Antifouling building composition containing a cationic resin and a nonionic resin blend

Abstract

Disclosed herein are stable nonionic resin compositions that are compatible with cationic resin compositions, and blends of the nonionic resins and cationic resins. Primer and topcoat compositions containing such blends are capable of preventing stains from migrating to the top of the paint film and resisting the effects of water sensitivity.

Description

Field of the Invention

[0001] The present invention relates to low VOC, waterborne, antifouling building compositions including, but not limited to, primer or topcoat compositions comprising a cationic resin blended with a stable nonionic resin composition. Background of the Invention

[0003] Certain substrates to be painted, such as wood, contain tannins, which are astringent polyphenolic biomolecules that can penetrate paint films (including primer layers) and stain topcoat layers, becoming undesirable visible stains on the painted substrate. Other stains include crayons, lipstick, markers, coffee, wine, etc. and other stains on walls, and water drop stains on ceilings, which can penetrate paint films.

[0004] Conventional solvent-based alkyd coatings block stains but have odor and high volatile organic component (VOC) emissions. Hydrophobic waterborne acrylic resins have been used to block stains by forming a hydrophobic paint film layer. In these hydrophobic waterborne systems, stains still penetrate into the primer layer and eventually the topcoat.

[0005] Most stains are anionic in nature and can be prevented from migrating by cationic resins in waterborne building compositions. Cationic resins restrict the migration of water-soluble stains in waterborne coating applications. Cationic resins form complexes with anionic stains in an ion exchange setting, rendering the stains insoluble and trapped or locked in the primer film as it dries. However, cationic resins are generally highly hydrophilic and can increase the water sensitivity of building compositions and paint films. Increased water sensitivity in cationic coatings can result in loss of wet adhesion, scrub resistance, and blister resistance.

[0006] As discussed in U.S. Pat. No. 5,312,863, conventional water-based latex coatings are typically anionic. Anionic latex polymer binders are typically prepared by aqueous emulsion polymerization techniques using nonionic and / or anionic surfactants. These anionic latex polymer binders are blended with opacifying pigments, extender pigments, and dispersed with anionic pigment dispersants to form water-based latex coatings or paints. The anionic binders typically contain anionic functional groups such as sulfate and carboxylate groups. Functionalization of these anionic latex polymers with amines, acetoacetates, or amides (such as ethylene urea derivatives) can improve wet adhesion to substrates. The '863 patent and the references cited therein are incorporated by reference in their entirety.

[0007] However, heretofore, cationic resins have not been blended or mixed with anionic resins to alleviate the water sensitivity problems associated with cationic resins. Blending or mixing cationic resins with anionic resins tends to result in coarse particle formation or gelation and generally results in a loss of performance and physical properties.

[0008] Therefore, there is still a need for water-based formulations with improved stain resistance and that can prevent stain migration from the substrate to the topcoat while minimizing the water sensitivity of the paint film. More specifically, such anti-stain formulations utilize the stain-locking ability of cationic resins while mitigating the negative effects of their water sensitivity by blending the cationic resins with nonionic resins. Summary of the invention

[0009] Thus, the present invention relates to novel waterborne building compositions that pair a stain-binding cationic resin with a novel stable waterborne composition that minimizes or eliminates the water sensitivity of the cationic resin. Preferably, the stable waterborne composition of the present invention includes a nonionic waterborne resin composition that acts as a carrier for the cationic resin. The nonionic resin composition of the present invention is stable and compatible with the cationic resin, i.e., the nonionic resin composition of the present invention does not form grit or gel when blended with the cationic resin.

[0010] In one embodiment of the present invention, the blend of the nonionic resin and cationic resin of the present invention in an aqueous paint composition provides balanced properties including antifouling ability, anti-fouling and improved adhesion to substrates. The cationic resin provides dirt lock ability and the nonionic resin enhances film formation and adhesion to substrates.

[0011] Preferably, the nonionic resin of the present invention contains no or substantially no acid monomers, such as monomers with carboxylic acids, and contains no or substantially no monomers with anionic groups, such as monomers with phosphates, sulfonates, and other anionically charged monomers. As used herein, substantially free of monomers (e.g., acid monomers or monomers with anionic groups) refers to a low level of less than 0.25 wt%, preferably less than 0.125 wt%, more preferably less than 0.1 wt% of the total monomer content. More preferably, the nonionic resin of the present invention contains no acid monomers, i.e., substantially no acid monomers or other monomers with anionic groups.

[0012] Without being bound by any particular theory, the inventors of the present invention have found that when a polymerizable nonionic hydrophilic component (such as a polymerizable polyethylene glycol monomer or a polymerizable polypropylene glycol monomer) is copolymerized with a film-forming monomer and a nonionic surfactant to form micelles, polymerization (preferably emulsion polymerization) can be carried out in the absence of an acid monomer. In one embodiment, only nonionic surfactants are used to form micelles and latex particles.

[0013] The nonionic surfactant is preferably present in less than about 5 wt%, preferably about 1 wt% to about 4 wt%, preferably about 1.5 wt% to about 3.5 wt%. Alternatively, the nonionic surfactant is present in about 1 wt% to about 4.5 wt%, preferably about 1.25 wt% to about 4.25 wt%, and preferably about 1.5 wt% to about 3.75 wt%. The nonionic surfactant preferably has an (HLB) value of about 14 to about 18, preferably about 14 to about 17, preferably about 15 to about 18.

[0014] The nonionic polymerizable hydrophilic component, such as methoxy polyethylene glycol methacrylate or methoxy polypropylene glycol methacrylate, is preferably present in an amount of 0 wt % to about 10 wt % (i.e., less than 10 wt %), 0 wt % to about 5 wt % (i.e., less than 5 wt %), or preferably about 1.5 wt % to about 3.5 wt %. Alternatively, the nonionic polymerizable hydrophilic component is present in an amount of about 1 wt % to about 5 wt %, preferably about 1.25 wt % to about 4.5 wt %, preferably about 1.5 wt % to about 3.5 wt %, preferably about 1.75 wt % to about 3.25 wt %.

[0015] In one embodiment, a small amount of anionic surfactant can be used to replace nonionic surfactant in the initial inoculation stage to better control the particle size of seed formation. The total amount of anionic surfactant can be from 0 wt % to about 0.25 wt %, preferably from 0.01 wt % to about 0.25 wt %, preferably from about 0.05 wt % to about 0.15 wt % based on the total monomer content. Alternatively, the range of anionic surfactants used in the inoculation process can be from 0.035 wt % to about 0.15 wt % based on the total monomer content. Without being limited to any particular theory, the inventors of the present invention believe that anionic surfactants are more effective in controlling particle size and are compatible with latex and cationic paints at low levels of anionic surfactants.

[0016] Without being bound by any particular theory, the inventors believe that the seeds polymerized using the anionic surfactant are covered by the monomers polymerized using the nonionic surfactant during the polymerization of the latex particles. In the nonionic latex resin of the present invention, the seeds formed using the anionic surfactant are chemically isolated, and the anionic seeds do not react with the cationic latex resin or the reaction level is insufficient to produce coarse particles, gels or other precipitated particles.

[0017] Alternatively, the seeds may be polymerized with a nonionic surfactant that produces a nonionic latex resin with a larger particle size. Alternatively, the seeds may be prepared separately, or may be purchased commercially and used for polymerization.

[0018] The percentages of the components of the nonionic resins described herein are given as weight percent of active ingredients, including the weight of solid monomers and active ingredients of additives, excluding water.

[0019] For primer compositions that can be applied to substrates including metal substrates, flash rust inhibitors are preferred. In addition, organic flash rust inhibitors are preferred due to their efficiency and compatibility.

[0020] One embodiment of the present invention is directed to a paint composition comprising a blend of a cationic latex resin and a substantially nonionic latex resin. The substantially nonionic latex resin is polymerized from:

[0021] A monomer mixture comprising at least one nonionic (meth)acrylate monomer, a polymerizable nonionic hydrophilic component, wherein the monomer mixture is substantially free of acid monomers or other monomers with anionic groups, and

[0022] a nonionic surfactant ranging from about 1 wt % to about 4 wt %, preferably from about 1.5 wt % to about 3.5 wt %; and

[0023] wherein the polymerizable hydrophilic component is present in an amount of about 1.5 wt % to about 3.5 wt %,

[0024] The weight percentages stated do not include water.

[0025] Another embodiment of the present invention is directed to another paint composition comprising a blend of a cationic latex resin and a substantially nonionic latex resin. The substantially nonionic latex resin is polymerized from:

[0026] A monomer mixture comprising at least one nonionic (meth)acrylate monomer, a polymerizable nonionic hydrophilic component, wherein the monomer mixture is substantially free of acid monomers or other monomers with anionic groups, and

[0027] A nonionic surfactant in the range of about 1 wt % to about 4.5 wt %, preferably about 1.25 wt % to about 4.25 wt %, preferably about 1.5 wt % to about 3.75 wt %, wherein the HLB value of the nonionic surfactant is in the range of about 14 to about 18, preferably about 14 to about 17, preferably about 15 to about 18.

[0028] wherein the polymerizable hydrophilic component is present in an amount of about 1 wt % to about 5 wt %, preferably about 1.25 wt % to about 4.5 wt %, preferably about 1.5 wt % to about 3.5 wt %, preferably about 1.75 wt % to about 3.25 wt %,

[0029] The weight percentages stated do not include water.

[0030] The monomer mixture of the paint composition of the present invention preferably does not contain acid monomers or other monomers with anionic groups. Alternatively, the acid monomers or other monomers with anionic groups in the monomer mixture are less than 0.25% by weight, preferably less than 0.125% by weight of the total monomer content.

[0031] In one embodiment, the substantially nonionic resin is additionally polymerized with an inoculum amount of anionic surfactant, the inoculum amount ranging from about 0.01 wt % to about 0.25 wt %, preferably from about 0.05 wt % to about 0.15 wt %, based on the total monomer content. Alternatively, the substantially nonionic resin is additionally polymerized with an inoculum amount of anionic surfactant, the inoculum amount ranging from about 0.035 wt % to about 0.15 wt %, based on the total monomer content.

[0032] The blend of the nonionic resin and the cationic resin of the present invention ranges from

[0033] a. from 80 wt % cationic resin and 20 wt % nonionic resin to 20 wt % cationic resin and 80 wt % nonionic resin,

[0034] b. from 70 wt % cationic resin and 30 wt % nonionic resin to 30 wt % cationic resin and 70 wt % nonionic resin,

[0035] c. from 60 wt % cationic resin and 40 wt % nonionic resin to 40 wt % cationic resin and 60 wt % nonionic resin, or

[0036] d. from 55 wt % cationic resin and 45 wt % nonionic resin to 45 wt % cationic resin and 55 wt % nonionic resin,

[0037] e. wherein the weight % of the cationic resin and the nonionic resin are dry weight.

[0038] The paint composition of the present invention may contain a rust inhibitor.

[0039] The polymerizable hydrophilic component comprises a polymerizable polyethylene glycol monomer or a polymerizable polypropylene glycol monomer. The polymerizable polyethylene glycol monomer is preferably a methoxy polyethylene glycol methacrylate monomer.

[0040] The HLB value of the nonionic surfactant may range from about 14 to about 18, preferably from about 14 to about 17, and preferably from about 15 to about 18.

[0041] In certain embodiments, only nonionic surfactants are used in the polymerization, ie, to form micelles and the substantially nonionic latex resin.

[0042] Another embodiment of the present invention is directed to a method for blocking stains on a substrate from migrating to a paint film covering the substrate while minimizing adverse water sensitivity issues between the substrate and the paint film, wherein the method comprises the steps of:

[0043] i. blending a cationic resin with a nonionic resin to form a blended resin composition without forming coarse particles or gels;

[0044] ii. preparing a paint composition, preferably a primer or topcoat composition, comprising the blended resin composition and an opacifying pigment; and

[0045] iii. covering the substrate with the paint composition, wherein the paint composition dries and forms the paint film.

[0046] Preferably, the nonionic resin is substantially free of acid monomers or other monomers with anionic groups during polymerization. Alternatively, the acid monomers or other monomers with anionic groups are less than 0.25% by weight, preferably less than 0.125% by weight, more preferably less than about 0.1% by weight of the total monomer content. Preferably, the nonionic resin is free of acid monomers or other monomers with anionic groups during polymerization.

[0047] Preferably, the nonionic resin is polymerized from a monomer mixture comprising at least one nonionic (meth)acrylate monomer, a polymerizable nonionic hydrophilic component and a nonionic surfactant. Preferably, the nonionic resin utilized in the method is the nonionic resin of the present invention discussed herein.

[0048] As used herein, "substantially nonionic latex resin" refers to a nonionic latex resin that is substantially free of acid monomers or monomers with anionic groups, and that may include an inoculum amount of anionic surfactant used in the inoculum stage of the polymerization process to control the particle size of the latex resin, as those terms are defined and used herein. Preferably, no acid monomers and no monomers with anionic groups are used in the polymerization of the nonionic resin.

[0049] Specific implementation methods of the preferred embodiment

[0050] Although capable of locking in stains and minimizing the ability of stains to migrate through a paint film, cationic resins can cause water sensitivity problems such as loss of wet adhesion, reduced scrub resistance, and reduced blister resistance due to their hydrophilic nature. As shown in the following experiments, cationic paints and primers suffer from water sensitivity such as blistering on the paint film when used alone. The present invention solves this problem by blending cationic resins with novel stable nonionic resins. The stable nonionic resin compositions of the present invention are advantageously compatible with cationic resins and do not form grit or gels when blended with cationic resins.

[0051] U.S. Pat. No. 4,981,759 discloses that a nonionic acrylic resin can be obtained by (co)polymerizing at least one unsaturated monomer selected from alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; (meth)acrylic acid; aromatic vinyl compounds such as styrene and its derivatives (e.g., α-methylstyrene); (meth)acrylonitrile; and butadiene, depending on the desired properties.

[0052] Typical emulsion polymerizations (such as those described in the '759 patent) include acrylic, vinyl or styrene monomers, and a small amount of an acid monomer, such as (meth)acrylic acid, is added to stabilize the polymerization. Generally, in the absence of an acid monomer, the emulsion process is unstable and often unsuccessful. The inventors of the present invention have determined that the use of an acid monomer such as (meth)acrylic acid in the polymerization renders the resulting polymer anionic. Without being bound by any particular theory, it is believed that the side chains on the (meth)acrylic acid in the latex polymer lose protons and become anionic.

[0053] Without being limited to any particular theory, the inventors of the present invention have found that when a polymerizable nonionic hydrophilic component such as a polymerizable polyethylene glycol or a polymerizable polypropylene glycol monomer is copolymerized with a film-forming monomer and a nonionic surfactant to form micelles, polymerization (preferably emulsion polymerization) can be performed in the absence of an acid monomer. In certain embodiments, the only surfactant used to form micelles and latex particles is a nonionic surfactant. In other embodiments, a small amount of anionic surfactant is used during the initial seeding process.

[0054] In a preferred embodiment of the present invention, acid monomers are omitted or substantially omitted from the polymerization to prevent these moieties from forming anions on the polymer. In order to impart stability to the nonionic polymer resin, a hydrophilic nonionic surfactant is used in the polymerization. In addition, a polymerizable nonionic hydrophilic component is added to the polymerization, such as a polymerizable polyethylene glycol monomer or a polymerizable polypropylene glycol monomer (e.g., methoxy polyethylene glycol methacrylate (molecular weight 750 Daltons, 50% in water)). In this embodiment, in order to seed the polymerization, a small amount of anionic surfactant is added in the initial stage of the polymerization. The anionic surfactant is preferably the only ionic component in the polymerization and effectively provides seeds for the latex polymer.

[0055] The acid monomers are preferably kept below 0.25 wt%, preferably below 0.125 wt%, and preferably below 0.1 wt% and more preferably 0 wt%.

[0056] The nonionic surfactant is preferably present in an amount of 0% by weight to about 5% by weight (less than 5% by weight), preferably about 1% by weight to about 4% by weight, preferably about 1.5% by weight to about 3.5% by weight. Alternatively, the nonionic surfactant is present in an amount of about 1% by weight to about 4.5% by weight, preferably about 1.25% by weight to about 4.25% by weight, and preferably about 1.5% by weight to about 3.75% by weight. The anionic surfactant is preferably present in an amount of 0% by weight to about 0.25% by weight, preferably 0.01% by weight to about 0.25% by weight, preferably about 0.05% by weight to about 0.15% by weight. In addition, the anionic surfactant may be present in an amount of about 0.035% by weight to about 0.15% by weight.

[0057] The nonionic polymerizable hydrophilic component, such as methoxy polyethylene glycol methacrylate or methoxy polypropylene glycol methacrylate, is preferably present in an amount of 0 wt % to about 10 wt % (less than 10 wt %), 0 wt % to about 5 wt % (less than 5 wt %), or about 1.5 wt % to about 3.5 wt %. Alternatively, the nonionic polymerizable hydrophilic component is present in an amount of about 1 wt % to about 5 wt %, preferably about 1.25 wt % to about 4.5 wt %, preferably about 1.5 wt % to about 3.5 wt %, preferably about 1.75 wt % to about 3.25 wt %.

[0058] The percentages of the components of the nonionic resins described herein are given as weight percent of active ingredients, including the weight of active ingredients of solid monomers and additives, excluding water.

[0059] Suitable polymerizable nonionic hydrophilic components include, but are not limited to, methoxy polyethylene glycol methacrylate; methoxy polypropylene glycol methacrylate; other polymerizable polyethylene glycol monomers; other polymerizable polypropylene glycol monomers; meth(acrylic acid), vinyl, allyl-polyethylene glycol; and meth(acrylic acid), vinyl, allyl-polypropylene glycol. Suitable polymerizable nonionic hydrophilic components also include polymerizable nonionic surfactants, such as allyl-functional polymerizable nonionic hydrophilic surfactants, which are commercially available as Adeka Reasoap ER-## series, where ## represents the EO units on the surfactant.

[0060] The ratio between nonionic surfactant and nonionic polymerizable hydrophilic component is preferably 1:1 (by weight), and at most 1.5 or 2.0 or 3 parts by weight of nonionic surfactant to 1 part by weight of nonionic polymerizable hydrophilic component.

[0061] Example 1. Exemplary Inventive Nonionic Resins without Acid MonomersThe reactor seed was added to a nitrogen purged 4-neck reactor and the temperature was then raised to 60°C. Next, 30 g of the premixed monomer emulsion was added to the reactor, followed by the redox initiator, the oxidizing agent tert-butyl hydroperoxide (70%) and the reducing agent FF6M solution. The mixture is then reacted for 15 minutes. The remaining monomer emulsion, oxidant solution and reductant solution are simultaneously fed into the reactor over a period of 3.5 hours. 15 grams of water are used to rinse the monomer emulsion flask. The latex formed in the reactor is maintained at 60°C for 1 hour. The reactor is cooled to 25°C and the biocide solution is subsequently added. The nonionic latex adhesive has a Flory-Fox glass transition temperature of -2°C and a measured minimum film-forming temperature of 0°C. The particle size is 242 nanometers. (Unless otherwise noted, the particle size of the latex particles is the average volume.) The solid content is 40.6%. In Example 1, the initiator is a redox pair (tBHp and BruggoliteFF6M).

[0062]

[0063]

[0064] Example 2. Another exemplary inventive nonionic resin without acid monomers .The reactor seed was added to a nitrogen purged 4-neck reactor and the temperature was then raised to 80°C. Next, 31 g of the premixed monomer emulsion was added to the reactor followed by the seed initiator solution. The mixture was then allowed to react for 15 minutes. The remaining monomer emulsion was fed simultaneously to the reactor over a period of 3.5 hours. 30 g of water was used to rinse the monomer emulsion flask. The latex formed in the reactor was maintained at 80°C for 1 hour. The reactor was cooled to 60°C and tert-butyl hydroperoxide and FF6M solution. The reactor was then cooled to room temperature and the biocide solution was added. The nonionic latex binder had a Flory-Fox glass transition temperature of -2°C and a measured minimum film forming temperature of 0°C. The particle size of the latex was 249 nanometers. The solids content was 42.6%. In Example 2, the initiator was sodium persulfate.

[0065]

[0066]

[0067]

[0068] Example 3A. Another exemplary invention nonionic resin without an acid monomer.Example 3A is disclosed in parent U.S. Provisional Patent Application Serial No. 63 / 388,080. The weight percentages reported in this example do not include water. Typically, MPEG 750MA is available in a 50% aqueous solution and the (meth)acrylate monomer is available as a 40-42 wt % solid in aqueous solution. A small amount of anionic surfactant is added to Example 3A to seed the polymerization. No acid monomers are copolymerized and sodium persulfate is the initiator.

[0069]

[0070]

[0071] Example 3B Similar to Example 3A, except it utilizes more nonionic surfactant during the polymerization process.

[0072]

[0073] In Examples 3A and 3B, the glass transition temperature (Tg) of the nonionic resin ranges from about -5°C to about 15°C, preferably from about -5°C to about 5°C, with typical values ​​of 1°C to 10°C calculated using Fox's equation. The Fox calculation may ignore small components (e.g., less than 3 wt%) that do not have readily available Tg values, such as poly(ethylene or propylene) oxide or wet adhesion monomers. The minimum film forming temperature (MFFT) ranges from about -2°C to about 2°C, preferably from about -2°C to about 6°C, as determined by ISO 2115 standards. The particle size (mean volume, mV) is from about 155nm to about 175nm, and the pH is from about 5 to about 6. For Example 3A, the number average molecular weight is 70,047 Daltons and the weight average molecular weight is 243,139 Daltons, as measured by GPC (RI detector) using polystyrene standards.

[0074] Example 4. Another exemplary invention of nonionic resin without an acid monomer. The nonionic resin was prepared in the same manner as in Example 2 except that

[0075] - 1.5 g of ethoxylated tridecanol was replaced with 3.3 g of anionic phosphate surfactant (25% solids) for seeding, and

[0076] - The seed monomer mixture does not contain polyethylene glycol methacrylate. Polyethylene glycol methacrylate is added to the monomer emulsion after the seed monomer mixture is charged to the reactor.

[0077] Anionic surfactants comprise 0.11 wt% (solids); nonionic surfactants comprise 2.48 wt% (solids); and polyethylene glycol methacrylate comprises 1.91 wt% (solids). The polymer has a particle size of 164.9 nanometers. The polymer has a Flory-Fox glass transition temperature of -2°C and a minimum film forming temperature measured of 0°C. It has a solids content of 40.6%. Sodium persulfate is an initiator.

[0078] Example 5. Another exemplary invention of nonionic resin without an acid monomer. A nonionic copolymer resin was prepared similarly to Example 4, except that 80 grams of DAAM crosslinking monomer was added to the monomer mixture. Anionic surfactant accounted for 0.10 wt % (solids); nonionic surfactant accounted for 2.25 wt % (solids); and polyethylene glycol methacrylate accounted for 1.74 wt % (solids). The resin had a particle size of 168 nm and a solids content of 43.6%.

[0079] Example 6. Another exemplary invention of nonionic resin without an acid monomer. A nonionic copolymer was prepared similarly to Example 5, except that 80 grams of DAAM was replaced with 80 grams of AAEM crosslinking monomer. Anionic surfactant accounted for 0.10 wt % (solids); nonionic surfactant accounted for 2.25 wt % (solids); and polyethylene glycol methacrylate accounted for 1.74 wt % (solids). The resin had a particle size of 161 nm and a solids content of 44.0%.

[0080] Listed below is a summary of certain components and their particle sizes for Examples 1-6.

[0081]

[0082]

[0083] As shown in Examples 1-6, when anionic surfactants are used during the inoculation process (Examples 3A, 3B, 4, 5 and 6), the particle size (mV) of the nonionic latex particles can be better controlled than when nonionic surfactants are used during the inoculation process (Examples 1 and 2).

[0084] It is worth noting that in Examples 1-6, the reported weight percentages are based on all solids. By excluding small amounts of solids, i.e., buffers, initiators, chasers, and biocides, the weight percentage of surfactant or MPEG based on total monomer content can be easily calculated. Since the weight percentage of surfactant based on total monomer content is determined, the surfactant will be included in the percentage calculation. The weight percentage based on total monomer content and the weight percentage based on total solids are essentially the same.

[0085] In Resin Examples 1-6, the nonionic surfactant has an HLB value of 14.5 or 16.3. The preferred HLB value range is from about 14 to about 18, preferably from about 14 to about 17, preferably from about 15 to about 18. Without being bound by any particular theory, a higher hydrophilicity is required to stabilize the latex particles because the nonionic nature of these latexes results in no static stability.

[0086] In Examples 7A and 7B, exemplary paint compositions utilizing blends of the nonionic resins of the present invention with commercially available cationic resins are shown below. The weight percentages given in Examples 7A-7B include water.

[0087] Example 7A.

[0088]

[0089]

[0090] Example 7B.

[0091]

[0092]

[0093] In Example 7A, the cationic resin I contains about 57% water and the nonionic resin contains about 59% water. Therefore, the ratio of cationic resin to nonionic resin - dry weight - is (0.43x31.312):(0.41x22.166) or 13.46:9.09 or about 59.6:40.4 (or 60:40) cationic resin to nonionic resin. The total resin amount is about 22.55% solid resin (dry) in the total formula (including water). The rust inhibitor can range from 0% to about 1% by weight, preferably 0.15% to 0.5% by weight. The ratio of cationic resin to nonionic resin is about the same as Example 7B.

[0094] The cationic resin I used in this experiment is a commercially available aqueous emulsion polymerized resin.

[0095] The blends shown in Examples 7A and 7B and other blends of other ratios of the inventive nonionic resins from Examples 3A and 3B to the commercial cationic resin shown in Experiment 8 did not form grit or gels and therefore did not negatively affect the properties of the paint films formed from the blends.

[0096] In Experiment 8, various dried paint films from different paint / building combinations were tested on a cedar board surface with stain. Contrast ratio readings were taken on the stained and non-stained areas. A Δb* measurement was taken on the stained area of ​​each paint film. The dried paint films were also checked for blistering. The results are shown below.

[0097] Experiment 8.

[0098]

[0099] - Cationic resin II is a commercially available aqueous, hydrophilic, solution polymerized resin. Blends (E, F and G) employ Cationic resin I.

[0100] - Ratios expressed in blends (E, F and G) are based on solids only.

[0101] --C / R is the contrast ratio. The contrast ratio is the ratio of the Y value of the paint on the stained area divided by the lightness (Y) value of the paint color on the non-stained area. The best C / R score is theoretically 100.

[0102] - Blistering resistance was tested at 90°C and rated 1-5, with 1 being the worst.

[0103] - Δb* is a measure of yellowness by measuring the intensity of light of a specific wavelength (e.g., the wavelength of yellow) with a spectrophotometer. The higher the reading, the more stain there is.

[0104] In Experiment 8, various compositions of anionic paint, cationic paint, and blends of the nonionic resin and cationic resin of the present invention were tested and compared with the reference primer composition (D). The primer film formed from the reference primer showed good contrast ratio only in the primer film (97.8), the topcoat film (99.5), and showed good Δb* value (2.52) and good blister resistance (4).

[0105] Experiment 8 shows that the conventional anionic primer composition (A) has good anti-blistering properties (4), but only the contrast ratio of the primer layer (79.5) is low, while the contrast ratio of the topcoat (90.1) is the lowest among all experiments. The Δb* value (5.14) is the highest, that is, the stain is most obvious. Experiment 8 also shows that the commercially available cationic resin primer compositions (B and C) have high contrast ratios on the primer film (98.4, 99.6) and the highest contrast ratios on the topcoat (99.7, 100.1), but the blister ratings are the worst (1.5, 1).

[0106] The three blends (E)-(G) of the nonionic resin and cationic resin of the present invention performed comparably well in contrast ratio values ​​for the primer layer (97.3, 97.8, 98.6 vs. 97.8) compared to the benchmark, and were comparable in contrast ratio values ​​for the topcoat (97.6, 98.2, 98.8 vs. 99.5). The Δb* values ​​(2.26, 1.93, 1.57 vs. 2.52) and blister resistance (5, 4.5, 4 vs. 4) of the blends were superior to the benchmark.

[0107] Experiment 8 shows that the cationic resin (EG) blended with the nonionic resin composition of the present invention at a ratio of 70:30 to 50:50 produces good anti-blistering properties while exhibiting high anti-fouling properties on the primer layer and on the topcoat layer.

[0108] Preferably, the blend of nonionic resin and cationic resin of the present invention ranges from 80 wt% cationic resin and 20 wt% nonionic resin to 20 wt% cationic resin and 80 wt% nonionic resin. The blend may also range from 70 wt% cationic resin and 30 wt% nonionic resin to 30 wt% cationic resin and 70 wt% nonionic resin. The blend may also range from 60 wt% cationic resin and 40 wt% nonionic resin to 40 wt% cationic resin and 60 wt% nonionic resin. The blend may also range from 55 wt% cationic resin and 45 wt% nonionic resin to 45 wt% cationic resin and 55 wt% nonionic resin.

[0109] In blends with cationic resins, the nonionic resins of the present invention provide good adhesion and good resistance to blistering.

[0110] Exposure experiment. Wooden boards painted with commercial primers and primer blends of nonionic resins and cationic resins of the present invention were placed outdoors for two years to test the durability of the paint. Some painted boards were kept in a horizontal position, and some were kept at an angle of approximately 45° to the south. Some boards were also painted with a topcoat layer. Most of the primer paints remained good, and all primer and topcoat paints remained good. The growth of microbial organisms was observed on the boards painted with only commercial primers. Less growth or no growth was observed on the boards painted with the blends of nonionic resins and cationic resins of the present invention. The boards painted with the blends of nonionic resins and cationic resins of the present invention performed better in resisting microbial growth than the boards painted with the benchmark primer and commercial primers. The boards painted with the blends of nonionic resins and cationic resins of the present invention performed better in water sensitivity and adhesion than the boards painted with the benchmark primer, and had less cracking and peeling on the horizontally placed boards.

[0111] Exemplary "cationic" resins include latex resins polymerized with commonly used (meth)acrylic monomers including styrene or vinyl acetate and one or more cationic monomers. Exemplary cationic monomers include one or more dimethylamino functional monomers, wherein the one or more dimethylamino functional monomers have the formula:

[0112]

[0113] wherein R1 represents hydrogen or methyl; R2 represents hydrogen or C1-6 alkyl, and n is 2 to 6.

[0114] Preferably, the dimethylamino functional monomers include N,N-dimethylaminoethyl methacrylate (DMAEMA), dimethylaminopropyl methacrylate (DMAPMA), butylaminoethyl methacrylate (TBAEMA) and N-[3-(dimethylamino)propyl]methacrylamide (DMAPMAA).

[0115] Other suitable "cationic" monomers include, but are not limited to, N,N-dimethylaminoethyl acrylate, N-2-N,N-dimethylaminoethyl methacrylamide, N-3-N,N-dimethylaminopropyl acrylamide, N-3-N,N-dimethylaminopropyl methacrylamide, N,N-diethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N-tert-butylaminoethyl acrylate, N-tert-butylaminoethyl methacrylate, N,N-dimethylaminopropyl acrylamide, N,N-diethylaminopropyl acrylamide, N,N-diethylaminopropyl methacrylamide. Other suitable "cationic" monomers are disclosed in US2014 / 0121146 (paragraph

[0042] ), US2015 / 0374634 (paragraph

[0123] ), US2009 / 0269406 (paragraph

[0034] ), US 7,319,117 (columns 11 and 17). These references are incorporated herein in their entirety.

[0116] Embodiment 4: Preparation of cationic acrylic latex emulsions containing 1 wt % and 3 wt % DMAPMAA.

[0117] Example 4 describes a method for producing a cationic latex emulsion. A 5-L glass reactor equipped with a mechanical stirrer and a condenser was used to incorporate the "cationic" functional monomer DMAPMAA into the resin through a semi-continuous MMA / BA emulsion copolymerization process. The reaction temperature was controlled by a water bath. The solution pH was maintained between 8 and 9. DMAPMAA was added to the last 20-50% of the pre-emulsion. The pre-emulsion was added at a constant feed rate over 4 hours, and the initiator solution was added at a constant feed rate over 4.5 hours. All polymerizations were performed at 80°C at 50% solid content (monomer mass relative to total reaction mass). DMAPMAA monomer accounts for approximately 1% or 3% by weight (or mass) of the total monomers. The preparation of the copolymer adhesive may or may not add 0.1-1% crosslinking agent.

[0118] The particle size of the resulting emulsion was 140-150 nm; the nonvolatile content was 50-51%. Table 1 describes non-inventive control and inventive compositions containing DMAPMAA monomer.

[0119] Composition of acrylic latex emulsions containing 1% and 3% DMAPMAA.

[0120]

[0121]

[0122] Suitable nonionic surfactants include those available from Rhodia Solvay 2525,

[0123] Suitable free radical initiators include 4,4'-azobis(4-cyanovaleric acid) or C 12 H 16 N4O4 and sodium persulfate.

[0124] Suitable latex particles include, but are not limited to, acrylic acid, vinyl, vinyl-acrylic acid or styrene-acrylic acid polymers or copolymers. The latex particles coalesce and / or crosslink to form a paint film on a substrate. As shown in the embodiments herein, latexes made primarily of acrylic acid monomers are preferred for the present invention. Exemplary non-limiting monomers suitable for forming latex particles of the present invention are described below.

[0125] Generally speaking, any (meth)acrylic acid monomer can be used in the present invention. Suitable (meth)acrylic acid monomers include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, alkyl (meth)acrylates such as methyl (meth)acrylate, (meth)acrylic acid, wet adhesion monomers such as N-(2-methacryloyl)methacrylate, The present invention also provides a kind of monomers for the present invention, for example, alkyl (meth)acrylate monomers ...

[0126] Preferred monomers containing aromatic groups are styrene and α-methylstyrene. Other suitable monomers containing aromatic groups include, but are not limited to, 2,4-diphenyl-4-methyl-1-pentene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, 2,3,4,5,6-pentafluorostyrene, (vinylbenzyl)trimethylammonium chloride, 2,6-dichlorostyrene, 2-fluorostyrene, 2-isopropenylaniline, 3 (trifluoromethyl)styrene, 3-fluorostyrene, α-methylstyrene, 3-vinylbenzoic acid, 4-vinylbenzyl chloride, α-bromostyrene, 9-vinylanthracene, and combinations thereof.

[0127] Preferred monomers containing primary amide groups are (methyl) acrylamide. Suitable monomers containing amide groups include, but are not limited to, N-vinylformamide or any vinylamide, N,N-dimethyl (methyl) acrylamide, N-(1,1-dimethyl-3-oxobutyl) (methyl) acrylamide, N-(hydroxymethyl) (methyl) acrylamide, N-(3-methoxypropyl) (methyl) acrylamide, N-(butoxymethyl) (methyl) acrylamide, N-(isobutoxymethyl) acryl (methyl) acrylamide, N-[tris (hydroxymethyl) methyl] acryl (methyl) acrylamide, 7-[4-(trifluoromethyl) coumarin] (methyl) acrylamide, 3-(3-fluorophenyl)-2-acrylamide, 3-(4-methylphenyl) (methyl) acrylamide, N-(tert-butyl) (methyl) acrylamide and combinations thereof. These monomers can be polymerized with the acrylic monomers listed above. The general formula of vinyl (formamide) is:

[0128]

[0129] And the general formula of (meth)acrylamide is:

[0130]

[0131] Wherein R1 and R2 can be -H, -CH3, -CH2CH3 and other substituted organic functional groups, and R3 can be -H, alkyl or aryl.

[0132] In one embodiment, styrene monomers, such as styrene, methylstyrene, chlorostyrene, methoxystyrene, and the like, are preferably copolymerized with (meth)acrylamide monomers.

[0133] In one embodiment, the aqueous latex polymer may also contain a vinyl monomer. Monomers of this type suitable for use according to the present invention include any compound having a vinyl functional group (i.e., a -CH=CH2 group). Preferably, the vinyl monomer is selected from the group consisting of vinyl esters, vinyl aromatic hydrocarbons, vinyl aliphatic hydrocarbons, vinyl alkyl ethers, and mixtures thereof.

[0134] Suitable vinyl monomers include vinyl esters such as, for example, vinyl acetate, vinyl propionate, vinyl laurate, vinyl pivalate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl butyrate, vinyl hexanoate, vinyl benzoate, vinyl isopropyl acetate and similar vinyl esters; nitrile monomers such as (meth) acrylonitrile and the like; vinyl aromatics such as, for example, styrene, methyl styrene and similar lower alkyl styrenes, chlorostyrene, vinyl toluene, vinyl naphthalene and divinylbenzene; vinyl aliphatic hydrocarbon monomers such as, for example, vinyl chloride and vinylidene chloride, and alpha olefins such as, for example, ethylene, propylene, isobutylene, and conjugated dienes such as 1,3-butadiene, methyl-2-butadiene, 1,3-pentylene, 2,3-dimethylbutadiene, isoprene, cyclohexene, cyclopentadiene and dicyclopentadiene; and vinyl alkyl ethers such as, for example, methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether.

[0135] Additives may be added to the polymerization process including surfactants, initiators, chaser solutions, biocides, rheology modifiers, and the like.

[0136] JV Koleske, R. Springate, and D. Brezinski describe surfactants in the Additives Reference Guide, pp. 83-88 (2013), and these pages are incorporated herein in their entirety. The following discussion of surfactants is based on Koleske et al.

[0137] Nonionic surfactants usually refer to polyoxyethylene derivatives, although other surfactants also belong to this class. They are usually prepared by the addition reaction of ethylene oxide with a hydrophobic compound containing one or more active hydrogen atoms. Examples of such hydrophobic compounds are fatty alcohols, alkylphenols, fatty acids, fatty amines, alkanolamines, fatty mercaptans, fatty amines and certain polyols. The polyols may include oxypropylene polyols, polyesters, etc. These surfactants are uncharged and will not dissociate. Their surface active characteristics come from the oxyethylene portion of the molecule. The nature of the hydrophobe and the length of the oxyethylene chain both affect the surface active characteristics.

[0138] In general, these groups are weakly hydrophilic compared to the hydrophobic part of the molecule. Weak ester bonds and amide bonds are also present in many nonionic surfactants. Nonionic surfactants are generally compatible with ionic surfactants. For example, many nonionic surfactants work well with anionic surfactants. In such a combination, they give aqueous systems good freeze-thaw stability and are less detrimental to mechanical properties than ionic compounds. Nonylphenol ethoxylate (NPE) is a typical example of such a surfactant. Other examples are: octylphenol ethoxylate (OPE), secondary alcohol ethoxylates, trimethylnonanol ethoxylate (TMN), specialty alkoxylates, and amine ethoxylates. In emulsion polymerization, alkyl ether sulfates are one of the main surfactants necessary to provide micelle stabilization. Traditionally, these sulfates have been based on alkylphenol ethoxylates (APEO). Typically, emulsion polymerization uses two types of surfactants - one nonionic and the other anionic. Each provides a separate stabilization mechanism for micelles, but the combination provides better stabilization, especially as temperature increases. Nonionic surfactants create spatial separation between micelle groups, while anionic surfactants create charged repulsion between micelles. Nonionic surfactants generally perform well over a range of pH values, and their foams are generally smaller than anionic and cationic surfactants. However, in complex coating formulations, nonionic surfactants may not reduce surface tension as well as anionic or cationic surfactants. There are nonionic polymeric fluorochemical surfactants that can provide low surface tension in organic coating systems. The lower the surface tension, the better the coating wetting, leveling and spreading. Therefore, these are excellent wetting agents, leveling agents and flow control agents for a variety of water-based, solvent-based and high-solid coating systems. Most fluorosurfactants are soluble and compatible with most polymers and continue to be active throughout the drying or curing process. When used in water-based systems, they tend to reduce the water / organic interfacial tension and remain surface active in the organic part of the polymer system. There is also an anionic fluorosurfactant based on ammonium salts on the market that is soluble in water.

[0139] Anionic surfactants carry a negative charge on the hydrophilic portion of the molecule. They are typically phosphates, sulfates, and sulfonates. These surfactants may or may not contain oxyethylene chains in their structure. Examples of anionic surfactants are sulfosuccinates, dioctyl sulfosuccinate (DOSS), polyether sulfates, polyether sulfonates, polyether phosphates, sodium lauryl sulfate, and phosphate-modified alcohol-ethoxylates.

[0140] Surface-active phosphates are a class of anionic surfactants prepared by the reaction of alcohols with activated phosphoric acid derivatives (including phosphoric anhydride and acid chloride). Typically, commercial phosphate products consist of a mixture of monoesters, diesters, free phosphoric acid and free alcohols used in their preparation. The properties of the final phosphate product are primarily determined by the composition of the starting alcohol used and the four different substances. On the contrary, the properties of the final phosphate product can be customized by changing the alcohol used in the preparation and controlling the ratio of the four different components present in the final product. Phosphate surfactants are made in free acid form, but can also be neutralized to a salt form using any alkali (including sodium hydroxide, potassium hydroxide, ammonium hydroxide or any organic amine).

[0141] Typically, phosphate ester surfactants are added to the formulation during the paint preparation process - either at the grind or at letdown, depending on the formulation. These additives have also been tested as post-paint formulation additives and have shown comparable properties. It is presumed, and the focus of much research, that the use of phosphate ester surfactants prior to the paint formulation stage (using phosphate esters in emulsion polymerization and post-polymerization stabilizers or additives in pigment dispersion) should only benefit the final properties of the paint and reduce the deleterious effects of additional surfactants in the paint system.

[0142] Cationic surfactants carry a positive charge, and quaternary ammonium compounds are the most common cationic surfactants. Compounds such as alkyltrimethylammonium chloride are representatives of these surfactants.

[0143] The hydrophilic lipophilic balance (HLB) system is a numbering system for evaluating the relative hydrophilicity of surfactants. The system is based on an arbitrary numerical scale, wherein zero is designated as a surfactant of extreme hydrophobicity, and 20 is designated as a surfactant of extreme hydrophilicity. The numbers assigned to a surfactant represent a measure of the balance between its hydrophilic strength and hydrophobic strength. A surfactant with an HLB of 10 has a balance of lipophilic and hydrophilic groups.

[0144] Examples of initiator and chaser solutions useful in the polymerization process may include, but are not limited to, ammonium persulfate, sodium persulfate, azo initiators (such as azoisobutyronitrile), redox systems (such as sodium hydroxymethanesulfinate (sodium formaldehyde sulfoxylate; reducing agent) and tert-butyl-hydroperoxide (oxidizing agent)), and the like, and combinations thereof, typically in aqueous solution. Either or both of these components may optionally contain additional surfactants and / or pH adjusters if desired to stabilize the emulsion.

[0145] Examples of pH adjusters useful in the polymerization process may include, but are not limited to, ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, ammonia, amines such as trimethylamine, triethylamine, dimethylaminoethanol, diethylaminoethanol, AMP-95, and the like, and combinations thereof. In some cases, compounds considered to be pH adjusters may be added for purposes other than adjusting pH, such as emulsion stabilization, but are still characterized herein as pH adjusters.

[0146] Polymer molecular weight controllers are intended to control (usually limit) the molecular weight of a growing polymer. Although polymer molecular weight controllers may include substances such as radiation, they are typically molecules added to a polymerization mixture. Examples of polymer molecular weight controllers include, but are not limited to, chain transfer agents (CTAs), for example, alkyl mercapto esters such as isooctyl mercaptopropionate, alkyl mercaptans, etc., and combinations thereof. Chain transfer agents typically act as polymer molecular weight controller molecules, for example, catalytically or consumably terminating growing polymer chains by also initiating new growing polymer chains. In this way, the amount of chain transfer agents can be adjusted to reduce the target polymer molecular weight in a set of polymerization systems, or alternatively, in combination with calculating the amount of initiator, the amount of chain transfer agents can be calculated to target a specific average polymer molecular weight (e.g., within a given range) of a polymerization system.

[0147] Titanium dioxide is often used as an opacifying pigment, as shown in Examples 2A and 2B. Zinc oxide can also be used as an opacifying pigment. Extender pigments are often added to paints, and include aluminum silicate and diatomaceous earth, as shown in Examples 2A and 2B. Other suitable extender pigments include, but are not limited to, calcium carbonate, magnesium silicate, potassium aluminum silicate, nepheline syenite, and are discussed in commonly owned U.S. Patent No. 11,518,893, which is incorporated herein by reference in its entirety.

[0148] Although the exemplary embodiments of the present invention disclosed herein obviously achieve the above-mentioned purpose, it should be understood that those skilled in the art can design numerous modifications and other embodiments. Therefore, it should be understood that the appended claims are intended to cover all such modifications and embodiments, which will fall within the spirit and scope of the present invention.

Claims

1. A paint composition comprising a blend of: Cationic latex resin, and A substantially nonionic latex resin, wherein the substantially nonionic latex resin is polymerized from: A monomer mixture comprising at least one nonionic (meth)acrylate monomer, a polymerizable nonionic hydrophilic component, wherein the monomer mixture is substantially free of acid monomers or other monomers with anionic groups, and a nonionic surfactant ranging from about 1 wt % to about 4 wt %, preferably from about 1.5 wt % to about 3.5 wt %; and wherein the polymerizable hydrophilic component is present in an amount of about 1.5 wt % to about 3.5 wt %, The weight percentages stated do not include water.

2. A paint composition comprising a blend of: Cationic latex resin, and A substantially nonionic latex resin, wherein the substantially nonionic latex resin is polymerized from: A monomer mixture comprising at least one nonionic (meth)acrylate monomer, a polymerizable nonionic hydrophilic component, wherein the monomer mixture is substantially free of acid monomers or other monomers with anionic groups, and A nonionic surfactant in the range of about 1 wt % to about 4.5 wt %, preferably about 1.25 wt % to about 4.25 wt %, preferably about 1.5 wt % to about 3.75 wt %, wherein the HLB value of the nonionic surfactant is in the range of about 14 to about 18, preferably about 14 to about 17, preferably about 15 to about 18, wherein the polymerizable hydrophilic component is present in an amount of about 1 wt % to about 5 wt %, preferably about 1.25 wt % to about 4.5 wt %, preferably about 1.5 wt % to about 3.5 wt %, preferably about 1.75 wt % to about 3.25 wt %, The weight percentages stated do not include water.

3. The paint composition of claim 1 or 2, wherein the monomer mixture does not contain acid monomers or other monomers with anionic groups.

4. A paint composition as claimed in claim 1 or 2, wherein the acid monomer or other monomer with anionic group is less than 0.25% by weight, preferably less than 0.125% by weight of the total monomer content.

5. The paint composition of claim 1 or 2, wherein the substantially nonionic resin is additionally polymerized with an anionic surfactant in an inoculum amount ranging from about 0.01 wt % to about 0.25 wt %, preferably from about 0.05 wt % to about 0.15 wt %, based on the total monomer content.

6. The paint composition of claim 1 or 2, wherein the substantially nonionic resin is additionally polymerized with an inoculum amount of anionic surfactant, the inoculum amount ranging from about 0.035 wt % to about 0.15 wt % based on total monomer content.

7. The paint composition of claim 1 or 2, wherein the blend of the substantially nonionic resin and the cationic resin ranges from 80 wt % cationic resin and 20 wt % nonionic resin to 20 wt % cationic resin and 80 wt % nonionic resin, The weight % of the cationic resin and the nonionic resin are dry weight.

8. The paint composition of claim 1 or 2, wherein the blend of the substantially nonionic resin and the cationic resin ranges from 70 wt % cationic resin and 30 wt % nonionic resin to 30 wt % cationic resin and 70 wt % nonionic resin, The weight % of the cationic resin and the nonionic resin are dry weight.

9. The paint composition of claim 1 or 2, wherein the blend of the substantially nonionic resin and the cationic resin ranges from 60 wt % cationic resin and 40 wt % nonionic resin to 40 wt % cationic resin and 60 wt % nonionic resin, The weight % of the cationic resin and the nonionic resin are dry weight.

10. The paint composition of claim 1 or 2, wherein the blend of the substantially nonionic resin and the cationic resin ranges from 55 wt. % cationic resin and 45 wt. % nonionic resin to 45 wt. % cationic resin and 55 wt. % nonionic resin, The weight % of the cationic resin and the nonionic resin are dry weight.

11. The paint composition according to claim 1 or 2, further comprising a rust inhibitor.

12. The paint composition of claim 1 or 2, wherein the polymerizable hydrophilic component comprises a polymerizable polyethylene glycol monomer or a polymerizable polypropylene glycol monomer.

13. The paint composition of claim 12, wherein the polymerizable polyethylene glycol monomer is a methoxy polyethylene glycol methacrylate monomer.

14. The paint composition of claim 1, wherein the HLB value of the nonionic surfactant ranges from about 14 to about 18, preferably from about 14 to about 17, preferably from about 15 to about 18.

15. The paint composition of claim 1 or 2, wherein only nonionic surfactants are used in the polymerization to form micelles and the substantially nonionic latex resin.

16. A method for blocking stains on a substrate to prevent migration to a paint film covering the substrate while minimizing adverse water sensitivity issues between the substrate and the paint film, wherein the method comprises the steps of: i. blending a cationic resin with a nonionic resin to form a blended resin composition without forming coarse particles or gels; ii. preparing a paint composition, preferably a primer or topcoat composition, comprising the blended resin composition and an opacifying pigment; and iii. covering the substrate with the paint composition, wherein the paint composition dries and forms the paint film.

17. The method of claim 16, wherein the nonionic resin is polymerized in the substantial absence of acid monomers or other monomers with anionic groups.

18. The method of claim 17, wherein the acid monomer or other monomer with anionic groups is less than 0.25 wt. %, preferably less than 0.125 wt. %, more preferably less than about 0.1 wt. % of the total monomer content.

19. The method of claim 17, wherein the nonionic resin is polymerized in the absence of acid monomers or other monomers with anionic groups.

20. The method of any one of claims 16-19, wherein the nonionic resin is polymerized from a monomer mixture comprising at least one nonionic (meth)acrylate monomer, a polymerizable nonionic hydrophilic component, and a nonionic surfactant.