JP2021014399A - Substrate with low reflective film and method for manufacturing the same - Google Patents

Abstract

To provide a substrate with a low reflective film, which shows little changes in reflected light or hues between the main surface and a side surface thereof when viewed and which has high display property, even when the substrate is used as a front substrate or the like disposed with the side surface exposed.SOLUTION: A substrate with a low reflective film 10 includes a transparent substrate 11, a first low reflective film 12 disposed on one major surface of the transparent substrate 11, and a second low reflective film 13 disposed on a side surface of the transparent substrate 11. The first low reflective film 12 disposed on one major surface shows a luminous reflectance R1 of 0.6% or less; and the second low reflective film 13 disposed on the side surface shows a luminous reflectance Rs of 2.5% or less and a chromaticity a* of 0 to 4 and b* of 3 to 9.SELECTED DRAWING: Figure 1

Description

The present invention relates to a substrate with a low-reflection film having a low-reflection film on the main surface and side surfaces of the transparent substrate, and a method for producing the substrate with the low-reflection film.

In recent years, in display devices such as tablet PCs (Personal Computers), smartphones, car navigation devices, and touch panels, a front substrate such as a cover glass is provided on the visible side of the display panel for the purpose of protecting the display panel. There is. In this front substrate, a low reflection film is generally provided on the main surface on the viewing side for the purpose of suppressing reflection due to light reflection and improving the visibility of the display. Further, in the front substrate with such a low-reflection film, light such as a black printing layer is applied to the peripheral portion of the main surface on the non-visual side where the low-reflection film is not provided for the purpose of improving the design and aesthetics. A shielding portion is also provided (see, for example, Patent Document 1).

Further, in such a front substrate for a display, many products are exposed to the side surface of the front substrate from the viewpoint of design.

By the way, in the front substrate that exposes not only the main surface on the visual side but also the side surface in this way, after forming a low reflection film on the main surface of the front substrate, the substrate is cut to a desired size to manufacture. The side surface is not treated with a low-reflection film, and there is a problem that glare becomes remarkable due to the difference in chromaticity from the main surface and the presence or absence of light reflection. Further, even if a low-reflection film is formed on the side surface, a technique for matching the color on the main surface and the side surface is not known. Therefore, in that case, the people who visually recognize the front substrate are made to perceive a large change such as reflected light and color when they visually recognize it.

Japanese Unexamined Patent Publication No. 2005-242265

The present invention has been made in response to the above problems, and even in a front substrate or the like which is arranged with its side surface exposed, there is little change in reflected light or color between the main surface and the side surface when visually recognized. An object of the present invention is to provide a substrate with a low-reflection film, which has high displayability and can maintain an aesthetic appearance.

The substrate with a low-reflection film of the present invention includes a transparent substrate, a first low-reflection film provided on one main surface of the transparent substrate, and a second low-reflection film provided on the side surface of the transparent substrate. A substrate with a low-reflection film comprising ,, wherein the visual reflectance R1 of the first low-reflection film provided on one of the main surfaces is 0.6% or less, and the substrate is provided on the side surface. The second low-reflection film is characterized in that the visual reflectance Rs is 2.5% or less, the chromaticity a ^* is 0 to 4, and b ^* is 3 to 9.

The display device of the present invention is characterized by having a display and a substrate with a low reflection film of the present invention provided as a front substrate on the front surface of the display.

In the method for producing a substrate with a low reflection film of the present invention, a transparent substrate is fixed to a carrier substrate for fixing the transparent substrate at a predetermined interval via a spacer, and one main surface of the transparent substrate is fixed. A method for manufacturing a substrate with a low-reflection film, in which a first low-reflection film is simultaneously formed on a side surface of the transparent substrate and a second low-reflection film is simultaneously formed on the side surface of the transparent substrate by sputtering, and is provided on one of the main surfaces. The visual reflectance R1 of the first low-reflective coating is 0.6% or less, and the visual reflectance Rs of the second low-reflection film provided on the side surface is 2.5% or less, and the chromaticity. It is characterized in that a ^* is 0 to 4 and b ^* is 3 to 9.

Since the substrate with a low-reflection film of the present invention has a low-reflection film on the main surface and side surfaces of the substrate in which the visual reflectance for incident light from the low-reflection film side is adjusted, light is emitted on the main surface and side surfaces. It is visually recognized that changes in reflection and color are small, and it is excellent in terms of displayability and aesthetics. Therefore, by using such a substrate with a low-reflection film as the front substrate, it is possible to improve the visibility of the display of the display device, and it is possible to impart excellent design and aesthetics.

It is sectional drawing which shows typically one Embodiment of the substrate with a low reflection film of this invention. It is a figure which shows typically the route of the light incident from the low-reflection film side in the substrate with a low-reflection film of this invention. It is sectional drawing which shows typically the other embodiment of the substrate with a low reflection film of this invention. It is sectional drawing which shows still another Embodiment of the substrate with a low reflection film of this invention schematically. It is a figure which showed an example of the sputtering operation used in the manufacturing method of the substrate with a low reflection film of this invention.

Hereinafter, modes for carrying out the present invention will be described. The present invention is not limited to the following embodiments, and various modifications and substitutions may be added to the embodiments without departing from the scope of the present invention.

FIG. 1 is a cross-sectional view schematically showing an embodiment of the substrate with a low-reflection film of the present invention.

As shown in FIG. 1, the substrate 10 with a low-reflection film of the embodiment shown here includes a transparent substrate 11, a first low-reflection film 12 formed on one main surface of the transparent substrate 11, and a transparent substrate. It includes a second low-reflection film 13 formed on the side surface of 11, and a black printing portion 14 formed on a part of the other main surface of the transparent substrate 11.

In the substrate 10 with a low-reflection film of the present embodiment, the visual reflectance Rtot measured with respect to the incident light from the first low-reflection film 12 side is 1.5% or less, and the first The visual reflectance Rs measured with respect to the incident light from the low reflective film 13 side of No. 2 is 2.5% or less, the chromaticity a ^* is 0 to 4, and b ^* is 3 to 9. There is.

Here, the visual reflectance is a reflection stimulus value Y defined in JIS Z8701. In the present invention, the main surface Rtot uses a spectrophotometer (manufactured by Konica Minolta, model: CM-2600d) to measure specular and diffuse reflected light together under a D65 light source. The reflected light was measured by the Include) method, and the Rs on the side surface was measured by a specular light measuring device (USPM RUIII, manufactured by Olympus). The visual reflectance is calculated using the reflectance measured in this way.

The first visual reflectance Rtot can be obtained by measurement at a position close to the side surface to some extent, and can be obtained, for example, by measurement within a range of 50 mm from the ridgeline which is the boundary between the side surface and the main surface. It is preferable that it is determined by measurement within the range of 5 to 30 mm. With such a range, the visual reflectance Rtot and Rs obtained on the main surface and the side surface can be expressed in a good correlation with the color change and the like that are felt when actually visually recognized.

The chromaticity a ^* and b ^* are the chromaticity in the L ^* a ^* b ^* color system, and the L ^* a ^* b ^* color system is standardized by the International Lighting Commission (CIE) in this specification. CIE 1976 (L ^* a ^* b ^* ) color space (CIELAB), which means the brightness (L ^* ) in the F2 light source and the chromaticity (a ^* , b ^* ) of the reflected light in the F2 light source. The chromaticity may be measured by measuring the tint in reflection, and the reflection spectrum may be acquired. The reflection spectrum can be acquired using a spectrophotometer or a spectrophotometer, and the chromaticity can be calculated.

The visual reflectance Rtot in the first low-reflection film and the visual reflectance Rs and the chromaticities a ^* and b ^* in the second low-reflection film are mainly satisfied by satisfying the above relationships. It is visually recognized that the difference in color and the like is small between the surface and the side surface, and there is little discomfort.

In the present embodiment, the visual reflectance Rtot is preferably 1.5% or less, more preferably 1.2% or less, still more preferably 1% or less.

In the black printing section 14, the chromaticity a ^* is more than -6 and less than 6, and b ^* is more than -6 and less than 6 as the tint of the first reflective film 12 provided on one main surface of the transparent substrate 11. The chromaticity a ^* is more preferably more than -5 and less than 3, b ^* is more preferably more than -6 and less than 3, the chromaticity a ^* is more preferably more than -4 and less than 2, and b ^* is more preferably more than -4 and less than 2. By setting the range to such a range, the coloring of the reflected light can be minimized, and it becomes easy to match with the color of the side surface.

Similarly, the visual reflectance Rs is preferably 2.5% or less, more preferably 2% or less, still more preferably 1.8% or less.

(Measurement of visual reflectance of the main surface)
Hereinafter, a method of calculating the visual reflectance Rtot of the main surface will be described with reference to FIG. FIG. 2 is a diagram schematically showing a route (optical path) of incident light from the first low-reflection film 12 side to the base 10 with a low-reflection film of the present invention. In FIG. 2, the same components as those in FIG. 1 are designated by the same reference numerals.

In the region of the substrate 10 with a low reflection film that does not have the black printed portion 14, the incident light L1 incident on the first low reflection film 12 from one main surface side is partially reflected and reflected by the low reflection film surface. The light becomes L2, and the balance becomes the transmitted light L3 that passes through the first low-reflection film 12 and the transparent substrate 11 in this order. A part of the transmitted light L3 is reflected by the other main surface of the transparent substrate 11, and this reflected light is transmitted to the outside as the emitted light L4 after being transmitted through the transparent substrate 11 and the first low reflection film 12 in this order. .. This light route is referred to as the first route.

The visual reflectance RG of the light of the first route is the visual reflectance related to the reflected light L2, that is, the visual reflectance R1 of the first low-reflection film 12 and the visual reflectance R4 related to the emitted light L4. Is the sum of.

Here, the visual reflectance R4 is expressed by the equation (I) using each reflectance along the light route, and the visual reflectance RG of the light of the first route is expressed by the equation (II), respectively. .. However, R0 is the one-sided visual reflectance from the other main surface of the transparent substrate 11.
R4 = (1-R1) × R0 × (1-R1) ……… (I)
RG = R1 + (1-R1) x R0 x (1-R1) ... (II)

On the other hand, in the region of the substrate 10 with the low reflection film 10 provided with the black printing portion 14, the incident light L5 incident on the first low reflection film 12 from one main surface side is partially reflected and becomes the reflected light L6. The rest is the transmitted light L7 that passes through the first low-reflection film 12 and the transparent substrate 11 in this order. A part of the transmitted light L7 is reflected at the interface between the other main surface of the transparent substrate 11 and the black printing portion 14, and the reflected light is transmitted through the transparent substrate 11 and the first low-reflection film 12 in this order. , Is emitted to the outside as emitted light L8. This light route is referred to as the second route.

The visual reflectance Rtot of the second route is the sum of the visual reflectance related to the reflected light L6, that is, the visual reflectance R1 of the first low-reflection film 12 and the visual reflectance R8 related to the emitted light L8. Is.

Here, the visual reflectance R8 is expressed by the equation (III) using each reflectance along the light route, and the visual reflectance Rtot of the second route is expressed by the equation (IV), respectively. However, R2 is the visual reflectance of the black printed portion 14 at the interface with the transparent substrate 11.
R8 = (1-R1) x R2 x (1-R1) ……… (III)
Rtot = R1 + (1-R1) x R2 x (1-R1) ... (IV)

In the substrate 10 with a low-reflection film, the visual reflectance RG in the region not having the black printing portion 14 and the visual reflectance Rtot in the region having the black printing portion 14 are measurable amounts. Therefore, R1 can be calculated from the above formula (II) and R2 can be calculated from the above formula (IV) on the premise of the reflectance R0 of the given transparent substrate. As described above, Rtot corresponds to the visual reflectance R measured with respect to the incident light from the first low-reflection film 12 side in the region having the black printed portion 14, and is low in the present embodiment. It is 2% or less in the substrate 10 with a reflective film. Further, R0 can be calculated by, for example, using an ellipsometer to obtain the refractive index of the back surface of the region having no black printing portion 14, that is, the side having no low reflective film.

Further, when the first low-reflection film 12 absorbs the absorption rate A1, the above can be obtained by setting (1-R1) to (1-R1-A1) in the formulas (II) and (IV). R1 and R2 can be calculated in the same manner as in. The transmittance A1 of the first low-reflection film 12 is calculated by comparing the transmittance Tg of the region having no black printed portion 14 on the other main surface of the transparent substrate 11 with the transmittance T0 of only the transparent substrate 11. it can.

Actually, for example, of the transmitted light L3, a part of the light that is reflected by the other main surface of the transparent substrate 11 and is transmitted through the transparent substrate 11 and the first low-reflection film 12 in this order is the emitted light L4. Is emitted from the inside of the glass, a part of the glass is reflected at the glass / air interface, returns to the inside of the glass, passes through the transparent substrate 11, and a part of the glass is reflected on the other main surface of the transparent substrate 11. Emitted from the inside. Further, a route in which this cycle is repeated arbitrarily is conceivable, but if R1 and R2 are in the above range, the contribution from the route after L8 is sufficiently small to be ignored.

The visual reflectance R1 of the first low-reflection film 12 can be arbitrarily adjusted depending on the constituent materials of each layer constituting the first low-reflection film 12, the number of layers, the thickness of each layer, the order of lamination, and the like. R1 is preferably 1% or less, preferably 0.6% or less, and even more preferably 0.5% or less. When a substrate with a low reflection film is attached to a liquid crystal display or the like as a cover glass, reflection between the back surface of the substrate and the front surface of the display is generally sufficiently suppressed by optical adhesion. Therefore, the reflectance of the display with the cover glass substrate is mainly contributed by the reflectance from R1 and the inside of the display. When R1 is in this range, the reflection from the surface of the laminate can be sufficiently suppressed as compared with the reflection from the inside of the display. The visual reflectance R2 of the black printing unit 14 at the interface with the transparent substrate 11 can be adjusted by the type and film thickness of the material (black ink or the like) constituting the black printing unit 14. However, R2 is usually in the range of 0.3% to 0.8%, and it is difficult to adjust it depending on the type of ink, the film thickness, and the like.

(Measurement of lateral visual reflectance Rs)
As for the visual reflectance of the side surface, the spectral reflectance of the side surface was acquired by a microspectroscopy (USPM RUIII manufactured by Olympus Corporation). When performing the measurement, the position and angle of the substrate having the maximum reflectance were obtained in advance, and the adjustment was made so that the correct specular reflectance could be obtained. From the spectral reflectance, the visual reflectance (stimulation value Y of reflection defined in JIS Z8701) and the tint (L ^* a ^* b ^* ) were obtained.

(Relationship between main surface and side visual reflectance)
In the present embodiment, the ratio (Rs / Rtot) of the visual reflectance Rtot to the visual reflectance Rs is preferably 1 to 3, preferably 1 to 2. By setting such a range, the difference in color tone between the main surface and the side surface becomes small, the visual recognition becomes more natural, and the discomfort becomes less. It is preferable that Rs is larger than Rtot. This is because when Rs is smaller than Rtot, it becomes difficult to visually recognize the color of the side surface surface, and the rear portion of the bonded housing can be seen through, which makes color matching difficult.

Regarding the tint, the reflection color b ^{* on} the side surface should be larger than the reflection color b ^* on the main surface, and the reflection color a ^* on the side surface is the reflectance a ^* on the main surface ^. It was found that the one with the same code as is more naturally visible. This is because the reflectance of the side surface measures specular reflection, but when actually visually recognizing it, the side surface is viewed at an extremely high angle, and it is presumed that the difference is due to the difference. That is, it was found that the color tone in specular reflection should satisfy the above relationship in order to be visually recognized naturally when viewed from a high angle. Specifically, the b ^{* on} the side surface is 1.5 times or more, preferably 2 times or more the b ^* on the main surface.

(Transparent substrate)
The transparent substrate 11 is not particularly limited as long as it is made of a transparent material that is generally required to be imparted with low reflectivity by a low-reflection film, and is, for example, glass, resin, or a combination thereof (composite material, laminated). Materials, etc.) are preferably used. Further, the form of the transparent substrate 11 is not particularly limited, and may be, for example, a rigid plate shape, a flexible film shape, or the like.

Examples of the resin substrate used as the transparent substrate 11 include an acrylic resin substrate such as polymethylmethacrylate, an aromatic polycarbonate resin substrate such as carbonate of bisphenol A, and an aromatic polyester resin substrate such as polyethylene terephthalate.

Examples of the polymer film (film-like transparent substrate 11) include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, polyvinyl chloride films, acrylic resin films, polyether sulfone films, and polyarylates. Examples include films and polycarbonate films.

As the glass substrate used as the transparent substrate 11, a substrate made of general glass containing silicon dioxide as a main component, for example, glass such as soda lime silicate glass, aluminosilicate glass, borosilicate glass, non-alkali glass, and quartz glass. Can be mentioned.

When a glass substrate is used as the transparent substrate 11, the composition of the glass is preferably a composition that can be strengthened by molding or chemical strengthening treatment, and preferably contains sodium.

The composition of the glass is not particularly limited, and glass having various compositions can be used. For example, aluminosilicate glass having the following composition in molar% notation based on oxides can be mentioned. For example, "containing 0 to 15% of MgO" means that MgO may be contained up to 15%, although it is not essential.

(I) SiO ₂ is 50 to 80%, Al ₂ O ₃ is 2 to 25%, Li ₂ O is 0 to 10%, Na ₂ O is 0 to 18%, K ₂ O is 0 to 10%, and Mg O is added. Glass containing 0-15%, CaO 0-5% and ZrO ₂ 0-5%

(Ii) SiO ₂ is 50 to 74%, Al ₂ O ₃ is 1 to 10%, Na ₂ O is 6 to 14%, K ₂ O is 3 to 11%, Mg O is ₂ to 15%, and Ca O is 0 to 0. Contains 6% and ZrO ₂ from 0 to 5%, total content of SiO ₂ and Al ₂ O ₃ is 75% or less, total content of Na ₂ O and K ₂ O is 12 to 25%, MgO and Glass with a total CaO content of 7-15%

(Iii) SiO ₂ is 68 to 80%, Al ₂ O ₃ is 4 to 10%, Na ₂ O is 5 to 15%, K ₂ O is 0 to 1%, Mg O is 4 to 15%, and ZrO ₂ is 0. Glass containing ~ 1%

(Iv) SiO ₂ is 67 to 75%, Al ₂ O ₃ is 0 to 4%, Na ₂ O is 7 to 15%, K ₂ O is 1 to 9%, Mg O is 6 to 14%, and ZrO ₂ is 0. It contains ~ 1.5%, the total content of SiO ₂ and Al ₂ O ₃ is 71 to 75%, the total content of Na ₂ O and K ₂ O is 12 to 20%, and contains CaO. Glass whose content is less than 1%

As the transparent substrate 11, a glass substrate is preferable.
The method for manufacturing the glass substrate is not particularly limited. It can be produced by putting a desired glass raw material into a melting furnace, heating and melting it at 1500 to 1600 ° C. to clarify it, and then supplying it to a molding apparatus to form the molten glass into a plate shape and slowly cooling it. The method for forming the glass substrate is not particularly limited, and for example, a down draw method (for example, an overflow down draw method, a slot down method, a redraw method, etc.), a float method, a rollout method, a press method, and the like can be used. ..

When a glass substrate is used as the transparent substrate 11, in order to increase the strength of the obtained substrate 1 with a low reflection film, the main surface of the glass substrate (for example, the main surface subjected to the antiglare treatment described later) is chemically treated. It is preferably chemically tempered glass that has been tempered.

The chemical strengthening treatment method is not particularly limited, and the main surface of the glass substrate is ion-exchanged to form a surface layer in which compressive stress remains. Specifically, alkali metal ions having a small ionic radius (for example, Li ion and Na ion) contained in the glass near the main surface of the substrate at a temperature below the glass transition point are used, and alkali metal ions having a larger ionic radius (for example, Li ion and Na ion) For example, Li ion is replaced with Na ion or K ion, and Na ion is replaced with K ion). As a result, compressive stress remains on the main surface of the glass substrate, and the strength of the glass substrate is improved.

The glass substrate as the transparent substrate 11 preferably satisfies the following conditions. Such conditions can be satisfied by performing the above-mentioned chemical strengthening treatment.

That is, the surface compressive stress (hereinafter referred to as CS) of the glass substrate is preferably 400 MPa or more and 1200 MPa or less, more preferably 650 MPa or more and 950 MPa or less, and further preferably 700 MPa or more and 900 MPa or less. When CS is 400 MPa or more, it is sufficient as a practical strength. Further, if the CS is 1200 MPa or less, it can withstand its own compressive stress and there is no concern that it will break naturally. When the substrate 10 with a low reflective film of the present invention is used as the front substrate (cover glass) of the display device, the CS of the glass substrate is particularly preferably 700 MPa or more and 850 MPa or less.

Further, the depth of the stress layer of the glass substrate (hereinafter referred to as DOL) is preferably 15 to 60 μm, more preferably 15 to 50 μm, still more preferably 20 to 40 μm. If the DOL is 15 μm or more, there is no concern that it will be easily scratched and destroyed even if a sharp jig such as a glass cutter is used. Further, if the DOL is 40 μm or less, the substrate itself can withstand the compressive stress and there is no concern that it will spontaneously break. When the substrate 10 with a low reflective film of the present invention is used as a front substrate (cover glass) of a display device or the like, the DOL of the glass substrate is particularly preferably 25 μm or more and 35 μm or less.

The thickness of the transparent substrate 11 can be appropriately selected depending on the intended use. For example, in the case of a plate-shaped transparent substrate 11 such as a resin substrate or a glass substrate, the thickness is preferably 0.1 to 5 mm, more preferably 0.2 to 2 mm. When the transparent substrate 11 is in the form of a film such as a polymer film, its thickness is preferably 50 to 200 μm, more preferably 75 to 150 μm.

When a glass substrate is used as the transparent substrate 11 and the chemical strengthening treatment is performed, the thickness of the glass substrate is usually preferably 5 mm or less, and more preferably 3 mm or less in order to effectively perform this treatment.

Further, the dimensions when the transparent substrate 11 is a glass substrate can be appropriately selected depending on the intended use. When used as a cover glass for mobile devices, it is 30 mm x 50 mm to 300 x 400 mm and has a thickness of 0.1 to 2.5 mm. When used as a cover glass for display devices, it is 50 mm x 100 mm to 2000 x 1500 mm. The thickness is preferably 0.5 to 4 mm. The transparent substrate 11 may have a bent portion, and may have an opening or a recess.

(Anti-glare treatment)
The substrate 10 with a low-reflection film may be formed so that the main surface of the transparent substrate 11 has an uneven shape in order to impart antiglare properties. It is preferable that the main surface having an uneven shape is at least one main surface of the transparent substrate 11, and the main surface on the side provided with at least the first low-reflection film 12 is a surface having an uneven shape.

A specific configuration of the substrate with a low-reflection film subjected to such an antiglare treatment is illustrated in FIG. The substrate 10a with a low-reflection film of FIG. 3 includes a transparent substrate 11a whose main surface is antiglare-treated, and a first low-reflection film 12a formed on the antiglare-treated surface. It is composed of a second low-reflection film 13 formed on the side surface of the transparent substrate 11a and a black printing portion 14. In FIG. 3, the low-reflection film 12a is formed so as to fill the uneven shape formed on the main surface of the transparent substrate 11a, but is not limited to this, and the uneven shape formed on the main surface of the transparent substrate 11a is not limited to this. It may be formed so as to follow.

As a method for forming the uneven shape, a known method such as antiglare treatment can be applied. As the antiglare treatment, for example, when a glass substrate is used as the transparent substrate 11, a method of forming an uneven shape having a desired surface roughness on at least one main surface of the glass substrate by chemical or physical surface treatment, or A method of applying a coating treatment such as a wet coat can be used.

Specific examples of the method of chemically performing the antiglare treatment include a method of performing a frost treatment. The frost treatment can be carried out, for example, by immersing a glass substrate as an object to be treated in a mixed solution of hydrogen fluoride and ammonium fluoride.

Further, as a method of physically performing the antiglare treatment, for example, a so-called sandblast treatment in which crystalline silicon dioxide powder, silicon carbide powder or the like is sprayed on the main surface of the glass substrate with pressurized air, or crystalline silicon dioxide powder , A method of rubbing a brush to which silicon carbide powder or the like is attached with a water-moistened brush can be used.

Among these, the frost treatment is preferable as a method for performing an antiglare treatment on a glass substrate because microcracks are less likely to occur on the surface of the object to be treated and mechanical strength is less likely to decrease.

The main surface of the glass substrate that has been chemically or physically antiglare-treated in this way is preferably etched in order to adjust the surface shape. As the etching process, for example, a method of immersing a glass substrate in an etching solution which is an aqueous solution of hydrogen fluoride and chemically etching can be used. The etching solution may contain an acid such as hydrochloric acid, nitric acid, or citric acid in addition to hydrogen fluoride. By containing these acids, it is possible to suppress the local generation of precipitates due to the reaction between cations such as Na ions and K ions contained in the glass substrate and hydrogen fluoride, and the surface to be etched is treated. It is made to proceed uniformly within.

When performing the etching process, the etching amount is adjusted by adjusting the concentration of the etching solution, the immersion time of the glass substrate in the etching solution, etc., thereby adjusting the haze value of the antiglare-treated surface of the glass substrate to a desired value. Can be adjusted to. Further, when the antiglare treatment is performed by a physical surface treatment such as sandblasting, cracks may occur, and such cracks can be removed by the etching treatment. In addition, the etching treatment also has the effect of suppressing glare on the substrate 1 with a low-reflection film. The glare means that when a substrate with a low-reflection film is used as the front substrate of the display element, many light particles are observed on the surface of the front substrate, which hinders visibility. The more the glare is suppressed, the more difficult it is to observe light particles, and the better the visibility.

The surface roughness (root mean square roughness, RMS) of the main surface of the glass substrate after the antiglare treatment and the etching treatment are preferably 0.01 to 0.5 μm. The surface roughness (RMS) is more preferably 0.01 to 0.3 μm, still more preferably 0.01 to 0.2 μm. By setting the surface roughness (RMS) in the above range, the haze value of the glass substrate after the antiglare treatment can be adjusted to 1 to 30%, and as a result, the obtained substrate 1 with a low reflection film has excellent antiglare properties. Can be granted. The haze value is a value defined by JIS K 7136: (2000).

Surface roughness (RMS) can be measured according to the method specified in JIS B 0601: (2001). Specifically, a laser microscope (trade name: VK-9700, manufactured by KEYENCE CORPORATION) is used to set a viewing range of 300 μm × 200 μm with respect to the measurement surface of the glass substrate after antiglare treatment, which is a sample. Measure the height information of. The surface roughness (RMS) can be calculated by performing cutoff correction on the measured value and obtaining the root mean square of the obtained height. As the cutoff value, it is preferable to use 0.08 mm.

The surface of the glass substrate after the antiglare treatment and the etching treatment has an uneven shape, and when observed from above the surface of the glass substrate, it looks like a circular depression. The size (diameter) of the opening of the circular recess observed in this way is preferably 1 μm or more and 10 μm or less. Within this range, both glare prevention and anti-glare properties can be achieved. The antiglare property means a performance of reducing the glare of the reflected light due to the reflection of the light source by mainly scattering the reflected light, and the higher the antiglare property, the more the glare can be reduced.

In a normal usage environment, light is incident from various angles. The evaluation of the visibility between the main surface and the side surface is also performed under such a situation. It has been found that the visibility of the main surface and the side surface under normal usage environment correlates with the visual reflectance measured by the above-mentioned SCI method. Further, the visual reflectance does not change depending on the presence or absence of the antiglare treatment of the transparent substrate 11. Therefore, it is considered that the visibility of the main surface and the side surface is not affected by the presence or absence of the antiglare treatment on the transparent substrate 11.

(Low reflective film)
In the substrate 10 with a low-reflection film of the present embodiment, the first low-reflection film 12 is formed on one main surface of the transparent substrate 11, and the second low-reflection film 13 is formed on the side surface of the transparent substrate 11. When the transparent substrate 11 is subjected to the antiglare treatment, it is preferable that the first low reflection film 12 is formed on the main surface on which the antiglare treatment is performed.

The configuration of the first low-reflection film 12 and the second low-reflection film 13 is not particularly limited as long as it can suppress the reflection of light within a predetermined range, and for example, a high refractive index layer and a low refractive index layer. Can be laminated. Here, the high refractive index layer means, for example, a layer having a refractive index of 1.9 or more for light having a wavelength of 550 nm, and a low refractive index layer means a layer having a refractive index of 1.6 or less for light having a wavelength of 550 nm. ..

The number of layers of the high-refractive index layer and the low-refractive index layer in the first low-reflective film 12 and the second low-reflective film 13 may be one layer each, but two or more layers each. It may be a configuration including. In the case of a configuration including one high refractive index layer and one low refractive index layer, it is preferable that the high refractive index layer and the low refractive index layer are laminated in this order on the main surface of the transparent substrate 11. Further, in the case of a configuration including two or more layers each having a high refractive index layer and a low refractive index layer, it is preferable that the high refractive index layer and the low refractive index layer are alternately laminated in this order.

In order to enhance the low reflection performance, the first low reflection film 12 and the second low reflection film 13 are preferably a laminated body in which a plurality of layers are laminated, and the laminated body is, for example, 2 in total. Lamination of 2 or more and 8 or less layers is preferable, 2 or more and 6 or less layers are more preferable, and 2 or more and 4 or less layers are further preferable. As described above, the laminated body is preferably one in which high refractive index layers and low refractive index layers are alternately laminated, and the total number of layers of high refractive index layers and low refractive index layers is in the above range. Is preferable. Further, the layer may be added within a range that does not impair the optical characteristics. For example, in order to prevent Na diffusion from the glass substrate, a SiO ₂ film may be inserted between the glass and the first layer of the low reflection film provided on the glass side.

In order to control the visual reflectance R1 of the first low-reflection film 12 to a desired range, the layer thickness of the high-refractive index layer and the layer thickness of the low-refractive index layer of the first low-reflection film 12 are appropriately adjusted. It is preferable to be done. Similarly, in order to control the visual reflectance Rs of the second low-reflection film 13 within a desired range, the thickness of the high-refractive index layer and the layer of the low-refractive index layer of the second low-reflection film 13 are controlled. The thickness is preferably adjusted as appropriate.

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

From the viewpoint of productivity and refractive index, it is preferable that the high refractive index layer is made of one selected from niobium oxide, tantalum oxide, and silicon nitride, and the low refractive index layer is made of silicon oxide.

(Anti-fouling film)
In the substrate 10 with a low-reflection film of the present invention, it is preferable to further form an antifouling film on at least one upper surface of the first low-reflection film 12 and the second low-reflection film 13. FIG. 4 illustrates a substrate 20 with a low-reflection film, which has the same configuration as the substrate 10a with a low-reflection film shown in FIG. 3 and further has an antifouling film. The substrate 20 with a low-reflection film further forms an antifouling film 24 on a transparent substrate 21, a first low-reflection film 22 and a second low-reflection film 23 provided on one of the main surfaces thereof. It is a thing.

The constituent material of the antifouling film can be appropriately selected from materials capable of imparting antifouling property, water repellency, and oil repellency. Specific examples thereof include fluorine-containing organosilicon compounds. The fluorine-containing organosilicon compound can be used without particular limitation as long as it can impart antifouling property, water repellency and oil repellency.

As the fluorine-containing organosilicon compound, for example, an organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group can be preferably used. The polyfluoropolyester group is a divalent group having a structure in which polyfluoroalkylene groups and etheric oxygen atoms are alternately bonded.

Commercially available products of fluorine-containing organic silicon compounds having one or more groups selected from the group consisting of polyfluoropolyether groups, polyfluoroalkylene groups, and perfluoroalkyl groups include KP-801, KY-178, and KY-. 130, KY-185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Optool DSX, Optool AES (trade name, all manufactured by Daikin Co., Ltd.) and the like can be preferably used.

Fluorine-containing organosilicon compounds are generally stored by mixing with a solvent such as a fluorine-based solvent in order to suppress deterioration due to a reaction with moisture in the atmosphere, but include these solvents. If it is subjected to the film forming process as it is, the durability of the obtained thin film may be adversely affected. Therefore, when the antifouling film is formed by the vacuum vapor deposition method according to the procedure described later, it is preferable to use a fluorine-containing organosilicon compound which has been subjected to a solvent removal treatment in advance before heating in a heating container.

Here, as the solvent used when preserving the above-mentioned fluorine-containing organosilicon compound, for example, polyfluorohexane, metaxylene hexafluoride (C ₆ H ₄ (CF ₃ ) ₂ ), hydrofluoropolyether. , HFE7200 / 7100 (trade name, manufactured by Sumitomo 3M Ltd., HFE7200 is represented by the formula: C ₄ F ₉ -OC ₂ H ₅ , HFE 7100 is represented by the formula: C ₄ F _9- O-CH ₃ ), etc. Can be mentioned. For example, the concentration of the solvent contained in the solution of the fluorine-containing organosilicon compound is preferably 1 mol% or less, more preferably 0.2 mol% or less. It is particularly preferable to use a solvent-free fluorine-containing organosilicon compound.

The treatment for removing the solvent from the fluorine-containing organosilicon compound solution containing the fluorine-based solvent can be carried out, for example, by vacuum exhausting the container containing the solution of the fluorine-containing organosilicon compound. The time for vacuum exhaust varies depending on the exhaust line, the exhaust capacity of the vacuum pump, the amount of the solution, and the like, and is not limited. For example, vacuum exhaust may be performed for 10 hours or more.

When forming the antifouling film made of the above-mentioned fluorine-containing organosilicon compound, it is preferable to use a vacuum vapor deposition method for the film formation. When the vacuum vapor deposition method is used, the solvent removal treatment is performed at room temperature after introducing the fluorine-containing organosilicon compound solution into the heating container of the film forming apparatus for forming the antifouling film and before raising the temperature. It can be carried out by vacuum exhausting the inside. In addition, the solvent can be removed in advance by an evaporator or the like before the introduction into the heating container.

Fluorine-containing organosilicon compounds having a low solvent content or not containing a solvent are more likely to be deteriorated by contact with the atmosphere than those containing a solvent. Therefore, as the storage container for the fluorine-containing organosilicon compound having a low (or no solvent content), use a container in which the inside of the container is replaced with an inert gas such as nitrogen and sealed, and the exposure time to the atmosphere when handling is used. Is preferably shortened.

Specifically, it is preferable to introduce the fluorine-containing organosilicon compound into the heating container of the film forming apparatus for forming the antifouling film immediately after opening the storage container. After the introduction, it is preferable to evacuate the inside of the heating container or replace it with an inert gas such as nitrogen or a rare gas to remove the atmosphere (air) contained in the heating container. It is more preferable that, for example, the storage container and the heating container are connected by a pipe with a valve so that the storage container (storage container) can be introduced into the heating container of the film forming apparatus without coming into contact with the atmosphere.

Then, after introducing the fluorine-containing organosilicon compound into the heating container and replacing the inside of the container with a vacuum or an inert gas, it is preferable to immediately start heating for film formation.

In the present invention, the film thickness of the antifouling film 24 formed on the second low-reflection film 22 is not particularly limited, but is preferably 2 to 20 nm, more preferably 2 to 15 nm. It is more preferably 2 to 10 nm. When the film thickness is 2 nm or more, the antifouling film 24 uniformly covers the surfaces of the low-reflection films 22 and 23, and the film can withstand practical use from the viewpoint of abrasion resistance. Further, when the film thickness is 20 nm or less, the optical characteristics such as the haze value in the state where the antifouling film is laminated are good.

The antifouling film film forming method includes a vacuum vapor deposition method, an ion beam assisted vapor deposition method, an ion plate method, a sputtering method, a dry method such as a plasma CVD method, a spin coating method, a dip coating method, a casting method, and a slit coating method. Both wet methods such as the method and the spray method can be used. From the viewpoint of scratch resistance, it is preferable to use a dry film forming method.

(Black printing section)
The substrate 10 with a low-reflection film of the present invention may include a black printing portion 14 on a part of the other main surface of the transparent substrate 11 that forms the first low-reflection film 12. The black printing unit 14 is a light shielding unit that enhances the visibility and aesthetics of the display by shielding a portion that enters the view and interferes with the view when viewing the display, such as a wiring circuit arranged on the outer peripheral portion of the display panel. It may be a printing part such as a character or a pattern. The black printing portion may be formed before the first low-reflection film 12 and the second low-reflection film 13 are formed, or may be formed after these low-reflection films are formed.

In the present invention, the "region having a black printed portion" means a region where the substrate with a low-reflection film has a black printed portion in a vertical cross section (a cross section along the thickness direction). In the following description, the "region having a black printed portion" is also referred to as a "region having a black printed portion". Further, a region in which the substrate with a low-reflection film does not have a black printed portion in a vertical cross section is also referred to as a “region having no black printed portion”.

The black printing unit 14 is formed by a method of printing black ink. Examples of the printing method include a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, a screen method, an inkjet method, etc., which can be easily printed and printed on various substrates. In addition, the screen printing method is preferable because it can be printed according to the size of the base material.

Black ink can be used without particular limitation. As the black ink, an inorganic ink containing a fired ceramic body or the like and an organic ink containing a colorant such as a dye or pigment and an organic resin can be used.

Ceramics contained in the black inorganic ink include oxides such as chromium oxide and iron oxide, carbides such as chromium carbide and tungsten carbide, carbon black, and mica. The black printing unit 14 is obtained by melting the ink composed of the ceramics and silica, printing in a desired pattern, and then firing. This inorganic ink requires melting and firing steps, and is generally used as a glass-only ink.

The organic ink is a composition containing a black dye or pigment and an organic resin. Examples of the organic resin include epoxy resin, acrylic resin, polyethylene terephthalate, polyether sulfone, polyarylate, polycarbonate, transparent ABS resin, phenol resin, acrylonitrile-butadiene-styrene resin, polyurethane, polymethyl methacrylate, polyvinyl, and Examples thereof include homopolymers such as polyvinyl butyral, polyether ether ketone, polyethylene, polyester, polypropylene, polyamide and polyimide, and resins composed of copolymers of monomers of these resins and copolymerizable monomers. Further, the dye or pigment can be used without particular limitation as long as it is black.

Since the firing temperature of the inorganic ink and the organic ink is low, it is preferable to use the organic ink. Further, from the viewpoint of chemical resistance, an organic ink containing a pigment is preferable.

Here, the fact that the print is black means that the visual reflectance R2 calculated by the above method for the black printed portion is 1% or less, preferably 0.8% or less, and more preferably 0.6% or less. Therefore, the chromaticity value (a ^* , b ^* ) defined by JIS Z8781-4: 2013 measured under the light source of D65 is (0 ± 2,0 ± 2). The chromaticity values (a ^* , b ^* ) are preferably (0 ± 1.5, 0 ± 1.5), and more preferably (0 ± 1, 0 ± 1).

Since the substrate 10 with a low-reflection film of the present embodiment has a low-reflection film having an adjusted visual reflectance on the main surface and side surfaces, the black printing portion for light shielding and the like in the outer peripheral portion extends from the side surface. It is difficult to confirm a large change in visibility. Therefore, when the substrate 10 with a low reflection film of the present embodiment is used as a front substrate such as a cover glass of a display device, the visibility of the display can be improved and good design and aesthetics can be imparted.

[Manufacturing method of substrate with low reflective film]
(Formation of low reflective film)
First, the transparent substrate 11 described above is prepared, and then a low-reflection film is formed on one of the main surfaces and side surfaces of the transparent substrate 11.

The method for forming the respective layers constituting the first low-reflection film 12 and the second low-reflection film 13 is not particularly limited, and various film-forming methods can be used. For example, a physical vapor deposition method such as a vacuum vapor deposition method, an ion beam assisted vapor deposition method, an ion plate method, a sputtering method, or a plasma CVD method can be used. Among these film forming methods, it is preferable to use the sputtering method because a dense and highly durable film can be formed. In particular, it is preferable to form a film by a sputtering method such as a pulse sputtering method, an AC sputtering method, or a digital sputtering method.

In this film formation, the first low-reflection film 12 and the second low-reflection film 13 may be formed in separate steps or may be formed at the same time. When they are formed at the same time, the stacking direction is different between the main surface and the side surface, so that the film formation conditions should be paid special attention so that a desired low-reflection film can be formed.

When a low-reflection film is formed by, for example, a pulse sputtering method, a transparent substrate 11 such as a glass substrate is arranged in a chamber having a mixed gas atmosphere of an inert gas and an oxygen gas to obtain a desired composition. The target is selected and a film is formed. At this time, the gas type of the inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used.

The pressure in the chamber due to the mixed gas of the inert gas and the oxygen gas is not particularly limited, but by setting it in the range of 0.5 Pa or less, the surface roughness of the film to be formed is in a preferable range. It is easy to say. This is considered to be due to the following reasons. That is, when the pressure in the chamber due to the mixed gas of the inert gas and the oxygen gas is 0.5 Pa or less, the mean free path of the film-forming molecules is secured, and the film-forming molecules reach the substrate with more energy. .. Therefore, it is considered that the rearrangement of the film-forming molecules is promoted and a film having a relatively dense and smooth surface is formed. The lower limit of the pressure in the chamber due to the mixed gas of the inert gas and the oxygen gas is not particularly limited, but is preferably 0.1 Pa or more, for example.

When a high refractive index layer and a low refractive index layer are formed by the pulse sputtering method, the layer thickness of each layer can be adjusted by, for example, adjusting the discharge power, adjusting the film forming time, and the like.

Further, when the film is formed at the same time by sputtering, as shown in FIG. 5, a spacer 52 is provided between the transparent substrate 11 and the carrier substrate 51 holding the transparent substrate 11 in the chamber 50, and the transparent substrate 11 and the carrier substrate are formed. It may be held at a predetermined distance from the 51, and in this state, sputtering may be performed using the sputtering target 53 to form a film.

At this time, a film thickness that does not depend on the size of the spacer 52 is deposited on the main surface, but on the side surface, a component that directly adheres to the side surface of the transparent substrate 11 from the target 53 and reflection from the target 53 by the carrier substrate 51. Then, there is a component that forms a film on the side surface of the transparent substrate 11. This component ratio can be changed by the distance between the target and the transparent substrate and the distance between the carrier substrate and the transparent substrate. As a result, the relationship between the film thickness of the main surface and the film thickness of the side surface can be changed, and the color of the side surface can be changed while the color of the main surface is fixed. This method can be effectively used by a method in which film particles fly in a relatively high vacuum. If it is a physical film formation, it can be carried out by a vacuum vapor deposition method, an ion beam assisted vapor deposition method, an ion plate method, or a sputtering method.

Since the plasma CVD method has a relatively low vacuum and the mean free path of the film particles is short, it is difficult to control the color difference between the side surface and the main surface by this method. The mean free path of the film particles is determined by the pressure in the chamber during film formation, and is preferably 1 Pa or less, more preferably 0.5 Pa or less. At this time, it can be carried out by the same operation as normal sputtering except that the above interval is provided.

By holding the transparent substrate 11 and the carrier substrate 51 so as to have a predetermined distance in this way, in addition to the main surface of the transparent substrate 11 on the sputtering target side, the transparent substrate is reflected from the carrier substrate 51 or the like. A film can be formed on the side surface of 11 at the same time. At this time, if the distance between the sputtering target 53 and the transparent substrate 11 is 50 to 90 mm, the distance between the transparent substrate 11 formed by the spacer 52 and the carrier substrate 51 may be, for example, although it depends on other film forming conditions. 1 to 6 mm is preferable.

The substrate with a low-reflection film thus obtained is suitable as a front substrate for a display. That is, in a display device having a display and a substrate with a low-reflection film of the present embodiment provided as a front substrate on the front surface of the display, there is a difference between the visibility of the display and the visibility of the side surface of the front substrate. It looks small and natural. That is, by using this substrate with a low-reflection film, it is possible to improve the visibility of the display of the display device, and it is possible to impart excellent design and aesthetics.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

In the following, first, the processing procedure of the glass substrate will be described. In both the examples and the comparative examples, Dragon Trail (trade name, manufactured by Asahi Glass Co., Ltd., thickness 1.3 mm, hereinafter also referred to as "DT"), which is a glass substrate for chemical strengthening, was used as the glass substrate.

(Example 1)
(1) First, an acid-resistant protective film (hereinafter, also simply referred to as “protective film”) is attached to one main surface of the DT, and then the substrate is immersed in a 3 wt% hydrogen fluoride solution for 3 minutes for etching. By doing so, the dirt adhering to the substrate surface was removed.

Next, the decontaminated glass substrate was immersed in a mixed solution of 15% by weight of hydrogen fluoride and 15% by weight of potassium fluoride for 3 minutes to perform frost treatment (antiglare treatment), and then 10% by weight. The haze value was adjusted to 25% by immersing in a% hydrogen fluoride solution for 6 minutes. The haze value was measured using a haze meter (trade name: HZ-V3, manufactured by Suga Test Instruments Co., Ltd.) based on JIS K 7136.

(2) Next, the substrate was cut into a size of 150 mm × 250 mm. The chamfer was C0.2 with a No. 600 grindstone (manufactured by Tokyo Dia). At this time, the rotation speed of the grindstone was 6500 rpm, the moving speed of the grindstone was 5000 mm / min, and the cutting allowance was 0.2 mm.

(3) Next, the chemical strengthening treatment was performed according to the following procedure.
The substrate from which the protective film has been removed is immersed in potassium nitrate melted by heating to 450 ° C. for 2 hours, then pulled up from the molten salt and cooled to room temperature in 1 hour to perform chemical strengthening treatment, resulting in surface compressive stress ( A chemically strengthened glass substrate having a CS) of 730 MPa and a stress layer depth (DOL) of 30 μm was obtained.

(4) Then, this substrate was immersed in an alkaline solution (Sunwash TL-75 manufactured by Lion Corporation) for 4 hours.

(5) Next, screen printing was performed on the surface of the substrate that was not antiglare-treated by the following procedure. A black frame-shaped print having a width of 2 cm was printed on the four sides of the outer peripheral portion of the main surface of the glass substrate which was not antiglare-treated to form a black printed portion. First, a black ink (GLSHF (trade name, manufactured by Teikoku Printing Inks)) was applied to a thickness of 5 μm by a screen printing machine, and then held at 150 ° C. for 10 minutes to dry to form a first printing layer. .. Next, black ink was applied to a thickness of 5 μm on the first print layer in the same procedure as above, and then held at 150 ° C. for 40 minutes to dry to form a second print layer. In this way, a black printing portion in which the first printing layer and the second printing layer were laminated was formed, and a glass substrate having a black printing portion on the outer peripheral portion of one main surface was obtained.

(6) Next, low-reflection films were formed on the main surface and the side surface, which were antiglare-treated by the following method.
First, a 2 mm thick, 50 mm square PEEK resin was adhered to a central portion sufficiently far from the side surface of the glass substrate with double-sided tape. The PEEK resin portion was attached to the center of a large glass (called a carrier substrate) having a thickness of 2 mm and a square size of 1000 mm. The material of the carrier substrate at this time is not particularly limited, and a resin or metal material may be used. By doing so, the incident angle of the film-forming particles reflected by the carrier substrate on the back surface and incident on the side surface of the substrate can be controlled, and the film formation on the side surface can be performed at the same time.

First, the distance between the target and the substrate was set to 70 mm with the substrate attached to the carrier substrate.

Next, while introducing a mixed gas obtained by mixing 10% by volume of oxygen gas with argon gas, using a niobium oxide target (manufactured by AGC Ceramics Co., Ltd., trade name: NBO target), pressure 0.3 Pa, frequency 20 kHz, power. Pulse sputtering was performed under the conditions of a density of 3.8 W / cm ² and an inversion pulse width of 5 μsec to form a high refractive index layer made of niobium oxide (niobia) having a thickness of 13 nm on the main surface. The thickness of the film can be calculated by fitting the spectrum of R1 calculated as described above from the equation of interference of the optical thin film using the refractive index of the material constituting the film. The calculation of the film thickness is not limited to this, and the film thickness may be obtained from the value of the crystal oscillator that can indirectly grasp the film thickness during sputtering.

Next, while introducing a mixed gas obtained by mixing 40% by volume of oxygen gas with argon gas, using a silicon target, conditions of pressure 0.3 Pa, frequency 20 kHz, power density 3.8 W / cm ² , and inverting pulse width 5 μsec. A low refractive index layer made of silicon oxide (silica) having a thickness of 35 nm was formed on the high refractive index layer.

Next, in the same manner as the first layer, a high refractive index layer made of niobium oxide (niobium) having a thickness of 115 nm was formed on the low refractive index layer.

Then, in the same manner as the second layer, a low refractive index layer made of silicon oxide (silica) having a thickness of 80 nm was formed.

In this way, a low-reflection film in which niobium oxide (niobia) and silicon oxide (silica) were alternately laminated in a total of four layers was formed.

As for the film thickness, the low-reflection film was formed so that the first low-reflection film and the second low-reflection film had the same film thickness.

(7) Next, an antifouling film was formed by the following method. The substrate was put in while being attached to the carrier substrate, and a film was formed on the main surface on which the low-reflection film was formed, and at the same time, an antifouling film was efficiently formed on the side surface. First, as a material for the antifouling film, a material for forming a fluorine-containing organosilicon compound film was introduced into a heating container. After that, the inside of the heating container was degassed with a vacuum pump for 10 hours or more to remove the solvent in the solution to obtain a composition for forming a fluorine-containing organosilicon compound film (hereinafter referred to as an antifouling film forming composition). ..

Next, the heating container containing the antifouling film forming composition (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KY-185) is heated to 270 ° C., and after reaching 270 ° C., it takes 10 minutes until the temperature stabilizes. It kept that state. Next, after the glass substrate on which the low-reflection film is formed is installed in the vacuum chamber, the nozzle connected to the heating container containing the antifouling film-forming composition is directed toward the low-reflection film of the glass substrate. The composition for forming an antifouling film was supplied and a film was formed.

The film formation was carried out while measuring the film thickness with a crystal oscillator monitor installed in the vacuum chamber until the film thickness of the fluorine-containing organosilicon compound film on the low-reflection film became 4 nm. Next, the glass substrate taken out from the vacuum chamber was placed on a hot plate with the fluorine-containing organosilicon compound film surface facing upward, and heat-treated at 150 ° C. in the air for 60 minutes.

(8) By the above operation, a glass substrate 1 with a low reflection film having a predetermined film structure formed on the glass substrate was manufactured.

(Example 2)
In the description of Example 1, the glass substrate 2 with a low reflection film was manufactured by the same operation as in Example 1 except that (7) the film formation treatment of the antifouling film was not performed.

(Example 3)
In the description of Example 1, (1) the antiglare treatment is not performed, (6) the distance between the target and the substrate is set to 60 mm during the film formation treatment of the low reflection film, and (7) the film formation of the antifouling film. Example 1 except that the resin composition used during the treatment was an antifouling film forming composition (Optool DCY manufactured by Daikin Co., Ltd.) and the thickness of the PEEK resin between the glass substrate and the carrier substrate was 3 mm. The glass substrate 3 with a low reflective film was manufactured by the same operation as in the above.

(Example 4)
In the description of Example 1, except that (6) the distance between the target and the substrate was set to 80 mm and the thickness of the PEEK resin between the glass substrate and the carrier substrate was set to 4 mm during the film formation treatment of the low reflection film. , A glass substrate 4 with a low reflective film was manufactured by the same operation as in Example 1.

(Example 5)
(6) In the film forming process of the low-reflection film in the description of Example 1, the glass substrate 5 with the low-reflection film is manufactured by the same operation as in Example 1 except that the low-reflection film is the following laminated film. did.

As the low-reflection film, first, while introducing a mixed gas obtained by mixing 50% by volume of nitrogen gas with argon gas, using a silicon target, a pressure of 0.3 Pa, a frequency of 20 kHz, and a power density of 3.8 W / cm ² , Pulse sputtering was performed under the condition of an inverting pulse width of 5 μsec to form a high refractive index layer made of silicon nitride having a thickness of 15 nm.

Next, while introducing a mixed gas obtained by mixing 40% by volume of oxygen gas with argon gas, using a silicon target, conditions of pressure 0.3 Pa, frequency 20 kHz, power density 3.8 W / cm ² , and inverting pulse width 5 μsec. A low refractive index layer made of silicon oxide (silica) having a thickness of 70 nm was formed on the high refractive index layer.

Next, as the third layer, a high refractive index layer made of silicon nitride having a thickness of 17 nm is formed on the low refractive index layer in the same manner as in the first layer, and as the fourth layer, in the same manner as in the second layer. , A low refractive index layer made of silicon oxide (silica) having a thickness of 105 nm was formed.

Next, as the fifth layer, a high refractive index layer made of silicon nitride having a thickness of 15 nm is formed on the low refractive index layer in the same manner as in the first layer, and as the sixth layer, in the same manner as in the second layer. , A low refractive index layer made of silicon oxide (silica) having a thickness of 50 nm was formed.

Next, as the 7th layer, a high refractive index layer made of silicon nitride having a thickness of 120 nm is formed on the low refractive index layer in the same manner as the 1st layer, and as the 8th layer, the same as the 1st layer. A high refractive index layer made of silicon nitride having a thickness of 80 nm was formed on the low refractive index layer.

In this way, a low-reflection film in which a total of eight layers of silicon nitride and silicon oxide (silica) were alternately laminated was formed.

(Comparative Example 1)
In the description of Example 1, the distance between the glass substrate and the carrier substrate is increased except that the glass substrate is directly adhesively fixed to the carrier substrate in (6) the film formation process of the low reflection film (that is, without using PEEK resin). In the case of 0 mm), a substrate C1 with a low reflection film was obtained by the same operation as in Example 1.

(Comparative Example 2)
In the explanation of Example 1, the substrate C2 was obtained by the same operation as in Example 1 except that (6) the film formation treatment of the low reflection film was not performed.

(Comparative Example 3)
In the description of Example 1, except that (6) the distance between the target and the substrate was set to 180 mm and the thickness of the PEEK resin between the glass substrate and the carrier substrate was set to 30 mm during the film formation treatment of the low reflection film. , A glass substrate C3 with a low reflective film was manufactured by the same operation as in Example 1.

<Characteristics of substrate with low reflective film>
The following evaluations were carried out on the glass substrates with a low reflection film obtained in Examples 1 to 5 and Comparative Examples 1 to 3. These results are also shown in Table 1 together with the configuration of the substrate with a low-reflection film.

(Visual reflectance of the main surface)
The spectral reflectance is measured in SCI mode with a spectrocolorimeter (manufactured by Konica Minolta, model: CM-2600d) on the main surface of the substrate on which the black printed portion is formed on the back surface. , The visual reflectance Rtot (stimulation value Y of reflexes specified in JIS Z8701: 1999) was determined.

(Side visual reflectance, color)
The spectral reflectance of the side surface of the substrate was obtained with a microspectroscopy (USPM RUIII manufactured by Olympus Corporation). When performing the measurement, the position of the substrate having the maximum reflectance was obtained in advance, and adjustment was made so that the specular reflectance could be obtained. From the spectral reflectance, the visual reflectance Rs (stimulation value Y of the reflection specified in JIS Z8701: 1999) and the tint (L ^* a ^* b ^* ) were obtained.

(Contact angle)
A contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., device name) is made by dripping about 1 μL of pure water droplets on the surface of the glass substrate on the side where the low-reflection film is provided (Comparative Example 2 is the surface subjected to antiglare treatment). The contact angle with water was measured using DM-51).

(Evaluation of color difference between main surface and side surface)
A frame 0.5 mm larger than the glass substrate was prepared, and the glass substrate was placed and fixed so as to come to the center of the frame. The depth of the frame was 0.8 mm, and the structure was such that glass was exposed by about 0.5 mm. The color of the frame was black. In that state, the substrate was visually recognized from various angles under a fluorescent lamp, and it was visually confirmed whether the colors were smoothly connected from the main surface to the side surface. Five inspectors confirmed and judged good or bad.

From Table 1, in the glass substrate with the low reflective film of Examples 1 to 5, the visual reflectance of the main surface and the visual reflectance and chromaticity of the side surfaces each satisfy a predetermined range, and the main surface is satisfied. It was possible to suppress a large change in light reflection and color when the side surface was visually recognized, and the visibility was good. On the other hand, in the glass substrates with low reflection film of Comparative Examples 1 and 3 in which the visual reflectance and the chromaticity were out of the predetermined range, the light reflection and the change in color between the main surface and the side surface were significantly noticeable. , The visibility was poor. Further, in Comparative Example 2, it was found that the visual reflectance Rtot of the first low-reflection film was large, and the visibility of the display portion was lowered.

In the substrate with a low reflection film of the present invention, light reflection and changes in color are suppressed on the main surface and the side surfaces, and the changes are difficult to see. Therefore, the substrate with a low-reflection film of the present invention is suitable as a front substrate of a display device, and can impart excellent design and aesthetics as well as good display visibility.

10,10a ... Substrate with low-reflection film, 11,11a ... Transparent substrate, 12,12a ... First low-reflection film, 13 ... Second low-reflection film, 14 ... Black printing section

Claims (14)

A substrate with a low-reflection film, comprising a transparent substrate, a first low-reflection film provided on one main surface of the transparent substrate, and a second low-reflection film provided on a side surface of the transparent substrate. hand,
The visual reflectance R1 of the first low-reflective film provided on one of the main surfaces is 0.6% or less, and the visual reflectance Rs of the second low-reflection film provided on the side surface is 0.6% or less. Is 2.5% or less, the chromaticity a ^* is 0 to 4, and b ^* is 3 to 9, a substrate with a low reflection film. The substrate with a low-reflection film according to claim 1, which has a black printed portion on a part of the other main surface of the transparent substrate. The low according to claim 2, wherein in the black printing portion, the chromaticity a ^{* of} the first low-reflection film provided on one of the main surfaces is more than -6 and less than 6, and b ^* is more than -6 and less than 6. A substrate with a reflective film. The substrate with a low-reflection film according to any one of claims 1 to 3, wherein the visual reflectance R1 of the first low-reflection film is 0.5% or less. The substrate with a low-reflection film according to any one of claims 1 to 4, wherein the low-reflection film provided on the side surface has a visual reflectance Rs of 2% or less. The substrate with a low-reflection film according to any one of claims 1 to 5, wherein the transparent substrate has an uneven shape on one of the main surfaces and the side surface by antiglare treatment. The substrate with a low-reflection film according to any one of claims 1 to 6, wherein the transparent substrate is a glass substrate. The substrate with a low-reflection film according to claim 7, wherein the glass substrate is chemically tempered glass. The substrate with a low reflective film according to claim 8, wherein the surface compressive stress of the chemically strengthened glass is 400 MPa or more and 1200 MPa or less. The substrate with a low-reflection film according to claim 9, wherein the depth of the surface compressive stress layer of the chemically strengthened glass is 15 to 60 μm. The substrate with a low-reflection film according to any one of claims 1 to 10, further comprising an antifouling film on the upper surface of at least one of the first low-reflection film and the second low-reflection film. With the display
The substrate with a low-reflection film according to any one of claims 1 to 11 provided as a front substrate on the front surface of the display.
A display device characterized by having. The transparent substrate is fixed to the carrier substrate for fixing the transparent substrate at a predetermined interval via a spacer, and a first low-reflection film is applied to one main surface of the transparent substrate of the transparent substrate. A method for manufacturing a substrate with a low-reflection film, in which a second low-reflection film is simultaneously formed on the side surface by a physical vapor deposition method, and the visual reflectance of the first low-reflection film provided on one of the main surfaces. R1 is 0.6% or less, the visual reflectance Rs of the second low-reflection film provided on the side surface is 2.5% or less, the chromaticity a ^* is 0 to 4, and b ^* is 3. A method for producing a substrate with a low-reflection film, which is characterized by being ~ 9. The method for producing a substrate with a low-reflection film according to claim 13, wherein the physical vapor deposition method is sputtering.

Images