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WO2025125280A1 - Composition de revêtement utilisant un polysilazane de viscosité élevée - Google Patents

Composition de revêtement utilisant un polysilazane de viscosité élevée Download PDF

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Publication number
WO2025125280A1
WO2025125280A1 PCT/EP2024/085591 EP2024085591W WO2025125280A1 WO 2025125280 A1 WO2025125280 A1 WO 2025125280A1 EP 2024085591 W EP2024085591 W EP 2024085591W WO 2025125280 A1 WO2025125280 A1 WO 2025125280A1
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Prior art keywords
polysilazane
coating composition
repeating unit
viscosity
composition according
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Pending
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PCT/EP2024/085591
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English (en)
Inventor
Christoph LANDMANN
Gianfranco PIRONTI
Ralf Grottenmueller
Thomas KRASEMANN
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Merck Patent GmbH
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Merck Patent GmbH
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Publication of WO2025125280A1 publication Critical patent/WO2025125280A1/fr
Pending legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc

Definitions

  • the present invention relates to a coating composition, comprising (i) a mixture of organic polysilazanes having together an adjusted viscosity of a specific target viscosity; (ii) an acrylic based adhesion promoter in a concentration of more than 1 wt.% and less than 10 wt.% based on the solid content of the coating composition and (iii) a radical starter and (iv) metal particles or a dispersion of metal particles and a method of preparing said coating composition and a method for preparing a coated article by using said coating composition.
  • Polymers with silazane repeating units -[SiR2-NR’-] are typically referred to as polysilazanes (PSZ). If all substituents R and R’ are hydrogen, the material is called perhydropolysilazane (PHPS) and, if at least one of R and R’ is an organic moiety, the material is called organopolysilazane (OPSZ). PHPS and OPSZ are used for a variety of functional coatings to impart certain properties to surfaces. Hence, silazanes are widely used for functional coatings for various applications. A basic information on polysilazanes and their structures is described in Brewer S.D. et al, J. Am. Chem. Soc, 1948, 70, 3888, EP0303498 B1 and WO0136427 A1 which are incorporated by reference.
  • Coating compositions comprising polymers with silazane repeating units are particularly suitable for the preparation of functional coatings on various base material substrates to provide improved physical and chemical surface properties such as, in particular, improved mechanical resistance and durability (including improved surface hardness, improved scratch resistance, improved abrasion resistance and/or improved smoothness); improved wetting and adhesion properties (including hydro- and oleophobicity, easy-to- clean effect and/or anti-graffiti effect); improved chemical resistance (including improved corrosion resistance (e.g. against solvents, acidic and alkaline media and corrosive gases) and/or improved anti-oxidation effect); improved optical effects (improved light fastness); and improved physical barrier or sealing effects.
  • improved mechanical resistance and durability including improved surface hardness, improved scratch resistance, improved abrasion resistance and/or improved smoothness
  • improved wetting and adhesion properties including hydro- and oleophobicity, easy-to- clean effect and/or anti-graffiti effect
  • improved chemical resistance including improved corrosion resistance (e.g. against solvents,
  • polysilazanes are liquid polymers which become solid at molecular weights of ca. > 10,000 g/mol. In most applications, liquid polymers of moderate molecular weights, typically in the range from 200 to 10,000 g/mol, are used.
  • a curing step is required which is carried out after applying the material on a substrate, either as a pure material or as a formulation. The curing should be as fast as possible. As long as the coating is liquid, some defect formation of the film can occur. For example, the liquid coating may reflow and cause some film thickness variations or the wet film is sensitive to absorption of airborn impurities (e.g. dust) which stick on the wet surface.
  • Another disadvantage is a delay time in the processing of the substrates until the coating is dry. In general, it is possible to speed up the drying time by applying higher temperatures, radiation or an atmosphere with higher humidity. Polysilazanes may act as preceramic polymers.
  • said compositions shall be designed for protecting the steel sheet from unwanted oxidation and oxide formation that occurs during the metallurgical process of heat-stamping.
  • JP3414489 B2 describes the use of acrylic resins together with perhydropolysilazane and solvent-soluble fluororesins.
  • US6296805 B1 describes a hot-rolled steel sheet coated with an aluminum-based or aluminum alloy coating, manufactured for example by dipping the steel sheet in an aluminum bath containing either from 8% to 11% silicon and 2% to 4% iron, or from 2% to 4% iron, or even in an aluminum bath preferably containing from 9% to 10% silicon and 2% to 3.5% iron. It is reported that the presence of the coating at the time of thermal treatment of the castings makes it possible to prevent any decarbonization of the base metal as well as any oxidation.
  • Xiao et al, Ceramics International 2014, 40, 745-752 describes crack-free ceramic coatings using polysilazane as a preceramic polymer and aluminum powder as an active filler.
  • the coating compositions contained 10 to 40 vol% Al powder, 0.5 wt.% Dicumyl peroxide, a polysilazane of formula -[SiNH(CHaCH2)]x-[NHSiNH(CH3)]y- having a molecular weight of 600 to 1 ,000 and xylene as solvent.
  • LIS2011041913 A1 describes formulations containing perhydropolysilazane, a solvent and a catalyst and may comprise a substance influencing the viscosity of the formulation.
  • US20220267617 A1 describes an oxidation-protective coating composition for steel sheets comprising the chemical components of: an aromatic organic solvent; at least one source of aluminum; a silazane; an organic synthesis catalyst; or an organophosphorus compound.
  • US20230124254 A1 and US20230212425 A1 describe an oxidative-protective coating composition for steel sheets comprising an aromatic organic solvent, at least one source of aluminum, a silazane, and an organic synthesis catalyst.
  • viscosity within the desired application window is challenging since polysilazanes (PSZ) often react with viscosity modifying additives.
  • PSZ polysilazanes
  • viscosities in the range of 70 to 200 mPas are used as target measured by using e.g. an Anton Paar Modular Compact Rheometer MCR 92 equipped with a measuring Cone CP50-1 , at a shear rate of 1000s' 1 , and at a temperature of 25°C.
  • an Anton Paar Modular Compact Rheometer MCR 92 equipped with a measuring Cone CP50-1 , at a shear rate of 1000s' 1 , and at a temperature of 25°C.
  • various types of coating compositions are known, there is still a need for adjustment of coating formulation parameters like viscosity and curing speed within the desired application window.
  • the maximum total coating thickness is 30 to 50 pm.
  • the object of the present invention is furthermore to manufacture a coating composition fulfilling application targets for coil coatings.
  • the coating composition according to the invention is preferably a steel protective coating composition.
  • a coating composition containing a mixture of polysilazanes as preceramic polymers having an adjusted viscosity of a specific target viscosity together with an acrylic based adhesion promoter in the presence of a radical starter and metal particles is able to allow forming of a desired film thickness of a surface coating while being curable at a specific time at a specific peak metal temperature while having high adhesion.
  • a coating composition containing a mixture of polysilazanes having an adjusted viscosity of a specific target viscosity together with an acrylic based adhesion promoter in the presence of a radical starter and metal particles is able to fulfill all application targets known in the art and expected for coil coatings. Furthermore, the coating compositions allow an easy application by user-friendly coating methods so that functional surface coatings may be obtained in an efficient and easy manner under targeted conditions.
  • the invention therefore relates to a coating composition, comprising
  • the invention furthermore relates to a method for preparing a coating composition as described before or preferably described in the following, wherein the method comprising the following steps:
  • the invention furthermore relates to a method for preparing a coated article, wherein the method comprises the following steps:
  • composition is also used synonymously alongside the term “preparation” or “formulation”.
  • viscosity is the dynamic viscosity measured in mPas.
  • the dynamic viscosity is determined by using an Anton Paar Modular Compact Rheometer MCR 92 with a Cone-Plate System equipped with a measuring Cone CP50-1 in accordance with the ASTM D7042 standard, "Standard Test Method for Dynamic Viscosity and Density of Liquids” by Stabinger Viscometer from ASTM International.
  • the term “functional coating” as used herein refers to coatings which impart one or more specific properties to a surface. Generally, coatings are needed to protect surfaces or impart specific effects to surfaces.
  • a preferred surface is a metal panel, metal sheet or coil.
  • cure means conversion to a crosslinked polymer network or a ceramic binder network (for example, through catalysis).
  • polymer includes, but is not limited to, homopolymers, copolymers, for example, block, random, and alternating copolymers, terpolymers, quaterpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible configurational isomers of the material. These configurations include, but are not limited to isotactic, syndiotactic, and atactic symmetries.
  • a polymer is a molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units (i.e. repeating units) derived, actually or conceptually, from molecules of low relative mass (i.e. monomers). Typically, the number of repeating units is higher than 10, preferably higher than 20, in polymers. If the number of repeating units is less than 10, the polymers may also be referred to as oligomers.
  • copolymer generally means any polymer derived from more than one species of monomer, wherein the polymer contains more than one species of corresponding repeating unit.
  • the copolymer is the reaction product of two or more species of monomer and thus comprises two or more species of corresponding repeating unit. It is preferred that the copolymer comprises two, three, four, five or six species of repeating unit. Copolymers that are obtained by copolymerization of three monomer species can also be referred to as terpolymers. Copolymers that are obtained by copolymerization of four monomer species can also be referred to as quaterpolymers. Copolymers may be present as block, random, and/or alternating copolymers.
  • block copolymer stands for a copolymer, wherein adjacent blocks are constitutionally different, i.e. adjacent blocks comprise repeating units derived from different species of monomer or from the same species of monomer but with a different composition or sequence distribution of repeating units.
  • random copolymer refers to a polymer formed of macromolecules in which the probability of finding a given repeating unit at any given site in the chain is independent of the nature of the adjacent repeating units. Usually, in a random copolymer, the sequence distribution of repeating units follows Bernoullian statistics.
  • alternating copolymer stands for a copolymer consisting of macromolecules comprising two species of repeating units in alternating sequence.
  • polysilazane refers to a polymer in which silicon and nitrogen atoms alternate to form the basic backbone. Since each silicon atom is bound to at least one nitrogen atom and each nitrogen atom to at least one silicon atom, both chains and rings of the general formula -[SiR’R”-NR’”-] m (silazane repeating unit) occur, wherein R’ to R’” may be hydrogen atoms, organic substituents or heteroorganic substituents; and m is an integer. If at least one substituent R’ to R’” is an organic or heteroorganic substituent, the polymer is designated as organopolysilazane.
  • Polysilazane A refers to one or more polysilazane polymers having a lower viscosity as a target viscosity having a cyclic, linear, branched and/or cross-linked form or any mixture thereof.
  • Polysilazane B refers to one or more polysilazane polymers having a higher viscosity as a target viscosity having a cyclic, linear, branched and/or cross-linked form or any mixture thereof.
  • the mixture of organic polysilazanes having an adjusted viscosity of a specific target viscosity consists of of one or more polysilazane polymers having a lower viscosity as the target viscosity (Polysilazane A) and one or more polysilazane polymers having a higher viscosity as the target viscosity (Polysilazane B).
  • the ratio of Polysilazane A to Polysilazane B allows the design of a mixture having a specific target viscosity.
  • R 6 is hydrogen or a bond to a Si atom of a further repeating unit where the further repeating unit might be the same or different to M1 or M2. In a particularly preferred embodiment, R 6 is hydrogen or a bond to a Si atom of a further repeating unit where the further repeating unit might be the same to M1 or M2.
  • Polysilazane A and Polysilazane B comprise a repeating unit M1 and a repeating unit M2, wherein M1 and M2 have a meaning as described before or having substituents as preferably described before.
  • Polysilazane A consists of repeating units M1 and M2, wherein M1 and M2 have a meaning as described before or having substituents as preferably described before.
  • Polysilazane B consists of repeating units M1 and M2, wherein M1 and M2 have a meaning as described before or having substituents as preferably described before.
  • Polysilazane A and Polysilazane B are copolymers such as random copolymers or block copolymers or copolymers containing at least one random sequence section and at least one block sequence section. More preferably, each Polysilazane A and Polysilazane B is a random copolymer or a block copolymer.
  • the Polysilazane A and Polysilazane B have a molecular weight distribution.
  • the silazane-containing polymers used in the present invention have a mass average molecular weight M w , as determined by GPC, of at least 1 ,000 g/mol, more preferably of at least 1 ,200 g/mol, even more preferably of at least 1 ,500 g/mol.
  • the mass average molecular weight M w of the silazane-containing polymers is less than 100,000 g/mol. More preferably, the molecular weight M w of the silazane-containing polymers is in the range from 1 ,500 to 50,000 g/mol.
  • Suitable organic polysilazanes to be used according to the invention as described before are commercially available e.g. Durazane 1800 (Merck Electronics KGaA, Germany) or IOTA OPSZ 1800 (IOTA Corporation Ltd.). Suitable organic polysilazanes to be used according to the invention are easily manufactured based on manufacturing processes as described in the prior art e.g. WO0136427 A1 or Zhang Z. et al, Journal of Materials Chemistry 2012, 22, 5300-5303.
  • Polysilazane A is Durazane 1800 or IOTA OPSZ 1800.
  • Polysilazane B is manufactured by using Polysilazane A as described before or preferably described before or below.
  • the coating composition of the present invention comprises one or more solvents.
  • Suitable solvents are organic solvents such as, for example, aliphatic and/or aromatic hydrocarbons, which may be halogenated, such as 1-chloro-4- (trifluoromethyl)benzene, esters such as ethyl acetate, n-butyl acetate or tert-butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl ether, and also mono- or polyalkylene glycol dialkyl ethers (glymes), or mixtures thereof.
  • organic solvents such as, for example, aliphatic and/or aromatic hydrocarbons, which may be halogenated, such as 1-chloro-4- (trifluoromethyl)benzene, esters such as ethyl acetate, n-butyl acetate or tert-butyl acetate,
  • the coating composition according to the invention comprises beside of the mixture of organic polysilazanes Polysilazane A and Polysilazane B having together an adjusted viscosity of a specific target viscosity as described before or preferably described before and optionally an organic solvent or an organic synthesis catalyst an acrylic based adhesion promoter in a concentration of more than 1 wt.% and less than 10 wt.% based on the solid content of the coating composition.
  • Adhesion promoters are chemicals that act at the interface between an organic polymer and an inorganic substrate to enhance adhesion between the two materials.
  • An adhesion promoter in its optimal sense, will act effectively at the organic-inorganic interface to chemically and physically wed these dissimilar materials into a strong cohesive bond structure.
  • Adhesion pomoters are chemical materials that contain dual functionality in the molecular structure.
  • Critical to performance of the coating composition according to the invention is the concentration of the acrylic based adhesion promoter. Concentration ⁇ 1 ,0 wt.% do not show significant improvement of adhesion properties. Concentration > 10 wt.% lead to delamination effects, sometimes also during coil curing process at elevated temperature (100°C to 300°C) because of high acrylic concentration which is not heat stable at such high temperatures.
  • concentration as defined before in formulation delivers best adhesion properties without burn effects of the acrylic backbone.
  • the organic polysilazane content is high enough to built in acrylic resin and protect from disintegration of acrylic backbone.
  • the invention therefore relates to a coating composition as described before or preferably described below wherein the acrylic based adhesion promoter is a solution or a dispersion containing an acrylic resin.
  • Said acrylate or methacrylate polymers may contain polymerized monomers containing carboxyl groups or salts thereof, anhydrides or other monomers such as vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumalic acid monoester, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, vinyl chloride.
  • anhydrides or other monomers such as vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumalic acid monoester, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, vinylidene
  • Luperox TBEC 2,2'-(diazene-1,2-diyl)bis(2,4-dimethylpentane nitrile), decanoyl peroxide, di(tert-butylcyclohexyl) peroxydicarbonate, lauroyl peroxide, tert-butyl peroxydiethylacetate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2- ethylhexanoate, VA-086, 1 ,1’-azodi(hexahydrobenzonitrile), 1,1-bis(tert-butylperoxy)- 3,3,5-trimethylcyclohexane, peroxy dicarbonate, and also photochemical initiators, such as Darocur 2273, Darocur 3331 , Darocur 1164, Irgacur 1850, Darocur 1700, Darocur 1173, Irgacur 184, Daro
  • the coating composition according to the invention comprises beside of the mixture of organic polysilazanes Polysilazane A and Polysilazane B having together an adjusted viscosity of a specific target viscosity as described before or preferably described before, the acrylic based adhesion promoter as described before or preferably described before, the radical starter as described before or preferably described before and optionally an organic solvent or an organic synthesis catalyst metal particles or a dispersion of metal particles.
  • the metal particles are preferably metal particles of aluminum, zinc, copper or mixtures thereof, particularly preferably metal particles of aluminum.
  • Said metal particles may exhibit any shape or form and are provided, for example, in a platelet shape, a spherical, spheroidal, lenticular or in an irregular granular shape.
  • a platelet shape is preferred to ensure a thin, smooth and homogeneous surface structure of the surface coating of an article as described below.
  • Said metal particles when used as a substrate may be further coated with one or more passivation layers or inorganic coating which does not decompose at temperatures up to 500°C.
  • a preferred inorganic coating is silicon dioxide.
  • the size of the flaky metal particle/substrate is not critical per se. In general, all types of flaky metal particles/substrates, which are available in the market, in particular those of the materials as described above, may be used according to the present invention.
  • the flaky metal particles or substrates exhibit an average particle size of from 2 to 100 pm and an average thickness of from 0.005 to 5 pm, more preferably an average particle size of from 5 to 50 pm and an average thickness of from 0.01 to 2 pm, and particularly preferably an average size of from 5 to 30 pm and an average thickness of from 0.02 to 2 pm.
  • the coating composition as described before or preferably described comprises 15 wt.% to 40 wt.% of metal particles as described before or 15 wt.% to 40 wt.% of a dispersion of metal particles as described before based on the total weight of the coating composition and where the dispersion of metal particles has a content of 5 wt.% to 45 wt.% of an organic solvent based on the total weight of the dispersion.
  • the metal particle or dispersion of metal particles is commercially available and is preferably selected from STAPA Metallic R 507 R (art. no. 057307G70, Eckart GmbH), Hydrolan® 501 (art. no. 005332HV0, Eckart GmbH), Toyal 1100 NA (TOYO Aluminum K.K.) or Toyal 1260 M-S (TOYO Aluminum K.K.) or aluminum powder from Beijing Dekedaojin Co. Ltd.
  • the coating compositions of the present invention are storage-stable formulations, which can be applied by conventional coating methods such as e.g. coil coating, spray coating, dip coating, spin coating, slit or slot coating or other coating methods and which can be easily cured to functional surface coatings especially at high temperatures up to 450°C.
  • conventional coating methods such as e.g. coil coating, spray coating, dip coating, spin coating, slit or slot coating or other coating methods and which can be easily cured to functional surface coatings especially at high temperatures up to 450°C.
  • the present invention further relates to a method for preparing a coated article, wherein the method comprises the following steps:
  • the coating composition is applied in step (a) by an application method suitable for applying liquid compositions to a surface of an article.
  • application methods include, for example, coil coating, spray coating, dip coating, spin coating, flow coating, roll-to-roll coating, slit or slot coating or other coating methods.
  • Coil coating, dip coating and roll-to- roll coating are particularly preferred. Coil coating is most preferred.
  • the coating composition is applied in step (a) as a layer in a thickness of 1 pm to 50 pm, preferably 5 pm to 20 pmm, particularly preferably 7 pm to 15 pm, to the surface of the article.
  • the coating composition is applied as a thin layer having a thickness of 8 pm to 12 pm.
  • the curing of the coating in step (b) may be carried out under various conditions, preferably by thermal curing up to 450°C substrate temperature, preferably under a temperature of 100°C to 300 °C.
  • the curing is carried out in the absence of moisture, preferably under inert gas atmosphere, typically under nitrogen atmosphere.
  • the curing time for step (b) is from 10 seconds to 5 minutes, more preferably from 15 seconds to 1 minute, still more preferably from 20 seconds to 40 seconds, depending on the coating composition and coating thickness.
  • the silazane-containing polymers are crosslinked to form a coating on the surface of the article.
  • the coating obtained by the above method forms a rigid and dense functional coating which is excellent in adhesion to the surface which is preferably a surface of a metal sheet or metal panel made from steel, wherein said steel surface can be pretreated with nonpermanent passivation layers, such as phosphatization layers.
  • the coating composition according to the present invention may be applied in so called “direct” or “indirect” hot forming/stamping processes.
  • a flat substrate as described before or preferably described before coated with the protective coating composition according to the invention is sequentially pre-stamped, heated and then hot stamped.
  • the coated flat substrate as described before or preferably described before is first heated and then hot stamped.
  • a coated article which is obtainable or obtained by the above- mentioned preparation method.
  • a preferred coated article is a coated coil prior to heatstamping it.
  • Durazane 1800 commercially available from Merck Electronics KGaA, Germany, art. no. 214049, is a low viscous clear and colorless to slightly yellow liquid with a density of 0,95- 1,05 g/cm 3 (at a temperature of 25°C) and a viscosity of 10 to 40 mPas according to the specification. Since it is a material of oligomeric to polymeric nature the viscosity may vary from batch to batch in the specified viscosity range.
  • Example 1 Increasing viscosity for Durazane 1800 by thermal treatment
  • An amount of 300ml of pure Durazane 1800 having a viscosity of 37 mPas [by using e.g. an Anton Paar Modular Compact Rheometer MCR 92 equipped with a measuring Cone CP50-1 , at a shear rate of 1000s' 1 , and at a temperature of 25°C] are filled into a 500ml three necked glass flask equipped with a Nitrogen inlet, a thermometer measuring the inside temperature and a mechanical stirrer placed in an oil bath on a heating device. Under stirring the flask is purging with Nitrogen for 1h. The complete reaction is done under Nitrogen atmosphere. Then the temperature is increased to the value shown in Table 1 and kept for the time as shown in Table 1. After cooling down to ambient temperature the viscosity of the heat treated Durazane is again measured and the result is shown in Table 1.
  • the dynamic viscosity is determined using an Anton Paar Modular Compact Rheometer MCR 92 Cone-Plate System equipped with a measuring Cone CP50-1 in accordance with the ASTM D7042 standard, "Standard Test Method for Dynamic Viscosity and Density of Liquids” by Stabinger Viscometer from ASTM International.
  • Example 2 Adjusting viscosity by mixing of high and low viscous polysilazanes derived from commercially available Durazane 1800, art. no. 214049, Merck Electronics KGaA, Germany
  • Durazane 1800 material A (Material A) and Durazane 1800 material B (Material B) either commercially available or synthesized according to Example 1 with viscosities and in amounts as specified in Table 2 are filled into a 500ml three necked glass flask equipped with a Nitrogen inlet and a mechanical stirrer. Under Nitrogen atmosphere the mixture is stirred for 4h at a temperature of 25°C. Then the viscosity of the Durazane 1800 mixture is measured and results are shown in Table 2.
  • Table 2 Viscosities are given in mPas and are measured as described; amounts are given in g
  • the coating composition is produced by stirring viscosity adjusted organic polysilazane (Tab. 1 material 2.3) while slowly adding a dispersion of aluminum particles (Hydrolan 501). After 5 min stirring time the formulation is ready to use without degassing or similar actions. Details of said coating composition are given in Table 3.

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Abstract

La présente invention concerne une composition de revêtement, comprenant (i) un mélange de polysilazanes organiques ayant ensemble une viscosité ajustée d'une viscosité cible spécifique ; (ii) un promoteur d'adhérence à base d'acrylique à une concentration supérieure à 1 % en poids et inférieure à 10 % en poids sur la base de la teneur en solides de la composition de revêtement et (iii) un initiateur radicalaire et (iv) des particules métalliques ou une dispersion de particules métalliques et un procédé de préparation de ladite composition de revêtement et un procédé de préparation d'un article revêtu à l'aide de ladite composition de revêtement.
PCT/EP2024/085591 2023-12-15 2024-12-11 Composition de revêtement utilisant un polysilazane de viscosité élevée Pending WO2025125280A1 (fr)

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EP23217239 2023-12-15
EP23217239.5 2023-12-15

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WO2025125280A1 true WO2025125280A1 (fr) 2025-06-19

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US5459114A (en) 1992-11-26 1995-10-17 Tonen Corporation Method for producing ceramic products
WO2001036427A1 (fr) 1999-11-12 2001-05-25 Kion Corporation Composes silazane et/ou polysilazane; procedes de fabrication
US6296805B1 (en) 1998-07-09 2001-10-02 Sollac Coated hot- and cold-rolled steel sheet comprising a very high resistance after thermal treatment
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US20230124254A1 (en) 2021-02-23 2023-04-20 Thor Custom Steel Coatings LLC Steel Protective Coating Compositions, Methods of Their Manufacture, and Methods of Their Use
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CN116121603A (zh) * 2023-01-18 2023-05-16 江门市盈德餐厨实业有限公司 一种硅化钢铝材料

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