IP Library Granted Patent US 12,441,817
Granted Patent B2
US 12,441,817 · App. 18/656,283 · Granted Oct 14, 2025

Multi-stage polymeric latexes, coating compositions containing such latexes, and articles coated therewith

Inventors: Robert M. O'Brien (Monongahela, PA); Mark Stuetelberg (Hiawatha, KS); Joseph D. Desousa (Pittsburgh, PA); Mary Jo Scandolari (Coraopolis, PA); Nikolaus Koch (Greensburg, PA); Stephen Pollin (Ambridge, PA); Nusrah Hussain (Gibsonia, PA)
Assignee: SWIMC LLC
C08F2/001B65D25/14C09D5/024C09D7/40C09D133/12C09D133/26
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 12,441,817
App. No.
18/656,283
Granted
Oct 14, 2025
Kind
B2
Abstract

An aqueous coating composition useful in coating a variety of substrates, including interior or exterior portions of food or beverage cans. The coating composition includes a multi-stage polymeric latex having two or more emulsion polymerized stages in an aqueous carrier liquid, wherein the latex has one or both of: (i) a lower glass transition temperature (Tg) emulsion polymerized stage having a calculated Tg that is at least 20° C. lower than a calculated Tg of a higher Tg emulsion polymerized stage, or (ii) a gradient Tg with at least a 20° C. differential in the calculated Tg of monomers fed at the start of polymerization compared to monomers fed at the end of polymerization. When spray-applied on the interior of a food or beverage can, the composition exhibits a global extraction result of less than 50 ppm and a metal exposure value of less than 3 mA.

Claims (44)

1. An aqueous interior spray beverage container coating composition comprising a multi-stage polymeric latex having two or more emulsion polymerized ethylenically unsaturated monomer stages, wherein the latex has a lower Tg emulsion polymerized stage having a calculated Tg that is at least 35° C. lower than a calculated Tg of a higher Tg emulsion polymerized stage, wherein the coating composition includes, based on total resin solids, at least 50 wt. % of the two or more emulsion polymerized stages;

wherein the coating composition includes from 15 wt. % to 25 wt % of solids, is substantially free of each of bisphenol A, bisphenol F, and bisphenol S, and includes or is derived from no more than 0.5 wt. % of acrylamide-type monomers, if any, based on the aggregate weight of polymerizable monomers employed to make the latex;

wherein the coating composition, when spray applied onto an interior of a 355 mL no. 211 two-piece drawn and ironed aluminum beverage can at 115 milligrams per can coating weight and cured at 188° C. to 199° C. (measured at the can dome) for 55 seconds exhibits:

(i) a global extraction result of less than 50 ppm,

(ii) a metal exposure of less than 3 mA on average when the can is filled with 1% NaCl in deionized water and tested pursuant to the Initial Metal Exposure test method disclosed herein,

(iii) a metal exposure of less than 3.5 mA when tested pursuant to the Metal Exposure after Drop Damage test disclosed herein, and

(iv) a measured Tg of at least 50° C.

2. The coating composition of claim 1 , wherein the coating composition, when spray applied onto an interior of a 355 mL no. 211 two-piece drawn and ironed aluminum beverage can at 115 milligrams per can coating weight and cured at 188° C. to 199° C. (measured at the can dome) for 55 seconds, exhibits a measured Tg of at least 60° C.

3. The coating composition of claim 2 , wherein the aggregate of monomers used to form the two or more emulsion polymerized stages include at least 85 wt. % of one or more (meth)acrylates.

4. The coating composition of claim 2 , wherein the latex has a higher Tg emulsion polymerized stage having a calculated Tg of greater than 60° C.

5. The coating composition of claim 1 , wherein more than 50 weight percent of the emulsion polymerized stages have a calculated Tg of at least 60° C.

6. The coating composition of claim 2 , wherein organic solvent constitutes at least 10% by weight of the aqueous carrier liquid of the coating composition.

7. The coating composition of claim 1 , wherein the coating composition, when spray applied onto an interior of a 355 mL no. 211 two-piece drawn and ironed aluminum beverage can at 115 milligrams per can coating weight and cured at 188° C. to 199° C. (measured at the can dome) for 55 seconds, exhibits a measured Tg of at least 70° C.

8. The coating composition of claim 1 , wherein the coating composition, when spray applied onto an interior of a 355 mL no. 211 two-piece drawn and ironed aluminum beverage can at 115 milligrams per can coating weight and cured at 188° C. to 199° C. (measured at the can dome) for 55 seconds, exhibits a measured Tg of at least 80° C.

9. The coating composition of claim 1 , wherein the lower Tg emulsion polymerized stage has a calculated Tg that is at least 50° C. lower than the calculated Tg of the higher Tg emulsion polymerized stage.

10. The coating composition of claim 1 , wherein the lower Tg emulsion polymerized stage has a calculated Tg that is at least 60° C. lower than the calculated Tg of the higher Tg emulsion polymerized stage.

11. The coating composition of claim 1 , wherein the weight ratio of the lower Tg emulsion polymerized stage relative to the higher Tg emulsion polymerized stage ranges from 20:80 to 70:30.

12. The coating composition of claim 1 , wherein the coating composition is not prepared using halogenated monomers.

13. The coating composition of claim 1 , wherein the monomers used to form at least one of the emulsion polymerized stages includes at least 85 wt. % of one or more (meth)acrylates.

14. The coating composition of claim 1 , wherein two or more of the emulsion polymerized stages are formed from monomers having in the aggregate a calculated Tg of at least 50° C.

15. The coating composition of claim 1 , wherein the aqueous coating composition includes, based on total resin solids, at least 60 wt. % of the two or more emulsion polymerized stages.

16. The coating composition of claim 1 , wherein the aqueous coating composition includes, based on total resin solids, at least 70 wt. % of the two or more emulsion polymerized stages.

17. The coating composition of claim 1 , wherein organic solvent constitutes at least 5% by weight of the aqueous carrier liquid of the coating composition.

18. The coating composition of claim 1 , wherein at least one of the emulsion polymerized stages is formed from monomers including a multi-ethylenically unsaturated monomer.

19. The coating composition of claim 1 , wherein the coating composition is substantially free of styrene and substituted styrene compounds.

20. The coating composition of claim 1 , wherein the coating composition does not contain any structural units derived from a bisphenol.

21. The coating composition of claim 1 , wherein the aqueous coating composition further comprises a phenoplast crosslinker.

22. The coating composition of claim 1 , wherein the coating composition, when spray applied onto an interior of a 355 mL no. 211 two-piece drawn and ironed aluminum beverage can at 115 milligrams per can coating weight and cured at 188° C. to 199° C. (measured at the can dome) for 55 seconds, is capable of passing a necking and flanging test as indicated by a change of metal exposure after necking of less than 1.0 mA.

23. An aqueous interior spray beverage container coating composition comprising a multi-stage polymeric latex having two or more emulsion polymerized ethylenically unsaturated monomer stages, wherein the latex has a lower Tg emulsion polymerized stage having a calculated Tg that is at least 40° C. lower than a calculated Tg of a higher Tg emulsion polymerized stage, wherein the coating composition includes, based on total resin solids, at least 70 wt. % of the two or more emulsion polymerized stages;

wherein the coating composition:

includes from 15 wt. % to 25 wt % of solids,

has a viscosity of from 20 to 80 seconds (Ford Cup #2, 25° C.),

is substantially free of each of bisphenol A, bisphenol F, and bisphenol S,

is not prepared using halogenated monomers, and

includes or is derived from no more than 0.5 wt. % of acrylamide-type monomers, if any, based on the aggregate weight of polymerizable monomers employed to make the latex;

wherein the coating composition, when spray applied onto an interior of a 355 mL no. 211 two-piece drawn and ironed aluminum beverage can at 115 milligrams per can coating weight and cured at 188° C. to 199° C. (measured at the can dome) for 55 seconds exhibits:

(i) a global extraction result of less than 50 ppm,

(ii) a metal exposure of less than 3 mA on average when the can is filled with 1% NaCl in deionized water and tested pursuant to the Initial Metal Exposure test method disclosed herein,

(iii) a metal exposure of less than 3.5 mA when tested pursuant to the Metal Exposure after Drop Damage test disclosed herein, and

(iv) a measured Tg of at least 70° C.

24. The coating composition of claim 23 , wherein the coating composition, when spray applied onto an interior of a 355 mL no. 211 two-piece drawn and ironed aluminum beverage can at 115 milligrams per can coating weight and cured at 188° C. to 199° C. (measured at the can dome) for 55 seconds, is capable of passing a necking and flanging test as indicated by a change of metal exposure after necking of less than 1.0 mA.

25. The coating composition of claim 23 , wherein the weight ratio of the lower Tg emulsion polymerized stage relative to the higher Tg emulsion polymerized stage ranges from 25:75 to 48:52.

26. The coating composition of claim 23 , wherein organic solvent constitutes at least 10% by weight of the aqueous carrier liquid of the coating composition.

27. The coating composition of claim 23 , wherein at least one of the emulsion polymerized stages is formed from monomers including at least 80 wt. % of one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.

Continuity (6)
Continuation 17882330 · Aug 5, 2022
Continuation 16805579 · Feb 28, 2020
Continuation PCTUS2018049059 · Aug 31, 2018
Provisional Application 62725196 · Aug 30, 2018
Provisional Application 62553309 · Sep 1, 2017
Related Publication 20240400724A1 · Dec 5, 2024
References Cited (170)
US 3888224A · Okuhara · 1975 [cited by examiner]
US 3943187A · Wu · 1976 [cited by applicant]
US 3947617A · Gerek · 1976 [cited by examiner]
US 3960979A · Khanna · 1976 [cited by examiner]
US 4071163A · Martin · 1978 [cited by applicant]
US 4071463A · Steinhauer · 1978 [cited by applicant]
US 4076676A · Sommerfeld · 1978 [cited by applicant]
US 4150005A · Gehman et al. · 1979 [cited by applicant]
US 4247439A · Matthews et al. · 1981 [cited by applicant]
US 4285847A · Ting · 1981 [cited by applicant]
US 4289674A · Christenson et al. · 1981 [cited by applicant]
US 4305859A · McEwan et al. · 1981 [cited by applicant]
US 4413015A · Anderson et al. · 1983 [cited by applicant]
US 4443568A · Woo · 1984 [cited by applicant]
US 4446258A · Chu et al. · 1984 [cited by applicant]
US 4452374A · Hitchcock · 1984 [cited by examiner]
US 4452375A · Marcus · 1984 [cited by examiner]
US 4476262A · Chu et al. · 1984 [cited by applicant]
US 4487859A · Martino · 1984 [cited by applicant]
US 4499212A · Martino · 1985 [cited by applicant]
US 4503173A · Martino et al. · 1985 [cited by applicant]
US 4522961A · Martino et al. · 1985 [cited by applicant]
US 4522962A · Abbey et al. · 1985 [cited by applicant]
US 4684708A · Deets et al. · 1987 [cited by applicant]
US 4948834A · Baker et al. · 1990 [cited by applicant]
US 4963602A · Patel · 1990 [cited by applicant]
US 5043380A · Cole · 1991 [cited by applicant]
US 5157078A · Woo et al. · 1992 [cited by applicant]
US 5201436A · Owens et al. · 1993 [cited by applicant]
US 5264469A · Mysliwczyk et al. · 1993 [cited by applicant]
US 5296525A · Spencer · 1994 [cited by applicant]
US 5306763A · Matsumoto et al. · 1994 [cited by applicant]
US 5308890A · Snyder · 1994 [cited by applicant]
US 5387625A · Parekh et al. · 1995 [cited by applicant]
US 5527840A · Chutko et al. · 1996 [cited by applicant]
US 5532297A · Woo et al. · 1996 [cited by applicant]
US 5714539A · Perez et al. · 1998 [cited by applicant]
US 5830952A · Pedersen et al. · 1998 [cited by applicant]
US 5869552A · Pedersen et al. · 1999 [cited by applicant]
US 5877239A · Craun et al. · 1999 [cited by applicant]
US 5922817A · Pedersen et al. · 1999 [cited by applicant]
US 6008273A · Leibelt et al. · 1999 [cited by applicant]
US 6710113B2 · Weitzel · 2004 [cited by applicant]
US 6992121B1 · Peters et al. · 2006 [cited by applicant]
US 7037584B2 · Wind et al. · 2006 [cited by applicant]
US 7189787B2 · O'Brien et al. · 2007 [cited by applicant]
US 7592047B2 · O'Brien et al. · 2009 [cited by applicant]
US 7682699B2 · Wind et al. · 2010 [cited by applicant]
US 7695770B2 · Dombrowski · 2010 [cited by applicant]
US 8057893B2 · Killilea et al. · 2011 [cited by applicant]
US 8092876B2 · O'Brien et al. · 2012 [cited by applicant]
US 8105744B2 · Matsumura · 2012 [cited by applicant]
US 8142868B2 · O'Brien et al. · 2012 [cited by applicant]
US 8173265B2 · O'Brien et al. · 2012 [cited by applicant]
US 8202578B2 · Killilea et al. · 2012 [cited by applicant]
US 8617663B2 · O'Brien et al. · 2013 [cited by applicant]
US 8835012B2 · O'Brien et al. · 2014 [cited by applicant]
US 8907005B2 · Dombrowski et al. · 2014 [cited by applicant]
US 8932718B2 · Garner et al. · 2015 [cited by applicant]
US 9012027B2 · Nabuurs et al. · 2015 [cited by applicant]
US 9029470B2 · Rademacher et al. · 2015 [cited by applicant]
US 9181448B2 · Li et al. · 2015 [cited by applicant]
US 9242763B2 · O'Brien et al. · 2016 [cited by applicant]
US 9394456B2 · Rademacher et al. · 2016 [cited by applicant]
US 9404006B2 · Li · 2016 [cited by applicant]
US 9409219B2 · Niederst et al. · 2016 [cited by applicant]
US 9415900B2 · O'Brien et al. · 2016 [cited by applicant]
US 9862854B2 · O'Brien et al. · 2018 [cited by applicant]
US 9962734B2 · Stokes · 2018 [cited by examiner]
US 10023997B2 · Haven et al. · 2018 [cited by applicant]
US 10214321B2 · Stokes · 2019 [cited by examiner]
US 11124661B2 · Barics · 2021 [cited by examiner]
US 11466162B2 · O'Brien et al. · 2022 [cited by applicant]
US 20030059618A1 · Takai · 2003 [cited by applicant]
US 20040236005A1 · Scheerder et al. · 2004 [cited by applicant]
US 20060100366A1 · O'Brien et al. · 2006 [cited by applicant]
US 20070265391A1 · Yang et al. · 2007 [cited by applicant]
US 20070292643A1 · Renn · 2007 [cited by examiner]
US 20080075868A1 · Dombrowski et al. · 2008 [cited by applicant]
US 20090012207A1 · Leyrer et al. · 2009 [cited by applicant]
US 20100068433A1 · Gibanel et al. · 2010 [cited by applicant]
US 20100243506A1 · Cleaver · 2010 [cited by examiner]
US 20110142899A1 · Lagaron Abello · 2011 [cited by examiner]
US 20120067763A1 · Ozawa · 2012 [cited by examiner]
US 20120091150A1 · Kanazawa · 2012 [cited by examiner]
US 20120184682A1 · Dasgupta · 2012 [cited by examiner]
US 20120302690A1 · Cunningham et al. · 2012 [cited by applicant]
US 20130105472A1 · Beaudry et al. · 2013 [cited by applicant]
US 20130206755A1 · Myerscough · 2013 [cited by examiner]
US 20130281574A1 · Li et al. · 2013 [cited by applicant]
US 20130316109A1 · Niederst et al. · 2013 [cited by applicant]
US 20140151370A1 · Chang · 2014 [cited by examiner]
US 20150004374A1 · Nahm · 2015 [cited by examiner]
US 20150004420A1 · Hill et al. · 2015 [cited by applicant]
US 20150031830A1 · Wu · 2015 [cited by applicant]
US 20150197597A1 · Gallucci et al. · 2015 [cited by applicant]
US 20150197657A1 · Niederst · 2015 [cited by examiner]
US 20160009941A1 · Rademacher · 2016 [cited by applicant]
US 20160024325A1 · Li · 2016 [cited by applicant]
US 20160096655A1 · Stokes · 2016 [cited by examiner]
US 20160145430A1 · Junk et al. · 2016 [cited by applicant]
US 20160297992A1 · Lalgudi · 2016 [cited by examiner]
US 20160297994A1 · Kuo et al. · 2016 [cited by applicant]
US 20160376446A1 · Gibanel et al. · 2016 [cited by applicant]
US 20170002227A1 · Gibanel et al. · 2017 [cited by applicant]
US 20170096521A1 · Niederst et al. · 2017 [cited by applicant]
US 20170096579A1 · Gibanel · 2017 [cited by examiner]
US 20170130076A1 · Most · 2017 [cited by examiner]
US 20170233140A1 · McMunn · 2017 [cited by examiner]
US 20170369603A1 · Gibanel et al. · 2017 [cited by applicant]
US 20180072840A1 · Lalgudi · 2018 [cited by examiner]
US 20180305492A1 · Taden · 2018 [cited by applicant]
US 20190002724A1 · DeSousa · 2019 [cited by examiner]
US 20190048300A1 · Gatewood · 2019 [cited by examiner]
US 20190329929A1 · Pang · 2019 [cited by examiner]
US 20190330491A1 · Maral · 2019 [cited by examiner]
US 20200199396A1 · O'Brien · 2020 [cited by applicant]
US 20230044013A1 · O'Brien · 2023 [cited by applicant]
US 20230047189A1 · O'Brien · 2023 [cited by applicant]
CN 105315735A · 2016 [cited by applicant]
EP 0256391 · 1988 [cited by applicant]
EP 0101307B1 · 1989 [cited by applicant]
EP 0401565 · 1990 [cited by applicant]
EP 0590984A1 · 1994 [cited by applicant]
GB 1555868 · 1979 [cited by applicant]
GB 1574721 · 1980 [cited by applicant]
JP 5339387 · 1978 [cited by applicant]
JP 5043830 · 1998 [cited by applicant]
JP 2002155234 · 2002 [cited by applicant]
JP 2008001888 · 2008 [cited by applicant]
JP 2016065130 · 2016 [cited by applicant]
KR 20100137850A · 2010 [cited by applicant]
WO WO199514063 · 1995 [cited by applicant]
WO WO02064691A2 · 2002 [cited by applicant]
WO WO2005121595 · 2005 [cited by applicant]
WO WO2010097353 · 2010 [cited by applicant]
WO WO2011009024 · 2011 [cited by applicant]
WO WO2012089747 · 2012 [cited by applicant]
WO WO2012170623 · 2012 [cited by applicant]
WO WO2013191825 · 2013 [cited by applicant]
WO WO2014025411 · 2014 [cited by applicant]
WO WO2014134442 · 2014 [cited by applicant]
WO WO2014139971 · 2014 [cited by applicant]
WO WO2014139973 · 2014 [cited by applicant]
WO WO2015002958 · 2015 [cited by applicant]
WO WO2015002961 · 2015 [cited by applicant]
WO WO2015015827 · 2015 [cited by applicant]
WO WO2015121595 · 2015 [cited by applicant]
WO WO2015158588A1 · 2015 [cited by applicant]
WO WO2016105502A1 · 2016 [cited by applicant]
WO WO2016105504A1 · 2016 [cited by applicant]
WO WO2016196174A1 · 2016 [cited by applicant]
WO WO2016196190A1 · 2016 [cited by applicant]
WO WO2017079437A1 · 2017 [cited by applicant]
WO WO20170012837 · 2017 [cited by applicant]
WO WO2017180895A1 · 2017 [cited by applicant]
WO WO2018013766A1 · 2018 [cited by applicant]
International Search Report and Written Opinion for International Application No. PCT/US2018/049059 date mailed Nov. 19, 2018. [cited by applicant]
International Search Report and Written Opinion for International Application No. PCT/US2018/049143 date mailed Dec. 21, 2018. [cited by applicant]
Wikipedia, “Acid Dissociation Constant”, Feb. 17, 2019. https://en.wikipedia.org/wiki/Acid_dissociation_constant. [cited by applicant]
Wikipedia, “Vinyl group”, Nov. 20, 2018. https://en.wikipedia.org/Vinyl_group. [cited by applicant]
Teng et al., “Effect of Introduction Mode of Hydroxyl Functionality on Morphology and Film Properties of Cycloaliphatic Diepoxide Crosslinkable Core-Shell Latex”, Journal of Polymer Science Part A Polymer Chemistry 40(2… [cited by applicant]
Chakraborty et al., “Assessment of Solubilization Characteristics of Different Surfactants for Carvedilol Phosphate as a Function of pH”, Journal of Colloid and Interface Science 335 (2009) 242-249. [cited by applicant]
Cytec, “Specialty Additives: Surfactants for Emulsion Polymerization and Specialty Applications,” 2010, 7 pages. [cited by applicant]
ADEKA Corporation, “New Reactive Surfactant ADEKA REASOAP ER/SR Series Technical Datasheet,” Sep. 30, 2011, 8 pages. [cited by applicant]
The Polymer Property Database accessed online at https:polymerdatabase.com/polymer%20Physics/Polymer%20Tg.html, 6 pages. 2021. [cited by applicant]
Sigma-Aldrich, Dihexyl sodium sulfosuccinate for synthesis, Jul. 2020, 2 pages. [cited by applicant]
GEO Specialty Chemicals, “Bisomer PEM 6 LD Technical Data Sheet,” Oct. 2020, 2 pages. [cited by applicant]
Notice of Rejection from JP Patent Appln No. 2020-511960 dated Apr. 12, 2022, 13 pages. [cited by applicant]
Korean Notice of Allowance for KR Application No. 10-2020-7008917, issued by the Korean Patent Office on Jul. 12, 2024; 10 pgs. including English translation. [cited by applicant]