Soil-resistant, stain-resistant fluorine-free coatings and methods of applying on materials

Patent metadata

Field	Value
Publication number	US-11142867-B2
Application number	US-201515526497-A
Country	US
Kind code	B2
Filing date	Nov 12, 2015
Priority date	Nov 12, 2014
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

A process of fabricating the waterproof coating may include selecting a textile material substrate, utilizing a sol-gel comprising a silane or silane derivative and metal oxide precursor to coat the substrate, and optionally coating the substrate with a hydrophobic chemical agent and/or other chemical agents to create a surface with nanoscopic or microscopic features. The process may utilize an all solution process or controlled environment for fabricating a fluorine-free waterproof coating that prevent wetting or staining of a substrate, or may utilize a controlled environment. The composition coatings for treating textile materials improve soil-resistance and stain-resistance of the textile materials while the compositions contain no fluorine-based chemicals. In addition, the composite solution may impart additional properties such as physical strength to the textile whilst retaining the original appearance.

First claim

What is claimed is:

1. A method for treating a substrate for improved soil-resistance or stain-resistance, the method comprising:
selecting a substrate to be coated;
preparing a composite solution that is fluorine-free, wherein the composite solution consists of water, acid, first solvent, base chemical reagent, plasticizer and bonding agent, the composite solution comprises 3-8 vol. % of the water, 20-30 vol. % of the first solvent, 40-60 vol. % of the base chemical reagent, 15-20 vol. % of the plasticizer, and 5-10 vol. % of the bonding agent,
wherein further the base chemical reagent is selected from an alkoxysilane, metal oxide precursor, or a combination thereof having a general formula of M(OR) 4 , where M=Si, Al, Ti, In, Sn or Zr, and R comprises hydrogen, a substituted or unsubstituted alkyl,
the bonding agent is selected from an alkoxysilane, metal oxide precursor, or a combination thereof having a general formula of M(OR) x R′ y R″ z (M=Si, Al, In, Sn or Ti; x is the integer 1, 2 or 3; y is the integer 0, 1 or 2; z is the integer 1, 2 or 3, provided that the sum of x, y and z equals 4), where R comprises hydrogen, a substituted or unsubstituted alkyl or derivatives thereof; R′ comprises hydrogen, a substituted or unsubstituted alkyl or derivatives thereof and R″ comprises a substituted or unsubstituted epoxy or glycidoxy, and
the plasticizer is selected from an alkoxysilane, metal oxide precursor, or a combination thereof having a general formula of M(OR) 4-x R′ x (M=Si, Al, In, Sn or Ti; x is the integer 1, 2 or 3), where R comprise hydrogen, a substituted or unsubstituted alkyl or derivatives thereof and R′ comprise a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl or derivatives thereof;

utilizing the composite solution to coat the substrate to form a superhydrophobic coating, wherein the composite solution is deposited via an all solution process, and a degree of polymerization of the composite solution is equal to or less than 100;
coating the substrate with a hydrophobic solution that is fluorine-free, wherein the hydrophobic solution comprises a hydrophobic chemical agent and a third solvent; and
drying or curing the substrate at equal to or between 25-200° C. to allow a fluorine-free composite coating to form for improving soil-resistance or stain resistance.

2. The method of claim 1 , wherein the composite solution is prepared under acidic condition where pH is equal to or less than 5.

3. The method of claim 2 , wherein the preparation step further comprises stirring the composite solution at an elevated temperature in a range of 50-100° C.

4. The method of claim 3 , wherein the stirring at the elevated temperature is performed for ½ hour to 12 hours.

5. The method of claim 1 , wherein the composition coating formed on the substrate does not change the feel and texture of the substrate before coating.

6. The method of claim 1 , wherein the first solvent is selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol acetone, acetonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide or a mixture thereof.

7. The method of claim 1 , wherein the hydrophobic chemical agent is an alkylsilane [CH 3 (CH 2 ) a ] b SiR c X d ; where X comprise Cl, Br, I or other suitable organic leaving groups, R comprise a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl or derivatives thereof, and a is the integer 0, 1, 2, 3 . . . to 20, b is the integer 1, 2 or 3, c is the integer 0, 1, 2, 3 and d is the integer 1, 2 or 3, provided that the sum of b, c and d equals 4.

8. The method of claim 7 , wherein the alkylsilane is selected from chlorosilane, dichlorosilane, trichlorosilane, chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, chlorophenylsilane, dichlorophenylsilane, trichlorophenylsilane, chloromethylphenylsilane, chlorodimethylphenylsilane, dichloromethylphenylsilane, chlorodimethylphenethylsilane, dichloromethylphenethylsilane, trichlorophenethylsilane, chlorodimethyloctylsilane, dichloromethyloctylsilane trichlorooctylsilane, chlorodimethyldodecylsilane, dichloromethyldodecylsilane, trichlorododecylsilane, chlorodecyldimethylsilane, dichlorodecylmethylsilane, trichlorodecylsilane, chlorodimethyloctadecylsilane, dichloromethyloctadecylsilane, trichlorooctadecylsilane, chlorodimethylthexylsilane, dichloromethylthexylsilane, trichlorothexylsilane, allyldichloromethylsilane, allylchlorodimethylsilane, allyltrichlorosilane, (cyclohexylmethyl)chlorodimethylsilane, (cyclohexylmethyl)dichloromethylsilane, or (cyclohexylmethyl)trichlorosilane.

9. The method of claim 1 , wherein the third solvent is selected from toluene, benzene, xylene, trichloroethylene, 1,2-dichloroethane, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, n-propyl bromide, diethyl ether, acetone, diisopropyl ether, methyl-t-butyl ether, petroleum ethers or petroleum hydrocarbons.

10. The method of claim 1 , wherein the hydrophobic chemical agent is an alkoxyalkylsilane [CH 3 (CH 2 ) a ] b SiR c [alkoxy] d ; where [alkoxy] comprise methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or a combination thereof; R comprise a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl or derivatives thereof, and a is the integer 0, 1, 2, 3 . . . to 20, b is the integer 1, 2 or 3, c is the integer 0, 1, 2, 3 and d is the integer 1, 2 or 3, provided that the sum of b, c and d equals 4.

11. The method of claim 10 , wherein the alkoxyalkylsilane is selected from trimethoxyisobutylsilane, triethoxyisobutylsilane, dimethoxydiisobutylsilane, diethoxydiisobutylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, trimethoxy(hexyl)silane, triethoxy(hexyl)silane, tripropoxy(hexyl)silane, triisopropoxy(hexyl)silane, trimethoxy(octyl)silane, triethoxy(octyl)silane, tripropoxy(octyl)silane, triisopropoxy(octyl)silane, trimethoxy(decyl)silane, triethoxy(decyl)silane, tripropoxy(decyl)silane, triisopropoxy(decyl)silane, trimethoxy(dodecyl)silane, triethoxy(dodecyl)silane, tripropoxy(dodecyl)silane, or triisopropoxy(dodecyl)silane.

12. The method of claim 10 , wherein the hydrophobic chemical agent is prepared by mixing and heating the hydrophobic agent and the third solvent.

13. The method of claim 12 , wherein the mixing and heating the hydrophobic agent and the third solvent occurs in an acidic environment with pH equal to or less than 1.

14. The method of claim 12 , wherein the mixing and heating the hydrophobic agent and the third solvent occurs at an elevated temperature equal to or between 50 to 100° C.

15. The method of claim 13 , wherein the mixing and heating the hydrophobic agent and the third solvent occurs for equal to or between 1 hour to 7 days.

16. The method of claim 1 , wherein the third solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, acetonitrile, dioxane, tetrahydrofuran, tetrachloroethylene, dimethylformamide, dimethyl sulfoxide, or water.

Assignees

• Univ Houston System

Inventors

• Curran Seamus
• Liao Kang-Shyang
• Alley Nigel
• Haldar Amrita
• Wang Alexander

Classifications

• D06M13/503 Primary

  without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom · CPC title

• C09D5/00

  Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes · CPC title

• D06M23/10

  Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof · CPC title

• D06M2200/12

  Hydrophobic properties · CPC title

• D06M13/513 Primary

  with at least one carbon-silicon bond · CPC title