TW201811943A - Protective coating composition with anti-skid function, coating product and preparation method thereof - Google Patents

Abstract

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

Description

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

The invention relates to a protective coating composition with a non-slip function, a coated product and a preparation method thereof.

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

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

At present, non-slip coatings usually use alkyd resin, chlorinated rubber, phenolic resin, epoxy resin or urethane resin as the film-forming resin, and are filled with quartz sand, corundum, titanium oxide, alumina or rubber. Granules and other non-slip granules. The shape of these non-slip granules is irregular and protrudes from the coating surface, which can increase the roughness and friction of the surface and reduce the sliding of people or other objects on the surface, thereby achieving the purpose of anti-slip.

In recent years, another study found that the requirement of anti-skid can be achieved only by special coating without filling with anti-skid particles. CN104926369 (Yinlong, etc.) discloses a non-slip coating using a ceramic tile substrate, including a first silane and a solvent, wherein the first silane is an epoxy silane or an orthosilicate, and the solvent is selected from water or alcohol. However, the non-slip coating cannot meet the requirements of higher wear resistance and scratch resistance. In order to meet the higher abrasion and scratch resistance requirements in some occasions, the abrasion resistance and scratch resistance of the non-slip coating need to be further improved.

The formulations of US20100209719 and US20100015339 both disclose hydrolysates of siloxane containing epoxy functional groups, and their role is to react with other components to achieve the antiseptic function.

The present invention aims to provide a protective coating composition with a non-slip function, so as to meet the demand of anti-slip under the wet and slippery environment of the dry coating and coated products prepared by using the protective coating composition. The dry coating and the coated product have good abrasion resistance and scratch resistance at the same time, and can play a role of durable protection of the substrate.

According to one aspect of the present invention, the present invention provides a protective coating composition having a non-slip function. Based on the total weight of the coating composition as 100 wt.%, The reaction product includes the following reaction components: 1) A reaction solution, the first reaction solution includes reaction products of the following reaction components: 1-30 wt.% Of a siloxane oligomer and / or polymer A containing an epoxy functional group, The siloxane oligomer and / or polymer A containing an epoxy functional group has a linear, branched, or cyclic structure, and can be represented by the general formula I: HO- [ SiR ¹ (OR ³ ) -O] _a- [SiR ² (OR ³ ) -O] _b- [Si (OH) ₂ -O] _c -H (Ⅰ), where 0 <a ≤ 100; 0 <b ≤ 100; 0 ≤ c ≤ 100; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed and / or hydrolyzed epoxy functional group, including one or more of the following groups: 3-shrink Glyceryl etheroxypropyl, 3- (2,3-dihydroxypropoxy) propyl, 2- (3,4-epoxycyclohexyl) ethyl and 2- (3, 4-hydroxycyclohexyl Yl) ethyl; R ³ represents a hydrogen atom or a C 1-4 alkyl group, including the group of one or more of: methyl, ethyl, n-propyl, isopropyl, n-butyl, di Butyl, isobutyl and tertiary butyl; 1-15 wt.% Of silane functional group B containing epoxy functional group, the silane compound B containing epoxy functional group may It is represented by the general formula II: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II), where 0 ≤ d ≤ 2; R ⁴ represents an Organic groups, including one or more of the following groups: 3- (2, 3-epoxypropoxy) propyl, 3- (2, 3-dihydroxypropoxy) propyl, 2- (3,4-Ethoxycyclohexyl) ethyl and 2- (3,4-dihydroxycyclohexyl) ethyl; R ³ represents a hydrogen atom or Alkyl groups 1-4, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and tertiary butyl ; Said siloxane functional group containing siloxane oligomer and / or polymer The weight ratio of A to the epoxy functional group-containing silane compound B is at least 1: 1; 45-96 wt.% Water; and acid; the pH value of the first reaction solution is less than or equal to 5; 2) 0.2-5 wt.% Silane compound C containing amino functional group, the silane compound C containing amino functional group can be represented by general formula III: [(R ³ O ) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (III), where 0 ≤ e ≤ 1; 0 ≤ f ≤ 1; 1 ≤ g ≤ 6; 0 ≤ h ≤ 1; 0 ≤ i ≤ 6; 0 ≤ j ≤ 2; 0 ≤ k ≤ 2; R ⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl, alkenyl or benzyl group having a carbon number of 1-6; R ⁶ represents a carbon number of 1-6 Linear, branched, or cyclic alkyl or alkenyl; R ³ represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, including one or more of the following groups: methyl, ethyl, N-propyl, isopropyl, n-butyl, secondary butyl, isobutyl and tertiary butyl; 3) 0.2-5 wt.% Orthosilicate, which can be used The general formula IV represents: Si (OR) ₄ (IV), wherein R represents an alkyl group having a carbon number of 1-4, and includes one or more of the following groups: methyl, ethyl, n-propyl, isopropyl , N-butyl, secondary butyl, isobutyl, and tertiary butyl.

According to another aspect of the present invention, the present invention provides a coated article including a substrate and a dry coating applied on the substrate, the dry coating including applying the coating composition to the The surface of the substrate is a coating obtained by drying.

According to another aspect of the present invention, the present invention provides a method for preparing a coated product, including the following steps: applying the coating composition on the surface of the substrate, and forming a wet coating composition on the surface of the substrate And drying the wet coating composition liquid film to obtain a dry coating, and the dry coating is adhered to the surface of the substrate.

It should be understood that those skilled in the art can envision other various embodiments and modifications to them based on the teachings of this specification without departing from the scope or spirit of the invention. Therefore, the following specific embodiments are not restrictive.

Unless otherwise indicated, all numbers expressing quantities and physicochemical properties used in this specification and the scope of the patent application should be understood to be modified in all cases by the term "about". Therefore, unless stated to the contrary, the numerical parameters listed in the above description and the scope of the appended patent applications are approximate values. Those skilled in the art can use the teachings disclosed herein to seek for the required characteristics and appropriately change these. approximation. The use of a numerical range represented by an endpoint includes all digits in the range and any range in the range, for example, 1, 2, 3, 4 and 5 include 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5 and so on.

Coating composition

The protective coating composition with anti-slip function provided by the present invention includes the reaction products of the following reaction components based on the total weight of the coating composition as 100 wt.%: 1) a first reaction solution, said The first reaction solution includes the reaction products of the following reaction components: 1-30 wt.% Of a siloxane-containing siloxane oligomer and / or polymer A, which contains cyclic The siloxane functional siloxane oligomer and / or polymer A has a linear, branched, or cyclic structure and can be represented by the general formula I: HO- [SiR ¹ (OR ³ ) -O] _a- [SiR ² (OR ³ ) -O] _b- [Si (OH) ₂ -O] _c -H (I) where 0 <a ≤ 100; 0 <b ≤ 100; 0 ≤ c ≤ 100; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed and / or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyl etheroxypropyl, 3- (2,3-dihydroxypropoxy) propyl, 2- (3,4-epoxycyclohexyl) ethyl, and 2- (3, 4 - dihydroxy cyclohexyl) ethyl; R ³ represents hydrogen Or 1-4 alkyl groups, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl and tertiary Butyl; 1-15 wt.% Silane compound B containing epoxy functional group, the silane compound B containing epoxy functional group can be represented by general formula II: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) where 0 ≤ d ≤ 2; R ⁴ represents an organic group containing at least one unhydrolyzed and / or hydrolyzed epoxy functional group, including one of the following groups or Various: 3-glycidyl etheroxypropyl, 3- (2, 3-dihydroxypropoxy) propyl, 2- (3, 4-epoxyoxycyclohexyl ) Ethyl and 2- (3,4-dihydroxycyclohexyl) ethyl; R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups : Methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and tertiary butyl; said siloxane containing epoxy functional groups Oligomer and / or polymer A with said containing oxygen The weight ratio of the silane compound B of the functional group is at least 1: 1; 45-96 wt.% Water; and acid; the pH value of the first reaction solution is less than or equal to 5; 2) 0.2-5 wt.% Silane compound C containing amino functional group, the silane compound C containing amino functional group can be represented by the general formula III: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (Ⅲ) where 0 ≤ e ≤ 1; 0 ≤ f ≤ 1; 1 ≤ g ≤ 6; 0 ≤ h ≤ 1; 0 ≤ i ≤ 6; 0 ≤ j ≤ 2; 0 ≤ k ≤ 2; R ⁵ represents a hydrogen atom or a carbon number of Linear, branched or cyclic alkyl, alkenyl or benzyl of 1-6; R ⁶ represents linear, branched or cyclic carbon having 1-6 Alkyl or alkenyl; R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, Secondary butyl, isobutyl and tertiary-butyl; 3) 0.2-5 wt% of n-silicon ester, the ester can be represented by n-silicon formula Ⅳ: Si (OR) ₄ ( ) Where R represents an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl And tertiary butyl.

The general formula of the siloxane oligomer and / or polymer A containing epoxy functional group is preferably HO- [SiR ¹ (OR ³ ) -O] _a- [SiR ² ( OR ³ ) -O] _b- [Si (OH) ₂ -O] _c -H (I) where 0 <a ≤ 20; 0 <b ≤ 20; 0 ≤ c ≤ 20; R ¹ and R ² are independent Ground represents an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyl etheroxypropyl and 2- (3, 4-epoxy ring Hexyl) ethyl; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, and isopropyl.

The content of the epoxy group-containing siloxane oligomer and / or polymer A is 1-30 wt.%, Preferably 1-25 wt.%, And particularly preferably 4.5-25 wt. .%, Based on 100 wt.% Of the total weight of the coating composition. If the content of the epoxy functional group-containing siloxane oligomer and / or polymer A is less than 1 wt.%, It may be difficult to form a dry coating of sufficient thickness on the surface of the substrate , So that the slip resistance and abrasion resistance of the coated product provided by the present invention cannot be achieved. If the content of the epoxy functional group-containing siloxane oligomer and / or polymer A is greater than 30 wt.%, The first reaction solution and the amino functional group-containing silane compound C and normal silicon The reaction speed of the acid ester may be too fast, and the appearance of the dried coating obtained therefrom may have many defects, which may cause the appearance of the obtained coated product to have obvious defects.

The general formula of the silane compound B containing epoxy functional group is preferably: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) wherein 0 ≤ d ≤ 2; R ⁴ represents An organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyl etheroxypropyl and 2- (3, 4-epoxycyclohexyl) ) Ethyl; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, and isopropyl.

The epoxy functional group-containing silane compound B includes one or more of the following groups: 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxy Silane, 3-Glycidyletheroxypropylmethyldimethoxysilane, 3-Glycidyletheroxypropylmethyldiethoxysilane, 3-Glycidyletheroxypropylethyldimethyl Oxysilane, 3-glycidyl etheroxypropylethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxy Cyclohexyl) ethyltriethoxysilane.

The content of the silane compound B containing epoxy functional groups is 1-15 wt.%, Preferably 1-13 wt.%, Particularly preferably 3-13 wt.%, And the coating composition is combined The total weight is calculated as 100 wt.%. If the content of the epoxy functional group-containing silane compound B is less than 1 wt.%, The first reaction solution is reacted with the amino functional group-containing silane compound C and orthosilicate to obtain a coating composition. The anti-slip properties of the dried coatings and coated products obtained by further preparing the coating composition may not be good enough to achieve the anti-slip properties of the coated products provided by the present invention. If the content of the epoxy functional group-containing silane compound B is greater than 15 wt.%, The reaction rate of the first reaction solution with the amino functional group-containing silane compound C and orthosilicate may be too fast. There may be many defects in the appearance of the resulting dried coating, resulting in obvious defects in the appearance of the obtained coated product.

The weight ratio of the epoxy functional group-containing siloxane oligomer and / or polymer A to the epoxy functional group-containing silane compound B is at least 1: 1 , Preferably 1.2: 1, and particularly preferably 1.5: 1. If the weight ratio of the epoxy functional group-containing siloxane oligomer and / or polymer A to the epoxy functional group-containing silane compound B is less than 1: 1 , After the first reaction solution is mixed with the amino functional group-containing silane compound C and the orthosilicate, precipitation occurs, and it cannot be used to further prepare the dried coating or coated product provided by the present invention.

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

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

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

The amino functional group-containing silane compound C includes one or more of the following groups: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl Methyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylethyl Dimethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethyl Oxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltriethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propylmethyl Dimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propylmethyldiethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyl Trimethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyl Triethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzene 3-aminopropyltriethoxysilane, N, N-dimethyl-3-aminopropyltrimethoxysilane, N, N-diethyl-3-aminopropyltrimethoxysilane, N , N-Diethyl-3-aminopropyltriethoxysilane, N-ethyl-3-trimethoxysilyl-2-methylpropylamine, N- [3- (trimethoxysilyl) propyl Propyl] n-butylamine, bis [(3-trimethoxysilyl) -propyl] amine, bis [(3-triethoxysilyl) -propyl] amine.

The content of the amino functional group-containing silane compound C is 0.2-5 wt.%, Preferably 0.2-3 wt.%, Particularly preferably 0.8-3 wt.%, With the coating composition. The total weight is calculated as 100 wt.%. If the content of the amino functional group-containing silane compound C is less than 0.2 wt.%, When it is reacted with the first reaction solution and the orthosilicate to obtain a coating composition, the coating composition is applied to It may be difficult to completely cure the surface of the substrate, and the slip resistance, abrasion resistance, and scratch resistance of the further obtained dried coatings and coated products may be poor, so that the coated products provided by the present invention cannot be achieved. With anti-skid performance, wear resistance and scratch resistance. If the content of the amino functional group-containing silane compound C is greater than 5 wt.%, When it is reacted with the first reaction solution and the orthosilicate to obtain a coating composition, the coating composition is further used to prepare the coating composition. The anti-slip properties, abrasion resistance, and scratch resistance of the obtained dried coatings and coated products may be poor, so that the slip resistance, abrasion resistance, and scratch resistance of the coated products provided by the present invention may not be achieved. Trace performance.

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

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

The content of the orthosilicate is 0.2-5 wt.%, Preferably 0.2-3 wt.%, And particularly preferably 0.7-3 wt.%, Based on the total weight of the coating composition as 100 wt.%. If the content of the orthosilicate is less than 0.2 wt.%, When it is reacted with the first reaction solution and the silane compound C containing an amino functional group to obtain a coating composition, the coating composition is further used. The anti-slip properties of the prepared dry coatings and coated products may not be good enough to achieve the anti-slip performance possessed by the coated products provided by the present invention. If the content of the orthosilicate is more than 5 wt.%, When it reacts with the first reaction solution and the silane compound C containing an amino functional group to obtain a coating composition, the coating composition is applied. The bonding force may be poor on the surface of the substrate, and the abrasion resistance and scratch resistance of the further obtained dried coatings and coated products may be poor, so that the coated products provided by the present invention cannot be achieved. Abrasion resistance and scratch resistance.

The coating composition according to the present invention may further include surface epoxy-modified silica particles. The surface epoxy-modified silicon dioxide particles can further improve the abrasion resistance and scratch resistance of the coated product provided by the present invention. The surface epoxy-modified silicon dioxide particles are surface epoxy-modified silicon dioxide particles having a single average particle diameter, and may also be surface epoxy-modified with two or more average particle diameters. A combination of silica particles. The particle size described herein and in the scope of the patent application refers to the length of the longest axis of the particle. The surface epoxy modification described herein and in the scope of the patent application means that the reactive groups (such as SiOH groups) inherent in the surface of the silica particles are replaced with organic groups bearing at least one epoxy functional group. The average particle diameter of the surface epoxy-modified silicon dioxide particles is less than or equal to 50 nm, preferably less than or equal to 20 nm, and particularly preferably less than or equal to 15 nm. Examples of commercially available surface epoxy-modified silica sols include surface epoxy-modified silica sols available from AkzoNobel under the trade name Bindzil in water or in aqueous alcohol solutions. A useful surface epoxy-modified silica sol having an average particle size of 7 nm and a nominal solids content of 28 wt.% Is available as Bindzil CC301. Surface epoxy-modified from AkzoNobel Corporation Silica sol. Other commercially available surface epoxy-modified silica sols include surface epoxy-modified silica sols available as Bindzil CC151 HS and Bindzil CC401 from AkzoNobel.

The content of the surface epoxy-modified silica particles is 0.01-10 wt.%, Preferably 0.5-10 wt.%, And particularly preferably 0.5-5 wt.%, Based on the total weight of the coating composition. 100 wt.%. If the content of the surface epoxy-modified silicon dioxide particles is greater than 10 wt.%, A coating is obtained when it is reacted with the first reaction solution, the silane compound C containing an amino functional group, and the orthosilicate The appearance of the composition and the dry coating further prepared by using the coating composition may not be good enough to achieve the good appearance of the coated product provided by the present invention.

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

The content of the organic solvent is 0.01 to 5 wt.%, Preferably 0.01 to 3 wt.%, And particularly preferably 0.01 to 2 wt.%, Based on the total weight of the coating composition as 100 wt.%. If the content of the organic solvent is more than 5 wt.%, When it is reacted with the first reaction solution, the silane compound C containing an amino functional group and the orthosilicate to obtain a coating composition, the coating combination is used. The anti-slip properties of the dried coatings and coated products obtained by further preparations may not be good enough to achieve the anti-slip properties possessed by the coated products provided by the present invention.

The coating composition according to the present invention may further include an additive. The additives include one or more of the following groups: detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders. The surfactant is a non-ionic surfactant, which can improve the wettability of the coating composition to the surface of the substrate. The nonionic surfactant may be selected from one or more of the following groups: polyoxyethylene nonionic surfactant, polyhydric alcohol nonionic surfactant, alkyl alcohol amide type nonionic surfactant, fluorine Carbon type nonionic surfactant, silicone type nonionic surfactant and modified silicone type nonionic surfactant.

The content of the non-ionic surfactant is 0.01-2 wt.%, Preferably 0.01-1 wt.%, And particularly preferably 0.05-0.5 wt.%, Based on the total weight of the coating composition as 100 wt.% . If the content of the non-ionic surfactant is more than 2 wt.%, When it is reacted with the first reaction solution, the silane compound C containing an amino functional group and the orthosilicate to obtain a coating composition, the coating composition is used. The anti-slip properties of the dried coatings and coated products obtained by further preparing the coating composition may not be good enough to achieve the anti-slip properties of the coated products provided by the present invention.

Coated products

The coated article provided by the present invention includes a substrate and a dry coating applied on the substrate. The substrate includes one or more of the following groups: a ceramic tile substrate, a glass substrate, a stone substrate, and a metal substrate. The "ceramic tiles" described herein and in the scope of the patent application are applicable to porcelain materials including refractory clay, bricks, concrete, ceramics, marble, limestone, and other stones or slate. The ceramic tile substrate includes one or more of the following groups: vitrified tiles, glazed tiles, antique tiles, microcrystalline stones, polished tiles, imitation granite tiles, and imitation marble tiles. The stone substrate includes one or more of the following groups: marble, granite, and artificial stone. The metal substrate includes one or more of the following groups: a stainless steel substrate, a cold-rolled steel substrate, a galvanized steel substrate, an aluminum substrate, and an aluminum alloy substrate.

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

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

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

Preparation method of coated product

The method for preparing a coated article provided by the present invention includes the steps of: applying the coating composition provided by the present invention on the surface of the substrate, forming a wet coating composition liquid film on the surface of the substrate, and applying the The wet coating composition liquid film is dried to obtain a dry coating, and the dry coating is adhered to the surface of the substrate.

For a description of the coating composition, substrate, and coated article, see the "Coating Composition" and "Coated Article" sections of the description of the present invention for details.

The coating composition may be applied to the surface of the substrate by a method known in the art, and the method is preferably one or more of the following group: a blade coating method, a wipe coating method, a brush coating method, Dipping and spraying.

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

The present invention provides a plurality of preferred embodiments regarding a coating composition, a coated article, and a method for preparing the same.

Preferred embodiment 1 is a protective coating composition having a non-slip function. Based on the total weight of the coating composition as 100 wt.%, The reaction product includes the following reaction components: 1) a first reaction solution, The first reaction solution includes a reaction product of the following reaction components: 1-30 wt.% Of a siloxane oligomer and / or polymer A containing an epoxy functional group, the The siloxane functional group siloxane oligomer and / or polymer A has a linear, branched, or cyclic structure and can be represented by the general formula I: HO- [SiR ¹ (OR ³ ) -O] _a- [SiR ² (OR ³ ) -O] _b- [Si (OH) ₂ -O] _c -H (I) where 0 <a ≤ 100; 0 <b ≤ 100; 0 ≤ c ≤ 100; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed and / or hydrolyzed epoxy functional group, including one or more of the following group: 3-glycidyl etheroxypropyl , 3- (2,3-dihydroxypropoxy) propyl, 2- (3,4-epoxycyclohexyl) ethyl, and 2- (3, 4-dihydroxycyclohexyl) ethyl; R ³ generation Table hydrogen atoms or alkyl groups having 1-4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and Tertiary butyl; 1-15 wt.% Silane compound B containing epoxy functional group, the silane compound B containing epoxy functional group can be represented by general formula II: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) where 0 ≤ d ≤ 2; R ⁴ represents an organic group containing at least one unhydrolyzed and / or hydrolyzed epoxy functional group, including the following groups One or more: 3-glycidyl etheroxypropyl, 3- (2, 3-dihydroxypropoxy) propyl, 2- (3, 4-epoxycyclohexane ) Ethyl and 2- (3,4-dihydroxycyclohexyl) ethyl; R ³ represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, including one of the following groups Or more: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and tertiary butyl; said silicon containing epoxy functional groups Oxane oligomer and / or polymer A with said ring containing The functional ratio of the silane compound B is at least 1: 1; 45-96 wt.% Water; and acid; the pH value of the first reaction solution is less than or equal to 5; 2) 0.2-5 wt. % Silane compound C containing amino functional group, the silane compound C containing amino functional group can be represented by general formula III: [(R ³ O) _3-j R ³ _j Si- R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (Ⅲ) where , 0 ≤ e ≤ 1; 0 ≤ f ≤ 1; 1 ≤ g ≤ 6; 0 ≤ h ≤ 1; 0 ≤ i ≤ 6; 0 ≤ j ≤ 2; 0 ≤ k ≤ 2; R ⁵ represents a hydrogen atom or carbon Linear, branched, or cyclic alkyl, alkenyl, or benzyl of 1-6; R ⁶ represents linear, branched, or cyclic carbon of 1-6 Alkyl or alkenyl; R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl Base, secondary butyl, isobutyl and tertiary butyl; 3) 0.2-5 wt.% Orthosilicate, which can be represented by the general formula IV: Si (OR) ₄ (IV) wherein R represents an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, Isobutyl and tertiary butyl.

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

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

Preferred embodiment 4 is a coating composition according to preferred embodiment 1, wherein the general formula of the silane compound B containing an epoxy functional group is: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) wherein 0 ≤ d ≤ 2; R ⁴ represents an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyl etheroxy Propyl and 2- (3,4-epoxycyclohexyl) ethyl; R ³ represents a hydrogen atom or an alkyl group having 1-3 carbon atoms, including one or more of the following groups : Methyl, ethyl, n-propyl and isopropyl.

Preferred embodiment 5 is a coating composition according to preferred embodiment 4, wherein the epoxy group-containing silane compound B includes one or more of the following group: 3-glycidyl ether oxygen Propyltrimethoxysilane, 3-glycidyletheroxypropyltriethoxysilane, 3-glycidyletheroxypropylmethyldimethoxysilane, 3-glycidyletheroxypropylmethyl Didiethoxysilane, 3-glycidyl etheroxypropylethyldimethoxysilane, 3-glycidyl etheroxypropylethyldiethoxysilane, 2- (3, 4-epoxy Cyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

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

Preferred embodiment 7 is a coating composition according to preferred embodiment 1, wherein the siloxane oligomer and / or polymer A containing an epoxy functional group and the containing The weight ratio of the silane functional group B of the epoxy functional group is at least 1.2: 1.

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

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

Preferred embodiment 10 is a coating composition according to preferred embodiment 9, wherein the amino functional group-containing silane compound C includes one or more of the following group: 3-aminopropyltrimethyl Oxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldimethyl Oxysilane, 3-aminopropylethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-amino Propyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethyl Oxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltriethoxysilane, 3 -[2- (2-aminoethylamino) ethylamino] propylmethyldimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propylmethyldiethoxy Silane, 3- (N, N- Methylaminopropyl) -aminopropyltrimethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylamine (Propyl) -aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N, N- Dimethyl-3-aminopropyltrimethoxysilane, N, N-diethyl-3-aminopropyltrimethoxysilane, N, N-diethyl-3-aminopropyltriethoxysilane , N-ethyl-3-trimethoxysilyl-2-methylpropylamine, N- [3- (trimethoxysilyl) propyl] n-butylamine, bis [(3-trimethoxysilyl) -Propyl] amine, bis [(3-triethoxysilyl) -propyl] amine.

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

Preferred embodiment 12 is a coating composition according to preferred embodiment 11, wherein the orthosilicate comprises one or more of the following group: methyl orthosilicate, ethyl orthosilicate, orthosilicate N-propyl ester and isopropyl orthosilicate.

Preferred embodiment 13 is a coating composition according to preferred embodiment 1, wherein the coating composition further comprises 0.01-10 wt.% Surface epoxy-modified silica particles, and the coating The total weight of the layer composition is 100 wt.%.

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

Preferred embodiment 15 is a coating composition according to preferred embodiment 1, wherein the coating composition further comprises 0.01-5 wt.% Organic solvent, and the total weight of the coating composition is 100%. In terms of wt.%, the organic solvent is miscible with water and includes one or more of the following group: alcohol, ketone, ester, and ether having a molecular weight of less than 250.

Preferred embodiment 16 is a coating composition according to preferred embodiment 1, wherein the coating composition further comprises 0.01-2 wt.% Additives, and the total weight of the coating composition is 100 wt. In%, the additives include one or more of the following groups: detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders.

Preferred embodiment 17 is a coating composition according to preferred embodiment 16, wherein the surfactant is a nonionic surfactant and includes one or more of the following groups: a polyoxyethylene type nonionic surfactant Polyol-based nonionic surfactants, Alkanolamine-based nonionic surfactants, fluorocarbon-based nonionic surfactants, silicone-based nonionic surfactants, and modified silicone-based nonionic surfactants .

Preferred embodiment 18 is a coated article including a substrate and a dry coating applied on the substrate, the dry coating including applying the coating composition according to preferred embodiments 1-17 to the substrate. A coating obtained by drying the surface of the substrate.

Preferred embodiment 19 is a coated article according to 18, wherein the substrate comprises one or more of the following groups: a ceramic tile substrate, a glass substrate, a stone substrate, and a metal substrate.

Preferred embodiment 20 is a coated article according to preferred embodiment 19, wherein the ceramic tile substrate comprises one or more of the following groups: vitrified tiles, glazed tiles, antique tiles, microcrystalline stones, polished tiles , Imitation granite tiles and imitation marble tiles.

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

Preferred embodiment 22 is a coated article according to preferred embodiment 19, wherein the metal substrate includes one or more of the following groups: stainless steel substrate, cold rolled steel substrate, galvanized steel substrate, aluminum substrate And aluminum alloy substrates.

Preferred embodiment 23 is a method for preparing a coated product, including the following steps: applying the coating composition according to preferred embodiments 1-17 on the surface of the substrate, and forming a wet coating layer on the surface of the substrate The composition liquid film is obtained by drying the wet coating composition liquid film to obtain a dry coating, and the dry coating is adhered to the surface of the substrate.

Preferred embodiment 24 is a preparation method according to preferred embodiment 23, wherein the coating composition is applied to the surface of the substrate by the following method: a blade coating method, a wipe coating method, a brush coating method, or a dip coating method. Method and spray method.

Examples

The examples and comparative examples provided below are helpful for understanding the present invention, and these examples and comparative examples should not be construed as limiting the scope of the present invention. Unless otherwise indicated, all parts and percentages are by weight.

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

Table 1 Raw materials used in Examples and Comparative Examples

The present invention mainly evaluates the anti-slip performance of the dried coatings or coated products provided by the examples and comparative examples by testing the dry and wet static friction coefficients. On this basis, the present invention evaluates the abrasion resistance of the dried coatings or coated articles provided in the examples and comparative examples through a dry grinding test. The present invention uses a pencil hardness test to evaluate the scratch resistance of the dried coatings or coated articles provided in the examples and comparative examples. In addition, the present invention further evaluates the influence of the dry coatings provided in the examples and comparative examples on the appearance of the substrate through a surface gloss test.

Anti-slip performance test

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

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

A coating composition is coated on the surface of the substrate, and a dried coating is formed on the surface of the substrate after drying to obtain a coated product including the substrate and the dried coating.

ASM 825A static friction coefficient tester was used to measure the dry static friction coefficient on the surface of the coated product. Take any three different areas on the surface of the coated product, measure the dry static friction coefficient, and take the average value.

After the surface of the coated product was completely wetted with deionized water, the wet static friction coefficient of the surface of the coated product was measured with an ASM 825A static friction coefficient tester. Take any three different areas on the surface of the coated product, measure the wet static friction coefficient, and take the average value.

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

The average value of the static friction coefficients of several states is greater than 0.6, which indicates that the surface of the coated product has good anti-skid performance under dry conditions, and the larger the value, the better its anti-skid performance.

If the average value of the wet static friction coefficient is greater than 0.6, it means that the surface of the coated product has good anti-skid performance under wet conditions, and the larger the value, the better its anti-skid performance.

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

Abrasion resistance test

The present invention uses a dry milling test to characterize the abrasion resistance of a dried coating or coated article.

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

A coating composition is coated on the surface of the substrate, and a dried coating is formed on the surface of the substrate after drying to obtain a coated product including the substrate and the dried coating.

Under the condition of a load of 2.2 kg, the surface of the coated product was rubbed with a friction material. The friction material is a 3M 5100 brush, which can be purchased from 3M Company. The wet static friction coefficient is tested once every 500 times of friction. When the wet static friction coefficient is less than or equal to 0.6, the test is stopped and the number of friction loops tested is recorded (a friction loop refers to one back and forth friction). If the wet static friction coefficient is still greater than 0.6 when the number of friction cycles reaches 20,000, the test is stopped and the number of friction cycles is recorded as 20,000.

If the measured number of friction loops of a coated product is greater than 5000, it indicates that the coated product has good abrasion resistance.

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

Scratch resistance test

The present invention uses a pencil hardness test to characterize the scratch resistance of a dried coating or coated article.

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

A coating composition is coated on the surface of the substrate, and a dried coating is formed on the surface of the substrate after drying to obtain a coated product including the substrate and the dried coating.

A special mechanical pencil sharpener sharpened one end of a series of Chinese-style premium drawing pencils (increased in hardness from 9B to 9H) to about 5mm-6mm of wood, leaving the original, unscratched, smooth cylindrical pencil pen core. Hold the pencil vertically, move the pencil back and forth on the sandpaper at a 90-degree angle with the sandpaper, smooth the tip of the pencil refill to a right angle, and continue to move the pencil until a complete and smooth circular cross-section is obtained. Place the coated product on a level, stable table, fix the pencil to the instrument at a 45-degree angle with the fixture, keep the instrument level, and place the tip of the pencil on the surface of the coated product. Under the conditions, push the pencil uniformly at a speed of 0.5mm / s-1mm / s in a direction away from the operator by a distance of at least 7mm. A pencil of the same hardness was repeatedly tested 5 times at different positions on the surface of the coated article. Wipe the surface of the coated product with absorbent cotton dipped in an inert solvent, and visually observe whether the surface of the coated product has defects such as plastic deformation and / or cohesive failure. Stop the test if defects such as plastic deformation and / or cohesive failure have occurred, and record the hardness of the pencil used for the test. If defects such as plastic deformation and / or cohesive failure do not occur, repeat the above test with a pencil with a higher hardness until the surface of the coated product has defects such as plastic deformation and / or cohesive failure. Record the pencil used in the last test. Of hardness.

If the measured pencil hardness of a coated product is greater than 4H, it indicates that the coated product has good scratch resistance.

The test results of the scratch resistance properties of the dried coatings or coated articles provided in the examples and comparative examples of the present invention are shown in Table 4.

Surface gloss test

The present invention uses a surface gloss test to characterize the effect of a dry coating on the appearance of a substrate.

The instrument for testing the surface gloss is a Micro-Tri-Gloss gloss meter, which can be purchased from BYK-Gardner.

A coating composition is coated on the surface of the substrate, and a dried coating is formed on the surface of the substrate after drying to obtain a coated product including the substrate and the dried coating.

The surface gloss value of the coated article was measured with a Micro-Tri-Gloss gloss meter. Take any three different areas on the surface of the coated product, measure the surface gloss values at 20 °, 60 °, and 85 °, and take the average value of each angle.

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

Preparation of coating composition

Example 1

Add 0.50 grams of Dynasylan® HYDROSIL 2926 and 15.22 grams of deionized water (DI H ₂ O) to a 50-ml glass bottle; add 0.20 grams of 3-glycidyl etheroxypropyl dropwise while stirring on a magnetic stirrer Trimethoxysilane (GPTMS); After stirring at room temperature for 1 hour, add 0.04g of 3-aminopropyltriethoxysilane (APTES); After stirring for 10 minutes, add 0.04g of methyl orthosilicate ( TMOS); After stirring for 30 minutes, 4.00 g of a 10 wt.% Aqueous solution of TRITON ™ BG-10 surfactant was added; after stirring for 15 minutes, a yellow-brown slightly turbid coating composition was obtained.

Example 2-5

The coating compositions of Examples 2-5 were prepared in the same manner as in Example 1. The types and contents of the components included in the coating composition are listed in Table 2.

Example 6

5.02 g of COATOSIL MP 200, 10.20 g of deionized water (DI H ₂ O) and 1.00 g of ethanol (EtOH) were added to a 50 ml glass bottle; 0.10 g of 13.30 wt was added dropwise while stirring on a magnetic stirrer. % Nitric acid (HNO ₃ ) in water, adjust the pH to 1-2; After stirring at room temperature for 1 hour, add 2.56 g of 3-glycidyl etheroxypropyltrimethoxysilane (GPTMS); continue to stir 1 After hours, add 0.60 g of 3-aminopropyltriethoxysilane (APTES); after stirring for 10 minutes, add 0.60 g of methyl orthosilicate (TMOS); after stirring for 30 minutes, a colorless, slightly cloudy coating is obtained层 组合 物。 Layer composition.

Example 7

The coating composition of Example 7 was prepared in the same manner as in Example 1. The types and contents of the components included in the coating composition are listed in Table 2.

Comparative Example 1

Add 1.50 grams of 3-glycidyl etheroxypropyltrimethoxysilane (GPTMS) and 19.00 grams of deionized water (DI H ₂ O) to a 50-ml glass bottle; drop while stirring on a magnetic stirrer Add 0.20 g of a 5.48 wt.% Aqueous solution of hydrochloric acid (HCl) to adjust the pH to 2-3. After stirring at room temperature for 1 hour, add 0.36 g of 3-aminopropyltriethoxysilane (APTES); continue After stirring for 30 minutes, 0.72 g of a 10 wt.% Aqueous solution of TRITON BG-10 surfactant was added; after stirring for 10 minutes, a slightly yellow and slightly cloudy coating composition was obtained.

Comparative Example 2

The coating composition of Comparative Example 2 was prepared in the same manner as Comparative Example 1. The types and contents of the components included in the coating composition are listed in Table 2.

Table 2 Formulation of coating composition

Preparation and performance test of coated products

Example 8

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

The anti-slip properties of the coated products obtained are tested, and the test results are listed in Table 3. The abrasion resistance and scratch resistance of the coated products obtained are tested, and the test results are listed in Table 4. The surface gloss and test results are shown in Table 5.

Examples 9-18

Coated products were prepared in the same manner as in Example 8. The substrate types, blade coating conditions, and heat treatment conditions of the coated products are shown in Table 3.

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

The anti-slip properties of the coated products obtained are tested, and the test results are listed in Table 3. The abrasion resistance and scratch resistance of the coated products obtained are tested, and the test results are listed in Table 4. The surface gloss and test results are shown in Table 5.

Example 19

The dip coating method is used to prepare coated products, which includes the following steps: a glass substrate (180mm × 100mm × 3mm) is used as the substrate of the coated product, and detergent (white cat brand, available from Shanghai and Yellow White Cat Limited) Company) clean the surface of the glass substrate, rinse it with deionized water, and blow dry it with compressed air; pour 200 g of the coating composition obtained in Example 4 into a 400 ml stainless steel tank (150 mm x 150 mm × 20mm); at room temperature, the glass substrate is dip-coated in the coating composition with an automatic dip coating machine (SKVDX2S-500, available from KSV NIMA); The immersion speed is 300mm / min, the immersion time is 1 minute, and the pulling speed is 300mm / min, which are listed in Table 3. The glass substrate after dipping is heated and dried in an oven at 100 ° C for 15 minutes, then taken out and cooled to the room. Warm to obtain a coated product.

The anti-slip properties of the coated products obtained are tested, and the test results are listed in Table 3. The abrasion resistance and scratch resistance of the coated products obtained are tested, and the test results are listed in Table 4. The surface gloss and test results are shown in Table 5.

Example 20

The method of preparing coated products by rubbing method includes the following steps: using 304 stainless steel (200mm × 100mm × 1mm) as the base material of the coated products, first using detergent (white cat brand, available from Shanghai and Yellow White Cat Co., Ltd.) ) Wash the surface of 304 stainless steel, then rinse it with deionized water, and blow dry it with compressed air; Spunbond polypropylene non-woven fabric (available from 3M company) is cut into 50mm × 20mm strips, using drops 6 g of the coating composition obtained in Example 4 was taken from a tube, and 3 g was added dropwise to one end of 304 stainless steel, and another 3 g was added dropwise to the middle of 304 stainless steel. One end of the coating composition is uniformly applied to one end of the non-coating composition; the wiped 304 stainless steel is dried at room temperature for 24 hours to obtain a coated product.

The anti-slip properties of the coated products obtained are tested, and the test results are listed in Table 3. The abrasion resistance and scratch resistance of the coated products obtained are tested, and the test results are listed in Table 4. The surface gloss and test results are shown in Table 5.

Comparative Example 3

The coated product is prepared by a knife coating method, including the steps: using vitrified tiles (225mm × 150mm × 10mm) as the substrate of the coated product, first using detergent (white cat brand, available from Shanghai and Yellow White Cat Limited) Company) clean the surface of the vitrified tile, then rinse it with deionized water, and blow dry it with compressed air; use a 200-mesh filter to filter 10 g of the coating composition obtained in Comparative Example 1 twice; An automatic bar coater (K303 Multicoater, available from RK Print Coat Instruments) was placed on one end of the vitrified tile, and 5 g of the filtered coating composition was evenly dropped with a dropper between the wire rod and the vitrified tile. In the gap between the layers; at a room temperature, use an automatic doctor coater to scrape the coating composition on the surface of the vitrified tile; during the doctor blade coating process, the wet film thickness of the coating composition is about 6 μm, denoted as T-6, As shown in Table 3, the coated vitrified tile was dried at room temperature for 24 hours to obtain a coated product.

The anti-slip properties of the coated products obtained are tested, and the test results are listed in Table 3. The abrasion resistance and scratch resistance of the coated products obtained are tested, and the test results are listed in Table 4. The surface gloss and test results are shown in Table 5.

Comparative Example 4

A coated product was prepared in the same manner as Comparative Example 3, and as Comparative Example 4, the substrate types, blade coating conditions, and heat treatment conditions of the coated products are listed in Table 3.

The anti-slip properties of the coated products obtained are tested, and the test results are listed in Table 3. The abrasion resistance and scratch resistance of the coated products obtained are tested, and the test results are listed in Table 4. The surface gloss and test results are shown in Table 5.

Comparative Examples 5-11

As Comparative Examples 5-11, vitrified tiles, glazed tiles, microcrystalline stones, artificial stones, marble, glass substrates, and stainless steel substrates without using a dry coating were used, as shown in Table 3.

The anti-slip properties of the coated products obtained are tested, and the test results are listed in Table 3. The abrasion resistance and scratch resistance of the coated products obtained are tested, and the test results are listed in Table 4. The surface gloss and test results are shown in Table 5.

Table 3 Preparation of coated products and test of their slip resistance

It can be seen from Table 3 that the wet-state static friction coefficients of the uncoated dry-coating substrates provided in Comparative Examples 5-10 are all less than 0.6, so their anti-skid performance is poor under wet conditions. According to the coated products provided in Examples 8-19, the dry static friction coefficient is slightly improved or unchanged compared with the substrate without the dry coating, and the wet static friction coefficient is higher than that of the substrate without the dry coating. The material has been greatly improved, and both are significantly greater than 0.6, so these coated products have good anti-slip performance in both dry and wet conditions. Both the dry static friction coefficient and the wet static friction coefficient of the stainless steel substrate without the dry coating provided in Comparative Example 11 were greater than 1.0. According to the coated product provided in Example 20, both the dry static friction coefficient and the wet static friction coefficient are slightly improved, so the coated product has good anti-slip performance under both dry and wet conditions.

Table 4 Abrasion resistance and scratch resistance test of coated products

As can be seen from Table 4, according to the coated product provided in Comparative Example 3, the number of loops in the abrasion resistance test was 3500, and its pencil hardness was 3H. According to the coated product provided in Comparative Example 4, the number of loops in the abrasion resistance test was 4000, and its pencil hardness was 3H. According to the coated products provided in Examples 9-17, 19, and 20, the number of loops in the abrasion resistance test was significantly improved compared to the coated products provided in Comparative Example 3-4, and Both are significantly greater than 5000, and their pencil hardness is greatly improved compared to the coated products provided in Comparative Example 3-4, and they are significantly greater than 4H. Therefore, these coated products have good abrasion resistance and scratch resistance.

Table 5 Surface gloss test of coated products

It can be seen from Table 5 that according to the coated products provided in Examples 9-16, the surface gloss is basically unchanged or slightly different from that of the uncoated dry coating substrates provided in Comparative Examples 3-9. Lift, so these coated articles have good appearance.

Although the above specific implementation includes many specific details for the purpose of illustration, those of ordinary skill in the art should understand that many variations, modifications, substitutions and changes of these details are all within the scope of the present invention protected by the scope of the patent application. Therefore, the disclosure described in the detailed description does not impose any restrictions on the invention protected by the scope of the patent application. The proper scope of the invention should be defined by the scope of the patent application and its appropriate legal equivalents. All cited references are incorporated herein by reference in their entirety.

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Claims (24)

A protective coating composition having a non-slip function, based on a total weight of the coating composition of 100 wt.%, Includes a reaction product of the following reaction components: 1) a first reaction solution, the first reaction solution A reaction product including the following reaction components: 1-30 wt.% Of an siloxane functional group-containing siloxane oligomer and / or polymer A, which contains an epoxy group Functional siloxane oligomers and / or polymers A have linear, branched, or cyclic structures and can be represented by the general formula I: HO- [SiR ¹ (OR ³ ) -O] _a -[SiR ² (OR ³ ) -O] _b- [Si (OH) ₂ -O] _c -H (I) where 0 <a ≤ 100; 0 <b ≤ 100; 0 ≤ c ≤ 100; R ¹ And R ² each independently represent an organic group containing at least one unhydrolyzed and / or hydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyl etheroxypropyl, 3- (2 , 3-dihydroxypropoxy) propyl, 2- (3,4-epoxycyclohexyl) ethyl and 2- (3,4-dihydroxy) cyclohexyl) ethyl; R ³ represents a hydrogen atom or a C 1-4 alkyl groups, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and tertiary butyl; 15 wt.% Silane functional group-containing silane compound B, the silane functional group-containing silane compound B can be represented by the general formula II: R ⁴ -SiR ³ _d (OR ³ ) _3-d (II) where 0 ≤ d ≤ 2; R ⁴ represents an organic group containing at least one unhydrolyzed and / or hydrolyzed epoxy functional group, including one or more of the following groups: 3-shrink Glyceryl etheroxypropyl, 3- (2,3-dihydroxypropoxy) propyl, 2- (3,4-epoxycyclohexyl) ethyl and 2- (3,4-dihydroxycyclohexyl) ethyl; R ³ represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, including one or more of the following groups: methyl, ethyl Groups, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and tertiary butyl; said siloxane oligomers containing epoxy functional groups and / Or polymer A with the epoxy-containing functional group The weight ratio of the silane compound B is at least 1: 1; 45-96 wt.% Water; and acid; the pH value of the first reaction solution is less than or equal to 5; 2) 0.2-5 wt.% Containing ammonia The functional group of the silane compound C, the amino group-containing silane compound C can be represented by the general formula III: [(R ³ O) _3-j R ³ _j Si-R ⁶ ] _{2- e} R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (Ⅲ) where 0 ≤ e ≤ 1; 0 ≤ f ≤ 1; 1 ≤ g ≤ 6; 0 ≤ h ≤ 1; 0 ≤ i ≤ 6; 0 ≤ j ≤ 2; 0 ≤ k ≤ 2; R ⁵ represents a hydrogen atom or a carbon number of 1-6 Linear, branched or cyclic alkyl, alkenyl or benzyl; R ⁶ represents a linear, branched or cyclic alkyl or Alkenyl; R ³ represents a hydrogen atom or an alkyl group having a carbon number of 1-4, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl Base, isobutyl and tertiary butyl; 3) 0.2-5 wt.% Orthosilicate, which can be represented by the general formula IV: Si (OR) ₄ (IV) where R Represents an alkyl group having 1 to 4 carbon atoms, including one or more of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and tertiary base. The coating composition according to item 1 of the scope of patent application, wherein the general formula of the siloxane oligomer and / or polymer A containing epoxy functional group is: HO- [ SiR ¹ (OR ³ ) -O] _a- [SiR ² (OR ³ ) -O] _b- [Si (OH) ₂ -O] _c -H (I) where 0 <a ≤ 20; 0 <b ≤ 20; 0 ≤ c ≤ 20; R ¹ and R ² each independently represent an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyl etheroxypropyl And 2- (3,4-epoxycyclohexyl) ethyl; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: Group, ethyl, n-propyl and isopropyl. The coating composition according to claim 1 in the application, wherein the content of the siloxane oligomer and / or polymer A containing epoxy functional group is 4.5-25 wt. % Based on the total weight of the coating composition as 100 wt.%. The coating composition according to item 1 of the scope of patent application, wherein the general formula of the silane compound B containing an epoxy functional group is: R ⁴ -SiR ³ _d (OR ³ ) _{3- d} (II) where 0 ≤ d ≤ 2; R ⁴ represents an organic group containing at least one unhydrolyzed epoxy functional group, including one or more of the following groups: 3-glycidyl etheroxypropyl and 2 -(3,4-epoxycyclohexyl) ethyl; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, including one or more of the following groups: methyl, Ethyl, n-propyl and isopropyl. The coating composition according to item 4 of the scope of patent application, wherein the silane compound B containing an epoxy functional group includes one or more of the following group: 3-glycidyl etheroxypropyltrimethyl Oxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-glycidyl etheroxypropylmethyldimethoxysilane, 3-glycidyl etheroxypropylmethyldiethoxy Silyl, 3-glycidyl etheroxypropylethyldimethoxysilane, 3-glycidyl etheroxypropylethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) Ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. The coating composition according to item 1 of the scope of patent application, wherein the content of the silane compound B containing epoxy functional groups is 3-13 wt.%, With the coating composition The total weight is calculated as 100 wt.%. The coating composition according to item 1 of the patent application scope, wherein the siloxane oligomer and / or polymer A containing an epoxy functional group and the epoxy containing The functional ratio of the silane compound B is at least 1.2: 1. The coating composition according to item 1 of the scope of patent application, wherein the acid is an inorganic acid or an organic acid, and the inorganic acid includes one or more of the following group: hydrochloric acid, nitric acid, and phosphoric acid; the organic acid includes One or more of the following groups: formic acid and acetic acid. The coating composition according to item 1 of the scope of the patent application, wherein the general formula of the silane compound C containing an amino functional group is: [(R ³ O) _3-j R ³ _j Si- R ⁶ ] _2-e R ⁵ _e R ⁵ _f N-[(CH ₂ ) _g -NR ⁵ _h H _(1-h) ] _i -R ⁶ -SiR ³ _k (OR ³ ) _3-k (Ⅲ) where , 0 ≤ e ≤ 1; 0 ≤ f ≤ 1; 1 ≤ g ≤ 6; 0 ≤ h ≤ 1; 0 ≤ i ≤ 6; 0 ≤ j ≤ 2; 0 ≤ k ≤ 2; R ⁵ represents a hydrogen atom or carbon A linear, branched or cyclic alkyl or alkenyl group having a number of 1-4; R ⁶ represents a linear, branched or cyclic alkyl group having a carbon number of 1-4; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and includes one or more of the following groups: methyl, ethyl, n-propyl, and isopropyl. The coating composition according to item 9 of the scope of the patent application, wherein the amino group-containing silane compound C includes one or more of the following group: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethyl Oxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldiethoxysilane, 3- [2 -(2-aminoethylamino) ethylamino] propyltrimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltriethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propylmethyldimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propylmethyldiethoxysilane, 3 -(N, N-dimethylaminopropyl) -amine Trimethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropyltriethoxysilane, 3- (N, N-dimethylaminopropyl) -aminopropylmethyl Dimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N, N-dimethyl-3-aminopropyl Trimethoxysilane, N, N-diethyl-3-aminopropyltrimethoxysilane, N, N-diethyl-3-aminopropyltriethoxysilane, N-ethyl-3-trimethyl Oxysilyl-2-methylpropylamine, N- [3- (trimethoxysilyl) propyl] -n-butylamine, bis [(3-trimethoxysilyl) -propyl] amine, bis [( 3-triethoxysilyl) -propyl] amine. The coating composition according to item 1 of the scope of patent application, wherein the general formula of the orthosilicate is: Si (OR) ₄ (IV) wherein R represents an alkyl group having 1-3 carbon atoms, including One or more of the following groups: methyl, ethyl, n-propyl, and isopropyl. The coating composition according to item 11 of the application, wherein the orthosilicate comprises one or more of the following groups: methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, and n- orthosilicate Isopropyl silicate. The coating composition according to item 1 of the scope of patent application, wherein the coating composition further comprises 0.01 to 10 wt.% Of surface epoxy-modified silicon dioxide particles. Total weight is calculated as 100 wt.%. The coating composition according to item 13 of the scope of patent application, wherein the average particle diameter of the surface epoxy-modified silica particles is less than or equal to 15 nm. The coating composition according to item 1 of the scope of patent application, wherein the coating composition further comprises 0.01-5 wt.% Organic solvent, and the total weight of the coating composition is calculated as 100 wt.% The organic solvent is miscible with water and includes one or more of the following group: alcohol, ketone, ester, and ether having a molecular weight of less than 250. The coating composition according to item 1 of the scope of the patent application, wherein the coating composition further comprises 0.01-2 wt.% Additives, and the total weight of the coating composition is calculated as 100 wt.%, The additives include one or more of the following groups: detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, perfumes, dyes, pigments, and organic polymer binders. The coating composition according to item 16 of the scope of patent application, wherein the surfactant is a non-ionic surfactant, including one or more of the following groups: a polyoxyethylene-type non-ionic surfactant, a polyol type Nonionic surfactants, alkyl alcohol ammonium nonionic surfactants, fluorocarbon nonionic surfactants, silicone nonionic surfactants, and modified silicone nonionic surfactants. A coated article includes a substrate and a dry coating applied on the substrate, the dry coating including applying the coating composition according to any one of claims 1-17 The surface of the substrate is a coating obtained by drying. The coated article according to item 18 of the scope of patent application, wherein the substrate comprises one or more of the following groups: a ceramic tile substrate, a glass substrate, a stone substrate, and a metal substrate. The coated article according to item 19 of the scope of patent application, wherein the ceramic tile substrate comprises one or more of the following groups: vitrified tiles, glazed tiles, antique tiles, microcrystalline stones, polished tiles, imitation granite tiles And imitation marble tiles. The coated article of claim 19, wherein the stone substrate comprises one or more of the following groups: marble, granite, and artificial stone. The coated article according to item 19 of the application, wherein the metal substrate comprises one or more of the following groups: a stainless steel substrate, a cold-rolled steel substrate, a galvanized steel substrate, an aluminum substrate, and an aluminum alloy Substrate. A method for preparing a coated product includes the following steps: applying the coating composition according to any one of claims 1-17 on the surface of the substrate to form a wet coating on the surface of the substrate Layer composition liquid film, drying the wet coating composition liquid film to obtain a dry coating, and the dry coating is adhered to the surface of the substrate. The preparation method according to item 23 of the scope of patent application, wherein the coating composition is applied to the surface of the substrate by the following methods: a blade coating method, a wipe coating method, a brush coating method, a dip coating method, and a spray coating method .