IP Library › Granted Patent US 12,331,141
Granted Patent B2
US 12,331,141 · App. 18/370,816 · Granted Jun 17, 2025

Styrene-free copolymers and coating compositions containing such copolymers

Inventors: Robert M. O'Brien (Monongahela, PA); Mark Stuetelberg (Hiawatha, KS); Sebastien Gibanel (Givry, FR)
Assignee: SWIMC LLC
C08F220/1802B65D25/14C08F2/22C09D4/06C09D133/10C09D133/12C09D201/02B05D7/227B05D2202/25C08F220/14C08F220/1804
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 12,331,141
App. No.
18/370,816
Granted
Jun 17, 2025
Kind
B2
Abstract

An aqueous coating composition is provided that is preferably substantially free of styrene and structural units derived from styrene. The coating composition includes a resin system that preferably includes a water-dispersible polymer and an emulsion polymerized ethylenically unsaturated monomer component. The resin system is preferably formed using a process that includes emulsion polymerizing the ethylenically unsaturated monomer component in the presence of an aqueous dispersion including the water-dispersible polymer. In certain preferred embodiments, the water-dispersible polymer is a salt of an acid- or anhydride-functional aromatic polyether polymer.

Claims (44)

1. An inside spray beverage can coating composition comprising:

an aqueous carrier comprising at least 5 wt-% of organic solvent; and

a resin system dispersed in the aqueous carrier, wherein the resin system is substantially free of styrene and comprises:

a water-dispersible polymer having an acid number from 40 to 400 milligrams KOH per gram and comprising an acrylic polymer; and

an emulsion polymerized ethylenically unsaturated monomer component polymerized in the presence of an aqueous dispersion of the water-dispersible polymer, wherein the ethylenically unsaturated monomer component: (i) comprises at least 70 wt-% of (meth)acrylate monomers, wherein the ethylenically unsaturated monomer component includes at least 30 wt-% of one or more methacrylate monomers and (ii) has a Tg of at least 20° C.;

wherein the total combined weight of the water-dispersible polymer and the emulsion polymerized ethylenically unsaturated monomer component is at least 50 wt-% of the total resin solids present in the coating composition;

wherein the coating composition has a viscosity of from 20 to 80 seconds (Ford Cup #2, 25° C.); and

wherein the coating composition, when spray applied onto the interior of a standard 12 ounce two-piece aluminum drawn and ironed beverage can at a dry film weight of 115 milligrams per can and baked for at least 50 seconds at an oven temperature of at least 370° F. to achieve a dome peak metal temperature of at least 390° F., exhibits:

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

(ii) a drop damage of less than about 3.5 mA on average when the can is filled with 1% NaCl in deionized water and tested pursuant to the Metal Exposure After Drop Damage test method disclosed herein.

2. The coating composition of claim 1 , wherein the one or more methacrylate monomers comprise more than 50 wt-% of the ethylenically unsaturated monomer component.

3. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer component includes at least 50 wt-% of one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.

4. The coating composition of claim 3 , wherein one or more monomer having a C1-C3 alkyl group comprise at least 40 wt-% of the ethylenically unsaturated monomers.

5. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer component includes at least 60 wt-% of one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.

6. The coating composition of claim 5 , wherein one or more of methyl methacrylate and ethyl acrylate comprise at least 60 wt-% of the ethylenically unsaturated monomers.

7. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer component includes at least 70 wt-% of one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.

8. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer component includes at least 80 wt-% of one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.

9. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer component comprises at least 95 wt-% of (meth)acrylates.

10. The coating composition of claim 1 , wherein the emulsion polymerized ethylenically unsaturated monomer component includes, if any, less than 5 wt-% of vinyl aromatic compounds.

11. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer does not contain any acrylamide-type monomers.

12. The coating composition of claim 11 , wherein the ethylenically unsaturated monomer component does not include any oxirane-group-containing monomers.

13. The coating composition of claim 1 , wherein the water-dispersible polymer is phosphated.

14. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer component has a glass transition temperature greater than 50° C.

15. The coating composition of claim 3 , wherein the acrylic polymer has an acid number of at least about 70 to less than about 200 milligrams KOH per gram of the polymer, and wherein the ethylenically unsaturated monomer component has a glass transition temperature greater than 60° C.

16. The coating composition of claim 1 , wherein the total combined weight of the water-dispersible polymer and the emulsion polymerized ethylenically unsaturated monomer component is at least 80 wt-% of the total resin solids present in the coating composition.

17. The coating composition of claim 16 , wherein the coating composition has a total solids weight ranging from greater than about 15% to less than about 25%.

18. The coating composition of claim 1 , wherein the coating composition has a total solids weight ranging from about 18% to about 22%.

19. The coating composition of claim 1 , wherein the coating composition contains at least about 1% by weight and up to about 15% by weight of a beta-hydroxyalkyl-amide crosslinking agent, based on the total resin solids weight of the coating composition.

20. The coating composition of claim 1 , wherein a cured coating formed from the coating composition has a glass transition temperature greater than 50° C.

21. The coating composition of claim 3 , wherein a cured coating formed from the coating composition has a glass transition temperature greater than 70° C.

22. An inside spray beverage can coating composition comprising:

an aqueous carrier comprising at least 5 wt-% of organic solvent; and

a resin system dispersed in the aqueous carrier, wherein the resin system is substantially free of styrene and comprises:

a water-dispersible polymer having an acid number from 40 to 400 milligrams KOH per gram, a number average molecular weight from 2,000 to 20,000, and comprising an acrylic polymer; and

an emulsion polymerized ethylenically unsaturated monomer component polymerized in the presence of an aqueous dispersion of the acrylic polymer, wherein the ethylenically unsaturated monomer component: (i) does not contain any acrylamide-type monomers, (ii) comprises at least 60 wt-% of one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate, and (iii) has a Tg of at least 50° C.;

wherein the total combined weight of the water-dispersible polymer and the emulsion polymerized ethylenically unsaturated monomer component is at least 80 wt-% of the total resin solids present in the coating composition;

wherein the coating composition has a viscosity of from 20 to 80 seconds (Ford Cup #2, 25° C.); and

wherein the coating composition, when spray applied onto the interior of a standard 12 ounce two-piece aluminum drawn and ironed beverage can at a dry film weight of 115 milligrams per can and baked for at least 50 seconds at an oven temperature of at least 370° F. to achieve a dome peak metal temperature of at least 390° F., exhibits:

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

(ii) a drop damage of less than about 3.5 mA on average when the can is filled with 1% NaCl in deionized water and tested pursuant to the Metal Exposure After Drop Damage test method disclosed herein.

23. The coating composition of claim 22 , wherein the ethylenically unsaturated monomer component comprises 99 wt-% or more of (meth)acrylates.

24. The coating composition of claim 23 , wherein a cured coating formed from the coating composition has a glass transition temperature greater than 50° C.

25. The coating composition of claim 24 , wherein one or more methacrylate monomers comprise at least 50 wt-% of the ethylenically unsaturated monomer component.

26. The coating composition of claim 22 , wherein one or more methacrylate monomers comprise at least 70 wt-% of the ethylenically unsaturated monomer component.

Continuity (7)
Continuation 17720928 · Apr 14, 2022
Continuation 17097568 · Nov 13, 2020
Continuation 16705421 · Dec 6, 2019
Continuation 16160579 · Oct 15, 2018
Continuation PCTUS2017027453 · Apr 13, 2017
Provisional Application 62323314 · Apr 15, 2016
Related Publication 20240279375A1 · Aug 22, 2024
References Cited (134)
US 3943187A · Wu · 1976 [cited by applicant]
US 4071463A · Steinhauer · 1978 [cited by applicant]
US 4076676A · Sommerfeld · 1978 [cited by applicant]
US 4212781A · Evans et al. · 1980 [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 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 4517322A · Birkmeyer 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 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 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 9540484B2 · Craun et al. · 2017 [cited by applicant]
US 9605177B2 · Tang et al. · 2017 [cited by applicant]
US 9862854B2 · O'Brien et al. · 2018 [cited by applicant]
US 10306168B2 · Ohmaru · 2019 [cited by applicant]
US 10501639B2 · O'Brien et al. · 2019 [cited by applicant]
US 10836915B2 · O'Brien et al. · 2020 [cited by applicant]
US 20020155235A1 · Taylor et al. · 2002 [cited by applicant]
US 20030059618A1 · Takai · 2003 [cited by applicant]
US 20030170396A1 · Yokoi et al. · 2003 [cited by applicant]
US 20040236005A1 · Scheerder et al. · 2004 [cited by applicant]
US 20050196629A1 · Bariatinsky et al. · 2005 [cited by applicant]
US 20060100366A1 · O'Brien et al. · 2006 [cited by applicant]
US 20100068433A1 · Gibanel et al. · 2010 [cited by applicant]
US 20120302690A1 · Cunningham et al. · 2012 [cited by applicant]
US 20130206756A1 · Niederst et al. · 2013 [cited by applicant]
US 20130281574A1 · Li et al. · 2013 [cited by applicant]
US 20130316109A1 · Niederst et al. · 2013 [cited by applicant]
US 20140322465A1 · Kaleem et al. · 2014 [cited by applicant]
US 20150004420A1 · Hill et al. · 2015 [cited by applicant]
US 20150021323A1 · Niederst et al. · 2015 [cited by applicant]
US 20150038635A1 · Martinez-Castro · 2015 [cited by applicant]
US 20150197597A1 · Gallucci et al. · 2015 [cited by applicant]
US 20150197657A1 · Niederst et al. · 2015 [cited by applicant]
US 20160009941A1 · Rademacher · 2016 [cited by applicant]
US 20160017171A1 · Li et al. · 2016 [cited by applicant]
US 20160024325A1 · Li · 2016 [cited by applicant]
US 20160107818A1 · Kaleem et al. · 2016 [cited by applicant]
US 20160122581A1 · You et al. · 2016 [cited by applicant]
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 20170369603A1 · Gibanel et al. · 2017 [cited by applicant]
US 20200109293A1 · O'Brien et al. · 2020 [cited by applicant]
US 20200385601A1 · Gibanel et al. · 2020 [cited by applicant]
EP 0256391A2 · 1988 [cited by applicant]
EP 0101307B1 · 1989 [cited by applicant]
GB 1555868A · 1979 [cited by applicant]
GB 1574721A · 1980 [cited by applicant]
JP S5339387A · 1978 [cited by applicant]
JP S62223211A · 1987 [cited by applicant]
JP S63020311A · 1988 [cited by applicant]
JP H0543830A · 1993 [cited by applicant]
JP H05132647A · 1993 [cited by applicant]
JP H08231925A · 1996 [cited by applicant]
JP 2002155234A · 2002 [cited by applicant]
WO WO2002064691A2 · 2002 [cited by applicant]
WO WO2005121595A2 · 2005 [cited by applicant]
WO WO2010097353A1 · 2010 [cited by applicant]
WO WO2011009024A1 · 2011 [cited by examiner]
WO WO2012089747A1 · 2012 [cited by examiner]
WO WO2012170623A2 · 2012 [cited by applicant]
WO WO2013191825A1 · 2013 [cited by applicant]
WO WO2014025411A1 · 2014 [cited by applicant]
WO WO2014089410A1 · 2014 [cited by applicant]
WO WO2014134442A1 · 2014 [cited by applicant]
WO WO2014139971A1 · 2014 [cited by applicant]
WO WO2014139973A1 · 2014 [cited by applicant]
WO WO2014186285A1 · 2014 [cited by applicant]
WO WO2015002958A1 · 2015 [cited by applicant]
WO WO2015057932A1 · 2015 [cited by applicant]
WO WO2015160788A1 · 2015 [cited by applicant]
WO WO2015164703A1 · 2015 [cited by applicant]
WO WO2015179064A1 · 2015 [cited by applicant]
WO WO2016105504A1 · 2016 [cited by applicant]
WO WO2016196174A1 · 2016 [cited by applicant]
WO WO2016196190A1 · 2016 [cited by applicant]
WO WO2016201407A1 · 2016 [cited by applicant]
WO WO2017079437A1 · 2017 [cited by applicant]
WO WO2017112837A1 · 2017 [cited by applicant]
WO WO2017180895A1 · 2017 [cited by applicant]
WO WO2018013766A1 · 2018 [cited by applicant]
“New Reactive Surfactant ADEKA REASOAP ER/SR Series”, Surface Active Agents, Technical Information, ADEKA Amazing Chemicals, ADEKA Corporation, 8 pages (2011). [cited by applicant]
Extended European Search Report for EP Application No. EP 17783149.2, dated Nov. 29, 2019, 7 pages. [cited by applicant]
Office Action for Japanese Patent Application No. 2018-553140 dated Feb. 12, 2021, 6 pages. [cited by applicant]
Surfactants Products List, Surface Active Agents, ADEKA Amazing Chemicals, ADEKA Corporation, 16 pages (2013). [cited by applicant]