Borosilicate glass article with low boron content

Abstract

A chemically temperable borosilicate glass article has a low boron content and a corresponding Na.sub.2O content. The articles have good diffusivities and hydrolytical resistance values. When chemically tempered, the borosilicate glass article exhibits a compressive stress CS >400 MPa and a penetration depth DoL >20 μm. A pharmaceutical primary packaging including the borosilicate glass article is also disclosed.

Claims

1. A borosilicate glass article, comprising a glass comprising a composition comprising B.sub.2O.sub.3 and Na.sub.2O and a ratio B.sub.2O.sub.3/Na.sub.2O in mol % of less than 1.20 and further having a diffusivity of 6 μm.sup.2/h to 25 μm.sup.2/h and a hydrolytic resistance of HGA1 according to ISO720:1985, wherein the composition comprises (in mol % on oxide basis): TABLE-US-00020 SiO.sub.2 65.0-80.0; B.sub.2O.sub.3  3.0-10.0; Al.sub.2O.sub.3  3.0-8.0; Na.sub.2O  8.0-12.5; and MgO   >0-3.2, wherein the composition has a ratio of B.sub.2O.sub.3/MgO in mol% that is less than 10.0.

2. The glass article of claim 1, wherein the composition comprises 3.6-8.5 mol % B.sub.2O.sub.3.

3. The glass article of claim 1, wherein the composition comprises (in mol % on oxide basis): TABLE-US-00021 Li.sub.2O 0-2.5; K.sub.2O 0-2.0; and CaO 0-2.5.

4. The glass article of claim 1, wherein the composition comprises CaO and a cumulative amount of MgO and CaO is less than 4 mol %.

5. The glass article of claim 1, wherein the composition has a ratio of B.sub.2O.sub.3/MgO in mol % of at least 1.4.

6. The glass article of claim 3, wherein a ratio of molar concentrations of B.sub.2O.sub.3 relative to the sum of concentrations of B.sub.2O.sub.3 and Al.sub.2O.sub.3 is at least 0.30.

7. The glass article of claim 1, wherein the ratio B.sub.2O.sub.3/Na.sub.2O in mol % is at least 0.10.

8. The glass article of claim 3, wherein the composition further comprises (in mol % on oxide basis): one or more refining agents 0.01-2.0.

9. The glass article of claim 1, wherein the glass exhibits a compaction of from 20 to 70 μm per 100 mm article length.

10. The glass article of claim 1, wherein the diffusivity is from 6.3 μm.sup.2/h to 20.5 μm.sup.2/h.

11. The glass article of claim 1, wherein the glass has a coefficient of thermal expansion (CTE.sub.20 to 300°c) of from 5.1*10.sup.−6/K to 7.3*10.sup.−6/K.

12. The glass article of claim 1, wherein the glass has a crystallization rate not exceeding a limit of 0.1 μm/min in a temperature range limited by a liquidus temperature and a temperature at which a viscosity of the glass is 10.sup.6.5-7.0 dPa.Math.s.

13. The glass article of claim 1, wherein a ratio E/ρ of Young's E modulus to density p of the glass is at least 303*10.sup.6 m.sup.2/s.sup.2.

14. The glass article of claim 1, wherein the article is chemically tempered to have at least one of a compressive stress >400 MPa or a penetration depth DoL >20 μm.

15. A method of making a glass article, the method comprising: drawing a glass melt to form the glass article or a glass article precursor, the glass melt comprising a composition comprising B.sub.2O.sub.3 and Na.sub.2O and a ratio B.sub.2O.sub.3/Na.sub.2O in mol % of less than 1.20 and further having a diffusivity of 6 μm.sup.2/h to 25 μm.sup.2/h and a hydrolytic resistance of HGA1 according to ISO720:1985, wherein the composition comprises (in mol % on oxide basis): TABLE-US-00022 SiO.sub.2 65.0-80.0; B.sub.2O.sub.3  3.0-10.0; Al.sub.2O.sub.3  3.0-8.0; Na.sub.2O  8.0-12.5; and MgO   >0-3.2, wherein the composition has a ratio of B.sub.2O.sub.3/MgO in mol % that is less than 10.0; and cooling the glass article or the glass article precursor.

16. A pharmaceutical product, comprising: a glass article comprising a glass comprising a composition comprising B.sub.2O.sub.3 and Na.sub.2O and a ratio B.sub.2O.sub.3/Na.sub.2O in mol % of less than 1.20 and further having a diffusivity of 6 μm.sup.2/h to 25 μm.sup.2/h and a hydrolytic resistance of HGA1 according to ISO720:1985, wherein the composition comprises (in mol % on oxide basis): TABLE-US-00023 SiO.sub.2 65.0-80.0; B.sub.2O.sub.3  3.0-10.0; Al.sub.2O.sub.3  3.0-8.0; Na.sub.2O  8.0-12.5; and MgO   >0-3.2, wherein the composition has a ratio of B.sub.2O.sub.3/MgO in mol % that is less than 10.0; and a drug formulation contained in the glass article.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Exemplary embodiments provided according to the present invention are described in greater detail with reference to example embodiments and comparative examples, which illustrate the teaching of the invention but are not intended to restrict it.

EXAMPLES

(2) 16 different borosilicate glasses (glass compositions A1 to A16) were produced, the compositions of each of which have the following properties: the borosilicate glasses are chemically temperable; the diffusivity is at least 6 μm.sup.2/h, the ratio (1): B.sub.2O.sub.3/Na.sub.2O <1.20 [mol %]; and the glasses have excellent hydrolytic resistance.

(3) The detailed borosilicate glass compositions with the individual components and the various properties based on the calculated and measured parameters are summarized in the following Tables 1 and 2:

(4) TABLE-US-00010 TABLE 1 A1 A2 A3 A4 A5 A6 A7 A8 SiO.sub.2 78.0 75.8 76.0 76.7 76.8 73.9 75.4 77.6 B.sub.2O.sub.3 5.1 5.1 4.3 6.9 6.8 7.0 6.9 6.9 Al.sub.2O.sub.3 4.2 4.9 6.1 4.2 3.7 4.9 3.6 3.7 Li.sub.2O 0.8 1.0 0.8 0.8 Na.sub.2O 10.3 10.9 10.0 9.8 8.8 10.9 10.8 8.9 K.sub.2O 0.3 0.6 0.7 0.3 0.3 0.7 MgO 0.8 0.8 0.8 0.8 0.8 0.8 CaO 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Cl 0.5 0.6 0.4 0.5 0.5 0.6 0.6 0.5 F.sup.− 1.1 1.1 1.1 BaO Sb.sub.2O.sub.3 0.1 TOTAL 100 100 100 100 100 100 100 100 B.sub.2O.sub.3/Na.sub.2O < 1.2 0.50 0.47 0.43 0.70 0.77 0.64 0.64 0.78 B.sub.2O.sub.3/R.sub.2O < 1.2 0.50 0.43 0.37 0.70 0.72 0.58 0.58 0.72 R.sub.2O = Σ (Na.sub.2O + K.sub.2O + Li.sub.2O) B.sub.2O.sub.3/MgO 6.4 5.4 8.5 8.8 8.6 8.6 B.sub.2O.sub.3/(B.sub.2O.sub.3 + Al.sub.2O.sub.3) 0.55 0.51 0.41 0.6 0.65 0.59 0.66 0.65 CTE [10.sup.−6/K] 6.4 7.2 7.1 6.2 6.1 7.2 7.1 6.0 Tg [° C.] 512 535 540 510 505 530 525 540 VA [° C.] 1140 1110 1170 1120 1140 1070 1050 1150 USP660 Glass 0.089 0.078 0.084 0.074 Grains (Titration)* [ml] Limit Type 1 (according 89% 78% 84% 74% to USP 660)** HGA Class (according 1 1 1 1 1 1 1 1 to ISO 720) CS [MPa] at 450° C./9 h 438 505 533 453 429 531 510 467 DOL [μm] at 450° C./9 h 24 27 32 22 22 22 21 23 D [μm.sup.2/h] at 450° C. 8.2 10.3 14.5 6.9 6.9 6.9 6.3 7.5 Density ρ [g/cm.sup.3] 2.351 2.376 2.372 2.352 2.352 2.384 2.380 2.356 Young's modulus E 70.977 71.488 72.066 71.937 71.706 72.444 71.483 71.135 [Gpa] E/ρ [*10.sup.6m.sup.2s.sup.2] 301.896 300.852 303.763 305.803 304.811 3030.889 300.343 301.990 *Consumption of 0.02N HCl per g of glass grains in [ml]. **the specified percentages indicate the extent to which the value corresponds to the Limit of 0.10.

(5) In this description “CTE” is the coefficient of thermal expansion at 20 to 300° C., “Tg” is the glass transition temperature, “VA” is the processing temperature in ° C. (the temperature at a glass viscosity of 10.sup.4 dPa s).

(6) TABLE-US-00011 TABLE 2 A9 A10 A11 A12 A13 A14 A15 A16 SiO.sub.2 73.1 76.7 74.3 76.7 76.85 73.3 74.8 75.0 B.sub.2O.sub.3 7.1 4.3 4.2 4.2 4.4 4.3 4.4 4.4 Al.sub.2O.sub.3 6.2 6.2 6.2 6.1 6.2 6.4 6.1 6.2 Li.sub.2O 1.0 1.0 1.1 1.0 1.1 2.0 1.0 Na.sub.2O 10.0 10.0 10.0 9.9 10.1 10.0 10.1 10.0 K.sub.2O 0.6 0.6 0.6 0.0 0.6 0.6 0.6 1.3 MgO 0.8 0.8 1.6 0.8 0.0 3.0 0.7 0.8 CaO 0.8 0.8 1.6 0.8 0.0 0.8 0.8 0.8 Cl 0.4 0.6 0.5 0.4 0.35 0.5 0.5 0.5 F.sup.− BaO 0.5 SB.sub.2O.sub.3 TOTAL 100 100 100 100 100 100 100 100 B.sub.2O.sub.3/Na.sub.2O < 1.2 0.71 0.43 0.42 0.42 0.44 0.43 0.44 0.44 B.sub.2O.sub.3/R.sub.2O <1.2 0.61 0.41 0.36 0.38 0.38 0.37 0.35 0.36 R.sub.2O = Σ (Na.sub.2O + K.sub.2O + Li.sub.2O) B.sub.2O.sub.3/MgO 8.9 5.4 2.6 5.3 1.4 6.3 5.5 B.sub.2O.sub.3/(B.sub.2O.sub.3+ Al.sub.2O.sub.3) 0.53 0.41 0.41 0.41 0.42 0.40 0.42 0.42 CTE [10.sup.−6/K] 7.1 6.8 7.0 6.7 5.1 7.1 7.3 7.3 Tg [° C.] 535 560 540 545 510 540 520 540 VA [° C.] 1110 1210 1210 1190 1225 1220 1130 1160 USP660 Glass 0.063 0.067 0.084 0.068 0.053 0.076 0.086 0.077 Grains (Titration)* [ml] Limit Type 1 (according 63% 67% 84% 68% 53% 76% 86% 77% to USP 660)** HGA Class (according to 1 1 1 1 1 1 1 1 ISO 720) CS [MPa] at 450° C./9 h 544 534 560 530 488 554 513 487 DOL [μm] at 450° C./9 h 25 38 28 29 31 30 34 26 D [μm.sup.2/h] at 450° C. 8.9 20.5 11.1 11.9 13.6 12.8 16.4 9.6 Density ρ [g/cm.sup.3] 2.381 2.363 2.389 2.365 2.359 2.391 2.381 2.380 Young's modulus E [GPa] 73.465 71.685 72.579 72.224 71.806 73.123 72.552 72.017 E/ρ [*10.sup.6m.sup.2s.sup.2] 308.515 303.399 303.775 305.394 304.338 305.845 304.733 302.580 *Consumption of 0.02N HCl per g of glass grains in [ml]. **the specified percentages indicate the extent to which the value corresponds to the limit of 0.10.

(7) In the glass compositions for all example embodiments A1 to A16 the ratio B.sub.2O.sub.3/Na.sub.2O [in mol %] is less than 1.20. These borosilicate glasses not only show excellent properties but can also be tempered well, i.e. good values are achieved both for compressive stress (CS) and penetration depth (DoL).

(8) In addition, borosilicate glasses were produced as comparative examples, in which the ratio (1) B.sub.2O.sub.3/Na.sub.2O for the glass compositions V1 and V2 [in mol %] is greater than 1.20 and the ratio (2) B.sub.2O.sub.3/R.sub.2O for the glass compositions V1 and V2 [in mol %] is greater than 1.20.

(9) The detailed borosilicate glass compositions V1 and V2 with the individual components and the various properties based on the calculated and measured parameters are summarized in the following Table 3.

(10) TABLE-US-00012 TABLE 3 Oxide [mol %] V1 V2 SiO.sub.2 78.3 76.9 B.sub.2O.sub.3 9.3 9.2 Al.sub.2O.sub.3 3.3 4.4 Li.sub.2O Na.sub.2O 7.2 6.2 K.sub.2O 1.4 MgO CaO 1.6 1.1 Cl 0.2 F— 0.3 BaO 0.6 TOTAL 100.0 100.0 B.sub.2O.sub.3/Na.sub.2O > 1.20 1.29 1.48 B.sub.2O.sub.3/R.sub.2O > 1.20 1.29 1.21 R.sub.2O = Σ (Na.sub.2O, K.sub.2O, Li.sub.2O) CTE [10.sup.−6/K] 5 5 Tg [° C.] 565 567 VA [° C.] 1165 1182 USP660 Glass 0.055 Grains (Titration) [ml] Limit Type 1 (according 55% to USP 660) HGA Class (according 1 to ISO 720) CS [MPa] at 450° C./9 h 362 DOL [μm] at 450° C./9 h 16 D [μm2/h] 3.6 <6.0

(11) The ratio (1): B.sub.2O.sub.3/Na.sub.2O at 1.29 lies outside the claimed range for example V1.

(12) In the borosilicate glass composition V2, the Na.sub.2O content of 6.2 mol % is not within the previously described glass composition range; in addition, the ratio (1): B.sub.2O.sub.3/Na.sub.2O of 1.48 is outside the previously described range.

(13) The ratio (1) B.sub.2O.sub.3/Na.sub.2O and also the ratio (2) B.sub.2O.sub.3/R.sub.2O in the comparative examples V1 and V2 is therefore >1.20 as in the typical state-of-the-art borosilicate glasses, so that the limitations provided according to the invention for ratio (1) and (2) are not satisfied. Particularly since the ratio (1) B.sub.2O.sub.3/Na.sub.2O and also the ratio (2) B.sub.2O.sub.3/R.sub.2O in the comparative examples is >1.20, these glasses could indeed not be tempered as well as the glasses provided according to the invention set out in Tables 1 and 2.

(14) The example embodiments (A1-A16) in Tables 1 and 2 show significantly better tempering behavior/diffusivity with the same tempering parameters relative to the comparative examples (Table 3). In the comparative examples, only a low or rather low chemical tempering can be achieved, especially with regard to the penetration depth DoL compared to the example embodiments. Nevertheless, the comparative examples show a hydrolytic class HGA1, although its strength is considerably lower than that of borosilicate glass provided in accordance with the invention that has been well tempered. The comparative examples do not satisfy the necessary ratio B.sub.2O.sub.3/Na.sub.2O <1.2, so that the good tempering values of CS >400 MPa and at the same time DoL >20 μm could not be achieved.

(15) Thus, according to the invention, a glass article made of borosilicate glass is provided, such as a pharmaceutical primary packaging material. The glass article has an increased strength compared to prior art borosilicate glass articles, since better chemical tempering is possible.

(16) The following table lists example glasses disclosed in U.S. Patent Application Publication No. 2015/0152003 including their densities, Young's modulus and ratio E/p. None of the glasses has a density of below 2.4 g/cm.sup.3. None of the glasses has the desired density and modulus with low Al.sub.2O.sub.3 content.

(17) TABLE-US-00013 TABLE 4.1 20 21 22 23 26 27 28 29 SiO.sub.2 70.4 70.9 71.9 72.5 68.6 69.1 70.1 70.6 Al.sub.2O.sub.3 8.1 8.2 6.8 6.9 8.1 8.2 6.8 6.9 B.sub.2O.sub.3 3.7 3.7 3.6 3.6 6.4 6.5 6.4 6.4 Na.sub.2O 12.3 10.3 12.2 10.2 11.3 9.3 11.2 9.3 K.sub.2O 0.7 2 0.7 2 0.7 2 0.7 2 MgO 4.7 4.8 4.7 4.7 4.8 4.8 4.7 4.7 CaO 0 0 0 0 0 0 0 0 SnO.sub.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Density 2.41 2.4 2.41 2.4 2.4 2.39 2.4 2.39 (g/cm.sup.3) E-modulus 73.291113 73.2135623 72.4559939 72.3698046 74.4944231 74.4332161 73.6872537 73.54366 (GPa) E/ρ 304.112502 305.056509 300.647278 301.540852 310.393429 311.436051 307.030224 307.714059 (*10.sup.6m.sup.2/s.sup.2)

(18) TABLE-US-00014 TABLE 4.2 76 77 78 79 80 81 82 83 SiO.sub.2 70.6 69.1 69.2 68.7 70.1 70.1 69.6 69.2 Al.sub.2O.sub.3 8.7 8.7 8.8 8.8 8.7 8.8 8.7 8.8 MgO 4.8 4.8 4.8 4.8 4 4 4 4.8 B.sub.2O.sub.3 2.7 3.7 3.3 3.4 3.5 3.6 3.8 2.6 Li.sub.2O 0 0.02 0 0 0 0 0 0.02 Na.sub.2O 12.4 12.9 12.8 12.9 12.9 12.4 12.5 13.9 K.sub.2O 0.7 0.7 1 1.3 0.7 1 1.3 0.7 SnO.sub.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Density 2.41 2.42 2.42 2.42 2.41 2.41 2.42 2.43 (g/cm.sup.3) E-modulus 73.2593755 73.6974959 73.4990076 73.3150731 73.2526187 73.4085896 73.5018026 73.1797672 (GPa) E/ρ 303.980811 304.535107 303.714908 302.954848 303.952775 304.599957 303.726457 301.151305 (*10.sup.6m.sup.2/s.sup.2)

(19) TABLE-US-00015 TABLE 4.3 84 85 86 87 88 89 90 91 92 SiO.sub.2 69.7 69.9 70 69.8 69.7 70.6 70.9 70.4 69.9 Al.sub.2O.sub.3 8.8 8.7 8.7 8.6 8.7 8.8 8.8 8.7 8.7 MgO 4.8 4.8 4.8 4.7 4.7 4 4 4 3.9 B.sub.2O.sub.3 1.2 2.3 1.6 1.4 0.9 2.8 2.1 1.6 0.9 Li.sub.2O 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Na.sub.2O 14.7 13.7 14.4 14.9 15.5 13.3 13.7 14.8 16 K.sub.2O 0.7 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 SnO.sub.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Density 2.43 2.42 2.43 2.43 2.43 2.41 2.42 2.43 2.44 (g/cm.sup.3) E-modulus 72.2730842 72.9661817 72.6746131 72.2922941 71.8908841 73.0202065 72.8702011 72.4084246 71.8745868 (GPa) E/ρ 297.4201 301.513147 299.072482 297.499153 295.84726 302.988409 301.116533 297.977056 294.567979 (*10.sup.6m.sup.2/s.sup.2)

(20) Prior art document EP 2 796 426 A1 discloses further glasses that are shown in the tables below. None of the glasses has the desired density and modulus with low Al.sub.2O.sub.3 content.

(21) TABLE-US-00016 TABLE 5.1 A B C D E F SiO.sub.2 70.8 72.8 74.8 76.8 76.8 77.4 Al.sub.2O.sub.3 7.5 7 6.5 6 6 7 Na.sub.2O 13.7 12.7 11.7 10.7 11.6 10 K.sub.2O 1 1 1 1 0.1 0.1 MgO 6.3 5.8 5.3 4.8 4.8 4.8 CaO 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.2 0.2 0.2 0.2 0.2 0.2 Density 2.43838578 2.425128 2.41065774 2.39498374 2.39500279 2.38690093 (g/cm.sup.3) E-modulus 71.4784098 71.1719441 70.8286853 70.4487711 70.5616302 71.6879501 (GPa) E/ρ 293.138232 293.477062 293.814772 294.151355 294.620242 300.339027 (*10.sup.6m.sup.2/s.sup.2)

(22) TABLE-US-00017 TABLE 5.2 G H 1 1 2 3 SiO.sub.2 76.965 76.852 76.962 76.919 76.96 77.156 Al.sub.2O.sub.3 5.943 6.974 7.958 8.95 4.977 3.997 Na.sub.2O 11.427 10.473 9.451 8.468 12.393 13.277 K.sub.2O 0.101 0.1 0.102 0.105 0.1 0.1 MgO 4.842 4.878 4.802 4.836 4.852 4.757 CaO 0.474 0.478 0.481 0.48 0.468 0.462 SnO.sub.2 0.198 0.195 0.197 0.197 0.196 0.196 Density 2.388 2.384 2.381 2.382 2.392 2.396 (g/cm.sup.3) E-modulus 70.4070598 71.3862325 72.3762273 73.4885151 69.4723465 68.5497881 (GPa) E/ρ 294.836934 299.438895 303.974075 308.516016 290.436231 286.100952 (*10.sup.6m.sup.2/s.sup.2)

(23) TABLE-US-00018 TABLE 5.3 J K L 4 5 6 SiO.sub.2 76.99 77.1 77.1 77.01 76.97 77.12 Al.sub.2O.sub.3 5.98 5.97 5.96 5.96 5.97 5.98 Na.sub.2O 11.38 11.33 11.37 11.38 11.4 11.34 K.sub.2O 0.1 0.1 0.1 0.1 0.1 0.1 MgO 5.23 4.79 3.78 2.83 1.84 0.09 CaO 0.07 0.45 1.45 2.46 3.47 5.12 SnO.sub.2 0.2 0.19 0.19 0.19 0.19 0.19 Density 2.384 2.387 2.394 2.402 2.41 2.42 (g/cm.sup.3) E-modulus 70.4365858 295.123573 70.3395635 70.285402 70.2285741 70.0687577 (GPa) E/ρ 295.499079 295.123573 293.816055 292.611998 291.404872 289.540321 (*10.sup.6m.sup.2/s.sup.2)

(24) TABLE-US-00019 TABLE 5.4 M N O 7 8 9 SiO.sub.2 76.86 76.778 76.396 74.78 73.843 72.782 Al.sub.2O.sub.3 5.964 5.948 5.919 5.793 5.72 5.867 B.sub.2O.sub.3 0 0.214 0.777 2.84 4.443 4.636 Na.sub.2O 11.486 11.408 11.294 11.036 10.58 11.099 K.sub.2O 0.101 0.1 0.1 0.098 0.088 0.098 MgO 4.849 4.827 4.801 4.754 4.645 4.817 CaO 0.492 0.48 0.475 0.463 0.453 0.465 SnO.sub.2 0.197 0.192 0.192 0.188 0.183 0.189 Density 2.388 2.389 2.39 2.394 2.392 2.403 (g/cm.sup.3) E-modulus 70.3920964 70.5336512 70.8095063 71.756441 72.4734649 72.7412116 (GPa) E/ρ 294.774273 295.243412 296.274085 299.734507 302.982713 302.709994 (*10.sup.6m.sup.2/s.sup.2)

(25) Regarding the densities, the values given in U.S. Patent Application Publication No. 2015/0152003 were used. Where no densities were given, the respective values have been calculated according to Fluegel, Global Model for Calculating Room-Temperature Glass Density from the Composition, J. Am. Ceram. Soc., 90 [8]2622-2625 (2007), wherein SnO.sub.2 was treated as “remainder”. There was no need for normalization because the proportions added up to 100%. Young's modulus was obtained according to Makishima and Mackenzie, wherein compositions were normalized to obtain 100%, if necessary.

(26) While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.