Combinations of crosslinkers to improve coating properties

Abstract

A multiphase polymer comprising a crosslinking monomer and a multifunctional amine is disclosed. The multiphase polymer comprises T g The first phase polymer is 60°C to 240°C, T g The second phase polymer and T g A soft phase polymer having a temperature of ‑25° C. to 30° C. The crosslinking monomers include triacrylates such as trimethylolpropane triacrylate, unsaturated alkoxysilanes, and unsaturated ketone monomers reacted with multifunctional amines. Contrary to conventional wisdom, the incorporation of trimethylolpropane triacrylate reduces the minimum film forming temperature of the multiphase polymer. This unusual reduction in MFFT helps reduce VOC requirements to form good films at low VOCs. Other crosslinking monomers including unsaturated alkoxysilanes and unsaturated ketone monomers reacted with multifunctional amines can improve print resistance, anti-blocking properties, and reduce the viscosity of the coating film. The multiphase polymer is particularly suitable for deep base coatings.

Description

Technical Field

[0001] The present disclosure relates to a coating composition including a binder that exhibits a low minimum film forming temperature, high pendulum hardness, high blocking resistance, high printing resistance, and low tack. Background Art

[0002] Coatings with low pigment volume concentration (PVC), such as deep-based architectural coatings, are softer than coatings with high PVC. Due to the presence of soft polymers that are generally used to form good films under low volatile organic compound (VOC) concentrations, these coatings become softer. A large amount of low VOC water-based colorants are usually included in these coatings to achieve dark color, thereby further softening the coating. The soft and tacky deep-based coatings produced by low PVC, soft polymers and a large amount of water-based colorants carrying soft materials combine to cause surface tackiness, poor anti-blocking and poor printability. It is necessary to solve the tackiness and poor anti-blocking and printability of low PVC, low VOC and deep-based coatings. Compositions and methods described herein meet these and other requirements. Summary of the invention

[0003] Disclosed herein are multiphase polymer particles comprising a combination of crosslinking monomers and multifunctional amines, which form films at low VOCs and provide improved hardness, improved printability, improved anti-blocking and lower viscosity in deep base coatings. In some cases, the multiphase polymer particles comprise multifunctional acrylate trimethylolpropane triacrylate, unsaturated alkoxysilanes such as vinyl triethoxysilane, unsaturated ketone monomers such as methacrylate acetoacetoxyethyl or diacetone acrylamide, and polyamines reacted with ketone monomers. Compared with conventional knowledge, the incorporation of trimethylolpropane triacrylate reduces the minimum film forming temperature of the multiphase polymer particles. This unusual reduction in MFFT helps to reduce VOC requirements to form good films at low VOCs. Other crosslinking monomers including unsaturated alkoxysilanes and unsaturated ketone monomers reacted with multifunctional amines improve the printability, anti-blocking and reduce viscosity of deep base coatings. The polymer particles are synthesized in multiple phases with different Tgs.

[0004] In some embodiments, the first phase is a hard phase polymer having a glass transition temperature of 60°C to 240°C, the second phase polymer has a glass transition temperature of 40°C to 240°C, and the third phase is a soft phase polymer having a glass transition temperature of -25°C to 30°C. The first phase polymer typically has no acid groups from polymerized monomers, while the second phase polymer has acid groups from polymerized unsaturated monomers such as carboxylic acid monomers, sulfuric acid monomers, or phosphorous acid monomers. The soft phase polymer may or may not have any acid groups from polymerized unsaturated monomers. These polymer particles, which are unusually crosslinked by a variety of crosslinking agents, provide improved hardness, improved anti-blocking properties, improved print resistance, and lower adhesion to low VOC and low PVC deep base coatings.

[0005] In some examples, the multiphase polymer may include T g The first phase polymer is 60°C to 240°C (e.g., 80°C to 240°C, or 80°C to 150°C); T g A second phase polymer having a temperature of 40° C. to 240° C. (e.g., 60° C. to 240° C., or 70° C. to 120° C.), and the second phase polymer is derived from monomers comprising an ethylenically unsaturated acid monomer, one or more multifunctional crosslinking monomers, one or more (meth)acrylates, and optionally an unsaturated ketone monomer, an unsaturated silane monomer, a multifunctional amine reactive with the ketone monomer, styrene, or a combination thereof; and T g A soft phase polymer having a temperature of -25°C to 30°C (e.g., -25°C to 15°C, or -15°C to less than 15°C), and the soft phase polymer is derived from monomers including one or more multifunctional crosslinking monomers, one or more (meth)acrylates, unsaturated ketone monomers, unsaturated silane monomers, multifunctional amines reactive with the unsaturated ketone monomers, and optionally styrene.

[0006] The first phase polymer can be derived from monomers including methacrylate monomers, vinyl aromatic monomers or combinations thereof. For example, based on the total weight of the first phase polymer, the first phase polymer can contain styrene in an amount greater than 0 wt %, such as 10 wt % to 100 wt %, or preferably 40 wt % to 100 wt %. In certain embodiments, the first phase polymer is a polystyrene seed polymer. Based on the total weight of the multiphase polymer, the first phase polymer can be present in an amount of 10 wt % or less, preferably 0.1 wt % to 10 wt %, or more preferably 1 wt % to 5 wt %. The first phase polymer can have a volume average particle size of 60 nm or less, such as 5 nm to 30 nm.

[0007] In some aspects, the second phase polymer can be derived from an ethylenically unsaturated acid monomer, one or more multifunctional crosslinking monomers, one or more (meth)acrylates, unsaturated ketone monomers, unsaturated silane monomers, multifunctional amines reacted with the ketone monomers, and optional styrene. The ethylenically unsaturated acid monomers in the second phase polymer can be selected from carboxylic acid monomers, phosphorous acid monomers, sulfuric acid monomers, or mixtures thereof. Examples of suitable ethylenically unsaturated acid monomers include acrylic acid; methacrylic acid; itaconic acid; maleic acid; fumaric acid; crotonic acid; phosphorous acid monomers; vinylphosphonic acid; allylphosphonic acid; 2-acrylamide-2-methylpropanephosphonic acid; phosphonostyrene; 2-methacrylamide-2-methylpropanephosphonic acid; phosphates or phosphonates of hydroxyalkyl unsaturated monomers, such as 2-phosphoethyl (meth)acrylate; 2-phosphopropyl (meth)acrylate; 3-phosphopropyl (meth)acrylate; 3-phospho-2-hydroxypropyl (meth)acrylate; 2-acrylamide-2-methylpropanesulfonic acid; styrenesulfonic acid; mixtures thereof or salts thereof. The phosphorous acid monomer may have the formula CH2=C(R)-C(O)-O-(R 1 O) n -P(O)(OH)2, where R is H or CH3, R 1 is an alkyl group, and n is 0 to 50. Alternatively, the phosphorous acid monomer may be one sold under the trade name PAM 100, PAM 200, Sipomer PAM 600 or Monomers sold as PAM 4000. The ethylenically unsaturated acid monomer may be present in the second phase polymer in an amount of from 0.01% to 6%, preferably from 0.5% to 3.0% by weight of the second phase polymer.

[0008] As described herein, the soft phase polymer may or may not include an acid monomer. In some embodiments, one or both of the soft phase polymer and the first phase polymer do not include an acid monomer. In some embodiments, only the first phase polymer does not include an acid monomer. When present, the ethylenically unsaturated acid monomer may be present in the soft phase polymer in an amount of 0.01% to 6%, preferably 0.5% to 3.0%, by weight of the soft phase polymer.

[0009] The second phase polymer and the soft phase polymer both include one or more multifunctional crosslinking monomers. The multifunctional crosslinking monomer can include two or more polymerizable carbon-carbon double bonds. For example, the multifunctional crosslinking monomer can be selected from divinyl monomer, diallyl monomer, trivinyl monomer, triallyl monomer, di(methyl)acrylate, tri(methyl)acrylate, tetra(methyl)acrylate, penta(methyl)acrylate), or a combination thereof. Multifunctional crosslinking monomers also include divinyl (methyl)acrylate, diallyl (methyl)acrylate, allyl (methyl)acrylate, trivinyl (methyl)acrylate, triallyl (methyl)acrylate, divinylbenzene, trivinyl benzene, diallyl maleate or a combination thereof. In some instances, the multifunctional crosslinking monomer includes tri(methyl)acrylate, preferably trimethylolpropane triacrylate.

[0010] Without wishing to be bound by theory, it is believed that the inclusion of trimethylolpropane triacrylate in both the second phase polymer and the soft phase polymer increases the phase separation between the second phase polymer and the soft phase polymer. This increase in phase separation therefore reduces the minimum film forming temperature of the multiphase polymer. The amount of multifunctional crosslinking monomers such as trimethylolpropane triacrylate present in the second phase polymer can be 0.01-5% by weight of the second phase polymer, such as 0.2-5% by weight, or preferably 0.5-5% by weight. The amount of multifunctional crosslinking monomers such as trimethylolpropane triacrylate present in the soft phase polymer can be 0.01-5% by weight of the soft phase polymer, such as 0.2-5% by weight, or preferably 0.5-5% by weight. The amount of multifunctional crosslinking monomers such as trimethylolpropane triacrylate present in the multiphase polymer can be 0.02-10% by weight, 0.2-10% by weight, 0.2-5% by weight, or 0.5-5% by weight of the multiphase polymer.

[0011] The multiphase polymer also includes an unsaturated ketone monomer. The unsaturated ketone monomer can be selected from diacetone acrylamide, acetoacetoxyalkyl (meth) acrylates such as acetoacetoxyethyl methacrylate, or a combination thereof. The unsaturated ketone monomer is present in the soft phase polymer in an amount of 0.01%-15%, 0.01%-10%, preferably 0.5%-10%, and more preferably 0.5%-5% by weight of the soft phase polymer. The unsaturated ketone monomer is also present in the second phase polymer in an amount of 0.01%-15%, preferably 0.5%-15%, and more preferably 0.5%-5% by weight of the second phase polymer.

[0012] As described herein, the multiphase polymer includes a multifunctional amine, such as a polyetheramine or a polyhydrazide. The multifunctional amine reacts with the ketone of the ketone monomer present in the soft phase polymer and / or the second phase polymer. After the soft phase polymer and / or the second phase polymer are formed, the multifunctional amine reacts with the unsaturated ketone monomer and can therefore exist as a side group of the polymer backbone. The multifunctional amine can be present in the multiphase polymer in an amount of 0.01%-3%, preferably 0.5%-2%, by weight of the multiphase polymer. In some embodiments, the polyetheramine or polyhydrazide or a combination thereof is incorporated in a ratio of 1:0.1 to 1:1.2 of the equivalent ratio of the ketone group to the amine group or the hydrazide group or the combination of the amine group and the hydrazide group.

[0013] The multiphase polymer may also include unsaturated silane monomers, such as unsaturated alkoxysilanes. Suitable unsaturated silane monomers include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(2-methoxyethoxysilane), vinyl triisopropoxysilane, (3-methacryloxypropyl)-trimethoxysilane, (3-methacryloxypropyl)-triethoxysilane, (3-methacryloxypropyl)-triisopropoxysilane, 2-methyl-2-acrylic acid 3-[tri-(1-methylethoxy)-silyl]-propyl ester, (3-methacryloxypropyl)-methyldiethoxysilane, oligomers thereof, polymers thereof, or combinations thereof. The unsaturated silane monomer may be present in the soft phase polymer in an amount of 0.01%-5%, preferably 0.5%-5%, based on the weight of the soft phase polymer. The unsaturated silane monomer may be present in the second phase polymer in an amount of 0.01%-5%, preferably 0.5%-5%, based on the weight of the second phase polymer. It is believed that the inclusion of unsaturated silane monomers can improve the anti-blocking properties of the multiphase polymer. In some embodiments, aminoalkoxysilane or its epoxyalkoxysilane oligomer can be added to the multiphase polymer. Specific examples include 3-aminopropyltrialkoxysilane, 3-epoxypropyltrialkoxysilane, etc.

[0014] The multiphase polymer also includes one or more (meth) acrylate monomers. In some cases, the multiphase polymer includes at least one methacrylate monomer and at least one acrylate monomer. The methacrylate monomer can be selected from methyl methacrylate, ureido methacrylate, n-butyl methacrylate, isobornyl methacrylate or a combination thereof. The acrylate monomer can be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate or a combination thereof. In some embodiments, the second phase polymer can include methacrylate monomers in an amount of 40% to 90% by weight (e.g., 60% to 90% by weight) of the second phase polymer and acrylate monomers in an amount of 1% to 20% by weight (e.g., 1% to 10% by weight or 1% to 5% by weight) of the second phase polymer. In some embodiments, the soft phase polymer may include methacrylate monomers in an amount of 5 wt % to 40 wt % (e.g., 10 wt % to 40 wt % or 10 wt % to 30 wt %) of the soft phase polymer and acrylate monomers in an amount of 40 wt % to 90 wt % (e.g., 60 wt % to 85 wt %) of the soft phase polymer. In general, the one or more (meth)acrylate monomers may be present in an amount of 80 wt % to 97 wt % of the multiphase polymer.

[0015] The multiphase polymer may include one or more other monomers. The one or more other monomers may include (meth) acrylonitrile monomer, (meth) acrylamide monomer, (meth) glycidyl acrylate, (meth) hydroxyalkyl acrylate such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate, or a combination thereof. The one or more other monomers may be present in the first phase, the second phase and / or the soft phase. For example, one or both of the second phase polymer and the soft phase polymer may include styrene.

[0016] In some examples, the second phase polymer and the soft phase polymer in the multiphase polymer can be derived from monomers including 0.1 wt%-5 wt% of a multifunctional crosslinking monomer, the multifunctional crosslinking monomer including a tri(meth)acrylate monomer, preferably trimethylolpropane triacrylate; 0.5 wt%-10 wt% of an unsaturated ketone monomer, the unsaturated ketone monomer including diacetone acrylamide or acetoacetoxyalkyl (meth)acrylate, such as acetoacetoxyethyl methacrylate; 0.1 wt%-5 wt% of an unsaturated silane monomer, preferably an unsaturated alkoxysilane; 0.1 wt%-8 wt% or 0.1 wt%-5 wt% of urea (meth)acrylate; and 80 wt%-97 wt% of two or more (meth)acrylates, comprising at least one methacrylate monomer and at least one acrylate monomer, wherein the weight percentages are based on the total amount of monomers in the second phase polymer and the soft phase polymer. The second phase polymer may also include an acid monomer.

[0017] In certain embodiments, the Tg of the second phase polymer may be 25°C or less, preferably 5°C-25°C, more preferably 5°C-15°C lower than the Tg of the first phase polymer. In certain embodiments, the Tg of the soft phase polymer may be 50°C or more, preferably 50°C-120°C, more preferably 70°C-110°C lower than the Tg of the second phase polymer. Based on the total weight of the multiphase polymer, the second phase polymer may be present in an amount of 50 wt% or less, preferably 10 wt%-50 wt%, 15 wt%-40 wt%, more preferably 15 wt%-35 wt%. Based on the total weight of the multiphase polymer, the soft phase polymer may be present in an amount of 50 wt% or more, preferably 50 wt%-85 wt%, more preferably 50 wt%-70 wt%, most preferably 60 wt%-70 wt%.

[0018] As described herein, the multiphase polymer may exhibit a low MFFT, preferably less than the MFFT of the same polymer without a multifunctional crosslinking monomer in one or both of the second phase polymer and the soft phase polymer. In some examples, the MFFT of the multiphase polymer is 40°C or less. The multiphase polymer may have a volume average particle size of 400 nm or less, preferably 60 nm to 300 nm, more preferably 80 nm to 220 nm, even more preferably 100 nm to 220 nm.

[0019] Also disclosed herein is a coating composition comprising the multiphase polymer. The coating composition may include an amount of 10% to 90% by weight of the coating composition, preferably 30% to 80% by weight of the multiphase polymer. The coating composition may also include a colorant, an inorganic filler, a film-forming aid, a defoamer, a thickener, a tackifier, or a combination thereof. When present, the inorganic filler may be selected from calcium carbonate, titanium dioxide, clay, kaolin, bentonite, mica, talc, natural silica, synthetic silica, natural silicate, synthetic silicate, feldspar, nepheline syenite, wollastonite, diatomaceous earth, barite, glass, attapulgite, zeolite, or a mixture thereof. The inorganic filler may be present in an amount greater than 0% to 70% by weight of the total weight of the coating composition, preferably 5% to 50% by weight, more preferably 5% to 30% by weight.

[0020] The coating composition can be a coating, preferably a deep base coating. The colorant can be present in an amount of 2 wt % to 20 wt % of the deep base coating. The colorant can include a colored pigment, a surfactant, a pigment dispersant and an inorganic filler.

[0021] The pigment volume concentration (PVC) of the coating composition may be 45% or less, preferably 1-30% by volume, and more preferably 1-10% by volume.

[0022] Also disclosed herein is a film prepared from a coating composition comprising a multiphase polymer. When applied as a film to a surface, a coating formulated using a combination of the present polymer and a crosslinker can form a less viscous film at room temperature in less than 24 hours as measured by a cotton ball tack test compared to a coating formulated with the same polymer but without a crosslinker. The film has a print resistance according to ASTM D2064-91; and an anti-blocking property according to ASTM D4946. After curing for 24 hours, the film may also have a print resistance rating of at least 4, preferably 6-10 or 6-8 according to ASTM D2064-91. After curing for 24 hours, the film may have an anti-blocking rating of at least 5 according to ASTM D4946-89 at 50°C. As determined by ASTM D4366-16, the film has a pendulum hardness of at least 6 or at least 7.

[0023] Disclosed herein is a method for preparing a multiphase polymer composition. The method may include a) polymerizing monomers including ethylenically unsaturated acid monomers, multifunctional crosslinking monomers, and one or more (meth)acrylates by emulsion polymerization to form a second phase polymer having a Tg of 40°C to 240°C (preferably 60°C to 240°C, or more preferably 70°C to 120°C), wherein the monomers of step a) are polymerized in the presence of a first phase polymer, and wherein the Tg of the first phase polymer is 60°C to 240°C, preferably 80°C to 240°C, or more preferably 80°C to 150°C. The method disclosed herein also includes step b) polymerizing monomers including one or more multifunctional crosslinking monomers, one or more (meth)acrylates, unsaturated ketone monomers, and unsaturated alkoxysilane monomers by emulsion polymerization to form a soft phase polymer having a Tg of -25°C to 30°C (preferably -25°C to 15°C, or more preferably -15°C to less than 15°C), wherein the monomers of step b) are polymerized in the presence of the first phase polymer and the second phase polymer. Step a) optionally further comprises polymerizing a ketone monomer, an unsaturated alkoxysilane monomer, or a combination of these monomers. The method for preparing a multiphase polymer composition further comprises reacting a multifunctional amine comprising polyhydrazide with the product formed by step b) and step a) to produce a multiphase polymer. In some cases, the multiphase polymer comprises latex particles having a second phase polymer disposed on the surface of the first phase polymer, preferably wherein the first phase polymer forms an inner phase and the second phase polymer surrounds the inner phase. The soft phase polymer may or may not encapsulate the second phase polymer and may form acorn or Janus type particles.

[0024] The details of one or more embodiments are set forth in the description which follows. Other features, objects, and advantages will be apparent from the description and from the claims. DETAILED DESCRIPTION

[0025] The compositions and methods described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein.

[0026] Before disclosing and describing the compositions and methods of the present invention, it should be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, which can of course vary. It should also be understood that the terminology used herein is only for the purpose of describing specific aspects and is not intended to be limiting.

[0027] Throughout this specification and the claims that follow, reference will be made to a number of terms which will be defined to have the following meanings.

[0028] Throughout the description and claims of this specification, the words "comprise", "include" and other forms of these terms, such as "comprising", "comprises", "including" and "includes" are open, non-limiting terms and do not exclude additional elements, such as additional additives, components, integers or steps. Although the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments and are also disclosed.

[0029] As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural forms unless the context clearly dictates otherwise. Thus, for example, reference to "a composition" includes two or more compositions, reference to "an adhesion enhancer" includes two or more adhesion enhancers, reference to "the monomer" includes two or more monomers, etc.

[0030] It should be understood that throughout this specification, the identifiers "first" and "second" are only used to help distinguish the various components and steps of the disclosed subject matter. The identifiers "first" and "second" are not intended to imply any particular order, quantity, preference, or importance of the components or steps modified by these terms.

[0031] As used herein, "(meth)acrylic acid..." includes acrylic acid... and methacrylic acid... and also includes diacrylic acid..., dimethacrylic acid... and polyacrylic acid... and polymethacrylic acid... For example, the term "(meth)acrylate monomer" includes acrylate and methacrylate monomers, diacrylate and dimethacrylate monomers, and other polyacrylate and polymethacrylate monomers.

[0032] The term "polymer" includes homopolymers, copolymers or mixtures thereof.

[0033] Multiphase polymers

[0034] Compositions comprising a multiphase polymer are described herein, wherein the multiphase polymer comprises a combination of crosslinking monomers. Coating formulations comprising the multiphase polymer and methods of making and using the same are also described herein.

[0035] As used herein, the term "multiphase" means that the polymer particle includes two or more phases. For example, the multiphase polymer particle may include two or more phases, three or more phases, four or more phases, or five or more phases.

[0036] The multiphase polymer may comprise (i) T g A first phase or hard phase polymer having a temperature of 60°C to 240°C (eg, 80°C to 240°C, or 80°C to 150°C); (ii) T g The second phase polymer has a temperature of 40°C to 240°C (e.g., 60°C to 240°C, or 70°C to 120°C), and the second phase polymer is derived from monomers comprising an ethylenically unsaturated acid monomer, a multifunctional crosslinking monomer, one or more (meth)acrylates and optionally an unsaturated ketone monomer, an unsaturated silane monomer, a multifunctional amine, styrene, or a combination thereof; and (iii) T g A third phase or soft phase polymer having a temperature of -25°C to 30°C (e.g., -25°C to 15°C, or -15°C to less than 15°C), and the third phase or soft phase polymer is derived from monomers including one or more multifunctional crosslinking monomers, one or more (meth)acrylates, unsaturated ketone monomers, unsaturated silane monomers and multifunctional amines.

[0037] As used herein, the term "theoretical glass transition temperature" or "theoretical T g ” refers to the estimated T of a polymer or copolymer calculated using the Fox equation g The Fox equation can be used to estimate the glass transition temperature of a polymer or copolymer, as described, for example, in LH Sperling, "Introduction to Physical Polymer Science", 2nd ed., John Wiley & Sons, New York, p. 357 (1992) and TG Fox, Bull. Am. Phys. Soc., 1, 123 (1956), both of which are incorporated herein by reference. For example, the theoretical glass transition temperature of a copolymer derived from monomers a, b, ... and i can be calculated according to the following equation

[0038]

[0039] where w a is the weight fraction of monomer a in the copolymer, T ga is the glass transition temperature of the homopolymer of monomer a, w b is the weight fraction of monomer b in the copolymer, T gb is the glass transition temperature of the homopolymer of monomer b, w i is the weight fraction of monomer i in the copolymer, T gi is the glass transition temperature of the homopolymer of monomer i, and T gis the theoretical glass transition temperature of the copolymer derived from monomers a, b, ..., and i. The calculation of the theoretical Tg excludes multifunctional unsaturated monomers, unsaturated ketone monomers, and unsaturated silane monomers.

[0040] In some embodiments, the theoretical T of the first phase polymer is g In some embodiments, the first phase polymer T may be at least 60°C (e.g., at least 65°C, at least 70°C, at least 75°C, at least 80°C, at least 85°C, at least 90°C, at least 95°C, at least 100°C, at least 105°C, at least 110°C, at least 120°C, at least 125°C, at least 130°C, at least 140°C, at least 150°C, at least 160°C, at least 170°C, at least 180°C, at least 190°C, at least 200°C, at least 210°C, at least 220°C, at least 230°C, or at least 240°C). g Theory T g The theoretical T of the first phase polymer may be 240°C or less (e.g., 230°C or less, 220°C or less, 210°C or less, 200°C or less, 190°C or less, 180°C or less, 170°C or less, 160°C or less, 150°C or less, 140°C or less, 130°C or less, 120°C or less, 115°C or less, 110°C or less, 105°C or less, 100°C or less, 95°C or less, 90°C or less, 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, or 60°C or less). g can range from any of the above minimum values ​​to any of the above maximum values. For example, the second theoretical T of the first phase polymer is g It may be 60°C to 240°C (e.g., 60°C to 215°C, 60°C to 200°C, 60°C to less than 180°C, 60°C to 150°C, 70°C to 215°C, 70°C to 200°C, 70°C to less than 180°C, 70°C to 150°C, 80°C to 240°C, 80°C to 210°C, 80°C to less than 200°C, 80°C to 180°C, 80°C to 150°C, 90°C to 160°C, or 90°C to 130°C).

[0041] In some embodiments, the theoretical T of the second phase polymer is gIn some embodiments, the theoretical T of the second phase polymer may be at least 40°C (e.g., at least 45°C, at least 50°C, at least 55°C, at least 60°C, at least 65°C, at least 70°C, at least 75°C, at least 80°C, at least 85°C, at least 90°C, at least 95°C, at least 100°C, at least 105°C, at least 110°C, at least 120°C, at least 125°C, at least 130°C, at least 140°C, at least 150°C, at least 160°C, at least 170°C, at least 180°C, at least 190°C, at least 200°C, at least 210°C, at least 220°C, at least 230°C, or at least 240°C). g The theoretical T of the second phase polymer may be 240°C or less (e.g., 230°C or less, 220°C or less, 210°C or less, 200°C or less, 190°C or less, 180°C or less, 170°C or less, 160°C or less, 150°C or less, 140°C or less, 130°C or less, 120°C or less, 115°C or less, 110°C or less, 105°C or less, 100°C or less, 95°C or less, 90°C or less, 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, 60°C or less, 55°C or less, 50°C or less, 45°C or less, or 40°C or less). g can range from any of the above minimum values ​​to any of the above maximum values. For example, the theoretical T of the second phase polymer is g Range of 40°C to 240°C (e.g., 60°C to 240°C, 60°C to 120°C, 40°C to 120°C, 60°C to 100°C, 40°C to 100°C, 80°C to 110°C, or 70°C to 100°C)

[0042] In some embodiments, the theoretical T of the soft phase polymer is g The theoretical T of the soft phase polymer may be 30°C or less (e.g., 25°C or less, 20°C or less, 15°C or less, 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10°C or less, -15°C or less, -20°C or less, or -25°C or less). In some embodiments, the theoretical T of the soft phase polymer may be 30°C or less (e.g., 25°C or less, 20°C or less, 15°C or less, 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10°C or less, -15°C or less, -20°C or less, or -25°C or less). g The theoretical T of the soft phase polymer may be at least -25°C, at least -20°C, at least -15°C, at least -10°C, at least -5°C, at least -0°C, at least 5°C, at least 10°C, at least 15°C, at least 20°C, or at least 25°C. g can range from any of the above minimum values ​​to any of the above maximum values. For example, the theoretical T of a soft phase polymer is gThe range can be from -25°C to 30°C (e.g., from -25°C to 25°C, from -25°C to 10°C, from -25°C to 0°C, -20°C to 30°C, -10°C to 30°C, -10°C to 25°C, or -0°C to 20°C).

[0043] Theoretical T of the second phase polymer g Greater than the theoretical T of the soft phase polymer g In some embodiments, the theoretical T g The theoretical T of soft phase polymer can be compared g At least 20°C higher (e.g., at least 25°C higher, at least 30°C higher, at least 35°C higher, at least 40°C higher, at least 45°C higher, at least 50°C higher, at least 55°C higher, at least 60°C higher, at least 65°C higher, at least 70°C higher, at least 75°C higher, at least 80°C higher, at least 85°C higher, at least 90°C higher, at least 95°C higher, at least 100°C higher, at least 105°C higher, at least 110°C higher, at least 115°C higher, or at least 120°C higher).

[0044] In some examples, the multiphase polymer can be in the form of a multilayer particle, which comprises (i) a first layer comprising a first phase polymer; and (ii) a second layer surrounding at least a portion of the first layer, the first layer comprising a second phase polymer. The multilayer particle can include a first layer and a second layer surrounding at least a portion of the first layer. For example, the multilayer particle can range from a core-shell particle to a so-called "acorn" particle, wherein the second layer surrounds most of the first layer in a continuous, semi-continuous or discontinuous manner (e.g., such that the second layer forms at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% of the particle surface). In some embodiments, the first layer and the second layer form a first and second domain within the multilayer particle, wherein the second layer surrounds at least a portion of the first layer. The third soft phase polymer can be separated from the particle comprising the first polymer and the second polymer. In some embodiments, at least a portion of the third polymer forms a shell on the second polymer, thereby producing an acorn-like morphology. In some embodiments, at least a portion of the third polymer forms a shell on the first polymer. In some embodiments, at least a portion of the third polymer forms particles that do not include the first polymer or the second polymer. In some embodiments, the multiphase polymer particles have multiple domains of different phases.

[0045] The weight ratio of the first phase polymer (or first polymer) to the second phase polymer can be 1:30 or greater (e.g., 1:25 or greater, 1:20 or greater, 1:18 or greater, 1:15 or greater, 1:12 or greater, 1:10 or greater, 1:9.5 or greater, 1:9 or greater, 1:8.5 or greater, 1:8 or greater, 1:7.5 or greater, 1:7 or greater, 1:6.5 or greater, 1:6 or greater, 1:5.5 or greater, 1:5 or greater, 1:4.5 or greater, 1:4 or greater, 1:3.5 or greater, or 1:3 or greater). The weight ratio of the first phase polymer (or first polymer) to the second phase polymer can be 1:3 or less (e.g., at least 1:3.5 or less, 1:4 or less, 1:4.5 or less, 1:5 or less, 1:5.5 or less, 1:6 or less, 1:6.5 or less, 1:7 or less, 1:7.5 or less, 1:8 or less, 1:8.5 or less, 1:9 or less, 1:9.5 or less, 1:10 or less, 1:12 or less, 1:15 or less, 1:18 or less, 1:20 or less, 1:22 or less, 1:25 or less, 1:28 or less, or 1:30 or less). The weight ratio of the first phase polymer (or first polymer) to the second phase polymer can range from any of the minimum ratios recited above to any of the maximum ratios recited above. For example, the weight ratio of the first phase polymer (or first polymer) to the second phase polymer can be 1:30 to 1:3 (eg, 1:30 to 1:5, or 1:10 to 1:5).

[0046] The weight ratio of the second phase polymer to the soft phase polymer (or the third polymer) can be 1:5 or greater (e.g., 1:4.5 or greater, 1:4 or greater, 1:3.5 or greater, 1:3 or greater, 1:2.5 or greater, 1:2 or less, 1:1.5 or greater, or 1:1 or greater). The weight ratio of the second phase polymer to the soft phase polymer (or the third polymer) can be 1:1 or less (e.g., at least 1:1.5 or less, 1:2 or less, 1:2.5 or less, 1:3 or less, 1:3.5 or less, 1:4 or less, 1:4.5 or less, 1:5 or less, or 1:5.5 or less). The weight ratio of the second phase polymer to the soft phase polymer (or the third polymer) can range from any of the minimum ratios described above to any of the maximum values ​​described above. For example, the weight ratio of the second phase polymer to the soft phase polymer (or the third polymer) can be from 1:5 to 1:1 (e.g., 1:5 to 1:1.5 or 1:4 to 1:2).

[0047] The multiphase polymer can, for example, be derived from greater than 0 weight percent of the first phase polymer (e.g., 0.1% or more, 0.25% or more, 0.5% or more, 0.75% or more, 1% or more, 1.5% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, 5% or more, 6% or more, 7% or more, or 8% or more), based on the total weight of the multiphase polymer. In some examples, the multiphase polymer can be derived from 15 wt % or less of the first phase polymer (e.g., 12 wt % or less, 10 wt % or less, 9 wt % or less, 8 wt % or less, 7 wt % or less, 6 wt % or less, 5 wt % or less, 4.5 wt % or less, 4 wt % or less, 3.5 wt % or less, 3 wt % or less, 2.5 wt % or less, 2 wt % or less, 1.5 wt % or less, 1 wt % or less, 0.75 wt % or less, or 0.5 wt % or less), based on the total weight of the multiphase polymer. The amount of the first phase polymer from which the multiphase polymer is derived can range from any of the minimum values ​​recited to any of the maximum values ​​recited. For example, the multiphase polymer can be derived from greater than 0 wt % to 15 wt % of the first phase polymer (e.g., from greater than 0 wt % to 10 wt %, 0.1 wt % to 10 wt %, 1 wt % to 10 wt %, 1 wt % to 8 wt %, 1.5 wt % to 10 wt %, 1.5 wt % to 6 wt %, or 1.5 wt % to 5 wt %), based on the total weight of the multiphase polymer.

[0048] The multiphase polymer can, for example, be derived from greater than 15 wt % of the second phase polymer (e.g., 18 wt % or more, 20 wt % or more, 22 wt % or more, 25 wt % or more, 28 wt % or more, 30 wt % or more, 32 wt % or more, 35 wt % or more, 37 wt % or more, 40 wt % or more, 42 wt % or more, 45 wt % or more, or 50 wt % or more, based on the total weight of the multiphase polymer. In some examples, the multiphase polymer can be derived from 50 wt % or less of the second phase polymer (e.g., 48 % or less, 45 % or less, 40 % or less, 38 % or less, 36 % or less, 35 % or less, 34 % or less, 32 % or less, 30 % or less, 28 % or less, 25 % or less, 26 % or less, 24 % or less, 22 % or less, 20 % or less, 18 % or less, or 15 % or less, based on the total weight of the multiphase polymer. The amount of the second phase polymer from which the multiphase polymer is derived can range from any of the minimum values ​​recited above to any of the maximum values ​​recited above. For example, the multiphase polymer can be derived from greater than 15% to 50% by weight of the second phase polymer (e.g., from greater than 15% to 50%, 20% to 45%, 20% to 40%, 25% to 40%, or 25% to 35%), based on the total weight of the multiphase polymer.

[0049] The multiphase polymer can, for example, be derived from 40% by weight or more of a soft phase polymer (e.g., 45% or more, 47% or more, 50% or more, 52% or more, 55% or more, 58% or more, 60% or more, 62% or more, 64% or more, 65% or more, 68% or more, 70% or more, or 75% or more), based on the total weight of the multiphase polymer. In some instances, the multiphase polymer can be derived from 80% by weight or less of a soft phase polymer (e.g., 75% or less, 72% or less, 70% or less, 68% or less, 66% or less, 65% or less, 64% or less, 62% or less, 60% or less, 58% or less, 55% or less, 52% or less, 50% or less, 48% or less, 46% or less, 45% or less, or 40% or less), based on the total weight of the multiphase polymer. The amount of the soft phase polymer from which the multiphase polymer is derived can range from any of the above minimum values ​​to any of the above maximum values. For example, the multiphase polymer can be derived from greater than 45% to 80% by weight of the soft phase polymer (e.g., from greater than 45% to 75%, 50% to 75%, 50% to 70%, 55% to 70%, or 55% to 65%), based on the total weight of the multiphase polymer.

[0050] First Phase Polymer

[0051] The first phase polymer may be a homopolymer derived from a single ethylenically unsaturated monomer or a copolymer derived from an ethylenically unsaturated monomer. In some embodiments, the first phase polymer comprises an acrylic polymer. Acrylic-based polymers include polymers derived from one or more (meth)acrylate monomers. Acrylic-based polymers may be pure acrylic polymers (i.e., polymers derived only from (meth)acrylate monomers), styrene-acrylic polymers (i.e., copolymers derived from styrene and one or more (meth)acrylate monomers), or vinyl-acrylic polymers (i.e., copolymers derived from one or more vinyl ester monomers and one or more (meth)acrylate monomers). In some embodiments, the first phase polymer comprises a vinyl aromatic-based polymer, such as a pure vinyl aromatic-based polymer (i.e., a polymer derived only from vinyl aromatic monomers such as styrene).

[0052] The first phase polymer may be derived from one or more hard ethylenically unsaturated monomers. As used herein, the term "hard ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer that, when homopolymerized, forms a T as measured using DSC. gPolymers with a temperature greater than 0°C. Hard ethylenically unsaturated monomers are known in the art and include, for example, methyl acrylate (Tg = 10°C), methyl methacrylate (Tg = 120°C), ethyl methacrylate (Tg = 65°C), n-butyl methacrylate (Tg = 20°C), tert-butyl methacrylate (Tg = 118°C), tert-butyl acrylate (Tg = 44°C), isobutyl methacrylate (Tg = 53°C), vinyl acetate (Tg = 30°C), hydroxyethyl acrylate (Tg = 15°C), hydroxyethyl methacrylate (Tg = 57°C), cyclohexyl acrylate (Tg = 19°C), cyclohexyl methacrylate (Tg = 92°C), 2-ethoxyethyl methacrylate (Tg = 16°C), 2-phenoxyethyl methacrylate (Tg = 54°C), benzyl acrylate (Tg = 6°C), benzyl methacrylate (Tg = 54°C), hydroxypropyl methacrylate (Tg = 76°C), styrene (Tg = 100°C), 4-acetylstyrene (Tg = 116°C), acrylamide (Tg = 165°C), acrylonitrile (Tg = 125°C), 4-bromostyrene (Tg = 118°C), n-tert-butylacrylamide (Tg = 128°C), 4-tert-butylstyrene (Tg = 127°C), 2,4-dimethylstyrene (Tg = 112°C), 2,5-dimethylstyrene (Tg = 143°C), 3,5-dimethylstyrene (Tg = 104°C), isobornyl acrylate (Tg = 94°C), isobornyl methacrylate (Tg = 110°C), 4-methoxystyrene (Tg = 113°C), methylstyrene (Tg = 20°C), 4-methylstyrene (Tg = 97°C), 3-methylstyrene (Tg = 97°C), 2,4,6-trimethylstyrene (Tg = 162°C), and combinations thereof.

[0053] In some embodiments, the first phase polymer may be derived from one or more hard ethylenically unsaturated monomers that, when homopolymerized, form a polymer having a theoretical Tg of at least 60°C (e.g., at least 80°C, at least 85°C, at least 90°C, at least 95°C, at least 100°C, at least 105°C, at least 110°C, at least 115°C, or at least 120°C). In some embodiments, the first phase polymer may be derived from greater than 50% by weight or more of one or more hard ethylenically unsaturated monomers (e.g., 65% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 88% by weight or more, 90% by weight or more, 91% by weight or more, 92% by weight or more, 93% by weight or more, 94% by weight or more, or 95% by weight or more of hard ethylenically unsaturated monomers, based on the total weight of the monomers used to form the first phase polymer.

[0054] In some embodiments, the first phase polymer may be derived from one or more hard ethylenically unsaturated monomers selected from the group consisting of methyl methacrylate, styrene, and combinations thereof. In certain embodiments, the first phase polymer is derived from at least 90 wt% (e.g., at least 90 wt%, at least 91 wt%, at least 92 wt%, at least 93 wt%, at least 94 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%) of one or more hard ethylenically unsaturated monomers selected from the group consisting of methyl methacrylate, styrene, and combinations thereof, based on the total weight of the monomers used to form the first phase polymer. In some instances, the first phase polymer may contain greater than 0 wt% styrene, preferably 10 wt% to 100 wt% styrene, or more preferably 40 wt% to 100 wt% styrene, based on the total weight of the first phase polymer. In certain embodiments, the first phase polymer is derived from at least 85 wt % styrene (e.g., at least 86 wt %, at least 87 wt %, at least 88 wt %, at least 89 wt %, at least 90 wt %, at least 91 wt %, at least 92 wt %, at least 93 wt %, at least 94 wt %, at least 95 wt %, at least 96 wt %, at least 97 wt %, at least 98 wt %, or at least 99 wt %) based on the total weight of monomers used to form the first phase polymer. The first phase polymer can be a seed polymer, such as a polystyrene seed.

[0055] In addition to one or more hard ethylenically unsaturated monomers, the first phase polymer may also be derived from one or more additional ethylenically unsaturated monomers (e.g., (meth)acrylate monomers, carboxylic acid-containing monomers, acetoacetoxy monomers, phosphorus-containing monomers, etc.). In certain embodiments, the first phase polymer is substantially free of (i.e., derived from less than 0.25 weight percent of) acetoacetoxy monomers and / or phosphorus-containing monomers. In certain embodiments, the first phase polymer is substantially free of (i.e., derived from less than 0.25 weight percent of) carboxylic acid-containing monomers.

[0056] Typically, the average volume average particle size of the first phase polymer is about 60 nm or less, such as 50 nm or less, or 40 nm or less. For example, the first phase polymer may have an average volume average particle size of about 10 nm to about 60 nm, such as about 20 nm to about 50 nm, or about 20 nm to about 40 nm.

[0057] Second Phase Polymer

[0058] The second phase polymer can be derived from ethylenically unsaturated monomers and one or more crosslinking monomers. Exemplary ethylenically unsaturated monomers include (meth)acrylate monomers, vinyl aromatic monomers (e.g., styrene), ethylenically unsaturated aliphatic monomers (e.g., butadiene), vinyl ester monomers (e.g., vinyl acetate), and combinations thereof.

[0059] In some embodiments, the second phase polymer may include an acrylic acid-based copolymer. Acrylic acid-based copolymers include copolymers derived from one or more (meth)acrylate monomers. The term "(meth)acrylate monomer" as used herein includes acrylate, methacrylate, diacrylate, and dimethacrylate monomers. (Meth)acrylate monomers may include esters of α,β-monoethylenically unsaturated monocarboxylic acids and dicarboxylic acids having 3 to 6 carbon atoms and alkanols having 1 to 20 carbon atoms (e.g., acrylic acid, methacrylic acid, maleic acid, fumaric acid, or itaconic acid with C1-C 20 、C4-C 20 、C1-C 16 or C4-C 16 The acrylic-based copolymer may be a pure acrylic polymer (i.e., a copolymer derived primarily from (meth)acrylate monomers), a styrene-acrylic polymer (i.e., a copolymer derived from styrene and one or more (meth)acrylate monomers), or a vinyl-acrylic polymer (i.e., a copolymer derived from one or more vinyl ester monomers and one or more (meth)acrylate monomers).

[0060] The second phase polymer may be derived from one or more hard ethylenically unsaturated monomers. In some embodiments, the second phase polymer may be derived from one or more hard ethylenically unsaturated monomers including, but not limited to, methyl acrylate, ureido methacrylate, isobornyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, isobutyl methacrylate, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxypropyl methacrylate, styrene, 4-acetylstyrene, acrylamide, acrylonitrile, 4-bromostyrene, n-tert-butylacrylamide, 4-tert-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, isobornyl acrylate, isobornyl methacrylate, 4-methoxystyrene, methylstyrene, 4-methylstyrene, or a combination thereof. In certain embodiments, the second phase polymer may be derived from a hard ethylenically unsaturated monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ureido methacrylate, n-butyl methacrylate, isobornyl methacrylate, and combinations thereof.

[0061] The second phase polymer can be derived from at least 10 weight percent of one or more hard ethylenically unsaturated monomers (e.g., at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 35 weight percent, at least 40 weight percent, at least 45 weight percent, at least 50 weight percent, at least 55 weight percent, at least 60 weight percent, at least 65 weight percent, at least 70 weight percent, at least 75 weight percent, at least 80 weight percent, at least 85 weight percent, at least 90 weight percent, at least 95 weight percent, or at least 98 weight percent), based on the total weight of monomers used to form the second phase polymer. The second phase polymer can be derived from up to 98 weight percent of one or more hard ethylenically unsaturated monomers (e.g., up to 97 weight percent, up to 95 weight percent, up to 90 weight percent, up to 85 weight percent, up to 80 weight percent, up to 75 weight percent, up to 70 weight percent, up to 65 weight percent, up to 60 weight percent, up to 55 weight percent, up to 50 weight percent, up to 45 weight percent, up to 40 weight percent, up to 35 weight percent, up to 30 weight percent, up to 25 weight percent, up to 20 weight percent, or up to 15 weight percent), based on the total weight of monomers used to form the second phase polymer. The second phase polymer can be derived from an amount of one or more hard ethylenically unsaturated monomers ranging from any of the minimum percentages recited above to any of the maximum percentages recited above. For example, the second phase polymer can be derived from 15 to 99 wt % of one or more hard ethylenically unsaturated monomers (e.g., 50 to 99 wt %, 50 to 95 wt %, 15 to 90 wt %, 25 to 90 wt %, 30 to 95 wt %, or 35 to 95 wt %), based on the total weight of monomers used to form the second phase polymer.

[0062] The second phase polymer may be derived from one or more soft ethylenically unsaturated monomers. As used herein, the term "soft ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer that, when homopolymerized, forms a polymer having a glass transition temperature (as measured using differential scanning calorimetry (DSC)) of 0°C or less. Soft ethylenically unsaturated monomers are known in the art and include, for example, ethyl acrylate (T g =-24°C), butyl acrylate (n-butyl acrylate, T g =-54°C), sec-butyl acrylate (T g =-26°C), sec-butyl acrylate (T g =-26°C), isobutyl acrylate (T g =-24°C), n-hexyl acrylate (T g =-45°C), n-hexyl methacrylate (T g =-5°C), 2-ethylhexyl acrylate (T g =-85°C), 2-ethylhexyl methacrylate (Tg =-10℃), octyl methacrylate (T g =-20°C), n-decyl methacrylate (T g =-30°C), isodecyl acrylate (T g =-55°C), dodecyl acrylate (T g =-3°C), dodecyl methacrylate (T g =-65°C), 2-ethoxyethyl acrylate (T g =-50°C), 2-methoxyacrylate (T g =-50°C) and 2-(2-ethoxyethoxy)ethyl acrylate (T g =-70°C).

[0063] In some embodiments, the second phase polymer may be derived from a soft ethylenically unsaturated monomer that, when homopolymerized, forms a polymer having a glass transition temperature (as measured using DSC) of 10°C or less (e.g., 0°C or less, -10°C or less, -20°C or less, -30°C or less, -40°C or less, -50°C or less, -60°C or less, -70°C or less, or -80°C or less). In certain embodiments, the soft ethylenically unsaturated monomer may be a (meth)acrylate monomer. In certain embodiments, the second phase polymer may be derived from a soft ethylenically unsaturated monomer selected from the group consisting of butyl acrylate, 2-ethylhexyl acrylate, and combinations thereof.

[0064] The second phase polymer can be derived from at least 0.5 wt %, at least 1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 3 wt %, at least 3.5 wt %, at least 4 wt %, at least 4.5 wt %, at least 5 wt %, at least 5.5 wt %, at least 6 wt %, at least 6.5 wt %, at least 7 wt %, at least 7.5 wt %, at least 8 wt %, at least 8.5 wt %, at least 9 wt %, at least 9.5 wt %, at least 10 wt %, at least 12 wt %, at least 14 wt %, at least 15 wt %, at least 18 wt %, at least 20 wt %, at least 22 wt %, at least 24 wt %, or at least 25 wt %, based on the total weight of monomers used to form the second phase polymer. The second phase polymer can be derived from up to 25 wt% of one or more soft ethylenically unsaturated monomers (e.g., up to 22 wt%, up to 20 wt%, up to 18 wt%, up to 15 wt%, up to 12 wt%, up to 10 wt%, up to 9 wt%, up to 8 wt%, up to 7 wt%, up to 6 wt%, up to 5 wt%, up to 4.5 wt%, up to 4 wt%, or up to 3 wt%) based on the total weight of the monomers used to form the second phase polymer. The second phase polymer can be derived from an amount of one or more soft ethylenically unsaturated monomers ranging from any of the minimum percentages recited above to any of the maximum percentages recited above. For example, the second phase polymer can be derived from 0.5 wt% to 25 wt% of one or more soft ethylenically unsaturated monomers (e.g., 0.5 wt% to 20 wt%, 2 wt% to 20 wt%, 2 wt% to 10 wt%, or 2.5 wt% to 8 wt%) based on the total weight of the monomers used to form the second phase polymer.

[0065] The second phase polymer may include ethylenically unsaturated acid monomers. Suitable ethylenically unsaturated strong acid monomers include any monomer having a pendant acid group with a pKa (in water at 20°C) less than 4 or a salt of such a monomer. Suitable salts of the acid monomer include ammonium, sodium, potassium and lithium salts. The ethylenically unsaturated acid monomer may be selected from carboxylic acid monomers, phosphorous acid monomers, sulfuric acid monomers or combinations thereof.

[0066] In some embodiments, the second phase polymer may be derived from one or more carboxylic acid-containing monomers. Suitable carboxylic acid-containing monomers are known in the art and include α,β-monoethylenically unsaturated monocarboxylic acids and dicarboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, dimethacrylic acid, ethacrylic acid, allyl acetic acid, vinyl acetic acid, mesaconic acid, methylenemalonic acid, citraconic acid, and combinations thereof.

[0067] In some embodiments, the second phase polymer may be derived from one or more phosphite monomers. Suitable phosphorous acid monomers are known in the art and include alkyl phosphoacrylates or methacrylates (e.g., ethyl phosphoacrylate or methacrylate, propyl phosphoacrylate or methacrylate, butyl phosphoacrylate or methacrylate, phosphate esters of polyethylene glycol acrylate or methacrylate, and phosphate esters of polypropylene glycol acrylate or methacrylate); alkyl phosphocrotonates; alkyl maleate phosphoesters; alkyl fumarate phosphoesters; dialkyl phosphoacrylate or methacrylate; dialkyl phosphocrotonates; allyl phosphates; vinyl phosphonic acid; allyl phosphonic acid; 2-acrylamido-2-methylpropanephosphonic acid; α-phosphonostyrene; 2-methacrylamido-2-methylpropanephosphonic acid; 2-phosphoethyl (meth)acrylate; 2-phosphopropyl (meth)acrylate; 3-phosphopropyl (meth)acrylate; 3-phospho-2-hydroxypropyl (meth)acrylate; mixtures thereof, or salts thereof, or combinations thereof. In some embodiments, the phosphorous acid monomer may have the formula CH2=C(R)-C(O)-O-(R 1 O) n -P(O)(OH)2, where R is H or CH3, R 1 is an alkyl group, and n is 0 to 50. In some embodiments, the phosphorous acid monomer may be obtained under the trade name PAM 100, PAM 200 or PAM 4000 is sold as a single unit.

[0068] In some embodiments, the second phase polymer can be derived from one or more sulfuric acid-containing monomers. Suitable sulfuric acid-containing monomers are known in the art and include 2-acrylamido-2-methylpropanesulfonic acid; styrenesulfonic acid; 1-allyloxy-2-hydroxypropanesulfonic acid; vinylsulfonic acid; alkylallylsulfosuccinic acid; sulfoethyl acrylate, sulfoethyl methacrylate; salts thereof; or combinations thereof.

[0069] The second phase polymer can be derived from greater than 0 wt % of one or more ethylenically unsaturated acid monomers (e.g., at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt %, at least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 3 wt %, at least 3.5 wt %, at least 4 wt %, at least 4.5 wt %, at least 5 wt %, at least 5.5 wt %, or at least 6 wt %, based on the total weight of monomers used to form the second phase polymer. The second phase polymer can be derived from 6 wt % or less of one or more ethylenically unsaturated acid monomers (e.g., 5.5 wt % or less, 5 wt % or less, 4.5 wt % or less, 4 wt % or less, 3.5 wt % or less, 3 wt % or less, 2.5 wt % or less, 2 wt % or less, 1.5 wt % or less, 1 wt % or less, or 0.5 wt % or less), based on the total weight of monomers used to form the second phase polymer. The second phase polymer can be derived from an amount of one or more ethylenically unsaturated acid monomers ranging from any of the minimum percentages described above to any of the maximum percentages described above. For example, the second phase polymer can be derived from greater than 0 wt % to 6 wt % of one or more ethylenically unsaturated acid monomers (e.g., 0.01 wt % to 6 wt %, 0.5 wt % to 5 wt %, or 0.5 wt % to 3 wt % of one or more ethylenically unsaturated acid monomers, based on the total weight of monomers used to form the second phase polymer.

[0070] The second phase polymer disclosed herein can also be derived from a multifunctional crosslinking agent. The general term "crosslinking" agent or "crosslinking" monomer refers to an ethylenically unsaturated monomer, through which crosslinking is produced or will be produced. As used herein, the term "multifunctional" crosslinking monomer refers to a crosslinking monomer having two or more (e.g., three or more, four or more, or five or more) reactive functional groups such as two or more polymerizable unsaturated groups in one molecule. In some embodiments, the multifunctional crosslinking monomer may include two or more polymerizable carbon-carbon double bonds. Exemplary multifunctional crosslinking agents include but are not limited to divinyl monomers, diallyl monomers, trivinyl monomers, triallyl monomers, di(methyl)acrylates, tri(methyl)acrylates, tetra(methyl)acrylates, penta(methyl)acrylates or combinations thereof. Multifunctional crosslinking monomers also include divinyl (methyl)acrylate, diallyl (methyl)acrylate, allyl (methyl)acrylate, trivinyl (methyl)acrylate, triallyl (methyl)acrylate, divinylbenzene, trivinylbenzene, diallyl maleate or combinations thereof.

[0071] In some examples, the multifunctional crosslinking monomer comprises a tri(meth)acrylate, preferably trimethylolpropane triacrylate. Without wishing to be bound by theory, it is believed that the inclusion of trimethylolpropane triacrylate in both the second phase polymer and the soft phase polymer increases the phase separation between the second phase and the soft phase polymer, thereby reducing the minimum film forming temperature of the multiphase polymer.

[0072] The amount of the multifunctional crosslinker can be 0.01% or more (e.g., 0.05% or more, 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.6% or more, 1.7% or more, 1.8% or more, 1.9% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, or 4% or more) based on the total amount of monomers in the second phase polymer. In some examples, the amount of multifunctional crosslinker can be 5% or less (e.g., 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5% or less, 1.4% or less, 1.3% or less, 1.2% or less, 1.1% or less, 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, or 0.2% or less) based on the total amount of monomers in the second phase polymer. The amount of multifunctional crosslinker employed can range from any of the above minimum values ​​to any of the above maximum values. For example, the amount of the multifunctional crosslinker can be 0.05% to 5% (e.g., 0.2% to 5%, 0.5% to 5%, 0.05% to 2.5%, 2.5% to 2%, 0.05% to 0.5%, 0.5% to 1%, 1% to 1.5%, 1.5% to 2%, 2% to 2.5%, 2.5% to 3%, 3% to 3.5%, 3.5% to 4%, 4% to 4.5%, 4.5% to 5%, 0.05% to 4%, 0.05% to 3%, or 0.05% to 2%) based on the total amount of monomers in the second phase polymer.

[0073] The second phase polymer also includes an unsaturated ketone monomer. The unsaturated ketone monomer can be selected from diacetone acrylamide, acetoacetoxy alkyl (meth) acrylate or a combination thereof. Suitable acetoacetoxy monomers are known in the art and include acetoacetoxy alkyl (meth) acrylates, such as acetoacetoxy ethyl (meth) acrylate (AAEM), acetoacetoxy propyl (meth) acrylate, acetoacetoxy butyl (meth) acrylate and 2,3-di (acetoacetoxy) propyl (meth) acrylate; allyl acetoacetate; vinyl acetoacetate; and combinations thereof.

[0074] The second phase polymer can be derived from greater than 0 wt % unsaturated ketone monomer (e.g., at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt %, at least 0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 3 wt %, at least 3.5 wt %, at least 4 wt %, at least 4.5 wt %, at least 5 wt %, at least 5.5 wt %, at least 6 wt %, at least 6.5 wt %, at least 7 wt %, at least 7.5 wt %, at least 8 wt %, at least 8.5 wt %, at least 9 wt %, at least 10 wt %, at least 11 wt %, at least 12 wt %, at least 13 wt %, at least 14 wt %, or at least 15 wt %, based on the total weight of monomers used to form the second phase polymer. The second phase polymer can be derived from 15 wt % or less of one or more unsaturated ketone monomers (e.g., 14 wt % or less, 13 wt % or less, 12 wt % or less, 11 wt % or less, 10 wt % or less, 9.5 wt % or less, 8 wt % or less, 8.5 wt % or less, 8 wt % or less, 7.5 wt % or less, 7 wt % or less, 6.5 wt % or less, 6 wt % or less, 5.5 wt % or less, 5 wt % or less, 4.5 wt % or less, 4 wt % or less, 3.5 wt % or less, 3 wt % or less, 2.5 wt % or less, 2 wt % or less, 1.5 wt % or less, 1 wt % or less, or 0.5 wt % or less, based on the total weight of monomers used to form the second phase polymer. The second phase polymer can be derived from an amount of one or more unsaturated ketone monomers ranging from any of the minimum percentages recited above to any of the maximum percentages recited above. For example, the second phase polymer can be derived from greater than 0 wt % to 15 wt % of one or more unsaturated ketone monomers (e.g., 0.01 wt % to 10 wt % of one or more unsaturated ketone monomers, 0.5 wt % to 10 wt % of one or more unsaturated ketone monomers, 1 wt % to 10 wt % of one or more unsaturated ketone monomers, 0.01 wt % to 5 wt % of one or more unsaturated ketone monomers, 0.5 wt % to 5 wt % of one or more unsaturated ketone monomers, or 0.1 wt % to 3.5 wt % of one or more unsaturated ketone monomers, based on the total weight of monomers used to form the second phase polymer.

[0075] The second phase polymer may include an alkoxysilane crosslinker monomer, preferably an unsaturated alkoxysilane monomer. In some embodiments, the unsaturated alkoxysilane monomer may be represented by the formula

[0076] (R 1 )-Si-(OR 2 )3Formula I

[0077] Where R 1 is a vinyl group, a (meth)acryloyl group; and R 2 In each occurrence, independently selected from C1-C 10 alkyl.

[0078] In some embodiments, the unsaturated alkoxysilane monomer may be represented by the formula

[0079] (R 1 )-Si-(OR 2 )1(R 2 )2 Formula II

[0080] or

[0081] (R 1 )-Si-(OR 2 )2(R 2 )1 Formula III

[0082] Where R 1 is a vinyl group, a (meth)acryloyl group; and R 2 In each occurrence, independently selected from C1-C 10 alkyl.

[0083] In some examples, the unsaturated alkoxysilane includes vinyl silane. Exemplary unsaturated alkoxysilanes may include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(2-methoxyethoxysilane), vinyl triisopropoxysilane, (meth) acryloxypropyl trimethoxysilane, γ-(meth) acryloxypropyl trimethoxysilane, γ-(meth) acryloxypropyl triethoxysilane, (3-methacryloxypropyl)-trimethoxysilane, (3-methacryloxypropyl)-triethoxysilane, (3-methacryloxypropyl)-triisopropoxysilane, 2-methyl-2-acrylic acid 3-[tri-(1-methylethoxy)-silyl]-propyl ester, (3-methacryloxypropyl)-methyldiethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, or mixtures thereof.

[0084] In some embodiments, the unsaturated alkoxysilane comprises a polyvinylsiloxane alkoxysilane oligomer having the following structure:

[0085]

[0086] wherein n is an integer from 1 to 50 (e.g., 10). Other examples of suitable polyvinylsiloxane alkoxysilane oligomers include DYNASYLAN 6490 (a polyvinylsiloxane oligomer derived from vinyltrimethoxysilane) and DYNASYLAN 6498 (a polyvinylsiloxane oligomer derived from vinyltriethoxysilane), both of which are commercially available from Evonik Degussa GmbH, Essen, Germany. Other suitable polyvinylsiloxane alkoxysilane oligomers include VMM-010 (a vinylmethoxysiloxane homopolymer) and VEE-005 (a vinylethoxysiloxane homopolymer), both of which are commercially available from Gelest, Morrisville, PA.

[0087] The second phase polymer can, for example, be derived from greater than 0 wt %, e.g., 0.05 wt % or more, of an unsaturated alkoxysilane monomer (e.g., 0.1 % or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.8% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, or 5% or more), based on the total monomer weight of the second phase. In some examples, the second phase polymer can be derived from 15 wt % or less of unsaturated alkoxysilane monomers (e.g., 13% or less, 12% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5.5% or less, 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, or 1.5% or less), based on the total monomer content of the second phase. The amount of silane monomer in the second phase polymer can range from any of the above minimum values ​​to any of the above maximum values. For example, the second phase polymer can be derived from greater than 0 wt % to 15 wt % of unsaturated alkoxysilane monomers, such as 1 wt % to 15 wt % of unsaturated silane monomers (e.g., 1% to 10%, 1.5% to 8%, or 1.5% to 5%), based on the total monomer weight of the second phase.

[0088] The second phase polymer can, for example, be derived from greater than 0 wt %, e.g., 0.05 wt % or more of a crosslinking monomer (e.g., 0.1 % or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.8% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, or 5% or more), based on the total monomer weight of the second phase. In some examples, the second phase polymer can be derived from 15 wt% or less of a crosslinking monomer (e.g., 13% or less, 12% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5.5% or less, 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, or 1.5% or less), based on the total monomer content of the second phase. The amount of crosslinking monomer from which the second phase polymer is derived can range from any of the minimum values ​​recited above to any of the maximum values ​​recited above. For example, the second phase polymer can be derived from greater than 0 wt% to 15 wt% of a crosslinking monomer, such as 1 wt% to 15 wt% of a crosslinking monomer (e.g., 1% to 10%, 1.5% to 8%, or 1.5% to 5%), based on the total monomer weight of the second phase.

[0089] The second phase polymer can be derived from one or more other ethylenically unsaturated monomers greater than 0 wt % to 35 wt %. For example, the second phase polymer can further include vinyl aromatic compounds with up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, (methyl) acrylonitrile, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons with 2 to 8 carbon atoms and one or two double bonds, silane-containing monomers, (methyl) acrylamide, (methyl) acrylamide derivatives, thio monomers or combinations of these monomers. Suitable vinyl aromatic compounds include styrene, α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, vinyl toluene and combinations thereof. Carboxylic acid vinyl esters with up to 20 carbon atoms include, for example, vinyl laurate, vinyl stearate, vinyl propionate, tert-butyl carbonate, vinyl acetate and combinations thereof. Vinyl halides can include ethylenically unsaturated compounds substituted by chlorine, fluorine or bromine, such as vinyl chloride and vinylidene chloride. Vinyl ethers may include, for example, vinyl ethers of alcohols containing 1 to 4 carbon atoms, such as vinyl methyl ether or vinyl isobutyl ether. Aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds may include, for example, hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds, such as butadiene, isoprene and chloroprene. (Meth)acrylamide derivatives include, for example, ketone-containing amide-functional monomers defined by the following general formula:

[0090] CH2=CR1C(O)NR2C(O)R3

[0091] Wherein R1 is hydrogen or methyl; R2 is hydrogen, C1-C4 alkyl or phenyl; and R3 is hydrogen, C1-C4 alkyl or phenyl. For example, the (meth)acrylamide derivative can be diacetone acrylamide (DAAM) or diacetone methacrylamide. Sulfur-containing monomers include, for example, sulfonic acids and sulfonic acid esters, such as vinyl sulfonic acid, 2-sulfoethyl methacrylate, sodium styrene sulfonate, and 2-sulfoxyethyl methacrylate. When present, the sulfur-containing monomer is typically present in an amount greater than 0% to 5% by weight.

[0092] For example, the second phase polymer can be derived from a multifunctional amine group. As used herein, the term "multifunctional amine" refers to an amine-containing molecule comprising two or more amine groups. After the second phase polymer is polymerized, the multifunctional amine group reacts with an unsaturated ketone monomer. At least a portion of the multifunctional amine can exist as a side group on the copolymer backbone. For example, the multifunctional amine reacts with an unsaturated ketone monomer present in the copolymer backbone to form a side group. In these examples, the multifunctional amine can react with an unsaturated ketone monomer present in the copolymer backbone after polymerization. In other examples, a portion of one or more multifunctional amines may be present in the composition but not covalently bonded to the multiphase polymer.

[0093] The example of suitable multifunctional amine includes polyetheramine, polyalkyleneamine, polyhydrazide or its combination.The specific example of multifunctional amine includes the polyamine sold under the trade name Baxxodur, Jeffamine and dytek.In some embodiments, amine is difunctional or higher multifunctional amine-terminated polyoxyalkylene polyol (for example, Jeffamines or Baxxodur amine, example is polyetheramine T403, polyetheramine D230, polyetheramine D400, polyetheramine D2000 or polyetheramine T5000).In some embodiments, amine includes Dytek A, Dytek EP, Dytek HMD, Dytek BHMT and Dytek DCH-99.In some embodiments, amine is the polyhydrazide derived from aliphatic and aromatic polycarboxylic acid, including adipic acid dihydrazide, succinic acid dihydrazide, citric acid trihydrazide, phthalic acid dihydrazide, phthalic acid dihydrazide, trimellitic acid trihydrazide etc. Other amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexyleneheptamine, heptaethyleneoctamine, octaethylenenonylamine, higher polyimines, such as polyethyleneimine and polypropyleneimine, bis(3-aminopropyl)amine, bis(4-aminobutyl)amine, bis(5-aminopentyl)amine, bis(6-aminohexyl)amine, 3-(2-aminoethyl)aminopropylamine, N,N-bis(3-aminopropyl)ethylenediamine, N',N-bis(3-aminopropyl)ethylenediamine, N,N-bis(3-aminopropyl)propane-1,3-diamine, N,N-bis(3-aminopropyl)butane-1,4-diamine, N,N'-bis(3-aminopropyl)propane-1,3-diamine, N,N'-bis(3-aminopropyl)butane-1,4-diamine, N,N,N'N'-tetrakis(3-aminopropyl)ethylenediamine, N,N,N'N'-tetrakis(3-aminopropyl)-1,4-butanediamine, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, tris(3-aminopropyl)amine, tris(2-aminobutyl)amine, tris(3-aminobutyl)amine, tris(4-aminobutyl)amine, tris(5-aminopentyl)amine, tris(6-aminohexyl)amine, trisaminohexane, trisaminononane, 4-aminomethyl-1,8-octamethylenediamine.

[0094] The second phase polymer can, for example, be derived from greater than 0 wt %, e.g., 0.05 wt % or more of a polyfunctional amine (e.g., 0.1 % or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1 % or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.8% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, or 5% or more), based on the total monomer weight of the second phase. In some examples, the second phase polymer can be derived from 15 wt % or less of the polyfunctional amine (e.g., 13 % or less, 12 % or less, 10 % or less, 9 % or less, 8 % or less, 7 % or less, 6 % or less, 5.5 % or less, 5 % or less, 4.5 % or less, 4 % or less, 3.5 % or less, 3 % or less, 2.5 % or less, 2 % or less, or 1.5 % or less) based on the total monomer content of the second phase. The amount of the polyfunctional amine from which the second phase polymer is derived can range from any of the minimum values ​​recited above to any of the maximum values ​​recited above. For example, the second phase polymer can be derived from greater than 0 wt % to 15 wt % of the polyfunctional amine, such as 1 wt % to 15 wt % of the polyfunctional amine (e.g., 1 % to 10 %, 1.5 % to 8 %, or 1.5 % to 5 %) based on the total monomer weight of the second phase.

[0095] In some embodiments, the second phase polymer is derived from:

[0096] (i) one or more (meth)acrylate monomers;

[0097] (ii) one or more carboxylic acid-containing monomers;

[0098] (iii) one or more multifunctional crosslinking monomers;

[0099] (iv) one or more unsaturated ketone monomers;

[0100] (v) one or more unsaturated alkoxysilane monomers

[0101] (vi) one or more polyfunctional amines; and

[0102] (vii) optionally, one or more additional ethylenically unsaturated monomers, excluding monomers (i), (ii), (iii) and (iv).

[0103] The second phase polymer can be derived from at least 55 wt % of one or more (meth)acrylate monomers (e.g., at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, at least 80 wt %, at least 85 wt %, at least 88 wt %, at least 90 wt %, at least 91 wt %, at least 92 wt %, at least 93 wt %, at least 94 wt %, or at least 95 wt %), based on the total weight of monomers used to form the second phase copolymer.

[0104] In certain embodiments, the second phase polymer is derived from

[0105] (i) 0.1 to 5 wt. % of a soft ethylenically unsaturated monomer;

[0106] (ii) 80 to 99 weight percent of a hard ethylenically unsaturated monomer;

[0107] (iii) greater than 0 to 5 weight percent acid monomers;

[0108] (iv) greater than 0 to 5 weight percent of a multifunctional crosslinking monomer;

[0109] (v) greater than 0 to 10 wt. % or greater than 0 to 5 wt. % of one or more unsaturated ketone monomers;

[0110] (vi) greater than 0 to 5 weight percent of one or more polyfunctional amines; and

[0111] (vii) optionally greater than 0 to 5 weight percent of one or more unsaturated alkoxysilane monomers.

[0112] In certain embodiments, the second phase polymer is derived from

[0113] (i) 1.5-50 wt % of acrylate monomers;

[0114] (ii) 50-98 wt% of methacrylate monomer;

[0115] (iii) greater than 0 to 5 weight percent acid monomers;

[0116] (iv) greater than 0 to 5 weight percent of a multifunctional crosslinking monomer;

[0117] (v) greater than 0 to 10 wt. % or greater than 0 to 5 wt. % of one or more unsaturated ketone monomers;

[0118] (vi) greater than 0 to 5 weight percent of one or more polyfunctional amines; and

[0119] (vii) optionally greater than 0 to 5 weight percent of one or more unsaturated alkoxysilane monomers.

[0120] In certain embodiments, the second phase polymer is derived from

[0121] (i) 1.5-50 wt % of an acrylate monomer selected from methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or a combination thereof;

[0122] (ii) 50-98 wt% of a methacrylate monomer selected from methyl methacrylate, ethyl methacrylate, ureido methacrylate, n-butyl methacrylate, isobornyl methacrylate, or a combination thereof;

[0123] (iii) greater than 0 to 5 weight percent of an acid monomer selected from acrylic acid, itaconic acid, phosphorous acid monomers or salts thereof;

[0124] (iv) greater than 0 to 5 weight percent of a multifunctional crosslinking monomer comprising a tri(meth)acrylate monomer;

[0125] (v) greater than 0 to 10 wt% or greater than 0 to 5 wt% of an unsaturated ketone monomer selected from diacetone acrylamide or acetoacetoxyalkyl (meth)acrylate;

[0126] (vi) greater than 0 to 5 weight percent of one or more polyfunctional amines; and

[0127] (vii) optionally greater than 0 to 5 weight percent of one or more unsaturated alkoxysilane monomers.

[0128] Third (soft) phase polymer

[0129] As described herein, the soft phase polymer may be derived from ethylenically unsaturated monomers and crosslinking monomers. In some embodiments, the soft phase polymer may include an acrylic-based copolymer, such as a pure acrylic polymer, a styrene-acrylic polymer, or a vinyl-acrylic polymer.

[0130] The soft phase polymer may be derived from one or more soft ethylenically unsaturated monomers. In certain embodiments, the soft phase polymer may be derived from a soft ethylenically unsaturated monomer selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, and combinations thereof.

[0131] The soft phase polymer can be derived from at least 10 wt % of one or more soft ethylenically unsaturated monomers (e.g., at least 15 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 35 wt %, at least 40 wt %, at least 45 wt %, at least 50 wt %, at least 55 wt %, at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, or at least 80 wt %) based on the total weight of the monomers used to form the soft phase polymer. The soft phase polymer can be derived from up to 85 wt % of one or more soft ethylenically unsaturated monomers (e.g., up to 80 wt %, up to 75 wt %, up to 70 wt %, up to 65 wt %, up to 60 wt %, up to 55 wt %, up to 50 wt %, up to 45 wt %, up to 40 wt %, up to 35 wt %, up to 30 wt %, up to 25 wt %, up to 20 wt %, or up to 15 wt %) based on the total weight of the monomers used to form the soft phase polymer. The soft phase polymer can be derived from an amount of one or more soft ethylenically unsaturated monomers ranging from any of the minimum percentages described above to any of the maximum percentages described above. For example, based on the total weight of the monomers used to form the soft phase polymer, the soft phase polymer can be derived from 15 wt % to 85 wt % of one or more soft ethylenically unsaturated monomers (e.g., 15 wt % to 60 wt %, 25 wt % to 60 wt %, 30 wt % to 60 wt %, or 35 wt % to 55 wt %).

[0132] The soft phase polymer may also be derived from one or more hard ethylenically unsaturated monomers. In some embodiments, the soft phase polymer may be derived from one or more hard ethylenically unsaturated monomers, including but not limited to methyl acrylate, ureido methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobornyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, isobutyl methacrylate, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxypropyl methacrylate, styrene, 4-acetylstyrene, acrylamide, acrylonitrile, 4-bromostyrene, n-tert-butylacrylamide, 4-tert-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, isobornyl acrylate, isobornyl methacrylate, 4-methoxystyrene, methylstyrene, 4-methylstyrene, or a combination thereof.

[0133] The soft phase polymer can be derived from at least 10 wt % of one or more hard ethylenically unsaturated monomers (e.g., at least 15 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 35 wt %, at least 40 wt %, at least 45 wt %, at least 50 wt %, at least 55 wt %, at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, or at least 80 wt %) based on the total weight of the monomers used to form the soft phase polymer. The soft phase polymer can be derived from up to 85 wt % of one or more hard ethylenically unsaturated monomers (e.g., up to 80 wt %, up to 75 wt %, up to 70 wt %, up to 65 wt %, up to 60 wt %, up to 55 wt %, up to 50 wt %, up to 45 wt %, up to 40 wt %, up to 35 wt %, up to 30 wt %, up to 25 wt %, up to 20 wt %, or up to 15 wt %) based on the total weight of the monomers used to form the soft phase polymer. The soft phase polymer can be derived from an amount of one or more hard ethylenically unsaturated monomers ranging from any of the above minimum percentages to any of the above maximum percentages. For example, based on the total weight of the monomers used to form the soft phase polymer, the soft phase polymer can be derived from 15 wt % to 85 wt % of one or more hard ethylenically unsaturated monomers (e.g., 15 wt % to 60 wt %, 25 wt % to 60 wt %, 30 wt % to 60 wt %, or 35 wt % to 55 wt %).

[0134] In some embodiments, soft phase polymer can include ethylenically unsaturated acid monomers.When present, ethylenically unsaturated acid monomers can be selected from carboxylic acid monomers, phosphorous acid monomers, sulfuric acid monomers or their combinations.In other embodiments, soft phase polymer does not include ethylenically unsaturated acid monomers.Based on the gross weight of the monomers for forming soft phase polymers, soft phase polymer can be derived from 0 wt % or more of one or more ethylenically unsaturated acid monomers (for example, at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt %, at least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 3 wt %, at least 3.5 wt %, at least 4 wt %, at least 4.5 wt %, at least 5 wt %, at least 5.5 wt % or at least 6 wt %). Based on the total weight of the monomers used to form the soft phase polymer, the soft phase polymer can be derived from 6 wt % or less of one or more ethylenically unsaturated acid monomers (e.g., 5.5 wt % or less, 5 wt % or less, 4.5 wt % or less, 4 wt % or less, 3.5 wt % or less, 3 wt % or less, 2.5 wt % or less, 2 wt % or less, 1.5 wt % or less, 1 wt % or less or 0.5 wt % or less). The soft phase polymer can be derived from an amount of one or more ethylenically unsaturated acid monomers ranging from any of the above minimum percentages to any of the above maximum percentages. For example, based on the total weight of the monomers used to form the soft phase polymer, the soft phase polymer can be derived from greater than 0 wt % to 6 wt % of one or more ethylenically unsaturated acid monomers (e.g., 0.01 wt % to 6 wt %, 0.5 wt % to 5 wt %, or 0.5 wt % to 3 wt % of one or more ethylenically unsaturated acid monomers).

[0135] The soft phase polymer disclosed herein can also be derived from the multifunctional crosslinking agent described herein. For example, the soft phase polymer may include tri(meth)acrylate, preferably trimethylolpropane triacrylate. Based on the total amount of monomers in the soft phase polymer, the amount of the multifunctional crosslinking agent can be 0.01% or more (e.g., 0.05% or more, 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.6% or more, 1.7% or more, 1.8% or more, 1.9% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more or 4% or more). In some examples, the amount of the multifunctional crosslinker can be 5% or less (e.g., 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5% or less, 1.4% or less, 1.3% or less, 1.2% or less, 1.1% or less, 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, or 0.2% or less) based on the total amount of monomers in the soft phase polymer. The amount of the multifunctional crosslinker employed can range from any of the above minimum values ​​to any of the above maximum values. For example, the amount of the multifunctional crosslinker can be 0.05% to 5% (e.g., 0.2% to 5%, 0.5% to 5%, 0.05% to 2.5%, 2.5% to 2%, 0.05% to 0.5%, 0.5% to 1%, 1% to 1.5%, 1.5% to 2%, 2% to 2.5%, 2.5% to 3%, 3% to 3.5%, 3.5% to 4%, 4% to 4.5%, 4.5% to 5%, 0.05% to 4%, 0.05% to 3%, or 0.05% to 2%) based on the total amount of monomers in the soft phase polymer.

[0136] The soft phase polymer further comprises an unsaturated ketone monomer as described herein. Preferably, the unsaturated ketone monomer may be selected from diacetone acrylamide, acetoacetoxyalkyl (meth)acrylate or a combination thereof. The soft phase polymer can be derived from greater than 0 wt % unsaturated ketone monomer (e.g., at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt %, at least 0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 3 wt %, at least 3.5 wt %, at least 4 wt %, at least 4.5 wt %, at least 5 wt %, at least 5.5 wt %, at least 6 wt %, at least 6.5 wt %, at least 7 wt %, at least 7.5 wt %, at least 8 wt %, at least 8.5 wt %, at least 9 wt %, at least 10 wt %, at least 11 wt %, at least 12 wt %, at least 13 wt %, at least 14 wt %, or at least 15 wt %) based on the total weight of monomers used to form the soft phase polymer. The soft phase polymer can be derived from 15 wt % or less of one or more unsaturated ketone monomers (e.g., 14 wt % or less, 13 wt % or less, 12 wt % or less, 11 wt % or less, 10 wt % or less, 9.5 wt % or less, 8 wt % or less, 8.5 wt % or less, 8 wt % or less, 7.5 wt % or less, 7 wt % or less, 6.5 wt % or less, 6 wt % or less, 5.5 wt % or less, 5 wt % or less, 4.5 wt % or less, 4 wt % or less, 3.5 wt % or less, 3 wt % or less, 2.5 wt % or less, 2 wt % or less, 1.5 wt % or less, 1 wt % or less, or 0.5 wt % or less) based on the total weight of the monomers used to form the soft phase polymer. The soft phase polymer can be derived from an amount of one or more unsaturated ketone monomers ranging from any of the above minimum percentages to any of the above maximum percentages. For example, the soft phase polymer can be derived from greater than 0 wt % to 15 wt % of one or more unsaturated ketone monomers (e.g., 0.01 wt % to 15 wt % of one or more unsaturated ketone monomers, 0.01 wt % to 10 wt % of one or more unsaturated ketone monomers, 0.5 wt % to 10 wt % of one or more unsaturated ketone monomers, 0.01 wt % to 5 wt % of one or more unsaturated ketone monomers, 0.5 wt % to 5 wt % of one or more unsaturated ketone monomers, or 0.1 wt % to 3.5 wt % of one or more unsaturated ketone monomers, based on the total weight of monomers used to form the soft phase polymer.

[0137] The soft phase polymer may include a silane crosslinker as described herein. The silane crosslinker may be derived from an organoalkoxysilane, preferably an unsaturated alkoxysilane monomer as described herein.

[0138] In some embodiments, the unsaturated alkoxysilane monomer may be represented by the formula

[0139] (R 1 )-Si-(OR 2 )3Formula I

[0140] Where R 1 is a vinyl group, a (meth)acryloyl group; and R 2 In each occurrence, independently selected from C1-C 10 alkyl.

[0141] In some embodiments, the unsaturated alkoxysilane monomer may be represented by the formula

[0142] (R 1 )-Si-(OR 2 )1(R 2 )2 Formula II

[0143] or

[0144] (R 1 )-Si-(OR 2 )2(R 2 )1 Formula III

[0145] Where R 1 is a vinyl group, a (meth)acryloyl group; and R 2 In each occurrence, independently selected from C1-C 10 alkyl.

[0146] In some examples, the organoalkoxysilane includes vinyl alkoxysilane. Exemplary organoalkoxysilanes may include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxysilane), vinyl triisopropoxysilane, (meth)acryloxypropyl trimethoxysilane, γ-(meth)acryloxypropyl trimethoxysilane, γ-(meth)acryloxypropyl triethoxysilane, (3-methacryloxypropyl)-trimethoxysilane, (3-methacryloxypropyl)-triethoxysilane, (3-methacryloxypropyl)-triisopropoxysilane, 2-methyl-2-acrylic acid 3-[tris-(1-methylethoxy)-silyl]-propyl ester, (3-methacryloxypropyl)-methyldiethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, or mixtures thereof.

[0147] In some embodiments, the unsaturated alkoxysilane monomer may include a polyvinylsiloxane alkoxysilane oligomer having the following structure:

[0148]

[0149] wherein n is an integer from 1 to 50 (e.g., 10). Other examples of suitable polyvinylsiloxane alkoxysilane oligomers include DYNASYLAN 6490 (a polyvinylsiloxane oligomer derived from vinyltrimethoxysilane) and DYNASYLAN 6498 (a polyvinylsiloxane oligomer derived from vinyltriethoxysilane), both of which are commercially available from Evonik Degussa GmbH, Essen, Germany. Other suitable polyvinylsiloxane alkoxysilane oligomers include VMM-010 (a vinylmethoxysiloxane homopolymer) and VEE-005 (a vinylethoxysiloxane homopolymer), both of which are commercially available from Gelest, Morrisville, PA.

[0150] The soft phase polymer can, for example, be derived from greater than 0 wt %, e.g., 0.05 wt % or more of an unsaturated alkoxysilane monomer (e.g., 0.1 % or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1 % or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.8% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, or 5% or more), based on the total monomer weight of the soft phase. In some examples, the soft phase polymer can be derived from 15 wt % or less of unsaturated alkoxysilane monomers (e.g., 13% or less, 12% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5.5% or less, 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, or 1.5% or less) based on the total monomer content of the soft phase. The amount of alkoxysilane monomer used to derive the soft phase polymer can be in the range of any of the above minimum values ​​to any of the above maximum values. For example, the soft phase polymer can be derived from greater than 0 wt % to 15 wt % of unsaturated silane monomers, such as 1 wt % to 15 wt % of unsaturated silane monomers (e.g., 1% to 10%, 1.5% to 8%, or 1.5% to 5%) based on the total monomer weight of the soft phase polymer.

[0151] The soft phase polymer may be derived from one or more additional polyamine crosslinking monomers reacted with a ketone monomer such as adipic acid dihydrazide (ADDH).

[0152] The soft phase polymer can, for example, be derived from greater than 0 wt %, e.g., 0.05 wt % or more of a crosslinking monomer (e.g., 0.1 % or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1 % or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.8% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, or 5% or more), based on the total monomer weight of the soft phase polymer. In some examples, the soft phase polymer can be derived from 15 wt % or less of crosslinking monomers (e.g., 13% or less, 12% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5.5% or less, 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, or 1.5% or less) based on the total monomer content of the soft phase polymer. The amount of crosslinking monomer from which the soft phase polymer is derived can range from any of the minimum values ​​described above to any of the maximum values ​​described above. For example, the soft phase polymer can be derived from greater than 0 wt % to 15 wt % of crosslinking monomers, such as 1 wt % to 15 wt % of crosslinking monomers (e.g., 1% to 10%, 1.5% to 8%, or 1.5% to 5%) based on the total monomer weight of the soft phase polymer.

[0153] As described herein, the soft phase polymer can be derived from greater than 0 wt% to 35 wt% of one or more additional ethylenically unsaturated monomers. When present, the one or more additional ethylenically unsaturated monomers are typically present in an amount greater than 0 wt% to 5 wt%.

[0154] As described herein, soft phase polymers can be, for example, derived from multifunctional amine groups. Examples of suitable multifunctional amines include polyetheramines, polyalkyleneamines, polyhydrazides or combinations thereof. Specific examples of multifunctional amines include polyamines sold under the trade names Baxxodur, Jeffamine and dytek. In some embodiments, amines are difunctional or higher multifunctional amine-terminated polyoxyalkylene polyols (e.g., Jeffamines or Baxxodur amines, examples being polyetheramine T403, polyetheramine D230, polyetheramine D400, polyetheramine D2000 or polyetheramine T5000). In some embodiments, amines include Dytek A, Dytek EP, Dytek HMD, Dytek BHMT and Dytek DCH-99. In some embodiments, the amine is a polyhydrazide derived from aliphatic and aromatic polycarboxylic acids, including adipic acid dihydrazide, succinic acid dihydrazide, citric acid trihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide, trimellitic acid trihydrazide, and the like. Other amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexyleneheptamine, heptaethyleneoctamine, octaethylenenonylamine, higher polyimines, such as polyethyleneimine and polypropyleneimine, bis(3-aminopropyl)amine, bis(4-aminobutyl)amine, bis(5-aminopentyl)amine, bis(6-aminohexyl)amine, 3-(2-aminoethyl)aminopropylamine, N,N-bis(3-aminopropyl)ethylenediamine, N',N-bis(3-aminopropyl)ethylenediamine, N,N-bis(3-aminopropyl)propane-1,3-diamine, N,N-bis(3-aminopropyl)butane-1,4-diamine, N,N'-bis(3-aminopropyl)propane-1,3-diamine, N,N'-bis(3-aminopropyl)butane-1,4-diamine, N,N,N'N'-tetrakis(3-aminopropyl)ethylenediamine, N,N,N'N'-tetrakis(3-aminopropyl)-1,4-butanediamine, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, tris(3-aminopropyl)amine, tris(2-aminobutyl)amine, tris(3-aminobutyl)amine, tris(4-aminobutyl)amine, tris(5-aminopentyl)amine, tris(6-aminohexyl)amine, trisaminohexane, trisaminononane, 4-aminomethyl-1,8-octamethylenediamine.

[0155] The soft phase polymer can, for example, be derived from greater than 0 wt %, e.g., 0.05 wt % or more of a polyfunctional amine (e.g., 0.1 % or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1 % or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.8% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, or 5% or more), based on the total monomer weight of the soft phase polymer. In some examples, the soft phase polymer can be derived from 15 wt % or less of the polyfunctional amine (e.g., 13 % or less, 12 % or less, 10 % or less, 9 % or less, 8 % or less, 7 % or less, 6 % or less, 5.5 % or less, 5 % or less, 4.5 % or less, 4 % or less, 3.5 % or less, 3 % or less, 2.5 % or less, 2 % or less, or 1.5 % or less) based on the total monomer content of the soft phase polymer. The amount of the polyfunctional amine from which the soft phase polymer is derived can range from any of the minimum values ​​described above to any of the maximum values ​​described above. For example, the soft phase polymer can be derived from greater than 0 wt % to 15 wt % of the polyfunctional amine, such as 1 wt % to 15 wt % of the polyfunctional amine (e.g., 1 % to 10 %, 1.5 % to 8 %, or 1.5 % to 5 %) based on the total monomer weight of the soft phase polymer.

[0156] In some embodiments, the soft phase polymer is derived from:

[0157] (i) one or more (meth)acrylate monomers;

[0158] (ii) one or more carboxylic acid-containing monomers;

[0159] (iii) one or more multifunctional crosslinking monomers;

[0160] (iv) one or more unsaturated ketone monomers;

[0161] (v) one or more polyfunctional amines;

[0162] (vi) one or more unsaturated alkoxysilane monomers; and

[0163] (vii) optionally, one or more additional ethylenically unsaturated monomers, excluding monomers (i), (ii), (iii) and (iv).

[0164] The soft phase polymer can be derived from at least 55 wt % of one or more (meth)acrylate monomers (e.g., at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, at least 80 wt %, at least 85 wt %, at least 88 wt %, at least 90 wt %, at least 91 wt %, at least 92 wt %, at least 93 wt %, at least 94 wt %, or at least 95 wt %), based on the total weight of monomers used to form the soft phase polymer.

[0165] In certain embodiments, the soft phase polymer is derived from

[0166] (i) 15 to 80 wt. % of a soft ethylenically unsaturated monomer;

[0167] (ii) 15 to 80 wt. % of a hard ethylenically unsaturated monomer;

[0168] (iii) 0 to 5 wt % of an acid monomer;

[0169] (iv) greater than 0 to 5 weight percent of a multifunctional crosslinking monomer;

[0170] (v) greater than 0 to 10 wt. % or greater than 0 to 5 wt. % of one or more unsaturated ketone monomers;

[0171] (vi) greater than 0 to 5 weight percent of one or more polyfunctional amines; and

[0172] (vii) greater than 0 to 5 weight percent of one or more unsaturated alkoxysilane monomers,

[0173] Based on total monomer weight of soft phase monomers.

[0174] In certain embodiments, the soft phase polymer is derived from

[0175] (i) 50-80 wt % of acrylate monomers;

[0176] (ii) 15-35 wt. % of methacrylate monomer;

[0177] (iii) 0 to 5 wt % of an acid monomer;

[0178] (iv) greater than 0 to 5 weight percent of a multifunctional crosslinking monomer;

[0179] (v) greater than 0 to 10 wt. % or greater than 0 to 5 wt. % of one or more unsaturated ketone monomers;

[0180] (vi) greater than 0 to 5 weight percent of one or more polyfunctional amines; and

[0181] (vii) greater than 0 to 5 weight percent of one or more unsaturated alkoxysilane monomers,

[0182] Based on total monomer weight of soft phase monomers.

[0183] In certain embodiments, the soft phase polymer is derived from

[0184] (i) 50-80 wt % of an acrylate monomer selected from methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or a combination thereof;

[0185] (ii) 15-35 wt% of a methacrylate monomer selected from methyl methacrylate, ethyl methacrylate, ureido methacrylate, n-butyl methacrylate, isobornyl methacrylate, or a combination thereof;

[0186] (iii) 0 to 5 wt % of an acid monomer selected from acrylic acid, itaconic acid, a phosphorous acid monomer, a sulfuric acid monomer or a salt thereof;

[0187] (iv) greater than 0 to 5 weight percent of a multifunctional crosslinking monomer comprising a tri(meth)acrylate monomer;

[0188] (v) greater than 0 to 10 wt% or greater than 0 to 5 wt% of an unsaturated ketone monomer selected from diacetone acrylamide or acetoacetoxyalkyl (meth)acrylate;

[0189] (vi) greater than 0 to 5 weight percent of one or more polyfunctional amines; and

[0190] (vii) greater than 0 to 5 weight percent of one or more unsaturated alkoxysilane monomers,

[0191] Based on total monomer weight of soft phase monomers.

[0192] In addition to the monomers present in the multiphase polymer as described above with respect to the first phase polymer, the second phase polymer and the soft phase polymer, the multiphase polymer may contain one or more additional monomers in one or more phases. The one or more additional monomers present in the multiphase polymer may include one or more (meth)acrylates. Embodiments of the one or more (meth)acrylate monomers include, but are not limited to, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, heptadecan ... 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate The (meth)acrylate monomers include butyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, stearyl methacrylate, behenyl methacrylate, allyl methacrylate, ethyl diglycol acrylate, iso-4-hydroxybutyl acrylate, hydroxyethyl caprolactone acrylate, 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, and combinations thereof. In some examples, the (meth)acrylate monomers include butyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or a combination thereof. For example, the (meth)acrylate monomers include butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, or a combination thereof.

[0193] The multiphase polymer in one or more phases can be derived from a carboxylic acid anhydride. The carboxylic acid anhydride typically has ethylenic unsaturation and can be derived, for example, from a monocarboxylic acid, a dicarboxylic acid, or a combination thereof. Examples of suitable carboxylic acid anhydrides include, but are not limited to, (meth)acrylic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, and combinations thereof. In some instances, the carboxylic acid anhydride can be selected from the group consisting of itaconic anhydride, maleic anhydride, and combinations thereof. In some instances, the carboxylic acid anhydride includes maleic anhydride.

[0194] In some embodiments, the multiphase polymer in one or more phases may include an aminosilane. The aminosilane may be represented by the formula H2N-R 1 -Si(OR 2 )3 means that R 1 and R 2 In each occurrence, independently selected from C1-C10 Exemplary aminoalkoxysilanes may include 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl-3-aminopropyl)-trimethoxysilane, or combinations thereof.

[0195] The multiphase polymer in one or more phases may be derived from other monomers. For example, the multiphase polymer in one or more phases may be derived from vinyl aromatic monomers, vinyl esters of branched monocarboxylic acids having a total of 2 to 12 carbon atoms and a total of 4 to 14 carbon atoms in the acid residue portion, such as vinyl acetate, vinyl 2-ethylhexanoate, vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate, vinyl neododecanoate, and mixtures thereof, diene monomers such as 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene and isoprene, and copolymerizable surfactant monomers (e.g., those sold under the trademark ADEKA REASOAP).

[0196] Suitable vinyl aromatic monomers for the copolymer can include styrene or alkyl styrenes such as α- and p-methyl styrene, α-butyl styrene, p-n-butyl styrene, p-n-decyl styrene, vinyl toluene, and combinations thereof. The vinyl aromatic monomer can be present in an amount of 0 wt % or greater (e.g., 1 wt % or greater, 2 wt % or greater, 5 wt % or greater, 10 wt % or greater, 15 wt % or greater, 20 wt % or greater, 25 wt % or greater, 0 wt % to 45 wt %, 2 wt % to 40 wt %, 5 wt % to 35 wt %, 0 wt % to 15 wt %, 0 wt % to 10 wt %, 2 wt % to 10 wt %, or 0 wt % to 5 wt %) based on the total weight of the monomers from which the heterophasic polymer is derived.

[0197] In some embodiments, the multiphase polymer in one or more phases may include (meth)acrylamide or a derivative thereof. (Meth)acrylamide derivatives include, for example, ketoamide-functional monomers defined by the following general formula VI:

[0198] CH2=CR1C(O)NR2C(O)R3 (VI)

[0199] wherein R1 is hydrogen or methyl; R2 is hydrogen, C1-C4 alkyl or phenyl; and R3 is hydrogen, C1-C4 alkyl or phenyl. For example, the (meth)acrylamide derivative may be diacetone acrylamide (DAAM).

[0200] In some embodiments, the multiphase polymer in one or more phases may include an acetoacetoxy monomer or a derivative thereof. Suitable acetoacetoxy monomers that may be included in the multiphase polymer include acetoacetoxyalkyl (meth) acrylates, such as acetoacetoxyethyl (meth) acrylate (AAEM), acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, and 2,3-bis (acetoacetoxy) propyl (meth) acrylate; allyl acetoacetate; vinyl acetoacetate; and combinations thereof. Sulfur-containing monomers that may be included in the multiphase polymer include, for example, sulfonic acids and sulfonates, such as vinyl sulfonic acid, 2-sulfoethyl methacrylate, sodium styrene sulfonate, 2-sulfoethyl methacrylate, vinyl butyl sulfonate, sulfones such as vinyl sulfone, sulfoxides such as vinyl sulfoxide, and sulfides such as 1- (2-hydroxyethylthio) butadiene. Examples of suitable phosphorus-containing monomers that may be included in the multiphase polymer include dihydrogen phosphate esters of alcohols, wherein the alcohol contains a polymerizable vinyl or olefinic group, allyl phosphates, alkyl (meth) phosphate esters such as 2-phosphoethyl (meth) acrylate (PEM), 2-phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, and butyl (meth) phosphate, 3-phospho-2-hydroxypropyl (meth) acrylate, mono- or di-phosphate esters of bis(hydroxymethyl) fumarate or itaconate; phosphate esters of hydroxyalkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ethylene oxide condensates of (meth) acrylates, H2C=C(CH3)COO(CH2CH2O) n P(O)(OH)2, and similar propylene oxide and butylene oxide condensates, wherein n is an amount of 1 to 50, crotonic acid alkyl phosphate, maleic acid alkyl phosphate, fumaric acid alkyl phosphate, (meth) acrylic acid dialkyl phosphate, crotonic acid dialkyl phosphate, vinyl phosphonic acid, allyl phosphonic acid, 2-acrylamido-2-methylpropane phosphinic acid, 2-acrylamido-2-methylpropane sulfonic acid or its salt (such as sodium salt, ammonium salt or potassium salt), α-phosphonostyrene, 2-methacrylamido-2-methylpropane phosphinic acid, (meth) acrylic acid (hydroxy) phosphinyl alkyl ester, (hydroxy) phosphinyl methacrylate and combinations thereof. In some embodiments, the multiphase polymer comprises 2-acrylamido-2-methylpropane sulfonic acid.

[0201] Hydroxy (meth)acrylates that may be included in one or more phases of the multiphase polymer include, for example, hydroxyl functional monomers defined by the following general formula VII

[0202]

[0203] Where R 1R is hydrogen or methyl and R2 is hydrogen, C1-C4 alkyl or phenyl. For example, the hydroxy(meth)acrylate may include hydroxypropyl(meth)acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate (HEA) and hydroxyethyl methacrylate (HEMA).

[0204] Other suitable additional monomers that may be included in the multiphase polymer in one or more phases include (meth)acrylonitrile, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds, phosphorus-containing monomers, acetoacetoxy monomers, thiol monomers, hydroxy(meth)acrylate monomers, methyl(meth)acrylate, ethyl(meth)acrylate, alkyl crotonates, di-n-butyl maleate, dioctyl maleate, acetoacetoxyethyl(meth)acrylate, acetoacetoxypropyl(meth)acrylate, allyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, and hydroxy(meth)acrylate monomers. Cyclohexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol (meth)acrylate, benzyl (meth)acrylate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, methyl polyethylene glycol (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, or a combination thereof.

[0205] When present, the one or more additional monomers can be present in a small amount (e.g., 10 wt % or less, 7.5 wt % or less, 5 wt % or less, 4 wt % or less, 3 wt % or less, 2 wt % or less, 1.5 wt % or less, 1 wt % or less, or 0.5 wt % or less), based on the total weight of the monomers from which the multiphase polymer is derived. When present, the one or more additional monomers can be present in an amount greater than 0 wt %, 0.1 wt % or more, 0.3 wt % or more, 0.5 wt % or more, 0.75 wt % or more, or 1 wt % or more, based on the total weight of the monomers from which the multiphase polymer is derived.

[0206] In some embodiments, the monomers in each phase of the multiphase polymer can be polymerized in the presence of a chain transfer agent. As used herein, "chain transfer agent" refers to a compound that can be used to control the molecular weight of a polymer, to reduce gelation when performing polymerization and copolymerization involving diene monomers, and / or to prepare polymers and copolymers having useful chemical functional groups at their chain ends. Chain transfer agents react with growing polymer free radicals, resulting in termination of the growing chain and the generation of new reactive species that can initiate polymerization. The phrase "chain transfer agent" is used interchangeably with the phrase "molecular weight regulator".

[0207] Suitable chain transfer agents for use during the polymerization of the multiphase polymers disclosed herein may include compounds having carbon-halogen bonds, sulfur-hydrogen bonds, silicon-hydrogen bonds, or sulfur-sulfur bonds; allyl alcohols or aldehydes. In some embodiments, chain transfer agents contain sulfur-hydrogen bonds and are referred to as thiols. In some embodiments, chain transfer agents may include C3-C 20 Mercaptan. Specific examples of the chain transfer agent may include octyl mercaptan such as n-octyl mercaptan and tert-octyl mercaptan, decyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, dodecyl mercaptan such as n-dodecyl mercaptan and tert-dodecyl mercaptan, tert-butyl mercaptan, mercaptoethanol such as β-mercaptoethanol, 3-mercaptopropanol, mercaptopropyltrimethoxysilane, tert-nonyl mercaptan, tert-dodecyl mercaptan, 6-mercaptomethyl-2-methyl-2-octanol, 4-mercapto-3-methyl-1-butanol, methyl-3-mercaptopropionate, butyl-3-mercaptopropionate, isooctyl-3-mercaptopropionate, isodecyl-3-mercaptopropionate, dodecyl-3-mercaptopropionate, octadecyl-3-mercaptopropionate, and 2-phenyl-1-mercapto-2-ethanol. Other suitable examples of chain transfer agents that can be used during the polymerization of the multiphase polymer include thioglycolic acid, methyl thioglycolate, n-butyl thioglycolate, isooctyl thioglycolate, dodecyl thioglycolate, octadecyl thioglycolate, ethyl acrylate, terpinolene. In some examples, the chain transfer agent can include tert-dodecyl mercaptan.

[0208] In some embodiments, the monomers in the heterophasic polymer are polymerized in the absence of a chain transfer agent.

[0209] When used, the amount of chain transfer agent used during polymerization can be present in an amount of at least 0.1 parts per hundred parts by weight of monomer present in the multiphase polymer. For example, the chain transfer agent can be present during polymerization in an amount of at least 1 to 4 parts, 1.5 to 4 parts, 1 to 3.5 parts, 1.5 to 3.5 parts, 1 to 3 parts, 1.5 to 3 parts, or 1 to 2.5 parts per hundred parts by weight of monomer present in the multiphase polymer. When a chain transfer agent is used, the resulting multiphase polymer can contain from about 0.01% to about 4% by weight, from about 0.05% to about 4% by weight, from about 0.1% to about 4% by weight, or from about 0.1% to about 3.5% by weight of chain transfer agent.

[0210] The volume average particle size of the multiphase polymer can be less than 400nm. In some embodiments, the volume average particle size of the multiphase polymer can be 280nm or less (e.g., 260nm or less, 250nm or less, 240nm or less, 230nm or less, 220nm or less, 200nm or less, 180nm or less, 170nm or less, 160nm or less, 150nm or less, 140nm or less, 120nm or less or 100nm or less). In some embodiments, the volume average particle size of the multiphase polymer can be 100nm to 400nm, 100nm to 300nm, 100nm to 250nm or 100nm to 180nm.

[0211] Composition

[0212] The multiphase polymer disclosed herein can be used for a wide range of applications, including coating compositions such as coatings. In certain embodiments, the coating composition may include an amount of 10% to 90% by weight of the coating composition, preferably 30% to 80% by weight of the multiphase polymer. For example, based on the total amount of polymer in the composition as described herein, the multiphase polymer can be present in an amount of 10% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 75% by weight or more, 85% by weight or more, or up to 100% by weight or more. For example, based on the gross weight of the composition as described herein, the multiphase polymer can be present in an amount of 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, or up to 100% by weight. In some examples, the multiphase polymer can be present in an amount from 10% to 100%, 10% to 95%, 10% to 65%, 10% to 50%, 20% to 65%, 30% to 95%, 40% to 90%, or 50% to 90%, by weight of the composition.

[0213] The coating composition may also include a colorant, an inorganic filler, an adhesion enhancer, a film-forming aid, a defoamer, a thickener, a tackifier or a combination thereof. When present, the inorganic filler may be selected from calcium carbonate, titanium dioxide, clay, kaolin, bentonite, mica, talc, natural silica, synthetic silica, natural silicate, synthetic silicate, feldspar, nepheline syenite, wollastonite, diatomaceous earth, barite, glass, attapulgite, zeolite or a mixture thereof. The inorganic filler may be present in an amount greater than 0% by weight to 70% by weight of the gross weight of the coating composition, preferably 5% by weight to 50% by weight, more preferably 5% by weight to 30% by weight.

[0214] The multiphase polymer can be used for base coatings. Base coatings are usually divided into groups of three or four base coatings (light, medium, dark and optional transparent colors) to cover the color range of each product type. The multiphase polymer disclosed herein is particularly suitable for deep base coatings. The art generally understands deep base coatings as base coatings that are intended to have a high level of colored pigment added thereto to achieve the desired color, usually a very bright or dark color. As disclosed herein, deep base coatings refer to any coating formulation designed to accept larger volumes of pigments, although such coating formulations are sometimes not only referred to as deep bases, but also as accent bases (accent base), ultra-deep bases and neutral bases. These formulations are designed to accept larger volumes (and weight percentages) of colored pigments. In one embodiment, a coating formulation comprising a pigment size pigment (e.g., TiO2) less than 60 pounds / 100 gallons is considered to be a deep base formulation. As known in the art, deep base formulations can be designed to have any coating finish, such as high gloss, semi-gloss, satin, eggshell and flat.

[0215] The deep base paint coating can be in the form of an aqueous latex paint composition, which includes water, a multiphase polymer as a film-forming polymer binder in an amount sufficient to form a paint film or coating when dried, one or more pigments and various additives, such as a thickener. Typically, the clear base paint is colored with a colorant to achieve the desired dark color. The colorant is a water-based dispersion of a relatively large volume of a colored pigment in a relatively small volume of water, including other components, such as one or more surfactants, a pigment dispersant that promotes the dispersion of the pigment component, and an optional inorganic filler. The colorant may be present in an amount of 2% to 20% by weight of the deep base paint coating. An example of a colorant is PureOptions sold by BASF Corporation. TM Colorants (see, e.g., U.S. Pat. No. 9,040,624), ColorCast from Sherwin Williams Company and CCA colorants for architectural coatings from the American Color Corporation.

[0216] In some embodiments, the PVC of the coating described herein may be about 45% or less, such as about 1% to about 45%, about 1% to about 30%, or about 1% to about 10%. Pigment volume concentration (PVC) is generally related to the coating finish, although multiple finishes may have overlapping PVC ranges. PVC is the percentage of the unit volume of the pigment to the volume of the pigment plus the volume of the binder. In certain embodiments, the coating is a "high gloss coating" with a low PVC. In certain embodiments, the coating is a "semi-gloss coating" with a relatively low PVC. In certain other embodiments, the coating is a "satin coating" with a relatively high PVC. In further other embodiments, the coating is a "flat coating" with a relatively high PVC compared to a satin coating. In addition to gloss, it is well known in the art to formulate coating compositions to allow the addition of desired pigments for coloring. For example, in the case of a near-white coating, a large amount of TiO2 can be used and a small amount of coloring pigment is required. On the contrary, in the case of a dark color preferred in the final coating, a large amount of coloring pigment is required and a corresponding reduction in the amount of TiO2 is necessary.

[0217] The coating compositions described herein can be formulated to have a low VOC (volatile organic compound) content, for example, less than 150 grams per liter (g / L), preferably less than 100 g / L or less than 50 g / L. In some embodiments, the coating composition is substantially free of volatile organic compounds. "Substantially free" refers to the extent to which the dispersion contains volatile organic compounds, the content of which does not cause the U.S. Environmental Protection Agency to classify it as a material that contributes to the formation of ground-level ozone or smog. For example, the coating composition may contain less than 0.1%, less than 0.01%, less than 0.001%, less than 0.0001%, or 0% of volatile organic compounds based on an aqueous composition. In some embodiments, the coating composition comprises less than or equal to 50 g / L (e.g., 45 g / L or less, 40 g / L or less, 35 g / L or less, 30 g / L or less, 25 g / L or less, 20 g / L or less, 15 g / L or less, 10 g / L or less, 9 g / L or less, 8 g / L or less, 7 g / L or less, 6 g / L or less, 5 g / L or less, 4 g / L or less, 3 g / L or less, 2 g / L or less, or 1 g / L or less) of volatile organic compounds. Without wishing to be bound by theory, a multifunctional crosslinking agent, when included in a multiphase polymer, results in enhanced phase separation of the multiphase polymer, which imparts a softer domain or surface to the multiphase polymer. The softer domain or surface promotes interdiffusion of polymer chains of the latex from one particle to another. This event can result in suppression of the minimum film forming temperature. Thus, the level of volatile organic solvents added to the composition to promote coalescence can be significantly reduced or eliminated.

[0218] Inorganic fillers

[0219] As described herein, the composition may further include at least one inorganic filler, also referred to herein as a pigment or mineral pigment. Examples of suitable inorganic fillers that may be included in the composition may be selected from TiO2 (in anatase and rutile forms), clay (aluminum silicate), CaCO3 (in ground and precipitated forms), alumina, silica, magnesium oxide, talc (magnesium silicate), bentonite, barite (barium sulfate), zinc oxide, zinc sulfite, sodium oxide, zeolite, potassium oxide, and mixtures thereof. Examples of commercially available titanium dioxide pigments are available from Kronos WorldWide, Inc. 2101, 2310, available from DuPont R-900 is commercially available from Millennium Inorganic Chemicals AT1. Titanium dioxide is also available in the form of concentrated dispersions. Examples of titanium dioxide dispersions are also available from Connos Global Ltd. 4311. Suitable pigment blends of metal oxides are sold under the trademark (oxides of silicon, aluminum, sodium and potassium commercially available from Unimin Specialty Minerals), (alumina and silica commercially available from Celite Company) and (commercially available from Imerys Performance Minerals). Exemplary fillers also include clays (such as attapulgite clay and kaolin), including and Clay sold under the trademark BASF (commercially available from BASF Corporation). Additional fillers include nepheline syenite (25% nepheline, 55% albite and 20% potassium feldspar), feldspar (aluminum silicate), diatomaceous earth, calcined diatomaceous earth, talc (hydrated magnesium silicate), aluminosilicates, silica (silicon dioxide), alumina (aluminum oxide), mica (hydrated potassium aluminum silicate), pyrophyllite (aluminum silicate hydroxide), perlite, barite (barium sulfate), wollastonite (calcium metasilicate) and combinations thereof. More preferably, the at least one filler includes TiO2, CaCO3 and / or clay.

[0220] Typically, the average particle size of the inorganic filler is from about 0.01 to about 50 microns. For example, the calcium carbonate particles used in the composition can have a median particle size of from about 0.15 to about 10 microns, such as from about 0.5 to about 7 microns or from about 0.5 to about 5 microns. The filler can be added to the composition in the form of a powder or slurry.

[0221] Based on the gross weight of the composition as described herein, the inorganic filler can be present in an amount of 0 wt % or more. For example, based on the gross weight of the composition as described herein, the inorganic filler can be present in an amount of 5 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 45 wt % or more, 50 wt % or more, 55 wt % or more, 60 wt % or more, 65 wt % or more, or up to 80 wt % or more. In some embodiments, based on the gross weight of the composition as described herein, the inorganic filler can be present in an amount of 0 wt % to 80 wt %, for example, greater than 0 wt % to 80 wt %, 5 wt % to 80 wt %, 20 wt % to 80 wt %, 40 wt % to 80 wt %, 50 wt % to 80 wt %, 30 wt % to 75 wt %, 45 wt % to 65 wt %. In some embodiments, the composition such as the coating composition does not include filler.

[0222] In some examples, the composition may further include at least one organic filler, such as polyolefin fibers, preferably polyethylene fibers.

[0223] Film-forming aids

[0224] The composition may further comprise a film-forming aid (i.e., a plasticizer). Such materials are preferably water-free, miscible with the multiphase polymer, and do not include reactive groups. Suitable film-forming aids are known in the art and may include alkyl phthalates, such as dialkyl phthalates (wherein alkyl phthalates are mixed C7, C9 and C 11 Straight chain), carbonyl phthalate, diisododecyl phthalate, dioctyl phthalate or dibutyl phthalate, diisononyl phthalate, adipates such as dioctyl adipate, azelate and sebacate, polyols such as polyoxyalkylene polyols or polyester polyols, organic phosphates and sulfonates or polybutene, hydrogenated terpenes, trioctyl phosphate, epoxy plasticizers, chlorinated paraffins, adipates, n-methylpyrrolidone and alkyl naphthalene. Other suitable plasticizers include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, butyl benzyl phthalate or a combination thereof. Examples of film-forming aids include some with and Optifilm TM A film-forming aid sold under the name ANTI-FIT.

[0225] A film-forming aid may be added to the composition to increase the glass transition temperature (T g) is lowered to below the drying temperature to allow good film formation. Based on the dry weight of the multiphase polymer, the film-forming aid may be present in an amount of 1% to 15%. For example, based on the dry weight of the multiphase polymer, the film-forming aid may be present in an amount of 5% to 15% or 7% to 15%. In some embodiments, the film-forming aid may be present in an effective amount to provide a composition having a measured Tg less than ambient temperature (e.g., 20°C). In some embodiments, the composition does not include a plasticizer or a film-forming aid. Other suitable plasticizers are described in U.S. Patent No. 9,534,158, which is incorporated by reference in its entirety.

[0226] Coagulation aid

[0227] In some embodiments, the composition may include one or more coalescing aids. Suitable coalescing aids that contribute to film formation during drying include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alkyl benzoate or a combination thereof. In some embodiments, the composition may include one or more coalescing aids, such as propylene glycol n-butyl ether and / or dipropylene glycol n-butyl ether.

[0228] Other suitable additives to the composition may include defoamers. Defoamers are used to minimize foaming during mixing and / or application of the components. Suitable defoamers include organic defoamers such as mineral oils, silicone oils, and silica-based defoamers. Exemplary silicone oils include polysiloxanes, polydimethylsiloxanes, polyether-modified polysiloxanes, or combinations thereof. Exemplary defoamers include BYK-035 available from BYK USA Inc., series of defoamers, available from Ashland Inc. series of defoamers and those available from BASF Corporation NXZ.

[0229] Examples of suitable rheology modifiers (thickeners) may include cellulosic thickeners, alkali-swellable polycarboxylic acid polymer thickeners, polyether-based thickeners, polyurethane thickeners, waxes such as polyamide waxes, hydrogenated castor oil derivatives, bentonite, laponite, attapulgite, pyrogenic silicic acid, fumed silica-based thickeners, and metal soaps (e.g., calcium stearate, aluminum stearate, barium stearate) and mixtures thereof. In some embodiments, the filler may provide rheological properties to the composition.

[0230] As described herein, the multiphase polymers described herein can be used in coating compositions, particularly deep-base coating compositions. In some embodiments, the coating composition can include a multiphase polymer, a colorant, an inorganic filler, an adhesion enhancer, a film-forming aid, a defoamer, a thickener, a tackifier, or a combination thereof. The multiphase polymer and the colorant can be present in the composition in different amounts to provide a resulting composition having properties desired for a particular application.

[0231] Properties of the coating composition

[0232] Multiphase polymers allow the production of polymer particle dispersions with lower minimum film-forming temperatures (MFFT). As used herein, the MFFT of a polymer is the temperature at which a polymer particle dispersion forms a smooth and crack-free coating or film. Contrary to conventional wisdom, the incorporation of trimethylolpropane triacrylate reduces the minimum film-forming temperature of polymer particles. This unusual crosslinking behavior helps to reduce VOC requirements to form good films at low VOCs. In particular, the polymers typically form films at low MFFTs of 40°C or less. In water-based polymer dispersions, the MFFT lower limit of the composition will be the freezing point of the aqueous carrier phase. This is typically about 0°C, and in some cases, slightly lower due to any dissolved ingredients. Therefore, as determined by ASTM D 2354-10, the MFFT range of the polymer composition is typically about 40°C or less, for example, from about -5°C to about 30°C, or from about -5°C to about 20°C. The minimum film-forming temperature (MFFT) of a polymer composition can be measured by initially casting a film using a 75 μm gap bar. Allow the film to equilibrate for two hours. Temperature measurements were obtained on the MFFT bar where the film transitioned from a continuous clear film to a cloudy or broken film (break point).

[0233] The multiphase polymer also achieves good coating pendulum hardness according to ASTM D 4366-16, printing resistance according to ASTM D2064-91; blocking resistance according to ASTM D4946; and scrub resistance determined according to ASTM D2486-06.

[0234] In certain embodiments, when applied as a film to a surface, a coating composition formulated using a polymer dispersion as described herein can form a less tackier surface in less than 24 hours at room temperature compared to a coating composition formulated using the same polymer dispersion but without the crosslinker incorporated therein. For example, a composition comprising a multiphase polymer as disclosed herein can form a less tackier surface in less than 20 hours, less than 18 hours, less than 15 hours, or less than 12 hours. Tests for determining tack-free time are described in the experimental section.

[0235] The film can also exhibit a print resistance rating of at least 4, such as from 4 to 10 or from 6 to 8, after 24 hours according to ASTM D2064-91.

[0236] The film can show a minimal tendency to block the coated substrate (i.e., the adhesion of the coated surface to another coated surface, or the adhesion of the coated surface to an uncoated surface). The adhesion of the film can be measured using the method described in ASTM D 4946-89 (2012), entitled "Standard Test Method for Anti-Blocking of Architectural Coatings". In short, the film was applied to a Leneta plain white chart with a 7mil wet film thickness and allowed to dry for a specified time (1 day, 3 days, and 7 days) before testing. A 1000g weight was placed on the rubber stopper on top of the face-to-face sample and kept at room temperature or 50°C for 30 minutes. The samples are cooled to room temperature and rated using a ten-point scale as described in the ASTM standard (10 = no tack, perfect; 9 = slightly tack, excellent; 8 = slightly tack, very good; 7 = slightly tack, good; 6 = moderate tack, good; 5 = moderate tack, fair; 4 = severe tack, no seal, fair; 3 = 5-25% seal, poor; 2 = 25-50% seal, poor; 1 = 50-75% seal, poor; 0 = completely sealed, very poor tack). In some embodiments, the film exhibits a blocking resistance of at least 5 or at least 7 at 50°C as measured according to ASTM D 4946-89.

[0237] The film may exhibit a Pendulum Hardness of at least 6 or at least 7 as determined by ASTM D 4366-16.

[0238] method

[0239] In some examples, the multiphase polymer is prepared by polymerizing the monomers using free radical emulsion polymerization. Emulsion polymerization can be performed in a batch process, a semi-batch process, or in a continuous process. In some embodiments, a portion of the monomers can be heated to the polymerization temperature and partially polymerized, and then the remainder of the monomer batch can be fed to the polymerization zone continuously, stepwise, or in a superposition of a concentration gradient. In some embodiments, the method of preparing a multiphase polymer includes

[0240] (i) polymerizing monomers including an ethylenically unsaturated acid monomer, a multifunctional crosslinking monomer, and one or more (meth)acrylates by emulsion polymerization to form a g The second phase polymer is 40°C to 240°C, wherein step i) is polymerized in the presence of the first phase polymer, wherein the first phase polymer has a T g It is 60°C to 240°C, preferably 80°C to 240°C, or more preferably 80°C to 150°C.

[0241] (ii) polymerizing monomers including one or more multifunctional crosslinking monomers, one or more (meth)acrylates, unsaturated ketone monomers and unsaturated alkoxysilane monomers by emulsion polymerization to form a g A soft phase polymer of -25°C to 30°C, preferably -25°C to 15°C, or more preferably -15°C to less than 15°C, wherein the monomer of step ii) is polymerized in the presence of the second phase polymer; and

[0242] (iii) Polymer A multifunctional amine is added to the product formed from step ii) to prepare a heterophasic polymer.

[0243] Emulsion polymerization can be carried out using a variety of auxiliaries, including water-soluble initiators and regulators. Examples of water-soluble initiators for emulsion polymerization are ammonium salts and alkali metal salts of peroxodisulfuric acid, such as sodium peroxodisulfate, hydrogen peroxide or organic peroxides, such as tert-butyl hydroperoxide. Reduction-oxidation (redox) initiator systems are also suitable as initiators for emulsion polymerization. Redox initiator systems consist of at least one (usually inorganic) reducing agent and an organic or inorganic oxidizing agent. The oxidizing component includes, for example, the initiators specified above for emulsion polymerization. The reducing component is, for example, an alkali metal salt of sulfurous acid, such as sodium sulfite, sodium bisulfite, an alkali metal salt of metabisulfite, such as sodium metabisulfite, addition compounds of bisulfite with fatty aldehydes and ketones, such as acetone bisulfite, or a reducing agent, such as hydroxymethanesulfinic acid and its salts, or ascorbic acid. Redox initiator systems can be used together with soluble metal compounds in which the metal component can exist in multiple valence states. Typical redox initiator systems include, for example, ascorbic acid / iron sulfate (II) / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium metabisulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinic acid or tert-butyl hydroperoxide / ascorbic acid. A single component, such as a reducing component, may also be a mixture, such as a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium metabisulfite. The compound is typically used in the form of an aqueous solution, wherein a lower concentration is determined by the amount of water acceptable in the dispersion, while a higher concentration is determined by the solubility of the corresponding compound in water. Based on the solution, the concentration may be 0.1% to 30% by weight, 0.5% to 20% by weight or 1.0% to 10% by weight. Based on the monomer to be polymerized, the amount of initiator is typically 0.1% to 10% by weight or 0.5% to 5% by weight. Two or more different initiators may also be used in emulsion polymerization. In order to remove residual monomers, an initiator may be added after the end of the emulsion polymerization.

[0244] In the polymerization, a molecular weight regulator or chain transfer agent can be used to reduce the molecular weight of the polymer, and the amount of the molecular weight regulator or chain transfer agent, for example, is 0 to 0.8 parts by weight based on 100 parts by weight of the monomer to be polymerized. Suitable examples include compounds with thiol groups, such as tert-butyl mercaptan, thioglycolic acid ethyl acrylate, mercaptoethanol, mercaptopropyl trimethoxysilane and tert-dodecyl mercaptan. In addition, regulators without thiol groups, such as terpinolene, can be used. In some embodiments, the emulsion polymer is prepared in the presence of at least one molecular weight regulator greater than 0% to 0.5% by weight based on the amount of monomer. In some embodiments, the emulsion polymer is prepared in the presence of a molecular weight regulator less than less than 0.3% by weight or less than 0.2% by weight (e.g., 0.10% to 0.15% by weight).

[0245] Dispersants, such as surfactants, can also be added during the polymerization process to help maintain the dispersion of the monomers in the aqueous medium. For example, the polymerization can include less than 3% by weight or less than 1% by weight of surfactant. In some embodiments, the polymerization reaction is substantially free of surfactants and can include less than 0.05% by weight or less than 0.01% by weight of one or more surfactants. In other embodiments, the first emulsion polymerization step and / or the second polymerization step further include an aryl phosphate surfactant. (For example, a tristyrylphenol alkoxylated phosphate surfactant).

[0246] Anionic and nonionic surfactants may be used during the polymerization process. Suitable surfactants include ethoxylated C8-C 36 or C 12 -C 18 Fatty alcohols, ethoxylated mono-, di- and tri-C4-C 12 or C4-C9 alkylphenol, alkali metal salt of dialkyl sulfosuccinate, C8-C 12 Alkali metal and ammonium salts of alkyl sulfates, C 12 -C 18 Alkali metal and ammonium salts of alkylsulfonic acids and C9-C 18 Alkali metal and ammonium salts of alkylarylsulfonic acids.

[0247] In some cases, the multiphase polymer comprises latex particles having a second phase polymer disposed on the surface of a first phase polymer, preferably wherein the first phase polymer forms an inner phase and the second phase polymer surrounds the inner phase.The soft phase polymer may or may not encapsulate the second phase polymer.

[0248] As disclosed herein, multiphase polymers can be used in a variety of compositions. The composition can be used in a variety of applications, including coatings such as deep base coatings. The composition can be applied to the surface by any suitable coating technique, including spraying, rolling, brushing or spreading (for example, using a trowel). Depending on the needs of a specific application, the composition can be applied with a single coating or with multiple continuous coatings (for example, with two coatings or with three coatings). Typically, the composition is dried under ambient conditions. However, in certain embodiments, the composition can be dried, for example, by heating and / or by circulating air on the composition. The composition can have a dry film thickness of 2 mil or more, such as a dry film thickness of 5 mil or more, 10 mil or more, 15 mil or more, 20 mil or more, or 25 mil or more. In some embodiments, the composition can have a dry film thickness of 30 mil or less, such as a dry film thickness of 25 mil or less, 20 mil or less, 15 mil or less, 10 mil or less, or 5 mil or less.

[0249] By way of non-limiting illustration, examples of certain embodiments of the present disclosure are given below.

[0250] Example

[0251] Example 1: Preparation of high gloss deep base coating

[0252] Low PVC coatings, such as deep base architectural coatings (dark colors, such as blue, green, red, etc.) are soft and tacky. Low PVC reduces the hardness of the coating. This situation is exacerbated by the need for soft polymers that form good films at low VOC. The large amount of low VOC colorants with soft materials used to obtain dark colors further exacerbates this situation. These coatings are soft and tacky, which results in poor blocking resistance and print resistance.

[0253] In this example, multiphase polymer particles comprising a multifunctional acrylate trimethylolpropane triacrylate, an unsaturated alkoxysilane vinyl triethoxysilane and an unsaturated ketone monomer (acetoacetoxyethyl methacrylate or diacetone acrylamide) and a multifunctional amine are prepared. The polymer particles form films at low VOCs and provide good hardness in deep base coatings. Contrary to conventional wisdom, the incorporation of trimethylolpropane triacrylate reduces the minimum film forming temperature of the polymer particles. This unusual reduction in MFFT combined with crosslinking of the ketone monomer, alkoxysilane monomer, and polyamine helps to improve the toughness of the coating while reducing the VOC requirement to form a good film at low VOCs.

[0254] Synthesis of the first phase polymer: 941.5 grams of water, 0.53 grams of Trilon BX and 77.35 grams of Calsoft L40S surfactant were added to a polymerization vessel equipped with a stirrer, metering device and temperature regulator under a nitrogen atmosphere. The initial charge was heated to 80°C with stirring. A solution of 4.9 grams of sodium persulfate in 93.1 grams of water was added to the polymerization vessel at 80°C. A separate feed of 700 grams of styrene and a solution of 205.6 grams of Calsoft L40S surfactant in 237.1 grams of water was then fed to the reactor over 3 hours. 0.7 grams of sodium persulfate in 13.3 grams of water was then added to the reactor over one hour. 30 minutes after the end of the sodium persulfate feed, the polymer was cooled to room temperature and a solution of 66.5 grams of Calsoft L40S surfactant in 191.7 grams of water was added and mixed for 10 minutes. The resulting polymer had a solid content of 33.4% and a particle size of 28 nm.

[0255] Synthesis of the second phase polymer and the soft phase polymer: The reactor feeds (Tables 1 and 2) were charged under nitrogen atmosphere in a polymerization vessel equipped with a metering device and a temperature regulator. The initial charge was heated to 85°C with stirring. When the set temperature was reached, 12.0 g of feed 1 (31%) were added and the mixture was stirred for 5 minutes. Thereafter, feed 2 was metered in over 0.85 hours. 3 minutes after the end of feed 2, feed 3 and the remaining 69% of feed 1 were added over 1.8 hours. The monomer container and feed line were then rinsed with feed 4 water. Ten minutes after the end of feeds 1 and 3, the temperature was lowered to 80°C. 30 minutes after the end of feeds 1 and 3, feeds 5 and 6 were metered in parallel over one hour. 30 minutes after the end of feeds 5 and 6, feed 7 was added and the batch was cooled to 50°C. Feed 8 was added over 10 minutes, and then feed 9 was added over 20 minutes in the case of Examples 4, 5 and 6. The feed line was rinsed with feed 10. In the case of Example 1, Example 2, Example 3 and Example 6, the pH of the polymer dispersion was adjusted to 8.5 using 19% ammonia solution. The weight percent solids, pH, particle size and minimum film forming temperature (MFFT) of the polymer dispersion were measured.

[0256] Coatings were prepared according to Tables 3 and 4 using the multiphase polymers from Tables 1 and 2 and the colorants described in Table 5. The properties of the coating compositions are shown in Table 6.

[0257] Table 1: Synthesis of heterogeneous polymers.

[0258]

[0259]

[0260] Table 2: Synthesis of heterogeneous polymers.

[0261]

[0262]

[0263]

[0264] Table 3: Clear base coating formulation

[0265]

[0266] Table 4: Deep base paint coating formula

[0267] Element S7* S8 S9 S10 S11 S12 S1(g) 100 S2(g) 100 S3(g) 100 S4(g) 100 S5(g) 100 S6(g) 100 Colorant mixture (g) 17.3 17.3 17.3 17.3 17.3 17.3 <![CDATA[Velate TM 368(g)]]> 0.4 0.0 0.0 0.0 0.0 0.0 gross weight 117.3 117.3 117.3 117.3 117.3 117.3

[0268] *-Due to the higher MFFT of the heterophasic polymer particles used, more coalescing agent (Velate TM 368) to form crack-free films. These polymer particles are synthesized in the absence of multifunctional cross-linking monomers.

[0269] Table 5: Colorant mixture

[0270] Colorants Mass(g) <![CDATA[PureOptions TM Colorant BL*]]> 109.5 <![CDATA[PureOptions TM EUL Dye*]]> 96 <![CDATA[PureOptions TM Colorant LL*]]> 164.7 <![CDATA[Pure Options TM Colorant KXL*]]> 277.5 total 647.7

[0271] *- Available from BASF

[0272] Table 6: Coating properties

[0273]

[0274] Test method:

[0275] Printing resistance testing was carried out according to ASTM D 2064-91 with minor modifications: the coating was applied with a 255 μm (instead of 150 μm) Erichsen applicator model 97181; the weight used was 500 g (instead of 500 g), and the test temperature was 50°C.

[0276] Block Resistance Test The test was conducted according to ASTM D 4946-89 test method as follows: The coating was applied on Leneta plain white seal paper using a BYK 7mil Dow latex film caster and cured for 24 hours at 50% humidity and 76°F.

[0277] Cotton Ball Tack Test: Paint was applied on Leneta plain white seal paper using a BYK 7mil Dow latex film caster and cured for 24 hours at 50% humidity and 76°F. A cotton ball was placed on the paint surface and a 500 gram weight was placed on the cotton ball. The sample was placed in a 50°C oven for one hour. After one hour, the sample was cooled to ambient temperature for 30 minutes and the cotton ball was removed. The test sample was rated on a scale of 0 to 5, with 0 indicating no cotton fibers adhered to the paint surface and 5 indicating a thick layer of cotton fibers adhered to the entire test paint surface area. The amount of cotton fibers increased as the paint surface tack increased.

[0278] Pendulum hardness testing is performed according to ASTM D 4366-16 and the results are reported in seconds.

[0279] Minimum Film Forming Temperature (MFFT) was measured according to ASTM D 2354-10. A 75 μm one inch cube applicator was used.

[0280] Low Temperature Film Formation (LTC): The coating, BYK 10mil Dow latex film caster and Leneta Form 19BR Penopec sheet were placed in an environmental chamber at 5°C temperature and 50% humidity for one hour. The coating was then quickly applied to the Penopec sheet using the film caster and immediately placed in an environmental chamber at 5°C temperature and 50% humidity. After 24 hours, the sheet was removed from the environmental chamber and inspected for any cracks in the film. Films without cracks were rated as acceptable and films with cracks were rated as unacceptable.

[0281] Summary The coating compositions provided in this example achieve deep base coatings with low PVC and low VOC. The coatings formulated in combination with a crosslinker are harder, resulting in a less sticky surface and good anti-blocking and printing resistance, while surprisingly reducing the need for VOC coalescing agents.

[0282] The scope of the compositions and methods of the appended claims is not limited by the specific compositions and methods described herein, which are intended to illustrate several aspects of the claims, and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. In addition to the compositions and methods shown and described herein, various modifications to the methods are intended to fall within the scope of the appended claims. Further, although only certain representative compositions and method steps disclosed herein are specifically described, other combinations of these compositions and method steps are also intended to fall within the scope of the appended claims, even if not specifically described. Therefore, combinations of steps, elements, components, or ingredients may be explicitly mentioned herein, however, less other combinations of steps, elements, components, and ingredients are included, even if not explicitly stated. As used herein, the term "comprising" and its variants are used synonymously with the term "including" and its variants, and are open, non-restrictive terms. Although the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, and are also disclosed. Except in the examples or where otherwise indicated, all numbers used in the specification and claims indicating quantities of ingredients, reaction conditions, and the like should at least be understood, rather than attempting to limit the application of the doctrine of equivalents to the scope of the claims, to be interpreted in light of the number of significant figures and ordinary rounding methods.

Claims

1. A multiphase polymer comprising: The first phase polymer, whose T g 60℃ to 240℃; The second phase polymer, its T g is 40° C. to 240° C., and is derived from monomers including an ethylenically unsaturated acid monomer, a multifunctional crosslinking monomer, and one or more (meth)acrylates, Soft phase polymer, its T g The temperature is from -25°C to 30°C and is derived from monomers including one or more multifunctional crosslinking monomers, one or more (meth)acrylates, unsaturated ketone monomers, unsaturated alkoxysilane monomers and multifunctional amines, wherein the multifunctional crosslinking monomer includes tri(meth)acrylate.

2. The multiphase polymer of claim 1, wherein the first phase polymer is derived from monomers comprising methacrylate monomers, vinyl aromatic monomers, or combinations thereof.

3. The multiphase polymer according to claim 1 or 2, wherein: The first phase polymer includes styrene.

4. The multiphase polymer of claim 1 wherein the first phase polymer is derived from greater than 0 weight percent styrene based on the total weight of the first phase polymer.

5. The multiphase polymer of claim 1, wherein the first phase polymer is present in an amount greater than 0 wt% and less than or equal to 10 wt%, based on the total weight of the multiphase polymer.

6. The multiphase polymer of claim 1, wherein the ethylenically unsaturated acid monomers in the second phase polymer are selected from carboxylic acid monomers, phosphorous acid monomers, sulfuric acid monomers, or mixtures thereof.

7. The multiphase polymer of claim 6, wherein the ethylenically unsaturated acid monomer is selected from acrylic acid; Methacrylic acid; itaconic acid; maleic acid; fumaric acid; crotonic acid; vinylphosphonic acid; allylphosphonic acid; 2-Acrylamide-2-methylpropanephosphonic acid; a-phosphonostyrene; 2-methacrylamide-2-methylpropanephosphonic acid; 2-phosphoethyl (meth)acrylate; 2-phosphopropyl (meth)acrylate; 3-phosphopropyl (meth)acrylate; 3-phosphopropyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; 2-acrylamide-2-methylpropanesulfonic acid; styrenesulfonic acid; mixtures thereof or salts thereof.

8. The multiphase polymer of claim 1 wherein the ethylenically unsaturated acid monomer is present in the second phase polymer in an amount from 0.01% to 6% by weight of the second phase polymer.

9. The multiphase polymer of claim 1 wherein one or both of the soft phase polymer, the first phase polymer, do not include an acid monomer.

10. The multiphase polymer of claim 1, wherein the multifunctional crosslinking monomer is selected from divinyl monomers, diallyl monomers, trivinyl monomers, triallyl monomers, allyl (meth)acrylates, di(meth)acrylates, tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates, or combinations thereof.

11. The multiphase polymer of claim 1 wherein the multifunctional crosslinking monomer comprises trimethylolpropane triacrylate.

12. The multiphase polymer of claim 1, wherein the multifunctional crosslinking monomer is present in the second phase polymer in an amount from 0.01% to 5% by weight of the second phase polymer.

13. The multiphase polymer of claim 1, wherein the multifunctional crosslinking monomer is present in the soft phase polymer in an amount of 0.01 wt% to 5 wt% of the soft phase polymer.

14. The heterophasic polymer of claim 1, wherein the multifunctional crosslinking monomer is present in an amount from 0.02% to 10% by weight of the heterophasic polymer.

15. The multiphase polymer of claim 1 wherein the one or more (meth)acrylates comprises at least one methacrylate monomer and at least one acrylate monomer.

16. The multiphase polymer of claim 1, wherein the one or more (meth)acrylates comprise a methacrylate monomer selected from methyl methacrylate, ureido methacrylate, n-butyl methacrylate, isobornyl methacrylate, or combinations thereof.

17. The multiphase polymer of claim 1, wherein the one or more (meth)acrylates comprise an acrylate monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or combinations thereof.

18. The multiphase polymer of claim 15, wherein the second phase polymer comprises at least one methacrylate monomer in an amount from 40% to 90% by weight of the second phase polymer and at least one acrylate monomer in an amount from 1% to 10% by weight of the second phase polymer.

19. The multiphase polymer of claim 15, wherein the soft phase polymer comprises at least one methacrylate monomer in an amount of 5 to 40 weight percent of the soft phase polymer and at least one acrylate monomer in an amount of 40 to 90 weight percent of the soft phase polymer.

20. The multiphase polymer of claim 1, wherein the one or more (meth)acrylates are present in an amount from 80% to 97% by weight of the multiphase polymer.

21. The heterophasic polymer of claim 1, wherein the unsaturated ketone monomer comprises diacetone acrylamide, acetoacetoxyalkyl (meth)acrylate, or a combination thereof.

22. The multiphase polymer of claim 1 wherein the unsaturated ketone monomer is present in the soft phase polymer in an amount from 0.01 wt% to 15 wt% of the soft phase polymer.

23. The multiphase polymer of claim 1 wherein the second phase polymer further comprises an unsaturated ketone monomer, and a multifunctional amine.

24. The multiphase polymer of claim 23 wherein the unsaturated ketone monomer is present in the second phase polymer in an amount from 0.01% to 15% by weight of the second phase polymer.

25. The multiphase polymer of claim 1 wherein the unsaturated alkoxysilane monomer is present in the soft phase polymer in an amount from 0.01 wt% to 5 wt% of the soft phase polymer.

26. The multiphase polymer of claim 1 wherein the second phase polymer further comprises an unsaturated alkoxysilane monomer.

27. The multiphase polymer of claim 26, wherein the unsaturated alkoxysilane monomer is present in the second phase polymer in an amount from 0.01% to 5% by weight of the second phase polymer.

28. The multiphase polymer of claim 1 or 26, wherein the unsaturated alkoxysilane monomer is selected from vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxysilane), vinyl triisopropoxysilane, (3-methacryloxypropyl)-trimethoxysilane, (3-methacryloxypropyl)-triethoxysilane, (3-methacryloxypropyl)-triisopropoxysilane, 2-methyl-2-acrylic acid 3-[tris-(1-methylethoxy)-silyl]-propyl ester, (3-methacryloxypropyl)-methyldiethoxysilane, oligomers thereof, polymers thereof, or combinations thereof.

29. The multiphase polymer of claim 1 wherein the multifunctional amine comprises a polyetheramine or a polyhydrazide.

30. The heterophasic polymer of claim 1 wherein the polyfunctional amine is reacted with the unsaturated ketone monomer.

31. The multiphase polymer of claim 30, wherein the multifunctional amine is pendant from the backbone of the soft phase polymer and / or the second phase polymer.

32. The heterophasic polymer of claim 1 wherein the multifunctional amine is present in an amount from 0.01% to 3% by weight of the heterophasic polymer.

33. The multiphase polymer of claim 1 wherein one or both of the second phase polymer and the soft phase polymer comprises styrene.

34. The multiphase polymer of claim 1, wherein the multiphase polymer comprises one or more additional monomers.

35. The multiphase polymer of claim 34, wherein the one or more additional monomers comprise (meth)acrylonitrile monomers, (meth)acrylamide monomers, glycidyl (meth)acrylates, hydroxyalkyl (meth)acrylates, or combinations thereof.

36. The multiphase polymer of claim 1, wherein the second phase polymer and the soft phase polymer are derived from monomers comprising: 0.1 wt % to 5 wt % of a multifunctional crosslinking monomer including a tri(meth)acrylate monomer; 0.5 to 10 wt% of an unsaturated ketone monomer including diacetone acrylamide or acetoacetoxyalkyl (meth)acrylate; 0.1 to 5 wt% of an unsaturated alkoxysilane monomer, 0.1 to 8% by weight of urea (meth)acrylate; 0.1 to 5 wt% of a polyfunctional amine and 80 to 97 weight percent of two or more (meth)acrylates comprising at least one methacrylate monomer and at least one acrylate monomer, The weight percentages are based on the total weight of the monomers in the second phase and the soft phase.

37. The multiphase polymer of claim 1, wherein the second phase polymer is present in an amount greater than 0 wt% and less than or equal to 50 wt%, based on the total weight of the multiphase polymer.

38. The heterophasic polymer of claim 1, wherein the soft phase polymer is present in an amount greater than or equal to 50 wt% and less than 100 wt%, based on the total weight of the heterophasic polymer.

39. The multiphase polymer of claim 1 wherein the Tg of the second phase polymer is 25°C or less below the Tg of the first phase polymer.

40. The multiphase polymer of claim 1 wherein the Tg of the soft phase polymer is 50°C or more lower than the Tg of the second phase polymer.

41. The multiphase polymer of claim 1, wherein the multiphase polymer has a minimum film forming temperature (MFFT) that is less than the minimum film forming temperature of the same multiphase polymer without the multifunctional crosslinking monomer in one or both of the second phase polymer and the soft phase polymer.

42. The multiphase polymer of claim 1, wherein the multiphase polymer has a minimum film forming temperature of 40°C or less.

43. The multiphase polymer of claim 1 wherein the first phase polymer has a particle size of 60 nm or less.

44. The multiphase polymer of claim 1, wherein the multiphase polymer has a particle size of 400 nm or less.

45. A coating composition comprising: a multiphase polymer according to any one of claims 1-44.

46. ​​The coating composition of claim 45, wherein the multiphase polymer is present in an amount from 10% to 90% by weight of the coating composition.

47. The coating composition of claim 45, further comprising a colorant, an inorganic filler, a film-forming aid, a defoaming agent, a thickener, a tackifier, or a combination thereof.

48. The coating composition of claim 47, wherein the coating composition comprises an inorganic filler.

49. The composition of claim 47 or 48, wherein the inorganic filler is present in an amount from greater than 0 wt% to 70 wt% of the total weight of the coating composition.

50. The coating composition of claim 45, wherein the coating composition is a paint.

51. The coating composition of claim 50, wherein the coating composition is a deep base paint and comprises the colorant, wherein the colorant is present in an amount of 2% to 20% by weight of the deep base paint.

52. The coating composition of claim 51, wherein the colorant comprises a colored pigment, a surfactant, a pigment dispersant, and an inorganic filler.

53. The coating composition of claim 45, wherein the coating composition has a PVC of 45% or less.

54. The coating composition of claim 45, wherein when applied as a film to a surface, forms a less tacky surface in less than 24 hours at room temperature compared to a coating formulated using the same multiphase polymer without the combination of the crosslinking agent, the multifunctional crosslinking monomer, the unsaturated ketone monomer, the unsaturated alkoxysilane monomer, and the polyamine.

55. A film derived from the coating composition of any one of claims 45-54, after application as a coating to a substrate and after drying.

56. The film of claim 55, wherein the film has a print resistance rating of at least 4 according to ASTM D2064-91 after drying for 24 hours.

57. The film of any of claims 55-56, wherein the film has a blocking resistance rating of at least 5 at 50°C after drying for 24 hours according to ASTM D 4946-89.

58. The film of claim 55, wherein the film has a pendulum hardness of at least 6 seconds after drying for 24 hours as determined by ASTM D4366-16.

59. A method for preparing a multiphase polymer, the method comprising: a) by emulsion polymerization, comprising an ethylenically unsaturated acid monomer, a multifunctional crosslinking monomer and one or more (formaldehyde) The monomers of the acrylic acid ester are polymerized to form T g A second phase polymer having a temperature of 40°C to 240°C; wherein the monomers of step a) are polymerized in the presence of a first phase polymer, and wherein the T g 60℃ to 240℃; b) polymerizing monomers including one or more multifunctional crosslinking monomers, one or more (meth)acrylates, unsaturated ketone monomers and unsaturated alkoxysilane monomers by emulsion polymerization to form T g -25℃ to Soft phase polymer at 30°C, wherein the monomers of step b) are polymerized in the presence of a first phase polymer and a second phase polymer; and c) reacting a polyfunctional amine with the product formed from step b) to produce said heterophasic polymer.

60. The method of claim 59, wherein the multiphase polymer has an average particle size of less than 400 nm.

61. The method of claim 59 or 60, wherein the multiphase polymer comprises latex particles having the second phase polymer disposed on surfaces of the first phase polymer.

62. The method of claim 59, wherein the multiphase polymer comprises latex particles having the soft phase polymer disposed on the surface of the second phase polymer, or wherein the soft phase polymer and the second phase polymer form acorn or Janus type particles.

63. The method of claim 59, wherein the first phase polymer is derived from monomers comprising methacrylate monomers, vinyl aromatic monomers, or combinations thereof.

64. The method of claim 59, wherein the first phase polymer is present in an amount of 10 weight percent or less based on the total weight of the multiphase polymer.

65. The method of claim 59, wherein the second phase polymer and the soft phase polymer are derived from monomers comprising: 0.1 wt % to 5 wt % of a multifunctional crosslinking monomer including a tri(meth)acrylate monomer; 0.5 to 10 wt% of an unsaturated ketone monomer including acetoacetoxyalkyl (meth)acrylate, diacetone acrylamide, or a combination thereof 0.1 wt % to 5 wt % of an unsaturated alkoxysilane monomer; 0.1 to 8% by weight of urea (meth)acrylate; 0.1 wt % to 5 wt % of a polyfunctional amine; and 80 to 97 weight percent of two or more (meth)acrylates comprising at least one methacrylate monomer and at least one acrylate monomer, The weight percentages are based on the total weight of the monomers in the second phase and the soft phase.

66. The method of claim 59, wherein the multifunctional amine comprises a polyetheramine, a polyhydrazide, or a combination thereof.

67. The method of claim 66, wherein the polyetheramine and / or polyhydrazide is incorporated in a ratio of keto groups to amine groups or hydrazide groups or a combination of amine groups and hydrazide groups of 1:0.1 to 1:1.

2.

68. The method of claim 59, wherein the second phase polymer is present in an amount greater than 0 wt% and less than or equal to 50 wt%, based on the total weight of the multiphase polymer.

69. The method of claim 59, wherein the soft phase polymer is present in an amount greater than or equal to 50 wt% and less than 100 wt%, based on the total weight of the multiphase polymer.

70. The method of claim 59, wherein the Tg of the second phase polymer is 25°C or less below the Tg of the first phase polymer.

71. The method of claim 59, wherein the soft phase polymer has a Tg of 50°C or greater that is less than the second phase polymer.

Images