Glass for pharmaceutical container and glass tube for pharmaceutical container

Abstract

Provided are: a glass for pharmaceutical containers, which has excellent chemical durability, transparency and devitrification resistance; and a glass tube for pharmaceutical containers, which is obtained therefrom. This glass for pharmaceutical containers is characterized by containing, as a glass composition, 65%-80% of SiO2, 1%-10% of Al2O3, 5%-20% of B2O3, more than 0% but not more than 0.1% of MoO3, 0-10% of MgO + CaO + SrO + BaO, and 1%-20% of Li2O + Na2O + K2O.

Description

Technical Field

[0001] The present invention relates to glass for pharmaceutical containers and a glass tube for pharmaceutical containers used in glass vials such as vials and ampoules and syringe barrels of syringes. Background Art

[0002] Glass used for pharmaceutical containers such as vials and ampoules requires the following properties.

[0003] (a) The components in the filling liquid do not react with the components in the glass;

[0004] (b) High chemical durability to avoid contamination of the filled liquid;

[0005] (c) Low operating temperature, so that vials, ampoules, etc. can be processed at low temperatures.

[0006] For example, as described in Patent Document 1, the glass for pharmaceutical containers that meets these required properties contains SiO2, B2O3, Al2O3, Na2O, K2O, CaO, BaO, and a small amount of clarifier as constituent components. 4.0 Temperature at dPa·s.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-237562

[0010] Patent Document 2: International Publication No. 2019 / 078188 Summary of the Invention

[0011] Technical problem that the invention aims to solve

[0012] In recent years, the development of liquid medicines has continued to advance, and more effective liquid medicines are being used. These liquid medicines contain complex molecular structures such as proteins and m-RNA, which are expected to improve the therapeutic effect.

[0013] However, these chemical solutions are more reactive than conventional chemical solutions composed of low-molecular-weight compounds. Consequently, if glass components erode during storage and leach into the chemical solution, the glass components react with the chemical solution, potentially significantly reducing the activity of the chemical solution. Consequently, glass containers are required to exhibit higher chemical durability than before.

[0014] Generally speaking, for the glass composition described in Patent Document 1, increasing the content of SiO2 and Al2O3, which are components of the glass network structure, is considered to improve chemical durability. However, this method tends to increase the working temperature of the glass. Therefore, for example, Patent Document 2 describes a glass for pharmaceutical containers that achieves a low working temperature and improves chemical durability, particularly hydrolysis resistance, by limiting the amount and ratio of CaO and BaO and adding BaO preferentially over CaO. However, BaO is a component that easily reacts with alumina-based refractory materials during glass melting, causing celsium feldspar crystallization and precipitation. This can easily deteriorate devitrification resistance and reduce productivity.

[0015] Furthermore, as mentioned above, when glass containers are corroded by low-stability, high-molecular-weight components in a drug solution, or when these components aggregate due to external stimuli such as heat, light, and vibration, insoluble foreign matter may form within the drug solution. If ingested by the human body, such foreign matter can form blood clots, causing pain and irritation. Therefore, foreign matter inspections are performed using both visual and imaging methods before drug solutions are shipped. Important for foreign matter inspections is easy visual inspection of the container's interior, i.e., transparency. In glass containers, transparency depends on the content of components such as iron and titanium that contribute to coloration.

[0016] In view of the above circumstances, the technical object of the present invention is to provide a glass for pharmaceutical containers having excellent chemical durability, transparency, and resistance to devitrification, and a glass tube for pharmaceutical containers obtained therefrom. It should be noted that in this specification, hydrolysis resistance and alkali resistance are collectively referred to as chemical durability.

[0017] Technical means to solve the problem

[0018] The inventors conducted intensive research and discovered that the aforementioned problems can be solved by strictly limiting the content of each glass component, which they have proposed as the present invention. Specifically, the glass for pharmaceutical containers of the present invention is characterized by comprising, in terms of mass %, the following: SiO₂ 65% to 80%, Al₂O₃ 1% to 10%, B₂O₃ 5% to 20%, MoO₃ greater than 0 and less than 0.1%, MgO+CaO+SrO+BaO 0% to 10%, and Li₂O+Na₂O+K₂O 1% to 20%. This allows for the production of pharmaceutical container glass that exhibits excellent chemical durability, transparency, and devitrification resistance.

[0019] Here, "Li2O+Na2O+K2O" is the total content of Li2O, Na2O, and K2O. "MgO+CaO+SrO+BaO" is the total content of MgO, CaO, SrO, and BaO.

[0020] The pharmaceutical container glass of the present invention preferably has a Na2O content of 5% to 9% and a K2O content of 0.1% to 3%. This improves chemical durability, particularly hydrolysis resistance, and facilitates the realization of pharmaceutical container glass with low thermal expansion and a low operating temperature.

[0021] In the glass for pharmaceutical containers of the present invention, the CaO content is preferably 0.1% to 2%, and the BaO content is preferably 0.1% to less than 1.3%. This facilitates the realization of a glass for pharmaceutical containers with a low working point.

[0022] In the glass for pharmaceutical containers of the present invention, the content of MgO + CaO + SrO + BaO is preferably 0.2% to 10%, and the content ratio (Li₂O + Na₂O + KO₂O) / (MgO + CaO + SrO + BaO) is 3 to 10. This improves the chemical durability of the glass, particularly its hydrolysis resistance, and facilitates achieving a low operating point. Here, "(Li₂O + Na₂O + KO₂O) / (MgO + CaO + SrO + BaO)" is the value obtained by dividing the total content of Li₂O, Na₂O, and KO₂O by the total content of MgO, CaO, SrO, and BaO.

[0023] The glass for pharmaceutical containers of the present invention preferably has an Fe2O3 content of 0.001% to 0.05%, a TiO2 content of 0.001% to 0.05%, a content ratio of MoO3 / (Fe2O3 + TiO2) of 0.0001 to 0.1, and a visible light transmittance of 80% or greater at a thickness of 1 mm. This facilitates the production of pharmaceutical container glass that maintains high transparency and exhibits excellent devitrification resistance. Here, "MoO3 / (Fe2O3 + TiO2)" is the value obtained by dividing the MoO3 content by the combined content of Fe2O3 and TiO2.

[0024] In the glass for pharmaceutical containers of the present invention, the content of F+Cl+Sb2O3+As2O3+SnO2+CeO2 is preferably 0.01% to 0.5%. This improves the transparency and foaming properties of the glass. Here, "F+Cl+Sb2O3+As2O3+SnO2+CeO2" refers to the total content of F, Cl, Sb2O3, As2O3, SnO2, and CeO2.

[0025] In the glass for pharmaceutical containers of the present invention, the content of Fe2O3+TiO2+MoO3+SnO2+CeO2 is preferably 0.5% or less, and the visible light transmittance at a thickness of 1 mm is 85% or greater. This facilitates improved transparency of the glass. Here, "Fe2O3+TiO2+MoO3+SnO2+CeO2" refers to the combined content of Fe2O3, TiO2, MoO3, SnO2, and CeO2.

[0026] The glass for pharmaceutical containers of the present invention preferably has a Li₂O content of 0-0.1%, a MgO content of 0-0.1%, a SrO content of 0-0.1%, a Li₂O+Na₂O+K₂O content of 5.1%-12.1%, and a MgO+CaO+SrO+BaO content of 0.2% to less than 2.5%. This improves the glass's meltability, formability, and chemical durability.

[0027] The glass for pharmaceutical containers of the present invention preferably has a thermal expansion coefficient of 40×10 -7 / ℃~60×10 -7 / °C. This makes it less likely that breakage due to thermal shock will occur during the glass manufacturing process, processing process, sterilization process, etc.

[0028] The glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention are characterized in that, as a glass composition, the following are contained, by mass%, in the following amounts: SiO2 68% to 77%, Al2O3 6.5% to 8%, B2O3 9% to 12%, MoO3 greater than 0 and 0.1% or less, CaO 0.1% to 2%, BaO 0.1% to less than 1.3%, MgO+CaO+SrO+BaO 0.2% to less than 2.5%, Na2O 5% to 9%, K2O 0.1% to 3%, Li2O+Na2O+K2O 5.1% to 12.1%, Fe2O3 0.001% to 0.05%, TiO2 0.001% to 0.05%, F+Cl+Sb2O3+As2O3+SnO2+CeO2 0.01% to 0.5%, and the content ratio of MoO3 / (Fe2O3+TiO2) is 0.0001 to 0.1. This makes it easy to obtain pharmaceutical container glass and pharmaceutical container glass tubes that maintain high transparency and have excellent chemical durability, devitrification resistance, and foaming properties.

[0029] The pharmaceutical container glass and pharmaceutical container glass tube of the present invention are characterized by having a Cl content of 0.001% to 0.1% and a Sb2O3 content of 0.001% to 0.05%. This makes it easier to obtain pharmaceutical container glass and pharmaceutical container glass tubes that are less likely to cause defects when processed into pharmaceutical containers such as vials and ampoules.

[0030] Effects of the Invention

[0031] According to the present invention, it is possible to provide glass for pharmaceutical containers that is excellent in chemical durability, transparency, and resistance to devitrification, and a glass tube for pharmaceutical containers obtained therefrom. DETAILED DESCRIPTION

[0032] First, the reasons for limiting the content ranges of the components in the pharmaceutical container glass and pharmaceutical container glass tube of the present invention will be described. It should be noted that in the following description, "%" means "mass %" unless otherwise specified.

[0033] SiO2 is one of the components that make up the network structure of glass. The lower the SiO2 content, the better the formability. However, too little SiO2 can deteriorate chemical durability and make vitrification difficult. Furthermore, the coefficient of thermal expansion tends to increase, and thermal shock resistance can decrease. Therefore, the SiO2 content is 65% or higher, preferably 65.5%, 66%, 66.5%, 67%, 67.5%, and 68% or higher, with 68% or higher being particularly preferred. On the other hand, a higher SiO2 content improves chemical durability, but too much SiO2 increases the viscosity of the glass, tending to raise the working point, and the liquidus temperature, making devitrification more likely. Therefore, the SiO2 content is 80% or lower, preferably 79.5%, 79%, 78.5%, 78%, 77.5%, and 77% or lower, with 77% or lower being particularly preferred.

[0034] Al2O3 is one of the components that form the network structure of glass. It improves chemical durability, particularly hydrolysis resistance. However, if the Al2O3 content is too low, hydrolysis resistance can deteriorate. Therefore, the Al2O3 content is preferably 1% or higher, preferably 2%, 3%, 4%, 4.5%, 5%, 5.5%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, and particularly preferably 6.5% or higher. On the other hand, if the Al2O3 content is too high, the viscosity of the glass increases, and the glass is prone to devitrification, making it difficult to shape. Therefore, the Al2O3 content is preferably 10% or lower, preferably 9.5%, 9%, 8.9%, 8.8%, 8.7%, 8.6%, 8.5%, 8.4%, 8.3%, 8.2%, 8.1%, and particularly preferably 8% or lower.

[0035] B2O3 has the effect of reducing the viscosity of glass, improving its meltability and formability, and lowering its density and Young's modulus. Therefore, the B2O3 content is 5% or more, preferably 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.3%, 8.5%, 8.8%, and particularly preferably 9% or more. However, excessive B2O3 content can deteriorate chemical durability, particularly alkali resistance. Therefore, the B2O3 content is 20% or less, preferably 19%, 18%, 17%, 16%, 15%, 14%, 13.5%, 13%, 12.5%, and particularly preferably 12%.

[0036] MoO3 is a component that reduces the amount of water in glass. When the amount of water in glass decreases, the liquidus viscosity increases, which can improve the glass's resistance to devitrification. Furthermore, when glass is melted by electric melting, Mo is sometimes used as a component of electrodes, and sometimes is mixed into the glass during the melting process. Therefore, by adding MoO3 to the glass raw materials and melting the glass by electric melting, the glass's resistance to devitrification can be further improved. It should be noted that electric melting is a melting method that is more energy efficient than conventional burner flame-based melting methods. Using electric melting to melt glass can also help suppress CO2 emissions during glassmaking. Therefore, the content of MoO3 is greater than 0%, preferably 0.00001% or more, 0.00002% or more, 0.00003% or more, 0.00004% or more, 0.00005% or more, 0.00006% or more, 0.00007% or more, 0.00008% or more, 0.00009% or more, 0.0001% or more, 0.00015% or more, 0.0002% or more, 0.00025% or more, and particularly preferably 0.0003% or more. On the other hand, if the content of MoO3 is too high, the glass will be colored black, and the transmittance of visible light will decrease. Therefore, the content of MoO3 is less than 0.1%, preferably less than 0.05%, less than 0.04%, less than 0.03%, less than 0.02%, less than 0.01%, less than 0.009%, less than 0.008%, less than 0.007%, less than 0.006%, less than 0.005%, less than 0.004%, less than 0.003%, and particularly preferably less than 0.003%.

[0037] Li2O reduces the viscosity of glass, improving its meltability and formability. Among alkali metal oxides, Li2O has the greatest effect in reducing the viscosity of glass, followed by Na2O and K2O. However, excessive Li2O content can deteriorate chemical durability and easily cause devitrification. Therefore, the Li2O content is preferably 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, 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, or 0.2% or less, and particularly preferably 0.1% or less.

[0038] Like Li₂O, Na₂O reduces the viscosity of glass, improving its meltability and formability. It also improves devitrification resistance and its reaction devitrification with the refractory materials of the formed body, particularly alumina refractory materials. Too little Na₂O can easily reduce devitrification resistance. Therefore, the Na₂O content is preferably 0.1% or higher, 0.5% or higher, 1% or higher, 1.5% or higher, 2.0% or higher, 2.5% or higher, 3.0% or higher, 3.5% or higher, 4.0% or higher, 4.5% or higher, and particularly preferably 5.0% or higher. On the other hand, excessive Na₂O content can easily deteriorate chemical durability, particularly hydrolysis resistance. Therefore, the Na₂O content is preferably 15% or lower, 14% or lower, 13% or lower, 12% or lower, 11% or lower, 10% or lower, 9.8% or lower, 9.5% or lower, 9.3% or lower, 9.1% or lower, and particularly preferably 9% or lower.

[0039] While K₂O does not have the same effects as Li₂O and Na₂O, it does have the effect of reducing the viscosity of the glass and improving its meltability and formability. If the K₂O content is too low, devitrification resistance may be reduced. Therefore, the K₂O content is preferably greater than 0%, 0.01% or higher, 0.03% or higher, 0.05% or higher, 0.08% or higher, and particularly preferably 0.1% or higher. On the other hand, if the K₂O content is too high, chemical durability, particularly hydrolysis resistance, tends to deteriorate. Therefore, the K₂O content is preferably 5% or lower, 4.5% or lower, 4% or lower, 3.9% or lower, 3.8% or lower, 3.7% or lower, 3.6% or lower, 3.5% or lower, 3.4% or lower, 3.3% or lower, 3.2% or lower, 3.1% or lower, and particularly preferably 3% or lower.

[0040] Alkali metal oxides (RO) such as Li2O, Na2O, and KO are components that disrupt the glass network structure, reducing its viscosity and improving its meltability and formability. The content of Li2O+Na2O+KO is 1% or higher, preferably 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.1%, 6%, or 7%, and particularly preferably 7.5% or higher. On the other hand, excessive Li2O+Na2O+KO content can deteriorate chemical durability, particularly hydrolysis resistance, and increase the thermal expansion coefficient, reducing thermal shock resistance. Therefore, the content of Li2O+Na2O+K2O is less than 20%, preferably less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14.5%, less than 14%, less than 13.5%, less than 13%, less than 12.5%, less than 12.1%, less than 11%, less than 10%, and especially less than 9.5%.

[0041] Among alkali metal oxides (RO), Li2O is most effective in reducing the viscosity of glass, followed by Na2O and K2O. However, since Li2O deteriorates the devitrification resistance of glass, the relationship between the alkali metal oxide contents is preferably Na2O ≥ K2O ≥ Li2O, Na2O > K2O ≥ Li2O, or Na2O ≥ K2O > Li2O, with Na2O > K2O > Li2O being particularly preferred. Furthermore, if the proportion of K2O in the alkali metal oxide is too high, it becomes difficult to achieve both chemical durability and a low operating point. Therefore, Na2O > K2O is particularly preferred.

[0042] Reducing the moisture content in glass affects its chemical durability, particularly its hydrolysis resistance. The lower the moisture content in glass, the higher its hydrolysis resistance. Since MoO₃ reduces the moisture content in glass, its inclusion contributes to improved hydrolysis resistance. Among the components included in the glass composition of the present invention, Li₂O, Na₂O, and KO are examples of those that have a significant impact on reducing hydrolysis resistance. The order of impact on reducing hydrolysis resistance is K₂O > Na₂O > Li₂O > MoO₃. In contrast to MoO₃, increasing the content of Li₂O, Na₂O, and KO degrades hydrolysis resistance. Therefore, to improve hydrolysis resistance, the lower limit of the content ratio (100×MoO₃ / (Li₂O + Na₂O + KO)) is preferably 0.00001 or higher, 0.0001 or higher, 0.0003 or higher, 0.0005 or higher, or 0.001 or higher, and particularly preferably 0.003 or higher. On the other hand, as mentioned above, MoO₃ is also a component that affects the transmittance of glass. Excessive MoO₃ content can cause glass coloration and reduce transmittance. Therefore, the upper limit of the content ratio (100×MoO₃ / (Li₂O+Na₂O+K₂O)) is preferably 10 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, and particularly preferably 1 or less.

[0043] MgO, like alkali metal oxides, disrupts the glass network, reducing high-temperature viscosity and improving meltability and formability. It also affects chemical durability. Excessive MgO content can deteriorate chemical durability, particularly hydrolysis resistance, and increase the tendency for glass to devitrify. Therefore, the MgO content is preferably 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, 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, 0.05% or less, 0.03% or less, less than 0.03%, 0.01% or less, or less than 0.01%, particularly preferably less than 0.001%.

[0044] CaO, like alkali metal oxides, is a component that disrupts the glass network, reduces high-temperature viscosity, and improves meltability and formability. Furthermore, because CaO can be obtained more cheaply than other alkaline earth metal oxides, it can improve meltability and formability while reducing manufacturing costs. Therefore, the CaO content is preferably greater than 0%, at least 0.05%, at least 0.1%, and particularly preferably at least 0.3%. Furthermore, CaO also affects chemical durability; excessive CaO content can reduce chemical durability, particularly hydrolysis resistance. Therefore, the CaO content is preferably 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, or 0.9% or less, and particularly preferably 0.8% or less.

[0045] BaO, like alkali metal oxides, is a component that disrupts the glass network, reduces high-temperature viscosity, and improves meltability and formability. Therefore, the BaO content is preferably greater than 0%, ranging from 0.1% or greater, 0.3% or greater, 0.5% or greater, or 0.7% or greater, and particularly preferably from 1% or greater. Furthermore, BaO affects chemical durability. Excessive BaO content can reduce chemical durability, particularly hydrolysis resistance. Furthermore, during glass melting or tube forming, BaO reacts with alumina-based refractory materials, aptly leading to the precipitation of celsium feldspar crystals. The BaO content is preferably 5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5% or less, 1.4% or less, 1.3% or less, or less than 1.3%, and particularly preferably from 1.25% or less.

[0046] SrO, like alkali metal oxides, disrupts the glass network, reducing high-temperature viscosity and improving meltability and formability. It also affects chemical durability. Excessive SrO content can reduce chemical durability, particularly hydrolysis resistance. The SrO content is preferably 1% or less, 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, 0.05% or less, 0.03% or less, less than 0.03%, 0.01% or less, or less than 0.01%, with less than 0.001% being particularly preferred.

[0047] MgO, CaO, SrO, and BaO, which are alkaline earth metal oxides (R'O), are components that disrupt the glass network structure, similar to alkali metal oxides, and also have the effect of reducing the viscosity of the glass. Excessive MgO+CaO+SrO+BaO content can easily deteriorate chemical durability, particularly hydrolysis resistance, and reduce devitrification resistance. Therefore, the MgO+CaO+SrO+BaO content is 10% or less, preferably 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3.4% or less, 3.3% or less, 3.2% or less, 3.1% or less, 3% or less, 2.9% or less, 2.8% or less, 2.7% or less, 2.6% or less, 2.5% or less, or less than 2.5%, and particularly preferably 2.2% or less. The content of MgO+CaO+SrO+BaO is above 0%, but in order to improve the solubility and workability of the glass, it is preferably greater than 0, above 0.1%, above 0.2%, above 0.3%, above 0.4%, above 0.5%, above 0.7%, above 1%, above 1.5%, and particularly preferably above 1.7%.

[0048] Research from the perspectives of glass properties and manufacturing costs has concluded that CaO and BaO are preferred alkaline earth metal oxides for glass. However, excessive CaO and BaO content increases alkali leaching from the glass, leading to an increase in the thermal expansion coefficient and a decrease in thermal shock resistance. The CaO+BaO content is preferably 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3.3% or less, 3% or less, 2.8% or less, 2.5% or less, or 2.2% or less, and particularly preferably 2% or less. Here, "CaO+BaO" refers to the combined content of CaO and BaO. On the other hand, if the CaO and BaO content is too low, achieving a low operating point becomes difficult. Therefore, the CaO+BaO content is preferably greater than 0%, 0.2% or more, 0.5% or more, 1% or more, or 1.3% or more, and particularly preferably 1.5% or more.

[0049] The contents of CaO and BaO in the present invention are preferably such that CaO ≤ BaO. More preferably, CaO < BaO. When the CaO / BaO ratio is too high, hydrolysis resistance tends to deteriorate. On the other hand, the smaller the CaO / BaO ratio, the better the hydrolysis resistance of the resulting glass. A particularly preferred relationship between the CaO and BaO contents is CaO / BaO, i.e., the value obtained by dividing the CaO content by the BaO content, which is preferably less than 1, 0.9 or less, 0.8 or less, 0.7 or less, and particularly preferably 0.65 or less, preferably 0.1 or more, 0.2 or more, and particularly preferably 0.3 or more.

[0050] Alkali metal oxides (RO) and alkaline earth metal oxides (R'O) are both components that disrupt the network structure of glass and also have the effect of reducing the viscosity of glass. They also affect chemical durability. However, if the content of either alkali metal oxide (RO) or alkaline earth metal oxide (R'O) is too high or too low, it is difficult to achieve excellent chemical durability, especially hydrolysis resistance, low thermal expansion, and a low operating temperature. Therefore, in the present invention, the upper limit of the content ratio (Li2O + Na2O + KO) / (MgO + CaO + SrO + BaO) is preferably 100 or less, 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less, and particularly preferably 10 or less. The lower limit is preferably 0.1 or more, 0.5 or more, 1 or more, 1.5 or more, 2 or more, 2 or more, 2.5 or more, 2.6 or more, 2.7 or more, 2.8 or more, or 2.9 or more, and particularly preferably 3 or more.

[0051] SiO2, Al2O3, and B2O3 form the glass network structure, while alkali metal oxides (RO) and alkaline earth metal oxides (R'O) cut the glass network. The content ratio (R2O + R'O - Al2O3) / (SiO2 + Al2O3 + B2O3) represents the ratio of the components that cut the glass network structure to the components that form it. By properly controlling this content ratio, the viscosity of the glass is prevented from increasing excessively, achieving high workability and producing glass with excellent chemical durability, particularly excellent hydrolysis resistance. Specifically, the lower limit of the content ratio (R2O + R'O - Al2O3) / (SiO2 + Al2O3 + B2O3) is preferably 0 or greater, 0.001 or greater, 0.003 or greater, 0.005 or greater, 0.007 or greater, or 0.009 or greater, and particularly preferably 0.01 or greater. The upper limit is preferably 0.1 or less, 0.09 or less, 0.07 or less, 0.055 or less, 0.05 or less, and particularly 0.045 or less. If the above content ratio is too low, the viscosity of the glass becomes too high, and workability is likely to decrease. On the other hand, if the above content ratio is too high, chemical durability, particularly hydrolysis resistance, is likely to deteriorate.

[0052] In addition to the above-mentioned components, other components may be introduced into the glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention.

[0053] Fe2O3 is a component that is frequently incorporated as an impurity from raw materials and manufacturing equipment. Excessive Fe2O3 content can tint the glass and reduce visible light transmittance. Therefore, the upper limit of the Fe2O3 content is preferably 0.5% or less, 0.3% or less, 0.1% or less, 0.05% or less, 0.04% or less, 0.03% or less, or 0.02% or less, and particularly preferably 0.01% or less. On the other hand, Fe2O3 is easily incorporated as an impurity, so completely removing it tends to increase the cost of the glass raw materials. Therefore, to reduce manufacturing costs, the lower limit of the Fe2O3 content is preferably 0.00001%, 0.0001%, 0.001%, or more, and particularly preferably 0.01% or more.

[0054] Like Fe2O3, TiO2 is a component that is frequently introduced as an impurity from raw materials and manufacturing equipment. Excessive TiO2 content can cause the glass to appear black, reducing the transmittance of visible light. Therefore, the upper limit of the TiO2 content is preferably 0.5% or less, 0.3% or less, 0.1% or less, 0.05% or less, or 0.04% or less, with 0.03% or less being particularly preferred. On the other hand, completely removing TiO2 can increase the cost of glass raw materials. Therefore, to reduce manufacturing costs, the lower limit of the TiO2 content is preferably 0.00001%, 0.0001%, 0.001%, or more, with 0.01% or more being particularly preferred.

[0055] MoO3 is a component that reduces the amount of water in glass and contributes to the glass's resistance to devitrification, but it also affects the coloring of the glass. Furthermore, compared to TiO2 and Fe2O3, which also affect the coloring of glass like MoO3, the magnitude of its influence is MoO3 > Fe2O3 > TiO2. Therefore, the MoO3 content is preferably less than the contents of Fe2O3 and TiO2. In order to improve devitrification resistance while maintaining high transmittance, the upper limit of the content ratio MoO3 / (Fe2O3 + TiO2) is preferably 1 or less, 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, or 0.1 or less, and particularly preferably 0.05 or less. The lower limit of MoO3 / (Fe2O3+TiO2) in terms of content ratio is preferably 0.00001 or more, 0.00002 or more, 0.00003 or more, 0.00004 or more, 0.00005 or more, 0.00006 or more, 0.00007 or more, 0.00008 or more, 0.00009 or more, 0.0001 or more, 0.0005 or more, 0.001 or more, 0.002 or more, 0.003 or more, 0.004 or more, and particularly preferably 0.005 or more.

[0056] SnO2 acts as a clarifier for molten glass. The inclusion of SnO2 improves glass foaming, making it easier to produce glass with fewer defects. On the other hand, excessive SnO2 content can cause the glass to appear brown and reduce visible light transmittance. Therefore, the SnO2 content is preferably 3% or less, 1% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.45% or less, 0.4% or less, or 0.3% or less, and particularly preferably 2.5% or less. Excessively low SnO content increases the time required for foaming and may increase the amount of glass containing bubble defects. Therefore, to achieve glass with excellent foaming properties, the SnO2 content is preferably greater than 0%, 0.0001% or more, or 0.005% or more.

[0057] ZrO2 is a component that improves chemical durability, and is particularly effective in improving hydrolysis resistance and alkali resistance. However, excessive ZrO2 content increases the viscosity of the glass and tends to reduce devitrification resistance. Therefore, the ZrO2 content is preferably 0-3%, 0-2.5%, 0-2%, 0-1.5%, 0.1-0.8%, and particularly preferably 0.2-0.6%.

[0058] ZnO is a component that reduces high-temperature viscosity without reducing low-temperature viscosity. However, excessive ZnO content can deteriorate chemical durability, particularly hydrolysis resistance, and increase the likelihood of glass phase separation. Furthermore, devitrification resistance can be reduced, and density tends to increase. Therefore, the ZnO content is preferably 0-4%, 0-1%, and particularly preferably 0-0.01%.

[0059] P2O5 is a component that reduces high-temperature viscosity, improving meltability and formability. It also reduces Young's modulus. However, excessive P2O5 content can easily lead to turbidity in the glass due to phase separation and reduced acid resistance. Therefore, the P2O5 content is preferably 0-5%, 0-4%, 0-3.5%, and particularly preferably 0-3%.

[0060] In addition to SnO₂, one or more of the following may be introduced as fining agents: F, Cl, Sb₂O₃, As₂O₃, CeO₂, SO₃, etc. To achieve glass with improved foaming properties, the content of each of these fining agents is preferably greater than 0%, 0.00001% or greater, 0.0001% or greater, and particularly preferably 0.001% or greater. On the other hand, excessive amounts of these fining agents may cause coloration of the glass, or cause haze or blackening during processing into containers such as vials and ampoules, thereby reducing transmittance. Therefore, to achieve glass with higher transmittance, the content is preferably 5% or less, 1% or less, 0.5% or less, 0.1% or less, and particularly preferably 0.05% or less.

[0061] Fe2O3, TiO2, MoO3, SnO2, and CeO2 are components that can color glass if their contents are excessive. Therefore, in the pharmaceutical container glass and pharmaceutical container glass tube of the present invention, the Fe2O3+TiO2+MoO3+SnO2+CeO2 content is preferably 1% or less, 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, and particularly preferably less than 0.3%.

[0062] The higher the amount of clarifier, the better the foaming properties. However, excessive amounts can cause glass coloring, fogging or blackening during processing into containers such as vials and ampoules, and reduce transmittance. Therefore, in the pharmaceutical container glass and pharmaceutical container glass tube of the present invention, the upper limit of the F+Cl+Sb2O3+As2O3+SnO2+CeO2 content is preferably 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.35% or less, 0.3% or less, or 0.2% or less, and particularly preferably 0.1% or less. The lower limit is preferably 0.0001% or more, 0.001% or more, 0.005% or more, 0.01% or more, and particularly preferably 0.05% or more. This reduces the risk of defects due to the clarifier and achieves excellent foaming properties.

[0063] In order to improve chemical durability and reduce high-temperature viscosity, Cr2O3, PbO, La2O3, WO3, Nb2O3, Y2O3, etc. can be contained in amounts of less than 3%, less than 2%, less than 1%, less than 1%, and less than 0.5%, respectively.

[0064] As impurities, H2, CO2, CO, H2O, He, Ne, Ar, N2 and other components may be contained at up to 0.1%. In addition, precious metal elements such as Pt, Rh, and Au may be contained in an amount of 500 ppm or less, and further 300 ppm or less.

[0065] The glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention preferably have the following properties.

[0066] The pharmaceutical container glass and pharmaceutical container glass tube of the present invention preferably have a transmittance of at least 50% at a thickness of 1 mm in visible light with a wavelength of 380 to 760 nm. More preferably, the transmittance is 60% or higher, 70% or higher, 80% or higher, 85% or higher, 86% or higher, 87% or higher, 88% or higher, or 89% or higher, and particularly preferably 90% or higher. Higher transmittance improves visibility inside the glass container, making it easier to detect foreign matter after filling the container with pharmaceuticals.

[0067] In the glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention, the working point is preferably 1350° C. or lower, 1300° C. or lower, or 1260° C. or lower, and particularly preferably 1250° C. or lower. If the working point is too high, the molding temperature of the molten glass increases, and the life of the molding equipment tends to be shortened.

[0068] In the glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention, the viscosity of the glass melt is 10 2.5 dPa·s, the temperature is preferably 1700°C or lower, 1650°C or lower, 1640°C or lower, 1630°C or lower, 1620°C or lower, 1610°C or lower, and particularly preferably 1600°C or lower. The viscosity of the glass melt is 10 2.5 dPa·s, the lower the temperature, the lower the melting temperature, the less burden on glass manufacturing equipment such as melting furnaces, and the easier it is to improve the quality of the bubble. 2.5 dPa·s, the lower the temperature, the easier it is to reduce the manufacturing cost of the glass tube. On the other hand, if the viscosity of the glass melt is 10 2.5 As the temperature at dPa·s increases, the refractory in the melting furnace and the electrodes used for electric melting are more likely to be corroded by the glass, and the life of the forming equipment is likely to be shortened.

[0069] The glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention preferably have a grade of at least HGA2, particularly preferably HGA1, in a hydrolysis resistance test (acetone cleaning) according to ISO 720.

[0070] Furthermore, the alkali elution amount calculated as Na2O based on the hydrolysis resistance test (acetone cleaning) in accordance with ISO 720 is preferably less than 527 μg / g, 200 μg / g or less, 100 μg / g or less, 90 μg / g or less, 80 μg / g or less, 70 μg / g or less, less than 62 μg / g, 60 μg / g or less, 57 μg / g or less, 55 μg / g or less, or 53 μg / g or less, and particularly preferably 50 μg / g or less. If the alkali elution amount is too high, the alkali component will be eluted from the glass, causing fine defects on the surface, making the glass more susceptible to breakage due to collision, etc.

[0071] Here, the "hydrolysis resistance test (acetone cleaning) in accordance with ISO 720" refers to the following test.

[0072] (1) A glass sample was pulverized in an alumina mortar and classified with a sieve to a particle size of 300 to 425 μm.

[0073] (2) The obtained powder sample was washed with acetone and dried in an oven at 140°C.

[0074] (3) Place 10 g of the dried powder sample in a quartz flask, add 50 mL of purified water, cover, and autoclave. The autoclave is heated at 1°C / min from 100°C to 121°C, then hold at 121°C for 30 minutes and then cool to 100°C at 0.5°C / min.

[0075] (4) After the autoclave treatment, the solution in the quartz flask was transferred to another beaker, and the inside of the quartz flask was further rinsed three times with 15 mL of purified water, and the rinse solution was also added to the beaker.

[0076] (5) Add methyl red indicator to a beaker and titrate with 0.02 mol / L hydrochloric acid aqueous solution.

[0077] (6) Calculate the alkali elution amount per 1 g of glass by assuming that 1 mL of 0.02 mol / L hydrochloric acid aqueous solution is equivalent to 620 μg of Na2O.

[0078] Note that "the grade in the hydrolysis resistance test (acetone cleaning) according to ISO 720 is at least HGA2" means that the amount of alkali elution per 1g of glass calculated as Na2O determined by the above test is 527 μg / g or less.

[0079] Furthermore, the alkali resistance according to the test in accordance with ISO 695 is preferably at least grade 2. Here, the "alkali resistance test in accordance with ISO 695" refers to the following test.

[0080] (1) Prepare the surface area Acm where all mirror finishes are applied 2 (where A is set to 10 to 15 cm 2 ) sample. First, as a pretreatment, prepare a solution of hydrofluoric acid (40% by mass) 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 three times for 2 minutes using purified water and two times for 1 minute using ethanol.

[0081] (2) The sample was then dried in an oven at 110°C for 1 hour and allowed to cool naturally in a desiccator for 30 minutes.

[0082] (3) Measure the mass m1 of the sample to an accuracy of ±0.1 mg and record it.

[0083] (4) Prepare 800 mL of a solution of a sodium hydroxide aqueous solution (1 mol / L) and a sodium carbonate aqueous solution (0.5 mol / L) in a volume ratio of 1:1. Place this solution in a stainless steel container and bring it to a boil using a mantle heater. Next, place a sample suspended by a platinum wire in the container and hold for 3 hours. Remove the sample and perform ultrasonic cleaning three times for 2 minutes using purified water and two times for 1 minute using ethanol. Then, dry the sample in an oven at 110°C for 1 hour and allow it to cool naturally in a desiccator for 30 minutes.

[0084] (5) Measure the mass m2 of the sample to an accuracy of ±0.1 mg and record it.

[0085] (6) According to the mass m1, m2 (mg) before and after being put into the boiling alkali solution and the surface area A (cm 2 ), the mass reduction per unit area was calculated by the following calculation formula and used as the measured value of the alkali resistance test.

[0086] (Mass reduction per unit area) = 100 × (m1-m2) / A

[0087] Note that "alkali resistance based on the test in accordance with ISO 695 is level 2" means that the mass reduction per unit area determined as above is 175 mg / dm 2 It should be noted that if the mass reduction per unit area calculated as above is 75 mg / dm 2 Hereinafter, "alkali resistance according to the test in accordance with ISO 695 is Class 1". The mass reduction per unit area of ​​the glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention is preferably 130 mg / dm 2 Below, particularly preferably 75 mg / dm 2 If the mass loss increases, alkali components will be eluted from the glass, resulting in fine defects on the surface, making the glass more likely to break when struck by an object.

[0088] The β-OH value is an indicator of the amount of water in glass. Lowering the β-OH value can increase the strain point Ps, annealing point Ta, and softening point Ts. Therefore, even with the same glass composition and at the same temperature, glass with a low β-OH value is less likely to soften and flow, making it easier to achieve the desired devitrification resistance. Furthermore, when processing the glass into a container shape, excessive softening and deformation can be suppressed, making it easier to process into the desired shape. On the other hand, if the β-OH value is too low, the amount of infrared light absorbed by the glass during processing into the container shape tends to decrease, making it difficult to transfer heat from the burner and requiring a large amount of processing energy. Therefore, the β-OH value of the glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention is preferably 0.85 / mm or less, 0.80 / mm or less, 0.75 / mm or less, and particularly preferably 0.70 / mm. It is also preferably 0.3 / mm or more, 0.35 / mm or more, 0.4 / mm or more, and particularly preferably 0.45 / mm or more.

[0089] In addition, the β-OH value which shows the amount of water in glass can be calculated|required using the following formula.

[0090] β-OH=(1 / t)×log 10 (T1 / T2)t: Glass wall thickness (mm)

[0091] T1: Reference wavelength 3846cm -1 Transmittance at (2600nm) (%)

[0092] T2: Hydroxyl absorption wavelength 3600cm -1 Transmittance at (2800nm) (%)

[0093] In the present invention, T1 and T2 are measured using FT-IR Spectrometer Frontier manufactured by PerkinElmer.

[0094] The following methods can be used to reduce the β-OH value of the glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention. (1) Selecting a raw material with a low water content. For example, anhydrous borax containing no water can be used as a raw material for B2O3. (2) Heating the glass using electrodes, heaters, etc. during melting. (3) Adding a component (such as MoO3) that reduces β-OH to the glass.

[0095] The liquidus viscosity of the glass for pharmaceutical containers of the present invention is preferably 4.0 or greater, 4.3 or greater, 4.5 or greater, 4.8 or greater, 5.1 or greater, or 5.3 or greater, and particularly preferably 5.5 or greater, in terms of logη. If the liquidus viscosity is too low, devitrification resistance decreases, making it difficult to produce a glass tube using the Danner method or the like.

[0096] The glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention preferably have a thermal expansion coefficient of 40 to 60×10 -7 / ℃. The thermal expansion coefficient is more preferably 50 to 58×10 -7 / ℃, more preferably 51 to 55×10 -7 / ℃, and the most preferred range is 51~53×10 -7 / ℃. If the thermal expansion coefficient is lower than 40×10 -7 / °C, the viscosity of the glass tends to increase, the melting temperature and the forming temperature increase, and it becomes difficult to manufacture the glass. In addition, if the thermal expansion coefficient is higher than 60×10 -7 / °C, the possibility of breakage due to thermal shock in the glass manufacturing process, processing process, sterilization process, etc. becomes high.

[0097] Next, a method for producing the pharmaceutical container glass and pharmaceutical container glass tube of the present invention will be described. It should be noted that the method for producing the pharmaceutical container glass tube described below is the Danner method.

[0098] First, glass raw materials are mixed to form the above-mentioned glass composition to produce a glass batch. Next, the glass batch is continuously fed into a melting furnace at 1550-1700°C for melting and clarification. The resulting molten glass is then wound around a rotating refractory while air is blown from the top of the refractory, and the glass is pulled out in a tubular shape from the top.

[0099] The drawn tubular glass is then cut into predetermined lengths to produce glass tubes for pharmaceutical containers. These tubes are then used to manufacture vials and ampoules.

[0100] The glass tube for pharmaceutical containers of the present invention is not limited to the Danner method, and may be manufactured using any conventionally known method. For example, the Bello method or the down-draw method are effective methods for manufacturing the glass tube for pharmaceutical containers of the present invention.

[0101] Alternatively, containers can be formed directly from molten glass using methods such as blow molding. Containers formed using these methods are suitable not only for pharmaceuticals such as oral and parenteral drugs, but also for beverages, cosmetics, and other storage containers.

[0102] The pharmaceutical container glass and pharmaceutical container glass tube of the present invention can also be treated with ion exchange to form compressive stress on the surface. By forming compressive stress on the glass surface, it is possible to reduce glass breakage caused by falling or collision with other objects. The conditions of the ion exchange treatment are not particularly limited; the optimal conditions can be selected by considering the viscosity characteristics, application, thickness, internal tensile stress, dimensional changes, etc. of the glass. In particular, by ion-exchanging the K ions in the KNO molten salt with the Na component in the glass, a compressive stress layer on the surface can be efficiently formed.

[0103] The number of ion exchange treatments is not particularly limited and can be performed only once or multiple times. If the number of ion exchange treatments is limited to one, the manufacturing cost of the glass for pharmaceutical containers can be reduced. When multiple ion exchange treatments are performed, the number of ion exchange treatments is preferably two. This increases the stress depth and reduces the total amount of tensile stress accumulated within the glass.

[0104] The pharmaceutical container glass and pharmaceutical container glass tube of the present invention can also be etched with an acidic solution such as hydrofluoric acid or an alkaline solution. Etching the inner surface of the container is particularly preferred. Etching can remove damage, surface roughness, and foreign matter layers on the surface that occur during container processing, minimizing their effects.

[0105] Example

[0106] The present invention will be described below based on examples. The following examples are merely illustrative and the present invention is not limited to the following examples.

[0107] Tables 1 to 3 show examples of the present invention (samples No. 1 to No. 16).

[0108] [Table 1]

[0109] [wt%] No.1 No.2 No.3 No.4 No.5 No.6 <![CDATA[SiO2]]> 70.3 71.2 72.1 73.1 73.2 73.7 <![CDATA[Al2O3]]> 8.0 7.5 7.0 6.5 6.5 6.5 <![CDATA[B2O3]]> 12.0 11.5 11.0 10.5 10.0 9.5 <![CDATA[Li2O]]> 0.0 0.0 0.0 0.0 0.0 0.0 <![CDATA[Na2O]]> 6.9 6.4 5.9 5.4 8.0 7.0 <![CDATA[K2O]]> 0.9 1.4 1.9 2.4 1.0 2.0 MgO 0.0 0.0 0.0 0.0 0.0 0.0 CaO 0.7 0.7 0.7 0.7 1.0 10 SrO 0.0 0.0 0.0 0.0 0.0 0.0 BaO 1.2 1.2 1.2 1.2 0.1 0.1 <![CDATA[ZrO2]]> 0.0 0.0 0.0 0.0 0.0 0.0 F 0.0 0.0 0.0 0.0 0.0 0.0 Cl 0.0 0.1 0.1 0.1 0.1 0.1 <![CDATA[Sb2O3]]> 0.010 0.005 0.001 0.013 0.008 0.016 <![CDATA[As2O3]]> 0.0 0.0 0.0 0.0 0.0 0.0 <![CDATA[Fe2O3]]> 0.008 0.014 0.017 0.010 0.016 0.015 <![CDATA[TiO2]]> 0.007 0.020 0.025 0.017 0.041 0.055 <![CDATA[MoO3]]> 0.00001 0.00004 0.00013 0.00022 0.00044 0.001 <![CDATA[SnO2]]> 0.0 0.0 0.0 0.0 0.0 0.0 <![CDATA[CeO2]]> 0.0 0.0 0.0 0.0 0.0 0.0 <![CDATA[Li2O+Na2O+K2O(R2O)]]> 7.8 7.8 7.8 7.8 9.0 9.0 <![CDATA[100×MoO3 / R2O]]> 0.00013 0.00051 0.00167 0.00282 0.00489 0.01111 MgO+CaO+SrO+BaO(R'O) 1.9 1.9 1.9 1.9 1.1 1.1 <![CDATA[R2O / R'O]]> 4.1 4.1 4.1 4.0 8.2 8.2 CaO+BaO 1.9 1.9 1.9 1.9 1.1 1.1 CaO / BaO 0.6 0.6 0.6 0.6 10.0 10.0 <![CDATA[(R2O+R'O-Al2O3) / (SiO2+Al2O3+B2O3)]]> 0.019 0.024 0.030 0.036 0.040 0.040 <![CDATA[MoO3 / (Fe2O3+TiO2)]]> 0.0007 0.0012 0.0031 0.0081 0.0077 0.0143 <![CDATA[Fe2O3+TiO2+MoO3+SnO2+CeO2]]> 0.01501 0.03404 0.04213 0.02722 0.05744 0.071 <![CDATA[F+Cl+Sb2O3+As2O3+SnO2+CeO2]]> 0.010 0.105 0.101 0.113 0.108 0.116 transparency transparent transparent transparent transparent transparent transparent Transmittance [%] NA NA 92 NA NA NA Ps [℃] NA NA 528 NA NA NA Ta [℃] NA NA 571 NA NA NA Ts [℃] NA NA 786 NA NA NA <![CDATA[Operating point (10 4.0 dPa.s)[℃]]]> NA NA 1174 NA NA NA <![CDATA[10 2.5 dPa.s[℃]]]> NA NA 1636 NA NA NA Water degradation resistance test [μg / g] NA NA 19.2 NA N / A. NA <![CDATA[Alkali resistance test (ISO 695) [mg / dm 2 > NA NA NA NA NA NA β-OH NA NA 0.49 NA NA NA Liquidus temperature [℃] NA NA 912 NA NA NA logη NA NA 6.0 NA NA NA Heat expansion number (20-300℃) NA NA NA NA NA NA

[0110] [Table 2]

[0111] [wt%] No.7 No.8 No.9 No.10 No.11 No.12 <![CDATA[SiO2]]> 74.2 73.2 73.0 72.0 72.2 75.9 <![CDATA[Al2O3]]> 6.5 7.0 7.0 7.0 7.0 6.5 <![CDATA[B2O3]]> 9.0 110 11.0 11.0 11.0 9.0 <![CDATA[Li2O]]> 0.0 0.0 0.0 0.0 0.0 0.1 <![CDATA[Na2O]]> 6.0 6.0 6.5 7.4 5.0 7.6 <![CDATA[K2O]]> 3.0 2.0 2.0 0.1 3.0 0.1 MgO 0.0 0.0 0.0 0.0 0.0 0.1 CaO 1.0 0.1 0.1 1.0 0.5 0.1 SrO 0.0 0.0 0.0 0.0 0.0 0.1 BaO 0.1 0.5 0.1 1.2 1.0 0.1 <![CDATA[ZrO2]]> 0.0 0.0 0.0 0.0 0.0 0.1 F 0.0 0.0 0.1 0.0 0.0 0.0 Cl 0.1 0.1 0.0 0.1 0.1 0.1 <![CDATA[Sb2O3]]> 0.021 0.033 0.042 0.050 0.015 0.017 <![CDATA[As2O3]]> 0.0 0.0 0.1 0.0 0.0 0.0 <![CDATA[Fe2O3]]> 0.014 0.017 0.010 0.016 0.065 0.043 <![CDATA[TiO2]]> 0.020 0.033 0.066 0.083 0.027 0.023 <![CDATA[MoO3]]> 0.002 0.00001 0.00004 0.00013 0.00004 0.1 <![CDATA[SnO2]]> 0.0 0.0 0.0 00 0.1 0.0 <![CDATA[CeO2]]> 0.0 0.0 0.0 0.1 0.0 0.0 <![CDATA[Li2O+Na2O+K2O(R2O)]]> 9.0 8.0 8.5 7.5 8.0 7.8 <![CDATA[100×MoO3 / R2O]]> 0.02222 0.00013 0.00047 0.00173 0.00050 1.28205 MgO+CaO+SrO+BaO(R'O) 1.1 0.6 0.2 2.2 1.5 0.4 <![CDATA[R2O / R'O]]> 8.2 13.3 42.5 3.4 5.3 19.5 CaO+BaO 1.1 0.6 0.2 2.2 1.5 0.2 CaO / BaO 10.0 0.2 1.0 0.8 0.5 1.0 <![CDATA[(R2O+R'O-Al2O3) / (SiO2+Al2O3+B2O3)]]> 0.040 0.018 0.019 0.030 0.028 0.019 <![CDATA[MoO3 / (Fe2O3+TiO2)]]> 0.0588 0.0002 0.0005 0.0013 0.0004 1.5152 <![CDATA[Fe2O3+TiO2+MoO3+SnO2+CeO2]]> 0.036 0.05 0.076 0.199 0.192 0.166 <![CDATA[F+Cl+Sb2O3+As2O3+SnO2+CeO2]]> 0.121 0.133 0.242 0.250 0.215 0.117 transparency transparent transparent transparent transparent transparent transparent Transmittance [%] NA NA NA NA NA NA Ps [℃] NA NA NA NA NA NA Ta [℃] NA NA NA NA NA NA Ts [℃] NA NA NA NA N / A. NA <![CDATA[Operating point (10 4.0 dPa.s)[℃]]]> NA NA NA NA NA NA <![CDATA[10 2.5 dPa.s[℃]]]> NA NA NA NA NA NA Water degradation resistance test [μg / g] NA NA NA NA NA NA <![CDATA[Alkali resistance test (ISO 695 [mg / dm 2 > NA NA NA NA NA NA β-OH NA NA NA NA NA NA Liquidus temperature [℃] NA NA NA NA NA NA logη NA NA NA NA NA NA Heat expansion number (20-300℃) NA NA NA NA NA NA

[0112] [Table 3]

[0113] [wt%] No.13 No.14 No.15 No.16 <![CDATA[SiO2]]> 73.3 75.3 73.2 75.1 <![CDATA[Al2O3]]> 6.9 5.4 6.4 6.0 <![CDATA[B2O3]]> 11.1 10.8 11.0 10.5 <![CDATA[Li2O]]> 0.0 0.0 0.0 0.0 <![CDATA[Na2O]]> 7.2 6.9 6.6 6.7 <![CDATA[K2O]]> 0.7 0.0 1.6 0.7 MgO 0.0 0.0 0.0 0.0 CaO 0.6 1.3 1.0 0.5 SrO 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 <![CDATA[ZrO2]]> 0.0 0.0 0.0 0.0 F 0.0 0.2 0.0 0.2 Cl 0.1 0.0 0.1 0.2 <![CDATA[Sb2O3]]> 0.001 0.001 0.001 0.001 <![CDATA[As2O3]]> 0.0 0.0 0.0 0.0 <![CDATA[Fe2O3]]> 0.015 0.016 0.019 0.016 <![CDATA[TiO2]]> 0.009 0.025 0.009 0.014 <![CDATA[MoO3]]> 0.0001 0.0002 0.0006 0.0009 <![CDATA[SnO2]]> 0.0 0.0 0.0 0.0 <![CDATA[CeO2]]> 0.0 0.0 0.0 0.0 <![CDATA[Li2O+Na2O+K2O(R20)]]> 7.9 6.9 8.2 7.4 <![CDATA[100×MoO3 / R2O]]> 0.00127 0.00290 0.00732 0.01216 MgO+CaO+SrO+BaO(R'O) 0.6 1.3 1..0 0.5 <![CDATA[R2O / R’O]]> 13.2 5.3 8.2 14.8 CaO+BaO 0.6 1.3 1.0 0.5 CaO / BaO - - - - <![CDATA[(R2O+R’O-Al2O3) / (SiO2+Al2O3+B2O3)]]> 0.018 0.031 0.031 0.021 <![CDATA[MoO3 / (Fe2O3+TiO2)]]> 0.0042 0.0049 0.0214 0.0300 <![CDATA[Fe2O3+TiO2+MoO3+SnO2+CeO2]]> 0.0241 0.0412 0.0286 0.0309 <![CDATA[F+Cl+Sb2O3+As2O3+SnO2+CeO2]]> 0.101 0.201 0.101 0.401 transparency transparent transparent transparent transparent Transmittance [%] NA NA NA NA Ps [℃] 511 522 525 517 Ta [℃] 556 564 567 562 Ts [℃] 778 777 777 787 <![CDATA[Operating point (10 4.0 dPa.s)[℃]]]> 1165 1152 1144 1177 <![CDATA[10 2。5 dPa.s[℃]]]> 1596 1554 1541 1592 Water degradation resistance test [μg / g] 19 22 19 16 <![CDATA[Alkali resistance test (ISO 695) [mg / dm 2 > 141 115 NA NA β-OH 0.59 NA NA NA Liquidus temperature [℃] 942.0 NA NA NA logη 5.6 NA NA NA Thermal expansion coefficient (20-300℃) 51.7 48.5 53.6 49.0

[0114] The samples in the table were prepared as follows. First, 550 g of a batch was prepared to obtain the glass composition shown in the table and melted at 1600°C for 18 hours using a platinum crucible. It should be noted that in order to improve the homogeneity of the sample, stirring was performed twice during the melting process. Then, in order to reduce bubbles in the glass, the sample was melted at 1650°C for 2 hours. The molten glass was then flowed out to make ingots, which were then processed into the shapes required for measurement for various evaluations. The results are shown in the table.

[0115] Transparency was assessed visually on the two levels of transparency and coloration of the fabricated ingots. As a benchmark, when the text was clearly visible through the sample, the ingot was considered transparent, while when the text was not clearly visible, the ingot was considered colored.

[0116] Transmittance was measured using a 30 × 30 × 1 mm plate of glass with a mirror-finished surface. Measurements were made using a spectrophotometer (V-670 manufactured by JASCO Corporation) with a wavelength range of 380 to 760 nm, a bandwidth of 5 nm, a medium response, a scan speed of 200 nm, and a data acquisition interval of 1 nm. The table shows the lowest transmittance values ​​within the 380 to 760 nm wavelength range.

[0117] The strain point Ps was determined by a fiber drawing method according to ASTM C336. The annealing point Ta and the softening point Ts were determined by a fiber drawing method according to ASTM C388.

[0118] Working point (viscosity of glass is 10 4.0 dPa·s) and the viscosity of the glass is 10 2.5 The temperature in dPa·s was obtained by the platinum ball pulling method.

[0119] The hydrolysis resistance test was performed in accordance with the hydrolysis resistance test (acetone washing) in accordance with ISO 720. The detailed test procedure is as described above.

[0120] The liquidus temperature is as follows: a platinum boat of approximately 120×20×10 mm is filled with crushed glass, and after being placed in an electric furnace with a linear temperature gradient for 24 hours, the crystallization precipitation site is determined by observation under a microscope, and the temperature corresponding to the crystallization precipitation site is determined based on the temperature gradient curve of the electric furnace.

[0121] For the liquidus viscosity logη (η is the viscosity of the glass at the liquidus temperature (dPa·s)), the viscosity curve of the glass is obtained based on the strain point, annealing point, softening point, working point, and Fulcher's viscosity calculation formula, and the viscosity of the glass at the liquidus temperature is calculated based on this viscosity curve.

[0122] The thermal expansion coefficient was measured using a dilatometer at a temperature range of 20 to 300° C. using a glass sample formed into a rod of approximately 5 mmφ×20 mm as a measurement sample.

[0123] As can be seen from Tables 1 to 3, Examples Nos. 1 to 16 have high transparency. Furthermore, Examples Nos. 3 and 13 to 16 have high chemical durability and, due to their high strain points Ps, annealing points Ta, and softening points Ts, are believed to also have high devitrification resistance. In fact, the liquidus temperatures of Examples Nos. 3 and 13 are as low as 942°C or below.

[0124] Industrial Applicability

[0125] The glass for pharmaceutical containers and the glass tube for pharmaceutical containers of the present invention are suitable as materials for pharmaceutical containers such as vials, ampoules, and syringe barrels.

Claims

1. A glass for pharmaceutical containers, characterized in that: The glass composition includes, by mass%, SiO2 65% to 80%, Al2O3 1% to 10%, B2O3 5% to 20%, MoO3 greater than 0 and less than 0.1%, MgO+CaO+SrO+BaO0 to 10%, and Li2O+Na2O+K2O 1% to 20%.

2. The glass for pharmaceutical containers according to claim 1, wherein The content of Na2O is 5% to 9%, and the content of K2O is 0.1% to 3%.

3. The glass for pharmaceutical containers according to claim 2, wherein: The content of CaO is 0.1% to 2%, and the content of BaO is 0.1% to less than 1.3%.

4. The glass for pharmaceutical containers according to claim 2 or 3, wherein: MgO+CaO+SrO+BaO is 0.2% to 10%, and the content ratio (Li2O+Na2O+K2O) / (MgO+CaO+SrO+BaO) is 3 to 10.

5. The glass for pharmaceutical containers according to claim 2 or 3, wherein: The content of Fe2O3 is 0.001% to 0.05%, the content of TiO2 is 0.001% to 0.05%, the content ratio MoO3 / (Fe2O3+TiO2) is 0.0001 to 0.1, and the visible light transmittance at a thickness of 1 mm is above 80%.

6. The glass for pharmaceutical containers according to claim 2 or 3, wherein: F+Cl+Sb2O3+As2O3+SnO2+CeO2 is 0.01% to 0.5%.

7. The glass for pharmaceutical containers according to claim 2 or 3, wherein: Fe2O3+TiO2+MoO3+SnO2+CeO2 is less than 0.5%, and the visible light transmittance at a thickness of 1 mm is more than 85%.

8. The glass for pharmaceutical containers according to claim 2 or 3, wherein: The content of Li2O is 0-0.1%, the content of MgO is 0-0.1%, the content of SrO is 0-0.1%, Li2O+Na2O+K2O is 5.1%-12.1%, and MgO+CaO+SrO+BaO is 0.2%-less than 2.5%.

9. The glass for pharmaceutical containers according to claim 2 or 3, wherein: The thermal expansion coefficient at 20℃~300℃ is 40×10 -7 / ℃~60×10 -7 / ℃.

10. A glass for pharmaceutical containers, characterized in that: The glass composition, in mass%, contains: SiO2 68% to 77%, Al2O3 6.5% to 8%, B2O3 9% to 12%, MoO3 greater than 0 and less than 0.1%, CaO 0.1% to 2%, BaO 0.1% to less than 1.3%, MgO + CaO + SrO + BaO 0.2% to less than 2.5%, Na2O 5% to 9%, K2O 0.1% to 3%, Li2O + Na2O + K2O 5.1% to 12.1%, Fe2O3 0.001% to 0.05%, TiO2 0.001% to 0.05%, F + Cl + Sb2O3 + As2O3 + SnO2 + CeO2 0.01%~0.5%, the content ratio MoO3 / (Fe2O3+TiO2) is 0.0001~0.

1.

11. The glass for pharmaceutical containers according to claim 10, wherein: The Cl content is 0.001% to 0.1%, and the Sb2O3 content is 0.001% to 0.05%.

12. A glass tube for a pharmaceutical container, characterized in that: The glass composition comprises, in mass%, SiO2 68% to 77%, Al2O3 6.5% to 8%, B2O3 9% to 12%, CaO 0.1% to 2%, BaO 0.1% to less than 1.3%, MoO3 greater than 0 and less than 0.1%, MgO + CaO + SrO + BaO 0.2% to less than 2.5%, Na2O 5% to 9%, K2O 0.1% to 3%, Li2O + Na2O + K2O 5.1% to 12.1%, Fe2O3 0.001% to 0.05%, TiO2 0.001% to 0.05%, F + Cl + Sb2O3 + As2O3 + SnO2 + CeO2 0.01%~0.5%, the content ratio MoO3 / (Fe2O3+TiO2) is 0.0001~0.

1.

13. The glass tube for a pharmaceutical container according to claim 12, wherein: The Cl content is 0.001% to 0.1%, and the Sb2O3 content is 0.001% to 0.05%.