KR20130041221A - Non-alkali glass - Google Patents

Abstract

The alkali-free glass of the present invention is a glass composition, SiO ₂ 50 ~ 70% by _{mol%, Al 2 O 3 9 ~} 15%, B 2 O 3 11 ~ 20%, containing CaO 8 ~ 12%, and the molar ratio ( The value of MgO + CaO + SrO + BaO) / Al ₂ O ₃ is 0.8 to 1.2, and the density is 2.37 g / cm ³ or less and the temperature at 10 ^2.5 dPa · s is 1600 ° C. or less.

Description

Alkali free glass {NON-ALKALI GLASS}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to alkali-free glass, and in particular, glass substrates for flat displays such as liquid crystal monitors and organic EL displays, chip size packages (CSPs), charge coupled devices (CCDs), equally close proximity solid state imaging devices (CIS), and the like. It is related with the alkali free glass suitable for the glass substrate for image sensors.

In recent years, image sensors such as CSP have become smaller, thinner, and lighter. Conventionally, although these sensor parts were protected by the package of resin, in order to advance further miniaturization etc., the method of pasting and protecting a glass substrate on a Si chip is employ | adopted in recent years.

In addition, in order to reduce the size and the like of this glass substrate, further thinning is required, and a glass substrate having a small plate thickness (for example, a glass substrate having a plate thickness of 0.5 mm or less) is employed.

In order to prevent the diffusion of alkali ions into the film-formed semiconductor material in the heat treatment step, an alkali free glass that is substantially free of an alkali metal oxide is usually used as the glass substrate (see Patent Document 1).

(Prior art document)

(Patent Document 1) Japanese Unexamined Patent Publication No. 2006-344927

As described above, for applications such as CSP, the glass substrate and the Si chip are directly attached. However, when the thermal expansion coefficients of alkali free glass and Si do not match, curvature will generate | occur | produce in a glass substrate by the thermal expansion coefficient difference of both. In particular, the smaller the plate thickness of the glass substrate, the more likely the warpage occurs in the glass substrate.

In order to solve this problem, it is necessary to precisely match the thermal expansion coefficient of alkali free glass and Si. However, the thermal expansion coefficient of Si is very low at ^{32-34x10 <-7>} / degreeC, and when the thermal expansion coefficient of an alkali free glass is reduced so that it may match with Si thermal expansion coefficient, it will become difficult to produce a high quality glass substrate. That is, in alkali free glass, when the coefficient of thermal expansion is lowered, the viscosity of the glass is increased, so that it is difficult to improve the bubble quality, and as a result, it is difficult to obtain a high quality glass substrate.

In addition, since an image sensor such as a CSP contains information about millions of pixels in a Si chip of about 2 mm, it may be a problem that a very small defect is not comparable with pixels such as a liquid crystal display or an organic EL display. Can be. In addition, since the process of bonding an image sensor and a glass substrate is a final process, when the yield of a device will fall by the fault of a glass substrate, productivity of a device will fall remarkably.

Therefore, the alkali free glass used for this use is especially (1) having a thermal expansion coefficient matched with Si, (2) excellent bubble quality, (3) being capable of forming a thin sheet with low cost, (4 ) Light weight and the like are required.

In view of the above circumstances, it is a technical object of the present invention to provide an alkali-free glass capable of satisfying various properties required for applications such as CSP, particularly an alkali-free glass having a thermal expansion coefficient matched with Si.

As a result of repeating various experiments, the present inventors have found that the above technical problem can be solved by strictly regulating the content range of each component in the alkali-free glass and regulating the glass properties in a predetermined range. It is proposed as the present invention. That is, the alkali-free glass of the present invention containing a glass _{composition, SiO 2 50 ~ 70%,} Al 2 O 3 9 ~ 15%, B 2 O 3 11 ~ 20%, CaO 8 ~ 12% in mol%, The molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O _{3 has} a value of 0.8 to 1.2, a density of 2.37 g / cm ³ or less and a temperature at 10 ^2.5 dPa · s, characterized by being 1600 ° C. or less. By regulating such a glass composition range, devitrification resistance improves and it becomes easy to match with the thermal expansion coefficient of Si. Here, "alkali-free" is the content of alkali metal oxides _{(Li 2 O, Na 2 O} , K 2 O) in the glass composition shows the case of less than 1000ppm (parts by mass). "MgO + CaO + SrO + BaO" is the total amount of MgO, CaO, SrO and BaO. "Density" can be measured by the Archimedes method. "The temperature in 10 ^2.5 dPa * s" can be measured by a platinum ball pulling-up method.

Secondly, the alkali-free glass of the present invention is a glass composition, in mol%, 50 to 70% SiO ₂ , 9 to 15% Al ₂ O ₃ , 12 to 20% B ₂ O ₃ , CaO 9 to 12%, Sb. ₂ 0 ₃ 0-0.03%, molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ value is 0.8 ~ 1.05, density is 2.35 g / cm ³ or less, strain point 630 ℃ or more, 10 ^2.5 It is preferable that the thermal expansion coefficient in the temperature range of 1540 degreeC or less and 30-380 degreeC in dPa * s is 32-40 * 10 <^-7> / ^degreeC . Here, a "strain point" shows the value measured based on the method of ASTM C336. "The thermal expansion coefficient in the temperature range of 30-380 degreeC" shows the value measured with the dilatometer.

Thirdly, the alkali-free glass of the present invention is a glass composition, in mol%, 55 to 70% SiO ₂ , 9.5 to 14% Al ₂ O ₃ , 14 to 20% B ₂ O ₃ , 9.2 to 11% CaO, and Sb. ₂ O ₃ 0 to 0.03%, the molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ value is 0.83 ~ 1.0, the density is 2.35 g / cm ³ or less, strain point 635 ℃ or more, 10 It is preferable that the thermal expansion coefficient in the temperature range of 1530 degreeC or less and 30-380 degreeC is 32-38x10 <^-7> / degreeC in the temperature in ^2.5 dPa * s.

Fourthly, the alkali free glass of the present invention is a glass composition, in mol%, 55 to 70% SiO ₂ , 10.5 to 14% Al ₂ O ₃ , 15 to 20% B ₂ O ₃ , 9.5 to 10.5% CaO, and Sb. ₂ O ₃ containing 0 to 0.03%, and the molar ratio of (MgO + CaO + SrO + BaO ) / Al 2 O ₃ value of a is 0.85 ~ 0.90, the density was 2.35g / cm ³ or less, strain point over 635 ℃, 10 It is preferable that the thermal expansion coefficient in the temperature range of 1520 degreeC or less and 30-380 degreeC is 32-36x10 <^-7> / degreeC in the temperature in ^2.5 dPa * s.

Fifthly, the alkali-free glass of the present invention is a glass composition, in mol%, 55 to 70% SiO ₂ , 10.8 to 14% Al ₂ O ₃ , 15.5 to 20% B ₂ O ₃ , 9.5 to 10% CaO, and Sb. ₂ O ₃ 0 to 0.03%, the molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ value is 0.87 ~ 0.90, the density is 2.35 g / cm ³ or less, strain point 640 ℃ or more, 10 It is preferable that the thermal expansion coefficient in the temperature range of 1520 degreeC or less and 30-380 degreeC is 32-36x10 <^-7> / degreeC in the temperature in ^2.5 dPa * s.

Sixthly, it is preferable that the alkali free glass of this invention is 10 ^5.0 dPa * s or more in liquid phase viscosity. Here, "liquid viscosity" is the value which measured the viscosity of the glass in liquidus temperature by the platinum ball pulling-up method. "Liquid temperature" is passed through a standard 30 mesh (500㎛), put the glass powder remaining in the 50 mesh (300㎛) in a platinum boat, and maintained for 24 hours in a temperature gradient path, by measuring the temperature of crystal precipitation It is possible to calculate. In addition, the higher the liquid phase viscosity and the lower the liquidus temperature, the better the devitrification resistance and moldability.

Seventh, it is preferable that the alkali free glass of this invention is shape | molded by the overflow down-draw method. Here, the "overflow down draw method" is also called the fusion method, and the molten glass is overflowed from both sides of the heat-resistant grooved cylindrical structure and stretched downward while joining the overflowed molten glass to the lower end of the grooved cylindrical structure. It is a method of forming into a plate shape.

Eighth, it is preferable to use the alkali free glass of this invention for the board | substrate of CSP.

The alkali-free glass according to the embodiment of the present invention is a glass composition, contains _{SiO 2, Al 2 O 3,} B 2 O 3, CaO, MgO, SrO, BaO. In addition, in description of content of each following component,% display represents mol%.

The content of SiO ₂ is 50 to 70%, preferably 55 to 70%, more preferably 60 to 70%, still more preferably 62 to 69%, most preferably 62 to 67%. When the content of SiO ₂ is less than 50%, the density tends to increase. On the other hand, when the content of SiO ₂ is much higher than the high temperature viscosity of 70%, in addition to which is likely to decrease the melting property, it is liable to have defects such as devitrification crystal (cristobalite) occurs in the glass.

The content of Al ₂ O ₃ is 9 to 15%. When the content of Al ₂ O ₃ is less than 9%, it becomes difficult to increase the heat resistance, the high temperature viscosity becomes high, and the meltability tends to decrease. In addition, Al ₂ O ₃ has When a content of the Young's modulus, but the ability to increase the Young's modulus ratio, Al ₂ O ₃ is less than 9%, the Young's modulus tends to be lowered. The preferred lower limit of Al ₂ O ₃ is at least 9.5%, at least 10.2%, at least 10.5%, in particular at least 10.8%. On the other hand, when the content of Al ₂ O ₃ is more than 15%, the liquidus temperature increases, so that the devitrification resistance tends to decrease. The upper limit of Al ₂ O ₃ is preferably at most 14%, at most 13%, at most 12%, in particular at most 11.5%.

B ₂ O ₃ is lower the high temperature viscosity capabilities, and as flux, is a component to increase the melting property. The content of B ₂ O ₃ is 11 to 20%. The content of B ₂ O ₃ is less than the 11% since it is difficult to act as a flux, increases the high temperature viscosity, it is easy to decrease the bubble quality of the glass. In addition, the density tends to increase. The preferred lower limit of B ₂ O ₃ is at least 12%, at least 13%, at least 14%, at least 15%, in particular at least 15.5%. On the other hand, when the content of B ₂ O ₃ is more than 20%, the strain point, the Young's modulus tends to be lowered. The preferred upper limit of B ₂ O ₃ is 19% or less, 18% or less, particularly 17% or less.

MgO + CaO + SrO + BaO is a component that lowers the liquidus temperature and makes it hard to generate crystalline foreign matter in the glass, and is a component that enhances meltability and formability. The content of MgO + CaO + SrO + BaO is preferably 5 to 12%, 7 to 11%, 8 to 10.5%, 8.5 to 10%, and particularly 9 to 10%. When the content of MgO + CaO + SrO + BaO is small, the function as a flux cannot be sufficiently exhibited, and in addition to the decrease in meltability, the thermal expansion coefficient becomes too low, making it difficult to match the thermal expansion coefficient of Si. On the other hand, when there is much content of MgO + CaO + SrO + BaO, a density will rise, it will become difficult to reduce glass weight, the specific Young's modulus will fall, and also a thermal expansion coefficient will become high too much.

The molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ is 0.8-1.2. When the value of the molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ becomes small, the devitrification resistance tends to decrease, and molding by the overflow downdraw method becomes difficult. On the other hand, when the value of the molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ becomes large, the density and the thermal expansion coefficient become too high. The molar ratio (MgO + CaO + SrO + BaO ) / Al 2 O ₃ A preferred numerical range of 0.8 to 1.05, 0.8 to 1.0, 0.83 to 1.0, 0.85 ~ 0.95, 0.85 ~ 0.90, in particular 0.87 ~ 0.90.

MgO is a component that lowers the high temperature viscosity and increases the meltability without lowering the strain point, and is a component that has the effect of lowering the density among the alkaline earth metal oxides. The content of MgO is preferably 0 to 8%, 0 to 6%, 0 to 2%, 0 to 1%, 0 to 0.5%, and particularly 0 to 0.1%. However, when there is too much content of MgO, liquidus temperature will rise and a devitrification resistance will fall easily. Moreover, glass becomes easy to powder, and transparency falls easily.

When this mass ratio above 0.6 the value of the MgO / B ₂ O _3, the glass is likely to have phase separation. Therefore, the mass ratio MgO / B ₂ O ₃ value is preferably 0.5 or less, 0.3 or less, 0.1 or less, less than 0.08, particularly less than 0.05.

CaO is a component that lowers the high temperature viscosity and significantly improves the meltability 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. Moreover, when the content rate of CaO is relatively increased in alkaline-earth metal oxide, density will fall easily. The preferred lower limit of CaO is at least 8%, at least 8.5%, at least 9%, at least 9.2%, at least 9.4%, in particular at least 9.5%. On the other hand, when there is too much content of CaO, a thermal expansion coefficient and density will become too high, the component balance of a glass composition will be impaired, and devitrification resistance will fall easily. The upper limit with preferable CaO is 12% or less, 11% or less, 10.5% or less, especially 10% or less.

SrO is a component that lowers the high temperature viscosity and increases the meltability without lowering the strain point. However, when the content of SrO increases, the density and the coefficient of thermal expansion tend to increase. In addition, when the content of SrO increases, in order to match the thermal expansion coefficient of Si, it is not obtained that the content of CaO and MgO is not relatively reduced. As a result, the devitrification resistance or the high temperature viscosity tends to increase. The content of SrO is preferably 0 to 2%, 0 to 1.5%, 0 to 1%, and 0 to 0.5%, particularly 0 to 0.1%.

BaO is a component that lowers the high temperature viscosity and increases the meltability without lowering the strain point. However, when the content of BaO increases, the density and the coefficient of thermal expansion tend to increase. In addition, when the content of BaO increases, in order to match the thermal expansion coefficient of Si, it is not possible to obtain a relatively low content of CaO and MgO. As a result, the devitrification resistance or the high temperature viscosity tends to increase. The content of BaO is preferably 0 to 2%, 0 to 1.5%, 0 to 1%, and 0 to 0.5%, particularly less than 0 to 0.1%.

In addition to the above components, for example, the following components may be added to the glass composition. In addition, 25% or less, especially 15% or less of content of components other than the said component are preferable in total from a viewpoint which exhibits the effect of this embodiment correctly.

SnO ₂ is a component that exhibits good blue light action in the high temperature range and is a component that lowers the high temperature viscosity. The content of SnO ₂ is preferably 0 to 1%, 0.001 to 1%, 0.01 to 0.5%, 0.05 to 0.3%, and particularly 0.1 to 0.3%. If the content of SnO ₂ is more than 1%, the devitrification determination of the SnO ₂ is likely to precipitate in the glass. Further, if the content of SnO ₂ is less than 0.001% makes it difficult to exhibit the above effect.

Although ZnO is a component which improves meltability, when it contains a large amount in glass composition, glass will be easily devitrified, a strain point will fall, and density will also increase easily. Therefore, the content of ZnO is preferably 0 to 5%, 0 to 3%, 0 to 0.5%, particularly 0 to 0.3%, and preferably substantially free of content. Here, "it does not contain ZnO substantially" shows the case where content of ZnO in glass composition is 0.1% or less.

ZrO ₂ is a component that increases the Young's modulus. The content of ZrO ₂ is preferably 0 to 5%, 0 to 3%, 0 to 0.5%, particularly 0 to 0.2%, and preferably substantially free of content. When the content of ZrO ₂ is too large, the liquidus temperature increases, devitrification is likely to determine the precipitation of zircon. Further, since the content of ZrO ₂ becomes too large, α of the line count value is liable to increase, it is difficult to apply to the device, such as a CSP. Here, "does not substantially contain ZrO _2" column shows the case of not more than 0.01%, the content of ZrO ₂ in the glass composition. Further, when there is a need to increase the Young's modulus it may be high, the content of ZrO ₂ 0.01% or more.

TiO ₂ is a component that lowers high temperature viscosity and enhances meltability and inhibits solarization. However, when TiO ₂ is contained in a glass composition, glass becomes colored and transmittance easily decreases. Therefore, the content of TiO ₂ is preferably 0 to 5%, 0 to 3%, and 0 to 1%, particularly 0 to 0.02%.

Although P ₂ O ₅ is a component improving the devitrification, when a lot contained in the glass composition, in addition to phase separation, resulting in a milky glass, the water resistance is lowered significantly. Therefore, the content of P ₂ O ₅ is preferably 0 to 5%, 0 to 1%, and 0 to 0.5%, particularly 0 to 0.1%.

Y ₂ O ₃ has a function of increasing the strain point, Young's modulus, and the like. However, when the content of Y ₂ O ₃ is too much, the density is liable to increase. Therefore, the content of Y ₂ O ₃ is not more than 5% is preferred. Nb ₂ O ₅ has a function of increasing the strain point, Young's modulus and the like. However, the content of the components of Nb ₂ O ₅ is too large, it is easy to increase the density. Therefore, the content of Nb ₂ O ₅ is preferably 5% or less. La ₂ O ₃ has a function of increasing the strain point, Young's modulus and the like. However, when the content of La ₂ O ₃ is too much, the density is liable to increase. Therefore, the content of La ₂ O ₃ is preferably 5% or less.

As mentioned above, although SnO ₂ winds as a blue light agent, unless it impairs glass characteristics, it can be used as a blue light agent by 5% of CeO ₂ , SO ₃ , C, and metal powder (eg Al, Si, etc.). Can be added.

As ₂ O ₃ and Sb ₂ O ₃ also function effectively as a blue light agent, and the alkali-free glass of the present embodiment does not completely exclude the inclusion of these components, but from an environmental point of view, the content of these components is 0.1, respectively. Preference is given to less than%, in particular less than 0.05%. In addition, halogen such as F and Cl lowers the melting temperature and promotes the action of the brightener. As a result, it is possible to reduce the melting cost and extend the life of the glass-making kiln. However, when there are too many content of F and Cl, the wiring pattern of the metal formed on a glass substrate may corrode in uses, such as CSP. Therefore, the content of F and Cl is preferably 1% or less, 0.5% or less, less than 0.1%, 0.05% or less, 0.03% or less, particularly 0.01% or less.

In the alkali free glass of this embodiment, density is 2.37g / cm <^3> or less, Preferably it is 2.35g / cm <^3> or less. If the density is large, it is difficult to reduce the weight of the glass, and in the case of a flat plate, the glass is easily bent due to its own weight.

The bubble quality of glass affects not only the yield rate of glass but also the yield rate of a device. For this reason, it is important to lower high temperature viscosity and to raise the bubble quality of glass. In the alkali free glass of this embodiment, the temperature in 10 ^2.5 dPa * s is 1600 degrees C or less, 1540 degrees C or less, 1530 degrees C or less, especially 1520 degrees C or less are preferable. When the temperature in 10 ^2.5 dPa * s is higher than 1600 degreeC, since low-temperature melting becomes difficult and the bubble quality of glass falls easily, not only the manufacturing cost of glass but also the manufacturing cost of a device becomes high easily.

In the alkali free glass of this embodiment, a strain point is 630 degreeC or more, 635 degreeC or more, especially 640 degreeC or more is preferable. In the case of uses, such as CSP, glass may be adhere | attached with resin etc. In that case, when a strain point is lower than 630 degreeC, there exists a possibility that glass quality may fall at the time of sticking glass. Moreover, when a strain point is lower than 630 degreeC, when using as a glass substrate for organic EL, glass will become easy to heat-shrink in the manufacturing process of p-Si * TFT.

In the alkali free glass of this embodiment, the thermal expansion coefficient in the temperature range of 30-380 degreeC is 32-40 * 10 <^-7> / degreeC, 32-38 * 10 <^-7> / degreeC, 32-36 * 10 <^-7>. / ° C., particularly 33 to 35 × 10 ⁻⁷ / ° C. When the coefficient of thermal expansion falls outside the above range, the amount of warpage of the glass substrate tends to increase when the glass substrate and the Si chip are bonded to each other. In addition, the smaller the plate thickness of the glass substrate, the larger the amount of warpage of the glass substrate resulting from the difference in thermal expansion coefficient. Therefore, when the plate | board thickness of a glass substrate is small (for example, when plate | board thickness of a glass substrate is 0.2 mm or less), the meaning which regulates a thermal expansion coefficient within the said range becomes large.

In the alkali free glass of this embodiment, liquid phase temperature is 1180 degrees C or less, 1150 degrees C or less, 1130 degrees C or less, 1110 degrees C or less, 1090 degrees C or less, Especially 1070 degrees C or less is preferable. In this case, devitrification crystals are less likely to occur in the glass, so that it is easy to mold by the overflow downdraw method or the like. As a result, the manufacturing cost of glass can be reduced, and the surface quality of glass can be raised.

In the alkali free glass of the present embodiment, the liquid phase viscosity is preferably 10 ^5.0 dPa · s or more, 10 ^5.2 dPa · s or more, 10 ^5.3 dPa · s or more, 10 ^5.5 dPa · s or more, particularly 10 ^5.7 dPa · s or more. Do. In this case, devitrification crystals are less likely to occur at the time of molding, and therefore, molding is easily performed by the overflow downdraw method or the like. As a result, the manufacturing cost of glass can be reduced, and the surface quality of glass can be raised.

The alkali free glass of this embodiment puts the glass raw material combined so that it may become a predetermined glass composition to a continuous glass melting kiln, and heat-melts this glass raw material, and supplies the obtained molten glass to a shaping | molding apparatus on the clean state, It can manufacture by shape | molding to flat form etc.

It is preferable that the alkali free glass of this embodiment is shape | molded by the overflow downdraw method. In the overflow down-draw method, the surface to be the surface of the glass is formed in the state of the free surface without contacting the groove-like refractory material. For this reason, the flat glass of good surface quality can be manufactured at low cost by unpolishing. In addition, the structure and material of the groove-shaped structure used by the overflow down draw method are not specifically limited as long as a desired dimension and surface precision can be achieved. Moreover, when performing extending | stretching downward, the method of applying a force is not specifically limited, either. For example, the method of extending | stretching by rotating the heat resistant roll which has a sufficiently large width in contact with glass may be employ | adopted, and the method of extending | stretching by contacting several pairs of heat resistant rolls only in the vicinity of the end surface of glass may be employ | adopted. .

The alkali free glass of this embodiment can employ | adopt various shaping | molding methods besides the overflow down draw method. For example, the down draw method (slot down method etc.), the float method, the rollout method, etc. can be employ | adopted.

It is preferable that the alkali free glass of this embodiment has a flat plate shape. In this way, it is applicable to glass substrates for flat displays, such as a liquid crystal monitor and an organic electroluminescent display, and glass substrates for image sensors, such as CSP, CCD, and CIS. Moreover, when the alkali free glass of this embodiment is flat form, the plate | board thickness is 0.6 mm or less, 0.5 mm or less, 0.3 mm or less, 0.2 mm or less, especially 0.1 mm or less is preferable. The smaller the plate thickness, the lighter the glass, and consequently, the device is also easier to lighter. Moreover, since the alkali free glass of this embodiment has a high liquid phase viscosity, it has the property which is easy to shape | mold by the overflow down draw method. By shaping by the overflow downdraw method, it is possible to manufacture a plate-shaped glass having good surface quality by inexpensive polishing at low cost.

(Example 1)

Hereinafter, embodiments of the present invention will be described. However, the following Example is a mere illustration. The present invention is not limited to the following examples at all.

Tables 1 to 3 show examples (sample Nos. 1 to 13) of the present invention.

Example No.1 No.2 No.3 No.4 Glass composition
(mole%) SiO ₂ 64.8 64.7 64.6 63.6 Al ₂ O ₃ 10.0 9.6 9.3 11.0 B ₂ O ₃ 15.5 16.0 16.4 15.6 CaO 9.7 9.7 9.7 9.8 SnO ₂ 0.1 0.1 0.1 0.1 (Mg + Ca + Sr + Ba) / Al 0.97 1.02 1.04 0.89 Density [g / cm ³ ] 2.33 2.33 2.32 2.34 α [× 10 ^-7 / ° C] 34 34 34 34 Ps [℃] 637 634 630 642 Ta [℃] 692 689 684 698 Ts [℃] 937 935 931 937 10 ⁴ dPas [° C] 1267 1268 1269 1255 10 ³ dPas [° C] 1435 1436 1441 1417 10 ^2.5 dPas [° C] 1541 1543 1551 1519 TL [℃] 1055 1050 1045 1110 Log ₁₀ ηTL [dPas] 6.0 6.0 6.0 5.3 Young's modulus [GPa] 66 66 65 67

Example No.5 No.6 No.7 No.8 No.9 Glass composition
(mole%) SiO ₂ 63.9 64.4 64.4 65.2 64.2 Al ₂ O ₃ 10.6 10.6 11.0 11.0 11.4 B ₂ O ₃ 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 - - SnO ₂ 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 / cm ³ ] 2.34 2.34 2.35 2.36 2.36 α [× 10 ^-7 / ° C] 34 34 34 34 34 Ps [℃] 641 645 650 656 653 Ta [℃] 697 702 707 713 710 Ts [℃] 936 941 946 952 948 10 ⁴ dPas [° C] 1261 1268 1271 1281 1268 10 ³ dPas [° C] 1424 1432 1434 1444 1429 10 ^2.5 dPas [° C] 1527 1535 1537 1545 1528 TL [℃] Unmeasured Unmeasured Unmeasured Unmeasured Unmeasured Log ₁₀ ηTL [dPas] Unmeasured Unmeasured Unmeasured Unmeasured Unmeasured Young's modulus [GPa] 67 67 68 68 68

Example No.10 No.11 No.12 No.13 Glass composition
(mole%) SiO ₂ 62.2 62.9 62.1 63.7 Al ₂ O ₃ 11.4 11.8 12.5 11.1 B ₂ O ₃ 16.2 15.3 15.4 15.2 CaO 9.5 8.9 8.9 8.9 SrO 0.6 One One One BaO - - - - SnO ₂ 0.1 0.1 0.1 0.1 (Mg + Ca + Sr + Ba) / Al 0.89 0.84 0.8 0.89 Density [g / cm ³ ] 2.36 2.36 2.37 2.36 α [× 10 ^-7 / ° C] 35 34 34 34 Ps [℃] 637 645 646 643 Ta [℃] 692 701 702 700 Ts [℃] 930 941 942 940 10 ⁴ dPas [° C] 1239 1252 1241 1263 10 ³ dPas [° C] 1397 1410 1395 1424 10 ^2.5 dPas [° C] 1496 1507 1491 1523 TL [℃] Unmeasured Unmeasured Unmeasured Unmeasured Log ₁₀ ηTL [dPas] Unmeasured Unmeasured Unmeasured Unmeasured Young's modulus [GPa] 67 68 68 67

Sample No.1-13 was produced as follows. First, the glass raw material combined so that it might become the glass composition in a table | surface was put into the platinum crucible, melted at 1600 degreeC for 24 hours, and flowed out on the carbon plate, and shape | molded to the equilibrium plate shape. For each sample obtained next, at a density, a thermal expansion coefficient (α), a strain point (Ps), a slow cooling point (Ta), a softening point (Ts), a temperature at 10 ⁴ dPa · s, and 10 ³ dPa · s. The temperature, the temperature in 10 ^2.5 dPa * s, liquidus temperature TL, liquidus viscosity log _{10 (} eta) TL, and Young's modulus were evaluated.

Density is the value measured by the well-known Archimedes method.

Thermal expansion coefficient (alpha) is the value measured with the dilatometer and is an average value in the temperature range of 30-380 degreeC.

The strain point (Ps), the standpoint (Ta), and the softening point (Ts) are values measured according to the method of ASTM C336.

The temperature at 10 ^4.0 dPa · s, the temperature at 10 ^3.0 dPa · s, and the temperature at 10 ^2.5 dPa · s are values measured by the platinum ball pulling-up method.

The liquidus temperature (TL) is passed through a standard 30 mesh (500 μm), and the glass powder remaining at 50 mesh (300 μm) is placed in a platinum boat, held for 24 hours in a temperature gradient, and then the crystal precipitation temperature is measured. One value.

Liquid phase viscosity (log10 (eta) TL) is the value which measured the viscosity of the glass in liquidus temperature (TL) by the platinum ball pulling-up method.

Young's modulus is the value measured by the resonance method. Moreover, in the alkali free glass of this invention, 64 GPa or more is preferable for a Young's modulus. Since the specific Young's modulus (Young's modulus / density) increases as the Young's modulus increases, in the case of flat plate shape, glass becomes difficult to bend by its own weight.

As apparent from Tables 1 to 3, the samples No. 1 to 13 have a glass composition regulated in a predetermined range, so that the density is 2.37 g / cm ³ or less, the strain point is 630 ° C. or more, and 10 ^2.5 dPa · s. The temperature was 1600 degrees C or less. In addition, sample No.1 ~ 13 is that the bubbles goods containing no _{As 2 O 3, Sb 2 O} 3 in the glass composition was found to be satisfactory.

(Example 2)

After melt | dissolving sample No. 1-4 of Table 1 in a test melting furnace, it shape | molded in the flat form of thickness 0.1mm by the overflow downdraw method. At the time of molding, the surface of the glass plate by appropriately adjusting the speed of the tension roller, the speed of the cooling roller, the temperature distribution of the heating apparatus, the temperature of the molten glass, the flow rate of the molten glass, the pulling speed, the rotation speed of the stirring stirrer, and the like. I adjusted the elegance. When the surface quality of the obtained glass plate was measured, curvature was 0.075% or less, curvature (WCA) was 0.15 micrometer or less (cutoff fh: 0.8 mm, fl: 8 mm), and surface roughness Ry was 20 kPa or less (cutoff lambda c: 9 micrometers). Was. In addition, "bending" is the value measured using the thickness gauge described in JIS B-7524, putting a glass plate on the optical surface plate. "Bending" is a value obtained by measuring WCA (filtration centerline bending) described in JIS B-0610 using a stylus type surface measuring device, and a method for measuring surface bending of SEMI STD D15-1296 "FPD glass substrate. It is the value measured by the method based on ". "Average surface roughness (Ry)" is the value measured by the method based on SEMI D7-94 "The measuring method of the surface roughness of a FFP glass substrate."

Claims (8)

As the glass composition, SiO ₂ 50 ~ 70% by _{mol%, Al 2 O 3 9 ~} 15%, B 2 O 3 11 ~ 20%, and containing CaO 8 ~ 12%, the molar ratio (MgO + CaO + SrO + BaO ) / Al ₂ O _{3 has} a value of 0.8∼1.2,
The density is 2.37 g / cm <^3> or less and the temperature in 10 ^2.5 dPa * s is 1600 degrees C or less, The alkali free glass characterized by the above-mentioned. As a glass composition containing _{SiO 2 50 ~ 70%, Al} 2 O 3 9 ~ 15%, B 2 O 3 12 ~ 20%, CaO 9 ~ 12%, Sb 2 O 3 0 ~ 0.03% in mol%, Molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ value is 0.8 ~ 1.05,
The thermal expansion coefficient in the temperature range of 2.35 g / cm <^3> or less, strain point 630 degreeC or more, 10 ^2.5 dPa * s in the temperature range of 1540 degreeC or less and 30-380 degreeC is 32-40 * 10 <^-7> / An alkali free glass characterized by the above-mentioned. As a glass composition containing _{SiO 2 55 ~ 70%, Al} 2 O 3 9.5 ~ 14%, B 2 O 3 14 ~ 20%, CaO 9.2 ~ 11%, Sb 2 O 3 0 ~ 0.03% in mol%, The molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ is 0.83 to 1.0,
Density is 2.35 g / cm ³ or less, Strain point is 635 degreeC or more, the temperature in 10 ^2.5 dPa * s is 1530 degrees C or less, and the thermal expansion coefficient in the temperature range of 30-380 degreeC is 32-38x10 <^-7> / An alkali free glass characterized by the above-mentioned. As a glass composition containing _{SiO 2 55 ~ 70%, Al} 2 O 3 10.5 ~ 14%, B 2 O 3 15 ~ 20%, CaO 9.5 ~ 10.5%, Sb 2 O 3 0 ~ 0.03% in mol%, The molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O ₃ is 0.85 to 0.90,
The thermal expansion coefficient in the temperature range of 2.35 g / cm <^3> or less, strain point 635 degreeC or more, 10 ^2.5 dPa * s in the temperature range of 1520 degreeC or less and 30-380 degreeC is 32-36x10 <^-7> / An alkali free glass characterized by the above-mentioned. As a glass composition containing _{SiO 2 55 ~ 70%, Al} 2 O 3 10.8 ~ 14%, B 2 O 3 15.5 ~ 20%, CaO 9.5 ~ 10%, Sb 2 O 3 0 ~ 0.03% in mol%, The molar ratio (MgO + CaO + SrO + BaO) / Al ₂ O _{3 has} a value of 0.87-0.90,
Density 2.35g / cm ³ Hereinafter, the strain point is 640 degreeC or more, the temperature in 10 ^2.5 dPa * s is 1520 degrees C or less, and the thermal expansion coefficient in the temperature range of 30-380 degreeC is 32-36x10 <^-7> / degreeC Alkali glass. 6. The method according to any one of claims 1 to 5,
The liquid-free viscosity is 10 ^5.0 dPa * s or more, The alkali free glass characterized by the above-mentioned. 7. The method according to any one of claims 1 to 6,
An alkali free glass formed by the overflow downdraw method. The method according to any one of claims 1 to 7,
An alkali free glass, which is used for a substrate of a chip size package.