(19)
(11)EP 2 245 087 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
12.08.2015 Bulletin 2015/33

(21)Application number: 09702572.0

(22)Date of filing:  16.01.2009
(51)International Patent Classification (IPC): 
C08J 9/00(2006.01)
C09K 8/584(2006.01)
(86)International application number:
PCT/US2009/000309
(87)International publication number:
WO 2009/091592 (23.07.2009 Gazette  2009/30)

(54)

LATEX BINDERS, AQUEOUS COATINGS AND PAINTS HAVING FREEZE-THAW STABILITY AND METHODS FOR USING SAME

LATEXBINDEMITTEL, WÄSSRIGE BESCHICHTUNGEN UND ANSTRICHMITTEL MIT FROST-TAU-STABILITÄT UND VERFAHREN ZU IHRER VERWENDUNG

LIANTS LATEX, REVÊTEMENTS AQUEUX ET PEINTURES PRÉSENTANT UNE STABILITÉ AU GEL/DÉGEL ET PROCÉDÉS D'UTILISATION CORRESPONDANTS


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

(30)Priority: 18.01.2008 US 22206
21.01.2008 US 22443
21.11.2008 US 199936

(43)Date of publication of application:
03.11.2010 Bulletin 2010/44

(60)Divisional application:
13188193.0 / 2703433
13188195.5 / 2703434

(73)Proprietor: Rhodia Opérations
93306 Aubervilliers (FR)

(72)Inventors:
  • ZONG, Zhengang
    Pennington NJ 08534 (US)
  • LI, Yi-zhong
    East Brunswick NJ 08816 (US)
  • RUIZ, Jose
    Burlington NJ 08016 (US)

(74)Representative: Busher, Samantha Jane et al
Elkington and Fife LLP 3-4 Holborn Circus
London, EC1N 2HA
London, EC1N 2HA (GB)


(56)References cited: : 
WO-A2-2005/019353
US-B2- 6 933 415
US-B2- 6 410 655
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    CROSS REFERENCE TO RELATED APPLICATIONS



    [0001] This application claims the benefit of U.S. Provisional Application Serial No. 61/022,206, filed January 18, 2008, U.S. Provisional Application Serial No. 61/022,443, filed January 21, 2008 and U.S. Provisional Application Serial No. 61/199,936, filed November 21, 2008.

    FIELD OF THE INVENTION



    [0002] The present invention relates to the use of a particular family of alkoxylated compounds, e.g alkoxylated tristyrylphenol and alkoxylated tributylphenol, for improving freeze-thaw stability and open time of aqueous coating compositions such as paint and paper coating compositions. In particular, the present invention relates to the use of certain reactive alkoxylated compound based monomers, surface active alkoxylated compound surfactants, and surface active alkoxylated compound additives for freeze-thaw stability of aqueous latex dispersions, aqueous latex binders and aqueous latex paints.

    BACKGROUND OF THE INVENTION



    [0003] Latex paints are used for a variety of applications including interior and exterior, and flat, semi-gloss and gloss applications. However, paints and aqueous latex dispersions, particularly low VOC paints and latex dispersions, suffer from a lack of freeze-thaw stability. This is particularly a problem during transportation and storage.

    [0004] Latex freeze-thaw (sometimes herein referred to as "F/T") stability, including the freezing-thawing process, destabilization mechanism, and polymer structures, have been extensively studied since 1950. Blackley, D.C., Polymer Lattices-Science and Technology, 2nd Ed., Vol. 1, Chapman & Hall, 1997, gives a comprehensive review of colloidal destabilization of latexes by freezing. The freezing process starts with the decrease of temperature which leads to the formation of ice crystals. The ice crystal structures progressively increase the latex particle concentration in the unfrozen water. Eventually latex particles are forced into contact with each other at the pressure of growing ice crystal structures, resulting in particle aggregation or interparticle coalescence. To make a stable latex dispersion in aqueous medium or latex paints with freeze-thaw stability, various approaches have been employed. The addition of antifreeze agents, e.g. glycol derivatives, has been applied to latex paint to achieve freeze-thaw stability. Thus, latex paints include anti-freeze agents to allow the paints to be used even after they have been subjected to freezing conditions. Exemplary anti-freeze agents include ethylene glycol, diethylene glycol and propylene glycol.

    [0005] See, Bosen, S.F., Bowles, W.A., Ford, E.A., and Person, B.D., "Antifreezes," Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A3, VCH Verlag, pages 23-32, 1985. However, a low or no VOC requirement means the glycol level that can be used has to be reduced or eliminated. Aslamazova, T. R., Colloid Journal, Vol. 61, No. 3, 1999, pp. 268-273, studied the freeze resistance of acrylate latexes and revealed the role of electrostatic contribution to the potential energy of latex particle interactions. Using electrostatic effects on colloidal surface, the interactions of Coulombic repulsion between the charged latex particles lead to higher potential energy. The electrical effects stabilize the latex particles in the freezing and thawing process.

    [0006] Rajeev Farwaha et. al. (U.S. Patent: no. 5,399,617) discloses the copolymerizable amphoteric surfactants and discloses latex copolymers comprising the copolymerizable amphoteric surfactants impart freeze-thaw stability to the latex paints.

    [0007] Cheng-Le Zhao et. al. (U.S. Patent no. 6,933,415 B2) discloses latex polymers including polymerizable alkoxylated surfactants and discloses the low VOC aqueous coatings have excellent freeze-thaw stability.

    [0008] Rajeev Farwaha et. al. (U.S. Patent no. 5,610,225) discloses incorporating a monomer with long polyethylene glycol structures to achieve stable freeze-thaw latex.

    [0009] Masayoshi Okubo et. al. (U.S. Patent: no. 6,410,655 B2) discloses freeze-thaw stability of latex polymers including ethylenic unsaturated monomers.

    [0010] The additives used as anti-freeze agents are effective for their purposes but are becoming more and more undesirable because they are volatile organic compounds (VOC's). After application of the latex paint to a substrate, the VOC's slowly evaporate into the surroundings.

    [0011] With strict environmental legislation requiring the reduction of the amount of Volatile Organic Compounds (VOC) in coatings, it is desirable to have paint formulations without or with substantially reduced VOC content, which would include coalescing agents and freeze-thaw agents, among others. Latex binder manufactures are thus forced to develop low VOC binders to meet the requirements of paints and coatings industry. However, low VOC coatings and paints must meet or exceed coating performance standards set in the industry.

    [0012] In traditional latex binders for architectural coatings, the glass transition temperature is between above 10°C to about 40 °C. However, such architectural coatings often need and contain coalescent agents to soften such latex binders (i.e., soften the latex binders having relatively Tg in the range of above 10 °C to about 40 °C) or anti-freeze agents; both of which are typically high VOC solvents. Thus, these traditional architectural coatings with higher Tg latex binders cannot be formulated to be low VOC without solvents.

    [0013] For the low VOC application (i.e., low Tg) binders, the average Tg is close to or below 0 °C. However, the latex binder with low Tg causes grit when subjected to freeze/thaw cycles as well as exposure to mechanical shear. The resulting coating films are softer and tackier, even after fully dried, and are susceptible to blocking and dirt pick-up effects. Also, such low Tg latex binders and resulting latex paints are not stable, and gel in a cold environmental storage or transportation process. Freeze-Thaw stability of low Tg latex binders and low VOC paints is critically important for transportation, storage, and practical applications. Thus, there is a need to develop latex paints and latex particle dispersions using emulsion polymer technology which meet zero or low VOC requirement and at the same provide excellent mechanical and film performance without sacrificing the freeze-thaw stability of those paints.

    [0014] WO 2005/019353 discloses copolymer surfactants and their use in coatings. WO'353 also discloses dispersing coloured pigments using the copolymer surfactant.

    SUMMARY OF THE INVENTION



    [0015] The present invention relates to the use of a particular family of alkoxylated compounds with bulky hydrophobic groups, e.g., alkoxylated tristyrylphenols or alkoxylated tributylphenols, for improving freeze-thaw stability, as well as other properties such as open time, low temperature film formation, stain resistance, film gloss, dispersibility, hiding and scrub resistance, foam resistance, block resistance, adhesion and water sensitivity, among others, of latex binders, paints and coatings. During the thawing process of the freeze-thaw process in latex dispersions and paint formulation, it is believed that the latex particles with high Tg are easy to recover, while the particles with relatively low Tg can not recover from the aggregation or coalescence states which gel.

    [0016] While not being bound to theory, it is theorized the present invention in part stabilizes the latex particles using steric effects of larger hydrophobic groups to form a protective layer on the surfaces of soft latex particles. The large hydrophobic groups adsorbed or grafted onto the latex particles or co-polymerized into the latex particles prevent these latex particles from approaching the surfaces of other soft latex particles and increase the distance of separation between soft latex particles. The alkylene, e.g., ethylene oxide units from the surfactant of the alkoxylated compounds chains also form a layer which interacts with aqueous medium.

    [0017] In accordance with the invention, aqueous coating compositions (e.g. latex paints, latex dispersion) including an alkoxylated compound can be produced having excellent freeze-thaw stabilities with the addition of little or no other anti-freeze agents such as glycol, coalescents and high VOC components, more typically with no anti-freeze agents. Freeze-thaw stability or being freeze-thaw stable generally is understood to mean that the composition/formulation does not gel in 3 or more F/T cycles, typically 5 or more F/T cycles.

    [0018] The alkoxylated compounds can be employed in a number of ways for improving freeze-thaw stability of latex binders, paints and coatings. The present invention may employ polymerizable reactive alkoxylated monomers as a reactant during emulsion polymerization to form the latex polymer. The present invention may employ one or more surface active alkoxylated compounds described herein as a surfactant (emulsifier) during emulsion polymerization to form the latex polymer. The present invention may employ a surface active alkoxylated compound as an additive to a latex polymer-containing aqueous dispersion or concentrate.

    [0019] In one aspect, the present invention is a latex polymer binder derived from at least one first monomer and at least one polymerizable reactive alkoxylated second monomer having the structural formula IA:

    wherein R1, R2 and R3 are independently selected from:



    wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms; wherein n is an integer of from 1 to 100, wherein R comprises an ethylenically unsaturated group; and wherein the latex binder has a glass transition temperature (Tg) of between -15°C and 12°C. In one embodiment, R can be acrylate, C1-C6 alkyl acrylate, allyl, vinyl, maleate, itaconate or fumarate. R can also be selected from acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleimido, styrenyl, and/or α-alkyl styrenyl groups.

    [0020] In another embodiment, R has a chemical structure: RaCH=C(Rb)COO-, wherein if Ra is H, then Rb is H, C1-C4 alkyl, or -CH2COOX; if Ra is -C(O)OX, then Rb is H or -CH2C(O)OXa; or if Ra is CH3, then Rb is H and Xa is H or C1-C4 alkyl. R can, in another embodiment, have chemical structure: -HC=CYZ or - OCH=CYZ, wherein Y is H, CH3, or Cl ; Z is CN, Cl, - COORc, -C6H4Rc, -COORd, or -HC=CH2; Rd is C1 -C8 alkyl or C2-C8 hydroxy alkyl; Rc is H, Cl, Br, or C1-C4 alkyl.

    [0021] In another aspect, the present invention is a latex polymer binder derived from at least one first monomer and at least one second monomer having the structural formula IB:

    wherein n is an integer of from 1 to 100, and R4 is selected from H and C1-C6 alkyl. In one embodiment, n is an integer of from 3 to 80, typically, 10 to 60, and more typically from 20 to 50. The at least one first monomer can, in one embodiment, comprise at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. In another embodiment, the latex polymer can be derived from one or more monomers selected from styrene, alpha-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, ethylene, or C4-C8 conjugated dienes.

    [0022] The composition of the present invention is freeze-thaw stable and the latex polymer binder has a glass transition temperature (Tg) of between -15°C and 12°C, more typically between -5°C and 5°C, and even more typically between -5°C and 0°C.

    [0023] In another embodiment, the latex polymer binder of the present invention has a mean particle size (sometimes referred to as mean particle diameter, D50) of less than 200 nm, more typically a mean particle size of less than 190 nm, and most typically a mean particle size of less than 175 nm.

    [0024] In a further embodiment, the composition of the present invention is freeze-thaw stable, and the latex polymer binder has a Tg of between -15°C and 12°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 200 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 190 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 175 nm.

    [0025] In another aspect, the present invention is a latex coating composition comprising: (a) a latex polymer binder as described above or as described anywhere herein; and (b) water. It is understood that the latex coating composition can contain other additive/ingredients including but not limited to biocides, surfactants, pigments, dispersants, etc. The latex coating composition can further comprise a freeze-thaw additive comprising an ethoxylated tristyrylphenol having the structural formula IIC or IIC-1:

    or

    wherein, n is an integer of from 1 to 100, wherein R5 is -OH, -OCH3,-OC2H5, -OC3H7, -OC4H9, -OC5H11, -OC6H13, -Cl, -Br, -CN, Phosphonate (-PO3-M+), Phosphate (PO4-M+), Sulfate (SO4-M+), Sulfonate (SO3-M+), carboxylate (COO-M+), a nonionic group, or a quaternary ammonium ion, wherein M+ is a cation including but not limited to H+, Na+, NH4+, K+ or Li+. In one embodiment, n is an integer of from 1 to 40.

    [0026] In one embodiment, the latex coating composition contains a freeze-thaw additive in an amount effective to impart freeze-thaw stability to the composition. In one embodiment, the effective amount is greater than 1.3% by weight of the latex polymer binder, typically in an amount greater than 1.6% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive in an amount greater than 2% by weight of the latex polymer binder, typically in an amount greater than 4% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive in an amount greater than 7.5% by weight of the latex polymer binder, typically in an amount greater than 8% by weight of the latex polymer binder. In yet another embodiment, the latex coating composition contains a freeze-thaw additive in an amount greater than 10% by weight of the latex polymer binder. In yet another embodiment, the latex coating composition contains a freeze-thaw additive in an amount greater than 20% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive in an amount between 1.6% and 7.5% by weight of the latex polymer binder.

    [0027] The aforementioned latex coating composition is freeze-thaw stable and the latex polymer binder comprises a glass transition temperature (Tg) of between -15°C and 12°C, typically between -5°C and 5°C, more typically between -5°C and 0°C. In another embodiment, a latex polymer binder in the aforementioned latex coating has a mean particle size of less than 200 nm, more typically less than 190 nm, most typically, less than 175 nm.

    [0028] In yet another aspect, the present invention is a method of preparing a latex polymer binder, comprising copolymerizing (1) at least one first monomer with (2) at least one second monomer, the second monomer a polymerizable reactive tristyrylphenol having the structural formula IA:

    wherein R1, R2 and R3 are independently selected from:



    wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms; wherein n is in the range of 1-100, wherein R is an ethylenically unsaturated group including but not limited to acrylate, C1-C6 alkyl acrylate, allyl, vinyl, maleate, itaconate or fumarate. R can also be selected from acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleimido, styrenyl, and/or α-alkyl styrenyl groups; and wherein the latex binder has a glass transition temperature (Tg) of between -15°C and 12°C.

    [0029] In a further aspect, the present invention is a method of preparing latex polymer binder, comprising copolymerizing (1) at least one latex monomer with (2) at least one polymerizable reactive tristyrylphenol having the structural formula IB:

    wherein n is an integer of from 1 to 100, and R4 is selected from H and C1-C10 alkyl, typically C1-C6 alkyl.

    [0030] In one or both of the aforementioned methods, an aqueous dispersion of the polymer is freeze-thaw stable, where the polymer comprises a glass transition temperature (Tg) of between -15°C and 12°C, more typically between-5°C and 0°C. In another embodiment, the polymer utilized in one or more of the above-referenced methods comprises a mean particle size of less than 200 nm, more typically a mean particle size of less than 190 nm, and most typically a mean particle size of less than 175 nm.

    [0031] In yet another aspect, the present invention is a method of preparing freeze-thaw stable latex polymer binder, comprising copolymerizing (1) at least one first monomer with (2) at least one second monomer having the structural formula IB:

    wherein n is in the range of 1-100, R4 is selected from the group consisting of H and C1-C8 alkyl, and wherein the polymer has a glass transition temperature (Tg) of between -15°C and 12°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 200 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 190 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 175 nm.

    [0032] These and other features and advantages of the present invention will become more readily apparent to those skilled in the art upon consideration of the following detailed description, which describe both the preferred and alternative embodiments of the present invention.

    BRIEF DESCRIPTION OF DRAWINGS



    [0033] FIG. 1 is a chart illustrating the Glass Transition temperature (Tg) of latex binders (prepared from the '514 application description) using different emulsifying surfactants during emulsion polymerization.

    DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS



    [0034] The present invention relates to the use of a particular family of alkoxylated compounds, e.g., alkoxylated tristyrylphenols and alkoxylated tributylphenols, provided with an ethylene oxide chain for improving freeze-thaw stability of latex binders and paints. This family of alkoxylated compounds can improve other properties as well, for example, open time, stain resistance, film gloss, dispersibility, hiding and scrub resistance, low temperature film formation, foam resistance, block resistance, adhesion and water sensitivity, among others.

    [0035] As used herein, the term "alkyl" means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.

    [0036] As used herein, the term "cycloalkyl" means a saturated hydrocarbon radical that includes one or more cyclic alkyl rings, such as, for example, cyclopentyl, cyclooctyl, and adamantanyl.

    [0037] As used herein, the term "hydroxyalkyl" means an alkyl radical, more typically an alkyl radical, that is substituted with a hydroxyl groups, such as for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.

    [0038] As used herein, the term "alkylene" means a bivalent acyclic saturated hydrocarbon radical, including but not limited to methylene, polymethylene, and alkyl substituted polymethylene radicals, such as, for example, dimethylene, tetramethylene, and 2-methyltrimethylene.

    [0039] As used herein, the term "alkenyl" means an unsaturated straight chain, branched chain, or cyclic hydrocarbon radical that contains one or more carbon-carbon double bonds, such as, for example, ethenyl, 1-propenyl, 2-propenyl.

    [0040] As used herein, the term "aryl" means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, which may be substituted one or more of carbons of the ring with hydroxy, alkyl, alkenyl, halo, haloalkyl, or amino, such as, for example, phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl.

    [0041] As used herein, the term "aralkyl" means an alkyl group substituted with one or more aryl groups, such as, for example, phenylmethyl, phenylethyl, triphenylmethyl.

    [0042] As used herein, the terminology "(Cn-Cm)" in reference to an organic group, wherein n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.

    [0043] As used herein, the terminology "ethylenic unsaturation" means a terminal (that is, e.g., α, β) carbon-carbon double bond.

    [0044] The present invention includes latex polymer binders and latex dispersions having low-VOC content and excellent freeze-thaw stability and open time properties compared to conventional aqueous coating compositions, as well as methods of use. Such latex polymer binders can include at least one latex polymer copolymerized or blended with a particular family of alkoxylated compounds. The latex polymer binder has a Tg in the range of from -15°C to 12°C, more typically from -5°C to 5°C, more typically in the range from -5°C to 0°C. In one embodiment, the latex polymer binder of the present invention has a weight average molecular weight of from 1,000 to 5,000,000, typically 5,000 to 2,000,000. In another embodiment, the latex polymer of the present invention has a weight average molecular weight of from 10,000 to 250,000.

    [0045] The present invention provides aqueous compositions, for example, aqueous coating compositions, having low-VOC content and excellent freeze-thaw stability and open time properties comparable to conventional aqueous coating compositions. The aqueous compositions of the invention are aqueous polymer dispersions which include at least one latex polymer copolymerized or blended with a particular family of alkoxylated compounds, e.g., alkoxylated tristyrylphenol. Generally, the latex polymer binder is present in such aqueous compositions or paints from 15% to 40% by weight of the composition for semigloss and from 5% to up to 75%, typically 5% to 50% by weight of the composition for flat paint. Paints or other aqueous coatings of the present invention typically further include at least one pigment.

    [0046] The members of the particular family of alkoxylated compounds, e.g., alkoxylated tristyrylphenols and/or tributylphenols, can be employed in a number of ways for improving freeze-thaw stability of latex binders and paints. The present invention may employ polymerizable reactive alkoxylated monomers to form a latex comonomer, surface active alkoxylated compounds as a surfactant (emulsifier) to be present during latex polymer formation, and/or surface active alkoxylated compounds as an additive to an aqueous dispersion of latex polymer or copolymer.

    Reactive polymerizable tristyrylphenol ethoxylates



    [0047] In one embodiment, polymerizable reactive alkoxylated (second) monomer of the following formula IA can be copolymerized (with a first monomer) into the backbone of the latex polymer binder.

    wherein B is a single ring aromatic hydrocarbon having a 6 membered ring, i.e., a benzene ring;
    R1, R2 and R3 are independently selected from:



    wherein, X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms; n is an integer of from 1 to 100, for example from 4 to 80 or 8 to 25; wherein R is an ethylenically unsaturated group; and wherein the latex binder has a glass transition temperature (Tg) of between -15°C and 12°C. In one embodiment, n is an integer of from 4 to 80. In one embodiment, n is an integer of from 4 to 60. In one embodiment, n is an integer of from 10 to 50. In one embodiment, n is an integer of from 10 to 25.

    [0048] Typically, R includes acrylate, or C1-C6 alkyl acrylate, e.g., methacrylate, allyl, vinyl, maleate, itaconate or fumarate, typically R is acrylate or methacrylate.

    [0049] Suitable polymerizable functional groups R include, for example, acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleimido, styrenyl, and α-alkyl styrenyl groups.

    [0050] For example, suitable polymerizable functional groups R have the chemical structure: RaCH=C(Rb)COO-, wherein if Ra is H, then Rb is H, C1-C4 alkyl, or -CH2COOX; if Ra is -C(O)OX, then Rb is H or -CH2C(O)OXa; or if Ra is CH3, then Rb is H and X2 is H or C1-C4 alkyl.

    [0051] For example, other suitable polymerizable functional groups R have the chemical structure: -HC=CYZ or -OCH=CYZ, wherein Y is H, CH3, or Cl ; Z is CN, Cl, - COORc, -C6H4Rc, -COORd, or -HC=CH2; Rd is C1 -C8 alkyl or C2-C8 hydroxy alkyl; Rc is H, Cl, Br, or C1-C4 alkyl.

    [0052] The monomer has the formula IA:

    wherein, R, R1, R2, R3, X and n are as defined for the structure of formula IA and wherein the latex binder has a glass transition temperature (Tg) of between -15°C and 12°C. If desired, the aromatic ring shown in structural formula IA may be saturated. For example, such a saturated monomer may be made by saturating a form of the monomer wherein H is in the R position and then replacing the H in the R position with one of the other above-listed R groups.

    [0053] In one embodiment, at least one monomer can be copolymerized with a second monomer having structure IB-1:

    wherein R is

    R1, R2 and R3 are each independently:



    R7 is a divalent linking group, O, (C1-C6) alkylene,

    or absent,
    R8 is H or methyl,
    R9 is O or NR10,
    R10 is H or (C1-C4) alkyl; n is an integer of from 2 to 4, and m is an integer of from 1 to 100.

    [0054] In one embodiment, R can be acrylate, C1-C6 alkyl acrylate, allyl, vinyl, maleate, itaconate or fumarate. In one embodiment, R is at least one of acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleimido, styrenyl, and/or α-alkyl styrenyl groups.

    [0055] In another embodiment, the monomer is an ethoxylated tristyrylphenol. The polymerizable reactive ethoxylated tristyrylphenols have the structural formula IB, as follows:

    wherein, n is an integer of from 1-100, for example, 4 to 60 or 8 to 25;
    R4 is a member of the group H, C1-C8 hydroxy alkyl, C1-C6 alkyl, for example, CH3 or C2H5.

    [0056] Thus, the reactive polymerizable ethoxylated tristyrylphenol monomer has a tristyrylphenol portion, an alkylene oxide portion and a reactive substituted or unsubstituted acrylic end group for polymerization. If desired, the ethylene oxide group shown in structural formula IB may be replaced with the above discussed - (OX)- group to form an alkoxylated tristyrylphenol, and the -C(O)-CHR4CH2 end group may be replaced by allyl, vinyl, maleate, itaconate or fumarate.

    [0057] Tristyrylphenol ethoxylates, for other uses, are disclosed by US patent number 6,146,570, published PCT patent application number WO 98/012921 and WO 98/045212.

    [0058] If desired the aromatic rings of the styryl groups in Formula IB may be saturated.

    [0059] When reactive polymerizable alkoxylated monomer of IA, IA-1 and/or IB is copolymerized into the backbone of the latex polymer binder, the latex polymer binder is made from a mixture wherein the reactive tristyrylphenol monomer is 1 to 20 parts per 100 parts by weight of monomers used to form the copolymer, more typically 2 to 15, 2 to 8, or 2 to 6 parts per 100 parts by weight of monomers used to form the copolymer.

    Other Monomers



    [0060] In addition to the polymerizable tristyrylphenol monomer, there are other monomers from which the at least one latex polymer binder used in the aqueous coating composition, e.g., paint, is typically derived. For purposes of this description, these other monomers from which latex polymer binders may be derived are termed latex monomers. Typically, these other latex monomers comprise at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. In addition, the other monomers for making the latex polymer can optionally be selected from one or more monomers selected from the group consisting of styrene, a-methyl styrene, vinyl chloride, acrylonitrile, methacrylonitrile, ureido methacrylate, vinyl acetate, vinyl esters of branched tertiary monocarboxylic acids (e.g. vinyl esters commercially available under the mark VEOVA from Shell Chemical Company or sold as EXXAR Neo Vinyl Esters by ExxonMobil Chemical Company), itaconic acid, crotonic acid, maleic acid, fumaric acid, and ethylene. It is also possible to include C4-C8 conjugated dienes such as 1,3-butadiene, isoprene and chloroprene. Typically, the monomers include one or more monomers selected from the group consisting of n-butyl acrylate, methyl methacrylate, styrene and 2-ethylhexyl acrylate. The latex polymer is typically selected from the group consisting of pure acrylics (comprising acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers); styrene acrylics (comprising styrene and acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers); vinyl acrylics (comprising vinyl acetate and acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers); and acrylated ethylene vinyl acetate copolymers (comprising ethylene, vinyl acetate and acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers). The monomers can also include other main monomers such as acrylamide and acrylonitrile, and one or more functional monomers such as itaconic acid and ureido methacrylate, as would be readily understood by those skilled in the art. In a particularly preferred embodiment, the latex polymer binder is a pure acrylic such as a butyl acrylate/methyl methacrylate copolymer derived from monomers including butyl acrylate and methyl methacrylate.

    [0061] In one embodiment, the other monomer is an ethoxylated tristyrylphenol, which may have the structural formula IC, as follows:

    wherein, n is an integer of from 1-100, for example, 4 to 60 or 8 to 25 and R4 is a member of the group H, C1-C8 hydroxy alkyl, C1-C6 alkyl, for example, CH3 or C2H5.

    [0062] In one embodiment, the reactive polymerizable alkoxylated monomer of formula IA, IA-1 and/or IB are utilized and copolymerized with one of the monomers listed under "other monomers" into the backbone of a latex polymer binder under reaction conditions. In another embodiment, the reactive polymerizable alkoxylated monomer of formula IA, IA-1 and/or IB are utilized and copolymerized with two or more of the monomers listed under "other monomers" into the backbone of a latex polymer binder under reaction conditions. In another embodiment, one or more reactive polymerizable alkoxylated monomers of formula IA, IA-1 and/or IB are utilized and copolymerized with one or more of the monomers listed under "other monomers" into the backbone of a latex polymer binder under reaction conditions.

    [0063] The latex polymer dispersion typically includes from 30 to 75% solids and a mean latex polymer binder particle size of from 70 to 650 nm. In another embodiment, the polymer of the present invention has a mean particle size of less than 400nm, typically a mean particle size of less than 200 nm, more typically a mean particle size of less than 190 nm, and most typically a mean particle size of less than 175 nm. In another embodiment, the latex polymer binder has a mean particle size of from 75 nm to 400 nm.

    [0064] The latex polymer binder is typically present in the aqueous coating composition in an amount from 5 to 60 percent by weight, and more typically from 8 to 40 percent by weight (i.e. the weight percentage of the dry latex polymer based on the total weight of the coating composition).

    [0065] The resulting aqueous coating composition containing the latex polymer binder of the present invention is freeze-thaw stable without having to add anti-freeze agents, or adding small amounts of anti-freeze agents, as described above. Therefore, aqueous coating compositions can be produced in accordance with the invention that possess lower VOC levels than conventional aqueous coating compositions and thus that are more environmentally desirable.

    [0066] In another embodiment, the resulting latex polymer may be incorporated into an aqueous coating composition along with an emulsion surfactant as described below and/or a freeze-thaw additive as described below. The addition of the freeze-thaw additive has little or no effect on the VOC levels of the aqueous coating composition, and, thus, aqueous coating compositions can be produced in that possess lower VOC levels than conventional aqueous coating compositions. In such an embodiment, the latex coating composition contains a freeze-thaw additive as described herein in an amount greater than 1.3% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive as described herein in an amount greater than 1.6% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive as described herein in an amount greater than 2% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive as described herein in an amount greater than 4% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive as described herein in an amount greater than 7.5% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive as described herein in an amount greater than 8% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive in an amount between 1.6% and 7.5% by weight of the latex polymer binder. In another embodiment, the latex coating composition contains a freeze-thaw additive in an amount between 1.6% and 45% by weight of the latex polymer binder, typically between 1.6% and 35% by weight of the latex polymer binder.

    [0067] In a further embodiment, the latex polymer binder of the present invention is freeze-thaw stable, and can have a Tg of between -15°C and 12°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 200 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 190 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 175 nm.

    [0068] The latex polymer including the reactive polymerizable alkoxylated monomer of formula IA, IA-1 and/or IB can be used in combination with other ionic or non-ionic type of surfactants that are either polymerizable or non-polymerizable, in the aqueous coating composition. In particular, the polymer latex binder can be prepared using emulsion polymerization by feeding the monomers used to form the latex binder to a reactor in the presence of at least one initiator and the at least one reactive polymerizable alkoxylated monomer of formula IA, IA-1 and/or IB and polymerizing the monomers to produce the latex binder. The monomers fed to a reactor to prepare the polymer latex binder typically include at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. In addition, the monomers can include styrene, vinyl acetate, or ethylene. The monomers can also include one or more monomers selected from the group consisting of styrene, [alpha]-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, and ethylene. It is also possible to include C4-C8 conjugated dienes such as 1,3-butadiene, isoprene or chloroprene. Typically, the monomers include one or more monomers selected from the group consisting of n-butyl acrylate, methyl methacrylate, styrene and 2-ethylhexyl acrylate. The initiator can be any initiator known in the art for use in emulsion polymerization such as ammonium or potassium persulfate, or a redox system that typically includes an oxidant and a reducing agent. Commonly used redox initiation systems are described e.g., by A. S. Sarac in Progress in Polymer Science 24(1999), 1149-1204.

    [0069] The polymer latex binder can be produced by first preparing an initiator solution comprising the initiator and water. A monomer pre-emulsion is also prepared comprising at least a portion of the monomers to be used to form the latex polymer binder, one or more surfactants (emulsifiers), water, and additional additives such as NaOH. The one or more surfactants in the monomer pre-emulsion include any of the reactive polymerizable alkoxylated monomers of the present invention. The initiator solution and monomer pre-emulsion are then continuously added to the reactor over a predetermined period of time (e.g. 1.5-5 hours) to cause polymerization of the monomers and to thereby produce the latex polymer binder. Typically, at least a portion of the initiator solution is added to the reactor prior to adding the monomer pre-emulsion. Prior to the addition of the initiator solution and the monomer pre-emulsion, a seed latex such as a polystyrene seed latex can be added to the reactor. In addition, water, one or more surfactants, and any monomers not provided in the monomer pre-emulsion can be added to the reactor prior to adding the initiator and adding the monomer pre-emulsion. The reactor is operated at an elevated temperature at least until all the monomers are fed to produce the polymer latex binder. Once the polymer latex binder is prepared, it is typically chemically stripped thereby decreasing its residual monomer content. Typically, it is chemically stripped by continuously adding an oxidant such as a peroxide (e.g. t-butylhydroperoxide) and a reducing agent (e.g. sodium acetone bisulfite), or another redox pair such as those described by A. S. Sarac in Progress in Polymer Science 24(1999), 1149-1204, to the latex binder at an elevated temperature and for a predetermined period of time (e.g. 0.5 hours). The pH of the latex binder can then be adjusted and a biocide or other additives added after the chemical stripping step.

    [0070] The aqueous coating composition is a stable fluid that can be applied to a wide variety of materials such as, for example, paper, wood, concrete, metal, glass, ceramics, plastics, plaster, and roofing substrates such as asphaltic coatings, roofing felts, foamed polyurethane insulation; or to previously painted, primed, undercoated, worn, or weathered substrates. The aqueous coating composition of the invention can be applied to the materials by a variety of techniques well known in the art such as, for example, brush, rollers, mops, air-assisted or airless spray, electrostatic spray, and the like.

    Latex Polymer Binder Compositions Comprising Surface Active (emulsifier) Compound



    [0071] In another embodiment a surface active compound of structural formula IIA can be used as an emulsifier during the emulsion polymerization reaction used to make latex polymer binder.

    wherein B is a 5 or 6 membered cycloalkyl ring, e.g., a cyclohexyl ring, or a single ring aromatic hydrocarbon having a 6 membered ring, e.g., a benzene ring;
    R1, R2 and R3 are independently selected from:
    -H, tertbutyl, butyl,



    with the proviso that one or none of R1, R2 and R3 is -H.
    wherein, X is at least one member of the group consisting of C2H4, C3H6, and C4H8, or wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms; n is 1-100, for example, 3 to 80, 4 to 50, 4 to 40 or 8 to 25;
    wherein R is -OH, -OCH3, -OC2H5, -OC3H7, -OC4H9, -OC5H11,-OC6H13, -Cl, -Br, -CN, Phosphonate (-PO3-M+), Phosphate (PO4-M+), Sulfate (SO4-M+), Sulfonate (SO3-M+), carboxylate (COO- M+), a nonionic group, or a quaternary ammonium ion, wherein M+ is a cation including but not limited to H+, Na+, NH4+, K+ or Li+,

    [0072] In one emboidment, R5 is selected from a quaternary ammonium ion:



    [0073] In one embodiment, n is an integer of from 4 to 80. In one embodiment, n is an integer of from 4 to 60. In one embodiment, n is an integer of from 10 to 50. In one embodiment, n is an integer of from 10 to 25.

    [0074] Typically the alkoxylated surface active compound has the formula IIB:

    wherein, R, R1, R2, R3, X and n are as defined for the structure of formula IIA. If desired, the aromatic ring shown in structural formula IIB may be saturated.

    [0075] More typically a surface active alkoxylated tristyrylphenol, e.g., ethoxylated tristyrylphenol, or a surface active alkoxylated tributylphenol, e.g., ethoxylated tributylphenol can be used as an emulsifier during the emulsion polymerization reaction used to make latex polymer. The surface active ethoxylated tristyrylphenols have the structural formula IIC and the surface active ethoxylated tributylphenols have the structural formula IIC-1, respectively, as follows:



    wherein, n is an integer of from 1 to 100 for example, 4 to 60 or 8 to 25, wherein R5 is -OH, -OCH3, -OC2H5, -OC3H7, -OC4H9, -OC5H11, -OC6H13, -Cl,-Br, -CN, Phosphonate (-PO3-M+), Phosphate (PO4-M+), Sulfate (SO4-M+), Sulfonate (SO3-M+), carboxylate (COO- M+), a nonionic group, or a quaternary ammonium ion, wherein M+ is a cation including but not limited to H+, Na+, NH4+, K+ or Li+.

    [0076] In one embodiment, R5 is selected from a quaternary ammonium ion:



    [0077] In one embodiment, n is an integer of from 4 to 80. In one embodiment, n is an integer of from 4 to 60. In one embodiment, n is an integer of from 10 to 50. In one embodiment, n is an integer of from 10 to 25.

    [0078] When surface active ethoxylated tristyrylphenol or ethoxylated tributylphenol is employed as an emulsifier in emulsion polymerization to form the latex polymer binder, the latex polymer binder is made from a mixture wherein the surface active emulsifier utilized is. In one embodiment, the emulsifier is added in an amount greater than 1.3% by weight of the polymer or monomers used to form the latex polymer binder, in an amount greater than 1.6% by weight of the polymer or monomers used to form the latex polymer binder, typically in an amount greater than 2% by weight of the polymer or monomers used to form the latex polymer binder, more typically in an amount greater than 4% by weight of the polymer or monomers used to form the latex polymer binder, and most typically in an amount greater than 7.5% by weight of the polymer or monomers used to form the latex polymer binder. In another embodiment, the latex coating composition contains an emulsifier in an amount greater than 8% by weight of the polymer or monomers used to form the latex polymer binder, or greater than 10% by weight of the polymer or monomers. In another embodiment, the emulsifier is added is between 1.6% and 7.5% by weight of the polymer or monomers used to form the latex polymer binder. In another embodiment, emulsifier added is between 1.6% and 45% by weight of the polymer or monomers used to form the latex polymer binder, typically between 1.6% and 35% by weight of the polymer or monomers used to form the latex polymer binder

    [0079] If desired the ethylene oxide repeating units of the ethylene oxide chain of formula IIC or IIC-1 may be replace by the above-described -(OX)- group to form alkoxylated tristyrylphenol or alkoxylated tributylphenol.

    [0080] The typical monomers from which the at least one latex polymer binder (sometimes referred to herein as first monomer or third monomer) is formed are described above in the section entitled "Other Monomers".

    [0081] As described above, the polymer latex binder can be produced by first preparing an initiator solution comprising the initiator and water. A monomer pre-emulsion is also prepared comprising at least a portion of the monomers to be used to form the latex polymer binder, one or more surfactants (emulsifiers), water, and additional additives such as NaOH. The one or more surfactants in the monomer pre-emulsion include the surface active alkoxylated compound of the invention. Thus, the alkoxylated compound is employed as an emulsifier to form a blend rather than as a reactant which copolymerizes with the other monomers which form the polymer latex binder. The initiator solution and monomer pre-emulsion are then continuously added to the reactor over a predetermined period of time (e.g. 1.5-5 hours) to cause polymerization of the monomers and to thereby produce the latex polymer binder. Typically, at least a portion of the initiator solution is added to the reactor prior to adding the monomer pre-emulsion. Prior to the addition of the initiator solution and the monomer pre-emulsion, a seed latex such as a polystyrene seed latex can be added to the reactor. In addition, water, one or more surfactants, and any monomers not provided in the monomer pre-emulsion can be added to the reactor prior to adding the initiator and adding the monomer pre-emulsion. The reactor is operated at an elevated temperature at least until all the monomers are fed to produce the polymer latex binder. Once the polymer latex binder is prepared, it is typically chemically stripped thereby decreasing its residual monomer content. Typically, it is chemically stripped by continuously adding an oxidant such as a peroxide (e.g. t-butylhydroperoxide) and a reducing agent (e.g. sodium acetone bisulfite), or another redox pair such as those described by A. S. Sarac in Progress in Polymer Science 24(1999), 1149-1204, to the latex binder at an elevated temperature and for a predetermined period of time (e.g. 0.5 hours). The pH of the latex binder can then be adjusted and a biocide or other additives added after the chemical stripping step.

    [0082] The incorporation of the surface active alkoxylated compound surfactant (emulsifier) in the emulsion polymerization reaction mixture enables the coating composition to have a lower VOC content while maintaining the freeze-thaw stability of the aqueous coating composition at desirable levels.

    Additive to an aqueous latex dispersion



    [0083] In another embodiment the above-described surface active alkoxylated compound of structural formula IIA, IIB, IIC or IIC-1 (sometimes referred to as the freeze-thaw additive) can be used as an additive to an already formed aqueous dispersion of latex polymer binder. It is understood, that the freeze-thaw additive can be added any point in the production of the aqueous coating composition, including but not limited to during the emulsification step, during formulation, etc. It is also understood that the freeze-thaw additive can be post-added to the aqueous coating composition or a concentrate thereof.

    [0084] This results in an aqueous composition comprising the surface active alkoxylated compound and the latex polymer binder. When the surface active alkoxylated compound is employed as an additive to an already formed aqueous latex dispersion, the resulting composition has alkoxylated compound additive in an amount of 1 to 10, Typically 2 to 8 or 2 to 6, parts per 100 parts by weight of monomers used to form the latex polymer binder.

    [0085] The typical monomers from which the latex polymer binder is formed are described above in the section entitled "Other Monomers" and are copolymerized with the reactive monomers of the present invention as described above.

    [0086] The present invention further includes a method of preparing a latex binder composition, comprising adding the at least one surface active alkoxylated compound surfactant (emulsifier) of structural formula IIA, IIB, IIC and/or IIC-1 as described above to an aqueous dispersion of a latex polymer to produce the latex binder. The at least one pigment and other additives can then be mixed with the resulting latex binder to produce the aqueous coating composition in any appropriate order. The addition of the surface active alkoxylated compound of structural formula IIA, IIB, IIC or IIC-1 to the latex polymer binder forms a mixture having a lower VOC content while maintaining the freeze-thaw stability of the mixture at desirable levels.

    [0087] In another embodiment the above-described surface active compound of structural formula IIA, IIB, IIC or IIC-1 (sometimes referred to as the freeze-thaw additive) can be used as an additive to an during formulation of paint or aqueous coating composition. Formulation is the stage at which additives are added to a base aqueous latex polymer dispersion to make it into final product such as a paint or coating. When the surface active alkoxylated compound is employed as an additive to an already formed paint or aqueous coating composition, e.g., aqueous latex coating dispersion, the resulting composition has alkoxylated compound additive typically in an amount greater than 1.3% by weight of the polymer or monomers used to form the latex polymer binder, more typically in an amount greater than 1.6% by weight of the polymer or monomers used to form the latex polymer binder, yet more typically in an amount greater than 2% by weight of the polymer or monomers used to form the latex polymer binder, even more typically in an amount greater than 4% by weight of the polymer or monomers used to form the latex polymer binder, and most typically in an amount greater than 7.5% by weight of the polymer or monomers used to form the latex polymer binder. In another embodiment, the latex coating composition contains surface active alkoxylated compound in an amount between 1.6% and 7.5% by weight of the polymer or monomers used to form the latex polymer binder. In another embodiment, the latex coating composition contains surface active alkoxylated compound in an amount between 1.6% and 45% by weight of the polymer or monomers used to form the latex polymer binder, typically between 1.6% and 35%. Pigment is a typical additive, for example, added during formulation of paint from raw aqueous latex polymer dispersion.

    [0088] The aqueous coating compositions of the present invention are freeze-thaw stable where the freeze-thaw additive is present in the aqueous coating composition in the amounts by weight of the latex polymer binder as described above, where the polymer has a Tg of between -15°C and 12°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 200 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 200 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 190 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 190 nm, or a Tg of between -15°C and 12°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 5°C and a mean particle size of less than 175 nm, or a Tg of between -5°C and 0°C and a mean particle size of less than 175 nm. As described above, the mean particle size is typically between 75 nm to 400 nm. The aqueous coating composition can be characterized by an open time of greater than 2 minutes, an open time of greater than 4 minutes, an open time of greater than 6 minutes or an open time of greater than 12 minutes.

    [0089] The present invention further includes a method of preparing a paint or aqueous coating composition, comprising adding the at least one surface active alkoxylated compound of structural formula IIA, IIB, IIC and/or IIC-1 as described above during formulation of paint or aqueous coating composition comprising at least one pigment and other additives to produce the final paint or aqueous coating composition. The addition of the surface active alkoxylated compound surfactant (emulsifier) during formulation of paint or aqueous coating composition forms a coating composition having a lower VOC content while maintaining the freeze-thaw stability of the aqueous coating composition at desirable levels.

    Other Additives



    [0090] The aqueous coating compositions of the invention include at least one latex polymer binder of the present invention. The aqueous coating compositions of the invention include less than 2 % by weight and typically less than 1.0% by weight of anti-freeze agents based on the total weight of the aqueous coating composition. More typically, the aqueous coating compositions are substantially free of anti-freeze agents.

    [0091] The aqueous coating composition typically includes at least one pigment. The term "pigment" as used herein includes non-film-forming solids such as pigments, extenders, and fillers. The at least one pigment is typically selected from the group consisting of TiO2 (in both anastase and rutile forms), clay (aluminum silicate), CaCO3 (in both ground and precipitated forms), aluminum oxide, silicon dioxide, magnesium oxide, talc (magnesium silicate), barytes (barium sulfate), zinc oxide, zinc sulfite, sodium oxide, potassium oxide and mixtures thereof. Suitable mixtures include blends of metal oxides such as those sold under the marks MINEX (oxides of silicon, aluminum, sodium and potassium commercially available from Unimin Specialty Minerals), CELITES (aluminum oxide and silicon dioxide commercially available from Celite Company), ATOMITES (commercially available from English China Clay International), and ATTAGELS (commercially available from Engelhard). More typically, the at least one pigment includes TiO2, CaCO3 or clay. Generally, the mean particle sizes of the pigments range from 0.01 to 50 microns. For example, the TiO2 particles used in the aqueous coating composition typically have a mean particle size of from 0.15 to 0.40 microns. The pigment can be added to the aqueous coating composition as a powder or in slurry form. The pigment is typically present in the aqueous coating composition in an amount from 5 to 50 percent by weight, more typically from 10 to 40 percent by weight.

    [0092] The coating composition can optionally contain additives such as one or more film-forming aids or coalescing agents. Suitable firm-forming aids or coalescing agents include plasticizers and drying retarders such as high boiling point polar solvents. Other conventional coating additives such as, for example, dispersants, additional surfactants (i.e. wetting agents), rheology modifiers, defoamers, thickeners, biocides, mildewcides, colorants such as colored pigments and dyes, waxes, perfumes, co-solvents, and the like, can also be used in accordance with the invention. For example, non-ionic and/or ionic (e.g. anionic or cationic) surfactants can be used to produce the polymer latex. These additives are typically present in the aqueous coating composition in an amount from 0 to 15% by weight, more typically from 1 to 10% by weight based on the total weight of the coating composition.

    [0093] As mentioned above, the aqueous coating composition in some embodiments can include less than 2.0% of anti-freeze agents based on the total weight of the aqueous coating composition. Exemplary anti-freeze agents include ethylene glycol, diethylene glycol, propylene glycol, glycerol (1,2,3-trihydroxypropane), ethanol, methanol, 1-methoxy-2-propanol, 2-amino-2-methyl-1-propanol, and FTS-365 (a freeze-thaw stabilizer from Inovachem Specialty Chemicals). More typically, the aqueous coating composition includes less than 1.0% or is substantially free (e.g. includes less than 0.1 %) of anti-freeze agents. Accordingly, the aqueous coating composition of the invention typically has a VOC level of less than 100 g/L and more typically less than or equal to 50 g/L. Despite the fact that the aqueous coating compositions of the invention include little or no anti-freeze agents, the compositions possess freeze-thaw stabilities at levels desirable in the art.

    [0094] For example, the aqueous coating compositions of the invention can be subjected to freeze-thaw cycles using ASTM method D2243-82 or ASTM D2243-95 without coagulation.

    [0095] The balance of the aqueous coating composition of the invention is water. Although much of the water is present in the polymer latex dispersion and in other components of the aqueous coating composition, water is generally also added separately to the aqueous coating composition. Typically, the aqueous coating composition includes from 10% to 85% by weight and more typically from 35% to 80% by weight water. Stated differently, the total solids content of the aqueous coating composition is typically from 15% to 90%, more typically, from 20% to 65%.

    [0096] The coating compositions are typically formulated such that the dried coatings comprise at least 10% by volume of dry polymer solids, and additionally 5 to 90% by volume of non-polymeric solids in the form of pigments. The dried coatings can also include additives such as plasticizers, dispersants, surfactants, rheology modifiers, defoamers, thickeners, biocides, mildewcides, colorants, waxes, and the like, that do not evaporate upon drying of the coating composition.

    [0097] In one preferred embodiment of the invention, the aqueous coating composition is a latex paint composition comprising at least one latex polymer binder of the present invention; at least one pigment and water.

    [0098] The present invention further includes a method of preparing an aqueous coating composition by mixing together at least one latex polymer binder of the present invention as described above, and at least one pigment. Typically, the latex polymer binder is in the form of a latex polymer dispersion. The additives discussed above can be added in any suitable order to the latex polymer binder, the pigment, or combinations thereof, to provide these additives in the aqueous coating composition. In the case of paint formulations, the aqueous coating composition typically has a pH of from 7 to 10.

    [0099] The present invention will now be further described by the following non-limiting examples. As described above, the present invention may employ (I) surface active alkoxylated compounds as a surfactant (emulsifier) to be present during latex polymer formation, (II) polymerizable reactive alkoxylated monomers to form a latex comonomer, and/or (III) surface active alkoxylated compounds as an additive to an aqueous dispersion of latex polymer or copolymer.

    EXAMPLES



    [0100] The following Example 1 and its subsets describe surface active alkoxylated compounds utilized as a surfactant (emulsifier) to be present during latex polymer formation.

    Example 1



    [0101] Freeze Thaw Stability Study - Example 1 compares a control with compositions, which incorporate various levels of TSP -EO and 1% MAA (methacrylic acid). TSP - EO is a surface active ethoxylated tristyrylphenol according to the above-listed structural formula IIC in which the R group is H.

    [0102] Sample 1 has 2% TSP - EO, 1% MAA (methacrylic acid); Sample 2 has 4% TSP - EO, 1 % MAA; and Sample 3 has 6% TSP - EO, 1 % MAA were made. TABLE 1 shows the ingredients of Sample 2 with 4% TSP - EO, 1% MAA.
    TABLE 1
    SAMPLE 2 INGREDIENTS
    Recipe:Ingredient weight (grams)% BOTM
    Kettle Charge    
    Deionized Water 200.00  
         
    Monomer Emulsion    
    Deionized Water 176.25  
    Alkyl sulfate surfactant 18.75 1.50
    Non-ionic surfactant 5.00 0.50
    TSP - EO 20.00 4.00
    Methylmethacrylate (MMA) 200.00 40.00
    butylacrylate (BA) 295.00 59.00
    (methyl acrylic acid) MAA 5.00 1.00
         
    Initiator Solution    
    Deionized Water 98.00  
    Ammonium Persulfate 2.00 0.40
         
    Total 1020.00 106.40
    Total 1020.00  
    Theoretical % Solids =    


    [0103] "BOTM" is an abbreviation for "Based On Total Monomer." The monomer emulsion contains typical monomers for making latex. As mentioned above, TSP - EO contains a surface active tristyrylphenol with from about 10 to about 50 ethylene oxide groups in its alkoylate chain according to the above-listed structural formula IIC in which the R group is H. RHODACAL A-246/L and ABEX are emulsifiers available from Rhodia Inc., Cranbury, NJ

    [0104] TABLE 2 shows the ingredients employed in a control tested in this example.
    TABLE 2
    CONTROL INGREDIENTS
    Recipe:Ingredient weight (g)% BOTM
    Kettle Charge    
    Deionized Water 320.00  
         
    Monomer Emulsion    
    Deionized Water 282.00  
    Alkyl sulfate surfactant 30.00 1.50
    Non-ionic surfactant 8.00 0.50
    Methylmethacrylate (MMA) 320.00 40.00
    butylacrylate (BA) 472.00 59.00
    (methyl acrylic acid) MAA 8.00 1.00
         
    Initiator Solution    
    Deionized Water 156.80  
    Ammonium Persulfate 3.20 0.40
         
    Total 1600.00 102.40
    Total    
    Theoretical %Solids =    


    [0105] PROCEDURE: The control and the Sample 1, 2 and 3 ingredients were respectively each employed in an emulsion polymerization reaction procedure as follows:
    1. 1. Heat kettle charge to about 80°C while purging with N2. Maintain N2 blanket throughout run.
    2. 2. Prepare Monomer emulsion and Initiator solution based on the above described recipe.
    3. 3. At about 80°C add Initiator solution and Monomer emulsion to the kettle.
    4. 4. Hold at about 80°C for about 10-20 minutes.
    5. 5. Slowly add the remainder of the Monomer emulsion and Initiator solution over 3 hours while maintaining the reaction temperature at about 80 ±1°C.
    6. 6. After addition of the Monomer emulsion and Initiator solution is completed, the reaction mixture temperature was heated to about 85°C and held over 30 minutes.
    7. 7. Cool reactor contents to below about 30°C. Adjust the pH of final reaction to 8-9.
    8. 8. Filter the batch through a 100 mesh filter and store in a closed container for characterization.


    [0106] Sample 1 contained 4% TSP - EO. The procedure was repeated for 2% TSP - EO and 6% TSP - EO samples that were the same as the 4% TSP - EO sample except for the amount of TSP - EO.

    [0107] TABLE 3 shows the results of the control, the 2% TSP - EO sample (Sample 1), the above-described 4% TSP - EO sample (Sample 2), and the 6% TSP - EO sample (Sample 3). The freeze-thaw stability of polymer dispersions and formulated paints was measured based on ASTM standard test Method D2243-95. The latexes or formulated paints are tested using a half pint of sample. The sample was kept in a freezer at 0°F (-18°C) over 17 hours and then taken out from the freezer and allowed to thaw for 7 hours at room temperature. The freeze-thaw cycles were continued until the latex or paint coagulated, or to a maximum of five (5) cycles.
    TABLE 3
     Control2% TSP - EO (Sample 1)4% TSP - EO (Sample 2)6% TSP - EO (Sample 3)
    1. Coagulum (based on total latex) 0.5 17 0.5 0.5
             
    2.pH of aqueous latex dispersion after 8.86 8.83 8.9 8.81
    neutralization        
             
    3. Latex Solid in dispersion, % 50.78 49.94 51.1 51.6
             
    4. Brookfield Viscosity of aqueous latex polymer dispersion        
    Spindle/ Instrument Used LV3/ LVT Model LV3/ LVT Model LV3/ LVT Model LV3/ LVT Model
    at 60 rpm (cps) 100 90 70 70
             
    5. Particle Size        
    Weight Average 180.6 172.8 164.2 156.3
    Std. Dev. % 11.73 6.73 9.8 9.9
             
    6. Freeze-Thaw Stability        
    Cycle1 (cps) gelled 400 600 1560
    Cycle 2   520 680 1500
    Cycle 3   500 580 1300


    [0108] TABLE 3 shows the additive prevented gelling at conditions which gelled the control. Coagulum particles are formed as a byproduct of making latex. The Tg of the latex, as measured using the DSC method as generally known in the art, was 3.63 °C.

    Example 1-1



    [0109] The above-described procedure was repeated with a variety of anionic or nonionic ethoxylated tristerylphenolic (TSP) compounds having from about 6 ethylene oxide groups to about 60 ethylene oxide groups. TABLE 4 presents the results of these examples.
    TABLE 4:
    Effects of Additives on Freeze-Thaw Stability of Water-Borne Paints2
    AdditivesFreeze-Thaw Stability
    Viscosity (KU)1
    Starting Viscosity1 cycle2 cycles3 cycles4 cycles5 cycles
    TSP-EO #1 102.4 103.8 104.3 104 104 105.4
    TSP-EO #2 98.3 101.9 102.2 101.2 100.2 101.3
    TSP-EO #3 82.9 86.6 88.8 89.4 90.4 91.5
    TSP-EO #4 78 88.3 90.2 91.6 93.3 101.4
    TSP-EO #5 78.4 82 86.4 86 85.4 87.1
    TSP-EO #6 80.8 91.9 95.1 96.2 96.5 97.6
    Ethoxylated nonylphenol3 95.5 Failed (gelled)        
    Control (Low VOC Commercial Paint) 121.1 Failed (gelled)        
    Notes:
    1. Additive loading level: 1.0 Wt% of total paint weight.
                 
    2. Water-borne commercial paint:
    Weight per Gallon: 10.24 pounds per gallon;
    pH: 8.67;
    VOC: < 50 g/L;
    Gloss at 60 degrees: 52.
                 
    3. Nonylphenol moiety attached to 9EO


    [0110] Example 2 illustrates comparative examples of the present invention as against the disclosure of International Publication Number WO 2007/117512 (hereinafter sometimes referred to as the "'512 Application" or "Stepan").

    Example 2



    [0111] The seed latex according to the '512 Application (p.20) was prepared:
    Seed Latex Preparation using Sodium Lauryl Sulfate (SLS)
    Formulas: 
    Water 50
    Sulfate*: (29.5) 2.44
    Monomers: 
    Styrene 7.2
    MMA 12.24
    BA 15.84
    AA 0.72
    Total 100
    Initiator Solution  
    Ammonium Persulfate 0.26
    Water 14


    [0112] Procedure: 1. Add 150 water and 7.32g surfactant (SLS) to the kettle and heat to ∼ 83oC. 2. Add 42.78 g initiator solution. 3. Add 108 monomer mixture to kettle and hold at ∼83oC over 2-3 hours. 4. Measure the particle size during emulsion polymerization process. 5. Cool to room temperature and keep the seed latex for future usage. The active wt% of the seed latex was 36 wt%.

    [0113] Tables 5 and 6 illustrate emulsion polymerization of a styrene-acrylic latex polymer using SLS (control) and using SLS in combination with a TSP having from about 10 to 40 ethylene oxide groups as surfactant emulsifiers, respectively.
    TABLE 5
    Styrene-Acrylic Latex Polymer - Sodium Lauryl Sulfate (Control)
    Recipe:Ingredient weight (g)% BOTM
    Kettle Charge    
    Deionized Water 220.00  
    NaHCO3 solution 25.00  
    Styrene-Acrylic Seed 30.00  
         
    Monomer Emulsion    
    Deionized Water 150.00  
    Sodium Lauryl Sulfate 11.19 0.65
    TSP 0 0.00
    Styrene 100.00 20.00
    MMA 170.00 34.00
    BA 220.00 44.00
    AA 10.00 2.00
         
    Initiator Solution    
    Deionized Water 95.50  
    Ammonium Persulfate 3.50 0.70
    NaHCO3 Solution    
    NaHCO3 Solution 125.00  
    Total 1160.19  
    Total 1160.19  
    Theoretical %Solids =    
    Scale-up factor =    
    Seed = ME 30.00  
    IS 20.00  
    Table 6
    TABLE 6
    Styrene-Acrylic Latex Polymer - Sodium Lauryl Sulfate & TSP -EO
    Recipe:Ingredient weight (g)% BOTM
    Kettle Charge    
    Deionized Water 220.00  
    NaHCO3 solution 25.00  
    Styrene-Acrylic Seed 30.00  
         
    Monomer Emulsion    
    Deionized Water 150.00  
    Sodium Lauryl Sulfate 11.19 0.65
    TSP - EO 6.5 1.3
    Styrene 100.00 20.00
    MMA 170.00 34.00
    BA 220.00 44.00
    AA 10.00 2.00
         
    Initiator Solution    
    Deionized Water 95.50  
    Ammonium Persulfate 3.50 0.70
         
    NaHCO3 Solution    
    NaHCO3 Solution 125.00  
    Total 1166.69  
    Total 1166.69  
    Theoretical %Solids =    
    Scale-up factor =    
    Seed = ME 30.00  
    IS 20.00  

    PROCEDURE (for Tables 5 and 6):



    [0114] 1) Charge water and 25g of NaHCO3 solution and 30 g seed latex to a kettle and heat the kettle to about 83°C at a stirring rate of 150 rpm while purging with N2. Maintain N2 blanket throughout run. 2) Prepare monomer emulsion and initiator solution based on the recipe. 3) At ∼83°C add 20.2% Initiator solution (20.0g) and hold for 8 minutes. 4) Feed remainder of Monomer emulsion over about 180 minutes and maintain the reaction temperature at about 83 ±1 oC. 5) After 10 minutes of monomers additions, 79 g solution of ammonium persulfate solution with 125.0g NaHCO3 solution was fed for 180 minutes. 6) After addition, heat the reaction temperature to 83°C and hold over 60 minutes at 83±1°C. 7) Cool batch to below 30°C, and adjust pH to 8.5 ± 0.1 with concentrated (28%) ammonium hydroxide solution. 8) Filter the batch through a 100 mesh filter and store in a closed container for characterization.

    [0115] 
    Table 7 - Resulting Properties of styrene-acrylic latex polymer using SLS (control) and using SLS in combination with a TSP as surfactant emulsifiers
     Control - Polymer with Sodium Lauryl Sulfate (SLS)Polymer with SLS + TSP-EO
    PROPERTIES:  
     %Coagulum 0.08 0.21
     %Solids 44.27 45.33
     %Conversion 98.16 100
     pH (init) 5.10 5.05
     pH (adjust) 8.50 8.50
     Particle size (nm) 200.7 200
     Viscosity (cps) 100 80
    LV3, 60    
     F/T cycles Yes Yes


    [0116] Table 8 - Freeze-Thaw Stability of latex binder using SLS (control) and TDA Sodium Sulfate (control), as compared to using SLS in combination with a TSP as surfactant emulsifiers and using TDA Sodium Sulfate in combination with a TSP as surfactant emulsifiers, respectively.
    Latex BindersTable 8 - Freeze-Thaw Stability of Latex
    Viscosity (cPs, Brookfield) (LV4, 60rpm)
    Initial Vis.1 cycle2 cycles3 cycles4 cycles5 cycles
    Latex Binder with SLS 150 950 900 600 650 550
    Latex Binder with SLS/TSP-EO 150 700 650 550 550 550
    Latex Binder with TDA sodium Sulfate 150 800 650 700 600 510
    Latex Binder with TDA sodium Sulfate/TSP-EO 150 600 500 550 550 500


    [0117] Referring to Tables 7 and 8, the properties of the latex polymer dispersions prepared in Table 5 (Sodium Lauryl Sulfate used as the emulsifying surfactant) and Table 6 (Sodium Lauryl Sulfate and TSP used as emulsifying surfactants) both exhibit freeze thaw (F/T) stability. Using the DSC method generally known in the art, the measured Tg of the latex dispersion of Tables 5 and 6 ranged from about 24 °C - 27 °C.

    [0118] Referring to FIG. 1, the Tg of various latex polymers prepared under the '512 application are illustrated: (1) emulsion polymerization of the latex polymer using SLS, which has a measured Tg of about 26.5 °C; (2) emulsion polymerization of the latex polymer using SLS in combination with a TSP - EO as surfactant emulsifiers, which has a measured Tg of about 25.3 °C; (3) emulsion polymerization of the latex polymer using TDA Sodium Sulfate, which has a measured Tg of about 24.5 °C; and (4) emulsion polymerization of the latex polymer using TDA Sodium Sulfate in combination with a TSP - EO as surfactant emulsifiers, which has a measured Tg of about 26.5 °C.

    [0119] The following Example 3 and its subsets describe the present invention as polymerizable reactive alkoxylated monomers (reactive monomers) used to form a latex comonomer or polymer binder.

    Example 3



    [0120] The following examples relate to use of tristyrylphenol (TSP) ethoxylates utilized as reactive monomers in preparing latex and comparative examples which relate to use of tributylphenol (TBP) ethoxylates utilized as reactive monomers in preparing latex.

    Example 3-1 - Preparing latex polymers



    [0121] Referring to Table 9, a control latex polymer was prepared from emulsion polymerization without the use of TSP/TBP ethoxylated monomers. Referring to Table 10, a latex polymer was prepared from emulsion polymerization using TSP ethoxylated monomers of the present invention and TBP ethoxylated monomers. The procedure for preparing the latex polymer was as follows:

    [0122] Heat kettle charge to while purging with N2. Maintain N2 blanket throughout run. Prepare monomer emulsion and initiator solution. Add initiator solution and monomer emulsion. Hold at steady temperature and feed remainder of monomer emulsion and Initiator solution. Cool to reactor below 30°C and then filter the batch through cheesecloth.
    Table 9
    TABLE 9
    Emulsion Polymerization without TSP/TBP ethoxylated monomer
    Recipe:Ingredient weight (g)% BOTM
    Kettle Charge  
    Deionized Water 320.00  
         
         
    Monomer Emulsion  
    Deionized Water 282.00  
    Alkyl sulfate surfactant 30.00 1.50
    Non-ionic surfactant 8.00 0.5
    MMA 320.00 40.00
    BA 472.00 59.00
    MAA 8.00 1.00
    Initiator Solution    
    Deionized Water 156.80  
    Ammonium Persulfate 3.20 0.40
         
    Chaser Solution    
    Total 1600.00  
    Total 1600.00  
    Theoretical %Solids =    
    Scale-up factor =    
    Seed = ME 56.00  
    IS 40.00  
    Table 10
    TABLE 10
    Emulsion Polymerization utilizing TSP ethoxylated monomer
    Recipe:Ingredient weight (g)% BOTM
    Kettle Charge  
    Deionized Water 200.00  
         
         
    Monomer Emulsion  
    Deionized Water 176.25  
    Alkyl sulfate surfactant 18.75 1.50
    Non-ionic surfactant 5.00 0.50
    TSP-EO 16.60 2.00
    MMA 200.00 40.00
    BA 295.00 59.00
    MAA 1.68 1.00
         
    Initiator Solution  
    Deionized Water 98.00  
    Ammonium Persulfate 2.00 0.40
         
    Chaser Solution  
    Total 1013.28  
    Total 1013.28  
    Theoretical %Solids =    
    Scale-up factor =    
    Seed = ME 35.66  
    IS 25.00  

    Example 3-2 - Paint formulations



    [0123] Tables 11, 12 and 13 illustrate paint formulations utilizing a commercially low VOC available paint whose polymer latex is believed to have a Tg of about 2.4 °C and a D50 of between 130-160, a similar formulation utilizing pure acrylic as the latex polymer, and a similar formulation utilizing the synthesized latexes of the present invention as the latex polymer, respectively.
    Table 11 - Paint Formulations
    Table 11 - Paint Formulation Control - Commercially available Low VOC paint (Comm. Paint)
    Raw materialsPoundsGallonsWeight Percent
    Pigment Grind   
    Water 80 9.62 9.560
    Ethylene Glycol 0 0 0
    AMP-95 1 0.13 0.10
    Rhodoline 286N 8 0.91 0.76
    Antarox BL-225 4 0.48 0.38
    Rhodoline 643 0.5 0.06 0.05
    Attagel 50 5 0.253 0.48
    Titanium dioxide Tiona 595 230 7 22.0
    Water 89.6 10.77 6.64
    Sub Total 418.1 29.22  
    Letdown   
    Comm. latex (undisclosed) 480 54.2 45.9
    Texanol 0 0 0
    Rhodoline 643 2.5 0.41 0.29
    Aquaflow NHS310 28 3.23 2.68
    Water 95 11.42 9.1
    Acrysol™ SCT-275 14 1.634 0.67
    Polyphase 663 4 0.418 0.38
    Total 1041.6 100.53 100.0
    Table 12
    Table 12 - Paint Formulation Control - Pure Acrylic
    Raw materialsPoundsGallonsWeight Percent
    Pigment Grind   
    Water 80 9.62 9.560
    Ethylene Glycol 0 0 0.00
    AMP-95 1 0.13 0.10
    Rhodoline 286N 8 0.91 0.76
    Antarox BL-225 4 0.48 0.38
    Rhodoline 643 0.5 0.06 0.05
    Attagel 50 5 0.253 0.48
    Titanium dioxide Tiona 595 230 7 22.0
    Water 89.6 10.77 6.64
    Sub Total 418.1 29.22  
    Letdown   
    Pure Acrylic - Control 480 54.2 45.9
    Texanol 0 0 0.0
    Rhodoline 643 2.5 0.41 0.29
    Aquaflow NHS310 28 3.23 2.68
    Water 95 11.42 9.1
    Acrysol™ SCT-275 14 1.634 0.67
    Polyphase 663 4 0.418 0.38
    Total 1041.6 100.53 100.0


    [0124] Table 13 - Paint Formulation with synthesized latex including TSP ethoxylate unit.
    Table 13 - Paint Formulation with synthesized latex including TSP ethoxylate unit
    Raw materialsPoundsGallonsWeight Percent
    Pigment Grind   
    Water 80 9.62 9.560
    Ethylene Glycol 0 0 0.00
    AMP-95 1 0.13 0.10
    Rhodoline 286N 8 0.91 0.76
    Antarox BL-225 4 0.48 0.38
    Rhodoline 643 0.5 0.06 0.05
    Attagel 50 5 0.253 0.48
    Titanium dioxide Tiona 595 230 7 22.0
    Water 89.6 10.77 6.64
    Sub Total 418.1 29.22  
    Letdown   
    Latex -2% - TSP/TBP reactive monomer 480 54.2 45.9
    Texanol 0 0 0.0
    Rhodoline 643 2.5 0.41 0.29
    Aquaflow NHS310 28 3.23 2.68
    Water 95 11.42 9.1
    Acrysol™ SCT-275 14 1.634 0.67
    Polyphase 663 4 0.418 0.38
    Total 1041.6 100.53 100.0


    [0125] Table 14 illustrates the resulting paint properties of the above referenced paint formulations using low Tg commercial latex, pure acrylic latex, and varying TSP/TBP ethoxylated monomers having ethoxylate groups from about 3 to 80.
    Table 14Comm. LatexPure AcrylicR-TSP #1R-TSP #2R-TSP #3R-TSP #4R-TSP #5R-TSP #6R-TSP #7R-TBP #1R- TBP #2
    Viscosity:           
    Initial KU 106.8 103 101.5 100.3 97 84.5 80.1 95.6 86.6 98.6 88.4
    Initial, ICI 1.2 1.4 1.6 1.5 1.6 1.3 1.4 1.3 1.4 1.7 1.4
    Viscosity, equilibrium                      
    KU 113.4 106.3 103.8 103.1 99.4 88.7 82.3 93.6 87.1 101 93.8
    ICI 1.3 1.4 1.6 1.6 1.4 1.2 1.4 1.4 1.3 1.6 1.2
    pH 8.3 8.55 8.47 8.6 8.42 8.51 8.55 8.54 8.44 8.55 8.45
    WPG 10.42 10.36 10.39 10.4 10.38 10.28 10.34 10.32 9.88 10.27 10.35
    Gloss 20/60/85 20.1 /57.9/ 88.4 21.2/ 60.3/ 89.4 19.2/ 56.9/ 86.4 21.7/ 60.8/ 89.6 20.3/ 59.2/ 87.3 20.8/ 59/ 87.8 21.3/ 59.9/ 88.4 12.3/ 52.6/ 81.6 2.9/ 21.5/ 40.6 16.5/ 54.5/ 87.6 17.0/ 54.8/ 87.5


    [0126] The paint formulations utilizing Comm. Latex and Pure Acrylic latex gelled only after one F/T cycle as opposed to formulations using latexes incorporating several TSP/TBP ethoxylated monomers, which exhibited F/T stability.

    Example 3-3



    [0127] The properties of paint formulations using a control latex (pure acrylic), a commercially-available low Tg latex, and the TSP reactive monomers of the present invention were tested. It is observed that the resulting paint formulations wherein the above-referenced latexes varied produced comparable properties aside from F/T stability. Accordingly, the imparting of F/T stability using the reactive TSP and TBP monomer ethoxylates into latex polymers of the present invention does not detract from other desirable properties of the paint formulation (10 being the highest to 1 being the lowest).
    Table 15 - paint properties
     Control - Pure AcrylicBenchmark - Low VOC commercial paint (Comm. Latex)R-TSP-EO #1R-TSP-EO #2
    WPG 9.35 10.03 9.6 9.37
    pH 8.55 8.3 8.54 8.49
    Viscosity 77 109 94 77
    ICI 1.00 1.60 1.05 1.05
    Gloss-@20/60/85° 16.5/54.3/90.7 21.2/60.6/92.9 17.2/56.4/86.4 15.3/55.5/95.3
    Reflectance 93.9 94 93.5 93.8
    Contrast Ratio 0.972 0.977 0.972 0.971
    Low Temp. Film Formation, 40°F        
    Sealed 10 10 10 10
    Unsealed 10 10 10 10
    Surfactant Leaching        
    24 hours Dry 8 7 7 8
    3 Days Dry 8 7 7 8
    7 Days Dry 9 7 7 8
    Foam Dab Test 9 9 9 9
    Leveling - ASTM D4062 10 8 9 8
    Block Resistance, ASTM D 4946        
    RT 7 7 7 7
    Dry Adhesion, 7 Days        
    Aluminum 0B 2B 1B 2B
    Alkyd 5B 5B 5B 4B
    Open Time, minutes        
    0 10 10 10 10
    2 10 10 10 10
    4 9 8 9 9
    6 8 7 8 8
    8 8 6 7 6
    10 7 5 5 5
    12 6 4 4 4
    14 5 3 3 3
    Color Acceptance        
    E Colorant 9 10 8 10
    B Colorant 9 10 7 10
    Table 16 - Scrub resistance of the present invention as compared to the control (pure acrylic latex).
    Scrub ResistanceR-TSP-EO #1ControlR-TSP-EO #2Control
    Run 1 838 1393 978 1206
    Run 2 818 1370 1086 1337
    Table 17 - Scrub resistance of the present invention as compared to a low VOC commercially- available paint formulation (Comm. Latex).
    Scrub ResistanceR-TSP-EO #1Comm. PaintR-TSP-EO #2Comm. Paint
    Run 1 736 2218 1078 1897
    Run 2 838 2115 943 1930
    Table 18 - stain removal properties of the present invention as compared to the control (pure acrylic latex).
    Stain RemovalR-TSP-EO #1ControlR-TSP-EO #2Control
    Purple Crayon 10 10 10 10
    Pencil 10 10 10 10
    Red Lipstick 6 7 6 7
    Ball Point Pen Black 5 5 5 5
    Washable Marker Black 7 7 7 7
    Sanford Highlighter Yellow 10 10 10 10
    Gulden's Mustard 6 6 6 6
    Coffee 6 6 5 6
    Red Wine 4 5 5 5
    Table 19 - stain removal properties of the present invention as compared to a low VOC commercially- available paint formulation (using low Tg Comm. Latex).
    Stain RemovalR-TSP-EO #1Comm. PaintR-TSP-EO #2Comm. Paint
    Purple Crayon 10 10 10 10
    Pencil 10 10 10 10
    Red Lipstick 6 7 7 7
    Ball Point Pen Black 4 5 5 6
    Washable Marker Black 7 7 7 7
    Sanford Highlighter Yellow 10 10 10 10
    Gulden's Mustard 5 5 5 5
    Coffee 6 6 6 6
    Red Wine 4 4 4 4


    [0128] The following Example 4 and its subsets describe surface active alkoxylated compounds utilized as one or more additives to an aqueous dispersion of latex polymer or copolymer.

    Example 4


    Surface active alkoxylated compounds as additives.



    [0129] Non-ionic TSP surfactants having ethylene oxide groups greater than about 3 to about 80 was added at 10 Ibs/ 100 gals in Pure acrylic - White base, and the formulation exhibited freeze-thaw stability.

    [0130] Table 20 shows anionic TSP surfactants (10 lbs/ 100 gals) as F/T additives (in Pure acrylic - White base).
    Commercial Semigloss Paint with varying amounts of (anionic) F/T additiveTable 20 - Freeze-Thaw Stability of Low VOC Paints
    Stormer Viscosity (Krebs Unit, KU)
    Initial Vis.1 cycle2 cycles3 cycles4 cycles5 cycles
    TSP -EO phosphate ester salt 82.9 86.6 88.8 89.4 90.4 91.5
    Low nonionic TSP -EO phosphate ester salt 77.8 85.6 87.4 88.0 89.6 91.2
    TSP -EO TEA salt 81.7 91.0 93.5 94.0 95.5 97.9
    TSP-EO Ammonium Sulfate Salt 78.0 88.3 90.2 91.6 93.3 101.4
    TSP-EO Potassium Salt 1 76.6 84.8 85.1 86.2 85.9 86.7
    TSP-EO Potassium Salt 2 81.3 90.7 92.6 93.8 93.3 94.7
    TSP - EO-PO 81.3 92.6 95.3 97.8 102.2 104.9

    Example 4-1



    [0131] Table 21 shows the effects of the TSP ethoxylate on the binder particle size. The mean particle size was measured using a Zetasizer Nano ZS device utilizing the Dynamic Light Scattering (DLS) method. The DLS method essentially consists of observing the scattering of laser light from particles, determining the diffusion speed and deriving the size from this scattering of laser light, using the Stokes-Einstein relationship.
    TSPLow VOC Comm. Paint (3.0 wt%)Table 21 - Effects of TSP Ethoxylate on Particle sizes of Low Tg Binder
    Mean Particle Size (nm)
    Initial Vis.1 cycle2 cycles3 cycles4 cycles5 cycles
    TSP-EO A 220.75 + 6.62 142.8 137.5 149.9 154.3 158.8 145.4
    TSP-EO B 220.75 + 8.28 146.9 161.1 158.3 169.7 164.2 189.0

    Example 4-2



    [0132] Table 22 shows the loading level of TSP Ethoxylate on F/T Stability of low VOC Paints.
    TSP-EO (wt% based on dry polymer weight)Table 22 - Loading Level of TSP - EO on Freeze-Thaw Stability of Low VOC Semigloss Paints
    Viscosity (Krebs Units, KU)
    Initial Vis.1 cycle2 cycles3 cycles4 cycles5 cycles
    0 115.4 Gel -- -- -- --
    0.86 114.6 126.3 gel -- -- --
    1.30 101.4 128.7 > 140 gel -- --
    1.71 110.5 109 113.6 120.2 129.3 gel
    2.57 106.6 102.3 103.8 103.8 106.9 109.2
    3.43 105.1 102.3 102.6 102.6 103.8 105.8
    4.29 104.1 100.9 101.4 101.2 102.3 104.1
    8.00 93.2 97.5 98.5 98.8 100.3 101.2


    [0133] Referring to Table 23, F/T stability is observed at or above about 1.3% based on the total polymer weight using the TSP-EO.
    Table 23
    TSP-EO (wt% based on dry polymer weight)Table 23 - Loading Level of TSP -EO on Freeze-Thaw Stability of Low VOC Flat Paints
    Viscosity (Krebs Units, KU)
    Initial Vis.1 cycle2 cycles3 cycles4 cycles5 cycles
    280.5 + 0.00 104.8 gel - - - -
    280.5 + 0.56 102.4 108.6 116.6 122 131.4 136
    280.5 + 1.11 100.4 104.2 108.5 111.8 117.5 120.5
    280.5 + 1.67 98.5 100.1 102.4 104 106.7 109.6
    280.5 + 2.22 96 97.2 98.5 99.7 102 104.2
    280.5 + 2.78 95.5 95.4 96.4 97.3 99.2 100.3

    Example 4-3



    [0134] TSP ethoxylates in varying amounts were added to low or zero VOC commercial paints and tested for freeze thaw stability. Table 24 shows the effects of TSP-EO on F/T Stability of various Low/Zero VOC Commercial Paints. The control contained no TSP ethoxylated surfactant (TSP-EO).
    Table 24
    Low/Zero VOC Commercial PaintsStarting ViscosityFreeze-Thaw Stability
    Control10.0lbs/100 gals15.0 lbs/100 galsViscosity, (KU) after 1, 2, 3, 4, and 5 cycles
    Control10.0lbs/100 gals of added F/T additive15.0 lbs/100 gals of added F/T additive
    Paint 1 (advertised as 0 VOC) 112.1 91.2 88.3 130/ >140/ 140.0/ 139.4/ 139.2 101.9/ 116.2/ 123.1/ 102.2/ 102.6 88.3/ 98.3/ 121.8/ 103.8/ 100.7
    Paint 2 (advertised as 37g/L) 109.2 98.5 95 gel/ -- 105.2/ 106.5/ 102.9/ 100.9/ 100.0 95.6/ 95.7/ 93.8/ 94.3/ 94.4
    Paint 3 (advertised as 0 VOC) 102.3 80.8 73.8 gel/ -- 91/107.8/108.0/ 108.6/ 111.4 85.9/ 99.8/ 99.9/ 99.2/ 100.0
    Paint 4 (advertised as Low VOC) 99.9 97.6 101.1 gel/ -- 123.8/ gel/ -- 126.4/ gel/ --
    Paint 5 (advertised as 41 g/L) 108.4 86.6 80.8 gel/ -- 120.1/ gel/ -- 106.9/89.4/115.2/ 117.1/118.2
    Paint 6 (advertised as 0 VOC) 111.5 93.7 87.2 gel/ -- gel/ -- 98.6/ 107.6/ 99.4/ 100.4/99.5
    Paint 7 (advertised as 0 VOC) 105.5 87 85 gel/ -- 96.5/ 114.5/ 107.7/ 106.9/107.3 92.4/109.4/103.8/ 106.2/ 104.9
    Paint 8 (advertised as 0 VOC) 102.7 84 79.3 121.1/ gel/ -- 86.3/ 97.7/ 97.1/ 91.3/ 92.2 82.8/ 96.1/ 85.9/ 88.0/ 88.4
    Paint 9 (advertised as 50 g/L) 119.4 89.8 87.6 gel/ -- 126.2/ gel/ -- 127.1/ gel/ --
    Paint 10 (advertised as 50 (advertised as 112.5 88.7 83.2 gel/ -- 93.7/ 93.7/ 92.0/ 94.1/ 91.0 87.8/ 93.5/ 86.3/ 86.6/ 86.7
    Paint 11 (advertised as 50 g/L) 107.2 91 84.8 gel/ -- gel/ -- 102.2/ 98.4/ 95.0/ 95.6/94.5
    Paint 12 (advertised as 50 g/L) 120.6 95.1 84.3 gel/ -- 114.3/ gel/ -- 94.4/ 109.4/ 102.0/ 102.5/102.5

    Example 4-5



    [0135] Open time - Tables 25 and 26 show the effects of TSP Ethoxylate nonionic surfactants on "open time" of Low VOC Paints and the Effects of TSP Ethoxylate Anionic Surfactants on "open time" of Low VOC Paints, respectively. Open time is generally understood to be the interval, after the paint is applied, during which it can be blended with additional painted regions (at the "wet edge"). Open time refers to the amount of time a newly-applied layer of paint remains workable before brush strokes and other signs of manipulation become visible in dried films. The method for measuring Open Time is generally as follows: a 10 mils film is drawn down on a piece of black scrub test paper. The paint film is then cross-hatched in two-inch intervals with the eraser end of a pencil. The first cross hatch then brushed over in one direction 15 times; this is then repeated in two-minute intervals for each successive cross-hatch. After 48 hrs, the dry films are examined for the earliest times at which traces of cross-hatch at discernable. This is performed under constant humidity, room temp. It is desirable for paint formulations to have an open time of greater than 4 minutes, typically, greater than 6 minutes. The amount of reagent (both nonionic surfactants and anionic surfactants) varied from about 2.5 grams surfactant to about 4.25 grams surfactant per 256 grams of paint.
    Table 25
    Reagent (Nonionic Surfactants)starting viscosity (KU)open time (minutes)
    sampleControl
    TSP - EO #1 89.9 > 14 4
    TSP - EO #2 85 > 14 4
    TSP - EO #3 82 14 2 to 4
    TSP - EO #4 81.2 > 14 4
    TSP - EO #5 89.9 4 2
    Table 26
    Reagent (Anionic Surfactants)starting viscosity (KU)open time (minutes)
    sampleControl
    TSP -EO TEA salt 83.3 14 2 to 4
    TSP-EO Ammonium Sulfate Salt 83.5 8 to 10 2
    TSP -EO Potassium Salt 1 86.4 8 to 12 2
    TSP - EO-PO 83.5 > 14 4


    [0136] Referring back to Tables 25 and 26, it is observed that open time increased significantly when utilizing either the non-ionic TSP additives or anionic TSP additives, respectively.

    [0137] In the above detailed description, preferred embodiments are described in detail to enable practice of the invention. Although the invention is described with reference to these specific preferred embodiments, it will be understood that the invention is not limited to these preferred embodiments. But to the contrary, the invention includes numerous alternatives, modifications and equivalents as will become apparent from consideration of the following detailed description. It is understood that upon reading the above description of the present invention, one skilled in the art could make changes and variations therefrom.


    Claims

    1. A latex polymer binder derived from at least one first monomer and at least one second monomer according to structural formula IA:

    wherein R1, R2 and R3 are independently selected from the group consisting of:



    wherein X is a divalent hydrocarbon radical comprising a linear or branched alkylene radical having from 2 to 8 carbon atoms; wherein n is an integer of from 1 to 100; wherein R is an ethylenically unsaturated group; and wherein the latex binder has a glass transition temperature (Tg) of between -15°C and 12°C.
     
    2. The latex polymer binder of claim 1 wherein R is selected from the group consisting of acrylate, C1-C6 alkyl acrylate, allyl, vinyl, maleate, itaconate, fumarate, acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleimido, styrenyl, α-alkyl styrenyl, RaCH=C(Rb)COO-,
    wherein if Ra is H, then Rb is H, C1-C4 alkyl, or -CH2COOX; if Ra is-C(O)OX, then Rb is H or -CH2C(O)OXa; or is Ra is CH3, then Rb is H and Xa is H or C1-C4 alkyl; or
    -HC=CYZ or -OCH=CYZ,
    wherein Y is H, CH3, or Cl; Z is CN, Cl,- COORc,-C6H4Rc, -COORd, or-HC=CH2; Rd is C1-C8 alkyl or C2-C8 hydroxy alkyl; Rc is H, Cl, Br, or C1-C4 alkyl.
     
    3. The latex polymer binder according to claim 1 wherein the second monomer is according to structural formula IB:

    wherein n is in the range of 1-100, and
    R4 is selected from the group consisting of H1, C1-C6 alkyl and C2-C8 hydroxy alkyl.
     
    4. The latex polymer binder according to claim 3 wherein n is an integer of from 3 to 80, preferably from 10 to 50, preferably from 20 to 50.
     
    5. The latex polymer binder according to claim 1 wherein the first monomer comprises at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters and mixtures thereof, preferably wherein the polymer is further derived from at least one third monomer selected from the group consisting of styrene, alpha-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, ethylene, and C4-C8 conjugated dienes.
     
    6. The latex polymer binder of any one of claims 1 to 5 wherein the glass transition temperature (Tg) is between -5°C and 5°C, preferably between -5°C and 0°C.
     
    7. The latex polymer binder of any one of claims 1 to 6 wherein the latex polymer binder has a mean particle size of less than 200 nm, preferably less than 190 nm, preferably less than 175 nm.
     
    8. A latex coating composition comprising:

    (a) at least one latex polymer binder of any one of claims 1 to 7; and

    (b) water,

    whereby the coating composition is freeze-thaw stable.
     
    9. The latex coating composition of claim 8 further comprising a freeze-thaw additive according to structural formula:

    or

    wherein, n is an integer of from 1 to 100, wherein R5 is selected from the group consisting of -OH, -OCH3, -OC2H5, -OC3H7, -OC4H9, -OC5H11, -OC6H13,-Cl, -Br, -CN, Phosphonate (-PO3-M+), Phosphate (PO4-M+), Sulfate (SO4-M+), Sulfonate (SO3-M+), carboxylate (COO-M+), a nonionic group, and a quaternary ammonium ion, wherein M+ is a cation.
     
    10. The latex coating composition of claim 9 wherein the freeze-thaw additive is present in an amount greater than 1.3% by weight of the latex polymer binder, preferably greater than 1.6% by weight, preferably greater than 2% by weight, preferably greater than 4% by weight, preferably greater than 7.5% by weight, preferably greater than 8% by weight, preferably greater than 10% by weight.
     
    11. A method of preparing a latex polymer binder as defined in any one of claims 1 to 7, comprising copolymerizing (1) at least one first monomer with (2) at least one second monomer according to structural formula IA:

    wherein R1, R2 and R3 are independently selected from the group consisting of:



    wherein X is a divalent hydrocarbon radical comprising a linear or branched alkylene radical having from 2 to 8 carbon atoms; wherein n is an integer of from 1 to 100; wherein R is an ethylenically unsaturated group; and wherein the latex binder has a glass transition temperature (Tg) of between -15°C and 12°C.
     


    Ansprüche

    1. Latexpolymerbindemittel, gewonnen aus mindestens einem ersten Monomer und mindestens einem zweiten Monomer gemäß der Strukturformel IA:

    wobei R1, R2 und R3 unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus:



    wobei es sich bei X um ein zweiwertiges Kohlenwasserstoffradikal, umfassend ein lineares oder verzweigtes Alkylenradikal, handelt, das zwischen 2 und 8 Kohlenstoffatome aufweist; wobei es sich bei n um eine ganze Zahl zwischen 1 und 100 handelt; wobei es sich bei R um eine ethylenisch ungesättigte Gruppe handelt und wobei das Latexbindemittel eine Glasübergangstemperatur (Tg) zwischen -15°C und 12°C aufweist.
     
    2. Latexpolymerbindemittel nach Anspruch 1, wobei R ausgewählt ist aus der Gruppe, bestehend aus Acrylat, C1-C6- Alkylacrylat, Allyl, Vinyl, Maleat, Itaconat, Fumarat, Acryl-, Methacryl-, Acrylamid-, Methacrylamid-, Diallylamin-, Allylether-, Vinylether-, α-Alkenyl-, Maleimid-, Styrenyl-, α-Alkylstyrenylgruppen, RaCH=C(Rb)COO-,
    wobei, wenn es sich bei Ra um H handelt, dann handelt es sich bei Rb um H, C1-C4-Alkyl oder-CH2COOX; wenn es sich bei Ra um -C(O)OX handelt, dann handelt es sich bei Rb um H oder-CH2C(O)OXa, oder wenn es sich bei Ra um CH3 handelt, dann handelt es sich bei Rb um H und bei Xa um H oder C1-C4-Alkyl; oder
    -HC=CYZ oder -OCH=CYZ,
    wobei es sich bei Y um H, CH3 oder Cl handelt; bei Z um CN, Cl, - COORc, -C6H4Rc, -COORd oder -HC=CH2 handelt; es sich bei Rd um C1-C8-Alkyl oder C2-C8 Hydroxyalkyl handelt; es sich bei Rc um H, Cl, Br, oder C1-C4-Alkyl handelt.
     
    3. Latexpolymerbindemittel nach Anspruch 1, wobei das zweite Monomer der Strukturformel IB entspricht:

    wobei es sich bei n um den Bereich von 1-100 handelt und
    R4 ausgewählt ist aus der Gruppe, bestehend aus H1, C1-C6-Alkyl und C2-C8-Hydroxyalkyl.
     
    4. Latexpolymerbindemittel nach Anspruch 3, wobei es sich bei n um eine ganze Zahl zwischen 3 und 80 handelt, vorzugsweise zwischen 10 und 50, vorzugsweise zwischen 20 und 50.
     
    5. Latexpolymerbindemittel nach Anspruch 1, wobei das erste Monomer mindestens ein Acrylmonomer umfasst, das ausgewählt ist aus der Gruppe, bestehend aus Acrylsäure, Acrylsäureestern, Methacrylsäure, Methacrylsäureestern und Mischungen davon, wobei das Polymer weiterhin bevorzugt aus mindestens einem dritten Monomer gewonnen wird, das ausgewählt ist aus der Gruppe, bestehend aus Styrol, alpha-Methylstyrol, Vinylchlorid, Acrylnitril, Methacrylnitril, Ureidomethacrylat, Vinylacetat, Vinylester verzweigter tertiärer Monocarbonsäuren, Itaconsäure, Crotonsäure, Maleinsäure, Fumarsäure, Ethylen und C4-C8-konjugierte Diene.
     
    6. Latexpolymerbindemittel gemäß einem der Ansprüche 1 bis 5, wobei die Glasübergangstemperatur (Tg) zwischen -5°C und 5°C, vorzugsweise zwischen -5°C und 0°C liegt.
     
    7. Latexpolymerbindemittel gemäß einem der Ansprüche 1 bis 6, wobei das Latexpolymerbindemittel eine mittlere Partikelgröße kleiner als 200 nm, vorzugsweise kleiner als 190 nm, vorzugsweise kleiner als 175 nm aufweist.
     
    8. Latexbeschichtungszusammensetzung, umfassend:

    (a) mindestens ein Latexpolymerbindemittel nach einem der Ansprüche 1 bis 7; und

    (b) Wasser,

    wobei die Beschichtungszusammensetzung gefrier-auftaustabil ist.
     
    9. Latexbeschichtungszusammensetzung nach Anspruch 8, ferner umfassend einen Gefrier-Auftauzusatzstoff gemäß der folgenden Strukturformel:

    oder

    wobei es sich bei n um eine ganze Zahl zwischen 1 und 100 handelt, wobei R5 ausgewählt ist aus der Gruppe, bestehend aus -OH, -OCH3, -OC2H5, -OC3H7, -OC4H9, -OC5H11, -OC6H13, -Cl, -Br, -CN, Phosphonat (-PO3-M+), Phosphat (PO4-M+), Sulfat (SO4-M+), Sulfonat (SO3-M+), Carboxylat (COO-M+), einer nicht ionischen Gruppe und einem quaternären Ammoniumion, wobei es sich bei M+ um ein Kation handelt.
     
    10. Latexbeschichtungszusammensetzung nach Anspruch 9, wobei der Gefrier-Auftauzusatzstoff in einer Menge vorliegt, die größer als ungefähr 1,3 Gewichtsprozent des Latexpolymerbindemittels ist, vorzugsweise größer als ungefähr 1,6 Gewichtsprozent, vorzugsweise größer als ungefähr 2 Gewichtsprozent, vorzugsweise größer als ungefähr 4 Gewichtsprozent, vorzugsweise größer als ungefähr 7,5 Gewichtsprozent, vorzugsweise größer als ungefähr 8 Gewichtsprozent, vorzugsweise größer als ungefähr 10 Gewichtsprozent ist.
     
    11. Verfahren zur Herstellung eines Latexpolymerbindemittels nach einem der Ansprüche 1 bis 7, umfassend das Copolymerisieren (1) von mindestens einem ersten Monomer mit (2) mindestens einem zweiten Monomer gemäß der Strukturformel IA:

    wobei R1, R2 und R3 unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus:



    wobei es sich bei X um ein zweiwertiges Kohlenwasserstoffradikal, umfassend ein lineares oder verzweigtes Alkylenradikal, handelt, das zwischen 2 und 8 Kohlenstoffatome aufweist; wobei es sich bei n um eine ganze Zahl zwischen 1 und 100 handelt; wobei es sich bei R um eine ethylenisch ungesättigte Gruppe handelt und wobei das Latexbindemittel eine Glasübergangstemperatur (Tg) zwischen -15°C und 12°C aufweist.
     


    Revendications

    1. Liant polymère de latex dérivé d'au moins un premier monomère et d'au moins un deuxième monomère selon la formule structurelle IA :

    où R1, R2 et R3 sont sélectionnés indépendamment parmi le groupe consistant en :



    où X est un radical d'hydrocarbure divalent comprenant un radical alkylène linéaire ou ramifié ayant 2 à 8 atomes de carbone ; où n est un entier compris entre 1 et 100 ; où R est un groupe non saturé par éthylène ; et où le liant de latex présente une température de transition vitreuse (Tg) comprise entre-15°C et 12°C.
     
    2. Liant polymère de latex selon la revendication 1 où R est sélectionné parmi le groupe consistant en acrylate, acrylate alkyle C1-C6, allyle, vinyle, maléate, itaconate, fumarate, acrylo, méthacrylo, acrylamido, méthacrylamido, diallylamino, éther allyle, éther vinyle, α-alkényle, maléimido, styrényel, styrényle α-alkyle, RaCH=C(Rb)COO-,
    où si Ra est H, alors Rb est H, alkyle C1-C4ou-CH2COOX; si Ra est -C(O)OX, alors Rb est H ou -CH2C(O)OXa ; ou si Ra est CH3, alors Rb est H et Xa est H ou alkyle C1-C4 ; ou
    -HC=CYZ ou -OCH=CYZ,
    où Y est H, CH3, ou Cl ; Z est CN, Cl,- COORc,-C6H4Rc, -COORd, ou -HC=CH2 ;
    Rd est alkyle C1-C8 ou alkyle hydroxy C2-C8 ; Rc est H, Cl, Br ou alkyle C1-C4.
     
    3. Liant polymère de latex selon la revendication 1 où le deuxième monomère est selon la formule structurelle IB :

    où n est compris dans la fourchette allant de 1 à 100, et
    R4 est sélectionné parmi le groupe consistant en H1, alkyle C1-C6 et alkyle hydroxy C2-C8.
     
    4. Liant polymère de latex selon la revendication 3 où n est un entier compris entre 3 et 80, de préférence entre 10 et 50, de préférence entre 20 et 50.
     
    5. Liant polymère de latex selon la revendication 1 où le premier monomère comprend au moins un monomère acrylique sélectionné parmi le groupe consistant en acide acrylique, esters d'acide acrylique, acide méthacrylique, esters d'acide méthacryliques et leurs mélanges, de préférence où le polymère est en outre dérivé d'au moins un troisième monomère sélectionné parmi le groupe consistant en styrène, styrène alpha-méthyle, chlorure de vinyle, acrylonitrile, méthacrylonitrile, méthacrylate uréido, acétate de vinyle, esters de vinyle,d'acides monocarboxyliques tertiaires ramifiés, acide itaconique, acide crotonique, acide maléique, acide fumarique, éthylène et diènes conjugués C4-C8.
     
    6. Liant polymère de latex selon l'une quelconque des revendications 1 à 5, où la température de transition vitreuse (Tg) est comprise entre -5°C et 5°C, de préférence entre -5°C et 0°C.
     
    7. Liant polymère de latex selon l'une quelconque des revendications 1 à 6, où le liant polymère de latex présente une taille de particules moyenne inférieure à 200 nm, de préférence inférieure à 190 nm, de préférence inférieure à 175 nm.
     
    8. Composition d'enrobage de latex comprenant :

    (a) au moins un liant polymère de latex selon l'une quelconque des revendications 1 à 7 ; et

    (b) de l'eau,

    où la composition d'enrobage est stable à la congélation et la décongélation.
     
    9. Composition d'enrobage de latex selon la revendication 8 comprenant en outre un additif de congélation et de décongélation selon la formule structurelle :

    ou

    où n est un entier compris entre 1 et 100, où R5 est sélectionné parmi le groupe consistant en -OH, -OCH3, -OC2H5, -OC3H7, -OC4H9, -OC5H11, -OC6H13, -Cl, -Br, -CN, phosphonate (-PO3M+), phosphate (PO4-M+), sulfate (SO4-M+), sulfonate (SO3-M+), carboxylate (COO-M+), un groupe non ionique et un ion d'ammonium quaternaire, où M+ est a cation.
     
    10. Composition d'enrobage de latex selon la revendication 9 où l'additif de congélation et de décongélation est présent dans une quantité supérieure à 1,3 % en poids du liant polymère de latex, de préférence supérieure à 1,6 % en poids, de préférence supérieure à 2 % en poids, de préférence supérieure à 4 % en poids, de préférence supérieure à 7,5 % en poids, de préférence supérieure à 8 % en poids, de préférence supérieure à 10 % en poids.
     
    11. Procédé d'élaboration d'un liant polymère de latex tel que défini dans l'une quelconque des revendications 1 à 7, comprenant la copolymérisation (1) au moins un premier monomère avec (2) au moins un deuxième monomère selon la formule structurelle IA :

    où R1, R2 et R3 sont sélectionnés indépendamment parmi le groupe consistant en :



    où X est un radical d'hydrocarbure divalent comprenant un radical alkylène linéaire ou ramifié ayant 2 à 8 atomes de carbone ; où n est un entier compris entre 1 et 100 ; où R est un groupe non saturé par éthylène; et où le liant de latex présente une température de transition vitreuse (Tg) comprise entre -15°C et 12°C.
     




    Drawing








    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description




    Non-patent literature cited in the description