JPH0474731A - Borosilicate glass medical use - Google Patents
Borosilicate glass medical useInfo
- Publication number
- JPH0474731A JPH0474731A JP18013890A JP18013890A JPH0474731A JP H0474731 A JPH0474731 A JP H0474731A JP 18013890 A JP18013890 A JP 18013890A JP 18013890 A JP18013890 A JP 18013890A JP H0474731 A JPH0474731 A JP H0474731A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- thermal expansion
- borosilicate glass
- viscosity
- medical use
- 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.)
- Pending
Links
- 239000005388 borosilicate glass Substances 0.000 title abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 abstract description 21
- 239000000126 substance Substances 0.000 abstract description 15
- 229910052788 barium Inorganic materials 0.000 abstract description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010433 feldspar Substances 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000007791 liquid phase Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 13
- 239000003513 alkali Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 206010040925 Skin striae Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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
- C03C3/089—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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、医薬用アンプル、バイヤル、注射器等の医療
器具及び化学用体積針に使用される無色透明な医薬用硼
珪酸ガラスに関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a colorless and transparent pharmaceutical borosilicate glass used for medical instruments such as pharmaceutical ampoules, vials, and syringes, and chemical volumetric needles. .
［従来技術とその問題点］
従来より医薬用アンプル、バイヤル、注射器等の医療器
具及び化学用体積針に使用されるガラスとしては、化学
的耐久性を向上するためにＢａＯを添加した硼珪酸ガラ
スが使用されている。[Prior art and its problems] As the glass conventionally used for medical instruments such as pharmaceutical ampoules, vials, and syringes, and chemical volumetric needles, borosilicate glass to which BaO is added to improve chemical durability has been used. is used.
しかしながら一般にＢａＯを添加した硼珪酸ガラスは、
ガラス溶融時あるいは成管時にＢａＯ成分とアルミナ系
耐火物との反応によってバリウム長石結晶が析出しやす
く、生産歩留りが低下すると共に薬品中の硫酸イオンと
ガラス中のバリウムとが反応して沈殿物が生じる恐れが
ある。However, in general, borosilicate glass doped with BaO,
Barium feldspar crystals tend to precipitate due to the reaction between BaO components and alumina refractories during glass melting or tube forming, which lowers production yields and also causes precipitates to form due to the reaction between sulfate ions in the chemicals and barium in the glass. There is a possibility that this may occur.
このような事情からＢａＯを含有しない医薬用硼珪酸ガ
ラスが各種提案されており、例えば特公昭６３−１１２
９３号公報には、ＢａＯを含有せず、優れた化学的耐久
性、成形性を具備する医薬用硼珪酸ガラスが開示され、
また特開昭６４−１８９３９号公報には、ＢａＯを含有
せず、優れた化学的耐久性を具備する医薬用硼珪酸ガラ
スが開示されている。Under these circumstances, various medical borosilicate glasses that do not contain BaO have been proposed; for example, Japanese Patent Publication No. 63-112
Publication No. 93 discloses a pharmaceutical borosilicate glass that does not contain BaO and has excellent chemical durability and formability,
Further, JP-A-64-18939 discloses a medical borosilicate glass that does not contain BaO and has excellent chemical durability.
しかしながら特公昭Ｇ３−１１２９３号公報の硼珪酸ガ
ラスは、５ＩＯ３を７４．０％以下しか含有しないため
、熱膨張係数が大きなりすぎて耐熱性が低下し、その結
果二次熱加工した場合、直ちに徐冷しないとガラス加工
品が破損する恐れがある。However, since the borosilicate glass disclosed in Japanese Patent Publication No. Sho G3-11293 contains only 74.0% or less of 5IO3, the coefficient of thermal expansion is too large and the heat resistance is reduced. If the glass is not slowly cooled, the glass product may be damaged.
さらに特開昭８４−１８９３９号公報の硼珪酸ガラスは
、Ａｌ２Ｏ３を６．０％以下しか含有しないため、液相
温度の粘度が低くなりすぎ、成管中に結晶を析出しやす
くなって生産歩留りが低下するという問題がある。Furthermore, since the borosilicate glass disclosed in JP-A-84-18939 contains only 6.0% or less of Al2O3, the viscosity at the liquidus temperature is too low, and crystals are likely to precipitate during pipe forming, resulting in a decrease in production yield. There is a problem that the amount decreases.
［発明の目的］
本発明の目的は、ＢａＯを含有しないためにバリウム長
石結晶が析出せず、優れた化学的耐久性を有し、熱膨張
係数が３０〜３８０℃で４６〜５３Ｘ１０“７／℃、液
相温度の粘度がｌｏｇ ｌで５．０以上である医薬用硼
珪酸ガラスを提供することである。[Objective of the Invention] The object of the present invention is that barium feldspar crystals do not precipitate because it does not contain BaO, has excellent chemical durability, and has a thermal expansion coefficient of 46 to 53 x 10"7/ at 30 to 380°C. An object of the present invention is to provide a pharmaceutical borosilicate glass having a viscosity at a liquidus temperature of 5.0 or more in log l.
［発明の構成コ
本発明の医薬用硼珪酸ガラスは、重量百分率で５ｉｎ２
７４．５〜７６．５％、８２Ｏ３ ’９．５〜１１．５
％、Ａｌ２Ｏ３［ｆ、１〜７．５％、Ｎａ２Ｏ５，０〜
７．５％、Ｋ２Ｏ０，５〜２．０％、ＣａＯＯ，５〜１
．５％の組成を有し、液相温度の粘度がｌｏｇηで５．
０以上であり、熱膨張係数が３０〜３８０℃で４６〜５
３Ｘ １０−７／ ’Ｃであることを特徴とする。[Constitution of the Invention] The pharmaceutical borosilicate glass of the present invention has a weight percentage of 5in2
74.5-76.5%, 82O3'9.5-11.5
%, Al2O3 [f, 1-7.5%, Na2O5, 0-
7.5%, K2O0.5-2.0%, CaOO,5-1
．． It has a composition of 5%, and a viscosity at a liquidus temperature of log η of 5.
0 or more, and the coefficient of thermal expansion is 46 to 5 at 30 to 380°C
It is characterized by being 3X 10-7/'C.
本発明のガラス組成を上記のように限定した理由を以下
に説明する。The reason why the glass composition of the present invention is limited as described above will be explained below.
５１０□は、主要なガラス形成酸化物であるが、７６゜
５％より多い場合は、ガラスの溶融性及び加工性が著し
く悪（なり、一方７４．５％より少ない場合は、熱膨張
係数が大きくなりすぎて、加工したガラスが破損しやす
くなる。510□ is the main glass-forming oxide, but if it is more than 76°5%, the meltability and processability of the glass will be extremely poor (while if it is less than 74.5%, the coefficient of thermal expansion will be poor). If it becomes too large, the processed glass will be easily damaged.
Ｂ２Ｏ３は、ガラスの溶融性を向上させる成分であるが
、１１．５％より多い場合は、化学的耐久性が悪くなり
、一方９．５％より少ない場合は、上記効果が得られ難
い。B2O3 is a component that improves the meltability of glass, but if it is more than 11.5%, the chemical durability deteriorates, while if it is less than 9.5%, it is difficult to obtain the above effects.
Ａｌ２Ｏ，は、ガラスの失透を抑制し、化学的耐久性を
向上させる成分であるが、７．５％より多い場合は、ガ
ラスの溶融性が悪くなって、脈理や泡が発生しやすくな
り、一方６．１％より少ない場合は、液相温度の粘度が
ｌｏｇ １で５．０以下となり、成管中に結晶が析出し
やすくなる。Al2O is a component that suppresses devitrification of glass and improves chemical durability, but if it exceeds 7.5%, the meltability of glass deteriorates and striae and bubbles are likely to occur. On the other hand, when it is less than 6.1%, the viscosity at the liquidus temperature becomes 5.0 or less in log 1, and crystals tend to precipitate during tube forming.
Ｎａ、Ｏは、ガラスの溶融性を向上すると共に熱膨張係
数を向上させる効果があるが、７．５％より多い場合は
、化学的耐久性が悪くなると共に熱膨張係数が高くなり
すぎて加工したガラスが破損しやすくなり、一方５．０
％より少ない場合は、上記効果が得られない。Na and O have the effect of improving the meltability of glass and the coefficient of thermal expansion, but if it exceeds 7.5%, the chemical durability will deteriorate and the coefficient of thermal expansion will become too high, making it difficult to process. 5.0 glass is more likely to break.
%, the above effects cannot be obtained.
Ｎａ２Ｏの一部をに２Ｏで置換すると化学的耐久性が向
上し、液相温度が下がって失透しにくくなるが、Ｋ、０
が２．０％より多い場合は、ガラスの粘度が上がって溶
融性が悪くなり、一方０．５％より少ない場合は、上記
効果が得られ難い。Substituting a part of Na2O with 2O improves chemical durability, lowers the liquidus temperature and makes it difficult to devitrify, but K, 0
If the amount is more than 2.0%, the viscosity of the glass will increase and the meltability will deteriorate, while if it is less than 0.5%, the above effects will be difficult to obtain.
ＣａＯは、ガラスの溶融性及び化学的耐久性を向上させ
るが、１．５％より多い場合は、熱膨張係数が高くなり
すぎて、０．５％より少ない場合は、上記効果が得られ
難い。CaO improves the meltability and chemical durability of glass, but if it is more than 1.5%, the coefficient of thermal expansion becomes too high, and if it is less than 0.5%, it is difficult to obtain the above effects. .
［実施例］ 以下、本発明を実施例に基づいて詳細に説明する。[Example] Hereinafter, the present invention will be explained in detail based on examples.
次表は、本発明のガラス（試料Ｎｏ、１〜５）及び比較
例のガラス（試料Ｎｏ、８〜８）の組成、熱膨張係数、
徐冷点、軟化点、作業点、液相温度、液相温度の粘度、
バリウム長石結晶の析出温度、日本薬局方アルカリ溶出
試験およびＪＩＳ Ｒ３５０２アルカリ溶出試験による
アルカリ溶出量を示すものである。The following table shows the composition, thermal expansion coefficient, and
Annealing point, softening point, working point, liquidus temperature, viscosity at liquidus temperature,
It shows the precipitation temperature of barium feldspar crystals, the amount of alkali elution according to the Japanese Pharmacopoeia alkali elution test and the JIS R3502 alkali elution test.
以 下 余 白 表の各試料は、以下のようにして調製した。Below, remaining white Each sample in the table was prepared as follows.
まず表の組成になるようにガラス原料を調合した後、白
金ルツボに入れ、ｌ５５０°Ｃ１６時間の条件で溶融し
、各特性の測定に供するために必要な形状に成形した。First, glass raw materials were prepared to have the composition shown in the table, then placed in a platinum crucible, melted at 1550°C for 16 hours, and formed into the necessary shapes for measurement of each property.
表から明らかなように本発明のガラスは、熱膨張係数カ
４７．０〜５２．ＯＸ １０−’／’Ｃ１液相温度の粘
度が５．６〜５．７であり、またバリウム長石結晶が析
出せず、アリカリ溶出量が少なく、優れた化学的耐久性
を有していることがわかる。As is clear from the table, the glass of the present invention has a thermal expansion coefficient of 47.0 to 52. The viscosity at OX 10-'/'C1 liquidus temperature is 5.6 to 5.7, and barium feldspar crystals do not precipitate, the amount of alkali elution is small, and it has excellent chemical durability. I understand.
それに対し、比較例であるＮｏ 、Ｇ〜８の各試料は、
アルカリ溶出量は少なかったが、Ｎｏ、６の試料はバリ
ウム長石結晶が析出し、またＮｏ 、７の試料は熱膨張
係数が５５ＸＩＯ−７／℃と高く、耐熱性が悪いと思わ
れる。さらにＮｏ 、８の試料は液相温度の粘度が４゜
８と低かった。On the other hand, each sample of No. G to 8, which is a comparative example,
Although the amount of alkali elution was small, barium feldspar crystals were precipitated in the sample No. 6, and the thermal expansion coefficient of the sample No. 7 was as high as 55XIO-7/°C, which suggests that the sample No. 7 has poor heat resistance. Furthermore, sample No. 8 had a low viscosity at liquidus temperature of 4°8.
尚、表中の熱膨張係数は、約５φＸ ５０ｍｍのロッド
状に成形した試料を用いて平均線熱膨張測定器によって
測定した。The coefficient of thermal expansion in the table was measured using an average linear thermal expansion measuring device using a sample molded into a rod shape of about 5φ x 50mm.
液相温度は、約１２Ｏ Ｘ ２ＯＸ １０ｍｍの大きさ
の白金ボートに粉砕した試料を充填し、これを温度勾配
炉内に入れて１６時間保持した後、炉内からボートを取
り出して放冷し、顕微鏡を用いてガラス中の結晶の有無
を調べ、結晶の析出した最高温度をそのガラスの液相温
度と見做した。また液相温度の粘度は、徐冷点、軟化点
、作業点とＦｕｌｃｈｅｒの粘性計算式によって計算し
て求めた。The liquidus temperature was determined by filling a platinum boat with a size of approximately 120 x 20 x 10 mm with a crushed sample, placing it in a temperature gradient furnace and holding it for 16 hours, then taking out the boat from the furnace and leaving it to cool. The presence or absence of crystals in the glass was examined using a microscope, and the highest temperature at which crystals precipitated was regarded as the liquidus temperature of the glass. Further, the viscosity at the liquidus temperature was determined by calculating the annealing point, softening point, working point, and Fulcher's viscosity calculation formula.
バリウム長石結晶の析出温度は、上記白金ボートに粉砕
した試料と３ Ｘ５ Ｘ１００ｍｍのシリマナイト耐火
物片を入れ、１３００℃で５時間溶融し、これを温度勾
配炉内に入れて１００時間保持し、ガラスと耐火物との
界面でバリウム長石の結晶が析出した最高温度を示した
。The precipitation temperature of barium feldspar crystals was determined by placing the crushed sample and a 3 x 5 x 100 mm piece of sillimanite refractory in the above platinum boat, melting it at 1300°C for 5 hours, placing it in a temperature gradient furnace, holding it for 100 hours, and melting the glass. The maximum temperature at which barium feldspar crystals precipitated at the interface between the steel and the refractory was shown.
［発明の効果コ
以上のように本発明の医薬用硼珪酸ガラスは、ＢａＯを
含有しないためバリウム長石結晶を析出せず、熱膨張係
数が低いために耐熱性が高く、また液相温度の粘度がｌ
ｏｇηで５．０以上であるため、成管中に結晶を析出し
て失透することがない。さらに日本薬局方及びＪＩＳ
Ｒ３５Ｑ２に規定のあるアルカリ溶出量を満足するため
、医薬用アンプル、バイヤル、注射器等の医療器具及び
化学用体積針に使用される無色透明の医薬用硼珪酸ガラ
スとして好適である。[Effects of the Invention] As described above, the medical borosilicate glass of the present invention does not contain BaO and therefore does not precipitate barium feldspar crystals, has a low coefficient of thermal expansion and thus has high heat resistance, and has a low viscosity at the liquidus temperature. is l
Since og η is 5.0 or more, crystals are not precipitated and devitrified during tube formation. Furthermore, Japanese Pharmacopoeia and JIS
Since it satisfies the alkali elution amount specified in R35Q2, it is suitable as a colorless and transparent pharmaceutical borosilicate glass used in medical instruments such as pharmaceutical ampoules, vials, and syringes, and chemical volumetric needles.
特許出願人 日本電気硝子株式会社 代表者 岸 １）清 作Patent applicant: Nippon Electric Glass Co., Ltd. Representative Kishi 1) Kiyoshi Saku
Claims (1)
、Ｂ＿２Ｏ＿３９．５〜１１．５％、Ａｌ＿２Ｏ＿３６
．１〜７．５％、Ｎａ＿２Ｏ５．０〜７．５％、Ｋ＿２
Ｏ０．５〜２．０％、ＣａＯ０．５〜１．５％の組成を
有し、液相温度の粘度がｌｏｇηで５．０以上であり、
熱膨張係数が３０〜３８０℃で４６〜５３×１０＾−＾
７／℃であることを特徴とする医薬用硼珪酸ガラス。(1) In weight percentage, SiO_274.5-76.5%
, B_2O_39.5-11.5%, Al_2O_36
．． 1-7.5%, Na_2O5.0-7.5%, K_2
It has a composition of 0.5 to 2.0% O, 0.5 to 1.5% CaO, and has a viscosity at the liquidus temperature of log η of 5.0 or more,
Thermal expansion coefficient is 46-53 x 10^-^ at 30-380℃
7/℃ for pharmaceutical use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18013890A JPH0474731A (en) | 1990-07-06 | 1990-07-06 | Borosilicate glass medical use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18013890A JPH0474731A (en) | 1990-07-06 | 1990-07-06 | Borosilicate glass medical use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0474731A true JPH0474731A (en) | 1992-03-10 |
Family
ID=16078075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18013890A Pending JPH0474731A (en) | 1990-07-06 | 1990-07-06 | Borosilicate glass medical use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0474731A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118541A (en) * | 1995-09-30 | 1997-05-06 | Schott Ruhrglas Gmbh | Highly chemical-resistant and lowly viscous borosilicate glass containing zirconium oxide and lithium oxide |
| WO2002008134A1 (en) * | 2000-07-22 | 2002-01-31 | Schott Glas | Borosilicate glass with high chemical resistance and use thereof |
| JP2007039315A (en) * | 2005-06-29 | 2007-02-15 | Nippon Electric Glass Co Ltd | Optical glass |
| WO2014069177A1 (en) * | 2012-10-31 | 2014-05-08 | 日本電気硝子株式会社 | Medicinal glass and medicinal glass tube |
| JP2014169209A (en) * | 2013-03-05 | 2014-09-18 | Nippon Electric Glass Co Ltd | Medicine container and method for producing the same |
| EP2796431A1 (en) * | 2013-04-26 | 2014-10-29 | Schott AG | Borosilicate glass with improved hydrolytic resistance preferably for use in the pharmaceutical industry |
| JP2015098430A (en) * | 2013-09-02 | 2015-05-28 | 日本電気硝子株式会社 | Borosilicate glass for medicament container |
| CN105366922A (en) * | 2014-08-14 | 2016-03-02 | 肖特股份有限公司 | Process for producing glass tubes and use thereof |
| WO2019181207A1 (en) * | 2018-03-22 | 2019-09-26 | 日本電気硝子株式会社 | Precision glass tube and method for producing same |
-
1990
- 1990-07-06 JP JP18013890A patent/JPH0474731A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118541A (en) * | 1995-09-30 | 1997-05-06 | Schott Ruhrglas Gmbh | Highly chemical-resistant and lowly viscous borosilicate glass containing zirconium oxide and lithium oxide |
| WO2002008134A1 (en) * | 2000-07-22 | 2002-01-31 | Schott Glas | Borosilicate glass with high chemical resistance and use thereof |
| JP2004504258A (en) * | 2000-07-22 | 2004-02-12 | カール ツァイス スティフツンク | Borosilicate glass with high chemical resistance and its use |
| US6794323B2 (en) | 2000-07-22 | 2004-09-21 | Schott Glas | Borosilicate glass with high chemical resistance and use thereof |
| JP2007039315A (en) * | 2005-06-29 | 2007-02-15 | Nippon Electric Glass Co Ltd | Optical glass |
| WO2014069177A1 (en) * | 2012-10-31 | 2014-05-08 | 日本電気硝子株式会社 | Medicinal glass and medicinal glass tube |
| JP2014169209A (en) * | 2013-03-05 | 2014-09-18 | Nippon Electric Glass Co Ltd | Medicine container and method for producing the same |
| JP2014214084A (en) * | 2013-04-26 | 2014-11-17 | ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ | Borosilicate glass having improved hydrolysis resistance suitable for use in pharmaceutical field |
| CN104118989A (en) * | 2013-04-26 | 2014-10-29 | 肖特股份有限公司 | Borosilicate glass with improved hydrolytic resistance preferably for use in the pharmaceutical industry |
| US20140323287A1 (en) * | 2013-04-26 | 2014-10-30 | Schott Ag | Borosilicate glass having improved hydrolytic resistance for preferred use in the pharmaceutical sector |
| EP2796431A1 (en) * | 2013-04-26 | 2014-10-29 | Schott AG | Borosilicate glass with improved hydrolytic resistance preferably for use in the pharmaceutical industry |
| US9643882B2 (en) * | 2013-04-26 | 2017-05-09 | Schott Ag | Borosilicate glass having improved hydrolytic resistance for preferred use in the pharmaceutical sector |
| CN110128011A (en) * | 2013-04-26 | 2019-08-16 | 肖特股份有限公司 | It is preferred for the Pyrex of the hydrolytic resistance with improvement of field of medicaments |
| CN110128011B (en) * | 2013-04-26 | 2021-06-01 | 肖特股份有限公司 | Borosilicate glass with improved hydrolysis resistance, preferably for use in the medical field |
| JP2015098430A (en) * | 2013-09-02 | 2015-05-28 | 日本電気硝子株式会社 | Borosilicate glass for medicament container |
| JP2018193297A (en) * | 2013-09-02 | 2018-12-06 | 日本電気硝子株式会社 | Borosilicate glass for medicament container |
| CN105366922A (en) * | 2014-08-14 | 2016-03-02 | 肖特股份有限公司 | Process for producing glass tubes and use thereof |
| JP2016041650A (en) * | 2014-08-14 | 2016-03-31 | ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ | Method of manufacturing glass tube and use thereof |
| WO2019181207A1 (en) * | 2018-03-22 | 2019-09-26 | 日本電気硝子株式会社 | Precision glass tube and method for producing same |
| JPWO2019181207A1 (en) * | 2018-03-22 | 2021-03-11 | 日本電気硝子株式会社 | Precision glass tube and its manufacturing method |
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