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WO2014069177A1 - Verre médical et tube en verre médical - Google Patents

Verre médical et tube en verre médical Download PDF

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Publication number
WO2014069177A1
WO2014069177A1 PCT/JP2013/077271 JP2013077271W WO2014069177A1 WO 2014069177 A1 WO2014069177 A1 WO 2014069177A1 JP 2013077271 W JP2013077271 W JP 2013077271W WO 2014069177 A1 WO2014069177 A1 WO 2014069177A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
pharmaceutical
viscosity
content
mass
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/JP2013/077271
Other languages
English (en)
Japanese (ja)
Inventor
拡志 澤里
長壽　研
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
Publication of WO2014069177A1 publication Critical patent/WO2014069177A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • 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 glass and pharmaceutical glass tubes used for pharmaceutical containers and the like.
  • Pharmaceutical glass is required to have high devitrification resistance (high liquid phase viscosity) from the viewpoint of high chemical stability, low working point, low coefficient of thermal expansion, and productivity.
  • Borosilicate from such required properties a typical pharmaceutical glass, comprising a glass composition SiO 2, B 2 O 3, Al 2 O 3, Na 2 O, K 2 O, CaO, and BaO and a small amount of fining agents Made from acid glass.
  • Patent Document 1 proposes a pharmaceutical glass that does not contain BaO and suppresses a decrease in liquid phase viscosity by adjusting the content of components such as Na 2 O.
  • Patent Document 1 has a problem that the working point is as high as 1165 ° C. or higher and the processability is poor.
  • Patent Document 2 proposes a pharmaceutical glass that does not contain BaO and has a working point of 1140 ° C. or lower by adjusting the content of components such as Al 2 O 3 . .
  • Patent Document 2 since the glass disclosed in Patent Document 2 has a high content of B 2 O 3 , there is a problem that a heterogeneous layer such as so-called scum is easily formed in the melting step, and productivity is easily deteriorated.
  • an object of the present invention is to provide a pharmaceutical glass and a pharmaceutical glass tube having higher productivity and chemical durability than conventional products.
  • the present inventors have found that the above technical problem can be solved by regulating the glass composition within a predetermined range, and propose the present invention. That is, the pharmaceutical glass of the present invention is SiO 2 72.0 to 80%, B 2 O 3 5 to 12.4%, Al 2 O 3 5 to 15%, Na 2 O 0 to 10% by mass. , K 2 O 0 to 10%, Na 2 O + K 2 O 7.6 to 15%, CaO 0 to 5%, BaO 0.1 to 1.9%.
  • the pharmaceutical glass of the present invention preferably has a mass reduction amount per unit area of 1.0 (mg / dm 2 ) or less.
  • the pharmaceutical glass of the present invention is, by mass%, SiO 2 73-75.5%, B 2 O 3 5-12%, Al 2 O 3 5-15%, Na 2 O 0-9%, K 2 O. Contains 0-9%, Na 2 O + K 2 O 7.6-9%, CaO 0-5%, BaO 0.1-1.9%, ZrO 2 0-0.5%, Cl 0-5% It is preferable.
  • the pharmaceutical glass of the present invention preferably has a value of SiO 2 / (Al 2 O 3 + B 2 O 3 ) of 4.75 or less by mass ratio.
  • the temperature at which the viscosity of the glass is 10 4 dPa ⁇ s is preferably 1160 ° C. or lower.
  • the temperature at which the viscosity of the glass is 10 4 dPa ⁇ s is referred to as a working point.
  • the medicinal glass of the present invention preferably has a liquidus viscosity of 10 5 dPa ⁇ s or more.
  • the pharmaceutical glass of the present invention a pharmaceutical glass having higher productivity and chemical durability than conventional products can be obtained. More specifically, the pharmaceutical glass of the present invention has a liquid phase viscosity that can be molded by the Danner method and has high chemical durability by appropriately regulating the content of SiO 2 or alkali metal. Obtainable.
  • composition of the present invention has a glass composition, in mass%, SiO 2 72.0 ⁇ 80% , B 2 O 3 5 ⁇ 12.4%, Al 2 O 3 5 ⁇ 15%, Na 2 O 0 ⁇ 10%, K 2 O 0-10%, Na 2 O + K 2 O 7.6-15%, CaO 0-5%, BaO 0.1-1.9%.
  • the reason for limiting the content range of each component as described above will be described below.
  • “%” represents mass% unless otherwise specified, and the numerical range expressed using “to” is the numerical value described before and after “to”. Is included as a lower limit and an upper limit.
  • SiO 2 is a component that forms a network of glass.
  • the content of SiO 2 is 72.0 to 80%, preferably 72.0 to 77%, more preferably 73 to 75.5%.
  • the content of SiO 2 is less than 72%, the acid resistance and chemical durability of the glass tend to decrease.
  • the content of SiO 2 is more than 80%, the liquid phase viscosity is lowered, and the moldability and productivity are easily deteriorated.
  • B 2 O 3 is a component having an effect of suppressing devitrification by increasing the liquidus viscosity of the glass.
  • the content of B 2 O 3 is 5 to 12.4%, preferably 7 to 12.4%, more preferably 9 to 12%.
  • the content of B 2 O 3 is less than 5%, it is difficult to obtain the effect of increasing the liquid phase viscosity and the effect of suppressing devitrification. If the content of B 2 O 3 is more than 12.4%, a heterogeneous layer such as scum is likely to be formed in the melting step or the like.
  • Al 2 O 3 is a component that has the effect of increasing the liquidus viscosity of glass to improve devitrification resistance and improving water resistance.
  • the content of Al 2 O 3 is 5 to 15%, preferably 5 to 10%, more preferably 5 to 7%.
  • the content of Al 2 O 3 is less than 5%, it is difficult to obtain an effect of improving devitrification resistance and an effect of improving water resistance.
  • the content of Al 2 O 3 is more than 15%, the viscosity of the glass increases, meltability and moldability tends to deteriorate.
  • Both B 2 O 3 and Al 2 O 3 are components that stabilize SiO 2 in the glass network.
  • SiO 2 / (Al 2 O 3 + B 2 O 3 ) increases, it may be difficult to stabilize SiO 2 in the glass network. Therefore, cristobalite is likely to be precipitated in the glass, and the liquid phase viscosity may be lowered. Therefore, the value of SiO 2 / (Al 2 O 3 + B 2 O 3 ) is preferably 4.75 or less, and more preferably 4.70 or less.
  • Na 2 O is a component having an effect of reducing the viscosity of the glass and adjusting the thermal expansion coefficient.
  • the content of Na 2 O is 0 to 10%, preferably 3 to 10%, more preferably 5 to 9%. When the content of Na 2 O is greater than 10%, thermal shock resistance is deteriorated thermal expansion coefficient of the glass is increased considerably.
  • K 2 O like Na 2 O, is a component that has the effect of reducing the viscosity of the glass and increasing the thermal expansion coefficient.
  • the content of K 2 O is 0 to 10%, preferably 0.1 to 7%, more preferably 1 to 3%. When the content of K 2 O is more than 10%, thermal shock resistance is deteriorated thermal expansion coefficient is increased greatly.
  • the total amount of Na 2 O and K 2 O is 7.6 to 15%, preferably 7.6 to 9%, more preferably 7.6 to 8.5%.
  • the total amount of Na 2 O and K 2 O is less than 7.6%, the working point becomes high and the moldability tends to deteriorate.
  • the total amount of Na 2 O and K 2 O is more than 15%, the thermal expansion coefficient of the glass increases and the thermal shock resistance tends to deteriorate.
  • CaO is a component that has the effect of improving the solubility of glass.
  • the content of CaO is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1.1%. When there is more content of CaO than 5%, the acid resistance of glass will fall and chemical durability will deteriorate easily.
  • BaO is a component having an effect of adjusting the thermal expansion coefficient of glass and lowering the viscosity.
  • the content of BaO is 0.1 to 1.9%, preferably 0.1 to 1.5%, and more preferably 0.1 to 1.3%.
  • the viscosity of the glass increases and the working point becomes too high. If the viscosity of the glass is decreased by increasing the content of Na 2 O, K 2 O, and CaO without containing BaO, the thermal expansion coefficient becomes too high and the thermal shock resistance tends to deteriorate. . This is because the amount of increase in the thermal expansion coefficient per content of Na 2 O, K 2 O, and CaO is larger than that of BaO.
  • the pharmaceutical glass of the present invention may further contain ZrO 2 .
  • ZrO 2 is a component that improves the chemical durability and heat resistance of glass.
  • the content of ZrO 2 is preferably 0 to 0.5%, more preferably 0 to 0.2%. When the content of ZrO 2 is more than 0.5%, the viscosity of the glass increases and the working point may be increased.
  • the pharmaceutical glass of the present invention may contain one or more kinds of Cl, Sb 2 O 3 , As 2 O 3 , SnO 2 , Na 2 SO 4 and the like as a fining agent, and among them, Cl is preferable. .
  • the total content of these fining agents is preferably 0 to 5%, more preferably 0 to 1%, and even more preferably 0 to 0.5%. If the total content of the clarifying agent is more than 5%, elution of the clarifying agent into the chemical solution stored in the medical glass container and alteration of the chemical component may occur.
  • the pharmaceutical glass of the present invention may contain TiO 2 or Fe 2 O 3 for the purpose of improving the shielding performance of ultraviolet rays and visible rays.
  • the total content of TiO 2 and Fe 2 O 3 is preferably 0 to 10%.
  • the medicinal glass of the present invention is improved in chemical durability, high temperature viscosity, etc.
  • P 2 O 5 , Cr 2 O 3 , PbO, La 2 O 3 , WO 3 , Nb 2 O 5 , Y 2 O 3 and the like may be added up to 3% each.
  • the pharmaceutical glass of the present invention may contain, for example, H 2 , CO 2 , CO, H 2 O, He, Ne, Ar, and N 2 up to 0.1% as impurities. Further, Pt, Rh, and Au may be contained up to 500 ppm or less as impurities. The content of each of Pt, Rh, and Au is more preferably 300 ppm or less.
  • the borosilicate glass for pharmaceutical use of the present invention preferably has a mass loss per unit area of 1.0 (mg / dm 2 ) or less in an acid resistance test according to DIN (German Industrial Standard) 12116. If the amount of mass loss is greater than 1.0 (mg / dm 2 ), that is, if there is a large amount of eluate from the glass, when the pharmaceutical glass is used as a pharmaceutical container, the filled medicine is likely to be altered. Tend. Therefore, the mass reduction amount is more preferably 0.95 (mg / dm 2 ) or less, further preferably 0.8 (mg / dm 2 ) or less, and most preferably 0.5 (mg / dm 2 ) or less. is there.
  • the working glass (temperature at which the viscosity of the glass becomes 10 4 dPa ⁇ s) is preferably 1160 ° C. or less in the pharmaceutical glass of the present invention.
  • the working point is more preferably 1157 ° C. or less, further preferably 1155 ° C. or less, and most preferably 1150 ° C. or less.
  • the working point is higher than 1160 ° C., it is necessary to increase the processing temperature when producing a medical container such as an ampoule or glass for a tube from the medical glass of the present invention formed into a tubular shape.
  • processing temperature becomes high, the evaporation amount of the alkali component in glass will increase remarkably, and the evaporated alkali component will adhere easily to the inner surface of a pharmaceutical container. If the alkali component adhering to the inner surface of the medical container is eluted into the chemical solution during storage of the chemical solution or in an autoclave treatment after filling the chemical solution, the pH of the chemical solution may be increased or the chemical component
  • the liquid phase viscosity of the pharmaceutical glass of the present invention is preferably 10 5 dPa ⁇ s or more.
  • the liquid phase viscosity is more preferably 10 5.2 dPa ⁇ s or more, and still more preferably 10 5.4 dPa ⁇ s or more. If the liquid phase viscosity is lower than 10 5 dPa ⁇ s, it may be difficult to form a glass using the Danner method or the like, and thus it may be difficult to produce a pharmaceutical glass tube in large quantities at low cost.
  • the liquidus temperature of the pharmaceutical glass of the present invention is preferably 1010 ° C. or lower.
  • the liquidus temperature is more preferably 970 ° C. or lower, and further preferably 950 ° C. or lower.
  • the liquidus temperature is an important index for considering the devitrification resistance of glass. As the liquidus temperature is higher, devitrification is more likely to occur in the production process and the processing process.
  • the pharmaceutical glass of the present invention preferably has a thermal expansion coefficient of 50 to 60 ⁇ 10 ⁇ 7 / ° C. at 30 to 380 ° C.
  • the thermal expansion coefficient is more preferably 50 to 58 ⁇ 10 ⁇ 7 / ° C., further preferably 51 to 55 ⁇ 10 ⁇ 7 / ° C., and most preferably 51 to 53 ⁇ 10 ⁇ 7 / ° C. If the thermal expansion coefficient is lower than 50 ⁇ 10 ⁇ 7 / ° C., the viscosity of the glass tends to increase, and the melting temperature and the molding temperature may increase, making it difficult to produce the glass. Further, if the thermal expansion coefficient is higher than 60 ⁇ 10 ⁇ 7 / ° C., there is a high possibility that the glass will be damaged by a thermal shock in the glass manufacturing process, processing process, sterilization process, and the like.
  • the Danner method is suitable as a method for producing the pharmaceutical glass tube of the present invention.
  • a glass raw material is prepared so as to have the above glass composition to produce a glass batch.
  • this glass batch is 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, The medical glass tube is pulled out from the tip.
  • the manufacturing method of the glass tube for pharmaceuticals of this invention is not restricted to the Danner method, You may use the conventional method.
  • the bellows method is also an effective method for producing the pharmaceutical glass tube of the present invention.
  • Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 6) and comparative examples (samples No. 7 and 8).
  • the obtained glass batch was put in a platinum crucible and melted at 1600 ° C. for 4 hours.
  • a predetermined annealing treatment furnace cooling in an electric furnace set at 650 ° C.
  • the obtained glass sample was processed into the shape suitable for the following characteristic evaluation, and various characteristics were evaluated.
  • the acid resistance test was carried out in accordance with DIN (German Industrial Standard) 12116.
  • DIN12116 the total surface area of the sample is defined as 100 cm 2 , but in the acid resistance test of this example, the total surface area of the sample was 50 cm 2 .
  • DIN12116 the volume of the eluate (6 mol / L hydrochloric acid) is regulated to 1500 mL, but in the acid resistance test of this example, the volume of the eluate was set to 800 mL.
  • the detailed test procedure is as follows. First, all the surfaces of the glass sample were mirror-polished and a sample piece having a total surface area of 50 cm 2 was prepared. Next, the sample piece was immersed in a solution in which hydrofluoric acid (40% by mass) and hydrochloric acid (2 mol / L) were mixed at a volume ratio of 1: 9, and stirred with a magnetic stirrer for 10 minutes. Next, the sample piece was taken out and subjected to ultrasonic cleaning for 2 minutes with ultra pure water three times, and then ultrasonic cleaning for 1 minute with ethanol was performed twice. The sample piece was then 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 was measured to an accuracy of ⁇ 0.1 mg and recorded.
  • 800 mL of 6 mol / L hydrochloric acid was put into a beaker made of quartz glass and heated until boiling using an electric heater. After boiling, a sample piece suspended with a platinum wire was put into hydrochloric acid and held for 6 hours. Thereafter, the sample piece was taken out and subjected to ultrasonic cleaning for 2 minutes with ultrapure water three times, and then ultrasonic cleaning for 1 minute with ethanol was performed twice. 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 was measured to an accuracy of ⁇ 0.1 mg and recorded.
  • the mass reduction amount ⁇ m per unit area is calculated by the following formula 1, and the acid resistance test was measured. It can be said that the smaller the mass reduction amount ⁇ m, the more excellent the acid resistance.
  • Strain point and annealing point are values measured based on the method of ASTM C336.
  • Softening point is a value measured based on the method of ASTM C338.
  • Working point is a value obtained by measuring the temperature at which the viscosity of the glass is 10 4.0 dPa ⁇ s at a platinum ball pulling method.
  • the liquid phase temperature passed through a standard sieve 30 mesh (500 ⁇ m), the glass powder remaining in 50 mesh (300 ⁇ m) was placed in a platinum boat, held in a temperature gradient furnace for 24 hours, and then the temperature at which crystals precipitated was measured. Value.
  • Liquid phase viscosity refers to the value of glass viscosity at the liquidus temperature calculated from the viscosity curve of the glass obtained from the strain point, annealing point, softening point, working point and Fulcher's viscosity calculation formula.
  • the thermal expansion coefficient is a value obtained by measuring an average thermal expansion coefficient in a temperature range of 30 to 380 ° C. using a dilatometer.
  • Sample No. Nos. 1 to 6 were glasses having a mass reduction amount ⁇ m in an acid resistance test of 1.0 mg / dm 2 or less, and having few alkali elutions and excellent acid resistance.
  • Sample No. No. 8 was a glass having a mass reduction amount ⁇ m in the acid resistance test of more than 1.0 mg / dm 2 and a large amount of alkali elution.
  • Sample No. 7 and 8 were glasses having high work points and poor workability.
  • the medicinal glass and medicinal glass tube of the present invention are suitable as materials for medicinal containers.

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  • 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)

Abstract

L'invention concerne un verre médical et un tube en verre médical qui peuvent être produits à une productivité élevée et qui présentent une durabilité chimique élevée. Le verre médical comprend, en % en masse, 72,0-80 % de SiO2, 5-12,4 % de B2O3, 5-15 % d'Al2O3, 0-10 % de Na2O, 0-10 % de K2O, 7,6-15 % de Na2O+K2O, 0-5 % de CaO et 0,1-1,9 % de BaO. Le verre médical présente de préférence une perte de masse par unité de surface de 1,0 (mg/dm2) ou moins, comme déterminé par un test de résistance à l'acide selon la norme DIN12116.
PCT/JP2013/077271 2012-10-31 2013-10-07 Verre médical et tube en verre médical Ceased WO2014069177A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012239843A JP2014088293A (ja) 2012-10-31 2012-10-31 医薬用ガラス及び医薬用ガラス管
JP2012-239843 2012-10-31

Publications (1)

Publication Number Publication Date
WO2014069177A1 true WO2014069177A1 (fr) 2014-05-08

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PCT/JP2013/077271 Ceased WO2014069177A1 (fr) 2012-10-31 2013-10-07 Verre médical et tube en verre médical

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JP (1) JP2014088293A (fr)
WO (1) WO2014069177A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105800926A (zh) * 2016-03-01 2016-07-27 盐城市华鸥实业有限公司 用于玻璃仪器的化学稳定性好的高硼硅玻璃及制备方法
CN111386250A (zh) * 2018-03-22 2020-07-07 日本电气硝子株式会社 精密玻璃管及其制造方法
JP2023553170A (ja) * 2020-12-10 2023-12-20 コーニング インコーポレイテッド 車両のフロントガラス用の特有の破壊挙動を備えたガラス

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015214431B3 (de) * 2015-07-29 2016-12-22 Schott Ag Bor-armes Zirkonium-freies Neutralglas mit optimiertem Alkaliverhältnis
CN111225884B (zh) * 2017-10-20 2022-12-06 日本电气硝子株式会社 医药品容器用玻璃和医药品容器用玻璃管

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0474731A (ja) * 1990-07-06 1992-03-10 Nippon Electric Glass Co Ltd 医薬用硼珪酸ガラス
JPH04219343A (ja) * 1990-12-18 1992-08-10 Nippon Electric Glass Co Ltd 医療用紫外線吸収性ガラス
JPH04280833A (ja) * 1991-03-08 1992-10-06 Nippon Electric Glass Co Ltd ホウケイ酸ガラス
WO1996033954A2 (fr) * 1995-04-28 1996-10-31 Technische Glaswerke Ilmenau Gmbh Verre borosilicate
JPH09118541A (ja) * 1995-09-30 1997-05-06 Schott Ruhrglas Gmbh 酸化ジルコニウム及び酸化リチウムを含有する高耐薬品性且つ低粘性のホウケイ酸ガラス及びその用途
JP2004504258A (ja) * 2000-07-22 2004-02-12 カール　ツァイス　スティフツンク 耐薬品性の高いホウケイ酸ガラス、およびその使用
US20090315002A1 (en) * 2008-04-30 2009-12-24 Franz Ott Borosilicate glass with UV-blocking properties for pharmaceutical packaging

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0474731A (ja) * 1990-07-06 1992-03-10 Nippon Electric Glass Co Ltd 医薬用硼珪酸ガラス
JPH04219343A (ja) * 1990-12-18 1992-08-10 Nippon Electric Glass Co Ltd 医療用紫外線吸収性ガラス
JPH04280833A (ja) * 1991-03-08 1992-10-06 Nippon Electric Glass Co Ltd ホウケイ酸ガラス
WO1996033954A2 (fr) * 1995-04-28 1996-10-31 Technische Glaswerke Ilmenau Gmbh Verre borosilicate
JPH09118541A (ja) * 1995-09-30 1997-05-06 Schott Ruhrglas Gmbh 酸化ジルコニウム及び酸化リチウムを含有する高耐薬品性且つ低粘性のホウケイ酸ガラス及びその用途
JP2004504258A (ja) * 2000-07-22 2004-02-12 カール　ツァイス　スティフツンク 耐薬品性の高いホウケイ酸ガラス、およびその使用
US20090315002A1 (en) * 2008-04-30 2009-12-24 Franz Ott Borosilicate glass with UV-blocking properties for pharmaceutical packaging

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105800926A (zh) * 2016-03-01 2016-07-27 盐城市华鸥实业有限公司 用于玻璃仪器的化学稳定性好的高硼硅玻璃及制备方法
CN111386250A (zh) * 2018-03-22 2020-07-07 日本电气硝子株式会社 精密玻璃管及其制造方法
JP2023553170A (ja) * 2020-12-10 2023-12-20 コーニング インコーポレイテッド 車両のフロントガラス用の特有の破壊挙動を備えたガラス

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