JP6323139B2 - Glass for pharmaceutical or cosmetic containers - Google Patents
Glass for pharmaceutical or cosmetic containers Download PDFInfo
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- JP6323139B2 JP6323139B2 JP2014085570A JP2014085570A JP6323139B2 JP 6323139 B2 JP6323139 B2 JP 6323139B2 JP 2014085570 A JP2014085570 A JP 2014085570A JP 2014085570 A JP2014085570 A JP 2014085570A JP 6323139 B2 JP6323139 B2 JP 6323139B2
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- 239000011521 glass Substances 0.000 title claims description 101
- 239000002537 cosmetic Substances 0.000 title claims description 30
- 238000004031 devitrification Methods 0.000 claims description 16
- 239000003814 drug Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 13
- 238000000071 blow moulding Methods 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 229910006404 SnO 2 Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000005356 container glass Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Description
本発明は、医薬品用または化粧品用の容器製造に適したガラスに関する。 The present invention relates to a glass suitable for manufacturing a container for pharmaceuticals or cosmetics.
医薬品や化粧品の容器として使用されるガラス容器の構成材料としては、従来、ソーダライムガラスやホウケイ酸ガラスが用いられている。しかしながら、これらアルカリ金属成分を含有するガラス材料を医薬品や化粧品の容器に用いた場合、ガラスに含まれるアルカリ金属成分と、医薬品や化粧品に含まれる成分と、の反応を抑制するため、容器内面に二酸化珪素皮膜を形成する（特許文献１）、または、容器内面に金属酸化物をコーティングし、加熱処理により該金属酸化物をガラス化して、容器内面にガラス化した膜を形成する（特許文献２）等により、容器からアルカリ金属成分が溶出するのを抑制する必要であった。しかしながら、これら皮膜を形成する措置は、容器の製造コストの増加につながるため、望ましくない。 Conventionally, soda lime glass and borosilicate glass have been used as a constituent material of glass containers used as containers for pharmaceuticals and cosmetics. However, when a glass material containing these alkali metal components is used in a pharmaceutical or cosmetic container, in order to suppress the reaction between the alkali metal component contained in the glass and the component contained in the pharmaceutical or cosmetic, A silicon dioxide film is formed (Patent Document 1), or a metal oxide is coated on the inner surface of the container, and the metal oxide is vitrified by heat treatment to form a vitrified film on the inner surface of the container (Patent Document 2). ) Etc., it was necessary to suppress the elution of the alkali metal component from the container. However, measures for forming these films are undesirable because they lead to an increase in the manufacturing cost of the container.
一方、特許文献３では、医薬品容器用ガラスとして、アルカリ金属成分を含有しない特定の組成の無アルカリガラスを提案している。しかしながら、ソーダライムガラスやホウケイ酸ガラスといったアルカリ金属成分を含有するガラスに比べて、無アルカリガラスは、医薬品や化粧品の容器に成形する温度域の粘性が高い傾向があるため、医薬品や化粧品の容器に成形する際の成形性という点で問題がある。
医薬品や化粧品の容器の成形法としては、ブロー成形やプレス成形が好ましく用いられる。これらの成形法による成形性の指標としては、ガラスの粘性がｌｏｇη＝７となる温度Ｔ7が用いられるが、特許文献３に記載の医薬品容器ガラスは、そのガラス組成から、温度Ｔ7が高くなるため、ブロー成形やプレス成形を用いて、医薬品や化粧品の容器に成形するのが困難である。
On the other hand, Patent Document 3 proposes a non-alkali glass having a specific composition that does not contain an alkali metal component as glass for a pharmaceutical container. However, compared to glass containing alkali metal components such as soda lime glass and borosilicate glass, non-alkali glass tends to have a higher viscosity in the temperature range to be molded into pharmaceutical and cosmetic containers. There is a problem in terms of formability when forming into a sheet.
Blow molding or press molding is preferably used as a method for molding a pharmaceutical or cosmetic container. As an index of moldability by these molding methods, a temperature T 7 at which the viscosity of the glass becomes log η = 7 is used. However, the pharmaceutical container glass described in Patent Document 3 has a high temperature T 7 due to its glass composition. Therefore, it is difficult to form a medicine or cosmetic container using blow molding or press molding.
本発明は、上記した問題点を解決するため、アルカリ金属成分を含有せず、かつ、ブロー成形やプレス成形による成形性に優れた、医薬品または化粧品の容器用ガラスの提供を目的とする。 In order to solve the above-described problems, an object of the present invention is to provide a glass for a pharmaceutical or cosmetic container that does not contain an alkali metal component and has excellent moldability by blow molding or press molding.
上記した目的を達成するため、本発明は、モル％表示で実質的に、
ＳｉＯ2 ５５〜６４％、
Ａｌ2Ｏ3 ６〜１４％、
Ｂ2Ｏ3 ５〜１０％
ＭｇＯ ２〜１２％、
ＣａＯ ２〜１２％、
ＳｒＯ ２〜１２％、
ＢａＯ ０〜１２％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １６〜２８％
よりなり、アルカリ金属酸化物を実質的に含有せず、ガラス粘度がｌｏｇη＝７となる温度Ｔ7が９５０℃以下である、医薬品または化粧品の容器用ガラスを提供する。
In order to achieve the above-described object, the present invention is substantially represented by mol%,
SiO 2 55~64%,
Al 2 O 3 6-14%,
B 2 O 3 5-10%
MgO 2-12%,
CaO 2-12%,
SrO 2-12%,
BaO 0-12%,
MgO + CaO + SrO + BaO 16-28%
More becomes, substantially free of alkali metal oxides, the temperature T 7 in which a glass viscosity of log [eta = 7 is 950 ° C. or less, to provide a container glass for pharmaceuticals or cosmetics.
本発明の医薬品または化粧品の容器用ガラスは、３０〜３００℃での平均熱膨張係数が３０×１０-7〜８０×１０-7／℃であることが好ましい。 The glass for containers for pharmaceuticals or cosmetics of the present invention preferably has an average coefficient of thermal expansion at 30 to 300 ° C. of 30 × 10 −7 to 80 × 10 −7 / ° C.
本発明の医薬品または化粧品の容器用ガラスは、失透温度が１２００℃以下であることが好ましい。 The glass for containers for pharmaceuticals or cosmetics of the present invention preferably has a devitrification temperature of 1200 ° C. or lower.
本発明の医薬品または化粧品の容器用ガラスは、アルカリ金属酸化物を実質的に含有しないため、このガラスを用いた医薬品または化粧品の容器では、ガラスに含まれるアルカリ金属成分と、医薬品や化粧品に含まれる成分と、の反応が抑制される。このため、容器内面に皮膜を形成することが不要である。
また、ガラス粘度がｌｏｇη＝７となる温度Ｔ7が９５０℃以下と低いため、ブロー成形やプレス成形により医薬品用容器や化粧品容器を成形する際の成形性が良好である。
Since the glass for pharmaceutical or cosmetic containers of the present invention does not substantially contain an alkali metal oxide, the pharmaceutical or cosmetic container using this glass contains an alkali metal component contained in the glass and the pharmaceutical or cosmetic. Reaction with the components to be suppressed. For this reason, it is unnecessary to form a film on the inner surface of the container.
Further, since the temperature T 7 at which the glass viscosity becomes log η = 7 is as low as 950 ° C. or less, the moldability when molding a pharmaceutical container or a cosmetic container by blow molding or press molding is good.
本発明の医薬品または化粧品の容器用ガラス（以下、「本発明のガラス」という。）は、アルカリ金属酸化物を実質的に含有しない。
なお、本明細書において、含有量といった場合、原料中における各成分の含有量ではなく、製造されたガラスにおける各成分の含有量を指す。
The glass for containers for pharmaceuticals or cosmetics of the present invention (hereinafter referred to as “the glass of the present invention”) contains substantially no alkali metal oxide.
In the present specification, the term “content” refers to the content of each component in the produced glass, not the content of each component in the raw material.
本発明のガラスにおいて、ＳｉＯ2はネットワークフォーマであり、必須である。ＳｉＯ2はガラスの化学耐久性を高める効果が大きいため含有量が多いことは好ましい。但し、ＳｉＯ2が多すぎると、失透特性や、容器への成形性に劣るため、６４モル％以下とする。好ましくは６２モル％以下である。逆に含有量が少ないと、化学耐久性の劣化につながるため好ましくない。本発明のガラスはＳｉＯ2の含有量が５５モル％以上である。 In the glass of the present invention, SiO 2 is a network former and is essential. Since SiO 2 has a large effect of enhancing the chemical durability of glass, it is preferable that the content thereof is large. However, if there is too much SiO 2 , the devitrification property and the moldability to the container are inferior. Preferably it is 62 mol% or less. Conversely, if the content is small, it is not preferable because it leads to deterioration of chemical durability. The glass of the present invention has a SiO 2 content of 55 mol% or more.
本発明のガラスにおいて、Ａｌ2Ｏ3はガラスの分相性を抑制し、少量であれば化学的耐久性が向上するため添加される。ガラスの分相が起こらなければ添加する必要がないが、分相を抑制するために６モル％以上添加する。好ましくは８モル％以上である。但し、多すぎると失透特性、化学耐久性、容器への成形性を劣化させるので好ましくない。本発明のガラスは、Ａｌ2Ｏ3を１４モル％以下含有する。 In the glass of the present invention, Al 2 O 3 is added because it suppresses the phase separation of the glass, and if it is in a small amount, chemical durability is improved. If glass phase separation does not occur, it is not necessary to add, but in order to suppress phase separation, 6 mol% or more is added. Preferably it is 8 mol% or more. However, if the amount is too large, devitrification properties, chemical durability, and moldability to containers are deteriorated. The glass of the present invention contains 14 mol% or less of Al 2 O 3 .
本発明のガラスにおいて、Ｂ2Ｏ3は容器への成形性を向上させ、またガラスの溶解反応性をよくし、失透特性を向上させ、線膨張係数を小さくすることができるので必須である。本発明のガラスは、Ｂ2Ｏ3の含有量が５モル％以上である。但し、Ｂ2Ｏ3の含有量が多すぎると化学耐久性が低下するため好ましくない。本発明のガラスは、Ｂ2Ｏ3の含有量が１０モル％以下である。 In the glass of the present invention, B 2 O 3 is essential because it can improve the moldability of the container, improve the melting reactivity of the glass, improve the devitrification characteristics, and reduce the linear expansion coefficient. . The glass of the present invention has a B 2 O 3 content of 5 mol% or more. However, if the content of B 2 O 3 is too large, the chemical durability is lowered, which is not preferable. The glass of the present invention has a B 2 O 3 content of 10 mol% or less.
本発明のガラスにおいて、ＭｇＯはアルカリ土類金属酸化物の中でも、容器への成形性を向上させ、線膨張係数を高くしないという特徴を有し、溶解性も向上させるので必須である。本発明のガラスにおいて、ＭｇＯの含有量は２モル％以上である。但し、多すぎるとガラスが分相したり、失透特性や化学耐久性が劣化し好ましくない。本発明のガラスにおいて、ＭｇＯの含有量は１２モル％以下である。 In the glass of the present invention, MgO is essential among alkaline earth metal oxides because it improves the moldability into containers and does not increase the linear expansion coefficient, and improves the solubility. In the glass of the present invention, the content of MgO is 2 mol% or more. However, if the amount is too large, the glass is not preferable because it causes phase separation, devitrification characteristics and chemical durability. In the glass of the present invention, the content of MgO is 12 mol% or less.
本発明のガラスにおいて、ＣａＯはアルカリ土類金属酸化物の中ではＭｇＯに次いで線膨張係数を高くせず、化学耐久性を向上させ、容器への成形性を向上させるという特徴を有し、溶解性も向上させるので必須である。本発明のガラスにおいて、ＣａＯの含有量は２モル％以上である。但し、多すぎると失透特性の劣化や線膨張係数の増大、化学耐久性の低下をまねくため好ましくない。本発明のガラスにおいて、ＣａＯの含有量は１２モル％以下である。 In the glass of the present invention, CaO has the characteristics that it does not increase the coefficient of linear expansion next to MgO among alkaline earth metal oxides, improves the chemical durability, and improves the moldability to the container. It is essential because it improves the performance. In the glass of the present invention, the content of CaO is 2 mol% or more. However, too much is not preferable because it causes deterioration of devitrification characteristics, an increase in linear expansion coefficient, and a decrease in chemical durability. In the glass of the present invention, the content of CaO is 12 mol% or less.
本発明のガラスにおいて、ＳｒＯはＣａＯと同様に、ＢａＯに比べれば線膨張係数を高くせず、化学耐久性を向上させ、容器への成形性を向上させるという特徴を有し、溶解性も向上させ、失透特性を改善するため必須である。本発明のガラスにおいて、ＳｒＯの含有量は２モル％以上である。特に、本発明のガラスがＢａＯを含む場合、ＳｒＯは、後述するＢａＯを含む場合の問題点を改善する効果があるので、２モル％以上含有することが必須である。但し、多く含有しすぎると失透特性の劣化や線膨張係数の増大、化学耐久性の低下をまねくため好ましくない。本発明のガラスにおいて、ＳｒＯの含有量は１２モル％以下である。 In the glass of the present invention, SrO, like CaO, has the characteristics of not increasing the linear expansion coefficient compared to BaO, improving chemical durability, and improving moldability to containers, and improving solubility. And is essential for improving devitrification properties. In the glass of the present invention, the content of SrO is 2 mol% or more. In particular, when the glass of the present invention contains BaO, SrO has an effect of improving the problems when BaO described later is contained, so it is essential to contain 2 mol% or more. However, too much content is not preferable because it causes deterioration of devitrification characteristics, an increase in coefficient of linear expansion, and a decrease in chemical durability. In the glass of the present invention, the content of SrO is 12 mol% or less.
本発明のガラスにおいて、ＢａＯは、溶解性を低下させ、線膨張係数を高くするため、あまり含有させない方が好ましい。ただし、ガラスの分相および失透特性の向上、化学的耐久性の向上、容器への成形性の向上に効果があるため適量含有してもよく、２モル％以上含有することが好ましい。本発明のガラスにおいて、ＢａＯの含有量は１２モル％以下である。 In the glass of the present invention, BaO is preferably not contained so much in order to lower the solubility and increase the linear expansion coefficient. However, since it is effective in improving the phase separation and devitrification characteristics of glass, improving chemical durability, and improving moldability to a container, it may be contained in an appropriate amount, and preferably 2 mol% or more. In the glass of the present invention, the BaO content is 12 mol% or less.
本発明のガラスは、アルカリ土類金属酸化物（ＲＯ）の含有量の総和、すなわちＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが低いとガラスの粘性が高くなり、溶解性が悪化する。本発明のガラスにおいて、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯは１６モル％以上である。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが１６モル％未満であると、粘性がｌｏｇη＝２となる温度（Ｔ2）が１６００℃超となり、ガラスの溶解性が悪化し、容器への成形性が低下する。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯは、好ましくは２０モル％以上である。但し、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが多すぎると線膨張係数が増大する。本発明のガラスにおいて、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯは２８モル％以下である。 In the glass of the present invention, when the total content of alkaline earth metal oxides (RO), that is, MgO + CaO + SrO + BaO is low, the viscosity of the glass increases and the solubility deteriorates. In the glass of the present invention, MgO + CaO + SrO + BaO is 16 mol% or more. When MgO + CaO + SrO + BaO is less than 16 mol%, the temperature (T 2 ) at which the viscosity becomes log η = 2 exceeds 1600 ° C., the solubility of the glass deteriorates, and the moldability to the container decreases. MgO + CaO + SrO + BaO is preferably 20 mol% or more. However, when there is too much MgO + CaO + SrO + BaO, the linear expansion coefficient increases. In the glass of the present invention, MgO + CaO + SrO + BaO is 28 mol% or less.
本発明のガラスは、上記成分以外にガラスの溶解性、清澄性、成形性を改善するため、清澄剤として、Ｆ、Ｃｌ、ＳＯ3、ＳｎＯ2、ＴｉＯ2、ＭｎＯ2、ＣｅＯ2、ＺｒＯ2、Ｆｅ2Ｏ3またはＮｂ2Ｏ5を添加することが好ましく、特にＦ、Ｃｌ、ＳＯ3、ＳｎＯ2、ＴｉＯ2、ＭｎＯ2、ＣｅＯ2、ＺｒＯ2またはＦｅ2Ｏ3を添加することが好ましい。これらは単独で添加してもよく、または２種以上を併用してもよい。添加する場合、Ｆは０〜４ｗｔ％、Ｃｌは０〜４ｗｔ％、ＳＯ3は０〜４ｗｔ％、ＳｎＯ2は０〜４ｗｔ％、ＴｉＯ2は０〜４ｗｔ％、ＭｎＯ2は０〜４ｗｔ％、ＣｅＯ2は０〜４ｗｔ％、ＺｒＯ2は０〜４ｗｔ％であり、Ｆｅ2Ｏ3は０〜２ｗｔ％添加する。前記ｗｔ％は成形後のガラス質量に対する質量％である。但し、過剰泡発生、失透特性の劣化、着色等の問題があるので、総含有量で１５ｗｔ％以下とする。
また、添加による所望の効果を得るためには、１ｐｐｍ以上添加することが好ましい、より好ましくは１０ｐｐｍ以上、さらに好ましくは１００ｐｐｍ以上、さらに好ましくは０．１ｗｔ％以上である。
具体的には、Ｆ＋Ｃｌ＋ＳＯ3＋ＳｎＯ2＋ＴｉＯ2＋ＣｅＯ2＋ＺｒＯ2＋Ｆｅ2Ｏ3は１ｐｐｍ〜１５ｗｔ％が好ましく、またＦ＋Ｃｌ＋ＳＯ3＋ＳｎＯ2＋ＴｉＯ2＋ＭｎＯ2＋ＣｅＯ2＋ＺｒＯ2＋Ｆｅ2Ｏ3が１ｐｐｍ〜１５ｗｔ％であることが特に好ましい。
In addition to the above components, the glass of the present invention improves the solubility, clarification, and moldability of the glass. Therefore, as a clarifier, F, Cl, SO 3 , SnO 2 , TiO 2 , MnO 2 , CeO 2 , ZrO 2 are used. Fe 2 O 3 or Nb 2 O 5 is preferably added, and in particular, F, Cl, SO 3 , SnO 2 , TiO 2 , MnO 2 , CeO 2 , ZrO 2 or Fe 2 O 3 is preferably added. . These may be added alone or in combination of two or more. If added, F is 0~4wt%, Cl is 0~4wt%, SO 3 is 0~4wt%, SnO 2 is 0~4wt%, TiO 2 is 0~4wt%, MnO 2 is 0~4wt%, CeO 2 is 0 to 4 wt%, ZrO 2 is 0 to 4 wt%, and Fe 2 O 3 is added in an amount of 0 to 2 wt%. Said wt% is mass% with respect to the glass mass after molding. However, since there are problems such as generation of excessive bubbles, deterioration of devitrification characteristics, and coloring, the total content is set to 15 wt% or less.
Moreover, in order to obtain the desired effect by addition, it is preferable to add 1 ppm or more, more preferably 10 ppm or more, still more preferably 100 ppm or more, and further preferably 0.1 wt% or more.
Specifically, F + Cl + SO 3 + SnO 2 + TiO 2 + CeO 2 + ZrO 2 + Fe 2 O 3 is preferably 1 ppm to 15 wt%, and F + Cl + SO 3 + SnO 2 + TiO 2 + MnO 2 + CeO 2 + ZrO 2 + Fe 2 O 3 is 1 ppm to 15 wt%. It is particularly preferred.
本発明のガラスは、本発明のガラスを用いて製造する医薬品容器または化粧品容器に関する要求に応じて上記以外の成分を添加してもよい。たとえば、医薬品容器や化粧品容器は無色透明なものもあれば、太陽光による内容物の劣化を防止するために暗色に着色された容器とする場合もある。また、ガラス容器の意匠性を向上するために着色された容器とする場合もある。このため、着色された容器とする目的で、Ｃｏ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ｃｒ、Ｖ、Ｚｎ、Ｂｉ、Ｅｒ、Ｔｍ、Ｎｄ、Ｓｍ、Ｓｎ、Ｃｅ、Ｐｒ、Ｅｕ、Ａｇ、および、Ａｕからなる群から選択される少なくとも１種の元素を着色剤として添加してもよい。 The glass of the present invention may be added with components other than those described above according to the requirements relating to pharmaceutical containers or cosmetic containers manufactured using the glass of the present invention. For example, some pharmaceutical containers and cosmetic containers are colorless and transparent, while others are dark colored containers to prevent deterioration of contents due to sunlight. Moreover, it may be set as the colored container in order to improve the designability of a glass container. Therefore, for the purpose of forming a colored container, Co, Mn, Fe, Ni, Cu, Cr, V, Zn, Bi, Er, Tm, Nd, Sm, Sn, Ce, Pr, Eu, Ag, and At least one element selected from the group consisting of Au may be added as a colorant.
本発明のガラスは、Ｐ2Ｏ5、ＰｂＯ、Ａｓ2Ｏ3、Ｓｂ2Ｏ3およびＺｎＯは、環境を考慮し実質的に含有しないことが好ましい。ここで、実質的に含有しないといった場合、工業原料中の不可避不純物以外には上記成分を含有しないことを意味し、例えば０．１モル％以下である。これらの物質を実質的に含有しないことは、ガラスをリサイクルする上でも好都合である。 The glass of the present invention preferably contains substantially no P 2 O 5 , PbO, As 2 O 3 , Sb 2 O 3 and ZnO in consideration of the environment. Here, when it does not contain substantially, it means not containing the said component other than the inevitable impurity in an industrial raw material, for example, is 0.1 mol% or less. The fact that these substances are not substantially contained is advantageous in recycling the glass.
本発明のガラスは、粘性がｌｏｇη＝７となる温度Ｔ7が９５０℃以下であることが好ましい。上述したように、医薬品や化粧品の容器の成形法としては、ブロー成形やプレス成形が好ましく用いられる。Ｔ7は、これらの成形法での成形性の目安となる温度である。Ｔ7が９５０℃以下であると、ブロー成形やプレス成形で医薬品容器または化粧品容器を成形する上で好ましい。より好ましくは９００℃以下、さらに好ましくは８５０℃以下、さらに好ましくは８００℃以下である。 In the glass of the present invention, the temperature T 7 at which the viscosity becomes log η = 7 is preferably 950 ° C. or lower. As described above, blow molding or press molding is preferably used as a method for molding a pharmaceutical or cosmetic container. T 7 is a temperature that is a measure of moldability in these molding methods. When T 7 is at 950 ° C. or less, preferable for molded pharmaceutical containers or cosmetics containers blow molding or press molding. More preferably, it is 900 degrees C or less, More preferably, it is 850 degrees C or less, More preferably, it is 800 degrees C or less.
本発明のガラスは、粘性がｌｏｇη＝２となる温度Ｔ2が１６００℃以下であることが好ましい。Ｔ2はガラスの溶解性の目安となる温度であり、１６００℃以下であると、ガラスを溶解する上で好ましい。より好ましくは１５５０℃以下であり、さらに好ましくは １５００℃以下である。 In the glass of the present invention, the temperature T 2 at which the viscosity becomes log η = 2 is preferably 1600 ° C. or lower. T 2 is a temperature that is a measure of the solubility of the glass, and it is preferably 1600 ° C. or lower for melting the glass. More preferably, it is 1550 degrees C or less, More preferably, it is 1500 degrees C or less.
本発明のガラスにおいて、ブロー成形やプレス成形で医薬品容器または化粧品容器を成形する温度域で分相が起こると、着色（白色化）や化学耐久性の低下が問題となる。このため、本発明のガラスは、失透温度が１２００℃以下であることが好ましく、より好ましくは１１５０℃以下、さらに好ましくは１１００℃以下である。 In the glass of the present invention, when phase separation occurs in a temperature range in which a pharmaceutical container or a cosmetic container is molded by blow molding or press molding, coloring (whitening) and chemical durability are problematic. For this reason, the glass of the present invention preferably has a devitrification temperature of 1200 ° C. or lower, more preferably 1150 ° C. or lower, and further preferably 1100 ° C. or lower.
本発明のガラスは、５０〜３５０℃における平均熱膨張係数は８０×１０-7／℃以下であることが好ましい。本発明のガラスを用いて製造する医薬品容器または化粧品容器は、蓋付きの容器とする場合もある。このような場合に、ガラスの熱膨張係数が大きいと、温度変化により、容器の密閉性が低下するおそれがある。５０〜３５０℃における平均熱膨張係数は８０×１０-7／℃以下であると、蓋付き容器とした場合に、温度変化により容器の密閉性が低下するおそれがない。より好ましくは７０×１０-7／℃以下、さらに好ましくは６０×１０-7／℃以下である。 The glass of the present invention preferably has an average coefficient of thermal expansion of 50 × 10 −7 / ° C. or less at 50 to 350 ° C. The pharmaceutical container or cosmetic container manufactured using the glass of the present invention may be a container with a lid. In such a case, if the coefficient of thermal expansion of the glass is large, the hermeticity of the container may be lowered due to a temperature change. When the average thermal expansion coefficient at 50 to 350 ° C. is 80 × 10 −7 / ° C. or less, there is no possibility that the sealing property of the container is lowered due to temperature change when a container with a lid is used. More preferably, it is 70 × 10 −7 / ° C. or less, and further preferably 60 × 10 −7 / ° C. or less.
本発明のガラスは、クラック抵抗の値が、好ましくは７００ｇｆ以上、より好ましくは８００ｇｆ以上、更に好ましくは９００ｇｆ以上、もっとも好ましくは１０００ｇｆ以上である。クラック抵抗の値は、ガラスの傷つきやすさを表す数値である。クラック抵抗値が７００ｇｆより低いと、医薬品容器や化粧品容器に成形する際に傷がつき易くなり、ガラスの機械的強度が低下し易くなる。 The glass of the present invention has a crack resistance value of preferably 700 gf or more, more preferably 800 gf or more, still more preferably 900 gf or more, and most preferably 1000 gf or more. The value of the crack resistance is a numerical value that indicates how easily glass is damaged. When the crack resistance value is lower than 700 gf, the glass tends to be damaged when molded into a pharmaceutical container or a cosmetic container, and the mechanical strength of the glass tends to be lowered.
本発明のガラスは、ヨーロッパ薬局方第7.0版 3.2（European Pharmacopeia 7.0 3.2 Containers, 3.2.1 Glass containers for pharmaceutical us, Test B. Hydrolytic resistance of glass grains）に記載の耐水性試験における中和滴定で使用される塩酸消費量が０．０３ｍｌ／ｇ・ｇｌａｓｓ以下であることが好ましい。塩酸消費量が０．０３ｍｌ／ｇ・ｇｌａｓｓより多いと、すなわちガラスからのアルカリ溶出量が多いと、医薬品容器として用いた場合に、充填された薬剤が変質し易くなる傾向がある。したがって、上記塩酸消費量は、より好ましくは、０．０２ｍｌ／ｇ・ｇｌａｓｓ以下、もっとも好ましくは０．０１ｍｌ／ｇ・ｇｌａｓｓ以下である。 The glass of the present invention is used in neutralization titration in a water resistance test described in European Pharmacopeia 7.0 edition 3.2 (European Pharmacopeia 7.0 3.2 Containers, 3.2.1 Glass containers for pharmaceutical us, Test B. Hydrolytic resistance of glass grains). The amount of hydrochloric acid consumed is preferably 0.03 ml / g · glass or less. If the amount of hydrochloric acid consumed is more than 0.03 ml / g · glass, that is, if the amount of alkali elution from the glass is large, when used as a pharmaceutical container, the charged medicine tends to be easily altered. Therefore, the consumption of hydrochloric acid is more preferably 0.02 ml / g · glass or less, and most preferably 0.01 ml / g · glass or less.
本発明のガラスは、例えば次のような方法で製造できる。
通常使用される各成分の原料を目標成分になるように調合し、これを溶解炉に連続的に投入し、１５００℃〜１６６０℃の温度範囲、好ましくは１５００℃〜１６００℃の温度範囲に加熱して溶融する。この溶融ガラスをブロー成形またはプレス成形により医薬品容器または化粧品容器に成形する。
The glass of the present invention can be produced, for example, by the following method.
The raw materials of each component that are usually used are prepared so as to become target components, which are continuously charged into a melting furnace and heated to a temperature range of 1500 ° C to 1660 ° C, preferably 1500 ° C to 1600 ° C. And melt. This molten glass is formed into a pharmaceutical container or a cosmetic container by blow molding or press molding.
上記の手順で製造された医薬品容器や化粧品容器は、必要に応じて表面処理を施してもよい。たとえば、容器の意匠性向上のため、容器外面にフロスト処理を施してもよい。 The pharmaceutical container and the cosmetic container manufactured by the above procedure may be subjected to surface treatment as necessary. For example, a frost treatment may be applied to the outer surface of the container to improve the design of the container.
以下に、実施例を用いて本発明を詳細に説明する。ただし、本発明はこれに限定されるものではない。
（実施例１、比較例１）
下記表に実施例１、および、比較例１のガラスの組成をモル％で示した。
各成分の原料を、成形後のガラスが下記に示す組成になるように調合し、白金坩堝を用いて１５００〜１６６０℃の温度で溶解した。溶解にあたっては、白金スターラーを用い撹拌しガラスの均質化を行った。次いで溶解ガラスをそのまま流し出し所望の厚さの板状に成形した後、徐冷して実施例１および比較例１のガラスを得た。また、実施例１のガラスを用いて、宙吹き（フリーブロー）により、直径が８ｃｍで高さが９ｃｍのガラス容器を作製した。
下記表には、得られたガラスの特性として、５０℃〜３５０℃における平均線膨張係数（×１０-7／℃））、ブロー成形やプレス成形での成形性の目安となる、ｌｏｇη＝７（ポイズ）となる温度Ｔ7（℃）、溶解性の目安となるｌｏｇη＝２（ポイズ）となる温度Ｔ2（℃）、および、失透温度（℃）を示した。下記表に示す各項目は、各々以下に示す手順で測定または計算した。
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this.
(Example 1, Comparative Example 1)
The composition of the glass of Example 1 and Comparative Example 1 is shown in mol% in the following table.
The raw materials of each component were prepared so that the glass after molding had the composition shown below, and melted at a temperature of 1500 to 1660 ° C. using a platinum crucible. In melting, the mixture was stirred using a platinum stirrer to homogenize the glass. Next, the molten glass was poured out as it was, formed into a plate having a desired thickness, and then slowly cooled to obtain the glass of Example 1 and Comparative Example 1. Further, using the glass of Example 1, a glass container having a diameter of 8 cm and a height of 9 cm was produced by air blowing (free blow).
In the table below, as a characteristic of the obtained glass, an average linear expansion coefficient (× 10 −7 / ° C.) at 50 ° C. to 350 ° C., log η = 7, which is a measure of formability in blow molding or press molding, is shown. The temperature T 7 (° C.) at which (poise) is obtained, the temperature T 2 (° C.) at which log η = 2 (poise), which is a measure of solubility, and the devitrification temperature (° C.) are shown. Each item shown in the following table was measured or calculated by the following procedure.
［平均熱膨張係数］
５０℃〜３５０℃の平均線膨脹係数は指差熱膨張計（ＴＭＡ）を用いて測定した。
［Ｔ7、Ｔ2］
Ｔ7およびＴ2は、回転粘度計を用いて測定した。
［失透温度］
失透温度は、複数のガラス片をそれぞれ異なる温度で１７時間加熱溶解し、結晶が析出しているガラスの中で最も温度が高いガラスのガラス温度と結晶が析出していないガラスの中で最も温度が低いガラスのガラス温度との平均値を失透温度とした。
The average linear expansion coefficient between 50 ° C. and 350 ° C. was measured using a differential thermal dilatometer (TMA).
[T 7, T 2]
T 7 and T 2 were measured using a rotational viscometer.
[Devitrification temperature]
The devitrification temperature is determined by heating and melting a plurality of glass pieces at different temperatures for 17 hours, and the glass temperature of the glass having the highest temperature among the glasses in which crystals are precipitated and the glass in which no crystals are precipitated are the most. The average value with the glass temperature of glass with low temperature was made into the devitrification temperature.
本発明のガラスは、ブロー成形やプレス成形により、医薬品容器や化粧品容器を成形するのに好適である。 The glass of the present invention is suitable for forming a pharmaceutical container or a cosmetic container by blow molding or press molding.
Claims (3)
ＳｉＯ2 ５５〜６４％、
Ａｌ2Ｏ3 ６〜１４％、
Ｂ2Ｏ3 ５〜１０％、
ＭｇＯ ２〜１２％、
ＣａＯ ２〜１２％、
ＳｒＯ ２〜１２％、
ＢａＯ ０〜１２％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １６〜２８％
よりなり、アルカリ金属酸化物を実質的に含有せず、ガラス粘度がｌｏｇη＝７となる温度Ｔ7が９５０℃以下である、医薬品または化粧品の容器用ガラス。 In terms of mol%,
SiO 2 55~64%,
Al 2 O 3 6-14%,
B 2 O 3 5-10%,
MgO 2-12%,
CaO 2-12%,
SrO 2-12%,
BaO 0-12%,
MgO + CaO + SrO + BaO 16-28%
A glass for a pharmaceutical or cosmetic container, which is substantially free of alkali metal oxide and has a temperature T 7 at which the glass viscosity becomes log η = 7 is 950 ° C. or lower.
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| US5508237A (en) * | 1994-03-14 | 1996-04-16 | Corning Incorporated | Flat panel display |
| DE19739912C1 (en) * | 1997-09-11 | 1998-12-10 | Schott Glas | New alkali-free aluminoborosilicate glass |
| JP5109225B2 (en) * | 2003-12-26 | 2012-12-26 | 旭硝子株式会社 | Alkali-free glass and liquid crystal display panel |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |