Coating compositions having improved properties comprising polymers formed from polymerizable surfactants - Patent Application 20070122999

Abstract

The present invention generally relates to coating compositions comprising a polymer formed from at least one polymerizable surfactant, the coating compositions having improved performance properties, such as improved stain resistance (DPUR), improved hardness, and improved blocking resistance.

Description

[Technical Field]

[0001] The present invention generally relates to a coating composition comprising a polymer formed from at least one polymerizable surfactant. More specifically, the present invention generally relates to a coating composition comprising a polymer formed from at least one polymerizable surfactant, the coating composition having improved performance properties, such as improved stain resistance (DPUR), improved hardness, and improved blocking resistance. The present invention also relates to methods for making such coating compositions, using the polymerizable surfactant, and using such coating compositions on the surface of a substrate, where the coating composition provides its improved DPUR, hardness, and blocking resistance. [Background technology]

[0002] Surfactants are used in a variety of applications and for a variety of purposes, including, for example, dispersion and emulsification across numerous industries. For example, surfactants are used in coatings, paints, adhesives, home care products, personal care products, construction, paper, inks, etc. Often, products contain surfactants to aid in their stabilization or to improve specific properties, such as foaming, viscosity, or wetting, of the product. However, surfactants can also be used in processes and industrial reactions. For example, surfactants can be used in polymerization reactions via a process called emulsion polymerization.

[0003] In emulsion polymerization processes, polymers are formed in micelles formed by surfactants. In particular, surfactants can help stabilize the micelles, allowing the reaction to continue, thus allowing polymer formation and propagation. For the preparation of latex (e.g., aqueous latex) in conventional emulsion polymerization processes, the non-polymerizable surfactant is often an anionic surfactant or a mixture of anionic and non-ionic surfactants. The non-polymerizable surfactant is present in the emulsion polymerization process at a concentration sufficient to enable and promote the polymerization of monomers to form latex polymers, resulting in the formation of latex particles. These non-polymerizable surfactants, along with the reaction conditions, determine the polymer's properties, such as the particle size of the latex particles. For example, anionic surfactants can provide shear stability to prevent loss due to coagulation. Non-ionic surfactants can provide electrolyte or chemical stability to the growing latex particles. The type and structure of one or more surfactants used during an emulsion polymerization process can dramatically affect the emulsification properties, which can dramatically affect the formation of a latex (and whether a latex is formed), including latex particle size, latex particle size distribution, and latex viscosity. Thus, surfactants play an important role not only in emulsion polymerization processes in general, but also in emulsion polymerization processes for producing latexes more specifically.

[0004] However, while surfactants can play an important role in forming polymers during emulsion polymerization processes, surfactants that remain in or associate with the polymer, or that otherwise migrate from the process to the product, can adversely affect product properties. That is, while surfactants may be required in the polymerization process, the same surfactants can degrade the performance of the resulting product. For example, in paints and other coatings, the presence of excess surfactants can contribute to increased water sensitivity and water whitening, adversely affecting the resulting coating or film. DPUR, hardness, blocking resistance, weatherability, durability, and adhesion can also be affected. In particular, surfactants in paints, adhesives, including pressure-sensitive adhesives (PSAs), inks, stains, and other coatings can reduce the resilience and durability of the resulting coating or film.

[0005] It is generally understood that the decline in the beneficial properties of a coating or film is primarily due to surfactant mobility. That is, traditional surfactants used in polymerization processes can be free or separate surfactant molecules within the coating or film. For example, locally high concentrations of surfactant molecules can form in a coating or film from the coalescence of surfactant-coated micellar spheres. When the coating is exposed to water, the surfactant molecules can be extracted or washed away from the coating or film, causing the coating or film to become more porous. Simply put, when the surfactant is washed away, the coating or film is no longer uniform but rather may have pinholes, thin spots, or pathways to the substrate surface that can be penetrated by water or other solvents or liquids. This not only compromises the integrity of the coating or film, but can also result in water or other solvents or liquids that can lead to degradation or damage to the underlying substrate surface (e.g., rust, damage, deterioration, etc.). Whitening, blooming, or blushing can also occur when surfactants are present in the coating or film. This can result in the coating or film becoming cloudy or white, reducing the coating's or film's inherent gloss.

[0006] To address these issues, surfactants that are polymerizable (i.e., polymerizable surfactants), also known as reactive surfactants, can be used in the polymerization process. Unlike traditional surfactants used in polymerization processes, which are generally only used to form micelles, polymerizable surfactants also act as monomers or form part of the resulting polymer in the reaction. This minimizes and reduces the undesirable consequences of having free or isolated surfactant molecules in the coating or film, which can then weaken the resulting coating or film and make it less resilient and durable.

[0007] However, even when polymerizable surfactants are generally used in polymerization processes, coatings or films containing polymers formed from the process may still lack desired properties. For example, the coating or film may still lack certain properties, such as sufficient DPUR, hardness, and blocking resistance. This is because the polymerizable surfactant acts as a monomer or forms part of the resulting polymer in the polymerization process, and thus becomes part of the resulting polymer, which is then used in the coating or film. Furthermore, benzophenone can typically be added to enhance certain properties of the coating, such as increasing DPUR and hardness. However, the use of benzophenone in coatings is facing increased regulatory scrutiny, and therefore there are moves to limit or even stop the use of benzophenone in coatings. In such situations, coatings that do not contain benzophenone may not have sufficiently desirable properties compared to coatings that contain benzophenone.

[0008] In view of the above problems, there remains a need in the art for coating compositions having polymers formed from polymerizable surfactants that provide improved properties such as improved DPUR, hardness, and blocking resistance. There also remains a need in the art for coating compositions having polymers formed from polymerizable surfactants that not only provide improved properties such as improved DPUR, hardness, and blocking resistance, but also have sufficient or improved adhesion (e.g., adhesion to substrate surfaces, including metal surfaces), durability, and weatherability, while simultaneously having minimal or reduced water sensitivity, water whitening resistance, blooming, and blushing. Furthermore, there remains a need in the art for coating compositions that have the above-mentioned properties without the need for benzophenone. That is, there remains a need in the art for coatings that can eliminate or reduce the need for benzophenone while maintaining or even increasing coating properties, including, but not limited to, increased DPUR and hardness. Summary of the Invention [Means for solving the problem]

[0009] In general, the present invention relates to a coating composition comprising a polymer formed from at least one polymerizable surfactant. In one embodiment, the present invention generally relates to a coating composition comprising a polymer formed from at least one polymerizable surfactant, wherein the polymerizable surfactant has the formula (I): [ka] (In the formula: R1 is C8~C 14 Alkyl groups, preferably C 10 ~C 14 an alkyl group, a bicyclic group, or a combination thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and equal to 30, preferably 12 to 20, and more preferably 14 to 18; M + is H + , Na + , NH4 + , K. + , Li + , or a combination thereof).

[0010] In another embodiment, the invention generally relates to a method of making a coating composition comprising a polymer formed from at least one polymerizable surfactant, the method comprising emulsion polymerizing the at least one polymerizable surfactant with at least one other monomer, wherein the at least one polymerizable surfactant has Formula (I): [ka] (In the formula: R1 is C8~C 14 Alkyl groups, preferably C 10 ~C 14 an alkyl group, a bicyclic group, or; It is a combination of; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and equal to 30, preferably 12 to 20, and more preferably 14 to 18; M + is H + , Na + , NH4 + , K. + , Li + , or a combination thereof).

[0011] In yet another embodiment, the present invention generally provides compounds of formula (I): [ka] (In the formula: R1 is C8~C 14 Alkyl groups, preferably C 10 ~C 14an alkyl group, a bicyclic group, or a combination thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and equal to 30, preferably 12 to 20, and more preferably 14 to 18; M + is H + , Na + , NH4 + , K. + , Li + or a combination thereof) of the polymerizable surfactant The present invention relates to the use of the composition for forming polymers for coating compositions.

[0012] In a further embodiment, the present invention generally relates to the use of a coating composition comprising a polymer formed from at least one polymerizable surfactant, wherein the polymerizable surfactant has the formula (I): [ka] (In the formula: R1 is C8~C 14 Alkyl groups, preferably C 10 ~C 14 an alkyl group, a bicyclic group, or a combination thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and equal to 30, preferably 12 to 20, and more preferably 14 to 18; M + is H + , Na + , NH4 + , K. + , Li + or a combination thereof) of the polymerizable surfactant Preferably, the coating composition is for use to coat at least a portion of a surface of a substrate, providing improved stain resistance (DPUR), hardness, blocking resistance, or a combination thereof.

[0013] Another aspect of certain embodiments includes methods of utilizing the polymerizable surfactants of formula (I) to prepare polymers, including but not limited to latex polymer emulsions and paints. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows the pendulum hardness before cure of an elastomeric coating containing a latex polymer prepared from a polymerizable surfactant and an elastomeric coating containing a latex polymer prepared by using a conventional non-polymerizable surfactant. [Figure 2] FIG. 2 shows the pendulum hardness after curing of an elastomeric coating containing a latex polymer prepared from a polymerizable surfactant and an elastomeric coating containing a latex polymer prepared by using a conventional non-polymerizable surfactant. [Figure 3] FIG. 3 shows the blocking resistance results of test panels coated with an elastomeric paint containing a latex polymer prepared from a polymerizable surfactant and an elastomeric paint containing a latex polymer prepared by using a conventional non-polymerizable surfactant. The panels were tested under 1 kg load at 50°C for 30 minutes in accordance with ASTM D4946. [Figure 4] FIG. 4 shows the DPUR of an elastomeric coating containing a latex polymer prepared from a polymerizable surfactant and an elastomeric coating containing a latex polymer prepared by using a conventional non-polymerizable surfactant. [Figure 5] FIG. 5 shows the blocking resistance results of test panels coated with an acrylic paint containing a latex polymer prepared from a polymerizable surfactant and an acrylic paint containing a latex polymer prepared by using a conventional non-polymerizable surfactant. The panels were tested under a 1 kg load at 50°C for 30 minutes in accordance with ASTM D4946. [Figure 6]FIG. 6 shows the DPUR of an acrylic paint containing a latex polymer prepared from a polymerizable surfactant and an acrylic paint containing a latex polymer prepared by using a conventional non-polymerizable surfactant. DETAILED DESCRIPTION OF THE INVENTION

[0015] general definition The terms and expressions used herein, "invention," "present invention," "instant invention," and similar terms and expressions, are non-limiting and are not intended to limit the inventive subject matter to any single embodiment, but rather encompass all possible embodiments described.

[0016] Throughout the description, including the claims, the terms "a" and "at least one" are synonymous; similarly, unless otherwise specified, the terms "including one" or "shall be understood to be synonymous with the term" include at least one. Furthermore, "among" is to be understood as including limits. Furthermore, throughout the description, including the claims, the terms "comprising" and "having" can be used interchangeably and should be understood to be synonymous.

[0017] It should be noted that in specifying any range of concentrations, weight ratios, or amounts, any particular upper concentration, weight ratio, or amount may be associated with any particular lower concentration, weight ratio, or amount, respectively.

[0018] As used herein, the term "alkyl" or "alkyl group" means a saturated hydrocarbon radical, which may be straight-chained, branched, or cyclic, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl, and the like.

[0019] As used herein, the term "bicyclic" or "bicyclic group" means a group that contains at least two connected rings that have at least two common atoms. In certain embodiments, a bicyclic group can contain at least two rings that can be fused, bridged, or both.

[0020] As used herein, the term "cycloalkyl" or "cycloalkyl group" means a saturated hydrocarbon radical containing one or more cyclic alkyl rings, such as, for example, cyclopentyl, cyclooctyl, and adamantanyl.

[0021] As used herein, the term "hydroxyalkyl" or "hydroxyalkyl group" refers to an alkyl radical, more typically an alkyl radical substituted with a hydroxyl group, such as, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.

[0022] As used herein, the terms "alkylene" or "alkylene group" mean 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.

[0023] As used herein, the term "alkenyl" or "alkenyl group" 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, etc.

[0024] As used herein, the term "aryl" or "aryl group" 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.

[0025] As used herein, the terms "aralkyl" or "aralkyl group" refer to an alkyl group substituted with one or more aryl groups, such as phenylmethyl, phenylethyl, triphenylmethyl, and the like.

[0026] As used herein, "AGE" is allyl glycidyl ether.

[0027] As used herein, the terminology relating to organic groups is "(C n ~C m )" (where n and m are each integers) indicates that the group may contain from n carbon atoms to m carbon atoms per group.

[0028] As used herein, the term "ethylenically unsaturated," "ethylenically unsaturated," or similar terms means terminal (ie, for example, α, β) carbon-carbon double bonds.

[0029] As used herein, "DPUR" means dirt pick-up resistant.

[0030] Coating Composition It has been found that the coating composition comprising the polymer formed from at least one polymerizable surfactant according to the present invention can have unexpectedly excellent advantages.For example, in one embodiment, the coating composition comprising the polymer formed from at least one polymerizable surfactant according to the present invention can have unexpectedly excellent DPUR, hardness, or blocking resistance.In certain embodiments, the coating composition comprising the polymer formed from at least one polymerizable surfactant according to the present invention can have an unexpectedly excellent combination of the aforementioned properties, for example, an unexpectedly excellent DPUR, hardness, blocking resistance, or a combination of properties.

[0031] In particular, coating compositions according to the present invention may have unexpectedly superior DPUR, hardness, blocking resistance, or combinations of properties compared to coating compositions having polymers formed from emulsion polymerization processes using conventional (i.e., non-polymerizable) surfactants, as well as coating compositions having polymers formed from emulsion polymerization processes using polymerizable surfactants other than those of the present invention. That is, the presently claimed coating compositions having polymers comprising the polymerizable surfactants of the present invention may have unexpectedly superior DPUR, hardness, blocking resistance, or combinations of properties when compared to coating compositions having polymers comprising polymerizable surfactants other than those of the present invention. The presently claimed coating compositions may also have unexpectedly superior DPUR, hardness, blocking resistance, or combinations of properties compared to coating compositions having polymers formed by using conventional non-polymerizable surfactants.

[0032] In addition to the above, the coating compositions of the present invention can also have various desirable properties in addition to unexpectedly better DPUR, hardness, blocking resistance, or a combination of properties. In other words, in various embodiments, the coating compositions of the present invention can have unexpectedly excellent DPUR, hardness, blocking resistance, or a combination of properties without having to sacrifice, reduce, or decrease other desirable properties of the coating composition. This is important because increasing a particular desirable property often comes at the expense of having to sacrifice other properties. In this regard, not only can the coating compositions of the present invention have unexpectedly excellent DPUR, hardness, blocking resistance, or a combination of properties, but the coating compositions can have such properties without significantly reducing other beneficial properties of the coating composition.

[0033] In addition to the above, the coating compositions of the present invention can provide unexpectedly excellent DPUR, hardness, blocking resistance, or a combination of properties without the need for the addition of benzophenone. Benzophenone is a common coating additive and can be used to enhance certain properties of coatings, such as increasing the DPUR and hardness of the coating. Nevertheless, it is desirable to reduce or even eliminate the need for benzophenone in coatings. Surprisingly, it has been unexpectedly discovered that coating compositions of the present invention can not only have unexpectedly excellent DPUR, hardness, blocking resistance, or a combination of properties, particularly unexpectedly excellent DPUR and hardness, but also that the coating compositions can have such excellent properties with or without benzophenone. In this regard, in certain embodiments, the coating compositions of the present invention have unexpectedly excellent DPUR, hardness, blocking resistance, or a combination of properties, particularly unexpectedly excellent DPUR and hardness, without the addition of benzophenone.

[0034] In view of the above, in certain embodiments, coating compositions of the present invention can have improved DPUR as measured by ASTM D3719. In this regard, in certain embodiments, coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention can have an improved DPUR of at least about 5%, at least about 10%, or at least about 12% increase in DPUR as measured by ASTM D3719 compared to coating compositions comprising a polymer not formed from at least one polymerizable surfactant of the present invention. In certain other embodiments, coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention can have an improved DPUR of at least about 8%, at least about 14%, or at least about 16% increase in DPUR as measured by ASTM D3719 compared to coating compositions comprising a polymer not formed from at least one polymerizable surfactant of the present invention.

[0035] Also as noted above, in certain embodiments, coating compositions of the present invention can have improved hardness as measured by ASTM D4366, as well as improved blocking resistance as measured by ASTM D4946. With respect to embodiments having improved hardness, such embodiments include coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention, wherein the hardness is increased by at least about 5%, at least about 8%, or at least about 10%, as measured by ASTM D4366, compared to a coating composition comprising a polymer not formed from at least one polymerizable surfactant of the present invention. With respect to embodiments having improved blocking resistance, such embodiments include coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention, which have an increase in blocking resistance of about 50% or more, about 100% or more, about 150% or more, about 200% or more, about 250% or more, about 300% or more, about 350% or more, about 400% or more, or about 450% or more, as measured by ASTM D4946, compared to a coating composition comprising a polymer not formed from at least one polymerizable surfactant of the present invention.

[0036] Also, as noted above, the coating compositions of the present invention can have excellent DPUR, hardness, blocking resistance, or a combination of properties.

[0037] Additionally, various types of coating compositions of the present invention can include a polymer formed from at least one polymerizable surfactant. For example, in some embodiments, the coating composition can be an elastomeric coating, an architectural coating, or both. Furthermore, in certain embodiments, the coating composition can be a latex coating. In this regard, in various embodiments, the coating composition can generally have a glass transition temperature (Tg) of -40°C to 40°C as measured by ASTM D3418. In certain embodiments, the coating composition can have a glass transition temperature (Tg) of -40°C to -10°C, preferably -40°C to -20°C, as measured by ASTM D3418. In other embodiments, the coating composition can have a glass transition temperature (Tg) of -5°C to 40°C, preferably 10°C to 40°C, as measured by ASTM D3418.

[0038] In embodiments where the coating composition is an elastomeric coating, the coating composition may have a glass transition temperature (Tg) of -40°C to 40°C, preferably -40°C to -10°C, and more preferably -40°C to -20°C, as measured by ASTM D3418. In embodiments where the coating composition is an architectural coating, the coating composition may have a glass transition temperature (Tg) of -40°C to 40°C, preferably -5°C to 40°C, and more preferably 10°C to 40°C, as measured by ASTM D3418.

[0039] Polymerizable surfactants Like non-polymerizable surfactants, polymerizable surfactants are typically molecules with hydrophobic and hydrophilic groups, such as ionic and / or polar groups. The hydrophobic groups preferentially adsorb to the surface of the polymer particles during and after particle polymerization. In the context of emulsion polymerization processes to form latexes, the hydrophobic groups preferentially adsorb to the surface of the latex polymer particles during and after the polymerization process. The hydrophilic groups on the surfactant extend into the aqueous solution phase, providing a steric barrier or charge repulsion against particle aggregation and coagulation.

[0040] However, unlike their non-polymerizable counterparts, polymerizable surfactants additionally contain reactive groups on the molecule, e.g., on hydrophobic groups, that can covalently bond to the latex surface. Typically, this is a moiety such as a terminally unsaturated carbon group, such as a vinyl or olefin group, that can participate in a free-radical emulsion polymerization reaction. When used in emulsion polymerization, the majority of the polymerizable surfactant molecules become irreversibly bound to the emulsion polymer chains and droplets. This can improve latex stability and reduce foaming, among other desirable properties. It can also reduce or minimize the amount of free or separated surfactant molecules. In the context of this application, a polymer formed from at least one polymerizable surfactant and a polymer comprising at least one polymerizable surfactant are synonymous and equivalent. That is, unlike conventional non-polymerizable surfactants, the polymerizable surfactants of the present invention form part of a polymer (i.e., the polymer comprises the polymerizable surfactant).

[0041] As mentioned above, it has been surprisingly found that the coating composition comprising the polymer formed by at least one polymerizable surfactant according to the present invention can have unexpectedly excellent advantages.In this regard, it has been surprisingly found that when the polymerizable surfactant described herein is used to prepare polymer, and particularly used to prepare latex, the coating composition having the polymer therein has excellent properties, such as excellent DPUR, hardness, blocking resistance or a combination of properties.

[0042] The polymerizable surfactants described herein are prepared from readily available raw materials, and their preparation generally does not require special equipment or special handling. In certain embodiments, the polymerizable surfactant is an ethylenically unsaturated salt of allyl (poly)ether sulfate. 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 surfactant is prepared using water as a solvent, although other solvents, such as alcohol or other conventional solvents, can be used. Mixtures of solvents, including mixtures of water, alcohol, or other conventional solvents, can also be used to prepare the polymerizable surfactants of the present invention. A solvent or mixture of solvents can be used to make an aqueous solution of the polymerizable surfactant. In one embodiment, the polymerizable surfactants described herein also include the surfactant as a salt in dry form; 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 polymerizable surfactant solution. 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.

[0043] The coating of the present invention can be obtained from an aqueous dispersion containing at least one polymerizable surfactant according to the present invention. An effective amount of a conventional non-polymerizable surfactant can also be used together with the polymerizable surfactant. In certain embodiments, in addition to the above advantages, the coating of the present invention containing at least one polymerizable surfactant can have better water whitening resistance in a hot water (90°C) whitening test. In one specific embodiment, C 12 / C 14 -2.6AGE-15EO-sulfate sodium salt, C 12 / C 14Not only do Nopol-2.6AGE-15EO-ammonium sulfate, Nopol-2.6AGE-15EO-sodium sulfate, Nopol-2.6AGE-15EO-ammonium sulfate, and combinations thereof exhibit improved hot water whitening resistance compared to when non-reactive conventional surfactants (i.e., conventional non-polymerizable surfactants) are used, this particular embodiment can provide superior DPUR, hardness, blocking resistance, or combination of properties.

[0044] More generally, in one embodiment, the polymerizable surfactant has the formula (I): [ka] (In the formula: R1 is C8~C 14 Alkyl groups, preferably C 10 ~C 14 an alkyl group, a bicyclic group, or a combination thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and equal to 30, preferably 12 to 20, and more preferably 14 to 18; M + is H + , Na + , NH4 + , K. + , Li + , or a combination thereof).

[0045] In certain embodiments, the polymerizable surfactant may be a mixture of two or more polymerizable surfactants of formula (I), wherein R1 is two or more different C8-C 14alkyl group, two or more different bicyclic groups, or a mixture thereof, where both x and y can be any of the ranges described above and can vary for each particular surfactant of formula (I) in the mixture, and M+ can be a mixture and can vary for each particular surfactant of formula (I). As a non-limiting example, in certain embodiments, the polymerizable surfactant may be a mixture of two or more polymerizable surfactants of formula (I), where at least one surfactant of formula (I) is a C8-C9 14 Alkyl groups, preferably C 10 ~C 14 and at least one different polymerizable surfactant of formula (I) has R1 which is an alkyl group, ... 10 ~C 14 R1 is an alkyl group, x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; M + is H + , Na + , NH4 + , K. + , Li + , or a combination thereof.

[0046] When R1 is a bicyclic group, the bicyclic group may be substituted or unsubstituted and may be attached to the oxygen radical by an alkyl, alkylene, or alkenyl group. [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").

[0047] 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, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted at one or more ring carbon atoms with one or two (C1-C6) alkyl groups per carbon atom.

[0048] In one embodiment, R1 is a straight chain or branched C8-C 14 Alkyl groups, preferably linear or branched C 10 ~C 14 alkyl group, or mixtures thereof, and in other embodiments, R1 is a straight or branched C6-C 18 It is an alkyl group.

[0049] Additionally, R1: (i) a bicyclo 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 bicyclo bonded through the 2- or 3-carbon atom and substituted at the 7-carbon atom, typically by one or two (C1-C6) alkyl radicals, more typically by two methyl radicals; [3.1.1] Heptyl or bicyclo [2.2.1] It can be any one or any combination of heptenyl groups.

[0050] Suitable bicyclic groups for R1 include, but are not limited to, 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]

[0051] For example, R1 can be derived from the bicycloheptenyl intermediate compound (VII), also known as "nopol": [ka] It can be produced by reacting β-pinene with formaldehyde.

[0052] R1 can also be derived from the bicycloheptyl intermediate compound (VIII), known as "Arbanol": [ka] It can be made by isomerization of α-pinene to camphene and ethoxyhydroxylation of camphene.

[0053] In one embodiment, R1 can be derived from a bicycloheptyl- or bicycloheptenyl-intermediate that 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 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, according to well-known methods, typically at temperatures ranging from about 100° C. to about 250° C. and pressures ranging from about 1 to about 4 bar.

[0054] The bicycloheptyl or bicycloheptenyl-polyether monomer can then be 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.

[0055] In some embodiments of the polymerizable surfactant, the sulfate group comprises the corresponding salt form, and the cation includes, but is not limited to, Na+, NH4+, K+, or Li+. In other embodiments, M+ can be, but is not limited to, H+, Na+, NH4+, K+, or Li+. In certain embodiments, M+ is Na+, NH4+, or a combination thereof. In a preferred embodiment, M+ is NH4+.

[0056] In more particular embodiments, the polymerizable surfactant has formula (II): [ka] (In the formula: x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and equal to 30, preferably 12 to 20, and more preferably 14 to 18; M + is H + , Na + , NH4 + , K. + , Li + , or a combination thereof).

[0057] In yet other particular embodiments, the polymerizable surfactant has formula (III): [ka] (In the formula: x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and less than 30, preferably 12 to 20, and more preferably 14 to 18. can have:

[0058] In a particularly preferred embodiment, the polymerizable surfactant is Nopol-2.6AGE-15EO sulfate sodium salt, which has the following formula (IIIa): [ka] (In the formula: x has an average of 2.6; and y is 15) It is expressed as:

[0059] In certain embodiments, the polymerizable surfactant is specifically C 12 / C 14 -2.6AGE-15EO-ammonium sulfate, C 12 / C 14 Nopol-2.6AGE-15EO-sulfate sodium salt, Nopol-2.6AGE-15EO-sulfate sodium salt, Nopol-2.6AGE-15EO-sulfate ammonium salt, and mixtures thereof. Thus, a particular embodiment may be a compound represented by formula (IV): [ka] (In the formula: x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and less than 30, preferably 12 to 20, and more preferably 14 to 18. The polymerizable surfactant may include:

[0060] In one embodiment, the polymerizable surfactant is C 12 / C 14 -2.6AGE-15EO-sulfate sodium salt. More generally, the polymerizable surfactant may be of formula (V): [ka] (In the formula: x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and less than 30, preferably 12 to 20, and more preferably 14 to 18. can have:

[0061] In another particular embodiment, the polymerizable surfactant is C 12 / C 14-2.6AGE-15EO-ammonium sulfate. More generally, the polymerizable surfactant may be of formula (VI): [ka] (In the formula: x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 and less than 30, preferably 12 to 20, and more preferably 14 to 18. can have:

[0062] With respect to x and y in formulas (I)-(VI), these values ​​can be calculated based on the starting charge, by NMR analysis, or both.

[0063] It is important to note that the polymerizable surfactants useful in the present invention can include any combination of the polymerizable surfactants herein, including any combination of the various polymerizable surfactants of Formulas (I)-(VI), as well as any combination of specific salts of the polymerizable surfactants.

[0064] The polymerizable surfactants described herein may be used in applications where reactive surfactants containing one or more polyether groups have previously 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 agents, paints, etc.

[0065] 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 with other emulsifiers (surfactants) for emulsion polymerization. However, it is generally 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 other embodiments, conventional non-reactive surfactants (i.e., non-polymerizable surfactants) other than the polymerizable surfactants described herein can be utilized during the emulsion polymerization process. Such conventional non-reactive surfactants commonly used in emulsion polymerization processes include both anionic surfactants and non-ionic surfactants. In one embodiment, at least one polymerizable surfactant described herein can be used with one or more anionic surfactants. In other embodiments, at least one polymerizable surfactant described herein can be used with one or more cationic surfactants. In one embodiment, at least one polymerizable surfactant described herein can be used with one or more non-ionic surfactants. Additionally, the polymerizable surfactants or combinations of polymerizable surfactants described herein can be used with any combination of one or more anionic surfactants and one or more nonionic surfactants.

[0066] Non-limiting examples of anionic surfactants that can be used in conjunction with the polymerizable surfactants described herein, including emulsion polymerization processes, include sodium alkylbenzene sulfonate, alkyl sulfosuccinate, alkyldiphenyloxide disulfonate, ethoxylated alkylphenol sulfates and phosphates, fatty alcohol sulfates and phosphates, and the like, or any salts thereof. Non-limiting examples of nonionic surfactants that can be used in conjunction with the polymerizable surfactants described herein, including emulsion polymerization processes, include 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.

[0067] There are no particular limitations on the monomers that can be used in the emulsion polymerization process using the polymerizable surfactant, but preferably, the polymerizable surfactant of the present specification can be used in the emulsion polymerization process of 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, vinyl chloride emulsion, etc.

[0068] Non-limiting examples of suitable monomers that can be polymerized under the emulsion polymerization conditions described herein include ethylenically unsaturated monomers, such as vinyl monomers, acrylic monomers, acrylate monomers, and mixtures thereof. Typical vinyl monomers suitable for use include, but are not limited to, vinyl esters such as vinyl acetate, vinyl esters of carboxylic acids higher than acetic acid, including vinyl versatate, vinyl benzoate, vinyl propionate, vinyl aromatic hydrocarbons such as styrene, other vinyl aromatics such as methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, and mixtures thereof. Olefins such as C2-C4 olefins, including, but not limited to, ethylene, propylene, butylene, butadiene, and mixtures thereof, can also be used. Methacrylates and blends thereof can also be used. Halogenated vinyl monomers such as vinyl chloride, vinylidene chloride, and mixtures thereof can also be used.

[0069] Non-limiting examples of suitable acrylic monomers include compounds with acrylic functionality, such as alkyl acrylates and methacrylates, acrylic and methacrylic acids, and acrylamides and acrylonitriles, as well as mixtures thereof. Typical acrylic monomers include, but are not limited to, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and methacrylate, benzyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, decyl and dodecyl acrylate and methacrylate, and mixtures thereof. 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, amino acrylates and methacrylates, and mixtures thereof.

[0070] Other examples of (co)polymerizable monomers in acrylate emulsions include, but are not limited to, (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.

[0071] The polymerizable surfactant of the present invention can be used to prepare a coating composition. That is, the polymerizable surfactant of the present invention can be used to form a polymer for a coating composition. Furthermore, the polymerizable surfactant of the present invention can be used to prepare a coating composition, and the coating composition is used to coat at least a portion of a substrate to provide improved DPUR, hardness, blocking resistance, or a combination thereof, preferably improved DPUR, hardness, and blocking resistance.

[0072] In another aspect, a method for preparing polymers (including, but not limited to, latex polymer emulsions and paints) comprises using a polymerizable surfactant of the present invention in combination with at least one other surfactant that is not a polymerizable surfactant of the present invention. In one embodiment, the surfactant can be selected sodium alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl oxide disulfonates, ethoxylated alkyl phenol sulfates and phosphates, and fatty alcohol sulfates and phosphates. In another embodiment, the surfactant is selected from C 10 ~C 16 Alcohol ethoxylate sulfate or any salt thereof.

[0073] More generally, in certain embodiments, polymerizable surfactant can comprise any polymerizable surfactant in combination with at least one other surfactant that is not the polymerizable surfactant of the present invention.In one embodiment, non-polymerizable 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, fatty alcohol sulfate and phosphate or any salt thereof.In another embodiment, surfactant can be alkyl alcohol ethoxylate sulfate or any salt thereof.

[0074] 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.

[0075] In addition to the superior benefits described above, including superior DPUR, hardness, blocking resistance, or combination of properties, the use of the polymerizable surfactants described herein in emulsion polymerization imparts at least one of the following advantages to latex and / or coating applications: water whitening resistance, high temperature whitening resistance, moderate reactivity, PME stability, good process control, and superior application performance (e.g., water sensitivity).

[0076] The following examples are illustrative of preferred embodiments of polymerizable surfactants, coating compositions having polymers formed from at least one polymerizable surfactant, and methods of making and using the same, but are not intended to be limiting. All composition percentages are based on a total equal to 100% by weight unless otherwise specified. [Example]

[0077] Preparation of polymerizable surfactants Example 1. Polymerizable surfactant C 12 C 14 Preparation of -2.6AGE-15EO ammonium sulfate To 320 g of Alfol 1214 was added 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 inches 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 water content of 0.09%.

[0078] 470.1 g of allyl glycidyl ether was added to the reactor over 120 minutes within a temperature range of 95-105°C. After 30 minutes, the reactor contents were heated to 120°C. After an additional 6 hours within a temperature range of 120-123°C, a sample of the reactor contents was titrated with 0.1 M perchloric acid in acetic acid to naphtholbenzein indicator, which showed 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.

[0079] 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 inches of mercury and held at these conditions for 30 minutes. After breaking the vacuum with nitrogen and applying a positive nitrogen pressure of 1.1 bar, the reactor contents were heated to 155°C, and then 541 g of ethylene oxide was fed subsurface to 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 again with nitrogen gas for 10 minutes before being discharged. 889 g of clear liquid product was recovered from the reactor.

[0080] 647.3 g of the aforementioned adduct was charged to a 1-liter reactor, which was then stirred at 350 RPM, a nitrogen sparge at approximately 25 ml / min was started, and heated to 65°C. Dicyandiamide (0.36 g) was charged to the reactor, which was 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 dividing the charge into five 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.

[0081] 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 added to the stirring water. 524.9 g of the above adduct, with an activity level of 100% by the Hyamine test, was slowly added in a steady stream to the water, ensuring the pH remained above 7. An additional 231 g of deionized water was added to give an estimated 27% active solution. Agitation was maintained for 30 minutes. The clear, amber liquid was bottled. The % actives was determined to be 29.1%.

[0082] 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 water content of 0.06%.

[0083] 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 using naphtholbenzein indicator to show an alkalinity of 0.125 mmol / g in the presence of tetrabutylammonium bromide, indicating essentially 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.

[0084] 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 inches of mercury 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 to 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, then purged again with nitrogen gas for 10 minutes before being discharged. 876 g of clear liquid product was recovered from the reactor.

[0085] 691.4 g of the aforementioned adduct was charged to a 1-liter reactor, which was then stirred at 350 RPM, a nitrogen sparge at approximately 25 ml / min was started, and heated to 65°C. Dicyandiamide (0.39 g) was charged to the reactor, which was then sparged for 1 hour to help reduce / remove dissolved oxygen, which contributes to color. 84.65 g of sulfamic acid was charged to the reactor over 1 hour by dividing the charge into five 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 25%.

[0086] 1165.61 g of deionized water was placed in a 2-gallon, open-top 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 the Hyamine test, was slowly added in a steady stream to the water, ensuring 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 % active matter was determined to be 29.27%.

[0087] Examples 1 and 2. Polymerizable surfactants A and B for Examples 1 and 2 are summarized in Table 1 below, and the molar ratios of the starting materials are adjusted accordingly.

[0088] [Table 1]

[0089] Preparation of latex polymer Example 3. Preparation of latex polymer by emulsion polymerization using surfactant A Deionized water (245.0 g) and polymerizable surfactant A (29.10% solids, 7.5 g) were added to a reactor suitable for emulsion polymerization equipped with stirring, heating, and cooling means with a slow, continuous nitrogen purge. Under continuous stirring, the temperature of the reactor was increased to 80°C. At 80°C, 31.50 g of monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (103 g), polymerizable surfactant A (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g) with 20 g of DI water, 2.4 g of ammonium bicarbonate, 1.7 g of zinc oxide, and 7 g of a 28% ammonia complex solution. Once the reactor temperature stabilized at 80°C, a solution of ammonium persulfate (0.6g dissolved in 10g deionized water) was added to the reactor.

[0090] After 25 minutes, a sample was taken from the reactor for particle size analysis. The remaining monomer pre-emulsion and initiator solution (1.5g dissolved in 60g deionized water) were then continuously added to the reactor over a 3-hour period at a temperature of 80-83°C. The monomer pre-emulsion addition was completed over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. A chaser solution (0.4g t-butyl hydroperoxide dissolved in 5g DI water and 0.2g Bruggolite FF6 dissolved in 5g DI water) was then charged to the reactor. The reactor was held at 80°C for an additional 30 minutes until the final solids value was constant or approached the maximum theoretical value. The resulting polymer dispersion had a solids content of 51.2% and an average particle size of 134.2 d.nm. The reactor was cooled to below 40°C, and the resulting latex was filtered through a 200µm polyester filter. The calculated Tg of this polymer is about −35° C. The latex properties are shown in Table 2.

[0091] Example 4. Preparation of latex polymer by using surfactant A in the presence of benzophenone via emulsion polymerization A similar latex polymer was prepared following the same emulsion polymerization procedure as described in Example 3, except that benzophenone was present in the reaction.

[0092] Deionized water (248.0 g) and polymerizable surfactant A (29.10% solids, 7.5 g) were added to a reactor suitable for emulsion polymerization equipped with stirring, heating, and cooling means with a slow, continuous nitrogen purge. Under continuous stirring, the temperature of the reactor was increased to 80°C. At 80°C, 31.50 g of monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (109.6 g), polymerizable surfactant A (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g), as well as benzophenone (4 g), adjusted with 20 g of DI water, 2.4 g of ammonium bicarbonate, 1.7 g of zinc oxide, and 7 g of a 28% ammonia complex solution. Once the reactor temperature stabilized at 80°C, a solution of ammonium persulfate (0.6g dissolved in 10g deionized water) was added to the reactor.

[0093] After 25 minutes, a sample was taken from the reactor for particle size analysis. The remaining monomer pre-emulsion and initiator solution (1.5 g dissolved in 60 g deionized water) were then continuously added to the reactor over a 3-hour period at a temperature of 80-83°C. The monomer pre-emulsion addition was completed over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. A chaser solution (0.4 g t-butyl hydroperoxide dissolved in 5 g DI water and 0.2 g Bruggolite FF6 dissolved in 5 g DI water) was then charged to the reactor. The reactor was held at 80°C for an additional 30 minutes until the final solids value was constant or approached the maximum theoretical value. The resulting polymer dispersion had a solids content of 51.2% and an average particle size of 128.3 d.nm. The reactor was cooled to below 40°C, and the resulting latex was filtered through a 200 μm polyester filter. The calculated Tg of this polymer is about −35° C. The latex properties are shown in Table 2.

[0094] Comparative Example 5. Preparation of Latex Polymer by Emulsion Polymerization Using Comparative Conventional Surfactants (i.e., Non-Polymerizable Surfactants) A comparative latex polymer was prepared according to the same emulsion polymerization procedure described in Example 3, except that a conventional non-polymerizable surfactant was used in place of the polymerizable surfactant.

[0095] Deionized water (245.0 g) and surfactant Aerosol EF810 (30% solids, 7.5 g), a non-polymerizable surfactant, were added to a reactor suitable for emulsion polymerization equipped with stirring, heating, and cooling means with a slow, continuous nitrogen purge. Under continuous stirring, the temperature of the reactor was increased to 80°C. At 80°C, 31.50 g of monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (103 g), Aerosol EF810 (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g), adjusted with 20 g of DI water, 2.4 g of ammonium bicarbonate, 1.7 g of zinc oxide, and 7 g of a 28% ammonia complex solution. Once the reactor temperature stabilized at 80°C, a solution of 6% ammonium persulfate (0.6g dissolved in 10g deionized water) was added to the reactor.

[0096] After 25 minutes, a sample was taken from the reactor for particle size analysis. The remaining monomer pre-emulsion and initiator solution (1.5g dissolved in 60g deionized water) were then continuously added to the reactor over a 3-hour period at a temperature of 80-83°C. The monomer pre-emulsion addition was completed over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. A chaser solution (0.4g t-butyl hydroperoxide dissolved in 5g DI water and 0.2g Bruggolite FF6 dissolved in 5g DI water) was then charged to the reactor. The reactor was held at 80°C for an additional 30 minutes until the final solids value was constant or approached the maximum theoretical value. The resulting polymer dispersion had a solids content of 51.5% and an average particle size of 131.1 d.nm. The reactor was cooled to below 40°C, and the resulting latex was filtered through a 200µm polyester filter. The calculated Tg of this polymer is about −35° C. The latex properties are shown in Table 2.

[0097] Comparative Example 6. Preparation of Latex Polymer by Using Comparative Conventional Surfactants (i.e., Non-Polymerizable Surfactants) in the Presence of Benzophenone by Emulsion Polymerization A comparative latex polymer was prepared following the same emulsion polymerization procedure as described in Comparative Example 5 (i.e., by using a conventional non-polymerizable surfactant), except that benzophenone was also present in the reaction.

[0098] Deionized water (245.0 g) and Aerosol EF810 surfactant (30% solids, 7.5 g), a non-polymerizable surfactant, were added to a reactor suitable for emulsion polymerization equipped with stirring, heating, and cooling means with a slow, continuous nitrogen purge. Under continuous stirring, the reactor temperature was increased to 80°C. At 80°C, 31.50 g of monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (103 g), Aerosol EF810 (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g), as well as benzophenone (4 g), adjusted with 20 g of DI water, 2.4 g of ammonium bicarbonate, 1.7 g of zinc oxide, and 7 g of a 28% ammonia complex solution. Once the reactor temperature stabilized at 80°C, a solution of 6% ammonium persulfate (0.6g dissolved in 10g deionized water) was added to the reactor.

[0099] After 25 minutes, a sample was taken from the reactor for particle size analysis. The remaining monomer pre-emulsion and initiator solution (1.5g dissolved in 60g deionized water) were then continuously added to the reactor over a 3-hour period at a temperature of 80-83°C. The monomer pre-emulsion addition was completed over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. A chaser solution (0.4g t-butyl hydroperoxide dissolved in 5g DI water and 0.2g Bruggolite FF6 dissolved in 5g DI water) was then charged to the reactor. The reactor was held at 80°C for an additional 30 minutes until the final solids value was constant or approached the maximum theoretical value. The resulting polymer dispersion had a solids content of 51.1% and an average particle size of 122.1 d.nm. The reactor was cooled to below 40°C, and the resulting latex was filtered through a 200µm polyester filter. The calculated Tg of this polymer is about −35° C. The latex properties are shown in Table 2.

[0100] [Table 2]

[0101] Example 7. The latex polymers prepared in Examples 3 and 4 and Comparative Examples 5 and 6 were formulated into a 45% PVC exterior elastomeric paint for masonry or other building substrates. The paint formulation is shown in Table 3a.

[0102] [Table 3]

[0103] The hardness, blocking resistance, and DPUR of formulated exterior paints containing the latex polymers prepared in Examples 3 and 4 and Comparative Examples 5 and 6 were evaluated according to the following methods. The paints were drawn down on different substrates and allowed to dry for 1 to 7 days according to the applicable ASTM method. Pendulum hardness properties were measured according to ASTM D4366, and the results are shown in Table 3b below and illustrated in Figures 1 and 2. The paints were drawn down on glass panels, and values ​​were averaged based on three tests for each panel. As can be seen, the latex polymers prepared using polymerizable surfactants improved the hardness of the paints, with and without benzophenone, compared to paints with latex polymers prepared using conventional non-polymerizable surfactants.

[0104] [Table 4]

[0105] The blocking resistance of the formulated exterior paints containing the latex polymers prepared in Examples 3 and 4 and Comparative Examples 5 and 6 was also evaluated. Blocking resistance was measured in accordance with ASTM D4946. Blocking resistance tests were conducted both at room temperature and at elevated temperatures (i.e., 50°C). High-temperature blocking resistance tests were conducted at 50°C for 30 minutes under the condition of a 1 kg weight based on standard methods, and the test panels are shown in Figure 3. As can be clearly seen, the test panels coated with the paint containing the latex polymer prepared using the polymerizable surfactant exhibit significantly superior performance. That is, the latex polymer prepared using the polymerizable surfactant significantly improved the blocking resistance of the paint.

[0106] DPUR performance was tested according to ASTM D3719. Test panels were painted using formulated exterior paints containing the latex polymers prepared in Examples 3 and 4 and Comparative Examples 5 and 6. The test panels were then placed outdoors and stain resistance tested by visually inspecting the paint surface over time. Color L values ​​were also measured according to ASTM D5326 at the start of the test and after outdoor exposure. The test results are shown in Table 3c below and in Figure 4 after two months of outdoor exposure. As can be seen, the paints containing the latex polymers prepared using the polymerizable surfactant exhibited lower delta (Δ) L value changes, indicating improved DPUR.

[0107] [Table 5]

[0108] Example 8. Preparation of latex polymer by using surfactant B in an all-acrylic latex by emulsion polymerization Deionized water (145.6 g) and polymerizable surfactant B (29.27% ​​solids, 4.4 g) were slowly added to a reactor suitable for emulsion polymerization equipped with stirring, heating, and cooling means while continuously purging with nitrogen. The temperature of the reactor was increased to 80°C under continuous stirring. At 80°C, 10.9 g of Monomer Pre-Emulsion I was charged to the reactor. Monomer Pre-Emulsion I was prepared by mixing water (28.2 g), polymerizable surfactant B (3.5 g), methyl methacrylate (11 g), butyl acrylate (62.2 g), methacrylic acid (0.44 g), and Sipomer PAM 600 (3.94 g). Once the reactor temperature stabilized at 80°C, a solution of ammonium persulfate (0.61 g dissolved in 4.87 g of deionized water) was added to the reactor.

[0109] After 25 minutes, a sample was taken from the reactor for particle size analysis. The remaining monomer pre-emulsion I [28.2 g water, 3.5 g polymerizable surfactant B, 11 g methyl methacrylate, 62.2 g butyl acrylate, 0.44 g methacrylic acid, 3.94 g Sipomer PAM600] and initiator solution (0.31 g dissolved in 30.3 g deionized water) were then continuously added to the reactor at a temperature of 80–83 °C within 1 hour. Monomer pre-emulsion II [50.6 g water, 0.9 g polymerizable surfactant A, 99.2 g methyl methacrylate, 41.5 g butyl acrylate, 4.0 g methacrylic acid] was then continuously added to the reactor within 2 hours. A chaser solution (0.18 g t-butyl hydroperoxide dissolved in 2.45 g DI water and 0.18 g isoascorbic acid dissolved in 2.45 g DI water) was then charged to the reactor. The reactor was held at 80°C for an additional 30 minutes until the final solids value was constant or approached the maximum theoretical value. The resulting polymer dispersion had a solids content of 45.5% and an average particle size of 121.8 d.nm. The reactor was cooled to below 40°C, and the resulting latex was filtered through a 200 μm polyester filter. The calculated Tg of this polymer was approximately 10°C. The latex properties are shown in Table 4.

[0110] Example 9. Preparation of Latex Polymer by Using Surfactant B in an All-Acrylic Latex by Emulsion Polymerization Deionized water (145.6 g) and polymerizable surfactant B (29.27% ​​solids, 4.4 g) were slowly added to a reactor suitable for emulsion polymerization equipped with stirring, heating, and cooling means while continuously purging with nitrogen. The temperature of the reactor was increased to 80°C under continuous stirring. At 80°C, 10.9 g of Monomer Pre-Emulsion I was charged to the reactor. Monomer Pre-Emulsion I was prepared by mixing water (78.9 g), polymerizable surfactant A (4.4 g), methyl methacrylate (110.3 g), butyl acrylate (63.9 g), methacrylic acid (5.5 g), and Sipomer PAM 600 (3.94 g). Once the reactor temperature stabilized at 80°C, a solution of ammonium persulfate (0.61 g dissolved in 4.87 g of deionized water) was added to the reactor.

[0111] After 25 minutes, a sample was taken from the reactor for particle size analysis. The remaining monomer pre-emulsion and initiator solution (0.31 g dissolved in 30.3 g deionized water) were then continuously added to the reactor within 2 hours at a temperature of 80-83 °C. Then, the monomer pre-emulsion (butyl acrylate [a mixture of 39.7 g and Pre-emulsion I (26.7 g)]) was continuously fed into the reactor within 1 hour. Then, chaser solutions (0.18 g t-butyl hydroperoxide dissolved in 2.45 g DI water and 0.18 g isoascorbic acid dissolved in 2.45 g DI water) were dosed into the reactor. The reactor was held at 80 °C for an additional 30 minutes until the final solids value was constant or approached the maximum theoretical value. The resulting polymer dispersion had a solids content of 44.0% and an average particle size of 123.2 d.m. The reactor was cooled to below 40° C. and the resulting latex was filtered through a 200 μm polyester filter. The calculated Tg of this polymer was approximately 10° C. The latex properties are shown in Table 4.

[0112] Comparative Example 10. Preparation of Latex Polymer by Emulsion Polymerization Using Comparative Conventional Surfactants (i.e., Non-Polymerizable Surfactants) Deionized water (240 g) and Rhodapon UB STD surfactant (30% solids, 6.1 g) were added to a reactor suitable for emulsion polymerization equipped with stirring, heating, and cooling means with a slow, continuous nitrogen purge. Under continuous stirring, the reactor temperature was increased to 80°C. At 80°C, 25.1 g of monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (130 g), Rhodapon UB STD surfactant (12.2 g), methyl methacrylate (180 g), butyl acrylate (169.2 g), and methacrylic acid (10.8 g). Once the reactor temperature stabilized at 80°C, a solution of ammonium persulfate (1.0 g dissolved in 8 g of deionized water) was added to the reactor.

[0113] After 25 minutes, a sample was taken from the reactor for particle size analysis. The remaining monomer pre-emulsion and initiator solution (0.5 g dissolved in 50 g deionized water) were then continuously added to the reactor within 3 hours at a temperature of 80-83°C. A chaser solution (0.3 g t-butyl hydroperoxide dissolved in 4 g DI water and 0.3 g isoascorbic acid dissolved in 4 g DI water) was then added to the reactor. The reactor was held at 80°C for an additional 30 minutes until the final solids value remained constant or approached the maximum theoretical value. The solids content of the resulting polymer dispersion was 44.7% and the average particle size was 117.4 d.nm. The reactor was cooled to below 40°C, and the resulting latex was filtered through a 200 μm polyester filter. The calculated Tg of this polymer was approximately 10°C. The latex properties are listed in Table 4.

[0114] [Table 6]

[0115] Example 11. The latex polymers prepared in Examples 8 and 9 along with Comparative Example 10 were formulated into a 22% PVC semi-gloss exterior paint. The paint formulation is shown in Table 5a.

[0116] [Table 7]

[0117] As above, the block resistance and DPUR of the formulated exterior paints in Table 5a were evaluated according to the following methods. The paints were drawn down onto different substrates and allowed to dry for 1 to 7 days according to the applicable ASTM method. Block resistance was tested according to ASTM D4946. Hot-block resistance tests were conducted at 50°C for 30 minutes under a 1 kg weight condition according to standard methods. Test results were reported on a scale of 1 to 10, with 1 being the worst and 10 being the best. The test results are shown in Table 5b below and in Figure 5. As can be seen, the paints containing the latex polymer prepared using the polymerizable surfactant exhibit significantly superior performance.

[0118] [Table 8]

[0119] DPUR performance was tested according to a modified procedure based on ASTM D3719. Test panels were painted using formulated exterior paints containing the latex polymers prepared in Examples 8 and 9, along with Comparative Example 10. After coating with each formulated exterior paint, the test panels were allowed to dry for 7 days. A uniform coating of brown iron oxide (BIO) slurry was then brushed onto a portion of the surface of the test panel without contaminating the surface of the test panel. Only a portion of the surface of the test panel was coated with the BIO slurry; the remaining surface of the test panel was not coated with the BIO slurry for comparison purposes. A brown oxide slurry was formed by dissolving two drops of Rhodoline® 111 in 250 g of water, then adding 125 g of BIO pigment, and then dispersing the pigment with a benchtop stirrer until homogeneous. The brown oxide slurry-coated test panel was then air-dried until the slurry was completely dry (i.e., a minimum of four hours, or preferably overnight, to ensure the slurry was completely dry). The test panel is then gently washed under running water, rubbing gently and evenly with a clean piece of cheesecloth, including the area where the brown oxide slurry was applied and dried. All excess slurry is removed. Reflectance readings are then reported according to ASTM D5326, making sure to average at least three readings for both treated and untreated areas of the test sample. DPUR is recorded as % removed - higher numbers indicate better DPUR. Test results are shown in Table 5c below and in Figure 6. The results indicate that paints containing latex polymers prepared using polymerizable surfactants exhibit improved DPUR.

[0120] [Table 9]

[0121] It will be apparent that the subject matter thus described may be modified or varied in many ways, including equivalents thereof. Such modifications and variations should not be regarded as a departure from the spirit and scope of the subject matter, and all such modifications and variations, including equivalents thereof, are intended to be included within the scope of the appended claims.

Claims

1. 1. A coating composition comprising a polymer formed from at least one polymerizable surfactant, the polymerizable surfactant having formula (I): 【Chemistry 1】 (In the formula: R １ is C ８ ~C １４ Alkyl group, preferably C １０ ~C １４ an alkyl group, a bicyclic group, or a combination thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; M ＋ Is, H ＋ , Na ＋ , NH4 ＋ , K. ＋ , Li ＋ , or a combination thereof) A coating composition comprising:

2. M ＋ Na ＋ , NH4+, or a combination thereof.

3. 3. The coating composition according to claim 1, wherein x is 2 to 4 and y is 14 to 18.

4. The coating composition of any one of claims 1 to 3, wherein the coating composition is an elastomeric coating, an architectural coating, or both.

5. The coating composition of any one of claims 1 to 4, wherein the coating composition is a latex coating.

6. 6. The coating composition of any one of claims 1 to 5, wherein the coating composition has a glass transition temperature (Tg) of -40°C to -20°C as measured by ASTM D3418.

7. 6. The coating composition of any one of claims 1 to 5, wherein the coating composition has a glass transition temperature (Tg) of 10°C to 40°C as measured by ASTM D3418.

8. R １ However, one or more (C １ ~C ６ ) a bicyclo optionally substituted on one or more ring carbon atoms by an alkyl group; ［ｄ．ｅ．ｆ］ Heptyl group or bicyclo ［ｄ．ｅ．ｆ］ 8. The coating composition of claim 1, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5.

9. The coating composition of any one of claims 1 to 8, wherein the coating composition has improved stain resistance (DPUR) as measured by ASTM D3719.

10. The coating composition of any one of claims 1 to 9, wherein the coating composition has improved hardness as measured by ASTM D4366.

11. The coating composition of any one of claims 1 to 10, wherein the coating composition has improved resistance to blocking as measured by ASTM D4946.

12. The coating composition of any one of claims 1 to 11, wherein the coating composition is completely benzophenone-free.

13. 10. A method for producing a coating composition comprising a polymer formed from at least one polymerizable surfactant according to claim 1, the method comprising emulsion polymerizing the at least one polymerizable surfactant with at least one other monomer.

14. 14. The method of claim 13, wherein the at least one other monomer is selected from an acrylate monomer, a styrene monomer, a vinyl ester monomer, or a combination thereof.

15. 15. The method of claim 13 or 14, wherein the at least one other monomer is selected from methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylate and blends thereof, acrylic acid, methacrylic acid, styrene, vinyl toluene, vinyl acetate, vinyl esters of carboxylic acids higher than acetic acid including vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride, and the like, and mixtures thereof.

16. 16. The method of any one of claims 13 to 15, further comprising a surfactant selected from sodium alkylbenzene sulfonate 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, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof, alkyl alcohol ethoxylate sulfate or any salt thereof, and combinations thereof.

17. 17. The method of any one of claims 13 to 16, further comprising at least one component selected from a chain transfer agent, an additive for adjusting pH, a compound utilized as a protective colloid, and combinations thereof.

18. The method of any one of claims 13 to 17, wherein the coating composition is completely benzophenone-free.

19. Formula (I): 【Chemistry 2】 (In the formula: R １ is C ８ ~C １４ Alkyl group, preferably C １０ ~C １４ an alkyl group, a bicyclic group, or a combination thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; M ＋ Is, H ＋ , Na ＋ , NH4 ＋ , K. ＋ , Li ＋ , or a combination thereof) 10. Use of the polymerizable surfactant of claim 1 to form a polymer for use in a coating composition.

20. 20. The use of claim 19, wherein the coating composition is an elastomeric coating, an architectural coating, or both.

21. 21. The use according to claim 19 or 20, wherein the coating composition is a latex coating.

22. The use according to any one of claims 19 to 21, further comprising at least one component selected from a chain transfer agent, an additive for adjusting pH, a compound utilized as a protective colloid, and combinations thereof.

23. Use according to any one of claims 19 to 22, wherein the coating composition is completely benzophenone-free.

24. 1. Use of a coating composition comprising a polymer formed from at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (I): 【Transformation 3】 (In the formula: R １ is C ８ ~C １４ Alkyl group, preferably C １０ ~C １４ an alkyl group, a bicyclic group, or a combination thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; M ＋ Is, H ＋ , Na ＋ , NH4 ＋ , K. ＋ , Li ＋ , or a combination thereof) 10. The use of a polymerizable surfactant of claim 1 to coat at least a portion of a surface of a substrate, wherein the coating composition provides improved stain resistance (DPUR), hardness, blocking resistance, or a combination thereof.

25. 25. The use of claim 24, wherein the coating composition is completely benzophenone-free.

Images