TW202400541A - Method for producing glass article, glass article, and layered product - Google Patents

Abstract

A method for producing a glass article which comprises: a preparation step S1 in which an alkali aluminosilicate glass having a glass composition containing an alkali metal oxide is prepared as a glass to be treated; and a water treatment step S3 in which the glass to be treated is kept in contact with treatment water for 0.5-15 hours, excluding 15 hours.

Description

Glass product manufacturing method, glass product and laminated body

The present invention relates to a glass product manufacturing method, a glass product, and a laminated body including the glass product.

Chemically strengthened glass is mostly used as cover glass for components such as various electronic terminals and display components. Among such devices, so-called foldable-type devices that can fold the display surface of a display have also been developed. Chemically strengthened glass is sometimes used as the cover glass of such foldable-type devices.

Chemically strengthened glass has a compressive stress layer formed on the surface by ion exchange treatment, thereby suppressing the formation and progression of cracks on the surface, thereby achieving high strength. It is considered that the strength of tempered glass can be improved by adjusting the formation form of such a compressive stress layer (for example, Patent Document 1). [Prior art documents] [Patent Document]

Patent Document 1: International Publication No. 2013/088856

[Problem to be solved by the invention] However, there is still room for improvement in obtaining higher impact resistance in glass products used in cover glass and the like. Particularly in the case of components for pen input using a stylus pen, local impact is easily applied to glass products. Therefore, there is a need to develop a glass product that can sufficiently withstand such pen input and has high pen-down strength.

An object of the present invention is to provide a glass product with high writing strength.

[Means to solve the problem] (1) The glass product manufacturing method of the present invention created to solve the above-mentioned problems is characterized by including a preparation step of preparing processing glass including an alkaline aluminosilicate glass as a glass an alkali metal oxide of composition; and a water treatment step in which the glass for treatment is contacted with the treatment water for more than 0.5 hours and less than 15 hours.

As a result of diligent research, the present inventors have found that when the processing glass is alkaline aluminosilicate glass, by performing the water treatment step of contacting the processing glass with the processing water for the predetermined time, the processing glass The writing intensity is greatly improved. Furthermore, this writing strength improving effect continues even after the water treatment step, that is, after the contact between the treatment glass and the treatment water is released. Therefore, a glass product having high writing strength can be provided.

(2) In the structure of (1) above, in the water treatment step, it is preferable that the glass for treatment is immersed in the treatment water of 46°C to 100°C.

In this way, if the temperature of the treatment water is increased, the writing strength of the treatment glass can be efficiently increased in a short time. That is, the processing time (the contact time between the processing glass and the processing water) until the desired writing strength is obtained can be relatively shortened. Therefore, glass products with high writing strength can be efficiently produced.

(3) The structure according to (1) above, wherein in the water treatment step, the processing glass can be immersed in the processing water reaching 100° C. or higher in a pressurized environment.

In this way, if the temperature of the treatment water is increased, the writing strength of the treatment glass can be efficiently increased in a short time. That is, the processing time until the desired writing intensity is obtained can be relatively shortened. Therefore, glass products with high writing strength can be efficiently produced.

(4) The structure according to any one of (1) to (3), wherein in the water treatment step, the conductivity of the treated water is preferably 3 mS/m or less.

In this way, if treatment water with low electrical conductivity is used, the writing strength of the treatment glass can be further improved. Therefore, the writing strength of the glass product produced from the said processing glass is also further improved.

(5) The structure according to any one of (1) to (4) above, wherein the processing glass is preferably in the form of a plate or sheet with a thickness of 0.005 mm to 0.1 mm.

In this way, if the processing glass is thinned, a glass product made of the processing glass can be suitably used for a foldable type element. On the other hand, the impact resistance of glass products is bound to be easily reduced, and the improvement of pen drop strength becomes more important. Therefore, the writing strength improving effect of the present invention is more useful.

(6) The structure as described in (5), which may further include a thinning step, wherein the processing glass is thinned to the thickness by etching before the water treatment step. Within the range (0.005 mm ~ 0.1 mm).

(7) The structure as described in (5), wherein the processing glass can be preformed into the thickness range (0.005 mm to 0.1 mm) by an overflow down-drawing method.

(8) The structure according to any one of the above (1) to (7), which preferably further includes a chemical strengthening step. The chemical strengthening step is to make the treatment glass and alkali metal nitric acid before the water treatment step. Salt contact forms a compressive stress layer with a maximum compressive stress of more than 100 MPa on the surface.

In this case, the processing glass and the glass product become chemically strengthened glass having a compressive stress layer on the surface. Therefore, while the writing strength of the glass product can be improved, the bending strength can also be improved. In this way, if it is a glass product with improved bending strength, it can be suitably used for a foldable type element.

(9) The structure as described in (8), wherein in the water treatment step, the temperature of the treated water is preferably 50°C to 95°C, and the contact time between the glass for treatment and the treated water is 0.5 hours to 10 hours. .

In this case, when the glass for processing is chemically strengthened glass, water treatment conditions are particularly suitable, and the drop strength of glass products including chemically strengthened glass can be efficiently improved.

(10) The structure according to (8) or (9) above, wherein the glass composition for processing is preferably 50% to 80% SiO ₂ and 5% to 25% Al in molar %. ₂ O ₃ , 0% to 35% B ₂ O ₃ , 0% to 20% Li ₂ O, 1% to 20% Na ₂ O, 0% to 10% K ₂ O, in the chemical strengthening step , alkali metal nitrates are molten salts containing potassium nitrate.

In this case, even when the glass for processing is thin, it is easy to improve both the writing strength and the bending strength of the glass product.

(11) The structure according to any one of (8) to (10), which preferably further includes a surface layer etching step, which is performed after the ion exchange step and before the water treatment step, and in a relatively compressed state. The processing glass is etched within a shallow range of the stress layer.

If so, surface defects formed in the glass for processing can be reduced during the ion exchange step, thereby improving the pen-down strength and/or bending strength of the glass product.

(12) The glass product of the present invention created to solve the above problems is a plate-shaped or sheet-shaped glass product with a thickness of 0.005 mm to 0.1 mm, and is characterized by having a spherical tip of 0.7 mm in diameter. In the pen drop test where a ballpoint pen was dropped onto the main surface, 60% of the damage height was more than 5 cm.

If so, it will be a glass product that can fully withstand pen input and has high pen-down strength.

(13) The structure according to (12) above, preferably including a compressive stress layer having a maximum compressive stress of 100 MPa or more on the surface.

If so, in addition to improving the writing strength, the bending strength is also improved, so it can be suitably used for foldable type components.

(14) The laminated body of the present invention created to solve the above problems is characterized by including: a glass product having a structure as described in (12) or (13); and a protective layer or a reinforcing layer laminated in the glass product. at least one of its main surfaces.

If so, the glass product can be protected by a protective layer to achieve higher writing strength, or the glass product can be reinforced by a reinforcing layer to achieve higher bending strength.

[Effects of the invention] According to the present invention, a glass product with high writing strength can be provided.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, by assigning the same reference numerals to corresponding structural members in each embodiment, overlapping descriptions may be omitted. When only a part of the structure is described in each embodiment, the structure of the other embodiments described previously can be applied to the other parts of the structure. In addition, not only the configurations explicitly stated in the description of each embodiment are possible, but as long as the combination does not cause any particular obstacles, the configurations of the plurality of embodiments may be partially combined with each other even if not stated clearly.

(first embodiment) ＜Glass products＞ As shown in FIG. 1 , the glass product 1 according to the first embodiment is plate-shaped or sheet-shaped. The thickness t of the glass product 1 is not particularly limited, but is preferably 0.005 mm to 0.1 mm. The invention is particularly effective with such thin glass.

For glass product 1, in a pen drop test in which a 5.7 g pen having a spherical tip with a diameter of 0.7 mm is dropped onto the main surface, the 60% destruction height is preferably 5 cm or more. The 60% destruction height of the glass product 1 is more preferably 7 cm or more, 10 cm or more, or 15 cm or more.

In this embodiment, the glass product 1 is chemically strengthened glass obtained by chemical strengthening through ion exchange, and includes a compressive stress layer 2 and a tensile stress layer 3 . In this way, in addition to improving the writing strength, the bending strength can also be improved.

When the glass product 1 is chemically strengthened glass, the two-point bending strength of the glass product 1 is preferably 900 MPa or more. The two-point bending strength of the glass product 1 is more preferably 1000 MPa or more, 1100 MPa or more, or 1200 MPa or more.

The compressive stress layer 2 is formed on the surface layer portion of the glass product 1 including the main surface 1a and the end surface 1b. The tensile stress layer 3 is formed inside the glass product 1 , that is, at a deeper position than the compressive stress layer 2 . Here, the main surface refers to the front and back surfaces of the entire plate-shaped or sheet-shaped glass surface excluding the end surfaces.

An example of the stress distribution of the glass product 1 is shown in FIG. 2 . In Figure 2, the vertical axis represents the stress value, and the horizontal axis represents the depth from the surface. Furthermore, FIG. 2 is an image diagram schematically showing the stress distribution by linear approximation. The stress distribution can be approximated by other functions (for example, a single curve function or a combination of multiple curve functions). In this specification, unless otherwise specified, the magnitude of each stress is expressed as an absolute value. The stress distribution of the glass product 1 is not limited to the form shown in FIG. 2 .

The stress distribution shown in FIG. 2 illustrates the case where the glass product 1 is tempered glass that has been subjected to one stage of ion exchange treatment. In the stress distribution of glass product 1, the compressive stress on the surface is the maximum (maximum compressive stress CS), and the stress gradually decreases the deeper it is from the surface, and at the depth DOC, the stress is zero. That is, DOC and the depth of compressive stress have the same meaning. A tensile stress layer 3 having tensile stress extends in a region deeper than the depth DOC. The stress distribution of the glass product 1 is preferably symmetrical on the front and back as shown in Figure 2 .

The tensile stress layer 3 includes a first region A1 in which the tensile stress varies in the thickness direction of the glass product 1 and a second region A2 in which the tensile stress becomes constant in the thickness direction. More specifically, the first region A1 is a region extending from the depth DOC of the compressive stress layer 2 to the tensile stress convergence depth DCT. The deeper the depth, the greater the absolute value of the tensile stress (as shown in FIG. 2 The area marked by gradually decreasing negative numbers). The second region A2 extends deeper than the tensile stress convergence depth DCT and is a region in which the tensile stress becomes constant in the thickness direction. In addition, "tensile stress is constant" means that the change amount of stress in the depth direction is 0.5 MPa/μm or less. This change amount can be calculated from the differential value of the stress taken at intervals of 0.1 μm in depth, for example.

The depth DOC of the compressive stress layer 2 of the glass product 1 is preferably 20 μm or less, 1 μm or more and 19 μm or less, 2 μm or more and 18 μm or less, 3 μm or more and 17.5 μm or less, or 4 μm or more and 17 μm or less. The inventors conducted various studies on the compressive stress value of the surface and the critical value of the depth of the compressive stress layer that will not cause dangerous damage when it breaks. As a result, they found that the effective ones are, for example, 0.1 mm or less. In thin glass, the depth of the compressive stress layer should be 20 μm or less. This ensures sufficient strength against bending and ensures safety.

The maximum compressive stress CS in the compressive stress layer 2 of the glass product 1 is preferably 100 MPa or more, 200 MPa or more and 1000 MPa or less, 300 MPa or more and 900 MPa or less, 400 MPa or more and 870 MPa or less, 430 MPa or more and 850 MPa or more. Below MPa, above 450 MPa and below 800 MPa. By setting CS in the above range, high bending strength can be obtained.

The depth DOC of the compressive stress layer 2 and the thickness t of the glass product 1 satisfy the following equation (2). DOC/t≦0.25 (2) By limiting the ratio of DOC to t within the above range, sufficient strength with respect to bending can be obtained and safety can be ensured. The upper limit range of DOC/t is preferably 0.23 or less. The lower limit range of DOC/t is preferably from 0.03 to 0.10.

The tensile stress convergence depth DCT can be calculated from the following equation (3). DCT=(CS+CT)/(CS/DOC) (3)

The upper limit range of the maximum tensile stress CT in the second region A2 is preferably 1000 MPa or less, 500 MPa or less, 400 MPa or less, 285 MPa or less, 250 MPa or less, 240 MPa or less, 230 MPa or less, 220 MPa or less, 210 MPa. Below, below 200 MPa, below 190 MPa, below 180 MPa, below 170 MPa, below 160 MPa, below 150 MPa, below 145 MPa, below 140 MPa, below 130 MPa, below 120 MPa, below 110 MPa, below 100 MPa, Below 95 MPa, below 85 MPa, below 70 MPa. The lower limit range of the maximum tensile stress CT is preferably 10 MPa or more, 20 MPa or more, 35 MPa or more, 50 MPa or more, 55 MPa or more, or 60 MPa or more. By limiting CT as described above, it is possible to ensure safety so that no dangerous damage pattern occurs when broken, and at the same time, strength relative to bending is ensured.

Furthermore, numerical values related to stresses such as CS, DOC, DCT, and CT can be derived by measuring the stress distribution of glass using a measuring device such as FSM-6000 or SLP-1000 manufactured by Orihara Seisakusho.

The lower limit range of the Young's modulus of the glass product 1 is preferably 55 GPa or more, 57 GPa or more, 60 GPa or more, or 62 GPa or more. The upper limit range of the Young's modulus of the glass product 1 is preferably 90 GPa or less.

From the viewpoint of cost and throughput, the overflow down-drawing method is suitable as a method for forming the glass product 1 into a sheet. However, the thinner the sheet, the faster the glass is cooled, the lower the CS, and the lower the DOC. Deep tendency. In addition, it is known that when thin glass is ion-exchanged, it is difficult to obtain high CS compared with thick glass because there is less glass inside to suppress the volume expansion of the ion-exchange portion. Therefore, for thin glass, balancing high CS and shallow DOC at a high level does not easily exceed simple design matters. That is, it is necessary to appropriately select the glass composition, glass forming method, and strengthening conditions. Therefore, the glass product 1 is suitable for alkaline aluminum silicate glass suitable for chemical strengthening. Among alkaline aluminum silicate glasses, a composition that can also obtain a high surface compressive stress value is particularly suitable. Furthermore, in order to be able to utilize Forming by the overflow down-draw method is preferred to achieve a composition balance such as high liquid phase viscosity.

The glass product 1 preferably contains, for example, a glass composition of 50% to 80% SiO ₂ , 5% to 25% Al ₂ O ₃ , 0% to 35% B ₂ O ₃ , and 0% in molar %. ~20% Li ₂ O, 1% ~ 20% Na ₂ O, 0% ~ 10% K ₂ O.

SiO ₂ is a component that forms the network of glass. If the content of SiO ₂ is too small, vitrification is difficult, the thermal expansion coefficient becomes too high, and the thermal shock resistance is likely to decrease. Therefore, the suitable lower limit range of SiO ₂ is 50% or more, 55% or more, 57% or more, 59% or more, and especially 61% or more in mol%. On the other hand, if the content of _SiO2 is too high, the meltability or formability is likely to decrease, and the thermal expansion coefficient becomes too low, making it difficult to match the thermal expansion coefficient of surrounding materials. Therefore, the suitable upper limit range of SiO ₂ is 80% or less, 70% or less, 68% or less, 66% or less, 65% or less, especially 64.5% or less.

Al ₂ O ₃ is a component that improves ion exchange performance, and also improves strain point, Young's modulus, fracture toughness, and Vickers hardness. Therefore, the suitable lower limit range of Al ₂ O ₃ is 5% or more, 8% or more, 10% or more, 11% or more, or 11.2% or more in mol%. On the other hand, if the content of Al ₂ O ₃ is too high, the high-temperature viscosity increases, and the meltability or formability is likely to decrease. In addition, devitrification crystals tend to precipitate in glass, making it difficult to form into a plate shape by overflow down-drawing or the like. Especially when an alumina-based refractory is used as a molded refractory and a glass plate is formed by the overflow down-draw method, devitrification crystals of spinel are likely to precipitate at the interface with the alumina-based refractory. Furthermore, the acid resistance also decreases, making it difficult to apply to the acid treatment step. Therefore, the suitable upper limit range of Al ₂ O ₃ is 25% or less, 21% or less, 20.5% or less, 20% or less, 19.9% or less, 19.5% or less, 19.0% or less, especially 18.9% or less. If the content of Al ₂ O ₃ , which has a large influence on ion exchange performance, is within an appropriate range, CS/DOC can be easily designed to have a high value even in thin glass.

B ₂ O ₃ is a component that reduces high-temperature viscosity or density, stabilizes glass so that crystals are less likely to precipitate, and lowers the liquidus temperature. In addition, it is a component that suppresses Young's modulus and improves bending strength or crack resistance. However, if the content of B ₂ O ₃ is too high, surface coloring called yellowing due to ion exchange treatment may occur, water resistance may decrease, or the compressive stress value of the compressive stress layer may decrease. Therefore, the suitable lower limit range of B ₂ O ₃ is 0% or more, 0.01% or more, 0.02% or more, 0.1% or more, and 0.3% or more in terms of mol%, and the suitable upper limit range is 35% or less and 30% or less. , below 25%, below 22%, below 20%, especially below 15%. Furthermore, from the viewpoint of preferentially increasing CS, the content of B ₂ O ₃ can be further preferably set to 0.2% to 5% or 0.3% to 1%. In addition, from the viewpoint of improving chemical durability for the purpose of suppressing defects during etching, the upper limit of the content of B ₂ O ₃ is preferably 1% or more, 1.5% or more, or 2% or more. The lower limit range can be set to 5% or less, 4.5% or less, 4% or less, or 3% or less. On the other hand, from the viewpoint of preferentially suppressing Young's modulus, the content of B ₂ O ₃ can be further preferably set to 10% to 25%, 15% to 23%, or 18% to 22%.

Li ₂ O is an ion exchange component, and in particular, Li ions contained in the glass are ion exchanged with K ions in the molten salt to obtain a high surface compressive stress value. Li ₂ O is a component that reduces high-temperature viscosity and improves meltability or formability. Therefore, the suitable lower limit range of Li ₂ O is 0% or more, 3% or more, 4% or more, 4.2% or more, 5% or more, 5.5% or more, 6.5% or more, 7% or more, 7.3% in mol%. % or more, 7.5% or more, 7.8% or more, especially 8% or more. Therefore, the suitable upper limit range of Li ₂ O is 20% or less, 15% or less, 13% or less, 12% or less, 11.5% or less, 11% or less, 10.5% or less, less than 10%, especially 9.9% or less, 9 % or less, 8.9% or less.

Na ₂ O is an ion exchange component and is a component that reduces high-temperature viscosity and improves meltability or formability. In addition, Na ₂ O is also a component that improves devitrification resistance and reaction devitrification with formed refractories, especially alumina refractories. If the content of Na ₂ O is too small, the meltability will decrease, the thermal expansion coefficient will decrease too much, or the ion exchange rate will tend to decrease. Therefore, the suitable lower limit range of Na ₂ O is 1% or more, 5% or more, 7% or more, 8% or more, 8.5% or more, 9% or more, 9.5% or more, 10% or more, 11% in mol%. % or more, 12% or more, especially 12.5% or more. On the other hand, if the content of Na ₂ O is too high, phase separation occurs and the viscosity is likely to decrease. In addition, the acid resistance may be reduced, or the component balance of the glass composition may be lacking, and the devitrification resistance may be reduced instead. Therefore, a suitable upper limit range of Na ₂ O is 20% or less, 19.5% or less, 19% or less, 18% or less, 17% or less, 16.5% or less, 16% or less, 15.5% or less, especially 15% or less.

K ₂ O is a component that reduces high-temperature viscosity and improves meltability or formability. Furthermore, it is a component that improves devitrification resistance or increases Vickers hardness. However, if the content of K ₂ O is too high, phase separation occurs and the viscosity is likely to decrease. In addition, the acid resistance tends to decrease, or the component balance of the glass composition is lacking, and the devitrification resistance tends to decrease. Therefore, the suitable lower limit range of K ₂ O is 0% or more, 0.01% or more, 0.02% or more, 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, 2% or more, 2.5% in mol%. % or more, 3% or more, especially 3.5% or more, and the suitable upper limit range is 10% or less, 5.5% or less, 5% or less, especially less than 4.5%.

Both Li ₂ O and Na ₂ O are components that perform ion exchange with K ions in the molten salt to obtain high surface compressive stress values, and are essential components in the present invention. Therefore, the suitable lower limit range of Li ₂ O + Na ₂ O is 1% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% in mol%. More than %, more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, more than 15%, more than 16%, more than 17%, more than 18%, especially more than 18.5%. On the other hand, if the content of Li ₂ O + Na ₂ O is too high, the thermal expansion coefficient becomes too high, and the thermal shock resistance is likely to decrease. In addition, the component balance of the glass composition may collapse, and the devitrification resistance may decrease instead. Therefore, a suitable upper limit range of Li ₂ O+Na ₂ O is 20% or less, especially 19% or less.

In addition to the above-mentioned components, the glass product 1 may also contain, for example, the following components as a glass composition.

MgO is a component that reduces high-temperature viscosity and improves meltability or formability, or increases strain point or Young's modulus. MgO is a component that is most effective in improving ion exchange performance among alkaline earth metal oxides. However, if the content of MgO is too high, the density or thermal expansion coefficient is likely to be high, and the glass is likely to be devitrified. Therefore, the suitable upper limit range of MgO is 12% or less, 10% or less, 8% or less, 6% or less, especially 5% or less. Furthermore, when MgO is introduced into the glass composition, a suitable lower limit range of MgO is 0.1% or more, 0.5% or more, 1% or more, and especially 2% or more in mol%.

Compared with other components, CaO has a greater effect of reducing high-temperature viscosity without reducing devitrification resistance, improving meltability or formability, and increasing strain point or Young's modulus. The content of CaO is preferably 0% to 10%. However, if the CaO content is too high, the density or thermal expansion coefficient will be high, and the component balance of the glass composition will be lacking. On the contrary, the glass will easily devitrify, or the ion exchange performance will easily decrease. Therefore, the suitable content of CaO is 0% to 5%, 0.01% to 4%, 0.1% to 3%, and especially 1% to 2.5% in terms of molar %.

SrO is a component that reduces high-temperature viscosity without reducing devitrification resistance, improves meltability or formability, or increases strain point or Young's modulus. However, if the content of SrO is too high, the density or thermal expansion coefficient will be high, or the ion exchange performance will be reduced, or the component balance of the glass composition will be lacking, and the glass will be prone to devitrification. The suitable content range of SrO is 0% to 5%, 0% to 3%, 0% to 1%, and especially 0% to less than 0.1% in molar %.

BaO is a component that reduces high-temperature viscosity without reducing devitrification resistance, improves meltability or formability, or increases strain point or Young's modulus. However, if the content of BaO is too high, the density or thermal expansion coefficient will increase, or the ion exchange performance will decrease, or the component balance of the glass composition will be lacking, and the glass will be prone to devitrification. The suitable content range of BaO is 0% to 5%, 0% to 3%, 0% to 1%, and especially 0% to less than 0.1% in terms of molar %.

ZnO is a component that improves ion exchange performance and is particularly effective in increasing the compressive stress value. In addition, it is a component that reduces the high-temperature viscosity without reducing the low-temperature viscosity. However, if the content of ZnO is too high, the glass tends to separate, the devitrification resistance decreases, the density increases, or the stress depth of the compressive stress layer decreases. Therefore, the content of ZnO is preferably 0% to 6%, 0% to 5%, 0% to 1%, 0% to 0.5%, especially 0% to less than 0.1% in terms of molar %.

ZrO ₂ is a component that significantly improves ion exchange performance and increases the viscosity or strain point near the liquid phase viscosity. However, if its content is too high, the devitrification resistance may significantly decrease, and the density may become excessive. High risk. Therefore, the suitable upper limit range of ZrO ₂ is 10% or less, 8% or less, 6% or less, and especially 5% or less in mol%. Furthermore, when it is desired to improve the ion exchange performance, it is preferable to introduce ZrO ₂ into the glass composition. In this case, the suitable lower limit range of ZrO ₂ is 0.001% or more, 0.01% or more, 0.5%, especially More than 1%.

P ₂ O ₅ is a component that improves ion exchange performance, and particularly increases the stress depth of the compressive stress layer. In addition, it is a component that suppresses Young's modulus to a low level. However, if the content of P ₂ O ₅ is too high, the glass will easily separate into phases. Therefore, the suitable upper limit range of P ₂ O ₅ is 10% or less, 8% or less, 6% or less, 4% or less, 2% or less, 1% or less, and especially less than 0.1% in molar %.

As a clarifier, 0 ppm to 30000 ppm (3%) of a group selected from As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , F, Cl, SO ₃ (preferably SnO ₂ , Cl, One or more of the groups SO ₃ ). From the viewpoint of reliably enjoying the clarification effect, the content of SnO ₂ +SO ₃ +Cl is preferably 0 ppm to 10000 ppm, 50 ppm to 5000 ppm, 80 ppm to 4000 ppm, 100 ppm to 3000 ppm, and especially 300 ppm. ppm～3000 ppm. Here, "SnO ₂ +SO ₃ +Cl" means the total amount of SnO ₂ , SO ₃ and Cl.

The suitable content range of SnO ₂ is 0 ppm to 10000 ppm, 0 ppm to 7000 ppm, especially 50 ppm to 6000 ppm. The suitable content range of Cl is 0 ppm to 1500 ppm, 0 ppm to 1200 ppm, 0 ppm to 800 ppm, 0 ppm to 500 ppm, especially 50 ppm to 300 ppm. The suitable content range of SO ₃ is 0 ppm to 1000 ppm, 0 ppm to 800 ppm, especially 10 ppm to 500 ppm.

Rare earth oxides such as Nd ₂ O ₃ and La ₂ O ₃ are components that increase Young's modulus, and are components that can cause color loss and control the color of glass when a complementary color is added. However, the cost of the raw material itself is high, and if introduced in large amounts, the devitrification resistance is likely to decrease. Therefore, the content of the rare earth oxide is preferably less than 4%, less than 3%, less than 2%, less than 1%, especially less than 0.5%.

From environmental considerations, the glass product 1 is preferably substantially free of As ₂ O ₃ , F, PbO, and Bi ₂ O ₃ . Here, "substantially does not contain As ₂ O ₃ " means that although As ₂ O ₃ is not actively added as a glass component, it is allowed to be mixed in at an impurity level. Specifically, it means that As ₂ O ₃ The content is less than 500 ppm. "Substantially does not contain F" means that although F is not actively added as a glass component, it is allowed to be mixed in at an impurity level. Specifically, it means that the content of F is less than 500 ppm. The term "substantially does not contain PbO" means that although PbO is not actively added as a glass component, it is allowed to be mixed in at an impurity level. Specifically, it means that the content of PbO is less than 500 ppm. The term "substantially does not contain Bi ₂ O ₃ " means that although Bi ₂ O ₃ is not actively added as a glass component, it is allowed to be mixed in at an impurity level. Specifically, it means that the content of Bi ₂ O ₃ is less than 500 ppm.

As an example, the glass product 1 may not contain B ₂ O ₃ as a glass component, or the content of B ₂ O ₃ may be limited to a very small amount. That is, the glass product 1 may contain 50% to 80% SiO ₂ , 5% to 25% Al ₂ O ₃ , 0% to 1% B ₂ O ₃ , 0% to 20% Li ₂ O, 1% to 20% Na ₂ O, 0% to 10% K ₂ O.

As another example, the glass product 1 may contain B ₂ O ₃ as a glass composition as an essential component. That is, the glass product 1 may contain 50% to 80% SiO ₂ , 5% to 25% Al ₂ O ₃ , 1% to 5% B ₂ O ₃ , 0% to 20% Li ₂ O, 1% to 20% Na ₂ O, 0% to 10% K ₂ O.

Furthermore, when the glass product 1 contains B ₂ O ₃ as an essential component of the glass composition, there is a concern that the formability of the glass is reduced. Therefore, in order to achieve a balance, for example, the content of other components such as Al ₂ O ₃ may be limited. That is, the glass product 1 may contain 50% to 80% SiO ₂ , 5% to 10% Al ₂ O ₃ , 1% to 5% B ₂ O ₃ , 0% to 20% Li ₂ O, 1% to 20% Na ₂ O, 0% to 10% K ₂ O.

＜Glass product manufacturing method＞ As shown in FIG. 3 , the glass product manufacturing method of the first embodiment includes a preparation step S1, a chemical strengthening step S2, and a water treatment step S3 in sequence.

In the preparation step, glass (hereinafter referred to as processing glass) as a base of the glass product 1 is prepared. The processing glass is glass composed of the same shape, size and glass composition as the glass product 1 .

Glass for processing is, for example, plate-like or sheet-like mother glass obtained by forming methods such as overflow down-drawing, orifice down-drawing, float, down-drawing, etc., cut into small pieces of glass and processed And get. In order to obtain a smooth surface, it is preferable to use the overflow down-draw method as the forming method. In addition, if the overflow down-draw method is used, processing glass with a thickness of 0.005 mm to 0.1 mm can be easily formed without polishing (including mechanical polishing and etching) after forming. Furthermore, in the case of molding by the overflow down-draw method, the processing glass has a molding merging surface inside.

The end surface of the processing glass is preferably chamfered by grinding, heat treatment, etching, or the like, or treated to increase strength. The main surface of the processing glass may be ground. For example, when the main surface is smoothly formed in advance by the overflow down-drawing method or when the thickness is uniform and accurately formed, the main surface does not need to be ground. You can use the non-abrasive surface directly. Furthermore, when it is formed by the overflow down-drawing method and is not polished, the main surface of the processing glass becomes a molded surface.

In the chemical strengthening step S2, the processing glass is subjected to ion exchange treatment. In this embodiment, the glass for processing is immersed in the molten salt for ion exchange processing. By forming the processing glass into chemically strengthened glass by the ion exchange treatment in this way, the bending strength of the processing glass is improved.

The molten salt is a salt containing a component capable of ion exchange with a component in the chemically strengthened glass, and is typically an alkali metal nitrate. Examples of alkali metal nitrates include NaNO ₃ , KNO ₃ , LiNO ₃ and the like, and these may be used individually (100% by mass) or in combination of multiple types. The mixing ratio when mixing multiple alkali metal nitrates can be determined arbitrarily. For example, it can be 5% to 95% NaNO ₃ and 5% to 95% KNO ₃ in terms of mass %, and preferably it can be 30%. ~80% of NaNO ₃ and 20% to 70% of KNO ₃ , more preferably 50% to 70% of NaNO ₃ and 30% to 50% of KNO ₃ .

The temperature of the molten salt is, for example, 350°C to 500°C, preferably 355°C to 470°C, 360°C to 450°C, 365°C to 430°C, or 370°C to 410°C. In addition, the immersion time is, for example, 3 minutes to 300 minutes, preferably 5 minutes to 120 minutes, and 7 minutes to 100 minutes. Of course, conditions such as the temperature of the molten salt and the immersion time can be appropriately changed depending on the glass composition and the like within the range in which the stress characteristics are obtained.

In the water treatment step S3, the treatment glass is brought into contact with the treatment water for 0.5 hours or more and less than 15 hours. By bringing the processing glass into contact with the processing water in this way, the writing strength of the processing glass is improved. In addition, after the water treatment step S3, the drop strength of the glass for processing is also maintained, and therefore the drop strength of the glass product 1 made of the glass for processing is also improved. Furthermore, whether the contact time between the processing glass and the processing water (hereinafter referred to as water processing time) is too short or too long, the effect of improving the writing strength cannot be fully enjoyed. Therefore, it is important to set the water treatment time within the stated numerical range.

The lower limit range of the water treatment time is preferably 0.75 hours or more, 1 hour or more, 1.25 hours or more, or 1.5 hours or more. The upper limit range of the water treatment time is preferably 14 hours or less, 13 hours or less, 12 hours or less, or 11 hours or less.

The temperature of the treatment water is, for example, 10°C to 100°C. The lower limit range of the temperature of the treated water is preferably 20°C or higher, 30°C or higher, 40°C or higher, or 46°C or higher. The upper limit range of the temperature of the treated water is preferably 95°C or lower, 90°C or lower, or 85°C or lower. As the temperature of the treatment water becomes higher, the treatment time until the desired writing strength is obtained tends to become shorter.

When the glass for processing is chemically strengthened glass, in the water treatment step S3, it is preferable that the temperature of the treatment water is 50°C to 95°C, and the water treatment time is 0.5 hours to 10 hours.

The conductivity of the treated water is preferably 3 mS/m or less. The conductivity of the treated water is preferably 1 mS/m or less, 0.1 mS/m or less, or 0.01 mS/m or less. As the electrical conductivity of the treatment water becomes lower, the writing strength of the treatment glass becomes easier to increase. The treated water preferably does not contain detergents and other materials (eg, surfactants, water softeners, metal sealants, pH adjusters, stabilizers), etc.

An example of the embodiment of the water treatment step S3 is shown in FIG. 4 . As shown in FIG. 4 , the processing glass 6 is immersed in the processing water 5 stored in the container 4 . In the treated water 5 , for example, a plurality of sheets of processing glass 6 are supported by the support table 7 in a vertical position at predetermined intervals in the thickness direction. And the container 4 containing the processing glass 6 and the processing water 5 is accommodated in the thermostat (temperature adjustment device) 8 maintained at a predetermined time and a predetermined temperature, and the processing glass 6 is subjected to water treatment.

The method of bringing the treatment water into contact with the treatment glass is not particularly limited. As mentioned above, a method of immersing the treatment glass in the treatment water stored in the container is preferred. At this time, it is preferable to leave the processing glass in the processing water without imparting vibrations other than ultrasonic waves or the like to the processing water. If it is immersed in the treatment water in this way, the entire treatment glass can be brought into efficient contact with the treatment water, and the effect of improving the writing strength can be easily enjoyed. Furthermore, the treatment water may be sprayed onto the treatment glass from a nozzle or the like, or the flowing water may flow to the entire surface of the treatment glass.

The treatment glass can move relative to the treatment water. Specifically, for example, the processing glass immersed in the processing water may be moved in the processing water, or the processing glass may be moved in a region where the processing water is sprayed and supplied by a nozzle or the like.

(Second Embodiment) ＜Laminated body＞ As shown in FIG. 5 , the laminated body 9 of the second embodiment includes the above-mentioned glass product 1 , a protective layer 10 a laminated on one of the main surfaces 1 a (for example, the surface) of the glass product 1 , and the other main surface 1 a of the glass product 1 . Reinforcement layer 10b for surface 1a (eg backside). If so, since the glass product 1 is protected by the protective layer 10a, higher writing strength can be achieved. In addition, the reinforcing layer 10b can improve the bending strength of the glass product 1 and suppress damage during bending. It is preferable that the protective layer 10a is provided on the surface side of the glass product 1 that is in contact with the pen and the like, and the reinforcement layer 10b is provided on the back side of the glass product 1 that is not in contact with the pen and the like. Furthermore, only one of the protective layer 10a and the reinforcement layer 10b may be provided.

Examples of the protective layer 10a and the reinforcing layer 10b include plate-like or sheet-like resin, metal, glass, and the like, and these may be formed into a single layer or a combination of multiple layers. Among them, when the laminated body 9 is applied to a foldable type device, it is preferable that the protective layer 10a and the reinforcing layer 10b are resins that can easily provide flexibility.

The thickness of the resin contained in the protective layer 10a and the reinforcing layer 10b is preferably 0.5 μm to 200 μm, 1 μm to 150 μm, or 2 μm to 100 μm. Examples of the material of the resin contained in the protective layer 10 include: polycarbonate (PC), acrylic, polyethylene terephthalate (PET), polyetheretherketone (polyetheretherketone) ketone (PEEK), polyamide (PA), polyvinyl chloride (PVC), polyethylene (polyethylen, PE), polypropylene (PP), polyethylene naphthalate (polyethylene naphthalate (PEN), polyimide (PI), cyclo olefin polymer (COP), epoxy, etc.

The protective layer 10a and the reinforcing layer 10b are laminated on the main surface 1a of the glass product 1 via the adhesive layer 11, for example. The thickness of the adhesive layer 11 is preferably 0.1 μm to 100 μm, 0.2 μm to 90 μm, or 0.3 μm to 80 μm. Examples of the material of the adhesive layer 11 include: acrylic adhesive, silicone adhesive, rubber adhesive, ultraviolet curable acrylic adhesive, ultraviolet curable epoxy adhesive, thermosetting adhesive Epoxy adhesive, thermosetting melamine adhesive, thermosetting phenol adhesive, ethylene vinyl acetate (EVA), polyvinyl butyral (PVB), cyclic olefin polymer (COP) etc. Furthermore, the protective layer 10 can be directly formed on the main surface 1 a of the glass product 1 by any method such as coating without interposing the adhesive layer 11 .

(Third Embodiment) ＜Glass product manufacturing method＞ As shown in FIG. 6 , the glass product manufacturing method of the third embodiment sequentially includes a preparation step S11 , a chemical strengthening step S12 , a surface etching step S13 , and a water treatment step S14 . Among them, the steps other than the surface layer etching step S13 are the same as those corresponding to the above-described embodiment, and therefore detailed descriptions are omitted.

The surface layer etching step S13 is a step in which, after the chemical strengthening step S12 and before the water treatment step S14, the processing glass is etched in a range shallower than the compressive stress layer. By performing the surface layer etching step S13 in this manner, surface defects formed in the processing glass in the chemical strengthening step S12 and the like can be reduced. Therefore, the writing strength and/or the bending strength of the glass or glass product for handling can be improved.

In the surface layer etching step S13, for example, the entire processing glass is immersed in a liquid etching medium and the entire surface of the processing glass is wet etched. By such a process, the entire glass for processing can be etched uniformly, and therefore the occurrence of variations in thickness caused by the etching process can be suppressed. When such an etching process is performed, the surface of the glass for processing is an etching surface.

As the etching medium, an acidic or alkaline aqueous solution capable of etching glass can be used.

As an acidic etching medium, for example, an acidic aqueous solution containing hydrofluoric acid (hydrogen fluoride, HF) can be used. When an aqueous solution containing HF is used, the etching rate for glass is high and the production efficiency is good.

The aqueous solution containing HF is, for example, an aqueous solution containing only HF or a combination of HF and HCl, HF and HNO ₃ , HF and H ₂ SO ₄ , or HF and NH ₄ F. The concentration of each compound of HF, HCl, HNO ₃ , H ₂ SO ₄ and NH ₄ F is preferably 0.1 mol/L to 30 mol/L. During etching using an aqueous solution containing HF, fluoride containing a glass component is generated as a by-product, which may cause a decrease in the etching rate or cause _defects . Mixed acids with other acids such as ₂ SO ₄ can decompose this by-product and suppress the decrease in productivity. When etching is performed using an acidic aqueous solution, the temperature of the acidic aqueous solution is, for example, 10°C to 30°C, and the time for immersing the processing glass is preferably, for example, 0.1 minutes to 60 minutes.

As an alkaline etching medium, an alkali aqueous solution containing NaOH or KOH can be used. The alkali aqueous solution has a relatively small etching rate for glass compared with the etching medium containing the HF, and therefore has the advantage of being easy to precisely control the etching amount. This is particularly suitable when it is necessary to control the thickness of glass, DOC, etc. in units of several μm.

In an aqueous solution containing NaOH or KOH, the concentration of the alkali component is preferably 1 mol/L to 20 mol/L. When etching is performed using an alkali aqueous solution, the temperature of the alkali aqueous solution is, for example, 10°C to 130°C, and the time for immersing the processing glass is preferably, for example, 0.5 minutes to 120 minutes. Furthermore, when increasing the etching rate and improving productivity, it is preferable to heat the alkali aqueous solution to 80° C. or higher. On the contrary, when it is desired to control the etching amount with higher accuracy, it is preferable to limit the temperature of the alkali aqueous solution to 70° C. or lower. In addition, when more emphasis is placed on the etching rate, it is preferable to use an aqueous solution of NaOH.

The removal thickness of the surface layer portion of the processing glass in the surface layer etching step S13 is preferably 0.25 μm or more and 3 μm or less. The removed thickness of the surface layer portion of the processing glass is more preferably 0.4 μm or more and 2.7 μm or less, 0.6 μm or more and 2.5 μm or less, or 0.8 μm or more and 2.3 μm or less. By setting the etching amount within such a range, the variation in the maximum compressive stress or compressive stress depth before and after etching can be reduced.

It is preferable that the entire surface of the glass product manufactured through the surface etching step S13, that is, the two main surfaces of the front and back and the end surface, is composed of etched surfaces. If so, defects will be reduced on the entire surface of the glass product, and high strength, especially high writing strength, can be achieved.

(Fourth Embodiment) ＜Glass product manufacturing method＞ As shown in FIG. 7 , the glass product manufacturing method of the fourth embodiment includes a preparation step S21, a thinning step S22, a chemical strengthening step S23, a surface etching step S24, and a water treatment step S25. Among them, the steps other than the thinning step S22 are the same as those corresponding to the above-described embodiment, and therefore detailed descriptions are omitted. Furthermore, the surface layer etching step S24 may not be provided.

The thinning step S22 is a step of thinning the thickness of the processing glass to a range of 0.005 mm to 0.1 mm by etching. By performing the thinning step S22 in this way, even if a thick processing glass is prepared in the preparation step S21, the thickness of the processing glass can be thinned to an appropriate range.

In the thinning step S22, for example, the entire processing glass is immersed in a liquid etching medium and the entire surface of the processing glass is wet etched. As the etching medium, the same etching medium used in the surface layer etching step S24 can be used.

The thickness of the removed surface layer of the processing glass in the thinning step S22 depends on the original thickness (initial thickness) of the processing glass before the thinning step S22 and is therefore not particularly limited. However, it may be greater than that in the surface layer etching step. The thickness of the surface layer of the processing glass removed in S24.

(fifth embodiment) ＜Glass product manufacturing method＞ As shown in FIG. 8 , the glass product manufacturing method of the fifth embodiment includes a preparation step S31, a thinning step S32, and a water treatment step S33 in sequence. Each step is the same as the corresponding step in the above embodiment, but the difference is that the chemical strengthening step is not included in this embodiment.

According to this manufacturing method, in the water treatment step S33, the unstrengthened treatment glass comes into contact with the treatment water. In this case, the writing strength of the processing glass tends to be higher than when the chemically strengthened processing glass is brought into contact with the processing water. Therefore, even in the glass product produced through the water treatment step S33 of bringing unstrengthened treatment glass into contact with the treatment water, high writing strength can be obtained. That is, in the present invention, the glass product is not limited to chemically strengthened glass. Among them, chemically strengthened glass products tend to have higher bending strength. Therefore, from the viewpoint of taking into consideration both writing strength and bending strength, the glass product is preferably chemically strengthened glass.

In this embodiment, the case where the thinning step S32 is provided is exemplified. However, in the preparation step S31, it is possible to prepare processing glass that is preformed to a thickness of 0.005 mm to 0.1 mm by an overflow down-draw method or the like. , the thinning step S32 may not be provided.

(Sixth Embodiment) ＜Glass product manufacturing method＞ In the glass product manufacturing method of 6th Embodiment, the modification of the water treatment step in the said embodiment is shown. In the above embodiment, the temperature of the treated water in the water treatment step is 100°C or lower. However, in this embodiment, the temperature of the treated water is set to 100°C or higher.

As an example of the water treatment step of this embodiment, immersing the glass for treatment in the treatment water reaching 100 degreeC or more under a pressurized environment is mentioned. Specifically, the processing glass is immersed in the processing water stored in the container. Then, with the container accommodated in the pressurizing device, the inside of the pressurizing device is pressurized to heat the treated water to 100° C. or higher. By setting the treated water to 100° C. or higher in this way, an effect can be expected to shorten the water treatment time until the desired writing strength is obtained.

The temperature of the treated water is preferably over 100°C and below 200°C. The lower limit range of the temperature of the treated water is more preferably 105°C or higher, 110°C or higher, or 120°C or higher. The upper limit range of the temperature of the treated water is more preferably 190°C or lower, 180°C or lower, or 170°C or lower.

The pressure in the pressurized environment is preferably 0.15 MPa to 2.0 MPa. The lower limit range of the pressure in the pressurized environment is more preferably 0.17 MPa or more, 0.2 MPa or more, or 0.25 MPa or more. The upper limit range of the pressure in the pressurized environment is further preferably 1.9 MPa or less, 1.8 MPa or less, or 1.7 MPa or less.

The lower limit range of the water treatment time is preferably 0.6 hours or more, 0.75 hours or more, or 1 hour or more. The upper limit range of the water treatment time is preferably 12 hours or less, 11 hours or less, or 10 hours or less.

Instead of immersing the processing glass in the processing water of 100°C or higher, the processing water may be sprayed onto the processing glass as superheated vapor at 100°C or higher.

Furthermore, although the embodiment of the present invention has been described, the embodiment of the present invention is not limited thereto, and various modifications can be made without departing from the gist of the present invention.

In the above embodiment, the shape of the glass product is not particularly limited. The shape of the glass product may be, for example, square, rectangular, circular, oval, etc. when viewed from above.

In the above embodiment, the glass product may also be subjected to three-dimensional bending processing if necessary. Specifically, by performing a three-dimensional bending process on all or part of the processing glass in advance, a three-dimensional curved shape can be given to the finally manufactured glass product.

In the above embodiment, the case where the chemical strengthening step (ion exchange treatment) is performed once is exemplified, but the chemical strengthening step may be performed two or three times or more. In addition, heat treatment can also be performed before and after ion exchange. Heat treatment can relax stress or promote ion diffusion to control the depth of the compressive stress layer. When the chemical strengthening step is performed, it is preferable to clean and dry the processing glass after the chemical strengthening step and before the water treatment step. Furthermore, when multiple chemical strengthenings are performed as described above, the stress distribution of the strengthened glass product may have more than one buckling point, maximum value, minimum value or inflection point in the area of the compressive stress layer 2. At least either one.

In the embodiment, the tensile stress in the tensile stress layer 3 may be in a non-constant form in the thickness direction. For example, when the DOC of the glass product is set large relative to the thickness t (for example, when DOC≧0.20t), the stress distribution in the tensile stress layer 3 can be formed along the thickness of the glass product. The distribution shape of a downwardly convex quadratic curve with a minimum value in the center.

In the above embodiment, the stress distribution of the glass product may also be asymmetrical between the front and back. The asymmetric stress distribution on the front and back is obtained by grinding one of the main surface sides of the strengthened glass product more than the other side, or by providing one of the main surface sides with an ion-exchange-impeding surface. Chemical strengthening is carried out in the film state. [Example]

Hereinafter, the glass product of this invention is demonstrated based on an Example. Furthermore, the following examples are only examples, and the present invention is not limited by the following examples.

Samples were prepared as follows. First, processing glass having the glass composition described in Table 1 is prepared. In addition, the Young's modulus shown in Table 1 is a value measured using the resonance method.

[Table 1] (mol%) A B SiO ₂ 66.4 69.9 Al ₂ O ₃ 11.5 8.67 MgO 4.8 4.7 CaO 0.1 0.1 B ₂ O ₃ 0.5 2.3 ZnO - - ZrO ₂ - - Li ₂ O 0.02 0.03 Na ₂ O 15.2 13.7 K ₂ O 1.4 0.45 P ₂ O ₅ - - SnO ₂ 0.1 0.15 Young's modulus (GPa) 72.1 70.1

Specifically, glass raw materials were prepared so as to have the composition described in Table 1 and melted in a test melting furnace. Then, the obtained molten glass is shaped into a plate or sheet shape by an overflow down-drawing method, and cut into a predetermined size to obtain glass for processing.

Next, the plate-like or sheet-like processing glass is processed under the conditions described in Tables 2 to 8 to produce plate-like or sheet-like glass products. The thinning step and the surface layer etching step are performed by immersing the glass for processing in an HF aqueous solution. The chemical strengthening step is performed by immersing the treatment glass in 100% molten salt of KNO ₃ . The water treatment step is performed by immersing the glass for treatment in the treatment water. In Tables 2 to 8, No. 1 to No. 29 are examples of the present invention, and Nos. 30 to No. 45 are comparative examples.

[Table 2] No. 1 2 3 4 5 6 7 8 composition A A A B A B A A thickness Initial thickness after thinning and surface etching 50 μm - - 50 μm - - 50 μm - - 50 μm - - 50 μm - - 50 μm - - 50 μm 47 μm - 300 μm 50 μm - Thin wall Etching solution concentration temperature time - - - - - - HF 0.1 mol/L 30℃ 20 minutes HF 5 mol/L 30℃ 36 minutes chemical strengthening molten salt temperature time - - - - - - - - Surface etching Etching solution concentration temperature time - - - - - - - - water treatment conductivity temperature time pressurization 0.01 mS/m 80℃ 1 hour- 0.1 mS/m 80℃ 2 hours- 1 mS/m 80℃ 4 hours- 0.1 mS/m 80℃ 4 hours- 0.1 mS/m 150℃ 1 hour 0.8 MPa 0.1 mS/m 150℃ 2 hours 0.8 MPa 0.1 mS/m 80℃ 2 hours- 0.1 mS/m 80℃ 2 hours- Protective layer (laminate) Material thickness - - - - - - - - Pen down strength Maximum damage height 60% of damage height 15 cm 13 cm 14 cm 11 cm 12 cm 11 cm 15 cm 12 cm 14 cm 12 cm 14 cm 11 cm 14 cm 11 cm 13 cm 11 cm Two point bending strength central value maximum value minimum value - 691 MPa 1728 MPa 310 MPa - - - - - -

[table 3] No. 9 10 11 12 13 14 15 16 composition A A A B A B A A thickness Initial thickness after thinning and surface etching 50 μm - - 50 μm - - 50 μm - - 50 μm - - 50 μm - - 50 μm - - 50 μm 47 μm - 300 μm 50 μm - Thin wall Etching solution concentration temperature time - - - - - - HF 0.1 mol/L 30℃ 20 minutes HF 5 mol/L 30℃ 36 minutes chemical strengthening molten salt temperature time KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes Surface etching Etching solution concentration temperature time - - - - - - - - water treatment conductivity temperature time pressurization 0.01 mS/m 80℃ 1 hour- 0.1 mS/m 80℃ 2 hours- 1 mS/m 80℃ 4 hours- 0.1 mS/m 80℃ 4 hours- 0.1 mS/m 150℃ 1 hour 0.8 MPa 0.1 mS/m 150℃ 2 hours 0.8 MPa 0.1 mS/m 80℃ 2 hours- 0.1 mS/m 80℃ 2 hours- Protective layer (laminate) Material thickness - - - - - - - - Pen down strength Maximum damage height 60% of damage height 8 cm 5 cm 7 cm 5 cm 6 cm 5 cm 6 cm 5 cm 7 cm 6 cm 7 cm 6 cm 7 cm 6 cm 7 cm 6 cm Two point bending strength central value maximum value minimum value - 1443 MPa 2253 MPa 1051 MPa - 1490 MPa 2104 MPa 1023 MPa - - - - CS - 669MPa - - - - - - DOL - 11.2 μm - - - - - - CT - 133MPa - - - - - -

[Table 4] No. 17 18 19 20 twenty one twenty two twenty three twenty four composition A A A B A A A B thickness Initial thickness after thinning and surface etching 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm Thin wall Etching solution concentration temperature time - - - - - - - - chemical strengthening molten salt temperature time KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes Surface etching Etching solution concentration temperature time HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes water treatment conductivity temperature time pressurization 0.01 mS/m 80℃ 1 hour- 0.1 mS/m 80℃ 2 hours- 1 mS/m 80℃ 4 hours- 0.1 mS/m 80℃ 4 hours- 0.1 mS/m 20℃ 10 hours- 0.1 mS/m 50℃ 5 hours- 0.1 mS/m 150℃ 1 hour 0.8 MPa 0.1 mS/m 150℃ 2 hours 0.8 MPa Protective layer (laminate) Material thickness - - - - - - - - Pen down strength Maximum damage height 60% of damage height 10 cm 9 cm 9 cm 9 cm 8 cm 7 cm 9 cm 7 cm 8 cm 7 cm 8 cm 7 cm 9 cm 8 cm 10 cm 8 cm Two point bending strength central value maximum value minimum value - 3837 MPa 5165 MPa 1956 MPa - - - - - - CS - 588MPa - - - - - - DOL - 10.3 μm - - - - - - CT - 92 MPa - - - - - -

[table 5] No. 25 26 27 28 29 composition A A A A A thickness Initial thickness after thinning and surface etching 50 μm 48 μm 47 μm 300 μm 50 μm 47 μm 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm Thin wall Etching solution concentration temperature time HF 0.1 mol/L 30℃ 13 minutes HF 0.1 mol/L 30℃ 36 minutes - - - chemical strengthening molten salt temperature time KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes Surface etching Etching solution concentration temperature hours HF 0.1 mol/L 30℃ 7 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes water treatment conductivity temperature time pressurization 0.1 mS/m 80℃ 2 hours- 0.1 mS/m 80℃ 2 hours- 0.1 mS/m 80℃ 2 hours- 0.1 mS/m 80℃ 2 hours- 0.1 mS/m 80℃ 2 hours- Protective layer (laminate) Material thickness - - PET film 50 μm PET film 50 μm PI coating 20 μm Pen down strength Maximum damage height 60% of damage height 11 cm 9 cm 10 cm 9 cm 25 cm 22 cm 23 cm 21 cm 14 cm 13 cm Two point bending strength central value maximum value minimum value - - - - -

[Table 6] No. 30 31 32 33 34 35 36 37 composition A B A A A B A A thickness Initial thickness after thinning and surface etching 50 μm - - 50 μm - - 50 μm 47 μm - 300 μm 50 μm - 50 μm - - 50 μm - - 50 μm 47 μm - 300 μm 50 μm - Thin wall Etching solution concentration temperature time - - HF 0.1 mol/L 30℃ 20 minutes HF 5 mol/L 30℃ 36 minutes - - HF 0.1 mol/L 30℃ 20 minutes HF 5 mol/L 30℃ 36 minutes chemical strengthening molten salt temperature time - - - - KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes Surface etching Etching solution concentration temperature time - - - - - - - - water treatment conductivity temperature time pressurization - - - - - - - - Protective layer (laminate) Material thickness - - - - - - - - Pen down strength Maximum damage height 60% of damage height 4 cm 3 cm 6 cm 5 cm 4 cm 3 cm 3 cm 2 cm 3 cm 2 cm 4 cm 3 cm 3 cm 2 cm 3 cm 2 cm Two point bending strength central value maximum value minimum value 760 MPa 1753 MPa 337 MPa 682 MPa 1374 MPa 282 MPa - - 1516 MPa 2124 MPa 1057 MPa - - - CS - - - - 674 MPa - - - DOL - - - - 11.7 μm - - - CT - - - - 135 MPa - - -

[Table 7] No. 38 39 40 41 composition A B A A thickness Initial thickness after thinning and surface etching 50 μm - 47 μm 50 μm - 47 μm 50 μm 48 μm 47 μm 300 μm 50 μm 47 μm Thin wall Etching solution concentration temperature time - - HF 0.1 mol/L 30℃ 13 minutes HF 5 mol/L 30℃ 36 minutes chemical strengthening molten salt temperature time KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 15 minutes Surface etching Etching solution concentration temperature time HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 7 minutes HF 0.1 mol/L 30℃ 20 minutes water treatment conductivity temperature time pressurization - - - - Protective layer (laminate) Material thickness - - - - Pen down strength Maximum damage height 60% of damage height 3 cm 3 cm 4 cm 3 cm 4 cm 3 cm 3 cm 3 cm Two point bending strength central value maximum value minimum value 3733 MPa 5302 MPa 2050 MPa - - - CS 597MPa - - - DOL 10.5 μm - - - CT 103MPa - - -

[Table 8] No. 42 43 44 45 composition A A A A thickness Initial thickness after thinning and surface etching 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm 50 μm - 47 μm Thin wall Etching solution concentration temperature time - - - - chemical strengthening molten salt temperature time KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes KNO ₃ 390℃ 15 minutes KNO ₃ 390℃ 30 minutes Surface etching Etching solution concentration temperature time HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes HF 0.1 mol/L 30℃ 20 minutes water treatment conductivity temperature time pressurization 0.1 mS/m 80℃ 0.1 hour- 0.1 mS/m 80℃ 0.25 hours- 0.1 mS/m 80℃ 15 hours- 0.1 mS/m 80℃ 30 hours- Protective layer (laminate) Material thickness - - - - Pen down strength Maximum damage height 60% of damage height 4 cm 3 cm 6 cm 4 cm 6 cm 4 cm 5 cm 4 cm Two point bending strength central value maximum value minimum value - - - -

＜Manufacturing method of glass products or laminates＞ (1) In No. 1 to No. 6 of Table 2, perform a water treatment step on the glass for processing to produce glass products. In No. 7 to No. 8 of Table 2, the glass for processing was subjected to a thinning step and a water treatment step in order to produce glass products. That is, in No. 1 to No. 8 of Table 2, the processing glass was not subjected to the chemical strengthening step. Furthermore, in No. 1 to No. 6, the initial thickness of the processing glass is consistent with the thickness of the glass product, and in No. 7 to No. 8, the thickness of the processing glass after the thinning step is consistent with the thickness of the glass product. The thickness is consistent.

(2) In No. 9 to No. 14 of Table 3, the glass for treatment is sequentially subjected to a chemical strengthening step and a water treatment step to produce glass products. In No. 15 to No. 16 of Table 3, the glass for processing was subjected to a thinning step, a chemical strengthening step, and a water treatment step in order to produce glass products. Furthermore, in No. 9 to No. 14, the initial thickness of the processing glass is consistent with the thickness of the glass product, and in No. 15 to No. 16, the thickness of the processing glass after the thinning step is consistent with the thickness of the glass product. The thickness is consistent.

(3) In No. 17 to No. 24 of Table 4, the chemical strengthening step, the surface layer etching step, and the water treatment step are sequentially performed on the glass for processing to produce glass products. Furthermore, in Nos. 17 to 24, the thickness of the processing glass after the surface layer etching step is consistent with the thickness of the glass product.

(4) In No. 25 to No. 26 of Table 5, the glass for processing is sequentially subjected to a thinning step, a chemical strengthening step, a surface etching step, and a water treatment step to produce a glass product. In No. 27 to No. 29 of Table 5, the chemical strengthening step, the surface layer etching step, and the water treatment step were sequentially performed on the glass for processing to produce glass products. Furthermore, in No. 27 to No. 29 of Table 5, a protective layer (PET film, PA film, PI coating) was laminated on one of the main surfaces of the glass product to produce a laminated body. PET film and PA film are bonded to glass products through a pressure-sensitive adhesive (PSA) sheet with a thickness of 5 μm. The PI coating is formed by coating PI on the main surface of the glass product. Furthermore, in Nos. 25 to 29, the thickness of the processing glass after the surface layer etching step is consistent with the thickness of the glass product.

(5) In No. 30 and No. 31 of Table 6, the glass for treatment was made into glass products in an untreated state. In No. 32 and No. 33 of Table 6, the processing glass was subjected to a thinning step to produce glass products. In No. 34 and No. 35 of Table 6, a chemical strengthening step was performed on the glass for processing to produce glass products. In No. 36 and No. 37 of Table 6, the thinning step and the chemical strengthening step were performed in order to produce glass products. That is, in No. 30 to No. 33 of Table 6, the chemical strengthening step and the water treatment step were not performed on the glass for processing. In No. 34 to No. 37 of Table 6, the water treatment step was not performed on the glass for treatment. Furthermore, in No. 30, No. 31, No. 34, and No. 35, the initial thickness of the processing glass is consistent with the thickness of the glass product. In No. 32, No. 33, No. 36, and No. 37, the thickness of the processing glass after the thinning step is consistent with the thickness of the glass product.

(6) In No. 38 to No. 39 of Table 7, perform a chemical strengthening step and a surface etching step on the glass for processing in order to produce glass products. In No. 40 to No. 41 of Table 7, the glass for processing was subjected to a thinning step, a chemical strengthening step, and a surface etching step in order to produce a glass product. That is, in No. 38 to No. 41 of Table 7, the water treatment step was not performed on the glass for processing. Furthermore, in Nos. 38 to 41, the thickness of the processing glass after the surface layer etching step is consistent with the thickness of the glass product.

(7) In No. 42 to No. 45 of Table 8, the chemical strengthening step, the surface layer etching step, and the water treatment step are sequentially performed on the glass for processing to produce glass products. Furthermore, in Nos. 42 to 45, the thickness of the processing glass after the surface layer etching step is consistent with the thickness of the glass product. Furthermore, in Nos. 42 to 45, the glass for treatment is subjected to a water treatment step, and the water treatment time is less than 0.5 hours or more than 15 hours.

In Examples and Comparative Examples in which a part of the chemical strengthening step was performed, CS, DOC, and CT of the glass products were measured. CS, DOC, and CT in Tables 1 to 8 are values measured on each glass product (sample) using a surface stress meter FSM-6000LE manufactured by Orihara Seisakusho.

＜Pen drop test＞ As shown in FIG. 9 , in the pen-down test, the pen tip of the ball-point pen 18 is dropped onto the measurement sample 12 to evaluate the strength (pen-down strength) of the glass product 13 included in the measurement sample 12 .

In the writing test of Nos. 1 to 26 and Nos. 30 to 45, as the measurement sample 12, a glass product 13, a PSA sheet 14, a PET sheet 15, a PSA sheet 16, and a SUS sheet were sequentially laminated. 17 samples. On the other hand, in the pen-down tests of Nos. 27 to 29, a protective layer (PET film, PA film, PI coating) was further provided on the upper surface of the glass product 13 in the measurement sample 12. That is, in the pen-down tests No. 1 to No. 26 and No. 30 to No. 45, the pen tip of the ball-point pen 18 was in direct contact with the glass product 13. In the pen-down tests No. 27 to No. 29, the tip of the ball-point pen 18 was in direct contact with the glass product 13. The pen tip is in direct contact with the protective layer.

The top view dimensions of the glass product 13, PSA sheet 14, PSA sheet 16, PET plate 15 and protective layer are respectively set to 50 mm × 50 mm. The top view size of the SUS board 17 is set to 55 mm×55 mm. The thickness of the glass product 13 and the protective layer is as described in Tables 2 to 8. The thickness of the PSA sheets 14 and 16 was set to 50 μm. The thickness of the PET plate 15 was set to 125 μm. The thickness of the SUS board 17 is set to 3 mm.

In the pen drop test, five measurement samples 12 of No. 1 to No. 45 are prepared, and the tip of the ballpoint pen 18 is dropped to the center of each measurement sample 12 . At this time, the ballpoint pen 18 is passed through the inner hole of the vertically held guide tube 19 and dropped to the measurement sample 12 so that the tip of the ballpoint pen 18 falls vertically relative to the measurement sample 12 . The ballpoint pen 18 is orange EG 0.7 manufactured by BIC Company, with a ball diameter of 0.7 mm and a mass of 5.7 g. The height of the tip of the pen before dropping based on the upper surface of the measurement sample 12 was set as the drop height H, and the pen tip was dropped with its initial value set to 1 cm. When the glass product 13 included in the measurement sample 12 is not damaged by dropping the ballpoint pen 18, it is raised to a height of 1 cm and dropped again. In this way, the rise and fall of the drop height H are repeatedly attempted until the glass product 13 included in the measurement sample 12 is damaged. Furthermore, the 60% damage height and the maximum damage height were determined as the writing strength. The 60% damage height is the drop height H when the glass product 13 contained in three of the five measurement samples 12 is damaged. The maximum damage height is the drop height H when all the glass products 13 included in the five measurement samples 12 are damaged.

Based on the results of the pen-down test, it was confirmed that the appropriate water treatment step was performed in the Examples (No. 1 to No. 29) and the Comparative Example (No. 1) in which the water treatment step was not completely performed or the appropriate water treatment step was not performed. .30～No.45), the damage height is increased by 60%.

＜Bend failure test＞ As shown in FIG. 10 , in the bending failure test, a measurement sample 20 including a glass product is sandwiched between two plate-shaped bodies 21 and is pressed and bent to produce a U-shaped bend, so-called two-point bending. Strength is evaluated by bending (two-point bending strength). The two-point bending strength was evaluated only by No.2, No.10, No.18, No.30, No.34, and No.38, and 30 measurement samples corresponding to these glass products were prepared. 20. The plan view size of the measurement sample 20 is 140 mm×70 mm. The thickness of the measured sample 20 was as described in Tables 2 to 8, and was set to 50 μm in No. 2, No. 10, No. 30, and No. 34, and was set to 47 in No. 18 and No. 38. μm. Then, the measurement sample 20 is arranged between the plate-shaped bodies 21 so as to be bent in a U-shape along the long side (140 mm side).

The two-point bending strength is calculated based on the following equation (4) using the distance D between the two plate-shaped bodies 21 when the glass product 20 is broken due to press bending. Furthermore, as the two-point bending strength, the central value, the maximum value, and the minimum value were obtained. The median value of the two-point bending strength is the median value when the two-point bending strength data of 30 measured samples are arranged in descending order. The maximum value of the two-point bending strength is the maximum value among the two-point bending strengths of the 30 measured specimens. The minimum value of the two-point bending strength is the minimum value among the two-point bending strengths of the 30 measured specimens. σ=1.198[E×t/(D-t)] (4) Among them, σ represents the two-point bending strength [MPa], E represents the Young's modulus of the glass product [MPa], and t represents the thickness of the glass product [mm].

According to the results of the bending failure test, it was confirmed that among the chemically strengthened glass products (No. 10, No. 18, No. 34, and No. 38), the glass products that were not chemically strengthened (No. 2, No.30), the two-point bending strength is improved. In particular, it was confirmed that the two-point bending strength was greatly improved in the glass products (No. 18 and No. 38) that were subjected to a surface etching step after chemical strengthening. Therefore, from the viewpoint of simultaneously improving the pen-down strength and the two-point bending strength of glass products, it is found that it is preferable to perform a chemical strengthening step and then perform an appropriate water treatment step. [Industrial availability]

The glass product of the present invention can be used, for example, in cover glass for smartphones, mobile phones, tablets, personal computers, digital cameras, touch panel displays, other display components, in-vehicle display components, in-vehicle panels, and the like.

1:Glass products 1a: Main surface 1b: End face 2: Compressive stress layer 3: Tensile stress layer 4:Container 5: Treat water 6: Glass for handling 7: Support platform 8: Thermostatic device (temperature adjustment device) 9: Laminated body 10a:Protective layer 10b: Enhancement layer 11:Adhesive layer 12: Measure the sample 13:Glass products 14:PSA piece 15:PET board 16:PSA piece 17:SUS board 18:Ballpoint pen 19: Guide cylinder 20: Measurement sample (glass products) 21: plate-like body A1: The first area A2:Second area CS: maximum compressive stress CT: maximum tensile stress D:interval DCT: tensile stress convergence depth DOC: depth H: drop height S1, S11, S21, S31: Preparatory steps S2, S12, S23: chemical strengthening steps S3, S14, S25, S33: water treatment steps S13, S24: Surface etching step S22, S32: Thin-walling step t:Thickness

FIG. 1 is a schematic cross-sectional view showing a glass product according to the first embodiment of the present invention. FIG. 2 is an image diagram of stress distribution in the thickness direction of the glass product according to the first embodiment of the present invention. Fig. 3 is a flow chart of the glass product manufacturing method according to the first embodiment of the present invention. 4 is a cross-sectional view showing an embodiment of the water treatment step included in the glass product manufacturing method according to the first embodiment of the present invention. FIG. 5 is a schematic diagram showing a cross section of a laminated body according to a second embodiment of the present invention. Fig. 6 is a flow chart of the glass product manufacturing method according to the third embodiment of the present invention. Fig. 7 is a flow chart of a glass product manufacturing method according to the fourth embodiment of the present invention. Fig. 8 is a flow chart of the glass product manufacturing method according to the fifth embodiment of the present invention. FIG. 9 is a side view showing an embodiment of the pen-down test. Fig. 10 is a side view showing an embodiment of the bending failure test.

S1: Preparatory steps

S2: Chemical strengthening step

S3: Water treatment steps

Claims (14)

A method for manufacturing a glass product, including: a preparation step of preparing a treatment glass including an alkaline aluminosilicate glass containing an alkali metal oxide as a glass component; and In the water treatment step, the glass for treatment is contacted with the treatment water for more than 0.5 hours and less than 15 hours. The glass product manufacturing method according to claim 1, wherein in the water treatment step, the glass for treatment is immersed in the treatment water at 46°C to 100°C. The glass product manufacturing method according to claim 1, wherein in the water treatment step, the glass for treatment is immersed in the treatment water reaching 100° C. or higher in a pressurized environment. The glass product manufacturing method according to any one of claims 1 to 3, wherein in the water treatment step, the conductivity of the treated water is 3 mS/m or less. The method for manufacturing a glass product according to any one of claims 1 to 4, wherein the processing glass is in the form of a plate or sheet with a thickness of 0.005 mm to 0.1 mm. The glass product manufacturing method according to claim 5, further comprising a thinning step, which thins the processing glass to the thickness by etching before the water treatment step. within the range. The glass product manufacturing method according to claim 5, wherein the processing glass is preformed into the thickness range by an overflow down-drawing method. The method for manufacturing glass products according to any one of claims 1 to 7, further comprising a chemical strengthening step, which, before the water treatment step, brings the treatment glass into contact with an alkali metal nitrate. A compressive stress layer with a maximum compressive stress of more than 100 MPa is formed on the surface. The glass product manufacturing method according to claim 8, wherein in the water treatment step, the temperature of the treatment water is 50°C to 95°C, and the contact time between the treatment glass and the treatment water is 0.5 hours to 10 hours. The manufacturing method of glass products according to claim 8 or 9, wherein the glass for processing contains 50% to 80% SiO ₂ , 5% to 25% Al ₂ O ₃ , 0% to 35% B ₂ O ₃ , 0% to 20% Li ₂ O, 1% to 20% Na ₂ O, 0% to 10% K ₂ O, in the chemical strengthening step, The alkali metal nitrate is a molten salt containing potassium nitrate. The method for manufacturing glass products according to any one of claims 8 to 10, further comprising a surface etching step, which is performed after the chemical strengthening step and before the water treatment step. The processing glass is etched within a shallow range. A glass product, which is a plate-shaped or sheet-shaped glass product with a thickness of 0.005 mm to 0.1 mm, wherein, In a pen-drop test in which a 5.7-g ballpoint pen with a spherical tip with a diameter of 0.7 mm was dropped onto the main surface, the 60% damage height was 5 cm or more. The glass product according to claim 12, including a compressive stress layer having a maximum compressive stress of 100 MPa or more on the surface. A laminated body including: the glass product according to claim 12 or 13; and A protective layer or reinforcing layer is laminated on at least one of the main surfaces of the glass product.