CN109095789A - The manufacturing method of chemically reinforced glass - Google Patents
The manufacturing method of chemically reinforced glass Download PDFInfo
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- CN109095789A CN109095789A CN201810630799.0A CN201810630799A CN109095789A CN 109095789 A CN109095789 A CN 109095789A CN 201810630799 A CN201810630799 A CN 201810630799A CN 109095789 A CN109095789 A CN 109095789A
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- Prior art keywords
- glass
- alkali
- mentioned
- chemically reinforced
- manufacturing
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Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B11/00—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto
- B08B11/04—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto specially adapted for plate glass, e.g. prior to manufacture of windshields
-
- 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 relates to the manufacturing methods of chemically reinforced glass.The purpose of the present invention is to provide a kind of methods that manufacture has both the chemically reinforced glass of intensity and exterior quality.The present invention relates to a kind of manufacturing methods of chemically reinforced glass, it includes: chemical strengthening process, by contacting the glass containing sodium with the inorganic salts containing specific salt, the K ion in Na ion and above-mentioned inorganic salts in above-mentioned glass is thus made to carry out ion exchange；Acid treatment process carries out sour processing to above-mentioned glass after above-mentioned chemical strengthening process；Alkali process process carries out alkali process to above-mentioned glass after above-mentioned acid treatment process.First embodiment of the invention be by ultrasonic cleaning frequency and acoustic pressure be set as specific condition.In addition, second embodiment of the present invention is to carry out under wet environment from above-mentioned acid treatment process to the series of processes of above-mentioned alkali process process.
Description
Technical field
The present invention relates to the manufacturing methods of chemically reinforced glass.
Background technique
For digital camera, mobile phone or portable information terminal PDA (Personal Digital Assistants) etc.
Panel display apparatus for, proceeded as follows to protect display and improve beautiful: comparing image displaying part to be formed
The mode in broader region is divided to protect configurations of glass in the front surface of display thin plate.Although glass theoretical strength
Height, but intensity can be significantly reduced because of damage, for the protection glass of desired strength, using by ion exchange etc. in glass
Glass surface is formed with the chemically reinforced glass of compressive stress layer.
Along with the requirement of lightweight and slimming to panel display apparatus, it is desirable that protection glass itself is also thinning.Cause
This, for protecting glass, in order to meet above-mentioned purpose, to the higher intensity of surface requirements.
As one of the method for intensity for improving glass, a kind of manufacture of chemically reinforced glass is disclosed in patent document 1
Method, wherein after the chemical strengthening process carried out using the inorganic salts containing specific salts, carry out at acid treatment process and alkali
Science and engineering sequence.According to manufacturing method documented by patent document 1, after chemical strengthening without grind or using hydrofluoric acid etc. erosion
Quarter processing, the available significantly higher chemistry of surface intensity compared with the chemically reinforced glass obtained by previous chemical strengthening
Strengthened glass.
On the other hand, in the volume production process of chemically reinforced glass, implement ultrasonic cleaning between each process.In ultrasonic wave
In cleaning, by glass-impregnated in cleaning solution, ultrasonic activation is applied to the cleaning solution.At this point, the hydrone etc. in cleaning solution
Vibrate to particle high speed to which water is quickly vaporization and generate bubble, which sharp condenses and disappears, the phenomenon repeatedly into
Row, is partially formed the state of high temperature and pressure.The phenomenon is known as cavitation.Pollutant is removed from glass by cavitation, and is easy
Ground is dispersed in cleaning solution, therefore, the cleaning of glass can be effectively performed.Especially it is difficult to carry out the physics such as scrubbing in cleaning
In the case where the glass of the shape of cleaning, ultrasonic cleaning is effective method.
A kind of manufacturing method of glass substrate for disc is disclosed in patent document 2, it includes to glass substrate for disc
Carry out the cleaning process of ultrasonic cleaning, wherein, will when the size as the foreign matter for removing object is mainly 1.0 μm or less
The frequency of ultrasonic wave is set as 80kHz~120kHz, and the acoustic pressure of ultrasonic wave is set as 1.5mV~2.5mV.
In addition, disclosing following method in patent document 3: cleaning agent is used, by ultrasonic cleaning to glass product
Hickie (white ヤ ケ) carries out cleaning to removing hickie from glass product, wherein by the frequency of 20kHz~400kHz and
The ultrasonic cleaning of the acoustic pressure of 10mV~150mV cleans the hickie of glass product.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2015/008763
Patent document 2: Japanese Unexamined Patent Publication 2010-238298 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2007-253065 bulletin
Summary of the invention
Problem to be solved by the invention
As shown in Figure 1A, in the patent document 1 of the chemical strengthening process comprising being carried out using the inorganic salts containing specific salts
The manufacturing method of documented chemically reinforced glass is (hereinafter, also referred to as comprising utilizing the inorganic salts progress containing specific salts
The manufacturing method of chemical strengthening process) in, in order to improve the cleannes of glass, it is usually preferred to after carrying out chemical intensification treatment
Cleaning process after water in cleaning process, acid treatment process rinses, the water in alkali process process rinses and alkali process process,
These cleaning treatments are set as applying ultrasonic wave and the ultrasonic cleaning that carries out sometimes.
In addition, as shown in Figure 1B, in the existing chemical strengthening work comprising being carried out using the inorganic salts without containing specific salts
In the manufacturing method (hereinafter, also referred to as comprising the manufacturing method of existing chemical strengthening process) of the chemically reinforced glass of sequence,
In general, carrying out cleaning process after chemical strengthening process.
The inventors discovered that containing compared with the manufacturing method comprising existing chemical strengthening process by the inclusion of utilizing
The manufacturing method for the chemical strengthening process that the inorganic salts of specific salts carry out, although the surface intensity of obtained chemically reinforced glass flies
It improves to jump property, but there are the following problems: implementing under typical conditions to guarantee the exterior quality of chemically reinforced glass
When ultrasonic cleaning, glass tape is damaged, the surface intensity of chemically reinforced glass is reduced to and by the inclusion of existing chemical strong
The chemically reinforced glass equal extent that the manufacturing method of chemical industry sequence obtains.
Contain specific salts by the inclusion of utilization just because of compared with the manufacturing method comprising existing chemical strengthening process
The manufacturing method of chemical strengthening process that carries out of inorganic salts can be realized significantly higher surface intensity, such problems just becomes
Become apparent project.
Therefore, the side of the chemically reinforced glass of intensity and exterior quality is had both the purpose of the present invention is to provide a kind of manufacture
Method.
The means used to solve the problem
The inventors discovered that carrying out sour processing after the chemical strengthening process carried out using the inorganic salts containing specific salts
In the manufacturing method of the chemically reinforced glass of process and alkali process process, by the item that ultrasonic cleaning is set as to particular range
Part or by under wet environment carry out from acid treatment process to the series of processes of alkali process process, thus, it is possible to inhibition
The intensity for learning strengthened glass is reduced because of ultrasonic cleaning, also, in the case where implementing the cleaning of repeated ultrasonic wave, by wet
The process between ultrasonic cleaning and ultrasonic cleaning is carried out under environment, can obtain having both intensity and the chemistry of exterior quality is strong
Change glass, so as to complete the present invention.
That is, the present invention is as described below.
1. a kind of manufacturing method of chemically reinforced glass, it includes chemical strengthening process, by make the glass containing sodium with
Containing potassium nitrate and selected from by K2CO3、Na2CO3、KHCO3、NaHCO3、K3PO4、Na3PO4、K2SO4、Na2SO4, KOH and NaOH structure
At at least one of group salt or alkali inorganic salts contact, thus make in the Na ion and above-mentioned inorganic salts in above-mentioned glass
K ion carries out ion exchange；Acid treatment process carries out sour processing to above-mentioned glass after above-mentioned chemical strengthening process；At alkali
Science and engineering sequence carries out alkali process to above-mentioned glass after above-mentioned acid treatment process, wherein the manufacturing method also includes to be selected from down
State at least one of (1)~(4) cleaning treatment.
(1) during above-mentioned acid treatment process, be 25kHz or more and 80kHz or less using frequency and acoustic pressure is
The cleaning treatment that 80mV ultrasonic wave below carries out；
(2) after above-mentioned acid treatment process and before above-mentioned alkali process process, using frequency be 25kHz or more and
80kHz or less and acoustic pressure are the cleaning treatment that 80mV ultrasonic wave below carries out；
(3) during above-mentioned alkali process process, be 25kHz or more and 80kHz or less using frequency and acoustic pressure is
The cleaning treatment that 80mV ultrasonic wave below carries out；
(4) after above-mentioned alkali process process, be 25kHz or more and 80kHz or less using frequency and acoustic pressure is
The cleaning treatment that 80mV ultrasonic wave below carries out.
2. the manufacturing method of the chemically reinforced glass as described in above-mentioned 1, wherein repeatedly carrying out selected from above-mentioned (1)~(4)
At least one of in the case where cleaning treatment, the process during the cleaning treatment is carried out under wet environment.
3. the manufacturing method of the chemically reinforced glass as described in above-mentioned 1 or 2, wherein wrapped after above-mentioned alkali process process
Containing drying process, the process before from above-mentioned acid treatment process to above-mentioned drying process is carried out under wet environment.
4. the manufacturing method of the chemically reinforced glass as described in above-mentioned any one of 1~3, wherein above-mentioned chemical strengthening glass
Glass is protection glass.
5. the manufacturing method of the chemically reinforced glass as described in above-mentioned any one of 1~4, wherein carry out selected from above-mentioned (1)
When the cleaning treatment of at least one of~(4), the cleaning solution of the cleaning treatment temperature is 5 DEG C or more and 100 DEG C or less.
6. the manufacturing method of the chemically reinforced glass as described in above-mentioned any one of 1~5, wherein carry out selected from above-mentioned (1)
When the cleaning treatment of at least one of~(4), the cleaning treatment time is 1 minute~100 minutes.
7. a kind of manufacturing method of chemically reinforced glass, it includes chemical strengthening process, by make the glass containing sodium with
Containing potassium nitrate and selected from by K2CO3、Na2CO3、KHCO3、NaHCO3、K3PO4、Na3PO4、K2SO4、Na2SO4, KOH and NaOH structure
At at least one of group salt or alkali inorganic salts contact, thus make in the Na ion and above-mentioned inorganic salts in above-mentioned glass
K ion carries out ion exchange；Acid treatment process carries out sour processing to above-mentioned glass after above-mentioned chemical strengthening process；At alkali
Science and engineering sequence carries out alkali process to above-mentioned glass after above-mentioned acid treatment process, wherein carries out at above-mentioned acid under wet environment
Series of processes of the science and engineering sequence to above-mentioned alkali process process.
Invention effect
The manufacturing method of chemically reinforced glass of the invention is in the chemistry carried out using the inorganic salts containing specific salt
Strengthen the manufacturing method that process carries out acid treatment process and alkali process process later.First embodiment according to the present invention is led to
The ultrasonic cleaning processing comprising frequency and acoustic pressure in particular range is crossed, caused by preventing because of ultrasonic cleaning
The generation of the damage of submicron order inhibits the reduction of surface intensity improved tremendously, can manufacture and have both intensity and outer
See the chemically reinforced glass of quality.
In addition, second embodiment according to the present invention, by being carried out under wet environment from above-mentioned acid treatment process to upper
The series of processes of alkali process process is stated, can guarantee exterior quality without ultrasonic cleaning as a result, can be manufactured
Have both the chemically reinforced glass of intensity and exterior quality.
Detailed description of the invention
Figure 1A is the chemical strengthening for illustrating the chemical strengthening process comprising carrying out using the inorganic salts containing specific salts
The schematic diagram of the process of the manufacturing method of glass.In addition, Figure 1B is for illustrating comprising utilizing the inorganic salts for not containing specific salts
The schematic diagram of the process of the manufacturing method of the chemical strengthening process of progress, existing chemically reinforced glass.
Fig. 2 is the schematic diagram for illustrating to measure the method for the acoustic pressure in ultrasonic cleaning.
Fig. 3 (a)~Fig. 3 (d) is the schematic diagram for indicating the manufacturing process of chemically reinforced glass of the invention.
Fig. 4 is the schematic diagram for illustrating the method for ball and ring test.
Fig. 5, which is shown, comments the surface intensity of chemically reinforced glass obtained in embodiment or comparative example (composition: glass A)
The result of valence.
Fig. 6, which is shown, comments the surface intensity of chemically reinforced glass obtained in embodiment or comparative example (composition: glass B)
The result of valence.
Fig. 7, which is shown, comments the surface intensity of chemically reinforced glass obtained in embodiment or comparative example (composition: glass C)
The result of valence.
Fig. 8, which is shown, comments the surface intensity of chemically reinforced glass obtained in embodiment or comparative example (composition: glass D)
The result of valence.
Appended drawing reference
11 ultrasonic wave sound pressure meters
12 Sensor sections
13 rinse baths
14,15,16 glass plate
1 glass plate
2 press fixtures
3 bear fixture
10 low-density layers
20 compressive stress layers
30 middle layers
Specific embodiment
Hereinafter, being described in detail to the present invention, but the present invention is not limited to following embodiments, are not departing from this
In the range of the purport of invention, it can arbitrarily be deformed and be implemented.Here, in the present specification, " quality % " and " weight
Measuring % ", " quality ppm " and " weight ppm " is respectively identical meanings.In addition, indicating " weight in the case where being abbreviated as " ppm "
ppm”。
The manufacturing method (hereinafter also referred to as the manufacturing method of the present invention) of chemically reinforced glass of the invention includes: chemistry
Strengthen process, by making the glass containing sodium and containing potassium nitrate and be selected from by K2CO3、Na2CO3、KHCO3、NaHCO3、K3PO4、
Na3PO4、K2SO4、Na2SO4, at least one of the group that constitutes of KOH and NaOH salt or alkali inorganic salts contact, thus make above-mentioned
The K ion in Na ion and above-mentioned inorganic salts in glass carries out ion exchange；Acid treatment process, in above-mentioned chemical strengthening process
Sour processing is carried out to above-mentioned glass later；Alkali process process carries out alkali process to above-mentioned glass after above-mentioned acid treatment process.
[ultrasonic cleaning]
First embodiment of the invention is characterized in that, comprising at the cleaning of at least one of following (1)~(4)
Reason.
(1) during above-mentioned acid treatment process, be 25kHz or more and 80kHz or less using frequency and acoustic pressure is
The cleaning treatment that 80mV ultrasonic wave below carries out；
(2) after above-mentioned acid treatment process and before above-mentioned alkali process process, using frequency be 25kHz or more and
80kHz or less and acoustic pressure are the cleaning treatment that 80mV ultrasonic wave below carries out；
(3) during above-mentioned alkali process process, be 25kHz or more and 80kHz or less using frequency and acoustic pressure is
The cleaning treatment that 80mV ultrasonic wave below carries out；
(4) after above-mentioned alkali process process, be 25kHz or more and 80kHz or less using frequency and acoustic pressure is
The cleaning treatment that 80mV ultrasonic wave below carries out.
The cleaning treatment of above-mentioned (1)~(4) is illustrated below.
About above-mentioned (1), by carrying out ultrasonic cleaning during acid treatment process, thereby, it is possible to from glass surface height
Effect ground removes the attachments such as inorganic salts used in chemical strengthening process, the glass leachable generated in acid treatment process, energy
It is enough to improve the intensity and cleannes that glass is improved by acid processing bring effect.Ultrasonic wave during acid treatment process is clear
The acoustic pressure washed is 80mV or less, preferably 60mV or less, more preferably 40mV or less.By by the acoustic pressure be set as 80mV with
Under, thus, it is possible to inhibit because of ultrasonic cleaning caused by surface intensity reduction.
As a result, can about above-mentioned (2) by carrying out ultrasonic cleaning after acid treatment process and before alkali process process
It is enough that the attachments such as acid used in acid treatment process, glass leachable are efficiently removed from glass surface, it can be improved by alkali
Processing bring effect is to improve the intensity and cleannes of glass.It is carried out after acid treatment process and before alkali process process
The acoustic pressure of ultrasonic cleaning is 80mV or less, preferably 60mV or less, more preferably 40mV or less.By the way that the acoustic pressure is set as
80mV hereinafter, surface intensity caused by thus, it is possible to inhibit because of ultrasonic cleaning reduction.
About above-mentioned (3), by carrying out ultrasonic cleaning during alkali process process, thereby, it is possible to from glass surface height
Effect ground removes the attachments such as acid used in acid treatment process, the glass leachable generated in alkali process process, can be improved
The intensity and cleannes of glass are improved by alkali process bring effect.The acoustic pressure of the ultrasonic cleaning is 80mV or less, excellent
It is selected as 60mV or less, more preferably 40mV or less.By the way that the acoustic pressure is set as 80mV hereinafter, thus, it is possible to inhibit because of ultrasonic wave
The reduction of surface intensity caused by cleaning.
About above-mentioned (4), by carrying out ultrasonic cleaning after alkali process process, thereby, it is possible to from glass surface height
Effect ground removes the attachments such as alkali, glass leachable used in alkali process process, can be improved the intensity and cleannes of glass.
The acoustic pressure of the ultrasonic cleaning is 80mV or less, preferably 60mV or less, more preferably 40mV or less.By the way that the acoustic pressure is set
For 80mV hereinafter, the reduction of surface intensity caused by thus, it is possible to inhibit because of ultrasonic cleaning.
About above-mentioned (1)~(4), the lower limit of the output power of ultrasonic wave is not particularly limited, collateral security exterior quality
Viewpoint considers that acoustic pressure is generally preferably set as 10mV or more.
The acoustic pressure of ultrasonic cleaning can use commercially available ultrasonic wave sound pressure meter (for example, Kaijo company of Co., Ltd. manufactures
11003 type sensor of 19001D type main body) be measured.According to the composition in the position and rinse bath of ultrasonic oscillator, have
When in rinse bath generate acoustic pressure distribution, therefore, rinse bath internal upper part, middle part, lower part respectively manually inswept Sensor section,
Measure maximum acoustic pressure.
The schematic diagram that shall illustrate the measuring method of acoustic pressure is shown in Figure 2.As shown in Fig. 2, upper in rinse bath 13
The glass plate 14 in portion, the glass plate 15 at middle part, lower part glass plate 16 each position, in the direction of the arrow manually inswept ultrasonic wave
The Sensor section 12 of sound pressure meter 11 measures maximum sound pressure.
About above-mentioned (1)~(4), the frequency of ultrasonic wave is 25kHz or more, preferably 38kHz or more.In addition, being 80kHz
It below, is preferably 78kHz or less.By the way that the frequency of ultrasonic wave is set as 25kHz or more and 80kHz hereinafter, available right
The effective cleaning effect of the foreign matter adhered in protection glass process etc..In general, the value of frequency is smaller to be more easy to produce cavitation, more
Cleaning effect can be improved.On the other hand, the value of frequency is bigger, can more reduce the shadow as caused by ultrasonic cleaning to surface intensity
Loudness.
It is not particularly limited, such as can be arranged for the cleaning solution of ultrasonic cleaning about above-mentioned (1)~(4)
It lifts: having used aqueous alkalinity or cleaning agent, pure water, ion exchange water of neutrality of surfactant etc..Exist as above-mentioned (1)
Ultrasonic cleaning and above-mentioned (3) during acid treatment process for the cleaning solution of the ultrasonic cleaning during alkali process process,
From the viewpoint of never interfering acid processing and alkali process, preferably pure water or ion exchange water.As alkalinity or neutral cleaning agent
For, such as can enumerate: on a small quantity containing sodium hydroxide, the cleaning agent of potassium hydroxide, glycols cleaning agent.
About above-mentioned (1)~(4), for the temperature of cleaning solution when as ultrasonic cleaning, it is often preferred that 5 DEG C with
Above, more preferably 10 DEG C or more, in addition, it is often preferred that 100 DEG C or less, more preferably 90 DEG C or less.
About above-mentioned (1)~(4), the time of ultrasonic cleaning is shorter, face caused by being more able to suppress because of ultrasonic cleaning
The reduction of intensity.The time of ultrasonic cleaning is not particularly limited, and can suitably set, it is often preferred that 1 minute~100 points
Clock, more preferably 3 minutes~60 minutes.
[wet environment]
In the first embodiment of the present invention, it is repeatedly carrying out at least one of above-mentioned (1)~(4) cleaning
In the case where reason, the process between the cleaning treatment is preferably carried out under wet environment.Thereby, it is possible to improve intensity and exterior quality.
In addition, in the first embodiment of the present invention, being carried out from acid treatment process to alkali process preferably under wet environment
The series of processes of process, thus, it is possible to further increase exterior quality.For example, in the first embodiment in alkali process process
Later also comprising the work in the case where drying process, before being carried out from acid treatment process to drying process preferably under wet environment
Sequence.
Second embodiment of the present invention is characterized in that, is carried out under wet environment from acid treatment process to alkali process process
Series of processes.By carrying out under wet environment from acid treatment process to the series of processes of alkali process process, even if as a result,
It can also guarantee exterior quality without ultrasonic cleaning.
In the present specification, " series of processes is carried out under wet environment " refer to that maintenance soaks glass for example between each process
Stain state in water or the state that cannot not be maintained at dryly glass while being sprayed water to glass.
Hereinafter, being illustrated to each process in the manufacturing method of the present invention.
[chemical strengthening process]
Chemical strengthening process be process as described below: by make the glass containing sodium with containing potassium nitrate and selected from by
K2CO3、Na2CO3、KHCO3、NaHCO3、K3PO4、Na3PO4、K2SO4、Na2SO4, at least one of the group that constitutes of KOH and NaOH
Thus the contact of the inorganic salts of salt or alkali makes the K ion in Na ion and above-mentioned inorganic salts in above-mentioned glass carry out ion exchange,
To the compressive stress layer after glass surface forms ion exchange.
By above-mentioned ion exchange, ion exchange is carried out to the surface of glass, forms the remaining superficial layer of compression.Specifically
For, pass through the ion exchange alkali metal that the ionic radius of glass pane surface is small at glass transition temperature temperature below
Ion (typically Li ion, Na ion) is replaced into the bigger alkali metal ion of ionic radius (typically, relative to Li ion
For be Na ion or K ion, for Na ion be K ion).As a result, in the remained on surface compression of glass, glass
Intensity improve.
Glass used in the manufacturing method of the present invention contains sodium, as long as having can shape and can lead to
The glass of composition crossing chemical intensification treatment and being strengthened, can be used the glass of various compositions.Specifically, for example can be with
It enumerates: 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 manufacture in the following way: desired glass raw material is thrown
Enter continuous fusion furnace, glass raw material is preferably subjected to heating melting at 1500 DEG C~1600 DEG C, is clarified, is then supplied to
Then forming device moltens glass into plate, and carries out slow cooling.
It should be noted that the forming of glass can use various methods.For example, can be using glass tube down-drawing (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.
The thickness of glass is not particularly limited, in order to which chemical intensification treatment is effectively performed, it is often preferred that 5mm or less,
More preferably 3mm or less.In addition, from the viewpoint for particularly showing the improvement effect by aftermentioned acid processing bring surface intensity
Consider, the thickness of glass is more preferably 1mm or less, particularly preferably 0.7mm or less.On the other hand, the thickness mistake of glass
Bao Shi cannot fully guarantee the intensity of glass, therefore preferably 0.4mm or more sometimes.
In addition, the shape of glass is not particularly limited.Such as the writing board shape with uniform plate thickness can be used, just
The glass of various shapes such as the shape of at least one of face and the back side with curved surface and the three-dimensional shape with bending section etc..
As being not particularly limited for the composition of glass, such as following compositions can be enumerated.
(i) mole % with oxide benchmark indicate form in containing 50%~80% SiO2, 2%~25%
Al2O3, 0~10% Li2O, 0~18% Na2O, 0~10% K2O, 0~15% MgO, 0~5% CaO and 0~5%
ZrO2Glass；
(ii) mole % with oxide benchmark indicate form in containing 50%~74% SiO2, 1%~10%
Al2O3, 6%~14% Na2O, 3%~11% K2O, 2%~15% MgO, 0~6% CaO and 0~5%
ZrO2、SiO2And Al2O3Content add up to 75% or less, Na2O and K2The content of O add up to 12%~25%, MgO and
The glass for adding up to 7%~15% of the content of CaO；
(iii) mole % with oxide benchmark indicate form in containing 68%~80% SiO2, 4%~10%
Al2O3, 5%~15% Na2O, 0~1% K2O, the ZrO of 4%~15% MgO and 0~1%2Glass；
(iv) mole % with oxide benchmark indicate form in containing 67%~75% SiO2, 0~4%
Al2O3, 7%~15% Na2O, 1%~9% K2O, the ZrO of 6%~14% MgO and 0~1.5%2、SiO2And Al2O3's
Content adds up to 71%~75%, Na2O and K2The content of O add up to 12%~20%, it contains containing CaO
Measure the glass less than 1%；
(v) mole % with oxide benchmark indicate form in containing 55.5%~80% SiO2, 8%~20%
Al2O3, 8%~25% Na2O, 0~3% K2O, 0~1% TiO2, 0~5% ZrO2, 1% or more alkaline-earth metal
The glass of RO (RO MgO+CaO+SrO+BaO)；
(vi) mole % with oxide benchmark indicate form in containing 56%~72% SiO2, 8%~20%
Al2O3, 3%~20% B2O3, 8%~25% Na2O, 0~5% K2O, 0~15% MgO, 0~15% CaO and
0~1% TiO2Glass；
(vii) mole % with oxide benchmark indicate form in containing 55.5%~76.5% SiO2, 5%~
20% Al2O3, 8%~25% Na2O, 0~5% K2O, 0.1% or more P2O5, 1% or more alkaline-earth metal RO (RO
For the glass of MgO+CaO+SrO+BaO)；
(viii) mole % with oxide benchmark indicate form in containing 64%~71% SiO2, 2.1%~
4.6% Al2O3, 12%~18% Na2O, 6%~9% CaO, 5%~8% MgO, Na2O and K2The content of O adds up to
For 12%~19% glass；
(ix) mole % with oxide benchmark indicate form in containing 67%~74% SiO2, 0.9%~2%
Al2O3, 10%~14% Na2O, 7%~10% CaO, 5%~8% MgO, Na2O and K2The content of O adds up to
10%~15% glass.
In the manufacturing method of the present invention, chemical strengthening is by making glass and containing potassium nitrate (KNO3) inorganic salts contact
Come carry out.The K ion in Na ion and inorganic salts by thus making glass surface carries out ion exchange, to form high density
Compressive stress layer.For the method for contacting glass with inorganic salts, can on glass be coated with paste salt method,
The method of the aqueous solution of salt is sprayed on glass, makes method of the glass-impregnated in the salt bath for the fuse salt for being heated to fusing point or more
Deng, in these methods, the method that is preferably immersed in fuse salt.
For inorganic salts, preferably the strain point (usual 500 DEG C~600 DEG C) of the glass of chemical strengthening is being carried out below
Inorganic salts with fusing point are in the present invention the inorganic salts containing potassium nitrate (330 DEG C of fusing point).By containing potassium nitrate, by
In the strain point of glass, the following are molten conditions for this, and operate and become easy in use temperature range, therefore preferably.It is inorganic
The content of potassium nitrate in salt is preferably 50 mass % or more.
Inorganic salts also contain selected from by K2CO3、Na2CO3、KHCO3、NaHCO3、K3PO4、Na3PO4、K2SO4、Na2SO4、KOH
And at least one of group of NaOH composition salt or alkali.Wherein, it preferably comprises selected from by K2CO3、Na2CO3、KHCO3And NaHCO3
At least one of group of composition salt.
Above-mentioned salt (hereinafter, otherwise referred to as " flux ") has cutting using Si-O-Si key as the network of the glass of representative
Property.The temperature for carrying out chemical intensification treatment is up to hundreds of DEG C, and therefore, the covalent bond between the Si-O of glass is fitted at such a temperature
Degree cutting, aftermentioned low-densityization processing become easy progress.
It should be noted that the degree of cutting covalent bond is according to glass composition, the type of used salt (flux), progress
The chemical intensification treatments condition such as temperature, time of chemical intensification treatment and it is different, it is believed that selection from 4 covalent bonds that Si extends
The condition of the cut-off degree of 1~2 key be preferred.
Such as using K2CO3In the case where as flux, the content of the flux in inorganic salts is set as 0.1 mole of %
Above, when chemical intensification treatment temperature being set as 350 DEG C~500 DEG C, the chemical intensification treatment time is preferably 1 minute~10 small
When, more preferably 5 minutes~8 hours, further preferably 10 minutes~4 hours.
From the viewpoint of control surface hydrogen concentration, the additive amount of flux is preferably 0.1 mole of % or more, more preferably 1
Mole % or more, particularly preferably 2 moles of % or more.In addition, the saturation of preferably each salt dissolves from the viewpoint of productivity
Below degree.In addition, when flux is excessively added, it is possible to lead to the corrosion of glass.For example, using K2CO3The case where as flux
Under, preferably 24 moles of % or less, more preferably 12 moles of % or less, particularly preferably 8 moles of % or less.
In inorganic salts, other than potassium nitrate and flux, it can contain in the range of not interfering effect of the present invention other
Chemical species, such as can enumerate: the alkali metal chlorizated salts such as sodium chloride, potassium chloride, Boratex, potassium borate or alkali borate
Deng.It is a variety of that they individually can add or combine addition.
Hereinafter, illustrating chemistry for by way of making method of the glass-impregnated in fuse salt carry out chemical strengthening
Strengthen process.
(manufacture 1 of fuse salt)
Fuse salt can be manufactured by process as shown below.
Process 1a: the preparation of potassium nitrate fuse salt
Process 2a: flux is added into potassium nitrate fuse salt
(preparation-of process 1a- potassium nitrate fuse salt)
In process 1a, potassium nitrate is put into container, the temperature of fusing point or more is heated to and is melted, thus prepared molten
Melt salt.Be melted in the fusing point (330 DEG C) of potassium nitrate in the range of boiling point (500 DEG C) at a temperature of carry out.Especially from can
It is more excellent from the viewpoint of the balance and enhanced time of the bearing stress (CS) and compressive stress layer depth (DOL) that assigned to glass
Melting temperature is set as 350 DEG C~470 DEG C by choosing.
Make the container of nitric acid kali fusion that metal, quartz, ceramics etc. can be used.Wherein, excellent from the viewpoint of durability
Metal material is selected, preferred stainless steel (SUS) material from the viewpoint of corrosion resistance.
(process 2a- adds flux-into potassium nitrate fuse salt)
In process 2a, above-mentioned flux is added in the potassium nitrate fuse salt for preparing in process 1a, is kept the temperature at certain
In range, and at the same time by stirring blade etc. so that entirety is mixed in the way of becoming uniform.It is being used together by more than one flux
In the case where, there is no limit can also add order of addition simultaneously.
The temperature of fuse salt is preferably the fusing point of potassium nitrate or more, i.e. 330 DEG C or more, and more preferably 350 DEG C~500 DEG C.
In addition, mixing time is preferably 1 minute~10 hours, more preferably 10 minutes~2 hours.
(manufacture 2 of fuse salt)
In the manufacture 1 of above-mentioned fuse salt, the method that flux is added after the preparation of the fuse salt of potassium nitrate is instantiated, but
Fuse salt can also be manufactured by process as shown below.
Process 1b: the mixed processes of potassium nitrate and flux
Process 2b: the melting of the salt-mixture of potassium nitrate and flux
(mixing-of process 1b- potassium nitrate and flux)
In process 1b, by potassium nitrate and flux investment container, mixed using stirring blade etc..It is molten being used together by more than one
In the case where agent, there is no limit can also add order of addition simultaneously.Container can be used with used in above-mentioned operation 1a
The same container of container.
(melting-of the salt-mixture of process 2b- potassium nitrate and flux)
In process 2b, the salt-mixture heating melting that will be obtained by process 1b.It is melted in fusing point (330 DEG C) and the boiling of potassium nitrate
It is carried out at a temperature of in the range of point (500 DEG C).Especially from can to glass assign bearing stress (CS) and compression
From the viewpoint of the balance and enhanced time of layer depth (DOL), melting temperature is more preferably set as 350 DEG C~470 DEG C.Stirring
Time is preferably 1 minute~10 hours, 10 minutes~2 hours more preferable.
For by fuse salt obtained from above-mentioned operation 1a and process 2a or process 1b and process 2b, due to
Addition flux and in the case where generating precipitate, before the chemical intensification treatment for carrying out glass, stand until the precipitation
Object is deposited in the bottom of container.Exist in the precipitate comprising having exceeded the cation of the flux of amount of saturation solubility, flux
The salt obtained from exchanging in fuse salt.
The Na concentration of above-mentioned fuse salt is preferably 500 weight ppm or more, more preferably 1000 weight ppm or more.By molten
Melting the Na concentration in salt is 500 weight ppm or more, and as a result, by aftermentioned acid treatment process, low-density layer is easy to deepen, because
This is preferably.The upper limit of Na concentration is not particularly limited, and can permit the Na until that can obtain desired bearing stress (CS)
Concentration.
It should be noted that containing being dissolved out from glass in carry out the fuse salt after chemical intensification treatment more than once
Sodium.Therefore, if within the above range, the sodium from glass can be used directly as the source Na, in Na in Na concentration
It, can be inorganic by addition sodium nitrate etc. in the case that concentration is inadequate or in the case where using the not used fuse salt of chemical strengthening
Sodium salt is adjusted.
More than, by above-mentioned operation 1a and process 2a or process 1b and process 2b, fuse salt can be prepared.
Then, chemical intensification treatment is carried out using prepared fuse salt.Chemical intensification treatment is by existing glass-impregnated
Make in fuse salt metal ion (Na ion) in glass and the big metal ion (K ion) of the ionic radius in fuse salt into
Line replacement carries out.The composition for changing glass surface by the ion exchange is capable of forming the pressure of glass surface densification
Stressor layers 20 [Fig. 3 (a)~(b)].Compression is generated by the densification of the glass surface, therefore can be strong by glass
Change.
It should be noted that in fact, the middle layer 30 at the density of chemically reinforced glass from the center for being present in glass is (main
Body) outer rim to the gradually densification of compressive stress layer surface, therefore, between middle layer and compressive stress layer there is no density sharply
The specific boundary of variation.Here, middle layer indicates layer being present in center of glass portion, being clipped by compressive stress layer.Among this
Layer is different from compressive stress layer, is the layer for not carrying out ion exchange.
Chemical intensification treatment can specifically be carried out by following processes 3.
Process 3: the chemical intensification treatment of glass
(chemical intensification treatment-of process 3- glass)
It is molten by what is prepared in above-mentioned operation 1a and process 2a or process 1b and process 2b by preheating glass in process 3
Melt salt to be adjusted to carry out the temperature of chemical strengthening.Then, the glass after preheating is impregnated into fuse salt the stipulated time, then will
Glass lifts from fuse salt, and carries out natural cooling.It should be noted that for glass, preferably at chemical strengthening
Shape processing corresponding with purposes is carried out before reason, the mechanicalness such as processing cutting, end face processing and aperture is processed.
The preheating temperature of glass depends on temperature when being immersed in fuse salt, it is often preferred that 100 DEG C or more.
Carry out chemical strengthening temperature be preferably be reinforced glass strain point (usual 500 DEG C~600 DEG C) hereinafter, in order to
Obtain higher compressive stress layer depth, particularly preferably 350 DEG C or more.
The dip time in fuse salt of glass is preferably 1 minute~10 hours, more preferably 5 minutes~8 hours, into
One step is preferably 10 minutes~4 hours.When for the range, the change of the balancing good of the depth of available intensity and compressive stress layer
Learn strengthened glass.
From the viewpoint of collateral security intensity and exterior quality, utilized preferably between chemical strengthening process and acid treatment process
The cleaning of the progress glass such as industrial water, ion exchange water.The condition of cleaning is different according to used cleaning solution, is using
In the case where ion exchange water, from the viewpoint of completely removing accompanying salt, preferably cleaned at 0 DEG C~100 DEG C.
Ultrasonic wave can be applied when cleaning, for condition, specifically, it is preferable that: frequency is preferably set to 25kHz or more
And 80kHz is hereinafter, be preferably set to 80mV or less for acoustic pressure.
[acid treatment process]
Acid treatment process is the process for carrying out sour processing to glass after above-mentioned chemical strengthening process.The acid processing of glass
Carried out by being immersed in chemically reinforced glass in acid solution, thus, it is possible to by the Na on chemically reinforced glass surface and/
Or K is replaced into H.
Solution is then not particularly limited if it is acidity, and less than 7, used acid can may be pH for weak acid
Strong acid.Specifically, it is preferable that the acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid and citric acid.These acid can be single
It solely uses, can also be applied in combination a variety of.
Carry out the temperature of the sour processing also difference according to the type of used acid or concentration, time, preferably 100 DEG C with
Lower progress.Although the time of the sour processing of progress difference according to type or concentration, the temperature of used acid, from productivity
Viewpoint considers 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 mass of mass %~20 %.
From the viewpoint of collateral security intensity and exterior quality, ultrasonic wave can be applied in acid treatment process.It is handled in acid
In the case where applying ultrasonic wave in process, for specific condition, for example, it is preferable that: frequency is preferably set to
25kHz or more and 80kHz are hereinafter, being preferably set to 80mV or less for acoustic pressure, being more preferably set as 60mV or less.
In addition, ultrasonic cleaning can be carried out during acid treatment process, in this case, for [ultrasonic cleaning]
Speech, preferably carries out ultrasonic cleaning under the above-mentioned condition about (1).
By passing through acid treatment process, also have the surface layer of compressive stress layer 20 modified, specifically in glass surface
The low-density layer 10 [Fig. 3 (b)~(c)] of low-density.Low-density layer is formed in the following way: Na, K from compressive stress layer most
Outer surface is detached from (leaching) instead H enters (displacement).
Low-density layer is removed by aftermentioned alkali process, therefore, the more thick easier quilt of then glass surface of low-density layer
It removes.Therefore, from the viewpoint of glass surface removal amount, the thickness of low-density layer is preferably 5nm or more, more preferably 20nm
More than.The thickness of low-density layer can be controlled by flux density, na concn, temperature, time in chemical strengthening process etc..
From the viewpoint of glass surface removability, 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) measurement
Period, (Δ θ) was found out.The density of low-density layer can be found out by the critical angle (θ c) measured by XRR.It should be noted that simple
Singly by observing the section of glass using scanning electron microscope (SEM), it is also able to confirm that formation and the layer of low-density layer
Thickness.
From the viewpoint of collateral security intensity and exterior quality, work is utilized preferably between acid treatment process and alkali process process
Industry water, ion exchange water etc. carry out the cleaning of glass.In the case where applying ultrasonic wave in cleaning, for [ultrasonic cleaning]
For, ultrasonic cleaning is preferably carried out under the above-mentioned condition about (2).
[alkali process process]
Alkali process process is the process for carrying out alkali process to glass after above-mentioned acid treatment process.Pass through alkali process work
Sequence can remove part or all of [Fig. 3 (c)~(d)] that low-density layer 10 is formed by until acid treatment process.
Alkali process is carried out by being immersed in chemically reinforced glass in alkaline solution, and thus, it is possible to remove low-density layer
Part or all.Solution is then not particularly limited if it is alkalinity, and pH is greater than 7, and weak base, which can be used, also can be used
Highly basic.Specifically, it is preferable that the alkali such as sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate.These alkali can be used alone,
It can be applied in combination a variety of.
Carry out the temperature of the alkali process also difference according to the type of used alkali or concentration, time, preferably 0 DEG C~
100 DEG C, more preferably 10 DEG C~80 DEG C, particularly preferably 20 DEG C~60 DEG C.If in the temperature range, without glass
The risk corroded, therefore preferably.
Although time of alkali process also difference according to the type of used alkali or concentration, temperature is carried out, from production
Preferably 10 seconds~5 hours from the viewpoint of rate, it is 1 minute~2 hours more preferable.Although carry out alkali process solution concentration according to
The type of used alkali or time, temperature and difference, but from the viewpoint of glass surface removability, preferably 0.1 matter
Measure the mass of %~20 %.
From the viewpoint of collateral security intensity and exterior quality, ultrasonic wave can be applied in alkali process process.In alkali process
In the case where applying ultrasonic wave in process, for specific condition, such as it is preferably: frequency is preferably set to
25kHz or more and 80kHz are hereinafter, being preferably set to 80mV or less for acoustic pressure, being more preferably set as 60mV or less.
In addition, ultrasonic cleaning can be carried out during alkali process process, in this case, about [ultrasonic cleaning],
It is preferred that carrying out ultrasonic cleaning according to the above-mentioned condition about (3).
By above-mentioned alkali process, part or all for being infiltrated with the low-density layer of H is removed, and available surface intensity mentions
High chemically reinforced glass.In addition, be present in the scar of glass surface by removing low-density layer also while being removed, therefore,
Think to consider that also contributing to intensity improves from this point.
It should be noted that the amount of the low-density layer removed depends on the condition of alkali process.It is shown in Fig. 3 (d) low close
The form that degree layer 10 is completely removed is removed but it is also possible to be a part of low-density layer 10 and a part remains.From intensity
From the viewpoint of raising, available effect low-density layer is not removed totally, but from steadily ensuring the saturating of glass
It penetrates from the viewpoint of rate, preferably all removes low-density layer.
From the viewpoint of collateral security exterior quality, after alkali process process preferably by industrial water, ion exchange water etc. into
The cleaning of row glass.In the case where applying ultrasonic wave in cleaning, about [ultrasonic cleaning], preferably about the above-mentioned of (4)
Under the conditions of carry out ultrasonic cleaning.
Manufacturing method according to the invention can safely and efficiently obtain surface intensity and significantly improve and have both appearance
The chemically reinforced glass of quality.The manufacturing method of the present invention is preferably as the protection glass for requiring excellent surface intensity and exterior quality
Glass and ultrasonic cleaning are suitable as the 2.5D glass of cleaning method or the manufacturing method of 3D glass etc..
The intensity (surface intensity) for the chemically reinforced glass that manufacturing method through the invention obtains can be according to passing through ball
(Ball on Ring；BoR the BoR intensity of measurement is tested) to be evaluated.The test method and condition of BoR test are specifically
As described below.
By the glass plate of plate thickness t (mm) be configured at diameter 30mm, contact portion with radius of curvature 2.5mm circularity by not
It becomes rusty on the ring that steel is constituted, in the state of making the sphere being made of steel and the contact glass sheet of diameter 10mm, to by quiet
At the center of the ring, the BoR intensity F (N) to the BoR test measurement that the sphere applies load is evaluated under state load-up condition.
Schematic diagram for illustrating the test of BoR used in the present invention is shown in Fig. 4.In BoR test, by glass plate 1
In the state of level mounting, using SUS304 press fixture 2 (hardened steel, diameter 10mm, mirror finish) to glass plate 1 into
Row pressurization, measures the intensity of glass plate 1.
In Fig. 4, SUS304 receiving fixture 3 (diameter 30mm, the curvature R2.5mm of contact portion, contact portion be hardening
Steel, mirror finish) on be horizontally disposed with glass plate 1 as sample.In the top of glass plate 1, setting is for carrying out glass plate 1
The press fixture 2 of pressurization.
From the top of glass plate 1, the middle section to glass plate 1 pressurizes.It should be noted that experimental condition is as follows
It is described.The decrease speed of press fixture 2: 1.0 (mm/ minutes)
At this point, the breaking load (unit N) when glass is destroyed is used as BoR intensity, the average value that 20 times are measured is made
For BoR mean intensity.But in the case where the destruction starting point of glass plate and ball pressing position deviate 2mm or more, by its from
It is excluded in the data for calculating average value.
The chemically reinforced glass that manufacturing method through the invention obtains preferably satisfies F >=1300 × t2, more preferably F >=
1500×t2[in formula, F is by the BoR intensity (N) of BoR test measurement, and t is the plate thickness (mm) of glass substrate].It is strong by BoR
F (N) is spent within the above range, even if also showing that excellent intensity in the case where having carried out thin plate.
In the present specification, it " ensure that exterior quality " to refer in glass surface without the state of the foreign matters such as spot, refer to
Do not have defective state in the case where observing glass surface by visual observation under conditions of 1500 lux of illumination.
The chemically reinforced glass that manufacturing method through the invention obtains preferably does not grind scratch on surface.Here, this
Grinding in invention refers to be smoothed and being ground glass surface using abrasive grain.In addition, grinding the presence or absence of scratch can be with
By utilizing AFM (Atomic Force Microscope；Atomic force microscope) carry out surface observe to judge, at 10 μm
There is no in the case where two or more 5 μm of length or more and 0.1 μm of width or more of scratch in × 5 μm of regions, it is properly termed as table
The state of scratch is not ground in face.
Embodiment
The present invention is concretely demonstrated hereinafter, enumerating embodiment, but the present invention is not limited to these examples.
< evaluation method >
(surface intensity)
For glass surface intensity, BoR intensity is determined according to the test method of above-mentioned ball and ring test and condition.BoR
The plate thickness of the glass of intensity evaluation is set as 0.7mm, to the top surface as the face not contacted with molten metal in float tank
(face T) or the bottom surface opposite with the top surface (face B) is evaluated.
About the BoR intensity F (N) measured, for F >=2000 × t2In the case where be evaluated as " ◎ ", for F >=1500
×t2In the case where be evaluated as "○", for F >=1300 × t2In the case where be evaluated as " △ ", for 1300 × t of F <2The case where
Under be evaluated as "×".
(surface stress)
The value of compressive stress of the compressive stress layer of chemically reinforced glass of the invention and the depth of compressive stress layer can use surface
Stress meter (for example, the former production of folding manufactured FSM-6000) etc. measures.In addition, the depth of compressive stress layer can use use
The ion exchange depth of the measurements such as EPMA (Electron Probe Micro Analyzer, electron probe microanalyzer) comes
Instead of.In embodiment, bearing stress value (CS, unit MPa) and the depth (DOL, unit are μm) of compressive stress layer utilize
The surface stress meter (FSM-6000) of Zhe Yuan manufacturing company manufacture is determined.
(removal amount)
The removal amount thickness of glass is found out in the following way: utilizing analysis electronics Libra (HR-202i；AND manufacture)
The weight of chemical reagent before and after the processing is measured, and carries out thickness conversion using following formula.
(the removal amount thickness of every one side)=[(weight before handling)-(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.
(exterior quality)
Under conditions of 1500 lux of illumination, glass surface is observed by visual observation, and there will be no spot or foreign matters etc. to lack
The case where the defects of sunken situation is denoted as zero, spot will be present or foreign matter is denoted as ×.
The manufacture > of < chemically reinforced glass
[embodiment 1~16 and comparative example 1~7,10~13,16~19 and 21~26]
(chemical strengthening process)
Potassium nitrate 5100g, potassium carbonate 637g, sodium nitrate 220g are added in the cup of SUS, are added using sheathing formula heater
Heat to 450 DEG C, thus be prepared for containing the sodium of 8 moles of % potassium carbonate and 10000 weight ppm using potassium nitrate as main component
Fuse salt.Prepare the glass formed shown in 50mm × 50mm × 0.7mm table 1, is preheated to 200 DEG C~400 DEG C respectively, then
Impregnated 120 minutes in 450 DEG C of fuse salt, carried out ion-exchange treatment, then cool to room temperature near, thus carry out
Chemical intensification treatment.Obtained chemically reinforced glass is washed, for subsequent handling.
The composition (being indicated with a mole % for oxide benchmark) of glass A~D is as described below.
Glass 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%
Glass B:SiO268.0%, Al2O310.0%, Na2O 14.0, MgO 8.0%
Glass C:SiO267%, B2O34%, Al2O313%, Na2O 14%, K2O < 1%, MgO 2%, CaO < 1%
Glass D:SiO268.7%, Al2O33.0%, Na2O 14.2%, K2O 0.2%, MgO 6.2%, CaO 7.8%
(acid treatment process)
For glass A~C, prepare the nitric acid (HNO of 6.0 weight % in beaker3；The manufacture of Northeast chemical company) water
Solution carries out temperature using water-bath and is adjusted to 40 DEG C.Make the nitre of each glass after adjustment obtained in above-mentioned chemical strengthening process
It is impregnated 120 seconds in aqueous acid, carries out sour processing, then cleaned repeatedly using pure water.For glass D, by same
The step of, it is impregnated 600 seconds in the aqueous solution of nitric acid that temperature is adjusted to 60 DEG C.
(alkali process process)
For glass A~C, prepare the sodium hydrate aqueous solution of 4.0 weight % in beaker, carries out temperature using water-bath
Degree is adjusted to 40 DEG C.Make to impregnate 120 in the sodium hydrate aqueous solution of each glass after adjustment obtained in above-mentioned acid treatment process
Second, alkali process is carried out, has then been cleaned repeatedly using pure water.For glass D, by same step, adjusted in temperature
To be impregnated 600 seconds in 60 DEG C of sodium hydrate aqueous solutions.
(ultrasonic cleaning)
Ultrasound has been carried out to glass according to condition shown in table 1 using the supersonic wave cleaning machine with following ultrasonic oscillators
Wave cleaning.26kHz, 600W ultrasonic oscillator, the frequency 40kHz:Branson for having used frequency 26kHz:Kaijo company to manufacture
40kHz, 600W ultrasonic oscillator, the alkaline cleaner of company's manufacture (are diluted using the TL-110 that pure water manufactures Lion company
30 times).
For the acoustic pressure in ultrasonic cleaning: by the above method in [ultrasonic cleaning], utilizing Co., Ltd.
The 11003 type sensor of 19001D type main body of Kaijo company manufacture, passes through manually respectively in rinse bath internal upper part, middle part, lower part
Inswept Sensor section, to determine maximum sound pressure.
[comparative example 8,14,20 and 27]
(chemical strengthening process)
The plate glass that glass shown in 50mm × 50mm × 0.7mm, table 1 forms is preheated to respectively in the lab
350 DEG C~400 DEG C, then made in fuse salt as main component in 450 DEG C of the sodium containing 2000 mass ppm with potassium nitrate
Dipping 120 minutes, carried out ion-exchange treatment, then cool to room temperature near, thus carried out chemical intensification treatment.
[comparative example 9,15 and 28]
Ultrasonic cleaning is carried out after chemical strengthening process under the conditions shown in Table 1, in addition to this respectively with comparative example 8,
14 and 27 are carried out similarly.
Various evaluations have been carried out to the chemically reinforced glass obtained in this way.By the treatment conditions and evaluation of glass
As a result in shown in table 1 and Fig. 5~8.In table 1, " under wet environment " is that "○" expression has carried out handling work from acid under wet environment
Series of processes of the sequence to alkali process process.
As shown in table 1 and Fig. 5~8, compared with the chemically reinforced glass of comparative example, manufacturing method through the invention is obtained
Chemically reinforced glass surface intensity with higher, and ensure that exterior quality.
With the chemical strengthening glass for the comparative example 9,15 and 28 for having carried out ultrasonic cleaning after existing chemical strengthening process
Glass is compared, and the chemically reinforced glass that manufacturing method through the invention obtains has significantly higher surface intensity and exterior quality.
In addition we know, the effect based on first embodiment of the invention under wet environment by carrying out from acid treatment process to alkali process
The series of processes of process and further increase.
In addition, using the fuse salt containing specific salt do not carry out after chemical strengthening ultrasonic cleaning and
It has carried out protecting from acid treatment process to the chemically reinforced glass of the embodiment 1 of the series of processes of alkali process process under wet environment
Exterior quality is demonstrate,proved.On the other hand, ultrasonic wave is not carried out after having carried out chemical strengthening using the fuse salt containing specific salt
It cleans and carries out not under wet environment from acid treatment process to the chemistry of the comparative example 7 of the series of processes of alkali process process
Strengthened glass not can guarantee exterior quality.
In addition, being carried out under wet environment from acid treatment process to the series of processes of alkali process process and in acid processing
It has carried out the embodiment 2 of ultrasonic cleaning and has carried out under wet environment from acid treatment process to a series of of alkali process process
Process and acid processing when and carried out when alkali process ultrasonic cleaning embodiment 3 chemically reinforced glass all have compared with
High surface intensity and it ensure that exterior quality.
For use alkaline cleaner as cleaning solution embodiment 7 and 16 and comparative example 6 and 26 chemical strengthening glass
For glass, with the embodiment 6 and 15 and comparative example 5 handled under the same conditions other than having used pure water and
25 chemically reinforced glass is compared, and higher surface intensity is respectively illustrated.It is thought that because are as follows: the usual surface of alkaline cleaner
Power is low, therefore hampers cavitation generation.
In addition, as shown in Figures 5 and 6, it is known that: by carrying out acid treatment process and alkali after chemical intensification treatment process
Treatment process, surface intensity increase tremendously, but as ultrasonic power output increases, and surface intensity reduces.It is thought that because are as follows:
By ultrasonic cleaning, glass surface is damaged.
According to these results: by the inclusion of frequency specified in (1) in first embodiment of the invention~(4)
And ultrasonic cleaning of the acoustic pressure in particular range is handled or as specified in second embodiment of the present invention wet
It is carried out under environment from acid treatment process to the series of processes of alkali process process, thereby, it is possible to inhibit by using containing specific
Salt inorganic salts chemical strengthening after carry out surface intensity significantly higher brought by acid treatment process and alkali process process because
Ultrasonication and reduce, and can guarantee exterior quality.
Industrial applicability
The manufacturing method of chemically reinforced glass according to the present invention, can be after chemical strengthening without grinding or using
The chemically reinforced glass that surface intensity is very high and exterior quality is excellent is obtained in the case where the etching process of hydrofluoric acid etc..That is, can
To obtain, there is no the bad orders as caused by the expansion of the potential scratch along with the etching process using the progress such as hydrofluoric acid
Or along with grinding grinding scratch, surface intensity and the excellent chemically reinforced glass of exterior quality.
Therefore, unrelated with the presence or absence of the surface scratch of the glass before chemical intensification treatment, potential scratch or degree, Neng Gouying
For all glass, versatility is high.It is each being easy reply and due to that can be handled by dipping in the solution
Kind glass shape, glass of large area etc. are effective.In addition, compared with the etching process for having used hydrofluoric acid etc., peace
Quan Xinggao and at low cost.
The present invention is described in detail and with reference to specific embodiment, but to those skilled in the art
It is readily apparent that various changes, amendment can be subject to without departing from the spirit and scope of the present invention.
The Japanese patent application 2017-121419 that the application was proposed based on June 21st, 2017, content are used as with reference to simultaneously
Enter herein.
Claims (7)
1. a kind of manufacturing method of chemically reinforced glass, it includes:
Chemical strengthening process, by making the glass containing sodium and containing potassium nitrate and be selected from by K2CO3、Na2CO3、KHCO3、
NaHCO3、K3PO4、Na3PO4、K2SO4、Na2SO4, at least one of the group that constitutes of KOH and NaOH salt or alkali inorganic salts connect
Thus touching makes the K ion in Na ion and the inorganic salts in the glass carry out ion exchange；
Acid treatment process carries out sour processing to the glass after the chemical strengthening process；
Alkali process process carries out alkali process to the glass after the acid treatment process,
Wherein, the manufacturing method also include selected from least one of following (1)~(4) cleaning treatment,
(1) during the acid treatment process, using frequency be 25kHz or more and 80kHz or less and acoustic pressure be 80mV with
Under ultrasonic wave carry out cleaning treatment；
(2) after the acid treatment process and before the alkali process process, using frequency be 25kHz or more and 80kHz with
Lower and acoustic pressure is the cleaning treatment that 80mV ultrasonic wave below carries out；
(3) during the alkali process process, using frequency be 25kHz or more and 80kHz or less and acoustic pressure be 80mV with
Under ultrasonic wave carry out cleaning treatment；
(4) after the alkali process process, using frequency be 25kHz or more and 80kHz or less and acoustic pressure be 80mV with
Under ultrasonic wave carry out cleaning treatment.
2. the manufacturing method of chemically reinforced glass as described in claim 1, wherein repeatedly carrying out selected from above-mentioned (1)~(4)
At least one of in the case where cleaning treatment, the process during the cleaning treatment is carried out under wet environment.
3. the manufacturing method of chemically reinforced glass as claimed in claim 1 or 2, wherein wrapped after the alkali process process
Containing drying process, the process before from the acid treatment process to the drying process is carried out under wet environment.
4. the manufacturing method of chemically reinforced glass according to any one of claims 1 to 3, wherein the chemical strengthening glass
Glass is protection glass.
5. the manufacturing method of chemically reinforced glass as described in any one of claims 1 to 4, wherein carry out selected from above-mentioned (1)
When the cleaning treatment of at least one of~(4), the cleaning solution of the cleaning treatment temperature is 5 DEG C or more and 100 DEG C or less.
6. such as the manufacturing method of chemically reinforced glass according to any one of claims 1 to 5, wherein carry out selected from above-mentioned (1)
When the cleaning treatment of at least one of~(4), the cleaning treatment time is 1 minute~100 minutes.
7. a kind of manufacturing method of chemically reinforced glass, it includes:
Chemical strengthening process, by making the glass containing sodium and containing potassium nitrate and be selected from by K2CO3、Na2CO3、KHCO3、
NaHCO3、K3PO4、Na3PO4、K2SO4、Na2SO4, at least one of the group that constitutes of KOH and NaOH salt or alkali inorganic salts connect
Thus touching makes the K ion in Na ion and the inorganic salts in the glass carry out ion exchange；
Acid treatment process carries out sour processing to the glass after the chemical strengthening process；
Alkali process process carries out alkali process to the glass after the acid treatment process,
Wherein, it carries out under wet environment from the acid treatment process to the series of processes of the alkali process process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017121419A JP2019006615A (en) | 2017-06-21 | 2017-06-21 | Manufacturing method of chemically strengthened glass |
| JP2017-121419 | 2017-06-21 |
Publications (2)
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Cited By (4)
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| CN111847901A (en) * | 2020-07-30 | 2020-10-30 | 万津实业(赤壁)有限公司 | Strengthened glass articles and methods of making the same |
| WO2020259087A1 (en) * | 2019-06-25 | 2020-12-30 | 成都光明光电股份有限公司 | Glass, and glass product and preparation method therefor |
| CN112939485A (en) * | 2019-12-10 | 2021-06-11 | 三星显示有限公司 | Window manufacturing method |
| CN113716881A (en) * | 2021-09-04 | 2021-11-30 | 冉康乐 | Production process of toughened glass lens |
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| 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 |
| CN114620928A (en) * | 2022-03-24 | 2022-06-14 | 邱亮 | Toughened glass processing technology |
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| JP2019006615A (en) | 2019-01-17 |
| CN109095789B (en) | 2023-03-28 |
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