WO2015171360A1

WO2015171360A1 - Slip resistant liquid, slip resistant article and the method for preparing the same

Info

Publication number: WO2015171360A1
Application number: PCT/US2015/027970
Authority: WO
Inventors: Long Yin; Zhigang Yu; Shupeng WU; Naiyong Jing
Original assignee: 3M Innovative Properties Company
Priority date: 2014-05-09
Filing date: 2015-04-28
Publication date: 2015-11-12
Also published as: CN105086794B; CN105086794A

Abstract

The present invention provides a slip resistant liquid comprising a reaction product of a reaction mixture comprising: 0.2-5 wt.% of a polymer; 0.5-10 wt.% of silica particles with an average particle size of less than or equal to 60 nm; 1-10 wt.% of a first silane represented by the general formula of 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 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; 80-97 wt.% of water; and an acid, wherein the slip resistant liquid has a pH value of less than or equal to 5, the above percentages by weight are all based on the total weight of the slip resistant liquid as 100 wt.%. The slip resistant liquid provided by the present invention can form a slip resistant coating on the surface of the substrate to obtain a slip resistant article having good slip resistance performance.

Description

SLIP RESISTANT LIQUID, SLIP RESISTANT ARTICLE AND THE METHOD FOR

PREPARING THE SAME

Cross Reference To Related Application

This application claims priority to CN Patent Application 201410196078.5, filed on May 9, 2014, the disclosure of which is incorporated by reference in its entirety.

FIELD OF THE INVENTION

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

BACKGROUND OF THE INVENTION

The surface of ceramic tile substrate, glass substrate and polyvinyl chloride substrate will become slippery after experiencing water, which makes people tend to slip down and get injured or the like. Therefore, it is important for the surface of the above substrates to be treated for improved slip resistance.

One of the common approaches for slip resistant treatment is to apply a slip resistant coating on the surface of the substrate to increase the surface friction of the substrate, and to increase the friction coefficient to a safe level so as to achieve the slip resistant effect, thereby reducing accidents of slipping down and getting injured and the like.

Currently, the slip resistant coating usually uses alkyd resin, chlorinated rubber, phenolic resin, epoxy resin, or urethane resin as film-forming resin, which is filled with slip resistant pellets of quartz sand, corundum, titanium oxide, aluminum oxide or rubber grains and the like. These pellets have irregular shapes and protrude from the surface of the coating, which can increase surface roughness and friction and reduce the sliding tendency of a person or other objects on the surface, so as to achieve slip resistance. For example, CN101328379 (Yuan Jun and Xinhua Sun) discloses an epoxy cement-based road slip resistant coating, which is composed of three components: epoxy emulsion, curing agents and powder, and the curing agent is made by mixing triethylene triamine or triethylene tetramine and low molecular weight polyamide resin. The powder is composed of Portland cement, quartz sand and water reducer, wherein the powder is fixed on the cement road by cured epoxy resin to achieve the slip resistant effect.

WO20101 14700 (Jing et al.) discloses a composition, method for preparing the composition, and method for using the composition to coat the substrate, the composition comprising an aqueous continuous liquid phase and core/shell particles dispersed in the aqueous continuous liquid phase, and each core/shell particle comprises a polymer core surrounded by a shell and a non-porous spherical silica particle shell disposed on the polymer core.

WO2012045204 (Jing et al.) discloses a method for making an article, comprising the steps of: coating the composition comprising aqueous continuous liquid phase, silica nanoparticles dispersed in the aqueous continuous liquid phase and the polymer latex dispersion on the surface of the substrate, and then heating the coated substrate to at least 300°C.

SUMMARY OF THE INVENTION

The present invention aims to provide a new slip resistant liquid to satisfy the requirement of providing better slip resistance performance under wet and slippery conditions.

According to one aspect of the present invention, a slip resistant liquid is provided, which comprises a reaction product of a reaction mixture comprising:

0.2-5 wt.% of a polymer, based on the total weight of the slip resistant liquid as 100 wt.%;

0.5-10 wt.% of silica particles, based on the total weight of the slip resistant liquid as 100 wt.%, and the silica particles have an average particle size of less than or equal to 60 nanometers (nm);

1-10 wt.% of a first silane, based on the total weight of the slip resistant liquid as 100 wt.%, and the first silane is represented by the general formula of R¹ _aSi(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;

80-97 wt.% of water, based on the total weight of the slip resistant liquid as 100 wt.%; and an acid, wherein the slip resistant liquid has a pH value of less than or equal to 5. According to another aspect of the present invention, a slip resistant article is provided, which comprises a substrate and a slip resistant coating disposed on a surface of the substrate. The slip resistant coating is obtained by applying a layer of a slip resistant liquid as described above to the surface of the substrate and then drying the layer.

According to another aspect of the present invention, a method for preparing the slip resistant article is provided, which includes the steps of: applying the slip resistant liquid described above to a surface of the substrate, forming a layer of wet slip resistant liquid coating on the surface of the substrate, and drying the layer of wet slip resistant liquid to form a slip resistant coating attached to the substrate.

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 include 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, and so on.

The slip resistant liquid

The slip resistant liquid provided by the present invention comprises a reaction product of a reaction mixture comprising: 0.2-5 wt.% of a polymer, based on the total weight of the slip resistant liquid as 100 wt.%; 0.5-10 wt.% of silica particles, based on the total weight of the slip resistant liquid as 100 wt.%, and the silica particles have an average particle size of less than or equal to 60 nm; 1-10 wt.% of a first silane, based on the total weight of the slip resistant liquid as 100 wt.%, and the first silane is represented by the general formula of R¹ _aSi(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; 80-97 wt.% of water, based on the total weight of the slip resistant liquid as 100 wt.%; and an acid, wherein the slip resistant liquid has a pH value of less than or equal to 5.

The polymer may comprise any polymer, typically one that can be prepared as an emulsion, more typically as an alkaline pH stable emulsion. The polymer may be one or more selected from the group consisting of: acrylic polymer, styrene polymer, vinyl acetate-ethylene copolymer, polyvinyl acetate, styrene -butadiene rubber, polyurethane (including polyurethane-acrylic polymer), polyester, and polyamide. Preferably, the polymer is a film-forming polymer. The polymer may be thermosetting or thermoplastic, and more preferably, the polymer comprises polyurethane, acrylic or a combination thereof. Examples of commercially available polymer emulsions include those aqueous aliphatic polyurethane emulsions available as NeoRez R-620, NeoRez R-961 and NeoRez R-966 from DSM; aqueous acrylic emulsion available as NeoCryl A-612 from DSM; aqueous polyurethane-acrylic compolymer emulsion NeoPac E- 180 from DSM. The content of the polymer is 0.2-5 wt.%, preferably 0.2-3 wt.%, and more preferably 0.2-1.5 wt.%, based on the total weight of the slip resistant liquid as 100 wt.%. If the content of the polymer is less than 0.2 wt.%, the binding force of the slip resistant coating further prepared from this slip resistant liquid and the substrate may be weak, therefore it may be difficult to achieve the slip resistance performance possessed by the slip resistant article of the present invention; if the content of the polymer is greater than 5 wt.%, the stability of the slip resistant liquid may be poor, and it may be difficult to obtain a uniform coating having slip resistance performance.

The slip resistant liquid may comprise silica particles with a single average particle size, and may also comprise the combination of the silica particles with two or more average particle sizes. The particle size herein and in the claims refers to the length of the largest axis of the particle. The average particle size of the silica particles is less than or equal to 60 nm, preferably less than or equal to 20 nm, and more preferably less than or equal to 5 nm. The silica particles in aqueous media (sols) are well known in the art and are available commercially; for example, as silica sols in water or aqueous alcohol solutions under the trade designations Nalco from Nalco Chemical Company. One useful silica sol with an average particle size of 5 nm and a nominal solid content of 15 wt.%, is available as Nalco 2326 from Nalco Chemical Company. Other useful commercially available silica sols include those available as Nalco 1115 and Nalco 1050 from Nalco Chemical Co., and as LI-0515 from Evonik Industry Group. The content of the silica particles is 0.5-10 wt.%, preferably 0.5-7 wt.%, and more preferably 0.5-4 wt.%, based on the total weight of the slip resistant liquid as 100 wt.%. If the content of the silica particles is less than 0.5 wt.%, the stability of the slip resistant liquid may be poor, and it may be difficult to obtain a uniform coating having slip resistance performance. If the content of the silica particles is greater than 10 wt.%, the slip resistance performance of the slip resistant coating further prepared from this slip resistant liquid may be poor, therefore it may be difficult to achieve the slip resistance performance possessed by the slip resistant article of the present invention.

The slip resistant liquid is obtained by reacting the first silane with other reaction components, and the slip resistant coating or slip resistant article further prepared from this slip resistant liquid has good slip resistance performance. The first silane may be one or more selected from the group consisting of: tetramethyl orthosilicate, tetraethyl orthosilicate, 3-glycidoxypropyltrimethoxysilane,

3-glycidoxypropylmethyldiethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and more preferably tetraethyl orthosilicate and 3-glycidoxypropyltrimethoxysilane. The content of the first silane is 1-10 wt.%, preferably 1-8 wt.%, and more preferably 1-5 wt.%, based on the total weight of the slip resistant liquid as 100 wt.%. If the content of the first silane is less than 1 wt.%, the slip resistance performance of the slip resistant coating further prepared from this slip resistant liquid may be poor, therefore it may be difficult to achieve the slip resistance performance possessed by the slip resistant article of the present invention; if the content of the first silane is greater than 10 wt.%, it may be difficult to obtain a uniform coating having slip resistance performance.

The content of water is 80-97 wt.%, based on the total weight of the slip resistant liquid as 100 wt.%. If the content of water is less than 80 wt.%, the stability of the slip resistant liquid may be poor, and it may be difficult to obtain a uniform coating having slip resistance performance. If the content of water is greater than 97 wt.%, it may be more difficult to form a slip resistant coating with sufficient thickness on the substrate, therefore it may be difficult to achieve the slip resistance performance possessed by the slip resistant article of the present invention.

The acid may be inorganic acid or organic acid. The inorganic acid may be one or more selected from the group consisting of: hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, and more preferably hydrochloric acid and phosphoric acid. The organic acid may be one or more selected from the group consisting of: formic acid, acetic acid, propionic acid, oxalic acid, citric acid, benzoic acid and benzenesulfonic acid, and more preferably formic acid, acetic acid, oxalic acid and citric acid. The slip resistant liquid may also comprise the combination of inorganic acid and organic acid. The content of the acid is not particularly limited, as long as it enables the pH value of the slip resistant liquid to be less than or equal to 5, preferably less than or equal to 4, and more preferably less than or equal to 3. If the pH value of the slip resistant liquid is greater than 5, it may be difficult to obtain a uniform coating having slip resistance performance.

The slip resistant liquid described by the present invention can further comprise organosilicon quaternary ammonium salt. The organosilicon quaternary ammonium salt can increase the stability of the slip resistant liquid. The organosilicon quaternary ammonium salt is represented by the general formula of Si(OR)3R³N⁺(R⁴)3-X^", wherein R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group, oxygen-containing group or nitrogen-containing group, R⁴ represents hydrocarbyl group having 1 to 20 carbon atoms, and X represents an acid radical anion. R³ may be one or more selected from the group consisting of: -CH₂-, -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂COCH₂CH₂- and

-(CH₂)₃NHCH₂CH₂-. R⁴ may be one or more selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, and n-butyl. X may be one or more selected from the group consisting of: chloride, sulphate, nitrate and phosphate. The organosilicon quaternary ammonium salt is preferably

N-trimethoxysilyl- propyl-N,N,N-trimethyl ammonium chloride. The content of the organosilicon quaternary ammonium salt is 0.01-0.5 wt.%, preferably 0.03-0.5 wt.%, and more preferably 0.03-0.1 wt.%, based on the total weight of the slip resistant liquid as 100 wt.%. If the content of the

organosilicon quaternary ammonium salt is greater than 0.5 wt.%, the slip resistance performance of the slip resistant coating further prepared from this slip resistant liquid may be poor, therefore it may be difficult to achieve the slip resistance performance possessed by the slip resistant article of the present invention.

The slip resistant liquid of the present invention may further comprise organic solvent. The organic solvent is miscible with water, and can improve the invasiveness of the slip resistant liquid to the surface of the substrate. The organic solvent may be one or more selected from the group consisting of: alcohols, ketones, esters and low molecular weight ethers. The alcohols are 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 low molecular weight ethers are 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 content of the organic solvent is 0.01-5wt.%, preferably 0.05-3 wt.%, and more preferably 0.05-2 wt.%, based on the total weight of the slip resistant liquid as 100 wt.%. If the content of the organic solvent is greater than 5 wt.%, the slip resistance performance of the slip resistant coating further prepared from this slip resistant liquid may be poor, therefore it may be difficult to achieve the slip resistance performance possessed by the slip resistant article of the present invention.

The slip resistant liquid according to the present invention can further comprise nonionic surfactant. The nonionic surfactant can improve the invasiveness of the slip resistant liquid to the surface of the substrate. The nonionic surfactant may be one or more selected from the group consisting of: a polyoxyethylene-type nonionic surfactant, a polyol-type nonionic surfactant, an alkanolamide-type nonionic surfactant, a fluorocarbon-type nonionic surfactant, a silicone-type nonionic surfactant, and a modified silicone-type nonionic surfactant. The content of the nonionic surfactant is 0.01-2 wt.%, preferably 0.01-1 wt.%, and more preferably 0.05-0.5 wt.%, based on the total weight of the slip resistant liquid as 100 wt.%. If the content of the nonionic surfactant is greater than 2 wt.%, the slip resistance performance of the slip resistant coating further prepared from this slip resistant liquid may be poor, therefore it may be difficult to achieve the slip resistance performance possessed by the slip resistant article of the present invention. The slip resistant article

The slip resistant article provided by the present invention comprises a substrate and slip resistant coating applied to the surface of the substrate. The substrate is ceramic tile substrate, glass substrate or polyvinyl chloride substrate; the "ceramic tile" herein and in the claims is suitable for ceramic material including those prepared from fire-resistant clay, brick material, concrete, ceramics, marble, limestone, other rock material and slate. The substrate is one or more selected from the group consisting of: ceramic tile substrate, glass substrate or polyvinyl chloride substrate, and the ceramic tile substrate is one or more selected from the group consisting of: vitrified tiles, glazed tiles, microlite stones and artificial stones.

The slip resistant coating includes the coating obtained by drying the slip resistant liquid provided by the present invention. The slip resistant coating is completely or partially free of water, and preferably completely free of water. The description of the slip resistant liquid can be found in the "slip resistant liquid" section of the description of the present invention in detail.

The slip resistant coating can significantly improve the slip resistance performance of the substrate under wet and slippery conditions. The slip resistant coating can be of any suitable thickness as required, and the slip resistant coating can have a thickness of 100-2000 nm, or 200-1500 nm, or 200- 1000 nm.

Method for preparing the slip resistant article

The method for preparing the slip resistant article provided by the present invention comprises the steps of: applying the slip resistant liquid provided by the present invention to the surface of a substrate, forming a layer of wet slip resistant liquid on the surface of the substrate, and drying the layer to form a slip resistant coating attached to the substrate.

The description of the slip resistant liquid, the substrate, the slip resistant coating and the slip resistant article can be found in the "slip resistant liquid" and "slip resistant article" sections of the description of the present invention in detail.

The known methods in the art can be used to coat the slip resistant liquid on the surface of the substrate, 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.

Suitable drying methods known in the art can be used to dry the slip resistant liquid, and this drying process can be performed above room temperature, e.g., 40-150°C, or 60-120°C, or 80-120^ooC.

The present invention provides a plurality of preferred embodiments about the slip resistant liquid, the slip resistant article, and the methods for preparing the same.

The preferred embodiment 1 is a slip resistant liquid comprising a reaction product of a reaction mixture comprising:

(a) 0.2-5 wt.% of a polymer, based on the total weight of the slip resistant liquid as 100 wt.%; (b) 0.5-10 wt.% of silica particles, based on the total weight of the slip resistant liquid as 100 wt.%, and the silica particles having an average particle size of less than or equal to 60 nm;

(c) 1-10 wt.% of a first silane, based on the total weight of the slip resistant liquid as 100 wt.%, and the first silane is represented by the general formula of 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;

(d) 80-97 wt.% of water, based on the total weight of the slip resistant liquid as 100 wt.%; and

(e) an acid, wherein the slip resistant liquid has a pH value of less than or equal to 5.

The preferred embodiment 2 is a slip resistant liquid according to the preferred embodiment 1 , wherein the polymer comprises a film-forming thermoplastic polymer.

The preferred embodiment 3 is a slip resistant liquid according to the preferred embodiment 2, wherein the film- forming thermoplastic polymer comprises polyurethane, acrylic polymer or a combination thereof.

The preferred embodiment 4 is a slip resistant liquid according to any one of the preferred embodiments 1 to 3, wherein the slip resistant liquid further comprises 0.01-0.5 wt.% of organosilicon quaternary ammonium salt, based on the total weight of the slip resistant liquid as 100 wt.%, and the organosilicon quaternary ammonium salt is represented by the general formula of Si(OR)3R³N⁺(R⁴)3-X^", wherein R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group, oxygen-containing group or nitrogen-containing group, R⁴ represents hydrocarbyl group having 1 to 20 carbon atoms, and X represents an acid radical anion.

The slip resistant coating or slip resistant article further prepared by using the slip resistant liquid according to the preferred embodiments 1 to 4 has good slip resistance performance.

The preferred embodiment 5 is a slip resistant liquid according to any one of the preferred embodiments 1 to 4, wherein the slip resistant liquid further comprises 0.01-5 wt.% of organic solvent, based on the total weight of the slip resistant liquid as 100 wt.%.

The preferred embodiment 6 is a slip resistant liquid according to any one of the preferred embodiments 1 to 5, wherein the slip resistant liquid further comprises 0.01-2 wt.% of nonionic surfactant, based on the total weight of the slip resistant liquid as 100 wt.%.

Using the slip resistant liquid according to the preferred embodiments 5 to 6 not only infiltrates the surface of the substrate better, but also enables the slip resistant coating or slip resistant article further prepared from the slip resistant liquid to have good slip resistance performance.

The preferred embodiment 7 is a slip resistant article, comprising a substrate and a slip resistant coating disposed on the substrate, wherein the slip resistant coating is obtained by applying a layer of any slip resistant liquid according to claims 1 to 6 to the surface of the substrate and then drying the layer.

The preferred embodiment 8 is a slip resistant article according to the preferred embodiment 7, wherein the substrate comprises one or more selected from the group consisting of: ceramic tile substrate, glass substrate or polyvinyl chloride substrate.

The preferred embodiment 9 is a slip resistant article according to the preferred embodiment 8, wherein the ceramic tile substrate comprises one or more selected from the group consisting of: vitrified tiles, glazed tiles, microlite stones and artificial stones.

The slip resistant articles according to the preferred embodiments 7 to 9 have good slip resistance performance.

The preferred embodiment 10 is a method for preparing the slip resistant article, comprising the steps of: applying any slip resistant liquid according to the preferred embodiments 1 to 6 to the surface of a substrate, forming a layer of wet slip resistant liquid on the surface of the substrate, and drying the layer to form a slip resistant coating attached to the substrate.

The preferred embodiment 11 is a preparation method according to the preferred embodiment 10, wherein the slip resistant liquid is applied to the surface of the substrate by the following methods: bar coating, wipe coating, brush coating, dip coating, and spray coating.

The slip resistant articles prepared by using the methods according to the preferred embodiments 10 to 11 have good slip resistance performance. 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

Product Name Chemical Property / Specification Supplier Polyurethane aqueous emulsion, with a solid

NeoRez R-620

content of 35-37 wt.%

Polyurethane aqueous emulsion, with a solid

NeoRez R-961

content of 34 wt.%

Polyurethane aqueous emulsion,

NeoRez R-966 DSM Group with a solid content of 33 wt.%

Acrylic aqueous emulsion,

NeoCryl A-612

with a solid content of 31-33 wt.%

Polyurethane-acrylic copolymer aqueous

NeoPac E-180

emulsion, with a solid content of 31-33 wt.%

An aqueous dispersion of silica Evonik

LI-0515 nanoparticles, with a solid content of 16- 18 Industry wt.%, and an average particle size of 4-5 nm Group

An aqueous dispersion of silica

Nalco 8699 nanoparticles, with a solid content of 15-16

wt.%, and an average particle size of 2-4 nm

An aqueous dispersion of silica

Nalco 1115 nanoparticles, with a solid content of 15

wt.%, and an average particle size of 4 nm

An aqueous dispersion of silica

Nalco 2326 nanoparticles, with a solid content of 15 Nalco Co.

wt.%, and an average particle size of 5 nm

An aqueous dispersion of silica

Nalco 1050 nanoparticles, with a solid content of 50

wt.%, and an average particle size of 20 nm

An aqueous dispersion of silica

Nalco 1060 nanoparticles, with a solid content of 50

wt.%, and an average particle size of 60 nm

Tetraethyl orthosilicate Purity >98.5 wt.% Sinopharm Chemical

Reagent Co., Ltd.

Shanghai -Glycidoxypropyltrimet Yaohua

Purity >98.0 wt.%

hoxysilane Chemical

Plant

N-trimethoxysilyl-

U.S. Gelest propyl-N,N,N-trimethyl 50 wt.% in methanol

Co. ammonium chloride

Acetone Purity >99.5 wt.%

Propylene glycol Sinopharm

Purity >99.5 wt.%

monomethyl ether Chemical

Hydrochloric acid HC1, purity =36—38 wt.% Reagent Co.,

Phosphoric acid H3PO₄, purity >85.0 wt.% Ltd.

Acetic acid HAc, purity >99.5 wt.%

Alkylpolyglucoside surfactant, TRITON Dow BG-10, with water solution of 70 wt.% Chemical Co.

Nonionic surfactant

Polyether-modified silicone-based BYK surfactants, BYK-349, purity of 100 wt.% Chemical Co.

Vitrified tile 225mmx 150mmx 10mm Shanghai

Glazed tile 300mmx300mm l0mm Bohao

Microlite stone 300mmx300mmx l0mm Building

Materials

Artificial stone 200mmx200mmx20mm

Co., Ltd.

Shanghai Jinqiao

Glass substrate 180mmx l00mmx3mm

Trading Co., Ltd. Black, Brand BN-004, Shanghai

300mmx300mmx2mm Yangguang

Polyvinyl chloride (PVC)

Decoration substrate Stone grain, Brand YP- 1004 ,

Materials 3 OOmmx 3 OOmmx 3mm

Co., Ltd.

The present invention evaluates the slip resistance performance of the slip resistant coatings or slip resistant articles provided by the Examples and Comparative Examples mainly through the wet static friction coefficient test. On this basis, through the surface gloss test, the present invention further assesses the impact of slip resistant coatings provided by the Examples and Comparative Examples on the appearance of the substrate.

Slip Resistance Performance test

Static friction coefficient is an important indicator for evaluating the slip resistance safety performance of the ground. The slip resistance performance of slip resistant coatings or slip resistant articles under wet and slippery conditions is characterized by the wet static friction coefficient in the present invention.

The equipment for testing the wet static friction coefficient is ASM 825A, commercially available from American Slip Meter Company. Friction medium for testing the wet static friction coefficient is Neolite rubber (Shore hardness of 93-96, commercially available from Goodyear Tire and Rubber Company).

A slip resistant liquid is applied to the surface of the substrate, and the dried slip resistant liquid 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.

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 standards once provided by Underwriters Laboratories (UL) and the American Society for Testing and Materials (ASTM) : Static friction coefficient range Safety level

0.00-0.34 Extremely dangerous

0.35-0.39 Very dangerous

0.40-0.49 dangerous

0.50-0.59 Basically safe

Above 0.60 Very safe

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 and slippery conditions. The larger the value is, the better the slip resistance performance is.

The test results of the wet static friction coefficient of the slip resistant coatings and slip resistant articles provided by the Examples and Comparative examples of the present invention are listed in Table 3.

Surface Gloss Test

The present invention characterizes the impact of the slip resistant coatings on the appearance of the substrate through the surface gloss test.

The equipment for testing the surface gloss is Micro-Tri-Gloss gloss meter, commercially available from BYK-Gardner Company.

Slip resistant liquid is coated on the surface of the substrate, forming a slip resistant coating on the surface of the substrate after drying, to obtain a slip resistant article comprising the substrate and the slip resistant coating.

Micro-Tri-Gloss gloss meter is used to measure the surface gloss value of the slip resistant article. Three different regions are randomly taken from the surface of the slip resistant article, and the surface gloss values of 20°, 60° and 85° are measured respectively, taking the average value of each angle.

The test results of the surface gloss of the slip resistant coatings and slip resistant articles provided by the Examples and Comparative examples of the present invention are listed in Table 4.

Preparation of the Slip Resistant Liquid Example 1

4.92 g of LI-0515 silica nanoparticle aqueous dispersion liquid (with a solid content of 16-18 wt.%) is added to a 250 ml glass bottle;

88.34 g of deionized water is added while stirring on a magnetic stirrer;

After stirring continuously for 10 minutes, 3.62 g of NeoRez R-966 polyurethane aqueous emulsion (with a solid content of 33 wt.%) is added;

After stirring continuously for 10 minutes, 3.12 g of tetraethylorthosilicate is added.

After stirring continuously for 16 hours at room temperature, 3.81 g (17 wt.%) solution of phosphoric acid in water is added dropwise, and the pH is adjusted to 2 to 3.

After stirring continuously for 1 hour, 1.00 g (50 wt.%) solution of N-trimethoxysilyl- propyl-N,N,N-trimethyl ammonium chloride in methanol is added;

After stirring continuously for 30 minutes, the slip resistant liquid of Example 1 is obtained.

Example 2

The slip resistant liquid of Example 2 is prepared in the same method as in Example 1, wherein the types and contents of components included in the slip resistant liquid are listed in Tables 2-1 and 2-2.

Example 3

1.58 g of Nalco 1060 silica nanoparticle aqueous dispersion liquid (with a solid content of 50 wt.%) is added to a 250 ml glass bottle;

96.77 g of deionized water is added while stirring on a magnetic stirrer;

After stirring continuously for 10 minutes, 0.55 g of NeoRez R-961 polyurethane aqueous emulsion (with a solid content of 38 wt.%) is added;

After stirring continuously for 1 hour at room temperature, 1.01 g (17 wt.%) solution of phosphoric acid in water is added dropwise, and the pH is adjusted to 2 to 3.

After stirring continuously for 1 hour, 1.10 g of 3-glycidoxypropyltrimethoxysilane is added;

After stirring continuously for 1 hour, 1.00 g of acetone is added;

After stirring continuously for 30 minutes, the slip resistant liquid of Example 3 is obtained. Example 4 to 9

The slip resistant liquid of Examples 4 to 9 is prepared in the same method as in Example 3, wherein the types and contents of components included in the slip resistant liquid are listed in Tables 2- 1 and 2-2.

Table 2-1. Slip resistant liquid formulations

Table 2-2. Slip resistant liquid formulations

Preparation and Performance Test for the Slip resistant article

Example 10

The slip resistant article is prepared using the bar coating method, comprising the following steps: 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 firstly 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 liquid 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 liquid 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 liquid 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 30 minutes and then taken out, and cooled to room temperature to obtain a slip resistant article.

The slip resistance performance and surface gloss of the obtained slip resistant article are tested, and the results are listed in Table 3 and Table 4.

Example 11 to 22

The slip resistant articles are prepared using the same method as in Example 10, 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 during the bar-coating process is 1.5 μηι, it is recorded as T- 1.5; if the wet film thickness during the bar-coating process is 3 μηι, it is recorded as T-3; if the wet film thickness of the slip resistant liquid during the bar-coating process is 6 μηι, it is recorded as T-6; if the wet film thickness of the slip resistant liquid during the bar-coating process is 12 μηι, it is recorded as T- 12. The slip resistance performance and surface gloss of the obtained slip resistant article are tested, and the results are listed in Table 3 and Table 4.

Example 23

The slip resistant article is prepared by using the dip coating method, comprising the steps of:

A glass substrate (180 mm* 100 mm><3 mm) is used as the substrate of a slip resistant article. The surface of the glass substrate is firstly 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;

200 g of slip resistant liquid obtained in Example 7 is poured into a 400 ml stainless steel tank

(150mm 150mm 20mm);

At room temperature, by using an automatic dip coater (SKVDX2S-500, commercially available from KSV NIMA Company), the glass substrate is dip-coated in the slip resistant liquid;

The immersion speed of the dip coating process is 300 mm/min, the immersion time is 1 minute, and the pulling speed is 300 mm/min, as listed in Table 3 in detail.

The dip-coated glass substrate is heated in an oven to dry at 120 C for 30 minutes and then taken out, and cooled to room temperature to obtain a slip resistant article.

Example 24

The slip resistant article is prepared by using the wipe coating method, comprising the following steps:

A PVC substrate (black, 300 mm x 300 mm x 2 mm) is used as the substrate of the slip resistant article. The surface of the PVC substrate is firstly 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. 10 g of the slip resistant liquid obtained in Example 4 is drawn off with a dropper. 5 g of the slip resistant liquid is dropped to one end of the PVC substrate, and the other 5 g is dropped to the middle of the PVC substrate. The non-woven fabric is pressed by hand on the PVC substrate, and the substrate is coated uniformly once from the end with the slip resistant liquid to the end without the liquid.

The wipe-coated PVC substrate is heated in an oven to dry at 60^°C for 90 minutes and then taken out, and cooled to room temperature to obtain a slip resistant article.

Example 25

The slip resistant article is prepared by using the brush coating method, comprising the following steps:

A PVC substrate (Stone grain, 300 mmx300 mmx3 mm) is used as the substrate of the slip resistant article. The surface of the PVC substrate is firstly 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 mounted on the application instrument (Standard Doodleduster Holder, commercially available from 3M Company). 20 g of the slip resistant liquid obtained in Example 4 is dropped with a dropper to one end of the PVC substrate. The application instrument is controlled by hand to coat uniformly once on the PVC substrate from one end with the slip resistant liquid to the end without the liquid.

The brush-coated PVC substrate is heated in an oven to dry at 60 C for 90 minutes and then taken out, and cooled to room temperature to obtain a slip resistant article.

Comparative Example 1 to 7

The vitrified tiles, glazed tiles, microlite stones, artificial stones, glass substrates, PVC substrates

(black) and PVC substrates (stone grain) not coated with the slip resistant coating are used as

Comparative Examples 1 to 7, and the detailed information thereof is listed in Table 3 and Table 4.

The slip resistance performance and the surface gloss of the substrate not coated with the slip resistant coating are tested, and the results are listed in Table 3 and Table 4.

Table 3. Preparation of the slip resistant articles and slip resistance performance test

8 (Bar T-3⁽³⁾)

Example Bar coating

Example 22 Vitrified tile 120°C/30mins 0.96

9 (Bar T- 1.5⁽⁴⁾)

Dip

coating(Immersion &

Example pulling speed

Example 23 Glass substrate 120°C/30mins 0.88

7 300mm/min,

immersion time 1

min)

Example PVC substrate

Example 24 Wipe coating 60°C/90mins 1.22

4 (Black)

Example PVC substrate

Example 25 Brush coating 60°C/90mins 1.29

4 (Stone grain)

Comparative

— Vitrified tile — — 0.17 Example 1

Comparative

— Glazed tile — — 0.45 Example 2

Comparative

— Microlite stone — — 0.22 Example 3

Comparative

— Artificial stone — — 0.47 Example 4

Comparative

— Glass substrate — — 0.31 Example 5

Comparative PVC substrate

— — — 0.64 Example 6 (Black)

Comparative PVC substrate

— — — 0.67 Example 7 (Stone grain

Note: ⁽¹⁾ T-6: The wet film thickness is controlled to be approximately 6 μηι 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) ^. _wet gj_m Sickness is controlled to be approximately 3 μηι by the bar used during the bar coating process.

⁽⁴⁾ T-1.5: The wet film thickness is controlled to be approximately 1.5 μηι by the bar used during the bar coating process.

As shown in Table 3, the substrates provided by Comparative Examples 1 to 5 are not coated with the slip resistant coating, and their wet static friction coefficients are all less than 0.6, therefore their slip resistance performance is poor under wet and slippery conditions. The substrates provided by

Comparative Examples 6 to 7 are not coated with the slip resistant coating, and although their wet static friction coefficients are slightly greater than 0.6, their slip resistance performance under wet and slippery conditions are still not satisfactory. The wet static friction coefficients of slip resistant articles provided according to Examples 10 to 25 have increased dramatically compared to the substrates not coated with slip resistant coating, and are all significantly greater than 0.6. Therefore, these slip resistant articles have good slip resistance performance under wet and slippery conditions.

Table 4. Surface gloss test for slip resistant articles

Comparative Example 1 Vitrified tile 68.0 73.0 85.2

Comparative Example 3 Microlite stone 67.6 80.0 87.3

Comparative Example 4 Artificial stone 71.0 84.8 86.4

Comparative Example 6 PVC substrate (Black) 0.7 6.3 12.1

PVC substrate

Comparative Example 7 41.7 78.7 83.0

(Stone grain)

As can be seen from Table 4, the surface gloss of the slip resistant articles provided according to certain preferred embodiments of the present invention can increase or remain unchanged compared to the substrates not coated with the slip resistant coating. Therefore, the slip resistant articles provided by these preferred Examples also have good appearance.

Although for purposes of illustration, the specific embodiments described above contain many specific details, but a skilled person in the art will appreciate that many variations, modifications, substitutions and changes of such details fall 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 liquid comprising a reaction product of a reaction mixture comprising:

0.5-10 wt.% of silica particles, based on the total weight of the slip resistant liquid as 100 wt.%, and the silica particles have an average particle size of less than or equal to 60 nm;

80-97 wt.% of water, based on the total weight of the slip resistant liquid as 100 wt.%; and an acid, wherein the slip resistant liquid has a pH value of less than or equal to 5.

2. The slip resistant liquid according to claim 1, wherein the polymer comprises a film-forming thermoplastic polymer.

3. The slip resistant liquid according to claim 2, wherein the film-forming thermoplastic polymer comprises polyurethane, acrylic polymer or a combination thereof.

4. The slip resistant liquid according to any one of claims 1 to 3, wherein the slip resistant liquid further comprises 0.01-0.5 wt.% of organosilicon quaternary ammonium salt, based on the total weight of the slip resistant liquid as 100 wt.%, and the organosilicon quaternary ammonium salt is represented by the general formula of Si(OR)3R³N⁺(R⁴)3-X^", wherein R represents alkyl group having 1 to 4 carbon atoms, R³ represents hydrocarbyl group, oxygen-containing group or nitrogen-containing group, R⁴ represents hydrocarbyl group having 1 to 20 carbon atoms, and X represents an acid radical anion.

5. The slip resistant liquid according to any one of claims 1 to 4, wherein the slip resistant liquid further comprises 0.01-5 wt.% of organic solvent, based on the total weight of the slip resistant liquid as 100 wt.%.

6. The slip resistant liquid according to any one of claims 1 to 5, wherein the slip resistant liquid further comprises 0.01-2 wt.% of nonionic surfactant, based on the total weight of the slip resistant liquid as 100 wt.%.

7. A slip resistant article comprising a substrate and a slip resistant coating disposed on the substrate, wherein the slip resistant coating is obtained by applying a layer of any slip resistant liquid according to claims 1 to 6 to the surface of the substrate and then drying the layer.

8. The slip resistant article according to claim 7, wherein the substrate comprises one or more selected from the group consisting of: ceramic tile substrate, glass substrate and polyvinyl chloride substrate.

9. The slip resistant article according to claim 8, wherein the ceramic tile substrate comprises one or more selected from the group consisting of: vitrified tiles, glazed tiles, microlite stones and artificial stones.

10. A method for preparing a slip resistant article, comprising the steps of: applying any slip resistant liquid according to claims 1 to 6 to the surface of a substrate, forming a layer of wet slip resistant liquid on the surface of the substrate, and drying the layer to form a slip resistant coating attached to the substrate.

11. The preparation method according to claim 10, wherein the slip resistant liquid is applied to the surface of the substrate by the following methods: bar coating, wipe coating, brush coating, dip coating, and spray coating.