Synthetic resin emulsion, aqueous coating composition containing the same, and coating method using the aqueous coating composition

Abstract

To provide synthetic resin emulsion for an aqueous coating composition which can suppress transition of a plasticizer contained in a coated object into a coated film, and can be easily produced.SOLUTION: There is provided a synthetic resin emulsion for an aqueous coating composition, wherein the synthetic resin is a polymer containing 40-90 wt.% of (A) ethyl acrylate, 1-5 wt.% of (B) a carboxyl group-containing vinyl-based acid monomer, and 0.5-5 wt.% of (C) an epoxy group or alkoxysilyl group-containing vinyl-based monomer. The synthetic resin emulsion for the aqueous coating composition using the same enables formation of a coated film capable of preventing occurrences of softening and sticking due to transition of a plasticizer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a synthetic resin emulsion that can inhibit the migration of plasticizers contained in various sealants, vinyl chloride coatings, etc. into coating films, an aqueous coating composition containing the same, and a coating method that can prevent softening and stickiness of coating films caused by plasticizers by applying the aqueous coating composition to the surfaces of various sealants, vinyl chloride coatings, etc. [Background technology]

[0002] Paints are sometimes applied or reapplied to the surfaces of plasticizer-containing sealants, vinyl chloride products, vinyl chloride-coated steel sheets, vinyl chloride wallpaper, and other products to create coatings for aesthetic purposes, protection, or to provide various functionalities. In this case, the plasticizers in the coated object (plasticizer-containing product) or primer coating (plasticizer-containing coating) can migrate to the coating and plasticize the resin in the coating. This can cause the coating to soften and stick, leading to peeling and contamination.

[0003] A plasticizer is an additive that is added to resins that are brittle and difficult to deform or process in their original state to improve their fluidity when softened, and their flexibility and pliability when hardened, making them easier to mold. For example, plasticizers used for polyvinyl chloride include dibutyl phthalate (DBP), dioctyl phthalate (DOP), and tricresyl phosphate (TCP).

[0004] For this reason, a method has been proposed in which a specific aqueous primer consisting of a two-component composition of an epoxy resin / amine curing agent is applied to the surface of a material containing a plasticizer to form a primer coating film suitable for preventing the leaching of the plasticizer (Patent Document 1).

[0005] Another proposed aqueous surface treatment agent composition includes, as Component A, an aqueous emulsion of a (meth)acrylic copolymer resin obtained by copolymerizing specific amounts of (a) methyl methacrylate, (b) a silicone macromonomer having a (meth)acryloyl group at one end, (c) an ethylenically unsaturated monomer having a hydroxyl group, (d) an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group, and (e) an ethylenically unsaturated monomer other than methyl methacrylate, and a specific amount of a hydrazine derivative having at least two hydrazino groups per molecule as Component B (Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-247070 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-56978 Summary of the Invention [Problem to be solved by the invention]

[0007] However, since the paint of Patent Document 1 is a two-component type, strict control of the mixing ratio, pot life, etc. is required, which poses a problem of inefficient work.

[0008] The technology of Patent Document 2 relates to a one-component cross-linking aqueous coating composition that prevents plasticizers added to resin sheets from bleeding into the coating film, causing stickiness and dirt adhesion. However, this technology does not form crosslinks during the production of the coating composition, but rather forms crosslinks during the process of forming a film after the coating composition is applied. Therefore, the cross-linking reaction does not proceed in a short time, resulting in poor cross-linking efficiency. Therefore, there is a problem in that excessive amounts of cross-linking monomer and cross-linking agent are required to compensate for this.

[0009] Therefore, the present invention aims to solve the above-mentioned problems by providing an easily producible synthetic resin emulsion that can suppress the migration of plasticizers contained in the object to be coated into the coating film, an aqueous coating composition containing the same, and a coating method that can form a coating film that can prevent softening and stickiness using the aqueous coating composition. [Means for solving the problem]

[0010] As a means for achieving this, the present invention provides a synthetic resin emulsion for an aqueous coating composition, characterized in that the synthetic resin is a polymer containing (A) 40 to 90% by weight of ethyl acrylate, (B) 1 to 5% by weight of a carboxyl group-containing vinyl acid monomer, and (C) 0.5 to 5% by weight of an epoxy group- or alkoxysilyl group-containing vinyl monomer.

[0011] The present invention also provides an aqueous paint composition containing the above-mentioned synthetic resin emulsion, and a coating method for applying the aqueous paint composition to the surface of a product or coating made of a material containing a plasticizer.

[0012] In the present invention, the expression "XX to XX" indicating a numerical range means "not less than XX and not more than XX" unless otherwise specified. [Effects of the Invention]

[0013] The synthetic resin emulsion of the present invention contains ethyl acrylate (EA) as a main component. Conventional acrylic resin-based architectural paint resins typically use (meth)acrylic acid esters, which have good water resistance, as monomers. (Meth)acrylic acid refers to acrylic acid or methacrylic acid. Representative examples include methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate. Therefore, ethyl acrylate, which is more hydrophilic than these and therefore less water-resistant, has rarely been used as a monomer for architectural paint resins.

[0014] However, resins primarily composed of hydrophilic monomers such as ethyl acrylate are less susceptible to the effects of plasticizers, typically phthalate esters, than resins primarily composed of (meth)acrylic acid esters, which are commonly used in architectural coatings. The present invention utilizes this property to develop a novel synthetic resin emulsion for coatings, primarily composed of ethyl acrylate. This emulsion prevents plasticizers from migrating into coating films from plasticizer-containing products and coatings, such as various sealants, vinyl chloride products, vinyl chloride-coated steel sheets, and vinyl chloride wallpaper, thereby preventing the coating films from softening and becoming sticky.

[0015] On the other hand, in the present invention, in order to compensate for the reduced water resistance of the coating film caused by ethyl acrylate, a crosslinkable functional group-containing vinyl monomer that crosslinks ethyl acrylate is blended. This allows the crosslinkable functional group-containing vinyl monomer to be copolymerized during emulsion polymerization of a resin whose main component is ethyl acrylate, making it easy to crosslink the resin in advance within the emulsion particles. This makes it possible to prevent the plasticizer from migrating into the coating film while maintaining good water resistance, even when ethyl acrylate is the main component. DETAILED DESCRIPTION OF THE INVENTION

[0016] (Synthetic resin emulsion) The synthetic resin emulsion used in the aqueous coating composition of the present invention is a vinyl copolymer containing at least (A) ethyl acrylate and (B) and (C) vinyl monomers having crosslinkable functional groups in a synthetic resin (hereinafter sometimes simply referred to as resin), and is obtained by emulsion polymerization using water as the dispersion medium, and can be produced by known production methods.

[0017] The content of (A) ethyl acrylate as a monomer in the resin is 40 to 90% by weight, preferably 55 to 75% by weight. If the content of (A) ethyl acrylate is less than 40% by weight, the plasticizer resistance becomes insufficient, and the coating film becomes prone to softening and stickiness. On the other hand, if the content of (A) ethyl acrylate exceeds 90% by weight, the water resistance of the coating film decreases significantly, making it impractical.

[0018] The crosslinked structure of the resin according to the present invention can be formed during emulsion polymerization of the synthetic resin emulsion. The vinyl monomers having crosslinkable functional groups for this purpose include (B) a carboxyl group-containing vinyl acid monomer and (C) an epoxy group- or alkoxysilyl group-containing vinyl monomer. Specific examples of methods for ensuring intramolecular and / or intermolecular crosslinking of the resin during emulsion polymerization of the synthetic resin emulsion include crosslinking between (B) a carboxyl group-containing vinyl acid monomer and (C) an epoxy group-containing vinyl monomer, or crosslinking by condensation of (C) an alkoxysilyl group-containing vinyl monomer, and these methods can also be used in combination.

[0019] When a resin crosslink is formed using (B) a carboxyl group-containing vinyl acid monomer and (C) an epoxy group-containing vinyl monomer, a known production method can be used in which vinyl monomer components containing both are copolymerized by emulsion polymerization while simultaneously allowing an acid-epoxy crosslinking reaction to proceed.

[0020] Examples of (B) carboxyl group-containing vinyl acid monomers include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, as well as their anhydrides; and monoesters of unsaturated dicarboxylic acids such as methyl maleate and methyl itaconate. Among these, methacrylic acid and acrylic acid are preferred for their general utility. These (B) components may be used alone or in combination of two or more.

[0021] The content of (B) carboxyl group-containing vinyl acid monomer in the resin is 1 to 5 wt%, preferably 2 to 4 wt%. If the content of (B) component is less than 1 wt%, crosslinking with (C) epoxy group-containing vinyl monomer is reduced, resulting in insufficient water resistance of the coating film. On the other hand, if the content exceeds 5 wt%, the coating film will also have insufficient water resistance.

[0022] The (C) epoxy group-containing vinyl monomer is a C3-30 epoxide having one or more polymerizable unsaturated groups. Examples of the (C) epoxy group-containing vinyl monomer include glycidyl group-containing (meth)acrylates having 6 to 20 carbon atoms, such as glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate; alicyclic epoxy group-containing vinyl monomers having 6 to 20 carbon atoms, such as 4-vinyl-1,2-epoxycyclohexane and 5-vinyl-2,3-epoxynorbornane; and glycidyl group-containing acrylamides having 6 to 20 carbon atoms, such as N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylmethyl)acrylamide. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of polymerizability with the (B) carboxyl group-containing vinyl acid monomer. These (C) epoxy group-containing vinyl monomers may be used alone or in combination of two or more.

[0023] When forming a resin crosslink using (C) an alkoxysilyl group-containing vinyl monomer, a known production method can be used, in which (C) an alkoxysilyl group-containing vinyl monomer is copolymerized into a resin skeleton by emulsion polymerization, and then a dehydration condensation reaction of silanol groups generated by hydrolysis of the alkoxysilyl groups is allowed to proceed.

[0024] The silyl group of the (C) alkoxysilyl group-containing vinyl monomer is preferably a trialkoxysilyl group or a dialkoxysilyl group, since this increases the crosslink density. Examples of such (C) alkoxysilyl group-containing vinyl monomer include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. These (C) alkoxysilyl group-containing vinyl monomers may be used alone or in combination of two or more.

[0025] The content of component (C) in the resin is 0.5 to 5% by weight, preferably 1 to 3% by weight. If the content of component (C) is less than 0.5% by weight, the water resistance of the coating film will be insufficient. On the other hand, if the content of component (C) is more than 5% by weight, the polymerization stability of the synthetic resin emulsion will decrease, making it difficult to prepare an aqueous coating composition.

[0026] The crosslinked structure of the resin according to the present invention is formed during emulsion polymerization of the synthetic resin emulsion, but can also be formed supplementarily by adding a curing agent or crosslinking agent during preparation of the aqueous coating composition or before use. Examples of such crosslinking systems include carbonyl and hydrazide groups, hydroxyl and isocyanate groups, epoxy and amino groups, epoxy and carboxyl groups, alkoxysilyl groups, carboxyl and carbodiimide groups, carboxyl and polyvalent metal ions, and carboxyl and aziridine groups, and combinations of these can also be used.

[0027] Furthermore, the resin of the synthetic resin emulsion of the present invention may contain other vinyl copolymerizable monomers other than the above components (A) to (C), which have been conventionally used in synthetic resin emulsions for aqueous coating compositions of this type. Representative examples include (meth)acrylic acid esters. Examples of acrylic acid esters include methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylonitrile, acrylamide, and hydroxyethyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methacrylonitrile, methacrylamide, and hydroxyethyl methacrylate. Of these, methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferred. These other vinyl copolymerizable monomers may be used alone or in combination of two or more.

[0028] (Water-based paint composition) The synthetic resin emulsion is used to prepare an aqueous coating composition. The content of the synthetic resin emulsion in the aqueous coating composition is preferably 10% by weight or more, more preferably 15% by weight or more, calculated as solids. If the content of the synthetic resin emulsion is less than 10% by weight, it becomes difficult to obtain a coating film in which plasticizer resistance effectively functions. Since the aqueous coating composition can also be made using the synthetic resin emulsion alone, the upper limit of the content of the synthetic resin emulsion in the aqueous coating composition is not particularly limited (it may be 100% by weight of emulsion). In general, to maintain a stable state, the solid content of the synthetic resin emulsion is often adjusted to an upper limit of 60% by weight. Therefore, the content of the synthetic resin emulsion in the aqueous coating composition calculated as solids is preferably 60% by weight or less, and more preferably 55% by weight or less, considering the flexibility of blending other additives. In addition, one type of synthetic resin emulsion may be used alone in the aqueous coating composition, or two or more types may be used in combination.

[0029] For the purpose of improving weather resistance, adhesion to the substrate, etc., a wide range of conventionally known synthetic resin emulsions can be mixed into the aqueous coating composition of the present invention without particular restriction, as long as the effects of the present invention are not impaired. Specific examples include acrylic resin emulsions, acrylic / styrene copolymer resin emulsions, acrylic silicone resin emulsions, fluororesin composite acrylic resin emulsions, urethane resin emulsions, and vinyl acetate / ethylene copolymer resin emulsions. These emulsions may be self-crosslinking types or known reactive curing types that are cured by a curing agent.

[0030] In order to thicken the coating film and impart hiding power and coloring properties, a pigment can be blended into the aqueous coating composition within a range that does not reduce the dispersion stability of the coating. In this case, the pigment content is preferably 600 parts by weight or less, more preferably 450 parts by weight or less, and even more preferably 300 parts by weight or less, per 100 parts by weight of the solid content of the synthetic resin emulsion. If the pigment content exceeds 600 parts by weight per 100 parts by weight of the solid content of the synthetic resin emulsion, the dispersion stability of the coating will decrease, making production difficult and the plasticizer resistance will be insufficient.

[0031] Pigments can be classified into extender pigments and color pigments. Examples of extender pigments include calcium carbonate, precipitated barium sulfate, talc, clay, diatomaceous earth, and mica. Examples of color pigments include titanium oxide, red iron oxide, yellow iron oxide, carbon black, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, indigo pigments, dioxazine pigments, perylene pigments, isoindolinone pigments, and diketopyrrolopyrrole pigments.

[0032] In addition to the above components, various additives can also be blended into the aqueous coating composition to the extent that they do not impair the effects of the present invention, for the purpose of imparting and improving functions such as storage stability, coating workability, finish, weather resistance, etc. Specific examples include dispersants, thickeners, film-forming aids, antifoaming agents, preservatives, mildew inhibitors, anti-algae agents, antifreeze agents, ultraviolet absorbers, light stabilizers, etc.

[0033] (Painting method) The aqueous coating composition is applied to the surface of a substrate containing a plasticizer, i.e., a product or coating made of a material containing a plasticizer, to form a coating film. The coating film formed thereby can prevent the softening and stickiness of the coating film, and also prevents peeling and contamination caused by these. Therefore, the coating film formed with the aqueous coating composition of the present invention can be used as the outermost coating film, or a different topcoat paint can be further applied to the surface of the coating film for coloring or protection purposes. In particular, the coating film formed with the aqueous coating composition of the present invention is characterized by its plasticizer resistance, and therefore is particularly effective when a topcoat paint is applied.

[0034] The method for applying the aqueous coating composition is not particularly limited, and may be any conventionally known method such as spray coating, roller coating, bar coating, trowel coating, or spatula coating.

[0035] Specific examples of objects to be painted include various sealants containing plasticizers, vinyl chloride products, vinyl chloride-coated steel sheets, vinyl chloride wallpaper, etc., as well as buildings primed with paint containing plasticizers, etc. Examples of areas to be painted on buildings include exterior walls, foundations, eaves, interior walls, ceilings, floors, etc. [Example]

[0036] EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to the following examples.

[0037] <Preparation of synthetic resin emulsion> The types and amounts (wt%) of the monomer components of the synthetic resin emulsions used in the examples, as well as their polymerization stability, are shown in Table 1, and the types and amounts (wt%) of the monomer components of the synthetic resin emulsions used in the comparative examples, as well as their polymerization stability, are shown in Table 2. Each of these synthetic resin emulsions was prepared by a known production method in which various monomers were copolymerized by emulsion polymerization using water as the dispersion medium, while simultaneously allowing an acid-epoxy crosslinking reaction to proceed. In all cases, the solid content was adjusted to 45 wt%. The specific procedures for these are described below.

[0038] (Example 1-1) Monomer components (total 100 parts) consisting of 40.0 parts of ethyl acrylate (EA), 33.0 parts of methyl methacrylate (MMA), 25.5 parts of n-butyl acrylate (n-BA), 1.0 parts of methacrylic acid (MAA), and 0.5 parts of glycidyl methacrylate (GMA) were emulsified by mixing 2 parts of sodium polyoxyethylene alkyl ether sulfate (solids content 25%) as an anionic emulsifier, 8.3 parts of polyoxyethylene polycyclic phenyl ether sulfate salt (solids content 30%), and 28 parts of ion-exchanged water to prepare an emulsion of the monomer mixture. Next, a thermometer, a stirrer, a dropping device, and a reflux condenser were added to a reactor equipped with 59 parts of ion-exchanged water and 0.3 parts of sodium polyoxyethylene alkyl ether sulfate (solids content 25%). The internal temperature was raised to 85 ° C. While maintaining this temperature, 1 part of a 20% aqueous solution of ammonium persulfate was added, and the previously prepared emulsion of the monomer mixture was immediately added dropwise over a period of 3 hours to effect emulsion polymerization. In parallel with this, 5 parts of a 5% aqueous solution of ammonium persulfate was added dropwise. After the addition was complete, the mixture was aged at 85°C for 2 hours, cooled to room temperature, and neutralized by adding aqueous ammonia. Ion-exchange water was then added to adjust the concentration, yielding an emulsion of an acrylic ester copolymer with a solids content of approximately 45% by weight and a pH of approximately 8.

[0039] (Examples 1-2 to 1-9 and Comparative Examples 1-10 to 1-15) Acrylic acid ester copolymer emulsions were obtained in the same manner as in Example 1-1, except that the monomer components in Example 1-1 were changed to Examples 1-2 to 1-9 shown in Table 1 and Comparative Examples 1-10 to 1-15 shown in Table 2.

[0040] The monomer components in Tables 1 and 2 are as follows: EA: Ethyl acrylate MAA: methacrylic acid AA: acrylic acid GMA: Glycidyl methacrylate MPTMS: 3-methacryloxypropyltrimethoxysilane MMA: Methyl methacrylate n-BA: n-butyl acrylate 2-EHA: 2-ethylhexyl acrylate

[0041] <Polymerization stability> The stability of the synthetic resin emulsion during preparation was evaluated according to the following criteria. ⊚: The viscosity did not increase significantly, and no aggregation of emulsion particles occurred, making it suitable for use. ◯: Although the viscosity is somewhat high, no agglomerates of emulsion particles are formed and the emulsion is usable. x: The emulsion particles aggregated or the viscosity increased significantly, making it unusable.

[0042] [Table 1]

[0043] [Table 2]

[0044] The results in Table 1 show that stable synthetic resin emulsions could be prepared in Examples 1-1 to 1-9, in which components (A) to (C) were mixed in appropriate amounts. On the other hand, the results in Table 2 show that Comparative Example 1-14, in which the content of component (C) was 7% by weight and the content of component (A) exceeded 90% by weight, could not be used to prepare an aqueous coating composition because of the significant generation of emulsion particle aggregates. Comparative Example 1-15 also showed significant thickening, and was therefore excluded from the preparation of an aqueous coating composition.

[0045] <Preparation of aqueous coating composition> Using the synthetic resin emulsions for each of the Examples and Comparative Examples obtained in the above tests (Comparative Examples 1-14 and 1-15 could not be used), the materials shown in Table 3 were added sequentially to a container in the amounts (% by weight) shown in Table 3 while being mixed with a stirrer to prepare the aqueous coating compositions of the Examples and Comparative Examples. In Table 3, the parts by weight of pigment per 100 parts by weight of resin is the total parts by weight of pigment per 100 parts by weight of resin.

[0046] The materials used in Table 3 are as follows: Pigment dispersant: Poise 530 (Kao Corporation) Coalescence agent: Texanol (manufactured by Eastman Chemical Japan Co., Ltd.) Antifoaming agent: BYK021 (manufactured by BYK-Chemie GmbH) White pigment: titanium oxide JR-600A (manufactured by Teika Co., Ltd.) Extender pigment: calcium carbonate NS#400 (manufactured by Nitto Funka Kogyo Co., Ltd.) Thickener: Adekanol UH-472 (manufactured by ADEKA Corporation)

[0047] The physical properties of each coating film obtained are also shown in Table 3. These were evaluated as follows. <Test specimen preparation method> (plasticizer resistance) SR Seal S70 (manufactured by Sunrise Co., Ltd.), a sealant containing a plasticizer, was applied evenly to a thickness of approximately 5 mm using a spatula on a 4 mm thick flexible plate specified in JIS A 5430, and dried at 23°C for 3 days. Next, the coating compositions of each Example and Comparative Example were applied thereon using a brush at a rate of 0.3 kg / m. 2 The paint was applied to one side of the board and dried at 23°C for 16 hours. Then, a glossy synthetic resin emulsion paint, Laughton EM Enamel (manufactured by Suzuka Fine Co., Ltd.), was sprayed twice (0.15 kg / m) on only the other side as a top coat. 2 The test specimens were then dried at 23°C for 7 days (1 coat / coating, 4 hours between coats).

[0048] (water resistance) The coating compositions of each example and comparative example were applied by brush at a rate of 0.3 kg / m to a 4 mm thick flexible plate as specified in JIS A 5430. 2 The paint was applied to the surface and dried at 23°C for 16 hours. Then, two coats of Rafter EM enamel (0.15 kg / m) were applied by spray coating. 2The test specimen was then coated twice with Rafter EM enamel (4-hour interval between coats) and dried for 24 hours. Finally, the back and periphery were brushed with two coats of Rafter EM enamel, and dried at 23°C for 14 days.

[0049] <Evaluation method> (plasticizer resistance) The test specimens were left standing at 50°C for 7 days, and then at 23°C for 24 hours. The plasticizer resistance was evaluated on the uncoated and coated sides based on the degree of adhesion of the coating film when touched with a finger, using the following criteria: ◎: There is almost no stickiness even when the fingertip is pressed against the coating surface. ○: When a fingertip is pressed against the coating surface, it sticks weakly, but the fingertip can be instantly pulled away. △: When a fingertip is pressed against the coating surface, it sticks and the fingertip cannot be easily removed. ×: When a fingertip is pressed against the coating surface, it adheres strongly and force is required to pull the fingertip away.

[0050] (water resistance) The test specimen was immersed in deionized water at 23°C for 96 hours, and the water resistance was visually evaluated according to the following criteria. ○: No blistering occurs in the coating film. ×: Blisters appear on the coating film.

[0051] [Table 3]

[0052] The results in Table 3 show that Examples 2-1 to 2-11, which satisfied the conditions specified by the present invention, all achieved good results in plasticizer resistance, water resistance, and tensile strength. On the other hand, Comparative Example 2-1, which used a non-crosslinked synthetic resin emulsion that did not contain component (C), exhibited strong adhesion to the topcoat film, resulting in insufficient plasticizer resistance, and also insufficient water resistance. Comparative Examples 2-2 and 2-3, which used synthetic resin emulsions with too low a content of component (A), had acceptable water resistance but insufficient plasticizer resistance. Comparative Example 2-4, which used a synthetic resin emulsion containing a large amount of component (B), exhibited good plasticizer resistance, but on the other hand, insufficient water resistance.

Claims

[Claim 1] (A) 40 to 90% by weight of ethyl acrylate; (B) 1 to 5% by weight of a carboxyl group-containing vinyl acid monomer; (C) 0.5 to 5% by weight of a vinyl monomer containing an epoxy group or an alkoxysilyl group; An aqueous coating composition containing an emulsion of a synthetic resin made of a polymer containing A coating method in which a coating is applied to the surface of a product or film made of a material containing a plasticizer.

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