阅读说明：本技术 玻璃板 (Glass plate ) 是由 三代均 野濑雄彦 玉田稔 河合洋平 和田直哉 于 2018-06-19 设计创作，主要内容包括：本发明涉及一种玻璃板,具有第一主面和与上述第一主面对置的第二主面,在上述第一主面具有防眩光部和非防眩光部,上述防眩光部和上述非防眩光部的粗糙度曲线的要素的平均长度(RSm)分别为1μm以上,上述防眩光部的RSm与上述非防眩光部的RSm之差为100μm以下。(The present invention relates to a glass plate having a first main surface and a second main surface opposed to the first main surface, wherein the first main surface has an antiglare portion and a non-antiglare portion, the average lengths (RSm) of elements of roughness curves of the antiglare portion and the non-antiglare portion are each 1 μm or more, and the difference between the RSm of the antiglare portion and the RSm of the non-antiglare portion is 100 μm or less.)

1. A glass plate having a first main surface and a second main surface opposed to the first main surface,

the first main surface has an antiglare portion and a non-antiglare portion,

RSm, which is an average length of elements of the roughness curves of the anti-glare part and the non-anti-glare part, is 1 μm or more, respectively, and a difference between the RSm of the anti-glare part and the RSm of the non-anti-glare part is 100 μm or less.

2. The glass plate according to claim 1, wherein the haze of the transmitted light in the visible light region in the antiglare portion is 2% to 40%, and the haze of the transmitted light in the visible light region in the non-antiglare portion is less than 2%.

3. The glass plate according to claim 1 or 2, wherein an absolute value of a difference in height in a plate thickness direction between the glass plate of the antiglare portion and the glass plate of the non-antiglare portion is 20 μm or less.

4. The glass plate according to any one of claims 1 to 3, wherein an arithmetic average surface roughness Ra of the non-antiglare portion is less than 100 nm.

5. The glass plate according to any one of claims 1 to 4, wherein Ra, which is an arithmetic average surface roughness of the antiglare portion, is 20nm or more.

6. The glass plate according to any one of claims 1 to 5, wherein the non-glare part has a profile of 0.5mm or less per 10 mm.

7. The glass plate according to any one of claims 1 to 6, wherein a parallelism of the non-antiglare portion and the second main surface is 10 μm or less per 20 mm.

8. The glass plate according to any one of claims 1 to 7, wherein a flatness of the non-antiglare portion and the second main surface is 10 μm or less per 20 mm.

9. The glass plate according to any one of claims 1 to 8, wherein the non-antiglare portion is formed by coating with a visible light transmissive ink.

10. The glass plate according to any one of claims 1 to 9, wherein a fluorine-containing organosilicon compound coating film is formed on the first main surface.

11. The glass plate according to any one of claims 1 to 9, wherein a low reflection film and a fluorine-containing organosilicon compound coating film are laminated in this order on the first main surface.

12. A method for manufacturing a glass plate having a first main surface and a second main surface opposed to the first main surface, the first main surface having an antiglare portion and a non-antiglare portion,

the non-antiglare portion is formed by printing a visible light-transmissive ink on a part of the first main surface of a glass plate having the first main surface subjected to an antiglare treatment.

13. The method for manufacturing a glass sheet as claimed in claim 12, wherein the ink contains a resin and does not contain a pigment and/or a dye.

Technical Field

The present invention relates to a glass sheet.

Background

In recent years, a cover made of glass is disposed on the display surface side of a display device such as an lcd (liquid Crystal display) device in order to protect the display device. However, when such a glass plate is provided on a display device, there is a case where objects provided in the periphery are often reflected when a display image of the display device is viewed through the glass plate. If such reflection occurs in the glass plate, it is difficult for an observer of the display image to observe the display image, and an unpleasant impression is given.

Therefore, in order to suppress such reflection, for example, an anti-glare treatment for forming an uneven shape on the surface of the glass plate has been attempted.

In the antiglare treatment, for example, means such as etching the surface of a glass plate (for example, see patent document 1) and forming a film having an uneven shape on the surface of the glass plate (for example, see patent document 2) is described.

With the spread of lcd (liquid Crystal display) devices and the like, new functions are required. For example, as a measure against a dozing of a driver of an automobile, an electric train, or the like, a system or the like for monitoring a state of the driver with a camera may be mounted on an instrument panel, particularly, a combination meter or the like in which a meter or the like provided in front of the driver is housed.

Such a glass plate having a portion subjected to the anti-glare treatment and a portion not subjected to the anti-glare treatment has a problem that the glass plate has different portions, and the touch feeling is poor when the glass plate is touched with a finger, and the boundary is distinct, so that the appearance is sometimes deteriorated.

Disclosure of Invention

The invention aims to provide a glass plate which is provided with an anti-dazzle part and a non-anti-dazzle part and has excellent hand touch and appearance.

A glass plate according to an aspect of the present invention includes a first main surface and a second main surface opposed to the first main surface, and has an antiglare portion and a non-antiglare portion on the first main surface, wherein average lengths (RSm) of elements of roughness curves of the antiglare portion and the non-antiglare portion are 1 μm or more, respectively, and a difference between the RSm of the antiglare portion and the RSm of the non-antiglare portion is 100 μm or less.

According to the embodiment of the present invention, a glass plate having an antiglare portion and a non-antiglare portion excellent in hand touch and appearance can be provided.

Drawings

Fig. 1 is a perspective view schematically showing one embodiment of a glass plate according to an embodiment of the present invention.

Fig. 2 is a sectional view obtained by cutting an area including an antiglare portion and a non-antiglare portion along line a-a' in fig. 1.

Fig. 3 is a perspective view schematically showing another embodiment of the glass plate according to the embodiment of the present invention.

Fig. 4 is a sectional view obtained by cutting an area including the antiglare portion and the non-antiglare portion along line B-B' in fig. 3.

Fig. 5 is a perspective view schematically showing one aspect of a glass plate according to another embodiment of the present invention.

Fig. 6 is a sectional view obtained by cutting an area including the antiglare portion and the non-antiglare portion along a line C-C' in fig. 5.

Fig. 7 is a perspective view schematically showing one form of a glass plate according to another embodiment of the present invention.

Fig. 8 is a sectional view obtained by cutting an area including the antiglare portion and the non-antiglare portion along a line D-D' in fig. 7.

Detailed Description

The present invention is not limited to the following embodiments, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

In the present specification, unless otherwise specified, the term AG means an anti-glare, and the term non-AG means a non-anti-glare.

The glass plate of the present embodiment will be described with reference to fig. 1. Fig. 1 is a perspective view schematically showing a glass plate according to the present embodiment. In the glass plate 10A shown in fig. 1, the upper surface is a first main surface, and the lower surface facing the first main surface is a second main surface. The glass plate 10A of the present embodiment has an Antiglare (AG) portion 20 and a non-antiglare (non-AG) portion 30 on a first main surface.

In the present specification, as one of the indexes of the antiglare property, the haze of transmitted light in the visible light region is used. Hereinafter, the term "haze" in the present specification refers to the haze of transmitted light in the visible light region.

In the glass plate 10A of the present embodiment, the haze of the AG portion 20 is higher than the haze of the non-AG portion 30. The haze of the AG portion 20 is preferably 2% to 40%. When the haze is 2% or more, it is visually confirmed that reflection of light is significantly suppressed as compared with a substrate without antiglare processing, and when the haze is larger than 40%, light is diffusely reflected, and when the haze is used as a cover member of a display device or a substrate integrated with a touch panel, the visibility of display of the display device may be reduced.

The haze of the AG portion 20 is more preferably 2% to 35%, and still more preferably 3% to 30%.

On the other hand, the haze of the non-AG portion 30 is preferably 0.01% or more and less than 2%, more preferably 1% or less, and further preferably 0.5% or less. If the haze is less than 2%, the antiglare effect is not observed, and visibility is good even when observed through a glass plate. In order to make the haze less than 0.01%, thorough cleaning is necessary in the manufacturing process. By setting the haze to 0.01% or more, the production cost can be reduced.

The AG portion 20 can be formed by subjecting the surface of the first main surface of the glass plate to surface treatment to form a concave-convex shape.

Fig. 2 is a cross-sectional view of the AG portion 20 and the non-AG portion 30 taken along line a-a' in fig. 1. In fig. 2, the AG portion 20 has a plurality of fine concave portions 12 formed in a concave-convex shape on the first main surface of the glass plate 10A. On the other hand, in the non-AG portion 30, the visible light transmissive ink 40 is applied to the concave portion 12, and the convex portion which is the boundary between the concave portions is slightly exposed.

In the glass plate of the present embodiment, the non-AG portion 30 is not a flat surface, and the convex portion which is the boundary between the concave portions 12 is exposed from the first main surface, so that various functional films such as an antifouling film and a low reflection film are easily formed on the first main surface of the glass plate 10A. In addition, when various functional films are formed, optical characteristics are less likely to be blurred.

Further, even in the absence of various functional films, a difference in tactile sensation is unlikely to occur between the AG portion 20 and the non-AG portion 30.

The AG portion 20 shown in fig. 2 is formed by, for example, physical or chemical surface treatment by forming a plurality of fine concave portions 12 on the first main surface of the glass plate 10A to form a concave-convex shape on the first main surface. As the surface treatment performed for the above purpose, for example, a method of performing a frosting treatment (フロスト treatment) on the first main surface of the glass sheet 10A may be mentioned. The frosting treatment may be performed by immersing the first main surface of the glass plate 10A as the object to be treated in a mixed solution of hydrofluoric acid and ammonium fluoride, a mixed solution of hydrofluoric acid and potassium fluoride, or the like, and chemically surface-treating the immersed surface. In particular, the method of the frosting treatment in which the chemical surface treatment is performed using a chemical solution such as hydrofluoric acid is preferably used as a surface treatment method in which a plurality of fine concave portions 12 are formed on the first main surface of the glass plate 10A because the surface to be treated is less likely to be microcracked and less likely to be degraded in mechanical strength.

In addition to the method based on the chemical treatment, for example, a so-called sand blasting method in which crystalline silica powder, silicon carbide powder, alumina powder, or the like is blown to the first main surface of the glass plate 10A by pressurized air, a so-called wet blasting method in which crystalline silica powder, silicon carbide powder, alumina powder, or the like is dispersed in water and blown to the first main surface of the glass plate 10A by pressurized air, or a physical surface treatment method in which polishing is performed by a brush wetted with water to which crystalline silica powder, silicon carbide powder, alumina powder, or the like is attached, may be used as a surface treatment method for forming the fine recessed portions 12 in the first main surface of the glass plate 10A.

In this way, after the plurality of fine recesses 12 are formed on the first main surface of the glass plate 10A, the first main surface of the glass plate 10A may be chemically etched to adjust the surface shape. In this way, the haze can be adjusted to a desired value by the etching amount, cracks generated by sandblasting or the like can be removed, and glare can be suppressed.

As the etching, a method of immersing a glass plate as a subject to be processed in a solution containing hydrofluoric acid as a main component is preferably used. The hydrofluoric acid may contain hydrochloric acid, nitric acid, citric acid, or the like. By containing these components, it is possible to suppress local precipitation reaction due to reaction between the alkali component incorporated into the glass and hydrogen fluoride, and to perform etching uniformly in the plane.

In fig. 2, a plurality of concave portions 12 are formed on the first main surface of the glass plate 10A, and the first main surface is formed in a concave-convex shape.

Fig. 3 is a perspective view schematically showing a glass plate according to another embodiment of the present invention. In the glass plate 10B shown in fig. 3, the upper surface is a first main surface, and the lower surface facing the first main surface is a second main surface. The glass plate 10B has an AG portion 20 and a non-AG portion 30 on the first main surface. In fig. 3, when a plurality of fine protrusions 13 are formed on the first main surface of the glass pane 10B, the haze values of the AG portion 20 and the non-AG portion 30 are the same as the ranges described for the glass pane 10A.

Fig. 4 is a cross-sectional view of the AG portion 20 and the non-AG portion 30 taken along the line B-B' in fig. 3.

The AG portion 20 shown in fig. 4 is formed by surface treatment of the first main surface of the glass plate 10B to form a plurality of fine protrusions 13, thereby forming the first main surface into a concave-convex shape. As the surface treatment to be carried out for the above purpose, there is a method of applying a coating liquid containing fine particles mainly composed of silica to the first main surface. In the present specification, the term "comprising silica as a main component" means that SiO is contained₂50% by mass or more, and more preferably 90% by mass or more.

The fine particles containing silica as a main component may contain a small amount of components other than silica. Examples of the component include one or more ions and/or oxides selected from Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi and lanthanoids.

The fine particles mainly composed of silica may be solid particles or hollow particles.

In the non-AG portion 30 shown in fig. 4, the visible light transmissive ink 40 is applied to the concave portion 12 which is provided on the first main surface of the glass plate 10B and which is the boundary between the convex portions 13, and only the upper portion of the convex portion 13 is exposed from the first main surface. In fig. 4, the ink 40 is shown in black to facilitate the identification of other components, but is a visible light transmissive ink.

Fig. 5 is a perspective view schematically showing a glass plate according to another embodiment of the present embodiment. In the glass plate 10C shown in fig. 5, the upper surface is a first main surface, and the lower surface facing the first main surface is a second main surface. The glass plate 10C has an AG portion 20 and a non-AG portion 30 on the first main surface. The haze of the AG portion 20 and the non-AG portion 30 is in the same range as described for the glass plate 10A.

Fig. 6 is a cross-sectional view of the AG portion 20 and the non-AG portion 30 taken along the line C-C' in fig. 5.

In the AG portion 20 of the glass plate 10C shown in fig. 6, the concave-convex shape is formed on the first main surface of the glass plate 10C by the same method as the surface treatment applied to the glass plate 10A. On the other hand, in the non-AG portion 30 of the present embodiment, the visible light transmissive ink 40 covers the entire surface of the glass plate 10C, and the convex portions 13 on the surface of the glass plate 10C, which are the boundaries between the concave portions 12, are not exposed. Although not shown, the non-AG portion 30 has a slight unevenness in a manner similar to the unevenness of the surface of the glass plate 10C.

In the glass plate of the present embodiment, it is preferable that the entire region of the non-AG portion 30 is covered with the visible light transmissive ink 40 for the following reason. As compared with the case where the visible light transmissive ink is applied only to the recessed portions 12 on the surface of the glass plate 10C, the film thickness of the visible light transmissive ink can be increased, and the surface shape can be easily controlled. In particular, the average length (RSm) and the arithmetic average surface roughness (Ra) of the elements of the roughness curve can be controlled to be within desired ranges. Further, by covering the entire area of the non-AG portion 30 with the visible light transmissive ink 40, the surface reflectance can be made uniform, and in the case of a camera having a built-in non-AG portion, the uniformity of the brightness of the camera field of view can be improved.

Fig. 7 is a perspective view schematically showing a glass plate according to another embodiment of the present invention. In the glass plate 10D shown in fig. 7, the upper surface is a first main surface, and the lower surface facing the first main surface is a second main surface. The glass plate 10D has an AG portion 20 and a non-AG portion 30 on the first main surface. The haze of the AG portion 20 and the non-AG portion 30 is in the same range as described for the glass plate 10A.

Fig. 8 is a sectional view of the AG portion 20 and the non-AG portion 30 cut along the line D-D' in fig. 7.

The AG portion 20 of the glass plate 10D shown in fig. 8 can be formed into a concave-convex shape on the surface of the first main surface of the glass plate 10D by the same method as the surface treatment applied to the glass plate 10B. On the other hand, in the non-AG portion 30 of the present embodiment, the visible light transmissive ink 40 covers the surface of the glass plate 10D over the entire region, and the convex portion 13 is not exposed. Although not shown, the non-AG portion 30 has a slight unevenness in a manner simulating the unevenness of the surface of the glass plate 10D.

In the glass plate of the present embodiment, the entire region of the non-AG portion 30 is preferably covered with the visible light transmissive ink 40 for the following reason. As compared with the case where the visible light transmissive ink is applied only to the concave portions 12 which are boundaries between the convex portions 13, the film thickness of the visible light transmissive ink can be increased, and the surface shape can be easily controlled. In particular, the average length (RSm) and the arithmetic average surface roughness (Ra) of the elements of the roughness curve can be controlled to be within desired ranges. Further, since the entire area of the non-AG portion 30 is covered with the visible light transmissive ink 40, the surface reflectance can be made uniform, and when the camera is built in the non-AG portion, the uniformity of the brightness of the camera field of view can be improved.

The ink applied to the first main surface of the glass plates 10A, 10B, 10C, and 10D for the purpose of forming the non-AG portion 30 in the glass plates 10A, 10B, 10C, and 10D is not particularly limited as long as it is visible light transmissive, and may be inorganic or organic.

The inorganic ink may contain, for example, a material selected from SiO₂、ZnO、B₂O₃、Bi₂O₃、Li₂O、Na₂O and K₂More than 1 of O selected from CuO and Al₂O₃、ZrO₂、SnO₂And CeO₂More than 1 of (1) and Fe₂O₃And TiO₂The composition of (1).

As the organic ink, various inks in which a resin is dissolved in a solvent can be used. For example, as the resin, resins such as acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin, vinyl acetate resin, phenol resin, olefin resin, ethylene-vinyl acetate copolymer resin, polyvinyl acetal resin, natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyester polyol, polyether urethane polyester, and the like can be selected and used. The above resin is preferably transparent.

As the solvent for these inks, water, alcohols, esters, ketones, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents can be used. For example, isopropanol, methanol, ethanol, and the like can be used as alcohols, ethyl acetate can be used as esters, and methyl ethyl ketone can be used as ketones. As the aromatic hydrocarbon solvent, toluene, xylene, Solvesso 100, Solvesso150 and the like can be used, and as the aliphatic hydrocarbon solvent, hexane and the like can be used. These are given as examples, and various inks can be used.

These inks may contain a colorant such as a pigment or a dye, and preferably do not contain such a colorant, as long as the visible light transmittance is not impaired.

The means for applying the visible light transmissive ink to the first main surface of the glass plates 10A, 10B, 10C, and 10D is not particularly limited, but the visible light transmissive ink is preferably printed on the first main surface. As a printing method, for example, inkjet printing or screen printing can be used.

In the present embodiment, when focusing on the height of the glass sheet 10 in the thickness direction, the absolute value h of the difference between the heights of the glass sheets 10A, 10B, 10C, 10D in the thickness direction of the AG portion 20 and the non-AG portion 30 is preferably 20 μm or less. In the present specification, the absolute value h of the difference in height between the glass plates 10A, 10B, 10C, 10D in the thickness direction of the AG portion 20 and the non-AG portion 30 means the difference in height between the highest portion in the AG portion 20 and the lowest portion in the non-AG portion 30. The absolute value is calculated by taking the highest height portion of the AG portion 20 as a reference, taking the lowest height portion of the non-AG portion 30 as a negative value when it is higher than the highest height portion, and taking the lowest height portion of the non-AG portion 30 as a positive value when it is lower than the highest height portion, as an absolute value h of the height difference.

If the absolute value h of the difference in height exceeds 20 μm, the touch feeling upon finger touch is deteriorated, and the hand touch feeling is deteriorated. In addition, since the boundary is conspicuous, the appearance is deteriorated. In contrast, the absolute value h of the difference in height is 20 μm or less, so that the hand feeling and the appearance can be improved even if the AG portion 20 and the non-AG portion 30 are provided on the first main surface.

The absolute value h of the difference in height is preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 5 μm or less.

In order to stabilize the process of forming the non-AG portion, the absolute value h of the difference in height is preferably 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 1 μm or more.

In the non-AG portion 30 of the glass sheets 10A and 10B, only the convex portion 13 that forms the boundary between the concave portions 12 is slightly exposed from the first main surface. In the non-AG portion 30 of the glass plates 10C, 10D, the entire region is covered with the visible light transmissive ink 40. In any case, the absolute value h of the difference in height exceeds 0 μm.

In the present embodiment, in order to determine the surface properties of the AG portion 20 and the non-AG portion 30, the average length (RSm) and the arithmetic average surface roughness (Ra) of the elements of the roughness curves of these portions are used.

In the present embodiment, RSm in the AG unit 20 and the non-AG unit 30 is 1 μm or more, respectively. That is, RSm measured with respect to the AG section 20 is 1 μm or more, and RSm measured with respect to the non-AG section 30 is 1 μm or more. The reason why RSm of each of the AG section 20 and the non-AG section 30 is preferably 1 μm or more is as follows.

When RSm is less than 1 μm, when the surface of the glass plate is touched with a finger, the finger comes into surface contact with the surface of the glass plate, and resistance increases, which may result in deterioration of finger touch feeling. On the other hand, if RSm is 1 μm or more, the finger makes point contact with the surface of the glass plate, and the finger does not easily feel the resistance of the glass plate.

The RSm of the AG portion 20 is more preferably 3 μm or more, and still more preferably 5 μm or more. The RSm of the AG section 20 is preferably 40 μm or less, more preferably 30 μm or less, and still more preferably 25 μm or less.

The RSm of the non-AG portion 30 is more preferably 5 μm or more, and still more preferably 10 μm or more. The RSm of the non-AG portion 30 is preferably 150 μm or less, more preferably 100 μm or less, further preferably 70 μm or less, and particularly preferably 60 μm or less.

In the present embodiment, the difference between RSm of the AG unit 20 and RSm of the non-AG unit 30 is 100 μm or less.

The reason why the difference between RSm of the both is preferably in the above range is as follows.

If the difference between RSm exceeds 100 μm, the light scattering properties at the AG portion and the non-AG portion are significantly different, and they are significantly different in appearance. As a result, the design of the glass sheet may be impaired. By setting the difference between RSm to 100 μm or less, the difference in light scattering properties between the AG portion and the non-AG portion can be reduced. In addition, the difference in hand touch feeling between the AG portion and the non-AG portion can be reduced.

The difference in RSm between the two is preferably 50 μm or less, more preferably 30 μm or less. The lower limit of the difference in RSm is preferably 1 μm or more.

The non-AG portion 30 is provided in a region in front of the camera or a region in which the fingerprint sensor is provided when the glass plate of the present embodiment is used as a cover glass of a portable electronic device, for example, and is provided in a region through which visible light or radio waves for sensing are transmitted when the glass plate is used as a protective member for other sensors. Therefore, in the present embodiment, since the camera function, the fingerprint sensor function, and the like are not hindered, the non-AG portion 30 preferably has an Ra of less than 100nm, more preferably less than 40nm, still more preferably less than 20nm, and particularly preferably less than 15 nm. The Ra of the non-AG portion 30 is preferably 3nm or more, more preferably 5nm or more, and further preferably 7nm or more.

On the other hand, Ra of the AG portion 20 is preferably 20nm or more, more preferably 40nm or more, and further preferably 100nm or more. When Ra is 20nm or more, the antiglare property of the AG portion can be sufficiently exhibited.

In the present embodiment, the boundary between the AG portion 20 and the non-AG portion 30 is preferably a smooth line in appearance. Therefore, the contour of the non-AG portion 30 that forms the boundary between the AG portion 20 and the non-AG portion 30 is preferably 0.5mm or less, and more preferably 0.3mm or less per 10 mm.

The profile of the present specification is based on the profile of the line of JISB-0621 (2001).

As described above, the non-AG portion 30 is provided in the region in front of the camera, the region in which the fingerprint sensor is provided, and the region through which visible light or radio waves for sensing are transmitted, for example, according to the use of the glass plate of the present embodiment. Therefore, if the parallelism and flatness of the non-AG portion 30 and the second main surface are low, problems occur such as deterioration in the appearance of the glass plate 10 and deterioration in the optical characteristics of the non-AG portion 30.

In the present embodiment, the parallelism of the non-AG portion 30 to the second main surface is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 2 μm or less per 20 mm.

In order to stabilize the process of forming the non-AG portion, the parallelism between the non-AG portion 30 and the second main surface is preferably 0.1 μm or more, more preferably 0.5 μm or more per 20 mm.

In the present embodiment, the flatness of the non-AG portion 30 and the second main surface is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 2 μm or less per 20 mm.

In order to stabilize the process of forming the non-AG portion, the flatness of the non-AG portion 30 and the second main surface is preferably 0.1 μm or more, more preferably 0.5 μm or more per 20 mm.

The parallelism and the flatness in the present specification are based on those of JISB-0621 (2001).

As described above, since the non-AG portion 30 of the present embodiment is formed by applying the visible light transmissive ink 40, the visible light transmittance of the non-AG portion 30 is good. Specifically, the visible light transmittance of the non-AG portion 30 is preferably 88% or more, more preferably 90% or more, and particularly preferably 92% or more.

In the present embodiment, various functional films may be formed on the first main surfaces of the glass plates 10A, 10B, 10C, and 10D. An example of a functional film formed for this purpose is an antifouling film. The antifouling film may be formed by coating a fluorine-containing organosilicon compound on the first main surface of the glass plate, for example. The fluorine-containing organosilicon compound used for forming the coating film is not particularly limited as long as it imparts antifouling property, water repellency, and oil repellency. For example, KP-801 (trade name manufactured by shin-Etsu chemical Co., Ltd.), KY-178 (trade name manufactured by shin-Etsu chemical Co., Ltd.), KY-130 (trade name manufactured by shin-Etsu chemical Co., Ltd.), KY-185 (trade name manufactured by shin-Etsu chemical Co., Ltd.), OPTOOL (registered trade name) DSX, OPTOAES (both trade names manufactured by Dajin chemical Co., Ltd.), S-550 (trade name manufactured by Asahi Nitro Kabushiki Kaisha) and the like can be preferably used as the commercially available fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group. The thickness of the fluorine-containing organosilicon compound coating film is not particularly limited, but is preferably 1 to 20nm, more preferably 2 to 10 nm.

The glass plates 10A, 10B, 10C, and 10D of the present embodiment have preferable characteristics in forming a fluorine-containing organosilicon compound coating film.

If the absolute value h of the difference in height between the AG portions 20 and the non-AG portions 30 in the plate thickness direction is large, the fluorine-containing organosilicon compound is likely to aggregate at the boundary between the AG portions 20 and the non-AG portions 30. If the fluorine-containing organosilicon compound aggregates, hydrophobic groups of the fluorine-containing organosilicon compound are bonded to each other at the boundary, and there is a possibility that the function as an antifouling agent is impaired. In addition, there is a concern that the fluorine-containing organosilicon compound may agglomerate to cause a reduction in appearance.

In the present embodiment, since the absolute value h of the difference between the heights of the AG portion 20 and the non-AG portion 30 in the plate thickness direction of the glass plates 10A, 10B, 10C, and 10D is 20 μm or less, when the fluorine-containing organosilicon compound coating is formed on the first main surface of the glass plates 10A, 10B, 10C, and 10D, the possibility of occurrence of coagulation of the fluorine-containing organosilicon compound at the boundary between the AG portion 20 and the non-AG portion 30 is low, and the above-described problem is unlikely to occur.

In addition, as another example of the functional film formed for the above purpose, a low reflection film can be given. The material of the low reflection film is not particularly limited, and various materials can be used as long as they can suppress reflection. For example, the low reflection film may be formed by laminating a high refractive index layer and a low refractive index layer.

The high refractive index layer and the low refractive index layer may be in the form of including 1 layer, or may be in the form of including 2 or more layers. When the high refractive index layer and the low refractive index layer each include 2 or more layers, the high refractive index layer and the low refractive index layer are preferably alternately stacked.

In order to provide sufficient antireflection performance, the low reflection film is preferably a laminate in which a plurality of films (layers) are laminated. For example, the laminate is preferably a laminate of 2 to 6 layers, and more preferably a laminate of 2 to 4 layers. The laminate is preferably a laminate in which a high refractive index layer and a low refractive index layer are laminated as described above, and the total number of layers of the high refractive index layer and the low refractive index layer is preferably in the above range.

The material of the high refractive index layer and the low refractive index layer is not particularly limited, and may be selected in consideration of the desired degree of antireflection, productivity, and the like. As the material constituting the high refractive index layer, for example, one selected from niobium oxide (Nb)₂O₅) Titanium oxide (TiO)₂) Zirconium oxide (ZrO)₂) Silicon nitride (Si)₃N₄) Tantalum oxide (Ta)₂O₅) 1 or more of them. As a material constituting the low refractive index layer, silicon oxide (SiO) is preferably used₂). Niobium oxide is particularly preferably used as the high refractive index layer in view of productivity and refractive index. Therefore, the low reflection film is more preferably a laminate of a niobium oxide layer and a silicon oxide layer. The film thickness is preferably 40nm to 500nm, more preferably 100nm to 300 nm.

Both a fluorine-containing organosilicon compound coating film and a low reflection film may be formed on the first main surface of the glass plates 10A, 10B, 10C, 10D. In this case, the low reflection film and the fluorine-containing organosilicon compound coating film are laminated in this order from the first main surface side.

(examples)

The present invention will be described below by referring to specific examples, but the present invention is not limited to these examples. Examples 1 to 6 are examples, and examples 7 to 11 are comparative examples.

(1) Sample preparation

[ example 1]

The glass plate of the present embodiment is manufactured in the following procedure.

In this example, a non-strengthened aluminosilicate glass (product name: Dragontrail (registered trademark) size: 300 mm. times.300 mm, thickness: 1.3mm, manufactured by Asahi glass Co., Ltd.) was used as a glass plate.

First, an acid-resistant protective film is bonded to the main surface of the glass plate on the side where the AG portion is not formed.

Then, an anti-glare treatment was performed in the following order to form an AG portion on the glass plate.

The glass plate was immersed in a 3 mass% hydrofluoric acid solution for 3 minutes to remove contaminants adhering to the main surface of the glass plate on the side where the protective film was not attached, and the thickness of the glass plate was removed as a pre-processing to remove 10 μm. Further, the glass plate was immersed in a mixed solution of 8 mass% hydrofluoric acid and 8 mass% potassium fluoride for 3 minutes, and the main surface of the glass plate on the side to which the protective film was not attached was subjected to a frosting treatment, thereby forming a plurality of fine recesses on the main surface of the glass plate. The frosted glass plate was immersed in a 10 mass% hydrofluoric acid solution for 3 minutes (etching time 4 minutes) to adjust the haze to 15%.

Thereafter, the protective film was peeled off, and the glass plate was immersed in a molten salt of potassium nitrate heated to 450 ℃ for 1 hour, and then taken out of the molten salt, and slowly cooled to room temperature for 1 hour. Thereby, the glass sheet is chemically strengthened.

Next, 1 layer of visible light-transmissive ink (trade name: HF-GV3 RX01-800 medium, manufactured by Seiko ink K.K.) was applied to the main surface of the glass plate on the side where the antiglare treatment was performed by screen printing so as to form a circle having a diameter of 10mm using a screen printer. After applying the visible light-transmitting ink, the glass plate was cured by holding at 150 ℃ for 30 minutes to form a non-AG portion on the main surface of the glass plate.

In the glass plate of example 1, the portion of the main surface on the side subjected to the antiglare treatment, to which the visible light-transmissive ink was applied, was a non-AG portion, and the portion other than the non-AG portion was an AG portion.

[ example 2]

A glass plate was obtained in the same manner as in example 1 except that the antiglare treatment was performed as follows.

The glass plate was immersed in a 3 mass% hydrofluoric acid solution for 3 minutes to remove contaminants adhering to the main surface of the glass plate on the side where the protective film was not attached, and the thickness of the glass plate was removed as a pre-processing to remove 10 μm. Further, the glass plate was immersed in a mixed solution of 8 mass% hydrofluoric acid and 8 mass% potassium fluoride for 3 minutes, and the main surface of the glass plate on the side to which the protective film was not attached was subjected to a frosting treatment, thereby forming a plurality of fine concave portions on the main surface of the glass plate. The frosted glass plate was immersed in a 10 mass% hydrofluoric acid solution for 2 minutes (etching time: 3 minutes), whereby the haze was adjusted to 25%.

Next, a non-AG portion was formed on the main surface of the glass plate in the same manner as in example 1 except that 2 layers of visible light transmissive ink were applied by screen printing.

In the glass plate of example 2, the portion of the main surface on the side subjected to the anti-glare treatment, on which the visible light transmissive ink was applied, was a non-AG portion, and the portion other than the non-AG portion was an AG portion.

[ example 3]

A glass plate (product name: Dragnail (registered trademark) size: 300 mm. times.300 mm, thickness: 1.3mm, manufactured by Asahi glass Co., Ltd.) was used, which was chemically strengthened by the same method as in example 1. The glass plate was subjected to a spray anti-glare treatment according to the following procedure.

After the surface of the glass plate was washed with sodium bicarbonate water, it was washed with ion-exchange water and dried. Next, the glass plate was heated in an oven so that the surface temperature became 80 ℃, and the glass plate was sprayed by a spraying method at a spraying pressure: 0.4MPa, coating liquid amount: 7 mL/min, nozzle moving speed: 750 mm/min, spray spacing: 22mm, distance between the nozzle tip and the glass plate: 115mm, droplet diameter: 6.59 μm coated with the hollow silica fine particle dispersion, a plurality of fine protrusions were formed on the main surface of the glass plate. The amount of coating was such that the height of the projections was 10 μm.

Next, visible light-transmitting ink was applied to the main surface of the glass plate on the side subjected to the spray anti-glare treatment in the same manner as in example 2, and cured to form a non-AG portion on the main surface of the glass plate.

In the glass plate of example 3, the portion of the main surface on the side subjected to the spray antiglare treatment, to which the visible light-transmitting ink was applied, was a non-AG portion, and the portion other than the non-AG portion was an AG portion.

[ example 4]

A glass plate was obtained in the same manner as in example 3, except that the conditions for the spray antiglare treatment were changed to the following conditions.

After the surface of the glass plate was washed with sodium bicarbonate water, washed with ion-exchange water, and dried. Next, the glass plate was heated in an oven so that the surface temperature became 80 ℃, and the glass plate was sprayed by a spraying method at a spraying pressure: 0.4MPa, coating liquid amount: 7 mL/min, nozzle moving speed: 500 mm/min, spray spacing: 22mm, distance between the nozzle tip and the glass plate: 115mm, droplet diameter: the hollow silica fine particle dispersion was coated to 6 μm to form a plurality of fine protrusions on the main surface of the glass plate. The amount of coating was such that the height of the projections was 10 μm.

A visible light-transmitting ink was applied and cured in the same manner as in example 3, thereby forming a non-AG portion on the main surface of the glass plate.

In the glass plate of example 4, the portion of the main surface on the side subjected to the spray antiglare treatment, to which the visible light-transmitting ink was applied, was a non-AG portion, and the portion other than the non-AG portion was an AG portion.

[ example 5]

In this example, a glass plate (product name: Dragontrail (registered trademark) size: 300 mm. times.300 mm, thickness: 1.3mm, manufactured by Asahi glass Co., Ltd.) was used without strengthening.

On one main surface of the glass plate, an anti-glare treatment was performed as follows. First, a main surface on the side where the AG portion was formed was subjected to wet blasting using a wet blasting apparatus (manufactured by MAKO K.K., apparatus name: W8MN-Q062Jr. TypeII). White alumina particles (#2000) were used as abrasive grains, and the pressure was 0.25 MPa. Next, after an acid-resistant protective film was bonded to the main surface of the glass plate on the side where no AG portion was formed, the glass plate was immersed in a 10 mass% hydrofluoric acid solution and etched to a depth of 43 μm.

Thereafter, the protective film was peeled off, and the glass plate was immersed in a molten salt of potassium nitrate heated to 450 ℃ for 1 hour, and then taken out of the molten salt, and slowly cooled to room temperature for 1 hour. Thereby, the glass sheet is chemically strengthened.

Next, 1 layer of visible light-transmissive silicone ink was applied to the main surface of the glass plate on the side subjected to the antiglare treatment by screen printing so as to form a circular shape of 10mm diameter using a screen printer. After applying the visible light-transmitting ink, the glass plate was cured by holding at 200 ℃ for 60 minutes to form a non-AG portion on the main surface of the glass plate.

In the glass plate of example 5, the portion of the main surface on the side subjected to the anti-glare treatment, on which the visible light-transmissive ink was applied, was a non-AG portion, and the portion other than the non-AG portion was an AG portion.

[ example 6]

A glass plate was obtained in the same manner as in example 5, except that the antiglare treatment was performed as described below. First, a main surface on the side where the AG portion was formed was subjected to wet blasting using a wet blasting apparatus (manufactured by MAKO K.K., apparatus name: W8MN-Q062 Jr.TypeII). White alumina particles (#1500) were used as abrasive grains, and the pressure was 0.25 MPa. Next, after an acid-resistant protective film was bonded to the main surface of the glass plate on the side where no AG portion was formed, the glass plate was immersed in a 10 mass% hydrofluoric acid solution, and etching was performed to a depth of 38 μm.

Next, chemical strengthening treatment of the glass plate was performed in the same manner as in example 5, and then, visible light-transmissive ink was applied and cured in the same manner as in example 5, thereby forming a non-AG portion on the main surface of the glass plate.

In the glass plate of example 6, the portion of the main surface on the side subjected to the anti-glare treatment and applied with the visible light-transmissive ink was a non-AG portion, and the portion other than the non-AG portion was an AG portion.

[ example 7]

The acid-resistant protective film was subjected to the anti-glare treatment and the chemical strengthening treatment in the same manner as in example 1, with the protective film cut to have a diameter of 20mm being bonded to the substantially central portion of the main surface of the glass plate on the side where the AG portion was formed.

Next, the glass plate was immersed in a 3 mass% hydrofluoric acid solution for 3 minutes to remove contaminants adhering to the main surface of the glass plate on the side where the protective film was not attached, and the thickness of the glass plate was removed as a pre-processing to remove 10 μm. Further, the glass plate was immersed in a mixed solution of 8 mass% hydrofluoric acid and 8 mass% potassium fluoride for 3 minutes, and the main surface of the glass plate on the side not bonded with the protective film was subjected to a frosting treatment. The frosted glass plate was immersed in a 10% hydrofluoric acid solution for 3 minutes (etching time 4 minutes) to adjust the haze to 15%.

In the glass plate of example 7, the central portion of the main surface on which the antiglare treatment was applied, to which the protective film of 20mm in diameter was applied, was a non-AG portion, and the portions other than the non-AG portion were AG portions.

[ example 8]

After the antiglare treatment was performed in the same manner as in example 1, the substantially central portion of the antiglare treated surface was polished using a conical polishing grindstone having a diameter of 5mm and a cerium oxide abrasive grain having a knoop hardness of 3000, and the antiglare treated surface was removed at a depth of 15 μm in a range of 20 mm. Thereafter, chemical strengthening was performed in the same manner as in example 1.

In the glass plate of example 8, the main surface on the side subjected to the anti-glare treatment was polished to form a non-AG portion, and the portion other than the non-AG portion was an AG portion.

[ example 9]

After the antiglare treatment was performed in the same manner as in example 1, the surface antiglare-treated at a depth of 12 μm was removed by removing a region of 20mm in diameter from the center of the antiglare-treated surface, attaching a protective film thereto, and polishing with a tape using #10000 ceramic abrasive grains. Thereafter, chemical strengthening was performed in the same manner as in example 1.

In the glass plate of example 9, the central portion of the antiglare-treated main surface, which had a diameter of 20mm and was not coated with the protective film, was an AG portion, and the portions other than the AG portion were non-AG portions.

[ example 10]

The acid-resistant protective film was subjected to the spray antiglare treatment and the chemical strengthening treatment in the same manner as in example 3, with the protective film cut to have a diameter of 20mm being bonded to the substantially central portion of the main surface of the glass plate on the side where the AG portion was formed.

In the glass solid plate of example 10, the central portion of the main surface on which the antiglare treatment was applied by spraying, to which the protective film having a diameter of 20mm was applied, was a non-AG portion, and AG portions were provided at portions other than the non-AG portion.

[ example 11]

After the antiglare treatment and chemical strengthening were performed in the same manner as in example 1, a transparent film processed into a circular shape of 10mm was attached to the antiglare-treated main surface of the glass plate to form a non-Antiglare (AG) portion.

In the glass plate of example 11, the portion of the main surface of the glass plate on the side subjected to the antiglare treatment to which the transparent film was bonded was a non-AG portion, and AG portions were provided except for the non-AG portion.

(2) Evaluation method

The following describes a method for evaluating the characteristics of the glass sheets produced in examples 1 to 11.

(measurement of surface shape)

The glass plates produced in examples 1 to 11 were measured for surface shape on the side having AG portions and non-AG portions by a surface roughness/profile shape measuring instrument (product name SURFCOM, manufactured by tokyo co., ltd.) to obtain a plane profile. Then, from the obtained plane profile, an absolute value h of a difference in height between the AG portion and the non-AG portion, Ra and RSm of the AG portion and the non-AG portion are obtained in accordance with JIS B0601 (2001).

(haze)

For the glass plates produced in examples 1 to 11, the transmission haze (%) of the AG portion and the non-AG portion was measured. The haze was measured using a haze meter (product name: HZ-V3, manufactured by Suga test machine Co., Ltd.).

(degree of profile)

The glass plates produced in examples 1 to 11 were measured for the profile of the non-AG area using a CNC image measuring system (model number: CNC image measuring system NEXIV VMR-10080, manufactured by Nikon instruments Co., Ltd.).

(parallelism)

The glass plates produced in examples 1 to 11 were measured using a laser microscope (trade name: laser displacement meter LK-GD500, manufactured by Kinzhi Co., Ltd.) under the conditions of Cut Off: and (3) measuring the parallelism of the non-AG part and the second main surface (the main surface opposite to the main surface on which the AG part is formed) at 0.8-8 mm.

(flatness)

The glass plates produced in examples 1 to 11 were measured using a surface roughness/profile measuring instrument (SURFCOM, product name: SURFCOM, manufactured by Tokyo K.) and set to a Filter: 2RC, Cut Off: 0.8-8 mm, Control length: 20mm, and the flatness of the non-AG portion and the second main surface was measured.

(touch feeling)

For the glass sheets produced in examples 1 to 11, 10 persons felt the first main surface formed with the AG portion and the non-AG portion in accordance with 1: very good, 2: good and 3: no problem, 4: difference, 5: evaluation was performed very poorly in these 5 stages, and evaluation was performed as an average value.

(degree of image)

The glass sheets produced in examples 1 to 11 were evaluated by 10 persons at 3 stages of good image quality at ○, slightly poor image quality at △ and poor image quality at x, and the average value was evaluated.

(fingerprint wiping test)

With respect to the glass sheets produced in examples 1 to 11, a fluorine-containing organosilicon compound coating was formed on the first main surface on which the AG portion and the non-AG portion were formed in the following order.

First, a fluorine-containing organosilicon compound coating material (product name: KY-185, manufactured by shin-Etsu chemical Co., Ltd.) was introduced into a heating vessel. Then, the inside of the heating vessel is degassed by a vacuum pump for 10 hours or more to remove the solvent in the solution, thereby forming a composition for forming a fluorine-containing organosilicon compound coating film.

Next, the heating vessel containing the composition for forming a fluorine-containing organosilicon compound coating film was heated to 270 ℃. After reaching 270 ℃, the state was maintained for 10 minutes until the temperature stabilized. Then, the composition for forming a fluorine-containing organosilicon compound coating film is supplied from a nozzle connected to a heating vessel containing the composition for forming a fluorine-containing organosilicon compound coating film, and the composition is formed on the first main surface of the glass plate placed in the vacuum chamber.

In the film formation, the film thickness was measured by a crystal oscillator monitor installed in a vacuum chamber, and the film formation was performed until the film thickness of the fluorine-containing organosilicon compound film formed on the glass plate became 10 nm. The supply of the raw material from the nozzle was stopped at the time when the film thickness of the fluorine-containing organosilicon compound film became 10nm, and then the film was taken out from the vacuum chamber. The glass plate taken out was placed on a hot plate with the film surface facing upward, and heat-treated at 150 ℃ for 60 minutes in the air.

The fingerprint wiping performance of the fluorine-containing organosilicon compound coating film formed by the above procedure was confirmed by the following procedure, the fingerprint was pressed against the stepped portion of each sample with the same pressing force using artificial sweat, then, a wiping test was performed using gauze with alcohol added thereto, and the number of times until the fingerprint was removed was confirmed, and the case where the fingerprint was wiped off within 10 times was evaluated as ○, the case where the fingerprint was removed by wiping 11 to 50 times was evaluated as △, and the case where the fingerprint could not be removed even by wiping 50 times was evaluated as x.

The evaluation results of examples 1 to 11 are shown in the following tables.

[ TABLE 1]

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							AG treatment method	Upper cream	Upper cream	Spray AG	Spray AG	Wet sand blasting	Wet sand blasting
Method for forming non-AG part	Printing	Printing	Printing	Printing	Printing	Printing
							Height difference h (mum)	7	2	5	2	2	6
AG part Ra (nm)	150	120	220	240	240	350
							Ra (nm) in non-AG part	14	10	8	8	26	33
AG part RSm (mum)	8	7	8	12	34	27
							non-AG part RSm (mum)	12	13	32	56	60	55
AG haze (%)	15	25	12	5	20	32
							Haze% of non-AG portion	0.3	0.4	1.2	0.3	0.4	0.4
Profile tolerance (mm/10mm)	0.1	0.2	0.3	0.25	0.2	0.2
							Parallelism (μm/20mm)	0.8	0.7	1.3	0.2	1.5	1.9
Flatness (μm/20mm)	0.5	0.3	1.2	1.5	1.3	1.6
							Tactile sensation	1	1	1	1	1	1
Fingerprint wiping test	○	○	○	○	○	○
							Degree of image	○	○	○	○	○	○

[ TABLE 2]

	Example 7	Example 8	Example 9	Example 10	Example 11
						AG treatment method	Upper cream	Upper cream	Upper cream	Spray AG	Upper cream
Method for forming non-AG part	Protective film	Grinding of cylindrical grindstones	Adhesive tape grinding	Protective film	Transparent adhesive tape
						Height difference h (mum)	30	15	12	15	50
AG part Ra (nm)	150	150	150	220	150
						Ra (nm) in non-AG part	0.2	42	55	0.3	0.5
AG part RSm (mum)	8	8	7	11	8
						non-AG part RSm (mum)	0.01 or less	180	220	0.01 or less	0.01 or less
AG haze (%)	15	15	15	12	15
						Haze% of non-AG portion	0.1	1.5	1.2	0.1	0.1
Profile tolerance (mm/10mm)	1.8	0.3	0.5	0.8	0.3
						Parallelism (μm/20mm)	0.4	3.2	4.3	0.5	0.7
Flatness (μm/20mm)	0.5	18.2	20.5	0.3	0.5
						Tactile sensation	4	4	4	4	4
Fingerprint wiping test	△	△	△	△	△
						Degree of image	○	△	△	△	△

As is clear from tables 1 and 2, examples 1 to 6 in which RSm of the AG portion and that of the non-AG portion are both 1 μm or more and the difference between RSm of the AG portion and that of the non-AG portion is 100 μm or less are excellent in touch feeling, fingerprint test and image quality. In contrast, the results of the touch and fingerprint wiping tests were poor in examples 7, 10 and 11 in which RSm of the non-AG portion was less than 1 μm. In addition, even if the RSm of the non-AG portion is 1 μm or more, the results of the touch and fingerprint wiping tests in examples 8 and 9 in which the difference between the RSm of the AG portion and the RSm of the non-AG portion exceeds 100 μm are inferior.

The present invention is described in detail with reference to specific embodiments, but it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application was made based on japanese patent application 2017-120170, filed on 2017, month 6 and day 20, the contents of which are incorporated herein by reference.

Description of the symbols

10A, 10B, 10C, 10D glass plate

12 recess

13 convex part

20 anti-glare part

30 non-glare section

40 ink