Polymerizable surfactants having water-whitening resistance and methods of use

Abstract

Ethylenically unsaturated salts of allyl (poly)ether sulfates are disclosed which are utilized as reactive surfactants or emulsifiers during emulsion polymerization.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 842,806, filed May 3, 2019.

[0002] The present invention relates to polymerizable surfactants utilized in the preparation of polymers by emulsion polymerization. [Background technology]

[0003] Surfactants are utilized in a variety of applications, such as for dispersing, emulsifying, wetting, and foaming, across many industries, including coatings, adhesives, home care, personal care, construction, paper, and inks. Surfactants are often included in products, such as paints and coatings, because they are needed to stabilize the product or during the manufacture of the product. However, in many cases, the presence of surfactants in the final product adversely affects the desired properties of such final products. For example, in paints, the presence of excess surfactants can contribute to increased water sensitivity and increased water whitening.

[0004] Emulsifiers are surfactants used in the preparation of polymers by a process called emulsion polymerization.Typically, such emulsifiers are understood to affect, among other things, the mechanical and chemical stability of the resulting emulsion.Furthermore, emulsifiers play a role in the physical properties of emulsions, such as viscosity, particle size, etc.Emulsifiers also play a role in the physical properties of films, such as weather resistance, durability, and adhesion.

[0005] The resulting latex is typically used in coating applications such as paints, inks, dyes, and pressure sensitive adhesives ("PSA"). Once a latex-containing product is applied to a surface as part of a protective or decorative coating, the surfactant is no longer necessary or desired. The presence of the surfactant often reduces the moisture sensitivity of the coating. Furthermore, other coating properties, such as adhesion to the substrate surface, can be adversely affected. This adverse effect is typically understood to be primarily due to the mobility of the surfactant polymer. For example, locally high concentrations of surfactant molecules can form in the coating from coalescence of surfactant-coated micellar spheres. When the coating is exposed to water, these unbound surfactant molecules can be extracted from the coating, leaving thin spots or pathways to the substrate surface. This can result in a pinhole effect and attack of the substrate by water. Other undesirable effects include whitening, blooming, or fogging of the coating film, which occurs as a result of the surfactant migrating to the surface when the film comes into contact with water. As a result, the film can become hazy or white and lose its original gloss.

[0006] These problems are believed to be caused by surfactant still remaining in free form in polymer.One way to reduce the content of such free surfactant is to react such surfactant with polymer during polymerization, or otherwise ensure that such surfactant does not remain in free form in product or intermediate product, i.e. reactive surfactant or "polymerizable surfactant".It is understood that the terms "reactive surfactant" and "polymerizable surfactant" are used interchangeably herein. Summary of the Invention

[0007] In one aspect, described herein is a compound of formula (I): [ka] (Wherein, R1 is H, C8 to C 14Alkyl group or bicyclo[ d.e.f ]heptyl or bicyclo[ d.e.f ]heptenyl group, where d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5; d.e.f ]heptyl or bicyclo[ d.e.f ] The heptenyl group may be optionally substituted at one or more of the ring carbon atoms by one or more (C1-C6) alkyl groups (otherwise referred to herein as "Nopol"); "x" is an integer from 1 to 5, and "y" is an integer from 5 to 15, M+ is, but is not limited to, H+, Na+, NH4+, K+, or Li+. is a reactive or polymerizable surfactant.

[0008] In another embodiment, R1 is H, a group according to formula (II) (otherwise referred to herein as “Nopol”), or a linear or branched: 50 Alkyl groups, C1-C 40 Alkyl groups, C2-C 30 Alkyl groups, C4-C 20 Alkyl groups, C6-C 20 Alkyl groups, C8-C 14 Alkyl group or C6-C 18 In another embodiment, "x" is an integer from 1 to 20, and "y" is an integer from 1 to 50, provided that x+y is equal to or greater than 1. In another embodiment, "x" is an integer from 0 to 40, and "y" is an integer from 0 to 40.

[0009] In yet another embodiment, M+ is H+, Na+, NH4+, K+, or Li+. In a preferred embodiment, M+ is Na+ or NH4+. In a more preferred embodiment, M+ is NH4+.

[0010] In another aspect, described herein is a method for preparing polymers (including, but not limited to, latex polymer emulsions and paints) utilizing the reactive surfactant of formula (I) above as an emulsifier. In another aspect, described herein is a method for preparing polymers (including, but not limited to, latex polymer emulsions and paints) utilizing the polymerizable surfactant composition (or reactive surfactant composition) of formula (I) as an emulsifier in combination with at least one surfactant. In one embodiment, the surfactant is sodium alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl oxide disulfonate, ethoxylated alkyl phenol sulfates and phosphates, sulfates and phosphates of fatty alcohols. In another embodiment, the surfactant is sodium alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl oxide disulfonate, ethoxylated alkyl phenol sulfates and phosphates, sulfates and phosphates of fatty alcohols. 10 ~C 16 Alcohol ethoxylate sulfate or any salt thereof. [Brief description of the drawings]

[0011] [Figure 1] 1 shows a photograph of the improved paint of the present invention (white and pigmented with 5% colorant) compared to the prior art. [Diagram 2] Water whitening resistance and water fastness tests at room temperature are shown. [Diagram 3] The results show water whitening resistance and water resistance tests at 90°C. [Figure 4] 4 shows the color delta L value of water whiteness change (90° C. for 50 minutes) in the examples. [Diagram 5] 4 shows the color Delta E values ​​of water whiteness change (50 min at 90° C.) of the examples. [Figure 6] The opacity (%) values ​​of the polymers in Table 6, including Surfactant A and Surfactant B, are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] In this Summary of the Invention and in this Detailed Description, each numerical value should be read once as modified by the term "about" (unless already expressly modified) and then read again as unmodified unless the context dictates otherwise.

[0013] As used herein, the term "alkyl" means a saturated hydrocarbon radical, which may be straight chain, branched or cyclic, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl, etc.

[0014] As used herein, the term "cycloalkyl" means a saturated hydrocarbon radical containing one or more cyclic alkyl rings, such as, for example, cyclopentyl, cyclooctyl, and adamantanyl.

[0015] As used herein, the term "hydroxyalkyl" refers to an alkyl radical, more typically an alkyl radical substituted with a hydroxyl group, such as, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.

[0016] As used herein, the term "alkylene" means a divalent acyclic saturated hydrocarbon radical, including, but not limited to, methylene, polymethylene, and alkyl-substituted polymethylene radicals, such as dimethylene, tetramethylene, and 2-methyltrimethylene.

[0017] As used herein, the term "alkenyl" means an unsaturated straight-chain, branched-chain or cyclic hydrocarbon radical containing one or more carbon-carbon double bonds, such as, for example, ethenyl, 1-propenyl, 2-propenyl, and the like.

[0018] As used herein, the term "aryl" means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings, where the unsaturation may be represented by three conjugated double bonds and one or more of the ring carbons may be substituted with hydroxy, alkyl, alkenyl, halo, haloalkyl, or amino, such as phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl, and the like.

[0019] As used herein, the term "aralkyl" refers to an alkyl group substituted with one or more aryl groups, e.g., phenylmethyl, phenylethyl, triphenylmethyl, and the like.

[0020] As used herein, the term “(C n ~C m )" (where n and m are each integers) indicates that the group can contain from n carbon atoms to m carbon atoms per group.

[0021] As used herein, the term "ethylenically unsaturated" means terminal (ie, for example, α, β) carbon-carbon double bonds.

[0022] Emulsion polymerization is typically utilized in the preparation of aqueous latexes used in coatings such as paints and inks. The polymerization reaction generally occurs in micelles where the monomer droplets are stabilized by surfactants. The surfactants are often anionic surfactants of a mixture of anionic and nonionic surfactants under conditions that promote polymerization. These surfactants, along with the reaction conditions, determine the polymer properties such as particle size. For example, anionic surfactants can provide shear stability to prevent losses due to coagulation. Nonionic surfactants can provide electrolyte or chemical stability to the growing latex particles. The type and structure of the surfactant can dramatically affect emulsion properties such as particle size, particle size distribution, and latex viscosity.

[0023] Like non-polymerizable surfactants, polymerizable surfactants are typically molecules that have a hydrophobic segment and an ionizable and / or polar group. The hydrophobic segment preferentially adsorbs to the surface of the polymer particle (e.g., latex polymer particle) during and after particle polymerization. The hydrophilic group extends into the aqueous phase and provides a steric barrier or charge repulsion against particle aggregation and coagulation.

[0024] However, unlike their non-polymerizable counterparts, polymerizable surfactants contain additional reactive groups in the hydrophobic segment that can be covalently bonded to the latex surface. Usually, these are sites such as terminal unsaturated carbon groups, such as vinyl or olefin groups, that can participate in free radical emulsion polymerization reactions. When used in emulsion polymerization, the majority of the surfactant molecules become irreversibly bonded to emulsion polymer chains and droplets. This can improve the stability of the latex and reduce foaming, among other desirable properties.

[0025] The polymerizable surfactants described herein are prepared from readily available raw materials and generally, their preparation does not require any equipment or special handling. The polymerizable surfactants described herein can be prepared in batch or continuous mode. The polymerizable surfactants can be prepared in various forms, including but not limited to liquids, solutions, flakes, powders, solids, semi-solids, gels, ringing gels, or pastes. In one embodiment, the polymerizable surfactants are prepared in a conventional solvent, such as water, a solvent (such as an alcohol), or a mixture thereof, to produce an aqueous solution of the polymerizable surfactant. In one embodiment, the polymerizable surfactants described herein also include the surfactant as a salt in a dry form, and in another embodiment, the polymerizable surfactants described herein also include the surfactant as an aqueous solution. The salt of the polymerizable surfactant can be isolated by drying the solution of the polymerizable surfactant. The solution of the polymerizable surfactant can be prepared by dissolving the salt of the polymerizable surfactant in water, a solvent, or a mixture thereof.

[0026] The coating comprising the PSA is obtained from an aqueous dispersion containing an effective amount of a surfactant, including at least one ionic polymerizable surfactant. The coating comprised of at least one polymerizable surfactant exhibits good water-whitening resistance in a hot water (90° C.) whitening test. In one embodiment, specifically, 12 / C 14 -2.6AGE-5EO-sulfate sodium salt, C 12 / C 14 -2.6AGE-15EO-sulfate sodium salt and Nopol-2.6AGE-15EO-sulfate sodium salt exhibit improved hot water whitening resistance compared to non-reactive conventional surfactants. As used herein, "AGE" is allyl glycidyl ether.

[0027] In one embodiment, Nopol-2.6AGE-15EO-sulfate sodium salt is: [ka] (In the formula, "x" is an integer of 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, and "y" is an integer of 1 to 50, or 1 to 40, or 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, or 3 to 50, or 3 to 40, or 3 to 30, or 3 to 25, or 3 to 20, or 3 to 15, or 3 to 10, or 3 to 5, or 5 to 50, or 5 to 40, or 5 to 30, or 5 to 25, or 5 to 20, or 5 to 15, or 5 to 10, or 5 to 7). It can be expressed as follows.

[0028] In one embodiment, specifically, 12 / C 14 -2.6AGE-5EO-ammonium sulfate, C 12 / C 14 -2.6AGE-15EO-ammonium sulfate and Nopol-2.6AGE-15EO-ammonium sulfate exhibit improved hot water whitening resistance compared to non-reactive conventional surfactants.

[0029] In one embodiment, Nopol-2.6AGE-15EO-ammonium sulfate salt is: [ka] (In the formula, "x" is an integer of 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, and "y" is an integer of 1 to 50, or 1 to 40, or 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, or 3 to 50, or 3 to 40, or 3 to 30, or 3 to 25, or 3 to 20, or 3 to 15, or 3 to 10, or 3 to 5, or 5 to 50, or 5 to 40, or 5 to 30, or 5 to 25, or 5 to 20, or 5 to 15, or 5 to 10, or 5 to 7). It can be expressed as follows.

[0030] In one embodiment, C 12 / C 14 -2.6AGE-15EO-sulfate sodium salt is: [ka] (In the formula, "x" is an integer of 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, and "y" is an integer of 1 to 50, or 1 to 40, or 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, or 3 to 50, or 3 to 40, or 3 to 30, or 3 to 25, or 3 to 20, or 3 to 15, or 3 to 10, or 3 to 5, or 5 to 50, or 5 to 40, or 5 to 30, or 5 to 25, or 5 to 20, or 5 to 15, or 5 to 10, or 5 to 7). It can be expressed as follows.

[0031] In one embodiment, C 12 / C 14 -2.6AGE-15EO-ammonium sulfate salt is as follows: [ka] (In the formula, "x" is an integer of 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, and "y" is an integer of 1 to 50, or 1 to 40, or 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 1 to 5, or 3 to 50, or 3 to 40, or 3 to 30, or 3 to 25, or 3 to 20, or 3 to 15, or 3 to 10, or 3 to 5, or 5 to 50, or 5 to 40, or 5 to 30, or 5 to 25, or 5 to 20, or 5 to 15, or 5 to 10, or 5 to 7). It can be expressed as follows.

[0032] The polymerizable surfactants described herein may be used in applications where reactive surfactants containing one or more polyether groups have heretofore been used, particularly as emulsifiers for emulsion polymerization, dispersants for suspension polymerization, resin modifiers (to improve water repellency, adjust hydrophilicity, improve antistatic properties, improve antifogging properties, improve waterproof properties, improve adhesion, improve dyeability, improve film forming properties, improve weather resistance, improve antiblocking properties, etc.), fiber processing aids, non-dripping agents, stain resistant finishes, paints, and the like.

[0033] When any one of the polymerizable surfactants described herein is used as an emulsifier for emulsion polymerization, it can be used in any desired ratio within the ratio range with other emulsifiers (surfactants) for emulsion polymerization. However, it can generally be used in a ratio of preferably 0.1 to 20% by weight, typically 0.2 to 10% by weight based on one or more monomers of the raw materials, and in other embodiments, in a ratio of 0.2 to 5% by weight based on one or more monomers of the raw materials. Furthermore, in another embodiment, surfactants other than the polymerizable surfactants described herein can be utilized during the emulsion polymerization process. Non-reactive surfactants commonly used in emulsion polymerization processes include both anionic and nonionic molecules. In one embodiment, the reactive surfactants described herein can be utilized with one or more anionic surfactants. In one embodiment, the reactive surfactants described herein can be utilized with one or more cationic surfactants. In one embodiment, the reactive surfactants described herein can be utilized with one or more nonionic surfactants. In one embodiment, the reactive surfactants described herein can be utilized with any combination of one or more anionic surfactants and one or more nonionic surfactants.

[0034] Anionic surfactants used in conjunction with the reactive surfactants described herein (in emulsion polymerization processes) are as follows: sodium alkylbenzenesulfonate, alkyl sulfosuccinate, alkyldiphenyloxide disulfonate, ethoxylated alkylphenol sulfates and phosphates, sulfates and phosphates of fatty alcohols, and the like, or any salts thereof. Nonionic surfactants used in conjunction with the reactive surfactants described herein (in emulsion polymerization processes) are as follows: alcohol ethoxylates, alkylphenol ethoxylates, and the like, or any salts thereof. In one embodiment, the anionic surfactant is C 10~16 Alcohol ethoxylate sulfate or any salt thereof.

[0035] There are no particular limitations on the monomers to be subjected to emulsion polymerization, but the polymerizable surfactants utilized in emulsion polymerization can be preferably used for acrylate emulsion, styrene emulsion, vinyl acetate emulsion, SBR (styrene / butadiene) emulsion, ABS (acrylonitrile / butadiene / styrene) emulsion, BR (butadiene) emulsion, IR (isoprene) emulsion, NBR (acrylonitrile / butadiene) emulsion, etc.

[0036] Suitable monomers that can be polymerized under the emulsion polymerization conditions described herein include ethylenically unsaturated monomers, such as vinyl monomers and acrylic monomers.Typical vinyl monomers suitable for use include, but are not limited to, vinyl esters such as vinyl acetate, vinyl benzoate, vinyl propionate, vinyl aromatic hydrocarbons such as styrene, methylstyrene, other vinyl aromatics such as vinyl toluene, vinyl naphthalene, divinyl benzene, etc.Halogenated vinyl monomers such as vinyl chloride, vinylidene chloride, etc. can also be used.

[0037] Suitable acrylic monomers typically include compounds with acrylic functionality, such as alkyl acrylates and methacrylates, acrylic and methacrylic acids, and acrylamides and acrylonitriles.Typical acrylic monomers include, but are not limited to, methyl acrylate and methyl methacrylate, ethyl, propyl and butyl acrylate and methacrylate, benzyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, decyl and dodecyl acrylate and methacrylate, and the like.Other acrylic monomers include hydroxyalkyl acrylates and methacrylates, such as hydroxypropyl and hydroxyethyl acrylate and methacrylate, acrylic acids, such as methacrylic acid and acrylic acid, and amino acrylates and methacrylates.

[0038] Other examples of (co)polymerizable monomers in acrylate emulsions may include (meth)acrylic acid (acrylate) alone, (meth)acrylic acid (acrylate) / styrene, (meth)acrylic acid (acrylate) / vinyl acetate, (meth)acrylic acid (acrylate) / acrylonitrile, (meth)acrylic acid (acrylate) / butadiene, (meth)acrylic acid (acrylate) / vinylidene chloride, (meth)acrylic acid (acrylate) / allylamine, (meth)acrylic acid (acrylate) / vinylpyridine, (meth)acrylic acid (acrylate) / alkylolamide, (meth)acrylic acid (acrylate) / N,N-dimethylaminoethyl ester, and (meth)acrylic acid (acrylate) / N,N-diethylaminoethyl vinyl ether.

[0039] Other additives or ingredients known to those skilled in the art may also be used in accordance with the present invention, including chain transfer agents used to control molecular weight, additives to adjust pH, and compounds utilized as protective colloids to provide additional stability to the latex particles.

[0040] In one embodiment, the polymerizable surfactant has formula (I): [ka] (Wherein, R1 is H or C8 to C 14 an alkyl group, "x" is an integer from 1 to 5, "y" is an integer from 5 to 15, and M+ is H+, Na+, NH4+, K+ or Li+, preferably M+ is Na+ or NH4+. In certain embodiments, the polymerizable surfactant may be a mixture of two or more surfactants of formula (I), where R1 is two different C8-C 14is an alkyl group, "x" is an integer from 1 to 5, "y" is an integer from 5 to 15, and M+ is H+, Na+, NH4+, K+ or Li+, preferably M+ is Na+ or NH4+. For example, in certain embodiments, the polymerizable surfactant can be a mixture of two or more surfactants of formula (I), wherein at least one surfactant of formula (I) is a C8-C 14 Alkyl groups, preferably C 10 ~C 14 At least one different surfactant of formula (I) has R1 which is an alkyl group, and at least one different surfactant of formula (I) has a different C8-C 14 Alkyl groups, preferably different C 10 ~C 14 It has R1 which is an alkyl group, "x" is an integer from 1 to 5, "y" is an integer from 5 to 15, and M+ is H+, Na+, NH4+, K+ or Li+, preferably M+ is Na+ or NH4+.

[0041] In one embodiment, R1 is bicyclo [d.e.f] Heptyl or bicyclo [d.e.f] heptenyl group, where d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5; [d.e.f] Heptyl or bicyclo [d.e.f] The heptenyl group may be optionally substituted at one or more of the ring carbon atoms with one or more (C1-C6) alkyl groups (otherwise referred to herein as "Nopol").

[0042] In another embodiment, R1 is a bicyclic group, or more specifically, in one embodiment, a bicycloheptyl-polyether, a bicycloheptenyl-polyether, or a branched (C5-C 50 ) alkyl-polyether groups, where the bicycloheptyl-polyether or bicycloheptenyl-polyether groups may optionally be substituted at one or more ring carbon atoms with one or two (C1-C6) alkyl groups per carbon atom.

[0043] In one embodiment, R1 is a linear or branched: C1-C 50 Alkyl groups, C1-C 40 Alkyl groups, C2-C 30 Alkyl groups, C4-C 20 Alkyl groups, C6-C 20 Alkyl groups, C8-C 14 Alkyl group or C6-C 18 It is an alkyl group.

[0044] In another embodiment, "x" is an integer from 1 to 30, or from 1 to 25, or from 1 to 20, or from 1 to 15, or from 1 to 10, or from 1 to 5.

[0045] In another embodiment, "y" is an integer from 1 to 50, or from 1 to 40, or from 1 to 30, or from 1 to 25, or from 1 to 20, or from 1 to 15, or from 1 to 10, or from 1 to 5, or from 3 to 50, or from 3 to 40, or from 3 to 30, or from 3 to 25, or from 3 to 20, or from 3 to 15, or from 3 to 10, or from 3 to 5, or from 5 to 50, or from 5 to 40, or from 5 to 30, or from 5 to 25, or from 5 to 20, or from 5 to 15, or from 5 to 10, or from 5 to 7.

[0046] In another embodiment, M+ is, but is not limited to, H+, Na+, NH4+, K+, or Li+. In a preferred embodiment, M+ is Na+ or NH4+. In a more preferred embodiment, M+ is NH4+.

[0047] In another embodiment, R1 is bicyclo [d.e.f] Heptyl or bicyclo [d.e.f] heptenyl, where d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5; [d.e.f] Heptyl or bicyclo [d.e.f] The heptenyl may be optionally substituted at one or more of the ring carbon atoms by one or more (C1-C6) alkyl groups.

[0048] More typically, R1 is: (i) a bicycloalkyl group bonded through the 2-carbon atom and substituted at the 6-carbon atom, typically by one or two (C1-C6) alkyl radicals, more typically by two methyl radicals; [3.1.1] Heptyl or bicyclo [3.1.1] a heptenyl group, or (ii) a bicycloalkyl group bonded through the 2- or 3-carbon atom and typically substituted at the 7-carbon atom by one or two (C1-C6) alkyl radicals, more typically two methyl radicals; [3.1.1] Heptyl or bicyclo [2.2.1] Heptenyl group.

[0049] Suitable bicyclic groups include bicycloheptyl and bicycloheptenyl moieties, which may be derived, for example, from terpene compounds having a core (unsubstituted) 7 carbon atom bicyclic ring system according to structures (XII)-(XVII). [ka]

[0050] For example, the bicycloheptenyl intermediate compound (II), also known as "Nopol": [ka] is made by reacting β-pinene with formaldehyde to give a bicycloheptyl intermediate compound known as "albanol" (XIX): [ka] is made by isomerization of α-pinene to camphene and ethoxyhydroxylation of camphene.

[0051] In one embodiment, the bicycloheptyl or bicycloheptenyl intermediate is alkoxylated by reacting the bicycloheptyl or bicycloheptenyl intermediate with one or more alkylene oxide compounds, such as ethylene oxide or propylene oxide, to form a bicycloheptyl or bicycloheptenyl-polyether intermediate. The alkoxylation can be carried out according to well-known methods in the presence of a catalyst, such as a strong base, an aliphatic amine or a Lewis acid, and an inert gas, such as nitrogen or argon, typically at a temperature ranging from about 100° C. to about 250° C. and a pressure ranging from about 1 to about 4 bar.

[0052] The bicycloheptyl or bicycloheptenyl-polyether monomer is then formed by adding a polymerizable functional group to the bicycloheptyl or bicycloheptenyl-polyether intermediate, for example by esterifying the bicycloheptyl or bicycloheptenyl-polyether intermediate with, for example, methacrylic anhydride, under suitable reaction conditions.

[0053] In some embodiments, the sulfate or phosphate groups include their corresponding salt forms, where the cations include, but are not limited to, Na+, NH4+, K+, or Li+.

[0054] In another embodiment, M+ is, but is not limited to, H+, Na+, NH4+, K+, or Li+. In a typical embodiment, M+ is Na+ or NH4+. In a preferred embodiment, M+ is NH4+.

[0055] The use of the reactive surfactants described herein in emulsion polymerization provides at least one of the following advantages to latex and / or coating applications: blush resistance, high temperature blush resistance, moderate reactivity, PME stability, good process control, and excellent application performance (e.g., water sensitivity).

[0056] Polymerizable surfactant composition (or reactive surfactant composition) may comprise any reactive surfactant according to formula (I) as emulsifier in combination with at least one surfactant.In one embodiment, the surfactant is sodium alkylbenzenesulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyldiphenyloxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, sulfate and phosphate of fatty alcohol or any salt thereof.In another embodiment, the surfactant is alkyl alcohol ethoxylate sulfate or any salt thereof. EXAMPLES

[0057] Preparation of polymerizable surfactants Example 1. Polymerizable surfactant C 12 C 14 -2. Preparation of 6AGE-15EO ammonium sulfate 320 g of Alfol 1214 was added with 10.0 g of 45% potassium hydroxide solution at 80° C. while stirring in a reactor with a subsurface purge of nitrogen gas. After heating to 100° C., the gas flow was stopped and the flask was evacuated to approximately 20" Hg using a vacuum pump. After 1 hour, the vacuum was broken with nitrogen and a sample was analyzed by Karl Fischer titration to be 0.09% moisture content.

[0058] 470.1 g of allyl glycidyl ether was added to the reactor over 120 minutes within the temperature range of 95-105°C. After 30 minutes, the reactor contents were heated to 120°C. After an additional 6 hours within the temperature range of 120-123°C, a sample of the reactor contents was titrated with 0.1 M perchloric acid in acetic acid to naphthol benzein indicator to show an alkalinity of 0.101 mmol / g in the presence of tetrabutylammonium bromide, indicating complete reaction of the added epoxy compound. 780 g of clear liquid product was recovered from the reactor.

[0059] 360 g of the aforementioned adduct was placed in a stirred autoclave reactor and heated to 110°C with a subsurface purge of nitrogen gas. The reactor was evacuated to approximately 27" Hg and held at these conditions for 30 minutes. After breaking the vacuum with nitrogen and applying a positive pressure of 1.1 bar of nitrogen, the reactor contents were heated to 155°C and then 541 g of ethylene oxide was fed subsurface of the liquid at 155-156°C over 140 minutes, reaching a maximum pressure of 5.3 bar. After 1 hour, the pressure was released and the reactor contents were cooled to 115°C and then purged once more with nitrogen gas for 10 minutes before being discharged. 889 g of clear liquid product was recovered from the reactor.

[0060] 647.3 g of the aforementioned adduct was charged to a 1 liter reactor, then stirred at 350 RPM, nitrogen sparging at approximately 25 ml / min was started, and heated to 65° C. Dicyandiamide (0.36 g) was charged to the reactor, then sparged for 1 hour to help reduce / remove dissolved oxygen which contributes to color. 71.13 g of sulfamic acid was charged to the reactor over 1 hour by splitting the charge into 5 approximately equal additions. The reaction temperature was increased to 90° C. and maintained for 5 hours. The reaction mass was cooled to below 40° C. and the dark amber liquid was bottled. % activity was determined using the Hyamine test.

[0061] 1172.22 g of deionized water was placed in a 2 gallon open reaction flask equipped with a stainless steel turbine agitator. Agitation was started at 350 RPM. 18.5 g of 29% ammonium hydroxide was charged to the stirring water. 524.9 g of the above adduct, which has an activity level of 100% by the Hyamine test, was slowly charged in a steady stream into the water, ensuring that the pH remained above 7. An additional 231 g of deionized water was charged to give an estimated 27% active solution. Agitation was maintained for 30 minutes. The clear amber liquid was bottled. The % activity was determined to be 29.6%.

[0062] Example 2. Preparation of polymerizable surfactant Nopol-2.6AGE-15EO ammonium sulfate 11.1 g of 45% potassium hydroxide solution was added to 283 g of Nopol with stirring at 100° C. in a reactor with a subsurface purge of nitrogen gas. The gas flow was stopped and the flask was evacuated to approximately 22" Hg using a vacuum pump. After 1 hour, the vacuum was broken with nitrogen and a sample was analyzed by Karl Fischer titration to have a moisture content of 0.06%.

[0063] 505.8 g of allyl glycidyl ether was added to the reactor over 120 minutes within a temperature range of 93-96°C. After 30 minutes, the reactor contents were heated to 120°C. After an additional 5 hours within a temperature range of 118-120°C, a sample of the reactor contents was titrated with 0.1 M perchloric acid in acetic acid to naphthol benzein indicator to show an alkalinity of 0.125 mmol / g in the presence of tetrabutylammonium bromide, indicating substantially complete reaction of the added epoxy compound (2 mol% residual epoxy = 98 mol% conversion of allyl glycidyl ether). 773 g of clear liquid product was recovered from the reactor.

[0064] 351 g of the aforementioned adduct was placed in a stirred autoclave reactor and heated to 110°C with a subsurface purge of nitrogen gas. The reactor was evacuated to approximately 27" Hg and held at these conditions for 30 minutes. After breaking the vacuum with nitrogen and applying a positive pressure of 1.0 bar of nitrogen, the reactor contents were heated to 155°C and then 546 g of ethylene oxide was fed subsurface of the liquid at 155-156°C over 130 minutes, reaching a maximum pressure of 5.6 bar. After 1 hour, the pressure was released and the reactor contents were cooled to 110°C and then purged once more with nitrogen gas for 10 minutes before being discharged. 876 g of clear liquid product was recovered from the reactor.

[0065] 691.4g of the aforementioned adduct was charged to a 1 liter reactor, then stirred at 350 RPM, nitrogen sparging at approximately 25ml / min was started, and heated to 65°C. Dicyandiamide (0.39g) was charged to the reactor, then sparged for 1 hour to help reduce / remove dissolved oxygen which contributes to color. 84.65g of sulfamic acid was charged to the reactor over 1 hour by splitting the charge into 5 approximately equal additions. The reaction temperature was increased to 90°C and maintained for 5 hours. The reaction mass was cooled to below 40°C and bottled. The % activity was determined by using the Hyamine test for use in dilution to the desired % activity of 30%.

[0066] 1165.61 g of deionized water was placed in a 2 gallon open reaction flask equipped with a stainless steel turbine agitator. Agitation was started at 350 RPM. 16.0 g of 29% ammonium hydroxide was added to the stirring water to obtain a pH of 10.62. 529.5 g of the above adduct, having an activity level of 99.8% by Hyamine test, was slowly added in a steady stream to the water, ensuring that the pH remained above 7. An additional 50.2 g of deionized water was added to obtain an approximately 30% active solution. Agitation was maintained for 30 minutes. The clear amber liquid was bottled. The % activity was determined to be 30.5%.

[0067] Examples 3-9. Polymerizable surfactants A-I of Examples 1-9 shown in Table 1 were prepared according to the procedure described in Example 1, adjusting the molar ratios of the starting materials accordingly.

[0068] [Table 1]

[0069] Example 10. Preparation of latex polymer by using surfactant A in all-acrylic emulsion polymerization Deionized water (230.0 g) and Polymerizable Surfactant A (29.10% solids, 3.2 g) were added to a reactor suitable for emulsion polymerization equipped with stirring, heating and cooling means with a slow continuous nitrogen purge. With continuous stirring, the temperature of the reactor was increased to 80° C. At 80° C., monomer pre-emulsion (26.07 g) [5.0% total pre-emulsion prepared by mixing water (115 g), Polymerizable Surfactant A (5.8 g), methyl methacrylate (40 g), 2-ethylhexyl acrylate (296 g), acrylic acid (12 g), Sipomer BCEA (4 g), and chain transfer agent (0.5 g), adjusted with ammonia (6.4 g)] was added to the reactor. Once the reactor temperature stabilized at 80° C., a 5% solution of ammonium persulfate (0.5 g dissolved in deionized water (10 g)) was added to the reactor.

[0070] After 25 minutes, a sample was taken from the reactor for particle size analysis. The seed particle size was 79.5 nm. After 5 minutes, continuous addition of the remaining monomer pre-emulsion and initiator solution (1 g dissolved in 100 g deionized water) was started for 3 hours at a temperature of 80° C. The monomer pre-emulsion was completed for addition in over 2 hours 45 minutes. The initiator addition was completed in 3 hours. The reactor was held at 80° C. for an additional 30 minutes until the final solids value was constant or approaching the maximum theoretical value. The resulting polymer dispersion had a solids content of 44.51% and an average particle size of 137.9 d.nm. The reactor was cooled to below 40° C. and the resulting latex was filtered through a 200 um polyester filter. The properties of the latex were listed in Table 2.

[0071] Example 11. Following the same procedure as described in Example 10, the preparation of latex polymers by using the polymerizable surfactant samples prepared in Examples 2-9 and the latex formulations are listed in Table 2.

[0072] [Table 2]

[0073] Comparative Example 12. Preparation of latex polymer by using comparative non-polymerizable surfactant. The polymerization recipe is listed in Table 3, and the process is similar to that of Example 10. Conventional non-polymerizable surfactants, RHODACAL DS-10 (sodium dodecylbenzenesulfonate, Comparative Sample A) and RHODAFAC PA12 (oleyl ether ethoxylated phosphate, Comparative Sample B), were used. The properties of the latex are listed in Table 4.

[0074] [Table 3]

[0075] [Table 4]

[0076] Example 13. Water-whitening resistance and water resistance testing for pressure sensitive adhesive (PSA) applications. The latex polymers prepared in Examples 10-12 were tested for water-whitening resistance and water resistance performance in PSA applications. Water-whitening resistance was measured at both room temperature and hot water conditions (approximately 90° C.).

[0077] Water-whitening resistance testing was performed according to the following test method: The latex polymer was applied to a PET film with a 90 μm applicator and dried in an oven at 110° C. for 3 minutes. The film was allowed to cool overnight. The film was then immersed in a water bath at room temperature for up to 24 hours and at elevated temperatures of 90° C. for up to 50 minutes. Water-whitening resistance and water resistance were tested on a scale of 0 to 5, with 0 being the worst and 5 being the best. Water-whitening measurements were also evaluated by checking the change in color delta L and color delta E values ​​before and after immersing the film in water. The test results are shown in Figures 2 to 5.

[0078] FIG. 2 shows the water whitening resistance and water fastness test at room temperature.

[0079] FIG. 3 shows the water whitening resistance and water resistance test at 90° C.

[0080] FIG. 4 shows the color delta L values ​​of water whiteness change (90° C. for 50 minutes) for the examples.

[0081] FIG. 5 shows the color Delta E values ​​of water brightness change (50 min at 90° C.) for the examples.

[0082] Test data showed that the polymerizable surfactants prepared according to the present invention significantly improved the water-whitening resistance and water resistance of latex polymers in pressure sensitive adhesive applications compared to conventional surfactants.

[0083] Example 14. Preparation of latex polymers by using the polymerizable surfactant samples (Surfactant A and Surfactant B) prepared in Examples 1 and 2 in styrene acrylic emulsion polymerization according to the following procedure. Latex polymers were also prepared using comparative surfactant sample, Comparative Sample C (-allylethoxylate sulfate sodium salt), Comparative Sample D (tristyrenephenol EO-PO sulfate sodium salt) and Comparative Sample E (tristyrenephenol EO phosphate ammonium salt). The formulations of these latex polymers are shown in Table 5.

[0084] [Table 5]

[0085] Deionized water (DI) (233.5 g) and sample Surfactant A (8.3 g) were mixed and added to a reactor suitable for emulsion polymerization equipped with stirring, heating and cooling means with a slow continuous nitrogen purge. With continuous stirring, the temperature of the reactor was increased to 80.0° C. At 80.0° C., monomer pre-emulsion (28.3 g) [5.0% of a total of 560 g of monomer pre-emulsion was prepared by mixing deionized water (149.7 g), Surfactant A (8.3 g), styrene (194 g), butyl acrylate (190 g), acrylic acid (10 g), acrylamide (6 g) and vinyl trimefoxysilane (2 g)] was added to the reactor (the pre-emulsion was stabilized prior to addition) followed by a solution of ammonium persulfate (10.5 g) [ammonium persulfate (0.5 g) dissolved in deionized water (10 g)].

[0086] The seed was held for 15 minutes. A small sample was taken to check the particle size. Continuous addition of the remaining monomer pre-emulsion (532.7 g) and initiator solution [ammonium persulfate (1.50 g) dissolved in deionized water (70.0 g)] was set to end at 3 hours. The reactor was held at 80°C for another 30 minutes until the final solids value was constant or near the maximum theoretical value. The reactor was then cooled to below 40°C and the resulting latex was filtered through a polyester filter. The polymer was neutralized to pH 8-8.5 using 28% ammonium hydroxide. The resulting polymer dispersion had a solids content of 44.3%, a viscosity of 1373 cP and an average particle size of 119.2 d.nm. The properties of the latex are given in the table below. Other polymers were also prepared following a similar procedure and the properties are listed in Table 6.

[0087] [Table 6]

[0088] The water-whitening resistance and water resistance performance of the prepared polymers were tested by the following methods.

[0089] Prepare test samples in MFFT: 3% Texanol (3 g texanol / 100 g latex) at <1.5°C.

[0090] 2. Clean the black glass panel with ethanol to ensure there is no contamination.

[0091] 3. Prepare duplicates of each sample by applying a 120um wet latex film to a clean black glass panel.

[0092] 4. Keep the black glass panel at room temperature for 1 day.

[0093] 5. Immerse the black glass panel in deionized water for three days.

[0094] 6. Remove the glass panel from the water and gently dry the film and glass with soft paper, being careful not to destroy the latex film. Immediately measure the opacity value with a spectrophotometer.

[0095] The opacity value indicates the water whitening resistance and water resistance performance of the latex and paint films. A lower opacity value indicated less water whitening and therefore better water resistance. Figure 6 shows the opacity (%) values ​​of these polymers, with samples Surfactant A and Surfactant B showing improved water whitening resistance and water resistance properties over the comparative sample.

[0096] Example 15. Preparation of latex polymer by using the polymerizable surfactant sample prepared in Example 2 (Surfactant B) in a styrene acrylic emulsion polymerization according to the procedure described in Example 14. The latex polymer formulation is shown in Table 7. A comparative surfactant sample, Comparative Sample E (Tristyrenic Phenol EO Phosphate Ammonium Salt), was also used in the preparation of the latex polymer.

[0097] [Table 7]

[0098] The properties of these polymers are listed in Table 8.

[0099] [Table 8]

[0100] The latex polymer was formulated in a 49% PVC exterior paint for masonry or other building substrates. The paint formulation is shown in Table 9.

[0101] [Table 9]

[0102] The watermark resistance and surfactant leaching characteristics of the formulated exterior paints were evaluated according to the following method. Results are reported on a scale of 1 to 10, with 1 being the worst and 10 being the best. The surfactants of the present invention significantly improved the watermark resistance and surfactant leaching characteristics of the paints.

[0103] 1. Apply one coat of paint (150μ-WFT) to the substrate and allow to dry for 24 to 28 hours.

[0104] 2. Apply a drop of water to the paint film and allow the drop to rest for 10 minutes.

[0105] 3. Lift the panel vertically and allow the water to drip off.

[0106] 4. Keep the panel in a vertical position and observe the watermark after drying.

[0107] FIG. 1 shows the improved watermark resistant white base paint and the paint tinted with 5% colorant.

[0108] Description of the Invention The following description also explains features that the present invention may have.

[0109] Description 1. A polymerizable surfactant composition comprising: Formula (I): [ka] (Wherein, R1 is C8 to C 14 is an alkyl group or a bicyclic group, "x" is an integer from 1 to 20, "y" is an integer from 1 to 30, M + is H + , Na + , NH4 + , K + Or Li + is) and a polymerizable surfactant of Optionally, at least one surfactant; 1. A polymerizable surfactant composition comprising:

[0110] Description 2.M + is Na+ or NH4+.

[0111] Statement 3. The polymerizable surfactant composition of statement 1 or 2, wherein "x" is an integer from 1 to 40 and "y" is an integer from 1 to 50.

[0112] Statement 4. The polymerizable surfactant composition of any of Statements 1 to 3, further comprising a surfactant comprising any one of sodium alkylbenzene sulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyl diphenyloxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof, and alkyl alcohol ethoxylate sulfate or any salt thereof.

[0113] Statement 5.R1 is bicyclo [d.e.f] Heptyl or bicyclo [d.e.f] heptenyl group, where d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5; [d.e.f]Heptyl or bicyclo [d.e.f] Any of the polymerizable surfactant compositions described above, wherein the heptenyl group may optionally be substituted at one or more of the ring carbon atoms by one or more (C1-C6) alkyl groups.

[0114] Statement 7. The polymerizable surfactant composition of any of the preceding statements, wherein "y" is an integer from 5 to 15.

[0115] Statement 8. A process for preparing a coating comprising introducing a composition of any of the preceding statements as an emulsifier during emulsion polymerization.

[0116] Statement 9. A polymerizable composition comprising: Formula (I): [ka] (Wherein, R1 is C8 to C 14 is an alkyl group or a bicyclic group, "x" is an integer from 1 to 20, "y" is an integer from 1 to 30, M + is H + , Na + , NH4 + , K + Or Li + is) and a polymerizable surfactant of one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers or vinyl ester monomers; Optionally, at least one surfactant; 1. A polymerizable composition comprising:

[0117] Description 10.M + is Na+ or NH4+.

[0118] Statement 11. The polymerizable composition of statements 9 or 10, wherein "x" is an integer from 1 to 40 and "y" is an integer from 1 to 50.

[0119] Statement 12. The polymerizable composition of statements 9, 10, or 11, further comprising a surfactant comprising any one of sodium alkylbenzene sulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyl diphenyloxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, or fatty alcohol phosphate or any salt thereof.

[0120] Statement 13.R1 is bicyclo [d.e.f] Heptyl or bicyclo [d.e.f] heptenyl group, where d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5; [d.e.f] Heptyl or bicyclo [d.e.f] 13. The polymerizable composition of any of statements 9-12, wherein the heptenyl group may be optionally substituted at one or more of the ring carbon atoms by one or more (C1-C6) alkyl groups.

[0121] Statement 14. The polymerizable composition of any of statements 9-13, wherein "x" is an integer from 1 to 5.

[0122] Statement 15. The polymerizable composition of any of statements 9-14, wherein "y" is an integer from 5 to 15.

[0123] Statement 16. The polymerizable surfactant composition of any one of Statements 1 to 8 or any one of Statements 9 to 15, further comprising at least one component selected from a chain transfer agent, an additive for adjusting pH, and a compound used as a protective colloid.

[0124] Statement 17. A pressure-sensitive adhesive comprising the polymerizable surfactant composition of any one of statements 1 to 8.

[0125] Statement 18. The pressure sensitive adhesive of statement 17 having improved water-whitening resistance and water resistance properties compared to a polymerizable surfactant composition not comprising a polymerizable surfactant of formula (I).

[0126] Statement 19. A pressure-sensitive adhesive comprising the polymerizable composition of any one of statements 9 to 15.

[0127] Statement 20. The pressure sensitive adhesive of statement 19 having improved water-whitening resistance and water resistance properties compared to a polymerizable surfactant composition not comprising a polymerizable surfactant of formula (I).

[0128] Statement 21. A coating having improved watermark resistance and surfactant leaching resistance properties comprising the polymerizable surfactant composition of any of statements 1-8.

[0129] Statement 22. The coating of claim 21, further comprising an acrylic latex.

[0130] Statement 23. A method comprising polymerizing by emulsion polymerization a mixture of a polymerizable polymer and the polymerizable surfactant composition of any of statements 1-8.

[0131] Statement 24. A method comprising emulsion polymerizing the polymerizable composition of any of statements 9-15 by emulsion polymerization.

[0132] Statement 25. A polymerizable surfactant composition comprising: Formula (I): [ka] (Wherein, R1 is C8 to C 14 is an alkyl group or a bicyclic group, "x" is an integer from 1 to 20, "y" is an integer from 1 to 30, M + is H + , Na + , NH4 + , K + Or Li + is) and a polymerizable surfactant of Optionally, at least one further surfactant; 1. A polymerizable surfactant composition comprising:

[0133] Embodiments other than those expressly described herein are clearly within the spirit and scope of the appended claims. Accordingly, the invention is not defined by the above description, but is intended to be accorded the full scope of the appended claims to encompass any and all equivalent compositions and methods.

Claims

1. 1. A polymerizable surfactant composition comprising: Formula (I): (In the formula, R １ is bicyclo ［ｄ．ｅ．ｆ］ Heptyl or bicyclo ［ｄ．ｅ．ｆ］ heptenyl group, where d is 2, 3 or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5; ［ｄ．ｅ．ｆ］ Heptyl or bicyclo ［ｄ．ｅ．ｆ］ A heptenyl group may optionally have one or more (C １ ~C ６ ) may be substituted by an alkyl group; "x" is an integer from 1 to 10, "y" is an integer from 3 to 20, M ＋ H ＋ , Na ＋ , NH4 ＋ , K ＋ Or Li ＋ (It is) and a polymerizable surfactant of Optionally, at least one surfactant; 1. A polymerizable surfactant composition comprising:

2. M ＋ is Na ＋ or NH4+.

3. 2. The polymerizable surfactant composition of claim 1, further comprising a surfactant comprising any one of sodium alkylbenzene sulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyl diphenyloxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof, alkyl alcohol ethoxylate sulfate or any salt thereof.

4. 2. The polymerizable surfactant composition of claim 1, wherein "x" is an integer from 1 to 5.

5. 2. The polymerizable surfactant composition of claim 1, wherein "y" is an integer from 5 to 15.

6. 13. A process for preparing a coating comprising introducing the composition of claim 1 as an emulsifier during emulsion polymerization.

7. 1. A polymerizable composition comprising: Formula (I): In the formula, R １ is bicyclo ［ｄ．ｅ．ｆ］ Heptyl or bicyclo ［ｄ．ｅ．ｆ］ heptenyl group, where d is 2, 3 or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5; ［ｄ．ｅ．ｆ］ Heptyl or bicyclo ［ｄ．ｅ．ｆ］ A heptenyl group may optionally have one or more (C １ ~C ６ ) may be substituted by an alkyl group; "x" is an integer from 1 to 10, "y" is an integer from 3 to 20, M ＋ H ＋ , Na ＋ , N.H. ４ ＋ , K ＋ Or Li ＋ (It is) and a polymerizable surfactant of one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers or vinyl ester monomers; Optionally, at least one surfactant; 1. A polymerizable composition comprising:

8. M ＋ is Na ＋ or NH ４ The polymerizable composition according to claim 7, wherein

9. 8. The polymerizable composition of claim 7, further comprising a surfactant comprising any one of sodium alkylbenzene sulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyl diphenyloxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof.

10. 8. The polymerizable composition of claim 7, wherein "x" is an integer from 1 to 5.

11. 8. The polymerizable composition of claim 7, wherein "y" is an integer from 5 to 15.

12. 10. The polymerizable surfactant composition of claim 1, further comprising at least one component selected from a chain transfer agent, an additive for adjusting pH, and a compound utilized as a protective colloid.

13. 8. The polymerizable composition of claim 7, further comprising at least one component selected from a chain transfer agent, an additive for adjusting pH, and a compound utilized as a protective colloid.

14. 10. A pressure sensitive adhesive having improved water-whitening resistance and water resistance properties comprising a polymer obtained from the polymerizable surfactant composition of claim 1.

15. A pressure sensitive adhesive having improved water whitening resistance and water resistance properties comprising a polymer obtained from the polymerizable composition of claim 7.

16. 10. A coating composition having improved watermark resistance and surfactant leaching resistance properties comprising a polymer resulting from polymerization of the polymerizable surfactant composition of claim 1.

17. A coating having improved watermark resistance and surfactant leaching resistance properties comprising a polymer obtained from polymerization of the polymerizable composition of claim 7.

18. 18. The coating of claim 16 or 17, further comprising an acrylic latex.

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