CN102351421A - Preparation method of alkali aluminosilicate glass used for protective cover plates for display parts - Google Patents

Abstract

The invention discloses chemical toughened glass used for protective cover plates for display parts. The glass belongs to an alkali-aluminum-silicon system and comprises, by weight, 54 to 65% of SiO2, 10 to 17% of Al2O3, 8 to 16% of Na2O, 0 to 0.5% of Li2O, 0 to 6% of K2O, 0.01 to 3% of B2O3, 0.1 to 5% of MgO, 0.1 to 5% of CaO, 0.01 to 2% of SrO, 0.01 to 1% of ZrO2 and 0.01 to 1% of SnO2. The alkali aluminosilicate glass provided in the invention does not contain arsenic and antimony which pose pollution to environment; difficulty of manufacturing the glass is reduced through reasonable design of components. After specific chemical toughening treatment is carried out on the glass, surface hardness, scratch resistance and wear resistance of the glass are greatly improved, and the glass is a glass material applicable to a variety of protective cover plates for display parts.

Description

A kind of display device is with the preparation method of the alkali alumina silicate glass of cover sheet

Technical field

The invention belongs to glass art, relate to a kind of alkali alumina silicate glass, especially be fit to chemical tempering, be used for the preparation method of the alkali alumina silicate glass of display device cover sheet.

Technical background

Along with the development of technique of display is upgraded day by day; No matter be in common many occasions or as individual or family expenses; Various handwriting inputs and touch sensible equipment are increasing; Adaptability to environment for use has proposed new requirement, and touch-screen electronic product (mobile phone, palm PC, the demonstration of various terminal and common information query facility etc.) obtains unprecedented development.Portable electric appts move or use in contact with other article generation and rub unavoidably: key; Lighter; Coin; All kinds of magnetic cards etc.; More Ke Ke situation also happens occasionally; Owing to touch continually in the use; Add casual delineation; Touching; Consequent cut accumulation directly causes display screen surface coarse; Smooth finish descends; The unrest diffusing (instead) that has increased light is penetrated; Reduced transmitance; Brightness (colourity) homogeneity and resolving power; And be inhomogeneous and at random to the influence of screen, this just requires this series products surface to have higher intensity and anti-scraped finish performance.

The cover sheet that organic materials was once used as the aforementioned display device part, but, use additional cover plate scheme to bring extra disadvantageous effect to display screen because the defective of material itself (be prone to wear out, transmitance relatively poor) in addition, be not widely used.And glass is critical material indispensable in the technique of display evolution always; The composition that changes glass surface through chemical tempering (the less alkali metal cation of alkali metal cation replacement ionic radius that ionic radius is bigger) improves glass intensity, makes this kind glass on the cover sheet of aforementioned display device part, the ample scope for abilities arranged.Chemical tempering Study on Process and application all have long history; The chemically toughened glass research that is used for cover sheet is also more; Like Corning Incorporated, the bright photoelectricity in Chengdu company; The former has used in overcoming the clarification difficult procedures that high viscosity brings such as the finings friendly inadequately to environment such as arsenic, antimony; And the latter introduces more zirconium white in component, in the overflow downdraw process, is easy to generate the crystallization product of zirconium.

Summary of the invention

The object of the invention is to provide a kind of suitable chemical tempering; Basically do not contain the bigger elements of environmental pollution such as arsenic, antimony in the component; The glass of this method preparation has brought the glass mechanical property significantly to improve; Make invention gained glass have higher surface hardness, resistance to compression, anti-scraping performance all are greatly improved.

The present invention seeks to realize through following technical proposals.

A kind of display device is with the preparation method of the alkali alumina silicate glass of cover sheet, and this method comprises the steps:

1) according to the following raw material of the accurate weighing of mass percent:

The SiO of 54-65%₂, 10-17% Al₂O₃, 0-0.5% Li₂The Na of O, 8-16%₂The K of O, 0-6%₂The B of O, 0.01-3%₂O₃, the MgO of 0.1-5%, the CaO of 0.1-5%, the SrO of 0.01-3%, the ZrO2 of 0.01-1% and the SnO of 0.01-1%₂

2) the above-mentioned raw materials thorough mixing evenly is placed in the platinum rhodium crucible; Put into the container that refractory materials is built into again; Utilize Si-Mo rod that the temperature in the container is risen to 1550-1650 ℃, react after 5 hours, the temperature in the container is reduced to 1600 ℃ of insulations 60-120 minute;

3) glass metal in the crucible is poured into rapidly be cooled to tabularly in the metal form of preheating, place 500-600 ℃ of High Temperature Furnaces Heating Apparatus to anneal again 4-6 hour plate glass;

4) cutting and the grinding and polishing sheet glass after annealing is placed on for 3-5 time in 430-500 ℃ fused potassium nitrate liquid, rubidium nitrate liquid or the cesium nitrate liquid with deionized water glass cleaning plate surface and is incubated 4-10 hour;

5) take out sheet glass and be cooled to room temperature, glass cleaning plate surface is 3-5 time once more, promptly gets the alkali alumina silicate glass.

In the present invention, SiO₂Mass percentage content is 54-65%.SiO₂As the main component that forms glass, the raising of content helps the glass lightweight, and chemical-resistant improves, and other performance of glass also will improve.But along with SiO₂The increase high temperature viscosity of content will raise, and this is unfavorable for producing, so SiO₂Content is decided to be 54-65%, and more excellent is 58-64%.

Al₂O₃Mass percentage content be 10-17%, more excellent is 12-16%.High-load Al₂O₃Help the improvement of strain point of glass, bending strength, the raising of the strength of glass behind the chemical tempering is had stronger promoter action, this is because in the alkali alumina silicate glass, non-bridging oxygen and Al that basic metal is introduced³⁺Form aluminum-oxygen tetrahedron [AlO₄], this aluminum-oxygen tetrahedron is than silicon-oxy tetrahedron [SiO₄] volume is bigger, in glass structure, can produce bigger space, and help the carrying out of ion-exchange, finally obtain the better product of chemical tempering effect.But Al₂O₃The too high easy crystallization of glass that then makes can increase the difficulty of founding of glass simultaneously.

Na₂O is that this glass carries out being cemented out the necessary component of realizing this technology of chemical tempering by the bigger potassium ion of volume in chemical tempering (ion-exchange) process.As network outer body, it plays the effect of suspension in glass structure, can reduce the viscosity of glass simultaneously.Too much can cause a series of performances of glass such as variation such as chemical resistant properties, mechanical property, cross the low chemical tempering effect that then can reduce this glass, the tendency towards devitrification of glass also can increase, Na of the present invention₂The O mass percentage content is controlled at 8-16%, and more excellent is 12-15%.(Na in the said glass₂O+K₂O) content>=Al₂O₃Content.

B₂O₃Effect more special, it can generate glass, B under the high temperature melting condition separately₂O₃Be difficult to form [BO₄], can reduce high temperature viscosity, B has the free oxygen of capturing to form [BO again during low temperature₄] trend, structure is tending towards closely, improve the low temperature viscosity of glass, prevent the generation of crystallization.Introduce a certain amount of B among the present invention₂O₃Mainly be the fusing that promotes glass, mass percentage content is controlled at 0.01-3%, and more excellent is 1-2.5%.

Introduce K₂O mainly is the mixed alkali effect that utilizes itself and Na, reaches the effect that promotes glass melting, and the impact of performance of the introducing of a certain amount of K simultaneously after to chemical tempering improves and have certain promotion.K among the present invention₂The O mass percentage content is controlled at 0-6%, and more excellent is 1-5%.Be all alkalimetal oxide, (K₂O+Na₂O) content>=Al₂O₃Content.

MgO, CaO, SrO, BaO belong to alkaline-earth metal oxide together, and all are network outer body, introduce a certain amount of equal fusing that can promote glass.Have only and do not have Al₂O₃, B₂O₃Mg just gets into network with [MgO during Deng oxide compound₄] exist.MgO introduces and too much can cause glass loose, and density descends, and hardness reduces.MgO can also reduce crystallization tendency and crystallization velocity, improves the chemical stability and the physical strength of glass.But its content should be not too much, otherwise can cause the easy crystallization of glass and the coefficient of expansion too high.The content of MgO of the present invention is 0.1-5%, is preferably 1-3%.The effect of CaO and MgO is similar, and Ca works the effect of gathering to glass structure.The CaO scalable reduces high temperature viscosity and significantly improves the glass melting performance and do not reduce the strain point of glass, and too much CaO then can reduce the glass chemical resistant properties.Here, the mass percentage content scope of CaO is chosen in 0.1-5%, and more excellent is 0.5-2%.

SrO and BaO all have increases glass chemical-resistant stability and the effect that improves the anti-crystallization of glass.But a large amount of SrO and BaO can cause the glass density and the coefficient of expansion to increase.SrO and BaO have special improvement glass chemical-resistant component, and the total content of these components must surpass 0.2% or higher.Require with regard to improving chemical resistant properties, the content of SrO and BaO is preferably high as far as possible, but hopes then that with regard to glass density and the coefficient of expansion aspect content of SrO and BaO is low as far as possible, therefore the content of SrO and BaO need be controlled in certain scope.Simultaneously be considered to a kind of certain toxic heavy metal that has based on Ba, the present invention does not contain BaO basically, and the SrO mass percentage content is controlled at 0.01-3%, is preferably 0.5-2%, and optimum is 0.8-1.5%.

ZrO₂Can effectively improve glass chemical stability, reduce the glass swelling coefficient and significantly improve the Young's modulus of glass, ZrO₂Also help the performance of the acid resistance, elasticity, bending strength and the thermal expansion aspect that improve glass.But because its solubleness in glass is little, can increase the high temperature viscosity and raising glass liquidus temperature of glass, the tendency towards devitrification of glass is increased.Zirconium white mass percentage content of the present invention is controlled at 0.01-1%, or basic oxygen-free zirconium.

The finings that uses of the present invention is stannic oxide, does not contain arsenic and antimony basically, does not introduce the commonly used halogenide of glass industry in producing, vitriol, rare-earth oxide etc. as finings but do not get rid of.Other helps reducing the environment amenable element or the compound of glass defect also not get rid of introducing.

The stressor layers degree of depth is 30-110um behind the said glass chemistry toughening.

Because the glass mechanical property of behind chemical tempering, bringing is significantly improved, make invention gained glass have higher surface hardness, resistance to compression, anti-scraping performance all are greatly improved, and can be widely used in the cover sheet of display device.

Embodiment

Below further specify the present invention with embodiment, but the purpose of data is explanation and example, and does not limit the present invention in any way.

Table 1 is instances more of the present invention, and instance is pressed composition requirement:

1) prepare burden according to mass percent, every part of material degree is 100%, heavy 1000g;

2) the above-mentioned raw materials thorough mixing evenly is placed in the platinum rhodium crucible; Put into the container that refractory materials is built into again; Utilize Si-Mo rod that the temperature in the container is risen to 1550-1650 ℃; Guarantee to be no more than 1650 ℃; After reacting about 5-10 hour; Temperature in the container is reduced to 1580-1600 ℃ of insulation about 60-120 minute, guarantees to be no more than 120 minutes;

3) after insulation finishes glass metal in the crucible poured into rapidly and be cooled in the metal form of preheating that tabular (about 100mm * 200mm * 10mm), place 500-600 ℃ of High Temperature Furnaces Heating Apparatus to carry out anneal again was generally 4-6 hour;

4) cutting of the sample after the annealing and grinding and polishing become the thin glass plate of 50 * 50 * 1mm, glass pane surface is fully cleaned in the fused potassium nitrate liquid that is placed on 430-500 ℃ for 3-5 time be incubated 4-10 hour; Definition according to chemical tempering also can be used other saline solution, like metal-salts such as potassium, rubidium, caesiums.

5) insulation finishes, and takes out sheet glass and is cooled to room temperature, and glass cleaning plate surface is 3-5 time once more, promptly gets the alkali alumina silicate glass, the test of the line correlation performance of going forward side by side.Transmitance is greater than 90% behind the glass chemistry toughening.

Table 1 measures according to mass percentage content for the present invention prepares display device with the embodiment of the alkali alumina silicate glass of cover sheet and the test result of correlated performance:

Above content is to combine concrete preferred implementation to further explain that the present invention did; Can not assert that the specific embodiment of the present invention only limits to this; Those of ordinary skill for technical field under the present invention; Under the prerequisite that does not break away from the present invention's design; Can also make some simple deduction or replace, like the method for forming: float glass process drawing, overflow down draw, build moulding etc. and all should be considered as belonging to the present invention and confirm scope of patent protection by claims of being submitted to.

Claims (10)

1. a display device is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet this method comprises the steps:

1) according to the following raw material of the accurate weighing of mass percent:

The SiO of 54-65%₂, 10-17% Al₂O₃, 0-0.5% Li₂The Na of O, 8-16%₂The K of O, 0-6%₂The B of O, 0.01-3%₂O₃, the MgO of 0.1-5%, the CaO of 0.1-5%, the SrO of 0.01-3%, the ZrO of 0.01-1%₂SnO with 0.01-1%₂

2) the above-mentioned raw materials thorough mixing evenly is placed in the platinum rhodium crucible; Put into the container that refractory materials is built into again; Utilize Si-Mo rod that the temperature in the container is risen to 1550-1650 ℃, react after 5-10 hour, the temperature in the container is reduced to 1580-1600 ℃ of insulation 60-120 minute;

3) glass metal in the crucible is poured into rapidly be cooled to tabularly in the metal form of preheating, place 500-600 ℃ of High Temperature Furnaces Heating Apparatus to anneal again 4-6 hour plate glass;

4) cutting and the grinding and polishing sheet glass after annealing is placed on for 3-5 time in 430-500 ℃ the molten nitrate liquid with deionized water glass cleaning plate surface and is incubated 4-10 hour;

5) take out sheet glass and be cooled to room temperature, glass cleaning plate surface is 3-5 time once more, promptly gets the alkali alumina silicate glass.

2. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet in molten nitrate liquid, being incubated in the said step 4) is fused potassium nitrate liquid, rubidium nitrate liquid or cesium nitrate liquid.

3. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet, SiO in the said glass₂Mass percentage content is 58-64%.

4. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet, Al in the said glass₂O₃Mass percentage content is 12-16%.

5. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet, Na in the said glass₂The O mass percentage content is 12-15%.

6. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet, B in the said glass₂O₃Mass percentage content is 1-2.5%.

7. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet, Na in the said glass₂O+K₂O mass percentage content>=Al₂O₃Content.

8. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet the MgO mass percentage content is 1-3% in the said glass.

9. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet the CaO mass percentage content is 0.5-2% in the said glass.

10. a kind of display device as claimed in claim 1 is characterized in that with the preparation method of the alkali alumina silicate glass of cover sheet the SrO mass percentage content is 0.8-1.5% in the said glass.