79 Amino Resins 79.1 Introduction 79-1 History 79.2. Amino Resin Synthesis and Background. 79-2 ‘Ure-Forialdehyde Resins» Metane-Formaldchyde Resins 79.3. Coatings 793 in Formation — Crow Linking » Catalyse» Automotive ostings — Clear Costs 79.4. Other Amino Resins 79.6 George D. Vaughn* 795. Future Trends 79.6 Strface Specaies Melamine References 796 79.1 Introduction Amino, or aminoplast, resins are an important class of cross-linkers for industrial coatings.* Amino, resins are usually water-white, viscous materials that may contain added solvent to reduce viscosity for ease of handling. Most amino resins do not consist of a single chemical entity but are mixtures of monomeric and oligomeric molecules, Properties of the resin are dictated by the amount of each ‘molecule type present in the mixture. These resins are used in thermoset and ambient cure systems, Figure 79.1 shows various types of amino resin precursors. The amino resins are made by reacting these precursors with formaldehyde (CH,=O) and then with primary alcohols (ROH). The resulting ether is >NCHLOR. Of these, the melamine-formaldehyde (MF) and urea-formaldehyde (UF) resins are the ‘most widely used commercially. ‘This chapter will focus on the chemistries of the melamine and urea molecules. A short summary of the other resin systems is included at the end of the chapter. 79.1.1 History ‘The first amino resins used in coatings were made from the reaction of utea or melamine with form- aldehyde followed by butanol (ether n- oF iso-). They were essentially polymeric and therefore were offered at 50 to 60% solids in butanol/xylene mixtures. These have been commercially available for neatly 70 years.> ‘The higher solids (80 to 100%) amino resi With either methanol only or mixtures of methanol and other primary alcohols. These higher solids resins are now more important industrially because of the many regulations put in place, by government ‘mandates, to reduce the level of volatile organic compounds (VOCs)® emitted by paints. hhave been available for about 40 years. These are made 7 Garrent afillaion: Cytec Surface Specialties. 79-179.2. Coatings Technology Handbook, Third Edition See \y AA N CoH, aa a — v no oT Sno ws yh FIGURE 79.1. Amino resin precursors. H:NCONH,+CH,0 = —==—=——H.NCONHCH,OH — H,NCONHCH,OH+CH,O === ——HOCH.NHCONHCH.OH HOCH.NHCONHCH.OH+AOH = ==—=—=—=—_HOCH,NHCONHCH_OR + H.0 HOCH,NHCONHCH,OR+AOH = ==——=——ROCH,NHCONHCH,OR + H,0 FIGURE 79.2 Ures-ormaldehyde resin synthesis. 79.2 Amino Resin Synthesis and Background 79.2.1 Urea-Formaldehyde Resins ‘The equations shown in Figure 79.2 represent the stepwise synthesis of UF resins, All four reactions are equilibrium driven, The first two can be catalyzed by acid or base. The second two are acid cat ‘The extent of reaction is dependent upon the raw material charges and catalyst ratios and, additions for the third and forth reactions, the extent the water is removed from the reaction. 79.2.2 Melamine-Formaldehyde Resins ‘The reactions used to generate MF resins are analogous to those illustrated above. The notable exception, is that only two of the four available hydrogens on the urea molecule are easily substituted, whereas all, six hydrogens on the melamine molecule are available for substitution. Figure 79.3 shows all the possible bonding combinations for a MF resin. Present are imino (>NH), methylol (>NCH,OH), alkoxymethyl (>NCH,OR), acetal (>NCH,OCH,OR), methylene bridge (©NCH,.), and methylene ether bridge (>NCH,-O-CH,-) groups. The last two bonding modes con- tribute to oligomeric species. Conventional ME resins consist of monomers and oligomers of melaraine with a mixture of the possible functional groups. The amount of oligomers formed depends on the reaction conditions. 79.2.2.1 ‘Types of High-Solids Melamine-Formaldehyde Resins ‘This section will include resins with solids at 280%. One unique class of ME resins (partially acrylated) can participate in a dual-cure, ultraviolet (UV)/thermal process.”Amino Resins 79.3 poco, ipuen Wt NTO Yoo ‘A N “~™ Hoc, “oH. — FIGURE 79.3. Functional groups in typical MEF resins, 79.22.11 Highly Methylated MF Resins Formulations made with these resins, composed of methoxy ether groups only, cure faster than either those composed of methoxy-alkoxy groups of other alkoxy groups only. They can cure at temperatures down to 60°C (140°P) Some wood coatings use ambient cure conditions. Specific acid catalysts are used. for cure (see Section 79.3.2), These resins can be used in waterborne (WB) coatings and normally have a longer shel-ife than WB formulations made with high imino-containing resins. 79.2.2.1.2 Imino-Containing MF Resins! ‘These resins can be formulated to cure at temperatures of ~110°C (230°F) with no catalysts. When. catalysts are required, general acid catalysts are chosen (see Section 79.3.2). high level of self-conden- sation of the MF resin is responsible for the cure response. Because of the self-condensation, coatings made with these resins are harder and more brittle. These resins can be used in waterborne coatings. 79.22.13 Methoxy-Butoxy MF Resins! Formulations made with these resins show improved flow and leveling properties, and the cured systems demonstrate enhanced adhesion characteristics, and telegraphing resistance. Specific acid catalysts are used for cure (see Section 79.3.2) 79.3 Coatings Urea-formaldehyde resins are used in formulations for wood (board, kitchen cabinet), paper, and some coil and general industrial coatings. Most applications are for interior finishes, because UF coatings have sensitivity to hydrolysis and have poor exterior UV durability. Melamine-formaldehyde resins ate more widely used. Coatings made with MF resins have better chemical resistance and demonstrate better exterior durability. In addition to the coating applications listed for UF resins, MF resins can be used in container, automotive, and appliance coatings. Even though MF resins provide bette stain and water resistance in coatings versus UF resins, UF resins are used in wood coatings because they can be cured with litle of no heat. They also are generally less expensive than MF resins 79.3.1 Film Formation — Cross-Linking, Urea-formaldehyde and MF resins can undergo self-condensation, Figure 79.4 shows how MF resins can self-condense. In addition to water alcohols may also be evolved. Industrial baking finishes must possess flexibility exceeding that of self-condensed amino resins alone. Therefore, the coreactant must intto- duce flexibility. The common resin types employed are acrylics, alhyds, and polyesters. These resins must possess functionality that will react with the amino resins, The principal functionalities are primary and. secondary hydroxyl, carboxyl, carbamate,’ and amide. The reaction ofthe cross-linker withthe coreactant is called cocondensation (Figure 79.5). Both self-condensation and cocondensation reactions are catalyzed. by acid (see Section 79.3.2)794 Coatings Technology Handbook, Third Edition a m ‘. Ne X WSO Nowon ‘ /\ HoH. “H,OA A. cri0cr, f ee Hf yf ( ~ No,on a “Metyene Ether Line “Methylene Bridge" y termed water eeved I won, Nou,of Bi. cH,00H, \ f SO Senor q “™~ i on on cHock, cH,ocH, Hogs root, Son Noo wh 00s § ole Sno sot ~ Ho === yy i s ZN. cnyoc%, Yenoon, ono, Yowoor, on on FIGURE 79.5 Cure by transetherfcation of a ME resin and a hydroxyl functional coreactant 79.3.2 Catalysts Many researchers have studied the role thatthe catalyst plays in coating performance." The type of catalysis has been divided into two categories: general and specific. Weak acids, such as carboxylic and phosphoric, can be used to initiate the cure, under certain conditions. When the conditions are met, this, type of cure is called general acid catalyzed. When a strong acid, such as an organic sulfonic acid oF hydrochloric acid, is used, the cure is designated specific acd catalyzed. The cure temperature aso playsAmino Resins 795 1 major role. For MF resin systems, low temperature [<110°C (230°F)] cures ean only be achieved with specific acid catalysts. Examples will he given in later sections, Besides cure, the catalyst also influences the coating’s durability. Too much residual acid will accelerate the coating’s degradation, especially when exterior durability isa key property. Therefore, an optimum, level of aca, and its composition, must be determined experimentally in every case. 7932.1 Sulfonic Acid Catalysts Sulfonic acids are the most widely used catalyst type. There are aliphatic and aromatic sulfonie acids commercially available. Methanesulfonic acid should be a good choice for many applications, but early versions were likely high in sulfuric acid, This caused hydrolysis problems and yellowing of coatings in Which it was tested. p-Toluenesulfonic acid (p-TSA) is by far the most used acid because of cost, and because it can be easily purified (white crystalline solid). However, in the most demanding coating applications where long-term exterior exposure must be achieved, other acids are preferred. Two worth, ‘mentioning are mixed isomers of dodecylbenzenesulfonic acid (DDBSA) oF dinonylnaphthalenedisu- fonic acid (ONNDSA). Both are more hydrophobic than p-TSA, and thus, they contribute less to film failures caused by water absorption. 79,3.2.2. Paint Stability”: 793.2.2.1 Blocked Catalysts Blocked catalysts are used so that the catalyzed paint hasa reasonable shelf life. Amines are used extensively as blocking agents. At room temperatuce, in the paint, the amine is protonated by the acid catalyst, thus reducing the acidity of the system. When the paint is applied, the amine will volatilize, because the blocking reaction is an equilibrium process. This allows the cross-linking to begin. Oven cures are ‘normally used when blocked catalysts have been employed. The choice of the amine is critical to coating performance. Some amine/acid combinations are not usable because the amine/acid complex may not be soluble in the formulation. Depending on the cure temperature, certain amines may volatilize 100 quickly and can cause severe wrinkling inthe coating, This effect is due toa differential cure throughout the thickness of the coating, The concentration of the amine is lowest at the surface, soit cures faster than the interior, thus leading to a wrinkled appearance. Other amines, such as 2-amino-2-methyl- propanol (AMP) can cause auxiliary cross-linking," “These amine-blocked catalysts are ionic (charged species) in character. Another type is covalently blocked.” The advantage of ths type is that it can be used in electrostatic spray equipment where the paint should have low conductivity. However, covalently blocked catalysts require a cure temperature 110°C (230°F) to deblock. Certain amine blocked systems deblock at 63°C (149°F), 79.3.2.2.2 Primary Alcohols Note in Figuee 79.5, the by-product of the cross-linking is aleohol formation. A few percent ofa primary alcohol in the formulated paint can prolong the stability of the system, The added alcohol effect ean be explained by Le Chitelier’s principle (when an equilibrium system is perturbed, the equilibrium will always be displaced in such a way as to oppose the applied change). Methanol would be the best choice because it would volatilize the fastest, however, it is also flammable. Most formulators choose butanol, as the retarder. Added alcohol, along with a blocked catalyst, provides systems with the highest stability. It is worth noting that four times more n-butanol and more amine were required to stabilize a paint made with a 559% solids partially butylated MF resin than was required when a high-solids hexam ethoxymethylmelamine (HMMM) was used." 79.3.3 Automotive Coatings — Clear Coats ‘This topic could filla hook in itself. Melamine-formaldehyde resins impart characteristics such as superior distinctness-of-image (DO1), high gloss, and excellent mar resistance to automotive clear coats. There has been some partial replacement of MF resins with isocyanate cross-linkers, because coatings made with MF resins do not achieve the same level of acid-etch resistance.” Vaughn etal. reviewed acid-etch, ©2009 Tyr Ar Gap.79.6, Coatings Technology Handbook, Third Edition testing and described a straightforward accelerated test2! This accelerated testis supposed to mimic a coating exposed to acid rain. However, when mar resistance is the issue, coatings made with MF resins substantially outperform isocyanate systems. 79.4 Other Amino Resins Benzoguanamine resins impart flexibility and superior resistance to alkali and alkaline detergent resis tance versus MF resins, They also produce flexible coatings. They cost more than MF resins and have poorer UV durability, so they are used only when the above properties dictate their use. Benzoguanamine has been used significantly in can coatings. Gycoluril resin formulations require higher cure temperatures or higher catalyst levels but have excellent corrosion and humidity resistance. High cost limits thei use. ‘The acrylamide-type amino resins have had very limited use, Some applications include coil coatings for exterior use’ and self-cross-linkable coatings 79.5 Future Trends Amino resins will be with us for quite a while, because, as a class of cross-link, they are very economical and give excellent performance. Government regulations have already forced amino resin producers to ‘make high-solids resins. Now these resins can be supplied at lower free formaldehyde levels. A new low free formaldehyde MF resin* was introduced that can cure at 82°C (180°F) with as little as 0.59% acid. catalyst. ‘Some paint suppliers have developed new vehicle resins so that MF resins can continue to be used in high performance applications (again mainly cost driven). Carbamate-*>* and silane-containing” vehicle resins provide enhanced exterior durability benefits when cross-linked with MF resins, The desire to use amino resins in paint will keep formulators busy for years to come, References 1. EN. Jones and P.S. Ramachandran, Polym. Mater. Sci. & Eng., 77, 389 (1997). 2. D.E Erickson and T. P. Golden, Paint & Coat. Ind, August, 0 (1995). 3. P. Swargj, Ed, Surfuce Coatings: Science and Technology, 2d ed, Chichester: John Wiley, 1997, pp 861-865, G.D. Vaughn, Paint & Coat, nd, August, 38 (1998). J.0. Santer, Prog. nt Org. Coat. 12, 309 (1984). ‘Standard ‘Test Method for Volatile Content of Coatings,” ASTM D2369-04, J.J. Gummeson, J. Coat. Technol, June, 43 (1990). G_ D. Vaughn and J. D. Jacquin, Presented at the 77th Annual Meeting of the FSCT, Dallas, TX, October 20-22, 1999, 9. HP Higginbottom, G. R. Bowers, PE. Ferrell, and L.H. Hil, J. Coat. Technol, July, 49 (1999), 10. W.J. Blank, J. Coat. Technol, April, 26 (1982). LL. A. Berge, B. Kvaeven, and J. Ugelstad, Eur Polym. J, 6, 981 (1970). 12. L.Calbo, J. Coat. Technol, January, 75 (1980). ‘Standard Test Method for Package Stability of Paint, ASTM D1849.95. M4. Z.W. Wicks, Jr. and G. -F. Chen, J. Coat Technol, March, 39 (1978). 15, LW. Hill and Z. W. Wicks, Je, Prog. Org. Coat, 8, 161 (1980), 16. P.E. Ferrell. J. Gummeson, L. W. Hill, and L. J. Truesdell-Snider, Presented at the 73rd Annual ‘Meeting of the FSCT, St Louis, MO, October 9-11, 1995, 17, W.J. Blank, US. Patent 5 102 961, 1992. 18. J. C. Brogan and N. Albrecht, Proceedings of the Fourth International Paint C Brazil, 1995, p. 839,Amino Resins 79.7 1s. 20, 21 2, 23, 24, 25, 26. 27, J.W. Holubka, P. J Schmitz, and L. -F Xu, J. Coat, Technol, Febuary, 77 (2000). PJ. Schmitz, J. W. Holubka, and L. -F Xu, J. Coat. Technol, May, 39 (2000) G.D. Vaughn, J. B Downie, and P.E. Ferrell, Paint & Coat. Ind, August, 74 (2001), B, Pourdeyhimi, X. Wang, and E. Lee, Eur. Coat, J, 4, 100 (1999). J.L. Courter and E. A. Kamenetaky, Eur. Coat. [, 7-8, 24 (1999), (M.T. Keck, R. J. Lewarchik, and J.C. Allman, U.S. Patent 5 688 598, 1997. S. Swarup and M. A. Mayo, US, Patent 5 618 586, 1997. J.D. McGee and B. D. Bammel, Presented atthe Eighth Annual ESD Advance Conierence, Dettoit, MI, September 28-29, 1998, I. Hazan, Presented at the Eighth Annual ESD Advance Coatings Technology Conference, Detroit, ML, September 28-29, 1998, tings Technology ©2009 Tyr Ar Gap.