TW200800827A - Alkali free glass and alkali free glass substrate - Google Patents

Abstract

The present invention provides a glass, which has a coefficient of thermal expansion about 40 to 50*10<SP>-7</SP>/ DEG C and a viscosity character which is suitable for stably fabricating thin and large glass substrates. Moreover, the glass is suitable for TFT LCD and particularly for an amorphous silicon type TFT LCD. An alkali free glass is characterized in that it has a composition as follows(the percentage being in weight percentage), 45 to 65% SiO2, 12 to 17% Al2O3, 7.5 to 15% B2O3, 0 to 3% MgO, 5.5 to 15% CaO, 0 to 5% SrO, 5 to 15% BaO, 0 to 5% ZnO, 15 to 23% MgO+CaO+SrO+BaO+ZnO, 0 to 5% ZrO2, 0 to 5% TiO2, 0 to 5% P2O5. The alkali free glass is also characterized in that it is substantially alkali metal oxide-free; a value of (CaO+BaO-MgO)/SiO2 in the alkali free glass is 0.25 to 0.4 by weight fraction; and an average coefficient of thermal expansion of the alkali free glass is 40 to 50*10<SP>-7</SP>/ DEG C in the temperature range of 30 to 380 DEG C.

Description

200800827 24402pif.doc IX. Description of the invention: [Technical field to which the invention pertains]

The present invention relates to a flat panel display substrate such as a liquid crystal display (hereinafter referred to as LCD) or an electroluminescence (EL) display, a charge coupled device (CCD) or an equal magnification type. Solid-state imaging elements (such as contact image sensors (Contact Image Sens®, cis)) are glass-covered (giass eover) for image sensors, and alkali-free glass and alkali-free glass substrates for substrates for solar cells. [Prior Art] Electronic components such as a thin-film transistor-type active matrix liquid crystal display (hereinafter referred to as TFT-LCD) are thinner and consume less package, so they are car navigation systems (carnavigati (10)), The camera is used in various applications such as screens for personal computers and televisions in recent years. Before I, glass was widely used as a flat phase display substrate for LCDs, ELs, and the like. In addition, it is well known that the TFT_LCD panel Weishang manufactures several components on a glass substrate (prime panel) formed by each manufacturer, and then divides each το^^ into products, thereby achieving improvement and reduction. In the case of the computer, the size of the screen of the display screen of the personal computer is only increased, and in order to perform the chamfering of the above-mentioned components a plurality of times, a large-sized glass substrate such as mm is required. In particular, it is important to increase the size of the kneading surface in terms of electricity, and it is important to make the technology for manufacturing large glass substrates in 200800827, 24402pif.doc. Further, in the use of a television, an amorphous germanium TFT-LCD (hereinafter referred to as a-Si TFT-LCD) is generally used (see Japanese Patent Laid-Open Publication No. Hei 7-277762). The glass substrate used for 'a_Si, TFT-LCD, etc., needs to have the following characteristics. (1) If the glass contains an alkali metal oxide, the alkali ions will be expanded into the film-forming semiconductor material during the heat treatment, resulting in deterioration of the film characteristics. Therefore, the glass does not substantially contain the metal oxide. . (2) It has a good temperament, that is, it does not deteriorate due to various acids, tests, etc. used in the optical etching step. Upper &quot;(3) does not shrink heat during heat treatment steps such as film formation, annealing, and the like. For this purpose, the glass needs to have a high strain point (Strain Point). In addition, in consideration of meltability and formability, such a glass substrate is required to have the following characteristics. φ (4) is excellent in meltability so that a poor melting defect as a glass substrate does not occur in the glass. In particular, there are no bubble defects. (5) The opacity-resistant character is excellent so that foreign matter generated during melting and molding does not exist in the smashing. ^(6) Glass having 40~5〇xl (T7/°C thermal expansion) is required for the following reasons. Since the heat treatment step in the manufacturing step of the TF Ding_LCD is repeated, the glass substrate is repeatedly heated rapidly and rapidly cooled, so that it is applied to the glass. In addition, when the glass substrate is increased in size, not only the temperature distribution is likely to occur in the glass substrate, but also a slight flaw is generated on the end surface, and the rate of the i〇c becomes high, and the heat treatment step is further performed. The glass substrate is damaged: and n. In order to solve this problem, the most effective is to reduce the thermal stress caused by the left of the thermal expansion coefficient, so that the thermal expansion coefficient of the glass substrate is smaller, and the silk force generated by the 埶 treatment On the other hand, if the number of thermal expansion turns is small, the melting property and the formability of the glass material tend to be impaired. Therefore, it is not the best policy to improve the expansion of the age. Therefore, it can be said that the glass must be made.

The coefficient of thermal expansion of the glass substrate is controlled within an appropriate range. In addition, it is also important to integrate the LCD and the glass substrate with the heat of the various materials formed on the glass plate. If it does not adhere to the thermal coefficient of the film, it will cause the warpage of the glass substrate, and it may cause damage to the glass substrate. Since the film formed on the glass substrate has various films such as a low expansion oxide film of SiNx and a high expansion metal film such as A, it is necessary to set the thermal expansion coefficient of the glass substrate in consideration of the thermal expansion coefficient of the film. In view of the above, the coefficient of thermal expansion of the glass is preferably 40 to 5 〇χ 1 (Γ7/.^. φ. Further, for the following reasons, it is necessary to (7) the viscosity characteristic is suitable for stably making the enamel plate, Glass for large glass substrates. In portable devices such as mobile phones and notebook PCs, the device is required to be light and light in consideration of the convenience of carrying it, and the glass substrate is required to be light in weight. It is effective to thin the glass substrate. At present, the standard thickness of the TFT-LCD glass substrate is about 〇·7 mm and is very thin. On the other hand, the thinner the glass substrate becomes, the more difficult it is to manufacture, but if it is cooled It is advantageous to form a thin-plate type glass substrate flatly with a glass having a rapidly increasing viscosity. Especially in the case of down draw forming, the furnace distance for slow cooling (8) 〇w 8 200800827 24402pif.doc coojmg) is There are restrictions on the design of the device, so the glass base / V ^ 5, for example, from the forming temperature i until the poem 'up / liter ^ minutes. Therefore, it is advantageous to pull down the glass and quickly increase the viscosity of the glass during cooling. • To be large and medium, in order to remove multiple faces of the display, the matte glass substrate. It is advantageous that the glass substrate has a larger glass with a higher enthalpy. Especially for the down-draw molding, it is necessary for the slow cooling and the inlet limit 1&quot;*1 'for example, from the self-forming temperature to the room temperature, and the viscosity is rapidly increased during the drawing down, if the glass substrate is in the plate width direction. The presence of temperature causes bending or a slight curvature, so that it is flat and difficult to open. In order to solve the temperature unevenness, it is important to control the temperature of the glass substrate. However, when the viscosity is lowered until cooling, when the flat substrate is manufactured, the glass is cooled to a temperature less than 2 times, it is difficult to control the temperature. In particular, it is more difficult to make a flat glass in the length direction of the (4) 0 mm glass. Therefore, ^^ = the material is rapidly rising, and the alkali-free glass which can be rapidly formed into a glass substrate shape has a viscosity which gradually rises due to cooling: = determines the thickness of the glass, the width direction, or the bow The shape makes it difficult to form a large, thin glass substrate flatly. 9 200800827 24402pif.doc [Summary of the Invention] Therefore, the technical object of the present invention is to obtain a glass which satisfies the above-mentioned required characteristics (1) to (5), and (6) has 40 to 5 〇 xl (T7/°C). The coefficient of thermal expansion, and (7) the viscosity characteristic is suitable for the stable production of thin plates and large glass substrates, and thus is suitable for FT-LCDs, especially a-Si, TFT-LCD. The result of active efforts of the present invention and others is It was found that the glass composition was controlled to be φ in terms of weight percent (wt%), the content of Si〇2 was 45 to 65%, Al2〇3 was 12 to 17%, B2〇3 was 7·5 to 15%, and MgO was 〇~3%, CaO is 5.5~15%, Sr〇 is 0~5%, BaO is 5~15%, ZnO is 0~5%, MgO + CaO + SrO + BaO + ZnO is 15~23%, Zr02 It is 〇~5/〇, Ti〇2 is 0~5%, and P2〇5 is 〇~50/^, which does not substantially contain alkali gold. It is an oxide and will be based on the weight fraction (Ca). The value of 〇+ Ba〇-Mg0)/Si02 is controlled to 0.25~〇·4, and will be 30~380. (The average thermal expansion coefficient in the temperature range of 3 is controlled to 4〇~5〇xKr7/°c, thereby • Solve the speed communication, 攸In the present invention, the term "substantially no alkali metal oxide" is used in the present invention, and the content of the alkali metal oxide in the glass composition is 1000 ppm or less. In the present invention, "3〇~380" The average coefficient of thermal expansion in the temperature range of C means the value measured using a dilatometer. If the glass composition is controlled within the above range, it is possible to obtain a pull-down forming, especially an overflow pull-down (overfl〇wd). 〇wndraw) viscous characteristics of the molding. Further, if the glass composition is controlled within the above range, glass having good opacity can be obtained, and the overflow down-draw formation can be stably performed 10 200800827 24402pif.doc (overflow dmw- Therefore, the alkali glass of the present invention can be said to be a glass suitable for overflow down-drawing. Further, if the breakage is controlled within the above range, it can be easily obtained to satisfy the demand and care. The glass of the second ^ (7). Moreover, the invention does not exclude the forming method under the overflow; the forming = the outer forming method. Even if the overflow is pulled down into a forming method outside the gamma, the manufacturing step is made, when the glass is _ It is not easy to pass through the age, and the manufacturing efficiency of the rotating wire board, so the hair _ New Glass can be applied to other forming methods. If the glass group is made in the above-mentioned range _, the viscosity is quickly increased when it is cooled, and it can be quickly Since the alkali-free glass of the present invention is formed by rapidly forming a thin-plate type glass substrate when the viscosity is rapidly increased during cooling, it is advantageous. The rapid rise = ^ can be formed in a large glass substrate, which is advantageous. In addition, when = ^, the slow cooling (4) internal distance has a limited cooling time for the board in terms of equipment design. For example, the viscosity increases rapidly from the forming temperature: = so the 'lower forming time' cooling m manufacturing step There is no 1 in the =2 invention without the surface of the bismuth, the double ion in the heat treatment process, the yttrium η = film semiconductor material, resulting in _ inferiority ^ has damaged the reliability of the TFT-LCD. In the grade glass of the present invention, it will be based on the weight fraction _ called 200800827 24402pif.doc

The value of BaO Mg〇)/Si〇2 is controlled to 〇·25~〇·4. If the value of (CaO + Ba〇-MgO) / Si 〇 2 by weight fraction is controlled within the above range, the opacity resistance is not lowered, specifically, 1 〇 54 dPa · s can be achieved. The liquid phase viscosity and the high temperature viscosity can be lowered to obtain a viscosity characteristic suitable for pull-down forming. Further, in order to lower the high-temperature viscosity, it is effective to increase the alkaline earth metal oxide and reduce the Si〇2 content. However, if the alkaline earth metal oxide is increased and the Si〇2 content is decreased, the strain point is lowered. When the value of (Ca0 + Ba〇-Mg0)/SiO2 by weight fraction is controlled within the above range, even if the alkaline earth metal oxide is increased and the Si〇2 content is decreased, the strain point is not lowered. Reduce high temperature viscosity. Also, the anti-opacity is not deteriorated. Therefore, if the value of (CaO + BaO-MgO) / Si 〇 2 by weight fraction is controlled within the above range, the disadvantages caused by the increase of the alkaline earth metal oxide and the reduction of the Si 〇 2 content can be eliminated. . Further, as described below, if a large amount of Mg 含有 is contained, the resistance to unclearness is impaired. In the alkali-free glass of the present invention, the average thermal expansion coefficient in the temperature range of 30 to 380 ° C is controlled to 40 to 5 〇 x 1 (ryc. If the thermal expansion coefficient of the glass is controlled within the above range, the peripheral material can be realized. Integration of thermal expansion coefficients (especially organic materials or metals), thereby reducing the probability of breakage of the glass substrate in the manufacturing process of the TFT-LCD. Further, if the thermal expansion coefficient of the glass is controlled within the above range, thermal expansion can be reduced. The thermal stress generated by the difference can reduce the probability of breakage of the glass substrate in the heat treatment step, and as a result, the following situation can be effectively avoided, that is, the production efficiency of the manufacturing line is lowered or broken due to the broken glass substrate; 12 200800827 24402pif.doc The fine glass frit produced by the time is attached to the glass substrate and the patterning is poor. The second line of the invention is characterized in that the non-inspective glass of the present invention is characterized by (Mg〇+ Ca0 + Sr0 + Ba〇+ Zn〇)/Si〇2 is the value of 〇 〇 ^ Third, the non-test glass of the present invention is characterized by 4 Sb2Q3 + Sn〇2 + C1 on the paste. The content is changed by the above oxide; wt/〇 is 〇~3%. In the present invention, the phrase "substantially does not contain &amp;# means that the content of strontium 3 is 1 〇〇〇 ppm or less. 2 3" 'Fourth, the alkali-free glass of the present invention is characterized in that substantially 7 persons = 2〇3, Sb2Q3, and the SbOA content is converted by the above oxides =

0~1%. In the present invention, the phrase "substantially does not contain _3" means a case where the content is 0.05 wt%/〇 or less. 2 J Fifth, the non-inspective glass crucible of the present invention is characterized in that the liquid phase temperature is 115 CTC and/or the liquid phase viscosity is greater than or equal to 1 〇 5·4 gam·s. The "liquidus temperature" in the above refers to the smashing of the glass which remains in the 5 〇 mesh _ by the standard: mesh (MeshXSOO _), which is placed in the Ming boat and kept in the temperature gradient furnace for 2 hours. The temperature in the junction glass. In addition, the "liquid phase viscosity" as used in the present invention means the glass complementivity at the liquidus temperature' and the viscosity is a value measured by the fiber d〇ngation method or the surface ball pull-up method. . The sixth invention of the present invention is characterized in that the content of SnS in the glass group is Q to Qx in terms of the above oxide, and when Sn 〇 2 is added until Sn 〇 2 is 0.5 Å, the obtained Glass 13 200800827 24402pif.doc ==: described in the second... The temperature, that is, as another temperature = night phase temperature, means that the bottom glass composition is sn 〇 2 is 0.5 wt% f Boli until wt% ), the glass is melted, and the autumn is measured as 1 〇〇. The glass powder obtained by passing through a standard sieve 30 mesh (5 〇〇 glass sample) is placed at a temperature from the boat _ crystal. The temperature gradient furnace is maintained - After the week, the knot-free glass of the present invention is characterized in that it adds 1 wt% of Zr09 b, and the miscellaneous w H and the middle 1 boot. The secret of the present invention: (4) When it is less than or equal to, the liquidus temperature in which the glass composition is added with 1 wt% of ZrO glass refers to the temperature at which the phase is added to the amount of the raw material required. Quantity = composition from the surface for a total of 101, after the glass, 乂 /, after the powder sample obtained by the powder, will be passed through the standard two The glass powder of the 5〇 mesh is placed in a uranium boat, and the temperature of crystallization is maintained after one week in the furnace. The eighth. The alkali-free glass of the present invention is characterized in that the strain point is larger than the equivalent. C. In the present invention, the "strain point" refers to a value measured by a method based on ASTM C336. The ninth's alkali-free glass of the present invention is characterized in that the high-temperature viscosity is 1 〇 2.5 "P ^ The temperature is less than or equal to 1,535 ft. Further, the degree of twist at a temperature of 1 〇 2·3 dPa · S as described in the present invention means a value measured by a well-known uranium ball pull-up method. 14 200800827 24402pif.doc Tenth, the alkali-free glass of the present invention is characterized in that when the temperature at a high temperature viscosity of 10 ^ dPa · S is T ((c), and the strain point is TfC), "T is satisfied" - T2 S 880 ° C relationship. Eleventh, the alkali-free glass of the present invention is characterized in that when the temperature at a high temperature viscosity of 104 dPa·s is set to (.〇, the softening point is T4fc), the relationship of 1 to T4$330t: is satisfied. . In the present invention, the "temperature at a high temperature viscosity of 104 dPa·s" means a value measured by a well-known platinum ball pull-up method, and the "softening point" means a value measured by a method based on ASTMC338. Twelfth, the alkali-free glass of the present invention is characterized by being in the rib. The amount of erosion after immersion for 24 hours in a 10% aqueous solution of HCL was equal to 5 Hm. In the present invention, "the amount of rhyme after 24 hours in a 1%% hcl aqueous solution of rc" means that the both sides of the glass sample are first optically polished, and then a part of the glass is masked and adjusted to 1 〇%HCL water-soluble ^C solution is dipped in 24 (4) and then 'removal of the mask, using the surface roughness = the value of the step difference between the mask part and the erosion part. Again, the measurement is relieved ^^3, this The invention of the invention is characterized in that, in 2GX: 13 〇 = gas mic acid solution _4 shame: 4.6 wt%, qing: % = minutes after the amount of impurities is less than or equal to 2 Qing said in the invention ^ read acid money towel After immersion (four) minutes; under: _" 30 buffer gas acid solution Saki clock: the value of the 疋 measured, and means that first, each of the = 15 200800827 24402pif.doc optical grinding, after which part of the cover, in The mixture was adjusted to the above concentration of 2 〇. After the immersion in the sputum solution, the mask was removed, and the surface roughness meter was used to measure the difference between the mask portion and the invading portion. Further, the money was applied to both sides of the glass sample. After the optical polishing, the chemical treatment was carried out under the above conditions, and then the mask was removed.

Fourteenth, the alkali-free glass of the present invention is characterized by being in the rib. After immersing in H)%HCL aqueous solution for 3 hours, the surface was visually observed to be white turbid and wrinkled. x Fifteenth, the alkali-free glass of the present invention is characterized in that the surface is visually observed after being immersed in a 2 〇t: buffered hydrogen acid solution (HF: 6 wt%, NHF4: 3 〇 wt%). Observed without sputum white turbidity, enemy pleats. 〇

Sixteenth, the non-test glass filling of the present invention is characterized in that the Young's modulus and the Young's modulus are 27 GPa/(g · cnf3) or more. Further, the "Bian Young's modulus" as referred to in the mouth I is a value obtained by dividing the Young's modulus by the density ^, and "Young's modulus" is a value measured by the resonance method. The seventeenth aspect of the invention is characterized in that the non-inspective substrate is characterized by the alkali-free glass according to any one of the inventions. Upper Article Eighteenth, the alkali-free glass substrate of the present invention is formed by the special drawing. The present invention is based on the nineteenth aspect, and the alkali-free glass substrate of the present invention is characterized in that it is formed by down-drawing. The I-alkali glass substrate of the present invention is characterized in that the black glass substrate of the tenth embodiment is characterized in that it is used for 16 200800827 24402pif.doc LCD. Twenty-first, the non-inspective glass substrate of the present invention is characterized in that it is used for a-Si · FT-LCD 〇 23, and the alkali-free glass substrate of the present invention is characterized in that the substrate has a size of 32 大于 or more. . [Embodiment] The reason for limiting the glass composition range as described above will be described in detail. The % below φ is the percentage by weight (wt%) except for the specific case.

The Si〇2疋 forms a composition of a glass network having a content of 45 to 65%, preferably 48 to 62%, more preferably 50 to 60%, and most preferably 52 to 58%. When the content of Si〇2 is less than 45%, chemical resistance, particularly acid resistance, is deteriorated, and density is increased. On the other hand, when the content of Si〇2 is more than 65%, the high-temperature viscosity is high and the meltability is deteriorated, and the opaque foreign matter (erist〇t) alite is easily generated in the glass. The Al2〇3 is a component which is effective for increasing the strain point of the glass and which increases the Young's modulus, and is contained in an amount of 12 to 17%, preferably 14 to 16.5%, more preferably 15 to 16%. If the content of A1203 is less than 12%, the effect of increasing the strain point is deteriorated. Further, when the content of Al2?3 is less than 12%, the Young's modulus tends to decrease. On the other hand, when the content of Al2〇3 is more than 17〇/〇, the liquidus temperature becomes high and it is easy to become opaque. B2〇3 acts as a melting agent, and is a component which is effective for lowering the viscosity of the glass, improving the melting property, and lowering the liquidus temperature, and the content thereof is 7.5 to 15%, preferably 7·7 to 13%, more preferably It is 8 to 12%. If the content of B2〇3 is less 200800827 24402pif.doc at 7·)/. The j of the (five) agent is not sufficient, and the buffer-resistant hydrogen-donated acid gamma (10) Na) (hereinafter, referred to as "blue-resistant") is deteriorated. Further, if the content of the secret is less than 7·:)%, it tends to become opaque, so that the liquidus temperature rises = direction. In addition, if the content of the right BA3 is more than ls%, the intersection of the glassy soil may be lowered and the heat resistance may be lowered, and the Wei character may be deteriorated. In addition, if the secret is 15/〇 ‘Bei 4, the Young’s modulus decreases and the Young’s modulus decreases.

MgO is a member that increases the Young's modulus of glass, lowers the high-temperature viscosity, improves =, and is the most effective component of the soil-based metal oxide. However, if the content of Mg〇 is large, it is lowered, and it is easy to become opaque, and it may also be caused by the following reaction of Mg 〇 卿 卿 卿 四 四 四 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或The glass substrate is cloudy, so the content of Mg〇 is limited. Therefore, the content of Μ§〇 is 〇~3%, preferably 0~1%, more preferably 0~〇·5%, further preferably 〇~〇.3%, and the best is 〇 ~〇.2%, ideally, it is best not to contain MgO. Here, the fact that the content of MgO is less than or equal to 〇.〇5% is not included in the sprout.

CaO is a knives that does not lower the strain point of the glass and lowers the high-temperature viscosity, and the opaque anti-opacity component is 5,5 to Μ%, preferably 6 to 14%, more preferably 6.5 to 14%, further better is 7 to 12%. Since the glass composition of the present invention is difficult to melt and bubbles easily remain in the glass, bubbles are often generated in the glass substrate. In order to reduce the bubble defects, it is important to increase the meltability of the glass. Glass composition of the invention 18 200800827 24402pif.doc

In the system, when the amount of Si 〇 2 is decreased, the meltability is improved, but the acid resistance is extremely lowered, and the density and the thermal expansion coefficient are increased. Therefore, in the glass of the present invention, in order to improve the solubility of the two glasses, CaO is contained in an amount of 5.5% or more. On the other hand, when the content of Ca 多于 is more than 15%, the BHF resistance of the glass is deteriorated, and the surface of the glass substrate is easily corroded. In addition, Sb may be caused to cause the reaction product to adhere to the surface of the glass substrate. The glass substrate is turbid. Further, if the content of Ca 多于 is more than 15%, the density or coefficient of thermal expansion becomes too high.

SrO 疋 尚 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦 墦~3 5%, good - money is 〇 ~ ^ If the content of (10) is more than 5%, the density or coefficient of thermal expansion increases, or the valley is easy to change opaque.

Ba〇疋 improves the chemical resistance of the surface and resists impermeability, thereby improving the super component's content of 5~15%, preferably 7~14%, and more Ge ^疋'13/〇进-step better Yes. # ea〇 2: ^5% is more resistant to opacity, density or thermal expansion coefficient. If the content of Ba0 is less than 5%, the liquid phase is weaker and the valley is opaque. As mentioned above, it is effective to guide people to change the anti-smartness. If it contains the (C) Ca〇, Qing can enjoy the advantages of fender, extended-life-life, but it will produce the following shortcomings; glass substrate. Therefore, if the iron is lowered, it is difficult to prepare P ^ ^ / there is an appropriate amount of BaQ, and the system can be lowered, and the liquid viscosity can be improved. 19 200800827 24402pif.doc 、 疋 钱 钱 钱 耐 耐 耐 纟 纟 纟 纟 纟 纟 钱 钱 钱 钱 钱 钱 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 融 融 融 融 融 融 融 融 为 右 右 右 右Therefore, the content of Zn〇 is 〇~5% - ^ 3%, more preferably 〇~1%, and most preferably 〇~〇·5%. ...疋0~

In order to obtain a viscosity characteristic suitable for pull-down forming, it is effective to increase the content of the soil-like metal oxide which is lowered and to reduce the SiQ (10) content. However, if the soil-based metal oxide is increased and the amount is reduced by 2, the strain point is lowered. In order not to deteriorate the anti-opacity, the viscosity of the liquid phase is 105.4 dPa · s or 1 〇 5.4 dPa · s or more and the high-temperature viscosity is lowered '(Ca〇+(10)二MgO)/ by weight fraction. The value of Si〇2 is 0.25 to 〇.4〇, preferably 〇26 to 〇39, more preferably 0.27 to 0.38, and most preferably 〇.30 to 〇36. That is, by limiting the value of (CaO + BaO-MgO) / Si〇2 to 〇25~〇4〇, ^ does not lower the strain point and lowers the high temperature viscosity, and the anti-opacity is not evil KK^aO + BaO-MgOySiC^Ufo.Mu^^ Degrees change south' or easily become opaque. On the other hand, if (Ca〇 + Ba〇 -

When the value of MgO)/SiQ2 is larger than _, the density tends to be high and the thermal expansion coefficient tends to be high.

When two or more components are mixed in the respective components of MgO, CaO, SrO, BaO, and Zn0, the liquidus temperature of the glass is lowered, and crystal foreign matter is less likely to be generated in the glass, and as a result, the meltability and the molding can be improved. Sex. The total amount of the above components (MgO + CaO + SrO + Ba〇 + ZnO) is 15 to 23%, preferably 17 to 22%, more preferably 18 to 21%. If the total amount is less than 15%, the effect as a melt is insufficient, and the meltability is easily aggravated. On the other hand, if the amount of the upper Wei is more than 23%, the density and the coefficient of thermal expansion increase, and the Young's modulus decreases, and it tends to become opaque. &amp;02 is a component which improves the chemical resistance of the glass, particularly acid resistance, and increases the Young's modulus, and the content thereof is 〇~5%, preferably G~3%, which is good for „m. If Zr〇2 The content is more than 5%, and the temperature of the _ phase rises, so that the valley is prone to such opaque foreign matter as zircon.

Ti〇2 is a component that improves the (four) properties of the glass, especially for acidity, and lowers the high-temperature viscosity to improve the meltability, and the content thereof is 0 to 5%, preferably θ 〇曰 3%, more preferably 〇 〜 1%, the better step is q ~ not full 〇. ' Take the best is 0 ~ G.3%. If the content is more than 5%, the glass is colored and the transmittance thereof is lowered, so that it is difficult to use for display. P2〇5 is a component for improving the opacity of the glass, and its content is Q 〜5%, preferably 〇~3%, more preferably 〇~1%, and more preferably 〇~ underfill 0.5%, the best is 〇~0.3%. If? When the content of 2〇5 is more than 5〇^, the phase separation and the milk are generated in the glass, and the acid resistance is remarkably deteriorated. As described above, if the contents of Sn 〇 2 and Zr 〇 2 are both large, the enamel is likely to be opaque. However, the value of L (Mg 〇 + CaO + Sr 〇 + Ba0 + Zn 〇) / Si 〇 2 is preferably limited to (10) Μ Μ, more preferably 〇 32 〇 39 39 The best is 〇·34~〇·38, then the Sn〇2 or ζΓ〇2 system is opaque. In the alkali-free glass of the present invention, a long-term component may be added in addition to the above components, for example, it may contain up to 5% of Can 3, Can 2 5 5 2 2 3: The upper component has a strain point for increasing the glass, Young's modulus, etc., but if it is 5% of each ash, there is a tendency for density to increase. 200800827 24402pif.doc

, Ida / JEL ^ The surface composition of the present invention (4), previously, is the MO3 that acts directly on the high circulation. However, in recent years, attention has been paid to 222. It is better to try not to use AS2〇3. This kind of environment is negative LSn0^AS2〇3, and it has a clear at high temperature to melt the alkali-free glass of the present invention. The clarifying agent is very effective. ^ 1 lx Ming of a few alkali glass, the content of Sn 〇 2 is better 〇 ~ 5%, ~ 〇 35 〇 / 'two into the female better 疋〇 ~ 0.5%, the best is 〇 Hair is easy to be opaque. Further, as the clarifying agent, it is possible to efficiently produce a glass substrate which is not defective in the form of a vesicle without adding a clarifying agent such as Sn02 to the right. The glass U has a silky fruit of the (four) _, and has a long-life component which is melted at a low temperature and has a long-life component of the manufacturing equipment, and the point is lowered. , 2 2 3 / 〇. If the content is more than 3%, it may be strained (4). The chlorinated chloride-based metal oxide chloride or the reduced raw material may be used as a raw material of the C1 component. Hole: It is a clarifying agent without glass in the present invention, but 'the alkali-free glass is generally melted 2, so it is also desirable to: when the agent is used, it is desirable to increase the amount of addition, or to use the fish to clear Sexual ingredients combine to reduce the temperature of the health / if it is greater than or equal to %, there is a tendency to increase the density, and the right side is 〇~2. /. , better | SQ /, the spoon is added better, better 疋 G ~ L)%. In addition, for some or all of Sb2〇3 in a raw material of 22 200800827 24402pif.doc, (4) in addition, when the benefit of the present invention is better, the use of (10) 3 as clarification or And one of the groups of C1, the ratio of which is particularly good is 秘 2 is 〇·〇!~1%, C1 is 〇~1%. Caused negative === Although the poison ship, Na is the environment containing Sb203. Second, from the point of view, it is preferable that the substance is not toxic, so that the crane is a halogen such as volatilization of the glass. Here, the content of i in the composition of the glass is small and unrealistic. It means that the glass 〇h 〇α ～ 取 疋 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 贯 = = = = = = = = = = = = = = = = = )

Sn 0 H Wt% is contained as 0 to 1% (preferably (10) 1 to 1%) such as 20 Å as a clarifying agent. ' Contains:: Equivalent = di-alkali glass, as long as it does not damage its properties, it can contain small F, S〇3, c, etc. as a clarifying agent. Further, a metal powder such as Si may be used as the clarification cut. This is used as a clarifying agent in 5% (10), Fe203 or the like. It is good to contain ΐϊ成范财, (4) it is possible to arbitrarily combine the components of the glass; work = choose a better range of glass composition, wherein the SiO 1 glass composition range is not broken, ~, in wt% ^~50~60%, Al2〇3 is 14~16.5%, B is 3•0, 峋〇 is 〇~0.5%, Cao is 6~14%, Sr〇 is 200800827 24402pif.doc 0~3.5%, BaO is 7 to 14%, ZnO is 0 to 3%, IvigO-f CaO + SrO + BaO + ZnO is 17 to 22%, Zr02 is 0 to 1%, and Ti〇2 is 〇 to 3%. 2〇5 is 〇~3%, and substantially does not contain an alkali metal oxide, and the value of (CaO + BaO - MgO) / SiO 2 is 0.25 〇 4 4, and j gt 〜 380 C The average thermal expansion coefficient in the temperature dry circumference is 42 to 48&gt;&lt; 10 / C. The right side of the glass is limited to the above range, which can be large

The web improves resistance to opacity and reliably ensures the viscosity characteristics necessary for overflow drawdown. A more preferable aspect of the alkali glass is exemplified by a glass having a content of 52% to 58%, an Al2?3 of 15 to 16%, and a B2q3 of g to 12%. MgO is 〇~〇.5%, Ca〇 is 7~12%, and Sr〇 is 〇~3%.

BaO is 1〇~13%, Zn〇 is 〇~0 5%, Mg〇+Ca〇+ Sr〇+ BaO + ZnO is 18~21%, ZK&gt;4 G~”/., now Q~〇5 %, P2〇5 is 0~0.5%, which does not contain metal oxide in nature, and the value of 〇2 is 0.25~0.4, and 30 47:1 in terms of dryness (Ca〇+ Ba〇-〇). The average coefficient of thermal expansion in the range of 44 is required to be 'sexual' and can reliably ensure that the overflow is pulled down to a level within the temperature range of 3G to WC, and the coefficient of swell is 4〇~5〇χ1〇 · 7 Τ 49xum:, better is 43~48. Parent = 42~ ~ 47xur7/t:. If | C is even better, 44 can't get with the surrounding material in 4 readings, then maybe | (especially 疋 organic Material or metal) thermal expansion system 24 200800827 24402pif.doc integration of the number. Another surface, if the average thermal expansion coefficient is greater than the outline ~.c, the damage probability of the glass substrate in the TFT-LCD manufacturing step becomes higher. In the use of LCDs, the thermal shock resistance of glass substrates is also an important requirement. The end faces of glass substrates are finely wounded or cracked even if they are chamfered. The tensile stress is concentrated on the flaw or crack, ^ 1 The substrate will be broken. If the substrate is damaged, the following conditions may occur, that is, not only the production efficiency of the manufacturing line is lowered, but also the damage generated when the substrate is broken. The fine glass frit adheres to the glass substrate to cause poor wire breakage or poor patterning, etc. In the manufacturing steps of TFT-LCD, especially polycrystalline switch ly SiliC〇n TFT-LCD (P-Si4FT_LCD), heat treatment Since the glass substrate is subjected to rapid heating and rapid cooling, the thermal shock to the glass substrate is further increased. Further, as described above, the glass substrate tends to be large, and the large glass substrate is not only susceptible to temperature during the heat treatment step. Poor, and the probability of micro-scratches and cracks on the end faces is also changed, so that the probability of breakage of the glass substrate in the heat treatment step becomes high. • The most fundamental and effective way to solve this problem is to reduce the heat generated by the difference in thermal expansion. Stress, therefore, a glass having a low coefficient of thermal expansion is required, and specifically, a glass having a thermal expansion coefficient of 5 〇 x 1 or less (T7/t:) is required. In the alkali-free glass, the liquidus temperature is preferably 1150 ° C or less, more preferably 108 or less (rc, further preferably 1050 ° C or less, and most preferably 103 CTC or less. In the pull-down forming, especially in the overflow down-draw forming, the viscosity of the glass is higher than that of the other forming force method. Therefore, the opaque resistance of the right glass is poor, and an opaque substance is formed during the forming process, and it is difficult to form a glass substrate. Specifically, if the liquid 25 200800827 24402pif.doc is used, the overflow down-draw molding becomes difficult, and it is necessary to adopt a molding or surface substrate such as a float fbnning, and a processing step is imposed, and "," The method of forming the alkali surface suffers from an inappropriate TO: the shape of the crucible having the desired surface quality. Further, the lower the liquid phase μ degree, the better the opacity resistance of the glass. : In the alkali-free glass of the invention, the liquid phase viscosity s. A 妒 丄 & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & The forming side is broken. In addition, the surface quality of === In the non-test glass of the present invention, the number of months and the side of the moon are good. It contains 0 to 0.5 wt% of Sna, and it is called the conversion of the seven substances. When the domain is less than or equal to mot:, it is better that it is small _. It is preferable that internal defects such as bubbles prevent the glass substrate from being fatally defective. - Generally speaking ^^ 200800827 24402pif.doc. The probability of remaining bubbles is increased, and the bubble is increased. The productivity of the glass substrate is lowered. Therefore, the technology of the probability of good defects becomes important. The method of reducing the amount of clarifying agent contained in the bubbles contained in the glass and the method of lowering the high-temperature viscosity are as follows: Q|1 _. As the clarifying agent for the alkali-free glass, the most effective one is "environmental load chemical substance, Therefore, it is necessary to reduce the use of I3, but due to the AS2〇3 environmental point of view, the study introduces Sn〇7 as As.: 2 3 2

Internal defects in glass &amp; substrates. Therefore, if it is relative to (4) ΙΙΓα S Sn〇2 : ί 4 and Ming ', I - and realize the manufacturing efficiency of the glass substrate to some extent, assuming that the Sn electrode is dissolved in the glass = = too much relative to Sn 〇 2 It is difficult to produce opaque glass. In other words, according to the invention, even if the glass shirt, J丨: 2, rises to 0.5% in summer, the liquid phase of the obtained glass can be made smaller than the dish. Miscellaneous 115 (rc, therefore, can maximize the above effects. On the other hand, when the Sn02 content in the glass composition is 05%, if the (four) glass (four) liquid phase temperature obtained is higher than (10).c, it is difficult to Effect 0 ~ In the non-glass of the present invention, when 1% of ruthenium 2 is added to the glass composition, the obtained glass-liquid phase temperature is preferably (10). C, more preferably less than or equal to Cong. It is effective to reduce the manufacturing cost of the slabs, and it is effective to reduce the life of the melting kiln and reduce the frequency of repairing the melting f. For this reason, it is difficult to invade the bribes. The surface &amp; refractory, however, the more the Zr-based refractory is used, The more easily it is, the crystallized foreign matter (which is not known), which can be an internal defect that breaks away from the substrate. Therefore, if it is opaque glass with respect to Zr〇2#, the shell 4 even uses &amp; Since the refractory is used as the refractory of H, it is difficult to produce opacity due to this threat. Therefore, the manufacturing cost of the low-glass squeegee can be considered to be non-f effective. In this respect, the 无 ' '本|' Adding 1% of Zr〇2 to the glass composition, the liquid phase temperature of the obtained glass can be made less than or equal to mere, so that the above effect can be maximized. On the other hand, there is 1% in the glass. In the case of 〇2, it is difficult to enjoy the above effect if the liquidus temperature of the obtained glass is at 1150 C'. In the alkali-free glass of the present invention, the temperature at a high temperature viscosity of 1 〇 2.5 dPa·s is preferably smaller than It is equal to 1535t, more preferably less than or equal to 15 machine-step-by-fourth (four) is small material test. c, especially good is less than or equal to 15=, and most preferably less than or equal to 15(10).c. As mentioned above, if at high temperature Lower (four) molten glass, although it can reduce bubbles or foreign matter in the glass Internal defects', but the melting in the high temperature region will increase the burden of breaking the melt. For example, 'fines make (4) oxidation_oxidation refractories, the temperature Vietnam is heavily invaded by the glazed glass, and then (four) empty The A cycle (Hfe cyde) is also shortened. In addition, it is used to maintain the interior of the kiln. The miming cost is higher than the melting of the glass at low temperatures. The melting in the ancient and θ domains is not conducive to manufacturing The substrate, here, is to be melted at a low temperature. In this respect, the glass without glass according to the present invention, 28 200800827 24402pif.doc can have a high temperature viscosity of l〇2·5 dPa · S when the temperature is less than or equal to 1535 〇c, so you can enjoy the above effects. On the other hand, if the high temperature viscosity is Μ. When the temperature at dPa's is higher than i535 °C, it is difficult to enjoy the above effects. In addition, when the high temperature viscosity is 102.5 dPa · s, the temperature of the molten glass corresponds to the melting temperature. - The strain point of the non-glass of the present invention is preferably greater than or equal to 6] 0 C, more preferably greater than 635 C, further preferably greater than equal to 64 ° C, and most preferably greater than Equal to 645t:. Further, the glass substrate is supplied to the high-temperature heat treatment in the manufacturing process of the TFT-LCD. If the heat resistance of the glass substrate is low, for example, when the glass substrate is exposed to a high temperature of the hoppers (10) to (10), a small size shrinkage called heat shrinkage may occur, which may cause the pixel pitch of the TFT to shift. Become a cause of poor display. Further, if the heat resistance of the glass substrate is lower, the glass substrate may be deformed, warped, or the like. Further, in order to prevent the glass substrate from being thermally shrunk without causing pattern shift in the TFT-LCD manufacturing step such as the film forming step, it is also required to have excellent heat resistance. In this respect, according to the alkali-free glass of the present invention, ^ can be made to have a strain point of 630 ° C or more, so that the above problem is difficult to occur. On the other hand, if the strain point is less than 630 ° C, the above problem becomes serious. In addition, compared with a-Si TFT-LCD, the heat treatment temperature is higher in the manufacturing process of P-Si TFT-LCD, so the glass substrate with higher strain point is suitable for p-si • TFT-LCD. In the alkali-free glass of the present invention, when the temperature at 1〇2·5 dPa·S is LOG) and the strain point is LfC), it is preferable to satisfy the relationship of D2$88 (TC). At the melting temperature, and corresponding to the temperature in the kiln melting 29 200800827 24402pif.doc glass breaking, the better. Generally, if the index of 眭 2 is lowered, the higher the Τ 2 heat resistance is 2 Τ] rise, however In order to reduce the breakage H, and if it is improved and the heat resistance is excellent, it is preferable to melt at a low temperature, which is 870 or less. 〇, Τ Τ 2 is less than or equal to 88 crc, and more preferably less than or equal to More preferably, it is less than or equal to 86 〇 ° C, and the lowest temperature melting and heat resistance are achieved. Right 2 is still at 880 ° C, it is difficult to invent the alkali-free glass, and the softening point will be set. _, the degree of ^ ^ ^ 4 $ 33 .. The relationship between the thickness of the broken glass Τ &quot;: LI: The temperature of the molten glass is determined from the process of forming the temperature to reach the heart and the red. Because of another good person The county 祜TJU is reduced to the right Ding 3 - T4, specifically, the Ding 3 ~ Τ 4 is less than or equal to 33 〇〇 c, 3? 5 〇Γ &Gt; e text good 疋 less than the temple in 5C is less than 32 〇t, it is easier to control the thickness of the glass substrate, the warping or bending shape of the viewing direction. Another T3yT4$33 () C, then cooling When the viscosity is rapidly increased, the shape of the glass substrate can be rapidly formed. That is, if T3 - 4 is less than or equal to 33 〇〇 c, it is easy to form the thin glass substrate flatly. Further, if Τ3 - Τ4 is less than or equal to 330X: It is easy to form a large glass substrate flatly. In addition, when the shape is pulled down, the slow cooling time of the glass substrate for the slow cooling of the furnace is limited. For example, it is necessary to cool for several minutes from the molding / m degree to room temperature. Therefore, the above viscosity characteristics are very advantageous. On the other hand, if I -I is higher than 33 〇t:, the thickness of the glass substrate and the direction of the sheet width are controlled. The warp or curved shape becomes necessary. In addition, 30 200800827 24402pif.doc TS corresponds to the forming temperature. The density of the non-glass of the present invention is preferably 々g/cm, more preferably less than or equal to 2 7〇3, into —牛于寺 at 2.80 at 2 .68 g / cm;, the best two more / is the lower the density, the lighter weight of the glass can be achieved, the Η-LCD _ quantization m of the fruit-glass granule helps to achieve the density of _ If it becomes lower, then the temperament will deteriorate and the ambiguity will increase from the rise: while Μ = glass, the degree is lower, and the second is not bad, so the overflow can not be pulled down: Rongda County plate. Therefore, the self-occupation of the affiliation is found in ^ g / em (ideally greater than or equal to 2 • (9) g / cm 3). T乂 疋 疋 每 每 每 每 ( ( (9)

After 24 hours in the aqueous solution, the intrusion 〇HCL ^ inch was in the barrier, and/or immersed in the 〉7> gluten solution for 3 hours, and the surface was observed to be opaque and wrinkled. Further, preferably, the amount of erosion of the non-inspected glass of the present invention after immersion in a 20 C bOBHF solution for 3 minutes is less than or equal to 2 μm and the mass is at 20. . After the minute of 63 Qingyi, the surface observation was not found to be white turbid or wrinkled. On the surface of the TFT-LCD glass substrate, a transparent conductive film, an insulating film, a semiconductor film, and a metal film are formed, and the light is removed from the shadow (10) gamma 叩 ^ ^ ^ ( ( ( ( , photoetchmg) formed with various circuits or patterns. In addition, in the film forming and photo-etching steps, various heat treatments or medicines are applied to the glass substrate, and the film formation step is performed in a step-by-step process. Class-series=two:: For the etching of lanthanum], the lanthanide film is treated with a phosphoric acid solution as a solution of ΪΪ^ΗΓΤ〇(ΐη&quot;ίΠηΐ ^ 〇Xide 5 7 +HN〇3) as a lithography solution for SiNx , SiO 2 , etc., using a variety of liquid medicines such as _ solution as the upper part of the money engraving liquid, considering the cost reduction, is not a one-time circulation (four) flow. If the comparison of the surface substrate is likely to cause the following problems in the _ ^ = =, the shield ring liquid flow of the coffee, or by; =: the surface of the second sputum is white turbid ' or the etch rate due to the composition of the etchant Become unstable and so on.尤1 夂匕 : Because of the strong invasion of the glass substrate: it is easy

In other words, the BIiF resistance of the glass substrate is required to be excellent, and the second step in the step of blocking the tortoise is not only in the glass substrate, but also in the chemical resistance of the two sheets, and in the aspect of not changing the appearance of the car. It is more important, and the appearance of the glass does not produce white turbidity. The treatment of the glass-based TFT-LCD by the liquid chemical treatment is characterized by the fact that the light transmittance is more important and the change in the amount of the button and the appearance change. For example, even if the glass shows the same amount of money invading, and the reason is not widespread, the appearance change after the treatment of the drug is not in the aspect of the invention, according to the invention 200800827 24402pif.doc 24 hours in 10% HCL aqueous solution After that, the amount of erosion can be less than or equal to $ _, and immersed in 8 〇. After 3 hours in a 10% aqueous solution of HCL, the surface observation was visually observed to reveal that no turbidity or wrinkles were formed, so that the above problem can be reliably solved. In particular, the alkali-free glass according to the present invention, even if immersed in 2 〇 Its 130BHF; in the liquid for 3 minutes, the amount of money invading can also be less than or equal to 2 twists, and ^ ^ Wen collapsed in 2 (TC 63 solution in 30 minutes, visual observation of the surface can not be found white turbid, Wrinkles, so can solve the above problems reliably.

In the alkali-free glass of the invention, the Young's modulus (the value obtained by dividing the Young's modulus by the density) is preferably 27 GPa/g · cm -3 or more, and more preferably 28 GPa / g or more. · The best cm' is greater than or equal to 29 G. If the ratio of Young's modulus is greater than or equal to 27, 哗 咖 _ _ 3, then # = type and the binding plate can also suppress the amount of bending to no problem ^ This = no test _ substrate can be used by In the manner of L glass raw material to achieve the desired glass composition into the melting furnace, followed by heating and melting, rinsing, 'beauty-shaped device and forming the molten glass into a plate shape, and then proceeding to give the cost of the invention The alkali glass substrate is preferably a pull-down from the viewpoint of the ?7 &amp; substrate: two: good glass forming of the shell. The reason for this is that when the overflow is drawn down, it should be formed in a state where the overflow is pulled down, whereby the glass substrate on the free surface can be omitted. Here, the overflow is pulled down to "^ The surface quality is good. The method of breaking the heat from the two sides of the heat-flowing trough-like structure, so that melting, touching, and then overflowing 200800827 24402pif.doc

The molten glass is produced at the lower end of the launder structure, and the glass substrate is produced. The size or surface quality of the 4::: square-stretched glass substrate of the launder structure is: "From the quality of the glass substrate for breaking TFT-lcd, 4::: now available for downward For extension molding, it is possible to use any of the following: =:: In addition, the force can be extended, for example, in a contact-resistant state in which the width is sufficiently large, or the wire-formed roller can only be joined to the vicinity of the end surface of the glass substrate. d ground = glass is excellent in opacity resistance, and the viscosity is in the form of an open-flow down-draw. y (In addition to the shape of the method for producing an alkali-free glass substrate of the present invention, various methods may be employed. Can be taken = drop down (8) (four) face (four) forming, pull again (four) called "two

Mi〇m) forming each thief-shaped method. In addition, in terms of cheap soil and a board, it is preferred to form a floating method. ~ Soil The alkali-free glass of the present invention is preferably used as a glass substrate. In the present invention, various methods of forming the alkali-breaking glass can be employed. However, the alkali-free glass of the present invention is excellent in opaque resistance and has an appropriate [occupancy characteristic], so that it can be favorably formed into glass. The substrate and the glass substrate ς are suitable for displays such as LCDs. As described above, the glass substrate tends to increase in size. However, if the substrate size becomes large, the probability of occurrence of an opaque substance in the substrate becomes high, and the yield is drastically lowered. Therefore, the alkali-free glass substrate 'of the present invention which is excellent in opacity resistance is advantageous in producing a large-sized glass substrate. For example, the substrate ruler 34 200800827 24402pif.doc is greater than or equal to 0·1 m2 (specifically, the size is greater than or equal to 320 mm x 42 () mm), especially greater than or equal to 〇·5 m2 (specifically, the size is greater than or equal to 63〇mmx830 Mm), greater than or equal to 〇·〇m2 (specifically, the size is greater than or equal to 950 mmxll50mm), further greater than or equal to 2.3 m2 (specifically, the size is greater than or equal to 14〇〇mmxn〇〇mm), greater than or equal to 3·5 m2 (specifically, the size is 1750 mm x 2050 mm or more), and is greater than or equal to 4 8 m 2 (specifically, the size is 2 i 〇〇 mm x 23 〇〇 mm), and the larger the substrate size is as described above, the more advantageous it is. In terms of the face size of the display, the substrate size is preferably 32 Å or more, more preferably 36 Å or more, and still more preferably 40 Å or more. Further, according to the ethylenic glass substrate which is too bright, the characteristic X of low density and high specific Young's modulus can be obtained, and in addition to the above, the thin glass substrate can be formed with high precision. For example, if the wall thickness is less than or equal to 0.8 mm (preferably less than or equal to 〇.7 mm, more preferably less than or equal to 0.5 mm, and the step-by-step is preferably less than or equal to 〇4 mm), it is effective Enjoy the advantages of the present invention. In addition, the glass substrate of the present invention and the first substrate can reduce the amount of bending of the glass substrate even if the thickness of the glass substrate is small, so that it is easy to prevent the glass substrate from being placed in a bracket or a self-cutting bracket. Damage at the time of removal = day, it is better to use the glass substrate to meet the requirements of the LCD financial board (1) ( ^ and the viscosity characteristics are suitable for overflow pull-down forming: impervious to the moon, so It can effectively manufacture large and /200800827 24402pif.doc or thin glass substrates, so that the large-scale requirements of glass substrates (especially glass substrates for TV sets) can be reliably satisfied. In addition, the alkali-free glass substrate of the present invention is also It is suitable for p-Si · TFT - glass substrate for LCD. [Examples] The present invention will be described in detail based on the examples, and the glass of the comparative example of the glass of the comparative example (samples Νο·1 to 38) is

Mouth Ν〇.α, β). 36 200800827 24402pif.doc [Table 1]

37 200800827 24402pif.doc [Table 2]

38 200800827 24402pif.doc [Table 3]

39 200800827 24402pif.doc [Table 4]

Example 19 20 21 22 23 24 Glass composition (wt%) Si02 55 54.5 55 55 55 54.5 Ai2〇3 15.5 15.5 15.5 15.5 15.5 15.5 B2O3 8.5 9 8.5 8.5 8.5 9 MgO 0 0 0 0 0 0 CaO 9 9 8 8 7 7 SrO 0 0 0 1 2 1 BaO 11 11 12 11 Π 12 Sb2〇3 1 1 1 1 1 1 (CaO + BaO - MgO) / SiO 2 036 0.37 0.36 0.35 0.33 0.35 (MgO + Ca.0 ~r SrO+BeO -l· ^ ZnO)/SiO 2 0.36 0.37 0.36 036 0.36 0.37 Density (g/cn〇2.63 2.63 2.63 2.63 2.63 2.63 a3〇-38〇r(xl〇-7/°C) 45 45 45 45 45 44 strain point T2 (°C) 655 651 653 655 655 652 Slow cooling point (°C) 705 701 704 705 706 703 Undercut point T4 (°c) 918 911 921 920 926 922 South temperature viscosity (°C) 104 dPa · s T3 1220 1215 1236 1232 1245 1238 103dPa· s 1380 1374 1399 1394 1409 1406 102·5 dPa· sT] 1484 1478 1505 1500 1515 1518 Ti-T2 (°C) 829 827 852 845 860 866 T3-T4CC) 302 304 315 313 320 317 Young's modulus (Gpa) 76 Not measured Not measured Not measured Not measured Unmeasured specific Young's modulus (Gpa/(g/cm·3)) 29 Not measured Not measured Not measured Not measured Not measured Unmeasured anti-opaque liquid Phase temperature (°C) 1035 1030 1045 1025 1020 1010 Liquid viscosity logrj(dPa · s) 5.9 5.8 5.8 6.0 6.2 6.2 Anti-Zr02* transparency anti-Sn02 opacity 〇〇〇〇〇〇 chemical resistance HC1 (erosion/appearance) ◎/〇◎/〇◎/〇◎/〇◎/〇◎/〇BHF resistance (erosion/appearance) ◎/〇◎/〇◎/〇◎/〇◎/〇 ◎/〇40 200800827 24402pif.doc [Table 5]

Example 25 26 27 28 29 30 Glass composition (wt%) Si02 55.7 55.2 54.7 54.7 54.7 55.2 Al2〇3 15 15.5 15 15 16 15.5 B2O3 9 9 9 9 9 9 MgO 0 0 0 0 0 0 CaO 10 10 10 10 10 8 SrO 0 0 1 0 0 0 BaO 10 10 10 11 10 12 Sn02 0.3 0.3 0.3 0.3 0.3 0.3 CCa0+Ba0-Mg0)/SiO 2 036 036 0.37 0.38 0.37 0.36 (MgO + CaO + SrO + Ba〇 + Zn0) / Si02 0.36 0.36 0.38 0.38 0.37 036 Density (g/cm勹2.61 2.62 2.63 2.64 2.62 2.62 a3〇-38〇t(xl〇'7/cC) 46 46 47 47 46 45 Strain point T2(t:) 655 657 655 655 658 658 Slow cooling point 702 703 701 702 706 705 Softening point T4rc) 907 908 901 902 912 921 High temperature viscosity (°C) 104dPa· sT3 1206 1201 1183 1190 1202 1230 103 dPa · s 1366 1363 1342 1345 1359 1397 102 5dPa· s Ding i 1471 1466 1443 1449 1460 1503 T]-T2(°C) 816 811 790 797 804 847 τ3-τ4(°〇301 299 284 290 292 311 Young's modulus (Gpa) 77 76 78 77 77 76 Than Young Modulus (Gpa/(g/Ciif3)) 29 29 29 29 29 29 Anti-opaque liquid temperature (t) 1040 1020 1020 1025 1055 1005 Liquid viscosity logT|(dPa · s) 5.6 5.7 5.7 5.6 5.4 6.3 Anti- &amp; 02 opacity 〇〇〇〇〇〇 anti-Sn 〇 2 opacity 〇〇〇〇〇〇 chemical resistance HC1 resistance (erosion / appearance) ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ /〇◎/〇BHF resistance (erosion/appearance) ◎/〇◎/〇◎/〇◎/〇◎/〇◎/〇41 200800827 24402pifdoc [Table 6]

Example 31 32 33 34 35 36 Glass composition (wt%) Si02 58.7 56.7 56.7 56.7 56.7 55.7 ai2o3 15 15 15 15 15 16 Β2〇3 8 8 8 8 8 8 MgO 0 0 0 0 0 0 CaO 11 6.5 6.5 8 8 10 Sr〇0 3.5 5 2 5 0 BaO 7 10 8.5 10 7 10 Sn02 0.3 0.3 0.3 0.3 0.3 0.3 (Ca0 + Ba0-Mg0) / Si02 031 0.29 0.26 0.32 0.26 0.36 (MgO + CaO + SrO + BaO + Zn0) / Si02 0.31 0.35 0.35 0.35 0.35 0.36 Density (g/cml 2.66 2.62 2.63 2.62 2.62 2.62 ^3〇-380^(xl〇V 〇45 44 44 45 46 46 strain point T2cc) 666 660 661 661 662 663 Slow cooling point (t ) 714 711 711 711 711 712 Softening point T4fc) 925 931 931 927 924 921 High temperature viscosity (°c) 104dPa · sT3 1218 1252 1246 1239 1223 1219 103dPa· s 1380 1422 1417 1407 1392 1379 102-5dPa· sTi 1484 1532 1523 1514 ]499 1483 T丨-T2rc) 820 874 864 855 839 822 T3—T4cc) 295 323 317 314 301 300 Young's modulus (Gpa) 77 Not determined Not determined Not determined Not determined 78 Specific Young's modulus (Gpa/( g/ciT〇) 29 Not determined Not determined Not measured Not measured 29 Anti-opaque liquid temperature (°C) 1070 1055 1055 1045 1060 1 060 liquid viscosity logrj (dPa · s) 5.4 5.8 5.8 5.8 5.6 5.5 anti-Zr02 opacity 〇〇〇〇〇〇 anti-Sn02f transparency 〇〇〇〇〇〇 chemical resistance HC1 resistance (erosion / appearance) ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ / 〇 BHF (erosion / appearance) ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ / 〇 ◎ / 〇 42 200800827 24402pi £ doc [table 7] Example Comparative Example 37 38 AB Glass composition (wt%) Si02 53 53 64 46 AI2O3 17 17 16 17 B2O3 9 12 11 15 MgO 1 0 0 0 CaO 9 6 3 10 SrO 5 3 6 2 BaO 5 8 0 10 Sb^Os 1 1 0 0 (CaO + BaO-MgO) / Si〇2 0.25 0.26 0.05 0.43 (MgO + CaO + SrO + BaO + Zn0) / Si02 038 0.32 0.14 0.48 Density (g/cm. ) 2.63 2.58 2.43 2.65 a3〇-38〇r(xl〇'7/°C) 48 43 32 51 Strain point τ2(ΐ;) 659 637 670 626 Slow cooling point (°C) 702 685 722 670 Softening point T4rc) 887 915 992 866 High temperature viscosity (°c) 104 dPa · s T3 1153 1195 1309 1112 ]03dPa· s 1289 1346 1467 1256 102·5 dPa · s T] 1375 1441 1542 1358 Τι-Τ2 (°〇716 804 872 732 T3 -T4(°C) 266 280 317 246 Young's modulus (Gpa) 82 75 74 77 Specific Young's modulus (Gpa/(g/crrT3)) 31 29 31 29 Anti-opaque liquid temperature fc) Not determined Measurement unmeasured unmeasured liquid phase viscosity logr|(dPa · s) Not measured Not measured Not measured Not measured Anti-Zr02 opacity 〇〇 Not measured Not measured Anti-Sn02 opacity 〇〇 Not measured Not measured Chemical resistance HC1 resistance ( Erosive/appearance) ◎/〇◎/〇 Not measured Not measured BHF resistance (erosion/appearance) ◎/〇◎/〇 Not measured Not measured

Each of the glass samples in the table was made in the following manner. First, the glass material will be blended to achieve the composition of the table. The amount of the material in the table is 43. The amount of the material is 'into the turn (four), and the second layer is melted at 155 (rc) and the plate is shaped like this. The obtained glass samples: test, detection, heat secret coefficient, strain point, 'slow cooling point, softening point, ancient, pull adhesion ^ Young's modulus, specific Young's modulus, anti-opaque (_temperature = phase 'degree), various properties of the quality of the product (resistantness, yttrium resistance), and are shown in the table. Density is determined by the Arehimedes method. The average value in the temperature range of the 3〇~boots measured by the dilatometer. The strain point and the slow cooling point are measured by the method based on ASTMC336. The higher the value of the strain point and the slow cooling point, the glass resistance The higher the New Zealand. The chemical point is measured by ASTM C338. The high temperature viscosity is 104·0 dPa · s, 1〇3.0 dPa · s, ΐ〇2·5 dPa

The temperature at each time is known by the county. The a a-S Young's modulus measured by the ball pull-up method is measured by a resonance method. The ratio of Young's modulus is calculated by dividing the Young's modulus by the density. The use of the cutting liquid phase means that the glass samples are pulverized, and the glass powder remaining in the 5 mesh (_4) through a standard mesh (500 μm) is placed in a boat and kept in a temperature gradient furnace for 24 hours. The degree of crystallization out into the glass. The liquidus temperature at the time of the addition of Sn02 (in the table, the anti-Sn〇2 means that Sn 〇 2 is added to the secondary charge amount as a raw material until the SnOj is 0.5% in the middle, under the same conditions as above. Make glass = 44 200800827 24402pif.doc After 'crushing glass sample: will pass the standard sieve 30 mesh temperature ladder = 〇) 〇 mesh (3 〇 ° (four) glass powder into the platinum boat, in / dish and furnace kept - Week, the crystallization is measured and no opacity is found in the next generation. "^" "Liquid temperature of human two H ab forces for 2 days (in the table is anti-Zr02 opacity). Add phase # Glass composition of 苴 =, private: 2 \ under the same conditions as above to make the glass melt, forming, 222 glass inspection products, will pass the standard sieve 3G mesh (5GG _) and the residue (class (four) of the fine powder fine From (4), and at the temperature ladder week 'measure the date of the end of the day (4) temperature. Second 'will be recorded in the case of 1150t;; the case of alum is recorded as "x", no opaque person is found under 115叱 = Viscosity is the viscosity of the glass at the liquidus temperature. The glass viscosity is determined by the two-two: ί ball pull-up method. The lower the liquidus temperature and the higher the attacking part, the more excellent the opacity resistance is. The JBHF and HC1 resistance are evaluated by the following method. H 1: The two sides of the sample are optically ground and masked- In part, in the pre-two = hood = agricultural medicinal liquid dipping for a predetermined time. The step of the medicinal liquid is measured by the i-meter to determine the amount of money invaded by the mask part and the invading rice section. In addition, each measurement is After the optical treatment of the two sides of each glass was carried out, the chemical liquid treatment was carried out under the following conditions. 45 200800827 24402pif.doc After removing the mask, the amount of erosion resistance to BHf was 13 〇 for the chemical solution and the processing conditions. BHF solution (ΝΗ4Ηι?2: 4·6 tree%, NH4F: 36wt%) and measured under 2 (rc, 3 〇 minutes of treatment conditions. For BHF resistance, if the amount of erosion is less than 〖μπι is recorded as "◎", if it is 1~2 μπι, it is marked as "〇". The resistance to the (four) nature is measured by the use of the heart acid solution in 8 (TC, 24 hours of processing conditions, if the resistance (four) invade money If the amount is less than 2·5, it is recorded as “◎”, if it is 2·5~5 _ $ for “〇”, if it is greater than 5 μπι, it is recorded as “X”. For the evaluation of the appearance of the liquid and the treatment conditions, the BHF resistance was carried out using a 63 BHF solution (HF: 6 wt%, rain $: 3 〇 wt%) under 2 叱: W minutes of treatment, and the Hcm resistance was The aqueous solution of w hydrochloric acid was used under the conditions of _ and 3 small _ treatment conditions. The surface of the glass was observed by visual observation, and no turbidity, _, or cracking was observed on the surface of the glass = "." 'The surface of the glass was cloudy, wrinkled, Or the case of cracking Lu Xing made 1 X" 〇 施 即 即 即 即 即 N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N The strain point is greater than or equal to 637. (: In addition, the Young's modulus is two, 29 GP: /g · cm'. In addition, the high temperature viscosity of each of the above samples is Pa · s, the temperature is less than or equal to (5), so it is easy to melt, and the liquidus temperature Less than or equal to 1G7 (rc, liquid viscosity is greater than or equal to ig54 dpa · = opacity is excellent. Therefore, it can be judged that the glass of each sample of the example is a New Zealand good. Moreover, the image resistance of each sample is implemented, It is excellent in the resistance and the appearance evaluation is good. If the above-mentioned side 46 200800827 24402pif.doc is considered, it can be considered that each sample of the embodiment is suitable as a glass substrate for TFT-LCD. On the other hand, the glass sample A of the comparative example The value of (Ca〇+ Ba〇_MgO)/SiO: was 0.05, and the temperature at a high temperature viscosity of 1〇2.5 milk·s was higher at 1542° C. In addition, the glass sample B of the comparative example, (Ca The value of 〇+ Ba0-Mg0)/SiO 2 is G.43, and the strain point is 626 χ: and is lower. Further, the glass of the sample N〇17 of the example is melted in a test melting furnace, and a secret flow down-draw is performed, The glass substrate for a display having a substrate size of 9 Å and a thickness of 0.5 mm is used for the glass substrate. The warpage of the board is less than or equal to 〇.〇5%, the bending (WCA, (c) may be center line Waviness) is less than or equal to 0.1 μηη, and the surface roughness (four) is less than or equal to 50 Α (age: 9 (four), excellent from * surface product f, applicable It is used as a glass substrate for LCD. In addition, the temperature of the stretching roll, the speed of the cold_roll, the temperature distribution of the ageing, and the increase in the temperature of the forming roll are appropriately adjusted: 1⁄2, surface flow rate, and plate speed The surface quality of the glass substrate is adjusted by the number of rotations of the agitator, etc. In addition, the "warming" is to place the glass substrate on the optical plate and measure it using a clearance gauge described in JIS B-7524. "Bending" is a value obtained by using a stylus-type garment 1' to receive JIS B to G61. The W-wave center line is curved.) The measurement is used to make a pass (10) i ΪΓ , Ι TM , ^ 4 Φ f # ^ ^ ^ ^ ^ ^ ^ The interception at the time of measurement is 〇.8—, and the length of the 敎 surface in the direction perpendicular to the extraction direction of the glass kiwi. “Average surface roughness (Ry)” is utilized. Coffee D? - 94 "FpD glass substrate 47 200800827 24402pi£doc surface roughness The value of the measurement method is based on the method. [Industrial Applicability] Therefore, the alkali-free glass of the present invention is suitable for a flat panel display substrate such as an LCD or an EL display, a charge coupled device (CCD) or the like. A glass cover for an image sensor such as a close-type solid-state imaging device (CIS), and a substrate for a solar cell. [Simplified description of the drawing] No [Main component symbol description]

Claims (1)

200800827 24402pif.doc X. Application for Patent Park: 1. An alkali-free breaking, characterized in that: in terms of weight percentage (wt%), the glass composition of the alkali-free glass is The content of Si02 is 45 to 65%, Al2〇3 is 12 to 17%, B2〇3 is 7.5 to 15%, MgO is 〇~3%, Ca〇 is 5, 5 to 15%, and sT〇 is 〇~5. %, BaO is 5 to 15%, ZnO is 0 to 5%, MgG + CaO + SrO + BaO + ZnO is 15 to 23 %, zr 〇 2 is 0 to 5%, Ti 〇 2 is 〇 5% to 5%, P2 〇5 is 0 to 5 %; the alkali-free glass is substantially free of alkali metal oxide; the value of (CaO + Ba〇-Mg〇) / Si〇2 is 0.25 to 0.4 in terms of weight fraction; The alkali-free glass has an average coefficient of thermal expansion of 40 to 5 〇 x Ur7/°c in a temperature range of ~380 °C. 2. The non-glass of the invention described in the first paragraph of the patent application is in the range of weight fraction (MgO + CaO + SrO + BaO + ZnO) / Si〇2 is 0·3~〇·4 〇3 · As stated in the first or second item of the patent application scope! The glass was examined to be substantially free of As203, and the content of 813203 + such as 02 + €:1 was 〇 to 3% in terms of wt% in terms of the above oxide. 4. The alkali-free glass according to the first or second aspect of the patent application, which substantially does not contain As203 and Sb203, and the content of Sn02 is 0 to 1% in terms of wt% in terms of the above oxide. 5. If the alkali-free glass described in item 1 or 2 of the patent application scope has a liquidus temperature of 115 or less (TC and/or liquid phase viscosity is greater than or equal to 1〇5.4 49 200800827 24402pif.doc dPa * s 〇 6. If the application of the patent Fanyuan 2, μ, the glass composition described in the 2 items of the non-test glass '0 to G. 5wt%, and add, = ^ the above oxide conversion of wi% ^, The enthalpy of n〇2 up to Sn〇2 is 〇5 wt*% 7. As claimed in the patent No. 2, the liquid phase temperature of the glass is less than #2 plus 2 At the time, the alkali-free glass mentioned in the first or second item of the patent scope of the Boliday II application, Xingying, Xiao' is larger than the temple at 63〇.〇. 苴φ9”:!ΐ Patent scope item 1 Or the alkali-free glass mentioned in item 2, and the mid-south w degree is 10 dpa, and the temperature at s is less than or equal to 153 rc. Gans! Applies to find the non-test glass described in item 1 or item 2, Where the viscosity is GG, the temperature change point is set to D 2 (. When 〇, the relationship of Ti - T2 $ 880 ° C should be satisfied. 11 The application of the non-test glass described in item 1 or 2 of the patent application scope In the case where the temperature at the temperature of 1鬲4 dPa·s is set to Id) and the softening point is set to T4fC), τ satisfies the relationship of τ3 to □4$330. 〇. Or the non-test glass according to item 2, wherein the amount of erosion after immersing in a 10% HCl aqueous solution of 8 〇t for 24 hours is less than or equal to 5 μπι. 13 · As claimed in item i or item 2 Alkali-free glass, 50 200800827 &gt;: 44UVpii.d〇C The invaded amount after impregnation in a 130 buffered hydrofluoric acid solution at 20 ° C for 30 minutes is less than or equal to 2 μπι. The alkali-free glass according to item 1 or 2, wherein after immersing in a 10% HCl aqueous solution at 80 ° C for 3 hours, the surface was observed by visual observation, and no white turbidity or wrinkles were observed. The alkali-free glass according to item 1 or 2, wherein after immersing in a 63 buffered hydrofluoric acid solution at 20 ° C for 30 minutes, the surface was visually observed, and no white turbidity or wrinkles were observed. An alkali-free glass as described in claim 1 or 2, wherein the specific Young's modulus is greater than 27 GPa / (g · cm.) 17. An alkali-free glass substrate, which is composed of the non-test glass according to any one of claims 1 to 16. The alkali-free glass substrate according to Item 17, wherein the non-inspective glass is formed by down-draw molding. 19. The alkali-free glass substrate of claim 18, wherein the pull-down is formed into an overflow down-draw. 20. The alkali-free glass substrate according to any one of claims 17 to 19, wherein the alkali-free glass substrate is used for a display. 21. The non-inspective glass substrate of claim 20, wherein the display is a liquid crystal display. 22. The glass-free substrate of claim 21, wherein the display is an amorphous germanium TFT liquid crystal display. The alkali-free glass substrate according to claim 17, wherein the alkali-free glass substrate has a size of 32 Å or more. 52 200800827 24402pif.doc VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: