CN107129160A - The manufacture method of chemically reinforced glass and chemically reinforced glass - Google Patents
The manufacture method of chemically reinforced glass and chemically reinforced glass Download PDFInfo
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- CN107129160A CN107129160A CN201710102390.7A CN201710102390A CN107129160A CN 107129160 A CN107129160 A CN 107129160A CN 201710102390 A CN201710102390 A CN 201710102390A CN 107129160 A CN107129160 A CN 107129160A
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- Prior art keywords
- glass
- chemically reinforced
- reinforced glass
- amount
- cation amount
- Prior art date
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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
-
- 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
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
Abstract
The present invention relates to the manufacture method of chemically reinforced glass and chemically reinforced glass.Even if being ground it is an object of the invention to provide one kind to glass surface, surface intensity also excellent chemically reinforced glass.The present invention relates to a kind of chemically reinforced glass, it has compressive stress layer on top layer, and meets the condition of following (1)~(5)：(1) there is grinding damage on surface；(2) grain direction index (Stdi) is more than 0.70；(3) the surface silanol groups amount obtained using following formula (i) is less than 1, (surface silanol groups amount)=(the cation amount of inside glass) (the cation amount of glass surface) ... formula (i)；(4) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than 0.070mol/L；(5) surface roughness (Ra) determined using AFM under conditions of 1 μm of square is below 0.35nm.
Description
Technical field
The present invention relates to the manufacture method of chemically reinforced glass and chemically reinforced glass.
Background technology
In digital camera, mobile phone or portable data assistance PDA (Personal Digital Assistants, individual number
Word assistant) etc. in panel display apparatus, contact panel display device, in order to improve the protection of display and attractive in appearance, carry out with into
The protective glass of thin tabular is configured in the front of display for the mode in the region more broader than image displaying part.
According to the lightweight to panel display apparatus and the requirement of slimming, protective glass also requires that thinning in itself.In addition,
For panel display apparatus, contact panel display device, it is desirable to excellent outward appearance, intensity and water proofing property, for protection glass
For glass, in order to meet the purpose, it is desirable to improve surface intensity.
Although the theoretical strength of glass is high, because of damage intensity is greatly reduced, therefore, handed over using by ion
Change etc. and be used as the protection of desired strength in glass surface formation compressive stress layer so as to improve the chemically reinforced glass of surface intensity
Glass.
There is the pollutant (pollution) using the attachment of fuse salt as representative on the glass plate after chemical enhanced.In addition, because
The surface intensity for the being present such that glass reduction of hydrogen (moisture) in glass plate top layer, therefore, generally carries out following process：Pass through
Glass surface after chemical enhanced is ground or is immersed in the method such as to be etched in hydrofluoric acid etc. attached to remove
The pollutant in glass pane surface or the layer containing hydrogen (moisture) of glass pane surface.
Record and chemically reinforced glass plate has been lost in patent document 1 using the aqueous solution containing fluoride compound
The damaging glass plate of impact resistance at quarter.Record to have in patent document 2 and made glass article and essentially without fluoride
The method for the step of water miscible acidic treatment medium contacts and forms acid treatment strengthened glass article.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application Publication 2013-516387 publications
Patent document 2：Japanese Unexamined Patent Application Publication 2014-534945 publications
The content of the invention
Invent problem to be solved
Being ground to the glass surface after chemical enhanced the pollutant or glass of glass surface are attached to so as to remove
In the method for the layer containing hydrogen (moisture) of plate surface, it is possible to cause glass surface to produce damage because of grinding, face is strong on the contrary
Degree reduction.In addition, only ensuring the face of glass by acid treatment as the method described in patent document 1 and patent document 2
During intensity, the silanol group of glass surface is caused because of acid treatment to be increased, therefore pollutant is easily attached to glass surface.Tight
When adhering to pollutant like this before being connected into membrane process, cause pollutant to protrude because of film forming sometimes, cause bad order.
Therefore, even if being ground it is an object of the invention to provide one kind to glass surface and there is grinding damage, face
Intensity is also excellent, and the chemically reinforced glass for inhibiting the pollutant of glass surface to adhere to.
The means used to solve the problem
The inventors discovered that：By by the grain direction index (Stdi) on chemically reinforced glass surface, surface layer of glass
Hydrogen concentration distribution and surface roughness (Ra) are adjusted to specific scope, have grinding damage also being capable of raising even in surface
The surface intensity of strengthened glass is learned, in addition, by the way that surface silanol groups amount is adjusted into specific scope, can suppress chemical enhanced
The pollutant attachment of glass, so as to complete the present invention.
That is, the present invention is as described below.
[1] a kind of chemically reinforced glass, wherein, the chemically reinforced glass has compressive stress layer on top layer, and meets
The condition of following (1)~(5)：
(1) there is grinding damage on surface；
(2) grain direction index (Stdi) is more than 0.70；
(3) the surface silanol groups amount obtained using following formula (i) is less than 1；
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atom of each element of glass surface by using X-ray photoelectron spectroscopy
Concentration is simultaneously obtained using following formula (ii),
The cation amount of inside glass determines glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
The atomic concentration of internal each element is simultaneously obtained using following formula (ii),
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii)；
(4) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L；
(5) surface roughness (Ra) determined using AFM under conditions of 1 μm of square is below 0.35nm.
[2] chemically reinforced glass as described above described in [1], wherein, the texture aspect ratio of the chemically reinforced glass
(Str20) it is more than 0.5.
[3] chemically reinforced glass as described above described in [1] or [2], wherein, the core roughness of the chemically reinforced glass
Depth (Sk) is below 1nm.
[4] chemically reinforced glass as described above described in [1] or [2], wherein, the BOR centre planes of the chemically reinforced glass
Intensity is more than 800N.
[5] chemically reinforced glass as described above described in [1] or [2], wherein, the glass is alumina silicate glass, aluminium boron
Silicate glass or soda-lime glass.
[6] a kind of chemically reinforced glass, wherein, the chemically reinforced glass has compressive stress layer on top layer, and meets
The condition of following (1)~(3)：
(1) grain direction index (Stdi) is more than 0.70；
(2) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L；
(3) surface roughness (Ra) determined using AFM under conditions of 1 μm of square is below 0.35nm.
[7] chemically reinforced glass as described above described in [6], wherein, the chemically reinforced glass meets following condition：
The surface silanol groups amount that (condition) is obtained using following formula (i) is less than 1,
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atom of each element of glass surface by using X-ray photoelectron spectroscopy
Concentration is simultaneously obtained using following formula (ii),
The cation amount of inside glass determines glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
The atomic concentration of internal each element is simultaneously obtained using following formula (ii),
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii).
[8] chemically reinforced glass as described above described in [6] or [7], it has grinding damage on surface.
[9] chemically reinforced glass as described above described in [6] or [7], wherein, the texture aspect ratio of the chemically reinforced glass
(Str20) it is more than 0.5.
[10] chemically reinforced glass as described above described in [6] or [7], wherein, the core of the chemically reinforced glass is coarse
It is below 1nm to spend depth (Sk).
[11] chemically reinforced glass as described above described in [6] or [7], wherein, the BOR centre planes of the chemically reinforced glass
Intensity is more than 800N.
[12] chemically reinforced glass as described above described in [6] or [7], wherein, the glass is alumina silicate glass, aluminium boron
Silicate glass or soda-lime glass.
[13] a kind of manufacture method of chemically reinforced glass, it includes：
By ion-exchange surface layer of glass formation compressive stress layer ion-exchange process and
The glass surface treatment process of alkali process is carried out after above-mentioned ion-exchange process, wherein,
Above-mentioned surface treatment procedure is that above-mentioned glass surface is handled in the way of meeting following (a)~(c)
Surface treatment procedure,
(a) grain direction index (Stdi) is more than 0.70；
(b) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L；
(c) using the AFM surface roughnesses (Ra) determined under conditions of scan size is 1 μm of 1 μ m be 0.35nm with
Under.
[14] manufacture method of chemically reinforced glass as described above described in [13], wherein, the surface treatment procedure be with
The surface treatment procedure that following (d) mode is handled the glass surface is also met,
(d) the surface silanol groups amount obtained using following formula (i) is less than 1,
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atom of each element of glass surface by using X-ray photoelectron spectroscopy
Concentration is simultaneously obtained using following formula (ii),
The cation amount of inside glass determines glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
The atomic concentration of internal each element is simultaneously obtained using following formula (ii),
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii).
[15] manufacture method of chemically reinforced glass as described above described in [13] or [14], wherein, the manufacture method bag
Include it is after above-mentioned surface treatment procedure, be more than 0.70 parsing the grain direction index (Stdi) obtained using afm image
In the case of be judged as suitable sampling check.
[16] manufacture method of chemically reinforced glass as described above described in [13] or [14], wherein, the manufacture method bag
The grinding step for including after above-mentioned ion-exchange process and being ground before above-mentioned surface treatment procedure to glass surface.
Invention effect
According to the present invention chemically reinforced glass, by by the grain direction index (Stdi) on chemically reinforced glass surface,
Hydrogen concentration distribution and surface roughness (Ra) in surface layer of glass are adjusted to specific scope, it is possible to increase chemically reinforced glass
Surface intensity, in addition, by the way that surface silanol groups amount is adjusted into specific scope, the pollutant of glass surface can be suppressed.
Brief description of the drawings
Fig. 1 is to show grain direction index (Stdi) and the figure of the correlation of surface intensity (the average surface intensities of BOR).
Fig. 2 is the schematic diagram illustrated for the method to ball-ring test.
Fig. 3 is the figure for showing texture aspect ratio (Str20) and the correlation of surface intensity (the average surface intensities of BOR).
Fig. 4 is the figure for being used to illustrate core roughness depth (Sk).
Fig. 5 is illustrated in core roughness depth (Sk) [unit：Nm] with the correlation of surface intensity (BOR average surface intensity)
Figure.
Embodiment
The present invention is described in detail below, but the present invention is not limited to following embodiment, is not taking off
In the range of purport from the present invention, it can arbitrarily deform and implement.
<Chemically reinforced glass>
The chemically reinforced glass of the first embodiment of the present invention is that have compressive stress layer on top layer and meet following
(1) chemically reinforced glass of the condition of~(5).
(1) there is grinding damage on surface；
(2) grain direction index (Stdi) is more than 0.70；
(3) the surface silanol groups amount obtained using following formula (i) is less than 1；
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atom of each element of glass surface by using X-ray photoelectron spectroscopy
Concentration is simultaneously obtained using following formula (ii),
The cation amount of inside glass determines glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
The atomic concentration of internal each element is simultaneously obtained using following formula (ii),
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii)；
(4) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L；
(5) surface roughness (Ra) determined using AFM under conditions of 1 μm of square is below 0.35nm.
The chemically reinforced glass of second embodiment of the present invention is that have compressive stress layer on top layer and meet following
(1) chemically reinforced glass of the condition of~(3).
(1) grain direction index (Stdi) is more than 0.70；
(2) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L；
(3) surface roughness (Ra) determined using AFM under conditions of 1 μm of square is below 0.35nm.
The chemically reinforced glass of the present invention has the compressive stress layer by ion-exchange formation on top layer.Compressive stress layer is
Refer to by contact the inorganic salts such as the glass as raw material and potassium nitrate and make K in the Na ions and inorganic salts of glass surface from
Son carries out high-density layer formed by ion exchange.
[grinding damage]
The chemically reinforced glass of the present invention can have grinding damage on surface.Here, the grinding in the present invention refers to profit
Glass surface is ground with abrasive particle and smoothed.The method of surface grinding is not particularly limited.In addition, grinding damage
The presence or absence of can be by using AFM (Atomic Force Microscope；AFM) surface observation judge,
In the case of the grinding damage that there is more than 5 μm of one or more length in 5 μ m, 5 μm of regions, it is properly termed as having on surface
The state of grinding damage.
[grain direction index (Stdi)]
Grain direction index (Stdi) is to represent the texture (property that finished surface equably has in glass surface formation
Matter, state) directionality good and bad index, take the value from 0 to 1.In the case where texture has predominant direction, Stdi is approached
0.On the other hand, in the case where texture does not have directionality, Stdi is close to 1.That is, have in the texture as grinding damage
In the case of predominant direction, Stdi takes the value close to 0.But it is believed that by making, grinding damage is smoothened, texture becomes unclear
Chu, Stdi is close to 1.
The present inventor to Stdi and surface intensity [BOR (ball-ring) surface intensity determined by ball described later-ring test, below
Also referred to as BOR surface intensities] correlation analyzed, as a result find that there is correlation as shown in Figure 1.As shown in figure 1,
Stdi is higher closer to 1 surface intensity.The Stdi of the chemically reinforced glass of the present invention is more than 0.70, preferably more than 0.75,
More preferably more than 0.80.
For the chemically reinforced glass of the present invention, it is believed that by Stdi be the scope, grinding damage is smoothened, face
Intensity is improved.Stdi can using AFM (AFM) obtain shape image after using image analysis software (for example,
The SPIP of Image Metrology companies manufacture) obtain.
[ball-ring test]
Schematic diagram for being illustrated to ball-ring test is shown in Fig. 2.In ball-ring (Ball on Ring；BOR) try
In testing, in the state of the level of glass plate 1 is loaded, press fixture 2 (hardened steel, diameter 10mm, mirror manufactured using SUS304
Face is finished) glass plate 1 is pressurizeed, and the surface intensity of glass plate 1 is measured.
In Fig. 2, (diameter 30mm, the curvature R2.5mm of contact site, contact site are to quench to the support fixture 3 manufactured in SUS304
Fiery steel, minute surface finishing) on be horizontally disposed with as sample glass plate 1.It is provided in the top of glass plate 1 to glass plate 1
The press fixture 2 pressurizeed.
The middle section of glass plate 1 is pressurizeed from the top of glass plate 1.It should be noted that experimental condition is as follows
It is shown.
The decrease speed of press fixture 2：1.0 (mm/ minutes)
Now, the breaking load (unit N) when glass is destroyed is as BOR surface intensities, by the average value of 20 measure
It is used as the average surface intensities (BOR mean intensities) of BOR.But, by the destruction starting point of glass plate apart from more than ball pressing position 2mm
Situation is excluded from the data for calculating average value.
The average surface intensities of the BOR of the chemically reinforced glass of the present invention are preferably more than 800N, and more preferably more than 900N is special
You Xuanwei not more than 1000N.
[surface silanol groups amount]
The present invention first embodiment chemically reinforced glass surface silanol groups amount for less than 1, preferably 0.9 with
Under, more preferably less than 0.85.
The surface silanol groups amount of the chemically reinforced glass of second embodiment of the present invention is preferably less than 1, more preferably
For less than 0.9, more preferably less than 0.85.
[surface silanol groups quantity measuring method]
Surface silanol groups amount by it is following 1)~5) the step of obtain.
1) atomic concentration of each element of glass surface is determined using X-ray photoelectron spectroscopy (XPS).
2) the cation amount of glass surface is calculated using following formula (ii).
3) after being sputtered using C60, the atom that each element of inside glass is determined using X-ray photoelectron spectroscopy is dense
Degree.
4) the cation amount of inside glass is calculated using following formula (ii).
5) using formula (i), the cation amount of inside glass subtracts the cation amount of glass surface, obtains surface silanol groups
Amount.
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii)
It is less than 1 by above-mentioned surface silanol groups amount, pollutant is difficult to adhere to, after the cleaning that can suppress protective glass
Film formation process in pollutant.
[hydrogen concentration]
On the chemically reinforced glass of the present invention, the hydrogen concentration distribution in surface layer of glass is in specific scope.It is specific and
Speech, the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass be less than 0.070mol/L,
Preferably below 0.060mol/L.0.070mol/L is less than by hydrogen concentration C, it is possible to increase the surface intensity of chemically reinforced glass.
Surface intensity on glass, it is known that the surface intensity of glass is reduced because of the presence of the hydrogen (moisture) in surface layer of glass,
But intensity decreases behind chemical intensification treatment sometimes.Carry out the result presumption of various researchs：It is primarily due to gas
Moisture in atmosphere enters glass and generates chemical imperfection.
When hydrogen concentration in surface layer of glass is high, hydrogen in the form of Si-OH to enter in the Si-O-Si key networks of glass, Si-O-
Si keys are cut off.Think：When hydrogen concentration in surface layer of glass is high, the cut-off part of Si-O-Si keys is increased, easily generation chemistry
Defect, surface intensity reduction.
Hydrogen concentration C is particular range in the region of X=0.1 μm~0.4 μm of the depth started at from outmost surface.By from
Although son exchanges the thickness of the compressive stress layer formed depending on chemical enhanced degree, the shape in the range of 5 μm~50 μm
Into.Moreover, the entrance depth of hydrogen in glass depends on diffusion coefficient, temperature and time, for the inlet of hydrogen, except
Also influenceed beyond these by the amount of moisture in atmosphere.On the hydrogen concentration after chemical enhanced, outmost surface highest, towards not formed
The deep (main body) of compressive stress layer is gradually reduced.At outmost surface (X=0 μm), moisture concentration be possible to because through when it is rotten and become
Change, therefore, it is particular range that hydrogen concentration C is made in the region of near surface (X=0.1 μm~0.4 μm) for thinking the not influence.
[hydrogen concentration distribution assay method]
Here, hydrogen concentration distribution (the H in surface layer of glass2O converted scores, mol/L) it is to be determined under the conditions of following analysis
Distribution.Secondary ion mass spectrometry (Secondary Ion Mass are used in the measure of hydrogen concentration distribution in surface layer of glass
Spectrometory：SIMS).
In the case where obtaining quantitative hydrogen concentration distribution using SIMS, it is necessary to standard specimen known to hydrogen concentration.Below
Describe the preparation method and hydrogen concentration quantitative approach of standard specimen.
1) part for the glass of measure object is cut out.
2) more than 50 μm of the region from surface of the glass cut out is removed by grinding or chemical etching.Removing is handled
Can all it be carried out to two-sided.That is, two-sided removing thickness amounts to more than 100 μm.Using the removing handle after glass as
Standard specimen.
3) infra-red sepectrometry (Infrared spectroscopy are implemented to standard specimen：IR), IR spectrograms are obtained
3550cm-1The absorbance height A of neighbouring summit3550And 4000cm-1Absorbance height A4000(baseline).
4) the thickness of slab d (cm) of the measurement of plate thickness device bioassay standard samples such as micrometer is utilized.
5) S.Ilievski et al., Glastech.Ber.Glass Sci.Technol. are referred to, 73 (2000) 39 will
The H of glass2O infrared actual extinction coefficient epsilonpract[L/ (molcm)] is set to 75, and the hydrogen of standard specimen is obtained using formula (a)
Concentration (H2O converts, mol/L).
The hydrogen concentration of standard specimen=(A3550-A4000)/(εpractD) ... formula (a)
Standard specimen known to the hydrogen concentration obtained by the glass of measure object and by the above method is filled to SIMS simultaneously
Interior transport is put, is measured successively, is obtained1H-With30The depth direction distribution of Si- intensity.Then, use1H-Distribution divided by30Si-
Distribution, is obtained1H-/30The depth direction distribution of Si- strength ratios.
By standard specimen1H-/30The depth direction distribution of Si- strength ratios, is calculated in region of the depth from 1 μm to 2 μm
Be averaged1H-/30Si- strength ratios, to make the standard curve (mark of a level of the value and hydrogen concentration by way of origin
The standard curve of quasi- sample).Using the standard curve, by the longitudinal axis of the distribution of the glass of measure object1H-/30Si- strength ratios
It is transformed to hydrogen concentration.Thus, the hydrogen concentration distribution of the glass of measure object is obtained.
It should be noted that SIMS and IR condition determination is as described below.
[SIMS condition determination]
Device：The ADEPT1010 of ULVACPHI companies manufacture
Primary ion species：Cs+
The accelerating potential of primary ion：5kV
The current value of primary ion：500nA
The incidence angle of primary ion：Normal relative to sample face is 60 °
The raster size of primary ion：300×300(μm2)
The polarity of primary ion：It is negative
The detection zone of primary ion：60×60(μm2) (the 4% of the raster size of primary ion)
Electrostatic analyzer input lens (ESA Input Lens)：0
Use neutralization rifle
Transverse axis is transformed to the method for depth from sputtering time：Utilize contact pin type surface shape measuring device (Veeco company systems
The Dektak150 made) depth for analyzing arc crater is measured, obtain the sputter rate of primary ion.Using the sputter rate,
Transverse axis is transformed to depth from sputtering time.
1H-Field shaft potential (Field Axis Potential) during detection：The optimum value of each device is likely to occur change
Change.Measure person is noted while setting the value of field shaft potential with so that background is substantially eliminated.
[IR condition determination]
Device：The Nic-plan/Nicolet 6700 of Thermo Fisher Scientific companies manufacture
Resolution ratio：4cm-1
It is accumulative：16
Detector：TGS detectors
[surface roughness (Ra)]
On the chemically reinforced glass of the present invention, determined using AFM under conditions of scan size is 1 μ m, 1 μm of square
Surface roughness (Ra) be below 0.35nm, more preferably preferably below 0.3nm, below 0.2nm.Pass through surface roughness
(Ra) it is below 0.35nm, it is possible to increase the surface intensity of chemically reinforced glass.
[texture aspect ratio (Str20)]
Texture aspect ratio (Str20) can be obtained as follows.I.e., it is possible to obtain shape graph using AFM (AFM)
Picture, then using image analysis software (the SPIP image analysis softwares version 6.4.3 of Image Metrology companies manufacture),
Implement smooth (レ べ リ Application グ) processing and the L- filtering process (2.0 μm of ISO values) of shape image, obtained using roughness parsing
Texture aspect ratio (Str20).
The present inventor is analyzed Str20 and the correlation of surface intensity (the average surface intensities of BOR), as a result finds exist such as
Correlation shown in Fig. 3.As shown in figure 3, Str20 is higher closer to 1 surface intensity.The chemically reinforced glass of the present invention
Str20 is preferably more than 0.5, more preferably more than 0.6, more preferably more than 0.65, particularly preferably more than 0.75.
In addition, the Str20 of the chemically reinforced glass of the present invention is the scope, it is taken as that being damaged with concavo-convex small grinding
Wound can not confirm the glass of grinding damage.
[core roughness depth (Sk)]
Core roughness depth (Sk) (DIN 4776) is the index on concavo-convex deviation.Ai Bute (ア shown in Fig. 4
ボ ッ ト) bearing curve (ベ ア リ Application グ song Line) in the curve histogrammic integrated value of distribution (height) proximal line in, extraction
Reach that " Sk " shown in Fig. 4 in the case of the line of minimum slope is core roughness depth, " Spk " is reduces summit height
The small high さ of サ ミ ッ ト of (Shrink), " Svk " is the small high さ of バ レ ー of diminution the lowest point height (Shrink).
The present inventor is analyzed Sk and the correlation of surface intensity (the average surface intensities of BOR), is as a result found that presence
Correlation as shown in Figure 5.The Sk of the chemically reinforced glass of the present invention is preferably below 1nm.Think：The model is in by Sk
Enclose, the ratio increase shared by small bumps, surface intensity is improved.Sk can obtain shape image using AFM (AFM)
Asked afterwards using image analysis software (such as the SPIP image analysis softwares version 6.4.3 of Image Metrology companies manufacture)
Go out.
(glass composition)
As long as the glass used in the present invention contains sodium, as long as having can shape, can utilize chemical enhanced place
Managing the composition strengthened can be with using the glass of various compositions.Specifically, such as alumina silicate glass, sodium can be enumerated
Lime glass, borosilicate glass, lead glass, alkali barium glass and aluminium borosilicate glass etc..Wherein, preferably alumina silicate glass,
Aluminium borosilicate glass and soda-lime glass.
The manufacture method of glass is not particularly limited, can by by desired frit put into continuous melting stove in,
Frit is subjected to heating fusing, clarification at preferably 1500 DEG C~1600 DEG C, then will be molten after supply to building mortion
Melt forming of glass for tabular, and annealed, thus manufactured.
It should be noted that various methods can be used in the shaping of glass.It is for instance possible to use glass tube down-drawing (for example,
Overflow downdraw, slot draw method and traction method (リ ド ロ ー methods) etc. again), float glass process, the various shaping sides such as roll-in method and pressing
Method.
The thickness of glass is not particularly limited, in order to effectively carry out chemical intensification treatment, it is often preferred that below 5mm,
More preferably below 3mm.
In addition, the shape of the glass used in the present invention is not particularly limited.Can for example use has uniform thickness of slab
At least one of writing board shape, surface and the back side have the shape of curved surface and the three-dimensional shape with bending section etc. etc. various
The glass of shape.
As the composition of the chemically reinforced glass of the present invention, it is not particularly limited, the group of for example following glass can be enumerated
Into.
(i) by represented by mole % constitute in terms of, contain 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) by represented by mole % constitute in terms of, contain 50%~74% SiO2, 1%~10% Al2O3, 6%~
14% Na2O, 3%~11% K2O, 2%~15% MgO, 0%~6% CaO and 0%~5% ZrO2, SiO2With
Al2O3Content add up to less than 75%, Na2O and K2O content adds up to 12%~25%, MgO and CaO content is added up to
7%~15% glass
(iii) by represented by mole % constitute in terms of, contain 68%~80% SiO2, 4%~10% Al2O3, 5%
~15% Na2O, 0%~1% K2O, 4%~15% MgO and 0%~1% ZrO2Glass
(iv) by represented by mole % constitute in terms of, contain 67%~75% SiO2, 0%~4% Al2O3, 7%~
15% Na2O, 1%~9% K2O, 6%~14% MgO and 0%~1.5% ZrO2, SiO2And Al2O3Content add up to
For 71%~75%, Na2O and K2O content adds up to 12%~20%, and its content is less than 1% in the case of containing CaO
Glass
<The manufacture method of chemically reinforced glass>
The manufacture method of the chemically reinforced glass of the present invention includes：
By ion-exchange surface layer of glass formation compressive stress layer ion-exchange process and
The glass surface treatment process of alkali process is carried out after above-mentioned ion-exchange process.
Surface treatment procedure is the surface treatment work handled in the way of meeting following (a)~(c) glass surface
Sequence.Additionally, it is preferred that being the surface treatment procedure handled in the way of meeting following (d) glass surface.
(a) grain direction index (Stdi) is more than 0.70.
(b) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L。
(c) it is using the AFM surface roughnesses (Ra) determined under conditions of scan size is 1 μ m, 1 μm of square
Below 0.35nm.
(d) the surface silanol groups amount obtained using following formula (i) is less than 1,
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atom of each element of glass surface by using X-ray photoelectron spectroscopy
Concentration is simultaneously obtained using following formula (ii).
The cation amount of inside glass determines glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
The atomic concentration of internal each element is simultaneously obtained using following formula (ii).
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii)
Hereinafter, each operation is illustrated.
[ion-exchange process]
The chemically reinforced glass of the present invention has in glass surface passes through compressive stress layer formed by ion exchange.In ion
In exchange process, ion exchange is carried out to the surface of glass, the superficial layer for remaining compression is formed.Specifically, in vitrifying
At temperature below transition temperature, by ion exchange, (it is typically by the small alkali metal ion of the ionic radius of surface layer of glass
Li ions, Na ions) be replaced as the larger basic ion of ionic radius (typically, for Li ions be Na ions or K ions, it is right
In Na ions be K ions).Thus, in the remained on surface compression of glass, the surface intensity of glass is improved.
The method of ion-exchange treatment is not particularly limited, and can use known method.It is used as ion-exchange treatment
Method, as long as the Li of surface layer of glass can be made2O or Na2The O and Na in fuse salt2O or K2O carries out the method for ion exchange just
It is not particularly limited, can enumerates for example：By glass-impregnated after the heating contain potassium nitrate (KNO3) fuse salt in side
Method.
The condition of ion-exchange treatment is not particularly limited, although different according to the thickness of glass, but temperature conditionss
Preferably less than 520 DEG C, more preferably less than 500 DEG C, additionally, it is preferred that for more than 350 DEG C, more preferably more than 400 DEG C.
In addition, the time for carrying out ion-exchange treatment is preferably 1 hour~72 hours, more preferably 2 hours~24 hours.
In order to improve productivity ratio, preferably less than 12 hours.As fuse salt, such as KNO can be enumerated3Deng.
Specifically, for example, being typically the KNO by glass at 400 DEG C~500 DEG C31 hour~72 are impregnated in fuse salt
Hour.In addition, after ion-exchange treatment, the purpose of the attachments such as the fuse salt of glass etc. is attached to for removing, preferably by
Water is cleaned.
[grinding step]
In the manufacture method of the chemically reinforced glass of the present invention, it can be included in after above-mentioned ion-exchange process and aftermentioned
Surface treatment procedure before the grinding step that is ground to glass surface.Grinding step is while ground slurry is supplied
The process being ground using grinding pad to glass.Grinding condition is not particularly limited, and can reach desired rough surface
Carried out under conditions of degree.By being ground to glass surface, the macroscopic damage of glass surface is removed.
Grinding step can make proportion 0.9 for example, by being dispersed in water the cerium oxide of about 0.7 μm of average grain diameter
Slurry, the surface of glass is entered under conditions of grinding pressure is 10kPa using the grinding pad of non-woven fabric type or suede type
The general methods such as grinding of the row per more than 0.5 μm of one side are carried out.
Glass surface is entered using the grinding abrasive particle that the mean particle diameter (d50) of cerium oxide is usually 0.5 μm~1.5 μm
In the case of row grinding, if remaining the grinding damage produced by the grinding in glass surface, surface intensity is likely to decrease, but
It is that, by carrying out surface treatment procedure described later after grinding step, the grinding damage can be made thinning and make Stdi be defined
Scope, thus improves surface intensity.
[surface treatment procedure]
In the manufacture method of the chemically reinforced glass of the present invention, preferably carry out including alkali process after ion exchange treatment
Surface treatment.Furthermore it is possible to which alkali process and acid treatment or etching process are combined.Think the water by alkali process removing surface
Layer is closed, the surface that glass surface crackle is difficult extension can be obtained.It is additionally contemplated that：By alkali process, surface silanol groups are formed
Amount meets the top layer of above-mentioned specific relational expression (i), the pollutant thus, it is possible to suppress to be attached to glass surface.
By above-mentioned surface treatment, the hydrogen in surface layer of glass is removed, hydrogen concentration C reaches defined scope.It is additionally contemplated that：It is logical
Above-mentioned surface treatment is crossed, while also removing the damage for being present in glass surface, Stdi and surface roughness (Ra) reach defined
Scope, thus surface intensity raising.
More than 5nm, more preferably more than 50nm are preferably generally by being surface-treated the surface removal amount produced.By inciting somebody to action
Surface removal amount is set as more than 5nm, in the case where there is grinding damage, can reduce the bumps produced by the damage, energy
Enough manufacture the high chemically reinforced glass of surface intensity.Surface removal amount can be by suitably adjusting the group for chemical enhanced glass
Temperature of solution or concentration for being used into, surface treatment etc. are adjusted.
(alkali process)
Alkali process is carried out by making chemically reinforced glass be immersed in alkaline solution.As long as solution is alkalescence just without spy
Do not limit, the pH of solution both can use weak base to use highly basic more than 7.Specifically, preferably lithium hydroxide,
The alkali such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, ammonia or organic amine.These alkali, which both can be used alone, to be combined
Using a variety of.Furthermore it is possible to add acylate etc. as chelating agent.
Although the temperature for carrying out alkali process is different according to species or concentration, the time of used alkali, it is preferred that being
10 DEG C~80 DEG C, more preferably 20 DEG C~70 DEG C, particularly preferably 40 DEG C~60 DEG C.If the temperature range, then glass is not
It can corrode, therefore preferably.
Although the time for carrying out alkali process is different according to species or concentration, the temperature of used alkali, from production
It is preferably 1 minute~120 minutes, more preferably 1 minute~60 minutes from the viewpoint of rate.Carry out the concentration of the solution of alkali process
Although according to the species of used alkali, the time, temperature and it is different, from the viewpoint of glass surface removability be preferably
The mass % of 0.1 mass %~10 mass %, more preferably 1 mass %~5.
(acid treatment)
Acid treatment can be by making chemically reinforced glass dipping carry out in an acidic solution.As long as solution does not just have for acidity
There is special limitation, the pH of solution is less than 7, and used acid both can be that weak acid can also be strong acid.Specifically, preferably
The acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid or citric acid.These acid both can be used alone and can also combine
Using a variety of.
Although the temperature for carrying out acid treatment is different according to used sour species or concentration, time, it is preferred that
Less than 100 DEG C progress.Although the time for carrying out acid treatment is different according to used sour species or concentration, temperature,
It it is preferably 10 seconds~5 hours, more preferably 1 minute~2 hours from the viewpoint of productivity ratio.
Although carry out acid treatment solution concentration according to used sour species, the time, temperature and it is different, it is excellent
The concentration for selecting the possibility of container corrosion small, specifically the mass % of preferably 0.1 mass %~20.
(etching process)
As the etching solution used in etching process, the aqueous solution of the chemicals containing glass biodissolution is used.It is used as glass
The deliquescent chemicals of glass, preferably comprises the aqueous solution of fluoride.As fluoride, can enumerate for example hydrogen fluoride, ammonium fluoride,
Potassium fluoride and sodium fluoride etc..In addition, at least one of inorganic acid and organic acid can be contained in these aqueous solution.It is used as nothing
Machine acid, one or more can selects from hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid etc., as organic acid, can from acetic acid with
Selected in butanedioic acid etc. one or more kinds of.
Etch-rate is preferably below 0.1 μm/minute, below more preferably 0.05 μm/minute.By the way that etch-rate is set
It is set to below 0.1 μm/minute, the small chemically reinforced glass of the roughness of glass surface can be manufactured.Etch-rate can pass through
Suitably adjust for the composition of glass of ion-exchange process, the temperature of etching solution or concentration etc. to be adjusted.
Etch temperature is preferably generally 10 DEG C~60 DEG C, more preferably 20 DEG C~40 DEG C.In addition, etching period is generally preferable
For 30 seconds~30 minutes, more preferably 1 minute~10 minutes.On the condition of these etchings, those skilled in the art can be with
Material according to used glass etc. suitably selects to cause not evolution reaction product.
The manufacture method of chemically reinforced glass is different according to purposes, is used as the surface treatment after above-mentioned ion-exchange process
Other processes beyond process, are not particularly limited.It is following to show one, but the present invention is not limited to the example.
First, by the glass blanket of preparation by cutting, perforate, otch, grinding or gently the process such as chamfering (yarn face takes り) into
Shape is desired size, the shape finally finished.Now, in order to improve subsequent handling operability and cut down technique into
This, can be previously cut to the size bigger than the desired size finally finished, after whole manufacturing procedures terminate, shaping is scheduled to last
Size, the shape of prestige.
Glass after shaping carried out by ion-exchange process it is chemical enhanced, then by surface treatment procedure except depolluting
Thing and the layer containing moisture, so as to obtain chemically reinforced glass.To chemically reinforced glass carry out for example printing, antireflection coating and
Laminating of functional membrane etc., so as to manufacture protective glass.After surface treatment procedure, it can carry out asking using afm image parsing
The grain direction index (Stdi) gone out be more than 0.70 in the case of be judged as suitable sampling check.
The chemically reinforced glass of the present invention can be used in what is used in mobile phone, digital camera, on-vehicle display etc.
The display protective glass of panel display apparatus, contact panel display device etc..
Embodiment
Embodiments of the invention are specifically illustrated below, but the present invention is not limited to these embodiments.
<Evaluation method>
Various evaluations in the present embodiment are carried out by analysis method as follows.
[removal amount]
The removal amount thickness of glass is by using analysis electronic balance (HR-202i；AND is manufactured) determine before agent treatment
Weight afterwards, and carry out thickness conversion using following formula and obtain.
(the removal amount thickness per one side)=[(before processing weight)-(weight after processing)]/(specific gravity of glass)/(process face
Product)/2
Now, specific gravity of glass is set to 2.41 (g/cm3) calculated.
[grain direction index (Stdi)]
First, AFM (PA400 of Seiko Instruments companies manufacture), mode determination are utilized：Rap
Pattern, scan size：11 μm of μ m, sweep speed：1Hz, cantilever：Cantilever (SI-DF40 of SII companies manufacture) is obtained
Shape image.Then, image analysis software (the SPIP image analysis software versions of Image Metrology companies manufacture are utilized
6.2.6) implement the smooth processing of shape image, grain direction index (Stdi) is obtained by Roughness analysis.
[texture aspect ratio (Str20)]
First, AFM (PA400 of Seiko Instruments companies manufacture), mode determination are utilized：Rap
Pattern, scan size：11 μm of μ m, sweep speed：1Hz, cantilever：Cantilever (SI-DF40 of SII companies manufacture) is obtained
Shape image.Then, image analysis software (the SPIP image analysis software versions of Image Metrology companies manufacture are utilized
6.2.6) implement the smooth processing of shape image, texture aspect ratio (Str20) is obtained by Roughness analysis.
[core roughness depth (Sk)]
First, AFM (PA400 of Seiko Instruments companies manufacture), mode determination are utilized：Rap
Pattern, scan size：11 μm of μ m, sweep speed：1Hz, cantilever：Cantilever (SI-DF40 of SII companies manufacture) is obtained
Shape image.Then, image analysis software (the SPIP image analysis software versions of Image Metrology companies manufacture are utilized
6.2.6) implement the smooth processing of shape image, core roughness depth (Sk) is obtained by bearing curve.
[surface intensity]
Glass surface intensity passes through ball-ring (Ball on Ring；BOR) experiment is measured.Shown in Fig. 2 for this
The schematic diagram that the ball-ring test used in invention is illustrated.In the state of the level of glass plate 1 is loaded, SUS304 is used
The press fixture 2 (hardened steel, diameter 10mm, minute surface finishing) of manufacture is pressurizeed to glass plate 1, determines the face of glass plate 1
Intensity.
In Fig. 2, (diameter 30mm, the curvature R2.5mm of contact site, contact site are to quench to the support fixture 3 manufactured in SUS304
Fiery steel, minute surface finishing) on be horizontally disposed with as sample glass plate 1.It is provided in the top of glass plate 1 to glass plate 1
The press fixture 2 pressurizeed.
In the present embodiment, central area of the top of the glass plate 1 obtained from embodiment and comparative example to glass plate 1
Pressurizeed in domain.It should be noted that experimental condition is as described below.The decrease speed of press fixture 2：1.0 (mm/ minutes)
Now, the breaking load (unit N) when glass is destroyed is as BOR surface intensities, by the average value of 20 measure
It is used as the average surface intensities of BOR.But, by destruction more than the start point distance ball pressing position 2mm of glass plate situation from for calculating
Excluded in the data of average value.
[hydrogen concentration]
Hydrogen concentration distribution is determined according to the method described in above-mentioned [hydrogen concentration distribution assay method].
[surface silanol groups amount]
According to the method described in above-mentioned [surface silanol groups quantity measuring method], X-ray photoelectron spectroscopy is utilized
(XPS) analysis of glass surface is carried out, surface silanol groups amount is determined.It is as follows on XPS analysis method and apparatus.
(XPS analysis)
Device：The ESCA5500 of ULVACPHI companies manufacture
For each sample face, wide range is determined first, confirmation whether there is surface contaminant, then for C (carbon), O (oxygen), Na
(sodium), Mg (magnesium), Al (aluminium), Si (silicon) and K (potassium) determine narrow spectrum, and calculate the surface composition and surface silanol groups of glass
The Si standard values of amount.Condition determination is as described below.
Step resolution：0.5eV/ is walked
Logical energy：117.4eV
Analyzed area：800 μm of Φ of diameter
[surface roughness (Ra)]
Surface roughness (Ra) utilizes AFM (PA400 of Seiko Instruments companies manufacture), measure
Pattern：Tapping-mode, scan size：11 μm of μ m, sweep speed：1Hz, cantilever：Cantilever (the SI- of SII companies manufacture
DF40 shape image) is obtained, Ra is obtained.
[wetability]
Using the PCA-1 for interface science company manufacture of coordinating, 2 μ L water are supplied to glass surface, contact angle is determined, to wetting
Property is evaluated.
<Test example 1>
(making of glass plate)
The glass for manufacturing following compositions using float glass process causes thickness of slab to be 0.7mm, and cuts into 50mm × 50mm, so as to make
Go out glass plate.
Composition：Contain 64% SiO in terms of mole %2, 7.5% Al2O3, 13% Na2O, 11% MgO composition
In following examples, appropriately combined following each operations are carried out.
(ion-exchange process)
Glass plate is impregnated in KNO3In fuse salt, ion-exchange treatment is carried out, near room temperature is subsequently cooled to, thus enters
Go chemical enhanced.Now, KNO3The temperature of fuse salt is set as 430 DEG C, and dip time is set as 3.5 hours.Resulting
Chemically reinforced glass is washed, for subsequent processing.
(being ground after reinforcing)
Mean particle diameter (d50) is dispersed in water for 0.8 μm of cerium oxide and produce slurry as ground slurry,
Glass plate is carried out using grinding pad (non-woven fabric type) with the grinding rate (one side) of 0.25 μm/minute using resulting slurry
Grinding.
(alkali process 1)
Prepare 5.0 mass % sodium hydrate aqueous solution in resinous groove, heater (Off ッ is coated using fluororesin
Plain Trees fat is coated to ヒ ー タ ー) (KKS14A；Eight photoelectricity machines are manufactured) temperature adjustment is carried out to 40 DEG C.By glass plate after adjustment
Impregnated 10 minutes or 30 minutes in sodium hydrate aqueous solution and carry out alkali process, it is then multiple using pure water cleaning, then pass through
Air blowing is dried.
(alkali process 2)
Prepare 1M potassium hydroxide aqueous solution in resinous groove, heater (KKS14A is coated using fluororesin；Eight light
Motor manufacturing) temperature adjustment is carried out to 40 DEG C.It will impregnate 10 minutes and enter in the potassium hydroxide aqueous solution of glass plate after adjustment
Row alkali process, it is then multiple using pure water cleaning, then it is dried by blowing.
(etching process)
Prepare 0.2 volume % aqueous hydrogen fluoride solutions in resinous groove, heater (KKS14A is coated using fluororesin；
Eight photoelectricity machines are manufactured) temperature adjustment is carried out to room temperature.It will be impregnated 20 seconds, 60 seconds in the aqueous hydrogen fluoride solution of glass plate after adjustment
Or 2 minutes and be etched, then, using pH10 NaOH aqueous cleanings 30 seconds, recycle pure water cleaning multiple,
Then it is dried by blowing.
Shown in table 1 for the chemically reinforced glass obtained by the above method to Stdi, Str20, Sk and BOR centre plane
The result that intensity is evaluated.Example 1~6 is that embodiment, example 7~10 are comparative example.In addition, based on the numerical value shown in table 1, will be right
Result obtained from the average surface intensities of Stdi and BOR are drawn is shown in Figure 1, and the average surface intensities of Str20 and BOR will be carried out
Result is shown in Figure 3 obtained from drawing, and result obtained from being drawn to the average surface intensities of Sk and BOR is shown in Figure 5.
On 1~example of example 10, the hydrogen concentration in the region for 0.1 μm~0.4 μm of the depth started at from the outmost surface of glass
Less than 0.070mol/L.In addition, on 1~example of example 6, surface roughness (Ra) is below 0.35nm.
[table 1]
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |
| Ground after reinforcing | Have | Have | Have | Nothing | Nothing | Nothing | Have | Have | Have | Have |
| Grinding damage | Have | Have | Have | Nothing | Nothing | Nothing | Have | Have | Have | Have |
| Alkali process 1 | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Have | Have | Nothing | Nothing |
| Alkali process 2 | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Have | Nothing |
| Etching process | Have | Have | Have | Have | Have | Have | Nothing | Nothing | Nothing | Nothing |
| Processing time (minute) | 0.3 | 1 | 2 | 0.3 | 1 | 2 | 10 | 30 | 10 | 0 |
| Surface removal amount [nm] | 74 | 158 | 270 | 52 | 97 | 196 | 19 | 40 | 11 | |
| Stdi | 0.74 | 0.79 | 0.8 | 0.77 | 0.78 | 0.78 | 0.35 | 0.65 | 0.54 | 0.59 |
| Str20 | 0.76 | 0.77 | 0.86 | 0.86 | 0.81 | 0.75 | 0.22 | 0.46 | 0.19 | 0.38 |
| sk[nm] | 0.89 | 0.99 | 0.99 | 0.86 | 0.9 | 0.93 | 1.2 | 1.09 | 1.14 | 1.56 |
| BOR mean intensities [N] | 906 | 1063 | 1123 | 1093 | 956 | 971 | 659 | 619 | 654 | 615 |
| Hydrogen concentration [mol/L] | 0.065 | 0.06 | 0.063 | 0.067 | 0.068 | 0.062 | 0.053 | 0.052 | 0.049 | 0.058 |
| Ra[nm] | 0.277 | 0.345 | 0.312 | 0.267 | 0.28 | 0.291 | 0.358 | 0.494 | 0.361 | 0.38 |
As shown in Figure 1, it is known that：There is dependency relation in Stdi, with surface intensity by making Stdi average for more than 0.70, BOR
Surface intensity reaches more than 800N, can realize high surface intensity.
In addition, it can be seen from the result shown in Fig. 3：There is dependency relation in Str20, with surface intensity by making Str20 be 0.5
More than, the average surface intensities of BOR reach more than 800N, can realize high surface intensity.
In addition, as shown in Figure 5, it is known that：There is dependency relation in Sk, by making Sk be below 1nm, BOR is average with surface intensity
Surface intensity reaches more than 800N, can realize high surface intensity.
<Test example 2>
[embodiment 2-1]
The glass of following compositions is manufactured by float glass process so that thickness of slab is 0.7mm, and cuts into 50mm × 50mm, so as to make
Go out glass plate.
Composition：Contain 64% SiO in terms of mole %2, 7.5% Al2O3, 13% Na2O, 11% MgO composition
(ion-exchange process)
Glass plate is immersed in KNO3In fuse salt, ion-exchange treatment is carried out, near room temperature is subsequently cooled to, thus enters
Row is chemical enhanced.Now, KNO3The temperature of fuse salt be set as 430 DEG C, dip time be set as 3.5 hours.Resulting change
Learn strengthened glass to be washed, for subsequent processing.
(alkali process)
Prepare 4.0 mass % sodium hydrate aqueous solution in resinous groove, heater is coated using fluororesin
(KKS14A；Eight photoelectricity machines are manufactured) temperature adjustment is carried out to 40 DEG C.It will be soaked in the sodium hydrate aqueous solution of glass plate after adjustment
Stain 30 minutes and carry out alkali process, it is then multiple using pure water cleaning, be then dried by blowing.
Embodiment 2-1 chemically reinforced glass is obtained through the above way.
[embodiment 2-2]
Following flash of light processing (Off レ ア processing) are carried out after ion-exchange process in embodiment 2-1 and before alkali process,
Embodiment 2-2 chemically reinforced glass has been obtained in the same manner as embodiment 2-1 in addition.
(flash of light processing)
The flash of light processing for preparing the hydrogen fluoride containing 5.0 mass % and 5.0 mass % nitric acid in resinous groove is used
The aqueous solution.The glass plate obtained in above-mentioned ion-exchange process is impregnated 2 minutes in the flash of light processing aqueous solution of preparation, entered
Row flash of light is handled, then multiple using pure water cleaning.By so obtained glass plate for alkali process.
[embodiment 2-3]
Following acid treatments are carried out after ion-exchange process in embodiment 2-1 and before alkali process, in addition with reality
Apply the chemically reinforced glass that a 2-1 has similarly obtained embodiment 2-3.
(acid treatment)
Prepare 1M nitric acid in resinous groove, heater (KKS14A is coated using fluororesin；Eight photoelectricity machines are manufactured)
Temperature adjustment is carried out to 40 DEG C.30 points will be impregnated in the nitric acid of the glass plate obtained in above-mentioned ion-exchange process after adjustment
Clock, carries out acid treatment, then multiple using pure water cleaning.By so obtained glass for alkali process.
[comparative example 2-1]
In embodiment 2-2, after ion-exchange process, without alkali process after flash of light processing, flash of light processing is only carried out,
It is same with embodiment 2-2 in addition.
[comparative example 2-2]
In embodiment 2-3, after ion-exchange process, without alkali process after acid treatment, acid treatment is only carried out, except this
It is same with embodiment 2-3 in addition.
For the chemically reinforced glass of resulting embodiment and comparative example, evaluated by XPS analysis and to wetability
Result be shown in Table 2.In wettability evaluation, after handling glass, preserve 4 days, then surveyed in toilet
It is fixed.
[table 2]
| Embodiment 2-1 | Embodiment 2-2 | Embodiment 23 | Comparative example 21 | Comparative example 22 | |
| Flash of light is handled | Nothing | Have | Nothing | Have | Nothing |
| Acid treatment | Nothing | Nothing | Have | Nothing | Have |
| Alkali process | Have | Have | Have | Nothing | Nothing |
| Surface removal amount [nm] | 65 | 2984 | 65 | 2903 | 48 |
| C1s | 2.08 | 2.28 | 1.17 | 0.64 | 0.34 |
| O1s | 3.05 | 2.88 | 2.78 | 2.49 | 2.43 |
| Na2s | 0.05 | 0.05 | 0.06 | 0.03 | 0.02 |
| Mg2s | 0.01 | 0.14 | 0.05 | 0.01 | 0.02 |
| A12p | 0.21 | 0.25 | 0.22 | 0.13 | 0.09 |
| Si2p | 1 | 1 | 1 | 1 | 1 |
| K2s | 0.13 | 0.1 | 0.13 | 0.05 | 0.04 |
| Surface cation amount | 0.83 | 1.18 | 0.96 | 0.49 | 0.37 |
| Surface silanol groups amount | 0.81 | 0.46 | 0.68 | 1.15 | 1.27 |
| Contact angle [°] | 14.3 | 16.3 | 15.5 | 8.2 | 7.7 |
As shown in table 2, compared with the comparative example 2-1 and 2-2 that do not carry out alkali process, the embodiment 2-1 of alkali process has been carried out
In~2-3, glass surface silanol base unit weight is less than 1, and contact angle is more than 14 °.It can be seen from the result：By being handed in ion
Change after process and alkali process is carried out to glass surface, the silanol base unit weight of glass surface can be reduced, being capable of contaminant restraining attachment
In glass surface.
The present invention is described for the detailed and specific embodiment of reference, but to those skilled in the art
It is evident that：Various changes, amendment can be carried out without departing from the spirit and scope of the present invention.
The application was based on 2 months 2016 Japanese patent application 2016-036084 filed in 26 days, and its content is as with reference to simultaneously
Enter in the application.
Claims (16)
1. a kind of chemically reinforced glass, wherein, the chemically reinforced glass has on top layer below compressive stress layer, and satisfaction
(1) condition of~(5)：
(1) there is grinding damage on surface；
(2) grain direction index (Stdi) is more than 0.70；
(3) the surface silanol groups amount obtained using following formula (i) is less than 1,
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atomic concentration of each element of glass surface by using X-ray photoelectron spectroscopy
And obtained using following formula (ii),
The cation amount of inside glass determines inside glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
Each element atomic concentration and using following formula (ii) obtain,
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii)；
(4) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L；
(5) surface roughness (Ra) determined using AFM under conditions of 1 μm of square is below 0.35nm.
2. chemically reinforced glass as claimed in claim 1, wherein, the texture aspect ratio (Str20) of the chemically reinforced glass
For more than 0.5.
3. chemically reinforced glass as claimed in claim 1 or 2, wherein, the core roughness depth of the chemically reinforced glass
(Sk) it is below 1nm.
4. chemically reinforced glass as claimed in claim 1 or 2, wherein, the average surface intensities of BOR of the chemically reinforced glass are
More than 800N.
5. chemically reinforced glass as claimed in claim 1 or 2, wherein, the glass is alumina silicate glass, aluminoborosilicate
Glass or soda-lime glass.
6. a kind of chemically reinforced glass, wherein, the chemically reinforced glass has on top layer below compressive stress layer, and satisfaction
(1) condition of~(3)：
(1) grain direction index (Stdi) is more than 0.70；
(2) the hydrogen concentration C in the region for depth X=0.1~0.4 (μm) started at from the outmost surface of glass is less than
0.070mol/L；
(3) surface roughness (Ra) determined using AFM under conditions of 1 μm of square is below 0.35nm.
7. chemically reinforced glass as claimed in claim 6, wherein, the chemically reinforced glass meets following condition：
The surface silanol groups amount that (condition) is obtained using following formula (i) is less than 1,
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atomic concentration of each element of glass surface by using X-ray photoelectron spectroscopy
And obtained using following formula (ii),
The cation amount of inside glass determines inside glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
Each element atomic concentration and using following formula (ii) obtain,
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii).
8. chemically reinforced glass as claimed in claims 6 or 7, it has grinding damage on surface.
9. chemically reinforced glass as claimed in claims 6 or 7, wherein, the texture aspect ratio of the chemically reinforced glass
(Str20) it is more than 0.5.
10. chemically reinforced glass as claimed in claims 6 or 7, wherein, the core roughness depth of the chemically reinforced glass
(Sk) it is below 1nm.
11. chemically reinforced glass as claimed in claims 6 or 7, wherein, the average surface intensities of BOR of the chemically reinforced glass
For more than 800N.
12. chemically reinforced glass as claimed in claims 6 or 7, wherein, the glass is alumina silicate glass, aluminium borosilicic acid
Salt glass or soda-lime glass.
13. a kind of manufacture method of chemically reinforced glass, it includes：
By ion-exchange surface layer of glass formation compressive stress layer ion-exchange process and
The glass surface treatment process of alkali process is carried out after the ion-exchange process,
Wherein,
The surface treatment procedure is the surface handled in the way of meeting following (a)~(c) the glass surface
Treatment process,
(a) grain direction index (Stdi) is more than 0.70；
(b) it is less than 0.070mol/ from the hydrogen concentration C in the region that the outmost surface of glass starts at depth X=0.1~0.4 (μm)
L；
(c) it is below 0.35nm using the AFM surface roughnesses (Ra) determined under conditions of scan size is 1 μm of 1 μ m.
14. the manufacture method of chemically reinforced glass as claimed in claim 13, wherein, the surface treatment procedure is with also full
The surface treatment procedure that the mode of (d) under being enough is handled the glass surface,
(d) the surface silanol groups amount obtained using following formula (i) is less than 1,
(surface silanol groups amount)=(the cation amount of inside glass)-(the cation amount of glass surface) ... formula (i)
The cation amount of glass surface determines the atomic concentration of each element of glass surface by using X-ray photoelectron spectroscopy
And obtained using following formula (ii),
The cation amount of inside glass determines inside glass after being sputtered by using C60 using X-ray photoelectron spectroscopy
Each element atomic concentration and using following formula (ii) obtain,
(cation amount)=K/Si+Na/Si+2 × Mg/Si+3 × Al/Si ... formulas (ii).
15. the manufacture method of the chemically reinforced glass as described in claim 13 or 14, wherein, the manufacture method is included in institute
State situation after surface treatment procedure, being more than 0.70 in the grain direction index (Stdi) obtained using afm image parsing
Under be judged as suitable sampling check.
16. the manufacture method of the chemically reinforced glass as described in claim 13 or 14, wherein, the manufacture method is included in institute
The grinding step stated after ion-exchange process and be ground before the surface treatment procedure to glass surface.
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