TWI600725B - Protective coating composition with anti-skid function, coating product and preparation method thereof - Google Patents

Description

Protective coating composition with anti-slip function, coated article and preparation thereof method

The present invention relates to a protective coating composition having a non-slip function, a coated article and a method of preparing the same.

Ceramic tile substrates, glass substrates, stone substrates and metal substrates sold on the building materials market will become wet and slippery when exposed to water, which may cause safety accidents such as slipping and falling. Therefore, it is necessary to perform anti-slip treatment on the surface of the substrate.

One of the common anti-slip treatment methods is to apply a non-slip coating on the surface of the substrate to increase the friction of the surface of the substrate, so as to increase the friction coefficient to a safe level and achieve the anti-slip effect, thereby reducing accidents such as slipping and falling. happened.

At present, the anti-slip coating layer generally uses an alkyd resin, a chlorinated rubber, a phenol resin, an epoxy resin or a polyurethane resin as a film-forming resin, and is filled with anti-slip pellets such as quartz sand, silicon carbide, titanium oxide, aluminum oxide or rubber particles. These non-slip pellets are irregular in shape and protrude from the surface of the coating. It can increase the roughness and friction of the surface and reduce the slidability of people or other objects on the surface to achieve the purpose of anti-slip.

In recent years, it has been found that the anti-slip particles are not filled, and the anti-slip requirements can be achieved only by special coatings. CN104926369 (Silver Dragon et al.) discloses a non-slip coating using a ceramic tile substrate comprising a first decane and a solvent, wherein the first decane is an epoxy decane or a decanoic acid ester, wherein the solvent is selected from water or an alcohol. However, the non-slip coating does not meet some of the requirements for higher wear and scratch resistance. In order to meet the higher wear and scratch resistance requirements in some occasions, it is necessary to further improve the wear resistance and scratch resistance of the non-slip coating.

Hydrolysates of oxiranes containing epoxy functional groups are disclosed in the formulations of US Pat. No. 6,100, 209, 719 and U.S. Patent No. 2,001,015, 339, the disclosure of which is incorporated herein by reference.

The present invention is directed to providing a protective coating composition having an anti-slip function to meet the need for the dry coating and coated articles obtained by further preparation thereof to be slip resistant in a slippery environment. The dried coating and the coated article have both good abrasion resistance and scratch resistance, and can function as a durable protective substrate.

According to an aspect of the invention, there is provided a protective coating composition having an anti-slip function, comprising 100% by weight of the total weight of the coating composition, comprising the reaction product of the following reaction components: 1) first a reaction solution comprising the reaction product of the following reaction components: 1-30 wt.% of a cyclooxyl group-containing oxirane oligomer and/or polymer A, said epoxy group-containing functional group The oxane oligomer and/or polymer A has a linear, branched or cyclic structure and can be represented by the formula I: HO-[SiR ¹ (OR ³ )-O] _a -[SiR ² (OR ³ )-O] _b -[Si(OH) ₂ -O] _c -H(I), where 0<a 100;0<b 100;0 c 100; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl, 3-(2,3-dihydroxypropoxy)propyl, 2-(3,4-epoxycyclohexyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ represents A hydrogen atom or an alkyl group having a carbon number of 1-4, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tri Butyl butyl; 1-15 wt.% of a decyl compound B containing an epoxy functional group, which may be represented by the general formula II: R ⁴ -SiR ³ _d (OR ³ ) _{3- d} (II), where, 0 d 2; R ⁴ represents an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-(2,3-epoxypropoxy)propyl , 3-(2,3-dihydroxypropoxy)propyl, 2-(3,4-epoxycyclohexyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ An alkyl group representing a hydrogen atom or a carbon number of 1-4, including one or more of the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, butyl, isobutyl and a tertiary butyl group; the weight ratio of the epoxy functional group-containing fluorene oxide oligomer and/or polymer A to the epoxy group-containing decane compound B is at least 1:1; 45-96 wt. % of water; and acid; the first reaction solution has a pH of less than or equal to 5; 2) 0.2-5 wt.% of an amino-functional decane compound C, and the amino-functional decane compound C can be used as a general formula III represents: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i - R ⁶ -SiR ³ _k (OR ³ ) _3-k (III), where 0 e 1;0 f 1;1 g 6;0 h 1;0 i 6;0 j 2;0 k 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl, alkenyl or benzyl group having a carbon number of 1-6; and R ⁶ represents a linear, branched or cyclic group having a carbon number of 1-6. An alkyl group or an alkenyl group; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-4, and includes one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, di Butyl butyl, isobutyl and tert-butyl; 3) 0.2-5 wt.% n-decanoate, which can be represented by the general formula IV: Si(OR) ₄ (IV), wherein R represents an alkyl group having a carbon number of 1-4, and includes one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tertiary Butyl.

According to another aspect of the present invention, there is provided a coated article comprising a substrate and a dried coating applied to the substrate, the dried coating comprising applying the coating composition to the The surface of the substrate, the dried coating.

According to another aspect of the present invention, there is provided a process for the preparation of a coated article comprising the steps of applying the coating composition to the surface of the substrate to form a wet coating composition on the surface of the substrate. The liquid film of the wet coating composition is dried to obtain a dry coating attached to the surface of the substrate.

It is to be understood that those skilled in the art can devise various other embodiments and can be modified in accordance with the teachings of the present disclosure without departing from the scope and spirit of the invention. Therefore, the following specific embodiments are not limiting.

All numbers expressing quantities and physicochemical properties used in the specification and claims are to be understood as being modified in all instances by the term "about" unless otherwise indicated. Accordingly, the numerical parameters set forth in the above description and the appended claims are approximations unless otherwise indicated, and those skilled in the art are able to use the teachings disclosed herein. approximation. The use of a range of values by the endpoints includes all digits within the range and any ranges within the range, for example, 1, 2, 3, 4, and 5 include 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

Coating composition

The protective coating composition having anti-slip function provided by the present invention comprises the reaction product of the following reaction components in a total weight of the coating composition of 100 wt.%: 1) a first reaction solution, the first A reaction solution comprises the reaction product of the following reaction components: 1-30 wt.% of a cyclooxyl group-containing oxirane oligomer and/or polymer A, said epoxy functional group-containing oxirane oligomer And/or polymer A has a linear, branched or cyclic structure and can be represented by the general formula I: HO-[SiR ¹ (OR ³ )-O] _a -[SiR ² (OR ³ )-O] _b -[ Si(OH) ₂ -O] _c -H (I) where 0<a 100;0<b 100;0 c 100; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl, 3-(2,3-dihydroxypropoxy)propyl, 2-(3,4-epoxycyclohexyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ represents A hydrogen atom or an alkyl group having a carbon number of 1-4, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tri Butyl butyl; 1-15 wt.% of a decyl compound B containing an epoxy functional group, which may be represented by the general formula II: R ⁴ -SiR ³ _d (OR ³ ) _{3- d} (II) where 0 d 2; R ⁴ represents an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl, 3-(2, 3 -dihydroxypropoxy)propyl, 2-(3,4-epoxycyclohexyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ represents a hydrogen atom or has a carbon number of Alkyl groups of 1-4, including one or more of the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tert-butyl; a weight ratio of the epoxy group-containing siloxane oxide oligomer and/or polymer A to the epoxy group-containing decane compound B of at least 1:1; 45-96 wt.% of water; and an acid; The pH of the first reaction solution is less than or equal to 5; 2) 0.2-5 wt.% of the amino-functional decane compound C, and the amino-functional decane compound C can be represented by the general formula III: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k ( OR ³ ) _3-k (III) where 0 e 1;0 f 1;1 g 6;0 h 1;0 i 6;0 j 2;0 k 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl, alkenyl or benzyl group having a carbon number of 1-6; and R ⁶ represents a linear, branched or cyclic group having a carbon number of 1-6. An alkyl group or an alkenyl group; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-4, and includes one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, di Butyl butyl, isobutyl and tert-butyl; 3) 0.2-5 wt.% n-decanoate, which can be represented by the general formula IV: Si(OR) ₄ (IV) wherein R An alkyl group having a carbon number of 1-4, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tert-butyl base.

The general formula of the epoxy functional group-containing fluorene oxide oligomer and/or polymer A is preferably: HO-[SiR ¹ (OR ³ )-O] _a -[SiR ² (OR ³ )-O] _b -[Si(OH) ₂ -O] _c -H (I) where 0<a 20;0<b 20;0 c 20; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl and 2-(3, 4-Epoxycyclohexyl)ethyl; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-3, and includes one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

The content of the epoxy functional group-containing siloxane oxide oligomer and/or polymer A is from 1 to 30 wt.%, preferably from 1 to 25 wt.%, particularly preferably from 4.5 to 25 wt.%, in combination with the coating The total weight of the material is calculated as 100 wt.%. If the content of the epoxy functional group-containing siloxane oxide oligomer and/or polymer A is less than 1 wt.%, it may be difficult to form a dry coating of a sufficient thickness on the surface of the substrate so as not to reach The anti-slip property and the abrasion resistance of the coated article provided by the present invention. If the content of the epoxy functional group-containing oxirane oligomer and/or polymer A is more than 30 wt.%, the reaction speed of the first reaction solution with the amino group-containing decane compound C and the n-decanoate may be excessive. Fast, there may be more defects depending on the appearance of the dried coating obtained therefrom, resulting in significant defects in the appearance of the resulting coated article.

The general formula of the cyclooxy compound-containing decane compound B is preferably: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) wherein 0 d 2; R ⁴ represents an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl and 2-(3,4-epoxy rings) Hexyl)ethyl; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-3, and includes one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

The epoxy group-containing decane compound B includes one or more of the following groups: 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3 - glycidyloxypropylmethyldimethoxydecane, 3-glycidyloxypropylmethyldiethoxydecane, 3-glycidoxypropylethyldimethoxydecane, 3-glycidyloxypropylethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and 2-(3,4-epoxycyclohexyl) Ethyltriethoxydecane.

The content of the epoxy group-containing decane compound B is 1 to 15 wt.%, preferably 1 to 13 wt.%, particularly preferably 3 to 13 wt.%, based on 100 wt.% of the total weight of the coating composition. . If the content of the epoxy group-containing decane compound B is less than 1 wt.%, the first reaction solution The reaction composition is reacted with a decane compound C containing an amino functional group and a decanoic acid ester to obtain a coating composition, and the dry coating layer and the coated article further prepared by using the coating composition may have poor slip resistance, so that the invention cannot be achieved. The anti-slip properties of the coated products provided. If the content of the epoxy group-containing decane compound B is more than 15% by weight, the reaction speed of the first reaction solution with the amino group-containing decane compound C and the n-decanoate may be too fast, and the dried coating obtained therefrom may be obtained. The appearance may have more defects, resulting in significant defects in the appearance of the resulting coated article.

The weight ratio of the epoxy functional group-containing fluorene oxide oligomer and/or polymer A to the epoxy group-containing decane compound B is at least 1:1, preferably 1.2:1, particularly preferably 1.5: 1. If the weight ratio of the epoxy functional group-containing decane oxide oligomer and/or polymer A to the epoxy group-containing decane compound B is less than 1:1, the first reaction solution and the amino group-containing group The precipitation of the decane compound C and the decanoic acid ester may occur after it is mixed, and it is not possible to further prepare the dried coating or coated article provided by the present invention.

The acid may be an inorganic acid or an organic acid. The inorganic acid includes one or more of the following groups: hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and particularly preferably hydrochloric acid and phosphoric acid. The organic acid includes one or more of the group consisting of formic acid, acetic acid, propionic acid, benzoic acid, and benzenesulfonic acid, with formic acid and acetic acid being particularly preferred. The pH of the first reaction solution is less than or equal to 5, preferably less than or equal to 4. If the pH of the first reaction solution is greater than 5, when it is reacted with a decane compound C containing an amino functional group and a decanoic acid ester to obtain a coating composition, the dried coating layer and coating are further prepared using the coating composition. The anti-slip properties, abrasion resistance and scratch resistance of the article may be poor, so that the anti-slip properties, abrasion resistance and scratch resistance properties of the coated articles provided by the present invention are not achieved.

The formula of the amino group-containing decane compound C is preferably: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g - NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (III)

Among them, 0 e 1;0 f 1;1 g 6;0 h 1;0 i 6;0 j 2;0 k 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl or alkenyl group having a carbon number of from 1 to 4; and R ⁶ represents a linear, branched or cyclic alkyl group having a carbon number of from 1 to 4; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-3, and includes one or more of the following groups: methyl group, ethyl group, n-propyl group and isopropyl group.

The amino-functional decane compound C includes one or more of the following groups: 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropylmethyldimethoxy Decane, 3-aminopropylmethyldiethoxydecane, 3-aminopropylethyldimethoxydecane, 3-aminopropylethyldiethoxydecane, N-(2-aminoethyl) -3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxydecane, N-(2-aminoethyl)-3-aminopropylethyldimethoxydecane , N-(2-Aminoethyl)-3-aminopropylethyldiethoxydecane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxydecane, 3- [2-(2-Aminoethylamino)ethylamino]propyltriethoxydecane, 3-[2-(2-aminoethylamino)ethylamino]propylmethyldimethoxydecane, 3-[2-(2-Aminoethylamino)ethylamino]propylmethyldiethoxydecane, 3-(N,N-dimethylaminopropyl)-aminopropyltrimethoxydecane, 3-(N,N-dimethylaminopropyl)-aminopropyltriethoxy Alkane, 3-(N,N-dimethylaminopropyl)-aminopropylmethyldimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3- Aminopropyltriethoxydecane, N,N-dimethyl-3-aminopropyltrimethoxydecane, N,N-diethyl-3-aminopropyltrimethoxydecane, N,N-di Ethyl-3-aminopropyltriethoxy Decane, N-ethyl-3-trimethoxycarboxylidene-2-methylpropylamine, N-[3-(trimethoxyindolyl)propyl]-n-butylamine, bis[(3-trimethoxyindolyl) )-propyl]amine, bis[(3-triethoxyindolyl)-propyl]amine.

The content of the amino-functional decane compound C is from 0.2 to 5% by weight, preferably from 0.2 to 3% by weight, particularly preferably from 0.8 to 3% by weight, based on 100% by weight of the total weight of the coating composition. If the content of the amino-functional decane compound C is less than 0.2 wt.%, when it is reacted with the first reaction solution and the decanoic acid ester to obtain a coating composition, the coating composition may be applied to the surface of the substrate. It is difficult to completely cure, and the anti-slip property, abrasion resistance and scratch resistance of the further obtained dry coating and coated article may be poor, so that the anti-slip property and resistance of the coated article provided by the present invention cannot be achieved. Grinding performance and scratch resistance. If the content of the amino-functional decane compound C is more than 5 wt.%, when it is reacted with the first reaction solution and the n-decanoate to obtain a coating composition, the dried coating and the coating are further prepared using the coating composition. The anti-slip property, the abrasion resistance and the scratch resistance of the cloth product may be unsatisfactory, so that the anti-slip property, the abrasion resistance and the scratch resistance of the coated article provided by the present invention are not attained.

The formula of the n-decanoate is preferably: Si(OR) ₄ (IV) wherein R represents an alkyl group having a carbon number of 1-3, and includes one or more of the following groups: methyl, ethyl, and Propyl and isopropyl.

The n-nonanoate includes one or more of the following groups: methyl n-decanoate, ethyl n-decanoate, n-propyl n-decanoate and isopropyl n-decanoate.

The content of the n-nonanoate is 0.2-5 wt.%, preferably 0.2-3 wt.%, particularly preferably 0.7-3 wt.%, based on 100 wt.% of the total weight of the coating composition. If the content of the n-nonanoic acid ester is less than 0.2 wt.%, when it is reacted with the first reaction solution and the decane compound C containing an amino functional group to obtain a coating composition, the dried coating layer is further prepared using the coating composition. The slip resistance of the coated article and the coated article may be poor to achieve the anti-slip properties of the coated article provided by the present invention. If the content of the n-nonanoic acid ester is more than 5 wt.%, when it reacts with the first reaction solution and the decane compound C containing an amino functional group to obtain a coating composition, the coating composition may be applied to the surface of the substrate to be bonded. Poor force, the resulting dry coating and coated article may have poor abrasion resistance and scratch resistance, so that the abrasion resistance and scratch resistance of the coated article provided by the present invention cannot be achieved. performance.

The coating composition of the present invention may further comprise surface epoxy modified cerium oxide particles. The surface epoxy-modified ceria particles can further enhance the abrasion resistance and scratch resistance of the coated article provided by the present invention. The surface epoxy-modified cerium oxide particles are surface epoxy-modified cerium oxide particles having a single average particle diameter, or may be modified by surface epoxy having two or more average particle diameters. A combination of cerium oxide particles. The particle size as referred to herein and in the scope of the patent application refers to the length of the longest axis of the particles. The surface epoxy modification described herein and in the scope of the patent application means that the reactive group (for example, a SiOH group) inherent to the surface of the ceria particle is substituted with an organic group having at least one epoxy functional group. The surface epoxy-modified cerium oxide particles have an average particle diameter of less than or equal to 50 nm, preferably less than or equal to 20 nm, particularly preferably less than or equal to 15 nm. Examples of commercially available surface epoxy modified cerium oxide sols include cerium oxide which can be surface-epoxidized in water or in an aqueous alcohol solution under the trade name Bindzil from AkzoNobel. Sol. A useful surface epoxy modified cerium oxide sol having an average particle size of 7 nm and a nominal solids content of 28 wt.% can be used as a surface epoxy modification of Binzil CC301 from AkzoNobel. A cerium oxide sol. Other commercially available surface epoxy modified cerium oxide sols include surface epoxy modified cerium oxide sols available from AkzoNobel as Bindzil CC151 HS and Bindzil CC401.

The content of the surface epoxy-modified cerium oxide particles is 0.01-10 wt.%, preferably 0.5-10 wt.%, particularly preferably 0.5-5 wt.%, and 100 wt.% based on the total weight of the coating composition. meter. If the content of the surface epoxy-modified ceria particles is more than 10 wt.%, when it is reacted with the first reaction solution, the amino-functional decane compound C and the n-decanoate to obtain a coating composition, the coating is used. The dried coating obtained by further preparation of the composition may be poor in appearance so as to fail to achieve the good appearance of the coated article provided by the present invention.

The coating composition of the present invention may further comprise an organic solvent. The organic solvent is miscible with water and can improve the wettability of the coating composition on the surface of the substrate. The organic solvent may include one or more of the group consisting of alcohols, ketones, esters, and ethers having a molecular weight of less than 250. The alcohol is preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, ethylene glycol, propylene glycol, glycerol and triethylene glycol. The ketone is preferably acetone and butanone. The ester is preferably methyl acetate and ethyl acetate. The ether having a molecular weight of less than 250 is preferably ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, ethylene Alcohol dimethyl ether, propylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether.

The content of the organic solvent is from 0.01 to 5 wt.%, preferably from 0.01 to 3 wt.%, particularly preferably from 0.01 to 2 wt.%, based on 100 wt.% of the total weight of the coating composition. If the content of the organic solvent is more than 5 wt.%, when it is reacted with the first reaction solution, the amino group-containing decane compound C and the n-decanoate to obtain a coating composition, the coating composition is further used to prepare the dried coating. The slip resistance of the layers and coated articles may be poor to achieve the slip resistance of the coated articles provided by the present invention.

The coating composition of the present invention may further comprise an additive. The additive comprises one or more of the group consisting of detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders. The surfactant is a nonionic surfactant capable of improving the wettability of the coating composition on the surface of the substrate. The nonionic surfactant may be selected from one or more of the group consisting of polyoxyethylene type nonionic surfactants, polyol type nonionic surfactants, alkyl alcohol oxime type nonionic surfactants, and fluorine. A carbon type nonionic surfactant, an organic quinoid type nonionic surfactant, and a modified organic quinoid type nonionic surfactant.

The nonionic surfactant is present in an amount of from 0.01 to 2 wt.%, preferably from 0.01 to 1 wt.%, particularly preferably from 0.05 to 0.5 wt.%, based on 100 wt.% of the total weight of the coating composition. If the content of the nonionic surfactant is more than 2 wt.%, when it is reacted with the first reaction solution, the amino group-containing decane compound C and the n-decanoate to obtain a coating composition, the coating composition is further prepared. The slip resistance of the dried coating and coated article may be poor to achieve the slip resistance of the coated article provided by the present invention.

Coated product

The coated article provided by the present invention comprises a substrate and a dried coating applied to the substrate. The substrate comprises one or more of the group consisting of a ceramic tile substrate, a glass substrate, a stone substrate, and a metal substrate. The "ceramic tiles" described herein and in the scope of the patent application are suitable for use in porcelain materials prepared from refractory clay, brick, concrete, ceramic, marble, limestone and other stone or slate. The ceramic tile substrate comprises one or more of the following groups: vitrified tiles, glazed tiles, antique tiles, microcrystalline stones, polished tiles, imitation granite tiles, and imitation marble tiles. The stone substrate comprises one or more of the group consisting of marble, granite, and artificial stone. The metal substrate comprises one or more of the group consisting of a stainless steel substrate, a cold rolled steel substrate, a galvanized steel substrate, an aluminum substrate, and an aluminum alloy substrate.

The coated article comprises a coating obtained by drying the coating composition provided by the present invention. The coated article is completely or partially free of water, preferably completely free of water.

For a description of the coating composition, see the "Coating Composition" section of the specification of the present invention.

The coated article is capable of greatly improving the slip resistance of the substrate under wet conditions. The coated article may have any suitable thickness as needed, and the coated article may have a thickness of 100 nm to 100 μm, or 200 nm to 50 μm, or 500 nm to 20 μm.

Method for preparing coated article

The method for preparing a coated article provided by the present invention comprises the steps of: applying a coating composition provided by the present invention to a surface of the substrate to form a wet coating composition liquid film on the surface of the substrate, The wet coating composition liquid film is dried to give a dried coating which adheres to the surface of the substrate.

For a description of the coating composition, substrate and coated article, see the "Coating Composition" and "Coated Products" portions of the specification of the present invention.

The coating composition can be applied to the surface of the substrate by methods known in the art, preferably one or more of the following groups: knife coating, wiping, brushing, Dip coating and spray coating.

The slip resistant liquid may be dried using a suitable drying method known in the art, and the drying process may be carried out at room temperature or higher, for example, the temperature may be 20-180 ° C, or 20- 150 ° C, or 20-120 ° C.

The present invention provides a number of preferred embodiments relating to coating compositions, coated articles, and methods of making the same.

Preferred Embodiment 1 is a protective coating composition having an anti-slip function, comprising 100% by weight of the total weight of the coating composition, including the reaction product of the following reaction components: 1) a first reaction solution, The first reaction solution comprises a reaction product of the following reaction components: 1-30 wt.% of a cyclooxyl group-containing oxirane oligomer and/or polymer A, which contains an epoxy functional group-containing oxirane oligomerization And/or polymer A has a linear, branched or cyclic structure and can be represented by the general formula I: HO-[SiR ¹ (OR ³ )-O] _a -[SiR ² (OR ³ )-O] _b - [Si(OH) ₂ -O] _c -H (I) where 0<a 100;0<b 100;0 c 100; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl, 3-(2,3-dihydroxypropoxy)propyl, 2-(3,4-epoxycyclohexyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ represents A hydrogen atom or an alkyl group having a carbon number of 1-4, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tri Butyl butyl; 1-15 wt.% of a decyl compound B containing an epoxy functional group, which may be represented by the general formula II: R ⁴ -SiR ³ _d (OR ³ ) _{3- d} (II) where 0 d 2; R ⁴ represents an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl, 3-(2, 3 -dihydroxypropoxy)propyl, 2-(3,4-epoxycyclohexyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ represents a hydrogen atom or has a carbon number of Alkyl groups of 1-4, including one or more of the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tert-butyl; a weight ratio of the epoxy group-containing siloxane oxide oligomer and/or polymer A to the epoxy group-containing decane compound B of at least 1:1; 45-96 wt.% of water; and an acid; The pH of the first reaction solution is less than or equal to 5; 2) 0.2-5 wt.% of the amino-functional decane compound C, and the amino-functional decane compound C can be represented by the general formula III: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k ( OR ³ ) _3-k (III) where 0 e 1;0 f 1;1 g 6;0 h 1;0 i 6;0 j 2;0 k 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl, alkenyl or benzyl group having a carbon number of 1-6; R ⁶ represents a linear, branched or cyclic group having a carbon number of 1-6. An alkyl group or an alkenyl group; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-4, and includes one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, di Butyl butyl, isobutyl and tert-butyl; 3) 0.2-5 wt.% n-decanoate, which can be represented by the general formula IV: Si(OR) ₄ (IV) wherein R An alkyl group having a carbon number of 1-4, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tert-butyl base.

The preferred embodiment 2 is the coating composition according to the preferred embodiment 1, wherein the epoxy group-containing oxirane oligomer and/or polymer A has the formula: HO-[SiR ¹ (OR ³ )-O] _a -[SiR ² (OR ³ )-O] _b -[Si(OH) ₂ -O] _c -H (I) wherein 0<a 20;0<b 20;0 c 20; R1 and R2 each independently represent an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl and 2-(3,4- Epoxycyclohexyl)ethyl; R3 represents a hydrogen atom or an alkyl group having a carbon number of 1-3, and includes one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

The preferred embodiment 3 is the coating composition according to the preferred embodiment 1, wherein the epoxy group-containing siloxane oxide oligomer and/or polymer A is contained in an amount of from 4.5 to 25 wt.%.

The preferred embodiment 4 is the coating composition according to the preferred embodiment 1, wherein the octane compound B having an epoxy functional group has the formula: R ⁴ -SiR ³ _d (OR ³ ) _3-d ( II) where 0 d 2; R ⁴ represents an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidoxypropyl and 2-(3,4-epoxy rings) Hexyl)ethyl; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-3, and includes one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

A preferred embodiment 5 is the coating composition according to the preferred embodiment 4, wherein the epoxy group-containing decane compound B comprises one or more of the following groups: 3-glycidyloxypropyltrimethyl Oxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidyloxypropylmethyldimethoxydecane, 3-glycidyloxypropylmethyldiethoxylate Baseline, 3-glycidoxypropylethyldimethoxydecane, 3-glycidyloxypropylethyldiethoxydecane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane.

The preferred embodiment 6 is the coating composition according to the preferred embodiment 1, wherein the epoxy group-containing decane compound B is contained in an amount of from 3 to 13 wt.%.

The preferred embodiment 7 is the coating composition according to the preferred embodiment 1, wherein the epoxy functional group-containing decane oxide oligomer and/or polymer A and the epoxy group-containing decane are used. The weight ratio of Compound B is at least 1.2:1.

The preferred embodiment 8 is the coating composition according to the preferred embodiment 1, wherein the acid is an inorganic acid or an organic acid, and the inorganic acid comprises one or more of the following groups: hydrochloric acid, nitric acid, and phosphoric acid; The organic acid includes one or more of the following groups: formic acid and acetic acid.

The preferred embodiment 9 is the coating composition according to the preferred embodiment 1, wherein the amino group-containing decane compound C has the formula: [(R ³ O) _3-j R ³ _j Si-R ⁶ _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (III) where 0 e 1;0 f 1;1 g 6;0 h 1;0 i 6;0 j 2;0 k 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl or alkenyl group having a carbon number of from 1 to 4; and R ⁶ represents a linear, branched or cyclic alkyl group having a carbon number of from 1 to 4; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-3, and includes one or more of the following groups: methyl group, ethyl group, n-propyl group and isopropyl group.

The preferred embodiment 10 is the coating composition according to the preferred embodiment 9, wherein the amino-functional decane compound C comprises one or more of the following groups: 3-aminopropyltrimethoxydecane, 3- Aminopropyltriethoxydecane, 3-aminopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, 3-aminopropylethyldimethoxydecane, 3- Aminopropylethyldiethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxy Decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxydecane, N- (2-Aminoethyl)-3-aminopropylethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylethyldiethoxydecane, 3-[2-( 2-aminoethylamino)ethylamino]propyltrimethoxydecane, 3-[2-(2-aminoethylamino)ethylamino]propyltriethoxydecane, 3-[2-(2 -aminoethylamino)ethylamino]propylmethyldimethoxydecane, 3-[2-(2-aminoethylamino)ethylamino]propylmethyldiethoxydecane, 3-( N,N-dimethylamine -Aminopropyltrimethoxydecane, 3-(N,N-dimethylaminopropyl)-aminopropyltriethoxydecane, 3-(N,N-dimethylaminopropyl)-amine Propylmethyldimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N,N-dimethyl-3 -aminopropyltrimethoxyfluorene Alkane, N,N-diethyl-3-aminopropyltrimethoxydecane, N,N-diethyl-3-aminopropyltriethoxydecane, N-ethyl-3-trimethoxymethyl矽alkyl-2-methylpropylamine, N-[3-(trimethoxyindolyl)propyl]-n-butylamine, bis[(3-trimethoxyindolyl)-propyl]amine, bis[(3-three) Ethoxymethyl)-propyl]amine.

A preferred embodiment 11 is the coating composition according to the preferred embodiment 1, wherein the n-decanoate has the formula: Si(OR) ₄ (IV) wherein R represents a carbon number of 1-3 Alkyl groups, including one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

A preferred embodiment 12 is the coating composition of the preferred embodiment 11, wherein the n-nonanoic acid ester comprises one or more of the group consisting of methyl ortho-decanoate, ethyl ortho-decanoate, n-decanoic acid. N-propyl ester and isopropyl ortho-decanoate.

A preferred embodiment 13 is the coating composition of the preferred embodiment 1, wherein the coating composition further comprises 0.01 to 10 wt.% of surface epoxy-modified ceria particles, the coating The total weight of the composition is based on 100 wt.%.

A preferred embodiment 14 is the coating composition of the preferred embodiment 13, wherein the surface epoxy-modified cerium oxide particles have an average particle diameter of less than or equal to 15 nm.

The preferred embodiment 15 is the coating composition according to the preferred embodiment 1, wherein the coating composition further comprises 0.01-5 wt.% of an organic solvent, and the total weight of the coating composition is 100 wt. In terms of %, the organic solvent is miscible with water and includes one or more of the following groups: alcohols, ketones, esters, and ethers having a molecular weight of less than 250.

The preferred embodiment is a coating composition according to the preferred embodiment 1, wherein the coating composition further comprises 0.01-2 wt.% of the additive, and the total weight of the coating composition is 100 wt.%. The additive includes one or more of the group consisting of detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders.

A preferred embodiment is the coating composition of the preferred embodiment 16, wherein the surfactant is a nonionic surfactant, including one or more of the group consisting of polyoxyethylene type nonionic surfactants. , polyol type nonionic surfactant, alkyl alcohol guanamine type nonionic surfactant, fluorocarbon type nonionic surfactant, organic bismuth type nonionic surfactant and modified organic bismuth type nonionic surfactant .

Preferred Embodiment 18 is a coated article comprising a substrate and a dried coating applied to the substrate, the dried coating comprising applying the coating composition as described in Preferred Embodiments 1-17 to The surface of the substrate, the dried coating.

A preferred embodiment is the coated article of claim 18, wherein the substrate comprises one or more of the group consisting of a ceramic tile substrate, a glass substrate, a stone substrate, and a metal substrate.

A preferred embodiment of the invention is the coated article of the preferred embodiment 19, wherein the ceramic tile substrate comprises one or more of the group consisting of: a vitrified tile, a glazed tile, an antique tile, a microcrystalline stone, a polished tile Imitation granite tiles and imitation marble tiles.

The coated article of the preferred embodiment 19, wherein the stone substrate comprises one or more of the group consisting of marble, granite, and artificial stone.

A preferred embodiment is the coated article of the preferred embodiment 19, wherein the metal substrate comprises one or more of the group consisting of: a stainless steel substrate, a cold rolled steel substrate, a galvanized steel substrate, an aluminum base Materials and aluminum alloy substrates.

A preferred embodiment 23 is a method of producing a coated article comprising the steps of applying a coating composition as described in preferred embodiments 1-17 to the surface of the substrate to form a wet coating on the surface of the substrate. The liquid film of the composition is dried to obtain a dried coating which adheres to the surface of the substrate.

The preferred embodiment is a preparation method according to the preferred embodiment 23, wherein the coating composition is applied to the surface of the substrate by the following methods: blade coating, wiping, brushing, dip coating Method and spray method.

Example

The following examples and comparative examples are provided to aid the understanding of the invention, and these examples and comparative examples are not to be construed as limiting the scope of the invention. All parts and percentages are by weight unless otherwise indicated.

The materials used in the examples and comparative examples of the present invention are shown in Table 1 below.

The present invention evaluates the slip resistance of the dried coating or coated article provided by the examples and comparative examples mainly by the dry and wet static friction coefficient tests. On the basis of this, the present invention evaluates the abrasion resistance of the dried coating or coated article provided by the examples and the comparative examples by a dry grinding test. The present invention evaluates the scratch resistance of the dried coating or coated article provided by the examples and comparative examples by a pencil hardness test. Furthermore, the present invention further evaluates the effect of the dried coating provided by the examples and comparative examples on the appearance of the substrate by a surface gloss test.

Anti-slip performance test

The static friction coefficient is an important indicator for evaluating the safety performance of the ground slip. The present invention characterizes the slip resistance of a coating composition or coated article under dry conditions by a dry static coefficient of friction. The present invention characterizes the slip resistance of a coating composition or coated article under wet conditions by a wet static coefficient of friction.

The instrument for testing the dry and wet static coefficients of friction is ASM 825A, available from American Slip Meter. The friction medium for testing the dry and wet static friction coefficients was Neolite rubber (Shore hardness 93-96, available from Goodyear Tire and Rubber).

A coating composition is applied to the surface of the substrate, and after drying, a dry coating is formed on the surface of the substrate to obtain a coated article comprising the substrate and the dried coating.

The dry static coefficient of the surface of the coated article was measured using an ASM 825A static friction coefficient tester. Three different regions were taken on the surface of the coated article, and the dry static friction coefficient was measured and the average value was taken.

After the surface of the coated article was completely wetted with deionized water, the wet static coefficient of friction of the surface of the coated article was measured using an ASM 825A static friction coefficient tester. Three different regions were placed on the surface of the coated article, and the wet static friction coefficient was measured and the average value was taken.

According to the standards provided by Underwriters Laboratories (UL) and the American Society for Testing and Materials (ASTM):

The average value of several static friction coefficients is greater than 0.6, indicating that the surface of the coated article has good anti-slip properties under dry conditions, and the larger the value, the better the anti-slip performance.

If the average value of the wet static friction coefficient is greater than 0.6, the surface of the coated article has good anti-slip properties under wet conditions, and the larger the value, the better the anti-slip performance.

The test results of the dry and wet static friction coefficients of the dried coating or coated article provided by the examples of the present invention and the comparative examples are shown in Table 3.

Wear resistance test

The present invention characterizes the abrasion resistance of dried coatings or coated articles by dry milling testing.

The instrument for testing wear resistance is BYK Abrasion Tester, which is available from BYK.

A coating composition is applied to the surface of the substrate, and after drying, a dry coating is formed on the surface of the substrate to obtain a coated article comprising the substrate and the dried coating.

The surface of the coated article was rubbed with a friction material of 2.3 M kg under a load of 2.2 kg, which was a 3M 5100 brush, available from 3M Company. The wet static friction coefficient was tested once every 500 times. When the wet static friction coefficient was less than or equal to 0.6, the test was stopped, and the number of friction loops tested (one friction loop refers to rubbing back and forth once). If the wet static friction coefficient is still greater than 0.6 when the number of friction loops reaches 20000, the test is stopped and the number of friction loops is recorded to be 20000.

If the measured number of friction turns of a coated article is greater than 5000, the coated article has good wear resistance.

The test results of the abrasion resistance of the dried coating or coated article provided by the examples of the present invention and the comparative examples are shown in Table 4.

Scratch resistance test

The present invention characterizes the scratch resistance of a dried coating or coated article by a pencil hardness test.

The instrument for testing pencil hardness was Elcometer 3086, available from Elcometer.

A coating composition is applied to the surface of the substrate, and after drying, a dry coating is formed on the surface of the substrate to obtain a coated article comprising the substrate and the dried coating.

Use a special mechanical pencil sharpener to cut a piece of Zhonghua high-grade drawing pencil (hardness from 9B to 9H) to a piece of wood of about 5mm-6mm, leaving the original, unscratched, smooth cylindrical pencil core. Hold the pencil vertically, keep the pencil at a 90 degree angle with the sandpaper, and move the pencil back and forth on the sandpaper. The tip of the pencil refill is flattened at right angles and the pencil is continuously moved until a complete smooth circular cross section is obtained. Place the coated product on a level, stable table top, attach the pencil to the instrument at a 45-degree angle with the clamp to maintain the level of the instrument, and place the tip of the pencil on the surface of the coated article at a load of 750 g. Under conditions, the pencil is pushed at a constant speed of 0.5 mm/s to 1 mm/s to push the distance of at least 7 mm away from the operator. Pencils of the same hardness were tested 5 times at different locations on the surface of the coated article. The surface of the coated article was wiped with an absorbent solvent, and the surface of the coated article was visually observed for defects such as plastic deformation and/or cohesive failure. If the defects such as plastic deformation and/or cohesive failure have occurred, stop the test and record the hardness of the pencil used in the test. If defects such as plastic deformation and/or cohesive failure do not occur, repeat the above test with a pencil with a higher hardness until the surface of the coated product has defects such as plastic deformation and/or cohesive failure, and record the pencil used in the last test. Hardness.

If the measured pencil hardness of a coated article is greater than 4H, the coated article has good scratch resistance.

The test results of the scratch resistance of the dried coating or coated article provided by the examples of the present invention and the comparative examples are shown in Table 4.

Surface gloss test

The present invention characterizes the effect of a dry coating on the appearance of a substrate by a surface gloss test.

The instrument for testing surface gloss is a Micro-Tri-Gloss gloss meter available from BYK-Gardner.

A coating composition is applied to the surface of the substrate, and after drying, a dry coating is formed on the surface of the substrate to obtain a coated article comprising the substrate and the dried coating.

The surface glossiness values of the coated articles were measured using a Micro-Tri-Gloss gloss meter. Three different areas were taken on the surface of the coated article, and the surface gloss values of 20°, 60°, and 85° were measured, and the average values of the respective angles were taken.

The test results of the surface gloss of the dried coating or coated article provided by the examples of the present invention and the comparative examples are shown in Table 5.

Preparation of coating composition

Example 1

0.50 g of Dynasylan® HYDROSIL 2926 and 15.22 g of deionized water (DI H ₂ O) were added to a 50 ml glass vial; 0.20 g of 3-glycidoxypropyl was added dropwise during stirring on a magnetic stirrer Trimethoxy decane (GPTMS); after stirring at room temperature for 1 hour, 0.04 g of 3-aminopropyltriethoxydecane (APTES) was added; after stirring for 10 minutes, 0.04 g of methyl ortho-decanoate (0.04 g) was added ( of TMOS); after stirring was continued for 30 minutes, 4.00 grams of 10wt% aqueous TRITON ^TM BG-10 surfactant; after stirring was continued for 15 minutes to obtain yellowish brown slightly cloudy coating compositions.

Example 2-5

The coating compositions of Examples 2 to 5 were prepared in the same manner as in Example 1, in which the kinds and contents of the components included in the coating composition are shown in Table 2.

Example 6

5.02 g of COATOSIL MP 200, 10.20 g of deionized water (DI H ₂ O) and 1.00 g of ethanol (EtOH) were added to a 50 ml glass vial; 0.10 g of 13.30 wt was added dropwise during stirring on a magnetic stirrer. % aqueous solution of nitric acid (HNO ₃ ), adjusted to pH 1-2; after stirring at room temperature for 1 hour, add 2.56 g of 3-glycidoxypropyltrimethoxydecane (GPTMS); continue stirring 1 After the hour, 0.60 g of 3-aminopropyltriethoxydecane (APTES) was added; after stirring for 10 minutes, 0.60 g of methyl ortho-decanoate (TMOS) was added; after stirring for further 30 minutes, a colorless slightly turbid coating was obtained. Layer composition.

Example 7

The coating composition of Example 7 was prepared in the same manner as in Example 1, wherein the kinds and contents of the components included in the coating composition are shown in Table 2.

Comparative Example 1

1.50 g of 3-glycidoxypropyltrimethoxydecane (GPTMS) and 19.00 g of deionized water (DI H ₂ O) were added to a 50 ml glass vial; during the stirring on a magnetic stirrer Add 0.20 g of 5.48 wt.% aqueous solution of hydrochloric acid (HCl) to adjust the pH to 2-3; after stirring at room temperature for 1 hour, add 0.36 g of 3-aminopropyltriethoxydecane (APTES); continue After stirring for 30 minutes, 0.72 g of a 10 wt.% aqueous solution of TRITON BG-10 surfactant was added; after stirring for a further 10 minutes, a slightly yellowish slightly turbid coating composition was obtained.

Comparative Example 2

The coating composition of Comparative Example 2 was prepared in the same manner as in Comparative Example 1, wherein the kinds and contents of the components included in the coating composition are shown in Table 2.

Preparation of coated articles and performance testing

Example 8

The coated article is prepared by a doctor blade method, including the steps of: using a vitrified brick (225 mm × 150 mm × 10 mm) as a substrate for a coated product, first using detergent (white cat brand, available from Shanghai and Huangbai cat limited) Company) clean the surface of the vitrified tile, then rinse it with deionized water, and then blow it dry with compressed air; filter 10 g of the coating composition obtained in Example 1 twice with a 200 mesh sieve; A bar of a knife coater (K303 Multicoater, available from RK Print Coat Instruments) was placed at one end of the vitrified tile, and 5 g of the filtered coating composition was evenly dropped between the bar and the vitrified tile using a dropper. In the gap; at room temperature, the coating composition is scraped on the surface of the vitrified tile by an automatic knife coater; during the blade coating, the wet film thickness of the coating composition is about 12 μm, which is recorded as T-12, such as Table 3 shows that the coated tile was dried at room temperature for 12 hours to obtain a coated article.

The anti-slip properties of the coated articles obtained were tested, and the test results are shown in Table 3; the abrasion resistance and scratch resistance of the coated articles obtained were tested, and the test results are shown in Table 4; the coated articles obtained by the test were tested. Surface gloss, the test results are listed in Table 5.

Example 9-18

A coated article was prepared in the same manner as in Example 8, in which the substrate type, the blade coating condition and the heat treatment conditions of the coated article are shown in Table 3.

As shown in Table 3, if the wet film thickness during the blade coating is 1.5 μm, it is recorded as T-1.5; if the wet film thickness of the coating composition during the blade coating is 3 μm, it is recorded as T-3; The wet film thickness of the coating composition during the coating process was 6 μm, which is denoted as T-6; and if the wet film thickness of the coating composition during the blade coating was 12 μm, it was recorded as T-12.

The anti-slip properties of the coated articles obtained were tested, and the test results are shown in Table 3; the abrasion resistance and scratch resistance of the coated articles obtained were tested, and the test results are shown in Table 4; the coated articles obtained by the test were tested. Surface gloss, the test results are listed in Table 5.

Example 19

The coated article is prepared by dip coating method, including the steps of: using a glass substrate (180 mm×100 mm×3 mm) as a substrate for the coated product, first using detergent (white cat brand, available from Shanghai and Huangbai cat limited) The company cleaned the surface of the glass substrate, then rinsed it with deionized water, and then dried it with compressed air; 200 g of the coating composition obtained in Example 4 was poured into a 400 ml stainless steel tank (150 mm x 150 mm). ×20 mm); the glass substrate is dip coated in the coating composition by an automatic dip coater (SKVDX2S-500, available from KSV NIMA) at room temperature; The immersion speed was 300 mm/min, the immersion time was 1 minute, and the pulling speed was 300 mm/min, which is specifically listed in Table 3. The dip-coated glass substrate was dried by heating in an oven at 100 ° C for 15 minutes, and then taken out, and cooled to room. Warm, a coated article is obtained.

The anti-slip properties of the coated articles obtained were tested, and the test results are shown in Table 3; the abrasion resistance and scratch resistance of the coated articles obtained were tested, and the test results are shown in Table 4; the coated articles obtained by the test were tested. Surface gloss, the test results are listed in Table 5.

Example 20

The coated article is prepared by the wiping method, including the steps of: using 304 stainless steel (200 mm×100 mm×1 mm) as the substrate of the coated product, first using detergent (white cat brand, which can be purchased from Shanghai and Huangbai Cat Co., Ltd. The surface of the 304 stainless steel is cleaned, then rinsed with deionized water, and then blown dry with compressed air; the spunbonded polypropylene non-woven fabric (available from 3M Company) is cut into strips of 50 mm × 20 mm, with drops 6 g of the coating composition obtained in Example 4 was taken out, 3 g was added dropwise to one end of 304 stainless steel, and 3 g was added dropwise to the middle of 304 stainless steel, and the non-woven fabric was pressed by hand on 304 stainless steel. One end of the coating composition was uniformly applied to one end of the uncoated composition; the wiped 304 stainless steel was dried at room temperature for 24 hours to obtain a coated article.

The anti-slip properties of the coated articles obtained were tested, and the test results are shown in Table 3; the abrasion resistance and scratch resistance of the coated articles obtained were tested, and the test results are shown in Table 4; the coated articles obtained by the test were tested. Surface gloss, the test results are listed in Table 5.

Comparative Example 3

The coated article is prepared by a doctor blade method, including the steps of: The vitrified brick (225mm×150mm×10mm) is used as the substrate of the coated product. The surface of the vitrified tile is cleaned with detergent (white cat brand, available from Shanghai and Huangbai Cat Co., Ltd.), and then used. Ionized water was rinsed off and then blown dry with compressed air; 10 g of the coating composition obtained in Comparative Example 1 was filtered twice with a 200-mesh screen; an automatic knife coater (K303 Multicoater, available from RK) The print bar of Print Coat Instruments) is placed at one end of the vitrified tile, and 5 g of the filtered coating composition is evenly dropped on the gap between the bar and the vitrified tile with a dropper; at room temperature, with automatic The coating machine scrapes the coating composition on the surface of the vitrified tile; during the blade coating, the wet film thickness of the coating composition is about 6 μm, which is recorded as T-6, as shown in Table 3; The tiles were dried at room temperature for 24 hours to obtain a coated article.

The anti-slip properties of the coated articles obtained were tested, and the test results are shown in Table 3; the abrasion resistance and scratch resistance of the coated articles obtained were tested, and the test results are shown in Table 4; the coated articles obtained by the test were tested. Surface gloss, the test results are listed in Table 5.

Comparative Example 4

A coated article was prepared in the same manner as in Comparative Example 3, as Comparative Example 4, in which the substrate type, the blade coating condition and the heat treatment conditions of the coated article are shown in Table 3.

The anti-slip properties of the coated articles obtained were tested, and the test results are shown in Table 3; the abrasion resistance and scratch resistance of the coated articles obtained were tested, and the test results are shown in Table 4; the coated articles obtained by the test were tested. Surface gloss, the test results are listed in Table 5.

Comparative Example 5-11

Vitrified bricks, glazed tiles, microcrystalline stone, artificial stone, marble, glass substrate, and stainless steel substrate which were not coated with a dry coating were used as Comparative Examples 5-11, and are specifically shown in Table 3.

The anti-slip properties of the coated articles obtained were tested, and the test results are shown in Table 3; the abrasion resistance and scratch resistance of the coated articles obtained were tested, and the test results are shown in Table 4; the coated articles obtained by the test were tested. Surface gloss, the test results are listed in Table 5.

As can be seen from Table 3, the uncoated dry coating substrates provided in Comparative Examples 5-10 had a wet static friction coefficient of less than 0.6, and thus their slip resistance under wet conditions was poor. According to the coated articles provided in Examples 8-19, the dry static friction coefficient is slightly increased or remains unchanged compared to the uncoated dry coating substrate, and the wet static friction coefficient is lower than that of the uncoated dry coating. The materials have been greatly improved, and both are significantly greater than 0.6, so these coated products have good anti-slip properties in both dry and wet conditions. The uncoated dry coated stainless steel substrate provided in Comparative Example 11 had a dry static coefficient of friction and a wet static friction coefficient of more than 1.0. According to the coated article provided in Example 20, both the dry static friction coefficient and the wet static friction coefficient were slightly improved, so that the coated article had good anti-slip properties under both dry and wet conditions.

As can be seen from Table 4, according to the coated article provided in Comparative Example 3, the number of loops in the abrasion resistance test was 3,500, and the pencil hardness was 3H. According to the coated article provided in Comparative Example 4, the number of loops in the abrasion resistance test was 4000, and the pencil hardness was 3H. According to the coated articles provided in Examples 9-17, 19 and 20, the number of loops in the abrasion resistance test was greatly improved compared with the coated articles provided in Comparative Examples 3-4, and Both were significantly greater than 5000, and the pencil hardness was significantly improved compared with the coated articles provided in Comparative Examples 3-4, and both were significantly greater than 4H, so these coated articles have good abrasion resistance and scratch resistance.

As can be seen from Table 5, the coated articles provided according to Examples 9-16 have substantially the same surface gloss as the substrates of the uncoated dry coating provided in Comparative Examples 3-9. Lifting, so these coated articles have a good appearance.

While the invention has been described with respect to the specific embodiments of the present invention, many modifications, changes, substitutions and changes in the details of the invention are within the scope of the invention as claimed. Therefore, the disclosure described in the detailed description does not impose any limitation on the invention as claimed. The proper scope of the invention should be defined by the scope of the claims and their appropriate legal equivalents. All cited references are hereby incorporated by reference in their entirety.

Claims (24)

A protective coating composition having an anti-slip function, comprising 100% by weight of the total weight of the coating composition, comprising the reaction product of the following reaction components: 1) a first reaction solution, the first reaction solution comprising Reaction product of the following reaction components: 1-30 wt.% of an epoxy functional group-containing decane olefin oligomer and/or polymer A, said epoxy functional group-containing oxirane oligomer and/or polymerization The substance A has a linear, branched or cyclic structure and can be represented by the general formula I: HO-[SiR ¹ (OR ³ )-O] _a -[SiR ² (OR ³ )-O] _b -[Si(OH) ₂ -O] _c -H (I) where 0<a 100;0<b 100;0 c 100; R ¹ and R ² each independently represent one or more of the following groups: 3-glycidoxypropyl, 3-(2,3-dihydroxypropoxy)propyl, 2-(3, 4-epoxycyclohexyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ represents a hydrogen atom or one or more of the following groups: methyl, ethyl, n-propyl, Isopropyl, n-butyl, secondary butyl, isobutyl and tert-butyl; 1-15 wt.% of a decyl compound B containing an epoxy functional group, the octane compound B containing an epoxy functional group may Expressed by the general formula II: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) wherein 0 d 2; R ⁴ represents one or more of the following groups: 3-glycidoxypropyl, 3-(2,3-dihydroxypropoxy)propyl, 2-(3,4-epoxy ring Ethyl)ethyl and 2-(3,4-dihydroxycyclohexyl)ethyl; R ³ represents a hydrogen atom or one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl a base, a secondary butyl group, an isobutyl group, and a tertiary butyl group; the weight of the epoxy functional group-containing fluorene oxide oligomer and/or polymer A and the epoxy group-containing decane compound B a ratio of at least 1:1; 45-96 wt.% water; and an acid; the first reaction solution has a pH of less than or equal to 5; 2) 0.2-5 wt.% of an amino-functional decane compound C, The decane compound C containing an amino functional group can be represented by the general formula III: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (III) where 0 e 1;0 f 1;1 g 6;0 h 1;0 i 6;0 j 2;0 k 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl, alkenyl or benzyl group having a carbon number of 1-6; and R ⁶ represents a linear, branched or cyclic group having a carbon number of 1-6. An alkyl or alkenyl group; R ³ represents a hydrogen atom or one or more of the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl and tert-butyl 3) 0.2-5 wt.% of n-decanoate, which can be represented by the general formula IV: Si(OR) ₄ (IV) wherein R represents one or more of the following groups: methyl , ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl and tert-butyl. The coating composition according to claim 1, wherein the epoxy group-containing siloxane oxide oligomer and/or polymer A has the formula: HO-[SiR ¹ (OR ³ ) -O] _a -[SiR ² (OR ³ )-O] _b -[Si(OH) ₂ -O] _c -H (I) where 0<a 20;0<b 20;0 c 20; R ¹ and R ² each independently represent one or more of the following groups: 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl; R ³ represents a hydrogen atom. Or one or more of the following groups: methyl, ethyl, n-propyl and isopropyl. The coating composition of claim 1, wherein the epoxy functional group-containing siloxane oxide oligomer and/or polymer A is present in an amount of from 4.5 to 25 wt.%, in the coating The total weight of the composition is based on 100 wt.%. The coating composition according to claim 1, wherein the epoxy group-containing decane compound B has the formula: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) wherein 0 d 2; R ⁴ represents one or more of the following groups: 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl; R ³ represents a hydrogen atom or one of the following groups Or a variety of: methyl, ethyl, n-propyl and isopropyl. The coating composition according to claim 4, wherein the epoxy group-containing decane compound B comprises one or more of the following groups: 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidyloxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3 - glycidyloxypropylethyldimethoxydecane, 3-glycidyloxypropylethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Alkane and 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane. The coating composition according to claim 1, wherein the epoxy group-containing decane compound B is contained in an amount of from 3 to 13% by weight, based on 100% by weight of the total weight of the coating composition. meter. The coating composition according to claim 1, wherein the epoxy functional group-containing fluorene oxide oligomer and/or polymer A and the epoxy group-containing decane compound B are used. The ratio is at least 1.2:1. The coating composition of claim 1, wherein the acid is an inorganic acid or an organic acid, and the inorganic acid comprises one or more of the group consisting of hydrochloric acid, nitric acid, and phosphoric acid; One or more of the following groups: formic acid and acetic acid. The coating composition according to claim 1, wherein the amino group-containing decane compound C has the formula: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (III) where 0 e 1;0 f 1;1 g 6;0 h 1;0 i 6;0 j 2;0 k 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl or alkenyl group having a carbon number of from 1 to 4; and R ⁶ represents a linear, branched or cyclic alkyl group having a carbon number of from 1 to 4; R ³ represents a hydrogen atom or one or more of the following groups: methyl, ethyl, n-propyl and isopropyl. The coating composition of claim 9, wherein the amino-functional decane compound C comprises one or more of the group consisting of 3-aminopropyltrimethoxydecane, 3-aminopropyltri Ethoxy decane, 3-aminopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, 3-aminopropylethyldimethoxydecane, 3-aminopropyl B Diethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxydecane, N-(2-Ammonia Ethyl)-3-aminopropylethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylethyldiethoxydecane, 3-[2-(2-amino-ethyl) Ethylamino)ethylamino]propyltrimethoxydecane, 3-[2-(2-aminoethylamino)ethylamino]propyltriethoxydecane, 3-[2-(2-aminoethyl) Amino)ethylamino]propylmethyldimethoxydecane, 3-[2-(2-aminoethylamino)ethylamino]propylmethyldiethoxydecane, 3-(N,N- Dimethylaminopropyl)-aminopropyltrimethoxy Decane, 3-(N,N-dimethylaminopropyl)-aminopropyltriethoxydecane, 3-(N,N-dimethylaminopropyl)-aminopropylmethyldimethoxy Decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N,N-dimethyl-3-aminopropyltrimethoxydecane , N,N-Diethyl-3-aminopropyltrimethoxydecane, N,N-diethyl-3-aminopropyltriethoxydecane, N-ethyl-3-trimethoxyformane Benzyl-2-methylpropylamine, N-[3-(trimethoxyindolyl)propyl]-n-butylamine, bis[(3-trimethoxyindolyl)-propyl]amine, bis[(3-tri-B) Oxyfluorenyl)-propyl]amine. The coating composition of claim 1, wherein the n-decanoate has the formula: Si(OR) ₄ (IV) wherein R represents one or more of the following groups: methyl, Ethyl, n-propyl and isopropyl. The coating composition of claim 11, wherein the n-nonanoic acid ester comprises one or more of the group consisting of methyl n-decanoate, ethyl n-decanoate, n-propyl n-decanoate and a positive Isopropyl citrate. The coating composition of claim 1, wherein the coating composition further comprises 0.01 to 10 wt.% of surface epoxy-modified ceria particles, to total of the coating composition. Re-press 100wt.%. The coating composition of claim 13, wherein the surface epoxy-modified cerium oxide particles have an average particle diameter of less than or equal to 15 nm. The coating composition of claim 1, wherein the coating composition further comprises 0.01 to 5 wt.% of an organic solvent, based on 100 wt.% of the total weight of the coating composition. The organic solvent is miscible with water and comprises one or more of the following groups: alcohols, ketones, esters and ethers having a molecular weight of less than 250. The coating composition of claim 1, wherein the coating composition further comprises 0.01-2 wt.% of an additive, based on 100 wt.% of the total weight of the coating composition. Additives include one or more of the following groups: detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymeric binders. The coating composition of claim 16, wherein the surfactant is a nonionic surfactant, including one or more of the group consisting of polyoxyethylene type nonionic surfactants, and polyol types. Nonionic surfactant, alkyl alcohol amide type nonionic surfactant, fluorocarbon type A nonionic surfactant, an organic quinoid nonionic surfactant, and a modified organic quinoid nonionic surfactant. A coated article comprising a substrate and a dried coating applied to the substrate, the dried coating comprising applying the coating composition of any one of claims 1-17 to The surface of the substrate is dried to obtain a coating. The coated article of claim 18, wherein the substrate comprises one or more of the group consisting of a ceramic tile substrate, a glass substrate, a stone substrate, and a metal substrate. The coated article of claim 19, wherein the ceramic tile substrate comprises one or more of the group consisting of: vitrified tiles, glazed tiles, antique tiles, microcrystalline stones, polished tiles, and imitation granite tiles. And imitation marble tiles. The coated article of claim 19, wherein the stone substrate comprises one or more of the group consisting of marble, granite, and artificial stone. The coated article of claim 19, wherein the metal substrate comprises one or more of the group consisting of a stainless steel substrate, a cold rolled steel substrate, a galvanized steel substrate, an aluminum substrate, and an aluminum alloy. Substrate. A method of preparing a coated article, comprising the step of applying a coating composition according to any one of claims 1 to 17 on the surface of the substrate to form a wet coating on the surface of the substrate. The layer composition liquid film is dried to obtain a dried coating which adheres to the surface of the substrate. The preparation method according to claim 23, wherein the coating composition is applied to the surface of the substrate by the following methods: a doctor blade method, a wipe coating method, a brush coating method, a dip coating method, and a spray coating method. .