CN108727979B

CN108727979B - Coating composition and coating material and coating layer and silicon oxide coating layer and article having the coating layer and method for forming coating layer on substrate surface

Info

Publication number: CN108727979B
Application number: CN201810669401.4A
Authority: CN
Inventors: 赵莉; 张宗波; 徐彩虹
Original assignee: Institute of Chemistry CAS; Midea Group Co Ltd; Guangdong Midea Kitchen Appliances Manufacturing Co Ltd
Current assignee: Institute of Chemistry CAS; Midea Group Co Ltd; Guangdong Midea Kitchen Appliances Manufacturing Co Ltd
Priority date: 2018-06-26
Filing date: 2018-06-26
Publication date: 2021-05-07
Anticipated expiration: 2038-06-26
Also published as: CN108727979A

Abstract

A coating composition comprising a perhydropolysilazane, a siloxane in which substituents on silicon atoms are each independently an alkyl group, an aryl group or a hydrogen atom, an inorganic particle, optionally a catalyst, and optionally a silane coupling agent, and a coating layer and an article having the coating layer and a method of forming a coating layer on a surface of a substrate are disclosed. The coating formed on the surface of the substrate by the coating formed by the coating composition has excellent adhesion performance, good temperature resistance and scratch resistance, low-energy surface characteristics and easy cleaning.

Description

Coating composition and coating material and coating layer and silicon oxide coating layer and article having the coating layer and method for forming coating layer on substrate surface

Technical Field

The invention relates to the technical field of coatings. In particular, the present invention relates to a coating composition and a coating formed from the coating composition, to a coating formed from the coating, to a silica coating, and further to an article having the coating and to a method of forming a coating on a surface of a substrate.

Background

Along with the development of economic society, the living standard of people is increasingly improved, the requirements of people on various properties of household appliances are increasingly high and meticulous, and the requirements on basic physical properties and special functionality of materials are increasingly increased. Coatings have received increasing attention and importance as the primary carrier of material functionality.

The household appliances are in environments of high and low temperature, oil stain and the like to different degrees, and have higher requirements on the performances of high and low temperature resistance, wear resistance, corrosion resistance, hardness, surface energy, compactness, transparency and the like of the coating. For example, kitchen electrical products such as microwave ovens, range hoods, cooking utensils and the like have extremely high requirements on high temperature resistance, low surface energy, wear resistance, compactness and high-temperature oxidation resistance of materials due to high temperature, high oil stain and other working environments; refrigerators, air conditioners and the like are in low-temperature environments for a long time, and the requirement on the anti-frosting (icing) performance of the material is high; products with metal pipelines such as water heaters and refrigerators are prone to corrosion and the like after long-term use, have certain influence on the long-term effectiveness and safety of the products, and how to realize corrosion resistance protection of the metal pipelines in high-low temperature and high-humidity environments becomes a challenge.

In the aspect of low surface energy material technology, the materials mainly used in the household appliance industry at present comprise: two traditional non-stick materials of organic silicon and teflon (PTFE) and SiO of hybrid organic silicon taking polysiloxane as precursor emerging in recent years₂Organosilicon hybrid system material. However, the three materials all have the performance problems of low hardness, poor scratch resistance, poor adhesion performance with a substrate and the like, and particularly Teflon has various problems in recent years, and the food safety problem thereof is even more troubling a plurality of household appliance manufacturers.

In the aspect of high wear resistance and high hardness materials, the most widely used material in the household appliance industry is the enamel material at present, but the enamel material has high brittleness, is easy to explode, has a complex process and low yield, and is a technical barrier which is difficult to exceed by the enamel material.

Stainless steel materials are the most widely used materials for high-end products in the household appliance industry due to high-grade appearance, but the stainless steel materials are easy to adhere to oil stains to cause difficulty in cleaning or cause scratches on the surfaces of the stainless steel materials due to the use of cleaning materials, are the biggest pain points of household appliance consumers when using the products, and are easy to oxidize and turn yellow at high temperature in high-temperature use environments (ovens, microwave ovens, kitchen ranges and the like), so that the appearance of the stainless steel products is seriously influenced.

Table 1 below sets forth performance data for coatings formed from the above materials.

TABLE 1

In summary, there are many problems to be solved in the field of materials in the current home appliance industry, wherein providing a coating technology with properties of high temperature resistance, wear resistance, corrosion resistance, high density, high hardness, oxidation resistance and easy cleaning (including frost prevention) is a technology that must be overcome in the whole industry at present and is also an important support for the development of the whole industry.

Disclosure of Invention

The invention aims to overcome the technical problem that a coating with high temperature resistance, wear resistance, high hardness, oxidation resistance and easy cleaning (including frost prevention) performance is difficult to obtain for the coating used in the household appliance industry, and provides a coating with good comprehensive performance.

According to a first aspect of the present invention, there is provided a coating composition comprising perhydropolysilazane, a siloxane in which substituents on silicon atoms are each independently an alkyl group, an aryl group or a hydrogen atom, an inorganic particle, optionally a catalyst, and optionally a silane coupling agent.

According to a second aspect of the present invention there is provided a coating comprising a liquid dispersant and a coating composition according to the first aspect of the present invention, the components of the coating composition being dispersed in the liquid dispersant.

According to a third aspect of the present invention, there is provided a coating formed from the paint of the second aspect of the present invention.

According to a fourth aspect of the present invention, there is provided a silica coating having a hardness of 6H to 9H; the temperature resistance is 350-500 ℃; the water contact angle is 90-120 degrees.

According to a fifth aspect of the present invention there is provided an article having a coating, the article comprising a substrate and a coating adhered to at least part of a surface of the substrate, wherein the coating is a coating according to the third aspect of the present invention or a silica coating according to the fourth aspect of the present invention.

According to a sixth aspect of the present invention, there is provided a method of forming a coating on a surface of a substrate, the method comprising applying a coating according to the second aspect of the present invention to at least part of the surface of the substrate to form a coating layer; curing the substrate with the coating layer in the presence of water and oxygen.

The coating formed by applying the coating formed by the coating composition on the surface of a substrate has excellent adhesion performance, good temperature resistance and scratch resistance, low-energy surface characteristics and easy cleaning (including anti-frosting performance). Specifically, the adhesive force of the coating formed by the coating composition can reach 0 grade, the temperature resistance can reach more than 400 ℃, the hardness can reach more than 9H, and the contact angle with water is more than 105 degrees.

Drawings

FIG. 1 is used to illustrate the conversion mechanism for forming a silicon oxide coating from perhydropolysilazane.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a coating composition comprising perhydropolysilazane, a siloxane, inorganic particles, optionally a catalyst, and optionally a silane coupling agent.

In the coating composition according to the present invention, SiH in the perhydropolysilazane₁And SiH₂May be in the range of 1 to 40, preferably 4 to 20, more preferably 8 to 18. In the present invention, SiH₁And SiH₂The molar ratio of (A) is determined by NMR spectroscopy.

The average molecular weight of the perhydropolysilazane (PHPS) may be 300-10000, preferably 400-2000, and more preferably 500-1000. The average molecular weight is determined by gel permeation chromatography.

The perhydropolysilazanes are commercially available or can be prepared by conventional methods, such as: with H₂SiCl₂As a raw material, H₂SiCl₂Dispersing in solvent to form reaction liquid, introducing NH into the reaction liquid₃And carrying out ammonolysis reaction on the gas, filtering the reaction mixture obtained by the ammonolysis reaction, and concentrating the filtrate to obtain the perhydropolysilazane. Wherein NH₃And H₂SiCl₂The molar ratio of (a) may be from 5 to 50, preferably from 8 to 15. The solvent can be one or more of chloroform, dichloromethane, tetrahydrofuran, petroleum ether, dibutyl ether, xylene, toluene, hexane, octane, heptane, decane, ethyl acetate, amyl acetate, isoamyl acetate, acetone, methyl butanone and methyl isobutyl ketone. The aminolysis reaction may be carried out at a temperature of from-80 ℃ to 0 ℃, preferably from-40 ℃ to-10 ℃. The duration of the ammonolysis reaction can be between 4 and 60 hours, preferably between 20 and 30 hours. The filtration is carried out in an inert atmosphere, for example, an atmosphere formed by a group zero gas and/or nitrogen gas. The concentration is preferably distillation under vacuum and reduced pressure.

According to the coating composition of the present invention, the substituents on the silicon atom in the siloxane are the same or different and each is independently an alkyl group, an aryl group or a hydrogen atom. The substituent on the silicon atom in the siloxane is selected from alkyl, aryl and hydrogen atoms, so that the siloxane can be prevented from generating chemical reaction with other components in the coating composition to influence the functions of the components.

Preferably, the substituents on the silicon atoms in the siloxane are each independently an alkyl group, an aryl group or a hydrogen atom, preferably C₁-C₂₂Alkyl of (C)₆-C₁₂Aryl group of (2) or a hydrogen atom.

In the present invention, C₁-C₂₂Alkyl of (2) includes C₁-C₂₂Straight chain alkyl of (2) and C₃-C₂₂Specific examples thereof may include, but are not limited to: methyl, ethyl, propyl (including isomers of propyl), butyl (including isomers of butyl), pentyl (including isomers of pentyl), hexyl (including isomers of hexyl), heptyl (including isomers of heptyl), octyl (including isomers of octyl), nonyl (including isomers of nonyl), decyl (including isomers of decyl), undecyl (including isomers of undecyl), dodecyl (including isomers of dodecyl), tridecyl (including isomers of tridecyl), tetradecyl (including isomers of tetradecyl), pentadecyl (including isomers of pentadecyl), hexadecyl (including isomers of hexadecyl), heptadecyl (including isomers of heptadecyl), octadecyl (including isomers of octadecyl), nonadecyl (including isomers of nonadecyl), Eicosyl (including isomers of eicosyl), heneicosyl (including isomers of heneicosyl) and docosyl (including isomers of docosyl).

In the present invention, C₆-C₁₂Specific examples of the aryl group of (a) may include, but are not limited to: phenyl, naphthyl, methylphenyl (e.g., 2-methylphenyl, 3-methylphenyl, 4-methylphenyl) and ethylphenyl (e.g., 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl).

In a preferred embodiment, the siloxane is one or more selected from the group consisting of a siloxane represented by formula I, a silane represented by formula II, and a cyclosiloxane represented by formula III.

The siloxanes of formula I are shown below,

in the formula I, n represents

The number of repeats of (b) may be in the range of 1 to 500, preferably in the range of 2 to 100, more preferably in the range of 2 to 50, further preferably in the range of 2 to 20, further preferably in the range of 2 to 10, and for example may be 2, 3, 4, 5, 6, 7, 8, 9 or 10.

In the formula I, n R₁N R₃、R₂And R₄Identical or different, each independently is C₁-C₂₂Alkyl (preferably C)₁-C₁₀Alkyl group of (1), C₆-C₁₂Aryl group of (2), hydrogen atom or

R₇、 R₈And R₉Identical or different, each independently is C₁-C₂₂Alkyl (preferably C)₁-C₁₀Alkyl group of (1), C₆-C₁₂Aryl group of (2) or a hydrogen atom.

In the formula I, R₅And R₆Are the same or different and are each independently selected from C₁-C₂₂Alkyl (preferably C)₁-C₁₀Alkyl group of (1), C₆-C₁₂Aryl group of (2) or a hydrogen atom.

The silane is represented by the following formula II,

in the formula II, R₁₀、R₁₁、R₁₂And R₁₃Identical or different, each independently is C₁-C₂₂Alkyl of (C)₆-C₁₂Aryl group of (2), hydrogen atom or

And R is₁₀、R₁₁、R₁₂And R₁₃At least one of which is

R₁₄、R₁₅And R₁₆Identical or different, each independently is C₁-C₂₂Alkyl of (C)₆-C₁₂Aryl group of (2) or a hydrogen atom. In the formula II, R₁₀、R₁₁、R₁₂And R₁₃One, two, three or four of

The cyclosiloxane is represented by the following formula III,

in formula III, m may be in the range of 2 to 500, preferably in the range of 2 to 100, more preferably in the range of 2 to 50, and still more preferably in the range of 2 to 20, and may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

In the formula III, m R₁₇And m R₁₈Identical or different, each independently is C₁-C₂₂Alkyl (preferably C)₁-C₁₀More preferably C₁-C₅Alkyl group of (1), C₆-C₁₂Aryl group of (2) or a hydrogen atom.

Specific examples of the siloxane according to the coating composition of the present invention may include, but are not limited to: 1,1,5, 5-tetramethyl-3, 3-diphenyltrisiloxane, 1,1,1,3,5,5, -heptamethyltrisiloxane, 3- (dimethylsiloxy) -1,1,5, 5-tetramethyl-3-phenyltrisiloxane, 1,1,1,3,5,5,5, -heptamethyl-3-octyltrisiloxane, 1,1,3, 3-tetramethyldisiloxane, 1,3, 5-trimethyl-1, 3, 5-triphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,1,3,3,5, 5-hexamethyltrisiloxane, methyl-tris (dimethylsiloxy) silane, dodecamethylcyclohexasiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenylcyclotetrasiloxane, 1,3,3,5,5,7, 7-octamethyltetrasiloxane, 1,3, 3-tetramethoxy-1, 3-dimethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, 1,3,3,5,5,7, 7-octaethylcyclotetrasiloxane, tetrakis (dimethylsiloxy) silane, 1,3,3,5,5,7,7,9, 9-decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, pentamethyldisiloxane, hexaethyldisiloxane, 1,5, 5-tetraphenyl-1, 3,3, 5-tetramethyltrisiloxane, 1,3,5, 5-pentamethyl-3-phenyltrisiloxane, 1,1,3,5,5, 5-heptamethyl-3-phenyltrisiloxane, dodecylheptamethyltrisiloxane, 1, 3-bis (4-methylphenyl) -1,1,3, 3-tetramethyldisiloxane, 3, 3-diphenyl-hexamethyltrisiloxane, 2,4, 6-trimethyl-cyclotrisiloxane, 2,4,6, 8-tetramethyl-2- (trimethoxysilyl) ethylcyclotetrasiloxane, dodecamethylpentasiloxane, decamethyltetrasiloxane, hexaphenyldisiloxane, 1,3,5, 7-tetramethyl-1, 1,3,5,7, 7-hexaphenyltetrasiloxane, methyltri (trimethylsiloxy) silane, 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane, Phenyltris (trimethylsiloxy) silane, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, ethyltris (dimethylsiloxy) silane, ethyltris (trimethylsiloxy) silane, 1,1,1,5,5, 5-hexamethyltrisiloxane, 1,3,5, 7-tetraethylcyclotetrasiloxane, 3, 5-diphenyloctamethyltetrasiloxane, tetradecylhexasiloxane, 1, 3-dimethyl-1, 1,3, 3-tetraphenyldisiloxane, 1, 3-octyltetramethyldisiloxane, 2,4, 4-tetramethyl-6, 6,8, 8-tetraphenylcyclotetrasiloxane, 2,4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, 1,1,3, 3-tetramethoxy-1, 3-diphenyldisiloxane, 3-ethylheptamethyltrisiloxane, 1,1,1,5,5, 5-hexaethyl-3-methyltrisiloxane, 1,1, 1-triethyl-3, 3, 3-trimethyltrisiloxane, 1,1,1,3,5,7,7, 7-octamethyl-3, 5-bis (trimethylsiloxy) tetrasiloxane, hexa (2-ethylbutoxy) disiloxane, 1,1,3, 3-tetraethyl-1, 3-dimethyldisiloxane, 1,1,1,5,5, 5-hexamethyl-3-octyl-3- [ (trimethylsilyl) oxy ] trisiloxane, 1,1,1,5,5, 5-hexamethyl-3- (2-phenylethyl) -3- [ (trimethylsilyl) oxy ] trisiloxane, Polyphenylmethylsiloxane, cetylmethylheptasiloxane, thirty-methylcyclopentadecasiloxane, twenty-octamethylcyclotetradecylsiloxane, thirty-dimethylcyclohexadecylsiloxane, thirty-octamethylcyclononasiloxane, 2,4,4,6, 6-hexamethyl-8, 8-diphenylcyclotetrasiloxane, twenty-dimethylcycloundecaniloxane, twenty-methylcyclodecasiloxane, twenty-tetramethylcyclododecasiloxane, 1,3,3,5,5, 7-hexamethyl-1, 1,7, 7-tetraphenyltetrasiloxane, hexadecylcyclooctasiloxane, octadecylcyclononasiloxane, eicosylnonasiloxane, docosyloxysiloxane, hexachloromethyldodecasiloxane, twenty-octamethyltridenesiloxane, thirty-hexamethylheptadecasiloxane, 2, 5-diphenylhexamethylcyclotetrasiloxane, Undecamethylpentasiloxane, dotriacontathylhexadecasiloxane, hexamethyltrisiloxane, 1,3, 5-trimethyl-1, 1,3,5, 5-pentaphenyltrisiloxane, 1,1,3, 3-tetramethyl-1, 3-diphenyldisiloxane, 1,1,1,3,3,5, 5-heptamethyltrisiloxane, 1,1,3,3,5,5,7, 7-octamethyltetrasiloxane, decamethylcyclopentasiloxane, diethyldiethoxysilane, 1,1,1,5,5, 5-hexamethyl-3, 3-bis [ (trimethylsilyl) oxy ] -trisiloxane, 1,1,3,5, 5-pentaphenyl-1, 3, 5-trimethylsiloxane, 3, 5-bis (dimethylsilyloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyl tetrasiloxane, 3,5, 7-triphenyl nonamethyl pentasiloxane, 2,4, 4-tetramethyl-6, 6,8, 8-tetraphenyl cyclotetrasiloxane, 1,3, 3-tetramethyl disiloxane, polydiethylsiloxane and polydimethylsiloxane. The siloxane is preferably one or more of 1,1,1,3,5,5,5, -heptamethyl-3-octyltrisiloxane, hexadecylheptamethylheptasiloxane, 1,1,1,3,5,5,5, -heptamethyltrisiloxane, octamethylcyclotetradecylsiloxane, 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane, octadecyl heptamethyltrisiloxane, 3, 5-diphenyl octamethyltetrasiloxane, 2,4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, or dodecamethylcyclohexasiloxane.

According to the coating composition of the present invention, two or more kinds of siloxanes are preferably used in combination, which can further improve the properties of the formed coating layer. In a preferred embodiment, the siloxane comprises a first siloxane which is 1,1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane and/or 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane and a second siloxane which is 3, 5-bis (dimethylsiloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane and/or 1,1,1,5,5, 5-hexamethyl-3- (2-phenylethyl) -3- [ (trimethylsilyl) oxy ] trisiloxane. In this preferred embodiment, the weight ratio of the first siloxane to the second siloxane is preferably 1: 0.1 to 1.5, more preferably 1: 0.2-1.2.

In another preferred embodiment, the siloxane comprises a first siloxane which is hexadecyl heptamethyl siloxane and a second siloxane which is dodecyl heptamethyl trisiloxane. In this preferred embodiment, the weight ratio of the first siloxane to the second siloxane is preferably 1: 0.2 to 0.8, more preferably 1: 0.4-0.6.

In yet another preferred embodiment, the siloxane comprises a first siloxane which is one or more of octamethylcyclotetradecasiloxane, tetraethylcyclotetrasiloxane and dodecamethylcyclohexasiloxane, and a second siloxane which is one or more of tridodecylcyclohexadecylcyclohexasiloxane, octadecylheptamethyltrisiloxane and docosyltetrasiloxane. In this preferred embodiment, the weight ratio of the first siloxane to the second siloxane is preferably 1: 0.1 to 3, more preferably 1: 0.2-2.5.

The content of the siloxane in the coating composition according to the present invention may be 0.1 to 400 parts by weight, preferably 1 to 300 parts by weight, relative to 100 parts by weight of perhydropolysilazane.

According to the coating composition of the present invention, the inorganic particles may be conventionally selected as a filler. Preferably, the inorganic particles are one or more of silica particles, zinc oxide particles, alumina particles and boron trioxide particles. More preferably, the inorganic particles are silica particles. Further preferably, the inorganic particles are fumed silica particles. The average particle diameter of the inorganic particles is preferably 2 to 50nm, more preferably 5 to 30nm, and further preferably 8 to 20 nm.

According to the coating composition of the present invention, the content of the inorganic particles may be 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 5 to 40 parts by weight, relative to 100 parts by weight of perhydropolysilazane.

The coating composition according to the present invention preferably further comprises a catalyst to promote ceramming of the perhydropolysilazane and siloxane in the coating composition to form a coating. The catalyst may be an amine-based catalyst and/or a metal-based catalyst. The amine catalyst can be one or more than two of aliphatic amine, alicyclic amine, alcohol amine and aromatic amine. The metal-based catalyst may be an organotin catalyst and/or a palladium catalyst. Specific examples of the catalyst may include, but are not limited to: one or more of diethylamine, triethylamine, triethylenetetramine, triethylenediamine, piperazine, piperidine, morpholine, N-dimethylethanolamine, diisopropanolamine, N-diethylethanolamine, aniline, o-phenylenediamine, benzidine, N-dimethylaniline, dibutyltin dilaurate, stannous octoate, dimethyltin, triphenyltin, palladium-carbon, palladium chloride, palladium propionate, palladium acetate and tetrakis (triphenylphosphine) palladium.

According to the coating composition of the present invention, the catalyst may be contained in an amount of 0 to 8 parts by weight, preferably 1 to 6 parts by weight, and more preferably 2 to 6 parts by weight, relative to 100 parts by weight of perhydropolysilazane.

The coating composition according to the present invention preferably further contains a silane coupling agent to further improve the dispersibility of the inorganic particles in the matrix in the coating layer formed from the coating composition and to further improve the bonding strength of the inorganic particles in the matrix. The silane coupling agent may be of conventional choice. Preferably, the silane coupling agent is triethoxy-3-thiocyanopropylsilane, tetraethoxysilane, bis [3- (trimethoxysilyl) propyl ] ethylenediamine, triethoxyoctylsilane, (trimethoxysilyl) ethylene, N-phenylaminomethyltriethoxysilane, one or more of bis [3- (triethoxysilyl) propyl ] disulfide, trimethoxymethylsilane, 3-glycidoxypropyltrimethoxysilane, 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, 6-ethyl-6- (2-methoxyethoxy) -2,5,7, 10-tetraoxa-6-silaundecane, and 3-chloropropyltrimethoxysilane.

According to the coating composition of the present invention, the silane coupling agent may be contained in an amount of 0 to 50 parts by weight, preferably 1 to 45 parts by weight, and more preferably 2 to 40 parts by weight, relative to 100 parts by weight of perhydropolysilazane.

The liquid dispersant may be a liquid substance capable of dissolving and dispersing perhydropolysilazane, a fluorine-containing compound and siloxane, and may be, for example, C₃-C₁₀Alkane, C₄-C₁₀Ether of (C)₃-C₁₀Ketone (b), C₇-C₁₂Aromatic hydrocarbons and C₄-C₂₀One or more than two of the esters (b). Specific examples of the liquid dispersant may include, but are not limited to: hexane (including various isomers of hexane, such as n-hexane), heptane (including various isomers of heptane, such as n-heptane), octane (including various isomers of octane, such as n-octane), nonane (including various isomers of nonane, such as n-nonane), decane (including various isomers of decane, such as n-decane), chloroform, dichloromethane, dichloroethylene, diethyl ether, petroleum ether, dibutyl ether, acetone, 1-butanone, cyclohexanone, isophorone, toluene, xylenes (such as p-xylene and o-xylene), chlorobenzene, ethyl acetate, butyl acetate, ethylene glycol diacetate, diglycerin dipropionate, trimethylolpropane dicaprylate, ethylene glycol dicarbamate, 2-ethylpentanoate, 2-methylbutyl hexanoate, 3-dimethyl-1-butylacetate, 3-dimethyll-1-butylacetate, ethylene glycol diacetate, ethylene glycol dipropionate, ethylene glycol dicaprylate, ethylene glycol dicarbamate, 2-ethylp, Cinnamyl valerate, ethylene glycol dibutyrate, 3-methoxybutyl-3-methoxypropanoateOne or more than two of 2-ethoxy ethyl hexanoate and 1-methyl amyl valerate.

The amount of the liquid dispersant is such that a uniform dispersion of the components of the coating composition is formed. Preferably, the content of the liquid dispersant may be 50 to 10000 parts by weight, preferably 60 to 5000 parts by weight, and more preferably 70 to 2000 parts by weight, relative to 100 parts by weight of perhydropolysilazane.

The coating according to the invention may also contain other auxiliaries, such as: one or more than two of leveling agent, defoaming agent and viscosity regulator. The defoaming agent may be various substances commonly used which can suppress the formation of foam, destroy the formed foam and/or remove the formed foam from the system, and for example, may be an organopolysiloxane-based defoaming agent, a polyether-based defoaming agent and a higher alcohol-based defoaming agent. The leveling agent is used for promoting the coating to form a more flat, smooth and uniform coating in the drying and curing process, and can be a polyacrylate leveling agent. The viscosity regulator is used for regulating the viscosity of the coating and can be one or more than two of polyamide wax, organic bentonite, hydrogenated castor oil, metal soap, hydroxyalkyl cellulose and derivatives thereof, polyvinyl alcohol and polyacrylate.

The coating according to the invention can be obtained by dispersing the components of the coating composition and optionally auxiliaries in a liquid dispersant. Preferably, perhydropolysilazane is dissolved in at least a part of the liquid dispersant to form a perhydropolysilazane diluent, and siloxane and inorganic particles are dispersed in the diluent to form a precursor dispersion; when the coating composition contains a catalyst and/or a silane coupling agent, the catalyst and the silane coupling agent are dissolved in the remaining portion of the liquid dispersant to form a catalyst and/or coupling agent solution. The precursor dispersion is mixed with a catalyst and/or coupling agent solution to obtain the coating according to the invention.

The thickness of the coating can be selected according to the particular application. Generally, the thickness of the coating may be from 0.1 to 20 microns, preferably from 0.5 to 15 microns, more preferably from 2 to 12 microns.

The coating formed from the coating material according to the second aspect of the present invention not only has good adhesion properties, but also exhibits improved hardness and temperature resistance properties, while also exhibiting low surface energy characteristics.

In particular, the coating according to the third aspect of the present invention may have a hardness of 6H to 9H, preferably 8H to 9H; the temperature resistance can be 350-500 ℃, and is preferably 400-450 ℃; the water contact angle may be from 90 to 120, preferably from 95 to 110.

According to a fourth aspect of the present invention, there is provided a silica coating having a hardness of from 6H to 9H, preferably from 8H to 9H; the temperature resistance can be 350-500 ℃, and is preferably 400-450 ℃; the water contact angle may be from 90 to 120, preferably from 95 to 110.

According to the silicon oxide coating of the fourth aspect of the invention, the high temperature oxidation resistance Δ E may be 0.8 or less, typically 0.2 to 0.6; the wear resistance can be more than 3500 times, generally 4000-5000 times.

The silica coating according to the fourth aspect of the present invention, wherein the molar ratio of nitrogen element to silicon element in the silica coating may be 0.01 to 10: 100, preferably 0.1 to 5: 100, more preferably 0.1 to 1: 100, more preferably 0.1 to 0.3: 100. in the silicon oxide coating, the molar ratio of nitrogen element to silicon element is determined by X-ray photoelectron spectroscopy.

The thickness of the silica coating may be selected according to the particular application. Generally, the silica coating may have a thickness of 0.1 to 20 microns, preferably 0.5 to 15 microns, more preferably 2 to 12 microns.

The silica coating according to the fourth aspect of the present invention may be formed using the coating composition according to the first aspect of the present invention or the coating according to the second aspect of the present invention.

According to a fifth aspect of the present invention there is provided a coated article comprising a substrate and a coating adhered to at least part of a surface of the substrate, wherein the coating is a coating according to the third aspect of the present invention or a silica coating according to the fourth aspect of the present invention.

The thickness of the coating can be selected according to the specific use requirements. Generally, the thickness of the coating may be from 0.1 to 20 microns, preferably from 0.5 to 15 microns, more preferably from 2 to 12 microns.

According to the product of the present invention, the material of the substrate is not particularly limited, and may be a metal substrate, a glass substrate, a ceramic substrate, an enamel substrate, a polymer substrate, or a composite substrate of two or more of the above substrates. Specific examples of the metal substrate may include, but are not limited to: stainless steel substrates, aluminum-plated substrates, zinc-plated substrates, and cast iron substrates. Specific examples of the polymer substrate may include, but are not limited to: one or more of a Polycarbonate (PC) substrate, an acrylonitrile-butadiene-styrene terpolymer (ABS) substrate, a polypropylene (PP) substrate, a Polyoxymethylene (POM) substrate, a polybutylene terephthalate (PBT) substrate, and a polyethylene terephthalate (PET) substrate.

The articles according to the invention have a high adhesion of the coating to the substrate, typically of the order 0.

The articles according to the invention may be in various forms, in various sheets and profiles, and also in various shaped appliances, such as various household appliances, specific examples of which may include but are not limited to: microwave ovens, range hoods, stoves, dust collectors, dishwashers, air conditioners, refrigerators, water heaters and washing machines.

The coating may be applied to at least part of the surface of the substrate (the surface on which the coating is to be formed) using conventional methods, for example: one or the combination of more than two of spray coating, spin coating, curtain coating, dip coating and roller coating. Prior to application of the coating, the substrate may be cleaned using conventional methods, such as: degreasing and/or water washing are performed.

The thickness of the coating sprayed on the surface of the substrate can be selected according to the thickness requirement of the finally formed coating. Typically, the coating is sprayed onto the substrate surface to a thickness such that the resulting coating has a thickness of 0.1 to 20 microns, preferably 0.5 to 15 microns, more preferably 2 to 12 microns.

According to the method of the sixth aspect of the invention, the substrate with the coating layer is cured in the presence of water and oxygen. As shown in fig. 1, in the presence of water and oxygen, perhydropolysilazane is converted into silicon oxide by the action of water and oxygen, and a silicon oxide coating is formed on the surface of the substrate.

The curing conditions are such that the perhydropolysilazane is converted to silicon oxide. Preferably, the curing conditions are such that the molar ratio of nitrogen element to silicon element in the finally formed coating is 0.1-10: 100, preferably 0.1 to 5: 100, more preferably 0.1 to 1: 100, more preferably 0.1 to 0.3: 100.

generally, the curing may be carried out in an oxygen-containing atmosphere having a relative humidity of 45 to 90%. The oxygen-containing atmosphere may be a pure oxygen atmosphere, or may be an atmosphere of oxygen and other gases, for example, an atmosphere of oxygen and an inert gas, for example, a group zero gas (e.g., helium and/or argon) and/or nitrogen. More preferably, the curing is carried out in an air atmosphere having a relative humidity of 50-75%.

The curing may be carried out with or without heating, or may be carried out under irradiation of ultraviolet light. Generally, the curing may be carried out at a temperature of from 25 to 350 ℃, preferably at a temperature of from 50 to 320 ℃, more preferably at a temperature of from 100 ℃ to 300 ℃, even more preferably at a temperature of from 200 ℃ to 280 ℃. The duration of the curing can be selected according to the manner of curing and the temperature of curing, so that complete or substantially complete conversion of the perhydropolysilazane to silicon oxide is achieved. Preferably, the duration of the curing is 0.5 to 10 hours. More preferably, the duration of the curing is 1 to 8 hours. Further preferably, the duration of the curing is 2-4 hours.

According to the method of the sixth aspect of the present invention, the substrate having the coating layer is preferably dried to remove volatile components from the coating layer before curing. The drying may be carried out at a temperature of 20-100 ℃ at room temperature.

According to the method of the sixth aspect of the present invention, the material of the substrate is not particularly limited, and may be a metal substrate, a glass substrate, a ceramic substrate, an enamel substrate, a polymer substrate, or a composite substrate of two or more of the above substrates. Specific examples of the metal substrate may include, but are not limited to: stainless steel substrates, aluminum-plated substrates, zinc-plated substrates, and cast iron substrates. Specific examples of the polymer substrate may include, but are not limited to: one or more of a Polycarbonate (PC) substrate, an acrylonitrile-butadiene-styrene terpolymer (ABS) substrate, a polypropylene (PP) substrate, a Polyoxymethylene (POM) substrate, a polybutylene terephthalate (PBT) substrate, and a polyethylene terephthalate (PET) substrate.

The substrate can be various plates or profiles, and can also be arranged in various forming appliances, preferably household appliances, preferably microwave ovens, range hoods, stoves, dust collectors, dishwashers, air conditioners, refrigerators, water heaters or washing machines.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

In the following examples and comparative examples, perhydropolysilazanes were used and purchased from the institute of chemistry, national academy of sciences. In the following examples and comparative examples, the average molecular weight of perhydropolysilazane was measured by gel permeation chromatography, and the SiH content of perhydropolysilazane was measured by NMR₁And SiH₂In a molar ratio of (a).

In the following examples and comparative examples, the molar ratio of nitrogen element and silicon element in the coating layer was measured by X-ray photoelectron spectroscopy.

In the following examples and comparative examples, the hardness of the coating was measured by the method specified in GB/T6739-2006; the adhesion of the coating is measured by a cross-cut method according to the method specified in GB/T9286-1998; the water contact angle of the coating was measured using a full-automatic water contact angle instrument, model DSA100, from germany, at 25 ℃ and 1 standard atmosphere.

In the following examples and comparative examples, the temperature resistance of the coating was measured by a water contact angle method, i.e., after the prepared coating was heated in an oven to various temperatures and maintained at the same temperature for 2 hours, the water contact angle was measured, if the water contact angle is less than 90 °, it was judged that the temperature resistance was lost, and the temperature was taken as the highest temperature resistant, and the higher the temperature, the better the temperature resistance of the coating.

In the following examples and comparative examples, the high temperature oxidation resistance of the coating was measured using a color difference change test method, and the color difference between the sample after high temperature oxidation and the sample without oxidation was measured, and the smaller the color difference value, the better the high temperature oxidation resistance of the coating, and specifically, the color values of the coating before and after oxidation were measured and the difference between the two was calculated when the prepared coating was heated to 400 ℃ in an oven and maintained at that temperature for 2 ℃.

In the following examples and comparative examples, the abrasion resistance of the coating was measured by using a 3M sandpaper reciprocating friction method, and if the coating was exposed and peeled off, the number of times of friction occurred was used as the data of abrasion resistance, and the abrasion resistance was obtained by rounding according to the rule of proximity, and the higher the abrasion resistance value, the better the abrasion resistance of the coating.

Examples 1-17 are intended to illustrate the invention.

Example 1

(1) 40 parts by weight of perhydropolysilazane (average molecular weight 600, SiH)₁And SiH₂11) to 42 parts by weight of butyl acetate, and stirred at room temperature (25 c) to form a homogeneous and stable diluted PHPS.

(2) 1 part by weight of (3-trimethoxysilylpropyl) diethylethylenediamine and 2 parts by weight of dibutyltin dilaurate were added to 11 parts by weight of butyl acetate, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 1 part by weight of 1,1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane (available from carbofuran technologies, Ltd., the same below), 1 part by weight of 3, 5-bis (dimethylsilyloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane (available from carbofuran technologies, Ltd., the same below) and 2 parts by weight of fumed silica (average particle size of 12nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred at room temperature (25 ℃ C.) to be uniform, to obtain a coating according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of a 304 stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 60 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 200 ℃ for 2 hours in an air atmosphere having a relative humidity of 60%, to obtain a substrate having a coating layer (thickness of 5 μm). The properties of the coatings were tested and the results are listed in table 2.

Comparative example 1

A coated substrate was prepared by the same method as in example 1 except that 1,1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane and 3, 5-bis (dimethylsiloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane were not used in step (3) (i.e., the coating was prepared without siloxane). The properties of the coatings were tested and the results are listed in table 2.

Comparative example 2

A coated substrate was prepared in the same manner as in example 1, except that in step (3), 1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane and 3, 5-bis (dimethylsiloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane were not used, but 2 parts by weight of diphenyldichlorosilane was used. The properties of the coatings were tested and the results are listed in table 2.

Example 2

A coated substrate was prepared in the same manner as in example 1, except that 3, 5-bis (dimethylsilyloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane was not used in the step (3), and 1,1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane was used in an amount of 2 parts by weight. The properties of the coatings were tested and the results are listed in table 2.

Example 3

A coated substrate was prepared in the same manner as in example 1, except that in step (3), 1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane and 3, 5-bis (dimethylsiloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane were not used in an amount of 2 parts by weight. The properties of the coatings were tested and the results are listed in table 2.

TABLE 2

Example 4

(1) 35 parts by weight of perhydropolysilazane (average molecular weight 600, SiH)₁And SiH₂At a molar ratio of 12) was added to 47.2 parts by weight of dibutyl ether and stirred at room temperature (25 ℃ C.) to form a homogeneous and stable PHPS dilution.

(2) 1 part by weight of triethoxyoctylsilane and 1.8 parts by weight of palladium acetate were added to 10 parts by weight of dibutyl ether, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 2 parts by weight of hexadecylmethylheptasiloxane, 1 part by weight of dodecylheptamethyltrisiloxane, and 2 parts by weight of fumed silica (average particle size of 16nm) were added to the PHPS dilution, followed by addition of the coupling agent catalyst solution prepared in step (2), and stirring was carried out at room temperature (25 ℃ C.) to obtain a coating material according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the glass substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 60 ℃ in vacuum, and removing the solvent in the coating layer. Then, the cured product was cured at 250 ℃ for 2 hours in an air atmosphere having a relative humidity of 50%, to obtain a substrate having a coating layer (thickness of 8 μm). The properties of the coatings were tested and the results are listed in table 3.

Example 5

A coated substrate was prepared in the same manner as in example 4, except that in step (3), dodecylheptamethyltrisiloxane was not used and that 3 parts by weight of hexadecylheptamethylheptosiloxane was used. The properties of the coatings were tested and the results are listed in table 3.

Comparative example 3

A coated substrate was prepared in the same manner as in example 4, except that in the step (3), dodecylheptamethyltrisiloxane and hexadecylheptamethylheptosiloxane were not used, but 3 parts by weight of dicarboxydimethylsiloxane (degree of polymerization: 7) was used. The properties of the coatings were tested and the results are listed in table 3.

TABLE 3

Example 6

(1) 30 parts by weight of perhydropolysilazane (average molecular weight 800, SiH)₁And SiH₂At a molar ratio of 12) was added to 50.5 parts by weight of ethylene glycol dibutyrate, and stirred at room temperature (25 ℃ C.) to form a homogeneous and stable PHPS dilution.

(2) 1 part by weight of 3-glycidoxypropyltrimethoxysilane and 1.5 parts by weight of dimethyltin were added to 11 parts by weight of diethyl ether, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 2 parts by weight of octamethylcyclotetradecasiloxane, 2 parts by weight of thirty dimethylcyclohexadecylsiloxane, and 2 parts by weight of fumed silica (average particle size 15nm) were added to the PHPS diluent, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 60 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 240 ℃ for 2.5 hours in an air atmosphere with a relative humidity of 55%, to obtain a substrate having a coating layer (thickness of 6 μm). The properties of the coatings were tested and the results are listed in table 4.

Example 7

(1) 25 parts by weight of perhydropolysilazane (average molecular weight 800, SiH)₁And SiH₂14) to 56 parts by weight of ethyl acetate, and stirred at room temperature (25 ℃) to form a homogeneous and stable diluted PHPS.

(2) 0.5 part by weight of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate and 1.2 parts by weight of diphenyltin were added to 10.3 parts by weight of p-xylene, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 1 part by weight of 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane, 4 parts by weight of 1,1,1,5,5, 5-hexamethyl-3- (2-phenylethyl) -3- [ (trimethylsilyl) oxy ] trisiloxane and 2 parts by weight of fumed silica (average particle size 15nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating material according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 60 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 260 ℃ for 2 hours in an air atmosphere having a relative humidity of 50%, to obtain a substrate having a coating layer (thickness of 12 μm). The properties of the coatings were tested and the results are listed in table 4.

Example 8

A coated substrate was prepared by the same method as in example 7, except that 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane was not used in the step (3), and 1,1,1,5,5, 5-hexamethyl-3- (2-phenylethyl) -3- [ (trimethylsilyl) oxy ] trisiloxane was used in an amount of 5 parts by weight. The properties of the coatings were tested and the results are listed in table 4.

Example 9

A coated substrate was prepared by the same method as in example 7, except that 1,1,1,5,5, 5-hexamethyl-3- (2-phenylethyl) -3- [ (trimethylsilyl) oxy ] trisiloxane and 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane were not used in an amount of 5 parts by weight in the step (3). The properties of the coatings were tested and the results are listed in table 4.

TABLE 4

Example 10

(1) 20 parts by weight of perhydropolysilazane (average molecular weight 500, SiH)₁And SiH₂At a molar ratio of 10) to 51 parts by weight of 1-methylpentylvalerate and stirred at room temperature (25 deg.C) to form a homogeneous and stable dilution of PHPS.

(2) 0.8 part by weight of N-phenylaminomethyltriethoxysilane and 1.0 part by weight of palladium chloride were added to 15.2 parts by weight of petroleum ether, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 7 parts by weight of octadecylheptamethyltrisiloxane, 3 parts by weight of tetraethylcyclotetrasiloxane and 2 parts by weight of fumed silica (average particle size of 8nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 45 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 220 ℃ for 3 hours in an air atmosphere having a relative humidity of 70%, to obtain a substrate having a coating layer (thickness of 8 μm). The properties of the coatings were tested and the results are listed in table 5.

Example 11

(1) 15 parts by weight of perhydropolysilazane (average molecular weight 800, SiH)₁And SiH₂At a molar ratio of 12) was added to 43 parts by weight of ethylene glycol dibenzoate, and stirred at room temperature (25 ℃ C.) to form a homogeneous and stable PHPS dilution.

(2) 1.2 parts by weight of trimethoxymethylsilane and 0.5 part by weight of stannous octoate were added to 23.3 parts by weight of ethylene glycol diformate, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 6 parts by weight of 3, 5-diphenyl octamethyltetrasiloxane, 9 parts by weight of hexachloromethyldodecasiloxane and 2 parts by weight of fumed silica (average particle size 10nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 50 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 230 ℃ for 3 hours in an air atmosphere having a relative humidity of 50%, to obtain a substrate having a coating layer (thickness of 5 μm). The properties of the coatings were tested and the results are listed in table 5.

Example 12

(1) 10 parts by weight of perhydropolysilazane (average molecular weight 600, SiH)₁And SiH₂At a molar ratio of 10) to 46.2 parts by weight of trimethylolpropane dicaprylate, and stirred at room temperature (25 ℃ C.) to form a homogeneous and stable PHPS dilution.

(2) 1.5 parts by weight of triethoxy-3-thiocyanopropylsilane and 0.4 part by weight of dibutyltin dilaurate were added to 19.9 parts by weight of trimethylolpropane dioctoate, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 5 parts by weight of 2,4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, 15 parts by weight of hexamethyltrisiloxane and 2 parts by weight of fumed silica (average particle size of 10nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 55 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 200 ℃ for 3 hours in an air atmosphere having a relative humidity of 75% to obtain a substrate having a coating layer (thickness of 4 μm). The properties of the coatings were tested and the results are listed in table 5.

Example 13

(1) 5 parts by weight of perhydropolysilazane (average molecular weight 600, SiH)₁And SiH₂12) to 41 parts by weight of 2-methylbutyl hexanoate, and stirring at room temperature (25 ℃) to form a homogeneous and stable diluted PHPS.

(2) 2 parts by weight of triethoxyoctylsilane and 0.1 part by weight of triphenyltin were added to 24.9 parts by weight of dibutyl ether, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 11 parts by weight of dodecamethylcyclohexasiloxane, 4 parts by weight of behenyldidecasiloxane, and 2 parts by weight of fumed silica (average particle size of 10nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating material according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 50 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 230 ℃ for 5 hours in an air atmosphere having a relative humidity of 65%, to obtain a substrate having a coating layer (thickness of 5 μm). The properties of the coatings were tested and the results are listed in table 5.

Example 14

(1) 40 parts by weight of perhydropolysilazane (average molecular weight 800, SiH)₁And SiH₂At a molar ratio of 10) was added to 25 parts by weight of butyl acetate and stirred at room temperature (25 ℃ C.) to form a homogeneous and stable diluted PHPS.

(2) 1 part by weight of (3-trimethoxysilylpropyl) diethylethylenediamine and 2 parts by weight of dibutyltin dilaurate were added to 5 parts by weight of butyl acetate, and the mixture was stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 12 parts by weight of 1,1,1,3,5,5,5, -heptamethyl-3-octyltrisiloxane, 13 parts by weight of 3, 5-bis (dimethylsilyloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane and 2 parts by weight of fumed silica (average particle size of 12nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating material according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 50 ℃ in vacuum, and removing the solvent in the coating layer. Then, the cured product was cured at 220 ℃ for 5 hours in an air atmosphere having a relative humidity of 60%, to obtain a substrate having a coating layer (thickness of 6 μm). The properties of the coatings were tested and the results are listed in table 5.

Example 15

(1) 5 parts by weight of perhydropolysilazane (average molecular weight 1000, SiH)₁And SiH₂8) to 54 parts by weight of butyl acetate, and stirred at room temperature (25 c) to form a homogeneous and stable diluted PHPS.

(2) 1 part by weight of [ (3-trimethoxysilylpropyl) diethylethylenediamine and 0.2 part by weight of dibutyltin dilaurate were added to 31 parts by weight of butyl acetate, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent catalyst solution.

(3) 3 parts by weight of 1,1,1,3,5,5,5, -heptamethyl-3-octyltrisiloxane, 2 parts by weight of 3, 5-bis (dimethylsilyloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane and 2 parts by weight of fumed silica (average particle size of 10nm) were added to the PHPS dilution, and then the coupling agent catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating material according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 50 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 230 ℃ for 3 hours in an air atmosphere having a relative humidity of 70%, to obtain a substrate having a coating layer (thickness of 4 μm). The properties of the coatings were tested and the results are listed in table 5.

Example 16

(1) 40 parts by weight of perhydropolysilazane (average molecular weight 600, SiH)₁And SiH₂12) to 40 parts by weight of butyl acetate, and stirred at room temperature (25 c) to form a homogeneous and stable diluted PHPS.

(2) 2 parts by weight of dibutyltin dilaurate were added to 11 parts by weight of butyl acetate, and the mixture was stirred at room temperature (25 ℃ C.) to form a uniform catalyst solution.

(3) 4 parts by weight of 1,1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane, 1 part by weight of 3, 5-bis (dimethylsilyloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane and 2 parts by weight of fumed silica (average particle size 15nm) were added to the PHPS dilution, and then the catalyst solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating material according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 45 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 200 ℃ for 2 hours in an air atmosphere having a relative humidity of 65%, to obtain a substrate having a coating layer (thickness of 2 μm). The properties of the coatings were tested and the results are listed in table 5.

Example 17

(1) 40 parts by weight of perhydropolysilazane (average molecular weight 800, SiH)₁And SiH₂14) to 41 parts by weight of butyl acetate, and stirred at room temperature (25 c) to form a homogeneous and stable diluted PHPS.

(2) 1 part by weight of 1,1,1,3,5,5,5, -heptamethyl-3-octyltrisiloxane was added to 14 parts by weight of butyl acetate, and stirred at room temperature (25 ℃ C.) to form a uniform coupling agent solution.

(3) 1 part by weight of 1,1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane, 1 part by weight of 3, 5-bis (dimethylsilyloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane and 2 parts by weight of fumed silica (average particle size of 10nm) were added to the PHPS dilution, and then the coupling agent solution prepared in step (2) was added and stirred uniformly at room temperature (25 ℃ C.), to obtain a coating material according to the present invention.

(4) And (4) applying the coating prepared in the step (3) to the surface of the stainless steel substrate by adopting a spraying method to form a coating layer. And (3) drying the substrate with the coating layer at 50 ℃ in vacuum, and removing the solvent in the coating layer. Then, cured at 200 ℃ for 4 hours in an air atmosphere with a relative humidity of 55%, to obtain a substrate having a coating layer (thickness of 5 μm). The properties of the coatings were tested and the results are listed in table 5.

TABLE 5

The results of examples 1 to 17 demonstrate that coatings formed from the coating compositions of the present invention not only have excellent adhesion properties, but also have good temperature resistance, corrosion resistance and scratch resistance, while also exhibiting low energy surface characteristics and being easy to clean (including anti-frosting properties), on the surface of a substrate.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A coating composition comprising perhydropolysilazane, a siloxane in which substituents on silicon atoms are each independently an alkyl group, an aryl group or a hydrogen atom, an inorganic particle, optionally a catalyst, and optionally a silane coupling agent,

the siloxane is one or more than two selected from siloxane shown in formula I, silane shown in formula II and cyclosiloxane shown in formula III,

in the formula I, n R₁N R₃、R₂And R₄Identical or different, each independently is C₁-C₂₂Alkyl of (C)₆-C₁₂Aryl group of (2), hydrogen atom or

R₇、R₈And R₉Identical or different, each independently is C₁-C₂₂Alkyl of (C)₆-C₁₂An aryl group or a hydrogen atom of (a),

R₅and R₆Are the same or different and are each independently selected from C₁-C₂₂Alkyl radical, C₆-C₁₂An aryl group or a hydrogen atom of (a),

n is in the range of 1-500;

And R is₁₀、R₁₁、R₁₂And R₁₃At least one of which is

R₁₄、R₁₅And R₁₆Identical or different, each independently is C₁-C₂₂Alkyl of (C)₆-C₁₂An aryl group of (a) or a hydrogen atom;

in the formula III, m R₁₇And m R₁₈Identical or different, each independently is C₁-C₂₂Alkyl of (C)₆-C₁₂An aryl group or a hydrogen atom of (a),

m is in the range of 2-500.

2. The coating composition of claim 1, wherein n is in the range of 2-100.

3. The coating composition of claim 2, wherein n is in the range of 2-50.

4. The coating composition of claim 3, wherein n is in the range of 2-20.

5. The coating composition of claim 4, wherein n is in the range of 2-10.

6. The coating composition of claim 1, wherein m is in the range of 2-100.

7. The coating composition of claim 6, wherein m is in the range of 2-50.

8. The coating composition of claim 7, wherein m is in the range of 2-20.

9. The coating composition according to claim 1, wherein the siloxane comprises a first siloxane which is 1,1,1,3,5,5, 5-heptamethyl-3-octyltrisiloxane and/or 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane and a second siloxane which is 3, 5-bis (dimethylsiloxy) -1,1,7, 7-tetramethyl-3, 5-diphenyltetrasiloxane and/or 1,1,1,5,5, 5-hexamethyl-3- (2-phenylethyl) -3- [ (trimethylsilyl) oxy ] trisiloxane.

10. The coating composition of claim 9, wherein the weight ratio of the first siloxane to the second siloxane is 1: 0.1-1.5.

11. The coating composition of claim 10, wherein the weight ratio of the first siloxane to the second siloxane is 1: 0.2-1.2.

12. The coating composition of claim 1, wherein the siloxane comprises a first siloxane and a second siloxane, the first siloxane being hexadecyl heptamethyl siloxane and the second siloxane being dodecyl heptamethyl trisiloxane.

13. The coating composition of claim 12, wherein the weight ratio of the first siloxane to the second siloxane is 1: 0.2-0.8.

14. The coating composition of claim 13, wherein the weight ratio of the first siloxane to the second siloxane is 1: 0.4-0.6.

15. The coating composition of claim 1, wherein the siloxane comprises a first siloxane and a second siloxane, the first siloxane being one or more of octamethyl cyclotetradecasiloxane, tetraethylcyclotetrasiloxane, and dodecamethyl cyclohexasiloxane, and the second siloxane being one or more of trimethyl cyclohexasiloxane, octadecyl heptamethyl trisiloxane, and docosyl decasiloxane.

16. The coating composition of claim 15, wherein the weight ratio of the first siloxane to the second siloxane is 1: 0.1-3.

17. The coating composition of claim 16, wherein the weight ratio of the first siloxane to the second siloxane is 1: 0.2-2.5.

18. The coating composition according to claim 1, wherein the inorganic particles are one or two or more of silica particles, zinc oxide particles, alumina particles, and boron trioxide particles.

19. The coating composition of claim 1 or 18, wherein the inorganic particles have an average particle size of 2-50 nm.

20. The coating composition of claim 19, wherein the inorganic particles have an average particle size of 5-30 nm.

21. The coating composition of claim 20, wherein the inorganic particles have an average particle size of 8-20 nm.

22. The coating composition of claim 1, wherein the catalyst is an amine-based catalyst and/or a metal-based catalyst;

the silane coupling agent is triethoxy-3-thiocyanopropylsilane, tetraethoxysilane, [ (3-trimethoxysilyl) propyl ] diethylethylenediamine, triethoxyoctylsilane, (trimethoxysilyl) ethylene and N-phenylaminomethyl triethoxysilane, one or more of bis [3- (triethoxysilyl) propyl ] disulfide, trimethoxymethylsilane, 3-glycidoxypropyltrimethoxysilane, 3- (trimethoxysilyl) propyl-2-methyl-2-acrylate, 6-ethyl-6- (2-methoxyethoxy) -2,5,7, 10-tetraoxa-6-silaundecane, and 3-chloropropyltrimethoxysilane.

23. The coating composition of claim 22, wherein the catalyst is one or more of an aliphatic amine, a cycloaliphatic amine, an alcohol amine, an aromatic amine, an organotin catalyst, and a palladium catalyst.

24. The coating composition of claim 23, wherein the catalyst is one or more of diethylamine, triethylamine, triethylenetetramine, triethylenediamine, piperazine, piperidine, morpholine, N-dimethylethanolamine, diisopropanolamine, N-diethylethanolamine, aniline, o-phenylenediamine, benzidine, N-dimethylaniline, dibutyltin dilaurate, stannous octoate, dimethyltin, triphenyltin, palladium on charcoal, palladium chloride, palladium propionate, palladium acetate, and palladium triphenylphosphine.

25. The coating composition according to any one of claims 1 to 18 and 22 to 24, wherein the siloxane is contained in an amount of 0.1 to 400 parts by weight, the inorganic particles are contained in an amount of 0.1 to 50 parts by weight, the catalyst is contained in an amount of 0 to 8 parts by weight, and the silane coupling agent is contained in an amount of 0 to 50 parts by weight, relative to 100 parts by weight of perhydropolysilazane.

26. The coating composition according to claim 25, wherein the siloxane is contained in an amount of 1 to 300 parts by weight, the inorganic particles are contained in an amount of 1 to 40 parts by weight, the catalyst is contained in an amount of 1 to 6 parts by weight, and the silane coupling agent is contained in an amount of 1 to 45 parts by weight, relative to 100 parts by weight of perhydropolysilazane.

27. A coating material comprising a liquid dispersant and the coating composition of any one of claims 1 to 26, wherein the components of the coating composition are dispersed in the liquid dispersant.

28. The coating of claim 27, wherein the liquid dispersant is C₃-C₁₀Alkane, C₄-C₁₀Ether of (C)₃-C₁₀Ketone (b), C₇-C₁₂Aromatic hydrocarbons and C₄-C₂₀One or more than two of the esters (b).

29. The coating material according to claim 27 or 28, wherein the content of the liquid dispersant is 50 to 10000 parts by weight relative to 100 parts by weight of perhydropolysilazane.

30. The coating of claim 29, wherein the liquid dispersant is present in an amount of 60 to 5000 parts by weight per 100 parts by weight of perhydropolysilazane.

31. The coating of claim 30, wherein the liquid dispersant is present in an amount of 70 to 2000 parts by weight per 100 parts by weight of perhydropolysilazane.

32. A coating formed from the coating of any one of claims 27-31.

33. An article having a coating, the article comprising a substrate and a coating adhered to at least a portion of a surface of the substrate, wherein the coating is the coating of claim 32.

34. The article of claim 33, wherein the substrate is a metal substrate, a glass substrate, a ceramic substrate, an enamel substrate, a polymer substrate, or a composite substrate of two or more of the foregoing.

35. The article of claim 33 or 34, wherein the article is a household appliance.

36. The article of claim 35, wherein the article is a microwave oven, an oven, a range hood, a cooking utensil, a vacuum cleaner, a dishwasher, an air conditioner, a refrigerator, a water heater, or a washing machine.

37. A method of forming a coating on a surface of a substrate, the method comprising applying a coating according to any one of claims 27 to 31 to at least part of the surface of the substrate to form a coating layer; curing the substrate with the coating layer in the presence of water and oxygen.

38. The method of claim 37, wherein the curing is performed in an air atmosphere having a relative humidity of 45-90%.

39. The method of claim 37 or 38, wherein the curing conditions are such that the molar ratio of nitrogen element to silicon element in the finally formed coating is 0.01-10: 100.

40. the method of claim 39, wherein the curing conditions are such that the molar ratio of elemental nitrogen to elemental silicon in the finally-formed coating is in the range of 0.1-5: 100.

41. the method of claim 40, wherein the curing conditions are such that the molar ratio of elemental nitrogen to elemental silicon in the finally-formed coating is in the range of 0.1-1: 100.

42. the method of claim 41, wherein the curing conditions are such that the molar ratio of elemental nitrogen to elemental silicon in the finally-formed coating is in the range of 0.1-0.3: 100.

43. the method of claim 37 or 38, wherein the curing is performed at a temperature of 25-350 ℃ and the duration of the curing is 0.5-10 hours.

44. The method of claim 43, wherein the curing is performed at a temperature of 50-320 ℃ and the duration of the curing is 1-8 hours.

45. The method of claim 44 wherein the curing is carried out at a temperature of 100-300 ℃ and the duration of the curing is 2-4 hours.

46. The method of claim 45 wherein the curing is performed at a temperature of 200-280 ℃.

47. The method of claim 37, wherein the substrate is a metal substrate, a glass substrate, a ceramic substrate, an enamel substrate, a polymer substrate, or a composite substrate of two or more of the foregoing substrates.

48. A method according to claim 37 or 47, wherein the substrate is provided in a domestic appliance.

49. The method of claim 48, wherein the household appliance is a microwave oven, an oven, a range hood, a cooking appliance, a vacuum cleaner, a dishwasher, an air conditioner, a refrigerator, a water heater, or a washing machine.