Polysilazane hard coating composition

Abstract

The present invention relates to a coating composition comprising a silazane polymer (A), a silane coupling agent (B), and inorganic nanoparticles (C), where components (A), (B), and (C) are present in a certain ratio. The coating composition is particularly suitable for producing hard coatings on the surfaces of various base material substrates.

Description

[Technical Field]

[0001] The present invention relates to a coating composition comprising a silazane polymer (A), a silane coupling agent (B), and inorganic nanoparticles (C), wherein components (A), (B), and (C) are present in a specific ratio. The coating composition is particularly suitable for producing hard coatings on the surfaces of various base material substrates. Hard coatings result in improved physical and chemical surface properties, such as improved mechanical resistance and durability (including improved surface hardness, improved scratch resistance, and / or improved abrasion resistance); improved wetting and adhesion properties (including hydrophobicity and oleophobicity, easy cleaning effect, and / or graffiti resistance); improved chemical resistance (improved corrosion resistance (e.g., against solvents, acidic and alkaline media, and corrosive gases, and / or improved antioxidant effect)); and improved physical barrier or sealing effect. The coating composition according to the present invention enables the creation of hard coatings with maximum mechanical resistance and durability, particularly in terms of maximum surface hardness, scratch resistance, and abrasion resistance. In addition, harmful behaviors such as the formation of cloudy thin films and wetting problems are avoided. Furthermore, the coating composition according to the present invention exhibits high adhesion to various substrate surfaces, enabling easy application using an easy-to-use coating method, and allowing for efficient and easy acquisition of hard coatings. The present invention relates to a method for producing an article coated using the above-described coating composition, and further to an article coated by the above-described method. Further, the use of the above-described coating composition is provided for forming a hard coating on the surface of a base material, thereby improving one or more of the above-described surface properties. [Background technology]

[0002] Polymers containing the silazane repeating unit -[SiR2-NR'-] are typically called polysilazanes. When all substituents R and R' are hydrogen, the material is called a perhydropolysilazane (PHPS), and when at least one of R and R' is an organic moiety, the material is called an organopolysilazane (OPSZ). PHPS and OPSZ are used for various functional coatings to impart certain properties to surfaces, such as graffiti resistance, scratch resistance, corrosion resistance, or hydrophobicity and oleophobicity. Therefore, silazanes are widely used in functional coatings for a variety of applications. Polysilazanes consist of one or more different silazane repeating units, while polysiloxazanes further contain one or more different siloxane repeating units. Polysiloxazanes combine the chemical and behavioral characteristics of both polysilazanes and polysiloxanes. Polysilazanes and polysiloxazanes are resins used to produce functional coatings for various types of applications.

[0003] Typically, both polysilazanes and polysiloxazanes are liquid polymers that solidify at molecular weights of approximately >10,000 g / mol. Most applications utilize liquid polymers with medium molecular weights, typically in the range of 2,000–8,000 g / mol. To produce solid coatings from such liquid polymers, a curing step is required, which is performed after applying the material, either as a pure material or as a compound, to a substrate. Polysilazanes or polysiloxazanes can be crosslinked by hydrolysis, for example, by reaction with moisture in the air. This leads to an increase in molecular weight and solidification or hardening of the material. Therefore, the terms "hardening" and "crosslinking," and the corresponding verbs "to harden" and "to crosslink," are used interchangeably as synonyms in this application when referring to silazane polymers such as polysilazanes and polysiloxazanes. Hardening is usually carried out by hydrolysis under ambient conditions or at high temperatures. Hardened polysilazanes exhibit excellent adhesion, high hardness, and good scratch resistance.

[0004] One of the inherent properties of polysilazane coatings is their high crosslink density after complete curing. As a result, such coatings have high hardness and are applied particularly as hard coats for scratch protection of soft materials such as plastics. Low molecular weight alkoxysilanes (silane coupling agents) such as H2N-(CH2)3-Si(OEt)3 (i.e., 3-aminopropyltriethoxysilane, AMEO) or (MeO)3Si-(CH2)3-NH-(CH2)3-Si(OMe)3 (i.e., bis[3-(trimethoxysilyl)propyl]amine, AMEO-dimer) are used to increase the curing rate due to moisture in the ambient atmosphere. Such additives also increase the hardness after complete curing. Another technique commonly used to increase the hardness and scratch resistance of polysilazane coatings is the addition of nanoparticles. If the coating maintains optical transparency, the size of the nanoparticles should be ≤20 nm in diameter. Typically, inorganic nanoparticles are used, with inorganic oxide nanoparticles being the most commonly used. Silicon oxide nanoparticles are particularly preferred because they offer good performance and are readily available commercially.

[0005] U.S. Patent Application Publication No. 2003 / 0083453 relates to water-curable polysiloxanes and polysilazanes used to produce surface coatings prepared by heating polysilazanes or polysiloxazanes in the presence of an alkoxysilyl reagent. Furthermore, it is suggested that ceramic powders and glass be incorporated to obtain coatings with higher hardness. U.S. Patent Application Publication No. 2020 / 0199406 relates to a transparent coating thin film composition based on polysilazane, and the use of AMEO as a catalyst for such a composition. International Publication No. 2007 / 028511 relates to the use of polysilazanes as permanent coatings on metal and polymer surfaces for preventing corrosion, increasing scratch resistance, and facilitating easier cleaning. For example, inorganic nanoparticles such as SiO2, TiO2, ZnO, ZrO2, or Al2O3 are described as further components of such polysilazane formulations. In addition, the catalytic use of AMEO is described in the examples. Chinese Patent Application Publication No. 108727979 relates to a coating composition comprising a perhydropolysilazane, a siloxane, inorganic particles, an optional catalyst, and an optional silane coupling agent. This coating composition is used to form a coating layer on the surface of a base material having good adhesion, temperature resistance, and scratch resistance, as well as low energy surface properties and easy cleaning properties. European Patent Application Publication No. 3546498 relates to polysilazane compositions comprising organopolysilazane compounds that do not contain a Si-H structure, and organoxysilane compounds having at least two silicon atoms in the molecule, such as bis(trimethoxysilylpropyl)amine or bis(triethoxysilylpropyl)amine. While the aforementioned coating compositions and the surface coatings produced therefrom exhibit several advantageous properties, such as good chemical or mechanical resistance, they do not meet the requirements of modern high-performance surface coatings regarding a combination of high mechanical, chemical, and durability. Therefore, particularly in hard coating applications, there is always a need to further improve the surface coating compositions known at this stage of the art.

[0006] Objective of the present invention Therefore, the object of the present invention is to overcome the drawbacks of the prior art and provide a novel coating composition particularly suitable for producing hard coatings on the surfaces of various base material substrates in order to improve physical and chemical surface properties such as improved mechanical resistance and durability (including improved surface hardness, improved scratch resistance, and / or improved abrasion resistance); improved wetting and adhesion properties (including hydrophobicity and oleophobicity, easy cleaning effect, and / or graffiti resistance); improved chemical resistance (improved corrosion resistance (e.g., against solvents, acidic and alkaline media, and corrosive gases, and / or improved antioxidant effect)); and improved physical barrier or sealing effect. In particular, it is desirable to provide a new coating composition that enables the creation of hard coatings with maximum mechanical resistance and durability, such as maximum surface hardness, scratch resistance, and abrasion resistance. In addition, it is desirable to avoid harmful behaviors such as the formation of cloudy thin films and wetting problems. Furthermore, in addition to the advantages mentioned above, an object of the present invention is to provide a new coating composition that exhibits high adhesion to various substrate surfaces and enables easy application by an easy-to-use coating method, allowing for efficient and easy acquisition of hard coatings. A further object of the present invention is to provide a method for producing a coated article, and a coated article produced by the above method and exhibiting the above-described advantages. Finally, an object of the present invention is to provide a coating composition that can be used to form a hard coating on the surface of various base materials to improve one or more of the aforementioned surface properties, particularly surface hardness, scratch resistance, and abrasion resistance. [Overview of the project]

[0007] The inventors have surprisingly found that a coating composition comprising a silazane polymer (A), a silane coupling agent (B), and inorganic nanoparticles (C), wherein these components are present in a specific mixing ratio, achieves the above-mentioned objectives and, in particular, provides a surface coating having high hardness, high scratch resistance, and high abrasion resistance.

[0008] Considering this, the inventors have surprisingly found that the above objective is (i) Silazane polymer (A), (ii) Silane coupling agent (B), and (iii) Inorganic nanoparticles (C) A coating composition comprising the elements individually or in any combination thereof, We found that a coating composition in which the mass ratio [A]:[B] of silazane polymer (A) to silane coupling agent (B) is in the range of 75:25 to 40:60, and the mass ratio [A+B]:[C] of silazane polymer (A) and silane coupling agent (B) to inorganic nanoparticles (C) is in the range of 80:20 to 50:50, can be achieved. In addition, a method for producing coated articles, (a) the step of applying a coating composition according to the present invention to the surface of an article, and (b) A step of curing the above coating composition to obtain a coated article. A method including this is provided. Furthermore, the present invention provides a coated article that can be obtained or obtained by the above-described method for producing a coated article. The present invention further relates to the use of the coating composition according to the present invention for forming a hard coating on the surface of a base material.

[0009] Preferred embodiments of the present invention are described in the dependent claims. [Brief explanation of the drawing]

[0010] [Figure 1] This figure shows the analysis results of experiments 1-A1 to 1-D6 for coatings derived from formulations 1-A1 to 1-D6. [Figure 2] This figure shows the analysis results of experiments 2-A1 to 2-D6 for coatings derived from formulations 2-A1 to 2-D6. [Figure 3]This figure shows the analysis results of experiments 3-A1 to 3-C5 for coatings derived from formulations 3-A1 to 3-C5. [Modes for carrying out the invention]

[0011] definition The term “polymer” includes, but is not limited to, homopolymers, copolymers, such as block, random, and alternating copolymers, terpolymers, quarterpolymers, etc., as well as their formulations and modifications. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all conceivable configuration isomers of the substance. Such configurations include, but are not limited to, isotactic symmetry, syndiotactic symmetry, and atactic symmetry. Polymers are molecules with high relative molecular weight, and their structure essentially consists of multiple repetitions of units (i.e., repeating units) that actually or conceptually originate from molecules with low relative mass (i.e., monomers). Typically, the number of repeating units in a polymer is more than 10, preferably more than 20. When the number of repeating units is less than 10, polymers may also be called oligomers. As used herein, the term "monomer" refers to a molecule that undergoes polymerization, thereby contributing its constituent units (repeating units) to the essential structure of a polymer. As used herein, the term "homopolymer" refers to a polymer derived from one species of monomer (actual, implicit, or hypothetical).

[0012] As used herein, the term "copolymer" generally refers to any polymer derived from more than one monomer and containing more than one corresponding repeating unit. In one embodiment, the copolymer is a reaction product of two or more monomers and therefore contains two or more corresponding repeating units. The copolymer preferably contains two, three, four, five, or six repeating units. A copolymer obtained by copolymerizing three monomer species may also be called a terpolymer. A copolymer obtained by copolymerizing four monomer species may also be called a quarterpolymer. The copolymer may exist as a block copolymer, a random copolymer, and / or an alternating copolymer. As used herein, the term "block copolymer" refers to a copolymer in which adjacent blocks are constitutively different, that is, adjacent blocks are derived from different types of monomers or from the same type of monomers but contain repeating units with different compositions or arrangement distributions of repeating units. Furthermore, as used herein, the term "random copolymer" refers to a polymer formed from polymers in which the probability of finding a given repeating unit at any given site in the chain does not depend on the properties of adjacent repeating units. Typically, in random copolymers, the arrangement distribution of repeating units follows Bernoulli statistics. As used herein, the term "alternating copolymer" refers to a copolymer comprising a polymer containing two types of repeating units in an alternating arrangement.

[0013] As used herein, the term "polysilazane" refers to a polymer in which silicon and nitrogen atoms alternate to form a basic framework. Each silicon atom is bonded to at least one nitrogen atom, and each nitrogen atom is bonded to at least one silicon atom, hence the general formula is -[SiR 1 R 2 -NR 3 -] m (Silazan repeating unit), in the formula R 1 ~R 3may be a hydrogen atom, an organic substituent, or a heteroorganic substituent, and both a chain and a ring of the general formula where m is an integer occur. Substituent R 1 ~R 3 When all are hydrogen atoms, the polymer is called perhydropolysilazane, polypelhydrosilazane, or inorganic polysilazane (-[SiH2-NH-] m ). When at least one of the substituents R 1 ~R 3 is an organic substituent or a heteroorganic substituent, the polymer is called an organopolysilazane. The term "polysiloxazane" as used herein refers to a polysilazane further containing a portion where silicon atoms and oxygen atoms alternate. Such a portion can be represented, for example, by -[O-SiR[[ID=1�]] 7 R 8 -] n , where R 7 and R 8 may be a hydrogen atom, an organic substituent, or a heteroorganic substituent, and n is an integer. When all the substituents of the polymer are hydrogen atoms, the polymer is called perhydropolysiloxazane. When at least one of the substituents of the polymer is an organic or heteroorganic substituent, the polymer is called an organopolysiloxazane.

[0014] The term "functional coating" as used herein refers to a coating that imparts one or more specific properties to a surface. Generally, a coating is required to protect a surface or impart a specific effect to a surface. There are various effects that can be imparted by a functional coating. For example, mechanical resistance, surface hardness, scratch resistance, abrasion resistance, antibacterial effect, antifouling effect, wetting effect (against water), hydrophobicity and oleophobicity, smoothing effect, durability effect, antistatic effect, anti-pollution effect, anti-fingerprint effect, easy-cleaning effect, anti-graffiti effect, chemical resistance, corrosion resistance, antioxidant effect, physical barrier effect, sealing effect, heat resistance, flame retardancy, low shrinkage, UV barrier effect, light resistance, and / or optical effect. The term "curing" means conversion to a crosslinked polymer network (e.g., by heat or irradiation with or without a catalyst).

[0015] As used herein, the term "silane coupling agent" refers to a compound that has the ability to form durable bonds between organic and inorganic materials. Typical silane coupling agents generally exhibit two classes of functionality. [ka] X is a hydrolyzable group, typically an alkoxy, acyloxy, halogen, or amine. After hydrolysis, a reactive silanol group is formed, which can condense with other silanol groups, for example, those formed during the hydrolysis of polysilazane, to form a siloxane linkage. R is a non-hydrolyzable organic functional group that may have functionalities that confer desired properties. In the context of the present invention, the silane coupling agent is an alkoxysilane compound containing one or more alkoxysilyl groups, as further described below. Silane coupling agents are sometimes called alkoxysilyl reagents.

[0016] As used herein, the term "structural unit" refers to a structural molecular unit having one, two, three, or more binding sites. As used herein, the term "alkyl" means a linear, branched, or cyclic alkyl group which may be substituted. The term "aryl," as used herein, means any monocyclic, bicyclic, tricyclic, or polycyclic aromatic or heteroaromatic group, which may be substituted. A heteroaromatic group contains one or more heteroatoms (e.g., N, O, S, and / or P) in its heteroaromatic system. As used herein, the term "arylalkyl" means any monovalent radical derived from an alkyl radical by replacing one or more hydrogen atoms with an aryl group.

[0017] Preferred Embodiment The present invention (i) Silazane polymer (A), (ii) Silane coupling agent (B), and (iii) Inorganic nanoparticles (C) A coating composition comprising, The present invention relates to a coating composition in which the mass ratio [A]:[B] of silazane polymer (A) to silane coupling agent (B) is in the range of 75:25 to 40:60, and the mass ratio [A+B]:[C] of silazane polymer (A) and silane coupling agent (B) to inorganic nanoparticles (C) is in the range of 80:20 to 50:50.

[0018] Silazane polymer (A) In a preferred embodiment of the present invention, the silazane polymer (A) is of formula (1): -[SiR 1 R 2 -NR 3 -] Formula (1) The iteration unit M is represented by 1 Includes, In the formula, R 1 , R 2 , and R 3 These are either the same or different from each other, and are independently selected from hydrogen, organic groups, or heteroorganic groups. R 1 , R 2 , and R 3Suitable organic and heteroorganic groups include alkyl, alkylcarbonyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylsilyl, alkylsilyloxy, arylsilyl, arylsilyloxy, alkylamino, arylamino, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, aryloxy, aryloxycarbonyl, arylcarbonyloxy, and arylalkyloxy, and combinations thereof (preferably alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkyloxy, and combinations thereof); preferably groups having 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms, even more preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms (e.g., methyl, ethyl, or vinyl)). The group may be further substituted with one or more substituents such as halogens (fluorine, chlorine, bromine, and iodine), alkoxy, alkoxycarbonyl, amino, carboxyl, hydroxyl, and nitro, and combinations thereof.

[0019] In a preferred embodiment, R 1 and R 2 These are the same or different from each other and are independently selected from hydrogen, alkyl having 1 to 30 (preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 6) carbon atoms, alkenyl having 2 to 30 (preferably 2 to 20, more preferably 2 to 10, most preferably 2 to 6) carbon atoms, or aryl having 2 to 30 (preferably 3 to 20, more preferably 4 to 10, most preferably 6) carbon atoms, and one or more hydrogen atoms bonded to carbon atoms may be replaced by fluorine; R 3The element is selected from hydrogen, alkyl having 1 to 30 (preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 6) carbon atoms, alkenyl having 2 to 30 (preferably 2 to 20, more preferably 2 to 10, most preferably 2 to 6) carbon atoms, or aryl having 2 to 30 (preferably 3 to 20, more preferably 4 to 10, most preferably 6) carbon atoms, and one or more hydrogen atoms bonded to the carbon atoms may be replaced by fluorine. In a more preferred embodiment, R 1 and R 2 R is the same or different from one another, independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or phenyl, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine; 3 fluorine is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, vinyl, or phenyl, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine.

[0020] In a particularly preferred embodiment, R 1 and R 2 These are either the same or different from each other, independently selected from the list consisting of -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH=CH2, and -C6H5, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine; R 3 The molecule is selected from a list consisting of -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH=CH2, and -C6H5, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine. In the most preferred embodiment, R 1 and R 2 These are either the same or different from each other, independently selected from -H and -CH3, and the number ratio of H:CH3 in the silazane polymer (A) is preferably in the range of 100:0 to 10:90, more preferably in the range of 60:40 to 25:75. In a preferred embodiment of the present invention, the silazane polymer (A) is of formula (2): -[SiR 4 R 5 -NR 6 -] Formula (2) The iteration unit M is represented by 2 It further includes, In the formula, R 4 , R 5 , and R 6 These are either the same or different from each other, and are independently selected from hydrogen, organic groups, or heteroorganic groups.

[0021] R 4 , R 5 , and R 6 Suitable organic groups and heteroorganic groups include alkyl, alkylcarbonyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylsilyl, alkylsilyloxy, arylsilyl, arylsilyloxy, alkylamino, arylamino, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, aryloxy, aryloxycarbonyl, arylcarbonyloxy, and arylalkyloxy, and combinations thereof (preferably alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkyloxy, and combinations thereof); preferably groups having 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms, even more preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms (e.g., methyl, ethyl, or vinyl)). Such groups may be further substituted with one or more substituents such as halogens (fluorine, chlorine, bromine, and iodine), alkoxy, alkoxycarbonyl, amino, carboxyl, hydroxyl, and nitro, and combinations thereof.

[0022] In a preferred embodiment, R 4 and R 5R is independently selected from hydrogen, alkyl having 1 to 30 (preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 6) carbon atoms, alkenyl having 2 to 30 (preferably 2 to 20, more preferably 2 to 10, most preferably 2 to 6) carbon atoms, or aryl having 2 to 30 (preferably 3 to 20, more preferably 4 to 10, most preferably 6) carbon atoms, and one or more hydrogen atoms bonded to carbon atoms may be replaced by fluorine; R 6 The element is selected from hydrogen, alkyl having 1 to 30 (preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 6) carbon atoms, alkenyl having 2 to 30 (preferably 2 to 20, more preferably 2 to 10, most preferably 2 to 6) carbon atoms, or aryl having 2 to 30 (preferably 3 to 20, more preferably 4 to 10, most preferably 6) carbon atoms, and one or more hydrogen atoms bonded to the carbon atoms may be replaced by fluorine. In a more preferred embodiment, R 4 and R 5 R is the same or different from one another, independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or phenyl, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine; 6 fluorine is selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, vinyl, or phenyl, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine. In the most preferred embodiment, R 4 and R 5 These are either the same or different from each other, independently selected from the list consisting of -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH=CH2, and -C6H5, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine; R 6The molecule is selected from a list consisting of -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH=CH2, and -C6H5, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine. In a preferred embodiment of the present invention, the silazane polymer (A) is of formula (3): -[SiR 7 R 8 -O-] Formula (3) The iteration unit M is represented by 3 It further includes, In the formula, R 7 and R 8 These are either the same or different from each other, and are independently selected from hydrogen, organic groups, or heteroorganic groups. R 7 and R 8 Suitable organic and heteroorganic groups include alkyl, alkylcarbonyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylsilyl, alkylsilyloxy, arylsilyl, arylsilyloxy, alkylamino, arylamino, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, aryloxy, aryloxycarbonyl, arylcarbonyloxy, and arylalkyloxy, and combinations thereof (preferably alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkyloxy, and combinations thereof); preferably groups having 1 to 30 carbon atoms (more preferably 1 to 20 carbon atoms, even more preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms (e.g., methyl, ethyl, or vinyl)). Such groups may be further substituted with one or more substituents such as halogens (fluorine, chlorine, bromine, and iodine), alkoxy, alkoxycarbonyl, amino, carboxyl, hydroxyl, and nitro, and combinations thereof.

[0023] In a preferred embodiment, R 7 and R 8These are either the same or different from each other and are independently selected from hydrogen, alkyl having 1 to 30 (preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 6) carbon atoms, alkenyl having 2 to 30 (preferably 2 to 20, more preferably 2 to 10, most preferably 2 to 6) carbon atoms, or aryl having 2 to 30 (preferably 3 to 20, more preferably 4 to 10, most preferably 6) carbon atoms, where one or more hydrogen atoms bonded to the carbon atoms may be replaced by fluorine.

[0024] In a more preferred embodiment, R 7 and R 8 These are either the same or different from each other, independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or phenyl, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine. In the most preferred embodiment, R 7 and R 8 These are either the same or different from each other, independently selected from the list consisting of -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH=CH2, and -C6H5, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine. Silazane polymers have repeating units M 1 and further iteration units M 2 Includes M 1 and M 2 It is preferable that these are different silazan repeat units. Furthermore, silazane polymers have repeating units M 1 and further iteration units M 3 Includes M 1 is a silazane repeating unit, M 3 It is preferable that it is a siloxane repeating unit. Furthermore, silazane polymers have repeating units M 1 , further iteration units M 2 , and further iteration units M 3 Includes M 1 and M 2are different silazane repeating units, and M 3 is preferably a siloxane repeating unit. In one embodiment, the silazane polymer is a polysilazane which may be perhydropolysilazane or organopolysilazane. Preferably, the polysilazane has repeating units M 1 and optionally further repeating units M 2 and M 1 and M 2 are different silazane repeating units.

[0025] In an alternative embodiment, the silazane polymer is a polysiloxazane which may be perhydropolysiloxazane or organopolysiloxazane. Preferably, the polysiloxazane has repeating units M 1 and further repeating units M 3 where M 1 is a silazane repeating unit and M 3 is a siloxane repeating unit. Preferably, the polysiloxazane has repeating units M 1 further repeating units M 2 and further repeating units M 3 where M 1 and M 2 are different silazane repeating units and M 3 is a siloxane repeating unit. Preferably, the silazane polymer is a copolymer such as a random copolymer, or a block copolymer, or a mixed random block copolymer containing at least one random segment and at least one block segment. More preferably, the silazane polymer is a random copolymer or a block copolymer.

[0026] The silazane polymer used in the present invention preferably does not have a monocyclic structure. More preferably, the silazane polymer has a mixed polycyclic, linear structure, and / or a branched structure. Silazane polymers have a molecular weight distribution. Preferably, the silazane polymer used in the coating composition of the present invention has a mass-average molecular weight M, measured by GPC, of ​​at least 1,000 g / mol, more preferably at least 1,200 g / mol, and even more preferably at least 1,500 g / mol. w It has the following characteristics. Preferably, the mass-average molecular weight M of the silazane polymer. w It is less than 100,000 g / mol. More preferably, the molecular weight M of the silazane polymer. w This ranges from 1,500 to 50,000 g / mol. Preferably, the total content of the silazane polymer in the coating composition is in the range of 10 to 90% by mass, preferably 20 to 60% by mass, based on the total mass of the coating composition.

[0027] Silane coupling agent (B) The silane coupling agent (B) contained in the coating composition according to the present invention preferably contains one or more alkoxysilyl groups. More preferably, the silane coupling agent (B) contained in the coating composition according to the present invention contains one, two, three, or four alkoxysilyl groups. In a preferred embodiment of the present invention, the silane coupling agent (B) is of formula (a): [ka] Formula (a) It is represented by, In the formula, Z is a structural unit containing one or more carbon atoms and / or silicon atoms. R IThese are linear alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, each independently of the others in each occurrence, and optionally comprising one or more -O- and / or -Si(CH3)2- groups, branched alkoxy groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms, or cyclic alkoxy groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. R II In each occurrence, these are, independently of each other, a linear alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; a branched alkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms; or a cyclic alkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. k is 0, 1, or 2, preferably 0. n is 1, 2, 3, or 4, preferably 1 or 2.

[0028] In a more preferred embodiment of the present invention, the silane coupling agent (B) is of formula (b) to (e): [ka] Formula (b) Formula (c) [ka] Formula (d) Formula (e) It is represented by one of the following: In the formula, X b (CH3)2N-, [HO-(CH2) m ]2N-,AcO-,CH3(CH2) m-NH-, CH3-NH-, Cl-, H2C=C(CH3)-CH2-NH-, H2C=C(CH3)-CO-O-, H2C=C(CH3)-O-CH2-CH(OH)-CH2-N H-, H2C=CH-, H2C=CH-CH2-NH-, H2C=CH-CO-CH2-CH(OH)-CH2-NH-, H2C=CH-CO-O-, H2N-, H2N-(CH2) m -NH-, H2N-(CH2) m -NH-(CH2) n -, H2N-(CH2) m -NH-(CH2) n -NH-, H2N-(CH2) m -NH-C4H6-, H2N-(CH2) m NH-CH2-C4H6-, H2N-(CH2) m -OC(CH3)2-CH=CH-, H2N-C6H4-, H2N-C6H4-O-, H3C-, H3C-(CH2) m -, H3C-(CH2) m -O-, H3CO-, HO-, HS-, NCS-, Ph2N-, Ph-CO-O-, Ph-NH-, and [ka] Selected from a list consisting of, m is an integer between 1 and 10, preferably between 1 and 6, more preferably between 1 and 3. n is an integer between 1 and 10, preferably between 1 and 6, more preferably between 1 and 3. X c is, -(CH2) p -, -NH-, -NH-(CH2) p Selected from the list consisting of -NH-, -O-, -S-, -S2-, -S3-, -S4-, -Si(CH3)2-, and -Si(CH3)2-O-Si(CH3)2-, p is an integer between 1 and 20, preferably between 1 and 12, more preferably between 1 and 8. X d teeth, [ka] and [ka] Selected from a list consisting of, X e teeth, [ka] Selected from a list consisting of, Y is either absent, or a linear alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; a branched alkylene group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms; or a cyclic alkylene group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. R I These are linear alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, each independently of the others in each occurrence, and optionally containing one or more -O- and / or -Si(CH3)2- groups, branched alkoxy groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms, or cyclic alkoxy groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. R II In each occurrence, these are, independently of each other, a linear alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; a branched alkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms; or a cyclic alkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. k is 0, 1, or 2, preferably 0.

[0029] X d and X e In the above structure, the wavy lines indicate the bonding sites.

[0030] The preferred silane coupling agent (B) of formula (b) is selected from the following list: (3-Acryloxypropyl)dimethylmethoxysilane, (3-Acryloxypropyl)methyldimethoxysilane, (3-Acryloxypropyl)trimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, (methacryloxymethyl)dimethylethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(3-aminopropoxy)-3,3-dimethyl-1-propenyl-trimethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, 3-(N-arylamino)propyltrimethoxysilane, 3-(trimethoxysilyl)-1-propanethol, 3-amino Propyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltris(methoxyethoxyethoxy)silane, 3-chloropropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltris(methoxyethoxy)silane, 4-aminobutyltriethoxysilane, 6-ethyl-6-(2-methoxyethoxy)-2,5,7,10-Tetraoxa-6-silaundecane, Acetoxymethyltriethoxysilane, Acetoxymethyltrimethoxysilane, Acetoxypropyltrimethoxysilane, Benzoyloxypropyltrimethoxysilane, Hydroxymethyltriethoxysilane, m-Aminophenyltrimethoxysilane, Methacryloxymethyltriethoxysilane, Methacryloxymethyltrimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-(6-aminohexyl)aminopropyltrimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, N,N-Bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, N, 1 -(3-trimethoxysilylpropyl)diethylenetriamine, N-methylaminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminomethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, tetraethoxysilane, triethoxy(3-thiocyanato)propylsilane, triethoxy(octyl)silane, trimethoxymethylsilane, and vinyltriethoxysilane.

[0031] The preferred silane coupling agent (B) of formula (c) is selected from the following list: 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, 1-(trimethoxysilyl)-2-(dimethylmethoxysilyl)ethane, 1-(trimethoxysilyl)-2-(methyldimethoxysilyl)ethane, 1,2-bis(dimethylmethoxysilyl)ethane, 1,2-bis(methyldimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(triethoxysilylethyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(trimethoxysilylethyl)-1,1,3,3-tetramethyldisiloxane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(trimethoxysilyl)octane, bis( 3-(triethoxysilyl)-1-propyl) disulfide, bis(3-(trimethoxysilyl)-1-propyl) disulfide, bis(3-(trimethoxysilyl)-1-propyl) tetrasulfide, bis[2-(triethoxysilyl)ethyl]dimethylsilane, bis[3-(triethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl] sulfide, bis[2-(trimethoxysilyl)ethyl]dimethylsilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(trimethoxysilyl)propyl] sulfide, bis[3-(triethoxysilyl)propyl] ether, bis[3-(trimethoxysilyl)propyl] ether, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine.

[0032] The preferred silane coupling agent (B) of formula (d) is selected from the following list: Tris(triethoxysilylethyl)methylsilane, Tris(triethoxysilylethyldimethylsiloxy)methylsilane, Tris(triethoxysilylpropyl)amine, Tris(triethoxysilylpropyl)methylsilane, Tris(trimethoxysilylethyl)methylsilane, Tris(trimethoxysilylethyldimethylsiloxy)methylsilane, Tris(trimethoxysilylpropyl)amine, and Tris(trimethoxysilylpropyl)methylsilane. The preferred silane coupling agent (B) of formula (e) is selected from the following list: Tetrakis(triethoxysilylethyl)silane, tetrakis(triethoxysilylpropyl)silane, and tetrakis(trimethoxysilylpropyl)silane. Particularly preferred silane coupling agents (B) are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine, tris(trimethoxysilylpropyl)amine, and tris(triethoxysilylpropyl)amine.

[0033] The coating composition according to the present invention preferably contains one of the above-mentioned silane coupling agents, or a combination of two, three, or more of the above-mentioned silane coupling agents.

[0034] Inorganic nanoparticles (C) In preferred embodiments of the present invention, inorganic nanoparticles (C) are selected from the list of carbides, diamonds, nitrides, oxides, silicates, sulfates, sulfides, sulfites, and titanates, which may optionally be surface-modified with a capping agent. In a more preferred embodiment of the present invention, the inorganic nanoparticles (C) are selected from the list consisting of boron carbide, silicon carbide, titanium carbide, tungsten carbide, diamond, boron nitride, silicon nitride, titanium nitride, aluminum oxide, molybdenum oxide, silica, titania, and zirconia. In the most preferred embodiment of the present invention, the inorganic nanoparticle (C) is silica (SiO2). The coating composition according to the present invention may contain one, two, or more types of the above-mentioned inorganic nanoparticles (C). Preferably, the inorganic nanoparticles (C) have a particle size of ≤100 nm, more preferably ≤60 nm, even more preferably ≤40 nm, and most preferably ≤25 nm. Preferably, the inorganic nanoparticles (C) have a particle size in the range of 1 to 100 nm, more preferably 5 to 60 nm, even more preferably 10 to 40 nm, and most preferably 10 to 25 nm. The particle size can be determined by any standard method known to those skilled in the art, such as dynamic light scattering. Apparatus and methods for determining the size of nanoscale particles are available, for example, from Malvern Panalytical (https: / / www.malvernpanalytical.com / en / products / product-range / zetasizer-range / zetasizer-advance-range / zetasizer-pro).

[0035] mass ratio In the coating composition according to the present invention, the mass ratio [A]:[B] of silazane polymer (A) to silane coupling agent (B) is in the range of 75:25 to 40:60, and the mass ratio [A+B]:[C] of silazane polymer (A) and silane coupling agent (B) to inorganic nanoparticles (C) is in the range of 80:20 to 50:50. The mass ratio [A]:[B] of the silazane polymer (A) to the silane coupling agent (B) is preferably in the range of 66:34 to 45:55, and the mass ratio [A+B]:[C] of the silazane polymer (A) and silane coupling agent (B) to inorganic nanoparticles (C) is preferably in the range of 73:27 to 55:45. The mass ratio [A]:[B] of the silazane polymer (A) to the silane coupling agent (B) is preferably in the range of 60:40 to 50:50, and the mass ratio [A+B]:[C] of the silazane polymer (A) and silane coupling agent (B) to inorganic nanoparticles (C) is more preferably in the range of 70:30 to 60:40.

[0036] Further ingredients The coating composition according to the present invention preferably contains one or more solvents. Suitable solvents include, for example, halogenated aliphatic and / or aromatic hydrocarbons such as 1-chloro-4-(trifluoromethyl)benzene, esters such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, or tert-butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl ether, and further organic solvents such as mono or polyalkylene glycol dialkyl ethers (Glymm), or alpha alkyl omega alkyl carbonyl mono or polyglycols such as butyl diglycol acetate, or mixtures thereof. Furthermore, the coating composition according to the present invention may preferably include one or more additives selected from the following list: additives affecting evaporation behavior, additives affecting thin film formation, adhesion promoters, corrosion inhibitors, crosslinking agents, dispersants, fillers, functional pigments (e.g., for providing functional effects such as electrical conductivity or thermal conductivity, magnetic properties, etc.), optical pigments (e.g., for providing optical effects such as color, refractive index, pearlescent effect, etc.), particles that reduce thermal expansion, primers, rheology modifiers (e.g., thickeners), surfactants (e.g., wetting agents and spreaders, or additives for improving hydrophobicity or oleophobicity and graffiti resistance), viscosity modifiers, and other types of resins or polymers.

[0037] The curing of the coating composition can be accelerated by adding one or more catalysts. Examples of useful catalysts include Lewis acids such as boron-, aluminum-, tin-, or zinc-alkyl, aryl, or carboxylates; Brønsted acids such as carboxylic acids; bases such as primary, secondary, or tertiary amines or phosphazenes; or metal salts of carboxylates, acetylacetonates, or alkoxylates such as Pd, Pt, Al, B, Sn, or Zn salts. When using silazanes having both Si-H and Si-CH=CH2 groups, well-known hydrosilylation catalysts such as Pt or Pd salts or complexes can be used. When using silazanes having only Si-CH=CH2 or both Si-H and Si-CH=CH2 groups, UV or thermal radical initiators such as peroxides or azo compounds can be used. In preferred embodiments, the coating composition according to the present invention comprises one or more of the catalysts described above. Those skilled in the art will understand that the above-mentioned preferred, more preferred, particularly preferred, and most preferred embodiments relating to the definitions of coating compositions and their components can be freely combined in any desired manner.

[0038] method The present invention relates to a method for producing a coated article, (a) the step of applying a coating composition according to the present invention to the surface of an article, and (b) A step of curing the above coating composition to obtain a coated article. Further details regarding methods including Preferably, the coating composition applied in step (a) is a homogeneous liquid having a viscosity in the range of 0.5 to 1,000 mPas, more preferably 1 to 250 mPas. The viscosity of the composition can be adjusted by the type and content of the solvent, as well as the type, ratio, and / or molecular weight of the silazane polymer (A), silane coupling agent (B), and inorganic nanoparticles (C).

[0039] The coating composition is preferably applied in step (a) by an application method suitable for applying the liquid composition to the surface of the article. Such methods include, for example, cloth wiping, sponge wiping, dip coating, spray coating, flow coating, roller coating, slit coating, slot coating, spin coating, dispensing, screen printing, stencil printing, or inkjet printing. Dip coating and spray coating are particularly preferred.

[0040] The coating composition of the present invention can be applied to the surfaces of various articles, such as buildings, dentures, furnishings, furniture, sanitary fixtures (toilets, washbasins, bathtubs, etc.), signs, signboards, plastic products, glass products, ceramic products, metal products, wood products, and vehicles (road vehicles, railway vehicles, ships, and aircraft). The surface of the article is preferably made of one of the base materials described below for use. Typically, the coating composition is applied to the surface of the article in step (a) as a layer with a thickness of 0.1 μm to 100 μm, preferably 0.5 μm to 50 μm. In a preferred embodiment, the coating composition is applied as a thin layer having a thickness of 1 to 30 μm. The curing of the coating in step (b) can be carried out under various conditions, such as ambient curing, thermal curing, and / or irradiation curing. The curing is optionally carried out in the presence of moisture, preferably in the form of water vapor. For this purpose, an artificial climate chamber can be used. Ambient curing is preferably carried out at a temperature in the range of 10 to 40°C. Thermal curing is preferably carried out at a temperature in the range of 100 to 200°C, preferably 120 to 180°C. Irradiation curing is preferably carried out by IR irradiation or UV irradiation. Preferred IR irradiation wavelengths are in the range of 7 to 15 μm, or 1 to 3 μm in the case of substrate absorption. Preferred UV irradiation wavelengths are in the range of 300 to 500 nm.

[0041] Preferably, the curing in step (b) is carried out in a furnace or artificial climate chamber. Alternatively, when coating very large items (e.g., buildings, vehicles, etc.), the curing is preferably carried out under ambient conditions. Preferably, the curing time in step (b) is 0.01 to 24 hours, more preferably 0.10 to 16 hours, even more preferably 0.15 to 8 hours, and most preferably 0.20 to 5 hours, depending on the coating composition and coating thickness. Other preferred curing conditions are: 1. Thermosetting (vulcanization) in the presence of a catalyst such as a peroxide or sulfur compound. 2. UV curing in the presence of a UV-activated photoinitiator That is the case. After curing in step (b), the coating composition is chemically crosslinked to form a hard coating on the surface of the article. The coating obtained by the above method is a hard coating with maximum surface hardness, scratch resistance, abrasion resistance, and other maximum mechanical resistance and durability. Furthermore, harmful behaviors such as the formation of cloudy thin films and wetting problems are avoided.

[0042] Goods Furthermore, coated articles that can be obtained or are obtained by the above-described manufacturing method are provided. use The present invention further relates to the use of the coating composition according to the present invention for forming a hard coating on the surface of a base material. Preferred base materials to which the coating composition according to the present invention is applied include, for example, metals (iron, steel, silver, zinc, aluminum, nickel, titanium, vanadium, chromium, cobalt, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, silicon, boron, tin, lead, or manganese, or alloys thereof optionally coated with oxide or plating films); plastics (polymethyl methacrylate (PMMA), polyurethane, polyester (PET), polyaryl diglycol carbonate (PADC), polycarbonate, polyimide, polyamide, epoxy resin). Examples of materials include a wide variety of materials such as oil, ABS resin, polyvinyl chloride, polyethylene (PE), polypropylene (PP), polythiocyanate, or polytetrafluoroethylene (PTFE); glass (fused silica, soda-lime silica glass (window glass), sodium borosilicate glass (Pyrex®), lead oxide glass (crystal glass), aluminosilicate glass, or germanium oxide glass, etc.); and building materials (brick, cement, ceramic, clay, concrete, gypsum, marble, mineral wool, mortar, stone, or wood, and mixtures thereof, etc.).

[0043] The base material may be treated with a primer to enhance the adhesion of the hard coating. Such primers include, for example, silanes, siloxanes, or silazanes. When using plastic materials, it may be advantageous to perform pretreatment by flame treatment, corona treatment, or plasma treatment, which can improve the adhesion of the functional coating. When using building materials, it may be advantageous to perform precoating with a lacquer, varnish, or paint, such as polyurethane lacquer, acrylic lacquer, and / or dispersion paint. The present invention has been further illustrated by the following embodiments, which should not be construed as limiting in any way. Those skilled in the art will recognize that various modifications, additions, and changes can be made to the present invention without departing from the spirit and scope of the invention. [Examples]

[0044] Raw materials used The following raw materials were used in the examples described herein. • DBU[1,8-diazabicyclo[5.4.0]undeca-7-ene], available from Sigma-Aldrich. • Anhydrous n-butyl acetate is available from Sigma-Aldrich. • Nanopol(registered trademark) C784, 50% by mass in butyl acetate, average particle size 20 nm, colloidal silica, available from Evonik. • 3-aminopropyltriethoxysilane (AMEO), available from Sigma-Aldrich: [ka] • Bis[3-(trimethoxysilyl)propyl]amine (AMEO-dimer), available from Sigma-Aldrich: [ka] Durazane® 1000:n:m=0:100, Durazane® 1033:n:m=33:67, Durazane® 1066:n:m=66:34, Durazane® 1085:n:m=85:15, all available from Merck KGaA: [ka]

[0045] I. Preparation of a formulation containing Durazane® as the silazane polymer (A) and AMEO as the silane coupling agent (B) A formulation containing Durazane® as the silazane polymer (A) and AMEO as the silane coupling agent (B) was prepared according to the following basic procedure. The exact amounts used are shown in Table 1. First, AMEO was mixed with the solvent n-butyl acetate. Then, Durazane® was added. The mixture was vigorously stirred for 8 hours, and a clear solution was finally obtained. [Table 1]

[0046] II. Preparation of a formulation containing Durazane® as the silazane polymer (A), AMEO-dimer as the silane coupling agent (B), and DBU. A formulation containing Durazane® as the silazane polymer (A), AMEO-dimer as the silane coupling agent (B), and DBU was prepared according to the following basic procedure. The exact amounts used are shown in Table 2. First, the AMEO-dimer was mixed with the solvent n-butyl acetate, then DBU was added, and the mixture was vigorously stirred for 4 hours. Next, Durazane® was added, and the mixture was vigorously stirred for a further 8 hours. Finally, a clear solution was obtained. [Table 2]

[0047] III. Preparation of a formulation containing Durazane® as a silazane polymer (A), AMEO-dimer as a silane coupling agent (B), and inorganic nanoparticles (C). A formulation containing Durazane® as a silazane polymer (A), AMEO as a silane coupling agent (B), and inorganic nanoparticles (C) was prepared according to the following basic procedure. The exact amounts used are shown in Table 3. First, AMEO was mixed with the solvent n-butyl acetate, then inorganic nanoparticles were added, and the mixture was vigorously stirred for 4 hours. Next, Durazane® was added, and the mixture was vigorously stirred for another 4 hours. Finally, a clear to slightly milky white solution was obtained. [Table 3]

[0048] IV. Application All formulations were spin-coated onto 10cm x 10cm glass plates. The spin coater's rotation speed was adjusted to 250-2,000 rpm to achieve a thin film thickness of 2.0-2.5 μm. All coated glass plates were cured for 14 days under ambient conditions of 25°C and 50% relative humidity.

[0049] Measurement and evaluation of coating performance: After curing for 14 days, the entire coating was visually analyzed for turbidity, heterogeneity, cracks, delamination, and other obvious thin-film defects. The hardness of the coating was analyzed using a nanoindenter [Helmut Fisher FISCHERSCOPE HM2000 S nanoindenter model, Vickers diamond pyramid] according to DIN EN ISO 14577-1 / ASTM E 2546. The results are shown in Tables 4, 5, and 6. [Table 4]

[0050] The results in Table 4 and Figure 1 show that hardness increases almost linearly with increasing AMEO content. However, when the AMEO content reaches 60 mass%, the coating exhibits wettability defects and no longer forms a closed thin film. For the Durazane® type, the higher the amount of -[Si(H)CH3-NH]- monomer units in the polymer, the higher the nanoindenter martens hardness. [Table 5] TIFF0007839166000017.tif135154

[0051] Similar to Table 4 / Figure 1, Table 5 / Figure 2 shows that hardness increases almost linearly with increasing amount of AMEO-dimer. In contrast to AMEO, the dimer AMEO-dimer shows a greater effect when used in smaller amounts. However, when the amount of AMEO reaches 60 mass%, the coating exhibits wet defects and no longer forms a closed thin film. When mixed with Durazane® (Durazane® 1066 and Durazane® 1085) containing a larger amount of -[Si(CH3)2-NH]-monomer units, a cloudy thin film is formed. For the types of Durazane®, in this case as well, the higher the amount of -[Si(H)CH3-NH]-monomer units in the polymer, the higher the nanoindenter martens hardness. [Table 6]

[0052] Table 6 and Figure 3 show that hardness increases almost linearly with increasing nanoparticle content for all three Durazane® 1033:AMEO ratios. However, when the nanoparticle content reaches 60% by mass, cracks form in the coating after curing.

[0053] In summary, we can draw the following basic conclusions: 1. A higher ratio of -[Si(H)CH3-NH]- monomer units in the Durazane® polymer results in a harder coating. 2. A higher amount of silane coupling agent relative to the Durazane® polymer results in a harder coating. However, too much silane coupling agent can cause the coating to exhibit thin-film defects. 3. A higher amount of nanoparticles relative to the total amount of Durazane® polymer and silane coupling agent results in a harder coating. However, when the amount of nanoparticles exceeds 60%, the coating exhibits thin-film defects. Another aspect of the present invention may be as follows: [1] (i) silazane polymer (A), (ii) Silane coupling agent (B), and (iii) Inorganic nanoparticles (C) A coating composition comprising, A coating composition in which the mass ratio [A]:[B] of the silazane polymer (A) to the silane coupling agent (B) is in the range of 75:25 to 40:60, and the mass ratio [A+B]:[C] of the silazane polymer (A) and the silane coupling agent (B) to the inorganic nanoparticles (C) is in the range of 80:20 to 50:50. [2] The coating composition according to [1], wherein the mass ratio [A]:[B] of the silazane polymer (A) to the silane coupling agent (B) is in the range of 66:34 to 45:55, and the mass ratio [A+B]:[C] of the silazane polymer (A) and the silane coupling agent (B) to the inorganic nanoparticles (C) is in the range of 73:27 to 55:45. [3] The coating composition according to [1], wherein the mass ratio [A]:[B] of the silazane polymer (A) to the silane coupling agent (B) is in the range of 60:40 to 50:50, and the mass ratio [A+B]:[C] of the silazane polymer (A) and the silane coupling agent (B) to the inorganic nanoparticles (C) is in the range of 70:30 to 60:40. [4] The silazane polymer (A) is a repeating unit M represented by formula (1) 1 Includes, -[SiR 1 R 2 -NR 3 -] Formula (1) In the formula, R 1 、R 2 , and R 3 The coating composition according to any one of the above [1] to [3], wherein the elements are the same or different from each other and are independently selected from hydrogen, an organic group, or a heteroorganic group. 〔5〕R 1 and R 2 R is either the same or different from each other, independently selected from hydrogen, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to carbon atoms may be replaced by fluorine; 3 The coating composition according to [4] above, wherein is selected from hydrogen, an alkyl having 1 to 30 carbon atoms, an alkenyl having 2 to 30 carbon atoms, or an aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to carbon atoms may be replaced by fluorine. [6] The silazane polymer (A) is a repeating unit M represented by formula (2) 2 It further includes, -[SiR 4 R 5 -NR 6 -] Formula (2) In the formula, R 4 、R 5 , and R 6 The coating composition according to [4] or [5], wherein the groups are the same or different from each other and are independently selected from hydrogen, organic groups, or heteroorganic groups. 〔7〕R 4 and R 5 R is either the same or different from each other, independently selected from hydrogen, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to carbon atoms may be replaced by fluorine; 6 The coating composition according to [6], wherein is selected from hydrogen, an alkyl having 1 to 30 carbon atoms, an alkenyl having 2 to 30 carbon atoms, or an aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to carbon atoms may be replaced by fluorine. [8] The coating composition according to any one of the above [1] to [7], wherein the silane coupling agent (B) comprises one or more alkoxysilyl groups. [9] The silane coupling agent (B) is represented by formula (a), TIFF0007839166000019.tif930 Formula (a) In the formula, Z is a structural unit containing one or more carbon atoms and / or silicon atoms. R I In each occurrence, independently of each other, one or more -O- and / or -Si(CH) 3 ) 2 - A linear alkoxy group having 1 to 20 carbon atoms, a branched alkoxy group having 3 to 20 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, which may contain a - group. R II In each occurrence, these are, independently of each other, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. k is 0, 1, or 2. n is 1, 2, 3, or 4. The coating composition according to any one of the above items [1] to [8].

[10] The silane coupling agent (B) is represented by one of formulas (b) to (e), JPEG0007839166000020.jpg13150 Formula (b) Formula (c) JPEG0007839166000021.jpg32150 Formula (d) Formula (e) In the formula, X b (CH 3 ) 2 N- [HO-(CH 2 ) m ] 2 N-, AcO-, CH 3 (CH 2 ) m -NH-, CH 3 -NH-, Cl-, H 2 C=C(CH 3 )-CH 2 -NH-, H 2 C=C(CH 3 )-CO-O-, H 2 C=C(CH 3 )-O-CH 2 -CH(OH)-CH 2 -NH-, H 2 C=CH-, H 2 C=CH-CH 2 -NH-, H 2 C=CH-CO-CH 2 -CH(OH)-CH 2 -NH-, H 2 C=CH-CO-O-, H 2 N-, H 2 N-(CH 2 ) m -NH-, H 2 N-(CH 2 ) m -NH-(CH 2 ) n -、H 2 N-(CH 2 )m -NH-(CH 2 ) n -NH-, H 2 N-(CH 2 ) m -NH-C 4 H 6 -、H 2 N-(CH 2 ) m NH-CH 2 -C 4 H 6 -、H 2 N-(CH 2 ) m -OC(CH 3 ) 2 -CH=CH-, H 2 NC 6 H 4 -、H 2 NC 6 H 4 -O-, H 3 C-, H 3 C-(CH 2 ) m -、H 3 C-(CH 2 ) m -O-, H 3 CO-, HO-, HS-, NCS-, Ph 2 N-, Ph-CO-O-, Ph-NH-, and JPEG0007839166000022.jpg1033 Selected from a list consisting of, m is an integer between 1 and 10. n is an integer between 1 and 10. X c is, -(CH 2 ) p -, -NH-, -NH-(CH 2 ) p -NH-, -O-, -S-, -S 2 -、-S 3 -、-S 4 -, -Si(CH 3 ) 2 -, and -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 - Selected from a list consisting of, p is an integer between 1 and 20. X d teeth, JPEG0007839166000023.jpg1718 and JPEG0007839166000024.jpg1818 Selected from a list consisting of, X e teeth, JPEG0007839166000025.jpg1717 Selected from a list consisting of, Y is either absent, or is a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms. R I In each occurrence, independently of each other, one or more -O- and / or -Si(CH) 3 ) 2 - A linear alkoxy group having 1 to 20 carbon atoms, a branched alkoxy group having 3 to 20 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, which may contain a - group. R II In each occurrence, these are, independently of each other, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. k is 0, 1, or 2. The coating composition according to any one of the above items [1] to [9].

[11] The silane coupling agent (B) is (i) (3-Acryloxypropyl)dimethylmethoxysilane, (3-Acryloxypropyl)methyldimethoxysilane, (3-Acryloxypropyl)trimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, (methacryloxymethyl)dimethylethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(3-aminopropoxy)-3,3-dimethyl-1-propenyl-trimethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, 3-(N-arylamino)propyltrimethoxysilane, 3-(trimethoxysilyl)-1-propanethol, 3-amino Propyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltris(methoxyethoxyethoxy)silane, 3-chloropropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltris(methoxyethoxy)silane, 4-aminobutyltriethoxysilane, 6-ethyl-6-(2-methoxyethoxy)-2,5,7,10-Tetraoxa-6-silaundecane, Acetoxymethyltriethoxysilane, Acetoxymethyltrimethoxysilane, Acetoxypropyltrimethoxysilane, Benzoyloxypropyltrimethoxysilane, Hydroxymethyltriethoxysilane, m-Aminophenyltrimethoxysilane, Methacryloxymethyltriethoxysilane, Methacryloxymethyltrimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-(6-aminohexyl)aminopropyltrimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, N,N-Bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, N, 1 Monofunctional silane coupling agents selected from -(3-trimethoxysilylpropyl)diethylenetriamine, N-methylaminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminomethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, tetraethoxysilane, triethoxy(3-thiocyanato)propylsilane, triethoxy(octyl)silane, trimethoxymethylsilane, and vinyltriethoxysilane; (ii) 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, 1-(trimethoxysilyl)-2-(dimethylmethoxysilyl)ethane, 1-(trimethoxysilyl)-2-(methyldimethoxysilyl)ethane, 1,2-bis(dimethylmethoxysilyl)ethane, 1,2-bis(methyldimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(triethoxysilylethyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(trimethoxysilylethyl)-1,1,3,3-tetramethyldisiloxane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(trimethoxysilyl)octane, bis(3-(triethoxysilyl) A bifunctional silane coupling agent selected from ryl)-1-propyl) disulfide, bis(3-(trimethoxysilyl)-1-propyl) disulfide, bis(3-(trimethoxysilyl)-1-propyl) tetrasulfide, bis[2-(triethoxysilyl)ethyl]dimethylsilane, bis[3-(triethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl] sulfide, bis[2-(trimethoxysilyl)ethyl]dimethylsilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(trimethoxysilyl)propyl] sulfide, bis[3-(triethoxysilyl)propyl] ether, bis[3-(trimethoxysilyl)propyl] ether, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; (iii) Trifunctional silane coupling agents selected from tris(triethoxysilylethyl)methylsilane, tris(triethoxysilylethyldimethylsiloxy)methylsilane, tris(triethoxysilylpropyl)amine, tris(triethoxysilylpropyl)methylsilane, tris(trimethoxysilylethyl)methylsilane, tris(trimethoxysilylethyldimethylsiloxy)methylsilane, tris(trimethoxysilylpropyl)amine, and tris(trimethoxysilylpropyl)methylsilane; and (iv) A tetrafunctional silane coupling agent selected from tetrakis(triethoxysilylethyl)silane, tetrakis(triethoxysilylpropyl)silane, and tetrakis(trimethoxysilylpropyl)silane. A coating composition according to any one of the above items [1] to

[10] , selected from the list consisting of the above.

[12] The coating composition according to any one of [1] to

[11] , wherein the inorganic nanoparticles (C) may be surface-modified with a capping agent, and are selected from the list of carbides, diamonds, nitrides, oxides, silicates, sulfates, sulfides, sulfites, and titanates.

[13] The coating composition according to any one of the above [1] to

[12] , wherein the inorganic nanoparticles (C) are selected from the list consisting of boron carbide, silicon carbide, titanium carbide, tungsten carbide, diamond, boron nitride, silicon nitride, titanium nitride, aluminum oxide, molybdenum oxide, silica, titania, and zirconia.

[14] The coating composition according to any one of the above [1] to

[13] , wherein the inorganic nanoparticles (C) have a particle size in the range of 1 to 100 nm, more preferably 5 to 60 nm, even more preferably 10 to 40 nm, and most preferably 10 to 25 nm.

[15] The coating composition according to any one of the above items [1] to

[14] , further comprising one or more solvents.

[16] A method for producing a coated article, (a) the step of applying the coating composition described in any one of the above items [1] to

[15] to the surface of an article, (b) A step of curing the coating composition to obtain a coated article. A method that includes this.

[17] A coated article that can be obtained by the method described in

[16] above.

[18] Use of the coating composition described in any one of the above items [1] to

[15] for forming a hard coating on the surface of a base material.

Claims

1. (i) A silazane polymer (A) which is an organopolysilazane having a mixed polycyclic, linear, and / or branched chain structure. (ii) Silane coupling agent (B), and (iii) Inorganic nanoparticles (C) A coating composition comprising, A coating composition in which the mass ratio [A]:[B] of the silazane polymer (A) to the silane coupling agent (B) is in the range of 66:34 to 50:50, and the mass ratio [A+B]:[C] of the silazane polymer (A) and the silane coupling agent (B) to the inorganic nanoparticles (C) is in the range of 73:27 to 50:

50.

2. The coating composition according to claim 1, wherein the mass ratio [A]:[B] of the silazane polymer (A) to the silane coupling agent (B) is in the range of 60:40 to 50:50, and the mass ratio [A+B]:[C] of the silazane polymer (A) and the silane coupling agent (B) to the inorganic nanoparticles (C) is in the range of 70:30 to 50:

50.

3. The silazane polymer (A) is a repeating unit M represented by formula (1) 1 Includes, - [SiR] 1 R 2 -NR 3 -] Equation (1) In the formula, R 1 , R 2 , and R 3 The coating composition according to claim 1 or 2, wherein R1, R2, and R3 are the same or different from each other and are independently selected from hydrogen, organic groups, or heteroorganic groups, provided that R1, R2, and R3 are not hydrogen at the same time.

4. R 1 and R 2 are the same or different from each other and are independently selected from hydrogen, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to the carbon atom may be replaced by fluorine; R 3 is selected from hydrogen, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to the carbon atom may be replaced by fluorine, provided that R1, R2, and R3 are not simultaneously hydrogen, The coating composition according to claim 3.

5. The silazane polymer (A) is a repeating unit M represented by formula (2) 2 It further includes, - [SiR] 4 R 5 -NR 6 -] Equation (2) In the formula, R 4 , R 5 , and R 6 The coating composition according to claim 3 or 4, wherein R4, R5, and R6 are the same or different from each other and are independently selected from hydrogen, organic groups, or heteroorganic groups, except that R4, R5, and R6 are not hydrogen at the same time.

6. R 4 and R 5 R is the same or different from each other, independently selected from hydrogen, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to carbon atoms may be replaced by fluorine; R 6 The coating composition according to claim 5, wherein R4, R5, and R6 are selected from hydrogen, an alkyl having 1 to 30 carbon atoms, an alkenyl having 2 to 30 carbon atoms, or an aryl having 2 to 30 carbon atoms, and one or more hydrogen atoms bonded to a carbon atom may be replaced by fluorine, provided that R4, R5, and R6 are not simultaneously hydrogen.

7. The coating composition according to any one of claims 1 to 6, wherein the silane coupling agent (B) comprises one or more alkoxysilyl groups.

8. The silane coupling agent (B) is represented by formula (a), 【Chemistry 1】 Formula (a) In the formula, Z is a structural unit containing one or more carbon atoms and / or silicon atoms. R I In each occurrence, independently of each other, one or more -O- and / or -Si(CH) 3 ) 2 - A linear alkoxy group having 1 to 20 carbon atoms, a branched alkoxy group having 3 to 20 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, which may contain a - group. R II In each occurrence, these are, independently of each other, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. k is 0, 1, or 2. n is 1, 2, 3, or 4. The coating composition according to any one of claims 1 to 7.

9. The silane coupling agent (B) is represented by one of formulas (b) to (e), 【Chemistry 2】 Formula (b) Formula (c) 【Transformation 3】 Formula (d) Formula (e) In the formula, X b is (CH 3 ), 2 N-, [HO-(CH 2 ), m 2 N-, AcO-, CH 3 (CH 2 ), m -NH-, CH 3 -NH-, Cl-, H 2 C=C(CH 3 )-CH 2 -NH-, H 2 C=C(CH 3 )-CO-O-, H 2 C=C(CH 3 )-O-CH 2 -CH(OH)-CH 2 -NH-, H 2 C=CH-, H 2 C=CH-CH 2 -NH-, H 2 C=CH-CO-CH<OO00048>-CH(OH)-CH 2 -NH-, H 2 C=CH-CO-O-, H 2 N-, H 2 N-(CH 2 ), m -NH-, H 2 N-(CH 2 ), m -NH-(CH[[ID=OT]] 2 ), n -, H 2 N-(CH 2 ), m -NH-(CH 2 ), n -NH-, H 2 N-(CH 2 ), m -NH-C 4 H 6 -, H 2 N-(CH 2 ), m NH-CH 2 -C 4 H 6 -, H 2 N-(CH 2 ), m -O-C(CH 3 ), 2 -CH=CH-, H 2 N-C 6 H 4 -, H 2 N-C 6 H 4 -O-, H 3 C-, H 3 C-(CH 2 ) m -, H 3 C-(CH 2 ) m -O-, H 3 CO-, HO-, HS-, NCS-, Ph 2 N-, Ph-CO-O-, Ph-NH-, and 【Chemistry 4】 Selected from a list consisting of, m is an integer between 1 and 10. n is an integer between 1 and 10. X c is selected from the list consisting of -(CH 2 ), -NH-, -NH-(CH 2 ), -NH-, -O-, -S-, -S 2 -, -S 3 -, -S 4 -, -Si(CH 3 ), -Si(CH 3 ), -Si(CH 2 )-O-Si(CH 3 ), and 2 2 ​​​​​​​ p is an integer between 1 and 20. X d teeth, 【Transformation 5】 and 【Transformation 6】 Selected from a list consisting of, X e teeth, 【Transformation 7】 Selected from a list consisting of, Y is either absent, or a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms. R I In each occurrence, independently of each other, one or more -O- and / or -Si(CH) 3 ) 2 - A linear alkoxy group having 1 to 20 carbon atoms, a branched alkoxy group having 3 to 20 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, which may contain a - group. R II In each occurrence, these are, independently of each other, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. k is 0, 1, or 2. The coating composition according to any one of claims 1 to 7.

10. The silane coupling agent (B) is (i) (3-Acryloxypropyl)dimethylmethoxysilane, (3-Acryloxypropyl)methyldimethoxysilane, (3-Acryloxypropyl)trimethoxysilane, (Aminoethylaminomethyl)phenethyltrimethoxysilane, (Methacryloxymethyl)dimethylethoxysilane, 3-(2-Aminoethylamino)propylmethyldiethoxysilane, 3-(2-Aminoethylamino)propyltrimethoxysilane, 3-(3-Aminopropoxy)-3,3-dimethyl-1-propenyl-trimethoxysilane, 3-(m-Aminophenoxy)propyltrimethoxysilane, 3-(N-Arylamino)propyltrimethoxysilane, 3-(Trimethoxysilyl)-1-propanethol, 3-Amino Propyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltris(methoxyethoxyethoxy)silane, 3-chloropropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltris(methoxyethoxy)silane, 4-aminobutyltriethoxysilane, 6-ethyl-6-(2-methoxyethoxy)-2,5,7,10-Tetraoxa-6-silaundecane, Acetoxymethyltriethoxysilane, Acetoxymethyltrimethoxysilane, Acetoxypropyltrimethoxysilane, Benzoyloxypropyltrimethoxysilane, Hydroxymethyltriethoxysilane, m-Aminophenyltrimethoxysilane, Methacryloxymethyltriethoxysilane, Methacryloxymethyltrimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-(6-aminohexyl)aminopropyltrimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, N, 1 Monofunctional silane coupling agents selected from -(3-trimethoxysilylpropyl)diethylenetriamine, N-methylaminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminomethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, tetraethoxysilane, triethoxy(3-thiocyanato)propylsilane, triethoxy(octyl)silane, trimethoxymethylsilane, and vinyltriethoxysilane; (ii) 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, 1-(trimethoxysilyl)-2-(dimethylmethoxysilyl)ethane, 1-(trimethoxysilyl)-2-(methyldimethoxysilyl)ethane, 1,2-bis(dimethylmethoxysilyl)ethane, 1,2-bis(methyldimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(triethoxysilylethyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(trimethoxysilylethyl)-1,1,3,3-tetramethyldisiloxane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(trimethoxysilyl)octane, bis(3-(triethoxysilyl) Bifunctional silane coupling agents selected from bis(3-(trimethoxysilyl)-1-propyl) disulfide, bis(3-(trimethoxysilyl)-1-propyl) disulfide, bis(3-(trimethoxysilyl)-1-propyl) tetrasulfide, bis[2-(triethoxysilyl)ethyl]dimethylsilane, bis[3-(triethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl] sulfide, bis[2-(trimethoxysilyl)ethyl]dimethylsilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(trimethoxysilyl)propyl] sulfide, bis[3-(triethoxysilyl)propyl] ether, bis[3-(trimethoxysilyl)propyl] ether, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; (iii) Trifunctional silane coupling agents selected from tris(triethoxysilylethyl)methylsilane, tris(triethoxysilylethyldimethylsiloxy)methylsilane, tris(triethoxysilylpropyl)amine, tris(triethoxysilylpropyl)methylsilane, tris(trimethoxysilylethyl)methylsilane, tris(trimethoxysilylethyldimethylsiloxy)methylsilane, tris(trimethoxysilylpropyl)amine, and tris(trimethoxysilylpropyl)methylsilane; and (iv) A tetrafunctional silane coupling agent selected from tetrakis(triethoxysilylethyl)silane, tetrakis(triethoxysilylpropyl)silane, and tetrakis(trimethoxysilylpropyl)silane. A coating composition according to any one of claims 1 to 9, selected from the list comprising:

11. The coating composition according to any one of claims 1 to 10, wherein the inorganic nanoparticles (C) may be surface-modified with a capping agent and are selected from the list consisting of carbides, diamonds, nitrides, oxides, silicates, sulfates, sulfides, sulfites, and titanates.

12. The coating composition according to any one of claims 1 to 11, wherein the inorganic nanoparticles (C) are selected from the list consisting of boron carbide, silicon carbide, titanium carbide, tungsten carbide, diamond, boron nitride, silicon nitride, titanium nitride, aluminum oxide, molybdenum oxide, silica, titania, and zirconia.

13. The coating composition according to any one of claims 1 to 12, wherein the inorganic nanoparticles (C) have a particle size in the range of 1 to 100 nm, 5 to 60 nm, 10 to 40 nm, or 10 to 25 nm.

14. A coating composition according to any one of claims 1 to 13, further comprising one or more solvents.

15. A method for producing a coated article, (a) the step of applying a coating composition according to any one of claims 1 to 14 to the surface of an article, (b) A step of curing the coating composition to obtain a coated article. A method that includes this.

16. A coated article that can be obtained by the method of claim 15.

17. Use of the coating composition according to any one of claims 1 to 14 for forming a hard coating on the surface of a base material.

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