WO2012165107A1 - Fingerprint stain-resistant substrate - Google Patents
Fingerprint stain-resistant substrate Download PDFInfo
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- WO2012165107A1 WO2012165107A1 PCT/JP2012/061705 JP2012061705W WO2012165107A1 WO 2012165107 A1 WO2012165107 A1 WO 2012165107A1 JP 2012061705 W JP2012061705 W JP 2012061705W WO 2012165107 A1 WO2012165107 A1 WO 2012165107A1
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- fingerprint
- hole
- substrate
- base material
- smooth surface
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/77—Coatings having a rough surface
Definitions
- the present invention provides a substrate having a concave hole that collects fingerprint components on the surface, whereby the above-mentioned problems are solved.
- the optical microscope photograph showing a mode that the pseudo fingerprint was made to adhere to the base material (float glass which performed the water- and oil-repellent treatment) obtained by the comparative example 1 of this invention.
- the film examples include a sol-gel film, a glass thin plate, or a polymer film, and specific materials include inorganic compounds such as silica, titania, alumina, zirconia, indium-containing tin oxide, antimony-containing tin oxide, aluminum, Metals such as tin, zinc, silver, gold, copper, platinum, nickel, cobalt, chromium, polyester, polyamide, polyimide, polyacrylate, polyolefin, polycarbonate, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl chloride Examples thereof include organic compounds such as vinylidene, silicone, cellulose resin, and fluorine resin, or organic-inorganic hybrid materials, and combinations thereof.
- the material of the substrate having a film is not particularly limited, and examples thereof include glass and plastic.
- fingerprint contamination resistance can be obtained by having a concave hole on the smooth surface of the substrate.
- capillary force acts on the hole, and the fingerprint component is trapped in the hole.
- FIG. 4 shows the fingerprint component 6 trapped in a part or all of the hole 3. Since the fingerprint component trapped in this way is present in the hole as a collective droplet, it is visually observed. Less noticeable.
- the average depth of the holes (here, “depth” is the difference between the height of the reference surface and the height of the bottom of the hole, and is the length indicated by d in FIGS. 2 and 3).
- depth is usually from 0.2 to 50 ⁇ m. If it is smaller than 0.2 ⁇ m, it will approach a flat state, and fingerprint stain resistance will not be obtained substantially. On the other hand, if it is larger than 50 ⁇ m, the cloth fibers often do not reach the bottom surface of the pattern when wiping with a cloth with a small force, resulting in poor wiping performance. More preferably, it is 0.5 to 20 ⁇ m.
- the distance between the hole at the fingerprint-resistant stain-resistant portion and the hole adjacent to the hole may be optimized depending on the use of the base material and the shape of the hole, but is usually about 1 to 300 ⁇ m.
- the thickness is preferably 10 to 100 ⁇ m. If it is narrower than 1 ⁇ m, the fibers of the cloth will be caught on the wall surface of the hole when wiping the cloth.
- the fingerprint component may remain as fine droplets, and the attached fingerprint component may be easily visible.
- the arrangement pattern of the holes on the substrate surface is preferably regular.
- it is a regular pattern, for example, when it is used as a cover glass of a display, the visibility becomes high.
- moire occurs, which is not preferable. In that case, it is necessary to adjust the frequency of the pattern, that is, the distance between the patterns, or adjust the pattern so that it approaches an irregular arrangement. There is.
- the method for processing the shape of the hole on the surface of the base material is not particularly limited. In consideration of the characteristics of the base material to be obtained (optical characteristics, roughness of the processed surface, strength, etc.) Of these, a desired method may be selected. For example, a method of forming the hole on the smooth surface of the substrate by performing a masking process corresponding to the shape of the hole with a photoresist or the like and then performing surface grinding or etching such as a sand blast method. In addition, for example, a mold press molding method, a screen printing method, an ink jet printing method, an imprint method, and the like can be given.
- the square root of the projected area is calculated to be 44 ⁇ m.), The average depth is 5 ⁇ m, the hole area ratio to the observation region (100%) is 20%, and the distance between the hole and the hole adjacent to the hole is 50 ⁇ m. A substrate was obtained.
- This observation region indicates, for example, the area of the entire photomicrograph in FIG.
- the anti-fingerprint anti-fouling property for the base material after pseudo-fingerprint adhesion, the base material after pseudo-fingerprint wiping, and the base material after pseudo-fingerprint reattachment are as follows. evaluated. 1. Visual evaluation (after adhesion: ⁇ not noticeable, ⁇ difficult to judge, ⁇ equivalent to unprocessed substrate; after wiping: ⁇ no fingerprint trace left, ⁇ fingerprint trace left, ⁇ fingerprint trace spread; after reattachment: ⁇ Inconspicuous, ⁇ difficult to judge, ⁇ equivalent to unprocessed substrate) 2.
- Tables 2 and 3 show the evaluation results of the base material of Example 1. Float glass with an area ratio of 20%, a hole with dimensions of 44 ⁇ m and depth of 5 ⁇ m, the fingerprint trace after attaching the pseudo fingerprint is not noticeable visually, and the fingerprint trace after wiping is not visually confirmed It was. Furthermore, the fingerprint trace after the pseudo fingerprint was reattached to the wiped portion was not visually noticeable. Further, the change in initial haze was 4%, and the change in reattachment haze was 5%.
- the above-mentioned hole is high in fingerprint contamination resistance as compared with a base material in which the above-described hole is not processed and the float glass is only given water and oil repellency. It has been found that having an anti-finger is very effective in improving the resistance to fingerprint contamination.
- Examples 2 to 23 After obtaining a substrate having holes shown in Table 1 in the same manner as in Example 1, perfluoropolyalkylene ether-modified silane (Dow Corning 2634: manufactured by Toray Dow Corning, Inc., or KY-130) shown in Table 1 was further obtained. : Shin-Etsu Chemical Co., Ltd.) 1 part by weight and fluorinated inert liquid (FC-3283: Sumitomo 3M Co., Ltd.) 500 parts by weight is mixed with the dip coating on the substrate, and the substrate is heated at 150 ° C. By heating for 10 minutes, a base material imparted with water and oil repellency was obtained.
- Tables 2 and 3 show the evaluation results of the substrates of Examples 2 to 23, respectively. Anti-fingerprint stain resistance was confirmed on all the substrates of the examples. Taking the optical microscope observation of Example 2 as an example, as shown in FIG. 8, most of the pseudo-fingerprint attached to the base material is trapped in a hole in the base material surface, Only a few fingerprint components were present. Also, as shown in FIG. 9, after one reciprocation wiping test, the fingerprint component is removed from the hole, and a small amount of fine fingerprint component remains in the hole. It was confirmed that almost no fingerprint component remained. Furthermore, as shown in FIG. 10, most of the pseudo-fingerprints reattached to the wiping portion are trapped in the holes in the surface of the substrate, and the fingerprint component existing on the reference surface is very small. .
- Example 11 taking the optical microscope observation of Example 11 as an example, as shown in FIG. 11, most of the pseudo-fingerprints attached to the base material are trapped in holes formed on the base material surface, and are collected. It was a droplet and the fingerprint component present on the reference surface was very small. Also, as shown in FIG. 12, the fingerprint component is almost removed from the hole after one reciprocal wiping test, the fingerprint component is hardly left on the reference surface, and the residual amount of the fingerprint component is extremely small. Was confirmed. Furthermore, as shown in FIG. 13, the pseudo-fingerprint reattached to the wiping portion is trapped in the hole on the substrate surface, and is formed into a droplet, which is present on the reference surface. The fingerprint component to be performed was slight.
- a base material was obtained by imparting water and oil repellency to the glass substrate of one type of general-purpose float glass and two types of glass substrates obtained by processing the fine structure of the float glass in the same manner as in the examples. Details of the manufacturing conditions are shown in Table 1 as Comparative Examples 1 to 7.
- the pseudo fingerprint attached to the float glass that has only been given water and oil repellency becomes droplets on the substrate, and the droplet size becomes small after one round of wiping test. It was observed that it remained in
- the fingerprint stain-resistant substrate of the present invention exhibits excellent fingerprint stain resistance in an environment where a finger or the like is easily touched and a fingerprint component is easily attached.
- architectural window glass and showcases for store products, dolls, etc.
- partition base materials and resin materials for store products, dolls, etc.
- decorative decorative plates for store products, dolls, etc.
- partition base materials and resin materials for store products, dolls, etc.
- decorative decorative plates for store products, dolls, etc.
- metal plates for store products, dolls, etc.
- furniture electricity, electronic equipment (TVs, mobile phones)
- Base material 2 which has a hole Reference surface 3 of a base material 4 Recessed hole 4
- Base material which has a layer which has a hole 5 Layer which has a hole 6 Fingerprint component trapped in a part or the whole of a hole
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- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
Disclosed is a fingerprint stain-resistant substrate characterized by comprising, at positions with which fingers are brought into contact of a smooth surface of a substrate having light transmittance, light reflectivity or gloss, concave holes which each collect a fingerprint component adhering to the smooth surface by capillary force, and characterized in that the sizes of the square roots of the projected areas of the holes in front view are 10-300 μm, the mean depth of the holes is 0.2-50 μm, and the area ratio of the total area of the holes present in an observation region of the smooth surface to the area of the observation region is 10-85%. This substrate has an excellent fingerprint stain resistance.
Description
本発明は、優れた耐指紋汚染性を有する基材に関するものである。
The present invention relates to a substrate having excellent fingerprint stain resistance.
ガラス、プラスチック、金属等の光透過性、光反射性、または光沢性を有する基材は、電子機器や自動車部品、建築物等の材料として汎用されている。これらの基材は使用部分によっては、人の手に触れる機会が多く、指紋や皮脂などの生体由来の汚れ（以降、単に「指紋成分」と記載する）が付着しやすく、かつその汚れを容易に拭き取ることができない性質があった。そのため、付着した指紋成分および／または完全には拭き取れなかった指紋成分が非常に目立ちやすく、基材の美観を著しく損ねる（以後、単に「指紋汚染性」と記載する場合もある）という問題があった。
A base material having light transmissivity, light reflectivity, or glossiness such as glass, plastic, or metal is widely used as a material for electronic devices, automobile parts, buildings, and the like. Depending on the part of use, these base materials have many opportunities to be touched by human hands, so that dirt derived from living organisms such as fingerprints and sebum (hereinafter simply referred to as “fingerprint component”) can easily adhere to them. There was a property that could not be wiped off. Therefore, there is a problem that the attached fingerprint component and / or the fingerprint component that has not been completely wiped off are very noticeable, and the appearance of the substrate is remarkably impaired (hereinafter, simply referred to as “fingerprint contamination”). It was.
上記問題を解決するために、基材を表面処理し、基材表面の表面エネルギーを低下させることで、指紋成分を基材に付着しにくくし、また馴染みにくく（濡れにくく）することで、指紋成分に対する耐性を高める試みが行われている。例えば特許文献１では、基材の表面に、下記一般式（Ｉ）で表され、数平均分子量が５×１０2 ～１×１０5 であるケイ素含有有機含フッ素ポリマーの層を形成したことを特徴とする防汚性基材が記載されている。
In order to solve the above problems, the surface treatment of the base material and the surface energy of the base material surface are reduced, thereby making it difficult for the fingerprint component to adhere to the base material and making it difficult to become familiar (hard to get wet). Attempts have been made to increase resistance to ingredients. For example, in Patent Document 1, a layer of a silicon-containing organic fluorine-containing polymer represented by the following general formula (I) and having a number average molecular weight of 5 × 10 2 to 1 × 10 5 is formed on the surface of a substrate. A characteristic antifouling substrate is described.
特許文献２では、基材表面の加工により基材に撥水撥油性を付与し表面エネルギーを低下させる方法が開示されており、具体的には少なくともひとつの表面が撥水撥油性を示し、水または油の少なくともひとつの液滴の接触角が減少することを避けるための凹型構造を持っている幾何学的特徴を有し、その寸法が異なる複数の組を持つガラス基材が記載されている。
Patent Document 2 discloses a method of imparting water / oil repellency to a substrate by processing the surface of the substrate to reduce surface energy. Specifically, at least one surface exhibits water / oil repellency, Or a glass substrate having a plurality of sets with different geometrical features having a concave structure to avoid a decrease in the contact angle of at least one droplet of oil .
しかしながら、指紋成分を基材に完全に付着させないことは難しく、近年では上記問題に対する別のアプローチとして、指紋成分の付着を目立ちにくく、または馴染みやすくすることが課題とされている。例えば特許文献３ではステンレス鋼板の表面に複数の凹凸構造をランダムに配列し表面に透明な有機樹脂被膜を形成することにより、指紋成分の目立ちにくいステンレス鋼板を提供している。また、特許文献４では特定の微細構造を基材上に形成することにより、該微細構造の凸部から凹部へ指紋成分を拡散することで、特許文献５では凹凸部を有する層を基材に持たせることにより、凹部へ指紋成分を誘導することで、目立たなくする方法がそれぞれ開示されている。
However, it is difficult to completely prevent the fingerprint component from adhering to the substrate. In recent years, as another approach to the above problem, it has been a problem to make the fingerprint component less noticeable or familiar. For example, Patent Document 3 provides a stainless steel plate in which fingerprint components are hardly noticeable by randomly arranging a plurality of uneven structures on the surface of the stainless steel plate and forming a transparent organic resin film on the surface. In Patent Document 4, a specific fine structure is formed on a base material to diffuse a fingerprint component from the convex portion to the concave portion of the fine structure. In Patent Document 5, a layer having an uneven portion is used as a base material. Each of the methods has been disclosed to make it inconspicuous by guiding the fingerprint component into the recess.
特許文献４や特許文献５のように指紋成分が馴染みやすい効果を付与した場合、一度付着した指紋成分の除去性は「指紋成分が付着しにくい」基材に比べて劣る、或いは考慮されない場合がほとんどである。上記の微細構造の中に入り込んだ指紋成分が、布等で拭き取りを行っても、残留し易い場合、該微細構造表面に再度指紋成分が付着した場合、微細構造に収容しきれなくなった指紋成分が基材表面に大量に存在するようになり、指紋成分の付着を目立ちにくくする効果が著しく損なわれてしまう恐れがある。そのため、一旦付着した指紋成分を、微細構造も含めた基材表面から、布等での拭き取りで容易に除去することは重要であり、本発明では、従来技術とは異なる微細構造によって、付着した指紋成分が目立ちにくく、かつ、付着した指紋成分が布等による乾拭きで拭き取りやすい基材であり、拭き取り部分に再度指紋成分が付着した場合であっても、該指紋成分が目立ちにくい基材を提供することを課題とする。
When the effect that the fingerprint component is easy to be familiar is given as in Patent Document 4 and Patent Document 5, the removability of the fingerprint component once attached may be inferior or not considered in comparison with the substrate that is “hard to attach the fingerprint component”. Is almost. If the fingerprint component that has entered the fine structure is likely to remain even after wiping with a cloth, etc., if the fingerprint component adheres again to the surface of the fine structure, the fingerprint component that can no longer be accommodated in the fine structure May be present in a large amount on the surface of the substrate, and the effect of making the fingerprint component less noticeable may be significantly impaired. Therefore, it is important that the fingerprint component once adhered is easily removed from the substrate surface including the fine structure by wiping with a cloth or the like. In the present invention, the fingerprint component is adhered by a fine structure different from the prior art. Provides a base material that does not stand out easily even if the fingerprint component does not stand out easily and the attached fingerprint component is easy to wipe off by dry wiping with a cloth, etc. The task is to do.
本発明は、表面に指紋成分を集めるような凹型の穴を有した基材を提供するものであり、そのことにより前記課題が解決される。
The present invention provides a substrate having a concave hole that collects fingerprint components on the surface, whereby the above-mentioned problems are solved.
本発明において、「耐指紋汚染性」とは付着した指紋成分が目立ちにくく、かつ、付着した指紋成分が布等を用いて拭き取りやすく、さらに、拭き取った部分に再度指紋成分が付着した場合であっても、該指紋成分が目立ちにくいことを意味する。後述する実施例において「耐指紋汚染性」の評価方法を記載する。
In the present invention, “fingerprint contamination resistance” refers to the case where the attached fingerprint component is not noticeable, the attached fingerprint component is easily wiped off with a cloth, and the fingerprint component adheres again to the wiped portion. However, this means that the fingerprint component is not noticeable. An evaluation method of “anti-fingerprint stain resistance” will be described in Examples described later.
本発明に依れば、光透過性、光反射性、または光沢性を有する基材の平滑な面の指が接触する箇所に、該平滑な面に付着した指紋成分を毛細管力で集める凹型の穴を有し、該穴の正面視での投影面積の二乗根の寸法が１０～３００μｍであり、該穴の平均深さが０．２～５０μｍであり、該平滑な面の観察領域の面積（１００％）に対する、観察領域内に存在する該穴の合計面積の面積比が１０～８５％であることを特徴とする、耐指紋汚染性基材（第１基材）が提供される。
According to the present invention, the concave shape that collects the fingerprint component adhering to the smooth surface by capillary force at the place where the finger of the smooth surface of the base material having light transmission property, light reflection property, or glossiness contacts. The hole has a square root size of the projected area in front view of the hole is 10 to 300 μm, the average depth of the hole is 0.2 to 50 μm, and the area of the observation area of the smooth surface There is provided a fingerprint-fouling-resistant substrate (first substrate), wherein the area ratio of the total area of the holes existing in the observation region to (100%) is 10 to 85%.
第１基材は、前記穴の正面視での形状が、１～６個の角を有することを特徴とする、耐指紋汚染性基材（第２基材）であってもよい。
The first substrate may be a fingerprint-fouling-resistant substrate (second substrate) in which the shape of the hole in front view has 1 to 6 corners.
第１又は第２基材は、耐指紋汚染性部分における前記穴の面積比が１３～６０％であることを特徴とする、耐指紋汚染性基材（第３基材）であってもよい。ここでいう「耐指紋汚染性部分」とは、基材の平滑な面において耐指紋汚染性を付与したい部分のことである。
The first or second substrate may be a fingerprint stain-resistant substrate (third substrate), wherein an area ratio of the holes in the fingerprint stain-resistant portion is 13 to 60%. . The “fingerprint contamination resistant portion” referred to here is a portion to which fingerprint contamination resistance is desired to be imparted on the smooth surface of the substrate.
第１乃至第３基材のいずれか１つは、前記穴が、該穴の形状に対応したマスキング処理を施した後、表面研削またはエッチングを施すことにより前記基材の平滑な面に形成されたものであることを特徴とする、耐指紋汚染性基材（第４基材）であってもよい。
Any one of the first to third substrates is formed on the smooth surface of the substrate by subjecting the hole to a masking process corresponding to the shape of the hole, followed by surface grinding or etching. It may also be a fingerprint-fouling resistant base material (fourth base material), characterized in that
第１乃至第４基材のいずれか１つは、前記基材の平滑な面がフロートガラスのトップ面またはボトム面であることを特徴とする、耐指紋汚染性基材（第５基材）であってもよい。
Any one of the first to fourth substrates is a fingerprint-fouling-resistant substrate (fifth substrate), wherein the smooth surface of the substrate is a top surface or a bottom surface of float glass It may be.
第１乃至第５基材のいずれか１つは、前記基材表面に撥水撥油性膜を有することを特徴とする、耐指紋汚染性基材（第６基材）であってもよい。
Any one of the first to fifth substrates may be a fingerprint-resistant substrate (sixth substrate) characterized in that it has a water / oil repellent film on the substrate surface.
本発明によれば、付着した指紋成分が目立ちにくく、かつ布等を用いた乾拭きで拭き取りやすい基材であり、拭き取り部分に再度指紋成分が付着した場合であっても、該指紋成分が目立ちにくい基材を提供することができる。
According to the present invention, the attached fingerprint component is inconspicuous, and is a substrate that can be easily wiped off by dry wiping using a cloth or the like. Even when the fingerprint component adheres again to the wiped portion, the fingerprint component is inconspicuous A substrate can be provided.
本発明は付着した指紋成分を集めるための穴を表面に有し、集めた指紋成分を除去しやすい基材を提供するものである。本発明の実施形態の一つとして図２に示すように基材１の表面２（以降、基材の穴では無い部分の表面を「基準面」と記載する）に対して凹型の穴３が直接形成されたものがある。本発明の耐指紋汚染性基材は、前記基準面に直接指紋が接触した際に、指紋成分が前記穴に収容され易く、優れた耐指紋汚染性を発現するものである。また、前記基材表面に撥水撥油性膜を有する場合も、基準面上の撥水撥油性膜に指紋が接触した際に、同様に優れた耐指紋汚染性を発現するものである。
The present invention provides a substrate that has holes on the surface for collecting attached fingerprint components and that can easily remove collected fingerprint components. As an embodiment of the present invention, as shown in FIG. 2, a concave hole 3 is formed with respect to the surface 2 of the base material 1 (hereinafter, the surface of the portion that is not a hole of the base material is referred to as “reference surface”). Some are directly formed. The fingerprint stain-resistant substrate of the present invention exhibits excellent fingerprint stain resistance because the fingerprint component is easily accommodated in the hole when the fingerprint directly contacts the reference surface. In addition, even when the substrate surface has a water / oil repellent film, when the fingerprint comes into contact with the water / oil repellent film on the reference surface, the same excellent fingerprint stain resistance is exhibited.
本発明の基材は、光透過性、光反射性、または光沢性を有するものであればよく、材質は特に制限はないが、ガラスやプラスチックが好ましい。具体的には、例えば、ソーダライムシリケートガラス、アルミノシリケートガラス、石英ガラス、無アルカリガラス、その他の各種ガラスなどからなるガラスが挙げられる。ガラス以外に、例えば、ポリエステル、ポリアミド、ポリアクリレート、ポリオレフィン、ポリカーボネート、ポリスチレン、ポリウレタン、ポリビニルアルコール、ポリビニルブチラール、ポリ塩化ビニル、ポリ塩化ビニリデンなどからなるプラスチックも挙げられる。本発明の基材としては、元々平滑な表面を有する基材の該表面に前記の穴を形成したものが好ましい。この場合、穴が形成されなかった部分、すなわち元々の平滑な面が前記基準面に相当する。剛性、耐摩耗性及び、耐加傷性の観点からガラスが好ましい。
The base material of the present invention is not particularly limited as long as it is light transmissive, light reflective, or glossy, but glass or plastic is preferable. Specifically, for example, glass made of soda lime silicate glass, aluminosilicate glass, quartz glass, alkali-free glass, and other various glasses can be used. In addition to glass, for example, plastics made of polyester, polyamide, polyacrylate, polyolefin, polycarbonate, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinylidene chloride, and the like are also included. As the base material of the present invention, a base material having a smooth surface and the above-described holes formed on the surface is preferable. In this case, the portion where the hole is not formed, that is, the original smooth surface corresponds to the reference surface. Glass is preferred from the viewpoints of rigidity, wear resistance and scratch resistance.
また、別の実施形態としては、図３のように基準面２に凹型の穴３を形成した膜状の基材５と別の基材４との複合基材であってもよい（ここで膜とは「フィルム」、「シート」、「板」、「被膜」や「コーティング」といった概念を含むものである）。膜としては、ゾルゲル膜、ガラスの薄板等、又は高分子膜があり、具体的な材質としては、シリカ、チタニア、アルミナ、ジルコニア、インジウム含有酸化スズ、アンチモン含有酸化スズなどの無機化合物、アルミニウム、スズ、亜鉛、銀、金、銅、白金、ニッケル、コバルト、クロムなどの金属、ポリエステル、ポリアミド、ポリイミド、ポリアクリレート、ポリオレフィン、ポリカーボネート、ポリスチレン、ポリウレタン、ポリビニルアルコール、ポリビニルブチラール、ポリ塩化ビニル、ポリ塩化ビニリデン、シリコーン、セルロース系樹脂、フッ素系樹脂などの有機化合物、又は、有機―無機ハイブリッド材料、及びこれらの組み合わせが挙げられる。また、膜を有する基材の材質は特に制限はないが、例えばガラスやプラスチックなどが挙げられる。
Further, as another embodiment, a composite base material of a film-like base material 5 in which a concave hole 3 is formed on the reference surface 2 and another base material 4 as shown in FIG. The term “film” includes concepts such as “film”, “sheet”, “plate”, “film” and “coating”). Examples of the film include a sol-gel film, a glass thin plate, or a polymer film, and specific materials include inorganic compounds such as silica, titania, alumina, zirconia, indium-containing tin oxide, antimony-containing tin oxide, aluminum, Metals such as tin, zinc, silver, gold, copper, platinum, nickel, cobalt, chromium, polyester, polyamide, polyimide, polyacrylate, polyolefin, polycarbonate, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl chloride Examples thereof include organic compounds such as vinylidene, silicone, cellulose resin, and fluorine resin, or organic-inorganic hybrid materials, and combinations thereof. The material of the substrate having a film is not particularly limited, and examples thereof include glass and plastic.
前記基材の形状は用途によって適宜決定される。好ましくはシート状およびフィルム状である。
The shape of the substrate is appropriately determined depending on the application. Preferably they are a sheet form and a film form.
前記基材において、指紋成分を集めるための凹型の穴を有する面が、片面であるか両面であるか、また、前記基材表面の全体であるか一部であるかは、特に限定されない。前記基材の耐指紋汚染性を付与したい部分（以降、単に「耐指紋汚染性部分」と記載する）に該穴を有していれば良く、用途によって適宜決定すればよい。換言すれば、指が接触する箇所に、該穴を設けると、耐指紋汚染性が有効となる。また、基材の基準面は平面であっても曲面であってもよい。
In the base material, it is not particularly limited whether the surface having the concave hole for collecting the fingerprint component is one side or both sides, and whether it is the whole surface or a part of the base material surface. What is necessary is just to have the said hole in the part (henceforth only described as a "fingerprint stain-resistant part") which wants to provide the fingerprint stain resistance of the said base material, and should just determine suitably according to a use. In other words, if the hole is provided at a location where the finger comes into contact, fingerprint contamination resistance is effective. The reference surface of the substrate may be a flat surface or a curved surface.
本発明では基材の平滑な面に凹型の穴を有することで耐指紋汚染性が得られる。凹型の穴を有することで、該穴に毛細管力が働き、指紋成分は該穴の中にトラップされる。図４には穴３の一部又はすべてにトラップされた指紋成分６が表されているが、このようにトラップされた該指紋成分はまとまった液滴として該穴中に存在するため、目視で目立ちにくくなる。
In the present invention, fingerprint contamination resistance can be obtained by having a concave hole on the smooth surface of the substrate. By having a concave hole, capillary force acts on the hole, and the fingerprint component is trapped in the hole. FIG. 4 shows the fingerprint component 6 trapped in a part or all of the hole 3. Since the fingerprint component trapped in this way is present in the hole as a collective droplet, it is visually observed. Less noticeable.
また、指紋成分の拭き取りやすさの観点からは、液滴が該穴にまとまっているため、汎用の布を用いた乾拭きの場合でも、該布の繊維の空隙に働く毛細管力よって該指紋成分が布に吸い上げられる効果が向上し容易に拭き取ることが可能となる。穴の断面形状は、図２、３、４及び７に示すように、底部が平らであるのが好ましい。底部が、例えば、V型又はドーム型では、穴の底の狭い領域に指紋成分が溜り、該領域に働く毛細管力の方が繊維の空隙に働く毛細管力より大となり、指紋成分の拭き取りが難しくなる。また、布の繊維が該穴の底に届き難いため、指紋成分の拭き取りが難しくなる。なお、上記拭き取りには、タオル等の汎用の布を用いることができ、メガネ拭き用の布のようなさらに細かい繊維の布であれば、より拭き取りやすいため好ましい。
In addition, from the viewpoint of easy wiping of the fingerprint component, since the droplets are collected in the hole, the fingerprint component is caused by the capillary force acting on the voids of the fiber of the cloth even in the case of dry wiping using a general-purpose cloth. The effect of being sucked up by the cloth is improved and can be easily wiped off. The cross-sectional shape of the hole is preferably flat at the bottom, as shown in FIGS. For example, when the bottom is V-shaped or dome-shaped, the fingerprint component accumulates in a narrow area at the bottom of the hole, and the capillary force acting on the area becomes larger than the capillary force acting on the fiber gap, making it difficult to wipe off the fingerprint component. Become. Further, since the fibers of the cloth are difficult to reach the bottom of the hole, it is difficult to wipe off the fingerprint component. Note that a general-purpose cloth such as a towel can be used for wiping, and a cloth with finer fibers such as a cloth for wiping glasses is preferable because it is easier to wipe off.
該穴が存在しない場合、基材に付着した指紋成分は液滴サイズの小ささから布方向に吸い上げる力が生じず、指紋成分の液滴を移動させるのみである。加えてその拭き取り過程で指紋成分の液滴が分裂し、液滴サイズが更に小さくなってしまうため、液滴サイズがＭｉｅ散乱の領域となってしまい、その散乱特性から指紋払拭跡が白っぽく浮いたように見え基材の美観を損ねる。
When the hole does not exist, the fingerprint component adhering to the substrate does not generate a force to suck in the cloth direction from the small droplet size, and only moves the fingerprint component droplet. In addition, the droplet of the fingerprint component breaks up during the wiping process, and the droplet size further decreases, so the droplet size becomes a Mie scattering region, and the fingerprint wiping traces appear whitish due to the scattering characteristics. It looks like it detracts from the aesthetics of the substrate.
前記穴の形状は、指紋成分をまとまった液滴に集められる形状であれば特に限定はされないが、該穴の正面視での形状が、１～６個の角を有したものが好ましい。例えば、図５に示すように、1つの角を有する、略涙滴型を平面投影した形状のもの、２つの角を有する、略紡錘型を平面投影した形状のもの、略三角形、略四角形、略五角形、略六角形などが挙げられるが、各角度や形状を構成する曲線の形状は用途によって適宜決定される。正面視での形状で１～６個の角を有した凹型の穴には、角の角度が適切であるために、少ない指紋成分でも、角に指紋成分が集められ、該穴の正面視での形状が円よりも布で拭き取り易く好ましい（図６、７参照）。７個以上の角を有した場合は、１つの角当たりの角度が大きく、該穴の正面視での形状が円の場合と比較して効果に差がない。より好ましいのは、１～４個の角を有したものである。更に好ましいのは該穴の正面視での形状は略三角形又は略四角形である。指紋成分を集める性状を損なわない範囲で、角の形状は穴の加工精度に応じて、ｒ（円弧状）が付いていても良い。
The shape of the hole is not particularly limited as long as it is a shape that can be collected in a droplet containing a fingerprint component. However, the shape of the hole in front view is preferably one having 1 to 6 corners. For example, as shown in FIG. 5, a shape having a single corner, a shape obtained by planar projection of a substantially teardrop shape, a shape having two angles, a shape obtained by planarly projecting a spindle type, a substantially triangular shape, a substantially rectangular shape, Although a substantially pentagon, a hexagon, etc. are mentioned, the shape of the curve which comprises each angle and shape is suitably determined by a use. For concave holes with 1 to 6 corners in front view, the corner angle is appropriate, so even with a small amount of fingerprint components, fingerprint components are collected at the corners. The shape of is easier to wipe off with a cloth than a circle (see FIGS. 6 and 7). When there are seven or more corners, the angle per corner is large, and there is no difference in effect compared to the case where the shape of the hole in a front view is a circle. More preferred is one having 1 to 4 corners. More preferably, the shape of the hole in a front view is a substantially triangular shape or a substantially rectangular shape. As long as the property of collecting fingerprint components is not impaired, the shape of the corner may be r (arc-shaped) depending on the processing accuracy of the hole.
該穴の寸法（ここで寸法とは「穴の投影面積の二乗根」のことである）は、１０～３００μｍである。１０μｍ未満であると、該穴の大きさが小さすぎるため、一般的な指紋払拭の布の繊維では該穴の指紋成分と接触が難しくなり、極細繊維を用いた特殊なものでないと拭き取れないなどの問題が生じる。また３００μｍより大きいと、該穴に働く毛細管力が実質的に失われてしまう。該穴の形状及び寸法は統一されている必要はなく、任意の組み合わせで基材表面に存在することができる。
The dimension of the hole (here, the dimension is “the square root of the projected area of the hole”) is 10 to 300 μm. If the size is less than 10 μm, the size of the hole is too small, so that it is difficult to contact the fingerprint component of the hole with a fiber of a general fingerprint wiping cloth, and it cannot be wiped unless it is a special one using ultrafine fibers. Problem arises. On the other hand, if it is larger than 300 μm, the capillary force acting on the hole is substantially lost. The shape and dimensions of the holes need not be uniform, and can be present on the surface of the substrate in any combination.
前記穴の平均深さ（ここで「深さ」とは基準面の高さと穴の底部の高さの差のことであり、図２、３においてｄで示される長さである。）は、その基材の用途によって適宜変更できるが、通常は０．２～５０μｍである。０．２μｍよりも小さいとフラットな状態に近づき、実質的に耐指紋汚染性が得られない。また５０μｍよりも大きいと、布で小さい力で拭き取る際に布の繊維がパターンの底面まで届かないことが多く、拭き取り性で劣るようになる。より好ましくは０．５～２０μｍである。
The average depth of the holes (here, “depth” is the difference between the height of the reference surface and the height of the bottom of the hole, and is the length indicated by d in FIGS. 2 and 3). Although it can be appropriately changed depending on the use of the substrate, it is usually from 0.2 to 50 μm. If it is smaller than 0.2 μm, it will approach a flat state, and fingerprint stain resistance will not be obtained substantially. On the other hand, if it is larger than 50 μm, the cloth fibers often do not reach the bottom surface of the pattern when wiping with a cloth with a small force, resulting in poor wiping performance. More preferably, it is 0.5 to 20 μm.
前記基材表面において、耐指紋汚染性部分での前記穴の面積比は１０～８５％である。ここでいう面積比とは、任意に矩形領域（観察領域）を指定した場合の、矩形領域の面積（１００％）に対する穴の面積の総和の割合のことである。１０％未満だと実質的に耐指紋汚染性が得られない。８５％よりも大きいと布拭きの際に加工した該穴によってひっかかるようになるため滑りが悪くなる。より好ましくは１３～６０％である。また、穴の分布密度には偏りがあっても差し支えなく、指紋付着頻度が高い部分により密な加工を施してもよい。
In the substrate surface, the area ratio of the holes in the fingerprint resistant part is 10 to 85%. The area ratio here is the ratio of the total area of the holes to the area (100%) of the rectangular area when a rectangular area (observation area) is arbitrarily designated. If it is less than 10%, the fingerprint contamination resistance cannot be obtained substantially. If it is larger than 85%, it will be caught by the hole processed when wiping the cloth, and slipping will be worse. More preferably, it is 13 to 60%. In addition, the distribution density of the holes may be biased, and dense processing may be performed on a portion where the fingerprint adhesion frequency is high.
前記基材表面において、耐指紋汚染性部分での前記穴と該穴に隣り合う穴との間隔は、基材の用途と該穴の形状によって最適化されればよいが、通常１～３００μｍ程度であることが好ましく、より好ましくは１０～１００μｍである。１μｍよりも狭い場合、布拭きの際に該布の繊維が該穴の壁面にひっかかるようになるため滑りが悪くなり好ましくなく、３００μｍよりも広い場合、布拭きした後に基材表面の基準面に指紋成分が微細な液滴として残り、付着した指紋成分が目視で見えやすくなることがある。
On the surface of the base material, the distance between the hole at the fingerprint-resistant stain-resistant portion and the hole adjacent to the hole may be optimized depending on the use of the base material and the shape of the hole, but is usually about 1 to 300 μm. The thickness is preferably 10 to 100 μm. If it is narrower than 1 μm, the fibers of the cloth will be caught on the wall surface of the hole when wiping the cloth. The fingerprint component may remain as fine droplets, and the attached fingerprint component may be easily visible.
前記穴の基材表面での配列パターンは、規則的にされていることが好ましい。規則的なパターンであると、例えばディスプレイのカバーガラスとして用いる場合、視認性が高くなる。一方で画素ピッチとパターンの間で干渉が起こるとモアレが生じるため好ましくなく、その場合は、パターンの頻度即ちパターン間距離を調整したり、パターンを不規則配列に近づくように調整したりする必要がある。
The arrangement pattern of the holes on the substrate surface is preferably regular. When it is a regular pattern, for example, when it is used as a cover glass of a display, the visibility becomes high. On the other hand, if interference occurs between the pixel pitch and the pattern, moire occurs, which is not preferable. In that case, it is necessary to adjust the frequency of the pattern, that is, the distance between the patterns, or adjust the pattern so that it approaches an irregular arrangement. There is.
前記基材表面に前記穴の形状を加工する方法は特に制限されるものではなく、得られる基材の特性（光学特性や加工面の粗さ、強度等）を考慮して、各種加工法のうち所望の方法を選択すればよい。例えばフォトレジスト等により前記穴の形状に対応したマスキング処理を施した後、サンドブラスト法などの表面研削またはエッチングを施すことにより前記基材の平滑な面に前記穴を形成する方法が挙げられる。その他にも、例えば、モールドプレス成形法、スクリーン印刷法、インクジェット印刷法、インプリント法などが挙げられる。
The method for processing the shape of the hole on the surface of the base material is not particularly limited. In consideration of the characteristics of the base material to be obtained (optical characteristics, roughness of the processed surface, strength, etc.) Of these, a desired method may be selected. For example, a method of forming the hole on the smooth surface of the substrate by performing a masking process corresponding to the shape of the hole with a photoresist or the like and then performing surface grinding or etching such as a sand blast method. In addition, for example, a mold press molding method, a screen printing method, an ink jet printing method, an imprint method, and the like can be given.
また、上記の加工をした基材は表面処理剤を用いて撥水撥油性を付与してもよい。表面処理剤は例えば、市販品のパーフルオロポリアルキレンエーテル変性シランであるオプツールＤＳＸ（ダイキン工業社製）、ＫＹ－１３０（信越化学工業社製）、Ｄｏｗ Ｃｏｒｎｉｎｇ２６３４（東レ・ダウコーニング社製）などが挙げられる。また表面処理は一般的に知られている方法であればどのような方法を用いてもよく、ディップコーティング法、手塗り法、スプレー法、スピンコーティング法、フローコーティング法、蒸着法、刷毛塗り、ロールコーティング法などが挙げられ、さらに乾燥（加熱乾燥）を行う方法が挙げられる。
Further, the base material subjected to the above processing may be imparted with water and oil repellency by using a surface treatment agent. Examples of the surface treatment agent include commercially available perfluoropolyalkylene ether-modified silane OPTOOL DSX (manufactured by Daikin Industries), KY-130 (manufactured by Shin-Etsu Chemical Co., Ltd.), Dow Corning 2634 (manufactured by Dow Corning Toray). Can be mentioned. Any surface treatment may be used as long as it is a generally known method, such as dip coating, hand coating, spraying, spin coating, flow coating, vapor deposition, brush coating, Examples thereof include a roll coating method, and further a method of performing drying (heat drying).
詳細を下記に述べるが、本発明はこれら実施例のみに限定されるものではない。
Details will be described below, but the present invention is not limited to these examples.
［実施例１］
〔基材の準備〕
１００ｍｍ角、厚み２ｍｍのフロートガラス基板のトップ面上にフォトレジストを塗布し、表１に記載の加工パターンを施したマスクを介して露光させた後、現像および洗浄を行い、続いて加工深さが５μｍになるまでサンドブラスト処理を行った。その後基板からレジストを除去し、洗浄することで、表１に示すとおり、正面視での穴の形状が円形であり、寸法が４４μｍ（該穴の形状は直径５０μｍの円であり、該穴の投影面積の二乗根を算出すると４４μｍとなる。）、平均深さが５μｍ、観察領域（１００％）に対する穴の面積比が２０％、穴と該穴に隣り合う穴との間隔が５０μｍである基材を得た。この観察領域とは、例えば図８の顕微鏡写真全体の面積を指す。 [Example 1]
[Preparation of substrate]
A photoresist is applied on the top surface of a 100 mm square, 2 mm thick float glass substrate, exposed through a mask provided with the processing pattern shown in Table 1, and then developed and washed, followed by processing depth. Sand blasting was performed until the thickness became 5 μm. Thereafter, the resist is removed from the substrate and washed. As shown in Table 1, the shape of the hole in the front view is circular, and the dimension is 44 μm (the shape of the hole is a circle having a diameter of 50 μm. The square root of the projected area is calculated to be 44 μm.), The average depth is 5 μm, the hole area ratio to the observation region (100%) is 20%, and the distance between the hole and the hole adjacent to the hole is 50 μm. A substrate was obtained. This observation region indicates, for example, the area of the entire photomicrograph in FIG.
〔基材の準備〕
１００ｍｍ角、厚み２ｍｍのフロートガラス基板のトップ面上にフォトレジストを塗布し、表１に記載の加工パターンを施したマスクを介して露光させた後、現像および洗浄を行い、続いて加工深さが５μｍになるまでサンドブラスト処理を行った。その後基板からレジストを除去し、洗浄することで、表１に示すとおり、正面視での穴の形状が円形であり、寸法が４４μｍ（該穴の形状は直径５０μｍの円であり、該穴の投影面積の二乗根を算出すると４４μｍとなる。）、平均深さが５μｍ、観察領域（１００％）に対する穴の面積比が２０％、穴と該穴に隣り合う穴との間隔が５０μｍである基材を得た。この観察領域とは、例えば図８の顕微鏡写真全体の面積を指す。 [Example 1]
[Preparation of substrate]
A photoresist is applied on the top surface of a 100 mm square, 2 mm thick float glass substrate, exposed through a mask provided with the processing pattern shown in Table 1, and then developed and washed, followed by processing depth. Sand blasting was performed until the thickness became 5 μm. Thereafter, the resist is removed from the substrate and washed. As shown in Table 1, the shape of the hole in the front view is circular, and the dimension is 44 μm (the shape of the hole is a circle having a diameter of 50 μm. The square root of the projected area is calculated to be 44 μm.), The average depth is 5 μm, the hole area ratio to the observation region (100%) is 20%, and the distance between the hole and the hole adjacent to the hole is 50 μm. A substrate was obtained. This observation region indicates, for example, the area of the entire photomicrograph in FIG.
〔耐指紋汚染性の評価方法〕
得られた基材の耐指紋汚染性の評価として、以下の（１）～（３）を行った。 [Fingerprint contamination resistance evaluation method]
The following (1) to (3) were carried out as evaluation of the fingerprint resistance of the obtained substrate.
得られた基材の耐指紋汚染性の評価として、以下の（１）～（３）を行った。 [Fingerprint contamination resistance evaluation method]
The following (1) to (3) were carried out as evaluation of the fingerprint resistance of the obtained substrate.
（１）擬似指紋の付着試験
直径２９ｍｍのシリコーンゴム栓の端面をＪＩＳ Ｒ６２５２に規定された基材Ｃｗ、研磨材Ａ、粒度Ｐ２４０の研磨紙を用いて粗らした人工指として用い、アクリル基板上に膜厚０．５ｍｍでスピンコーティングされたオレイン酸を人工指紋液として用いることで、定量的な擬似指紋付着試験を行った。アクリル基板に対して人工指を２５０ｇ／ｃｍ2で垂直に押し付けることで人工指紋液を人工指に転写し、評価する基材に対して同様に２５０ｇ／ｃｍ2で垂直に押し付けることで、基材に擬似指紋を付着させた。後述する、拭き取り試験後の基材に再度擬似指紋を付着させる場合も、上記と同様に行った。 (1) Pseudo-fingerprint adhesion test The end surface of a 29 mm diameter silicone rubber plug is used as an artificial finger roughened with a base material Cw, abrasive material A, and abrasive paper of particle size P240 specified in JIS R6252, on an acrylic substrate. A quasi-fingerprint adhesion test was conducted by using oleic acid spin-coated with a thickness of 0.5 mm as an artificial fingerprint liquid. By artificially pressing an artificial finger against an acrylic substrate at 250 g / cm 2 , the artificial fingerprint liquid is transferred to the artificial finger, and similarly at 250 g / cm 2 against the substrate to be evaluated, the substrate is pressed vertically. A pseudo-fingerprint was attached to the surface. When pseudo fingerprints were again attached to the substrate after the wiping test, which will be described later, the same procedure as described above was performed.
直径２９ｍｍのシリコーンゴム栓の端面をＪＩＳ Ｒ６２５２に規定された基材Ｃｗ、研磨材Ａ、粒度Ｐ２４０の研磨紙を用いて粗らした人工指として用い、アクリル基板上に膜厚０．５ｍｍでスピンコーティングされたオレイン酸を人工指紋液として用いることで、定量的な擬似指紋付着試験を行った。アクリル基板に対して人工指を２５０ｇ／ｃｍ2で垂直に押し付けることで人工指紋液を人工指に転写し、評価する基材に対して同様に２５０ｇ／ｃｍ2で垂直に押し付けることで、基材に擬似指紋を付着させた。後述する、拭き取り試験後の基材に再度擬似指紋を付着させる場合も、上記と同様に行った。 (1) Pseudo-fingerprint adhesion test The end surface of a 29 mm diameter silicone rubber plug is used as an artificial finger roughened with a base material Cw, abrasive material A, and abrasive paper of particle size P240 specified in JIS R6252, on an acrylic substrate. A quasi-fingerprint adhesion test was conducted by using oleic acid spin-coated with a thickness of 0.5 mm as an artificial fingerprint liquid. By artificially pressing an artificial finger against an acrylic substrate at 250 g / cm 2 , the artificial fingerprint liquid is transferred to the artificial finger, and similarly at 250 g / cm 2 against the substrate to be evaluated, the substrate is pressed vertically. A pseudo-fingerprint was attached to the surface. When pseudo fingerprints were again attached to the substrate after the wiping test, which will be described later, the same procedure as described above was performed.
（２）擬似指紋の拭き取り試験
直径３３ｍｍの金属円柱底面に一般用タオル１２０匁を二枚重ねで固定し、加重４０ｇ／ｃｍ2で擬似指紋付着部を１往復させることにより乾拭きを行った。 (2) Pseudo-fingerprint wiping test Two 120 towels of general towels were fixed to the bottom of a metal cylinder having a diameter of 33 mm, and dry wiping was performed by reciprocating the pseudo-fingerprint adhering portion with a load of 40 g / cm 2 .
直径３３ｍｍの金属円柱底面に一般用タオル１２０匁を二枚重ねで固定し、加重４０ｇ／ｃｍ2で擬似指紋付着部を１往復させることにより乾拭きを行った。 (2) Pseudo-fingerprint wiping test Two 120 towels of general towels were fixed to the bottom of a metal cylinder having a diameter of 33 mm, and dry wiping was performed by reciprocating the pseudo-fingerprint adhering portion with a load of 40 g / cm 2 .
（３）耐指紋汚染性の評価
擬似指紋付着後の基材、擬似指紋拭き取り後の基材、及び擬似指紋再付着後の基材に対して、耐指紋汚染性を下記の三種類の方法で評価した。
１．目視評価（付着後：○目立たない、△判定しにくい、×未加工の基材と同等；拭き取り後：○指紋跡が残らない、△指紋跡が残る、×指紋跡が拡がる；再付着後：○目立たない、△判定しにくい、×未加工の基材と同等）
２．ヘーズの変化量（擬似指紋付着前と擬似指紋付着後のヘーズ値を測定し、それぞれの値の差を求めた（以降、「初回付着ヘーズ変化」と記載する）。また、擬似指紋拭き取り後の基材と擬似指紋再付着後のヘーズ値を測定し、それぞれの値の差を求めた（以降、「再付着ヘーズ変化」と記載する）。）
３．光学顕微鏡観察（擬似指紋付着後、擬似指紋拭き取り後、及び擬似指紋再付着後の基材表面を観察した。） (3) Evaluation of anti-fingerprint contamination The anti-fingerprint anti-fouling property for the base material after pseudo-fingerprint adhesion, the base material after pseudo-fingerprint wiping, and the base material after pseudo-fingerprint reattachment are as follows. evaluated.
1. Visual evaluation (after adhesion: ○ not noticeable, △ difficult to judge, × equivalent to unprocessed substrate; after wiping: ○ no fingerprint trace left, Δ fingerprint trace left, × fingerprint trace spread; after reattachment: ○ Inconspicuous, △ difficult to judge, × equivalent to unprocessed substrate)
2. Amount of change in haze (measured haze values before and after pseudo-fingerprint attachment, and found the difference between the values (hereinafter referred to as “first-time adhesion haze change”). The haze value after the substrate and pseudo-fingerprint reattachment was measured, and the difference between the values was obtained (hereinafter referred to as “reattachment haze change”).
3. Observation with an optical microscope (the surface of the base material was observed after the pseudo fingerprint was attached, after the pseudo fingerprint was wiped off, and after the pseudo fingerprint was reattached)
擬似指紋付着後の基材、擬似指紋拭き取り後の基材、及び擬似指紋再付着後の基材に対して、耐指紋汚染性を下記の三種類の方法で評価した。
１．目視評価（付着後：○目立たない、△判定しにくい、×未加工の基材と同等；拭き取り後：○指紋跡が残らない、△指紋跡が残る、×指紋跡が拡がる；再付着後：○目立たない、△判定しにくい、×未加工の基材と同等）
２．ヘーズの変化量（擬似指紋付着前と擬似指紋付着後のヘーズ値を測定し、それぞれの値の差を求めた（以降、「初回付着ヘーズ変化」と記載する）。また、擬似指紋拭き取り後の基材と擬似指紋再付着後のヘーズ値を測定し、それぞれの値の差を求めた（以降、「再付着ヘーズ変化」と記載する）。）
３．光学顕微鏡観察（擬似指紋付着後、擬似指紋拭き取り後、及び擬似指紋再付着後の基材表面を観察した。） (3) Evaluation of anti-fingerprint contamination The anti-fingerprint anti-fouling property for the base material after pseudo-fingerprint adhesion, the base material after pseudo-fingerprint wiping, and the base material after pseudo-fingerprint reattachment are as follows. evaluated.
1. Visual evaluation (after adhesion: ○ not noticeable, △ difficult to judge, × equivalent to unprocessed substrate; after wiping: ○ no fingerprint trace left, Δ fingerprint trace left, × fingerprint trace spread; after reattachment: ○ Inconspicuous, △ difficult to judge, × equivalent to unprocessed substrate)
2. Amount of change in haze (measured haze values before and after pseudo-fingerprint attachment, and found the difference between the values (hereinafter referred to as “first-time adhesion haze change”). The haze value after the substrate and pseudo-fingerprint reattachment was measured, and the difference between the values was obtained (hereinafter referred to as “reattachment haze change”).
3. Observation with an optical microscope (the surface of the base material was observed after the pseudo fingerprint was attached, after the pseudo fingerprint was wiped off, and after the pseudo fingerprint was reattached)
実施例１の基材の評価結果を表２、３に示す。面積比が２０％で、寸法４４μｍ、深さ５μｍの穴を有するフロートガラスは、擬似指紋を付着させた後の指紋跡は目視では目立たず、また、拭き取り後の指紋跡は目視では確認できなかった。さらに、拭き取り部分に擬似指紋を再付着させた後の指紋跡は目視では目立たなかった。また、初回付着ヘーズ変化は４％であり、再付着ヘーズ変化は５％であった。
Tables 2 and 3 show the evaluation results of the base material of Example 1. Float glass with an area ratio of 20%, a hole with dimensions of 44 μm and depth of 5 μm, the fingerprint trace after attaching the pseudo fingerprint is not noticeable visually, and the fingerprint trace after wiping is not visually confirmed It was. Furthermore, the fingerprint trace after the pseudo fingerprint was reattached to the wiped portion was not visually noticeable. Further, the change in initial haze was 4%, and the change in reattachment haze was 5%.
さらに、擬似指紋を付着させた該基材表面を光学顕微鏡にて観察をしたところ、穴にほとんどの指紋成分がトラップされており、基準面に存在する指紋成分はわずかであることが確認できた。また、擬似指紋拭き取り後の基材表面を光学顕微鏡にて観察をしたところ、前記穴から指紋成分が除去されて該穴の中には液滴の細かい指紋成分がわずかに残っている程度であり、基準面に指紋成分がほぼ残っていないことが確認できた。
Furthermore, when the surface of the base material on which the pseudo fingerprint was adhered was observed with an optical microscope, most of the fingerprint components were trapped in the holes, and it was confirmed that the fingerprint components existing on the reference surface were small. . In addition, when the surface of the base material after wiping off the pseudo-fingerprint was observed with an optical microscope, the fingerprint component was removed from the hole, and only a small amount of fine fingerprint component remained in the hole. It was confirmed that almost no fingerprint component remained on the reference surface.
さらに、拭き取り部分に擬似指紋を再付着させた後の基材表面を光学顕微鏡にて観察をしたところ、穴にほとんどの指紋成分がトラップされており、基準面に存在する指紋成分はわずかであることが確認できた。このように、フロートガラスに上記のような穴を加工することで、優れた耐指紋汚染性が得られることがわかった。
Furthermore, when the surface of the substrate after the pseudo fingerprint was reattached to the wiped portion was observed with an optical microscope, most of the fingerprint component was trapped in the hole, and the fingerprint component existing on the reference surface was slight. I was able to confirm. Thus, it was found that excellent fingerprint contamination resistance can be obtained by processing the above-described holes in the float glass.
さらに、後述する比較例（比較例１）で、上記のような穴を加工せずフロートガラスに撥水撥油性を持たせただけの基材に比べて耐指紋汚染性が高く、上記の穴を有することが耐指紋汚染性向上に非常に有効であることがわかった。
Furthermore, in the comparative example (Comparative Example 1) to be described later, the above-mentioned hole is high in fingerprint contamination resistance as compared with a base material in which the above-described hole is not processed and the float glass is only given water and oil repellency. It has been found that having an anti-finger is very effective in improving the resistance to fingerprint contamination.
［実施例２～２３］
実施例１と同様の方法で表１に記載の穴を有する基材を得た後に、さらに表１に示すパーフルオロポリアルキレンエーテル変性シラン（Ｄｏｗ Ｃｏｒｎｉｎｇ２６３４：東レ・ダウコーニング社製、またはＫＹ－１３０：信越化学工業社製）１重量部とフッ素系不活性液体（ＦＣ－３２８３：住友３Ｍ社製）５００重量部を混合した薬液を、該基材にディップコートし、該基材を１５０℃で１０分間加熱することで、撥水撥油性が付与された基材を得た。 [Examples 2 to 23]
After obtaining a substrate having holes shown in Table 1 in the same manner as in Example 1, perfluoropolyalkylene ether-modified silane (Dow Corning 2634: manufactured by Toray Dow Corning, Inc., or KY-130) shown in Table 1 was further obtained. : Shin-Etsu Chemical Co., Ltd.) 1 part by weight and fluorinated inert liquid (FC-3283: Sumitomo 3M Co., Ltd.) 500 parts by weight is mixed with the dip coating on the substrate, and the substrate is heated at 150 ° C. By heating for 10 minutes, a base material imparted with water and oil repellency was obtained.
実施例１と同様の方法で表１に記載の穴を有する基材を得た後に、さらに表１に示すパーフルオロポリアルキレンエーテル変性シラン（Ｄｏｗ Ｃｏｒｎｉｎｇ２６３４：東レ・ダウコーニング社製、またはＫＹ－１３０：信越化学工業社製）１重量部とフッ素系不活性液体（ＦＣ－３２８３：住友３Ｍ社製）５００重量部を混合した薬液を、該基材にディップコートし、該基材を１５０℃で１０分間加熱することで、撥水撥油性が付与された基材を得た。 [Examples 2 to 23]
After obtaining a substrate having holes shown in Table 1 in the same manner as in Example 1, perfluoropolyalkylene ether-modified silane (Dow Corning 2634: manufactured by Toray Dow Corning, Inc., or KY-130) shown in Table 1 was further obtained. : Shin-Etsu Chemical Co., Ltd.) 1 part by weight and fluorinated inert liquid (FC-3283: Sumitomo 3M Co., Ltd.) 500 parts by weight is mixed with the dip coating on the substrate, and the substrate is heated at 150 ° C. By heating for 10 minutes, a base material imparted with water and oil repellency was obtained.
実施例２～２３の基材の、それぞれの評価結果を表２、３に示す。実施例のすべての基材で耐指紋汚染性が確認された。実施例２の光学顕微鏡観察を例にとると、図８に示すように、基材に付着させた擬似指紋はその大部分が基材表面に有する穴の中にトラップされており、基準面に存在する指紋成分はわずかであった。また、図９に示すように、１往復の拭き取り試験後は前記穴から指紋成分が除去されて該穴の中には液滴の細かい指紋成分がわずかに残っている程度であり、基準面に指紋成分がほぼ残っていないことが確認できた。さらに、図１０に示すように、前記拭き取り部分に再付着させた擬似指紋はその大部分が基材表面に有する穴の中にトラップされており、基準面に存在する指紋成分はわずかであった。
Tables 2 and 3 show the evaluation results of the substrates of Examples 2 to 23, respectively. Anti-fingerprint stain resistance was confirmed on all the substrates of the examples. Taking the optical microscope observation of Example 2 as an example, as shown in FIG. 8, most of the pseudo-fingerprint attached to the base material is trapped in a hole in the base material surface, Only a few fingerprint components were present. Also, as shown in FIG. 9, after one reciprocation wiping test, the fingerprint component is removed from the hole, and a small amount of fine fingerprint component remains in the hole. It was confirmed that almost no fingerprint component remained. Furthermore, as shown in FIG. 10, most of the pseudo-fingerprints reattached to the wiping portion are trapped in the holes in the surface of the substrate, and the fingerprint component existing on the reference surface is very small. .
また、実施例１１の光学顕微鏡観察を例にとると、図１１に示すように、基材に付着させた擬似指紋はその大部分が基材表面に有する穴の中にトラップされて、まとまった液滴となっており、基準面に存在する指紋成分はわずかであった。また、図１２に示すように、１往復の拭き取り試験後は前記穴から指紋成分がほぼ除去されており、基準面にも指紋成分がほぼ残っておらず、指紋成分の残留量が極めて少ないことが確認できた。さらに、図１３に示すように、前記拭き取り部分に再付着させた擬似指紋はその大部分が基材表面に有する穴の中にトラップされて、まとまった液滴となっており、基準面に存在する指紋成分はわずかであった。
Further, taking the optical microscope observation of Example 11 as an example, as shown in FIG. 11, most of the pseudo-fingerprints attached to the base material are trapped in holes formed on the base material surface, and are collected. It was a droplet and the fingerprint component present on the reference surface was very small. Also, as shown in FIG. 12, the fingerprint component is almost removed from the hole after one reciprocal wiping test, the fingerprint component is hardly left on the reference surface, and the residual amount of the fingerprint component is extremely small. Was confirmed. Furthermore, as shown in FIG. 13, the pseudo-fingerprint reattached to the wiping portion is trapped in the hole on the substrate surface, and is formed into a droplet, which is present on the reference surface. The fingerprint component to be performed was slight.
なお、実施例１３および実施例１６では、拭き取りの際の作業性は、ひっかかり易くやや滑り難い傾向があった。それ以外のすべての実施例では、拭き取りの際の作業性は、滑り易く良好であった。
In Example 13 and Example 16, the workability at the time of wiping tended to be easily caught and slightly slippery. In all other examples, the workability during wiping was slippery and good.
［比較例］
汎用のフロートガラス１種、実施例と同様にフロートガラスに微細構造を加工したガラス基板２種について、実施例と同様に撥水撥油性を付与することで基材を得た。作製条件の詳細を表１に比較例１～７として示す。 [Comparative example]
A base material was obtained by imparting water and oil repellency to the glass substrate of one type of general-purpose float glass and two types of glass substrates obtained by processing the fine structure of the float glass in the same manner as in the examples. Details of the manufacturing conditions are shown in Table 1 as Comparative Examples 1 to 7.
汎用のフロートガラス１種、実施例と同様にフロートガラスに微細構造を加工したガラス基板２種について、実施例と同様に撥水撥油性を付与することで基材を得た。作製条件の詳細を表１に比較例１～７として示す。 [Comparative example]
A base material was obtained by imparting water and oil repellency to the glass substrate of one type of general-purpose float glass and two types of glass substrates obtained by processing the fine structure of the float glass in the same manner as in the examples. Details of the manufacturing conditions are shown in Table 1 as Comparative Examples 1 to 7.
それぞれの評価結果を表２、３に示す。比較例１のように、フロートガラスに撥水撥油性を持たせるような表面処理をしただけの基材では、擬似指紋を付着させたときの指紋跡は、表面処理をしていない未加工のフロートガラスの場合の指紋跡と差がなく、また、拭き取り後の指紋跡は基材表面に拡がってしまい、しっかりと拭き取れていないことが確認できた。
Each evaluation result is shown in Tables 2 and 3. As in Comparative Example 1, with a base material that has only been subjected to a surface treatment for imparting water and oil repellency to the float glass, the fingerprint trace when the pseudo fingerprint is attached is not processed surface treatment. It was confirmed that there was no difference from the fingerprint trace in the case of the float glass, and the fingerprint trace after wiping spread on the surface of the base material and was not wiped off firmly.
また、穴の寸法が小さすぎると、耐指紋汚染性は充分に得られず（比較例２）、穴の寸法が大きすぎても充分な耐指紋汚染性が得られなかった（比較例３）。また、穴の深さが小さすぎる場合も、耐指紋汚染性は充分に得られず（比較例４）、穴の深さが大きすぎる場合も、耐指紋汚染性は充分に得らなかった（比較例５）。また、穴の面積比が低すぎる場合も、耐指紋汚染性は充分に得られず（比較例６）、穴の面積比が高すぎる場合も、耐指紋汚染性は充分に得らなかった（比較例７）。
In addition, when the size of the hole is too small, sufficient anti-fingerprint resistance cannot be obtained (Comparative Example 2), and when the size of the hole is too large, sufficient anti-fingerprint resistance cannot be obtained (Comparative Example 3). . Also, when the depth of the hole is too small, sufficient anti-fingerprint resistance cannot be obtained (Comparative Example 4), and when the depth of the hole is too large, sufficient anti-fingerprint resistance cannot be obtained ( Comparative Example 5). In addition, when the hole area ratio is too low, sufficient anti-fingerprint resistance is not obtained (Comparative Example 6), and when the hole area ratio is too high, the anti-fingerprint resistance is not sufficiently obtained ( Comparative Example 7).
図１４、１５に示すように、撥水撥油性を付与しただけのフロートガラスに付着させた擬似指紋は基材上で液滴となり、１往復の拭き取り試験後は液滴サイズが小さくなって大量に残る様子が観察された。
As shown in FIGS. 14 and 15, the pseudo fingerprint attached to the float glass that has only been given water and oil repellency becomes droplets on the substrate, and the droplet size becomes small after one round of wiping test. It was observed that it remained in
本発明の耐指紋汚染性基材は、指等が触れやすく指紋成分が付着しやすい環境下で優れた耐指紋汚染性を示す。具体的には、建築用の窓ガラスやショーケース（店の商品用、人形用など）、間仕切り用基材・樹脂資材、装飾用化粧板、金属板、家具、電気、電子機器（テレビ、携帯電話、ＰＣ、ＡＴＭ、フォトプレートなど）用ディスプレイパネルやタッチパネル、保護フィルム、電気、電子機器筐体の金属部や樹脂コーティング、鏡、飲料用瓶、飲料用グラス等に用いることで優れた耐指紋汚染性を付与できる。
The fingerprint stain-resistant substrate of the present invention exhibits excellent fingerprint stain resistance in an environment where a finger or the like is easily touched and a fingerprint component is easily attached. Specifically, architectural window glass and showcases (for store products, dolls, etc.), partition base materials and resin materials, decorative decorative plates, metal plates, furniture, electricity, electronic equipment (TVs, mobile phones) Excellent fingerprint resistance when used for display panels, touch panels, protective films, electrical and electronic equipment metal parts, resin coatings, mirrors, beverage bottles, beverage glasses, etc. for telephones, PCs, ATMs, photo plates, etc. Contamination can be imparted.
１ 穴を有する基材
２ 基材の基準面
３ 凹型の穴
４ 穴を有する層を持つ基材
５ 穴を有する層
６ 穴の一部又は全体にトラップされた指紋成分 DESCRIPTION OFSYMBOLS 1 Base material 2 which has a hole Reference surface 3 of a base material 4 Recessed hole 4 Base material which has a layer which has a hole 5 Layer which has a hole 6 Fingerprint component trapped in a part or the whole of a hole
２ 基材の基準面
３ 凹型の穴
４ 穴を有する層を持つ基材
５ 穴を有する層
６ 穴の一部又は全体にトラップされた指紋成分 DESCRIPTION OF
Claims (6)
- 光透過性、光反射性、または光沢性を有する基材の平滑な面の指が接触する箇所に、該平滑な面に付着した指紋成分を毛細管力で集める凹型の穴を有し、該穴の正面視での投影面積の二乗根の寸法が１０～３００μｍであり、該穴の平均深さが０．２～５０μｍであり、該平滑な面の観察領域の面積に対する、観察領域内に存在する該穴の合計面積の面積比が１０～８５％であることを特徴とする、耐指紋汚染性基材。 A concave hole that collects the fingerprint component adhering to the smooth surface by capillary force at a location where the finger of the smooth surface of the base material having light transmissivity, light reflectivity, or glossiness comes into contact with the hole. The square root size of the projected area in front view is 10 to 300 μm, the average depth of the hole is 0.2 to 50 μm, and exists in the observation area with respect to the area of the observation area of the smooth surface A fingerprint-fouling-resistant substrate, wherein the area ratio of the total area of the holes is 10 to 85%.
- 前記穴の正面視での形状が、１～６個の角を有することを特徴とする、請求項１に記載の耐指紋汚染性基材。 2. The fingerprint contamination-resistant substrate according to claim 1, wherein the shape of the hole in a front view has 1 to 6 corners.
- 耐指紋汚染性部分における前記穴の面積比が１３～６０％であることを特徴とする、請求項１または請求項２に記載の耐指紋汚染性基材。 The fingerprint resistant substrate according to claim 1 or 2, wherein an area ratio of the holes in the fingerprint resistant portion is 13 to 60%.
- 前記穴は、該穴の形状に対応したマスキング処理を施した後、表面研削またはエッチングを施すことにより前記基材の平滑な面に形成されたものであることを特徴とする、請求項１乃至請求項３のいずれか１項に記載の耐指紋汚染性基材。 The said hole is formed in the smooth surface of the said base material by performing the surface grinding or the etching after giving the masking process corresponding to the shape of this hole, The 1 thru | or characterized by the above-mentioned. The fingerprint-fouling-resistant substrate according to claim 3.
- 前記基材の平滑な面がフロートガラスのトップ面またはボトム面であることを特徴とする、請求項１乃至請求項４のいずれか１項に記載の耐指紋汚染性基材。 The fingerprint-fouling-resistant substrate according to any one of claims 1 to 4, wherein the smooth surface of the substrate is a top surface or a bottom surface of float glass.
- 前記基材表面に撥水撥油性膜を有することを特徴とする、請求項１乃至請求項５のいずれか１項に記載の耐指紋汚染性基材。 The fingerprint-fouling-resistant substrate according to any one of claims 1 to 5, further comprising a water- and oil-repellent film on the surface of the substrate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-121969 | 2011-05-31 | ||
| JP2011121969 | 2011-05-31 | ||
| JP2012-094140 | 2012-04-17 | ||
| JP2012094140A JP2013010684A (en) | 2011-05-31 | 2012-04-17 | Fingerprint stain-resistant substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012165107A1 true WO2012165107A1 (en) | 2012-12-06 |
Family
ID=47258971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/061705 WO2012165107A1 (en) | 2011-05-31 | 2012-05-08 | Fingerprint stain-resistant substrate |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2013010684A (en) |
| TW (1) | TW201302650A (en) |
| WO (1) | WO2012165107A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3675610A4 (en) * | 2017-10-13 | 2020-11-11 | Huawei Technologies Co., Ltd. | High strength fingerprint-proof glass and preparation method therefor, and exterior member of high strength fingerprint-proof glass and preparation method therefor |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6003731B2 (en) * | 2013-03-15 | 2016-10-05 | 旭硝子株式会社 | Water and oil repellent articles |
| CN105189386A (en) * | 2013-03-20 | 2015-12-23 | 旭硝子欧洲玻璃公司 | Glass sheet having high infrared radiation transmission |
| CN105189387A (en) * | 2013-03-20 | 2015-12-23 | 旭硝子欧洲玻璃公司 | Glass sheet having high infrared radiation transmission |
| EP2994433B1 (en) * | 2013-05-07 | 2021-12-08 | AGC Glass Europe | Sheet of glass with high infrared radiation transmission |
| WO2019227010A1 (en) * | 2018-05-24 | 2019-11-28 | Nbd Nanotechnologies, Inc. | Invisible fingerprint coatings and process for forming same |
| JP7274690B2 (en) * | 2018-09-25 | 2023-05-17 | 国立大学法人 熊本大学 | Concave-convex body manufacturing method and concavo-convex body |
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| JPH04275925A (en) * | 1990-12-21 | 1992-10-01 | Saint Gobain Vitrage Internatl | Diffusible glass and method and device for manufacture thereof |
| JP2004359504A (en) * | 2003-06-05 | 2004-12-24 | Central Glass Co Ltd | Chemically tempered glass and its manufacturing method |
| JP2008225169A (en) * | 2007-03-14 | 2008-09-25 | Saitama Univ | Method for forming geometrical pattern |
| WO2010017503A1 (en) * | 2008-08-07 | 2010-02-11 | Uni-Pixel Displays, Inc. | Microstructures to reduce the apperance of fingerprints on surfaces |
| JP2010202497A (en) * | 2009-02-04 | 2010-09-16 | Fujifilm Corp | Heat-ray reflective film, heat-ray reflective structure, and production method thereof |
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2012
- 2012-04-17 JP JP2012094140A patent/JP2013010684A/en active Pending
- 2012-05-08 WO PCT/JP2012/061705 patent/WO2012165107A1/en active Application Filing
- 2012-05-30 TW TW101119406A patent/TW201302650A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04275925A (en) * | 1990-12-21 | 1992-10-01 | Saint Gobain Vitrage Internatl | Diffusible glass and method and device for manufacture thereof |
| JP2004359504A (en) * | 2003-06-05 | 2004-12-24 | Central Glass Co Ltd | Chemically tempered glass and its manufacturing method |
| JP2008225169A (en) * | 2007-03-14 | 2008-09-25 | Saitama Univ | Method for forming geometrical pattern |
| WO2010017503A1 (en) * | 2008-08-07 | 2010-02-11 | Uni-Pixel Displays, Inc. | Microstructures to reduce the apperance of fingerprints on surfaces |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3675610A4 (en) * | 2017-10-13 | 2020-11-11 | Huawei Technologies Co., Ltd. | High strength fingerprint-proof glass and preparation method therefor, and exterior member of high strength fingerprint-proof glass and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013010684A (en) | 2013-01-17 |
| TW201302650A (en) | 2013-01-16 |
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