Source: https://patents.justia.com/patent/10597322
Timestamp: 2020-06-05 17:04:19
Document Index: 327880327

Matched Legal Cases: ['Application No. 12781017', 'Application No. 11201408732', 'Application No. 2014', 'Application No. 2016', 'Application No. 2016', 'Application No. 2014', 'Application No. 2014117028', 'Application No. 17198848', 'Application No. 17198854', 'Application No. 17198854', 'Application No. 17198848', 'Application No. 2016', 'Application No. 2018114258', 'Application No. 2018', 'Application No. 2017']

US Patent for Glass compositions with improved chemical and mechanical durability Patent (Patent # 10,597,322 issued March 24, 2020) - Justia Patents Search
Justia Patents Calcium Oxide ContainingUS Patent for Glass compositions with improved chemical and mechanical durability Patent (Patent # 10,597,322)
Mar 3, 2017 - CORNING INCORPORATED
TEMPORARY BONDING USING POLYCATIONIC POLYMERS
The present application is a continuation of U.S. Non-Provisional patent application Ser. No. 14/551,773, filed Nov. 24, 2014 and entitled “Glass Compositions With Improved Chemical And Mechanical Durability” which is a continuation of U.S. Non-Provisional patent application Ser. No. 13/660,450, filed Oct. 25, 2012 and entitled “Glass Compositions With Improved Chemical And Mechanical Durability” (now U.S. Pat. No. 8,980,777) and which claims priority to U.S. Provisional Patent Application Ser. No. 61/551,163, filed Oct. 25, 2011 entitled “Glass Compositions With Improved Chemical and Mechanical Durability,” each of which is incorporated by reference herein in their entireties.
One approach to improving the mechanical durability of the glass package is to thermally temper the glass package. Thermal tempering strengthens glass by inducing a surface compressive stress during rapid cooling after forming. This technique works well for glass articles with flat geometries (such as windows), glass articles with thicknesses >2 mm, and glass compositions with high thermal expansion. However, pharmaceutical glass packages typically have complex geometries (vial, tubular, ampoule, etc.), thin walls (˜1-1.5 mm), and are produced from low expansion glasses (30-55×10−7K−1) making glass pharmaceutical packages unsuitable for strengthening by thermal tempering.
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 herein was assessed according to three established material testing standards: DIN 12116 dated March 2001 and entitled “Testing of glass—Resistance to attack by a boiling aqueous solution of hydrochloric acid—Method of test and classification”; ISO 695:1991 entitled “Glass—Resistance to attack by a boiling aqueous solution of mixed alkali—Method of test and classification”; and ISO 720:1985 entitled “Glass—Hydrolytic resistance of glass grains at 121 degrees C. —Method of test and classification.” The chemical durability of the glass may also be assessed according to ISO 719:1985 “Glass—Hydrolytic resistance of glass grains at 98 degrees C. —Method of test and classification,” in addition to the above referenced standards. The ISO 719 standard is a less rigorous version of the ISO 720 standard and, as such, it is believed that a glass which meets a specified classification of the ISO 720 standard will also meet the corresponding classification of the ISO 719 standard. The classifications associated with each standard are described in further detail herein.
The ion exchangeability of the glass composition is primarily imparted to the glass composition by the amount of the alkali oxide Na2O initially present in the glass composition prior to ion exchange. Accordingly, in the embodiments of the glass compositions described herein, the alkali oxide present in the glass composition includes at least Na2O. Specifically, in order to achieve the desired compressive strength and depth of layer in the glass composition upon ion exchange strengthening, the glass compositions include Na2O in an amount from about 2 mol. % to about 15 mol. % based on the molecular weight of the glass composition. In some embodiments the glass composition includes at least about 8 mol. % of Na2O based on the molecular weight of the glass composition. For example, the concentration of Na2O may be greater than 9 mol. %, greater than 10 mol. % or even greater than 11 mol. %. In some embodiments, the concentration of Na2O may 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. %.
The ISO 720 standard is a measure of the resistance of the glass to degradation in purified, CO2-free water. In brief, the ISO 720 standard protocol utilizes crushed glass grains which are placed in contact with the purified, CO2-free water under autoclave conditions (121° C., 2 atm) for 30 minutes. The solution is then titrated colorimetrically with dilute HCl to neutral pH. The amount of HCl required to titrate to a neutral solution is then converted to an equivalent of Na2O extracted from the glass and reported in μg Na2O per weight of glass with smaller values indicative of greater durability. The ISO 720 standard is broken into individual types. Type HGA1 is indicative of up to 62 μg extracted equivalent of Na2O per gram of glass tested; Type HGA2 is indicative of more than 62 μg and up to 527 μg extracted equivalent of Na2O per gram of glass tested; and Type HGA3 is indicative of more than 527 μg and up to 930 μg extracted equivalent of Na2O per gram of glass tested.
Table 1 also shows that the non-ion exchanged test samples of exemplary glass compositions A-F all demonstrated a hydrolytic resistance of at least Type HGA2 following testing according to the ISO 720 standard with exemplary glass compositions C-F having a hydrolytic resistance of Type HGA1. The hydrolytic resistance of exemplary glass compositions C-F is believed to be due to higher amounts of SiO2 and the lower amounts of Na2O in the glass compositions relative to exemplary glass compositions A and B.
SiO2 70.8 72.8 74.8 76.8 76.8 77.4 Al2O3 7.5 7 6.5 6 6 7 Na2O 13.7 12.7 11.7 10.7 11.6 10 K2O 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 SnO2 0.2 0.2 0.2 0.2 0.2 0.2 DIN 12116 3.2 2.0 1.7 1.6 1.2 1.7 (mg/dm2) classification S3 S3 S3 S3 S2 S3 ISO 695 60.7 65.4 77.9 71.5 76.5 62.4 (mg/dm2) classification A1 A1 A2 A1 A2 A1 ISO 720 100.7 87.0 54.8 57.5 50.7 37.7 (μg Na2O/g glass) classification HGA2 HGA2 HGA1 HGA1 HGA1 HGA1 ISO 720 60.3 51.9 39.0 30.1 32.9 23.3 (with IX) (μg Na2O/g glass) classification HGA1 HGA1 HGA1 HGA1 HGA1 HGA1
SiO2 76.99 77.10 77.10 77.01 76.97 77.12 Al2O3 5.98 5.97 5.96 5.96 5.97 5.98 Na2O 11.38 11.33 11.37 11.38 11.40 11.34 K2O 0.10 0.10 0.10 0.10 0.10 0.10 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 SnO2 0.20 0.19 0.19 0.19 0.19 0.19 Strain (° C.) 585 579 568 562 566 561 Anneal (° C.) 641 634 620 612 611 610 Softening 902 895 872 859 847 834 (° C.) Expansion 67.9 67.1 68.1 68.8 69.4 70.1 (10−7 K−1) Density 2.384 2.387 2.394 2.402 2.41 2.42 (g/cm3) SOC nm/ 3.12 3.08 3.04 3.06 3.04 3.01 mm/Mpa ISO720 83.2 83.9 86 86 88.7 96.9 (non-IX) ISO720 29.1 28.4 33.2 37.3 40.1 (IX450° C.- 5 hr) Fraction of RO 0.014 0.086 0.277 0.465 0.654 0.982 as CaO CS@t = 0 707 717 713 689 693 676 (MPa) CS/√t −36 −37 −39 −38 −43 −44 (MPa/hr1/2) D (μm2/hr) 57.2 50.8 40.2 31.4 26.4 20.7
SiO2 76.860 76.778 76.396 74.780 73.843 72.782 Al2O3 5.964 5.948 5.919 5.793 5.720 5.867 B2O3 0.000 0.214 0.777 2.840 4.443 4.636 Na2O 11.486 11.408 11.294 11.036 10.580 11.099 K2O 0.101 0.100 0.100 0.098 0.088 0.098 MgO 4.849 4.827 4.801 4.754 4.645 4.817 CaO 0.492 0.480 0.475 0.463 0.453 0.465 SnO2 0.197 0.192 0.192 0.188 0.183 0.189 Strain (° C.) 579 575 572 560 552 548 Anneal (° C.) 632 626 622 606 597 590 Softening 889 880 873 836 816 801 (° C.) Expansion 68.3 67.4 67.4 65.8 64.1 67.3 (10−7 K−1) Density 2.388 2.389 2.390 2.394 2.392 2.403 (g/cm3) SOC 3.13 3.12 3.13 3.17 3.21 3.18 (nm/mm/MPa) ISO720 86.3 78.8 68.5 64.4 52.7 54.1 (non-IX) ISO720 32.2 30.1 26 24.7 22.6 26.7 (IX450° C.- 5 hr) B2O3/ 0.000 0.038 0.142 0.532 0.898 0.870 (R2O—Al2O3) CS@t = 0 703 714 722 701 686 734 (MPa) CS/√t −38 −38 −38 −33 −32 −39 (MPa/hr1/2) D (μm2/hr) 51.7 43.8 38.6 22.9 16.6 15.6
a type HGB1 hydrolytic resistance according to ISO 719;
a compressive stress layer with a depth of layer of greater than 25 μm;
a surface compressive stress of greater than or equal to 350 MPa, wherein the glass article is ion exchange strengthened and the ion exchange strengthening comprises treating 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.;
SiO2 in an amount greater than or equal to 67 mol.% and less than or equal to 80 mol.%;
alkaline earth oxide in an amount greater than or equal to 3 mol.% and less than or equal to 13 mol.%, wherein 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;
X mol.% Al2O3 wherein X is greater than 5 mol.% and less than or equal to about 10 mol.%; and
Y mol.% alkali oxide wherein Y is greater than or equal to 2 mol.% and less than or equal to 18 mol.%, wherein the glass article is a pharmaceutical package.
2. The glass article of claim 1, wherein the amount of the alkaline earth oxide is greater than or equal to 4 mol.% and less than or equal to 8 mol.%.
3. The glass article of claim 1, wherein the alkaline earth oxide comprises from 0.1 mol.% to less than or equal to 1.0 mol.% CaO.
4. The glass article of claim 1, wherein the alkaline earth oxide comprises from 3 mol.% to 7 mol.% MgO.
5. The glass article of claim 1, wherein the alkali oxide comprises greater than or equal to 9 mol.% Na2O and less than or equal to 15 mol.% Na2O.
6. The glass article of claim 1, wherein the alkali oxide comprises K2O in an amount greater than or equal to 0.01 mol.% and less than or equal to 1.0 mol.%.
7. The glass article of claim 1, wherein X is greater than 5 mol.% and less than or equal to 7 mol.%.
8. The glass article of claim 1, wherein a ratio of Y:X is greater than or equal to 1 and less than or equal to 2.
9. The glass article of claim 1, wherein the glass composition is free of boron and compounds of boron.
10. The glass article of claim 1, wherein the glass article has a type HGA1 hydrolytic resistance according to ISO 720 after ion exchange strengthening.
11. The glass article of claim 1, wherein the glass article has a threshold diffusivity of greater than 16 μm2/hr at a temperature of less than or equal to 450° C.
12. The glass article of claim 11, wherein the threshold diffusivity is greater than or equal to 20 μm2/hr at a temperature of less than or equal to 450° C.
13. A glass pharmaceutical container comprising:
at least a class A2 base resistance or better according to ISO 695;
a Type 1 chemical durability according to USP <660>;
a compressive stress layer with a depth of layer of greater than 25 μm; and a surface compressive stress of greater than or equal to 150 MPa, wherein the glass pharmaceutical container is ion exchange strengthened and the ion exchange strengthening comprises treating the glass pharmaceutical container in a molten salt bath for a time less than or equal to 10 hours at a temperature less than or equal to 450° C.;
SiO2 in an amount greater than or equal to 70 mol.% and less than or equal to 78 mol.%;
alkaline earth oxide in an amount greater than or equal to 4 mol.% and less than or equal to 8 mol.%;
X mol.% Al203, wherein X is greater than 5 mol.% and less than or equal to 7 mol.%;
Y mol.% alkali oxide wherein Y is greater than or equal to 8 mol.% and less than or equal to 18 mol.%; a ratio of a concentration of B2O3 (mol.%) in the glass pharmaceutical container to (Y mol.% −X mol.%) is less than 0.3; and a ratio of Y:X is greater than 1.
14. The glass pharmaceutical container of claim 13, wherein 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.
15. The glass pharmaceutical container of claim 13, wherein the alkaline earth oxide comprises from 3 mol.% to 7 mol.% MgO.
16. The glass pharmaceutical container of claim 13, wherein the alkaline earth oxide comprises CaO in an amount greater than or equal to 0.1 mol.% and less than or equal to 1.0 mol.%.
17. The glass pharmaceutical container of claim 13, wherein the alkali oxide comprises greater than or equal to 9 mol.% Na2O and less than or equal to 13 mol.% Na2O.
18. The glass pharmaceutical container of claim 13, wherein the alkali oxide further comprises K2O in a concentration greater than or equal to 0.01 mol.% and less than or equal to 1.0 mol.%.
19. The glass pharmaceutical container of claim 13, wherein the ratio of Y:X is less than or equal to 2.
20. The glass pharmaceutical container of claim 13, wherein a ratio of Y:X is greater than 1.3.
21. The glass pharmaceutical container of claim 13, wherein the glass pharmaceutical container is free from boron and compounds of boron.
22. The glass pharmaceutical container of claim 13, wherein the concentration of B2O3 is greater than or equal to 0.01 mol.%.
23. The glass pharmaceutical container of claim 22, wherein the concentration of B2O3 is less than 4 mol.%.
24. The glass pharmaceutical container of claim 13, wherein the surface compressive stress is greater than or equal to 250 MPa.
3054686 September 1962 Hagedorn
RE25456 October 1963 Bacon et al.
3351474 November 1967 Hagedorn et al.
4161556 July 17, 1979 Lenard et al.
4312953 January 26, 1982 Mills et al.
6156399 December 5, 2000 Spallek et al.
6333285 December 25, 2001 Chopinet et al.
6413892 July 2, 2002 Koyama et al.
6627569 September 30, 2003 Naumann et al.
8551898 October 8, 2013 Danielson
8753994 June 17, 2014 Danielson
8980777 March 17, 2015 Danielson
9012343 April 21, 2015 Yamamoto et al.
9145329 September 29, 2015 Drake
9186295 November 17, 2015 Weeks
9198829 December 1, 2015 Weeks
9241869 January 26, 2016 Weeks
9340447 May 17, 2016 Danielson
9474688 October 25, 2016 Weeks
9474689 October 25, 2016 Weeks
9624125 April 18, 2017 Danielson
9701567 July 11, 2017 Aitken
9718721 August 1, 2017 Drake et al.
20070293388 December 20, 2007 Zuyev et al.
20090298669 December 3, 2009 Akiba et al.
20100255350 October 7, 2010 Endo et al.
20110135938 June 9, 2011 Kim et al.
20110226658 September 22, 2011 Tata-Venkata et al.
20120100329 April 26, 2012 Baratta
20120234368 September 20, 2012 Cintora et al.
20140154440 June 5, 2014 Iida et al.
20150037571 February 5, 2015 Danielson et al.
20150079318 March 19, 2015 Danielson et al.
20150232374 August 20, 2015 Danielson et al.
20170081239 March 23, 2017 Schwall et al.
20170174554 June 22, 2017 Danielson
102010054967 July 2012 DE
2098491 September 2009 EP
2876092 May 2015 EP
H04-219343 August 1992 JP
H09-124338 May 1997 JP
H09-124339 May 1997 JP
H09-241033 September 1997 JP
H1129344 February 1999 JP
H1143345 February 1999 JP
H11180727 July 1999 JP
H11180728 July 1999 JP
H11240735 September 1999 JP
H11328601 November 1999 JP
H11335133 December 1999 JP
2001247332 September 2001 JP
2002193635 July 2002 JP
2004315317 November 2004 JP
2005048142 February 2005 JP
2010202413 September 2010 JP
2012184118 September 2012 JP
1006303090000 September 2006 KR
2173673 September 2001 RU
200743644 December 2007 TW
1996024559 August 1996 WO
1997025932 July 1997 WO
1999005070 February 1999 WO
2007142324 December 2007 WO
2008062847 May 2008 WO
2011007785 January 2011 WO
2013021975 February 2013 WO
International Search Report & Written Opinion dated Jan. 30, 2013 for International Patent Application No. PCT/US2012/061939 filed Oct. 25, 2012. pp. 1-14.
International Search Report & Written Opinion dated Jan. 30, 2013 for International Patent Application No. PCT/US2012/061867 filed Oct. 25, 2012. pp. 1-16.
Non-Final Office Action dated Mar. 14, 2013, relating to U.S. Appl. No. 13/660,394, filed Oct. 25, 2012. pp. 1-7.
Notice of Allowance dated Jun. 27, 2013, relating to U.S. Appl. No. 13/660,394, filed Oct. 25, 2012. pp. 1-7.
Corrected Notice of Allowance dated Sep. 11, 2013, relating to U.S. Appl. No. 13/660,394, filed Oct. 25, 2012. pp. 1-2.
Non-Final Office Action dated Nov. 4, 2013, relating to U.S. Appl. No. 14/011,376, filed Aug. 27, 2013. pp. 1-11.
International Search Report & Written Opinion dated Oct. 28, 2013 for PCT/US2013/048589 filed Jun. 28, 2013 pp. 1-15.
Notice of Allowance dated Mar. 11, 2014 relating to U.S. Appl. No. 14/011,376, filed Aug. 27, 2013; pp. 1-11.
Non-Final Office Action dated May 15, 2014, relating to U.S. Appl. No. 13/660,683, filed Oct. 25, 2012. pp. 1-12.
Non-Final Office Action dated Sep. 9, 2014 relating to U.S. Appl. No. 14/057,697, filed Oct. 18, 2013. pp. 1-15.
Non-Final Office Action dated Mar. 20, 2014 relating to U.S. Appl. No. 14/057,697, filed Oct. 18, 2013. pp. 1-14.
U.S. Pharmacopeial Convention Medicines Compendium, “<660> Containers—Glass” [online], (2014). Retrieved from the Internet: <URL: https://mc.usp.org/general-chapters>. pp. 1-5.
European Pharmacopeia, 5th edition, 3.2 Containers, [online]. Retrieved from the Internet: <URL: http://pharmacyebooks.com/2009/09/european-pharmacopoeia-5-0-online.html>. pp. 1-4.
Ciullo, P.A., Industrial Minerals and Their Uses—A Handbook and Formulary. William Andrew Publishing/Noyes, (1996). ISBN: 0-8155-1408-5. Online version available at: <http://app.knovel.com/hotlink/toc/id:kpIMTUAHFB/industrial-minerals-their/industrial-minerals-their>. pp. 1-7.
Non-Final Office Action dated Jul. 15, 2014 relating to U.S. Appl. No. 13/660,450, filed Oct. 25, 2012. pp. 1-14.
Notice of Allowance dated Nov. 12, 2014, relating to U.S. Appl. No. 13/660,450, filed Oct. 25, 2012. pp. 1-9.
Non-Final Office Action dated Dec. 3, 2014 relating to U.S. Appl. No. 13/660,141, filed Oct. 25, 2012. pp. 1-13.
Non-Final Office Action dated Jun. 16, 2015 relating to U.S. Appl. No. 14/701,185, filed Apr. 30, 2015. pp. 1-16.
Derwent Abstract 1984-211366 of RO 83460 A issued Mar. 30, 1984. pp. 1-2.
Non-Final Office Action dated Jun. 10, 2015 relating to U.S. Appl. No. 14/272,189, filed May 7, 2014. pp. 1-22.
Non-Final Office Action dated Jun. 18, 2015 relating to U.S. Appl. No. 14/551,773, filed Nov. 24, 2014. pp. 1-15.
Final Office Action dated Dec. 4, 2015 relating to U.S. Appl. No. 14/272,189, filed May 7, 2014. pp. 1-13.
Non-Final Office Action dated Feb. 2, 2016 relating to U.S. Appl. No. 14/520,722, filed Oct. 22, 2014. pp. 1-9.
European Communication pursuant to Article 94(3) EPC dated Feb. 4, 2016 for EP Patent Application No. 12781017.4. pp. 1-4.
Singapore Search Report & Written Opinion dated Jan. 12, 2016 for SG Patent Application No. 11201408732U. pp. 1-9.
Japanese 1st Office Action dated Jan. 26, 2016 for JP Patent Application No. 2014-538997. pp. 1-8.
Varshneya, A.K., “Chemical Strengthening of Glass: Lessons Learned and yet to be Learned,” International Journal of Applied Glass Science, vol. 1 (2), p. 131-142 (2010).
Japanese 1st Office Action dated Aug. 9, 2016 for JP Patent Application No. 2016-124363. pp. 1-4.
Japanese 1st Office Action dated Aug. 9, 2016 for JP Patent Application No. 2016-124365. pp. 1-7.
Japanese 2nd Office Action & Search Report dated Feb. 14, 2017, for JP Patent Application No. 2014-538893. pp. 1-7.
K.K. Mallick et al., “Strengthening of container glasses by ion-exchange dip coating”, (2005), Journal of Non-Crystalline Solids, U.S., 351/30-32, p. 2524-2536.
Russian Decision to Grant and Search Report with English Translations dated Dec. 25, 2017, for RU Patent Application No. 2014117028. pp. 1-13.
Partial European Search Report dated Feb. 16, 2018 for EP Patent Application No. 17198848.8. pp. 1-13.
Partial European Search Report dated Feb. 22, 2018 for EP Patent Application No. 17198854.6. pp. 1-17.
European Search Report and Written Opinion dated Jun. 21, 2018 for EP Patent Application No. 17198854.6. pp. 1-16.
European Search Report and Written Opinion dated Jun. 25, 2018 for EP Patent Application No. 17198848.8. pp. 1-16.
Japanese 2nd Office Action dated Jul. 24, 2018, for JP Patent Application No. 2016-217932. pp. 1-5.
English translation of Russian 1st Office Action and Search Report dated Dec. 21, 2018, for RU Patent Application No. 2018114258. pp. 1-14.
English Translation of Japanese 1st Office Action dated Feb. 13, 2019 for JP Patent Application No. 2018-019178. pp. 1-5.
Non-Final Office Action dated Mar. 29, 2019 relating to U.S. Appl. No. 15/664,796, filed Jul. 31, 2017. pp. 1-15.
English Translation of Japanese 2nd Office Action dated Jul. 24, 2019 for JP Patent Application No. 2017-168242. pp. 1-6.
Patent Publication Number: 20170174555
Application Number: 15/449,766
Current U.S. Class: Calcium Oxide Containing (501/70)
International Classification: C03C 3/087 (20060101); C03C 4/20 (20060101); C03C 21/00 (20060101); C03C 3/091 (20060101); C03C 4/18 (20060101); A61J 1/00 (20060101);