Silicone resin-based, fluorine-free non-stick coating for cookware applications

Abstract

The invention relates to fluorine-free, silicone resin-based non-stick coatings, comprising at least one organopolysiloxane (A), at least one end-position-terminated, hydroxy-functional polysiloxane diol (B) and at least one condensation catalyst (C), for cookware application, and to a method for producing these coatings.

Description

[0001] WA12415S / WI 1 Silicone resin-based, fluorine-free non-stick coating for cookware applications The invention relates to fluorine-free, silicone resin-based non-stick coatings comprising at least one organopolysiloxane (A), at least one terminally terminated, hydroxy-functional polysiloxane diol (B), and at least one condensation catalyst (C) for cookware applications, as well as a method for producing these coatings. Background of the invention: The present invention relates to fluorine-free, silicone resin-based non-stick coatings for cookware applications based on reactive organopolysiloxanes (silicone resins, so-called...Silicone intermediates), in combination with suitable functional, reactive, terminally terminated hydroxy-functional polysiloxanediols (silicone polymers), organic solvents, and a condensation catalyst, which can be applied as a thin film to a support substrate, typically steel or aluminum, and cured at elevated temperatures (approx. 30 min. at 250°C–300°C). The coating is characterized by a long-lasting non-stick effect, high durability, and good flexibility. State of the art: Non-stick coatings based on fluoropolymers have long been known in the art, for example, for coating baking molds or cookware (e.g., pots and pans). Polytetrafluoroethylene (PTFE) is a very commonly used fluoropolymer in this context.PTFE coatings possess excellent non-stick properties due to their low surface energy and high temperature resistance due to their high CF bond energies. WA12415S / WI 2 However, in addition to the advantages described, fluoropolymer coatings have a number of disadvantages. Due to its high melt viscosity, PTFE can only be processed at very high temperatures. The curing temperatures used are around 410°C. This processing temperature is above the decomposition temperature of PTFE, which can release toxic and aggressive decomposition products such as trifluoroacetic acid and carbonyl fluoride (fluorophosgene). Furthermore, the production of fluoropolymers often involves the use of fluorine-containing wetting agents (PFAS), which, due to their lack of biodegradability, can accumulate in the environment and pose a risk to human, animal, and environmental health.Fluorine-free non-stick coatings are also known from the prior art. Silicone-modified polyesters, in which part of the polyester is replaced by silicones, often exhibit insufficient temperature resistance and non-stick properties, as the polyester component oxidizes (burns) easily at high temperatures above 230°C. Finally, fluorine-free non-stick coatings are known from the prior art, such as those described in EP 2177 580 B1, which are produced using the sol-gel process. These coatings are very temperature-resistant but are also very hard and brittle. These non-stick coatings, often also referred to as ceramic coatings, are often only conditionally suitable as non-stick coatings for cookware due to their brittleness and insufficient non-stick effect. Patent US 7510774 describes a silicone resin-based, fluorine-free non-stick coating based on standard silicone resins available on the market (e.g., [example needed]).SILRES MK, SILRES SY 409) in combination with a “silicone fluid”, an inorganic filler (referred to as a “durability agent”). Our tests have shown that this formulation is well suited for baking pans (use temperature range 180°C – 200°C), but also rather unsuitable for cookware due to discoloration in the temperature range 250°C – 300°C (= typical use temperature of cookware) and a very rapid decrease in the effectiveness of the non-stick properties. Patent EP 4265697 A1 describes non-stick coatings based on silicone resin in combination with a low molecular weight polysiloxanediol with 4–50 repeat units. Our tests have shown that short-chain silicone oils (polysiloxanediols) in combination with the aforementioned silicone resins do not exhibit sufficient non-stick properties for cookware applications.Subject of the invention: This invention has succeeded in developing a fluorine-free non-stick coating based on highly reactive, low-molecular-weight organopolysiloxanes, so-called silicone intermediates, which, in combination with suitable terminally terminated, hydroxy-functional polysiloxane diols (silicone polymers), organic solvents and catalysts, achieve a durable non-stick coating for cookware with additional good flexibility. Among other things, the use of highly reactive, low-molecular-weight organopolysiloxanes, so-called silicone intermediates, distinguishes this invention from the prior art, such as the aforementioned document US 7510774. A first object of the invention is thus a fluorine-free curable composition comprising (A) at least one organopolysiloxane (A) with a weight-mean molecular weight MW in the range of 800 g / mol – 50 000 g / mol containing units of the general formula (I) WA12415S / WI 4 R. a Si(OR1 ) b O (4-a-b) / 2 (I) wherein:R is the same or different and represents a monovalent, SiC-bound, optionally substituted C1-C20 hydrocarbon residue, R 1 is the same or different and represents a hydrogen atom or a monovalent C1-C6 alkyl group, a and b each have a value of 0, 1, 2 or 3, provided that the sum a + b ≤ 3, and a has the value 1 in at least 30% of all units of formula (I) and a has an average value of 0.9 to 1.9 over all units of formula (I) and b has an average value of 0.1 to 1.8 over all units of general formula (I), (B) at least one terminally terminated, hydroxy-functional polysiloxanediol (B) with a molecular weight of 22,000 – 370,000 g / mol of general formula (II) HO[SiR3 20]mH (II), wherein R 3 is the same or different and has a C1-C30 alkyl group, a C5-C 10-Cyclocylakyl residue, a C6-C 10 -Aryl residue or a C7-C 14(A) comprises an aralykl residue, which may optionally be substituted, and where WA12415S / WI 5m has a value of 300–5000, preferably from 300 to 3500, particularly from 300 to 1500, and (C) at least one condensation catalyst (C). Possible substituents are hydroxy groups, nitrogen-containing groups such as amino groups, or sulfur-containing groups such as thiol groups. The molecular weight of the described organopolysiloxane (A), expressed as a weight average Mw, is preferably in the range of 800 g / mol–40,000 g / mol, particularly preferably in the range of 1,000 g / mol–20,000 g / mol, and most preferably in the range of 1,000 g / mol–5,000 g / mol. The molecular weight can be determined by methods known to those skilled in the art, such as Size exclusion chromatography. Preferably, the organopolysiloxane (A) consists exclusively of units of formula (I).R preferably represents a methyl, ethyl, propyl, or phenyl residue.Particularly preferably, R represents methyl and / or phenyl, wherein preferably all units of formula (I) exclusively comprise units R in which R represents methyl and / or phenyl. Preferably, at least 50% of all units of formula (I), and particularly preferably at least 70% of all units of formula (I), comprise a phenyl unit. Particularly preferably, the units of formula (I) that comprise a phenyl unit do not comprise any further unit R (a=1). R1 ​​preferably represents a methyl, ethyl, or propyl group, and particularly preferably a methyl group. In a particularly preferred embodiment, the organopolysiloxane (A) is a methylphenylpolysiloxane, WA12415S / WI 6, and in particular a reactive, solvent-free, low-molecular-weight, alkoxy-functional methylphenylpolysiloxane.The variable a preferably has the value 1 in 50% of all units of formula (I), particularly preferably in 70% of all units of formula (I), and especially preferably in 90% of all units of formula (I). The variable b preferably has a value of 1 or 2, wherein a, averaged over all units of formula (I), preferably has a value of 1.1 to 1.5. Examples of the organopolysiloxane (A) are organopolysiloxane resins which consist essentially, preferably exclusively, of units selected from (Q) units of formula SiO. 4 / 2 , Si(OR 2 )O3 / 2, Si(OR 2 )2O2 / 2 and Si(OR 2 )3O1 / 2, (T)-units of the formulas PhSiO3 / 2, PhSi(OR 2 )O2 / 2 and PhSi(OR 2 )2O1 / 2, T-units of the formulas MeSiO 3 / 2 , MeSi(OR 2 )O 2 / 2 and MeSi(OR 2 )2O 1 / 2 , (D)-units of the formulas Me2SiO2 / 2 and Me2Si(OR 2)O1 / 2 and (M) units of the formula Me3SiO1 / 2, where Me is for methyl group, Ph is for phenyl group and R 2 for hydrogen atom or optionally with halogen atoms substituted alkyl groups with 1 to 10 carbon atoms, preferably for unsubstituted alkyl groups with 1 to 4 carbon atoms, wherein the resin preferably contains 0-2 mol (Q) units, 0-2 mol (D) units and 0-2 mol (M) units per mol (T) units. Preferred examples of the organopolysiloxane (A) are organopolysiloxane resins which consist essentially, preferably exclusively, of units selected from T units of the formulas PhSiO3 / 2, PhSi(OR 2 )O2 / 2 and PhSi(OR 2 )2O1 / 2 and D-units of the formulas Me2SiO 2 / 2 and Me2Si(OR 2 )O 1 / 2 , where Me represents methyl group, Ph represents phenyl group and R 2for hydrogen atom or optionally halogen-substituted alkyl groups with 1 to 10 carbon atoms, preferably for unsubstituted alkyl groups with 1 to 4 carbon atoms. WA12415S / WI 7 Further preferred examples of the organopolysiloxane (A) are organopolysiloxane resins which consist essentially, preferably exclusively, of units selected from T-units of the formulas PhSiO 3 / 2 , PhSi(OR 2 )O 2 / 2 and PhSi(OR 2 )2O 1 / 2 , T-units of the formulas MeSiO3 / 2, MeSi(OR 2 )O2 / 2 and MeSi(OR 2 )2O1 / 2 as well as D units of the formulas Me2SiO2 / 2 and Me2Si(OR 2 )O1 / 2, where Me represents methyl group, Ph represents phenyl group and R 2For hydrogen atoms or, optionally, halogen-substituted alkyl groups with 1 to 10 carbon atoms, preferably for unsubstituted alkyl groups with 1 to 4 carbon atoms, with a molar ratio of phenylsilicone to methylsilicone units of 0.5 to 4.0. The D-unit content in these silicone resins is preferably below 10 wt.%. Naturally, the silicone resin binders described in the preceding three paragraphs can also be used in any mixtures. Mixtures of silicone resin binders, as described in the last two paragraphs, are particularly preferred.The recommended polysiloxanediols (B) are preferably those with a mean chain length of m = 300–5,000 repeat units and a molecular weight of 22,000–370,000 g / mol, and particularly preferably with a mean chain length of m = 300–3,500 repeat units and a molecular weight of 22,000–259,000 g / mol, especially with a mean chain length of m = 300–1,500 repeat units and a molecular weight of 22,000–111,000 g / mol. In a preferred embodiment, the fluorine-free composition according to the invention is free of polysiloxanediols (B) with a mean chain length of m < 300. WA12415S / WI 8 The remainder R. 3The catalyst is preferably selected independently of one another from methyl, ethyl, or phenyl, particularly preferably methyl or ethyl, and especially methyl. The at least one condensation catalyst (C) is preferably selected from acids, bases, or organometallic compounds, such as metal chelates or metal alkoxylates, and particularly selected from organometallic compounds. Examples of acids suitable as acidic catalysts are preferably mineral acids such as hydrochloric acid, nitric acid, or phosphoric acid, with hydrochloric acid being particularly preferred; poly-acids such as polyphosphoric acid, polyacrylic acid, and polyvinyl sulfuric acid; or preferably carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, adipic acid, benzoic acid, phthalic acid, or citric acid. The acidic catalysts are used in amounts of 1 ppm to 1 wt.%, preferably less than 0.1 wt.%, based on the total weight of the silicone resin.The concentration of these aqueous solutions is 5–35%, preferably 10–30%, and particularly 25%. 25% aqueous solutions of hydrochloric acid are especially preferred. Examples of bases suitable as basic catalysts include hydroxides, methanolates, ethanolates, and isopropanolates, ammonia, amines, alkali and alkaline earth hydroxides, carbonates and hydrocarbons of the alkali and alkaline earth metals, silanolates and siliconates of the alkali metals, ammonium and phosphonium hydroxides or their silanolates, and ammonium and phosphonium alkoxides. A basic condensation catalyst is preferably used as the basic catalyst or as part of the component. This catalyst boils, sublimes, or decomposes, losing its basic properties, at a pressure of 0.1 MPa and temperatures up to 600°C. WA12415S / WI 9 In particular, quaternary ammonium and / or phosphonium compounds are suitable, especially those of formulas (2) and (3): Formula (2): R. 4 4NOR 5Formula (3): R 6 4POR 7 where R4 and R6 have meaning independently of R and R5 and R 7 independent of R 1 a remnant of the type R 1 This means that compounds of formulas (2) and (3) are in particular the tetra(C1bisC) compounds. 18 -hydrocarbon)ammonium hydroxides and the tetra(C1 to C18 hydrocarbon)phosphonium hydroxides are preferred, wherein the hydrocarbon residues are in particular alkyl, aryl, alkaryl and aralkyl residues. The tetra(C1 to C 12The catalysts are ammonium hydroxides (C1 to C18 hydrocarbons) and tetra(C1 to C18 hydrocarbons)phosphonium hydroxides and / or their silanolates. The latter are produced by reacting the quaternary ammonium and phosphonium hydroxides with organosilanes or organosiloxanes. Benzyltrimethylammonium hydroxide is particularly preferred, which decomposes at 0.1 MPa and 130°C into benzyl alcohol and gaseous trimethylamine. Tetramethylammonium hydroxide is also preferred. Tetra-n-butylphosphonium hydroxide is also particularly preferred, which decomposes at 0.1 MPa and 150°C into tri-n-butylphosphine oxide and butane, the latter of which can escape as a gas. The basic catalysts are used in amounts of 100 ppm to 1 wt.%, preferably less than 0.5 wt.% based on the total weight of the silicone resin. The concentration of these aqueous or alcoholic solutions is 5–75%, preferably 10–50%, particularly 40%.Particularly preferred are 40% WA12415S / WI 10 methanolic or ethanolic solutions of benzyl trimethylammonium hydroxide. Examples of metal chelates as condensation catalysts (C) are titanium chelates, which can be used as a single compound or as a mixture of monomeric titanium chelates. Suitable chelating ligands include, among others, diketo compounds such as ethyl acetoacetate, methyl acetoacetate, and acetylacetoacetate. The titanium chelates can be pure compounds or be formed in situ by mixing alkyl titanates with the chelating ligands. Preferably, pure compounds are used. Such titanium chelate complexes are commercially available from various suppliers such as DuPont Tyzor®, Borica Tytan®, and JohnsonMatthey Vertec®. Suitable examples include Tyzor® AA, AA-65, AA-75, AA-105, GBA, GBO, DC, TE, and PITA from DuPont. VERTECTM XL 165, KE2, KE4, KE6 from Johnson Matthey Catalyst, TYTANTM S2, S4, S6 from Borica Co.Preferably, ethylacetoacetate complexes of titanium, such as TYZOR® PITA, are used as a condensation catalyst (C). Examples of metal alkoxylates are alkoxylates of titanium, in particular titanium tetrabutanoate. Metal alkoxylates are particularly preferred as a condensation catalyst (C). In a preferred embodiment, the curable composition further comprises at least one organic solvent (D). Aromatic solvents such as xylene, toluene, benzene, or mixtures of aliphatic hydrocarbons (such as Isopar E from ExxonMobil Chemical, Crystal Oil K-30 or K-60 from Shell) can be used as solvents (D). Esters such as isomeric butyl acetate or ethyl acetate can also be used. Alcohols (such as n-butyl alcohol) have proven advantageous for stabilization. In a preferred embodiment, the amount of at least one organopolysiloxane (A) is 20-80 wt.-% based on the total mass of the fluorine-free curable composition. In a preferred embodiment, the amount of at least one polysiloxanediol (B) is 0.05–0.5 wt.% based on the total mass of the fluorine-free curable composition. In a preferred embodiment, the amount of at least one condensation catalyst (C) is 1.0–3.0 wt.% based on the total mass of the fluorine-free curable composition. In a preferred embodiment, the amount of at least one organic solvent (D) is 16.5–78.5 wt.% based on the total mass of the fluorine-free curable composition. In a preferred embodiment, the fluorine-free composition according to the invention consists of components (A), (B), (C), and optionally (D).A further object of the present invention is directed to a method for producing a fluorine-free non-stick coating on a substrate, comprising (i) applying the curable formulation according to the invention to a substrate, and (ii) treating the formulation applied in step (i) by heating. The substrate is preferably a metal suitable for cookware applications, in particular steel or aluminum. The substrate is, in particular, a surface of cookware. The application in step (i) is preferably achieved by spraying, doctoring, spin coating, or brushing the substrate with the curable composition according to the invention. It is recommended to apply the coating with a dry film thickness in the range of 10–100 µm, in particular in the range of 15–30 µm.Preferably, the temperature treatment in step (ii) is carried out at 200-500 °C, preferably at 250-300 °C for a period of 10-120 min, preferably 20-60 min. Another object of the present invention is a carrier, in particular cookware, coated with the fluorine-free composition according to the invention.

[0002] WA12415S / WI 13 Examples: The following examples serve to further explain the invention. They are to be understood as illustrative, not limiting. All percentages refer to weight. Unless otherwise stated, all manipulations are carried out at room temperature of 23°C and under normal pressure (1.013 bar). Unless otherwise stated, all data for describing product properties apply at room temperature of 23°C and under normal pressure (1.013 bar). The apparatus used are commercially available laboratory instruments, such as those offered for sale by numerous manufacturers. Ph means one phenyl group = C6H5-. Me means one methyl group = CH3-. Me2 means two methyl groups accordingly. HCl means hydrogen chloride. In this text, substances are characterized by stating data obtained by means of instrumental analysis.The underlying measurements are either performed according to publicly available standards or determined using specially developed methods. To ensure clarity of the communicated teaching, the methods used are specified below. In all examples, the values ​​of parts and percentages refer to weight unless otherwise stated. WA12415S / WI 14 Viscosity: Unless otherwise stated, viscosities are determined by rotational viscometric measurement according to DIN EN ISO 3219. Unless otherwise stated, all viscosity values ​​are at 25°C and standard pressure of 1013 mbar. Molecular compositions: Molecular compositions are determined by nuclear magnetic resonance spectroscopy (for terminology, see ASTM E 386: High-resolution nuclear magnetic resonance spectroscopy (NMR): Terms and symbols), whereby the... 1 H-core and the 29 The silicon core will be measured. Description 1¹H NMR Measurement Solvent: CDCl3, 99.8%d Sample concentration: approx. 50 mg / 1 ml CDCl3 in 5 mm NMR tube Measurement without addition of TMS, spectral reference of residual CHCl3 in CDCl3 to 7.24 ppm Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Sample head: 5 mm BBO sample head or SMART sample head (Bruker) Measurement parameters: Pulprog = zg30 TD = 64kΩ NS = 64 or 128 (depending on the sensitivity of the sample head) SW = 20.6 ppm AQ = 3.17 s D1 = 5 s WA12415S / WI 15 SFO1 = 500.13 MHz O1 = 6.175 ppm Processing parameters: SI = 32kΩ WDW = EM LB = 0.3 Hz Depending on the type of spectrometer used, individual adjustments to the measurement parameters may be necessary. Description 29Si-NMR Measurement Solvent: C6D6 99.8%d / CCl4 1:1 v / v with 1 wt% Cr(acac)3 as relaxation reagent Sample concentration: approx. 2 g / 1.5 ml solvent in 10 mm NMR tube Spectrometer: Bruker Avance 300 Probe: 10 mm 1H / 13C / 15N / 29Si glass-free QNP probe (Bruker) Measurement parameters: Pulprog = zgig60 TD = 64kΩ NS = 1024 (depending on the sensitivity of the probe) SW = 200 ppm AQ = 2.75 s D1 = 4 s SFO1 = 300.13 MHz O1 = -50 ppm Processing parameters: SI = 64kΩ WDW = EM LB = 0.3 Hz WA12415S / WI 16 Depending on the type of spectrometer used, individual adjustments of the measurement parameters may be necessary. Molecular weight distributions: Molecular weight distributions are determined as weight mean (Mw) and number mean (Mn) using gel permeation chromatography (GPC or size exclusion chromatography (SEC)) with a polystyrene standard and refractive index detector (RI detector). Unless otherwise specified, THF is used as the eluent and DIN 55672-1 is applied.Polydispersity is the quotient Mw / Mn. Example formulation 1: 44.5 wt% of a methylphenylsilicone resin intermediate with a mean molecular weight Mw of 1050 g / mol (number mean Mn = 730; polydispersity 1.4) and a viscosity of 140 mm² / s, which carries 13.6 wt% silicon-bound methoxy groups and 0.24 wt% silicon-bound OH groups on the surface and which consists on average of 59 mol% PhSiO3 / 2 units and 41 mol% Me2SiO2 / 2 units, wherein the methoxy and OH groups are distributed among the specified structural units. 0.25 wt% of a terminal Si-OH functional polysiloxanediol with a mean molecular weight Mw of 47,000 g / mol (Mn = 24,600 g / mol, PDI = 1.5), which consists on average of 600 repeat units of the formula Me2SiO. 2 / 2The coating is composed of: 1.0 wt% titanium tetrabutylate, 1.5 wt% n-butanol, 52.75 wt% xylene. The described coating can be applied to common cookware substrates (e.g., steel, WA12415S / WI 17 aluminum) using standard application methods (e.g., spraying, doctor blade application, spin coating, or brushing). The recommended dry film thickness is approximately 20 µm, and the recommended curing conditions are 250°C – 300°C for 30 minutes. The specified tests were performed according to the following standards: Pencil hardness: ISO 15184; Cross-cut test: DIN EN ISO 2409; Methyl ethyl ketone double rub test: DIN EN ISO 13523-11; Coefficient of friction: DIN EN ISO 8295; Fried egg non-stick test: according to CMA (cookware manufacture association) 22.2.1. The resulting non-stick coating exhibits high hardness (e.g., pencil hardness 4H), high temperature resistance (e.g., pencil hardness 2H at 250°C), and excellent solvent resistance (e.g.,Methyl ethyl ketone double rub test > 200), very good adhesion to steel and aluminum (e.g., cross-cut test GT 0 with and without adhesive tape), a low coefficient of friction (e.g., static 0.16 & dynamic 0.09), and excellent non-stick properties, which were tested with the so-called "fried egg test," in which a fried egg is cooked on the coated substrate. The results of the "fried egg test" are shown in the following table:

[0003] WA12415S / WI 18 Table 1: T est 1 Test 2 Test 3 Rating of color changes - Rating of color changes - Rating r ung derEgg coating test after application: 0 no 0 no 0 Egg coating test after 5x frying + 5x cleaning: 0 no 0 no 0 Egg coating test after 3h boiling water, 1x frying egg, 1x cleaning: 0 no 0 no 0 Egg coating test after 2x3h boiling water, 2x frying egg, 2x cleaning: 0 no 0 no 0 Egg coating test after 3x3h boiling water, 3x frying egg, 3x cleaning: 0 no 0 no 0 Egg coating test after 4x3h boiling water, 4x frying egg, 4x cleaning: 0-1 no 0 no 0 Egg coating test after 5x3h boiling water, 5x frying egg, 5x cleaning: 1 no 1 no 0 Test 1: After 2.5 min. frying time, the substrate was rotated from horizontal to vertical. Rating: 0 = Fried egg slides completely off the substrate without any aids. 1 = The fried egg can be removed with the help of a spatula. 2 = The fried egg cannot be completely removed from the substrate even with the help of a spatula. Test 2: Assessment of the residue.Rating: 0 = no residue 1 = residue < 10% WA12415S / WI 192 = residue 10% – 50% 3 = residue > 50% Test 3: Rating after cleaning with a soft household sponge and cold water. Rating: 0 = no residue 1 = residue < 10% 2 = residue 10% – 50% For comparison (state of the art), the above formulation was tested with standard silicone resins: Example formulation 2: 27.3 wt% of a methylphenyl silicone liquid resin with a molecular weight mean Mw of 1900 g / mol (number mean Mn = 1050; polydispersity 1.7) and a viscosity of 70 mm² / s, which carries 3.5 wt% silicon-bound OH groups on the surface and which consists on average of 53 mol% PhSiO3 / 2 units and 47 mol% Me2SiO2 / 2 units. 27.3 wt.% of a methylphenylsilicone solid resin with a molecular weight mean Mw of 3250 g / mol (number mean Mn = 1300; polydispersity 2.5), of which 5.2 wt.-% silicon-bound OH groups and on the surface, and which consists on average of 55 mol% PhSiO3 / 2 units, 39 mol% MeSiO3 / 2 units and 6 mol% Me2SiO2 / 2. 1.0 wt% titanium tetrabutylate 1.5 wt% n-butanol 42.9 wt% xylene. This coating exhibits the following properties after curing (30 min. 300°C): WA12415S / WI 20 pencil hardness 4H, pencil hardness under temperature stress (250°C) 2H, adhesion test with cross-cut test Gt 0 without and with adhesive tape, solvent resistance (methyl ethyl ketone double rub test > 200), coefficient of friction static 0.19, dynamic 0.08. Table 2: T. est 1 Test 2 Test 3 Rating of color changes - Rating of color changes - Rating r ung derEgg coating test after application: No. Egg coating test after 5 fryings + 5 cleanings: No. Egg coating test after 3 hours of boiling water, frying egg once, cleaning once: No. Egg coating test after 2 x 3 hours of boiling water, frying egg twice, cleaning twice: No. Egg coating test after 3 x 3 hours of boiling water, frying egg twice, cleaning twice: No. Egg coating test after 4 x 3 hours of boiling water, frying egg four times, cleaning four times: No. Egg coating test after 5 x 3 hours of boiling water, frying egg five times, cleaning five times: No. Egg coating test after 5 x 3 hours of boiling water, frying egg five times, cleaning five times: No. Egg coating test after 5 x 3 hours of boiling water, frying egg five times, cleaning five times: No. Egg coating test after 5 x 3 hours of boiling water, frying egg five times, cleaning five times: No. Egg coating test after 5 x 3 hours of boiling water, frying egg five times, cleaning five times: No. Egg coating test after 2.5 minutes of frying time, the substrate was turned from horizontal to vertical. Rating: 0 = Fried egg slides completely off the substrate without aids 1 = The fried egg can be removed with the aid of a spatula WA12415S / WI 21 2 = The fried egg cannot be completely removed from the substrate even with the aid of a spatula Test 2: Assessment of the residue.Rating: 0 = no residue 1 = residue < 10% 2 = residue 10% – 50% 3 = residue > 50% Test 3: Rating after cleaning with a soft sponge and cold water. Rating: 0 = no residue 1 = residue < 10% 2 = residue 10% – 50% For further comparison, the above formulation was prepared with a low molecular weight terminally terminated hydroxy-functional polysiloxanediol (with 15 repeating units, molecular weight approx. 1100 g / mol): Example formulation 3: 44.5 wt% of a methylphenylsilicone resin intermediate with a molecular weight mean Mw of 1030 g / mol (number mean Mn = 730; polydispersity 1.4) and a viscosity of 140 mm² / s, which carries 12.3 wt% silicon-bound methoxy groups and 0.24 wt% silicon-bound OH groups on the surface and which consists on average of 59 mol% PhSiO. 3 / 2-units and 41 mol% Me2SiO2 / 2 units, wherein the methoxy and OH groups are distributed over the specified structural units 0.25 wt% of a terminal Si-OH functional polysiloxanediol with a mean molecular weight Mw of 1,100 g / mol, (Mn = WA12415S / WI 22,800 g / mol, PDI = 1.4) which consists of an average of 15 repeat units of the formula Me2SiO 2 / 2 The coating consists of 1.0 wt% titanium tetrabutylate, 1.5 wt% n-butanol, and 52.75 wt% xylene. After curing (30 min. at 300°C), this coating exhibits the following properties: pencil hardness 3H, pencil hardness under temperature stress (250°C) F, adhesion test with cross-cut test Gt 0-1 with and without adhesive tape, solvent resistance (methyl ethyl ketone double rub test) > 200, coefficient of friction static 0.50, dynamic 0.43. Table 3: T est 1 Test 2 Test 3 Rating of color changes - Rating of color changes - Rating r ung derCoating test - Fried egg test after application: 1-2 no 2 no 0 Fried egg test after 5x frying + 5x cleaning: 2 no 3 no 2 Further tests were not carried out due to the poor non-stick properties. Test 1: After 2.5 min. frying time, the substrate was turned from horizontal to vertical. Rating: 0 = Fried egg slides completely off the substrate without aids 1 = Fried egg can be removed with the aid of a spatula WA12415S / WI 23 2 = The fried egg cannot be completely removed from the substrate even with the aid of a spatula. Test 2: Rating of the residue. Rating: 0 = no residue 1 = residue < 10% 2 = residue 10% – 50% 3 = residue > 50% Test 3: Rating after cleaning with a soft household sponge and cold water. Rating: 0 = no deficit, 1 = deficit < 10%, 2 = deficit 10% – 50%

Claims

WA12415S / WI 24 Claims 1. Fluorine-free curable composition comprising (A) at least one organopolysiloxane (A) having a weight-mean molecular weight MW in the range of 800 g / mol – 50 000 g / mol containing units of the general formula (I) R a Si(OR 1 ) b O (4-a-b) / 2 (I) wherein:R is the same or different and represents a monovalent, SiC-bound, optionally substituted C1-C20 hydrocarbon residue, R 1is the same or different and represents a hydrogen atom or a monovalent C1-C6 alkyl group, a and b each have a value of 0, 1, 2 or 3, provided that the sum a + b ≤ 3, and a has the value 1 in at least 30% of all units of formula (I) and a has an average value of 0.9 to 1.9 over all units of formula (I) and b has an average value of 0.1 to 1.8 over all units of general formula (I), (B) at least one terminally terminated, hydroxy-functional polysiloxanediol (B) with a molecular weight of 22,000 – 370,000 g / mol of general formula (II) WA12415S / WI 25 H O[SiR32O]mH (II), in which R 3 is the same or different and a C1-C 301. alkyl group, a C5-C10 cyclocylakyl group, a C6-C10 aryl group, or a C7-C14 aryl group, which may optionally be substituted, and m assumes a value of 300–5000, and (C) at least one condensation catalyst (C).

2. Fluorine-free curable composition according to claim 1, wherein the organopolysiloxane (A) consists exclusively of units of formula (I).

3. Fluorine-free curable composition according to claim 1 or 2, wherein R represents a methyl, ethyl, propyl, or phenyl group.

4. Fluorine-free curable composition according to any one of the preceding claims, wherein R1 represents a methyl, ethyl, or propyl group.

5. Fluorine-free curable composition according to any one of the preceding claims, wherein the organopolysiloxane (A) is a methylphenylpolysiloxane.

6. Fluorine-free curable composition according to any one of the preceding claims, wherein m in formula (II) takes on a value of 300-3500. 7.Fluorine-free curable composition according to any one of the preceding claims, wherein the remainder R. 3 Each one is independently selected from methyl, ethyl, or phenyl. WA12415S / WI 268. Fluorine-free curable composition according to any one of the preceding claims, wherein the at least one condensation catalyst (C) is selected from acids, bases, and organometallic compounds.

9. Fluorine-free curable composition according to claim 8, wherein the acid is hydrochloric acid.

10. Fluorine-free curable composition according to claim 8, wherein the base is a quaternary ammonium and / or phosphonium compound.

11. Fluorine-free curable composition according to claim 8, wherein the organometallic compound is a metal chelate or a metal alkoxylate compound.

12. Fluorine-free curable composition according to claim 11, wherein the organometallic compound is a butylate complex of titanium, in particular titanium tetrabutanoate.

13. Fluorine-free curable composition according to any one of the preceding claims, further comprising at least one organic solvent (D). 14.Method for producing a fluorine-free non-stick coating on a support substrate, comprising (i) applying a fluorine-free, curable composition according to any one of claims 1-13 to a support substrate, and (ii) treating the composition applied in step (i) by heating. WA12415S / WI 2715. Coated carrier obtainable by a method for producing a fluorine-free non-stick coating on a carrier substrate according to claim 14.