WO2018151095A1 - Article having antiglare surface - Google Patents

Article having antiglare surface Download PDF

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Publication number
WO2018151095A1
WO2018151095A1 PCT/JP2018/004884 JP2018004884W WO2018151095A1 WO 2018151095 A1 WO2018151095 A1 WO 2018151095A1 JP 2018004884 W JP2018004884 W JP 2018004884W WO 2018151095 A1 WO2018151095 A1 WO 2018151095A1
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Prior art keywords
antiglare
glass
article
protrusions
examples
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PCT/JP2018/004884
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French (fr)
Japanese (ja)
Inventor
耕司 池上
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日本電気硝子株式会社
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to JP2018568532A priority Critical patent/JP7044078B2/en
Publication of WO2018151095A1 publication Critical patent/WO2018151095A1/en

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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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to an article used for a pen input device and having an antiglare surface.
  • Patent Document 1 an antireflection film having a low refractive index layer is provided on a base material, and the main surface of the low refractive index layer is antiglare-treated to provide not only an antireflection function but also an antiglare function.
  • the formation of a protective film is described.
  • Patent Document 2 and Patent Document 3 disclose that an antiglare-treated glass article is used as a cover glass for a pen input device.
  • a member that receives a pen input operation such as a cover glass of a pen input device, obtains a writing feeling close to an actual writing when the pen input operation is performed, that is, has good writing quality.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide an article having an antiglare surface, which has excellent writing quality when a pen input operation is performed.
  • An article for achieving the above object is an article used in a site where a pen input operation is performed, and includes a base material and an antiglare surface provided on at least one surface of the base material.
  • the number per 1 mm 2 of protrusions having a diameter of 1 ⁇ m or more and a height of 1 ⁇ m or more present on the surface is 50 or more.
  • the antiglare surface is preferably composed of an antiglare film containing at least one selected from SiO 2 , Al 2 O 3 , ZrO 2 , and TiO 2 .
  • the number of the protrusions per 1 mm 2 is preferably 100 or more.
  • writing quality when a pen input operation is performed is improved.
  • a glass article 10 that is a transparent article includes a glass substrate 11 that is a plate-like transparent substrate.
  • glass which comprises the glass base material 11 well-known glass, such as an alkali free glass, an aluminosilicate glass, soda-lime glass, can be used, for example.
  • tempered glass such as chemically tempered glass or crystallized glass such as LAS-based crystallized glass can be used.
  • aluminosilicate glass is used as the glass substrate 11, and in particular, SiO 2 : 50 to 80% by mass, Al 2 O 3 : 5 to 25% by mass, B 2 O 3 : 0 to 15 It is preferable to use chemically tempered glass containing 10% by mass, Na 2 O: 1 to 20% by mass, and K 2 O: 0 to 10% by mass.
  • an antiglare film 12 having an antiglare surface having an uneven structure for scattering light is provided on one main surface of the glass substrate 11.
  • the concavo-convex structure of the antiglare film 12 and the antiglare surface is constituted by a matrix made of, for example, SiO 2 , Al 2 O 3 , ZrO 2 , or TiO 2 .
  • As an example of the concavo-convex structure serving as an antiglare surface for example, an island-shaped concavo-convex structure having a flat portion between a plurality of island-shaped convex portions can be given.
  • the surface roughness Ra of the surface of the antiglare film 12, that is, the antiglare surface is preferably 5 to 600 nm, for example.
  • the anti-glare film 12 can be formed, for example, by applying a coating material containing a matrix precursor and a liquid medium dissolving the matrix precursor to the glass substrate 11 and heating.
  • a coating material containing a matrix precursor and a liquid medium dissolving the matrix precursor examples include inorganic precursors such as a silica precursor, an alumina precursor, a zirconia precursor, and a titania precursor.
  • a silica precursor is preferable because the refractive index of the antiglare film 12 is lowered and the reactivity is easily controlled.
  • silica precursor examples include a silane compound having a hydrocarbon group and a hydrolyzable group bonded to a silicon atom, a hydrolysis condensate of a silane compound, a silazane compound, and the like. Even when the anti-glare film 12 is formed thick, it is preferable that at least one or both of the silane compound and the hydrolysis condensate thereof is included because cracks of the film can be sufficiently suppressed.
  • the silane compound has a hydrocarbon group bonded to a silicon atom and a hydrolyzable group.
  • the hydrocarbon group is one or two selected from —O—, —S—, —CO—, and —NR′— (R ′ is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms. You may have the group which combined two or more.
  • 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 alkenylene group, and an arylene group.
  • hydrolyzable groups examples include alkoxy groups, acyloxy groups, ketoxime groups, alkenyloxy groups, amino groups, aminoxy groups, amide groups, isocyanate groups, halogen atoms, and the like. From the viewpoint of balance with ease, an alkoxy group, an isocyanate group, and a halogen atom (especially a chlorine atom) are preferable. 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.
  • silane compounds include alkoxysilanes (tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, etc.), alkoxysilanes having an alkyl group (methyltrimethoxysilane, ethyltriethoxysilane, etc.), and alkoxysilanes having a vinyl group.
  • alkoxysilanes having an epoxy group (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.
  • alkoxysilanes having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.) and the like.
  • silane compounds it is preferable to use either one or both of alkoxysilane and its hydrolysis condensate, and it is more preferable to use a hydrolysis condensate of 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 low molecular weight silazane compounds include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, etc. Is mentioned.
  • Examples of the alumina precursor include aluminum alkoxide, hydrolysis condensate of aluminum alkoxide, water-soluble aluminum salt, aluminum chelate and the like.
  • Examples of the zirconia precursor include zirconium alkoxide, a hydrolysis condensate of zirconium alkoxide, and the like.
  • Examples of the titania precursor include titanium alkoxide, hydrolysis condensate of titanium alkoxide, and the like.
  • the liquid medium contained in the coating agent is a solvent that dissolves the matrix precursor, and is appropriately selected according to the type of the matrix precursor.
  • the liquid medium include water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds and the like.
  • Examples of alcohols include methanol, ethanol, isopropanol, butanol, diacetone alcohol and the like.
  • Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.
  • Examples of ethers include tetrahydrofuran, 1,4-dioxane and the like.
  • Examples of cellosolves include methyl cellosolve and ethyl cellosolve.
  • Examples of esters include methyl acetate and ethyl acetate.
  • Examples of glycol ethers include ethylene glycol monoalkyl ether.
  • nitrogen-containing compounds include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and the like.
  • sulfur-containing compound examples include dimethyl sulfoxide.
  • a liquid medium may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the liquid medium is preferably a liquid medium containing water, that is, water or a mixed liquid of water and another liquid medium.
  • a liquid medium containing water
  • water that is, water or a mixed liquid of water and another liquid medium.
  • alcohols are preferable, and methanol, ethanol, isopropyl alcohol, and butanol are particularly preferable.
  • the coating agent may contain an acid catalyst that promotes hydrolysis and condensation of the matrix precursor.
  • the acid catalyst is a component that promotes hydrolysis and condensation of the matrix precursor and forms the antiglare film 12 in a short time. Prior to the preparation of the coating agent, the acid catalyst may be added for hydrolysis and condensation of raw materials (alkoxysilane, etc.) during the preparation of the matrix precursor solution. It may be further added after preparation.
  • the acid catalyst include inorganic acids (such as nitric acid, sulfuric acid, and hydrochloric acid) and organic acids (such as formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid).
  • coating methods for coating agents include known wet coating methods (spray coating method, spin coating method, dip coating method, die coating method, curtain coating method, screen coating method, ink jet method, flow coating method, gravure coating method, Bar coating method, flexo coating method, slit coating method, roll coating method, etc.).
  • a spray coating method is preferable from the viewpoint of easily forming irregularities.
  • nozzles used in the spray coating method include a two-fluid nozzle and a one-fluid nozzle.
  • the particle size of the coating agent droplets discharged from the nozzle is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m. If the particle size of the droplet is 0.1 ⁇ m or more, it is possible to form irregularities that sufficiently exhibit the antiglare effect in a short time. If the particle size of the droplet is 100 ⁇ m or less, it is easy to form moderate irregularities that can sufficiently exhibit the antiglare effect.
  • the particle size of the droplets of the coating agent can be appropriately adjusted depending on the type of nozzle, spray pressure, liquid amount, and the like. For example, in a two-fluid nozzle, the higher the spray pressure, the smaller the droplet, and the larger the liquid volume, the larger the droplet.
  • the droplet diameter is the Sauter average particle diameter measured by a laser measuring device.
  • the surface temperature of the glass substrate 11 when applying the coating agent is, for example, 20 to 75 ° C., preferably 35 ° C. or more, and more preferably 60 ° C. or more.
  • a method for heating the glass substrate 11 for example, it is preferable to use a warm water circulation type heating device.
  • the humidity at the time of applying the coating agent is, for example, 20 to 80%, preferably 50% or more.
  • the protrusions are protrusions having a diameter (average particle diameter) of 1 ⁇ m or more and a height of 1 ⁇ m or more.
  • the diameter of the protrusion is an equivalent circle diameter.
  • the height of the protrusion is preferably 20 ⁇ m or less.
  • the large protrusions can be confirmed as a granular portion raised from the surface.
  • the height of the protrusion can be confirmed by taking an image with respect to the antiglare surface of the antiglare film 12 with a scanning electron microscope. For example, an image is obtained in a state where an angle formed by an electron beam irradiation direction of a scanning electron microscope and one main surface of the glass substrate 11 on which the antiglare film 12 is formed is 17 °.
  • the actual height of the protrusion can be obtained by obtaining the height H of the protrusion at and dividing the height H by “cos 17 °”. It is considered that the protrusions are formed when the antiglare film 12 is formed by aggregating and granulating the film forming material and adhering to the surface (antiglare surface) of the antiglare film 12.
  • the number of protrusions per unit area of the antiglare surface in the antiglare film 12 is set to a specific value or more. That is, the number of the protrusions per 1 mm 2 in the glass article 10 is 50 or more. And the number per 1 mm ⁇ 2 > of the said protrusion becomes like this. Preferably it is 76 or more, More preferably, it is 100 or more, More preferably, it is 300 or more. By setting the number of the protrusions in this way, the pen tip is appropriately caught on the protrusion, and the same writing feeling as when writing characters or the like on the actual paper can be obtained. That is, the writing quality when a pen input operation is performed is improved.
  • FIG. 3 is an optical micrograph of transmitted light with a magnification of 200 times (objective lens 20 times, eyepiece lens 10 times). In the optical micrograph, the protrusions can be confirmed as black dots.
  • the number of protrusions can be controlled by changing the film formation conditions of the antiglare film 12. For example, when the antiglare film 12 is formed by applying a coating agent by a spray coating method, the distance from the nozzle to the glass substrate 11 that is a film formation target (hereinafter referred to as a spray distance) is changed. As a result, the number of the protrusions also changes.
  • the inventor's research has revealed that there is an appropriate range for the spray distance, and that the protrusions are reduced outside the range.
  • the appropriate spray distance varies depending on the type of coating agent, viscosity, and spray conditions (temperature, humidity), but in order to increase the number of protrusions, it is better to set the spray distance longer, for example, 60 mm or more.
  • the upper limit of spray distance is not specifically limited, For example, it is preferable that it is 200 mm.
  • the number of protrusions can also be increased by setting the surface temperature of the glass substrate 11 when applying the coating agent and the humidity when applying the coating agent within the above-mentioned range.
  • the glass article 10 of this embodiment is used by being arranged on the input surface of the pen input device.
  • the glass article 10 may be a member attached on the input surface of the pen input device. That is, the glass article 10 may be a member that is attached to the pen input device afterwards.
  • a glass article 10 which is a transparent article used for a part where a pen input operation is performed includes a glass substrate 11 which is a transparent substrate and an antiglare film 12 provided on the glass substrate 11. Yes.
  • the number per 1 mm 2 of protrusions having a diameter of 1 ⁇ m or more and a height of 1 ⁇ m or more present on the surface of the antiglare film 12, that is, the antiglare surface, is 50 or more. According to the above configuration, the writing quality when a pen input operation is performed is improved.
  • the spray distance when forming the anti-glare film 12 by applying a coating agent containing a matrix precursor to the glass substrate 11 by a spray coating method is 60 mm or more, it is formed on the surface of the glass article 10 It is possible to increase the number of protrusions to be formed. Therefore, it is possible to easily manufacture the glass article 10 that is excellent in writing when a pen input operation is performed.
  • this embodiment can also be changed and embodied as follows.
  • -An anti-glare film having an anti-glare surface may be provided on two or more of the surfaces of the substrate.
  • an antireflection layer and an antifouling layer may be provided between the substrate and the antiglare film and at least one on the antiglare film.
  • resin base materials such as a polycarbonate base material.
  • the anti-glare surface in the said embodiment is formed of the anti-glare film
  • the antiglare surface is the surface of an antiglare film, and the antiglare film is formed by applying a coating agent containing a matrix precursor to the transparent substrate by a spray coating method, and the coating agent is formed by a spray coating method.
  • a method for producing a transparent article, wherein a spray distance during application is 60 mm or more.
  • Test Examples 1 to 14 Glass articles of Test Examples 1 to 14 having different antiglare film forming conditions were produced. That is, with a spray coating apparatus having a nozzle diameter of 0.6 mm on the surface of a glass substrate (Nippon Electric Glass Co., Ltd .: Dinorex (registered trademark)) made of tempered glass having a length of 150 mm, a width of 300 mm, and a thickness of 1.1 mm. Then, an antiglare film was formed by applying a coating agent prepared by dissolving a precursor of an antiglare film (tetraethyl orthosilicate) in a liquid medium containing water. The coating amount per unit area of the coating agent on the glass substrate was 3 ⁇ 10 ⁇ 5 g / mm 2 . Table 1 shows the atmospheric temperature, atmospheric humidity, spray moving speed (nozzle moving speed), and spray distance during film formation.
  • the number of protrusions having a diameter of 1 ⁇ m or more and a height of 1 ⁇ m or more increases as the spray distance increases. Further, the number of protrusions per 1 mm 2 is compared to the test examples 7 to 14 is less than 50, Test Examples 1 to 6 above projections per 1 mm 2 is 50 or more, the evaluation of writing taste The result was high. Among Test Examples 1 to 6, Test Examples 1 to 4 in which the number of protrusions per 1 mm 2 is 100 or more, particularly Test Example 1 in which the number of protrusions per 1 mm 2 is 300 or more are written. The taste evaluation was very high.
  • the writing quality when the pen input operation is performed changes according to the number of protrusions. Further, by making the number of the protrusions per 1 mm 2 to 50 or more, it can be seen that becomes the writing feeling when performing the pen input operation is excellent.

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 µm or greater in diameter and 1 µm 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

アンチグレア面を有する物品Articles having an antiglare surface
　本発明は、ペン入力装置に用いられ、アンチグレア面を有する物品に関する。 The present invention relates to an article used for a pen input device and having an antiglare surface.
　従来、表示装置の視認性を向上する観点から、表示装置の表示面上に反射防止層やアンチグレア層を設けることが提案されている。例えば、特許文献１には、低屈折率層を有する反射防止膜を基材の上に設けるとともに、低屈折率層の主面をアンチグレア処理し、反射防止機能だけでなく防眩機能も兼ね備える反射防止膜を形成することが記載されている。 Conventionally, from the viewpoint of improving the visibility of a display device, it has been proposed to provide an antireflection layer or an antiglare layer on the display surface of the display device. For example, in Patent Document 1, an antireflection film having a low refractive index layer is provided on a base material, and the main surface of the low refractive index layer is antiglare-treated to provide not only an antireflection function but also an antiglare function. The formation of a protective film is described.
　また、特許文献２及び特許文献３には、アンチグレア処理されたガラス物品をペン入力装置のカバーガラスとして用いることが開示されている。 Further, Patent Document 2 and Patent Document 3 disclose that an antiglare-treated glass article is used as a cover glass for a pen input device.
特開平１０－２２１５０６号公報Japanese Patent Laid-Open No. 10-221506 特開２００４－２４０５４８号公報JP 2004-240548 A 国際公開ＷＯ２０１５／０７２２９７号International Publication WO2015 / 072297
　ところで、ペン入力装置のカバーガラス等のようにペン入力操作を受ける部材は、ペン入力操作を行った際に、実際の筆記に近い筆記感が得られること、すなわち書き味の良いことが好ましい。 By the way, it is preferable that a member that receives a pen input operation, such as a cover glass of a pen input device, obtains a writing feeling close to an actual writing when the pen input operation is performed, that is, has good writing quality.
　本発明は、こうした実情に鑑みてなされたものであり、その目的は、ペン入力操作を行った際の書き味に優れた、アンチグレア面を有する物品を提供することにある。 The present invention has been made in view of such circumstances, and an object thereof is to provide an article having an antiglare surface, which has excellent writing quality when a pen input operation is performed.
　上記の目的を達成するための物品は、ペン入力操作が行われる部位に用いられる物品であって、基材と、前記基材における少なくとも一つの面に設けられたアンチグレア面とを備え、前記アンチグレア面に存在する、直径が１μｍ以上、高さが１μｍ以上である突起の１ｍｍ２あたりの個数が５０個以上である。 An article for achieving the above object is an article used in a site where a pen input operation is performed, and includes a base material and an antiglare surface provided on at least one surface of the base material. The number per 1 mm 2 of protrusions having a diameter of 1 μm or more and a height of 1 μm or more present on the surface is 50 or more.
　上記物品において、前記アンチグレア面は、ＳｉＯ２、Ａｌ２Ｏ３、ＺｒＯ２、ＴｉＯ２から選ばれる少なくとも一種を含有するアンチグレア膜により構成されることが好ましい。 In the above article, the antiglare surface is preferably composed of an antiglare film containing at least one selected from SiO 2 , Al 2 O 3 , ZrO 2 , and TiO 2 .
　上記物品において、前記突起の１ｍｍ２あたりの個数が１００個以上であることが好ましい。 In the above article, the number of the protrusions per 1 mm 2 is preferably 100 or more.
　本発明によれば、ペン入力操作を行った際の書き味が向上する。 According to the present invention, writing quality when a pen input operation is performed is improved.
ガラス物品の説明図。Explanatory drawing of a glass article. ガラス物品の表面の走査型電子顕微鏡写真。Scanning electron micrograph of the surface of a glass article. ガラス物品の表面の透過光による光学顕微鏡写真。The optical microscope photograph by the transmitted light of the surface of a glass article.
　以下、本発明の一実施形態を説明する。
　図１に示すように、透明な物品であるガラス物品１０は、板状の透明基材であるガラス基材１１を備えている。ガラス基材１１を構成するガラスとしては、例えば、無アルカリガラス、アルミノシリケートガラス、ソーダライムガラス等の公知のガラスを用いることができる。また、ガラス基材１１としては、化学強化ガラス等の強化ガラスやＬＡＳ系結晶化ガラス等の結晶化ガラスを用いることもできる。なお、ガラス基材１１として、これらのなかでも、アルミノシリケートガラスを用いること、特に、ＳｉＯ２：５０～８０質量％、Ａｌ２Ｏ３：５～２５質量％、Ｂ２Ｏ３：０～１５質量％、Ｎａ２Ｏ：１～２０質量％、Ｋ２Ｏ：０～１０質量％を含有する化学強化ガラスを用いることが好ましい。 Hereinafter, an embodiment of the present invention will be described.
As shown in FIG. 1, a glass article 10 that is a transparent article includes a glass substrate 11 that is a plate-like transparent substrate. As glass which comprises the glass base material 11, well-known glass, such as an alkali free glass, an aluminosilicate glass, soda-lime glass, can be used, for example. Further, as the glass substrate 11, tempered glass such as chemically tempered glass or crystallized glass such as LAS-based crystallized glass can be used. Of these, aluminosilicate glass is used as the glass substrate 11, and in particular, SiO 2 : 50 to 80% by mass, Al 2 O 3 : 5 to 25% by mass, B 2 O 3 : 0 to 15 It is preferable to use chemically tempered glass containing 10% by mass, Na 2 O: 1 to 20% by mass, and K 2 O: 0 to 10% by mass.
　ガラス基材１１の一方の主面には、光を散乱させる凹凸構造を有するアンチグレア面を有するアンチグレア膜１２が設けられている。アンチグレア膜１２及びアンチグレア面の凹凸構造は、例えば、ＳｉＯ２、Ａｌ２Ｏ３、ＺｒＯ２、ＴｉＯ２からなるマトリックスにより構成されている。アンチグレア面たる凹凸構造の例としては、例えば、複数の島状の凸部間に平坦部分を有する島状の凹凸構造が挙げられる。アンチグレア膜１２の表面、すなわちアンチグレア面の表面粗さＲａは、例えば、５～６００ｎｍが好ましい。 On one main surface of the glass substrate 11, an antiglare film 12 having an antiglare surface having an uneven structure for scattering light is provided. The concavo-convex structure of the antiglare film 12 and the antiglare surface is constituted by a matrix made of, for example, SiO 2 , Al 2 O 3 , ZrO 2 , or TiO 2 . As an example of the concavo-convex structure serving as an antiglare surface, for example, an island-shaped concavo-convex structure having a flat portion between a plurality of island-shaped convex portions can be given. The surface roughness Ra of the surface of the antiglare film 12, that is, the antiglare surface is preferably 5 to 600 nm, for example.
　アンチグレア膜１２は、例えば、マトリックス前駆体、及びマトリックス前駆体を溶解する液状媒体を含むコーティング剤をガラス基材１１に塗布し、加熱することにより形成することができる。コーティング剤に含まれるマトリックス前駆体の例としては、例えば、シリカ前駆体、アルミナ前駆体、ジルコニア前駆体、チタニア前駆体等の無機前駆体が挙げられる。アンチグレア膜１２の屈折率を低くする点、反応性を制御しやすい点から、シリカ前駆体が好ましい。 The anti-glare film 12 can be formed, for example, by applying a coating material containing a matrix precursor and a liquid medium dissolving the matrix precursor to the glass substrate 11 and heating. Examples of the matrix precursor contained in the coating agent include inorganic precursors such as a silica precursor, an alumina precursor, a zirconia precursor, and a titania precursor. A silica precursor is preferable because the refractive index of the antiglare film 12 is lowered and the reactivity is easily controlled.
　シリカ前駆体の例としては、ケイ素原子に結合した炭化水素基及び加水分解性基を有するシラン化合物、シラン化合物の加水分解縮合物、シラザン化合物等が挙げられる。アンチグレア膜１２を厚く形成した場合でも膜のクラックが充分に抑えられる点から、シラン化合物及びその加水分解縮合物のいずれか一方又は両方を少なくとも含むことが好ましい。 Examples of the silica precursor include a silane compound having a hydrocarbon group and a hydrolyzable group bonded to a silicon atom, a hydrolysis condensate of a silane compound, a silazane compound, and the like. Even when the anti-glare film 12 is formed thick, it is preferable that at least one or both of the silane compound and the hydrolysis condensate thereof is included because cracks of the film can be sufficiently suppressed.
　シラン化合物は、ケイ素原子に結合した炭化水素基、及び加水分解性基を有する。炭化水素基は、炭素原子間に－Ｏ－、－Ｓ－、－ＣＯ－、及び－ＮＲ’－（Ｒ’は水素原子または１価の炭化水素基である。）から選ばれる１つ又は２つ以上を組み合わせた基を有していてもよい。 The silane compound has a hydrocarbon group bonded to a silicon atom and a hydrolyzable group. The hydrocarbon group is one or two selected from —O—, —S—, —CO—, and —NR′— (R ′ is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms. You may have the group which combined two or more.
　炭化水素基は、１つのケイ素原子に結合した１価の炭化水素基であってもよく、２つのケイ素原子に結合した２価の炭化水素基であってもよい。１価の炭化水素基の例としては、アルキル基、アルケニル基、アリール基等が挙げられる。２価の炭化水素基の例としては、アルキレン基、アルケニレン基、アリーレン基等が挙げられる。 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 alkenylene group, and an arylene group.
　加水分解性基の例としては、アルコキシ基、アシロキシ基、ケトオキシム基、アルケニルオキシ基、アミノ基、アミノキシ基、アミド基、イソシアネート基、ハロゲン原子等が挙げられ、シラン化合物の安定性と加水分解のしやすさとのバランスの点から、アルコキシ基、イソシアネート基、及びハロゲン原子（特に塩素原子）が好ましい。アルコキシ基としては、炭素数１～３のアルコキシ基が好ましく、メトキシ基又はエトキシ基がより好ましい。 Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoxime groups, alkenyloxy groups, amino groups, aminoxy groups, amide groups, isocyanate groups, halogen atoms, and the like. From the viewpoint of balance with ease, an alkoxy group, an isocyanate group, and a halogen atom (especially a chlorine atom) are preferable. 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.
　シラン化合物の例としては、アルコキシシラン（テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン等）、アルキル基を有するアルコキシシラン（メチルトリメトキシシラン、エチルトリエトキシシラン等）、ビニル基を有するアルコキシシラン（ビニルトリメトキシシラン、ビニルトリエトキシシラン等）、エポキシ基を有するアルコキシシラン（２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン等）、アクリロイルオキシ基を有するアルコキシシラン（３－アクリロイルオキシプロピルトリメトキシシラン等）等が挙げられる。これらのシラン化合物のなかでも、アルコキシシラン及びその加水分解縮合物のいずれか一方又は両方を用いることが好ましく、アルコキシシランの加水分解縮合物を用いることがより好ましい。 Examples of silane compounds include alkoxysilanes (tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, etc.), alkoxysilanes having an alkyl group (methyltrimethoxysilane, ethyltriethoxysilane, etc.), and alkoxysilanes having a vinyl group. (Vinyltrimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilanes having an epoxy group (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilanes having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.) and the like. Among these silane compounds, it is preferable to use either one or both of alkoxysilane and its hydrolysis condensate, and it is more preferable to use a hydrolysis condensate of alkoxysilane.
　シラザン化合物は、その構造内にケイ素と窒素の結合（－ＳｉＮ－）をもった化合物である。シラザン化合物としては、低分子化合物でも高分子化合物（所定の繰り返し単位を有するポリマー）であってもよい。低分子系のシラザン化合物の例としては、ヘキサメチルジシラザン、ヘキサフェニルジシラザン、ジメチルアミノトリメチルシラン、トリシラザン、シクロトリシラザン、１，１，３，３，５，５－ヘキサメチルシクロトリシラザン等が挙げられる。 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 low molecular weight silazane compounds include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, etc. Is mentioned.
　アルミナ前駆体の例としては、アルミニウムアルコキシド、アルミニウムアルコキシドの加水分解縮合物、水溶性アルミニウム塩、アルミニウムキレート等が挙げられる。ジルコニア前駆体の例としては、ジルコニウムアルコキシド、ジルコニウムアルコキシドの加水分解縮合物等が挙げられる。チタニア前駆体の例としては、チタンアルコキシド、チタンアルコキシドの加水分解縮合物等が挙げられる。 Examples of the alumina precursor include aluminum alkoxide, hydrolysis condensate of aluminum alkoxide, water-soluble aluminum salt, aluminum chelate and the like. Examples of the zirconia precursor include zirconium alkoxide, a hydrolysis condensate of zirconium alkoxide, and the like. Examples of the titania precursor include titanium alkoxide, hydrolysis condensate of titanium alkoxide, and the like.
　コーティング剤に含まれる液状媒体は、マトリックス前駆体を溶解する溶媒であり、マトリックス前駆体の種類に応じて適宜、選択される。液状媒体の例としては、例えば、水、アルコール類、ケトン類、エーテル類、セロソルブ類、エステル類、グリコールエーテル類、含窒素化合物、含硫黄化合物等が挙げられる。 The liquid medium contained in the coating agent is a solvent that dissolves the matrix precursor, and is appropriately selected according to the type of the matrix precursor. Examples of the liquid medium include water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds and the like.
　アルコール類の例としては、メタノール、エタノール、イソプロパノール、ブタノール、ジアセトンアルコール等が挙げられる。ケトン類の例としては、アセトン、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。エーテル類の例としては、テトラヒドロフラン、１，４－ジオキサン等が挙げられる。セロソルブ類の例としては、メチルセロソルブ、エチルセロソルブ等が挙げられる。エステル類の例としては、酢酸メチル、酢酸エチル等が挙げられる。グリコールエーテル類の例としては、エチレングリコールモノアルキルエーテル等が挙げられる。含窒素化合物の例としては、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドン等が挙げられる。含硫黄化合物の例としては、ジメチルスルホキシド等が挙げられる。液状媒体は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of alcohols include methanol, ethanol, isopropanol, butanol, diacetone alcohol and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Examples of ethers include tetrahydrofuran, 1,4-dioxane and the like. Examples of cellosolves include methyl cellosolve and ethyl cellosolve. Examples of esters include methyl acetate and ethyl acetate. Examples of glycol ethers include ethylene glycol monoalkyl ether. Examples of nitrogen-containing compounds include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and the like. Examples of the sulfur-containing compound include dimethyl sulfoxide. A liquid medium may be used individually by 1 type, and may be used in combination of 2 or more type.
　なお、液状媒体は、水を含む液状媒体、すなわち、水、又は水と他の液状媒体の混合液であることが好ましい。他の液状媒体としては、アルコール類が好ましく、メタノール、エタノール、イソプロピルアルコール、ブタノールが特に好ましい。 The liquid medium is preferably a liquid medium containing water, that is, water or a mixed liquid of water and another liquid medium. As other liquid media, alcohols are preferable, and methanol, ethanol, isopropyl alcohol, and butanol are particularly preferable.
　また、コーティング剤は、マトリックス前駆体の加水分解及び縮合を促進する酸触媒を含むものであってもよい。酸触媒は、マトリックス前駆体の加水分解及び縮合を促進し、アンチグレア膜１２を短時間で形成させる成分である。酸触媒は、コーティング剤の調製に先立って、マトリックス前駆体の溶液の調製の際に、原料（アルコキシシラン等）の加水分解、縮合のために添加されたものであってもよく、必須成分を調製した後にさらに添加されたものであってもよい。酸触媒としては、無機酸（硝酸、硫酸、塩酸等）、有機酸（ギ酸、シュウ酸、酢酸、モノクロル酢酸、ジクロル酢酸、トリクロル酢酸等）が挙げられる。 The coating agent may contain an acid catalyst that promotes hydrolysis and condensation of the matrix precursor. The acid catalyst is a component that promotes hydrolysis and condensation of the matrix precursor and forms the antiglare film 12 in a short time. Prior to the preparation of the coating agent, the acid catalyst may be added for hydrolysis and condensation of raw materials (alkoxysilane, etc.) during the preparation of the matrix precursor solution. It may be further added after preparation. Examples of the acid catalyst include inorganic acids (such as nitric acid, sulfuric acid, and hydrochloric acid) and organic acids (such as formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid).
　コーティング剤の塗布方法の例としては、公知のウェットコート法（スプレーコート法、スピンコート法、ディップコート法、ダイコート法、カーテンコート法、スクリーンコート法、インクジェット法、フローコート法、グラビアコート法、バーコート法、フレキソコート法、スリットコート法、ロールコート法等）等が挙げられる。塗布方法としては、凹凸を形成しやすい点から、スプレーコート法が好ましい。 Examples of coating methods for coating agents include known wet coating methods (spray coating method, spin coating method, dip coating method, die coating method, curtain coating method, screen coating method, ink jet method, flow coating method, gravure coating method, Bar coating method, flexo coating method, slit coating method, roll coating method, etc.). As a coating method, a spray coating method is preferable from the viewpoint of easily forming irregularities.
　スプレーコート法に用いるノズルの例としては、２流体ノズル、１流体ノズル等が挙げられる。ノズルから吐出されるコーティング剤の液滴の粒径は、通常０．１～１００μｍであり、１～５０μｍが好ましい。液滴の粒径が０．１μｍ以上であれば、防眩効果が充分に発揮される凹凸を短時間で形成できる。液滴の粒径が１００μｍ以下であれば、防眩効果が充分に発揮される適度な凹凸を形成しやすい。コーティング剤の液滴の粒径は、ノズルの種類、スプレー圧力、液量等により適宜、調整できる。例えば、２流体ノズルでは、スプレー圧力が高くなるほど液滴は小さくなり、また、液量が多くなるほど液滴は大きくなる。なお、液滴の粒径は、レーザ測定器によって測定されるザウター平均粒子径である。 Examples of nozzles used in the spray coating method include a two-fluid nozzle and a one-fluid nozzle. The particle size of the coating agent droplets discharged from the nozzle is usually 0.1 to 100 μm, preferably 1 to 50 μm. If the particle size of the droplet is 0.1 μm or more, it is possible to form irregularities that sufficiently exhibit the antiglare effect in a short time. If the particle size of the droplet is 100 μm or less, it is easy to form moderate irregularities that can sufficiently exhibit the antiglare effect. The particle size of the droplets of the coating agent can be appropriately adjusted depending on the type of nozzle, spray pressure, liquid amount, and the like. For example, in a two-fluid nozzle, the higher the spray pressure, the smaller the droplet, and the larger the liquid volume, the larger the droplet. The droplet diameter is the Sauter average particle diameter measured by a laser measuring device.
　コーティング剤を塗布する際のガラス基材１１の表面温度は、例えば、２０～７５℃であり、３５℃以上であることが好ましく、６０℃以上であることが更に好ましい。ガラス基材１１を加熱する方法としては、例えば、温水循環式の加熱装置を用いることが好ましい。また、コーティング剤を塗布する際の湿度は、例えば、２０～８０％であり、５０％以上であることが好ましい。 The surface temperature of the glass substrate 11 when applying the coating agent is, for example, 20 to 75 ° C., preferably 35 ° C. or more, and more preferably 60 ° C. or more. As a method for heating the glass substrate 11, for example, it is preferable to use a warm water circulation type heating device. Further, the humidity at the time of applying the coating agent is, for example, 20 to 80%, preferably 50% or more.
　ガラス物品１０におけるアンチグレア膜１２が設けられている側の外表面（アンチグレア面）には、アンチグレア膜１２の凹凸構造と比較して１０～１００倍程度の高さの突起が形成される場合がある。上記突起は、直径（平均粒径）が１μｍ以上、高さが１μｍ以上の突起である。なお、上記突起の平面形状が円でなく、楕円や多角形のような非円形である場合、上記突起の直径は、円相当直径である。また、上記突起の高さは２０μｍ以下であることが好ましい。 On the outer surface (antiglare surface) of the glass article 10 on the side where the antiglare film 12 is provided, there are cases where protrusions having a height of about 10 to 100 times compared to the uneven structure of the antiglare film 12 are formed. . The protrusions are protrusions having a diameter (average particle diameter) of 1 μm or more and a height of 1 μm or more. When the planar shape of the protrusion is not a circle but a non-circular shape such as an ellipse or a polygon, the diameter of the protrusion is an equivalent circle diameter. The height of the protrusion is preferably 20 μm or less.
　図２に示される倍率２００００倍の走査型電子顕微鏡写真において、上記の大きな突起は、表面から盛り上がった粒状の部分として確認することができる。上記突起の高さは、走査型電子顕微鏡によりアンチグレア膜１２のアンチグレア面に対して斜めから撮影することにより確認することができる。例えば、走査型電子顕微鏡の電子ビームの照射方向と、アンチグレア膜１２が形成されたガラス基材１１の一方の主面とのなす角が１７°となる状態で画像を撮像し、得られた画像における突起の高さＨを求め、高さＨを「ｃｏｓ１７°」で割ることにより、実際の突起の高さを求めることができる。上記突起は、アンチグレア膜１２の成膜時に、成膜材料が凝集及び粒状化してアンチグレア膜１２の表面（アンチグレア面）に付着することにより形成されると考えられる。 In the scanning electron micrograph at a magnification of 20000 shown in FIG. 2, the large protrusions can be confirmed as a granular portion raised from the surface. The height of the protrusion can be confirmed by taking an image with respect to the antiglare surface of the antiglare film 12 with a scanning electron microscope. For example, an image is obtained in a state where an angle formed by an electron beam irradiation direction of a scanning electron microscope and one main surface of the glass substrate 11 on which the antiglare film 12 is formed is 17 °. The actual height of the protrusion can be obtained by obtaining the height H of the protrusion at and dividing the height H by “cos 17 °”. It is considered that the protrusions are formed when the antiglare film 12 is formed by aggregating and granulating the film forming material and adhering to the surface (antiglare surface) of the antiglare film 12.
　本実施形態のガラス物品１０においては、アンチグレア膜１２におけるアンチグレア面の単位面積あたりの上記突起の個数が特定の値以上に設定されている。すなわち、ガラス物品１０における上記突起の１ｍｍ２あたりの個数は、５０個以上である。そして、上記突起の１ｍｍ２あたりの個数は、好ましくは７６個以上であり、より好ましくは１００個以上であり、更に好ましくは３００個以上である。このように上記突起の個数を設定することにより、ペン先が上記突起に適度に引っ掛かり、実際の紙に文字等を記載した時と同様の書き味が得られる。すなわち、ペン入力操作を行った際の書き味が向上する。なお、ガラス物品１０における上記突起の１ｍｍ２あたりの個数の上限は特に限定されるものではないが、例えば、１５００個であることが好ましく、１０００個であることがより好ましく、５００個であることが更に好ましい。図３は、倍率２００倍（対物レンズ２０倍、接眼レンズ１０倍）の透過光による光学顕微鏡写真であり、この光学顕微鏡写真において上記突起は、黒い点として確認することができる。 In the glass article 10 of the present embodiment, the number of protrusions per unit area of the antiglare surface in the antiglare film 12 is set to a specific value or more. That is, the number of the protrusions per 1 mm 2 in the glass article 10 is 50 or more. And the number per 1 mm < 2 > of the said protrusion becomes like this. Preferably it is 76 or more, More preferably, it is 100 or more, More preferably, it is 300 or more. By setting the number of the protrusions in this way, the pen tip is appropriately caught on the protrusion, and the same writing feeling as when writing characters or the like on the actual paper can be obtained. That is, the writing quality when a pen input operation is performed is improved. In addition, although the upper limit of the number per 1 mm < 2 > of the said protrusion in the glass article 10 is not specifically limited, For example, it is preferable that it is 1500 pieces, it is more preferable that it is 1000 pieces, and it is 500 pieces. Is more preferable. FIG. 3 is an optical micrograph of transmitted light with a magnification of 200 times (objective lens 20 times, eyepiece lens 10 times). In the optical micrograph, the protrusions can be confirmed as black dots.
　上記突起の個数は、アンチグレア膜１２の成膜条件を変更することによって制御することができる。例えば、スプレーコート法によりコーティング剤を塗布してアンチグレア膜１２を形成する場合であれば、ノズルから成膜対象であるガラス基材１１までの距離（以下、スプレー距離と記載する。）を変更することで上記突起の個数も変化する。スプレー距離には適切な範囲があり、その範囲外では上記突起が少なくなることが本発明者の研究によって判明した。適切なスプレー距離は、コーティング剤の種類や粘度、スプレー条件（温度、湿度）によって異なるが、上記突起の個数を多くするためには、スプレー距離を長く設定する方がよく、例えば、６０ｍｍ以上に設定することが好ましい。なお、スプレー距離の上限は特に限定されるものではないが、例えば、２００ｍｍであることが好ましい。また、コーティング剤を塗布する際のガラス基材１１の表面温度や、コーティング剤を塗布する際の湿度を上述の範囲内とすることによっても、上記突起の個数を多くすることができる。 The number of protrusions can be controlled by changing the film formation conditions of the antiglare film 12. For example, when the antiglare film 12 is formed by applying a coating agent by a spray coating method, the distance from the nozzle to the glass substrate 11 that is a film formation target (hereinafter referred to as a spray distance) is changed. As a result, the number of the protrusions also changes. The inventor's research has revealed that there is an appropriate range for the spray distance, and that the protrusions are reduced outside the range. The appropriate spray distance varies depending on the type of coating agent, viscosity, and spray conditions (temperature, humidity), but in order to increase the number of protrusions, it is better to set the spray distance longer, for example, 60 mm or more. It is preferable to set. In addition, although the upper limit of spray distance is not specifically limited, For example, it is preferable that it is 200 mm. The number of protrusions can also be increased by setting the surface temperature of the glass substrate 11 when applying the coating agent and the humidity when applying the coating agent within the above-mentioned range.
　本実施形態のガラス物品１０は、ペン入力装置の入力面に配されて使用される。ガラス物品１０は、ペン入力装置の入力面の上に取り付けられる部材であってもよい。すなわち、ガラス物品１０は、ペン入力装置に事後的に取り付けられる部材であってもよい。 The glass article 10 of this embodiment is used by being arranged on the input surface of the pen input device. The glass article 10 may be a member attached on the input surface of the pen input device. That is, the glass article 10 may be a member that is attached to the pen input device afterwards.
　次に、本実施形態の効果について記載する。
　（１）ペン入力操作が行われる部位に用いられる、透明な物品であるガラス物品１０は、透明基材であるガラス基材１１と、ガラス基材１１に設けられたアンチグレア膜１２とを備えている。アンチグレア膜１２の表面、すなわちアンチグレア面に存在する、直径が１μｍ以上、高さが１μｍ以上である突起の１ｍｍ２あたりの個数が５０個以上である。上記構成によれば、ペン入力操作を行った際の書き味が向上する。 Next, the effect of this embodiment will be described.
(1) A glass article 10 which is a transparent article used for a part where a pen input operation is performed includes a glass substrate 11 which is a transparent substrate and an antiglare film 12 provided on the glass substrate 11. Yes. The number per 1 mm 2 of protrusions having a diameter of 1 μm or more and a height of 1 μm or more present on the surface of the antiglare film 12, that is, the antiglare surface, is 50 or more. According to the above configuration, the writing quality when a pen input operation is performed is improved.
　（２）突起の１ｍｍ２あたりの個数が１００個以上であれば、ペン入力操作を行った際の書き味が更に向上する。
　（３）ガラス基材１１に対して、マトリックス前駆体を含むコーティング剤をスプレーコート法により塗布してアンチグレア膜１２を形成する際のスプレー距離を６０ｍｍ以上とすれば、ガラス物品１０の表面に形成される上記突起の個数を多くすることができる。したがって、ペン入力操作を行った際の書き味に優れたガラス物品１０を容易に製造することができる。 (2) If the number of protrusions per 1 mm 2 is 100 or more, the writing quality when performing a pen input operation is further improved.
(3) If the spray distance when forming the anti-glare film 12 by applying a coating agent containing a matrix precursor to the glass substrate 11 by a spray coating method is 60 mm or more, it is formed on the surface of the glass article 10 It is possible to increase the number of protrusions to be formed. Therefore, it is possible to easily manufacture the glass article 10 that is excellent in writing when a pen input operation is performed.
　なお、本実施形態は、次のように変更して具体化することも可能である。
　・基材の面のうちの二つ以上の面にアンチグレア面を有するアンチグレア膜が設けられていてもよい。 In addition, this embodiment can also be changed and embodied as follows.
-An anti-glare film having an anti-glare surface may be provided on two or more of the surfaces of the substrate.
　・基材とアンチグレア膜との間、及びアンチグレア膜の上の少なくとも一方に、反射防止層や防汚層等のその他の層が設けられていてもよい。
　・透明基材として、ガラス基材１１の代わりに、ポリカーボネート基材等の樹脂基材を用いてもよい。 Other layers such as an antireflection layer and an antifouling layer may be provided between the substrate and the antiglare film and at least one on the antiglare film.
-As a transparent base material, instead of the glass base material 11, you may use resin base materials, such as a polycarbonate base material.
　・上記実施形態におけるアンチグレア面は、コーティング剤をガラス基材１１に塗布し、加熱することにより形成されたアンチグレア膜１２によって形成されているが、アンチグレア面は、ガラス基材１１の表面をエッチング処理して形成されてもよい。 -Although the anti-glare surface in the said embodiment is formed of the anti-glare film | membrane 12 formed by apply | coating a coating agent to the glass base material 11 and heating, an anti-glare surface etch-processes the surface of the glass base material 11 May be formed.
　次に、上記実施形態及び変更例から把握できる技術的思想について記載する。
　・前記アンチグレア面は、ウェットコート法により塗布されてなるアンチグレア膜により構成されている前記透明物品。 Next, the technical idea that can be grasped from the embodiment and the modified examples will be described.
-The transparent article in which the anti-glare surface is constituted by an anti-glare film applied by a wet coat method.
　・透明基材と、前記透明基材における少なくとも一つの面に設けられたアンチグレア面とを備える透明物品の表面に存在する、直径が１μｍ以上、高さが１μｍ以上である突起の１ｍｍ２あたりの個数に基づいて透明物品の表面の書き味を評価する評価方法。 -Per 1 mm 2 of protrusions having a diameter of 1 μm or more and a height of 1 μm or more present on the surface of a transparent article comprising a transparent substrate and an antiglare surface provided on at least one surface of the transparent substrate An evaluation method for evaluating the writing quality of the surface of a transparent article based on the number.
　・ペン入力操作が行われる部位に用いられる透明物品の製造方法であって、前記透明物品は、透明基材と、前記透明基材における少なくとも一つの面に設けられたアンチグレア面とを備え、
前記アンチグレア面はアンチグレア膜の表面であり、前記アンチグレア膜は、前記透明基材に対して、マトリックス前駆体を含むコーティング剤をスプレーコート法により塗布して形成され、前記コーティング剤をスプレーコート法で塗布する際のスプレー距離が６０ｍｍ以上であることを特徴とする透明物品の製造方法。 A method for producing a transparent article used in a site where a pen input operation is performed, the transparent article comprising a transparent substrate and an antiglare surface provided on at least one surface of the transparent substrate;
The antiglare surface is the surface of an antiglare film, and the antiglare film is formed by applying a coating agent containing a matrix precursor to the transparent substrate by a spray coating method, and the coating agent is formed by a spray coating method. A method for producing a transparent article, wherein a spray distance during application is 60 mm or more.
　（試験例１～１４）
　アンチグレア膜の成膜条件を異ならせた試験例１～１４のガラス物品を作製した。すなわち、縦１５０ｍｍ、横３００ｍｍ、厚さ１．１ｍｍの強化ガラスからなるガラス基材（日本電気硝子社製：Ｄｉｎｏｒｅｘ（登録商標））の表面に対して、ノズル径０．６ｍｍのスプレーコーティング装置により、水を含む液状媒体にアンチグレア膜の前駆体（オルトケイ酸テトラエチル）を溶解することで調製したコーティング剤を塗布することによりアンチグレア膜を形成した。ガラス基材に対するコーティング剤の単位面積あたりの塗布量は３×１０－５ｇ／ｍｍ２とした。また、成膜時における雰囲気温度、雰囲気湿度、スプレー移動速度（ノズルの移動速度）、及びスプレー距離は、表１に示すとおりである。 (Test Examples 1 to 14)
Glass articles of Test Examples 1 to 14 having different antiglare film forming conditions were produced. That is, with a spray coating apparatus having a nozzle diameter of 0.6 mm on the surface of a glass substrate (Nippon Electric Glass Co., Ltd .: Dinorex (registered trademark)) made of tempered glass having a length of 150 mm, a width of 300 mm, and a thickness of 1.1 mm. Then, an antiglare film was formed by applying a coating agent prepared by dissolving a precursor of an antiglare film (tetraethyl orthosilicate) in a liquid medium containing water. The coating amount per unit area of the coating agent on the glass substrate was 3 × 10 −5 g / mm 2 . Table 1 shows the atmospheric temperature, atmospheric humidity, spray moving speed (nozzle moving speed), and spray distance during film formation.
　（突起数の測定）
　試験例１～１４のガラス物品について、アンチグレア膜のアンチグレア面に存在する、直径が１μｍ以上、高さが１μｍ以上の突起の数を測定した。突起数の測定は、光学顕微鏡（倍率２００倍）を用いて、図３に示すような黒点の個数を数えることにより行った。具体的には、アンチグレア面から１ｍｍ２（縦１ｍｍ×横１ｍｍ）の領域を無作為に５箇所選定し、それらの各領域内に存在する上記突起の数を数えるとともに、その平均値を算出した。その結果を表１に示す。 (Measurement of the number of protrusions)
For the glass articles of Test Examples 1 to 14, the number of protrusions present on the antiglare surface of the antiglare film and having a diameter of 1 μm or more and a height of 1 μm or more was measured. The number of protrusions was measured by counting the number of black spots as shown in FIG. 3 using an optical microscope (200 times magnification). Specifically, five areas of 1 mm 2 (1 mm long × 1 mm wide) were randomly selected from the antiglare surface, the number of the protrusions present in each of these areas was counted, and the average value was calculated. . The results are shown in Table 1.
　（書き味の評価）
　３０人のパネラーに、入力ペン（ワコム社製：プロペン（ＫＰ－５０３Ｅ））を用いて各試験例のガラス物品の表面に描画する操作を行わせ、紙に近い質感で書き味が良いと感じるか否かを評価させた。その結果を表１の「書き味」欄に示す。なお、「書き味」欄においては、書き味が良いと評価した人数が２６人以上のものを「◎」、書き味が良いと評価した人数が２１人以上２５人以下のものを「○」、書き味が良いと評価した人数が１６人以上２０人以下のものを「△」、書き味が良いと評価した人数が１５人以下のものを「×」で示している。 (Evaluation of writing quality)
Thirty panelists were asked to draw on the surface of the glass article of each test example using an input pen (Wacom: Propen (KP-503E)), and feel good writing with a texture close to paper It was evaluated whether or not. The results are shown in the “writing quality” column of Table 1. In the “writing quality” column, “◎” indicates that the number of people who evaluated that the writing quality is good is 26 or more, and “○” indicates that the number of people evaluated that the writing quality is good is 21 or more and 25 or less. “△” indicates that the number of people evaluated that writing quality is good is 16 or more and 20 or less, and “×” indicates that the number of people evaluated that writing quality is good is 15 or less.
Figure JPOXMLDOC01-appb-T000001
 　表１に示すように、スプレー距離が長くなるにしたがって、直径が１μｍ以上、高さが１μｍ以上の突起数が増加することが分かる。また、１ｍｍ２あたりの上記突起数が５０個未満である試験例７～１４と比較して、１ｍｍ２あたりの上記突起数が５０個以上である試験例１～６は、書き味の評価が高い結果となった。そして、試験例１～６のなかでも、１ｍｍ２あたりの上記突起数が１００個以上である試験例１～４、特に１ｍｍ２あたりの上記突起数が３００個以上である試験例１は、書き味の評価が非常に高い結果となった。この結果から、上記突起数に応じてペン入力操作を行った際の書き味が変化することが分かる。また、１ｍｍ２あたりの上記突起数を５０個以上とすることにより、ペン入力操作を行った際の書き味が優れたものとなることが分かる。
Figure JPOXMLDOC01-appb-T000001
 As shown in Table 1, it can be seen that the number of protrusions having a diameter of 1 μm or more and a height of 1 μm or more increases as the spray distance increases. Further, the number of protrusions per 1 mm 2 is compared to the test examples 7 to 14 is less than 50, Test Examples 1 to 6 above projections per 1 mm 2 is 50 or more, the evaluation of writing taste The result was high. Among Test Examples 1 to 6, Test Examples 1 to 4 in which the number of protrusions per 1 mm 2 is 100 or more, particularly Test Example 1 in which the number of protrusions per 1 mm 2 is 300 or more are written. The taste evaluation was very high. From this result, it can be seen that the writing quality when the pen input operation is performed changes according to the number of protrusions. Further, by making the number of the protrusions per 1 mm 2 to 50 or more, it can be seen that becomes the writing feeling when performing the pen input operation is excellent.
　１０…ガラス物品、１１…ガラス基材、１２…アンチグレア膜。 10 ... Glass article, 11 ... Glass substrate, 12 ... Anti-glare film.

Claims (3)

  1. 　ペン入力操作が行われる部位に用いられる物品であって、
    　基材と、前記基材における少なくとも一つの面に設けられたアンチグレア面とを備え、
    　前記アンチグレア面に存在する、直径が１μｍ以上、高さが１μｍ以上である突起の１ｍｍ２あたりの個数が５０個以上であることを特徴とする物品。     An article used for a part where a pen input operation is performed,
    A substrate and an anti-glare surface provided on at least one surface of the substrate;
    An article characterized in that the number per 1 mm 2 of protrusions having a diameter of 1 μm or more and a height of 1 μm or more present on the antiglare surface is 50 or more.
  2. 　前記アンチグレア面は、ＳｉＯ２、Ａｌ２Ｏ３、ＺｒＯ２、ＴｉＯ２から選ばれる少なくとも一種を含有するアンチグレア膜により構成されることを特徴とする請求項１に記載の物品。 The anti-glare surface The article of claim 1, characterized in that it is constituted by an anti-glare film containing at least one selected from SiO 2, Al 2 O 3, ZrO 2, TiO 2.
  3. 　前記突起の１ｍｍ２あたりの個数が１００個以上であることを特徴とする請求項１又は請求項２に記載の物品。 The article according to claim 1 or 2, wherein the number of the projections per 1 mm 2 is 100 or more.
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