Water-based paint composition

Abstract

To provide an aqueous paint composition that hardly oozes even when diluted with water and applied to a hydrophilic and coarse substrate such as a cotton cloth, a hemp cloth, and drawing paper.SOLUTION: An aqueous paint composition contains at least acryl resin emulsion, hydrophobic dry silica, and calcium sulfate and thus produces a loose aggregate even when diluted with water for a low-viscosity state. The composition prevents oozing and offset by suppressing movement of a pigment on a cloth and allowing only water to penetrate through the cloth.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to water-based paint compositions suitable for application to fabric. [Background technology]

[0002] It is known to use synthetic resin emulsions to impart water resistance to water-based paints. Water-based paint compositions using such resin emulsions can be diluted with water to adjust their concentration and application performance, can impart water resistance and washability to the dried coated surface, and can be used on materials other than paper, such as cloth, plastic, glass, and wood.

[0003] Patent Document 1 describes a water-based paint composition that uses a pigment, an acrylic resin emulsion, and calcium carbonate or silicon dioxide as an extender pigment, and has predetermined flow characteristics and produces a coating that is water-resistant.

[0004] Patent Document 2 describes a water-based paint composition that uses wet silica as an extender pigment and a vinyl acetate-acrylic resin emulsion.

[0005] Furthermore, Patent Document 3 describes a base paint that contains synthetic gypsum dihydrate (calcium sulfate) and chalk (calcium carbonate) as extender pigments, and that, when applied to a linen canvas or the like, exhibits absorbency for paints applied on top. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-059878 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-024391 [Patent Document 3] Japanese Patent Application Publication No. 59-105062 Summary of the Invention [Problem to be solved by the invention]

[0007] The embodiments of Patent Documents 1 and 2 are formulations of typical acrylic paints, and calcium carbonate and wet silica, which are excellent in cost and hiding power, are commonly used as extender pigments. However, when such aqueous paint compositions are diluted with water to achieve a desired concentration, particularly a pale color or tone, problems arise such as bleeding on coarse, hydrophilic surfaces such as cotton, linen, or drawing paper, or the pigment bleeds through to the back, resulting in poor color development, making it difficult to draw as desired, and the coating film lacks water resistance.

[0008] The embodiment of Patent Document 3 is a paint that can be used on cloth canvas using gypsum dihydrate, but since it is intended for use as a primer and its composition is such that it exerts its absorbent effect when applied thickly without dilution, it absorbs a lot of water when not repainted on top, making it poor in water resistance, and when diluted and applied to cloth, the pigment bleeds through.

[0009] To provide a water-based paint composition which is hard to bleed, has good color development without causing pigment strike-through, and does not reduce the water resistance of a coating film even when the paint is diluted with water to a desired concentration and applied to a coarse hydrophilic coating surface such as cotton cloth, linen cloth or drawing paper. [Means for solving the problem]

[0010] The present invention relates to a water-based paint composition suitable for application to fabric, which contains at least an acrylic resin emulsion, hydrophobic dry silica, and calcium sulfate. [Effects of the Invention]

[0011] The aqueous paint composition of the present invention, when combined with an acrylic resin emulsion, hydrophobic dry silica, and calcium sulfate, results in an aqueous paint composition that is resistant to bleeding during application. While bleeding resistance is generally controlled by the viscosity of the paint, the aqueous paint composition of the present invention has been found to be sufficiently resistant to bleeding, even when applied to a coarse, hydrophilic surface, even when diluted with water to a desired concentration and at a low viscosity, with no breakthrough of the pigment, good color development, and no reduction in the water resistance of the coating film. By diluting the aqueous paint composition appropriately with water and applying it, when the acrylic resin emulsion loosely aggregates with calcium sulfate, the network-structured hydrophobic dry silica forms an aggregate complex with the acrylic resin structural portion of the acrylic resin emulsion, separating the pigment, its fixing agent, and the acrylic resin emulsion from the water, allowing painting without bleeding or breakthrough even at high dilutions and low viscosities. DETAILED DESCRIPTION OF THE INVENTION

[0012] Water is used as the primary solvent in water-based paint compositions.

[0013] The acrylic resin emulsion of the present invention can be an acrylic copolymer resin, an acrylonitrile-acrylic copolymer resin, a styrene-acrylic copolymer resin, a vinyl acetate-acrylic copolymer resin, a vinyl chloride-acrylic copolymer resin, or a silicone-acrylic copolymer resin. The acrylic resin emulsion forms loose aggregates with calcium sulfate while maintaining stability over time, thereby improving its anti-bleeding performance. The acrylic resin emulsion that can be used in the present invention is obtained by emulsion polymerization of an acrylic monomer and, if necessary, other monomers. Examples of acrylic monomers that can be used include alkyl acrylate monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, and stearyl acrylate, and alkyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. These acrylic monomers can be used alone or in combination of two or more.Furthermore, examples of other monomers that can be used alone or in combination with the acrylic monomer as needed include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, and citraconic acid; ethylenic carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and ethylvinylbenzene; saturated fatty acid vinyl monomers such as vinyl acetate, vinyl propionate, and vinyl versatate; olefinic monomers such as vinyl chloride, ethylene, propylene, and butadiene; hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxymethyl methacrylate; ethylenic carboxylic acid amides such as acrylamide, methacrylamide, and diacetone acrylamide; and 2-(dimethylamino)ethyl methacrylate and 2-(diethylamino)ethyl methacrylate.

[0014] If the glass transition temperature (Tg) is higher than room temperature, the coating film will become cloudy and crack when dried at room temperature, resulting in reduced water resistance. Therefore, a Tg of 30°C or lower is preferred. Acrylic resin emulsions with a Tg of -15°C or lower produce soft coatings after drying and are less stiff on fabric, making them ideal for paints intended for application to fabric. Two or more acrylic resin emulsions with different Tgs can also be used in combination. In this case, it is preferable for 40% or more of the resin solids to have a Tg of -15°C or lower, as this maintains the coating film's softness. The resin solids content of the acrylic resin emulsion is preferably 5 to 45% by weight, with 10 to 35% being particularly preferred, based on the total weight of the aqueous paint composition. This is because there is a sufficient amount of resin to form a coagulated complex sufficient to prevent the pigment from bleeding into the surrounding area even when diluted. Furthermore, after drying, the coating exhibits sufficient adhesion to the surface of any material, and the coating film has sufficient water resistance to withstand washing. For paints intended for application to fabric, emulsions designed for pigment printing or formaldehyde-free formulations are desirable. Also, those with a pH between 6.0 and 10.0 are preferred as fixing acrylic resin emulsions, as they have excellent fixing power and stability over time.

[0015] Acrylic resin emulsions with a Tg of -15°C or less are not particularly limited, but commercially available examples include Rikabond FK-284 (Tg -40°C, resin solids 30%), FK-471 (Tg -20°C, resin solids 55%), FK-489 (Tg -19°C, resin solids 33%), FK-3830 (Tg -29°C, resin solids 48%), FK-3840 (Tg -40°C, resin solids 48%), FK-6100 (Tg -33°C, resin solids 44%), Mowinyl 952B (Tg -38°C, resin solids 46%), and Mowinyl 966A (Tg -32°C, resin solids 45%) (all manufactured by Japan Coating Resins). Co., Ltd.), AICA AIBO M-581 (Tg -25°C, 59%), M-583 (Tg -26°C, 55%), M-584 (Tg -30°C, 55%) (all from AICA Kogyo Co., Ltd.), Boncoat AB-782-ES (Tg -30°C, 45%), Boncoat AB-886 (Tg -40°C, 50%) (all from DIC Corporation), Vinyblanc 2600 (Tg -27°C, 48%), Vinyblanc 4003 (Tg -15°C, 50%) (all from Nissin Chemical Industry Co., Ltd.), and Sumikaflex 900HL (Tg -20°C, 60%) (all from Sumika Chemtex Co., Ltd.). Among these, Rikabond FK-284, FK-471, FK-489, AICA AIBOND M-581, M-583, M-584, and Boncoat AB-782-ES and AB-886 are emulsions suitable for pigment printing and, because they do not contain formaldehyde, are particularly recommended as paint fixatives intended for application to fabric and with safety in mind.

[0016] Representative acrylic resin emulsions with a Tg of above -15°C and below 30°C include Primal AC-261T (Tg 24°C, resin solids 49.5%), DirtShield 08 (Tg 12°C, resin solids 45.5%) (both Dow Chemical Japan Co., Ltd.), Vinizol 911 (Tg -12°C, resin solids 50%), Vinizol 1637 (Tg -13°C, resin solids 50%), Vinizol 900 (Tg 30°C, resin solids 50%), and Vinizol 1117 (Tg 24°C, resin solids 40%) (all Daido Chemical Industry Co., Ltd.), Pegal LS8146 (Tg -8°C, resin solids 45%), and Vinizol LS8970 (Tg -10°C, resin solids 50.7%) (all High Pressure Gas Industry Co., Ltd.). These emulsions can be used in combination with acrylic resin emulsions with a Tg of -15°C or less to adjust the strength, heat resistance, wet friction, stickiness (tackiness), and flexibility of the coating film.

[0017] The calcium sulfate used in this invention can form loose agglomerates with the hydrophobic portion of the acrylic resin during application without affecting the initial or aging dispersion of emulsion particles or pigments in the acrylic resin emulsion. This loose agglomeration is maintained even when diluted with water, preventing bleeding even when applied to rough surfaces such as fabric. Examples of calcium sulfate that can be used here include Type III anhydrate, 1 / 2 hydrate, and dihydrate. Specific examples include, but are not limited to, commercially available products such as calcium sulfate A (calcium sulfate dihydrate), accelerator (calcium sulfate dihydrate), cherry blossom gypsum special grade (calcium sulfate 1 / 2 hydrate) (all Yoshino Gypsum Co., Ltd.), drying gypsum (calcium sulfate Type III anhydrate) (San-Esu Gypsum Co., Ltd.), and commercially available reagents. The amount of calcium sulfate added, including hydrates, must be calculated excluding the weight of the hydrate. The amount of addition is preferably 0.05 to 2.0% by weight, particularly preferably 0.1 to 1.0% by weight, of calcium sulfate excluding hydrates contained in the total amount of the aqueous paint composition.

[0018] Extender pigments are generally used to adjust the viscosity and transparency of paints. The hydrophobic dry silica used as the bleed-preventing extender pigment in this invention is silica produced by a dry process, to which hydrophobicity has been imparted by surface treatment. Dry silica produced by conventional methods can be used, such as dry silica obtained by flame hydrolysis of silicon tetrachloride. The surface of dry silica can also be hydrophobized by conventional methods. Hydrophobized silica tends to have a hydrophobic surface, higher purity, and finer particles than wet silica. This hydrophobic dry silica forms a network-structured aggregate. Because the network-structured surface of hydrophobic dry silica is hydrophobic, it easily forms an aggregated complex with the hydrophobic portion of the acrylic copolymer emulsion, calcium sulfate, and pigment, improving the stability of the pigment in the aqueous paint composition over time. This effect is particularly pronounced for bright pigments with large particle sizes. When diluted with water during application, the network structure prevents the pigments once incorporated into the aggregated complex from redispersing in the water, and by incorporating different types of pigments for each color into the aggregate of the acrylic copolymer emulsion using hydrophobic dry silica, it is possible to create images on fabric that do not bleed, separate colors, or show-through, regardless of the type of pigment.To prevent the viscosity from becoming too high during normal application and to form an aggregated complex sufficient to prevent bleeding even when diluted, the content of hydrophobic dry silica is preferably 0.01% by weight or more and 5% by weight or less, and especially 0.1% by weight or more and 3% by weight or less, based on the total weight of the aqueous paint composition.

[0019] The hydrophilic calcium carbonate and wet-process silica extender pigments described in Prior Art 1 and Prior Art 2 have hydrophilic surfaces, making them insufficiently water-resistant for use in fabric paints intended for laundering. In particular, wet-process silica, commonly used in paints, has poor dispersibility in acrylic resin emulsions. Its large primary particle size (hundreds to thousands of nanometers) prevents it from penetrating the gaps in the emulsion that form loose aggregates with calcium sulfate. In both wet- and dry-processed methods, hydrophilic silica does not undergo hydrophobic interactions with acrylic resin, preventing it from forming pigment-engulfing aggregate complexes. Instead, the acrylic resin and calcium sulfate aggregates surround the hydrophilic silica aggregates, forming very large, hard aggregates that impair pigment dispersion and impair color development and appearance. Furthermore, when the silica precipitates on the coating surface during drying after application, its porous nature, high refractive index, and large particle size cause the surface to appear whitish, impairing the color development and texture of the dried coating in low-brightness or glossy colors. Additionally, calcium carbonate and wet silica tend to retain water within their pores, slowing drying and promoting bleeding on fabric. Calcium carbonate is typically added to adjust the hiding power and viscosity of paints, but because its oil absorption is much lower than wet or dry silica, large amounts must be added to achieve the desired hiding power and viscosity, reducing the flexibility of the paint film and making it unsuitable for use on fabric. Hydrophobic dry silica interacts with the hydrophobic portion of acrylic resin emulsions, providing good dispersibility and preventing precipitation on the surface of the paint film, improving the adhesion of the pigment and acrylic resin to the surface. There are no pores on the particle surface, and the oil absorption performance comes from the structure of the particles, so moisture is released quickly and water is less likely to remain in the paint film.The aggregated complex structure that entangles the pigment within the paint film improves the strength of the paint film after drying, giving the coated surface excellent water resistance and washability.Because of its high oil absorption, only a small amount needs to be added to adjust the viscosity.Because the particles are transparent and fine, it is possible to form a paint film that retains the color, texture, and brightness of the coloring pigment even in low-brightness, glossy, or bright colors.

[0020] Furthermore, when the aggregated complex of acrylic resin emulsion, pigment, and hydrophobic silica begins to form a film on the spot and separate from the water, the silica network structure in the aggregated complex acts as a sieve, allowing only the water to penetrate through the aggregated complex and preventing the pigment from bleeding into the surrounding area.Other extender pigments tend to separate from the acrylic resin emulsion, retaining water and moving onto or into the fabric along with the water, causing the pigment to bleed out or penetrate into the fabric surface along with the water, resulting in bleed-through.

[0021] The hydrophobic dry silica is not particularly limited, but one having an average primary particle diameter of 5 nm to 50 nm can be used, with 7 nm to 20 nm being particularly preferred. Furthermore, the pH value of a 4% dispersion of hydrophobic dry silica in a 1:1 water:methanol solution of 3.0 to 8.0 is preferred. Specific examples include Aerosil R972 (average primary particle diameter 16 nm, pH 4.0 to 5.5), Aerosil R972V (16 nm, pH 4.0 to 5.5), Aerosil R972CF (16 nm, pH 4.0 to 5.5), Aerosil R974 (12 nm, pH 3.8 to 5.0), Aerosil R976 (7 nm, pH 3.8 to 5.0), Aerosil R976S (7 nm, pH 4.0 to 5.5), and Aerosil R9200 (16 nm). m, pH 3.0 to 5.0), RY200 (12 nm, pH 4.0 to 7.0), R202 (14 nm, pH 4.0 to 6.0), R805 (12 nm, pH 3.5 to 5.5) (bottom), R812 (7nm, pH 5.5 to 8.0), RA200H (12nm, pH 8.5 to 10.5), R711 (12nm, pH 4.0 to 6.0), NX90G (20nm, pH 4.0 to 6.0), Rheolosil MT-10 (15 nm, pH 4.8), DM-10 (15 nm, pH 4.8), DM-20S (12 nm, pH 4.8) (Nippon Aerosil Co., Ltd.) 4.8), DM-30 (7 nm, pH 4.5), DM-30S (7 nm, pH 4.5), KS-20SC (12 nm, pH 5.1), HM-20L (12 nm, pH 6.0), HM-30 Examples include Aerosil S (7 nm, pH 6.6), ZD-30ST (7 nm, pH 6.4), PM-09 (22 nm, pH 5.2), PM-20 (12 nm, pH 5.2), X-20 (12 nm, pH 5.3), and X-30 (7 nm, pH 5.3) (all manufactured by Tokuyama Corporation), and particularly preferred are Aerosil R972, R972V, R972CF, Reolosil MT-10, and DM-10.

[0022] In addition, conventionally known extender pigments such as wet silica, hydrophilic dry silica, light calcium carbonate, heavy calcium carbonate, talc, sericite, mica, kaolin, aluminum silicate, and barium sulfate can be used alone or in combination of two or more types, as long as they do not affect bleeding or washability. The amount added is preferably 5% by weight or less of the total amount of the aqueous paint composition.

[0023] The color pigment may be selected from conventionally known pigments. For example, Pigment Yellow 100 may be used as an organic pigment. 1, 2, 3, 5, 6, 10, 12, 13, 14, 16, 17, 24, 55, 62, 65, 73, 7 4, 81, 83, 93, 94, 95, 97, 98, 100, 104, 108, 109, 110, 111, 115, 117, 119, 128, 129, 137, 138, 139, 150, 151, 152, 154, 155, 166, 167, 170, 173, 175, 180, 181, 183, 185, 190, Pigment Orange 1, 5, 13, 16, 22, 34, 36, 43, 48, 49, 61, 62, 64, 66, 67, 68, 69, 71, 73, 81, 206, Pigment Red 1, 2, 3, 4, 5, 8, 9, 17, 22, 23, 31, 38, 41, 48, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 49:3, 52:1, 53:1, 57:1, 58:2, 58:4, 63:1, 63:2, 64:1, 81, 81:1, 81:3, 81:4, 83, 88, 90, 112, 114, 122, 1 23, 144, 146, 149, 150, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 184, 1 85, 188, 190, 194, 202, 206, 207, 208, 209, 216, 221, 242, 254, 255, 257, 260, 264, 272, Pigment Violet 1, 3:3, 19, 23, 29, 37, 38, 39, 42, 50, Pigment Blue 1, 9, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17:1, 18, 25, 60, 66, 75, 79, Pigment Green 4,These include Pigment 5, Pigment 7, Pigment 8, Pigment 36, Pigment 41, Pigment 58, Pigment Brown 23, Pigment 25, Pigment Black 1, Pigment 31, Pigment Green B, Industrene Brilliant Orange GK, Permanent Brown FG, Fire Red, Thioindigo Red, Bordeaux 5B, Carmine Lake, Fast Violet B, Industrene Violet, Acid Green Lake, and Alkaline Blue. Inorganic pigments include Pigment White 1, 4, 5, 6, 14, 18, 19, 20, 21, 22, 24, 26, 27, 28, Pigment Black 6, 7, 8, 9, 10, 11, 26, 27, 28, 35, Pigment Yellow 34, 35, 35:1, 37, 37:1, 40, 41, 42, 43, 46, 53, 157, 184, Pigment Orange 20, 20:1, 21, Pigment Red 101, 102, 104, 105, 106, 108, 108:1, 259, Pigment Violet Pigment Blue 14, 15, 47, 49, Pigment Blue 27, 28, 29, 33, 35, 36, Pigment Green 15, 17, 18, 19, 21, 23, 24, 26, 50, Pigment Brown 6, 7, 8, 9, 11, 24, 33, etc. As the special pigment, conventionally known pigments such as colored resin particles, fluorescent pigments, luminescent pigments, and phosphorescent pigments can be used. Commercially available colored resin particles, which are resin powders colored with dyes or pigments, include GT-21 Corona Magenta, GT-11 Aurora Pink, GT-13 Rocket Red, GT-14N Fire Orange, GT-15N Blaze Orange, GT-17N Saturn Yellow, GT-11 Aurora Pink, GT-12 Neon Red, GT-13 Rocket Red, GT-14 Fire Orange, GT-15 Blaze Orange, GT-16 Arc Yellow, GT-17N Saturn Yellow, GT-18 Signal Green, and GT-19 Horizon Blue (Day-Glo Corporation), and NKP-8301, NKP-8312, NKP-8303, NKP-8304, NKP-8315, NKP-8306, NKP-8307, NKP-8327, NKP-8328, NKP-8337, NKP-8347, and NKP-8377 (Nippon Fluorescent Chemical Co., Ltd.). For safety reasons, fluorescent pigments containing trace amounts of formaldehyde are generally not permitted in paints intended for use on fabrics or in paints that comply with the European Toy Safety Directive. Therefore, formaldehyde-free fluorescent pigments are used, such as GWT-10 Chartreuse, 11 Green, 13 Orange, 15 Red, 17 Pink, and 19 Blue (all from Radiant Co., Ltd.), SX-103 Red, 104 Orange, 105 Yellow, 106 Orange Yellow, 108 Conc Blue, and 117 Pink (all from Shin-Roihi Co., Ltd.). Luminous pigments that can be used include metal powder pigments such as aluminum powder and bronze powder, titanium oxide surface-treated with alumina and / or silica and / or zirconia, pearl pigments, glitter pigments, and holographic pigments. Luminous pigments have a larger particle size distribution than common organic pigments, inorganic pigments, and other coloring pigments, and the uneven distribution of fine particles or coloring pigments used in conjunction with them in the bleeding area can easily result in a coating surface with blurred and unclear boundaries, but by preventing bleeding, a luminous coating surface with clear boundaries can be obtained. These pigments can be used after being washed with water and dried, surface treated, or pH adjusted with pH adjusters such as alkaline agents, and can be used alone or in a mixture of two or more types. Commercially available pearlescent pigments include Pearl Glaze MM100R (silver, particle size 15 μm or less), which is made by coating the surface of natural mica with metal oxide,MF-100 (silver, particle size 5-30μm), MF100RN (silver, particle size 5-30μm), ME-100 (silver, particle size 10-60μm), ME-100R (silver, particle size 10-60μm), MS-100R (silver, particle size 20-100μm), ML-100R (silver, particle size 20-200μm), MXL-100R (silver, particle size 45-500μm), MY-100RF (interference color gold, particle size 5-30μm), MY-100R (interference color gold, particle size 10-60μm), MY2100R (interference color gold, MY100RL (interference color gold, particle size 10-125μm), MR-100R (interference color red, particle size 10-60μm), MR2100R (interference color red, particle size 10-60μm), MRB-100RF (interference color red-blue, particle size 5-30μm), MRB100R (interference color red-blue, particle size 10-60μm), MRB2100R (interference color red-blue, particle size 10-60μm), MRB100RL (interference color red-blue, particle size 10-125μm), MV-100RF (interference color violet, particle size 5-30μm), MV-100R (interference color violet, particle size 10-60μm), MV-2100R (interference color violet, particle size 10-60μm), MB-100RF (interference color blue, particle size 5-30μm), MB-100R (interference color blue, particle size 10-60μm), MB-2100R (interference color blue, particle size 10-60μm), MB-100RL (interference color blue, particle size 10-125μm), MG-100RF (interference color green, particle size 5-30μm), MG-100R (interference color green, particle size 10-60μm), MG-2100R (interference color green, particle size 10 ~60μm), MG-100RL (interference color green, particle size 10~125μm), MDY-100 (pale gold, particle size 10~60μm), MC-302 (gold, particle size 5~30μm), MRY-100 (gold, particle size 10~60μm), MC-351 (gold, particle size 10~100μm), MC-323R (slightly reddish gold, particle size 5~30μm), MC-303R (slightly reddish gold, particle size 10~60μm), MC-355R (slightly reddish gold, particle size 30~100μm), MC-326 (reddish gold, particle size 5~30μm),MC-325R (reddish gold, particle size 5-30μm), MC-305R (reddish gold, particle size 10-60μm), MC-520 (bronze, particle size 5-30μm), MC-500 (bronze, particle size 10-60μm), MC-530 (bronze, particle size 15-125μm), MC-522 (reddish brown, particle size 5-20μm), MC-502 (reddish brown, particle size 10-60μm), MC-532 (reddish brown, particle size 10-125μm) ), MC-524 (red, particle size 5-30 μm), MC-504 (red, particle size 10-60 μm), MC-534 (red, particle size 10-125 μm), MC-505 (red-blue, particle size 10-60 μm) (all manufactured by Nihon Koken Kogyo Co., Ltd.), as well as the Twinkle Pearl series (Nihon Koken Kogyo Co., Ltd.), in which the surface of synthetic mica is coated with metal oxide, and the Metashine series (Nippon Sheet Glass Co., Ltd.), in which the surface of glass flakes is coated with metal oxide. Other glitter and hologram pigments include Diamond Piece No. 55 (silver, LG gold, DG gold, green, blue, red, etc., 14 colors in total, average particle size 100 μm), No. 501 (same color, average particle size 200 μm), No. 530 (same color, average particle size 300 μm), and No. 580 (same color, average particle size 800 μm) (all from Diamond Industrial Co., Ltd.), which are finely cut films with aluminum vapor-deposited on them; and Crystal Color X-5 (opane, topaz, blue topaz, emerald, coral, sapphire, diamond, aquamarine, perry dot, bloom), which are finely cut multilayer films whose color changes depending on the viewing angle due to the interference of light. Green (average particle size 100μm), X-20 (same color, average particle size 200μm), X-40 (same color, average particle size 400μm) (all from Diamond Industrial Co., Ltd.), Aurora Flake Red 0.01, 0.05, Aurora Flake Green 0.01, 0.05, Aurora Flake Blue 0.01, 0.05, Aurora Flake Violet 0.01, 0.05 (average particle size for each color: 0.01: 150μm, 0.05: 200μm) (all from Kakuhachi Fish Scale Foil Co., Ltd.), Diamond Hologram HG-S20 (silver, LG gold,Examples include DG. Gold (average particle size 200 μm) and HG-S40 Silver (average particle size 400 μm) (both manufactured by Diamond Industrial Co., Ltd.). These photoluminescent pigments can be used alone, or in combination with two or more photoluminescent pigments with different particle sizes, colors, and compositions, or in combination with organic pigments, inorganic pigments, or other specialty pigments to adjust brightness and color. Furthermore, water-resistant phosphorescent pigments can be used, such as strontium aluminate compounds such as Alpha Vega GDK11010WP, GDK11025WP, GDK11060WP, BDK11025WP, GDK13025WP, and BDK13030WP (all manufactured by LTI Co., Ltd.), and Luminova G-300M, BG-300M, BS-300M, and R-300M (all manufactured by Nemoto Specialty Chemical Co., Ltd.). These pigments can also be used in combination with titanium dioxide, which has high hiding power, photoluminescent pigments, or other coloring pigments to enhance the luminescence in the dark. When safety is a consideration, it is preferable to use organic or inorganic pigments as specified in the European standard EN71-7:2014. For example, CIPIGMENT YELLOW 1, 3, 12, 13, 14, 17, 74, 138, 139, 151, 154, 155, 185, 42; CIPIGMENT ORANGE 13, 34, 43, 71; CIPIGMENT RED 48:2, 57:1, 63:1, 68, 83, 122, 181, 214, 242, 254, 255, 264, 272, 101; CIPIGMENT VIOLET 19, 23; CIPIGMENT BLUE 15, 16, 60, 29; CIPIGMENT GREEN 7, 36; CIPIGMENT WHITE There are 6, 18, 19, 21, 25, CIPIGMENT BLACK 6, 7, and 11. In addition, any pigment other than those listed here can be added as long as it does not impair the object of the present invention. The amount of color pigment used can be adjusted appropriately depending on the type of pigment and the desired color tone, luster, and hiding power, but it is preferably 0.01 to 40% by weight based on the total amount of the aqueous paint composition.

[0024] Conventionally known viscosity modifiers and rheology modifiers that can be used to adjust the ease of application of aqueous paint compositions, prevent bleeding, prevent pigment sedimentation, and adjust the build-up properties of the compositions include water-soluble pastes, thickening acrylic resin emulsions, inorganic thickeners, etc. Water-soluble pastes are used to improve the ease of application of aqueous paint compositions, and specific examples of water-soluble resins that can be used include natural water-soluble polymers such as gum arabic (Acaciasenegal, Acaciaseyal, etc.), glue, yellow dextrin, white dextrin, and British gum, as well as water-soluble resins such as locust bean gum, guar gum, tara gum, tragacanth gum, yellow dextrin, white dextrin, British gum, carboxyalkyl cellulose, hydroxyalkyl cellulose, methyl cellulose, polyvinyl alcohol, xanthan gum, polyvinylpyrrolidone, casein, alginate, and water-soluble acrylic resins. In order to allow the paint to spread easily and penetrate at an appropriate rate, making it easy to apply, and to maintain the water resistance of the coating film, it is preferable to use a solids content of 0.01 to 5.0% based on the total amount of the aqueous paint composition. Acrylic resin emulsions with thickening properties have unneutralized carboxyl groups, and are not intended to create a waterproof coating; instead, they are neutralized with alkali to dissolve or swell in the water-based paint composition and thicken it. From the perspective of the paint composition's stability over time and the flexibility of the coated surface, it is preferable to use an acrylic resin emulsion with a resin solids content of 0.1% by weight to 5.0% by weight based on the total amount of the water-based paint composition. Inorganic thickeners such as bentonite, hectorite, saponite, and montmorillonite can be used, preferably in amounts of 5.0% by weight or less based on the total amount of the aqueous paint composition. To obtain the required rheological properties, various water-soluble pastes, thickening acrylic resin emulsions, and inorganic thickeners can be used alone or in combination of two or more.

[0025] The water-soluble thickening agent is not particularly limited, but particularly preferred commercially available examples include the Metolose SM series (methylcellulose), Metolose SH series (hydroxypropyl methylcellulose), Metolose SE series (hydroxyethyl methylcellulose), Tylose H series P type (hydroxyethyl cellulose), and Tylose O series P type (hydroxypropyl cellulose) (all from Shin-Etsu Chemical Co., Ltd.), the Cellogen series (carboxymethylcellulose, Dai-ichi Kogyo Seiyaku Co., Ltd.), and the NISSO HPC series (hydroxypropyl cellulose, Nippon Soda Co., Ltd.).

[0026] There is no particular limitation on the acrylic resin emulsion with thickening properties, but commercially available examples include Primal ASE-60 (resin solids content 28%) (Dow Chemical Japan Co., Ltd.), Vinizol 1020 (resin solids content 29%) (Daido Chemical Industry Co., Ltd.), Viscarex HV30 (resin solids content 30%) (Ciba Specialty Chemicals Co., Ltd.), Aron B-300 (resin solids content 44%), Aron A-7070 (resin solids content 20%) (all manufactured by Toa Gosei Co., Ltd.), AICA AIBO K-50 (resin solids content 45%), and AIBO V-280 (resin solids content 28%) (all manufactured by AICA Kogyo Co., Ltd.).

[0027] The inorganic thickener is not particularly limited, but commercially available examples include Kunipia-F, Kunipia-G4, Kunipia-G (all refined bentonite), Sumecton SA (synthetic saponite), Sumecton-SWN, Sumecton SWF (all synthetic hectorite) (all Kunimine Kogyo Co., Ltd.).

[0028] The basic compound is used as an alkali agent to thicken the thickening acrylic resin emulsion or to improve the dispersion stability of non-thickening acrylic resin emulsions, and as a pH adjuster for aqueous paint compositions. Both inorganic and organic compounds can be used as basic substances. Inorganic compounds include ammonia, sodium hydroxide, and potassium hydroxide, while organic compounds include triethanolamine, triisopropanolamine, triethylamine, tributylamine, and tetrahydroparaoxazine. These compounds can be used alone or in combination. A particularly preferred basic compound is triethanolamine alone or in combination with sodium hydroxide. The preferred amounts of triethanolamine and sodium hydroxide are 0.1% to 5.0% by weight of the total aqueous paint composition, and 10% aqueous sodium hydroxide solution is 10.0% or less by weight. The pH of the aqueous paint composition is adjusted to between 8.0 and 11.0 within these amounts to prevent thickening and gelation over time.

[0029] Water-soluble high-boiling solvents are used for purposes such as drying regulators, antifreeze agents, and improving low-temperature film-forming properties of aqueous paint compositions. Specific examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, 1,5-pentanediol, and glycerin, as well as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylcyclohexane, ethyl glycol acetate, propylene glycol monomethyl acetate, 2-pyrrolidone, N-methyl-2-pyrrolidone, triethanolamine, and diisononyl cyclohexane dicarboxylate. The preferred amount of these solvents is 0.5% by weight or more and 20% by weight or less of the total weight of the aqueous paint composition to maintain adequate drying properties, freeze resistance, fluidity, and viscosity.

[0030] The preservative prevents mold growth and the proliferation of spoilage bacteria in the aqueous paint composition over time. Preservatives commonly used in aqueous paint compositions can be used, including, but not limited to, phenol, chloroacetamide, 2-pyridinethiol-1-oxide sodium salt, sodium dehydroacetate, sodium benzoate, sodium sorbate, potassium sorbate, phenoxyethanol, triclosan, sodium 2-phenylphenol, 2-bromo-2-nitropropane-1,3-diol, 3-iodo-2-propynyl butylcarbamate, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-2H-isothiazol-3-one, thiabendazole, sodium fluoride, 4-(2-nitrobutyl)morpholine, and 1,3-dimorpholino. -2-ethyl-2-nitripropane, zinc pyrithione, 2,2'-dithiobis(N-methylbenzamide), methylene dithiocyanate, 2-butylbenzo[d]isothiazol-3(2H)-one, 4,5-dichloro-2-octyl-4-isothiazolin-3-one, 2,2-dibromo-2-cyanoacetamide, carbendazim, silver zinc zeolite, diiodomethyl-p-tolylsulfone, 3-(4-chlorophenoxy)-1,2-propanediol, caprylyl glycol, decylene glycol, ethylhexylglycerin, methylparaben, ethylparaben, propylparaben, butylparaben, 5-chloro-2-(2,4-dichlorophenoxy)phenol, thymol, isopropylmethylphenol, etc., which can be used alone or in combination of two or more.

[0031] Particularly preferred preservatives that provide high antifungal and antiseptic effects in small amounts and do not affect pigment dispersion in acrylic paints are 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-butylbenzo[d]isothiazol-3(2H)-one, 4,5-dichloro-2-octyl-4-isothiazolin-3-one, and carbendazim, which can be used alone or in combination. Also highly safe preservatives that do not affect pigment dispersion in acrylic paints are particularly preferred, and can be used alone or in combination. Zinc pyrithione, 2,2'-dithiobis(N-methylbenzamide), 2-pyridinethiol-1-oxide sodium salt, triclosan, sodium 2-phenylphenol, isopropylmethylphenol, and diiodomethyl-p-tolylsulfone are particularly preferred, and can be used alone or in combination. The type and amount of additives can be adjusted appropriately depending on the desired performance, for example, by combining a type that is highly effective with a small amount of additive with a type that is highly safe. Also, it is possible to combine known additives that are expected to produce a synergistic effect when combined.

[0032] The antifoaming agent assists in the defoaming of bubbles that are generated during stirring or dispersion in formulations containing a large amount of synthetic resin emulsion. Silicone-based antifoaming agents and mineral oil-based antifoaming agents commonly used in aqueous compositions can be used, including, but not limited to, Aqualene 8021N, SB-520, SB-630, and Florene AO-5 (all manufactured by Kyoeisha Chemical Co., Ltd.), SN Deformer 113, 393, 399, 1311, 1315, 5016, Noptum 777-F, 3590, and 8034-F (all manufactured by San Nopco Co., Ltd.). If the amount used is too small, sufficient defoaming effect cannot be obtained, while if too much, the gloss, water resistance, and smoothness of the coating film are impaired. Therefore, the amount is preferably 0.05% by weight or more and 2.0% by weight or less.

[0033] In addition, a defoaming agent, a deaerating agent, a surfactant, etc. may also be used in combination as needed.

[0034] The water-based paint composition of the present invention can be easily produced by mixing and dispersing the components using a conventionally known agitator or disperser such as a disperser, homogenizer, turbo mixer, Henschel mixer, reduced pressure Henschel mixer, three-roll mill, horizontal ball mill, or horizontal bead mill. [Example]

[0035] Example 1 AICA AIBO M-584 (acrylic resin emulsion, Tg-30℃, resin solids 5 5%, pH approx. 7, manufactured by Aica Kogyo Co., Ltd.) 60.0 parts by weight Aerosil R972 (hydrophobic dry silica, average primary particle diameter 16 nm, pH 4.0 or higher) 0.5 or less, manufactured by Nippon Aerosil Co., Ltd.) 1.0 parts by weight Calcium sulfate A (calcium sulfate dihydrate, manufactured by Yoshino Gypsum Co., Ltd.) 0.3 parts by weight (Calcium sulfate excluding internal hydrate: 0.24 parts by weight) Vinizol 1020 (acrylic resin emulsion for thickening, resin solids 29%, Daido Kasei) Kogyo Co., Ltd.) 2.2 parts by weight Tylose H4000P 4% aqueous solution (hydroxyethyl cellulose, Shin-Etsu Chemical Co., Ltd.) ) 4.0 parts by weight Triethanolamine (alkali agent) 2.0 parts by weight Propylene glycol (humectant) 12.0 parts by weight Phthalocyanine green (organic pigment) 4.0 parts by weight Densil P (preservative, active ingredient: 2,2'-dithiobis(N-methylbenzamide), (manufactured by SANZA JAPAN Co., Ltd.) 0.2 parts by weight SN Deformer 113 (antifoaming agent, manufactured by San Nopco Co., Ltd.) 0.3 parts by weight Water 14.0 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a green water-based paint composition.

[0036] Example 2 Rikabond FK-284 (acrylic resin emulsion, Tg-40℃, resin solids 30 %, pH approx. 7, manufactured by Japan Coating Resin Co., Ltd.) 50.0 parts by weight Aerosil R974 (hydrophobic dry silica, average primary particle diameter 12 nm, pH 3.8 or higher) 0.0 or less, manufactured by Nippon Aerosil Co., Ltd.) 6.0 parts by weight Special grade calcined gypsum (calcium sulfate 1 / 2 hydrate, manufactured by Yoshino Gypsum Co., Ltd.) 2.0 parts by weight (Calcium sulfate excluding internal hydrate: 1.85 parts by weight) Cellogen 7A 4% aqueous solution (carboxymethyl cellulose, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.0 parts by weight Triethanolamine 1.0 parts by weight 10% aqueous solution of sodium hydroxide (alkali agent) 2.0 parts by weight Propylene glycol 5.0 parts by weight Pigment Black 7 (inorganic pigment) 15.0 parts by weight Tama Pearl TP-111 (light calcium carbonate, manufactured by Okutama Kogyo Co., Ltd.) 4.0 parts by weight Sodium Omadine 40% aqueous solution (preservative, active ingredient: sodium pyrithione, Lonza J Pan Co., Ltd.) 0.2 parts by weight SN Deformer 113 0.3 parts by weight Water 14.0 parts by weight The above components were stirred in a lab mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a black aqueous paint composition.

[0037] Example 3 AICA AIBO M-581 (acrylic resin emulsion, Tg-25℃, resin solids 5 9%, pH approx. 8, manufactured by Aica Kogyo Co., Ltd.) 70.0 parts by weight Aerosil R972 0.05 parts by weight Calcium sulfate A 0.3 parts by weight (Calcium sulfate excluding internal hydrate: 0.24 parts by weight) Vinizol 1020 2.1 parts by weight NISSO HPC H 4% aqueous solution (hydroxypropyl cellulose, manufactured by Nippon Soda Co., Ltd.) 4.0 parts by weight Triethanolamine 1.0 parts by weight 2.0 parts by weight of 10% aqueous sodium hydroxide solution Propylene glycol 5.0 parts by weight Pigment Blue 15 (organic pigment) 5.0 parts by weight Densil P 0.2 parts by weight SN Deformer 113 0.5 parts by weight Water 9.85 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a blue aqueous paint composition.

[0038] Example 4 AICA AIBO M-584 40.0 parts by weight Aerosil R972 2.0 parts by weight Special grade calcined gypsum 0.5 parts by weight (Calcium sulfate excluding internal hydrate: 0.46 parts by weight) Vinizol 1020 3.0 parts by weight Triethanolamine 1.0 parts by weight 2.0 parts by weight of 10% aqueous sodium hydroxide solution Propylene glycol 9.0 parts by weight Pigment Red 101 (inorganic pigment) 11.0 parts by weight Carplex 1120 (hydrophilic wet silica, manufactured by Evonik Japan Co., Ltd.) 1.0 parts by weight Biocut TR-120 (preservative, active ingredient: organic nitrogen compound (thiazoline), (manufactured by Nippon Soda Co., Ltd.) 0.2 parts by weight Orotan 1288 (dispersant, acrylic acid polymer sodium salt, Dow Chemical Japan) Co., Ltd.) 0.2 parts by weight SN Deformer 113 0.3 parts by weight Water 29.8 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a brown water-based paint composition.

[0039] Example 5 Rikabond FK-284 50.0 parts by weight Aerosil R974 0.7 parts by weight D-101A (type III anhydrous gypsum, manufactured by Noritake Co., Ltd.) 0.5 parts by weight Vinizol 1020 2.0 parts by weight Tyrose H4000P 4% aqueous solution 3.5 parts by weight Triethanolamine 1.0 parts by weight Propylene glycol 10.0 parts by weight Pearl Glaze MC-502 (pearl pigment, red-brown, particle size 10-60 μm, Japan) Koken Kogyo Co., Ltd.) 10.0 parts by weight Pearl Glaze MC-532 (Pearl pigment, red-brown, particle size 10-125 μm, Japan) Koken Kogyo Co., Ltd.) 10.0 parts by weight Sodium Omadine 40% aqueous solution 0.2 parts by weight Water 12.1 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a copper-colored, high-brilliance aqueous paint composition.

[0040] Example 6 DirtShield08 (acrylic resin emulsion, Tg 12°C, resin solids 45 0.5%, pH 7.5 to 8.5, manufactured by Dow Chemical Japan Co., Ltd.) 30.0 parts by weight Aerosil RA200H (hydrophobic dry silica, average primary particle diameter 12 nm, pH 8.5 or higher) (10.5 or less, manufactured by Nippon Aerosil Co., Ltd.) 7.0 parts by weight Calcium sulfate A 3.0 parts by weight (Calcium sulfate excluding internal hydrate: 2.37 parts by weight) Tyrose H4000P 4.0% aqueous solution 0.5 parts by weight Triethanolamine 1.0 parts by weight 10% aqueous solution of sodium hydroxide 5.0 parts by weight Propylene glycol 10.0 parts by weight Pearl Glaze ML-100R (Pearl pigment, silver, particle size 20-200 μm, Nippon Kogyo) (manufactured by Kenkogyo Co., Ltd.) 7.0 parts by weight Pearl Glaze MC-502 1.0 parts by weight Densil P 0.2 parts by weight Water 35.3 parts by weight The above components were stirred in a lab mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a light copper-colored, high-brilliance aqueous paint composition.

[0041] Example 7 AICA AIBO M-581 50.0 parts by weight Aerosil RA200H 4.5 parts by weight D-101A 2.1 parts by weight Vinizol 1020 2.0 parts by weight Tyrose H4000P 4.0% aqueous solution 3.0 parts by weight Triethanolamine 1.0 parts by weight 10% aqueous solution of sodium hydroxide 5.0 parts by weight Propylene glycol 15.0 parts by weight Pearl Glaze ML-100R 5.0 parts by weight Aurora Flake Blue 0.05 (multilayer film glitter pigment, polarized blue, average particle size 200 μm, manufactured by Kakuhachi Fish Scale Foil Co., Ltd.) 5.0 parts by weight Sodium Omadine 40% aqueous solution 0.2 parts by weight SN Deformer 113 0.2 parts by weight Water 7.0 parts by weight All of the above ingredients except for water and Aurora Flake Blue 0.05 were stirred in a laboratory mixer for 15 minutes, then passed three times through a three-roll mill, and while stirring at low speed, the water and Aurora Flake Blue mixture was added to obtain a polarized blue high-gloss water-based paint composition.

[0042] Example 8 AICA AIBO M-581 50.0 parts by weight Aerosil R974 1.0 parts by weight Calcium sulfate A 0.1 parts by weight (Calcium sulfate excluding internal hydrate: 0.08 parts by weight) Vinizol 1020 2.2 parts by weight NISSO HPC H 4% aqueous solution 3.0 parts by weight Triethanolamine 1.0 parts by weight Propylene glycol 9.0 parts by weight Aurora Flake Blue 0.05 7.0 parts by weight Aurora Flake Red 0.05 (Multilayer Film Glitter Pigment, Polarized Red, Average Particle Size 200 μm, manufactured by Kakuhachi Fish Scale Foil Co., Ltd.) 8.0 parts by weight Densil P 0.2 parts by weight SN Deformer 113 0.2 parts by weight Water 18.3 parts by weight All of the above ingredients except for water, Aurora Flake Blue 0.05, and Aurora Flake Red 0.05 were stirred in a laboratory mixer for 15 minutes, and then the mixture was passed through a three-roll mill three times. While stirring at low speed, the mixture of water, Aurora Flake Blue 0.05, and Aurora Flake Red 0.05 was added, yielding a high-brilliance aqueous paint composition that reflects blue and red polarized colors.

[0043] Example 9 AICA AIBO M-584 50.0 parts by weight Aerosil R974 1.0 parts by weight Calcium sulfate A 0.5 parts by weight (Calcium sulfate excluding internal hydrate: 0.4 parts by weight) Vinizol 1020 2.2 parts by weight Tyrose H4000P 3.0 parts by weight Triethanolamine 1.0 parts by weight 1.0 parts by weight of 10% aqueous sodium hydroxide solution Propylene glycol 9.0 parts by weight Diethylene glycol monomethyl ether 1.0 parts by weight Pearl Glaze ME-100 (Pearl pigment, silver, particle size 10-60 μm, Nippon Koken Kogyo) (manufactured by Gyo Co., Ltd.) 5.0 parts by weight Alpha Vega GDK11010WP (luminous pigment, luminous color green, body color light yellow-green, average particle size 15.0 parts by weight of 10 μm thick cellulose nitrate (manufactured by LTI Co., Ltd.) Biocut TR-120 0.2 parts by weight SN Deformer 113 0.2 parts by weight Water 10.9 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed three times through a three-roll mill to obtain a pale yellow-green high-gloss aqueous paint composition that glows green in the dark.

[0044] Example 10 AICA AIBO M-584 60.0 parts by weight Aerosil R972 1.5 parts by weight Calcium sulfate A 0.2 parts by weight (Calcium sulfate excluding internal hydrate: 0.16 parts by weight) Vinizol 1020 2.2 parts by weight Tyrose H4000P 4% aqueous solution 4.0 parts by weight Triethanolamine 2.0 parts by weight Propylene glycol 5.0 parts by weight Pigment Blue 15 5.0 parts by weight Pearl Glaze ME-100 5.0 parts by weight Pearl Glaze MB-100R (Pearl pigment, interference color blue, particle size 10-60μm, Japan) Koken Kogyo Co., Ltd.) 5.0 parts by weight Densil P 0.2 parts by weight SN Deformer 113 0.3 parts by weight Water 9.6 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a blue high-gloss aqueous paint composition.

[0045] Comparative Example 1 A green aqueous paint composition was obtained by replacing calcium sulfate A in Example 1 with Tamapearl TP-111 (calcium carbonate), and then stirring in a lab mixer for 15 minutes, followed by passing the mixture through a three-roll mill three times.

[0046] Comparative Example 2 A green aqueous paint composition was obtained by replacing AICA AIBO M-584 in Example 1 with Sumikaflex 201HQ (ethylene-vinyl acetate resin emulsion, Tg -20°C, resin solids content 55%, pH approximately 3.0 to 6.0, manufactured by Sumika Chemtex Co., Ltd.), and stirring the mixture in a lab mixer for 15 minutes, then passing the mixture through a three-roll mill three times.

[0047] Comparative Example 3 The same mixture as in Example 1, but replacing Aerosil R-972 with Carplex 1120, was stirred in a lab mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a green water-based paint composition.

[0048] Comparative Example 4 Primal AC-261T (acrylic resin emulsion, Tg 24°C, resin solids 49 0.5%, pH 8.5 to 9.1, manufactured by Dow Chemical Japan Co., Ltd.) 30.0 parts by weight DirtShield08 30.0 parts by weight Vinizol 1020 2.3 parts by weight Cerogen 7A 3.0 parts by weight Triethanolamine 2.0 parts by weight 1.0 parts by weight of 10% aqueous sodium hydroxide solution Propylene glycol 5.0 parts by weight Pigment Blue 15 5.0 parts by weight Pearl Glaze ME-100 5.0 parts by weight Pearl Glaze MB-100R 5.0 parts by weight Carplex 1120 1.0 parts by weight Proxel GXL (preservative, active ingredient: 1,2-benzisothiazolin-3-one, lon The Japan Co., Ltd.) 0.2 parts by weight Biocut TR-120 0.2 parts by weight SN Deformer 113 0.3 parts by weight Water 10.0 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a blue high-gloss aqueous paint composition.

[0049] Comparative Example 5 AICA AIBO M-584 60.0 parts by weight Aerosil R972 1.0 parts by weight Vinizol 1020 2.0 parts by weight NISSO HPC H 4% aqueous solution 2.0 parts by weight Triethanolamine 1.0 parts by weight 1.5 parts by weight of 10% aqueous sodium hydroxide solution Propylene glycol 12.0 parts by weight Pigment Black 7 5.0 parts by weight Pearl Glaze MB-100R 5.0 parts by weight Proxel GXL 0.3 parts by weight SN Deformer 113 0.2 parts by weight Water 10.0 parts by weight The above components were stirred in a lab mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a black high-gloss aqueous paint composition.

[0050] Comparative Example 6 AICA AIBO M-584 60.0 parts by weight Calcium sulfate A 0.3 parts by weight (Calcium sulfate excluding internal hydrate: 0.24 parts by weight) Vinizol 1020 2.5 parts by weight Tyrose H4000P 4% aqueous solution 4.0 parts by weight Triethanolamine 1.0 parts by weight 10% aqueous solution of sodium hydroxide 3.0 parts by weight Propylene glycol 9.0 parts by weight Pigment Blue 15 5.0 parts by weight Biocut TR-120 0.2 parts by weight SN Deformer 113 0.3 parts by weight Water 14.7 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a blue aqueous paint composition.

[0051] Comparative Example 7 Dextrin 45% aqueous solution (fixing agent) 40.0 parts by weight Aerosil R972 1.0 parts by weight Calcium sulfate A 1.0 parts by weight (Calcium sulfate excluding internal hydrate: 0.8 parts by weight) Cerogen 7A 4% aqueous solution 4.5 parts by weight Glycerin (humectant) 10.0 parts by weight Pigment Red 101 15.0 parts by weight Tama Pearl TP-111 15.0 parts by weight Densil P 0.5 parts by weight Water 13.0 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a brown water-based paint composition.

[0052] Comparative Example 8 AICA AIBO M-584 60.0 parts by weight Nipsil SS-50F (hydrophobic wet silica, average particle size 0.6 μm or more and 1.7 μm or less) (pH 6.5 to 8.5, manufactured by Tosoh Silica Corporation) 1.0 part by weight Calcium sulfate A 0.3 parts by weight (Calcium sulfate excluding internal hydrate: 0.24 parts by weight) Vinizol 1020 2.2 parts by weight Tyrose H4000P 4.0 parts by weight Triethanolamine 2.0 parts by weight Propylene glycol 5.0 parts by weight Pigment Blue 15 5.0 parts by weight Pearl Glaze ME-100 5.0 parts by weight Pearl Glaze MB-100R 5.0 parts by weight Densil P 0.2 parts by weight Water 10.3 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a blue high-gloss aqueous paint composition.

[0053] Comparative Example 9 A blue high-brilliance aqueous paint composition was obtained by replacing Nipsil SS-50F of Comparative Example 8 with Aerosil 200 (hydrophilic dry silica, average primary particle diameter of approximately 12 nm, pH 4.0 to 4.5, manufactured by Nippon Aerosil Co., Ltd.), and stirring the mixture in a lab mixer for 15 minutes, followed by passing the mixture through a three-roll mill three times.

[0054] Comparative Example 10 AICA AIBO M-584 20.0 parts by weight Aerosil R974 1.0 parts by weight Vinizol 1020 2.2 parts by weight Tyrose H4000P 4% aqueous solution 4.0 parts by weight Triethanolamine 1.0 parts by weight 1.0 parts by weight of 10% aqueous sodium hydroxide solution Propylene glycol 5.0 parts by weight Pigment Green 7 20.0 parts by weight Tama Pearl TP-111 30.0 parts by weight Proxel GXL 0.2 parts by weight Water 15.6 parts by weight The above components were stirred in a laboratory mixer for 15 minutes, and then passed through a three-roll mill three times to obtain a green water-based paint composition.

[0055] The aqueous paint compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 10 were subjected to a bleeding test, a washing fastness test, a stability test over time, and color development test, and the results are shown in Table 1.

[0056] [Table 1]

[0057] Bleeding test: In a room with temperature and humidity controlled at 25°C and 40%, a piece of cloth (cotton broadcloth #60) approximately 15cm long and 8cm wide was attached to an embroidery frame in a taut state without slack, ensuring that the backside of the cloth did not touch the ground. 1g of water was added to 1g of water-based paint composition and dissolved uniformly. The water-based paint composition dissolved in water was drawn up with a micropipette and dropped onto the fabric in five locations, each at 0.45μL. After the dropped sample had completely dried, the fabric was removed from the embroidery frame, and the diameters of five circles on the sample that had spread were measured and the average calculated. The results of each example and comparative example were evaluated for bleeding at high dilution according to the following criteria. ◎: Less than 10mm (very unlikely to bleed) ○: 10mm or more, less than 12mm (less likely to bleed) △: 12mm or more, less than 15mm (slightly less likely to bleed) ×: 15mm or more (easily bleeds)

[0058] Washing fastness test: In a room with controlled temperature and humidity (25°C, 40%), 1 g of water-based paint composition was mixed with 0.5 g of water and dissolved uniformly. A piece of cloth (60 cotton broadcloth) approximately 15 cm long and 8 cm wide was attached to an embroidery frame, with the back of the cloth stretched tightly so that it did not touch the ground. The mixture was then applied with a brush to a width of approximately 2 cm long and 8 cm wide. Other colors were applied in the same manner and allowed to dry for one day. The cloth was then cut in half lengthwise, with one half serving as the pre-wash sample and the other as the wash sample. All of the wash samples from each example and comparative example, along with four face towels, were placed in a vertical washing machine (NA-F60H1, Panasonic Corporation) and washed in 40 L of water with 30 g of powder detergent (Attack Highly Active Bio EX, Kao Corporation) (the recommended amount relative to the water volume) in fully automatic mode, with a wash cycle of 10 minutes, rinsing (20 minutes), and spin-drying (10 minutes). Once the laundry sample had dried, the color difference between the pre-washed and post-washed samples was measured. To measure the color difference, a spectrophotometer SE7700 manufactured by Nippon Denshoku Industries Co., Ltd. was used to measure the chromaticity at a D65 light source and a 10° field of view, and the color difference ΔE00 was calculated. The results of each example and comparative example were evaluated according to the following criteria. ◎: ΔE00 is less than 1.0 (very good washing fastness) ○: ΔE00 is 1.0 or more and less than 2.0 (relatively high washing fastness) △: ΔE00 is 2.0 or more and less than 3.0 (slightly insufficient washing fastness) ×: ΔE00 is 3.0 or more (poor washing fastness)

[0059] Stability testing: 12mL of the aqueous paint composition was filled into a plastic tube used for Pentel Co., Ltd.'s F Watercolor (WFC1-12), and left to stand in a 50°C thermostatic chamber for three months, then removed and allowed to cool to room temperature before being compared with the initial quality. Evaluation items included adding 0.5g of water to 1g of the aqueous paint composition, dissolving it uniformly, applying it with a brush to a cloth (cotton broadcloth #60) to check dispersion and color development, and measuring hardness using JIS K 5101 Pigment Testing Method 10.1 Spread Method. ◎: There is no difference in quality between the product stored at 50°C for 3 months and the initial quality, and there are no problems with actual use between the product stored at 50°C for 3 months and the initial quality (high stability over time) ○: There is little difference in quality between the product stored at 50°C for 3 months and the initial quality, and there are no problems in actual use between the product stored at 50°C for 3 months and the initial quality (high stability over time) △: There is a difference in quality between the product stored at 50°C for 3 months and the initial product, but there are no problems with actual use between the product stored at 50°C for 3 months and the initial product (stability over time is within the acceptable range) ×: There is a large difference in quality between the product stored at 50°C for 3 months and the initial product, and the product stored at 50°C for 3 months has problems in practical use (low stability over time).

[0060] Color: The test pieces prepared for the washing fastness test were dried for one day and then visually inspected for color development before washing, and evaluated according to the following criteria. ◎: No uneven color and very good color development ○: No uneven color and good color development △: There is some color unevenness, but the color is generally good ×: Color unevenness and poor color development (pigment bleed-through and hard aggregation)

[0061] Examples 1 to 10 are good in the bleeding test, washing fastness test, stability over time test, and color development test. In particular, in Examples 1, 9, and 10, the content of calcium sulfate excluding hydrates is 0.05% by weight or more and 2.0% by weight or less relative to the total amount of the aqueous paint composition, the amount of hydrophobic dry silica added is 0.05% by weight or more and 5% or less relative to the total amount of the aqueous paint composition, and the ratio of the content of hydrophobic dry silica contained in the aqueous paint composition to the content of calcium sulfate contained in the aqueous paint composition excluding hydrates is 2 or more and 10 or less, and the total is 0.5% by weight or more and 2.0% by weight or less relative to the total amount of the aqueous paint composition, so that the paints have very little bleeding, very clear color development with no color unevenness, and are also washable. Comparative Examples 1 to 10 do not contain either an acrylic resin emulsion, hydrophobic dry silica, or calcium sulfate, and therefore do not form an aggregate complex to prevent bleeding, making it impossible to prevent bleeding. Comparative Example 1 uses calcium carbonate instead of calcium sulfate as a conventional extender pigment, but it is prone to bleeding, shows through, and exhibits poor color development. Comparative Example 2 uses an ethylene-vinyl acetate resin emulsion instead of an acrylic resin emulsion, resulting in poor bleeding and color development, as well as poor stability over time. Comparative Example 3 uses hydrophilic wet silica instead of hydrophobic dry silica, but the hydrophilic surface and large particle size of the wet silica result in poor bleeding and color development. Comparative Example 4 does not contain calcium sulfate or hydrophobic dry silica, resulting in poor bleeding and color development. Comparative Example 5 does not contain calcium sulfate, resulting in poor bleeding and color development. Comparative Example 6 does not contain hydrophobic dry silica, resulting in poor bleeding and color development. In Comparative Example 7, a water-soluble thickener was added instead of a resin emulsion, causing the coating to dissolve in water, resulting in poor bleeding and washing fastness. In Comparative Example 8, hydrophobic wet silica was added instead of hydrophobic dry silica, but wet silica's large particle size causes it to form very large aggregates, resulting in poor color development and stability over time. In Comparative Example 9, hydrophilic wet silica was added instead of hydrophobic dry silica, but because it is hydrophilic, it does not interact with the acrylic resin emulsion, resulting in poor bleeding and color development. In Comparative Example 10, the acrylic gouache formulation contains little acrylic resin emulsion and a high solid content of pigments and extenders, resulting in little viscosity loss even at high dilutions. However, calcium sulfate was not added, resulting in poor bleeding and color development. Wash fastness was also poor.

[0062] As explained in detail above, the aqueous paint composition according to the present invention has excellent bleeding resistance, washing fastness and color development, and has the excellent properties of not causing gelation or hard aggregation over time.

Claims

1. An aqueous paint composition comprising at least an acrylic resin emulsion, hydrophobic dry silica, and calcium sulfate.

2. 2. The aqueous paint composition according to claim 1, wherein the content of calcium sulfate contained in the aqueous paint composition, excluding hydrates, is 0.05% by weight or more and 2.0% by weight or less based on the total amount of the aqueous paint composition.

3. 3. The aqueous paint composition according to claim 1, wherein the content of the hydrophobic dry silica contained in the aqueous paint composition is 0.05% by weight or more and 5% by weight or less based on the total amount of the aqueous paint composition.

4. 4. The aqueous paint composition according to any one of claims 1 to 3, wherein the content of the hydrophobic dry silica contained in the aqueous paint composition relative to the content of the calcium sulfate contained in the aqueous paint composition excluding hydrates is 2 to 10%, and the total of these is 0.5 to 2.0% by weight based on the total amount of the aqueous paint composition.

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