 20000 W or less is preferable from the viewpoint of preventing cracking of the target and abnormal discharge.

During the film formation of the adhesion layer 102, it is preferable to be exposed to high-energy particles such as a plasma source, an ion source, and a radical source (plasma assist). Plasma assist is preferably performed every time a film of 100 nm or less is formed. It is more preferably 1 nm or less, and further preferably 0.5 nm or less. The high-energy particle source is not particularly limited in any method, but an in-beam, a radical source, an ECR plasma source such as a plasma beam, an ion beam, a linear ion beam, an ECR plasma source, a radical source, or a low impedance antenna plasma source is preferable.

The above steps are preferably performed by, for example, a sputtering apparatus capable of carrying out the post-oxidation sputtering method (for example, RAS1100B II, manufactured by Syncron Co., Ltd.). When forming a SiO ₂ film as the adhesion layer 102, it is preferable to use a Si target, use argon gas and oxygen gas as the discharge gas in the film forming chamber, and use argon and oxygen as the discharge gas in the reaction chamber. In this device, a drum that holds the substrate is placed in a vacuum chamber divided into a film forming chamber and a reaction chamber, and the drum that holds the substrate alternately passes through the film forming chamber and the reaction chamber at high speed, for example, at 100 rpm. Rotate. As a result, a very thin thin film of several nm or less is formed in the film forming chamber. After that, energy may be added to the membrane sent to the reaction chamber by the active gas reacted by the plasma source, or the unreacted portion may be reacted.

In order to increase the hardness of the adhesion layer 102, it is preferable to use an apparatus of such a post-oxidation process method, and further, after forming a fully oxidized SiO ₂ film in the film forming chamber, the reaction chamber It is preferable to apply energy to the SiO ₂ film by using the plasma source of.

(Step S403)
Next, the antifouling layer 103 is formed on the adhesion layer 102.
The method for forming the antifouling layer is not particularly limited, and is represented by a wet method such as a spin coating method, a dip coating method, a casting method, a slit coating method, a spray coating method, or a vacuum vapor deposition method on the adhesion layer 103. The dry method can be mentioned. In order to form an antifouling layer having high adhesion and high wear resistance, it is preferably formed by a vacuum vapor deposition method. Examples of the vacuum vapor deposition method include resistance heating method, electron beam heating method, high frequency induction heating method, reactive vapor deposition method, molecular beam epitaxy method, hot wall vapor deposition method, ion plating method, cluster ion beam method and the like. Be done. Preferably, the resistance heating method makes the apparatus simple and low cost.

The pressure in the chamber during vacuum deposition is preferably 5 × 10 ^-3 Pa or less. If the pressure in the chamber is within this range, vacuum deposition can be carried out without any problem. On the other hand, when the pressure in the chamber during vacuum deposition is 1 × 10 ^-4 Pa or more, the vapor deposition rate of the antifouling layer can be maintained above a certain level, which is preferable.

When the vapor deposition output is 200 kA / m ² or more in terms of current density, it is possible to prevent water from adsorbing to the antifouling layer and stable film formation can be performed, which is preferable. It is known that if water is adsorbed before the antifouling layer is formed on the adhesion layer 102, the antifouling agent is dimerized and does not exhibit sufficient wear durability. More preferably, it is 300 kA / m ² or more, and even more preferably 350 kA / m ² or more. On the other hand, when the vapor deposition output is 1000 kA / m ² or less, it is possible to prevent the components of steel wool and crucible impregnated with the raw material of the antifouling layer from evaporating, which is preferable.

The vapor-deposited sample is preferably held in the form of impregnating a pellet-shaped copper container with a fluorine-containing organic compound. The impregnation work should be performed in a nitrogen atmosphere. By doing so, it is possible to increase the number of layers in which the fluorine-containing organic compound is deposited as a monatomic atom, and the wear resistance of the antifouling layer 103 is improved.

(Modification example)
Next, a modified example of the manufacturing method in the present invention will be described. Hereinafter, the antireflection layer forming step and the antiglare treatment step will be described as modification examples, but the manufacturing method in the present invention is not limited to this, and a layer having other functions on the first main surface 101a of the glass substrate is described. May be formed. Other treatments may be applied to the first main surface 101a itself known as glass.

(Anti-reflection layer forming process)
As shown in FIG. 2, the glass substrate 100 with an antifouling layer may have an antireflection layer 104 between the glass substrate 101 and the adhesion layer 102. The step of forming the antireflection layer 104 is performed between steps S401 and S402, for example, in the manufacturing flow of FIG.

The method for forming the antireflection layer 104 is not particularly limited, but it can be formed by, for example, a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method. Examples of the physical vapor deposition method include a vacuum vapor deposition method and a sputtering method.

(Anti-glare treatment process)
The first main surface 101a of the glass substrate 101 may have an uneven shape in order to impart antiglare properties. The antiglare treatment is not particularly limited, and is applied to the first main surface 101a of the glass substrate 101 by a chemical method or a physical method. Specific examples of the antiglare treatment by a chemical method include a method of applying a frost treatment. The frost treatment is performed, for example, by immersing the glass substrate 101, which is the object to be treated, in a mixed solution of hydrogen fluoride and ammonium fluoride. As antiglare treatment by a physical method, for example, so-called sandblasting treatment in which crystalline silicon dioxide powder, silicon carbide powder or the like is sprayed on the surface of the glass substrate 5 with pressurized air, or crystalline silicon dioxide powder, silicon carbide powder or the like is adhered. This is done by moistening the brush with water and polishing the surface of the glass substrate 101 using the brush. Among them, the frost treatment, which is a chemical surface treatment, can be preferably used because microcracks on the surface of the object to be treated are unlikely to occur and the strength of the glass substrate 101 is unlikely to decrease.

Further, instead of the antiglare treatment, an antiglare layer may be formed on the first main surface 101a of the glass substrate 101. The antiglare layer is a coating liquid containing fine particles such as resin and metal, which is coated with a wet coating method (spray coating method, electrostatic coating method, spin coating method, dip coating method, die coating method, curtain coating method, screen coating method, inkjet). It is formed by coating by a method, a flow coating method, a gravure coating method, a bar coating method, a flexographic coating method, a slit coating method, a roll coating method, etc.).

(Measurement / test method)
Next, the evaluation method of the glass substrate 100 with an antifouling layer in the present invention will be described.

(Vickers hardness measurement)
With the adhesion layer formed on the glass substrate, the hardness of the outermost layer of the adhesion layer is measured by the international standard ISO14577 instrumentation indentation test. The maximum test force load is 10 mN.

(Water contact angle measurement)
As a method of evaluating the antifouling property of the antifouling layer, the water contact angle is measured. The larger the water contact angle, the better the antifouling property. About 1 μL of pure water droplets are deposited on the surface of the antifouling layer of the glass substrate with the antifouling layer, and the contact angle with respect to water is measured using a contact angle meter.

(Measurement of charge)
The triboelectric charge amount is determined by the D method (triboelectric attenuation measurement method) described in JIS L1094: 2014.

(Eraser friction wear test)
Using a flat surface wear tester, the surface of the antifouling layer is worn 7500 times with an eraser having a diameter of 6 mm under the conditions of a load of 1 kgf, a stroke width of 40 mm, a speed of 40 rpm, and 25 ° C. and 50% RH. Then, the water contact angle on the surface of the antifouling layer is measured.

(Steel wool wear test)
Using a flat surface wear tester, the surface of the antifouling layer is worn 7500 times with # 0000 steel wool attached to a 1 cm ² indenter under the conditions of a load of 1 kgf, a stroke width of 20 mm, a speed of 80 rpm, and 25 ° C. and 50% RH. Then, the water contact angle on the surface of the antifouling layer is measured.

Next, examples of the glass substrate with an antifouling layer of the present invention will be described. In this embodiment, an adhesive layer was formed between the glass substrate and the antifouling layer according to the first embodiment of the glass substrate with the antifouling layer described above. An adhesion layer was formed on the first main surface of the glass substrate. The conditions and evaluation results of each example and comparative example are summarized in Table 1 below.

(Example 1)
As a glass substrate, a glass having the following composition (composition example 1) in terms of mass percentage based on oxide was prepared.
SiO ₂ 69.6%
Al ₂ O ₃ 12.7%
MgO 4.7%
ZrO ₂ 2.0%
Li ₂ O 4.0%
Na ₂ O 5.4%
K ₂ O 1.6%
The glass substrate was cut to a size of 10 cm × 10 cm, and the first main surface of the glass substrate was polished.
The surface of the glass substrate was first strengthened by immersing the glass substrate in a 100% by weight sodium nitrate solution at a temperature of 410 ° C. for 4 hours, and then the glass substrate was prepared into a mixed solution of 99% by weight potassium nitrate and 1% by weight sodium nitrate at a temperature of 440 ° C. The surface was secondarily strengthened by immersing for 1 hour. After chemical strengthening, the glass substrate was washed by immersing it in pure water and an alkaline detergent. Then, the first main surface of the glass substrate was irradiated with plasma to perform plasma cleaning.

Next, an adhesion layer was formed on the first main surface of the glass substrate by a sputtering method. A RAS1100B II, manufactured by Syncron Co., Ltd. was used as the sputtering apparatus, the adhesion layer was SiO _2, and polycrystalline Si (manufactured by Chemiston, purity 5N) was used as the sputtering target. After confirming that the pressure in the film forming chamber was 5 × 10 ^-5 Pa or less, the following operation was started.

50 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber became 0.08 Pa. Next, a power of 7000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

Next, an antifouling layer was formed on the first surface of the adhesion layer. A fluorine-containing organic compound (UD-509, manufactured by Daikin Corporation) was used as the material of the antifouling layer, and a film was formed by a vacuum vapor deposition method by resistance heating. The sample was used in a state where the SW-encapsulated pelletized copper container was impregnated with the sample solution in a nitrogen atmosphere for 30 minutes on the night before, and then supported by vacuuming. The pressure in the vacuum chamber at the time of film formation was 3.0 × 10 ^-3 Pa, and the vapor deposition output was 318.5 kA / m ² for 300 seconds. The thickness of the antifouling layer was 15 nm.

In Examples 2 to 12 and Comparative Examples 1 to 3, the same as in Example 1 except for the conditions for forming the adhesion layer.
(Example 2)
In Example 2, argon was introduced as a discharge gas in the film forming chamber by 80 sccm and oxygen gas was introduced by 100 sccm, and the pressure in the film forming chamber was 0.10 Pa. Next, a power of 7000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 3)
In Example 3, 100 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.12 Pa. Next, a power of 7000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 4)
In Example 4, 50 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.08 Pa. Next, a power of 6000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 5)
In Example 5, argon was introduced as a discharge gas in the film forming chamber by 80 sccm and oxygen gas was introduced by 100 sccm, and the pressure in the film forming chamber was 0.10 Pa. Next, a power of 6000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 6)
In Example 6, 100 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.12 Pa. Next, a power of 6000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 7)
In Example 7, argon was introduced as a discharge gas in the film forming chamber by 50 sccm and oxygen gas was introduced by 100 sccm, and the pressure in the film forming chamber was 0.08 Pa. Next, a power of 5000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 8)
In Example 8, argon was introduced as a discharge gas in the film forming chamber by 80 sccm and oxygen gas was introduced by 100 sccm, and the pressure in the film forming chamber was 0.10 Pa. Next, a power of 5000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 9)
In Example 9, 100 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.12 Pa. Next, a power of 5000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was set to 4500 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 10)
In Example 10, 50 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.08 Pa. Next, a power of 5000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gas, and the electric power of the RF plasma source was 4000 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 11)
In Example 11, argon was introduced as a discharge gas in the film forming chamber by 80 sccm and oxygen gas was introduced by 100 sccm, and the pressure in the film forming chamber was 0.10 Pa. Next, a power of 5000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gas, and the electric power of the RF plasma source was 4000 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Example 12)
In Example 12, 100 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.12 Pa. Next, a power of 5000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gas, and the electric power of the RF plasma source was 4000 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Comparative Example 1)
In Comparative Example 1, 100 sccm of argon was introduced as the discharge gas in the film forming chamber, and oxygen gas was not introduced. The pressure in the film forming chamber was 0.08 Pa. Next, a power of 7000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 200 sccm of oxygen was introduced into the reaction chamber as a discharge gas, and argon was not introduced. Discharging was performed with the power of the RF plasma source set to 4500 W. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Comparative Example 2)
In Comparative Example 2, 300 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.35 Pa. Next, a power of 7000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and an RF plasma source was not used. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Comparative Example 3)
In Comparative Example 3, 100 sccm of argon and 100 sccm of oxygen gas were introduced as the discharge gas in the film forming chamber, and the pressure in the film forming chamber was 0.15 Pa. Next, a power of 7000 W was applied to the sputtering target. As a result, it was confirmed that the target surface of the film forming chamber was sufficiently oxidized to reach the discharge voltage in the reactive mode. Subsequently, 100 sccm of argon and 10 sccm of oxygen were introduced into the reaction chamber as discharge gases, and the electric power of the RF plasma source was 1000 W for discharge. Under the above conditions, the thickness of the adhesion layer was adjusted to 10 nm, and a film was formed.

(Evaluation method)
The glass substrates with the antifouling layer obtained in the above Examples and Comparative Examples were evaluated by the following methods.
(Vickers hardness measurement)
With the adhesion layer formed on the glass substrate, the hardness of the outermost layer of the adhesion layer is measured by the international standard ISO14577 instrumentation indentation test. The maximum test force load is 10 mN. The Vickers hardness of the main surface of the glass substrate itself used in Examples and Comparative Examples was 6.61 HV.

(Water contact angle measurement)
The water contact angle was measured as a method for evaluating the antifouling property of the antifouling layer. About 1 μL of pure water droplets were deposited on the surface of the antifouling layer of the glass substrate with the antifouling layer, and the contact angle with respect to water was measured using a contact angle meter.

(Measurement of charge)
The triboelectric charge amount was determined by the D method (triboelectric attenuation measurement method) described in JIS L1094: 2014.

(Eraser friction wear test)
Antifouling layer surface under the conditions of load 1 kgf, stroke width 40 mm, speed 40 rpm, 25 ° C. 50% RH, using a flat surface wear tester (triple type) (manufactured by Daiei Kagaku Seiki Seisakusho, device name: PA-300A). Was abraded 7500 times with an eraser (pink pencil manufactured by WOOJIN) having a diameter of 6 mm. Then, the water contact angle on the surface of the antifouling layer was measured.

(Steel wool wear test)
Using a flat surface wear tester (triple type) (manufactured by Daiei Kagaku Seiki Seisakusho, device name: PA-300A), an indenter of 1 cm ² under the conditions of load 1 kgf, stroke width 20 mm, speed 80 rpm, 25 ° C. 50% RH. The surface of the antifouling layer was abraded 7500 times with # 0000 steel wool attached to. Then, the water contact angle on the surface of the antifouling layer was measured.

Table 1 below shows the implementation conditions and evaluation results in Examples 1 to 12 and Comparative Examples 1 to 3. As can be seen from this, when the hardness of the adhesion layer is 7.5 HV or more, the water contact angle of the antifouling layer is 80 ° or more even after the eraser test, and it can be seen that the wear resistance is good. Further, when the hardness of the adhesion layer is 8.5 or more, the water contact angle of the antifouling layer is 90 ° or more even after the eraser test, and it can be seen that the wear resistance is more excellent. In particular, when the hardness of the adhesion layer was 9.1 or more, the water contact angle of the antifouling layer was 100 ° or more even after the eraser test, and it was found that the abrasion resistance was the best. Further, it can be seen that when the adhesion layer is formed on the glass substrate, the hardness measured with respect to the outermost layer of the adhesion layer is higher than the hardness of the glass substrate itself (6.61 HV). On the other hand, it was found that as the thickness of the adhesion layer was increased, the hardness gradually decreased.

(Example of composition of glass substrate)
Next, Table 2 shows an example of a glass composition preferably used for the glass substrate in the present invention. The composition is shown in terms of oxide-based mass percentage.

100 Glass substrate with antifouling layer 101 Glass substrate 101a First main surface of glass substrate 101b Second main surface of glass substrate
102 Adhesion layer 102a First surface of adhesion layer 102b Second surface of adhesion layer 103 Antifouling layer 103a First surface of antifouling layer 103 103a Second surface of antifouling layer 103 104 Antireflection layer

Claims (5)

A glass substrate having a pair of main surfaces facing each other,
With the adhesion layer formed on at least one main surface of the glass substrate,
A glass substrate with an antifouling layer provided with an antifouling layer formed on the surface of the adhesive layer.
A glass substrate with an antifouling layer having a Vickers hardness of 7.5 HV or more as measured by an instrumentation indentation test (international standard ISO14577) of the adhesive layer. The glass substrate with an antifouling layer according to claim 1, wherein the thickness of the adhesion layer is 5 nm or more and 20 nm or less. The glass substrate with an antifouling layer according to claim 1 or 2, wherein the adhesion layer is a film containing silicon dioxide. The glass substrate with an antifouling layer according to any one of claims 1 to 3, wherein the glass substrate is chemically tempered glass. The composition of the glass substrate is expressed as an oxide-based mass percentage.
SiO ₂ 55-80%,
Al ₂ O ₃ 10-28%,
B ₂ O ₃ 0-10%,
Li ₂ O 2-10%,
Na ₂ O 0.5-11%,
K ₂ O 0-10%,
(MgO + CaO + SrO + BaO) 0-10%, and (ZrO ₂ + TiO ₂ ) 0-5%,
The glass substrate with an antifouling layer according to any one of claims 1 to 4, which is contained.

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