Glass for pharmaceutical containers, glass tubes for pharmaceutical containers using the same, and pharmaceutical containers

Abstract

This invention provides a glass for pharmaceutical containers that combines excellent hydrolysis resistance and processability, as well as glass tubes and pharmaceutical containers using the same. [Solution] The glass for pharmaceutical containers of the present invention is characterized in that, as a glass composition, it contains, in molar percentages, SiO2 60-85%, Al2O3 3-20%, B2O3 0-5%, Li2O 0-9%, Na2O 0-12%, K2O 0-6%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, and BaO 0-1%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.60 or less and a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 50 or less.

Description

[Technical Field]

[0001] This invention relates to a glass for pharmaceutical containers that is excellent in processability and hydrolysis resistance, a glass tube for pharmaceutical containers using the same, and a pharmaceutical container. [Background technology]

[0002] Traditionally, various glass containers have been used as filled containers for storing pharmaceuticals. Pharmaceuticals are broadly classified into two types: oral and parenteral drugs. Parenteral drugs, in particular, require extremely high quality glass containers because the medication, filled and stored in glass containers, is administered directly into the patient's bloodstream.

[0003] Furthermore, pharmaceutical containers are required to prevent the deterioration of the drug components they contain. If glass components leach into the drug, it can alter the drug's properties and potentially affect the patient's health, and even their life. For this reason, the amount of glass components that leach from pharmaceutical container glass is restricted by national pharmacopoeias.

[0004] Therefore, borosilicate glass is used as a glass material that meets the standards for components leached from glass.

[0005] In recent years, advancements in medicine and pharmacology have led to the development of highly effective drugs. However, a problem has arisen with the use of glass containers containing high levels of B2O3 to store such drugs. This process, known as delamination, causes the inner surface of the glass container to erode, leading to the peeling of the inner surface and the floating flakes of material within the drug. Insoluble foreign matter generated by delamination, when injected into a patient's body along with the drug, can be harmful to the human body, potentially forming blood clots in blood vessels.

[0006] Furthermore, in order to accommodate such highly effective drugs, there is a demand for glass that exhibits less leaching of glass components into water and drugs than conventional glass, and that is more resistant to hydrolysis.

[0007] Because glass for pharmaceutical containers, such as ampoules, vials, pre-filled syringes, and cartridges, requires processing into complex shapes, it is also desirable that the glass has low viscosity and excellent processability. Furthermore, regarding the working temperature during processing, if the working temperature is high, components contained in the glass are more likely to evaporate during processing, which may contaminate the inner surface of the container and, consequently, the drug inside the glass container. [Prior art documents] [Patent Documents]

[0008] Patent document 1: WO2013 / 063275 publication [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] Given the circumstances described above, Patent Document 1 proposes glass with reduced B2O3 content for the purpose of reducing delamination. However, reducing B2O3 increases the viscosity of the glass, so a large amount of Na2O is added to lower the viscosity of the glass. As a result, there is a problem of poor hydrolysis resistance.

[0010] The technical problem of the present invention is to obtain a glass for pharmaceutical containers that achieves both excellent hydrolysis resistance and processability, as well as a glass tube and pharmaceutical container using the same. [Means for solving the problem]

[0011] The inventors of this invention have conducted thorough research on each component that makes up glass and have found that the above problems can be solved by strictly regulating the content of each component, and propose this as the present invention.

[0012] Specifically, the glass for pharmaceutical containers of the present invention improves the hydrolysis resistance of the glass by strictly controlling the amount of Na2O, which easily affects the hydrolysis resistance of the glass. Furthermore, by strictly controlling the molar ratios of K2O / (Li2O+Na2O+K2O) and Al2O3 / (Li2O+Na2O+K2O), it is possible to achieve both excellent hydrolysis resistance and processability.

[0013] In other words, the glass for pharmaceutical containers of the present invention is characterized in that, as a glass composition, it contains, in molar percentages, SiO2 60-85%, Al2O3 3-20%, B2O3 0-5%, Li2O 0-9%, Na2O 0-12%, K2O 0-6%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, and BaO 0-1%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.60 or less and a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 50 or less. Here, "Li2O+Na2O+K2O" refers to the total amount of Li2O, Na2O, and K2O contained, "K2O / (Li2O+Na2O+K2O)" refers to the value obtained by dividing the amount of K2O by the total amount of Li2O, Na2O, and K2O contained, and "Al2O3 / (Li2O+Na2O+K2O)" refers to the value obtained by dividing the amount of Al2O3 contained by the total amount of Li2O, Na2O, and K2O contained.

[0014] This approach makes it easier to obtain glass for pharmaceutical containers that combines excellent hydrolysis resistance with processability.

[0015] The glass for pharmaceutical containers of the present invention preferably contains Li2O 0-7%, Na2O 0-7.9%, and K2O 0-3% as its glass composition.

[0016] This makes it easier to obtain better hydrolysis resistance.

[0017] The glass for pharmaceutical containers of the present invention preferably has a combined content of 0 to 5 mol% of MgO, CaO, SrO, and BaO.

[0018] By doing so, it becomes easy to obtain more excellent hydrolysis resistance.

[0019] The glass for pharmaceutical containers of the present invention preferably contains MgO 0 to 0.5%, CaO 0 to 0.5%, SrO 0 to 0.3%, and BaO 0 to 0.3% in mol%.

[0020] By doing so, it becomes easy to obtain more excellent hydrolysis resistance.

[0021] The glass for pharmaceutical containers of the present invention preferably has a value of the molar ratio K2O / (Li2O + Na2O + K2O) of 0.24 or less.

[0022] By doing so, it becomes easy to obtain more excellent workability.

[0023] The glass for pharmaceutical containers of the present invention preferably has a value of the molar ratio Al2O3 / (Li2O + Na2O + K2O) of 0.85 or less.

[0024] By doing so, it becomes easy to obtain more excellent workability.

[0025] The glass for pharmaceutical containers of the present invention preferably has a B2O3 content of 0.01 to 1 mol%.

[0026] By doing so, it is possible to obtain good workability while suppressing the occurrence of delamination.

[0027] The glass for pharmaceutical containers of the present invention preferably has a ZrO2 content of 0 to 2 mol%.

[0028] The glass for pharmaceutical containers of the present invention is characterized in that, as a glass composition, it contains, in molar percent, SiO2 60-85%, Al2O3 5-17.5%, B2O3 0-4%, Li2O 0-6%, Na2O 0-8.3%, K2O 0-5%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, BaO 0-1%, and MgO+CaO+SrO+BaO 0-5%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.24 or less and a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 0.67 or less.

[0029] The glass for pharmaceutical containers of the present invention is characterized in that, as a glass composition, it contains, in molar percent, SiO2 60-85%, Al2O3 5-17.5%, B2O3 0-5%, Li2O 0-7%, Na2O 0-8.3%, K2O 0-5%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, BaO 0-1%, and MgO+CaO+SrO+BaO 0-3.7%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.24 or less and a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 0.67 or less.

[0030] The glass for pharmaceutical containers of the present invention is characterized by containing, in molar percentages, SiO2 60-85%, Al2O 35-20%, B2O 30-5%, Li2O+Na2O+K2O 0.1-26%, and MgO+CaO+SrO+BaO 0-3%.

[0031] The glass for pharmaceutical containers of the present invention is characterized in that, as a glass composition, it contains, in molar percent, SiO2 60-85%, Al2O3 3-7%, B2O3 0-5%, Li2O 0-7%, Na2O 0-8.3%, K2O 0-5%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, BaO 0-1%, and MgO+CaO+SrO+BaO 0-3.7%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.24 or less, a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 0.5 or less, and a molar ratio of SiO2 / Al2O3 of 16 or less.

[0032] Furthermore, it is preferable that the glass for pharmaceutical containers of the present invention has a class of at least HGA1 in the hydrolysis resistance test (acetone washing) in accordance with ISO720.

[0033] In this invention, "hydrolysis resistance test in accordance with ISO 720 (acetone cleaning)" refers to the following test. (1) The glass sample is crushed in an alumina mortar and then classified into 300-425 μm particles using a sieve. (2) Wash the obtained powder sample with acetone and dry it in an oven at 140°C. (3) Place 10 g of the dried powder sample into a quartz flask, add 50 mL of purified water, cover, and process in an autoclave. The process is carried out under the following conditions: raise the temperature from 100°C to 121°C at a rate of 1°C / min, hold at 121°C for 30 minutes, and then lower the temperature to 100°C at a rate of 0.5°C / min. (4) After autoclaving, transfer the solution in the quartz flask to another beaker, then wash the inside of the quartz flask three times with 15 mL of purified water, and add the washing solution to the beaker. (5) Add methyl red indicator to the beaker and titrate with 0.02 mol / L hydrochloric acid solution. (6) Convert the amount of alkali eluted per gram of glass by assuming that 1 mL of 0.02 mol / L hydrochloric acid aqueous solution is equivalent to 620 μg of Na2O.

[0034] Furthermore, "the class in the hydrolysis resistance test (acetone washing) in accordance with ISO720 is at least HGA1" means that the amount of alkali eluted per gram of glass, calculated as Na2O by the above test, is 62 μg / g or less.

[0035] The glass for pharmaceutical containers of the present invention preferably has a working point of 1300°C or lower. The "working point" is defined as the viscosity of the glass being 10°C or lower. 4.0 This refers to the temperature at which the temperature becomes dPa·s.

[0036] This method eliminates the need to raise the processing temperature when manufacturing pharmaceutical containers, thus reducing the evaporation of glass components during processing and making it easier to suppress contamination of the inner surface of the container.

[0037] The glass tube for pharmaceutical containers of the present invention is preferably made of the above-described glass for pharmaceutical containers.

[0038] The pharmaceutical container of the present invention is preferably made of the above-described glass for pharmaceutical containers. The glass for pharmaceutical containers of the present invention has high hydrolysis resistance. Furthermore, because the processing temperature can be lowered, evaporation of glass components during processing can be reduced, making it easier to suppress contamination of the inner surface of the container. As a result, it is easier to obtain a pharmaceutical container with excellent hydrolysis resistance and, consequently, chemical durability. [Modes for carrying out the invention]

[0039] The reasons for limiting the composition range of each component are explained below. Unless otherwise specified, "%" in the following explanation refers to "molar percent".

[0040] SiO2 is one of the components that make up the network structure of glass. If the SiO2 content is too low, vitrification becomes difficult, and the coefficient of thermal expansion increases, making it easier for thermal shock resistance to decrease. On the other hand, if the SiO2 content is too high, the liquidus temperature rises, making it easier for devitrification to occur. Therefore, the SiO2 content is preferably 60-85%, 65-85%, 68-83%, and especially 70-80%.

[0041] Al2O3 is one of the components that make up the network structure of glass and has the effect of improving the hydrolysis resistance of glass. If the Al2O3 content is too low, the hydrolysis resistance tends to deteriorate. On the other hand, if the Al2O3 content is too high, the viscosity increases. Therefore, the Al2O3 content is preferably 3-20%, 4-20%, 4-17.5%, 4.5-17.5%, 5-15%, 5.3-14%, 5.4-13%, 5.5-12.4%, 5.6-12%, 5.7-11.5%, 5.8-11%, 5.9-10%, and especially 6-9%.

[0042] B2O3 has the effect of lowering the viscosity of glass and improving its meltability and processability. However, B2O3 is considered to be one of the factors that cause delamination, and if its content becomes too high, the delamination resistance deteriorates and flake formation becomes more likely. Therefore, the B2O3 content is preferably 0-5%, and is particularly good if it is 0.01-4%, 0.02-3%, 0.03-2%, 0.04-1%, 0.04-0.8%, and especially 0.05-0.5%.

[0043] Alkali metal oxides (R2O), namely Li2O, Na2O, and K2O, have the effect of reducing the viscosity of glass and improving its processability and meltability. The lower limit of the total R2O content is preferably 0.1% or more, and is also 0.5% or more, 1% or more, 2% or more, 3% or more, 4% or more, 4.5% or more, 5% or more, 5.5% or more, 6% or more, 6.5% or more, 7% or more, 7.5% or more, and especially 8% or more. When the processability of the glass is particularly important, the lower limit of the total R2O content is 8.5% or more, 9% or more, 9.5% or more, 10% or more, 10.5% or more, and 11% or more. On the other hand, if the total content of these components is too high, the hydrolysis resistance of the glass deteriorates, and the coefficient of thermal expansion increases, reducing its thermal shock resistance. Therefore, the upper limit of the total R2O content is preferably 26% or less, and is also 23% or less, 20% or less, 18% or less, 17.5% or less, 17% or less, less than 17%, 16% or less, 15% or less, 14% or less, 13.9% or less, 13% or less, 12% or less, and especially 11% or less.

[0044] As previously mentioned, Li2O has the effect of reducing the viscosity of glass, thereby improving its processability and meltability. Among R2Os, Li2O is the most effective at reducing the viscosity of glass, followed by Na2O and then K2O. However, if the Li2O content is too high, hydrolysis resistance tends to deteriorate. Therefore, the Li2O content is preferably 0-9%, and also 0-8%, 0-7%, 0-6.5%, 0-6.3%, 0-6.1%, 0-6%, 0-5.9%, 0-5.8%, 0-5.7%, 0-5.5%, 0-5%, 0-4.5%, 0-4%, and especially 0-3.5%. In particular, devitrification resistance is less likely to occur when the Li2O content is 6% or less.

[0045] Furthermore, if the processability of the glass is important, the Li2O content is preferably 0.1 to 9%, but may also be 0.5 to 8%, 1 to 7%, 2 to 6.5%, 2.5 to 6.3%, 3 to 6.1%, 3.5 to 6%, or especially 4 to 5%.

[0046] Furthermore, when prioritizing both processability and hydrolysis resistance of the glass, the Li2O content is preferably 2-8%, 2.5-7%, and particularly 3-6.5%.

[0047] Na2O, like Li2O, has the effect of reducing the viscosity of glass and improving processability and meltability. However, if the content is too low, the devitrification resistance may decrease. On the other hand, as mentioned above, if the content of Na2O is too high, it particularly worsens hydrolysis resistance. Therefore, the Na2O content is preferably 0-12%, and is also suitable in the ranges of 0-10%, 0-9%, 0-8.5%, 0-8.3%, 0-8%, 0-7.9%, 0-7.5%, 0-7%, 0-6.5%, 0-6%, 0-5.5%, and especially 0-5%.

[0048] Furthermore, if the processability of the glass is important, the Na2O content is preferably 0.1 to 12%, but may also be 0.5 to 11%, 1 to 10%, 2 to 9%, 2.5 to 8.5%, 3 to 8%, 3.5 to 7.9%, 4 to 7.5%, 4.5 to 7%, and especially 5 to 6.5%.

[0049] Although K2O is present in lower amounts compared to Li2O and Na2O, it has the effect of reducing the viscosity of glass and improving processability and meltability. However, if the K2O content is too high, hydrolysis resistance deteriorates. On the other hand, if the content is too low, devitrification resistance may decrease. Therefore, the K2O content is preferably 0-6%, and is also acceptable at 0-5%, 0-4%, 0-3%, 0-2.9%, 0-2.8%, 0-2.7%, 0-2.6%, 0-2.5%, 0-2%, and especially less than 0-2%.

[0050] Furthermore, if the processability of the glass is important, the K2O content is preferably 0.01 to 11%, but may also be 0.05 to 10%, 0.1 to 8%, 0.5 to 6%, 0.8 to 5.5%, 1 to 5%, 1.2 to 4%, 1.4 to 3.5%, and especially 1.5 to 3%.

[0051] Among the alkali metal oxides (R2O) mentioned above, Li2O is most effective in reducing the viscosity of glass, followed by Na2O and then K2O. Therefore, from the viewpoint of reducing the viscosity of glass, the relationship between their respective contents is preferably Li2O≧Na2O≧K2O, Li2O≧Na2O>K2O, or Li2O>Na2O≧K2O, and in particular, Li2O>Na2O>K2O is preferable. Furthermore, if the proportion of K2O is too high, it becomes difficult to maintain both good viscosity and hydrolysis resistance in the glass. Therefore, from the viewpoint of achieving both viscosity and hydrolysis resistance, Na2O>K2O is preferable.

[0052] If the proportion of Li2O in the alkali metal oxide (R2O) contained in the glass is too high, the devitrification resistance of the glass decreases. Therefore, in some embodiments, from the viewpoint of devitrification resistance, the relationship Na2O > Li2O may be satisfied among the alkali metal oxide (R2O). Furthermore, K2O has the greatest effect in improving the devitrification resistance of glass, followed by Na2O and then Li2O. From the viewpoint of achieving both hydrolysis resistance and devitrification resistance of glass, it is preferable that Li2O ≥ Na2O ≥ K2O, Li2O ≥ K2O > Na2O, or Li2O > Na2O ≥ K2O, and in particular, Li2O > K2O > Na2O is preferred.

[0053] Furthermore, if the proportion of K2O in the alkali metal oxide (R2O) is too high, the effect of reducing the viscosity of the glass will be reduced. Therefore, the upper limit of the molar ratio K2O / (Li2O+Na2O+K2O) is preferably 0.60 or less, and is particularly 0.50 or less, 0.40 or less, 0.24 or less, 0.22 or less, 0.21 or less, 0.18 or less, and especially 0.15 or less. This makes it easier to reduce the viscosity of the glass. On the other hand, if the value of the molar ratio K2O / (Li2O+Na2O+K2O) is too low, the hydrolysis resistance of the glass may deteriorate. Therefore, the lower limit of the molar ratio K2O / (Li2O+Na2O+K2O) is preferably greater than 0, 0.01 or more, particularly 0.03 or more, 0.05 or more, 0.8 or more, 0.1 or more, and 0.13 or more.

[0054] Increasing the Al2O3 content improves hydrolysis resistance but increases the viscosity of the glass. Conversely, increasing the Li2O, Na2O, and K2O content worsens hydrolysis resistance but decreases the viscosity of the glass. In this invention, in order to achieve both hydrolysis resistance and processability of the glass, it is necessary to strictly control the balance of the content of the components related to these properties. Therefore, the molar ratio Al2O3 / (Li2O+Na2O+K2O) is preferably 50 or less, and is also 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, 3 or less, 2 or less, 1.2 or less, 0 to 1, 0 to 0.85, 0 to 0.8, greater than 0 to 0.74, 0.01 to 0.7, 0.1 to 0.67, 0.2 to 0.65, 0.3 to 0.61, 0.33 to 0.60, 0.34 to 0.59, 0.4 to 0.55, and especially greater than 0.4 to 0.5. As described above, limiting the content of Al2O3, Li2O, Na2O, and K2O makes it easier to achieve both good hydrolysis resistance and processability. In particular, when the molar ratio Al2O3 / (Li2O+Na2O+K2O) is 0.67 or less, it becomes even easier to achieve both hydrolysis resistance and processability.

[0055] If the Al2O3 content is too low relative to SiO2, the hydrolysis resistance and devitrification resistance of the glass deteriorate. In the present invention, in order to maintain good devitrification resistance in addition to hydrolysis resistance and processability of the glass, it is desirable to strictly control the component balance of SiO2 and Al2O3. Therefore, the upper limit range of the molar ratio SiO2 / Al2O3 is preferably 30 or less, 20 or less, 18 or less, 17 or less, 16 or less, and particularly 15 or less. Also, if the Al2O3 content is too high relative to SiO2, it becomes difficult to achieve both hydrolysis resistance and processability. Therefore, the lower limit range of the molar ratio SiO2 / Al2O3 is preferably 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, and particularly 12 or more.

[0056] To achieve both hydrolysis resistance and processability in the glass, it is preferable to regulate the balance between the content of SiO2, which is the most abundant component in this invention, and the content of Li2O, Na2O, and K2O, which have the effect of reducing viscosity. Therefore, the molar ratio SiO2 / (Li2O+Na2O+K2O) is preferably 10 or less, and is 8 or less, 7.9 or less, 7 or less, 6.9 or less, 6.5 or less, 6.1 or less, 6.0 or less, 5.9 or less, and particularly 5.7 or less. By limiting the content of SiO2 and Li2O, Na2O, and K2O as described above, it becomes easier to achieve both good hydrolysis resistance and processability. In particular, when the molar ratio SiO2 / (Li2O+Na2O+K2O) is 6.9 or less, it becomes even easier to achieve both hydrolysis resistance and processability.

[0057] Furthermore, it is preferable to appropriately regulate the value of Li2O / (Na2O+K2O) in alkali metal oxides (R2O). In this way, the effect of Li2O, which is highly effective in reducing viscosity among alkali metal oxides, can be enjoyed while suppressing the effect of Na2O, which particularly worsens hydrolysis resistance. For this reason, the lower limit of Li2O / (Na2O+K2O) is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, and particularly preferably 0.7 or more. On the other hand, if Li2O / (Na2O+K2O) is too large, the raw material cost will increase. For this reason, the upper limit of the molar ratio Li2O / (Na2O+K2O) of the total amount of Li2O, Na2O and K2O is preferably 2.0 or less, and is 1.5 or less, 1.2 or less, 1.1 or less, 1.0 or less, less than 1.0, 0.9 or less, 0.8 or less, and less than 0.8.

[0058] Alkaline earth metal oxides (R'O), such as MgO, CaO, SrO, and BaO, have the effect of reducing the viscosity of glass. They also affect hydrolysis resistance. If the content of these components is too high, the hydrolysis resistance and devitrification resistance of the glass will decrease, and there is a risk that R'O leached from the glass into the chemical will precipitate as carbonates or sulfates. Therefore, the total amount of R'O is preferably 0 to 10%, and is preferably 0 to 5%, 0 to 4%, 0 to 3.7%, 0 to 3%, 0 to 2%, 0 to 1%, 0 to 0.9%, 0 to 0.8%, 0 to 0.7%, 0 to 0.6%, 0 to 0.5%, 0 to 0.4%, 0 to 0.3%, 0 to 0.2%, 0 to 0.1%, 0 to 0.01%, less than 0.01%, or not present at all. In this invention, "not containing" means not actively adding it, and does not mean that unavoidable impurities are excluded.

[0059] Here, the ease with which carbonates or sulfates of R'O precipitate depends on the solubility of each salt. Specifically, MgO has the highest solubility, followed by CaO, SrO, and BaO in decreasing order of solubility. Therefore, MgO is the least likely to precipitate, and BaO is the most likely to precipitate. Thus, when focusing on solubility, the R'O content should preferably be MgO≧CaO≧SrO≧BaO, and more preferably MgO>CaO>SrO>BaO.

[0060] On the other hand, BaO is most effective at reducing the viscosity of glass, followed by SrO, CaO, and MgO in decreasing order of effectiveness. Therefore, when processability is a priority, the R'O content should preferably be BaO≧SrO≧CaO≧MgO, and BaO>SrO>CaO>MgO more preferably.

[0061] Furthermore, it is preferable to restrict the MgO content in the pharmaceutical container glass of the present invention. As mentioned above, MgO has high solubility as a carbonate or sulfate, making it a component that is less prone to salt precipitation. However, since Mg ions readily react with hydrated silicic acid, if Mg ions dissolve from the glass, there is a risk that the hydrated silicic acid formed on the glass surface will react with the Mg ions to form an insoluble magnesium silicate hydrate film. This film may peel off due to vibration or other factors, becoming a flaky, insoluble foreign substance. Also, if the MgO content is too high, the hydrolysis resistance deteriorates. For this reason, it is preferable to strictly restrict the MgO content in the present invention. Therefore, the MgO content is preferably 0-10%, and also includes 0-8%, 0-5%, 0-3%, 0-1%, 0-0.9%, 0-0.8%, 0-0.7%, 0-0.6%, 0-0.5%, 0-0.4%, 0-0.3%, 0-0.2%, 0-0.1%, 0-0.05%, 0-0.03%, less than 0-0.03%, 0-0.01%, and less than 0-0.01%. Furthermore, it is preferable that MgO is not included. However, if the processability of the glass is particularly important, it may contain 0.01% or more of MgO.

[0062] Furthermore, in order to improve hydrolysis resistance, it is preferable to strictly limit the CaO content of the pharmaceutical container glass of the present invention. The CaO content is preferably 0 to 10%, and is also 0 to 8%, 0 to 5%, 0 to 3%, 0 to 1%, 0 to 0.9%, 0 to 0.8%, 0 to 0.7%, 0 to 0.6%, 0 to 0.5%, 0 to 0.4%, 0 to 0.3%, 0 to 0.2%, 0 to 0.1%, 0 to 0.05%, 0 to 0.03%, less than 0 to 0.03%, 0 to 0.01%, and less than 0 to 0.01%. It is also preferable that the glass does not contain CaO. However, if the processability of the glass is particularly important, it may contain 0.01% or more CaO.

[0063] Furthermore, in order to suppress the precipitation of carbonates or sulfates and improve hydrolysis resistance, it is preferable to strictly control the SrO content in the pharmaceutical container glass of the present invention. The SrO content is preferably 0 to 1%, and is preferably 0 to 0.9%, 0 to 0.8%, 0 to 0.7%, 0 to 0.6%, 0 to 0.5%, 0 to 0.4%, 0 to 0.3%, 0 to 0.2%, 0 to 0.1%, 0 to 0.01%, less than 0 to 0.01%, or particularly none.

[0064] Furthermore, in order to suppress the precipitation of carbonates or sulfates and improve hydrolysis resistance, it is preferable to strictly control the BaO content in the pharmaceutical container glass of the present invention. The BaO content is preferably 0 to 1%, and is preferably 0 to 0.9%, 0 to 0.8%, 0 to 0.7%, 0 to 0.6%, 0 to 0.5%, 0 to 0.4%, 0 to 0.3%, 0 to 0.2%, 0 to 0.1%, 0 to 0.01%, less than 0 to 0.01%, or particularly none.

[0065] Furthermore, as mentioned above, MgO has high solubility for carbonates or sulfates, making it a component that is less prone to salt precipitation. On the other hand, Mg ions readily react with hydrated silicic acid, which may lead to the formation of an insoluble magnesium silicate hydrate film. For this reason, it is preferable to regulate the molar ratio MgO / (MgO+CaO+SrO+BaO) in the pharmaceutical container glass of the present invention. The molar ratio MgO / (MgO+CaO+SrO+BaO) is preferably 1 or less, and is particularly 0, less than 1, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, less than 0.5, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less.

[0066] Furthermore, the MgO+CaO value is preferably 0-10%, and is also preferably 0-5%, 0-4%, 0-3.7%, 0-3%, 0-2%, 0-1%, 0-0.9%, 0-0.8%, 0-0.7%, 0-0.6%, 0-0.5%, 0-0.4%, 0-0.3%, 0-0.2%, 0-0.1%, 0-0.01%, less than 0-0.01%, or particularly preferably none. This makes it less likely for carbonate or sulfate to precipitate. Note that "MgO+CaO" refers to the total amount of MgO and CaO contained.

[0067] Furthermore, the molar ratio of MgO to CaO, MgO / CaO, is preferably less than 9.0, and is 8.0 or less, 6.0 or less, less than 5.0, less than 3.0, 1.0 or less, less than 1.0, or 0.5 or less. More preferably, it is 0.9 or less, less than 0.7, less than 0.5, less than 0.4, less than 0.3, less than 0.2, or less than 0.1. By doing so, hydrolysis resistance can be improved. Also, as mentioned above, in the present invention, MgO may form an insoluble magnesium silicate hydrate film, but CaO is a component that reacts less readily with SiO2 than MgO, and is less likely to form an insoluble film. Therefore, by regulating the molar ratio MgO / CaO, the safety of the container can be improved. In addition, the viscosity of the glass can be lowered, so excellent processability can be obtained.

[0068] Furthermore, in order to achieve both hydrolysis resistance and processability, it is more preferable to regulate the balance of CaO and Li2O content in the glass for pharmaceutical containers of the present invention. The molar ratio of CaO to Li2O, CaO / Li2O, is preferably 2.0 or less, and is 1.5 or less, 1.2 or less, 1.1 or less, 1.0 or less, less than 1.0, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, and particularly preferably 0.

[0069] Furthermore, the pharmaceutical container glass of the present invention preferably has a total content of SiO2, Al2O3, B2O3, Li2O, Na2O, K2O, MgO, CaO, SrO, and BaO of 90% or more, and more preferably 93% or more, 95% or more, 96% or more, 97% or more, 98% or more, 98.5% or more, and particularly 99% or more. By doing so, the effects of the above-mentioned components can be obtained efficiently, making it easier to achieve both excellent hydrolysis resistance and processability.

[0070] Furthermore, the glass for pharmaceutical containers of the present invention may contain other components as part of its glass composition. For example, ZrO2 may be included to improve the alkali resistance of the glass. However, if the ZrO2 content is too high, the viscosity of the glass will increase and its devitrification resistance will also decrease. When ZrO2 is included, its content is preferably 0-3%, 0-2.5%, 0-2%, 0-1.5%, 0.1-0.8%, and particularly preferably 0.2-0.6%.

[0071] Furthermore, the pharmaceutical container glass of the present invention may contain ZnO. While ZnO has the effect of reducing the viscosity of the glass, if its content is too high, it will affect the hydrolysis resistance of the glass. In the present invention, the ZnO content is preferably 0 to 4%, 0 to 1%, or preferably none.

[0072] Furthermore, if you want to color the glass, you can add TiO2 and Fe2O3 to the batch raw materials. In this case, the total amount of standard TiO2 and Fe2O3 content is preferably 7% or less, 6% or less, 5% or less, 1% or less, and even 0.5% or less.

[0073] Furthermore, one or more fining agents such as F, Cl, Sb2O3, SnO2, and SO3 may be included. In this case, the standard fining agent content is preferably 5% or less in total, particularly 1% or less, and even more preferably 0.5% or less.

[0074] Furthermore, to improve chemical durability, high-temperature viscosity, etc., P2O5, Cr2O3, PbO, La2O3, WO3, Nb2O3, Y2O3, etc. may be added in amounts of 3% or less, 2% or less, 1% or less, less than 1%, and 0.5% or less, respectively.

[0075] Furthermore, impurities such as H2, CO2, CO, H2O, He, Ne, Ar, and N2 may be included in amounts up to 0.1% each. Preferably, the amount of noble metal elements such as Pt, Rh, and Au is 500 ppm or less, and even more preferably 300 ppm or less.

[0076] In addition to the composition ranges mentioned above, for example, a glass composition containing, in molar percentages, SiO2 60-85%, Al2O3 5-17.5%, B2O3 0-4%, Li2O 0-6%, Na2O 0-8.3%, K2O 0-5%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, BaO 0-1%, and MgO+CaO+SrO+BaO 0-5%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.24 or less and a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 0.67 or less can be exemplified. The reasons for limiting each component and their preferred ranges overlap with what has already been described, so an explanation is omitted here.

[0077] In addition to the composition ranges mentioned above, other examples of glass compositions include those containing, in molar percentages, SiO2 60-85%, Al2O3 5-17.5%, B2O3 0-5%, Li2O 0-7%, Na2O 0-8.3%, K2O 0-5%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, BaO 0-1%, and MgO+CaO+SrO+BaO 0-3.7%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.24 or less and a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 0.67 or less. The reasons for limiting each component and their preferred ranges are the same as those previously described, so we will omit further explanation here.

[0078] Furthermore, as another embodiment of the pharmaceutical container glass of the present invention, in addition to the composition range described above, examples include glass containing, in mole percent, SiO2 60-85%, Al2O 35-20%, B2O 30-5%, Li2O+Na2O+K2O 0.1-26%, and MgO+CaO+SrO+BaO 0-3%. The reasons for limiting each component and their preferred ranges overlap with what has already been described, so we will omit further explanation here.

[0079] Furthermore, as another embodiment of the pharmaceutical container glass of the present invention, in addition to the composition range described above, for example, a glass containing, in molar percent, SiO2 60-85%, Al2O3 3-7%, B2O3 0-5%, Li2O 0-7%, Na2O 0-8.3%, K2O 0-5%, Li2O+Na2O+K2O 0.1-26%, SrO 0-1%, BaO 0-1%, and MgO+CaO+SrO+BaO 0-3.7%, with a molar ratio of K2O / (Li2O+Na2O+K2O) of 0.24 or less, a molar ratio of Al2O3 / (Li2O+Na2O+K2O) of 0.5 or less, and a molar ratio of SiO2 / Al2O3 of 16 or less can also be exemplified. The reasons for limiting each component and the preferred ranges are the same as described above, so the explanation is omitted here.

[0080] Furthermore, it is preferable that the glass for pharmaceutical containers of the present invention has a class of at least HGA1 in the hydrolysis resistance test (acetone washing) in accordance with ISO720.

[0081] Furthermore, the glass for pharmaceutical containers of the present invention preferably has an alkali elution amount in terms of Na2O, measured by hydrolysis resistance testing (acetone washing) in accordance with ISO 720, of less than 62 μg / g, and is 60 μg / g or less, 57 μg / g or less, 55 μg / g or less, 53 μg / g or less, and particularly less than 50 μg / g. If the alkali elution amount is too high, when the glass is processed into ampoules or vials, filled with drugs, and stored, there is a risk that the drug components may be altered by the alkali components eluted from the glass.

[0082] Furthermore, the alkali resistance of glass is one indicator for determining its resistance to delamination. The glass for pharmaceutical containers of the present invention preferably has an alkali resistance of at least Class 2, as determined by testing in accordance with ISO 695. Here, "alkali resistance test in accordance with ISO 695" refers to the following test. (1) Surface area Acm² with all surfaces mirror-finished 2 (However, A is 10-15cm) 2 Prepare a glass sample of ( ). First, as a pretreatment, prepare a solution by mixing hydrofluoric acid (40 wt%) and hydrochloric acid (2 mol / L) in a volume ratio of 1:9. Immerse the sample in this solution and stir with a magnetic stirrer for 10 minutes. Remove the sample and perform ultrasonic cleaning with purified water for 2 minutes three times, followed by ultrasonic cleaning with ethanol for 1 minute twice. (2) After that, the sample is dried in an oven at 110°C for 1 hour and then allowed to cool in a desiccator for 30 minutes. (3) Measure and record the mass m1 of the sample with an accuracy of ±0.1 mg. (4) Prepare 800 mL of solution by mixing sodium hydroxide aqueous solution (1 mol / L) and sodium carbonate aqueous solution (0.5 mol / L) in a volume ratio of 1:1. Place the solution in a stainless steel container and bring it to a boil using a mantle heater. Add the sample suspended by platinum wire and hold for 3 hours. Remove the sample and perform ultrasonic cleaning with purified water for 2 minutes three times, followed by ultrasonic cleaning with ethanol for 1 minute twice. Then, dry the sample in an oven at 110°C for 1 hour and allow it to cool in a desiccator for 30 minutes. (5) Measure the mass m2 of the sample to an accuracy of ±0.1 mg and record it. (6) From the masses m1 and m2 (mg) before and after immersion in the boiling alkaline solution and the surface area A (cm 2 ), calculate the mass reduction per unit area according to the following calculation formula and use it as the measurement value of the alkali resistance test. (Mass reduction per unit area) = 100 × (m1 - m2) / A Note that "alkali resistance according to the test in accordance with ISO695 is class 2" means that the mass reduction per unit area obtained as described above is 175 mg / dm 2 or less. Note that if the mass reduction per unit area obtained as described above is 75 mg / dm 2 or less, "alkali resistance according to the test in accordance with ISO695 is class 1". The glass for pharmaceutical containers of the present invention preferably has a mass reduction per unit area of preferably 130 mg / dm 2 or less, particularly preferably 75 mg / dm 2 or less.

[0083] Delamination often occurs when a glass container is filled and stored with a drug using a solution that exhibits strong alkaline behavior even near neutral pH, such as citric acid or phosphate buffer solution. When the mass reduction per unit area determined by the test in accordance with ISO695 is greater than 175 mg / dm 2 , the possibility of causing delamination increases. Therefore, the glass for pharmaceutical containers of the present invention preferably has the above mass reduction per unit area of preferably 130 mg / dm 2 or less, particularly preferably 75 mg / dm 2 or less.

[0084] Further, the glass for pharmaceutical containers of the present invention preferably has a mass reduction per unit area of preferably 1.5 mg / dm 2 or less, particularly 0.7 mg / dm 2The following applies: If the mass loss is large, when bottle containers such as ampoules and vials are prepared, filled, and stored, the amount of glass components that leach out may increase significantly, potentially causing deterioration of the drug components. Note that "acid resistance test in accordance with YBB00342004" refers to the following test.

[0085] Here, "acid resistance test in accordance with YBB00342004" refers to the following test: (1) Surface area Acm² with all surfaces mirror-finished 2 (However, A is 100±5cm) 2 Prepare a glass sample of ( ). First, as a pretreatment, prepare a solution by mixing hydrofluoric acid (40 wt%) and hydrochloric acid (2 mol / L) in a volume ratio of 1:9. Immerse the sample in this solution and stir with a magnetic stirrer for 10 minutes. Remove the sample and perform ultrasonic cleaning with purified water for 2 minutes three times, followed by ultrasonic cleaning with ethanol for 1 minute twice. (2) After that, the sample is dried in an oven at 110°C for 1 hour and then allowed to cool in a desiccator for 30 minutes. (3) Measure and record the mass m1 of the sample with an accuracy of ±0.1 mg. (4) Prepare 800 mL of hydrochloric acid solution (6 mol / L). Place the solution in a silica glass container and bring it to a boil using an electric heater. Add the sample suspended by platinum wire and hold for 6 hours. Remove the sample and perform ultrasonic cleaning with purified water for 2 minutes three times, followed by ultrasonic cleaning with ethanol for 1 minute twice. Then, dry the sample in an oven at 110°C for 1 hour and allow it to cool in a desiccator for 30 minutes. (5) Measure and record the mass m2 of the sample with an accuracy of ±0.1 mg. (6) Masses m1 and m2 (mg) before and after immersion in boiling acid solution, and surface area A (cm²) of the sample. 2 From this, half of the mass loss per unit area is calculated using the following formula and used as the measured value for the acid resistance test: (Mass loss per unit area) = 1 / 2 × 100 × (m1 - m2) / A Furthermore, the working point of the pharmaceutical container glass of the present invention is preferably 1350°C or lower, 1300°C or lower, 1260°C or lower, and particularly 1250°C or lower. When the working point is high, the processing temperature when processing the glass tube into an ampoule or vial becomes higher, and the evaporation of alkaline components contained in the glass increases significantly. The evaporated alkaline components adhere to the inner wall of the glass tube, and the glass tube is processed into a glass container. Such glass containers can cause deterioration of pharmaceuticals when filled and stored. In addition, in glass containing a large amount of boron, when the working point is high, the evaporation of boron also increases, which can cause delamination.

[0086] The glass for pharmaceutical containers of the present invention can form a compressive stress layer on its surface by subjecting it to a chemical strengthening treatment. Specifically, the compressive stress value of the compressive stress layer formed when the glass for pharmaceutical containers of the present invention is subjected to a chemical strengthening (ion exchange) treatment by immersion in a molten KNO3 salt at 475°C for 7 hours is preferably 100 MPa or more, 200 MPa or more, and particularly preferably 300 MPa or more. Furthermore, the depth of the compressive stress layer is preferably 10 μm or more, 20 μm or more, and particularly preferably 30 μm or more.

[0087] The compressive stress value (CS) and depth from the sample surface (DOL) after chemical strengthening (ion exchange) can be measured as follows. First, both surfaces of the sample are mirror-polished, and then the sample is immersed in molten KNO3 at 475°C for 7 hours to perform chemical strengthening (ion exchange). Next, the surface of the sample is cleaned, and the compressive stress value (CS) and depth from the sample surface (DOL) of the compressive stress layer on the surface are calculated from the number and spacing of interference fringes observed using a surface stress meter (FSM-6000, Orihara Seisakusho Co., Ltd.). For the calculation, the refractive index of the sample is assumed to be 1.50 and the photoelastic constant is assumed to be 29.5 [(nm / cm) / MPa]. Although the glass composition at the surface of the glass differs microscopically before and after chemical strengthening, the glass composition as a whole is substantially the same.

[0088] Next, a method for manufacturing glass tubes for pharmaceutical containers according to the present invention will be described. The following description is an example using the Danner process.

[0089] First, glass raw materials are mixed to create a glass batch with a predetermined glass composition. Next, this glass batch is continuously fed into a melting furnace at 1550-1700°C for melting and clarification. Then, the resulting molten glass is wrapped around a rotating refractory material, and air is blown from the tip of the refractory material while the glass is drawn out in a tubular shape from that tip.

[0090] Next, the extracted tubular glass is cut to a predetermined length to obtain glass tubes. The glass tubes obtained in this way are used in the manufacture of vials and ampoules.

[0091] Furthermore, the glass tubes for pharmaceutical containers of the present invention may be manufactured using any conventionally known method, not limited to the Dannah method. For example, the Bellows method or the downdraw method are effective methods for manufacturing the glass tubes for pharmaceutical containers of the present invention.

[0092] Next, a method for manufacturing the pharmaceutical container of the present invention will be described. The following is an example of manufacturing a pharmaceutical container by processing a glass tube using a vertical processing method.

[0093] First, prepare a glass tube. Next, with the glass tube standing vertically, heat one end of the glass tube with a burner and use a shaping tool to form the shoulder and mouth. Then, heat the portion of the glass tube above the shoulder with the burner and melt it.

[0094] Next, the cut portion is heated and molded with a burner to form the bottom, thereby obtaining a pharmaceutical container.

[0095] The cut portion of the glass tube is then opened by heating it with a burner and used for manufacturing the next container. By repeating the molding process described above, multiple pharmaceutical containers can be obtained from a single glass tube.

[0096] Furthermore, by immersing pharmaceutical containers such as ampoules and vials obtained using the glass tubes for pharmaceutical containers of the present invention in a molten KNO3 salt and performing ion exchange, chemically strengthened pharmaceutical containers can be obtained.

[0097] Furthermore, the glass tube for pharmaceutical containers of the present invention can be coated on its outer surface. The coating can be made from any material selected from inorganic coatings such as fluorine, silicon, and surfactants, as well as organic coatings.

[0098] Furthermore, pharmaceutical containers such as ampoules and vials obtained using the glass tubes for pharmaceutical containers of the present invention can also be coated on their inner and / or outer surfaces. The coating can be made from any material selected from inorganic coatings and organic coatings such as fluorine, silicon, and surfactants. [Examples]

[0099] The present invention will be described below based on examples.

[0100] Tables 1-5 show examples of the present invention (Nos. 1-15, 17-63) and comparative examples (No. 16).

[0101] [Table 1]

[0102] [Table 2]

[0103] [Table 3]

[0104] [Table 4]

[0105] [Table 5] Each sample was prepared as follows:

[0106] First, a 550g batch was prepared to the composition shown in the table, and melted in a platinum crucible at 1550°C for 2.5 hours. To improve the homogeneity of the sample, it was stirred twice during the melting process. To further improve the homogeneity of the sample, the glass was granulated with water and dried, then melted again in a platinum crucible at 1550°C for 1 hour, with one stirring. To reduce bubbles in the sample, it was melted at 1600°C for 2 hours. After melting, an ingot was prepared, processed into the shape required for measurement, and subjected to various evaluations. The results are shown in Tables 1-3.

[0107] The hydrolysis resistance test was performed according to ISO 720 (acetone washing). The detailed test procedure is as follows: The glass sample was crushed in an alumina mortar using an alumina pestle and classified into particles of 300-425 μm using a sieve. The resulting powder was washed with acetone and dried in an oven at 140°C. 10 g of the dried powder sample was placed in a quartz flask, and 50 mL of purified water was added before capping. The quartz flask containing the sample was placed in an autoclave for processing. The processing conditions were to raise the temperature from 100°C to 121°C at a rate of 1°C / min, hold at 121°C for 30 minutes, and then cool to 100°C at a rate of 0.5°C / min. The solution in the quartz flask was transferred to another beaker, and the quartz flask was washed three times with 15 mL of purified water, and the washing water was also added to the beaker. Methyl red indicator was added to the beaker and titrated with 0.02 mol / L hydrochloric acid solution. The amount of alkali elution was calculated by converting 1 mL of 0.02 mol / L hydrochloric acid solution to be equivalent to 620 μg of Na2O, and this was used as the measurement value for hydrolysis resistance.

[0108] The alkali resistance of the glass was evaluated by testing in accordance with ISO 695.

[0109] The acid resistance of the glass was evaluated by an acid resistance test in accordance with YBB00342004.

[0110] Furthermore, the strain point Ps was determined using a fiber stretching method in accordance with ASTM C336, and the viscosity of the glass was 10 14.5 We determined the temperature at which Pa·s occurs.

[0111] The annealing point Ta and softening point Ts were determined using a fiber stretching method in accordance with ASTM C388, with a glass viscosity of 10 7.6 The temperature at which the pressure becomes dPa·s was determined.

[0112] Working point (when the viscosity of the glass is 10 4.0 The temperature at which it becomes dPa·s and the viscosity of the glass is 10 3.0 The temperature at which the temperature reaches dPa·s was determined using the platinum sphere pulling method.

[0113] The linear thermal expansion coefficient was measured using a dilatometer with a glass sample molded into a rod shape of approximately 5 mmφ × 20 mm, over a temperature range of 20 to 300°C.

[0114] To measure the liquidus temperature, a platinum boat measuring approximately 120 × 20 × 10 mm was filled with the crushed glass sample and placed in an electric furnace with a linear temperature gradient for 24 hours. Subsequently, crystal deposition sites were identified by microscopic observation, and the temperatures corresponding to these crystal deposition sites were calculated from the electric furnace's temperature gradient graph. This temperature was defined as the liquidus temperature.

[0115] The liquid-phase viscosity was calculated by determining the viscosity curve of the glass from the strain point, slow cooling point, softening point, working temperature, and Fulcher's viscosity formula. From this viscosity curve, the viscosity of the glass at the liquid-phase temperature was calculated, and this viscosity was defined as the liquid-phase viscosity.

[0116] The compressive stress (CS) and depth from the sample surface (DOL) of the sample after chemical strengthening (ion exchange) were determined using a surface stress meter (FSM-6000, manufactured by Orihara Manufacturing Co., Ltd.).

[0117] As is clear from Tables 1-5, the embodiments of the present invention had a working point of 1321°C or lower and an alkali elution amount of 58.9 μg / g or lower in the hydrolysis resistance test. [Industrial applicability]

[0118] The glass for pharmaceutical containers of the present invention is suitable for manufacturing pharmaceutical containers such as ampoules, vials, pre-filled syringes, and cartridges. It can also be applied to pharmaceutical containers for oral medications and beverage bottles.

Claims

1. As a glass composition, in mol%, SiO ２ 70 to 85%, Al ２ O ３ 3 to 20%, B ２ O ３ 0 to 4%, Li ２ O 0 to 5%, Na ２ O 0 to 12%, K ２ O 0 to 6%, Li ２ O + Na ２ O + K ２ O 0.1 to 26%, SrO 0 to 1%, BaO 0 to 1%, and has a molar ratio of K ２ O / (Li ２ O + Na ２ O + K ２ O) value of 0.24 or less, a molar ratio of Al ２ O ３ / (Li ２ O + Na ２ O + K ２ O) value of 50 or less, a molar ratio of SiO ２ / (Li ２ O + Na ２ O + K ２ O) value of 6.5 or less, and a molar ratio of MgO / (MgO + CaO + SrO + BaO) value of 0.8 or less, and is characterized as a glass for pharmaceutical containers.

2. The glass for pharmaceutical containers according to claim 1, characterized in that the glass composition satisfies the requirement of CaO ≥ MgO in mol%.

3. As for the glass composition, in mol%, Na ２ O 0-7.9%, K ２ A glass container for pharmaceuticals according to claim 1 or 2, characterized by containing 0-3% of O.

4. A glass for pharmaceutical containers according to any one of claims 1 to 3, characterized in that the glass composition contains, in mol% terms, 0-0.5% MgO, 0-0.5% CaO, 0-0.3% SrO, and 0-0.3% BaO.

5. B ２ O ３ A glass container for pharmaceuticals according to any one of claims 1 to 4, characterized in that the content of is 0.01 to 1 mol%.

6. ZrO ２ A glass container for pharmaceuticals according to any one of claims 1 to 5, characterized in that the content of is 0 to 2 mol%.

7. The glass for pharmaceutical containers according to any one of claims 1 to 6, characterized in that the class in the hydrolysis resistance test (acetone washing) in accordance with ISO 720 is at least HGA1.

8. A glass for pharmaceutical containers according to any one of claims 1 to 7, characterized in that the working temperature is 1300°C or lower.

9. A glass tube for pharmaceutical containers, characterized by being made of the glass for pharmaceutical containers described in any one of claims 1 to 8.

10. A pharmaceutical container characterized by being made of the glass for pharmaceutical containers described in any one of claims 1 to 8.

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