Acrylate-siloxane copolymers and use thereof in soil-repellent coatings

Abstract

The present invention relates to the field of easy-to-clean compositions using fluorine-free polymers based on acrylate-siloxane copolymer. The invention therefore firstly provides a polymer obtainable by free-radical polymerization of a starting mixture comprising: (i) at least one reaction initiator which is not an azo initiator, (ii) at least one organic solvent, (iii) 5-95 wt% of at least one monomer of the chemical formula (I), (iv) 5-95 wt% of iv-a) at least one monomer of the chemical formula (II) and / or iv-b) at least one acrylonitrile monomer, (v) 1-80 wt% of v-a) at least one monomer of the chemical formula (III) and / or v-b) at least one styrene monomer and (vi) 0.1-30 wt% of at least one ethylenically unsaturated monomer which, in addition to the ethylenically unsaturated group, has at least one further functional group, where component (vi) is different from components (iii) to (v) and is not an ester or diester of itaconic acid, wherein the specified percentages by weight are based on the total weight of components (iii) to (vi). The invention further provides a process for preparing the polymers of the invention, the use thereof in soil-repellent coatings, and the substrates coated therewith.

Description

[0001] CO12402 / We

[0002] Acrylate siloxane copolymers and their use in dirt-repellent coatings

[0003] The present invention relates to the field of easy-to-clean compositions using fluorine-free acrylate-siloxane copolymers, processes for producing these acrylate-siloxane copolymers, their use in dirt-repellent coatings, and the substrates coated therewith.

[0004] Currently, perfluorinated polymer materials dominate easy-to-clean applications for mineral substrates, metal, plastic, wood, paper products, leather, textile, glass, paint and foam due to their excellent omniphobicity.

[0005] The technical term "easy-to-clean" (German: Pflegeleichtbeschichtung) is a common term used to characterize omniphobic surfaces. Omniphobic surfaces exhibit hydrophobic and, in particular, additionally oleophobic properties. Easy-to-clean surfaces can be cleaned of both aqueous and oily dirt simply by wiping.

[0006] Extensive studies have been conducted in the scientific literature on why fluorinated materials might be omniphobic. It is assumed that the electronegativity of the fluorine atom plays a crucial role, and that in a perfluorinated molecule, the fluorine atoms form a kind of "protective shell" against chemical attack. In perfluorinated polymers, weak interchain forces, close packing of the perfluorinated side chains, and the stiffness of these chains contribute to a low surface energy and thus omniphobicity. CO12402 / We

[0007] 2

[0008] Despite their excellent application properties, perfluorinated materials are considered highly problematic from an ecological perspective, as they are persistent materials with toxic transformation and degradation products that remain in the environment and ecosystems. A short-term solution to this problem has been proposed: the use of fluorinated materials with shorter perfluoroalkyl chains of four to six carbon atoms, which are not considered bioaccumulative. However, the performance of fluoropolymers decreases significantly as their fluorinated chains become shorter, so simply shortening the chain is not a viable solution.

[0009] The European Chemicals Agency (ECHA) recently published a proposal that would largely prohibit the production, use, and placing on the market (including import) of per- and polyfluoroalkyl substances (PFAS). This would affect approximately 10,000 PFAS compounds in Europe alone.

[0010] This impending ban acts as a regulatory driver, thus demanding the rapid provision of fluorine-free alternatives with the described omniphobic properties, which can be used as high-performance alternatives in easy-to-clean applications. However, achieving such omniphobic properties on a wide variety of surfaces is very difficult without the use of PFAS, as most PFAS-free coatings result in either exclusively water-repellent or oil-repellent coatings.

[0011] Based on previous studies in scientific publications (such as H. Lei et al., Progress in Organic Coatings 103 (2017) 182-192), it is assumed that the influencing factors for the surface energy of the fluorinated polymer or the oil / water repellency affect the length of the CO12402 / We

[0012] 3

[0013] The perfluorine chain (PF), the orientation of the PF chain, the distribution of PF on the surface, and the stiffness and roughness of the surface are all relevant factors. It has been shown that the surface energy can be adjusted by manipulating the molecular structure and surface composition of materials.

[0014] Apart from fluorinated materials, silicone- and olefin-containing materials can exhibit very low critical surface tensions. However, silicone is typically an oleophilic material. To make silicone-containing materials oil-repellent, the critical surface tension must be lower than the surface tension of O1.

[0015] To achieve this, H. Lei et al. propose using acrylate-siloxane copolymers as omniphobic, fluorine-free coatings.

[0016] The group of acrylate-siloxane copolymers has been known for decades from the state of the art for various applications such as functional coatings or cosmetic formulations (compare, for example, EP1834969 A2 or WO2022093497 Al (solution polymers from organic / alcoholic solvents) or EP4103569 Bl (aqueous copolymer dispersions)).

[0017] H. Lei et al. demonstrate that the polymer composition has a significant influence on the resulting critical surface tension and thus on the achievable omniphobic properties. This is primarily influenced by the type of monomers used and their proportion in the resulting copolymer. Further influencing factors include the copolymer concentration, the coating process, and the solvent used.

[0018] Various copolymers consisting of tris(trimethylsiloxy)silyl-functionalized acrylate units, hydroxy-, CO12402 / We

[0019] 4

[0020] Copolymers consisting of trimethoxysilyl or triethoxysilyl-functionalized acrylates and propyl methacrylate units have been shown to exhibit omniphobic properties on masonry and textile substrates. The copolymers were prepared in toluene using azobis(isobutyronitrile) (AIBN) as a radical initiator via radical polymerization.

[0021] A particular disadvantage of these compositions is the use of AIBN, which has been shown to form toxic byproducts (see P. Nesvadba in Encyclopedia of Radicals in Chemistry, Biology and Materials (eds.: C. Chatgilialoglu, A. Studer), John Wiley & Sons Ltd., 2012), as well as the use of toluene as a solvent, which is known to be carcinogenic, mutagenic, and reprotoxic (CMR) substances. Easy-to-clean compositions contaminated with these toxic (byproducts) cannot be used for omniphobic coatings of substrates in sensitive applications such as food contact, which significantly limits their application potential. Furthermore, the formulations described in H. Lei et al. The described compositions only produce limited dirt-repellent effects on natural stones, which are not yet satisfactory, especially in industrial applications (see comparative example VI in Table 2).

[0022] As shown in H. Lei et al. using the structure-activity relationship, not just any prior art acrylate-siloxane copolymers, which are produced in organic solvents as in H. Lei et al., are equally suitable as high-performance omniphobic coatings.

[0023] Even the aqueous dispersions of acrylate-siloxane copolymers known in the prior art are unsuitable as high-performance omniphobic coatings, since water per se as a solvent and in combination with the emulsifiers used brings with it numerous disadvantages such as low formulation CO12402 / We

[0024] 5. Variation and further application-related difficulties such as limited or difficult-to-control processing time and film formation, all of which result in limited performance of the omniphobic coating from aqueous systems. The effectiveness of such coatings on a wide variety of substrates also appears to be another limiting factor.

[0025] Against this background, the task was therefore to provide improved fluorocarbon alternatives based on acrylate-siloxane copolymers and a method for producing these copolymers, which can be used as easy-to-clean compositions with excellent omniphobic properties in coatings on a variety of substrates.

[0026] This problem is solved by the present invention.

[0027] Surprisingly, it has been shown that the use of the polymers according to the invention, based on acrylate-siloxane copolymers, yields excellent omniphobic properties on a wide variety of substrates, such as mineral substrates, metal, plastics, wood, paper products, leather, textiles, glass, paint, foam, or composite materials made from these. These omniphobic properties can be further enhanced by adding additives (c) to the easy-to-clean compositions comprising the polymers according to the invention. This technical effect was not expected in light of the easy-to-clean compositions based on acrylate-siloxane copolymers previously available in the field as fluorocarbon substitutes and is therefore particularly surprising. CO12402 / We

[0028] 6

[0029] A first object of the present invention is directed to a polymer obtainable by radical polymerization of a starting mixture comprising:

[0030] (i) at least one reaction initiator that is not an azo initiator,

[0031] (ii) at least one organic solvent,

[0032] (iii) 5-95 wt% of at least one monomer of the following chemical formula (I)

[0033] [ Formula I ] , wherein

[0034] RI H or a hydrocarbon residue with 1-6

[0035] C atoms is,

[0036] Y Methylene or ethylene is,

[0037] R2 is H or Methyl, n is 0 or 1,

[0038] Z Methylene or 0 is and

[0039] R3, R4 and R5 are the same or different and are each independently CHa, C2H5, n-propyl, iso-propyl, OSi-(CHa)3, OSi-(C2Hs)3, O-Si-(n-propyl)3 or O-Si-(iso-propyl)3,

[0040] (iv) 5-95 wt% CO12402 / We iv-a) at least one monomer of the following chemical formula (II)

[0041] [ Formula II] , wherein

[0042] RI H or a hydrocarbon residue with 1-6 C atoms is and

[0043] R6 is a hydrocarbon residue with 1 or 2 C atoms and / or iv-b) at least one monomer acrylonitrile,

[0044] (v) 1-80 wt.% va) of at least one monomer of the following chemical formula (III)

[0045] [Formula III] , wherein CO12402 / We

[0046] 8

[0047] RI H or a hydrocarbon residue with 1-6 C atoms and R7 is a hydrocarbon residue with 3 or more C atoms, and / or vb) at least one monomer styrene and (vi) 0.1-30 wt% at least one ethylene-unsaturated monomer having at least one additional functional group besides the ethylene-unsaturated group, wherein component (vi) is different from components (iii) to (v) and is not an ester or diester of itaconic acid, wherein the wt% given are based on the total weight of components (iii) to (vi).

[0048] A preferred embodiment of the present invention relates to a polymer obtainable by radical polymerization of a starting mixture consisting of:

[0049] (i) at least one reaction initiator that is not an azo initiator,

[0050] (ii) at least one organic solvent,

[0051] (iü) 5-95 wt% of at least one monomer of the following chemical formula (I) CO12402 / We

[0052] [ Formula I ] , wherein

[0053] RI H or a hydrocarbon residue with 1-6

[0054] C atoms is,

[0055] Y Methylene or ethylene is,

[0056] R2 is H or Methyl, n is 0 or 1,

[0057] Z Methylene or 0 is and

[0058] R3, R4 and R5 are the same or different and are each independently CHa, C2H5, n-propyl, iso-propyl, OSi-(CHa)3, OSi-(C2Hs)3, O-Si-(n-propyl)3 or O-Si-(iso-propyl)3,

[0059] (iv) 5-95 wt.% iv-a) of at least one monomer of the following chemical formula (II)

[0060] [Formula II] , wherein CO12402 / We

[0061] 10

[0062] RI H or a hydrocarbon residue with 1-6 C atoms is and

[0063] R6 is a hydrocarbon residue with 1 or 2 C atoms and / or iv-b) at least one monomer acrylonitrile, 0 wt. at least one monomer of the following chemical formula (III)

[0064] [ Formula III] wherein

[0065] RI H or a hydrocarbon residue with 1-6 C atoms is and

[0066] R7 is a hydrocarbon residue with 3 or more C atoms, and / or vb) at least one monomer styrene and CO12402 / We

[0067] 11

[0068] (vi) 0.1-30 wt% of at least one ethylene-unsaturated monomer having at least one further functional group in addition to the ethylene-unsaturated group, wherein component (vi) is different from components (iii) to (v) and is not an ester or diester of itaconic acid, wherein the wt% indicated are based on the total weight of components (iii) to (vi).

[0069] Another object of the present invention is directed to a process for producing the polymer, in which a starting mixture comprising

[0070] (i) at least one reaction initiator that is not an azo initiator,

[0071] (ii) at least one organic solvent,

[0072] (iii) 5-95 wt% of at least one monomer of the following chemical formula (I)

[0073] [ Formula I ] , wherein

[0074] RI H or a hydrocarbon residue with 1-6

[0075] C atoms is, CO12402 / We

[0076] 12

[0077] Y Methylene or ethylene is,

[0078] R2 is H or Methyl, n is 0 or 1,

[0079] Z Methylene or 0 is and

[0080] R3, R4 and R5 are the same or different and are each independently CHs, C2H5, n-propyl, iso-propyl, OSi- (CH3)3, OSi- (C2H5)3, O-Si- (n-propyl)3 or O-Si- (iso-propyl)3

[0081] (iv) 5-95 wt.% iv-a) of at least one monomer of the following chemical formula (II)

[0082] [ Formula II] , wherein

[0083] RI H or a hydrocarbon residue with 1-6 C atoms is and

[0084] R6 is a hydrocarbon residue with 1 or 2 C atoms, and / or iv-b) at least one monomer acrylonitrile, CO12402 / We

[0085] 13

[0086] (v) 1-80 wt.% va) of at least one monomer of the following chemical formula (III)

[0087] [Formula III] , wherein

[0088] RI H or a hydrocarbon residue with 1-6 C atoms is and

[0089] R7 is a hydrocarbon residue with 3 or more carbon atoms, vb) and / or at least one monomer styrene and

[0090] (vi) 0.1–30 wt.% of at least one ethylene-unsaturated monomer having, in addition to the ethylene-unsaturated group, at least one further functional group, wherein component (vi) is different from components (iii) to (v) and is not an ester or diester of itaconic acid, wherein the wt.% indicated are based on the total weight of components (iii) to (vi), and is polymerized by radicals. CO12402 / We

[0091] 14

[0092] A preferred embodiment of the present invention is directed to a process for producing the polymer, in which a starting mixture consisting of

[0093] (i) at least one reaction initiator that is not an azo-

[0094] The initiator is,

[0095] (ii) at least one organic solvent,

[0096] (iii) 5-95 wt% of at least one monomer of the following chemical formula (I)

[0097] [ Formula I ] , wherein

[0098] RI H or a hydrocarbon residue with 1-6

[0099] C atoms is,

[0100] Y Methylene or ethylene is,

[0101] R2 is H or Methyl, n is 0 or 1,

[0102] Z Methylene or 0 is and

[0103] R3, R4 and R5 are the same or different and each independently of each other CHs, C2H5, n-propyl, iso-propyl, OSi- (CH3)3, OSi- (C2H5)3, O-Si- (n- CO12402 / We

[0104] Propyl) 3 or O-Si- (iso-propyl) 3 are,

[0105] (lv) 5-95 wt. iv-a) at least one monomer of the following chemical formula (II)

[0106] [ Formula II] , wherein

[0107] RI H or a hydrocarbon residue with 1-6 C atoms is and

[0108] R6 is a hydrocarbon residue with 1 or 2 C atoms, and / or iv-b) at least one monomer acrylonitrile,

[0109] 1-80 wt. va) of at least one monomer of the following chemical formula (III) CO12402 / We

[0110] 16

[0111] [Formula III] , wherein RI is H or a hydrocarbon residue with 1-6 C atoms and R7 is a hydrocarbon residue with 3 or more C atoms, vb) and / or at least one monomer styrene and (vi) 0.1-30 wt% at least one ethylene-unsaturated monomer having at least one further functional group in addition to the ethylene-unsaturated group, wherein component (vi) is different from components (iii) to (v) and is not an ester or diester of itaconic acid, wherein the wt% given are based on the total weight of components (iii) to (vi) , is polymerized by radicals.

[0112] To avoid making the description of the present invention too lengthy, only the preferred embodiments of the individual features are listed below. The reader skilled in the art should understand this type of disclosure CO12402 / We

[0113] 17, however, should be understood explicitly as meaning that every combination of different levels of preference is explicitly revealed and explicitly desired.

[0114] Preferably, RI is H or a hydrocarbon residue with 1-3 C atoms, particularly preferably H or a hydrocarbon residue with 1-2 C atoms, very particularly preferably H or methyl and most preferably methyl.

[0115] At least one of R3, R4 and R5 is in particular selected from CHa, OSi (CHa)3, OSi (C2Hs)3 or O-Si- (iso-Propyl ) 3 and especially preferably OSi (CHa)3.

[0116] In a preferred embodiment, R3, R4 and R5 are the same.

[0117] Preferably Y and Z are methylene, R2 is H, n is 0 and R3, R4 and R5 are O-Si (CH3)3.

[0118] Preferably, R7 is a hydrocarbon residue with 3-30 C atoms, particularly preferably with 4-22 C atoms.

[0119] Preferably, the monomer of chemical formula (I) 3-[Tris(trimethylsiloxy)silyl] propyl methacrylate (CLA30) , 3-(1,1,3,3,3-pentamethyldisiloxan-yl) propyl methacrylate, 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl) propyl methacrylate, 2-(3-(1,1,3,3,3-pentamethyldisiloxan-yl)propoxy) ethyl methacrylate, 2-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propoxy) ethyl methacrylate or 2-(3-(1,1, 1, 3, 5, 5, 5-Heptamethyltrisiloxan-3-yl)propoxy)ethyl methacrylate, preferably 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (CLA30).

[0120] Preferred monomers of chemical formula (II) are methyl(meth)acrylate, ethyl(meth)acrylate, or acrylonitrile. CO12402 / We

[0121] 18

[0122] Preferably the monomer of chemical formula (III) is n-butyl (meth) acrylate, 2-ethylhexyl acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate or styrene.

[0123] In the case of stearyl (meth) acrylate, this includes both the pure compounds (R? = CisHa? ) and mixtures, for example with R7 = C18H37 and R7 = C16H33.

[0124] In the case of behenyl (meth) acrylate, this includes both the pure compounds (R7 = C22H45) and mixtures, for example with R7 = C22H45, R7 = C20H41, R7 = C18H37 and R7 = C16H33 includes .

[0125] The ethylene-unsaturated monomer (vi ) has at least one additional functional group besides the ethylene-unsaturated group, wherein component (vi ) is different from components (iii ) to (v) and is not an ester or diester of itaconic acid.

[0126] Preferably, the component (vi) of the polymer according to the invention is different from the additives (c) of the Easy-to-Clean composition according to the invention.

[0127] A functional group is defined as a group of atoms in a compound that significantly determines the compound's properties and reactivity. A compound can also contain multiple functional groups with different properties. Functional groups are classified according to the atoms involved into functional groups with heteroatoms (usually O, N, S, P, halogens, Si) and those without heteroatoms (such as C=C double bonds, C=C triple bonds, or aromatics).

[0128] In a preferred embodiment, the ethylene-unsaturated monomer (vi) is selected from the group consisting of monomers with C=C double bonds, C=C triple bonds, CO12402 / We

[0129] 19

[0130] Aromatic, O-containing, N-containing, S-containing, P-containing, halogen-containing and Si-containing functional groups.

[0131] Preferably the monomer (vi ) is selected from the group consisting of vinyl esters, vinyl aromatics, ethylene unsaturated mono- or dicarboxylic acids, ethylene unsaturated carboxylic acid amides, sulfuric acid monomers, phosphoric acid monomers, vinyl halogen compounds and silane monomers .

[0132] Non-exhaustive examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethyl hexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate, or a vinyl ester of α-branched monocarboxylic acids with 9-11 carbon atoms, for example VeoVa9® or VeoVal O® (trade names of the company Resolution), with vinyl acetate being particularly preferred.

[0133] Non-exhaustive examples of vinyl aromatics include alpha-methylstyrene, an isomeric vinyltoluene, vinylxylene, or divinylbenzene.

[0134] Non-exhaustive examples of ethylene-unsaturated mono- or dicarboxylic acids are (meth)acrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride.

[0135] Non-exhaustive examples of ethylene-unsaturated carboxylic acid amides are acrylamide, N-methylolacrylamide, or diacetoneacrylamide.

[0136] Non-exhaustive examples of sulfuric acid monomers include sulfoethyl(meth)acrylate, sulfopropyl(meth)acrylate, styrenesulfonic acid, and ethylene-unsaturated sulfonic acids or their salts, such as vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid. CO12402 / We

[0137] 20

[0138] Phosphoric acid monomes can be, for example, phosphonic acid, phosphonate and dihydrogen phosphate esters of an alcohol substituted with a polymerizable ethylene unsaturated group.

[0139] Non-exhaustive examples of dihydrogen phosphate esters are phosphates of hydroxyalkyl (meth) acrylates, which include phosphoethyl (meth) acrylate and phosphopropyl (meth) acrylate.

[0140] Non-exhaustive examples of vinyl halogen compounds include vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl iodide, or vinylidene iodide.

[0141] Nicht abschließende Beispiele für Silanmonomere sind 3- (Meth) acrylamidopropyltrimethoxysilan, 3- (Meth) acrylamidopro- pyltriethoxysilan, N- ( 3- (Meth) acryloxy-2-hydroxypropyl ) -3-ami- nopropyltrimethoxysilan, N- ( 3- (Meth) acryloxy-2-hydroxypropyl ) - 3-aminopropyltriethoxysilan, (Meth) acryloxymethyltrimethoxy- silan, (Meth) acryloxymethyltriethoxysilan, 0- [ (Meth) acry- loxyethyl ] -N- ( trimethoxysilylpropyl ) carbamat , 0- [ (Meth) acry- loxyethyl ] -N- ( triethoxysilylpropyl ) carbamat , 3- ( Trimethoxy- silyl ) propyl (meth) acrylat , 3- ( Triethoxysilyl ) propyl (meth) acrylat , 3- ( Triisopropoxysilyl ) propyl (meth) acrylat , ( 3- (Meth) ac- ryloxypropyl ) methyldimethoxysilan, ( 3- (Meth) acryloxypropyl ) me- thyldiethoxysilan, [ (Meth) acryloxymethyl ] methyldimethoxysilan, [ (Meth) acryloxymethyl ] methyldiethoxysilan, 3- ( 3-methoxy- 1 , 1 , 1 , 5 , 5 , 5-hexamethyltrisiloxan-3-yl ) propyl (meth) acrylat , ( 3- (Meth) acryloxypropyl ) dimethylmethoxysilan,(3-(Meth)acryloxypropyl)dimethylethoxysilane, (3-(Meth)acryloxymethyl)dimethylmethoxysilane or (3-(Meth)acryloxymethyl)dimethylethoxysilane. CO12402 / We,

[0142] 21

[0143] Preferably the monomer (vi ) is selected from the group of pre-crosslinking monomers such as polyethylene unsaturated monomers, for example divinyl adipate, diallyl maleate, allyl (meth) acrylate or triallyl cyanurate, or post-crosslinking monomers, for example acrylamidoglycolic acid, methyl methylacrylamidoglycolic acid ester, N-methylol (meth)-acrylamide, N-methylolallylcarbamate and alkyl ethers such as the isobutoxy ether or esters of N-methylol (meth)acrylamide or N-methylolallylcarbamate.

[0144] Preferred as monomers (vi) are also ethylenic unsaturated epoxide-functional monomers such as glycidyl (meth) acrylate, as well as monomers with hydroxy or CO groups, for example (meth)-acrylic acid hydroxyalkyl esters, such as hydroxyethyl-, hydroxypropyl- or hydroxybutylmeth) acrylate, as well as compounds such as diacetone acrylamide or acetylacetoxyethyl (meth) acrylate.

[0145] In a particularly preferred embodiment, the ethylene-unsaturated monomer (vi) is selected from the group consisting of (meth)acrylic acid, maleic anhydride, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, N-methylol (meth)acrylamide, acetoacetoxyethyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate and 3-(triethoxysilyl)propyl (meth)acrylate.

[0146] In a preferred embodiment, the starting mixture j comprises exactly one monomer of each of the components (iii) to (vi).

[0147] The starting mixture can further comprise at least one reaction initiator (i), which may be thermally or redox-initiated. The reaction initiator is preferably at least partially soluble in organic solvents. CO12402 / We

[0148] 22

[0149] A thermally initiated reaction initiator is known to decompose after thermal treatment into reactive components that initiate the polymerization reaction. As is known in the field, redox-initiated reaction initiators are combinations of oxidizing and reducing compounds used to initiate radical polymerizations.

[0150] Preferably, the reaction initiator is a peroxide, preferably selected from the group consisting of sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, potassium peroxodiphosphate, t-amyl peroxypivalate, t-butyl peroxopivalate (PW), t-butyl peroxy-2-ethylhexanoate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, dicumyl peroxide, preferably PW.

[0151] Since azo initiators are known to form toxic byproducts upon decomposition, their use in the present invention is excluded.

[0152] It has proven preferable to use the reaction initiator in combination with a redox system. Redox-reaction initiator combinations utilize the initiators mentioned above in conjunction with a reducing agent. Suitable reducing agents include sulfites and bisulfites of monovalent cations, such as sodium sulfite; derivatives of sulfoxylic acid, such as zinc or alkali formaldehyde sulfoxylates, for example, sodium hydroxymethanesulfonate; and ascorbic acid, particularly sodium hydroxymethanesulfonate.

[0153] Redox reaction initiator combinations have the advantage that the polymerization reaction already occurs at lower CO12402 / We

[0154] 23

[0155] Temperatures can be started. In addition to reduced energy consumption, the monomers can also be protected from potential thermal decomposition.

[0156] In addition, small amounts of a metal compound soluble in the polymerization medium can be introduced, the metal component of which is redox-active under the polymerization conditions, such as those based on iron or vanadium, for example ferric ammonium sulfate.

[0157] In the case of reactions following radical solution polymerization in organic solvents, predominantly oil-soluble initiators are used, such as cumene hydroperoxide, isopropylbenzene monohydroperoxide, dibenzoyl peroxide, dilauryl peroxide, t-amyl peroxypivalate, PPV, or t-butyl peroxy-2-ethylhexanoate. PPV is a particularly preferred reaction initiator for the process according to the invention.

[0158] An overview of suitable initiators, in addition to the representatives described above, can be found in the "Handbook of Free Radical Initiators", E. T. Denisov, T. G. Denisova, T. S. Po-kidova, 2003, Wiley Publishing.

[0159] The reaction initiator (i) is used in amounts typical for radical polymerizations for those skilled in the art.

[0160] The starting mixture may further comprise at least one organic solvent (ii). This may be any organic solvent that a person skilled in the art uses for radical polymerizations. CO12402 / We

[0161] 24

[0162] To make the process more sustainable, organic solvents are preferably used, which are environmentally safe and do not belong to the so-called CMR substances.

[0163] Preferably the starting mixture comprises an organic solvent ( ii ) .

[0164] Preferably, aromatic-free solvents are used as the organic solvent (ii).

[0165] In a particularly preferred embodiment, ethyl acetate, butyl acetate or 2-ethylhexyl acetate is used as the organic solvent (ii).

[0166] Predominantly aqueous solvents are not used as organic solvents (ii). Residual amounts of water up to 10 wt% based on the total amount of solvent used, or aqueous azeotropes, are not considered predominantly aqueous solvents. Non-exhaustive examples of aqueous azeotropes include alcohol / water such as ethanol / water, aromatics / water such as toluene / water, 1,4-dioxane / water, ethyl acetate / water, and acetonitrile / water.

[0167] In the polymer according to the invention, the amount of the at least one monomer (iii) of chemical formula (I) can be 5-95 wt.%, preferably 10-90 wt.%, more preferably 15-80 wt.% and most preferably 20-60 wt.%, based on the total weight of components (iii) to (vi) .

[0168] In a preferred embodiment, the amount of the at least one monomer (iii) of chemical formula (I) can be 30-60 wt.%, particularly preferably 25-60 wt.%, based on the total weight of components (iii) to (vi). CO12402 / We

[0169] 25

[0170] In the polymer according to the invention, the amount of the at least one monomer (iv) can be 5-95 wt.%, preferably 10-90 wt.%, more preferably 15-80 wt.% and most preferably 20-70 wt.%, based on the total weight of components (iii) to (vi) .

[0171] In the polymer according to the invention, the amount of the at least one monomer (v) can be 1-80 wt.%, preferably 1-60 wt.%, more preferably 1-50 wt.% and most preferably 1-40 wt.%, based on the total weight of components (iii) to (vi) .

[0172] In the polymer according to the invention, the amount of the at least one ethylene-unsaturated monomer (vi) can be 0.1-30 wt.%, preferably 0.1-20 wt.%, more preferably 0.1-15 wt.% and most preferably 0.1-10 wt.%, based on the total weight of components (iii) to (vi).

[0173] In a preferred embodiment, the amount of the at least one ethylene-unsaturated monomer (vi) can be 0.1-30 wt.%, preferably 0.1-20 wt.%, more preferably 0.1-15 wt.% and most preferably 0.1-10 wt.%, based on the total weight of components (iii) to (vi).

[0174] A preferred embodiment of the present invention is directed to a polymer obtainable by radical polymerization of a starting mixture comprising (i) PW, (ii) ethyl acetate, butyl acetate or 2-ethylhexyl acetate, (iii) 40 wt.% 3-[tris(trimethylsiloxy)silyl]propyl methacrylate, (iv) 40 wt.% methyl methacrylate, (v) 15 wt.% of a monomer (v), wherein monomer (v) is stearyl(meth)acrylate, and 5 wt.% of a monomer (vi), wherein monomer (vi) is selected from the group consisting of methyl acrylic acid, hydroxyethyl methacrylate and CO12402 / We

[0175] 26

[0176] Maleic anhydride, wherein the stated wt. % are based on the total weight of components (iii) to (vi).

[0177] As already explained, the polymer is obtained by radical polymerization of a starting mixture.

[0178] A radical polymerization according to the present invention can be described as a chain polymerization in which the two carbon atoms of the unsaturated C2 unit (ethylenic or acetylenic) of one monomer are each covalently linked to a carbon atom of an unsaturated C2 unit of any other monomer. In this process, the multiple bonds of these ethylenic or acetylenic unsaturated C2 units are converted to single or double bonds, respectively. This linkage reaction is described below by way of example for an ethylenic unsaturated C2 unit and proceeds analogously for an acetylenic unsaturated C2 unit, forming a double bond: The linkage reaction is initiated by reaction initiators that release radicals (INIT-).The radicals bind to the ethylene-unsaturated C2 units (C=C) to form a primary radical (INIT-CC-), which in turn chain-polymerizes with further unsaturated C2 units. Finally, the backbone of the resulting copolymer is formed from the covalently bonded C2 units.

[0179] The radical polymerization is carried out in at least one organic solvent. The starting mixture preferably exhibits the properties typical for radical polymerization. The radical polymerization is preferably a solution polymerization. CO12402 / We

[0180] 27

[0181] The procedure includes, in particular, the following steps in the specified order:

[0182] (1a) Separate provision of components (i) , (ii) and

[0183] ( iii ) to ( vi ) :

[0184] (1a±) Providing at least one reaction initiator (i) , optionally in combination with a redox system as described above

[0185] (lau) Providing at least one organic

[0186] solvent (ii) ,

[0187] (lam) Provision of the starting mixture comprising at least one monomer of each of components (iii) to (vi),

[0188] (Iß) Homogenizing the provided starting mixture from step (lam) , preferably by stirring, dispersing, ultrasonic treatment and / or pressure treatment,

[0189] (ly) Adding the at least one reaction initiator (i) from step (1a±) and the homogenized starting mixture from step (1b) to the at least one organic solvent (ii) from step (1a) at a temperature of 0-100°C, preferably 5-80°C, more preferably 30-80°C, over a period of several hours, preferably in the range of 1-8 hours, more preferably 2-6 hours,

[0190] (15) Reacting the reaction mixture obtained according to (ly) at a temperature of 30-100°C, preferably 30-80°C, for a period of several hours, preferably in the range of 0.1-8 hours, more preferably 0.5-6 hours, optionally with the addition of further reaction initiator (i) from CO12402 / We

[0191] 28

[0192] Step (a1±) and addition of further solvent (ii) from step (a1±i) and

[0193] ( le ) Cooling the reacted reaction mixture obtained according to ( 15 ) to room temperature .

[0194] The reaction initiator can be added as a solid or dissolved in an organic solvent, which may be the same as or different from the organic solvent ( 11 ).

[0195] The polymerization can be carried out discontinuously or continuously, with all or individual components of the reaction mixture, with partial initial addition and subsequent addition of individual components of the reaction mixture, or by a dosing method without initial addition. All additions are preferably made in proportion to the consumption of the respective component. Batch polymerization is particularly preferred.

[0196] It can be particularly advantageous to purify the cooled reaction mixture obtained after ( s ) or to use it without further purification.

[0197] The copolymers obtained in the polymer are either statistical copolymers with a random arrangement of the monomers in the copolymer, gradient copolymers with a gradual change in the copolymer composition along the copolymer chain, alternating copolymers with an alternating arrangement of the individual monomers in the copolymer, or graft copolymers in which monomers are grafted laterally onto a main polymer chain. The copolymers obtained in the polymer are CO12402 / We

[0198] 29 preferably statistical copolymers or gradient copolymers .

[0199] The term copolymer is to be understood as a polymer that consists of at least two different monomers.

[0200] The copolymers obtained in the polymer preferably exhibit a weight-average molar mass M wfrom 5,000-500,000 g / mol, more preferably from 8,000-300,000 g / mol and most preferably from 10,000-150,000 g / mol.

[0201] The weight-average molar masses M w They can be determined, for example, via SEC, GPC, LC, MALDI-TOF or ESI-MS.

[0202] The polymers obtained preferably have a solids content of 10-80%, more preferably 15-70% and most preferably a solids content of 25-65% or are adjusted to this.

[0203] Another object of the present invention is a polymer powder obtainable by drying the polymer according to the invention.

[0204] To produce the polymer powder according to the invention, the polymer according to the invention, which results from the radical polymerization of the starting mixture in at least one organic solvent, is preferably dried in a manner known to those skilled in the art, for example by the spray drying process.

[0205] Drying the polymer into a powder significantly reduces the product volume. This results in lower transport costs and therefore a smaller CO2 footprint. Furthermore, removing the CO12402 / We reduces

[0206] The potential hazards of 30 organic solvents with regard to ecological and safety-related aspects, such as fire load, are reduced. The polymers according to the invention, dried in this way, are stable for storage and, as is customary for those skilled in the art, can be easily converted into a ready-to-use solution before use by mixing them with a suitable organic solvent.

[0207] Another object of the present invention is an easy-to-clean composition comprising

[0208] ( a ) the polymer according to the invention ,

[0209] (b) where appropriate at least one organic solvent and

[0210] (c) optionally at least one additive.

[0211] A particular advantage of the present invention is that the polymer (a) according to the invention can be used directly (i.e., without prior purification, without the addition of an organic solvent (b) and / or additive (c)) as an easy-to-clean composition for the treatment of the substrates according to the invention. Since an additional purification step of the polymer is unnecessary, the economic efficiency of the easy-to-clean compositions according to the invention is significantly improved.

[0212] The easy-to-clean composition comprising the polymer according to the invention may preferably contain at least one organic solvent (b). The amount of solvent (b) contained is then calculated according to the mathematical formula (IV): CO12402 / We

[0213] 31

[0214] Quantity of solvent (b) [wt.%] = (Total weight of Easy-to-Clean composition [100 wt.%] ) - (Quantity of polymer according to the invention (a) [wt.%] )

[0215] [Formula IV]

[0216] The easy-to-clean composition comprising the polymer according to the invention may preferably contain at least one additive (c). The amount of the additive (c) contained is then calculated according to the mathematical formula (V):

[0217] Amount of additive (c) [wt.%] = (Total weight of Easy-to-Clean composition [100 wt.%] ) - (Amount of polymer according to the invention (a) [wt.%] )

[0218] [Formula V]

[0219] In a preferred embodiment, the easy-to-clean composition comprising the polymer according to the invention can contain at least one organic solvent (b) and at least one additive (c). The sum of the amounts of component (a)- (c) [in wt.%] then gives the total weight of the easy-to-clean composition [100 wt.%].

[0220] In a particularly preferred embodiment, the amount of the polymer according to the invention (a) is preferably 0.1-80 wt.%, more preferably 1-70 wt.% and most preferably 2-60 wt.%, based on the total weight of the Easy-to-Clean composition, and the amount of the additive (c) is 0-80 wt.%, more preferably 0.001-70 wt.% and most preferably 0.01-60 wt.%, based on the total weight of the Easy-to-Clean composition.

[0221] The amount of solvent (b) that may be contained is then calculated according to the mathematical formulas (IV) or (VI): CO12402 / We

[0222] 32

[0223] Quantity of solvent (b) [wt.%] = (Total weight of Easy-to-Clean composition [100 wt.%] ) - (Quantity of polymer according to the invention (a) [wt.%] - (Quantity of additive (c) [wt.%] )

[0224] [Formula VI]

[0225] Another object of the present invention is an easy-to-clean composition comprising

[0226] (d) the polymer powder according to the invention,

[0227] (b) at least one organic solvent and

[0228] (c) optionally at least one additive.

[0229] A particular advantage of the present invention is that the polymer powder (d) according to the invention can be used directly (i.e., without prior purification and without the addition of an additive (c)) as an easy-to-clean composition for treating the substrates according to the invention, with the addition of at least one organic solvent. Since an additional purification step of the polymer powder is unnecessary, the economic efficiency of the easy-to-clean compositions according to the invention is significantly improved.

[0230] The easy-to-clean composition comprising the polymer powder according to the invention contains at least one organic solvent (b). The amount of solvent (b) contained is then calculated according to the mathematical formula (VII):

[0231] Quantity of solvent (b) [wt.%] = (Total weight of Easy-to-Clean composition [100 wt.%] ) - (Quantity of polymer powder according to the invention (d) [wt.%] )

[0232] [Formula VII] CO12402 / We

[0233] 33

[0234] In a preferred embodiment, the easy-to-clean composition comprising the polymer powder according to the invention can contain at least one organic solvent (b) and at least one additive (c). The sum of the amounts of component (b) - (d) [in wt.%] then gives the total weight of the easy-to-clean composition [100 wt.%].

[0235] In a particularly preferred embodiment, the amount of the polymer powder (d) according to the invention is preferably 0.1–80 wt.%, more preferably 0.5–35 wt.%, and most preferably 1–30 wt.%, based on the total weight of the easy-to-clean composition, and the amount of the additive (c) is 0–80 wt.%, more preferably 0.001–70 wt.%, and most preferably 0.01–60 wt.%, based on the total weight of the easy-to-clean composition. The amount of the solvent (b) contained is then calculated according to mathematical formulas (VII) or (VIII):

[0236] Quantity of solvent (b) [wt.%] = (Total weight of Easy-to-Clean composition [100 wt.%] ) - (Quantity of polymer powder according to the invention (d) [wt.%] - (Quantity of additive (c) [wt.%] )

[0237] [Formula VIII]

[0238] The Easy-to-Clean composition according to the invention is in particular an Easy-to-Clean solution.

[0239] The easy-to-clean composition may further comprise at least one organic solvent (b). This may be any organic solvent in which the polymer or polymer powder is soluble.

[0240] To make the process more sustainable, organic solvents (b) are preferably used, which are environmentally safe and do not belong to the so-called CMR substances. CO12402 / We

[0241] 34

[0242] Preferably, the easy-to-clean composition comprises an organic solvent (b).

[0243] The organic solvent (b) may preferably be the same or different from the organic solvent (ii) used in the polymer according to the invention.

[0244] Preferably, aromatic-free solvents are used as the organic solvent (b).

[0245] In a particularly preferred embodiment, butyl acetate is used as an organic solvent (b ).

[0246] Further particularly preferred organic solvents (b) are dearomatized (I so ) paraffins or mixtures of esters and dearomatized (I so ) paraffins .

[0247] Predominantly aqueous solvents are not used as solvents (b). Residual amounts of water up to 10 wt.% based on the total amount of solvent used, or aqueous azeotropes, are not considered predominantly aqueous solvents. Non-exhaustive examples of aqueous azeotropes are alcohol / water, such as ethanol / water; aromatics / water, such as toluene / water; 1,4-dioxane / water; ethyl acetate / water; and acetonitrile / water.

[0248] Preferably, the easy-to-clean composition comprises one additive (c) or a combination of two different additives (c).

[0249] Preferably the additive (c) is selected from the group consisting of silanes, silicones, silicone resins, crosslinkers, fillers and curing catalysts.

[0250] Non-exhaustive examples of silanes are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-CO12402 / We

[0251] 35

[0252] Propyltriethoxysilan, n-Butyltrimethoxysilan, n-Butyltriethoxy- silan, I sobutyltrimethoxysilan, I sobutyltriethoxysilan, I sooctyltrimethoxysilan, I sooctyltriethoxysilan, n-Octyltrime- thoxysilan, n-Octyltriethoxysilan, Decyltrimethoxysilan, De- cyltriethoxysilan, Dodecyltrimethoxysilan, Dodecyltriethoxy- silan, Tetradecyltrimethoxysilan, Tetradecyltriethoxysilan, He- xadecyltrimethoxysilan, Hexadecyltriethoxysilan, Phenyltrime- thoxysilan, Phenyltriethoxysilan, Tetraethoxysilan, Epoxysilane , wie beispielsweise Glycidoxypropyltrimethoxy- silane , Glycidoxypropylmethyldimethoxysilan, Glycidoxypropy- Itriethoxysilan, Glycidoxypropylmetyhldiethoxysilan, 2- ( 3 , 4- epoxycyclohexyl ) ethyltriethoxysilan, 2- ( 3 , 4-epoxycyclohe- xyl ) ethyltrimethoxysilan,

[0253] 2- ( 3-Triethoxysilylproypl ) maleinsäureanhydrid, N- ( 3-Trimethoxy- silylpropyl ) harnstof f , N- ( 3-Triethoxysilylpropyl ) harnstof f ,

[0254] N- ( Trimethoxysilylmethyl ) harnstof f , N- (Methyldimethoxysilyme- thyl ) harnstof f , N- ( 3-Triethoxysilylmethyl ) harnstof f , N- ( 3-Me- thyldiethoxysilylmethyl ) harnstof f ,

[0255] 3-Mercaptopropyltrimethoxysilan, 3-Mercaptopropyltriethoxysilan, 3-Mercaptopropylmethyldimethoxysilan, 3-Mercaptopropylmethyldiethoxysilan, O-Methylcarbamatomethyl-methyldimethoxysilan, O-Methylcarbamatomethyl-trimethoxysilan, O-Ethylcar- bamatomethyl-methyldiethoxysilan, O-Ethylcarbamatomethyl-tri- ethoxysilan,

[0256] Aminosilane , wie beispielsweise 3-Aminopropyltrimethoxysilan, N- ( 2-Aminoethyl ) -3-aminopropyltrimethoxysilan, N- ( 2-Aminoethyl ) -3-aminopropylmethyldimethoxysilan, N- Cyclohexyl- 3-aminopropyltrimethoxysilan, 3- Aminopropyltriethoxysilan, N- ( 2-Aminoethyl ) -3- aminopropyltriethoxysilan, N- ( 2-Aminoethyl ) -3- aminopropylmethyldiethoxysilan, N- Cyclohexyl- 3- CO12402 / We

[0257] 36 aminopropyltriethoxysilan, Aminomethyltrimethoxysilan, Aminomethyltriethoxysilan, N-Methylaminomethyltriethoxysilan, N-Ethylaminomethyltriethoxysilan, N-n- Propylaminomethyltriethoxysilan, N-n-Butylaminomethyltriethoxysilan, N-cyclo- Hexylaminomethyltriethoxysilan, N- Phenylaminomethyltriethoxysilan, N, N- Dimethylaminomethyltriethoxysilan, N, N- Diethylaminomethyltriethoxysilan, N, N-Di-n- propylaminomethyltriethoxysilan, N, N-Di-n- butylaminomethyltriethoxysilan, Aminomethyltrimethoxysilan, N-Methylaminomethyltrimethoxysilan, N- Ethylaminomethyltrimethoxysilan, N-n- Propylaminomethyltrimethoxysilan, N-n- Butylaminomethyltrimethoxysilan, N-cyclo- Hexylaminomethyltrimethoxysilan, N- Phenylaminomethyltrimethoxysilan, N, N- Dimethylaminomethyltrimethoxysilan, N, N- Diethylaminomethyltrimethoxysilan, N, N-Di-n- propylaminomethyltrimethoxysilan, N, N-Di-n- butylaminomethyltrimethoxysilan, 4- ( Triethoxysilylmethyl ) tetrahydro-1 , 4-oxazin, 4- ( Trimethoxysilylmethyl ) tetrahydro-1 ,4-oxazine, ureidopropyltrimethoxysilane, ureidopropyltriethoxysilane and their partial condensates.

[0258] Alkylsilanes are preferred, such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, n-Octyltrimethoxysilane, n-Octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, CO12402 / We

[0259] 37

[0260] Hexadecyltriethoxysilane and aminosilanes, such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane.

[0261] Non-exhaustive examples of silicones and silicone resins are those containing units of the chemical formula ( IX ).

[0262] R8 X (0R9 ) y S i O ( 4 -xy) / 2 [ Formula IX ] , where

[0263] R8 is the same or different and, if applicable, represents substituted hydrocarbon residues interrupted by oxygen atoms.

[0264] R9 is the same or different and either H or, if applicable, substituted hydrocarbon residues interrupted by oxygen fractions, means x takes values ​​from 0 to 3 and y takes values ​​from 0 to 4.

[0265] Preferably, residue R8 is a monovalent hydrocarbon residue with 1 to 18 carbon atoms, optionally combined with halogen atoms, amino groups, ether groups, ester groups, epoxy groups, mercapto groups, cyano groups or

[0266] (Poly)glycol residues are substituted, the latter being constructed from oxyethylene and / or oxypropylene units, particularly preferably around alkyl residues with 1 to 12 carbon atoms CO12402 / We

[0267] 38 or amino-functionalized alkyl group with 2 to 12 carbon atoms.

[0268] Particularly preferably, the silicones are commercially available linear silicone oils, which consist of at least 30 wt.%, preferably at least 50 wt.%, and in particular at least 60 wt.%, D units of chemical formula (X)

[0269] R8 X (OR9) y SiO2 / 2 [Formula X] , where R8 and R9 have the meaning given above and x takes values ​​from 0 to 2 and y takes values ​​from 0 to 2, where x + y = 2, exist .

[0270] The silicone oils are particularly preferred to be commercially available, essentially linear, OH-, carbinol- or (di) methoxy-terminated organopolysiloxanes such as products of the WACKER® POLYMER FD or WACKER® IM or WACKER® POLYMER AL series from Wacker Chemie AG.

[0271] Particularly preferred are commercially available aminopropyl-terminated linear silicone oils such as WACKER® FLUID NH types or other commercially available aminofunctional silicone oils, such as WACKER® FINISH WR 1100 or WR 1300 from Wacker Chemie AG.

[0272] Particularly preferably, the silicone resins are commercially available branched T-resins comprising at least 30 wt.%, preferably at least 50 wt.%, and in particular at least 60 wt.%, T-units of chemical formula (XI) CO12402 / We

[0273] 39

[0274] R8 X (OR9) y SiO3 / 2

[0275] [ Formula XI ] , where R8 and R9 have the meaning given above and x takes values ​​of 0 or 1 and y takes values ​​of 0 or 1, where x + y = 1, exist .

[0276] Furthermore, the silicone resins are particularly preferably commercially available branched MQ resins, which consist of Q units of the chemical formula to at least 20 wt.%, preferably at least 30 wt.%, and in particular at least 40 wt.%.

[0277] (XII)

[0278] SiC>4 / 2

[0279] [Formula XII] exist.

[0280] The remaining M units are units of the

[0281] Types with chemical formula (XIII)

[0282] R8 X (0R9) y Si0i / 2 [Formula XIII] , where R8 and R9 have the meaning given above and x takes values ​​from 0 to 3 and y takes values ​​from 0 to 3, where x + y = 3. CO12402 / We

[0283] 40

[0284] Preferably in the case of T resins, R8 is phenyl or an alkyl group with up to 18 carbon atoms; in the case of MQ resins, R8 is preferably methyl.

[0285] The silicone resins used are, for example, commercially available silicone resins from the SILRES® BS series, such as SILRES® MSE 100, SILRES® BS 1260, SILRES® MK Powder, SILRES® MK Scales or WACKER® MQ 803 (TF) from Wacker Chemie AG.

[0286] Non-exhaustive examples of crosslinking agents include diisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene-1,3-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 4,4'-methylenebis(phenyl isocyanate), dimethylphenyl diisocyanate, polyisocyanates with more than two isocyanate groups such as polymethylene polyphenyl polyisocyanate esters of lysine triisocyanate, phenolic resins, amino resins, epoxy resins, beta-hydroxy(alkyl)amide resins, alkylated carbamate resins, isocyanates, polyacids, anhydrides, organometals, acid-functionalized materials, polyamines, polyamides, or aminoplasts.

[0287] Non-limiting examples of suitable aminoplasts include condensates of amines and / or amides with aldehydes. The most common amines or amides are melamine, urea, or benzoguanamine. For example, the condensate of melamine with formaldehyde is a suitable aminoplast.

[0288] Other examples of crosslinking agents are polyamine compounds. Particularly suitable examples of this class of substances are dihydrazides and trihydrazides of aliphatic and aromatic dicarboxylic acids with 2 to 20 carbon atoms. Examples of suitable polyamines include ethylenediamine, isophoronediamine, diethylenetriamine, and dibutylenetriamine. Furthermore, polyhydrazides can be described as CO12402 / We

[0289] 41

[0290] Polyamine compounds can be used, such as oxalic acid dihydrazide, adipic acid dihydrazide, succinic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, phthalic or terephthalic acid dihydrazide, or itaconic acid dihydrazide. Water-soluble hydrazines such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, and butylene-1,4-dihydrazine can also be used. Further examples of crosslinking agents include polyaziridines, polycarbodiimides, and organosilanes such as alkoxysilanes, which crosslink via a condensation reaction with hydroxyl, silanol, or carboxylic acid functionalities of the copolymer. Polyfunctional aldehydes such as glyoxal or furaldehyde can also be used as crosslinking agents.

[0291] Non-exhaustive examples of non-reinforcing fillers, i.e., fillers with a BET surface area of ​​preferably up to 50 m² 2 / g, are quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolites, metal oxide powders such as aluminum, titanium, iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders such as polyacrylonitrile powder.

[0292] Non-exhaustive examples of reinforcing fillers, i.e., fillers with a BET surface area of ​​more than 50 m² 2 / g, are pyrogenic silica, precipitated silica, precipitated chalk and silicon-aluminum mixed oxides, carbon black, such as furnace and acetylene carbon black of large BET surface area, aluminum trihydroxide, hollow spherical fillers such as ceramic microspheres, elastic plastic spheres, glass spheres or fibrous fillers.

[0293] The fillers mentioned can be made hydrophobic, for example by treatment with organosilanes or organosilanes CO12402 / We

[0294] 42 or with stearic acid or by etherification of hydroxyl groups to alkoxy groups.

[0295] Preferably, the fillers used are silica. The preferred silica is commercially available pyrogenic silica such as HDK® types from Wacker Chemie AG.

[0296] Non-exhaustive examples of metal-containing hardening catalysts include organic titanium and tin compounds, such as titanium acid esters, e.g., tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate, tin compounds, e.g., dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxides and corresponding dioctyltin compounds.

[0297] Non-exhaustive examples of metal-free hardening catalysts include basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,1,2,2-tetramethylguanidine, 1,1,2,3-tetramethylguanidine, N,N-bis(N,N-dimethyl-2-aminoethyl)-methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, and N-ethylmorpholine.

[0298] Acidic compounds, such as phosphoric acid and its partially esterified derivatives, toluenesulfonic acid, sulfuric acid, nitric acid, or organic carboxylic acids like acetic acid and benzoic acid, can also be used as hardening catalysts. CO12402 / We

[0299] 43

[0300] The additives (c) of the Easy-to-Clean composition according to the invention are preferably different from the component (vi) used in the polymer according to the invention.

[0301] In a preferred embodiment, the additive (c) is selected from the group consisting of linear OH-, carbinol or alkoxy-terminated silicone oils, NH-functionalized silicone oils, T resins, MQ resins, alkylsilanes, aminosilanes and tetraal koxyt it anate en .

[0302] In a particularly preferred embodiment, the additive (c) is selected from the group consisting of NH-functionalized silicone oils, T-resins, GENIOSIL® GF 91 and butyl titanate.

[0303] The production of the Easy-to-Clean composition is preferably carried out according to methods known to a person skilled in the art.

[0304] When using the polymer (a) according to the invention, the process comprises in particular the following steps: (2a) Providing the polymer (a) according to the invention, optionally

[0305] (2ß) Adding at least one organic solvent (b) ,

[0306] (2y) Homogenizing the mixture obtained from step (2ß), preferably by stirring, dispersing, ultrasonic treatment and / or pressure treatment, if necessary

[0307] (25) Add at least one additive (c) and, if appropriate, CO12402 / We

[0308] 44

[0309] (2s) Homogenizing the mixture obtained from step (25), preferably by stirring, dispersing, ultrasonic treatment and / or pressure treatment.

[0310] When using the polymer powder (d) according to the invention, the process comprises in particular the following steps:

[0311] (3a) Providing the polymer powder according to the invention (d) ,

[0312] (3ß) Adding at least one organic solvent (b) ,

[0313] (3y) Homogenizing the mixture obtained from step (3ß), preferably by stirring, dispersing, ultrasonic treatment and / or pressure treatment, if necessary

[0314] (35) Adding at least one additive (c) and, if necessary,

[0315] (3s) Homogenizing the mixture obtained from step (35), preferably by stirring, dispersing, ultrasonic treatment and / or pressure treatment.

[0316] Preferably, at least one additive (c) is added directly after step (15).

[0317] Homogenization can preferably be carried out at room temperature or at an elevated temperature of 25-60°C, preferably 25-40°C. Homogenization is preferably carried out at room temperature.

[0318] In a preferred embodiment, homogenization is carried out at a temperature that corresponds to the homogenization at CO12402 / We

[0319] 45

[0320] The procedure was carried out by adjusting the room temperature without additional heating or cooling.

[0321] Preferably, homogenization is carried out at a temperature of 0-50 °C, more preferably at 10-50 °C and most preferably at 15-50 °C.

[0322] The sequence of the process steps for the production of the Easy-to-Clean composition according to the invention is not decisive for the quality of the Easy-to-Clean composition obtained, i.e., the sequence of the process steps for the production of the Easy-to-Clean composition according to the invention can be carried out as described above or in a different sequence.

[0323] Another object of the present invention is a method for producing a dirt-repellent coating on a substrate, comprising the following steps in the specified order:

[0324] (A) Providing the substrate ,

[0325] (B) Wetting the substrate with the Easy-to-Clean composition according to the invention, optionally

[0326] (C) Removing the supernatant of the Easy-to-Clean composition according to the invention from the wetted substrate obtained after step (B) and

[0327] (D) Drying of the wetted substrate obtained after step (B) and, if applicable, step (C). CO12402 / We

[0328] 46

[0329] The wetting of the substrate with the Easy-to-Clean composition according to the invention in step (B) can be carried out in any manner suitable for the treatment of the substrates, for example by dipping, brushing, pouring, spraying, rolling, squeegeeing, printing, fouling or foaming.

[0330] Wetting refers in particular to complete wetting. Complete wetting within the meaning of the invention means that 70-100% of the total surface area of ​​the substrate is brought into contact with the Easy-to-Clean composition according to the invention, more preferably 80-100%, most preferably 90-100%.

[0331] Preferably, wetting takes place at room temperature or a temperature of 0-40 °C, more preferably at 10-35 °C and most preferably at 15-30 °C.

[0332] Wetting is preferably carried out at room temperature.

[0333] Preferably, after wetting, an exposure time of 10 s to 14 d takes place, more preferably 10 s to 7 d and particularly preferably 10 s to 3 d.

[0334] The exposure time preferably takes place at the same temperature as the wetting.

[0335] The optional removal of the supernatant of the Easy-to-Clean composition according to the invention in step (C) is preferably carried out manually or mechanically, depending on the substrate used, for example by wiping, scraping, pipetting, suction or dabbing.

[0336] Preferably, the wetted substrate obtained after step (B) or, if applicable, (C), is dried at room temperature or at an elevated temperature of 25–200 °C, and more preferably at 25–180 °C. CO12402 / We

[0337] 47

[0338] Preferably, the wetted substrate obtained after step (B) or optionally (C) is dried at room temperature or elevated temperature of 0-200°C, more preferably 10-200°C and most preferably at 15-180°C.

[0339] Drying is preferably carried out at room temperature.

[0340] Following drying, the coated substrate is then preferably stored at room temperature for a further 1-10 days.

[0341] Another object of the present invention is a coated substrate obtainable according to the inventive method for producing a dirt-repellent coating on a substrate, as shown in detail above.

[0342] Preferably, the coated substrate according to the invention is artificial stone, natural stone, terracotta, concrete, mortar, metal, plastic, wood, paper, leather, artificial leather, textile, glass, lacquer, foam or a composite material made up of these.

[0343] Preferably, the substrate according to the invention is a planar substrate.

[0344] The substrate according to the invention is particularly preferably a flat mineral substrate, in particular a flat substrate made of artificial or natural stone, terracotta, concrete or mortar.

[0345] Artificial stones within the meaning of the present invention are to be understood as mineral, cement- or resin-bound materials produced with aggregates of gravel, sand, and rock flour. CO12402 / We

[0346] 48

[0347] Non-exhaustive examples of such artificial stones are agglomerate marble, quartz stone, terrazzo, cultured stone, solid surface, polymer concrete or onyx imitation.

[0348] Natural stones within the meaning of the present invention are to be understood as generally all naturally occurring rocks.

[0349] Non-exhaustive examples of such natural stones include silicates, slate, quartzite, limestone, travertine, marble, bluestone, granite or basalt.

[0350] Artificial leather within the meaning of the present invention is to be understood as leather imitations that can be made from synthetic or plant-based materials. Such compounds mimic the appearance and feel of natural leather.

[0351] Non-exhaustive examples of such synthetic leathers include polyester, polyurethane, polyvinyl chloride, silicone leather, or textiles with a polyvinyl chloride or polyethylene coating.

[0352] Non-exhaustive examples of such plant-based artificial leathers include cork leather, oceanic leather, pineapple leather, cactus leather, mushroom leather or apple leather.

[0353] Textiles within the meaning of the present invention are to be understood as textile substrates, i.e., substrates which are formed from fibers. The textile substrate comprises, for example, at least one natural fiber or at least one synthetic fiber or a mixture thereof.

[0354] Non-exhaustive examples of such natural fibers are cotton, linen, hemp, wool, such as sheep's wool, alpaca wool, angora wool, CO12402 / We

[0355] 49

[0356] Cashmere, mohair, yak, or merino wool, silk and blends thereof.

[0357] Non-exhaustive examples of such synthetic fibers include viscose, polyester, polyethylene terephthalate, polyamide, polyethylene, polypropylene, elastane, and mixtures thereof.

[0358] The substrates terracotta, concrete, mortar, metal, plastic, wood, paper, leather, glass, lacquer and foam include all materials that are generally understood by the expert in the relevant sense.

[0359] By using the polymers according to the invention, based on acrylate-siloxane copolymers, excellent omniphobic properties can be achieved on a wide variety of substrates such as mineral substrates, metal, plastic, wood, paper products, leather, textiles, glass, paint, and foam or composite materials made from these. In particular, these omniphobic properties can be further enhanced by adding additives to the easy-to-clean compositions comprising the polymers according to the invention. The reaction process of radical polymerization according to the invention leads to excellent conversion, making the polymerization process both economical and environmentally friendly (resource-conserving).Furthermore, the use of reaction initiators that are not azo initiators avoids the formation of toxic byproducts, and it has also been proven that solvents not belonging to the relevant CMR substances can be used, resulting in a significantly improved toxicological profile for the manufacturing process according to the invention compared to conventional manufacturing processes. CO12402 / We.

[0360] 50

[0361] Examples of implementation:

[0362] The present invention and the surprising technical advantages associated with it will be further explained by the following exemplary embodiments, without, however, limiting them to the contents disclosed therein.

[0363] Unless otherwise specified, the following examples are carried out at atmospheric pressure, i.e., at approximately 1,010 hPa, at a mean relative humidity between 40% and 60%, and at room temperature, i.e., approximately 25°C or a temperature that occurs when the components are combined at room temperature without additional heating or cooling.

[0364] Raw materials used:

[0365] Table 1 shows the names of the raw materials used in alphabetical order and their sources. All raw materials listed were used without further purification.

[0366] Table 1: Names of the raw materials used and their sources CO12402 / We

[0367] 51

[0368] Production of the polymers:

[0369] The following describes the preparation of polymers according to the invention (Examples 1-11) as well as a polymer not according to the invention without a component according to the invention (iv) and the use of a non-inventive azo initiator as a reaction initiator (i) and toluene as a solvent (ii) (Comparative Example VI) CO12402 / We

[0370] 52 described. The synthesis of comparative example VI was carried out according to H. Lei et al., Progress in Organic Coatings 103 (2017) 182-192 (example with lowest surface energy (see Fig.

[0371] 15, M3T = CLA30, 36 mol-% corresponds to 62 wt% in the specified composition). In addition, as comparative example V2, another polymer not according to the invention is presented, in which comparative example VI was modified such that a peroxide according to the invention was used as the reaction initiator (i) and ethyl acetate as the solvent (ii).

[0372] The stated wt% are based on the total weight of the monomers used.

[0373] Determination of solids content:

[0374] At the end of the reaction, the solids content of the polymer is determined using a commercially available electronic moisture analyzer from Sartorius. A defined quantity of polymer is placed onto an aluminum dish. The aluminum dish containing the polymer is inserted into the instrument and heated to 160°C. The solids content is calculated as the ratio of the remaining solids to the original total mass of the polymer (solids content = m (remaining solids) / m (initial mass of polymer)). The solids content of a polymer is adjusted using methods familiar to those skilled in the art. For example, the solids content of a polymer can be increased by distilling off the solvent. The solids content of the polymer can be reduced by diluting the polymer with solvent.Unless otherwise specified, the polymer is preferably diluted with the solvent in which the reaction was carried out. CO12402 / We.

[0375] 53

[0376] Comparative example VI: (non-inventive)

[0377] CLA30 / PMA / GENIOS IL® GF 31 (62:28:10 wt.%), toluene, AIBN

[0378] In a 500 ml flask equipped with a KPG stirrer and reflux condenser, 30.9 g of CLA30, 14.1 g of PMA, 5.1 g of GENIOSIL® GF 31, 260 g of toluene, and 0.50 g of AIBN were placed and the mixture inerted by purging with argon for 15 minutes. The reaction mixture was heated to 70°C for 48 h. The solvent was then distilled off, and the residue was dissolved in 75 ml of white spirit. The polymer was adjusted to a solids content of 40% within the limits of experimental accuracy.

[0379] Comparative example V2: (non-inventive)

[0380] CLA30 / PMA / GENIOSIL® GF 31 (62:28:10 wt.%), ethyl acetate, PW

[0381] 10 ml of ethyl acetate were placed in a 250 ml four-necked flask equipped with a KPG stirrer, reflux condenser, dropping funnel and septum.

[0382] The solvent was degassed with argon for 15 minutes. In a separate vessel, the monomer mixture consisting of 30.9 g CLA30, 14.1 g PMA, and 5.1 g GENIOSIL® GF 31 was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 0.75 g PPV (75 wt% in white spirit) and 10 ml ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78°C, 5 wt% of the monomer mixture was added to the flask, followed by the remaining monomer mixture over 4 hours and the initiator mixture over 5 hours, added concurrently. After the initiator mixture was added, 15 ml ethyl acetate was added. The reaction was post-polymerized twice by adding 0.5 g of PPV (75 wt% in white spirit) to 2.5 ml of ethyl acetate at 78°C for 1 h, followed by 2 h of stirring. The reaction mixture was then cooled to room temperature. The CO12402 / We

[0383] 54

[0384] The polymer was adjusted to a solids content of 45% within the limits of experimental accuracy.

[0385] Example 1: (according to the invention)

[0386] CLA30 / MMA / SMA / MAA (40:40:15:5 wt.%)

[0387] In a 2-liter reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 250 ml of ethyl acetate were placed. The solvent was degassed with argon for 15 minutes. In a separate vessel, the monomer mixture, consisting of 200.0 g CLA30, 200.0 g MMA, 75.0 g SMA, and 25.0 g MAA, was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture, consisting of 7.5 g PPV (75% in white spirit) and 100 ml of ethyl acetate, was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, followed by the remaining monomer mixture over 4 hours and the initiator mixture over 5 hours, all added concurrently. After the initial dose, 125 ml of ethyl acetate were added and the mixture was stirred for 1 h at 78°C. The polymerization was then repeated twice by adding 5.0 g of PPV (75% in white spirit) to 12.5 ml of ethyl acetate at 78°C for 1 h, followed by 1 h of stirring.The reaction mixture was treated with 150 ml of ethyl acetate and cooled to room temperature. The polymer was adjusted to a solids content of 40% within the limits of experimental accuracy.

[0388] Example 2: (according to the invention)

[0389] CLA30 / MMA / SA / MAA (40:40:15:5 wt.%)

[0390] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 120 ml of ethyl acetate were placed. The solvent was heated with argon CO12402 / We for 15 min.

[0391] 55. Degassed. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 80.0 g MMA, 30.0 g SA, and 10.0 g MAA was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 3.0 g PPV (75% in white spirit) and 40 ml ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, followed by the remaining monomer mixture over 4 h and the initiator mixture over 5 h, added concurrently. After the addition, 30 ml ethyl acetate was added, and the mixture was stirred for 1 h at 78 °C. The reaction was post-polymerized by adding 2.0 g of PPV (75% in white spirit) to 5 ml of ethyl acetate at 78°C for 1 h, followed by 1 h of stirring. The reaction mixture was then cooled to room temperature. The polymer was adjusted to a solids content of 50% within the limits of experimental accuracy.

[0392] Example 3: (according to the invention)

[0393] CLA30 / MMA / EHA / MAA (40:39:15:6 wt.%)

[0394] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 120 ml of 2-ethylhexyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 78.0 g MMA, 30.0 g EHA, and 12.0 g MAA was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 3.0 g PPV (75% in white spirit) and 40 ml of 2-ethylhexyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, and the initiator mixture was added over 5 h. After 1 h, the remaining monomer mixture was added over 4 h. After the addition, 100 ml of 2-CO12402 / We were measured.

[0395] 56

[0396] Ethylhexyl acetate was added and the mixture was stirred for a further 3 h at 78°C. The reaction was post-polymerized twice by adding 2.0 g of PPV (75% in white spirit) to 10 ml of ethyl acetate at 78°C for 1 h, followed by 1 h of stirring. The reaction mixture was then cooled to room temperature. The polymer was adjusted to a solids content of 50% within the limits of experimental accuracy.

[0397] Example 4: (according to the invention)

[0398] CLA30 / MMA / BA / MAA (40:39:15:6 wt.%)

[0399] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 95 ml of 2-ethylhexyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 60.0 g CLA30, 58.5 g MMA, 22.5 g BA, and 9.0 g MAA was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 2.25 g PPV (75% in white spirit) and 30 ml of ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, and then the remaining monomer mixture was added over 4 h, and the initiator mixture over 5 h, in parallel. After the initial dose, 30 ml of ethyl acetate were added and the mixture was stirred for 1 h at 78 °C. A second polymerization was then performed by adding 1.5 g of PPV (75% in white spirit) to 3.5 ml of 2-ethylhexyl acetate at 78 °C for 1 h, followed by 1 h of stirring.The reaction mixture was treated with 100 ml of 2-ethylhexyl acetate and then cooled to room temperature. The polymer was adjusted to a solids content of 35% within the limits of experimental accuracy. CO12402 / We.

[0400] 57

[0401] Example 5: (according to the invention)

[0402] CLA30 / MA / SMA / MAA (40:39:15:6 wt%)

[0403] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 130 ml of 2-ethylhexyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 78.0 g MA, 30.0 g SMA, and 12.0 g MAA was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 3.0 g PPV (75% in white spirit) and 40 ml of ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, and then the remaining monomer mixture was added over 4 h, and the initiator mixture over 5 h, in parallel. After the initial dose, 30 ml of ethyl acetate were added and the mixture was stirred for 1 h at 78 °C. The polymerization was then repeated twice by adding 2.0 g of PPV (75% in white spirit) to 5 ml of 2-ethylhexyl acetate at 78 °C for 1 h, followed by 1 h of stirring.The reaction mixture was then cooled to room temperature. The polymer was adjusted to a solids content of 40% within the limits of experimental accuracy.

[0404] Example 6: (according to the invention)

[0405] CLA30 / EA / AN / BA / MAA (40:34:20:1:5 wt.%)

[0406] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 55 ml of ethyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 68.0 g EA, 40.0 g AN, 2.0 g BA, and 10.0 g MAA was mixed with stirring and transferred to the dropping funnel. In CO12402 / We

[0407] In a separate vessel, the initiator mixture, consisting of 3.0 g PPV (75% in white spirit) and 40 ml ethyl acetate, was prepared and transferred to a syringe for dosing via a syringe pump. After heating to 68 °C, 5% of the monomer mixture was added to the flask, and the initiator mixture was added over 3 hours. After 1 hour, the remaining monomer mixture was added over 2 hours. During the dosing process, 230 ml ethyl acetate was added portionwise to the reaction mixture. After the initiator solution was added, the mixture was stirred for 1 hour at 68 °C, and then 150 ml ethyl acetate was added. A post-polymerization step was performed by adding 2.0 g PPV (75% in white spirit) in 5 ml ethyl acetate at 68 °C over 1 hour and stirring for 2 hours. During the post-polymerization, the reaction mixture was diluted with a total of 150 ml ethyl acetate. The reaction mixture was then cooled to room temperature.

[0408] The polymer was adjusted to a solids content of 40% within the limits of experimental accuracy.

[0409] Example 7: (according to the invention)

[0410] CLA30 / MMA / SMA / AM (40:40:15:5 wt.%)

[0411] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 120 ml of ethyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 80.0 g MMA, 30.0 g SMA, 10.0 g AM, 10.0 ml ethyl acetate, and 20.0 ml ethanol was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 3.0 g PPV (75% in white spirit) and 40 ml ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78°C, 5% of the monomer mixture was added to the flask, and the initiator mixture was added over 5 h. After 1 hour, the remaining monomer mixture was added in parallel over 4 hours. (According to CO12402 / We)

[0412] After the final dose of 59, 50 ml of ethyl acetate was added and the reaction mixture was stirred for 1 h at 78°C. Then, another 50 ml of ethyl acetate was added. A second polymerization step was performed by adding 2.0 g of PPV (75% in white spirit) to 5 ml of ethyl acetate at 78°C for 1 h, followed by 2 h of stirring. The reaction mixture was then treated with 100 ml of ethyl acetate and cooled to room temperature. The polymer was adjusted to a solids content of 50% within the limits of experimental accuracy.

[0413] Example 8: (according to the invention) CLA30 / MMA / SMA / GMA (40:40:15:5 wt.%)

[0414] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 75 ml of 2-ethylhexyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 60.0 g CLA30, 60.0 g MMA, 22.5 g SMA, and 7.5 g GMA was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 2.25 g PPV (75% in white spirit) and 40 ml of ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, and then the remaining monomer mixture was added over 4 h, and the initiator mixture over 5 h, in parallel. After the initial dose, 30 ml of ethyl acetate were added and the mixture was stirred for 1 h at 78 °C. A second polymerization was then performed by adding 1.5 g of PPV (75% in white spirit) to 3.5 ml of 2-ethyl acetate at 78 °C for 1 h, followed by 1 h of stirring.The reaction mixture was then cooled to room temperature and stirred with 80 ml of ethyl acetate. The polymer was adjusted to a solids content of 40% within the limits of experimental accuracy. CO12402 / We.

[0415] 60

[0416] Example 9: (according to the invention)

[0417] CLA30 / MMA / SMA / HEMA (40:40:15:5 wt.%)

[0418] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 120 ml of ethyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 80.0 g MMA, 30.0 g SMA, and 10.0 g HEMA was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 3.0 g PPV (75% in white spirit) and 40 ml of ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, and then the remaining monomer mixture was added over 4 h, and the initiator mixture over 5 h, in parallel. After the initial dose, 30 ml of ethyl acetate were added and the mixture was stirred for 1 hour at 78 °C. A second polymerization was then performed by adding 2.0 g of PPV (75% in white spirit) to 5 ml of ethyl acetate at 78 °C for 1 hour and stirring for 1 hour.The reaction mixture was then cooled to room temperature. The polymer was adjusted to a solids content of 65% within the limits of experimental accuracy.

[0419] Example 10: (according to the invention)

[0420] CLA30 / MMA / SMA / MSA (40:40:15:5 wt.%)

[0421] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 120 ml of ethyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 80.0 g MMA, 30.0 g SMA, and 10.0 g MSA was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of CO12402 / We

[0422] 61

[0423] 3.0 g of PPV (75% in white spirit) and 40 ml of ethyl acetate were prepared and transferred to a syringe for dosing via a syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, followed by the remaining monomer mixture over 4 h and the initiator mixture over 5 h in parallel. After the addition, 50 ml of ethyl acetate was added and stirred for 1 h at 78 °C. The reaction was postpolymerized twice by adding 2.0 g of PPV (75% in white spirit) to 5 ml of ethyl acetate at 78 °C over 1 h, stirring for 1 h each time, with 50 ml of ethyl acetate added after each addition. The reaction mixture was then cooled to room temperature and diluted with 125 ml of ethyl acetate while stirring. The polymer was adjusted to a solids content of 40% within the limits of experimental accuracy.

[0424] Example 11: (according to the invention)

[0425] CLA30 / MMA / SMA / AM / GENIOSIL® GF 31 (40:40:15:2:3 wt.%)

[0426] In a 500 ml reactor equipped with a KPG stirrer, reflux condenser, dropping funnel, and syringe pump with syringe, 120 ml of ethyl acetate were placed. The solvent was degassed with argon for 15 min. In a separate vessel, the monomer mixture consisting of 80.0 g CLA30, 80.0 g MMA, 30.0 g SMA, 4.0 g AM, 6.0 g GENIOSIL® GF 31, and 20.0 ml ethanol was mixed with stirring and transferred to the dropping funnel. In another vessel, the initiator mixture consisting of 3.0 g PPV (75% in white spirit) and 40 ml ethyl acetate was prepared and transferred to a syringe for dosing via syringe pump. After heating to 78 °C, 5% of the monomer mixture was added to the flask, and the initiator mixture was added over 5 h. After 1 hour, the remaining monomer mixture was added in parallel over 4 hours. Once the addition was complete, the reaction mixture was stirred for 1 hour at 78°C. Then, another 4.0 g of CO12402 / We were added.

[0427] 62

[0428] Methyltrimethoxysilane (hydrolysis stabilizer) and 30 ml of ethyl acetate were added. The mixture was postpolymerized by adding 2.0 g of PPV (75% in white spirit) to 5 ml of ethyl acetate at 78 °C for 1 h, followed by 2 h of stirring. The reaction mixture was then treated with 100 ml of ethyl acetate, cooled to room temperature, and subsequently diluted with a further 200 ml of ethyl acetate while stirring. The polymer was adjusted to a solids content of 40% within the limits of experimental accuracy.

[0429] Production of the Easy-to-Clean compositions:

[0430] The following describes the preparation of easy-to-clean compositions according to the invention (Examples 12-27) and two non-inventive easy-to-clean compositions (Comparative Examples V3 and V4). Comparative Examples V3 and V4 use the non-inventive polymers from Comparative Examples VI and V2, respectively. Examples 23 and 24 are differently additivated easy-to-clean compositions with the polymer from Example 9. Examples 25-27 are differently additivated easy-to-clean compositions with the polymer from Example 10. White spirit (Comparative Example V3) or butyl acetate (Comparative Example V4 and Examples 12-27) are used as organic solvents (b).

[0431] The manufacturing process according to the invention comprises steps 2a, 2ß, 2y by stirring and optionally 25 and optionally 2s by stirring. CO12402 / We

[0432] 63

[0433] Comparative example V3: (non-inventive)

[0434] Easy-to-clean composition with polymer from comparative example VI, White Spirit

[0435] 4 g of the polymer from comparative example VI was diluted with 12 g of white spirit to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0436] Comparative example V4: (non-inventive)

[0437] Easy-to-clean composition with polymer from comparison example V2

[0438] 4 g of the polymer from comparison example V2 was diluted with 14 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0439] Example 12: (according to the invention)

[0440] Easy-to-clean composition with polymer from example 1

[0441] 4 g of the polymer from Example 1 was diluted with 12 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0442] Example 13: (according to the invention)

[0443] Easy-to-clean composition with polymer from example 2

[0444] 4 g of the polymer from Example 2 was diluted with 16 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild. CO12402 / We

[0445] 64

[0446] Example 14: (according to the invention)

[0447] Easy-to-clean composition with polymer from example 3

[0448] 4 g of the polymer from Example 3 was diluted with 16 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0449] Example 15: (according to the invention)

[0450] Easy-to-clean composition with polymer from example 4

[0451] 4 g of the polymer from Example 4 was diluted with 10 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0452] Example 16: (according to the invention)

[0453] Easy-to-clean composition with polymer from example 5

[0454] 4 g of the polymer from Example 5 was diluted with 12 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0455] Example 17: (according to the invention)

[0456] Easy-to-clean composition with polymer from example 6

[0457] 4 g of the polymer from Example 6 was diluted with 12 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild. CO12402 / We

[0458] 65

[0459] Example 18: (according to the invention)

[0460] Easy-to-clean composition with polymer from example 7

[0461] 4 g of the polymer from Example 7 was diluted with 16 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0462] Example 19: (according to the invention)

[0463] Easy-to-clean composition with polymer from example 8

[0464] 4 g of the polymer from Example 8 was diluted with 12 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0465] Example 20: (according to the invention)

[0466] Easy-to-clean composition with polymer from example 9

[0467] 4 g of the polymer from Example 9 was diluted with 22 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0468] Example 21: (according to the invention)

[0469] Easy-to-clean composition with polymer from example 10

[0470] 4 g of the polymer from Example 10 was diluted with 12 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild. CO12402 / We

[0471] 66

[0472] Example 22: (according to the invention)

[0473] Easy-to-clean composition with polymer from example 11

[0474] 4 g of the polymer from Example 11 was diluted with 12 g of butyl acetate to a final solids content of 10% and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0475] Example 23: (according to the invention)

[0476] Easy-to-clean composition with polymer from example 9, Trasil, tetra-n-butyl titanate

[0477] 3.08 g of the polymer from Example 9 was diluted with 16.92 g of butyl acetate to a final solids content of 10%. 1.0 g of Trasil and 0.02 g of tetra-n-butyl titanate were added and the mixture was homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0478] Example 24: (according to the invention)

[0479] Easy-to-clean composition with polymer from example 9, SILRES® MSE 100

[0480] 3.08 g of the polymer from Example 9 was diluted with 16.92 g of butyl acetate to a final solids content of 10%. 1.0 g of SILRES® MSE 100 was added and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0481] Example 25: (according to the invention)

[0482] Easy-to-clean composition with polymer from example 10, WACKER® Fluid NH 15

[0483] 5.0 g of the polymer from Example 10 was diluted with 15.0 g of butyl acetate to a final solids content of 10%. CO12402 / We

[0484] 0.2 g of WACKER® Fluid NH 15 was added to step 67 and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0485] Example 26: (according to the invention)

[0486] Easy-to-clean composition with polymer from example 10, GENIOS IL® GF 91

[0487] 5.0 g of the polymer from Example 10 was diluted with 15.0 g of butyl acetate to a final solids content of 10%. 0.04 g of GENIOS IL® GF 91 was added and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0488] Example 27: (according to the invention)

[0489] Easy-to-clean composition with polymer from example 10, tetra-n-butyl titanate

[0490] 5.0 g of the polymer from Example 10 was diluted with 15.0 g of butyl acetate to a final solids content of 10%. 0.04 g of tetra-n-butyl titanate was added and homogenized for 20 s using a commercially available speed mixer from Hausschild.

[0491] Production of the coated substrates:

[0492] The following describes the production of coated substrates according to the invention using the easy-to-clean compositions according to the invention from Examples 12-27, as well as coated substrates not according to the invention using the easy-to-clean compositions not according to the invention from Comparative Examples V3 and V4. CO12402 / We

[0493] 68

[0494] The manufacturing process according to the invention comprises steps A, B, C and D and was carried out as follows:

[0495] The easy-to-clean formulations were applied twice in a thin layer (approximately 0.1 - 0.4 g / dm²) using a brush. 2 The coating was applied to uncoated natural stone slabs (L 15 cm x W 15 cm x D 0.8 cm) made of Chinese granite (source: Pollety Naturstein), Carrara marble (source: Pollety Naturstein), and Solnhofen limestone (source: Pollety Naturstein). After approximately 1.5 minutes of exposure at room temperature, the excess was removed with a paper towel. The coated substrate was then stored at room temperature for 6 days to dry.

[0496] Evaluation of the omniphobicity of the coated substrates using a dirt test:

[0497] The dirt test described below and the assessment of the omniphobicity of the coated substrates were developed in the laboratory and are based on the methodology described in H. Lei et al., Progress in Organic Coatings 103 (2017) 182-192 under 2.3.1.

[0498] Various aqueous and oily household stains (espresso, red wine, ketchup, mustard, mayonnaise, pumpkin seed oil, and safflower oil) were applied to the coated substrate at room temperature in a grid-like pattern with sufficient spacing between them (to prevent contamination). This application pattern was identical for all coated substrates. 150 pL each of the low-viscosity liquids espresso and red wine, and approximately 90 pL each of pumpkin seed oil and safflower oil, were pipette-applied to the coated substrate. Of the higher-viscosity stains ketchup, mustard, and mayonnaise, CO12402 / We

[0499] 69 samples were each injected with approximately 0.4 g onto the coated substrate at room temperature using a syringe. After a contact time of 1 day at room temperature, the household dirt was removed with a cloth and water.

[0500] The residue of each household dirt was then rated on a scale of 0 to 4 (0: no stains visible, 1: faint stain visible, 2: noticeable stain visible, 3: noticeable stain visible and dirt partially absorbed into the substrate, 4: dirt completely absorbed into the substrate). To ensure comparability of the dirt test, the ratings were always performed by the same person. For each coated substrate, the ratings for all household dirts were added together (individual rating per substrate). Two substrates were coated per natural stone. Tables 2 to 4 present the arithmetic mean of the two substrates per natural stone as results (two-fold rating per natural stone). The lower this two-fold rating, the better the omniphobic properties of a coating on the respective natural stone used.The overall omniphobic rating is calculated by summing the individual ratings for each of the three natural stones used (overall natural stone rating). The lower this overall rating, the better the omniphobic properties of a coating.

[0501] Results :

[0502] Table 2 shows the results of the dirt tests and the associated omniphobia ratings (two ratings per natural stone and overall rating of natural stone) for untreated substrates (reference), the comparison examples V3 and V4, and the inventive examples 12-15 on the three natural stones CO12402 / We

[0503] 70 Chinese granite (Granite ), Carrara marble (Marble ) and Solnhofen natural stone (SN) .

[0504] Table 2: Results of the dirt tests and assessment of omniphobia for untreated substrates, comparison examples V3 and V4 as well as examples 12-15

[0505] Table 3 shows the results of the dirt tests and the associated assessments of omniphobia (two-fold assessment per natural stone and overall assessment of natural stone) for the inventive examples 16-22 on the three natural stones Chinese granite (Granite ), Carrara marble (Marble) and Solnhofen natural stone (SN) .

[0506] Table 3: Results of the dirt tests and assessment of omniphobia for examples 16-22

[0507] Comparative example V3 shows improved omniphobia compared to all uncoated substrates (references), but a significantly worse overall rating compared to examples 12-22 according to the invention. In comparative example V4, CO12402 / We

[0508] 71

[0509] Comparative Example V3 was modified such that a peroxide according to the invention was used as the reaction initiator (i) and ethyl acetate as the solvent (ii). The overall evaluation of Comparative Example V4 shows no improvement in the omniphobic properties. From this, it can be concluded that improved omniphobicity can only be achieved with a polymer according to the invention, as demonstrated by Examples 12-22.

[0510] Table 4 shows the results of the dirt tests and the associated omniphobicity ratings (two ratings per natural stone and overall rating for the natural stone) for Examples 20 and 21 according to the invention, which contain the polymers according to the invention from Examples 9 and 10 respectively, as well as Examples 23-27 according to the invention on the three natural stones Chinese granite (Granite), Carrara marble (Marble), and Solnhofen natural stone (SN). Examples 23-24 are differently additivated easy-to-clean compositions with the polymer from Example 9. Examples 25-27 are differently additivated easy-to-clean compositions with the polymer from Example 10. Examples 20 and 21 are thus the non-additivated easy-to-clean base compositions for Examples 23-24 and 25-27 respectively.

[0511] CO12402 / We

[0512] Table 4: Results of the dirt tests and assessment of omniphobia for examples 20 and 21 as well as 23-27

[0513] Examples 23-27 demonstrate, in comparison to the non-additived Easy-to-Clean base compositions from Examples 20 and 21, that the omniphobic properties can be significantly improved by targeted additives.

Claims

CO12402 / We 73 Patent claims:

1. Polymer obtained by radical polymerization of a starting mixture comprising: (i) at least one reaction initiator that is not an azo initiator, (ii) at least one organic solvent, (iii) 5-95 wt% of at least one monomer of the following chemical formula (I) [ Formula I ] , wherein RI H or a hydrocarbon residue with 1-6 C atoms, Y Methylene or ethylene is, R2 is H or Methyl, n is 0 or 1, Z Methylene or 0 is and R3, R4 and R5 are the same or different and each independently of each other CHs, C2H5, n-propyl, iso-propyl, OSi- (CH3)3, OSi- (C2H5)3, O-Si- (n- CO12402 / We 74 Propyl) 3 or O-Si- (iso-propyl) 3 are, (lv) 5-95 wt.% iv-a) of at least one monomer of the following chemical formula (II) [ Formula II] , wherein RI H or a hydrocarbon residue with 1-6 C atoms is and R6 is a hydrocarbon residue with 1 or 2 C atoms and / or iv-b) at least one monomer acrylonitrile, (v) 1-80 wt.% va) of at least one monomer of the following chemical formula (III) CO12402 / We [Formula III] , wherein RI H or a hydrocarbon residue with 1-6 C atoms is and R7 is a hydrocarbon residue with 3 or more carbon atoms, and / or vb) at least one monomer styrene and (vi) 0.1-30 wt% of at least one ethylene-unsaturated monomer having at least one further functional group in addition to the ethylene-unsaturated group, wherein component (vi) is different from components (iii) to (v) and is not an ester or diester of itaconic acid, wherein the wt% indicated are based on the total weight of components (iii) to (vi).

2. Polymer according to claim 1, wherein RI is H or methyl.

3. Polymer according to claim 1 or 2, wherein Y and Z respectively Methylene are, where R2 is H, CO12402 / We 76 where n is 0 and where R3, R4 and R5 are O-Si (CH3)3.

4. Polymer according to any one of claims 1 to 3, wherein R7 is a hydrocarbon residue with 3-22 C atoms.

5. Polymer according to any one of claims 1 to 4, wherein the ethylene-unsaturated monomer (vi) is selected from the group consisting of monomers with C=C double bonds, C=C triple bonds, aromatics, O-containing, N-containing, S-containing, P-containing, halogen-containing and Si-containing functional groups.

6. Polymer according to any one of claims 1 to 5, wherein the ethylene-unsaturated monomer (vi) is selected from the group consisting of (meth)acrylic acid, maleic anhydride, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, N-methylol (meth)acrylamide, acetoacetoxyethyl (meth)acrylate, 3-(Trimethoxysilyl)propyl(meth)acrylate and 3-(Triethoxysilyl)propyl(meth)acrylate.

7. Polymer according to any one of claims 1 to 6, wherein the starting mixture contains 25-60 wt% of at least one monomer (iii) contains the chemical formula (I).

8. Method for producing the polymer according to any one of claims 1 to 7, wherein a starting mixture comprising (i) at least one reaction initiator which is not Azo initiator is, CO12402 / We (ii) at least one organic solvent, (iii) 5-95 wt% of at least one monomer of the following chemical formula (I) [ Formula I ] , wherein RI H or a hydrocarbon residue with 1-6 C atoms, Y Methylene or ethylene is, R2 is H or Methyl, n is 0 or 1, Z Methylene or 0 is and R3, R4 and R5 are the same or different and are each independently CHs, C2H5, n-propyl, iso-propyl, OSi- (CH3)3, OSi- (C2H5)3, O-Si- (n-propyl)3 or O-Si- (iso-propyl)3 (iv) 5-95 wt.% iv-a) of at least one monomer of the following chemical formula (II) CO12402 / We [Formula II] wherein RI H or a hydrocarbon residue with 1-6 C atoms is and R6 a hydrocarbon residue with 1 or 2 C atoms, and / or iv-b) at least one monomer acrylonitrile, 1-80 wt. va) of at least one monomer of the following chemical formula (III) [Formula III] wherein RI H or a hydrocarbon residue with 1-6 C atoms is and R7 is a hydrocarbon residue with 3 or more C atoms is, CO12402 / We 79 vb) and / or at least one monomer Styrene and (vi) 0.1-30 wt% of at least one ethylene-unsaturated monomer having at least one further functional group in addition to the ethylene-unsaturated group, wherein component (vi) is different from components (iii) to (v) and is not an ester or diester of itaconic acid, wherein the wt% indicated are based on the total weight of components (iii) to (vi), is polymerized by radicals.

9. Polymer powder obtainable by drying the polymer according to any one of claims 1-7.

10. Easy-to-clean composition, comprehensive (a) the polymer according to any one of claims 1-7, (b) where appropriate at least one organic solvent and (c) optionally at least one additive.

11. Easy-to-Clean composition according to claim 10, wherein the amount of polymer (a) is 0.1-80 wt.%, based on the total weight of the Easy-to-Clean composition and CO12402 / We 80 the amount of additive (c) is 0-80 wt.%, based on the total weight of the Easy-to-Clean composition.

12. Easy-to-clean composition, comprehensive (d) the polymer powder according to claim 9, (b) at least one organic solvent and (c) optionally at least one additive.

13. Easy-to-Clean composition according to claim 12, wherein the amount of polymer powder (d) is 0.1-80 wt.%, based on the total weight of the Easy-to-Clean composition and the amount of additive (c) is 0-80 wt.%, based on the total weight of the Easy-to-Clean composition.

14. Easy-to-Clean composition according to any one of claims 10 to 13, wherein the additive (c) is selected from the group consisting of silanes, silicones, silicone resins, crosslinkers, fillers and curing catalysts.

15. Method for producing a dirt-repellent coating on a substrate, comprising the following steps in the specified order: (A) Providing the substrate, (B) Wet the substrate with the Easy-to-Clean Composition according to any one of claims 10 to 14, CO12402 / We 81 if necessary (C) Removal of the supernatant of the Easy-to-Clean composition according to any one of claims 10 to 14 from the wetted substrate obtained after step (B) and (D) Drying the wetted substrate obtained after step (B) and, if applicable, step (C).

16. Coated substrate available according to a method for producing a dirt-repellent coating on a substrate according to claim 15.

17. Coated substrate according to claim 16, wherein the substrate is artificial stone, natural stone, terracotta, concrete, mortar, metal, plastic, wood, paper, leather, artificial leather, textile, glass, lacquer, foam or a composite material thereof.

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