JP6724643B2 - Glass plate manufacturing method, glass article manufacturing method, glass plate, glass article, and glass article manufacturing apparatus - Google Patents

Description

The present invention relates to a glass article, a glass plate and the like, and particularly to a chemically strengthened glass article, a glass plate and the like.

For example, in a field such as a cover glass of an electronic device, a window glass for a building material, and a glass member for a vehicle, a glass article used may be required to have high strength. In such cases, chemical strengthening treatments are often applied to the glass substrate from which the glass article is based.

In the chemical strengthening treatment, a glass substrate is immersed in a molten salt containing an alkali metal, and alkali metal ions having a smaller atomic diameter present on the surface of the glass substrate are replaced with alkali metal ions having a larger atomic diameter present in the molten salt. Is the process of replacing.

By the chemical strengthening treatment, alkali metal ions having a larger atomic diameter than the original atoms are introduced into the surface of the glass substrate. Therefore, a compressive stress layer is formed on the surface of the glass substrate, which improves the strength of the glass substrate.

In addition, generally, glass articles chemically strengthened,
(I) a step of preparing a large-sized glass material,
(II) cutting and collecting a plurality of product-shaped glass substrates from a glass material, and (III) chemically strengthening the collected glass substrates,
Is manufactured through.

U.S. Patent Application Publication No. 2015/0166393 Special table 2013-536081 gazette U.S. Patent Application Publication No. 2012/0196071

In the conventional manufacturing method, it is necessary to handle many glass substrates in the final shape after the cutting in (II) and the chemical strengthening treatment in (III). However, at this stage, since the glass substrate has not been chemically strengthened yet, the end face is particularly likely to be scratched, and sufficient careful handling is required. For example, when chemically strengthening the glass substrate in the final shape, sufficient measures must be taken regarding the method of supporting or holding the glass substrate in the molten salt, or the contact between the glass substrate and the jig used.

As described above, the conventional manufacturing method has a problem that handling of the glass substrate is complicated. Further, there is a problem that it is difficult to secure strength quality mainly in the finally obtained glass article, and the production yield of the glass article cannot be increased so much.

On the other hand, in order to avoid such a problem, a method of manufacturing a chemically strengthened glass article by performing a chemical strengthening treatment on a glass material having a large size in advance and cutting the glass material is considered. To be

However, such a method has a problem that it is difficult to cut a glass article from the glass material because the surface of the glass material is reinforced. Further, even if the glass article can be cut out, the glass article obtained thereby has an end face that is not chemically strengthened, so that there is a problem that sufficient strength cannot be obtained.

The present invention has been made in view of such a background, and in the present invention, it is possible to obtain a glass article having good strength while significantly suppressing the deterioration of the appearance quality due to scratches. It is an object to provide a glass article and a method for manufacturing a glass plate. Moreover, it aims at providing the glass article and glass plate which can be manufactured by such a manufacturing method. Furthermore, this invention aims at providing the manufacturing apparatus of such a glass article.

In the present invention, a method for manufacturing a glass plate,
(1) a step of preparing a glass material having a first main surface and a second main surface facing each other,
(2) By irradiating the first main surface of the glass material with a laser, an in-plane void region in which a plurality of voids are arranged is formed on the first main surface, and the in-plane void is also formed. Forming a plurality of internal void rows in which one or more voids are arranged from the region toward the second main surface;
(3) a step of chemically strengthening the glass material on which the internal void rows are formed,
There is provided a manufacturing method having.

In this manufacturing method, the glass material in the step (1) may be manufactured by a person who carries out the manufacturing method or purchased from a third party.

Further, in the present invention, a method of manufacturing a glass article,
A step of manufacturing a glass plate by the method for manufacturing a glass plate having the above-mentioned characteristics, wherein the glass plate is a third main surface corresponding to the first main surface of the glass material, and the glass material. Having a fourth major surface corresponding to the second major surface of
Separating one or more glass articles from the glass sheet along the in-plane void regions and the plurality of internal void rows;
A manufacturing method is provided, which comprises:

Further, in the present invention, a glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
A glass plate having a compressive stress layer formed by a chemical strengthening treatment in the center of a cut surface obtained when the glass plate is cut through the in-plane void region and the plurality of internal void rows is provided. It

Further, in the present invention, a glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
In a cut surface obtained when the glass plate is cut so as to pass through the in-plane void regions and the plurality of internal void rows, a predetermined alkali metal ion extending from the first main surface to the second main surface The concentration profile has a profile in which the concentration of the predetermined alkali metal ion is higher than the bulk concentration of the glass plate,
A glass plate is provided, wherein the predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces. It

Further, in the present invention, a glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
In a cut surface obtained when the glass plate is cut so as to pass through the in-plane void regions and the plurality of internal void rows, a predetermined alkali metal ion extending from the first main surface to the second main surface The concentration profile has a profile in which the concentration of the predetermined alkali metal ion is higher toward the first main surface side and the second main surface side as compared with the central portion of the thickness of the glass plate,
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass plate is provided in which the concentration of the predetermined alkali metal ion in the concentration profile is higher than the bulk concentration of the glass plate on the cut surface.

Further, in the present invention, a glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
In a cut surface obtained when the glass plate is cut so as to pass through the in-plane void regions and the plurality of internal void rows, a predetermined alkali metal ion extending from the first main surface to the second main surface The concentration profile has a substantially parabolic profile in which the concentration of the predetermined alkali metal ion is higher toward the first main surface side and the second main surface side,
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass plate is provided in which the concentration of the predetermined alkali metal ion in the concentration profile is higher than the bulk concentration of the glass plate on the cut surface.

Further, in the present invention, a glass article,
A first main surface and a second main surface facing each other, and at least one end surface joining both main surfaces;
On the end face, having a compressive stress layer formed by a chemical strengthening treatment,
A glass article is provided in which a crack depth in a direction perpendicular to the end face is shallower than a depth of the compressive stress layer in a direction perpendicular to the end face.

Further, in the present invention, a glass article,
A first main surface and a second main surface facing each other, and at least one end surface joining both main surfaces;
In the end surface, the concentration profile of the predetermined alkali metal ion extending from the first main surface to the second main surface has the first main surface side and the second main surface side as compared to the central portion in the thickness direction. Has a profile in which the concentration of the alkali metal ion is higher toward the main surface of
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass article is provided in which the concentration of the predetermined alkali metal ion in the concentration profile at the end face is higher than the bulk concentration of the glass article.

Further, in the present invention, a glass article,
A first main surface and a second main surface facing each other, and at least one end surface joining both main surfaces;
In the end face, the concentration profile of a predetermined alkali metal ion extending from the first main surface to the second main surface is such that the alkali metal ion is closer to the first main surface side and the second main surface side. Has a high parabolic profile with a high concentration of
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass article is provided in which the concentration of the predetermined alkali metal ion in the concentration profile at the end face is higher than the bulk concentration of the glass article.

Furthermore, in the present invention, a glass article manufacturing apparatus,
A separating means for separating one or more glass articles from the glass plate,
The glass plate is a glass plate having the characteristics described above,
The separating means is
Applying a pressing force along the in-plane void region to the glass plate,
Deforming the glass plate so that the first main surface or the second main surface is convex, and applying tensile stress due to thermal stress along the in-plane void region to the glass plate By one or more selected from
A manufacturing apparatus is provided for separating the one or more glass articles from the glass plate.

INDUSTRIAL APPLICABILITY The present invention can provide a glass article and a method for producing a glass plate that can significantly suppress the deterioration of the appearance quality due to scratches and can obtain a glass article having good strength. Moreover, the glass article and glass plate which can be manufactured by such a manufacturing method can be provided. Further, the present invention can provide an apparatus for manufacturing such a glass article.

It is the figure which showed typically the flow of the manufacturing method of the glass article by one Embodiment of this invention. FIG. 3 is a diagram schematically showing the form of a glass material that can be used in the method for manufacturing a glass article according to the embodiment of the present invention. It is a schematic diagram for demonstrating the form of an in-plane void area|region and an internal void row. It is the figure which showed typically one form of the in-plane void area|region. It is the figure which showed typically the state in which the some in-plane void area|region was formed in the 1st main surface of a glass material. It is the figure which showed an example of the in-plane void area typically. It is the figure which showed typically another example of the in-plane void area|region. It is the figure which showed typically the state which several glass articles were isolate|separated from the glass plate. It is the figure which showed typically an example of the apparatus which can be used when separating a glass article from a glass plate in a 1st manufacturing method. It is the figure which showed typically an example of another apparatus which can be used when separating a glass article from a glass plate in a 1st manufacturing method. It is the figure which showed typically the flow of the manufacturing method of the glass plate by one Embodiment of this invention. 1 is a diagram schematically showing a glass article according to an embodiment of the present invention. FIG. 3 is a diagram schematically showing a concentration profile of introduced ions in one end face of a glass article according to one embodiment of the present invention in a thickness direction. 1 is a diagram schematically showing a glass plate according to an embodiment of the present invention. It is a SEM photograph showing an example of the 1st main surface and section of the 1st glass plate. 3 is a SEM photograph showing an example of an internal void row on a virtual end face of a glass plate according to an embodiment of the present invention. 3 is a SEM photograph showing an example of an internal void row on a virtual end face of a glass plate according to an embodiment of the present invention. 3 is a SEM photograph showing an example of an internal void row on a virtual end face of a glass plate according to an embodiment of the present invention. It is the figure which showed the relationship between the glass substrate and the sample which were extract|collected in an Example. It is a figure showing the in-plane stress distribution result measured in the 1st end surface of sample A. It is a figure showing the in-plane stress distribution result measured in the 1st end surface of sample B. It is a figure showing the in-plane stress distribution result measured in the 1st end surface of sample C. 6 is a graph showing the results of potassium ion concentration analysis obtained for sample A. 6 is a graph showing the results of potassium ion concentration analysis obtained for sample B. 9 is a graph showing the results of potassium ion concentration analysis obtained for sample C. It is the figure which showed the structure of the flat bending test apparatus typically. It is the figure which showed the structure of the longitudinal bending test apparatus typically. It is the figure (Weibull distribution chart) which showed collectively the result of the flat bending test obtained in each sample. It is the figure (Weibull distribution chart) which showed collectively the result of the longitudinal bending test obtained in each sample.

An embodiment of the present invention will be described below with reference to the drawings.

(The manufacturing method of the glass article by one Embodiment of this invention)
A method for manufacturing a glass article according to an embodiment of the present invention will be described with reference to FIGS.

FIG. 1 schematically shows a flow of a method for manufacturing a glass article (hereinafter, referred to as “first manufacturing method”) according to an embodiment of the present invention.

As shown in FIG. 1, the first manufacturing method is
A step of preparing a glass material having a first main surface and a second main surface facing each other (glass material preparation step) (step S110),
A step of irradiating the first main surface of the glass material with a laser to form an in-plane void region on the first main surface and forming an internal void row inside the glass material (laser irradiation step) (step S120) )When,
A step of chemically strengthening the glass material (chemical strengthening step) (step S130),
A step of separating a glass article from a glass plate which is a chemically strengthened glass material along the in-plane void region and an internal void row (separation step) (step S140),
Have.

Hereinafter, each step will be described with reference to FIGS. 2 to 10 are diagrams schematically showing one step of the first manufacturing method.

(Step S110)
First, a glass material having a first main surface and a second main surface facing each other is prepared.

The glass composition of the glass material is not particularly limited as long as it can be chemically strengthened. The glass material may be, for example, soda lime glass, aluminosilicate glass, alkali aluminosilicate glass, or the like.

At this stage, the glass material may be chemically strengthened or may not be chemically strengthened. It should be noted that the chemical strengthening process here is different from the chemical strengthening process performed in the subsequent step S130.

In order to clarify this point, the chemical strengthening treatment at this stage is hereinafter referred to as “preliminary chemical strengthening treatment”, and is distinguished from the subsequent chemical strengthening treatment.

The number of preliminary chemical strengthening treatments may be once or twice or more, and is not particularly limited. When the preliminary chemical strengthening treatment is performed twice or more, the profile of the residual stress layer in the direction orthogonal to the main surface can be made different from the profile obtained when the preliminary chemical strengthening treatment is performed only once. ..

The thickness of the glass material is not particularly limited, but may be in the range of 0.03 mm to 6 mm, for example.

The glass material may be provided in a plate shape or a roll shape. When a roll-shaped glass material is used, it can be transported more easily than a plate-shaped material. In the case of a plate-shaped glass material, the first and second main surfaces do not necessarily have to be flat and may be curved.

FIG. 2 schematically shows the form of the plate-shaped glass material 110 as an example. The glass material 110 has a flat first main surface 112, a flat second main surface 114, and an end surface 116.

(Step S120)
Next, the plate-shaped glass material 110 is irradiated with laser. Thereby, an in-plane void region is formed on the first main surface 112 of the glass material 110. A plurality of internal void rows are formed below the in-plane void region, that is, on the second main surface 114 side.

Here, the “in-plane void region” means a linear region formed by arranging a plurality of surface voids in a predetermined arrangement. The "internal void row" means a linear region formed by arranging one or more voids in the glass material from the first main surface toward the second main surface. ..

Hereinafter, the forms of the “in-plane void region” and the “internal void row” will be described in more detail with reference to FIG. FIG. 3 schematically shows an in-plane void region and an internal void row formed in the glass material.

As shown in FIG. 3, one in-plane void region 130 and a plurality of internal void rows 150 corresponding to the in-plane void region 130 are formed in the glass material 110.

As described above, the in-plane void region 130 means a linear region in which the plurality of surface voids 138 are arranged in a predetermined arrangement. For example, in the example of FIG. 3, a plurality of surface voids 138 are arranged in a fixed direction (X direction) on the first main surface 112 of the glass material 110, whereby an in-plane void region 130 is formed. ..

Each surface void 138 corresponds to a laser irradiation position on the first main surface 112, and has a diameter of, for example, 1 μm to 5 μm. However, the diameter of the surface void 138 changes depending on the laser irradiation conditions, the type of the glass material 110, and the like.

The center-to-center distance P between adjacent surface voids 138 is arbitrarily determined based on the composition and thickness of the glass material 110, laser processing conditions, and the like. For example, the center-to-center distance P may be in the range of 2 μm to 10 μm. The center-to-center distance P between the surface voids 138 does not have to be equal at all positions, and may be different depending on the location. That is, the surface voids 138 may be arranged at irregular intervals.

On the other hand, as described above, the internal void row 150 is formed by arranging one or more voids 158 in the glass material 110 from the first main surface 112 toward the second main surface 114. Means a linear region.

The shape, size, and pitch of the void 158 are not particularly limited. The void 158 may have a shape such as a circle, an ellipse, a rectangle, or a triangle when viewed from the Y direction. The maximum dimension of the void 158 when viewed from the Y direction (corresponding to the length of the void 158 along the extending direction of the internal void row 150 in the normal case) is, for example, in the range of 0.1 μm to 1000 μm. It may be.

Each inner void row 150 has a corresponding surface void 138. For example, in the example shown in FIG. 3, a total of 18 internal void rows 150 corresponding to each of the 18 surface voids 138 are formed.

In the example of FIG. 3, the voids 158 forming one internal void row 150 are arranged along the thickness direction (Z direction) of the glass material 110. That is, each internal void row 150 extends in the Z direction. However, this is merely an example, and the voids forming the internal void row 150 may be arranged from the first major surface 112 to the second major surface 114 in a state of being inclined with respect to the Z direction. ..

Further, in the example of FIG. 3, each internal void row 150 is configured by an array of a total of three voids 158, except for the surface voids 138. However, this is merely an example, and each internal void row 150 may be made up of one or two voids 158, or four or more voids 158. Further, the number of voids 158 included in each internal void row 150 may be different. Additionally, some voids 158 may be interlocked with surface voids 138 to form "long" surface voids 138.

Furthermore, each internal void row 150 may or may not have voids (second surface voids) opened at the second major surface 114.

As is clear from the above description, the in-plane void region 130 is not a region that is actually formed as a continuous “line”, but a virtual one that is formed when the surface voids 138 are connected. It should be noted that it represents a linear region.

Similarly, it should be noted that the internal void row 150 represents an imaginary linear region formed when the voids 158 are connected, rather than a region that is actually formed as a continuous “line”. There is.

Further, one in-plane void region 130 does not necessarily have to be recognized as one "line" (row of surface voids 138), and one in-plane void region 130 is placed in close proximity to each other. It may be formed as an aggregate of a plurality of parallel “lines”.

FIG. 4 shows an example of the in-plane void region 130 recognized as an aggregate of a plurality of such “lines”. In this example, two parallel surface void rows 138A and 138B are formed on the first main surface 112 of the glass material 110, and these form one in-plane void region 130. .. The distance between both surface void rows 138A and 138B is, for example, 5 μm or less, and preferably 3 μm or less.

Note that, in the example of FIG. 4, the in-plane void region 130 is composed of two surface void arrays 138A and 138B, but the in-plane void region 130 may be composed of more surface void arrays. ..

Hereinafter, the in-plane void region composed of such a plurality of surface void rows is particularly referred to as “multi-line in-plane void region”. Further, the in-plane void region 130 composed of one surface void row as shown in FIG. 3 is particularly referred to as “single line in-plane void region”, and is distinguished from “multi-line in-plane void region”.

The in-plane void region 130 and the internal void row 150 described above can be formed by irradiating the first main surface 112 of the glass material 110 with a laser.

More specifically, first, by irradiating the first position of the first main surface 112 of the glass material 110 with a laser, the first main surface 112 and the second main surface 114 are covered with the first main surface 112. A first internal void row including surface voids is formed. Next, by changing the irradiation position of the laser on the glass material 110 and irradiating the laser on the second position of the first main surface 112 of the glass material 110, the second main surface 112 is changed from the first main surface 112 to the second main surface 112. A second array of internal voids is formed over the surface 114, the second row of internal voids including the second surface voids. By repeating this operation, the in-plane void region 130 and the internal void row 150 corresponding thereto can be formed.

In addition, when the laser irradiation is performed once, an internal void row having voids 158 sufficiently close to the second main surface 114 is not formed, that is, the void closest to the second main surface 114 in the voids 158 is not formed. , If it is still far enough from the second major surface 114 (for example, in the void closest to the second major surface 114, the distance from the first major surface 112 is less than 1 of the thickness of the glass material 110). /2 or less), the laser irradiation may be performed twice or more at substantially the same irradiation position. Here, the "substantially the same (irradiation) position" is meant to include not only a case where the two positions are completely coincident with each other but also a case where the two positions are slightly deviated (for example, a displacement of 3 μm at maximum).

For example, laser irradiation is performed a plurality of times along the first direction parallel to the first main surface 112 of the glass material 110 to form the first in-plane void region 130 and the internal void row 150 corresponding thereto. After (first pass), laser irradiation is performed in substantially the same direction and substantially the same irradiation position as in the first pass (second pass), so that a “deeper” corresponding to the first in-plane void region 130 is obtained. The internal void row 150 may be formed.

Depending on the thickness of the glass material 110, the distance from the center of the void closest to the second main surface 114 among the voids 158 forming the internal void row 150 to the second main surface 114 is , 0 μm to 10 μm is preferable.

Examples of lasers that can be used for such processing include short pulse lasers having a pulse width of femtosecond order to nanosecond order, that is, 1.0×10 ^{−15 to} 9.9×10 ⁻⁹ seconds. Such a short pulse laser beam is preferably a burst pulse because the internal voids are efficiently formed. Further, the average output during the irradiation time of such a short pulse laser is, for example, 30 W or more. When this average output of the short pulse laser is less than 10 W, sufficient voids may not be formed. As an example of the burst pulse laser light, one internal void train is formed by a burst laser having a pulse number of 3 to 10, the laser output is about 90% of the rating (50 W), the burst frequency is about 60 kHz, and the burst time is The width may be 20 picoseconds to 165 nanoseconds. As a time range of burst, a preferable range is 10 nanoseconds to 100 nanoseconds.

As a laser irradiation method, a method of utilizing self-focusing of a beam based on the Kerr-effect, a method of using a Gaussian-Bessel beam together with an axicon lens, and a line focus forming beam by an aberration lens are used. There are ways. In any case, any method may be used as long as the in-plane void region and the internal void row can be formed.

For example, when a burst laser device (Patent Document 2) is used, the size of each void forming the internal void row 150, the number of voids included in the internal void row 150, and the like can be obtained by appropriately changing the laser irradiation conditions. Can be changed to some extent.

In the description below, a plane including the in-plane void region 130 and the internal void row 150 corresponding to the in-plane void region 130 (a plane 170 indicated by a hatch in FIG. 3) is referred to as a “virtual end face”. In some cases." The virtual end surface 170 substantially corresponds to the end surface of the glass article manufactured by the first manufacturing method.

FIG. 5 schematically shows, as an example, a state in which a plurality of in-plane void regions 130 are formed on the first main surface 112 of the glass material 110 by the step S120.

In the example of FIG. 5, five in-plane void regions 130 are formed on the first main surface 112 of the glass material 110 in the horizontal direction (X direction) and in the vertical direction (Y direction). Although not visible from FIG. 5, one or more voids are intermittent toward the second main surface 114 below each in-plane void region 130, that is, on the side of the second main surface 114. And a plurality of internal void rows arranged in a line.

A portion surrounded by the four in-plane void regions 130 and the corresponding inner void rows, that is, a virtual portion surrounded by four virtual end faces is referred to as a glass piece 160.

The shape of the in-plane void region 130 and the shape of the glass piece 160 substantially correspond to the shape of the glass article obtained after step S140. For example, in the example of FIG. 5, 16 rectangular glass articles are finally manufactured from the glass material 110. Further, as described above, the virtual end face including each in-plane void region 130 and the corresponding internal void row 150 corresponds to one end face of the glass article manufactured after step S140.

The arrangement form of the in-plane void region 130 and the glass piece 160 shown in FIG. 5 is merely an example, and these are formed in a predetermined arrangement according to the shape of the final glass article.

6 and 7 schematically show an example of another form of the assumed in-plane void region.

In the example of FIG. 6, each in-plane void region 131 is arranged as one closed line (loop) having a substantially rectangular shape, and has a curved portion at a corner portion. Therefore, the glass piece 161 surrounded by the in-plane void region 131 and the internal void row (not visually recognized) has a substantially rectangular plate shape having curved portions at the corners.

Further, in the example of FIG. 7, each in-plane void region 132 is arranged as a substantially circular closed line (loop). Therefore, the glass piece 162 has a substantially disc shape.

Moreover, in these examples, the end surface of the glass article is formed by one virtual end surface, and thus the end surface of the glass article obtained is one.

As described above, the in-plane void regions 130, 131, and 132 may be formed in a linear shape, a curved shape, or a combination of both. Further, the glass pieces 160, 161, 162 may be surrounded by a single virtual end face or a plurality of virtual end faces.

(Step S130)
Next, the glass material 110 is chemically strengthened.

The conditions for the chemical strengthening treatment are not particularly limited. The chemical strengthening may be performed, for example, by immersing the glass material 110 in a molten salt at 430°C to 500°C for 1 minute to 2 hours.

Nitrate may be used as the molten salt. For example, when replacing lithium ions contained in the glass material 110 with larger alkali metal ions, a molten salt containing at least one of sodium nitrate, potassium nitrate, rubidium nitrate, and cesium nitrate may be used. Moreover, when replacing the sodium ion contained in the glass material 110 with a larger alkali metal ion, the molten salt containing at least one of potassium nitrate, rubidium nitrate, and cesium nitrate may be used. Furthermore, when the potassium ions contained in the glass material 110 are replaced with larger alkali metal ions, a molten salt containing at least one of rubidium nitrate and cesium nitrate may be used.

Note that one or more salts such as potassium carbonate may be added to the molten salt. In this case, a low-density layer having a thickness of 10 nm to 1 μm can be formed on the surface of the glass material 110.

By chemically strengthening the glass material 110, a compressive stress layer can be formed on the first main surface 112 and the second main surface 114 of the glass material 110, whereby the first main surface 112 and the first main surface 112 can be formed. The strength of the second main surface 114 can be increased. The thickness of the compressive stress layer corresponds to the penetration depth of the alkali metal ions for substitution. For example, when replacing sodium ions with potassium ions using potassium nitrate, the thickness of the compressive stress layer can be set to 8 μm to 27 μm in soda lime glass, and the thickness of the compressive stress layer can be set to 10 μm to 100 μm in aluminosilicate glass. Can be In the case of aluminosilicate glass, the depth at which alkali metal ions penetrate is preferably 10 μm or more, more preferably 20 μm or more.

As described above, in the conventional method for producing a chemically strengthened glass article,
(I) a step of preparing a large-sized glass material,
(II) A step of cutting and collecting a large number of product-shaped glass substrates from a glass material, and (III) a step of chemically strengthening the collected glass substrates,
After that, a glass article is manufactured.

On the other hand, in the first manufacturing method, the chemical strengthening process is performed using the glass material 110 as the object to be processed. In this case, unlike the conventional case where a glass article having a product shape is chemically strengthened, the object to be processed is easily handled during the chemical strengthening.

For example, even if the end surface 116 (see FIG. 5) of the glass material 110 is scratched, this portion is not included in the final glass article. Further, during the chemical strengthening treatment, for example, the outer peripheral portion of the glass material 110, which is not used as a glass article, can be utilized to support or grip the object to be treated.

Therefore, according to the first manufacturing method, it becomes easier to secure the appearance without damage and the quality of strength of the glass article to be manufactured, as compared with the conventional method, and it is possible to increase the manufacturing yield.

Here, in the first manufacturing method, since the glass material 110 is chemically strengthened before forming the shape of the glass article, the glass article obtained after the separating step S140 has an end surface that is not chemically strengthened. You may have. In this case, the glass article cannot have sufficient strength.

However, the inventors of the present application introduced the glass material 110 after the step S130 of the first manufacturing method, that is, in the glass material 110 after the chemical strengthening treatment, by the chemical strengthening treatment even on the virtual end face (that is, the end face of the cut glass article). It was found that there are generated alkali metal ions (hereinafter referred to as "introduced ions"). Further, it has been found that since the smoothness of the virtual end face is high, the processing step for improving the smoothness of the end face can be omitted.

As will be described later, on the virtual end face, unlike the first main surface 112 and the second main surface 114, the introduced ions show a non-uniform concentration distribution in the plane and the thickness direction of the glass material 110. The concentration of the introduced ions decreases toward the central portion of. However, the alkali metal ions introduced by the chemical strengthening treatment exist on the entire virtual end face, and the introduced ions also exist in the central portion in the thickness direction, and the concentration thereof is not zero.

This fact is that in the first manufacturing method, the fine surface voids 138 formed on the surface of the glass material 110 by laser irradiation and the inside of the glass material 110 were formed during the chemical strengthening treatment in step S130. This suggests that the molten salt is introduced into the glass material 110 through the fine voids 158, and further that a substitution reaction occurs between the introduced molten salt and the virtual end face. is there. As far as the applicant knows, such a phenomenon has not been reported so far.

Further, as a result of supporting this phenomenon, the glass article manufactured through the first manufacturing method, that is, step S110 to step S140, is a conventional glass article manufactured through the above-mentioned steps (I) to (III). It has been confirmed to have sufficient strength comparable to that of Details will be described later.

As described above, in the first manufacturing method, after the step S130, the glass material 110 in which the first main surface 112, the second main surface 114, and each virtual end surface are chemically strengthened can be obtained. ..

(Step S140)
Next, the glass article is separated from the chemically strengthened glass material 110, that is, the glass plate 175.

FIG. 8 schematically shows a state in which a total of 16 glass articles 180 are separated from the glass plate 175. Each glass article 180 has four end faces 186.

When separating the glass article 180 from the glass plate 175, the aforementioned virtual end face is used. In other words, the glass piece 160 surrounded by the virtual end face described above is separated from the glass plate 175 to form the glass article 180. Therefore, each end surface 186 of glass article 180 corresponds to one of the aforementioned virtual end surfaces.

As described above, the chemically strengthened glass material usually has a problem that it is difficult to separate the glass article from the glass plate 175 because the first and second main surfaces are strengthened.

However, in the first manufacturing method, the virtual end surface of the glass plate 175 has a plurality of surface voids 138 and voids 158 included in the in-plane void region 130 and the corresponding inner void row 150 in the surface. Therefore, when the glass article 180 is separated from the glass plate 175, these voids 138 and 158 function as if they were “perforations formed in the plane and inside”. Therefore, in the first manufacturing method, it is possible to easily separate from the glass plate 175 by using the virtual end face. In particular, when the in-plane void region 130 is a “multi-line in-plane void region”, the glass article 180 can be more easily separated.

Here, as described above, the in-plane void region 130 is composed of the plurality of voids 138, and the internal void row 150 is composed of the plurality of voids 158. The in-plane void region 130, the internal void row 150, and the voids 138 and 158 are different from, for example, a through hole formed so as to penetrate in the thickness direction of the glass plate.

Further, as described above, the glass plate 175 is also chemically strengthened on the virtual end surface. Thus, the resulting glass article 180 also has chemically strengthened end faces 186. Therefore, the first manufacturing method has a problem in the conventional method of chemically strengthening a glass material and then separating the glass article, that is, since the glass article has an end surface that is not chemically strengthened, sufficient strength is obtained for the glass article. The problem of not being present can be avoided.

The specific method for carrying out step S140 is not particularly limited. For example, one or more glass articles 180 may be separated from glass plate 175 by mechanical or thermal methods.

FIG. 9 schematically shows an example of an apparatus that can be used when separating a glass article from a glass plate in step S140 of the first manufacturing method. In this device 200, one or more glass articles 180 can be separated from the glass plate 175 by a mechanical method.

As shown in FIG. 9, the device 200 includes a pedestal 210 and a roller 220. The roller 220 can move or rotate along an arbitrary direction in the XY plane according to a command from a controller (not shown). Further, the pressing force and the moving speed of the roller 220 can be adjusted in synchronization by the controller.

When separating the glass article from the glass plate using the apparatus 200, first, the glass plate 175 is placed on the pedestal 210. A protective sheet (not shown) may be arranged between the pedestal 210 and the glass plate 175 to prevent scratches.

Next, the roller 220 is placed on the glass plate 175 such that the tip of the roller 220 contacts the glass plate 175. At this time, a protective sheet (not shown) may be further arranged on the glass plate 175 to prevent scratches.

When a command from the controller is received in this state, the roller 220 moves on the glass plate 175 along the in-plane void region 130. The tip of the roller 220 has a ridge angle or a hemispherical shape. Therefore, the glass plate 175 is divided along the virtual end face by the pressing force of the roller 220. By repeating this operation along each in-plane void region 130, one or more glass articles 180 can be separated from the glass plate 175.

In addition, in the example of FIG. 9, each in-plane void region 130 is linear. However, for example, with respect to the curved in-plane void regions 131 and 132 as shown in FIGS. 6 and 7, the same operation is performed to separate one or more glass articles 180 from the glass plate 175. be able to.

FIG. 10 schematically shows an example of another device that can be used in separating a glass article from a glass plate. In this device 250, one or more glass articles 180 can be separated from the glass plate 175 by a mechanical method.

As shown in FIG. 10, the device 250 has a structure that supports a glass plate 175 along a support member 270 via a deformable sheet-shaped member 260.

The support member 270 in the apparatus 250 may be a general cylindrical roll shape when each in-plane void region has a linear shape. When transported on the support member 270, the glass plate 175 bends, and a bending moment along the in-plane void region acts. As a result, the in-plane void region is divided at high speed. In the next step, cutting along another direction is repeated. Further, in the case of the curved in-plane void regions 131 and 132 as shown in FIGS. 6 and 7, the supporting member 270 is a flat plate or is a sheet which is curved upwardly and is deformable into the supporting member 270. The one or more glass articles 180 are separated from the glass plate 175 by causing the deformation of the glass plate 175 to follow the support member 270 via the member 260 and applying a bending moment along the in-plane void region. be able to. In this case, it is preferable that the sheet-like member 260 is preliminarily adhered to the glass plate 175 with sufficient adhesive force in advance and the sheet-like member 260 is stretched and deformed at the time of separation. As the material of the sheet-shaped member 260, a flexible material capable of being stretched and deformed enough to be separated, for example, a rubber material or the like is used.

On the other hand, when separating one or more glass articles 180 from the glass plate 175 by a thermal method, a “surface absorption method” or an “internal absorption method” may be used.

Among these, in the “surface absorption method”, the glass article 180 is separated from the glass plate 175 by locally heating the first main surface 112 of the glass plate 175 using a heat source to generate thermal stress. As the heat source, for example, a laser (CO ₂ laser or the like) having a relatively long wavelength, a burner, a heater wire, or the like is used. By concentrating the heat from the heat source in the in-plane void regions 130, thermal stress is generated in the in-plane void regions 130 and further in the virtual end faces, and the glass plate 175 is broken along these virtual end faces. Thereby, the glass article 180 can be separated.

On the other hand, in the “internal absorption method”, a laser having a relatively short wavelength (CO laser or the like) is used. When the glass plate 175 is irradiated with such a laser, the heat of the laser is absorbed inside the glass plate 175. Therefore, by irradiating the laser along the in-plane void region 130, it is possible to locally generate internal stress on the virtual end face and break it from other portions. As a result, the glass article 180 is separated from the glass plate 175.

In the above description, the embodiment of the separation method has been described by taking the method of obtaining one or two or more glass articles 180 from one glass plate 175 as an example. However, the above-described method (mechanical method and “internal absorption method”) may be performed by stacking a plurality of glass plates 175. In this case, more glass articles 180 can be manufactured at one time.

Generally, when separating a glass article from a glass material, the glass material is cut using a glass cutter or the like. In this case, the end surface of the glass article tends to be a “rough” end surface having irregularities.

However, in the first manufacturing method, when the glass article 180 is separated, it is not always necessary to use a cutting means such as a glass cutter. Therefore, when the glass article 180 is separated, a relatively smooth end surface 186 is formed. Obtainable.

However, in particular cases, such as when the smooth end face 186 is not required, the glass article 180 may be separated by cutting the glass plate 175 along the virtual end face using a glass cutter or the like. .. Also in this case, the presence of the virtual end face allows the glass plate 175 to be cut more easily than in the case of normal cutting.

Through the above steps, one or more glass articles 180 can be manufactured.

In addition, in order to protect the end surface 186 of the obtained glass article 180, a material such as a resin may be applied to the end surface 186.

According to the first manufacturing method, due to the above-described characteristics, it is possible to significantly suppress the deterioration of the appearance quality of the glass article 180 and to obtain the glass article 180 having good strength.

Heretofore, one manufacturing method for manufacturing a glass article has been described by taking the first manufacturing method as an example. However, the first manufacturing method is merely an example, and various modifications can be made when actually manufacturing the glass article.

For example, the chemical strengthening treatment in step S130 of the first manufacturing method does not necessarily have to be performed on both the first main surface 112 and the second main surface 114 of the glass material 110, but one main surface. In this case, a mode in which the chemical strengthening treatment is not performed may be considered.

Further, for example, after the step S130 and before the step S140, a step of adding various functions to the glass plate 175 (additional step) may be performed.

The additional step is not limited to this, but may be performed, for example, to add an additional function such as a protective function to the surface of the glass plate 175 or to modify the surface.

Such an additional step is, for example, a step of attaching a functional film to the first main surface 112, the second main surface and/or the end surface 116 of the glass plate 175 (hereinafter, these are collectively referred to as “exposed surface”). And a step of performing surface treatment (including surface modification) on at least a part of the exposed surface.

Examples of the surface treatment method include etching treatment, film forming treatment, and printing treatment. The film forming process may be performed using, for example, a coating method, a dipping method, a vapor deposition method, a sputtering method, a PVD method, a CVD method, or the like. The surface treatment also includes cleaning using a chemical solution.

By surface treatment, for example, a low reflection film, a high reflection film, a wavelength selection film such as an IR absorption film or a UV absorption film, an anti-glare film, an anti-fingerprint film, an anti-fog film, printing, an electronic circuit and a multi-layered film of these. May be formed.

Furthermore, before or after step S120, or both, that is, before or after forming the in-plane void region 130, or both, a groove may be formed in at least one main surface of the glass material 110.

For example, when the in-plane void region 130 is already formed on the first main surface 112 of the glass material 110, the groove may be formed along the in-plane void region 130. Alternatively, if the in-plane void region 130 is not yet formed on the first main surface 112 of the glass material 110, a groove may be formed along the in-plane void region 130 that will be formed in the future.

The shape of the groove is not particularly limited. The groove may have, for example, a substantially V-shaped cross section, a substantially U-shaped cross section, a substantially inverted trapezoidal shape, and a substantially concave shape. In addition, in the form of these grooves, the opening portion of the first main surface 112 or the second main surface 114 of the groove may be round.

When the groove having such a cross-sectional shape is formed, in the glass article 180 obtained after step S140, the connection portion of the end surface 186 with the first main surface 112 and/or the second main surface 114 is chamfered or rounded. It will be in a state of being. Therefore, the post-processing step for the glass article 180 can be omitted.

The depth of the groove is, for example, less than 1/2 of the thickness of the glass material 110. The depth of the groove is preferably 0.01 mm or more.

The groove forming means may be, for example, a grindstone or a laser. In particular, laser processing is preferable in terms of groove accuracy and quality.

(The manufacturing method of the glass plate by one Embodiment of this invention)
Next, with reference to FIG. 11, a method for manufacturing a glass plate according to an embodiment of the present invention will be described.

FIG. 11 schematically shows a flow of the method for manufacturing a glass plate (hereinafter, referred to as “second manufacturing method”) according to the embodiment of the present invention.

As shown in FIG. 11, the second manufacturing method is
A step of preparing a glass material having a first main surface and a second main surface facing each other (glass material preparing step) (step S210),
A step of irradiating the first main surface of the glass material with a laser to form an in-plane void region on the first main surface and forming an internal void row inside the glass material (laser irradiation step) (step S220) )When,
A step of chemically strengthening the glass material (chemical strengthening step) (step S230),
Have.

As is apparent from FIG. 11, the second manufacturing method corresponds to the first manufacturing method shown in FIG. 1 described above in which the separation step of step S140 is omitted.

That is, in this second manufacturing method, the glass plate has one or more virtual end faces, that is, in-plane void regions and the corresponding internal void rows, as shown in FIGS. Glass material is manufactured.

In other words, in the present application, the “glass plate” means an intermediate in the process from the glass material to the production of the glass article, that is, the processed glass material.

In such a "glass plate", when the step of processing the glass material (for example, step S210 to step S230) and the step of separating the glass article from the glass plate are performed by another person or another place. , Or when they are performed at appropriate intervals in time, it is significant.

It will be apparent to those skilled in the art that the second manufacturing method as described above can also achieve the same effect as the first manufacturing method described above. That is, the glass plate obtained by the second manufacturing method has a virtual end face chemically strengthened, and when the glass product is separated from this glass plate, a glass product having good strength can be obtained. Moreover, the deterioration of the quality of the obtained glass article is significantly suppressed.

(Glass article according to an embodiment of the present invention)
Next, with reference to FIG. 12, a glass article according to an embodiment of the present invention will be described.

FIG. 12 schematically shows a glass article according to an embodiment of the present invention (hereinafter referred to as “first glass article”).

As shown in FIG. 12, the 1st glass article 380 has the 1st main surface 382 and the 2nd main surface 384 which mutually oppose, and the end surface 386 which connects both. The first main surface 382 corresponds to the first main surfaces of the glass base plates that face each other, and the second main surface 384 corresponds to the second main surfaces of the glass base plates that face each other. ..

In the example of FIG. 12, the first glass article 380 has substantially rectangular main surfaces 382 and 384 and four end surfaces 386-1 to 386-4. Further, each of the end faces 386-1 to 386-4 extends parallel to the thickness direction (Z direction) of the first glass article 380.

However, this is merely an example, and various forms are possible as the form of the first glass article 380. For example, the first main surface 382 and the second main surface 384 may have a rectangular shape, a circular shape, an elliptical shape, a triangular shape, or a polygonal shape. Further, the number of the end faces 386 may be, for example, one, three, or four or more depending on the form of the first main surface 382 and the second main surface 384. Furthermore, the end surface 386 may extend at an angle from the Z direction (that is, in a direction not parallel to the Z direction). In this case, a "tilted" end face is obtained.

The thickness of the first glass article 380 is not particularly limited. The thickness of the first glass article 380 may be in the range of 0.03 mm to 6 mm, for example.

Here, in the first glass article 380, the first main surface 382 and the second main surface 384 are chemically strengthened. In addition, the end surface 386 of the first glass article 380 is chemically strengthened.

However, the main surfaces 382 and 384 and the end surface 386 are different in the state of chemical strengthening, that is, the state of distribution of introduced ions (alkali metal ions introduced by the chemical strengthening treatment).

This will be described in more detail with reference to FIG. Here, it is assumed that the end surface 386 extends in a direction perpendicular to the main surfaces 382 and 384.

FIG. 13 schematically shows the concentration profile of introduced ions in the thickness direction (Z direction) at one end surface 386 (for example, 386-1) of the first glass article 380. In FIG. 13, the horizontal axis is the relative position t (%) in the thickness direction, the first main surface 382 side corresponds to t=0%, and the second main surface 384 side corresponds to t=100%. Correspond. The vertical axis represents the concentration C of introduced ions. As described above, the introduced ions impart a compressive stress layer to the alkali metal ions introduced by the chemical strengthening treatment, that is, the first major surface and the second major surface of the glass article, so that these major surfaces It means an alkali metal ion for increasing strength.

Here, this concentration C is an alkali metal ion of the same kind as the introduced ion, which is contained in the main surface 382, 384 of the glass article 380, and the portion other than the end faces 386-1 to 386-4, that is, the bulk portion of the glass article 380. It is calculated by subtracting the concentration (bulk concentration). Therefore, the bulk concentration is almost the same as the arithmetic average concentration of alkali metal ions with respect to the volume of the glass base plate before the chemical strengthening treatment.

The density profile as shown in FIG. 13 can be measured at each in-plane position of the end face 386-1 (arbitrary position along the Y direction). However, within the same end surface 386-1 of the glass article 380, the tendency of the density profile is almost the same regardless of the position of the end surface 386-1.

As shown in FIG. 13, on the end face 386-1, the concentration C of introduced ions along the thickness direction has a profile larger than the bulk concentration on the entire end face, and in this example, shows a substantially parabolic profile. That is, the concentration C of introduced ions exhibits the maximum value C _max on the first main surface 382 side (t=0%) and the second main surface 384 side (t=100%), and The minimum value C _min tends to be exhibited in the central portion (t=50%). Here, the minimum value C _min >0.

The shape of the concentration profile of the introduced ions changes depending on the thickness and material of the first glass article 380, the manufacturing conditions (chemical strengthening treatment conditions, etc.), etc. It becomes larger, and as an example, such a substantially parabolic profile is generated. However, due to the influence of the method of chemical strengthening and the like, the concentration C of the introduced ions on the side of the first main surface 382 (t=0%) and on the side of the second main surface 384 (t=100%). It is often accepted that the two do not exactly match. That is, it often happens that only the concentration C on any of the main surfaces becomes C _max . Further, the substantially parabolic profile here is different from the mathematical definition of a parabola in that the concentration C of introduced ions is different from that of the central portion in the thickness direction on the first main surface side and the second main surface side. The introduced ion concentration in the concentration profile that increases on the main surface side is higher than the bulk concentration of the glass article. Therefore, this substantially parabolic profile is a profile in which the introduced ion concentration is higher than the bulk concentration of the glass article, and the introduced ion C has a relatively trapezoidal shape in which the introduced ion C changes relatively gently in the central portion in the thickness direction. Contains profiles.

Here, assuming that the concentration (atomic ratio) of introduced ions normalized by silicon ions, that is, (concentration C of introduced ions)/(concentration of Si ions) is Cs, the minimum value of Cs at the target end surface with respect to Cs in the bulk is calculated. The ratio is preferably 1.6 or more, more preferably 1.8 or more, still more preferably 2.2 or more.

At the first major surface 382 and the second major surface 384, the concentration of introduced ions is substantially constant in the plane, and such a concentration profile of the end face 386-1 is characteristic. In addition, the first glass article 380 having such a chemically strengthened end surface 386 has not been recognized so far.

For example, when a product-shaped glass article is cut out from a glass material and the glass article is chemically strengthened, the concentration of introduced ions at the end surface of the obtained glass article is substantially constant in the plane. In that case, typically, a profile as shown by a broken line in FIG. 13 is obtained. That is, C=C _max regardless of the position. In addition, for example, when a glass material having a product shape is cut out after chemically strengthening a glass material, introduced ions are hardly detected on the end surface of the obtained glass article. That is, C≈0.

Since the end surface 386 has such a characteristic concentration profile of introduced ions, the first glass article 380 has a better strength than the glass article obtained by cutting out the conventional chemically strengthened glass material. Have.

The surface compressive stress of the first main surface 382 and the second main surface 384 of the first glass article 380 is, for example, in the range of 200 MPa to 1000 MPa, preferably in the range of 500 MPa to 850 MPa. The surface compressive stress of the end faces 386-1 to 386-4 of the first glass article 380 has a minimum value of more than 0 MPa, for example, 25 MPa to 1000 MPa or more, preferably 50 MPa to 850 MPa, more preferably 100 MPa to 850 MPa. It is a range. The surface compressive stress can be measured using, for example, a surface stress measuring device FSM-6000LE or FSM-7000H manufactured by Orihara Manufacturing Co., Ltd., which utilizes a photoelastic analysis method.

Note that the first glass article 380 may include one or more additional members on the first main surface 382, the second main surface 384, and/or the end surface 386.

Such additional members may be provided in the form of, for example, layers, membranes, films and the like. Also, such additional members may be provided on the first major surface 382, the second major surface 384, and/or the end surface 386 to provide features such as low reflection properties and protection.

The first glass article 380 is used, for example, in electronic devices (for example, information terminal devices such as smartphones and displays), camera and sensor cover glasses, architectural glass, industrial transport glass, and biomedical glass devices. Can be applied.

(Glass plate according to an embodiment of the present invention)
Next, with reference to FIG. 14, a glass plate according to an embodiment of the present invention will be described.

FIG. 14 schematically shows a glass plate (hereinafter, referred to as “first glass plate”) according to an embodiment of the present invention.

As shown in FIG. 14, the first glass plate 415 has a first main surface 417 and a second main surface 419 facing each other, and four end faces 420 (420-1 to 420-4) connecting the both. ) And. The first main surface 417 corresponds to the first main surfaces of the glass base plates that face each other, and the second main surface 419 corresponds to the second main surfaces of the glass base plates that face each other. ..

The glass composition of the first glass plate 415 is not particularly limited as long as it can be chemically strengthened. The first glass plate 415 may be, for example, soda lime glass, aluminosilicate glass, alkali aluminosilicate glass, or the like.

The thickness of the first glass plate 415 is not particularly limited, but may be in the range of 0.1 mm to 6 mm, for example.

The shapes of first main surface 417 and second main surface 419 of first glass plate 415 are not particularly limited. These may be rectangular, circular, or elliptical, for example. It should be noted that first main surface 417 and second main surface 419 do not necessarily have to be flat, and may be curved.

The first glass plate 415 has a plurality of in-plane void regions 431 on the first main surface 112, and corresponds to the lower side (the side of the second main surface) of each in-plane void region 431. A plurality of internal void rows (not visible) are formed. The internal void row may extend parallel to the thickness direction (Z direction) of the first glass plate 415, or may extend obliquely with respect to the thickness direction.

The portion surrounded by each in-plane void region 431 and the corresponding inner void row, that is, the portion surrounded by the virtual end surface is referred to as a glass piece 461.

As is clear from FIG. 14, the first glass plate 415 corresponds to the glass material 110 shown in FIG. 5 described above. That is, the first glass plate 415 is used as an intermediate in a process until a glass article is manufactured from a glass material, in other words, is used as a glass material before separating a glass article having a desired shape.

More specifically, in the first glass plate 415, a glass article (corresponding to the glass piece 461) can be obtained by separating the glass piece 461 from the first glass plate 415 along the virtual end surface. it can.

In such a first glass plate 415, a step of manufacturing the first glass plate 415 from a glass material and a step of separating the glass article from the first glass plate 415 are performed by another person or another place. It is significant when it is carried out, or when it is carried out at appropriate intervals in time.

Here, the in-plane void region 431 and the internal void row included in the first glass plate 415 will be described in more detail with reference to FIGS.

FIG. 15 shows an example of the SEM photograph including the first main surface 417 and the cross section of the first glass plate 415 shown in FIG. In FIG. 15, the upper side corresponds to the first main surface 417 of the first glass plate 415, and the lower side corresponds to the cross section of the first glass plate 415.

Two rows of surface voids are formed in the horizontal direction on the first main surface 417 of the first glass plate 415, and each row corresponds to the in-plane void region 431 shown in FIG. .. In this example, each surface void has a diameter of about 2 μm and the distance P between adjacent surface voids is about 50 μm.

Around each surface void, an altered portion (a whitish ring-shaped region) having a width of about 1 μm to 2 μm is formed. This is considered to be a residual stress portion formed by melting the components of the first glass plate 415 during laser irradiation and then solidifying.

On the other hand, the cross section of the first glass plate 415 is substantially cut along one in-plane void region 431 and the corresponding internal void row, and thus this cross section is the first glass plate 415. 415 corresponding to the virtual end face. Note that due to manual cutting, the cross section shown does not include the leftmost surface void to be precise. However, also in FIG. 15, the form of the virtual end face can be substantially grasped. Therefore, the cross-sectional portion in FIG. 15 is also called a virtual end face.

In FIG. 15, in the shown virtual end face, three vertically extending internal void rows are recognized. When referring to the center internal void row which is most clearly visible, it can be seen that a plurality of fine voids are intermittently arranged like "perforations" in this internal void row. In the internal void example, some whisker-like cracks occurring in an oblique direction, specifically, the three whisker-like cracks that can be seen in the central inner void row are due to manual cutting, and Not a void.

FIG. 16 shows an example of an SEM photograph of another virtual end face of the first glass plate 415. In FIG. 16, the upper side corresponds to the first main surface 417 side of the first glass plate 415, and the lower side corresponds to the second main surface 419 side.

From this photograph, a large number of voids are formed in a line on the virtual end face from the first main surface 417 to the second main surface 419, whereby one internal void line is formed. I understand.

In the photograph of FIG. 16, each void forming the internal void row has a maximum length (longitudinal length) of about 0.5 μm to about 1.5 μm, and the voids have a substantially circular shape or a substantially oval shape. , And a substantially rectangular shape. The partition wall between adjacent voids has a dimension of about 0.2 μm to 0.5 μm.

17 and 18 each show an example of another SEM photograph of the virtual end face of the first glass plate 415.

In the example shown in FIG. 17, one internal void row formed on the virtual end face is composed of voids having a size of about 0.5 μm to 1.5 μm. The form of the void is substantially circular or elliptical. The partition wall between adjacent voids has a size of about 0.1 μm to 2 μm.

On the other hand, in the example shown in FIG. 18, one internal void row formed on the virtual end face is composed of an elongated void having a size of about 3 μm to 6 μm. The size of the partition wall between the adjacent voids is about 0.8 μm.

As described above, the form of the internal void row included in the virtual end surface of the first glass plate 415, and further, the group of voids forming the internal void row is not particularly limited. These change variously depending on the glass composition of the first glass plate 415, laser irradiation conditions, and the like. Incidentally, the void group, due to the stress at the time of void generation, microcracks occur along the internal void rows, the void groups may be connected by the microcracks to the extent that the glass material is not separated along the inner surface void region. .. This is preferable from the viewpoint of the penetration of the molten salt into the glass material during the chemical strengthening treatment.

However, typically, the dimension of the voids forming the internal void row in the direction along the internal void row is in the range of 0.1 μm to 1000 μm, preferably 0.5 μm to 100 μm, and more preferably 0 μm. It is in the range of 0.5 μm to 50 μm. The shape of the voids forming the internal void row is a rectangle, a circle, an ellipse, or the like. Further, the thickness of the partition wall between adjacent voids is usually in the range of 0.1 μm to 10 μm.

Similarly, the dimensions of the surface voids forming the in-plane void region 431 also vary depending on the glass composition of the first glass plate 415, the laser irradiation conditions, and the like.

However, the diameter of the surface void is typically in the range of 0.2 μm to 10 μm, for example, in the range of 0.5 μm to 5 μm. The center-to-center distance P between adjacent surface voids (see FIG. 3) is in the range of 1 μm to 20 μm, for example, in the range of 2 μm to 10 μm. The smaller the center-to-center distance P, the easier it is to separate the glass article from the first glass plate 415, but since the number of repetitions of laser irradiation increases, the processing speed is restricted and a high-power oscillator is required. Becomes

Referring again to FIG. 14, in first glass plate 415, first main surface 417 and second main surface 419 are chemically strengthened. The four end surfaces 420 may or may not be chemically strengthened. In addition, in the first glass plate 415, the periphery of each glass piece 461, that is, the virtual end surface is chemically strengthened.

However, the main surfaces 417 and 419 are different from the virtual end faces in the state of chemical strengthening, that is, the state of distribution of introduced ions.

That is, on the virtual end face, the introduced ions exhibit a substantially parabolic concentration profile as shown in FIG. 13 described above along the extending direction of the internal void rows.

It should be noted that the density profile as shown in FIG. 13 does not change much even if the measurement position in the virtual end face is changed, and if the position is within the same virtual end face, the density profile does not tend to be evaluated at any position. It is almost the same.

In the first main surface 417 and the second main surface 419 of the first glass plate 415, the concentration of the introduced ions is substantially constant in the plane, and the concentration profile of the introduced ions on such an imaginary end face is obtained. Is characteristic. Further, the first glass plate 415 having the virtual end face in such a chemically strengthened state has not been recognized so far.

According to the inventors of the present application, the virtual end surface of the first glass plate 415 has a first main surface 417 when a general chemical strengthening treatment process is performed on the first glass plate 415. And with the second major surface 419 to be chemically strengthened.

Therefore, in the virtual end face, during the chemical strengthening treatment of the glass base plate of the first glass plate 415, the molten salt is introduced into the first glass plate 415 through the intermittent voids included in the virtual end face. It is considered that the substitution reaction occurs between the introduced molten salt and the virtual end surface, and the chemical strengthening occurs.

The 1st glass plate 415 which has such a characteristic can be utilized as a supply member which provides a glass article. In particular, since the virtual end surface of the first glass plate 415 is chemically strengthened, the glass article obtained from the first glass plate 415 has a chemically strengthened end portion. Therefore, by using the first glass plate 415, it is possible to provide a glass article having good strength. In addition, since the first glass plate 415 does not have an end surface to be a glass article from before chemical strengthening to separation, it can be handled as a larger plate than a glass article, so that the surface of the glass plate and the virtual end surface are not scratched. Difficult to attach, and the deterioration of strength is suppressed.

Note that the first glass plate 415 may include one or more additional members on at least one of the first main surface 417, the second main surface 419, and the end surface 420.

Such additional members may be provided in the form of, for example, layers, membranes, films and the like. Further, such an additional member includes a low reflection function, a high reflection function, a wavelength selection function such as IR absorption function or UV absorption function, an anti-glare function, an anti-fingerprint function, an anti-fog function, printing, and a multilayer structure function thereof. Also, it may be provided on at least one of the first main surface 417, the second main surface 419, and the end surface 420 in order to exert a function such as protection.

Next, examples of the present invention will be described.

By the following methods, samples of various glass articles were manufactured and their characteristics were evaluated.

(Method for manufacturing sample A)
A glass substrate made of aluminosilicate glass having a vertical and horizontal length L of 100 mm and a thickness t of 1.3 mm was prepared. The glass substrate corresponds to a glass material. As the glass substrate, a raw plate of Dragonrail (registered trademark) before being chemically strengthened was used. Therefore, the glass composition of the glass substrate is the same as in the case of Dragontrail except for the alkali metal component that is replaced by the chemical strengthening treatment. This glass substrate was irradiated with laser from one main surface side to form a plurality of in-plane void regions in the vertical and horizontal directions.

As the laser, a burst laser (pulse number: 3) manufactured by Rofin (Germany) capable of emitting a short pulse laser of picosecond order was used. The laser output was 90% of the rating (50 W). The frequency of one burst of the laser is 60 kHz, the pulse width is 15 picoseconds, and the burst width is 66 nanoseconds.

Further, the number of laser irradiations was set to only once in each in-plane void region (hence, laser irradiation in one pass). Further, in each in-plane void region, the center-to-center distance P between adjacent surface voids was set to 5 μm.

As shown in FIG. 19, on first main surface 802 of glass substrate 800, two in-plane void regions 831 were formed in the vertical direction, and nine in-plane void regions 832 were formed in the horizontal direction. The interval R between the in-plane void regions 831 in the vertical direction was 60 mm, and the interval Q between the in-plane void regions 832 in the horizontal direction was 10 mm.

The laser was applied to the first main surface 802 in a direction perpendicular to the main surface 802. Therefore, the internal void rows formed below the in-plane void regions 831 and 832 extend substantially parallel to the thickness direction of the glass substrate 800.

Next, a chemical strengthening treatment was performed on the obtained glass substrate 800.

The chemical strengthening treatment was performed by immersing the entire glass substrate 800 in a molten potassium nitrate salt. The processing temperature was 435° C., and the processing time was 1 hour.

Next, by pressing the glass substrate 800 along the in-plane void regions 831 and 832, a total of eight samples 880 from the central portion (thick frame portion in FIG. 19) of one glass substrate 800. Was collected. Each sample 880 has a length (see length R in FIG. 19) of about 60 mm and a width (see length Q in FIG. 19) of about 10 mm. Each of the four end faces of each sample 880 corresponds to the above-mentioned virtual end face. When the state of the end surface of each sample was visually confirmed, no problems such as scratches were confirmed.

The sample 880 manufactured in this manner is referred to as sample A.

(Method for manufacturing sample B)
A glass substrate similar to the glass substrate used in sample A was cut after forming in-plane void regions and internal void rows under the same laser conditions as in sample A, and a plurality of samples having a length of 60 mm and a width of 10 mm were collected. Then, each sample was subjected to a chemical strengthening treatment to manufacture sample B. The conditions for the chemical strengthening treatment are the same as in the case of Sample A described above.

In addition, in the manufacturing method of this sample B, it was found that some of the samples had scratches on the end faces and were not in a healthy state. Therefore, only a sample in a healthy state was visually selected to prepare a sample B. Since the scratches were subjected to the chemical strengthening treatment on the sample after cutting, it is expected that the scratches occurred somewhere in the middle of the process before the chemical strengthening.

(Method for manufacturing sample C)
Sample C was manufactured using a glass substrate similar to the glass substrate used in Sample A. In the case of Sample C, the laser irradiation was not performed, and the chemical strengthening treatment was directly performed on the glass substrate. The conditions for the chemical strengthening treatment are the same as in the case of Sample A described above.

Then, the chemically strengthened glass substrate was cut under the same laser conditions as the sample A, and a plurality of samples C having a length of 60 mm and a width of 10 mm were collected.

In addition, in the manufacturing method of this sample C, it turned out that a part of samples have a flaw in the end surface and include those which are not in a healthy state. Therefore, only a sample in a healthy state was visually selected to prepare a sample C. It is expected that this scratch was caused by the difficulty of cutting after the chemical strengthening treatment.

(Evaluation)
The following evaluation was performed using each sample AC manufactured as mentioned above.

(Evaluation of stress distribution)
The stress distribution on the end faces of the samples A to C was evaluated. This stress is mainly due to the chemical strengthening treatment. A birefringence imaging device (abrio: manufactured by CRi Inc., USA) was used for evaluation. In each sample, the evaluation target surface was an end surface having a length of 60 mm and a thickness of 1.3 mm (hereinafter, referred to as “first end surface”).

20 to 22 show in-plane stress distribution results measured on the first end faces of Samples A to C, respectively. In these figures, the stress distribution is not so clear because it is black and white data, but a relatively small tensile stress occurs in the center area on the right side of the figure, and the dark area entering from the end on the left side of the figure to the right side. In the figure, a tensile stress smaller than that in the central area on the right side of the figure occurs, and in the upper left and lower left corners, and on the left side edge, the darker the area, the greater the compressive stress (outside the white area). Area).

In addition, the device used includes not only the information of the evaluation target surface but also the information of the depth direction of the evaluation target surface (Q=10 mm portion in this evaluation). For this reason, in this evaluation, a so-called integrated result of stress values up to 10 mm in the depth direction from the evaluation target surface is obtained.

As shown in FIG. 20, in sample A, a large compressive stress is applied to three outer surfaces, that is, two upper and lower main surfaces and an end face having a width of 10 mm and a thickness of 1.3 mm (hereinafter, referred to as “second end face”). Exists. In particular, the "second end face" has a large compressive stress throughout regardless of the position in the thickness direction.

Further, as shown in FIG. 21, also in the case of sample B, large compressive stress exists on all three outer surfaces.

On the other hand, as shown in FIG. 22, in the case of the sample C, although large compressive stress exists on the upper and lower two main surfaces, the second end surface, especially the central portion in the thickness direction, has a substantial compressive stress. There is no compressive stress.

As described above, it was found that the second end surface of the sample A has the same compressive stress as that of the end surface of the sample B over the entire thickness direction.

(Analysis of potassium ion)
Next, the samples A to C were used to analyze the potassium ion concentration at the first end face. Specifically, line analysis using the EDX method (energy dispersive X-ray spectroscopy: Energy Dispersive X-ray Spectrometry) was performed on the first end face of each sample.

23 to 25 show the results of concentration analysis obtained for each sample. In these figures, the horizontal axis is the distance from the first main surface of the first end face, and the distance is from 0 (first main surface) to 1300 μm (second main surface). Change. The vertical axis (left axis) is the concentration (atomic ratio) of potassium ions normalized by silicon ions. 23 and 24, for reference, the right vertical axis shows the profile of the penetration depth of potassium ions. This penetration depth represents the penetration depth of potassium ions in the direction perpendicular to the first end face, measured by the EDX method. That is, this value represents the penetration depth of potassium ions in the depth direction from the first end face, measured at each position along the direction of the distance defined as described above on the first end face. ing.

Note that these analyzes were performed at several positions on the first end face of each sample, but the obtained results were almost the same.

From the results of FIG. 23, it is understood that in the case of Sample A, the concentration of potassium ions at the first end surface shows a substantially parabolic profile along the first main surface to the second main surface. That is, the potassium ion concentration tends to be high on the first main surface side and the second main surface side and low on the intermediate portion between both main surfaces.

Here, the potassium ion concentration (K/Si) originally contained in the glass substrate used for manufacturing sample A is 0.118 in bulk concentration, that is, about 0.12. On the other hand, in the profile of FIG. 23, the minimum value of potassium ion concentration (value at a depth of about 650 μm) is 0.19 to 0.20. Therefore, in the case of Sample A, it can be said that potassium ions are introduced throughout the first end surface. This is because the depth of penetration of potassium ions does not depend much on the distance from the first main surface, and even at a position of 650 μm, potassium ions are introduced up to about 20 μm. it is obvious. Here, the ratio of the minimum value of K/Si of the profile to the bulk concentration of K/Si is 1.6.

FIG. 24 shows the analysis result in the case of sample B. In the case of sample B, the first end surface is chemically strengthened, like the first main surface and the second main surface. Therefore, the potassium ion concentration does not depend on the distance on the horizontal axis, and shows a substantially constant high value at any distance.

On the other hand, as shown in FIG. 25, in the case of sample C, since the sample was cut out after the chemical strengthening treatment was performed on the glass substrate, most potassium ions were introduced into the first end face. Absent. That is, the potassium ion concentration is equal to 0.12, which is the concentration of potassium ions originally contained in the glass substrate, regardless of the distance along the horizontal axis.

As described above, in sample A, it was confirmed that potassium ions were introduced into the end face, even though the sample was collected after the chemical strengthening treatment.

(Strength evaluation)
Next, strength evaluation by a 4-point bending test was performed using each of the samples A to C.

The 4-point bending test was carried out by the following two methods (a flat bending test and a vertical bending test).

(Flat bending test)
FIG. 26 schematically shows the configuration of the flat bending test apparatus.

As shown in FIG. 26, the flat bending test apparatus 900 has a set of fulcrum members 920 and a set of load members 930. The center-to-center distance L1 of the fulcrum member 920 is 30 mm, and the center-to-center distance L2 of the load member 930 is 10 mm. The fulcrum member 920 and the load member 930 have a sufficiently long total length (length in the Y direction) as compared with the width (10 mm) of the sample used for the test.

During the test, the sample 910 is placed horizontally on the two fulcrum members 920. The sample 910 is arranged such that the respective second end surfaces 918 are equidistant from the centers of the fulcrum members 920. The sample 910 is arranged so that the first main surface 912 or the second main surface 914 faces downward.

Next, the two load members 930 are arranged above the sample 910 such that their centers correspond to the center of the sample 910.

Next, by pressing the load member 930 against the sample 910, a load is applied to the sample 910 from the upper portion of the sample 910. The head speed is 5 mm/min. The room temperature during the test is about 23° C. and the relative humidity is about 60%. The maximum tensile stress obtained from the load when the sample 910 is broken by such a test is defined as the flat bending breaking stress.

(Vertical bending test)
FIG. 27 schematically shows the configuration of the vertical bending test device.

As shown in FIG. 27, the vertical bending test apparatus 950 has a set of fulcrum members 970 and a set of load members 980. The center-to-center distance L1 of the fulcrum member 970 is 50 mm, and the center-to-center distance L2 of the load member 980 is 20 mm. The fulcrum member 970 and the load member 980 have a sufficiently long total length (length in the Y direction) as compared with the thickness (1.3 mm) of the sample used for the test.

During the test, the sample 910 is placed horizontally on the two fulcrum members 970. The sample 910 is arranged such that the respective second end surfaces 918 are equidistant from the centers of the fulcrum members 970. The sample 910 is arranged so that the first end surface 916 faces upward. The sample 910 is supported so as not to fall. In this support, friction is prevented from occurring between the sample 910 and the supporting member.

Next, the two load members 980 are arranged above the sample 910 such that the centers of the two load members 980 correspond to the center of the sample 910.

Next, by pressing the load member 980 against the sample 910, a load is applied to the sample 910 from above the sample 910. The head speed is 1 mm/min. The room temperature during the test is about 23° C. and the relative humidity is about 60%. The maximum tensile stress obtained from the load when the sample 910 is broken by such a test is defined as the longitudinal bending breaking stress.

(Test results)
FIG. 28 collectively shows the results of the flat bending test (Weibull distribution chart) obtained in Samples A to C. The straight line obtained by fitting the Weibull plot for each sample in the figure was obtained by the method of least squares.

As shown in FIG. 28, it was found that in sample C, the breaking stress was not so high and the sample did not show good strength. On the other hand, it was found that the sample A and the sample B have almost the same good strength.

In addition, in the Weibull distribution diagram, it is generally known that the slope of a straight line correlates with the variation between samples. That is, it can be said that the smaller the variation between samples, the steeper the slope of the straight line.

In the results shown in FIG. 28, the slope of the straight line of sample A is steeper than that of sample B. Therefore, it can be said that sample A has less variation in strength between samples than sample B. The reason for this is that in sample A, the internal void rows that are the end portions of the sample A are covered with the glass itself during the chemical strengthening process, so that scratches are less likely to occur and variations in strength are reduced.

Next, in FIG. 29, the results (Weibull distribution chart) of the longitudinal bending test obtained in Samples A to C are shown together. The straight line obtained by fitting the Weibull plot for each sample in the figure was obtained by the method of least squares.

As shown in FIG. 29, it was found that Sample C did not have a high breaking stress and did not exhibit good strength. On the other hand, it was found that Sample A and Sample B exhibit good strength. The breaking stress of sample A is slightly lower than the breaking stress of sample B because there is a difference in potassium ion concentration due to the chemical strengthening treatment on the first end face described above.

Further, as described above, since the slope of the straight line of sample A is steeper than that of sample B, it can be said that sample A has less variation in intensity between samples than sample B. The reason for this is that in sample A, the internal void rows that are the end portions of the sample A are covered with the glass itself during the chemical strengthening process, so that scratches are less likely to occur and variations in strength are reduced.

As described above, it was confirmed that in the sample A, potassium ions were introduced into the end faces during the chemical strengthening treatment of the glass substrate, and as a result, the sample A exhibited good strength.

Next, another embodiment of the present invention will be described.

(Other Example 1)

(Sample preparation)
The sample A described above was used as a sample. As shown in FIG. 23, in the case of this sample, the penetration depth of the alkali metal ions at the first end face is constant at approximately 20 μm regardless of the distance from the first main surface. Hereinafter, the sample used in this example is particularly referred to as “sample D”.
(Measurement of surface roughness of the first end face)
The surface roughness (arithmetic mean roughness Ra) of the first end surface of Sample D was measured. The arithmetic mean roughness Ra was measured using Surfcom1400D manufactured by Tokyo Seimitsu Co., Ltd. according to JIS B0601 (2013). The measurement length was 8.0 mm along the longitudinal direction of the first end face. The cutoff value of the λc contour curve filter was 0.8 mm. The measurement speed was 0.3 mm/sec.

The measurement was performed using 12 samples D. Each sample was measured at three locations.

(Measurement of crack depth of the first end face)
The crack depth of the first end surface of Sample D was measured by the following method. The measurement direction of the crack depth was perpendicular to the first end face.

Sample D was etched under the following conditions in order to facilitate observation of cracks before measurement.
(1) Preparation of Etching Solution An etching solution was prepared by mixing 100 ml of water with 100 ml of 46.0 mass% hydrofluoric acid (HF) and 1000 ml of 36 mass% hydrochloric acid (HCl).
(2) Etching treatment Sample D was immersed in the etching solution prepared in (1) for 1 minute to perform isotropic etching of about 3 μm.
(3) Brush Polishing After etching, sample D was brush-polished to remove the residue.

A scanning confocal laser microscope (LEXT OLS3000: manufactured by Olympus) was used to measure the crack depth.

The measurement was performed on the first end surface of Sample D in a substantially central region (a region of 36 mm in the longitudinal direction×1.3 mm in the thickness direction).

Among the observed cracks, the deepest crack depth was set as the apparent crack depth D ₀ of the sample D. However, the actual crack depth (referred to as D ₁ ) was calculated by adding to this D ₀ the length reduced by brush polishing. It should be noted that this actual crack depth D ₁ is a value that includes the effect of the above-described etching process.

(Evaluation)
Table 1 collectively shows the evaluation results of the surface roughness of the first end face and the crack depth D ₁ obtained for each of the 12 samples D. For reference, Table 1 also shows the pitch between the surface voids in the in-plane void region of the first main surface in each sample D.

From Table 1, it can be seen that the arithmetic average roughness Ra (average value) in each sample D is in the range of 0.5 μm to 0.6 μm, and the crack depth D ₁ is 5.5 μm or less.

The crack depth D ₁ shown in Table 1 is the maximum value of the cracks observed in the observation target region of the first end surface. In fact, there may be a crack having a larger crack depth D ₁ on (the unobserved region of) the first end face.

Therefore, the obtained results are as follows. When the number of samples is 12, the crack depth D when the standard deviation is 0.47 μm observed in the region of 36 mm in the longitudinal direction of the first end face and 1.3 mm in the thickness direction. It can be regarded as showing an average value of ₁ .

Experiments showing that the crack depth becomes about 7 μm or more regardless of the composition of the glass when the end surface of the glass is ground by a conventional method, for example, a #1000 diamond grindstone or a coarser diamond grindstone. There is data.

From this, the result of this time shows that the crack depth in the crack existing in the first end face is significantly suppressed as compared with the crack in the end face polished by the conventional diamond grindstone.

Here, the crack depth of the end face described in FIG. 12 of Patent Document 1 described above is about 10 times the crack depth measured in Sample D this time. Therefore, in Patent Document 1, it is considered that the crack depth in the direction perpendicular to the end face is deeper than the penetration depth of alkali metal ions in the direction perpendicular to the end face.

As described above, the surface roughness of the first end surface of sample D is significantly reduced, and the crack depth in the direction perpendicular to the first end surface of sample D is equal to the alkali metal ion on the first end surface. It was found to be shallower than the penetration depth of.

It can be said that this result is consistent with the result of the strength evaluation for the sample A described above. In addition, the surface roughness of the first end face is smooth and excellent in appearance quality after the laser irradiation, the chemical strengthening treatment, the separation, and the end face polishing treatment after separation. Can be said.

(Other Example 2)
Three kinds of samples E, F, and G were manufactured by the method as described in the above (manufacturing method of sample A).

However, sample E was manufactured from a glass substrate (glass material) having a thickness t of 0.5 mm, and sample F was manufactured from a glass substrate (glass material) having a thickness t of 0.85 mm. On the other hand, sample G was manufactured from a glass substrate (glass material) having a thickness t of 1.3 mm. That is, sample G was manufactured by the same method as sample A.

As described above, these samples E to G have undergone the step of chemically strengthening the glass material in the process of manufacturing. The phenomenon that the sample separated from the material did not occur.

For each of the samples E to G, the potassium ion concentration in the above-mentioned “first end face” was analyzed using the EPMA method (Electron Probe Micro Analyzer).

The analysis was performed at the following three locations on the first end face:
Any position corresponding to the first main surface of the glass material, that is, any position corresponding to one side having a length of 60 mm (referred to as "measurement area 1"),
Any position that has moved by 1/4 along the thickness direction of the sample (direction toward the second main surface of the glass material) from the position corresponding to the first main surface of the glass material (“measurement area 2 ,) and any position moved by 1/2 along the thickness direction of the sample from the position corresponding to the first main surface of the glass material (referred to as “measurement area 3”).

Table 2 below shows the analysis results of the potassium concentration obtained in each measurement region of Samples E to G.

The potassium ion concentration is represented by the concentration (atomic ratio) of potassium ions normalized by silicon ions, that is, Cs. Strictly speaking, in each measurement region, the potassium ion concentration becomes maximum near the surface slightly in the depth direction (width direction of the sample) orthogonal to the surface of each measurement region. Therefore, here, in each measurement region, the Cs value at the position where the analysis value of K is maximum in the vicinity of the surface is adopted as the Cs in that measurement region.

The value of Cs obtained by the EPMA method may be different from the result of the EDX method described above. However, there is no impact on the profile evaluation.

In addition, Table 2 also shows the values of the penetration depth of potassium ions in each measurement region. This penetration depth represents the penetration depth along the depth direction (the width direction of the sample) at which there is no change in potassium ions from the first end surface.

Further, Table 2 shows the ratio of Cs of each measurement region to Cs of the bulk calculated in the measurement region 3 (hereinafter, referred to as “Cs ratio”).

From the results of Table 2, in Samples E to G, potassium ions are introduced into the entire first end face, and the concentration of potassium ions increases from the central portion of the thickness toward the first main surface. It was confirmed to show a profile. Further, it was confirmed that the concentration of potassium ions on the first end face was 1.8 times or more higher than the concentration of potassium ions (bulk concentration) originally contained in the sample.

110 glass material 112 1st main surface 114 2nd main surface 116 end surface 130, 131, 132 in-plane void area 138 surface void 138A, 138B surface void row 150 internal void row 158 void 160, 161, 162 glass piece 170 virtual End surface 175 Glass plate 180 Glass article 186 End surface 200 Device 210 Pedestal 220 Roller 250 Device 260 Sheet member 270 Support member 380 First glass article 382 First main surface 384 Second main surface 386 (386-1 to 386-) 4) End surface 415 1st glass plate 417 1st main surface 419 2nd main surface 420 (420-1 to 420-4) End surface 431 In-plane void area 461 Glass piece 800 Glass substrate 802 1st main surface 831 , 832 in-plane void region 880 sample 900 flat bending test apparatus 910 sample 912 first main surface 914 second main surface 918 second end surface 920 fulcrum member 930 load member 950 longitudinal bending test apparatus 916 first end surface 918 fourth 2 end face 970 fulcrum member 980 load member

Claims (18)

A method of manufacturing a glass plate,
(1) a step of preparing a glass material having a first main surface and a second main surface facing each other,
(2) By irradiating the first main surface of the glass material with a laser, an in-plane void region in which a plurality of voids are arranged is formed on the first main surface, and the in-plane void is also formed. Forming a plurality of internal void rows in which one or more voids are arranged from the region toward the second main surface;
(3) a step of chemically strengthening the glass material on which the internal void rows are formed,
And a manufacturing method. The manufacturing method according to claim 1, wherein in the in-plane void region, an interval between adjacent voids is in a range of 3 μm to 10 μm. In the step (2), after the in-plane void region is formed by the first pass laser irradiation, the laser irradiation is further repeated at least once along the in-plane void region, whereby the The manufacturing method according to claim 1, wherein the internal void row is formed from a first main surface to the second main surface. Furthermore, in the step (2) above,
Forming a groove along the in-plane void region in at least one of the first main surface and the second main surface after forming the in-plane void region, or forming the in-plane void region First, a step of forming a groove along at least one of the first main surface and the second main surface along an in-plane void region formed later,
The manufacturing method according to any one of claims 1 to 3, further comprising: A method of manufacturing a glass article, comprising:
It is the process of manufacturing a glass plate by the manufacturing method of the glass plate as described in any one of Claim 1 thru|or 4, Comprising: The said glass plate is a 3rd corresponding to the said 1st main surface of the said glass material. And a fourth major surface corresponding to the second major surface of the glass material, and
Separating one or more glass articles from the glass sheet along the in-plane void regions and the plurality of internal void rows;
And a manufacturing method. In the step of separating the glass article,
Applying a pressing force along the in-plane void region to the glass plate,
Deforming the glass plate such that the third main surface or the fourth main surface is convex, and applying tensile stress due to thermal stress along the in-plane void region to the glass plate ,
The manufacturing method according to claim 5, wherein the one or more glass articles are obtained by one or more selected from the following. A glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
A glass plate having a compressive stress layer formed by a chemical strengthening treatment in the center of a cut surface obtained when the glass plate is cut through the in-plane void region and the plurality of internal void rows. A glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
A predetermined alkali metal ion extending from the first main surface to the second main surface in a cut surface obtained when the glass plate is cut so as to pass through the in-plane void region and the plurality of internal void rows. The concentration profile has a profile in which the concentration of the predetermined alkali metal ion is higher than the bulk concentration of the glass plate,
The glass plate, wherein the predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces. A glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
In a cut surface obtained when the glass plate is cut so as to pass through the in-plane void regions and the plurality of internal void rows, a predetermined alkali metal ion extending from the first main surface to the second main surface The concentration profile has a profile in which the concentration of the predetermined alkali metal ion is higher toward the first main surface side and the second main surface side as compared with the central portion of the thickness of the glass plate,
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass plate in which the concentration of the predetermined alkali metal ion in the concentration profile is higher than the bulk concentration of the glass plate on the cut surface. A glass plate,
Having a first major surface and a second major surface opposite each other,
The first main surface has an in-plane void region in which a plurality of voids are arranged,
There are a plurality of internal void rows in which one or more voids are arranged from the in-plane void region toward the second main surface,
In a cut surface obtained when the glass plate is cut so as to pass through the in-plane void regions and the plurality of internal void rows, a predetermined alkali metal ion extending from the first main surface to the second main surface The concentration profile has a substantially parabolic profile in which the concentration of the predetermined alkali metal ion is higher toward the first main surface side and the second main surface side,
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass plate in which the concentration of the predetermined alkali metal ion in the concentration profile is higher than the bulk concentration of the glass plate on the cut surface. The glass plate according to claim 7, wherein in the in-plane void region, an interval between adjacent voids is in a range of 3 μm to 10 μm. The glass plate according to any one of claims 7 to 11, wherein the cut surface corresponds to an end face when a glass article is separated from the glass plate. The glass plate according to claim 12, wherein the end face has a connection portion with the first main surface and/or a connection portion with the second main surface chamfered or rounded. A glass article,
A first main surface and a second main surface facing each other, and at least one end surface joining both main surfaces;
In the end surface, the concentration profile of the predetermined alkali metal ion extending from the first main surface to the second main surface has the first main surface side and the second main surface side as compared to the central portion in the thickness direction. Has a profile in which the concentration of the alkali metal ion is higher toward the main surface of
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass article in which the concentration of the predetermined alkali metal ion in the concentration profile at the end face is higher than the bulk concentration of the glass article. A glass article,
A first main surface and a second main surface facing each other, and at least one end surface joining both main surfaces;
In the end face, the concentration profile of a predetermined alkali metal ion extending from the first main surface to the second main surface is such that the alkali metal ion is closer to the first main surface side and the second main surface side. Has a high parabolic profile with a high concentration of
The predetermined alkali metal ion is an alkali metal ion for imparting a compressive stress layer to the first main surface and the second main surface to increase the strength of both main surfaces,
A glass article in which the concentration of the predetermined alkali metal ion in the concentration profile at the end face is higher than the bulk concentration of the glass article. The glass article according to claim 14 or 15 , wherein a crack depth in a direction perpendicular to the end face is shallower than a penetration depth of the predetermined alkali metal ion in a direction perpendicular to the end face. The glass article according to any one of claims 14 to 16 , wherein the predetermined alkali metal ion is a sodium ion and/or a potassium ion. 18. The end surface according to any one of claims 14 to 17 , wherein a connection portion with the first main surface and/or a connection portion with the second main surface is chamfered or rounded. The glass article described.