TW570905B - Glass composition of a substrate for display - Google Patents

Abstract

A glass composition of a substrate for display consisting essentially of, as calculated in weight percent on an oxide basis, of 56.0% to 62.0% SiO2, 13.0% to 18.0% Al2O3, 9.0% to 13.5% B2O3, 1.0% to 8.0% SrO, 0.1% to 8.0% BaO, 3.5% to 8.5% CaO, 0% to 1.0% MgO, 0.1% to 1.5% ZnO, 0.1% to 1.5% ZrO2 and 0% to 1.0% BeO, provided that the total weight percent of CaO, MgO, ZnO, ZrO2 and BeO is preferably within 4.0 to 9.0%.

Description

570905

Background of the invention: (1) Field of the invention: The present invention relates to a flat glass formulation used for the production of displays with a thickness of about 0.2 mm (1 to 2 mm), especially a substrate glass that can be used to produce liquid crystal displays. . (2) Previous technology: According to the general, it is generally used to produce active matrix liquid crystal displays, such as thin film transistor liquid crystal displays or similar displays. The substrate glass used is a kind of aluminosilicate glass. It contains only a very small amount of alkali metal oxide components, and can be made into flat glass by forming methods such as the float method or the pull-down method. The float method is suitable for production scales with a daily output of 30% or more, and the pull-down method is suitable for daily output. Production scale of about 3 ~ 10 tons. Generally speaking, when the flat glass is manufactured by the down-draw method, the high-temperature and fluid glass paste first passes through a glass melting furnace, a clarification tank, and a cooling pipe, and then flows to a distribution tank with an average glass flow function. Then, the molten glass is pulled down through a glass plate extraction device, and then slowly cooled to make flat glass. The down-draw molding method can reliably produce ultra-thin flat glass, so it is suitable as a molding method for manufacturing substrate glass for liquid crystal displays. In the process, when the glass paste flows through the melting furnace and the clarification tank, the temperature is high, and With fluidity, second: When cooling the tube, the cooling tube will reduce its temperature. When it flows to the distribution tank with the function of evenly distributing the glass flow, it can be lowered to the temperature required for molding, that is, its viscosity range is maintained at 104. · Temperature range of 6 (poise). Generally speaking, when the glass lean temperature decreases, it is easy to cause glass devitrification or production.

570905 V. Description of the invention (2) Crystallization phenomenon 'defines the highest temperature of glass devitrification or crystallization, namely the glass liquidus temperature (TL). Therefore, when the glass paste temperature is above the glass liquidus temperature (TL), After a long period of heat treatment, devitrification or crystallization will not occur. However, because the glass forming temperature is often close to the glass liquidus temperature, if the glass paste temperature is below the glass liquidus temperature for a long time, it is very easy to produce devitrification or crystallization, causing defects on the glass surface or inside, which reduces the product Yield, therefore, in the glass forming process, there should be a proper separation between the glass forming temperature and the glass liquid phase temperature, and according to practical experience, the glass forming temperature should be about 40% higher than the glass liquid phase temperature. 〇 above, can effectively prevent the glass from devitrification or crystallization during the molding process. Traditionally, when the alumino-silicate glass is manufactured by the down-draw molding method, the temperature is controlled between about 1 085 and 1 250 t. Therefore, in order to reduce defects such as devitrification or crystallization of the glass surface or internal σ 卩, generally By increasing the glass forming μ degree or lowering the glass liquidus temperature, the glass forming temperature is more than 40 ° C higher than the glass liquidus temperature. First, in terms of increasing the glass molding temperature, 'because the viscosity of the glass lean will decrease with the temperature of the glass paste, so, raising the molding temperature will reduce the viscosity of the glass paste during molding, and it is difficult to maintain the dimensional accuracy of the product shape. Increasing the molding temperature will also enable cooling pipes, distribution tanks with a function of evenly distributing glass flow, and glass plate cooling devices to operate at higher temperatures. In this way, in addition to increasing energy consumption, it will also shorten the above devices. The service life will be caused by the glass paste and the above-mentioned device under the two-temperature reaction, so that more impurities, impurities and pollutants are mixed into the flat glass after molding, so the product yield can not always be improved, which is not in line with economic benefits. Therefore, in practice, it ’s less inclined to adopt a method of increasing the glass forming temperature,

Page 5 570905 V. Description of the Invention (3) — It is the more commonly used solution to reduce the liquidus temperature of the glass. When adjusting the liquidus temperature of glass, it is generally adjusted by adjusting the glass composition, that is, the liquidus temperature of the glass composition is lowered to 1 0 8 5 C, which is 4 0 c lower than the lower limit temperature of the molding (that is, 104 ° C). ), Or lower temperature, but once the glass composition changes, in addition to the temperature of the liquid phase of the glass, other important physical characteristics, such as thermal expansion coefficient, strain point and density, will often also change. Some properties may even deteriorate to prevent normal use of glass products. Therefore, how to adjust the composition so that while lowering the liquidus temperature of the glass, other important physical properties will not be excessively deteriorated, which will become a key focus when adjusting the composition of the glass. In addition, for the glass used in the production of liquid crystal displays, especially the glass used in the production of thin-film transistor liquid crystal displays, the physical characteristics are particularly strict. Therefore, the thermal expansion coefficient, strain point and density of glass are important characteristics. , It must be included in the evaluation considerations. Generally, the thermal expansion coefficient of thin-film transistor liquid crystal display glass should be lower than 40 × 10-V ° c. If it is too high, it will affect the accuracy of the subsequent liquid crystal display process. F The glass substrate is difficult to assemble and assemble, and its strain point Generally, it should be higher than 65 ° c. “Right lowering too much” will also affect the accuracy of the process, causing deviations in the alignment of lithographic etching. “Serious, it will also cause the circuit to be short-circuited or disconnected, which will degrade its electrical performance. If it is lower than 2.55 g / cm3, if it is too large, it will increase the weight of the LCD panel, which is unfavorable for use in portable products. In recent years, the designers and manufacturers of substrate glass for liquid crystal displays have also developed many new systems for the composition of these substrate glasses.

570905 V. Description of the invention (4) 1 Working technology 'such as: U.S. Patent Nos. 58 1 1 36 1, 58 5 1 9 3 9 and 6060 1 68, etc.' Glass composition disclosed in these patents The glass-based f of the fabricated glass still has a high liquidus temperature, about 1090. 〇 Above, therefore, when these glasses are formed by the pull-down method, the aforementioned various problems will occur. 0 The outline of the invention has the ingredients and the oxidized stone of the liquid crystal temperature change point and the composition of the display. Boron, 1.0% including calcium oxide, although it accounts for the weight of magnesium in the substrate glass when it is glass, 0.1 · 0% of the substrate glass for oxygen devices, and research experience, it has a physical Characteristics, such as aluminosilicate glass in providing a significant percentage of alumina, 9. 0% and 0.1% to 8. 0%, rhenium oxide and relatively low, but from the resolution, has a very important 8. 5% oxidation, 0.1% to 1., oxidation ballast, oxygen in the field of traditional liquid crystal display manufacturing and the practical experience of the substrate glass group, while other important degrees, etc. 'are still the same One of the goals of the Ming Dynasty is that the main ingredients include 14.0% to 18.0% to 8% of gill oxide, magnesium oxide, and the percentage of the total weight of the oxide. Glass paste viscosity and glass melting process are still divided. Ratio of 3.5% 1% to 1.5% oxidation Beryllium, but calcium oxide has been in the composition for a long time. The inventor has developed one of the inventions based on many years. The glass below 1045 ° C: The coefficient of thermal expansion should be similar. The substrate glass for the indicator is 56.0% to 62.0% to 13.5% of oxidized barium oxide, and the remaining five types include beryllium oxide and other components. These components have important effects on melting, so the amount of each component Word, 0 to 1.0% of oxygen oxidation error and 0% to zinc, hafnium oxide and oxygen page 7

I 570905

$ The total content of beryllium and other ingredients is described in the most detailed range between 40% and 90% by weight: = The invention is to provide _ kinds of substrate glass for display, the glass system: the following 2 materials, according to _ Weight percent, combined: (2) (3) (4) (5) (6) (7) (8) (9) (10) Silicon oxide (Si〇2) with a weight percentage of 56.0% to 62.0%; 13.0% to 18.0% by weight of alumina (Al203); 9.0% to 13.5% by weight of boron oxide () 82〇3); 1.0% to 80% by weight of gill oxide (Sr〇) , Percentage 0.1% to 8.0% barium oxide (Ba0) weight, percentage 3.5% to 8.5% calcium oxide (Ca〇) weight ^ percentage 0% to 1.0% magnesium oxide (Mg〇); weight f 0.1% to 1.5% of zinc oxide (Zn〇); 0.1% to 1.5% by weight of zirconia (Zr〇2); 0% to 10% of beryllium oxide (Be〇); beryllium 2: Calcium oxide, magnesium oxide, zinc oxide, zirconia, and oxide in Λ; ^ " Physical = hair;;: plate: = weight percentage of the composition will be used according to its ^ ^ ^ ^ ^ ^ The characteristics, structure, and production of glass are limited by the following reasons: Therefore, each composition The weight percentage must be in the composition of the field and oxygen. The five ingredients of stone oxide, oxidized oxide, oxidized shed, and oxygen ^ barium # accounted for more weight percentages.

V. Description of the invention (6) The characteristics, structure, and system of glass used for the board are important. Therefore, these components = surface. The effect caused by the glass is more important than the main components of the glass network board, which is oxidized R9 n0 / 〇 And the king body, its preferred content is 56.0% to devitrification ° ,, a milk formula: Xi contains Λ less than 56.0% 'The glass produced will be easily melted and warm to produce Taigu: ί fossil Xi content At 62.0%, it will cause devitrification of the glass; ytterbium oxide is used to increase = 1: structure :; = 丄 series is between 13. °% and 18. °%, if the content of oxide is small: two devitrification is also vulnerable External water vapor or chemical tests ^ Μ ′ In addition, the content of oxides is more than 18.0%, which will also lead to the use of glass and is not conducive to the use of general decontamination furnaces to make dysprosium; the operation of the oxidation shed is: flux, t must be used for Reduce the viscosity of glass paste when making glass: 0%] = the amount is 9.0% to 13.5%, if the boron oxide content is less than * 3%, the effect of 1 large Λ cannot be fully exerted, and if the content of the oxide butterfly is more than the use 11 The strain point of glass is not conducive to subsequent processes. It should be easy to devitrify, and it is more similar. Its preferred content is 0.1% to 8.0%, === oxidized pin 1%. It is easy to devitrify, if the content of barium oxide: dioxin, containing 1 less: 0. It will be too high, and the strain point will be greatly reduced. Evening;.%, Glass density in the glass for substrates of the present invention, with the exception of components such as boron monoxide, gill oxide, and barium oxide; silicon, alumina, 570905 V. Description of the invention (7) Overall ^ 1 percentage Lower, but because these ingredients have a very important impact on the glass's lean viscosity and melting degree when melting glass, it still has a decisive weight in the process of manufacturing glass for substrates, among which the role of calcium oxide, For glass melting, its preferred content is between 3.5% and 8 5% $: chemical split content = less than 3.5% 'will not effectively reduce the viscosity of glass: number: more than 8.5%' glass It is easy to devitrify and thermal expansion is applied in subsequent processes. Magnesium oxide is used to reduce the bubbles or impure content of the glass paste paste glass core. ; Zinc oxide is also used to promote the glass to 0.1% M.5%, if the content of oxidant is less than 0. U, will not play the role of promoting the melting of glass, at 1.5% 'glass will easily devitrify :: "Even: yes, low glass viscosity, with oxygen = no effect to promote glass dissolution As a result, if oxygen is less than 1%, it is also easy to devitrify; beryllium oxide is also used to promote: zeta solution of glass: "Glass will" especially require special attention: the above-mentioned dagger m] ". Ci, Although the ingredients such as emulsification error and wrinkle are $ & emulsified and adjusted the thermal expansion coefficient of glass, the solubility of the oxide dance, the total content of the components such as zirconia and beryllium oxide, etc.

If the total content of oxide, magnesium oxide, zinc oxide, and oxidation percentage is less than 4, the melting temperature of glass will be too high; Taicheng J Page 10 570905

:: The total content of calcium, magnesium sulphide, oxide, oxidized oxide, and beryllium oxide is less than 9 · (U, the glass will be easily devitrified, and the coefficient of thermal expansion of the glass will be first implemented in the present invention. After the aforementioned composition is uniformly mixed, the mixed raw materials are introduced into a glass melting tank, and after melting into glass paste, the two temperatures are reduced to the temperature range required for molding, that is, the viscosity range is maintained at $ 104 · 6 to 1052p. ise (poise) temperature range, and then draw-molded to produce a glass substrate with a predetermined thickness, and then slowly cooling the glass substrate, it can be cut and processed into a glass substrate finished product for liquid crystal displays. Each composition is mixed with different weight percentages, and then different glass samples are made according to the foregoing procedures, and these glass samples are taken as examples. The thermal expansion coefficient, strain point, density, and glass liquid temperature are described in the list. The difference between the equal characteristic values is shown in Table 1 (Examples 1 to 6). The composition and characteristics of the breakage σ made according to the present invention are shown in the example of the present invention. 2 °°) shows a comparative example of the composition invention different from the glass samples made in the present invention. The glass samples in Tables 1 and 2 are made as follows:: such as = method, each component is made of commonly used raw materials, according to the corresponding The weight percentages are uniformly mixed 'and then melted in platinum for 6 to 8 hours at a temperature of 1600 ~ 1650 ° C. During the melting process, stir with a platinum stirrer for 2 hours to promote the glass The homogeneity of each component, and then the glass paste is poured into a metal template and cooled to form a plate. At this time, the glass sample 2 is tested to obtain the thermal expansion coefficient, strain point, density, and glass temperature, etc. Characteristic values, which are respectively listed in Table 1 and Table 2

570905

The upper 0 of the present invention, when detecting each characteristic value of each # σ & a ^ Sakazaki sample, is mainly tested in accordance with the following methods: Lower (1) coefficient of thermal expansion (Single ☆ · Ί 7 / >, ,,, Early position · 1 ο V c) The test is based on the American Materials Testing Association (Amerimn Qm · + £. Can Society f〇r Testing and

Materials' Hereinafter referred to as "with" the testing standard No. E228-95, using mechanical push rod type thermal expansion instrument and alumina as reference standards, heating and measuring the elongation of glass samples, the temperature range is from room temperature to glass, The temperature until elongation, even contraction due to softening, is 3 ° C per minute. The thermal expansion coefficient is calculated from the glass elongation of 100 to 4 00c. (2) Strain point stomach (unit: it) detection: Refer to ASTM C598-93, heat and measure the relationship between the deformation rate and temperature of the glass sample, and take the temperature corresponding to the specific deformation rate as the strain point. (3) Density (unit ·· g / cm3) detection: refer to ASTM c729_75, take about 2 grams of non-bubble glass, measure the density of the glass sample when it floats in the specific gravity liquid. (4) glass liquid temperature (unit: it) detection: based on astem C82 9-8 1 'Put glass shavings smaller than 850 // m in a platinum dish, and place it in a gradient furnace for 24 hours, then measure the crystallization of the glass with a microscope and determine its liquidus temperature. Table 1

Page 12 570905 V. Description of the invention (10) Example 1 Example 2 Example 3 Example 4— Example 5 Example 6 58.0 57.0 58.0 58.3 56.5 59.5 14.5 14.0 13.5 15.5 13.5 16.0 11.0 12.5 13.0 9.5 9.5 10.0 6.5 63 5 ^ 4.0 7.0 4.0 3.5 3.0 4.5 6.5 7.5 3.0 5.5 5.0 4.0 4.5 4.8 6.0 0 0.5 0 0.5 0.5 0.5 0.5 1.0 0.5 0.2 0.5 0.5 0.5 0.5 1.0 0.5 0.2 0.5 0 0 0 0.5 0 0 6.5 7.0 5.5 6.2 6.0 7.5 38.6 38.9 37.4 39.4 38.3 39.1 656 658 655 660 652 661 2.52 2.53 2.54 2.54 2.54 2.52 1030 1035 1035 1035 1030 1035 1030 si2) Weight percentage of aluminum oxide (A1A) Weight percentage of SSi (B203 :) Weight percentage of osmium oxide (S rO) Weight percentage of barium (BaO) weight percentage of calcium oxide (CaO) _magnesium ^ 20) weight percentage 1 weight percentage of zinc zinc (ZnO) weight percentage of chromium oxide (Zr02) weight percentage of beryllium oxide (BeO)

Mg0 + Ca0 + ZnQfZr02 + Be0 weight percent thermal expansion coefficient (10-7 / 〇C) strain point (° C) density (g / cm3) glass liquid temperature (° C) Example shown in Table 1 z — Chu observed that according to the various inspection data produced by the present invention, the glass substrate that can be cleared has a right edge of $ 1 η ς. Wide glass liquidus temperature, so it is very suitable for the following drawing forming method.

IH Page 13 570905 V. Description of the invention (π) Glass. In addition, the coefficient and its response value are the same as those described above. Therefore, in the comparative example of the traditional composition of the present invention, the temperature is 1 0 4 5 ° C. In the case of glass, it is very easy to occur in the detection data, the strain point of the thermal expansion coefficient is too low, and the glass has a thermal expansion point of less than 40 x 10-Vt. / cm3 and other special substrates for liquid crystal displays are very similar. The materials for glass substrates for liquid crystal displays are very similar. Ming also lists in Table 2 the comparative examples 7 to 12 using other treatments that are different from the treatment of the hair, and shows that the glass substrates produced have a higher liquid phase Temperature, it is a problem of devitrification or junction BΘ produced in the flat glass produced by the pull-molding method. In addition, each of Table 2 clearly shows that the glass substrates made in Comparative Example 7 are high, while the glass substrates made in Comparative Examples 9, 10, and 11 are made in Comparative Examples 8, 11 and 12 The density of the resulting glass substrate is not suitable as a material for a glass substrate for a liquid crystal display. Table II

Page 14 570905 V. Description of the invention (12) Example 7 Example 8 Example 9 fly! 110 Example 11 Example 12 Weight percentage of silicon oxide (Si02) 58.0 54.0 57.2 57.0 57.0 63.0 Weight percentage of alumina (A1203) 12.0 15.5 14.5 15.5 14.0 13.5 Weight percentage of boron oxide (B203) 9.5 11.5 14.5 11.5 9.5 9.5 Weight percentage of oxide saw (S rO) 7.0 8.5 2.3 5.5 4.0 9.0 Weight percentage of barium oxide (BaO) 3.5 3.5 1.5 3.0 9.0 1.0 Calcium oxide (CaO) Weight percentage 9.0 6.0 6.0 5.0 4.0 4.0 Weight percentage of magnesium oxide (MgO) 0.5 0 2.0 0 0 0 Weight percentage of zinc oxide (ZnO) 0.5 0.5 1.0 2.5 0 0 Weight percentage of chromium oxide (ZK) 2) 0 0.5 0.5 0 2.5 ~ 0 weight percentage 0 0 0.5 0 0 0 Mg0 + CaQfZnQfZr02 + Be0 weight percentage 10.0 7.0 10.0 7.5 6.5 4.0 coefficient of thermal expansion (10-7, C) 40.2 39.8 39.4 37.8 38.3 37.6 strain point (° c) 656 6-50 647 645 644 665 Density (g / cm3) 2.5 ^ 2.5 ^ 2.53 2.55 2.58 2.56 Temperature of the liquid phase of the glass (.1095 1100 110-0 0 1010 1090 1110) Glass composition of the present invention Parts, wear very prepared

At a glass liquidus temperature of 1045 t, the glass substrates produced by j all have a low temperature, their strain points are higher than 650 Γ, their thermal expansion coefficients are lower than 40 × L ′, and their density can be maintained.

570905

V. Description of the invention (13) Below 2.55g / cm3, and common aluminosilicate slopes, as a production thickness of about 0.2 mm (mm) to 1.2 cm; 'Extremely suitable = smart glass for utensils In order to effectively solve the aforementioned traditional substrate] many problems occurred in the production process of crystal display. The above description of the mouth and liquid is only a preferred embodiment of the present invention. However, the scope of the rights claimed by the present invention is not limited to this. According to the technical content disclosed by those skilled in the art according to the present invention, Equivalent changes that can be easily considered should all belong to the protection scope of the present invention. 570905 Schematic Description Page 17

Claims (1)

570905 VI. Tit nose 蓺 圊 ^ 1. A composition of a substrate glass for a display, including: a weight percentage of 56.0% to 62.0 ° /. 0% 至 8. 0% 的 Erbium oxide; weight percentage of 1.0% to 8.0% of boron oxide; silicon oxide; weight percentage of 13.0% to 18.0% of alumina; weight percentage of 9.0% to 13.5% of boron oxide; weight percentage of 1.0% to 8. 0% of hafnium oxide; weight percentage 1% to 8.0% of barium oxide; and a weight percentage of 3.5% to 8.5% of calcium oxide. 2. According to the composition of the substrate glass for display described in item 1 of the scope of the patent application, after the components are uniformly mixed, the mixed raw materials are introduced into a glass melting tank, and the glass paste is melted into a glass paste, and then The temperature is reduced to the temperature range required for molding, so that its viscosity range is maintained at a temperature range of 104.6 to 10.5.2 poise, and then pulled down to form a glass substrate of a predetermined thickness, and then the glass substrate After slowly cooling, it can be cut into glass substrates for liquid crystal displays. 3. The composition of the substrate glass for a display as described in item 2 of the scope of the patent application, which further includes a magnesium oxide content of 0% to 1.0% by weight. 4. The composition of the substrate glass for a display as described in item 2 of the scope of the patent application, further including a zinc oxide component in a weight percentage of from 0.1% to 1.5%. 5. The composition of the substrate glass for a display as described in item 2 of the scope of the patent application, further including an oxidation error component in a weight percentage of 0.1% to 1.5%. 6. The composition of the substrate glass for a display as described in item 2 of the scope of the patent application, which further includes a beryllium oxide component with a weight percentage of 0% to ι · 0%. 7. The composition of the substrate glass for a display as described in item 3 of the scope of the patent application, which further includes a zinc oxide component in a weight percentage of from 0.1% to 1.5%. 570905 VI. Scope of patent application 8. The composition of the substrate glass for display as described in item 3 of the scope of patent application, including zirconia components with a weight percentage of 0.1 · 1% to 1. · 5%. 9. The composition of substrate glass for display as described in item 3 of the scope of the patent application, which further includes a beryllium oxide component with a weight percentage of ι · 0%. 10. The composition of the substrate glass for a display device as described in item 4 of the scope of the patent application includes an oxidation error component of 1.5% by weight. 11. The composition of the substrate glass for a 1 indicator as described in item 4 of the scope of the patent application, which further includes a beryllium oxide content of 0% to 1.0% by weight. 1 2. The component of the substrate glass for display as described in item 5 of the scope of patent application, including the beryllium oxide content of 0% to 1.0% by weight. 1 3. The composition of the substrate glass for a display as described in item 7 of the scope of the patent application further includes a zirconia component in a weight percentage of 0.1% to 1.5%. 14. The composition of the substrate glass for a display as described in item 7 of the scope of the patent application further includes a beryllium oxide component in an amount of 0% to 1.0% by weight. 15 As described in item 12 of the patent application, the composition of the substrate glass for display devices ′ further includes a zinc oxide component with a weight percentage of 0.1% to 1.5%. 16. The group of substrate glass for display as described in item 15 of the scope of patent application, wherein the total weight percentage of the components such as calcium oxide, magnesium oxide, zinc oxide, hafnium oxide and beryllium oxide is between 4.0 % To 9.0%.