JP6653076B2 - Glass tube for pharmaceutical container and method for producing the same - Google Patents
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Description
本発明はバイアル、アンプル等の管瓶用ガラスや注射器のシリンジに使用される医薬容器用ガラス管及びその製造方法に関する。 The present invention relates to a glass tube for a vial, an ampule or the like, a glass tube for a medical container used for a syringe of a syringe, and a method for producing the same.
バイアル、アンプル等の作製に用いられる医薬容器用ガラス管には、下記に示すような特性が要求される。
（ａ）充填される薬液中の成分とガラス中の成分が反応しないこと
（ｂ）充填される薬液を汚染しないように化学的耐久性や加水分解抵抗性が高いこと
（ｃ）ガラス管の製造工程や、バイアル、アンプル等への加工時に、サーマルショックによる破損が生じ難いように低熱膨張係数であること
（ｄ）バイアル、アンプル等への加工後に、容器内面がガラスからの蒸発物などで劣化しないよう、加工時の熱量が低減できること
これらの要求特性を満足する標準的な医薬容器用ガラス管は、構成成分として、ＳｉＯ２、Ｂ２Ｏ３、Ａｌ２Ｏ３、Ｎａ２Ｏ、Ｋ２Ｏ、ＣａＯ、ＢａＯと少量の清澄剤を含有するホウケイ酸ガラスから作製される。
Glass tubes for pharmaceutical containers used for producing vials, ampules and the like are required to have the following properties.
(A) Components in the filled chemical do not react with components in the glass. (B) High chemical durability and hydrolysis resistance so as not to contaminate the filled chemical. (C) Manufacture of glass tubes. Low coefficient of thermal expansion so that damage due to thermal shock is unlikely to occur during the process or processing into vials, ampoules, etc. (d) After processing into vials, ampules, etc., the inner surface of the container is degraded by evaporation from glass etc. The amount of heat at the time of processing can be reduced so as not to cause such a problem. A standard glass tube for a medical container satisfying these required characteristics is composed of SiO 2 , B 2 O 3 , Al 2 O 3 , Na 2 O, and K 2 It is made from borosilicate glass containing O, CaO, BaO and a small amount of fining agent.
近年、充填される薬液の開発が進み、より薬効の高い薬液が使用されつつある。これらの薬液の中には、化学的に不安定で変性しやすく、ガラスとの反応性が高いものもある。これに伴い、バイアルやアンプルを構成する医薬容器用ホウケイ酸ガラスには、従来以上に化学的耐久性や加水分解抵抗性の高いガラスが要求されている。また、ガラスがＢａＯを含有していると、ガラス溶融時に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易くなり生産性が低下すると共に、ガラスから溶出したＢａイオンが薬液中の硫酸イオンと反応して不溶性の沈殿物を発生させる恐れがある。 In recent years, the development of a drug solution to be filled has progressed, and a drug solution having a higher medicinal effect is being used. Some of these chemicals are chemically unstable and easily denatured, and have high reactivity with glass. Along with this, borosilicate glass for pharmaceutical containers constituting vials and ampoules is required to have glass having higher chemical durability and hydrolysis resistance than ever before. Further, when the glass contains BaO, the barium feldspar crystal is easily precipitated by the reaction with the alumina-based refractory when the glass is melted, thereby lowering the productivity. In addition, Ba ions eluted from the glass are converted into sulfate ions in the chemical solution. And may form an insoluble precipitate.
このような事情から、例えば特許文献１では、ＢａＯを含有せず加水分解抵抗性が高いガラスが提案されている。 Under such circumstances, for example, Patent Document 1 proposes a glass that does not contain BaO and has high hydrolysis resistance.
ところで、バイアルやアンプルなどの医薬容器は、管ガラスを局所的にバーナーで加熱して加工することで作製される。このバーナー加熱時に、ガラス中のＢ２Ｏ３やＮａ２Ｏなどが蒸発し、医薬容器内面に凝縮し、異質層が形成される場合がある。異質層が形成されるとガラスの化学的耐久性や加水分解抵抗性が実質的に低下し、薬液の保存中や薬液充填後のオートクレーブ処理時に異質層からＢ２Ｏ３やＮａ２Ｏなどが溶出し、薬液成分の変質や薬液のｐＨ変化などを引き起こす可能性がある。特に特許文献１のようなＢａＯを含まないガラスは、ＢａＯを含むガラスに比べて加工性が低いことから、容器加工時に従来よりも大きな熱量が必要になる。その結果、ガラス中からのＢ２Ｏ３やＮａ２Ｏなどの蒸発量が増加し易い。 By the way, medical containers such as vials and ampoules are produced by locally processing tube glass with a burner. During the heating of the burner, B 2 O 3 , Na 2 O and the like in the glass evaporate and condense on the inner surface of the medicine container, and a foreign layer may be formed. When the foreign layer is formed, the chemical durability and hydrolysis resistance of the glass substantially decrease, and B 2 O 3 , Na 2 O, and the like are removed from the foreign layer during storage of the chemical solution or during autoclave treatment after filling the chemical solution. It may be eluted and may cause deterioration of the chemical component or a change in the pH of the chemical. In particular, glass that does not contain BaO as in Patent Literature 1 has lower workability than glass that contains BaO, and therefore requires a larger amount of heat when processing containers. As a result, the amount of evaporation of B 2 O 3 and Na 2 O from the glass tends to increase.
本発明の目的は、ＢａＯを含有しないホウケイ酸ガラスからなるにも関わらず、加工性の良い医薬容器用ガラス管とその製造方法を提供することである。 An object of the present invention is to provide a glass tube for a medical container having good workability and a method for producing the same, which is made of borosilicate glass containing no BaO.
本発明者等は種々の実験を行い、Ｂ２Ｏ３やＮａ２Ｏの蒸発量は、ガラス管の組成だけでなく、ガラス管の寸法精度とも関係があり、ガラス管の曲がりや偏肉を低減し、加工性を高めることで容器加工に必要な熱量を抑制できることを見出した。 The present inventors have conducted various experiments, and the amount of evaporation of B 2 O 3 and Na 2 O is related not only to the composition of the glass tube but also to the dimensional accuracy of the glass tube. It has been found that the amount of heat required for container processing can be suppressed by reducing and increasing the processability.
本発明の医薬容器用ガラス管は、ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ、Ｒ２Ｏ（ＲはＬｉ、Ｎａ、Ｋのいずれか１種類以上）を必須成分として含み、ＢａＯを実質的に含まないホウケイ酸ガラスからなり、ガラス管の曲がりが６．０ｍｍ以下であり、偏肉が１５％以下であることを特徴とする。なお「ＢａＯを実質的に含まない」とは、ＢａＯを積極的に添加しないという意味であり、不純物として混入するものまで排除する主旨ではない。より具体的にはＢａＯの含有量が質量％で０．０５％以下であることを意味する。また、「ガラス管の曲がり」とは管長１０００ｍｍあたりの曲がりを意味する。また、偏肉とは（最大肉厚−最小肉厚）／目標肉厚の値を意味し、ガラス管の最大肉厚と最小肉厚の差分を目標肉厚で除して百分率表示した値である。 The glass tube for a pharmaceutical container of the present invention contains SiO 2 , Al 2 O 3 , B 2 O, and R 2 O (R is at least one of Li, Na, and K) as essential components, and substantially contains BaO. , And is characterized in that the bend of the glass tube is 6.0 mm or less and the uneven thickness is 15% or less. Note that “substantially not containing BaO” means that BaO is not positively added, and is not intended to exclude substances that are mixed as impurities. More specifically, it means that the content of BaO is 0.05% by mass or less. The term “bend of the glass tube” means a bend around a tube length of 1000 mm. In addition, uneven thickness means a value of (maximum thickness−minimum thickness) / target thickness, and is a value expressed as a percentage by dividing the difference between the maximum thickness and the minimum thickness of the glass tube by the target thickness. is there.
上記構成によれば、ＢａＯを含有しないため、ガラス溶融時あるいは成形時にＢａＯ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ない。またガラスからのＢａイオンの溶出量が少なく、薬液中の硫酸イオンと不溶性の沈殿物を形成しにくいガラスが得られる。 According to the above configuration, since BaO is not contained, barium feldspar crystals do not precipitate due to the reaction between BaO and the alumina-based refractory during glass melting or molding. In addition, a glass is obtained in which the amount of Ba ions eluted from the glass is small and it is difficult to form insoluble precipitates with sulfate ions in the chemical solution.
また、上記構成によれば、ガラス管からアンプルやバイアル等のガラス容器を作製する際、ガラス管の曲がりが小さいためにバーナーの熱が回転するガラス管に対して均等に供給され易くなる。またガラス管の偏肉が小さいためにバーナーの熱によってガラス管が均一に昇温し易くなる。これらの相乗効果により、容器加工のための熱量を低減することが可能になる。これにより、容器加工時のＢ２Ｏ３やＮａ２Ｏなどの蒸発量を低減でき、内面に異質層が形成されにくい医薬容器を得ることができる。その結果、医薬容器の化学耐久性や加水分解抵抗性が高くなり、薬液の保存中や薬液充填後のオートクレーブ処理による、薬液成分の変質や薬液のｐＨ変化などを引き起こし難くなる。尚、「熱量」とはバーナーの炎から供給される熱量であり、ガラスの加熱に寄与する熱量とガラス以外のものの加熱に寄与する熱量の和に相当する
本発明の医薬容器用ガラス管は、質量％でＳｉＯ２ ７０．０〜７５．５％、Ａｌ２Ｏ３ ６．３〜１１．０％、Ｂ２Ｏ３ ３．０〜１１．５％、Ｎａ２Ｏ ４．０〜８．５％、Ｋ２Ｏ ０〜５．０％、Ｌｉ２Ｏ ０〜０．２％含有するホウケイ酸ガラスからなることが好ましい。
Further, according to the above configuration, when producing a glass container such as an ampule or a vial from the glass tube, the heat of the burner is easily supplied evenly to the rotating glass tube due to the small bending of the glass tube. Further, since the thickness of the glass tube is small, the temperature of the glass tube is easily increased uniformly by the heat of the burner. These synergistic effects make it possible to reduce the amount of heat for processing the container. This makes it possible to reduce the amount of evaporation of B 2 O 3 , Na 2 O, and the like at the time of container processing, and to obtain a pharmaceutical container in which a foreign layer is not easily formed on the inner surface. As a result, the chemical durability and hydrolysis resistance of the medical container are increased, and it becomes difficult to cause deterioration of the chemical solution component and pH change of the chemical solution due to autoclave treatment during storage of the chemical solution or after filling with the chemical solution. The `` heat amount '' is the heat amount supplied from the flame of the burner, and corresponds to the sum of the heat amount contributing to the heating of the glass and the heat amount contributing to the heating of something other than the glass. SiO 2 70.0-75.5% by mass%, Al 2 O 3 6.3~11.0% , B 2 O 3 3.0~11.5%, Na 2 O 4.0~8.5 %, K 2 O 0~5.0%, preferably made of borosilicate glass containing Li 2 O 0~0.2%.
上記構成によれば、化学的耐久性や加水分解抵抗性に優れたガラス管を得やすくなる。 According to the above configuration, it becomes easy to obtain a glass tube having excellent chemical durability and hydrolysis resistance.
本発明においては、さらにＭｇＯ、ＣａＯ及びＳｒＯの含有量が各々０〜４質量％であるホウケイ酸ガラスからなることが好ましい。 In the present invention, it is preferable that the borosilicate glass further contains MgO, CaO and SrO in a content of 0 to 4% by mass, respectively.
上記構成によれば、化学的耐久性や加水分解抵抗性の低下を抑制しつつ、作業温度の低いガラス管を得やすくなる。 According to the above configuration, it becomes easy to obtain a glass tube having a low working temperature while suppressing a decrease in chemical durability and hydrolysis resistance.
本発明においては、さらにＭｇＯ＋ＣａＯ＋ＳｒＯが０〜４質量％であるホウケイ酸ガラスからなることが好ましい。なお「ＭｇＯ＋ＣａＯ＋ＳｒＯ」とは、ＭｇＯ、ＣａＯ及びＳｒＯの含有量の合量を意味する。 In the present invention, it is preferable that MgO + CaO + SrO is made of borosilicate glass containing 0 to 4% by mass. “MgO + CaO + SrO” means the total content of MgO, CaO and SrO.
本発明においては、ＭｇＯ＋ＣａＯが０〜１質量％未満であるホウケイ酸ガラスからなることが好ましい。 In the present invention, MgO + CaO is preferably made of borosilicate glass having a content of 0 to less than 1% by mass.
本発明においては、さらにＮａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏが５〜１０質量％であるホウケイ酸ガラスからなることが好ましい。なお「Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ」とは、Ｎａ２Ｏ、Ｋ２Ｏ及びＬｉ２Ｏの合量を意味する。 In the present invention, it is preferable to further Na 2 O + K 2 O + Li 2 O is made of borosilicate glass is 5-10 wt%. Note that "Na 2 O + K 2 O + Li 2 O " means, Na 2 O, refers to the total amount of K 2 O and Li 2 O.
上記構成によれば、化学的耐久性や加水分解抵抗性の低下を抑制しつつ、作業温度の低いガラス管を得やすくなる。 According to the above configuration, it becomes easy to obtain a glass tube having a low working temperature while suppressing a decrease in chemical durability and hydrolysis resistance.
本発明においては、さらにＦｅ２Ｏ３の含有量が０〜０．２質量％未満であることが好ましい。 In the present invention, the content of Fe 2 O 3 is preferably 0 to less than 0.2% by mass.
上記構成によれば、ガラス管の着色を効果的に防止することが可能になる。 According to the above configuration, it is possible to effectively prevent coloring of the glass tube.
本発明においては、質量比で、（ＭｇＯ＋ＣａＯ＋ＳｒＯ）／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）の値が０．１０以下であるホウケイ酸ガラスからなることが好ましい。なお「（ＭｇＯ＋ＣａＯ＋ＳｒＯ）／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）」とは、ＭｇＯ、ＣａＯ及びＳｒＯの含有量の合量を、Ｎａ２Ｏ、Ｋ２Ｏ及びＬｉ２Ｏの含有量の合量で除した値である。 In the present invention, it is preferable to use a borosilicate glass having a mass ratio of (MgO + CaO + SrO) / (Na 2 O + K 2 O + Li 2 O) of 0.10 or less. Note that “(MgO + CaO + SrO) / (Na 2 O + K 2 O + Li 2 O)” means the total content of MgO, CaO, and SrO as the total content of Na 2 O, K 2 O, and Li 2 O. This is the divided value.
上記構成によれば、化学的耐久性や加水分解抵抗性の低下を抑制しつつ、作業温度の低いガラスを得やすくなる。 According to the above configuration, it is easy to obtain a glass having a low working temperature while suppressing a decrease in chemical durability and hydrolysis resistance.
本発明においては、質量比で、ＣａＯ／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）が、０〜０．１０であるホウケイ酸ガラスからなることが好ましい。なお「ＣａＯ／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）」とは、ＣａＯの含有量を、Ｎａ２Ｏ、Ｋ２Ｏ及びＬｉ２Ｏの含有量の合量で除した値である。 In the present invention, the mass ratio, CaO / (Na 2 O + K 2 O + Li 2 O) is preferably made of borosilicate glass is 0 to 0.10. “CaO / (Na 2 O + K 2 O + Li 2 O)” is a value obtained by dividing the content of CaO by the total content of Na 2 O, K 2 O, and Li 2 O.
上記構成によれば、加水分解抵抗性が高いガラス管が得られる。 According to the above configuration, a glass tube having high hydrolysis resistance can be obtained.
本発明においては、質量比で、Ｋ２Ｏ／Ｎａ２Ｏが、０．２〜１．０であるホウケイ酸ガラスからなることが好ましい。なお、Ｋ２Ｏ／Ｎａ２ＯとはＫ２Ｏの含有量をＮａ２Ｏの含有量で除した値である。 In the present invention, it is preferable that K 2 O / Na 2 O is made of borosilicate glass having a mass ratio of 0.2 to 1.0. Note that K 2 O / Na 2 O is a value obtained by dividing the content of K 2 O by the content of Na 2 O.
上記構成によれば、加水分解抵抗性の低下を抑制しつつ、作業温度の低いガラス管を得やすくなる。 According to the above configuration, it is easy to obtain a glass tube having a low working temperature while suppressing a decrease in hydrolysis resistance.
本発明においては、質量比で、Ａｌ２Ｏ３／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂ２Ｏ３）が０．３２以上であるホウケイ酸ガラスからなることが好ましい。なお「Ａｌ２Ｏ３／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂ２Ｏ３）」とは、Ａｌ２Ｏ３の含有量を、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢ２Ｏ３の含有量の合量で除した値である。 In the present invention, it is preferable that Al 2 O 3 / (Na 2 O + K 2 O + Li 2 O + MgO + CaO + SrO + B 2 O 3 ) is made of a borosilicate glass having a mass ratio of 0.32 or more. In addition, “Al 2 O 3 / (Na 2 O + K 2 O + Li 2 O + MgO + CaO + SrO + B 2 O 3 )” means that the content of Al 2 O 3 is expressed by Na 2 O, K 2 O, Li 2 O, MgO, CaO, SrO and This is a value obtained by dividing the total content of B 2 O 3 by the total amount.
上記構成によれば、ガラス管の加水分解抵抗性をさらに向上させることが可能になる。 According to the above configuration, the hydrolysis resistance of the glass tube can be further improved.
本発明においては、質量比でＡｌ２Ｏ３／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）が０．７〜１．５であるホウケイ酸ガラスからなることが好ましい。なお「Ａｌ２Ｏ３／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）」とは、Ａｌ２Ｏ３の含有量を、Ｎａ２Ｏ、Ｋ２Ｏ及びＬｉ２Ｏの含有量の合量で除した値である。 In the present invention, it is preferable that Al 2 O 3 / (Na 2 O + K 2 O + Li 2 O) is made of borosilicate glass having a mass ratio of 0.7 to 1.5. Note that “Al 2 O 3 / (Na 2 O + K 2 O + Li 2 O)” is a value obtained by dividing the content of Al 2 O 3 by the total content of Na 2 O, K 2 O, and Li 2 O. It is.
上記構成によれば、加水分解性能をさらに向上させることが可能になる。 According to the above configuration, it is possible to further improve the hydrolysis performance.
本発明においては、ＥＰ８．０に準じた加水分解抵抗性試験の粉末試験法において、単位ガラス質量当たりの０．０２ｍｏｌ／Ｌの塩酸の消費量が０．０３０ｍＬ以下であるホウケイ酸ガラスからなることが好ましい。 In the present invention, in a powder test method for a hydrolysis resistance test according to EP 8.0, the powder consists of borosilicate glass having a consumption of 0.02 mol / L hydrochloric acid per unit glass mass of 0.030 mL or less. Is preferred.
本発明においては、ＤＩＮ１２１１６に準じた耐酸性試験において、面積あたりの質量減少量が１．０ｍｇ／ｄｍ２以下となるホウケイ酸ガラスからなることが好ましい。 In the present invention, it is preferable to use a borosilicate glass having a mass reduction per area of 1.0 mg / dm 2 or less in an acid resistance test according to DIN12116.
本発明においては、１１５０℃〜１２５０℃の作業温度を有するホウケイ酸ガラスからなることが好ましい。なお作業温度とは、ガラスの粘度が１０４ｄＰａ・ｓとなる温度である。 In the present invention, it is preferably made of borosilicate glass having a working temperature of 1150C to 1250C. The working temperature is a temperature at which the viscosity of the glass becomes 10 4 dPa · s.
上記構成によれば、ガラス管からアンプルやバイアル等のガラス容器を作製する際の加工温度を低くすることが可能となり、ガラスからのＢ２Ｏ３やアルカリ金属酸化物成分の蒸発量を著しく低減できる。結果として、ガラス容器中に保管される薬液成分の変質や薬液のｐＨ上昇などを引き起こす事態を回避することができる。 According to the above configuration, it is possible to lower the processing temperature when producing a glass container such as an ampoule or a vial from a glass tube, and to significantly reduce the evaporation amount of B 2 O 3 and alkali metal oxide components from the glass. it can. As a result, it is possible to avoid a situation in which the chemical component stored in the glass container is altered or the pH of the chemical is increased.
本発明においては、１０４．５ｄＰａ・ｓ以上の液相粘度を有するホウケイ酸ガラスからなることが好ましい。 In the present invention, it is preferable to use a borosilicate glass having a liquidus viscosity of 10 4.5 dPa · s or more.
上記構成によれば、ガラス管の成形にダンナー法を採用した場合でも、成形時の失透が生じ難くなり好ましい。 According to the above configuration, even when the Danner method is used for molding the glass tube, devitrification during molding is less likely to occur, which is preferable.
本発明の医薬容器用ガラス管の製造方法は、ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ、Ｒ２Ｏ（ＲはＬｉ、Ｎａ、Ｋのいずれか１種類以上）を必須成分として含み、ＢａＯを実質的に含まないガラスとなるように調合した原料を溶融した後、管ガラスの曲がりが６．０ｍｍ以下、偏肉が１５％以下となるように管引き成形することを特徴とする。 The method for producing a glass tube for a pharmaceutical container according to the present invention includes SiO 2 , Al 2 O 3 , B 2 O, and R 2 O (R is at least one of Li, Na, and K) as an essential component, Is characterized in that after the raw material prepared to be a glass substantially containing no is melted, tube drawing is performed so that the bending of the tube glass is 6.0 mm or less and the uneven thickness is 15% or less.
本発明の医薬容器用ガラス管を構成するホウケイ酸ガラスは、ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３、Ｒ２Ｏ（ＲはＬｉ、Ｎａ及びＫから選ばれる１種類以上）を必須成分として含む。 The borosilicate glass constituting the glass tube for a pharmaceutical container of the present invention contains SiO 2 , Al 2 O 3 , B 2 O 3 , and R 2 O (R is at least one selected from Li, Na and K) as essential components. Included as
また本発明に係るホウケイ酸ガラスは、ＢａＯを実質的に含まない。ＢａＯがガラス組成中に含まれていると、前述のようにアルミナ系耐火物との反応や、ガラスから溶出したＢａイオンと薬液中の硫酸イオンとの反応によって結晶を析出させたり、沈殿物を発生させたりする恐れがある。 Further, the borosilicate glass according to the present invention does not substantially contain BaO. When BaO is contained in the glass composition, as described above, the reaction with the alumina-based refractory or the reaction between Ba ions eluted from the glass and sulfate ions in the chemical solution precipitate crystals or precipitates. May be generated.
本発明の医薬容器用ガラス管は、管の曲がりが６．０ｍｍ以下、好ましくは５．０ｍｍ以下、より好ましくは４．０ｍｍ以下である。この値が大きすぎると、容器加工時にガラス管を回転させる際、ガラス管の位置が安定せず、バーナーの炎による加熱ムラが発生する。加熱されにくい場所が所定の温度に昇温するまでの間、加熱されやすい場所は高温の状態で保持され、Ｂ２Ｏ３やＮａ２Ｏなどの蒸発量が多くなってしまう。また、一つの容器を成形するまでの時間も長くなり、容器加工の効率が著しく低下する。 The glass tube for a pharmaceutical container of the present invention has a tube bending of 6.0 mm or less, preferably 5.0 mm or less, more preferably 4.0 mm or less. If this value is too large, the position of the glass tube will not be stable when the glass tube is rotated during container processing, and uneven heating due to the burner flame will occur. Until the location that is difficult to heat rises to a predetermined temperature, the location that is likely to be heated is kept at a high temperature, and the amount of evaporation of B 2 O 3 and Na 2 O increases. In addition, the time required to form one container is increased, and the efficiency of container processing is significantly reduced.
またガラス管の偏肉は１５％以下、好ましくは１３％以下、より好ましくは１０％以下である。この値が大きすぎると、ガラス管の各部分の熱容量の違いが大きくなり、容器加工時にガラス管がバーナーによって均一に昇温しなくなる。肉厚が厚く、熱容量の大きい部分が所定の温度に昇温するまでの間、肉厚が薄く、熱容量の小さい部分は高温の状態で保持され、Ｂ２Ｏ３やＮａ２Ｏなどの蒸発量が多くなってしまう。また、一つの容器を成形するまでの時間も長くなり、容器加工の効率が著しく低下する。 The thickness deviation of the glass tube is 15% or less, preferably 13% or less, more preferably 10% or less. If this value is too large, the difference in heat capacity of each part of the glass tube becomes large, and the temperature of the glass tube cannot be uniformly increased by the burner during container processing. Until the thick part and the large heat capacity part are heated to a predetermined temperature, the thin part and the small heat capacity part are kept at a high temperature, and the evaporation amount of B 2 O 3 , Na 2 O, etc. Will increase. In addition, the time required to form one container is increased, and the efficiency of container processing is significantly reduced.
本発明において、ホウケイ酸ガラスの組成に特に制限はないが、質量％でＳｉＯ２ ７０．０〜７５．５％、Ａｌ２Ｏ３ ６．３〜１１．０％、Ｂ２Ｏ３ ３．０〜１１．５％、Ｎａ２Ｏ ４．０〜８．５％、Ｋ２Ｏ ０〜５．０％、Ｌｉ２Ｏ ０〜０．２％含有し、ＢａＯを実質的に含まないホウケイ酸ガラスであることが好ましい。以下、各成分の組成範囲を上記のように限定した理由を述べる。なお以下の説明において、特に断りがない限り、％表示は質量％を意味する。 In the present invention, no particular limitation on the composition of the borosilicate glass but, SiO 2 from 70.0 to 75.5% by mass%, Al 2 O 3 6.3~11.0% , B 2 O 3 3.0 ~11.5%, Na 2 O 4.0~8.5% , K 2 O 0~5.0%, Li 2 O containing 0 to 0.2%, borosilicate glass containing no BaO substantially It is preferred that Hereinafter, the reasons for limiting the composition range of each component as described above will be described. In the following description,% means mass% unless otherwise specified.
ＳｉＯ２はガラスネットワークを構成する成分の１つである。ＳｉＯ２の含有量は７０．０〜７５．５％、７０．０〜７５．５％未満、７０．０〜７５．０％、特に７０．０〜７４．７％であることが好ましい。ＳｉＯ２の含有量が少な過ぎると化学的耐久性が低下し、医薬容器用ホウケイ酸ガラスに求められる耐酸性が低くなる。一方、ＳｉＯ２の含有量が多過ぎると液相粘度が低下し、製造工程で失透が起こりやすくなって生産性が低下する。 SiO 2 is one of the components constituting the glass network. The content of SiO 2 is preferably from 70.0 to 75.5%, 70.0 to less than 75.5%, 70.0 to 75.0%, particularly preferably 70.0 to 74.7%. If the content of SiO 2 is too small, the chemical durability decreases, and the acid resistance required for the borosilicate glass for medical containers decreases. On the other hand, if the content of SiO 2 is too large, the liquidus viscosity decreases, devitrification tends to occur in the manufacturing process, and the productivity decreases.
Ａｌ２Ｏ３はガラスの失透を抑制し、また化学的耐久性及び加水分解抵抗性を向上させる成分である。Ａｌ２Ｏ３の含有量は６．３〜１１．０％、６．４〜１０．０％、６．５〜８．５％、特に６．７〜８．０％であることが好ましい。Ａｌ２Ｏ３の含有量が少な過ぎると上記の効果が得られない。一方、Ａｌ２Ｏ３の含有量が多過ぎるとガラスの粘度が上昇し、作業温度が高くなり、医薬容器に加工する際に必要な熱量が多くなってしまう。 Al 2 O 3 is a component that suppresses devitrification of glass and improves chemical durability and hydrolysis resistance. The content of Al 2 O 3 is 6.3 to 11.0%, 6.4 to 10.0%, from 6.5 to 8.5%, particularly preferably 6.7 to 8.0%. If the content of Al 2 O 3 is too small, the above effects cannot be obtained. On the other hand, if the content of Al 2 O 3 is too large, the viscosity of the glass increases, the working temperature increases, and the amount of heat required for processing into a medical container increases.
Ｂ２Ｏ３はガラスの融点を低下させるだけでなく、液相粘度を上昇させ、失透を抑制する効果を有する。そのため、Ｂ２Ｏ３の含有量は３．０〜１１．５％、５．５〜１１．４％、８．５〜１１．０％、特に９．０〜１１．０％未満である。Ｂ２Ｏ３の含有量が少な過ぎると作業温度が高くなり、医薬容器に加工する際に必要な熱量が多くなってしまう。一方、Ｂ２Ｏ３の含有量が多過ぎると加水分解抵抗性や化学的耐久性が低下する。 B 2 O 3 not only lowers the melting point of the glass, but also increases the liquidus viscosity and has the effect of suppressing devitrification. Therefore, the content of B 2 O 3 is 3.0 to 11.5%, 5.5 to 11.4%, 8.5 to 11.0%, in particular less than 9.0 to 11.0%. When the content of B 2 O 3 is too small, the working temperature becomes high, and the amount of heat required for processing into a medicine container increases. On the other hand, when the content of B 2 O 3 is too large, hydrolysis resistance and chemical durability are reduced.
Ｎａ２Ｏはガラスの粘度を低下させ、線熱膨張係数を上昇させる効果がある。Ｎａ２Ｏの含有量は４．０〜８．５％、４．２〜８．４％、４．５〜８．０％、特に５．０〜７．０％であることが好ましい。Ｎａ２Ｏの含有量が少なすぎると作業温度が高くなり、医薬容器に加工する際に必要な熱量が多くなってしまう。一方、Ｎａ２Ｏの含有量が多過ぎると加水分解抵抗性が低下する。 Na 2 O has an effect of reducing the viscosity of the glass and increasing the linear thermal expansion coefficient. The content of Na 2 O is preferably 4.0 to 8.5%, 4.2 to 8.4%, 4.5 to 8.0%, and particularly preferably 5.0 to 7.0%. If the content of Na 2 O is too small, the working temperature will increase, and the amount of heat required when processing into a pharmaceutical container will increase. On the other hand, when the content of Na 2 O is too large, the hydrolysis resistance decreases.
Ｋ２ＯもＮａ２Ｏと同様にガラスの粘度を低下させ、線熱膨張係数を上昇させる効果がある。Ｋ２Ｏの含有量は０〜５．０％、０．１〜５％、０．５〜４．５％、１．０〜３．０％、特に１．５〜３．０％であることが好ましい。Ｋ２Ｏの含有量が多過ぎると加水分解抵抗性が低下する。 K 2 O also reduces the viscosity of the glass as with Na 2 O, an effect of increasing the coefficient of linear thermal expansion. The content of K 2 O is 0 to 5.0%, 0.1% to 5%, 0.5 to 4.5%, 1.0% to 3.0%, in particular 1.5 to 3.0% Is preferred. If the content of K 2 O is too large, the hydrolysis resistance decreases.
なおＫ２ＯとＮａ２Ｏの両成分を併用すれば、混合アルカリ効果により、加水分解抵抗性が向上するため、望ましい。加水分解抵抗性を向上させるためには、質量比でＫ２Ｏ／Ｎａ２Ｏが０．２〜１．０、０．２０〜０．９５、０．２〜０．８、特に０．２〜０．７であることが好ましい。この比が小さいと加水分解抵抗性が低下する。一方、この比が大きいと作業温度が高くなり、医薬容器に加工する際に必要な熱量が多くなってしまう。 It is preferable to use both components of K 2 O and Na 2 O, since the hydrolysis resistance is improved by the mixed alkali effect. In order to improve the hydrolysis resistance, K 2 O / Na 2 O is 0.2 to 1.0, 0.20 to 0.95, 0.2 to 0.8, particularly 0.2 to 1.0 by mass ratio. It is preferably from 0.7 to 0.7. If this ratio is small, the hydrolysis resistance decreases. On the other hand, when this ratio is large, the working temperature becomes high, and the amount of heat required for processing into a medical container increases.
Ｌｉ２ＯはＮａ２ＯやＫ２Ｏと同様にガラスの粘度を低下させ、また線熱膨張係数を上昇させる効果がある。しかしＬｉ２Ｏを添加するとガラス溶融時に耐火物を侵食し易くなる。また生産コストの増加に繋がる。そのためＬｉ２Ｏの含有量は０〜０．２％、０〜０．１％、０〜０．０５％、特に０〜０．０１％とすることが好ましく、特段の事情がなければＬｉ２Ｏ以外の他のアルカリ金属酸化物を使用することが望ましい。 Li 2 O has an effect of lowering the viscosity of glass and increasing the linear thermal expansion coefficient, like Na 2 O and K 2 O. However, when Li 2 O is added, the refractory is easily eroded when the glass is melted. It also leads to an increase in production costs. The content of that for Li 2 O is 0 to 0.2% 0 to 0.1%, preferably be from 0 to 0.05%, in particular from 0 to 0.01%, if no special circumstances Li 2 It is desirable to use another alkali metal oxide other than O.
Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの含有量の合量は、好ましくは５〜１０％、特に６〜９％である。これらの成分の合量が少ないと、作業温度が高くなる。またこれらの成分の合量が多いと、化学耐久性や加水分解抵抗性が低下する。 The total content of Li 2 O, Na 2 O and K 2 O is preferably 5 to 10%, particularly 6 to 9%. When the total amount of these components is small, the working temperature increases. When the total amount of these components is large, chemical durability and hydrolysis resistance are reduced.
また本発明においては、上記以外にも種々の成分を添加することが可能である。 In the present invention, it is possible to add various components other than the above.
ＭｇＯは化学的耐久性向上の効果がある。ＭｇＯの含有量は、好ましくは０〜４．０％、０〜２．０％、特に０〜１．０％である。ＭｇＯの含有量が多すぎると加水分解抵抗性が低下する。 MgO has an effect of improving chemical durability. The content of MgO is preferably 0 to 4.0%, 0 to 2.0%, particularly 0 to 1.0%. If the content of MgO is too large, the hydrolysis resistance decreases.
ＣａＯはガラスの高温粘度を低下させる効果がある。ＣａＯの含有量は、好ましくは０〜４．０％、０〜１．５％、０〜１．１％、０〜０．９％、特に０〜０．５％である。ＣａＯ含有量が多過ぎると加水分解抵抗性が低下する。 CaO has the effect of lowering the high temperature viscosity of the glass. The content of CaO is preferably 0 to 4.0%, 0 to 1.5%, 0 to 1.1%, 0 to 0.9%, particularly 0 to 0.5%. If the CaO content is too large, the hydrolysis resistance decreases.
ＳｒＯは化学的耐久性向上の効果がある。ＳｒＯの含有量は、好ましくは０〜４．０％、０〜２．０％、特に０〜１．０％である。ＳｒＯの含有量が多すぎると加水分解抵抗性が低下する。 SrO has an effect of improving chemical durability. The content of SrO is preferably 0 to 4.0%, 0 to 2.0%, particularly 0 to 1.0%. If the content of SrO is too large, the hydrolysis resistance decreases.
ＭｇＯとＣａＯとＳｒＯの含有量の合量は、好ましくは０〜４．０％、０〜３．０％、０〜２．０％、０〜１．０％未満、特に０〜０．５％であることが好ましい。これらの成分の合量が多すぎると加水分解抵抗性が低下する。 The total content of MgO, CaO, and SrO is preferably 0 to 4.0%, 0 to 3.0%, 0 to 2.0%, less than 0 to 1.0%, particularly 0 to 0.5%. %. If the total amount of these components is too large, the hydrolysis resistance decreases.
ＭｇＯとＣａＯの含有量の合量は、好ましくは０〜１％未満、０〜０．８％、特に０〜０．５％である。これらの成分の合量が多すぎると加水分解性が低下する。 The total content of MgO and CaO is preferably 0 to less than 1%, 0 to 0.8%, particularly 0 to 0.5%. When the total amount of these components is too large, the hydrolyzability decreases.
ＴｉＯ２は加水分解抵抗性を向上させる効果がある。ＴｉＯ２の含有量は０〜７．０％未満であることが好ましく、０〜５．０％、０〜４．０％、特に０〜１．５％であることがより好ましい。ＴｉＯ２の含有量が多すぎると作業温度が高くなり、医薬容器に加工する際に必要な熱量が多くなってしまう。 TiO 2 has an effect of improving hydrolysis resistance. Preferably the content of TiO 2 is less than 0 to 7.0%, from 0 to 5.0% 0 to 4.0%, and more preferably in particular from 0 to 1.5%. If the content of TiO 2 is too large, the working temperature will increase, and the amount of heat required when processing into a pharmaceutical container will increase.
ＺｒＯ２は加水分解抵抗性を向上させる効果がある。ＺｒＯ２の含有量は０〜７．０％未満であることが好ましく、０〜５．０％、０〜４．０％、特に０〜１．５％であることがより好ましい。ＺｒＯ２の含有量が多すぎると作業温度が高くなり、医薬容器に加工する際に必要な熱量が多くなってしまう。 ZrO 2 has an effect of improving hydrolysis resistance. Preferably the content of ZrO 2 is less than 0 to 7.0%, from 0 to 5.0% 0 to 4.0%, and more preferably in particular from 0 to 1.5%. If the content of ZrO 2 is too large, the working temperature will increase, and the amount of heat required when processing into a pharmaceutical container will increase.
Ｆｅ２Ｏ３は、ガラスを着色させ可視域での透過率を低下させる恐れがあるため、その含有量は０．２%以下、０．１％以下、特には０．０２％以下に制限することが望ましい。 Since Fe 2 O 3 may color the glass and lower the transmittance in the visible region, its content is limited to 0.2% or less, 0.1% or less, particularly 0.02% or less. It is desirable.
また清澄剤としてＦ、Ｃｌ、Ｓｂ２Ｏ３、ＳｎＯ２、Ｎａ２ＳＯ４等のいずれか一種以上を含有しても良い。これらの清澄剤の含有量の合計は３％以下であり、好ましくは１％以下、より好ましくは０．５％以下である。またこれらの清澄剤の中では、溶融温度や環境への影響が少ないという理由からＣｌやＳｎＯ２を使用することが好ましい。Ｃｌを使用する場合、その含有量は３％以下、更に１％以下、特に０．２％以下であることが好ましい。ＳｎＯ２を使用する場合、その含有量は２％以下、より好ましくは０．５％以下であることが好ましい。 The F as a fining agent, Cl, Sb 2 O 3, SnO 2, may contain any one or more of such Na 2 SO 4. The total content of these fining agents is 3% or less, preferably 1% or less, more preferably 0.5% or less. Among these fining agents, it is preferable to use Cl or SnO 2 because the influence on the melting temperature and the environment is small. When Cl is used, its content is preferably 3% or less, more preferably 1% or less, particularly preferably 0.2% or less. When SnO 2 is used, its content is preferably 2% or less, more preferably 0.5% or less.
また、本発明においては、低粘度、高加水分解抵抗性のガラスを得るために、質量比で、（ＭｇＯ＋ＣａＯ＋ＳｒＯ）／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）の値を、０．１０以下、０．０８以下、０．０７以下、特に０．０７未満に調整することが好ましい。この値が大きすぎると加水分解抵抗性が低下する。同様の理由で、質量比で、ＣａＯ／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）の値を、０．１０以下、より好ましくは０．０８以下、特に０．０７以下さらに好ましくは０．０７未満に調整することが好ましい。この値が大きすぎると加水分解抵抗性が低下する。 In the present invention, in order to obtain a low viscosity, high hydrolytic resistance of the glass, at a mass ratio, the value of (MgO + CaO + SrO) / (Na 2 O + K 2 O + Li 2 O), 0.10 or less, 0. It is preferably adjusted to 08 or less, 0.07 or less, particularly less than 0.07. If this value is too large, the hydrolysis resistance decreases. For the same reason, the value of CaO / (Na 2 O + K 2 O + Li 2 O) is set to 0.10 or less, more preferably 0.08 or less, particularly 0.07 or less, and further preferably less than 0.07 by mass ratio. Adjustment is preferred. If this value is too large, the hydrolysis resistance decreases.
また本発明においては、加水分解抵抗性を向上させるが、ガラスの粘度を上昇させる成分であるＡｌ２Ｏ３と、ガラスの粘度を低下させるが、加水分解抵抗性を低下させる成分であるＮａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、Ｂ２Ｏ３の含有量のバランスを取ることが、加水分解抵抗性と良好な加工性を両立させる上で望ましい。具体的には質量比でＡｌ２Ｏ３／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂ２Ｏ３）が０．３２以上、特に０．３４以上であることが好ましく、またこの値が０．６０以下、特に０．５０以下であることが望ましい。なお「Ａｌ２Ｏ３／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂ２Ｏ３）」とは、Ａｌ２Ｏ３の含有量を、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢ２Ｏ３の含有量の合量で除した値である。 Further, in the present invention, Al 2 O 3 which is a component for increasing the viscosity of glass while improving the hydrolysis resistance, and Na 2 which is a component for decreasing the viscosity of the glass but which reduces the hydrolysis resistance, are used. It is desirable to balance the contents of O, K 2 O, Li 2 O, MgO, CaO, SrO, and B 2 O 3 in order to achieve both hydrolysis resistance and good workability. Specifically, the mass ratio of Al 2 O 3 / (Na 2 O + K 2 O + Li 2 O + MgO + CaO + SrO + B 2 O 3 ) is preferably at least 0.32, particularly preferably at least 0.34, and this value is at most 0.60, In particular, it is desirable to be 0.50 or less. In addition, “Al 2 O 3 / (Na 2 O + K 2 O + Li 2 O + MgO + CaO + SrO + B 2 O 3 )” means that the content of Al 2 O 3 is expressed by Na 2 O, K 2 O, Li 2 O, MgO, CaO, SrO and This is a value obtained by dividing the total content of B 2 O 3 by the total amount.
さらに質量比でＡｌ２Ｏ３／（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ）が０．７〜１．５、０．７５〜１．５、特に０．７５〜１．２であることが望ましい。この比率が小さ過ぎると加水分解抵抗性が低下し、高すぎると作業温度が高くなり、医薬容器に加工する際に必要な熱量が多くなってしまう。 Further, the mass ratio of Al 2 O 3 / (Na 2 O + K 2 O + Li 2 O) is desirably 0.7 to 1.5, 0.75 to 1.5, and particularly preferably 0.75 to 1.2. If this ratio is too small, the hydrolysis resistance will be reduced, and if it is too high, the working temperature will be high and the amount of heat required when processing into a pharmaceutical container will be large.
また本発明においては、モル比で（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ―Ａｌ２Ｏ３）／Ｂ２Ｏ３の値が、０．３１５〜０．３５０、好ましくは０．３２０〜０．３４５、０．３２０〜０．３４０、特に０．３２５〜０．３４０未満であることが望ましい。この値が大きすぎると、加工時の種々の熱処理により、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏといったアルカリ金属酸化物含有量が多いためにこれらの蒸発量が増え、化学的耐久性や加水分解抵抗性が低下するか、Ｂ２Ｏ３含有量が少ないために作業温度が高くなり、加工時の種々の熱処理により、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏといったアルカリ金属酸化物が蒸発しやすくなり、化学的耐久性や加水分解抵抗性が低下する。また、水分の気化に伴う泡が発生しやすくなる。一方、この値が小さすぎると、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏといったアルカリ金属酸化物含有量が少ないために作業温度が高くなり、加工時の種々の熱処理により、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２ＯやＢ２Ｏ３が蒸発しやすくなり、化学的耐久性や加水分解抵抗性が低下するとともに水分の気化に伴う泡が発生しやすくなるか、Ｂ２Ｏ３含有量が多いために容器加工前の時点で化学的耐久性や加水分解抵抗性が低下する。なお「Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ−Ａｌ２Ｏ３」とは、Ｎａ２Ｏ、Ｋ２Ｏ及びＬｉ２Ｏの合量からＡｌ２Ｏ３の含有量を引いた値である。「（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ−Ａｌ２Ｏ３）／Ｂ２Ｏ３」とは、（Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏ−Ａｌ２Ｏ３）の値をＢ２Ｏ３で除した値を意味する。 In the present invention, the molar ratio of (Na 2 O + K 2 O + Li 2 O—Al 2 O 3 ) / B 2 O 3 is 0.315 to 0.350, preferably 0.320 to 0.345, It is desirably 0.320 to 0.340, particularly preferably 0.325 to less than 0.340. If this value is too large, various heat treatments during processing increase the content of alkali metal oxides such as Na 2 O, K 2 O, and Li 2 O, thereby increasing the amount of evaporation of these components, and increasing the chemical durability and water content. The working temperature rises due to a decrease in decomposition resistance or a low B 2 O 3 content, and alkali metal oxides such as Na 2 O, K 2 O and Li 2 O are evaporated by various heat treatments during processing. And the chemical durability and hydrolysis resistance are reduced. In addition, bubbles accompanying moisture vaporization are likely to be generated. On the other hand, if this value is too small, the working temperature becomes high because the content of alkali metal oxides such as Na 2 O, K 2 O and Li 2 O is small, and Na 2 O, K 2 O, Li 2 O and B 2 O 3 are liable to evaporate, and the chemical durability and hydrolysis resistance are reduced and bubbles are easily generated due to the vaporization of water, or the B 2 O 3 content is reduced. Due to the large amount, chemical durability and hydrolysis resistance are reduced before processing the container. Note that “Na 2 O + K 2 O + Li 2 O—Al 2 O 3 ” is a value obtained by subtracting the content of Al 2 O 3 from the total amount of Na 2 O, K 2 O, and Li 2 O. “(Na 2 O + K 2 O + Li 2 O—Al 2 O 3 ) / B 2 O 3 ” means a value obtained by dividing the value of (Na 2 O + K 2 O + Li 2 O—Al 2 O 3 ) by B 2 O 3. means.
また本発明の医薬容器用ガラス管を構成するホウケイ酸ガラスは、以下の特性を有することが好ましい。 The borosilicate glass constituting the glass tube for a pharmaceutical container of the present invention preferably has the following characteristics.
ＥＰ８．０に準じた加水分解抵抗性試験の粉末試験法において、単位ガラス質量当たりの０．０２ｍｏｌ／Ｌの塩酸の消費量は、好ましくは０．０３０ｍＬ以下、０．０２８ｍＬ以下、０．０２６ｍＬ以下、特に０．０２５ｍＬ以下である。塩酸消費量が多すぎると、アンプルやバイアルなどの医薬容器を作製し、薬液を充填、保存した際、ガラス成分特にアルカリ金属成分の溶出が大幅に増加して薬液成分の変質を引き起こす恐れがある。 In the powder test method of the hydrolysis resistance test according to EP 8.0, the consumption of 0.02 mol / L hydrochloric acid per unit glass mass is preferably 0.030 mL or less, 0.028 mL or less, 0.026 mL or less. , Especially 0.025 mL or less. If the consumption of hydrochloric acid is too large, when a pharmaceutical container such as an ampoule or a vial is prepared, filled with a chemical solution, and stored, the elution of a glass component, particularly an alkali metal component, may be significantly increased, and the chemical component may be deteriorated. .
ＤＩＮ１２１１６に準じた耐酸性試験において、単位面積あたりの質量減少量は、好ましくは１．０ｍｇ／ｄｍ２以下、特に０．８ｍｇ／ｄｍ２以下である。質量減少量が多くなると、アンプルやバイアルなどの医薬容器を作製し、薬液を充填、保存した際、ガラス成分の溶出量が大幅に増加して薬液成分の変質を引き起こす恐れがある。 In the acid resistance test according to DIN 12116, the mass loss per unit area is preferably at most 1.0 mg / dm 2 , especially at most 0.8 mg / dm 2 . When the mass loss increases, when a medical container such as an ampoule or a vial is prepared, and a chemical solution is filled and stored, the elution amount of the glass component is significantly increased, and the chemical component may be deteriorated.
作業温度は１２５０℃以下、１１５０℃〜１２５０℃、より好ましくは１１５０℃〜１２４０℃、特に１１６０℃〜１２３０℃である。作業温度が高すぎると、ガラス管からアンプルやバイアル等のガラス容器を作製する際の加工温度が高くなり、ガラス中のＢ２Ｏ３やアルカリ金属酸化物の蒸発量が著しく増加する。 The working temperature is 1250 ° C. or lower, 1150 ° C. to 1250 ° C., more preferably 1150 ° C. to 1240 ° C., and particularly 1160 ° C. to 1230 ° C. If the working temperature is too high, the processing temperature when producing a glass container such as an ampoule or a vial from a glass tube increases, and the amount of evaporation of B 2 O 3 and alkali metal oxide in the glass increases significantly.
液相粘度は、好ましくは１０４．５ｄＰａ・ｓ以上、１０５．０ｄＰａ・ｓ以上、１０５．２ｄＰａ・ｓ以上、１０５．４ｄＰａ・ｓ以上、特に１０５．６ｄＰａ・ｓ以上である。液相粘度が低くなると、ダンナー法によるガラス管成形時に失透が起こり易くなり、生産性が低下する。 Liquidus viscosity is preferably 10 4.5 dPa · s or more, 10 5.0 dPa · s or more, 10 5.2 dPa · s or more, 10 5.4 dPa · s or more, particularly 10 5.6 dPa · s or more. When the liquidus viscosity is low, devitrification tends to occur at the time of glass tube molding by the Danner method, and productivity is reduced.
線熱膨張係数はガラスの耐熱衝撃性において重要なパラメータである。ガラスが十分な耐熱衝撃性を得るためには、３０〜３８０℃の温度範囲における線熱膨張係数は、好ましくは５８×１０−７／℃以下、特に４８〜５５×１０−７／℃である。 The linear thermal expansion coefficient is an important parameter in the thermal shock resistance of glass. In order for the glass to obtain sufficient thermal shock resistance, the linear thermal expansion coefficient in the temperature range of 30 to 380 ° C is preferably 58 × 10 −7 / ° C or less, and particularly preferably 48 to 55 × 10 −7 / ° C. .
次に本発明の医薬容器用ガラス管を製造する方法を説明する。以下の説明は、ダンナー法を用いた例である。 Next, a method for producing the glass tube for a pharmaceutical container of the present invention will be described. The following description is an example using the Danner method.
先ず、上記のガラス組成になるように、ガラス原料を調合してガラスバッチを作製する。次いで、このガラスバッチを１５５０〜１７００℃の溶融窯に連続投入して溶融、清澄した後、得られた溶融ガラスを回転する耐火物上に巻きつけながら、耐火物先端部からエアを吹き出しつつ、当該先端部からガラスを管状に引き出す。なおガラス管の曲がりや偏肉の調整は、マッフル炉内の温度分布やスリーブの回転速度等を調整することにより行えばよい。さらに引き出した管状ガラスを所定の長さに切断して本発明の医薬容器用ガラス管を得る。このようにして得られたガラス管は、バイアルやアンプルの製造に供される。 First, a glass batch is prepared by mixing glass raw materials so as to have the above-mentioned glass composition. Next, after continuously feeding the glass batch into a melting furnace at 1550 to 1700 ° C. to melt and clarify, while wrapping the obtained molten glass on a rotating refractory, while blowing air from a refractory tip, The glass is drawn out from the tip portion into a tube. Adjustment of the bending and uneven thickness of the glass tube may be performed by adjusting the temperature distribution in the muffle furnace, the rotation speed of the sleeve, and the like. Further, the drawn tubular glass is cut into a predetermined length to obtain a glass tube for a pharmaceutical container of the present invention. The glass tube thus obtained is used for the production of vials and ampules.
なお、本発明の医薬容器用ガラス管は、ダンナー法に限らず、従来周知の任意の手法を用いて製造しても良い。例えば、ベロー法やダウンドロー法も本発明の医薬容器用ガラス管の製造方法として有効な方法である。 In addition, the glass tube for medical containers of the present invention is not limited to the Danner method, and may be manufactured using any conventionally known method. For example, the bellows method and the downdraw method are also effective methods for producing the glass tube for a pharmaceutical container of the present invention.
以下、実施例に基づいて本発明を説明する。 Hereinafter, the present invention will be described based on examples.
表１、２は本発明の実施例（試料Ｎｏ．１〜６）、及び比較例（試料Ｎｏ．７、８）を示している。なお表中の「ΣＲ２Ｏ」は「Ｋ２Ｏ＋Ｎａ２Ｏ＋Ｌｉ２Ｏ」を表しており、ΣＲＯ)」は「ＭｇＯ＋ＣａＯ＋ＳｒＯ」を表している。 Tables 1 and 2 show examples of the present invention (samples Nos. 1 to 6) and comparative examples (samples Nos. 7 and 8). In the table, “ΣR 2 O” represents “K 2 O + Na 2 O + Li 2 O”, and “ΣRO)” represents “MgO + CaO + SrO”.
各試料は以下のようにして調製した。 Each sample was prepared as follows.
まず表に示す組成となるように、ガラス建て５００ｇのバッチを調合し、１５５０〜１７００℃の溶融窯に連続投入して溶融、清澄した。次いで溶融ガラスをダンナー装置に供給して外径２０ｍｍ、内径１８ｍｍ（目標肉厚１ｍｍ）のガラス管となるようにガラスを管状に引き出した。さらに引き出された管状ガラスを１５００ｍｍの長さに切断して医薬容器用ガラス管を得た。なおダンナー装置は、マッフル炉内に設置された耐火物スリーブと、ガラスを引き出す管引き機を有している。耐火物スリーブは、斜め下方に傾斜するとともにスリーブの中心軸を中心にして回転するように設けられており、スリーブ上に供給された溶融ガラスをスリーブの回転と傾きによってスリーブ表面に巻きつけながらスリーブ先端方向へと導くものである。またスリーブ先端にはエア吹き出し孔が設けられており、スリーブ先端から引き出されたガラス内にエアを供給してガラスが管形状を保つようにしている。管引き機は、対向する一対のローラーを有しており、スリーブ先端から離れた管状ガラスをローラーで挟持して所望の管径となるように引き伸ばすものである。 First, a 500 g batch made of glass was prepared so as to have the composition shown in the table, and was continuously charged into a melting furnace at 1550 to 1700 ° C. to be melted and refined. Next, the molten glass was supplied to a Danner device, and the glass was drawn into a tube so as to form a glass tube having an outer diameter of 20 mm and an inner diameter of 18 mm (target thickness 1 mm). Further, the drawn tubular glass was cut into a length of 1500 mm to obtain a glass tube for a medicine container. Note that the Danner device has a refractory sleeve installed in a muffle furnace and a tube drawing machine for drawing glass. The refractory sleeve is provided so as to tilt obliquely downward and rotate about the central axis of the sleeve, and the molten glass supplied on the sleeve is wound around the sleeve surface by the rotation and inclination of the sleeve. It leads to the tip direction. An air blowing hole is provided at the tip of the sleeve, and air is supplied into the glass drawn from the tip of the sleeve so that the glass maintains a tubular shape. The tube drawing machine has a pair of rollers facing each other, and is configured to hold the tubular glass separated from the distal end of the sleeve with the rollers and stretch the tube glass to a desired tube diameter.
このようにして得られたガラス管試料について各種の評価に供した。なおガラス管の曲がりや偏肉は、マッフル炉内の温度分布やスリーブの回転速度等を変更することにより調節した。 The glass tube sample thus obtained was subjected to various evaluations. The bending and uneven thickness of the glass tube were adjusted by changing the temperature distribution in the muffle furnace, the rotation speed of the sleeve, and the like.
表１から明らかなように、試料Ｎｏ．１〜６は良好な加水分解抵抗性及び化学的耐久性を示した。また、各試料とも１２２０℃以下の作業温度を有していることがわかった。また、ガラス組成中にＳｎを含むＮｏ．１、２、４について、加水分解抵抗性試験によるＳｎの溶出を評価したところ、何れの試料もＳｎ溶出量は検出下限未満であった。また、試料Ｎｏ．１〜６は、曲がりと偏肉が所定の範囲内にあり、バーナーによる容器加工時に効率良くガラスを加熱できた。それゆえＢａＯを含有しないにも関わらず、Ｂ２Ｏ３やＮａ２Ｏの蒸発量が増加しないと考えられる。比較例である試料Ｎｏ．７、８は、曲がりが大きく、バーナーによる容器加工時に効率良くガラスを加熱できなかった。それゆえガラス管の加工時に必要以上の熱量が必要となることから、Ｂ２Ｏ３やＮａ２Ｏの蒸発量が増加する懸念がある。 As is clear from Table 1, the sample No. 1 to 6 showed good hydrolysis resistance and chemical durability. It was also found that each sample had a working temperature of 1220 ° C. or less. In addition, No. 3 containing Sn in the glass composition. When the elution of Sn by the hydrolysis resistance test was evaluated for 1, 2, and 4, the elution amount of Sn was less than the lower detection limit in all samples. In addition, the sample No. In Nos. 1 to 6, the bend and uneven thickness were within a predetermined range, and the glass could be efficiently heated at the time of container processing by a burner. Therefore, it is considered that the amount of evaporation of B 2 O 3 and Na 2 O does not increase despite not containing BaO. Sample No. which is a comparative example In Nos. 7 and 8, the bend was large and the glass could not be efficiently heated at the time of processing the container by the burner. Therefore, an excessive amount of heat is required when processing the glass tube, and there is a concern that the amount of evaporation of B 2 O 3 and Na 2 O may increase.
なお線熱膨張係数の測定は、約５ｍｍφ×５０ｍｍのロッド状に成形したガラス試料を用い、ディラートメーターにより、３０〜３８０℃の温度範囲において行った。 Note that the linear thermal expansion coefficient was measured using a glass sample formed into a rod shape of about 5 mmφ × 50 mm by a dilatometer in a temperature range of 30 to 380 ° C.
歪点、徐冷点及び軟化点の測定はファイバーエロンゲーション法で行った。 The strain point, annealing point and softening point were measured by a fiber elongation method.
作業温度は、白金球引き上げ法によって求めた高温粘度とＦｕｌｃｈｅｒの粘度計算式からガラスの粘度曲線を求め、この粘度曲線から１０４ｄＰａ・ｓに相当する温度を求めた。 As the working temperature, a viscosity curve of the glass was obtained from the high-temperature viscosity obtained by the platinum ball pulling-up method and the Fulcher viscosity calculation formula, and a temperature corresponding to 10 4 dPa · s was obtained from the viscosity curve.
液相温度の測定は、約１２０×２０×１０ｍｍの白金ボートに粉砕したガラス試料を充填し、線形の温度勾配を有する電気炉に２４時間投入した。その後、顕微鏡観察にて結晶析出箇所を特定し、結晶析出箇所に対応する温度を電気炉の温度勾配グラフから算出し、この温度を液相温度とした。 For the measurement of the liquidus temperature, a platinum boat having a size of about 120 × 20 × 10 mm was filled with the crushed glass sample, and was placed in an electric furnace having a linear temperature gradient for 24 hours. Thereafter, the crystal deposition location was specified by microscopic observation, the temperature corresponding to the crystal deposition location was calculated from the temperature gradient graph of the electric furnace, and this temperature was taken as the liquidus temperature.
液相粘度の算出は、歪点、徐冷点、軟化点、作業温度とＦｕｌｃｈｅｒの粘度計算式からガラスの粘度曲線を求め、この粘度曲線から液相温度におけるガラスの粘度を算出し、この粘度を液相粘度とした。 The liquidus viscosity is calculated by calculating the viscosity curve of the glass from the strain point, the annealing point, the softening point, the working temperature and the Fulcher viscosity calculation formula, and calculating the viscosity of the glass at the liquidus temperature from the viscosity curve. Was taken as the liquidus viscosity.
加水分解抵抗性試験は、アルミナ製の乳鉢と乳棒を用いて試料を粉砕し、ＥＰ８．０の粉末試験法に準じた方法で行った。詳細な試験手順は以下の通りである。試料の表面をエタノールで良く拭き、アルミナ製の乳鉢と乳棒で試料を粉砕した後、ステンレス製の目開き７１０μｍ、４２５μｍ、３００μｍの３つの篩を用いて分級した。篩に残ったものは再度粉砕し、同じ篩操作を行い、３００μｍの篩上に残った試料粉末をエタノールで洗浄し、ビーカー等のガラス容器に投入した。その後、エタノールを入れてかき混ぜ、超音波洗浄機で１分間洗浄した後、上澄み液だけを流し出す操作を６回行った。その後、１１０℃のオーブンで３０分間乾燥させ、デシケーター内で３０分間冷却した。得られた試料粉末を、電子天秤を用いて１０ｇ精度±０．０００１ｇで秤量し、２５０ｍＬの石英フラスコに入れ、超純水５０ｍＬを加えた。密栓後、フラスコをオートクレーブに入れて１２１℃、３０分間保持した。１００℃から１２１℃までは１℃／分で昇温し、１２１℃から１００℃までは２℃／分で降温した。９５℃まで冷却後、試料をコニカルビーカーに取り出した。３０ｍＬの超純水でフラスコ内を洗浄し、コニカルビーカーに流し入れる操作を３回行った。試験後の液にメチルレッドを約０．０５ｍＬ滴下後、０．０２ｍｏｌ／Ｌの塩酸で中和滴定を行い、塩酸の消費量を記録し、試料ガラス１ｇあたりの塩酸消費量を算出した。 The hydrolysis resistance test was performed by pulverizing a sample using a mortar and pestle made of alumina and according to a method according to the powder test method of EP 8.0. The detailed test procedure is as follows. The surface of the sample was thoroughly wiped with ethanol, and the sample was pulverized with an alumina mortar and pestle, and then classified using three stainless steel sieves having openings of 710 μm, 425 μm, and 300 μm. What was left on the sieve was pulverized again and the same sieving operation was performed. The sample powder remaining on the 300 μm sieve was washed with ethanol and put into a glass container such as a beaker. Thereafter, the operation of adding ethanol, stirring, washing with an ultrasonic washing machine for 1 minute, and flowing out only the supernatant was performed six times. Then, it was dried in an oven at 110 ° C. for 30 minutes and cooled in a desiccator for 30 minutes. The obtained sample powder was weighed to an accuracy of ± 0.0001 g using an electronic balance, placed in a 250 mL quartz flask, and 50 mL of ultrapure water was added. After sealing, the flask was placed in an autoclave and kept at 121 ° C. for 30 minutes. The temperature was increased at a rate of 1 ° C./min from 100 ° C. to 121 ° C., and decreased at a rate of 2 ° C./min from 121 ° C. to 100 ° C. After cooling to 95 ° C., the sample was taken out into a conical beaker. The operation of washing the inside of the flask with 30 mL of ultrapure water and pouring it into a conical beaker was performed three times. After about 0.05 mL of methyl red was dropped into the liquid after the test, neutralization titration was performed with 0.02 mol / L hydrochloric acid, the consumption of hydrochloric acid was recorded, and the consumption of hydrochloric acid per 1 g of sample glass was calculated.
耐酸性試験は、試料表面積を５０ｃｍ２、溶出液である６ｍｏｌ／Ｌの塩酸の液量を８００ｍＬとし、ＤＩＮ１２１１６に準じて行った。詳細な試験手順は以下の通りである。まず全ての表面を鏡面研磨仕上げとした総表面積が５０ｃｍ２のガラス試料片を準備し、前処理として試料をフッ酸（４０質量％）と塩酸（２ｍｏｌ／Ｌ）を体積比で１：９となるように混合した溶液に浸漬し、１０分間マグネティックスターラーで攪拌した。次いで試料片を取出し、超純水中で２分間の超音波洗浄を３回行った後、エタノール中で１分間の超音波洗浄を２回行った。次に、試料片を１１０℃のオーブンの中で１時間乾燥させ、デシケーター内で３０分間冷却した。このようにして得られた試料片の質量ｍ１を精度±０．１ｍｇまで測定し、記録した。続いて石英ガラス製のビーカーに６ｍｏｌ／Ｌの塩酸８００ｍＬを入れ、電熱器を用いて沸騰するまで加熱し、白金線で吊した試料片を投入して６時間保持した。試験中の液量の減少を防ぐために、容器の蓋の開口部はガスケット及び冷却管で栓をした。その後、試料片を取り出し、超純水中で２分間の超音波洗浄を３回行った後、エタノール中で１分間の超音波洗浄を２回行った。さらに洗浄した試料片を１１０℃のオーブンの中で1時間乾燥し、デシケーター内で３０分間冷却した。このようにして処理した試料の質量片ｍ２を精度±０．１ｍｇまで測定し、記録した。最後に沸騰塩酸に投入する前後の試料の質量ｍ１、ｍ２ｍｇと試料の総表面積Ａｃｍ２から以下の式２によって単位面積当たりの質量減少量を算出し、耐酸性試験の測定値とした。 The acid resistance test was carried out in accordance with DIN12116 by setting the sample surface area to 50 cm 2 and the amount of 6 mol / L hydrochloric acid as an eluate to 800 mL. The detailed test procedure is as follows. First, a glass sample piece having a total surface area of 50 cm 2 with all surfaces mirror-polished was prepared. As a pretreatment, the sample was treated with hydrofluoric acid (40% by mass) and hydrochloric acid (2 mol / L) at a volume ratio of 1: 9. The resulting mixture was immersed in a mixed solution and stirred with a magnetic stirrer for 10 minutes. Next, the sample piece was taken out, subjected to ultrasonic cleaning three times in ultrapure water for 2 minutes, and then subjected to ultrasonic cleaning twice in ethanol for 1 minute. Next, the sample pieces were dried in an oven at 110 ° C. for 1 hour and cooled in a desiccator for 30 minutes. In this way the mass m 1 of the obtained sample pieces were measured to an accuracy ± 0.1 mg, it was recorded. Subsequently, 800 mL of 6 mol / L hydrochloric acid was placed in a quartz glass beaker, heated to boiling using an electric heater, and a sample piece suspended with a platinum wire was charged and held for 6 hours. The opening of the lid of the container was plugged with a gasket and cooling tube to prevent the liquid volume from decreasing during the test. Thereafter, the sample piece was taken out, subjected to ultrasonic cleaning for three minutes in ultrapure water for two minutes, and then subjected to ultrasonic cleaning for one minute in ethanol twice. Further, the washed sample was dried in an oven at 110 ° C. for 1 hour and cooled in a desiccator for 30 minutes. In this way the mass pieces m 2 of sample treated was measured to an accuracy ± 0.1 mg, were recorded. Finally, from the masses m 1 and m 2 of the sample before and after being introduced into boiling hydrochloric acid and the total surface area Acm 2 of the sample, the amount of mass reduction per unit area was calculated by the following equation 2, and the measured value was used as a measured value in the acid resistance test. .
［式２］ 単位面積当たりの質量減少量＝１００×（ｍ１−ｍ２）／２×Ａ
Ｓｎの溶出量は、加水分解抵抗性試験後の試験液について、ＩＣＰ発光分析装置（バリアン製）にて分析を行った。詳細な試験手順は以下の通りである。加水分解抵抗性試験後の試験溶液をメンブランフィルターでろ過して遠沈管に採取した。Ｓｎ含有量が０ｍｇ／Ｌ、０．０５ｍｇ／Ｌ、０．５ｍｇ／Ｌ、１．０ｍｇ／Ｌとなるように、Ｓｎ標準液（和光純薬工業製）を希釈して、標準溶液を作製した。それらの標準溶液から検量線を作成し、試験液中のＳｎ溶出量を算出した。Ｓｎの測定波長は１８９．９２５ｎｍとした。
[Equation 2] Mass loss per unit area = 100 × (m 1 −m 2 ) / 2 × A
The elution amount of Sn was analyzed using a test solution after the hydrolysis resistance test using an ICP emission spectrometer (manufactured by Varian). The detailed test procedure is as follows. The test solution after the hydrolysis resistance test was filtered through a membrane filter and collected in a centrifuge tube. A standard solution was prepared by diluting a Sn standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) so that the Sn content became 0 mg / L, 0.05 mg / L, 0.5 mg / L, and 1.0 mg / L. . A calibration curve was prepared from these standard solutions, and the amount of Sn eluted in the test solution was calculated. The measurement wavelength of Sn was 189.925 nm.
ガラス管の曲がりの測定は以下の手順で行った。平坦な板の上で１０００ｍｍに切断したガラス管の一端を押さえながら回転させ、平坦な板から浮き上がった高さの最大値を測定した。 The measurement of the bending of the glass tube was performed according to the following procedure. The glass tube cut to 1000 mm on a flat plate was rotated while holding one end thereof, and the maximum value of the height of the glass tube rising from the flat plate was measured.
ガラス管の偏肉測定は以下の手順で行った。ガラス管を５０ｍｍ程度に切断し、ガラス管を回転させながら肉厚を測定し、式２により偏肉を算出した。 The thickness deviation measurement of the glass tube was performed in the following procedure. The glass tube was cut to about 50 mm, the wall thickness was measured while rotating the glass tube, and the uneven thickness was calculated by Equation 2.
[式２]（最大肉厚−最小肉厚）／目標肉厚×１００
ガラスの加工性評価は、以下の手順により評価した。作製した管ガラスを回転させながら管端を一定時間、酸素バーナーにて加熱し、融封した。加熱後、融封した管端を目視で観察し、形状が良好である場合は○、形状が維持できない場合は×とした。
[Equation 2] (maximum thickness−minimum thickness) / target thickness × 100
The processability of the glass was evaluated according to the following procedure. The end of the tube was heated with an oxygen burner for a certain period of time while rotating the manufactured tube glass, and the tube was sealed. After heating, the end of the sealed tube was visually observed, and was evaluated as ○ when the shape was good, and x when the shape could not be maintained.
本発明の医薬容器用ガラス管は、アンプル、バイアル、プレフィルドシリンジ、カートリッジなど様々な医薬容器用材料として好適に使用できる。 The glass tube for a medical container of the present invention can be suitably used as a material for various medical containers such as ampules, vials, prefilled syringes, and cartridges.
Claims (17)
を必須成分として含み、ＢａＯを実質的に含まないホウケイ酸ガラスからなり、管ガラスの曲がりが６．０ｍｍ以下、偏肉が１５％以下であることを特徴とする医薬容器用ガラス管。 SiO 2 , Al 2 O 3 , B 2 O 3 , R 2 O (R is at least one of Li, Na, and K)
Is a borosilicate glass containing essentially no BaO and substantially no BaO, and the tube glass has a bend of 6.0 mm or less and an uneven wall thickness of 15% or less.
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| US15/757,155 US20180257975A1 (en) | 2015-09-03 | 2016-08-29 | Borosilicate glass for pharmaceutical container, glass tube for pharmaceutical container, and manufacturing method for pharmaceutical container |
| CN201680051403.6A CN107949547A (en) | 2015-09-03 | 2016-08-29 | The manufacture method of medical container borosilicate glass, medical container glass tube and medical container |
| EP16841770.7A EP3345876A4 (en) | 2015-09-03 | 2016-08-29 | Borosilicate glass for medicine containers, glass tube for medicine containers and method for producing medicine container |
| PCT/JP2016/075135 WO2017038738A1 (en) | 2015-09-03 | 2016-08-29 | Borosilicate glass for medicine containers, glass tube for medicine containers and method for producing medicine container |
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