陶氏水性環(huán)氧涂料

1、NEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 1VOC-free WaterborneEpoxy Emulsions and Dispersionsfor Ambient Cure CoatingsNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 2Waterborne Epoxy dispersions? Stricter legislation is limiting the use of solvents-Volatile Organ

2、ic Compounds (VOC) in paints e.g.European directive 1999/13/EC and amendment 2004/42/EC first stage implemented in 2007 second stage implemented in 2010U.S.: 3 major organizations driving the reduction of VOC Environmental Protection Agency (EPA, through Clean Air Act) South Coast Air Quality Manage

3、ment District (SCAQMD) Ozone Transportation Commission (OTC) “Green Image” environmental friendly coatings Low odor, low flammability Easy cleaning of equipment with waterMaking use of the excellent properties of Epoxy resins (e.g. corrosionresistance, chemical resistance, adhesion,) with minimal am

4、ounts of solvent to fulfill legal and environmental requirementsNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 3Drivers and alternative approachesTypical solvent borne formulations for Marine and Protective coatings are based on epoxy resin grades with an Epoxy Equivalent Weight of 5

5、00 gr/eq containing solvents like XyleneTypical solvent content of these solid epoxy resin solutions is 25%Major contributor to the overall VOC content of a solvent borne formulationSeveral approaches exist to minimize or eliminate the VOC content High solids coatings Powder coatings Radiation cured

6、 coatings Waterborne coatingsNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 4Dows Technology ApproachDow technology Non ionic surfactant was especially developed for WB epoxy resins Surfactant is epoxy functional so that it will be part of the cured matrix Unique dispersion process w

7、hich allows mono modular and submicron particle size distributions Submicron particle size distributions allow a good storage stability and film formation Formulator can use solvent of choice No additional solvent, so low VOC formulations can be preparedGrades Emulsion of a Liquid Epoxy Resin commer

8、cial grade Dispersion of an Epoxy Novolac Resin commercial grade Dispersion of a Solid Epoxy Resin commercial grade ChemistryProcessProperties+Ambient cured coatingsNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 5VOC free WB epoxy dispersionsAqueous dispersion based on LiquidEpoxyRes

9、inSolidEpoxyResin EpoxyNovolacResin GradeXZ 92598.00XZ 92533.00XZ 92546.00Epoxy Equivalent Weight (gr/eq)194 204475 500184 204Solid content60 - 75 %46 - 48 %56 - 59 %Viscosity 23 CBrookfield, mPas3000 - 30.0003000 - 90005000 - 10.000Typical average Particle size D4.3 0.5 m0.5 m0.5 mNEO Chemical Semi

10、nar 2007Toine Dinnissen / March 28th 2007Page 6Typical Particle Size distributions Particle Size Distribution 0.01 0.1 1 10 100 1000 10000 Particle Size (m)0 2 4 6 8 10 12 14 Volume (%)XZ 92533.00 T60B, Friday, November 12, 2004 3:15:26 PMParticle size distributionof an aqueous dispersionof a solid

11、epoxy resin Particle Size Distribution 0.01 0.1 1 10 100 1000 10000 Particle Size (m)0 2 4 6 8 10 12 14 16 Volume (%)XZ9254600 pure, Tuesday, June 14, 2005 11:12:10 AMParticle size distributionof an aqueous dispersionof an epoxy novolac resinNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007

12、Page 7Storage Stability Weeks ofstorageAverageparticle size D4.3EpoxyEquivalentWeightBrookfieldviscosity at 23C00.385 m190 g/eq4660 mPas270.385 m191 g/eq4200 mPas560.390 m191 g/eq4200 mPasSubmicron particle size distributions lead to excellent storage stabilitiesdemonstrated with the example of a WB

13、 epoxy novolac dispersion XZ 92546.00Only very light sediment after one year of storage at 23C which can be easily stirred inNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 8Viscosity profile of epoxy dispersionSolid contents up to 54% without solvents can be achieved if high viscosit

14、ies can be toleratedXZ 92533.00 Good shear thinning properties allowing good flow and spray properties0123456789100.11101001000s-1Pa*sXZ 92533.00 upXZ 92533.00 downNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 9Mechanical dispersion Process Process patented by Dow: Continuous feed o

15、f resin and water to the mixing unit under high shear High viscous resins can be dispersed without the addition of solvents Excellent transfer of process parameters from lab to pilot to manufacturing scale Submicron and mono modular particle size distributionsNEO Chemical Seminar 2007Toine Dinnissen

16、 / March 28th 2007Page 10Influence of process parametersParticle size can be influencedby the total flow rateI In nf fl l u ue en nc ce e o of f f fl l o ow w r ra at te es s o on n a av ve er ra ag ge e p pa ar rt ti i c cl l e e s si i z ze e o of f W W B B E Ep po ox xy y N N o ov vo ol l a ac c

17、D D i i s sp pe er rs si i o on n R R2 2 = = 0 0. .9 92 26 62 20 0. .3 30 00 0. .3 35 50 0. .4 40 00 0. .4 45 50 0. .5 50 00 0. .5 55 50 0. .6 60 00 0. .6 65 50 0. .7 70 00 0. .7 75 50 0. .8 80 00 05 50 00 01 10 00 00 01 15 50 00 02 20 00 00 02 25 50 00 0F Fl l o ow w r ra at te e, , g g/ / m m i i

18、n nV Vm m e ea an n p pa ar rt ti i c cl l e e s si i z ze e ( (m m i i c cr ro on ns s) )NEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 11Vi scosi ty versus parti cl e si ze for W B Epoxy N ovol ac di spersi on sam pl esVi scosi ty versus parti cl e si ze for W B Epoxy N ovol ac di

19、spersi on sam pl esVi scosi ty m easured by B rookfi el d D V-1 w i th Spi ndl e #3 at 5 rpm , 23 CVi scosi ty m easured by B rookfi el d D V-1 w i th Spi ndl e #3 at 5 rpm , 23 CR2 = 0.98840 02000200040004000600060008000800010000100001200012000140001400016000160000.2500.2500.3000.3000.3500.3500.400

20、0.4000.4500.4500.5000.5000.5500.550V M ean parti cl e si ze (m i crons)V M ean parti cl e si ze (m i crons)Vi scosi ty (m Pa*s)Vi scosi ty (m Pa*s)Significant increasein viscosity with decreasingparticle size distributionInfluence of process parametersNEO Chemical Seminar 2007Toine Dinnissen / March

21、 28th 2007Page 12Solid Epoxy Resin DispersionNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 13Cure RatePersoz H ardnessPersoz H ardness0501001502002503003501234567days of cure at 23 Cdays of cure at 23 Cs sC uri ng agent 1C uri ng agent 1C uri ng agent 2C uri ng agent 2Both Curing ag

22、entsare based on water soluble epoxy amine adductsDrying times based on drying time recorderCuring agent 1Curing agent 2End of gel tear2.9 h2.4 hEnd of scratch7 h9.4 hNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 14Pot lifeAs 2K WB epoxy systems dont have necessarily a visible end o

23、f pot lifelike their solvent borne counterparts other properties are testedSome 2K WB epoxy systems based on Dows dispersion technology show excellent gloss retention over timeGloss measurement over potlife XZ 92441.0102040608010012000.51234h206085NEO Chemical Seminar 2007Toine Dinnissen / March 28t

24、h 2007Page 15Anti-corrosive Primer WhiteComponent AWeight-%1 Curing Agent 213,42 Demineralised water29,13 TEGO Dispers 750W Tego-Chemie 1,64 BYK 019 / 024 (3:2)BYK Chemie0,55 Omya BLR 3 Omya17,56 Micro-Talc AT ExtraOmya9,07 Micro-Talc AT 1Omya8,08 Heucophos ZPAHeubach10,09 Kronos 2059Kronos10,010 Ae

25、rosil R 972Degussa0.9Total Component A:100,0Component B1-Type Dispersion87,0NEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 16Barrier properties Good barrier properties against solvents, water and basic materials The clear coated systems show some minor deficiencies against some acids

26、 Fully formulated systems based on commercial available anticorrosion pigments achieve 1000 hours of salt spray resistance on pretreated steel panels Corrosion/salt spray resistance on cold rolled steel of 1000 hours could be achieved with the help of adhesion promoters e.g. based on epoxy silane ch

27、emistryNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 17Salt-Spray Test DIN 50021 Exposure 1000 hours Blistering: none (m0g0) Under rusting: 1 mm Adhesion: GT1 Scratch-Test: o.k. (K0) Substrate Cold Rolled Steel, Type R-46 (Q-panel)NEO Chemical Seminar 2007Toine Dinnissen / March 28t

28、h 2007Page 18Institutional CoatingNEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 19Pot-life and DryingDry Times (1.5 mil dry films)Set-To-Touch0.4 hrs.Surface Dry0.6 hrs.Dry Through5.0 hrs.20 Degree GlossNo Induction10130 Min.1011 Hr.1012 Hr.923.5 Hrs.784.5 Hrs.65NEO Chemical Seminar 2007Toine Dinnissen / March 28th 2007Page 20Res