JP6694167B2 - Borosilicate glass for pharmaceutical containers - Google Patents

Description

  The present invention relates to glass for tube bottles such as vials and ampoules, and borosilicate glass for pharmaceutical containers used for syringes of syringes.

Borosilicate glass for pharmaceutical containers such as vials and ampoules is required to have the following characteristics.
(A) The components in the filled chemical liquid do not react with the components in the glass (b) High chemical durability and high hydrolysis resistance so as not to contaminate the filled chemical liquid (c) Manufacturing of glass tube Low thermal expansion so that damage due to thermal shock does not easily occur during processing or processing into vials, ampoules, etc. (d) Low working temperature so that processing into vials, ampoules, etc. can be performed at low temperatures. The standard borosilicate glass for pharmaceutical containers that satisfies the required characteristics contains SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , Na ₂ O, K ₂ O, CaO, and BaO as a constituent and a small amount of a fining agent. Contains.

US Pat. No. 4,386,164

  In recent years, the development of a drug solution to be filled has progressed, and a drug solution having a higher drug efficacy is being used. Along with this, as borosilicate glass for pharmaceutical containers constituting vials and ampoules, glass having higher chemical durability and hydrolysis resistance than ever before is required. In addition, when BaO is contained in the glass, barium feldspar crystals are likely to precipitate due to the reaction with the alumina refractory when the glass is melted, which lowers the production yield, and also reacts with the sulfate ion in the chemical solution to form a precipitate. May occur.

  Under such circumstances, for example, Patent Document 1 proposes a glass containing no BaO.

However, the working temperature rises if BaO is not contained. Therefore, Patent Document 1 proposes a glass in which a large amount of B ₂ O ₃ is added to reduce the viscosity of the glass, but this results in deterioration of hydrolysis resistance.

  An object of the present invention is to provide a borosilicate glass for pharmaceutical containers, which is a glass containing no BaO, has good chemical durability and hydrolysis resistance, and has a low working temperature.

The medicinal borosilicate glass of the present invention has a mass% of SiO _{2 of} 70.0 to 75.5%, Al ₂ O _{3 of} 6.3 to 11%, B ₂ O _{3 of 3 to} 11.5%, and Na ₂ O 4. _{.0~8.5%, K 2 O 0~5%} , Li 2 O containing from 0 to 0.2%, characterized in that it contains no BaO substantially. The phrase "substantially free of BaO" means that BaO is not positively added, and does not mean that impurities that are mixed as impurities are excluded. More specifically, it means that the content of BaO is 0.05% or less.

According to the above configuration, since BaO is not contained, barium feldspar crystals do not precipitate due to the reaction between BaO and the alumina refractory during glass melting or molding. In addition, a glass that does not easily react with the sulfate ion in the chemical solution can be obtained. Moreover, since this glass has a high content of Al ₂ O ₃ , it has excellent chemical durability and hydrolysis resistance. Further, since the content of Li ₂ O is strictly limited, it is possible to effectively prevent the refractory erosion at the time of melting the glass and reduce the raw material cost.

  In the present invention, it is preferable that the contents of MgO, CaO and SrO are each 0 to 4% by mass.

  According to the said structure, it becomes easy to obtain glass with low working temperature, suppressing a fall of chemical durability and hydrolysis resistance.

  In the present invention, it is further preferable that MgO + CaO + SrO is 0 to 4 mass%.

  According to the said structure, it becomes easy to obtain glass with low working temperature, suppressing a fall of chemical durability and hydrolysis resistance.

  In the present invention, MgO + CaO is preferably 0 to less than 1% by mass.

  According to the said structure, it becomes easy to obtain glass excellent in hydrolysis resistance.

In the present invention, it is preferable that the content of Na ₂ O + K ₂ O + Li ₂ O is 5 to 10% by mass.

  According to the said structure, it becomes easy to obtain glass with low working temperature, suppressing a fall of chemical durability and hydrolysis resistance.

In the present invention, the content of Fe ₂ O ₃ is preferably 0 to less than 0.2% by mass.

  According to the above configuration, it is possible to effectively prevent coloring of the glass.

In the present invention, the value of (MgO + CaO + SrO) / (Na ₂ O + K ₂ O + Li ₂ O) is adjusted to 0.10 or less by mass ratio in order to obtain a glass having low viscosity and excellent hydrolysis resistance. Preferably. Note that “(MgO + CaO + SrO) / (Na ₂ O + K ₂ O + Li ₂ O)” is a value obtained by dividing the content of MgO, CaO, and SrO by the total content of Na ₂ O, K ₂ O, and Li ₂ O. Is.

  According to the said structure, it becomes easy to obtain glass with low working temperature, suppressing a fall of chemical durability and hydrolysis resistance.

In the present invention, CaO / (Na ₂ O + K ₂ O + Li ₂ O) is preferably 0 to 0.10. The term “CaO / (Na ₂ O + K ₂ O + Li ₂ O)” is a value obtained by dividing the content of CaO by the total content of Na ₂ O, K ₂ O and Li ₂ O.

  According to the above-mentioned composition, glass with good workability and high hydrolysis resistance can be obtained.

In the present invention, the mass ratio of K ₂ O / Na ₂ O is preferably 0.2 to 1. In addition, "K ₂ O / Na ₂ O" is a value obtained by dividing the content of K ₂ O by the content of Na ₂ O.

  According to the said structure, it becomes easy to obtain glass with low working temperature, suppressing a fall of hydrolysis resistance.

In the present invention, the mass ratio of Al ₂ O ₃ / (Na ₂ O + K ₂ O + Li ₂ O + MgO + CaO + SrO + B ₂ O ₃ ) is preferably 0.32 or more. Note that “Al ₂ O ₃ / (Na ₂ O + K ₂ O + Li ₂ O + MgO + CaO + SrO + B ₂ O ₃ )” means that the content of Al ₂ O ₃ is Na ₂ O, K ₂ O, Li ₂ O, MgO, CaO, SrO and It is a value divided by the total content of B ₂ O ₃ .

  According to the above configuration, the hydrolysis performance can be further improved.

In the present invention, it is preferable that the mass ratio of Al ₂ O ₃ / (Na ₂ O + K ₂ O + Li ₂ O) is 0.7 to 1.5.

  According to the above configuration, the hydrolysis performance can be further improved.

  In the present invention, in the powder test method of the hydrolysis resistance test according to EP 7.0, the consumption of 0.02 mol / L hydrochloric acid per unit glass mass is preferably 0.030 mL or less.

In the present invention, the amount of mass reduction per area is preferably 1.0 mg / dm ² or less in the acid resistance test according to DIN12116.

In the present invention, it is preferable to have a working temperature of 1150 ° C to 1250 ° C. The working temperature is a temperature at which the viscosity of the glass becomes 10 ⁴ dPa · s.

  According to the above configuration, it is possible to lower the processing temperature when manufacturing a glass container such as an ampoule or a vial from a glass tube, and it is possible to significantly reduce the evaporation amount of the alkaline component in the glass. As a result, it is possible to avoid a situation in which the chemical liquid components stored in the glass container are deteriorated or the pH of the chemical liquid is increased.

In the present invention, it is preferable to have a liquidus viscosity of 10 ^4.5 dPa · s or more.

  According to the above configuration, even when the Dunner method is used for molding the glass tube, devitrification during molding is less likely to occur, which is preferable.

  The glass tube for a medicine container of the present invention is characterized by comprising the above borosilicate glass for a medicine container.

  The pharmaceutical container of the present invention is characterized by comprising the above borosilicate glass for a pharmaceutical container.

9 is a graph showing the evaluation results of Example 2.

  Hereinafter, the reason why the composition range of each component is limited as described above will be described. In addition, in the following description, unless otherwise specified,% indication means mass%.

SiO ₂ is one of the elements that make up the glass network. The content of SiO ₂ is 70.0 to 75.5%, preferably 70.0 to less than 75.5%, 70.0 to less than 75.0%, 70.0 to 74.7%, 70. 0.0 to less than 74.5%, particularly 71 to less than 74.5. If the content of SiO ₂ is too small, the chemical durability is lowered, and the acid resistance required for borosilicate glass for pharmaceutical containers cannot be satisfied. On the other hand, if the content of SiO ₂ is too large, the liquidus viscosity decreases, and devitrification is likely to occur in the manufacturing process.

Al ₂ O ₃ is a component that suppresses devitrification of glass, and also improves chemical durability and hydrolysis resistance. The content of Al ₂ O ₃ is 6.3 to 11%, preferably more than 6.3% and 10% or less, 6.4 to 8.5%, 6.4 to 8.3%, and particularly 6. It is 0.5 to 7.7%. If the content of Al ₂ O ₃ is too small, the above effect cannot be obtained. On the other hand, if the content of Al ₂ O ₃ is too large, the viscosity of the glass increases and the target working temperature cannot be obtained.

B ₂ O ₃ has the effect of not only lowering the melting point of glass but also increasing the liquidus viscosity and suppressing devitrification. _Therefore, the content is 3 to 11.5% B 2 _{O 3,} preferably less than 5.5 to 11.5%, more preferably less than 8.5 to 11.5%, more preferably 9 to 11.5 It is less than%. When the content of B ₂ O ₃ is too small, the high temperature viscosity increases. On the other hand, if the content of B ₂ O ₃ is too large, the hydrolysis resistance and the chemical durability decrease.

Na ₂ O has the effect of lowering the viscosity of glass and increasing the coefficient of linear thermal expansion. The content of Na ₂ O is 4.0 to 8.5%, preferably 4.0 to less than 8.5%, further 4.0 to 8.0%, 4.0 to 7.0%. It is more than 4.0% and 7.0%, especially 5.0 to 7.0%. If the content of Na ₂ O is too small, the high temperature viscosity increases. On the other hand, if the content of Na ₂ O is too large, the hydrolysis resistance deteriorates.

K ₂ O also has the effect of lowering the viscosity of glass and increasing the coefficient of linear thermal expansion similarly to Na ₂ O. The content of K ₂ O is 0 to 5%, preferably 0.1 to 5%, 0.5 to 4.5%, further 1.0 to 3%, and particularly 1.5 to 2.5%. is there. If the content of K ₂ O is too large, the hydrolysis resistance deteriorates.

It is preferable to use both K ₂ O and Na ₂ O in combination, because the combined alkali effect improves the hydrolysis resistance.

Further, in order to further improve the hydrolysis resistance, the value of K ₂ O / Na ₂ O is 0.2 to 1, 0.2 to 0.95, 0.2 to 0.8, particularly 0 in terms of mass ratio. It is desirable to be 0.2 to 0.7. If this ratio is too small, the hydrolysis resistance deteriorates. On the other hand, if this ratio is too large, the high temperature viscosity increases and the workability decreases.

Li ₂ O, like Na ₂ O and K ₂ O, has the effects of lowering the viscosity of glass and increasing the coefficient of linear thermal expansion. However, when Li ₂ O is added, the refractory is likely to erode when the glass is melted. It also leads to an increase in production cost. Therefore, the content of Li ₂ O is preferably 0 to 0.2%, 0 to less than 0.2%, 0 to 0.1%, 0 to 0.05%, and particularly 0 to 0.01%. Unless there are special circumstances, it is desirable to use an alkali oxide other than Li ₂ O.

The total content of Li ₂ O, Na ₂ O and K ₂ O is preferably 5-10%, especially 6-9%. If the total amount of these components is too small, workability becomes poor. On the other hand, if the total amount of these components is too large, the chemical durability and the resistance to hydrolysis deteriorate.

  Further, in the present invention, various components other than the above may be added.

  MgO has the effect of improving chemical durability. The content of MgO is preferably 0 to less than 4.0%, 0 to 2.0%, and particularly 0.05 to 1.0%. If the content of MgO is too large, the hydrolysis resistance deteriorates.

  CaO has the effect of reducing the high temperature viscosity of glass. The content of CaO is preferably 0 to less than 4.0%, 0 to 1.5%, 0 to 1.1%, 0 to 0.9%, and 0.1 to 0.5%. If the CaO content is too high, the hydrolysis resistance deteriorates.

  SrO has the effect of improving chemical durability. The content of SrO is preferably 0 to less than 4.0%, 0 to 2.0%, and particularly 0 to 1.0%. If the content of SrO is too large, the hydrolysis resistance deteriorates.

  The total content of MgO, CaO, and SrO is 0 to 4.0%, 0 to 3.0%, 0 to 2.0%, and 0 to less than 1.0%, particularly 0.1 to 0.5%. % Is preferable. If the total amount of these components is too large, the hydrolysis resistance deteriorates.

  The total content of MgO and CaO is 0 to less than 1%, more preferably 0 to 0.8% and 0.1 to 0.5%. If the total amount of these components is too large, the hydrolyzability deteriorates.

TiO ₂ has an effect of improving hydrolysis resistance. The content of TiO ₂ is 0 to less than 7.0%, preferably 0 to 5.0%, 0 to 4.0%, and particularly preferably 0.1 to 1.5%. If the content of TiO ₂ is too large, the high temperature viscosity increases.

ZrO ₂ has an effect of improving hydrolysis resistance. The content of ZrO ₂ is 0 to less than 7.0%, preferably 0 to 5.0%, 0 to 4.0%, and particularly preferably 0.1 to 1.5%. When the content of ZrO ₂ is too large, the high temperature viscosity increases.

Fe ₂ O ₃ may color the glass and reduce the transmittance in the visible range, so the content thereof is limited to 0.2% or less, 0.1% or less, and particularly 0.02% or less. Is desirable.

In addition, one or more of Cl, Sb ₂ O ₃ , SnO ₂ , Na ₂ SO _{4 and the} like may be contained as a fining agent. The total content of these fining agents is 3% or less, preferably 1% or less, more preferably 0.5% or less. Further, among these fining agents, it is preferable to use Cl or SnO ₂ because it has a low melting temperature and little harm to the human body. When Cl is used, its content is preferably 3% or less, particularly 0.1 to 1%. When SnO ₂ is used, its content is preferably 2% or less, particularly 0.01 to 0.5%.

  When BaO is contained in the glass composition, as described above, there is a possibility that crystals may be precipitated or precipitates may be generated due to the reaction with the alumina refractory or the reaction with the sulfate ion in the chemical solution. is there. Therefore, the present invention does not substantially contain BaO.

Further, in the present invention, in order to obtain a glass having low viscosity and high hydrolysis resistance, the value of (MgO + CaO + SrO) / (Na ₂ O + K ₂ O + Li ₂ O) is 0.10 or less, 0.08 or less by mass ratio. Hereafter, it is preferably adjusted to 0.07 or less, particularly less than 0.07. On the other hand, if this value is too large, the hydrolysis resistance decreases. The lower limit of the value of (MgO + CaO + SrO) / (Na ₂ O + K ₂ O + Li ₂ O) is preferably 0.01, and more preferably 0.02.

For the same reason, it is preferable to adjust the value of CaO / (Na ₂ O + K ₂ O + Li ₂ O) by mass ratio to 0.10 or less, 0.08 or less, 0.07 or less, and particularly less than 0.07. .. If this value is too large, the hydrolysis resistance decreases. The lower limit of the value of CaO / (Na ₂ O + K ₂ O + Li ₂ O) is preferably 0.01, particularly 0.02.

Further, in the present invention, Al ₂ O ₃ which is a component that improves the hydrolysis resistance but increases the viscosity of glass, and Na ₂ which is a component that decreases the viscosity of the glass but decreases the hydrolysis resistance. It is desirable to balance the contents of O, K ₂ O, Li ₂ O, MgO, CaO, SrO, and B ₂ O ₃ in order to achieve both hydrolysis resistance and good processability. Specifically, the mass ratio of Al ₂ O ₃ / (Na ₂ O + K ₂ O + Li ₂ O + MgO + CaO + SrO + B ₂ O ₃ ) is 0.32 or more, preferably 0.34 or more, and this value is 0.60 or less. It is particularly desirable that it is 0.50 or less.

Further, the mass ratio of Al ₂ O ₃ / (K ₂ O + Na ₂ O + Li ₂ O) is preferably 0.7 to 1.5, 0.75 to 1.5, and particularly 0.75 to 1.2. If this ratio is too small, hydrolysis resistance deteriorates, and if it is too high, workability decreases.

  Further, the borosilicate glass for a pharmaceutical container of the present invention preferably has the following characteristics.

  In the powder test method of the hydrolysis resistance test according to EP 7.0, the consumption of 0.02 mol / L hydrochloric acid per unit glass mass is preferably 0.030 mL or less, 0.028 mL or less, 0.026 mL or less. , Especially 0.025 mL or less. If the amount of hydrochloric acid consumed is too large, when a bottle container such as an ampoule or a vial is prepared, and a chemical solution is filled and stored, the elution of the glass component, particularly the alkaline component, may be significantly increased to cause the deterioration of the chemical solution component.

In the acid resistance test according to DIN12116, the amount of mass reduction per unit area is preferably 1.0 mg / dm ² or less, and particularly 0.8 mg / dm ² or less. When the amount of mass reduction is large, when a bottle container such as an ampoule or a vial is prepared, and a chemical solution is filled and stored, the amount of the glass component eluted may significantly increase and the chemical solution component may be deteriorated.

  By the way, when the hydrolysis resistance is improved, the working temperature and the melting temperature tend to rise. For example, Pyrex glass has excellent hydrolysis resistance, but its working temperature is as high as 1250 ° C or higher. However, the glass of the present invention can have a working temperature of 1250 ° C or lower, 1150 ° C to 1250 ° C, 1150 ° C to 1240 ° C, and particularly 1160 ° C to 1230 ° C, despite having high hydrolysis resistance. When the working temperature is high, the processing temperature for producing a glass container such as an ampoule or a vial from a glass tube becomes high, and the evaporation amount of the alkaline component in the glass remarkably increases. The evaporated alkaline component adheres to the inner surface of the glass container and elutes during storage of the chemical liquid or during autoclave treatment after filling the chemical liquid, which causes alteration of the chemical liquid component and increase of pH of the chemical liquid.

  Pharmaceutical containers such as ampoules and vials are processed by locally heating tube glass with a burner. Then, after processing, heat treatment is performed in an electric furnace to remove residual strain in the glass. Hydrolysis resistance may be deteriorated by local heating during processing and subsequent heat treatment. However, the glass of the present invention can maintain stable hydrolysis resistance even after processing and heat treatment.

The liquidus viscosity is preferably 10 ^4.5 dPa · s or more, 10 ^5.0 dPa · s or more, 10 ^5.2 dPa · s or more, 10 ^5.4 dPa · s or more, particularly 10 ^5.6 dPa · s. s or more. When the liquidus viscosity is low, devitrification is likely to occur at the time of forming a glass tube by the Danner method, and productivity is deteriorated.

The linear thermal expansion coefficient is an important parameter in the thermal shock resistance of glass. In order for the glass to obtain sufficient thermal shock resistance, the coefficient of linear thermal expansion in the temperature range of 30 to 380 ° C. is preferably 58 × 10 ⁻⁷ / ° C. or less, and particularly 48 to 55 × 10 ⁻⁷ / ° C. ..

  Next, a method for producing the glass tube for a pharmaceutical container of the present invention will be described. The following description is an example using the Dunner method.

  First, glass raw materials are prepared so as to have the above glass composition, and a glass batch is prepared. Then, this glass batch was continuously charged into a melting furnace at 1550 to 1700 ° C. to be melted and clarified, and then the obtained molten glass was wound around a rotating refractory, while blowing air from the tip of the refractory, The glass is tubularly drawn from the tip. The drawn tubular glass is cut into a predetermined length to obtain a glass tube for a medicine container. The glass tube thus obtained is used for manufacturing vials and ampoules.

  The glass tube for a medicine container of the present invention is not limited to the Dunner method, and may be manufactured by any conventionally known method. For example, the bellows method and the downdraw method are also effective methods for manufacturing the glass tube for a pharmaceutical container of the present invention.

Hereinafter, the present invention will be described based on examples.
(Example 1)
Tables 1 to 6 show Examples (Sample Nos. 1 to 10 and 13 to 38) of the present invention and Comparative Examples (Sample Nos. 11 and 12). In the table, “ΣR ₂ O” represents “K ₂ O + Na ₂ O + Li ₂ O”, “ΣRO” represents “MgO + CaO + SrO”, and “CaO / ΣR ₂ O” represents “CaO / (Na ₂ O + K ₂ O + Li ₂ O) ”and“ Al ₂ O ₃ / (B ₂ O ₃ + ΣR ₂ O + ΣRO) ”represents“ Al ₂ O ₃ / (Na ₂ O + K ₂ O + Li ₂ O + MgO + CaO + SrO + B ₂ O ₃ ) ”. ing.

  Each sample was prepared as follows.

  First, a glass-built batch of 500 g was prepared so as to have the composition shown in the table, and melted at 1650 ° C. for 4 hours using a platinum crucible. In addition, in order to remove bubbles in the melt, stirring was performed twice during the melting. After melting, an ingot was prepared, processed into a shape required for measurement, and subjected to various evaluations.

  As is clear from Tables 1 to 6, Sample No. 1 to 10 and sample No. 13-38 showed good hydrolysis resistance and chemical durability. It was also found that each sample had a working temperature of 1220 ° C. or lower. Further, when the elution of Sn by the hydrolysis resistance test was evaluated for the samples containing Sn in the glass composition, the Sn elution amount of each sample was below the lower limit of detection. On the other hand, Sample No. which is a comparative example. In Nos. 11 and 12, although no Sn elution was observed, the hydrolysis resistance was poor.

  The linear thermal expansion coefficient was measured by a dilatometer in the temperature range of 30 to 380 ° C. using a glass sample molded into a rod shape of about 5 mmφ × 50 mm.

  The strain point, the slow cooling point and the softening point were measured by the fiber elongation method.

Regarding the working temperature, the viscosity curve of glass was obtained from the high temperature viscosity obtained by the platinum ball pull-up method and the Fulcher viscosity calculation formula, and the temperature corresponding to 10 ⁴ dPa · s was obtained from this viscosity curve.

  The liquidus temperature was measured by charging a crushed glass sample in a platinum boat of about 120 × 20 × 10 mm and placing it in an electric furnace having a linear temperature gradient for 24 hours. After that, the crystal precipitation portion was specified by microscopic observation, the temperature corresponding to the crystal precipitation portion was calculated from the temperature gradient graph of the electric furnace, and this temperature was taken as the liquidus temperature.

  The liquidus viscosity is calculated by obtaining the viscosity curve of the glass from the strain point, the slow cooling point, the softening point, the working temperature and the Fulcher's viscosity calculation formula, and calculating the viscosity of the glass at the liquidus temperature from this viscosity curve. Was defined as the liquidus viscosity.

  The hydrolysis resistance test was conducted by crushing the sample using an alumina mortar and pestle and by a method according to the powder test method of EP 7.0. The detailed test procedure is as follows. The surface of the sample was wiped well with ethanol, the sample was crushed with an alumina mortar and pestle, and then classified using three sieves with openings 710 μm, 425 μm, and 300 μm made of stainless steel. What remained on the sieve was pulverized again, the same sieving operation was performed, and the sample powder remaining on the 300 μm sieve was washed with ethanol and put into a glass container such as a beaker. After that, ethanol was added, and the mixture was stirred, washed with an ultrasonic cleaner for 1 minute, and then the operation of pouring out only the supernatant was performed 6 times. Then, it was dried in an oven at 110 ° C. for 30 minutes and cooled in a desiccator for 30 minutes. The obtained sample powder was weighed with an electronic balance with an accuracy of 10 g ± 0.0001 g, put in a 250 mL quartz flask, and 50 mL of ultrapure water was added. After sealing, the flask was placed in an autoclave and kept at 121 ° C for 30 minutes. The temperature was raised from 100 ° C. to 121 ° C. at 1 ° C./min, and the temperature was lowered from 121 ° C. to 100 ° C. at 2 ° C./min. After cooling to 95 ° C, the sample was taken out into a conical beaker. The inside of the flask was washed with 30 mL of ultrapure water and poured into a conical beaker three times. After adding about 0.05 mL of methyl red to the liquid after the test, neutralization titration was performed with 0.02 mol / L hydrochloric acid, the consumption of hydrochloric acid was recorded, and the consumption of hydrochloric acid per 1 g of the sample glass was calculated.

The acid resistance test was performed according to DIN12116, with a sample surface area of 50 cm ² and a liquid amount of 6 mol / L hydrochloric acid as an eluent of 800 mL. The detailed test procedure is as follows. First, a glass sample piece having a total surface area of 50 cm ² with all surfaces mirror-polished was prepared. As a pretreatment, the sample was treated with hydrofluoric acid (40% by mass) and hydrochloric acid (2 mol / L) at a volume ratio of 1: 9. It was immersed in the mixed solution so that it was stirred with a magnetic stirrer for 10 minutes. Then, the sample piece was taken out, subjected to ultrasonic cleaning for 2 minutes in ultrapure water three times, and then ultrasonically cleaned for 1 minute in ethanol twice. Next, the sample piece was dried in an oven at 110 ° C. for 1 hour and cooled in a desiccator for 30 minutes. The mass m ₁ of the sample piece thus obtained was measured to an accuracy of ± 0.1 mg and recorded. Subsequently, 800 mL of 6 mol / L hydrochloric acid was placed in a beaker made of quartz glass, heated using an electric heater until boiling, and a sample piece hung with a platinum wire was put therein and held for 6 hours. The opening of the lid of the container was capped with a gasket and cooling tube to prevent loss of liquid volume during the test. Then, the sample piece was taken out, subjected to ultrasonic cleaning for 2 minutes in ultrapure water three times, and then ultrasonically cleaned for 1 minute in ethanol twice. Further, the washed sample piece was dried in an oven at 110 ° C. for 1 hour and cooled in a desiccator for 30 minutes. The mass piece m ₂ of the sample thus treated was measured to an accuracy of ± 0.1 mg and recorded. Finally, the mass reduction amount per unit area was calculated from the masses m ₁ and m ₂ mg of the sample before and after being added to boiling hydrochloric acid and the total surface area Acm ^{2 of the} sample by the following formula 1 and used as the measurement value of the acid resistance test. .

[Formula 1] Mass reduction amount per unit area = 100 × (m ₁ −m ₂ ) / 2 × A
The elution amount of Sn was analyzed by an ICP emission spectrometer (manufactured by Varian) for the test solution after the hydrolysis resistance test. The detailed test procedure is as follows. The test solution after the hydrolysis resistance test was filtered with a membrane filter and collected in a centrifuge tube. The Sn standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) was diluted to prepare a standard solution so that the Sn content was 0 mg / L, 0.05 mg / L, 0.5 mg / L, 1.0 mg / L. .. A calibration curve was prepared from these standard solutions, and the Sn elution amount in the test solution was calculated. The measurement wavelength of Sn was set to 189.925 nm.
(Example 2)
The change in hydrolysis resistance due to heat treatment was investigated. Table 7 shows the compositions of the example of the present invention (Sample No. 10 used in Example 1) and the comparative example (Sample No. 39). Sample No. 39 is Pyrex (registered trademark) glass.

  Each sample was prepared in the same manner as in Example 1. Next, each prepared sample was heat-treated at 600 ° C. and 900 ° C. for 5 hours in an electric furnace. It should be noted that 600 ° C. and 900 ° C. are temperatures assuming heat treatment after processing into a pharmaceutical container. The samples after heat treatment at each temperature were evaluated for hydrolysis resistance in the same manner as in Example 1. The results are shown in FIG. As shown in FIG. In Sample No. 39, hydrolysis resistance deteriorates depending on the heat treatment temperature, but Sample No. It can be seen that 10 has stable hydrolysis resistance even after various heat treatments.

The borosilicate glass for a pharmaceutical container of the present invention can be suitably used as a material for various pharmaceutical containers such as an ampoule, a vial, a prefilled syringe and a cartridge. Moreover, since the borosilicate glass for a pharmaceutical container of the present invention contains an alkali, the pharmaceutical container produced using this can be chemically strengthened.

Claims (10)

In mass%, SiO ₂ 70.0 to 75.5%, Al ₂ O ₃ 6.3 to 11%, B ₂ O _{3 3 to} 11.5%, Na ₂ O 4.0 to 8.5%, K ₂ O 2-5%, Li ₂ O 0-0.2%, MgO + CaO 0-0.5% are contained, BaO is not substantially contained , and K ₂ O / Na ₂ O is 0.32-by mass ratio. A borosilicate glass for pharmaceutical containers, which is 0.7 . _{Na 2 O + K 2 O +} Li 2 O pharmaceutical container borosilicate glass according to claim 1, characterized in that 5 to 10 wt%. _{(MgO + CaO + SrO) /} (Na 2 O + K 2 O + Li 2 O) the value of the pharmaceutical container borosilicate glass according to claim 1 or 2, characterized in that 0.10 or less. A mass _{ratio, CaO / (Na 2 O +} K 2 O + Li 2 O) The pharmaceutical container borosilicate glass according to claim 1, characterized in that the 0 to 0.10. Mass ratio _{K 2} O / Na 2 O pharmaceutical container borosilicate glass according to claim 1, characterized in that a 0.33-.41. A mass _{ratio, Al 2 O 3 / (Na} 2 O + K 2 O + Li 2 O + MgO + CaO + SrO + B 2 O 3) is a pharmaceutical container borosilicate glass according to claim 1, characterized in that at least 0.32 ..   In the powder test method of the hydrolysis resistance test according to EP 7.0, the consumption amount of 0.02 mol / L hydrochloric acid per unit glass mass is 0.030 mL or less, wherein Borosilicate glass for a pharmaceutical container according to any one of claims. SrO 0 to _4.0% by mass%, _TiO 2 0~7.0%, claim 1, characterized in that it contains _{ZrO 2 0~7.0%, Fe 2 O} 3 0~0.2% Borosilicate glass for a pharmaceutical container according to any one of to 7.   A glass tube for a pharmaceutical container, comprising the borosilicate glass for a pharmaceutical container according to any one of claims 1 to 8.   A pharmaceutical container comprising the borosilicate glass for a pharmaceutical container according to any one of claims 1 to 8.