Silicone-based powder coatings

For more than fifty years solvent-based silicone resins have been used for the coating of objects, which are exposed to high temperatures (>200 °C), such as boilers, engines, exhaust stacks, heat exchangers, mufflers, barbecue equipment, etc.

Due to environmental concerns and regulations, recent efforts by silicone resin manufacturers and powder coating formulators have expanded the utility of silicone-based technologies into the field of powder coatings [305, 306]. Silicone resins are structurally based on a framework of Si-O and Si-C bonds. They provide excellent heat and weathering resistance, but also inertness to chemicals and good electrical characteristics. These properties are due to the stability of the Si-O-Si bond, stability of organic radicals attached to the Si atom, (because of the screening effect of the siloxane bond), the formation of stable Si-O-Si bonds within the polymer upon partial disintegration (in contrast to organic radicals) thus preventing film disruption, and the insulating effect of the siloxane layer (formed during thermal oxidation).

Excellent heat-resistant properties will be provided by pure silicone polymers, but for most practical applications, the organic-modified silicones meet the requirements for the majority of specifications. Most silicone resins are produced by the co-hydrolysis of di- and trichlorosilanes. The resulting di- and trisilanol moieties are highly reactive and the majority will immediately condense to form a polymeric resin matrix. Therefore hydrolysis and polycondensation are generally performed in one step. Polycondensation between silanediols yield straight-chain polymers;

Whereas similar reactions between silanetriols result in the formation of highly crosslinked polymer molecules:

  • The strenght of the Si-O bond significantly exceeds that of the Si-Si or the Si-C bonds. That means there is a strong tendency for the two elements (Si and O) to combine and to build up polymers, in which the structural unit.
  • Reactions of carbon conpounds tend to produce only five-or six-membered rings, whereas silicone rings of relatively large size may be formed quite readily. It seems, therefore, according to Groggines that cyclization competes more seriously with chain-polymer formation in the reactions of the silicone atom, than it does in carbon chemistry.

Synthesis of the before mentioned chlorosilanes can be carried out by means of the wellknown Grignard reaction, by reacting silicon tetrachloride with alkyl magnesium bromide: Another, more direct way of preparing chlorosilanes, involving the reaction of silicon with alkyl- or arylchlorides, with the use of copper or silver catalysts is also possible [307]. Both
methods produce a mixture of the various chlorosilanes, which leads, after hydrolysis, also to a mixture of the various silanols.
Silanol groups, which remain unreacted during the following polycondensation, can be condensed after application of the coating or co-reacted with organic polymers. Due to the electro-negativity of the Si atom, a hydroxy group attached to a silicon atom is more polar and therefore more acidic than its carbon analog (carbinol).

As a result, reactions between silanol functional resins and hydroxyl functional organic polymers will take place at relatively low temperatures (110 to 115 °C).
The cure scheme for a silicone-based powder coating is dependent on the silicone content and the selection of the organic co-binder.

A typical cure for a coating, based on 100 % silicone would be 30 min at 230 to 250 °C. Cerium acetylacetonate can accelerate the stoving process [306]. Silicone resins are high molecular weight polysiloxanes, which mostly contain
methyl- and/or phenyl groups as organic substituents. Methyl silicone resins are harder and less thermoplastic than phenyl silicones, but less heat resistant, because of the greater sensitivity to oxidation of the CH3 groups. Pure methyl silicones have, due to the relative small mass of the methyl group, a lower C-content and a higher SiO2-content than the phenyl types. A disadvantage is that they are not compatible with other organic resins. Phenyl silicone resins have good heat stability up to temperatures of 250 °C, but like all organic groups, they will decompose at about 400 °C.

While they are claimed to be the betterchoice for heat resistance in the intermediate range (100 to 375 °C), it should be remarked, that when the organic component is oxidized, the losses in film weight of phenyl groups will be higher than those of methyl groups. Additionally, the reactive silanols, sharing a silicon atom with a phenyl group are sterically hindered. This can result in poor cure and reduced physical properties. The main advantage of phenyl silicones is their compatibility with other organic resins. Compatibility is essential to ensure miscibility with the resin components, reducing the tendency to cross-contamination problems and film disruption, and at the same time improving physical properties.

An important factor affecting the suitability of a silicone resin is the crosslink density or degree of substitution. In the natural state the four valency sites of a silicon atom are bound with oxygen. Silicone-based resins are created by substituting one, two, three or four of these oxygen atoms with a variety of moieties. The number of substituted oxygens per silicon atom is called the “degree of substitution”. In the case of conventional silicone-based coating resins, phenyl and methyl groups are most often utilized, and commercially available silicone resins possess degrees of substitution within a range from 1.0 to 1.8. In this range the physical form of the resin can vary from a hard brittle solid to a viscous liquid.

Physical properties are also affected by the molecular weight and residual silanol (SiOH) content of the resin. If highest heat resistance is required, a powder coating will be formulated with a 100 % silicone. This will provide the best thermal properties in applications, where heat resistance has a higher priority than organic compatibility. A resin with a balanced phenyl/methyl
ratio and highest allowable degree of substitution should be selected.

For less stringent applications a silicone resin with high phenyl content should be used allow for mixing with organic resins, to reduce raw material costs and to improve the physical properties of the coating. Selection of the right pigments to achieve maximum temperature resistance is very important. Coatings with short-term exposures (<1000 hours) at up to 350 °C, or long-term exposures up to 225 °C can be produced with TiO2 and mica. Applications with short-term up to 525 °C or long-term exposures up to 250 °C often include heat resistant black iron oxides.

Aluminum, zinc and stainless steel powders are used for high temperature applications, in the short term up to 650 °C or long term at 350 °C. The inclusion of metal pigments with their high thermal conductivity prolongs the life of the
coating by conducting heat away from the coated substrate. Additionally, the inclusion of metal pigments compensates for the
inevitable oxidation of the silicone resin at high temperatures by stabilizing the coating as the metal fuses with the resin to form a ceramic coating with stable metalsiloxane bonds. Similarly, ceramic frits are used to create durable coatings, which are stable up to 750 °C [305].

DuPont [308] claimed that the addition of up to 50 % of alkali tetraborate will lead to a heat stability of at least 550 °C, suitable in particular for boilers, ovens, heat exchangers, and cooking utensils. Enhancements to the thermal stability of the coating can also be achieved by increasing the amount of lamellar fillers (such as mica), or incorporation of anti-oxidants.
Table below [306, 309] gives typical formulations for a matt black and a glossy white silicone-based powder coating. In the mid-nineties, also silicone elastomeric powders have been introduced [305, 310].

 

A. Silicone powder coating with good color stability and heat resistance up to 300 °C

Material Parts by weight
Silres 604″  (1)” 56.3
Crylcoat 2617-3″ (2)” 11.0
“ß-hydroxyalkyl amide” (3) 0.7
Blanc Fixe F” (4)” 10.0
Synergy Red 6054″ (5)” 20.0
Resiflow PV88″ (6)” 1.5
Benzoin 0.5

 

Properties Value
Curing conditions 30min/230 to 250 °C
Properties: Film thickness 40 to 60 μm
Pencil hardness 4 H
Gloss 60° 74 %
Gloss 60° after 20 h 265 °C 29 %
Crosshatch GT 1
MEK-resistance >200 DR

 

B. Silicone powder coating with corrosion and high heat resistance

Material Parts by weight
Silres 604″ (1)” 47.5
FERRO PK 3095″ (7)” 15.0
“Glimmer TM” (8) 11.0
Heucophos SAPP” (9)” 13.5
Talkum EL–10″ (10)” 12.3
Resiflow PV88″ (6)” 0.3
Benzoin 0.4

 

Properties Value
Curing conditions 30min/230 to 250 °C
Properties: Film thickness 40 to 60 μm
Pencil hardness 4 H
Gloss 60° 15.4 %
Gloss 60° after 1 h 500 °C 12.8 %
Crosshatch GT 1
Impact resistance (dir.) > 80 inch·lbs

(1) Methyl polysiloxane (Wacker Chemie AG)
(2) Polyester (Cytec)
(3) “VESTAGON HA 320”(Evonik Industries) or “Primid XL-552” (Ems)
(4) various suppliers
(5) Pigment (Engelhard)

(6) flow agent, (Worlée)
(7) iron oxide (Ferro)
(8) mica filler (ASpanger Mineralwerke)
(9) anticorrosion pigment (Heubach GmbH)
(10) Talcum (Luzenac-Europe)

These soft and flexible spherical particles (average
particle size 3 to 5 µm) can be incorporated into powder coating formulations to create coatings with unique appearance, texture and feel. With doses of 5 to 15 % they give tough textured finishes. At higher levels suede or soft-feel coatings can be produced. DuPont [311] claims the use of low-melting glass particles to fill voids in the film and prevent adhesion failure.
Dow Corning have commissioned a study by the University of Southern Mississippi.The results of the study are described by researchers from Dow Corning, Dow Chemical and the University of South Mississippi [312]. The study concentrated on three themes: the effect of pigment volume concentration (pvc); the effect of silicone resin composition, using four Dow Corning silicone resins; and the compatibility and high temperature performance of silicone-polyester at ratios of 70:30 and 30:70.
For all their experiments they used a high temperature resistant spinel black pigment. The conclusions of their studies can be summarized as follows:

  • The most suitable PVC level is 24%.
  • Film thickness should be kept below 40 µm, to avoid solvent popping and wrinkling;
  • All tested solid silicone resins can be used to formulate high temperature resistant powder coating (a heat exposure test of 1000 hours at 45 C can be realized using the spinel black pigment);
  • It is important to match silicone/organic powder coating blends using polymers of similar viscosities and reactives.

The problem of solvent popping is thought to be caused by water, evolved due to silanolsilanol condensation.

Acrylic-silicone powder coating resins are described by a team of researchers at the Glidden Co. [313]. They blended a hydroxyl acrylic resin with a solid silicone resin and cured the blend with a blocked isophorone diisocyanate adduct. The preferred silicone resin is a hydroxy functional low molecular weight cyclic silicone intermediate (“DC-Z-6018”), having a number average molecular weight of about 600. The hydroxyl functional acrylic polymer and the silicone resin are dry blended in a weight ratio of between 50 and 75 % acrylic resin and between 25 and 50 % cyclic silicone. It is shown by accelerated weathering, that gloss retention is much higher for the silicone containing materials (particularly at the 50 % level) than for the acrylic resin without any silicone resin.

The same researchers [313] attempted to make a graft copolymer of silicone-acrylic, but this failed, due to the high reactivity of the silanol hydroxyl (SiOH) groups. But, upon reacting the silanol hydroxyl groups with fluorinated alcohols before grafting the acrylic monomers, a graft copolymer of silicone-acrylic can be successfully made. It is believed, that the weathering resistance of this fluorinated silicone-acrylic copolymer should be excellent.

In a patent [314] of Rohm and Haas the use of trifluoromethane sulfonic acid diethylamine salt as a wrinkling agent in silicone based powder coatings is claimed.

A paper by Rawlins and Thames [315] reports the synthesis, characterization and evaluation of novel silicone modified polymers as clear UV curable powder coatings. These polymers are described as acrylated, silylated diglycidyl ethers of bisphenol A (DGEBA).They are synthesized by reacting acrylic acid with DGEBA polymers in the presence of a base catalyst and free radical inhibitors. Silylation is realized by the addition of 10 mol-% excess of hexamethyl disilazane to the washed acrylated DGEBA. UV curable powders are made by adding two photoinitiators to each of the silicone modified polymers, and melt mixing and grinding them in the usual way.Though the silylated modifications of DGEBA polymers are likely to be of academic interest only [316], there are some interesting facts arising from this study. The most important ones concern the low melt viscosities, achieved with these polymers (without sacrificing storage stability) and the complete freedom from surface defects, such as cratering and orange peel, obtained without the addition of flow control agents.
Wacker [317] reported the use of solid silicone-polyesters in conventional thermoset powder coatings, leading to a higher heat- and UV resistance compared to the pure polyesters. Silicone modification reduces the polymer-Tg by nearly 32 % from the starting polymer.
The use of silicone resins for high-temperature resistant powder coatings is still in its infancy and a lot of new developments and applications are to be expected from this interesting field of special powder coatings in near future.

Reference:

Powder coating chemistry and technology

Author:

Pieter Gillis de lange

References
[1] Greenspan, F.P., Chemical Reactions of Polymers, Ed. E.M. Fettes Interscience, New York, 1964, p. 152
[2] Paul, S., Surface Coatings: Science and Technology, John Willey and Sons, 1985, p. 219
3] Wise, J.K., J. Paint Technol., 42, (540), 29, 1970
[4] Ranney, M.W., Epoxy Resins and Production: Recent Advances, Noyes Data Corp., 1977
[5] Brushwell, W., Am. Paint and Coat. J., Nov. 2, 65, 1981
[6] Brushwell, W., FARBE&LACK, 87, (3), 201, 1981
[7] Oldring, P., and Hayward, G., Resins for Surface Coatings, Vol. II, p. 4, SITA Technology, London, 1987
[8] Asahi Chemical Ind., Jap. Pat. 58.187.464, 1982
[9] Drake, R., Proc. 13th Internat. Conf. (PRA), Brussels, Nov. 1993, Paper 4
[10] Basf Coatings Japan, WO 2007138399, 2007
[11] Sumitomo Durez, Jap. Pat. 59.226.066 and 59.226.067, 1983
[12] Greensitt, E.A., Paint Technology, 28, (9), 16, 196
[13] Kimmo Peltonen, Thermal Degradation of Epoxy Powder Paints, Institute of Occupational Health, Helsinki, 1986
[14] Peltonen, K., Analyst, 111, 819, 1986
[15] General Electric Company, US 20050261398, 2005
[16] Dow Epoxy Resins in Powder Coatings, Dow Chemicals Brochure Ed. 1987 and 1991
[17] Barletta, M.; Bolelli, G.; Gisario, A.; Lusvarghi, L., Progress in Organic Coatings, 61(2-4), 262-282, 2008
[18] Hitachi Chemical KK, Jap. Pat. 58.087.123, 1981
[19] Wagemakers, NL Pat. 138.009 (1973)
[20] Shell Oil Company, US Pat. 3.824.035, 1974
[21] Wagemakers, NL Pat. 134.229 (1971)
[22] Dow Chemical Europe, EP 0.072.371, 1981
[23] Gulpen, N.J.H., Werff van de A.J., J. Paint Technol., 47, (608), 81, 1975
[24] DuPont De Nemours, WO 2007146388, 2007
[25] DuPont De Nemours, WO 2005023941, 2005
[26] Dow, WO 2009094235, 2009
[27] Schuetz, A.; Kaiser, W.-D., Farbe + Lack, 110(4), 22-24, 26-27, 2004
[28] Harris, S., PPCJ, Polymers Paint Colour Journal, 196(4497), 14, 2006
[29] Nguyen, T; Martin, J.W., Journal of Coating Technology Research, 1(2), 4, 82-92, 2004
[30] Dow, WO 2009058715, 2009
[31] Dow, WO 2011087486, 2011
[32] Dow, WO 2011068645, 2011
[33] Nitto Electric Industry, Jap. Pat. 57.042.760, 1980
[34] Yuka Shell Epoxy, Jap. Pat. 58.118.818, 1982
[35] Shell Chemicals, Epikote Resin Powder Coatings. Manual EK 2.10, 1989, p. 12
[36] Sumitomo Durez KK, Jap. Pat. 59.226.065, 1983
[37] Resolution Performance Products, US 20040147690 2004
[38] PPG, WO 2007002115, 2006
[39] Shell Chemicals, Epikote Powder Coatings – General Principles, Bulletin EK 2.3, p. 9, 1992
[40] Chemische Werke Hüls AG, EP 0.044.030, 1980
[41] Mitsubishi Electric Corp., Jap. Pat. 57.018.765, 1980
[42] Minnesota Mining and Manufacturing Company, US Pat. 3.876.606, 1975
[43] Sumitomo Bakelite Co., JP 2008248100, 2008
[44] Marx, E., et al., Intern. Waterb., High Solids and Powder Coat. Symp. New Orleans 2000
[45] Guo, H., IP.com Journal, 9(9A), 3-4, 2009
[46] Dow, WO 2008147641, 2008
[47] Krüger, A., FARBE&LACK 105, (9), 106 (1999)
[48] Shell Chemicals, Epikote Powder Coatings – General Principles, Bulletin EK 2.3., p. 10, 1992
[49] Wu, X., Reguxing Shuzhi, 21(4), 29-33, 2006
[50] DSM, WO 2008031589, 2008
[51] Sabic Innovative Plastics, WO 2009012391, 2009
[52] Hoechst AG, DE Pat. 1.913.923, 1969
[53] Misev, T., XIX FATIPEC Congress, Proceedings, Vol. III., Aachen, 19–23 Sept., 1988, p. 99
[54] Patton T.C., Off. Digest, 32, (430), 1544, 1960
[55] Lynas-Gray, J.I., Paint Technology, 11, (124), 129, 1946
[56] Lynas-Gray, J.I., Paint Technology, 12, (133), 7, 1947
[57] Burrel, H., Paint Oil and Chem. Rev., 110, 19, 1947
[58] Wangsness, I.L., Jerabek, R.D, Murphin A.T., and Naponen, G.E., Off. Digest, 26, 1062, 1954
[59] Seaborne, L.R., Paint Technology, 19, (208), 6, 1955
[60] Wiederhorn, N.M., Am. Paint J., 41, (2), 106, 1956
[61] Kraft, W.M., Off. Digest, 29, 780, 1957
[62] Vaughan, C.L.P. and Schmitt, F.E., Jr., Off. Digest, 30, (405), 1131, 1958
[63] Glaser, D.W., Off. Digest, 33, 642, 1961
[64] Patton T.C., Alkyd Resins Technology, Interscience Publishers., John Wiley, New York 1962
[65] Misev, T., Ban, N. and Bravar., M., Hemijska Industrija, 33, (5), 177, 1979
[66] Misev, T., Hemijska Industrija, 34, (6), 164, 1980
[67] Misev, T., Ban, N. and Bravar, M., Hemijska Industrija, 34, (7), 179, 1980
[68] Mleziva, J., in Polyestery, SNTL, Praha 1964
[69] Tysall, L.A., in Calculation Technique in the Formulation Alkyds and Related Resins, Paint Research
Association, May 1982 ed.
[70] Misev, T., J. Coat. Technol. 61, (772), 49, 1989
[71] Cargil Inc., US Pat. 4.275.189, 1980
[72] Kodak Ltd., WP 8.300.328, 1981
[73] Hüls AG, EP 317 741, 1987
[74] Mitsui Toatsu Chem. Inc., EP 314 447, 1987
[75] Chemische Werke Hüls AG, DE Pat. 3.004.876, 1980
[76] Chemische Werke Hüls AG, DE Pat. 3.322.719, 1983
[77] Eastman Kodak Co., EP 0.070.118, 1981
[78] Eastman Kodak Co., US Pat. 4.352.924, 1981
[79] Hexion Specialty Chemicals, WO 2009109313, 2009
[80] Bodnar, E., Product Finishing, August 1988, p.22
[81] UCB, BE Pat. 0.841.213, 1975
[82] UCB, BE Pat. 0.841.681, 1975
[83] Unilever N.V, US Pat. 4.147.737, 1979
[84] Goodyear Tire & Rubber Co., US Pat. 4.379.895, 1982
[85] DSM Resins BV, NL 8.204.206, 1982
[86] DSM Resins BV, BE. Pat.0.898.100, 1982
[87] DuPont, US Pat. 4.242.253, 1979
[88] Dainipon Ink Chem., Jap. Pat. 58.034.869, 1981
[89] Hitachi Chemical, Jap. Pat. 57.055.920, 1980
[90] Nippon Ester, Jap. Pat.59.011.375, 1982
[91] Nippon Ester, Jap. Pat. 57.135.829, 1981
[92] Nippon Ester, Jap. Pat. 57.126.822, 1981
[93] DSM Resins BV, BE Pat. 898.099, 1982
[94] DSM Resins BV, NL Pat. 8.204.206, 1982
[95] AMOCO-co-researchers, Proc. 25th Intern. Waterborne, High Solids and Powder Coatings Symp., New
Orleans, 18–20 Feb. 1998
[96] Johnson, L.K., and Sade, W.T., J. Coat. Technol., 65, (826), 19 (Nov. 1983)
[97] a) Noordover, B. A. J.; van Staalduinen, V. G.; Duchateau, R.; Koning, C. E.; van Benthem, R. A. T. M.; Mak,
M.; Heise, A.; Frissen, A. E.; van Haveren, J., Biomacromolecules, 7(12), 3406-3416, 2006
b) van Haveren, J.; Oostveen, E. A.; Micciche, F.; Noordover, B. A. J.; Koning, C. E.; van Benthem, R. A. T. M.;
Frissen, A. E.; Weijnen, J. G. J., Journal of Coatings Technology and Research, 4(2), 177-186, 2007
[98] Noordover, B. A. J.; Heise, A.; Malanowksi, P.; Senatore, D.; Mak, M.; Molhoek, L.; Duchateau, R.; Koning, C.
E.; van Benthem, R. A. T. M., Progress in Organic Coatings, 65(2), 187-196, 2009
[99] Battelle Memorial Institute, WO 2006102279, 2006
[100] Minnesota Mining and Manufacturing Company, US Pat. 3.340.212, 1961
[101] Huneke von H., Metalloberfläche, 24, 9, 315, 1970
[102] Unilever N.V., DE Pat. 2.163.962, 1971
[103] Hitachi Chemical, Jap. Pat. 57055.958, 1980
[104] Hitachi Chemical, Jap. Pat. 57.055.923, 1980
[105] Takeda Chemical Ind., Jap. Pat. 59.230.069, 1983
[106] Scado BV, US Pat. 3.624.232, 1970
[107] UCB SA, DE Pat. 2.352467, 1972
[108] SCM Corporation, EP 0.021.770, 1979 and US Pat. 4.271.277, 1979
[109] DuPont De Nemours, US 20070231580, 2007
[110] Pappas, S.P., Kunz, V.D. and Pappas, B.C., J. Coat. Technol. 63, (796), 39 (1991)
[111] BASF, WO 2010057922, 2010
[112] PPG, WO 2005033170, 2005
[113] Gedan-Smolka, M., Çetin, S., Lehmann, D., and Komber, H., FARBE&LACK, 103, (11), 48 (1997)
[114] Bergmans, A., Polym. Paint Colour J. (PPCJ), 191, (4445), 16 (Oct. 2001)
[115] a) Bayards, R.A., Groen, H., Koldijk, F., and Beukers, D., Proc. 7th Nuremberg Congres, April 2003
b) DSM Resins BV, Powder Coating Resins Brochures 1993, 1999, 2000
[116] Barletta, M.; Lusvarghi, L.; Mantini, F. P.; Rubino, G., Surface and Coatings Technology, 201(16-17),
7479-7504, 2007
[117] Ehsani, M.; Yousefi, A. A.; Yeganeh, S. S., e-Polymers, http://www.e-polymers.org/journal/papers/
mehsani_201209.pdf, 2009
[118] DSM Resins BV, BE Pat. 0.898.100, 1982
[119] Thames, S.F., Panjnani, K.G., Pace, S.D., and Blanton, M.D., European Coatings Journal (1994) 10, 705;
or same authors + Cumberland, B.R., J. Coat. Technol., 67, (841), 39(1995)
[120] Miller, R.S., and Joshi, V., Proc. 21st Intern. Waterborne, High Solids and Powder Coat. Symp. New Orleans,
9–11 Feb. 1994
[121] Frischinger, I., Cotting, J., Finter, J., Gottis, P. and Poget, C., Proceedings.4th Nuremberg Congress 1997
[122] BASF Coatings, WO 2005120724, 2005
[123] Metallgesellschaft AG, DE Pat. 1.905.825, 1969
[124] Unilever N.V., GB Pat. Appl. 61107-70, 1970
[125] DSM Resins BV, EP 0.107.888, 1982
[126] Hoppe, M., J. Coat. Technol., 60, (763), 58, 1988
[127] Merfeld, G.; Mordhorst, S.; Koeniger, R.; Acar, A. E.; Molaison, C.; Suriano, J.; Irwin, P.; Warner, R. S.; Gray, K.;
Smith, M.; Kovaleski, K.; Garrett, G.; Finley, S.; M., D.; Spicer, M.; Naguy, T., JCT Research,2(8), 661-668, 2005
[128] Maetens, D., Loutz, J., and Merck, Y., Proc. 13th Intern. PRA Conf. on Powd.Coat. Brussels, Nov. 1993
[129] Maetens, D., Progress in Organic Coatings, 58(2-3), 172-179, 2007
[130] Montserrat, S.; Calventus, Y.; Hutchinson, J. M., Progress in Organic Coatings, 55(1), 35-42, 2006
[131] Merck, Y., Maetens, D., Moens, L., and Buysens, K., European Coatings J. (ECJ) 12 (1999) p. 18
[132] UCB Chemicals WO 97/20895
[133] Malshe, V.; Hemantkumar, T.i R., Asia Pacific Coatings Journal, 17(4, Suppl.), 15-17, 2004
[134] Hoppe, M., J. Coat. Technol., 60, (763), 53–57, 1988
[135] Zhou, L., Thames, S.F., Smith, O.W., Smith, C.J., Boon, W.H., and Gwyn, D., Paint & Coatings Industry,
Vol. XVIII, (2), 52 (2002)
[136] Evonik Degussa GmbH, WO 2008068068, 2008
[137] DSM Resins BV, NL Pat. 8.204.206, 1982
[138] Gottis, P.G. and Cotting, J.A., XXIII. FATIPEC Congress book Vol. B, p. 216, Brussels, 1966
[139] Buysens, K., European Coatings Journal, 6, 18-22, 2005
[140] EMS-Chemie, “Primid” Technical Supplement 7.4 (1996)
[141] UCB, WO 2004083326, 2004
[142] UCB, WO 2004083325, 2004
[143] Nippon Paint Co., JP 2004196952, 2004
[144] Rohm and Haas Company, EP 1852453, 2007
[145] DSM, EP 1873183, 2008
[146] a) Cuijpers, J.; Buijsen, P.; Posthuma, C.; Verhoef, H. J.; Beukers, D.; Paauwe, J., European Coatings Journal,
(6), 38-41, 2009
b) DSM, WO 2010094811, 2010
[147] a) Hexion Specialty Chemicals, WO 2010069531, 2010
b) Capra, A.; Panero, I.; Lorenzo, D.D., Ghisolfi, S., European Coatings Show, Proceedings, 108, 2011
[148] Moens, L.; Bauters, E.; van Muylder, M., European Coatings Journal, (6), 25-28, 2010
[149] DSM, US 20090186973, 2009
[150] Kansai Paint Co., WO 2006038491, 2006
[151] De Lange, P.G., XX. FATIPEC Congress, Nice, p. 395, 1990
[152] DuPont De Nemours Co., US Pat. 4.402.983, 1980
[153] Bayer AG, EP 0.024.680, 1979
[154] Walz, G., and Kraft, K., Proc. 4th Intern. Conf. in Org. Coat. Sci. & Technol., Athens 1978, p. 56
[155] Basf, WO 2006089940, 2006
[156] Bayer Materialscience, EP 2159238, 2010
[157] Williams, F., Armengol, J., Grau, E., Monleon, J., and Schultz, E., Proc. 27th Int. Waterborne, High Solids and
Powder Coatings Symp. New Orleans, Feb. 2000
[158] Blank, W., XXVI FATIPEC Congress “Quo Vadis – Coatings”, Dresden 2002 in Macromol. Symposia 187,
p. 261, Ed. Wiley-VCH, Sept. 2002
[159] McLafferty, J.J., Figlioti, P.A., and Camilleri, L.T., J. Coat. Technol., 58, (733), 23, 1986
[160] Bronk, J.M., Proc. PRA Symp. “Powder Coat. – What’s Next”, Birmingham, Mar. 1999
[161] Evonik Degussa GmbH, WO 2008068073, 2008
[162] Wu, B., Padaki, S., and Maetens, D., Proc. 26th Int. Waterborne, High Solids & Powder Coatings Symp.,
New Orleans, 10–12 Feb. 1999
[163] Ratliff, K.; Eastman, J.; Faecke, T., Proceedings of the International Waterborne, High-Solids, and Powder
Coatings Symposium, 33rd 133-144, 2006
[164] Bayer AG, DE Pat. 3.232.463, 1982
[165] Freudenberg, U., Meier-Westhues, U., and Laas, H., European Coatings Journal 9/1997, 804
[166] Wenning, A., Weiss, J., and Grenda, W., Congress Papers Powder Coatings Europe 98 (PCE 98), Amsterdam,
Jan. 1998, Paper 10, p. 147
[167] Freudenberg, U., Thometzek, P., and Meier-Westhues, U., Proc. 26th Intern. Waterborne, High Solids & Powder
Coatings Symp., New Orleans, 10–12 Feb. 1999; or same authors: 5th Nuremberg Congr. 1999;
or FARBE&LACK, 105, (9), 46, 1999
[168] R.M. Gallas, Acrylic Modified Polyester System for Powder Coatings, Johnson Wax Brochure, 1988
[169] Horn, M.B., Acrylic Resins, Reinhold Publishing Corp., New York, 1960, p.15
[170] Adapted from Luskin, L.S., Myers, R.J., in Encyclopedia of Polymer Science and Technology,
Ed. N.M. Bikales, VolumeI, Interscience Publishers, New York, 1964, p. 299
[171] Fox, T.G., Bull. Am. Phys. Soc., 1, 3, 123, 1956
[172] The Glidden Company, EP 0.256.369, 1986
[173] DuPont De Nemours Co., EP 0.045.040, 1980
[174] Ford Motor Company, US Pat. 3.880.946, 1975
[175] Bayer AG, US Pat. 3.836.604, 1974
[176] BASF Farben & Faser, DE Pat. 3.310.545, 1981
[177] Deutsche Gold und Silber Scheideanstalt, US Pat. 3.867.347, 1975
[178] Yousuf, M.K., Modern Paints and Coatings, June 1989, p.48
[179] Dainippon Ink & Chemicals, EP 0.038.635, 1980
[180] Nippon Paint, Jap. Pat.115516, 1986
[181] R.M. Gallas, Acrylic Modified Polyester System for Powder Coatings, Internal Publication,
S.C. Johnson & Son Inc., 1988
[182] Yousuf, M.K., and Pfeffer, W.G., Dry-on-Dry Powder Coating Systems, Internal Publication,
S.C. Jonson & Son Inc., July, 1988
[183] Dumain, E., Coatings World, Vol. 1, no. 2, Oct. 1998, Part 1, p. 27
[184] Iwamura, G., Proc. 5th Nuremberg Congress 1999, Paper 20
[185] Kerssen, G.W., and Verlaak, J., XXIII FATIPEC Congress book, Vol. B. p. 419, Brussels, June 1996
[186] Miller, R. and Kerr, J., Powder Coating ’92, Conf. Proc. p. 79, (1992)
[187] N.N., FARBE&LACK, BASF L+F erfolgreich mit Pulverprimern 102, (8), (1996) p. 16
[188] Green, D., Paint & Coating Industry, Sept. 1995, p. 49
[189] Linak, E., Kishi, A., Yang, V., Thermosetting Powder Coatings, SRI CONSULTING, 2008
[190] Rohm and Haas Company, EP 2098575, 2009
[191] Cole, G.E., Industrial Paint & Powder, 69, (12), 24 (1993)
[192] Bailey, J.M., Industrial Paint & Powder, 70, (7), 12 (1994)
[193] Koop, J.M., Powder Coating, 5, (4), 52 (1994)
[194] Clark, P.D., Proc. Intern. Body Engin. Conf. IBEC ’94, 12, 44 (1994)
[195] Schmidt, H., 13th Intern. PRA Conf., paper 13, Brussels, Nov. 1993
[196] Bayer Materialscience AG, EP 1491567, 2004
[197] Schmidt, H. and Fink, D., Surface Coatings International, 2, 66 (1966)
[198] Kinza, W., JOT Conf. EPS ’97, Munich, 30–31 Jan. 1997, p. 131
[199] Dainippon Ink and Chemicals, WO 2005087881, 2005
[200] DuPont de Nemours, US 20080299323, 2008
[201] Gribble, P.R., Finishing ’93, Conf. Proc., Cincinnati, Ohio, 25–28 Oct. 1993
[202] Ortiz, C. and Winters, L., Proc. 1st Intern. Conf. on Car-Body Powder Coatings, Berlin, 22–23 June 1998
[203] Dornitz, R.A., Proc. 1st Intern. Conf. Car-Body Powder Coatings, Berlin, 1998
[204] Pearson, R., Proc. 1st Intern. Conf. Car-Body Powder Coatings, Berlin 1998
[205] Attinoto, R.A., Proc. 1st Intern. Conf. Car-Body Powder Coatings, Berlin 1998
[206] Gribble, P.R., Proc. 1st Intern. Conf. Car-Body Powder Coatings, Berlin 1998
[207] Higgins, R.J., Powder Coatings – European Supplement of PPCJ and Product Finishing, Jan. 1998, p. 9
[208] Kreis, W., Proc. 1st Intern. Conf. Car-Body Powder Coatings, Berlin, June 1998; and/or PPCJ, 188, (4411),
12 Dec. 1998)
[209] BASF, WO 2007082656, 2007
[210] Lendl, T., JOT, Journal fuer Oberflaechentechnik, 44(5), 40-42, 2004
[211] Wimmer, W., Congress Papers PCE ’98, Amsterdam, Jan. 1998, S.27, p. 433
[212] Yanagida, K., Kumata, M. and Yamamoto, M., J. Coat. Technol. 68, (859), 47, (1996)
[213] Rekowsky, V., Congress Papers PCE 2002, Nuremberg, Jan. 2002, p. 137
[214] DSM, WO 2010108963, 2010
[215] Williams, H., Plastic Inst. Trans., 24, 37, 1956
[216] Bayer AG, DE Pat. 1.105.610, 1961
[217] Feuer, S.S., Bockstahler, T.E., Brown, C.A., Rosenthal, I., Ind. Eng. Chem., 46, 1643, 1954
[218] Hayes, B.T., Read, W.J., Vaughan, V.H., Chem. & Ind., 1957, 1165
[219] Mleziva, J., Vladyka, J., FARBE&LACK, 68, 144, 1962
[220] DSM Resins BV, EP 0.188.846, 1984
[221] DSM Resins BV, EP 0.106.399, 1983
[222] Morton Thiokol, EP 309 088, 1987
[223] Stamicarbon BV, US Pat. 4.228.113, 1980
[224] Stamicarbon BV, US Pat. 4.287.310, 1980
[225] a) DSM, WO 2010136315, 2010
b) Schutte, M., European Coatings Congress, Proceedings, 112, 2011
[226] DSM, WO 2010052290, WO 2010052291, WO 2010052293, WO 2010052294, WO 2010052295, WO
2010052296, 2010; WO 2011138431, WO 2011138432, 2011
[227] Dohnt, W., Congress Papers PCE 2002, Nuremberg, Jan. 2002, p. 67
[228] Subramanian, R. and Sullivan, C., Congress Papers PCE 2002, Nuremberg, Jan. 2002, p. 231
[229] Boneza-Tomaszewski, Z.; Penczek, P.; Bankowska, A., FATIPEC Congress, 27th (Vol. 1), 87-95, 2004
[230] Boneza-Tomaszewski, Z.; Bankowska, A.; Penczek, P., Advances in Coatings Technology, International
Conference, 6th, Warsaw, Poland, Nov. 23-26, 2004
[231] Witte, F., De Jong, E.S., and Misev, T.A., RadTech Report 10, 13, Sep./Oct. 1996
[232] Udding-Louwrier, S., De Jong, E.S., and Bayards, R.A., Proc. RadTech ’98 Chicago (USA), 19–22 April 1998,
p. 106
[233] Schwarb, R.; Knoblauch, M.; Cox, J., CoatingsTech, 7(7), 44-49, 2010
[234] DSM Resins, WO 93/25596 (1993)
[235] a) BASF, EPA 650978, 650979 (1994) and 678562 (1995);
b) Bayer, EPA 350730 (1990)
[236] Maetens, D., Proc. RadTech ‘98 – Chicago (USA), April 19-22, 1998, p. 170
[237] Fink, D. and Brindoepke, G., a) Paper 29, 3rd Nuremberg Congress, Mar. 1995;
b) European Coatings Journal 1995, p. 606
[238] Hoechst, EPA 585742 (1994)
[239] Wenning, A., XXVI FATIPEC Congres “Quo Vadis-Coatings”, Dresden 2002, in Macromolec. Symposia 187,
p. 597, Ed. Wiley-VCH, Sept. 2002
[240] Williams, F.; Armengol, J. M..; Grau, E.; Chambat, C.; Laurens, C., RadTech Europe 05, Oct. 18-20, 1, 533-540, 2005
[241] Hult, A., Johannson, M., Jansson, A. and Malmström, E., Proc. RadTech Eur. ’99 Berlin, 8 Nov. 1999, p. 634
[242] Loewenhielm, P.; Nystroem, D.; Johansson, M.; Hult, A., Progress in Organic Coatings, 54(4), 269-275, 2005
[243] Wittig, M., and Gohmann, T., Polym. Paint Col. J. (PPCJ), 184, (4343), 34, 1994
[244] Ciba, EPA 667381 (1994)
[245] Finter, J., Frischinger, I., Haug, Th. and Marton,R., Proc. 4th Nuremberg Congress April 1997
[246] DSM Resins, EPA 636669 (1995)
[247] Blatter, K., Congress Papers PCE ’98, Amsterdam, Jan. 1998, p. 91
[248] Bayer Materialscience, EP 1538186, 2005
[249] UCB Chemicals, EPA 739922 (1995)
[250] Luo, Y., CN 1528846, 2004
[251] Spyrou, E.; Wenning, A.; King, C. L, UV & EB Technology Expo & Conference, Charlotte, NC, United States,
May 2-5, 394-400, 2004
[252] Bayards, R.A., Antonisse, M.M.G., Udding-Louwrier, S., and Meij, E., Proc. 6th Nuremberg Congress, April 2001] [253] Kersten, J., a) Congress Papers PCE 2002, Nuremberg, Jan. 2002, p. 257
b) FARBE&LACK, 108, (2), 86 (Feb. 2002)
[254] Paulus, W., Binder, H., Hennig, I., Rieger, J., Schrof, W., and Schwalm, R., FARBE&LACK, 107, (10), 46, 2001
[255] a) Spyrou, E., RadTech Europe 05, Oct. 18-20, 2, 269-276, 2005
b) Degussa AG, WO, 2007045609, 2007
[256] DSM, WO 2006082080, 2006
[257] Williams, F.; Armengol, J. M.; Grau, E.; Decomble, V.; Chambat, C., RadTech Europe 07, Nov. 13-15, 2007
[258] Malmström, E., and Hult, A., Proc. 26th Intern. Waterborne High Solids and Powder CoatingsSymp. New
Orleans, Febr. 1999
[259] Van Benthem, R.A.T.M., a) Proc. 25th Int. Conf. in Org. Coat., Athens, 1999, p.345;
b) Verfkroniek 73, p. 15 (April 2000)
[260] Kim, H.J., J. Pol. Sci. Polym. Chem., 36, (11), 1685, 1998
[261] Cheng, X.-E.; Huang, Z.; Liu, J.; Shi, W., Progress in Organic Coatings, 59(4), 284-290, 2007
[262] Biller, K.M. and McFadden, B., Industr. Paint & Powder, 1996, nr. 27, p. 22–25
[263] Witte, F.M., European Coatings Journal, 3/96, p. 115
[264] a) Misev, L., Kunz, M., Strobel, R., Proc. RadTech Europe ’95, Maastricht, p. 93
b) Witte, F., Kieft, G., et al. Proc. RadTech Europe ’95, Maastricht, p. 437
[265] Laver, H., and Chamberlin, D., Proc. PRA Powder Coatings – What’s Next ? Birmingham. U.K., Mar. 10,
1999, Paper 8
[266] Margraf, R., Laver, H., Bender, J., Lehmann, K. and Schmid, O., Proc. RadTech Europe ’99, Berlin,
8 Nov. 1999, p. 615
[267] Rawlins, J. W., Powder Coating, Aug. 2000, 37–41
[268] Tigerwerk Lack- und Farbenfabrik, WO 2005051552, 2005
[269] Udding-Louwrier, S., Bayards, R., and Feima, N., Proc. RadTech Europe ’99, Berlin, 8 Nov. 1999, p. 607
[270] Skinner, D., Proc. RadTech Europe ’99, Berlin, 8 Nov. 1999, p. 599
[271] Castell, P.; Wouters, M.; Fischer, H.; de With, G., Journal of Coatings Technology and Research, 4(4),
411-423, 2007
[272] Binda, P., a) Powder Coatings ’99 Symp., Birmingham, Mar. 10, 1999; b) Congress Papers PCE 2000,
Amsterdam, Jan. 2000, p. 377
[273] Udding-Louwrier, S., Bayards, R. and De Jong, E.S., Proc. 26th Int. Waterborne High Solids and Powder
Coatings Symp., New Orleans, Feb. 1999, p. 420
[274] Cytec Surface Specialties, WO 2006037493, 2006
[275] Misev, L., Schmid, O., Udding-Louwrier, S., De Jong, E.S. and Bayards, R., J. Coat. Technol., 71, (891),
37 (April 1999)
[276] Buysens, K., a) Rad Tech Report, 13, (4), 18 (July/August 1999);
b) Proc. RadTech Europe ’99, Berlin, Nov. 8th, 1999, p. 622
[277] Drummond, C.K., Mihalic, S., and Guskov, S., Congress Papers PCE 2000, Amsterdam, Jan. 2000, p. 125
[278] Knoblauch, M., Asia Pacific Coatings Journal, 19(2), 12-15, 2006
[279] Te Walvaart, C., Jahn, R., Lahaye, J., Laver, H. and Schmid, O., Congress Papers PCE 2000, Amsterdam,
Jan. 2000, p. 309
[280] Godan, A., Surface Coatings International, 91(1), 31-33, 2008
[281] Souris, Y., Buysens, K., Congr. Papers PCE 2002, Nuremberg, Jan 2002, p. 267
[282] Rohm and Haas, US 20040067304, 2004
[283] DuPont De Nemours, US 20050276917, 2005
[284] DuPont De Nemours, WO 2006069149, 2006
[285] DuPont De Nemours, WO 2007059133, 2007
[286] Wouters, M.; Muixi, P. C., Contact Angle, Wettability and Adhesion, 5, 207-227, 2008
[287] Blatter, K., Strid, M., Thiele, O., and Zimmermann, F., Congr. Papers PCE 2000, Amsterdam, Jan. 2000, p. 115
[288] Mitchell, S., Congr. Papers PCE 2002, Nuremberg, Jan. 2002, p. 73
[289] Römer, J., Congress Papers PCE 2002, Nuremberg, Jan. 2002, p. 113
[290] DuPont Powder Coatings AB, WO 97/05963
[291] Triab/Triline AB, WO 97/05964
[292] Hammerton, D., International Wood Composite Materials Symposium Proceedings, 39th 233-248, 2005
[293] Santandrea, S., RadTech Europe 05, Oct. 18-20, 1, 45-50, 2005
[294] Karlsson, L., Congress Papers PCE 2000, Amsterdam, Jan. 2000, p. 47
[295] a) Buysens, K., Congress Papers PCE 2000, Amsterdam, Jan. 2000, p. 253
b) Zune, C. and Buysens, K., European Coatings Journal 05/00 (2000), p. 18
[296] Bär, K., Sedlmeyr, M., Congr. Papers PCE 98, Amsterdam, Jan. 1998, p. 71and Polym. Paint Col.J. (PPCJ),
April 1998, p. 18
[297] Bär, K., and Sedlmeyr, M., Congr. Papers PCE 2000, Amsterdam 1998, p. 321
[298] DuPont, WO 99/41323
[299] DuPont De Nemours, WO 2004058417 2004
[300] DuPont De Nemours, WO 2005042648, 2005
[301] DuPont De Nemours, WO 2005078030, 2005
[302] De Lange, P.G., J. Coat. Technol. 56, (717), 23 (Oct. 1984) and in Proc. 6th Int. Conf. in Org. Coat. Sci. & Technol.,
Athens, 1980 p. 366
[303] DuPont de Nemours, US 20050255238, 2005
[304] DuPont Powd. Coat., Techn. Brochure “Ray-Tec” PowderCoating, by F.Zimmermann
[305] Witucki, G.L., Powder Coating, 8, (8), 19 (Nov. 1997)
[306] Witucki, G.L., Congress Papers PCE 2000, Amsterdam, Jan. 2000, p. 247
[307] Groggins, P.H., Unit Processes in Organic Synthesis. 3rd Ed., McGraw-Hill, New York, 1947, p. 843
[308] DuPont De Nemours, WO 2007126640, 2007
[309] Wacker-Chemie, “Silres”, Techn. Brochure, Munich, 1998
[310] Dow Corning, “Silicone Additives”, Techn. Brochure, 1991
[311] DuPont De Nemours, WO 2004076572, 2004
[312] Popa, P., Be A., Storey, R. and Baugh, D., Proc. 26th Int. Waterborne, High Solids and Powder Coatings
Symp., New Orleans, 10–12 Feb. 1999
[313] Glidden Research Team, Proc. 25th Int. Waterborne, High Solids and Powder Coatings Symp. New
Orleans, 18–20 Feb. 1998
[314] Rohm and Haas, EP 1403350, 2004
[315] Rawlins, J., Thames, S., Proc. 26th Int. Waterborne, High Solids and Powder Coatings Symp. New Orleans,10–12 Feb. 1999
[316] Harris, S., Focus on Powder Coatings, Sept. 1999
[317] Wacker Chemical Corporation, WO 2005063857, 2005