Glass for pharmaceutical packaging and preparation method thereof

Abstract

The invention relates to glass for pharmaceutical packaging and a preparation method thereof. The raw materials of the glass for pharmaceutical packaging include the following components in percentage by weight: 54-65% of silica sand, 12-21% of lithium feldspar, 10-18% of anhydrous borax, 1-6% of aluminum oxide, 0.2-5% of soda ash, 1-5% of titanium dioxide, 0.5-4% of barium carbonate, 0.1-3% of potassium carbonate, 1-3% of zircon powder, 0-2% of dolomite, 0.4-1.2% of sodium sulfate, and 0.1-0.4% of stannous oxide. The lithium feldspar contains Al2O3, SiO2, Li2O, Na2O, and K2O components, wherein Li2O+Na2O+K2O is greater than or equal to 8.0wt%, and the ratio of Li2O / (Li2O+Na2O+K2O) is between 0.2 and 0.5. Different from the existing technology, the above technical solution can obtain pharmaceutical packaging glass with good chemical durability and high ultraviolet shielding ability through the design of components and content, which is suitable for the pharmaceutical packaging field.

Description

Technical Field

[0001] The present application relates to the field of glass, and in particular to glass for pharmaceutical packaging and a preparation method thereof. Background Art

[0002] Glass has long been the preferred material for pharmaceutical packaging due to its superior properties compared to other materials, including airtightness, chemical durability, excellent glossiness, and ease of disinfection. However, traditional pharmaceutical packaging glass can undergo physical and chemical reactions when in contact with some new drugs. For example, some drugs are sensitive to metal ions. If metal ions in the glass migrate into the drug solution, they can catalyze certain degradation reactions of the drug, causing the solution color to darken and even produce precipitation and visible foreign matter. The migration of alkali metal ions in the glass also causes changes in the pH value of the drug solution. These changes can cause the drug to lose its effectiveness during its shelf life and even pose safety risks. In addition, certain drugs, such as injectables, can affect the tolerance of the inner surface of traditional pharmaceutical glass, reducing the protective effect of the glass container and even causing damage to the glass network structure. This can lead to the dissolution of large amounts of components and the generation of glass chips or flakes, causing safety issues.

[0003] With the development of modern medicine and the improvement of people's health and medical needs, higher requirements are placed on glass materials used in pharmaceutical packaging. Especially in recent years, due to the rapid progress of medicine, many types of biopharmaceuticals and new drugs have been produced. The drugs filled in pharmaceutical containers have changed. There are more and more new drugs such as biological agents, vaccines or anticancer agents. In addition, the emergence of some other more acidic or alkaline drugs has put forward higher requirements on the chemical durability of pharmaceutical glass materials.

[0004] Glass materials used in pharmaceutical packaging include colorless transparent glass and tinted glass. Tinted glass packaging containers require UV shielding to protect the pharmaceuticals contained within from deterioration due to light exposure. However, this type of tinted glass is difficult to melt during production due to its low light transmittance. After melting, the glass may exhibit defects such as numerous bubbles and unstable quality. Summary of the Invention

[0005] In response to the above-mentioned issues, the present application provides a pharmaceutical packaging glass with excellent chemical durability and high UV shielding capabilities, suitable for use in the pharmaceutical packaging field. Specifically, the present invention addresses the difficulties encountered during glass manufacturing, such as the difficulty in melting glass, the numerous internal defects such as bubbles after melting, and the resulting unstable quality, while also enabling low-cost production.

[0006] A first aspect of the present invention provides a glass for pharmaceutical packaging, wherein the raw materials of the glass for pharmaceutical packaging include the following components in percentage by mass:

[0007] Silica sand 54-65%

[0008] Lithium feldspar 12-21%

[0009] Anhydrous borax 10-18%

[0010] Alumina 1~6%

[0011] Soda ash 0.2~5%

[0012] Titanium dioxide 1~5%

[0013] Barium carbonate 0.5-4%

[0014] Potassium carbonate 0.1-3%

[0015] Zircon powder 1~3%

[0016] Dolomite 0~2%

[0017] Sodium sulfate 0.4~1.2%

[0018] Stannous oxide 0.1~0.4%

[0019] The lithium feldspar contains Al2O3, SiO2, Li2O, Na2O, and K2O components, and Li2O+Na2O+K2O≥8.0wt%, and the ratio of Li2O / (Li2O+Na2O+K2O) is between 0.2 and 0.5.

[0020] In the present invention, the use of lithium feldspar is mainly to introduce Li2O and Al2O3. On the one hand, Li2O can reduce the viscosity of glass more than Na2O and K2O, which is more conducive to the melting of glass. On the other hand, the Al2O3 provided by lithium feldspar reduces the amount of alumina powder used. At the same time, lithium feldspar also provides some SiO2, which also reduces the amount of silica sand used. The reduction in the amount of silica sand and alumina powder reduces the glass melting temperature, facilitates clarification and homogenization, and easily forms glass with fewer bubbles. It is known that Li + In the glass network structure, Na + and K + Because it has a strong agglomeration effect, replacing some Na2O and K2O with Li2O, while maintaining a constant alkali metal content, can also reduce the amount of alkali metal ion precipitation when pharmaceutical packaging glass comes into contact with pharmaceuticals, thereby enhancing the chemical durability of pharmaceutical packaging glass. Furthermore, using lithium feldspar to introduce Li2O can significantly reduce the raw material cost of introducing Li2O from lithium oxides or salts.

[0021] In the present invention, the total alkali content in the lithium feldspar is Li2O+Na2O+K2O≥8.0%. The mixed alkali can help melt the raw materials, especially the refractory raw material components such as alumina powder, zircon powder, and silica sand, effectively reduce the melting temperature, and improve the melting quality; at the same time, the lithium feldspar also introduces the alumina and silica required for pharmaceutical glass. These components have achieved good combination with the mixed alkali when introduced, making it easier to melt and manufacture; in addition, the mixed alkali introduced by the lithium feldspar can reduce the gas rate in the molten glass compared to introducing the alkali entirely through carbonate (in addition, it can reduce the cost by more than 4 times compared to introducing the alkali through carbonate), making it easier to manufacture glass for pharmaceutical packaging with less or no bubbles. When the content of Li2O+Na2O+K2O is lower than 8%, it means that the quality of the lithium feldspar ore source is not high, and there are many other unnecessary impurities associated with it, which is not suitable for pharmaceutical glass raw materials, so the lower limit of the total alkali content should be limited. Furthermore, due to the Li2O provided by Li2O in the glass, the Li + The aggregation effect of Li2O can reduce the thermal expansion coefficient of pharmaceutical glass, improve the light-shielding and ultraviolet (external radiation) interception performance, and also contribute to the water resistance of pharmaceutical glass. Therefore, the lower limit of its proportion should be limited. In addition, considering the synergistic effect of mixed alkali, the upper limit should also be limited. Therefore, the proportion of Li2O in the total alkali content is 0.2-0.5.

[0022] In the present invention, B2O3 is primarily introduced from anhydrous borax. B2O3 can promote the formation of a glass network structure, reduce the thermal expansion coefficient of glass, and promote glass melting. Furthermore, B2O3 in the glass network structure can inhibit the migration of alkali metal ions, thereby improving the chemical stability of the glass. Borax containing water of crystallization is not used because, during the manufacturing process of the pharmaceutical glass, a platinum channel is often used as a molten glass conveying device. Water (β-OH) in the glass is easily pyrolyzed into hydrogen and oxygen on the platinum channel tube wall. Hydrogen escapes from the platinum tube wall, while oxygen remains on the tube inner wall, forming oxygen bubble defects, which is not conducive to the production of glass with no bubbles or a small number of bubbles.

[0023] In the present invention, TiO2 is introduced via titanium dioxide, while ZrO2 is primarily introduced via zircon powder. TiO2 is essential for glass coloring. ZrO2 not only reduces the thermal expansion coefficient of glass, increases its density, and enhances its strength, but also improves its alkali resistance. Furthermore, ZrO2 increases the glass's refractive index, enhancing the UV shielding properties that it, along with TiO2, provides for glass used in pharmaceutical packaging.

[0024] In the present invention, CaO and MgO are primarily introduced via dolomite, and BaO is introduced via barium carbonate. Alkaline earth metal oxides reduce glass viscosity and improve its resistance to devitrification. Furthermore, while maintaining the total alkaline earth metal oxide content, increasing the BaO content effectively suppresses the dissolution of glass components.

[0025] The present invention uses a combination of sodium sulfate and stannous oxide as essential clarifier components. SnO exhibits reducing properties, which can lower the decomposition temperature of sodium sulfate. More importantly, SnO first oxidizes to SnO2 during its clarification process. During the high-temperature period of the melting process, around 1600°C to 1650°C, SnO2 releases O2 in a concentrated manner. This results in a better clarification effect than using tin oxide directly as a clarifier, making it easier to produce glass with no bubbles or a low bubble content.

[0026] This technical solution utilizes lithium feldspar, which not only primarily provides Li₂O and Al₂O₃ in the glass and supplements the SiO₂ primarily provided by silica sand, but also provides some Na₂O, K₂O, and small amounts of CaO and MgO. Li₂O, Na₂O, and K₂O can reduce glass viscosity and improve its melting properties. Crucially, controlling the Li₂O+Na₂O+K₂O ratio to ≥8.0 wt% and the Li₂O / (Li₂O+Na₂O+K₂O) ratio to between 0.2 and 0.5 creates a mixed alkali effect, increasing the glass's solubility without excessively increasing the thermal expansion coefficient. In particular, the introduction of an appropriate amount of Li₂O inhibits ion precipitation and improves the glass's hydrolysis resistance.

[0027] Different from the existing technology, this technical solution uses more common raw materials with relatively low cost, especially the use of lithium feldspar, dolomite, stannous oxide, etc., which can not only greatly reduce the cost of raw materials but also achieve high-quality production. This technical solution can produce glass with no bubbles or low bubble content; the obtained glass for pharmaceutical packaging has good chemical durability, reaching the acid and alkali resistance level 1 of the national pharmaceutical packaging material standard for pharmaceutical glass (YBB-2015 standard), the hydrolysis stability meets the European Pharmacopoeia 7.0 standard, and has outstanding ultraviolet shielding ability.

[0028] Furthermore, the raw materials of the glass for pharmaceutical packaging include the following components in percentage by mass:

[0029] Silica sand 55-62%

[0030] Lithium feldspar 14-19%

[0031] Anhydrous borax 11.5~16.4%

[0032] Alumina 1.5-5%

[0033] Soda ash 0.3~4%

[0034] Titanium dioxide 1~3.5%

[0035] Barium carbonate 0.8-3%

[0036] Potassium carbonate 0.2-2.5%

[0037] Zircon powder 1.5~2.5%

[0038] Dolomite 0.1~1.5%

[0039] Sodium sulfate 0.5~1%

[0040] Stannous oxide 0.15-0.25%;

[0041] The lithium feldspar contains Al2O3, SiO2, Li2O, Na2O, and K2O components, and Li2O+Na2O+K2O≥8.5wt%, and the ratio of Li2O / (Li2O+Na2O+K2O) is between 0.3 and 0.5.

[0042] Furthermore, the average thermal expansion coefficient of the glass for pharmaceutical packaging in the temperature range of 25 to 300°C is 48×10 -7 / ℃~56×10 -7 / ℃.

[0043] Furthermore, the glass for pharmaceutical packaging reaches 10 2.3 The viscosity of Poise is below 1670℃;

[0044] Furthermore, the glass for pharmaceutical packaging is 4 The working point temperature under the viscosity of Poise is lower than 1230℃;

[0045] Furthermore, the liquidus temperature of the glass for pharmaceutical packaging is lower than 1100°C.

[0046] Furthermore, the glass for pharmaceutical packaging has a thickness of 2 mm and a light transmittance of less than 18% at a wavelength of 290 to 450 nm, preferably less than 16%, and most preferably less than 14%.

[0047] Furthermore, the glass for pharmaceutical packaging complies with the requirements of the YBB-2015 national pharmaceutical packaging material standard for pharmaceutical glass and the European Pharmacopoeia 7.0 standard.

[0048] The acid resistance and alkali resistance both reach level 1 of the national pharmaceutical packaging material standard (YBB-2015 standard), and the hydrolysis resistance is excellent for the glass for pharmaceutical packaging of the present invention.

[0049] The consumption of 0.02 mol / L hydrochloric acid per unit mass of glass in the 121°C particle method hydrolysis stability test was less than 0.030 ml, which meets the European Pharmacopoeia 7.0 standard.

[0050] Furthermore, the glass for pharmaceutical packaging has a thickness of 2 mm and contains no more than one bubble with a diameter of 100 μm or more per 100 square centimeters.

[0051] The present invention also provides a method for preparing glass for pharmaceutical packaging, comprising the following steps:

[0052] Mixing: The above raw materials are uniformly mixed according to the component formula to obtain a mixture;

[0053] Melting: The mixture melts at a certain temperature to obtain molten glass;

[0054] Molding: After the glass liquid is clarified and homogenized, it enters the mold for molding;

[0055] Annealing: The formed glass is annealed at a temperature, and the glass for pharmaceutical packaging is obtained after the temperature is naturally lowered.

[0056] Furthermore, in the melting step, the melting temperature is 1600° C. to 1650° C., and the melting time is 4 to 6 hours.

[0057] Furthermore, in the annealing step, the annealing temperature is 580° C. to 620° C., and the annealing time is 2 to 3 hours.

[0058] The above-mentioned records related to the invention content are only an overview of the technical solution of this application. In order to enable ordinary technicians in this field to more clearly understand the technical solution of this application, and then implement it according to the written contents of the specification, and to make the above-mentioned purposes and other purposes, features and advantages of this application easier to understand, the following is an explanation in combination with the specific implementation methods of this application. DETAILED DESCRIPTION

[0059] In order to explain the technical content, structural features, achieved objectives and effects of the technical solution in detail, the following is a detailed description in conjunction with specific embodiments.

[0060] In order to explain in detail the possible application scenarios, technical principles, specific solutions that can be implemented, and the purpose and effects achieved by this application, the following is a detailed description of the specific embodiments listed. The embodiments described herein are only used to more clearly illustrate the technical solutions of this application and are therefore only examples and are not intended to limit the scope of protection of this application.

[0061] References to "embodiments" herein mean that the specific features, structures, or characteristics described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the word "embodiment" in various places in the specification does not necessarily refer to the same embodiment, nor does it particularly limit its independence or relevance to other embodiments. In principle, in this application, as long as there are no technical contradictions or conflicts, the various technical features mentioned in the embodiments can be combined in any manner to form a corresponding implementable technical solution.

[0062] Unless otherwise defined, the technical terms used herein have the same meanings as those generally understood by those skilled in the art to which this application belongs; the use of relevant terms herein is only for describing specific embodiments and is not intended to limit this application.

[0063] In the description of this application, the term "and / or" is used to describe a logical relationship between objects, indicating that three relationships can exist. For example, A and / or B means: A exists, B exists, and both A and B exist. In addition, the character " / " in this document generally indicates that the objects before and after are in a logical "or" relationship.

[0064] In this application, terms such as "first" and "second" are merely used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual quantity, priority or sequence relationship between these entities or operations.

[0065] Without further limitations, in this application, the words "include", "comprise", "have" or other similar expressions used in the sentences are intended to cover non-exclusive inclusion. These expressions do not exclude the presence of additional elements in the process, method or product including the elements, so that the process, method or product including a series of elements may include not only those defined elements, but also other elements not explicitly listed, or elements inherent to such process, method or product.

[0066] Consistent with the understanding in the Examination Guidelines, in this application, expressions such as "greater than," "less than," and "exceed" are understood to exclude the number itself; expressions such as "above," "below," and "within" are understood to include the number itself. Furthermore, in the description of the embodiments of this application, "multiple" means more than two (including two), and similar expressions related to "multiple" are also understood in this manner, such as "multiple groups," "multiple times," etc., unless otherwise specifically defined.

[0067] In the specific implementation manner, the limited weight ratio range of each raw material of the glass composition is further explained.

[0068] Silica sand is used to provide SiO2 in glass, forming a silicon-oxygen tetrahedron (SiO4) network within the glass. Too low a silica sand ratio can negatively impact the glass's acid and hydrolysis resistance, increase its expansion coefficient, and reduce its thermal shock resistance. Too high a silica sand ratio can reduce the glass's solubility and hinder glass melting. Therefore, the silica sand ratio should be controlled between 54% and 65%, preferably between 55% and 62%.

[0069] The Al2O3 and small amounts of CaO and MgO contained in lithium feldspar complement the Al2O3 in alumina powder and the CaO and MgO in dolomite. If the lithium feldspar dosage is too low, sufficient Li2O will not be introduced, which will negatively impact the glass's hydrolysis resistance and the melting process. If the lithium feldspar dosage is too high, the mineral raw materials will contain higher levels of other components that can degrade glass properties. Therefore, the lithium feldspar ratio is controlled between 12% and 21%, preferably between 14% and 19%.

[0070] Anhydrous borax is used to provide B2O3 and some Na2O in glass. B2O3 promotes the formation of a glass network, reduces the glass's thermal expansion coefficient, improves its thermal stability, and reduces its high-temperature viscosity, aiding its melting. If the anhydrous borax content is too low, these effects are difficult to achieve; if the anhydrous borax content is too high, the chemical durability of the glass can be reduced. The Na2O provided by the anhydrous borax can also improve the glass's solubility. Therefore, the proportion of anhydrous borax is controlled to 10% to 18%, preferably 11.5% to 16.4%.

[0071] Alumina powder provides Al2O3 in glass, a component that forms the glass network. The resulting [AlO4] integrates into the glass network, increasing its strength and improving its hydrolysis resistance. Too low a proportion of alumina powder will not produce these benefits; too high a proportion will increase the glass viscosity excessively, hindering glass melting. Furthermore, because the volume of [AlO4] exceeds that of [SiO4], ions in the glass easily permeate the [AlO4] network and precipitate. Therefore, the alumina powder content is controlled between 1% and 6%, preferably between 1.5% and 5%.

[0072] It is particularly important to point out that this technical solution does not use aluminum hydroxide to introduce Al2O3, because aluminum hydroxide will decompose H2O, which will easily increase the risk of oxygen bubbles when platinum channel equipment is used for mass production in the future.

[0073] Soda ash provides Na2O in the glass, and potassium carbonate provides K2O in the glass. Na2O and K2O are components that reduce the viscosity of the glass, just like Li2O. If the content of soda ash and potassium carbonate is too low, the thermal expansion coefficient decreases, the viscosity of the glass increases, and it is not conducive to glass melting; if the content of soda ash and potassium carbonate is too high, the amount of alkali metals precipitated from the glass increases, and the thermal expansion coefficient increases, and the thermal stability decreases. In particular, if the amount of soda ash is increased too much, the Na2O and K2O will decrease due to the increase in the viscosity of the glass. + The ionic radius is smaller than K +Radius, this precipitation tendency is more obvious. In addition, considering that the market price of potassium carbonate is more than twice that of soda ash. Therefore, the ratio of soda ash and potassium carbonate is controlled to be 0.2% to 5% and 0.1% to 3%, respectively, preferably 0.3% to 4% and 0.2% to 2.5%.

[0074] Dolomite provides CaO and MgO in glass, while barium carbonate provides BaO. Alkaline earth metal oxides can adjust the network structure of glass, reducing viscosity, increasing its resistance to devitrification, and improving its forming properties. If the dolomite and barium carbonate content is too low, these properties will be difficult to achieve; if the content is too high, the glass will be prone to crystallization, reducing its thermal stability and chemical durability. Therefore, the proportions of dolomite and barium carbonate are controlled to be 0% to 2% and 0.5% to 4%, respectively, preferably 0.1% to 1.5% and 0.8% to 3%.

[0075] Titanium dioxide provides the TiO2 in glass, while zircon powder provides ZrO2 and some SiO2. TiO2 and ZrO2 act as network modifiers, strengthening the glass's network structure and promoting the formation and stabilization of [AlO4] and [BO4]. SiO2 is a network former in glass. TiO2 and ZrO2 are also essential components for UV shielding. If the titanium dioxide and zircon powder content is too low, the glass's alkali resistance and other properties will not be fully realized. If the titanium dioxide and zircon powder content is too high, the glass's solubility will deteriorate, increasing the risk of quality instability. Therefore, the proportions of titanium dioxide and zircon powder should be controlled at 1% to 5% and 1% to 3%, respectively, preferably 1% to 3.5% and 1.5% to 2.5%.

[0076] Sodium sulfate and stannous oxide are used together as glass clarifiers. Sodium sulfate is anhydrous sodium sulfate Na2SO4, and stannous oxide is SnO. Na2SO4 is an oxidizing clarifier, and SnO has reducing properties. Adding SnO can lower the decomposition temperature of Na2SO4, thereby improving the clarification effect of the glass. More importantly, when SnO plays its clarification role, it is first oxidized to SnO2. In the high temperature section of the melting process, around 1600℃ to 1650℃, SnO2 releases O2 in a concentrated manner, further strengthening the clarification effect and making it easy to produce glass with no bubbles or low bubble content. Therefore, the proportions of sodium sulfate and stannous oxide are controlled to be 0.4% to 1.2% and 0.1% to 0.4%, respectively, and preferably 0.5% to 1% and 0.15% to 0.25%.

[0077] In addition to providing Li2O and Al2O3 in glass and supplementing the SiO2 primarily provided by silica sand, lithium feldspar also provides some Na2O, K2O, and small amounts of CaO and MgO. Li2O, Na2O, and K2O are known to reduce glass viscosity and improve its melting properties. More importantly, they create a mixed alkali effect, increasing the glass's solubility without excessively increasing its thermal expansion coefficient. In particular, the introduction of an appropriate amount of Li2O can inhibit ion precipitation and improve the glass's hydrolysis resistance.

[0078] The total alkali content in lithium feldspar is controlled to be Li2O+Na2O+K2O≥8.0%. The reason is that the mixed alkali content can help melt the raw materials, especially the refractory raw materials such as alumina powder, zircon powder, and silica sand, effectively reduce the melting temperature, and improve the melting quality. At the same time, lithium feldspar also introduces the alumina and silica required for pharmaceutical glass. These components have achieved good combination with the mixed alkali when introduced, making it easier to melt and manufacture. In addition, the mixed alkali introduced by lithium feldspar can reduce the gas rate in the molten glass compared to introducing alkali entirely through carbonate (in addition, it can reduce the cost by more than 4 times compared to introducing alkali through carbonate), making it easier to manufacture pharmaceutical packaging glass with less or no bubbles. When the content is lower than 8%, it means that the quality of the lithium feldspar ore source is not high, and there are many other unnecessary impurities, which is not suitable for pharmaceutical glass raw materials. Therefore, the lower limit of the total alkali content should be limited. Furthermore, due to the Li2O provided by Li in the glass, the + The aggregation effect of Li2O can reduce the thermal expansion coefficient of pharmaceutical glass, improve the light-shielding and ultraviolet (external radiation) interception performance, and also contribute to the water resistance of pharmaceutical glass. Therefore, the lower limit of its proportion should be limited. In addition, considering the synergistic effect of mixed alkali, the upper limit should also be limited. Therefore, the proportion of Li2O in the total alkali content is 0.2-0.5.

[0079] Therefore, the content of Li2O+Na2O+K2O in the lithium feldspar is controlled to be ≥8.0wt%, and the ratio of Li2O / (Li2O+Na2O+K2O) is between 0.2 and 0.5; preferably, the content of Li2O+Na2O+K2O in the lithium feldspar is controlled to be ≥8.5wt%, and the ratio of Li2O / (Li2O+Na2O+K2O) is between 0.3 and 0.5.

[0080] When implementing the present invention, each raw material component may also contain Fe2O3. Fe2O3 is essential for glass coloring, but excessive Fe2O3 content can increase the burden during the manufacturing process and hinder glass quality. Preferably, the iron content in silica sand is below 800 ppm, the iron content in lithium feldspar and dolomite is below 8000 ppm, the iron content in zircon powder and titanium dioxide is below 6000 ppm, and the iron content in the other raw materials is below 200 ppm.

[0081] Furthermore, the iron content in silica sand is below 700 ppm, the iron content in lithium feldspar and dolomite is below 7000 ppm, the iron content in zircon powder and titanium dioxide is below 5000 ppm, and the iron content in other component raw materials is below 150 ppm.

[0082] More preferably, the iron content in silica sand is below 600 ppm, the iron content in lithium feldspar and dolomite is below 6000 ppm, the iron content in zircon powder and titanium dioxide is below 4000 ppm, and the iron content in other component raw materials is below 100 ppm.

[0083] The thermal expansion coefficient of the glass for medical packaging of the present invention is 48×10 -7 / ℃~56×10 -7 / ℃, further 49×10 -7 / ℃~55×10 -7 / ℃, the most preferred is 50×10 -7 / ℃~54×10 -7 If the expansion coefficient is too low, the proportion of refractory components such as ZrO2, Al2O3, and SiO2 in the glass needs to be increased, which is not conducive to production; if the expansion coefficient is too high, the thermal stability will deteriorate, which is not conducive to the storage and use of the glass for pharmaceutical packaging under various harsh conditions.

[0084] The glass for pharmaceutical packaging of the present invention has a viscosity of 10 2.3 The temperature of the Poise is below 1670℃, preferably below 1650℃, and most preferably below 1630℃. The glass is easy to melt when the viscosity is low, and the glass is easy to clarify at low viscosity. The temperature is measured by the platinum ball pulling method and the Fulecher viscosity calculation formula is used. 4 The temperature at the time of Poise is also calculated using the same method.

[0085] The pharmaceutical packaging glass of the present invention has a working temperature below 1230°C, further below 1210°C, and most preferably below 1190°C. If the working temperature is too high, the subsequent processing temperature of the pharmaceutical glass into packaging containers such as vials and ampoules will also increase. Alkali components contained in the glass, including boron components when the boron content is high, will significantly volatilize. The volatile components will adhere to the inner wall of the medicine bottle, causing deterioration of the medicine solution during filling and storage.

[0086] The glass for pharmaceutical packaging of the present invention has a liquidus temperature of less than 1100° C., preferably less than 1090° C., and most preferably less than 1080° C. A low liquidus temperature makes the glass less susceptible to crystallization, facilitating molding and manufacturing.

[0087] Example:

[0088] The present invention will be described below with reference to the embodiments.

[0089] Table 1 shows the glass composition of Examples 1-8 and Comparative Examples 1-4 of the present invention and the performance test results of the prepared samples.

[0090] Each sample was prepared according to the following process: 500g of each raw material, accurately weighed according to the mass percentages in the formula listed in Table 1, was mixed uniformly in a small mixer to achieve a uniformity of at least 95%. The resulting mixture was then poured into an 800ml platinum-rhodium crucible and heated in a high-temperature lifting furnace from room temperature to 1650°C at a rate of 5°C / min. The temperature was then maintained at this temperature for 5 hours. During the melting process, the glass was stirred twice with a platinum rod to ensure uniform melting. The molten glass was then poured into a mold preheated to approximately 200°C and cast into a glass block. Once formed, the block was annealed in a muffle furnace at 600°C for 2 hours. Finally, the furnace was turned off and the temperature naturally cooled to below 100°C before removal. Further cold working was performed depending on the desired glass size.

[0091] Table 1 (1-2): Glass composition and test results of Examples 1-8 and Comparative Examples 1-4

[0092]

[0093]

[0094] Continuation of Table 1:

[0095]

[0096]

[0097] The following is a necessary explanation of the instruments and methods used for each evaluation indicator.

[0098] Transmittance: Measurements were made using a spectrophotometer (PerkinElmer Lambda 950) on 2 mm thick, surface-finished glass. The measurement wavelength range was 290–450 nm, the slit width was 4 nm, the scanning speed was medium, and the sampling interval was 1 nm.

[0099] Hydrolysis resistance: This refers to the 121°C particle method water resistance, expressed as milliliters of 0.02 mol / L HCl per gram of glass particles. According to the method in YBB00252003-2015, the glass sample is crushed in an alumina mortar with an alumina pestle and sieved to a particle size of 300-425 μm for testing.

[0100] Acid resistance test: Tested in accordance with YBB00342004-2015 "Test method for resistance of glass to boiling hydrochloric acid erosion".

[0101] Alkali resistance determination: Determined in accordance with YBB00352004-2015 "Determination of resistance of glass to corrosion by boiling mixed alkali aqueous solution".

[0102] Thermal expansion coefficient was determined using a horizontal dilatometer in accordance with ASTM E-228 and expressed as an average linear expansion coefficient.

[0103] Liquidus temperature was determined by the gradient furnace method according to ASTM C-829.

[0104] Determination of glass bubble quality: From the center of the ingot, cut a sample with a length*width*thickness of 100mm*100mm*2mm using a diamond wire cutting machine. After grinding two equilateral surfaces, observe with a microscope and measure the 100cm 2 If the number of bubbles larger than 100 μm was 1 or less, it was judged as O; if the number was more than 1, it was judged as ×.

[0105] It can be seen from the test results of Examples 1-8 in Table 1 that the glass prepared according to the weight ratio of each raw material in the formula of the present invention is 10 2.3 Poise (℃) below 1630℃, working point 10 4.0 Poise (℃) is below 1190℃, liquidus temperature (℃) is lower than 1070℃, linear thermal expansion coefficient (×10 -7 / ℃) at 50×10 -7 / ℃~54×10 -7 / ℃, 290~450nm wavelength transmittance (%) is below 14%, and the ability to shield ultraviolet rays is outstanding; acid and alkali resistance both meet the national pharmaceutical packaging material standard (YBB-2015 standard) level 1, and the consumption of 0.02mol / L hydrochloric acid per unit mass of glass in the 121℃ granular method hydrolysis stability test is less than 0.030ml, which meets the European Pharmacopoeia 7.0 standard. In addition, 2mm thick glass per 100cm 2 The number of bubbles larger than 100 μm is less than one, resulting in glass for pharmaceutical packaging with no bubbles or a low bubble content. This technical solution, through the design of components and content, can produce glass for pharmaceutical packaging with excellent chemical durability and high UV shielding capabilities, making it suitable for the pharmaceutical packaging field.

[0106] From Comparative Examples 1-2 in Table 1, it can be seen that since the weight proportion of stannous oxide is less than 0.1%, the bubble quality is still poor even if the weight proportion of alum is increased; in Comparative Example 3, since the weight proportion of lithium feldspar is less than 12% and the weight proportion of soda ash is increased, the hydrolysis resistance decreases; in Comparative Example 4, since the weight proportion of zircon powder is less than 1%, the alkali resistance is reduced to Level 2, the hydrolysis stability is significantly reduced, and the transmittance is increased.

[0107] Finally, it should be noted that although the above embodiments have been described in the specification of this application, this does not limit the scope of patent protection of this application. All technical solutions generated by replacing or modifying equivalent structures or equivalent processes based on the essential concepts of this application using the contents recorded in the specification of this application, as well as directly or indirectly implementing the technical solutions of the above embodiments in other related technical fields, are included in the scope of patent protection of this application.

Claims

1. A glass for pharmaceutical packaging, characterized in that: The raw materials of the glass for pharmaceutical packaging include the following components in percentage by mass: Silica sand 54-65% Lithium feldspar 12-21% Anhydrous borax 10-18% Alumina 1~6% Soda ash 0.2~5% Titanium dioxide 1~5% Barium carbonate 0.5-4% Potassium carbonate 0.1~3% Zircon powder 1~3% Dolomite 0~2% Sodium sulfate 0.4~1.2% Stannous oxide 0.1~0.4% The lithium feldspar contains Al2O3, SiO2, Li2O, Na2O, and K2O components, and Li2O+Na2O+K2O≥8.0wt%, and the ratio of Li2O / (Li2O+Na2O+K2O) is between 0.2 and 0.5; The average thermal expansion coefficient of the glass for pharmaceutical packaging in the temperature range of 25-300°C is 48×10 -7 / ℃~56×10 -7 / ℃.

2. The glass for pharmaceutical packaging according to claim 1, characterized in that: The raw materials of the glass for pharmaceutical packaging include the following components in percentage by mass: Silica sand 55-62% Lithium feldspar 14-19% Anhydrous borax 11.5~16.4% Alumina 1.5~5% Soda ash 0.3~4% Titanium dioxide 1~3.5% Barium carbonate 0.8~3% Potassium carbonate 0.2~2.5% Zircon powder 1.5~2.5% Dolomite 0.1~1.5% Sodium sulfate 0.5~1% Stannous oxide 0.15-0.25%; The lithium feldspar contains Al2O3, SiO2, Li2O, Na2O, and K2O components, and Li2O+Na2O+K2O≥8.5wt%, and the ratio of Li2O / (Li2O+Na2O+K2O) is between 0.3 and 0.

5.

3. The glass for pharmaceutical packaging according to claim 1, characterized in that: The glass used for pharmaceutical packaging reaches 10 2.3 The viscosity of the glass is below 1670℃; 4 The working point temperature at the viscosity of Poise is lower than 1230°C; the liquidus temperature of the glass for medical packaging is lower than 1100°C.

4. The glass for pharmaceutical packaging according to claim 1, wherein: The glass for medical packaging has a thickness of 2 mm and a light transmittance of less than 18% at a wavelength of 290 to 450 nm.

5. The glass for pharmaceutical packaging according to claim 1, wherein: The glass for pharmaceutical packaging complies with the requirements of the YBB-2015 national pharmaceutical packaging material standard for pharmaceutical glass, and the glass for pharmaceutical packaging complies with the European Pharmacopoeia 7.0 standard.

6. The glass for pharmaceutical packaging according to claim 1, wherein: The glass for medical packaging has a thickness of 2 mm and contains no more than one bubble with a diameter of 100 μm or more per 100 square centimeters.

7. The method for preparing glass for pharmaceutical packaging according to any one of claims 1 to 6, characterized in that: The following steps are involved: Mixing: uniformly mixing the raw materials of the glass for pharmaceutical packaging according to any one of claims 1 to 6 according to a component formula to obtain a mixture; Melting: The mixture melts at a certain temperature to obtain molten glass; Molding: After the glass liquid is clarified and homogenized, it enters the mold for molding; Annealing: The formed glass is annealed at a temperature, and the glass for medical packaging is obtained after the temperature is naturally lowered.

8. The method for preparing glass for pharmaceutical packaging according to claim 7, wherein: In the melting step, the melting temperature is 1600° C. to 1650° C., and the melting time is 4 to 6 hours.

9. The method for preparing glass for pharmaceutical packaging according to claim 7, wherein: In the annealing step, the annealing temperature is 580° C. to 620° C., and the annealing time is 2 to 3 hours.

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