Additive composition for powder coatings

Abstract

The present invention relates to an additive composition for use in powder coatings comprising a powder coating additive absorbed on a carrier, characterized in that the carrier is a foamed micro-porous thermoplastic polymer as well as its use in powder coating.

Description

[0001] 202200165 Foreign Filing 1

[0002] Additive composition for powder coatings

[0003] FIELD OF THE INVENTION

[0004] The invention relates to an additive composition suitable for the use in powder coatings. It in particular relates to an additive composition, more specifically for use in powder coatings comprising a carrier comprising a powder coating additive, wherein the carrier is a foamed micro-porous thermoplastic polymer (matrix polymer), a powder coating composition comprising said additive composition, a process for making this powder coating composition, and articles coated with said powder coating composition.

[0005] BACKGROUND OF THE INVENTION

[0006] Powder coating is a technique generally known in the art (cf. E. Spyrou, Powder Coatings Chemistry and Technology: 3rd Revised Edition, Hannover, Germany: Vincentz Network, 2014; J. Pietschmann, Industrial powder coating: 1stEdition, Wiesbaden, Germany: Springer Wiesbaden, 2023) and involves a pre-mixing of components, followed by extrusion, cooling of the extrudate, followed by grinding, such that the resulting powder can be applied to a substrate via e.g. fluidized bed coating or electrostatic spraying onto a substrate, and treatment to cure or melt the binder in the powder coating composition. Powder coatings typically contain additives to provide the coating with certain properties. Often these additives are liquid at room temperature or at higher temperatures, but below the temperatures commonly necessary for melting the binder in the powder coating extrusion process. This can lead to problems during the pre-mixing process, extrusion and inhomogeneity in the resulting powder coating composition, its application to a substrate and defects of the resulting coating. As a result, liquid coating additives as such are being avoided in the formulation of powder coating compositions.

[0007] This problem is solved in the state of the art by introducing the liquid additive as a masterbatch, wherein the additive is either dissolved or dispersed in a compatible resin or wax, or absorbed on a porous silica carrier. However, there are several drawbacks to these solutions.

[0008] When mixed with a compatible resin, the additive loading is generally limited to about 10 wt.-% of the masterbatch when the additive is liquid at room temperature, thereby requiring higher dosage levels of the masterbatch. Moreover, there are limitations to the type of resin used, as it can interfere with the main binder of the powder coating composition.

[0009] When loaded onto a porous silica carrier, loadings of up to 50-60 wt.-% can be achieved. However, the additive is oftentimes not fully released from the silica during curing and thus not fully utilized, thereby requiring higher loadings of costly additives. Moreover, the silica can influence the rheological properties of the powder melt during curing, thereby leading e.g.to the development of irregular surface and / or rough surface leveling of the coating, also referred to as orange peel effect. Moreover, silica leads to a matting effect of the coating, which oftentimes is undesired.

[0010] It is therefore an object of the invention to provide a way to introduce additives into powder coating compositions while overcoming at least one of the drawbacks faced by the methods known in the state of the art. In this regard, it is a particular objective of the invention to provide powder coating additives that do 202200165 Foreign Filing 2 not negatively affect the appearance of the resulting coating, in particular with respect to leveling and / or gloss.

[0011] DETAILED DESCRIPTION OF THE INVENTION

[0012] It was surprisingly found that the drawbacks faced by the solutions known in the state of the art may be overcome by using a foamed micro-porous thermoplastic polymer as carrier for the powder coating additive.

[0013] In one aspect the invention therefore relates to an additive composition suitable for use in powder coatings comprising a powder coating additive absorbed on a carrier, wherein the carrier is a foamed micro-porous thermoplastic polymer (matrix polymer).

[0014] Absorption of the powder coating additive can be accomplished by merely mixing the liquid powder coating additive with the carrier. If the powder coating additive is not liquid at room temperature, the mixing with the carrier can be executed at above the melting point of the powder coating additive but below the melting point of the matrix polymer, or by dissolving the powder coating additive in a suitable solvent, mixing with the carrier and removing the solvent, preferably at elevated temperature and reduced pressure (when compared to standard conditions).

[0015] In a preferred embodiment of the invention the weight ratio between the carrier and the powder coating additive is in the range of 1 :6 to 6:1 , preferably in the range of 1 :3 to 4:1 , more preferably in the range of 1 :2 to 3:1 , most preferably in the range of 1 :1 to 2:1 .

[0016] Carrier

[0017] The carrier according to the present invention is a foamed micro-porous thermoplastic polymer (matrix polymer).

[0018] Preferred carriers used in the invention have a porosity in the range of 40 to 90 vol.-%, more preferably 45 to 85 vol.-%, even more preferably 50 to 80 vol.-%, most preferably 60 to 75 vol.-%. Preferred carriers have an average pore size of at most 100 pm, more preferably at most 80 pm, most preferably at most 50 pm. It is further preferred for the average pore size to be at least 2 pm, more preferably at least 5 pm, more preferably at least 20 pm. Such carriers are particularly easy to load and retain the additive during extrusion of the powder coating composition. The method for producing suitable carriers and the determination of their porosity and pore size are described in WO 03 / 092982 A2.

[0019] Extrusion of the powder coating composition is typically executed in the range of 50 to 115°C, where a higher temperature is typically associated with an easier more homogenous mixing. It was found that it is preferred for the Vicat softening temperature measure according to method A50 in ISO 306 is preferably above 80°C, more preferably above 85°C, even more preferably above 90°C. It was also found to be advantageous and thus preferred for the melting point of the matrix polymer to be at least 95°C, preferably at least 100°C, more preferably at least 105°C, most preferably at least 110°C. Powder coating compositions are typically cured in the range of 120 to 200°C. It was found to be preferable for the melting point of the matrix polymer to be at most 200°C, more preferably at most 160°C, even more preferably at 202200165 Foreign Filing 3 most 140°C, most preferably at most 120°C. In a particularly preferred embodiment of the invention the melting point of the matrix polymer is from 95 to 200°C, more preferably from 100 to 160°C, more preferably from 105 to 140°C, most preferably from 110 to 120°C. The melting point of the matrix polymer can be determined by differential scanning calorimetry (DSC) according to ISO 11357-3:2018 with a heating and cooling rate of 10 K / min.

[0020] It is a particularly desirable goal in the art to provide to minimalize the impact of the method by which the additive is introduced into the powder coating composition onto the final powder coating itself. This would enable an easier way to formulate powder coating composition, only focusing on the core ingredients without having to balance out possible side effects with further additives or extensive experimentation. It was surprisingly found that the matrix polymers listed in the following are particularly suitable for this:

[0021] In a preferred embodiment of the invention the matrix polymer contains a polymer selected from the group of homo- or copolymers of polyolefins, polystyrenes, polyvinylalcohols, polyacrylates, polymethacrylates, polyesters, polyamides and polycarbonates.

[0022] In a more preferred embodiment the matrix polymer contains a polymer selected from the group consisting of high-density polyethylene, low-density polyetheylene, linear low-density polyethylene, polypropylene, polystyrene, poly(ethylene-co-methacrylate), poly(ethylene-co-vinylacetate), polybutylene(adipate-co- terephthalate), polyamide 6, polyamide 6.6, polyamide 12, poly(ethylene terephthalate), poly(styrene-co- butadiene) and polycarbonate, preferably poly(ethylene-co-vinylacetate) or polybutylene(adipate-co- terephthalate), most preferably polybutylene(adipate-co-terephthalate). It is further preferred for the matrix polymer to be a polymer selected from the above group.

[0023] Powder coating additives

[0024] In a preferred embodiment of the invention the powder coating additive is selected from the group consisting of additives to regulate the surface tension (surfactant), anti-crater agent, dispersant, effect agent, defoamer, texturing agent, scratch resistance agent, anti-blocking agent, lubricant, adhesion promoter, hydrophobic agent, hydrophilic agent, inhibitor, catalyst, corrosion inhibitor, light stabilizer, matting agent, wetting agent, structuring agent, leveling agent, and / or additives to improve chargeability, water resistance, chemical resistance. Particularly preferred among these are anti-crater agent, defoamer, texturing agent, scratch resistance agent, anti-blocking agent, structuring agent, leveling agent, and / or additives to improve chargeability, water resistance, adhesion promoter, chemical resistance, more preferably adhesion promoter.

[0025] Preferred classes of powder coating additives are selected from the group consisting of polysiloxanes, poly(meth)acrylates, maleic acid anhydride-copolymers, polybutadienes, polyolefins, polyester-polyethers, polyalkylene imines, polyamines, polyester resins, silanes, polyglycerol partial esters, phospholipids, acetylenic diols, polyethers, fatty acid amidoamines, phosphoric acid esters, triglycerides, fatty alcohol alkoxylates, and thioethers. Among polysiloxanes, organo-modified polysiloxanes, in particular polyether- modified polysiloxanes, and polyether-polysiloxane copolymers, in particular polyoxyalkylene-polysiloxane block-copolymers, are preferred. The above classes of compounds are meant to include derivatives thereof. 202200165 Foreign Filing 4

[0026] Preferred embodiments of these powder coating additives are provided in the following. In a particularly preferred embodiment of the invention the powder coating additive is selected from the group consisting of the compounds listed in the following:

[0027] Leveling agent

[0028] In a preferred embodiment of the invention a powder coating additive is a slip and / or leveling agent. A slip and / or leveling agent can be a polyether-modified polysiloxane. A preferred polyether-modified polysiloxane is disclosed in EP 3 898 850 A1 , adhering to general formula (I):

[0029] (formula (I)) with

[0030] Ra2= identical and / or different alkyl radicals having 1 to 8 carbon atoms, preferably having 1 - 4 carbon atoms, particularly preferably having 1 or 2 carbon atoms,

[0031] Ra1= Ra2and / or -CPiH2PiO[(C2H4O)xi(C3H6O)yi]Ra3, where p = 2, 3 or 4, with the proviso that at least one Ra1= -CpiH2piO[(C2H4O)xi(C3HeO)yi]-,

[0032] Ra3= alkyl radical having 1 to 6 carbon atoms, hydrogen, or C(O)R4, where R4is an alkyl radical having 1 to 6 carbon atoms; preferably methyl or acetyl, n1 > 3, preferably n > 45, more preferably > 50, particularly preferably n > 60,

[0033] - ml = 1 to 5,

[0034] - wherein x1 and y1 are selected such that the average molecular weight of the polyoxyalkylene block -[(C2H4O)xi(C3H6O)yi]- is > 1000 g / mol, preferably > 1000 g / mol, preferably the molar weight ratio of x1 to y1 is < 0.8, preferably < 0.75.

[0035] Preferably Ra3is methyl. It is further preferred for n < 500, more preferably < 300, most preferably < 200. Preferably the average molecular weight of the polyoxyalkylene block -[(C2H4O)xi(C3HeO)yi]- is less than 10000 g / mol, preferably less than 8000 g / mol and particularly preferably less than 5000 g / mol.

[0036] It was also found to be beneficiary for that the molar weight ratio x1 to y1 is not less than 0.05, preferably not less than 0.1 and particularly preferably not less than 0.2.

[0037] It is also preferred for the polyether-modified polysiloxane having exclusively pendant modifications where Ra1= -CpiH2piO[(C2H4O)xi(C3H6O)yi]R3, where p = 2, 3, 4, or 5. It is particularly preferred for the pendant- modified polysiloxane having a- and w-terminal modifications of alkyl radicals, especially methyl groups.

[0038] In an alternative embodiment, instead of-CPiH2piO[(C2H4O)xi(C3H6O)yi]Ra3at least one Ra1is replaced with -CH2CH(CH3)C(O)O-[(C2H4O)xi(C3H6O)yi]Ra3In this embodiment it is further preferred for all Ra1to be replaced accordingly. 202200165 Foreign Filing 5

[0039] When used in a powder coating, polyether-modified polysiloxane according to general formula (I) are preferably used in 0.001 to 5.0 wt.-%, more preferably 0.01 to 3.0 wt.-%, based on the total weight of the curable powder coating composition.

[0040] It was found that the use of a polyether-modified polysiloxane according to general formula (I) as described above leads to excellent surface slip and scratch resistance. Moreover, powder coatings produced with such a polyether-modified polysiloxane can be recoated.

[0041] A further preferred levelling agent are (meth)acrylate copolymers. The term “(meth)acrylate” is meant to comprise both acrylate and meth \ I Iaol >c - rylate. One preferred (meth)acry / la \ 2te copolymer comprises the buildings o < c- blocks according to formulas (Ila) and (lib): I _ _ I '

[0042] ?b1“

[0043] (formula (Ila)) (formula (lib)) where

[0044] Rb1is a methyl group or H, preferably H;

[0045] Rb2is a hydrocarbon group comprising 1 to 6 carbon atoms, preferably an aliphatic hydrocarbon group comprising 1 to 6 carbon atoms;

[0046] Rb3is a hydrocarbon group comprising 1 to 6 carbon atoms or H.

[0047] The copolymer comprising the buildings blocks according to formulas (Ila) and (lib) are preferably statistical copolymers. It is also preferred for the copolymers comprising the buildings blocks according to formulas (Ila) and (lib) to have an average molecular weight Mnin the range of 2500 to 25000 g / mol, preferably in the range of 5000 to 10000 g / mol.

[0048] Color compatibilizer

[0049] In an embodiment of the invention the powder coating additive comprises a color compatibilizer, i.e. a substance promoting the compatibility between pigment and the residual mixture of the powder coating. A preferred color compatibilizer works with both inorganic pigments and organic pigments. It was found that fatty acid amidoamines as disclosed in EP 3 305 840 A1 have excellent compatibilizing capabilities provided that the fatty acid amidoamine is the condensation product of a fatty acid or their corresponding ester or fatty oil and an aliphatic polyamine with an amine functionality of at least 2 and that the polyamine comprises at least one primary amine and at least one tertiary amine.

[0050] In a preferred embodiment the polyamine is selected from the group consisting of aminoethylpiperazine (AEP), dimethylaminopropylamine (DMAPA), diethylaminopropylamine, dimethylaminoethylamine, N- methyldipropylenetriamine and mixtures thereof, more preferably from the group consisting of aminoethylpiperazine (AEP), dimethylaminopropylamine (DMAPA), and mixtures thereof. It is further 202200165 Foreign Filing 6 preferred for the polyamine amine to comprise isophorone diamine (IPDA), methylenebis(cyclohexylamine) (PACM) or mixtures thereof, preferably in an amount up to 30 mol-% of total amine used.

[0051] The fatty acid is of general formula Rd1-COOH, where Rd1could be any aliphatic carbon chain with the number of carbons ranging from 1 to 25, preferably 3 to 25, more preferably 7 to 17. It is preferred for the fatty acid to be selected from the group consisting of tall oil fatty acid, coconut fatty acid, myristic acid, lauric acid, decanoic acid, nonanoic acid, octanoic acid and mixtures thereof, more preferably octanoic acid.

[0052] The resulting amidoamine preferably has an amine value of at least 50 mg KOH / g and an acid value of less than 60 mg KOH / g. The amine value of the amidoamine is preferably less than at least 100 mg KOH / g, more preferably at least 150 mg KOH / g. The amine value of the amidoamine is determined according to DIN 53176. The acid value is preferably less than 50 mg KOH / g, more preferably less than 40 mg KOH / g. The acid value of the amidoamine is determined according to DIN EN ISO 21 14.

[0053] For powder coating compositions comprising said color compatibilizer, it is preferred for the fatty acid amidoamine to lie in the range of 0.1 to 5.0 wt.-% based on the total weight of the powder coating composition.

[0054] It was found that the use of the above color compatibilizers is beneficial for the color strength of the powder coating. Additionally, it can lower the difference in color (delta E) of a rubbed-out area compared to unrubbed area determined according to ASTM D2244-15a.

[0055] Defoamer

[0056] In an embodiment of the invention a powder coating additive comprises a defoamer. A preferred defoamer is disclosed in EP 2 653 205 A1. This defoamer is a polyglycerol partial ester, in particular a polyglycerol partial ester of saturated or unsaturated, linear or branched fatty acids and / or aromatic monocarboxylic acids and polyfunctional carboxylic acids, obtainable by esterification of a polyglycerol mixture with saturated or unsaturated, linear or branched fatty acids having 4 to 22 carbon atoms and / or aromatic monocarboxylic acids having 7 to 22 carbon atoms and polyfunctional carboxylic acids having 4 to 54 carbon atoms and / or their anhydrides or esters.

[0057] Preferably the degree of esterification of the polyglycerol is between 76 and 100%, more preferably between 91 and 100%. The degree of esterification is determined via a volumetric determination of the acid value (AV). The acid value indicates the mass of mg of KOH which is necessary to neutralize the free acids present in 1 g of product. The acid value can be determined as described in DIN EN ISO 21 14.

[0058] The basis for the polyglycerol partial esters is the polyglycerol mixtures used which are based in particular on polyglycerols having an average degree of condenyxsation of > 2, i.e. with at least two repeat units, preferably with 2-20 repeat units, particularly preferably with 3-5 repeat units. These are technical-grade polyglycerol mixtures which are obtained e.g. by alkali-catalyzed condensation of glycerol at elevated temperatures, from which fractions with the desired degree of condensation can optionally be obtained by 202200165 Foreign Filing 7 distillation processes. Likewise of suitability are also polyglycerols which are obtained in a different way, e.g. from epichlorohydrin or glycidol.

[0059] Particularly suitable polyglycerols have the following oligomer distribution:

[0060] Glycerol: 0.01wt.-% to 20wt.-%, preferably 3 wt.-% to 12 wt.-%,

[0061] Diglycerols: 0.01wt.-% to 60wt.-%, preferably 20 wt.-% to 40 wt.-%,

[0062] Triglycerols: 0.01wt.-% to 60wt.-%, preferably 15 wt.-% to 35 wt.-%,

[0063] Tetraglycerols: 0.01wt.-% to 30wt.-%, preferably 5 wt.-% to 20 wt.-%,

[0064] Pentaglycerols: 0.01wt.-% to 20wt.-%, preferably 0.1 wt.-% to 15 wt.-%, and

[0065] Oligoglycerols: ad 100 wt.-%, where the stated percentages by weight refer to the total amount of polyglycerol used. The distribution of polyglycerol can be determined by gas chromatography (GC).

[0066] Preferred saturated or unsaturated, linear or branched fatty acid having 4 to 22 carbon atoms are isostearic acid, oleic acid and / or linolenic acid. Preferred polyfunctional carboxylic acids are selected from oxalic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic acid and / or their anhydrides or esters. Preferred aromatic monocarboxylic acids having 7 to 22 carbon atoms are in particular benzoic acid, phenylethanoic acid, 4- decyloxybenzoic acid, and / or 4-octadecyloxybenzoic acid or anhydrides or esters thereof, with benzoic acid being particularly preferred.

[0067] In a preferred embodiment the polyglycerol partial esters have in particular a polydispersity of at least 2, preferably of at least 5 and particularly preferably of 3.5 to 5. The preferred polydispersity indicates a branched or hyperbranched polymer structure. This branched or hyperbranched polymer structure contributes to the desired properties of the polyglycerol esters as defoamers.

[0068] In another embodiment of the invention the defoamer is a polysiloxane, in particular a polyether-modified polysiloxane, in particular linear polyether-modified polysiloxanes.

[0069] A preferred defoamer is disclosed in EP 2 094 761 A1 . The defoamer disclosed therein is a polyoxyalkylenepolysiloxane block polymers of the general formula (III):

[0070] C2-B1-(A1B1)a-C1

[0071] (formula (III)) in which

[0072] A1is a polyoxyalkylene block of the general formula -(CnH2n O)b -,

[0073] B1is a polysiloxane block of the general formula -(SiRe12-O)c-,

[0074] C1and C2are identical or different alkoxypolyoxyalkylene radicals of the general formula Z1- O-[CH2-CH(Re2)O]d-,

[0075] Re1are identical or different C1-4 alkyl radicals or phenyl radicals, with the proviso that at least 90% of the radicals Ri1are methyl radicals, 202200165 Foreign Filing 8

[0076] Re2are identical or different hydrogen, Ci-i2alkyl radicals or phenyl radicals,

[0077] Z1is an alkyl, alkylene, aryl or alkylaryl radical, a’ is 1 to 20, b’ is an average value from 10 to 130, c’ is 3 to 100, d’ is independently at each occurrence in C1 / C2values from 2 to 20, with the proviso that the average value is situated in the range 2 to < 15, n’ is 2 to 12, with an average numerical value of 2.7 to 4.0.

[0078] Another preferred defoamer is disclosed in EP 2 567 999 A1 and is a linear polyether-modified polysiloxane adhering to general formula (IV):

[0079] B2D1m”B2

[0080] (formula (IV) wherein

[0081] B2is [(CH3)2(A2)SiO-];

[0082] D1is [-(CH3)2SiO-],

[0083] A2is -(CH2)n”-O-(CH2-CH2-O)x2-(CH2-CH(CH3)-O)y2Z2, m” is 3 to 50, preferably 5 to 30, more preferably 10 to 30, n” is 1 to 6, preferably 1 to 6, more preferably 2-4, x2 is 0 to 20, preferably 0 to 10, more preferably 0 to 5 y2 is 2 to 50, preferably 4 to 30, more preferably 4 to 20, and

[0084] Z2comprises hydrogen, or methyl, butyl, or acetyl group, preferably methyl, butyl, or acetyl group, more preferably acetyl group.

[0085] A further preferred defoamer is a polyacrylate with an Mnin the range of 1 000 to 10 000 g / mol comprising the following repeating units:

[0086] (formula (Va)) (formula (Vb)) (formula (Vc)) where

[0087] Rt1is identical or different and is an alkyl radical of 1 to 4 carbon atoms, preferably methyl,

[0088] Rt2is identical or different and is a saturated or unsaturated alkyl radical of 12 to 22 carbon atoms, preferably oleyl,

[0089] Rt3is a hydrocarbon radical which carries at least one (meth)acryloxy group, preferably ethyl acrylate or propyl acrylate a’” is 10 to 50, b’” is 3 to 20, 202200165 Foreign Filing 9 c’” is 0 to 10, preferably 1 to 10.

[0090] Preferably the ratio a”’:(b”’+c”’) is from 0.25 to 4. It is also preferred for the ratio b”’:c”’ to be from 1 :0 to 1 :0.7, more preferably from 1 :0.1 to 1 :0.5. Such polyacrylates are disclosed in EP 0 990 665 A2 and are preferably used as defoamers for radiation-curing powder coatings.

[0091] Yet another preferred defoamer is polybutadiene. The polybutadiene used as a defoamer preferably has a Mnin the range of 800 to 10000 g / mol, more preferably in the range of 1000 to 6000 g / mol, even more preferably in the range of 1400 to 5000 g / mol, most preferably in the range of 1500 to 3000 g / mol.

[0092] Another preferred defoamer is wax, in particular natural wax, silicon wax, polyolefin wax, and mixtures thereof. Preferred polyolefin waxes comprise ethylene and / or propylene repeating units, in particular ethylene and propylene repeating units.

[0093] Surfactant / wetting agent / dispersant

[0094] In an embodiment of the invention the powder coating additive is used to regulate the surface tension (surfactant), e.g. as a wetting agent and / or dispersing additive.

[0095] A preferred surfactant is an acetylenic diol or alkoxylated derivatives thereof, preferably ethylene oxide and / or propylene oxide derivatives thereof.

[0096] Preferred are surfactants as disclosed in US 7,348,300 B2 or EP 3 865 548 A1 . In a preferred embodiment the surfactant is represented by general formula (Via):

[0097] (formula (Via)) where hi and h2 are 1 or 2, preferably 1 , i1 + i2 is 0 to 30, preferably 1 .3 to 30, more preferably 1 .3 to 15, k1 + k2 is 0 to 10, preferably 1 to 10, more preferably 1 to 3, most preferably 2, and with the ethylene oxide and propylene oxide units being distributed along the alkylene oxide chain in blocks or randomly.

[0098] In another preferred embodiment hi and h2 are 1 , k1 + k2 is 0, and i1 + i2 is in the range of 1 to 10, preferably 3 to 10. 202200165 Foreign Filing 10

[0099] In yet another preferred embodiment the surfactant comprises 2,4,7,9-tetramethyl-5-decyne-4,7-diol.

[0100] In a further preferred embodiment the surfactant comprises 2,4,7,9-tetramethyl-5-decyne-4,7-diol and alkoxylated derivatives thereof, preferably ethoxylated derivatives thereof.

[0101] Further preferred acetylenic diol-based surfactants are disclosed in EP 1 333 048 A1 . These surfactants are glycidyl ether-capped acetylenic diols ethoxylates adhering to general formula (lib):

[0102] (formula (VI b)) where

[0103] Rf1is hydrogen or a linear, branched, or cyclic alkyl group having from 1 to about 6 carbon atoms;

[0104] Rf2is a linear, branched, or cyclic alkyl group having from 1 to about 12 carbon atoms;

[0105] Rf3is -CH2ORM;

[0106] Rf4is a linear, branched, or cyclic alkyl, alkenyl, aryl, or aralkyl group having from 2 to about 30 carbon atoms;

[0107] (i3 +i4) is an average value from about 1 to about 100; and

[0108] (k3 + k4) is an average value from about 0.5 to about 5.

[0109] Rf1is preferably a methyl group. Rf2is preferably a linear or branched alkyl group having from 3 to about 6 carbon atoms, more preferably an isobutyl or isoamyl group, even more preferably isobutyl. Rf3is preferably a linear, branched, or cyclic alkyl, alkenyl, aryl, or aralkyl group having from 3 to about 20 carbon atoms, more preferably a 2-ethylhexyl group. Preferably (i3 +i4) is an average value from 1 .3 to 50, more preferably 10. Preferably (k3 + k4) is an average value from 1 to 3, more preferably 2. Most preferably R12is a methyl group, Rf2is isobutyl, (i3 +i4) is an average value of 10, and (k3 + k4) is an average value of 2.

[0110] Another preferred surfactant are alkane diols, in particular as disclosed in EP 1 297 876 A2 and adhering to general formula (VI I):

[0111] HOR9lR92C-[CH2]n ’-CR9l’R92’OH

[0112] (formula (VII)) where

[0113] Rs1and Rs1are independently selected from the group of alkyl radicals having from 3 to 6 carbon atoms, R92and R02are independently alkyl radicals having from 1 to 2 carbon atoms, and n1 is an integer from 1 to 6. 202200165 Foreign Filing 11

[0114] Preferably Rs1and Rs1are independently selected from the group of alkyl radicals having from 4 to 6 carbon atoms. Rs2and Rs2are preferably methyl. It is preferred for n’” to be in the range of 1 to 4, more preferably 2. In a preferred embodiment Rs1and Rs1are independently selected from the group of alkyl radicals having from 4 to 6 carbon atoms, R02and R02’ are preferably methyl, and n’” is 2. The most preferred compounds according to formula (VII) are 2,4,7,9-tetramethyldecane-4,7-diol and 2,5,8,11- tetramethyldodecane-5,8-diol.

[0115] In yet another preferred embodiment of the invention the surfactant adheres to general formula (VIII) as disclosed in EP 1 657 288 A1 :

[0116] Rh1OCH2CH(OH)CRh2Rh3-Rh5-Rh4(formula (VIII)) where

[0117] Rh1is selected from the group consisting of C3-C30 branched, linear, and cyclic alkyl, alkenyl, aryl, and aralkyl moieties; C3-C30 branched, linear, and cyclic alkyl, alkenyl, aryl, and aralkyl moieties bearing a carbonyl group or one or more heteroatoms selected from O, S, and N; glycol ether moieties of the formula Rh8(OCH2CH2)qi-; aminoethylene moieties of the formula Rh8(NHCH2CH2)qi-; and thioether moieties of the formula Rh8S(CH2)qi-; wherein R5 is H or linear C1-C12 alkyl;

[0118] Rh2and Rh3are each independently selected from the group consisting of H and linear or branched C1-C3 alkyl and alkenyl groups;

[0119] Rh4is selected from the group consisting of C3-C16 linear, cyclic, and branched alkyl, alkenyl, aryl, aralkyl, and alkaryl moieties, and any of these moieties substituted with carboxy, sulfo, or phospho substituents;

[0120] -CH2(CHOH)q2CH2OH;

[0121] -(CH2)2O(CH2)2Rh6;

[0122] -(CH2)q3Rh6; and -CH2CH(OH)CH2(C3H6O)q4O-Rh7(O(C3H6O)q4CH2CHOHCH2Rh6)2; wherein q2 is an integer from 2 to 4, q3 is an integer from 0 to 5, q4 is 1 or 2; q1 is an integer from 1 to 15, Rh6is SH or Rh5CRh2Rh3CH(OH)CH2ORh1, Rh7is a trimethylolpropane- or glycerol-based segment, and Rh5is S, SO, or SO2, provided that Rh5is not S when Rh4is -CH2(CHOH)q3CH2OH.

[0123] In one preferred embodiment Rh5is S. In a different preferred embodiment Rh5is SO or SO2. Preferably Rh2and Rh3are each H. Rh1is preferably a C4-C20 linear alkyl moiety, preferably selected from the group consisting of butyl, 2-ethylhexyl, octyl, decyl, dodecyl, tetradecyl, and mixtures thereof. It is particularly preferred for the compound according to formula (VIII) to comprise at least one thioether group.

[0124] In a further preferred embodiment the surfactant, in particular a wetting agent, is a fatty alcohol alkoxylate. The fatty alcohol preferably comprises 8 to 18 carbon atoms, more preferably 12 to 18 carbon atoms. It is preferred for the fatty alcohol to be branched, in particular 2-position methyl-branched. The fatty alcohol 202200165 Foreign Filing 12 alkoxylate preferably comprises on average 2 to 8 oxyalkylene units. Preferred oxyalkylene units in the fatty alcohol alkoxylate are ethylene oxide, propylene oxide, and / or butylene oxide. These can be present in a random distribution or as block copolymers.

[0125] In another preferred embodiment the surfactant comprises a eugenol-based polyether as disclosed in EP 3 189 093 A1 and EP 3 138 867 A1. Preferably the eugenol-based polyether adheres to general formula (IXa): where a = 1 to 1000, preferably 2 to 500, particularly preferably 3 to 500, more preferably greater than

[0126] 3 to 100, especially preferably 4 to 50, b = 0 to 1000, preferably 1 to 500, more preferably greater than 1 to 200, especially preferably

[0127] 0 to 50, c = 0 to 1000, preferably 1 to 100, more preferably greater than 1 to 80, especially preferably

[0128] 0 to 50, d = 0 to 1000, preferably 1 to 100, more preferably greater than 1 to 80, especially preferably

[0129] 0 to 50, e = 1 to 10, f = 0 to 500, preferably 1 to 300, particularly preferably 2 to 200 and especially preferably 0 to

[0130] 100, with the proviso that the sum of a + b + c + d + f is not less than 3 and with the proviso that the groups with the indices a, b, c, d, and f are freely permutable over the molecule chain and neither of the groups with the indices c and d may follow itself or the respective other group, and with the proviso that the different monomer units and the fragments with the indices a, b and f may be in a blockwise structure with one another, where individual blocks may also occur multiple times and may be randomly distributed among one another, or else are subject to a random distribution and further are freely permutable with one another, in the sense that they may be arranged in any desired sequence, subject to the restriction that neither of the groups with the indices c and d may follow itself or the respective other group, and where 202200165 Foreign Filing 13

[0131] Ri1= independently at each occurrence a hydrogen radical or a Ci-Ca alkyl group, preferably hydrogen, methyl or ethyl, especially preferably hydrogen,

[0132] R'2= independently at each occurrence a hydrogen radical, a C1-C20 alkyl group, an aryl or alkaryl group, preferably hydrogen, methyl, ethyl, octyl, decyl, dodecyl, phenyl, benzyl, more preferably hydrogen, methyl or ethyl, or Ri1and one of the radicals R'2may together form a ring which includes the atoms to which Ri1and Ri2are bonded, this ring preferably comprising 5 to 8 carbon atoms,

[0133] R'3= independently at each occurrence a saturated or unsaturated, aliphatic or aromatic, hydrocarbon radical comprising 2 to 30 carbon atoms, in particular up to 24 carbon atoms, which is optionally further substituted, or a polyoxyalkylene, preferably comprising ethylene oxide and / or propylene oxide units,

[0134] R'4, R'7= independently at each occurrence hydrogen and / or an organic radical, preferably alkyl, alkenyl, alkylidene, alkoxy, aryl and / or aralkyl groups, or else optionally R'4and / or R'7may be absent, where, when R'4and R'7are absent, there is a C=C double bond in place of the radicals R'4and R'7, the bridging fragment Z may be present or absent; when the bridging fragment Z is absent, then

[0135] R'5, R'6= independently at each occurrence hydrogen and / or an organic radical, preferably alkyl, alkenyl, alkylidene, alkoxy, aryl and / or aralkyl groups, where, when one of the radicals R'4or R'7is absent, the respective geminal radical (i.e. R'5when R'4is absent and Ri6when R'7is absent) is an alkylidene radical, preferably methylidene (= CH2); when the bridging fragment Z is present, then

[0136] RI5,Ri6 = hydrocarbon radicals which are bridged cycloaliphatically or aromatically via fragment Z, where Z represents a divalent alkylene or alkenylene radical which may be further substituted,

[0137] R'8, R'9= independently at each occurrence a hydrogen radical, a C1-C20 alkyl group, ary I- or alkaryl-group and / or alkoxy group, preferably a methyl group,

[0138] R'10= independently at each occurence a hydrogen radical or a Ci-Ca alkyl group or an ester group -C(O)-R'11or an acetoacetate group -C(O)-CH2-C(O)-R'12or a silyl ether group -Si(Ri13)3 or a urethane group -C(O)-N-(Ri14)2 or a phosphoric acid group -P(O)-(ORi15)2 with where R'11, R'12, R'13= independently at each occurrence a linear or branched, saturated or unsaturated, optionally further substituted C1-C30 alkyl group, an aryl or alkaryl group, and

[0139] R'14= independently at each occurence hydrogen and / or a linear or branched, saturated or unsaturated, optionally further substituted C1-C30 alkyl group, an aryl or alkaryl group,

[0140] R'15= independently hydrogen, alkyl group or polyether radical, preferably hydrogen, a methyl group, an acetyl group or an acetoacetate group, more preferably hydrogen or an acetyl group, and

[0141] R'16= independently allyl or 2-propenyl group 202200165 Foreign Filing 14

[0142] In a further embodiment the eugenol-based polyether can be used to prepare a eugenol-based polyether- modified polysiloxane. Eugenol-based polyether-modified polysiloxanes are available e.g. by reaction of a SiH-functional polysiloxane with a eugenol-based polyether. Preferred is a eugenol-based polyether- modified polysiloxane as disclosed in EP 3 189 093 A1 and EP 3 138 867 A1 , adhering to general formula (IXb):

[0143] Mm2 M' m3 Dd1 D'd2 D"d3 Tt Qq

[0144] (formula (IXb)) where

[0145] M = [R13SiOi / 2],

[0146] M' = [R2Rj12SiOi / 2],

[0147] D = [R12SiO2 / 2],

[0148] D' = [R2R1SiO2 / 2],

[0149] D" = [R3R1SiO2 / 2],

[0150] T = [R1SiO3 / 2],

[0151] Q = [SiO4 / 2], m2 = 0-20, preferably 0-10, more preferably 2, m3 = 0-20, preferably 0-10, more preferably 0, d1 = 0-1000, preferably 0-500, more preferably 0-200, d2 = 0-20, preferably 1-15, more preferably 1-10, d3 = 0-20, preferably 0-10, more preferably 0, t = 0-20, preferably 0-10, more preferably 0, q = 0-20, preferably 0-15, more preferably 0-10, with the proviso that the sum of m2 + m3 + d1 + d2 + d3 + t + q is not less than 3 and that the sum of m3 + d2 > 1 , and

[0152] Rj1= independently at each occurence identical or different C1-C16 hydrocarbon radicals, H, or OH, wherein the hydrocarbon radical can further comprise a double bond, preferably a vinyl group, an alcohol group, an epoxy group, a carbonic acid, or an amine, preferably methyl, ethyl or phenyl, more preferably methyl,

[0153] R2= independently at each occurence identical or different polyether radicals, with the proviso that at least 10% of the radicals are eugenol-based polyether radicals; preferably the eugenol-based polyether radicals correspond to general formula (IXc) 202200165 Foreign Filing 15

[0154] R4= independently n-propyl or / so-propyl, and preferred non-eugenol-based polyethers correspond to radicals of general formula (IXd), where the indices a-f and the radicals Ri1-Ri1° are as defined above,

[0155] R3= independently at each occurrence identical or different C1-C16 hydrocarbon radicals which also comprise heteroatoms and may be further substituted, preferably concerned are SiC-linked radicals resulting from allyl glycidic ether, glycerol monoallyl ether, allylanisole, eugenol, hexenol, hexadecene and methyl undecylenate, more preferably hexadecene, eugenol and glycerol monoallyl ether.

[0156] Other preferred polyether-modified polysiloxane- based surfactants adhere to general formula (IXe):

[0157] M"m2’ M"'m3’ D"'d1 ’ D""d2’ D d3' T't’ Qq’ (formula (IXe)) where

[0158] M" = [R13SiOi / 2],

[0159] M'" = [R2' Ri2SiOi / 2],

[0160] D'" = [R12SiO2 / 2],

[0161] D"" = [R2' R1 SiO2 / 2],

[0162] D . = [R3’ R1’SiO2 / 2],

[0163] T = [R1SiO3 / 2],

[0164] Q as defined above, m2’ = 0-20, preferably 0-10, more preferably 2, 202200165 Foreign Filing 16 m3’ = 0-20, preferably 0-10, more preferably 0, d1 ’ = 0-1000, preferably 0-500, more preferably 0-200, d2’ = 0-20, preferably 1-15, more preferably 1-10, d3’ = 0-20, preferably 0-10, more preferably 0, t’ = 0-20, preferably 0-10, more preferably 0, most preferably 0 q’ = 0-20, preferably 0-15, more preferably 0-10, most preferably 0 with the proviso that the sum of m2’ + m3’ + d1 ’ + d2’ + d3’ + t’ + q’ is not less than 3, and

[0165] R1= independently at each occurence identical or different C1-C16 hydrocarbon radicals, H, or OH, wherein the hydrocarbon radical can further comprise a double bond, preferably a vinyl group, an alcohol group, an epoxy group, a carbonic acid, or an amine, preferably methyl, ethyl or phenyl, more preferably methyl,

[0166] R2= independently at each occurence identical or different polyether radicals, preferably polyethers correspond to radicals of general formula (IXd), where the indices a-f and the radicals Ri1-Ri1° are as defined above,

[0167] R3’ = independently at each occurrence identical or different C1-C16 hydrocarbon radicals which also comprise heteroatoms and may be further substituted, preferably concerned are SiC-linked radicals resulting from allyl glycidic ether, glycerol monoallyl ether, allylanisole, eugenol, hexenol, hexadecene and methyl undecylenate, more preferably hexadecene, eugenol and glycerol monoallyl ether

[0168] Further preferred dispersants are phospholipids. A preferred phospholipid is lecithin, in particular naturally occurring lecithin, preferably isolated from eggs, soybean oil, legumes, grains, wheat germ, nuts, seeds, fish, and brewer’s yeast. Lecithin isolated from soybean oil is preferred for use with the present invention.

[0169] In a further preferred embodiment of the invention the dispersant as disclosed in EP 1 685 895 A2. The dispersant therein is a resin is obtainable from the full or partial reaction of the following components: 202200165 Foreign Filing

[0170] A) at least one amino-functional polymer,

[0171] B) at least one polyester of general formula (Xa) or (Xb)

[0172] (formula (Xb)

[0173] C) at least one polyether of general formula (Xia) or (XI b)

[0174] (formula (Xia))

[0175] T1

[0176] Rk1 Rk4— Rk3

[0177] (formula (XI b)) where

[0178] Rk1= is a hydrogen and / or a substituted or unsubstituted, linear or branched aryl, arylalkyl, alkyl or alkenyl radical having 1 to 24 carbon atoms,

[0179] Rk2= at least one divalent radical selected from the group of linear, branched, cyclic, and aromatic hydrocarbons,

[0180] Rk3= at least one radical selected from the group of sulfonic acids, sulfuric acids, phosphonic acids, phosphoric acids, carboxylic acids, isocyanates, epoxides, particularly epoxides of phosphoric acid and / or (meth)acrylic acid,

[0181] Rk4= is a divalent polyether radical of general formula -[(EO)si(PO)s2(BO)s3(SO)S4]- comprising ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and / or styrene oxide (SO), where s1 , s2 and s3 independently of one another are values from 0 to 100, with the proviso that the sum of s1 + s2 + s3 > 0, preferably 5 to 35, in particular 10 to 20, with the proviso that the sum of s1 + s2 + s3 + s4 > 0, s4 > 0, preferably 1 to 5, r1 and r2 independently of one another are > 2.

[0182] The at least one amino-functional polymer of component A) is preferably selected from the group consisting of amino-functional polyamino acids, amino-functional silicones, polyamidoamines, polyallylamines and 202200165 Foreign Filing poly(N-alkyl)allylamines, polyvinylamines, and polyalkyleneimines. In a further preferred embodiment the amino-functional polymer is crosslinked by reaction of some of the amino groups with one or more polyfunctional compounds selected from the group of isocyanates, carboxylic acids, (meth)acrylates, and epoxides. Preferably the amino-functional polymer has an average molecular weight of 400 g / mol to 600 000 g / mol.

[0183] The at least one polyester of component B) is preferably obtained by ring-opening polymerization of one or more lactones selected from the group of B-propiolactone, B-butyrolactone, y-butyrolactone, 3,6-dimethyl- 1 ,4-dioxane-2, 5-dione, 6-valerolactone, y-valerolactone, e-caprolactone, y-caprolactone, 4- methylcaprolactone, 2-methyl- caprolactone, 5-hydroxydodecanolactone, 12-hydroxydodecanolactone, 12- hydroxy-9-octa-decenoic acid, 12-hydroxyoctadecanoic acid. The polyester preferably has an average molecular weight Mnof 100 to 5000 g / mol, more preferably 200 to 2000 g / mol.

[0184] In such a resin the weight ratio of component B) to component C) is preferably in the range of 50:1 to 1 :9, more preferably 40:1 to 1 :5, most preferably 30:1 and 1 :1 .

[0185] A further preferred dispersant is disclosed in EP 2 418 234 A1 , which is a compound that is liquid at a temperature of 20°C and a pressure of 101325 Pa and of the general formula (XII):

[0186] [Rl-O(SO)tl (EO)t2(PO)t3(BO)t4]u1 -[PO-(ORl6)3-ul]u2-Rl5u3

[0187] (formula (XII)) where

[0188] R11= bond to the unit -O(SO)ti(EO)t2(CH2CHCH3O)t3(BO)t4-,

[0189] R12= identically or differently, H or -O(SO)ti(EO)t2(CH2CHCH3O)t3(BO)t4-[PO-(OH)2-ui (Rl5)ui ]u2- Rl4u3’,

[0190] R13= identically or differently, saturated or unsaturated aliphatic hydrocarbon radical having 15 carbon atoms and 25 to 31 hydrogen atoms,

[0191] R14= identically or differently, H, M+or alkyl having 1 to 4 C atoms,

[0192] R15= organic radical,

[0193] R16= identically or differently H or M+,

[0194] M+= metal or semi-metal cation or ammonium, preferably a silicon, an aluminium, an alkali metal or alkaline earth metal cation, t1 = 0 to 3, preferably 0, 1 or 2, more preferably 0 or 1 , t2 = 0 to 100, preferably at least 1 , more preferably 1 to 20, very preferably 6 to 12, t3 = 0 to 20, preferably 0 or 1 to 5, t4 = 0 to 3, preferably 0 or 2 or 3, 202200165 Foreign Filing 19 u1 = 1 to 3, preferably 1 or 2, more preferably 1 , u2 = 0 or 1 , preferably 1 , u3 = 0 or 1 , preferably 0, u1' = 0 to 2, preferably 0, u2' = 0 or 1 , preferably 0, u3' = 0 or 1 , preferably 1 , with SO being styrene oxide, EO being ethylene oxide, PO being propylene oxide, BO being butylene oxide, and with the provisos that u2 + u3 is = 1 , that when u3 = 1 , also u1 is = 1 , that u2' + u3' = 1 , that when u3' = 1 , also u1 ' is = 1 , that when t1 , t3 and t4 are = 0, t2 is from 1 to 12, preferably from 6 to 10, that when t3 or t4 is other than 0, one of the other indices t1 to t4 is likewise other than 0, and that the sum t1 + t2 + t3 + t4 (per unit -O(SO)ti(EO)t2PO)t3(BO)t4- present) is greater than 3.

[0195] In a preferred embodiment the compound according to formula (XII) R12is H, u2 is 1 and u3 is 0. It is further preferred for the units denoted with t1 , t2, t3 and / or t4 to be arrange blockwise. In a further preferred embodiment, the compound according to formula (XII) is derived from decarboxylated anacardic acid, a mixture of (Z,Z)-6-(pentadecanyl)salicylic acids. Particularly preferred compounds of the formula (XII) are those in which, of the radicals R13, 35 to 45 mol%, preferably approximately 42 mol%, are triply unsaturated, 30 to 40 mol%, preferably approximately 34 mol%, are doubly unsaturated, 15 to 25 mol%, preferably approximately 22 mol%, are singly unsaturated, and 0 to 5 mol%, preferably approximately 2 mol%, are saturated. Particularly preferred compounds of the formula (IX) are those in which t2 is other than 0, preferably 6 to 20, more preferably 6 to 12.

[0196] Particularly preferred compounds are those which, counting from cardanol radical R1as starting alcohol, have first an ethylene oxide block, then a propylene oxide block and finally an ethylene oxide block again, with preference being given to those compounds in which the ethylene blocks have in each case from 3 to 8, preferably 6, ethylene oxide units and the propylene oxide block has from 2 to 4, preferably 2, propylene oxide units. In the case of these preferred compounds of the formula (XII), it is additionally preferred if the radical R12is a hydrogen.

[0197] In a further preferred embodiment the dispersant is a phosphoric acid ester according to general formula (X):

[0198] (HO)3-vi-P(O)-[O(CwiH2wiO)v2-Rm1]vi

[0199] (formula (XIII)) where

[0200] Rm1= v1 = 1 or 2, 202200165 Foreign Filing 20 w1 = 2 to 18, v2 = 2 to 100, v3 = 2 to 100,

[0201] Rm2= H, or a linear or branched alkyl residue, which can optionally be substituted with at least one functional group, preferably H,

[0202] Rm3 = alkyl-, alkaryl-, alkenyl- or sulfopropyl-residue.

[0203] For compounds adhering to formula (XIII) it is preferred for the ratio of v2 / v3 to be in the range of 1 :10 to 10:1 , more preferably 1 :2 to 10:1. A compound according to formula (XIII) preferably has an molecular weight of 300 to 15 000 g / mol, more preferably 500 to 500 g / mol.

[0204] A further preferred dispersant is disclosed in EP 3 122 447 A1 . The dispersant disclosed therein is a resin, including salts thereof, comprising the following radicals:

[0205] D) a polyester based on dicarboxylic or polycarboxylic acids and diols or polyols,

[0206] E) a basic group or a radical comprising a basic group,

[0207] F) a terminal radical which ends polymerization.

[0208] Preferably the dicarboxylic or polycarboxylic acids are selected from phthalic acid, isophthalic acid, terephthalic acid, 1 ,2-cyclohexanedicarboxylic acid and isomers, succinic acid, sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, glutaric acid, citraconic acid, fumaric acid, itaconic acid, maleic acid, mesaconic acid, azelaic acid, pyromellitic acid and / or trimellitic acid, their acid anhydrides and / or low molecular mass alkyl esters. It is also preferred that the diols or polyols are selected from ethylene glycol, 1 ,2- and / or 1 ,3-propanediol, diethylene, dipropylene, triethylene and tetraethylene glycol, 1 ,2- and / or 1 ,4- butanediol, 1 ,3-butylethylpropanediol, 1 ,3-methylpropanediol, 1 ,5-pentanediol, cyclohexanedimethanol, Dicidol, glycerol, 1 ,6-hexanediol, neopentyl glycol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, norbornylene glycol, 1 ,4-benzyldimethanol, 1 ,4-benzyldiethanol and / or 2,4-dimethyl-2-ethylhexane-1 ,3- diol. Component E) is preferably polyallylamine or poly(C2-C4-alkenylamine).

[0209] Preferably the polyesters of component D) have an Mnof 700 to 10000 g / mol and an Mw of 1500 to 40000 g / mol. The preferred average molecular weight Mw of component E) is between 200 and 600000 g / mol. The weight ratio between component D) and component E) is preferably in the range of 30:1 to 1 :1 , more preferably 20:1 to 2:1 , most preferably 15:1 to 4:1.

[0210] A further preferred dispersant is disclosed in EP 3 222 650 A1 and is based on polyamines or polyimines (G) containing side chains based on two or more poly(oxy-Ci-6-alkylenecarbonyl) compounds (H) and side chains based on alkyl acids (J). Such a dispersant has a preferred acid number of < 10 mg KOH / g, preferably < 5 mg KOH / g. The preferred ratio of acid number to amine number is > 10, preferably > 20.

[0211] Preferably the poly(oxy-Ci-6-alkylenecarbonyl) compounds (H) are homopolymers but have different chain lengths. It is further preferred for the poly(oxy-Ci-6-alkylenecarbonyl) compounds (H) to be 6-valerolactone or e-caprolactone. 202200165 Foreign Filing 21

[0212] The alkyl acids (J) are preferably selected from the group of acetic, methoxyacetic acid, propionic acid, pentanoic acid, hexanoic acid, caprylic acid, capric acid, lauric acid, ricinoleic acid, stearic acid and hydroxystearic acid.

[0213] Preferably the polyimine (G) is a polyethyleneimine. The preferred average molecular weight Mwof the polyethyleneimine is between 200 and 600000 g / mol, preferably between 400 and 100000 g / mol, more preferably between 600 and 30000 g / mol.

[0214] It is further preferred for the sum total of poly(oxy-Ci-6-alkylenecarbonyl) compounds (H) and alkyl acids (J) to primary amino groups of the polyamines or polyimines is less than 1 , preferably less than 0.9. Preferably the molar ratio between the two or more different poly(oxy-Ci-6-alkylenecarbonyl) chains (H) and the alkyl acids (J) is between 90:10 and 10:90, preferably between (H) and (J) 80:20 and 20:80 and more preferably between 70:30 and 30:70.

[0215] In yet another preferred embodiment the dispersant is a triglyceride, more preferably an alkoxylated triglyceride. The alkoxylated triglyceride preferably comprises an average of 10 to 100, more preferably 20 to 80, most preferably 30 to 60, oxyalkylene repeating units. Preferably the alkoxylated triglyceride is alkoxylated with at least ethylene oxide, more preferably only ethylene oxide. The glyceride in the alkoxylated glyceride is preferably castor oil. The alkoxylated triglyceride is preferably an ethoxylated triglyceride.

[0216] In yet another embodiment the dispersant is a maleic acid anhydride-copolymer comprising amine oxide groups, preferably as disclosed in EP 1 026 178 A1. The maleic anhydride-copolymers containing amine oxide groups disclosed therein are obtainable by reacting at least 1 mol% of the anhydride groups of maleic anhydride copolymers with diamines from the group consisting of

[0217] HRs1N-Rs2-NRs3Rs4where

[0218] Rs1is hydrogen or a monovalent hydrocarbon radical having 1 to 24 carbon atoms,

[0219] Rs2is a divalent alkylene radical having 2 to 24 carbon atoms, and

[0220] Rs3and Rs4are aliphatic and / or alicyclic alkyl radicals having 1 to 12, preferably 1 to 6, carbon atoms, which can be identical or different, and subsequently carrying out oxidation to give amine oxide groups of the following general formula 202200165 Foreign Filing 22

[0221] The maleic acid anhydride-copolymer preferably comprises at least one further comonomer with a vinylic double bonds, preferably a monomer selected from the group consisting of styrene, alkylated styrene compounds, (meth)acrylic acid, (meth) acrylic esters, alkyl vinyl ethers, vinyl acetate, and itaconic esters or mixtures of monomers from this group. The most preferred comonomer is styrene.

[0222] The maleic acid anhydride-copolymer preferably has a Mwof from 1000 to 100,000, preferably from 2500 to 50,000, g / mol. It is further preferred for the carboxylic acid groups present in the polymer to have been neutralized to carboxylate salts.

[0223] Catalyst

[0224] In an embodiment a powder coating additive is a catalyst, e.g. a curing or crosslinking catalyst (used synonymously). Preferred catalysts are disclosed in EP 3 036 296 A1 .

[0225] In a preferred embodiment the catalyst contains no silicon atoms. The preferred catalyst is selected from the group of titanates, nitrogen-containing compounds, and mixtures thereof. A particularly preferred titanate is tetra-n-butoxytitanate (TnBT). Particularly preferred nitrogen-containing compounds are guanidines and amidines. Preferably the catalyst is selected from the group consisting of TnBT, 1 , 1 ,3,3- tetramethylguanidine (TMG) and 1 ,8-diazabicyclo[5.4.0]-7-undecene (DBU), and mixtures thereof. Particularly preferred mixtures comprise DBU as well as TMG or TnBT. Such catalysts are particularly suitable for powder coating compositions comprising at least one alkoxysilane, as well as alkoxy-functional arylpolysiloxanes and / or alkoxy-functional aryl-alkylpolysiloxanes, preferably alkoxy-functional phenylpolysiloxanes and / or alkoxy-functional phenylmethylpolysiloxanes. This applies in particular where the weight fraction of the alkoxy groups is at least 10 wt.-% based one the sum of the at least one alkoxysilane and the alkoxy-functional arylpolysiloxanes and / or alkoxy-functional aryl-alkylpolysiloxanes.

[0226] Further preferred catalysts are polymeric guanidine-group-containing compounds, in particular those disclosed in EP 3 143 066 A1 comprising the structural element according to to general formula (XIV): 202200165 Foreign Filing 23

[0227] (formula (XIV)) at least in one comb position, where Rn1, Rn2, Rn3, and Rn4, independently of one another, are a linear, cyclic or branched, aliphatic saturated or unsaturated hydrocarbon radical having 1 up to 30 carbon atoms, or an aromatic hydrocarbon radical having 6 up to 30 carbon atoms, which can also contain heteroatoms.

[0228] Yet another preferred catalyst comprises the guanidine-modified siloxane disclosed in EP 2 849 987 A1 , which adhere to general formula (XV):

[0229] M . m4MGm5D . d4DGd5T't”Qq”

[0230] (formula (XV)) where

[0231] M = [R°3SiOi / 2]

[0232] MG= [RGR°2SiOi / 2],

[0233] D = [R°2SiO2 / 2],

[0234] DG= [RG2SiO2 / 2],

[0235] T = [R°SiO3 / 2],

[0236] Q = [SiO4 / 2],

[0237] R° = are, independently of one another, identical or different and are ORoagroups and / or linear or branched, saturated or else mono- or polyunsaturated hydrocarbon radicals, which may be interrupted by heteroatoms and / or may be substituted one or more times by hydroxyl, amino, carboxyl or aryl radicals, preferably being substituted by amino radicals,

[0238] Roais identical or different and is hydrogen and / or alkyl groups having 1 to 12 carbon atoms,

[0239] RGis a radical containing guanidine groups and of the formula (XVIa) or (XVIb), the tautomers and / or salts thereof,

[0240] (formula (XVIa)) (formula (XVIb)) 202200165 Foreign Filing 24

[0241] R°1are divalent radicals which, independently of one another, are identical or different, linear or branched hydrocarbon radicals containing 1 to 50 carbon atoms, and may be interrupted by heteroatoms, preferred heteroatoms being oxygen, nitrogen or sulphur, and / or which may be substituted one or more times by hydroxyl or amino radicals,

[0242] R°2, R°3, R°4, and R°5are, independently of one another, identical or different and are hydrogen, linear or branched or cyclic hydrocarbons containing 1 to 15 carbon atoms, it being possible for the hydrocarbons also to contain 1 or 2 heteroatoms, preferred heteroatoms being nitrogen, oxygen and silicon with m4 = 0 to 10, m5 = 0 to 10, d4 = 0 to 350, d5 = 0 to 50, t” = 0 to 50, q” = O to 10, where the sum of the indices m5 and d4 is greater than or equal to 1 to 20.

[0243] Adhesion promoter

[0244] In one embodiment the adhesion promoter comprises a polyester resin. A preferred adhesion promoter comprising a polyester resin is disclosed in EP 2 853 551 A1 . Polyester resin powder coating additives are preferably based on at least one unsaturated dicarboxylic or polycarboxylic acids and alkoxylated diol or polyol. Preferably these polyester resins do not contain bisphenol A, B, C, F or derivatives thereof.

[0245] In a preferred embodiment the unsaturated dicarboxylic or polycarboxylic acid is citraconic, fumaric, itaconic, maleic and / or mesaconic acid. It is further preferred that that besides the unsaturated dicarboxylic or polycarboxylic acids, aromatic and / or aliphatic and / or cycloaliphatic monocarboxylic, dicarboxylic, polycarboxylic acids and / or phosphoric acids are included.

[0246] In a further preferred embodiment the alkoxylated diol or polyol is based on linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols or polyols, more preferably linear and / or branched, aliphatic and / or cycloaliphatic diols or polyols.

[0247] Preferably the molar ratio of the alkoxylated diol or polyol to the dicarboxylic or polycarboxylic acids is 0.5- 2:1 . The preferred polyesters have an acid number, determined according to DIN EN ISO 2114, of between 1 and 150 mg KOH / g and / or an OH number, determined according to DIN 53240-2, of between 1 and 200 mg KOH / g.

[0248] It is further preferred to use as alkoxylated diol or polyol, the ethoxylated or propoxylated tricyclodecanedimethanol of the isomeric compounds 3,8-bis(hydroxymethyl)tricyclo[5.2.1 .026]decane, 4,8-bis(hydroxymethyl)tricyclo[5.2.1 .026]decane and 5,8-bis(hydroxymethyl)tricyclo[5.2.1 .026]decane is 202200165 Foreign Filing 25 used, and as dicarboxylic or polycarboxylic acids, a mixture of fumaric acid and / or maleic acid and adipic acid. It was found that such polyester resin are particularly good adhesion-promoting additives.

[0249] Further preferred adhesion promoters comprise at least one group able to react with the substrate surface, preferably a silane, more preferably an alkoxysilane, even more preferably a trialkoxy silane, as well as at least one group that can react with the binder, preferably an amine or epoxide.

[0250] In a preferred embodiment the adhesion promoters comprise at least one group able to react with the substrate surface as well as at least one group that can react with the binder adheres to general formula (XI Va):

[0251] (Rp1O)3Si-(CH2)ai-(NHCH2CH2)a2-NH2

[0252] (formula (XVI la)) where

[0253] Rp1= linear or branched alkyl residue, preferably methyl or ethyl, more preferably methyl, a1 = 2-6, preferably 3, a2 = 0-4, preferably 0-1 , more preferably 1 .

[0254] Preferred adhesion promoters according to formula (XlVa) are N-(2-aminoethyl)-3-aminopropyl- trimethoxysilane, (3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-triethoxysilane, (3- aminopropyl)triethoxysilane, or mixtures thereof, more preferably N-(2-aminoethyl)-3-aminopropyl- trimethoxysilane or N-(2-aminoethyl)-3-aminopropyl-triethoxysilane, most preferably, N-(2-aminoethyl)-3- aminopropyl-tri methoxysilane.

[0255] In yet another preferred embodiment the adhesion promoters comprise at least one group able to react with the substrate surface as well as at least one group that can react with the binder adheres to general formula (XI Vb):

[0256] (Rp2O)3Si-(CH2)bi-(OCH2CH2)b2-OCH2CH(O)CH2

[0257] (formula (XVIIb)) where

[0258] Rp2= linear or branched alkyl residue, preferably methyl or ethyl, more preferably methyl, b1 = 2-6, preferably 3, b2 = 0-4, preferably 0-1 , more preferably 0.

[0259] Preferred adhesion promoters according to formula (XlVb) are (3-glycidyloxypropyl)trimethoxysilane and (3-glycidyloxypropyl)triethoxysilane, more preferably (3-glycidyloxypropyl)trimethoxysilane.

[0260] Further preferred adhesion promoters are based on polybutadiene. 202200165 Foreign Filing 26

[0261] One particularly preferred adhesion promoter based on polybutadiene is disclosed in EP 4 095 164 A1 and EP 4 095 164 A1 , which has at least one repeat unit selecting from the group consisting of divalent radicals wherein

[0262] Rq1is in each case independently a monovalent organic radical or a hydrogen radical, preferably in each case independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 6 carbon atoms, more preferably in each case independently selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms;

[0263] Rq2is in each case independently selected from the group consisting of radicals of the formula (XVI 11 a)

[0264] (formula (XVIIIa)), preferably in each case independently selected from the group consisting of radicals of the formula (XVIIIb)

[0265] (formula (XVIIIb)), more preferably in each case independently selected from the group consisting of radicals of the formula (XVI He)

[0266] Rq3is in each case independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 16 carbon atoms, 202200165 Foreign Filing 27 preferably in each case independently an alkyl radical having 1 to 16 carbon atoms or a phenyl radical, more preferably in each case independently a methyl radical, an ethyl radical or a phenyl radical; Rq4is a radical of the formula -CH2-O-Rq5;

[0267] Rq5is in each case independently selected from the group consisting of monovalent hydrocarbon radicals having 3 to 18 carbon atoms; preferably each independently an allyl radical, a butyl radical, an alkyl radical having 8 to 15 carbon atoms or a phenyl radical that may be substituted by monovalent radicals selected from hydrocarbon radicals having 1 to 4 carbon atoms; more preferably a tert-butylphenyl radical or an o-cresyl radical;

[0268] Rq6is each independently a monovalent organic radical having 1 to 18 carbon atoms or hydrogen, preferably hydrogen; and c1 , c2, c3, c4 and c5 are each independently 0 to 300, preferably 0 to 200, more preferably 0 to 100, with the proviso that the sum total of m, n, o, p and q is greater than 1 , preferably greater than 5, more preferably greater than 10; preferably the radical Rq2has at least one propylene oxide unit.

[0269] In this embodiment the number-average molar mass Mnof the polybutadiene moiety is preferably from 200 g / mol to 20 000 g / mol, preferably from 500 g / mol to 10 000 g / mol, more preferably from 700 g / mol to 5000 g / mol.

[0270] The number-average molar mass of the radical Rq2is preferably from 100 g / mol to 10 000 g / mol, preferably from 200 g / mol to 7500 g / mol, more preferably from 400 g / mol to 5000 g / mol.

[0271] It is preferred for c1 , c2, c3, c4 and c5 to each be independently 0 to 100, preferably 0 to 70, more preferably 0 to 50.

[0272] In one embodiment Rq6forms an ester with polyether moiety in Rq2. Such an ester is preferably obtainable from the reaction of the polyether Rq2with cyclic anhydrides, lactones, dilactides or cyclic carbonates. Preferably the cyclic anhydrides are selected from the group consisting of saturated, unsaturated or aromatic cyclic dicarboxylic anhydrides, preferably succinic anhydride, oct(en)yl-, dec(en)yl- and dodec(en)ylsuccinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, trimellitic anhydride, phthalic anhydride, hexahydro-, tetrahydro-, dihydro-, methylhexahydro- and methyltetrahydrophthalic anhydride. The lactones are preferably selected from selected from the group consisting of valerolactones, caprolactones and butyrolactones, which may be unsubstituted or substituted by organic radicals, preferably methyl groups, preferably e-caprolactone or 6- valerolactone.

[0273] Effect agent

[0274] A preferred effect agent is a polydimethylsiloxane, in particular a linear polydimethylsiloxane, with 3 to 100 dimethylsiloxane units with a,w-modifications, which are organic alcohols. Preferably the a,w-alcohol 202200165 Foreign Filing 28 modifications comprise 1 to 8 carbon atoms, more preferably 2 to 5 carbon atoms, most preferably are n- propanolyl groups. This effect agent can be used to enhance the easy-to-clean effect, in particular in combination with a polyurethane binder.

[0275] Unless mentioned otherwise acid numbers mentioned herein are determined according to DIN EN ISO 2114, OH number are determined according to DIN 53240-2, and average molecular weights are determined using gel permeation chromatography as described in ISO 16014:2019. Unless mentioned otherwise, “average molecular weight” refers to Mn.

[0276] Powder coatings

[0277] In another aspect the invention relates to the foamed micro-porous thermoplastic polymer, preferably as a carrier for a powder coating additive in an additive composition according to any of the previous claims, for powder coatings.

[0278] In a further aspect the invention pertains to a powder coating composition comprising a binder and the aforementioned additive composition.

[0279] The binder can be a thermosetting polymer or a thermoplastic polymer, preferably a thermosetting polymer. Preferably the binder is selected from the group consisting of epoxy resin, epoxy resin-polyester hybrid system, reactive polyester, reactive (meth)acrylate, reactive silicone, fluoroethylene vinylether, ketone resin, polyamide, polyethylene, polyvinyl chloride, polyvinylidene chloride, phenolic resin, more preferably from the group consisting of epoxy resin, epoxy resin-polyester hybrid system, reactive polyester, reactive (meth)acrylate. The term (meth)acrylate means that both methacrylate and acrylate derivates are comprised.

[0280] It was found to be preferable for the process when the binder has a glass transition temperature above 45°C. The glass transition temperature can be determined with DSC according to ISO 11357-2:2020.

[0281] The powder coating composition can further comprise a hardener, a filler, and / or a pigment.

[0282] Hardeners are used in case the binder is a thermosetting polymer. Preferred hardeners are phenols, dicyanamides, in particular dicyanamide, polyepoxide, in particular triglycidyl isocyanurate, hydroxyalkylamides, in particular p-hydroxyalkylamides, polycarboxylic acids, in particular dodecanedioic acid. How to choose suitable combinations of hardener and binder is commonly known in the art.

[0283] Preferred fillers are inorganic fillers, preferably selected from the group consisting of calcium silicates magnesium silicates, aluminum silicates, calcium silicates, zinc oxide, quartz, calcium carbonate, barium sulfate, calcium sulfate, aluminum oxide and combinations thereof.

[0284] Pigments can be organic or inorganic. Preferred organic pigments or colorants are azo- and / or diazo-dyes, phthalocyanines, dioxazines. Preferred inorganic pigments are carbon black, titanium dioxide, iron oxide, chromium oxide. 202200165 Foreign Filing 29

[0285] In another aspect the invention further pertains to a process for the preparation of these powder coatings, the process comprising the following steps:

[0286] (1) providing a binder and an additive composition,

[0287] (2) mixing the components of step (1) by extrusion,

[0288] (3) micronizing the composition obtained in step (2),

[0289] (4) optionally sieving the composition obtained in step (3).

[0290] Preferably the extrusion is carried above the melting temperature of the binder, but below the melting temperature of the matrix polymer. This way the additive composition is thoroughly mixed throughout the powder coating composition, but the coating additive only released when the composition is already applied to the substrate.

[0291] The invention relates in yet another aspect to a process for the preparation of a coated substrate, wherein the powder coating composition as described above is applied to a substrate by powder coating (5). A preferred method of powder coating is static spraying. In a subsequent step, the powder coating composition can be cured, preferably by heating or UV irradiation, if the binder is a thermosetting polymer (6a), or melting the composition if the binder is a thermoplastic polymer (6b). Optionally, a further coating can be applied (7) by repeating step (5), followed by either step (6a) or (6b). When step (7) is carried out, it was found to be preferable if the binder in the first coating is an epoxy-resin and the binder in the second coating is a polyester resin.

[0292] The examples adduced hereinafter describe the present invention by way of example, without any intention that the invention, the scope of application of which is apparent from the entirety of the description and the claims, be restricted to the embodiments specified in the examples.

[0293] Examples

[0294] General procedures

[0295] 1 . Manufacturing of additive compositions

[0296] The inventive additive compositions were prepared by combining the carrier with the powder coating additive and mixing for a period of 24-36h until the powder coating additive has penetrated the carrier and the additive composition appears dry. A drum mixer was used for mixing.

[0297] 2. Manufacturing of a powder coating composition

[0298] A premix was prepared by weighing out the raw materials into a plastic bag and shaking of the plastic bag until the mixture appears homogeneous. Subsequently this premix was extruded using a twin-screw extruder set for a temperature of 90°C and a screw speed of 300 rpm and dosing the premix at a utilization rate of up to 30% of the extruder. The extruded material is cooled to room temperature and milled using an ultra-centrifugal mill at 18000 rpm in combination with a cyclone. The resulting powder was sieved with a vibratory sieve shaker to obtain particles with a size less than 100 pm. 202200165 Foreign Filing 30

[0299] 3. Corona spray application and curing

[0300] The powder coating is spray applied by corona method onto cold-rolled steel panels, which have a nontreated surface. The particles are sprayed and charged by a funnel handgun with a pre-set application program which is designed for panels and flat parts. The average dry-film thickness is between 80-85 pm, as determined by coating thickness gauge.

[0301] After the application the panels are cured in a convection oven at a set temperature of 182°C. The curing condition is 15 minutes at an object temperature of 180°C.

[0302] 4. Test methods

[0303] The adhesion is tested via cross-cut in according to ISO 2409. Substrates for this test are cold-rolled steel panels, which are non-treated on the surface with a smooth finish.

[0304] Corrosion protection properties are tested in a constant salt spray test for up to 1440h stress. The test procedure is in according to DIN EN ISO 12944. The substrates for this test are cold-rolled steel panels, which are non-treated with a ground finish.

[0305] The impact on the appearance of the coating is tested via gloss and color measurement. The substrates used for this test are cold-rolled steel, which are non-treated with a smooth finish. The gloss measurement is tested in according to ISO 2813. For color measurement the L*a*b values measured via spectrophotometer are compared.

[0306] The extrusion behaviour was tested using the setup described above with a temperature range of 50 to 115°C. The extrusion behaviour is evaluated to the following grades:

[0307] +++ : The extruded material was homogeneous, exited the extruder at a constant flow rate, had a fluid consistency with a low viscosity similar to yoghurt

[0308] ++ : The extruded material had a less homogenous texture, exited in a variable flow rate and the formation of strings was observed

[0309] + : Inbetween ++ and -

[0310] - : Extrusion occurred in a stop and flow, the extruded materials exited the extruder as brittle material with lumps.

[0311] The slip was determined according to the method outlined in Figure 1 c of ASTM D 1894 on an Instron 3300 series universal testing system using a 200g measuring weight with a diameter of 4 cm at a velocity of 300 mm / min.

[0312] Example 1 : Addition of Inventive Coating Additive

[0313] Example 1 is a comparison of coated substrates made with powder compositions wherein a liquid at room temperature adhesion promoter (adhesion promoter 1) as disclosed in EP 2 853 551 A1 is either absent or incorporated as an additive composition according to the invention. Using the liquid additive without the 202200165 Foreign Filing 31 carrier according to the invention would lead to severe problems during extrusion of the mixture such that extrusion would become impossible. The inventive coating additive composition (ICA1) was manufactured as described above using 30 wt.-% adhesion promoter 1 and 70 wt.-% of a polybutylene(adipate-co- terephthalate)-based carrier (Accurel® XP 950 B, Evonik). The formulations of the tested compositions are described in Table 1 .

[0314] Table 1 : Test formulations with and without the inventive additive composition

[0315] It was found that the processing of comparative example 1 (CE1) and inventive example 1 (IE1) showed no difference, thereby proving that a liquid additive can be added to the coating composition by means of a carrier according to the invention. Results of the salt spray test after 860h are shown in Figure 1 : In the comparative example (Fig. 1A), the salt spray had infiltrated the substrate by 5 mm and the coating was substantially removed. Meanwhile, in the inventive example (Fig. 1 B), the coating remained largely intact, and the infiltration of the substrate was 1 mm.

[0316] By way of the inventive coating additive composition, liquid additives can therefore be introduced into coating compositions without negatively impacting the manufacturing process of the coating composition, while also facilitating a substantial release of the additive during curing of the coating - thereby leading to improved bonding in this specific example, as evidenced by the salt spray test.

[0317] 202200165 Foreign Filing 32

[0318] Example 2: Comparisons of inventive carrier with other carriers

[0319] The Examples are based on the formulation shown in Table 2:

[0320] Table 2: Test formulation for the comparison of inventive carriers with silica carriers

[0321] The inventive coating additive compositions (ICA) and comparative coating additive compositions are shown in Table 3. Slip and anti-crater agents 1 and 2 are according to the disclosure of EP 3 898 850 A1 . For the inventive examples Accurel® XP 950 B (Evonik) was used as the thermoplastic matrix polymer carrier, whereas for the comparative examples SIPERNAT® 22 S was as silica carrier, and DEUREX® H 7320 M (hybrid wax containing carnauba wax type 3 and Fischer-Tropsch waxes; drop point according to

[0322] ASTM D 3954 between 95°C and 105°C) and DEUREX® E 0920 M (micronized polyethylene wax; drop point according to ASTM D 3954 between 104°C and 118°C) were used as wax carriers.

[0323] Table 3: Coating additive compositions used for the comparison of inventive carriers with silica carriers 202200165 Foreign Filing 33

[0324] Adhesion promoter

[0325] An excerpt of photographs of IE2 and CE2a are shown in Figure 2 and measured properties listed in Table 4a:

[0326] Table 4a: Results of test methods of inventive example 2 (IE2) and comparative example 2a (CE2a)

[0327] The inventive coating additive composition leads to a superior behaviour during extrusion. The inventive and non-inventive powder coating additives comprising an adhesion additive both lead to good bonding, as evidenced by the cross cut test. The coating comprising a silica carrier, however, exhibits a much more structured surface as well as pinholes due to worse degassing behavior (cf. Figs. 2A and 2B, as well as zoomed in portions of the sections, highlighted with a dashed box, shown in Figs. 2C and 2D). In summary, the coating obtained using a coating additive composition according to the invention leads to a superior coating in terms of gloss, leveling, and degassing compared to when a silica carrier is used.

[0328] A comparison of the influence of the inventive carrier material to waxes used in the state of the art are shown in Table 4b:

[0329] Table 4b: Results of test methods of inventive example 2 (IE2) and comparative examples 2b (CE2b) and

[0330] 2c (CE2c)

[0331] Again, inventive coating additive composition leads to a superior behaviour during extrusion. Moreover, loading of the wax carriers with adhesion promoter 1 leads a sticky mixture, hence the coating additive composition could not comprise more than 35 wt.-% of adhesion promoter 1 . The inventive and non- inventive powder coating additives comprising an adhesion additive both lead to good bonding, as evidenced by the cross cut test. The compatibility of the wax carrier is however worse. Notably, wax carriers lead to a significant visible yellow-shift, as represented by color strength b*. In summary, the inventive 202200165 Foreign Filing 34 coating additive composition is easier to handle, leads to a coating with a higher gloss and now colour shift, unlike when a wax carrier is used.

[0332] Slip and anti-crater agent

[0333] An excerpt of photographs of IE3 and CE3 are shown in Figure 3 and measured properties listed in Table 5:

[0334] Table 5: Results of test methods of inventive example 3 (IE3) and comparative example 3 (CE3)

[0335] During extrusion, the coating additive composition according to the invention exhibited a superior performance. While both compositions performed similarly with regard to the cross cut test and gloss at medium angle, the inventive coating additive composition outperformed the comparative composition with respect to gloss at a low angle and drastically outperformed with respect to compatibility and leveling. The latter can also be seen in Figure 3 (in particular the zoomed in portions of the sections, highlighted with a dashed box, shown in Figs. 3C and 3D), where the CE3 exhibits a strong structuring, while IE3 has a smooth surface.

[0336] An excerpt of photographs of IE4 and CE4 are shown in Figure 4 and measured properties listed in Table 6:

[0337] Table 6: Results of test methods of inventive example 4 (IE4) and comparative example 4 (CE4)

[0338] Yet again, the extrusion behaviour of the inventive coating additive composition is superior. When the carriers are loaded with the slip and anti-crater agent, good bonding to the substrate is only observed for the inventive example IE4. This becomes particularly apparent from the cross cut test, wherein an adhesive failure of the coating is observed (cf. Figs. 4C and 4D, which are zoomed in views of Figs. 4A and 4B, respectively). Furthermore, when silica is used as a carrier, a significant reduction in gloss is observed compared to the carrier used according to the invention. The coating in IE4 also exhibits reduced friction, as shown from the slip measurements. Without being bound by theory, it is believed that this is due to a 202200165 Foreign Filing 35 complete release of the additive from the carrier in the inventive sample, whereas this is not the case for the silica carrier.

Claims

202200165 Foreign Filing 36CLAIMS1. Additive composition for use in powder coatings comprising a powder coating additive absorbed on a carrier, characterized in that the carrier is a foamed micro-porous thermoplastic polymer (matrix polymer).

2. Additive composition according to claim 1 , characterized in that the powder coating additive is selected from the group consisting of additives to regulate the surface tension (surfactant), anti-crater agent, dispersant, effect agent, defoamer, texturing agent, scratch resistance agent, anti-blocking agent, lubricant, adhesion promoter, hydrophobic agent, hydrophilic agent, inhibitor, catalyst, corrosion inhibitor, light stabilizer, matting agent, wetting agent, structuring agent, leveling agent, and / or additives to improve chargeability, water resistance, chemical resistance.

3. Additive composition according to claim 1 or 2, characterized in that the powder coating additive is an adhesion promoter.

4. Additive composition according to any of the previous claims, characterized in that the powder coating additive is selected from the group consisting of polysiloxanes, poly(meth)acrylates, maleic acid anhydride-copolymers, polybutadienes, polyolefins, polyester-polyethers, polyalkylene imines, polyamines, polyester resins, silanes, polyglycerol partial esters, phospholipids, acetylenic diols, polyethers, fatty acid amidoamines, phosphoric acid esters, triglycerides, fatty alcohol alkoxylates, and thioethers.

5. Additive composition according to any of the previous claims characterized in that the matrix polymer contains a polymer selected from the group of homo- or copolymers of polyolefins, polystyrenes, polyvinylalcohols, polyacrylates, polymethacrylates, polyesters, polyamides and polycarbonates.

6. Additive composition according to any of the previous claims, characterized in that the melting point of the matrix polymer is from 95 to 200°C, more preferably from 100 to 160°C, more preferably from 105 to 140°C, most preferably from 110 to 120°C.

7. Additive composition according to any of the previous claims, characterized in that the matrix polymer contains a polymer selected from the group consisting of high-density polyethylene, low-density polyetheylene, linear low-density polyethylene, polypropylene, polystyrene, poly(ethylene-co-methacrylate), poly(ethylene-co-vinylacetate), polybutylene(adipate-co- terephthalate), polyamide 6, polyamide 6.6, polyamide 12, poly(ethylene terephthalate), poly(styrene-co-butadiene) and polycarbonate preferably poly(ethylene-co-vinylacetate) or polybutylene(adipate-co-terephthalate), more preferably polybutylene(adipate-co- terephthalate).202200165 Foreign Filing 378. Additive composition according to any of the previous claims, characterized in that the matrix polymer contains polybutylene(adipate-co-terephthalate).

9. Additive composition according to claim 8, characterized in that the powder coating additive is selected from the group consisting of additives to regulate the surface tension (surfactant), anti-crater agent, dispersant, effect agent, defoamer, texturing agent, scratch resistance agent, anti-blocking agent, lubricant, adhesion promoter, hydrophobic agent, hydrophilic agent, inhibitor, catalyst, corrosion inhibitor, light stabilizer, matting agent, wetting agent, structuring agent, leveling agent, and / or additives to improve chargeability, water resistance, chemical resistance.

10. Additive composition according to claim 8, characterized in that the powder coating additive is selected from the group consisting of polysiloxanes, poly(meth)acrylates, maleic acid anhydride-copolymers, polybutadienes, polyolefins, polyester-polyethers, polyalkylene imines, polyamines, polyester resins, silanes, polyglycerol partial esters, phospholipids, acetylenic diols, polyethers, fatty acid amidoamines, phosphoric acid esters, triglycerides, fatty alcohol alkoxylates, and thioethers.11 . Additive composition according to any of the previous claims, characterized in that the weight ratio between the carrier and the powder coating additive is in the range of 1 :6 to 6:1 , preferably in the range of 1 :3 to 4:1 , more preferably in the range of 1 :2 to 3:1 , most preferably in the range of 1 :1 to 2:1 .

12. Use of a foamed micro-porous thermoplastic polymer, preferably as a carrier for a powder coating additive in an additive composition according to any of the previous claims, for powder coating.

13. Powder coating composition comprising a binder and an additive composition according to any of the claims 1 to 11 .

14. Powder coating composition according to claim 13, characterized in that binder is selected from the group consisting of epoxy resin, epoxy resin-polyester hybrid system, reactive polyester, reactive (meth)acrylate, reactive silicone, fluoroethylene vinylether, ketone resin, polyamide, polyethylene, polyvinyl chloride, polyvinylidene chloride, phenolic resin, preferably from the group consisting of epoxy resin, epoxy resin-polyester hybrid system, reactive polyester, reactive (meth)acrylate, more preferably reactive polyester, or epoxy-resin polyester hybrid system, most preferably reactive polyester.

15. Process for preparation of a powder coating composition according to claim 13 or 14, comprising the steps(1) providing a binder and an additive composition,(2) mixing the components of step (1) by extrusion,(3) micronizing the composition obtained in step (2),202200165 Foreign Filing 38(4) optionally sieving the composition obtained in step (3).

16. Process for preparation of a coated substrate comprising the steps(5) applying a powder coating composition according to claim 13 or 14 or obtained from a process according to claim 13 to a substrate by powder coating, preferably by static spraying, followed by(6a) curing the composition, preferably by heating or UV irradiation, preferably heating, if the binder is a thermosetting polymer, or(6b) melting the composition if the binder is a thermoplastic polymer,(7) optionally applying a further coating by repeating steps (5), and (6a) or (6b).

17. Coated article obtainable by a process according to claim 16.

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