TW201221498A - Alkali free glass - Google Patents

Abstract

An alkali free glass is characterized in including 50 to 70% of SiO2, 9 to 15% of Al2O3, 11 to 20% of B2O3, 8 to 12% of CaO based on mol% as composition of the glass. A value of mole ratio of (MgO+CaO+SrO+BaO)/Al2O3 is 0.8 to 1.2, a density is 2.37 g/cm<SP>3</SP> or less, a temperature at 10<SP>2.5</SP>dPa.s is 1600 DEG C.

Description

201221498^ VI. Description of the Invention: [Technical Field] The present invention relates to an alkali-free glass, and more particularly to a glass for a flat panel display suitable for a liquid crystal display, an organic electroluminescence (EL) display, or the like. Image sense of substrate, chip size package (CSP), charge coupling device (CCD), equal-magnification solid-state imaging device (contact image sensor, CIS) There is no glass for the glass substrate of the detector. [Prior Art] In recent years, image sensors such as CSP have become smaller, thinner, and lighter. In the past, the sensor portion of the image sensor was protected by a resin package. However, in recent years, in order to further reduce the size and the like, a glass substrate is attached and protected by attaching it to a Si wafer. In addition, in order to reduce the size of the device, the glass substrate is required to be further thinned, and a glass substrate having a small thickness (for example, a glass substrate having a thickness of 0.5 mm or less) is being used. Further, in order to prevent the fact that alkali ions diffuse into the semiconductor material to be formed in the heat treatment step, an alkali-free glass substantially free of the metal oxide is usually used as the glass substrate (see Patent Document). [Prior Art Document] [Patent Document 1] [Patent Document 1] As described above, in the case of use of CSP or the like, the glass substrate is directly attached to the 3 201221498 -r WA /pit si wafer. However, if the coefficient of thermal expansion of the alkali-free glass does not match the thermal expansion coefficient of Si, warpage will occur on the glass substrate due to the difference in thermal expansion coefficient between the two. In particular, the smaller the thickness of the glass substrate, the more likely the warpage will occur on the glass substrate. In order to solve this problem, it is necessary to strictly match the coefficient of thermal expansion of the alkali-free glass and Si. However, the coefficient of thermal expansion of Si is very low, which is 32χ10·7Λ: ~34xl0'7/°c 'if it is matched with the coefficient of thermal expansion of Si. When the coefficient of thermal expansion of the alkali-free glass is lowered, it is difficult to produce a high-quality glass substrate. That is, in the case of the alkali-free glass, when the coefficient of thermal expansion is lowered, The viscosity of the glass is increased, which makes it difficult to improve the quality of the bubbles. As a result, it is difficult to obtain a high-quality glass substrate. Moreover, in an image sensor such as CSP, millions of Si wafers are stored in an equivalent amount of about 2 mm. The information of the vegan, the liquid crystal display, the organic EL display, etc. can not be compared with the other, very small defects may also become a problem. Further, the step of bonding the image sensor to the glass substrate is roughly the final step, Therefore, if the yield of the device is lowered due to defects of the glass substrate, the productivity of the device is remarkably lowered. Therefore, the alkali-free glass used for the purpose is particularly required (1) and has a coefficient of thermal expansion matching with Si, (1) (1) It is possible to form a thin sheet at a low cost, (4) lightweight, etc. [Explanation] In view of the circumstances, it is a technical object of the present invention to provide various characteristics required for use such as CSP. The non-existing glass, in particular, provides a non-inspective glass having a coefficient of thermal expansion that matches Si.

S 4 201221498 The present inventors have repeatedly conducted various experiments, and as a result, it has been found that the above-described technical properties can be solved by strictly limiting the content range of each component in the non-inspected glass and limiting the glass characteristics to a predetermined range. The subject matter of the present invention has been made. That is, the alkali-free glass of the present invention is characterized by containing 50% to 70% of Si〇2, 9% to 15% of αι2ο3, ιι〇/0 to 20% of β2〇 in terms of mol%. 3, 8% ~ 12% Ca 〇 as a glass composition, the molar ratio of (MgO + CaO + SrO + BaO) / Al2 〇 3 is 〇. 8 ~ 1.2 'density is 2.37 g / cm3 or less, l 〇 2.5 The temperature under dPa.s is below 1600 C. If the glass composition range is thus limited, the devitrification resistance is improved and it is easy to match the coefficient of thermal expansion of Si. Here, "alkali-free" means a case where the content of the alkali metal oxide (Li20, Na20, K20) in the glass composition is less than 100 (^卩111 (weight)."]^0 + €&0+81〇 + ;8&0" is the sum of MgO, CaO, SrO, and BaO. "Density" can be measured by the Archimedes method. "The temperature under 102_5dPa.s" can be pulled by platinum ball pulling up. Secondly, in the non-test glass of the present invention, it is preferable to contain 50% to 70% of SiO 2 , 9% to 15% of Al 2 〇 3, and 12% to 20% of B2 in terms of mol%. 〇3, 9%~12% CaO, 0%~0.03% Sb203 as a glass composition, the molar ratio (MgO + CaO + SrO + BaO) / Al2 〇 3 is 0.8 ~ 1.05, and the density is 2.35 g / Below cm3, the strain point is above 630 °C, the temperature at 102 5dPa.s is below 1540 °C, and the thermal expansion coefficient in the temperature range of 30 °C to 380 °C is 32xKT7/°C~4〇xlO-7/° C. Here, the "strain point" refers to a value measured according to the method of ASTM C336. "30 ° C to 380. (The coefficient of thermal expansion in the temperature range is: 201221498, i ^| measured by a dilatometer Jlt value. Third, this In the alkali-free glass, it is preferable to contain 55% to 70% of SiO 2 , 9.5% to 14% of Al 2 〇 3, 14% to 20% of B203, and 9.2% to 11% of CaO, in terms of mole %. 0%~0.03% of Sb203 is composed of glass. The molar ratio of (Mg0 + Ca0+Sr0 + Ba0)/Al203 is 0.83 to 1.0, the density is 2.35 g/cm3 or less, and the strain point is 635 °C or higher, 102 5dPa. The temperature under .s is 1530 ° C or lower, and the thermal expansion coefficient in the temperature range of 30 ° C to 380 ° C is 32 x 10 7 / ° C to 38 x 1 (T 7 / ° C. Fourth, in the alkali-free glass of the present invention, preferably It is composed of 55% to 70% of SiO2, 10.5% to 14% of A1203, 15% to 20% of B203, 9.5% to 10.5% of CaO, and 0% to 0.03% of Sb203 as a glass composition. The molar ratio (MgO + CaO + Sr0 + Ba0) / Al203 is 0.85 to 0.90, the density is 2.35 g/cm3 or less, and the strain point is 635. (: Above, the temperature at 102_5dPa.s is 1520X: below, 30 (: ~380. (The temperature expansion coefficient of the temperature range is 32xl 〇 -7 / ° C ~ 36xl (T7 / ° C. Fifth, in the alkali-free glass of the present invention, preferably containing 55% ~ 70% by mole % Si02, 10.8%~14% Al2〇3, 15.5%~20% B2〇3, 9.5%~1〇〇/0 CaO, 0%~0.03% Sb203 as glass composition, molar ratio (MgO + The values of CaO + SrO + BaO ) / Al2 〇 3 are 〇.87 to 0.90, the density is 2.35 g/cm3 or less, the strain point is 64 〇ΐ or more, and the temperature at 102 5dPa.s is 152 (rc below '3〇) The thermal expansion coefficient of the temperature range of t to 38 为 is 32 &lt; 10-7 /. (: 〜 36 &gt;&lt; 10·7 Λ: 6. Sixth, in the alkali-free glass of the present invention, liquid viscosity is preferred. It is 105 GdPa.s or more. Here, "liquid phase viscosity" is a value obtained by measuring the viscosity of glass at a liquidus temperature of 6 201221498 &quot;tUJiypif by a platinum ball pulling method. "The liquidus temperature can be passed by The glass powder of the standard sieve of 30 mesh (5 〇〇μηη) and remaining in the 〇 〇 〇 μ μ 加入 加入 铂 铂 铂 铂 铂 铂 铂 铂 铂 铂 铂 铂 铂 铂 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In addition The higher the liquidus viscosity, the lower the liquidus temperature, the more excellent the devitrification resistance or the formability. Seventh, the alkali-free glass of the present invention is preferably formed by an overflow down draw method. Here, the "overflow down-draw method" is also called a melting method, and the molten glass is allowed to overflow from both sides of the heat-resistant product, and the molten glass that has overflowed is merged at the lower end of the groove-shaped structure, and is downward. A method of forming into a plate shape by extension molding. Eighth, the alkali-free glass of the present invention is preferably a substrate for CSP. [Embodiment] The alkali-free glass according to the embodiment of the present invention contains sio2, A12o3, B2〇3, CaO, MgO, SrO, and Bao are used as a glass composition, and % of the content of each component below is a molar %.

The content of SiO 2 is 50% to 70%, preferably 55% to 70%, more preferably 60% to 70%, still more preferably 62% to 0% to 69%, most preferably 62% to 67%. If the content of Si〇2 is less than 5 〇〇/〇, the density is liable to rise. On the other hand, when the content of Si〇2 is more than 7% by weight, the meltability is likely to be lowered in addition to the high-temperature viscosity, and defects such as devitrification crystals (cristobalite) are likely to occur in the glass. The content of strontium is 9% to 15%. If the content of a1203 is less than 9%, it is difficult to improve the heat resistance, or the high-temperature viscosity is increased and the meltability is liable to be lowered. Moreover, 'Ai2〇3 has the function of increasing the Young's modulus and the Young's modulus (specific 7 201221498 . • W A 〆 Y_g, _dulus), and the modulus is low. The lower limit of his suit L. m ΐ preferably is more than 10.5%, especially preferably (10) ❶ / ❶ above, on the other hand, the content of right Al2 〇 3 is more than 15%

High, and thus resistance to devitrification is low. It is suitable for ^J = lower, preferably 13% or less, more preferably 12% or less, and particularly preferably ^^ b2〇3 functions as a refining agent, and is a component for reducing the viscosity of high temperature. The secret content is 11%~2〇%. If the content of 仏〇3 is less than 11%, the female is used as a melting system, which is high from *high temperature, and the bubble quality of glass is easily lowered. Moreover, the density is easy to rise. A suitable lower limit range of 曰b2〇 is 12% or more, preferably 13% or more, more preferably 3 14% or more, and still more preferably 15% or more, and particularly preferably 155% or more. On the other hand, if the content of B2〇3 is more than 2%, the strain point and Young's modulus are liable to lower. A suitable upper limit range of Βζ〇3 is 19% or less, preferably 18% or less, and particularly preferably 17% or less.

MgO + CaO + SrO + BaO is a component which lowers the liquidus temperature and causes crystal foreign matter to be less likely to be generated in the glass, and is a component which improves meltability or formability. The content of MgO + CaO + SrO + BaO is 5% to 12%, preferably 7% to 11%, more preferably 8% to 10.5%, still more preferably 8.5 〇 / 〇 to 10%, and particularly preferably 9 %~1〇〇/. . When the content of MgO + CaO + SrO + BaO is small, the function of the flux is not sufficiently exhibited and the meltability is lowered. The thermal expansion coefficient is too low, and it is difficult to match the thermal expansion coefficient of Si. On the other hand, when the content of MgO + CaO + SrO + BaO is large, the density increases at 8 201221498t. It is difficult to reduce the weight of the glass, and the Young's modulus is lowered, and the coefficient of thermal expansion is too high. The molar ratio of MgO + CaO + SrO + BaO / Al2 〇 3 is 〇·8 to 1.2. When the value of the molar ratio (MgO + CaO + SrO + BaO) / Α12〇3 is decreased, the devitrification resistance is liable to lower, and it is difficult to form by the overflow down-draw method. On the other hand, if the value of the molar ratio (MgO + CaO + SrO + BaO) / Α12〇3 is increased, the density or the coefficient of thermal expansion becomes too high. A suitable numerical range of the molar ratio + Ca0 + Sr0 + Ba0) / Al203 is 〇5, preferably 0.8 to 1.0, more preferably 0.83 to 1.0' and further preferably 0.85 to 0.95, and more preferably 〇85 ~0.90, especially good is 0.87~0.90.

MgO is a component which lowers the viscosity to the temperature and improves the rain and meltability without lowering the strain point, and is the most effective component for reducing the density in the alkaline earth metal oxide. The content of MgO is from 〇% to 8%, preferably from 0% to 6%, more preferably from 0% to 2%, and further preferably from 〇% to 〇/〇, and more preferably from 〇% to 〇5%. , especially preferably 0%~0.1%. However, if the content of MgO is too large, the liquidus temperature rises, and the devitrification resistance is liable to lower. Moreover, the glass is easily separated, and the transparency is easily lowered. If the value of the mass 1 is more than 〇 6 or more than the value of MgO/B2 〇 3, the glass is likely to be a phase. Therefore, the value of the mass ratio Mg 〇 / B2 〇 3 is 〇 $ or less, preferably 0.3 or less, more preferably 〇.1 or less, still more preferably less than 〇 〇 8, and particularly preferably less than 0.05. C aO is a component which lowers the temperature and viscosity of the crucible and remarkably improves the smelting property without lowering the strain point, and is a component having a high effect of suppressing devitrification in the glass composition system of the present embodiment. Further, when the content ratio of CaO is relatively increased in the alkaline earth metal oxide 9 201221498, the density is liable to lower. A suitable lower limit range of CaO is 8% or more, preferably 8.5% or more, more preferably 9% or more and further preferably 9.2% or more, further preferably 9.4% or more, and particularly preferably 9.5% or more. On the other hand, if the content of CaO is too large, the coefficient of thermal expansion or density may become too high, or the balance of the composition of the glass composition may be impaired, and the devitrification resistance may be easily lowered. A suitable upper limit of CaO is 12% or less, preferably 11% or less, more preferably 10.5% or less, and particularly preferably 1% by weight.

SrO is a component which lowers the viscosity at high temperature and improves the meltability without lowering the strain point. However, if the content of SrO is increased, the density or the coefficient of thermal expansion is liable to rise. Further, when the content of SrO is increased, the content of CaO or MgO has to be relatively lowered in order to match the coefficient of thermal expansion of Si, and as a result, the resistance to devitrification is lowered, or the viscosity at high temperature is likely to increase. The content of Sr〇 is 〇°/°~2%, preferably 〇%~1.5%' more preferably 〇%~1%, and even more preferably 0%~0.5%, especially preferably 〇%~〇.1 〇/0.

BaO is a component which lowers the viscosity to the temperature and improves the meltability without lowering the strain point. However, if the content of BaO is increased, the density or the coefficient of thermal expansion is liable to increase. Further, when the content of BaO is increased, the content of CaO or MgO has to be relatively lowered in order to match the coefficient of thermal expansion of Si. As a result, the devitrification resistance is lowered, or the high-temperature viscosity is likely to increase. The content of Ba〇 is 0% to 2%, preferably 〇%~ι.5%, more preferably 〇%~1%, and even more preferably 0%~0.5% 'More preferably 〇%~ less than 〇. I〇/〇. In addition to the above components, for example, the following components may be added to the glass composition. In addition, the content of the other components other than the above-mentioned components is preferably 25% or less, and particularly preferably 15% or less, from the viewpoint of the effect of the present embodiment.

Sn〇2 is a forming tool which exhibits a good clearing action in a high temperature region, and is a component which lowers the viscosity of the souther temperature. The content of gn〇2 is 〇%~1%, and the ruthenium is preferably 0.001%~1%, more preferably 〇〇1%~〇5%, and even more preferably 0.05%~〇.3〇/0 'More For 〇, 1% ~ 〇 3%. When the content of Sn 〇 2 is more than 1% ', the devitrified crystal of Sn 〇 2 is easily precipitated in the glass. Further, when the content of Sn 〇 2 is less than 0.001%, it is difficult to enjoy the above effects.

ZnO is a component which improves the meltability. When the ZnO is contained in a large amount in the glass composition, the glass is devitrified easily, and the strain point is lowered, and the density is also likely to increase. Thus, the content of ZnO is from 〇% to 5%, preferably from 〇% to 3%, more preferably from 0% to 0.5%, still more preferably from 〇% to 0.3%, and more preferably substantially no ZnO. Here, "the substance does not contain Zn 〇" means that the content of ZnO in the glass composition is 0.1% or less.

Zr〇2 is a component that increases the Young's modulus. The content of Zr〇2 is 〇% to 5%, preferably 〇% to 3%, more preferably 〇% to 5%, and particularly preferably 〇% to 0.2%, and ideally, Zr〇2 is not substantially contained. . When the content of Zr〇2 is too large, the liquidus temperature rises, and the devitrified crystal of zirconium is easily precipitated. Further, when the content of Zr 〇 2 is too large, the count value of the α ray is likely to increase, and thus it is difficult to apply it to a device such as a CSP. Here, "substantially does not contain Zr〇2" means that the content of Zr〇2 in the glass composition is 〇〇1% or less. Further, when the necessity of increasing the Young's modulus is high, the content of Zr〇2 may be 0.01% or more. Τι〇2 is a component that lowers the viscosity of the high temperature and improves the meltability, and is a component of the solarization of 201221498 *TV/*/ 1 ^pif, but if the composition of the glass contains more of the Ti〇2, Then the glass is colored, and the transmittance is easily lowered. Therefore, the content of Ti of Ti 2 is 〇% to 5% 〜 is preferably 0% to 3%, more preferably 〇% to 1% Å is preferably 〇% to 0.02%. P2〇5 is a component for improving the devitrification resistance. However, if the ruthenium 5' is contained in a large amount in the glass composition, the water resistance is remarkably lowered in addition to the phase separation and whitening in the glass. Therefore, the content of P2〇5 is 〇% to 5%, preferably 〇% to 1% Å is more preferably 0% to 0.5%, and particularly preferably 〇% to 〇1%. Y2〇3 has an effect of increasing the strain point, the Young's modulus, and the like. However, if the content of γζ〇3 is too large, the density tends to increase. Therefore, the content of υ2〇3 is preferably 5% or less. Nb2〇5 has an effect of increasing the strain point, Young's modulus, and the like. However, if the content of the component of Νΐ2〇5 is too large, the density tends to increase. Therefore, the content of the sputum 5 is preferably 5% or less. U2〇3 has an effect of improving strain, two-dimensional modulus, and the like. However, if the content of strontium is too high, the glutinous grain tends to rise. Therefore, the content of La2〇3 is preferably 5〇/〇 or less. As described above, Sn 2 is suitable as a clearing agent. However, as long as the glass characteristics are not impaired, Ce〇2, S〇3, c, metal powder (for example, ai, Si, etc.) may be added to 5°/〇 as a clearing agent. Clearing agent.

As2〇3 and Sb2〇3 also function effectively as a clearing agent. The two forms of the form are included in the whole row. The content of some components is considered to be less than the content of the components. (4) Jia is less than G.G5%. Further, F, α, etc. are more effective in lowering the temperature and promoting the clarification effect, and as a result, the cost can be reduced and the life of the furnace can be extended. Autumn, if F

S 12 201221498 W A /^/lt is too large. In the case of use such as CSP, the wiring pattern of the metal formed on the glass substrate may be corroded. Therefore, the content of F and C1 is respectively 1% or less, preferably 0.5% or less, more preferably less than 〇1%, and preferably: 0.05% or less, and further preferably 〇.〇3% or less. Jia Wei is less than 1%. In the alkali-free glass of the present embodiment, the density is 2.37 g/cm3 or less, preferably 2.35 g/cm3 or less. When the density is increased, it is difficult to make the glass lightweight, and in the case of a flat plate shape, the glass is easily deflected by its own weight. The bubble quality of the glass not only affects the yield of the glass, but also affects the yield of the device. Therefore, it is important to lower the viscosity at high temperatures to improve the bubble quality of the glass. In the non-glass of the present embodiment, the temperature at 1025 dPa's is 1600 ° C or lower, preferably i540 ° C or lower, more preferably 1530 ° C or lower, and particularly preferably 1520 ° C or lower. If i 〇 25dpa.s; m degrees south of 1600 C ', it becomes difficult to melt at a low temperature, and the bubble quality of the glass is liable to be lowered. Therefore, not only the manufacturing cost of the glass is likely to increase, but also the manufacturing cost of the device is likely to increase. In the alkali-free glass of the present embodiment, the strain point is 630. (The above is preferably 635 ° C or higher, and more preferably 640 ° C or higher. In the case of use such as CSP, the glass is adhered to each other by a resin or the like. In this case, if the strain point is lower than 630 C ' When the glass is adhered to each other, there is a problem that the quality of the glass is lowered. Further, when the strain point is lower than 630 ° C, in the case of using a glass substrate for an organic EL, a poly silicon thin film is used. In the manufacturing process of the transistor 'p-SiTFT), the glass is easily thermally shrunk. In the alkali-free glass of the present embodiment, the temperature range of 30 ° C to 38 〇 t is 13 201221498 . . . — _ ρ, ΐ ΐ thermal expansion coefficient is 32×10_7/° C~4〇xl (T7/°C, preferably 32χ10·7Λ: ~38x1 (T7/°C, more preferably 32x10_7/°C~36x10_7/°C, especially good for 33xlO_7/°C~35xl〇- 7/° C. When the thermal expansion coefficient is outside the above range, the amount of warpage of the glass substrate tends to increase when the glass substrate is bonded to the Si wafer. Further, the smaller the thickness of the glass substrate, the coefficient of thermal expansion The amount of curvature of the glass substrate caused by the difference is larger. Therefore, when the thickness of the glass substrate is small, (For example, when the thickness of the glass substrate is 0.2 mm or less), it is important to limit the thermal expansion coefficient to the above range. In the alkali-free glass of the present embodiment, the liquidus temperature is preferably 18 or less, preferably It is 1150 C or less, more preferably 113 〇 ° C or less, further preferably 1110 ° C or less, and still more preferably 1 〇 9 〇. (: Hereinafter, it is preferably 1 〇 7 〇 ° C. Thus, glass Since the devitrified crystal is less likely to be formed, it is easy to form by the overflow down-draw method. As a result, the glass production cost can be reduced and the surface quality of the glass can be improved. In the alkali-free glass of the present embodiment, the liquidus viscosity is 1〇5. 〇dPa s or more, preferably 105 2dPa.s or more, more preferably 1 〇 5.3dPa.s or more, further preferably 1055dPa.s or more, and particularly preferably 1 〇 5.7dPa.s or more. Since it is difficult to generate devitrified crystals, it is easy to form by an overflow down-draw method or the like, and the heart-making can reduce the manufacturing cost of the lang, and the glass-free glass of the present embodiment can be produced by: After the glass material is put into the continuous surface melting furnace, ^玻璃^料崎加热(四), and the bribe (4) melted glass clear, and then supplied to the forming device to form a flat plate shape, etc. 201221498 • * ✓pit The alkali-free glass of the present embodiment is preferably formed by an overflow down-draw method. The overflow-drawing method "the surface to be the surface of the lang is not in contact with the grooved refractory, but is formed in a state of a free surface. Therefore, it is possible to inexpensively manufacture a flat-shaped glass which is not ground and has a good surface quality. . Further, the structure or material of the groove-like structure used in the overflow down-draw method is not particularly limited as long as the desired size or surface precision can be achieved. Further, the method of applying the force at the time of extending the molding to the lower side is not particularly limited. For example, it is possible to extend a heat-resistant roller having a sufficiently large width in a state of being in contact with the glass; or a pair of heat-resistant rollers can be extended only in contact with the vicinity of the end surface of the glass. Methods. In the alkali-free glass of the present embodiment, in addition to the overflow down-draw method, various molding methods are employed. For example, a down-draw method (a flow-down method, etc.), a floating method, a roll method, or the like can be employed. The alkali-free glass of the present embodiment preferably has a flat plate shape. In this way, it can be applied to a glass substrate for a flat panel display such as a liquid crystal display or an organic EL display, or a glass substrate for an image sensor such as a CSP, a CCD or a CIS. Further, in the case where the alkali-free glass of the present embodiment has a flat plate shape, the thickness thereof is 0.6 mm or less, preferably 0.5 mm or less, more preferably 0.3 mm or less, still more preferably 0.2111111 or less, and particularly preferably 01111111. the following. The smaller the plate thickness, the lighter the glass, and as a result, the device is also lighter in weight. Further, since the alkali-free glass of the present embodiment has a high liquid phase viscosity, it has a property of being easily formed by an overflow down-draw method. When it is formed by the overflow down-draw method, it is possible to inexpensively produce a flat-plate-shaped glass which is not polished and has a good surface quality. 15 201221498 . • ^ A 〆 1·^ i 丄 [Example 1] Hereinafter, an example of the present invention will be described. However, the following examples are merely illustrative. The invention is not limited by the following examples. Tables 1 to 3 show examples of the present invention (samples No. 1 to No. 13). [Table 1]

1 r Example No.l No.2 No.3 No.4 Glass composition (mol%) Si02 64.8 64.7 64.6 63.6 AI2O3 10.0 9.6 9.3 11.0 B2O3 15.5 16.0 16.4 15.6 CaO 9.7 9.7 9.7 9.8 Sn02 0.1 0.1 0.1 0.1 (Mg+Ca +Sr+Ba)/Al 0.97 1.02 1.04 0.89 Density [g/cnv3] 2.33 2.33 2.32 2.34 a[xl0'7°C] 34 34 34 34 Ps[°C] 637 634 630 642 Ta[°C] 692 689 684 698 s s s s s s s s s Logi〇TiTL[dPa_s] 6.0 6.0 6.0 5.3 Young's modulus [GPa] 66 66 65 67 16 201221498t [Table 2] Example No.5 No.6 No.7 No.8 No.9 Glass composition (mol%) Si02 63.9 64.4 64.4 65.2 64.2 AI2O3 10.6 10.6 11.0 11.0 11.4 B2O3 15.6 15.1 14.7 13.7 14.3 CaO 9.7 9.7 9.7 9.4 9.4 SrO 0.1 0.1 - 0.6 0.6 BaO - - 0.1 - - Sn02 0.1 0.1 0.1 0.1 0.1 (Mg+Ca+Sr+Ba) /Al 0.93 0.93 0.90 0.91 0.89 Density [g/cm3] 2.34 2.34 2.35 2.36 2.36 a[xlO'7°C] 34 34 34 34 34 PsfC] 641 645 650 656 653 Ta[°C] 697 702 707 713 710 Ts[ °C] 936 941 946 952 94 8 104dPa-s[°C] 1261 1268 1271 1281 1268 10JdPa-s[°C] 1424 1432 1434 1444 1429 102:,dPa-s[〇C] 1527 1535 1537 1545 1528 TL[°C] Not determined not determined Measurement not measured Log10TiTL [dPa_s] Not measured Not measured Not measured Not measured Not measured Young's modulus [GPa] 67 67 68 68 68 17 201221498, WA «/pit [Table 3]

No. 10 ~ 62.2 Tl.4 ~ Τβ.2 ~ 9.5 -0.6

0.1 ~ a89 2.36 35 ^37 ^92 ^30 1239 1^97 1496 定 67

Si02

Al2〇3 glass composition (mol%) B2O3

CaO

SrO

BaO

Sn〇2 (MgH-Ca+SH-Ba)/Al density [g^cm3] a[xlO'7/°C]

Ps[°C]

Ta[°C] Ts[^T—104dPa, s[°C丁103dPa-s[°cT 102-5dPa-s[ecl ~TL[°C]~

Logi〇xiTL[dPa_s] Young's modulus [GPa] Samples NcU to No. 13 were prepared as follows. First, a glass raw material having a glass composition which has been blended into a table is added to a platinum crucible, and after melting at 1600 &lt; t for 24 hours, the molten glass is discharged onto a carbon plate to form a flat plate. Then, for each of the obtained samples, the density, the coefficient of thermal expansion α, the strain point Ps, the slow cooling point Ta, the softening point Ts, the temperature at 104 dPa.s, the temperature at 103 dPa.s, and the temperature at 102 5 dPa.s were evaluated. Temperature, liquidus temperature TL, liquid viscosity, logu^TL, Young's modulus. Density is a value measured by the well-known Archimedes method. The coefficient of thermal expansion α is a value measured by a dilatometer, and is an average value of a temperature range of 3 〇 ° c to 380 ° C. The strain point Ps, the slow cooling point Ta, and the softening point Ts are values measured according to the method of ASTM C336 18 &amp; 201221498 vr - A 。. The temperature at 1040dPa.s, i〇30 (the temperature at iPa.s, and the temperature at i〇25dpa.s are the values measured by the platinum ball pulling method. The liquid phase 丨jbl degree TL疋 will pass the standard self-帛The glass powder remaining in 50 mesh (300 μm) of 30 mesh (5 μm) was placed in a Ming boat and kept in a temperature gradient furnace for 24 hours, and then the temperature at which the crystal was precipitated was measured. The viscosity is 〇gi〇r (TL is a value obtained by measuring the viscosity of the glass at the liquidus temperature TL by the Ming ball pulling method. The value of the modulus is measured by the resonance method. Further, the value of the present invention is measured by the resonance method. In the non-test glass, the Young's modulus is preferably 64 GPa or more. The larger the Young's modulus, the larger the Young's modulus (Young's modulus/density), so in the case of a flat shape, the glass It is difficult to flex due to its own weight. According to Tables 1 to 3, it is known that the sample composition No.1 to Νο·13 limits the glass composition to a predetermined range, so the density is 2.37 g/cm3 or less, and the strain point is 630 °C. Above, the temperature at 1025 dPa.s is 1600 ° C or less. In addition, samples No. 1 to No. 13 do not contain aS2〇3, sb203 in the glass composition. [Example 2] The samples No. 1 to No. 4 described in Table 1 were melted in a test melting furnace, and then formed into a flat plate shape having a thickness of 0 1 mm by an overflow down-draw method. At the time, the glass plate is adjusted by appropriately adjusting the speed of the stretching roll, the speed of the cooling roll, the temperature distribution of the heating device, the temperature of the molten glass, the flow rate of the molten glass, the pulling speed of the plate, the rotation speed of the agitator, and the like. Table

After the surface quality of the glass obtained by II II201221498 was measured, the surface was: /❶ below, and the bending (WCA) a15_ or less (cutoff • 0.8mm' fi: 8inm)' surface roughness (Ry) was 2〇a The following (cut λο. 9 μηι) ^ In addition, "light curve" is a value measured by placing a glass plate on an optical disk using a clearance gauge described in Jig Β-7524. "Bending" is a value obtained by measuring the WCA (filter center line bending) described in JIS B-0610 using a stylus type surface shape measuring device, and is based on the measurement of the surface curvature of the FPD glass substrate according to SEMISTDD15-1296. The value determined by the method of the method. The "average surface roughness (Ry)" is a value measured by a method based on SEMID 7-94 "Method for measuring the surface roughness of an FPD glass substrate". [Simple description of the diagram] [Explanation of main component symbols] Ο 20

Claims (1)

201221498 TV/*; 1 叩if VII. Patent application scope: 1. An alkali-free glass, characterized by: 50%~70% of Si〇2, 9%~15% of Al2 by mole/❶ 〇3, 11%~20% of B2〇3, 8%~12% of CaO is used as the glass composition, and the molar ratio of (MgO + CaO+SrO + BaO) / Al2〇3 is 〇.8 ～1.2, density It is 2.37 g/cm3 or less, and the temperature under l〇25dPa.s is 1600 ° C or less. 2. A non-existing glass, characterized by: 50% to 70% of SiO 2 , 9% to 15% of Al 2 〇 3, 12% to 20% of B 203, 9% to 12% by mole % CaO, 0%~0.03% of Sb203 is composed of glass, the molar ratio (MgO + CaO + SrO + BaO) / Al2 〇 3 is 0.8~1.05, the density is 2.35 g/cm3 or less, and the strain point is 630 °C. Above, the temperature at 1025dPa_s is 1540 ° C or less, 30. (: ~38 (the coefficient of thermal expansion of the temperature range of TC is 32χ10_7Α:~40&gt;&lt;10_7/. (: 3. 3. An alkali-free glass, characterized by: 55% to 70% by mole %) Si02, 9.5 ° /. ~ 14% Alieva% ~ 20% B203, 9.2% ~ 11% CaO, 0% ~ 0.03% Sb2 〇 3 as a glass composition, Mo Er ratio (MgO + CaO + SrO + BaO The value of /Al2〇3 is 0.83~io, the degree of pushing is 2.35 g/cm or less, and the temperature at the strain point of the horse L milk 丄1025dPa's is below i53〇°c, 30. (: 380°C temperature range The coefficient of thermal expansion is 32&gt;&lt;10_7/. (:~38xl〇-7/°C. 21 201221498 4. An alkali-free glass characterized by containing 55% to 70% of SiO 2 and 10.5% by mole % ~14% Al2〇3, 15%~20% B2〇3, 9.5%~10.5% CaO, 0%~0.03% Sb203 as glass composition, Mo Er ratio (MgO + CaO+SrO + BaO) / The value of A1203 is 0.85~0.90, the density is 2.35 g/cm3 or less, the strain point is 635 °C or higher, the temperature under 102 5dPa*s is 1520 °C or lower, and the temperature range is 30 °C to 380 °C. The coefficient of thermal expansion is 32xl (T7/°C~36xlO_7/°C. 5. Non-test glass, characterized by: 55% to 70% SiO2, 10.8% to 14% octa 1203, 15.5 ° / 〇 ~ 20% of 6203, 9.5% ~ 10% of €&amp; 0, 0%~0.03% of Sb2〇3 as a glass composition, the molar ratio (Mg〇+ CaO+SrO + BaO) / A1203 is 0.87~0.90, the density is 2.35 g/cm3 or less, and the strain point is 640°. Above C, the temperature at 1025dPa.s is below 15203⁄4, 30. (: The thermal expansion coefficient in the temperature range of ~380 °C is 32xl〇-7/°c~36xlCT7/°C. 6. If the scope of application is the third item The non-test glass according to any one of the items 5 to 5, wherein the liquid phase viscosity is l〇5. QdPa.s or more. 7. The method according to any one of claims 1 to 0. An alkali glass which is formed by an overflow down-draw method. 8. The optometry glass according to any one of the items 1 to 7 of the patent application, which is used for a substrate of a wafer size dragon. 22 6, 201221498 -r\j^ L IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0 201221498 'The 100th Chinese Patent No. 18 of the 10013 pocket is not underlined. 7. The scope of application: I. A non-test glass, characterized by: 50%~70% of SiO2, 9%~15 % Al2〇3, 11〇/0~2〇〇/0 b203, 8%~12% CaO as glass composition 'MerO ratio (MgO + CaO + SrO + BaO) / Al2〇3 has a value of 0.8 ~1.2, the density is 2.37 g/cm3 or less, and the temperature at 1025 dPa.s is 1600 °C or less. Ο Λ 2. A kind of non-test glass, characterized by: / containing 50% ~ 70% of SiO 2 , 9% ~ 15% of Al2 〇 3, 12% ~ 20% of B2 〇 3, 9 %~12% CaO, 0%~0.03% of Sb2〇3 as a glass composition, the molar ratio (MgO + CaO + SrO + BaO) / Al2〇3 is 0.8~1.05, and the density is 2.35 g/cm3 or less. The strain point is above 630 ° C, 1025 dPa, and the temperature under s is 1540 ° C or less, 30 ° C ~ 380. (The temperature expansion coefficient of the temperature range is 32xl (T7/°C~4〇xlO-7/°C. Ο 3.) An alkali-free glass characterized by: 55% to 70% by mole % Si02, 9.5%~14% Al2〇3, 14%~20% B203, 9.2%~11% CaO, 0%~0.03% Sb2〇3 as glass composition, molar ratio (MgO + CaO + SrO + BaO) / AI2O3 The value is 0.83~1.0, the density is 2.35 g/cm3 or less, the strain point is 635 °C or higher, and the temperature at 102 5dPa_s is 1530. (: The following, 30〇C~38 (TC temperature range) The coefficient of thermal expansion is 32xl (T7/°c~38xlO-7/°C. 21 201221498 wcuypirl is the patent scope of No. 100139618. There is no slash correction. This revision period: 100 years February 9th, the pure sign is: Al2 〇 3, 1, 5% Γ ^ move ~ view of Qing, _ ~ 14% of 0._ Sb2 〇 3 for: B2 〇 3, 9.5% ~ 1 〇. 5% Ca 〇, 〇% ~ + B :) The value of /Al2〇3 is the ear ratio (Mg〇+ Ca〇+ Sr〇1 n2.5^degree^2·35 g/cm3 or less, the strain point is 635°C or more, and the degree is 152〇°c or less. , 30 ° c ~ 380. (: The temperature secret coefficient of the temperature range is corrected ~ 36xl 〇 -%. 7 ' species. Alkali-free slope 螭, its It is characterized by: \ with Mohr / 〇 δ 10 containing 55% ~ 70% of SiO 2 , 10.8% ~ 14% of A12 〇 3 15.5 / 〇 ~ 20 〇 / 〇 B2O3, 9.5% ~ 10% of CaO, 0% ~ 0.03 /. Sb2 〇 3 as a broken glass composition, Mo Erbi + + + BaO) / A12Q3 value is Q 87 ~ said, density is 2.35 g / cm3 or less, strain point is 64 〇〇 c or more, 10 dPa 'S The temperature under the temperature is 1520 ° C or less, and the thermal expansion coefficient in the temperature range of 30 ° C to 380 ° C is 32 xi 〇 -7 / ° c ~ 36 χΐ〇 _ 7 / 1. 6 · As claimed in the first item to The alkali-free glass according to any one of the preceding claims, wherein the liquid phase viscosity is l〇5〇dPa.s or more. 7. The method according to any one of claims 1 to 5 The glass is formed by an overflow down-draw method. The alkali-free glass of any one of the above-mentioned items of the invention, which is used for a wafer-sized package.