# US 2021/0277260 A1 · Surface coating composition with long durability

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- Number: US 2021/0277260 A1
- Document ID: US20210277260A1
- Status: Published application
- Kind: A1
- Application number: 17/257,445
- Filed: 2019-07-01
- Published: 2021-09-09
- Earliest claimed: 2018-07-02
- Assignees: Evonik Operations GmbH
- Applicants: Evonik Operations GmbH
- Inventors: Jianmin XU; Lengfeng ZHENG; Oliver SCHALLER
- Web page: https://patentgrep.com/patent/US20210277260A1

## CPC

- C09D 7/62: modified by treatment with other compounds
- C09D 183/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
- C08G 77/02: Polysilicates
- C08G 77/08: characterised by the catalysts used
- C08G 77/16: to hydroxy groups
- C08G 77/18: to alkoxy or aryloxy groups
- C08G 77/24: halogen-containing groups
- C08G 77/26: nitrogen-containing groups
- C08G 77/80: {Siloxanes having aromatic substituents, e.g. phenyl side groups}
- C08K 3/36: Silica
- C08K 5/01: Hydrocarbons {(C08K5/0091 takes precedence)}
- C08K 5/02: Halogenated hydrocarbons {(C08K5/0091 takes precedence)}
- C08K 5/5419: containing at least one Si—C bond
- C08K 5/544: containing nitrogen
- C08K 9/06: with silicon-containing compounds
- C09D 7/63: organic
- C09D 7/65: macromolecular (C09D7/41-C09D7/48 take precedence)
- C09D 17/002: {in organic medium (C09D17/003, C09D17/004 take precedence)}
- C09D 183/06: containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence)
- C09K 3/18: for application to surfaces to minimize adherence of ice, mist or water thereto (rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30); Thawing or antifreeze materials for application to surfaces (used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00)
- C08K 2201/005: Additives being defined by their particle size in general
- C08K 2201/011: Nanostructured additives
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

The present invention relates to a coating composition comprising (A) hydrophobically modified fumed silica particles, (B) one or more compounds of hydrolyzed organosilanes, and (C) a solvent or mixture of solvents. The coating composition may be used to treat substrates such as glass surface to make the substrate surfaces possess valuable properties such as water repellency, dirt repellency and self-cleaning with water.

## Claims

### Claim at position 1

1-16. (canceled)

### Claim 17

A composition comprising the following components:
a) hydrophobically modified fumed silica particles with a median particle size of from 100 to 100,000 nm;
b) one or more organosilanol compounds selected from the group consisting of:
compounds of Formula (I), wherein Formula (I) is:
X—R—Si(OH)mY1nY2o (I)
wherein:
X is a non-hydrolyzable linear, branched or unbranched aliphatic alkyl residue with 1 to 12 carbon atoms, optionally substituted with fluorine or chlorine atoms; or is a functional group selected from the group consisting of: amino, epoxy, vinyl, methacrylate, or sulfur groups;
R is a spacer and is either an aryl or alkyl chain;
Y1 and Y2 are identical or different and each is independently a hydrolysable or non-hydrolyzable moiety selected from the group consisting of: linear, branched or unbranched, alkyl groups with 1 to 12 carbon atoms; aryl groups with 6 to 12 carbon atoms; halogens; alkoxy groups with 1 to 12, carbon atoms; and acyl groups with 1 to 12 carbon atoms; with the provisio that at least one of Y1 and Y2 is hydrolyzable and is selected from the group consisting of: halogens, alkoxy groups with 1 to 12 carbon atoms; and acyl groups with 1 to 12 carbon atoms;
m=1, 2 or 3;
n and o are each 0 or 1, but are selected such that m+n+o=3; and
dimeric compounds of Formula (I); trimeric compounds of Formula (I); and oligomeric compounds formed by a self-condensation reaction of up to 8 molecules according to Formula (I), provided that the compounds have at least one or two free —OH groups;
c) a solvent or mixture of solvents.

### Claim 18 (depends on 17)

The composition of claim 17, wherein:
X is a linear, branched or unbranched aliphatic alkyl residue with 1 to 6 carbon atoms, optionally substituted with fluorine or chlorine atoms;
R is (CH2)q wherein q=2 or 3;
Y1 and Y2 are identical or different and each is a hydrolysable or non-hydrolysable moiety selected from the group consisting of: methyl, ethyl and propyl groups; a cyclic aliphatic alkyl group with 1 to 6 carbon atoms; chlorine, an alkoxy selected from the group consisting of: methoxy, ethoxy, isopropoxy; and formyl or acetyl groups, with the provisio that at least one of Y1 and Y2 is selected from the group consisting of chlorine, methoxy, ethoxy, isopropoxy and n-propoxy; and a formyl or acetyl group;
m=2 or 3.

### Claim 19 (depends on 17)

The composition of claim 17, wherein:
X is a linear, branched or unbranched aliphatic alkyl residue with 1 to 6 carbon atoms, optionally substituted with fluorine;
Y1 and Y2 are each independently methyl; a cyclic aliphatic alkyl group with 1 to 6 carbon atoms; chlorine; or a methoxy, ethoxy, or isopropoxy group.

### Claim 20 (depends on 17)

The composition of claim 17, wherein component (B) of Formula I, is a reaction product of the hydrolyzation of an organosilane of Formula (II) with water and a catalyst, wherein Formula (II) is:
X—R—SiY1Y2Y3 (II)
and wherein X and R are defined as in claim 17 and Y1, Y2 and Y3 are identical or different and each is a hydrolysable or non-hydrolyzable moiety, with the proviso that at least one of Y′, Y2 and Y3 is hydrolysable.

### Claim 21 (depends on 20)

The composition of claim 20, wherein the hydrolyzable organosilane is a hydrolyzable fluoroalkylsilane of the general formula (III):
CF3(CF2)n(CH2)2Si(CH3)yX′3-y (III),
in which X′ is a group selected from chlorine, methoxy, ethoxy, isopropoxy, and n-propoxy;
n is a number from the series 3, 4, 5, 6, 7, 8, and 9; and
y is 0 or 1.

### Claim 22 (depends on 20)

The composition of claim 20, wherein the hydrolyzable organosilane is selected from the group consisting of: CF3—(CF2)5—(CH2)2—Si(OCH3)3; CF3—(CF2)5—(CH2)2—Si(OC2H5)3; CF3—(CF2)5—(CH2)2—SiCl3; CF3—(CF2)5—(CH2)2—Si(CH3)Cl2; CF3—(CF2)7—(CH2)2—SiCl3; CF3—(CF2)7—(CH2)2—Si(OCH3)3; CF3—(CF2)7—(CH2)2—Si(OC2H5)3; C10F21—(CH2)2—Si(OCH3)3; C10F21—(CH2)2—Si(OC2H5)3; C10F21—(CH2)2—SiCl3; and mixtures thereof.

### Claim 23 (depends on 17)

The composition of claim 17, wherein the amount of solvent or solvent mixture is from 30 wt. % to 99.89 wt. %, based on the total weight of the composition, and/or the solvent or solvent mixture is selected from the group consisting of: linear, branched or cyclic aliphatic hydrocarbons with 2 to 14 carbon atoms, optionally substituted with fluorine or chlorine atoms; aromatic hydrocarbons with 6 to 12 carbon atoms, optionally substituted with fluorine or chlorine atoms; monovalent linear or branched alcohols with 1 to 6 carbon atoms; ketones or aldehydes with 1 to 6 carbon atoms; ethers or esters with 2 to 8 carbon atoms; linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units; and mixtures thereof.

### Claim 24 (depends on 17)

The composition of claim 17, wherein the concentration of the hydrophobically modified fumed silica is not less than 0.1 wt. %, based on the total weight of the composition and/or the hydrophobically modified silica particles have a median particle size in the range of from 100 to 50,000 nm.

### Claim 25 (depends on 17)

The composition of claim 17, wherein the ratio of component (B), in sum of all individual components thereof, to the hydrophobically modified fumed silica in component (A) is in the range of 0.019:1 to 20.92:1; and/or the content of compounds of component B in claim 17 in sum in the composition, is higher than the content of polysiloxanes formed from compounds according to Formula (I).

### Claim 26 (depends on 17)

The composition of claim 17, wherein the composition further comprises component (D), a compound of general formula (IV) or (V):
(R1R2R3Si)2NR4 (IV)
—(R1R2SiNR4)m-(cyclo) (V)
wherein R1, R2, and R3 can be the same or different, and are independently selected from: hydrogen; linear or branched, saturated or unsaturated alkyl chain groups of from 1 to 8 carbon atoms; and aromatic groups of from 6 to 12 carbon atoms;
R4 is hydrogen or a methyl group; and
m is from 3 to 8.

### Claim 27 (depends on 17)

A process for the preparation of a composition of claim 17, wherein the process comprises the steps:
a) preparing a silica dispersion comprising hydrophobically modified fumed silica as defined in claim 17 and a solvent or solvent mixture selected from the group consisting of: linear, branched or cyclic aliphatic hydrocarbons with 2 to 14 carbon atoms, optionally substituted with fluorine or chlorine atoms; aromatic hydrocarbons with 6 to 12 carbon atoms, optionally substituted with fluorine or chlorine atoms; monovalent linear or branched alcohols with 1 to 6 carbon atoms; ketones or aldehydes with 1 to 6 carbon atoms; ethers or esters with 2 to 8 carbon atoms; linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units; and mixtures thereof;
b) preparing a hydrolyzed organosilane component (B) by hydrolyzation of:
i) at least one hydrolyzable organosilane according to Formula (II):
X—R—SiY1Y2Y3 (II)
wherein X, and R, are defined as in claim 17 and Y1, Y2 and Y3 are identical or different and are each a hydrolysable or non-hydrolyzable moiety, with the provisio that at least one of Y1, Y2 and Y3 is hydrolysable.
ii) a catalyst; and
iii) water;
c) mixing the silica dispersion from step a) with the hydrolyzed organosilane composition obtained in step b) and optionally a further solvent or solvent mixture.

### Claim 28 (depends on 20, 21, 27)

The process of claim 27, wherein the silica dispersion in step a) comprises from 60 to 95% by weight of a solvent or solvent mixture based on the overall weight of the dispersion; and/or the silica dispersion in step a) comprises 5 to 30 wt. % of hydrophobically modified fumed silica based on the overall composition of the dispersion; and/or the silica dispersion in step a) comprises 0.1 to 10 percent by weight of the total weight of the dispersion of compounds of Formula (II) as defined in claim 20 and/or Formula (III) as defined in claim 21.

### Claim 29 (depends on 27)

The process of claim 27, wherein shear forces are applied to the dispersion to adjust the average particle size distribution to a desired particle size.

### Claim 30 (depends on 27)

The process of claim 27, wherein step a) comprises:
a1) providing a pre-dispersion comprising hydrophobically modified fumed silica particles by stirring said silica particles into a solution comprising:
i) at least one compound of general Formula (IV) or (V), wherein R1, R2, R3 and R4 are defined as above; and
ii) a first solvent or solvent mixture selected from: straight or branched, linear or cyclic aliphatic, or aromatic hydrocarbons with 2 to 14 carbon atoms, optionally substituted with fluorine or chlorine atoms; monovalent linear or branched alcohols with 1 to 6 carbon atoms; ketones or aldehydes with 1 to 6 carbon atoms; ethers or esters with 2 to 8 carbon atoms; or linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,
wherein the concentration of the hydrophobically modified fumed silica particles in the pre-dispersion is from 10 to about 30 percent by weight of the total weight of the pre-dispersion, and wherein the concentration of any one of compounds according to Formula (IV) and/or (V) is between 0.1 and 10 percent by weight of the total weight of the pre-dispersion; and
a2) mixing said pre-dispersion with a disperser to provide a silica dispersion while reducing said silica particles to a median particle size as defined for component (A) above.

### Claim 31 (depends on 27)

The process of claim 27, wherein step b) comprises:
mixing the hydrolyzable organosilane of Formula (II) with water and a catalyst;
stirring the mixture thus obtained for 1 to 4 hours, at a temperature of 0 to 80° C.; and
choosing a molar ratio of hydrolyzable organosilane to water in a range of 1:4.5 to 1:9.

### Claim 32 (depends on 27)

The process of claim 27, wherein the solvent or solvent mixture added in step a) and c) are the same.

### Claim 33 (depends on 27)

The process of claim 27, wherein the solvent or solvent mixture added in step a) and c) are different.

### Claim 34 (depends on 27)

The process of claim 27, wherein the silica dispersion of step a) is prepared according to a process comprising: suspending hydrophobic particles having an average particle diameter of from 100 to 100,000 nm in a solution of a silicone wax in a highly volatile siloxane, wherein said silicone wax is liquid at room temperature and said highly volatile siloxane is liquid at room temperature and comprises at least one compound of general Formula (VI), a cyclic compound of general Formula (VII) or a mixture thereof:
wherein n is a number from 2 to 10.

### Claim 35 (depends on 17)

An article which comprises at least one surface treated by the composition of claim 17.