Coating with initial water resistance

Abstract

A coating composition is presented and described herein. The coating composition comprises (a) an active hydrogen-containing (meth)acrylic polymer, (b) an epoxy silane oligomer composition, (c) an emulsifier, (d) titanium oxide particles, (e) a silicate particulate filler, and (f) water, and optionally one or more additives, wherein the epoxy silane oligomer composition comprises 5 to 15 weight percent monomer, 5 to 20 weight percent dimer, 5 to 20 weight percent trimer, and 45 to 85 weight percent poly-oligomer components. The coating composition can provide an aqueous coating composition that exhibits initial water resistance, minimizing coating defects when exposed to water before the coating is fully cured.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and interest to U.S. Provisional Patent Application No. 62 / 754,725, “Coating with Initial Water Resistance,” filed on 2 November 2018, the disclosure thereof is incorporated herein by reference in its entirety.

[0002] The present invention relates to coating compositions, and more particularly to aqueous coating compositions comprising an emulsion of a (meth)acrylate polymer containing at least one functional group having active hydrogen, an epoxy-functionalized silane oligomer composition, titanium dioxide, and a siliceous filler. These aqueous coating compositions using the epoxy-functionalized silane oligomer composition provide a coating that exhibits initial water resistance against moisture blistering that may occur from exposure to moisture before the coating is fully cured. [Background technology]

[0003] Water-based coatings and paints may be exposed to water or moisture immediately after application to a surface and before the coating has had time to fully cure. Exposure to moisture can occur in indoor applications where the coating may be exposed to conditions containing a high percentage of moisture in the air, such as high humidity conditions or vapor or moisture generated in bathrooms or showers, and in outdoor applications where the coating may be exposed to moisture from environmental conditions such as dampness, fog, dew, rain, and snow. Exposure to moisture before the coating has cured can cause blistering and wrinkling of the coating. Blistering and wrinkling of the coating can reduce the adhesion of the coating and may lead to other defects such as peeling.

[0004] One conventional method to circumvent these problems is to increase the curing speed of the coating. For example, additives such as 2-amino-2-methyl-1-propanol have been used to increase the curing speed of coatings. While this can avoid some problems caused by initial exposure to moisture, it may ultimately sacrifice other coating properties such as the flexibility of the coating and the appearance of the surface.

[0005] Therefore, there remains a need to provide an aqueous coating composition that has good resistance to blistering and wrinkling when exposed to moisture immediately after the coating is applied to the substrate. [Overview of the project]

[0006] The present invention provides an aqueous coating composition that exhibits water resistance immediately after application to a substrate. In one embodiment, the aqueous coating composition comprises (a) an emulsion of a (meth)acrylic polymer containing at least one functional group having active hydrogen, and (b) an epoxysilane oligomer composition. The addition of the epoxysilane oligomer composition to the (meth)acrylic polymer emulsion has been found to improve resistance to blistering and wrinkling when exposed to water immediately after application to a substrate, often referred to as initial water resistance. The aqueous coating composition can provide a coating that exhibits initial water resistance so that defects in the coating are minimized if the coating is exposed to water before it has fully cured.

[0007] In one embodiment, a method for coating a substrate is provided, comprising applying an aqueous coating composition to the substrate, wherein the aqueous coating composition comprises an emulsion of a (meth)acrylic polymer and an epoxysilane oligomer composition having at least one functional group having active hydrogen.

[0008] In one embodiment, the aqueous coating composition is (a) A (meth)acrylic polymer comprising at least one functional group having active hydrogen; (b) An epoxy silane oligomer composition comprising the following (i) A monomer having the structure of formula (I) in an amount of about 5 to about 15 weight percent: (Z c ) a (R 1 O) 3-2a Si-R 2 (I) (ii) A dimer having the structure of formula (II) in an amount of about 5 to about 20 weight percent: (Z c ) b (R 1 O) 2-2b (R 2 )Si-O-Si(R 2 )(OR 1 ) 2-2c (Z c ) c (II); (iii) At least one trimer having a linear structure (III) or a cyclic structure (IV) in an amount of about 5 to about 20 weight percent:

Chemical formula

Chemical formula

Chemical formula

[0009] In one embodiment, the epoxysilane oligomer composition (b) is present in the coating composition in an amount of about 0.75 to about 2% by weight, preferably more than about 0.5% to about 5% by weight, based on the weight of the (meth)acrylic polymer (a) having at least one functional group having active hydrogen.

[0010] In one embodiment, the functional group containing active hydrogen is a carboxyl group (-C(=O)OH) or a hydroxyl group (-OH). In one embodiment, the functional group containing active hydrogen is in salt form -C(=O)O - M + It is a carboxyl group that is neutralized, and here, M + is Na + , K + , or ammonium ions.

[0011] In one embodiment, the amount of carboxyl group is sufficient to have an acid value of about 1 to about 780, as determined by potentiometric titration.

[0012] In one embodiment, the (meth)acrylic polymer (a) containing at least one functional group having active hydrogen is selected from the group consisting of pure acrylic, styrene acrylic, vinyl acrylic, and acrylic ethylene vinyl acetate copolymer.

[0013] In one embodiment, a (meth)acrylic polymer (a) containing at least one functional group having active hydrogen is prepared by emulsion polymerization.

[0014] In one embodiment, pure acrylic is prepared using acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers; styrene acrylic is prepared using styrene and acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers; vinyl acrylic is prepared using vinyl acetate and acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers; and acrylic ethylene vinyl acetate copolymer is prepared using ethylene, vinyl acetate and acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers.

[0015] In one embodiment, the (meth)acrylic polymer (a) having at least one functional group having active hydrogen is present in an amount of about 5 to about 60% by weight, based on the total weight of the (meth)acrylic polymer (a) having at least one functional group having active hydrogen, the epoxysilane oligomer composition (b), the emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f).

[0016] In one embodiment, R 1 R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl, and 1,3-dimethyl-3-hydroxybutyl; 3 R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl, and 1,3-dimethyl-3-hydroxybutyl; 4 is selected from the group consisting of ethylene, propylene, and 2-methylpropylene; and R 5The compounds are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl and 1,3-dimethyl-3-hydroxybutyl, (glycidoxypropyl)bis(2-methyl-3-hydroxypropoxy)silyl, and [(glycidoxypropyl)dimethoxysilyloxy]-(glycidoxypropyl)methoxysilyl.

[0017] In one embodiment, R 1 is methyl or ethyl, R 3 is methyl or ethyl; R 5 (I) is methyl, ethyl, (glycidoxypropyl)dimethoxysilyl; or (glycidoxypropyl)diethoxysilyl); and a, b, c, d, e, f, g, h, and i are 0.

[0018] In one embodiment, the epoxysilane oligomer composition (b) has a weight-average molecular weight of about 500 to about 2500.

[0019] In one embodiment, the epoxysilane oligomer composition (b) is in an amount ranging from more than about 0.5% by weight to about 5% by weight, based on the weight of the (meth)acrylic polymer (a) which contains at least one functional group having active hydrogen.

[0020] In one embodiment, the emulsifier (c) is a surfactant selected from the group consisting of polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonate salts, alkyl phosphate salts, alkyl allyl sulfate ester salts, polyoxyethylene alkyl phosphate ester salts, long-chain alkyltrimethylammonium salts, and di(long-chain alkyl)dimethylammonium salts.

[0021] In one embodiment, the emulsifier (c) is present in an amount of about 1.0% to about 15% by weight, based on the weight of the (meth)acrylic polymer (a) which contains at least one functional group having active hydrogen.

[0022] In one embodiment, titanium dioxide particles are present in an amount of about 0.5% to about 50% by weight, based on the total weight of a (meth)acrylic polymer (a) having at least one functional group having active hydrogen, an epoxysilane oligomer composition (b), an emulsifier (c), titanium dioxide particles (d), a siliceous particulate filler (e), and water (f).

[0023] In one embodiment, the siliceous particulate filler is selected from the group consisting of hydrated kaolin, mullite, pyrophyllite, kyanite, nepheline, clay, sillimanite, silica, and talc.

[0024] In one embodiment, based on the total weight of a (meth)acrylic polymer (a) having at least one functional group having active hydrogen, an epoxysilane oligomer composition (b), an emulsifier (c), titanium dioxide particles (d), a siliceous particulate filler (e), and water (f), the siliceous particulate filler (e) is in an amount of about 0.05 to about 25 weight percent.

[0025] In one embodiment, the epoxysilane oligomer composition is synthesized by the reaction of an epoxy-functionalized silane having the structure of formula (I), (Z c ) a (R 1 O) 3-2a Si-R 2 (I) Here's Z c is a divalent base -OR 4 O-, and here R 4 This is a divalent linear alkylene group of 2 to 6 carbon atoms or a branched alkylene group of 3 to 6 carbon atoms, however (i) The two oxygen atoms are R 4 It is bonded to two different carbon atoms, and (ii) The condition is that the open valence of each oxygen atom is bonded to the same Si atom to form a cyclic 1,3-dioxa-2-sila-cycloalkyl group, R 1 Each of these entities independently consists of a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, or -OR 4 It is an OH group; here R 4 R is independently a divalent linear alkylene group of 2 to 6 carbon atoms or a branched alkylene group of 3 to 6 carbon atoms; 2 Each of these entities is as follows: [ka] The subscript 'a' is an integer, where 'a' is 0 or 1, and the amount of water is 0.5 to 1.0 moles per mole of epoxy-functionalized silane in the presence of the catalyst, where the water is continuously supplied during the reaction.

[0026] In one embodiment, the aqueous coating composition of any of the embodiments described above is an aqueous coating composition having a gloss of 60 degrees between 10 and 40 gloss units (GU), more specifically between 15 and 25 gloss units (GU).

[0027] In another embodiment, a method for coating a substrate is provided, which includes applying a coating composition of any of the embodiments described above to the surface of the substrate.

[0028] One embodiment provides a method for coating a substrate, comprising: (a) providing a pre-formed aqueous stock coating composition comprising a (meth)acrylic polymer having at least one functional group having active hydrogen, an emulsifier, titanium dioxide, at least one siliceous filler, water, and an optional additive; (b) adding an epoxysilane oligomer composition to the pre-formed stock aqueous coating composition; and (c) applying the aqueous coating composition from step (b) to a substrate and evaporating the water from the aqueous coating composition to form a substrate comprising a dried coating having improved initial water resistance.

[0029] In one embodiment of the method, the composition from (b) is heat-aged before the composition is applied to the substrate. In another embodiment of the method, the composition from (b) is heat-aged at 50°C for 14 days.

[0030] The following description and drawings disclose various exemplary embodiments. While some improvements and novel embodiments may be clearly identifiable, others may be apparent from the description and drawings. Further objects of the present invention are partially obvious and partially apparent from the specification, and the scope of the invention will be set forth in the claims.

[0031] The attached drawings illustrate various systems, apparatus, devices, and related methods, and similar reference letters refer to similar parts throughout. [Brief explanation of the drawing]

[0032] [Figure 1] Figures 1a-1c are photographs of the stock aqueous coating composition of Comparative Example A coated on a substrate, after drying for 1 day (1a), 4 days (1b), and 7 days (1c) and then submerged in water. Severe blistering was observed after 1 day of drying, and some blistering was observed after 4 days of drying.

[0033] [Figure 2]Figures 2a-2c are photographs of a stock aqueous coating composition (Comparative Example B) containing 0.5 wt percent of 3-glycidoxypropyltrimethoxysilane based on the weight of a (meth)acrylic polymer having at least one functional group with active hydrogen. This was coated onto a substrate and dried for 1 day (2a), 4 days (2b), and 7 days (2c) after coating the substrate, and then submerged in water. Moderate swelling was observed after 1 day of drying, and slight swelling was observed after 4 days of drying.

[0034] [Figure 3] Figures 3a-3c are photographs of a stock aqueous coating composition (Comparative Example C) containing 2.0 wt percent of 3-glycidoxypropyltrimethoxysilane based on the weight of a (meth)acrylic polymer having at least one functional group with active hydrogen. This was coated onto a substrate and dried for 1 day (3a), 4 days (3b), and 7 days (3c) after coating, and then submerged in water. Fish eyes were observed after 1 day of drying, and small swellings were observed after 4 days of drying.

[0035] [Figure 4] Figures 4a-4c are photographs of a stock aqueous coating composition (Example 2) containing 0.5 weight percent of the epoxysilane oligomer composition prepared in Example 1, based on the weight of a (meth)acrylic polymer containing a functional group having at least one functional group with active hydrogen. This was coated onto a substrate and dried for 1 day (4a), 4 days (4b), and 7 days (4c) after coating the substrate, and then submerged in water. Blistering was observed after 1 day of drying, and very small amounts of blistering were observed after 4 days of drying. An amount of approximately 0.5 weight percent of the epoxysilane oligomer composition is insufficient to achieve initial water resistance.

[0036] [Figure 5]Figures 5a-5c are photographs of a stock aqueous coating composition (Example 2) containing 2.0 wt percent by weight of an epoxysilane oligomer composition prepared in Example 3, based on the weight of a (meth)acrylic polymer containing at least one functional group having active hydrogen. This was coated onto a substrate, dried for 1 day (5a), 4 days (5b), and 7 days (5c) after coating the substrate, and then submerged in water. The appearance of the coating observed after drying for 1, 4, and 7 days showed no significant blistering or fisheyes. [Modes for carrying out the invention]

[0037] Next, an exemplary embodiment is shown in the attached figure.

[0038] In the specification and claims of this application, the following terms and expressions should be understood as shown:

[0039] The singular forms "a," "an," and "the" include the plural forms, and references to specific numbers include at least that specific value unless the context clearly indicates something else.

[0040] Unless otherwise indicated in the examples or elsewhere, all numerical values ​​in the specification and claims, such as amounts of materials, reaction conditions, durations, and quantified properties of materials, should be understood in all examples to be modified by the term "approximately."

[0041] All methods described herein may be performed in any suitable order, unless otherwise indicated herein or unless the context clearly contradicts it. Any use of any examples or exemplary language provided herein (e.g., "etc.") is intended solely to further illustrate the invention and, unless otherwise claimed, does not limit the scope of the invention.

[0042] Nothing in the specification should be construed as indicating that any unclaimed element is essential to the implementation of the invention.

[0043] The terms “comprising,” “including,” “containing,” and “characterized by,” and their grammatical equivalents, are comprehensive or unrestricted terms that do not exclude additional, unquoted elements or steps of method, but are understood to also include the more restrictive terms “consisting of” and “consisting essentially of.”

[0044] It will be understood that any numerical range listed herein includes all subranges within that range, and any combination of various endpoints of such ranges or subranges.

[0045] As used herein, integer values ​​of stoichiometric subscripts refer to molecular species, while non-integer values ​​of stoichiometric subscripts refer to mixtures of molecular species on a molecular weight average basis, a number average basis, or a mole fraction basis.

[0046] In the following description, all weight percentages are based on the total weight percentage of organic material unless otherwise specified, and all ranges described herein include all subranges between them, and any combination of the ranges between them and / or subranges.

[0047] Any compound, material, or substance explicitly or implicitly disclosed in the specification and / or described in the claims as belonging to a group of compounds, materials, or substances that are structurally, compositionally, and / or functionally related is further understood to include individual representatives of that group and all combinations thereof.

[0048] The expression “hydrocarbon group” or “hydrocarbon radical” means any hydrocarbon composed of hydrogen and carbon atoms with one or more hydrogen atoms removed, and includes alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aralkyl, and arenyl groups. The groups may consist of hydrocarbon groups containing at least one heteroatom, and hydrocarbon groups containing at least one heteroatom of, for example, oxygen, nitrogen, or sulfur.

[0049] The term "alkyl" means any monovalent saturated linear or branched hydrocarbon group from which one hydrogen atom has been removed; the term "alkenyl" means any monovalent linear or branched hydrocarbon group containing one or more carbon-carbon double bonds, where the bonding site of the group may be either a carbon-carbon double bond or any other location within it; and the term "alkynyl" means any monovalent linear or branched hydrocarbon group containing one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds, where the bonding site of the group may be a carbon-carbon triple bond, a carbon-carbon double bond, or any other location within it. Examples of alkyl groups include methyl, ethyl, propyl, and isobutyl. Examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenylnorbornane, ethylidenenorbornyl, ethylidenylnorbornene, and ethylidenenorbornenyl. Examples of alkynyls include acetylenyl, propargyl, and methylacetylenyl.

[0050] The term "alkylene" refers to any divalent saturated straight-chain or branched-chain hydrocarbon group from which two hydrogen atoms have been removed. Examples of alkylene groups include, but are not limited to, methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), and 2-methylpropylene (-CH2CH(CH3)CH2-). In compound nomenclature, it should be understood that the use of divalent alkyl groups is common nomenclature, such as 3-glycidoxypropyltrimethoxysilane, which is an alkyl group from which one additional hydrogen atom has been removed, and propyl is a divalent alkyl group equivalent to propylene.

[0051] As used herein, the terms “example” and “illustration” mean actual examples or illustrations. The words “example” or “illustration” do not indicate an important or preferred manner or embodiment. The word “or” is intended to be inclusive, not exclusive, unless the context suggests otherwise. For example, the phrase “A uses B or C” includes any inclusive permutation (e.g., A uses B; A uses C; or A uses both B and C). Separately, the articles “a” and “an” are generally intended to mean “one or more” unless the context suggests otherwise.

[0052] As used herein, “water-based” means a coating that contains liquid water and can be used interchangeably with “water-based.”

[0053] An aqueous coating composition is provided comprising a (meth)acrylic polymer having at least one functional group having an active hydrogen group, an epoxy silane oligomer composition, an emulsifier, titanium dioxide, a siliceous particulate filler, water, and optionally other components. The aqueous coating composition of the present application exhibits initial moisture resistance. In particular, the aqueous coating composition shows a reduction in the size and / or frequency of defects, including blistering, fish eyes, and / or delamination, compared to a composition that does not contain the epoxy-modified silane oligomer composition.

[0054] Emulsions of (meth)acrylic polymers containing at least one functional group having active hydrogen in combination with other components are often called latex coatings or latex paints. Latex paints are used in a variety of applications, including interior and exterior. Depending on the needs of the specific application, latex paints can be supplied as flat, semi-gloss, gloss, or satin finishes. Latex is a dispersion of rubber or plastic polymer microparticles in an aqueous medium, where emulsifiers are used to stabilize the microparticles. Latex may be natural or synthetic.

[0055] (a) A (meth)acrylic polymer containing at least one functional group having active hydrogen.

[0056] The (meth)acrylic polymers of the present invention are, but are not limited to, carboxyl groups (-C(=O)OH), some of which are, for example, -C(=O)OH - M + , here, M + is Na + , K +Alternatively, it may be in the form of an ammonium ion neutralized salt, or it may have at least one functional group having active hydrogen, including a hydroxyl group (-OH). The polymer contains terminal or pendant carboxyl groups and / or hydroxyl groups. In particular, the polymer contains a sufficient amount of carboxyl groups to have an acid value between 1 and 780, preferably between 10 and 280, as determined by potentiometric titration. The potentiometric titration method is shown below: Wang, C., Tam, KC, Jenkins, RD, & Bassett, DR (2000), Potentiometric titration and dynamic light scattering of hydrophobically modified alkali soluble emulsion (HASE) polymer solutions, Physical Chemistry Chemical Physics, 2(9), 1967-1972, May 2000. doi:10.1039 / A910302N, the whole thereof is incorporated herein by reference. If the active hydrogen-containing group is a hydroxyl group, the amount of hydroxyl groups is determined using ASTM D4274-05, Standard Test Method for Testing Polyurethane Raw Materials: Determination of Hydroxyl Number of Polyols, which is incorporated herein by reference in its entirety. If hydroxyl groups are present, their number ranges from 1 to 25, more specifically from 5 to 15.

[0057] (Meth)acrylic polymers containing at least one functional group having active hydrogen are available in quantities from 1000 to 1 × 10⁻⁶. 8 It has a weight-average molecular weight in the gram / molar range. The weight-average molecular weight is determined using gel permeation chromatography. In one embodiment, the standard test method for the molecular weight average and molecular weight distribution of polystyrene by ASTM D5296-11 high-performance size exclusion chromatography (which is incorporated herein in its entirety) can be used.

[0058] (Meth)acrylic polymers (a) containing at least one functional group having active hydrogen can be prepared by emulsion polymerization. Emulsion polymerization involves polymerization of (meth)acrylic monomers in the presence of an emulsifier and water. A description of emulsion polymerization can be found in Emulsion Polymerization, D. Distler, Encyclopedia of Materials: Science and Technology (second edition), 2769-2774 (2001) (the entire text is incorporated herein).

[0059] (Meth)acrylic polymers (a) containing at least one functional group having active hydrogen are typically selected from pure acrylic, styrene acrylic, vinyl acrylic, and acrylate ethylene vinyl acetate copolymers.

[0060] Pure acrylic is prepared using acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers. Styrene acrylic is prepared using styrene and acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers. Vinyl acrylic is prepared using vinyl acetate and acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers. Acrylated ethylene vinyl acetate copolymer is prepared using ethylene, vinyl acetate, and acrylic acid, methacrylic acid, acrylate esters, and / or methacrylate esters as monomers. As will be readily apparent to those skilled in the art, monomers may also include other monomers such as acrylamide and acrylonitrile, as well as one or more functional monomers such as itaconic acid and ureidomethacrylate.

[0061] The carboxyl content of (meth)acrylic polymer (a) containing at least one functional group having active hydrogen is often incorporated into the polymer using acrylic acid or methacrylic acid monomers during the emulsion polymerization process. The carboxyl content of (meth)acrylic polymer (a) containing at least one functional group having active hydrogen can also be formed in situ during the emulsion polymerization reaction by hydrolysis of the ester functional group of (meth)acrylic polymer (a) containing at least one functional group having active hydrogen.

[0062] The (meth)acrylic polymer (a) of the present invention, which contains at least one functional group having active hydrogen, can be added to an aqueous coating composition as an emulsion comprising the (meth)acrylic polymer (a), an emulsifier (c), water (f), and any other optional components. The amounts of water (e) and emulsifier (c) may constitute some or all of the emulsifier and water (f) in the aqueous coating composition.

[0063] Emulsions of (meth)acrylic polymers (a) containing at least one functional group having active hydrogen are commercially available. Representative and non-limiting examples of emulsions of (meth)acrylic polymers (a) containing at least one functional group having active hydrogen include Joncryl® 60 polyacrylic resin and Joncryl® 67 polyacrylic resin, commercially available from BASF in Florham Park, New Jersey, and Acronal® PLUS 4670 acrylic resin and Acronal® PLUS 4130 acrylic latex resin, commercially available from BASF in Florham Park, New Jersey.

[0064] The selection of a (meth)acrylic polymer (a) containing at least one functional group having active hydrogen is used to determine the finish of the coating. In one embodiment, the (meth)acrylic polymer (a) containing at least one functional group having active hydrogen is a "complete acrylic" or a pure acrylic having a limited amount of styrene polymer or having no styrene polymer. In one embodiment, the (meth)acrylic polymer (a) containing at least one functional group having active hydrogen is mainly selected from butyl acrylate / methyl methacrylate copolymers derived from monomers containing butyl acrylate and methyl methacrylate.

[0065] In a typical acrylic paint composition, a (meth)acrylic polymer (a) containing at least one functional group having active hydrogen is composed of a mixture of about 50:50 by weight of one or more esters of acrylic acid or methacrylic acid, typically a high-Tg monomer derived from methyl methacrylate, and a low-Tg monomer such as butyl acrylate having acrylic acid or methacrylic acid in a small proportion of about 0.5 to about 2 by weight. Vinyl acrylic paints typically contain vinyl acetate and butyl acrylate and / or 2-ethylhexyl acrylate. In vinyl-acrylic paint compositions, at least about 50 percent of the formed polymer consists of vinyl acetate, with the remainder selected from esters of acrylic acid or methacrylic acid. Styrene / acrylic polymers are typically similar to acrylic polymers in which all or part of the methacrylate monomer is substituted with styrene.

[0066] Emulsions of (meth)acrylic polymer (a) containing at least one functional group having active hydrogen contain about 30 to about 75% solid and an average emulsion particle size of about 70 to about 650 nm.

[0067] The (meth)acrylic polymer (a) having at least one functional group having active hydrogen is preferably present in the aqueous coating composition in an amount of about 5 to about 60% by weight, about 8 to about 40% by weight, or about 15 to about 30% by weight, based on the total weight of the (meth)acrylic polymer (a) having at least one functional group having active hydrogen (d) (dry weight), epoxysilane oligomer composition (b), emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f).

[0068] Epoxysilane oligomer composition (b)

[0069] The epoxysilane oligomer composition (b) is a mixture of components containing epoxy functional groups and silicon atoms. The epoxysilane oligomer composition consists of the following: (i) A monomer having the structure of formula (I) in an amount of about 5 to about 15 weight percent: (Z c ) a (R 1 O) 3-2a Si-R 2 (I) (ii) Dimers having the structure of formula (II) in an amount of about 5 to about 20 weight percent: (Z c ) b (R 1 O) 2-2b (R 2 )Si-O-Si(R 2 )(OR 1 ) 2-2c (Z c ) c (II) (iii) At least one trimer having a linear structure (III) or a cyclic structure (IV) in an amount of about 5 to about 20 weight percent: [ka] [ka] Here, the total amount of trimer (iii) is the sum of the weights of the linear trimer of formula (III) and / or the cyclic trimer of formula (IV), and (iv) At least one polyoligomer having the structure of formula (V) in an amount of about 45 to about 85 weight percent: [ka] Here, the total amount of polyoligomer (iv) is the sum of the weights of each component having the structure of formula (V), Here Z c Each existence is independently a divalent base-OR 4 O-, and here R 4 This is a divalent linear alkylene group of 2 to 6 carbon atoms or a branched alkylene group of 3 to 6 carbon atoms, however (i) Two oxygen atoms are R 4 It is bonded to two different carbon atoms, and (ii) The open valence of each oxygen atom is bonded to the same Si atom to form a cyclic 1,3-dioxa-2-sila-cycloalkyl group, R 1 Each of these entities independently consists of a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, or -OR 4 It is an OH group, and here R 4 These are independently divalent linear alkylene groups of 2 to 6 carbon atoms or branched alkylene groups of 3 to 6 carbon atoms. R 2 Each of these entities is as follows: [ka] R 3 Each of these entities independently includes a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, and -OR 4 OH group, here R 4is, independently, a divalent linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms, or is as follows, [Chemical formula] where each occurrence of R 5 is, independently, a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, -OR 4 OH group, where R 4 is, independently, a divalent linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms, or is as follows, [Chemical formula] and the subscripts a, b, c, d, e, f, g, h, i, m, and n are integers, where a, b, c, d, e, f, g, h, and i are independently 0 or 1, m is from 0 to 5, and n is from 2 to 15, and where the weight percentages are based on the total combined weight of components (i), (ii), (iii), and (iv).

[0070] Representative and non-limiting examples of R 1 include methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl, and 1,3-dimethyl-3-hydroxybutyl.

[0071] Representative and non-limiting examples of R 3 include methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl, and 1,3-dimethyl-3-hydroxybutyl.

[0072] Representative and non-limiting examples of R 4 include ethylene, propylene, and 2-methylpropylene.

[0073] R 5 Representative and non-exclusive examples include methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl and 1,3-dimethyl-3-hydroxybutyl, (glycidoxypropyl)bis(2-methyl-3-hydroxypropoxy)silyl, and [(glycidoxypropyl)dimethoxysilyloxy]-(glycidoxypropyl)methoxysilyl.

[0074] In one embodiment, the epoxysilane oligomer composition, R 1 is methyl or ethyl, R 3 is methyl or ethyl, R 5 The components are methyl, ethyl, (glycidoxypropyl)dimethoxysilyl or (glycidoxypropyl)diethoxysilyl, and a, b, c, d, e, f, g, h, and i are 0.

[0075] In one embodiment, the epoxysilane oligomer composition is synthesized by the reaction of a glycidoxysilane having three hydrolyzable groups with water in the presence of a catalyst, where the water is continuously supplied during the reaction. The epoxysilane oligomer can also be synthesized using controlled hydrolysis and condensation of an epoxysilane monomer with the continuous introduction of water and a catalyst.

[0076] The catalyst can be selected from any suitable catalyst, including but not limited to strong cation exchange resin materials or acid catalysts such as acetic acid or sulfuric acid.

[0077] Representative and non-limiting examples of catalysts that can be used to prepare epoxysilane oligomer compositions include ion exchange resins, e.g., Purolite® CT-175 or CT275, available from Plurolite; Amberlite® IRA 400, 402, 904, 910 or 966, available from Sigma-Aldrich; Lewatit® M-500, M-504, M-600, M-500-A, M-500 or K-2641, available from Bayer; Dowex® SBR, SBR-P, SAR, MSA-1 or MSA 2, available from Dow; or DIAON® SA10, SA12, SA 20A, PA-302, PA-312, PA-412 or PA-308, available from Mitsubishi. The catalyst may also be an alkylammonium salt, for example, hexadecyltrimethylammonium chloride, tetra-n-butylammonium chloride, or benzyltrimethylammonium chloride or bromide, or a hydroxide form of these alkylammonium salts, either alone or in combination with a halide salt. Other useful catalysts are reaction products of quaternary ammonium organofunctional silanes and supports such as ceramics (including glass), silica gel, precipitated or fumed silica, alumina, and aluminosilicate.

[0078] Suitable examples of glycidoxysilanes include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriproxysilane, 3-glycidoxypropyl-tris-(2-methyl-3-hydroxypropoxy)silane, 3-glycidoxypropyl-tris-(3-hydroxybutoxy)silane, 2-(3-trimethoxysilylpropyl)-2-(3-hydroxypropoxy)-[1,3,2]-dioxasilinane, and 2-(3-trimethoxysilylpropyl)-2-(2-methyl-3-hydroxypropoxy)-5-methyl-[1,3,2]-dioxasilinane.

[0079] The molar ratio of water to the silane monomer can be from about 0.5:1.0 to about 1.0:1.0, or from about 0.65:1.0 to about 0.85:1.0.

[0080] The epoxy silane oligomer (ESO) can be synthesized in the presence of a chemically stable alcohol-free solvent, such as paraffin, aliphatic hydrocarbons, naphtha or mineral spirits, aromatic hydrocarbons such as toluene, xylene, or their higher-boiling homologs; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, amyl ketone, esters such as ethyl, n-propyl, n-butyl, or amyl acetate.

[0081] In another embodiment of the present invention, the by-product alcohol is continuously removed during the reaction.

[0082] The amount of each component of the epoxy silane oligomer composition can be determined using a reverse-phase high-pressure liquid chromatography (HPLC) method. The experimental conditions that can be used are an Affinity 2620 ELS detector, 60 °C under 1.60 SLPM N2 conditions, a LUNA C18 end cap, 5 micron, 300x4.6 mm column, solvent gradient [Table 1] a flow rate of 0.5 mL / min, and an injection volume of 0.5 microliters of a solution containing 0.1 gram of epoxy silane oligomer concentration in 4 mL of isopropanol. The individual components eluted from the reverse-phase high-pressure liquid chromatography analysis can be separated and further analyzed by mass spectrometry and nuclear magnetic resonance (NMR) techniques.

[0083] The epoxy silane oligomer composition can also use 0.05 M chromium acetylacetonate (Cr(AcAc)3) in DCCl3 relaxant 29 and can be analyzed using SiNMR technology.

[0084] The number-average and weight-average molecular weights of epoxysilane oligomer compositions can be determined by gel-phase chromatography (GPC). This method involves the use of an Agilent 2600 Infinity chromatograph equipped with Agilent 2600 Infinity PDA UV and Agilent 2600 Infinity ELS detectors, and data acquisition using an Agilent OpenLab system. Columns were fabricated by Phenomenex Spherogel Linear(2), consisting of a 100x4.6 mm guard column and a 300x7.6 mm linear mixed-bed column, with a reported molecular weight range of 100 to 20,000,000 (polystyrene). The columns were packed with styrenedivinylbenzene with a particle size of 5 microns, and had an inlet frit of 0.2 microns and an outlet frit of 0.5 microns. The solvent was methylene chloride at a flow rate of 1.0 mL / min. The injection volume was 1 microliter of a 1.0 to 1.5 wt percent solution of the epoxysilane oligomer composition, filtered through a 0.45 micron disposable filter to remove undissolved particulate matter. The system was calibrated using narrow Mw polydimethylsiloxane (range 12 from 230 to 1,250,000).

[0085] In one embodiment, the weight-average molecular weight of the epoxysilane oligomer composition is about 500 to about 2500, more specifically about 800 to about 1600, and even more specifically about 1100 to about 1500.

[0086] The epoxysilane oligomer composition may be present in amounts greater than 0.5% by weight and about 5% by weight, more specifically from about 0.75% by weight to about 3% by weight, and even more specifically from about 1.0% by weight to about 2.0% by weight, based on the weight of a (meth)acrylic polymer (a) having at least one functional group having active hydrogen.

[0087] The epoxysilane oligomer composition can be added to the coating composition during the mixing step of forming the aqueous coating composition, during the formation of an emulsion of a (meth)acrylic polymer (a) having at least one functional group having active hydrogen, or it can be added as a “post-addition” material to a stock aqueous coating composition containing a (meth)acrylic polymer (a) having at least one functional group having active hydrogen, an emulsifier (c), titanium dioxide (d), siliceous microparticle filler (e), water (f), and any other component. In embodiments, the epoxysilane oligomer is added to the stock aqueous coating composition as a “post-addition” material before the aqueous coating composition is applied to a substrate. In one embodiment, a stock aqueous coating composition containing components (a), (c), (d), (e), (f), and any other component is provided, and the epoxysilane oligomer composition (b) is added to and mixed with the stock aqueous coating composition to provide the aqueous coating composition of the present invention.

[0088] Emulsifier (c)

[0089] Emulsifier (c) is used to form an emulsion of (meth)acrylic polymer (a) containing at least one functional group having active hydrogen. Emulsifier (c) stabilizes (meth)acrylic polymer (a) containing at least one functional group having active hydrogen in water (f). Emulsifier (c) also functions to stabilize the epoxysilane oligomer composition in the aqueous (f) phase of the aqueous coating composition.

[0090] The emulsifiers (c) used herein include nonionic, anionic, and cationic surfactants or mixtures of surfactants. The mixtures include a mixture of at least one nonionic surfactant, or a mixture of a nonionic surfactant and at least one anionic surfactant or at least one cationic surfactant.

[0091] Representative and non-limiting examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Representative and non-limiting examples of anionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonate salts, alkyl phosphate salts, alkyl allyl sulfate ester salts, and polyoxyethylene alkyl phosphate ester salts. Representative and non-limiting cationic surfactants include quaternary ammonium salts, such as long-chain alkyltrimethylammonium salts and di(long-chain alkyl)dimethylammonium salts.

[0092] A further list of surfactants useful in the present invention may be found in 1994 McCutcheon's Vol. 2: Functional Materials, North American Edition (The Manufacturing Confectioner Publishing Co., Glen Rock), which is incorporated herein by reference.

[0093] The appropriate hydrophilic-lipophilic balance (HLB) of the surfactant is selected to correspond to the HLB of the (meth)acrylic polymer (a) containing at least one functional group having active hydrogen that is being emulsified. Methods for selecting the optimal HLB for a polymer are well known to those skilled in the art and are described, for example, in "The HLB System" by ICI Americas Inc.

[0094] Since emulsions of (meth)acrylic polymer (a) containing at least one functional group having active hydrogen, as defined by components (a), (c), and (f), can be prepared before the addition of epoxysilane oligomer composition (b), emulsifiers can also be selected so that their HLBs are close to those of the epoxysilane oligomer composition and help stabilize the epoxysilane oligomer in the aqueous coating composition.

[0095] The emulsifier (c) should be present in an amount of about 0.5 to about 50 weight percent, more specifically about 1.0 to about 15 weight percent, and even more specifically about 2.0 to about 7 weight percent, based on the weight of the (meth)acrylic polymer (a) having at least one functional group having active hydrogen.

[0096] Titanium dioxide particles

[0097] Titanium dioxide, also known as titanium(IV) oxide or titania, is a naturally occurring oxide of titanium with the chemical formula TiO2. When used as a pigment, it is called titanium white, pigment white 6 (PW6), or CI77891. It is commonly sourced from ilmenite, rutile, and anatate. Titanium dioxide exists in nature as the minerals rutile and anatate, and also as two further high-pressure forms. One of these is a monoclinic baddeleyite-like form known as akaogiite, and the other is an orthorhombic α-PbO2-like form known as brookite. Rutile contains approximately 98% titanium dioxide in its ore. The metastable anatate and brookite phases are irreversibly converted to the equilibrium rutile phase when heated above temperatures in the range of 600-800°C.

[0098] Titanium dioxide, in addition to rutile, anatate, rosacea, and brookite, has eight variants and can synthesize three metastable phases (monoclinic, tetragonal, and orthorhombic), as well as five high-pressure forms (α-PbO2-like, baddeleyite-like, cothnite-like, orthorhombic OI, and cubic phases). The most common mineral source is ilmenite.

[0099] Rutile mineral sand can also be purified by a chloride process or other processes. Ilmenite is converted to pigment-grade titanium dioxide via either a sulfate or chloride process. Both sulfate and chloride processes can produce titanium dioxide pigment in the form of rutile crystals. The chloride process converts ilmenite or other titanium sources to titanium tetrachloride by reaction with elemental chlorine, which is then purified by distillation, reacting with oxygen to regenerate chlorine, and then producing titanium dioxide. Titanium dioxide pigment can also be produced via a chloride acid process from high-titanium-content raw materials such as upgraded slag, rutile, and leucoxene.

[0100] Titanium dioxide particles may be in the form of a slurry, which contains other components including aluminum hydroxide, silica, and water.

[0101] Titanium dioxide particles can be classified using the method DIN EN ISO 591-1 (2000) Titanium dioxide pigments for coatings - Part 1: Test specifications and methods, as well as the ASTM D476 standard classification for dried titanium dioxide pigment products. In one embodiment, the classification by type is as follows: [Table 2]

[0102] In one embodiment, the titanium dioxide pigment is selected from types I, IV, and V.

[0103] The properties of a pigment can be determined by the ASTM D1208 - 96(2019) standard test method for the general properties of a particular pigment.

[0104] Titanium dioxide particles (pigments) are available from Chemors, Cristal Global, Venator-Huntsman, Kronos, and Tronox. Representative and non-exclusive examples of titanium include Ti-Pure® R-900, Ti-Pure® R-960, Ti-Pure® TS-6200, Ti-Pure® TS-6300, Ti-Pure® R-746, Ti-Pure® R-706, Ti-Pure® R-7411, and Ti-Pure® R-902, all commercially available from Chemors, Wilmington, Delaware.

[0105] The amount of titanium dioxide particles used in the aqueous coating composition ranges from about 0.5% by weight to about 50% by weight, more specifically from about 1.0% by weight to about 25% by weight, and even more specifically from about 5.0% by weight to about 20.0% by weight, where the weight percentage is based on the sum of the weights of (meth)acrylic polymer (a) (dry weight) containing at least one functional group having active hydrogen, epoxysilane oligomer composition (b), emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f).

[0106] Silicate particulate filler (e)

[0107] Silicate particulate fillers (e) are minerals containing silicates. Silicate particulate fillers (e) include aluminum silicate, for example, hydrated kaolin [Al2Si2O5(OH)4], mullite [Al2SiO5], pyrophyllite [Al2Si4O 10(OH)2], kyanite [Al2OSiO4], nephrite syenite [sodium, potassium aluminum silicate], clay [hydrated aluminum phyllosilicate], and sillimanite [Al2SiO5]; silica [SiO2], including fumed silica, precipitated silica, and crushed quartz; talc [Mg3Si4O 10 (OH)2]: and others can be selected.

[0108] The particle size distribution of siliceous particulate filler (e) can be determined by the ASTM C1070-01 (2014) standard test method for determining the particle size distribution of alumina or quartz by laser light scattering.

[0109] Representative and non-exclusive examples of siliceous particulate fillers (e) include Minex® 10 nephrite syenite, commercially available from Sibelco; Kaoplate®, manufactured by Thiele in Sandersville, Georgia; and Attagel® 50, available from BASF in Florham Park, New Jersey.

[0110] The amount of siliceous particulate filler (e) in the aqueous coating composition may be about 0.05 to about 25 weight percent, more specifically about 0.1 to about 15 weight percent, and even more specifically about 1 to about 5 weight percent, where the weight percent is based on the sum of the weights of (meth)acrylic polymer (a) (dry weight) having at least one functional group having active hydrogen, epoxysilane oligomer composition (b), emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f).

[0111] water (f)

[0112] Water, including tap water, deionized water, or distilled water, is present in amounts up to 100% of the total weight of the (meth)acrylic polymer (a) (dry weight) having at least one functional group having active hydrogen, epoxysilane oligomer composition (b), emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f), more specifically about 35 to about 90 weight percent, and even more specifically about 40 to about 80 weight percent, based on the total weight of the (meth)acrylic polymer (a) (dry weight) having at least one functional group having active hydrogen, epoxysilane oligomer composition (b), emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f).

[0113] Other additives

[0114] One or more additives are not particularly limited and can be selected from any additives suitable for the aqueous coating composition and for a particular purpose or intended use. In embodiments, the composition may include one or more additives selected from the group consisting of adhesion promoters, dispersants, wetting agents, rheological modifiers, defoamers, thickeners, biocides, fungicides, colorants, waxes, fragrances, and cosolvents.

[0115] In addition to the epoxysilane oligomer produced according to the present invention, the aqueous coating composition may contain non-epoxy monomer silanes such as vinylsilane, alkylsilane, or alkylenesilane. Typical non-epoxy monomer silanes include vinyltrimethoxysilane, commercially available from MomentivePerformance Materials, Inc. in Waterford, New York under the trade name Silquest® A-171 silane; vinyltriethoxysilane, commercially available from MomentivePerformance Materials, Inc. in Waterford, New York under the trade name Silquest® A-151 silane; vinylmethyldimethoxysilane, commercially available from MomentivePerformance Materials, Inc. in Waterford, New York under the trade name Silquest® A-2171 silane; vinyltriisopropoxysilane, commercially available from MomentivePerformance Materials, Inc. in Waterford, New York under the trade name CoatOSil® A-1706 silane; n-octyltriethoxysilane, commercially available from MomentivePerformance Materials, Inc. in Waterford, New York under the trade name Silquest® A-137 silane; and propyltriethoxysilane, commercially available from MomentivePerformance Materials, Inc. in Waterford, New York under the trade name Silquest® A-137 silane. Methyltrimethoxysilane, marketed under the trade name Silquest® A-138 silane by Momentive Performance Materials, Inc. in Waterford, New York; polyalkylene oxide trimethoxysilane, marketed under the trade name Silquest® A-1630 silane by Momentive Performance Materials, Inc. in Waterford, New York; 3-methacryloxypropyltrimethoxysilane, marketed under the trade name Silquest® A-1230 silane by Momentive Performance Materials, Inc. in Waterford, New York; Waterford,It may be marketed under the trade name Silquest® A-174 silane from Momentive Performance Materials, Inc. of New York, or as 3-methacryloxypropyltriisopropoxysilane, marketed under the trade name CoatOSil® A-1757 silane from Momentive Performance Materials, Inc. of Waterford, New York.

[0116] In one embodiment, the aqueous coating composition of any prior embodiment is a coating composition having a gloss of 60 degrees between 10 to 40 gloss units (GU); 15 to 35 gloss units; or 20 to 30 gloss units. The gloss can be evaluated using any suitable apparatus and method for measuring gloss. In one embodiment, the gloss is measured using a BYK Micro-TRI-GlossMeter according to the ASTM D 523 - 14(2018) standard test method for specular gloss.

[0117] The aqueous coating compositions of the present invention can be applied to any suitable substrate as desired for a particular purpose or intended use. In one embodiment, a method for coating a substrate is: (a) To provide a stock aqueous coating composition comprising (a) a (meth)acrylic polymer having at least one functional group having active hydrogen, an emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), water (f), and an optional additive, (b) Adding epoxysilane oligomer to the stock aqueous coating composition, (c)(b) comprises applying the composition of (c)(b) to a substrate and drying the composition to form a coating.

[0118] As used herein, drying means the removal of water from an aqueous coating composition. Drying includes methods such as evaporation under ambient temperature and pressure conditions, high temperature or reduced pressure, or both. It is understood that drying does not require the complete removal of water and may result in some residual water, including but not limited to less than about 10% by weight, more preferably less than about 5% by weight, and even more preferably less than about 1% by weight, based on the total weight of the (meth)acrylic polymer (a) having at least one functional group with active hydrogen, the epoxysilane oligomer composition (b), the emulsifier (c), titanium dioxide particles (d), the siliceous particulate filler (e), and water (f).

[0119] In one embodiment, the aqueous coating composition from (b) is applied to the substrate "as is," i.e., without further processing of the coating before application to the substrate. In one embodiment, the aqueous coating composition from (b) is heat-aged before the composition is applied to the substrate. Heat aging can be carried out at approximately 50°C for 2, 5, 7, 10, or 14 days. In one embodiment, the composition from (b) is heat-aged at 50°C for 14 days before the composition is applied to the surface of the substrate.

[0120] While not bound by any particular theory, initial water resistance is achieved by the rapid adsorption of a (meth)acrylic polymer (a) having at least one functional group with active hydrogen onto titanium dioxide particles (d) and siliceous particulate fillers (e), forming interactions between component (a) and components (d) and (e), where the epoxysilane oligomer composition (b) chemically reacts with these components to impart initial water resistance.

[0121] The aqueous coating composition is a stable fluid that can be applied to a wide variety of materials, such as paper, wood, concrete, metal, glass, ceramic, plastic, plaster, roofing substrates, such as asphalt coatings, roofing felt, and foamed polyurethane insulation; or to previously painted, primed, undercoated, worn, or weathered substrates. The aqueous coating composition of the present invention can be applied to materials by various techniques well known in the art, such as brushes, rollers, mops, air-assisted or airless sprays, and electrostatic sprays. [Examples]

[0122] example

[0123] Example 1. Preparation of epoxysilane oligomer composition

[0124] In a reactor equipped with an addition funnel, a water condenser, and a mechanical stirrer, 100 parts of 3-glycidoxypropyltrimethoxysilane (Silquest® A-187 silane, manufactured by Momentive Performance Materials, Inc.) and 35 parts of ion exchange resin (Amberlite® IRA 402 CL, available from Sigma-Aldrich) were added. Water was slowly and continuously introduced while stirring at atmospheric pressure and a temperature of approximately 70°C. The amount of water was 0.73 moles per mole of 3-glycidoxypropyltrimethoxysilane. After the addition was complete, the reaction mixture was stirred at high temperature to complete the reaction. Methanol formed from the reaction was removed from the reactor under reduced pressure of approximately 0.2 bar. The reaction mixture was cooled to room temperature. The reaction mixture was filtered to remove the ion exchange resin and approximately 80 parts of the product were obtained.

[0125] Reverse-phase high-pressure liquid chromatography detected 11.9 wt percent of 3-glycidoxypropyltrimethoxysilane, 13.3 wt percent of 1,3-bis-(3-glycidoxypropyl)-1,1,3,3-tetramethoxydisiloxane, 14.2 wt percent of 1,3,5-tris-(3-glycidoxypropyl)-1,1,3,3,5,5-hexamethoxy-1,3,5-tricila-2,4-dioxapentane, and 60.6 wt percent of high molecular weight polyoligomers. The weight-average molecular weight of the epoxysilane oligomer composition was 1300. 29 SiNMR analysis revealed that silicon atoms bonded to -OSi groups 0, 1, 2, and 3 accounted for 11.9 mole percent, 41.3 mole percent, 37.3 mole percent, and 9.5 mole percent, respectively.

[0126] Examples 2 and 3, as well as Comparative Example AC

[0127] Aqueous coating compositions according to aspects and / or embodiments of the present invention were evaluated for initial water resistance. The epoxysilane oligomer composition prepared in Example 1 was added to a commercially available satin exterior paint, and initial water resistance was tested using a water immersion test, and blistering was evaluated using ASTM D 714 (Standard Test Method for Evaluating the Blistering Degree of Paints). The commercially available satin exterior paint was Ultra Pure White No. 9850, trade name Premium Plus Ultra Exterior Satin Paint, purchased from Behr. The composition of the commercially available satin exterior paint contained 2-ethylhexyl benzoate, aluminum hydroxide, polymers based on butyl acrylate and methyl methacrylate monomers containing less than 2 wt percent methacrylic acid, amorphous and precipitated silica, and titanium dioxide pigment. The amount of (meth)acrylic polymer was about 27 wt percent based on the dry resin solid, and the amounts of silica and titanium dioxide were used at levels greater than 1 and 10 wt percent, respectively.

[0128] Samples of the aqueous coating compositions were prepared using a quarter-pint can lined with epoxy. A commercially available satin exterior paint (150 grams) was added to the can. Subsequently, epoxysilane, 3-glycidoxypropyltrimethoxysilane (Silquest® A-187, available from Momentive Performance Materials Inc.), or the epoxysilane oligomer composition of Example 1 was added to the satin exterior paint. The silane or epoxysilane oligomer composition was incorporated using a low-shear paddle blade. The samples were left to stand for 4 hours before performing the drawdown. The material was drawn onto an alkyd-cured black Leneta scrub chart using a 5-mil bard bar. The alkyd-cured black Leneta scrub chart containing the aqueous coating composition was dried (cured) for varying times at ambient temperature and humidity.

[0129] After a 24-hour curing time, the drawdown was cut into three equal 2.5 × 6.5 inch (6.35 × 16.51 cm) coated strips. The first strip was immersed in room temperature deionized water for 24 hours. The second strip was cured for a further 3 days and then immersed in room temperature deionized water for 24 hours. The last strip was cured for a further 6 days and then immersed in room temperature deionized water for 24 hours. After the approved curing and immersion times, the panels were removed from the deionized water, patted dry with a paper towel, and assessed for blistering using ASTM D714.

[0130] Once the drawdown was complete, the remaining material in the quarter-pint can was sealed with a suitable lid and placed in a 50°C oven for two weeks. After the samples were in the 50°C oven for two weeks, they were removed and left on a benchtop for four hours to return to room temperature. The above experiment was repeated with these aged aqueous coating composition samples.

[0131] The compositions used in the tests are shown in Table 1. [Table 3]

[0132] Overview of ASTM D 714 Evaluation

[0133] Under the ASTM D 714 test method, blistering is evaluated in terms of size and frequency. Blister size is evaluated on a numerical scale from 0 to 10, where 10 represents no blistering and 8 represents the smallest blister; 6, 4, and 2 represent progressively larger sizes. Blistering frequency is evaluated by the density of blistering within a specific area and is given the designation D (high density), MD (medium density), M (medium), or F (few). In the current test, blistering frequency is evaluated across the entire painted area of ​​the coated strip, which is the entire painted area of ​​a 2-inch x 2.5-inch (5.08cm x 6.35cm) drawdown of a placard cut to 2.5 x 6.5 inches (6.35 x 16.51cm).

[0134] Tables 2 and 3 show the results of the blistering evaluation observed for each coating. Table 2 shows the results of tests performed on the "manufacturing" coating, i.e., the coating applied to the substrate without further processing. Table 3 shows the results of the heat-aged coating as described in the Experiments section. [Table 4] [Table 5]

[0135] Figures 1 to 5 are photographs of coating samples using heat-aged coatings. Examples 2 and 3 exhibit better moisture resistance compared to Comparative Example A, which does not contain additional epoxysilane, as evidenced by the reduction in blistering evaluated at 1 and 4 days. Examples 2 and 3 also perform better than Comparative Examples B and C. Example 3, using a high concentration of epoxysilane oligomer, performs better than Comparative Examples B and C, which use monomer epoxysilane. Although Example 2 has a slightly higher density of blistering than Comparative Examples B and C, Example 2 performs better in that the coatings of Comparative Examples B and C exhibit other defects such as pinholes that are not seen in Examples 2 and 3.

[0136] The above descriptions include examples of those specified herein. Of course, it is impossible to describe all possible combinations of components or methodologies for the purposes described herein, but those skilled in the art will recognize that many more combinations and permutations of those specified herein are possible. Accordingly, this specification is intended to encompass all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, insofar as the term “includes” is used in either the detailed description or the claims, such term is intended to be comprehensive in the same manner as “comprising” is interpreted when the term “comprising” is used as a transitional term within a claim.

[0137] The foregoing description identifies various non-limiting embodiments of coating compositions, particularly latex coating compositions. Modifications may occur for those skilled in the art and those who can construct and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention or the subject matter described in the claims.

Claims

1. (a) A (meth)acrylic polymer comprising at least one functional group having active hydrogen; (b) an epoxysilane oligomer composition, (i) A monomer having the structure of formula (I) in an amount of 5 to 15 weight percent: (Z ｃ ) ａ (R) １ O) ３－２ａ Si-R ２ (I) (ii) Dimers having the structure of formula (II) in amounts of 5 to 20 weight percent: (Z ｃ ) ｂ (R １ O) ２－２ｂ (R ２ )Si-O-Si(R ２ )(OR １ ) ２－２ｃ (Z ｃ ) ｃ (--); (iii) At least one trimer having a linear structure (III) or a cyclic structure (IV) in an amount of 5 to 20 weight percent: 【Chemistry 1】 【Chemistry 2】 Here, the total amount of trimer (iii) is the sum of the weights of the linear trimer of formula (III) and / or the cyclic trimer of formula (IV), and (iv) At least one polyoligomer having the structure of formula (V) in an amount of 45 to 85 weight percent: 【Transformation 3】 Here, the total amount of polyoligomer (iv) is the sum of the weights of each component having the structure of formula (V), and the epoxysilane oligomer composition includes Here Z ｃ Each existence is independently a divalent base -OR ４ O-, and here R ４ These are independently divalent linear alkylene groups of 2 to 6 carbon atoms or branched alkylene groups of 3 to 6 carbon atoms, however (i) The two oxygen atoms are R ４ It is bonded to two different carbon atoms inside, and (ii) The condition is that the open valence of each oxygen atom is bonded to the same Si atom to form a cyclic 1,3-dioxa-2-sila-cycloalkyl group, R １ Each of these entities independently comprises a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, or R ４ As stated above - OR ４ It is an OH group, R ２ Each existence is as follows: 【Chemistry 4】 R ３ Each of these entities independently comprises a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, and R ４ As stated above - OR ４ OH group, or the following: 【Transformation 5】 Here R ５ Each of these entities independently comprises a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, and R ４ As stated above - OR ４ OH group, or the following: 【Transformation 6】 The subscripts a, b, c, d, e, f, g, h, i, m, and n are integers, where a, b, c, d, e, f, g, h, and i are 0, m is between 0 and 5, and n is between 2 and 15, and the weight percentage is based on the total weight of the sum of components (i), (ii), (iii), and (iv). (c) Emulsifier; (d) Titanium oxide particles; (e) siliceous particulate fillers; and (f) water; Includes, Here, the epoxysilane oligomer composition (b) is in an amount greater than 0.5% by weight and up to 5% by weight, based on the weight of the (meth)acrylic polymer (a) which contains at least one functional group having active hydrogen. Aqueous coating composition.

2. The aqueous coating composition according to claim 1, wherein the functional group containing active hydrogen is a carboxyl group (-C(=O)OH) or a hydroxyl group (-OH).

3. Functional groups containing active hydrogen are in salt form -C(=O)O － M ＋ It is a carboxyl group that is neutralized, and here M ＋ is Na ＋ _K ＋ The aqueous coating composition according to claim 2, wherein the ion is ammonium ion.

4. The aqueous coating composition according to claim 2, wherein the carboxyl group is present in an amount sufficient to have an acid value of 1 to 780, as determined by potentiometric titration.

5. The aqueous coating composition according to any one of claims 1 to 4, wherein the (meth)acrylic polymer (a) having at least one functional group having active hydrogen is selected from the group consisting of pure acrylic, styrene acrylic, vinyl acrylic, and acrylic ethylene vinyl acetate copolymer.

6. The aqueous coating composition according to claim 5, wherein the (meth)acrylic polymer (a) having at least one functional group having active hydrogen is prepared by emulsion polymerization.

7. The aqueous coating composition according to claim 6, wherein pure acrylic is prepared using acrylic acid, methacrylic acid, acrylate ester, and / or methacrylate ester as monomers; styrene acrylic is prepared using styrene and acrylic acid, methacrylic acid, acrylate ester, and / or methacrylate ester as monomers; vinyl acrylic is prepared using vinyl acetate and acrylic acid, methacrylic acid, acrylate ester, and / or methacrylate ester as monomers; and acrylic ethylene vinyl acetate copolymer is prepared using ethylene, vinyl acetate and acrylic acid, methacrylic acid, acrylate ester, and / or methacrylate ester as monomers.

8. The aqueous coating composition according to any one of claims 1 to 7, wherein the (meth)acrylic polymer (a) having at least one functional group having active hydrogen is in an amount of 5 to 60% by weight based on the total weight of the (meth)acrylic polymer (a) having at least one functional group having active hydrogen, the epoxysilane oligomer composition (b), the emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f).

9. R １ R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl, and 1,3-dimethyl-3-hydroxybutyl; ３ R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl, and 1,3-dimethyl-3-hydroxybutyl; ４ is selected from the group consisting of ethylene, propylene, and 2-methylpropylene; and R ５ The aqueous coating composition according to any one of claims 1 to 8, wherein is selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-methyl-3-hydroxypropyl, 3-hydroxybutyl and 1,3-dimethyl-3-hydroxybutyl, (glycidoxypropyl)bis(2-methyl-3-hydroxypropoxy)silyl and [(glycidoxypropyl)dimethoxysilyloxy]-(glycidoxypropyl)methoxysilyl.

10. R １ is methyl or ethyl, R ３ is methyl or ethyl; R ５ The aqueous coating composition according to any one of claims 1 to 8, wherein is methyl, ethyl, (glycidoxypropyl)dimethoxysilyl, or (glycidoxypropyl)diethoxysilyl; and a, b, c, d, e, f, g, h, and i are 0.

11. The epoxysilane oligomer composition (b) is the aqueous coating composition according to any one of claims 1 to 10, having a weight-average molecular weight of 500 to 2500.

12. The aqueous coating composition according to any one of claims 1 to 11, wherein the emulsifier (c) is a surfactant selected from the group consisting of polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate salt, alkyl phosphate salt, alkyl allyl sulfate ester salt, and polyoxyethylene alkyl phosphate ester salt.

13. The aqueous coating composition according to any one of claims 1 to 12, wherein the emulsifier (c) is in an amount of 1.0 to 15 percent by weight based on the weight of the (meth)acrylic polymer (a) having at least one functional group having active hydrogen.

14. The aqueous coating composition according to any one of claims 1 to 13, wherein titanium dioxide particles are present in an amount from 0.5% to 50% by weight based on the total weight of (meth)acrylic polymer (a) having at least one functional group having active hydrogen, epoxysilane oligomer composition (b), emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), and water (f).

15. The aqueous coating composition according to any one of claims 1 to 14, wherein the siliceous particulate filler is selected from the group consisting of hydrated kaolin, mullite, pyrophyllite, kyanite, nepheline, clay, sillimanite, silica, and talc.

16. The aqueous coating composition according to any one of claims 1 to 15, wherein the siliceous particulate filler (e) is in an amount of 0.05 to 25 weight percent based on the sum of the weights of the (meth)acrylic polymer (a) having at least one functional group having active hydrogen, the epoxysilane oligomer composition (b), the emulsifier (c), the titanium dioxide particles (d), the siliceous particulate filler (e), and water (f).

17. A method for coating a substrate, comprising applying an aqueous coating composition according to any one of claims 1 to 16 to the surface of the substrate, and drying the aqueous coating composition to form a coating.

18. The method according to claim 17, wherein the aqueous coating composition is formed by (A) providing a stock aqueous coating composition comprising (A) a (meth)acrylic polymer (a) having at least one functional group having active hydrogen, an emulsifier (c), titanium dioxide particles (d), a siliceous particulate filler (e), water (f), and one or more optional additives, and (B) adding an epoxysilane oligomer composition (b) to the stock aqueous coating composition.

19. The method for coating a substrate according to claim 17 or 18, wherein the aqueous coating composition in step is heat-aged before being applied to the substrate.

20. A method for coating a substrate according to any one of claims 17 to 19, wherein the aqueous coating composition applied to the substrate and dried has a gloss of 60 degrees between 10 and 40 gloss units (GU).

21. (A) To provide a stock aqueous coating composition comprising (a) a (meth)acrylic polymer having at least one functional group having active hydrogen, an emulsifier (c), titanium dioxide particles (d), siliceous particulate filler (e), water (f), and one or more optional additives. (B) Adding epoxysilane oligomer composition (b) to a stock aqueous coating composition to form an aqueous coating composition, and (C) The process includes applying the composition from (B) to a substrate and drying the composition to form a coating, Here, epoxysilane oligomer composition (b) is (i) A monomer having the structure of formula (I) in an amount of 5 to 15 weight percent: (Z c ) a (R 1 O) 3-2a Si-R 2 (I) (ii) Dimers having the structure of formula (II) in amounts of 5 to 20 weight percent: (Z c ) b (R 1 O) 2-2b (R 2 )Si-O-Si(R 2 ) (OR 1 ) 2-2c (Z c ) c (II) (iii) At least one trimer having a linear structure (III) or a cyclic structure (IV) in an amount of 5 to 20 weight percent: 【Transformation 7】 【Transformation 8】 Here, the total amount of trimer (iii) is the sum of the weights of the linear trimer of formula (III) and / or the cyclic trimer of formula (IV), and (iv) At least one polyoligomer having the structure of formula (V) in an amount of 45 to 85 weight percent 【Chemistry 9】 Here, the total amount of polyoligomer (iv) is the sum of the weights of each component having the structure of formula (V), Here Each of the Z c entities is independently a divalent group -OR 4 O-, where R 4 is independently a divalent linear alkylene group of 2 to 6 carbon atoms or a branched alkylene group of 3 to 6 carbon atoms, however (v) The two oxygen atoms are bonded to two different carbon atoms of R 4, and (vi) The condition is that the open valence of each oxygen atom is bonded to the same Si atom to form a cyclic 1,3-dioxa-2-sila-cycloalkyl group. Each of the R1 entities is independently a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, or an -OR4OH group where R4 is as described above. Each existence of R2 is as follows: 【Chemistry 10】 Each of the R3 entities is independently a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, a -OR 4OH group where R4 is as described above, or less. 【Chemistry 11】 Here, each of the R5 entities is independently a monovalent linear alkyl group containing 1 to 6 carbon atoms, a branched alkyl group containing 3 to 6 carbon atoms, a -OR 4OH group as described above for R4, or less. 【Chemistry 12】 The subscripts a, b, c, d, e, f, g, h, i, m, and n are integers, where a, b, c, d, e, f, g, h, and i are 0, m is from 0 to 5, and n is from 2 to 15, and the weight percentage is based on the total weight of the sum of components (i), (ii), (iii), and (iv). (c) Emulsifier; (d) Titanium oxide particles; (e) siliceous particulate fillers; and (f) Water Includes, Here, the epoxysilane oligomer composition (b) is in an amount ranging from more than 0.5% by weight to 5% by weight, based on the weight of the (meth)acrylic polymer (a) which contains at least one functional group having active hydrogen. A method for coating a substrate.

22. The functional group containing active hydrogen is a carboxyl group (-C(=O)OH), a hydroxyl group (-OH), or a carboxyl group (-C(=O)O) neutralized to a salt form. － M ＋ And here M ＋ is Na ＋ _K ＋ The method according to claim 21, wherein the ion is either ammonium ions.

23. The method according to claim 21 or 22, wherein the aqueous coating composition of step (b) is heat-aged before the aqueous coating composition is applied to the substrate.

24. The method according to any one of claims 21 to 23, wherein the aqueous coating composition, after being applied to a substrate and dried, has a gloss of 60 degrees between 10 and 40 gloss units (GU).

25. An article comprising a coating disposed on the surface of the article, wherein the coating is formed from an aqueous coating composition according to any one of claims 1 to 16.

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