WO2015142689A1

WO2015142689A1 - Slip resistant article and the method for preparing the same

Info

Publication number: WO2015142689A1
Application number: PCT/US2015/020651
Authority: WO
Inventors: Long Yin; Xin Yu; Zhigang Yu; Lin Yang; Wenyan Li; Naiyong Jing
Original assignee: 3M Innovative Properties Company
Priority date: 2014-03-19
Filing date: 2015-03-16
Publication date: 2015-09-24
Also published as: CN104926369B; CN104926369A

Abstract

The present invention provides a slip resistant article comprising a substrate and a slip resistant coating applied on the surface of the substrate. The substrate is a ceramic tile substrate. The slip resistant coating is further prepared from a slip resistant solution, and the slip resistant solution comprises the reaction product of the following reaction components: 1-83.5 wt.% of a first silane, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the first silane being R¹ _aSi (OR)_4-a-bR² _b, wherein the value of a is 0 to 3; when the value of a is 0, the value of b is 0; when the value of a is 1, the value of b is 0 to 2; when the value of a is 2, the value of b is 0 to 1; when a value of a is 3, the value of b is 0; R represents alkyl group having 1 to 4 carbon atoms; R¹ represents hydrocarbyl group with epoxy functional group; and R² represents alkyl group having 1 to 2 carbon atoms; and 16.5-99 wt.% of a first solvent, based on the total weight of the slip resistant solution as 100 wt.%, the first solvent being water and/or alcohol.

Description

SLIP RESISTANT ARTICLE AND THE METHOD FOR PREPARING THE SAME

Cross Reference To Related Application

This application claims the benefit of Chinese Patent Application No. 201410103305.5, filed March 19, 2014, the disclosure of which is incorporated by reference herein in its entirety.

Technical Field

The present invention relates to a slip resistant article and the method for preparing the same.

Background

Ceramic tiles (e.g., vitrified tiles, glazed tiles, archaized tiles, microlite stones, and polished tiles, etc.) that are commercially available for building materials will commonly become slippery when its surface is wetted by water. Slippery surfaces can easily lead to accidents such as slip-induced injures and the like. Therefore, it is important to carry out slip resistant treatments on ceramic tiles.

One of the common approaches for slip resistant treatments is to apply a slip resistant coating on the surface of the substrate to increase the surface friction of the substrate. As a result, the friction coefficient can be increased to a safe level so as to achieve the slip resistant effect, thereby reducing accidents of slip-induced injures and the like.

Currently, slip resistant coatings usually use alkyd resin, chlorinated rubber, phenolic resin, epoxy resin, or polyurethane resin as a film- forming resin, which is filled with slip resistant granules of quartz sand, corundum, titanium oxide, aluminum oxide or rubber grains and the like. The granules are irregular and protrude from the surface of coatings, which can increase the surface roughness and friction, and reduce the sliding of a person or other objects on the surface, so as to achieve the purpose of slip resistance. For example, CN101328379 (Yuan Jun and Xinhua Sun) discloses an epoxy slip resistant coating which consists of three components, namely epoxy latex, a curing agent and powder materials for cement-based roads. The curing agent is prepared from triethylenetriamine or triethylenetetramine and low molecular weight EL V AMIDE resin which are mixed. The powder materials, which consist of silicate cement, quartz sand and a water reducing agent, are fixed on cement-based roads by cured epoxy resin to achieve the slip resistant effect.

WO2007026121 (Morgan) discloses an aqueous composition consists of an alkyl polysaccharide surfactant, an alkoxysilane selected from the group consisting of 3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane, water, optionally alcohol (solely from hydrolysis of the

alkoxysilane), and optionally one or more selected from the group consisting of biocides, anitfoams and adhesion promoters, and its use in a method of coating a metal surface with a silane coating. The substrate used in this patent application is metal.

Summary of the Invention

The present invention aims to provide a new slip resistant article, which has good slip resistance performance under wet condition. According to one aspect of the present invention, a slip resistant article is provided, which comprises a substrate and a slip resistant coating applied on the surface of the substrate, the substrate is a ceramic tile substrate; the slip resistant coating is further prepared from a slip resistant solution, and the slip resistant solution comprises the reaction product of the following reaction components: 1-83.5 wt.% of a first silane, based on the total weight of the slip resistant solution as 100 wt.%, and the general formula of the first silane is R^Si (OR) 4-_a-bR²b, wherein the value of a is 0 to 3; when the value of a is 0, the value of b is 0; when the value of a is 1, the value of b is 0 to 2; when the value of a is 2, the value of b is 0 to 1 ; when the value of a is 3, the value of b is 0; R represents alkyl group having 1 to 4 carbon atoms; R¹ represents hydrocarbyl group with epoxy functional group; and R² represents alkyl group having 1 to 2 carbon atoms; and 16.5-99 wt.% of a first solvent, based on the total weight of the slip resistant solution as 100 wt.%, and the first solvent is one or more selected from the group consisting of: water and alcohol.

According to another aspect of the present invention, the present invention provides a method for preparing a slip resistant article, which includes the steps of: applying a slip resistant solution to a surface of a substrate to form a wet layer on the surface of the substrate, drying the wet layer to form a slip resistant coating, wherein the slip resistant coating is attached to the surface of the substrate.

According to these preferred embodiments, the slip resistant article provided by the present invention can be obtained with this method.

Detailed Description of the Invention It should be understood that without departing from the scope or spirit of the present invention, the person skilled in the art can conceive other various embodiments according to the teachings of this specification and can modify them. Therefore, the following embodiments are not in a limiting sense.

Unless otherwise indicated, all numbers used in this specification and claims for expressing the quantity and physicochemical properties should be understood as in all cases to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters listed in the foregoing specification and attached claims are all approximations, the person skilled in the art can use the teachings disclosed herein to obtain the desired properties, and to appropriately change these approximation. The use of numerical range represented by endpoints includes all numbers within that range and any range within that range, e.g., 1, 2, 3, 4 and 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, and so on.

The slip resistant article

The slip resistant article provided by the present invention comprises a substrate and a slip resistant coating applied on the surface of the substrate, wherein the substrate is a ceramic tile substrate; as used herein and in the claims, the term "ceramic tile" is intended to include tile made of fired clay, brick, concrete, porcelain, marble, travertine, and other stone or slate; the slip resistant coating is further prepared from the slip resistant solution, and the slip resistant solution comprises the reaction product of the following reaction components: 1-83.5 wt.% of a first silane, based on the total weight of the slip resistant solution as 100 wt.%, and the general formula of the first silane is R^Si (OR) 4-_a-bR²b, wherein the value of a is 0 to 3; when the value of a is 0, the value of b is 0; when the value of a is 1, the value of b is 0 to 2; when the value of a is 2, the value of b is 0 to 1 ; when the value of a is 3, the value of b is 0;

R represents alkyl group having 1 to 4 carbon atoms; R¹ represents hydrocarbyl group with epoxy functional group; and R² represents alkyl group having 1 to 2 carbon atoms; and 16.5-99 wt.% of a first solvent, based on the total weight of the slip resistant solution as 100 wt.%, and the first solvent is one or more selected from the group consisting of: water and alcohol. In the slip resistant article, the slip resistant coating is a coating obtained from the slip resistant solution after drying. The slip resistant coating is completely or partially free of water or alcohol, preferably free of water and alcohol. The slip resistant coating can significantly improve the slip resistance performance of the substrate under wet condition without significantly reducing the slip resistance performance of the substrate under dry condition. Further, since the slip resistant coating is transparent, it will not affect the appearance of the coated substrate. The slip resistant coating can be of any suitable thickness as needed, and the thickness of the slip resistant coating can be 100-5000 nanometers (nm), or 200-3000 nm, or 300-1000 nm.

The substrate is a ceramic tile substrate, and the ceramic tile substrate is one or more selected from the group consisting of: vitrified tile, glazed tile, archaized tile, microlite stone, polished tile, artificial granite tile, and artificial marble tile.

The first silane is one or more selected from the group consisting of:

3 -glycidoxypropyltrimethoxy silane, 3 -glycidoxypropylmethyldiethoxysilane,

2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, tetramethyl orthosilicate, and tetraethyl orthosilicate. The content of the first silane is 1-83.5 wt.%, preferably 1-20 wt.%, particularly preferably 5-20 wt.%, based on the total weight of the slip resistant solution as 100 wt.%. If the content of the first silane is less than 1 wt.%, it may be difficult to form a slip resistant coating having sufficient thickness, therefore it cannot achieve the slip resistance performance provided by the slip resistant article of the present invention; if the content of the first silane is greater than 83.5 wt.%, the appearance of the slip resistant coating obtained accordingly may have more defects, thereby causing the appearance of the obtained slip resistant article to have obvious defects.

The first solvent can be water or alcohol. The alcohol is one or more selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, and n-butanol.

The content of the first solvent is 16.5-99 wt.%, based on the total weight of the slip resistant solution as 100 wt.%. If the content of the first solvent is less than 16.5 wt.%, the appearance of the slip resistant coating obtained accordingly may have more defects, thereby causing the appearance of the obtained slip resistant article to have obvious defects; if the content of the first solvent is greater than 99 wt %, it may be difficult to form a slip resistant coating of sufficient thickness, therefore it cannot achieve the slip resistance performance provided by the slip resistant article of the present invention.

In the reaction components of the slip resistant solution, an acid may be further included. The acid can accelerate the reaction rate of reaction components in the slip resistant solution. The acid may be an inorganic acid, and may also be an organic acid. The inorganic acid may be one or more selected from the group consisting of: hydrochloric acid, nitric acid and phosphoric acid, particularly preferably phosphoric acid and hydrochloric acid. The organic acid may be one or more selected from the group consisting of: formic acid, acetic acid, oxalic acid and citric acid, particularly preferably formic acid and acetic acid. The content of the acid is not particularly limited, as long as it enables the pH value of the slip resistant solution to be less than or equal to 4, preferably 1 to 3, particularly preferably 2 to 3.

In the reaction components of the slip resistant solution, a second silane may be further included. The second silane can react with the epoxy groups and/or the alkoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution. The slip resistant coating further prepared from this new slip resistant solution may be cured at room temperature, and this slip resistant coating has good abrasion resistance performance. The general formula of the second silane is

R³cSi(OR)4-c dR⁴, wherein the value of c is 0 to 3; when the value of c is 1, the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms. The second silane may be one or more selected from the group consisting of: 3-aminopropyltriethoxysilane,

3-aminopropylmethyldiethoxysilane, 3-(2-aminoethyl)-aminopropyltrimethoxysilane,

3-(2-aminoethyl)-aminopropylmethyldimethoxysilane,

3-(N,N-dimethylaminopropyl)-aminopropylmethyldimethoxysilane, and bis(3-trimethoxysilylpropyl) amine. The content of the second silane is 0-3.0 wt.%, preferably 0-2.0 wt.%, particularly preferably 0.5-2.0 wt.%, based on the total weight of the slip resistant solution as 100 wt.%. If the content of the second silane is greater than 3.0 wt.%, when it reacts with the epoxy groups and/or the alkoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution, the slip resistance performance and the abrasion resistance performance of the slip resistant coating and the slip resistant article further prepared from this new slip resistant solution may be poor, therefore the slip resistance performance and the abrasion resistance performance provided by the slip resistant article of the present invention cannot be achieved.

In the reaction components of the slip resistant solution, a multifunctional amine may be further included. The multifunctional amine can react with the epoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution. The slip resistant coating further prepared from this new slip resistant solution may be cured at room temperature, and this slip resistant coating has good abrasion resistance performance. The multifunctional amine may be one or more selected from the group consisting of: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, and polyethyleneimine. The content of the multifunctional amine is 0- 1.4 wt.%, preferably 0-1.0 wt.%, particularly preferably 0.1-1.0 wt.%, based on the total weight of the slip resistant solution as 100 wt.%. If the content of the multifunctional amine is greater than 1.4 wt.%, when it reacts with the epoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution, the slip resistance performance and abrasion resistance performance of the slip resistant coating and the slip resistant article further prepared from this new slip resistant solution may be poor, therefore the slip resistance performance and the abrasion resistance performance provided by the slip resistant article of the present invention cannot be achieved.

In the reaction components of the slip resistant solution, an organosilicon quaternary ammonium salt may be further included. The organosilicon quaternary ammonium salt can react with the alkoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution, and the surface wettability of slip resistant coating further prepared from this new slip resistant solution can be adjusted by adding an appropriate amount of the organosilicon quaternary ammonium salt as needed. The general formula of the organosilicon quaternary ammonium salt is Si(OR)3R⁵N⁺(R⁶)3-X^~, wherein R represents alkyl group having 1 to 4 carbon atoms, R⁵ represents hydrocarbyl group, oxygen-containing group or nitrogen-containing group, R⁶ represents hydrocarbyl group having 1 to 20 carbon atoms, and X represents an acid radical. The content of the organosilicon quaternary ammonium salt is 0-2.5 wt.%, preferably 0-2.0 wt.%, particularly preferably 0.5-1.5 wt.%, based on the total weight of the slip resistant solution as 100 wt.%. If the content of the organosilicon quaternary ammonium salt is greater than 2.5 wt.%, when it reacts with the alkoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution, both the slip resistance performance and appearance of the slip resistant coating further prepared from this new slip resistant solution may be poor, therefore the slip resistance performance and good appearance provided by the slip resistant article of the present invention cannot be achieved.

In the reaction components of the slip resistant solution, a third silane may be further included. The third silane is alkyl silane and can react with the alkoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution, and the surface wettability of slip resistant coating further prepared from this new slip resistant solution can be adjusted by adding an appropriate amount of the third silane as needed. The general formula of the third silane is R⁷ _eSi(OR)4-_e, wherein the value of e is 1 to 3, R represents alkyl group having 1 to 4 carbon atoms, and R⁷ represents alkyl group having 1 to 20 carbon atoms. The third silane may be one or more selected from the group consisting of: methyl trimethoxy silane, n-octyl triethoxy silane, and hexadecyl trimethoxy silane. The content of the third silane is 0-3.0 wt.%, preferably 0-2.0 wt.%, particularly preferably 0.3-1.0 wt.%, based on the total weight of the slip resistant solution as 100 wt.%. If the content of the third silane is greater than 3.0 wt.%, when it reacts with the alkoxy groups of the first silane in the slip resistant solution together to obtain a new slip resistant solution, both the slip resistance performance and appearance of the slip resistant coating further prepared from this new slip resistant solution may be poor, therefore the slip resistance performance and good appearance provided by the slip resistant article of the present invention cannot be achieved.

In the reaction components of the slip resistant solution, a nonionic surfactant may be further included. The nonionic surfactant can be added into the slip resistant solution together with other reaction components to obtain a new slip resistant solution, and the surface wettability of the slip resistant coating further prepared from this new slip resistant solution can be adjusted by adding an appropriate amount of the nonionic surfactant as needed. The content of the nonionic surfactant is 0-2.0 wt.%, preferably 0- 1.0 wt.%, particularly preferably 0.05-0.5 wt.%, based on the total weight of the slip resistant solution as 100 wt.%. If the content of the nonionic surfactant is greater than 2.0 wt.%, when it is added into the slip resistant solution together with other reaction components to obtain a new slip resistant solution, both the slip resistance performance and the appearance of the slip resistant coating further prepared from this new slip resistant solution may be poor, therefore the slip resistance performance and good appearance provided by the slip resistant article of the present invention cannot be achieved.

A primer may be provided between the slip resistant coating and the substrate of the slip resistant article. The primer is a coating obtained from the dried primer solution, and the primer solution comprises the reaction product of the following reaction components: 0.1-2.0 wt.% of a fourth silane, based on the total weight of the primer solution as 100 wt.%, the general formula of the fourth silane is R³cSi(OR)4-c dR⁴d, wherein the value of c is 0 to 3; when the value of c is 1, the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms; and 98.0-99.9 wt.% of a second solvent, based on the total weight of the primer solution as 100 wt.%, the second solvent is one or more selected from the group consisting of: water and alcohol. The alcohol may be one or more selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, and n-butanol.

The primer can be completely or partially free of water or alcohol, preferably free of water and alcohol. The primer can be of any suitable thickness as needed, and the thickness of the primer can be 100-1000 nm, or 100-800 nm, or 200-600 nm.

The Preparation Method of the Slip Resistant Article

The present invention provides a method for preparing a slip resistant article, and the method comprises the steps of: applying a slip resistant solution to a surface of a substrate to form a wet layer on the surface of the substrate, drying the wet layer to form a slip resistant coating, wherein the slip resistant coating is attached to the surface of the substrate.

Description about the substrate, the slip resistant solution, the slip resistant coating, and the slip resistant article can be found in the "slip resistant article" section of the present specification in detail.

The slip resistant solution can be applied to the surface of the substrate by using methods known in the art, and the method may preferably be one or more selected from the group consisting of: bar coating, wipe coating, brush coating, dip coating, and spray coating. The slip resistant solution can be dried using suitable drying methods known in the art, and the drying process can be performed at room temperature or elevated temperature. For example, the temperature can be 20- 180°C, or 20 - 150°C, or 20-120°C.

Before applying a slip resistant solution to a surface of a substrate to form a wet layer on the surface of the substrate, a wet layer of a primer solution is applied on the surface of the substrate, then drying the wet layer to form a primer. The primer solution can be applied to the surface of the substrate by using methods known in the art, and the method may preferably be one or more selected from the group consisting of: bar coating, wipe coating, brush coating, dip coating, and spray coating. The primer solution can be dried using suitable drying methods known in the art. The drying process can be performed at room temperature or elevated temperature. For example, the temperature can be 20-120°C, or 20-100°C, or 20-80°C.

Various embodiments are provided that include slip resistant articles and methods of making slip resistant articles.

Embodiment 1 is a slip resistant article comprising a substrate and a slip resistant coating applied on the surface of the substrate, wherein: the substrate is a ceramic tile substrate; the slip resistant coating is further prepared from a slip resistant solution; the slip resistant solution comprises the reaction product of the following reaction components: 1-83.5 wt.% of a first silane, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the first silane being R^Si (OR) 4 a bR²b, wherein the value of a is 0 to 3; when the value of a is 0, the value of b is 0; when the value of a is 1, the value of b is 0 to 2; when the value of a is 2, the value of b is 0 to 1 ; when the value of a is 3, the value of b is 0; R represents alkyl group having 1 to 4 carbon atoms; R¹ represents hydrocarbyl group with epoxy functional group; and R² represents alkyl group having 1 to 2 carbon atoms; and 16.5-99 wt.% of a first solvent, based on the total weight of the slip resistant solution as 100 wt.%, the first solvent being one or more selected from the group consisting of: water and alcohol.

Embodiment 2 is the slip resistant article according to embodiment 1 , wherein: the ceramic tile substrate is one or more selected from the group consisting of: vitrified tile, glazed tile, archaized tile, microlite stone, polished tile, artificial granite tile, and artificial marble tile.

Embodiment 3 is the slip resistant article according to embodiment 1 , wherein: the first silane is one or more selected from the group consisting of: 3-glycidoxypropyltrimethoxysilane,

3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, tetramethyl orthosilicate, and tetraethyl orthosilicate.

Embodiment 4 is the slip resistant article according to embodiment 1 , wherein: the alcohol is one or more selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, and n-butanol.

Embodiment 5 is the slip resistant article according to embodiment 1 , wherein: the slip resistant solution further comprises an acid, and the pH of the slip resistant solution is less than or equal to 4.

Embodiment 6 is the slip resistant article according to embodiment 5, wherein: the acid is an inorganic acid or an organic acid; the inorganic acid is one or more selected from the group consisting of: hydrochloric acid, nitric acid and phosphoric acid; the organic acid is one or more selected from the group consisting of: formic acid, acetic acid, oxalic acid, and citric acid.

Embodiment 7 is the slip resistant article according to embodiment 1 , wherein: the slip resistant solution further comprises 0-3.0 wt.% of a second silane, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the second silane being R³ _cSi(OR)4-_c-dR⁴, wherein the value of c is 0 to 3; when the value of c is 1, the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms.

Embodiment 8 is the slip resistant article according to embodiment 7, wherein: the second silane is one or more selected from the group consisting of: 3-aminopropyltriethoxysilane,

3-(2-aminoethyl)-aminopropylmethyldimethoxysilane,

3-(N,N-dimethylaminopropyl)-aminopropylmethyldimethoxysilane, and

bis(3-trimethoxysilylpropyl)amine.

Embodiment 9 is the slip resistant article according to embodiment 1 , wherein: the slip resistant solution further comprises 0-1.4 wt.% of a multifunctional amine, based on the total weight of the slip resistant solution as 100 wt.%.

Embodiment 10 is the slip resistant article according to embodiment 9, wherein: the multifunctional amine is one or more selected from the group consisting of: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, and polyethyleneimine.

Embodiment 11 is the slip resistant article according to embodiment 1 , wherein: the slip resistant solution further comprises 0-2.5 wt.% of an organosilicon quaternary ammonium salt, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the organosilicon quaternary ammonium salt being Si(OR)3R⁵N⁺(R⁶)3-X^~, wherein R represents alkyl group having 1 to 4 carbon atoms, R⁵ represents hydrocarbyl group, oxygen-containing group or nitrogen-containing group, R⁶ represents hydrocarbyl group having 1 to 20 carbon atoms, and X represents an acid radical.

Embodiment 12 is the slip resistant article according to embodiment 11, wherein: the organosilicon quaternary ammonium salt is N-trimethoxysilylpropyl-N, N, N- trimethylammonium chloride.

Embodiment 13 is the slip resistant article according to embodiment 1 , wherein: the slip resistant solution further comprises 0-3.0 wt.% of a third silane, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the third silane being R⁷ _eSi(OR)4-_e, wherein the value of e is 1 to 3, R represents alkyl group having 1 to 4 carbon atoms, and R⁷ represents alkyl group having 1 to 20 carbon atoms.

Embodiment 14 is the slip resistant article according to embodiment 13, wherein: the third silane is one or more selected from the group consisting of: methyltrimethoxysilane, n-octyltriethoxysilane, and hexadecyltrimethoxysilane.

Embodiment 15 is the slip resistant article according to embodiment 1, wherein: the slip resistant solution further comprises 0-2.0 wt.% of a nonionic surfactant, based on the total weight of the slip resistant solution as 100 wt.%.

Embodiment 16 is the slip resistant article according to embodiment 1 , wherein: a primer is further provided between the slip resistant coating and the substrate, and the primer is further prepared from a primer solution, and the primer solution comprises the reaction product of the following reaction components: 0.1-2.0 wt.% of a fourth silane, based on the total weight of the primer solution as 100 wt.%, the general formula of the fourth silane being R³ _cSi(OR)4-_c-dR⁴d, wherein the value of c is 0 to 3; when the value of c is 1, the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms; and 98.0-99.9 wt.% of a second solvent, based on the total weight of the primer solution as 100 wt.%, and the second solvent is one or more selected from the group consisting of: water and alcohol.

Embodiment 17 is a method for preparing the slip resistant article according to embodiment 1 to 15, comprising the steps of: applying a slip resistant solution to a surface of a substrate to form a wet layer on the surface of the substrate, drying the wet layer to form a slip resistant coating, wherein the slip resistant coating is attached to the surface of the substrate.

Embodiment 18 is the preparation method according to embodiment 17, wherein: before applying a slip resistant solution to a surface of a substrate to form a wet layer on the surface of the substrate, a wet layer of a primer solution is applied on the surface of the substrate, then drying the wet layer to form a primer, and the primer solution comprises the reaction product of the following reaction components: 0.1-2.0 wt.% of a fourth silane, based on the total weight of the primer solution as 100 wt.%, the general formula of the fourth silane being R³ _cSi(OR)4-_c-dR⁴d, wherein the value of c is 0 to 3; when the value of c is 1 , the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms; and 98.0-99.9 wt.% of a second solvent, based on the total weight of the primer solution as 100 wt.%, and the second solvent is one or more selected from the group consisting of: water and alcohol.

Embodiment 19 is the preparation method according to embodiment 17, wherein: the slip resistant solution is applied to the surface of the substrate by the following means: bar coating, wipe coating, brush coating, dip coating, and spray coating.

Embodiment 20 is the preparation method according to embodiment 18, wherein: the primer solution is applied to the surface of the substrate by the following means: bar coating, wipe coating, brush coating, dip coating and spray coating.

Examples

The following Examples and Comparative Examples are provided to help understand the present invention, and these Examples and Comparative Examples should not be construed as the limitation for the scope of the invention. Unless otherwise indicated, all parts and percentages are calculated by weight.

The raw materials used in Examples and Comparative Examples of the present invention are shown in Table 1.

Table 1 : Raw materials used in Examples and Comparative Examples

Chemical Materials Co.

Sinopharm Chemical n-Octyltriethoxysilane Purity >95.0 wt.%

Reagent Co., Ltd.

Hexadecyltrimethoxysilane Purity >95.0 wt.%

N-trimethoxysilyl- 50 wt.% Methanol U.S. Gelest, Inc.

propyl-N,N,N-trimethylammonium chloride solution

Sinopharm Chemical

3 - Aminopropyltriethoxy silane Purity >98.0 wt.%

Reagent Co., Ltd.

3-Aminopropylmethyldiethoxysilane Purity >97.0 wt.%

3-(2-Aminoethyl)-aminopropyltrimethoxysil

Purity >97.0 wt.%

ane Zhangjiagang

3-(2-Aminoethyl)-aminopropylmethyldimeth Guotai-Huarong New

Purity >97.0 wt.%

oxysilane Chemical Materials Co.

3-(N,N-dimethylaminopropyl)-aminopropyl

Purity >95.0 wt.%

methyldimethoxysilane

Bis(3-trimethoxysilylpropyl)amine Purity >95.0 wt.% U.S. Gelest, Inc.

Sinopharm Chemical

Ethylene diamine Purity >99.0 wt.%

Reagent Co., Ltd.

TCI (Shanghai)

Diethylene triamine Purity >98.0 wt.%

Development Co., Ltd.

Sinopharm Chemical

Triethylene tetramine Purity >97.0 wt.%

Reagent Co., Ltd.

Sinopharm Chemical

Tetraethylene pentamine Purity >95.0 wt.%

Reagent Co., Ltd.

[CH₂CH₂NH]_n,

Polyethylene polyamine Molecular weight of Sigma- Aldrich Co.

about 423 50 wt.% Aqueous

solution, Molecular

Polyethyleneimine

weight of

600000- 1000000

Methanol (MeOH) Purity >98.0 wt.%

Jiangsu Qiangsheng

Ethanol (EtOH) Purity >99.7 wt.%

Chemical Co., Ltd.

Isopropanol (IPA) Purity >99.7 wt.%

Shanghai Lingfeng n-Propanol (PrOH) Purity >99.0 wt.%

Chemical Reagent Co., Ltd. n-Butanol (BuOH) Purity >99.0 wt.% Shanghai Wulian plant

Purity =36—38

Hydrochloric acid (HQ)

wt.%

Phosphoric acid (H3PO4) Purity >85.0 wt.% Sinopharm Chemical

Purity =65—68 Reagent Co., Ltd.

Nitric acid

wt.%

Acetic acid Purity >99.5 wt.%

Formic acid Purity >88.0 wt.% Shanghai Aibi Chemical

Citric acid Purity >99.5 wt.% Preparation Co., Ltd.

Shanghai Zhanyun Chemical

Oxalic acid Purity >99.5 wt.%

Co., Ltd.

Alkylpolyglucoside

surfactant, TRITON

BG- 10 , 70 wt.%

aqueous solution

Nonionic surfactant Dow Chemical Co.

Special alcohol

surfactant,

ECOSURF BD- 109,

90 wt.% 225 mm l50

Vitrified tile

mmx lO mm

200 mmx200

Glazed tile

mmx lO mm

200 mmx200 mmx9

Archaized tile

mm

300 mmx300 Shanghai Bohao Building

Microlite stone

mmx lO mm Materials Co., Ltd.

200 mmx200

Polished tile

mmx20 mm

500 mmx500

Artificial marble tile

mmx l4 mm

500 mmx500

Artificial granite tile

mmx l5 mm

The present invention evaluates the slip resistance performance of the slip resistant articles provided by the Examples and Comparative Examples mainly through the dry and wet static friction coefficient. On this basis, through abrasion resistance performance test or surface wettability test, the present invention further assesses other performances of the slip resistant articles provided by the Examples and Comparative Examples.

Slip Resistance Performance Test

Static friction coefficient is an important index for evaluating the slip resistance performance of the ground. In the present invention, the slip resistance performance under dry condition is characterized by the dry static friction coefficient. The slip resistance performance under wet condition is characterized by the wet static friction coefficient in the present invention.

The equipment for testing the dry and wet static friction coefficient is ASM 825A, commercially available from American Slip Meter Company. The friction medium for testing the dry and wet static friction coefficient is 4S rubber (IRD hardness of 90 ± 2).

A slip resistant solution is applied to the surface of the substrate, and the dried slip resistant solution forms a slip resistant coating on the surface of the substrate, to obtain a slip resistant article comprising the substrate and the slip resistant coating.

ASM 825A static friction coefficient tester is used to measure the dry static friction coefficient of the surface of the slip resistant article. Three different regions are randomly taken from the surface of the slip resistant article, and their dry static friction coefficients are measured respectively, and the average value is taken.

After the surface of the slip resistant article has been completely wetted by deionized water, the wet static friction coefficient of the surface of the slip resistant article is measured by using ASM 825A static friction coefficient tester. Three different regions are randomly taken from the surface of the slip resistant article, and their wet static friction coefficients are measured respectively, and the average value is taken.

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

If the average value of the dry static friction coefficient is greater than 0.6, it indicates that the surface of this slip resistant article has good slip resistance performance under dry condition. The larger is the value, the better is the slip resistance performance.

If the average value of the wet static friction coefficient is greater than 0.6, it indicates that the surface of this slip resistant article has good slip resistance performance under wet condition. The larger is the value, the better is the slip resistance performance.

The test results of dry and wet static friction coefficient of the slip resistant articles provided by the Examples and Comparative examples of the present invention are listed in Table 4.

Abrasion Resistance Performance Test In present invention, the abrasion resistance performance of the slip resistant article is characterized by the dry abrasion test.

The equipment for testing the abrasion resistance performance is BYK Abrasion Tester, which is commercially available from BYK Company.

Under the condition of 2.2 kg load, abrasion medium is used to scrub on the surface of the slip resistant coating. The abrasion medium is 3M 5100 pad, which is commercially available from 3M Company. A wet static friction coefficient is measured per 20 times of abrasion. When the wet static friction coefficient is less than or equal to 0.6, stop the test and record the number of friction cycles measured (one abrasion cycle refers to scrubbing back and forth once). If the wet static friction coefficient is still greater than 0.6 when the number of abrasion cycles reach 4000, then stop the test and record the number of abrasion cycles as 4000.

If the measured abrasion cycles of a certain slip resistant article are greater than 100, it indicates that this slip resistant article has good abrasion resistance performance.

The test results of abrasion resistance performance of the slip resistant articles provided by the Examples and Comparative examples of the present invention are listed in Table 5. Surface Wettability Test

The surface wettability of the slip resistant article is characterized by the contact angle in the present invention.

The equipment for testing the surface wettability is Kruss DSA100 automatic contact angle tester, which is commercially available from Kruss Company.

5 microliters of water droplets are dropwise added on the surface of the slip resistant article, and when the shape of water droplets no longer changes, its contact angle is tested. Three different regions are randomly taken from the surface of the slip resistant article, and their contact angles are measured respectively, and the average value is taken.

If the average value of the water droplet contact angle is less than 90 degrees, it indicates that the surface of the slip resistant article is hydrophilic. The smaller is the value, the better is the hydrophilicity of the surface; if the average value of the water droplet contact angle is greater than 90 degrees, it indicates that the surface of the slip resistant article is hydrophobic. The greater is the value, the better is the hydrophobicity of the surface.

The test results of the surface wettability of the slip resistant articles provided by the Examples and Comparative examples of the present invention are listed in Table 6.

Preparation of the Slip Resistant Solutions

Example 1

2.50 g of 3-glycidoxypropyltrimethoxysilane and 47.50 g of deionized water are added to a 100 ml glass bottle;

After stirring for 48 hours with a magnetic stirrer at room temperature, 10.00 g of 10 wt.% aqueous solution of TRITON BG-10 surfactant is added;

After stirring continuously for 10 minutes, a clear slip resistant solution is obtained.

Example 2 to 3

The slip resistant solution of Example 2 to 3 is prepared in the same manner as in Example 1 , wherein the types and contents of components included in the slip resistant solution are listed in Table 2A and 2B.

Example 4

2.50 g of 3-glycidoxypropyltrimethoxysilane and 47.50 g of isopropanol are added to a 100 ml glass bottle;

After stirring at room temperature for 1 hour with a magnetic stirrer, a clear slip resistant solution is obtained.

Example 5 to 7

The slip resistant solution of Example 5 to 7 is prepared in the same manner as in Example 4, wherein the types and contents of components included in the slip resistant solution are listed in Table 2A and Table 2B.

Example 8

2.50 g of 3-glycidoxypropyltrimethoxysilane and 45.00 g of methanol are added to a 100 ml glass bottle;

After stirring for 1 hour at room temperature with a magnetic stirrer, 2.50 g of 50 wt.%

N-trimethoxysilylpropyl- N, N, N- trimethylammonium chloride in methanol is added;

After stirring continuously for 30 minutes, a clear slip resistant solution is obtained.

Example 9

5.00 g of 3-glycidoxypropyltrimethoxysilane and 95.00 g of deionized water are added to a 250 ml glass bottle;

During the process of stirring on a magnetic stirrer, 0.95 g of acetic acid (1M) is added dropwise, and the pH is adjusted to 3 to 4;

After stirring continuously at room temperature for 1 hour, 2.00 g of 10 wt.% aqueous solution of TRITON BG- 10 surfactant is added;

Example 10 to 15

The slip resistant solution of Example 10 to 15 is prepared in the same manner as in Example 9, wherein the types and contents of components included in the slip resistant solution are listed in Table 2A and 2B.

Example 16

2.50 g of 3-glycidoxypropyltrimethoxysilane, 23.70 g of deionized water and 23.70 g of isopropanol are added to a 100 ml glass bottle;

During the process of stirring on a magnetic stirrer, 0.80 g of 85 wt.% phosphoric acid is added dropwise, and the pH is adjusted to 2 to 3;

After stirring continuously at room temperature for 1 hour, 1.00 g of 10 wt.% aqueous solution of TRITON BG- 10 surfactant is added;

Example 17 to 19

The slip resistant solution of Example 17 to 19 is prepared in the same manner as in Example 16, wherein the types and contents of components included in the slip resistant solution are listed in Table 2A and Table 2B.

Example 20

3.15 g of 3-glycidoxypropyltrimethoxysilane, 1.85 g of methyltrimethoxysilane, 2.50 g of deionized water and 45.00 g of n-butanol are added to a 100 ml glass bottle;

During the process of stirring on a magnetic stirrer, 10.00 g of 5 wt.% aqueous solution of oxalic acid is added dropwise, and the pH is adjusted to 3 to 4;

After stirring continuously at room temperature for 24 hours, a clear slip resistant solution is obtained.

Example 21 to 22

The slip resistant solution of Example 21 to 22 is prepared in the same manner as in Example 20, wherein the types and contents of components included in the slip resistant solution are listed in Table 2A and 2B.

Example 23

15.00 g of 3-glycidoxypropyltrimethoxysilane and 190.00 g of deionized water are added to a 500 ml glass bottle;

During the process of stirring on a magnetic stirrer, 2.00 g of 5.48 wt.% aqueous solution of hydrochloric acid is added dropwise, and the pH is adjusted to 2 to 3;

After stirring continuously at room temperature for 1 hour, 3.56 g of 3-aminopropyltriethoxysilane is added;

After stirring continuously for 30 minutes, 7.24 g of 10 wt.% aqueous solution of TRITON BG- 10 surfactant is added; After stirring continuously for 10 minutes, a slightly turbid slip resistant solution is obtained.

Example 24 to 30

The slip resistant solution of Example 24 to 30 is prepared in the same manner as in Example 23, wherein the types and contents of components included in the slip resistant solution are listed in Table 2.

Example 31

During the process of stirring on a magnetic stirrer, 0.50 g of 5.48 wt.% aqueous solution of hydrochloric acid is added dropwise, and the pH is adjusted to 1 to 2;

After stirring continuously at room temperature for 1 hour, 0.14 g of ethylene diamine is added;

After stirring continuously for 30 minutes, 1.00 g of 10 wt.% aqueous solution of TRITON BG- 10 surfactant is added;

After stirring continuously for another 10 minutes, a slightly turbid slip resistant solution is obtained.

Example 32 to 36

The slip resistant solution of Example 32 to 36 is prepared in the same manner as in Example 31, wherein the types and contents of components included in the slip resistant solution are listed in Table 2A and Table 2B.

Table 2A: Slip resistant formulations (silanes)

3 -Glycidoxypropyl-

Ex 2 19.80 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 3 76.59 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 4 5.00 — 0.00 — 0.00 trimethoxysilane

Tetramethyl

Ex 5 8.65 — 0.00 — 0.00 orthosilicate

Ex 6 Tetraethyl orthosilicate 5.00 — 0.00 — 0.00

Tetraethyl orthosilicate

&

Ex 7 5.00 — 0.00 — 0.00

3 -Glycidoxypropyl- trimethoxysilane ^

N-trimethoxy- silylpropyl-

3 -Glycidoxypropyl-

Ex 8 5.00 Ν,Ν,Ν-trimethyl 2.50 — 0.00 trimethoxysilane

ammonium

chloride

3 -Glycidoxypropyl-

Ex 9 4.86 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 10 4.84 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 11 4.90 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 12 0.97 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 13 37.38 — 0.00 — 0.00 trimethoxysilane

Ex 14 3 -Glycidoxypropyl- 57.14 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 15 83.47 — 0.00 — 0.00 trimethoxysilane

3 -Glycidoxypropyl-

Ex 16 4.84 — 0.00 — 0.00 trimethoxysilane

Ex 17 Tetraethyl orthosilicate 4.84 — 0.00 — 0.00

Ex 18 Tetraethyl orthosilicate 4.97 — 0.00 — 0.00

Tetraethyl orthosilicate

&

Ex 19 10.46 — 0.00 — 0.00

3 -Glycidoxypropyl- trimethoxysilane ^

3 -Glycidoxypropyl- Methyl

Ex 20 5.04 2.96 — 0.00 trimethoxysilane trimethoxysilane

Hexadecyl

Ex 21 Tetraethyl orthosilicate 5.17 0.51 — 0.00 trimethoxysilane

Tetraethyl orthosilicate

Octyl

Ex 22 & 3-Glycidoxypropyl- 5.88 0.39 — 0.00 triethoxysilane

trimethoxysilane ³⁾

3 -Glycidoxypropyl- 3-aminopropyl

Ex 23 6.89 — 0.00 1.63 trimethoxysilane triethoxysilane

3 -Glycidoxypropyl- 3-aminopropyl

Ex 24 4.71 — 0.00 2.92 trimethoxysilane triethoxysilane

3 -Glycidoxypropyl

3 - aminopropyl-methyl

Ex 25 methyldiethoxy- 4.85 — 0.00 1.11 diethoxysilane

silane

3 -Glycidoxypropyl- 3 - (2 - aminoethyl) - 3 - amino

Ex 26 4.83 — 0.00 0.58 trimethoxysilane propyl trimethoxysilane

2-(3,4-Epoxycyclohexyl 3 - (2 - aminoethyl) - 3 - amino

Ex 27 4.81 — 0.00 0.87 )ethyl- trimethoxysilane propyl trimethoxysilane 3 -(2-aminoethyl)-amino

3 -Glycidoxypropyl-

Ex 28 4.82 — 0.00 propylmethyl 0.73 trimethoxysilane

dimethoxysilane

3 -(N,N-dimethylamino

3 -Glycidoxypropyl-

Ex 29 5.09 — 0.00 propyl) - aminopropyl 0.86 trimethoxysilane

methyl dimethoxysilane

3 -Glycidoxypropyl- Bis(3 -trimethoxysilyl-

Ex 30 4.62 — 0.00 1.85 trimethoxysilane propyl) amine

3 -Glycidoxypropyl-

Ex 31 4.84 — 0.00 Ethylene diamine 0.27 trimethoxysilane

3 -Glycidoxypropyl-

Ex 32 4.85 — 0.00 Diethylene triamine 0.16 trimethoxysilane

3 -Glycidoxypropyl-

Ex 33 4.84 — 0.00 Triethylene tetramine 0.19 trimethoxysilane

3 -Glycidoxypropyl-

Ex 34 4.83 — 0.00 Tetraethylene pentamine 0.43 trimethoxysilane

3 -Glycidoxypropyl-

Ex 35 4.83 — 0.00 Polyethylene polyamine 0.54 trimethoxysilane

3 -Glycidoxypropyl-

Ex 36 4.79 — 0.00 Polyethyleneimine 1.36 trimethoxysilane

In Example 7, the molar ratio of tetraethyl orthosilicate and 3-Glycidoxypropyltrimethoxysilane is 1 : 1 ;

^{( }} In Example 19, the molar ratio of tetraethyl orthosilicate and 3-Glycidoxypropyltrimethoxysilane is 1 : 1 ;

⁽³⁾ In Example 22, the weight ratio of tetraethyl orthosilicate and 3-Glycidoxypropyltrimethoxysilane 2: 1.

Table 2B: Slip resistant formulations (solvent, acid, and nonionic surfactant)

Type

Type 1 (wt.%) iwt.%) Type pH Type iwt.%)

2

Ex 1 Water 94.90 — 0.00 — 6-7 BG-10 0.20

Ex 2 Water 79.21 — 0.00 — 6-7 BD-109 0.99

Ex 3 Water 23.21 — 0.00 — 6-7 BG-10 0.20

Ex 4 — 0.00 IPA 95.00 — — — 0.00

Ex 5 — 0.00 MeOH 91.35 — — — 0.00

Ex 6 — 0.00 IPA 95.00 — — — 0.00

Ex 7 — 0.00 IPA 95.00 — — — 0.00

Ex 8 — 0.00 MeOH 92.50 — — — 0.00

Ex 9 Water 94.89 — 0.00 Acetic acid 3-4 BG-10 0.19

Ex 10 Water 94.91 — 0.00 Nitric acid 2-3 BG-10 0.19

Ex 11 Water 92.95 — 0.00 Citric acid 2-3 BG-10 0.20

Ex 12 Water 98.77 — 0.00 HC1 2-3 BG-10 0.19

Formic

Ex 13 Water 58.32 — 0.00 2-3 BG-10 0.19 acid

Ex 14 Water 40.80 — 0.00 HC1 2-3 BD-109 1.90

Ex 15 Water 16.25 — 0.00 HC1 3-4 BG-10 0.17

Ex 16 Water 47.81 IPA 45.84 H3PO4 2-3 BG-10 0.19

Ex 17 Water 47.81 IPA 45.84 H3PO4 2-3 BG-10 0.19

Ex 18 Water 4.32 IPA 90.51 HC1 2-3 — 0.00

Ex 19 Water 3.96 EtOH 85.40 HC1 2-3 — 0.00

Ex 20 Water 19.20 BuOH 72.00 Oxalic acid 3-4 — 0.00

Ex 21 Water 4.17 IPA 89.97 HC1 1-2 — 0.00

Ex 22 Water 24.87 PrOH 68.72 HC1 1-2 — 0.00

Ex 23 Water 91.10 — 0.00 HC1 2-3 BG-10 0.33

Ex 24 Water 92.13 — 0.00 HC1 2-3 BG-10 0.19

Ex 25 Water 93.80 — 0.00 HC1 2-3 BG-10 0.19

Ex 26 Water 94.35 — 0.00 HC1 2-3 BG-10 0.19 Ex 27 Water 94.08 — 0.00 HC1 2-3 BG-10 0.19

Ex 28 Water 94.20 — 0.00 HC1 2-3 BG-10 0.19

Ex 29 Water 93.81 — 0.00 HC1 2-3 BG-10 0.19

Ex 30 Water 93.00 — 0.00 HC1 2-3 BG-10 0.48

Ex 31 Water 94.64 — 0.00 HC1 1-2 BG-10 0.19

Ex 32 Water 94.75 — 0.00 HC1 2-3 BG-10 0.19

Ex 33 Water 94.71 — 0.00 HC1 2-3 BG-10 0.19

Ex 34 Water 94.49 — 0.00 HC1 2-3 BG-10 0.19

Ex 35 Water 94.39 — 0.00 HC1 2-3 BG-10 0.19

Ex 36 Water 93.61 — 0.00 HC1 2-3 BG-10 0.19

Preparation and Performance Test for the Slip Resistant Article

Example 37

The slip resistant article is prepared using the bar coating method, the method comprises the steps of:

A vitrified tile (225 mm* 150 mm* 10 mm) is used as the substrate of the slip resistant article. The surface of the vitrified tile is first cleaned with liquefied detergent (White Cat brand, commercially available from SHANGHAI HEHUANG White Cat Ltd.), and then rinsed clean with deionized water, and subsequently blow-dried with compressed air;

The winding bar of the automatic bar coater (K303 Multicoater, commercially available from RK Print Coat Instruments Inc.) is placed at one end of the vitrified tile, and 5 g of the slip resistant solution obtained from Example 1 is dropped uniformly to the gap between the winding bar and the vitrified tile by a dropper;

At room temperature, the slip resistant solution is bar-coated on the surface of the vitrified tile by using an automatic bar coater;

During the bar coating process, the wet film thickness of the slip resistant solution is about 6 μιη, and is recorded as T-6, as shown in Table 3;

The bar-coated vitrified tile is heated in an oven to dry at 120°C for 1 hour. The tile was then removed from the oven and cooled to room temperature to obtain a slip resistant article. The slip resistance performance, abrasion resistance performance and surface wettability of the obtained slip resistant article are tested, and the results are listed in Table 4, Table 5 and Table 6, respectively.

Example 38 to 58

The slip resistant articles are prepared using the same method as in Example 37, wherein the types of the substrates, the bar coating conditions and heat treatment conditions of the slip resistant articles are listed in Table 3.

As shown in Table 3, if the wet film thickness of the slip resistant article during the bar coating process is 1.5 μηι, it is recorded as T-1.5; if the wet film thickness of the slip resistant article during the bar coating process is 3 μηι, it is recorded as T-3; if the wet film thickness of the slip resistant article during the bar coating process is 6 μηι, it is recorded as T-6; if the wet film thickness of the slip resistant article during the bar coating process is 12 μηι, it is recorded as T- 12. The slip resistance performance, the abrasion resistance performance and the surface wettability of the obtained slip resistant articles are tested, and the results are listed in Table 4, Table 5 and Table 6, respectively.

Example 59

The slip resistant article is prepared by using the bar coating method, and the method comprises the steps of:

A vitrified tile (225 mm* 150 mm* 10 mm) is used as the substrate of a slip resistant article. The surface of the vitrified tile is first cleaned with a liquefied detergent (White Cat brand, commercially available from SHANGHAI HEHUANG White Cat Ltd.), and then rinsed clean with deionized water, and subsequently blow-dried with compressed air;

10 g of slip resistant solution obtained from Example 23 is filtered twice using a 200-mesh filter screen;

The winding bar of the automatic bar coater (K303 Multicoater, commercially available from RK Print Coat Instruments Inc.) is placed at one end of the vitrified tile, and 5 g of filtered slip resistant solution is dropped uniformly to the gap between the winding bar and the vitrified tile by a dropper;

At room temperature, the slip resistant solution is bar-coated on the surface of the vitrified tile using an automatic bar coater; During the bar coating process, the wet film thickness of the slip resistant solution is about 6 μηι, and is recorded as T-6, as shown in Table 3;

The bar-coated vitrified tile is dried at room temperature for 18 hours to obtain the slip resistant article.

The slip resistance performance, the abrasion resistance performance and the surface wettability of the obtained slip resistant article are tested, and the results are listed in Table 4, Table 5 and Table 6, respectively.

Example 60 to 72

The slip resistant articles are prepared using the same method as in Example 59, wherein the types of the substrates, the bar coating conditions and the heat treatment conditions of the slip resistant articles are listed in Table 3.

The slip resistance performance, the abrasion resistance performance and the surface wettability of the obtained slip resistant articles are tested, and the results are listed in Table 4, Table 5 and Table 6, respectively.

Example 73

Then 0.01 g of 3-(2-aminoethyl)-3-aminopropyl trimethoxy silane is added to a 20 ml glass bottle. During the process of stirring on a magnetic stirrer, 9.99 g of deionized water is added. After stirring continuously for 10 minutes, a clear primer solution A is obtained.

The winding bar of the automatic bar coater (K303 Multicoater, commercially available from RK

Print Coat Instruments Inc.) is placed at one end of the vitrified tile, and 5 g of primer solution A is dropped uniformly to the gap between the winding bar and the vitrified tile by a dropper;

At room temperature, the primer solution A is bar-coated on the surface of the vitrified tile using an automatic bar coater.

During the bar coating process, the wet film thickness of the slip resistant solution A is about 6 μιη, and is recorded as T-6, as shown in Table 3;

The bar-coated vitrified tile is heated in an oven to dry at 120°C for 10 minutes and removed out, and then cooled to room temperature;

10 g of the slip resistant solution obtained from Example 26 is filtered twice using a 200-mesh filter screen;

The winding bar of the automatic bar coater is placed at one end of the vitrified tile coated with the primer solution A, and 5 g of the filtered slip resistant solution is dropped uniformly to the gap between the winding bar and the vitrified tile by a dropper;

At room temperature, the slip resistant solution is bar-coated on the surface of the vitrified tile using an automatic bar coater;

The bar-coated vitrified tile is dried at room temperature for 16 hours, to obtain the slip resistant article.

Example 74

0.05 g of bis(3-trimethoxysilylpropyl)amine is added to a 20 ml glass bottle. During the process of stirring on a magnetic stirrer, 9.95 g of isopropanol is added. After stirring continuously for 10 minutes, a clear primer solution B is obtained. The winding bar of the automatic bar coater (K303 Multicoater, commercially available from RK Print Coat Instruments Inc.) is placed at one end of the vitrified tile, and 5 g of primer solution B is dropped uniformly to the gap between the winding bar and the vitrified tile by a dropper;

At room temperature, the primer solution B is bar-coated on the surface of the vitrified tile using an automatic bar coater;

During the bar coating process, the wet film thickness of the slip resistant solution B is about 6 μηι, and is recorded as T-6, as shown in Table 3;

The bar-coated vitrified tile is heated in an oven to dry at 120°C for 10 minutes, and then removed out and cooled to room temperature;

10 g of slip resistant solution obtained from Example 10 is filtered twice using a 200-mesh filter screen;

The winding bar of the automatic bar coater is placed at one end of the vitrified tile coated with primer solution B, and 5 g of filtered slip resistant solution is dropped uniformly to the gap between the winding bar and the vitrified tile by a dropper;

During the bar coating process, the wet film thickness of the slip resistant solution is about 6 μηι, and is recorded as T-6, as shown in Table 3;

The bar-coated vitrified tile is dried at room temperature for 24 hours, to obtain the slip resistant article.

Example 75

A slip resistant article is prepared by using the bar coating method, and the method comprises the steps of:

0.20 g of 3-(N,N-dimethylaminopropyl)-aminopropylmethyl dimethoxy silane is added to a 20 ml glass bottle. During the process of stirring on a magnetic stirrer, 2.00 g of deionized water and 7.80 g of isopropanol are added. After stirring continuously for 10 minutes, a clear primer solution C is obtained.

Print Coat Instruments Inc.) is placed at one end of the vitrified tile, and 5 g of primer solution C is dropped uniformly to the gap between the winding bar and the vitrified tile by a dropper;

At room temperature, the primer solution C is bar-coated on the surface of the vitrified tile using an automatic bar coater.

During the bar coating process, the wet film thickness of the slip resistant solution C is about 6 μηι, and is recorded as T-6, as shown in Table 3;

The bar-coated vitrified tile is heated in an oven to dry at 120°C for 10 minutes. The tile is then removed from the oven and cooled to room temperature;

10 g of slip resistant solution obtained from Example 9 is filtered twice using a 200-mesh filter screen;

The winding bar of the automatic bar coater is placed at one end of the vitrified tile coated with primer solution C, and 5 g of filtered slip resistant solution is dropped uniformly to the gap between the winding bar and the vitrified tile using a dropper;

Example 76

The slip resistant article is prepared by using the wiping coat method, and the method comprises the steps of:

A glazed tile (200 mm x 200 mm x 10mm) is used as the substrate of the slip resistant article. The surface of the glazed tile is first cleaned with liquefied detergent (White Cat brand, commercially available from SHANGHAI HEHUANG White Cat Ltd.), and then rinsed clean with deionized water, and subsequently blow-dried with compressed air;

Spun-bonded polypropylene non-woven fabric (commercially available from 3M Company) is cut into a 50 mm x 20 mm strip. 6 g of the filtered slip resistant solution is drawn off with a dropper. 3 g of the filtered slip resistant solution is dropped to one end of the glazed tile, and the other 3 g is dropped to the middle of the glazed tile. The non- woven fabric is pressed by hand on the glazed tile, and the glazed tile is coated uniformly once from the end having the slip resistant solution to the end without the solution.

The wipe-coated glazed tile is dried at room temperature for 24 hours, to obtain the slip resistant article.

Example 77 to 79

The slip resistant articles are prepared using the same method as in Example 76, wherein the types of the substrates, the wipe coating conditions and the heat treatment conditions of the slip resistant articles are listed in Table 3.

Example 80

The slip resistant article is prepared by using the brush coating method, and the method comprises the steps of: An artificial marble tile (500 mm><500 mm* 14 mm) is used as the substrate of the slip resistant article. The surface of the artificial marble tile is first cleaned with liquefied detergent (White Cat brand, commercially available from SHANGHAI HEHUANG White Cat Ltd.), and then rinsed clean with deionized water, and subsequently blow-dried with compressed air;

50 g of slip resistant solution obtained from Example 23 is filtered twice using a 200-mesh filter screen;

Spun-bonded polypropylene non-woven fabric (commercially available from 3M Company) is mounted on the application instrument (Standard Doodleduster Holder, commercially available from 3M Company). 20 g of the filtered slip resistant solution is dropped with a dropper to one end of the artificial marble tile. The application instrument is controlled by hand and coated uniformly once on the artificial marble tile from one end having the slip resistant solution to the end without it.

The brush-coated artificial marble tile is dried at room temperature for 16 hours, to obtain the slip resistant article.

Example 81

The slip resistant articles are prepared using the same method as in Example 80, wherein the kinds of substrates, the brush coating conditions and the heat treatment conditions of the slip resistant articles are listed in Table 3.

The slip resistance performances, the abrasion resistance performance and the surface wettability of the obtained slip resistant articles are tested, and the results are listed in Table 4, Table 5 and Table 6, respectively.

Comparative Example 1 to 7

The vitrified tile, glazed tile, archaized tile, microlite stone, polished tile, artificial granite tile and artificial marble tile uncoated with the slip resistant solution are used as Comparative Example 1 to 7, and the detail information thereof is listed in Table 3.

The slip resistance performance, the abrasion resistance performance and the surface wettability of the obtained uncoated substrates are tested, and the results are listed in Table 4, Table 5 and Table 6, respectively.

Table 3 : Preparation of the slip resistant articles

Bar coating h(Bar

Example 57 Example 21 Vitrified tile 100°C/90 Minutes

T-6)

Example 58 Example 22 Vitrified tile Bar coatingC Bar T-6) 150°C/10 Minutes

Room temperature

Example 59 Example 23 Vitrified tile Bar coatingC Bar T-6)

/18 hours

Room

Example 60 Example 24 Vitrified tile Bar coatingC Bar T-6) temperature/20 hours

Room

Example 61 Example 25 Vitrified tile Bar coatingC Bar T-6) temperature/23 hours

Room

Example 62 Example 26 Vitrified tile Bar coating(Bar T-6) temperature/19 hours

Room

Example 63 Example 27 Vitrified tile Bar coatingC Bar T-6) temperature/24 hours

Room

Example 64 Example 28 Vitrified tile Bar coatingC Bar T-6) temperature/22 hours

Room

Example 65 Example 29 Vitrified tile Bar coatingC Bar T-6) temperature/22 hours

Room

Example 66 Example 30 Vitrified tile Bar coatingC Bar T-6) temperature/17 hours

Room

Example 67 Example 31 Vitrified tile Bar coatingC Bar T-6) temperature/24 hours Room

Example 68 Example 32 Vitrified tile Bar coatingC Bar T-6) temperature/24 hours

Room

Example 69 Example 33 Vitrified tile Bar coatingC Bar T-6) temperature/23 hours

Room

Example 70 Example 34 Vitrified tile Bar coatingC Bar T-6) temperature/24 hours

Room

Example 71 Example 35 Vitrified tile Bar coatingC Bar T-6) temperature/24 hours

Room

Example 72 Example 36 Vitrified tile Bar coatingC Bar T-6) temperature/26 hours

Primer solution

Bar coating(Bar T-6) 120°C/10 Minutes A

Example 73 Vitrified tile Room

Example 26 Bar coatingCBar T-6) temperature/16 hours

Primer solution

Bar coatingCBar T-6) 120°C/10 Minutes B

Example 74 Vitrified tile Room

Example 10 Bar coatingCBar T-6) temperature/24 hours

Primer solution

Example 75 Vitrified tile Bar coatingCBar T-6) 120°C/10 Minutes

C Room

Example 9 Bar coatingCBar T-6) temperature/16 hours

Room

Example 76 Example 23 Glazed tile Wipe coating temperature/24 hours

Room

Example 77 Example 23 Archaized tile Wipe coating temperature/21 hours

Room

Example 78 Example 23 Microlite stone Wipe coating temperature/24 hours

Room

Example 79 Example 23 Polished tile Wipe coating temperature/25 hours

Room

Artificial

Example 80 Example 23 Brush coating temperature/16 marble tile

hours

Room

Artificial

Example 81 Example 23 Brush coating temperature/16 granite tile

hours

Comparative

— Vitrified tile — — Example 1

Comparative

— Glazed tile — — Example 2

Comparative

— Archaized tile — — Example 3

Comparative

— Microlite stone — — Example 4 Comparative

— Polished tile — —

Example 5

Comparative Artificial

Example 6 marble tile

Comparative Artificial

Example 7 granite tile

^{( }} T-3 : The wet film thickness is controlled to be approximately 3 um by the bar used during the bar coating process;

^{( }} T-12: The wet film thickness is controlled to be approximately 12 μηι by the bar used during the bar coating process;

⁽³⁾ T- 1.5 : The wet film thickness is controlled to be approximately 1.5 μηι by the bar used during the bar coating process.

Table 4: Slip Resistance Performance Test of the Slip Resistant Articles

Example 49 1.10 358.33% 1.27 25.74%

Example 50 1.26 425.00% 1.16 14.85%

Example 51 1.32 450.00% 1.18 16.83%

Example 52 1.32 450.00% 1.14 12.87%

Example 53 0.99 312.50% 1.19 17.82%

Example 54 1.32 450.00% 1.20 18.81%

Example 55 1.32 450.00% 1.24 22.77%

Example 56 1.32 450.00% 1.29 27.72%

Example 57 1.04 333.33% 0.86 -14.85%

Example 58 1.19 395.83% 0.88 -12.87%

Example 59 1.20 400.00% 1.24 22.77%

Example 60 1.21 404.17% 1.21 19.80%

Example 61 1.32 450.00% 1.32 30.69%

Example 62 1.32 450.00% 1.25 23.76%

Example 63 0.82 241.67% 1.29 27.72%

Example 64 1.32 450.00% 1.22 20.79%

Example 65 1.32 450.00% 1.31 29.70%

Example 66 1.32 450.00% 1.25 23.76%

Example 67 1.32 450.00% 1.28 26.73%

Example 68 0.75 212.50% 1.13 11.88%

Example 69 1.10 358.33% 1.23 21.78%

Example 70 0.76 216.67% 1.09 7.92%

Example 71 1.30 441.67% 1.26 24.75%

Example 72 1.32 450.00% 1.24 22.77%

Example 73 0.93 287.50% 1.08 6.93%

Example 74 1.21 404.17% 1.27 25.74%

Example 75 1.32 450.00% 1.01 0.00%

Example 76 1.32 127.59% 1.27 23.30%

Example 77 1.32 153.85% 0.95 23.38% Example 78 1.32 388.89% 1.19 9.17%

Example 79 1.32 186.96% 1.11 4.72%

Example 80 1.32 169.39% 1.20 16.50%

Example 81 1.31 424.00% 1.30 17.12%

Comparative — —

0.24 1.01

Example 1

Comparative — —

0.58 1.03

Example 2

Comparative — —

0.52 0.77

Example 3

Comparative — —

0.27 1.09

Example 4

Comparative — —

0.46 1.06

Example 5

Comparative — —

0.49 1.03

Example 6

Comparative — —

0.25 1.11

Example 7

The increase percentage of the wet static friction coefficient in Table 4 is obtained by the following equation:

(Wet static friction coefficient of the slip resistant article— wet static friction coefficient of the corresponding substrate uncoated with the slip resistant coating) / wet static

friction coefficient of the corresponding substrate uncoated with the slip resistant

coating

The increase percentage of the dry static friction coefficient in Table 4 is obtained by the following equation:

(Dry static friction coefficient of the slip resistant article— dry static friction coefficient of the corresponding substrate uncoated with the slip resistant coating) / dry state

friction coefficient of the corresponding substrate uncoated with the slip resistant coating

As shown in Table 4, the dry static friction coefficients of the selected substrates are all greater than 0.6. Compared to the substrates uncoated with the slip resistant coatings, the wet static friction coefficients of the substrates provided according to Examples 37 to 56, and 59 to 81 have increased dramatically, and are all greater than 0.6. Compared to the substrates uncoated with the slip resistant coatings, their dry static friction coefficients have also been slightly improved or remained unchanged. For the slip resistant articles provided in Examples 57 and 58, the wet static friction coefficients have increased dramatically, and are all greater than 0.6. This is because the third silane with low surface energy is added to the slip resistant solution, thus increasing the hydrophobicity of the slip resistant articles. Although the dry static friction coefficient slightly decreased, it still remains within the safety range of the slip resistance performance under dry condition. Comparative Examples 1 to 7 provide the substrates uncoated with the slip resistant coatings, all of which have a wet static friction coefficient less than 0.6, therefore the slip resistance performance is poor under wet condition. Table 5: Wear Resistant Performance Test of the Slip Resistant Articles

In Table 5, Example 46 is the slip resistant article obtained from the slip resistant solution without adding a second silane or a multifunctional amine, and Examples 59 and 62 are respectively the slip resistant articles obtained from the slip resistant solution by adding different kinds of second silanes, and Examples 67 to 72 are respectively the slip resistant articles obtained from the slip resistant solution by adding different kinds of multifunctional amines. It can be seen that good abrasion resistance performance can be obtained by adding appropriate amounts of the second silane or multifunctional amine in the slip resistant solution.

Table 6: Surface Wettability Test of the Slip Resistant Articles

In Table 6, Example 55 is the slip resistant article obtained from the slip resistant solution without adding a third silane, an organosilicon quaternary ammonium salt or a surfactant; Examples 38 and 49 are the slip resistant articles obtained from the slip resistant solution by adding different kinds of nonionic surfactants; and Example 44 is the slip resistant article obtained from the slip resistant solution by adding a certain kind of organosilicon quaternary ammonium salt; and Examples 56-58 are the slip resistant articles obtained from the slip resistant solution by adding different kinds of third silanes. It can be seen that, adding appropriate amount of the organosilicon quaternary ammonium salt or surfactant can make the surface of the slip resistant article more hydrophilic, and adding appropriate amount of the third silicon can make the surface of the slip resistant article more hydrophobic, therefore adding the appropriate amount of the third silane, the organosilicon quaternary ammonium salt or surfactant can adjust the surface wettability of the slip resistant article.

Although for purposes of illustration, the specific embodiments described above contain many specific details, but the skilled person will appreciate that many variations, modifications, substitutions and changes of such details are within the protection scope of the present invention, which is indicated by the claims. Therefore, the disclosure described in the embodiment does not make any restriction of the protection scope of the present invention, which is indicated by the claims. The appropriate scope of the present invention should be defined by the claims and the appropriate legal equivalents. All cited references are incorporated herein by reference in its entirety.

Claims

We claim:

1. A slip resistant article comprising a substrate and a slip resistant coating applied on the surface of the substrate, characterized in that,

the substrate is a ceramic tile substrate;

the slip resistant coating is further prepared from a slip resistant solution; the slip resistant solution comprises the reaction product of the following reaction components:

1-83.5 wt.% of a first silane, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the first silane being R^Si (OR) 4-_a-bR²b, wherein the value of a is 0 to 3; when the value of a is 0, the value of b is 0; when the value of a is 1, the value of b is 0 to 2; when the value of a is 2, the value of b is 0 to 1 ; when the value of a is 3, the value of b is 0; R represents alkyl group having 1 to 4 carbon atoms; R¹ represents hydrocarbyl group with epoxy functional group; and R² represents alkyl group having 1 to 2 carbon atoms; and

16.5-99 wt.% of a first solvent, based on the total weight of the slip resistant solution as 100 wt.%, the first solvent being one or more selected from the group consisting of: water and alcohol.

2. The slip resistant article according to claim 1, characterized in that, the ceramic tile substrate is one or more selected from the group consisting of: vitrified tile, glazed tile, archaized tile, microlite stone, polished tile, artificial granite tile, and artificial marble tile. 3. The slip resistant article according to claim 1, characterized in that, the first silane is one or more selected from the group consisting of: 3-glycidoxypropyltrimethoxysilane,

3 -glycidoxypropylmethyldiethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltriethoxysilane, tetramethyl orthosilicate, and tetraethyl orthosilicate. 4. The slip resistant article according to claim 1, characterized in that, the alcohol is one or more selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, and n-butanol.

5. The slip resistant article according to claim 1, characterized in that, the slip resistant solution further comprises an acid, and the pH of the slip resistant solution is less than or equal to 4.

6. The slip resistant article according to claim 5, characterized in that, the acid is an inorganic acid or an organic acid; the inorganic acid is one or more selected from the group consisting of: hydrochloric acid, nitric acid and phosphoric acid; the organic acid is one or more selected from the group consisting of: formic acid, acetic acid, oxalic acid, and citric acid.

7. The slip resistant article according to claim 1, characterized in that, the slip resistant solution further comprises 0-3.0 wt.% of a second silane, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the second silane being R³ _cSi(OR)4-_c-dR⁴, wherein the value of c is 0 to 3; when the value of c is 1, the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms.

8. The slip resistant article according to claim 7, characterized in that, the second silane is one or more selected from the group consisting of: 3-aminopropyltriethoxysilane,

3-(2-aminoethyl)-aminopropylmethyldimethoxysilane,

3-(N,N-dimethylaminopropyl)-aminopropylmethyldimethoxysilane, and

bis(3-trimethoxysilylpropyl)amine.

9. The slip resistant article according to claim 1, characterized in that, the slip resistant solution further comprises 0- 1.4 wt.% of a multifunctional amine, based on the total weight of the slip resistant solution as 100 wt.%. 10. The slip resistant article according to claim 9, characterized in that, the multifunctional amine is one or more selected from the group consisting of: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, and polyethyleneimine.

11. The slip resistant article according to claim 1 , characterized in that, the slip resistant solution further comprises 0-2.5 wt.% of an organosilicon quaternary ammonium salt, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the organosilicon quaternary ammonium salt being Si(OR)3R⁵N⁺(R⁶)3-X^", wherein R represents alkyl group having 1 to 4 carbon atoms, R⁵ represents hydrocarbyl group, oxygen-containing group or nitrogen-containing group, R⁶ represents hydrocarbyl group having 1 to 20 carbon atoms, and X represents an acid radical.

12. The slip resistant article according to claim 11, characterized in that, the organosilicon quaternary ammonium salt is N-trimethoxysilylpropyl-N, N, N- trimethylammonium chloride.

13. The slip resistant article according to claim 1, characterized in that, the slip resistant solution further comprises 0-3.0 wt.% of a third silane, based on the total weight of the slip resistant solution as 100 wt.%, the general formula of the third silane being R⁷ _eSi(OR)4-_e, wherein the value of e is 1 to 3, R represents alkyl group having 1 to 4 carbon atoms, and R⁷ represents alkyl group having 1 to 20 carbon atoms. 14. The slip resistant article according to claim 13, characterized in that, the third silane is one or more selected from the group consisting of: methyltrimethoxysilane, n-octyltriethoxysilane, and

hexadecyltrimethoxysilane.

15. The slip resistant article according to claim 1, characterized in that, the slip resistant solution further comprises 0-2.0 wt.% of a nonionic surfactant, based on the total weight of the slip resistant solution as

100 wt.%.

16. The slip resistant article according to claim 1, characterized in that, a primer is further provided between the slip resistant coating and the substrate, and the primer is further prepared from a primer solution, and the primer solution comprises the reaction product of the following reaction components:

0.1-2.0 wt.% of a fourth silane, based on the total weight of the primer solution as 100 wt.%, the general formula of the fourth silane being R³ _cSi(OR)4-_c-dR⁴d, wherein the value of c is 0 to 3; when the value of c is 1 , the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms; and

98.0-99.9 wt.% of a second solvent, based on the total weight of the primer solution as 100 wt.%, and the second solvent is one or more selected from the group consisting of: water and alcohol.

17. A method for preparing the slip resistant article according to claims 1 to 15, comprising the steps of: applying a slip resistant solution to a surface of a substrate to form a wet layer on the surface of the substrate, drying the wet layer to form a slip resistant coating, wherein the slip resistant coating is attached to the surface of the substrate.

18. The preparation method according to claim 17, characterized in that, before applying a slip resistant solution to a surface of a substrate to form a wet layer on the surface of the substrate, a wet layer of a primer solution is applied on the surface of the substrate, then drying the wet layer to form a primer, and the primer solution comprises the reaction product of the following reaction components:

0.1-2.0 wt.% of a fourth silane, based on the total weight of the primer solution as 100 wt.%, the general formula of the fourth silane being R³ _cSi(OR)4-_c-dR⁴d, wherein the value of c is 0 to 3; when the value of c is 1, the value of d is 0 to 2; when the value of c is 2, the value of d is 0 to 1 ; when the value of c is 3, the value of d is 0; R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group with a primary, secondary or tertiary amino functional group, and R⁴ represents alkyl group having 1 to 2 carbon atoms; and

19. The preparation method according to claim 17, characterized in that, the slip resistant solution is applied to the surface of the substrate by the following means: bar coating, wipe coating, brush coating, dip coating, and spray coating.

20. The preparation method according to claim 18, characterized in that, the primer solution is applied to the surface of the substrate by the following means: bar coating, wipe coating, brush coating, dip coating and spray coating.