CN109803938A - The manufacturing method of chemically reinforced glass - Google Patents
The manufacturing method of chemically reinforced glass Download PDFInfo
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- CN109803938A CN109803938A CN201780060568.4A CN201780060568A CN109803938A CN 109803938 A CN109803938 A CN 109803938A CN 201780060568 A CN201780060568 A CN 201780060568A CN 109803938 A CN109803938 A CN 109803938A
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- glass
- chemically reinforced
- chemical strengthening
- intensity
- manufacturing
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The present invention provides a kind of intensity that will not weaken glass carrying out prolonged chemical intensification treatment at high temperature, shows the manufacturing method of deeper compressive stress layers (DOC) and the high chemically reinforced glass of surface intensity.The present invention relates to a kind of manufacturing methods of chemically reinforced glass, comprise the following steps: chemical strengthening process makes glass with the hydrogen ion exponent (pH) when 10 mass % aqueous solution is made for 7.5~10.5 and the inorganic salts containing at least one of sodium nitrate and potassium nitrate contacts and carry out ion exchange；And acid treatment process, the glass after making the chemical strengthening process contact with the acid solution of hydrogen ion exponent (pH) less than 7.0 and carry out sour processing.
Description
Technical field
The present invention relates to a kind of manufacturing methods of chemically reinforced glass.
Background technique
It is aobvious in plates such as digital camera, mobile phone, portable information terminal PDA (Personal Digital Assistants)
Show in device device, in order to protect display and improve beauty, implements to become the side in the region greater than image displaying part
Formula is by laminal cover configurations of glass in the front surface of display.Although glass theoretical strength is high, since damage will lead to by force
Degree is greatly reduced, and therefore, for the cover glass of desired strength, forms compression stress in glass surface using by ion exchange etc.
The chemically reinforced glass of layer.
Along with the requirement of lightweight and slimming to flat display devices, need cover glass itself also thinning.Cause
This, for cover glass, in order to meet the purpose and to the further intensity of surface requirements.
As one of the method for improving strength of glass, Patent Document 1 discloses utilize the inorganic salts containing specific salts
The sour method handled with alkali process is carried out after carrying out chemical strengthening.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2015/008763
Summary of the invention
However, the method for being recorded in patent document 1, if (being defined as pressing for the depth for improving compressive stress layers
Stress under compression value becomes zero depth, hereinafter, also referred to as DOC (Depth of Compression)) to obtain high-intensitive mesh
And carry out long-time chemical strengthening at high temperature, then there are the following problems: as side effect strength of glass reduce, and chemistry
Temperature condition, the limited time system of reinforcing.
In addition, it is previous, the raising of surface intensity is sought by being ground after chemical intensification treatment, it is likely that
Glass surface is caused to damage due to grinding, surface intensity declines instead.In turn, it is possible to since grinding increases the warpage of glass
Greatly.
Therefore, it is unrestricted to provide a kind of temperature condition of chemical strengthening, time by the present invention, even if being grown at high temperature
The chemical intensification treatment of time will not weaken the intensity of glass, show deeper DOC and the high chemical strengthening glass of surface intensity
The manufacturing method of glass.
Further investigation has been repeated in the inventors of the present invention, as a result, it has been found that passing through the pH for implementing to make salt used in chemical strengthening
The acid treatment process of sour processing is carried out for the chemical strengthening process of prescribed limit and to the glass after the chemical strengthening process,
Temperature condition, the time that chemical strengthening can be obtained are unrestricted, even if carrying out prolonged chemical intensification treatment at high temperature
Show deeper DOC and the high chemically reinforced glass of surface intensity, so as to complete the present invention.
That is, the present invention is as follows.
1. a kind of manufacturing method of chemically reinforced glass, comprises the following steps:
Chemical strengthening process, the hydrogen ion exponent (pH) when making glass and 10 mass % aqueous solution is made are 7.5~10.5
And the inorganic salts containing at least one of sodium nitrate and potassium nitrate contact and carry out ion exchange；With
Acid treatment process, acidity of the glass with hydrogen ion exponent (pH) less than 7.0 after making the chemical strengthening process are molten
Liquid contacts and carries out sour processing.
2. the manufacturing method of the chemically reinforced glass according to above-mentioned 1, wherein further comprise following process: at alkali
Science and engineering sequence, the glass after making the acid treatment process contact with the alkaline solution that hydrogen ion exponent (pH) is more than 7.0 and carry out alkali
Processing.
3. the manufacturing method of the chemically reinforced glass according to above-mentioned 1 or 2, wherein the chemical strengthening process is to make
The glass contacts 2 hours or more with 400 DEG C or more of the inorganic salts and the process that carries out ion exchange.
4. the manufacturing method of the chemically reinforced glass according to above-mentioned any one of 1~3, wherein the chemical strengthening
Glass after process has 35 μm of depth or more of compressive stress layers.
5. the manufacturing method of the chemically reinforced glass according to above-mentioned any one of 1~4, wherein the chemical strengthening
Glass after process passes through ball and ring test (ボ ー Le オ Application リ Application グ Shi test) the surface intensity F (N) that measures under the following conditions is opposite
In glass plate plate thickness t (mm) be F >=1000 × t2。
Ball and ring test condition:
By the glass plate configuration of plate thickness t (mm) in the fillet of diameter 30mm, contact portion with radius of curvature 2.5mm by not
Become rusty on the ring that steel is constituted, making the sphere of diameter 10mm being made of steel and in the state of the contact glass sheet, make the sphere with
Decrease speed 1mm/min declines and applies at the center of the ring and load, and the breaking load (unit N) when glass plate is destroyed is set
For BOR intensity, 20 measurement average value of the BOR intensity is set as surface intensity F (N).Wherein, from for calculating average value
The resulting data when the destruction starting point of glass plate leaves the load point 2mm or more of the sphere are excluded in data.
In the manufacturing method of chemically reinforced glass of the invention, by using pH be prescribed limit inorganic salts to glass into
Row chemical strengthening utilizes the OH in inorganic salts-The Si-O-Si key of glass is moderately cut off, compression is formed in glass surface and answers
The low-density layer that the surface layer of power layer is modified.Then, by carrying out sour processing, which can equably be removed, i.e.,
Make without milled processed, also can effectively significantly improve the surface intensity of glass.
Therefore, the manufacturing method of chemically reinforced glass according to the present invention can simply obtain the temperature of chemical strengthening
Condition, time are unrestricted, even if carrying out at high temperature, prolonged chemical intensification treatment also shows deeper DOC and face is strong
Spend high chemically reinforced glass.
Detailed description of the invention
Fig. 1 (a)~(d) is the schematic diagram for indicating the manufacturing process of chemically reinforced glass of the invention.
Fig. 2 is the schematic diagram for illustrating the method for ball and ring test.
Fig. 3 A is the afm image for the glass surface that there is surface grinding to hurt, and Fig. 3 B is the glass without surface grinding wound
The afm image on surface.
Fig. 4 A is the figure for indicating not generate the state of white haze in glass surface, Fig. 4 B be indicate to have in glass surface it is white
The figure of the state of mist.
Fig. 5 A indicates the stress distribution of chemically reinforced glass obtained in embodiment 1 and 3 and comparative example 1, and Fig. 5 B is indicated
The stress distribution of chemically reinforced glass obtained in embodiment 7 and 8 and comparative example 6, Fig. 5 C indicate embodiment 10 and 11 and
The stress distribution of chemically reinforced glass obtained in comparative example 11.
Fig. 6 A and Fig. 6 B indicate strong to the face of chemically reinforced glass obtained in embodiment 1 and 5 and comparative example 1,4 and 5
Result obtained by degree is evaluated.
Fig. 7 A and Fig. 7 B indicate to carry out the surface intensity of chemically reinforced glass obtained in embodiment 7 and 8 and comparative example 6
Result obtained by evaluation.
Fig. 8 A and Fig. 8 B indicate the surface intensity to chemically reinforced glass obtained in embodiment 10 and 11 and comparative example 11
Result obtained by being evaluated.
Specific embodiment
Hereinafter, the present invention is described in detail, but the present invention is not limited to the following embodiments and the accompanying drawings, can not take off
Implement from arbitrarily being deformed in the range of purport of the invention.
Here, " quality % " is respectively identical contain with " weight % ", " quality ppm " and " weight ppm " in this specification
Justice.In addition, being indicated " weight ppm " in the case where being only recorded as " ppm ".
In addition, in this specification, indicate "~" of numberical range using comprising numerical value documented by its front and back as lower limit value
It is used with the meaning of upper limit value, unless otherwise specified, then following "~" in the present specification is used with same meaning.
The manufacturing method > of < chemically reinforced glass
Hereinafter, to one of the method (hereinafter also referred to as method of the invention) for manufacturing chemically reinforced glass of the invention
Scheme is illustrated, but the present invention is not limited to this.It should be noted that unless otherwise specified, then the composition of glass is with oxygen
The molar percentage meter of compound benchmark.
(chemical strengthening process)
Chemical strengthening process in method of the invention is following process: when making glass and 10 mass % aqueous solution is made
Hydrogen ion exponent (pH) is 7.5~10.5 and the inorganic salts contact containing at least one of sodium nitrate and potassium nitrate, will be above-mentioned
The K in Na and above-mentioned inorganic salts in glass carries out ion exchange and forms compressive stress layers, and further shape in glass surface
Occur to be modified and the low-density layer of low-density at the surface layer of the compressive stress layers.
Hydrogen ion exponent (pH) of the inorganic salts when 10 mass % aqueous solution is made is 7.5 or more, preferably 8.0 or more,
More preferably 8.5 or more.In addition, the hydrogen ion exponent (pH) when 10 mass % aqueous solution is made is 10.5 hereinafter, preferably
10.0 hereinafter, more preferably 9.5 or less.
By making the pH above range of inorganic salts, the OH in inorganic salts can be utilized-By the Si-O-Si key appropriateness of glass
On the surface layer that glass surface forms compressive stress layers modified low-density layer occurs for ground cutting.The pH of inorganic salts can be at 25 DEG C
The pH meters such as manufactured portable pH meter D-71S are made using hole field to be measured.
Inorganic salts are preferably comprised selected from KNO2、NaNO2、K2CO3、Na2CO3、KHCO3、NaHCO3, in KOH or NaOH at least
A kind of salt can pass through the pH of the content appropriate adjustment inorganic salts of above-mentioned salt.
Inorganic salts contain at least one of sodium nitrate and potassium nitrate.By containing inorganic salts in sodium nitrate and potassium nitrate
At least one, become molten condition, and the general temperature when implementing chemical intensification treatment below the strain point of glass
Region is easy to operate.By making inorganic salts contain sodium nitrate, CTlimit value or less and the big chemically reinforced glass of DOC can be obtained.
It should be explained that, it is known that CTlimit value is empirically being -38.7 × ln (t)+48.2 [MPa].Here, t indicates the plate thickness of glass,
Unit is mm.
The content of sodium nitrate in inorganic salts is preferably 1 mass % or more, more preferably 5 mass % or more.Here, inorganic
The content of sodium nitrate in salt refers to that inorganic salts are the na concn of the liquid phase salt of liquid condition.It should be noted that as in inorganic salts
Sodium nitrate content the upper limit, be not particularly limited.
Content by the sodium nitrate in inorganic salts is 1 mass % or more, becomes molten below the strain point of glass
State, and the general temperature region when implementing chemical intensification treatment is easy to operate.The content of sodium nitrate in inorganic salts be with
The mode appropriate adjustment of desired surface compression stress value (CS, unit MPa) can be obtained and determine.
Inorganic salts can also contain it in the range of will not damage effect of the invention in addition to sodium nitrate or potassium nitrate
Its chemical seed, such as the alkali metal chlorizated salts such as sodium chloride, potassium chloride, Boratex and potassium borate and alkali borate can be enumerated
Deng.They can individually be added, and it is a variety of can also to combine addition.
Contain KNO in above-mentioned inorganic salts2In the case where, the KNO in inorganic salts2Content be preferably 0.2 mass % with
On, more preferably 0.4 mass % or more, further preferably 0.6 mass % or more.Additionally, it is preferred that be 10.0 mass % hereinafter,
More preferably 8.0 mass % are hereinafter, further preferably 6.0 mass % or less.By making KNO2Content be above range, energy
Enough make the pH 7.5~10.5 of inorganic salts when 10 mass % aqueous solution is made.
As the method for contacting glass with inorganic salts, it can be the method for the inorganic salts of coating paste, glass is sprayed
The method of the aqueous solution of inorganic salts, method by glass-impregnated in the salt bath of fuse salt for being heated to fusing point or more etc., they
Among, the method that is preferably impregnated in fuse salt.
As long as glass used in method of the invention contains sodium, it is able to carry out molding as long as having, utilizes chemistry
The composition that intensive treatment is strengthened can use various glass.Specifically, can for example enumerate alumina silicate glass, sodium calcium
Glass, borosilicate glass, lead glass, alkali barium glass and aluminium borosilicate glass etc..
The manufacturing method of glass is not particularly limited, can be by operating manufacture as follows: putting into and it is expected to continuous fusion furnace
Glass raw material after clarification, be supplied to molding machine, so by glass raw material preferably in 1500~1600 DEG C of progress heating meltings
Melten glass is shaped to plate and Slow cooling afterwards.
It should be noted that various methods can be used in the molding of glass.Such as can using glass tube down-drawing (for example, overflow downdraw,
Draw method and again traction method etc. under discharge orifice), float glass process, the various forming methods such as roll-in method and pressing.
The thickness of glass is not particularly limited, in order to which chemical intensification treatment, preferably 3mm is effectively performed hereinafter, more excellent
2mm is selected as hereinafter, further preferably 1mm or less.
In addition, the shape of glass used in method of the invention is not particularly limited.Such as it can be uniform using having
The shape of the writing board shape of plate thickness, at least one side in surface and the back side with curved surface and the three-dimensional shape with bending section etc.
Etc. glass of various shapes.
The concrete example of composition as glass used in method of the invention, such as the group of glass below can be enumerated
At.
(i) in terms of the molar percentage of oxide benchmark, contain 56~72% SiO2, 5~18% Al2O3, 0~
15% B2O3With 0.1~10% P2O5, and Na2O and K2The glass that total content of O is 3~30%.
(ii) in terms of the molar percentage of oxide benchmark, contain 55.5~80% SiO2, 12~20% Al2O3、8
~25% Na2O, 2.5% or more P2O5With the glass of 1% or more alkaline-earth metal RO (RO MgO+CaO+SrO+BaO).
(iii) in terms of the molar percentage of oxide benchmark, contain 57~76.5% SiO2, 12~18% Al2O3、8
~25% Na2O, 2.5~10% P2O5With the glass of 1% or more alkaline-earth metal RO.
(iv) in terms of the molar percentage of oxide benchmark, contain 56~72% SiO2, 8~20% Al2O3, 3~
20% B2O3, 8~25% Na2O, 0~5% K2O, 0~15% MgO, 0~15% CaO, 0~15% SrO2、0
The ZrO of~15% BaO and 0~8%2Glass.
(v) in terms of the molar percentage of oxide benchmark, contain 50~80% SiO2, 2~25% Al2O3, 0~
10% Li2O, 0~18% Na2O, 0~10% K2O, the ZrO of 0~15% MgO, 0~5% CaO and 0~5%2's
Glass.
(vi) in terms of the molar percentage of oxide benchmark, contain 50~74% SiO2, 1~10% Al2O3, 6~
14% Na2O, 3~11% K2O, the ZrO of 2~15% MgO, 0~6% CaO and 0~5%2, and SiO2With Al2O3
Total content be 75% hereinafter, Na2O and K2Total content that total content of O is 12~25%, MgO and CaO is 7~15%
Glass.
(vii) in terms of the molar percentage of oxide benchmark, contain 68~80% SiO2, 4~10% Al2O3, 5~
15% Na2O, 0~1% K2O, the ZrO of 4~15% MgO and 0~1%2Glass.
(viii) in terms of the molar percentage of oxide benchmark, contain 67~75% SiO2, 0~4% Al2O3, 7~
15% Na2O, 1~9% K2O, the ZrO of 6~14% MgO and 0~1.5%2, and SiO2With Al2O3Total content be
71~75%, Na2O and K2Total content of O is 12~20%, glass of its content less than 1% containing CaO.
(ix) in terms of the quality % of oxide benchmark, contain 65~75% SiO2, 0.1~5% Al2O3, 1~6%
The CaO of MgO and 1~15%, and Na2O+K2The glass that O is 10~18%.
(x) in terms of the quality % of oxide benchmark, contain 60~72% SiO2, 1~10% Al2O3, 5~12%
MgO, 0.1~5% CaO, 13~19% Na2The K of O and 0~5%2O, and RO/ (RO+R2It O) is 0.20~0.42 (formula
In, RO indicates alkaline earth oxide, R2O indicate alkali metal oxide) glass.
Chemical intensification treatment by molten salt bath by glass-impregnated in the fuse salt of inorganic salts, by the gold in glass
Belong to the big metal ion (K ion) of ionic radius that ion (Na ion) is replaced into fuse salt and carries out.It is handed over by the ion
It changes, the composition of glass surface can be changed, form the compressive stress layers 20 [Fig. 1 (a)~(b)] of glass surface densification.It is logical
It crosses the densification of the glass surface and generates compression stress, it therefore, can will be glass reinforced.
In chemical strengthening process in method of the invention, when carrying out chemical strengthening, by using 10 mass % are made
Hydrogen ion exponent (pH) when aqueous solution be 7.5~10.5 and the inorganic salts containing at least one of sodium nitrate and potassium nitrate into
Row chemical intensification treatment, to utilize the OH in inorganic salts-The Si-O-Si key of glass is moderately cut off, compression stress is formed
The surface layer of layer is modified and the low-density layer 10 [Fig. 1 (b)~(c)] of low-density.
It should be noted that in fact, the density of chemically reinforced glass is from the middle layer 30 (ontology) for being present in center of glass
Outer rim is to the slowly densification of compression stress layer surface, therefore, does not have density between middle layer 30 and compressive stress layers 20
Specific boundary jumpy.Here, middle layer refers to the layer for being present in center of glass portion and being clamped by compressive stress layers.It should
Middle layer is different from compressive stress layers, is the layer without ion exchange.
Chemical strengthening process can specifically carry out as follows.In chemical strengthening process, by preheating glass, by fuse salt tune
The whole treatment temperature to chemical strengthening.Then, after warmed-up glass being impregnated the stipulated time in fuse salt, from fuse salt
Lift glass, lets cool.It should be noted that it is preferred that before chemical intensification treatment depending on the application to glass carry out shape processing, such as
The machinings such as cutting, end face processing and aperture processing.
The preheating temperature of glass depends on the temperature impregnated in fuse salt, it is generally preferable to be 100 DEG C or more.
From the viewpoint of the chemically reinforced glass for the DOC for obtaining having deeper, the temperature for carrying out chemical strengthening is preferably
400 DEG C or more, more preferably 450 DEG C or more, further preferably 470 DEG C or more.The upper limit for carrying out the temperature of chemical strengthening does not have
There is special limitation to be preferably reinforced the strain point (usual 500~600 DEG C) of glass below for typical.
Dip time of the glass in fuse salt depends on chemical strengthening temperature, but from the change for the DOC for obtaining having deeper
From the viewpoint of learning strengthened glass, preferably 2 hours or more, more preferably 4 hours or more, further preferably 8 hours or more.
The upper limit is not particularly limited, and usually 48 hours hereinafter, if it is 24 hours hereinafter, then more excellent from the viewpoint of productivity
Choosing.
From the viewpoint of assigning sufficient intensity to glass, the pressure on the surface layer for being formed in glass after chemical strengthening process
The depth (DOC) of stress under compression layer is preferably 35 μm or more, more preferably 45 μm or more, further preferably 55 μm or more.
The compression stress value of the chemically reinforced glass manufactured by means of the present invention is preferably 100MPa or more, more preferably
For 200MPa or more, further preferably 300MPa or more.In addition, the upper limit is not particularly limited, it is typical for for 1200MPa with
Under.
EPMA (electron probe micro analyzer) or surface stress meter can be used in the depth of compressive stress layers
(for example, FSM-6000 manufactured by the former production of folding) etc. is measured.
Low-density layer is removed by aftermentioned acid treatment process, therefore, the more thicker easier removing glass table of low-density layer
Face.Therefore, from the viewpoint of glass surface removal amount, the thickness of low-density layer is preferably 10nm or more, more preferably 20nm
More than.The thickness of low-density layer can be controlled by na concn, temperature or the time etc. in the fuse salt of chemical strengthening process.
After removing low-density layer by acid treatment process, alkali process is carried out, thereby, it is possible to further remove low-density layer.
From the viewpoint of glass surface removability, the density of low-density layer is preferably shorter than answered than the compression through ion exchange
The density in the region (ontology) of power layer depth.
The period that the thickness of low-density layer is measured by passing through X ray reflection rate method (X-ray-Reflectometry, XRR)
(Δ θ) is found out.The density of low-density layer is found out by the critical angle (θ c) measured by XRR.It should be noted that simply by utilizing
Scanning electron microscope (SEM) observes the section of glass, is also able to confirm that the formation of low-density layer and the thickness of layer.
It can also be 7.5 with the hydrogen ion exponent (pH) when 10 mass % aqueous solution is made is utilized in chemical strengthening process
~10.5 and the above-mentioned chemical intensification treatment combination that carries out of inorganic salts containing at least one of sodium nitrate and potassium nitrate, it will be upper
The chemical intensification treatment stated and the composition for changing inorganic salts, hydrogen ion exponent, the temperature of chemical strengthening and chemical strengthening when
Between condition in the chemical intensification treatment process of at least one condition carried out before and after above-mentioned chemical intensification treatment process
Repeatedly.
After chemical strengthening process, the cleaning of glass is carried out using industrial water, ion exchange water etc..Wherein, preferably from
Sub- exchanged water.The condition of cleaning is also different according to the cleaning solution used, using ion exchange water, if 0
~100 DEG C are cleaned, then from the aspect of the salt for fully removing attachment removal preferably.
(acid treatment process)
In acid treatment process, the glass further progress acid cleaned after chemical strengthening process is handled.Glass
The acid processing of glass is by making to carry out and contact in glass and the acid solution of hydrogen ion exponent (pH) less than 7.0.
Solution used in acid processing is not particularly limited as long as acidity, used as long as pH is less than 7.0
Acid can be weak acid, or strong acid.Specifically, it is preferable that hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid or lemon
The acid such as lemon acid.These acid may be used alone, can also be used in combination a variety of.
The temperature of sour processing is carried out also according to the type of the acid used, concentration, time and difference, preferably 100 DEG C or less.Separately
Outside, from the viewpoint of easy removing low-density layer, preferably 20 DEG C or more.Although carrying out time of sour processing also according to using
Type, concentration, temperature and the difference of acid, but from the aspect of productivity, preferably 10 seconds~5 hours, more preferable 1 minute~2
Hour.
It is preferred to hold although carrying out the concentration of the solution of sour processing according to the type of the acid used, time, temperature and difference
The small concentration of the misgivings of device corrosion, specifically, it is preferable that 0.1 mass of mass %~20 %.
As the condition of acid processing, specifically, can for example enumerate the glass after making chemical strengthening process with preferably 35~
75 DEG C of the 0.1 mass % aqueous solution of nitric acid of mass %~10 contacts 1~15 minute condition.
By above-mentioned acid processing, accelerates the low-densityization of glass surface, expose part or all of quilt of low-density layer
The surface layer [Fig. 1 (c) and (d)] of removing.The chemically reinforced glass that surface intensity significantly improves can be obtained as a result,.In turn, pass through removing
Low-density layer is present in the damage of glass surface also while being removed, it is believed that also contributes to improving intensity in this aspect.
(alkali process process)
In the method for the invention, then alkali process can be carried out after handling by acid.By carrying out alkali process, handled with only acid
The case where compare, the removal amount of low-density layer can be increased and further increase surface intensity.
Solution used in alkali process is not particularly limited as long as alkalinity, as long as pH is more than 7.0, can be used
Highly basic also can be used in weak base.Specifically, it is preferable that the alkali such as sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate.These alkali
It may be used alone, can also be used in combination a variety of.
The temperature of alkali process is carried out also according to the type of the alkali used, concentration, time and difference, but preferably 0~100
DEG C, more preferably 10~80 DEG C, particularly preferably 20~60 DEG C.If it is the temperature range, not no misgivings of glass corrosion,
Therefore preferably.
Although carrying out the time of alkali process also according to the type of the alkali used, concentration, temperature and difference, from productivity
From the aspect of, preferably 10 seconds~5 hours, more preferably 1 minute~2 hours.Although carrying out the concentration root of the solution of alkali process
According to the type of the alkali used, time, temperature and difference, but from the viewpoint of glass surface removability, preferably 0.1 mass %
~20 mass %.
As the condition of alkali process, specifically, can for example enumerate the glass after making acid treatment process and preferably 35~75
DEG C the 0.1 mass % sodium hydrate aqueous solution of mass %~10% contact 1~15 minute condition.
Expose the table that low-density layer is further removed with the glass phase ratio after acid treatment process by above-mentioned alkali process
Layer.The chemically reinforced glass that surface intensity further increases can be obtained as a result,.Additionally, there are in glass surface damage also by into
One step removes, it is believed that also contributes to further increasing surface intensity in this aspect.
It should be noted that it is preferred that having between above-mentioned acid treatment process and alkali process process or after alkali process process
Cleaning process same as the cleaning process after chemical strengthening process.
It should be noted that the amount for the low-density layer being removed depends on acid treatment process and acid treatment process and alkali process
The condition of at least one of process.Fig. 1 (d) shows the pattern that low-density layer 10 is removed totally, but can also be by low-density
A part of layer 10 removes and remains a part.From the viewpoint of improving intensity, it is not entirely removed even if low-density layer
Effect can be obtained.
< chemically reinforced glass >
The surface intensity of the chemically reinforced glass manufactured by means of the present invention can by ball and ring test shown in following into
Row evaluation.
(ball and ring test)
It is evaluated by the BOR intensity F (N) measured by ball [Ball on Ring (BOR)] test, the ball and ring test
It is to configure glass plate on the ring being made of stainless steel of diameter 30mm, contact portion with the fillet of radius of curvature 2.5mm,
In the state of making the sphere being made of steel and the contact glass sheet of diameter 10mm, which is carried under the conditions of static load
The center of the ring.
F >=1000 × t is preferably satisfied by chemically reinforced glass produced by the present invention2, more preferable F >=1200 × t2[in formula, F
For the BOR intensity (N) measured by ball and ring test, t is the plate thickness (mm) of glass plate].It is the range by BOR intensity F (N),
Excellent intensity is also shown when carrying out thin plate.
Fig. 2 indicates the schematic diagram for illustrating ball and ring test.In ball [Ball on Ring (BOR)] test, carried in level
In the state of setting glass plate 1, using the press fixture 2 (hardened steel, diameter 10mm, mirror finish) of SUS304 to glass plate 1
It pressurizes, measures the intensity of glass plate 1.
In Fig. 2, in the receiving fixture 3 of SUS304, (diameter 30mm, the curvature R of contact portion are 2.5mm, and contact portion is to quench
Fiery steel, mirror finish) on be horizontally disposed with glass plate 1 as sample.Glass plate 1 top setting for glass plate 1 into
The press fixture 2 of row pressurization.In the form of this implementation, from the top of glass plate 1, the middle section to glass plate 1 adds
Pressure.
It should be noted that experimental condition is as follows.
The decrease speed of press fixture 2: 1.0 (mm/min)
At this point, the breaking load (unit N) when glass plate is destroyed is set as BOR intensity, by 20 surveys of the BOR intensity
Fixed average value is set as surface intensity F (N).Wherein, the feelings of the load point 2mm or more of the sphere are left in the destruction starting point of glass plate
Under condition, excluded from the data for calculating average value.
The depth (DOC) of the compressive stress layers of the chemically reinforced glass manufactured by method of the invention be preferably 35 μm with
On, more preferably 45 μm or more, further preferably 55 μm or more.
The thickness for the low-density layer being removed by acid treatment process, alkali process process is as described above, even if be greater than
10nm or so is also as the embodiment 1000nm or so, and therefore, for the depth (DOC) of compressive stress layers, chemistry is strong
The depth (DOC) formed in chemical industry sequence is roughly the same with depth (DOC) after acid treatment process, alkali process process.
The surface compression stress value (CS) of the chemically reinforced glass manufactured by means of the present invention be preferably 100MPa with
On, more preferably 200MPa or more, further preferably 300MPa or more.In addition, the upper limit is not particularly limited, it is for typical
1200MPa or less.
Compression stress value can be used EPMA (Electron Probe Micro Analyzer) or surface stress meter (for example,
The manufactured FSM-6000 of the former production of folding) etc. be measured.Japanese Unexamined Patent Publication 2016-142600 bulletin can be used in compression stress value
Disclosed in stress distribution calculation method and calculate.
The inner tensile stress (CT) of the chemically reinforced glass manufactured by means of the present invention be preferably 72MPa hereinafter,
More preferably 62MPa is hereinafter, further preferably 52MPa or less.In addition, lower limit is not particularly limited, it is 20MPa for typical
More than.Stress distribution is measured, which is integrated with thickness, finds out CT value.
Additionally, it is known that CTlimit value is empirically being -38.7 × ln (t)+48.2 [MPa].Here, t indicates the plate of glass
Thickness, unit mm.
The chemically reinforced glass manufactured by means of the present invention can also be carried out before chemical strengthening process to glass table
Grinding process that face is ground and manufacture.Here, the grinding in the present invention refers to by using abrasive grains glass-cutting surface
And it is smoothed.
In addition, the presence or absence of the grinding wound that can be generated by grinding process can be by utilizing AFM (Atomic Force
Microscope, atomic force microscope) surface observe to be distinguished, there is no 2 or more in 10 μ m, 5 μm of regions
In the case where 5 μm of length or more, 0.1 μm of width or more of scratch, it may be said that be not grind the state of wound on surface.In Fig. 3 A
State with surface grinding wound is shown, the state without surface grinding wound is shown in Fig. 3 B.
The chemically reinforced glass of manufacturing method manufacture through the invention, passes through the measurement range of the surface AFM Observe and measure
The surface roughness Ra of 10 5 μm of μ ms is preferably 0.2nm or more, more preferably 0.25nm or more.Additionally, it is preferred that for 1.5nm with
Under, more preferably 1.2nm or less.It should be noted that the surface roughness of the previous chemically reinforced glass plate not ground is usually
0.15nm is more than and less than 0.2nm.
Embodiment
Hereinafter, enumerating embodiment and the present invention is specifically described in comparative example, but the present invention is not limited to these realities
Apply example and comparative example.
[production of chemically reinforced glass]
The condition according to shown in following carry out chemical strengthening process after, successively carry out acid treatment process, alkali process process and
Grinding process makes chemically reinforced glass.It should be noted that about each embodiment and comparative example, the presence or absence of each process is shown in table 1
With 2.
(chemical strengthening process)
The material of inorganic salts is added in the cup of SUS in the way of becoming and form shown in table 1 and 2 with pH, utilizes
Mantle heater carries out heating until becoming temperature shown in table 1 and 2, prepares fuse salt.It is 50mm when preparing to overlook
Alumina silicate glass A~C of plate thickness shown in × 50mm and table 1 and 2, after being preheated to 200~400 DEG C, shown in table 1 and 2
Under the conditions of carry out ion-exchange treatment after, be cooled to room temperature near, thus carry out chemical strengthening process.Obtained chemical strengthening glass
Glass is washed, and subsequent processing is supplied to.It should be noted that the composition about inorganic salts, in addition to being formed shown in table 1 and 2, KNO3
Add up to 100 mass %.In addition, the pH of inorganic salts is to make manufactured portable pH meter D-71S using hole field at 25 DEG C
Measure value obtained by pH when 10 mass % aqueous solution is made.
(acid treatment process)
The aqueous solution of nitric acid for preparing 6 mass % in beaker carries out temperature using water-bath and adjusts to 40 DEG C.By above-mentioned chemistry
Glass obtained in reinforcing process impregnates 120 seconds in adjusted aqueous solution of nitric acid and carries out sour processing, then using pure
After water cleaning repeatedly, it is dried by air blast.By the obtained glass for subsequent processing.
(alkali process process)
The sodium hydrate aqueous solution for preparing 4.0 weight % in beaker carries out temperature using water-bath and adjusts to 40 DEG C.It will be sour
Glass obtained in treatment process impregnates 120 seconds in adjusted sodium hydrate aqueous solution and carries out alkali process, then sharp
After being cleaned repeatedly with pure water, it is dried by air blast.
(grinding process)
As grinding slurry, making average particle diameter (d50) is that 1 μm of cerium oxide is dispersed in water and makes slurry, is made
With obtained slurry, will be put down under conditions of pressure 0.1kPa using the non-woven fabrics grinding pad that hardness (Xiao A hardness) is 74
Total about 6 μm of the grinding in the two sides of glass sheet.
< evaluation method >
Various evaluations in the present embodiment are carried out by analysis method as shown below.
(surface removal amount)
The thickness of the removal amount of glass using analysis electronic balance (HR-202i, AND are manufactured) measurement reagent by being handled
Weight before and after (acid processing and alkali process), carries out thickness conversion using following formula and finds out.
(thickness of the removal amount of each single side)=[(weight before handling) ﹣ (weight after processing)]/(specific gravity of glass)/processing
Area/2
At this point, the specific gravity of glass of glass material (glass A, glass B and glass C) is as follows, calculated using these values.
Glass A:2.42 (g/cm3)
Glass B:2.48 (g/cm3)
Glass C:2.39 (g/cm3)
(surface intensity)
Glass surface intensity is measured by ball and ring test.Fig. 2 shows for illustrating ball and ring test used in the present invention
Schematic diagram.Glass plate 1 (in the state of mounting below in an example for alumina silicate glass A) is horizontal, is used SUS304
The press fixture 2 (hardened steel, diameter 10mm, mirror finish) of system pressurizes to glass plate 1, measures the intensity of glass plate 1.
In Fig. 2, in the receiving fixture 3 of SUS304, (diameter 30mm, the curvature R of contact portion are 2.5mm, and contact portion is to quench
Fiery steel, mirror finish) on be horizontally disposed with glass plate 1 as sample.Glass plate 1 top setting for glass plate 1 into
The press fixture 2 of row pressurization.
From the top of the glass plate 1 obtained by embodiment and comparative example, the middle section to glass plate 1 pressurizes.It should
Illustrate, experimental condition is as follows.
The decrease speed of press fixture 2: 1.0 (mm/min)
At this point, the breaking load (unit N) when glass is destroyed is set as BOR intensity, by 20 measurements of the BOR intensity
Average value be set as surface intensity F (N).Wherein, the load point 2mm of the sphere (press fixture) is left in the destruction starting point of glass plate
In the case where above, excluded from the data for calculating average value.
Surface intensity F (N) depends on the plate thickness t (mm) of glass plate, therefore, here, the plate thickness t (mm) by utilizing glass plate
It is standardized (benchmark) and is compared.It will be standardized obtained by (benchmark) using the plate thickness t (mm) of glass plate
Value is set as a (unit N/mm2).A value is by formula: a=F/t2It calculates.
(depth of surface compression stress, compressive stress layers)
The depth (DOC, unit are μm) of surface compression stress value (CS) and compressive stress layers uses Zhe Yuan manufacturing company
The surface stress meter (FSM-6000) of manufacture and measure.The depth (DOC) of compression stress value (CS) and compressive stress layers uses day
Stress distribution calculation method disclosed in this special open 2016-142600 bulletin and calculate.
(tensile stress)
Tensile stress values (CT, units MPa) use stress distribution meter disclosed in Japanese Unexamined Patent Publication 2016-142600 bulletin
Calculation method measures stress distribution, which is integrated with thickness and is calculated.
(grinding wound)
The presence or absence of grinding wound is distinguished by the surface observation using AFM.2 are not present in 10 μ m, 5 μm of regions
In the case where 5 μm of length or more, 0.1 μm of width or more above of the scratch, as the state for not grinding wound on surface.
(exterior quality)
Appearance is observed under higher source luminance and under conditions of becoming illumination 100000Lux, passes through following evaluation criteria
Exterior quality is evaluated.Fig. 4 A is the figure for indicating not generate the state of white haze in glass surface, and Fig. 4 B is indicated in glass
The figure of the state of white haze is generated in face.
Zero: not generating white haze in glass surface.
×: white haze is generated in glass surface.
The obtained results are shown in table 1 and 2 and Fig. 5~8.
[table 1]
[table 2]
As shown in table 1, the chemically reinforced glass for the embodiment 1~12 that manufacturing method through the invention obtains has been obtained,
The manufacturing method of the present invention comprises the following steps: making glass and pH 7.5~10.5 and containing in sodium nitrate and potassium nitrate
The inorganic salts of at least one contact and carry out the chemical strengthening process of ion exchange；And after making above-mentioned chemical strengthening process
Acid solution of the glass with pH less than 7 contacts and carries out the acid treatment process of sour processing.With chemistry obtained in comparative example 1~11
Strengthened glass is compared, even if the chemically reinforced glass of embodiment 1~12 carries out prolonged chemical intensification treatment, face at high temperature
Intensity is also high, and the depth (DOC) of compressive stress layers is also deep and shows higher surface compression stress value (CS), and in glass
White haze is not generated in face, it is also excellent in terms of exterior quality.
Compared with the chemically reinforced glass obtained in the embodiment, makes glass and pH 7.5~10.5 and containing sodium nitrate
Sour processing is not carried out after carrying out the chemical strengthening process of ion exchange with the contact of the inorganic salts of at least one of potassium nitrate
The surface intensity of the chemically reinforced glass of Comparative Examples 1 and 2,4,6,7,10 and 11 is low.In addition, the chemistry of Comparative Examples 1 and 2,4,8 and 9 is strong
Change glass and generates white haze in glass surface.
In addition, compared with other comparative examples, make glass and pH 7.5~10.5 and containing in sodium nitrate and potassium nitrate
The inorganic salts contact of at least one and do not carry out sour processing and be ground after carrying out the chemical strengthening process of ion exchange
Comparative example 5 chemically reinforced glass surface intensity it is slightly higher.But grinding wound is observed in glass surface, it is obtained with embodiment
To chemically reinforced glass compare, surface intensity is low.
In addition, carrying out chemistry in the inorganic salts using pH less than 7.5 compared with the chemically reinforced glass obtained in the embodiment
The chemically reinforced glass of the comparative example 3 of acid processing and alkali process is carried out after reinforcing process, is being more than 10.5 inorganic salts using pH
The comparative example 8 of sour processing is carried out after carrying out chemical strengthening process and be more than 10.5 inorganic salts progress chemical strengthening using pH
It is low with the surface intensity of chemically reinforced glass of comparative example 9 of alkali process that acid processing is carried out after process, is had in glass surface white
Mist.
Fig. 5 A indicates the stress distribution of chemically reinforced glass obtained in embodiment 1 and 3 and comparative example 1, and Fig. 5 B is indicated
The stress distribution of chemically reinforced glass obtained in embodiment 7 and 8 and comparative example 6, Fig. 5 C indicate embodiment 10 and 11 and
The stress distribution of chemically reinforced glass obtained in comparative example 11.
As shown in Figure 5A, the stress distribution of chemically reinforced glass obtained in embodiment 1 and comparative example 1 is unanimous on the whole.Separately
Outside, as shown in Figure 5 B, the stress distribution of chemically reinforced glass obtained in embodiment 7 and 8 and comparative example 6 is unanimous on the whole.Into
And as shown in Figure 5 C, the stress distribution of chemically reinforced glass obtained in embodiment 10 and 11 and comparative example 11 is unanimous on the whole.
Fig. 6 A and Fig. 6 B indicate strong to the face of chemically reinforced glass obtained in embodiment 1 and 5 and comparative example 1,4 and 5
Result obtained by degree is evaluated.As shown in Figure 6 A and 6 B, with the comparative example 1 that does not carry out sour processing after chemical strengthening process
With 4 and the comparative example 5 that does not carry out sour processing after chemical strengthening process and be ground is compared, in embodiment 1 and 5
To the surface intensity of chemically reinforced glass significantly improve.
Fig. 7 A and Fig. 7 B indicate to carry out the surface intensity of chemically reinforced glass obtained in embodiment 7 and 8 and comparative example 6
Result obtained by evaluation.As shown in figures 7 a and 7b, compared with the comparative example 6 for not carrying out sour processing after chemical strengthening process,
The surface intensity of chemically reinforced glass obtained in embodiment 7 and 8 significantly improves.
Fig. 8 A and Fig. 8 B indicate the surface intensity to chemically reinforced glass obtained in embodiment 10 and 11 and comparative example 11
Result obtained by being evaluated.As shown in Figure 8 A and 8 B, with the comparative example 11 that does not carry out sour processing after chemical strengthening process
It compares, the surface intensity of chemically reinforced glass obtained in embodiment 10 and 11 significantly improves.
According to these as a result, by being 7.5~10.5 and containing at least one of sodium nitrate and potassium nitrate using pH
Inorganic salts chemical strengthening process after carry out sour processing, even if available carry out prolonged chemical intensification treatment at high temperature
It will not weaken the intensity of glass, show deeper DOC and the high chemically reinforced glass of surface intensity.
It is described the invention in detail referring to specific scheme, but in the feelings for not departing from the spirit and scope of the present invention
It is clear for making various changes and modifications under condition to those skilled in the art.It should be noted that the application is based on 2016 9
The Japanese patent application (Japanese Patent Application 2016-193972) that the moon is filed an application on the 30th, quotes its entirety by reference.Separately
Outside, be incorporated in this all refer to be incorporated in this specification as a whole.
Symbol description
10 low-density layers
20 compressive stress layers
30 middle layers
1 glass plate
2 press fixtures
3 bear fixture
Claims (5)
1. a kind of manufacturing method of chemically reinforced glass, comprises the following steps:
Chemical strengthening process makes glass and hydrogen ion exponent when 10 mass % aqueous solution is made i.e. pH 7.5~10.5 and contains
There are the inorganic salts of at least one of sodium nitrate and potassium nitrate to contact and carry out ion exchange；With
Acid treatment process, acid solution of the glass with hydrogen ion exponent i.e. pH less than 7.0 after making the chemical strengthening process connect
It touches and carries out sour processing.
2. the manufacturing method of chemically reinforced glass according to claim 1, wherein further comprise following process: at alkali
Science and engineering sequence, the glass after making the acid treatment process contact with the hydrogen ion exponent i.e. pH alkaline solution for being more than 7.0 and carry out alkali
Processing.
3. the manufacturing method of chemically reinforced glass according to claim 1 or 2, wherein the chemical strengthening process is to make
The glass contacts 2 hours or more with 400 DEG C or more of the inorganic salts and the process that carries out ion exchange.
4. the manufacturing method of chemically reinforced glass described in any one of claim 1 to 3, wherein the chemical strengthening
Glass after process has 35 μm of depth or more of compressive stress layers.
5. the manufacturing method of chemically reinforced glass according to any one of claims 1 to 4, wherein the chemical strengthening
The surface intensity F that glass after process is measured under the following conditions by ball and ring test is F >=1000 relative to the plate thickness t of glass plate
×t2, the unit of the surface intensity F is N, and the unit of the plate thickness t is mm,
Ball and ring test condition:
By glass plate configuration being made of stainless steel in the fillet of diameter 30mm, contact portion with radius of curvature 2.5mm of plate thickness t
Ring on, making the sphere of diameter 10mm being made of steel and in the state of the contact glass sheet, make the sphere with decrease speed
1mm/min declines and applies at the center of the ring and load, and breaking load when glass plate is destroyed is set as BOR intensity, by this
20 measurement average value of BOR intensity is set as surface intensity F, wherein excludes from the data for calculating average value in glass
The destruction starting point of plate leaves resulting data when the load point 2mm or more of the sphere, here, the unit of the plate thickness t is mm, institute
The unit for stating breaking load is N, and the unit of the surface intensity F is N.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016193972 | 2016-09-30 | ||
| JP2016-193972 | 2016-09-30 | ||
| PCT/JP2017/034671 WO2018062141A1 (en) | 2016-09-30 | 2017-09-26 | Method for producing chemically toughened glass |
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| CN109803938A true CN109803938A (en) | 2019-05-24 |
| CN109803938B CN109803938B (en) | 2022-07-12 |
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| JP (1) | JP6919658B2 (en) |
| KR (1) | KR102436191B1 (en) |
| CN (1) | CN109803938B (en) |
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| CN111807718A (en) * | 2020-07-24 | 2020-10-23 | 江苏铁锚玻璃股份有限公司 | Preparation method of high-light-transmission and high-strength antibacterial glass |
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| JP7395939B2 (en) * | 2019-10-09 | 2023-12-12 | Ａｇｃ株式会社 | Manufacturing method of chemically strengthened glass |
| CN111122376A (en) * | 2020-01-06 | 2020-05-08 | 江苏奥天光学有限公司 | Tempering effect verification method of tempering mold |
| CN112062480A (en) * | 2020-09-11 | 2020-12-11 | 河南卓金光电科技股份有限公司 | Surface strengthening treatment method for ultrathin large-plate-surface glass |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04139034A (en) * | 1990-09-29 | 1992-05-13 | Nippon Sheet Glass Co Ltd | Formation of unevenness on surface of glass |
| CN1656037A (en) * | 2002-06-13 | 2005-08-17 | 国际商业机器公司 | PH adjustment of a melt for use in microetching glass substrates |
| CN104736495A (en) * | 2013-07-19 | 2015-06-24 | 旭硝子株式会社 | Method for manufacturing chemically reinforced glass |
| WO2015179345A1 (en) * | 2014-05-20 | 2015-11-26 | Corning Incorporated | Scratch resistant glass and method of making |
| CN105555731A (en) * | 2014-01-16 | 2016-05-04 | 旭硝子株式会社 | Chemically strengthened glass, and method for producing same |
| WO2016117479A1 (en) * | 2015-01-20 | 2016-07-28 | 旭硝子株式会社 | Glass substrate production method |
| WO2016117478A1 (en) * | 2015-01-20 | 2016-07-28 | 旭硝子株式会社 | Float glass |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5913455B2 (en) * | 1978-03-08 | 1984-03-29 | 石塚硝子株式会社 | How to manufacture frosted tempered glass products |
| US4687581A (en) * | 1984-01-30 | 1987-08-18 | Pedro B. Macedo | Method of separating and purifying cations by ion exchange with regenerable porous glass |
| US5232481A (en) * | 1991-12-26 | 1993-08-03 | Corning Incorporated | Glass dimensional control using ion exchange |
| US6638623B2 (en) * | 2001-12-18 | 2003-10-28 | International Business Machines Corporation | pH adjustment of a strengthening melt for use in strengthening glass substrates |
| US10202300B2 (en) * | 2013-08-23 | 2019-02-12 | Corning Incorporated | Strengthened glass articles, edge-strengthened laminated glass articles, and methods for making the same |
| TWI503184B (en) * | 2013-09-04 | 2015-10-11 | All Ring Tech Co Ltd | Dispenser and its material inspection of dust removal method |
| KR102235722B1 (en) * | 2013-10-14 | 2021-04-05 | 코닝 인코포레이티드 | Ion Exchange Processes and Chemically Strengthened Glass Substrates Resulting Therefrom |
| CN108463443B (en) * | 2016-04-12 | 2021-07-13 | 日本电气硝子株式会社 | Method for producing tempered glass and device for producing tempered glass |
-
2017
- 2017-09-26 WO PCT/JP2017/034671 patent/WO2018062141A1/en active Application Filing
- 2017-09-26 JP JP2018542579A patent/JP6919658B2/en active Active
- 2017-09-26 CN CN201780060568.4A patent/CN109803938B/en active Active
- 2017-09-26 KR KR1020197008010A patent/KR102436191B1/en active IP Right Grant
- 2017-09-28 TW TW106133281A patent/TWI728189B/en active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04139034A (en) * | 1990-09-29 | 1992-05-13 | Nippon Sheet Glass Co Ltd | Formation of unevenness on surface of glass |
| CN1656037A (en) * | 2002-06-13 | 2005-08-17 | 国际商业机器公司 | PH adjustment of a melt for use in microetching glass substrates |
| CN104736495A (en) * | 2013-07-19 | 2015-06-24 | 旭硝子株式会社 | Method for manufacturing chemically reinforced glass |
| CN104812718A (en) * | 2013-07-19 | 2015-07-29 | 旭硝子株式会社 | Chemically strengthened glass |
| CN105669050A (en) * | 2013-07-19 | 2016-06-15 | 旭硝子株式会社 | Chemically strengthened glass |
| CN105555731A (en) * | 2014-01-16 | 2016-05-04 | 旭硝子株式会社 | Chemically strengthened glass, and method for producing same |
| WO2015179345A1 (en) * | 2014-05-20 | 2015-11-26 | Corning Incorporated | Scratch resistant glass and method of making |
| WO2016117479A1 (en) * | 2015-01-20 | 2016-07-28 | 旭硝子株式会社 | Glass substrate production method |
| WO2016117478A1 (en) * | 2015-01-20 | 2016-07-28 | 旭硝子株式会社 | Float glass |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807718A (en) * | 2020-07-24 | 2020-10-23 | 江苏铁锚玻璃股份有限公司 | Preparation method of high-light-transmission and high-strength antibacterial glass |
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| CN109803938B (en) | 2022-07-12 |
| KR20190065255A (en) | 2019-06-11 |
| KR102436191B1 (en) | 2022-08-26 |
| TWI728189B (en) | 2021-05-21 |
| TW201817689A (en) | 2018-05-16 |
| JPWO2018062141A1 (en) | 2019-07-11 |
| JP6919658B2 (en) | 2021-08-18 |
| WO2018062141A1 (en) | 2018-04-05 |
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