CN104261676A - Neutral borosilicate glass and application thereof - Google Patents

Abstract

The invention relates to a pharmaceutical neutral borosilicate glass, the composition (by weight, based on oxides) is: SiO ₂ 70.0-80.0, B ₂ O ₃ 7.0-12.0, Al ₂ O ₃ 1.5-5.0, Na ₂ O 5.5-8.0, K ₂ O 0-1.0, Li ₂ O 0-1.5, CaO 1.5-3.0, BaO 0-3.5, MgO 0-2.0, NaCl 0.3-0.5, Na ₂ O+K ₂ O+Li ₂ O 6.0-9.5, CaO+BaO+MgO 1.5-6. It is a pharmaceutical neutral borosilicate glass that complies with the national pharmaceutical packaging container (material) standard YBB00022005-2, and is suitable for primary packaging materials for pharmaceuticals, such as ampoules, cartridges, and vials.

Description

A kind of neutral borosilicate glass and its application

technical field

The invention relates to a neutral borosilicate glass and its application.

Background technique

Medicinal neutral borosilicate glass is recognized as the best pharmaceutical packaging material in the world today, with stable chemical properties, first class water resistance, first class acid resistance, and second class alkali resistance. In developed countries such as the United States, Japan, and Europe, neutral borosilicate glass has been compulsorily used as the primary packaging material for injections, while soda-lime silica glass or semi-neutral glass with a thermal expansion coefficient of 7.0×10 ^-6 K ^-1 is generally used for pharmaceutical packaging in China. For borosilicate glass products, when these two packaging materials contain drugs with a high pH value, the amount of potassium and sodium precipitated exceeds the standard, and the drug and glass undergo a compatibility reaction, resulting in the clarity of the aqueous injection not meeting the standard, and the phenomenon of peeling off is very common, seriously endangering People's drug safety. Therefore, in order to ensure drug safety and meet international standards, it is imperative to replace soda-lime glass or semi-neutral borosilicate glass with neutral borosilicate glass.

At present, there are few domestic studies on the formulation of pharmaceutical neutral borosilicate glass whose performance meets the national drug packaging container (material) standard YBB00022005-2, especially borosilicate glass with a linear thermal expansion coefficient of 4.0-5.0*10 ^-6 K ^-1 The formulation research is less. For example, the linear thermal expansion coefficient α _20-300°C of the borosilicate glass involved in CN1203018C and CN101717189B is >5-6.0*10 ^-6 K ^-1 , and its thermal expansion coefficient fails to meet the requirements of the YBB standard. CN 101462824B belongs to the technical field of glass containing aluminum, boron, and 30% to 60% (weight) silicon dioxide, and its linear thermal expansion coefficient is 6.5-7.5*10 ^-6 K ^-1 , which is "semi-neutral borosilicate glass" . CN103058518A adds 1.0-2.5% coloring agent _Fe2O3 and _0.02-0.06 % CoO to the basic formula of borosilicate glass, so that the borosilicate glass is dark gray, and the visible light transmittance is 16-20%, but its linear thermal expansion coefficient α _20-300°C is 3.3±0.15*10 ^-6 K ^-1 , which cannot meet the performance requirements of pharmaceutical neutral borosilicate glass.

Contents of the invention

Summary of the invention

The purpose of the present invention is to provide a pharmaceutical neutral borosilicate glass that meets the national drug packaging container (material) standard YBB00022005-2 to solve the problems existing in the existing primary pharmaceutical packaging materials.

In order to achieve the above object, the technical solution of the first aspect of the present invention provides a neutral borosilicate glass, the composition of which is based on oxides by weight %:

Wherein, Na ₂ O+K ₂ O+Li ₂ O is 6.0-9.5 by weight % based on the oxide, and CaO+BaO+MgO is 1.5-6 by weight % based on the oxide.

The technical solution of the second aspect of the present invention provides the use of the above-mentioned neutral borosilicate glass as a pharmaceutical packaging material, and the pharmaceutical packaging material includes ampoules, cartridges, and vials.

Detailed description of the invention

According to the neutral borosilicate glass provided by the technical solution of the first aspect of the present invention, the content of SiO ₂ in the glass is 70.0-80.0% by weight, and the content of Al ₂ O ₃ is 1.5-5.0% by weight. SiO ₂ and Al ₂ O ₃ can increase the high-temperature viscosity of the glass, thereby reducing the volatilization of boric acid during the high-temperature melting process. At the same time, the two can reduce the thermal expansion coefficient of the glass and improve the thermal and chemical stability of the glass; If it is too low, boron volatilization cannot be reduced as much as possible. If it is too high, the high temperature viscosity will be too high, resulting in too high molding temperature, and the thermal _expansion coefficient will be lower than _4.0 *10 ^-6 K ^-1 ; The acid resistance does not meet the grade 1 standard.

The content of B ₂ O ₃ in the glass is 7.0-12.0% by weight. An appropriate amount of _B2O3 can reduce the melting temperature and molding temperature, reduce the linear thermal expansion coefficient of the glass, and improve the thermal and chemical stability of the glass. If the content is too low, the high temperature viscosity of _the glass is high, and the molding temperature is high. , the acid resistance of the glass deteriorates.

The content of Na ₂ O in the glass is 5.5-8.0% by weight, the content of K ₂ O is 0-1.0% by weight, the content of Li ₂ O is 0-1.5% by weight, ∑Na ₂ O+K ₂ O+Li ₂ O The content is 6-9% by weight. An appropriate amount of alkali metal oxide can reduce the melting temperature and high-temperature viscosity of the glass, making the glass easy to melt. If the content is too high, the linear thermal expansion coefficient>5.0*10 ^-6 K ^-1 , and the chemical stability of the glass will deteriorate. The introduction of K ₂ O will rapidly increase the coefficient of linear thermal expansion, the content should be less than 1% by weight, and the introduction of Li ₂ O should not be too much, because this component is more corrosive to refractory materials. In addition, considering factors such as cost, the amount of K ₂ O and Li ₂ O should be lower than the maximum content of the present invention, and the others should be introduced by Na ₂ O.

The content of CaO in the glass is 1.5-3.0% by weight, the content of BaO is 0-3.5% by weight, the content of MgO is 0-2.0% by weight, and ΣCaO+BaO+MgO≤6.0% by weight. A small amount of CaO can improve the acid resistance of the glass, a small amount of BaO can reduce the melting temperature and high temperature viscosity, and a small amount of MgO can slow down the hardening speed of the glass and improve the formability of the glass. However, the content of alkali metal should not be too high, because alkaline earth metal oxides are easy to react with drugs and destroy drug properties.

The NaCl content in the glass as a fining agent is 0.3-0.5% by weight. An appropriate amount of NaCl vaporizes and volatilizes at high temperature, which can promote the clarification of the glass, and too much NaCl can emulsify the glass.

In some embodiments, its composition is based on oxides in weight %:

In some embodiments, the neutral borosilicate glass is tested according to the standard GB/T 16920-1997, and the linear thermal expansion coefficient α _20-300°C is 4.0-5.0*10 ^-6 K ^-1 .

In some embodiments, the neutral borosilicate glass is tested according to the national drug packaging container (material) standard YBB00022005-2, the water resistance of the particle method at 98°C is grade 1, the water resistance of the particle method at 121°C is grade 1, and the acid resistance is grade 1. Alkali resistance grade 2, glass transition temperature T _g 560-605°C, expansion softening temperature T _f 640-685°C, density ρ2.2-2.4g/cm ³ .

All ranges cited herein are inclusive of endpoints unless expressly stated to the contrary. For example, "the content of CaO in the glass is 1.5-3.0% by weight" means that the percentage W of CaO in the glass is in the range of 1.5≤W≤3.0.

Numerals herein are approximate, regardless of whether words such as "about" or "approximately" are used. Numerical values may vary by 1%, 2%, 5%, 7%, 8%, 10%. Whenever a number with a value of N is disclosed, any number with N+/-1%, N+/-2%, N+/-3%, N+/-5%, N+/-7%, N+/-8%, or N+ Figures for values of /-10% are explicitly disclosed, where "+/-" means plus or minus, and ranges between N-10% and N+10% are also disclosed. For example, for "clarifier NaCl content 0.3% by weight", there are 0.3%*(1+/-1%), 0.3%*(1+/-2%), 0.3%*(1+/-3% ), 0.3%*(1+/-5%), 0.3%*(1+/-7%), 0.3%*(1+/-8%) and 0.3%*(1+/-10%) The value is disclosed at the same time, and at the same time, the concentration range between 0.3%*(1-10%) and 0.3%*(1+10%) also belongs to the disclosed range, that is, the value between 0.27%-0.33%, all Within the scope of clarification agent NaCl content.

Detailed ways

What is described below is the preferred implementation of the present invention, and the protection of the present invention is not limited to the following preferred implementation. It should be pointed out that for those skilled in the art, some modifications and improvements made on the basis of this inventive concept all belong to the protection scope of the present invention. The raw materials used in the examples are all commercially available.

Example

According to the formula in Table 1, the glass raw materials with a total weight of 300g were accurately weighed and mixed evenly. 5°C/min, the clarification time is 4 hours, then take out the crucible, pour the glass liquid into the preheated graphite mold, after forming, put the sample into the annealing furnace, the annealing temperature is 560°C±20°C, keep warm The time is half an hour. Cut or grind the glass blocks into blocks, strips, flakes, granules or powder samples of the size specified in YBB00022005-2, the size of the sample required for the 98°C water resistance test is 300μm-500μm, and the required size for the 121°C water resistance test The size of the sample is 600μm-1000μm, the total surface area of the sample required for the acid resistance test is 100±10cm ² , the total surface area of the sample required for the alkali resistance test is 10-15cm ² , and the size of the sample required for the linear thermal expansion coefficient is 4* 4*24.5mm.

The obtained samples were tested to measure their water resistance at 98°C by particle method, water resistance at 121°C by particle method, alkali resistance, acid resistance, linear thermal expansion coefficient α _20-300°C (*10 ^-6 K ^-1 ), glass transition temperature (°C ), glass expansion softening temperature (°C), density (mg/dm ² ). Among them, the water resistance of the granule method at 98°C is tested according to YBB00362004, the water resistance of the granule method at 121°C is tested according to YBB00252003, the alkali resistance is tested according to YBB00352004, the acid resistance is tested according to YBB00342004, and the coefficient of thermal expansion is tested according to the standard GB/T 16920-1997. The test results are shown in Table 2 .

The glass component composition of table 1 embodiment 1-7

Table 2 The test results of Examples 1-7.

From the test results of Examples 1-7, it can be seen that the borosilicate glass prepared according to the formula of the present invention has a grade 1 water resistance by the particle method at 98°C, a grade 1 water resistance by the particle method at 121°C, a grade 1 acid resistance, and a grade 1 alkali resistance. Grade 2, linear thermal expansion coefficient α _20-300℃ 4.0-5.0*10 ^-6 K ^-1 , glass transition temperature Tg 560-590℃, expansion softening temperature Tf 640-670℃, density ρ2.2-2.4g/cm ^3. Meet the performance requirements of the national drug packaging container (material) standard YBB00022005-2.

Claims (5)

1. a neutral boron silica glass, is characterized in that, it forms % by weight and based on oxide basis is:

Wherein, Na ₂o+K ₂o+Li ₂o by weight % based on oxide basis be 6.0-9.5, CaO+BaO+MgO by weight % be 1.5-6 based on oxide basis.

2. neutral boron silica glass according to claim 1, is characterized in that, it forms % by weight and based on oxide basis is:

3. neutral boron silica glass according to claim 1, is characterized in that, described neutral boron silica glass is tested according to standard GB/T16920-1997, coefficient of linear thermal expansion α _{20-300 DEG C}for 4.0-5.0*10 ^-6k ^-1.

4. neutral boron silica glass according to claim 1, is characterized in that, described neutral boron silica glass is tested according to standard YBB00022005-2,98 DEG C of particle method water tolerance 1 grade, 121 DEG C of particle method water tolerance 1 grade, acid resistance 1 grade, alkali resistance 2 grades, glass transformation temperature T _g560-605 DEG C, expansion softening temperature Tf 640-685 DEG C, density p 2.2-2.4g/cm ³.

5. as described in any one of claim 1-4, neutral boron silica glass is used for the purposes as acceptable packaging material, and described drug packing material comprises ampoule, clamped bottle, cillin bottle.