CN103359934B

CN103359934B - Resistance to deformation high yield strength zirconium Boroalumino silicate glasses in light weight

Info

Publication number: CN103359934B
Application number: CN201210092935.8A
Authority: CN
Inventors: 张广军; 范慧艳; 奥利弗·霍赫赖因
Original assignee: Schott Glass Technologies Suzhou Co Ltd
Current assignee: Schott Glass Technologies Suzhou Co Ltd
Priority date: 2012-03-31
Filing date: 2012-03-31
Publication date: 2018-02-13
Anticipated expiration: 2032-03-31
Also published as: DE102013103033A1; CN103359934A

Abstract

There are resistance to deformation, high yield strength, zirconium Boroalumino silicate glasses in light weight the present invention relates to a kind of, ZrO is included more particularly to one kind₂And B₂O₃Alumina silicate glass, it has following performance：Modulus of elasticity is 60GPa≤E≤78GPa after chemical tempering；Yield point is 620 DEG C of At≤850 DEG C；Thermal coefficient of expansion is 7.5 × 10^‑6/K≤CTE≤9.8×10^‑6/K；Density≤2.5g/cm³；Bearing stress is at least 700MPa；Surface stress layer thickness is at least 25 μm.The glass has a deformation resistance, and yield point temperature is high and in light weight.

Description

Resistance to deformation high yield strength zirconium boron-alumina silicate glass in light weight

Invention field

The present invention relates to a kind of alumina silicate glass containing zirconium and boron, the glass has deformation resistance, yield point temperature height With it is in light weight.The invention further relates to the glassware for passing through chemical tempering preparation by the zirconium boron-alumina silicate glass.The zirconium Boron-alumina silicate glass can be used in the mobile device or non-mobile device with display, can also be used in white domestic appliances and lead Domain.

Background of invention

Cover plate is generally used for electronic equipment, mobile electronic device, such as personal digital assistant, movement or honeycomb fashion electricity In words, wrist-watch, portable computer, notebook computer, digital camera, PDA, or the substrate glass as touch-screen, television set.It is right In these applications, user needs often to touch cover plate, and due to the touch to user, glass can produce, for example, surface The problems such as damage, scraping and deformation.These defects will influence the normal operation of equipment.Due to frequently contact, these protection glass Glass must have high intensity and want scratch-resistant and resistance to deformation.

Strength of glass is determined by the system and composition of glass.Thus seek with higher intensity, higher hard Degree, low fragility, anti-scratch and deformation resistance glass, first have to start with from glass system and composition, by adjust glass composition and Composition, modulus of elasticity, hardness and the fragility of glass can be improved, so as to obtain with high impact properties, high scratch resistance and height The glass of deformation resistance.

Traditional soda-lime-silica glass can not meet these requirements, such as high intensity, high deformation resistance and scratch resistance Requirement.

Alumina silicate glass has high intensity, high rigidity, stable chemical resistance, low thermal coefficient of expansion, high scratch resistance Wiping and impact resistance, it is suitable as the anti-of moving device (mobile phone, smart phone, tablet personal computer, notebook computer, PDA) Protect glass.This glass also is used as irremovable device (television set, PC, MTA equipment, digital camera, wrist-watch, work Industry display) cover plate, the cover plate of touch-screen, protective window, automotive window, train vehicle window, aviation machine window and hard Disk substrate.This glass can also be applied to white domestic appliances field, such as refrigerator and kitchen tools simultaneously.

After glass system and composition determine, can utilize chemical tempering method further improve strength of glass, hardness, Anti-scratch and deformation resistance.

Chemical tempering is widely used as the method for improving strength of glass.Chemical tempering is by under low temperature environment Ion-exchange process realize.At a temperature of less than strain point of glass, molten salt solution, such as NaNO are used₃、KNO₃Or NaNO₃And KNO₃Mixture, the temperature of the molten salt solution is 380 DEG C -500 DEG C, sometimes even more high.This causes glass table The sodium ion in face is replaced by the potassium ion from molten salt solution.These potassium ions are more than sodium ion, so as to be moved to when sodium ion When in potassium nitrate solution, potassium ion is wedged in the space left by smaller sodium ion, and this displacement of ion causes glass surface In compressive state, glass surface produces compression, and the heart produces tension compensating in glass.This chemical tempering can be carried substantially High strength of glass.

Although chemical tempering is widely used in processing glass, strength of glass is improved.But the need for developing and applying with technology Ask, for mobile device or the glass of non-mobile device, for example (,) it is mobile phone, smart phone, tablet personal computer, notebook, PDA, hand-held The glass of game machine, MP3 player, wrist-watch, television set, the protecting screen of industrial display, display screen or touch-screen needs to have Deformation resistance, so as to can be inside protection equipment when outer bound pair glass applies pressure electronic component it is without prejudice.It is this Application requirement glass can not have big deformation under external force, such as bend, and smaller deformation more can be inside protection equipment Electronic component it is without prejudice.Meanwhile a kind of new trend is that the thickness of mobile device or non-mobile device becomes increasingly Come thin.For example, the integral thickness of mobile phone has been reduced to 8mm, even less than 7mm.Relatively thin mobile device or non-mobile device need Want the cover plate of display or touch display that there is high dimensional accuracy, particularly glass does not deform under a certain pressure Or the deformation with very little, it is without prejudice so as to the internal electronic component of protection equipment.Therefore there is deformation resistance Glass be a kind of following demand.In order to obtain the glass with deformation resistance, it is necessary to consider to carry out existing glass composition Adjustment, such as, in order to obtain with small glass is deformed, the modulus of elasticity (E) of glass should be big.But in view of the entirety of glass Mechanical performance, such as intensity, the E of glass should be in the range of optimization.If E is too small, pressure effect is lower to cause big change Shape can destroy device interior electronic component.When E is excessive, glass becomes really up to the mark thus loses its toughness, so as to cause glass Resistance to crack expansibility reduces, and machinability reduces.In view of the chemical tempering in later stage, this glass should also have high bend Clothes point temperature, the less coefficient of expansion (CTE), to ensure that glass is indeformable during chemical tempering.

Relatively thin mobile device or non-mobile device is also required to glass in light weight as cover plate, touch-screen or display Glass.With the development of electronic device, portability is more and more next important, and weight is one of key issue.Thus, mitigate portable Device weight is a kind of new development trend.But the density of common soda-lime-silica glass is more than 2.5g/cm³, the density can not Meet the needs of this new development, and soda-lime-silica glass does not have good chemical tempering performance.Dol is general after chemical tempering Less than 10 μm.This thickness can not meet cover plate, touch-screen or the requirement for showing glass.

Density is less than 2.5g/cm³Foam glass can reduce the gross weight of equipment, equipment is easily facilitated carrying.Applying Add external force or due to deadweight in the case of, particularly in the case of large-sized touch/protection display, can reduce due to from Body weight and caused deformation, such as warpage or bending, and also help and reduce what is deformed during chemical tempering Probability.Meanwhile low density glass has open glass network structure, this can speed up the ion exchange during chemical tempering Speed, improve production efficiency.

In addition, after chemical tempering, if it is desired to the glass is directly assembled in electronic device, such as mobile phone, intelligence In phone, tablet personal computer, notebook computer, PDA etc., the size and dimension of glass is crucial.Need glass size after processing Change is smaller, the glass preferably without change in size and without deformation.Become increasing in the size of chemically toughened glass In the case of, this requires even more important.For example, the touch-screen on television set or giant display needs at least 1 × 2 meter of big chi Very little chemically toughened glass, such application requirement glass have least amount of deformation.In addition, chemical tempering is under the high temperature conditions Handling process, during chemical tempering, glass should be sufficiently stable, does not deform, and without warpage or bending, and to keep Size constancy.

Glass of the prior art is no can to meet chemically tempering, high deformation resistance, i.e., in chemical tempering mistake simultaneously Cheng Zhong, glass does not deform, warpage or bending, while keeps size constancy, and high yield strength temperature and low-density will Ask.

In terms of presently disclosed patent document, and the patent document of prior art described below can not all meet simultaneously Both can have deformation resistance, high yield strength temperature and requirement in light weight again with chemical tempering, so as to meet to for moving The demand of the cover plate or touch panel glass of dynamic equipment or non-mobile device.

Patent application publication US 2009/0142568 is described containing Al₂O₃And B₂O₃Alumina silicate glass, should Glass has high scratch resistance, and still, the glass has the high SiO more than 64wt%₂Content.High SiO₂Content causes glass It is difficult to melt, production cost is high, and chemical tempering performance is also difficult to be optimized.High SiO in glass₂Content can also increase Fragility, therefore, the resistance to crack expansibility deficiency of the glass.SiO₂The adjustment of the deformation resistance of the high glass of content is also limited System.Do not optimize the ratio between Network former and Network former and between Network former and Network modifier, from And the glass with high deformation resistance ability can not be provided.The deformation resistance and surrender temperature of glass are not referred in the publication Degree.

Chinese patent application CN 200910086806 is disclosed containing ZrO₂Alumina silicate glass, still, the glass is not Containing B₂O₃, the fragility of the glass is high, and resistance to crack expansibility is low.In addition, the glass bag contains CaO, the glass comprising CaO is easy Crystallization, and the CaO in glass is also unfavorable for chemical tempering.In addition, the glass also includes the disagreeableness Sb of environment₂O₃。

Patent application publication US 2009/0202808 describes a kind of glass of anti scuffing.But the glass bag contains SiO more than 64wt.%₂.High SiO₂Glass is caused to be difficult to melt, and chemical tempering performance is not easy to optimize.It is high in glass SiO₂The fragility of glass, therefore resistance to crack expansibility and the deformation resistance deficiency of the glass can be increased.In addition, the glass bag contains CaO, the CaO in glass are unfavorable for chemical tempering.MgO the ＞ 5wt.%, the MgO of such high content of glass in the patent document It is also unfavorable for chemical tempering.

Patent application publication US 2008/0286548 and US 2009/0220761 are described with high-mechanical property Alkali alumino-silicates glass.But the glass has high fusing point, it is difficult to melt.The glass bag is containing 64-68mol.%'s SiO₂(percentage by weight ＞ 64wt.%), this increases melting temperature, adds glass viscosity and number of bubbles.It is high in glass SiO₂Content can also increase fragility, therefore, resistance to crack expansibility and the deformation resistance deficiency of the glass.

United States Patent (USP) US 4055703 is described comprising P₂O₅Glass.But the glass has high P₂O₅Concentration, it is 2-20wt%.P₂O₅Concentration is high, easily causes glass opaque.Therefore, the patent needs more ZnO, still, more ZnO Easily cause to crystallize, it is in addition and uneconomic.

United States Patent (USP) US 5674790 describes the glass with good chemical tempering performance.But the glass has height Li₂O concentration, it is 8-10wt%, for batch production, cost is expensive for this.In addition, include Li₂O glass is direct Use KNO₃Requirement can not be reached by carrying out chemical tempering, it is necessary to carried out salt-mixture or two-step method tempering, be processed into so as to add This, limits the purposes of the glass.

Patent application publication US 2011/0201490 is described without ZrO₂Alumina silicate glass, the glass is crisp Property is low.But the hardness of the glass is low, Hv ＜ 520Kg/mm², and modulus of elasticity is also low.The glass is free of ZrO₂, glass is hard Spend low, be very easy to be scraped off, and under so low modulus of elasticity glass deformation resistance can be caused very poor, used in outer masterpiece It is lower to produce very big deflection, influence to use.

Summary of the invention

The inventors found that a kind of novel glass composition, the defects of can solve the problem that in the prior art, because And can provide a kind of has deformation resistance, high yield strength temperature and zirconium in light weight boron-alumina silicate glass.

It was found by the inventors of the present invention that multiple network is introduced in alumina silicate glass forms body, rather than simple use SiO as Network former₂And Al₂O₃, glass network structure can be optimized, make glass that there is high deformation resistance, high yield Point temperature, low-density, low fragility, high resistance to crack extension ability and high chemical tempering ion-exchange capacity.Adjust B₂O₃、 P₂O₅、ZrO₂With SiO₂、Al₂O₃Ratio, can enable glass that there are optimal combining properties.

It was found by the inventors of the present invention that addition ZrO₂And B₂O₃Glass deformation resistance, scratch resistance and cracking resistance can be improved Line expanding ability, fragility is reduced, while optimization and adjustment and P₂O₅、Al₂O₃、SiO₂Content and proportionate relationship, can make Glass has simultaneously is more suitable for chemical tempering, higher deformation resistance, high yield strength temperature and low-density.

Glass of the present invention is applied to chemical tempering.Zirconium boron-the alumina silicate glass has following performance：Bullet after chemical tempering Property modulus 60GPa≤E≤78GPa；620 DEG C≤At≤850 DEG C of yield point；Thermal coefficient of expansion is 7.5 × 10^-6/K≤CTE≤9.8 ×10^-6/K；Density≤2.5g/cm³；Bearing stress (CS) is at least 700MPa；Surface stress layer thickness (Dol) is at least 25 μm。

Zirconium boron-the alumina silicate glass for possessing this performance is a kind of high elastic modulus, high rigidity and low brittle glass Material.The glass material no deformation, warpage or bending during chemical tempering, and size constancy can be kept.In addition, The glass has low density, is easy to carry.

In the present invention, except as otherwise noted, the percetage by weight of all components is all based on the gross weight of glass all components Amount, and glass all components sum is 100%.

Therefore, the invention provides following technical scheme.

The invention provides one kind to contain ZrO₂And B₂O₃Alumina silicate glass, the glass bag contains：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 51wt.%,

0.004≤ZrO₂/Al₂O₃＜ 0.2,

0.07≤B₂O₃/SiO₂≤ 0.25,

0.16≤(P₂O₅+Al₂O₃)/SiO₂≤0.75。

On the other hand, the invention provides one kind to contain ZrO₂And B₂O₃Alumina silicate glass, the glass bag contains：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 39wt.%,

0.005≤ZrO₂/Al₂O₃≤ 0.17,

0.07≤B₂O₃/SiO₂≤ 0.2,

0.2≤(P₂O₅+Al₂O₃)/SiO₂≤0.6。

Another aspect of the invention provides one kind and contains ZrO₂And B₂O₃Alumina silicate glass, the glass bag contains：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%,

0.01≤ZrO₂/Al₂O₃≤ 0.14,

0.07≤B₂O₃/SiO₂≤ 0.19,

0.23≤(P₂O₅+Al₂O₃)/SiO₂≤0.55。

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, wherein 52wt.%≤ SiO₂≤ 61wt.%, preferably 52wt.%≤SiO₂≤ 59wt.%, more preferably 52wt.%≤SiO₂≤ 58wt.%.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, wherein 0.2wt.% ≤ZrO₂≤ 1.5wt.%, preferably 0.5wt.%≤ZrO₂≤ 1wt.%.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, wherein 4.5wt.% ≤B₂O₃≤ 8wt.%, preferably 4.5wt.%≤B₂O₃≤ 7.5wt.%.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, wherein 20.5wt.% ≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%, preferably 21wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, wherein 0.015≤ ZrO₂/Al₂O₃≤ 0.1, preferably 0.02≤ZrO₂/Al₂O₃≤0.1。

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, the bullet of the glass Property modulus is 60GPa≤E≤78GPa, preferably 69GPa ＜ E≤78GPa, more preferably 70GPa≤E≤78GPa.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, the glass bend Clothes point is 620 DEG C≤At≤850 DEG C, preferably 630 DEG C≤At≤830 DEG C, more preferably 650 DEG C≤At≤800 DEG C.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, wherein the glass Density≤2.50g/cm³, preferably≤2.49g/cm³, more preferably≤2.45g/cm³。

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, under external force, Deformation values≤5mm, preferably≤1mm, more preferably≤0.5mm.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, wherein the glass Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9×10^-6/ K, preferably 7.5 × 10^-6/K≤CTE≤8.8×10^-6/K。

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, Dol after chemical tempering >=25 μm, preferably Dol >=30 μm, more preferably Dol >=35 μm, most preferably Dol >=40 μm.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, CS after chemical tempering >=700MPa, preferably CS >=800MPa, more preferably CS >=900MP, most preferably CS >=1000MPa.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, it is hard after chemical tempering Degree >=530MPa, preferably >=580MPa, more preferably >=650MPa, most preferably >=700MPa.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, chemical tempering temperature For 350 DEG C~490 DEG C, the chemical tempering time is 1~16h；It is preferred that chemical tempering temperature is 350 DEG C~490 DEG C, during chemical tempering Between be 2~12h；More preferably chemical tempering temperature is 400~480 DEG C, and the chemical tempering time is 2~8h.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, the glass is thin Glass, thickness≤5.0mm, preferably≤4.0mm, more preferably≤2.0mm, particularly preferably≤1.0mm.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, the glass can lead to Cross under a variety of methods, such as micro- float glass process, glass tube down-drawing, discharge orifice to draw and draw method production under method or melting.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass in the mobile electricity of manufacture Conduct in words, smart phone, tablet personal computer, notebook computer, PDA, television set, PC, MTA machines, industrial display The purposes of cover plate.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass be used for manufacture touch-screen Purposes in cover plate, protective window, automotive window, train vehicle window, aviation machine window, hard disk base material.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass for white domestic appliances lead The purposes in domain, such as it is used for refrigerator or kitchen tools.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, it can act as moving The backboard of dynamic electronic device, the cover plate of portable device or notebook.

The present invention also provides one kind and contains ZrO₂And B₂O₃And be free of Li₂O and CaO alumina silicate glass, it is characterised by institute For the glass stated after chemical tempering, modulus of elasticity is 60GPa≤E≤78GPa, and yield point is 620 DEG C≤At≤850 DEG C, density For≤2.5g/cm³。

On the other hand, the present invention provides a kind of alumina silicate glass, is characterised by the glass after chemical tempering：

Modulus of elasticity 60GPa≤E≤78GPa；

620 DEG C≤At≤850 DEG C of yield point；

Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9.8×10^-6/K；

Density≤2.5g/cm³；

Bearing stress CS >=700MPa；

Surface stress layer thickness Dol >=25 μm.

Contain ZrO described in both of the aforesaid aspect in the present invention₂And B₂O₃Alumina silicate glass, be characterised by the glass Glass forms：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 51wt.%,

0.004≤ZrO₂/Al₂O₃＜ 0.2,

0.07≤B₂O₃/SiO₂≤ 0.25,

0.16≤(P₂O₅+Al₂O₃)/SiO₂≤0.75。

Being further characterized by the glass composition is：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 39wt.%,

0.005≤ZrO₂/Al₂O₃≤ 0.17,

0.07≤B₂O₃/SiO₂≤ 0.2,

0.2≤(P₂O₅+Al₂O₃)/SiO₂≤0.6。

Further it is characterised by that the glass composition is：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%,

0.01≤ZrO₂/Al₂O₃≤ 0.14,

0.07≤B₂O₃/SiO₂≤ 0.15,

0.23≤(P₂O₅+Al₂O₃)/SiO₂≤0.55。

Another aspect of the invention provide it is a kind of can be used in chemical tempering contain ZrO₂And B₂O₃Alumina silicate glass, make For usual mobile device or non-mobile device protecting screen, touch-screen or display screen when, under external force, deformation values≤5mm are excellent Choosing≤1mm, more preferably≤0.5mm.

Aforementioned schemes contain ZrO₂And B₂O₃Alumina silicate glass, be characterised by that glass composition is：

Wherein, 23wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 51wt.%,

0.004≤ZrO₂/Al₂O₃≤ 0.16,

0.07≤B₂O₃/SiO₂≤ 0.25,

0.16≤(P₂O₅+Al₂O₃)/SiO₂≤0.75。

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, the glass can By chemical tempering, Dol >=25 μm and CS >=700MPa after chemical tempering, wherein it is preferred that Dol >=30 μm, more preferably Dol >=35 μm, Most preferably Dol >=40 μm.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, the glass can By chemical tempering, Dol >=25 μm and CS >=700MPa after chemical tempering, wherein it is preferred that CS >=800MPa, more preferably CS >= 900MP, most preferably CS >=1000MPa.

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, be characterised by described Glass is after chemical tempering：

Modulus of elasticity 70GPa≤E≤78GPa；

630 DEG C≤At≤850 DEG C of yield point；

Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9×10^-6/K；

Density≤2.49g/cm³。

Contain ZrO described in foregoing either a program in the present invention₂And B₂O₃Alumina silicate glass, as usual mobile When equipment or non-mobile device protecting screen, touch-screen or display screen, it is characterised by the glass after chemical tempering：

Under external force, deformation values≤5mm, preferably≤1mm, more preferably≤0.5mm；

Modulus of elasticity 70GPa≤E≤78GPa；

620 DEG C≤At≤850 DEG C of yield point；

Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9×10^-6/K；

Density≤2.5g/cm³；

Bearing stress CS >=700MPa；

Surface stress layer thickness Dol >=25 μm.

Glass of the present invention is also suitable as such as personal digital assistant, movement or cellular phone, wrist-watch, portable computer With notebook computer, digital camera, PDA cover plate, or the substrate glass as touch-screen.The glass is also useful as electricity Subbase material, such as hard disk.The glass has high impact properties, high rigidity, high elastic modulus, low fragility, high deformation resistance, height Yield point temperature and low-density.The glass is suitable to the ion exchange by chemical tempering.

Detailed description of the Invention

The present invention relates to contain ZrO₂And B₂O₃Alumina silicate glass, its after chemical tempering modulus of elasticity be 60GPa≤ E≤78GPa；Yield point is 620 DEG C≤At≤850 DEG C；Thermal coefficient of expansion is 7.5 × 10^-6/K≤CTE≤9.8×10^-6/K；It is close Degree≤2.5g/cm³；Compression (CS) is at least 700MPa；Surface stress layer thickness (Dol) is at least 25 μm.In addition, the glass Glass has that deformation resistance, yield point temperature are high and in light weight, while this glass fragility is low, modulus of elasticity is high, resistance to Crack Extension Property good and hardness height.

SiO₂It is conventional Network former, in soda-lime-silica glass, SiO₂It is main Network former.In manosil AS In salt glass, SiO₂And Al₂O₃It is main Network former.But simple SiO₂And Al₂O₃The glass of Network former composition is crisp Property is big, and the ion-exchanging efficiency of intensity, deformation resistance and chemical tempering is not high enough.By introducing ZrO₂、B₂O₃And further Introduce P₂O₅Network structure is adjusted, the network structure of optimization can be formed, makes glass that there is high deformation resistance, height to bend Take temperature, low-density, low fragility, high resistance to crack extension ability and high chemical tempering ion-exchange capacity.Adjust B₂O₃、 P₂O₅、ZrO₂With SiO₂、Al₂O₃Ratio, can enable glass that there are optimal combining properties.

Introduce ZrO₂, use ZrO₂Instead of part Al₂O₃, glass microstructure can be changed, improve the modulus of elasticity of glass, The CTE of glass is reduced, effectively controls ZrO₂And Al₂O₃Ratio, it is possible to increase the non-deformability and yield point temperature of glass.

Introduce B₂O₃, use B₂O₃Instead of part SiO₂, glass network structure can be changed, so as to improve the CTE of glass And fragility.Effectively control B₂O₃And SiO₂Ratio, glass network structure can be changed, optimize glass properties, reach reduction, optimization The brittle purpose of CTE and glass of glass, improve glass resistance to crack extension ability.

Further, it is possible to introduce P₂O₅, adjust (P₂O₅+Al₂O₃)/SiO₂Content and ratio, can improve chemical tempering from Sub- switching performance, while optimize the deformation resistance, thermal coefficient of expansion and yield point temperature of glass, and glass is obtained suitably Melting temperature and optimization performance.

Strength of glass can be characterized with compression (CS) and thickness degree (Dol).High CS and height are needed in actual applications Dol.Generally, the CS higher than the 700MPa and Dol higher than 25 is favourable.

Yield point (At) is defined as the starting point temperature of glass deformation in the present invention.Deformation point temperature may be defined as by swollen On the thermal dilatometry of swollen meter measurement, deformation point is the point of elongation vanishing.When temperature reaches yield point, glass starts to become It is soft.Glass can even deform because of deadweight.If yield point is low, in hot environment, the probability of glass deformation is big；It is any Small deformation can all influence the shape and size of final products.

Yield point is usually 620 DEG C≤At≤850 DEG C.Chemical tempering temperature is 380-600 DEG C, including cryochemistry tempering With high temeperature chemistry tempering, the chemical tempering time is 1-30 hours.Chemical tempering is ion exchange process, and the temperature of chemical tempering is got over Height, the speed of ion exchange are faster.Yield point should be higher than chemical tempering temperature 250-300 DEG C.If yield point and chemical steel The difference for changing temperature is small, it may occur that compression relaxes.Yield point differs greatly with chemical tempering temperature, can reduce compression Loose probability, it can also reduce the probability of deformation.Yield point can be determined easily by dilatometer, so as to estimate chemical steel Change the upper limit of temperature.On the other hand, the cover plate with high yield strength can be used on the device that runs in high temperature environments, For example, the glass with high yield strength can be with air line, this glass does not occur soft at a high temperature of friction produces Change.

Deformation resistance is included in the deformation under load (pressure, impulsive force) effect in the present invention, during chemical tempering Change in shape and during chemical tempering size change.Deformation resistance refers to that glass is indeformable under the conditions of any of the above described Or deform less than critical value.Morphotropism during chemical tempering refers to that the increasing of glass size after ion exchange adds deduct It is small.For example, in K⁺Replace Na⁺After become large-sized.Generally, 7.5 × 10^-6/K≤CTE≤9.8×10^-6/ K glass is in chemical steel Size constancy can be kept during change, and modulus of elasticity will be very in 60GPa≤E≤78GPa, glass deformation after chemical tempering It is small, so as to protect electronic component under certain load from infringement.The modulus of elasticity of glass is defined as glass and become in elasticity In the shape stage, the ratio of direct stress and corresponding normal strain.

The deformation resistance of glass is described as follows：

Glass is placed on two strong points or on two support edges, two spans between the strong point or support edge are The maximum length L of glass, load forces F is applied to the top side of glass, and glass is horizontal during no load forces, and the horizontal plane claims For initial water plane, as load forces increase, glass deforms, and the distance between deformation point and initial water plane are deformation Value.Deformation values are bigger, and glass is more easily deformed, and deformation resistance is lower.

When the glass is used as the display of moving device, diagonal≤500mm of the glassware ,≤300mm, ≤200mm、≤120mm、≤100mm、≤95mm、≤90mm、≤80mm、≤75mm、≤70mm、≤60mm；The glass system Area≤500cm of product²、≤300cm²、≤100cm²、≤50cm²；When thickness is 0.2mm-3mm, deformation values≤5mm ,≤ 3mm、≤1mm、≤0.5mm、≤0.1mm。

During used as moving device, moving device means small size, size≤12 inch of mobile display ,≤ 9.7 inches ,≤4.3 inches ,≤3.8 inches.

For the cover plate for moving device, when glass size≤12 inch ,≤9.7 inches ,≤4.3 inches ,≤ 3.8 inches, when the thickness of glass is 0.2mm-3mm, glass deformation value is≤5mm ,≤3mm ,≤1mm ,≤0.5mm ,≤ 0.1mm。

For other devices, such as TV, large-sized display etc., size is generally larger.Size >=12 of display Inch, >=20 inches, >=30 inches, >=42 inches, >=55 inches or >=60 inches.

For for display cover plate, when glass size >=12 inch, >=20 inches, >=30 inches, >=42 inches, >=55 inches or >=60 inches, when thickness of glass is 1-5mm, glass deformation value is≤10mm ,≤5mm ,≤3mm ,≤1mm, ≤0.5mm、≤0.1mm。

Example in the present invention is used only to illustrate advantages of the present invention and characteristic, it is impossible to is considered as to the scope of the invention Limitation.

The rigidity of material is defined as the stress needed for the relative deformation of material generation unit elasticity.It is to characterize material resistance The mechanical performance index of elastic deformability.

Glass has the ability of certain resistance to deformation in the present invention, that is, has enough rigidity.

For resistance to deformation zirconium boron-alumina silicate glass of chemical tempering, rigidity is in about 0.75MPam^0.5-0.85MPam^0.5's In the range of, preferably in about 0.83MPam^0.5To about 0.85MPam^0.5In the range of.Rigidity is less than 0.75MPam^0.5, glass resistance to deformation Ability is relatively low, and is more than 0.85MPam^0.5The difficulty of glass processing will be caused due to too high stress.

When the fragility of glass is defined as transition temperature load applied below, glass do not occur it is any it is observed that plasticity (strain stress is 10 for deformation^-4Below), that is, it is broken.The fragility of glass is bigger, after stress glass be easy to do not have it is premonitory In the case of rupture suddenly, so as to cause personal injury and property loss.

For resistance to deformation zirconium boron-alumina silicate glass of chemical tempering, fragility is 6-9 μm after chemical tempering^-0.5, preferably 6- 8.5μm^-0.5, more preferably 6-8 μm^-0.5.Fragility is less than 6 μm^-0.5, glass hard (HRC65Yi Shang) is too small and is unfavorable for glass processing, holds in the application Scratch and crackle are also easy to produce, and fragility is more than 9 μm^-0.5Then the glass extended capability of resistance to crackle can be very poor, is produced in glass by external force After crackle, crackle can extend at once, cause glass breaking.

The present invention relates to deformation resistance, high yield temperature and low density glass, the glass is containing ZrO₂And B₂O₃Aluminium Silicate glass.Modulus of elasticity 60GPa≤E≤78GPa after the resistance to deformation glass chemistry toughening；620 DEG C≤At≤850 of yield point ℃；Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9.8×10^-6/K；Density≤2.5g/cm³.The glass is suitable to chemical tempering, And suitable for preparing the glassware of chemical tempering.

Glass of the present invention is free of Li₂O and CaO.

In addition, the glass be suitable to prepare thickness≤5.0mm ,≤4.0mm ,≤2.0mm ,≤1.0mm ,≤0.5mm it is thin Glass.

The glass is environment-friendly, and is free of As₂O₃And Sb₂O₃.The glass can be produced with float technology.

SiO₂It is main glass forming substance, and is one-component maximum in glass, strong network structure can be formed.Al₂O₃ And B₂O₃And glass forming substance.P₂O₅It can at least be crystallized in the form of four kinds, most common polymorph includes P₄O₁₀Molecule, it is other Polymorph be polymerization.P₂O₅Feature provide weak network structure.Strong network structure is unfavorable for ion exchange, is led Cause the reduction of ion-exchange speed and depth.Weak network structure can then reduce the stability of glass.Therefore, it should which optimization is strong netted Structure and weak network structure.As 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 51wt.%, preferably 20wt.%≤ZrO₂+B₂O₃ +P₂O₅+Al₂O₃≤ 39wt.%, more preferably 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃During≤33wt.%, it can not only obtain High Dol, and high CS can be obtained.Meanwhile the deformation resistance of glass, intensity can be improved, reduce glass fragility.Enter one Step, ZrO₂+B₂O₃+P₂O₅+Al₂O₃Summation is 20.5wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%, preferably 21wt.% ≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%.

SiO₂Content be 45- ＜ 64wt.%, more preferably preferably 50-63.5wt%, 52-62wt%.SiO₂At this Exist in a little glass using at least 45wt% amount as netted forming agent.Too low SiO₂The durable of glass can be negatively affected Property.The glass bag of many prior arts contains the SiO higher than 64wt%₂.Tetrahedron SiO₄ ^-It is the essential building blocks in glass, tightly Close and harder, such structure causes glass more crisp and resistance to crack expansibility reduces, while the ion with reduction is handed over Throw-over degree.In addition, SiO₂Ratio increase above 64wt% transition temperature and melting temperature can be caused to raise.SiO₂Amount be 50-63.5wt% helps to reduce CTE.Further, SiO₂Content can be 52wt.%≤SiO₂≤ 61wt.%, preferably 52wt.% ≤SiO₂≤ 59wt.%, more preferably 52wt.%≤SiO₂≤ 58wt.%.

Al₂O₃Content in the range of ＞ 10-28wt%.Al₂O₃Deformation resistance, thermal expansion system for improving glass Number, heat resistance, ion-exchange performance and modulus of elasticity etc. are effective.But work as Al₂O₃Content increase when, devitrification crystal is past Toward precipitating in glass, thermal coefficient of expansion becomes too small so that being difficult to be consistent with adjacent material, and at high temperature viscous Degree becomes higher, it is difficult to produces.Al₂O₃Less than the modulus of elasticity and intensity decreases that 10wt% will cause glass, thermal coefficient of expansion becomes Big and yield temperature point step-down.

ZrO₂The chemical stability of glass, increase viscosity, hardness can be improved, and reduces thermal coefficient of expansion, reduces glass Fragility.ZrO₂Content be 0.01-2wt.%.ZrO₂＞ 2wt.% easily cause glass crystallization, and ZrO₂＜ 0.01wt.%'s Glass does not have high chemical stability.ZrO2 contents are 0.1wt.%≤ZrO₂≤ 2wt.%, preferably 0.1wt.%≤ZrO₂≤ 2wt.%, more preferably 0.1wt.%≤ZrO₂≤ 1.5wt.%.Further, 0.2wt.%≤ZrO₂≤ 1.5wt.%, preferably 0.5wt.%≤ZrO₂≤ 1wt.%.

Further, 0.004≤ZrO₂/Al₂O₃＜ 0.2 can increase and keep glass to have high modulus of elasticity, improve glass Glass deformation resistance, the CTE and fragility for reducing glass.Only include Al₂O₃Glass fragility it is big, this causes the possibility of glass breaking Increase.Some ZrO are added in right amount₂So that 0.004≤ZrO₂/Al₂O₃＜ 0.2, glass is by the bullet with 60GPa≤E≤78GPa Property modulus and 7.5 × 10^-6/K≤CTE≤9.8×10^-6/ K thermal coefficient of expansion.By adding ZrO₂, Dol and CS are changed Enter, while the intensity of glass is also improved.ZrO₂Composition is similar with the acid proof mode of silica, therefore, containing ZrO₂'s Glass often has good acid resistance, or even in the case where dioxide-containing silica is low and such.Meanwhile the oxidation of mixing The tempering ability of thing glass is generally with including equivalent Al₂O₃Or ZrO₂TERNARY GLASS it is identical.ZrO₂/Al₂O₃For 0.004≤ ZrO₂/Al₂O₃＜ 0.2, preferably 0.005≤ZrO₂/Al₂O₃≤ 0.17, more preferably 0.01≤ZrO₂/Al₂O₃≤0.14.Further, 0.015≤ZrO₂/Al₂O₃≤ 0.1, preferably 0.02≤ZrO₂/Al₂O₃≤0.1。

Use B₂O₃Instead of part SiO₂The CTE and fragility of glass can be improved.0.07≤B₂O₃/SiO₂≤ 0.25 can reduce CTE and the fragility for reducing glass.Use B₂O₃Instead of SiO₂Glass network structure can be changed.SiO₄Tetrahedron and [3] BO₃([3] table Show the stratiform trihedral structure of two-dimensional space) plane triangle does not need charge compensation, therefore they form open netted knot Structure.[3] the specific plane structure of unit B also contributes to greatly be densified.[3] B Plain Triangular Elements are introduced SiO₂Cause network structure hardness step-down in main network structure so that be densified under stress.Open network structure and Planar structure causes densification to be easier, and it reduce the CTE of glass, density and fragility.B₂O₃In the range of 4-15wt%. B₂O₃There is the effect for reducing melting temperature, high temperature viscosity and density as effective fluxing agent.B₂O₃It is close glass can be reduced Degree, reduce thermal expansivity, increase ther-mal shock resistance and chemical resistance.Add B₂O₃Fragility and density can be reduced.Further, B₂O₃/SiO₂For 0.07≤B₂O₃/SiO₂≤ 0.25, preferably 0.07≤B₂O₃/SiO₂≤ 0.2, more preferably 0.07≤B₂O₃/SiO₂≤ 0.19。

In the glass composition of the present invention, to realize the glass properties of optimization, the purpose of the present invention is realized, it has been found that Increase P in glass₂O₅Can improve the velocity of ion exchange of glass.SiO₂It is main glass forming substance, and is in glass Maximum one pack system, can form strong network structure.P₂O₅And glass forming substance.P₂O₅It can at least be crystallized in the form of four kinds.It is most normal The polymorph seen includes P₄O₁₀Molecule.Other polymorph are polymerizations, but in all cases, phosphorus atoms are by tetrahedral Oxygen atom is connected, and one of oxygen atom forms end P=O keys.The combining form of this phosphorus oxygen key is not as some silicate In exist with silicon-oxy tetrahedron structure, but use by the P that is connected with each other₆O₆The layer structure that ring is formed.P₂O₅Feature provide Weak network structure.Strong network structure is unfavorable for ion exchange, causes the reduction of ion-exchange speed and depth.It is but weak Network structure can reduce the stability of glass.Therefore, it should optimize the ratio and composition of strong network structure and weak network structure.Just Locality combination is by force and weak glass forming substance can improve ion-exchange speed and depth.P₂O₅By opening glass structure and increasing Add diffusion velocity and the raising to glass tempering performance serves key effect.P₂O₅It is more excellent for 0-8wt%, preferably 0-4wt% Select 0.1-2wt%.P₂O₅Increase also advantageously increase yield point and adjustment glass melting temperature.But P₂O₅＞ 8wt.% will Chemical resistance and product uniform ingredients degree to glass have a negative impact, while P₂O₅＞ 8wt.%, glass are easy to devitrification. From the viewpoint of batch production cost, more than the substantial amounts of P of needs₂O₅It is undesirable.

Further, P is adjusted₂O₅、Al₂O₃And SiO₂Ratio can optimize glass tempering performance.0.16≤(P₂O₅+ Al₂O₃)/SiO₂≤ 0.75 can increase the speed of ion exchange, increase Dol, increase CS and bending strength.(P₂O₅+Al₂O₃)/ SiO₂Appropriate melting temperature and high can be obtained for 0.16-0.75, preferably 0.2-0.6, more preferably 0.23-0.55 glass Modulus of elasticity, and then the glass can obtain Dol >=25 μm and CS as >=700MPa after chemical tempering.

Na₂O exists with fluxing agent, and the position exchanged is provided for subsequent ion exchange.Na₂O ＞ 20wt.% can reduce glass Chemical resistance, usual glass should contain at least 9% Na₂O, the melting temperature of glass is maintained at practical level, and And make glass that there is significant ion-exchange performance.

MgO be reduce glass high temperature viscosity so as to improve the component of meltability and formability, and can improve strain point and Young's modulus.In addition, in alkaline earth oxide component, MgO can more be significantly improved ion-exchange performance.Correspondingly, lead to Often wish content in the range of 0- ＜ 3.5%.

CaO is not present in the glass composition.On the one hand, easily make devitrification of glass using CaO, produce devitrification, on the other hand, CaO has obvious negative effect to chemical tempering.

SrO is the component that can consider to add with various purposes.But when containing these substantial amounts of components, at some In the case of, density and the thermal coefficient of expansion increase of glass, increased devitrification resistance deteriorate, and cracking frequency uprises, compression after ion exchange The depth shallower of layer.

K₂O can reduce the viscosity of glass under high temperature, so as to improve the meltability of glass and moldable property, reduce crackle Incidence.In addition, K₂O is also the composition for improving devitrification behavior.K₂O content generally in the range of 0-8wt.%, when higher than During 8wt%, increased devitrification resistance deterioration.

TiO₂The viscosity of glass under high temperature can be made reduce, so as to improve the meltability of glass.TiO₂Content generally in 0- In the range of 5wt.%, when higher than 5wt%, the easy crystallization of glass.

The glass of the present invention can include a small amount of conventional fining agent.The total amount of the fining agent of addition is preferably up to 2.0wt%, more preferably up to it is 1.0wt%, this tittle is relative to the amount of the other remaining ingredients of glass, but addition will cause Glass composition components are 100wt%.At least one of following composition can be included according to the glass of the present invention and be used as fining agent (being added in addition in remaining glass ingredient with wt% amount)：

CeO₂0.01- ＜ 0.2%

F₂0-0.5%

SnO₂0.01-0.5%

In order to help to eliminate formation of gaseous inclusions, it is favourable to add other chemical fining agents.This kind of fining agent filling contains The bubble of the early formation of gas, so as to add their climbing speeds in melting.Typical fining agent includes but unlimited In：Arsenic oxide arsenoxide, antimony oxide, tin oxide and cesium oxide；Metal halide；Metal sulfate etc..But arsenic and antimony are typically considered to It is poisonous material, glass of the invention is free of arsenic and antimony.

Embodiment

Raw material used in the experiment of the embodiment of the present invention are that oxide, hydroxide, carbonate and nitrate etc. are (equal Purchased from Chemical Reagent Co., Ltd., Sinopharm Group, Suzhou, chemical grade).

The experiment of the embodiment of the present invention determines the transition temperature T of glass on the thermal dilatometer of resistance to relaxation (DIL402PC of resistance to relaxation)_g With thermal coefficient of expansion CTE.After glass sample is made into 50mm or so bar-shaped sample, heated up from room temperature by 5 DEG C/min of speed To being completed.

The density of glass is determined by Archimedes principle.Glass sample is put into the container for filling water and accurately measured The Volume Changes of container reclaimed water, so as to obtain the volume of sample.Using the example weight divided by volume that can accurately measure, obtain close Degrees of data.

Sample chemical tempering.(diameter 250 × 250mm, depth 400mm) is carried out by the small-sized salt bath furnace of laboratory level to carry out Tempering.Sample is positioned on special anticorrosion stainless steel specimen holder.In KNO₃Progress 4-8 is small at 370-480 DEG C in salt bath When ion-exchange treatment.

The stress and stress layer depth of glass are by FSM6000 and determination of polarized light microscopy.

The CMT6503 types universal testing machine that the modulus of elasticity of glass is provided by Mei Tesi industrial systems Co., Ltd is tested.

The hardness of glass is tested by HXD-1000 Vickers hardnesses instrument.

Advantages and features of the invention are had been illustrated in embodiments of the invention, and these embodiments are not construed as to this hair Bright any restrictions.

Table 1 is the illustrative embodiments in the range of preferably constituting.Glass described in embodiment is according to following step It is rapid to prepare：

After weighing and mixing, mixture is put into platinum crucible.It is melted in 1600-1660 DEG C of electric smelter, Then it is cast in and is preheated in the stainless steel mould of 500~600 DEG C of appropriate temperature, is then slowly cooled into glass.

When carrying out deformation resistance assessment, for embodiments of the invention, sample L is 20mm.Sample L elects 20mm as, is In order to illustrate advantages and features of the invention, the sample L in these embodiments is not construed as any limitation of the invention.

Glass in comparative example has low-yield or low E or high density or low Dol or low CS.That is, existing skill The glass of art can not meet high yield strength, high E, low-density, high Dol and high CS needs simultaneously.

The contrast of the embodiment of table 3. and comparative example

Composition/wt.%	Embodiment 1	Comparative example 1	Comparative example 2
				SiO₂	55.10	73.00	75.62
Al₂O₃	21.16	0.27	1.17
				Na₂O	11.19	13.70	14.38
K₂O	3.04	0.03	0.26
				ZrO₂	0.69
CeO₂	0.10
				SnO₂	0.38
F₂
				B₂O₃	7.10
P₂O₅	1.24
				MgO		4.00
CaO		9.00	0.05
				ZnO			8.52
ZrO₂/Al₂O₃	0.033	0	0
				B₂O₃/SiO₂	0.129	0	0
(P₂O₅+Al₂O₃)/SiO₂	0.407	0.004	0.015
				ZrO₂+Al₂O₃+P₂O₅+B₂O₃(wt.%)	30.20	0.27	1.17

The performance comparision of embodiment and comparative example is as shown in table 4.

Table 4

	Embodiment 1	Comparative example 1	Comparative example 2
				Density (g/cm³)	2.39	2.52	2.54
Tg(℃)	600	560	570
				CTE(1×10^-6K^-1)	8.40	8.60	9.93
At (yield point) DEG C	730	610	630
				Modulus of elasticity (GPa) (after tempering)	73	72	70
Thickness (mm)	0.71	0.71	0.71
				Deformation values (mm) under 30N	0.070	0.085	0.090
Hardness (MPa)	700	530	550
				The chemical tempering time (hour)	6	6	6
Chemical tempering temperature (DEG C)	420	420	420
				Dol(μm)	42	7	10
CS(MPa)	970	607	590

Claims

1. one kind contains ZrO₂And B₂O₃Alumina silicate glass, the glass bag contains：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 51wt.%,

0.004≤ZrO₂/Al₂O₃<0.2,

0.07≤B₂O₃/SiO₂≤ 0.25,

0.16≤(P₂O₅+Al₂O₃)/SiO₂≤ 0.75, and

The alumina silicate glass is free of Li₂O、CaO、As₂O₃And Sb₂O₃。

2. according to claim 1 contain ZrO₂And B₂O₃Alumina silicate glass, the glass bag contains：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 39wt.%,

0.005≤ZrO₂/Al₂O₃≤ 0.17,

0.07≤B₂O₃/SiO₂≤ 0.2,

0.2≤(P₂O₅+Al₂O₃)/SiO₂≤0.6。

3. according to claim 1 contain ZrO₂And B₂O₃Alumina silicate glass, the glass bag contains：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%,

0.01≤ZrO₂/Al₂O₃≤ 0.14,

0.07≤B₂O₃/SiO₂≤ 0.19,

0.23≤(P₂O₅+Al₂O₃)/SiO₂≤0.55。

4. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, wherein 52wt.%≤ SiO₂≤ 61wt.%.

5. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, wherein 0.2wt.%≤ ZrO₂≤ 1.5wt.%.

6. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, wherein 4.5wt.%≤ B₂O₃≤ 8wt.%.

7. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, wherein 20.5wt.% ≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%.

8. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, wherein 0.015≤ ZrO₂/Al₂O₃≤0.1。

9. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, the elasticity of the glass Modulus is 60GPa≤E≤78GPa.

10. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, the glass bend Clothes point is 620 DEG C≤At≤850 DEG C.

11. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, wherein the glass Density≤2.50g/cm³。

12. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, under external force, Deformation values≤5mm.

13. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, wherein the glass Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9×10^-6/K。

14. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, Dol after chemical tempering ≥25μm。

15. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, CS after chemical tempering ≥700MPa。

16. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, it is hard after chemical tempering Degree >=530MPa.

17. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, chemical tempering temperature For 350 DEG C~490 DEG C, the chemical tempering time is 1~16h.

18. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, the glass is thin Glass, thickness≤5.0mm.

19. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, the glass can lead to Cross under micro- float glass process, glass tube down-drawing, discharge orifice to draw and draw method production under method or melting.

20. contain ZrO according to any one of claim 1-3₂And B₂O₃Alumina silicate glass, it can act as moving The backboard of dynamic electronic device, the cover plate of portable device or notebook.

21. contain ZrO according to any one of claim 1-19₂And B₂O₃Alumina silicate glass in the mobile electricity of manufacture Purposes in words, smart phone, tablet personal computer, television set, PC, MTA machines, industrial display as cover plate.

22. contain ZrO according to any one of claim 1-19₂And B₂O₃Alumina silicate glass be used for manufacture touch Shield the purposes in cover plate, protective window, automotive window, train vehicle window, aviation machine window, hard disk base material.

23. contain ZrO according to any one of claim 1-19₂And B₂O₃Alumina silicate glass be used for white domestic appliances The purposes in field.

24. one kind contains ZrO₂And B₂O₃And be free of Li₂O、CaO、As₂O₃And Sb₂O₃Alumina silicate glass, be characterised by described Glass after chemical tempering, modulus of elasticity is 60GPa≤E≤78GPa, and yield point is 620 DEG C≤At≤850 DEG C, and density is ≤2.5g/cm³, wherein MgO content is 0- ＜ 3.5wt.%, wherein the composition of the glass is：

25. according to claim 24 contain ZrO₂And B₂O₃And be free of Li₂O、CaO、As₂O₃And Sb₂O₃Alumino-silicate glass Glass, it is characterised by the glass after chemical tempering：

Modulus of elasticity 60GPa≤E≤78GPa；

620 DEG C≤At≤850 DEG C of yield point；

Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9.8×10^-6/K；

Density≤2.5g/cm³；

Bearing stress CS >=700MPa；

Surface stress layer thickness Dol >=25 μm.

26. contain ZrO according to claim 24 or 25₂And B₂O₃And be free of Li₂O、CaO、As₂O₃And Sb₂O₃Manosil AS Salt glass,

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 51wt.%,

0.004≤ZrO₂/Al₂O₃<0.2,

0.07≤B₂O₃/SiO₂≤ 0.25,

0.16≤(P₂O₅+Al₂O₃)/SiO₂≤0.75。

27. contain ZrO according to claim 24 or 25₂And B₂O₃And be free of Li₂O、CaO、As₂O₃And Sb₂O₃Manosil AS Salt glass, it is characterised by that the glass composition is：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 39wt.%,

0.005≤ZrO₂/Al₂O₃≤0.17,

0.07≤B₂O₃/SiO₂≤0.2,

0.2≤(P₂O₅+Al₂O₃)/SiO₂≤0.6。

28. contain ZrO according to claim 24 or 25₂And B₂O₃And be free of Li₂O、CaO、As₂O₃And Sb₂O₃Manosil AS Salt glass, it is characterised by that the glass composition is：

Wherein, 20wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 33wt.%,

0.01≤ZrO₂/Al₂O₃≤0.14,

0.07≤B₂O₃/SiO₂≤0.15,

0.23≤(P₂O₅+Al₂O₃)/SiO₂≤0.55。

29. it is a kind of can be used in chemical tempering contain ZrO₂And B₂O₃Alumina silicate glass, as usual mobile device or non-shifting Dynamic equipment protection screen, when touch-screen or display screen, under external force, and deformation values≤5mm, and the alumina silicate glass is not Containing Li₂O、CaO、As₂O₃And Sb₂O₃, it is characterised by that the glass composition is：

30. it is according to claim 29 can be used in chemical tempering contain ZrO₂And B₂O₃Alumina silicate glass,

Wherein, 23wt.%≤ZrO₂+B₂O₃+P₂O₅+Al₂O₃≤ 51wt.%,

0.004≤ZrO₂/Al₂O₃≤ 0.16,

0.07≤B₂O₃/SiO₂≤ 0.25,

0.16≤(P₂O₅+Al₂O₃)/SiO₂≤0.75。

31. according to claim 29 or 30 can be used in chemical tempering contain ZrO₂And B₂O₃Alumina silicate glass, change Dol >=25 μm and CS >=700MPa after tempering.

32. according to claim 29 or 30 can be used in chemical tempering contain ZrO₂And B₂O₃Alumina silicate glass, change Dol >=25 μm and CS >=700MPa after tempering.

33. according to claim 29 or 30 can be used in chemical tempering contain ZrO₂And B₂O₃Alumina silicate glass, it is special Sign is the glass after chemical tempering：

Modulus of elasticity 70GPa≤E≤78GPa；

630 DEG C≤At≤850 DEG C of yield point；

Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9×10^-6/K；

Density≤2.49g/cm³。

34. according to claim 29 or 30 can be used in chemical tempering contain ZrO₂And B₂O₃Alumina silicate glass, make For usual mobile device or non-mobile device protecting screen, touch-screen or display screen when, be characterised by the glass in chemical tempering Afterwards：

Under external force, deformation values≤5mm；

Modulus of elasticity 70GPa≤E≤78GPa；

620 DEG C≤At≤850 DEG C of yield point；

Thermal coefficient of expansion 7.5 × 10^-6/K≤CTE≤9×10^-6/K；

Density≤2.5g/cm³；

Bearing stress CS >=700MPa；

Surface stress layer thickness Dol >=25 μm.