CN1759074A - Chemically reinforced glass and method for production thereof - Google Patents
Chemically reinforced glass and method for production thereof Download PDFInfo
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- CN1759074A CN1759074A CN 200480005573 CN200480005573A CN1759074A CN 1759074 A CN1759074 A CN 1759074A CN 200480005573 CN200480005573 CN 200480005573 CN 200480005573 A CN200480005573 A CN 200480005573A CN 1759074 A CN1759074 A CN 1759074A
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Abstract
The invention relates to a chemically reinforced glass having a compressive stress layer formed in the surface layer thereof by ion exchange, characterized in that it has two types of compressive stress curves in the compressive stress layer: an A curve present nearer to the surface of the glass, and a B curve present in the side of an inner layer of the glass; a first method and a second method for producing the chemically reinforced glass: a fist method, wherein, after the immersion treatment for ion exchange, a second immersion treatment is carried out at a temperature higher than that for the previous immersion treatment by 20 to 50 DEG C for 10 to 60 minutes, and a second method, wherein, after a first immersion treatment for ion exchange, a second immersion treatment is carried out at a temperature higher than that for the first immersion treatment by 20 to 50 DEG C for 10 to 60 minutes.
Description
Technical field
The present invention relates to chemically reinforced glass, especially use chemically reinforced glass and the manufacture method of using with field for building etc. thereof such as field of electronic materials, the automobile of touch-screen etc.
Background technology
From saving resource, the viewpoint of saving the energy or the variation of social needs, carrying out the thin plateization of chilled glass or improving the reinforcement degree.Because the general air-cooled reinforcement that uses is difficult to be produced and has following, the glass of the following thickness of slab of 2mm particularly of 3mm, so the glass below the 2mm often uses chemical enhanced method.In addition, chemically reinforced glass has and can make the high advantage of chilled glass that strength ratio generally adopts air cooling method.
As the reason that chemically reinforced glass is often accepted by market, except the reinforcement and high strength of aforesaid sheet glass, can enumerating under certain conditions, chilled glass also can cut off.And during the crack that air-quench toughened glass import to intend cuts off, because of slight crack much can not cut off.
For example, shown in Fig. 5 (referring to non-patent literature 1), this is the cause that chemically reinforced glass and air-cooled reinforcement (physical strengthening) glass differ widely at the inner stress curve that forms of glass.Air-quench toughened glass is owing to utilize the temperature head and the VISCOUS FLOW of surface layer of glass and internal layer, so the summary of its stress curve, for example one-tenth is similar to the shape of 2 curves.And chemically reinforced glass is for example owing to utilize ion-exchange on the top layer, so depend on the diffusion law of Fick closely, unusual near linear state often.The surface compression stress value that air-quench toughened glass will obtain setting, the tensile stress that is in internal layer increases inevitably.Because the destruction of glass depends on the tensile stress of glass internal layer, so under big tensile stress, produce the shred phenomenon.And, the occasion of chemically reinforced glass, even improve compression stress value, the tensile stress values of internal layer is also not too large under common condition.The tensile stress values of chemically reinforced glass becomes the function of surface compression stress value and stress under compression bed thickness mostly.
That is, no matter air-quench toughened glass or chemically reinforced glass are big as the strength at break of glass.In addition, the occasion of air-quench toughened glass can not be cut off, and the occasion of chemically reinforced glass, even the problem that possibility also has hard-to-break concurrently of cutting off is arranged.
In addition, considered the whole bag of tricks as the manufacture method of chemically reinforced glass.For example, the atomic substitutions of handlebar small ion radius becomes the method for the atom of heavy ion radius, the VISCOUS FLOW of utilizing glass the atomic substitutions of heavy ion radius become the atom of small ion radius method, utilize the coefficient of thermal expansion difference method, make method that crystallization separates out, with numerous methods such as method of above-mentioned method combination.General soda-lime glass uses the method that the atomic substitutions of small ion radius is become the atom of heavy ion radius mostly, and wherein, most chemically reinforced glass employings is flooded in chemical enhanced treatment trough, and so-called pickling process is made.That is, glass-impregnated at the chemical enhanced treatment solution of pyritous, for example in the potassium nitrate solution, by sodium ion in the glass and the potassium ion in the saltpetre are replaced, is formed compressive stress layers on the top layer.In addition, as the chemical enhanced treatment solution that contains the lithium occasion in the glass, use the mixing salt of SODIUMNITRATE or SODIUMNITRATE and saltpetre mostly.
Known technology for example discloses the technology (referring to patent documentation 1) of the glass that chemical enhanced use cuts off, as the determination techniques (referring to patent documentation 2) of the surface stress of the important factor of the condition of cut-out.In addition, the relevant chemical enhanced operation of hard disk drive:
1) preheating in fore-warmer tank (being warmed up to 380～500 ℃) with 0.5～2 hour
2) the chemical enhanced processing in the molten salt solution of saltpetre or SODIUMNITRATE (about 0.5～6 hour)
3) cooling in the air-supply cooling tank (is used 5～25m
3/ minute cooling air in face, force to be cooled to room temperature below the molten salt solution fusing point in 5 ℃ of the temperature heads)
The example that also has a detailed description (referring to patent documentation 3).
Patent documentation 1: the spy opens the 2002-160932 communique
Patent documentation 2: special public clear 59-37451 communique
Patent documentation 3: the spy opens the 2000-344550 communique
Non-patent literature 1:H.M.Gartinkel etc., The Glass Industry, 50 (1969), p.76.
Summary of the invention
The object of the invention provides has the chemically reinforced glass that cuts off of setting intensity.
Another object of the present invention provides the manufacture method of aforementioned chemically reinforced glass.
Feature according to the of the present invention the 1st, provide by ion-exchange to form in the chemically reinforced glass of compressive stress layers, two kinds of chemically reinforced glass that different stress curves is a feature of the stress under compression curve B of the stress under compression curve A of close glass surface and glass internal layer side are arranged in compressive stress layers at surface layer of glass.
Feature according to the of the present invention the 2nd, be provided at by ion exchange treatment in the manufacture method of the chemically reinforced glass of top layer formation compressive stress layers, after the dip treating that ion-exchange is used, remain the manufacture method (the 1st method) of the chemically reinforced glass of feature under than the high temperature environment more than 10 ℃ of this steeping fluid temperature.
In addition, according to the 2nd feature of the present invention, provide the chemically reinforced glass of the method manufacturing of adopting the 2nd feature.
According to the 3rd feature of the present invention, be provided at by ion exchange treatment in the manufacture method of the chemically reinforced glass of surface layer of glass formation compressive stress layers, after the 1st dip treating that ion-exchange is used, the 2nd dip treating of carrying out 10 minutes～60 minutes under～temperature of 50 ℃ higher 20 ℃ than this steeping fluid temperature is the manufacture method (the 2nd method) of the chemically reinforced glass of feature.
In addition, according to the 3rd feature of the present invention, provide the chemically reinforced glass of the method manufacturing of adopting the 3rd feature.
The chemically reinforced glass of the 1st feature according to the present invention can adopt the above-mentioned the 1st or the 2nd method manufacturing.
Description of drawings
Fig. 1 is the sketch of the stress curve that presents of embodiment 1.
Fig. 2 is the sketch of the stress curve that presents of embodiment 2.
Fig. 3 is the sketch of the stress curve that presents of comparative example 1.
Fig. 4 is the sketch of the stress curve that presents of comparative example 2.
Fig. 5 is the sketch of the stress curve of expression chemically reinforced glass and air-cooled (physics) chilled glass.
Fig. 6 is the sketch of the particular example of expression stress curve A.
Nomenclature
1: the surface of chemically reinforced glass
2: stress curve B
3: stress curve A
4: the extended line of stress curve B
D: surface compression stress bed thickness
σ: surface compression stress value
σ
B: by the surface compression stress value of stress curve B deduction
C: stress under compression
T: tensile stress
Embodiment
Below at length narrate above-mentioned the 1st feature of the present invention.According to the 1st feature, provide the chemically reinforced glass that to stablize cut-out.
In order to improve the cuttability of glass, use the glass that 2 kinds of different stress curves are arranged in the glass.The glass that use has 2 kinds of different stress curves not only has the stress under compression bed thickness of setting, and can become the chemically reinforced glass of easy cut-out.In other words, not that stress curve depends on the chemically reinforced glass of Fick law in the past, but not only depend on the Fick law, the chemically reinforced glass that the stress that especially produces is represented with other functional form near the top layer.
In addition, stress curve A and stress curve B are similar to the occasion of 1 function respectively, are the above-mentioned chemically reinforced glass that stress curve A and stress curve B have Different Slope.Do not have other stress curve, promptly have only the chemically reinforced glass in the past of a kind of stress curve, have the big value of strength at break, have the problem of hard-to-break, and will cut off easily, then strength at break diminishes.
In addition, be the chemically reinforced glass of the little value of the hypothesis surface stress value obtained than the line that extends to glass surface by stress curve B of the surface stress value obtained by stress curve A.Obviously, if be the occasion of big value, then hard-to-break.
In addition, the ratio of preferably being obtained by stress curve A surface stress value of obtaining and the line that is extended to glass surface by the stress under compression curve B of inferring the surface stress value is 0.8～0.95 above-mentioned chemically reinforced glass.The ratio of obtaining with the line that is extended to glass surface by stress curve B of inferring the surface stress value is 0.8～0.95.Surface compression stress diminishes during less than 0.8, the actual reduction of glass intensity.And surpassing at 0.95 o'clock, cuttability reduces.Be more preferably 0.85～0.93.
This occasion, according to the condition difference, the slope of stress curve A is opposite with stress curve B sometimes as shown in Figure 6.That is, the surface compression stress of the chemically reinforced glass in the past often stress value than internal layer is big, and chemically reinforced glass of the present invention, the value that presents less the stress value specific surface stress under compression of layer segment in little the entering sometimes is big.Chemically reinforced glass with such stress curve is also listed category of the present invention certainly in.
The stress under compression bed thickness that preferred in addition stress curve A forms is 2 μ m～15 μ m.The stress under compression bed thickness that stress curve A forms during less than 2 μ m the cut-out effect to glass diminish, the strength at break of chemically reinforced glass diminished in fact when the stress under compression bed thickness of stress curve A surpassed 15 μ m.Be more preferably 3 μ m～9 μ m.
In addition, should carry out the production management of chemically reinforced glass simply, illustrate that the stress curve in the chemically reinforced glass is similar to 1 time.But strictly say certainly and also the situation that stress curve can not be similar to 1 function can occur.This is that and diffusion law is not 1 function because the diffusion law according to Fick is gone up in ion-exchange substantially as previously mentioned, so strictly say and must depart from proximate collinear cause.In addition, the stress in the glass generates outside the deionization exchange, also is subjected to influence of various factors such as temperature distribution, distortion, thickness of slab.Occasion that like this can not near linear or be difficult to the occasion of near linear, the stress curve of generation can be with 1 function representation, and maybe should get back to needs 2 principles with superior function.Here, the approximate repeatedly function that does not use more than 3 times.Approximate use has an extreme point or does not have the function of extreme point.When using such approximation to function, can be chemically reinforced glass in the past with the situation of one function representation.And 2 occasions with superior function of essential use then are chemically reinforced glass of the present invention.In addition, the field as considering approximation to function should be the stress under compression field.This is because the cuttability and the strength at break of glass depend on compression stress value, and begins to become its stress generation instability of field of certain value sometimes in tensile stress, and this judgement might produce mistake.
The thickness of the compressive stress layers of chemically reinforced glass and the value of stress under compression since be subjected to treatment temp when chemical enhanced and treatment time, again be subject to processing the selection of liquid and activity characteristic thereof influence very big, so not simple.In addition, also because of ion-exchange situation in the glass or crystallization situation difference.But, be to obtain strength at break is remained on realistic scale, and improved the chemically reinforced glass of cuttability.
Below describe the 2nd feature of the present invention in detail.According to the 2nd feature, provide the manufacture method (the 1st method) of chemically reinforced glass with intensity and cuttability.
In the 1st method, under high temperature more than 10 ℃, handle very important after the dip treating to the cuttability that improves chemically reinforced glass than steeping fluid temperature.When treatment temp is lower than 10 ℃, be difficult to improve cuttability sometimes.
In addition, for example, under～temperature of 50 ℃ higher 10 ℃, kept 10 minutes～60 minutes after the dip treating than steeping fluid temperature.The cuttability of chemically reinforced glass reduces sometimes when being lower than 10 ℃, and the intensity of chemically reinforced glass reduces sometimes when surpassing 50 ℃.In addition, the problem that the deterioration of steeping fluid causes takes place sometimes.The problem of chemically reinforced glass product deformation and so on also takes place sometimes.Setting 10 minutes～60 minutes, is because the cuttability of chemically reinforced glass reduces the cause that the intensity of chemically reinforced glass reduces sometimes when being longer than 60 minutes sometimes when being less than 10 minutes.In addition, be because the problem of chemically reinforced glass product deformation and so on also takes place sometimes.
In addition, for example, the steeping fluid temperature can be set at 450 ℃～510 ℃.During 450 ℃ of less thaies, the difficult sometimes cuttability that improves chemically reinforced glass, so making sometimes needs the time long the production efficiency extreme difference.When surpassing 510 ℃, the problem that the intensity of chemically reinforced glass diminishes also takes place sometimes.
In addition, for example, can under～temperature of 150 ℃ higher 50 ℃, keep 1 minute～30 minutes after the dip treating than steeping fluid temperature.The cuttability of chemically reinforced glass reduces sometimes when being lower than 50 ℃, and the intensity of chemically reinforced glass reduces sometimes when surpassing 150 ℃ temperature.In addition, the problem that the deterioration of steeping fluid causes taking place also, set 1 minute～30 minutes, is because the cuttability of chemically reinforced glass reduces the cause that the intensity of chemically reinforced glass reduces sometimes when being longer than 30 minutes sometimes when being less than 1 minute.In addition, be because the problem of chemically reinforced glass product deformation and so on also takes place sometimes.
Keep 1 minute～30 minutes occasion after the dip treating under～temperature of 150 ℃ higher 50 ℃ than steeping fluid temperature, also can make the steeping fluid temperature is 410 ℃～500 ℃.
Below describe above-mentioned the 3rd feature of the present invention in detail.According to the 3rd feature, provide the method (the 2nd method) of stablizing the chemically reinforced glass that manufacturing can cut off.
In the 2nd method, make the 2nd steeping fluid temperature for than the 1st steeping fluid temperature high 20 ℃～50 ℃ temperature, be because the cuttability of the chemically reinforced glass that obtains during 20 ℃ of less thaies reduces the cause that the intensity of the chemically reinforced glass that obtains when surpassing 50 ℃ reduces.In addition, the problem that the deterioration of ion exchange liquid causes also can take place.
In addition, making for the 2nd dip treating time is 10 minutes～60 minutes, is because the cuttability of the chemically reinforced glass that less than obtained in the time of 10 minutes reduces, the cause that the intensity of the chemically reinforced glass that obtains in the time of more than 60 minutes reduces.
In addition, also can make the 1st dip treating temperature is 450 ℃～510 ℃.So the difficult cuttability that improves the chemically reinforced glass that obtains during 450 ℃ of less thaies needs the time long production efficiency extreme difference sometimes owing to make.The problem that the intensity of the chemically reinforced glass that also obtains sometimes when surpassing 510 ℃ diminishes.
The cuttability that adopts the chemically reinforced glass of the 1st method and the 2nd method manufacturing to become to have glass concurrently and the chemically reinforced glass of intensity.These chemically reinforced glass can have the characteristic based on the chemically reinforced glass of the present invention's the 1st feature.
The surface hardness that can obtain becoming the chemically reinforced glass of the 1st method of employing and the 2nd method manufacturing in addition is 560～590kgf/cm
2Chemically reinforced glass.It is said that the surface hardness of soda-lime chemically reinforced glass of method manufacturing in the past is 590～610kgf/cm
2And its surface hardness of the chemically reinforced glass that the method for the 2nd feature of the present invention makes is 560～590kgf/cm
2Surpass 590kgf/cm
2The time, poor with the same cuttability of chemically reinforced glass in the past, can not cut off sometimes.In addition, promptly enable to cut off, but depart from desirable cut-out line sometimes, and have the tendency of surperficial multiple glass powder.On the other hand, its surface hardness compares 560kgf/cm
2There is the little tendency of intensity in little chemically reinforced glass.In addition, measurement of hardness can use commercially available micro-hardness tester, but must be that the lifting capacity of measuring is little value, for example is below the 50g.The load of 200～1000g that the measurement of hardness of general soda-lime glass uses owing to misdeem sometimes, must be noted that.
The intensity that chemically reinforced glass of the present invention has an existing chemically reinforced glass near in the past has the feature of cuttability again.This is because of different with chemically reinforced glass in the past, becomes the cause of the stress curve that not only depends on the Fick law.Therefore, have surface hardness and some different features are arranged with the hardness of in the past chemically reinforced glass.
In addition, in the 1st method and the 2nd method, can also carry out ion exchange treatment to the soda-lime glass of 470 ℃～530 ℃ of strain points.It is low that strain point is lower than 470 ℃ soda-lime glass chemistry weather resistance or hardness, and the practicality of pretending to chemically reinforced glass reduces greatly.And strain point is higher than 530 ℃ soda-lime glass, and the cuttability of glass descends, and chemical enhanced property also reduces.In addition, the glass beyond the soda-lime glass is because production efficiency low price height, even have cuttability and its practicality of intensity also little.
Below, specifically describe the present invention according to embodiment.Embodiment 1-2, embodiment 3-6, embodiment 7-9 are respectively the examples that proves the 1st, the 2nd, the 3rd feature of the present invention for example.
Embodiment 1
The soda-lime float glass of thickness 0.7mm in 460 ℃ saltpetre melting salt, flood carried out ion exchange treatment in 10 hours after, chemically reinforced glass is moved on in the cooling tank that is set in 510 ℃, in this cooling tank, kept 60 minutes again.Then according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, the chemically reinforced glass that obtains setting.The stress curve of this glass is shown in Fig. 1.C among the figure represents stress under compression, and T represents tensile stress.So, be two kinds of chemically reinforced glass that curve is a feature in compressive stress layers with stress under compression curve B that the stress under compression of close glass surface side curve A and glass internal layer side are arranged.In addition, this stress curve is to represent that cutting out chemically reinforced glass grinds, and uses the result's of Babinet's compensator and observation by light microscope stress curve.The ratio of the hypothesis surface stress value of being obtained by stress curve A surface stress value of obtaining and the line that is extended to glass surface by the stress under compression curve B is 0.93.In addition, the stress under compression bed thickness of stress curve A formation is 4 μ m.
To this chemically reinforced glass use commercially available superhard ratch cutter, according to general cut-out operation rule (weighing load: 2kg) with cut off test, the result can cut off out of questionly.
The soda-lime float glass of thickness 0.55mm in 470 ℃ saltpetre melting salt, flood carried out the 1st secondary ion exchange in 4 hours and handle after, carrying out the exchange of the 2nd secondary ion in 20 minutes at 510 ℃ of dippings handles, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass of setting then.The stress curve of this glass is shown in Fig. 2.The ratio of the surface stress value of being obtained by stress curve A, the hypothesis surface stress value obtained with the line that is extended to glass surface by the stress under compression curve B is 0.89.In addition, the stress under compression bed thickness of stress curve A formation is 5 μ m.
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, the result can cut off out of questionly.
Comparative example 1
The soda-lime float glass of thickness 0.7mm in 460 ℃ saltpetre melting salt, flood carried out ion exchange treatment in 10 hours after, chemically reinforced glass is moved on in the cooling tank that is set in 380 ℃, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass of setting.The stress curve of this glass is shown in Fig. 3.1 kind of stress curve is arranged among the figure.Yes 1.0 for the ratio of the surface stress value of being obtained by stress curve A, the hypothesis surface stress value obtained with the line that is extended to glass surface by the stress under compression curve B.In addition, stress under compression bed thickness (stress curve A and B) is 33 μ m.
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, slight crack is remarkable as a result.In addition, (final weighing load: the result who 7kg) studies, the glass powder from the many wire of line generation can not use as the chemically reinforced glass goods to increase cut-out pressure.In addition, have and promptly to depart from the place that cuts off line along the line cut-off part.
Comparative example 2
The soda-lime float glass of thickness 0.7mm in 460 ℃ saltpetre melting salt, flood carried out ion exchange treatment in 10 hours after, chemically reinforced glass moved on in the cooling tank that is set in 550 ℃ cools off, in this cooling tank, kept 60 minutes again.According to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass of setting then.The stress curve of this glass is shown in Fig. 4.The ratio of the hypothesis surface stress value of being obtained by stress curve A surface stress value of obtaining and the line that is extended to glass surface by the stress under compression curve B is 0.7.In addition, the compressive stress layers of stress curve A formation is 17 μ m.
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, slight crack is remarkable as a result.In addition, weighing load is the result that 5kg studies, and this chemically reinforced glass destroys.
Result by above embodiment 1～2 shows, by increase above-mentioned operation of the present invention behind ion-exchange process, can make the chemically reinforced glass of easy cut-out.
The soda-lime float glass of thickness 0.7mm flooded in 460 ℃ saltpetre melting salt carried out ion exchange treatment in 10 hours.Immediately chemically reinforced glass is moved on in the cooling tank that is set in 510 ℃ after just having handled, in this cooling tank, kept 60 minutes again.Then, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass goods of setting.In addition, the surface hardness of these chemically reinforced glass goods is 570kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, the result can cut off out of questionly.
Embodiment 4
The soda-lime float glass of thickness 0.55mm flooded in 470 ℃ saltpetre melting salt carried out ion exchange treatment in 4 hours.Immediately chemically reinforced glass is moved on in the cooling tank that is set in 515 ℃ after just having handled, in this cooling tank, kept 20 minutes again.Then, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass of setting.In addition, the surface hardness of these chemically reinforced glass goods is 580kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, the result can cut off out of questionly.
Embodiment 5
The soda-lime float glass of thickness 0.7mm flooded in 410 ℃ saltpetre melting salt carried out ion exchange treatment in 24 hours.Immediately chemically reinforced glass is moved on in the cooling tank that is set in 550 ℃ after just having handled, in this cooling tank, kept 3 minutes again.Then, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass of setting.In addition, the surface hardness of these chemically reinforced glass goods is 585kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, the result can cut off out of questionly.
Embodiment 6
The soda-lime float glass of thickness 1.1mm carried out chemical enhanced processing in 2 hours in 490 ℃ saltpetre melting salt after, kept 2 minutes, make the chemically reinforced glass of setting at 540 ℃.In addition, the surface hardness of these chemically reinforced glass goods is 585kgf/cm
2
The result this chemically reinforced glass used commercially available superhard ratch cutter, rules, cuts off test, though finally can cut off in slightly sliding sense on glass out of questionly.
Comparative example 3
Adopt the operation identical to make the chemically reinforced glass goods of setting with comparative example 1.In addition, the surface hardness of these chemically reinforced glass goods is 600kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, slight crack is remarkable as a result.In addition, (final weighing load: the result who 7kg) studies, the glass powder from the many wire of line generation can not use as the chemically reinforced glass goods to increase cut-out pressure.In addition, have and promptly to depart from the place that cuts off line along the place that line is cut off.
Comparative example 4
The soda-lime float glass of thickness 0.55mm flooded in 470 ℃ saltpetre melting salt carried out ion exchange treatment in 4 hours.Then, chemically reinforced glass is moved on in the cooling tank that is set in 380 ℃,, make the chemically reinforced glass goods of setting according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling.In addition, the surface hardness of these chemically reinforced glass goods is 605kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, slight crack is remarkable as a result.In addition, (final weighing load: the result who 5kg) studies, this chemically reinforced glass destroys to increase cut-out pressure.
Comparative example 5
The aluminium boric acid of thickness 1.1mm be glass in 460 ℃ saltpetre melting salt, flood carried out ion exchange treatment in 10 hours after, chemically reinforced glass is moved on in the cooling tank that is set in 380 ℃, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass of setting.In addition, the surface hardness of these chemically reinforced glass goods is 640kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, slight crack is remarkable as a result.In addition, increase cut-out pressure (final weighing load: 5kg) study, but can not cut off along cutting off line.
Result by above embodiment 3～6 shows, by increase the operation of the 2nd feature of the present invention behind ion-exchange process, can make the chemically reinforced glass of easy cut-out.In addition, the surface hardness of glass is used commercially available Vickers hardness (alum is made made), all measures under the load of 50g.As above-mentioned, following embodiment 7～9th proves the example of the present invention's the 3rd feature for example.
Embodiment 7
The soda-lime float glass of thickness 0.7mm in 460 ℃ saltpetre melting salt, flood carried out the 1st time chemical enhanced (ion-exchange) in 10 hours and handle after.Under 510 ℃ of steeping fluid temperature, carry out secondary ion exchange in 60 minutes the 2nd and handle (in the saltpetre melting salt, flooding).After just having handled, immediately chemically reinforced glass is moved on in the cooling tank that is set in 500 ℃, in this cooling tank, kept 60 minutes again.Then, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass goods of setting.In addition, the surface hardness of these chemically reinforced glass goods is 565kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, the result can cut off out of questionly.
Embodiment 8
The soda-lime float glass of thickness 0.55mm in 470 ℃ saltpetre melting salt, flood carried out the 1st time chemical enhanced (ion-exchange) in 4 hours and handle after, under 510 ℃ steeping fluid temperature, carry out secondary ion exchange in 20 minutes the 2nd and handle (in the saltpetre melting salt, flooding).After just having handled, immediately chemically reinforced glass is moved on in the cooling tank that is set in 500 ℃, in this cooling tank, kept 20 minutes again.Then, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass goods of setting.In addition, the surface hardness of these chemically reinforced glass goods is 580kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, and ruling according to general cut-out operation, (weighing load: 2kg) with the cut-out test, the result can cut off out of questionly.
Embodiment 9
The soda-lime float glass of thickness 1.1mm in 505 ℃ saltpetre melting salt, flood carried out the 1st time chemical enhanced (ion-exchange) in 1 hour and handle after, under 525 ℃ steeping fluid temperature, carry out secondary ion exchange in 10 minutes the 2nd and handle (in the saltpetre melting salt, flooding).After just having handled, immediately chemically reinforced glass is moved on in the cooling tank that is set in 500 ℃, in this cooling tank, kept 3 minutes again.Then, according to the speed of cooling of carrying out usually (about 10 ℃/minute) cooling, make the chemically reinforced glass goods of setting.In addition, the surface hardness of these chemically reinforced glass goods is 585kgf/cm
2
This chemically reinforced glass is used commercially available superhard ratch cutter, according to general cut-out operation rule (weighing load: 2kg) with cut off test, though the sensation of result's slightly similar slippage on glass finally can be cut off out of questionly.
Comparative example 6
The soda-lime float glass of thickness 0.7mm in 460 ℃ saltpetre melting salt, flood carried out chemical enhanced (ion-exchange) in 10 hours and handle after, enter refrigerating work procedure manufacturing chemistry chilled glass immediately.
Use commercially available superhard ratch cutter to rule, cut off the result of test to this chemically reinforced glass, slight crack is remarkable.In addition, increase the result that cut-out pressure is studied, the glass powder from the many wire of line generation can not use as the chemically reinforced glass goods.And, can not cut off along line sometimes.
Comparative example 7
The soda-lime float glass of thickness 0.55mm in 470 ℃ saltpetre melting salt, flood carried out chemical enhanced (ion-exchange) in 4 hours and handle after, enter refrigerating work procedure manufacturing chemistry chilled glass immediately.
Use commercially available superhard ratch cutter to rule, cut off the result of test to this chemically reinforced glass, slight crack is remarkable.In addition, increase the result that cut-out pressure is studied, this chemically reinforced glass destroys.
Comparative example 8
The aluminium boric acid of thickness 1.1mm be glass in 460 ℃ saltpetre melting salt, flood carried out chemical enhanced (ion-exchange) in 10 hours and handle after, enter refrigerating work procedure manufacturing chemistry chilled glass immediately.
Use commercially available superhard ratch cutter to rule, cut off the result of test to this chemically reinforced glass, slight crack is remarkable.In addition, increase cut-out pressure and study, can not cut off this chemically reinforced glass along line.
Result by above embodiment 7～9 shows, can make the chemically reinforced glass of easy cut-out by the operation that increases the 3rd feature of the present invention after ion-exchange.
Claims (18)
1. chemically reinforced glass is to form the chemically reinforced glass of compressive stress layers by ion-exchange at surface layer of glass, it is characterized in that having in compressive stress layers two kinds of stress curves of the stress curve B of the stress curve A of close glass surface and glass internal layer side.
2. the described chemically reinforced glass of claim 1 is characterized in that the occasion of approximate 1 function respectively at stress curve A and stress curve B, and stress curve A has different slopes with stress curve B.
3. claim 1 or 2 described chemically reinforced glass is characterized in that the surface stress value of being obtained by stress curve A is to infer the little value of surface stress value than what the line that is extended to glass surface by stress curve B was obtained.
4. the described chemically reinforced glass of any one of claim 1～3 is characterized in that the ratio of inferring the surface stress value that surface stress value of being obtained by stress curve A and the line that is extended to glass surface by the stress under compression curve B are obtained is 0.8～0.95.
5. the described chemically reinforced glass of any one of claim 1～4 is characterized in that the stress under compression bed thickness that stress curve A forms is 2 μ m～15 μ m.
6. the manufacture method of chemically reinforced glass, it is characterized in that under than the high temperature environment more than 10 ℃ of this steeping fluid temperature, keeping after the dip treating that ion-exchange is used forming in the manufacture method of chemically reinforced glass of compressive stress layers at surface layer of glass by ion exchange treatment.
7. the manufacture method of the described chemically reinforced glass of claim 6 is characterized in that after the dip treating keeping 10 minutes～60 minutes under～temperature of 50 ℃ higher 10 ℃ than this steeping fluid temperature.
8. the manufacture method of the described chemically reinforced glass of claim 7, it is characterized in that making the steeping fluid temperature is 460 ℃～510 ℃.
9. the manufacture method of the described chemically reinforced glass of claim 6 is characterized in that after the dip treating keeping 1 minute～30 minutes under～temperature of 150 ℃ higher 50 ℃ than steeping fluid temperature.
10. the manufacture method of the described chemically reinforced glass of claim 9, it is characterized in that making the steeping fluid temperature is 410 ℃～500 ℃.
11. chemically reinforced glass is characterized in that adopting any one described method manufacturing of claim 6～10.
12. the described chemically reinforced glass of claim 11, the surface hardness that it is characterized in that chemically reinforced glass is 560～590kgf/cm
2
13. claim 11 or 12 described chemically reinforced glass is characterized in that the soda-lime glass of 470 ℃～530 ℃ of strain points is carried out ion exchange treatment.
14. the manufacture method of chemically reinforced glass, it is characterized in that forming in the manufacture method of chemically reinforced glass of compressive stress layers at surface layer of glass, in the 2nd dip treating of under～temperature of 50 ℃ higher 20 ℃, carrying out 10 minutes～60 minutes after the 1st dip treating that ion-exchange is used than this steeping fluid temperature by ion-exchange.
15. the manufacture method of the described chemically reinforced glass of claim 14, the steeping fluid temperature that it is characterized in that the 1st dip treating are 450 ℃～510 ℃.
16. chemically reinforced glass is characterized in that adopting the method manufacturing of claim 14 or 15.
17. the described chemically reinforced glass of claim 16 is characterized in that the surface hardness of the chemically reinforced glass that makes is 560～590kgf/cm
2
18. claim 16 or 17 described chemically reinforced glass is characterized in that the soda-lime glass of 470 ℃～530 ℃ of strain points is carried out ion exchange treatment.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP150001/2003 | 2003-05-28 | ||
| JP2003150000A JP4535692B2 (en) | 2003-05-28 | 2003-05-28 | Chemically tempered glass |
| JP150000/2003 | 2003-05-28 | ||
| JP160672/2003 | 2003-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1759074A true CN1759074A (en) | 2006-04-12 |
| CN100465119C CN100465119C (en) | 2009-03-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800055738A Expired - Fee Related CN100465119C (en) | 2003-05-28 | 2004-05-25 | Chemically reinforced glass and method for production thereof |
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| Country | Link |
|---|---|
| JP (1) | JP4535692B2 (en) |
| CN (1) | CN100465119C (en) |
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Family Cites Families (6)
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|---|---|---|---|---|
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2003
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2004
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100465119C (en) | 2009-03-04 |
| JP2004352535A (en) | 2004-12-16 |
| JP4535692B2 (en) | 2010-09-01 |
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