Metal sealing glass

Abstract

To provide a metal sealing glass having a high thermal expansion coefficient, less bubbles and striae, and high water resistance. The present invention provides a ceramic material containing, in mass % oxides, 60.0% to 75.0% of SiO2, 9.0% to 18.0% of B2O3, 3.0% to 9.0% of Al2O3, 5.0% to 12.0% of Na2O, and 0% to 1.65% of K2O, and has a thermal expansion coefficient of 60×10 -7 / K or more 72×10 -7 The above problems are solved by using a metal sealing glass with a dielectric constant of 0.15 / K or less.

Description

[Technical Field]

[0001] The present invention relates to a metal sealing glass that has a high coefficient of thermal expansion and has fewer bubbles, striae, etc., as well as high water resistance. [Background technology]

[0002] Patent Document 1 discloses borosilicate glass for sealing alumina that is particularly suitable for use as a window glass for an alumina package that houses a solid-state imaging device such as a CCD, and as a cap glass for a solid-state imaging device or a thin-film imaging device that is mounted on an alumina substrate.

[0003] Highly reliable alumina ceramics are used for the package. This package requires a window that allows light to pass through, so a glass plate is sealed to the alumina package using glass frit. Contact-type image sensors use an alumina ceramic substrate with thin-film elements such as amorphous silicon attached, or an array of silicon chips. In this case, the thin-film elements or solid-state elements are covered with a cap glass, which is hermetically sealed to the alumina substrate using glass frit.

[0004] The glass used for this application must not crack, warp, or distort when sealed with alumina. In other words, the thermal expansion coefficient of the glass must match that of the alumina. Also, light passing through this window glass or cap glass must reach the image sensor without distortion. This requires high-quality glass with few defects such as striae, bubbles, lumps, and dirt.

[0005] Patent Document 1 states that it has been discovered that the composition described therein makes it possible to obtain high-quality borosilicate glass for alumina sealing that is homogeneous and has few defects, and is suitable for alumina sealing. However, the composition described in Patent Document 1 has a problem in that it has low water resistance due to the high content of the K2O component. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 62-65954 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a metal sealing glass that has a high coefficient of thermal expansion, fewer bubbles, striae, etc., and also has high water resistance. [Means for solving the problem]

[0008] The present invention includes the following embodiments (configurations). (Configuration 1) In mass % based on oxides, SiO2 content of 60.0% or more and 75.0% or less, B2O3 content of 9.0% or more and 18.0% or less, Al2O3 component is 3.0% or more and 9.0% or less, Na2O component is 5.0% or more and 12.0% or less, K2O content: 0% to 1.65% Contains Thermal expansion coefficient is 60 x 10 -7 / K or more 72×10 -7 / K or less, Glass for metal sealing. (Configuration 2) In mass % based on oxides, CaO content: 0% to 4.0% BaO content: 0% to 6.0% ZnO content: 0% to 6.0% MgO content: 0% to 5.0% Sb2O3 component: 0% to 2.0% Contains 2. The metal sealing glass according to claim 1. (Configuration 3) In mass % based on oxides, The mass ratio B2O3 / K2O is 9.0 or more and 15.0 or less, 3. The glass for metal sealing according to configuration 1 or 2. (Configuration 4) In mass % based on oxides, The mass ratio of SiO2 / K2O is 45.0 or more and 65.0 or less. 4. The metal sealing glass according to any one of Configurations 1 to 3. (Configuration 5) In mass % based on oxides, The mass ratio (B2O3+SiO2) / K2O is 53.5 or more and 80.0 or less. 5. The metal sealing glass according to any one of the first to fourth aspects. [Effects of the Invention]

[0009] According to the present invention, by adjusting the contents of the B2O3 component and the SiO2 component, it is possible to provide a metal sealing glass having a high thermal expansion coefficient and fewer bubbles, striae, etc., and by adjusting the content of the K2O component, it is possible to improve the water resistance of the metal sealing glass.

[0010] The present invention can be used for glass that requires high thermal expansion coefficient, few bubbles and striae, and high water resistance, such as window glass and protective materials for electronic components. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, the embodiments and examples of the present invention will be described in detail, but the present invention is not limited to the following embodiments and examples, and can be practiced by making appropriate modifications within the scope of the object of the present invention. In other words, the following embodiments and examples are merely examples for facilitating understanding of the present invention, and they can be changed or improved without departing from the spirit of the present invention, and of course, the present invention includes equivalents thereof.

[0012] In this specification, unless otherwise specified, the content of each component is expressed in mass % based on the oxide. Here, "mass % based on the oxide" refers to the amount of oxide of each component contained in glass, expressed in mass %, when it is assumed that all components constituting the glass are decomposed and converted to oxides, and the total mass of the oxides is 100 mass %.

[0013] The metal sealing glass according to an embodiment of the present invention is In mass % based on oxides, SiO2 content of 60.0% or more and 75.0% or less, B2O3 content of 9.0% or more and 18.0% or less, Al2O3 component is 3.0% or more and 9.0% or less, Na2O component is 5.0% or more and 12.0% or less, K2O content: 0% to 1.65% Contains Thermal expansion coefficient is 60 x 10 -7 / K or more 72×10 -7 / K or less.

[0014] The composition ranges of the components constituting the metal sealing glass according to the embodiment of the present invention will be specifically described below.

[0015] The SiO2 component is the main component of the metal sealing glass according to the embodiment of the present invention, and is a basic component that forms the skeleton of the glass. If the content of the SiO2 component exceeds 75.0%, the viscosity of the melt becomes high, making it difficult to form the glass. In addition, bubbles, striae, etc. are generated, and the quality of the glass is likely to deteriorate. Therefore, the upper limit of the content of the SiO2 component is preferably 75.0% or less, 74.0% or less, 72.0% or less, or 70.0% or less. Furthermore, if the content of the SiO2 component is less than 60.0%, the thermal expansion coefficient becomes large, making the glass more likely to crack when sealed to metal. The water resistance of the glass also deteriorates. Furthermore, the glass is more likely to devitrify. Therefore, the lower limit of the content of the SiO2 component is preferably 60.0% or more, 61.0% or more, 62.0% or more, 63.0% or more, 64.0% or more, or 65.0% or more.

[0016] The B2O3 component is a component suitable for improving the meltability of the glass and for lowering the viscosity of the melt. By keeping the B2O3 content at 18.0% or less, it is possible to prevent a decrease in the thermal expansion coefficient and also to reduce the viscosity of the melt. Therefore, the upper limit of the B2O3 content is preferably 18.0% or less, 17.0% or less, 16.0% or less, 15.0% or less, 14.6% or less, or 14.0% or less. Furthermore, by making the content of the B2O3 component 9.0% or more, the meltability of the glass can be improved. Therefore, the lower limit of the content of the B2O3 component is preferably 9.0% or more, 10.0% or more, 11.0% or more, 12.0% or more, or 13.0% or more.

[0017] The Al2O3 component is a component suitable for improving the water resistance of the glass, and is also a component suitable for suppressing devitrification of the glass. If the content of the Al2O3 component exceeds 9.0%, the meltability of the glass deteriorates. Therefore, the upper limit of the content of the Al2O3 component is preferably 9.0% or less, 8.0% or less, 7.0% or less, or 6.0% or less. Furthermore, if the content of the Al2O3 component is less than 3.0%, it becomes difficult to improve water resistance and the glass is prone to devitrification. Therefore, the lower limit of the content of the Al2O3 component is preferably 3.0% or more, 4.0% or more, or 5.0% or more.

[0018] The Na2O component is a component that improves the meltability of the glass and has the effect of lowering the melting point of the glass when melted. If the content of the Na2O component exceeds 12.0%, the water resistance of the glass deteriorates. Therefore, the upper limit of the content of the Na2O component is preferably 12.0% or less, 11.5% or less, 11.0% or less, 10.0% or less, or 9.0% or less. Furthermore, if the content of the Na2O component is less than 5.0%, the meltability will be poor. Therefore, the lower limit of the content of the Na2O component is preferably 5.0% or more, 6.0% or more, 7.0% or more, or 8.0% or more.

[0019] The K2O component is a component that improves the water resistance and meltability of the glass, and also a component that increases the thermal expansion coefficient. By setting the content of the K2O component to 1.65% or less, the water resistance of the glass can be improved. Therefore, the upper limit of the content of the K2O component is preferably 1.65% or less, 1.5% or less, 1.4% or less, or 1.3% or less. Furthermore, by including the K2O component, it is possible to improve water resistance and meltability, and also to increase the thermal expansion coefficient. The lower limit of the content of the K2O component is preferably 0% or more, 0.5% or more, 0.6% or more, or 1.0% or more.

[0020] MgO is a suitable component for improving the water resistance of the glass. If the content of the MgO component exceeds 5.0%, the glass tends to devitrify and the water resistance tends to deteriorate. Therefore, the upper limit of the content of the MgO component is preferably 5.0% or less, 4.0% or less, 3.0% or less, or 2.0% or less. Furthermore, by including an MgO component, the meltability and water resistance of the glass can be improved, and devitrification can be suppressed. The lower limit of the content of the MgO component is preferably 0% or more, 0.1% or more, 0.2% or more, 0.3% or more, or 0.4% or more.

[0021] CaO is a suitable component for improving the water resistance of the glass. If the CaO content exceeds 4.0%, the glass is likely to devitrify and the water resistance is likely to deteriorate. Therefore, the upper limit of the CaO content is preferably 4.0% or less, 3.0% or less, or 2.0% or less. Furthermore, by including a CaO component, the meltability and water resistance of the glass can be improved, and devitrification can be suppressed. The lower limit of the content of the CaO component is preferably 0% or more, 0.5% or more, or 0.8% or more.

[0022] The BaO component is a component suitable for suppressing the phase separation phenomenon of glass and improving water resistance. If the content of the BaO component exceeds 6.0%, the glass tends to devitrify and the water resistance tends to deteriorate. Therefore, the upper limit of the content of the BaO component is preferably 6.0% or less, 5.0% or less, 4.0% or less, or 3.0% or less. Furthermore, by including a BaO component, the meltability of the glass can be improved, and also the water resistance can be improved. The lower limit of the content of the BaO component is preferably 0% or more, 1.0% or more, 1.5% or more, or 2.0% or more.

[0023] The ZnO component is a component that suppresses the evaporation of the B2O3 component and the alkaline component. If the ZnO content exceeds 6.0%, the glass tends to devitrify, and the B2O3 component and alkali components tend to evaporate. Therefore, the upper limit of the ZnO content is preferably 6.0% or less, 4.0% or less, 2.0% or less, or 1.0% or less. Furthermore, by including a ZnO component, the meltability and chemical durability of the glass can be improved, and coloration of the glass can be reduced. The lower limit of the ZnO content is preferably 0% or more, 0.2% or more, 0.4% or more, or 0.5% or more.

[0024] The Sb2O3 component is a component that has the effect of promoting defoaming and fining inside the glass. If the content of the Sb2O3 component exceeds 2.0%, alloying with other metals is likely to occur, and the internal quality is likely to deteriorate due to the occurrence of knots, etc. Therefore, the upper limit of the content of the Sb2O3 component is preferably 2.0% or less, 1.0% or less, or 0.5% or less. Furthermore, by including Sb2O3, the defoaming effect can be enhanced. The lower limit of the content of Sb2O3 is preferably 0% or more, 0.1% or more, or 0.15% or more.

[0025] Furthermore, as another optional component, the content of the Li2O component may be set to 0% or more and less than 0.5%, or even 0% or more and 0.3% or less.

[0026] The mass ratio B2O3 / K2O is preferably 9.0 or more and 15.0 or less. By adjusting the content of the B2O3 component and / or the K2O component within the above ranges to achieve this mass ratio of 9.0 to 15.0, the viscosity of the glass can be reduced, making the glass easier to mold, and the glass can be produced without reducing its chemical durability. Therefore, the upper limit of the mass ratio B2O3 / K2O is preferably 15.0 or less, more preferably 14.0 or less, even more preferably 13.5 or less, and even more preferably 12.0 or less. The lower limit of the mass ratio B2O3 / K2O is preferably 9.0 or more, more preferably 10.0 or more.

[0027] The mass ratio SiO2 / K2O is preferably 45.0 or more and 65.0 or less. By adjusting the content of the SiO2 component and / or the content of the K2O component within the above ranges to achieve this mass ratio of 45.0 to 65.0, the melting temperature of the glass is lowered, making it easier to melt, and enabling the production of glass without reducing chemical durability. Therefore, the upper limit of the mass ratio SiO2 / K2O is preferably 65.0 or less, more preferably 63.0 or less, even more preferably 62.0 or less, and even more preferably 60.0 or less. The lower limit of the mass ratio SiO2 / K2O is preferably 45.0 or more, more preferably 47.0 or more, even more preferably 50.0 or more, and even more preferably 53.0 or more.

[0028] The mass ratio (B2O3+SiO2) / K2O is preferably 53.5 or more and 80.0 or less. By adjusting the content of one or more components selected from the group consisting of the SiO2 component, the B2O3 component, and the K2O component within the above range to make this mass ratio 53.5 or more and 80.0 or less, a glass with a high thermal expansion coefficient can be obtained. Therefore, the upper limit of the mass ratio (B2O3+SiO2) / K2O is preferably 80.0 or less, more preferably 76.0 or less, even more preferably 70.0 or less, and even more preferably 67.0 or less. The lower limit of the mass ratio (B2O3+SiO2) / K2O is preferably 53.5 or more, more preferably 56.0 or more, even more preferably 60.0 or more, and even more preferably 64.0 or more.

[0029] The thermal expansion coefficient (×10 -7 / K) is preferably 72 × 10 -7 / K or less, preferably 71×10 -7 / K or less, more preferably 70×10 -7 / K or less, more preferably 69 × 10 -7 / K or less, more preferably 68×10 -7 / K or less, more preferably 67×10 -7 / K or less. The lower limit of the thermal expansion coefficient is preferably 60×10 -7 / K or more, preferably 62 × 10 -7 / K or more, more preferably 63 × 10 -7 / K or more. By increasing the thermal expansion coefficient in this way, the glass can be easily sealed to metal, and a stable metal sealing glass can be produced. Note that this thermal expansion coefficient is a value measured and calculated by the method described in the examples below.

[0030] Water resistance is an index of the likelihood of glass surface discoloration, and is determined by calculating the weight loss (wt%) of a glass sample before and after reagent treatment and then classifying the glass into grades. The smaller the weight loss of a glass sample before and after reagent treatment, the higher the water resistance of the glass tends to be. Therefore, the weight loss of a metal sealing glass according to an embodiment of the present invention before and after reagent treatment is preferably less than 0.05 wt%, more preferably 0.01 wt% or less. This weight loss is a value measured and calculated by the method described in the Examples below. [Example]

[0031] [Examples 1 to 5] 1. Preparation of metal sealing glass As raw materials for each component of the metal sealing glass, raw materials such as oxides, hydroxides, carbonates, and nitrates were selected, and these raw materials were weighed and mixed uniformly to obtain the composition shown in Table 1 below.

[0032] Next, the mixed raw materials were placed in a platinum crucible and melted in an electric furnace at 1350°C to 1450°C for 2 to 24 hours. The molten glass was then stirred to homogenize it, and the temperature was lowered to 1400°C before it was poured into a mold and slowly cooled (annealed) to produce the glass.

[0033] 2.Metal sealing glass evaluation method The obtained glass was measured for the following properties, and the results are shown in Table 1 below.

[0034] (1) Thermal expansion coefficient The thermal expansion coefficient was measured in accordance with Japan Optical Glass Industry Association Standard JOGIS-16 "Method for measuring the average linear expansion coefficient of optical glass near room temperature" and JOGIS-8 "Method for measuring the thermal expansion of optical glass" (2019). In the embodiment of the present invention, the thermal expansion coefficient was determined from the thermal expansion curve of the glass.

[0035] (2) Specific gravity The specific gravity is the ratio of the density of each glass type after annealing to that of pure water at 1 atmosphere and 4°C. The measurement method was in accordance with JIS Z 8807 "Method for measuring density and specific gravity by the liquid weighing method," in which the glass sample was weighed in air and in water, and the density thus determined was divided by the density of water to calculate the specific gravity.

[0036] (3) Water resistance The water resistance of the glasses of Examples 1 to 5 was measured in accordance with Japan Optical Glass Industry Association Standard JOGIS-06, "Method for Measuring Chemical Durability of Optical Glass (Powder Method)." Specifically, glass samples of a size that passed through a 600 μm test sieve and remained on a 425 μm test sieve were placed in a platinum cage in grams of specific gravity, placed in a glass round-bottom flask containing 0.01 N aqueous nitric acid solution, and treated in a boiling water bath for 60 minutes. After treatment, the mass loss (wt%) of the glass sample was calculated to determine the weight loss rate (wt%).

[0037] [Comparative Example 1] The composition and physical properties of Sample No. 5 described in Patent Document 1 are shown in Table 1 as Comparative Example 1. This sample has a problem of low water resistance due to the high content of K2O component.

[0038] [Table 1]

Claims

1. In mass % based on oxides, SiO 2 Ingredients: 60.0% or more and 75.0% or less, B 2 O 3 Ingredients: 9.0% or more and 18.0% or less, Al 2 O 3 Ingredients: 3.0% or more and 9.0% or less, Na 2 O component is 5.0% or more and 12.0% or less, K 2 O component: 0% to 1.65% Contains Thermal expansion coefficient is 60 x 10 -7 / K or more 72×10 -7 / K or less, Glass for metal sealing.

2. In mass % based on oxides, CaO component is 0% or more and 4.0% or less, BaO component is 0% or more and 6.0% or less, ZnO component is 0% or more and 6.0% or less, MgO component is 0% or more and 5.0% or less, Sb 2 O 3 Ingredients: 0% to 2.0% Contains The metal sealing glass according to claim 1 .

3. In mass % based on oxides, Mass ratio B 2 O 3 / K 2 O is 9.0 or more and 15.0 or less, The metal sealing glass according to claim 1 or 2.

4. In mass % based on oxides, Mass ratio SiO 2 / K 2 O is 45.0 or more and 65.0 or less, The metal sealing glass according to claim 1 or 2.

5. In mass % based on oxides, Mass ratio (B 2 O 3 +SiO 2 ) / K 2 O is 53.5 or more and 80.0 or less, The metal sealing glass according to claim 1 or 2.

Images