RMA crosslinkable compositions and RMA crosslinkable resins for easy to clean coatings

Abstract

A RMA crosslinkable coating composition, a method for the preparation thereof and a resulting coating having easy to clean properties useful in applications like graffiti resistant, sanitisable coatings and in flooring, the composition comprising RMA crosslinkable component with at least 2 RMA donor groups and at least 2 RMA acceptor groups characterized by having fatty components selected from the group of fatty acids, fatty alcohols, fatty amines, fatty thiols and dimeric fatty acid in an amount represented by an Oil Content OC between 0, preferably 4 and 40 wt %, and crosslinking density XLD of at least 1.4 a glass transition Tg of at least 290 in combination providing a easy to clean value ΔE less than 20. The invention also relates to RMA crosslinkable fatty resins for use in RMA crosslinkable top coatings.

Claims

1. A crosslinkable fatty resin comprising one or more fatty components selected from the group of fatty acids, fatty alcohols, fatty amines, fatty thiols and dimeric fatty acids and one or more reactive components A comprising at least 2 reactive groups which are acidic protons C—H in activated methylene or methine group, wherein fatty resin is modified with the one or more reactive components A having a structure according to formula 1: ##STR00002## wherein R is hydrogen, an alkyl, or an aryl, and Y and Y′ are identical or different substituent groups selected from alkyl, aralkyl, aryl, or alkoxy, or wherein the —C(═O)—Y and/or —C(═O)—Y′ is replaced by CN or aryl, wherein the crosslinkable fatty resin comprises predominantly malonate as the one or more reactive components A, predominantly meaning that more than 50% of the C—H reactive groups in the crosslinkable fatty resin are from malonate, wherein the crosslinkable fatty resin comprises the fatty components in an amount of 5 to 40 wt % relative to total weight of the crosslinkable fatty resin and comprises the one or more reactive components A in an amount between 10 and 40 wt % relative to total weight of the crosslinkable fatty resin, wherein the fatty components are chemically bonded to the crosslinkable fatty resin and the fatty components comprise fatty chains containing 10-40 carbons, wherein the fatty resin is further characterised by: a) a weight average molecular weight (Mw) between 2000 and 15000 dalton, b) a hydroxy value (OHV) between 20 and 300 mgKOH/gr, c) an acid value below 3 mg KOH/g, d) an equivalent weight (EQW) per reactive C—H group between 125 and 300 gr/mol, e) a functionality defined as number average number of reactive C—H per molecule between 4 and 12, and f) a glass transition temperature (Tg) between 220 and 320K as measured by DSC at heating rate of 10K/min.

2. The crosslinkable fatty resin of claim 1, wherein the one or more reactive components A are selected from the group consisting of malonate, acetoacetate, acetylacetone, acetoacetamide and propionylacetate.

3. The crosslinkable fatty resin of claim 1, wherein the one or more reactive components A in the crosslinkable fatty resins consist predominantly of malonate with acetoacetate or acetylacetone as the remainder reactive component A.

4. The crosslinkable fatty resin of claim 1, wherein more than 75% of the C—H reactive groups are from malonate.

5. The crosslinkable fatty resin of claim 1, having a hydroxy value OHV is between 50-300 mgKOH/gr.

6. The crosslinkable fatty resins of claim 1, wherein a) the molecular weight Mw (weight average) is between 2500-10000 Dalton, b) the hydroxy value OHV is between 50-300 mgKOH/gr, c) the acid value is below 2 mgKOH/gr, d) the equivalent weight EQW per C—H group is between 125-200 gr/mol, e) the functionality defined as number average number of C—H groups per molecule is between 4-12 and, f) the glass transition temperature Tg is from 230 to 300K as measured by DSC at heating rate of 10K/min.

7. The crosslinkable fatty resin of claim 1, comprising the fatty components in an amount of 10 to 40 wt % relative to total weight of the crosslinkable fatty resin.

8. The crosslinkable fatty resin of claim 1, comprising a polyol oligomer or polymer modified with fatty acids and the one or more reactive components A.

9. The crosslinkable fatty resin of claim 1, comprising a polyester, polyurethane, acrylic, epoxy or polyether polymer or mixtures thereof, modified with fatty acids and the one or more reactive components A.

10. The crosslinkable fatty resin of claim 1, wherein the fatty components are fatty acids derived from bio-based sources.

11. The crosslinkable resin of claim 1, wherein the fatty chains in the fatty components contain 10-30 carbons.

12. The crosslinkable resin of claim 1, wherein the fatty chains in the fatty components are linear and attached as pendant chains to the crosslinkable resin.

13. The crosslinkable resin of claim 1, comprising fatty acids comprising C10 to C18 chains with less than 20 wt % of the fatty acids being unsaturated fatty acids.

14. The crosslinkable resin of claim 13, wherein the fatty acids are coconut fatty acids.

15. The crosslinkable resin of claim 1, comprising fatty acids comprising C10 to C18 chains with 20 to 99 wt % of the fatty acids being unsaturated fatty acids.

16. An RMA crosslinkable coating composition comprising the crosslinkable fatty resin of claim 1, an RMA crosslinkable component comprising reactive component B comprising at least 2 activated unsaturated groups (C═C), a base catalyst (C) and optionally further comprising one or more reactivity moderators D, an alcohol, water, reactive solvents that are reactable with the reactive components A or B, organic solvents T, sag control agents E, adhesion promotors P, leveling agents, UV stabilisers, pigments, and fillers.

17. The RMA crosslinkable composition of claim 16, in the form of a kit of parts comprising one or more parts I comprising the base catalyst C for initiating the RMA crosslinking reaction and one or more parts II not comprising said base catalyst C and comprising the other components of the RMA crosslinkable composition.

18. A method for applying a top-coating comprising providing a RMA crosslinkable coating composition comprising the crosslinkable fatty resin of claim 1 and applying a layer of the RMA crosslinkable coating composition to form a top-coating.

19. A method for applying a coating comprising providing a RMA crosslinkable coating composition comprising the crosslinkable fatty resin of claim 1 and applying a layer of the RMA crosslinkable coating composition on a wood floor, a concrete floor, a vinyl floor, terrazo floor, cork floor, phenolic floor or a metal floor, or direct on a concrete floor without a sealer layer, or on hospital and toilet walls and floors to prepare graffiti resistant coatings and sanitizable coatings for hospital and toilet walls and floors.

Description

EXAMPLES

(1) The following is a description of certain embodiments of the invention, given by way of example only.

(2) The examples relate to compositions comprising a RMA crosslinkable alkyd resin and a carbondioxide blocked base catalyst which is a salt of a quaternary ammonium and an alkylsubstituted carbonate. Table 1 shows the catalyst compositions.

(3) Several malonated alkyds were synthesized as described in the examples 1-5 below. In Ex 1, the fatty acid was coconut fatty acid and reactive component A was malonate and introduced by transesterification of dimethyl malonate. This resin is mainly based on saturated fatty acids with low yellowing tendency. In Ex 5 the fatty acids were coconut fatty acid and epoxidized soybean methyl ester and reactive component A was dimethyl malonate.

(4) The components B of the RMA crosslinkable composition are TMPTA or DiTMPTA, which were mixed in the formulation as a pre-mix with the pigment paste or separately or both. Table 2 lists the components of the coating compositions.

Example 1: Malonated Alkyd 1 (MA1)

(5) A three-liter, four-necked reaction flask equipped with a condenser, agitator, heating mantle, sampling tube, thermocouple attached to a thermowatch and toluene-primed Dean-Stark trap was charged with 349.91 parts coconut fatty acid, 395.47 parts trimethylolpropane, 62.73 parts pentaerythritol, 100.10 parts of phthalic anhydride, 93.60 parts of Adipic acid and 0.94 parts of dibutyltin oxide and sparged with nitrogen at 0.5 standard cubic feet per hour (SCFH) for 15 minutes without agitation followed by 15 minutes with agitation. The reaction mixture was then heated to 450-455° F., discontinuing the nitrogen flow at the onset of distillation. The mixture was held at 450-455° F. for an acid value of <1 adding toluene as needed to maintain a steady reflux. Once the acid value was reached, the mixture was cooled to 180° F. under a nitrogen blanket. 742.89 parts of dimethyl malonate were added to the reaction mixture, a packed column was added to the reactor and the Dean-Stark trap drained. The resin was heated to 330° F. and held until methanol distillation ceased. The nitrogen sparge was then increased to 2.0 SCFH to remove the azeotrope solvent and the resin cooled and filtered. The resulting malonate-functional resin contained 11.4% residual dimethyl malonate and had a Gardner-Holdt viscosity of Z1-Z2 with an acid value of 0.5 and an APHA color of 98. The number average molecular weight was 1490 with a weight average molecular weight was 8530.

Example 5: Malonated Alkyd 5 (MA5)

(6) A four-necked reaction flask equipped with a condenser; agitator; heating mantle; addition funnel; thermocouple attached to a control box (Love control series 32A); and primed Dean-Stark trap with toluene, was charged with 21.4 parts (by weight) of coconut fatty acid, 29.2 parts of trimethylol propane, 11.6 parts of phthalic anhydride, 0.07 parts of dibutyltin oxide, and heated under 0.5 SCFH (standard cubic feet per hour) (0.014 m3 hr-1) nitrogen flow to 165° C. At 165° C., water started to distil azeotropically. The reaction temperature was increased to 230° C. and maintained at such temperature until an acid value<1.0 was attained. The alkyd was cooled to 110° C. To this resin, 30.9 parts of dimethyl malonate was added and the temperature was increased to 180° C. Minimum amount of toluene was added to distil methanol azeotropically. At 150° C., methanol started to distil out. The reaction temperature was kept at 180° C. to collect all the methanol. Once the ethanol stop coming, the reaction was cooled to 110° C. To this resin 20.2 parts of methyl epoxy soyate is added. The temperature increased to 180° C. Methanol started to distill out due to the transesterification of methyl ester at the chain end. The reaction was held at 180° C. to distill out all methanol. The nitrogen flow was increased to 2 SCFH (0.057 m3 hr-1) to remove all the toluene while cooling. The epoxy functional malonated alkyd was filtered and stored. The resulting resin had 98% non-volatile material (NVM); density 9.40 lb/gallon, Gardener-Holdt viscosity of Z5-Z6, an acid value of 0.42; a number average molecular weight (Mn) of 2500; a weight average molecular weight (Mw) of 8500; and a polydispersity of 3.4.

Example A: Preparation of Catalysts 1-3

(7) The catalysts 1 and 2 are carbondioxide blocked tetrabutylammonium hydroxide catalysts and were prepared as described in EP2556108 (catalyst C5). The composition is listed in Table 1:

(8) TABLE-US-00001 Component Catalyst 1 Catalyst 2 Aqueous TBAH (55%) 44.60 0 TBAH (40%) in Methanol 0 80 DI Water 4.90 0 Diethylcarbonate 20.10 0 Dimethylcarbonate 0 17.2 n-propanol 30.40 0 Methanol 0 13
Preparation of Catalyst 3

(9) Catalyst 3 is a homogeneous base catalyst according to WO2014166880A1. A magnetic stirrer was put into a flask containing 74.26 g of ethanol. With gentle mixing, 17.49 g of benzotriazole was added and then 8.25 g of KOH was slowly added. The solution was warmed to 49° C. and mixed for two hours to make KBZT catalyst (Catalyst 3). The base concentration was determined by titration to be 1.324 meq/g.

(10) Coating Formulations were prepared from the components mentioned in Table 2 by mixing the components and pre-dissolved components as indicated. The coating formulations do not contain catalyst yet. This is added later. The usual coating additives not explicitly identified and described are well known commercially available components for levelling, anti-foaming (Foamstar ST-2446), surfactants (Byk 310: 315 1:4), colorants (Chroma Chem 844-9955), surface modifiers (Silmer ACR-D2).

(11) TABLE-US-00002 TABLE 2 Paint Formula A Malonated Coconut-Alkyd 1 41.33 TMP-Triacetoacetate 7.29 Miramer M300 15.42 Miramer M410 18.83 Silmer ACR-D2 0.12 Subsequently add 17.02 Methyl Propyl Ketone TOTAL 100.0

Example B1

(12) 100 grams of Formulation A was mixed with 5.82 grams of Catalyst 3 and then applied onto a steel panel. The paint was thoroughly dried after 40 minutes. The potlife of the mixed paint was less than 1 hour. The next day Konig Pendulum Hardness was determined to be greater than 30 seconds. MEK resistance was determined to be greater than 100 double-rubs hence shows good chemical resistance

(13) Easy to Clean Tests:

(14) Example A1: 100 g of formulation in example A is mixed with 5.2 g of catalyst 2 and then applied on a Leneta chart and air dried for 72 hours. A dry erase marker was used to draw lines. The lines were then erased with a dry cloth after various time intervals. The results are summarized in Table 3 below.

(15) TABLE-US-00003 TABLE 3 Dry erase marker test results on malonated alkyd paint Dry-Erase Marker on Example A1 Minutes Marker Rating 30 0 60 0 100 0 1980 0 0 = No mark left

(16) A similar test was conducted side by side with a control malonated polyester (MPE1) based coating.

(17) Comparative example formulation CMark1: A clear coating formulation was prepared by mixing 53.8 g of MPE1 with 23.6 g of DTMPTA, 3 g of butylacetate and 3.1 g of n-propanol, and catalyzing it with 3.3 g of catalyst CAT4. Films were applied at a layer thickness of 50-60 mu, and dried for 20 hr at 80° C.

(18) Formulation Mark2: A clear coating formulation was prepared by mixing 52.1 g MA9 and 31.2 g of DTMPTA and catalyzing it with catalyst CAT4 at a level of 50 ueq/g solids. Films were applied at a layer thickness of 50-60 mu, and dried for 20 hr at 80° C.

(19) TABLE-US-00004 Permanent Board marker marker 1 36 132 240 1 36 Marker test hour hours hours hours hour hours White Board 1 1 3 4 20 16 CMark1 1 1 1 1 16 20 Mark2 1 1 1 1 10  8 1 48 165 240 1 48 hour hours hours hours hour hours

(20) Time indicated is the time after applying the marker ink. Lower numbers indicate a higher ease of cleaning. It can be seen that the RMA coating based on MA9 performs best.

(21) In a second test two different pigments were placed on the coatings made using malonated alkyd MA9 and malonated polyester MPE1 as comparative. After removal of the pigments the amount remaining on the coating is measured (see further description further below). This is also an indicator of the “easy to clean” characteristics, lower values indicating a better performance.

(22) TABLE-US-00005 TABLE 5 easy to clean test using 2 different pigments Material Remaining Applied coating CMark1 Mark2 Carbon Black  7.7% 3.7% Iron Oxide 42.9% 7.3%

(23) From the above data it is clear that the malonated alkyd MA9 based formulation had outstanding “easy to clean” characteristics.

(24) A further set of examples is given below. Abbreviations of constituting monomers in the following examples are given in Table 1.

(25) TABLE-US-00006 TABLE 1 Abbreviations DEM Diethyl malonate DMIPA Dimethyl isophthalate HHPA Hexahydrophthalic anhydride LME Lauric acid methyl ester M300 Trimethylolpropane triacrylate (Miwon) M370 Tris(2-hydroxy ethyl)isocyanurate Triacrylate (Miwon) M4004 Pentaerythritol (EO)n Tetraacrylate (Miwon) M410 Ditrimethylolpropane tetraacrylate (Miwon) MO methyl oleate NPG Neopentylglycol OME Octanoic acid methyl ester TMPAA Trimethylolpropane triacetoacetate (Lonzamon AATMP)
Malonated Polyester MPE1

(26) MPE1 is prepared as follows: Into a reactor provided with a distilling column filed with Raschig rings were brought 382 g of neopentyl glycol, 262.8 g of hexahydrophthalic anhydride and 0.2 g of butyl stannoic acid. The mixture was polymerised at 240° C. under nitrogen to an acid value of 0.2 mg KOH/g. The mixture was cooled down to 130° C. and 355 g of diethylmalonate was added. The reaction mixture was heated to 170° C. and ethanol was removed under reduced pressure. The resin was further cooled and diluted with butyl acetate to 85% solids, to yield a material with OH value 16 mg KOH/g, GPC Mn 1750, and a malonate equivalent weight of 350 (active C—H EQW 175).

(27) Malonated Alkyd 9 (MA9)

(28) MA9 is a malonated alkyd using coconut oil as the oil component, an oil length of 30%, an OH value of 108 mg KOH/g, a GPC Mn of 1800 and a Mw of 4350. The malonate equivalent weight of this material is 360 (active C—H equivalent weight 185).

(29) Malonated Alkyd 10 (MA10)

(30) A four-necked reaction flask equipped with a condenser; agitator; heating mantle; Hempel packed column; and a thermocouple attached to a control box was charged with 104.0 parts of methyl laurate, 505.5 parts of neopentyl glycol, 207.4 parts of hexahydrophthalic anhydride, 0.28 parts of n-butyltin hydroxide oxide, and heated under a nitrogen flow to 170° C. At 170° C., water started to distil. The reaction temperature was increased to 220° C. and maintained at such temperature until an acid value<1.0 was attained. The alkyd was cooled to 120° C. under a nitrogen flow, the packed column was removed and 479.7 parts of diethyl malonate was added. The reaction temperature was increased to 150° C. at which the ethanol started to distil out. The temperature was increased to 170° C. and maintained at such temperature until the ethanol stopped coming. The mixture was brought under vacuum at 170° C. and maintained as such to collect all the residual ethanol. The resulting alkyd had a hydroxyl value of 73 mg KOH/g; a malonate equivalent weight of 338 (C—H EQW 169); an oil length of 10%; a GPC Mn of 838; an Mw of 1267.

(31) General Procedure for Preparation of Malonated Alkyds from 11 to 14 (MA 11-14)

(32) Typical procedure for the preparation of malonated alkyd was as follows. A four-necked reaction flask equipped with a condenser; agitator; heating mantle; Hempel packed column; and a thermocouple attached to a control box was charged with 295.7 parts of methyl laurate, 455.5 parts of neopentyl glycol, 147.3 parts of dimethyl isophthalate, 0.27 parts of n-butyltin hydroxide oxide, and heated to 170° C. under a nitrogen flow. At 170° C., methanol started to distil out. The reaction temperature was increased to 200-220° C. and maintained at such temperature until methanol stopped coming. The alkyd was cooled to <120° C. under a nitrogen flow, the packed column was removed and 447.1 parts of diethyl malonate was added. The reaction temperature was increased to 150° C. at which the ethanol started to distil out. The temperature was increased to 170° C. and maintained at such temperature until the ethanol stopped coming. The mixture was brought under vacuum at 170° C. and maintained as such to collect all the residual ethanol. Once the ethanol stopped coming, the reaction was cooled at room temperature and the resulting resin was stored in a closed container.

(33) Malonated alkyd compositions and properties of examples 10 through 14 are given in Table 2

(34) TABLE-US-00007 TABLE 2 Malonated alkyd compositions and properties Parts of constituting monomers OH Alkyd LM HHP OM M NP DMIP DE value Oil CH- codes E A E O G A M Mn Mw D (KOH/g) length EQW* MA10  8 16 — — 39 — 37 838 1267 1.5 73 10 169.0 MA11 22 — — — 34 11 33 1029 1544 1.5 31 29 180.5 MA12 21 — — — 32 10 37 1070 1607 1.5 17 28 165.0 MA13 — — 16 — 34 11 39 1061 1751 1.7 38 23 159.6 MA14 — — — 25 31  9 35 1100 1760 1.6 31 34 185.4 *active CH- Equivalent Weights
Malonated Alkyd 15 (MA15)

(35) A four-necked reaction flask equipped with a condenser; agitator; heating mantle; and a thermocouple attached to a control box (Love control series 32A) was charged with 415.8 parts of lauryl alcohol, 178.8 parts of diethyl malonate, 0.11 parts of n-butyltin hydroxide oxide, and heated to 150° C. under a nitrogen flow. At 150° C., ethanol started to distil out. The reaction was increased to 170° C. and maintained at such temperature until the ethanol stopped coming. The mixture was brought under vacuum at 170° C. and maintained as such to collect all the residual ethanol. The resulting resin had a hydroxyl value of 36; a CH-EQW of 227; a GPC Mn of 519; a GPC Mw of 569.

(36) Malonated Polyester 16 (MP 16)

(37) A four-necked reaction flask equipped with a condenser; agitator; heating mantle; and a thermocouple attached to a control box (Love control series 32A) was charged with 185.1 parts of neopentyl glycol, 314.9 parts of diethyl malonate, 0.1 parts of n-butyltin hydroxide oxide, and heated to 150° C. under a nitrogen flow. At 150° C., ethanol started to distil out. The reaction was increased to 170° C. and maintained at such temperature until the ethanol stopped coming. The mixture was brought under vacuum at 170° C. and maintained as such to collect all the residual ethanol. The resulting resin had a hydroxyl value of 45.5; a CH-EQW of 89; a GPC Mn of 1350; an Mw of 2407; and a polydispersity of 1.8.

(38) Alkyd Resin 17 (A17)

(39) A four-necked reaction flask equipped with a condenser; agitator; heating mantle; and a thermocouple attached to a control box (Love control series 32A) was charged with 166.1 parts of neopentyl glycol, 683.6 parts of methyl laurate, 0.20 parts of n-butyltin hydroxide oxide, and heated to 170° C. under a nitrogen flow. At 170° C., methanol started to distil out. The reaction temperature was increased to 200° C. and maintained at such temperature until methanol stopped coming. The mixture was brought under vacuum at 170° C. and maintained as such to collect all the residual ethanol. The resulting alkyd resin had a hydroxyl value of 41; an oil length of 89%; a Mn of 461; an Mw of 542; 137 and a polydispersity of 1.2.

(40) Mercaptane-Modified Polyfunctional Acrylate (SH-M410)

(41) A single-neck reaction flask equipped with a magnetic bar coated with Teflon and a magnetic stir plate was charged with 20.0 parts of M410, 2.86 parts of triethylamine, and agitated at ambient temperature. Once the mixture was homogeneous, 8.64 parts of dodecanethiol, was added dropwise in the reaction flask. NMR was used to determine the percentage of reacted double bonds of M410. This was 25%. The resulting mercaptane-modified polyfunctional acrylate had an oil length of 30% and an Mn of 667.

(42) TABLE-US-00008 TABLE 3 The catalyst 4 (CAT4) composition (base content 0.928 mmole/g) Component Catalyst C Aqueous TBAH (55%) 100 Diethylcarbonate 45.1 n-propanol 181
General Procedure for Preparing and Applying Coating Formulations

(43) The donor and acceptor components, any additives, and the thinning solvents were transferred to a flask and mixed. After obtaining a homogeneous mixture the stated amount of catalyst 4 was added. The composition of the catalyst 4 is listed in Table 3.

(44) Coating formulations were drawn down on a glass panel (175×100×3 mm), to obtain a dry layer thickness of 50-60 micron. In most cases, curing was done at 80° C. for 24 h, to allow for maximum conversion and avoid film inhomogeneity through solvent entrapment. The easy-to-clean properties were tested at room temperature.

(45) Coatings formulation were prepared from the components mentioned in Table 4.

(46) TABLE-US-00009 TABLE 4 RMA formulations Component A1 A2 A3 A4 A5 A6 A7 grams MA9 0.0 0.0 14.7 0.0 0.0 0.0 29.3 grams MPE1 0.0 0.0 26.6 35.8 0.0 0.0 12.4 grams TMPAA 0.0 29.3 8.9 4.7 25.9 24.0 5.1 grams MP16 35.3 0.0 0.0 0.0 0.0 0.0 0.0 grams MA15 0.0 0.0 0.0 0.0 0.0 9.6 0.0 grams MA10 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA11 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams A17 0.0 0.0 0.0 8.6 8.6 0.0 0.0 grams MA12 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA13 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Pre-dissolve: grams 1,2,4-Triazole 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams Succinimide 0.0 0.0 0.0 0.0 0.0 0.0 0.0 n-propanol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Subsequently add and mix: grams M410 41.6 47.6 30.8 0.0 42.0 43.4 32.0 grams M4004 0.0 0.0 0.0 33.6 0.0 0.0 0.0 grams M300 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams M370 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams SH-M410 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams BuAc 2.1 2.1 1.7 1.5 2.2 2.1 1.9 grams n-propanol 16.8 16.8 13.2 12.1 17.7 16.8 15.1 Subsequently add and mix: grams Catalyst 4 4.1 4.2 4.1 3.7 3.7 4.1 4.1

(47) TABLE-US-00010 TABLE 5 RMA formulations Component A8 A9 A10 A11 A12 A13 A14 grams MA-9 7.3 32.5 0.0 38.6 43.0 44.4 44.3 grams MPE1 12.7 0.0 0.0 0.0 0.0 0.0 0.0 grams TMPAA 4.3 0.8 0.0 5.8 6.4 1.8 0.0 grams MP16 0.0 9.4 0.0 0.0 0.0 0.0 0.0 grams MA15 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA10 0.0 0.0 24.1 0.0 0.0 0.0 0.0 grams MA11 23.4 0.0 24.1 0.0 0.0 0.0 0.0 grams A17 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA12 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA13 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Pre-dissolve: grams 1,2,4-Triazole 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams Succinimide 0.0 0.0 0.0 0.0 0.0 0.0 0.0 n-propanol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Subsequently add and mix: grams M410 31.1 34.2 28.8 32.5 30.9 0.0 0.0 grams M4004 0.0 0.0 0.0 0.0 0.0 34.2 32.6 grams M300 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams M370 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams SH-M410 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams BuAc 1.9 2.1 2.1 2.1 1.7 9.5 2.1 grams n-propanol 15.0 16.8 16.8 16.8 13.7 5.7 16.8 Subsequently add and mix: grams Catalyst 4 4.2 4.1 4.1 4.1 4.3 4.3 4.2

(48) TABLE-US-00011 TABLE 6 RMA formulations Component A15 A16 A17 A18 A19 A20 A21 A22 grams MA-9 44.4 44.6 44.6 0.0 48.3 0.0 48.4 0.0 grams MPE1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams TMPAA 0.0 0.0 0.0 0.0 1.8 3.1 0.0 0.0 grams MP16 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA15 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA10 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA11 0.0 0.0 0.0 0.0 0.0 46.5 0.0 48.7 grams A17 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA12 0.0 0.0 0.0 54.5 0.0 0.0 0.0 0.0 grams MA13 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams MA14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Pre-dissolve: grams 1,2,4- 0.0 0.0 0.0 0.0 0.0 0.0 0.4 0.0 Triazole grams Succinimide 0.0 0.0 0.0 0.0 0.0 0.0 1.5 0.0 n-propanol 0.0 0.0 0.0 0.0 0.0 0.0 17.5 0.0 Subsequently add and mix: grams M410 0.0 0.0 0.0 33.9 30.2 27.4 29.0 28.3 grams M4004 32.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams M300 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams M370 0.0 32.4 32.4 0.0 0.0 0.0 0.0 0.0 grams SH-M410 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 grams BuAc 2.1 2.1 2.1 0.7 1.7 2.0 0.0 2.1 grams n-propanol 16.8 16.8 16.8 5.9 13.7 16.8 0.0 16.8 Subsequently add and mix: grams Catalyst 4 4.2 4.1 4.2 5.0 4.3 4.1 3.1 4.1

(49) TABLE-US-00012 TABLE 7 RMA formulations Component A23 A24 A25 A26 A27 A28 A29 A30 grams MA9 51.2 53.0 0.00 53.8 0.0 0.0 0.0 0.0 grams MPE1 0.0 0.0 0.0 0.0 0.0 0.0 58.8 57.2 grams MA5 0 0 58.8 0 0 0 0 0 grams TMPAA 1.9 0.0 0.00 2.2 18.7 0.0 0.0 1.9 grams MP16 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams MA15 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams MA10 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams MA11 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams A17 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams MA12 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams MA13 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams MA14 0.0 0.0 0.00 0.0 0.0 51.1 0.0 0.0 Pre-dissolve: grams 1,2,4- 0.0 0.4 0.00 0.0 0.0 0.0 0.0 0.0 Triazole grams 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 Succinimide n-propanol 0.0 7.1 0.00 0.0 0.0 0.0 0.0 0.0 Subsequently add and mix: grams M410 0.0 0.0 29.8 0.0 0.0 29.2 0.0 29.8 grams M4004 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams M300 27.3 26.9 0.00 21.0 0.0 0.0 26.9 0.0 grams M370 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 grams SH-M410 0.0 0.0 0.00 0.0 58.2 0.0 0.0 0.0 grams BuAc 5.7 8.1 0.00 2.2 2.1 1.7 1.2 0.7 grams n-propanol 9.6 0.0 7.9 16.8 16.9 13.6 8.9 6.1 Subsequently add and mix: grams Catalyst 4 4.4 4.5 3.55 4.1 4.1 4.4 4.1 4.4

(50) TABLE-US-00013 TABLE 8 Component A31 A32 A33 A34 A35 A36 grams MA9 0.0 0.0 23.1 0.0 0.0 0.0 grams MPE1 62.5 0.0 23.9 42.9 0.0 0.0 grams TMPAA 0.0 0.0 0.9 0.0 3.0 0.0 grams MP16 0.0 0.0 0.0 0.0 0.0 0.0 grams MA15 0.0 0.0 0.0 0.0 0.0 0.0 grams MA10 0.0 47.5 0.0 0.0 0.0 0.0 grams MA11 0.0 0.0 0.0 0.0 44.6 0.0 grams A17 0.0 0.0 0.0 0.0 0.0 0.0 grams MA12 0.0 0.0 0.0 0.0 0.0 0.0 grams MA13 0.0 0.0 0.0 0.0 0.0 48.2 grams MA14 0.0 0.0 0.0 0.0 0.0 0.0 Pre-dissolve: grams 1,2,4-Triazole 0.0 0.0 0.0 0.0 0.0 0.0 grams Succinimide 0.0 0.0 0.0 0.0 0.0 0.0 n-propanol 0.0 0.0 0.0 0.0 0.0 0.0 Subsequently add and mix: grams M410 0.0 29.5 0.0 0.0 0.0 31.8 grams M4004 23.9 0.0 0.0 0.0 29.5 0.0 grams M300 0.0 0.0 0.0 0.0 0.0 0.0 grams M370 0.0 0.0 32.7 0.0 0.0 0.0 grams SH-M410 0.0 0.0 0.0 40.4 0.0 0.0 grams BuAc 1.1 2.1 1.7 1.5 2.1 1.7 grams n-propanol 8.4 16.8 13.6 11.1 16.7 13.7 Subsequently add and mix: grams Catalyst 4 4.1 4.1 4.1 4.1 4.1 4.5
Procedure for Preparation of 2K Polyurethane Formulation C1

(51) The stated amount of Setalux 1774-SS70 (69% solids, 5% OH, a commercial Nuplex material) and methyl n-amyl ketone (MAK) were transferred to a flask and mixed. After obtaining a homogenous mixture, the stated amount of Setalux 91780 VS-55 (62% solids, 4.5% OH, a commercial Nuplex material), the levelling additive BYK-358N and MAK were added and mixed. Once the mixture was homogeneous, the stated amount of Tolonate HDT-LV (Vencorex) was added in the agitated mixture of acrylic polyols. The resulting mixture was applied on glass panels similarly as in the general procedure for preparation of RMA formulations. Curing was done at 140° C. for 2 hours. This resulted in coating with a dry layer thickness of 52 microns. The easy-to-clean property was tested after cooling of the cured film at room temperature.

(52) TABLE-US-00014 TABLE 9 Formulation of 2K polyurethane formulation C1 Component C1 Pre-mix: grams Setalux 1774-SS70 48.8 grams MAK 2.9 Mix and add: 0.0 grams Setalux 91780 VS-55 22.2 Subsequently mix and add: 0.0 grams BYK-358N 0.04 grams MAK 0.9 Subsequently mix and add: 0.0 grams Tolonate HDT-LV*** 25.1 ***Polyisocyanate with 100% non-volatiles and 23% NCO
Results of Easy-to-Clean Testing

(53) TABLE-US-00015 TABLE 10 Examples and comparative examples of the easy-to-clean properties of the formulated coating Coating OL XLD Tg ΔE A1a 0.0 5.1 364 15.4 A2  0.0 6.4 383 8.3 A3  5.3 2.8 303 5.7 A4  9.9 2.0 307 8.0 A5  10.0 5.5 381 2.5 A6  10.0 5.5 386 5.5 A7  10.8 3.3 337 14.3 A8  11.3 2.7 323 5.0 A9  12.3 3.6 344 2.6 A10 12.3 1.7 315 11.9 A11 14.6 3.5 343 2.9 Al2 15.5 3.2 340 2.7 A13 16.0 2.8 303 9.9 A14 16.7 2.7 305 6.9 A15 16.8 2.7 305 7.4 A16 16.8 1.5 342 18.2 A17 16.8 1.5 343 19.4 A18 16.9 2.1 312 6.8 A19 17.4 2.9 330 1.3 A20 17.5 1.7 295 7.5 A21 18.1 2.2 323 3.0 A22 18.3 1.9 312 2.9 A23 18.5 3.1 329 1.5 A24 19.2 2.8 326 1.2 A25 19.3 2.4 322 2.0 A26 20.3 2.2 314 2.1 A27 22.7 1.9 307 6.6 A28 21.8 2.1 315 6.2 Comparative examples A29 0.0 3.0 336 28.9 A30 0.0 2.3 333 24.0 A31 0.0 1.2 306 23.7 A32 6.3 1.7 321 31.2 A33 8.7 1.3 337 26.2 A34 15.8 0.9 294 34.8 A35 16.8 1.3 265 27.6 A36 13.9 2.7 330 30.7 C1 0.0 1.3 338 25.3

(54) Table 11 describes the effect of the development of properties upon ambient drying of the compositions of the invention, relative to the ‘final’ properties as indicated by the force dried compositions (80° C., 24 hrs). It can be seen that the EtC properties improve during initial drying, as the Tg and XLD properties of the coating develop to grow into the preferred ranges.

(55) TABLE-US-00016 TABLE 11 Effect of curing methods on easy-to-clean properties Coating .sup.a) OL XLD Tg ΔE A20″.sup.b) 18.1 n.a. n.a. 31.5 A20′.sup.c) 18.1 n.a. n.a. 7.8 A20 .sup.d) 18.1 2.2 323 3.0 A 23″.sup.b) 19.2 2.1 297 39.9 A 23′.sup.c) 19.2 2.1 308 12.4 A23 .sup.d) 19.2 2.8 326 1.2 .sup.a) A20″and A20′ same formulation of A20; A23″and A23′ same formulation of A23 .sup.b) Cured at room temperature for 4 h .sup.c) Cured at room temperature for > 120 h .sup.d) Post-cured at 80° C. for 24 h
General Procedure for Easy-to-Clean Testing Based on Color Measurements

(56) Prior to testing, the CIE 1976 (L,a,b) color of coated panels was measured using an AvaSpec-ULS2048 spectrometer at a wavelength of 550 nm. Carbon black pigment was applied to a coated panel as an 8% slurry in water on 6-8 different spots on the coating by using a pipette and left in contact with the coating for 24 hours at room temperature. The panels were turned upside-down; gently tapped on the back, and brushed using a 1-cm wild boar-hair until the resulting deposited dried carbon black stopped coming off. The color (L,a,b) of the tested panels at the position of the stained spots was measured using the spectrometer again.

(57) The CIE color difference ΔE of the coated panel before and after application of the carbon black is defined as:
ΔE=√{square root over (((ΔL).sup.2+(Δa).sup.2+(Δb).sup.2)}

(58) where ΔL, Δa and Δb represents the difference in L,a,b values between the reference color and the tested panel. This value is used as a measure of the easy-to-clean properties: the lower the □E value, the better these properties are considered to be.

(59) General Procedure for Easy-to-Clean Testing Based on Weight Measurements

(60) Prior to testing, the weight (0.1 mg precision) of coated panels was determined using an analytical balance. Similarly to the color measurement method, carbon black slurry was applied on the coated panels and let dried at room temperature for 24 hours. The panels were carefully weighted to determine the exact amount of the resulting dried carbon black. After weighting, the panels were turned upside-down and gently tapped on the back until the resulting deposited dried carbon black stopped coming off. The panels were weighed again to determine the weight-percent of carbon black picked up by the coating: the lower this value, the better the easy-to-clean properties of the coating. This experiment was run with a carbon black slurry, and also with an iron oxide slurry

(61) General Procedure for Easy-to-Clean Testing Based on a Permanent Marker

(62) Lines were drawn on the coating using a permanent marker. A paper wipe soaked with isopropyl alcohol was used for cleaning and the number of wipes needed to completely remove one line after a given time was counted (if the line is not fully removed, then the test stops when no more ink is visible on the paper wipe).

(63) General Procedure for Dynamic Mechanical Thermal Analysis

(64) Dynamic Mechanical Thermal Analysis (DMTA) measurements were performed on freestanding films of the materials of interest. Typically, the films applied on glass, used for the easy-to-clean tests, could be removed from the substrate for that purpose. In other cases, similar films were prepared on polypropylene (easy release) substrates. DMTA measurements were done by applying a 0.03% strain, at 11 Hz frequency, from −100 to 200° C., at a heating rate of 5° C./min.

(65) The Tg of the coating was determined from the temperature at which the loss modulus (E″) had a maximum: these are the Tg values used in this application, and referred to in the claims.

(66) The cross-linking density (XLD) was calculated according to rubber elasticity theory by applying the formula:

(67) $v_z=\frac{E^{\prime }}{3\mathrm{RT}}$

(68) where the minimum value of the elastic modulus (E′) at the rubber plateau was used. This value is in mmole/ml, this can be translated into mmole/g values when using the density of the organic coating: we have assumed this to be 1.2 g/ml for all systems described here.