JP2014088293A - Medical glass and medical glass tube - Google Patents

Medical glass and medical glass tube Download PDF

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JP2014088293A
JP2014088293A JP2012239843A JP2012239843A JP2014088293A JP 2014088293 A JP2014088293 A JP 2014088293A JP 2012239843 A JP2012239843 A JP 2012239843A JP 2012239843 A JP2012239843 A JP 2012239843A JP 2014088293 A JP2014088293 A JP 2014088293A
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glass
pharmaceutical
viscosity
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mass
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Hiroshi Sawazato
拡志 澤里
Ken Choju
研 長壽
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority to PCT/JP2013/077271 priority patent/WO2014069177A1/en
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    • 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

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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

PROBLEM TO BE SOLVED: To provide a medical glass and a medical glass tube having high productivity and chemical durability.SOLUTION: The medical glass contains, by mass%, SiOof 72 to 80%, BOof 5 to 12.4%, AlOof 5 to 15%, NaO of 0 to 10%, KO of 0 to 10%, NaO + KO of 7.6 to 15%, CaO of 0 to 5% and BaO of 0.1 to 1.9%. The medical glass preferably has weight reduction amount per unit area in the acid resistance test according to DIN12116 of 1.0 (mg/dm) or less.

Description

本発明は、医薬品容器等に用いられるガラスおよび医薬用ガラス管に関する。   The present invention relates to glass and pharmaceutical glass tubes used for pharmaceutical containers and the like.

医薬用ガラスには、高い化学的安定性、低い作業点、低い熱膨張係数、また生産性の観点から高い耐失透性（高い液相粘度）が要求される。このような要求特性から、一般的な医薬用ガラスは、ガラス組成としてＳｉＯ２、Ｂ２Ｏ３、Ａｌ２Ｏ３、Ｎａ２Ｏ、Ｋ２Ｏ、ＣａＯ、ＢａＯと少量の清澄剤を含むホウケイ酸ガラスから作製されている。 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.

上記成分のうちＢａＯは、医薬用ガラスの化学的耐久性を向上する成分であるが、ＢａＯの含有量が多すぎると、ＢａＯとアルミナ系耐火物の反応によってバリウム長石結晶が析出しやすくなる。そのため、液相粘度が低下し、生産性が悪化するという問題がある。このような問題に鑑み、特許文献１では、Ｎａ２Ｏ等の成分の含有量を調整することにより、ＢａＯを含まず且つ液相粘度の低下を抑制した医薬用ガラスが提案されている。 Of these components, BaO is a component that improves the chemical durability of pharmaceutical glass. However, if the content of BaO is too large, barium feldspar crystals are likely to precipitate due to the reaction between BaO and the alumina-based refractory. Therefore, there exists a problem that liquid phase viscosity falls and productivity deteriorates. In view of such a problem, 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.

しかしながら、特許文献１の医薬用ガラスは、作業点が１１６５℃以上と高く、加工性が悪いという問題がある。このような問題を解決すべく、特許文献２ではＡｌ２Ｏ３等の成分の含有量を調整することにより、ＢａＯを含まず且つ作業点を１１４０℃以下とした医薬用ガラスが提案されている。 However, the pharmaceutical glass of Patent Document 1 has a problem that the working point is as high as 1165 ° C. or higher and the processability is poor. In order to solve such a problem, 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 . .

特開平４−０７４７３１号公報JP-A-4-074731 特開平７−２０６４７２号公報JP-A-7-206472

しかしながら、特許文献２に開示されるガラスは、Ｂ２Ｏ３の含有量が多いため、溶融工程において、いわゆるスカム等の異質層が形成されやすく、生産性が悪化しやすいという問題があった。 However, 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.

また、近年、医薬用ガラス容器に充填される薬品の多様化が進んでおり、ガラス容器を侵食し易い薬品も開発されている。したがって、医薬用ガラスには、より高い化学的耐久性が要求されるようになっている。   In recent years, chemicals filled in medical glass containers have been diversified, and chemicals that easily corrode glass containers have been developed. Therefore, higher chemical durability is required for pharmaceutical glass.

このような問題に鑑み、本発明の目的は、従来品に比べて、高い生産性および化学的耐久性を有する医薬用ガラスおよび医薬用ガラス管を提供することである。   In view of such a problem, 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.

本発明者等は、鋭意検討を行なった結果、ガラス組成を所定範囲に規制することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明の医薬用ガラスは、質量％で、ＳｉＯ２ ７２〜８０％、Ｂ２Ｏ３ ５〜１２．４％、Ａｌ２Ｏ３ ５〜１５％、Ｎａ２Ｏ ０〜１０％、Ｋ２Ｏ ０〜１０％、Ｎａ２Ｏ＋Ｋ２Ｏ ７．６−１５％、ＣａＯ ０〜５％、ＢａＯ ０．１〜１．９％を含有することを特徴とする。 As a result of intensive studies, 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. In other words, pharmaceutical glass of the present invention, in mass%, SiO 2 72~80%, 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%, characterized in that it contains 0.1 to 1.9% BaO.

本発明の医薬用ガラスは、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が１．０（ｍｇ／ｄｍ２）以下であることが好ましい。 In the acid resistance test according to DIN12116, the pharmaceutical glass of the present invention preferably has a mass reduction amount per unit area of 1.0 (mg / dm 2 ) or less.

本発明の医薬用ガラスは、質量％で、ＳｉＯ２ ７３〜７５．５％、Ｂ２Ｏ３ ５〜１２％、Ａｌ２Ｏ３ ５〜１５％、Ｎａ２Ｏ ０〜９％、Ｋ２Ｏ ０〜９％、Ｎａ２Ｏ＋Ｋ２Ｏ ７．６−９％、ＣａＯ ０〜５％、ＢａＯ ０．１〜１．９％、ＺｒＯ２ ０〜０．５％、Ｃｌ ０〜５％を含有することが好ましい。 Pharmaceutical glass of the present invention, in 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 0~9%, Na 2 O + K 2 O 7.6-9%, CaO 0~5%, BaO 0.1~1.9%, ZrO 2 0~0.5%, containing 0 to 5% Cl It is preferable.

本発明の医薬用ガラスは、質量％比でＳｉＯ２／（Ａｌ２Ｏ３＋Ｂ２Ｏ３）の値が４．７５以下であることが好ましい。 The glass for pharmaceutical use of the present invention preferably has a value of SiO 2 / (Al 2 O 3 + B 2 O 3 ) of 4.75 or less in terms of mass%.

本発明の医薬用ガラスは、ガラスの粘度が１０４ｄＰａ・ｓとなる温度が１１６０℃以下であることが好ましい。なお、以下ではガラスの粘度が１０４ｄＰａ・ｓとなる温度を作業点と呼称する。 In the pharmaceutical glass of the present invention, the temperature at which the viscosity of the glass is 10 4 dPa · s is preferably 1160 ° C. or lower. Hereinafter, the temperature at which the viscosity of the glass is 10 4 dPa · s is referred to as a working point.

本発明の医薬用ガラスは、液相粘度が１０５ｄＰａ・ｓ以上であることが好ましい。 The medicinal glass of the present invention preferably has a liquidus viscosity of 10 5 dPa · s or more.

本発明の医薬用ガラスによれば、従来品に比べ高い生産性、および化学的耐久性を有する医薬用ガラスを得ることができる。より詳細には、本発明の医薬用ガラスは、Ｂ２Ｏ３の含有量を適切に規制することにより、溶融工程におけるスカム等の異質ガラスの発生を抑制することができる。また、ＳｉＯ２やアルカリ金属等の含有量を適切に規制することにより、ダンナー法で成形可能な液相粘度を有し、且つ高い化学的耐久性を得ることができる。 According to 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 can suppress the generation of extraneous glass such as scum in the melting step by appropriately regulating the content of B 2 O 3 . In addition, by appropriately regulating the content of SiO 2 , alkali metal, or the like, it has a liquid phase viscosity that can be molded by the Danner method, and high chemical durability can be obtained.

本発明の医薬用ガラスは、ガラス組成として、質量％で、ＳｉＯ２ ７２〜８０％、Ｂ２Ｏ３ ５〜１２．４％、Ａｌ２Ｏ３ ５〜１５％、Ｎａ２Ｏ ０〜１０％、Ｋ２Ｏ ０〜１０％、Ｎａ２Ｏ＋Ｋ２Ｏ ７．６−１５％、ＣａＯ ０〜５％、ＢａＯ ０．１〜１．９％含有する。上記のように各成分の含有範囲を限定した理由を以下に説明する。なお、以下の組成範囲の説明において、％表示は、特に断りがある場合を除き、質量％を表す。 The glass for pharmaceutical use of the present invention has, as a glass composition, 72% by weight of SiO 2, 5 to 12.4% of B 2 O 3 , 5 to 15% of Al 2 O 3 , and 0 to 10% of Na 2 O. , K 2 O 0~10%, Na 2 O + K 2 O 7.6-15%, CaO 0~5%, containing BaO 0.1 to 1.9%. The reason for limiting the content range of each component as described above will be described below. In the description of the composition range below,% display represents mass% unless otherwise specified.

ＳｉＯ２は、ガラスのネットワークを形成する成分である。ＳｉＯ２の含有量は７２〜８０％であり、好ましくは７２〜７７％、より好ましくは７３〜７５．５％である。ＳｉＯ２の含有量が７２％より少ないと、ガラスの耐酸性、化学的耐久性が低下する傾向がある。ＳｉＯ２の含有量が８０％より多くなると、液相粘度が低下し、成形性および生産性が悪化しやすくなる。 SiO 2 is a component that forms a network of glass. The content of SiO 2 is 72 to 80%, preferably 72 to 77%, more preferably 73 to 75.5%. When the content of SiO 2 is less than 72%, the acid resistance and chemical durability of the glass tend to decrease. When the content of SiO 2 is more than 80%, the liquid phase viscosity is lowered, and the moldability and productivity are easily deteriorated.

Ｂ２Ｏ３は、ガラスの液相粘度を増加させて、失透を抑制する効果のある成分である。Ｂ２Ｏ３の含有量は５〜１２．４％であり、好ましくは７〜１２．４％であり、より好ましくは９〜１２％である。Ｂ２Ｏ３の含有量が５％より少ないと、液相粘度の増加効果および失透抑制効果を得にくくなる。Ｂ２Ｏ３の含有量が１２．４％より多いと、溶融工程等においてスカム等の異質層が形成されやすくなる。 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%. When 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.

Ａｌ２Ｏ３は、ガラスの液相粘度を増加させて耐失透性を向上し、また耐水性を向上する効果のある成分である。Ａｌ２Ｏ３の含有量は５〜１５％であり、好ましくは５〜１０％、より好ましくは５〜７％である。Ａｌ２Ｏ３の含有量が５％より少ないと、耐失透性向上効果および耐水性向上効果を得にくくなる。Ａｌ２Ｏ３の含有量が１５％より多いと、ガラスの粘度が上昇し、溶融性および成形性が悪化しやすくなる。 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%. When the content of Al 2 O 3 is less than 5%, it becomes difficult to obtain the devitrification resistance improving effect and the water resistance improving effect. When the content of Al 2 O 3 is more than 15%, the viscosity of the glass increases, meltability and moldability tends to deteriorate.

また、Ｂ２Ｏ３とＡｌ２Ｏ３とは共に、ＳｉＯ２をガラスネットワーク中で安定化させる成分である。ＳｉＯ２／（Ａｌ２Ｏ３+Ｂ２Ｏ３）の値が大きくなると、ＳｉＯ２をガラスネットワーク中に安定化させることが難しくなる。そのため、ガラス中にクリストバライトが析出しやすくなり、液相粘度が低下する。したがって、ＳｉＯ２／（Ａｌ２Ｏ３+Ｂ２Ｏ３）の値は好ましくは４．７５以下であり、より好ましくは４．７０以下である。 Both B 2 O 3 and Al 2 O 3 are components that stabilize SiO 2 in the glass network. As the value of SiO 2 / (Al 2 O 3 + B 2 O 3 ) increases, it becomes difficult to stabilize SiO 2 in the glass network. Therefore, cristobalite is likely to be precipitated in the glass, and the liquid phase viscosity is 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.

Ｎａ２Ｏはガラスの粘度を低下させ、熱膨張係数を調整する効果のある成分である。Ｎａ２Ｏの含有量は０〜１０％であり、好ましくは３〜１０％であり、さらに好ましくは５〜９％である。Ｎａ２Ｏの含有量が１０％より多いと、ガラスの熱膨張係数が大幅に増加して耐熱衝撃性が悪化する。 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.

Ｋ２ＯもＮａ２Ｏと同様にガラスの粘度を低下させ、熱膨張係数を増加させる効果のある成分である。Ｋ２Ｏの含有量は０〜１０％であり、好ましくは０．１〜７％であり、さらに好ましくは１〜３％である。Ｋ２Ｏの含有量が１０％より多いと、熱膨張係数が大幅に増加して耐熱衝撃性が悪化する。 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.

Ｎａ２ＯおよびＫ２Ｏの合量は、７．６〜１５％であり、好ましくは７．６〜９％、より好ましくは７．６〜８．５％である。Ｎａ２ＯおよびＫ２Ｏの合量が７．６％より少ないと、作業点が高くなり成形性が悪化しやすくなる。Ｎａ２ＯおよびＫ２Ｏの合量が１５％より多いと、ガラスの熱膨張係数が増加して耐熱衝撃性が悪化しやすくなる。 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%. When 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. When 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は、ガラスの溶解性を向上させる効果のある成分である。ＣａＯの含有量は０〜５％であり、好ましくは０〜２％であり、より好ましくは０〜１．１％である。ＣａＯの含有量が５％より多いと、ガラスの耐酸性が低下し、化学的耐久性が悪化しやすくなる。   CaO is a component having an 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は、ガラスの熱膨張係数を調整し、また、粘度を低下させる効果のある成分である。ＢａＯの含有量は０．１〜１．９％であり、好ましくは０．１〜１．５％であり、さらに好ましくは０．１〜１．３％である。ＢａＯの含有量が１．９％より多いと、ガラスの液相粘度が低下し、耐失透性が悪化しやすくなる。また、ＢａＯを含有しない場合、ガラスの粘度が増加し、作業点が高くなり過ぎる。なお、ＢａＯを含有せずにＮａ２Ｏ、Ｋ２Ｏ、ＣａＯの含有量を増加させてガラスの粘度を低下させようとすると、熱膨張係数が高くなり過ぎて耐熱衝撃性が悪化しやすくなる。これは、Ｎａ２Ｏ、Ｋ２Ｏ、ＣａＯの含有量あたりの熱膨張係数の上昇量がＢａＯのそれに比べ大きいためである。 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%. When there is more content of BaO than 1.9%, the liquidus viscosity of glass will fall and devitrification resistance will deteriorate easily. Moreover, when it does not contain BaO, 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.

本発明の医薬用ガラスは、さらにＺｒＯ２を含有しても良い。ＺｒＯ２はガラスの化学的耐久性や耐熱性を向上する成分である。ＺｒＯ２の含有量は、好ましくは０〜０．５％であり、より好ましくは０〜０．２％である。ＺｒＯ２の含有量が０．５％より多いと、ガラスの粘度が上昇して、作業点が高くなりやすい。 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%. If the content of ZrO 2 is more than 0.5%, the viscosity of the glass increases, and the working point tends to be high.

本発明の医薬用ガラスは、清澄剤として、Ｃｌ、Ｓｂ２Ｏ３、Ａｓ２Ｏ３、ＳｎＯ２、Ｎａ２ＳＯ４等を一種類または二種類以上含有してもよい。これら清澄剤の含有量の合計は好ましくは０〜５％であり、より好ましくは０〜１％であり、さらに好ましくは０〜０．５％である。清澄剤の含有量の合計が５％より多いと、医薬用ガラス容器に保存した薬液への清澄剤の溶出と薬液成分の変質が起こりやすくなる。 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. The total content of these fining agents is preferably 0 to 5%, more preferably 0 to 1%, and still 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 solution components are likely to occur.

また、本発明の医薬用ガラスは、紫外線や可視光線の遮蔽性能を向上すること等を目的としてＴｉＯ２またはＦｅ２Ｏ３を含有しても良い。ＴｉＯ２とＦｅ２Ｏ３の含有量の合計は、０〜１０％であることが好ましい。本発明の医薬用ガラスにＴｉＯ２またはＦｅ２Ｏ３を含有させることによって、医薬用容器として用いた場合に、容器内に充填された薬品が紫外線や可視光線等により変質することを防ぐことができる。 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%. By containing TiO 2 or Fe 2 O 3 in the pharmaceutical glass of the present invention, it is possible to prevent chemicals filled in the container from being altered by ultraviolet rays or visible light when used as a pharmaceutical container. it can.

本発明の医薬用ガラスは、化学的耐久性、高温粘度等を改善するために上記成分以外に、Ｐ２Ｏ５、Ｃｒ２Ｏ３、ＰｂＯ、Ｌａ２Ｏ３、ＷＯ３、Ｎｂ２Ｏ５、Ｙ２Ｏ３等の成分を各々３％まで添加して良い。 In addition to the above components, the medicinal glass of the present invention is improved in chemical durability, high temperature viscosity, and the like, in addition to P 2 O 5 , Cr 2 O 3 , PbO, La 2 O 3 , WO 3 and Nb 2 O 5 , Y 2 O 3 and the like may be added up to 3% each.

また、本発明の医薬用ガラスは、不純物として、例えば、Ｈ２、ＣＯ２、ＣＯ、Ｈ２Ｏ、Ｈｅ、Ｎｅ、Ａｒ、Ｎ２を各々０．１％まで含有して良い。さらに不純物として、Ｐｔ、Ｒｈ、Ａｕを各々５００ｐｐｍ以下まで含有して良い。Ｐｔ、Ｒｈ、Ａｕ各々の含有量は、より好ましくは３００ｐｐｍ以下である。 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.

本発明の医薬用ホウ珪酸ガラスは、ＤＩＮ（ドイツ工業規格）１２１１６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が１．０（ｍｇ／ｄｍ２）以下であることが好ましい。上記質量減少量が１．０（ｍｇ／ｄｍ２）より多いと、すなわちガラスからの溶出物が多いと、医薬用ガラスを医薬用容器として用いた場合に、充填された薬剤が変質しやすくなる傾向がある。したがって、上記質量減少量は、より好ましくは０．９５（ｍｇ／ｄｍ２）以下、さらに好ましくは０．８（ｍｇ／ｄｍ２）以下、もっとも好ましくは０．５（ｍｇ／ｄｍ２）以下である。 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.

本発明の医薬用ガラスは、作業点（ガラスの粘度が１０４ｄＰａ・ｓとなる温度）が１１６０℃以下であることが好ましい。作業点は、より好ましくは、１１５７℃以下、さらに好ましくは１１５５℃以下、最も好ましくは１１５０℃以下である。作業点が１１６０℃より高くなると、管状に成形した本発明の医薬用ガラスからアンプルや管瓶用ガラス等の医薬用容器を作製する際の加工温度を高くする必要がある。そして、加工温度が高くなると、ガラス中のアルカリ成分の蒸発量が著しく増加し、蒸発したアルカリ成分が医薬用容器の内表面に付着しやすくなる。医薬用容器の内表面に付着したアルカリ成分が薬液の保存中や薬液充填後のオートクレーブ処理等において薬液中へ溶出すると、薬液のｐＨの上昇や薬液成分の変質を引き起こすおそれがある。 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. When 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. And when 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 may be altered.

本発明の医薬用ガラスの液相粘度は１０５ｄＰａ・ｓ以上であることが好ましい。液相粘度は、より好ましくは１０５．２ｄＰａ・ｓ以上、さらに好ましくは１０５．４ｄＰａ・ｓ以上である。液相粘度が１０５ｄＰａ・ｓより低いとダンナー法等を用いたガラスの成形が困難となるため、医薬用ガラス管を大量且つ安価に製造することが困難となる。 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 becomes difficult to form glass using the Danner method or the like, and thus it is difficult to manufacture a glass tube for medicine in large quantities and at low cost.

本発明の医薬用ガラスの液相温度は、１０１０℃以下であることが好ましい。液相温度は、より好ましくは９７０℃以下、さらに好ましくは９５０℃以下である。液相温度はガラスの耐失透性を考える上で重要な指標である。液相温度が高いほど、生産工程や加工工程において失透が起こりやすくなる。   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.

本発明の医薬用ガラスは、３０〜３８０℃における熱膨張係数が５０〜６０×１０−７／℃であることが好ましい。熱膨張係数は、より好ましくは５０〜５８×１０−７／℃、さらに好ましくは５１〜５５×１０−７／℃、もっとも好ましくは５１〜５３×１０−７／℃である。熱膨張係数が５０×１０−７／℃より低くなると、ガラスの粘度が上昇する傾向があり、溶融温度や成形温度が上昇してガラスを製造し難くなる。また、熱膨張係数が６０×１０−７／℃より高くなると、ガラスの製造工程、加工工程、滅菌工程等でサーマルショックにより破損する可能性が高くなる。 The pharmaceutical glass of the present invention preferably has a thermal expansion coefficient at 30 to 380 ° C. of 50 to 60 × 10 −7 / ° 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 increase, making it difficult to produce the glass. Moreover, if the thermal expansion coefficient is higher than 60 × 10 −7 / ° C., there is a high possibility of breakage due to thermal shock in the glass manufacturing process, processing process, sterilization process, and the like.

本発明の医薬用ガラス管の製造方法を例示する。本発明の医薬用ガラス管の製造方法としてはダンナー法が好適である。先ず、上記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、当該先端部から医薬用ガラス管を引き出す。なお、本発明の医薬用ガラス管の製造方法はダンナー法に限らず、従来の手法を用いて良い。例えば、ベロー法も本発明の医薬用ガラス管の製造方法として有効な方法である。   The manufacturing method of the glass tube for pharmaceuticals of this invention is illustrated. The Danner method is suitable as the method for producing the pharmaceutical glass tube of the present invention. First, glass raw materials are prepared so as to have the above glass composition, and a glass batch is prepared. Next, the glass batch was continuously charged into a melting furnace at 1550 to 1700 ° C., melted and clarified, and then the obtained molten glass was wound around a rotating refractory while blowing air from the tip of the refractory, The medical glass tube is pulled out from the tip. In addition, 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. For example, the bellows method is also an effective method for producing the pharmaceutical glass tube of the present invention.

以下、実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は単なる例示であり、本発明は、以下の実施例に何ら限定されない。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。   Hereinafter, based on an Example, this invention is demonstrated in detail. The following examples are merely illustrative, and the present invention is not limited to the following examples. Tables 1 and 2 show Examples (Sample Nos. 1 to 6) and Comparative Examples (Sample Nos. 7 and 8) of the present invention.

まず表１に記載のガラス組成になるように、ガラス原料を調合した後、得られたガラスバッチを白金坩堝に入れて１６００℃で４時間溶融した。次に、得られた溶融ガラスをカーボン製の型枠に流し出してインゴットを作成した後、所定のアニール処理（６５０℃に設定した電気炉内で炉冷）を行い、ガラス試料を得た。そして、得られたガラス試料を下記特性評価に適した形状に加工して、種々の特性を評価した。   First, after preparing glass raw materials so as to have the glass composition shown in Table 1, the obtained glass batch was put in a platinum crucible and melted at 1600 ° C. for 4 hours. Next, after the obtained molten glass was poured out into a carbon mold to create an ingot, a predetermined annealing treatment (furnace cooling in an electric furnace set at 650 ° C.) was performed to obtain a glass sample. And the obtained glass sample was processed into the shape suitable for the following characteristic evaluation, and various characteristics were evaluated.

耐酸性試験はＤＩＮ(ドイツ工業規格)１２１１６に準じた方法で行った。なお、ＤＩＮ１２１１６では試料の総表面積は１００ｃｍ２に規定されているが、本実施例の耐酸性試験では試料の総表面積を５０ｃｍ２とした。また、ＤＩＮ１２１１６では溶出液（６ｍｏｌ／Ｌ塩酸）の液量は１５００ｍＬに規定されているが、本実施例の耐酸性試験では溶出液の液量を８００ｍＬとした。 The acid resistance test was carried out in accordance with DIN (German Industrial Standard) 12116. In 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 . In 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.

詳細な試験手順は以下の通りである。先ず、ガラス試料の表面をすべて鏡面研磨仕上げとし、総表面積が５０ｃｍ２の試料片を準備した。次いで、試料片をフッ酸（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、超純水による２分間の超音波洗浄を３回行った後、エタノールによる１分間の超音波洗浄を２回行った。次いで、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。そして、試料片の質量ｍ1を精度±０．１ｍｇまで測定し、記録した。次いで、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、沸騰後、白金線でつるした試料片を塩酸内へ投入して６時間保持した。その後、試料片を取り出し、超純水による２分間の超音波洗浄を３回行った後、エタノールによる１分間の超音波洗浄を２回行った。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。試料片の質量ｍ2を精度±０．１ｍｇまで測定し、記録した。沸騰塩酸に投入する前後の試料の質量ｍ1、ｍ2（ｍｇ）と試料の総表面積Ａ（ｃｍ２）から、下記の式１によって単位面積当たりの質量減少量Δｍを算出し、耐酸性試験の測定値とした。質量減少量Δｍが小さいほど、耐酸性に優れるガラスであるといえる。

Δｍ＝１００×（ｍ1−ｍ2）／２×Ａ …（式１）
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. Next, 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. From the mass m 1 and m 2 (mg) of the sample before and after the boiling hydrochloric acid and the total surface area A (cm 2 ) of the sample, the mass reduction amount Δm 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 Δm, the more excellent the acid resistance.

Δm = 100 × (m 1 −m 2 ) / 2 × A (Formula 1)

歪点、徐冷点は、ＡＳＴＭ Ｃ３３６の方法に基づいて測定した値である。   The strain point and annealing point are values measured based on the method of ASTM C336.

軟化点は、ＡＳＴＭ Ｃ３３８の方法に基づいて測定した値である。   The softening point is a value measured based on the method of ASTM C338.

作業点は、ガラスの粘度が１０４．０ｄＰａ・ｓとなる温度を白金球引き上げ法で測定した値である。 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.

液相温度は、標準篩３０メッシュ（５００μｍ）を通過し、５０メッシュ（３００μｍ）に残るガラス粉末を白金ボートに入れ、温度勾配炉中に２４時間保持した後、結晶の析出する温度を測定した値である。   The liquid phase temperature passed through a standard sieve 30 mesh (500 μm), the glass powder remaining in 50 mesh (300 μm) 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.

液相粘度は、歪点、徐冷点、軟化点、作業点とＦｕｌｃｈｅｒの粘度計算式からガラスの粘度曲線を求め、この粘度曲線から算出した液相温度におけるガラスの粘度の値を指す。   The liquidus viscosity refers to the value of the viscosity of the glass at the liquidus temperature calculated from the viscosity curve obtained from the strain point, annealing point, softening point, working point, and Fulcher's viscosity calculation formula.

熱膨張係数は、ディラトメーターを用いて、３０〜３８０℃の温度範囲における平均熱膨張係数を測定した値である。   A thermal expansion coefficient is the value which measured the average thermal expansion coefficient in the temperature range of 30-380 degreeC using the dilatometer.

表から解るように、試料Ｎｏ．１〜６は、耐酸性試験における質量減少量Δｍが１．０ｍｇ／ｄｍ２以下であり、アルカリ溶出が少なく耐酸性に優れたガラスであった。一方、試料Ｎｏ．８は、耐酸性試験における質量減少量Δｍが１．０ｍｇ／ｄｍ２より多く、アルカリ溶出が多いガラスであった。また、試料Ｎｏ．７、８は、作業点が高く、加工性に劣るガラスであった。 As can be seen from the table, Sample No. Nos. 1 to 6 were glasses having a mass reduction amount Δm of 1.0 mg / dm 2 or less in the acid resistance test, and having few alkali elution and excellent acid resistance. On the other hand, sample No. No. 8 was a glass having a mass reduction amount Δm 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.

Claims (7)

質量％で、ＳｉＯ２ ７２〜８０％、Ｂ２Ｏ３ ５〜１２．４％、Ａｌ２Ｏ３ ５〜１５％、Ｎａ２Ｏ ０〜１０％、Ｋ２Ｏ ０〜１０％、Ｎａ２Ｏ＋Ｋ２Ｏ ７．６〜１５％、ＣａＯ ０〜５％、ＢａＯ ０．１〜１．９％を含有することを特徴とする医薬用ガラス。 By mass%, SiO 2 72~80%, 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% containing, The glass for pharmaceuticals characterized by the above-mentioned. 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が１．０ｍｇ／ｄｍ２以下であることを特徴とする請求項１に記載の医薬用ガラス。 2. The glass for pharmaceutical use according to claim 1, wherein a mass reduction amount per unit area is 1.0 mg / dm 2 or less in an acid resistance test according to DIN12116. 質量％で、ＳｉＯ２ ７３〜７５．５％、Ｂ２Ｏ３ ５〜１２％、Ａｌ２Ｏ３ ５〜１５％、Ｎａ２Ｏ ０〜９％、Ｋ２Ｏ ０〜９％、Ｎａ２Ｏ＋Ｋ２Ｏ ７．６〜９％、ＣａＯ ０〜５％、ＢａＯ ０．１〜１．９％、ＺｒＯ２ ０〜０．５％、Ｃｌ ０〜５％含有することを特徴とする請求項１または２に記載の医薬用ガラス。 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 0~9%, Na 2 O + K 2 O 7.6 to 9%, CaO 0 to 5%, BaO 0.1 to 1.9%, ZrO 2 0 to 0.5%, Cl 0 to 5%. 2. The glass for medical use according to 2. 質量％比でＳｉＯ２／（Ａｌ２Ｏ３＋Ｂ２Ｏ３）の値が４．７５以下であることを特徴とする請求項１〜３の何れかに記載の医薬用ガラス。 The glass for pharmaceutical use according to any one of claims 1 to 3, wherein a value of SiO 2 / (Al 2 O 3 + B 2 O 3 ) in a mass% ratio is 4.75 or less. ガラスの粘度が１０４ｄＰａ・ｓとなる温度が１１６０℃以下であることを特徴とする請求項1〜４の何れかに記載の医薬用ガラス。 The temperature at which the viscosity of the glass becomes 10 4 dPa · s is 1160 ° C or lower, and the glass for medical use according to any one of claims 1 to 4. 液相粘度が１０５ｄＰａ・ｓ以上であることを特徴とする請求項１〜５の何れかに記載の医薬用ガラス。 Liquid phase viscosity is 10 < 5 > dPa * s or more, The glass for pharmaceuticals in any one of Claims 1-5 characterized by the above-mentioned. 請求項１〜６の何れかに記載の医薬用ガラスからなる医薬用ガラス管。   A medical glass tube comprising the medical glass according to claim 1.
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