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

Abstract

The present invention relates to a fluorine-free, silicone resin-based non-stick coating for use in cookware comprising at least one organopolysiloxane (A), at least one terminal-terminated, hydroxy-functional polysiloxane diol (B), and at least one condensation catalyst (C), and a method for producing such coating.

Description

Technology Field

[0001] The present invention relates to a fluorine-free, silicone resin-based non-stick coating for use in cookware comprising at least one organopolysiloxane (A), at least one terminal-terminated, hydroxy-functional polysiloxane diol (B), and at least one condensation catalyst (C), and a method for producing such a coating.

[0002] Background of the present invention:

[0003] The present invention relates to a fluorine-free silicone resin-based non-stick coating for cookware based on a reactive organopolysiloxane (a silicone resin known as a silicone intermediate) combined with a suitable functional, reactive, terminal-terminated hydroxy-functional polysiloxane diol (silicone polymer), an organic solvent, and a condensation catalyst, which can be applied as a thin film on a carrier substrate, generally steel or aluminum, and forced baked at a high temperature (250°C to 300°C for about 30 minutes). The coating is characterized by a long-lasting non-stick effect, high resistance, and excellent flexibility. Background Technology

[0004] Non-stick coatings based on fluoropolymers have long been known from the prior art, for example, for coating baking tools or cookware (e.g., pots and pans). Polytetrafluoroethylene (PTFE) is a fluoropolymer very commonly used here. PTFE coatings have excellent non-stick properties due to their low surface energy and high heat resistance due to their high CF bond energy.

[0005] However, in addition to the advantages described, fluoropolymer coatings have many disadvantages. Due to its high melt viscosity, PTFE can only be processed at very high temperatures. The firing temperature used here is approximately 410°C. Since this processing temperature exceeds the decomposition temperature of PTFE, it allows for the release of toxic and corrosive (aggressive) decomposition products such as trifluoroacetic acid and carbonyl fluoride (fluorophosgene). Fluorine-containing wetting agents (PFAS) are also commonly used in the production of fluoropolymers; due to their lack of biodegradability, they can accumulate in nature and also threaten the health of humans, animals, and the environment.

[0006] Fluorine-free non-stick coatings are also known in the prior art. Silicone-modified polyesters, in which a portion of the polyester is replaced with silicone, exhibit poor heat resistance and non-stick properties because the polyester fraction oxidizes (burns) easily at high temperatures exceeding 230°C.

[0007] Finally, prior art such as EP 2 177 580 B1 describes a fluorine-free non-stick coating produced by a sol-gel process. Such coatings are highly heat-resistant but are also very hard and brittle. These non-stick coatings, also referred to as ceramic coatings, are often only partially suitable as non-stick coatings for cookware due to their brittleness and insufficient non-stick effect.

[0008] U.S. Patent Specification US7510774 describes a silicone resin-based, fluorine-free, non-stick coating based on a standard commercial silicone resin (e.g., SILRES MK, SILRES SY 409) combined with a “silicone fluid” and an inorganic filler (referred to as a “durability enhancer”). Tests by the inventors have shown that while this formulation is very suitable for baking utensils (operation temperature range of 180°C to 200°C), it appears to be likewise somewhat unsuitable for cookware due to discoloration and a very rapid decrease in non-stick effect at a temperature range of 250°C to 300°C (= typical operating temperature for cookware).

[0009] European Patent EP 4265697 A1 describes a silicone resin-based non-stick coating combined with a low molecular weight polysiloxanediol having 4 to 50 repeating units. Tests by the inventors showed that short-chain silicone oil (polysiloxanediol) combined with the said silicone resin does not exhibit a sufficient non-stick effect for cookware applications.

[0010] Through the present invention, it was possible to develop a fluorine-free non-stick coating based on a relatively reactive and low molecular weight organopolysiloxane known as a silicone intermediate, said organopolysiloxane combined with a suitable terminal-terminated hydroxy-functional polysiloxane diol (silicone polymer), an organic solvent, and a catalyst to achieve a long-lasting non-stick coating for cookware that also possesses excellent flexibility. A factor distinguishing the present invention from prior art such as the aforementioned document US 7510774 includes the use of a relatively reactive and low molecular weight organopolysiloxane known as a silicone intermediate. Specific details for implementing the invention

[0011] thus, First aspect of the present invention is a fluorine-free curable composition comprising the following (A), (B), and (C):

[0012] (A) Weight-average molecular weight M in the range of 800 g / mol to 50,000 g / mol W At least one organopolysiloxane (A) having the chemical formula (I) and containing a unit of the formula (I):

[0013]

[0014] In chemical formula (I),

[0015] R It is identical or different, monovalent, SiC-bonded, optionally substituted C1-C 20 It is a hydrocarbon radical, and

[0016] R 1 is identical or different, is a hydrogen atom or a monovalent C1-C6 alkyl radical, and

[0017] a and b are numbers having values ​​of 0, 1, 2, or 3, respectively, provided, a + b The sum of is 3 or less, and

[0018] a has a value of 1 in at least 30% of all units of chemical formula (I), and a It has an average value of 0.9 to 1.9 when averaged over all units of chemical formula (I), and

[0019] b It has an average value of 0.1 to 1.8 when averaged over all units of chemical formula (I).

[0020] (B) At least one terminal-terminated, hydroxy-functional polysiloxane diol (B) having a molecular weight of 22,000 to 370,000 g / mol and chemical formula (II):

[0021]

[0022] In chemical formula (II),

[0023] R 3 is identical or different, and C1-C 30 Alkyl radical, C5-C 10 Cycloalkyl radical, C6-C 10 aryl radical or C7-C 14 It is an aralkyl radical, which can be selectively substituted, and

[0024] m The amount is 300 to 5000, preferably 300 to 3500, more particularly 300 to 1500, and

[0025] (C) At least one condensation catalyst (C).

[0026] Possible substituents are hydroxyl groups, N-containing groups, such as amino groups, or S-containing groups, such as thiol groups.

[0027] The molecular weight of the described organopolysiloxane (A), expressed as weight average Mw, is preferably in the range of 800 g / mol to 40,000 g / mol, particularly preferably 1,000 g / mol to 20,000 g / mol, and very preferably 1,000 g / mol to 5,000 g / mol.

[0028] Molecular weight can be determined by methods known to those skilled in the art, such as size exclusion chromatography.

[0029] Preferably, the organopolysiloxane (A) consists only of units of the chemical formula (I).

[0030] R is preferably a methyl, ethyl, propyl, or phenyl radical. Particularly preferably, R is methyl and / or phenyl, and preferably all units of formula (I) are units R Having ten thousand, Ris methyl and / or phenyl. Preferably, at least 50% of all units of formula (I), particularly preferably at least 70% of all units of formula (I) have phenyl units. Particularly preferably, the units of formula (I) having phenyl units have no additional units R ( a = does not have 1).

[0031] R 1 It is preferably a methyl, ethyl, or propyl radical, particularly preferably a methyl radical.

[0032] In a particularly preferred embodiment, the organopolysiloxane (A) is a methylphenylpolysiloxane, more particularly a reactive, solvent-free, low molecular weight, alkoxy-functional methylphenylpolysiloxane.

[0033] Preferably 50% of all units of formula (I), particularly preferably 70% of all units of formula (I), and particularly preferably 90% of all units of formula (I) variable a has a value of 1.

[0034] variable b is preferably 1 or 2, and is averaged over all units of formula (I). a It preferably has a value of 1.1 to 1.5.

[0035] An example of an organopolysiloxane (A) is the chemical formula SiO₂ 4 / 2 , Si(O R 2 )O 3 / 2 , Si(O R 2 )2O 2 / 2 and Si(O R 2 )3O 1 / 2 (Q) unit, chemical formula PhSiO 3 / 2 , PhSi(O R 2 )O 2 / 2 and PhSi(O R 2 )2O 1 / 2(T) unit, chemical formula MeSiO 3 / 2 , MeSi(O R 2 )O 2 / 2 and MeSi(O R 2 )2O 1 / 2 T unit of, chemical formula Me2SiO 2 / 2 and Me2Si(O R 2 )O 1 / 2 (D) unit and chemical formula Me3SiO 1 / 2 The organopolysiloxane resin is essentially composed of a unit selected from the (M) unit, preferably composed solely of such unit, wherein Me is a methyl radical and Ph is a phenyl radical, and R 2 is an optionally halogen-atom-substituted alkyl radical having a hydrogen atom or 1 to 10 carbon atoms, preferably an unsubstituted alkyl radical having 1 to 4 carbon atoms, and the resin preferably contains 0 to 2 mol of (Q) units, 0 to 2 mol of (D) units and 0 to 2 mol of (M) units per 1 mol of (T) unit.

[0036] A preferred example of organopolysiloxane (A) is the chemical formula PhSiO 3 / 2 , PhSi(O R 2 )O 2 / 2 and PhSi(O R 2 )2O 1 / 2 The T unit and chemical formula Me2SiO 2 / 2 and Me2Si(O R 2 )O 1 / 2 It is an organopolysiloxane resin essentially composed of a unit selected from the D unit, preferably composed solely of this, wherein Me is a methyl radical and Ph is a phenyl radical, and R 2 is an optionally halogen-atom-substituted alkyl radical having a hydrogen atom or 1 to 10 carbon atoms, preferably an unsubstituted alkyl radical having 1 to 4 carbon atoms.

[0037] Further preferred examples of organopolysiloxane (A) are those with the chemical formula PhSiO 3 / 2 , PhSi(O R 2 )O 2 / 2 and PhSi(O R 2 )2O 1 / 2 T unit, chemical formula MeSiO 3 / 2 , MeSi(O R 2 )O 2 / 2 and MeSi(O R 2 )2O 1 / 2 The T unit and chemical formula Me2SiO 2 / 2 and Me2Si(O R 2 )O 1 / 2 It is an organopolysiloxane resin essentially composed of a unit selected from the D unit, preferably composed solely of this, wherein Me is a methyl radical and Ph is a phenyl radical, and R 2 is an optionally halogen-atom-substituted alkyl radical having a hydrogen atom or 1 to 10 carbon atoms, preferably an unsubstituted alkyl radical having 1 to 4 carbon atoms, and the molar ratio of phenylsilicon to methylsilicon units is 0.5 to 4.0. The content of D units in these silicone resins is preferably less than 10 weight%.

[0038] Of course, the silicone resin binders described in the preceding three paragraphs may also be used as any desired mixture. Particularly preferably, the silicone resin binder mixture described in the last two paragraphs is used.

[0039] The recommended polysiloxane diol (B) preferably has an average chain length of m = 300 to 5000 repeating units and a molecular weight of 22,000 to 370,000 g / mol, particularly preferably has an average chain length of m = 300 to 3500 repeating units and a molecular weight of 22,000 to 259,000 g / mol, more specifically has an average chain length of m = 300 to 1500 repeating units and a molecular weight of 22,000 to 111,000 g / mol.

[0040] In a preferred embodiment, the fluorine-free composition according to the present invention does not contain polysiloxane diol (B) having an average chain length of m < 300.

[0041] radical R 3 Preferably, each is independently selected from methyl, ethyl, or phenyl, in particular methyl or ethyl, more specifically methyl.

[0042] At least one condensation catalyst (C) is preferably selected from an acid, a base, or an organometallic compound, such as a metal chelate or a metal alkoxylate, and more specifically selected from an organometallic compound.

[0043] Examples of acids that can be used as acid catalysts are preferably inorganic acids such as hydrochloric acid, nitric acid, or phosphoric acid—wherein hydrochloric acid is particularly preferred—poly acids such as polyphosphoric acid, polyacrylic acid, and polyvinyl sulfate, or it is also preferably possible to use carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, adipic acid, benzoic acid, phthalic acid, and citric acid. The acid catalyst is used in an amount of 1 ppm to 1 weight%, preferably less than 0.1 weight%, based on the total weight of the silicone resin. The concentration of such an aqueous solution is 5% to 35%, preferably 10% to 30%, more specifically 25%. A 25% aqueous hydrochloric acid solution is particularly preferred.

[0044] Examples of bases that can be used as basic catalysts are hydroxides, methoxides, ethoxides and isopropoxides, ammonia, amines, alkali metal and alkaline earth metal hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals, silanolates and siliconates of alkali metals, ammonium and phosphonium hydroxides and their silanolates, and ammonium and phosphonium alkoxides. Preferably, as a basic catalyst or part of a component, a basic condensation catalyst that loses its basicity by boiling, sublimating, or decomposing at a pressure of 0.1 MPa and a temperature of up to 600°C is used.

[0045] More particularly, quaternary ammonium and / or phosphonium compounds, particularly those of formulas (2) and (3), are suitable:

[0046] Chemical formula (2):

[0047] Chemical formula (3):

[0048] In chemical formulas (2) and (3), R 4 and R 6 silver R Having this meaning independently of, R 5 and R 7 silver R 1 Type independently of R 1 It is a radical.

[0049] Compounds of chemical formulas (2) and (3), in particular tetra(C1 to C 18 Hydrocarbon) ammonium hydroxide and tetra(C1 to C 18 Hydrocarbon)phosphonium hydroxide is preferred, and the hydrocarbon radical is particularly alkyl, aryl, alkalil, and aralkyl radicals. In particular, tetra(C1 to C 12Hydrocarbon) ammonium hydroxide and tetra(C1 to C 18 Hydrocarbon) Phosphonium hydroxide and / or their silanolates are preferred. The latter is prepared by reacting quaternary ammonium and phosphonium hydroxide with an organosilane or organosiloxane.

[0050] Benzyltrimethylammonium hydroxide, which decomposes into benzyl alcohol and gaseous trimethylamine at 0.1 MPa and 130°C, is particularly preferred. Tetramethylammonium hydroxide is likewise preferred. Likewise, tetra-n-butylphosphonium hydroxide, which decomposes into tri-n-butylphosphine oxide and butane—the latter may be released in gaseous form—at 0.1 MPa and 150°C, is particularly preferred.

[0051] The basic catalyst is used in an amount of 100 ppm to 1 weight%, preferably less than 0.5 weight%, based on the total weight of the silicone resin. The concentration of such aqueous or alcohol solution is 5% to 75%, preferably 10% to 50%, more specifically 40%. Particularly preferred is a 40% methanol or ethanol solution of benzyltrimethylammonium hydroxide.

[0052] An example of a metal chelate as a condensation catalyst (C) is titanium chelate, which may be used as a single compound or consist of a mixture of monomeric titanium chelates. Suitable chelate ligands include diketo compounds such as ethyl acetoacetate, methyl acetoacetate, and acetylacetoacetate. Titanium chelate may be a pure compound or may be formed in situ by mixing alkyl titanates with chelate ligands. A pure compound is preferably used. Such titanium chelate complexes are commercially available from various suppliers such as DuPont’s Tyzor®, Borica Tytan®, and JohnsonMatthey Vertec®. Suitable examples include DuPont’s Tyzor® AA, AA-65, AA-75, AA-105, GBA, GBO, DC, TE, and PITA; Includes Johnson Matthey Catalyst’s VERTEC™ XL 165, KE2, KE4, KE6, and Borica Co.’s TYTANT™ S2, S4, S6.

[0053] Preferably, an ethyl acetoacetate complex of titanium, such as TYZOR® PITA, is used as a condensation catalyst (C).

[0054] Examples of metal alkoxylates are titanium alkoxylates, more particularly titanium tetrabutoxide.

[0055] Metal alkoxylates are particularly desirable as condensation catalysts (C).

[0056] In a preferred embodiment, the curable composition further comprises at least one organic solvent (D).

[0057] Aromatic solvents such as xylene, toluene, and benzene, or mixtures of aliphatic hydrocarbons (e.g., Isopar E from Exxon Mobil Chemical, Kristalloel K-30 or K-60 from Shell) are possible solvents (D). Esters such as isomer butyl acetate or ethyl acetate may also be used.

[0058] Alcohols (e.g., n-butyl alcohol) have been proven to be advantageous for stabilization.

[0059] In a preferred embodiment, the amount of at least one organopolysiloxane (A) is 20 to 80 weight percent based on the total mass of the fluorine-free curable composition.

[0060] In a preferred embodiment, the amount of at least one polysiloxane diol (B) is 0.05 to 0.5 weight% based on the total mass of the fluorine-free curable composition.

[0061] In a preferred embodiment, the amount of at least one condensation catalyst (C) is 1.0 to 3.0 weight% based on the total mass of the fluorine-free curable composition.

[0062] In a preferred embodiment, the amount of at least one organic solvent (D) is 16.5 to 78.5 weight% based on the total mass of the fluorine-free curable composition.

[0063] In a preferred embodiment, the fluorine-free composition according to the present invention comprises components (A), (B), (C) and optionally (D).

[0064] Further subject matter of the present invention is Further relating to a method for producing a fluorine-free non-stick coating on a carrier substrate,

[0065] (i) A step of applying a curable formulation according to the present invention to a carrier substrate, and

[0066] (ii) Step (i) of treating the formulation applied by heating

[0067] Includes

[0068] The carrier substrate is preferably a metal suitable for use in cookware, more particularly steel or aluminum.

[0069] The carrier substrate is, more specifically, the surface of the cooking utensil.

[0070] The coating in step (i) is preferably achieved by spraying, knife coating, spin coating, or spread-coating the carrier substrate with the curable composition according to the present invention.

[0071] It is recommended to apply the coating with a dry film thickness in the range of 10 to 100 μm, more particularly in the range of 15 to 30 μm.

[0072] Preferably, the temperature treatment in step (ii) is performed at a temperature of 200°C to 500°C, preferably 250°C to 300°C, for a period of 10 minutes to 120 minutes, preferably 20 minutes to 60 minutes.

[0073] Further subject matter of the present invention is A carrier coated with a fluorine-free composition according to the present invention, more particularly a cooking utensil.

[0074] Example:

[0075] The following examples are intended to further clarify the invention. They are illustrative and not intended to be limiting.

[0076] All percentages are based on weight. Unless otherwise specified, all operations are performed at room temperature of 23°C and standard pressure (1.013 bar).

[0077] Unless otherwise specified, all data describing the characteristics of the product refers to room temperature of 23°C and standard pressure (1.013 bar).

[0078] The device is a commercially available laboratory instrument, as it is commercially supplied by various instrument manufacturers.

[0079] pH represents the phenyl radical = C6H5-.

[0080] Me represents a methyl radical = CH3-. Me2 represents two methyl radicals.

[0081] HCl represents hydrogen chloride.

[0082] In this document, components are characterized by reporting data obtained through instrumental analysis. The measurements forming the basis of the data are performed according to publicly accessible standards or determined by specially developed methods. To ensure clarity of instruction, the techniques used are specified below.

[0083] In all embodiments, unless otherwise specified, reported parts and percentages refer to weights.

[0084] viscosity:

[0085] Unless otherwise specified, viscosity is determined by rotational viscometer measurements in accordance with DIN EN ISO 3219. Unless otherwise specified, all viscosity data are based on 25°C and a standard pressure of 1013 mbar.

[0086] Molecular composition:

[0087] Molecular composition was determined using nuclear magnetic resonance spectroscopy (for terminology, see ASTM E 386: High-resolution nuclear magnetic resonance (NMR) spectroscopy: Terms and Symbols). 1 H nucleus and 29 It is determined by measuring the Si nucleus.

[0088] 1 Explanation of H NMR measurement

[0089] menstruum: CDCl3, 99.8% d

[0090] Sample concentration: Approximately 50 mg / 1 ml CDCl3 in a 5 mm NMR tube

[0091] Reference to the spectrum for residual CHCl3 in CDCl3 at 7.24 ppm, measured without the addition of TMS.

[0092] spectrometer: Bruker Avance I 500 or Bruker Avance HD 500

[0093] Probe: 5 mm BBO probe or SMART probe (Bruker)

[0094] Measurement parameters:

[0095] Pulprog = zg30

[0096] TD = 64k

[0097] NS = 64 or 128 (depends on probe sensitivity)

[0098] SW = 20.6 ppm

[0099] AQ = 3.17 s

[0100] D1 = 5 s

[0101] SFO1 = 500.13 MHz

[0102] O1 = 6.175 ppm

[0103] Processing parameters:

[0104] SI = 32k

[0105] WDW = EM

[0106] LB = 0.3 Hz

[0107] Depending on the type of spectrometer used, individual adjustments to the measurement parameters may be required.

[0108] 29 Explanation of Si NMR Measurement

[0109] menstruum: C6D6 99.8% d / CCl4 1:1 v / v with 1 wt% Cr(acac)3 as a relaxation reagent

[0110] Sample concentration: Approximately 2 g / 1.5 ml solvent in a 10 mm NMR tube

[0111] spectrometer: Bruker Avance 300

[0112] Probe: 10 mm 1H / 13C / 15N / 29Si glass-free QNP probe (Bruker)

[0113] Measurement parameters:

[0114] Pulprog = zgig60

[0115] TD = 64k

[0116] NS = 1024 (depends on probe sensitivity)

[0117] SW = 200 ppm

[0118] AQ = 2.75 s

[0119] D1 = 4 s

[0120] SFO1 = 300.13 MHz

[0121] O1 = -50 ppm

[0122] Processing parameters:

[0123] SI = 64k

[0124] WDW = EM

[0125] LB = 0.3 Hz

[0126] Depending on the type of spectrometer used, individual adjustments to the measurement parameters may be required.

[0127] Molecular weight distribution:

[0128] The molecular weight distribution is determined as weight-average Mw and number-average Mn using gel permeation chromatography (GPC) or size exclusion chromatography (SEC) techniques with polystyrene standards and a refractive index detector (RI detector). Unless otherwise specified, THF is used as the eluent and follows DIN 55672-1. Polydispersity is the ratio of Mw / Mn.

[0129] Example Formulation 1:

[0130] Containing 13.6 wt% silicon-bonded methoxy groups and 0.24 wt% silicon-bonded OH groups on the surface, and on average PhSiO 3 / 2 Units 59 mol% and Me2SiO 2 / 2 Composed of 41 mol% units, with an average molecular weight Mw of 1050 g / mol (number-average Mn = 730; polydispersity 1.4) and a viscosity of 140 mm 2 44.5 wt% of a methylphenylsilicone resin intermediate having / s, wherein methoxy groups and OH groups are distributed in the mentioned structural units.

[0131] Chemical formula Me2SiO 2 / 2 0.25 wt% of terminal Si-OH functional polysiloxanediol having an average molecular weight Mw of 47,000 g / mol (Mn = 24,600 g / mol, PDI = 1.5) and consisting of an average of 600 repeating units.

[0132] Titanium tetrabutylate 1.0 wt%

[0133] n-butanol 1.5 wt%

[0134] Xylene 52.75 wt%

[0135] The described coating can be applied to a general cookware substrate (e.g., steel, aluminum) using a general application method (e.g., spray, knife coating, spin coating, or spread-coating). The recommended dry film thickness is about 20 μm, and the recommended curing conditions are 250°C to 300°C for 30 minutes.

[0136] The specified tests were performed according to the following standards:

[0137] Pencil Hardness: ISO 15184

[0138] Cross-cut test: DIN EN ISO 2409

[0139] Methyl ethyl ketone rubbing test: DIN EN ISO 13523-11

[0140] Coefficient of friction: DIN EN ISO 8295

[0141] Non-stick test for fried eggs: In accordance with CMA (Cookware Manufacturers Association) 22.2.1

[0142] The non-stick coating produced in this way demonstrated excellent non-stick properties through high hardness (e.g., pencil hardness 4H), high hardness under temperature stress (e.g., pencil hardness 2H at 250°C), excellent solvent resistance (e.g., methyl ethyl ketone friction test > 200), very good adhesion to steel and aluminum (e.g., cross-cut test GT 0 with or without adhesive tape), low coefficient of friction (e.g., static 0.16 and dynamic 0.09), and also the "fried egg test" in which an egg is fried on the coated substrate.

[0143] The results of the "fried egg test" are shown in the table below:

[0144]

[0145] Test 1: After a frying time of 2.5 minutes, the material was rotated from horizontal to vertical.

[0146] evaluation:

[0147] 0 = The fried egg slides completely off the substrate without any assistance

[0148] 1 = With the help of a spatula, the fried egg can be removed

[0149] 2 = The fried egg cannot be completely removed from the substrate despite the help of a spatula

[0150] Test 2: Evaluation of residues.

[0151] evaluation:

[0152] 0 = No residue

[0153] 1 = Residue < 10%

[0154] 2 = Residue 10% to 50%

[0155] 3 = Residue > 50%

[0156] Test 3: Evaluation after cleaning with a soft household sponge and cold water.

[0157] evaluation:

[0158] 0 = No residue

[0159] 1 = Residue < 10%

[0160] 2 = Residue 10% to 50%

[0161] As a comparison (prior art), the above formulation was tested with a standard silicone resin:

[0162] Example Formulation 2:

[0163] Containing 3.5 wt% silicon-bonded OH groups on the surface and, on average, PhSiO 3 / 2 Units 53 mol% and Me2SiO 2 / 2 Composed of 47 mol% units, with an average molecular weight Mw of 1900 g / mol (number-average Mn = 1050; polydispersity 1.7) and a viscosity of 70 mm 2 27.3 wt% of liquid methylphenylsilicone resin having / s.

[0164] It has an average molecular weight Mw of 3250 g / mol (number-average Mn = 1300; polydispersity 2.5), contains 5.2 wt% silicon-bonded OH groups on the surface, and averages PhSiO 3 / 2 Unit 55 mol%, MeSiO 3 / 2 Units 39 mol% and Me2SiO 2 / 2 27.3 wt% of solid methylphenylsilicone resin composed of 6 mol% units.

[0165] Titanium tetrabutylate 1.0 wt%

[0166] n-butanol 1.5 wt%

[0167] Xylene 42.9 wt%

[0168] After curing (30 minutes, 300℃), this coating exhibits the following characteristics:

[0169] Pencil hardness 4H, temperature load pencil hardness (250℃) 2H, cross-cut test Gt 0 regardless of adhesive tape presence or absence, solvent resistance (methyl ethyl ketone friction test) > 200, static friction coefficient 0.19, dynamic friction coefficient 0.08.

[0170]

[0171] Experiment 1: After a frying time of 2.5 minutes, the material was rotated from horizontal to vertical.

[0172] evaluation:

[0173] 0 = The fried egg slides completely off the substrate without any assistance

[0174] 1 = With the help of a spatula, the fried egg can be removed

[0175] 2 = The fried egg cannot be completely removed from the substrate despite the help of a spatula

[0176] Test 2: Evaluation of residues.

[0177] evaluation:

[0178] 0 = No residue

[0179] 1 = Residue < 10%

[0180] 2 = Residue 10% to 50%

[0181] 3 = Residue > 50%

[0182] Test 3: Evaluation after cleaning with a soft household sponge and cold water.

[0183] evaluation:

[0184] 0 = No residue

[0185] 1 = Residue < 10%

[0186] 2 = Residue 10% to 50%

[0187] For further comparison, the above composition was prepared using a low molecular weight, terminally terminated hydroxy-functional polysiloxane diol (15 repeating units, molecular weight approximately 1100 g / mol).

[0188] Example Formulation 3:

[0189] Containing 12.3 wt% silicon-bonded methoxy groups and 0.24 wt% silicon-bonded OH groups on the surface, and on average PhSiO 3 / 2 Units 59 mol% and Me2SiO 2 / 2 Composed of 41 mol% units, with an average molecular weight Mw of 1030 g / mol (number-average Mn = 730; polydispersity 1.4) and a viscosity of 140 mm 2 44.5 wt% of methylphenylsilicone resin intermediate having / s.

[0190] It has an average molecular weight Mw of 1100 g / mol (Mn = 800, PDI 1.4) and, on average, the chemical formula Me2SiO2 2 / 2 0.25 wt% of a terminated Si-OH functional polysiloxane diol consisting of 15 repeating units.

[0191] Titanium tetrabutylate 1.0 wt%

[0192] n-butanol 1.5 wt%

[0193] Xylene 52.75 wt%

[0194] After curing (30 minutes, 300℃), this coating exhibits the following characteristics:

[0195] Pencil hardness 3H, temperature load pencil hardness (250℃) F, cross-cut test Gt 0-1 regardless of adhesive tape presence or absence, solvent resistance (methyl ethyl ketone friction test) > 200, static friction coefficient 0.50, dynamic friction coefficient 0.43.

[0196]

[0197] Experiment 1: After a frying time of 2.5 minutes, the material was rotated from horizontal to vertical.

[0198] evaluation:

[0199] 0 = The fried egg slides completely off the substrate without any assistance

[0200] 1 = With the help of a spatula, the fried egg can be removed

[0201] 2 = The fried egg cannot be completely removed from the substrate despite the help of a spatula

[0202] Test 2: Evaluation of residues.

[0203] evaluation:

[0204] 0 = No residue

[0205] 1 = Residue < 10%

[0206] 2 = Residue 10% to 50%

[0207] 3 = Residue > 50%

[0208] Test 3: Evaluation after washing with a soft sponge and cold water.

[0209] evaluation:

[0210] 0 = No residue

[0211] 1 = Residue < 10%

[0212] 2 = Residue 10% to 50%

Claims

Claim 1 As a fluorine-free curable composition, (A) Weight-average molecular weight M in the range of 800 g / mol to 50,000 g / mol W At least one organopolysiloxane (A) having the chemical formula (I) and containing a unit of the formula (I): In chemical formula (I), R It is identical or different, monovalent, SiC-bonded, optionally substituted C1-C 20 It is a hydrocarbon radical, and R 1 is identical or different, is a hydrogen atom or a monovalent C1-C6 alkyl radical, and a and b are numbers having values ​​of 0, 1, 2, or 3, respectively, provided, a + b The sum of is 3 or less, and a has a value of 1 in at least 30% of all units of chemical formula (I), and a It has an average value of 0.9 to 1.9 when averaged over all units of chemical formula (I), and b is averaged over all units of chemical formula (I) to have a value of 0.1 to 1.8 on average, (B) At least one terminal-terminated, hydroxy-functional polysiloxane diol (B) having a molecular weight of 22,000 to 370,000 g / mol and chemical formula (II): In chemical formula (II), R 3 is identical or different, and C1-C 30 Alkyl radical, C5-C 10 Cycloalkyl radical, C6-C 10 aryl radical or C7-C 14 It is an aralkyl radical, which can be selectively substituted, and m ...takes a value of 300 to 5000, and (C) A fluorine-free curable composition comprising at least one condensation catalyst (C). Claim 2 In claim 1, the organic polysiloxane (A) is a fluorine-free curable composition composed only of units of chemical formula (I). Claim 3 In paragraph 1 or 2, R Fluorine-free curable composition, which is a methyl, ethyl, propyl, or phenyl radical. Claim 4 In any one of paragraphs 1 through 3, R 1 Fluorine-free curable composition, which is a methyl, ethyl, or propyl radical. Claim 5 A fluorine-free curable composition according to any one of claims 1 to 4, wherein the organic polysiloxane (A) is methylphenylpolysiloxane. Claim 6 In any one of paragraphs 1 to 5, in chemical formula (II) m A fluorine-free curable composition having a value of 300 to 3500. Claim 7 In any one of paragraphs 1 to 6, radical R 3 A fluorine-free curable composition, each independently selected from methyl, ethyl, or phenyl. Claim 8 A fluorine-free curable composition according to any one of claims 1 to 7, wherein at least one condensation catalyst (C) is selected from acids, bases, and organometallic compounds. Claim 9 A fluorine-free curable composition in which the acid is hydrochloric acid, as described in claim 8. Claim 10 A fluorine-free curable composition according to claim 8, wherein the base is a quaternary ammonium and / or phosphonium compound. Claim 11 A fluorine-free curable composition according to claim 8, wherein the organometallic compound is a metal chelate or metal alkoxylate compound. Claim 12 In claim 11, the organometallic compound is a titanium butyrate complex, more particularly titanium tetrabutoxide, a fluorine-free curable composition. Claim 13 A fluorine-free curable composition comprising at least one organic solvent (D) in any one of claims 1 to 12. Claim 14 (i) A step of applying a fluorine-free curable composition according to any one of claims 1 to 13 to a carrier substrate, and (ii) A method for producing a fluorine-free non-stick coating on a carrier substrate, comprising the step of treating the composition applied in step (i) by heating. Claim 15 A coated carrier obtainable by a method for producing a fluorine-free non-stick coating on a carrier substrate according to claim 14.

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