JP2020011880A - Glass laminate and method for producing the same - Google Patents

Abstract

To provide a glass laminate that resists stains thereon and a method of producing the same.SOLUTION: A glass laminate has: a glass plate 1 having a first face and a second face; a conductive layer 2 that is placed on the first face of the glass plate 1 and has irregularities of 25-200 nm in depth, on its surface; and a coating layer 3 that coats at least part of the surface of the conductive layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a glass laminate and a method for producing the same.

  Patent Document 1 discloses a glass laminate in which a conductive layer is formed on a surface of a glass plate. This glass laminate is used as a transparent substrate for a solar cell, and the conductive layer is formed of tin oxide having fine irregularities on the surface.

JP 2014-133665 A

  By the way, the glass laminate having conductivity as described above is used not only for solar cells but also for various devices such as touch panels. The surface of such a device may be touched by a finger, or may be touched or rubbed by various members. At this time, the rubbed member may remain on the unevenness, which may become conspicuous and conspicuous. The present invention has been made to solve the above problems, and has as its object to provide a glass laminate capable of suppressing the attachment of dirt and a method for producing the same.

Item 1. A glass plate having a first surface and a second surface;
A conductive layer laminated on the first surface of the glass plate and having irregularities with a depth of 25 to 200 nm on the surface;
A coating layer that covers at least a part of the surface of the conductive layer,
A glass laminate comprising:

Item 2. Item 2. The glass laminate according to Item 1, wherein the coating layer is formed of an insulating material, and is coated with the conductive layer such that at least a part of the protrusion on the surface of the conductive layer is exposed to the outside. .

Item 3. Item 2. The glass laminate according to Item 1, wherein the coating layer contains a conductive polymer and is coated so as to cover the entire surface of the conductive layer.

Item 4. On the end faces of the glass plate and the conductive layer, a chamfered processed surface is formed,
Item 4. The glass laminate according to Item 3, wherein the coating layer is coated so as to cover the conductive layer and at least a part of the processed surface.

Item 5. Item 5. The glass laminate according to Item 4, wherein the coating layer is coated so as to extend to a boundary between the end surface of the glass plate and the second surface.

Item 6. Item 6. The glass laminate according to any one of Items 1 to 5, wherein the conductive layer is formed of tin oxide containing fluorine.

Item 7. Item 7. The glass laminate according to any one of Items 1 to 6, having an electric resistance of 15 to 25Ω.

Item 8. Item 3. The glass laminate according to Item 1 or 2, wherein the visible light transmittance is 83 to 85%.

Item 9. Item 9. A tablet PC comprising a cover glass for a touch panel constituted by the glass laminate according to any one of Items 1 to 8.

Item 10. Item 9. A smartphone including a cover glass for a touch panel constituted by the glass laminate according to any one of Items 1 to 8.

Item 11. Item 9. A smart watch comprising a cover glass for a touch panel constituted by the glass laminate according to any one of Items 1 to 8.

Item 12. Forming the molten glass material into a glass ribbon on the molten metal;
Contacting a raw material gas on the surface of the glass ribbon on the molten metal to form a conductive layer having a depth of 25 to 200 nm on the surface,
Covering at least a part of the surface of the conductive layer with a coating layer,
A method for producing a glass laminate, comprising:

Item 13. The source gas contains at least a tin compound, water, oxygen, and hydrogen fluoride,
Item 13. The method for producing a glass laminate according to Item 12, wherein the conductive layer is formed of tin oxide containing fluorine.

Item 14. Item 12. The glass laminate according to Item 12 or 13, wherein the coating layer is formed of an insulating material, and is coated on the conductive layer such that at least a part of the protrusion on the surface of the conductive layer is exposed to the outside. How to make the body.

Item 15. Item 14. The method for producing a glass laminate according to Item 12 or 13, wherein the coating layer contains a conductive polymer and is coated so as to cover the entire surface of the conductive layer.

Item 16. Prior to the coating of the coating layer, the glass plate and the end surface of the conductive layer, by performing a chamfering process, further comprising a step of forming a processed surface,
Item 16. The method for producing a glass laminate according to Item 15, wherein the coating layer is coated so as to cover the conductive layer and at least a part of the processed surface.

  ADVANTAGE OF THE INVENTION According to this invention, adhesion of dirt can be suppressed.

It is a sectional view showing a 1st embodiment of a glass laminated body concerning the present invention. It is a figure which shows an example of the manufacturing method of a glass plate. It is sectional drawing which shows 2nd Embodiment of the glass laminated body which concerns on this invention. It is sectional drawing which shows the example which gave the processing surface by the chamfering process to the glass laminated body. It is sectional drawing which shows the example which gave the processing surface by chamfering to the glass laminated body. It is sectional drawing which shows the other example of a glass laminated body.

<A. First Embodiment>
Hereinafter, a first embodiment of a glass laminate according to the present invention will be described with reference to the drawings.

<1. Overview of glass laminate>
FIG. 1 is a cross-sectional view of the glass laminate according to the present embodiment. As shown in FIG. 1, this glass laminate includes a glass plate 1, a conductive layer 2 formed on an upper surface (first surface) of the glass plate 1, and a coating layer coated on the surface of the conductive layer 2. 3 is provided. Hereinafter, each member will be described.

<1-1. Glass plate>
The glass plate 1 can be formed of various glasses such as a transparent float plate glass. The glass plate 1 is formed flat, and has a thickness of, for example, preferably 0.5 to 10 mm, more preferably 0.6 to 5 mm, and more preferably 0.7 to 3 mm. Is particularly preferred.

  The composition of the glass plate 1 may be the same as the composition of a conventional template glass, architectural plate glass, automotive plate glass, or the like. Specifically, known soda lime silicate glass, aluminosilicate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, non-alkali glass, or the like can be used.

<1-2. Conductive layer>
The conductive layer 2 can be formed of various transparent materials. For example, the conductive layer 2 can be formed of tin oxide, titanium oxide, zinc oxide, silicon dioxide, or the like. ). For example, when the conductive layer 2 is formed of tin oxide, the proportion of tin oxide in the conductive layer 2 is preferably 90 mol% or more, and more preferably 95 mol% or more. On the other hand, the proportion of fluorine is preferably from 0.01 to 4 mol%, more preferably from 0.02 to 2 mol%.

  The thickness of the conductive layer 2 is preferably from 100 to 600 nm, more preferably from 150 to 500 nm. This is because the resistance value changes according to the thickness of the conductive layer 2, and the thickness of the conductive layer 2 may be changed according to a desired resistance value as described later.

  As shown in the enlarged view of FIG. 1, fine irregularities are formed on the surface of the conductive layer 2. Specifically, irregularities having a depth of 25 to 200 nm, more preferably a depth of 30 to 150 nm, are formed. Here, the depth of the unevenness means a maximum convex portion (a convex portion most protruding in the thickness direction of the conductive layer 2) and a maximum concave portion (a concave portion deepest in the thickness direction of the conductive layer 2). Means that the distance in the thickness direction of the conductive layer 2 is between 25 and 200 nm. Hereinafter, when the depth of the unevenness is described, it means the above contents.

  The unevenness as described above can be formed by various methods. For example, the unevenness can be formed by the following method. Hereinafter, an example of a method for manufacturing the conductive layer 2 for forming the above unevenness will be described. Here, a case where the conductive layer 2 is formed of tin oxide containing fluorine will be described.

This manufacturing method includes the following steps.
-Form the molten glass raw material into a glass ribbon on the molten metal.
-A raw material gas containing a tin compound, water (steam), oxygen, and hydrogen fluoride is sprayed on the surface of the glass ribbon on the molten metal. As the tin compound, an inorganic tin compound such as tin tetrachloride or an organic tin compound represented by monobutyltin trichloride or dimethyldichloride tin can be used. Further, the processing temperature at this time can be, for example, 550 to 750 ° C.

  This method can be performed using, for example, the apparatus shown in FIG. First, the glass raw material (molten glass) melted in the float kiln 51 flows out of the float kiln 51 to the float bath 52, becomes the glass ribbon 10, moves on the molten tin (molten metal) 55, and becomes a semi-solid. Thereafter, it is pulled up by the rollers 57 and sent into the annealing furnace 53. The glass ribbon solidified in the annealing furnace 53 is cut into a glass plate 1 having a predetermined size by a cutting device (not shown).

  A predetermined number of coaters 56 (three coaters 56a, 56b, 56c in the illustrated apparatus) are arranged in the float bath 52 at a predetermined distance from the surface of the glass ribbon 10 in the hot state on the molten tin 55. . The raw material gas described above is continuously supplied onto the glass ribbon 10 from at least one of these coaters 56a to 56c. Thereby, a crystal of fluorine-containing tin oxide is formed on the surface of the glass ribbon 10, and the crystal is grown to form the conductive layer 2. In this process, irregularities are formed on the surface of the tin oxide. The thickness of the conductive layer 2 and the depth of the unevenness can be adjusted by appropriately changing the concentration of the source gas, the temperature, and the processing time.

<1-3. Coating layer>
The coating layer 3 is formed of a transparent material. Further, as shown in the enlarged view of FIG. 1, the coating layer 3 is not coated on the entire surface of the conductive layer 2, but is coated on the concave and convex portions of the unevenness, and the convex portions (top portions) project from the coating layer 3. Coated. That is, although the surface of the glass laminate is covered with the coating layer 3, a part of the conductive layer 2, that is, the projection is exposed. However, not all the projections need to be exposed, and if they are slight, some of the projections may be covered with the coating layer 3.

  The coating layer 3 is formed of an insulating material, and is not particularly limited. For example, the coating layer 3 can be formed of a material containing silica, alumina, zirconia, or the like. In particular, silica is preferable because it easily forms an amorphous material and thus hardly takes a particle structure peculiar to crystals, and thus uniformly covers concave and convex portions.

  The method of forming the coating layer 3 is not particularly limited. For example, the surface of the conductive layer 2 can be coated with the coating layer 3 using dip coating, roll coating, spin coating, or the like.

<2. Physical properties of glass laminate>
The resistance value of the glass laminate is preferably 10 to 30 Ω / □, more preferably 12 to 25 Ω / □.

  The visible light transmittance of the glass laminate is, for example, preferably 83 to 90%, more preferably 85 to 88%, for light having a wavelength of 380 to 780 nm. Such physical property values can be made equal in a second embodiment described later.

<2. Features>
The glass laminate formed as described above can obtain the following effects.
(1) Since the unevenness on the surface of the conductive layer 2 is covered with the coating layer 3, the apparent depth of the unevenness is reduced. Therefore, when the surface of the glass laminate is rubbed with another member, even if the member is torn, it hardly remains in the concave and convex concave portions. Therefore, adhesion of dirt on the surface of the glass laminate can be prevented. Further, even when the surface of the glass laminate is touched with a finger, it is possible to prevent dirt from attaching. Even if the dirt remains on the unevenness, the unevenness is apparently shallow, so that the residue can be easily removed by wiping or the like. In particular, when the coating layer 3 is formed of a hard material such as silica, the scratch resistance can be improved.

(2) The coating layer 3 is not covered over the entire surface of the conductive layer 2 but is covered so that the projections of the conductive layer 2 are exposed. Therefore, even if the coating layer 3 has an insulating property, the conductive performance can be ensured by the conductive layer 2 exposed from the surface of the glass laminate.

(3) Since the coating layer 3 covers the concave portions of the irregularities on the surface of the conductive layer 2, the apparent depth of the irregularities is reduced. This reduces the diffusion of light applied to the surface of the glass laminate, thereby improving the transmittance of visible light. For example, in the case of tin oxide, it has a high refractive index itself, and when it comes to the outermost surface, the reflectance increases. Here, when the coating layer having a low refractive index is disposed on the outermost surface, the reflectance is reduced and the transmittance is improved.

(4) Such a glass laminate can be used for a cover glass for a touch panel such as a tablet PC, a smartphone, and a smart watch, a substrate for a solar cell, and the like, which require conductivity. Such use is the same in the second embodiment described below.

<B. Second Embodiment>
Hereinafter, a second embodiment of the glass laminate according to the present invention will be described with reference to the drawings.

  The glass laminate according to the second embodiment is different from the glass laminate of the first embodiment mainly in the configuration of the coating layer 3, and the configurations of the glass plate 1 and the conductive layer 2 are the same. Therefore, only the differences will be described below.

  FIG. 3 is a cross-sectional view of the glass laminate according to the second embodiment. As shown in FIG. 3, in the glass laminate according to the second embodiment, the coating layer 3 is formed so as to cover the entire surface of the conductive layer 2. That is, the conductive layer 2 is not exposed from the surface of the glass laminate. However, the conductive layer 2 may not be completely covered, and if it is slight, a part of the conductive layer 2 may be exposed.

  The coating layer 3 is formed of a transparent conductive polymer. Specifically, for example, poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate), polypyrrole, polyaniline, or the like can be used as the conductive polymer, but is not limited thereto. Therefore, even if the conductive layer 2 is not exposed on the surface of the glass laminate, the conductive performance can be secured by the coating layer 3.

  As a method for forming the coating layer 3, for example, the method described in the first embodiment can be appropriately used.

  As shown in FIG. 4, a processed surface 10 can be formed on the end surface of the glass laminate by chamfering. As the processing surface 10, for example, as shown in FIG. 4, an inclined surface extending from the surface on the side where the coating layer 3 is formed in the glass laminate to the end surface can be formed. Alternatively, as shown in FIG. 5, the end face of the glass laminate may be formed in an arc shape. The chamfering can be performed, for example, with a grinder.

  In the case of coating with a conductive polymer, the processed surface 10 can also be made conductive. For example, as shown in FIG. 6, after forming the conductive layer 2, chamfering is performed first, and then the coating layer 3 is coated. At this time, the coating layer 3 covers not only the surface of the conductive layer 2 but also the processed surface 10. Thereby, the glass laminate can have conductivity not only on the surface but also on the end face.

Therefore, in particular, the following effects can be obtained.
(1) A glass laminate having an end face having conductivity can conduct at the end face without providing wiring to the front side. Therefore, for example, it is useful as a cover glass for a touch panel.

(2) In particular, when the glass laminate according to the present embodiment is used as a cover glass for a touch panel such as a tablet PC, a smart phone, or a smart watch, the end face is obtained when the glass laminate having a small area is given a conductive property. In this case, conduction can be achieved, so that occurrence of conduction failure or the like can be suppressed. Further, since the entire surface of the cover glass can be used, it is advantageous in terms of design. Among them, since the area of the cover glass of the smart watch is particularly small, it is particularly advantageous to use the glass laminate according to the present embodiment as the cover glass.

(3) The coating layer 3 can be coated so as to reach the entire end face of the glass laminate, that is, from the conductive layer 2 to the boundary between the end face of the glass plate 1 and the lower surface (second surface). Thereby, for example, when an electric component is provided below the glass laminate, the glass laminate and the electric component can be electrically connected without providing a wiring. From this viewpoint, the coating layer 3 may further cover at least a part of the lower surface of the glass plate 1.

  As described above, according to the present embodiment, since the unevenness of the conductive layer 2 is covered with the covering layer, a stain prevention effect can be obtained as in the first embodiment. In addition, since the coating layer 3 has conductivity, a portion covered by the coating layer 3 can have conductivity as in the above-described processed surface. In this case, the coating layer 3 does not need to cover the entire end faces of the glass plate 1 and the conductive layer 2, and may be only a part (for example, only a chamfered portion).

<C. Modification>
As mentioned above, although one Embodiment of this invention was described, this invention is not limited to said Embodiment, A various change is possible unless it deviates from the meaning. The following modifications can be combined as appropriate.

<4-1>
In the first embodiment, the coating layer 3 is formed of an insulating material. However, the coating layer 3 may be formed of the same conductive polymer as that of the second embodiment. Further, similarly to the second embodiment, chamfering can be performed.

<4-2>
The shape of the glass plate 1 is not particularly limited, and various shapes are possible. That is, in addition to the rectangular shape, various shapes such as a circular shape, an elliptical shape, a polygonal shape, and an irregular shape can be adopted.

  In the above embodiment, the glass plate 1 is flat, but the glass plate 1 can be bent or bent into an L shape by press working or the like.

<4-3>
A shielding layer can be formed on any surface of the glass plate 1 with a dark ceramic or the like. For example, a shielding layer is laminated on the periphery of the glass plate 2, and a portion surrounded by the shielding layer can be used as a transmission region.

DESCRIPTION OF SYMBOLS 1 Glass plate 2 Conductive layer 3 Coating layer 10 Processing surface

Claims (16)

A glass plate having a first surface and a second surface;
A conductive layer laminated on the first surface of the glass plate and having irregularities with a depth of 25 to 200 nm on the surface;
A coating layer that covers at least a part of the surface of the conductive layer,
A glass laminate comprising:   2. The glass laminate according to claim 1, wherein the coating layer is formed of an insulating material, and is coated on the conductive layer such that at least a part of the protrusion on the surface of the conductive layer is exposed to the outside. body.   The glass laminate according to claim 1, wherein the coating layer contains a conductive polymer, and is coated so as to cover the entire surface of the conductive layer. On the end faces of the glass plate and the conductive layer, a chamfered processed surface is formed,
The glass laminate according to claim 3, wherein the coating layer is coated so as to cover the conductive layer and at least a part of the processed surface.   The glass laminate according to claim 4, wherein the coating layer is coated so as to extend to a boundary between an end surface of the glass plate and the second surface.   The glass laminate according to any one of claims 1 to 5, wherein the conductive layer is formed of tin oxide containing fluorine.   The glass laminate according to any one of claims 1 to 6, wherein the glass laminate has an electric resistance of 15 to 25 Ω.   The glass laminate according to claim 1 or 2, wherein the visible light transmittance is 83 to 85%.   A tablet PC, comprising: a cover glass for a touch panel formed of the glass laminate according to claim 1.   A smartphone, comprising: a cover glass for a touch panel configured by the glass laminate according to claim 1.   A smart watch, comprising: a cover glass for a touch panel formed of the glass laminate according to claim 1. Forming the molten glass material into a glass ribbon on the molten metal;
Contacting a raw material gas on the surface of the glass ribbon on the molten metal to form a conductive layer having a depth of 25 to 200 nm on the surface,
Covering at least a part of the surface of the conductive layer with a coating layer,
A method for producing a glass laminate, comprising: The source gas contains at least a tin compound, water, oxygen, and hydrogen fluoride,
The method for manufacturing a glass laminate according to claim 12, wherein the conductive layer is formed of tin oxide containing fluorine.   14. The glass according to claim 12, wherein the coating layer is formed of an insulating material, and is coated on the conductive layer such that at least a part of a protrusion on the surface of the conductive layer is exposed to the outside. A method for manufacturing a laminate.   14. The method for producing a glass laminate according to claim 12, wherein the coating layer contains a conductive polymer and is coated so as to cover the entire surface of the conductive layer. Prior to the coating of the coating layer, the glass plate and the end surface of the conductive layer, by performing a chamfering process, further comprising a step of forming a processed surface,
The method for manufacturing a glass laminate according to claim 15, wherein the coating layer is coated so as to cover the conductive layer and at least a part of the processed surface.