# US 7,612,126 B2 · Low-VOC aqueous coating compositions with excellent freeze-thaw stability

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- Number: US 7,612,126 B2
- Document ID: US7612126B2
- Status: Granted
- Kind: B2
- Application number: 10/580,250
- Filed: 2004-12-01
- Published: 2007-05-10
- Granted: 2009-11-03
- Earliest claimed: 2003-12-04
- Assignees: BASF SE
- Inventors: Konrad Roschmann; Joerg Leuninger; Rolf Dersch; Cheng-Le Zhao; Li Zhuo; Terri A. Cunningham
- Web page: https://patentgrep.com/patent/US7612126B2

## CPC

- C09D 151/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09D151/04, C09D151/06 take precedence)}
- C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof
- C08K 3/013: Fillers, pigments or reinforcing 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The present invention relates to an aqueous coating composition having excellent freeze-thaw stability and a low-VOC content, comprising a multi-stage polymer dispersion comprising (a) an inner phase comprising at least one latex polymer derived from at least one monomer and at least one polymerizable alkoxylated surfactant having the structure: R1—R2 wherein R1 is an allyl group selected from the group consisting of CH3—CH═CH— and CH2═CH—CH2—, or an acrylic group and R2 is a radical comprising at least two carbon atoms and at least one oxyethylene or oxypropylene unit; (b) an outer phase having a glass transition temperature of from 30° C. to 110° C. containing at least one ethylenic unsaturated monomer (c) at least one pigment; (d) water; and (e) less than 3.0% by weight based on the total weight of the aqueous coating composition of anti-freeze agents.

## Claims

### Claim 1

An aqueous coating composition, comprising a multi-stage polymer dispersion comprising
a) an inner phase comprising at least one latex polymer derived from at least one monomer and at least one polymerizable alkoxylated surfactant having the structure:
R1—R2
wherein R1 is an allyl group selected from the group consisting of CH3—CH═CH— and CH2═CH—CH2—, or an acrylic group and R2 is a radical comprising at least two carbon atoms and at least one oxyethylene or oxypropylene unit;
(b) an outer phase having a glass transition temperature of from 30° C. to 110° C. containing at least one ethylenic unsaturated monomer;
(c) at least one pigment;
(d) water; and
(e) less than 3.0% by weight based on the total weight of the aqueous coating composition of anti-freeze agents.

### Claim 2 (depends on 1)

The composition according to claim 1, comprising less than 1.0% by weight based on the total weight of the aqueous coating composition of anti-freeze agents.

### Claim 3 (depends on 1)

The composition according to claim 1, being substantially free of anti-freeze agents.

### Claim 4 (depends on 1)

The composition according to claim 1, wherein R2—C6H3(R3)—(O—CH2—CH2)n—R4, O—CH2—CH(CH2—O—C6H4—R3)—(O—CH2—CH2)n—R4, —(O—CH2—CH2)n—R4, —(O—CH2—CH(CH3))n—R4, —(O—CH2—CH2)m—(O—CH2—CH(CH3))n—R4 or —(O—CH2—CH(CH3))m—(O—CH2—CH2)n—R4; R3 is an alkyl group; R4 is hydroxy or a polar group with the provision that R4 cannot be (—SO4M) or (—PO4M) if R2 is (O—CH2—CH(CH3))n—R4 or —(O—CH2—CH(CH3))m—(O—CH2—CH2)n—R4; n is from about 5 to about 100; and m is from 0 to about 100.

### Claim 5 (depends on 4)

The composition according to claim 4, wherein n is from about 5 to about 40.

### Claim 6 (depends on 1)

The composition according to claim 1, wherein the alkoxylated surfactant in the inner soft phase is a monomer expressed by the formula
with n=6−12.

### Claim 7 (depends on 1)

The composition according to claim 1, wherein the alkoxylated surfactant in the inner soft phase is a monomer expressed by the formula
With n=5−10.

### Claim 8 (depends on 1)

The composition according to claim 1, further comprising up to 30% of a solvent.

### Claim 9 (depends on 1)

The composition according to claim 1, wherein the at least one pigment includes at least one pigment selected from the group consisting of TiO2, clay, CaCO3, aluminium oxide, silicon dioxide, magnesium oxide, talc (magnesium silicate), barytes (barium sulfate), zinc oxide, zinc sulfite, sodium oxide, potassium oxide and mixtures thereof.

### Claim 10 (depends on 1)

The composition according to claim 1, wherein the at least one pigment includes TiO2, calcium carbonate or clay.

### Claim 11 (depends on 1)

The composition according to claim 1, wherein the inorganic pigment includes TiO2.

### Claim 12 (depends on 1)

The composition according to claim 1, wherein the latex polymer is selected from the group consisting of pure acrylics, styrene acrylics, vinyl acrylics and acrylated ethylene vinyl acetate copolymers.

### Claim 13 (depends on 1)

The composition according to claim 1, wherein the latex polymer includes a pure acrylic.

### Claim 14 (depends on 1)

The composition according to claim 1, wherein the latex polymer is derived from at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters.

### Claim 15 (depends on 1)

The composition according to claim 1, wherein the latex polymer is further derived from one or more monomers selected from the group consisting of styrene, α-methyl styrene, vinyl chloride, acrylonitrile, methacrylonitrile, ureido methacrylate, vinyl acetate, vinyl esters of branched tertiary monocarboxylic acids, itaconic acid, crotonic acid, maleic acid, fumaric acid, acetyl acetoxy ethyl methacrylate, ethylene, and C4-C8 conjugated dienes.

### Claim 16 (depends on 1)

The composition according to claim 1, further comprising one or more additives selected from the group consisting of dispersants, surfactants, rheology modifiers, defoamers, thickeners, biocides, mildewcides, colorants, waxes, perfumes and co-solvents.

### Claim 17

A latex paint composition comprising a multi-stage polymer dispersion comprising
(a) an inner phase comprising at least one latex polymer derived from at least one monomer and at least one polymerizable alkoxylated surfactant having the structure:
wherein R1 is an allyl group selected from the group consisting of CH3—CH═CH— and CH2═CH—CH2—, or an acrylic group and R2 is a radical comprising at least two carbon atoms and at least one oxyethylene or oxypropylene unit;
(b) an outer phase having a glass transition temperature of from 30° C. to 110° C. containing at least one ethylenic unsaturated monomer;
(c) at least one pigment;
(d) water; and
(e) less than 3.0% by weight based on the total weight of the aqueous coating composition of anti-freeze agents.