glass compositions with better chemical and mechanical durability

专利摘要:
GLASS COMPOSITIONS WITH BETTER CHEMICAL AND MECHANICAL DURABILITY The embodiments described here refer to chemically and mechanically durable glass compositions and glass objects formed from it. In another embodiment, a glass composition can include from about 70 mol% to about 80 mol% of SiO2; from about 3 mol% to about 13 mol% of alkaline earth oxide, X mol% of Al2O3; and Y mol% of alkaline oxide. Alkali metal oxide can include Na 2 O in an amount greater than about 8 mol%. A Y: X ratio can be greater than 1 and the glass composition can be free of boron and boron compounds. In some embodiments, the glass composition may also be free of phosphorus and phosphorus compounds. Glass articles formed from the glass composition can have at least one resistance to class S3 acids according to DIN 12116, at least one resistance to class A2 according to ISO 695, and one hydrolytic resistance type HGA1 according to ISO 720.
公开号:BR112014009921B1
申请号:R112014009921-9
申请日:2012-10-25
公开日:2020-12-29
发明作者:Paul Stephen Danielson；Steven Edward Demartino；Melinda Ann Drake；Robert Michael Morena；Santona Pal；Robert Anthony Schaut
申请人:Corning Incorporated；
IPC主号:

专利说明:

Cross-reference for related applications
[0001] The present application claims the provisional priority Serial Patent Application No. 61 / 551,163, filed on October 25, 2011 (Attorney n ° SPl 1-240P) and entitled "Glass compositions with better chemistry and mechanics Durability , "the entirety of which is hereby incorporated by reference. Field of invention
[0002] The present specification refers generally to glass compositions and, more specifically, to mechanically resistant glass compositions that are suitable for use in pharmaceutical and chemical packaging. State of the art
[0003] Historically, glass has been used as the preferred material for packaging pharmaceutical products, due to its hermeticity, optical transparency and excellent chemical durability in relation to other materials. Specifically, the glass used in pharmaceutical packaging must have adequate chemical durability, so as not to affect the stability of the pharmaceutical compositions contained therein. Glasses with adequate chemical durability include glass compositions within the ASTM standard “Type IB” glass compositions, which have a proven history of chemical durability.
[0004] However, the use of glass for such applications is limited by the mechanical performance of the glass. Specifically, in the pharmaceutical industry, glass breaking is a safety concern for the end user as the broken package and / or the contents of the package can injure the end user. Breaking can be expensive for drug manufacturers, because breaking within a filling line requires that neighboring intact containers be discarded as the containers may contain fragments of the broken container. Breakage may also require that the filling line be slowed or stopped, decreasing the production yield. In addition, the breakdown can also result in the loss of active medication leading to increased costs. In addition, non-catastrophic rupture (that is, when glass cracks, but does not break) can cause the contents to lose their sterility, which, in turn, can result in expensive products recalls.
[0005] One method to improve the mechanical durability of the glass packaging is to thermally temper the glass packaging. Thermal quenching strengthens glass by inducing a surface compression stress during rapid cooling after formation. This technique works well for glass articles with flat geometry (such as windows), glass articles with thicknesses of> 2 mm, and glass compositions with high thermal expansion. However, pharmaceutical glass packets usually have complex geometries (vial, tubular, ampoules, etc.), thin-walled (-1 -1.5 mm), and are produced from low, small expansion glasses (30-55x10'7K -1), making pharmaceutical glass packaging unsuitable for strengthening thermal tempering.
[0006] Chemical quenching also strengthens glass by introducing surface compression stress. Pressure is introduced by immersing the article in the molten salt bath. As glass ions are replaced by larger ions from the molten salt, a compressive stress induced on the glass surface. The advantage of chemical quenching is that it can be used in complex geometries, fine samples, and is relatively insensitive to the thermal expansion characteristics of the glass substrate. However, glass compositions that exhibit moderate susceptibility to chemical tempering generally have little chemical durability and vice versa.
[0007] Consequently, there is a need for glass compositions that are chemically durable and susceptible to chemical strengthening by ion exchange for use in pharmaceutical glass packaging, and in similar applications. RESUME
[0008] According to one embodiment, a glass composition can include: Si0 2 in a concentration greater than about 70 mol% and Y mol% of alkaline oxide. Alkaline oxide can include Na2O in an amount greater than about 8 mol%. The glass composition can be free of boron and boron compounds.
[0009] According to another embodiment, a glass composition can include. Greater than about 68 mol% Si0 2; X mol% Al2O3, Y mol% alkaline oxide, and B2O3. Alkali metal oxide can include Na20 in an amount greater than about 8 mol%. The ratio (B2O3 (mol%) / (Y% mol -.X% mol) can be greater than 0 and less than 0.3.
[0010] In yet another embodiment, a glass article may have an HGB1-like hydrolytic resistance in accordance with ISO 719. The glass article may include more than about 8 mol% Na2O and less than about 4 mol%. B2O3.
[0011] In yet another embodiment, a glass pharmaceutical package may include: Si0 2 in an amount greater than about 70 mol%, the symbol X mol% Al2O3, and Y mol% of alkaline oxide. Alkaline oxide can include Na2O in an amount greater than about 8 mol%. A ratio of a B2O3 concentration (mol%) in the pharmaceutical glass packaging of (mol Y% - X mol%) can be less than 0.3. The glass pharmaceutical package can also have a hydrolytic resistance type HGB1 according to ISO 719.
[0012] In another embodiment, a glass composition can include from about 70 mol% to about 80 mol% SiO2; from about 3 mol% to about 13 mol% alkaline earth oxide, X mol% of Al2O3, and Y mol% of alkaline oxide. Alkaline oxide can include Na2O in an amount greater than about 8 mol%. A Y: X ratio can be greater than 1 and the glass composition can be free of boron and boron compounds.
[0013] In yet another embodiment, a glass composition can include from about 72 mol% to about 78 mol% SiO2; from about 4 mol% to about 8 mol% of alkaline earth oxide, X mol% Al2O3; and Y% in mol of alkaline oxide. The amount of alkaline earth oxide can be greater than or equal to about 4 mol% and less than or equal to about 8 mol%. Alkali metal oxide can include Na20 in an amount greater than or equal to about 9 mol% and less than or equal to about 15 mol%. A Y: X ratio can be greater than 1. The glass composition can be free of boron and boron compounds.
[0014] In yet another embodiment, a glass composition can include: from about 68 mol% to about 80 mol% SiO2; from about 3 mol% to about 13 mol% of alkaline earth oxide, X mol% Al2O3; and Y% in mol of alkaline oxide. Alkaline oxide can include Na2O in an amount greater than about 8 mol%. The composition of the glass may also include B2O3. The ratio (B2O3 (mol%) / (Y% mol - X mol%) can be greater than 0 and less than 0.3, and a Y: X ratio can be greater than 1.
[0015] In another embodiment, a glass composition can include from about 70 mol% to about 80 mol% Si02; from about 3 mol% to about 13 mol% of alkaline earth oxide, X mol% Al2O3; and Y mol% of alkaline oxide. of alkaline earth oxide may include CaO in an amount greater than or equal to about 0.1 mol% and less than or equal to about 1.0 mol%. X can be greater than or equal to about 2 mol% and less than or equal to about 10 mol% alkali metal oxide can include from about 0.01 mol% to about 1.0 mol% K20. A proportion of Y :. X can be greater than 1. The glass composition. it can be free of boron and boron compounds.
[0016] In yet another embodiment, a glass composition can include SiO2 in an amount greater than about 70 mol% and less than or equal to about 80 mol%, from about 3 mol% to about 13 mol% alkaline earth oxide; X mol% Al2O3; and Y% in mol of alkaline oxide. Alkaline oxide can include Na2O in an amount greater than about 8 mol%. A ratio of a B2O3 concentration (mol%) in the glass composition of (mol Y% - X mol%) can be less than 0.3. A Y: X ratio can be greater than 1.
[0017] In another embodiment, a glass article can have a hydrolytic resistance like HGB1 according to ISO 719. The glass article can also have a diffusivity threshold greater than 16 μm 2 / hr at a lower temperature or equal to 450 ° C.
[0018] In yet another embodiment, a glass article can have a hydrolytic resistance like HGB1 according to ISO 719. The glass article can also have a compression stress layer with a layer depth of greater than than 25 μm and a surface compression stress greater than or equal to 350 MPa. The glass article can be reinforced by ion exchange and for the reinforcement of ion exchange it can include the treatment of the glass article in a molten salt bath for a time less than or equal to 5 hours at a temperature less than or equal to 450 ° C.
[0019] Additional features and advantages will be presented in the detailed description that follows, and in part will be apparent to those skilled in the art from this description or recognized by the practice of the embodiments described here, including the detailed description that follows, the claims, as well as in the attached drawings.
[0020] It is to be understood that both the previous general description and the following detailed description describe various embodiments and are intended to provide an overview or structure for understanding the nature and characteristics of the claimed object. The attached drawings are included to provide a better understanding of the different embodiments, and are incorporated and form a part of this specification. The drawings illustrate the various embodiments described here, and together with the description they serve to explain the principles and operations of the claimed matter. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 graphically represents the relationship between the proportion of alkaline oxides to alumina (x-axis) and the stress point, annealing point and softening point (y-axis) of the glass compositions of the invention and comparatives;
[0022] FIG. 2 graphically represents the relationship between the proportion of alkali oxides and alumina (x-axis) and the maximum compression stress and stress change (y-axes) of glass compositions of the invention and comparatives;
[0023] FIG. 3 graphically represents the relationship between the proportion of alkaline oxides and alumina (x-axis) and the hydrolytic resistance as determined from the ISO 720 (y-axis) standard of glass compositions of the invention and comparatives;
[0024] FIG. 4 graphically describes the D diffusivity (y-axis) as a function of the ratio (CaO / (CaO + MgO)) (x-axis) for the glass compositions of the invention and comparatives;
[0025] FIG. 5 graphically represents the maximum compression stress (y-axis) as a function of the ratio (CaO / (CaO + MgO)) (x-axis) for the glass compositions of the invention and comparatives;
[0026] FIG. 6 graphically represents the D diffusivity (y-axis) as a function of the (B203 / (R20-Al203)) ratio (x-axis) for the inventive and comparative glass compositions and
[0027] FIG. 7 graphically represents the hydrolytic resistance, as determined from ISO 720 (y-axis) as a proportion of (B 203 / (R20-AI203)) (x-axis) for inventive and comparative glass compositions. DETAILED DESCRIPTION
[0028] Reference will now be made in detail to the various embodiments of the glass compositions that present chemical improvement and mechanical durability. Such glass compositions are suitable for use in a variety of applications, including, without limitation, as pharmaceutical packaging materials. The glass compositions can also be chemically reinforced, thus providing greater mechanical durability for the glass. The glass compositions described herein can generally comprise of silica (Si02), alumina (Al203), alkaline earth oxides (such as MgO and / or CaO), and alkali metal oxides (such as Na20 and / or K20) in amounts that give chemical durability to the glass composition. In addition, the alkaline oxides present in glass compositions facilitate chemical reinforcement of glass compositions by ion exchange. Various embodiments of the glass compositions will be described and further illustrated here with reference to the specific examples.
[0029] The term "softening point", as used herein, refers to the temperature at which the viscosity of the glass composition is 1x107'6 poise.
[0030] The term "annealing point", as used herein, refers to the temperature at which the viscosity of the glass composition is 1x1013 poise.
[0031] The term "stress point" and "T strain", as used herein, refers to the temperature at which the viscosity of the glass composition is 3x1014 poise.
[0032] The term "CTE," as used herein, refers to the coefficient of thermal expansion of the glass composition over a temperature range from about room temperature (RT) to about 300 ° C.
[0033] In the embodiments of the glass compositions described herein, the concentrations of the constituent components (for example, SiO2, A12O3, and the like) are specified in mole percent (mol%) on an oxide basis, unless otherwise specified.
[0034] The terms "free" and "substantially free", when used to describe the concentration and / or the absence of a particular constituent component in a glass composition, that is to say that the constituent component is not intentionally added to the glass composition. However, the glass composition may contain traces of the constituent component as a contaminant or bum in amounts of less than 0.01 mol%.
[0035] The term "chemical durability", as used herein, refers to the ability of the glass composition to resist degradation upon exposure to specified chemical conditions. Specifically, the chemical durability of the glass compositions described here were evaluated according to three established material test standards: DIN 12116 dated March 2001 and entitled "Glass test - Resistance to attack by a boiling aqueous hydrochloric acid solution - Test and classification method "; ISO 695: 1991 entitled "Glass Resistance to attack by a boiling aqueous solution of mixed alkaline - Test and classification method" and ISO 720: 1985, entitled "Glass-Hydro lytic resistance of glass grains at 121 ° C-Test method and classification. "The chemical durability of glass can also be assessed in accordance with ISO 719: 1985" Glass-Hydro lytic resistance of glass grains of 98 degrees C- Test and classification method ", in addition to the standards mentioned above. The ISO 719 standard is a less stringent version of the ISO 720 standard and, as such, it is believed that a glass that corresponds to a specific classification of the ISO 720 standard will also satisfy the corresponding classification of the ISO 719 standard. each of the patterns are described in more detail here.
The glass compositions described herein are the alkali metal aluminosilicate glass compositions, which can generally include a combination of SiO2 and one or more alkali metal oxides, such as Na2O and / or K2O. The glass composition may also include Al2O3 and at least one alkaline earth oxide. In some embodiments, the glass compositions can be free of boron and compounds containing boron. Glass compositions are resistant to chemical degradation and are also suitable for chemical reinforcement by ion exchange. In some embodiments, the glass compositions may further comprise minor amounts of one or more oxides such as, for example, SnO2, ZrO2, ZnO, TiO2, such as As2O3 or the like. These components can be added as refining agents and / or to further increase the chemical durability of the glass composition.
[0037] In the embodiments of the glass compositions described here SiO2 is the major constituent of the composition and, as such, is the main constituent of the resulting glass network. SiO2 increases the chemical durability of the glass and, in particular, the resistance of the acid decomposition glass composition and the resistance of the decomposition glass composition in water. Therefore, a high SiO2 concentration is generally desired. However, if the SiO2 content is too high, the formability of the glass can be reduced in terms of higher concentrations of SiO2 increasing the difficulty of melting the glass which, in turn, negatively impacts the formability of the glass. In the embodiments described herein, the glass composition generally comprises SiO2 in an amount greater than or equal to 67 mol% and less than or equal to about 80 mol% or even less than or equal to 78 mol%. In some embodiments, the amount of SiO2 in the glass composition can be greater than about 68 mol%, greater than about 69 mol% or even greater than about 70 mol%. In some other embodiments, the amount of SiO2 in the glass composition can be greater than 72 mol%, greater than 73 mol% or even greater than 74 mol%. For example, in some embodiments, the glass composition can include from about 68 mol% to about 80 mol% Or even up to 78 mol. % SiO2. In some other embodiments the glass composition can include from about 69 mol% to about 80 mol% Or even up to 78 mol. % SiO2. In some other embodiments, the glass composition may include from about 70 mol% to about 80 mol% or even up to 78% mol) SiO2. In still other embodiments, the glass composition comprises SiO2 in an amount greater than or equal to 70 mol% and less than or equal to 78 mol%. In some embodiments, SiO2 may be present in the glass composition in an amount of about 72 mol to about 78 mol%. In some other embodiments, SiO2 may be present in the glass composition in an amount of about 73 mol% to about 78 mol%. In other embodiments, SiO2 may be present in the glass composition in an amount of about 74 mol% to about 78 mol%. In still other embodiments, SiO2 may be present in the glass composition in an amount of about 70 mol% to about 76 mol%.
[0038] The glass compositions described herein may also include Al2O3. Al2O3, together with alkaline oxides present in glass compositions such as Na2O or similar, increases the glass's susceptibility to reinforce ion exchange. In the embodiments described herein, Al2O3 is present in glass compositions in X mol% while alkali metal oxides are present in the glass composition in Y% mol. The Y: X ratio in the glass compositions described here is greater than 1, in order to facilitate the susceptibility to reinforcement of ion exchange mentioned above. Specifically, the diffusion or diffusivity coefficient D of the glass composition refers to the rate at which alkaline ions penetrate the glass surface during ion exchange. Glasses that have a Y: X ratio greater than about 0.9 or even greater than about 1 have a higher diffusivity than glasses that have a Y: X ratio less than 0.9. Glasses in which alkaline ions have a greater diffusivity can obtain a greater depth of layer for a given ion exchange time and ion exchange temperature than in glasses where alkaline ions have a lower diffusivity. In addition, as the Y: X ratio increases, the breaking point, annealing point and softening point of the glass decrease, so that the glass is more easily moldable. In addition, for a given ion exchange time and ion exchange temperature, it was found that the compression efforts induced in glasses that have a Y: X index greater than about 0.9 and less than or equal to 2 are generally greater than those obtained in glasses in which the Y: X ratio is less than 0.9 or greater than 2. Therefore, in some embodiments, the proportion of Y: X is greater than 0.9, or even greater than 1. In some embodiments, the Y: X ratio is greater than 0.9, or even greater than 1 and less than or equal to about 2. In still other embodiments, the Y: X ratio can be greater than or equal to about 1.3 and less than or equal to about 2.0 in order to maximize the amount of compression stress induced in the glass by an ion exchange time and a determined specified ion exchange temperature.
[0039] However, if the amount of Al2O3 in the glass composition is very high, the resistance of the glass composition to acid attack is decreased. Therefore, the glass compositions described herein, generally include Al2O3, in an amount greater than or equal to about 2 mol% less than or equal to about 10 mol%. In some embodiments, the amount of Al2O3 in the glass composition is greater than or equal to about 4 mol% less than or equal to about 8 mol%. In some other embodiments, the amount of Al2O3 in the glass composition is greater than or equal to about 5 mol% less than or equal to about 7 mol%. In some other embodiments, the amount of Al2O3 in the glass composition is greater than or equal to about 6 mol% less than or equal to about 8 mol%. In still other embodiments, the amount of Al2O3 in the glass composition is greater than or equal to about 5% less than or equal to about 6 mol%.
[0040] Glass compositions also include one or more alkali metal oxides, such as Na 2 0 and / or K2O. Alkali oxides facilitate the ion exchangeability of the glass composition and, as such, facilitate chemically reinforcing the glass. Alkali metal oxide can include one or more of Na2O and K2O. Alkaline oxides are generally present in the glass composition at a total concentration of Y moles.%. In some embodiments described herein, Y may be greater than about 2 mol% less than or equal to about 18 mol%. In some other embodiments, Y may be greater than about 8 mol%, Greater than about 9 mol%, Greater than about 10 mol% or even greater than about 11 mol%. For example, in some embodiments described herein, Y is greater than or equal to about 8 mol% E less than or equal to about 18 mol%. In still other embodiments, Y can be greater than or equal to about 9 mol% E less than or equal to about 14 mol%.
[0041] The ion exchangeability of the glass composition is transmitted mainly to the glass composition by the amount of the alkaline metal oxide Na2O initially present in the glass composition before the ion exchange. Thus, in the embodiments of the glass compositions described herein, the alkali metal oxide present in the glass composition includes at least Na2O. Specifically, in order to achieve the desired compressive strength and depth of the glass composition layer on top of the ion exchange reinforcement, the glass compositions include Na2O in an amount from about 2 mol% to about 15 mol% with based on the molecular weight of the glass composition. In some embodiments, the glass composition includes at least about 8 mol% Na2O based on the molecular weight of the glass composition. For example, the Na2O concentration can be greater than 9 mol%, greater than 10 mol% or even greater than 11 mol%. In some embodiments, the Na 2 0 concentration can be greater than or equal to 9 mol% or even greater than or equal to 10 mol%. For example, in some embodiments the glass composition may include Na2O in an amount greater than or equal to about 9 mol% and less than or equal to about 15 mol% or even greater than or equal to about 9 mol% and less than or equal to 13 mol%.
[0042] As noted above, the alkali metal oxide in the glass composition can further include K2O. The amount of K2O present in the glass composition is also related to the ion exchangeability of the glass composition. Specifically, as the amount of K2O present in the glass composition increases, the compression stress can be obtained through ion exchange decreases as a result of the exchange of potassium and sodium ions. It is therefore desirable to limit the amount of K2O present in the glass composition. In some embodiments, the amount of K2O is greater than or equal to 0 mol% and less than or equal to 3 mol%. In some embodiments, the amount of K2O is less than or equal to 2 mol% or even less than or equal to 1.0 mol%. In embodiments where the glass composition includes K2O, K2O may be present in a concentration greater than or equal to about 0.01 mol% and less than or equal to about 3.0 mol% or even greater than or equal to about 0.01 mol% and less than or equal to about 2.0 mol%. In some embodiments, the amount of K2O present in the glass composition is greater than or equal to about 0.01 mol% and less than or equal to about 1.0 mol%. Therefore, it should be understood that K2O does not need to be present in the glass composition. However, when K 2 0 is included in the glass composition, the amount of K2O is generally less than about 3 mol% based on the molecular weight of the glass composition.
[0043] Alkaline earth oxides can be present in the composition to improve the melting ability of glass-forming materials and increase the chemical durability of the glass composition. In the glass compositions described here, the mole total.% Alkaline earth oxides present in the glass compositions is generally less than the mole total.% Alkaline oxides present in the glass compositions, in order to improve the exchangeability of ions in the glass composition. In the embodiments described herein, glass compositions generally include from about 3 mol% to about 13 mol% alkaline earth oxide. In some of these embodiments, the amount of alkaline earth oxide in the glass composition can be from about 4 mol% to about 8 mol% or even from about 4 mol% to about 7 mol%.
[0044] The alkaline earth oxide in the glass composition can include MgO, CaO, SrO, BaO, or combinations thereof. In some embodiments, alkaline earth oxide includes MgO, CaO or combinations thereof. For example, in the embodiments described herein, alkaline earth oxide includes MgO. MgO is present in the glass composition in an amount that is greater than or equal to about 3 mol% E less than or equal to about 8 mol% MgO. In some embodiments, MgO may be present in the glass composition in an amount that is greater than or equal to about 3 mol% E less than or equal to about 7 mol% Or even greater than or equal to 4 mol% E less than or equal to about 7 mol% by molecular weight of the glass composition.
[0045] In some embodiments, alkaline earth oxide may also include CaO. In these embodiments, CaO is present in the glass composition in an amount comprised between about 0 mol% Less than or equal to 6 mol% by molecular weight of the glass composition. For example, the amount of CaO present in the glass composition can be less than or equal to 5 mol%, Less than or equal to 4 mol%, Less than or equal to 3 mol%, Or even less than or equal to 2% mol. In some of these embodiments, CaO may be present in the glass composition in an amount greater than or equal to about 0.1 mol% and less than or equal to about 1.0 mol%. For example, CaO may be present in the glass composition in an amount greater than or equal to about 0.2 mol% AND less than or equal to about 0.7 mol% Or in an amount greater than or equal to about 0.3 mol.% and less than or equal to about 0.6 mol%.
[0046] In embodiments described here, glass compositions are generally rich in MgO, (i.e., the concentration of MgO in the glass composition is greater than the concentration of other alkaline earth oxides in the glass composition, including , without limitation, CaO). Forming the glass composition in such a way that the glass composition is MgO-rich improves the lithic hydraulic resistance of the resulting glass, particularly after reinforcing ion exchange. In addition, glass compositions that are MgO-rich generally perform better with ion exchange than glass compositions, which are rich in other alkaline earth oxides. Specifically, glasses formed from MgO-rich glass compositions generally have a higher diffusivity than glass compositions, which are rich in other alkaline earth oxides, such as CaO. The greater diffusivity allows the formation of a greater depth of glass layer. MgO-rich glass compositions also allow a higher compression stress to be achieved on the glass surface compared to glass compositions that are rich in other alkaline earth oxides, such as CaO. In addition, it is generally accepted that as product exchange process ions and alkaline ions penetrate more deeply into the glass, the maximum compressive stress achieved on the glass surface can decrease over time. However, glasses formed from glass compositions that are MgO-rich exhibit a lesser reduction in compression tension than glasses formed from glass compositions that are CaO-rich or rich in other alkaline earth oxides (or ie glasses that are MgO-poor). Thus, MgO-rich glass compositions allow glasses that have greater compressive stress on the surface and a greater depth of layer than glasses, which are rich in other alkaline earth oxides.
[0047] In order to fully understand the advantages of MgO in the glass compositions described here, it was determined that the relationship between the concentration of CaO to the sum of the concentration of CaO and MgO to the concentration in mol% (That is, (CaO / (CaO + MgO)) should be minimized. Specifically, it was determined that (CaO / (CaO + MgO)) must be less than or equal to 0.5. In some embodiments (CaO / (CaO + MgO)) is less than or equal to 0.3, or even less than or equal to 0.2 In some other embodiments (CaO / (CaO + MgO)) it may even be less than or equal to 0.1.
[0048]) boron oxide (B 2 0 3) is a flux that can be added to glass compositions to reduce viscosity at a given temperature (for example, strain, annealing and softening temperatures) thus improving deformability of the glass. However, it has been found that the addition of boron significantly decreases the diffusivity of sodium and potassium ions in the glass composition, which in turn negatively impacts the performance of the glass resulting from ion exchange. In particular, it has been found that the addition of boron significantly increases the time required to reach a certain depth of glass layer compared to compositions that are free of boron. Therefore, in some embodiments described herein, the amount of boron addition to the glass composition is minimized in order to improve the performance of the ion exchange glass composition.
[0049] For example, it has been determined that the impact of boron on the ion exchange performance of a glass composition can be mitigated by controlling the relationship between the concentration of B 2 0 3 for the difference between the total concentration of alkaline oxides ( that is, R 2 0, where R represents alkali metals) and alumina (ie, B 2 0 3 (mol%) / (R 2 0 (mol%), Al 2 0 3 (mol%)). In particular, it was determined that when the proportion of B 2 03 / (R 2 0 -Al 2 0 3) is greater than or equal to about 0 and less than about 0.3 or even less than about 0.2, the diffusivities of alkaline oxides in the glass compositions are not decreased and, as such, the performance of the ion exchange glass composition is maintained. Thus, in some embodiments, the proportion of B 2 O 3 / ( R 2 O-AI 2 O 3) is greater than 0 and less than or equal to 0.3 In some of these embodiments, the proportion of B 2 O3 / (R 2 O-AI 2 O 3) is greater than 0 and less than or equal to 0.2. In some tions, the proportion of B 2 O 3 / (R 2 O-AI 2 O 3) is greater than 0 and less than or equal to 0.15, or even less than or equal to 0.1. In some other embodiments, the proportion of B 2 O 3 / (R 2 O-AI 2 O 3) may be greater than 0 and less than or equal to 0.05. Maintain the B 2 O 3 / (R 2 O-AI 2 O 3) to be less than or equal to 0.3, or even less than or equal to 0.2 allows the inclusion of B 2 O 3 to decrease the stress point, the annealing point and softening point of the glass composition, without B 2 O 3 negatively impacting the performance of the ion exchange glass.
[0050] In embodiments described herein, the concentration of B 2 O 3 in the glass composition is generally less than or equal to about 4 moles.%, Less than or equal to about 3 mol%, less than or equal to about 2 mol%, or even less than or equal to 1 mol%. For example, in embodiments where B 2 O 3 is present in the glass composition, the concentration of B 2 O 3 can be greater than about 0.01 mol% and less than or equal to 4 mol%. In some of these embodiments, the concentration of B 2 O 3 may be greater than about 0.01 mol% and less than or equal to 3 mol% In some embodiments, B 2 O 3 may be present in an amount greater than or equal to about 0.01 mol% and less than or equal to 2 moles.%, or even less than or equal to 1.5 mol%. Alternatively, B 2 O 3 can be present in an amount greater than or equal to about 1 mole.% And less than or equal to 4 mole%, greater than or equal to about 1 mole.% And less than or equal to 3% mole or even greater than or equal to about 1 mole.% and less than or equal to 2 moles.%. In some of these embodiments, the concentration of B 2 O 3 can be greater than or equal to about 0.1 mol% and less than or equal to 1.0 mol%.
[0051] Although, in some embodiments, the concentration of B 2 O 3 in the glass composition is minimized to improve the glass forming properties, without impairing the ion exchange performance of the glass, in some other embodiments, the compositions of glass is free of boron and boron compounds, such as B 2 O 3. Specifically, it has been determined that the formation of the glass composition without boron or boron compounds improves the ion exchangeability of the glass compositions, reducing the time and / or the temperature required to obtain a specific stress value and / or the depth of the process compression layer.
[0052] In some embodiments, the glass compositions described herein, the glass compositions are free of phosphorus and compounds containing phosphorus, including, without limitation, P2O5. Specifically, it has been determined that the formulation of the glass composition, without phosphorus or phosphorus compounds, increases the chemical durability of the glass composition.
[0053] In addition to Si0 2, AI 2 O 3, alkaline oxides and alkaline earth oxides, the glass compositions described herein may optionally further comprise one or more clarifying agents, such as, for example, Sn0 2, NO 2 O 3, and / or Cl "(from NaCl or the like). When a clarifying agent is present in the glass composition, the clarifying agent can be present in an amount less than or equal to about 1 mole.% Or less than or equal to about 0.4 mole.% For example, in some embodiments the glass composition may include Sn0 2 as a clarifying agent. In these embodiments Sn0 2 may be present in the glass composition in a amount greater than about 0 mol% E less than or equal to about 1 mole.% Or even an amount greater than or equal to about 0.01 mol% E less than or equal to about 0.30 mol%.
[0054] In addition, the glass compositions described herein may comprise one or more additional metal oxides to further improve the chemical durability of the glass composition. For example, the glass composition can further include ZnO, Ti0 2, or Zr0 2, each of which further increases the resistance of the glass composition to chemical attack. In these embodiments, the additional metal oxide may be present in an amount that is greater than or equal to about 0 mol% E less than or equal to about 2 mol%. For example, when the additional metal oxide is ZnO, ZnO may be present in an amount greater than or equal to 1 mol% E less than or equal to about 2 moles.%. When the additional metal oxide is Zr0 2 Ti0 or 2, Zr0 2 or Ti0 2 may be present in an amount less than or equal to about 1 mol%.
[0055] As mentioned above, the presence of alkaline oxides in the glass composition facilitates chemically reinforcing the glass by ion exchange. Specifically, alkali metal ions, such as potassium ions, sodium ions and the like, are sufficiently mobile in the glass to facilitate ion exchange. In some embodiments, the glass composition is the exchangeable ion so as to form a compression stress layer having a layer depth greater than or equal to 10 μm. In some embodiments, the depth of the layer may be greater than or equal to about 25 μm or even greater than or equal to about 50 μm. In some other embodiments, the depth of the layer may be greater than or equal to 75 μm or even greater than or equal to 100 μm. In still other embodiments, the depth of the layer can be greater than or equal to 10 μm and less than or equal to about 100 μm. The associated surface tension compression can be greater than or equal to about 250 MPa, equal to or greater than 300 MPa, or even greater than or equal to about 350 MPa after the glass composition is treated in a molten salt of 100% KO 3 at a temperature of 350 ° C to 500 ° C for a period of time less than about 30 hours or even less than about 20 hours.
[0056] The glass articles formed from the glass compositions described here may have a resistance of hydrolytic HGB2 or even HGBl by ISO 719 and / or a resistance of hydroxy HGA2 or even HGA1 by ISO 720 (as described below), in addition to improving mechanical characteristics due to the strengthening of ion exchange. In some of the embodiments described here, glass articles may have compression stress layers that extend from the surface to the glass article at a layer depth greater than or equal to 25 μm or even greater than or equal to 35 μm. In some embodiments, the depth of the layer may be greater than or equal to 40 μm or even greater than or equal to 50 μm. The compressive stress of the glass article surface can be greater than or equal to 250 MPa, greater than or equal to 350 MPa, or even greater than or equal to 400 MPa. The glass compositions described herein facilitate reaching the aforementioned depths and the compression surface layer stresses more quickly and / or at lower temperatures than conventional glass compositions, due to the improved alkaline ion diffusivity of the glass compositions as described above . For example, layer depths (that is, greater than or equal to 25 μm) and compression stresses (that is, greater than or equal to 250 MPa) can be achieved by exchanging ions from the glass article in a molten salt bath of 100% KO 3 (or a mixed salt bath of KNO 3 and NaN0 3) for a period of time less than or equal to 5 hours, or even less than or equal to 4.5 hours, at a temperature less than or equal to 500 ° C or even less than or equal to 450 ° C. In some embodiments, the period of time to reach these layer depths and compression efforts can be less than or equal to 4 hours or even less than or equal to 3.5 hours. The temperature to reach these layer depths and compression stresses can be less than or equal to 400 ° C or even less than or equal to 350 ° C.
[0057] These improved ion exchange characteristics can be achieved when the glass composition has a threshold diffusivity greater than about 16 μm2 / hr at a temperature below or equal to 450 ° C or even greater than or equal to 20 μm2 / hr at a temperature less than or equal to 450 ° C. In some embodiments, the threshold diffusivity can be greater than or equal to about 25 μm2 / hr at a temperature less than or equal to 450 ° C or even 30 μm2 / hr at a temperature less than or equal to 450 ° C. In some other embodiments, the threshold diffusivity can be greater than or equal to about 35 μm2 / hr at a temperature less than or equal to 450 ° C or even 40 μm2 / hr at a temperature less than or equal to 450 ° C. In still other embodiments, the threshold diffusivity can be greater than or equal to about 45 μm2 / hr at a temperature less than or equal to 450 ° C or even 50 μm2 / hr at a temperature less than or equal to 450 ° C.
[0058] The glass compositions described herein can generally have a stress point greater than or equal to about 525 ° C and less than or equal to about 650 ° C. Glasses may also have an annealing point greater than or equal to about 560 ° C and less than or equal to about 725 ° C and a softening point greater than or equal to about 750 ° C and less than or equal to about 960 ° C.
[0059] In embodiments described here, the glass compositions have CTE of less than about 70x1-7K-1, or even less than about 60x10-7K-1. These lower CTE values improve the survivability of glass from thermal cycles or thermal stress conditions relative to higher CTE glass compositions.
[0060] In addition, as noted above, glass compositions are chemically durable and wear resistant, as determined by the DIN 12116 standard, the ISO 695 standard, and the ISO 720 standard.
[0061] More specifically, the standard DIN 12116 is a measure of the glass's resistance to decomposition when placed in an acidic solution. Soon, the standard DIN 12116 uses a sample of polished glass from a known surface area, which is weighed and then brought into contact with a proportional amount of 6 M hydrochloric acid boiling for 6 hours. The sample is then removed from the solution, dried and weighed again. Bulk glass lost during exposure to the acid solution is a measure of the acid durability of the sample with smaller numbers indicative of greater durability. The test results are presented in units of half mass per unit area, specifically mg / dm 2. The DIN 12116 standard is divided into individual lessons. Class SI indicates weight loss of up to 0.7 mg / dm 2, Class S2 indicates weight loss from 0.7 mg / dm 2 to 1.5 mg / dm 2; class S3 indicates weight loss of 1.5 mg / dm 2 to 15 mg / dm 2 and Class S4 indicates weight loss of more than 15 mg / dm 2
[0062] The ISO 695 standard is a measure of the glass's resistance to decomposition when placed in a basic solution. Soon, the ISO 695 standard uses a sample of polished glass, which is weighed and then placed in a boiling solution of 1M NaOH + 0.5 M Na 2 CO 3 for 3 hours. The sample is then removed from the solution, dried and weighed again. Bulk glass lost during exposure to the base solution is a measure of the durability of the sample base with smaller numbers indicating greater durability. As with the DIN 12116 standard, the results of the ISO 695 standard are presented in units of mass per unit area, specifically mg / dm 2. The ISO 695 standard is divided into individual lessons. Class Al indicates weight loss of up to 75 mg / dm 2, Class A2 indicates weight loss of 75 mg / dm 2 of up to 175 mg / dm 2 and Class A3 indicates weight loss of more than 175 mg / dm 2
[0063] The ISO 720 standard is a measure of the glass's resistance to degradation, purified C0 2 -free water. In summary, the ISO 720 standard protocol uses crushed glass grains, which are placed in contact with the purified, C0 2 -free water in autoclave conditions (121 ° C, 2 atm) for 30 minutes. The solution is then titrated by colorimetry with diluted HCl to neutral pH. The amount of HCl required to titrate to a neutral solution is then converted to an equivalent of Na 2 0 extracted from the glass and reported in mg of Na 2 0 per glass weight, with the lowest values indicating a longer durability. The ISO 720 standard is divided into individual types. Type HGA1 is indicative of up to 62 μg extracted equivalent of Na 2 0 per gram of tested glass; Type HGA2 is indicative of more than 62 mg and up to 527 mg equivalent extracted from Na 2 0 per gram of tested glass and Type HGA3 is indicative of more than 527 μg and 930 μg until extracted Na 2 0 per gram of tested glass .
[0064] The ISO 719 standard is a measure of the glass's resistance to degradation, purified C0 2 -free of water. In summary, the ISO 719 standard protocol uses crushed glass grains, which are placed in contact with the purified, 2-free water C0 at a temperature of 98 ° C at 1 atmosphere for 30 minutes. The solution is then titrated by colorimetry with diluted HCl to neutral pH. The amount of HCl required to titrate to a neutral solution is then converted to an equivalent of Na 2 0 extracted from the glass and reported in mg of Na 2 0 per glass weight, with the lowest values indicating a longer durability. The ISO 719 standard is divided into individual types. The ISO 719 standard is divided into individual types. Type HGB1 is indicative of up to 31 μg equivalents extracted from Na 2 0; Type HGB2 is indicative of more than 31 mg and up to 62 μg equivalent extracted from Na 2 0; Type HGB3 is indicative of more than 62 mg and up to 264 μg extracted from equivalent Na 2 0; Type HGB4 is indicative of more than 264 mg and up to 620 mg extracted from equivalent Na 2 0 and Type HGB5 is indicative of more than 620 μg and 1085 μg until extracted equivalent from Na 2 0. The glass compositions described here have a ISO 719 hydro lytic resistance of type HGB2 or better, with some realizations having a type HGB1 hydro lytic resistance.
[0065] The glass compositions described here have an acid resistance of at least class S3 according to DIN 12116 before and after the ion exchange reinforcement with some embodiments that have an acid resistance of at least class S2 or even SI class following ion exchange booster. In some other embodiments, the glass compositions may have an acid resistance of at least class S2, both before and after the ion exchange boost with some embodiments having an acid resistance of the next class SI exchange boost ionic. In addition, the glass compositions described here have a base resistance according to ISO 695 of at least class A2, before and after the ion exchange reinforcement with some modalities of having a class Al base resistance, in the after the reinforcement of ion exchange. The glass compositions described here also have an ISO 720 type HGA2 hydro lytic resistance, before and after reinforcement of ion exchange with some embodiments having a hydrolytic resistance type HGA1 after reinforcement of ion exchange and some other embodiments that have a hydrolytic resistance type HGA1, both before and after ion strengthening exchange. The glass compositions described here have an ISO 719 hydrolytic resistance of type HGB2 or better, with some embodiments having a type HGB1 hydrolytic resistance. It should be understood that, when referring to the above mentioned classifications according to DIN 12116, ISO 695, ISO 720 and ISO 719, a glass composition or glass article that has "at least" a specific classification means that the performance of the glass composition is as good or better than the specified rating. For example, a glass article that has a resistance to DIN 16 121 acids of "at least class S2" may have a DIN 12116 standard classified as SI or S2.
[0066] The glass compositions described here are formed by mixing a batch of raw materials glass (for example, Si0 2, A1 2 0 3 powders, alkali metal oxides, alkaline earth oxides and the like) in such a way so that the glass raw material batch has the desired composition. Thereafter, the batch of glass raw material is heated to form a molten glass composition, which is subsequently cooled and solidified to form a glass composition. During solidification (i.e., when the glass composition is plastically deformable), the glass composition can be shaped using conventional molding techniques to shape the glass composition to a desired final shape. Alternatively, the glass article can be shaped into an image form, such as a sheet, tube or the like, and subsequently reheated and shaped into the desired end shape.
[0067] The glass compositions described herein can be molded into glass articles that have various shapes, such as, for example, sheets, tubes or the like. However, given the chemical stability of the glass composition, the glass compositions described herein are particularly suitable for use in the formation of glass articles used as pharmaceutical packaging or pharmaceutical containers for pharmaceutical compositions containing, such as liquids, powders and the like. For example, the glass compositions described herein can be used to form glass containers that have various shapes of shapes, including, without limitation, Vacutainers ®, cartridges, syringes, ampoules, bottles, vials, ampoules, tubes, beakers, vials or the like. In addition, the ability to chemically strengthen glass compositions by means of ion exchange can be used to improve the mechanical durability of such glass containers or pharmaceutical articles formed from the glass composition. Therefore, it should be understood that, in at least one embodiment, the glass compositions are incorporated into a pharmaceutical package in order to improve the chemical durability and / or the mechanical durability of the pharmaceutical package. Examples
[0068] The embodiments of the glass compositions described here will be clarified through the following examples. EXAMPLE 1
[0069] Six exemplary glass compositions of the invention (AF compositions) were prepared. The specific compositions of each exemplary glass composition are reported below in Table 1. Several samples of each exemplary glass composition were produced. A set of samples from each composition was ion exchange in a molten salt bath of 100% KNO 3 at a temperature of 450 ° C for at least 5 hours, to induce a compression layer on the sample surface. The compression layer had a surface compression stress of at least 500 MPa, and a layer depth of at least 45 μm.
[0070] The chemical durability of each exemplary glass composition was determined using the DIN 12116 standard, the ISO 695 standard, and the ISO 720 standard described above then. Specifically, no ion exchange test samples from each of the exemplary glass compositions were tested according to one of the DIN 12116 standard, the ISO 695 standard, or the ISO 720 standard to determine acid resistance, base resistance , or the hydro lytic resistance of the test sample, respectively. The hydrolytic resistance of the exchanged ion samples of each exemplary composition was determined according to the ISO 720 standard. To determine the hydrolytic resistance of the ion exchanged samples, the glass was crushed to the required grain size in the ISO 720 standard, the ion exchange ion exchange in a molten salt bath of 100% KNO 3 at a temperature of 450 ° C for at least 5 hours to induce a compressive stress layer of the individual glass grains, and then tested according to the ISO 720 standard. The average results of all tested samples are reported below in Table 1.
[0071] As shown in Table 1, the exemplary AF glass compositions all demonstrated a loss of glass mass less than 5 mg / dm 2 and greater than 1 mg / dm 2 after testing according to DIN 12116 , with exemplary glass standard composition E having the smallest loss of glass mass of 1.2 mg / dm 2. Therefore, each of the exemplary glass compositions were classified in at least class S3 of the standard DIN 12116, with the exemplary glass composition E classified in class S2. Based on these test results, it is believed that the acid resistance of the glass samples increases with increasing Si0 2 content.
[0072] In addition, exemplary glass compositions AF all demonstrated a loss of glass mass less than 80 mg / dm 2 after testing according to ISO 695 standard with exemplary glass composition A having the least loss of glass mass at 60 mg / dm 2 Therefore, each of the exemplary glass compositions has been classified into at least class A2 of the ISO 695 standard, with exemplary glass compositions A, B, D and F classified in class Al. compositions with higher silica content showed lower base resistance and compositions with higher alkaline / alkaline content showed higher base resistance.
[0073] Table 1 also shows that the ion exchange does not test samples of exemplary AF glass compositions all demonstrated a hydrolytic resistance of at least Type HGA2 following testing in accordance with the ISO 720 standard with glass compositions that have an exemplary CF hydrolytic resistance of Type HGA1. The hydrolytic resistance of exemplary CF glass compositions is believed to be due to a higher amount of SiO2 and lower Na2O values in glass compositions compared to exemplary glass compositions A and B.
[0074] In addition, the ion exchange test samples of exemplary BF glass compositions demonstrated lower values of extracted Na 2 0 per gram of glass than the non-ion exchanged test samples with the same exemplary glass compositions following test according to 5 ISO 720 standard. Table 1: Composition and properties of glass specimens
EXAMPLE 2
[0075] Three exemplary inventive glass compositions> (G-I compositions) and three comparative glass compositions (compositions 1-3) were prepared. The proportion of alkaline oxides of alumina (i.e., Y: X) was varied in each of the compositions in order to evaluate the effect of this proportion on various properties of the resulting melt glass and glass. The specific compositions of each of the exemplary glass compositions of the invention and the comparative glass compositions are shown in Table 2. The breaking point, annealing point and softening point of the melts formed from each of the glass compositions were determined and are shown in Table 2. In addition, the thermal expansion coefficient (CTE), density, and optical stress coefficient (SOC) of the resulting cups were also determined and are shown in Table 2. The hydrolytic resistance of glass samples formed from each of the exemplary glass compositions of the invention and each comparative glass composition was determined according to ISO 720, both before by ion exchange and after ion exchange in a molten salt bath of 100% KNO 3 at 450 ° C for 5 hours. For samples that were exchanged ions, the compression voltage was determined with a fundamental stress meter (EFM) instrument, with the value of the compression voltage based on the measured optical stress coefficient (SOC). The FSM instrument couples light in and out of the birefringent glass surface. The measured birefringence is then related to stress through a constant material, optical stress or photoelastic coefficient (SOC or PEC) and two parameters are obtained: the maximum compression surface tension (CS) and the depth of the exchange layer (DOL ). The diffusivity of the alkaline ions in the glass and the change in voltage per square root of time were also determined. The diffusivity (D) of the glass is calculated from the depth of the measurement layer (DOL) and the ion exchange time (t) according to the relationship: DOL = -1.4 * sqrt (4 * D * t) . Diffusivity increases with temperature according to an Arrhenius relationship, and as such, it is reported at a specific temperature.
[0076] Table 2: Properties of glass as a function of alkali to alumina proportion
[0077] The data in Table 2 indicate that the alkali to alumina Y: X ratio influences the nature of fusion, hydrolytic resistance and the compression stress obtained by strengthening ion exchange. In particular, FIG. 1 graphically represents the stress point, annealing point and softening point as a function of the Y: X ratio for the glass compositions in Table 2. FIG. 1 shows that, as the Y: X ratio decreases below 0.9, a stress point, annealing point and the softening point of the glass increases rapidly. Thus, in order to obtain a glass that is easily meltable and moldable, the Y: X ratio must be greater than or equal to 0.9, or even greater than or equal to 1.
[0078] In addition, the data in Table 2 indicates that the diffusivity of glass compositions generally decreases with the Y: X ratio. Therefore, to achieve glasses that can be quickly ion exchanged, in order to reduce the process time (and the costs) the Y: X ratio must be greater than or equal to 0.9, or even greater than or equal to 1.
[0079] Furthermore, FIG. 2 indicates that, for a given ion exchange time and ion exchange temperature, the maximum compression efforts are obtained when the Y: X ratio is greater than or equal to about 0.9, or even greater than or equal to about 1, and less than or equal to about 2, namely greater than or equal to about 1.3 and less than or equal to about 2.0. Therefore, the greatest improvement in the load-bearing strength of glass can be obtained when the Y: X ratio is greater than about 1 and less than or equal to about 2. It is generally accepted that the maximum stress achievable per exchange ionic ion will decay with increasing ionic exchange duration, as indicated by the rate of voltage change (ie, the measured compression voltage divided by the square root of the ion exchange time). FIG. 2 generally shows that the rate of change in stress decreases as the Y: X ratio decreases.
[0080] FIG. 3 graphically describes the hydro lytic resistance (y-axis) as a function of the Y: X ratio (x-axis). As shown in FIG. 3, the hydrolytic resistance of glasses generally improves as the Y: X ratio decreases.
[0081] Based on the above, it should be understood that glass with a good fusion behavior, a superior ion exchange performance, and a superior hydrolytic resistance, can be achieved by maintaining the Y: X ratio in the glass of greater than or equal to about 0.9, or even greater than or equal to about 1, and less than or equal to about 2. EXAMPLE 3
[0082] Three exemplary glass compositions of the invention were prepared (JL) and three comparative glass compositions (compositions 4-6). The concentration of MgO and CaO in the glass compositions was varied to produce both MgO 5-rich compositions (i.e., JL and 4 compositions) and CaO-rich compositions (i.e., compositions 5-6). The relative amounts of MgO and CaO were also varied so that the glass compositions had different values for the ratio (CaO / (CaO + MgO)). The specific compositions of each of the exemplary glass compositions of the invention and the comparative glass compositions are shown below in Table 3. The properties of each composition were determined as described above in relation to Example 2.
[0083] Table 3: Properties of glass as a function of CaO content


[0084] FIG. 4 graphically describes the D diffusivity of the compositions listed in Table 3 as a function of the proportion of (CaO / (CaO + MgO)). Specifically, FIG. 4 indicates that as the ratio (CaO / (CaO + MgO)) increases, the diffusivity of alkaline ions in the resulting glass decreases thus decreasing the performance of the ion exchange glass. This trend is supported by the data in Table 3 and FIG. 5. FIG. 5 graphically represents the maximum compression stress and change in stress rate (y-axes) as a function of the ratio of (CaO / (CaO + MgO)). FIG.5 indicates that as the ratio (CaO / (CaO + MgO)) increases, the maximum compression stress obtained decreases for a given ion exchange temperature and the ion exchange time. FIG. 5 also indicates that as the ratio (CaO / (CaO + MgO)) increases, the rate of change in voltage increases (ie, it becomes more negative and less desirable).
[0085] Consequently, based on the data in Table 3 and Figs. 4 and 5, it should be understood that glasses with high diffusion coefficients can be produced by minimizing the ratio (CaO / (CaO + MgO)). It was determined that glasses with suitable diffusivities can be produced when the ratio ( CaO / (CaO + MgO)) is less than about 0.5. The values of the glass diffusivity when the ratio (CaO / (CaO + MgO)) is less than about 0.5 decrease the times of ion exchange processes necessary to reach a given level of compression stress and the depth of the layer. Alternatively, glass with high diffusion coefficients, due to the ratio (CaO / (CaO + MgO)) can be used to achieve a higher compression stress and the depth of the layer for a given ion exchange temperature and time ions exchange.
[0086] In addition, the data in Table 3 also indicates that the decrease in the ratio (CaO / (CaO + MgO)), increasing the MgO concentration generally improves the resistance of the glass to hydro lytic degradation as measured by the ISO 720 standard . EXAMPLE 4
[0087] Three exemplary compositions of the invention (MO) and three comparative glass compositions (compositions 7-9) were prepared. The concentration of B 2 O 3 in the glass compositions was varied from 0 mol% to about 4.6 mol% such that the resulting glasses had different values for the ratio B 2 0 3 / (R2 0-A1 2 0 3). The specific compositions of each of the exemplary glass compositions of the invention and the comparative glass compositions are shown below in Table 4. The properties of each glass composition were determined as described above in relation to Examples 2 and 3.
[0088] Table 4: Glass properties depending on the content of B2O3


[0089] FIG. 6 graphically depicts the D (y-axis) diffusivity of the glass compositions in Table 4 as a function of the B2O3 / (R2O-Al2O3) ratio (x-axis) to the glass compositions in Table 4. As shown in FIG. 6, the diffusivity of alkaline ions in glass 5 generally decreases as the proportion of B2O3 / (R2O-Al2O3) increases.
[0090] FIG. 7 graphically represents the hydrolytic resistance according to ISO 720 (y-axis) as a function of the B2O3 / (R2O-Al2O3) ratio (x-axis) for the glass compositions in Table 4. As shown in FIG. 6, the hydrolytic resistance of glass compositions 10 generally improves as the proportion of B2O3 / (R2O-Al2O3) increases.
[0091] Based on Figures 6 and 7, it should be understood that minimizing the B2O3 / (R2O-Al2O3) ratio improves the diffusion of alkaline ions in the glass, thus improving the ion exchange characteristics of the glass. In addition, increasing the proportion of B2O3 / (R2O-Al2O3) also generally improves the glass's resistance to hydrolytic degradation. In addition, it has been found that the resistance of glass to degradation in acidic solutions (as measured by standard DIN 12116) generally increases with decreasing B2O3 concentration. Thus, it was determined that maintaining the ratio of B2O3 / (R2O-Al2O3) to less than or equal to about 0.3 provides the glass with better hydrolytic and acid resistance, as well as providing improved ion exchange characteristics .
[0092] It should now be understood that the glass compositions described here have chemical durability, as well as mechanical durability in the sequence of ion exchange. These properties make the glass compositions suitable for use in various applications, including, without limitation, pharmaceutical packaging materials.
[0093] Based on the above, it should now be understood that the various aspects of glass compositions and glass objects formed from glass compositions are disclosed. According to a first aspect, a glass composition can include: SiO2 in a concentration greater than about 70 mol% and Y mol% of alkaline oxide. Alkaline oxide can include Na2O in an amount greater than about 8 mol%. The glass composition can be free of boron and boron compounds.
[0094] In a second aspect, the glass composition of the first aspect includes SiO2 in an amount greater than or equal to about 72 mol%.
[0095] In a third aspect, the glass composition of the first or second aspects is free of phosphorus and phosphorus compounds.
[0096] In a fourth aspect, the glass composition of any aspect of the first to the third further includes X mol% Al2O3, where the Y: X ratio is greater than 1.
[0097] In a fifth aspect, the glass composition of the Y: X ratio in the fourth aspect is less than or equal to 2.
[0098] In a sixth aspect, the glass composition of the amount of AI2O3 in the fourth or fifth aspect is greater than or equal to about 2 mol% less than or equal to about 10 mol%.
[0099] In a seventh aspect, the glass composition of any aspect of the first to the fifth further includes from about 3 mol% to about 13 mol% of alkaline earth oxide.
[00100] In an eighth aspect, the alkaline earth oxide of the seventh aspect includes MgO and CaO, CaO being present in an amount greater than or equal to about 0.1 mol% AND less than or equal to about 1.0 mol%, and a ratio (CaO (mol%) / (CaO (mol%) + MgO (mol%))) is less than or equal to 0.5.
[00101] In a ninth aspect, a glass composition can include more than about 68 mol% SiO2. X mol% Al2O3 and Y mol% of alkali oxide; and B2O3. Alkali metal oxide can include Na2O in an amount greater than about 8 mol%. The ratio (B2O3 (mol%) / (Y% mol X% mol) can be greater than 0 and less than 0.3.
[00102] In a tenth aspect, the glass composition of the ninth aspect includes SiO2 in an amount greater than or equal to about 72 mol%.
[00103] In an eleventh aspect, the glass composition of the ninth aspect or the eleventh aspect includes B2O3 in an amount greater than or equal to about 0.01 mol% and less than or equal to about 4 mole%.
[00104] In a twelfth aspect, the glass composition of any aspect of the ninth through XI, wherein the glass composition has a Y: X ratio is greater than 1.
[00105] In a XIII aspect, the proportion of Y: X of the twelfth aspect is less than or equal to 2.
[00106] An aspect XIV includes the glass composition of any aspect of the ninth through XIII where x is greater than or equal to about 2 mol% and less than or equal to about 10 mol%.
[00107] An aspect XV includes the glass composition of any aspect of the ninth through XIV wherein the glass composition is free of phosphorus and phosphorus compounds.
[00108] An aspect XVI includes the glass composition of any of the aspects of the ninth through XV, wherein the glass composition furthermore comprises MgO and CaO, the CaO being present in an amount greater than or equal to about 0.1% mol E less than or equal to about 1.0 mol%, and a ratio of (CaO (mol%) / (CaO (mol%) + MgO (mol%)) is less than or equal to 0.5.
[00109] In a XVII aspect, a glass article may have an HGB1 type hydro lytic resistance according to ISO 719. The glass article may include more than about 8 mol% Na2O and less than about 4 mol. % B2O3.
[00110] In an aspect XVIII, the glass article of aspect XVII further comprises X% mol) Al2O3 and Y% mol) alkali metal oxide, in which the ratio (B2O3 (% mol) / (Y% mol) -. X mol%) is greater than 0 and less than 0.3.
[00111] In a XIX aspect, the glass article of any aspect through XVII XVIII further comprises a compression stress layer that has a surface compression stress greater than or equal to about 250 MPa.
[00112] One aspect XX includes the glass article of any aspect through XVII XIX, in which the glass article has, at least, a resistance to class S3 acids according to DIN 12116.
[00113] A twenty-first aspect includes the glass article of any one of the XVII through XX aspect, in which the glass article has at least a basic resistance of class A2 according to ISO 695.
[00114] A twenty-second aspect includes the glass article of any one of the XVII through XXI aspects in which the glass article has a HGA1 type hydrolytic resistance according to the ISO 720 standard.
[00115] In a twenty-third aspect, a pharmaceutical glass package can include: SiO2 in an amount greater than about 70 mol%, the symbol X mol% Al 2 0 3, and Y mol% of alkaline oxide. Alkaline oxide can include Na 2 0 in an amount greater than about 8 mol%. A ratio of a concentration of B 2 0 3 (mol%) in the glass pharmaceutical packaging of (mol Y% - X mol%) can be less than 0.3. The glass pharmaceutical package can also have a lithium resistance type HGB1 hydro according to ISO 719.
[00116] A twenty-fourth aspect includes the glass pharmaceutical package of the twenty-third aspect, in which the amount of SiO2 is greater than or equal to 72 mol% and less than or equal to about 78 mol%.
[00117] A twenty-fifth aspect includes the glass pharmaceutical package from twenty-third to twenty-fourth aspects, where x is greater than or equal to about 4 mol% and less than or equal to about 8 mol%.
[00118] A twenty-sixth aspect includes the glass pharmaceutical package of the twenty-third through twenty-fifth aspects in which the Y: X ratio is greater than 1.
[00119] A twenty-seventh aspect includes the glass pharmaceutical package of the twenty-third through twenty-sixth aspects, in which the Y: X ratio is less than 2.
[00120] One twenty-eighth aspect includes the twenty-three by twenty-seven aspect pharmaceutical package which also comprises from about 4 mol% to about 8 mol% of alkaline earth oxide.
[00121] One twenty-ninth aspect includes the pharmaceutical glass package of the twenty-third through twenty-eighth aspects which further comprises MgO and CaO, CaO is present in an amount greater than or equal to about 0.2 mol% And less than or equal at about 0.7 mol% and a ratio of (CaO (mol%) / (CaO (mol%) + MgO (mol%))) is less than or equal to 0.5.
[00122] A thirtieth aspect includes the glass pharmaceutical package of the twenty-third through aspects twenty-ninth, in which the pharmaceutical package has a type HGA1 hydro lytic resistance according to ISO 720.
[00123] In a thirty-first aspect, a glass composition can include from about 70 mol% to about 80 mol% SiO2. from about 3 mole% to about 13 mole% alkaline earth oxide. X mol%. AI2O3; and Y% in mol of alkaline oxide. Alkaline oxide can include Na 2 0 in an amount greater than about 8 mol%. A Y: X ratio can be greater than 1 and the glass composition can be free of boron and boron compounds.
[00124] In a thirty-second aspect, a glass composition can include: from about 72 mol% to about 78 mol% SiO2; from about 4 mol% to about 8 mol% of alkaline earth oxide, X mol. % Al2O3, and Y% in mol of alkaline oxide. The amount of alkaline earth oxide can be greater than or equal to about 4 mol% and less than or equal to about 8 mol%. Alkali metal oxide can include Na2O in an amount greater than or equal to about 9 mol% and less than or equal to about 15 mol%. A Y: X ratio can be greater than 1. The glass composition can be free of boron and boron compounds.
[00125] In a thirty-third aspect, a glass composition can include from about 68 mol% to about 80 mol% SiO2O .; from about 3 mol% to about 13 mol% of alkaline earth oxide, X mol. % A12O3, and Y% in mol of alkaline oxide. Alkaline oxide can include Na 2 0 in an amount greater than about 8 mol%. The composition of the glass may also include B 2 0 3. The ratio (B203 (mol%) / (Y mol% - X mol%) can be greater than 0 and less than 0.3, and a ratio of Y: X can be greater than 1.
[00126] In a thirty-fourth aspect, a glass composition can include from about 70 mol% to about 80 mol% SiO2; from about 3 mol% to about 13 mol% of alkaline earth oxide, X mol%. A12O3 ;. and Y% in mol of alkaline oxide. Alkaline earth oxide can include CaO in an amount greater than or equal to about 0.1 mol% and less than or equal to about 1.0 mol%. X can be greater than or equal to about 2 mol% and less than or equal to about 10 mol%. Alkali metal oxide can include from about 0.01 mol% to about 1.0 mol%. K2O. A Y: X ratio can be greater than 1. The glass composition can be free of boron and boron compounds.
[00127] In a thirty-fifth aspect, a glass composition can include SiO2 in an amount greater than about 70 mol% and less than or equal to about 80 mol%, from about 3 mol% to about 13% mol alkaline earth oxide ;. X mol% Al2O3 ;. and Y% in mol of alkaline oxide. Alkaline oxide can include Na2O in an amount greater than about 8 mol%. A ratio of a B2O3 concentration (mol%) in the glass composition of (mol Y% - X mol%) can be less than 0.3. A Y: X ratio can be greater than 1.
[00128] In a thirty-sixth aspect, the glass composition of any one of the thirty-one and thirty-thirty-fifth aspects in which SiO2 is present in an amount less than or equal to 78 mol%.
[00129] A thirty-seventh aspect includes the glass composition of any one of thirty-one and a half thirty-sixth aspects, wherein an amount of alkaline earth oxide is greater than or equal to about 4 mol% less than or equal to about 8 mol%
[00130] A thirty-eighth aspect includes the glass composition of any one of the thirty-one to thirty-seventh aspects in which the alkaline earth oxide comprises MgO and CaO and a ratio (CaO (% mol) / (CaO (% mol) + MgO (mol%))) is less than or equal to 0.5.
[00131] A thirty-ninth aspect includes the glass composition of any one of the thirty-one by thirty eighth aspects, wherein the alkaline earth oxide comprises about 0.1 mol% Less than or equal to about 1 , 0 mol% CaO.
[00132] A fortieth aspect includes, the glass composition of any one of the thirty-one and thirty thirty-ninth aspects in which the alkaline earth oxide comprises from about 3 mol% to about 7 mol% MgO.
[00133] A forty-first aspect includes the glass composition of any one of the thirty-one, thirty-fourth aspects of thirty seconds, or, where X is greater than or equal to about 2 moles.% And less than or equal to about 10 mol%.
[00134] A forty-second aspect includes the glass composition of any one of the thirty-one and a half forty-first aspects, wherein the alkali metal oxide comprises more than or equal to about 9 mol% Na2O and less than or equal to about 15 mol% Na2O.
[00135] A forty-third aspect includes the glass composition of any one of the thirty-one and forty-second aspects, in which the Y: X ratio is less than or equal to 2.
[00136] A forty-fourth aspect includes the glass composition of any of the thirty-one and a half forty-third aspects, where the Y: X ratio is greater than or equal to 1.3 and less than or equal to 2.0 .
[00137] A forty-fifth aspect includes the glass composition of any one of the thirty-one and forty-fourth aspects, wherein the alkali metal oxide further comprises K2O in an amount less than or equal to about 3 mol%.
[00138] The forty-sixth aspect includes the glass composition of any of the thirty to forty-fifth aspects, wherein the glass composition is free of phosphorus and phosphorus compounds.
[00139] A forty-sixth includes the glass composition of any of the thirty-one and a half forty-sixth aspects, wherein the alkali metal oxide comprises K 2 0 in an amount greater than or equal to about 0.01 mol% and less than or equal to about 1.0 mol%.
[00140] A forty-eighth aspect includes the glass composition of any of the thirty-second or thirty-fourth aspects, that an amount of SiO2 is greater than or equal to about 70 mol%.
[00141] A forty-ninth aspect includes the glass composition of any of the thirty-second or thirty-fourth aspects, in which the ratio (B2O3 (mol%) / (Y% mol - X mol%) is less than 0.2 .
[00142] A fiftieth aspect includes the glass composition of any one of thirty seconds or thirty-fourth aspects, wherein an amount of B2O3 is less than or equal to about 4.0 mol%.
[00143] A fifty-first aspect includes the glass composition of the fifty-fifth aspect, wherein the amount of B2O3 is greater than or equal to about 0.01 mol%.
[00144] The fifty-second aspect includes the glass composition of the thirty-fourth aspect, wherein the glass composition is free of boron and boron compounds.
[00145] A fifty-third aspect includes the glass composition of any one of the thirty-one and thirty-thirty-fourth aspects, in which the Si0 2 concentration is greater than or equal to about 72 mol%.
[00146] A fifty-fourth aspect includes the glass composition of any of the thirty-first through fifty-third aspects, wherein the SiO2 concentration is greater than or equal to about 73 mol%.
[00147] In fifty-fifth aspects, a glass article is formed from the glass composition of any of the thirty-first through fifty-four aspects.
[00148] The fifty-sixth aspect includes the glass article of the fifty-fifth aspect, in which the glass article has a type HGB1 hydro lytic resistance according to ISO 719.
[00149] The fifty-seventh aspect includes the glass article of any of the fifty-fifth through fifty-sixth aspects, in which the glass article has a type HGA1 hydrolytic resistance according to ISO 720 after strengthening of ion exchange.
[00150] A fifty-eighth aspect includes the glass article of any of the fifty-fifth through fifty-seventh aspects, in which the glass article has an HGA1 type hydrolytic resistance according to ISO 720 before and after strengthening of ion exchange.
[00151] The fifty-ninth aspect includes the glass article of any one of the fifty-fifth through aspects fifty-eighth, in which the glass article has at least one acid class S3 resistance according to DIN 12116.
[00152] A sixtieth aspect includes, the glass article of any of the fifty-fifth through aspects fifty-ninth, in which the glass article has at least a class A2 resistance base according to ISO 695.
[00153] The sixty-first aspect includes the glass article of any of the fifty-fifth through sixty-fifth aspects, wherein the glass article is a pharmaceutical package.
[00154] The sixty-second aspect includes the glass article of any of the fifty-fifth through sixty-first aspects, in which the glass article is of ion-reinforced reinforcement.
[00155] A sixty-third aspect includes the glass article of any one of the fifty-fifth aspects over sixty seconds in which the glass article still has a compression stress layer with a layer depth greater than or equal to 10 μm and a compression surface tension greater than or equal to 250 MPa.
[00156] In sixty-fourth aspect, a glass article may have a type of HGB1 hydrolytic resistance in accordance with ISO 719. The glass article may also have a diffusivity threshold greater than 16 μm2 / hr at a temperature below or equal to 450 ° C.
[00157] A sixty-fifth aspect includes the glass article of the sixty-fourth aspect, in which the threshold diffusivity is greater than or equal to 20 μm2 / hr at a temperature less than or equal to 450 ° C.
[00158] The sixty-sixth aspect includes the glass article of any of the sixty-three by sixty-fourth aspects in which the glass article has an HGA1 type hydrolytic resistance according to ISO 720 after strengthening of ion exchange.
[00159] A sixty-seventh aspect includes the glass article of any one of the sixty-fourth aspects through LXVI aspects that further comprises a compressive stress with a layer depth greater than 25 μm.
[00160] A sixty-eighth aspect includes the glass article of the sixty-seventh aspect in which the layer depth is greater than 35 μm.
[00161] The sixty-ninth aspect includes the glass article from any of the sixty-three through sixty-eighth aspects in which the glass article is reinforced ion exchange and the strengthening of ion exchange consists of treating the glass article in a molten salt bath for less than or equal to 5 hours at a temperature less than or equal to 450 ° C.
[00162] An aspect seventy includes the glass article of any one of the sixty-three through aspects sixty-nine, which further comprises a surface compression stress greater than or equal to 350 MPa.
[00163] A seventy-first aspect includes the glass article of any one of the sixty-three by means of the seventieth aspects in which the surface compression stress is greater than or equal to 400 MPa.
[00164] The seventy-second aspect includes the glass article of any of the sixty-three by seventy-first aspects, in which the glass article is reinforced ion exchange and the strengthening of ion exchange consists of treating the glass article in a bath of molten salt for a time less than or equal to 5 hours at a temperature less than or equal to 450 ° C.
[00165] The seventy-second aspect includes the glass article of any of the sixty-three through seventy-second aspects, wherein the glass article is a pharmaceutical package.
[00166] In seventy-third aspect, a glass article may have a type of HGB1 hydrolytic resistance according to ISO 719. The glass article may also have a compression stress layer with a layer depth of greater than 25 μm and a surface compression stress greater than or equal to 350 MPa. The glass article can be reinforced by ion exchange and for the reinforcement of ion exchange it can include the treatment of the glass article in a molten salt bath for a time less than or equal to 5 hours at a temperature less than or equal to 450 ° C.
[00167] The seventy-fourth aspect includes, the glass article of the seventy-third aspect, in which the glass article has an HGA1 type hydrolytic resistance according to ISO 720 after strengthening of ion exchange.
[00168] A seventy-fifth aspect includes the glass article from any of the seventy-third to the seventy-fourth aspect, where the glass article has a diffusivity threshold greater than 16 μm2 / hr at a temperature of less than or equal to 450 ° C.
[00169] A seventy-sixth aspect includes the glass article from any of the seventy and third parties through aspects seventy-five, in which the threshold diffusivity is greater than or equal to 20 μm2 / hr at a temperature less than or equal to 450 ° C.
[00170] A seventy-seventh aspect includes the glass article from any of the seventy-third to the seventy-sixth aspect, wherein the glass article is a pharmaceutical package.
[00171] It will be evident to those skilled in the art that various modifications and variations can be made to the embodiments described here without departing from the spirit and scope of the claimed matter. Thus, the specification is intended to cover the modifications and variations of the various embodiments described herein, provided that such modification and variations are covered by the scope of the appended claims and their equivalents.

权利要求:
Claims (11)
[0001]
1. Glass composition characterized by the fact that it comprises: SiO2 in a concentration greater than 74 mol% and less than or equal to 80 mol%; X mol% of Al2O3 where X is greater than or equal to 2 mol% and less than or equal to 10 mol%; alkaline earth oxide, in a concentration of 3 mol% to 13 mol%, alkaline earth oxide comprising MgO and CaO and in which CaO is present in an amount greater than or equal to 0.1 mol% and less than or equal to 1.0 mol%, and a ratio of (CaO (mol%) / (CaO (mol%) + MgO (mol%))) is less than or equal to 0.5, and Y mol% of alkali metal oxide, wherein the alkali metal oxide comprises Na2O in an amount greater than 8 mol%, where a Y / X ratio is greater than 1 and less than or equal to 2 and the glass composition is free of boron and boron compounds.
[0002]
2. Glass composition according to claim 1, characterized by the fact that the proportion of Y: X is greater than or equal to 1.3 and less than or equal to 2.
[0003]
Glass composition according to claim 1, characterized by the fact that X is greater than or equal to 5 mol% and less than or equal to 7 mol%.
[0004]
4. Glass composition, according to claim 1, characterized by the fact that the ratio (CaO (% mol) / (CaO (% mol) + MgO (% mol)) is less than or equal to 0.3.
[0005]
5. Glass composition according to claim 1, characterized by the fact that it additionally comprises SnO2.
[0006]
6. Glass composition, according to claim 1, characterized by the fact that: the SiO2 concentration is 74 mol% to 78 mol%; the concentration of alkaline earth oxide is 4 mol% to 8 mol%; the X concentration is greater than or equal to 4 mol% and less than or equal to 8 mol%, and the Na2O concentration is greater than or equal to 9 mol% and less than or equal to 15 mol%.
[0007]
7. Glass composition, according to claim 6, characterized by the fact that the ratio (CaO (% mol) / (CaO (% mol) + MgO (% mol)) is less than or equal to 0.1.
[0008]
Glass composition according to claim 6, characterized by the fact that the alkaline earth oxide comprises 3 mol% to 7 mol% of MgO.
[0009]
Glass composition according to claim 6, characterized by the fact that the alkali metal oxide comprises K2O in an amount greater than or equal to 0.01 mol% and less than or equal to 1.0 mol%.
[0010]
10. Glass article characterized by the fact that it comprises glass with the composition as defined in claim 1.
[0011]
11.Glass article according to claim 10, characterized by the fact that the glass article has a threshold diffusivity greater than 16 μm2 / h at a temperature less than or equal to 450 ° C.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

USRE25456E|1963-10-08|Ultraviolet light absorbing glass |

---

US3054686A|1960-05-18|1962-09-18|Owens Illinois Glass Co|Glass composition having high chemical durability|

---

BE618739A|1962-03-23|

---

US3351474A|1963-12-16|1967-11-07|Owens Illinois Inc|Glass compositions resistant to discoloration, method of making and articles produced therefrom|

---

US3900329A|1965-12-07|1975-08-19|Owens Illinois Inc|Glass compositions|

---

US3844754A|1966-02-23|1974-10-29|Owens Illinois Inc|Process of ion exchange of glass|

---

US3490885A|1966-12-30|1970-01-20|Owens Illinois Inc|Manufacture of chemically-strengthened glass articles|

---

FR2051664B1|1969-07-10|1974-10-11|Asahi Glass Co Ltd|

---

FR2128031B1|1971-03-01|1976-03-19|Saint Gobain Pont A Mousson|

---

US4065317A|1971-10-28|1977-12-27|Nippon Electric Glass Company, Ltd.|Novel glass compositions|

---

DE2609931C3|1975-03-13|1978-07-20|Owens-Illinois, Inc., Toledo, Ohio |Process for producing a protective polymeric coating on a glass surface, which holds glass fragments in place, as well as glass containers|

---

SU990700A1|1980-03-03|1983-01-23|Белорусский технологический институт им.С.М.Кирова|Glass for chemical laboratory glassware|

---

US4312953A|1981-01-29|1982-01-26|Owens-Illinois, Inc.|Olive-green glass compositions|

---

RO83460B1|1981-11-17|1984-03-30|Institutul De Chimie|Packaging bottles showing a high fastness to acids|

---

US4689085A|1986-06-30|1987-08-25|Dow Corning Corporation|Coupling agent compositions|

---

US5114757A|1990-10-26|1992-05-19|Linde Harold G|Enhancement of polyimide adhesion on reactive metals|

---

JP3079579B2|1990-12-18|2000-08-21|日本電気硝子株式会社|Medical UV absorbing glass|

---

DE4113655A1|1991-04-26|1992-10-29|Basf Lacke & Farben|HAFTVERMITTLER|

---

JP2871440B2|1994-02-15|1999-03-17|日本板硝子株式会社|Manufacturing method of chemically strengthened glass|

---

US6096432A|1994-05-17|2000-08-01|Asahi Chemical Company, Limited|Glazing layer-forming composition for hot-coating of furnace refractories and method of forming glazing layer|

---

WO1996024560A1|1995-02-10|1996-08-15|Asahi Glass Company Ltd.|Scratch-resistant glass|

---

US5741745A|1995-02-10|1998-04-21|Asahi Glass Company Ltd.|Abrasion resistant glass|

---

JPH09124339A|1995-08-28|1997-05-13|Asahi Glass Co Ltd|Curved-face glass|

---

JPH09124338A|1995-08-28|1997-05-13|Asahi Glass Co Ltd|Tempered glass|

---

DE19536708C1|1995-09-30|1996-10-31|Jenaer Glaswerk Gmbh|Boro-silicate glass contg. zirconium and lithium oxide|

---

IL116815D0|1996-01-18|1996-05-14|Hadasit Med Res Service|Carpule for an interligamentary syringe|

---

JPH09241033A|1996-03-11|1997-09-16|Asahi Glass Co Ltd|Glass vessel for hermetical sealing|

---

US5908794A|1996-03-15|1999-06-01|Asahi Glass Company Ltd.|Glass composition for a substrate|

---

US6214429B1|1996-09-04|2001-04-10|Hoya Corporation|Disc substrates for information recording discs and magnetic discs|

---

US5854153A|1997-01-09|1998-12-29|Corning Incorporated|Glasses for display panels|

---

DE29702816U1|1997-02-18|1997-04-10|Schott Glaswerke|Sterilizable glass container for medical purposes, in particular for storing pharmaceutical or diagnostic products|

---

DE19706255C2|1997-02-18|2000-11-30|Schott Glas|Sterilizable glass container for medical purposes, in particular for storing pharmaceutical or diagnostic products|

---

FR2761978B1|1997-04-11|1999-05-07|Saint Gobain Vitrage|GLASS COMPOSITION AND CHEMICALLY TEMPERED GLASS SUBSTRATE|

---

JP3384286B2|1997-06-20|2003-03-10|日本板硝子株式会社|Glass substrate for magnetic recording media|

---

JP4077536B2|1997-07-11|2008-04-16|日本無機株式会社|Extra fine glass fiber|

---

JP4016455B2|1997-07-23|2007-12-05|旭硝子株式会社|Substrate glass composition|

---

GB9715446D0|1997-07-23|1997-09-24|British Ceramic Res Ltd|Glazes|

---

JPH11180728A|1997-12-22|1999-07-06|Central Glass Co Ltd|Substrate glass composition for display device|

---

JPH11180727A|1997-12-22|1999-07-06|Central Glass Co Ltd|Substrate glass composition for display device|

---

JPH11240735A|1998-02-27|1999-09-07|Asahi Glass Co Ltd|Glass composition for use as substrate|

---

GB2335423A|1998-03-20|1999-09-22|Pilkington Plc|Chemically toughenable glass|

---

JPH11328601A|1998-05-12|1999-11-30|Asahi Techno Glass Corp|Glass board for recording medium, recording medium using glass board and manufacture of glass board for recording medium|

---

JPH11335133A|1998-05-27|1999-12-07|Central Glass Co Ltd|Substrate glass for display device|

---

JP2000007372A|1998-06-19|2000-01-11|Asahi Techno Glass Corp|Glass for chemical tempering and glass base for magnetic recording medium|

---

JP3657453B2|1999-02-04|2005-06-08|日本板硝子株式会社|Information processing recording medium|

---

US6630420B1|1999-02-15|2003-10-07|Schott Glas|Glass with high proportion of zirconium-oxide and its uses|

---

DE19906240A1|1999-02-15|2000-08-17|Schott Glas|Glass composition used, e.g., as container glass for chemically aggressive liquids contains a high amount of zirconium oxide|

---

US6277777B1|1999-08-03|2001-08-21|Johns Manville International, Inc.|Boron-free glass composition and filtration media|

---

JP2001180969A|1999-12-28|2001-07-03|Central Glass Co Ltd|Manufacturing method of lithium-containing glass with high young's modulus and its glass product|

---

JP2001192239A|1999-12-28|2001-07-17|Asahi Techno Glass Corp|Method for manufacturing strengthened glass, strengthened glass and glass substrate|

---

JP4389257B2|2000-03-06|2009-12-24|日本電気硝子株式会社|Glass substrate for flat panel display|

---

JP2002003241A|2000-06-19|2002-01-09|Central Glass Co Ltd|Glass for press molding and glass substrate for information recording media|

---

JP2002025762A|2000-07-04|2002-01-25|Nippon Electric Glass Co Ltd|Glass board for inorganic el display|

---

DE10035801B4|2000-07-22|2008-04-03|Schott Ag|Borosilicate glass of high chemical resistance and its uses|

---

EP1193185A1|2000-10-02|2002-04-03|Heineken Technical Services B.V.|Glass container with improved coating|

---

US6472068B1|2000-10-26|2002-10-29|Sandia Corporation|Glass rupture disk|

---

RU2173673C1|2000-11-04|2001-09-20|Валеев Макарим Ямгутдинович|Medical glass|

---

JP4686858B2|2000-12-26|2011-05-25|日本電気硝子株式会社|Glass substrate for flat panel display|

---

JP2001229526A|2001-01-04|2001-08-24|Nippon Sheet Glass Co Ltd|Magnetic disk substrate consisting of glass composition for chemical strengthening and magnetic disk medium|

---

JP2001236634A|2001-01-04|2001-08-31|Nippon Sheet Glass Co Ltd|Magnetic disk substrate comprising glass composition for chemical strengthening and magnetic disk medium|

---

JP3995902B2|2001-05-31|2007-10-24|Ｈｏｙａ株式会社|Glass substrate for information recording medium and magnetic information recording medium using the same|

---

JP4590866B2|2001-11-05|2010-12-01|旭硝子株式会社|Glass ceramic composition|

---

GB0127942D0|2001-11-21|2002-01-16|Weston Medical Ltd|Needleless injector drug capsule and a method for filing thereof|

---

JP2002249340A|2001-11-30|2002-09-06|Hoya Corp|Cover glass for semiconductor package|

---

EP1460044B2|2001-12-28|2016-10-26|Nippon Sheet Glass Company, Limited|Sheet glass and photoelectric converter-use sheet glass|

---

DE10238930C1|2002-08-24|2003-11-20|Schott Glas|Aluminum-free borosilicate glass used in the production of ampoules and bottles in the pharmaceutical industry and for laboratory devices and equipment includes oxides of silicon and boron|

---

JP2004131314A|2002-10-09|2004-04-30|Asahi Glass Co Ltd|Chemically strengthened glass substrate with transparent conductive film and its manufacturing process|

---

CN1753840A|2003-02-25|2006-03-29|肖特股份公司|Antimicrobial active borosilicate glass|

---

JP2004315317A|2003-04-17|2004-11-11|Nippon Sheet Glass Co Ltd|Glass composition, sealed container formed of glass composition thereof, and quartz resonator using the sealed container|

---

JP2005048142A|2003-07-31|2005-02-24|Nippon Sheet Glass Co Ltd|Solution for forming colored film and method for producing glass base having colored film formed by using the same|

---

WO2005042428A2|2003-10-29|2005-05-12|Saint-Gobain Glass France|Tempered glass for thermal insulation|

---

DE102004011009A1|2004-03-08|2005-09-29|Schott Ag|Surface-modified, multi-component glass articles, e.g. light bulbs, optical elements or containers, having surface atoms replaced by other atoms to improve properties, e.g. chemical resistance or hardness|

---

US7470999B2|2004-09-29|2008-12-30|Nippon Electric Glass Co., Ltd.|Glass for semiconductor encapsulation and outer tube for semiconductor encapsulation, and semiconductor electronic parts|

---

US8152915B2|2005-09-02|2012-04-10|Basf Se|Process for preparation of a novel pigmented composition for use in gravure inks|

---

WO2008050500A1|2006-09-29|2008-05-02|Nippon Electric Glass Co., Ltd.|Protective plate for portable equipment display device|

---

US20070123410A1|2005-11-30|2007-05-31|Morena Robert M|Crystallization-free glass frit compositions and frits made therefrom for microreactor devices|

---

US7833919B2|2006-02-10|2010-11-16|Corning Incorporated|Glass compositions having high thermal and chemical stability and methods of making thereof|

---

KR100630309B1|2006-04-13|2006-10-02|한국나노글라스|The tempered glass for protecting a portable telephone LCD and the manufacturing method the tempered glass|

---

EP2022767B1|2006-05-19|2011-04-06|Toyo-sasaki Glass Co., Ltd.|Crystal glass article|

---

US8076014B2|2006-06-08|2011-12-13|Hoya Corporation|Glass for use in substrate for information recording medium, substrate for information recording medium and information recording medium, and their manufacturing method|

---

US20070293388A1|2006-06-20|2007-12-20|General Electric Company|Glass articles and method for making thereof|

---

EP2075237B1|2006-10-10|2019-02-27|Nippon Electric Glass Co., Ltd.|Reinforced glass substrate|

---

CN101541696A|2006-11-22|2009-09-23|旭硝子株式会社|Glass for information recording medium substrate|

---

JP2008195602A|2007-01-16|2008-08-28|Nippon Electric Glass Co Ltd|Method for manufacturing tempered glass substrate and tempered glass substrate|

---

JP5808069B2|2007-02-16|2015-11-10|日本電気硝子株式会社|Glass substrate for solar cell|

---

US7666511B2|2007-05-18|2010-02-23|Corning Incorporated|Down-drawable, chemically strengthened glass for cover plate|

---

JP2010530911A|2007-06-15|2010-09-16|マヤテリアルズインク|New multifunctional silsesquioxanes for painting|

---

JP2010202413A|2007-06-27|2010-09-16|Asahi Glass Co Ltd|Method for producing glass, method for producing glass raw material, and glass raw material|

---

JP5467490B2|2007-08-03|2014-04-09|日本電気硝子株式会社|Method for producing tempered glass substrate and tempered glass substrate|

---

EP2031124A1|2007-08-27|2009-03-04|Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO|Coating having low friction characteristics|

---

JP5743125B2|2007-09-27|2015-07-01|日本電気硝子株式会社|Tempered glass and tempered glass substrate|

---

DE102007063463B4|2007-12-20|2010-06-10|Schott Ag|Core glass in the alkali-zinc-silicate glass system for a fiber optic light guide and the use of the core glass in a light guide|

---

KR101579308B1|2008-02-25|2015-12-21|가부시키가이샤 노리타케 캄파니 리미티드|Ceramic product and ceramic member bonding method|

---

AU2009248885B2|2008-05-23|2015-02-05|Hospira, Inc.|Packaged iron sucrose products|

---

JP5444846B2|2008-05-30|2014-03-19|旭硝子株式会社|Glass plate for display device|

---

JP5867953B2|2008-06-27|2016-02-24|日本電気硝子株式会社|Tempered glass and tempered glass|

---

JP5614607B2|2008-08-04|2014-10-29|日本電気硝子株式会社|Tempered glass and method for producing the same|

---

JP2012500177A|2008-08-21|2012-01-05|コーニングインコーポレイテッド|Durable glass housing / enclosure for electronic devices|

---

CN102137819A|2008-09-01|2011-07-27|法国圣戈班玻璃厂|Process for obtaining glass and glass obtained|

---

JP5622069B2|2009-01-21|2014-11-12|日本電気硝子株式会社|Tempered glass, tempered glass and method for producing tempered glass|

---

US8535761B2|2009-02-13|2013-09-17|Mayaterials, Inc.|Silsesquioxane derived hard, hydrophobic and thermally stable thin films and coatings for tailorable protective and multi-structured surfaces and interfaces|

---

JP5699434B2|2009-04-02|2015-04-08|旭硝子株式会社|Glass for information recording medium substrate, glass substrate for information recording medium and magnetic disk|

---

FR2946637B1|2009-06-12|2012-08-03|Schott Ag|LOW NEUTRAL GLASS IN BORE WITH TITANIUM AND ZIRCONIUM OXIDE|

---

JP2012184118A|2009-07-16|2012-09-27|Asahi Glass Co Ltd|Glass plate for display device|

---

US8647995B2|2009-07-24|2014-02-11|Corsam Technologies Llc|Fusion formable silica and sodium containing glasses|

---

CN102471133B|2009-08-10|2014-10-15|Hoya株式会社|Glass for magnetic recording medium substrate, magnetic recording medium substrate and method for producing same, and magnetic recording medium|

---

US8802581B2|2009-08-21|2014-08-12|Corning Incorporated|Zircon compatible glasses for down draw|

---

DE102009038475B4|2009-08-21|2011-07-07|Schott Ag, 55122|Use of a glass for glass-metal connections|

---

CN101717189B|2009-08-28|2011-06-08|武汉力诺太阳能集团股份有限公司|High chemical resistance borosilicate glass and purpose thereof|

---

JP5115545B2|2009-09-18|2013-01-09|旭硝子株式会社|Glass and chemically tempered glass|

---

WO2011037001A1|2009-09-28|2011-03-31|コニカミノルタオプト株式会社|Glass substrate for information recording media and information recording medium|

---

KR20120098601A|2009-10-19|2012-09-05|아사히 가라스 가부시키가이샤|Glass plate for substrate, method for producing same, and method for producing tft panel|

---

JP5621239B2|2009-10-20|2014-11-12|旭硝子株式会社|GLASS PLATE FOR DISPLAY DEVICE, PLATE GLASS FOR DISPLAY DEVICE, AND METHOD FOR PRODUCING THE SAME|

---

TW201121914A|2009-10-20|2011-07-01|Asahi Glass Co Ltd|Glass sheet for cu-in-ga-se solar cells, and solar cells using same|

---

DE102009051852B4|2009-10-28|2013-03-21|Schott Ag|Borless glass and its use|

---

CN102092940A|2009-12-11|2011-06-15|肖特公开股份有限公司|Aluminum silicate glass for touch screen|

---

JP2011132061A|2009-12-24|2011-07-07|Asahi Glass Co Ltd|Glass substrate for information recording medium and magnetic disk|

---

CN102167509A|2010-02-26|2011-08-31|肖特玻璃科技有限公司|Chemical toughened glass capable of carrying out subsequent cutting|

---

CN102167507B|2010-02-26|2016-03-16|肖特玻璃科技有限公司|For the thin lithium aluminosilicate glass of 3D tight mould pressing|

---

KR20130072187A|2010-05-19|2013-07-01|아사히 가라스 가부시키가이샤|Glass for chemical strengthening and glass plate for display device|

---

WO2012026290A1|2010-08-24|2012-03-01|旭硝子株式会社|Cover glass for flat panel displays and production method|

---

IT1402048B1|2010-10-19|2013-08-28|Bormioli Luigi Spa|ITEM IN MATERIAL OVERLAPPED COMPOSITE AND ITS PREPARATION PROCEDURE|

---

DE102010054967B4|2010-12-08|2014-08-28|Schott Ag|Boreless universal glass and its use|

---

JP5834793B2|2010-12-24|2015-12-24|旭硝子株式会社|Method for producing chemically strengthened glass|

---

FR2972446B1|2011-03-09|2017-11-24|Saint-Gobain Glass France|SUBSTRATE FOR PHOTOVOLTAIC CELL|

---

TW201245080A|2011-03-17|2012-11-16|Asahi Glass Co Ltd|Glass for chemical strengthening|

---

TWI591039B|2011-07-01|2017-07-11|康寧公司|Ion exchangeable glass with high compressive stress|

---

DE112012003315T5|2011-08-10|2014-04-30|Asahi Glass Company, Limited|Glass for chemical hardening and glass housing|

---

JP6204920B2|2011-10-25|2017-09-27|コーニング インコーポレイテッド|Alkaline earth aluminosilicate glass composition with improved chemical and mechanical durability|

---

CA2966274C|2011-10-25|2020-02-18|Corning Incorporated|Glass compositions with improved chemical and mechanical durability|

---

US9517966B2|2011-10-25|2016-12-13|Corning Incorporated|Glass compositions with improved chemical and mechanical durability|

---

US10350139B2|2011-10-25|2019-07-16|Corning Incorporated|Pharmaceutical glass packaging assuring pharmaceutical sterility|

---

US9186295B2|2011-10-25|2015-11-17|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US10273048B2|2012-06-07|2019-04-30|Corning Incorporated|Delamination resistant glass containers with heat-tolerant coatings|

---

US9139469B2|2012-07-17|2015-09-22|Corning Incorporated|Ion exchangeable Li-containing glass compositions for 3-D forming|

---

JP2014037343A|2012-07-18|2014-02-27|Nippon Electric Glass Co Ltd|Glass for medicine container and glass tube using the same|

---

WO2014179140A2|2013-04-29|2014-11-06|Corning Incorporated|Photovoltaic module package|

---

DE102015116097B4|2015-09-23|2017-09-21|Schott Ag|Chemically resistant glass and its use|CN101910079A|2007-11-29|2010-12-08|康宁股份有限公司|Glass with improved toughness and scrath resistance|

---

JP6204920B2|2011-10-25|2017-09-27|コーニング インコーポレイテッド|Alkaline earth aluminosilicate glass composition with improved chemical and mechanical durability|

---

US9517966B2|2011-10-25|2016-12-13|Corning Incorporated|Glass compositions with improved chemical and mechanical durability|

---

CA2966274C|2011-10-25|2020-02-18|Corning Incorporated|Glass compositions with improved chemical and mechanical durability|

---

US10350139B2|2011-10-25|2019-07-16|Corning Incorporated|Pharmaceutical glass packaging assuring pharmaceutical sterility|

---

US9186295B2|2011-10-25|2015-11-17|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

EP3246298A1|2016-05-12|2017-11-22|Corning Incorporated|Pharmaceutical glass coating for achieving particle reduction|

---

US10273048B2|2012-06-07|2019-04-30|Corning Incorporated|Delamination resistant glass containers with heat-tolerant coatings|

---

JP2014037343A|2012-07-18|2014-02-27|Nippon Electric Glass Co Ltd|Glass for medicine container and glass tube using the same|

---

US10117806B2|2012-11-30|2018-11-06|Corning Incorporated|Strengthened glass containers resistant to delamination and damage|

---

US9717648B2|2013-04-24|2017-08-01|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9707155B2|2013-04-24|2017-07-18|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9849066B2|2013-04-24|2017-12-26|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9707153B2|2013-04-24|2017-07-18|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9713572B2|2013-04-24|2017-07-25|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9707154B2|2013-04-24|2017-07-18|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9700485B2|2013-04-24|2017-07-11|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9839579B2|2013-04-24|2017-12-12|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9717649B2|2013-04-24|2017-08-01|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9700486B2|2013-04-24|2017-07-11|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

US9603775B2|2013-04-24|2017-03-28|Corning Incorporated|Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients|

---

WO2014179140A2|2013-04-29|2014-11-06|Corning Incorporated|Photovoltaic module package|

---

JP6455799B2|2013-06-06|2019-01-23|日本電気硝子株式会社|Glass tubes for pharmaceutical containers and pharmaceutical containers|

---

US10442730B2|2013-11-25|2019-10-15|Corning Incorporated|Method for achieving a stress profile in a glass|

---

US10144198B2|2014-05-02|2018-12-04|Corning Incorporated|Strengthened glass and compositions therefor|

---

KR20170047344A|2014-08-28|2017-05-04|코닝 인코포레이티드|Laminated Glass Article with Ion Exchangeable Core and Clad Layers Having Diffusivity Contrast and Method of Making the Same|

---

AU2015374000B2|2014-12-31|2020-05-07|Corning Incorporated|Methods for treating glass articles|

---

RU2707210C2|2014-12-31|2019-11-25|Корнинг Инкорпорейтед|Methods of glass articles heat treatment|

---

DE102015116097B4|2015-09-23|2017-09-21|Schott Ag|Chemically resistant glass and its use|

---

US10043903B2|2015-12-21|2018-08-07|Samsung Electronics Co., Ltd.|Semiconductor devices with source/drain stress liner|

---

US20170320769A1|2016-05-06|2017-11-09|Corning Incorporated|Glass compositions that retain high compressive stress after post-ion exchange heat treatment|

---

CN109219526A|2016-05-31|2019-01-15|康宁股份有限公司|The anti-counterfeit measures of glassware|

---

TW201808837A|2016-06-07|2018-03-16|康寧公司|Methods and apparatuses for forming glass tubing from glass preforms|

---

EP3299347B1|2016-09-22|2018-09-26|Schott AG|Aluminium-free borosilicate glass|

---

EP3330234A1|2016-11-30|2018-06-06|Corning Incorporated|Lithium containing aluminosilicate glasses|

---

US11014849B2|2016-11-30|2021-05-25|Corning Incorporated|Systems and methods for ion exchanging glass articles|

---

DE102017102482B4|2017-02-08|2019-11-21|Schott Ag|Glasses with improved ion exchangeability and thermal expansion|

---

EP3601176A2|2017-03-31|2020-02-05|Corning Incorporated|High transmission glasses|

---

US11034613B2|2017-11-21|2021-06-15|Corning Incorporated|Methods for ion exchanging glass articles|

---

US20190161399A1|2017-11-30|2019-05-30|Corning Incorporated|Glass articles with low-friction coatings and methods for coating glass articles|

---

DE102018116460A1|2018-07-06|2020-01-09|Schott Ag|Highly resistant and chemically toughened glasses|

---

DE102018127528A1|2018-11-05|2020-05-07|Schott Ag|Glass containers and method of making same|

---

US20200156991A1|2018-11-20|2020-05-21|Corning Incorporated|Glass articles having damage-resistant coatings and methods for coating glass articles|

---

US20200171478A1|2018-11-29|2020-06-04|Corning Incorporated|Ion exchange systems and methods for ion exchanging glass articles|

---

RU2726812C1|2019-09-25|2020-07-15|Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации|Glass hardened by ion exchange|

---

WO2022020120A1|2020-07-20|2022-01-27|Corning Incorporated|Stress features for crack redirection and protection in glass containers|

法律状态:
2017-05-02| B15I| Others concerning applications: loss of priority|

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2017-07-11| B12F| Other appeals [chapter 12.6 patent gazette]|

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2019-05-14| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161551163P| true| 2011-10-25|2011-10-25|

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US61/551,163|2011-10-25|

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PCT/US2012/061867|WO2013063238A1|2011-10-25|2012-10-25|Glass compositions with improved chemical and mechanical durability|

---