Glass and preparation method thereof

Abstract

The present invention relates to a glass and a preparation method thereof, belonging to the technical field of glass. The glass provided by the present invention comprises silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxides, alkali metal oxides and other oxides. The glass has high heat resistance, high water resistance, high acid resistance, high alkali resistance and high folding resistance, and can reach HGB1 level water resistance, 1 level acid resistance and 1 level alkali resistance, and can be applied to packaging materials, especially primary packaging materials for alkaline drugs.

Description

Technical Field

[0001] The present invention relates to glass and a preparation method thereof, belonging to the technical field of glass, and in particular to borosilicate glass with high chemical resistance and mechanical properties and a preparation method and application thereof. Background Art

[0002] Glass products are widely used in the pharmaceutical field, and many medicines need to be contained in glass products. With the rapid development of the pharmaceutical industry, there are more and more alkaline drugs, which puts higher requirements on the alkali resistance of packaging materials. When using glass bottles that do not meet the requirements, under certain conditions, glass flakes will fall off from the inner surface of the glass container and directly enter the drug solution, which is sometimes difficult to detect with the naked eye. The presence of glass flakes in intravenous drugs may cause thrombosis and other vascular events (such as phlebitis); for subcutaneous injections, flake shedding may lead to the occurrence of foreign body granulomas, local injection site reactions, and increased immunogenicity.

[0003] The biggest disadvantage of glass products is that they are fragile, which can easily cause pharmaceutical glass bottles to break during transportation. Improving the flexural resistance and mechanical strength of glass products is very important for improving the compatibility of glass products.

[0004] At present, the containers of liquid medicines are developing from ordinary glass bottles to flexible packaging. As for plastic bottles, consumers are worried that plastic bottles will have compatibility issues with medicines. Once the medicines are compatible with plastic medicine bottles, the efficacy and quality of the medicines will be affected, and the health of the human body cannot be guaranteed.

[0005] For oral liquids and injections, liquids are more corrosive than solids. Freeze-dried powders or expensive medicines, such as injectable vaccines, contain highly corrosive substances, so these medicines need to be packaged in glass bottles with good chemical stability.

[0006] Chinese patent application CN1203018C discloses a highly chemically resistant borosilicate glass, which is composed of silicon dioxide, boron trioxide, aluminum trioxide, calcium oxide, magnesium oxide, sodium oxide, potassium oxide, strontium peroxide, zinc oxide, zirconium dioxide, etc., and has level 1 acid resistance and HGB1 level water resistance, but its alkali resistance can only reach level 2 alkali resistance.

[0007] Therefore, in order to solve the above technical problems, it is necessary to study a glass that has high water resistance, high acid resistance, high alkali resistance and high flexural strength. Summary of the invention

[0008] In order to solve the above problems, the present invention provides a glass and a preparation method and application thereof.

[0009] In a first aspect, the present invention provides a glass.

[0010] A glass comprising silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxides, alkali metal oxides and other oxides.

[0011] The alkaline earth metal oxide may include at least one selected from the group consisting of calcium oxide, barium oxide, strontium peroxide, and magnesium oxide.

[0012] The alkali metal oxide may include at least one selected from the group consisting of sodium oxide, potassium oxide, and lithium oxide.

[0013] The other oxides may include zirconium dioxide and yttrium trioxide, and optionally include zinc oxide. In some embodiments, the other oxides include zirconium dioxide and yttrium trioxide, which is conducive to obtaining glass with good water resistance, alkali resistance and acid resistance. In some embodiments, the other oxides include zirconium dioxide, yttrium trioxide and zinc oxide, which is not only conducive to improving the water resistance, alkali resistance and acid resistance of the obtained glass, but also can improve its flexural strength.

[0014] When the glass contains zinc oxide, it helps to improve the flexural strength of the glass. When the zinc oxide content is 0.5wt% to 2.5wt% based on the total weight of the glass, the glass has good flexural strength. In some preferred embodiments, the zinc oxide content is 0.80wt% to 1.92wt% based on the total weight of the glass, and the glass has good flexural strength. In some more preferred embodiments, the zinc oxide content is 0.84wt% to 1.50wt% based on the total weight of the glass, and the glass has better flexural strength. In some most preferred embodiments, when the zinc oxide content is 1.10wt% to 1.50wt% based on the total weight of the glass, the glass has the best flexural strength.

[0015] The content of zirconium dioxide can be 0.88wt% to 2.00wt% based on the total weight of the glass. In some preferred embodiments, the content of zirconium dioxide is preferably 0.90wt% to 1.52wt% based on the total weight of the glass, which helps to improve the alkali resistance of the glass and obtain high-performance glass.

[0016] The content of yttrium trioxide can be 1.70wt% to 3.01wt% based on the total weight of the glass. In some embodiments, the content of yttrium trioxide is preferably 1.86wt% to 2.67wt% based on the total weight of the glass, which helps to improve the alkali resistance of the glass and obtain high-performance glass.

[0017] The molar ratio of the zirconium dioxide and yttrium trioxide may be 0.50:1 to 2.10:1. In some embodiments, the molar ratio of the zirconium dioxide and yttrium trioxide is 0.50:1 to 1.50:1. In some embodiments, the molar ratio of the zirconium dioxide and yttrium trioxide is 0.67:1 to 1.50:1. In some embodiments, the molar ratio of the zirconium dioxide and yttrium trioxide is 0.50:1 to 0.53:1. In some embodiments, the molar ratio of the zirconium dioxide and yttrium trioxide is 1.83:1 to 2.10:1. In some embodiments, the molar ratio of the zirconium dioxide and yttrium trioxide is 1.50:1.

[0018] The glass may include zirconium dioxide and yttrium trioxide, and the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, preferably 1.50:1. Based on the total weight of the glass, the content of zirconium dioxide is 0.88wt% to 2.00wt%, the content of zirconium dioxide is preferably 0.90wt% to 1.52wt%, the content of yttrium trioxide is 1.70wt% to 3.01wt%, and the content of yttrium trioxide is preferably 1.86wt% to 2.67wt%. The glass has better alkali resistance.

[0019] Based on the total weight of the glass, the content of zinc oxide is 0.84wt% to 1.50wt%, the amount of zirconium dioxide is 0.90wt% to 1.52wt%, and the content of yttrium trioxide is 1.86wt% to 2.67wt%, which is beneficial to improving the alkali resistance and flexural strength of the glass.

[0020] Based on the total weight of the glass, the content of zinc oxide is 0.84wt% to 1.50wt%, the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, the amount of zirconium dioxide is 0.90wt% to 1.52wt%, and the content of yttrium trioxide is 1.86wt% to 2.67wt%, which is beneficial to improving the alkali resistance and flexural strength of the glass.

[0021] Based on the total weight of the glass, the total content of zirconium dioxide and yttrium trioxide can be 2.42wt% to 10.5wt%. In some embodiments, based on the total weight of the glass, the total content of zirconium dioxide and yttrium trioxide is 2.42wt% to 8.00wt%. In some embodiments, based on the total weight of the glass, the total content of zirconium dioxide and yttrium trioxide is 2.42wt% to 5.56wt%. In some embodiments, based on the total weight of the glass, the total content of zirconium dioxide and yttrium trioxide is 2.58wt% to 5.01wt%; the glass has better alkali resistance.

[0022] Based on the total weight of the glass, the content of the silicon dioxide may be 66.0 wt% to 74.0.0 wt%. In some embodiments, based on the total weight of the glass, the content of the silicon dioxide is 68.0 wt% to 72.0 wt%.

[0023] Based on the total weight of the glass, the content of diboron trioxide may be 8.0 wt% to 13.0.0 wt%. In some embodiments, based on the total weight of the glass, the content of diboron trioxide is 10.0 wt% to 12.0 wt%.

[0024] The content of aluminum oxide can be 2.0wt% to 7.0wt% based on the total weight of the glass. In some embodiments, the content of aluminum oxide is 3.2wt% to 5.5wt% based on the total weight of the glass. In some embodiments, the content of aluminum oxide is 4.2wt% to 5.5wt% based on the total weight of the glass. In some embodiments, the content of aluminum oxide is 4.0wt% to 4.5wt% based on the total weight of the glass.

[0025] In some embodiments of the present invention, a glass includes silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide and yttrium trioxide; based on the total weight of the glass, the content of zirconium dioxide is 0.88wt% to 2.00wt%, the content of zirconium dioxide is preferably 0.90wt% to 1.52wt%, the content of yttrium trioxide is 1.70wt% to 3.01wt%, and the content of yttrium trioxide is preferably 1.86wt% to 2.67wt%, which is beneficial to improving the alkali resistance of the glass.

[0026] In some embodiments of the present invention, a glass includes silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide and yttrium trioxide; based on the total weight of the glass, the content of zirconium dioxide is 0.88wt% to 2.00wt%, the content of zirconium dioxide is preferably 0.90wt% to 1.52wt%, the content of yttrium trioxide is 1.70wt% to 3.01wt%, and the content of yttrium trioxide is preferably 1.86wt% to 2.67wt%; the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, which is beneficial to improving the alkali resistance of the glass.

[0027] In some embodiments of the present invention, a glass includes silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.88wt% to 2.00wt%, the content of zirconium dioxide is preferably 0.90wt% to 1.52wt%, the content of yttrium trioxide is 1.70wt% to 3.01wt%, and the content of yttrium trioxide is preferably 1.86wt% to 2.67wt%; the alkaline earth metal oxide includes at least one selected from calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxide includes at least one selected from sodium oxide, potassium oxide and lithium oxide.

[0028] In some embodiments of the present invention, a glass includes silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxides, alkali metal oxides, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zinc oxide is 1.10wt% to 1.50wt%, the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, and the amount of zirconium dioxide is 0.90wt% to 1.52wt%, which is beneficial to improving the alkali resistance and flexural strength of the glass.

[0029] In some embodiments of the present invention, a glass includes silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zinc oxide is 0.84wt% to 1.50wt%, the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, and the amount of zirconium dioxide is 0.90wt% to 1.52wt%, which is beneficial to improving the alkali resistance and flexural strength of the glass.

[0030] In some embodiments of the present invention, a glass includes silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zinc oxide is 0.84wt% to 1.50wt%, the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, the amount of zirconium dioxide is 0.90wt% to 1.52wt%, and the content of yttrium trioxide is 1.86wt% to 2.67wt%, which is beneficial to improving the alkali resistance and flexural strength of the glass.

[0031] The total content of calcium oxide, barium oxide and magnesium oxide can be 0.5wt% to 3.5wt% based on the total weight of the glass. In some embodiments, the total content of calcium oxide, barium oxide and magnesium oxide is 1.0wt% to 2.5wt% based on the total weight of the glass. In some embodiments, the total content of calcium oxide, barium oxide and magnesium oxide is 1.5wt% to 2.0wt% based on the total weight of the glass.

[0032] The content of calcium oxide may be 1.0 wt% to 2.5 wt% based on the total weight of the glass. In some embodiments, the content of calcium oxide is 1.5 wt% to 2.0 wt% based on the total weight of the glass.

[0033] The content of the barium oxide can be 0-2.0 wt % based on the total weight of the glass. In some embodiments, the content of the barium oxide is 0.5 wt %-1.5 wt % based on the total weight of the glass. In some embodiments, the content of the barium oxide is 1.0 wt % based on the total weight of the glass.

[0034] The content of magnesium oxide can be 0-2.0 wt% based on the total weight of the glass. In some embodiments, the content of magnesium oxide is 0.5 wt%-1.5 wt% based on the total weight of the glass. In some embodiments, the content of magnesium oxide is 1.0 wt% based on the total weight of the glass.

[0035] The alkaline earth metal oxide may include at least one of calcium oxide, barium oxide and magnesium oxide, and based on the total weight of the glass, the content of calcium oxide is 1.0wt% to 2.5wt%, the content of barium oxide is 0 to 2.0wt%, and the content of magnesium oxide is 0 to 2.0wt%. When the total content of calcium oxide, barium oxide and magnesium oxide is 0.5wt% to 3.5wt%, the glass has low high-temperature viscosity, good chemical stability, and is not easy to crystallize.

[0036] The content of strontium peroxide can be 0-3.0wt% based on the total weight of the glass. The glass has low high temperature viscosity, good chemical stability, and is not easy to crystallize. In some embodiments, the content of strontium peroxide is 0.5wt%-2.5wt% based on the total weight of the glass. In some embodiments, the content of strontium peroxide is 1.0wt%-2.0wt% based on the total weight of the glass. In some embodiments, the content of strontium peroxide is 1.5wt% based on the total weight of the glass.

[0037] Based on the total weight of the glass, the total content of sodium oxide, potassium oxide and lithium oxide can be 4.5wt% to 10.5wt%. In some embodiments, the total content of sodium oxide, potassium oxide and lithium oxide is 6.0wt% to 9.0wt%, and the glass has a good linear thermal expansion coefficient and a low processing temperature. In some embodiments, the total content of sodium oxide, potassium oxide and lithium oxide is 7.0wt% to 8.0wt%, and the glass has a good linear thermal expansion coefficient and a low processing temperature.

[0038] The content of sodium oxide can be 3.0wt% to 9.0wt% based on the total weight of the glass. In some embodiments, the content of sodium oxide is 4.0wt% to 8.0wt% based on the total weight of the glass. In some embodiments, the content of sodium oxide is 5.0wt% to 7.0wt% based on the total weight of the glass. In some embodiments, the content of sodium oxide is 6.0wt% based on the total weight of the glass.

[0039] The content of potassium oxide can be 0-3.0 wt% based on the total weight of the glass. In some embodiments, the content of potassium oxide is 0.5 wt%-2.5 wt% based on the total weight of the glass. In some embodiments, the content of potassium oxide is 1.0 wt%-2.0 wt% based on the total weight of the glass. In some embodiments, the content of potassium oxide is 1.5 wt% based on the total weight of the glass.

[0040] The content of the lithium oxide can be 0-3.0 wt% based on the total weight of the glass. In some embodiments, the content of the lithium oxide is 0.5 wt%-2.5 wt% based on the total weight of the glass. In some embodiments, the content of the lithium oxide is 1.0 wt%-2.0 wt% based on the total weight of the glass. In some embodiments, the content of the lithium oxide is 1.5 wt% based on the total weight of the glass.

[0041] The alkali metal oxide may include at least one of sodium oxide, potassium oxide, and lithium oxide, and based on the total weight of the glass, the content of sodium oxide is 3.0wt% to 9.0wt%, the content of potassium oxide is 0 to 3.0wt%, the content of lithium oxide is 0 to 3.0wt%, and the total content of sodium oxide, potassium oxide and lithium oxide is 4.5wt% to 10.5wt%. The glass has a good linear thermal expansion coefficient and a low processing temperature.

[0042] In some embodiments of the present invention, a glass comprises silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.88wt% to 2.00wt%, and the content of yttrium trioxide is 1.70wt% to 3.01wt%; the molar ratio of zirconium dioxide to yttrium trioxide is 0.50:1 to 2.10:1; the alkaline earth metal oxide comprises at least one selected from calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxide comprises at least one selected from sodium oxide, potassium oxide and lithium oxide; the glass has not only good chemical resistance (water resistance, acid resistance and alkali resistance), but also good flexural strength, the glass has low high temperature viscosity, good chemical stability, is not easy to crystallize, has a good linear thermal expansion coefficient and a low processing temperature.

[0043] In some embodiments of the present invention, a glass comprises silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.88wt% to 2.00wt%, and the content of yttrium trioxide is 1.70wt% to 3.01wt%; the molar ratio of zirconium dioxide to yttrium trioxide is 0.50:1 to 2.10:1; the content of zinc oxide is 0.5wt% to 2.5wt%; the alkaline earth metal oxide comprises at least one selected from calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxide comprises at least one selected from sodium oxide, potassium oxide and lithium oxide; the glass has not only good chemical resistance (water resistance, acid resistance and alkali resistance), but also good flexural strength, the glass has low high temperature viscosity, good chemical stability, is not easy to crystallize, has a good linear thermal expansion coefficient and a low processing temperature.

[0044] In some embodiments of the present invention, a glass comprises silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.88wt% to 2.00wt%, the content of yttrium trioxide is 1.70wt% to 3.01wt%; the molar ratio of zirconium dioxide to yttrium trioxide is 0.50:1 to 2.10:1; the content of zinc oxide is 0.84wt% to 1.50wt%. t% (the content of zinc oxide is preferably 1.10wt% to 1.50wt%); the alkaline earth metal oxide includes at least one selected from calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxide includes at least one selected from sodium oxide, potassium oxide and lithium oxide; the glass not only has good chemical resistance (water resistance, acid resistance and alkali resistance), but also has good flexural strength, the glass has low high temperature viscosity, good chemical stability, is not easy to crystallize, has a good linear thermal expansion coefficient and a low processing temperature.

[0045] In some embodiments of the present invention, a glass comprises silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.90wt% to 1.52wt%, and the content of yttrium trioxide is 1.86wt% to 2.67wt%; the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1; the alkaline earth metal oxide comprises at least one selected from calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxide comprises at least one selected from sodium oxide, potassium oxide and lithium oxide; the glass has not only good chemical resistance (water resistance, acid resistance and alkali resistance), but also good flexural strength, the glass has low high temperature viscosity, good chemical stability, is not easy to crystallize, has a good linear thermal expansion coefficient and a low processing temperature.

[0046] In some embodiments of the present invention, a glass comprises silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.90wt% to 1.52wt%, and the content of yttrium trioxide is 1.86wt% to 2.67wt%; the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1; the content of zinc oxide is 0.5wt% to 2.5wt%; the alkaline earth metal oxide comprises at least one selected from calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxide comprises at least one selected from sodium oxide, potassium oxide and lithium oxide; the glass has not only good chemical resistance (water resistance, acid resistance and alkali resistance), but also good flexural strength, low high temperature viscosity, good chemical stability, not easy to crystallize, good linear thermal expansion coefficient and low processing temperature.

[0047] In some embodiments of the present invention, a glass comprises silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide, zirconium dioxide, yttrium trioxide and zinc oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.90wt% to 1.52wt%, the content of yttrium trioxide is 1.86wt% to 2.67wt%; the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1; the content of zinc oxide is 0.84wt% to 1.50wt%. t% (the content of zinc oxide is preferably 1.10wt% to 1.50wt%); the alkaline earth metal oxide includes at least one selected from calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxide includes at least one selected from sodium oxide, potassium oxide and lithium oxide; the glass not only has good chemical resistance (water resistance, acid resistance and alkali resistance), but also has good flexural strength, the glass has low high temperature viscosity, good chemical stability, is not easy to crystallize, has a good linear thermal expansion coefficient and a low processing temperature.

[0048] In the glass of the present invention, the mass content of silicon dioxide is 66.0wt% to 74.0.0wt%, preferably 68.0wt% to 72.0wt%, based on the total weight of the glass. Within this range, the network structure of the glass is highly dense and the various properties of the glass are excellent. When the content of silicon dioxide is higher than 75.0wt%, the high-temperature viscosity of the glass is increased, making the clarification of the glass more difficult, the melting temperature is higher, and the molding temperature is higher. If the content is lower than 60.0wt%, the structure of the glass will be loose, the thermal stability and chemical stability will not meet the requirements, and the thermal expansion coefficient will be too high, resulting in limited application of the glass.

[0049] In the present glass formula, the content of boron trioxide is 8.0wt% to 13.0.0wt% based on the total weight of the glass. Boron trioxide within this range can reduce the melting temperature and the molding temperature, reduce the linear expansion coefficient of the glass, and improve the thermal stability and chemical stability of the glass; in the present invention, when the content of boron trioxide is lower than 6.0wt%, the high-temperature viscosity of the glass is large and the molding temperature is high, and when the content of boron trioxide is higher than 15.0wt%, the acid resistance of the glass deteriorates. Further research has found that the greater the content of boron trioxide, the more serious the volatilization of boron, which will not only aggravate the erosion of refractory materials, increase the cost of glass, cause energy waste, but also lead to fluctuations in the chemical composition of the glass. In addition, a higher content of boron trioxide will also have an adverse effect on the acid resistance of the glass. Therefore, the content of boron trioxide should not be too low or too high, and the above content is the preferred range.

[0050] In the glass of the present invention, the content of aluminum oxide is 2.0wt% to 7.0wt%, preferably 4.2wt% to 5.5wt%, based on the total weight of the glass. Adding an appropriate amount of aluminum oxide to the glass can capture non-bridging oxygen to form "AlO4", enter the silicon oxygen network, connect the broken network, and make the glass structure tend to be compact, thereby improving the anti-analysis performance and mechanical strength of the glass. The addition of aluminum oxide can also slightly improve the chemical stability of the glass. Aluminum oxide can also reduce the erosion of glass on refractory materials. Aluminum oxide and silicon dioxide can increase the high-temperature viscosity of the glass, thereby reducing the volatilization of boron during the glass melting process. Since the raw material boron oxide in neutral borosilicate glass is relatively expensive, high viscosity has a great role in reducing production costs. However, if the high-temperature viscosity is too high, it will make it very difficult to clarify the glass, which greatly affects the yield of glass tubes / bottles. The above-mentioned silicon dioxide and aluminum oxide content is a preferred range.

[0051] When the network structure of glass is dense, the corresponding flexural strength of glass will be enhanced, and glass will be more difficult to be broken by external force, but this will inevitably lead to a significant increase in the viscosity of glass, which not only increases the difficulty of melting glass, but also increases the cost of glass exponentially. The inventor of this patent has found through a lot of research that in the present invention, the mutual polarization between ions has a significant effect on viscosity. Since polarization causes ions to deform, the bond strength of the Si-O covalent bond of the glass former is weakened, and the temperature corresponding to the same viscosity value is lower; zinc oxide is a very ideal oxide, and zinc oxide also increases viscosity at low temperatures, but reduces viscosity at high temperatures. By using the combined effect of these properties, a network with a higher viscosity at low temperatures can be obtained. By adding zinc oxide, the glass has greater flexural strength.

[0052] In the present invention, in some embodiments, based on the total weight of the glass, the calcium oxide content in the alkaline earth metal is 1.0wt% to 2.5wt%, the barium oxide content is 0 to 2.0wt%, the magnesium oxide content is 0 to 2.0wt%, and the total content of calcium oxide, barium oxide and magnesium oxide is 0.5wt% to 3.5wt%. This is because the alkaline earth metal oxide changes the "material length of the glass", that is, the processing temperature range of the glass; in addition, the alkaline earth metal oxide reduces the high-temperature viscosity of the glass through different network modification effects, improves the chemical stability, reduces the tendency of crystallization, and matches the viscosity characteristics and other properties of the glass with specific production and processing processes. In addition, calcium oxide improves acid resistance, and barium oxide reduces the processing temperature without adversely affecting water resistance. Too high an alkaline earth metal oxide content will lead to an increase in the linear thermal expansion coefficient, while too low a content will excessively damage the performance of the glass.

[0053] In the present invention, in some embodiments, based on the total weight of the glass, the content of alkali metal sodium oxide is 3.0wt% to 9.0wt%, the content of potassium oxide is 0 to 3.0wt%, the content of lithium oxide is 0 to 3.0wt%, and the total content of sodium oxide, potassium oxide and lithium oxide is 4.5wt% to 10.5wt%. This is because the alkali metal oxides adjust the glass properties within their respective upper limits. For example, the combination of the three plays an important role in adjusting the linear thermal expansion coefficient of the glass. Sodium oxide and lithium oxide reduce the glass melting temperature and processing temperature. Potassium oxide and / or lithium oxide play a beneficial role in reducing the crystallization of the glass. It is important to maintain a balanced ratio between them. When the respective upper limits are exceeded, the glass has an excessively high linear thermal expansion coefficient and is not conducive to reducing costs, while the alkali metal oxide content is too low, resulting in a too low linear thermal expansion coefficient. Therefore, when the alkali metal oxide content is limited to the above range, borosilicate glass that meets the requirements of linear thermal expansion coefficient and processing temperature can be obtained.

[0054] Through extensive research by the inventors, it is found that adding zirconium dioxide to the glass of the present invention can greatly increase the alkali resistance of the glass, but if the zirconium dioxide content is too high, it is easy to increase the forming temperature and melting temperature of the glass, resulting in a significant increase in production costs; in the glass of the present invention, through the inventors' research, it is found that introducing yttrium trioxide into the glass system can reduce the high-temperature viscosity of the glass liquid and the melting temperature and transition temperature of the glass, but the addition of yttrium trioxide makes the glass easy to crystallize and lose transparency (transparency is reduced). The inventors found that when zirconium dioxide and yttrium trioxide are added to the glass of the present invention together, it not only has good chemical resistance (water resistance, acid resistance and alkali resistance), but is also not easy to lose transparency. Through research, it was found that when the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, based on the total weight of the glass, the zirconium dioxide content is preferably 0.88wt% to 2.00wt%, and the zirconium oxide content is more preferably 0.90wt% to 1.52wt%. The glass system of the present invention not only has good chemical resistance (water resistance, acid resistance and alkali resistance), but also has good transparency.

[0055] The inventors of the present invention have discovered through research that by simultaneously adding a certain amount of zirconium dioxide, yttrium trioxide and zinc oxide to glass, the alkali resistance and flexural strength of the glass can be improved simultaneously, compared with glass to which only zirconium dioxide and yttrium trioxide are added without zinc oxide, or glass to which only zinc oxide is added without zirconium dioxide and yttrium trioxide.

[0056] The glass provided by the present invention not only has good chemical resistance (water resistance, acid resistance and alkali resistance), but also has good flexural strength, low high-temperature viscosity of the glass, good chemical stability (good water resistance, acid resistance and alkali resistance), is not easy to crystallize, has a good linear thermal expansion coefficient and a lower processing temperature.

[0057] In a second aspect, the present invention further provides a method for preparing the glass described in the first aspect.

[0058] A method for preparing the glass of the first aspect comprises: uniformly mixing silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxides, alkali metal oxides and other oxides, and then performing melting homogenization, molding and annealing to obtain the glass.

[0059] The melt homogenization includes two stages: the temperature of the first stage is 1250°C to 1350°C and is kept at 1250°C to 1350°C for 1-3 hours, and the temperature of the second stage is 1550°C to 1670°C and is kept at 1550°C to 1670°C for 3-5 hours.

[0060] The melt homogenization can be carried out in a corundum crucible.

[0061] The melting and homogenization can be carried out in a high-temperature silicon-molybdenum rod electric furnace.

[0062] The melting and homogenization can be carried out in a corundum crucible and a high-temperature silicon-molybdenum rod electric furnace.

[0063] The molding can be performed in a graphite mold preheated to 200°C to 300°C.

[0064] The annealing includes keeping the temperature in an annealing furnace at 550°C±50°C for 2 hours and then cooling the furnace to 10°C-30°C.

[0065] In some embodiments, a method for preparing the above-mentioned glass includes: mixing silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxides, alkali metal oxides and other oxides evenly; loading into a corundum crucible, placing the crucible in a high-temperature silicon-molybdenum rod electric furnace at room temperature, heating, and keeping it at 1250°C to 1350°C for 1-3 hours, and then heating it again, and keeping it at 1550°C to 1670°C for 3-5 hours to obtain melted glass liquid; then taking out the melted glass liquid and pouring it into a preheated graphite mold to form it; then placing the formed sample in an annealing furnace at a temperature of 500°C to 600°C, keeping it for 1-3 hours, and then cooling it to 10°C to 30°C with the furnace to obtain the glass.

[0066] In a third aspect, the present invention further provides a use of the glass described in the first aspect.

[0067] The glass described in the first aspect can be used in many aspects, including but not limited to packaging materials. The glass can be used as primary packaging materials for drugs, such as vials, ampoules, oral liquid bottles, infusion bottles, etc.; it can also be used in chemical reagent bottles, cosmetic packaging bottles, pesticide packaging bottles, food packaging bottles, and seasoning packaging bottles, etc.

[0068] Beneficial effects:

[0069] Compared with the prior art, the beneficial technical effects of the present invention include:

[0070] (1) Through research, it is found that conventional or simple addition of one or / and several oxides cannot achieve the goal of enhancing the alkali resistance and the flexural strength of glass at the same time. If zirconium dioxide and yttrium trioxide are not added to the formula, the strength of the glass can reach 80-90MPa, but the alkali resistance of the glass is weak and cannot meet the requirements of pharmaceutical glass. The addition of zirconium dioxide and yttrium trioxide can enhance the alkali resistance of glass within a certain range, making it meet the requirements of pharmaceutical glass, but its strength is generally weak, with a maximum of only 68.31MPa.

[0071] Without adding zirconium dioxide and yttrium trioxide, the alkali resistance of the obtained glass is poor. After adding zirconium dioxide and yttrium trioxide, the alkali resistance of the obtained glass reaches that of Class 1 glass.

[0072] In some embodiments, only by adding zinc oxide, zirconium dioxide and yttrium trioxide at a certain content, can the flexural strength (which can be used for anti-shattering bottles) be improved while meeting the chemical resistance (water resistance, acid resistance and alkali resistance). Glass to which only zirconium dioxide and yttrium trioxide are added without zinc oxide, or glass to which only zinc oxide is added without zirconium dioxide and yttrium trioxide, has a low flexural strength. When zirconium dioxide and yttrium trioxide or zinc oxide are added at the same time, and only the content of zinc oxide is 0.84wt% to 1.50wt% (preferably 1.10wt% to 1.50wt%) based on the total weight of the glass, and the molar ratio of zirconium dioxide to yttrium trioxide is 0.67:1 to 1.50:1, and the amount of zirconium dioxide is preferably 0.90wt% to 1.52wt%, the chemical resistance (water resistance, acid resistance and alkali resistance) and flexural strength of the glass can reach the best, compared with the glass with only zirconium dioxide and yttrium trioxide added but no zinc oxide, or the glass with only zinc oxide added but no zirconium dioxide and yttrium trioxide added, its alkali resistance and flexural strength are significantly improved. Within the scope of the patent formula, the flexural strength of the glass can reach a maximum of 135.34MPa, while the water resistance of the glass reaches level 1, the acid resistance reaches level 1, and the alkali resistance reaches level 1. The glass of the present invention is suitable for containing medicines, in particular for packaging glass bottles for alkaline medicines.

[0073] (2) The preparation method provided by the present invention has low melting temperature and molding temperature, and the preparation process is simple.

[0074] (3) When zirconium dioxide and yttrium trioxide are added together to the glass of the present invention, it not only has good chemical resistance (water resistance, acid resistance and alkali resistance), but is also not easy to lose transparency, and the obtained glass has good transparency.

[0075] Terminology Note:

[0076] wt% means weight percentage or weight %; n(zirconium dioxide) / n(yttrium trioxide) means the ratio of the molar ratio of zirconium dioxide to yttrium trioxide.

[0077] Room temperature refers to ambient temperature, which is between 0°C and 45°C, or between 10°C and 30°C, or between 20°C and 28°C.

[0078] The principle of flexural strength is to apply a bending load to a beam specimen with a rectangular cross-section until the specimen breaks. Assuming that the specimen material is isotropic and linear elastic, the bending strength of the specimen can be calculated based on the critical load at fracture, the size of the fixture and the specimen.

[0079] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction. DETAILED DESCRIPTION

[0080] In order to enable those skilled in the art to better understand the technical solution of the present invention, some non-limiting embodiments are further disclosed below to further describe the present invention in detail.

[0081] The reagents used in the present invention can be purchased from the market or prepared by the method described in the present invention.

[0082] Test methods for various performance parameters:

[0083] Water resistance test method: According to YBB00362004-2015, take a certain amount of glass particles of specified size, put them in a specified container, add a certain amount of water, and heat them under specified conditions. By titrating the leaching solution, the volume of hydrochloric acid titration solution (0.01mol / L) consumed per gram of glass particles is used to measure the degree of water erosion of the glass particles and classify them. Glass with a maximum volume of hydrochloric acid titration solution (0.01mol / L) consumed per gram of glass particles of 0.10mL belongs to HGB1 grade water-resistant glass. Glass with a volume of hydrochloric acid titration solution (0.01mol / L) consumed per gram of glass particles of greater than 0.10mL to less than or equal to 0.20mL belongs to HGB2 grade water-resistant glass. Glass with a volume of hydrochloric acid titration solution (0.01mol / L) consumed per gram of glass particles of greater than 0.20mL to less than or equal to 0.85mL belongs to HGB3 grade water-resistant glass.

[0084] Alkali resistance test method: According to YBB00352004-2015, the total surface area is 10cm 2 -15cm 2 A glass sample is etched with a boiling mixed solution of equal volumes of 0.5 mol / L sodium carbonate and 1.0 mol / L sodium hydroxide for 3 hours. The mass lost per unit surface area of ​​the glass sample is measured. Each example in the table gives the mass lost per unit surface area in mg / dm 2 The maximum weight loss of Class 1 alkali-resistant glass is 75 mg / dm 2The weight loss of the alkali-resistant glass of level 2 is greater than 75 mg / dm 2 To less than or equal to 175mg / dm 2 . Greater than 175mg / dm 2 It is level 3 alkali resistant.

[0085] Acid resistance test method: According to YBB00342004-2015, the 2 The glass sample was etched in boiling 6±0.2mol / L hydrochloric acid solution for 6 hours, and the mass loss per unit area was measured. Each example in the table gives the mass loss in mg / dm 2 The maximum weight loss of grade 1 acid-resistant glass is 0.7 mg / dm 2 The weight loss of glass belonging to grade 2 acid resistance is greater than 0.7 mg / dm 2 To less than or equal to 1.5mg / dm 2 . Greater than 1.5 mg / dm 2 To less than or equal to 15mg / dm 2 It is grade 3 acid resistant.

[0086] Test method for linear thermal expansion coefficient: the ratio of the change in length of a solid substance to its length at the original temperature (not necessarily 0°C) when the temperature changes by 1°C, with the unit of 1 / °C. Referring to YBB00202003-2015, a micro-controlled internal cutting machine (J5085-1 / ZF of Northwest Machinery Co., Ltd.) was used to cut the glass block into glass strips with length × width × height = 25 × 6 × 6 (error ± 0.1 mm), and then a thermal expansion instrument (NETZSCH DIL 402PC) was used to measure the α(20; 300)[10 -6 / K].

[0087] Test method for flexural strength of glass: refer to the test method for bending strength of fine ceramics (GB / T 6596-2006), first use a micro-controlled internal circle cutting machine (Northwest Machinery Co., Ltd. J5085-1 / ZF) to cut the glass block into glass strips with length × width × height = 50 × 6 × 5 (error ± 0.1mm), and then use the three-point bending method to test the bending strength (MPa) of the glass strips.

[0088] Example 1

[0089] Weigh each component according to the weight percentage of various raw material components in Table 1, with a total weight of 200g, mix them evenly in a mortar, and put them into a clean corundum crucible. Place the crucible in a high-temperature silicon-molybdenum rod electric furnace at room temperature, set the electric furnace heating rate to 10℃ / min, heat it to 1300℃, and keep it at 1300℃ for 2h, then set the heating rate to 5℃ / min, heat it to 1550℃~1670℃, and keep it at this temperature for 4h to fully melt the glass liquid to clarify. Take out the melted glass liquid and pour it into the preheated graphite mold. After forming, put the sample into an annealing furnace at a temperature of 580℃±30℃, keep it warm for 2h, and then cool it to room temperature with the furnace. Prepare the obtained glass block sample into the required shape / state according to the test requirements. The linear thermal expansion coefficient, water resistance, acid resistance, alkali resistance, and flexural strength of the glass will be determined according to the above test method. Detailed data are shown in Table 1.

[0090] Table 1: Composition (by total weight of glass, based on oxides) and main properties of the glass

[0091]

[0092]

[0093] Example 2

[0094] Weigh each component according to the weight percentage of each raw material component in Table 2, with a total weight of 200 g. The preparation method and detection method are the same as those described in Example 1. See Table 2 for detailed data.

[0095] Table 2: Composition (by total weight of glass, based on oxides) and main properties of the glass

[0096]

[0097]

[0098] Example 3

[0099] Weigh each component according to the weight percentage of each raw material component in Table 3-Table 4, with a total weight of 200 g. The preparation method and detection method are the same as those described in Example 1. Detailed data are shown in Table 3-Table 4.

[0100] Table 3: Composition (by total weight of glass, based on oxides) and main properties of the glass

[0101]

[0102]

[0103] Table 4: Composition (based on total weight of glass, oxides) and main properties of glass

[0104]

[0105]

[0106] Result analysis:

[0107] According to the results of A1-A7, B1-B7, C1-C14, it can be seen that conventional or simple addition of one or / and several oxides cannot achieve the goal of enhancing the alkali resistance and the flexural strength of glass at the same time. A1-A7 also show that if zirconium dioxide and yttrium trioxide are not added to the formula, the strength of the glass can reach 80-90MPa, but the alkali resistance of the glass is weak and cannot meet the requirements of pharmaceutical glass. B1-B7 show that the addition of zirconium dioxide and yttrium trioxide can enhance the alkali resistance of glass within a certain range to meet the requirements of pharmaceutical glass, but its strength is generally weak, with a maximum of only 68.31MPa.

[0108] From the results of A1-A7 and B1-B7, it can be seen that when zirconium dioxide and yttrium trioxide are not added, the alkali resistance of the obtained glass is poor. After adding zirconium dioxide and yttrium trioxide, a glass can be obtained which not only maintains HGB1 level of water resistance and level 1 of acid resistance, but also has level 1 of alkali resistance.

[0109] From the above results, it can be seen that only by adding zinc oxide, zirconium dioxide and yttrium trioxide at a certain content, can the flexural strength be improved while meeting the chemical resistance (water resistance, acid resistance and alkali resistance). From the results of A1-A7 and B1-B7, it can be seen that the flexural strength of the glass to which only zirconium dioxide and yttrium trioxide are added without zinc oxide, or the flexural strength of the glass to which only zinc oxide is added without zirconium dioxide and yttrium trioxide is low; from the results of C1-C14, it can be seen that zirconium dioxide and yttrium trioxide or zinc oxide are added at the same time, and the content of only zinc oxide is 0.84wt% to 1.50wt% (preferably 1.10wt% to 1.50wt%) based on the total weight of the glass, and the flexural strength of the glass to which only zinc dioxide and yttrium trioxide are added is low. The molar ratio of zirconium to yttrium trioxide is 0.67:1 to 1.50:1, and the amount of zirconium dioxide is preferably 0.90wt% to 1.52wt%, the chemical resistance (water resistance, acid resistance and alkali resistance) and flexural strength of the glass can reach the best, compared with the glass with only zirconium dioxide and yttrium trioxide added, without zinc oxide, or the glass with only zinc oxide added, without zirconium dioxide and yttrium trioxide added, its chemical resistance (water resistance, acid resistance and alkali resistance) and flexural strength are significantly improved. Within the scope of the patent formula, the flexural strength of the glass can reach a maximum of 135.34MPa, while the water resistance of the glass reaches HGB1 level, the acid resistance reaches level 1, and the alkali resistance reaches level 1. The glass of the present invention is suitable for the storage of drugs, especially for the packaging glass bottles of alkaline drugs.

[0110] The method of the present invention has been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications described herein within the content, spirit and scope of the present invention to implement and apply the technology of the present invention. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters. It is particularly important to point out that all similar replacements and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention.

Claims

1. A glass comprising silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxides, alkali metal oxides and other oxides, wherein the other oxides are zirconium dioxide, yttrium trioxide and zinc oxide; the alkaline earth metal oxides are calcium oxide, barium oxide, strontium peroxide and magnesium oxide; the alkali metal oxides are sodium oxide, potassium oxide and lithium oxide; based on the total weight of the glass, the content of zirconium dioxide is 0.90wt% to 1.52wt%; the content of yttrium trioxide is 1.86wt% to 3.01wt%; the molar ratio of zirconium dioxide to yttrium trioxide ... is 0.67:1 to 1.50:1; the content of zinc oxide is 1.10wt% to 1.50wt%; the content of silicon dioxide is 66.0wt% to 74.0wt%; the content of boron trioxide is 8.0wt% to 13.0wt%; the content of aluminum trioxide is 2.0wt% to 7.0wt%; the total content of calcium oxide, barium oxide and magnesium oxide in the alkaline earth metal oxide is 0.5wt% to 3.5wt%; and the total content of sodium oxide, potassium oxide and lithium oxide in the alkali metal oxide is 4.5wt% to 10.5wt%.

2. A method for preparing the glass according to claim 1, comprising: The glass is obtained by uniformly mixing silicon dioxide, boron trioxide, aluminum trioxide, alkaline earth metal oxide, alkali metal oxide and other oxides, and then melting, homogenizing, molding and annealing.

3. The method according to claim 2, wherein the melt homogenization comprises two stages: the temperature of the first stage is 1250°C to 1350°C, and the temperature is kept for 1-3 hours; the temperature of the second stage is 1550°C to 1670°C, and the temperature is kept for 3-5 hours.

4. The method according to claim 2 or 3, wherein the melt homogenization is carried out in a corundum crucible and / or a high-temperature silicon-molybdenum rod electric furnace; and / or the molding is carried out in a graphite mold preheated to 200°C to 300°C; and / or the annealing includes being kept in an annealing furnace at 500°C to 600°C for 1-3 hours and then cooled to 10°C to 30°C with the furnace.

5. Use of the glass according to claim 1 in packaging materials.

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