Aluminoborosilicate glass and preparation method and application thereof

Specific implementation

The endpoints and any values of the ranges disclosed herein are not limited to this precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For a numerical range, an endpoint value for each range, an endpoint value for each range, and a separate point value, and a separate point value may be combined with each other to obtain one or more new numerical ranges, which should be considered specifically disclosed herein.

The first The present invention provides an aluminoborosilicate glass, based on the total weight of each component in the composition of the glass, the composition of the glass 33 - 60 wt % comprising:₂ Unitunitunitaceous @ Al Al alloys 3 - 10 wt %, and mixtures of same₂ O₃ B 10 - 30 wt %₂ O₃ Unitunitunitdly @ ZnO 1 - 15 wt % + TiO (ZnO + TiO)₂ + Sc₂ O₃ Examples of the 7 - 27 wt % alkali-earth metal oxide RO include MgO, CaO, SrO, BaO. In addition, RO is a unitaceous @ type, such as MgO, CaO, SrO, and BaO 0.001 wt % ≤ Sc.₂ O₃ ≤ 111wt %.

, Based on the total weight of each component in the composition of the glass, the content of each component in the composition of the glass satisfies: (MgO + BaO)/(MgO + BaO)>. 0.6

In a preferred case, the content of each component in the composition of the glass is satisfied by weight percentage based on the total weight of each component in the composition of the glass: ZnO/(ZnO + TiO).₂ + Sc₂ O₃ )>0.6.

In the preferred case, based on the total weight of each component in the composition of the glass, the contents of each component in the composition of the glass are calculated as percentages by weight: 0.1 wt % ≤ Sc₂ O₃ ≤ 0 0 0 0 0%.

In the preferred case, based on the total weight of each component in the composition of the glass, the contents of each component in the composition of the glass are calculated as percentages by weight: 40 wt % ≤ SiO₂ + Al₂ O₃ ≤ 66665wt %.

In the preferred case, the content of each component in the composition of the glass is calculated based, on a weight percentage basis: the brittleness coefficient D is 0 - 1, still more preferably 0.2 - 0.8, still more preferably 0.3 - 0.6, where D is calculated from the following equation: D is calculated from the following formula.

D=P₁ * SiO₂ +2.0 * B₂ O₃ -2.0 * (Al)₂ O₃ + CaO) + 0000000000.0 * (MgO + ZnO + TiO)₂ + Sc₂ O₃ - 4 4 4 4 * Σ Q

Of these, wherein SiO is used₂ , B₂ O₃ , Al₂ O₃ , MgO, CaO, SrO, BaO, ZnO, TiO₂ , Sc₂ O₃ Each represents a percentage by weight, Σ Q, of the total composition of the component, and Σ Q means that SiO is removed from the composition.₂ , B₂ O₃ , Al₂ O₃ , MgO, CaO, SrO, BaO, ZnO, TiO₂ , Sc₂ O₃ The sum, among other components, is the sum of the percentages by weight. 33 wt % ≤ SiO₂ P ≤ 5454549% . P₁ Unitz 0.2,54 wt %-AOMARKENCODTX0AO_SiO₂ P ≤ 666608% . P₁ The value is -0.5.

In the preferred case, the density of the aluminoborosilicate glass is less 3g/cm.³ , 2.43 - 2.68g/cm Is more preferable.³ .

In the preferred case, the refractive index n of the aluminoborosilicate glass is increased._D More preferably greater than 1.52, further preferably 1.52 _AOMARKENCODTX0AO_n_D _AOMARKENCODTX0AO_ 1.55.

, The aluminoborosilicate glass has a coefficient of thermal 50 - 350 °C expansion that is less 45 ×10 than that of the aluminoborosilicate glass.^-7 / °C, further preferably 29 ×10.^-7 / °C.^-7 . Degree. C. degree.

In the preferred case, the bending coefficient C is ≤ 0 0 0 0 . 5mm of aluminoborosilicate glass_R Satisfying: 0-AOMARKENCODTX0AO_C_R _AOMARKENCODTX0AO_ 0.5, Further preferably 0 _AOMARKENCODTX0AO_C_R _AOMARKENCODTX0AO_ 0.45, Further preferably 0 _AOMARKENCODELTA AO_C_R _AOMARKENCODTX0AO_ 0.4, Wherein C, is ._R The values are calculated from the following equations:

C_R =(R * σ)/(E*d)

Wherein, E is Young's modulus, unit is MPa; d is the thickness, unit of the aluminoborosilicate glass is mm; R is the minimum radius, the unit is mm when the aluminoborosilicate glass is bent; σ is the bending stress when the radius of curvature R of the aluminoborosilicate glass is R, and the unit is MPa. Among them, C_R The smaller the value, the stronger the glass flexibility, the stronger the curability.

In a preferred embodiment, the strain point temperature of the aluminoborosilicate glass of the present invention is higher 680 °C than

, The molding temperature T of the aluminoborosilicate glass of the present invention is T.₄ Liquidus temperature T_l Difference between the differences is greater than the 100 °C. Wherein, T₄ The molding temperature corresponding to 40000 P viscosity.

In a preferred case, the Young's modulus of the aluminoborosilicate glass of the present invention is less 80 GPa.

In the preferred case, the transmittance of the aluminoborosilicate glass of the present invention is equal 91% to or higher

In second aspect, the present invention provides a method for preparing an aluminoborosilicate glass, the method comprising: providing a raw material composition, by sequentially subjecting the raw material composition to a melting treatment, a molding treatment, an annealing treatment, and a machining treatment according to the composition of the aluminoborosilicate glass according to the present invention.

In particular, the present invention also provides a raw material composition based on the weight of the composition, based on an oxide, the composition containing 33 - 60 wt %₂ Unitunitunitaceous @ Al Al alloys 3 - 10 wt %, and mixtures of same₂ O₃ B 10 - 30 wt %₂ O₃ Unitunitunitdly @ ZnO 1 - 15 wt % + TiO (ZnO + TiO)₂ + Sc₂ O₃ , Unitunitunitdly 7 - 27 wt %-@ alkaline earth metal oxide RO, wherein RO is at least one of MgO, CaO, SrO, and BaO. unitunit. 0.001 wt % ≤ Sc type₂ O₃ ≤ 111wt %.

SiO x in the raw material composition of the present invention.₂ As a matrix constituting the network structure, addition of the matrix to improve heat resistance and chemical durability of the glass, and a glass transition, it is helpful. , However, too much SiO₂ The melting temperature is increased, the brittleness increases, and the refractive index n is not improved._D In, too high requirements are provided for the production process. The inventors of the present invention have further found in the study, SiO x, as a percentage by mass.₂ When the content ≥ 3333wt %, the mechanical properties, chemical corrosion resistance and chemical corrosion resistance of the prepared glass can be further improved; and the glass flexibility. Thus, in order to further improve the comprehensive properties of the resulting glass and improve the flexibility, it is preferable that, based on the weight of the composition, based on the oxide, based on mass percentage, units @ are taken as the oxide. 33 wt % ≤ SiO₂ ≤ 66660.wt. %. It is further preferred, as a percentage by mass, of unitunits. 33 wt % ≤ SiO₂ ≤ 5454549%.

A raw material composition, B, of the present invention₂ O₃ As a matrix constituting the aluminoborosilicate glass, glass, which can improve the toughness, and B, can be separately produced.₂ O₃ It is also good cosolvent, can reduce glass melting temperature by a wide margin, also has the benefit; B in the vitrification process.₂ O₃ Content too high for thermal stability and refractive index n_D Hoist. Thus, the total consideration, based on the weight of the composition, is based on oxide, as a mass percentage, 10 wt % ≤ B₂ O₃ ≤ 33330.wt. %.

Al in the raw material composition of the present invention.₂ O₃ However, the glass structure tends to be rigid, the brittleness, the high-temperature surface tension and the high-temperature viscosity of the glass are too large, and the refractive index n is difficult to be improved._D , Increase glass production technology degree of difficulty etc. Thus, it is contemplated, based on the weight of the composition, that the Al, based on the weight of the composition, is calculated as an oxide.₂ O₃ The contents of ltoreq delustoman® range are included. 3 - 10 wt %

In the raw material composition of the present invention, in the preferred case, based, on the weight of the composition, an oxide, 40 wt % ≤ SiO₂ + Al₂ O₃ ≤ 66665wt %.

MgO, CaO, SrO, BaO, and BaO are all alkaline earth metal oxides, and their addition can effectively reduce the high temperature viscosity of the glass, thereby improving the meltability and moldability, and increasing the strain point and refractive index n of the glass._D , MgO, BaO, and the like have the characteristic of reducing glass crispiness. The content is excessive, the density is increased, cracks, devitrification, and phase separation are all improved, and excessive CaO is beneficial to the improvement. Thus, based on the weight of the composition, depending on the weight of the composition, alkaline-earth metal oxide RO, based on the 7 - 27 wt % weight of each component, is contained, where RO==MgO, CaO, SrO, BaO, or any one or more. , The composition is based, based on the weight of the composition, on oxide, (MgO + BaO)/(MgO + BaO)>. 0.6

ZnO, TiO in the raw material composition of the present invention.₂ , Sc₂ O₃ Can effectively reduce glass's high temperature viscosity and crystallization limit temperature, have promotion intensity, hardness below the softening point, increase glass's chemical resistance, increase pliability, show promotion index n._D The effect. However, too much ZnO, TiO₂ , Sc₂ O₃ Be unfavorable for the promotion. Thus, in consideration, ZnO + TiO based on the weight of the composition, on oxide, ZnO + TiO, is taken into consideration.₂ + Sc₂ O₃ The content of ZnO/(ZnO + 1 - 15 wt % + TiO x) is based, preferably, depending on this unit_@ range, preferably ZnO/(ZnO + TiO).₂ + Sc₂ O₃ )>0.6. Among them, Sc₂ O₃ Significantly improving heat resistance and refractive index n_D , The bending performance, but too much Sc, of the glass can be improved while the ultrathin glass is made.₂ O₃ It is detrimental to promote the stability, and therefore, is unitarily taken into the alpha.omega.dinitrile 0.001 wt % ≤ Sc₂ O₃ ≤ 111wt %, preferably, Dounitunitan 0.1 wt % ≤ Sc®.₂ O₃ ≤ 0 0 0 0 0%.

In the raw material composition of the present invention, according to the difference, the composition may contain at least one of a sulfate, a nitrate, a halide, a tin oxide, and a stannous oxide; based, on the weight of each component, the content of the fining agent is not more virginess. 1 wt % the clarifying agent is based on the weight of each component. The specific selection of the clarifying agent is not particularly limited, and various options commonly used in the art, for example, sulfate may be barium sulfate, the nitrate may be barium nitrate, and the halide may be barium chloride and/or calcium fluoride.

It should be understood by those skilled in the art, that the composition of the present invention contains SiO, as a raw material composition.₂ , B₂ O₃ , Al₂ O₃ , ZnO, TiO₂ , Sc₂ O₃ , MgO, CaO, SrO, and BaO means that the composition contains Si-containing compounds, B compounds, Al-containing compounds, Zn-containing compounds, Sr-containing compounds, Sr-containing compounds, phosphate, basic carbonates, oxides and the like, as is well known to those skilled in the art, and will not be described in further detail herein in this specification. and the present invention is not limited to these examples in all respects, and all such elements are not limited to these specific elements and their salts, such as carbonates, nitrates, sulfates, phosphates, basic carbonates, oxides, and the like, as previously mentioned.

In the raw material composition of the present invention, when aluminoborosilicate glass is prepared by using the same, the glass has the aforementioned excellent comprehensive properties, and is mainly attributable to the interaction, especially SiO, among the components in the composition.₂ , B₂ O₃ , Al₂ O₃ , ZnO, TiO₂ , Sc₂ O₃ , MgO, CaO, SrO, BaO cooperate, and more particularly, the respective components of the aforementioned specific content are matched to each other.

In the method of the present invention, preferably, the conditions of the melt treatment include: the temperature is lower than the unitunit_@, and 1550 °C the time is greater than 1h. The specific melting temperature and melting time can be determined by those skilled in the art according to the actual situation, which is well known to those skilled in the art, and will not be described in further detail herein.

In the method of the present invention, in the preferred case, the conditions for annealing treatment include: the temperature is substantially higher or less, 720 °C and the time is greater than 0.1h. The specific annealing temperature and annealing time can be determined by those skilled in the art according to practical situations, which is well known to those skilled in the art, and will not be repeated herein.

In the method of the present invention, the machining process is not particularly limited, and various machining methods commonly known in the art, for example, cutting, polishing, polishing, and the like may be performed for products obtained by the annealing treatment.

, The method further comprises subjecting the product resulting from the machining treatment to a second melt-draw treatment, further preferably, controlling conditions of the machining process or the secondary melt-draw process to produce a glass having a 0.1 mm thickness less than

In the method of the present invention, it is possible to produce flexible glass having a thickness that is higher by a float 0.1 mm, an overflow method, a 0.1 mm downdraw method, or the like (that is, a 0.1 mm flexible glass having a thickness of about unit_@ (that is, a primary molding method to obtain 0.1 mm thickness-AOMARKENCODTX0.AONS), and can also produce flexible glass having a thickness that is smaller by a secondary melt-draw method. Thus, the method may further comprise subjecting the product obtained by the mechanical processing treatment to a second melt-draw treatment, to produce a 0.1 mm flexible glass having a thickness less thanThere is no particular limitation, and a method, such as a secondary melt-draw process, may include, for example, a method such as a float, an overflow method, a downdraw method, and a glass manufacturing method such as a float method, an 1 mm overflow method, or a downdraw method, and conveys the sheet glass to a feed port, at an appropriate rate V, of a secondary stretch forming apparatus.₀ Mm / min is fed inwardly into a stretch forming furnace to control the viscosity of the stretch forming zone to be about 10.^5.5 -10⁷ V-line, in a poise range, at an appropriate rate V by a stretcher and a drum.₁ Winding, mm / min, roll-to-reel to obtain an ultra thin flexible glass sheet having a thickness 0.1 mm that is much less unitarily @, the draw rate V being equal to V.₁ Greater V₀ .

The third Aspects, the invention provides the aluminoborosilicate glass prepared by the method.

As described above, different processes can produce glass, with different thicknesses, such as float, overflow, downdraw, etc. and can produce flexible glass having 0.1 mm a thickness of more or less 0.1 mm unitarily @, and can be further produced by a secondary melt-draw process to produce a 0.1 mm flexible glass having a thickness less thanWherein, the thickness ≤ 0 0 0 0 . 5mm's flexible glass, bending coefficient C_R The value is less 0.5, preferably less 0.45, still more preferably less 0.4.

The fourth Aspects, the present invention provides the use, preferably in the preparation of display devices and/or solar cells, of substrate glass substrate materials and/or surface-encapsulated glass film materials, flexible display products, substrate glass substrate materials and/or screen surface protection glass film materials, flexible solar cells, and applications for other applications requiring high heat resistance, high flexibility, and easy bending of glass materials, and/or screen surface protective glass materials and/or screen surface protective glass film materials and/or screen surface protective glass film materials.

Embodiment

The present invention will be described in detail below by way of examples below. In the following examples, unless otherwise specified, each of the materials used may be obtained commercially, as is not specifically described, and the method used is a conventional method in the art.

In the following Examples and Comparative Examples, the glass density, in g / cm, was measured according ASTM C C C C C-693.³ .

The unitunit_@ type of glass thermal expansion coefficient was determined using a horizontal 50 - 350 °C expander with reference ASTM E E E E-228 by 10 units of unit.^-7 . Degree. C. degree.

For ASTM C C C C-623, the Young's modulus, in units of GPa.

The strain points, in units of °C . were determined using a three-point tester with reference ASTM C C C C C-336.

Perkin @ wavelength corresponding transmittance of the glass was determined using UV - 2600 ultraviolet-visible spectrophotometer. 550 nm

To ASTM C C C C C-829, the glass liquidus temperature T is determined using a gradient furnace method._l , Unit is °C.

The glass high temperature viscosity curve, in which 200 P viscosity corresponds to a melting temperature T ASTM C C C C C-965, is determined using a rotary high-temperature viscometer._m Molding temperature T corresponding to °C; 40000P viscosity and corresponding molding temperature T₄ , Unit is °C.

Using WAY Y Y Y-2S Abbe number refractometer, determining 587.6 nm refractive index n under lambda type (sodium yellow light) at room temperature_D .

The minimum radius of curvature and the curve stress of the glass having a thickness ≤ 0 0 0 0 . 5mm were measured using a radius of curvature and a curve stress tester, and a bending coefficient C was calculated by calculation._R .

Example 1 - 18, Comparative Example 1 - 8

Each of the components, was weighed according to the glass composition shown in Table 1 - 4, mixed, poured into a platinum crucible 1530 °C, unitarily @, 4 hours and stirred with a platinum rod to discharge the bubbles, while mixing the mixture into a platinum crucible. The molten glass solution is poured into a stainless cast iron grinding tool, formed into a prescribed block-shaped glass product, and then the glassware in an 2 hours annealing furnace, and the power source is switched off to be cooled by the furnace and is unitarily 25 °C. The glass product is subjected to cutting, grinding, polishing, then washed cleanly with deionized water and dried, and a glass finished product is prepared in the 0.5 mm approximate unitz @ thickness. The properties of the respective glass finished products were measured, respectively, and the results are shown in Table 1 - 4.

Table 1

Of these, in Table 1 - 4, there are five, CaF, and combinations of the clarifying agents listed in the Examples and Comparative Examples.₂ , SrCl₂ , BaSO₄ , SnO₂ , SnO. After the former three raw materials enter the furnace, most of the anion forms gas away from the glass solution, and the remainder is dissolved into the glass network structure. FF^. , Cl^. , SO₄^{2 .} Neither with O nor O^{2 .} A uniform grid, like a cation Ca, Sr, Ba, is formed in the network gap as well. Finally, cations Ca, Sr, Ba and more oxygen ions are covalently balanced. Thus, the embodiment and comparative examples of the present invention are CaF.₂ , SrCl₂ , BaSO₄ When the three clarifying agents participate D-value calculation, it should still be calculated according to the corresponding CaO, SrO, BaO, and should not be summarized in Σ Q; and SnO₂ , SnO should be generalized to Σ Q.

Table 2

Table 3

Table 4

Compared with the data in the table 1 - 4, the prepared glass has the characteristics of obviously higher low density, high refractive index, glass forming stability, low thermal expansion coefficient, high thermal stability, high flexibility, easiness in bending and the like.

The method comprises the following steps: cutting, grinding, polishing, cutting, grinding and polishing a plate glass obtained by cutting, grinding and polishing into a secondary stretch forming device feed port, and then V-shaped glass 0.5 mm is conveyed to 50 mm a feed port of the secondary stretch forming device.₀ The rate of mm / min is fed inwardly into a stretch forming furnace, controlling the viscosity P of the stretch forming region, and rate V by a stretcher and a drum.₁ The roll-to-roll winding, mm / min, resulted in a flexible glass having a thickness d1, a width d2, and the. The minimum radius of curvature attainable for each glass product was measured using a radius of curvature and a curve stress tester, and the conditions of the embodiments and corresponding bending coefficients are shown in Table 5.

Table 5

The results from Table 5 show, that the method of the present invention can produce aluminoborosilicate glass having a thickness ≤ 0 0 0 0 . 5mm, which has a bending coefficient C._R Less 0.5. C when bending occurs, C_R The smaller the value, the smaller bending stress, at the same bend radius, indicates that the glass pane can further reduce the radius, that is to say with a more excellent flexibility of flexibility.

Embodiments, however, of the present invention have been described in detail above, but the present invention is not limited thereto. The technical solution of the present invention is within the scope, and various simple modifications, including various technical features, can be made in any other suitable manner, and these simple variants and combinations should also be considered as disclosures of the present invention, all of which fall within the scope.