IP Library Granted Patent US 12,540,096
Granted Patent B2
US 12,540,096 · App. 17/396,277 · Granted Feb 3, 2026

Alkali-free glass

Inventors: Hirofumi Tokunaga (Tokyo, JP); Kazutaka Ono (Tokyo, JP)
Assignee: AGC Inc.
C03C3/091
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,540,096
App. No.
17/396,277
Granted
Feb 3, 2026
Kind
B2
Abstract

An alkali-free glass includes, in mol % in terms of oxides: SiO 2 : 63-75%; Al 2 O 3 : 10-16%; B 2 O 3 : 0-5%; MgO: 0.1-15%; CaO: 0.1-12%; SrO: 0-8%; and BaO: 0-6%. [MgO]/[CaO] is 1.5 or smaller. A value of Formula (A) is 82.5 or larger. A value of Formula (B) is 690 or larger and 800 or smaller. A value of Formula (C) is 100 or smaller. A value of Formula (D) is 20 or smaller. The alkali-free glass has a Young's modulus of 83 GPa or larger and a surface devitrification viscosity η c of 10 4.2 dPa·s or higher.

Claims (94)

1 . An alkali-free glass, comprising, in mol % in terms of oxides:

SiO 2 : 63-75%,

Al 2 O 3 : 10-16%;

B 2 O 3 : 1.5 to 5%;

MgO: 0.1-15%;

CaO: 0.1-12%;

SrO: 0-3%; and

BaO: 0-6%,

wherein:

[MgO]/[CaO] is 1.5 or smaller;

a value of Formula (A) is 82.5 or larger, Formula (A) being 1.131[SiO 2 ]+1.933[Al 2 O 3 ]+0.362[B 2 O 3 ]+2.049[MgO]+1.751[CaO]+1.471[SrO]+1.039[BaO]-48.25;

a value of Formula (B) is in a range of 690 to 800, Formula (B) being 35.59[SiO 2 ]+37.34[Al 2 O 3 ]+24.59[B 2 O 3 ]+31.13[MgO]+31.26[CaO]+30.78[SrO]+31.98[BaO]-2761;

a value of Formula (C) is 100 or smaller, Formula (C) being −9.01[SiO 2 ]+36.36[Al 2 O 3 ]+5.7[B 2 O 3 ]+5.13[MgO]+17.25[CaO]+7.65[SrO]+10.58[BaO];

a value of Formula (D) is 12 or smaller, Formula (D) being −0.731 [SiO 2 ]+1.461[Al 2 O 3 ]−0.157[B 2 O 3 ]+1.904[MgO]+3.36[CaO]+3.411[SrO]+1.723[BaO]+(−3.318[MgO][CaO]−1.675[MgO][SrO]+1.757[MgO][BaO]+4.72[CaO][SrO]+2.094[CaO][BaO]+1.086[SrO][BaO])/([MgO]+[CaO]+[SrO]+[BaO]); and

the alkali-free glass has a Young's modulus of 83 GPa or larger and a surface devitrification viscosity η c of 10 4.2 dPa·s or higher.

2 . The alkali-free glass according to claim 1 , further comprising:

at least one selected from the group consisting of Li 2 O, Na 2 O, and K 2 O in an amount of greater than 0% to 0.2% in total in mole % in terms of oxides.

3 . The alkali-free glass according to claim 1 , further comprising:

F in an amount of greater than 0 mol % to 1.5 mol %.

4 . The alkali-free glass according to claim 1 , further comprising:

SnO 2 in an amount of greater than 0% to 0.5% in mol % in terms of oxides.

5 . The alkali-free glass according to claim 1 , further comprising:

ZrO 2 in an amount of greater than 0% to 0.09% in mol % in terms of oxides.

6 . The alkali-free glass according to claim 1 , wherein a value of Formula (B) is in a range of 1.50 to 5.50, Formula (E) being 4.379[SIO 2 ]+5.043[Al 2 O 3 ]+4.805[B 2 O 3 ]+4.828[MgO]+4.968[CaO]+5.051[SrO]+5.159[BaO]−453.

7 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a strain point of 690° C. or higher.

8 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a density of 2.8 g/cm 3 or lower and an average thermal expansion coefficient in 50-350° C. of 30×10 −7 /° C. to 45× 10 −7 /° C.

9 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a temperature T 2 at which a glass viscosity becomes 10 2 dPa·s of 1800° C. or lower and a temperature T 4 at which the glass viscosity becomes 10 4 dPa·s of 1400° C. or lower.

10 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has an internal devitrification temperature of 1320° C. or lower.

11 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has an internal devitrification viscosity η d of 10 4.4 dPa·s or higher.

12 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a crystal growth rate of 100 μm/hr or lower.

13 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a glass β-OH value in a range of 0.01 mm −1 to 0.5 mm −1 .

14 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has an annealing point of 850° C. or lower.

15 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a compaction of 150 ppm or smaller when being held at 600° C. for 80 min.

16 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has an equivalent cooling rate in a range of 5° C./min to 800° C./min.

17 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a sludge volume when the glass is subjected to an etching process of 30 ml or smaller.

18 . The alkali-free glass according to claim 1 , wherein the alkali-free glass has a photoelastic constant of 31 nm/MPa/cm or smaller.

19 . A glass plate, comprising:

the alkali-free glass of claim 1 ,

wherein the glass plate has a length of a side of 2400 mm or longer and a thickness of 1.0 mm or smaller.

20 . The glass plate according to claim 19 , wherein the glass plate is obtained by a float process or a fusion process.

21 . An alkali-free glass, comprising, in mol % in terms of oxides:

SiO 2 : 50-80%;

Al 2 O 3 : 8-20%;

Li 2 O+Na 2 O+K 2 O: 0-0.2%;

B 2 O 3 : 1.5 to 5%;

MgO: 0.1-15%:

CaO: 0.1-12%;

SrO: 0-3%;

P 2 O 5 : 0-1%; and

BaO: 3.5 to 6%,

wherein

[MgO]/[CaO] is 1.5 or smaller, and

the alkali-free glass has:

a Young's modulus of 83 GPa or larger;

a strain point of 690° C. or higher;

a temperature T 4 at which a glass viscosity becomes 10 4 dPa·s of 1400° C. or lower;

a temperature T 2 at which the glass viscosity becomes 10 2 dPa·s of 1800° C. or lower;

an internal devitrification temperature of 1320° C. or lower;

an internal devitrification viscosity η d of 10 4.4 dPa·s or higher;

a surface devitrification viscosity η c of 10 4.2 dPa·s or higher;

a crystal growth rate of 100 μm/hr or lower;

a density of 2.8 g/cm 3 or lower;

an average thermal expansion coefficient in 50-350° C. of 30×10 −7 to 45×10 −7 /° C.:

a value of Formula (A) is 82.5 or larger, Formula (A) being 1.131[SiO 2 ]+1.933[Al 2 O 3 ]+0.362[B 2 O 3 ]+2.049[MgO]+1.751[CaO]+1.471[SrO]+1.039[BaO]−48.25; and

a value of Formula (D) is 12 or smaller, Formula (D) being −0.731[SiO 2 ]+1.461[Al 2 O 3 ]−0.157[B 2 O 3 ]+1.904[MgO]+3.36[CaO]+3,411[SrO]+1.723[BaO]+(−3.318[MgO][CaO]−1.675[MgO][SrO]+1.757[MgO][BaO]+4.72[Cao][SrO]+2.094[CaO][BaO]+1.086[SrO][BaO])/([MgO]+[CaO]+[SrO]+[BaO]).

22 . The alkali-free glass according to claim 21 , further comprising:

B 2 O 3 in an amount of 1.5-4% in mol % in terms of oxides.

23 . The alkali-free glass according to claim 21 , further comprising, in mol % in terms of oxides:

CaO: 3-10%; and

SrO: 0.1-3%.

24 . The alkali-free glass according to claim 21 , further comprising, in mol % in terms of oxides:

B 2 O 3 : 1.5-4%;

CaO: 3-10%; and

SrO: 0.1-3%.

25 . The alkali-free glass according to claim 21 , further comprising:

F in an amount of greater than 0 mol % to 1.5 mol %.

26 . The alkali-free glass according to claim 21 , further comprising:

SnO 2 in an amount of greater than 0% to 0.5% in mol % in terms of oxides.

27 . The alkali-free glass according to claim 21 , further comprising:

ZrO 2 in an amount of greater than 0% to 0.09% in mol % in terms of oxides.

28 . The alkali-free glass according to claim 21 , wherein a value of Formula (A) is 85 or larger.

29 . The alkali-free glass according to claim 21 , wherein a value of Formula (B) is in a range of 690 to 800, Formula (B) being 35.59[SiO 2 ]+37.34[Al 2 O 3 ]+24.59[B 2 O 3 ]+31.13[MgO]+31.26[CaO]+30.78[SrO]+31.98[BaO]−2761.

30 . The alkali-free glass according to claim 21 , wherein a value of Formula (C) is 100 or smaller, Formula (C) being −9.01[SiO 2 ]+36.36[Al 2 O 3 ]+5.7[B 2 O 3 ]+5.13[MgO]+17.25[CaO]+7.65[SrO]+10.58[BaO].

31 . The alkali-free glass according to claim 21 , wherein a value of Formula (E) is in a range of 1.50 to 5.50, Formula (E) being 4.379[SiO 2 ]+5.043[Al 2 O 3 ]+4.805[B 2 O;]+4.828[MgO]+4.968[CaO]+5.051[SrO]+5.159[BaO]−453.

32 . The alkali-free glass according to claim 21 , wherein the alkali-free glass has a glass β-OH value in a range of 0.01 mm −1 to 0.5 mm −1 .

33 . The alkali-free glass according to claim 21 , wherein the alkali-free glass has an annealing point of 850° C. or lower.

34 . The alkali-free glass according to claim 21 , wherein the alkali-free glass has a compaction of 150 ppm or smaller when being held at 600° C. for 80 min.

35 . The alkali-free glass according to claim 21 , wherein the alkali-free glass has an equivalent cooling rate in a range of 5° C./min to 800° C./min.

36 . The alkali-free glass according to claim 21 , wherein the alkali-free glass has a sludge volume when the glass is subjected to an etching process of 30 ml or smaller.

37 . The alkali-free glass according to claim 21 , wherein the alkali-free glass has a photoelastic constant of 31 nm/MPa/cm or smaller.

38 . A glass plate, comprising:

the alkali-free glass of claim 21 ,

wherein the glass plate has a length of at least one side of 2400 mm or longer and a thickness of 1.0 mm or smaller.

39 . The glass plate according to claim 38 , wherein the glass plate is obtained by a float process or a fusion process.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 6, 2021
From: TOKUNAGA, HIROFUMI; ONO, KAZUTAKA
To: AGC INC.
Reel/Frame 057108/0546 →
Priority Claims (5)
JP 2019-020257 · Feb 7, 2019 · national
JP 2019-051570 · Mar 19, 2019 · national
JP 2019-141422 · Jul 31, 2019 · national
JP 2019-186805 · Oct 10, 2019 · national
JP 2020-017691 · Feb 5, 2020 · national
Continuity (2)
Continuation PCTJP2020004848 · Feb 7, 2020
Related Publication 20210380466A1 · Dec 9, 2021
References Cited (87)
US 6329310B1 · Peuchert et al. · 2001 [cited by applicant]
US 9580352B2 · Koyama et al. · 2017 [cited by applicant]
US 20080127679A1 · Nishizawa et al. · 2008 [cited by applicant]
US 20120149544A1 · Nagai et al. · 2012 [cited by applicant]
US 20120282450A1 · Kawaguchi et al. · 2012 [cited by applicant]
US 20130059718A1 · Koyama et al. · 2013 [cited by applicant]
US 20130274086A1 · Tsujimura et al. · 2013 [cited by applicant]
US 20140049708A1 · Murata et al. · 2014 [cited by applicant]
US 20150045201A1 · Tokunaga et al. · 2015 [cited by applicant]
US 20150045203A1 · Tokunaga et al. · 2015 [cited by applicant]
US 20150072130A1 · Tokunaga et al. · 2015 [cited by applicant]
US 20150087494A1 · Tokunaga et al. · 2015 [cited by applicant]
US 20150087495A1 · Nishizawa et al. · 2015 [cited by applicant]
US 20150093561A1 · Tokunaga et al. · 2015 [cited by applicant]
US 20150218040A1 · Koyama et al. · 2015 [cited by applicant]
US 20150299028A1 · Nishizawa et al. · 2015 [cited by applicant]
US 20160002095A1 · Tsujimura et al. · 2016 [cited by applicant]
US 20160068427A1 · Tokunaga et al. · 2016 [cited by applicant]
US 20170222321A1 · Caratelli et al. · 2017 [cited by applicant]
US 20170329192A1 · Ono et al. · 2017 [cited by applicant]
US 20190047899A1 · Tokunaga et al. · 2019 [cited by applicant]
US 20190107762A1 · Nakamura et al. · 2019 [cited by applicant]
US 20190185368A1 · Tokunaga et al. · 2019 [cited by applicant]
US 20190317376A1 · Ono et al. · 2019 [cited by applicant]
US 20200021916A1 · Akiyama et al. · 2020 [cited by applicant]
US 20200131075A1 · Saito · 2020 [cited by applicant]
US 20200140314A1 · Tomamoto et al. · 2020 [cited by applicant]
US 20200161741A1 · Hiramatsu et al. · 2020 [cited by applicant]
US 20200199012A1 · Hayashi et al. · 2020 [cited by applicant]
US 20200238665A1 · Sakurai et al. · 2020 [cited by applicant]
US 20210103190A1 · Miyake · 2021 [cited by applicant]
US 20210363051A1 · Tokunaga et al. · 2021 [cited by applicant]
US 20220363585A1 · Saito · 2022 [cited by applicant]
US 20230140716A1 · Ono et al. · 2023 [cited by applicant]
US 20230142463A1 · Ono et al. · 2023 [cited by applicant]
CN 104350018A · 2015 [cited by applicant]
CN 104364212A · 2015 [cited by applicant]
CN 104854050A · 2015 [cited by applicant]
CN 105073670A · 2015 [cited by applicant]
CN 105271722A · 2016 [cited by applicant]
CN 105384335A · 2016 [cited by applicant]
CN 105722800A · 2016 [cited by applicant]
JP 2000302475A · 2000 [cited by applicant]
JP WO2011078258A1 · 2011 [cited by applicant]
JP 2012184146A · 2012 [cited by applicant]
JP 2012236759A · 2012 [cited by applicant]
JP 2013216562A · 2013 [cited by applicant]
JP 5702888B2 · 2015 [cited by applicant]
JP 5712922B2 · 2015 [cited by applicant]
JP 2015224150A · 2015 [cited by applicant]
JP 5849965B2 · 2016 [cited by applicant]
JP 2016029001A · 2016 [cited by examiner]
JP 201647794A · 2016 [cited by applicant]
JP 5907259B2 · 2016 [cited by examiner]
JP 201684242A · 2016 [cited by applicant]
JP 2016113363A · 2016 [cited by applicant]
JP 2016117641 · 2016 [cited by applicant]
JP 2016188148A · 2016 [cited by applicant]
JP 20177870A · 2017 [cited by applicant]
JP 2017063255A · 2017 [cited by applicant]
JP 2017509266A · 2017 [cited by applicant]
JP 201790617A · 2017 [cited by applicant]
JP 2018184332A · 2018 [cited by applicant]
JP 2019068368A · 2019 [cited by applicant]
KR 1020080022575A · 2008 [cited by applicant]
KR 20080085085A · 2008 [cited by applicant]
KR 1020150029632A · 2015 [cited by applicant]
WO WO2008093580A1 · 2008 [cited by applicant]
WO WO2011078258A1 · 2011 [cited by applicant]
WO WO2013161903A1 · 2013 [cited by applicant]
WO WO2013172307A1 · 2013 [cited by applicant]
WO WO2013180220A1 · 2013 [cited by applicant]
WO WO2013183569A1 · 2013 [cited by applicant]
WO WO2013183626A1 · 2013 [cited by applicant]
WO WO2016084952A1 · 2016 [cited by applicant]
WO WO2017188126A1 · 2017 [cited by applicant]
WO WO2017213191A1 · 2017 [cited by applicant]
WO WO2018016398A1 · 2018 [cited by applicant]
WO WO2018038059A1 · 2018 [cited by applicant]
WO WO2018181626A1 · 2018 [cited by applicant]
WO WO2019026963A1 · 2019 [cited by applicant]
WO WO2019070007A1 · 2019 [cited by applicant]
WO WO2019107514A1 · 2019 [cited by applicant]
International Search Report issued Mar. 24, 2020 in PCT/JP2020/004847 filed Feb. 7, 2020, 3 pages. [cited by applicant]
International Search Report issued Mar. 10, 2020 in PCT/JP2020/004848 filed Feb. 7, 2020 2 pages. [cited by applicant]
International Search Report issued Mar. 10, 2020 in PCT/JP2020/004850 filed Feb. 7, 2020 2 pages. [cited by applicant]
Chikao Tanaka, “Glass Melting Friendly to Environment: Especially on Technological Removal of Bubbles”, New Glass 83, vol. 21, No. 4,2006. pp. 31-36. (partial English Translation). [cited by applicant]