TW201837499A - Article having antiglare surface - Google Patents

Abstract

A glass article (10) used in a region where pen input operation is performed is provided with a glass substrate (11) that is a substrate and an antiglare film (12) provided on the glass substrate (11). The number of projections per mm2 of 1 [mu]m or greater in diameter and 1 [mu]m or greater in height that exist on the surface of the antiglare film (12), i.e., on an antiglare surface, is 50 or greater.

Description

Articles with anti-glare surface

The invention relates to an article having an anti-glare surface, which is used for a handwriting input device.

In the past, from the viewpoint of improving the visibility of a display device, it has been proposed to add an anti-reflection layer or an anti-glare layer to the display surface of the display device. For example, Patent Document 1 has the following description: an antireflection film having a low refractive index layer is provided above a substrate, and the main surface of the low refractive index layer is subjected to antiglare treatment to form both antireflection function and antiglare. Functional anti-reflection film.

Further, Patent Documents 2 and 3 disclose the use of a glass article subjected to anti-glare treatment as a cover glass of a handwriting input device.

Prior Art Literature Patent Literature Patent Literature 1: Japanese Patent Application Laid-Open No. 10-221506 Patent Literature 2: Japanese Patent Application Laid-Open No. 2004-240548 Patent Literature 3: International Publication WO2015 / 072297

Problems to be Solved by the Invention However, when a handwriting input operation such as a cover glass of a handwriting input device such as this is used for a handwriting input operation, it is better to obtain a writing feeling close to the actual writing, that is, a good stroke. .

The present invention has been made in view of the above-mentioned facts, and an object thereof is to provide an article having an anti-glare surface which has excellent strokes when performing a handwriting input operation.

Means for solving the problem The article for achieving the above-mentioned object is an article for a part for performing a handwriting input operation, and includes a base material and an anti-glare surface provided on at least one side of the base material; The number of protrusions having a diameter of 1 μm or more and a height of 1 μm or more is 50 or more per 1 mm ² .

In the article, it is preferable that the anti-glare surface is made of an anti-glare film containing at least one selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , and TiO ₂ .

In the article, it is preferable that the number of the protrusions is 100 or more per 1 mm ² .

EFFECT OF THE INVENTION According to the present invention, it is possible to improve the stroke when performing a handwriting input operation.

An embodiment of the present invention will be described below.

As shown in FIG. 1, a glass article 10 of a transparent article includes a plate-shaped glass substrate 11 of a transparent substrate. As the glass constituting the glass substrate 11, known glass such as alkali-free glass, aluminosilicate glass, and soda-lime glass can be used. In addition, as the glass substrate 11, tempered glass such as chemically strengthened glass or crystallized glass such as LAS-based crystallized glass can be used. Among them, the glass substrate 11 is preferably an aluminosilicate glass used among them, and in particular, it contains SiO ₂ : 50 to 80% by mass, Al ₂ O ₃ : 5 to 25% by mass, and B ₂ O ₃ : 0 to 15 Chemically strengthened glass with mass%, Na ₂ O: 1-20 mass%, and K ₂ O: 0-10 mass%.

An anti-glare film 12 having an anti-glare surface having an uneven structure that scatters light is provided on one main surface of the glass substrate 11. The uneven structure of the anti-glare film 12 and the anti-glare surface is made of, for example, a matrix composed of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , and TiO ₂ . An example of the uneven structure of the anti-glare surface is an island-like uneven structure having a flat portion between a plurality of island-like convex portions. The surface roughness of the anti-glare film 12, that is, the surface roughness Ra of the anti-glare surface is preferably, for example, 5 to 600 nm.

The anti-glare film 12 can be formed, for example, by applying a coating agent to the glass substrate 11 and heating the coating agent, and the coating agent includes a matrix precursor and a liquid medium in which the matrix precursor is dissolved. Examples of the matrix precursor contained in the coating agent include inorganic precursors such as a silicon dioxide precursor, an alumina precursor, a zirconia precursor, and a titanium oxide precursor. From the viewpoint of reducing the refractive index of the anti-glare film 12 and easily controlling the reactivity, a silicon dioxide precursor is preferred.

Examples of the silicon dioxide precursor include a silane compound having a hydrocarbon group and a hydrolyzable group bonded to a silicon atom, a hydrolyzed condensate of a silane compound, a silazane compound, and the like. From the viewpoint that cracking of the film can be sufficiently suppressed even when the thick anti-glare film 12 is formed, it is preferable to contain at least one or both of a silane compound and a hydrolyzed condensate thereof.

The silane compound has a hydrocarbon group bonded to a silicon atom and a hydrolyzable group. The hydrocarbon group may have one or a combination of two or more groups selected from the group consisting of -O-, -S-, -CO-, and -NR'- (where R 'is a hydrogen atom or a monovalent hydrocarbon group).

The hydrocarbon group may be a monovalent hydrocarbon group bonded to one silicon atom, or a divalent hydrocarbon group bonded to two silicon atoms. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. Examples of the divalent hydrocarbon group include an alkylene group, an alkylene group, and an alkylene group.

Examples of the hydrolyzable group include an alkoxy group, an alkoxy group, a ketoxime group, an alkenyl group, an amine group, an amineoxy group, a fluorenylamine group, an isocyanate group, a halogen atom, and the like. From the stability and easy hydrolysis of the silane compound From the viewpoint of balance, an alkoxy group, an isocyanate group, and a halogen atom (especially a chlorine atom) are preferred. The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group.

Examples of the silane compound include an alkoxysilane (tetramethoxysilane, triethoxysilane, tetraisopropoxysilane, etc.), an alkoxysilane having an alkyl group (methyltrimethoxysilane, ethyl Triethoxysilane, etc.), alkoxysilanes having vinyl groups (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilanes having epoxy groups (2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyl triethoxysilane, etc.), alkoxysilane (3-propenyloxypropyltrimethoxysilane, etc.) having acryloxy, and the like. Among these silane compounds, it is preferable to use either one or both of the alkoxysilane and the hydrolysis condensate thereof, and it is more preferable to use the hydrolysis condensation product of the alkoxysilane.

The silazane compound is a compound having a silicon-nitrogen bond (-SiN-) in its structure. The silazane compound may be a low-molecular compound or a high-molecular compound (a polymer having a predetermined repeating unit). Examples of the low-molecular silazane compound include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1 , 1,3,3,5,5-hexamethylcyclotrisilazane and so on.

Examples of the alumina precursor include alkoxides, hydrolyzed condensates of alkoxides, water-soluble aluminum salts, and aluminum clamp compounds. Examples of the zirconia precursor include zirconia alkoxide, hydrolyzed condensate of zirconia, and the like. Examples of the titanium oxide precursor include titanium alkoxides and hydrolyzed condensates of titanium alkoxides.

The liquid medium contained in the coating agent is a solvent that dissolves the matrix precursor, and can be appropriately selected depending on the type of the matrix precursor. Examples of the liquid medium include water, alcohols, ketones, ethers, sulose, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds, and the like.

Examples of the alcohols include methanol, ethanol, isopropanol, butanol, and diacetone alcohol. Examples of the ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ethers include tetrahydrofuran and 1,4-dioxane. Examples of the selenium class include methyl selenium and ethyl selenium. Examples of the esters include methyl acetate and ethyl acetate. Examples of the glycol ethers include ethylene glycol monoalkyl ether. Examples of the nitrogen-containing compound include N, N-dimethylacetamide, N, N-dimethylformamide, and N-methylpyrrolidone. Examples of the sulfur-containing compound include dimethylsulfine and the like. The liquid medium may be used singly or in combination of two or more kinds.

Among them, the liquid medium is preferably a liquid medium containing water, and specifically, water or a mixed liquid of water and other liquid medium. Other liquid media are preferably alcohols, and particularly preferred are methanol, ethanol, isopropanol, and butanol.

In addition, the coating agent may be an acid catalyst that promotes hydrolysis and condensation of the matrix precursor. The acid catalyst is a component that accelerates the hydrolysis and condensation of the matrix precursor and forms the anti-glare film 12 in a short time. Before preparing the coating agent, the acid catalyst may be added for the hydrolysis and condensation of the raw materials (alkoxysilane, etc.) when preparing the solution of the matrix precursor, or may be added after preparing the necessary components. Examples of the acid catalyst include inorganic acids (such as nitric acid, sulfuric acid, and hydrochloric acid) and organic acids (formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid).

Examples of the coating method of the coating agent include known wet coating methods (spray coating method, spin coating method, dip coating method, mold coating method, curtain coating method, screen coating method, inkjet method, and flow coating method). , Gravure coating method, bar coating method, flexographic coating method, slit coating method, roll coating method, etc.). The coating method is preferably a spray coating method from the viewpoint of easily forming unevenness.

Examples of the nozzle using the spray coating method include a two-fluid nozzle and a one-fluid nozzle. The particle diameter of the droplets of the coating agent discharged from the nozzle is usually 0.1 to 100 μm, and preferably 1 to 50 μm. When the particle diameter of the droplet is 0.1 μm or more, it is possible to form unevenness exhibiting a sufficient anti-glare effect in a short time. When the particle diameter of the droplets is 100 μm or less, it is easy to form appropriate irregularities exhibiting a sufficient anti-glare effect. The particle diameter of the droplets of the coating agent can be appropriately adjusted by the type of the nozzle, the spraying pressure, the amount of liquid, and the like. For example, in a two-fluid nozzle, the higher the spray pressure, the smaller the droplets, and the larger the liquid volume, the larger the droplets. Wherein, the particle diameter of the droplet is the Sauter Mean Diameter measured by a laser measuring instrument.

The surface temperature of the glass substrate 11 when the coating agent is applied is, for example, 20 to 75 ° C, preferably 35 ° C or higher, and more preferably 60 ° C or higher. The method of heating the glass substrate 11 is preferably a heating device of, for example, a warm water circulation type. The humidity when applying the coating agent is, for example, 20 to 80%, and preferably 50% or more.

The outer surface (anti-glare surface) of the side where the anti-glare film 12 is provided in the glass article 10 may have protrusions having a height of about 10 to 100 times higher than the uneven structure of the anti-glare film 12. The protrusions are protrusions having a diameter (average particle diameter) of 1 μm or more and a height of 1 μm or more. Wherein, when the planar shape of the protrusion is not circular, but is non-circular like a circle or a polygon, the diameter of the protrusion represents a diameter corresponding to a circle. The height of the protrusions is preferably 20 μm or less.

In the scanning electron microscope photograph at a magnification of 20,000 times shown in FIG. 2, the large protrusions described above can be confirmed as a granular portion bulging from the surface. The height of the protrusions can be confirmed by obliquely scanning the anti-glare surface of the anti-glare film 12 with a scanning electron microscope. For example, an image is taken in a state where the angle of the electron beam irradiation direction of the scanning electron microscope and one principal surface of the glass substrate 11 on which the anti-glare film 12 is formed is 17 °, and the protrusions in the obtained image are obtained The height H can be obtained by dividing the height H by "cos17 °". The protrusions are generally considered to be formed when the anti-glare film 12 is formed by aggregating and granulating the film-forming material to adhere to the surface (anti-glare surface) of the anti-glare film 12.

In the glass article 10 according to this embodiment, the number of the protrusions per unit area of the anti-glare surface in the anti-glare film 12 is set to a specific value or more. That is, the glass article 10 to the number of the projections per 1mm ² of 50 or more. The number of the protrusions per 1 mm ² is preferably 76 or more, more preferably 100 or more, and even more preferably 300 or more. By setting the number of the protrusions in this way, the pen tip is moderately pulled by the protrusions, so that it is possible to obtain the same strokes when writing characters and the like on actual paper. That is, it is possible to improve the stroke when performing a handwriting input operation. The upper limit of the number of the protrusions per 1 mm ² in the glass article 10 is not particularly limited. For example, it is preferably 1500, more preferably 1,000, and even more preferably 500. FIG. 3 is a photograph of a light-transmitting optical microscope with a magnification of 200 times (20 times for the objective lens and 10 times for the eyepiece lens). The protrusions in the optical microscope picture can be confirmed as black spots.

The number of the protrusions can be controlled by changing the film formation conditions of the anti-glare film 12. For example, if the anti-glare film 12 is formed by applying a coating agent by a spray coating method, the number of the protrusions may be changed by changing the distance from the nozzle to the glass substrate 11 to be film-formed (hereinafter referred to as the spray distance). Will change. The spraying distance has an appropriate range, and the inventor's research has confirmed that the above-mentioned protrusions become smaller outside this range. The appropriate spraying distance varies with the type or viscosity of the coating agent, and the spraying conditions (temperature, humidity). In order to increase the number of the protrusions, it is preferable to set the spraying distance to be longer, and it is preferably set to 60 mm or more. . The upper limit of the spraying distance is not particularly limited, but is preferably 200 mm, for example. The number of the protrusions can also be increased by setting the surface temperature of the glass substrate 11 when the coating agent is applied or the humidity when the coating agent is applied within the above-mentioned range.

The glass article 10 according to the present embodiment is used on an input surface of a handwriting input device. The glass article 10 may be a member mounted above the input surface of the handwriting input device. That is, the glass article 10 may be a member that is mounted on the handwriting input device afterwards.

Next, the effects on this embodiment will be described.

(1) A glass article 10 that is a transparent article for a part where a handwriting input operation is performed, includes a glass substrate 11 as a transparent substrate, and an anti-glare film 12 provided on the glass substrate 11. The number of protrusions existing on the surface of the anti-glare film 12 that is 1 μm or more in diameter and 1 μm or more in the anti-glare surface is 50 or more per 1 mm ² . According to the above configuration, it is possible to improve a stroke when performing a handwriting input operation.

(2) If the number of protrusions per 1 mm ² is 100 or more, the strokes during a handwriting input operation can be further improved.

(3) If the spray distance when the coating agent containing the matrix precursor is applied to the glass substrate 11 by the spray coating method to form the anti-glare film 12 is 60 mm or more, the protrusions formed on the surface of the glass article 10 can be increased. Number of. Therefore, it is possible to easily manufacture the glass article 10 having excellent strokes when performing a handwriting input operation.

However, the present embodiment may be embodied in the following changes.

An anti-glare film having an anti-glare surface may be added to two or more of the surfaces of the substrate.

Other layers such as an anti-reflection layer or an antifouling layer may be added between at least one of the substrate and the anti-glare film, and above the anti-glare film.

As the transparent substrate, a resin substrate such as a polycarbonate substrate may be used instead of the glass substrate 11.

The anti-glare surface in the above embodiment is formed by applying a coating agent to the glass substrate 11 and heating the formed anti-glare film 12. The surface of the glass substrate 11 may also be etched to form an anti-glare surface .

Next, technical ideas that can be grasped from the above-described embodiments and modifications are described.

A transparent article in which the anti-glare surface is composed of an anti-glare film coated by a wet coating method.

An evaluation method is based on a protrusion having a diameter of 1 μm or more and a height of 1 μm or more per 1 mm ^{2 of} a surface of a transparent article having a transparent substrate and an anti-glare surface provided on at least one of the transparent substrates. The number of strokes was evaluated on the surface of the transparent article.

A method for manufacturing a transparent article, which is a method for manufacturing a transparent article at a part for performing a handwriting input operation, characterized in that the transparent article includes a transparent substrate and anti-glare provided on at least one side of the transparent substrate. The anti-glare surface is the surface of an anti-glare film. The anti-glare film is formed by applying a coating agent containing a matrix precursor to the transparent substrate by a spray coating method, and applying the coating agent by a spray coating method. The spraying distance is more than 60mm.

Examples

(Test Examples 1 to 14) Glass articles of Test Examples 1 to 14 having different film formation conditions for anti-glare films were produced. Specifically, a coating agent prepared by dissolving a precursor of an anti-glare film (tetraethyl orthosilicate) in a liquid medium containing water was applied by a spray coating device having a nozzle diameter of 0.6 mm to a 150 mm wide, An anti-glare film was formed on the surface of a glass substrate (dinorex (registered trademark) manufactured by Nippon Electric Glass Co., Ltd.) made of tempered glass having a length of 300 mm and a height of 1.1 mm. The coating amount per unit area of the coating agent for the glass substrate was 3 × 10 ^-5 g / mm ² . In addition, Table 1 shows the atmospheric temperature, atmospheric humidity, spray moving speed (nozzle moving speed), and spray distance during film formation.

(Measurement of the number of protrusions) For the glass articles of Test Examples 1 to 14, the number of protrusions having a diameter of 1 μm or more and a height of 1 μm or more existing on the anti-glare surface of the anti-glare film was measured. The number of protrusions was measured by using an optical microscope (magnification 200 times), and counting the number of black spots as shown in FIG. 3. Specifically, five areas of 1 mm ² (width 1 mm × length 1 mm) are randomly selected from the anti-glare surface, the number of the protrusions existing in each of these areas is counted, and the average 値 is calculated. The results are shown in Table 1.

(Evaluation of strokes) 30 30 subjects used a stylus pen (produced by Wacom Corporation: Propen (KP-503E)) to perform drawing operations on the surface of the glass article of each test example, and evaluated whether the strokes were good and close to paper Texture. The results are shown in the "Stroke" column in Table 1. Among them, in the "Stroke" column, those with a good stroke evaluation of 26 or more indicate "◎", those with a good stroke evaluation of 21 or more and 25 or less indicate "○", and those with a good stroke evaluation of 16 The above 20 people indicate "△", and the number of people with a good stroke evaluation of 15 or less indicates "X".

[Table 1]

As shown in Table 1, it can be seen that as the spraying distance increases, the number of protrusions having a diameter of 1 μm or more and a height of 1 μm or more increases. In addition, Test Examples 1 to 6 in which the number of the protrusions per 1 mm ² was 50 or more were higher than those in Test Examples 7 to 14 in which the number of the protrusions per 1 mm ² was less than 50. In Test Examples 1 to 6, Test Examples 1 to 4 in which the number of the protrusions per 1 mm ² was 100 or more, and in particular, Test Example 1 in which the number of the protrusions per 1 mm ² was 300 or more, the evaluation of the strokes was very high. high. From this result, it can be seen that the stroke when the handwriting input operation is performed in accordance with the number of the protrusions changes. In addition, it was found that by setting the number of the protrusions to 50 or more per 1 mm ² , the stroke when performing a handwriting input operation becomes excellent.

10‧‧‧ Glass items

11‧‧‧ glass substrate

12‧‧‧Anti-glare film

FIG. 1 is an explanatory diagram of a glass article. FIG. 2 is a scanning electron microscope photograph of the surface of a glass article. Fig. 3 is a light-transmitting optical microscope photograph of the surface of a glass article.

Claims (3)

An article is an article for a part where a handwriting input operation is performed, comprising: a substrate; and an anti-glare surface provided on at least one of the substrates; a diameter of the anti-glare surface existing on the anti-glare surface is 1 μm or more; The number of protrusions having a height of 1 μm or more is 50 or more per 1 mm ² . The article according to claim 1, wherein the anti-glare surface is made of an anti-glare film containing at least one selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , and TiO ₂ . The article according to claim 1 or 2, wherein the number of the protrusions per 1 mm ² is 100 or more.