WO2014196655A1 - Glass for pharmaceutical containers - Google Patents

Glass for pharmaceutical containers Download PDF

Info

Publication number
WO2014196655A1
WO2014196655A1 PCT/JP2014/065394 JP2014065394W WO2014196655A1 WO 2014196655 A1 WO2014196655 A1 WO 2014196655A1 JP 2014065394 W JP2014065394 W JP 2014065394W WO 2014196655 A1 WO2014196655 A1 WO 2014196655A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
pharmaceutical containers
mol
sample
content
Prior art date
Application number
PCT/JP2014/065394
Other languages
French (fr)
Inventor
Kazuyuki Yamamoto
Ken Choju
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 EP14734252.1A priority Critical patent/EP3004005B1/en
Priority to EP18178731.8A priority patent/EP3403997A1/en
Priority to US14/895,089 priority patent/US10384975B2/en
Priority to CN201480031674.6A priority patent/CN105263875A/en
Publication of WO2014196655A1 publication Critical patent/WO2014196655A1/en
Priority to US15/974,257 priority patent/US10450217B2/en

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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • 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
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers

Definitions

  • the present invention relates to a glass for pharmaceutical containers, which has excellent chemical durability and also has excellent processibility.
  • glasses made of various materials have been used.
  • Pharmaceuticals are roughly divided into oral agents and parenteral agents.
  • parenteral agents a liquid medicine packed/stored in a glass container is directly administered into the patient's blood. Therefore, there are extremely rigorous quality requirements for such glass containers.
  • extractables from the glass into the liquid medicine may change the properties of the liquid medicine, seriously affecting the life and health of the patient. Therefore, the pharmacopoeia of each country prescribes the amount of extractables from the glass.
  • excellent viscosity characteristics are necessary for processing into various forms such as ampoules, vials, prefilled syringes, and cartridges.
  • Borosilicate glass for pharmaceutical containers normally contains, as constituents, Si0 2 , A1 2 0 3 , B 2 0 3 , Na 2 0, K 2 0, CaO, and BaO together with a small amount of fining agent.
  • boron component contained in borosilicate glass used as a glass for pharmaceutical containers evaporates during thermal processing, resulting in the formation of a silica rich layer, or the evaporated component recondenses on the container inner surface, which occasionally causes phase separation on the inner surface of the glass container; this is believed to be one of the causes of delamination.
  • An object of the present invention is to provide a glass for pharmaceutical containers, which is resistant to delamination and has excellent processibility.
  • the present inventors have conducted various studies, and, as a result, found that the problems mentioned above can be solved by the limitation of the B 2 0 3 content and the addition of Li 2 0. This finding is proposed as the present invention.
  • the glass for pharmaceutical containers of the present invention comprises, in mol% on an oxide basis, 69 to 81% of Si0 2 , 4 to 12% of A1 2 0 3 , 0 to 5% of B 2 0 3 , 5 to 20% of Li 2 0 + Na 2 0 + K 2 0, 0.1 to 12% of Li 2 0, and 0 to 10% of MgO + CaO + SrO + BaO.
  • Li 2 0 + Na 2 0 + K 2 0 herein means the total content of Li 2 0, Na 2 0, and
  • MgO + CaO + SrO + BaO herein means the total content of MgO, CaO, SrO, and BaO.
  • B 2 0 3 is 0 to 4% in mol% on an oxide basis.
  • Na 2 0 is 0 to 1 1% and K 2 0 is 0 to 5% in mol% on an oxide basis.
  • MgO is 0 to 9%
  • CaO is 0 to 4%
  • SrO is 0 to 4%
  • BaO is 0 to 4% in mol% on an oxide basis.
  • the glass further comprises 0 to 2 mol% of Zr0 2 .
  • the glass has a hydrolytic resistance of Class 1 in a test in accordance with the European pharmacopoeia (i.e., a hydrolytic resistance of Class 1 in a test in accordance with ISO 720).
  • the "hydrolytic resistance in a test in accordance with the European pharmacopoeia” refers to the degree of alkali extraction determined by the follow method.
  • a glass sample is ground in an alumina mortar and classified into 300 to 425 ⁇ through a sieve.
  • the solution in the quartz flask is transferred to another beaker. Further, the inside of the quartz flask is washed three times with 15 mL of distilled water, and the washing water is also added to the beaker.
  • a methyl red indicator is added to the beaker, followed by titration with a 0.02 mol/L hydrochloric acid solution.
  • the "hydrolytic resistance of Class 1 in a test in accordance with the European pharmacopoeia” means that the amount of alkali extracted as Na 2 0 determined as above is 62 ⁇ g/g or less.
  • the alkali resistance in a test in accordance with ISO 695 is at least Class 2.
  • the "test in accordance with ISO 695" herein refers to the follow test.
  • a 15 cm glass sample piece with an entirely mirror finished surface is prepared.
  • the sample is immersed in a solution containing fluoric acid (40 wt%) and hydrochloric acid (2 mol/L) mixed in a volume ratio of 1 :9, followed by stirring for 10 minutes with a magnetic stirrer, and then taken out.
  • the sample is ultrasonically cleaned for 2 minutes with ultrapure water three times, and then ultrasonically cleaned for 1 minute with ethanol twice.
  • the sample is dried in an oven at 1 10°C for 1 hour and allowed to cool for 30 minutes in a desiccator.
  • a 800 mL solution containing an aqueous sodium hydroxide solution (1 mol/L) and an aqueous sodium carbonate solution (0.5 mol/L) mixed in a volume ratio of 1 :1 is placed in a stainless steel container and heated to boiling using a mantle heater. After boiling, the sample suspended on a platinum wire is placed therein and maintained boiling for 3 hours.
  • the sample is dried in an oven at 110°C for 1 hour and allowed to cool for 30 minutes in a desiccator.
  • the "alkali resistance of Class 2 in a test in accordance with ISO 695" means that the measured value determined as above is 175 mg/dm 2 or less.
  • the glass has "an alkali resistance of Class 1 in a test in accordance with ISO 695".
  • the working point is 1260°C or less.
  • the “working point” herein means the temperature at which the viscosity of the glass is 10 4 dPa s.
  • the glass for pharmaceutical containers of the present invention comprises, in mol% on an oxide basis, 69 to 81% of Si0 2 , 4 to 12% of A1 2 0 3 , 0 to 5% of B 2 0 3 , 5 to 20% of Li 2 0 + Na 2 0 + K 2 0, 0.1 to 12% of Li 2 0, 0 to 11% of Na 2 0, 0 to 5% of K 2 0, and 0 to 10% of MgO + CaO + SrO + BaO, in which the Li 2 0 content is higher than the K 2 0 content.
  • the glass tube for pharmaceutical containers of the present invention is made of the glass for pharmaceutical containers mentioned above.
  • the glass for pharmaceutical containers of the present invention is resistant to delamination and also can be easily processed into a complex shape. In addition, it has . excellent hydrolytic resistance and is suitable as a glass material for pharmaceutical containers, such as ampoules, vials, prefilled syringes, and cartridges.
  • Si0 2 is one of the components forming the network of the glass.
  • the content of Si0 2 is too low, vitrification is difficult to occur, and also the coefficient of thermal expansion becomes too high, whereby thermal shock resistance is likely to decrease.
  • the acid resistance of the glass tends to be deteriorated.
  • the content of Si0 2 is too high, meltability and formability are likely to decrease. Therefore, the content is 69 to 81%, preferably 69 to 80%, still more preferably 70 to 79%, particularly preferably 70 to 78%, and most preferably 73 to 76%.
  • A1 2 0 3 is one of the components forming the network of the glass and is effective in improving the hydrolytic resistance of the glass.
  • the content is 4 to 12%, preferably 4.5 to 1 1%, still more preferably 5 to 10%, and most preferably 5.5 to 7%.
  • B 2 0 3 is effective in reducing the viscosity of the glass.
  • the content is 0 to 5%, 0 to 4%, 0 to 3%, 0 to 2%, 0 to 1%, and particularly 0 to 0.5%.
  • B 2 0 3 is believed to be one of the causes of delamination. When the content is high, delamination resistance decreases, and flakes likely to occur. That is, this easily results in a greater amount of Si0 2 extracted in a delamination resistance test in accordance with the method described in NPTL 1 than in the case of conventional borosilicate glass.
  • B 2 0 3 is contained as an essential component in view of the meltability and processability. In this case, it is preferable that the content of B 2 0 3 is 0.01% or more, particularly 0.05% or more.
  • Li 2 0, Na 2 0, and K 2 0, which are alkali metal oxides (R 2 0), are effective in reducing the viscosity of the glass.
  • R 2 0 alkali metal oxides
  • the total content of R 2 0 is 5 to 20%, preferably 7 to 17%, 10 to 15%, 10 to 14.5%, and still more preferably 10.5 to 14.5%.
  • Li 2 0 is the most effective in reducing the viscosity of the glass, followed by Na 2 0, and then K 2 0.
  • K 2 0 results in the greatest amount of alkali extracted from the glass, and Li 2 0 the smallest. Therefore, in the present invention, it is preferable that the content of R 2 0 is controlled to be Li 2 0 > Na 2 0 > K 2 0, particularly Li 2 0 > Na 2 0 > K 2 0.
  • Li 2 0 is contained as an essential component.
  • the specific content of Li 2 0 is 0.1 to 12%, preferably 1.5 to 12%, still more preferably 3 to 1 1.5%, and particularly 4.5 to 11.5%. It is preferable that the content of Na 2 0 is 0 to 1 1%, 1 to 10%, 1 to 8% and particularly 1 to 6%, and the content of K 2 0 is 0 to 5%, 0.1 to 5% and particularly 1 to 5%.
  • BaO, SrO, CaO, and MgO which are alkaline earth metal oxides (R'O)
  • R'O alkaline earth metal oxides
  • the content of R'O is controlled to be MgO > CaO > SrO > BaO, particularly MgO > CaO > SrO > BaO.
  • the glass can contain MgO.
  • MgO is contained as an essential component.
  • the content of MgO is 0 to 9%, 0.1 to 9%, 0.5 to 8.5%, and particularly 1 to 5%.
  • the content of CaO is 0 to 4%, 0 to 2%, 0.1 to 2%, and particularly 0.1 to 1%.
  • the content of SrO is 0 to 4%, particularly 0 to 1%, and, if possible, it is desirable that no SrO is contained. It is preferable that the content of BaO is 0 to 4%, particularly 0 to 1%, and, if possible, it is desirable that no BaO is contained.
  • Zr0 2 is effective in improving the alkali resistance of the glass. However, when much Zr0 2 is added, this results in an increase in viscosity and causes
  • Zr0 2 is not an essential component in the present invention, when added, it is preferable that the content is 0 to 2%, particularly 0 to 1%.
  • the total fining agent content is normally 5% or less, particularly preferably 1% or less, and still more preferably 0.5% or less.
  • Ti0 2 , Fe 2 0 3 , ZnO, P 2 0 5 , Cr 2 0 3 , Sb 2 0 3 , S0 3 , Cl 2 , PbO, La 2 0 3 , W0 3 , Nb 2 0 3 , Y 2 0 3 , and the like may be added each in an amount up to 3%.
  • Ti0 2 and Fe 2 0 3 may be added to the batch raw material.
  • the total content of Ti0 2 and Fe 2 0 3 is normally 10% or less.
  • impurities components such as 3 ⁇ 4, C0 2 , CO, H 2 0, He, Ne, Ar, N 2 , and the like may be contained each in an amount up to 0.1%.
  • the contents of noble metal elements incorporated as impurities, such as Pt, Rh, and Au are each 500 ppm or less, preferably 300 ppm or less.
  • the glass for pharmaceutical containers of the present invention has a hydrolytic resistance of Class 1 in a test in accordance with the European
  • the amount of alkali extracted as Na 2 0 in the above test is 62 xg!g or less.
  • the amount of alkali extracted is more than 62 ⁇ ig/g, when the glass is processed into an ampoule or vial, and a medicine is packed and stored therein, the alkali extracted from the glass may change the properties of medicine components.
  • the glass of the present invention has an alkali resistance of at least Class 2 in a test in accordance with ISO 695.
  • the mass loss per unit area in the above test is 175 mg/dm or less.
  • the mass loss per unit area is preferably 130 mg/dm 2 or less, particularly 75 mg/dm 2 or less. Delamination often occurs when a medicine using a citrate or phosphate buffer, or the like, which shows a strong alkaline behavior even at near neutral pH, is packed/stored in a glass container.
  • the alkali resistance of a glass can be an index of resistance to delamination. When the mass loss per unit area is more than 175 mg/dm 2 , the possibility of delamination increases.
  • the glass of the present invention has a working point of 1260°C or less, 1240°C or less, 1230°C or less, and particularly 1220°C or less.
  • the working point is high, the processing temperature at which a material glass tube is processed into an ampoule or vial increases, whereby a significantly increased amount of alkali component evaporates from the glass.
  • the evaporated alkali component adheres to the inner surface of the glass container and causes the change of properties of the medicine packed and stored therein.
  • the glass contains boron
  • boron evaporates and condensates, which can be the cause of delamination.
  • glass raw materials are formulated in the above glass composition to produce a glass batch.
  • the glass batch is continuously fed into a melting furnace at 1550 to 1700°C to perform melting and fining.
  • a melting furnace at 1550 to 1700°C to perform melting and fining.
  • air is blown out from the tip of the refractory, and the glass is drawn from the tip in the form of a tube.
  • the drawn tubular glass is cut into a predetermined length to give a glass tube for pharmaceutical containers.
  • the glass tube thus obtained is used for the production of a vial or ampoule.
  • the glass tube for pharmaceutical containers of the present invention can be produced not only by the Danner method but also using any of known techniques.
  • the Velio method and a down draw method are also effective as production methods for the glass tube for pharmaceutical containers of the present invention.
  • Tables 1 to 4 show the examples of the present invention (Samples No.l to 34) and Table 5 shows comparative examples (Samples No. 35 to 42).
  • the samples were prepared as follows.
  • a 500 g batch was formulated in the composition shown in the table and melted using a platinum crucible at 1650°C for 3.5 hours. Incidentally, stirring was performed twice during the melting process in order to reduce bubbles in the sample. After melting, an ingot was produced, processed into a shape required for measurement, and subjected to various kinds of evaluation. The results are shown in the tables.
  • the working point was 1257°C or less
  • the amount of alkali extracted in a hydrolytic resistance test was 62 ⁇ g/g or less
  • the amount of alkali extracted in an alkali resistance test was 107 mg/dm 2 or less.
  • the amount of Si0 2 extracted in a delamination resistance test was 2.89 ⁇ g/cm 2 or less.
  • the temperature at which the viscosity of the glass was 10 14 5 dPa s was determined by Fiber Elongation method in accordance with ASTM C336.
  • the temperature at which the viscosity of the glass was 10 13 0 dPa-s was determined by Fiber Elongation method in accordance with ASTM C336.
  • the temperature at which the viscosity of the glass was 10 7 6 dPa-s was determined by Fiber Elongation method in accordance with ASTM C338.
  • the temperature at which the viscosity of the glass was 10 4 0 dPa s was determined by a platinum ball pulling up method.
  • the hydrolytic resistance test was performed in accordance with the European pharmacopoeia.
  • the detailed test procedure is as follows.
  • a glass sample was ground in an alumina mortar and classified into 300 to 425 ⁇ through a sieve.
  • the obtained powder was washed with distilled water and ethanol and dried in an oven at 140°C.
  • 10 g of the dried powder sample was placed in a quartz flask, further 50 mL of distilled water was added, and the flask was capped.
  • the quartz flask containing the sample was placed in an autoclave and treated.
  • the treatment conditions were as follows: the temperature was raised from 100°C to 121 °C at 1 °C/min, then maintained at 121 °C for
  • the alkali resistance test was performed in accordance with ISO 695.
  • the detailed test procedure is as follows.
  • a 15 cm glass sample piece with an entirely mirror finished surface was prepared.
  • the sample was immersed in a solution containing fluoric acid (40 wt%) and hydrochloric acid (2 mol/L) mixed in a volume ratio of 1 :9, followed by stirring for 10 minutes with a magnetic stirrer.
  • the sample was then taken out, ultrasonically cleaned for 2 minutes with ultrapure water three times, and then ultrasonically cleaned for 1 minute with ethanol twice.
  • sample was dried in an oven at 110°C for 1 hour and allowed to cool for 30 minutes in a desiccator.
  • the mass of sample ml was measured to an accuracy of ⁇ 0.1 mg and recorded.
  • a 800 mL solution containing an aqueous sodium hydroxide solution (1 mol/L) and an aqueous sodium carbonate solution (0.5 mol/L) mixed in a volume ratio of 1 : 1 was placed in a stainless steel container and heated to boiling using a mantle heater. After boiling, the sample suspended on a platinum wire was placed therein and maintained boiling for 3 hours. The sample was taken out, ultrasonically cleaned for 2 minutes with ultrapure water three times, and then ultrasonically cleaned for 1 minute with ethanol twice.
  • the sample was dried in an oven at 110°C for 1 hour and allowed to cool for 30 minutes in a desiccator.
  • the mass of sample m2 was measured to an accuracy of ⁇ 0.1 mg and recorded. From the masses of sample before and after placed in the boiling alkaline solution, ml and m2 (mg), and the total surface area of sample A (cm ), the mass loss per unit area was calculated by the following equation as a measurement value of the alkali resistance test.
  • the delamination resistance test was performed in accordance with the method described in NPTL 1. However, because there are differences in the sample from, or the like, the method described in NPTL 1 was used with some modifications.
  • the detailed procedure is as follows. A glass piece with an entirely mirror finished surface having a surface area of about 13 cm 2 was prepared and, in order to replicate thermal processing for the production of a container, heated for 20 seconds at the softening point of each sample. Subsequently, a Teflon (registered trademark) container was filled with a 0.9% aqueous NaCl solution adjusted to pH 8.0 with an aqueous Na 2 HP0 4 solution. The sample was immersed therein, and the container was capped.
  • the Teflon container containing the sample was placed in an autoclave and treated.
  • the treatment conditions were as follows: the temperature was raised from 100°C to 121 °C at l°C/min, maintained at 121 °C for 1 hour, and lowered to 100°C at 0.5°C/min.
  • ICP-OES Inductively Coupled Plasma Optical Emission Spectrometry
  • the amount of Si0 2 that had been extracted into the solution through the treatment was determined as the amount of extractable relative to the surface area of the sample ⁇ g/cm ).
  • the amount of Si0 2 extracted is used as an index of delamination resistance. The smaller the amount of Si0 2 extracted is, the higher delamination resistance such a glass is considered to have.

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)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)

Abstract

An object of the present invention is to provide a glass for pharmaceutical containers, which is resistant to delamination and has excellent processibility. The glass for pharmaceutical containers of the present invention comprises, in mol% on an oxide basis, 69 to 81% of Si02, 4 to 12% of Al2O3, 0 to 5% of B2O3, 5 to 20% of Li2O+ Na2O + K2O, 0.1 to 12% of Li2O, and 0 to 10% of MgO + CaO + SrO + BaO. The glass has a hydrolytic resistance of Class 1 in a test in accordance with the European pharmacopoeia.

Description

DESCRIPTION GLASS FOR PHARMACEUTICAL CONTAINERS Technical Field
The present invention relates to a glass for pharmaceutical containers, which has excellent chemical durability and also has excellent processibility.
Background Art
As containers for packing and storing pharmaceuticals, glasses made of various materials have been used. Pharmaceuticals are roughly divided into oral agents and parenteral agents. Among them, in the case of parenteral agents, a liquid medicine packed/stored in a glass container is directly administered into the patient's blood. Therefore, there are extremely rigorous quality requirements for such glass containers. In particular, extractables from the glass into the liquid medicine may change the properties of the liquid medicine, seriously affecting the life and health of the patient. Therefore, the pharmacopoeia of each country prescribes the amount of extractables from the glass. In addition, for processing into various forms such as ampoules, vials, prefilled syringes, and cartridges, excellent viscosity characteristics are necessary.
As a glass material that meets these requirements, borosilicate glass has generally been used. Borosilicate glass for pharmaceutical containers normally contains, as constituents, Si02, A1203, B203, Na20, K20, CaO, and BaO together with a small amount of fining agent. Citation List
Patent Literature
[PTL 1] WO 2013/063275
Non-Patent Literature
[NPTL 1 ] PDA J Pharm Sci and Tech 2012, 66 1 16
Summary of Invention
Technical Problem In recent years, with the rapid advance of pharmaceutical sciences, a wide variety of medicines have been produced, and medicines to be packed in pharmaceutical containers have been changing, which is accompanied by an increase in the number of powerful medicines that corrode glass containers. When such a medicine is
packed/stored in a glass container, the inner surface of the container peels off and floats as flakes in the liquid medicine. This phenomenon, called delamination, has been a serious problem.
Various studies have been conducted to find out the causes of delamination. As in NPTL 1 , the boron component contained in borosilicate glass used as a glass for pharmaceutical containers evaporates during thermal processing, resulting in the formation of a silica rich layer, or the evaporated component recondenses on the container inner surface, which occasionally causes phase separation on the inner surface of the glass container; this is believed to be one of the causes of delamination.
Accordingly, as glasses for pharmaceutical containers for suppressing delamination, boron free and low boron glasses have been proposed as in PTL 1 , and some delamination suppressing effects can be seen. However, there is a problem in that the working points of these glasses are so high that processing into various forms is difficult.
An object of the present invention is to provide a glass for pharmaceutical containers, which is resistant to delamination and has excellent processibility.
Solution to Problem
The present inventors have conducted various studies, and, as a result, found that the problems mentioned above can be solved by the limitation of the B203 content and the addition of Li20. This finding is proposed as the present invention.
That is, the glass for pharmaceutical containers of the present invention comprises, in mol% on an oxide basis, 69 to 81% of Si02, 4 to 12% of A1203, 0 to 5% of B203, 5 to 20% of Li20 + Na20 + K20, 0.1 to 12% of Li20, and 0 to 10% of MgO + CaO + SrO + BaO.
The "Li20 + Na20 + K20" herein means the total content of Li20, Na20, and
K20. The "MgO + CaO + SrO + BaO" herein means the total content of MgO, CaO, SrO, and BaO. In the present invention, it is preferable that B203 is 0 to 4% in mol% on an oxide basis.
In the present invention, it is preferable that Na20 is 0 to 1 1% and K20 is 0 to 5% in mol% on an oxide basis.
In the present invention, it is preferable that MgO is 0 to 9%, CaO is 0 to 4%,
SrO is 0 to 4%, and BaO is 0 to 4% in mol% on an oxide basis.
In the present invention, it is preferable that the glass further comprises 0 to 2 mol% of Zr02.
In the present invention, it is preferable that the glass has a hydrolytic resistance of Class 1 in a test in accordance with the European pharmacopoeia (i.e., a hydrolytic resistance of Class 1 in a test in accordance with ISO 720). The "hydrolytic resistance in a test in accordance with the European pharmacopoeia" refers to the degree of alkali extraction determined by the follow method.
(1) A glass sample is ground in an alumina mortar and classified into 300 to 425 μιη through a sieve.
(2) The obtained powder sample is washed with distilled water and ethanol and dried in an oven at 140°C.
(3) 10 g of the dried powder sample is placed in a quartz flask, further 50 mL of distilled water is added, and the flask is capped and treated in an autoclave. The treatment is performed under the following conditions: the temperature is raised from 100°C to 121 °C at l°C/min, then maintained at 121 °C for 30 minutes, and lowered to 100°C at 0.5°C/min.
(4) After autoclaving, the solution in the quartz flask is transferred to another beaker. Further, the inside of the quartz flask is washed three times with 15 mL of distilled water, and the washing water is also added to the beaker.
(5) A methyl red indicator is added to the beaker, followed by titration with a 0.02 mol/L hydrochloric acid solution.
(6) With 1 mL of the 0.02 mol/L hydrochloric acid solution equivalent to 620 μg of Na20, the amount of alkali extracted per g of glass is calculated.
In addition, the "hydrolytic resistance of Class 1 in a test in accordance with the European pharmacopoeia" means that the amount of alkali extracted as Na20 determined as above is 62 μg/g or less. In the present invention, it is preferable that the alkali resistance in a test in accordance with ISO 695 is at least Class 2. The "test in accordance with ISO 695" herein refers to the follow test.
(1) A 15 cm glass sample piece with an entirely mirror finished surface is prepared. First, as a pretreatment, the sample is immersed in a solution containing fluoric acid (40 wt%) and hydrochloric acid (2 mol/L) mixed in a volume ratio of 1 :9, followed by stirring for 10 minutes with a magnetic stirrer, and then taken out. Next, the sample is ultrasonically cleaned for 2 minutes with ultrapure water three times, and then ultrasonically cleaned for 1 minute with ethanol twice.
(2) Subsequently, the sample is dried in an oven at 1 10°C for 1 hour and allowed to cool for 30 minutes in a desiccator.
(3) The mass of sample ml is measured to an accuracy of ±0.1 mg and recorded.
(4) A 800 mL solution containing an aqueous sodium hydroxide solution (1 mol/L) and an aqueous sodium carbonate solution (0.5 mol/L) mixed in a volume ratio of 1 :1 is placed in a stainless steel container and heated to boiling using a mantle heater. After boiling, the sample suspended on a platinum wire is placed therein and maintained boiling for 3 hours.
(5) The sample is taken out, ultrasonically cleaned for 2 minutes with ultrapure water three times, and then ultrasonically cleaned for 1 minute with ethanol twice.
Subsequently, the sample is dried in an oven at 110°C for 1 hour and allowed to cool for 30 minutes in a desiccator.
(6) The mass of sample m2 is measured to an accuracy of ±0.1 mg and recorded.
(7) From the masses of sample before and after placed in the boiling alkaline solution, ml and m2 (mg), and the total surface area of sample A (cm ), the mass loss per unit area is calculated by the following equation as a measurement value of the alkali resistance test.
(Mass loss per unit area) = 100 x (ml - m2)/A
The "alkali resistance of Class 2 in a test in accordance with ISO 695" means that the measured value determined as above is 175 mg/dm2 or less. Incidentally, when the measured value determined as above is 75 mg/dm2 or less, the glass has "an alkali resistance of Class 1 in a test in accordance with ISO 695". In the present invention, it is preferable that the working point is 1260°C or less. The "working point" herein means the temperature at which the viscosity of the glass is 104 dPa s.
The glass for pharmaceutical containers of the present invention comprises, in mol% on an oxide basis, 69 to 81% of Si02, 4 to 12% of A1203, 0 to 5% of B203, 5 to 20% of Li20 + Na20 + K20, 0.1 to 12% of Li20, 0 to 11% of Na20, 0 to 5% of K20, and 0 to 10% of MgO + CaO + SrO + BaO, in which the Li20 content is higher than the K20 content.
The glass tube for pharmaceutical containers of the present invention is made of the glass for pharmaceutical containers mentioned above.
Advantageous Effects of Invention
The glass for pharmaceutical containers of the present invention is resistant to delamination and also can be easily processed into a complex shape. In addition, it has . excellent hydrolytic resistance and is suitable as a glass material for pharmaceutical containers, such as ampoules, vials, prefilled syringes, and cartridges.
Description of Embodiments
The reasons for controlling the range of composition for each component will be described. Incidentally, "%" means "mol%" unless otherwise noted.
Si02 is one of the components forming the network of the glass. When the content of Si02 is too low, vitrification is difficult to occur, and also the coefficient of thermal expansion becomes too high, whereby thermal shock resistance is likely to decrease. In addition, the acid resistance of the glass tends to be deteriorated.
Meanwhile, when the content of Si02 is too high, meltability and formability are likely to decrease. Therefore, the content is 69 to 81%, preferably 69 to 80%, still more preferably 70 to 79%, particularly preferably 70 to 78%, and most preferably 73 to 76%.
A1203 is one of the components forming the network of the glass and is effective in improving the hydrolytic resistance of the glass. The content is 4 to 12%, preferably 4.5 to 1 1%, still more preferably 5 to 10%, and most preferably 5.5 to 7%. When the content of A1203 is law, it is difficult to achieve the hydrolytic resistance of Class 1 in a test in accordance with the European pharmacopoeia. Meanwhile, when the content of A1203 is high, it is difficult to achieve the working point of 1260°C or less. B203 is effective in reducing the viscosity of the glass. It is preferable that the content is 0 to 5%, 0 to 4%, 0 to 3%, 0 to 2%, 0 to 1%, and particularly 0 to 0.5%. B203 is believed to be one of the causes of delamination. When the content is high, delamination resistance decreases, and flakes likely to occur. That is, this easily results in a greater amount of Si02 extracted in a delamination resistance test in accordance with the method described in NPTL 1 than in the case of conventional borosilicate glass. Incidentally, it is preferable that B203 is contained as an essential component in view of the meltability and processability. In this case, it is preferable that the content of B203 is 0.01% or more, particularly 0.05% or more.
Li20, Na20, and K20, which are alkali metal oxides (R20), are effective in reducing the viscosity of the glass. However, when the total content of these
components is high, the amount of alkali extracted from the glass increases, and also the coefficient of thermal expansion increases, resulting in a decrease in thermal shock resistance. The total content of R20 is 5 to 20%, preferably 7 to 17%, 10 to 15%, 10 to 14.5%, and still more preferably 10.5 to 14.5%.
Among R20, Li20 is the most effective in reducing the viscosity of the glass, followed by Na20, and then K20. In addition, when the contents are the same, K20 results in the greatest amount of alkali extracted from the glass, and Li20 the smallest. Therefore, in the present invention, it is preferable that the content of R20 is controlled to be Li20 > Na20 > K20, particularly Li20 > Na20 > K20.
In addition, in the present invention, Li20 is contained as an essential component. The specific content of Li20 is 0.1 to 12%, preferably 1.5 to 12%, still more preferably 3 to 1 1.5%, and particularly 4.5 to 11.5%. It is preferable that the content of Na20 is 0 to 1 1%, 1 to 10%, 1 to 8% and particularly 1 to 6%, and the content of K20 is 0 to 5%, 0.1 to 5% and particularly 1 to 5%.
BaO, SrO, CaO, and MgO, which are alkaline earth metal oxides (R'O), are effective in reducing the viscosity of the glass. They also affect the amount of alkali extracted. However, in the case where these components are included in the glass composition, during use as a pharmaceutical container, an extremely small amount of R'O may be extracted from the glass into the liquid medicine, resulting in the precipitation of a carbonate or sulfate thereof. When the medicine is administered to a human body, such a precipitate may cause a thrombus, or the like, and thus is harmful. Therefore, the total content of R'O is 0 to 10%, preferably 0.1 to 10%, and more preferably 1 to 9%.
Incidentally, whether a carbonate or sulfate of R'O precipitates depends on the solubility of each salt. Specifically, the solubility of MgO is the highest, followed by CaO, SrO, and then BaO. That is, MgO has the lowest likelihood of salt precipitation, and BaO the highest. In addition, when the contents are the same, the amount of alkali extracted from the glass increases in the order of MgO, CaO, SrO, and then BaO.
Accordingly, it is preferable that the content of R'O is controlled to be MgO > CaO > SrO > BaO, particularly MgO > CaO > SrO > BaO.
In addition, in the present invention, the glass can contain MgO. Particularly, it is preferable that MgO is contained as an essential component. Specifically, it is preferable that the content of MgO is 0 to 9%, 0.1 to 9%, 0.5 to 8.5%, and particularly 1 to 5%.
It is preferable that the content of CaO is 0 to 4%, 0 to 2%, 0.1 to 2%, and particularly 0.1 to 1%.
It is preferable that the content of SrO is 0 to 4%, particularly 0 to 1%, and, if possible, it is desirable that no SrO is contained. It is preferable that the content of BaO is 0 to 4%, particularly 0 to 1%, and, if possible, it is desirable that no BaO is contained.
Zr02 is effective in improving the alkali resistance of the glass. However, when much Zr02 is added, this results in an increase in viscosity and causes
deterioration in devitrification resistance. Although Zr02 is not an essential component in the present invention, when added, it is preferable that the content is 0 to 2%, particularly 0 to 1%.
As a fining agent, one or more of F, CI, Sb203, As203, Sn02, Na2S04, and the like may also be contained. In this case, the total fining agent content is normally 5% or less, particularly preferably 1% or less, and still more preferably 0.5% or less.
Other components may also be contained in addition to the above components. For example, in order to improve chemical durability, high temperature viscosity, or the like, Ti02, Fe203, ZnO, P205, Cr203, Sb203, S03, Cl2, PbO, La203, W03, Nb203, Y203, and the like may be added each in an amount up to 3%.
Incidentally, when the glass is to be colored, Ti02 and Fe203 may be added to the batch raw material. In this case, the total content of Ti02 and Fe203 is normally 10% or less. In addition, as impurities, components such as ¾, C02, CO, H20, He, Ne, Ar, N2, and the like may be contained each in an amount up to 0.1%. Further, it is preferable that the contents of noble metal elements incorporated as impurities, such as Pt, Rh, and Au, are each 500 ppm or less, preferably 300 ppm or less.
The glass for pharmaceutical containers of the present invention has a hydrolytic resistance of Class 1 in a test in accordance with the European
pharmacopoeia. This means that the amount of alkali extracted as Na20 in the above test is 62 xg!g or less. In the case where the amount of alkali extracted is more than 62 ^ig/g, when the glass is processed into an ampoule or vial, and a medicine is packed and stored therein, the alkali extracted from the glass may change the properties of medicine components.
In addition, it is preferable that the glass of the present invention has an alkali resistance of at least Class 2 in a test in accordance with ISO 695. This means that the mass loss per unit area in the above test is 175 mg/dm or less. The mass loss per unit area is preferably 130 mg/dm2 or less, particularly 75 mg/dm2 or less. Delamination often occurs when a medicine using a citrate or phosphate buffer, or the like, which shows a strong alkaline behavior even at near neutral pH, is packed/stored in a glass container. Thus, the alkali resistance of a glass can be an index of resistance to delamination. When the mass loss per unit area is more than 175 mg/dm2, the possibility of delamination increases.
In addition, it is preferable that the glass of the present invention has a working point of 1260°C or less, 1240°C or less, 1230°C or less, and particularly 1220°C or less. When the working point is high, the processing temperature at which a material glass tube is processed into an ampoule or vial increases, whereby a significantly increased amount of alkali component evaporates from the glass. The evaporated alkali component adheres to the inner surface of the glass container and causes the change of properties of the medicine packed and stored therein. In addition, when the glass contains boron, boron evaporates and condensates, which can be the cause of delamination.
Next, a method for producing the glass tube for pharmaceutical containers of the present invention will be described. The following explains an example using the Danner method. First, glass raw materials are formulated in the above glass composition to produce a glass batch. Subsequently, the glass batch is continuously fed into a melting furnace at 1550 to 1700°C to perform melting and fining. Then, while winding the obtained molten glass around a rotatory refractory, air is blown out from the tip of the refractory, and the glass is drawn from the tip in the form of a tube. The drawn tubular glass is cut into a predetermined length to give a glass tube for pharmaceutical containers. The glass tube thus obtained is used for the production of a vial or ampoule.
Incidentally, the glass tube for pharmaceutical containers of the present invention can be produced not only by the Danner method but also using any of known techniques. For example, the Velio method and a down draw method are also effective as production methods for the glass tube for pharmaceutical containers of the present invention.
Examples
Hereinafter, the present invention will be described based on the examples. Tables 1 to 4 show the examples of the present invention (Samples No.l to 34) and Table 5 shows comparative examples (Samples No. 35 to 42).
Table 1
Figure imgf000011_0001
Table 2
Figure imgf000012_0001
Table 3
Figure imgf000013_0001
Table 4
Figure imgf000014_0001
Table 5
Figure imgf000015_0001
The samples were prepared as follows.
First, a 500 g batch was formulated in the composition shown in the table and melted using a platinum crucible at 1650°C for 3.5 hours. Incidentally, stirring was performed twice during the melting process in order to reduce bubbles in the sample. After melting, an ingot was produced, processed into a shape required for measurement, and subjected to various kinds of evaluation. The results are shown in the tables.
As is clear from the tables, with respect to Samples No.1 to 34, which are examples of the present invention, the working point was 1257°C or less, the amount of alkali extracted in a hydrolytic resistance test was 62 μg/g or less, and the amount of alkali extracted in an alkali resistance test was 107 mg/dm2 or less. In addition, the amount of Si02 extracted in a delamination resistance test was 2.89 μg/cm2 or less.
For the measurement of strain point Ps, the temperature at which the viscosity of the glass was 1014 5 dPa s was determined by Fiber Elongation method in accordance with ASTM C336.
For the measurement of annealing point Ta, the temperature at which the viscosity of the glass was 1013 0 dPa-s was determined by Fiber Elongation method in accordance with ASTM C336.
For the measurement of softening point Ts, the temperature at which the viscosity of the glass was 107 6 dPa-s was determined by Fiber Elongation method in accordance with ASTM C338.
For the measurement of working point, the temperature at which the viscosity of the glass was 104 0 dPa s was determined by a platinum ball pulling up method.
The hydrolytic resistance test was performed in accordance with the European pharmacopoeia. The detailed test procedure is as follows. A glass sample was ground in an alumina mortar and classified into 300 to 425 μηι through a sieve. The obtained powder was washed with distilled water and ethanol and dried in an oven at 140°C. 10 g of the dried powder sample was placed in a quartz flask, further 50 mL of distilled water was added, and the flask was capped. The quartz flask containing the sample was placed in an autoclave and treated. The treatment conditions were as follows: the temperature was raised from 100°C to 121 °C at 1 °C/min, then maintained at 121 °C for
30 minutes, and lowered to 100°C at 0.5°C/min. The solution in the quartz flask was transferred to another beaker. Further, the inside of the quartz flask was washed three times with 15 mL of distilled water, and the washing water was also added to the beaker. A methyl red indicator was added to the beaker, followed by titration with a 0.02 mol/L hydrochloric acid solution. With 1 mL of the 0.02 mol/L hydrochloric acid solution equivalent to 620 μg of Na20, the amount of alkali extracted was calculated.
The alkali resistance test was performed in accordance with ISO 695. The detailed test procedure is as follows. A 15 cm glass sample piece with an entirely mirror finished surface was prepared. First, as a pretreatment, the sample was immersed in a solution containing fluoric acid (40 wt%) and hydrochloric acid (2 mol/L) mixed in a volume ratio of 1 :9, followed by stirring for 10 minutes with a magnetic stirrer. The sample was then taken out, ultrasonically cleaned for 2 minutes with ultrapure water three times, and then ultrasonically cleaned for 1 minute with ethanol twice.
Subsequently, the sample was dried in an oven at 110°C for 1 hour and allowed to cool for 30 minutes in a desiccator. The mass of sample ml was measured to an accuracy of ±0.1 mg and recorded. A 800 mL solution containing an aqueous sodium hydroxide solution (1 mol/L) and an aqueous sodium carbonate solution (0.5 mol/L) mixed in a volume ratio of 1 : 1 was placed in a stainless steel container and heated to boiling using a mantle heater. After boiling, the sample suspended on a platinum wire was placed therein and maintained boiling for 3 hours. The sample was taken out, ultrasonically cleaned for 2 minutes with ultrapure water three times, and then ultrasonically cleaned for 1 minute with ethanol twice. Subsequently, the sample was dried in an oven at 110°C for 1 hour and allowed to cool for 30 minutes in a desiccator. The mass of sample m2 was measured to an accuracy of ±0.1 mg and recorded. From the masses of sample before and after placed in the boiling alkaline solution, ml and m2 (mg), and the total surface area of sample A (cm ), the mass loss per unit area was calculated by the following equation as a measurement value of the alkali resistance test.
(Mass loss per unit area) = 100 x (ml - m2)/A
The delamination resistance test was performed in accordance with the method described in NPTL 1. However, because there are differences in the sample from, or the like, the method described in NPTL 1 was used with some modifications. The detailed procedure is as follows. A glass piece with an entirely mirror finished surface having a surface area of about 13 cm2 was prepared and, in order to replicate thermal processing for the production of a container, heated for 20 seconds at the softening point of each sample. Subsequently, a Teflon (registered trademark) container was filled with a 0.9% aqueous NaCl solution adjusted to pH 8.0 with an aqueous Na2HP04 solution. The sample was immersed therein, and the container was capped. The Teflon container containing the sample was placed in an autoclave and treated. The treatment conditions were as follows: the temperature was raised from 100°C to 121 °C at l°C/min, maintained at 121 °C for 1 hour, and lowered to 100°C at 0.5°C/min. Using ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry), the amount of Si02 that had been extracted into the solution through the treatment was determined as the amount of extractable relative to the surface area of the sample ^g/cm ). The amount of Si02 extracted is used as an index of delamination resistance. The smaller the amount of Si02 extracted is, the higher delamination resistance such a glass is considered to have.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skill in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. All references cited herein are incorporated in their entirety. This application is based on Japanese patent application No. 2013-1 19894 filed on June 6, 2013, the entire contents of which are incorporated hereinto by reference.

Claims

1. A glass for pharmaceutical containers comprising, in mol% on an oxide basis, 69 to 81% of SiC-2, 4 to 12% of A1203, 0 to 5% of B203, 5 to 20% of Li20 + Na20 + K20, 0.1 to 12% of Li20, and 0 to 10% of MgO + CaO + SrO + BaO.
2. The glass for pharmaceutical containers according to claim 1, comprising, in mol% on an oxide basis, 0 to 4% of B203.
3. The glass for pharmaceutical containers according to claim 1 or 2, comprising, in mol% on an oxide basis, 0 to 1 1%» of Na20 and 0 to 5% of 20.
4. The glass for pharmaceutical containers according to any one of claims 1 to 3, comprising, in mol% on an oxide basis, 0 to 9% of MgO, 0 to 4% of CaO, 0 to 4% of SrO, and 0 to 4% of BaO.
5. The glass for pharmaceutical containers according to any one of claims 1 to 4, further comprising 0 to 2 mol% of Zr02.
6. The glass for pharmaceutical containers according to any one of claims 1 to 5, having a hydrolytic resistance of Class 1 in a test in accordance with the European pharmacopoeia.
7. The glass for pharmaceutical containers according to any one of claims 1 to 6, having an alkali resistance of at least Class 2 in a test in accordance with ISO 695.
8. The glass for pharmaceutical containers according to any one of claims 1 to 7, having a working point of 1260°C or less.
9. A glass for pharmaceutical containers comprising, in mol% on an oxide basis, 69 to 81% of Si02, 4 to 12% of A1203, 0 to 5% of B203, 5 to 20% of Li20 + Na20 + K20, 0.1 to 12% of Li20, 0 to 1 1% of Na20, 0 to 5% of K20, and 0 to 10% of MgO + CaO + SrO + BaO, wherein the Li20 content is higher than the K20 content.
10. A glass tube for pharmaceutical containers, made of the glass for pharmaceutical containers of any one of claims 1 to 9.
PCT/JP2014/065394 2013-06-06 2014-06-04 Glass for pharmaceutical containers WO2014196655A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP14734252.1A EP3004005B1 (en) 2013-06-06 2014-06-04 Glass for pharmaceutical containers
EP18178731.8A EP3403997A1 (en) 2013-06-06 2014-06-04 Glass for pharmaceutical containers
US14/895,089 US10384975B2 (en) 2013-06-06 2014-06-04 Glass for pharmaceutical containers
CN201480031674.6A CN105263875A (en) 2013-06-06 2014-06-04 Glass for pharmaceutical containers
US15/974,257 US10450217B2 (en) 2013-06-06 2018-05-08 Glass for pharmaceutical containers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013119894 2013-06-06
JP2013-119894 2013-06-06

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US14/895,089 A-371-Of-International US10384975B2 (en) 2013-06-06 2014-06-04 Glass for pharmaceutical containers
US15/974,257 Continuation US10450217B2 (en) 2013-06-06 2018-05-08 Glass for pharmaceutical containers

Publications (1)

Publication Number Publication Date
WO2014196655A1 true WO2014196655A1 (en) 2014-12-11

Family

ID=51033454

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/065394 WO2014196655A1 (en) 2013-06-06 2014-06-04 Glass for pharmaceutical containers

Country Status (5)

Country Link
US (2) US10384975B2 (en)
EP (2) EP3004005B1 (en)
JP (1) JP6455799B2 (en)
CN (2) CN113998886A (en)
WO (1) WO2014196655A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015116097A1 (en) 2015-09-23 2017-03-23 Schott Ag Chemically resistant glass and its use
WO2017155734A1 (en) * 2016-03-07 2017-09-14 Zebrasci, Inc. Micropatterning technique for creating morphologically specific free-floating structures for use as standards in the pharmaceutical industry
EP3241810A1 (en) 2016-05-04 2017-11-08 Schott AG Pharmaceutical packaging means with a chemically resistant glass
DE102017102900A1 (en) 2016-05-04 2017-11-09 Schott Ag Pharmaceutical packaging with a chemically resistant glass
WO2017210315A1 (en) * 2016-05-31 2017-12-07 Corning Incorporated Anti-counterfeiting measures for glass articles
US20180147114A1 (en) * 2016-11-30 2018-05-31 Corning Incorporated Lithium containing aluminosilicate glasses
EP3590902A1 (en) 2018-07-06 2020-01-08 Schott Ag Highly durable and chemically prestressable glasses
US11299419B2 (en) 2017-10-24 2022-04-12 Sunshine Lake Pharma Co., Ltd. UV-resistant and alkaline-resistant borosilicate glass and use thereof
US11319242B2 (en) * 2016-12-29 2022-05-03 Sunshine Lake Pharma Co., Ltd. Borosilicate glass with high chemical resistance and application thereof
WO2023107300A1 (en) * 2021-12-06 2023-06-15 Corning Incorporated Chemically durable borosilicate glass compositions for storing pharmaceutical compositions and articles formed therefrom
US11912618B2 (en) 2019-03-15 2024-02-27 Corning Incorporated Chemically durable aluminosilicate glass compositions and glass articles formed therefrom

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9359251B2 (en) 2012-02-29 2016-06-07 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
US9139469B2 (en) 2012-07-17 2015-09-22 Corning Incorporated Ion exchangeable Li-containing glass compositions for 3-D forming
JP6455799B2 (en) * 2013-06-06 2019-01-23 日本電気硝子株式会社 Glass tubes for pharmaceutical containers and pharmaceutical containers
US11079309B2 (en) 2013-07-26 2021-08-03 Corning Incorporated Strengthened glass articles having improved survivability
US9517968B2 (en) 2014-02-24 2016-12-13 Corning Incorporated Strengthened glass with deep depth of compression
TWI705889B (en) 2014-06-19 2020-10-01 美商康寧公司 Glasses having non-frangible stress profiles
TWI734317B (en) 2014-10-08 2021-07-21 美商康寧公司 Glasses and glass ceramics including a metal oxide concentration gradient
US10150698B2 (en) 2014-10-31 2018-12-11 Corning Incorporated Strengthened glass with ultra deep depth of compression
TWI666189B (en) 2014-11-04 2019-07-21 美商康寧公司 Deep non-frangible stress profiles and methods of making
WO2016163426A1 (en) * 2015-04-09 2016-10-13 ニプロ株式会社 Method for manufacturing medical vial
US10579106B2 (en) 2015-07-21 2020-03-03 Corning Incorporated Glass articles exhibiting improved fracture performance
US11613103B2 (en) 2015-07-21 2023-03-28 Corning Incorporated Glass articles exhibiting improved fracture performance
DE202016008722U1 (en) 2015-12-11 2019-03-21 Corning Incorporated Fusion-formable glass-based articles with a metal oxide concentration gradient
EP3904302A1 (en) 2016-04-08 2021-11-03 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
KR20180132077A (en) 2016-04-08 2018-12-11 코닝 인코포레이티드 A glass-based article comprising a stress profile comprising two regions, and a manufacturing method
EP3507254B1 (en) * 2016-10-12 2021-09-01 Corning Incorporated Methods for determining chemical heterogeneity of glass containers
WO2019209201A2 (en) * 2018-02-05 2019-10-31 Turkiye Sise Ve Cam Fabrikalari Anonim Sirketi Chambered thin glass product with complex shape and with increased resistance and the production method of said glass product
CA3109458A1 (en) * 2018-08-13 2020-02-20 Corning Incorporated Ion exchangeable borosilicate glass compositions and glass articles formed from the same
WO2020138063A1 (en) * 2018-12-27 2020-07-02 日本電気硝子株式会社 Glass for medicine container, and medicine container glass tube and medicine container using same
WO2020137779A1 (en) * 2018-12-27 2020-07-02 日本電気硝子株式会社 Medical glass container
CN113272261A (en) * 2019-01-23 2021-08-17 日本电气硝子株式会社 Glass for pharmaceutical containers, glass tube for pharmaceutical containers using same, and pharmaceutical container
EP3819268B1 (en) * 2019-11-08 2021-09-29 Schott AG Toughenable glass with high hydrolytic resistance and reduced color tinge
EP4144706A4 (en) * 2020-04-30 2024-05-22 Nippon Electric Glass Co Medicine container glass, medicine container glass tube, and medicine container
CN112551891B (en) * 2020-11-19 2022-10-14 江苏通鹏新材料研究院有限公司 Glass composition, glass tube, and preparation method and application thereof
US20230129031A1 (en) * 2021-10-26 2023-04-27 Corning Incorporated Ion exchangeable glasses having high fracture toughness
EP4186874A1 (en) * 2021-11-29 2023-05-31 Schott Ag Glass tube for pharmaceutical containers and process for the production of a glass tube
CN114634308B (en) * 2022-03-30 2022-11-15 安徽汉柔光电科技有限公司 Alkali aluminosilicate glass

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005070A1 (en) * 1997-07-23 1999-02-04 British Ceramic Research Limited Lead-free glaze for ceramic articles
US20120183812A1 (en) * 2009-09-28 2012-07-19 Hiroshi Kajita Glass Substrate for Information Recording Media and Information Recording Medium
US20130101596A1 (en) * 2011-10-25 2013-04-25 Steven Edward DeMartino Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US20130101764A1 (en) * 2011-10-25 2013-04-25 Corning Incorporated Glass Articles with Improved Chemical and Mechanical Durability
US20130101853A1 (en) * 2011-10-25 2013-04-25 Melinda Ann Drake Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19536708C1 (en) * 1995-09-30 1996-10-31 Jenaer Glaswerk Gmbh Boro-silicate glass contg. zirconium and lithium oxide(s)
DE10035801B4 (en) 2000-07-22 2008-04-03 Schott Ag Borosilicate glass of high chemical resistance and its uses
JP4790300B2 (en) * 2005-04-14 2011-10-12 株式会社日立製作所 Glass
CN101033115A (en) * 2007-02-13 2007-09-12 沧州四星玻璃有限公司 Medicinal glass pipe prepared by full electric melting wilo method and manufacturing method thereof
CN101679105B (en) 2007-06-07 2015-06-17 日本电气硝子株式会社 Hardened glass substrate, and method for production thereof
DE102009051852B4 (en) * 2009-10-28 2013-03-21 Schott Ag Borless glass and its use
US9156725B2 (en) * 2012-05-30 2015-10-13 Corning Incorporated Down-drawable chemically strengthened glass for information storage devices
WO2014025009A1 (en) * 2012-08-09 2014-02-13 日本電気硝子株式会社 Glass tube and strengthened glass tube
JP6455799B2 (en) * 2013-06-06 2019-01-23 日本電気硝子株式会社 Glass tubes for pharmaceutical containers and pharmaceutical containers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005070A1 (en) * 1997-07-23 1999-02-04 British Ceramic Research Limited Lead-free glaze for ceramic articles
US20120183812A1 (en) * 2009-09-28 2012-07-19 Hiroshi Kajita Glass Substrate for Information Recording Media and Information Recording Medium
US20130101596A1 (en) * 2011-10-25 2013-04-25 Steven Edward DeMartino Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US20130101764A1 (en) * 2011-10-25 2013-04-25 Corning Incorporated Glass Articles with Improved Chemical and Mechanical Durability
US20130101853A1 (en) * 2011-10-25 2013-04-25 Melinda Ann Drake Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
WO2013063275A1 (en) 2011-10-25 2013-05-02 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PDA J PHARM SCI AND TECH, vol. 66, 2012, pages 116

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10336646B2 (en) 2015-09-23 2019-07-02 Schott Ag Chemically resistant glass
DE102015116097A1 (en) 2015-09-23 2017-03-23 Schott Ag Chemically resistant glass and its use
EP3392219A1 (en) 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
EP3392218A1 (en) 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
EP3392217A1 (en) 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
EP3392216A1 (en) 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
EP3147265A1 (en) 2015-09-23 2017-03-29 Schott AG Chemically resistant glass and its use
WO2017155734A1 (en) * 2016-03-07 2017-09-14 Zebrasci, Inc. Micropatterning technique for creating morphologically specific free-floating structures for use as standards in the pharmaceutical industry
DE102017102900A1 (en) 2016-05-04 2017-11-09 Schott Ag Pharmaceutical packaging with a chemically resistant glass
EP3241810A1 (en) 2016-05-04 2017-11-08 Schott AG Pharmaceutical packaging means with a chemically resistant glass
US10315948B2 (en) 2016-05-04 2019-06-11 Schott Ag Pharmaceutical packaging comprising a chemically resistant glass
WO2017210315A1 (en) * 2016-05-31 2017-12-07 Corning Incorporated Anti-counterfeiting measures for glass articles
US10676240B2 (en) 2016-05-31 2020-06-09 Corning Incorporated Anti-counterfeiting measures for glass articles
US11932445B2 (en) 2016-05-31 2024-03-19 Corning Incorporated Anti-counterfeiting measures for glass articles
US11667434B2 (en) 2016-05-31 2023-06-06 Corning Incorporated Anti-counterfeiting measures for glass articles
RU2746048C2 (en) * 2016-05-31 2021-04-06 Корнинг Инкорпорейтед Anti-counterfeiting measures for glass products
US20180147114A1 (en) * 2016-11-30 2018-05-31 Corning Incorporated Lithium containing aluminosilicate glasses
US10640415B2 (en) 2016-11-30 2020-05-05 Corning Incorporated Lithium containing aluminosilicate glasses
US11572302B2 (en) 2016-11-30 2023-02-07 Corning Incorporated Lithium containing aluminosilicate glasses
US11319242B2 (en) * 2016-12-29 2022-05-03 Sunshine Lake Pharma Co., Ltd. Borosilicate glass with high chemical resistance and application thereof
US11299419B2 (en) 2017-10-24 2022-04-12 Sunshine Lake Pharma Co., Ltd. UV-resistant and alkaline-resistant borosilicate glass and use thereof
DE102018116460A1 (en) 2018-07-06 2020-01-09 Schott Ag Highly resistant and chemically toughened glasses
EP3590902A1 (en) 2018-07-06 2020-01-08 Schott Ag Highly durable and chemically prestressable glasses
US11912618B2 (en) 2019-03-15 2024-02-27 Corning Incorporated Chemically durable aluminosilicate glass compositions and glass articles formed therefrom
WO2023107300A1 (en) * 2021-12-06 2023-06-15 Corning Incorporated Chemically durable borosilicate glass compositions for storing pharmaceutical compositions and articles formed therefrom

Also Published As

Publication number Publication date
EP3004005A1 (en) 2016-04-13
EP3403997A1 (en) 2018-11-21
EP3004005B1 (en) 2018-08-01
JP6455799B2 (en) 2019-01-23
US10384975B2 (en) 2019-08-20
US10450217B2 (en) 2019-10-22
US20180265401A1 (en) 2018-09-20
JP2015013793A (en) 2015-01-22
CN113998886A (en) 2022-02-01
US20160107924A1 (en) 2016-04-21
CN105263875A (en) 2016-01-20

Similar Documents

Publication Publication Date Title
US10450217B2 (en) Glass for pharmaceutical containers
JP6501455B2 (en) Borosilicate glass with improved hydrolysis resistance preferred for use in the pharmaceutical field
US11807575B2 (en) Glass for medicine container and glass tube for medicine container
JP6694167B2 (en) Borosilicate glass for pharmaceutical containers
CN106687422B (en) Borosilicate glass for medical containers and glass tube for medical containers
JP6709501B2 (en) Glass for drug container and glass tube for drug container
CN107848871B (en) Borosilicate glass for medical containers
JP6627779B2 (en) Glass for pharmaceutical containers and glass tubes for pharmaceutical containers
WO2014069177A1 (en) Medicinal glass and medicinal glass tube
CN113272261A (en) Glass for pharmaceutical containers, glass tube for pharmaceutical containers using same, and pharmaceutical container
CN113227008B (en) Glass for medical container, glass tube for medical container, and medical container using same
WO2021220801A1 (en) Medicine container glass, medicine container glass tube, and medicine container
JP6653073B2 (en) Borosilicate glass for pharmaceutical containers
JP2017057096A (en) Glass tube for medical container

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480031674.6

Country of ref document: CN

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

Ref document number: 14734252

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2014734252

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14895089

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE