WO2015125498A1 - Optical member having antifouling film, and touchscreen - Google Patents

Optical member having antifouling film, and touchscreen Download PDF

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Publication number
WO2015125498A1
WO2015125498A1 PCT/JP2015/000925 JP2015000925W WO2015125498A1 WO 2015125498 A1 WO2015125498 A1 WO 2015125498A1 JP 2015000925 W JP2015000925 W JP 2015000925W WO 2015125498 A1 WO2015125498 A1 WO 2015125498A1
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WO
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Prior art keywords
film
antifouling
optical member
antifouling film
base
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PCT/JP2015/000925
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French (fr)
Japanese (ja)
Inventor
齋藤　崇
健志 小林
須藤　健二
哲也 村田
幸弘 堀江
Original Assignee
キヤノンオプトロン株式会社
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Priority to JP2016503987A priority Critical patent/JP6474383B2/en
Publication of WO2015125498A1 publication Critical patent/WO2015125498A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes

Definitions

  • the present invention relates to an optical member with an antifouling film and a touch panel display, and is particularly suitable for an optical member with an antifouling film formed by laminating an antifouling film on the surface of a base film formed on a substrate. .
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-58728
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-58728
  • the antireflection member described in Patent Document 1 is an antireflection member comprising a base material, a hard coat layer, and an antireflection layer, and the surface roughness Ra of the hard coat layer is represented by the following formulas (1) and (2): The condition indicated by is satisfied.
  • Ra1 1.4 nm to 13 nm (area 5 ⁇ m ⁇ 5 ⁇ m)
  • Ra2 2.2 nm to 26 nm (area 20 ⁇ m ⁇ 20 ⁇ m)
  • Ra (arithmetic mean roughness) is an index representing the surface roughness of the sample, and is a value defined in JIS-B0601: 2001.
  • AFM atomic force microscope
  • Patent Document 1 by satisfying the above formulas (1) and (2), even when the thickness of the layer (antireflection layer or part thereof) in contact with the hard coat layer is thin, the continuity of the layer is given. It is described that the adhesion can be improved without hindering. Further, Patent Document 1 describes that an antireflection member having a moderately rough surface of the hard coat layer has very high scratch resistance.
  • Patent Document 1 the antifouling property is evaluated by a contact angle measurement experiment, the adhesion property is evaluated by a cross-cut method, and the scratch resistance is rubbed with steel wool 20 times. Evaluation is made by visual judgment of the presence or absence of scratches. According to the evaluation described in Patent Document 1, the value of the surface roughness Ra of the base film (hard coat layer) on which the antireflection layer including the antifouling layer is formed is expressed by the above formula (1) and It is described that an antireflection member excellent in adhesion and scratch resistance can be obtained by satisfying the range of (2).
  • the oil-repellent substrate described in Patent Document 2 is a touch surface of touch panel type electronic devices such as bank ATMs and ticket vending machines, in addition to various displays, showcases, clocks and instrument cover glasses. It is described that it is applicable.
  • Patent Document 2 parameters Ra (center line average roughness), Rz (ten-point average height), and Pv (maximum valley depth) related to the surface roughness of the first film on which the film having oil repellency is formed.
  • the first film is irradiated with energetic particles so as to be in an appropriate range.
  • Patent Document 2 by setting these parameters to an appropriate range, an appropriate recess is formed on the surface of the first film, and the wear resistance of the oil-repellent film formed thereafter is practically endured. It is described that the level can be improved to the level obtained.
  • Patent Document 2 discloses that Ra of the first film is preferably 0.1 to 1000 nm, more preferably 1 to 100 nm, and further preferably 3 to 20 nm. Further, an example in which Ra of the first film is 1 to 13 nm is specifically disclosed as an oil-repellent substrate excellent in wear resistance.
  • the oil-repellent substrate described in Patent Document 2 has a maximum scratch count of only about 200 when the surface roughness Ra of the base film (first film) is 1 nm. In contrast, when the Ra value was 2 nm and 3 nm, the maximum number of scratches was 2200, and when the Ra value was 5 nm, the maximum number of scratches was 2800.
  • JP 2006-58728 A Japanese Patent No. 5036827
  • Patent Documents 1 and 2 are still sufficient for long-term durability.
  • applications such as touch panel displays such as smartphones are frequently exposed to shock and friction, and therefore, the demand from the market for durability of antifouling performance has become very high. Therefore, higher durability is required, for example, capable of withstanding a more severe steel wool friction test.
  • the present invention has been made to solve the above-described problems, and provides an antifouling film-coated optical member and a touch panel display that have improved wear resistance and exhibit excellent antifouling properties over a long period of time. For the purpose.
  • an optical member with an antifouling film is provided with an antifouling film in which a base film is formed on a substrate and the antifouling film is formed on the surface of the base film. It is an optical member, Comprising: Surface roughness Ra of the said base film is 0.25 nm or more and 0.76 nm or less.
  • the touchscreen type display in one Embodiment of this invention is provided with the optical member with an antifouling film in one embodiment of the above-mentioned this invention.
  • an antifouling film-coated optical member and a touch panel display that have improved wear resistance and exhibit excellent antifouling properties over a long period of time.
  • FIG. 5 is a schematic diagram illustrating a configuration of an optical member with an antifouling film according to a second embodiment of the present invention, and is a diagram illustrating a configuration example of an optical member with an antifouling film in which a base film is directly formed on a substrate. It is. It is the schematic which shows the structure in one Embodiment of the touchscreen type display which concerns on this invention.
  • An optical member with an antifouling film according to the present invention is an optical member with an antifouling film in which a base film is formed on a base material and an antifouling film is formed on the surface of the base film, and the surface roughness of the base film is The thickness Ra is not less than 0.25 nm and not more than 0.76 nm.
  • the surface roughness Ra of the base film is in the range of 0.25 to 0.76 nm, and the base film is smoothed by sufficiently reducing the unevenness, so that silanol groups on the surface of the base film are substantially eliminated. It can arrange
  • the silane coupling reaction means that the alkoxysilane component molecule of the antifouling film is hydrolyzed to form a hydrogen bond with the silanol group on the surface of the undercoat film, and a strong covalent bond to the undercoat film by dehydration condensation, that is, siloxane. It forms a bond and exhibits strong adhesion. Since the distance at which individual molecules of the antifouling film components can chemically bond with the silanol groups of the undercoat is limited, it is more likely that the silanol groups on the surface of the undercoat are located closer to the same plane. It becomes easy to combine with the reactive group.
  • the surface of the undercoat film can be smoothed and the silanol groups on the undercoat film can be arranged at positions close to substantially the same plane. Therefore, it is presumed that a siloxane bond can easily occur as described above. Thereby, stronger adhesiveness is obtained between the base film and the antifouling film, and the wear resistance of the optical member with the antifouling film can be greatly improved.
  • FIG. 1 is a schematic diagram showing the configuration of a first embodiment of an optical member with an antifouling film according to the present invention, wherein the antifouling film has a base film formed on the base material via another film.
  • the antifouling film-coated optical member of the present embodiment has a low refractive index material film 14a, 14c made of a low refractive index material and a high refractive index material made of a high refractive index material on a substrate 11.
  • a laminated film 14 in which the films 14b and 14d are alternately laminated is formed.
  • the antifouling film 13 is formed on the surface of the base film 12 which is a film made of a low refractive index material provided on the laminated film 14.
  • the laminated film 14 and the base film 12 exhibit an antireflection function (the laminated film 14 and the base film 12 constitute an antireflection film).
  • FIG. 1 schematically shows the film configuration of the optical member with an antifouling film, and the actual thicknesses of the base material 11, the laminated film 14, the base film 12, and the antifouling film 13 are expressed in an accurate ratio. It was n’t.
  • the substrate 11 only needs to be capable of laminating and forming the base film 12 and the antifouling film 13 and the like, for example, glass or plastic.
  • the substrate is preferably capable of transmitting visible light or light having a specific wavelength.
  • the films 14a and 14c laminated odd-numbered from the substrate 11 side are made of a low refractive index material, and the films 14b and 14d laminated even-numbered are highly refracted. Made of rate material.
  • the base film 12 is also made of a low refractive index material, like the low refractive index material films 14 a and 14 c, and is laminated on the laminated film 14 and exhibits an antireflection function together with the laminated film 14.
  • the base film 12 for forming the antifouling film 13 is a low refractive index material.
  • Examples of the low refractive index material include SiO 2 (silicon dioxide) and Al 2 O 3 added SiO 2 (alumina added silicon dioxide). However, the present invention is not limited to this.
  • Examples of the high refractive index material include alumina-containing titanium oxide-lanthanum oxide-based mixed materials, other mixed oxides mainly composed of titanium oxide, niobium oxide, mixed materials mainly composed of niobium oxide, and the like. However, the present invention is not limited to this.
  • the film thickness of the laminated film 14 and each film constituting the laminated film 14 there are no particular restrictions on the film thickness of the laminated film 14 and each film constituting the laminated film 14, but for example, the film thickness of each film constituting the laminated film 14 is 10 to 200 nm, and a necessary number of layers are laminated.
  • the membrane 14 can be configured.
  • the laminated film 14 in this embodiment has a four-layer structure (a five-layer antireflection film structure including the antifouling film 13 that exhibits an antireflection function), but the present invention is not limited to this. Instead, the number of layers may be any number.
  • the laminated film 14 is provided as a part of the antireflection film formed by alternately laminating the low refractive index layer and the high refractive index layer as described above. It is not limited at all. For example, at least one film having a function selected from other filters, mirrors, antistatics and the like may be formed between the base material 11 and the base film 12.
  • the undercoat film 12 is a layer serving as an undercoat for forming the antifouling film 13, and an adhesion between the antifouling film 13 and a layer provided in the lower layer of the undercoat film 12 (in this embodiment, the laminated film 14). It makes the quality good.
  • the base film 12 in order to further improve the wear resistance of the antifouling film 13 formed on the surface of the base film 12, the base film 12 is formed so that its surface roughness Ra is 0.76 nm or less, An antifouling film 13 is formed on the surface of the base film 12 by vapor deposition (for example, vacuum vapor deposition).
  • the present invention is not limited to the vapor deposition process, and the antifouling film 13 may be formed by a production method other than the vapor deposition process, such as a dipping method, a coating method, a spray method, or a spin coating method.
  • a production method other than the vapor deposition process such as a dipping method, a coating method, a spray method, or a spin coating method.
  • the film formation rate of the base film 12 is 0.5 to several liters / sec, that is, the film formation rate is slower than usual, the thickness of the base film 12 is adjusted, Adjustment of temperature, smoothing of the surface roughness of the substrate 11, and the like are necessary to achieve a surface roughness Ra of 0.76 nm or less.
  • ion assist that irradiates ions while forming the base film 12 may be performed. At this time, it is desirable to adjust the ion assist conditions because the surface roughness Ra can also be affected. By adjusting such various conditions, the base film 12 having a surface roughness Ra of 0.76 nm or less is obtained.
  • the film thickness of the base film 12 is not particularly limited, but is, for example, 2 nm to 150 nm, preferably 5 to 125 nm. As the film thickness of the base film 12 increases, the surface roughness Ra tends to increase.
  • the material for forming the base film 12 is preferably SiO 2, but may be any substance having a hydroxyl group on the surface.
  • a metal oxide thin film such as an ITO film having a hydroxyl group on the surface may be used.
  • SiO 2 is formed to a thickness of about 2 to 3 nm on a metal oxide film such as an ITO film.
  • the surface roughness Ra of the base film 12 is 0.25 nm or more.
  • the unevenness is further reduced, and a smoother undercoat film can be obtained, while the productivity is deteriorated.
  • noise is generated during measurement, causing variations, and there is a problem that a measurement result with good accuracy cannot be obtained.
  • the antifouling film 13 is formed for the purpose of preventing fingerprint adhesion on the surface of the laminated film 14 or the base film 12, improving slipperiness, improving dirt wiping property, and preventing water stains. Further, the antifouling film 13 is made of, for example, a molecule having alkoxysilane, and is preferably made of a fluorine-based compound having alkoxysilane. As the fluorine-based compound, for example, a perfluoroalkyl ether compound represented by the following formula is used.
  • Rf is a perfluoroalkyl ether group
  • X is an organic group containing a hydrolyzable group-containing silane having a plurality of hydrolyzable groups
  • Y is an organic group linking the Rf group and the X group.
  • X is an organic group containing a hydrolyzable group-containing silyl group having a plurality of hydrolyzable groups, preferably 2 to 18, more preferably 2 to 9.
  • the hydrolyzable group include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, an alkoxyalkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group, and an acetoxy group.
  • Examples thereof include an acyloxy group having 1 to 10 carbon atoms such as alkenyloxy group having 2 to 10 carbon atoms such as isopropenoxy group, a halogen group such as chloro group, bromo group and iodo group, and an amino group.
  • a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable.
  • Y is a divalent organic group, which is a linking group of Rf group and X group.
  • an unsubstituted or substituted carbon that may contain one or more structures selected from the group consisting of amide bonds, ether bonds, ester bonds, vinyl bonds, and diorganosylylene groups such as dimethylsilylene groups.
  • examples of the fluorine-based compound include trimethoxysilane, dimethoxysilane, triethoxysilane, triisopropenoxysilane, trichlorosilane, and triaminosilane having a perfluoroalkyl ether group.
  • trimethoxysilane having a perfluoroalkyl ether group is preferable.
  • the film thickness of the antifouling film 13 is not particularly limited, but is, for example, 10 to 20 nm. If the film thickness is too thin, sufficient antifouling properties may not be obtained, and if the film thickness is too thick, transparency may be impaired.
  • FIG. 2 is a schematic diagram showing the configuration of the optical member with an antifouling film according to the second embodiment of the present invention, and the configuration of the optical member with an antifouling film in which a base film is directly formed on a substrate. It is a figure which shows an example.
  • the optical member with an antifouling film shown in FIG. 2 has a configuration in which a base film 12 is directly formed on a substrate 11.
  • the base film 12 is formed as a single layer using a low refractive index material, and the antifouling film 13 is formed on the surface of the base film 12.
  • the low refractive index material of the base film 12 is assumed to be SiO 2 .
  • the optical member with the antifouling film of the present embodiment is different from the first embodiment in the layer configuration, but the other configurations are the same as those in the first embodiment. Therefore, the optical member with the antifouling film in the present embodiment can be the one described in the first embodiment for the configuration other than the layer configuration.
  • the antifouling film-coated optical member of the present embodiment has a configuration in which the laminated film 14 is removed from the first embodiment.
  • FIG. 2 also schematically shows the film configuration of the optical member with the antifouling film, and shows the actual thicknesses of the base material 11, the base film 12 and the antifouling film 13 in an accurate ratio. Absent.
  • FIG. 3 is a schematic diagram showing the configuration of an embodiment of the touch panel display according to the present invention.
  • it is a touch panel type display used for a smart phone, and the antifouling film-attached optical member according to the present invention described above is provided as the antifouling film-attached glass used for the display cover glass 31.
  • the display cover glass 31 is provided on a display unit 32 provided with a transparent electrode, and a main substrate 33 is provided on the opposite side of the display unit 32 from the display cover glass 31.
  • touch panel display is not limited to those used for smartphones, but, for example, other mobile phones, digital cameras, digital video cameras, portable audio players, game devices, car navigation systems, car audio systems, personal computers, tablets It can be used for terminals, liquid crystal displays, organic EL displays, plasma displays, various other display devices, copying machines, bank ATMs, ticket vending machines, and the like.
  • Example 1 Low refractive index material films 14a and 14c made of SiO 2 and high refractive index material films 14b and 14d made of an alumina-containing titanium oxide-lanthanum oxide mixed material are formed on a glass substrate 0.8 mm in thickness. Were alternately formed to form a laminated film 14 having a four-layer structure. Each layer constituting the laminated film 14 is formed by vapor deposition, and the film thickness is 15 nm for the low refractive index material film 14a, 16.5 nm for the high refractive index material film 14b, 35 nm for the low refractive index material film 14c, and a high refractive index material film. 14d was 136.5 nm. The low refractive index material film 14a is provided in contact with the base material 11 made of glass.
  • the base film 12 made of SiO 2 was formed on the laminated film 14 (high refractive index material film 14d located at the uppermost part) by vapor deposition.
  • the film formation rate of the base film 12 is 1 ⁇ / S (the film formation rate of the low refractive index film of the laminated film 14 is 7 ⁇ / S), and the temperature during film formation is about 150. C. It should be noted that only the base film 12 that needs to have the desired surface roughness Ra was slowed down and the film deposition speed of each film of the laminated film 14 was increased. This can increase productivity.
  • the film thickness of the base film 12 was 91 nm.
  • an antifouling film 13 made of a fluorine compound was formed on the base film 12 to produce an optical member with an antifouling film.
  • a fluorine-based compound SURFCLEAR100 (manufactured by Canon Optron Co., Ltd.) containing perfluoroalkyl ether-containing trimethoxysilane was used to form an antifouling film 13 having a thickness of 12 to 14 nm.
  • the structure of the obtained optical member with an antifouling film is the same as that of the optical member with an antifouling film shown in FIG.
  • Example 2 comparative example
  • An optical member with an antifouling film was produced in the same manner as in Example 1 except that the deposition rate of the base film 12 was changed.
  • Example 5 An optical member with an antifouling film was produced in the same manner as in Example 1 except that the laminated film 14 was not formed and the film formation rate of the base film 12 was changed. Moreover, the structure of the obtained optical member with an antifouling film is the same as that of the optical member with an antifouling film shown in FIG.
  • the abrasion resistance was evaluated by measuring the contact angle with water after friction with steel wool. Specifically, every time the steel wool was rubbed 1000 times, a droplet was made on the surface of the antifouling film 13 after the friction, and the contact angle with water was measured.
  • the water contact angle is an angle formed by a tangent to the water surface and a solid surface at a point where the solid and water contact. Here, the larger the value of the water contact angle, the smaller the surface of the antifouling film 13 is.
  • the water contact angle is measured when the water contact angle is measured at nine locations (measurement locations No. 1 to 9) on the surface of the antifouling film 13, and the water contact angle is 100 ° or more at all nine points. The case where even one point out of the nine points has a contact angle with water of less than 100 ° was regarded as unacceptable. In the measurement of the contact angle with water when the number of frictions was 0, only 5 points were measured because no scratches were caused by friction at any location.
  • Example 1 the value of the surface roughness Ra of the base film 12 is 0.31. As is apparent from Table 1 above, the number of scratches at the first failure was 14,000, and the pass condition was satisfied at least when the number of scratches was 13,000. Therefore, it can be seen that the maximum number of scratches that satisfy the pass condition regarding wear resistance is any value between 13,000 times and less than 14000 times. In Example 2, the value of the surface roughness Ra of the base film 12 is 0.75. The maximum number of scratches that satisfy the pass condition for wear resistance in Example 2 is any value between 8000 and less than 9000. On the other hand, in the comparative example, the value of the surface roughness Ra of the base film 12 is 1.25 (the value in the range shown in Patent Document 2). It can be seen that the maximum number of scratches that satisfy the pass condition regarding the wear resistance in the comparative example is less than 1000, which is inferior in wear resistance and does not provide excellent antifouling properties over a long period of time.
  • Example 3 the value of the surface roughness Ra of the base film 12 is 0.36.
  • the maximum number of scratches that satisfy the pass condition regarding wear resistance in Example 3 is any value between 9000 and less than 10,000.
  • Example 4 the value of the surface roughness Ra of the base film 12 is 0.25.
  • the maximum number of scratches that satisfy the pass condition regarding wear resistance in Example 4 is any value between 9000 and less than 10,000.
  • Example 5 the value of the surface roughness Ra of the base film 12 is 0.76.
  • the maximum number of scratches that satisfy the pass condition regarding wear resistance in Example 5 is any value between 6000 times and less than 7000 times.
  • Example 6 A tempered glass (Gorilla glass manufactured by Corning Co., Ltd.) cut to 4 inches having a thickness of 0.7 mm was used as a substrate, and the edge of this tempered glass was coated to produce a cover glass 31 for display. Furthermore, the display cover glass 31 was bonded to the display unit 32 including a transparent electrode.
  • tempered glass Gorilla glass manufactured by Corning Co., Ltd.
  • the display cover glass 31 was washed, it was set in a vacuum vapor deposition machine so that vapor deposition was possible on the surface of the display unit 32 opposite to the side to which it was attached. Subsequently, after vacuuming to a pressure of 1.0 ⁇ 10 ⁇ 3 [Pa], seven layers of Nb 2 O 5 (niobium pentoxide) and SiO 2 (silicon dioxide) were alternately formed. Further, a SiO 2 layer (underlayer) was deposited on the seventh Nb 2 O 5 layer at a deposition rate of 1 [ ⁇ / sec], which was slower than the sixth layer. .
  • the laminated film (a total of 8 layers including the base film) laminated on the display cover glass 31 had a film thickness of 306 nm. Then, an antifouling film was formed on this SiO 2 film using SURFCLEAR100 containing perfluoroalkyl ether-containing trimethoxysilane to a thickness of 12 to 16 nm.
  • the coated display cover glass 31 provided with the display unit 32 was combined with the main substrate 33 to produce a touch panel display.
  • This touch panel display had excellent antifouling performance and was able to maintain high durability.
  • the unevenness of the base film 12 is smoothed, the wear resistance of the antifouling film 13 can be greatly improved, and excellent antifouling properties are exhibited over a long period of time. I knew it was possible.

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Abstract

The purpose of this invention is to provide an optical member and a touchscreen, said optical member having an antifouling film, that exhibit improved resistance to wear and excellent long-term antifouling performance. A base film (12) is formed on top of a substrate (11), and an antifouling film (13) is formed on the surface of said base film (12). The surface roughness (Ra) of the base film (12) is between 0.25 and 0.76 nm, inclusive.

Description

防汚膜付光学部材およびタッチパネル式ディスプレイAnti-fouling optical member and touch panel display
　本発明は防汚膜付光学部材およびタッチパネル式ディスプレイに関し、特に、基材上に形成した下地膜の表面に防汚膜を積層してなる防汚膜付光学部材に好適に用いられるものである。 The present invention relates to an optical member with an antifouling film and a touch panel display, and is particularly suitable for an optical member with an antifouling film formed by laminating an antifouling film on the surface of a base film formed on a substrate. .
　ガラスやプラスチックの基材に付着した指紋などの汚れを拭き取りやすくするために、基材に撥油膜のコーティングを施して、防汚性能を持たせる技術が知られている。
　例えば特許文献１（特開２００６－５８７２８号公報）に記載の反射防止部材は、最上層に防汚性を有する層を備え、ディスプレイの表示画面の表面に適用可能であると記載されている。 In order to make it easy to wipe off dirt such as fingerprints adhering to a glass or plastic base material, a technique for providing an antifouling performance by applying an oil-repellent film to the base material is known.
For example, the antireflection member described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-58728) is described as being provided with a layer having antifouling property as the uppermost layer and applicable to the surface of a display screen of a display.
　ここで特許文献１に記載の反射防止部材は、基材、ハードコート層および反射防止層からなる反射防止部材において、ハードコート層の表面粗さＲａが以下の式（１）および式（２）で示される条件を満たす。
　　Ｒａ１＝１．４ｎｍ～１３ｎｍ（エリア５μｍ×５μｍ）　　・・・（１）
　　Ｒａ２＝２．２ｎｍ～２６ｎｍ（エリア２０μｍ×２０μｍ）・・・（２）
　なお、Ｒａ（算術平均粗さ)とは、試料の表面粗さを表わす指標であり、JIS-B0601：2001に定義された値である。ナノスケールの微小な表面形状においては、原子間力顕微鏡（ＡＦＭ＝Atomic Force Microscope）を用いることにより、Ｒａなどの数値化が可能である。 Here, the antireflection member described in Patent Document 1 is an antireflection member comprising a base material, a hard coat layer, and an antireflection layer, and the surface roughness Ra of the hard coat layer is represented by the following formulas (1) and (2): The condition indicated by is satisfied.
Ra1 = 1.4 nm to 13 nm (area 5 μm × 5 μm) (1)
Ra2 = 2.2 nm to 26 nm (area 20 μm × 20 μm) (2)
Ra (arithmetic mean roughness) is an index representing the surface roughness of the sample, and is a value defined in JIS-B0601: 2001. In the case of a nanoscale minute surface shape, Ra or the like can be quantified by using an atomic force microscope (AFM).
　特許文献１には、上記式（１）および（２）を満たすことで、ハードコート層に接する層（反射防止層あるいはその一部）の厚さが薄い場合においても、当該層の連続性を阻害することなく密着性を改善することができると記載されている。
　また、特許文献１では、ハードコート層の表面粗さが適度に粗い反射防止部材は、耐擦傷性が非常に高いと説明されている。 In Patent Document 1, by satisfying the above formulas (1) and (2), even when the thickness of the layer (antireflection layer or part thereof) in contact with the hard coat layer is thin, the continuity of the layer is given. It is described that the adhesion can be improved without hindering.
Further, Patent Document 1 describes that an antireflection member having a moderately rough surface of the hard coat layer has very high scratch resistance.
　ここで特許文献１では、防汚性については接触角測定の実験により評価を行い、密着性については碁盤目法により評価を行い、耐擦傷性については基材表面をスチールウールで２０回擦ったときの傷の有無の目視判定で評価を行っている。この特許文献１に記載の評価によれば、防汚性を有する層を含む反射防止層が形成される下地膜（ハードコート層）の表面粗さＲａの値が、上述した式（１）および（２）の範囲を満たすことで、密着性および耐擦傷性に優れる反射防止部材が得られることが記載されている。 Here, in Patent Document 1, the antifouling property is evaluated by a contact angle measurement experiment, the adhesion property is evaluated by a cross-cut method, and the scratch resistance is rubbed with steel wool 20 times. Evaluation is made by visual judgment of the presence or absence of scratches. According to the evaluation described in Patent Document 1, the value of the surface roughness Ra of the base film (hard coat layer) on which the antireflection layer including the antifouling layer is formed is expressed by the above formula (1) and It is described that an antireflection member excellent in adhesion and scratch resistance can be obtained by satisfying the range of (2).
　一方、特許文献２（特許５０３６８２７号公報）に記載の撥油性基材は、各種ディスプレイ、ショーケース、時計や計器のカバーガラスのほか、銀行ＡＴＭや切符券売機などのタッチパネル式電子機器のタッチ面などに適用可能であると記載されている。
　特許文献２では、撥油性を有する膜が形成される第１の膜の表面粗さに関するパラメータＲａ（中心線平均粗さ）、Ｒｚ（十点平均高さ）およびＰｖ（最大谷深さ）が適切な範囲となるように、エネルギーを持つ粒子を第１の膜に照射している。そして特許文献２には、これらのパラメータを適切な範囲とすることで第１の膜の表面に適切な凹部が形成され、その後に形成される撥油性を有する膜の耐摩耗性を実用に耐え得るレベルにまで向上させることができると記載されている。
　なお、特許文献２では、第１の膜のＲａが好ましくは０．１～１０００ｎｍであり、より好ましくは１～１００ｎｍ、さらに好ましくは３～２０ｎｍであることが開示されている。また、耐摩耗性に優れる撥油性基材として、第１の膜のＲａが１～１３ｎｍである例が具体的に開示されている。 On the other hand, the oil-repellent substrate described in Patent Document 2 (Patent No. 50368827) is a touch surface of touch panel type electronic devices such as bank ATMs and ticket vending machines, in addition to various displays, showcases, clocks and instrument cover glasses. It is described that it is applicable.
In Patent Document 2, parameters Ra (center line average roughness), Rz (ten-point average height), and Pv (maximum valley depth) related to the surface roughness of the first film on which the film having oil repellency is formed. The first film is irradiated with energetic particles so as to be in an appropriate range. In Patent Document 2, by setting these parameters to an appropriate range, an appropriate recess is formed on the surface of the first film, and the wear resistance of the oil-repellent film formed thereafter is practically endured. It is described that the level can be improved to the level obtained.
Patent Document 2 discloses that Ra of the first film is preferably 0.1 to 1000 nm, more preferably 1 to 100 nm, and further preferably 3 to 20 nm. Further, an example in which Ra of the first film is 1 to 13 nm is specifically disclosed as an oil-repellent substrate excellent in wear resistance.
　ここで特許文献２に記載の擦傷試験では、撥油性を有する第２の膜の表面をスチールウールで擦った後、試験面（第２の膜の表面）に油性マジックペンで線を描き、インクを乾燥布で拭き取れるか否かを評価している。特許文献２に記載の撥油性基材は、この擦傷試験の結果、下地膜（第１の膜）の表面粗さＲａの値が１ｎｍの場合に最大擦傷回数はわずか２００回程度であるのに対し、Ｒａの値が２ｎｍおよび３ｎｍの場合には最大擦傷回数が２２００回、Ｒａの値が５ｎｍの場合には最大擦傷回数が２８００回であった。 Here, in the scratch test described in Patent Document 2, after rubbing the surface of the second film having oil repellency with steel wool, a line is drawn on the test surface (the surface of the second film) with an oil-based magic pen, and the ink Whether or not can be wiped off with a dry cloth. As a result of this scratch test, the oil-repellent substrate described in Patent Document 2 has a maximum scratch count of only about 200 when the surface roughness Ra of the base film (first film) is 1 nm. In contrast, when the Ra value was 2 nm and 3 nm, the maximum number of scratches was 2200, and when the Ra value was 5 nm, the maximum number of scratches was 2800.
特開２００６－５８７２８号公報JP 2006-58728 A 特許５０３６８２７号公報Japanese Patent No. 5036827
　しかしながら、特許文献１に記載の実験では、防汚性を有する層（反射防止層を構成する低屈折率層）の表面をスチールウールで擦った後の防汚性については評価（接触角測定）を行っていない。すなわち、防汚性能の耐久性について充分な検討が為されていない。したがって、下地膜（ハードコート層）上に防汚膜（反射防止層を構成する低屈折率層）が成膜された状態で当該防汚膜の表面をスチールウールで２０回擦った場合に、防汚性が損なわれずに確保されているか否かが不明である。また、近年における防汚性能の耐久性に対する市場からの要求は非常に高く、例えばタッチパネルのタッチ面に適用する場合には防汚膜表面に対する接触回数は極めて多くなることから、上述したような２０回程度の摩擦に耐えられる程度では不充分である。
　また、特許文献２に記載された発明では、接触回数が極めて多くなるタッチパネルのタッチ面などに適用する場合、実用上の耐摩耗性を考慮すると、最大で２８００回の摩擦に耐えられる程度では未だ不充分と言える。 However, in the experiment described in Patent Document 1, the antifouling property after rubbing the surface of the antifouling layer (the low refractive index layer constituting the antireflection layer) with steel wool is evaluated (contact angle measurement). Not done. That is, sufficient investigation has not been made on the durability of the antifouling performance. Therefore, when the antifouling film (low refractive index layer constituting the antireflection layer) is formed on the base film (hard coat layer) and the surface of the antifouling film is rubbed with steel wool 20 times, It is unclear whether the antifouling property is ensured without being impaired. In recent years, the market demand for durability of antifouling performance is very high. For example, when applied to the touch surface of a touch panel, the number of times of contact with the antifouling film surface is extremely large. It is not enough to withstand the friction of about once.
In addition, in the invention described in Patent Document 2, when applied to the touch surface of a touch panel where the number of contacts is extremely large, considering the practical wear resistance, it is still not enough to withstand a maximum of 2800 times of friction. It can be said that it is insufficient.
　このように、特許文献１および２に記載された発明では長期的な耐久性について未だ充分であるとは言えない。特に近年、スマートフォンなどのタッチパネル式ディスプレイ等の用途では衝撃や摩擦に晒される頻度が高いため、防汚性能の耐久性に対する市場からの要求が非常に高度になってきている。したがって、例えばより厳しいスチールウール摩擦試験に耐え得るような、より高い耐久性が求められる。 Thus, it cannot be said that the inventions described in Patent Documents 1 and 2 are still sufficient for long-term durability. In particular, in recent years, applications such as touch panel displays such as smartphones are frequently exposed to shock and friction, and therefore, the demand from the market for durability of antifouling performance has become very high. Therefore, higher durability is required, for example, capable of withstanding a more severe steel wool friction test.
　そこで本発明は上記した問題を解決するために為されたものであり、耐摩耗性がより向上し、長期にわたり優れた防汚性を発揮する防汚膜付光学部材およびタッチパネル式ディスプレイを提供することを目的とする。 Accordingly, the present invention has been made to solve the above-described problems, and provides an antifouling film-coated optical member and a touch panel display that have improved wear resistance and exhibit excellent antifouling properties over a long period of time. For the purpose.
　上記した課題を解決するために、本発明の一実施形態における防汚膜付光学部材は、基材上に下地膜が形成され、前記下地膜表面に防汚膜が形成された防汚膜付光学部材であって、前記下地膜の表面粗さＲａが０．２５ｎｍ以上０．７６ｎｍ以下である。
　また、上記した課題を解決するために、本発明の一実施形態におけるタッチパネル式ディスプレイは、上記した本発明の一実施形態における防汚膜付光学部材を備える。 In order to solve the above-described problem, an optical member with an antifouling film according to an embodiment of the present invention is provided with an antifouling film in which a base film is formed on a substrate and the antifouling film is formed on the surface of the base film. It is an optical member, Comprising: Surface roughness Ra of the said base film is 0.25 nm or more and 0.76 nm or less.
Moreover, in order to solve an above-described subject, the touchscreen type display in one Embodiment of this invention is provided with the optical member with an antifouling film in one embodiment of the above-mentioned this invention.
　本発明によれば、耐摩耗性がより向上し、長期にわたり優れた防汚性を発揮する防汚膜付光学部材およびタッチパネル式ディスプレイを提供することができる。 According to the present invention, it is possible to provide an antifouling film-coated optical member and a touch panel display that have improved wear resistance and exhibit excellent antifouling properties over a long period of time.
本発明に係る防汚膜付光学部材の第１の実施形態における構成を示す概略図であって、基材上に他の膜を介して下地膜が形成されている防汚膜付光学部材の構成例を示す。BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows the structure in 1st Embodiment of the optical member with an antifouling film which concerns on this invention, Comprising: Of the optical member with an antifouling film in which the base film is formed through the other film | membrane on the base material A configuration example is shown. 本発明に係る防汚膜付光学部材の第２の実施形態における構成を示す概略図であって、基材上に下地膜が直接形成されている防汚膜付光学部材の構成例を示す図である。FIG. 5 is a schematic diagram illustrating a configuration of an optical member with an antifouling film according to a second embodiment of the present invention, and is a diagram illustrating a configuration example of an optical member with an antifouling film in which a base film is directly formed on a substrate. It is. 本発明に係るタッチパネル式ディスプレイの一実施形態における構成を示す概略図である。It is the schematic which shows the structure in one Embodiment of the touchscreen type display which concerns on this invention.
＜防汚膜付光学部材＞
　本発明に係る防汚膜付光学部材は、基材上に下地膜が形成され、前記下地膜表面に防汚膜が形成された防汚膜付光学部材であって、前記下地膜の表面粗さＲａが０．２５ｎｍ以上０．７６ｎｍ以下である。 <Optical member with antifouling film>
An optical member with an antifouling film according to the present invention is an optical member with an antifouling film in which a base film is formed on a base material and an antifouling film is formed on the surface of the base film, and the surface roughness of the base film is The thickness Ra is not less than 0.25 nm and not more than 0.76 nm.
　本発明に係る防汚膜付光学部材の構成について具体的に説明をするに先立ち、本発明の理解のため、まず、その効果を奏するメカニズムの推定について以下に述べる。 Prior to the specific description of the configuration of the optical member with an antifouling film according to the present invention, for the understanding of the present invention, first, the estimation of the mechanism that exerts the effect will be described below.
　本発明では、下地膜の表面粗さＲａを０．２５以上０．７６ｎｍ以下の範囲内とし、充分に凹凸を小さくすることで下地膜が平滑化され、下地膜の表面上のシラノール基をほぼ同一平面上に近い位置に配置させることができる。そのため、下地膜の表面に対して防汚膜を形成する際に、シランカップリング反応が起こる過程において、下地膜表面のシラノール基と防汚膜の成分の分子とが反応しやすい状態、つまり水素結合よりも強固なシロキサン結合が起こる状態になると推測される。 In the present invention, the surface roughness Ra of the base film is in the range of 0.25 to 0.76 nm, and the base film is smoothed by sufficiently reducing the unevenness, so that silanol groups on the surface of the base film are substantially eliminated. It can arrange | position to the position close | similar to the same plane. Therefore, when the antifouling film is formed on the surface of the undercoat film, the silanol group on the surface of the undercoat film and the molecules of the antifouling film easily react in the process of the silane coupling reaction, that is, hydrogen. It is assumed that a siloxane bond stronger than the bond occurs.
　ここでシランカップリング反応とは、防汚膜の成分の分子のアルコキシシランが加水分解し、下地膜表面のシラノール基と水素結合を形成し、脱水縮合により下地膜と強固な共有結合、つまりシロキサン結合を形成し、強固な密着性を発現するものである。防汚膜の成分の個々の分子が下地膜のシラノール基と化学結合可能な距離は限りがあるため、下地膜の表面のシラノール基が同一平面上に近い位置に配置されている方がより多くの反応基と結合しやすくなる。しかし、下地膜の表面の凹凸が大きいと下地膜のシラノール基の位置が適正な位置から外れ、防汚膜の成分の分子とシロキサン反応を形成するに至らずに弱い水素結合の状態のままで存在する部分ができてしまう。 Here, the silane coupling reaction means that the alkoxysilane component molecule of the antifouling film is hydrolyzed to form a hydrogen bond with the silanol group on the surface of the undercoat film, and a strong covalent bond to the undercoat film by dehydration condensation, that is, siloxane. It forms a bond and exhibits strong adhesion. Since the distance at which individual molecules of the antifouling film components can chemically bond with the silanol groups of the undercoat is limited, it is more likely that the silanol groups on the surface of the undercoat are located closer to the same plane. It becomes easy to combine with the reactive group. However, if the surface roughness of the undercoat film is large, the position of the silanol group in the undercoat film will deviate from the proper position, leaving a weak hydrogen bond without forming a siloxane reaction with the molecules of the antifouling film. An existing part is created.
　これに対して本発明では、下地膜の表面を平滑にし、下地膜上のシラノール基をほぼ同一平面上に近い位置に配置させることができる。そのため、前述のとおりシロキサン結合が起きやすい状態とすることができると推測される。これにより、下地膜と防汚膜との間においてより強固な密着性が得られ、防汚膜付光学部材の耐摩耗性を大きく向上させることができる。 On the other hand, in the present invention, the surface of the undercoat film can be smoothed and the silanol groups on the undercoat film can be arranged at positions close to substantially the same plane. Therefore, it is presumed that a siloxane bond can easily occur as described above. Thereby, stronger adhesiveness is obtained between the base film and the antifouling film, and the wear resistance of the optical member with the antifouling film can be greatly improved.
　ついで、本発明に係る防汚膜付光学部材の実施形態を図面に基づいて説明する。 Next, an embodiment of the optical member with an antifouling film according to the present invention will be described with reference to the drawings.
≪第１の実施形態≫
　図１は、本発明に係る防汚膜付光学部材の第１の実施形態における構成を示す概略図であって、基材上に他の膜を介して下地膜が形成されている防汚膜付光学部材の構成例を示す。
　図１に示すように、本実施形態の防汚膜付光学部材は、基材１１上に、低屈折率材料からなる低屈折率材料膜１４ａ，１４ｃと高屈折率材料からなる高屈折率材料膜１４ｂ，１４ｄとが交互に積層された積層膜１４が形成された構成である。そして、積層膜１４上に設けられた低屈折率材料からなる膜である下地膜１２の表面に、防汚膜１３が成膜された構成となっている。この積層膜１４と、下地膜１２と、で反射防止機能を発揮する（積層膜１４と、下地膜１２と、が反射防止膜を構成する）。
　なお、図１は防汚膜付光学部材の膜構成を模擬的に表わしたものであり、基材１１、積層膜１４、下地膜１２および防汚膜１３の実際の厚みを正確な比率で表したものではない。 << First Embodiment >>
FIG. 1 is a schematic diagram showing the configuration of a first embodiment of an optical member with an antifouling film according to the present invention, wherein the antifouling film has a base film formed on the base material via another film. The structural example of an attached optical member is shown.
As shown in FIG. 1, the antifouling film-coated optical member of the present embodiment has a low refractive index material film 14a, 14c made of a low refractive index material and a high refractive index material made of a high refractive index material on a substrate 11. In this configuration, a laminated film 14 in which the films 14b and 14d are alternately laminated is formed. The antifouling film 13 is formed on the surface of the base film 12 which is a film made of a low refractive index material provided on the laminated film 14. The laminated film 14 and the base film 12 exhibit an antireflection function (the laminated film 14 and the base film 12 constitute an antireflection film).
FIG. 1 schematically shows the film configuration of the optical member with an antifouling film, and the actual thicknesses of the base material 11, the laminated film 14, the base film 12, and the antifouling film 13 are expressed in an accurate ratio. It was n’t.
（基材１１）
　基材１１は下地膜１２および防汚膜１３等を積層形成可能なものであればよく、例えば、ガラスやプラスチック等からなる。防汚膜付光学部材をタッチパネル式ディスプレイ等に用いる場合、基材は可視光あるいは特定の波長の光を透過し得るものであることが好ましい。 (Substrate 11)
The substrate 11 only needs to be capable of laminating and forming the base film 12 and the antifouling film 13 and the like, for example, glass or plastic. When the antifouling film-coated optical member is used for a touch panel display or the like, the substrate is preferably capable of transmitting visible light or light having a specific wavelength.
（積層膜１４）
　図１に示すように、積層膜１４は、基材１１側から数えて奇数番目に積層された膜１４ａ，１４ｃが低屈折率材料からなり、偶数番目に積層された膜１４ｂ，１４ｄが高屈折率材料からなる。
　なお、本実施形態では下地膜１２も低屈折率材料膜１４ａ，１４ｃと同様に低屈折率材料からなり、積層膜１４上に積層され、積層膜１４と共に反射防止機能を発揮してなる。本実施形態では一例として積層膜１４を４層としているので、防汚膜１３を成膜するための下地膜１２は低屈折率材料となる。 (Laminated film 14)
As shown in FIG. 1, in the laminated film 14, the films 14a and 14c laminated odd-numbered from the substrate 11 side are made of a low refractive index material, and the films 14b and 14d laminated even-numbered are highly refracted. Made of rate material.
In the present embodiment, the base film 12 is also made of a low refractive index material, like the low refractive index material films 14 a and 14 c, and is laminated on the laminated film 14 and exhibits an antireflection function together with the laminated film 14. In this embodiment, since the laminated film 14 has four layers as an example, the base film 12 for forming the antifouling film 13 is a low refractive index material.
　低屈折率材料としては、例えば、ＳｉＯ2（二酸化ケイ素）、Ａｌ2Ｏ3添加ＳｉＯ2（アルミナ添加二酸化珪素）が挙げられる。ただし、本発明はこれに限定されるものではない。
　高屈折率材料としては、例えば、アルミナ含有酸化チタン－酸化ランタン系混合材料、酸化チタンを主成分とする他の混合酸化物、酸化ニオブあるいは酸化ニオブを主成分とする混合材料等が挙げられる。ただし、本発明はこれに限定されるものではない。 Examples of the low refractive index material include SiO 2 (silicon dioxide) and Al 2 O 3 added SiO 2 (alumina added silicon dioxide). However, the present invention is not limited to this.
Examples of the high refractive index material include alumina-containing titanium oxide-lanthanum oxide-based mixed materials, other mixed oxides mainly composed of titanium oxide, niobium oxide, mixed materials mainly composed of niobium oxide, and the like. However, the present invention is not limited to this.
　積層膜１４および積層膜１４を構成する各膜の膜厚については特に制限はないが、例えば、積層膜１４を構成する各膜の膜厚を１０～２００ｎｍとし、必要な数を積層して積層膜１４を構成することができる。
　なお、本実施形態における積層膜１４は４層構成（反射防止機能を発揮する防汚膜１３を含めると、５層の反射防止膜構成）であるが、本発明はこれに何ら限定されるものではなく、層数は何層であってもよい。 There are no particular restrictions on the film thickness of the laminated film 14 and each film constituting the laminated film 14, but for example, the film thickness of each film constituting the laminated film 14 is 10 to 200 nm, and a necessary number of layers are laminated. The membrane 14 can be configured.
The laminated film 14 in this embodiment has a four-layer structure (a five-layer antireflection film structure including the antifouling film 13 that exhibits an antireflection function), but the present invention is not limited to this. Instead, the number of layers may be any number.
　また、本実施形態では上述のように低屈折率層と高屈折率層とを交互に積層して形成された反射防止膜の一部としての積層膜１４を備えてなるが、本発明はこれに何ら限定されるものではない。例えば、他のフィルタやミラー、帯電防止等から選ばれる機能を有する少なくとも１つの膜を基材１１と下地膜１２との間に形成してもよい。 Further, in the present embodiment, the laminated film 14 is provided as a part of the antireflection film formed by alternately laminating the low refractive index layer and the high refractive index layer as described above. It is not limited at all. For example, at least one film having a function selected from other filters, mirrors, antistatics and the like may be formed between the base material 11 and the base film 12.
（下地膜１２）
　下地膜１２は、防汚膜１３を形成する下地となる層であり、当該下地膜１２の下層に設けられたもの（本実施形態の場合、積層膜１４）と、防汚膜１３との密着性を良好ならしめるものである。
　本実施形態では、下地膜１２の表面に成膜する防汚膜１３の耐摩耗性をより向上させるために、下地膜１２をその表面粗さＲａが０．７６ｎｍ以下となるように形成し、当該下地膜１２の表面に防汚膜１３を蒸着加工（例えば、真空蒸着）により成膜させて構成する。なお、本発明は蒸着加工に限られるものではなく、ディッピング法、塗布法、スプレー法、スピンコート法など蒸着加工以外の製法により防汚膜１３を形成してもよい。
　表面粗さＲａが０．７６ｎｍを超えると耐摩耗性が悪化し、長期に亘り優れた防汚性が発揮されず、好ましくない。 (Undercoat 12)
The undercoat film 12 is a layer serving as an undercoat for forming the antifouling film 13, and an adhesion between the antifouling film 13 and a layer provided in the lower layer of the undercoat film 12 (in this embodiment, the laminated film 14). It makes the quality good.
In the present embodiment, in order to further improve the wear resistance of the antifouling film 13 formed on the surface of the base film 12, the base film 12 is formed so that its surface roughness Ra is 0.76 nm or less, An antifouling film 13 is formed on the surface of the base film 12 by vapor deposition (for example, vacuum vapor deposition). The present invention is not limited to the vapor deposition process, and the antifouling film 13 may be formed by a production method other than the vapor deposition process, such as a dipping method, a coating method, a spray method, or a spin coating method.
When the surface roughness Ra exceeds 0.76 nm, the wear resistance is deteriorated, and the excellent antifouling property is not exhibited over a long period of time, which is not preferable.
　０．７６ｎｍ以下の表面粗さＲａを達成するには、種々の製造条件、下地膜１２以外の部材の条件など、様々な要因が影響するものであり、これらを好適な範囲に調整することが必要である。例えば、下地膜１２の成膜速度を０．５～数Å／ｓｅｃ、即ち通常よりも成膜速度を遅くすること、下地膜１２の厚さを調整すること、下地膜１２の成膜時の温度を調整すること、基板１１の表面粗さをなめらかにすることなどが０．７６ｎｍ以下の表面粗さＲａを達成するために必要である。この他、下地膜１２を成膜しながらイオンを照射するイオンアシストを行うようにしてもよい。このとき、イオンアシストの条件も表面粗さＲａに影響を与え得るため、調整することが望ましい。このような各種条件を調整し、０．７６ｎｍ以下の表面粗さＲａを有する下地膜１２が得られる。 In order to achieve a surface roughness Ra of 0.76 nm or less, various factors such as various manufacturing conditions and conditions of members other than the base film 12 influence, and these can be adjusted to a suitable range. is necessary. For example, the film formation rate of the base film 12 is 0.5 to several liters / sec, that is, the film formation rate is slower than usual, the thickness of the base film 12 is adjusted, Adjustment of temperature, smoothing of the surface roughness of the substrate 11, and the like are necessary to achieve a surface roughness Ra of 0.76 nm or less. In addition, ion assist that irradiates ions while forming the base film 12 may be performed. At this time, it is desirable to adjust the ion assist conditions because the surface roughness Ra can also be affected. By adjusting such various conditions, the base film 12 having a surface roughness Ra of 0.76 nm or less is obtained.
　下地膜１２の膜厚については特に制限はないが、例えば、２ｎｍ～１５０ｎｍ、好ましくは５～１２５ｎｍである。下地膜１２の膜厚が厚くなると、表面粗さＲａが大きくなる傾向がある。 The film thickness of the base film 12 is not particularly limited, but is, for example, 2 nm to 150 nm, preferably 5 to 125 nm. As the film thickness of the base film 12 increases, the surface roughness Ra tends to increase.
　下地膜１２を形成する材料はＳｉＯ2が望ましいが、表面にヒドロキシル基が存在する物質であればよい。例えば、表面にヒドロキシル基を有するＩＴＯ膜などの金属酸化物薄膜でもよい。好ましくはＩＴＯ膜などの金属酸化物膜の上にＳｉＯ2を２～３ｎｍ程度成膜したものがよい。 The material for forming the base film 12 is preferably SiO 2, but may be any substance having a hydroxyl group on the surface. For example, a metal oxide thin film such as an ITO film having a hydroxyl group on the surface may be used. Preferably, SiO 2 is formed to a thickness of about 2 to 3 nm on a metal oxide film such as an ITO film.
　なお、本発明では下地膜１２の表面粗さＲａが０．２５ｎｍ以上である。表面粗さＲａが０．２５ｎｍ未満であると、より凹凸が少なくなり、より平滑な下地膜が得られる一方で、生産性の悪化をもたらす。また、表面粗さＲａを０．２５ｎｍ未満としても、測定する際にノイズが発生するためばらつきが生じ、良好な精度の測定結果が得られないという問題もある。 In the present invention, the surface roughness Ra of the base film 12 is 0.25 nm or more. When the surface roughness Ra is less than 0.25 nm, the unevenness is further reduced, and a smoother undercoat film can be obtained, while the productivity is deteriorated. Further, even when the surface roughness Ra is less than 0.25 nm, noise is generated during measurement, causing variations, and there is a problem that a measurement result with good accuracy cannot be obtained.
・表面粗さＲａの測定方法
　表面粗さＲａは、原子間力顕微鏡（日立ハイテクサイエンス製、ＳＰＩ３８００Ｎ）を用いて、測定スケール２μｍ×２μｍ、バネ定数１５Ｎ／ｍ、共振周波数１１０－１５０ｋＨｚの条件にて測定を行い算出した。 ・ Measurement method of surface roughness Ra Surface roughness Ra is measured using an atomic force microscope (manufactured by Hitachi High-Tech Science, SPI3800N) under the conditions of a measurement scale of 2 μm × 2 μm, a spring constant of 15 N / m, and a resonance frequency of 110-150 kHz. And measured.
（防汚膜１３）
　防汚膜１３は、積層膜１４や下地膜１２の表面の指紋付着防止や滑り性の向上、汚れ拭き取り性の向上、水ヤケ防止などを目的として形成されるものである。
　また、防汚膜１３は、例えば、アルコキシシランを有する分子からなり、好ましくはアルコキシシランを有するフッ素系化合物からなる。フッ素系化合物としては、例えば、下式で表されるパーフルオロアルキルエーテル化合物が用いられる。 (Anti-fouling film 13)
The antifouling film 13 is formed for the purpose of preventing fingerprint adhesion on the surface of the laminated film 14 or the base film 12, improving slipperiness, improving dirt wiping property, and preventing water stains.
Further, the antifouling film 13 is made of, for example, a molecule having alkoxysilane, and is preferably made of a fluorine-based compound having alkoxysilane. As the fluorine-based compound, for example, a perfluoroalkyl ether compound represented by the following formula is used.
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒｆはパーフルオロアルキルエーテル基、Ｘは加水分解性基を複数有する加水分解性基含有シランを含む有機基、ＹはＲｆ基とＸ基とを連結する有機基である。）
Figure JPOXMLDOC01-appb-C000001
 (In the formula, Rf is a perfluoroalkyl ether group, X is an organic group containing a hydrolyzable group-containing silane having a plurality of hydrolyzable groups, and Y is an organic group linking the Rf group and the X group.)
　Ｘは、加水分解性基を複数、好ましくは２～１８個、より好ましくは２～９個有する加水分解性基含有シリル基を含む有機基である。
　加水分解性基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～１０のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基等の炭素数２～１０のアルコキシアルコキシ基、アセトキシ基等の炭素数１～１０のアシロキシ基、イソプロペノキシ基等の炭素数２～１０のアルケニルオキシ基、クロル基、ブロモ基、ヨード基等のハロゲン基やアミノ基などが挙げられる。中でも、メトキシ基、エトキシ基、イソプロペノキシ基、クロル基が好適である。 X is an organic group containing a hydrolyzable group-containing silyl group having a plurality of hydrolyzable groups, preferably 2 to 18, more preferably 2 to 9.
Examples of the hydrolyzable group include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, an alkoxyalkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group, and an acetoxy group. Examples thereof include an acyloxy group having 1 to 10 carbon atoms such as alkenyloxy group having 2 to 10 carbon atoms such as isopropenoxy group, a halogen group such as chloro group, bromo group and iodo group, and an amino group. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable.
　Ｙは、２価の有機基であり、Ｒｆ基とＸ基との連結基である。好ましくは、アミド結合、エーテル結合、エステル結合、ビニル結合、及びジメチルシリレン基等のジオルガノシリレン基から成る群より選ばれる１種又は２種以上の構造を含んでよい非置換、又は置換の炭素数２～１２の２価の有機基、好ましくは前記構造を含んでよい非置換又は置換の炭素数２～１２の２価の炭化水素基である。 Y is a divalent organic group, which is a linking group of Rf group and X group. Preferably, an unsubstituted or substituted carbon that may contain one or more structures selected from the group consisting of amide bonds, ether bonds, ester bonds, vinyl bonds, and diorganosylylene groups such as dimethylsilylene groups. A divalent organic group having 2 to 12 carbon atoms, preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms which may contain the above structure.
　フッ素系化合物としてより具体的には、パーフルオロアルキルエーテル基を有するトリメトキシシラン、ジメトキシシラン、トリエトキシシラン、トリイソプロペノキシシラン、トリクロロシランおよびトリアミノシランなどが挙げられる。これらの中でもパーフルオロアルキルエーテル基を有するトリメトキシシランが好ましい。 More specifically, examples of the fluorine-based compound include trimethoxysilane, dimethoxysilane, triethoxysilane, triisopropenoxysilane, trichlorosilane, and triaminosilane having a perfluoroalkyl ether group. Among these, trimethoxysilane having a perfluoroalkyl ether group is preferable.
　防汚膜１３の膜厚については特に制限はないが、例えば、１０～２０ｎｍである。膜厚が薄すぎると充分な防汚性が得られない場合があり、また、膜厚が厚すぎると透明性を損なう場合がある。 The film thickness of the antifouling film 13 is not particularly limited, but is, for example, 10 to 20 nm. If the film thickness is too thin, sufficient antifouling properties may not be obtained, and if the film thickness is too thick, transparency may be impaired.
≪第２の実施形態≫
　図２は、本発明に係る防汚膜付光学部材の第２の実施形態における構成を示す概略図であって、基材上に下地膜が直接形成されている防汚膜付光学部材の構成例を示す図である。
　図２に示す防汚膜付光学部材は、基材１１上に直接下地膜１２を形成した構成である。この下地膜１２は低屈折率材料を用いて単層で形成し、当該下地膜１２の表面に防汚膜１３を成膜した構成となっている。本実施形態では一例として、下地膜１２の低屈折率材料はＳｉＯ2であるとする。
　なお、本実施形態の防汚膜付光学部材は、層構成が上記第１の実施形態とは異なるが、これ以外の構成については上記第１の実施形態と同様である。したがって、本実施形態における防汚膜付光学部材は、層構成以外の構成については上記第１の実施形態において説明したものとすることができる。換言すると、本実施形態の防汚膜付光学部材は、上記第１の実施形態から積層膜１４を除いた構成である。
　また、この図２も防汚膜付光学部材の膜構成を模擬的に表わしたものであり、基材１１、下地膜１２および防汚膜１３の実際の厚みを正確な比率で表したものではない。 << Second Embodiment >>
FIG. 2 is a schematic diagram showing the configuration of the optical member with an antifouling film according to the second embodiment of the present invention, and the configuration of the optical member with an antifouling film in which a base film is directly formed on a substrate. It is a figure which shows an example.
The optical member with an antifouling film shown in FIG. 2 has a configuration in which a base film 12 is directly formed on a substrate 11. The base film 12 is formed as a single layer using a low refractive index material, and the antifouling film 13 is formed on the surface of the base film 12. In the present embodiment, as an example, the low refractive index material of the base film 12 is assumed to be SiO 2 .
The optical member with the antifouling film of the present embodiment is different from the first embodiment in the layer configuration, but the other configurations are the same as those in the first embodiment. Therefore, the optical member with the antifouling film in the present embodiment can be the one described in the first embodiment for the configuration other than the layer configuration. In other words, the antifouling film-coated optical member of the present embodiment has a configuration in which the laminated film 14 is removed from the first embodiment.
Further, FIG. 2 also schematically shows the film configuration of the optical member with the antifouling film, and shows the actual thicknesses of the base material 11, the base film 12 and the antifouling film 13 in an accurate ratio. Absent.
＜タッチパネル式ディスプレイ＞
　図３は本発明に係るタッチパネル式ディスプレイの一実施形態における構成を示す概略図である。
　本実施形態ではスマートフォンに用いられるタッチパネル式ディスプレイであり、ディスプレイ用カバーガラス３１に用いられる防汚膜付ガラスとして上述した本発明に係る防汚膜付光学部材が設けられてなる。
　ディスプレイ用カバーガラス３１は、透明電極を備えた表示部３２上に設けられ、表示部３２のディスプレイ用カバーガラス３１と反対側には主基板３３が設けられてなる。 <Touch panel display>
FIG. 3 is a schematic diagram showing the configuration of an embodiment of the touch panel display according to the present invention.
In this embodiment, it is a touch panel type display used for a smart phone, and the antifouling film-attached optical member according to the present invention described above is provided as the antifouling film-attached glass used for the display cover glass 31.
The display cover glass 31 is provided on a display unit 32 provided with a transparent electrode, and a main substrate 33 is provided on the opposite side of the display unit 32 from the display cover glass 31.
　なお、本発明に係るタッチパネル式ディスプレイはスマートフォンに用いられるものに限らず、例えば、その他の携帯電話、デジタルカメラ、デジタルビデオカメラ、ポータブルオーディオプレイヤー、ゲーム機器、カーナビゲーション、カーオーディオ、パーソナルコンピュータ、タブレット端末、液晶ディスプレイ、有機ＥＬディスプレイ、プラズマディスプレイ、その他各種表示機器、複写機、銀行ＡＴＭ、切符券売機等に用いることができる。 Note that the touch panel display according to the present invention is not limited to those used for smartphones, but, for example, other mobile phones, digital cameras, digital video cameras, portable audio players, game devices, car navigation systems, car audio systems, personal computers, tablets It can be used for terminals, liquid crystal displays, organic EL displays, plasma displays, various other display devices, copying machines, bank ATMs, ticket vending machines, and the like.
　以下、実施例を挙げて本発明をより詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（実施例１）
　基材１１である厚さ０．８ｍｍのガラス上に、ＳｉＯ2からなる低屈折率材料膜１４ａ，１４ｃ、及び、アルミナ含有酸化チタン－酸化ランタン系混合材料からなる高屈折率材料膜１４ｂ，１４ｄを交互に成膜し、４層構成の積層膜１４を形成した。積層膜１４を構成する各層は蒸着によって形成し、膜厚は低屈折率材料膜１４ａが１５ｎｍ、高屈折率材料膜１４ｂが１６．５ｎｍ、低屈折率材料膜１４ｃが３５ｎｍ、高屈折率材料膜１４ｄが１３６．５ｎｍであった。なお、低屈折率材料膜１４ａがガラスからなる基材１１に接するように設けられている。 Example 1
Low refractive index material films 14a and 14c made of SiO 2 and high refractive index material films 14b and 14d made of an alumina-containing titanium oxide-lanthanum oxide mixed material are formed on a glass substrate 0.8 mm in thickness. Were alternately formed to form a laminated film 14 having a four-layer structure. Each layer constituting the laminated film 14 is formed by vapor deposition, and the film thickness is 15 nm for the low refractive index material film 14a, 16.5 nm for the high refractive index material film 14b, 35 nm for the low refractive index material film 14c, and a high refractive index material film. 14d was 136.5 nm. The low refractive index material film 14a is provided in contact with the base material 11 made of glass.
　次いで、積層膜１４（最上部に位置する高屈折率材料膜１４ｄ）上にＳｉＯ2からなる下地膜１２を蒸着によって成膜した。所望の表面粗さＲａが得られるように、下地膜１２の成膜速度は１Å／Ｓ（積層膜１４の低屈折率膜の成膜速度は７Å／Ｓ）、成膜時の温度は約１５０℃とした。なお、所望の表面粗さＲａにすることを要する下地膜１２のみ成膜速度を遅くし、積層膜１４の各膜の成膜速度を速くした。こうすることで生産性を高めることができる。なお、下地膜１２の膜厚は９１ｎｍであった。 Next, the base film 12 made of SiO 2 was formed on the laminated film 14 (high refractive index material film 14d located at the uppermost part) by vapor deposition. In order to obtain the desired surface roughness Ra, the film formation rate of the base film 12 is 1 Å / S (the film formation rate of the low refractive index film of the laminated film 14 is 7 Å / S), and the temperature during film formation is about 150. C. It should be noted that only the base film 12 that needs to have the desired surface roughness Ra was slowed down and the film deposition speed of each film of the laminated film 14 was increased. This can increase productivity. In addition, the film thickness of the base film 12 was 91 nm.
　そして、下地膜１２の上にフッ素系化合物からなる防汚膜１３を形成し、防汚膜付光学部材を作製した。フッ素系化合物としては、パーフルオロアルキルエーテル含有トリメトキシシランを含むＳＵＲＦＣＬＥＡＲ１００（キヤノンオプトロン株式会社製）を用い、膜厚１２～１４ｎｍの防汚膜１３を形成した。また、得られた防汚膜付光学部材の構成は、図１に示す防汚膜付光学部材の構成と同様である。 Then, an antifouling film 13 made of a fluorine compound was formed on the base film 12 to produce an optical member with an antifouling film. As the fluorine-based compound, SURFCLEAR100 (manufactured by Canon Optron Co., Ltd.) containing perfluoroalkyl ether-containing trimethoxysilane was used to form an antifouling film 13 having a thickness of 12 to 14 nm. Moreover, the structure of the obtained optical member with an antifouling film is the same as that of the optical member with an antifouling film shown in FIG.
（実施例２、比較例）
　下地膜１２の成膜速度を変えた以外は実施例１と同様にして防汚膜付光学部材を作製した。 (Example 2, comparative example)
An optical member with an antifouling film was produced in the same manner as in Example 1 except that the deposition rate of the base film 12 was changed.
（実施例３～５）
　積層膜１４を形成せず、また、下地膜１２の成膜速度を変えた以外は実施例１と同様にして防汚膜付光学部材を作製した。また、得られた防汚膜付光学部材の構成は、図２に示す防汚膜付光学部材の構成と同様である。 (Examples 3 to 5)
An optical member with an antifouling film was produced in the same manner as in Example 1 except that the laminated film 14 was not formed and the film formation rate of the base film 12 was changed. Moreover, the structure of the obtained optical member with an antifouling film is the same as that of the optical member with an antifouling film shown in FIG.
（耐摩耗性試験）
　上記のように作製した実施例１～５および比較例の防汚膜付光学部材について、下記の方法に従い耐摩耗性試験を行った。
　スチールウール＃００００（径：約０．０１２ｍｍ、日本スチールウール株式会社製）を防汚膜付光学部材の防汚膜１３表面に載せ、１ｋｇ／ｃｍ2の荷重をかけた状態で、往復移動させて擦傷試験を行った。往復移動は移動速度６０往復／ｍｉｎ、移動距離１５ｍｍの条件で行った。 (Abrasion resistance test)
The antifouling film-coated optical members of Examples 1 to 5 and Comparative Example produced as described above were subjected to an abrasion resistance test according to the following method.
Steel wool # 0000 (diameter: about 0.012 mm, manufactured by Nippon Steel Wool Co., Ltd.) is placed on the surface of the antifouling film 13 of the optical member with the antifouling film and moved back and forth with a load of 1 kg / cm 2 applied. A scratch test was conducted. The reciprocating movement was performed under conditions of a moving speed of 60 reciprocating / min and a moving distance of 15 mm.
　また、スチールウールによる摩擦後、対水接触角の測定により耐摩耗性の評価を行った。具体的には、スチールウールで１０００回摩擦を行う毎に摩擦後の防汚膜１３の表面に液滴を作り、対水接触角を測定した。
　対水接触角とは、固体と水とが接触する点における水表面に対する接線と固体表面とがなす角度のことである。ここでは、この対水接触角の値が大きいほど、防汚膜１３の表面に傷が少ないことを表す。
　対水接触角の測定は、防汚膜１３の表面の９ヵ所（測定箇所Ｎｏ．１～９）において対水接触角を測定し、９点全てにおいて対水接触角が１００°以上である場合を合格、９点のうち１点でも対水接触角が１００°未満となる箇所がある場合を不合格とした。なお、摩擦回数０回における対水接触角の測定では、いずれの箇所においても摩擦による傷が生じていないため、５点のみ測定した。 In addition, the abrasion resistance was evaluated by measuring the contact angle with water after friction with steel wool. Specifically, every time the steel wool was rubbed 1000 times, a droplet was made on the surface of the antifouling film 13 after the friction, and the contact angle with water was measured.
The water contact angle is an angle formed by a tangent to the water surface and a solid surface at a point where the solid and water contact. Here, the larger the value of the water contact angle, the smaller the surface of the antifouling film 13 is.
The water contact angle is measured when the water contact angle is measured at nine locations (measurement locations No. 1 to 9) on the surface of the antifouling film 13, and the water contact angle is 100 ° or more at all nine points. The case where even one point out of the nine points has a contact angle with water of less than 100 ° was regarded as unacceptable. In the measurement of the contact angle with water when the number of frictions was 0, only 5 points were measured because no scratches were caused by friction at any location.
　実施例１～５および比較例の防汚膜付光学部材の耐摩耗性試験の結果を下記表１に示す。また、実施例１～５および比較例の防汚膜付光学部材を作製する際、防汚膜１３を形成する前の下地膜１２の表面粗さＲａを前述した測定方法により測定し、これを下記表１にあわせて示す。 The results of the abrasion resistance test of the optical members with antifouling films of Examples 1 to 5 and Comparative Example are shown in Table 1 below. Further, when the optical member with the antifouling film of Examples 1 to 5 and the comparative example was produced, the surface roughness Ra of the base film 12 before forming the antifouling film 13 was measured by the measurement method described above, and this It shows together with following Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１は、下地膜１２の表面粗さＲａの値が０．３１である。上記表１から明らかなように、最初に不合格となったときの擦傷回数は１４０００回であり、少なくとも擦傷回数が１３０００回の時点では合格の条件を満たしている。したがって、耐摩耗性に関する合格の条件を満たす最大擦傷回数は、１３０００回以上１４０００回未満の何れかの値ということがわかる。
　実施例２は、下地膜１２の表面粗さＲａの値が０．７５である。実施例２における耐摩耗性に関する合格の条件を満たす最大擦傷回数は、８０００回以上９０００回未満の何れかの値である。
　これに対し、比較例は、下地膜１２の表面粗さＲａの値が１．２５（特許文献２で示されている範囲の値）である。比較例における耐摩耗性に関する合格の条件を満たす最大擦傷回数は、１０００回未満であり、耐摩耗性に劣り、長期に亘って優れた防汚性が得られないことがわかる。 In Example 1, the value of the surface roughness Ra of the base film 12 is 0.31. As is apparent from Table 1 above, the number of scratches at the first failure was 14,000, and the pass condition was satisfied at least when the number of scratches was 13,000. Therefore, it can be seen that the maximum number of scratches that satisfy the pass condition regarding wear resistance is any value between 13,000 times and less than 14000 times.
In Example 2, the value of the surface roughness Ra of the base film 12 is 0.75. The maximum number of scratches that satisfy the pass condition for wear resistance in Example 2 is any value between 8000 and less than 9000.
On the other hand, in the comparative example, the value of the surface roughness Ra of the base film 12 is 1.25 (the value in the range shown in Patent Document 2). It can be seen that the maximum number of scratches that satisfy the pass condition regarding the wear resistance in the comparative example is less than 1000, which is inferior in wear resistance and does not provide excellent antifouling properties over a long period of time.
　実施例３は、下地膜１２の表面粗さＲａの値が０．３６である。実施例３における耐摩耗性に関する合格の条件を満たす最大擦傷回数は、９０００回以上１００００回未満の何れかの値である。
　実施例４は、下地膜１２の表面粗さＲａの値が０．２５である。実施例４における耐摩耗性に関する合格の条件を満たす最大擦傷回数は、９０００回以上１００００回未満の何れかの値である。
　実施例５は、下地膜１２の表面粗さＲａの値が０．７６である。実施例５における耐摩耗性に関する合格の条件を満たす最大擦傷回数は、６０００回以上７０００回未満の何れかの値である。 In Example 3, the value of the surface roughness Ra of the base film 12 is 0.36. The maximum number of scratches that satisfy the pass condition regarding wear resistance in Example 3 is any value between 9000 and less than 10,000.
In Example 4, the value of the surface roughness Ra of the base film 12 is 0.25. The maximum number of scratches that satisfy the pass condition regarding wear resistance in Example 4 is any value between 9000 and less than 10,000.
In Example 5, the value of the surface roughness Ra of the base film 12 is 0.76. The maximum number of scratches that satisfy the pass condition regarding wear resistance in Example 5 is any value between 6000 times and less than 7000 times.
（実施例６）
　基材として厚さ０．７ｍｍの４インチにカッティングされた強化ガラス（Corning社製Gorillaガラス）を用い、この強化ガラスの縁部に塗装を施し、ディスプレイ用カバーガラス３１を作製した。さらにディスプレイ用カバーガラス３１を、透明電極を備える表示部３２と貼り合わせた。 (Example 6)
A tempered glass (Gorilla glass manufactured by Corning Co., Ltd.) cut to 4 inches having a thickness of 0.7 mm was used as a substrate, and the edge of this tempered glass was coated to produce a cover glass 31 for display. Furthermore, the display cover glass 31 was bonded to the display unit 32 including a transparent electrode.
　このディスプレイ用カバーガラス３１を洗浄後、表示部３２の貼り付け側と反対側の面に蒸着可能となるように真空蒸着機にセットした。
　次いで、真空度１．０×１０-3［Ｐａ］の圧力まで真空引きした後、Ｎｂ2Ｏ5（五酸化ニオブ）とＳｉＯ2（二酸化ケイ素）とを交互に７層作成した。さらに、７層目のＮｂ2Ｏ5層の上に、６層目までと比較して成膜速度が遅い成膜速度１［Å／ｓｅｃ］でＳｉＯ2層（下地膜）を蒸着成膜した。ディスプレイ用カバーガラス３１上に積層された積層膜（下地膜を含めて合計８層）は、膜厚３０６ｎｍであった。
　そして、このＳｉＯ2膜上にパーフルオロアルキルエーテル含有トリメトキシシランを含むＳＵＲＦＣＬＥＡＲ１００を用いて１２～１６ｎｍの膜厚で成膜し、防汚膜を形成した。 After the display cover glass 31 was washed, it was set in a vacuum vapor deposition machine so that vapor deposition was possible on the surface of the display unit 32 opposite to the side to which it was attached.
Subsequently, after vacuuming to a pressure of 1.0 × 10 −3 [Pa], seven layers of Nb 2 O 5 (niobium pentoxide) and SiO 2 (silicon dioxide) were alternately formed. Further, a SiO 2 layer (underlayer) was deposited on the seventh Nb 2 O 5 layer at a deposition rate of 1 [Å / sec], which was slower than the sixth layer. . The laminated film (a total of 8 layers including the base film) laminated on the display cover glass 31 had a film thickness of 306 nm.
Then, an antifouling film was formed on this SiO 2 film using SURFCLEAR100 containing perfluoroalkyl ether-containing trimethoxysilane to a thickness of 12 to 16 nm.
　この表示部３２を備えたコーティング済みのディスプレイ用カバーガラス３１を主基板３３と組み合わせて、タッチパネルディスプレイを作製した。
　このタッチパネルディスプレイは優れた防汚性能を持ち、高い耐久性を維持することができた。 The coated display cover glass 31 provided with the display unit 32 was combined with the main substrate 33 to produce a touch panel display.
This touch panel display had excellent antifouling performance and was able to maintain high durability.
　以上説明した実施例１～６の構成によれば、下地膜１２の凸凹が平滑化され、防汚膜１３の耐摩耗性を大きく向上させることができ、長期に亘り優れた防汚性を発揮できることがわかった。 According to the configurations of Examples 1 to 6 described above, the unevenness of the base film 12 is smoothed, the wear resistance of the antifouling film 13 can be greatly improved, and excellent antifouling properties are exhibited over a long period of time. I knew it was possible.
　なお、上記実施形態は、何れも本発明を実施するにあたっての具体化の一例を示したものに過ぎず、これによって本発明の技術的範囲が限定的に解釈されてはならないものである。すなわち、本発明はその要旨、またはその主要な特徴から逸脱することなく、様々な形で実施することができる。 Note that each of the above-described embodiments is merely an example of the implementation of the present invention, and the technical scope of the present invention should not be construed in a limited manner. That is, the present invention can be implemented in various forms without departing from the gist or the main features thereof.
　この出願は２０１４年２月２４日に出願された日本国特許出願第２０１４－０３２９６０からの優先権を主張するものであり、その内容を引用してこの出願の一部とするものである。 This application claims priority from Japanese Patent Application No. 2014-032960 filed on February 24, 2014, the contents of which are incorporated herein by reference.
　１１　基材
　１２　下地膜
　１３　防汚膜
　１４　積層膜
　３１　ディスプレイ用カバーガラス
　３２　表示部
　３３　主基板 DESCRIPTION OF SYMBOLS 11 Base material 12 Base film 13 Antifouling film 14 Laminated film 31 Cover glass for display 32 Display part 33 Main board

Claims (11)

  1. 　基材上に下地膜が形成され、前記下地膜表面に防汚膜が形成された防汚膜付光学部材であって、
    　前記下地膜の表面粗さＲａが０．２５ｎｍ以上０．７６ｎｍ以下であることを特徴とする防汚膜付光学部材。     An antifouling film-coated optical member in which a base film is formed on a substrate and an antifouling film is formed on the surface of the base film,
    An optical member with an antifouling film, wherein the surface roughness Ra of the undercoat film is from 0.25 nm to 0.76 nm.
  2. 　前記下地膜は、前記基材上に直接形成されていることを特徴とする請求項１に記載の防汚膜付光学部材。 The optical member with an antifouling film according to claim 1, wherein the base film is directly formed on the substrate.
  3. 　前記下地膜は、低屈折材料からなることを特徴とする請求項２に記載の防汚膜付光学部材。 3. The optical member with an antifouling film according to claim 2, wherein the base film is made of a low refractive material.
  4. 　前記下地膜は、前記基材上に少なくとも１つの膜を介して形成されていることを特徴とする請求項１に記載の防汚膜付光学部材。 The optical member with an antifouling film according to claim 1, wherein the base film is formed on the base material via at least one film.
  5. 　前記下地膜は、前記基板上に積層膜を介して形成されてなり、
    　前記積層膜は、低屈折材料からなる膜と、高屈折材料からなる膜とが２層以上交互に積層されてなることを特徴とする請求項４に記載の防汚膜付光学部材。     The base film is formed on the substrate via a laminated film,
    5. The optical member with an antifouling film according to claim 4, wherein the laminated film is formed by alternately laminating a film made of a low refractive material and a film made of a high refractive material.
  6. 　前記下地膜は、表面にシラノール基を有することを特徴とする請求項１乃至５のいずれか一項に記載の防汚膜付光学部材。 The optical member with an antifouling film according to any one of claims 1 to 5, wherein the base film has a silanol group on a surface thereof.
  7. 　前記下地膜は、ＳｉＯ2からなることを特徴とする請求項１乃至６のいずれか一項に記載の防汚膜付光学部材。 The optical member with an antifouling film according to claim 1, wherein the base film is made of SiO 2 .
  8. 　前記防汚膜は、アルコキシシランを有する分子からなることを特徴とする請求項１乃至７のいずれか一項に記載の防汚膜付光学部材。 The optical member with an antifouling film according to any one of claims 1 to 7, wherein the antifouling film comprises a molecule having an alkoxysilane.
  9. 　前記アルコキシシランを有する分子がフッ素系化合物であることを特徴とする請求項８に記載の防汚膜付光学部材。 The optical member with an antifouling film according to claim 8, wherein the molecule having the alkoxysilane is a fluorine compound.
  10. 　前記防汚膜の表面にスチールウールを載せ、１ｋｇ／ｃｍ2の荷重をかけながら往復運動をさせて行う擦傷試験の合格回数が、６０００回以上であることを特徴とする請求項１乃至９のいずれか一項に記載の防汚膜付光学部材。 10. The pass number of the scratch test conducted by placing steel wool on the surface of the antifouling film and reciprocating while applying a load of 1 kg / cm 2 is 6000 times or more. The optical member with an antifouling film according to any one of the above.
  11. 　請求項１乃至１０のいずれか一項に記載の防汚膜付光学部材を備えることを特徴とするタッチパネル式ディスプレイ。 A touch panel display comprising the optical member with an antifouling film according to any one of claims 1 to 10.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014199991A1 (en) * 2013-06-11 2017-02-23 日本電気硝子株式会社 Cover member, display device, and method of manufacturing cover member
JP2017215480A (en) * 2016-05-31 2017-12-07 株式会社トプコン Optical member having modified surface
WO2019058825A1 (en) * 2017-09-21 2019-03-28 富士フイルム株式会社 Antireflection film, optical element, and optical system
WO2019208426A1 (en) * 2018-04-27 2019-10-31 コニカミノルタ株式会社 Optical thin film, optical member, and method for manufacturing optical thin film
KR20200004369A (en) * 2017-05-08 2020-01-13 코닝 인코포레이티드 Glass, glass-ceramic, and ceramic products with durable lubricity, fingerprint-resistant coatings over optical and scratch-resistant coatings, and methods of making the same
JP2020030247A (en) * 2018-08-20 2020-02-27 株式会社タムロン Optical element having stain resistant layer
JPWO2018193742A1 (en) * 2017-04-20 2020-05-21 信越化学工業株式会社 Antireflection member and manufacturing method thereof
US20230084928A1 (en) * 2016-11-18 2023-03-16 The Penn State Research Foundation Liquids and viscoelastic material repellent and anti-biofouling coatings
WO2023095760A1 (en) * 2021-11-26 2023-06-01 Ａｇｃ株式会社 Transparent substrate with metal oxide layers and method for producing same
US11971519B2 (en) 2020-07-09 2024-04-30 Corning Incorporated Display articles with antiglare surfaces and thin, durable antireflection coatings

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002297042A (en) * 2001-03-30 2002-10-09 Toray Ind Inc Plastic layered body and image display protective member
JP2003292342A (en) * 1997-12-04 2003-10-15 Nippon Sheet Glass Co Ltd Silica-based film coated article
WO2004113966A1 (en) * 2003-06-18 2004-12-29 Asahi Kasei Kabushiki Kaisha Antireflective film
JP2010037115A (en) * 2008-07-31 2010-02-18 Seiko Epson Corp Light-transmitting member, timepiece and method for producing the light-transmitting member

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004170962A (en) * 2002-11-06 2004-06-17 Pentax Corp Antireflective eyeglass lens and its manufacturing method
JP4688230B2 (en) * 2008-10-09 2011-05-25 株式会社シンクロン Deposition method
JP5857942B2 (en) * 2011-11-30 2016-02-10 信越化学工業株式会社 Fluorine surface treatment agent for vapor deposition and article vapor-deposited with the surface treatment agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003292342A (en) * 1997-12-04 2003-10-15 Nippon Sheet Glass Co Ltd Silica-based film coated article
JP2002297042A (en) * 2001-03-30 2002-10-09 Toray Ind Inc Plastic layered body and image display protective member
WO2004113966A1 (en) * 2003-06-18 2004-12-29 Asahi Kasei Kabushiki Kaisha Antireflective film
JP2010037115A (en) * 2008-07-31 2010-02-18 Seiko Epson Corp Light-transmitting member, timepiece and method for producing the light-transmitting member

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JPWO2018193742A1 (en) * 2017-04-20 2020-05-21 信越化学工業株式会社 Antireflection member and manufacturing method thereof
US10822271B2 (en) 2017-05-08 2020-11-03 Corning Incorporated Glass, glass-ceramic and ceramic articles with durable lubricious anti-fingerprint coatings over optical and scratch-resistant coatings and methods of making the same
KR102579362B1 (en) * 2017-05-08 2023-09-18 코닝 인코포레이티드 Glass, glass-ceramic and ceramic products having a durable, lubricating, anti-fingerprint coating over an optical and scratch-resistant coating and methods for making the same
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US11422290B2 (en) 2017-09-21 2022-08-23 Fujifilm Corporation Antireflection film, optical element, and optical system
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WO2019208426A1 (en) * 2018-04-27 2019-10-31 コニカミノルタ株式会社 Optical thin film, optical member, and method for manufacturing optical thin film
JP2020030247A (en) * 2018-08-20 2020-02-27 株式会社タムロン Optical element having stain resistant layer
US11971519B2 (en) 2020-07-09 2024-04-30 Corning Incorporated Display articles with antiglare surfaces and thin, durable antireflection coatings
US11977206B2 (en) 2020-07-09 2024-05-07 Corning Incorporated Display articles with diffractive, antiglare surfaces and thin, durable antireflection coatings
WO2023095760A1 (en) * 2021-11-26 2023-06-01 Ａｇｃ株式会社 Transparent substrate with metal oxide layers and method for producing same

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