CN108300299B

CN108300299B - Protective coating composition with anti-skid function, coated product and preparation method of coated product

Info

Publication number: CN108300299B
Application number: CN201610865606.0A
Authority: CN
Inventors: 银龙; 谢文祥
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2016-09-29
Filing date: 2016-09-29
Publication date: 2020-04-28
Anticipated expiration: 2036-09-29
Also published as: CN108300299A

Abstract

The invention relates to a protective coating composition with anti-slip function, comprising the reaction product of the following reaction components, based on 100 wt.% of the total weight of the coating composition: 1) a first reaction solution comprising the reaction product of the following reaction components: 1-30 wt% of siloxane oligomer and/or polymer A containing epoxy functional groups and having a linear, branched or cyclic structure, 1-15 wt% of silane compound B containing epoxy functional groups, and the weight ratio of the siloxane oligomer and/or polymer A containing epoxy functional groups to the silane compound B containing epoxy functional groups is at least 1: 1; 45-96 wt% water; and an acid; the pH value of the first reaction solution is less than or equal to 5; 2)0.2 to 5 wt.% of silane compounds C containing amino functional groups, 3)0.2 to 5 wt.% of orthosilicate.

Description

Protective coating composition with anti-skid function, coated product and preparation method of coated product

Technical Field

The invention relates to a protective coating composition with an anti-skid function, a coated product and a preparation method thereof.

Background

The surfaces of ceramic tile base materials, glass base materials, stone base materials and metal base materials sold in the building material market can become wet and slippery after meeting water, and safety accidents such as people slipping, falling and injury are easily caused. Therefore, it is necessary to perform an anti-slip treatment on the surface of the base material.

One of the common anti-skidding processing methods is to coat an anti-skidding coating on the surface of a base material so as to improve the friction force of the surface of the base material, increase the friction coefficient to a safe level and achieve the anti-skidding effect, thereby reducing the occurrence of accidents such as falling injury of personnel.

Currently, an anti-slip coating generally uses alkyd resin, chlorinated rubber, phenolic resin, epoxy resin or polyurethane resin as a film-forming resin, and silica sand, silicon carbide, titanium oxide, alumina or rubber particles and other anti-slip granules are filled in the film-forming resin. The anti-skid granules have irregular shapes and protrude out of the surface of the coating, so that the roughness and the friction force of the surface can be increased, and the sliding property of people or other objects on the surface is reduced, thereby achieving the aim of skid resistance.

In recent years, it has been found that the demand for non-slip properties can be satisfied by a special coating layer, not by filling non-slip particles. CN104926369 (silver dragon, etc.) discloses an anti-slip coating applied to ceramic tile substrate, comprising a first silane and a solvent, wherein the first silane is epoxy silane or orthosilicate ester, and wherein the solvent is selected from water or alcohol. However, the anti-slip coating cannot meet the requirements of higher wear resistance and scratch resistance. In order to meet the higher wear and scratch resistance requirements of some applications, it is necessary to further improve the wear and scratch resistance of the anti-slip coating.

Both US20100209719 and US20100015339 formulations disclose hydrolysis products of siloxanes containing epoxy functional groups, which function to react with other components to achieve a preservative function.

Disclosure of Invention

The invention aims to provide a protective coating composition with an anti-skid function so as to meet the requirement that a dried coating and a coated product which are further prepared by using the protective coating composition are anti-skid under a wet and slippery environment. The dry coating and the coated article have both good abrasion resistance and scratch resistance, and can serve to permanently protect the substrate.

According to one aspect of the present invention, there is provided a protective coating composition having an anti-slip function comprising the reaction product of the following reaction components, based on 100 wt.% of the total weight of the coating composition: 1) a first reaction solution comprising the reaction product of the following reaction components: 1-30 wt% of siloxane oligomer and/or polymer A containing epoxy functional group, the siloxane oligomer and/or polymer A containing epoxy functional group has linear, branched or cyclic structure and can be represented by general formula I: HO- [ SiR¹(OR³)-O]_a-[SiR²(OR³)-O]_b-[Si(OH)₂-O]_c-H (I), wherein 0<a≤100；0<b≤100；0≤c≤100；R¹And R²Each independently represents an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group comprising one or more of the following groups: 3-glycidyloxypropyl, 3- (2, 3-dihydroxypropoxy) propyl, 2- (3, 4-epoxycyclohexyl) ethyl and 2- (3, 4-dihydroxycyclohexyl) ethyl;R³represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl; 1 to 15 wt% of an epoxy functional group-containing silane compound B, which may be represented by the general formula ii: r⁴-SiR³ _d(OR³)_3-d(II), wherein d is more than or equal to 0 and less than or equal to 2; r⁴Represents 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 group, 3- (2, 3-dihydroxypropoxy) propyl group, 2- (3, 4-epoxycyclohexyl) ethyl group and 2- (3, 4-dihydroxycyclohexyl) ethyl group; r³Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl; the weight ratio of the siloxane oligomer and/or polymer A containing epoxy functional groups to the silane compound B containing epoxy functional groups is at least 1: 1; 45-96 wt% water; and an acid; the pH value of the first reaction solution is less than or equal to 5; 2)0.2 to 5% by weight of an amino-functional silane compound C, which can be represented by the general formula III: [ (R)³O)_3-jR³ _jSi-R⁶]_2-eR⁵ _eR⁵ _fN-[(CH₂)_g-NR⁵ _hH_(1-h)]_i-R⁶-SiR³ _k(OR³)_3-k(III), wherein e is more than or equal to 0 and less than or equal to 1; f is more than or equal to 0 and less than or equal to 1; g is more than or equal to 1 and less than or equal to 6; h is more than or equal to 0 and less than or equal to 1; i is more than or equal to 0 and less than or equal to 6; j is more than or equal to 0 and less than or equal to 2; k is more than or equal to 0 and less than or equal to 2; r⁵Represents a hydrogen atom or a linear, branched or cyclic alkyl, alkenyl or benzyl group having 1 to 6 carbon atoms; r⁶Represents a linear, branched or cyclic alkyl or alkenyl group having 1 to 6 carbon atoms; r³Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl; 3)0.2 to 5 wt% of an orthosilicate ester, said orthosilicate ester beingCan be represented by the general formula IV: si (OR)₄(IV), wherein R represents an alkyl group with a carbon number of 1-4, and comprises one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

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

According to another aspect of the present invention, there is provided a method of making a coated article comprising the steps of: applying the coating composition to the surface of the substrate to form a wet coating composition film on the surface of the substrate, and drying the wet coating composition film to obtain a dried coating, wherein the dried coating is attached to the surface of the substrate.

Detailed Description

It is to be understood that other various embodiments can be devised and modified by those skilled in the art in light of the teachings herein without departing from the scope or spirit of the invention. The following detailed description is, therefore, not to be taken in a limiting sense.

Unless otherwise indicated, all numbers expressing quantities and physical and chemical properties used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1, 2,3, 4, and 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.

Coating composition

The invention provides a protective coating composition with anti-skid function, which comprises the reaction product of the following reaction components in 100 wt% based on the total weight of the coating composition:

1) a first reaction solution comprising the reaction product of the following reaction components:

1-30 wt% of siloxane oligomer and/or polymer A containing epoxy functional group, the siloxane oligomer and/or polymer A containing epoxy functional group has linear, branched or cyclic structure and can be represented by general formula I:

HO-[SiR¹(OR³)-O]_a-[SiR²(OR³)-O]_b-[Si(OH)₂-O]_c-H (Ⅰ)

wherein, 0<a≤100；0<b≤100；0≤c≤100；R¹And R²Each independently represents an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group comprising one or more of the following groups: 3-glycidyloxypropyl, 3- (2, 3-dihydroxypropoxy) propyl, 2- (3, 4-epoxycyclohexyl) ethyl and 2- (3, 4-dihydroxycyclohexyl) ethyl; r³Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl;

1 to 15 wt% of an epoxy functional group-containing silane compound B, which may be represented by the general formula ii:

R⁴-SiR³ _d(OR³)_3-d(Ⅱ)

wherein d is more than or equal to 0 and less than or equal to 2; r⁴Represents an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyloxypropyl, 3- (2, 3-dihydroxypropoxy) propyl, 2- (3, 4-epoxycyclohexyl) ethyl and 2- (3, 4-dihydroxycyclohexyl) ethyl; r³Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl; said compound containing epoxy functional groupsThe weight ratio of siloxane oligomer and/or polymer A to the silane compound B containing epoxy functional groups is at least 1: 1;

45-96 wt% water; and

an acid; the pH value of the first reaction solution is less than or equal to 5;

2)0.2 to 5% by weight of an amino-functional silane compound C, which can be represented by the general formula III:

[(R³O)_3-jR³ _jSi-R⁶]_2-eR⁵ _eR⁵ _fN-[(CH₂)_g-NR⁵ _hH_(1-h)]_i-R⁶-SiR³ _k(OR³)_3-k(Ⅲ)

wherein e is more than or equal to 0 and less than or equal to 1; f is more than or equal to 0 and less than or equal to 1; g is more than or equal to 1 and less than or equal to 6; h is more than or equal to 0 and less than or equal to 1; i is more than or equal to 0 and less than or equal to 6; j is more than or equal to 0 and less than or equal to 2; k is more than or equal to 0 and less than or equal to 2; r⁵Represents a hydrogen atom or a linear, branched or cyclic alkyl, alkenyl or benzyl group having 1 to 6 carbon atoms; r⁶Represents a linear, branched or cyclic alkyl or alkenyl group having 1 to 6 carbon atoms; r³Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl;

3)0.2 to 5 wt% of an orthosilicate, which can be represented by formula iv:

Si(OR)₄(Ⅳ)

wherein R represents alkyl with carbon number of 1-4, and comprises one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

The siloxane oligomer and/or polymer a containing epoxy functional groups preferably has the general formula:

HO-[SiR¹(OR³)-O]_a-[SiR²(OR³)-O]_b-[Si(OH)₂-O]_c-H (Ⅰ)

wherein, 0<a≤20；0<b≤20；0≤c≤20；R¹And R²Each independently represents an organic group containing at least one unhydrolyzed epoxy functional group comprising one or more of the following groups: 3-glycidoxypropyl and 2- (3, 4-epoxycyclohexyl) ethyl; r³Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

The content of the siloxane oligomer and/or polymer A containing epoxy functional groups is from 1 to 30% by weight, preferably from 1 to 25% by weight, particularly preferably from 4.5 to 25% by weight, based on the total weight of the coating composition, based on 100% by weight. If the content of the siloxane oligomer and/or polymer a having an epoxy functional group is less than 1 wt%, it may be difficult to form a dried coating layer of sufficient thickness on the surface of the substrate so as not to achieve the anti-slip property and the abrasion resistance property of the coated article provided by the present invention. If the content of the epoxy functional group-containing siloxane oligomer and/or polymer A is more than 30 wt%, the reaction speed of the first reaction solution with the amino functional group-containing silane compound C and orthosilicate may be too fast, and the appearance of the resulting dried coating layer may have more defects according thereto, resulting in a coated article having a noticeable defect in appearance.

The general formula of the silane compound B containing an epoxy functional group is preferably:

R⁴-SiR³ _d(OR³)_3-d(Ⅱ)

wherein d is more than or equal to 0 and less than or equal to 2; r⁴Represents an organic group containing at least one unhydrolyzed epoxy functional group comprising one or more of the following groups: 3-glycidoxypropyl and 2- (3, 4-epoxycyclohexyl) ethyl; r³Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

The silane compound B containing epoxy functional groups comprises one or more of the following groups: 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropylethyldimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane.

The content of the silane compound B containing an epoxy functional group is 1 to 15 wt%, preferably 1 to 13 wt%, particularly preferably 3 to 13 wt%, based on the total weight of the coating composition, based on 100 wt%. If the content of the silane compound B containing an epoxy functional group is less than 1 wt%, the first reaction solution reacts with the silane compound C containing an amino functional group and the orthosilicate to obtain a coating composition, and the dried coating and the coated article further prepared using the coating composition may have poor anti-slip properties, so that the anti-slip properties possessed by the coated article provided by the present invention may not be achieved. If the content of the epoxy functional group-containing silane compound B is more than 15 wt%, the reaction speed of the first reaction solution with the amino functional group-containing silane compound C and the orthosilicate may be too fast, and the appearance of the resulting dried coating layer may have more defects according thereto, resulting in a coated article having a noticeable defect in appearance.

The weight ratio of the epoxy-functional siloxane oligomer and/or polymer A to the epoxy-functional silane compound B is at least 1:1, preferably 1.2:1, particularly preferably 1.5: 1. If the weight ratio of the epoxy-functional siloxane oligomer and/or polymer A to the epoxy-functional silane compound B is less than 1:1, precipitation occurs after mixing the first reaction solution with the amino-functional silane compound C and the orthosilicate, and the dry coating or coated article provided by the present invention cannot be further prepared using it.

The acid may be an inorganic acid or an organic acid. The inorganic acid comprises one or more of the following groups: hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, hydrochloric acid and phosphoric acid being particularly preferred. The organic acid comprises one or more of the following groups: 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 more than 5, when it reacts with the silane compound C having an amino functional group and the orthosilicate to obtain a coating composition, the dried coating and the coated article further prepared using the coating composition may have poor anti-slip properties, abrasion resistance and scratch resistance, so that the anti-slip properties, abrasion resistance and scratch resistance of the coated article provided by the present invention may not be achieved.

The general formula of the silane compound C containing an amino functional group is preferably:

wherein e is more than or equal to 0 and less than or equal to 1; f is more than or equal to 0 and less than or equal to 1; g is more than or equal to 1 and less than or equal to 6; h is more than or equal to 0 and less than or equal to 1; i is more than or equal to 0 and less than or equal to 6; j is more than or equal to 0 and less than or equal to 2; k is more than or equal to 0 and less than or equal to 2; r⁵Represents a hydrogen atom or a linear, branched or cyclic alkyl or alkenyl group having 1 to 4 carbon atoms; r⁶Represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms; r³Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

The silane compound C containing an amino functional group includes one or more of the following groups: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, N- (3-aminopropyl-ethyldiethoxysilane, N-propylmethyldimethoxysilane, N-propylmethyldiethoxysilane, N-, 3- [2- (2-aminoethylamino) ethylamino ] propyltrimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propyltriethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propylmethyldimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propylmethyldiethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltrimethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-isopropylaminopropyltrimethoxysilane, N-isopropylaminoethyldimethoxysilane, N-isopropylaminoethyltrimethoxysilane, N-isopropylaminoethyldimethoxysilane, N, N-phenyl-3-aminopropyltriethoxysilane, N-dimethyl-3-aminopropyltrimethoxysilane, N-diethyl-3-aminopropyltriethoxysilane, N-ethyl-3-trimethoxysilyl-2-methylpropylamine, N- [3- (trimethylsilyl) propyl ] N-butylamine, bis [ (3-trimethoxysilyl) -propyl ] amine, bis [ (3-triethoxysilyl) -propyl ] amine.

The content of the amino-functional silane compound C is 0.2 to 5 wt.%, preferably 0.2 to 3 wt.%, particularly preferably 0.8 to 3 wt.%, based on 100 wt.% of the total weight of the coating composition. If the content of the silane compound C having an amino functional group is less than 0.2 wt%, when it reacts with the first reaction solution and the orthosilicate to obtain a coating composition, it may be difficult to completely cure the coating composition applied on the surface of the substrate, and the anti-slip property, wear resistance and scratch resistance of the further obtained dried coating and coated article may be poor, so that the anti-slip property, wear resistance and scratch resistance of the coated article provided by the present invention may not be achieved. If the content of the silane compound C having an amino functional group is more than 5 wt%, when it reacts with the first reaction solution and the orthosilicate to obtain a coating composition, the dried coating and the coated article further prepared using the coating composition may have poor anti-slip property, wear resistance and scratch resistance, so that the anti-slip property, wear resistance and scratch resistance of the coated article provided by the present invention may not be achieved.

The orthosilicate is preferably of the formula:

Si(OR)₄(Ⅳ)

wherein R represents alkyl with carbon number of 1-3, and comprises one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

The orthosilicate includes one or more of the following group: methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate and isopropyl orthosilicate.

The orthosilicate is present in an amount of 0.2 to 5 wt.%, preferably 0.2 to 3 wt.%, particularly preferably 0.7 to 3 wt.%, based on 100 wt.% of the total weight of the coating composition. If the content of the orthosilicate is less than 0.2 wt%, when it reacts with the first reaction solution and the silane compound C having an amino functional group to obtain a coating composition, the dried coating and the coated article further prepared using the coating composition may have insufficient anti-slip properties to achieve the anti-slip properties possessed by the coated article provided by the present invention. If the content of the orthosilicate is more than 5 wt%, when it reacts with the first reaction solution and the silane compound C having an amino functional group to obtain a coating composition, the bonding force of the coating composition applied to the surface of the substrate may be poor, and further, the wear resistance and scratch resistance of the dried coating and the coated article may be poor, so that the wear resistance and scratch resistance of the coated article provided by the present invention may not be achieved.

The coating composition of the present invention may further comprise surface epoxy-modified silica particles. The surface epoxy modified silica particles can further improve the wear resistance and scratch resistance of the coated product provided by the invention. The surface epoxy-modified silica particles may be surface epoxy-modified silica particles having a single average particle diameter, or may be a combination of surface epoxy-modified silica particles having two or more average particle diameters. The particle size as used herein and in the claims refers to the length of the longest axis of the particle. Surface epoxy modification as used herein and in the claims means that the reactive groups (e.g. SiOH groups) inherent to the surface of the silica particles are replaced by organic groups bearing at least one epoxy functional group. The surface epoxy-modified silica particles have an average particle diameter of 50nm or less, preferably 20nm or less, and particularly preferably 15nm or less. Examples of commercially available surface epoxy-modified silica sols include surface epoxy-modified silica sols available as Bindzil from Akzo Nobel in water or in aqueous alcohol solutions. One useful surface epoxy-modified silica sol is a surface epoxy-modified silica sol having an average particle size of 7nm and a nominal solids content of 28 wt.% available as Bindzil CC301 from akzo nobel corporation. Other commercially available surface epoxy-modified silica sols that may be used include surface epoxy-modified silica sols available from Akzo Nobel as Bindzil CC151 HS and Bindzil CC 401.

The surface epoxy-modified silica particles are present in an amount of 0.01 to 10 wt.%, preferably 0.5 to 10 wt.%, particularly preferably 0.5 to 5 wt.%, based on the total weight of the coating composition, referred to 100 wt.%. If the content of the surface epoxy-modified silica particles is more than 10% by weight, when it is reacted with the first reaction solution, the amino functional group-containing silane compound C and the orthosilicate to obtain the coating composition, the appearance of the dried coating layer further prepared using the coating composition may be so poor as not to achieve the good appearance provided by 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 following group: 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, sec-butanol, tert-butanol, ethylene glycol, propylene glycol, glycerol and triethylene glycol. The ketones are preferably acetone and butanone. The esters are 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 ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether.

The organic solvent is present in an amount of 0.01 to 5 wt.%, preferably 0.01 to 3 wt.%, particularly preferably 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% by weight, when it reacts with the first reaction solution, the amino functional group-containing silane compound C and the orthosilicate to obtain a coating composition, the dried coating and the coated article obtained by further preparing using the coating composition may have insufficient anti-slip properties so as not to achieve the anti-slip properties possessed by the coated article provided by the present invention.

The coating composition of the present invention may further comprise additives. The additives include one or more of the following groups: detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders. The surfactant is a nonionic surfactant, and can improve the wettability of the coating composition on the surface of the base material. The nonionic surfactant may be selected from one or more of the following groups: polyoxyethylene type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylolamide type nonionic surfactant, fluorocarbon type nonionic surfactant, silicone type nonionic surfactant and modified silicone type nonionic surfactant.

The nonionic surfactant is contained in an amount of 0.01 to 2 wt%, preferably 0.01 to 1 wt%, particularly preferably 0.05 to 0.5 wt%, based on the total weight of the coating composition, based on 100 wt%. If the content of the nonionic surfactant is more than 2% by weight, when it reacts with the first reaction solution, the amino functional group-containing silane compound C and the orthosilicate to obtain a coating composition, the dried coating and the coated article obtained by further preparing using the coating composition may have insufficient anti-slip properties so as not to achieve the anti-slip properties possessed by the coated article provided by the present invention.

Coated articles

The present invention provides coated articles comprising a substrate and a dried coating applied to the substrate. The substrate comprises one or more of the following group: ceramic tile substrates, glass substrates, stone substrates, and metal substrates. "ceramic tiles" as used herein and in the claims is suitable for including ceramic materials made from refractory clays, bricks, concrete, ceramics, marble, limestone and other stones or slates. The ceramic tile substrate comprises one or more of the following groups: vitrified tiles, glazed tiles, archaized tiles, microlites, polished tiles, granite-like tiles, and marble-like tiles. The stone substrate comprises one or more of the following groups: marble, granite, and artificial stone. The metal substrate comprises one or more of the following group: stainless steel substrates, cold rolled steel substrates, galvanized steel substrates, aluminum substrates, and aluminum alloy substrates.

The coated article includes 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 present specification.

The coated article can greatly improve the anti-slip performance of the substrate under wet slip conditions. The coated article may have any suitable thickness as desired, and the thickness of the coated article may be from 100nm to 100 μm, or from 200nm to 50 μm, or from 500nm to 20 μm.

Method for preparing coated articles

The present invention provides a method of making a coated article comprising the steps of: applying the coating composition provided by the invention on the surface of the substrate to form a wet coating composition liquid film on the surface of the substrate, and drying the wet coating composition liquid film to obtain a dry coating, wherein the dry coating is attached to the surface of the substrate.

For a description of the coating composition, substrate and coated article, see the "coating composition" and "coated article" sections of the present specification.

The coating composition may be applied to the surface of the substrate by methods known in the art, preferably one or more of the following: blade coating, wiping, brushing, dipping and spraying.

The anti-slip fluid may be dried using suitable drying methods known in the art and may be carried out at ambient or elevated temperatures, for example, the temperature may be 20-180 c, alternatively 20-150 c, alternatively 20-120 c.

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

Preferred embodiment 1 is a protective coating composition having a slip-preventing function comprising the reaction product of the following reaction components, based on 100 wt% of the total weight of the coating composition:

HO-[SiR¹(OR³)-O]_a-[SiR²(OR³)-O]_b-[Si(OH)₂-O]_c-H (Ⅰ)

R⁴-SiR³ _d(OR³)_3-d(Ⅱ)

wherein d is more than or equal to 0 and less than or equal to 2; r⁴Represents an organic group containing at least one unhydrolyzed and/or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyloxypropyl, 3- (2, 3-dihydroxypropoxy) propyl, 2- (3, 4-epoxycyclohexyl) ethyl and 2- (3, 4-dihydroxycyclohexyl) ethyl; r³Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl; the weight ratio of the siloxane oligomer and/or polymer A containing epoxy functional groups to the silane compound B containing epoxy functional groups is at least 1: 1;

45-96 wt% water; and

3)0.2 to 5 wt% of an orthosilicate, which can be represented by formula iv:

Si(OR)₄(Ⅳ)

Preferred embodiment 2 is the coating composition of preferred embodiment 1, wherein the epoxy-functional siloxane oligomer and/or polymer a has the formula:

HO-[SiR¹(OR³)-O]_a-[SiR²(OR³)-O]_b-[Si(OH)₂-O]_c-H (Ⅰ)

Preferred embodiment 3 is the coating composition of preferred embodiment 1, wherein the content of the siloxane oligomer and/or polymer a having an epoxy functional group is 4.5 to 25 wt%.

Preferred embodiment 4 is the coating composition according to preferred embodiment 1, wherein the epoxy functional group-containing silane compound B has the general formula:

R⁴-SiR³ _d(OR³)_3-d(Ⅱ)

Preferred embodiment 5 is the coating composition of preferred embodiment 4, wherein the silane compound B having an epoxy functional group comprises one or more of the following groups: 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropylethyldimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane.

Preferred embodiment 6 is the coating composition of preferred embodiment 1, wherein the content of the silane compound B having an epoxy functional group is 3 to 13 wt%.

Preferred embodiment 7 is the coating composition of preferred embodiment 1, wherein the weight ratio of the epoxy-functional siloxane oligomer and/or polymer a to the epoxy-functional silane compound B is at least 1.2: 1.

Preferred embodiment 8 is a coating composition as described in preferred embodiment 1 wherein the acid is an inorganic or organic acid comprising one or more of the following group: hydrochloric acid, nitric acid and phosphoric acid; the organic acid comprises one or more of the following groups: formic acid and acetic acid.

Preferred embodiment 9 is the coating composition of preferred embodiment 1, wherein the amino functional group-containing silane compound C has the general formula:

wherein e is more than or equal to 0 and less than or equal to 1; f is more than or equal to 0 and less than or equal to 1; g is more than or equal to 1 and less than or equal to 6; h is more than or equal to 0 and less than or equal to 1; i is more than or equal to 0 and less than or equal to 6; j is more than or equal to 0 and less than or equal to 2; k is more than or equal to 0 and less than or equal to 2; r⁵Represents a hydrogen atom or a linear, branched or cyclic alkyl or alkenyl group having 1 to 4 carbon atoms; r⁶Represents a linear, branched or cyclic carbon number of 1 to 4Alkyl groups of (a); r³Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl and isopropyl.

Preferred embodiment 10 is the coating composition of preferred embodiment 9, wherein the silane compound C having an amino functional group comprises one or more of the following group: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, N- (3-aminopropyl-ethyldiethoxysilane, N-propylmethyldimethoxysilane, N-propylmethyldiethoxysilane, N-, 3- [2- (2-aminoethylamino) ethylamino ] propyltrimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propyltriethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propylmethyldimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propylmethyldiethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltrimethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-isopropylaminopropyltrimethoxysilane, N-isopropylaminoethyldimethoxysilane, N-isopropylaminoethyltrimethoxysilane, N-isopropylaminoethyldimethoxysilane, N, N-phenyl-3-aminopropyltriethoxysilane, N-dimethyl-3-aminopropyltrimethoxysilane, N-diethyl-3-aminopropyltriethoxysilane, N-ethyl-3-trimethoxysilyl-2-methylpropylamine, N- [3- (trimethylsilyl) propyl ] N-butylamine, bis [ (3-trimethoxysilyl) -propyl ] amine, bis [ (3-triethoxysilyl) -propyl ] amine.

Preferred embodiment 11 is the coating composition of preferred embodiment 1, wherein the orthosilicate has the formula:

Si(OR)₄(Ⅳ)

Preferred embodiment 12 is a coating composition as described in preferred embodiment 11, wherein the orthosilicate comprises one or more of the group consisting of: methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate and isopropyl orthosilicate.

Preferred embodiment 13 is a coating composition as described in preferred embodiment 1, wherein the coating composition further comprises 0.01 to 10 wt% of surface epoxy modified silica particles, based on the total weight of the coating composition taken as 100 wt%.

Preferred embodiment 14 is the coating composition of preferred embodiment 13, wherein the surface epoxy modified silica particles have an average particle size of less than or equal to 15 nm.

Preferred embodiment 15 is a coating composition as in preferred embodiment 1, wherein the coating composition further comprises 0.01 to 5 wt% of an organic solvent, the organic solvent being miscible with water and comprising one or more of the following group, based on the total weight of the coating composition taken as 100 wt%: alcohols, ketones, esters and ethers having a molecular weight of less than 250.

Preferred embodiment 16 is a coating composition as set forth in preferred embodiment 1 wherein said coating composition further comprises from 0.01 to 2 weight percent of an additive, said additive comprising one or more of the following group, based upon the total weight of said coating composition taken as 100 weight percent: detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders.

Preferred embodiment 17 is a coating composition as described in preferred embodiment 16 wherein the surfactant is a nonionic surfactant comprising one or more of the following group: polyoxyethylene type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylolamide type nonionic surfactant, fluorocarbon type nonionic surfactant, silicone type nonionic surfactant and modified silicone 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 a coating obtained by applying the coating composition of preferred embodiments 1-17 to the surface of the substrate and drying.

Preferred embodiment 19 is a coated article as in 18, wherein the substrate comprises one or more of the following group: ceramic tile substrates, glass substrates, stone substrates, and metal substrates.

Preferred embodiment 20 is a coated article as described in preferred embodiment 19, wherein the ceramic tile substrate comprises one or more of the following group: vitrified tiles, glazed tiles, archaized tiles, microlites, polished tiles, granite-like tiles, and marble-like tiles.

Preferred embodiment 21 is a coated article as in preferred embodiment 19, wherein the stone substrate comprises one or more of the following group: marble, granite, and artificial stone.

Preferred embodiment 22 is a coated article as in preferred embodiment 19, wherein the metal substrate comprises one or more of the following group: stainless steel substrates, cold rolled steel substrates, galvanized steel substrates, aluminum substrates, and aluminum alloy substrates.

Preferred embodiment 23 is a method of making a coated article comprising the steps of: the coating composition according to preferred embodiments 1 to 17 is applied to the surface of the substrate to form a wet coating composition liquid film on the surface of the substrate, and the wet coating composition liquid film is dried to obtain a dried coating layer, which is attached to the surface of the substrate.

Preferred embodiment 24 is a method of making as described in preferred embodiment 23 wherein the coating composition is applied to the surface of the substrate by: blade coating, wiping, brushing, dipping and spraying.

Examples

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

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

Table 1 raw materials used in examples and comparative examples

The dry coatings or coated articles provided in the examples and comparative examples were evaluated for their non-slip properties primarily by dry and wet static coefficient of friction tests. On this basis, the present invention evaluates the wear resistance of the dried coatings or coated articles provided in the examples and comparative examples by dry-grinding tests. The dry coatings or coated articles provided in the examples and comparative examples were evaluated for scratch resistance by the pencil hardness test. In addition, the effect of the dried coatings provided in the examples and comparative examples on the appearance of the substrate was further evaluated by the surface gloss test.

Test of anti-skid Property

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

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

Applying a coating composition to the surface of the substrate and drying to form a dried coating on the surface of the substrate to provide a coated article comprising the substrate and the dried coating.

The dry static coefficient of friction of the surface of the coated article was measured using an ASM 825A static coefficient of friction tester. The dry static friction coefficient was measured in any of three different areas on the surface of the coated article, and the average value was taken.

After completely wetting the surface of the coated article with deionized water, the wet static coefficient of friction of the surface of the coated article was measured with an ASM 825A static coefficient of friction tester. The wet static friction coefficient was measured in any of three different areas on the surface of the coated article, and the average value was taken.

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

range of coefficient of static friction	Level of security
		0.00-0.34	Extreme danger
0.35-0.39	Is very dangerous
		0.40-0.49	Danger of
0.50-0.59	Basic security
		0.60 or more	Is very safe

If the average value of the static friction coefficient is more than 0.6, the surface of the coated product has good anti-skid performance under the dry condition, and the anti-skid performance is better if the numerical value is larger.

If the average value of the wet static friction coefficient is more than 0.6, the surface of the coated product has good anti-skid performance under wet conditions, and the anti-skid performance is better when the numerical value is larger.

The dry and wet static coefficient of friction test results for the dry coatings or coated articles provided in the examples of the invention and comparative examples are listed in table 3.

Abrasion resistance test

The present invention characterizes the abrasion resistance of the dried coating or coated article by a dry abrasion test.

The instrument for testing wear resistance was a BYK Abrasion Tester, available from BYK corporation.

The surface of the coated article was rubbed with a friction material, a 3M5100 brush blade, available from 3M company, under a load of 2.2 kg. The wet static friction coefficient was measured 500 times per friction, and the test was stopped when the wet static friction coefficient was 0.6 or less, and the number of friction cycles of the test was recorded (one friction cycle means one back and forth friction). If the wet static friction coefficient is still greater than 0.6 at the friction cycle number of 20000, the test is stopped and the friction cycle number of 20000 is recorded.

If the number of friction cycles measured for a coated article is greater than 5000, the coated article exhibits good wear resistance.

The results of the abrasion resistance tests of the dried coatings or coated articles provided by the examples of the present invention and comparative examples are listed in table 4.

Scratch resistance test

The scratch resistance of the dried coating or coated article is characterized by the pencil hardness test.

The pencil hardness tester is Elcometer 3086, available from Elcometer corporation.

A series of chinese brand advanced drawing pencils (increasing in hardness from 9B to 9H) were shaved at one end with a special mechanical sharpener to remove approximately 5mm to 6mm of wood, leaving an intact, unscratched, smooth cylindrical pencil lead. And vertically holding the pencil, moving the pencil back and forth on the abrasive paper by keeping an angle of 90 degrees with the abrasive paper, grinding the tip of a pencil lead into a right angle, and continuously moving the pencil until a complete and smooth circular cross section is obtained. The coated article was placed on a horizontal, stable table, the pencil was held on the instrument at a 45 degree angle with a clamp, the instrument was held horizontal, and the tip of the pencil was placed on the surface of the coated article and pushed at a constant speed of 0.5mm/s to 1mm/s for a distance of at least 7mm away from the operator under a load of 750 g. Pencils of the same hardness were tested in duplicate 5 times at different locations on the surface of the coated article. Wiping the surface of the coated product with absorbent cotton dipped with an inert solvent, and visually observing whether the surface of the coated product has defects such as plastic deformation and/or cohesive failure. The test is stopped if defects such as plastic deformation and/or cohesive failure have occurred and the hardness of the pencil used for the test is recorded. If no defects such as plastic deformation and/or cohesive failure occur, the test is repeated with a pencil having a higher hardness until defects such as plastic deformation and/or cohesive failure occur on the surface of the coated article, and the hardness of the pencil used in the last test is recorded.

If the pencil hardness of a coated article is measured to be greater than 4H, it is an indication that the coated article has good scratch resistance.

The results of the scratch resistance tests of the dried coatings or coated articles provided by the examples of the present invention and comparative examples are listed in table 4.

Surface gloss measurement

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

The instrument for measuring surface Gloss was a Micro-Tri-Gloss instrument available from BYK-Gardner company.

The surface Gloss values of the coated articles were measured with a Micro-Tri-Gloss instrument. Surface gloss values were measured at 20 °, 60 ° and 85 ° in any of three different areas on the surface of the coated article, and the respective angles were averaged.

The results of the surface gloss tests of the dried coatings or coated articles provided by the examples of the invention and comparative examples are listed in table 5.

Preparation of the coating composition

Example 1

0.50 g

HYDROSIL 2926 and 15.22 grams deionized water (DI H)₂O) into a 50 ml glass bottle;

0.20 g of 3-Glycidoxypropyltrimethoxysilane (GPTMS) was added dropwise while stirring on a magnetic stirrer;

after stirring at room temperature for a further 1 hour, 0.04 g of 3-Aminopropyltriethoxysilane (APTES) are added;

after stirring for a further 10 minutes, 0.04 g of methyl orthosilicate (TMOS) was added;

after stirring for a further 30 minutes, 4.00 g of 10% by weight TRITON are added^TMBG-10 surfactant in water;

after stirring for a further 15 minutes, a tan slightly cloudy coating composition was obtained.

Examples 2 to 5

Coating compositions of examples 2 to 5 were prepared in the same manner as in example 1, wherein the coating compositions included the kinds and contents of the ingredients listed in Table 2.

Example 6

5.02 g of COATOSIL MP 200 and 10.20 gIonic water (DI H)₂O) and 1.00 g ethanol (EtOH) were added to a 50 ml glass bottle;

while stirring on a magnetic stirrer, 0.10 g of 13.30 wt% nitric acid (HNO) was added dropwise₃) Adjusting the pH of the aqueous solution to 1-2;

after stirring for a further 1 hour at room temperature, 2.56 g of 3-Glycidyloxypropyltrimethoxysilane (GPTMS) were added;

after stirring for a further 1 hour, 0.60 g of 3-Aminopropyltriethoxysilane (APTES) are added;

after stirring for a further 10 minutes, 0.60 g of methyl orthosilicate (TMOS) was added;

after stirring for a further 30 minutes, a colorless, slightly turbid coating composition was obtained.

Example 7

The coating composition of example 7, in which the kinds and contents of the ingredients included in the coating composition are listed in table 2, was prepared in the same manner as in example 1.

Comparative example 1

1.50 g of 3-Glycidyloxypropyltrimethoxysilane (GPTMS) and 19.00 g of deionized water (DIH)₂O) into a 50 ml glass bottle;

dripping 0.20 g of 5.48 wt% hydrochloric acid (HCl) aqueous solution while stirring on a magnetic stirrer, and adjusting the pH to 2-3;

after stirring at room temperature for a further 1 hour, 0.36 g of 3-Aminopropyltriethoxysilane (APTES) are added;

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 yellowish slightly cloudy coating composition was obtained.

Comparative example 2

The coating composition of comparative example 2, in which the kinds and contents of the ingredients included in the coating composition are listed in table 2, was prepared in the same manner as in comparative example 1.

Preparation of coated articles and Performance testing thereof

Example 8

A knife coating process is used to prepare a coated article comprising the steps of:

the method comprises the following steps of taking a vitrified tile (225mm multiplied by 150mm multiplied by 10mm) as a base material of a coating product, cleaning the surface of the vitrified tile by using a detergent (white cat brand, available from Shanghai and Huangbaimao Co., Ltd.), then washing the vitrified tile by using deionized water, and then drying the vitrified tile by using compressed air;

10 g of the coating composition obtained in example 1 was filtered twice with a 200 mesh sieve;

a wire rod of an automatic knife coater (K303 Multicoater, available from RK Print Coat Instruments) was placed at one end of the vitrified tile, and 5 grams of the filtered coating composition was uniformly dropped into the gap between the wire rod and the vitrified tile using a dropper;

coating the surface of the vitrified tile with a coating composition at room temperature by using an automatic coating machine;

the wet film thickness of the coating composition during the draw down was about 12 μm, designated T-12, as shown in Table 3;

and drying the coated vitrified tile at room temperature for 12 hours to obtain a coated product.

The resulting coated articles were tested for skid resistance and the test results are listed in table 3; the resulting coated articles were tested for abrasion and scratch resistance, with the test results listed in table 4; the resulting coated articles were tested for surface gloss and the results are shown in Table 5.

Examples 9 to 18

A coated article was produced in the same manner as in example 8, wherein the kind of the substrate, the blade coating conditions 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 was 1.5 μm, it was recorded as T-1.5; if the wet film thickness of the coating composition during the blade coating process is 3 μm, it is noted as T-3; if the wet film thickness of the coating composition during the knife coating process was 6 μm, it was noted as T-6; if the wet film thickness of the coating composition during the draw-down was 12 μm, it was noted as T-12.

Example 19

A coated article is prepared by a dip coating process comprising the steps of:

a glass substrate (180mm multiplied by 100mm multiplied by 3mm) is taken as a substrate of a coating product, the surface of the glass substrate is firstly cleaned by detergent (white cat brand, available from Shanghai and yellow white cat company, Ltd.), then is washed clean by deionized water, and then is dried by compressed air;

200 g of the coating composition obtained in example 4 were poured into a 400 ml stainless steel tank (150 mm. times.150 mm. times.20 mm);

dip coating the glass substrate in the coating composition with an automatic dip coater (SKVDX2S-500, available from KSV NIMA corporation) at room temperature;

the immersion speed in the dip coating process is 300mm/min, the immersion time is 1 minute, and the pulling speed is 300mm/min, which is specifically listed in table 3;

and (3) heating and drying the glass substrate subjected to dip coating in an oven at 100 ℃ for 15 minutes, taking out, and cooling to room temperature to obtain a coated product.

Example 20

A coated article is prepared using a wipe process comprising the steps of:

using 304 stainless steel (200mm × 100mm × 1mm) as a substrate of a coated product, cleaning the surface of the 304 stainless steel with a detergent (white cat brand, available from Shanghai and Huangbaimao Co., Ltd.), washing the cleaned stainless steel with deionized water, and drying the cleaned stainless steel with compressed air;

a spunbonded polypropylene nonwoven fabric (available from 3M company) was cut into a 50mm × 20mm strip, 6 g of the coating composition obtained in example 4 was extracted with a dropper, 3 g was dropped to one end of 304 stainless steel, and another 3 g was dropped to the middle of 304 stainless steel, and the nonwoven fabric was uniformly coated on 304 stainless steel from one end having the coating composition to one end having no coating composition by pressing it with a hand;

the wiped 304 stainless steel was dried at room temperature for 24 hours to obtain a coated article.

Comparative example 3

10 g of the coating composition obtained in comparative example 1 was filtered twice with a 200-mesh sieve;

the wet film thickness of the coating composition during the draw down was about 6 μm, designated T-6, as shown in Table 3;

and drying the coated vitrified tile at room temperature for 24 hours to obtain a coated product.

Comparative example 4

A coated article was prepared in the same manner as in comparative example 3, as comparative example 4, wherein the kind of the substrate, the blade coating conditions and the heat treatment conditions of the coated article are shown in Table 3.

Comparative examples 5 to 11

Vitrified tiles, glazed tiles, microlite, artificial stone, marble, glass substrates and stainless steel substrates, which were not coated with a dry coating, were used as comparative examples 5 to 11, which are specifically listed in table 3.

TABLE 3 preparation of coated articles and their non-skid testing

As can be seen from Table 3, the dry-coated substrates provided in comparative examples 5 to 10 each had a wet static coefficient of friction of less than 0.6, and therefore had poor anti-slip properties under wet conditions. The coated articles provided in examples 8-19 have dry static coefficients of friction that are improved or maintained slightly relative to the dry uncoated substrate and wet static coefficients of friction that are improved significantly relative to the dry uncoated substrate and are substantially greater than 0.6, thus providing good slip resistance in both dry and wet conditions. Comparative example 11 provides a dry uncoated stainless steel substrate having a dry static coefficient of friction and a wet static coefficient of friction greater than 1.0. The coated article provided in example 20 had a small increase in both dry and wet static coefficient of friction, and therefore the coated article had good anti-slip properties under both dry and wet conditions.

TABLE 4 abrasion and scratch resistance testing of the coated articles

Coated articles	Number of cycles in abrasion resistance test	Hardness of pencil
			Example 9	17500	5H
Example 10	20000	6H
			Example 11	16000	5H
Example 12	16500	5H
			Example 13	15000	5H
Example 14	17000	5H
			Example 15	15000	5H
Example 16	16500	5H
			Example 17	16000	5H
Example 19	17000	5H
			Example 20	17500	5H
Comparative example 3	3500	3H
			Comparative example 4	4000	3H

As can be seen from table 4, the coated article provided according to comparative example 3 had a cycle number of 3500 in the wear resistance test and a pencil hardness of 3H. The coated article provided according to comparative example 4 had a cycle number of 4000 in the abrasion resistance test and a pencil hardness of 3H. The coated articles provided according to examples 9-17, 19 and 20 all had a significantly improved number of cycles in the abrasion resistance test as compared to the coated articles provided in comparative examples 3-4, and all were significantly greater than 5000, and had a significantly improved pencil hardness as compared to the coated articles provided in comparative examples 3-4, and all were significantly greater than 4H, and thus had good abrasion resistance and scratch resistance.

Table 5 surface gloss testing of coated articles

As can be seen from Table 5, the coated articles provided according to examples 9-16 have substantially unchanged or improved surface gloss compared to the uncoated, dry-coated substrates provided in comparative examples 3-9, and thus have good appearance.

Although the foregoing detailed description contains many specific details for the purpose of illustration, it will be appreciated by those of ordinary skill in the art that numerous variations, alterations, substitutions and alterations to these details 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 determined by the appended claims and their proper legal equivalents. All cited references are incorporated herein by reference in their entirety.

Claims

1. A protective coating composition having anti-slip functionality comprising the reaction product of the following reaction components, based on 100 wt.% of the total weight of the coating composition:

HO-[SiR¹(OR³)-O]_a-[SiR²(OR³)-O]_b-[Si(OH)₂-O]_c-H (Ⅰ)

R⁴-SiR³ _d(OR³)_3-d(Ⅱ)

45-96 wt% water; and

3)0.2 to 5 wt% of an orthosilicate, which can be represented by formula iv:

Si(OR)₄(Ⅳ)

2. The coating composition of claim 1, wherein the epoxy-functional siloxane oligomer and/or polymer a has the general formula:

HO-[SiR¹(OR³)-O]_a-[SiR²(OR³)-O]_b-[Si(OH)₂-O]_c-H (Ⅰ)

wherein, 0<a≤20；0<b≤20；0≤c≤20；R¹And R²Each independently represents an organic group containing at least one unhydrolyzed epoxy functional group comprising one or more of the following groups: 3-glycidoxypropyl and 2- (3, 4-epoxycyclohexyl) ethyl; r³Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, ethylAlkyl, n-propyl and isopropyl.

3. The coating composition according to claim 1, wherein the content of the siloxane oligomer and/or polymer a containing an epoxy functional group is 4.5 to 25 wt%, based on the total weight of the coating composition, based on 100 wt%.

4. The coating composition of claim 1, wherein the epoxy functional group-containing silane compound B has the general formula:

R⁴-SiR³ _d(OR³)_3-d(Ⅱ)

5. The coating composition of claim 4 wherein the epoxy-functional silane compound B comprises one or more of the following group: 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropylethyldimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane.

6. The coating composition according to claim 1, wherein the content of the silane compound B containing an epoxy functional group is 3 to 13 wt%, based on 100 wt% of the total weight of the coating composition.

7. The coating composition of claim 1, wherein the weight ratio of the epoxy-functional siloxane oligomer and/or polymer a to the epoxy-functional silane compound B is at least 1.2: 1.

8. The coating composition of claim 1, wherein the acid is an inorganic or organic acid comprising one or more of the following group: hydrochloric acid, nitric acid and phosphoric acid; the organic acid comprises one or more of the following groups: formic acid and acetic acid.

9. The coating composition of claim 1, wherein the amino-functional silane compound C has the general formula:

10. The coating composition of claim 9, wherein the amino-functional silane compound C comprises one or more of the following group: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, N- (3-aminopropyl-ethyldiethoxysilane, N-propylmethyldimethoxysilane, N-propylmethyldiethoxysilane, N-, 3- [2- (2-aminoethylamino) ethylamino ] propyltrimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propyltriethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propylmethyldimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propylmethyldiethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltrimethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-isopropylaminopropyltrimethoxysilane, N-isopropylaminoethyldimethoxysilane, N-isopropylaminoethyltrimethoxysilane, N-isopropylaminoethyldimethoxysilane, N, N-phenyl-3-aminopropyltriethoxysilane, N-dimethyl-3-aminopropyltrimethoxysilane, N-diethyl-3-aminopropyltriethoxysilane, N-ethyl-3-trimethoxysilyl-2-methylpropylamine, N- [3- (trimethylsilyl) propyl ] N-butylamine, bis [ (3-trimethoxysilyl) -propyl ] amine, bis [ (3-triethoxysilyl) -propyl ] amine.

11. The coating composition of claim 1, wherein the orthosilicate is of the formula:

Si(OR)₄(Ⅳ)

12. The coating composition of claim 11, wherein the orthosilicate comprises one or more of the group consisting of: methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate and isopropyl orthosilicate.

13. The coating composition of claim 1, wherein the coating composition further comprises 0.01 to 10 wt% of surface epoxy modified silica particles, based on the total weight of the coating composition as 100 wt%.

14. The coating composition of claim 13, wherein the surface epoxy modified silica particles have an average particle size of less than or equal to 15 nm.

15. The coating composition of claim 1, wherein the coating composition further comprises 0.01 to 5 wt% of an organic solvent, the organic solvent being miscible with water, based on the total weight of the coating composition taken as 100 wt%, and comprising one or more of the following: alcohols, ketones, esters and ethers having a molecular weight of less than 250.

16. The coating composition of claim 1, wherein the coating composition further comprises 0.01 to 2 wt% of an additive comprising one or more of the following group, based on the total weight of the coating composition taken as 100 wt%: detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders.

17. The coating composition of claim 16, wherein the surfactant is a nonionic surfactant comprising one or more of the following group: polyoxyethylene type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylolamide type nonionic surfactant, fluorocarbon type nonionic surfactant, silicone type nonionic surfactant and modified silicone type nonionic surfactant.

18. A coated article comprising a substrate and a dried coating applied on said substrate, said dried coating comprising a coating obtained by applying the coating composition of any one of claims 1-17 to the surface of said substrate and drying.

19. The coated article of claim 18, wherein the substrate comprises one or more of the following group: ceramic tile substrates, glass substrates, stone substrates, and metal substrates.

20. The coated article of claim 19, wherein the ceramic tile substrate comprises one or more of the following group: vitrified tiles, glazed tiles, archaized tiles, microlites, polished tiles, granite-like tiles, and marble-like tiles.

21. The coated article of claim 19, wherein the stone substrate comprises one or more of the following group: marble, granite, and artificial stone.

22. The coated article of claim 19, wherein the metal substrate comprises one or more of the following group: stainless steel substrates, cold rolled steel substrates, galvanized steel substrates, aluminum substrates, and aluminum alloy substrates.

23. A method of making a coated article comprising the steps of: applying the coating composition of any one of claims 1 to 17 to a surface of a substrate to form a wet coating composition film on said substrate surface, and drying said wet coating composition film to provide a dried coating, said dried coating adhering to said surface of said substrate.

24. The method of making as defined in claim 23, wherein the coating composition is applied to the surface of the substrate by: blade coating, wiping, brushing, dipping and spraying.