CN108473368A - The manufacturing method of chemically reinforced glass - Google Patents
The manufacturing method of chemically reinforced glass Download PDFInfo
- Publication number
- CN108473368A CN108473368A CN201680076423.9A CN201680076423A CN108473368A CN 108473368 A CN108473368 A CN 108473368A CN 201680076423 A CN201680076423 A CN 201680076423A CN 108473368 A CN108473368 A CN 108473368A
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- China
- Prior art keywords
- glass
- manufacturing
- chemically reinforced
- reinforced glass
- ion exchange
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Classifications
-
- 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
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
Abstract
The present invention provides a kind of manufacturing method of the chemically reinforced glass of crackle compared with the past that can fully remove glass surface or potential cut.The present invention relates to a kind of manufacturing methods of chemically reinforced glass, which is characterized in that the manufacturing method of the chemically reinforced glass includes：Prepare the process of the glass plate containing alkali metal ion；Prepare the process of the inorganic salts containing the big other alkali metal ions of ionic radius than the alkali metal ion；Process in dew-point temperature in 20 DEG C or more of atmosphere, to carry out the ion exchange of the alkali metal ion of the glass plate and other alkali metal ions of the inorganic salts；And the process of the part on the surface of the glass plate after the removal ion exchange.
Description
Technical field
The present invention relates to a kind of manufacturing methods of chemically reinforced glass.
Background technology
In recent years, it using chemically reinforced glass as the protective glass of various display devices, and requires to further increase
Its intensity.In order to improve the intensity of chemically reinforced glass, disclose by make the glass containing sodium with containing the specific of potassium nitrate
Inorganic salts contact, and Na in the glass and K in the inorganic salts is made to carry out ion exchange, thus carried out at chemical strengthening
Reason, then carries out the processing (patent document 1) carried out using bronsted lowry acids and bases bronsted lowry.
It is recorded in patent document 1：Even if the glass surface after chemical intensification treatment is not ground or has been used hydrogen
The surface intensity of the etching process of fluoric acid etc., glass improves also tremendously.
Existing technical literature
Patent document
Patent document 1：International Publication No. 2015/008763
Invention content
Problem to be solved by the invention
However, in recent years, it is sometimes desirable to removal amounts more more than surface removal amount recorded in patent document 1.
In view of above-mentioned actual conditions, compared with the past surface removal amount can be improved the purpose of the present invention is to provide a kind of
Chemically reinforced glass manufacturing method.
The means used to solve the problem
Further investigation is repeated in the inventors of the present invention, as a result, it has been found that, by controlling steam vapour amount when chemical intensification treatment,
The surface removal amount of glass can be dramatically improved, so as to complete the present invention.
That is, the present invention relates to following 1 ＞ of ＜~＜, 19 ＞.
A kind of manufacturing methods of chemically reinforced glass of 1 ＞ of ＜, which is characterized in that the manufacturing method of the chemically reinforced glass
Including：
Prepare the process of the glass plate containing alkali metal ion；
Prepare the process of the inorganic salts containing the big other alkali metal ions of ionic radius than the alkali metal ion；
In dew-point temperature is 20 DEG C or more of atmosphere, carry out the alkali metal ion of the glass plate with it is described inorganic
The process of the ion exchange of other alkali metal ions of salt；And
The process for removing the part on the surface of the glass plate after the ion exchange.
The manufacturing method of chemically reinforced glass of 2 ＞ of ＜ as described in 1 ＞ of above-mentioned ＜, which is characterized in that the carry out ion
The process of exchange carries out in the atmosphere that the dew-point temperature is 30 DEG C or more.
The manufacturing method of chemically reinforced glass of 3 ＞ of ＜ as described in 2 ＞ of above-mentioned ＜ 1 ＞ or ＜, which is characterized in that it is described into
The process of row ion exchange carries out in the atmosphere that the dew-point temperature is 40 DEG C or more.
The manufacturing method of chemically reinforced glass of 4 ＞ of ＜ as described in any one of above-mentioned 1 ＞ of ＜~＜, 3 ＞, feature exist
In the process for carrying out ion exchange carries out in the atmosphere that the dew-point temperature is 50 DEG C or more.
The manufacturing method of chemically reinforced glass of 5 ＞ of ＜ as described in any one of above-mentioned 1 ＞ of ＜~＜, 4 ＞, feature exist
In the process for carrying out ion exchange carries out in the temperature atmosphere below that the dew-point temperature is the inorganic salts.
The manufacturing method of chemically reinforced glass of 6 ＞ of ＜ as described in any one of above-mentioned 1 ＞ of ＜~＜, 5 ＞, feature exist
In the atmosphere in the process for carrying out ion exchange is directed into institute by that will wrap steam-laden gas from vapor supply unit
It states the upper space of inorganic salts and is formed, and for the import volume of the steam-laden gas of packet, per 1cm3In
Vapor supply amount is 0.01mg/ minutes or more.
The manufacturing method of chemically reinforced glass of 7 ＞ of ＜ as described in any one of above-mentioned 1 ＞ of ＜~＜, 5 ＞, feature exist
It is directed into, atmosphere in the process for carrying out ion exchange by the way that steam-laden gas will be wrapped from bubbling portion described inorganic
It is formed in salt, and for the import volume of the steam-laden gas of packet, per 1cm3In vapor supply amount be
0.01mg/ minutes or more.
The manufacturing method of chemically reinforced glass of 8 ＞ of ＜ as described in any one of above-mentioned 1 ＞ of ＜~＜, 7 ＞, feature exist
In in the process for preparing inorganic salts, preparation is containing selected from by K2CO3、Na2CO3、KHCO3、NaHCO3、Li2CO3、
Rb2CO3、Cs2CO3、MgCO3、CaCO3And BaCO3The inorganic salts of at least one of group of composition salt and potassium nitrate.
The manufacturing method of chemically reinforced glass of 9 ＞ of ＜ as described in any one of above-mentioned 1 ＞ of ＜~＜, 8 ＞, feature exist
In the process of the part on the surface of the removal glass plate includes that the glass plate after the ion exchange is made to be contacted with acid
Process.
The manufacturing method of chemically reinforced glass of 10 ＞ of ＜ as described in 9 ＞ of above-mentioned ＜, which is characterized in that the removal glass
The process of the part on the surface of plate it is described with after the process of sour contact also include so that the glass plate is contacted with alkali work
Sequence.
The manufacturing method of chemically reinforced glass of 11 ＞ of ＜ as described in 10 ＞ of above-mentioned ＜, which is characterized in that it is described with it is sour
Also include the process for cleaning the glass plate between the process of contact and the process contacted with alkali.
The manufacturing method of chemically reinforced glass of 12 ＞ of ＜ as described in any one of above-mentioned 1 ＞ of ＜~＜, 11 ＞, feature
It is, between the process of the part on the process for carrying out ion exchange and the surface of the removal glass plate, also includes
The process for cleaning the glass plate.
The manufacturing method of chemically reinforced glass of 13 ＞ of ＜ as described in any one of above-mentioned 10 ＞ of ＜~＜, 12 ＞, feature
It is, also includes the process for cleaning the glass plate after the process contacted with alkali.
The manufacturing method of chemically reinforced glass of 14 ＞ of ＜ as described in any one of above-mentioned 9 ＞ of ＜~＜, 13 ＞, feature
It is, in the process with sour contact, 7 solution is less than using pH.
The manufacturing method of chemically reinforced glass of 15 ＞ of ＜ as described in 14 ＞ of above-mentioned ＜, which is characterized in that the pH is less than 7
Solution be weak acid.
The manufacturing method of chemically reinforced glass of 16 ＞ of ＜ as described in 14 ＞ of above-mentioned ＜, which is characterized in that the pH is less than 7
Solution be strong acid.
The manufacturing method of chemically reinforced glass of 17 ＞ of ＜ as described in any one of above-mentioned 10 ＞ of ＜~＜, 16 ＞, feature
It is, in the process contacted with alkali, 7 solution is more than using pH.
The manufacturing method of chemically reinforced glass of 18 ＞ of ＜ as described in 17 ＞ of above-mentioned ＜, which is characterized in that the pH is more than 7
Solution be weak base.
The manufacturing method of chemically reinforced glass of 19 ＞ of ＜ as described in 17 ＞ of above-mentioned ＜, which is characterized in that the pH is more than 7
Solution be highly basic.
According to the present invention it is possible to provide a kind of system of the chemically reinforced glass compared with the past that can improve surface removal amount
Make method.
Description of the drawings
Fig. 1 is the skeleton diagram of the method for illustrating ball and ring test.
Fig. 2 is the schematic diagram for the manufacturing process for indicating the chemically reinforced glass of the present invention.
Fig. 3 is the schematic diagram of the experimental system for the atmosphere being used to form in the process for carrying out ion exchange.
Specific implementation mode
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
It is arbitrarily deformed and is implemented in the range of purport from the present invention.In addition, in the present specification, indicating numberical range
"~" is used using the meaning comprising its front and back recorded numerical value as lower limiting value and upper limit value.
The manufacturing method ＞ of ＜ chemically reinforced glass
The manufacturing method of chemically reinforced glass of the present invention is characterized in that, it includes：
(a) prepare the process of the glass plate containing alkali metal ion；
(b) prepare the work of the inorganic salts containing the big other alkali metal ions of ionic radius than the alkali metal ion
Sequence；
(c) in dew-point temperature is 20 DEG C or more of atmosphere, carry out the alkali metal ion of the glass plate with it is described
The process of the ion exchange of other alkali metal ions of inorganic salts；And
(d) process for removing the part on the surface of the glass plate after the ion exchange.
(glass composition)
The glass used in the present invention contains alkali metal ion, as long as with can shape and pass through chemical strengthening
The glass of the composition of processing and reinforcing can then use the glass of various compositions.Wherein, sodium is preferably comprised, specifically, for example
It can enumerate：Alumina silicate glass, soda-lime glass, borosilicate glass, lead glass, alkali barium glass, aluminium borosilicate glass etc..
The manufacturing method of glass is not particularly limited, and can be manufactured in the following way：By desired glass original
In material input to continuous fusion stove, molten raw preferably is heated at 1500 DEG C~1600 DEG C, is clarified, is then supplied
To building mortion, then moltens glass into plate and carry out slow cooling.
It should be noted that various methods may be used in the forming of glass.For example, glass tube down-drawing may be used (for example, overflow
Draw method and again traction method etc. under glass tube down-drawing, discharge orifice), float glass process, the various manufacturing process such as roll-in method and pressing.Wherein, from easy
It is cracked at least part of glass surface, from the aspect of effect of the invention is significantly visible, preferably float glass process.
The thickness of glass is not particularly limited, in order to which chemical intensification treatment is effectively performed, it is often preferred that 5mm hereinafter,
More preferably 3mm hereinafter, further preferably 1mm hereinafter, particularly preferably 0.7mm or less.
In addition, the shape of the glass used in the present invention is not particularly limited.For example, may be used with uniform plate thickness
Writing board shape, in front and at least one of the back side shape with curved surface and the three-dimensional shape etc. with bending section etc.
Variously-shaped glass.
The composition of the chemically reinforced glass of the present invention is not particularly limited, such as can enumerate glass composition below：
(1) containing 50%~80% SiO in being formed what is indicated with mole % of oxide benchmark2, 2%~25%
Al2O3, 0~10% Li2O, 0~18% Na2O, 0~10% K2O, 0~15% MgO, 0~5% CaO and 0~5%
ZrO2Glass；
(2) it is formed containing 50%~74% SiO with what mole % of oxide benchmark was indicated2, 1%~10%
Al2O3, 6%~14% Na2O, 3%~11% K2O, the ZrO of 2%~15% MgO, 0~6% CaO and 0~5%2,
SiO2And Al2O3Content add up to 75% hereinafter, Na2O and K2The content of O adds up to 12%~25%, and MgO and CaO
Content the glass for adding up to 7~15%；
(3) it is formed containing 68%~80% SiO with what mole % of oxide benchmark was indicated2, 4%~10%
Al2O3, 5%~15% Na2O, 0~1% K2O, the ZrO of 4%~15% MgO and 0~1%2Glass；
(4) it is formed containing 67%~75% SiO with what mole % of oxide benchmark was indicated2, 0~4% Al2O3、
7%~15% Na2O, 1%~9% K2O, the ZrO of 6%~14% MgO and 0~1.5%2, SiO2And Al2O3Content
Add up to 71%~75%, Na2O and K2The content of O adds up to 12%~20%, and its content containing CaO
Glass less than 1%；
(5) it is formed containing 65%~75% SiO with what the quality % of oxide benchmark was indicated2, 0.1%~5%
Al2O3, 1%~6% MgO, 1%~15% CaO, and Na2O+K2The glass that O is 10%~18%；
(6) it is formed containing 60%~72% SiO with what the quality % of oxide benchmark was indicated2, 1%~10%
Al2O3, 5%~12% MgO, 0.1%~5% CaO, 13%~19% Na2O, 0~5% K2O, and RO/ (RO+R2O)
For 0.20 or more and 0.42 or less, (in formula, RO indicates alkaline earth oxide, R2O indicate alkali metal oxide) glass；
(7) it is formed containing 55.5%~80% SiO with what mole % of oxide benchmark was indicated2, 12%~20%
Al2O3, 8%~25% Na2O, 2.5% or more P2O5, 1% or more alkaline-earth metal RO (RO MgO+CaO+SrO+BaO)
Glass；
(8) it is formed containing 57%~76.5% SiO with what mole % of oxide benchmark was indicated2, 12%~18%
Al2O3, 8%~25% Na2O, 2.5%~10% P2O5, 1% or more alkaline-earth metal RO glass；
(9) it is formed containing 56%~72% SiO with what mole % of oxide benchmark was indicated2, 8%~20%
Al2O3, 3%~20% B2O3, 8%~25% Na2O, 0~5% K2O, 0~15% MgO, 0~15% CaO, 0~
15% SrO2, 0~15% BaO and 0~8% ZrO2Glass.
The chemically reinforced glass of the present invention has in glass surface through compressive stress layer obtained from ion exchange.It is handed in ion
It changes in method, ion exchange is carried out to the surface of glass, forms the remaining superficial layer of compression.Specifically, in glass transition
At temperature temperature below, by ion exchange by the smaller alkali metal ion of the ionic radius of glass pane surface (Li ions and/
Or Na ions) it is replaced into other alkali metal ions (Na ions and/or K ions) of ionic radius bigger.As a result, in the table of glass
Face remains compression, and the intensity of glass improves.
In the manufacturing method of the present invention, chemical intensification treatment carries out in the following way：Make to be more than containing ionic radius
The inorganic salts of other alkali metal ions of alkali metal ion contained in glass and the glass above-mentioned containing alkali metal ion
It contacts and carries out ion exchange.That is, other alkali metal contained in alkali metal ion and inorganic salts contained in glass from
Son carries out ion exchange.
In the case that contained alkali metal ion is Na ions in glass, inorganic salts are to contain potassium nitrate (KNO3)
Inorganic salts more preferably also contain selected from by K2CO3、Na2CO3、KHCO3、NaHCO3、Li2CO3、Rb2CO3、Cs2CO3、MgCO3、
CaCO3And BaCO3At least one of group of composition salt.
Such as in the case of containing potassium nitrate in inorganic salts, the fusing point of potassium nitrate is 330 DEG C, is carrying out chemical strengthening
The strain point (being usually 500 DEG C~600 DEG C) of glass has fusing point below.In addition, among above-mentioned salt, the salt in addition to potassium nitrate
(hereinafter, otherwise referred to as " flux ") has the property that will be cut off as the network of the glass of representative using Si-O-Si keys.Due to carrying out
The temperature of chemical intensification treatment is up to hundreds of DEG C, therefore at such a temperature, and the covalent bond between the Si-O of glass is moderately cut off, after
The low-densityization processing stated becomes easy progress.
It should be noted that by the degree of covalent bond cut-out also according to the kind of glass composition or used salt (flux)
Class carries out the chemical intensification treatments condition such as temperature, time of chemical intensification treatment and different, it is believed that selects 4 stretched out from Si
The condition of the cut-off degree of 1~2 key in covalent bond is preferred.
Ion friendship is carried out by the Na ions (or Li ions) and the K ions (or Na ions) in inorganic salts of glass surface
It changes, highdensity compressive stress layer is consequently formed.Can be coating paste for the method for making glass be contacted with inorganic salts
Glass-impregnated is being heated to the molten of fusing point or more by the method for inorganic salts, the method sprayed the aqueous solution of inorganic salts to glass
Melt the method etc. in the salt bath of salt, among those, the method being preferably immersed in fuse salt.
The additive amount of flux is preferably 0.1 mole of % or more, more preferably 0.5 mole of % or more, and further preferably 1 rubs
You are % or more, particularly preferably 2 moles of % or more.In addition, from the viewpoint of productivity, the saturation solubility of preferably each salt
Below.When excessively adding, it is possible to lead to the corrosion of glass.For example, by K2CO3In the case of as flux, preferably 24
Mole % hereinafter, more preferably 12 moles of % hereinafter, particularly preferably 8 moles of % or less.
In inorganic salts, in addition to potassium nitrate and flux, othersization are contained in the range of not interfering the effect of the present invention
Species are learned, such as can be enumerated：The alkali metal chlorizated salts such as sodium chloride, potassium chloride, Boratex, potassium borate or alkali borate
Deng.They can individually be added, and it is a variety of can also to combine addition.
(manufacture of fuse salt)
Fuse salt can be manufactured by well known process.For example, being the fuse salt containing potassium nitrate and flux in inorganic salts
In the case of, then flux can be added in the potassium nitrate fuse salt and obtained by preparing potassium nitrate fuse salt.Separately
Outside, as other methods, can by the way that potassium nitrate is mixed with flux, then make the salt-mixture of the potassium nitrate and flux melt and
It obtains.
The Na concentration of fuse salt used in the manufacturing method of the present application is preferably 500 weight ppm or more, more excellent
It is selected as 1000 weight ppm or more.By a concentration of 2000 weight ppm or more of Na in fuse salt, pass through following acid processing works
Sequence, low-density layer become easy in-depth, therefore further preferably.The upper limit of Na concentration is not particularly limited, can allow until
It can obtain the Na concentration of desired bearing stress (CS).
It is dissolved out from glass it should be noted that containing in the fuse salt for having carried out primary above chemical intensification treatment
Sodium.Therefore, if Na concentration within the above range, can use the sodium from glass directly as the sources Na, in Na
It, can be by adding sodium nitrate in the case of concentration is insufficient, or using not used fuse salt in chemical strengthening
Inorganic sodiums are waited to be adjusted.
(process for carrying out ion exchange)
Then, chemical intensification treatment is carried out using prepared fuse salt.Chemical intensification treatment carries out in the following way：
By the way that glass-impregnated in fuse salt, to be made to the alkali metal ion (Li ions or Na ions) in glass and the ion in fuse salt
The larger other alkali metal ions of radius (Na ions or K ions) carry out ion exchange (displacement).Make glass by the ion exchange
The composition on glass surface changes, and can form the compressive stress layer 20 [Fig. 2 (a)~(b)] of glass surface densification.By this
The densification of glass surface and generate compression, therefore can will be glass reinforced.
It should be noted that in fact, since the density of chemically reinforced glass is from the middle layer at the center for being present in glass
The outer rim of 30 (main bodys) is not present to the gradual densification in compressive stress layer surface, therefore between middle layer 30 and compressive stress layer 20
Density specific boundary jumpy.Here, middle layer indicate be present in center of glass portion, be clipped between compressive stress layer
Layer.The middle layer is different from compressive stress layer, is the layer for not carrying out ion exchange.
Chemical intensification treatment (process for carrying out ion exchange) in the present invention can specifically pass through sequence below
It carries out.
First, fuse salt above-mentioned is adjusted to carry out the temperature of chemical strengthening by Preheat glass.It then, will be preheated
Glass impregnates the defined time in the fuse salt of molten salt bath 27, then lifts glass from fuse salt, and carry out nature
It is cooling.It should be noted that it is preferred that carrying out shape processing corresponding with purposes, example to glass before chemical intensification treatment
Such as, the mechanical processings such as cutting, end face processing and trepanning processing.
The preheating temperature of glass depends on the temperature being immersed in fuse salt, it is often preferred that 100 DEG C or more.
Chemical strengthening temperature is preferably to be reinforced the strain point (being usually 500 DEG C~600 DEG C) of glass hereinafter, in order to obtain
Higher compressive stress layer depth, is particularly preferably 350 DEG C or more, in order to shorten processing time and low-density layer be promoted to be formed,
More preferably 400 DEG C or more, further preferably 430 DEG C or more.
The time of glass being immersed in fuse salt is preferably 1 minute~10 hours, more preferably 5 minutes~8 hours, into
One step is preferably 10 minutes~4 hours.In the range, the change of the balancing good of intensity and the depth of compressive stress layer can be obtained
Strengthened glass is learned, therefore preferably.
In the manufacturing method of the present invention, the steam vapour amount in fuse salt when impregnating glass by increase can thicken
Low-density layer formed in the aftermentioned process with sour contact.In the process contacted with alkali, the low-density can be removed
Layer, therefore, by being set as being present in the flat of the crackle of glass surface or potential cut (latent Injury) by the thickness of the low-density layer
More than equal depth, the crackle or potential cut can be removed while removing low-density layer.It is thereby achieved that chemical strengthening
The excellent surface intensity of glass.
The process for carrying out ion exchange carries out in the atmosphere that dew-point temperature is 20 DEG C or more.The dew point be preferably 30 DEG C with
On, more preferably 40 DEG C or more, further preferably 50 DEG C or more are still more preferably 60 DEG C or more.In addition, the upper limit is preferred
It is set as the temperature for carrying out the inorganic salts (fuse salt) of ion exchange or less.
For dew-point temperature (hereinafter, sometimes referred to simply as " dew point "), as long as the dew near at least interface of fuse salt
Within the above range, interface is nearby the atmosphere in the regions below interface 200mm of span fuse salt to point temperature.It can lead to
It crosses Vaisala DRYCAP (registered trademark) DMT346 dew point transmitters and measures dew point.It should be noted that in this specification
Dew point is value when reaching balance between the atmosphere thought near fuse salt and fuse salt interface.
Simultaneously by the process before the process for carrying out ion exchange and/or with progress ion exchange, vapor is led
Enter in the atmosphere to the interface of fuse salt and/or fuse salt, above-mentioned dew point may be implemented.For example, by molten salt bath
Vapor, can be directed into the atmosphere near the interface of fuse salt and/or fuse salt by upper additional vapor supply unit.
I.e., it is possible to directly blast vapor supplied by vapor supply unit itself in fuse salt or comprising vapor
Gas and water (liquid), vapor or the steam-laden gas of packet can also be directed into fuse salt upper space.In addition,
It can also be imported by being added dropwise to water (liquid) on fuse salt in itself in the range of steam explosion does not occur.
When importing vapor or the steam-laden gas of packet, water (liquid) (hereinafter, sometimes referred to simply as " vapor etc. "),
Whether stirring fuse salt or not, but from the aspect of shortening the time until reaching balance, is preferably stirred.
By from importing amount or water of the time until reaching balance such as vapor according to the gas or liquid imported
Vapor concentration, introduction method etc. and it is different, therefore can not lump together, but if the dew point of above-mentioned atmosphere is stable and as perseverance
It is fixed, then it may determine that have reached balance.
The gas for not influencing chemical intensification treatment can be used by wrapping steam-laden gas, such as can pass through such as Fig. 3 institutes
Show and the dry gas A of air, nitrogen, carbon dioxide gas etc. is directed into heated water 24, includes that water steams to be made
The higher gas of humidity (wrapping steam-laden gas) B of gas.
From the aspect of the incrustation scale deposition for inhibiting pipeline etc., it is preferable to use ion friendships for the water 24 as vapor supply source
Change the pure water such as water.In addition, water 24 is heated such as the water-bath by using sink 25.Alternatively, it is also possible to pass through example
Such as water 24 itself is heated using boiler and generate vapor.
As the introduction method of vapor etc., more specifically, it will includes that water steams that can enumerate (1) from vapor supply unit
The gas B of gas is directed into the upper space of inorganic salts (fuse salt 26), and (2) will wrap steam-laden gas B from bubbling portion and import
Into inorganic salts (fuse salt 26), or water (liquid) is introduced directly into inorganic salts (fuse salt 26) etc. by (3).Wherein, preferably logical
It crosses above-mentioned (1) or (2) forms the atmosphere.
As will wrap steam-laden gas B be directed into inorganic salts (fuse salt 26) upper space a mode and
Speech, such as have：The vapor etc. supplied from vapor supply unit is sprayed to top or the inorganic salts of inorganic salts using sprayer
Interface near method.Vapor etc. is imported by using sprayer, is easy the water vapor concentration of inorganic salts upper space
Control is substantially uniform, therefore preferably.
It should be noted that vapor supply unit, bubbling portion, the introduction part or atomiser device for importing water (liquid)
And be suitably set, it is not particularly limited.Specifically, sprayer can be single, or multiple.Especially
In the case where molten salt bath is big type groove, it is easy the water of inorganic salts upper space using multiple sprayers spraying vapor etc.
Vapor concentration control is substantially uniform.
In the case where that will wrap steam-laden gas and be directed into the upper space of fuse salt, per 1cm3The gas of middle importing
In vapor supply amount be preferably 0.01mg/ minutes or more, more preferably 0.02mg/ minutes or more.It is straight in Jiang Shui (liquid)
It connects in the case of being directed into fuse salt, per 1cm3The flow of the water of middle importing is preferably 0.01mg/ minutes or more, more preferably
0.02mg/ minutes or more.
In the case where that will wrap steam-laden gas and directly blast into inorganic salts (in fuse salt), per 1cm3Middle importing
Gas in vapor supply amount be preferably 0.01mg/ minutes or more, more preferably 0.02mg/ minutes or more.
By carrying out ion-exchange process, obtained chemical strengthening in the more fuse salt of steam vapour amount (amount of moisture)
The surface intensity of glass becomes higher, it is believed that itself the reason is as follows that.
When the carbanion of formation fuse salt reacts with water, it is shown below and generates bicarbonate ion and hydrogen-oxygen
Radical ion.
Here, when the amount of moisture in fuse salt is more, the balance in above formula is tilted to the right, and generates many bicarbonate ions
And hydroxide ion.Due to the ion that hydroxide ion is the cut-out for promoting glass network, therefore, it is considered that more by generating
Hydroxide ion and the formation for promoting the low-density layer of glass surface.
The sum of carbonate anion concentration and bicarbonate anion concentration as obtained from following formula in inorganic salts is excellent
It is selected as 4 moles of % or more, more preferably 6 moles of % or more.By a concentration of 4 moles of % or more, glass surface can be promoted
Low-density layer formed reaction, therefore preferably.
{ (carbonate anion concentration)+(bicarbonate anion concentration) } (mole %)={ (carbonate in inorganic salts
Anion amount)+(the bicarbonate anion amount in inorganic salts) } (mol)/(total anion amount in inorganic salts) (mol) × 100
It should be noted that due to can not directly measure carbonate anion concentration in fuse salt and bicarbonate radical the moon from
Sub- concentration, therefore fuse salt is taken out into a part, using anchracometer TiN-9004, dilute commercial standard solution using pure water
(NaHCO3) and make calibration curve, it then measures and is diluted to the sample solution after 130 times using pure water.At this point, due to carbonic acid
Hydrogen radical anion is all converted to carbonate anion, therefore the value phase of the carbonate anion concentration detected by measurement
When in the sum of carbonate anion concentration and bicarbonate anion concentration.
In addition, the sum of carbonate anion concentration and bicarbonate anion concentration be saturated carbon acid group anion concentration with
The sum of unsaturated carbonate hydrogen radical anion concentration is following.
The process contacted with acid in the process that the low-density layer passes through the part on the surface of aftermentioned removal glass plate
And formed, thickness is about 100nm~about 200nm in the process for the previous carry out ion exchange for not importing vapor, with
This is opposite, ion exchange is carried out in the atmosphere that dew-point temperature is 20 DEG C or more by importing vapor, it is possible thereby to should
Thickness is adjusted to 300nm or more.
Due to generated glass in the glass processing regimen in glass manufacture process or comprising chemical intensification treatment process
The mean depth of the crackle on surface or potential cut is about 500nm, therefore the thickness of low-density layer is more preferably 500nm or more,
Further preferably 600nm or more.
Being formed by low-density layer can be by the aftermentioned and alkali in the process for the part for removing the surface of glass plate
The process of contact and remove.Therefore, if the crackle of glass surface or the depth of potential cut are thicker than low-density layer
It spends shallow, then can all be removed these crackles and potential cut by the process contacted with alkali.
By the crackle for removing the glass surface for causing the intensity of chemically reinforced glass to decline or potential cut, chemistry can be made
The surface intensity higher of strengthened glass.
(process cleaned)
In the manufacturing method of the present invention, the part preferably in the process for carrying out ion exchange and the surface of removal glass plate
Process between also include cleaning glass plate process.In the process cleaned, industrial water, ion exchange water etc. are used
Carry out the cleaning of glass.Industrial water uses processed industrial water as needed.Wherein it is preferably ion exchange water.
The condition of cleaning is different according to used cleaning solution, using ion exchange water, from can be by institute
From the viewpoint of the salt of attachment completely removes, preferably cleaned at 0 DEG C~100 DEG C.
In the process cleaned, it can use and chemically reinforced glass is immersed in the sink equipped with ion exchange water etc.
In method or the method, the method by water jet to glass surface jet cleaning liquid that are exposed to glass surface in flowing water
Etc. various methods.
(process of the part on the surface of removal glass plate)
The process that the part on the glass plate after ion exchange into the surface for being about to the glass plate is removed.By glass plate
The process of the part removal on surface preferably comprises the process for making glass plate be contacted with acid, more preferably in described and sour contact work
Also include to make the process that glass plate is contacted with alkali after sequence.
(process contacted with acid)
In the manufacturing method of the present invention, as it is described carry out ion exchange process or the process cleaned it
The process of the part on the surface of removal glass plate afterwards, the process (acid treatment process) preferably contacted into enforcement glass and acid.
The acid processing of glass is carried out by being immersed in chemically reinforced glass in acid solution, and thus, it is possible to will be chemical
The Na and/or K on strengthened glass surface are replaced into H.That is, modified, tool has occurred on the glass surface also surface layer with compressive stress layer
The low-density layer that low-density has occurred for body and is formed.
Solution is not particularly limited if it is acidity, and pH is less than 7, and used acid can be that weak acid can also
For strong acid.Specifically, it is preferable that hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid and citric acid etc. are sour.These acid can be with
It is used alone, multiple combinations can also be used.
Although the temperature of the sour processing of progress difference according to type or concentration, the time of used acid, preferably 100
DEG C or less carry out.
Although the time of the sour processing of progress difference according to type or concentration, the temperature of used acid, from productivity
From the aspect of, preferably 10 seconds~5 hours, more preferably 1 minute~2 hours.
Although carry out the concentration of the solution of sour processing according to the type of used acid or time, temperature difference, it is excellent
The concentration that the worry to container corrosion is few is selected, specifically preferably 0.1 weight of weight %~20 %.
Since low-density layer can be removed by aftermentioned alkali process, low-density layer is thicker, then glass surface
More it is easily removed.The thickness of low-density layer as described above, from the viewpoint of glass surface removal amount, preferably 300nm with
On, more preferably 500nm or more, further preferably 600nm or more.
From the viewpoint of glass surface removal, the density of low-density layer is preferably shorter than than the compression after ion exchange
The density in the region (main body) of layer depth.The thickness of low-density layer can be by passing through X ray reflection rate method (X-ray-
Reflectometry：XRR) measure period (Δ θ) and find out.The density of low-density layer can be critical by being measured by XRR
Angle (θ c) and find out.
It should be noted that also can be true simply by the section for observing glass using scanning electron microscope (SEM)
Recognize the formation of low-density layer and the thickness of layer.
(process contacted with alkali)
In the manufacturing method of the present invention, preferably after the process by being contacted with acid, the work contacted with alkali is further carried out
Sequence (alkali process process).More preferably with after the process that contacts of acid and before the process contacted with alkali, by with it is above-mentioned
The process of the identical cleaning glass plate of process cleaned.
Alkali process is carried out by the solution that chemically reinforced glass is immersed in alkalinity, thus, it is possible to removing described and
Part or all for the low-density layer formed in process that acid contacts.
Solution is not particularly limited if it is alkalinity, and pH is more than 7, can use weak base that can also use highly basic.
Specifically, it is preferable that the alkali such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate.These alkali can be used alone, and can also incite somebody to action
Multiple combinations use.
Carry out alkali process temperature also according to used alkali type or concentration, time and difference, preferably 0 DEG C~
100 DEG C, more preferably 10 DEG C~80 DEG C, particularly preferably 20 DEG C~60 DEG C.If within this temperature range, sent out without glass
The risk of raw corrosion, is therefore preferred.
Although carry out alkali process time also according to used alkali type or concentration, temperature and difference, from production
It is preferably 10 seconds~5 hours, more preferably 1 minute~2 hours from the aspect of rate.
Although carry out the concentration of the solution of alkali process according to the type of used alkali or time, temperature difference, from
From the viewpoint of glass surface removal, preferably 0.1 weight of weight %~20 %.
By above-mentioned alkali process, part or all of low-density layer after H enters is removed, thus, it is possible to obtain face
The chemically reinforced glass that intensity improves.Especially in the present invention, the thickness of low-density layer can be made to be deeper than and is present in glass table
The depth of the crackle in face or potential cut.Therefore, it is considered that the crackle or potential cut and low-density of glass surface can be will be present in
Layer removes simultaneously, and the surface intensity to be more conducive to glass improves.It should be noted that it is preferred that after alkali process, also pass through
By with identical method is cleaned above process.
＜ chemically reinforced glass ＞
The manufacturing method of chemically reinforced glass according to the present invention can be deeper compared with previous chemical intensification treatment
Ground forms low-density layer, thus after removing the low-density layer obtained chemically reinforced glass surface layer, crackle or potential stroke
Trace is less.Therefore, through the invention obtained from chemically reinforced glass have very high surface intensity.
(glass surface intensity)
The surface intensity of chemically reinforced glass can be evaluated by ball and ring test.
(ball and ring test)
Chemically reinforced glass is by passing through ball (Ball on Ring；BoR the BoR surface intensities F (N) for) testing and measuring is carried out
Evaluation, the ball and ring test are that glass plate configuration is had the circularity that radius of curvature is 2.5mm in a diameter of 30mm, contact site
On the ring be made of stainless steel, in the state of making the sphere of a diameter of 10mm being made of steel with the contact glass sheet, quiet
Load is applied to the sphere at the center of the ring under state load-up condition.
1st interarea of chemically reinforced glass and the intensity of the 2nd interarea are preferably satisfied by F >=1500 × t2, more preferably F >=
1800×t2, further preferably F >=2000 × t2[in formula, F is the BoR surface intensities (N) measured by ball and ring test, and t is glass
The plate thickness (mm) of glass substrate].In the range by BoR surface intensities F (N), even if table if in the case where having carried out thin plate
Reveal excellent surface intensity.It should be noted that BoR experiments can be carried out by the method described in aftermentioned embodiment.
(compressive stress layer)
The value of compressive stress of the compressive stress layer of chemically reinforced glass and the depth of compressive stress layer can use EPMA (electron
Probe micro analyzer, electron probe microanalyzer) or surface stress meter (for example, manufactured by the former making of folding
) etc. FSM-6000 it is measured.
(removal amount of glass surface (low-density layer))
The removal amount (thickness) of glass surface (low-density layer) after alkali process can be found out in the following way：Using point
Analysis electronic balance measures the weight of chemical reagent before and after the processing, and carries out thickness conversion using following formula.
(the removal amount thickness per one side)=[(weight before processing)-(weight after processing)]/(specific gravity of glass)/process face
Product/2
At this point, specific gravity of glass is set as 2.48 (g/cm3) and calculated.
Embodiment
The present invention is concretely demonstrated hereinafter, enumerating embodiment, but the present invention is not limited to these examples.
＜ evaluation methods ＞
Various evaluations in the present embodiment are carried out by analysis method as shown below.
(the evaluation of glass：Surface intensity)
Glass surface intensity passes through ball (Ball on Ring；BoR) experiment is determined.It is shown in Fig. 1 for illustrating
The skeleton diagram of the ball and ring test used in the present invention.In the state of mounting that glass plate 1 is horizontal, the pressurization of SUS304 is used
Fixture 2 (hardened steel, diameter 10mm, mirror finish) pressurizes to glass plate, to determine the surface intensity of glass plate.
In Fig. 1, in the fixture 3 that bears of SUS304, (diameter 30mm, the curvature of contact site are R2.5mm, and contact site is hard
Change steel, mirror finish) on, it has been horizontally disposed with the glass plate as sample.It is provided with for glass in the top of glass plate
The press fixture that plate pressurizes.
In the present embodiment, it is pressurizeed from the top of obtained glass plate to the middle section of glass plate.It needs
It is noted that experimental condition is as described below.
The decrease speed of press fixture：1.0 (mm/ minutes)
At this point, the breaking load (unit N) when glass is destroyed is used as BoR surface intensities, the average value that 20 times are measured
It is averaged surface intensity as BoR.But in the case where the destruction starting point of glass plate and ball pressing position deviate 2mm or more, by it
It is excluded from the data for calculating average value.
(the evaluation of glass：Surface stress)
The bearing stress value (CS, unit MPa) of glass and the depth (DOL, unit are μm) of compressive stress layer are using folding
The surface stress meter (FSM-6000) of former manufacturing company's manufacture is determined.
(the evaluation of glass：Removal amount)
The removal amount thickness of glass is found out in the following way：Utilize analysis electronic balance (HR-202i；AND is manufactured)
The weight of chemical reagent before and after the processing is measured, and thickness conversion is carried out using following formula.
(the removal amount thickness per one side)=[(weight before processing)-(weight after processing)]/(specific gravity of glass)/process face
Product/2
At this point, specific gravity of glass is set as 2.48 (g/cm3) and calculated.
(the evaluation of glass：Crackle or potential cut)
About the crackle or the presence or absence of potential cut on glass surface, carried out under the light source of 1500 lux of illumination visual
It checks, if not capableing of the defect of visuognosis, is judged as that crackle or potential cut is not present.
1 ＞ of ＜ embodiments
(process for carrying out ion exchange)
Potassium nitrate 8454g, potassium carbonate 1324g, sodium nitrate 222g is added in the pot made to stainless steel (SUS), utilizes sheathing
Formula heater is heated to 490 DEG C, to be prepared for the fuse salt of 10 moles of % of potassium carbonate, 6000 weight ppm of sodium.By to melting
The air for being once directed into and being heated in 55 DEG C of water is passed through in atmosphere near the interface of salt, to make to be steamed comprising water in fuse salt
Gas.
Experimental system is shown in Fig. 3, uses air as dry gas A, is added using sink 25 by that will bypass air through
It is humidified in the water 24 of heat to 55 DEG C, to obtain the steam-laden gas of humidified packet (air) B.
Path after making the steam-laden gas B of the packet be heated by using ribbon heater and be directed into and carry out at chemical strengthening
Thus the upper space of the inorganic salts (fuse salt) 26 of the slot of reason has carried out the control of the dew point in the process of ion exchange
System.Every 1cm at this time3In vapor supply amount be 0.02mg/ minute, the dew point near the interface of fuse salt is 38 DEG C.
The glass plate A for preparing 50mm × 50mm × 0.7mm, is preheated to 350 DEG C~400 DEG C, then in 490 DEG C of fuse salt
It is middle dipping 1 hour, carry out ion-exchange treatment, then cool to room temperature near, thus carried out chemical intensification treatment.To gained
To chemically reinforced glass washed, and carry out subsequent process.
The glass composition (being indicated with a mole % for oxide benchmark) of glass plate A：SiO264.2%, Al2O38.0%,
Na2O 12.5%, K2O 4.0%, MgO 10.5%, CaO 0.1%, SrO 0.1%, BaO 0.1%, ZrO20.5%
(the process 1 of the part on removal surface：The process contacted with acid)
The nitric acid for preparing 6.0 weight % in beaker (dilutes (Northeast chemical company system of nitric acid 1.38 using ion exchange water
Make)), using water-bath, the temperature was then adjusted to 40 DEG C.By the glass obtained in the chemical strengthening process in prepared nitric acid
Dipping 120 seconds, to carry out sour processing.Then, which is washed, and carries out subsequent handling.
(the process 2 of the part on removal surface：The process contacted with alkali)
The sodium hydrate aqueous solution for preparing 4.0 weight % in beaker (dilutes 48% sodium hydroxide using ion exchange water
Solution (manufacture of Northeast chemical company)), using water-bath, the temperature was then adjusted to 40 DEG C.It will be cleaned after the process contacted with acid
Glass impregnated 120 seconds in prepared sodium hydrate aqueous solution, to carry out alkali process.Then, which is carried out
Wash and cleaned the alkali of glass surface.Then, it is dried by air blast.
By operating to have obtained the chemically reinforced glass of embodiment 1 above.
The presence of crackle and potential cut is not confirmed in obtained chemically reinforced glass.
2 ＞ of ＜ embodiments
The concentration of potassium carbonate of fuse salt in the process for carrying out ion exchange is set as 8 moles of %, by the boundary of fuse salt
Dew point near face is set as 71 DEG C, is set as carrying out 2 hours at 450 DEG C by chemical intensification treatment condition, in addition to this, with
Mode similarly to Example 1 has manufactured chemically reinforced glass.It is steamed comprising water it should be noted that being imported to control dew point
Every 1cm when the gas of gas3In vapor supply amount be 0.08mg/ minutes.In obtained chemically reinforced glass not really
Recognize the presence of crackle and potential cut.
1 ＞ of ＜ comparative examples
Other than the dew point near the interface of the fuse salt in the process for carrying out ion exchange is set as 9 DEG C, with
2 same mode of embodiment has manufactured chemically reinforced glass.It should be noted that not carrying out for controlling being steamed comprising water for dew point
The importing of the gas of gas.
The presence of crackle and potential cut is not confirmed in obtained chemically reinforced glass.
2 ＞ of ＜ comparative examples
Potassium carbonate is not added in fuse salt in the process for carrying out ion exchange, sodium is set as 2000 weight ppm, no
Sour processing and alkali process are carried out, has manufactured chemically reinforced glass in a manner of same as comparative example 1 in addition to this.Obtained
The presence of crackle and potential cut is not confirmed in glass.
3 ＞ of ＜ embodiments
Other than having used glass plate B, chemically reinforced glass has been manufactured under the condition that is similarly to Example 1.Institute
The presence of crackle and potential cut is not confirmed in obtained chemically reinforced glass.
The glass composition of glass plate B (mole % of oxide benchmark is indicated)：SiO268.0%, Al2O312.0%,
Na2O 18.6%, MgO 8.0%
4 ＞ of ＜ embodiments
Other than having used glass similarly to Example 3, manufactured under conditions of similarly to Example 2 chemical strong
Change glass.The presence of crackle and potential cut is not confirmed in obtained chemically reinforced glass.
3 ＞ of ＜ comparative examples
Other than having used glass similarly to Example 3, manufactured under the conditions of same as comparative example 1 chemical strong
Change glass.The presence of crackle and potential cut is not confirmed in obtained chemically reinforced glass.
4 ＞ of ＜ comparative examples
Other than having used glass similarly to Example 3, manufactured under the conditions of same as comparative example 2 chemical strong
Change glass.The presence of crackle and potential cut is not confirmed in obtained glass.
5 ＞ of ＜ embodiments
(process for carrying out ion exchange)
Glass plate C in addition to using thickness 0.55mmt, and by the dew point near the interface of fuse salt be set as 66 DEG C with
Outside, chemically reinforced glass has been manufactured under conditions of similarly to Example 2.It is not confirmed in obtained chemically reinforced glass
The presence of crackle and potential cut.
The glass composition of glass plate C (mole % of oxide benchmark is indicated)：SiO267%, B2O34%, Al2O3
13%, Na2O 14%, K2O ＜ 1%, MgO 2%, CaO ＜ 1%
5 ＞ of ＜ comparative examples
Other than having used glass similarly to Example 5, manufactured under the conditions of same as comparative example 2 chemical strong
Change glass.The presence of crackle and potential cut is not confirmed in obtained chemically reinforced glass.
Various evaluations have been carried out to chemically reinforced glass derived above.The treatment conditions of glass and evaluation result are shown in
Table 1.It should be noted that as BoR surface intensities, show that BoR is averaged surface intensity.
For Examples 1 to 5 and the Comparative Examples 1 to 5, carried out under the light source of 1500 lux of illumination
When visual inspection, the presence of crackle and potential cut is not confirmed.However, as shown in table 1, it is real compared with the Comparative Examples 1 to 5
It applies example 1~5 and shows higher BoR surface intensities F (N).
About compared with the Comparative Examples 1 to 5, Examples 1 to 5 show higher BoR surface intensities F (N) the reasons why, it is believed that reason
By as follows.In the manufacturing method of the present invention, by carrying out the glass plate in the atmosphere that dew-point temperature is 20 DEG C or more
The process of the alkali metal ion and the ion exchange of other alkali metal ions of the inorganic salts, can increase to glass
The steam vapour amount in fuse salt when carrying out chemical strengthening is present in the crackle of glass surface or potential cut to be formed to have
Mean depth more than depth low-density layer.Pass through one of the surface of the glass plate after the removal ion exchange
The process divided, can fully remove the crackle or potential cut or be substantially reduced while removing the low-density layer
Its quantity can realize higher BoR surface intensities F (N).
The present invention is illustrated in detail with reference to specific mode, but aobvious and easy to those skilled in the art
See, various modifications may be made without departing from the spirit and scope of the present invention and corrects.It should be noted that
The Japanese patent application (Patent 2015-256894) that the application was proposed based on December 28th, 2015, entirely through reference
It is cited.In addition, cited all references are incorporated herein as a whole.
Industrial applicability
The manufacturing method of chemically reinforced glass according to the present invention, can be after chemical strengthening without grinding or using
The very high chemically reinforced glass of surface intensity is obtained in the case of the etching process of hydrofluoric acid etc..I.e., it is possible to obtain a kind of chemistry
Strengthened glass, there is no caused by the expansion with the potential cut generated using the etching process of the progress such as hydrofluoric acid
Bad order or the grinding cut generated with grinding, and surface intensity is excellent.
Therefore, unrelated with the presence or absence of the surface damage of the glass before chemical intensification treatment, potential cut or degree, Ke Yiying
For all glass, versatility is higher.And due to can be handled by dipping in the solution, it is being easy to answer
Glass etc. to various glass shapes or large area is effective.In addition, with the etching process phase that has used hydrofluoric acid etc.
Than safe and at low cost.
Reference numeral
1 glass plate
2 press fixtures
3 bear fixture
10 low-density layers
20 compressive stress layers
30 middle layers
21 adjusters
22 flowmeters
23 check-valves
24 water
25 sinks
26 fuse salts
27 molten salt baths
Claims (19)
1. a kind of manufacturing method of chemically reinforced glass, which is characterized in that the manufacturing method of the chemically reinforced glass includes：
Prepare the process of the glass plate containing alkali metal ion；
Prepare the process of the inorganic salts containing the big other alkali metal ions of ionic radius than the alkali metal ion；
In the atmosphere that dew-point temperature is 20 DEG C or more, the alkali metal ion of the glass plate and the inorganic salts are carried out
The process of the ion exchange of other alkali metal ions；And
The process for removing the part on the surface of the glass plate after the ion exchange.
2. the manufacturing method of chemically reinforced glass as described in claim 1, which is characterized in that the work for carrying out ion exchange
Sequence carries out in the atmosphere that the dew-point temperature is 30 DEG C or more.
3. the manufacturing method of chemically reinforced glass as claimed in claim 1 or 2, which is characterized in that the carry out ion exchange
Process carried out in the dew-point temperature is 40 DEG C or more of atmosphere.
4. the manufacturing method of chemically reinforced glass according to any one of claims 1 to 3, which is characterized in that the progress
The process of ion exchange carries out in the atmosphere that the dew-point temperature is 50 DEG C or more.
5. the manufacturing method of chemically reinforced glass as described in any one of claims 1 to 4, which is characterized in that the progress
The process of ion exchange carries out in the temperature atmosphere below that the dew-point temperature is the inorganic salts.
6. such as the manufacturing method of chemically reinforced glass according to any one of claims 1 to 5, which is characterized in that the progress
Atmosphere in the process of ion exchange is directed into the inorganic salts by that will wrap steam-laden gas from vapor supply unit
Upper space and formed, and for the import volume of the steam-laden gas of the packet, per 1cm3In vapor supply
Amount is 0.01mg/ minutes or more.
7. such as the manufacturing method of chemically reinforced glass according to any one of claims 1 to 5, which is characterized in that the progress
Atmosphere in the process of ion exchange is formed by will wrap steam-laden gas and be directed into the inorganic salts from bubbling portion,
And for the import volume of the steam-laden gas of packet, per 1cm3In vapor supply amount be 0.01mg/ minutes
More than.
8. such as the manufacturing method of chemically reinforced glass according to any one of claims 1 to 7, which is characterized in that in the standard
In the process of standby inorganic salts, prepare containing selected from by K2CO3、Na2CO3、KHCO3、NaHCO3、Li2CO3、Rb2CO3、Cs2CO3、
MgCO3、CaCO3And BaCO3The inorganic salts of at least one of group of composition salt and potassium nitrate.
9. such as the manufacturing method of chemically reinforced glass according to any one of claims 1 to 8, which is characterized in that the removal
The process of the part on the surface of glass plate includes the process that the glass plate after making the ion exchange is contacted with acid.
10. the manufacturing method of chemically reinforced glass as claimed in claim 9, which is characterized in that the table of the removal glass plate
The process of the part in face it is described with after the process of sour contact also include so that the glass plate is contacted with alkali process.
11. the manufacturing method of chemically reinforced glass as claimed in claim 10, which is characterized in that in described and sour contact work
Also include the process for cleaning the glass plate between sequence and the process contacted with alkali.
12. the manufacturing method of the chemically reinforced glass as described in any one of claim 1~11, which is characterized in that described
It carries out between the process of ion exchange and the process of the part on the surface of the removal glass plate, also includes to clean the glass
The process of plate.
13. the manufacturing method of the chemically reinforced glass as described in any one of claim 10~12, which is characterized in that described
Also include the process for cleaning the glass plate after the process contacted with alkali.
14. the manufacturing method of the chemically reinforced glass as described in any one of claim 9~13, which is characterized in that described
In the process contacted with acid, 7 solution is less than using pH.
15. the manufacturing method of chemically reinforced glass as claimed in claim 14, which is characterized in that the pH is less than 7 solution
For weak acid.
16. the manufacturing method of chemically reinforced glass as claimed in claim 14, which is characterized in that the pH is less than 7 solution
For strong acid.
17. the manufacturing method of the chemically reinforced glass as described in any one of claim 10~16, which is characterized in that described
In the process contacted with alkali, 7 solution is more than using pH.
18. the manufacturing method of chemically reinforced glass as claimed in claim 17, which is characterized in that the pH is more than 7 solution
For weak base.
19. the manufacturing method of chemically reinforced glass as claimed in claim 17, which is characterized in that the pH is more than 7 solution
For highly basic.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2015-256894 | 2015-12-28 | ||
| JP2015256894 | 2015-12-28 | ||
| PCT/JP2016/088788 WO2017115765A1 (en) | 2015-12-28 | 2016-12-26 | Method for producing chemically toughened glass |
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| CN108473368A true CN108473368A (en) | 2018-08-31 |
| CN108473368B CN108473368B (en) | 2021-10-29 |
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| CN201680076423.9A Active CN108473368B (en) | 2015-12-28 | 2016-12-26 | Method for producing chemically strengthened glass |
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|---|---|
| JP (1) | JP6288392B2 (en) |
| KR (1) | KR20180098268A (en) |
| CN (1) | CN108473368B (en) |
| TW (2) | TWI710536B (en) |
| WO (1) | WO2017115765A1 (en) |
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| CN113454040A (en) * | 2019-02-22 | 2021-09-28 | Ａｇｃ株式会社 | Glass substrate with stain-proofing layer and method for producing glass substrate with stain-proofing layer |
| CN116639889A (en) * | 2019-12-26 | 2023-08-25 | Ａｇｃ株式会社 | Method for producing chemically strengthened glass and lithium ion adsorbent |
| CN116715451A (en) * | 2023-06-02 | 2023-09-08 | 河南曲显光电科技有限公司 | Method for reutilizing scrapped potassium nitrate, lithium-containing glass and strengthening method thereof |
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| WO2018043361A1 (en) * | 2016-09-02 | 2018-03-08 | 旭硝子株式会社 | Method for producing chemically toughened glass |
| CN113135672B (en) * | 2017-06-23 | 2023-03-24 | Ａｇｃ株式会社 | Chemically strengthened glass |
| JP7247454B2 (en) | 2017-06-27 | 2023-03-29 | Ａｇｃ株式会社 | Chemically strengthened glass manufacturing method and chemically strengthened glass |
| JP7024565B2 (en) * | 2018-04-04 | 2022-02-24 | Ａｇｃ株式会社 | Manufacturing method of chemically strengthened glass |
| JP2019199393A (en) * | 2018-05-18 | 2019-11-21 | Ａｇｃ株式会社 | Production method of chemically strengthened glass and chemically strengthened glass |
| US20210163349A1 (en) * | 2019-12-02 | 2021-06-03 | Corning Incorporated | Methods to mitigate haze induced during ion exchange with carbonate salts |
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| JP6870679B2 (en) * | 2016-07-08 | 2021-05-12 | 味の素株式会社 | Evaluation method for future risk of developing Alzheimer's disease |
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- 2016-12-26 CN CN201680076423.9A patent/CN108473368B/en active Active
- 2016-12-26 JP JP2017551359A patent/JP6288392B2/en active Active
- 2016-12-26 WO PCT/JP2016/088788 patent/WO2017115765A1/en active Application Filing
- 2016-12-26 KR KR1020187017943A patent/KR20180098268A/en not_active Application Discontinuation
- 2016-12-28 TW TW105143500A patent/TWI710536B/en active
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| CN101928110A (en) * | 2008-12-26 | 2010-12-29 | Hoya株式会社 | Glass substrate and method for manufacturing the same |
| CN104203859A (en) * | 2012-03-26 | 2014-12-10 | 旭硝子株式会社 | Glass plate which can be reduced in warping during chemical toughening |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109437598A (en) * | 2018-11-02 | 2019-03-08 | 文登市文胜玻璃有限公司 | A kind of the fast ionic Enhancement Method and sodium calcium silicon ion reinforcing glass of soda-lime-silica glass |
| CN113454040A (en) * | 2019-02-22 | 2021-09-28 | Ａｇｃ株式会社 | Glass substrate with stain-proofing layer and method for producing glass substrate with stain-proofing layer |
| CN113454040B (en) * | 2019-02-22 | 2023-09-05 | Ａｇｃ株式会社 | Glass substrate with antifouling layer and method for producing glass substrate with antifouling layer |
| CN116639889A (en) * | 2019-12-26 | 2023-08-25 | Ａｇｃ株式会社 | Method for producing chemically strengthened glass and lithium ion adsorbent |
| CN116715451A (en) * | 2023-06-02 | 2023-09-08 | 河南曲显光电科技有限公司 | Method for reutilizing scrapped potassium nitrate, lithium-containing glass and strengthening method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2017115765A1 (en) | 2017-12-28 |
| TW201736310A (en) | 2017-10-16 |
| WO2017115765A1 (en) | 2017-07-06 |
| KR20180098268A (en) | 2018-09-03 |
| TW202110768A (en) | 2021-03-16 |
| TWI725921B (en) | 2021-04-21 |
| JP6288392B2 (en) | 2018-03-07 |
| TWI710536B (en) | 2020-11-21 |
| CN108473368B (en) | 2021-10-29 |
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