[go: up one dir, main page]

WO2017115728A1 - Procédé de fabrication de verre aluminoborosilicaté pour récipients pharmaceutiques - Google Patents

Procédé de fabrication de verre aluminoborosilicaté pour récipients pharmaceutiques Download PDF

Info

Publication number
WO2017115728A1
WO2017115728A1 PCT/JP2016/088478 JP2016088478W WO2017115728A1 WO 2017115728 A1 WO2017115728 A1 WO 2017115728A1 JP 2016088478 W JP2016088478 W JP 2016088478W WO 2017115728 A1 WO2017115728 A1 WO 2017115728A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
pharmaceutical container
aluminoborosilicate
producing
aluminoborosilicate glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/088478
Other languages
English (en)
Japanese (ja)
Inventor
真人 六車
美樹 木村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP2017559168A priority Critical patent/JPWO2017115728A1/ja
Publication of WO2017115728A1 publication Critical patent/WO2017115728A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass

Definitions

  • the present invention relates to a method for producing aluminoborosilicate glass for pharmaceutical containers.
  • compositions include vials and ampoules, and the glass used for these is required to have the following characteristics.
  • A) The components in the chemical solution to be filled do not react with the components in the glass.
  • B) The chemical durability and the hydrolysis resistance are high so as not to contaminate the chemicals to be filled, and they are maintained even after various heat treatments such as processing the container.
  • C) The coefficient of thermal expansion is low so that damage due to thermal shock is unlikely to occur during the manufacturing process of the glass tube, which is an intermediate product, and the thermal processing process for pharmaceutical containers.
  • D The amount of heat in the thermal processing step can be reduced in order to suppress the formation of a heterogeneous layer on the inner surface of the container.
  • soda lime glass, borosilicate glass, and alumino borosilicate glass have been used as glass for pharmaceutical containers.
  • standard pharmaceutical container alumino borosilicate glass as a component, contains SiO 2, B 2 O 3, Al 2 O 3, Na 2 O, K 2 O, CaO, BaO and a small amount of fining agents There are many.
  • aluminoborosilicate glass for pharmaceutical containers is required to have higher chemical durability and hydrolysis resistance than ever before.
  • the aluminoborosilicate glass contains BaO
  • barium feldspar crystals are likely to precipitate due to reaction with the alumina-based refractory when the glass is melted, and the productivity is lowered.
  • the barium ions eluted from the water react with sulfate ions in the chemical solution to generate insoluble precipitates.
  • pharmaceutical containers such as vials and ampoules can be obtained by locally heating a glass tube made of aluminoborosilicate glass with a burner, followed by molding. During this thermal processing, B 2 O 3 , Na 2 O, etc. contained in the aluminoborosilicate glass may evaporate and condense on the inner surface of the pharmaceutical container, thereby forming a heterogeneous layer.
  • the formation of the heterogeneous layer substantially reduces the chemical durability and hydrolysis resistance of the pharmaceutical container. That is, B 2 O 3 , Na 2 O and the like are eluted from the heterogeneous layer during storage of the chemical solution or during autoclaving after filling with the chemical solution, causing alteration of the chemical component or pH change of the chemical solution.
  • this heterogeneous layer causes the inner surface of the pharmaceutical container to peel off, and causes insoluble foreign matter called flakes to be generated in the chemical solution.
  • Patent Document 1 proposes a glass in which BaO is not contained and the amount of K 2 O added is adjusted in order to improve hydrolysis resistance.
  • K 2 O itself is not only easily evaporated, but also has an insufficient effect of suppressing the evaporation of B 2 O 3 and Na 2 O. For this reason, the heterogeneous layer formed on the inner surface of the pharmaceutical container at the time of heat processing cannot be sufficiently suppressed. As a result, there is a concern that the chemical solution is deteriorated, the pH is increased, and further, the occurrence of flakes occurs.
  • An object of the present invention is to provide a method for producing an aluminoborosilicate glass for a pharmaceutical container that can suppress the evaporation of B 2 O 3 and Na 2 O by reducing the amount of heat required in the thermal processing step for molding the pharmaceutical container. Is to provide.
  • the inventors have conducted various experiments, and the evaporation amount of B 2 O 3 or Na 2 O that evaporates when the aluminoborosilicate glass for pharmaceutical containers is heat-processed is not only the composition of the glass but also the local composition. It was found to be related to homogeneity. That is, when striae showing local inhomogeneity of the glass composition was remarkable, it was found that a large amount of B 2 O 3 and Na 2 O were evaporated when thermally processed into a pharmaceutical container.
  • this striae is largely related to the composition of the Al-introducing raw material contained in the glass batch.
  • the method for producing an aluminoborosilicate glass for a pharmaceutical container according to the present invention is a pharmaceutical container for obtaining an aluminoborosilicate glass for a pharmaceutical container by melting a glass batch containing an Al-introducing raw material and then molding the obtained molten glass.
  • Al-containing natural mineral and Al-containing chemical product are included as Al-introducing raw materials, and Al / (Al + Al content in Al-containing natural mineral is included by mass ratio) It is characterized in that Al) in the chemical product is more than 0 to 0.9.
  • the aluminoborosilicate glass is glass containing SiO 2 , B 2 O 3 and Al 2 O 3 as essential components.
  • the glass batch of the present invention contains an Al-containing natural mineral and an Al-containing chemical product as an Al-introducing raw material.
  • the Al content in each raw material can be determined by XRF or chemical analysis.
  • a method of manufacturing a medicament container aluminoborosilicate glass of the present invention it is preferable to use Al-containing natural minerals containing 1 wt% or more of Al in terms of Al 2 O 3.
  • a feldspar group mineral as the Al-containing natural mineral.
  • an aluminoborosilicate glass for a pharmaceutical container it is preferable to use aluminum oxide and / or aluminum hydroxide as the Al-containing chemical product.
  • an alkali carbonate raw material and / or an alkali nitrate raw material it is preferable to further introduce an alkali carbonate raw material and / or an alkali nitrate raw material into the glass batch.
  • the manufacturing method of the aluminoborosilicate glass for pharmaceutical containers of the present invention has a glass composition of mass%, SiO 2 70.0-77.0%, Al 2 O 3 4.5-11%, B 2 O. 3 3.0 to 11.5%, Na 2 O 3.0 to 8.5%, K 2 O 0 to 5.5%, Li 2 O 0 to 3.5%, MgO + CaO 0 to less than 4.0%
  • the glass batch is preferably prepared so that an aluminoborosilicate glass for pharmaceutical containers containing 0 to less than 4.0% of SrO is obtained.
  • the manufacturing method of the aluminoborosilicate glass for pharmaceutical containers of this invention prepares a glass batch so that the aluminoborosilicate glass for pharmaceutical containers which does not contain BaO substantially as a glass composition may be obtained.
  • the value of Al 2 O 3 / (B 2 O 3 + Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO) is 0.20 to 0.2 by mass ratio in the glass composition. It is preferable to prepare the glass batch so as to obtain an aluminoborosilicate glass for a pharmaceutical container that is 0.70.
  • the obtained molten glass is preferably formed into a tubular shape.
  • the resulting glass has good compositional homogeneity, and local differences in properties such as glass viscosity, heat capacity, thermal conductivity, specific heat, etc. are reduced. Can do. For example, when it shape
  • the aluminoborosilicate glass for pharmaceutical containers obtained in the present invention can suppress the formation of a heterogeneous layer on the inner surface of the pharmaceutical container in the heat processing step, and thus has excellent chemical durability and after various heat treatments. Hydrolysis resistance can be maintained, and when this glass is used in a pharmaceutical container, it is possible to suppress alteration of chemical components, increase in pH of chemical solutions, and generation of flakes.
  • an Al-containing natural mineral and an Al-containing chemical product are contained as an Al-introducing raw material in the glass batch, and Al / (Al + Al-containing chemical product in the Al-containing natural mineral)
  • Al / (Al + Al-containing chemical product in the Al-containing natural mineral) In which the mass ratio of Al) exceeds 0, 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.20 or more, 0.25 or more, 0.30 or more, 0. It is preferably set to 32 or more, and more preferably 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less, 0.60 or less, or 0.57 or less.
  • the usage rate of the Al-containing natural mineral increases as the Al-introducing raw material in the glass batch.
  • Natural minerals generally have a broader particle size distribution compared to chemical products, and in glass batches, segregation and melting separation with differences in melting rates are likely to occur, making it difficult to melt glass homogeneously.
  • the compositional homogeneity of the glass decreases.
  • an excessive amount of heat is applied during heat processing, and a heterogeneous layer is formed on the inner surface of the pharmaceutical container, which decreases the chemical durability and hydrolysis resistance of the pharmaceutical container. Increases pH and causes flakes.
  • the Al-containing natural minerals form a solid solution with each other, the composition of the Al-containing natural mineral is not constant, and the resulting glass composition may vary.
  • the Al-containing natural mineral is a mixture of natural minerals, there is a concern not only of inhomogeneous mixing and segregation, but also the composition of the glass batch and the resulting glass composition may vary.
  • the mass ratio is too large, the use ratio of Al-containing chemical products such as aluminum oxide and aluminum hydroxide, which are hardly soluble raw materials, increases in the glass batch, making it difficult to melt the glass homogeneously. Homogeneity decreases. As a result, an excessive amount of heat is applied during heat processing, and a heterogeneous layer is formed on the inner surface of the drug container, resulting in a decrease in chemical durability and hydrolysis resistance of the drug container. Triggers the occurrence of flakes.
  • Al-containing chemical products such as aluminum oxide and aluminum hydroxide
  • the Al-containing natural mineral used in the present invention preferably contains Al in an amount of Al 2 O 3 of 1% or more, 2% or more, 5% or more, 10% or more, 15% or more, and 90% Hereinafter, it is preferable to contain 50% or less, 40% or less, or 30% or less.
  • Al-containing natural minerals include, but are not limited to, feldspar group minerals, kaolin, clay, and silica sand.
  • the feldspar group mineral is a raw material containing at least 5% by mass of feldspar such as soda feldspar (NaAlSi 3 O 8 ), potash feldspar (KAlSi 3 O 8 ), anorthite (CaAl 2 Si 2 O 8 ). It exists in various forms on the earth.
  • alkali feldspar is a feldspar in which soda feldspar and potash feldspar are dissolved
  • plagioclase is a feldspar in which soda feldspar and anorthite are dissolved.
  • the Al-containing natural mineral preferably contains feldspar in 5% by mass, 20% or more, 30% or more, 50% or more, 70% or more, 90% or more.
  • the feldspar exists abundantly on the earth, and since it is mined in large quantities, it is easy to obtain and contains a large amount of Al, which is suitable as an Al introducing raw material.
  • Al-containing chemical product aluminum oxide, aluminum hydroxide, aluminum metaphosphate and the like are preferable, but not limited thereto.
  • Aluminum oxide and aluminum hydroxide are suitable because they are inexpensive as Al-containing chemical products and are easy to obtain.
  • aluminum metaphosphate is suitable because it is difficult to deliquesce and easy to handle when it is desired to introduce the P 2 O 5 component into a glass batch.
  • Alkali is lithium, sodium, potassium, rubidium, or cesium.
  • the glass batch By introducing an alkali carbonate raw material or an alkali nitrate raw material, the glass batch is melted at a lower temperature, and the energy required for melting can be reduced.
  • an alkali carbonate or alkali nitrate having a higher alkali content than natural minerals may be added.
  • a polyvalent oxides such as SnO 2 or Sb 2 O 3
  • an alkali nitrate as oxidizing agent it is possible to promote the fining action.
  • the glass batch adjusted so that it may become the following aluminoborosilicate (or aluminosilicate) glass for the manufacturing method of this invention.
  • SiO 2 70.0-77.0% preferably 70.0-75.5%
  • Al 2 O 3 4.5-11% preferably 6.3-11%)
  • B 2 O 3 0 to 11.5% preferably 3.0 to 11.5%
  • Li 2 O 0-3.5% preferably 0-0.2%
  • SrO 0 to less than 4.0% preferably less than 4.0%
  • % display means mass%.
  • SiO 2 is one of the components constituting the glass network.
  • the content of SiO 2 is 70.0-77.0%, preferably 70.0-76.0%, 70.5-75.5%, 71.0-75.0%, In particular, it is 72.0-74.7%.
  • the content of SiO 2 is too small decreases chemical durability, acid resistance required for the pharmaceutical container is lowered.
  • the productivity decreases easily devitrified in the manufacturing process of the glass tube.
  • Al 2 O 3 is a component that suppresses the devitrification of glass and improves chemical durability and hydrolysis resistance.
  • the content of Al 2 O 3 is 4.5 to 11%, preferably 5.1 to less than 11%, 5.5 to 10%, 6.3 to 9%, more than 6.3% to 10%, More preferably, it is 6.4 to 8.5%, still more preferably 6.4 to 8.3%, particularly 6.4 to 8.0%. 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, the heat processing temperature increases, and the amount of evaporation of B 2 O 3 and Na 2 O increases when processed into a pharmaceutical container. End up.
  • B 2 O 3 not only lowers the melting point of the glass but also increases the liquid phase viscosity and suppresses devitrification. Therefore, the content of B 2 O 3 is 0 to 11.5%, more than 0 to 11.5%, 1 to 11.5%, 3 to 11.5%, preferably less than 5.5 to 11.5% More preferably, it is 8.5 to less than 11.5%, and further preferably 9 to less than 11.5%. If the content of B 2 O 3 is too small, the heat processing temperature becomes high, and the amount of evaporation of B 2 O 3 or Na 2 O increases when processing into a pharmaceutical container. On the other hand, B 2 when the content of O 3 is too much resistance to hydrolysis and chemical durability is lowered.
  • Li 2 O has an effect of decreasing the viscosity of the glass and increasing the linear thermal expansion coefficient.
  • the content of Li 2 O is 0 to 3.5%, preferably 0 to 3.0%, 0 to 2.0%, 0 to 0.1%, 0 to 0.5%, 0 to 0 0.2%, preferably 0 to 0.1%, more preferably 0 to 0.05%, and still more preferably 0 to 0.01%.
  • other alkalis other than Li 2 O It is desirable to use a metal oxide.
  • Na 2 O has the effect of lowering the viscosity of the glass and increasing the linear thermal expansion coefficient in the same manner as Li 2 O.
  • the content of Na 2 O is 3.0 to 8.5%, preferably 3.5 to less than 8.5%, more preferably 4.0 to 8.0%, and even more preferably 4.0 to 7%. 0.0%.
  • the heat processing temperature becomes high, and the amount of evaporation of B 2 O 3 and Na 2 O increases when processing into a pharmaceutical container.
  • hydrolysis resistance is deteriorated when the content of Na 2 O is too large.
  • K 2 O has the effect of reducing the viscosity of the glass and increasing the linear thermal expansion coefficient, like Li 2 O and Na 2 O.
  • the content of K 2 O is 0 to 5.5%, preferably more than 0 to 5.0%, 0.1 to less than 5.0%, more preferably 0.5 to 4.5%, still more preferably Is 1.0 to 3.0%, particularly 1.5 to 3.0%.
  • K 2 When the content of O is too large resistance to hydrolysis is reduced.
  • the value of K 2 O / Na 2 O in terms of mass ratio is 0 to 1, more than 0 to 0.99, 0.05 to 0.95, 0.1 to 0.00. 9, 0.2 to 0.85, more preferably 0.20 to 0.80, still more preferably 0.2 to 0.75, especially 0.2 to 0.7. If this ratio is small, the hydrolysis resistance decreases. On the other hand, when this ratio is large, the heat processing temperature becomes high, and the amount of evaporation of B 2 O 3 , Na 2 O and the like increases when processing into a pharmaceutical container.
  • the total content of Li 2 O, Na 2 O and K 2 O is 5 to 13%, preferably 5 to 12.5%, 5.5 to 10%, particularly 6 to 9%.
  • the heat processing temperature becomes high.
  • chemical durability and hydrolysis resistance will fall.
  • MgO has the effect of reducing the high temperature viscosity of the glass. In addition, there is an effect of improving chemical durability.
  • the content of MgO is 0 to 3.0%, preferably 0 to 2.0%, 0 to 1.0%, 0 to less than 1.0%, particularly 0 to 0.5%. When there is too much content of MgO, hydrolysis resistance will fall.
  • CaO has the effect of reducing the high temperature viscosity of the glass.
  • the content of CaO is 0 to 4.0%, preferably 0 to 2.0%, 0 to 1.5%, 0 to 1.0%, 0 to less than 1.0%, particularly 0 to 0.0. 5%. When there is too much CaO content, hydrolysis resistance will fall.
  • MgO + CaO is the total content of MgO and CaO, and is an important index for adjusting the high-temperature viscosity and hydrolysis resistance of glass to a preferred range.
  • MgO + CaO is 0 to 4.0%, preferably 0 to 3.0%, 0 to 2.0%, 0 to 1.0%, 0 to less than 1.0%, especially 0 to 0.5%. is there. When there is too much MgO + CaO, the high temperature viscosity of glass can be reduced, but the hydrolysis resistance of glass will fall.
  • SrO has the effect of improving chemical durability.
  • the SrO content is 0 to less than 4.0%, preferably 0 to 2.0%, more preferably 0 to 1.0%. When there is too much content of SrO, hydrolysis resistance will fall.
  • TiO 2 has the effect of improving hydrolysis resistance.
  • the content of TiO 2 is 0 to less than 7.0%, preferably 0 to 5.0%, more preferably 0 to 4.0%, and still more preferably 0 to 1.5%.
  • the heat processing temperature becomes high, and the amount of evaporation of B 2 O 3 , Na 2 O and the like increases when processed into a pharmaceutical container.
  • 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%, more preferably 0 to 4.0%, still more preferably 0 to 1.5%, 0 to 1.0%, 0 to less than 1.0%, especially 0 to 0.5%.
  • the heat processing temperature becomes high, and the amount of evaporation of B 2 O 3 , Na 2 O and the like increases when processed into a pharmaceutical container.
  • Fe 2 O 3 may color the glass and reduce the transmittance in the visible range, its content is 0.2% or less, preferably 0.1% or less, more preferably 0.02% or less. It is.
  • the F as a fining agent, Cl, Sb 2 O 3, SnO 2, SO 3 may contain one or more kinds of such.
  • the total content of these fining agents is 3% or less, preferably 1% or less, more preferably 0.5% or less.
  • Cl and SnO 2 are used because of environmental aspects, melting of the aluminoborosilicate glass for pharmaceutical containers of the present invention, compatibility with the fining temperature, and less harm to the human body. It is preferable to do.
  • Cl its content is preferably 3% or less, more preferably 1% or less, and particularly preferably 0.2% or less.
  • SnO 2 When SnO 2 is used, its content is 2% or less, preferably 0.5% or less.
  • the content of BaO is preferably 0 to 2.0%, 0 to 1.5%, 0 to 1.0%, and less than 0 to 1.0%.
  • the method for producing an aluminoborosilicate glass for pharmaceutical containers of the present invention It is more preferable that the glass batch does not substantially contain BaO as a glass composition.
  • substantially free of BaO means that BaO is not actively added, and is not intended to exclude substances that are mixed as impurities. More specifically, it means that the content of BaO is 0.05% or less by mass%.
  • BaO is contained in the glass, when it reacts with an alumina refractory during glass production or when used as a pharmaceutical container, crystals are formed by the reaction of Ba ions eluted from the glass with sulfate ions in the chemical solution. There is a risk of precipitation or generation of precipitates.
  • the values of Al 2 O 3 / (B 2 O 3 + Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO) by mass ratio are 0.20 to 0.70, 0.25 to 0.68, 0.30 to 0.66, It is preferable to prepare the glass batch so as to be 0.32 to 0.60 and 0.35 to 0.60.
  • Al 2 O 3 / (B 2 O 3 + Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO) is too small, the hydrolysis resistance of the glass will be lowered, and B 2 O 3 or Na when heated into a pharmaceutical container The amount of evaporation of alkali metal oxides such as 2 O increases.
  • the value of Al 2 O 3 / (B 2 O 3 + Li 2 O + Na 2 O + K 2 O + MgO + CaO + SrO) is too large, the viscosity of the glass becomes high, and the processing temperature when heat-processing into a pharmaceutical container increases. As a result, the amount of evaporation of alkali metal oxides such as B 2 O 3 and Na 2 O in the glass increases.
  • the obtained molten glass is preferably formed into a tubular shape.
  • each raw material is prepared to obtain a target composition to obtain a glass batch.
  • the glass batch is continuously charged into a melting furnace at 1550 to 1700 ° C., melted and clarified, and then the obtained glass melt is wound around a rotating refractory while air is blown out from the tip of the refractory. Then, the glass is drawn out from the tip portion into a tubular shape by the so-called Danner method. The drawn tubular glass is cut into a predetermined length to obtain a glass tube.
  • the glass tube obtained in the present invention is formed into a pharmaceutical container
  • a known method can be used. For example, a method of cutting a glass tube to a predetermined length, melting the end with a flame such as a burner, and simultaneously heat-molding and sealing the bottom and mouth, and a method of molding the mouth after molding the bottom is there.
  • the portion to be heated by a burner or the like may be any portion such as the outside, inside, and end of the glass tube as required.
  • the heating temperature varies depending on the melting temperature of the glass tube, but is generally about 1000 to 1300 ° C.
  • Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 6, 9 to 16, A to J) and comparative examples (samples No. 7, 8, F, and G).
  • glass raw materials were prepared so as to have the composition shown in the table to prepare a glass batch. Only aluminum oxide, aluminum hydroxide, and feldspar were used as the Al introduction raw material in the glass batch.
  • Al in the Al containing chemical product by mass ratio / Al in Al containing natural mineral + Al in Al containing chemical product
  • mass ratio / Al in Al containing natural mineral + Al in Al containing chemical product
  • these glass batches are continuously charged into a melting furnace at 1550 to 1700 ° C., melted and clarified, and then the obtained molten glass is wound around a rotating refractory while air is blown out from the tip of the refractory. Then, the glass is pulled out from the tip portion into a tubular shape. The drawn tubular glass was cut into a predetermined length to obtain a glass tube. The glass tube thus obtained was subjected to various evaluations.
  • sample no. Nos. 1 to 6 can suppress the amount of heat necessary for forming a pharmaceutical container, and can improve the chemical durability and hydrolysis resistance of the pharmaceutical container.
  • sample No. which is a comparative example. 7 and 8 were poor in hydrolysis resistance because the mass ratio of Al in the Al-containing chemical product / (Al in the Al-containing natural mineral + Al in the Al-containing chemical product) was outside the scope of the present invention. Furthermore, the dimensional accuracy of the glass tube was also outside the predetermined range.
  • Sample No. Nos. 9 to 16 use an Al-containing chemical product and an Al-containing natural mineral as an Al-introducing raw material. Further, Al in the Al-containing chemical product / (Al in the Al-containing natural mineral + Al in the Al-containing chemical product) Thus, the obtained glass tube had reduced dimensional accuracy of the glass tube, that is, bending or uneven thickness of the glass tube. From this, sample no. Nos. 9 to 16 can suppress the amount of heat required for forming a pharmaceutical container, and can improve the chemical durability and hydrolysis resistance of the pharmaceutical container.
  • Samples A to J in Table 2 show the same batch compositions other than the Al-introduced raw material 1 but the Al-introduced raw material was changed to produce a glass batch of 100 g glass.
  • surface has shown the mass of the raw material required in order to obtain 100g of glass.
  • soda feldspar NaAlSi 3 O 8
  • potash feldspar KOKAI 3 O 8
  • anorthite CaAl 2 SiO 8
  • aluminum oxide were used.
  • these glass batches are continuously fed into a melting furnace at 1550 to 1700 ° C. and melted and clarified.
  • the obtained molten glass is formed into a ribbon shape, cut into a length of 1 mm, and immersed in benzyl alcohol. The striae was observed from the direction.
  • composition stability of the glass batch ⁇ when there was no problem in composition variation of the glass batch, ⁇ when there was compositional variation but there was no practical problem, and composition variation was practically problematic was marked with x.
  • Samples A to E and H to J use both Al-containing chemicals and Al-containing natural minerals as Al introduction raw materials, and Al / (Al + Al-containing natural minerals in Al-containing natural minerals) Since the mass ratio of Al) was within a predetermined range, the striae were practically free from problems. Therefore, it is considered that the compositional homogeneity of the glass is excellent, and local differences are small with respect to glass viscosity, heat capacity, thermal conductivity, and specific heat. Therefore, when these samples are molded into a glass tube, the dimensional accuracy of the glass tube becomes good, and the amount of heat necessary for molding a pharmaceutical container can be suppressed. Therefore, it is considered that the obtained pharmaceutical container can maintain excellent chemical durability and hydrolysis resistance even after various heat treatments, and can suppress alteration of chemical component, pH increase of chemical solution, and generation of flakes.
  • sample F used only aluminum oxide, which is an Al-containing chemical product, as an Al-introducing raw material. Therefore, the hardly soluble aluminum oxide is difficult to dissolve, the glass composition is inhomogeneous, and strong striae are recognized.
  • Sample G only soda feldspar, which is an Al-containing natural mineral, was used as an Al introduction raw material. Therefore, the glass composition homogeneity and the glass batch composition stability were unstable.
  • the linear thermal expansion coefficient was measured in a temperature range of 30 to 380 ° C. with a dilatometer using a glass sample molded into a rod shape of about 5 mm ⁇ ⁇ 50 mm.
  • the strain point, annealing point, and softening point were measured by the fiber elongation method.
  • the working temperature was determined by obtaining a viscosity curve of the glass from the high temperature viscosity obtained by the platinum ball pulling method and the Fulcher viscosity calculation formula, and obtaining a temperature corresponding to 10 4 dPa ⁇ s from this viscosity curve.
  • the working temperature corresponds to the thermal processing temperature of the glass tube.
  • the liquid phase temperature was measured by filling 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. Then, the crystal precipitation location was identified by microscopic observation, the temperature corresponding to the crystal precipitation location was calculated from the temperature gradient graph of the electric furnace, and this temperature was defined as the liquidus temperature.
  • the liquid phase viscosity is calculated by calculating the glass viscosity curve from the strain point, annealing point, softening point, working temperature and Fulcher's viscosity formula, and calculating the viscosity of the glass at the liquid phase temperature from this viscosity curve.
  • the liquid phase viscosity was calculated by calculating the glass viscosity curve from the strain point, annealing point, softening point, working temperature and Fulcher's viscosity formula, and calculating the viscosity of the glass at the liquid phase temperature from this viscosity curve. was the liquid phase viscosity.
  • the hydrolysis resistance test was performed by pulverizing a sample using an alumina mortar and pestle and according to a powder test method of EP 8.0.
  • the detailed test procedure is as follows. The surface of the sample was thoroughly wiped with ethanol, and the sample was pulverized with an alumina mortar and pestle, and then classified using three sieves made of stainless steel having a size of 710 ⁇ m, 425 ⁇ m, and 300 ⁇ m. The material remaining on the sieve was pulverized again and subjected to the same sieve operation. The sample powder remaining on the 300 ⁇ m sieve was washed with ethanol and placed in a glass container such as a beaker.
  • an acid resistance test was performed in accordance with DIN12116 with a sample surface area of 50 cm 2 and a 6 mol / L hydrochloric acid solution as an eluent in an amount 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 a mirror polished finish on all surfaces was prepared. As a pretreatment, the sample was hydrofluoric acid (40 mass%) and hydrochloric acid (2 mol / L) at a volume ratio of 1: 9. It was immersed in the solution so mixed and stirred with a magnetic stirrer for 10 minutes.
  • the sample piece was taken out and subjected to ultrasonic cleaning for 2 minutes in ultrapure water three times, and then ultrasonic cleaning for 2 minutes in ethanol was performed twice.
  • 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.
  • 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 suspended with a platinum wire was added and held for 6 hours.
  • the opening of the lid of the container was plugged with a gasket and a cooling pipe. Thereafter, the sample piece was taken out and subjected to ultrasonic cleaning for 3 minutes in ultrapure water three times, and then ultrasonic cleaning for 2 minutes in ethanol was performed 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 m 2 of the sample piece treated in this way was measured to an accuracy of ⁇ 0.1 mg and recorded.
  • the elution amount of Sn was analyzed with an ICP emission analyzer (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 through a membrane filter and collected in a centrifuge tube.
  • the standard solution was prepared by diluting the Sn standard solution (manufactured by Wako Pure Chemical Industries) so that the Sn content was 0 mg / L, 0.05 mg / L, 0.5 mg / L, and 1.0 mg / L. .
  • Calibration curves were prepared from these standard solutions, and the Sn elution amount in the test solution was calculated.
  • the measurement wavelength of Sn was 189.925 nm.
  • the method for producing aluminoborosilicate glass for pharmaceutical containers of the present invention is used, for example, when the glass tube is molded, the bending and uneven thickness of the glass tube can be reduced, so that the amount of heat necessary for molding can be suppressed. As a result, a pharmaceutical container excellent in chemical durability and hydrolysis resistance can be obtained even after various heat treatments, and can be applied to various glass compositions.
  • the aluminoborosilicate glass for pharmaceutical containers according to the present invention can be suitably used as various pharmaceutical container materials such as ampoules, vials, prefilled syringes, cartridges and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne un procédé permettant de fabriquer du verre aluminoborosilicaté pour des récipients pharmaceutiques supprimant l'évaporation de B2O3 et Na2O en réduisant la quantité de chaleur requise au cours d'une étape de traitement thermique pour former les récipients pharmaceutiques. Dans ledit procédé permettant de fabriquer du verre aluminoborosilicaté pour des récipients pharmaceutiques, le verre aluminoborosilicaté pour les récipients pharmaceutiques est obtenu par fusion d'un lot de verre comprenant une charge Al et formant le verre fondu obtenu. Le procédé de fabrication du verre aluminoborosilicaté pour récipients pharmaceutiques selon l'invention est caractérisé en ce qu'il comprend un minéral naturel contenant Al et un produit chimique contenant Al comme charge Al, et par le rapport de masse d'Al dans le produit chimique contenant Al/(Al présent dans le minéral naturel contenant Al + Al présent dans le produit chimique contenant Al) étant supérieur à 0 et inférieur à 0,9.
PCT/JP2016/088478 2015-12-28 2016-12-22 Procédé de fabrication de verre aluminoborosilicaté pour récipients pharmaceutiques Ceased WO2017115728A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017559168A JPWO2017115728A1 (ja) 2015-12-28 2016-12-22 医薬品容器用アルミノホウケイ酸ガラスの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-256266 2015-12-28
JP2015256266 2015-12-28

Publications (1)

Publication Number Publication Date
WO2017115728A1 true WO2017115728A1 (fr) 2017-07-06

Family

ID=59225127

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/088478 Ceased WO2017115728A1 (fr) 2015-12-28 2016-12-22 Procédé de fabrication de verre aluminoborosilicaté pour récipients pharmaceutiques

Country Status (2)

Country Link
JP (1) JPWO2017115728A1 (fr)
WO (1) WO2017115728A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107601858A (zh) * 2017-07-26 2018-01-19 金玛瑙香水（明光）有限公司 一种能够提高阴凉环境的棕色玻璃瓶
CN112266166A (zh) * 2020-10-10 2021-01-26 中建材蚌埠玻璃工业设计研究院有限公司 一种用于制备中性医药玻璃管的复合辅助剂
CN112321152A (zh) * 2020-09-23 2021-02-05 湖南旗滨医药材料科技有限公司 硼硅酸盐玻璃及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174542A (ja) * 1983-03-24 1984-10-03 オ−エンス−イリノイ・インコ−ポレ−テツド バリウムを含まないｉ型ｂ級実験室用ソ−ダ−アルミナ−ケイホウ酸ガラス組成物
JP2005537211A (ja) * 2002-08-29 2005-12-08 コーニング インコーポレイテッド ガス発生フリットを用いたガラスの製造
JP2009040675A (ja) * 2007-07-18 2009-02-26 Nippon Electric Glass Co Ltd 珪酸塩ガラスの製造方法、珪酸塩ガラス熔融用混合原料及び電子材料用ガラス物品
CN103130415A (zh) * 2011-11-23 2013-06-05 四川天齐矿业有限责任公司 一种应用锂辉石的医药玻璃
JP2014073933A (ja) * 2012-10-04 2014-04-24 Nippon Electric Glass Co Ltd 長石質原料の製造方法
JP2014169209A (ja) * 2013-03-05 2014-09-18 Nippon Electric Glass Co Ltd 医薬品容器及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174542A (ja) * 1983-03-24 1984-10-03 オ−エンス−イリノイ・インコ−ポレ−テツド バリウムを含まないｉ型ｂ級実験室用ソ−ダ−アルミナ−ケイホウ酸ガラス組成物
JP2005537211A (ja) * 2002-08-29 2005-12-08 コーニング インコーポレイテッド ガス発生フリットを用いたガラスの製造
JP2009040675A (ja) * 2007-07-18 2009-02-26 Nippon Electric Glass Co Ltd 珪酸塩ガラスの製造方法、珪酸塩ガラス熔融用混合原料及び電子材料用ガラス物品
CN103130415A (zh) * 2011-11-23 2013-06-05 四川天齐矿业有限责任公司 一种应用锂辉石的医药玻璃
JP2014073933A (ja) * 2012-10-04 2014-04-24 Nippon Electric Glass Co Ltd 長石質原料の製造方法
JP2014169209A (ja) * 2013-03-05 2014-09-18 Nippon Electric Glass Co Ltd 医薬品容器及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107601858A (zh) * 2017-07-26 2018-01-19 金玛瑙香水（明光）有限公司 一种能够提高阴凉环境的棕色玻璃瓶
CN112321152A (zh) * 2020-09-23 2021-02-05 湖南旗滨医药材料科技有限公司 硼硅酸盐玻璃及其制备方法
CN112266166A (zh) * 2020-10-10 2021-01-26 中建材蚌埠玻璃工业设计研究院有限公司 一种用于制备中性医药玻璃管的复合辅助剂

Also Published As

Publication number Publication date
JPWO2017115728A1 (ja) 2018-10-18

Similar Documents

Publication Publication Date Title
JP6694167B2 (ja) 医薬容器用ホウケイ酸ガラス
JP6604521B2 (ja) 医薬容器用ホウケイ酸ガラス及び医薬容器用ガラス管
EP3345876A1 (fr) Verre borosilicate pour récipients de médicament, tube en verre pour récipients de médicament et procédé de production d'un conteneur de médicament
CN101808951A (zh) 无碱玻璃的制造方法
EP3326979B1 (fr) Verre de borosilicate pour récipient médical.
JPWO2020153294A1 (ja) 医薬品容器用ガラス、これを用いた医薬品容器用ガラス管及び医薬品容器
WO2017115728A1 (fr) Procédé de fabrication de verre aluminoborosilicaté pour récipients pharmaceutiques
JP6653076B2 (ja) 医薬容器用ガラス管及びその製造方法
JP2014237562A (ja) 医薬容器用ホウケイ酸ガラス
WO2014069177A1 (fr) Verre médical et tube en verre médical
WO2017110927A1 (fr) Matériau mixte pour verre de silicate et procédé de fabrication de tube en verre l'utilisant
JP2017048091A (ja) 医薬容器用ホウケイ酸ガラス
JP7118587B2 (ja) 医薬容器用ホウケイ酸ガラス
CN110510873B (zh) 硼硅酸盐玻璃及其制备方法
JP2017057096A (ja) 医薬容器用ガラス管
WO2022075171A1 (fr) Verre pour tube, récipient d'emballage primaire pharmaceutique et verre de silicate alcalin
JP6653073B2 (ja) 医薬容器用ホウケイ酸ガラス
JPWO2014103897A1 (ja) アルカリアルミノシリケートガラスの製造方法
WO2021220801A1 (fr) Verre pour récipient de médicament, tube de verre pour récipient de médicament et récipient de médicament

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16881703

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017559168

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16881703

Country of ref document: EP

Kind code of ref document: A1