Surface modifiers, waterborne coating compositions, articles, and methods for forming multilayer coatings

Abstract

This invention provides a surface modifier, an aqueous coating composition containing the surface modifier, an article coated with a coating agent containing the surface modifier, and a method for forming a multilayer coating film using an aqueous coating containing the surface modifier. The surface modifier prevents solvent bubbles generated during the formation of a multilayer coating film by wet-on-wet contact and does not impede topcoatability. The aqueous coating surface modifier comprises: a polymer (A) having an SP value of 6 to 12, a weight-average molecular weight of 200 to 1,000,000, and having at least three repeating units; and organic solid particles (B) which are in a solid state in the surface modifier at 25°C.

Description

Technical Field

[0001] This invention relates to a surface conditioner, a water-based coating composition, an article, and a method for forming a multilayer coating film. Background Technology

[0002] In the painting process of automobile bodies, etc., to impart corrosion resistance and design properties, a primer coating (such as electrophoretic coating), a first coat, and a second coat are usually applied, and a clear coat is applied as needed to form a multi-layer coating film on the substrate. As a method for forming such a multi-layer coating film on an automobile body, a widely used method is as follows: after forming a primer film on the substrate, a three-coat, two-bake (3C2B) process is performed sequentially, followed by the application of a first coat, baking and curing, the application of a second coat, the application of a clear coat, and baking and curing, to form a multi-layer coating film.

[0003] In contrast, in recent years, in order to reduce CO2 and save energy, a method for forming multi-layer coatings has been explored: a three-coat-one-bake (3C1B) method that omits the baking and curing process after the first coating is applied and instead sequentially applies the first coating, preheats (preheats), applies the second coating, preheats, applies the clear coat, and bakes and cures. That is, a so-called wet-on-wet method that does not perform coating curing in the coating stage of each coating layer but instead repeatedly applies the upper coating and performs multiple layers of baking and curing.

[0004] Furthermore, in recent years, from the perspective of environmental issues and health impacts, efforts are underway to reduce volatile organic compounds (VOCs) by replacing solvent-based coatings with water-based coatings. In automotive body painting, the trend of water-based first and second coatings is also increasingly active, particularly in the 3C1B system, which requires the use of water-based coatings as both the first and second coatings.

[0005] To make coatings water-based, it is necessary to improve the solubility and dispersibility of the resin forming the coating film in water. This is achieved by polarizing the resin through the introduction of hydrophilic groups or by adding surfactants. However, water-based coatings containing polarized resins and surfactants are prone to foaming, and these bubbles are easily stabilized. Therefore, preventing the introduction of air bubbles during the manufacturing and coating processes, and preventing residual air bubbles and solvent bubbles in the dried coating film, has become an important issue in water-based coatings. Various surface modifiers for water-based coatings have been proposed as additives to prevent the introduction of air bubbles during the manufacturing and coating processes.

[0006] For example, Patent Document 1 discloses an antifoaming agent for water-based coatings, which is added to water-based coatings to prevent bubbles (solvent bubbles) during the baking process. It contains a copolymer of an ether-containing alkyl (meth)acrylate monomer (A) and a (ether-free) alkyl (meth)acrylate monomer (B). Patent Document 2 discloses an antifoaming agent for water-based coatings, which is prepared by dissolving polyoxyethylene hydrogenated castor oil triisostearate and one or more of a mixture selected from polyalkyl vinyl ethers, polybutadiene, polybutene, and polyisoprene in a specific hydrophobic solvent.

[0007] Furthermore, Patent Document 3 discloses an defoamer composition as a silicone-based defoamer, which is composed of an organic polysiloxane modified with an organic ester having a specific structure and silica micropowder. This defoamer composition can be a defoamer composition that combines high defoaming performance, dispersibility, and coatability with various coating liquids.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2010-100796

[0011] Patent Document 2: Japanese Patent Application Publication No. 2010-075779

[0012] Patent Document 3: Japanese Patent Application Publication No. 2010-279889 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] However, when forming a multilayer coating film by a wet-on-wet method, air bubbles generated during the manufacturing and application of the first and second coatings, as well as air bubbles (entrapped air bubbles) generated during the manufacturing and application of the first and second coatings, remain in the uncured multilayer coating film. During the baking and curing process, "solvent bubbles" caused by these entrapped air bubbles remaining in the uncured multilayer coating film are sometimes generated. To date, no research has been conducted from the perspective of preventing the generation of such "solvent bubbles" caused by entrapped air bubbles in the multilayer coating film. Therefore, the inventors have focused on the problem of "preventing solvent bubbles generated by air bubbles entrapped during the manufacturing and application of the first and second coatings, as well as air bubbles entrapped in the uncured multilayer coating film when forming a multilayer coating film by a wet-on-wet method," and have studied means for solving such problems.

[0015] While Patent Documents 1 and 2 mention preventing solvent bubbles in single-layer coatings, they do not address the issue of preventing solvent bubbles in multilayer coatings caused by air bubbles entrapped during the manufacturing and application of the first and second coatings when forming multilayer coatings by a wet-on-wet method. Similarly, Patent Document 3 only evaluates the defoaming performance, dispersibility, and coatability of the defoamer composition, and like Patent Documents 1 and 2, it does not address the issue of preventing solvent bubbles in multilayer coatings caused by air bubbles entrapped during the manufacturing and application of the first and second coatings when forming multilayer coatings by a wet-on-wet method.

[0016] Furthermore, while silicone-based defoamers, as described in Patent Document 3, generally exhibit excellent defoaming properties due to their extremely low surface tension, they can also become a major cause of pinholes or hinder topcoatability due to the exudation of silicone components into the coating surface. Even if these adverse effects cannot be confirmed in the short term through laboratory-scale testing or actual coating processes, a single malfunction in mass production could result in significant losses. Therefore, silicone-based materials are generally avoided in coatings used in applications where a good appearance is crucial, in multi-layer coating systems, and in large-scale coating systems such as production line coatings. Silicone-based defoamers are also avoided as surface conditioners.

[0017] Therefore, the present invention has been made in view of the above circumstances, and its object is to provide a surface modifier, an aqueous coating composition containing the surface modifier, an article coated by a coating agent containing the surface modifier, and a method for forming a multilayer coating film using an aqueous coating containing the surface modifier, wherein the surface modifier can prevent air bubbles from being entangled during the manufacture and application of the coating, and can prevent solvent bubbles generated when forming a multilayer coating film by wet-on-wet method, and does not hinder topcoatability.

[0018] Methods for solving problems

[0019] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and found that a surface modifier for water-based coatings can be provided. Based on this insight, the present invention was completed: by adding a polymer having a specific range of SP values ​​and weight-average molecular weight and having at least three repeating units, as well as organic solid particles as components of the surface modifier, it is possible to prevent solvent bubbles generated when forming multilayer coatings by wet-on-wet method, without hindering the topcoatability.

[0020] That is, the present invention is a surface modifier for use in water-based coatings, characterized in that it comprises: a polymer (A) having an SP value of 6 to 12, a weight-average molecular weight of 200 to 1,000,000, and having at least three repeating units; and organic solid particles (B) which are in a solid state in the surface modifier at 25°C.

[0021] In one embodiment of the present invention, the polymer (A) may be one or more polymers selected from the group consisting of polyvinyl alkyl ethers, polybutadiene, polybutene, polyalphaolefins, poly(meth)acrylates, copolymers of dicarboxylic acid esters, polyvinyl fatty acid esters, polyalkylene glycols and their derivatives, polyamides, polyglycerol fatty acid esters and polyesters.

[0022] In another embodiment of the invention, the organic solid particles (B) may be one or more solid particles selected from the group consisting of amides, ureas, polyethylene, oxidized polyethylene, acid-modified polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, polypropylene, acid-modified polypropylene, and hydrogenated castor oil. In this case, the amide may be a fatty acid diamide obtained by reacting fatty acids with diamines, wherein the fatty acids are selected from the group consisting of alkyl fatty acids and hydroxy fatty acids, and contain at least one hydroxy fatty acid, and the diamines contain one or more diamines selected from the group consisting of alkylene diamines having 2 to 6 carbon atoms and m-phenylenediamine.

[0023] In another embodiment of the present invention, the aspect ratio of the organic solid microparticles (B) crystals may be 1.1 to 100.

[0024] In another embodiment of the present invention, the mode diameter of the organic solid particles (B) may be 0.1 to 150 μm.

[0025] In another embodiment of the invention, the surface conditioner may further comprise an organic medium (C) that is liquid at 25°C, excluding water, and the organic medium (C) has 0 to 2 repeating units. In this case, the organic medium (C) may be one or more selected from the group consisting of hydrocarbon oils, alcohols, diol ethers, diol esters, and polyol fatty acid esters.

[0026] Alternatively, based on other viewpoints, the present invention is a water-based coating composition comprising the above-mentioned surface conditioner and water-based resin.

[0027] Alternatively, the present invention, based on another perspective, is an article coated with a coating agent containing the aforementioned surface conditioning agent.

[0028] In addition, based on another viewpoint, the present invention is a method for forming a multilayer coating film, which includes the following film-forming process: after applying at least two or more water-based coatings sequentially to the surface of a substrate by wet-on-wet contact, the water-based coatings applied to the substrate are simultaneously heated and cured to form at least two or more coating films, wherein at least one of the two or more water-based coatings contains the aforementioned surface modifier.

[0029] In one embodiment of the present invention, in the film-forming process, as two or more water-based coatings, a first water-based coating containing coloring pigments and a second water-based coating containing glossy material pigments are used. At least one of the first water-based coating and the second water-based coating contains the surface conditioning agent. In the film-forming process, after the first water-based coating, the second water-based coating and the varnish coating are applied in sequence by wet-on-wet application, the first water-based coating, the second water-based coating and the varnish coating are simultaneously heated and cured, thereby forming a first water-based resin coating film, a second water-based resin coating film and a varnish coating film layered sequentially from the side of the coated object on the surface of the object.

[0030] Invention Effects

[0031] According to the present invention, a surface modifier, an aqueous coating composition containing the surface modifier, an article coated with a coating agent containing the surface modifier, and a method for forming a multilayer coating film using an aqueous coating containing the surface modifier are provided. The surface modifier contains specific polymers and organic solid particles as components of the surface modifier, thereby preventing solvent bubbles generated when forming a multilayer coating film by wet-on-wet method, and not hindering topcoatability when forming a multilayer coating film. Detailed Implementation

[0032] The preferred embodiments of the present invention will now be described in detail.

[0033] [Surface Conditioner]

[0034] The surface conditioner of the present invention is an additive having the following functions: acting as an antifoaming agent to suppress the generation of bubbles during the manufacturing and application of water-based coatings due to the presence of large amounts of water, polarized resins, various surfactants, etc., in the coating; and / or acting as an antifoaming agent to prevent residual bubbles in uncured multilayer coatings from appearing as solvent bubbles in the coating film during heat curing. Furthermore, the surface conditioner of the present invention contains a polymer (A) and organic solid particles (B) as essential components. The polymer (A) has a specific range of SP values ​​and weight-average molecular weights, and has at least three repeating units. Therefore, according to the present invention, a surface conditioner for water-based coatings can be provided that can prevent solvent bubbles generated during the formation of multilayer coatings by wet-on-wet contact, and does not hinder topcoatability during the formation of multilayer coatings. Furthermore, when applying a topcoat such as a clear varnish coating on top of the first and second coatings using a wet-on-wet method and simultaneously baking and curing it, or when recoating after the curing of multiple coatings for repair purposes, including the surface modifier of the present invention in the first and second coatings can prevent defects such as pinholes and deterioration of smoothness in the coating film of the topcoat or recoating. In particular, for clear varnish coatings as topcoats, from the viewpoint of reducing VOCs, there is a tendency to minimize the amount of organic solvents used (high solids content). When the coating has a high solids content, the hydroxyl value becomes high, thus there is a tendency for high polarity and deterioration of wettability relative to the substance. When wettability deteriorates, it is more susceptible to the influence of pinhole substances present in the second coating, thus easily causing coating defects such as pinholes. In such cases, even if the surface modifier of the present invention is included in the first and second coatings, since the surface modifier has the function of not deteriorating the wettability relative to the coating film of the clear varnish to be applied, defects such as pinholes and deterioration of smoothness can be prevented.

[0035] Here, "anti-foaming property" in this invention refers to the ability to prevent the following "solvent bubbles": bubbles generated during the manufacturing and application of the first and second coatings, and bubbles generated during the manufacturing and application of the first and second coatings (entrapped bubbles), which remain in the uncured multilayer coating during the baking and curing process, and "solvent bubbles" generated by entrapped bubbles remaining in the uncured multilayer coating. Furthermore, "topcoatability" in this invention refers to the ability to perform coating without pinholes or the like when a coating is applied to the surface of an already coated film (hereinafter referred to as "lower coating") to form an upper coating (hereinafter referred to as "upper coating") in a coating system consisting of multiple layers; and to prevent peeling or other problems between the upper and lower coatings.

[0036] (Polymer (A))

[0037] The polymer (A) of the present invention is a component for exhibiting defoaming properties and anti-foaming properties, and is a component added to improve the permeability of the surface conditioner to the bubble film. As the polymer (A), a polymer having an SP value of 6 to 12, a weight-average molecular weight of 200 to 1,000,000, and having at least three or more repeating units is used. Here, the polymer (A) in the present invention only needs to have an SP value of 6 to 12, a weight-average molecular weight of 200 to 1,000,000, and three or more repeating units derived from monomers as raw materials for synthesizing the polymer. That is, the polymer (A) of the present invention includes not only polymers as general high molecular compounds, but also trimers, oligomers, etc.

[0038] In addition, as the polymer (A), a polymer having a liquid or rubbery form, or a polymer that is solid at 25°C but is in a liquid state in the liquid medium contained in the composition at 25°C and does not exist in a solid state (that is, a polymer that does not exist as fine particles in the surface conditioner) can be selected. The liquid polymer can also be used alone, and the rubbery and solid polymers are used after being dissolved in the liquid component.

[0039] <SP value · weight-average molecular weight>

[0040] The SP value of the polymer (A) of the present invention is in the range of 6 to 12. When the SP value is less than 6, defects in the appearance of the coating film such as cratering and particles may occur. On the other hand, when the SP value exceeds 12, the defoaming effect is insufficient, and satisfactory defoaming properties and anti-foaming properties may not be obtained. In addition, in order to further improve the defoaming properties and anti-foaming properties, the SP value is preferably 7.5 to 10.5, more preferably 8.0 to 10.0, further preferably 8.0 to 9.5, and most preferably 8.5 to 9.5.

[0041] As the SP value in the present invention, the value calculated by the Fedors method is used, and the unit is (cal / cm 3 ). The Fedors method is a method for calculating the SP value from the molecular structure, and can calculate the SP value from the relationship between the cohesive energy (cal / mol) of each atomic group and the molar molecular volume (cm 1 / 2 / mol). 3 / mol).

[0042] Furthermore, the weight-average molecular weight of the polymer (A) of the present invention is in the range of 200 to 1,000,000. When the weight-average molecular weight is less than 200, sufficient defoaming and anti-foaming properties cannot be achieved. On the other hand, when the weight-average molecular weight exceeds 1,000,000, it is difficult to uniformly disperse the polymer (A) in the coating, resulting in problems such as pinholes and depressions. In addition, to further improve the defoaming and anti-foaming properties, the weight-average molecular weight is preferably 250 to 1,000,000, more preferably 300 to 300,000, and even more preferably 400 to 20,000.

[0043] The weight-average molecular weight in this invention is a value calculated from a chromatogram determined using gel permeation chromatography (GPC), based on the molecular weight of standard polystyrene.

[0044] <Specific example>

[0045] The polymer (A) of the present invention is a polymer having the above-mentioned SP value and weight-average molecular weight and having at least three repeating units. Here, "polymer having at least three repeating units" refers to a compound or its derivative having a degree of polymerization of 3 or more, with monomer units as repeating units. As polymer (A), for example, one or more polymers selected from the group consisting of polyvinyl alkyl ethers, polybutadiene, polybutene, polyalphaolefins, poly(meth)acrylates, copolymers of dicarboxylic acid esters, polyvinyl fatty acid esters, polyalkylene glycols and their derivatives, polyamides, polyglycerol fatty acid esters, and polyesters can be used.

[0046] The aforementioned polyvinyl alkyl ethers are obtained by polymerizing vinyl ether monomers having alkyl groups having 1 to 18 carbon atoms. Examples of such vinyl ether monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, isononyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, etc., and one or more of these monomers may be selected arbitrarily.

[0047] As polybutadiene, homopolymers and copolymers of 1,3-butadiene (CH2=CH-CH=CH2) or 1,2-butadiene (CH2=C=CH-CH3) can be used. Alternatively, commercially available polybutadiene can also be used. Commercially available polybutadiene includes homopolymers, hydrogenated forms, carboxyl-terminated forms, and hydroxyl-terminated forms. One or more of these polymers can be selected and used.

[0048] As polybutene, homopolymers of 1-butene and copolymers of 1-butene and isobutene can be used. Alternatively, commercially available polybutene can be used. Commercially available polybutene includes copolymers of 1-butene and isobutene, homopolymers of 1-butene, hydrogenated forms, etc. One or more of these polymers can be selected and used.

[0049] Examples of polyalphaolefins include poly(1-hexene), poly(1-octene), poly(1-decene), poly(1-dodecene), ethylene-propylene copolymers, etc., and one or more of them can be selected arbitrarily.

[0050] In addition, examples of poly(meth)acrylate alkyl esters include polymers or copolymers of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, isostearyl methacrylate, oleic acid methacrylate, behenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.

[0051] Examples of copolymers of diesters include polymers or copolymers of maleic acid monoesters or diesters, and polymers or copolymers of fumaric acid monoesters or diesters.

[0052] Polyvinyl fatty acid esters include, for example, polymers or copolymers of vinyl acetate, vinyl pentanoate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl laurate, vinyl palmitate, vinyl octanoate, 2,2-dimethyl vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl undecanoate, and other vinyl fatty acid esters (monomers).

[0053] Examples of polyalkylene glycols and their derivatives include polypropylene glycol, polybutane glycol, polyethylene glycol, propylene glycol, polypropylene glycol monobutyl ether, epoxide addition derivatives of hydrogenated castor oil, as well as polypropylene glycol and polybutane adducts and polyamides that are added to polyols such as glycerol, trimethylolpropane, and sugars.

[0054] In addition to those listed above, polyoxyalkylene glycol derivatives may also include polyoxyalkylene aliphatic ethers, polyoxyalkylene aromatic ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene polyol ethers, polyoxyalkylene alkylamides, polyoxyethylene-polyoxypropylene block copolymers, and polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymers.

[0055] Examples of polyoxyalkylene aliphatic ethers include, for example, polyoxypropylene aliphatic ethers, polyoxyethylene aliphatic ethers, and polyoxyethylene-polyoxypropylene aliphatic ethers. Examples of polyoxyalkylene aromatic ethers include, for example, polyoxypropylene aromatic ethers, polyoxyethylene aromatic ethers, and polyoxyethylene-polyoxypropylene aromatic ethers. Examples of polyoxyalkylene fatty acid esters include, for example, polyoxypropylene fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene-polyoxypropylene fatty acid esters. Examples of polyoxyalkylene polyol ethers include substances formed by adding alkylene oxides such as ethylene oxide, propylene oxide, and butane oxide to polyols such as glycerol, polyglycerol, trimethylolpropane, pentaerythritol, monosaccharides, disaccharides, trisaccharides, oligosaccharides, polysaccharides, sorbitol, and sorbitan anhydride. As a polyoxyethylene-polyoxypropylene block copolymer or a polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer, for example, a copolymer in which the total mass of ethylene oxide blocks within the copolymer molecules is 10% to 50% by mass, more preferably 10% to 20% by mass, and the weight-average molecular weight of the propylene oxide blocks is 700 to 4000, more preferably 3000 to 4000. Within the above range, a liquid-type block copolymer is further preferred.

[0056] Furthermore, copolymers of polyalkylene glycol (meth)acrylates and ethylene fatty acid esters can also be used as polyalkylene glycol derivatives. Examples of such copolymers include copolymers composed of combinations of polyalkylene glycol (meth)acrylates such as methoxy polyethylene glycol (meth)acrylate, stearoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol propylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene glycol propylene glycol di(meth)acrylate with the aforementioned ethylene fatty acid esters.

[0057] Polyamides can be polymers obtained by dehydrating and condensing polycarboxylic acids and polyamines. Dicarboxylic acids, such as those with 4 to 44 carbon atoms, can be used. Examples of such dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and dimer acids. Dimer acids are polymeric fatty acids obtained by polymerizing (dimerizing) unsaturated fatty acids (e.g., unsaturated fatty acids with 18 or 22 carbon atoms) obtained from vegetable oils such as soybean oil, tall oil, linseed oil, and cottonseed oil. Dimer acids with 36 or 44 carbon atoms are commonly available commercially. Tricarboxylic acids, such as those with 4 to 54 carbon atoms, can be used. Examples of such tricarboxylic acids include trimeric acids and pyromellitic acid. Trimeric acids are polymeric fatty acids whose trimeric content is increased through distillation and purification based on dimer acids. Commercially available trimeric acids typically have 54 carbon atoms. As a diamine in polyamines, for example, diamines with 2 to 54 carbon atoms can be used, such as: 1,2-diaminoethane (ethylenediamine: EDA), 1,2-diaminopropane (propylenediamine: PDA), 1,4-diaminobutane (tetramethylenediamine: TMDA), 1,6-diaminohexane (hexamethylenediamine: HMDA), 1,8-diaminooctane (octamethylenediamine: OMDA), trimethylhexamethylenediamine, 1,12-diaminododecane (dodecylmethylenediamine: DMDA), etc., aliphatic diamines; o-phenylenediamine, m-phenylenediamine (MXDA), p-phenylenediamine (PXDA), diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, methylene dichloroaniline, etc., aromatic diamines; piperazine, isophorone diamine, 1,3-diaminomethylcyclohexane, etc., alicyclic diamines. As the triamine, for example, an aliphatic triamine such as diethylenetriamine with 2 to 54 carbon atoms can be used. Furthermore, as the amine used in synthesizing the amide of the present invention, a diamine or triamine derived from a polymeric fatty acid can also be used as a polymeric fatty acid derivative. Examples of such polymeric fatty acid derivatives include dimeric diamine (DDA) as a dimer acid derivative and trimeric triamine (TTA) as a trimeric acid derivative. Dimeric diamine, as a dimer acid derivative, is a substance in which the two terminal carboxyl groups of the aforementioned dimer acid are replaced by primary aminomethyl or amino groups, and commercially available products can be used. Similarly, trimeric triamine, as a trimeric acid derivative, is a substance in which the three terminal carboxyl groups of the aforementioned trimeric acid are replaced by primary aminomethyl or amino groups, and commercially available products can be used.

[0058] Examples of polyglycerol fatty acid esters include polyglycerol caprylate, polyglycerol 2-ethylhexanoate, polyglycerol decanoate, polyglycerol laurate, polyglycerol myristate, polyglycerol stearate, polyglycerol oleate, polyglycerol isostearate, polyglycerol behenate, and polyglycerol condensed ricinoleate. One or more of these can be selected for use.

[0059] Polyesters can be categorized as condensates of hydroxy fatty acids, dimer acids, and other polymers of fatty acids and diols.

[0060] In the specific examples shown above, in order to improve anti-foaming properties and topcoatability, polyalkylene glycols and their derivatives, polyalkyl acrylates, polyvinyl alkyl ethers, polybutene, polyglycerol fatty acid esters, etc. are preferred.

[0061] <Content>

[0062] When the total mass of all components in the surface conditioner is set to 100% by mass, the content of the polymer (A) is preferably 10% to 99.9% by mass. By setting the content of polymer (A) to 10% to 99.9% by mass, sufficient defoaming and anti-foaming properties can be achieved. To further improve defoaming and anti-foaming properties, it is even more preferable to set the content of polymer (A) to 20% to 70% by mass.

[0063] (Organic solid particles (B))

[0064] The organic solid microparticles (B) of the present invention are components used to exert defoaming and anti-foaming properties. They are added to improve the defoaming effect and anti-foaming properties of surface modifiers. The organic solid microparticles (B) are selected from materials with a melting point of at least 50°C and are solid particles at 25°C. Such organic solid microparticles (B) are solid in the liquid medium contained in the composition at 25°C. Furthermore, the organic solid microparticles (B) are selected from particles that do not dissolve in surface modifiers at 25°C, or whose primary particle shape does not change.

[0065] Here, "primary particles" in this invention refers to isolated particles that will not be broken down into smaller particles even when diluted with a specified medium. Furthermore, as a method for investigating whether the organic solid particles (B) are in a solid state in the liquid medium contained in the surface conditioner at 25°C, known qualitative methods can be used for determination. For example, methods such as dispersing the organic solid particles in the liquid medium contained in the composition at a mass percentage not exceeding 50%, separating the non-flowing components from the dispersion by filtration or centrifugation, and then determining their melting points can be employed.

[0066] <Particle Shape>

[0067] Organic solid particles (B) are solid particles composed of organic compounds. Furthermore, when measuring their particle size distribution using methods such as laser diffraction / scattering, the particle size preferably has a peak value in the range of 0.1 to 150 μm. That is, the peak particle size (also called the "mode diameter") of the organic solid particles (B) is preferably in the range of 0.1 to 150 μm, more preferably 2 to 150 μm, and even more preferably 2 to 50 μm. By ensuring that the peak particle size of the organic solid particles (B) is within the above range, a surface conditioner with particularly excellent anti-foaming properties can be obtained.

[0068] Regarding particle shape, particles with uneven surfaces are preferred over perfectly spherical particles; porous particles and particles with spiky protrusions are even more desirable. Such particles can be, for example, clusters of particles whose primary particles have an aspect ratio of 1.1 to 100. Especially when using such clusters, a mixture of a defoaming liquid component (e.g., polymer (A)) and an organic medium (C) can be suitably maintained on the particle surface, resulting in particularly excellent anti-foaming properties. The aspect ratio of the primary particles can be controlled by appropriately adjusting the medium used for dissolution and precipitation, as well as the temperature at which the particles precipitate and crystallize during the production of the organic solid particles (B), and further adjusting the time required to maintain the temperature for particle precipitation and crystallization as needed.

[0069] When the aspect ratio is less than 1.1, it is difficult to form clusters, making it difficult to maintain the defoaming properties of the liquid component, and thus difficult to obtain excellent anti-foaming properties. On the other hand, when the aspect ratio exceeds 100, the gaps between the clusters become too large, making it difficult to maintain the defoaming properties of the liquid component, and in this case, it is also difficult to obtain excellent anti-foaming properties. From the viewpoint of further improving anti-foaming properties, the more preferred range of the above-mentioned aspect ratio is 1.5 to 50, the further preferred range is 1.5 to 30, and the most preferred range is 1.5 to 11.0.

[0070] The aspect ratio of the aforementioned primary particles can be calculated by measuring the shape of isolated particles during TEM or SEM observation. Specifically, it can be calculated, for example, by the following method: The particles to be tested are diluted and suspended in a suitable volatile organic solvent that will not dissolve the particles. This suspension is then dropped onto a TEM viewing grid or a SEM sample holder, and allowed to dry to prepare an observation sample. At this time, the type of solvent and dilution amount are adjusted appropriately to isolate the particles. Using a TEM or SEM, the prepared sample is set to a magnification that facilitates observation of the isolated particles, and the shape of the isolated particles is confirmed. If the particle shape can be considered elliptical, the distance between the minor axis and the major axis is measured separately, and the value of major axis / minor axis is calculated. The same measurement is performed on at least 10 particles, and the average value is taken as the aspect ratio of that particle. If the particles are fibrous and difficult to consider as elliptical, the central value of the measured fiber width is taken as the fiber width, and the value of fiber length / fiber width is calculated. The same measurement is performed on at least 10 isolated fibrous particles, and the average value is taken as the aspect ratio of that fibrous particle.

[0071] <Specific example>

[0072] As organic solid particles (B), there are no particular limitations, and for example, one or more of the following solid particles may be used: amide, urea, polyethylene, oxidized polyethylene, acid-modified polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, polypropylene, acid-modified polypropylene and hydrogenated castor oil.

[0073] Amides are obtained, for example, by condensing fatty acids with amines. The conditions of the condensation reaction (reaction temperature, proportions of each component, etc.) can be appropriately set using known methods. For example, fatty acids and amines are added as raw materials to a reaction vessel such as a four-necked flask, and the raw materials are stirred under an inert gas atmosphere (e.g., under a nitrogen flow) to form a mixture. Then, the mixture of raw materials is heated, and a condensation reaction is carried out at 150°C to 200°C for 2 to 10 hours, thereby synthesizing fatty acid amides. Monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids can be used as fatty acids, and monoamines, diamines, and triamines can be used as amines.

[0074] Examples of monocarboxylic acids that can be used include: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated castor oil fatty acids (12-hydroxystearic acid (hereinafter referred to as "12-HSA") obtained by saponification and decomposition of hydrogenated castor oil, and other fatty acids containing hydroxyl groups), arachidic acid, behenic acid (docosahexaenoic acid), and other saturated aliphatic monocarboxylic acids; as well as oleic acid, linoleic acid, ricinoleic acid, linolenic acid, eicosenoic acid, erucic acid, and mixed fatty acids obtained from natural oils (talc fatty acids, rice bran fatty acids, soybean oil fatty acids, tallow fatty acids, etc.), and other unsaturated aliphatic monocarboxylic acids. Among these monocarboxylic acids, in order to improve the defoaming and anti-foaming properties of water-based coatings, it is preferable that the monocarboxylic acid contains at least a hydroxy fatty acid such as 12-HSA. That is, as the amide used as the organic solid microparticle (B) of the present invention, it is preferable that at least one of the fatty acids is a hydroxy fatty acid.

[0075] As a dicarboxylic acid, for example, dicarboxylic acids with 4 to 44 carbon atoms can be used. Examples of such dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and dimer acids.

[0076] As a tricarboxylic acid, for example, tricarboxylic acids with 4 to 54 carbon atoms can be used. Examples of such tricarboxylic acids include trimeric acids and pyromellitic acid.

[0077] Examples of monoamines include ethylamine, monoethanolamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, decylamine, laurylamine, myristamine, cetylamine, stearylamine, 12-hydroxystearylamine, behenamine, etc.

[0078] As diamines, for example, diamines with 2 to 54 carbon atoms such as: 1,2-diaminoethane (ethylenediamine: EDA), 1,2-diaminopropane (propylenediamine: PDA), 1,4-diaminobutane (tetramethylenediamine: TMDA), 1,6-diaminohexane (hexamethylenediamine: HMDA), 1,8-diaminooctane (octamethylenediamine: OMDA), trimethylhexamethylenediamine, 1,12-diaminododecane (dodecylmethylenediamine: DMDA), etc., aliphatic diamines; o-phenylenediamine, m-phenylenediamine (MXDA), p-phenylenediamine (PXDA), diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, methylene dichloroaniline, etc., aromatic diamines; piperazine, isophorone diamine, 1,3-diaminomethylcyclohexane, etc., alicyclic diamines.

[0079] As a triamine, for example, triamines with 2 to 54 carbon atoms, such as aliphatic triamines like diethylenetriamine, can be used.

[0080] Furthermore, the amine used in synthesizing the amide of the present invention can also be a diamine or triamine derived from a polymeric fatty acid, which is a derivative of the polymeric fatty acid. Examples of such polymeric fatty acid derivatives include dimeric diamine (DDA) as a dimer acid derivative and trimeric triamine (TTA) as a trimer acid derivative.

[0081] One or more compounds may be selected as the fatty acid and amine compounds mentioned above.

[0082] From the viewpoint of further improving anti-foaming properties, the amide is preferably a diamide. A diamide can be obtained by reacting a fatty acid with a diamine or by reacting a monoamine with a dicarboxylic acid. Among the diamides, fatty acid diamides obtained by reacting the following fatty acids with the following diamines are particularly preferred. The fatty acids used in the synthesis of this fatty acid diamide are selected from the group consisting of alkyl fatty acids (saturated fatty acids) and hydroxy fatty acids, and contain at least one or more hydroxy fatty acids. Furthermore, the diamines used in the synthesis of the above-mentioned fatty acid diamides contain one or more diamines selected from the group consisting of alkylene diamines having 2 to 6 carbon atoms and m-phenylenediamine. In these fatty acid diamides, by using ethylene bis(12-hydroxystearic acid) diamide, 1,4-butane bis(12-hydroxystearic acid) diamide, hexamethylene bis(12-hydroxystearic acid) diamide, etc., as organic solid particles (B), waterborne coatings containing the surface modifier of the present invention can exhibit particularly excellent anti-foaming properties.

[0083] Ureas are polymers, oligomers, diureas, or monoureas containing urea bonds, obtained by reacting isocyanate compounds with amine compounds. One or more of the isocyanate and amine compounds can be selected from the following compounds, respectively.

[0084] Examples of isocyanate compounds include aromatic monoisocyanates, aliphatic monoisocyanates, alicyclic monoisocyanates, compounds in forms that render these monoisocyanates non-volatile and reduce their toxicity, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, compounds in forms that render these diisocyanates non-volatile and reduce their toxicity, adducts of these diisocyanates such as biuret, diketone, isocyanurate, and urethane, and low-molecular-weight polyurethane prepolymers. Examples of aromatic diisocyanates include toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), phenylenediethylene diisocyanate (XDI), and isophthalimide diisocyanate (MXDI). Examples of aliphatic diisocyanates include hexamethylene diisocyanate (HDI). Examples of alicyclic diisocyanates include isophorone diisocyanate (IPDI) and hydrogenated MDI. Commercially available products can be used as polyisocyanates. Examples of commercially available products include Aquanate 130, Aquanate 140, Aquanate 200 and Aquanate 210 (manufactured by Tosoh Corporation), Bayhydur 304, Bayhydur XP-2655, Bayhydur 401-70, Bayhydur 3100 (manufactured by Sumitomo Chemical Covestro Polyurethanes Co., Ltd.), Burnock DNW-5000, Burnock DNW-5500, Burnock DNW-6000 (manufactured by DIC Corporation), Resamine D-1063, Resamine D-2040 (manufactured by Dainippon Seika Co., Ltd.), etc.

[0085] Amine compounds include monoamines or polyamines.

[0086] Examples of monoamines that can be used include aliphatic monoamines, alicyclic monoamines, aromatic monoamines, and alkanolamines. Examples of aliphatic monoamines include alkyl monoamines and other aliphatic monoamines. Examples of alkyl monoamines include octylamine, dodecylamine, octadecylamine, and octadeceneamine. Examples of alicyclic monoamines include cyclohexylamine. Examples of aromatic monoamines include aniline and toluidine. Examples of alkanolamines include ethanolamine, 2-amino-2-methyl-1-propanol, and 12-hydroxystearylamine.

[0087] Examples of polyamines include aliphatic polyamines, alicyclic polyamines, and aromatic polyamines. Examples of aliphatic polyamines include alkylene polyamines, polyalkylene polyamines, and other aliphatic polyamines. Examples of alkylene polyamines include diaminomethane (methylenediamine), 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane. Examples of polyalkylene polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexamethylenetetramine. Other aliphatic polyamines include tetra(aminomethyl)methane, tetra(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, and polyethyleneimine. Alicyclic polyamines include 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-isopropylidenebis(cyclohexylamine), norbornenediamine, bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, and menthanediamine (MDA). Examples of aromatic polyamines include bis(cyanoethyl)diethylenetriamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(aminomethyl)naphthalene, and bis(aminoethyl)naphthalene.

[0088] Oxidized polyethylene is a wax obtained by oxidizing polyethylene and introducing polar groups. Additionally, acid-modified polyethylene and acid-modified polypropylene are obtained by grafting unsaturated carboxylic acids or their anhydrides onto polyethylene and polypropylene, respectively. Ethylene-vinyl acetate copolymers and ethylene-(meth)acrylic acid copolymers are copolymers of ethylene with polymeric monomers such as vinyl acetate and (meth)acrylic acid.

[0089] Hydrogenated castor oil (also known as "hardened castor oil") is a triglyceride of saturated fatty acids obtained by hydrogenating castor oil. Commercially available hydrogenated castor oils include C-Wax (manufactured by Kokura Synthetic Industries, Ltd.), Kao Wax 85P (manufactured by Kao Corporation), Hydrogenated Castor Oil A (manufactured by Ito Oil Co., Ltd.), and Hydrogenated Castor Oil (manufactured by Yamagata Sangyo Co., Ltd.).

[0090] In addition, as the organic solid particles (B) of the present invention, besides the examples mentioned above, for example, copolymers of poly(meth)acrylate, diacrylates, and copolymers of (meth)acrylate and ethylene fatty acid esters (wherein, they are in a solid state in the surface conditioner at 25°C (i.e., not belonging to polymer (A))) may also be used.

[0091] In the specific examples shown above, in order to improve defoaming and anti-foaming properties, it is preferable to use ethylene bis(12-hydroxystearic acid) diamide, 1,4-butane bis(12-hydroxystearic acid) diamide, hexamethylene bis(12-hydroxystearic acid) diamide, oxidized polyethylene, etc.

[0092] <Content>

[0093] When the total mass of all components in the surface modifier is set to 100% by mass, the content of the aforementioned organic solid particles (B) is preferably 0.1% to 10% by mass. By setting the content of organic solid particles (B) to 0.1% to 10% by mass, sufficient defoaming and anti-foaming properties can be achieved. To further improve the appearance of the coating film obtained from the waterborne coating composition containing the surface modifier, it is even more preferable to set the content of organic solid particles (B) to 1% to 5% by mass.

[0094] (Organic medium (C))

[0095] The organic medium (C) of the present invention is a component used to exert defoaming and anti-foaming properties together with the polymer (A) described above, and is a component added to improve the diffusion of the surface conditioner in the bubble film.

[0096] Liquidity

[0097] As the organic medium (C), any medium other than water that is liquid at 25°C can be used. Furthermore, as the organic medium (C), an organic medium having 0 to 2 repeating units is selected. That is, the organic medium (C) is a compound or its derivative that does not have repeating units, or a compound or its derivative that has one or two repeating units. By using such a medium, the diffusivity of the surface modifier of the present invention in the bubble film can be improved.

[0098] <Specific example>

[0099] As an organic medium (C), one or more of the group consisting of hydrocarbon oils, alcohols, diol ethers, diol esters and polyol fatty acid esters (none of which are included in the polymer (A)) may be suitably used.

[0100] As a hydrocarbon oil, for example, it can be selected from the general formula C n H 2n+2 The terms represent n-alkanes and isoalkanes, as well as those derived from C. n H 2n It represents one or more of the cycloalkanes.

[0101] As derived from the above general formula C n H 2n+2 Examples of n-alkanes include n-hexane, n-heptane, n-octane, n-decane, n-dodecane, and liquid alkanes. Furthermore, commercially available n-alkane-based mixed solvents can also be used. Commercially available n-alkane-based mixed solvents include, for example, Solvent L (ENEOS Corporation). One or more of these can be selected and used.

[0102] As derived from the above general formula C n H 2n+2 Examples of isoparaffins that can be represented include isohexane, isooctane, isododecane, and isohexadecane. Furthermore, commercially available mixed solvents based on isoparaffins can also be used. Other commercially available mixed solvents based on isoparaffins include IP Solvent, Merveille 30 (manufactured by Idemitsu Kosan Co., Ltd.), ShellSol T series (manufactured by Shell Chemicals), and Isopar series (manufactured by ExxonMobil Corporation). One or more of these can be selected and used.

[0103] As derived from the above general formula C n H 2n As an example of the cycloalkanes mentioned, commercially available cycloalkane solvents can be used. Commercially available cycloalkane solvents include, for example, methylcyclohexane, ethylcyclohexane, SWA Clean 150 (also known as a mixture of C9 and C10 alkylcyclohexanes) (manufactured by Maruzen Petrochemical Co., Ltd.), the Naphthesol series, and the CactusSolvent series (manufactured by ENEOS Co., Ltd.). One or more of these can be selected for use.

[0104] Alternatively, as the organic medium (C), it is also possible to use a mixture of the general formula C used in this invention, which has been mixed from the beginning. n H 2n+2 The terms represent n-alkanes and isoalkanes, as well as those derived from C.n H 2n A solvent that represents at least two or more cycloalkanes and is commercially available. Examples of such solvents include Naphthesol M (a trade name of ENEOS Corporation, representing 70% or more of cycloalkanes / isoalkanes / n-alkanes, representing 5-10% or less of 15%), Isosol 300 (a trade name of ENEOS Corporation), Isosol 400 (a trade name of ENEOS Corporation), EXXSOL D80 (a mixed solvent of alkanes and cycloalkanes, representing ExxonMobil Corporation), EXXSOL D110 (a mixed solvent of alkanes and cycloalkanes, representing ExxonMobil Corporation), EXXSOL D130 (a mixed solvent of alkanes and cycloalkanes, representing ExxonMobil Corporation), and EXXSOL D160 (a mixed solvent of alkanes and cycloalkanes, representing ExxonMobil Corporation). You can choose to use one or more of these.

[0105] Examples of alcohols that can be used include ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, 2-ethylhexanol, isostearyl alcohol, oleyl alcohol, and dodecyl alcohol esters. Examples of diol ethers that can be used include ethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. Examples of diol esters that can be used include propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate. Examples of polyol fatty acid esters that can be used include glycerol fatty acid esters, sorbitan fatty acid esters, trimethylolpropane fatty acid esters, and sucrose fatty acid esters.

[0106] Furthermore, as an organic medium (C), in addition to the above, the following can also be used: aromatic solvents such as xylene and toluene; ketone solvents such as methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and methyl pentyl ketone (MAK: also known as 2-heptanone); ether solvents such as cyclopentyl methyl ether; ester solvents such as acetates and ethyl 3-ethoxypropionate; amide solvents such as dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide; and oils and fats.

[0107] <Content>

[0108] The aforementioned organic medium (C) is not necessarily required to be included in the surface conditioner of the present invention. However, when the organic medium (C) is included, its content is preferably 0.5% to 95% by mass when the total mass of all components in the surface conditioner is set to 100% by mass. By setting the content of the organic medium (C) to 0.5% to 95% by mass, sufficient defoaming and anti-foaming properties can be achieved. To further improve the defoaming and anti-foaming properties, it is even more preferable to set the content of the organic medium (C) to 5% to 80% by mass.

[0109] (Any other ingredients)

[0110] To impart other functions, the surface modifier of the present invention may contain other components besides those shown above and other than organosilicon compounds, without impairing the characteristics of the present invention. For example, in order to uniformly dissolve or disperse the above components (A) to (C), or to improve the leveling properties, uniformity, etc., of the coating to which the surface modifier has been added, solvents, surfactants, amphiphilic compounds, or coating additives other than surface modifiers may be added. Specifically, examples include water, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, leveling agents, dispersants, etc. (but not included in the above polymer (A), organic solid particles (B), and organic media (C)).

[0111] (Components not included in the surface conditioner of this invention)

[0112] The surface conditioner of the present invention preferably does not contain organosilicon compounds (synthetic polymers having a backbone based on siloxane bonds). When the surface conditioner of the present invention contains organosilicon compounds, the leaching of the organosilicon components to the coating surface may become a major cause of pinholes or hinder topcoatability. Thus, when the surface conditioner of the present invention contains organosilicon compounds, it may adversely affect the appearance of the coating film applied using water-based paints containing such surface conditioners. Therefore, in the preferred embodiment of the surface conditioner of the present invention, it does not contain organosilicon compounds.

[0113] (Form of surface modifier)

[0114] Specifically, the forms of the surface modifier of the present invention can be listed as suspensions containing organic solid particles (B), oily suspensions dispersed in a water-based medium (O (suspension) / W type emulsion), water-based droplets dispersed in an oily suspension (W / O (suspension) type emulsion), and forms in which the above-mentioned W / O (suspension) type emulsion is further dispersed in a water-based medium (W / O (suspension) / W type emulsion), etc.

[0115] (Manufacturing method of surface conditioner)

[0116] There are no particular limitations on the method for manufacturing a surface conditioner containing the above-mentioned components. However, to facilitate the manufacture of a uniformly dispersed surface conditioner and to ensure excellent defoaming and anti-foaming properties, it is desirable to prepare a pre-dispersion of organic solid particles (B) (hereinafter referred to as "particle pre-dispersion") and add it to the mixture of the components. It is desirable to add the particle pre-dispersion while stirring using a disperser or similar device. The stirring speed and temperature can be appropriately set according to the dispersion state of the organic solid particles (B). There are no particular limitations on the method for preparing the particle pre-dispersion; methods known to those skilled in the art can be used. As such a method, for example, the following methods are known: The organic solid particles (B) to be formed into microparticles (B) are melted at a specified temperature, and the molten liquid is allowed to flow into a container pre-filled with polymer (A) and / or organic medium (C), thereby causing the microparticles (B) to precipitate while cooling in the polymer (A) and / or organic medium (C); The container pre-filled with organic solid (B'), polymer (A) and / or organic medium (C) is melted at a specified temperature, and the polymer (A) and / or organic medium (C) are allowed to flow into the molten liquid, thereby causing the microparticles (B) to precipitate while cooling; The microparticles (B) pre-adjusted to a specified particle size are heated while suspended in the polymer (A) and / or organic medium (C).

[0117] (Uses of surface conditioners)

[0118] The surface modifier of the present invention is suitable for use in water-based coatings without particular limitation, and is particularly suitable for applications requiring a good appearance and for coating systems based on multi-layer films. For example, when using the surface modifier of the present invention, it imparts sufficient defoaming properties during the manufacture, application, and drying of water-based base coatings for automobiles, water-based intermediate coatings for automobiles, water-based coatings for high-end furniture, floor coatings, interior and exterior wall coatings for buildings, anti-corrosion coatings, and household appliances, and can prevent coating defects such as solvent bubbles from forming during the baking process. In particular, it can effectively prevent the formation of solvent bubbles when forming multi-layer films through wet-on-wet coating. In addition, the surface modifier of the present invention is also suitable for use in situations where coating raw materials that are difficult to disperse in water are used, and in situations where coatings are recycled to prevent the sedimentation and separation of components in the coating. Furthermore, as described above, the surface modifier of the present invention has excellent defoaming, anti-foaming, and topcoatability properties, therefore, the surface modifier of the present invention is particularly preferred as a defoamer or anti-foaming agent for water-based coatings. That is, the surface modifier of the present invention is preferably a defoamer or anti-foaming agent.

[0119] (The mechanism of effect)

[0120] Those skilled in the art are familiar with the defoaming mechanism of defoaming droplets and hydrophobic microparticles. For example, it will be described as follows: Defoaming droplets and hydrophobic microparticles penetrate the bubble film. As the thickness of the bubble film decreases with the drainage within the bubble film, the defoaming components contained in the defoaming droplets and hydrophobic microparticles penetrate the bubble film. Subsequently, due to the high hydrophobicity of the penetrating defoaming components, water attempts to avoid the defoaming components, resulting in bubble bursting.

[0121] Furthermore, the formation mechanism of solvent bubbles is believed to be as follows: During coating, air bubbles entrained in the uncured coating film increase in diameter during the baking and curing process due to the intrusion of volatile solvents from the coating. Eventually, the bubble diameter grows to be equal to or greater than the film thickness. As a result, the presence of unbroken bubbles remaining in the cured coating film, as well as traces of broken bubbles remaining in the cured coating film, constitutes a coating defect known as a "solvent bubble." Therefore, the size of the solvent bubble is proportional to the film thickness; the thicker the film, the larger the solvent bubble.

[0122] To prevent the formation of such solvent bubbles, when using water-based coatings, it is necessary to break the entrained bubbles as much as possible during solidification, preheating, and baking. However, during solidification and preheating, the coating system is in a state of transition from an aqueous phase to a non-aqueous phase. In order to break the entrained bubbles during this phase transition, polymers with appropriate polarity ranges (SP values) and weight-average molecular weight ranges are required.

[0123] Furthermore, while defoaming effects can be expected during the solidification, preheating, and baking processes when forming a single-layer coating, multi-layer coatings are formed by wet-on-wet contact. The top layer is applied before the bottom layer has cured, and the multiple uncured layers are simultaneously baked and cured. Therefore, it is crucial to completely remove any entrapped air bubbles during solidification and preheating. Consequently, conventional surface modifiers (defoamers, anti-foaming agents) containing only polymer components cannot achieve sufficient defoaming effects. In contrast, while low-polarity polymers such as silicone compounds offer higher defoaming performance, they hinder topcoatability, thus limiting their use in multi-layer coating formation.

[0124] Therefore, the surface modifier of the present invention uses the aforementioned polymer (A) and organic solid particles (B) as essential components. It is believed that, according to such a surface modifier, by using a polymer (A) having a specified range of SP values ​​and weight-average molecular weights, and using organic solid particles (B) with a high affinity for the polymer (A), the defoaming effect of entrained air bubbles is excellent even during the phase transfer process of the coating system, and even when forming a multilayer coating film by wet-on-wet contact, entrained air bubbles can be removed only during solidification and preheating, thereby significantly improving the defoaming effect of the polymer component. To further improve the affinity between the organic solid particles and the polymer component, it is further desirable that the shape of the organic solid particles (B) has specific characteristics. Specifically, it is believed that the organic solid particles (B) have particularly excellent affinity for the polymer (A) when (1) they are porous particles, (2) they are particles with uneven surfaces, or (3) they are microcrystalline clusters with a specific aspect ratio.

[0125] [Water-based coating composition]

[0126] The waterborne coating composition of the present invention contains the above-mentioned surface conditioner and waterborne resin as essential components. Furthermore, the waterborne coating composition of the present invention may also contain other coating raw materials such as diluents, pigments, dispersants, lubricants, emulsifiers, viscosity modifiers, film-forming aids, and pH adjusters as optional components.

[0127] (Content of surface conditioner)

[0128] The content of the surface modifier of the present invention varies depending on the type of waterborne resin used as a binder in the waterborne coating composition, the formulation of the pigment, etc., and is generally preferably 0.1% to 5% by mass relative to the waterborne coating composition, more preferably 0.5% to 2% by mass. When the content of the surface modifier is less than 0.1% by mass, the effects of adding the surface modifier of the present invention, such as defoaming and anti-foaming properties, may not be fully realized. On the other hand, when the content of the surface modifier exceeds 5% by mass, it may lead to poor interlayer adhesion during repeated coating, uneven coating in the topcoat (upper layer) film, or poor water resistance of the dried film, and is therefore not preferred.

[0129] (Water-based resin)

[0130] The aqueous resin included as a binder in the aqueous coating composition of the present invention is a resin component dispersed in a water-based medium. Examples of resin components include acrylic resins, acrylic / silicone resins, alkyd resins, polyester resins, urethane resins, epoxy resins, silicone resins, and fluororesins. The aqueous resin can be classified according to its dispersion form as water-soluble, colloidal dispersion, or emulsion; any form is acceptable. These resins can be, for example, heat-curing, UV-curing, electron beam-curing, oxidative-curing, photocationic-curing, peroxide-curing, or resins that cure through a chemical reaction in the presence or absence of a catalyst. They can also be resins with high glass transition temperatures that do not undergo a chemical reaction and simply evaporate through a dilution medium to form a film. Furthermore, examples of curing agents include amino resins, melamine resins, isocyanate compounds, blocked isocyanate compounds, silane coupling agents, and epoxy compounds.

[0131] (pigment)

[0132] Examples of pigments include: calcium carbonate (heavy calcium carbonate (GCC), precipitated calcium carbonate (PCC), etc.), barium sulfate, silicon dioxide, aluminum hydroxide, talc, mica, organic fibers, glass powder, etc.; pigments such as titanium dioxide, carbon black, chrome yellow, cadmium yellow, ochre, titanium yellow, zinc chromate, iron oxide red, aluminosilicates, quinacridones, phthalocyanines, anthraquinones, diketopyrrolopyrroles, benzimidazolones, and isoindolinones; and glossy pigments such as metallic pigments and effect pigments (pearl pigments) made by coating metallic pigments with metal oxides such as titanium dioxide. Examples of metallic pigments include aluminum flakes, copper flakes, glass flakes, artificial crystals of alumina (as commercially available products, such as silanes manufactured by Merck (a registered trademark)), mica iron oxide, and mica.

[0133] (Other additives)

[0134] Without impairing its properties or the purpose of the invention, the waterborne coating composition of the present invention may contain other substances, such as dispersants, lubricants, emulsifiers, viscosity modifiers, dehydrating agents (e.g., silane coupling agents), adhesion promoters, surfactants, curing catalysts, film-forming aids, desiccants, antifouling agents, sensitizers, antioxidants, light stabilizers, ultraviolet absorbers, water-resistant agents, preservatives and mildew inhibitors, leveling agents, flame retardants, antistatic agents, stripping agents, deodorizers, pH adjusters, fragrances, and other additives.

[0135] Here, surfactants are typically used as dispersants to disperse pigments in coatings, wetting agents to improve the wetting and smoothness of pigments, emulsifiers for emulsifying non-aqueous resins, and viscosity modifiers for controlling the flowability of coatings. However, these surfactants can generate unwanted bubbles during the manufacturing or application of water-based coatings. By including the surface modifier of this invention in the water-based coating composition, the generation and residue of bubbles can be suppressed, or solvent bubbles can be prevented when forming multilayer coatings through wet-on-wet application. As a result, a coating with an excellent appearance can be formed, and topcoatability is not hindered.

[0136] (Method for manufacturing water-based coating compositions)

[0137] The waterborne coating composition of the present invention can be manufactured according to known methods for manufacturing waterborne coatings. For example, components other than the surface modifier and pigment are mixed while stirring in a water-based medium such as ion-exchanged water, and the pH is adjusted as needed to prepare a varnish coating. By adding the surface modifier and pigment to this varnish coating and dispersing them within the varnish coating, a waterborne coating composition can be manufactured.

[0138] Furthermore, the timing for adding the surface modifier of the present invention to the water-based coating can be during the pigment mixing process as described above, or it can be added after the water-based coating is manufactured, or it can be added after further preparation into a masterbatch. Additionally, the equipment used for dispersing the surface modifier and pigment can be any equipment commonly used in the manufacture of water-based coatings. Moreover, there are no particular limitations on the stirring speed and stirring time during the dispersion of the surface modifier and pigment; they can be appropriately set while monitoring the dispersion state of the surface modifier and pigment.

[0139] (Uses of water-based coating compositions)

[0140] The waterborne coating composition of the present invention is suitable for applications requiring a good appearance and for multi-layer coating systems (particularly in cases where multi-layer coatings are formed by wet-on-wet application). Examples of such applications include, for instance, coatings for automotive materials, coatings for high-end furniture materials, floor coatings, interior and exterior wall coatings, anti-corrosion coatings, and coatings for household appliances. Furthermore, the waterborne coating composition of the present invention is also preferably suitable for applications using coating raw materials that are difficult to disperse in water, and for applications where the coating is recycled to prevent sedimentation and separation of components.

[0141] [thing]

[0142] The article of the present invention is an article in which the surface of a substrate, which is a material to be coated, is coated with a coating agent containing the aforementioned surface conditioner. That is, the article of the present invention consists of a substrate and a coating film obtained by coating its surface with a coating agent.

[0143] (Substrate)

[0144] There are no particular limitations on the substrates used for the articles of this invention. Examples of substrates include those made of metal, plastic, wood, rubber, glass, stone, cement, mortar, paper, non-woven fabric, cloth, and ceramics.

[0145] (Coating)

[0146] The coating film of the article of the present invention is obtained, for example, by applying the above-described aqueous coating composition to the above-described substrate and then curing it. The coating film formed on the surface of the substrate can be a single layer or a coating film composed of multiple layers (multilayer coating film). The aqueous coating composition containing the surface conditioner of the present invention has excellent defoaming and anti-foaming properties. Therefore, even when using the aqueous coating composition in applications requiring extremely high appearance and topcoatability, a satisfactory appearance of the coating film can be obtained without hindering topcoatability.

[0147] (Coating agent)

[0148] The coating agent of the present invention used as a coating agent for the above-mentioned substrate can be exemplified by, for example, the above-mentioned water-based coating composition.

[0149] (The method of manufacturing the item)

[0150] The articles of the present invention can be manufactured by applying a coating agent, such as the water-based coating composition of the present invention, to the aforementioned substrate, followed by drying and curing. The coating method is not particularly limited, and examples include spraying, roller coating, brush coating, curtain coating, rod coating, doctor blade coating, slot coating, dip coating, and flow coating. The curing method is also not particularly limited, and examples include room temperature curing, heat curing, and ultraviolet curing.

[0151] Furthermore, in cases where a multilayer coating film (multilayer coating) is formed on the article of the present invention, it may include, for example, a first coating film obtained by applying the aqueous coating composition of the present invention to a substrate, and a second coating film stacked on all or part of the surface of the first coating film. The second coating used to form the second coating film may sometimes be the same coating used in the first coating film, and sometimes a different coating is used. Additionally, when forming a multilayer coating film, sometimes the second coating is applied after the first coating has completely dried or cured, and sometimes it is applied in a state where the first coating is not completely dried or cured, within a range where the second coating does not disturb it. The aqueous coating composition containing the surface conditioner of the present invention has excellent topcoatability; therefore, even when the aqueous coating composition is used for applications requiring extremely good appearance and topcoatability, the interlayer adhesion between the coating film obtained from the aqueous coating composition of the present invention and the coating film applied over it is excellent.

[0152] In the case of forming a multilayer coating on the article of the present invention, the multilayer coating is formed, for example, by coating all or part of the surface of a coating obtained by curing a first coating containing the surface modifier of the present invention with a second coating. Alternatively, the first water-based coating containing the surface modifier of the present invention may not be cured, but the second coating may be applied by a wet-on-wet method, and then the first and second coatings may be cured simultaneously.

[0153] In addition, there are no particular restrictions on the application and curing methods of the second coating; the same methods as those described above can be used.

[0154] (The purpose of the item)

[0155] The articles of the present invention are suitable for applications requiring a good appearance, and for coating systems based on multi-layer coatings (especially in cases where multi-layer coatings are formed by wet-on-wet methods). Examples of such applications include automotive parts, high-end furniture, and home appliances.

[0156] [Methods for forming multilayer coatings]

[0157] The method for forming a multilayer coating of the present invention is as follows: At least two types of water-based coatings are sequentially applied to the surface of an object using a wet-on-wet method, and then the water-based coatings applied to the object are simultaneously heated and cured to form at least two layers of coating. In this case, at least one of the two or more water-based coatings is a water-based coating composition containing the surface modifier of the present invention described above.

[0158] The substrate of the article of the present invention can be used as the object to be coated.

[0159] As one or more of the above-mentioned water-based coatings, for example, a first water-based coating containing the above-mentioned coloring pigment (equivalent to "first coating" in this specification), a second water-based coating containing the above-mentioned gloss material pigment (equivalent to "second coating" in this specification), and a varnish coating can be used. In this case, as at least one of the first water-based coating and the second water-based coating (i.e., only the first water-based coating, only the second water-based coating, or both the first water-based coating and the second water-based coating), a water-based coating composition containing the surface modifier of the present invention is used.

[0160] Furthermore, there are no particular limitations on the application method of the water-based coating to the substrate; examples include spraying, roller coating, brush coating, curtain coating, rod coating, doctor blade coating, slot coating, dip coating, and flow coating. There are also no particular limitations on the curing method of the water-based coating; examples include room temperature curing, heat curing, and ultraviolet curing. Additionally, when applying two or more water-based coatings wet-on-wet, it is preferable to apply the first water-based coating containing the surface modifier of this invention, followed by natural drying, forced air drying, or preheating drying as needed, to remove unwanted solvents (water, organic solvents, and other volatile components) without curing the first water-based coating, before applying the second water-based coating. Preheating drying is particularly preferred as the drying method for the first water-based coating.

[0161] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments. That is, it should be understood that other embodiments or various modifications that can be conceived by those skilled in the art within the scope of the invention as described in the claims also fall within the technical scope of the present invention.

[0162] Specifically, it includes the following inventions.

[0163] (1) A surface modifier for use in water-based coatings, characterized in that it comprises: a polymer (A) having an SP value of 6 to 12, a weight-average molecular weight of 200 to 1,000,000, and having at least three repeating units; and organic solid particles (B) which are in a solid state in the above-mentioned surface modifier at 25°C.

[0164] (2) The surface modifier according to (1) is characterized in that the polymer (A) is one or more polymers selected from the group consisting of polyvinyl alkyl ether, polybutadiene, polybutene, polyalphaolefin, poly(meth)acrylate, copolymers of dicarboxylic acid esters, polyvinyl fatty acid esters, polyalkylene glycols and their derivatives, polyamides, polyglycerol fatty acid esters and polyesters.

[0165] (3) The surface modifier according to (1) or (2) is characterized in that the above-mentioned organic solid particles (B) are one or more solid particles selected from the group consisting of amide, urea, polyethylene, oxidized polyethylene, acid-modified polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, polypropylene, acid-modified polypropylene and hydrogenated castor oil.

[0166] (4) The surface modifier according to (3) is characterized in that the amide is a fatty acid diamide obtained by reacting fatty acids with diamines, wherein the fatty acids are selected from the group consisting of alkyl fatty acids and hydroxy fatty acids and contain at least one or more hydroxy fatty acids, and the diamines contain one or more diamines selected from the group consisting of alkylene diamines and m-phenylenediamines having 2 to 6 carbon atoms.

[0167] (5) The surface conditioning agent according to any one of (1) to (4) is characterized in that the aspect ratio of the crystals of the organic solid microparticles (B) is 1.1 to 100.

[0168] (6) The surface conditioning agent according to any one of (1) to (5), characterized in that the modal diameter of the organic solid particles (B) is 0.1 to 150 μm.

[0169] (7) The surface conditioner according to any one of (1) to (6) is characterized in that it further comprises an organic medium (C) other than water that is liquid at 25°C, wherein the organic medium (C) has 0 to 2 repeating units.

[0170] (8) The surface modifier according to (7) is characterized in that the organic medium (C) is one or more selected from the group consisting of hydrocarbon oils, alcohols, diol ethers, diol esters and polyol fatty acid esters.

[0171] (9) A waterborne coating composition comprising any one of (1) to (8) a surface conditioner and a waterborne resin.

[0172] (10) An article coated with a coating agent comprising any one of (1) to (8).

[0173] (11) A method for forming a multilayer coating film, comprising the following film-forming steps: applying at least two or more water-based coatings sequentially to the surface of a substrate by wet-on-wet contact, and simultaneously heating and curing the water-based coatings applied to the substrate to form at least two or more coating films, wherein at least one of the two or more water-based coatings contains a surface modifier as described in any one of (1) to (8).

[0174] (12) The method for forming a multilayer coating as described in (11) is characterized in that, as two or more of the above-mentioned water-based coatings, a first water-based coating containing coloring pigments and a second water-based coating containing glossy material pigments are used, at least one of the first water-based coating and the second water-based coating contains the above-mentioned surface conditioning agent, and in the above-mentioned film-forming process, after the first water-based coating, the second water-based coating and the varnish coating are sequentially applied by wet-on-wet contact, the first water-based coating, the second water-based coating and the varnish coating are simultaneously heated and cured, thereby forming a first water-based resin coating, a second water-based resin coating and a varnish coating sequentially stacked from the side of the coated object on the surface of the object to be coated.

[0175] Example

[0176] The present invention will be specifically described below with reference to specific embodiments. However, the present invention is not limited to these embodiments. Additionally, unless otherwise stated, "%" and "parts" in the embodiments refer to "mass %" and "parts by mass".

[0177] [Preparation of surface conditioner samples]

[0178] Prepare surface conditioner samples E1~E33 and C1~C9 as follows.

[0179] (Polymer synthesis and preparation)

[0180] In this embodiment and comparative example, the raw materials listed in Table 1 below are used as the polymer component containing polymer (A). Furthermore, the raw material listed as "A" in Table 1 is an example of the polymer (A) of the present invention, while the raw materials listed as "non-A component" are raw materials that do not belong to the polymer (A) of the present invention. Hereinafter, a synthesis method for the raw materials whose "source" in Table 1 is "the manufacturing method described in this application" is shown.

[0181] <Synthesis of Polymer 1>

[0182] 95.3 parts of butyl acetate were added to a 500 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to reflux level under a nitrogen flow while stirring. A mixture consisting of 281.3 parts of vinyl lauryl ester, 93.8 parts of Blemmer AME-400 (methoxylated polyethylene glycol acrylate manufactured by Nippon Yusen Co., Ltd.), and 18.8 parts of tert-butylperoxy-2-ethylhexanoate was added to the dropping funnel as a dropping solution. The above dropping solution was then added dropwise over 120 minutes while maintaining the internal temperature of the reaction vessel at reflux. After the addition was completed, the reaction was continued at reflux for 40 minutes. After the reaction was completed, the solvent was removed using an evaporator to obtain polymer 1. The weight-average molecular weight of the synthesized polymer was 14700 (SP value: 9.3).

[0183] <Synthesis of Polymer 2>

[0184] 95.0 parts of butyl acetate and 159.4 parts of dibutyl fumarate were added to a 500 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to reflux for butyl acetate while stirring under a nitrogen stream. A mixture of 28.1 parts of dibutyl fumarate, 187.5 parts of ethyl acrylate, 30.0 parts of a 55% solution of 2,2-di(tert-amylperoxy)butane, and 7.5 parts of 2-ethylhexyl mercaptoacetate was added to the dropping funnel as a dropping solution. The dropping solution was then added dropwise over 120 minutes while maintaining the internal temperature of the reaction vessel at reflux. After the addition was complete, the reaction was continued at reflux for 120 minutes. After the reaction was complete, the solvent was removed using an evaporator to obtain polymer 2. The weight-average molecular weight of the synthesized polymer was 3500 (SP value: 10.1).

[0185] <Synthesis of Polymer 3>

[0186] 108.0 parts of butyl acetate were added to a 500 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to the reflux state of butyl acetate while stirring under a nitrogen stream. A mixture of 375.0 parts of 2-ethylhexyl acrylate and 17.2 parts of a 55% solution of 2,2-di(tert-amylperoxy)butane was added to the dropping funnel as a dropping solution. The dropping solution was then added dropwise over 120 minutes while maintaining the internal temperature of the reaction vessel at reflux. After the addition was complete, the reaction was continued at reflux for 60 minutes. After the reaction was complete, the solvent was removed using an evaporator to obtain polymer 3. The weight-average molecular weight of the synthesized polymer was 7800 (SP value: 9.2).

[0187] <Synthesis of Polymer 4>

[0188] 197.5 parts of Merveille 30 (an isoparaffin solvent manufactured by Idemitsu Kosan Co., Ltd.) were added to a 500 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to 95°C while stirring under a nitrogen flow. A mixture consisting of 250.0 parts lauryl methacrylate, 49.4 parts Merveille 30, and 3.1 parts of a 40% solution of tert-butylperoxy-2-ethylhexanoate was added to the dropping funnel as a dropping solution. The dropping solution was then added dropwise over 75 minutes while maintaining the internal temperature of the reaction vessel at 95°C. After the addition was complete, the reaction temperature was maintained at 95°C for 60 minutes, and then 0.7 parts of a 40% solution of tert-butylperoxy-2-ethylhexanoate was added, maintaining the temperature at 95°C for 45 minutes. The internal temperature of the reaction vessel was then raised to 100°C and the reaction was carried out for 30 minutes. After the reaction was completed, the heating residue was adjusted to 50% using Merveille 30 to obtain polymer 4. The weight-average molecular weight of the synthesized polymer was 178,900 (SP value: 9.0).

[0189] <Synthesis of Polymer 5>

[0190] 150.0 parts of toluene were added to a 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to 35°C while stirring under a nitrogen flow. Next, a mixture of 0.30 parts of boron trifluoride diethyl ether complex and 2.7 parts of diethyl ether was added to the reaction vessel. Then, 300.0 parts of ethyl vinyl ether were added to the dropping funnel as a dropping solution, and the solution was added dropwise uniformly over 120 minutes while maintaining the internal temperature of the reaction vessel at 35°C. After the addition was complete, the reaction was maintained at 35°C for 30 minutes, and then 15.00 parts of ethanol were added to the reaction vessel. After the reaction was complete, the solvent was removed using an evaporator to obtain polymer 5. The weight-average molecular weight of the synthesized polymer was 4000 (SP value: 8.6).

[0191] <Synthesis of Polymer 6>

[0192] 221.0 parts of dimer acid and 29.0 parts of hexamethylenediamine were added to a 500 mL reaction vessel equipped with a stirrer, water separator, reflux condenser, thermometer, and nitrogen inlet pipe. The internal temperature was then raised to 150°C under a nitrogen flow while stirring, and maintained at this temperature for 60 minutes. The internal temperature was then further raised to 175°C and maintained for 90 minutes to obtain polymer 6. The weight-average molecular weight of the synthesized polymer was 5800 (SP value: 9.6).

[0193] <Synthesis of Polymer 7>

[0194] 136.6 parts of dimer acid and 13.5 parts of hexamethylenediamine were added to a 500 mL reaction vessel equipped with a stirrer, water separator, reflux condenser, thermometer, and nitrogen inlet pipe. The internal temperature was then raised to 150°C under a nitrogen flow and maintained for 60 minutes. The internal temperature was then further raised to 175°C and maintained for 90 minutes. Next, 230.0 parts of Newpol (registered trademark) LB-625 (polypropylene glycol monobutyl ether manufactured by Sanyo Chemical Industry Co., Ltd.) were added to the reaction vessel, and the internal temperature was raised to 240°C while stirring and maintained for 7 hours to obtain polymer 7. The weight-average molecular weight of the synthesized polymer was 8700 (SP value: 9.0).

[0195] <Synthesis of Polymer 8>

[0196] 118.2 parts of butyl acetate were added to a 500 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to the reflux state of butyl acetate while stirring under a nitrogen flow. A mixture of 125.0 parts of vinyl lauryl ester and 6.8 parts of a 55% solution of 2,2-di(tert-amylperoxy)butane was added to the dropping funnel as a dropping solution. The dropping solution was then added dropwise over 120 minutes while maintaining the internal temperature of the reaction vessel at reflux. After the addition was complete, the reaction was continued at reflux for 60 minutes. After the reaction was complete, the solvent was removed using an evaporator to obtain polymer 8. The weight-average molecular weight of the synthesized polymer was 8100 (SP value: 9.2).

[0197] <Synthesis of Polymer 9>

[0198] 188.5 parts of Merveille 30 (an isoparaffin solvent manufactured by Idemitsu Kosan Co., Ltd.) were added to a 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to 95°C while stirring under a nitrogen flow. A mixture consisting of 250.0 parts lauryl methacrylate, 47.1 parts Merveille 30, and 12.5 parts of a 40% solution of tert-butylperoxy-2-ethylhexanoate was added to the dropping funnel as a dropping solution. The dropping solution was then added dropwise over 75 minutes while maintaining the internal temperature of the reaction vessel at 95°C. After the addition was complete, the reaction temperature was maintained at 95°C for 60 minutes, and then 0.7 parts of a 40% solution of tert-butylperoxy-2-ethylhexanoate was added, maintaining the temperature at 95°C for 45 minutes. The internal temperature of the reaction vessel was then raised to 100°C and the reaction was carried out for 30 minutes. After the reaction was completed, the heating residue was adjusted to 50% using Merveille 30 to obtain polymer 9. The weight-average molecular weight of the synthesized polymer was 74,100 (SP value: 9.0).

[0199] <Synthesis of Polymer 10>

[0200] 362.5 parts of ethanol and 12.50 parts of dimethyl 2,2'-azobisisobutyrate were added to a 500 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The internal temperature was then raised to 70°C while stirring under a nitrogen stream. A mixture of 125.0 parts of methacrylic acid and 6.25 parts of 2-ethylhexyl mercaptoacetate was added to the dropping funnel as a dropping solution. The dropping solution was then added dropwise over 120 minutes while maintaining the internal temperature of the reaction vessel at 70°C. After the addition was complete, the reaction temperature was maintained at 70°C for 180 minutes. After the reaction was complete, the solvent was removed using an evaporator, and the heating residue was adjusted to 50% to obtain polymer 10. The weight-average molecular weight of the synthesized polymer was 4000 (SP value: 12.5).

[0201] The SP values ​​of the polymers shown in Table 1 were calculated using the Fedors method. Furthermore, when determining the weight-average molecular weight of the polymers shown in Table 1, an HLC-8320GPC (manufactured by Tosoh Corporation) was used as the analytical instrument. TSKgel GMHxl×2, TSKgel G2500Hxl, TSKgel G2000Hxl, and TSKgel guardcolumn (all manufactured by Tosoh Corporation) were used as chromatographic columns. Tetrahydrofuran (THF) was used as the mobile phase. The column temperature was set to 40°C, the flow rate to 1 mL / min, and an RI detector was used. In addition, the weight-average molecular weights shown in Table 2 are values ​​calculated from chromatograms determined using gel permeation chromatography (GPC) based on the molecular weight of standard polystyrene.

[0202] [Table 1]

[0203] (Preparation and fabrication of solid particles)

[0204] In this embodiment and comparative example, the raw materials listed in Table 2 below were used as the solid particle component containing organic solid particles (B). Furthermore, the raw material listed as "B" in Table 2 is an example of the organic solid particles (B) of the present invention. The method for manufacturing the raw materials in Table 2 is shown below. Specifically, particles OC-1 to 17, examples of organic solid particles (B), were manufactured by the method shown below.

[0205] <oc-1>

[0206] Two moles of 12-hydroxystearic acid (12-HSA) and one mole of hexamethylenediamine were reacted at 190°C for 6 hours under a nitrogen atmosphere to remove the generated water, yielding diamide (a1) (Step 0). Next, a mixture of 10 parts of diamide (a1) as the particulate component and 90 parts of Merveille 30 (an isoparaffinic solvent manufactured by Idemitsu Kosan Co., Ltd.) as the organic medium (D) (particulate mixture) was heated to 165°C using a heater, causing the diamide (a1) to dissolve in Merveille 30, yielding a particulate solution (Step 1). Separately, 60 parts of Merveille 30 were added to a 500 mL container, and the above particulate solution was allowed to flow in while stirring, then cooled to a combined temperature of 97.0°C (Step 2). After cooling the mixture containing the above particulate solution to approximately 30°C, 40 parts of ethanol were added to the mixture, and stirring was performed (Step 3). Next, while maintaining stirring, the temperature of the mixture was adjusted to 46.5°C, and stirring was continued for 12 minutes to obtain a pre-dispersion of microparticles OC-1 (step 4).

[0207] <oc-2>

[0208] In steps 1 and 2, Newpol LB-625 (polypropylene glycol monobutyl ether manufactured by Sanyo Chemical Industries, Ltd.) is used instead of Merveille 30. In step 1, the particulate mixture is heated to 135°C, and in step 2, it is cooled to a mixed temperature of 42.9°C. In step 3, Newpol LB-625 is used instead of ethanol. Step 4 is not performed. Otherwise, the pre-dispersion of particulate OC-2 is obtained by the same method as OC-1.

[0209] <oc-3>

[0210] In step 0, diamide (a2) is obtained by reacting 2 moles of 12-HSA with 1 mole of ethylenediamine. In step 1, diamide (a2) is used instead of diamide (a1), and the particulate mixture is heated to 155°C. In step 2, the mixture is cooled to a temperature of 45.6°C. In step 4, the temperature of the mixture is adjusted to 45.5°C. Otherwise, a pre-dispersion of particulate OC-3 is obtained by the same method as OC-1.

[0211] <oc-4>

[0212] In step 0, diamide (a3) ​​is obtained by reacting 2 moles of 12-HSA with 1 mole of 1,4-diaminobutane. In step 1, diamide (a3) ​​is used instead of diamide (a1), and the particulate mixture is heated to 160°C. In step 2, the mixture is cooled to a temperature of 97.0°C. In step 4, the temperature of the mixture is adjusted to 42.0°C. Otherwise, a pre-dispersion of particulate OC-4 is obtained by the same method as OC-1.

[0213] <oc-5>

[0214] Step 0 is not performed. In step 1, hardened castor oil is used instead of diamide (a1). The particulate mixture is heated to 95°C. In step 2, it is cooled to a mixed temperature of 53.9°C. Step 4 is not performed. Otherwise, the pre-dispersion of particulate OC-5 is obtained by the same method as OC-1.

[0215] <oc-6>

[0216] Step 0 is not performed. In step 1, A-C629 (low-density oxidized polyethylene manufactured by Honeywell Corporation of Japan) is used instead of diamide (a1). The particulate mixture is heated to 150°C. In step 2, 100 parts of Merveille 30 are added and cooled to a mixed temperature of 46.7°C. Steps 3 and 4 are not performed. Otherwise, the pre-dispersion of particulate OC-6 is obtained by the same method as OC-1.

[0217] <oc-7>

[0218] In steps 1 and 2, Buticel (ethylene glycol monobutyl ether manufactured by KH Neochem Co., Ltd.) is used instead of Merveille 30. In step 1, the particulate mixture is heated to 120°C, and in step 2, it is cooled to a mixed temperature of 25.0°C. In step 3, Buticel is used instead of ethanol. Step 4 is not performed. Otherwise, a pre-dispersion of particulate OC-7 is obtained by the same method as OC-1.

[0219] <oc-8>

[0220] After step 3, instead of step 4, the mixture obtained in step 3 is placed in a bottle and heated to 70°C over 24 hours, and maintained at that temperature for 24 hours. Then, it is cooled to 25°C over 24 hours. Otherwise, a pre-dispersion of microparticles OC-8 is obtained by the same method as OC-1.

[0221] <oc-9>

[0222] In steps 1 and 2, DOWANOL (registered trademark) PM (propylene glycol monomethyl ether manufactured by Dow Toray Industries, Inc.) was used instead of Merveille 30. In step 1, the particulate mixture was heated to 110°C. In step 2, it was cooled to a mixed temperature of 48.5°C. In step 4, the temperature of the mixture was adjusted to 50.4°C. Otherwise, a pre-dispersion of particulate OC-9 was obtained by the same method as OC-1.

[0223] <oc-10>

[0224] In step 0, diamide (a4) is obtained by reacting 2 moles of 12-HSA with 1 mole of m-phenylenediamine. In step 1, diamide (a4) is used instead of diamide (a1), and the particulate mixture is heated to 150°C. In step 2, the mixture is cooled to a temperature of 46.5°C. In step 4, the temperature of the mixture is adjusted to 47.3°C. Otherwise, a pre-dispersion of particulate OC-10 is obtained by the same method as OC-1.

[0225] <oc-11>

[0226] In steps 1 and 2, 2-ethylhexanol (manufactured by Mitsubishi Chemical Corporation) is used instead of Merveille 30. In step 1, the particulate mixture is heated to 135°C. In step 2, it is cooled to a mixed temperature of 45.5°C. In step 4, the temperature of the mixture is adjusted to 62.1°C. Otherwise, a pre-dispersion of particulate OC-11 is obtained by the same method as OC-1.

[0227] <oc-12>

[0228] Step 0 is omitted. In steps 1 and 2, 2-ethylhexanol (manufactured by Mitsubishi Chemical Corporation) is used instead of Merveille 30, and A-C629 (low-density oxidized polyethylene manufactured by Honeywell Corporation of Japan) is used instead of diamide (a1). The particulate mixture is heated to 120°C. In step 2, 100 parts of 2-ethylhexanol are added, and the mixture is cooled to a temperature of 35.5°C. Steps 3 and 4 are omitted. Otherwise, a pre-dispersion of particulate OC-12 is obtained by the same method as OC-1.

[0229] <oc-13>

[0230] Step 0 is omitted. In steps 1 and 2, 2-ethylhexanol (manufactured by Mitsubishi Chemical Corporation) is used instead of Merveille 30, and Ceridust 3620 (polyethylene wax manufactured by Clariant Corporation of Japan) is used instead of diamide (a1). The particulate mixture is heated to 140°C. In step 2, 100 parts of 2-ethylhexanol are added, and the mixture is cooled to a temperature of 32.2°C. Steps 3 and 4 are omitted. Otherwise, a pre-dispersion of particulate OC-13 is obtained by the same method as OC-1.

[0231] <oc-14>

[0232] Step 0 is not performed. In step 1, Ceridust3620 (polyethylene wax manufactured by Clariant Corporation of Japan) is used instead of diamide (a1). The particulate mixture is heated to 130°C. In step 2, 100 parts of Merveille 30 are added and cooled to a mixed temperature of 35.3°C. Steps 3 and 4 are not performed. Otherwise, the pre-dispersion of particulate OC-14 is obtained by the same method as OC-1.

[0233] <oc-15>

[0234] Step 0 is omitted. In step 1, A-C405T (ethylene-vinyl acetate copolymer manufactured by Honeywell Corporation of Japan) is used instead of diamide (a1). The particulate mixture is heated to 100°C. In step 2, 100 parts of Merveille 30 are added and cooled to a mixed temperature of 35.9°C. Steps 3 and 4 are omitted. Otherwise, a pre-dispersion of particulate OC-15 is obtained by the same method as OC-1.

[0235] <oc-16>

[0236] Step 0 is omitted. In steps 1 and 2, 2-ethylhexanol (manufactured by Mitsubishi Chemical Corporation) is used instead of Merveille 30, and A-C540 (ethylene-acrylic acid copolymer manufactured by Honeywell Corporation of Japan) is used instead of diamide (a1). The particulate mixture is heated to 120°C. In step 2, 100 parts of 2-ethylhexanol are added, and the mixture is cooled to a temperature of 33.3°C. Steps 3 and 4 are omitted. Otherwise, a pre-dispersion of particulate OC-16 is obtained by the same method as OC-1.

[0237] <oc-17>

[0238] Step 0 is not performed. In step 1, Viscol 660-P (polypropylene wax manufactured by Sanyo Chemical Industries, Ltd.) is used instead of diamide (a1). The particulate mixture is heated to 120°C. In step 2, 100 parts of Merveille 30 are added and cooled to a mixed temperature of 30.1°C. Steps 3 and 4 are not performed. Otherwise, a pre-dispersion of particulate OC-17 is obtained by the same method as OC-1.

[0239] <Determination of Peak Particle Size>

[0240] For the particles OC-1 to OC-17 obtained as described above, the peak particle size was determined using a Microtrac MT-3000EXII / USVR particle size distribution measuring device (manufactured by Microtrac) and Merveille 30 as the circulating solvent. The peak particle size (μm) of each organic solid particle is shown in Table 2.

[0241] <Measurement of aspect ratio>

[0242] For the particles OC-1 to OC-17 obtained as described above, the aspect ratio is determined as follows (1) to (7) below.

[0243] 1) Use xylene to dilute the pre-dispersion of particles OC-1~OC-17 to 300 times, and irradiate with ultrasound for 30 seconds to disperse the particles in the diluent.

[0244] 2) On filter paper, add a drop of the diluted solution from 1) to the copper microgrid (grid spacing 150μm) with carbon-reinforced cotton support film, and let it dry naturally.

[0245] 3) Use carbon ribbon to fix the microgrid containing the microparticle sample obtained in 2) onto the SEM holder.

[0246] 4) SEM measurements were performed under the following conditions: Measurement device: SU3500 (manufactured by Hitachi High Technology Co., Ltd.), Measurement mode: high vacuum, low accelerating voltage, Image captured: reflected electron image, Magnification: 2000x, Brightness / Contrast: Auto, Focus: Manual.

[0247] 5) Image analysis: Using image analysis software (ImageJ), after brightness / contrast correction and smoothing correction, the image is binarized to remove noise, particles at image boundaries, and aggregated particles, and then particle analysis is performed.

[0248] 6) When the particles being measured consist only of convex shapes, perform particle analysis and calculate the aspect ratio (= aspect ratio / minor axis) based on the obtained major and minor axis values ​​of each particle. The average aspect ratio of more than 10 particles is taken as the aspect ratio of the particle sample (particles OC-1~OC-17).

[0249] 7) When the particles being measured contain both convex and non-convex shapes, use the Freehandline tool to measure the fiber length and the Straightline tool to measure the fiber width at the center of the particle. Calculate the aspect ratio (= fiber length value / fiber width value) and take the average aspect ratio of more than 10 particles as the aspect ratio of the sample.

[0250] Furthermore, the aforementioned "non-convex shape" refers to a shape where the area of ​​the particle's convex hull (the portion surrounded by a contractile virtual curve) is more than twice the actual area. Conversely, the aforementioned "convex shape" refers to a shape where the area of ​​the particle's convex hull is less than twice the actual area. The aspect ratios of each organic solid particle are shown in Table 2.

[0251] [Table 2]

[0252] (Preparation of organic media)

[0253] In this embodiment and comparative example, the raw materials listed in Table 3 below were used as the organic medium (C). Furthermore, the boiling points of some of the raw materials are listed in Table 3.

[0254] [Table 3]

[0255] (Preparation of surface conditioner samples)

[0256] Surface conditioner samples E1~E43 and C1~C11 were prepared using the methods described later. Details of the preparation methods for each surface conditioner sample are shown below.

[0257] <Surface Conditioner Sample E1>

[0258] Add 35.0 parts of Uniol (registered trademark) TG-4000R (polypropylene glycol glycerol ether manufactured by Nippon Oil Co., Ltd.) to a 100mL plastic cup. While stirring with a disperser, add 30.0 parts of the pre-dispersion of particulate OC-1 and mix at 2000rpm for 15 minutes to obtain surface conditioner sample E1.

[0259] <Surface Conditioner Sample E2>

[0260] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-3. Otherwise, surface conditioner sample E2 was obtained by the same method as surface conditioner sample E1.

[0261] <Surface Conditioner Sample E3>

[0262] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-4. Otherwise, surface conditioner sample E3 was obtained by the same method as surface conditioner sample E1.

[0263] <Surface Conditioner Sample E4>

[0264] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-5. Otherwise, surface conditioner sample E4 was obtained by the same method as surface conditioner sample E1.

[0265] <Surface Conditioner Sample E5>

[0266] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-6. Otherwise, surface conditioner sample E5 was obtained by the same method as surface conditioner sample E1.

[0267] <Surface Conditioner Sample E6>

[0268] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-10. Otherwise, surface conditioner sample E6 was obtained by the same method as surface conditioner sample E1.

[0269] <Surface Conditioner Sample E7>

[0270] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-9. Otherwise, surface conditioner sample E7 was obtained by the same method as surface conditioner sample E1.

[0271] <Surface Conditioner Sample E8>

[0272] The amount of Uniol TG-4000R added was changed to 52.0 parts, and the amount of pre-dispersion of microparticles OC-1 added was changed to 13.0 parts. Otherwise, surface conditioner sample E8 was obtained by the same method as surface conditioner sample E1.

[0273] <Surface Conditioner Sample E9>

[0274] The amount of Uniol TG-4000R added was changed to 13.0 parts, and the amount of the pre-dispersion of microparticle OC-1 added was changed to 52.0 parts. Otherwise, surface conditioner sample E9 was obtained by the same method as surface conditioner sample E1.

[0275] <Surface Conditioner Sample E10>

[0276] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-7. Otherwise, surface conditioner sample E10 was obtained by the same method as surface conditioner sample E1.

[0277] <Surface Conditioner Sample E11>

[0278] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-8. Otherwise, surface conditioner sample E11 was obtained by the same method as surface conditioner sample E1.

[0279] <Surface conditioning agent samples E12~15, E17, E19~E21, E23, E26~E27, E30~E31, E33, E43>

[0280] Uniol TG-4000R was changed to "A: Polymer" as recorded in Tables 5, 6 and 7. Otherwise, surface modifier samples E12~15, E17, E19~E21, E23, E26~E27, E30~E31, E33 and E43 were obtained by the same method as surface modifier sample E1.

[0281] <Surface Conditioner Sample E16>

[0282] The 35.0 parts of Uniol TG-4000R were replaced with 27.5 parts of polymer 3 and 7.5 parts of EMLEX (registered trademark) RWIS-320 (hydrogenated castor oil polyethylene glycol triisostearate manufactured by Nihon Emulsion Co., Ltd.). Otherwise, surface conditioner sample E16 was obtained by the same method as surface conditioner sample E1.

[0283] <Surface Conditioner Sample E18>

[0284] The 35.0 parts of Uniol TG-4000R were replaced with 35.0 parts of a Merveille 30 solution of polymer 4 (polymer concentration: 50% by mass). Otherwise, surface conditioner sample E18 was obtained by the same method as surface conditioner sample E1.

[0285] <Surface Conditioner Sample E22>

[0286] The 35.0 parts of Uniol TG-4000R were replaced with 7.5 parts of EMLEX RWIS-320 and 27.5 parts of PIBVE (a 60% by mass isoalkane solution) manufactured by Siwei Development Group Ltd. Otherwise, surface modifier sample E22 was obtained by the same method as surface modifier sample E1.

[0287] <Surface Conditioner Sample E24>

[0288] The 35.0 parts Uniol TG-4000R were replaced with a polymer diluent prepared by diluting 17.5 parts of polymer 6 with 17.5 parts 2-ethylhexanol. Otherwise, surface conditioner sample E24 was obtained by the same method as surface conditioner sample E1.

[0289] <Surface Conditioner Sample E25>

[0290] 35.0 parts Uniol TG-4000R were replaced with a polymer diluent prepared by diluting 28.0 parts polymer 7 with 7.0 parts 2-ethylhexanol. Otherwise, surface conditioner sample E25 was obtained by the same method as surface conditioner sample E1.

[0291] <Surface Conditioner Sample E28>

[0292] The pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-2, and Uniol TG-4000R was changed to Newpol LB-625. Otherwise, surface conditioner sample E28 was obtained by the same method as surface conditioner sample E1.

[0293] <Surface Conditioner Sample E29>

[0294] 35.0 parts of Uniol TG-4000R were replaced with 35.0 parts of a Merveille 30 (solvent) solution of polymer 9 (polymer concentration: 50% by mass). Otherwise, surface conditioner sample E29 was obtained by the same method as surface conditioner sample E1.

[0295] <Surface Conditioner Sample E32>

[0296] Uniol TG-4000R was changed to PTMG650 (polybutanediol manufactured by Mitsubishi Chemical Corporation), and the pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-11. Otherwise, surface conditioner sample E32 was obtained by the same method as surface conditioner sample E1.

[0297] <Surface Conditioner Sample E34>

[0298] Uniol TG-4000R was changed to SY Glister PO-3S (polyglycerol-4 pentaoleate manufactured by Sakamoto Pharmaceutical Co., Ltd.), and the pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-6. Otherwise, surface conditioner sample E34 was obtained by the same method as surface conditioner sample E1.

[0299] <Surface Conditioner Samples E35~E37>

[0300] Uniol TG-4000R was changed to "A: Polymer" as recorded in Table 7, and the pre-dispersion of microparticle OC-1 was changed to the pre-dispersion of microparticle OC-12. Otherwise, surface conditioner samples E35 to E37 were obtained by the same method as surface conditioner sample E1.

[0301] <Surface Conditioner Samples E38~E42>

[0302] The pre-dispersion of microparticle OC-1 was changed to "B: organic solid microparticles" and "C: organic medium" as recorded in Table 7. Otherwise, surface conditioner samples E38 to E42 were obtained by the same method as surface conditioner sample E1.

[0303] <Surface Conditioner Sample C1>

[0304] Using 24.0 parts Merveille 30 and 6.0 parts ethanol instead of 30.0 parts of the pre-dispersion of microparticles OC-1, surface conditioner sample C1 was obtained by the same method as surface conditioner sample E1.

[0305] <Surface Conditioner Sample C2>

[0306] Using 24.0 parts Merveille 30 and 6.0 parts ethanol instead of 30.0 parts of the pre-dispersion of particulate OC-1, surface conditioner sample C2 was obtained by the same method as surface conditioner sample E30.

[0307] <Surface Conditioner Sample C3>

[0308] Using 24.0 parts Merveille 30 and 6.0 parts ethanol instead of 30.0 parts of the pre-dispersion of particulate OC-1, surface conditioner sample C3 was obtained by the same method as surface conditioner sample E27.

[0309] <Surface Conditioner Sample C4>

[0310] As a surface modifier sample C4, a pre-dispersion of microparticles OC-1 was used.

[0311] <Surface Conditioner Sample C5>

[0312] Uniol TG-4000R was replaced with MFDG (dipropylene glycol monomethyl ether manufactured by Japan Emulsifier Co., Ltd.) as a non-A component. Otherwise, surface conditioner sample C5 was obtained by the same method as surface conditioner sample E1.

[0313] <Surface Conditioner Sample C6>

[0314] Uniol TG-4000R was replaced with an ethanol solution of polymer 10 (polymer concentration: 50% by mass) as a non-A component. Otherwise, surface conditioner sample C6 was obtained by the same method as surface conditioner sample E1.

[0315] <Surface Conditioner Sample C7>

[0316] 39.0 parts of FS1265-10000cst (fluorine-modified organosilicon manufactured by Dow Toray Industries, Ltd.) were diluted with methyl isobutyl ketone to obtain a polymer dilution. Next, the polymer dilution was added to a 100 mL plastic cup, and while stirring with a disperser, 13.0 parts of the pre-dispersion of particulate OC-1 were added. The mixture was stirred at 2000 rpm for 15 minutes to obtain surface conditioner sample C7.

[0317] <Surface Conditioner Sample C8>

[0318] Uniol TG-4000R was replaced with SY Glister MO-3S (polyglycerol-4 pentaoleate manufactured by Sakamoto Pharmaceutical Co., Ltd.) as a non-A component, and the pre-dispersion of microparticle OC-1 was replaced with the pre-dispersion of microparticle OC-12. Otherwise, surface conditioner sample C8 was obtained by the same method as surface conditioner sample E1.

[0319] <Surface Conditioner Sample C9>

[0320] Uniol TG-4000R was replaced with SY Glister PO-3S (polyglycerol-4 pentaoleate manufactured by Sakamoto Pharmaceutical Co., Ltd.), and 46.2 parts of Merveille 30 were used to replace the pre-dispersion of microparticles OC-1. Otherwise, surface conditioner sample C9 was obtained by the same method as surface conditioner sample E1.

[0321] <Surface Conditioner Sample C10>

[0322] As a surface conditioner sample C10, a mixture of hydrocarbons, hydrophobic silica, and alkoxy compounds, namely Agtan 295 (manufactured by MUNZING CHEMIE GmbH), was used.

[0323] <Surface Conditioner Sample C11>

[0324] As a surface conditioner sample C11, a mixture of organosilicon, hydrophobic microparticles, and polyethylene glycol, namely BYK-024 (manufactured by BYK Corporation), was used.

[0325] The compositions of the surface conditioner samples prepared as described above are shown in Tables 4 to 8 below.

[0326] [Table 4]

[0327] [Table 5]

[0328] [Table 6]

[0329] [Table 7]

[0330] [Table 8]

[0331] [Preparation of water-based coatings]

[0332] Two water-based coatings (Blank) were prepared according to the formulations shown in Tables 9 and 11 below. Table 9 shows the formulation for a first water-based colorant coating (BC-1) containing coloring pigments and surface modifiers, and Table 11 shows the formulation for a second water-based colorant coating (BC-2) containing coloring pigments, gloss pigments, and surface modifiers. For both the first and second water-based colorants, pigment pastes (P-1) and (P-2) used in their respective water-based coatings were prepared beforehand. These pigment pastes were then mixed with other coating components to produce the first and second water-based colorants. The formulations for pigment pastes (P-1) and (P-2) are shown in Tables 10 and 12, respectively. In addition, surface conditioner sample E27 was used in the production of the first water-based coloring coating (BC-1) and the second water-based coloring coating (BC-2). This surface conditioner was formulated to defoam the bubbles generated during the production of the first water-based coloring coating (BC-1) and the second water-based coloring coating (BC-2).

[0333] [Table 9]

[0334] [Table 10]

[0335] [Table 11]

[0336] [Table 12]

[0337] (Preparation of the first water-based coloring paint)

[0338] Following the proportions shown in Table 10, water-soluble acrylic resin, white pigment, black pigment, solvent, water, dispersant, and surface conditioner sample E27 were added to a container. Zirconia beads were then added to the mixture of these raw materials, and the mixture was dispersed for 60 minutes using a paint mixer to prepare the first water-based coloring paint pigment slurry (P-1). After dispersion, the zirconia beads were removed. Next, following the proportions described in Table 9, water-soluble acrylic resin, iminomethylated melamine resin, water, pH adjuster, solvent, and surface conditioner sample E27 were added sequentially to the pigment slurry (P-1), and the mixture was mixed using a laboratory disperser to obtain the first water-based coloring paint (BC-1).

[0339] (Preparation of the second water-based coloring coating)

[0340] Following the proportions shown in Table 12, black pigment, water, dispersant, and surface conditioner sample E27 were added to a container. Zirconia beads were then added to the mixture of these raw materials, and the mixture was dispersed for 60 minutes using a paint mixer to prepare a second water-based coloring paint pigment slurry (P-2). After dispersion, the zirconia beads were removed. Next, following the proportions described in Table 11, acrylic polyol dispersion, acrylic modified polyurethane dispersion, iminomethylated melamine resin, viscosity modifier, pH adjuster, water, solvent, and gloss pigment were added sequentially to the pigment slurry (P-2), and the mixture was mixed using a laboratory disperser to obtain a second water-based coloring paint (BC-2).

[0341] (Preparation of varnish coating)

[0342] First, synthesize the resins used in the varnish coating as follows.

[0343] Synthesis of Hydroxyl Acrylic Resin (C-1)

[0344] 330.0 parts of ethyl 3-ethoxypropionate were added to a 2000 ml reaction vessel equipped with a stirrer, reflux condenser, dropping device, thermometer, and nitrogen inlet tube. Then, the internal temperature was raised to 155°C while stirring under a nitrogen flow. A mixture consisting of 290.4 parts hydroxypropyl acrylate (trade name HPA: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 88.0 parts polypropylene glycol monomethacrylate (trade name Blemmer PP-1000: manufactured by Nippon Oil Co., Ltd.), 88.0 parts isoborneol acrylate (trade name IBXA: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 44.0 parts 2-hydroxyethyl methacrylate (trade name Acryester HO: manufactured by Mitsubishi Chemical Co., Ltd.), 44.0 parts 2-hydroxyethyl acrylate, 176.0 parts styrene, 132.0 parts methyl methacrylate (trade name Acryester M: manufactured by Mitsubishi Chemical Co., Ltd.), 17.6 parts methacrylic acid, and 36.96 parts di-tert-amyl peroxide (trade name Luperox DTA: manufactured by Arkemagifor Co., Ltd.) was added to the aforementioned dropping device as a dropping solution. Next, while maintaining the internal temperature of the reaction vessel at 155°C, the above-mentioned solution was added dropwise uniformly over 240 minutes. After the addition was complete, the reaction temperature was maintained for 120 minutes. After the reaction was complete, the internal temperature of the reaction vessel was cooled to 100°C, and 259.6 parts of butyl acetate were added. The resin solid content was adjusted to 60% using ethyl 3-ethoxypropionate / butyl acetate (56 / 44), yielding a hydroxyl-containing acrylic resin (C-1). The synthesized hydroxyl-containing acrylic resin had a weight-average molecular weight of 5500 (hydroxyl value: 200 mg KOH / g, SP value: 11.0).

[0345] <Preparation of Varnish Coating>

[0346] Next, according to the proportions shown in Table 13, isocyanate curing agent, diluent and surface conditioner (leveling agent) were added sequentially to the hydroxyl-containing acrylic resin (C-1), and mixed using a laboratory disperser to produce a clear varnish coating.

[0347] [Table 13]

[0348] [Evaluation Method]

[0349] Using the first water-based coloring paint, the second water-based coloring paint, and the varnish paint obtained as described above, evaluation tests were conducted as follows.

[0350] (Evaluation of anti-foaming properties)

[0351] A multilayer coating (hereinafter referred to as "anti-foaming evaluation coating") was prepared for evaluating anti-foaming properties, and the formation of solvent bubbles in the anti-foaming evaluation coating was observed to evaluate the anti-foaming properties. Details are as follows.

[0352] <Preparation of Anti-Fogging Evaluation Coating>

[0353] A first water-based coloring coating (BC-1) was applied to a glass plate using an OSP-80 non-winding bar coater. After standing at room temperature for 5 minutes, it was preheated at 80°C for 5 minutes. Next, a second water-based coloring coating was applied to the uncured film obtained from the first water-based coloring coating using a 6 mil applicator. After standing at room temperature for 5 minutes, it was preheated at 80°C for 5 minutes. This second water-based coloring coating had been treated by adding any one of the surface modifier samples E1-E43 and C1-C11 relative to the coating at a specified addition amount and dispersing it at 2000 rpm for 5 minutes using a disperser. Further, a clear varnish coating was applied to the uncured film obtained from the second water-based coloring coating using an OSP-80 non-winding bar coater. After standing at room temperature for 5 minutes, it was heated at 140°C for 30 minutes to allow the multilayer coating to cure and dry simultaneously, thereby obtaining the anti-foaming evaluation coatings of Examples 1-43 and Comparative Examples 1-11. The surface modifier samples added to the second waterborne coloring coating during the preparation of the anti-foaming evaluation coatings of each embodiment and comparative example are shown in Tables 14 and 15 below. Furthermore, as shown in Table 15, Blank's evaluation coatings were also prepared in which no surface modifier was added to the second waterborne coloring coating during the preparation of the anti-foaming evaluation coatings.

[0354] <Evaluation Methods for Anti-Fogging Coatings>

[0355] The anti-foaming properties of the coatings of Examples 1-43, Comparative Examples 1-11 and Blank were evaluated by visual observation of the formation of solvent bubbles, and were evaluated according to the following criteria in four levels.

[0356] A (Excellent): No solvent bubbles observed in the coating.

[0357] B (Good): A small amount of solvent bubbles are visible in the coating.

[0358] C (Acceptable): Solvent bubbles are visible in some areas of the coating.

[0359] D (Poor): Solvent bubbles are visible across the entire surface of the coating.

[0360] (Evaluation of topcoatability)

[0361] A multilayer coating film for evaluating topcoatability (hereinafter referred to as "topcoatability evaluation coating film") is prepared, and the appearance of the topcoatability evaluation coating film is observed to evaluate the topcoatability. Details are as follows.

[0362] <Topcoatability Evaluation and Coating Preparation>

[0363] A first water-based colorant (BC-1) was applied to an SPCC-SD electrodeposition coating plate (manufactured by PALTEK Co., Ltd.) using an OSP-80 non-winding bar coater and an AFA-standard automatic coating machine (manufactured by TQC Sheen). After standing at room temperature for 5 minutes, it was preheated at 80°C for 5 minutes. Next, a second water-based colorant was applied to the uncured film obtained from the first water-based colorant using the OSP-80 non-winding bar coater. After standing at room temperature for 5 minutes, it was preheated at 80°C for 5 minutes. The second water-based colorant had been treated as follows: any one of the surface conditioner samples E1~E43 and C1~C11 was added, dispersed at 2000 rpm for 5 minutes using a disperser, and degassed using a deaerator. Furthermore, on the uncured coating obtained from the second waterborne coloring coating, a clear varnish coating was applied using an OSP-80 non-winding bar coater. After standing at room temperature for 5 minutes, it was heated at 140°C for 30 minutes to simultaneously cure and dry the multiple coatings, thereby obtaining the topcoatability evaluation coatings of Examples 1-43 and Comparative Examples 1-11. Samples of surface modifiers added to the second waterborne coloring coating during the preparation of the topcoatability evaluation coatings of each example and comparative example are shown in Tables 14 and 15 below. In addition, as shown in Table 15, Blank's evaluation coatings without the addition of surface modifiers to the second waterborne coloring coating during the preparation of the topcoatability evaluation coatings were also prepared.

[0364] <Evaluation Methods for Topcoatability Evaluation>

[0365] The appearance of the coatings of Examples 1-43, Comparative Examples 1-11 and Blank obtained as described above was observed by visual inspection and evaluated according to the following criteria in four grades.

[0366] A (Excellent): Good coating appearance

[0367] B (Good): Coating smoothness is slightly poor.

[0368] C (Acceptable): Localized dents and foreign matter are visible in the coating.

[0369] D (Poor): Craters and foreign matter are visible throughout the coating.

[0370] [Evaluation Results]

[0371] The results of the performance evaluation as described above are shown in Tables 14 and 15.

[0372] [Table 14]

[0373] [Table 15]

[0374] The multilayer coatings (anti-foaming evaluation coatings and topcoat evaluation coatings) of Examples 1-43 all exhibit the properties required in this invention in both anti-foaming and topcoat evaluations.

[0375] As can be seen from Examples 1, 12-17, 19-21, 23, 25, 26, 27, 30, 31, 33, 43, etc., by using polyalkylene glycols and their derivatives, polyalkyl acrylates, polyvinyl alkyl ethers, polybutene, polyglycerol fatty acid esters, etc. as polymers (A), the anti-foaming properties and topcoat properties are particularly excellent.

[0376] Furthermore, as can be seen from Examples 1-7, 10, and 11, when the aspect ratio of the organic solid particles (B) is in the range of 1.5 to 30, the anti-foaming properties and topcoat properties are particularly excellent.

[0377] On the other hand, as surface conditioning agents, Comparative Examples 1-3 and 9, which do not contain organic solid particles (B), and Comparative Example 4, which does not contain polymers (A), all exhibit poor antifoaming properties.

[0378] Furthermore, Comparative Examples 5-8, which contain polymers (non-A components) that are not part of the polymer (A) of this invention, exhibit poor anti-foaming properties or poor topcoatability. In particular, Comparative Example 7, which contains an organosilicon compound as a polymer, exhibits excellent anti-foaming properties but poor topcoatability.

[0379] Furthermore, as surface conditioning agents, Comparative Example 10, which contained hydrophobic silica microparticles, and Comparative Example 11, which contained organosilicon hydrophobic microparticles, exhibited poor surface coating properties. Additionally, Comparative Example 11, which contained organosilicon hydrophobic microparticles, also showed poor anti-foaming properties.

Claims

1. A surface conditioner for use in water-based coatings, characterized in that, Include: Polymer (A), having an SP value of 6-12, a weight-average molecular weight of 200-1,000,000, and having at least three repeating units; and Organic solid particles (B) are in a solid state in the surface conditioner at 25°C.

2. The surface conditioner according to claim 1, characterized in that, The polymer (A) is one or more polymers selected from the group consisting of polyvinyl alkyl ethers, polybutadiene, polybutene, polyalphaolefins, poly(meth)acrylates, copolymers of dicarboxylic acid esters, polyvinyl fatty acid esters, polyalkylene glycols and their derivatives, polyamides, polyglycerol fatty acid esters and polyesters.

3. The surface conditioner according to claim 1, characterized in that, The organic solid particles (B) are one or more solid particles selected from the group consisting of amide, urea, polyethylene, oxidized polyethylene, acid-modified polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, polypropylene, acid-modified polypropylene and hydrogenated castor oil.

4. The surface conditioner according to claim 3, characterized in that, The amide is a fatty acid diamide obtained by reacting fatty acids with diamines. The fatty acids are selected from the group consisting of alkyl fatty acids and hydroxy fatty acids, and contain at least one or more hydroxy fatty acids. The diamines contain one or more diamines selected from the group consisting of alkylene diamines and m-phenylenediamines having 2 to 6 carbon atoms.

5. The surface conditioner according to claim 1, characterized in that, The aspect ratio of the organic solid microparticles (B) crystals is 1.1 to 100.

6. The surface conditioner according to claim 1, characterized in that, The mode diameter of the organic solid particles (B) is 0.1~150 μm.

7. The surface conditioner according to claim 1, characterized in that, It also includes organic media (C) that are liquid at 25°C, excluding water. The organic medium (C) has 0 to 2 repeating units.

8. The surface conditioner according to claim 7, characterized in that, The organic medium (C) is one or more selected from the group consisting of hydrocarbon oils, alcohols, diol ethers, diol esters and polyol fatty acid esters.

9. A waterborne coating composition comprising the surface conditioner and waterborne resin as described in any one of claims 1 to 8.

10. An article coated with a coating agent comprising any one of claims 1 to 8.

11. A method for forming a multilayer coating film, comprising the following film-forming steps: After applying at least two types of water-based coatings sequentially to the surface of an object through a wet-on-wet process, the water-based coatings applied to the object are simultaneously heated and cured, thereby forming at least two layers of coating film. At least one of the two or more water-based coatings contains the surface modifier according to any one of claims 1 to 8.

12. The method for forming a multilayer coating as described in claim 11, characterized in that, As two or more types of water-based coatings, a first water-based coating containing coloring pigments and a second water-based coating containing glossy material pigments are used. At least one of the first water-based coating and the second water-based coating contains the surface modifier. In the film-forming process, after the first water-based coating, the second water-based coating, and the varnish coating are applied in sequence by wet-on-wet contact, the first water-based coating, the second water-based coating, and the varnish coating are simultaneously heated and cured, thereby forming a first water-based resin film, a second water-based resin film, and a varnish film that are sequentially stacked from the side of the object to be coated on the surface of the object.

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