Resin composition for coating material

Abstract

The purpose of the present invention is to provide a resin composition that is for a coating material and that has excellent weather resistance. The present invention is a resin composition that is for a coating material and that contains a silicone-modified polymer emulsion, wherein the silicone-modified polymer emulsion has a structural unit derived from a polymerizable unsaturated monomer and a structure derived from a silane compound, wherein the proportion of the structure derived from the silane compound with respect to 100 mass% of the structural unit derived from the polymerizable unsaturated monomer is not less than 10 mass%.

Description

Resin composition for paint

[0001] The present invention relates to a resin composition for paints, and more particularly to a resin composition for paints that can be suitably used as a paint (exterior paint) for painting the exterior walls of buildings and as an anti-corrosion paint useful for metal members and the like.

[0002] Compared with organic solvent-based paints, paints containing resin emulsions can reduce health hazards to painters and residents, environmental pollution, etc., and are widely used in buildings, civil engineering structures, transportation equipment such as automobiles, etc. Furthermore, various developments and improvements have been made to the resin emulsions used in such paints.

[0003] To improve the stain resistance of paints for the exterior walls of buildings, etc., techniques have been developed that incorporate a water-soluble polymer that hydrophilizes the coating surface, allowing rainwater to blend with the coating surface and facilitate the rain's washing away of dirt (oil). For example, Patent Document 1 discloses an aqueous resin composition for paints that contains emulsion particles having at least two resin layers and a water-soluble polymer, wherein the outer layer of the emulsion particles is composed of a polymer obtained by polymerizing a monomer component containing 0.1 to 10% by mass of a carbonyl group-containing monomer, and the water-soluble polymer is obtained by polymerizing a monomer component containing 1 to 30% by mass of a carbonyl group-containing monomer.

[0004] Among paints, anti-rust paints are applied to steel machinery, building materials, etc. to prevent rust formation and deterioration of various structures, thereby providing a protective effect and preventing rust formation through the coating film that is formed. Such anti-rust paints are used not only for ships, railway vehicles, automobiles, building structures, etc., which are used in outdoor corrosive environments, but also for water pipes, piping in factory manufacturing plants, etc., and play an important role in preventing rust and increasing the durability of these metal parts.

[0005] Anti-rust paints are broadly divided into organic solvent-based and water-based anti-rust paints. Organic solvent-based anti-rust paints are excellent in terms of rust prevention, adhesion, water resistance, etc., but have been problematic due to the risk of solvent poisoning and fire, as well as environmental impacts such as air pollution. Therefore, in recent years, from the perspective of improving work safety and reducing environmental impact, there has been a desire to develop water-based anti-rust paints that exhibit excellent performance, and research is being actively conducted.

[0006] With regard to water-based anti-rust paints, Patent Document 2 discloses a water-based anti-rust paint composition comprising: (I) a monomer mixture (where (a) + (b) + (c) = 100 parts by mass) obtained by mixing 1 to 60 parts by mass of (a) a conjugated diene monomer, 0.5 to 10 parts by mass of (b) a monomer having a hydroxyalkyl group (excluding those corresponding to the (a) conjugated diene monomer), and 30 to 98.5 parts by mass of (c) other monomers copolymerizable therewith, wherein the proportion of (c1) ethylenically unsaturated carboxylic acid monomer among the (c) other monomers is 0 to 2.5 parts by mass relative to 100 parts by mass of the total of the monomers (a), (b), and (c); and (II) a rust-preventive pigment. Furthermore, Patent Document 3 discloses a rust-preventive coating film containing a vinylidene chloride resin (1) and an acrylic resin (2), the acrylic resin (2) having a glass transition temperature (Tg) of 20 to 40° C. Patent Document 4 discloses an aqueous resin dispersion containing a polymer (A) containing 0.1 to 5.0 mass% of alkoxysilane group-containing polymerizable monomer units (a) and 0.2 to 4.0 mass% of carboxyl group-containing polymerizable monomer units (b), and 0.05 to 0.5 mass% of Na or K.

[0007] JP 2016-188368 A JP 2014-074120 A JP 2014-231587 A JP 2019-35007 A

[0008] As described above, techniques for improving antifouling properties have been developed, and various anticorrosive paints and resins for use in anticorrosive paints have been disclosed. However, conventional resin compositions for paints have room for improvement in terms of weather resistance.

[0009] The present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide a resin composition for paints which has excellent weather resistance.

[0010] The present inventors have conducted extensive research into paint resin compositions and have found that the use of a silicone-modified polymer emulsion of a specific structure can provide paint resin compositions with excellent weather resistance. This led to the realization that the above-mentioned problems could be solved in an excellent manner, and has thus arrived at the present invention.

[0011] The present invention includes the following resin compositions for paints, etc. [1] A resin composition for paints containing a silicone-modified polymer emulsion, the silicone-modified polymer emulsion having structural units derived from a polymerizable unsaturated monomer and structures derived from a silane compound, and the proportion of the structures derived from the silane compound relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer is 10% by mass or more. [2] The silane compound is a compound represented by the following formula (1); R １ ｎ -Si-R ２ ４－ｎ (1) (wherein, R １ are the same or different and represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ２ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ does not have a polymerizable unsaturated group. n is an integer of 1 to 4. The coating resin composition according to the above item [1], which comprises a silane compound (a) represented by the formula (1) and a silane compound (b) having a polymerizable unsaturated group, and the proportion of structures derived from the silane compound (b) having a polymerizable unsaturated group in the silicone-modified polymer emulsion is 0.1 to 5 mass% relative to 100 mass% of structural units derived from the polymerizable unsaturated monomer. [3] The coating resin composition according to the above item [2], wherein the proportion of structures derived from the silane compound (a) represented by the formula (1) above relative to 100 mass% of structural units derived from the polymerizable unsaturated monomer is 10 mass% or more. [4] The silane compound (a) is a silane compound (a) represented by the formula (1) where n is 2 ２ ) and a silane compound (a) in which n is 3 in the above formula (1).３ [5] The resin composition for paint according to the above [2] or [3], which comprises the silane compound (a ２ ) to the silane compound (a ３ ) mass ratio (silane compound (a ３ ) / silane compound (a ２ )) is 0.7 to 10. [6] The silane compound (a) is a resin composition for paint according to the above [4], wherein R ２ [7] The resin composition for paint according to any one of the above [2] to [5], which contains a compound in which R in the above formula (1) in the silane compound (a) is a hydrocarbon group having 3 to 20 carbon atoms. ２ [8] The resin composition for paint according to any one of the above [2] to [6], wherein the proportion of the compound having a hydrocarbon group having 3 to 20 carbon atoms is 0.1 to 30 mass % relative to 100 mass % of the silane compound (a). (In the formula, R ３ are the same or different and represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ４ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X represents a direct bond or a divalent linking group. m is an integer of 1 to 3. R ５ , R ６ and R ７ are the same or different and represent a hydrogen atom or a methyl group.) The resin composition for paint according to any one of [2] to [7] above, wherein the resin composition for paint is a compound represented by the formula: [9] The resin composition for paint according to [1] above, wherein the resin composition for paint contains a hydrophilic polymer.

[10] The resin composition for paint according to [9] above, wherein the hydrophilic polymer has a solubility in water of 50 g / 100 g or more at 25°C.

[11] The hydrophilic polymer has a solubility parameter of 11 (cal / cm) of the homopolymer calculated by the following method. ３ ) １／２ The resin composition for paint according to the above [9] or

[10] , wherein the proportion of structural units derived from the monomers having the above structure is 70 to 100% by mass relative to 100% by mass of all structural units. <Method for calculating solubility parameter> The solubility parameter (δ) (cal / cm３ ) １／２ is calculated by the following calculation method based on the evaporation energy (Δei) and molar volume (Δvi) of the structural units forming the polymer: δ=(Δei / Δvi) １／２

[12] The coating resin composition according to any one of [9] to

[11] above, wherein the content of the hydrophilic polymer is 1.0 to 15 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomers in the silicone-modified polymer emulsion.

[13] The coating resin composition according to any one of [1] to

[12] above, wherein the silicone-modified polymer emulsion contains structural units derived from a monomer having a branched alkyl group in a proportion of 5 to 75 mass% relative to 100 mass% of all structural units derived from the polymerizable unsaturated monomers.

[14] The coating resin composition according to any one of [1] to

[13] above, wherein the silicone-modified polymer emulsion has a glass transition temperature of -20 to 50°C.

[15] The coating resin composition according to any one of [1] to

[14] above, wherein the silicone-modified polymer emulsion is in the form of emulsion particles having a multilayer structure.

[16] The coating resin composition according to any one of [1] to

[15] above, wherein the silicone-modified polymer emulsion is an emulsion particle having at least a three-layer structure consisting of an outer layer, an intermediate layer, and an inner layer, and the proportion of the inner layer relative to the total of the outer layer and the intermediate layer (100% by mass) is 10 to 100% by mass.

[17] The coating resin composition according to any one of [1] to

[16] above, wherein the silicone-modified polymer emulsion has structural units derived from an ultraviolet-absorbing monomer and / or an ultraviolet-stable monomer.

[18] The coating resin composition according to any one of [1] to

[17] above, further comprising a crosslinking agent.

[19] The coating resin composition according to any one of [1] to

[18] above, which is used for rust prevention.

[20] The coating resin composition according to any one of [1] to

[19] above, which is used for metal members.

[21] A method for producing a resin composition for paint containing a silicone-modified polymer emulsion, the method comprising a step of silicone-modifying a monomer component containing a polymerizable unsaturated monomer or a polymer thereof with a silane compound, in which the amount of silane compound used in the silicone-modifying step is 10 mass% or more relative to 100 mass% of the polymerizable unsaturated monomer.

[0012] The resin composition for coating of the present invention has the above-mentioned constitution and is excellent in weather resistance, and therefore can be suitably used as a coating material for painting the exterior walls of buildings.

[0013] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope that does not change the gist of the present invention. It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below also falls within the scope of preferred embodiments of the present invention. In this specification, "(meth)acryloyl" means "acryloyl" or "methacryloyl", "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)acrylic" means "acrylic" or "methacrylic".

[0014] [Paint Resin Composition] The paint resin composition of the present invention is a paint resin composition containing a silicone-modified polymer emulsion (hereinafter simply referred to as emulsion), the silicone-modified polymer emulsion having structural units derived from a polymerizable unsaturated monomer and structures derived from a silane compound, and the proportion of the silane compound-derived structures relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer is 10% by mass or more. The silicone-modified polymer emulsion has a structure in which at least one structural unit derived from a polymerizable unsaturated monomer and at least one structure derived from a silane compound are directly or indirectly bonded, and by having the silane compound-derived structures in the above proportion, it is thought that the network structure of the silane compound-derived structures exhibits barrier properties, thereby enabling the emulsion to exhibit excellent weather resistance.

[0015] The above-mentioned resin composition for paint preferably contains a hydrophilic polymer, which allows it to exhibit long-term stain resistance. The above-mentioned silicone-modified polymer emulsion has a predetermined structure, and exhibits barrier properties due to a network structure derived from the silane compound, and is thought to be able to exhibit long-term stain resistance by suppressing the elution of the hydrophilic polymer over time.

[0016] The proportion of the silicone-modified polymer emulsion in the coating resin composition of the present invention is not particularly limited, but is preferably 5 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, based on 100% by mass of the coating resin composition.

[0017] The proportion of the hydrophilic polymer in the coating resin composition of the present invention is not particularly limited, but is preferably 1.0 to 15% by mass relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer in the silicone-modified polymer emulsion. This further improves stain resistance. It is more preferably 2.0 to 12% by mass, even more preferably 2.5 to 10% by mass, and particularly preferably 3.0 to 10% by mass. From the viewpoint of long-term stain resistance, an embodiment in which the proportion of the hydrophilic polymer is 2.0 to 8% by mass or 2.5 to 5% by mass is also one of the preferred embodiments of the present invention.

[0018] The paint resin composition of the present invention may contain other components in addition to the silicone-modified polymer emulsion and the hydrophilic polymer. The proportion of the other components is not particularly limited, but is preferably 0.01 to 30% by mass relative to 100% by mass of the paint resin composition. It is more preferably 0.1 to 20% by mass, and even more preferably 0.1 to 10% by mass. In one embodiment, when the other components include a solvent, the proportion of the other components is preferably 20 to 95% by mass relative to 100% by mass of the paint resin composition. It is more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass.

[0019] The coating resin composition of the present invention may contain a crosslinking agent, and although there are no particular restrictions on the proportion thereof, it is preferably 0 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 2 to 10% by mass, relative to 100% by mass of the combined mass of the silicone-modified polymer emulsion and the hydrophilic polymer.

[0020] The essential components and optional components contained in the resin composition for coating of the present invention will be further described below.

[0021] <<Silicone-Modified Polymer Emulsion>> The silicone-modified polymer emulsion contained in the coating resin composition of the present invention has structural units derived from polymerizable unsaturated monomers and structures derived from silane compounds, and the ratio of the structures derived from silane compounds to 100% by mass of the structural units derived from polymerizable unsaturated monomers is 10% by mass or more. In the present invention, "structural units derived from polymerizable unsaturated monomers" refers to structural units having the same structure as the structural units formed by polymerization of polymerizable unsaturated monomers. Note that the structural units having the same structure as the structural units formed by polymerization of polymerizable unsaturated monomers are not limited to structural units formed by actual polymerization of polymerizable unsaturated monomers, but may also be structural units formed by other methods as long as they have the same structure as the structural units formed by polymerization of polymerizable unsaturated monomers. The silane compound may have a silicon-containing group and may further have a reactive group other than the silicon-containing group, such as a polymerizable unsaturated group. In the present invention, the term "silane compound-derived structure" refers to a structure identical to the structure formed by reaction of a silicon-containing group possessed by a silane compound and / or, if the silane compound has a reactive group other than a silicon-containing group, by reaction of the reactive group. In the silicone-modified polymer emulsion, the proportion of the silane compound-derived structure is preferably 10 to 120% by mass, more preferably 15 to 110% by mass, even more preferably 18 to 100% by mass, even more preferably 20 to 95% by mass, even more preferably 25 to 90% by mass, and particularly preferably 28 to 85% by mass, relative to 100% by mass of structural units derived from the polymerizable unsaturated monomer. In one aspect, an embodiment in which the proportion of the silane compound-derived structure is 20 to 50% by mass is also one of the preferred embodiments of the present invention. In one embodiment, the proportion of the structure derived from the silane compound is preferably 10 to 100% by mass, more preferably 15 to 90% by mass, even more preferably 20 to 80% by mass, even more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass. An embodiment in which the proportion of the structure derived from the silane compound is 20 to 40% by mass is also one of the preferred embodiments of the present invention.In this specification, the polymerizable unsaturated monomer does not include the silane compound (b) having a polymerizable unsaturated group, which will be described later, and the silane compound having a polymerizable unsaturated group is classified as a silane compound in this specification.

[0022] The silicone-modified polymer emulsion contains a silane compound represented by the following formula (1): １ ｎ -Si-R ２ ４－ｎ (1) (wherein, R １ are the same or different and represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ２ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ does not have a polymerizable unsaturated group. n is an integer of 1 to 4. It is preferable that the silane compound (a) has a structure derived from the silane compound (a) represented by the formula (1). By having a structure derived from the silane compound (a), it is possible to expect an effect of improving the sliding properties of the coating film. Furthermore, with regard to the structure derived from the silane compound (a) represented by the formula (1), when n is 1 and / or 2, it is possible to expect an effect of improving the flexibility of the coating film, and when n is 3 and / or 4, it is possible to expect an effect of improving the solvent resistance and coating hardness of the coating film.

[0023] The silane compound (a) is a compound represented by the formula (1) above, and is —Si—R １ In the present invention, the "structure derived from silane compound (a)" means a structure identical to the structure formed by a condensation reaction of the hydrolyzable silyl groups contained in silane compound (a). Note that the "structure identical to the structure formed by a condensation reaction of silane compound (a)" is not limited to only the structure formed by the actual condensation reaction of silane compound (a), but may also be a structure formed by another method as long as it has the same structure as the structure formed by the condensation reaction of silane compound (a).

[0024] In the silicone-modified polymer emulsion, the proportion of the structure derived from the silane compound (a) is not particularly limited, but is preferably 8 to 90% by mass relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer. By having the proportion of the structure derived from the silane compound (a) in the silicone-modified polymer emulsion within the above range, the weather resistance, solvent resistance, and hardness of the coating film can be expected to be improved. The proportion of the structure derived from the silane compound (a) is more preferably 10 to 85% by mass, even more preferably 15 to 80% by mass, even more preferably 15 to 70% by mass, and particularly preferably 20 to 65% by mass.

[0025] The silicone-modified polymer emulsion contains, as the silane compound (a), R ２ is a hydrocarbon group having 3 to 20 carbon atoms (hereinafter referred to as R ２Preferably, the silicone-modified polymer emulsion has a structure derived from the hydrophobic group-containing silane compound (a compound in which the hydrocarbon group having 3 to 20 carbon atoms is also referred to as a hydrophobic group-containing silane compound). This enables the formation of a coating film with higher barrier properties. The proportion of the structure derived from the hydrophobic group-containing silane compound in the silicone-modified polymer emulsion is not particularly limited, but is preferably 0.1 to 30 mass% relative to 100 mass% of the structure derived from silane compound (a). It is more preferably 0.5 to 28 mass%, and even more preferably 1 to 25 mass%. In one embodiment, the proportion of the structure derived from the hydrophobic group-containing silane compound may be 5 to 20 mass%. The silicone-modified polymer emulsion also preferably has a proportion of the hydrophobic group-containing silane compound structure in the range of 0.1 to 30 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomer. Having the proportion of the structure derived from the hydrophobic group-containing silane compound within the above range is expected to improve compatibility with acrylic polymers and film-forming properties of the coating film, thereby improving the appearance of the coating film. Furthermore, by ensuring that the proportion of the structure derived from the hydrophobic group-containing silane compound is within the above range, the water resistance and water stop properties of the coating film can be improved, and improved rust prevention properties of the coating film can be expected. The proportion of the structure derived from the hydrophobic group-containing silane compound is more preferably 0.1 to 20 mass%, even more preferably 0.2 to 15 mass%, even more preferably 0.5 to 10 mass%, and particularly preferably 1 to 10 mass%.

[0026] The silicone-modified polymer emulsion preferably contains, as the silane compound, a structure derived from a silane compound (b) having a polymerizable unsaturated group.

[0027] The silane compound (b) is a compound having a polymerizable unsaturated group and a silicon-containing group, and in the present invention, "structure derived from silane compound (b)" means the same structure as the structure formed by the polymerization of the polymerizable unsaturated group of silane compound (b) and / or the reaction of the silicon-containing group. Note that the same structure as the structure formed by the polymerization reaction of silane compound (b) is not limited to only the structure formed by the actual polymerization reaction of silane compound (b), and may also be a structure formed by other methods as long as it has the same structure as the structure formed by the polymerization reaction of silane compound (b).

[0028] In the silicone-modified polymer emulsion, the proportion of the structure derived from the silane compound (b) having a polymerizable unsaturated group is preferably 0.1 to 5 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomer. This ensures that the flexibility of the resulting coating film is within a suitable range. The proportion of the structure derived from the silane compound (b) is more preferably 0.01 to 5 mass%, even more preferably 0.05 to 5 mass%, and particularly preferably 0.1 to 4 mass%.

[0029] In one preferred embodiment of the present invention, the silicone-modified polymer emulsion has a crosslinked structure formed by silane compounds (a) and (b), the proportion of structures derived from the silane compounds is 10% by mass or more relative to 100% by mass of structural units derived from polymerizable unsaturated monomers, and the proportion of structures derived from silane compound (b) is 0.1 to 5% by mass. This allows the silicone-modified polymer emulsion to exhibit superior barrier properties against saltwater, light, heat, etc., and is therefore thought to have excellent rust prevention and weather resistance.

[0030] The silicone-modified polymer emulsion preferably contains structural units derived from a monomer having a branched alkyl group as the polymerizable unsaturated monomer. This is thought to further improve barrier properties by causing the branched alkyl groups to become entangled with each other, thereby further improving water blister resistance. The proportion of structural units derived from monomers having a branched alkyl group in the silicone-modified polymer emulsion is not particularly limited, but is preferably 5 to 75% by mass relative to 100% by mass of structural units derived from polymerizable unsaturated monomers. It is more preferably 10 to 70% by mass, even more preferably 15 to 65% by mass, and particularly preferably 20 to 60% by mass.

[0031] The weight average molecular weight of the silicone-modified polymer emulsion is not particularly limited, but it is preferable that the weight average molecular weight of the emulsion before the formation of a crosslinked structure is 100,000 or more. This results in the obtained coating film having better weather resistance and flexibility. The weight average molecular weight is more preferably 200,000 or more, even more preferably 500,000 or more, and particularly preferably 1,000,000 or more. The weight average molecular weight is preferably 10,000,000 or less. When the silicone-modified polymer emulsion has a multilayer structure, it is preferable that the weight average molecular weight of the resin constituting each layer (when the silicone-modified polymer emulsion has a crosslinked structure, the emulsion before the formation of the crosslinked structure) is 100,000 or more. It is more preferably 200,000 or more, even more preferably 500,000 or more, and particularly preferably 1,000,000 or more. The weight average molecular weight is preferably 10,000,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (Tosoh Corporation, product number: HLC-8120GPC, columns: TSKgel G-5000HXL and TSKgel GMHXL-L connected in series).

[0032] The silicone-modified polymer emulsion preferably has a glass transition temperature (Tg) of -20 to 50°C. This further improves film-forming properties and sufficiently suppresses cracking of the coating film. The Tg is more preferably -20 to 45°C, even more preferably -15 to 40°C, and particularly preferably -10 to 25°C. The Tg of the silicone-modified polymer emulsion can be calculated by the following method. <Method of Calculating Tg> In this specification, the glass transition temperature of an emulsion refers to a temperature calculated based on the Fox equation, expressed by the formula (I) using the glass transition temperature of a homopolymer of the monomer used in the monomer component constituting the emulsion: 1 / Tg=Σ(Wm / Tgm) / 100 (I) (where Wm is the content (mass%) of monomer m in the monomer component constituting the polymer, and Tgm is the glass transition temperature (absolute temperature: K) of the homopolymer of monomer m).

[0033] In the present invention, the glass transition temperature of an emulsion means the glass transition temperature calculated based on formula (I), unless otherwise specified.

[0034] The glass transition temperature of the entire resin layers constituting emulsion particles having a plurality of resin layers means the glass transition temperature calculated from the mass fraction of each monomer in all the monomer components used in the multistage emulsion polymerization and the glass transition temperature of the homopolymer of the corresponding monomer.

[0035] For monomers with unknown glass transition temperatures, such as special monomers and polyfunctional monomers, if the total amount of monomers with unknown glass transition temperatures in the monomer composition is 10% by mass or less, the glass transition temperature can be determined using only monomers with known glass transition temperatures. If the total amount of monomers with unknown glass transition temperatures in the monomer composition exceeds 10% by mass, the glass transition temperature of the polymer can be determined by differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermomechanical analysis (TMA), or the like.

[0036] The glass transition temperature of the emulsion can be easily adjusted by adjusting the composition of the monomer components. The composition of the monomer components can be determined taking into account the glass transition temperature of the polymer that constitutes the emulsion particles.

[0037] The glass transition temperature of the resin (polymer) is, for example, 83°C for a homopolymer of cyclohexyl methacrylate, 105°C for a homopolymer of methyl methacrylate, -70°C for a homopolymer of 2-ethylhexyl acrylate, -54°C for a homopolymer of n-butyl acrylate, 55°C for a homopolymer of 2-hydroxyethyl methacrylate, 106°C for a homopolymer of acrylic acid, 130°C for a homopolymer of methacrylic acid, 65°C for a homopolymer of diacetone acrylamide, 97°C for a homopolymer of isobornyl acrylate, -44°C for a homopolymer of 2-octyl acrylate, -45°C for isoamyl acrylate, 130°C for a homopolymer of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, and 130°C for a monomer of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine.

[0038] The silicone-modified polymer emulsion may have a single-layer structure, but is preferably in the form of emulsion particles having a multi-layer structure. The use of such emulsion particles results in a more favorable balance between flexibility and water resistance of the formed coating film.

[0039] When the silicone-modified polymer emulsion has a two-layer structure, the ratio of the inner layer to the outer layer is preferably 10 to 100% by mass, more preferably 10 to 70% by mass, even more preferably 10 to 65% by mass, and particularly preferably 15 to 60% by mass.

[0040] The silicone-modified polymer emulsion is more preferably an emulsion particle having a structure of at least three layers, namely, an outer layer, an intermediate layer, and an inner layer, and even more preferably an emulsion particle having a three-layer structure of an outer layer, an intermediate layer, and an inner layer. When the silicone-modified polymer emulsion has a structure of three or more layers, the outer layer refers to the layer that forms the outermost layer, the inner layer refers to the layer formed near the center (the innermost layer), and the intermediate layer refers to all layers located between the outer layer and the inner layer (synthesized in the middle). When the silicone-modified polymer emulsion has a structure of three or more layers, the proportion of the inner layer relative to the total of the outer layer and the intermediate layer (100% by mass) is preferably 10 to 100% by mass. It is more preferably 10 to 70% by mass, even more preferably 10 to 60% by mass, and particularly preferably 15 to 35% by mass.

[0041] When the silicone-modified polymer emulsion has a structure of three or more layers, the intermediate layer may have a structure derived from a silane compound, but the proportion thereof is preferably 5% by mass or less relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer constituting the intermediate layer.This makes the flexibility of the silicone-modified polymer emulsion more suitable.The proportion of the structure derived from a silane compound in the intermediate layer is more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0% by mass.

[0042] When the silicone-modified polymer emulsion has a structure of three or more layers, it is preferable that the outer layer and / or inner layer contain a structure derived from a silane compound. The use of such emulsion particles results in a coating film having a favorable balance between flexibility and water permeability resistance. More preferably, the outer and inner layers contain a structure derived from a silane compound. The proportion of the silane compound-derived structure in the outer layer is preferably 2 to 150% by mass relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer that constitute the outer layer. It is more preferably 3 to 100% by mass, even more preferably 4 to 80% by mass, and particularly preferably 5 to 70% by mass. The proportion of the silane compound-derived structure in the inner layer is preferably 10 to 250% by mass relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer that constitute the inner layer. It is more preferably 15 to 220% by mass, even more preferably 20 to 180% by mass, and particularly preferably 25 to 150% by mass.

[0043] When the silicone-modified polymer emulsion has a multilayer structure, the Tg of the resin constituting the innermost layer is preferably 40°C or higher, more preferably 45 to 130°C, even more preferably 50 to 120°C, and particularly preferably 70 to 100°C.

[0044] When the silicone-modified polymer emulsion has a multilayer structure, the Tg of the resin constituting the outermost layer is preferably −40 to 40° C., more preferably −35 to 35° C., and particularly preferably −30 to 30° C.

[0045] When the silicone-modified polymer emulsion has a structure of three or more layers, the Tg of the resin constituting the intermediate layer is preferably 10°C or less, more preferably 0°C or less, even more preferably -10°C or less, still more preferably -11°C or less, still more preferably -13°C or less, and particularly preferably -15°C or less.

[0046] When the silicone-modified polymer emulsion has a two-layer structure or a three-layer or greater structure, the difference in Tg between the resin constituting the inner layer and the resin constituting the outer layer (inner layer Tg - outer layer Tg) in the case of a two-layer structure, or the difference in Tg between the resin constituting the inner layer and the resin constituting the intermediate layer (inner layer Tg - intermediate layer Tg) in the case of a three-layer or greater structure, is preferably 40°C or greater. The use of such emulsion particles ensures that the coating film formed has a suitable balance between flexibility and water permeability resistance. The difference is more preferably 50°C or greater, even more preferably 60°C or greater, and particularly preferably 70°C or greater.

[0047] <MFT> From the viewpoint of improving the film-forming properties of the coating film, the minimum film-forming temperature (MFT) of the silicone-modified polymer emulsion is preferably 0 to 40° C. The minimum film-forming temperature of the silicone-modified polymer emulsion can be adjusted, for example, by adjusting the glass transition temperature of the entire emulsion particle or the glass transition temperature of the outermost layer.

[0048] The minimum film-forming temperature of the silicone-modified polymer emulsion refers to the boundary temperature between the film-forming area and the non-film-forming area when the emulsion is applied in a band shape to a flat plate having an appropriate temperature gradient, and is defined as "the minimum temperature at which a crack-free, uniform coating film is formed."

[0049] The minimum film-forming temperature of the silicone-modified polymer emulsion can be measured, for example, in accordance with JIS K6828-2 (2003). More specifically, using an MFT tester (manufactured by Tester Sangyo Co., Ltd., product number: TP-801 LT), a coating film of the resin emulsion having a dry thickness of 250 μm is formed with an applicator on a grooveless stainless steel plate, and the minimum temperature (°C) at which a crack-free, uniform coating film is formed is measured. The presence or absence of cracks in the coating film can be determined visually in accordance with JIS K6828-2. Note that if the minimum film-forming temperature of the coating film is 0°C or lower, the minimum film-forming temperature of the coating film is considered to be 0°C.

[0050] <Silane Compound> The silane compound constituting the silicone-modified polymer emulsion may be any compound having a silicon-containing group, but is preferably a compound having a hydrolyzable silyl group. When the silane compound is a compound having a hydrolyzable silyl group, the silane compounds react with each other and / or with reactive groups in structural units derived from polymerizable monomers to form a network structure, thereby further improving the barrier properties of the coating film.

[0051] The silane compound is represented by the following formula (1): １ ｎ -Si-R ２ ４－ｎ (1) (wherein, R １ are the same or different and represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ２ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ does not have a polymerizable unsaturated group, and n is an integer of 1 to 4. It is preferable that the silane compound (a) is represented by the following formula (I):

[0052] The silane compound is more preferably a compound containing a silane compound (a) and a silane compound (b). The silane compound (b) is a compound having a polymerizable unsaturated group and a silicon-containing group, and is polymerized with a polymerizable unsaturated monomer to form a polymer chain. The silicon-containing group in the structural unit derived from the silane compound (b) reacts with the silane compound (a), and the silane compound (a) can be incorporated as a side chain of the polymer chain. The silane compound (a) incorporated as a side chain of the polymer chain can further react with the silicon-containing group of the structural unit derived from the silane compound (a) or another polymer chain to form a denser network structure.

[0053] (Silane Compound (a)) The silane compound (a) is a compound represented by the above formula (1), and is —Si—R １ R in the above formula (1) has a hydrolyzable silyl group. １ are the same or different and are a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group.１ is preferably a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, and more preferably an alkoxy group having 1 to 20 carbon atoms.

[0054] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n -pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group. Among these, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups are preferred, and methoxy and ethoxy groups are more preferred.

[0055] The alkoxy group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0056] R in the above formula (1) ２ are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ When R is a hydrocarbon group, it is a group that does not have a polymerizable unsaturated group. １Preferably, the hydrocarbon group does not have a polymerizable unsaturated group. Examples of the hydrocarbon group that does not have a polymerizable unsaturated group include an alkyl group, an aryl group, and an aralkyl group.

[0057] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 1-methylpentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-ethylhexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, a neoheptyl group, an n-octyl group, an isooctyl group, and a sec -octyl group, tert-octyl group, neooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, n-tridecyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group, n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, n-pentadecyl group, isopentadecyl group, sec-pentadecyl group, tert-pentadecyl group, neopentadecyl group, n-hexadecyl group, isohexadecyl group, sec-hexadecyl group, tert-hexadecyl group, neohexadecyl group, n-heptadecyl group, isoheptadecyl group, sec-heptadecyl group, tert-heptadecyl group, neoheptadecyl group, n-octadecyl group, isooctadecyl group, sec-octadecyl group decyl group, tert-octadecyl group, neooctadecyl group, n-nonadecyl group, isononadecyl group, sec-nonadecyl group, tert-nonadecyl group, neononadecyl group, n-icosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl group,Examples include a cycloicosyl group.

[0058] Examples of the aryl group include a phenyl group, an o-, m-, or p-tolyl group, a 2,3-, or 2,4-xylyl group, a mesityl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a benzhydryl group, etc.

[0059] The above R ２ The number of carbon atoms in the hydrocarbon group in R is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4. In addition, the silane compound (a) is ２ is a hydrocarbon group having 3 to 20 carbon atoms, and in this case, R ２ The number of carbon atoms in the hydrocarbon group is preferably 3 to 18, more preferably 4 to 16, even more preferably 4 to 12, and particularly preferably 4 to 8. When the hydrocarbon group is an aryl group or an aralkyl group, the number of carbon atoms is preferably 6 to 20, more preferably 6 to 16, even more preferably 6 to 12, and particularly preferably 6 to 8. R in the hydrophobic group-containing silane compound ２ is preferably an aryl group or an aralkyl group, more preferably an aryl group, and even more preferably a phenyl group. From the viewpoint of further improving the barrier property and rust prevention performance of the coating film, n in formula (1) is 2 and two R ２ An embodiment containing a hydrophobic group-containing silane compound in which is an aryl group is one of the preferred embodiments of the present invention.

[0060] The hydrocarbon group having no polymerizable unsaturated group is preferably an alkyl group or an aryl group, and more preferably, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 1-methylpentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, or a neohexyl group. and alkyl groups having 1 to 8 carbon atoms such as 2-ethylhexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, and neooctyl; and phenyl groups, and more preferably alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; and phenyl groups.

[0061] In the above formula (1), n ​​is an integer of 1 to 4. n is preferably 2 or 3. As the silane compound (a), a silane compound (a) in which n in formula (1) is 2 is also preferred. ２ By using the silane compound (a), it is expected that the coating film will have both weather resistance and flexibility. ３ By using the silane compound (a), it is expected that the solvent resistance and hardness of the coating film will be improved. ２ ) and a silane compound (a) in which n is 3 in formula (1) ３ In this case, the ratio of hydroxyl groups, alkoxy groups, or acetoxy groups involved in condensation in the silane compound (a) tends to fall within a more suitable range, and a crosslinked structure with higher barrier properties can be formed when the resulting coating film is formed.

[0062] The silane compound (a) is ２ ) and the silane compound (a ３ ), the silane compound (a ２ ) to the silane compound (a３ ) mass ratio (silane compound (a ３ ) / silane compound (a ２ )) is preferably 0.7 to 10. This allows a crosslinked structure with higher barrier properties to be formed when the coating film is formed. The above mass ratio is more preferably 1 to 8, and even more preferably 2 to 7.

[0063] Silane compound (a) in which n is 1 in the above formula (1) １) may be, for example, trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, trimethyl-iso-propoxysilane, trimethyl-n-butoxysilane, trimethyl-sec-butoxysilane, trimethyl-tert-butoxysilane, trimethylphenoxysilane, triethylmethoxysilane, triethylethoxysilane, triethyl-n-propoxysilane, triethyl-iso-propoxysilane, triethyl-n-butoxysilane, triethyl-sec-butoxysilane, triethyl-tert-butoxysilane, triethylphenoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-propyl-n-propoxysilane, tri-n-propyl-iso-propoxysilane, tri-n-propyl-n-butoxysilane, tri-n-propyl-sec-butoxysilane, tri-n-propyl-tert-butoxysilane, tri-n-propylphenoxysilane, tri-i-propylmethoxysilane, tri-i-propylethoxysilane, tri-i-propyl-n-propoxysilane, tri-i-propyl-i so-propoxysilane, tri-i-propyl-n-butoxysilane, tri-i-propyl-sec-butoxysilane, tri-i-propyl-tert-butoxysilane, tri-i-propylphenoxysilane, tri-n-butylmethoxysilane, tri-n-butylethoxysilane, tri-n-butyl-n-propoxysilane, tri-n-butyl-iso-propoxysilane, tri-n-butyl-n-butoxysilane, tri-n-butyl-sec-butoxysilane, tri-n-butyl-tert-butoxysilane, tri-n-butylphenoxysilane , tri-sec-butylmethoxysilane, tri-sec-butylethoxysilane, tri-sec-butyl-n-propoxysilane, tri-sec-butyl-iso-propoxysilane, tri-sec-butyl-n-butoxysilane, tri-sec-butyl-sec-butoxysilane, tri-sec-butyl-tert-butoxysilane, tri-sec-butyl-tri-phenoxysilane, tri-t-butylmethoxysilane, tri-t-butylethoxysilane, tri-t-butyl-n-propoxysilane, tri-t-butyl-iso-propoxysilane,Examples of such silanes include tri-t-butyl-n-butoxysilane, tri-t-butyl-sec-butoxysilane, tri-t-butyl-tert-butoxysilane, tri-t-butylphenoxysilane, tri-phenylmethoxysilane, tri-phenylethoxysilane, tri-phenyl-n-propoxysilane, tri-phenyl-iso-propoxysilane, tri-phenyl-n-butoxysilane, tri-phenyl-sec-butoxysilane, tri-phenyl-tert-butoxysilane, and tri-phenylphenoxysilane.

[0064] Silane compound (a) in which n is 2 in the above formula (1) ２) may be, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di -tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-diphenoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane diisopropyl-di-isopropyl-propoxysilane, diisopropyl-di-n-butoxysilane, diisopropyl-di-sec-butoxysilane, diisopropyl-di-tert-butoxysilane, diisopropyl-diphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-isopropylpropoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n- butyl-di-tert-butoxysilane, di-n-butyl-diphenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, di-sec-butyl-di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-diphenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane,Di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-diphenoxysilane, dipentyldimethoxysilane, dipentyldiethoxysilane, dihexyldimethoxysilane, dihexyldiethoxysilane, diheptyldimethoxysilane, diheptyldiethoxysilane, dioctyldimethoxysilane, dioctyldimethoxysilane, Examples of the silane include ethyldiethoxysilane, dinonyldimethoxysilane, dinonyldiethoxysilane, didecyldimethoxysilane, didecyldiethoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, phenylmethyldimethoxysilane, and dicyclohexyldiethoxysilane. Among these, preferred are diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, dicyclohexyldimethoxysilane, and dicyclohexyldiethoxysilane, and more preferred are diphenyldimethoxysilane, diphenyldiethoxysilane, and phenylmethyldimethoxysilane.

[0065] Silane compound (a) in which n is 3 in the above formula (1) ３) may be, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane , i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-buthoxysilane t-butyltriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltri-iso-propoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane,t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, Examples of such silanes include trimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyltriethoxysilane, and dicyclohexyldiethoxysilane. Among these, preferred are methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, and cyclohexyltriethoxysilane, and more preferred are methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

[0066] (Silane Compound (b)) The silane compound (b) having a polymerizable unsaturated group may be a compound having a polymerizable unsaturated group and a silicon-containing group, but is preferably a compound having a polymerizable unsaturated group and a hydrolyzable silyl group. The hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom. More preferably, the silane compound (b) is a compound represented by the following formula (2):

[0067]

[0068] (In the formula, R ３ are the same or different and represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ４ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X represents a direct bond or a divalent linking group. m is an integer of 1 to 3. R ５ , R６ and R ７ are the same or different and represent a hydrogen atom or a methyl group.

[0069] R in the above formula (2) ３ are the same or different and are a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ３ is preferably a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, and more preferably an alkoxy group having 1 to 20 carbon atoms. ３ Specific examples and preferred forms of the alkoxy group in R １ As mentioned above. ３ is preferably a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, or a t-butoxy group, and more preferably a methoxy group or an ethoxy group.

[0070] R in the above formula (2) ４ are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ４ Examples of the hydrocarbon group in include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Specific examples of the alkyl group, the aryl group, and the aralkyl group are ２ As stated above.

[0071] The hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10, even more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4. When the hydrocarbon group is an aryl group or an aralkyl group, the hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 16, even more preferably 6 to 12, and particularly preferably 6 to 8 carbon atoms.

[0072] Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, and icosenyl groups. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecenyl, and icosenyl groups.

[0073] The above R ４ Preferred hydrocarbon groups in R ２ This is the same as the preferred form of the hydrocarbon group not having a polymerizable unsaturated group in the above.

[0074] R in the above formula (2) ５ , R ６ and R ７ are the same or different and each is a hydrogen atom or a methyl group. ５ , R ６ is a hydrogen atom, and R ７ is a hydrogen atom or a methyl group. More preferably, R ５ , R ６ is a hydrogen atom, and R ７ is a methyl group.

[0075] X in the above formula (2) is a direct bond or a divalent linking group. The divalent linking group in X is not particularly limited, but may be —OR ｘ’ --, --NHR ｘ’’ - and the like. ｘ’ , R ｘ’’is preferably an alkylene group having 1 to 20 carbon atoms. The alkylene group is not particularly limited, but examples thereof include a methylene group, a methylmethylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a neopentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group.

[0076] The number of carbon atoms in the alkylene group is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 8, even more preferably 1 to 6, and particularly preferably 1 to 4. The alkylene group is preferably a methylene group, a methylmethylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, or a tert-butylene group, and more preferably an ethylene group or an n-propylene group.

[0077] m is an integer of 1 to 3. m is preferably 2 or 3. This allows the condensation reaction with the silane compound (a) to proceed effectively, and a suitable network structure can be formed. m is more preferably 3.

[0078] Examples of the silane compound (b) include 1-(meth)acryloyloxymethyltrimethoxysilane, 1-(meth)acryloyloxymethylmethyldimethoxysilane, 1-(meth)acryloyloxymethyltriethoxysilane, 1-(meth)acryloyloxymethylmethyldiethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, 2-(meth)acryloyloxyethylmethyldimethoxysilane, 2-(meth)acryloyloxyethyltriethoxysilane, 2-(meth)acryloyloxyethylmethyldiethoxysilane, 3- (meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, 4-(meth)acryloyloxybutylmethyldimethoxysilane, 4-(meth)acryloyloxybutyltriethoxysilane, 4-(meth)acryloyloxybutylmethyldiethoxysilane, 5-(meth)acryloyloxypropyltrimethoxysilane, 5-(meth)acryloyloxypropylmethyldimethoxysilane, 5-(meth)acryloyloxypropyltriethoxysilane, 5-(meth)acryloyloxypropylmethyldiethoxysilane, 5-(meth)acryloyloxypropyltriethoxy ... hydroxypentyltrimethoxysilane, 5-(meth)acryloyloxypentylmethyldimethoxysilane, 5-(meth)acryloyloxypentyltriethoxysilane, 5-(meth)acryloyloxypentylmethyldiethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 6-(meth)acryloyloxyhexylmethyldimethoxysilane, 6-(meth)acryloyloxyhexyltriethoxysilane, 6-(meth)acryloyloxyhexylmethyldiethoxysilane, 7-(meth)acryloyloxyheptyl trimethoxysilane, 7-(meth)acryloyloxyheptylmethyldimethoxysilane, 7-(meth)acryloyloxyheptyltriethoxysilane, 7-(meth)acryloyloxyheptylmethyldiethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, 8-(meth)acryloyloxyoctylmethyldiethoxysilane, 3-(meth)acryloyloxypropylhydroxysilane,Examples include 3-(meth)acryloyloxypropylmethylhydroxysilane, 3-acrylamidopropyltriethoxysilane, and 3-acrylamidopropyltrimethoxysilane. Among these, 1-(meth)acryloyloxymethyltrimethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, and 3-(meth)acryloyloxypropyltrimethoxysilane are preferred, and 3-(meth)acryloyloxypropyltrimethoxysilane is more preferred.

[0079] <Polymerizable Unsaturated Monomer> The polymerizable unsaturated monomer is a monomer having a polymerizable unsaturated group, and the polymerizable unsaturated group is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, etc. The polymerizable unsaturated monomer preferably includes a monomer having a (meth)acryloyl group.

[0080] The polymerizable unsaturated monomer is not particularly limited, and examples thereof include acyclic alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, carbonyl group-containing monomers, hydroxyl group-containing (meth)acrylates, carboxyl group-containing monomers, aromatic monomers, nitrogen atom-containing monomers, oxo group-containing monomers, halogen atom-containing monomers, epoxy group-containing monomers, ultraviolet absorbing monomers, and ultraviolet stable monomers. These monomers may be used alone or in combination of two or more.

[0081] The polymerizable unsaturated monomer preferably contains a hydrophobic monomer such as an acyclic alkyl (meth)acrylate, an alicyclic structure-containing (meth)acrylate, or an aromatic monomer. This allows for the formation of a coating film with higher barrier properties. The total proportion of the acyclic alkyl (meth)acrylate, the alicyclic structure-containing (meth)acrylate, and the aromatic monomer is not particularly limited, but is preferably 60% by mass or more relative to 100% by mass of the polymerizable unsaturated monomer. More preferably, it is 70% by mass or more, and even more preferably, it is 80% by mass or more. The proportion of the hydrophobic monomer is preferably 99% by mass or less. Among hydrophobic monomers, acyclic alkyl (meth)acrylates and alicyclic structure-containing (meth)acrylates are preferred. A preferred embodiment of the present invention is one in which the total proportion of the acyclic alkyl (meth)acrylate and the alicyclic structure-containing (meth)acrylate is within the above-mentioned preferred range.

[0082] The silicone-modified polymer emulsion has a crosslinked structure formed by a silane compound, but may also have a crosslinked structure other than that formed by a silane compound. For example, when the silicone-modified polymer emulsion has a structural unit derived from a monomer having a reactive group, such as a carbonyl group-containing monomer, a hydroxyl group-containing (meth)acrylate, an unsaturated carboxylic acid monomer, an aromatic monomer, a nitrogen atom-containing monomer, or an oxo group-containing monomer, as a structural unit derived from a polymerizable unsaturated monomer, the reactive group can be reacted with a crosslinking agent or the like to form a crosslinked structure. More preferred examples of monomers having a reactive group include carbonyl group-containing monomers and nitrogen atom-containing monomers. Specific examples of monomers having a reactive group include diacetone acrylamide (DAAM). The proportion of the monomer having a reactive group in the polymerizable unsaturated monomer is not particularly limited, but is preferably 0 to 10% by mass relative to 100% by mass of the polymerizable unsaturated monomer. More preferred examples are 1 to 9% by mass, and even more preferred are 2 to 8% by mass. In one embodiment, the content is more preferably 0.1 to 5% by mass, and even more preferably 0.5 to 3% by mass.

[0083] The polymerizable monomer preferably contains an ultraviolet-absorbing monomer and / or an ultraviolet-stable monomer. This provides the silicone-modified polymer emulsion with superior weather resistance. The proportion of the ultraviolet-absorbing monomer and / or ultraviolet-stable monomer is not particularly limited, but the total proportion of the ultraviolet-absorbing monomer and the ultraviolet-stable monomer relative to 100% by mass of the polymerizable unsaturated monomer is preferably 0.1 to 10% by mass. It is more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass. When the silicone-modified polymer emulsion has a multilayer structure, from the viewpoint of weather resistance, it is preferable that the outermost layer contains structural units derived from the ultraviolet-absorbing monomer and / or the ultraviolet-stable monomer. The total proportion of the ultraviolet-absorbing monomer and the ultraviolet-stable monomer in the outermost layer is preferably 1 to 20% by mass relative to 100% by mass of the polymerizable unsaturated monomer forming the outermost layer. It is more preferably 2 to 10% by mass, and even more preferably 3 to 8% by mass.

[0084] When the silicone-modified polymer emulsion has structural units derived from an ultraviolet-absorbing monomer having an amino group and / or an ultraviolet-stable monomer in the outermost layer, the proportion of monomers having an acid group, such as carboxyl group-containing monomers, is preferably 10% by mass or less relative to 100% by mass of the polymerizable unsaturated monomers forming the outermost layer. This sufficiently prevents the amino group and the acid group in the outermost layer from reacting, thereby reducing the stability of the emulsion particles. The proportion of monomers having an acid group is more preferably 5% by mass or less, and even more preferably 1% by mass or less. An embodiment in which the outermost layer does not have structural units derived from monomers having an acid group is one of the preferred embodiments of the present invention.

[0085] When the silicone-modified polymer emulsion has a structure of three or more layers, it is preferable that the intermediate layer contains structural units derived from polar monomers such as hydroxyl group-containing (meth)acrylates and carboxyl group-containing monomers. The proportion of polar monomers in the intermediate layer is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and even more preferably 3 to 8% by mass, based on 100% by mass of the polymerizable unsaturated monomers that form the intermediate layer.

[0086] Examples of the acyclic alkyl(meth)acrylate include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, 2-butyl(meth)acrylate, tert-butyl(meth)acrylate, n-pentyl(meth)acrylate, isopentyl(meth)acrylate (isoamyl(meth)acrylate), 2-pentyl(meth)acrylate, tert-pentyl(meth)acrylate, 3-methyl(meth)acrylate, butyl-2-(meth)acrylate, 3-pentyl (meth)acrylate, neopentyl (meth)acrylate, 1-methylpentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, 2-hexyl (meth)acrylate, tert-hexyl (meth)acrylate, 3,3-dimethyl-2-butyl (meth)acrylate, 3-methyl-2-pentyl (meth)acrylate, neohexyl (meth)acrylate, 4-methyl-2-pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate acrylate, n-heptyl (meth)acrylate, isoheptyl (meth)acrylate, 2-heptyl (meth)acrylate, tert-heptyl (meth)acrylate, 2,4-dimethyl-3-pentyl (meth)acrylate, neoheptyl (meth)acrylate, 2-methyl-3-hexyl (meth)acrylate, 3-heptyl (meth)acrylate, 4-heptyl (meth)acrylate, 5-methyl-2-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate , tert-octyl (meth)acrylate, neooctyl (meth)acrylate, 2,2-dimethyl-3-hexyl (meth)acrylate, 2,5-dimethyl-3-hexyl (meth)acrylate, 3-octyl (meth)acrylate, 4-octyl (meth)acrylate, 5-methyl-2-heptyl (meth)acrylate, 5-methyl-3-heptyl (meth)acrylate, 6-methyl-2-heptyl (meth)acrylate, 6-methyl-3-heptyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate,2-nonyl(meth)acrylate, tert-nonyl(meth)acrylate, neononyl(meth)acrylate, n-decyl(meth)acrylate, isodecyl(meth)acrylate, 2-decyl(meth)acrylate, tert-decyl(meth)acrylate, neodecyl(meth)acrylate, n-undecyl(meth)acrylate, isoundecyl(meth)acrylate, 2-undecyl(meth)acrylate, tert-undecyl(meth)acrylate, neoundecyl(meth)acrylate, n-dodecyl(meth)acrylate tert-Dodecyl (meth)acrylate, neododecyl (meth)acrylate, n-Tridecyl (meth)acrylate, isotridecyl (meth)acrylate, 2-Tridecyl (meth)acrylate, tert-Tridecyl (meth)acrylate, neotridecyl (meth)acrylate, n-Tetradecyl (meth)acrylate, isotetradecyl (meth)acrylate, 2-Tetradecyl (meth)acrylate, tert- Tetradecyl (meth)acrylate, neotetradecyl (meth)acrylate, n-pentadecyl (meth)acrylate, isopentadecyl (meth)acrylate, 2-pentadecyl (meth)acrylate, tert-pentadecyl (meth)acrylate, neopentadecyl (meth)acrylate, n-hexadecyl (meth)acrylate, isohexadecyl (meth)acrylate, 2-hexadecyl (meth)acrylate, tert-hexadecyl (meth)acrylate, neohexadecyl (meth)acrylate, n-hexadecyl (meth)acrylate, Examples of the alkyl (meth)acrylate include acyclic alkyl (meth)acrylates having an alkyl group of 1 to 18 carbon atoms, such as butadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, 2-heptadecyl (meth)acrylate, tert-heptadecyl (meth)acrylate, neoheptadecyl (meth)acrylate, n-octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, 2-octadecyl (meth)acrylate, tert-octadecyl (meth)acrylate, and neooctadecyl (meth)acrylate. One or more of these may be used. Each of these monomers may be used alone,Two or more types may be used in combination. From the viewpoint of forming a coating film that is comprehensively superior in weather resistance, low-temperature film-forming properties, elongation, water resistance, frost resistance, and stain resistance, acyclic alkyl (meth)acrylates in which the alkyl group has 1 to 8 carbon atoms are preferred. Furthermore, from the viewpoint of improving water blister resistance and adjusting Tg, branched alkyl (meth)acrylates having a branched alkyl group are more preferred among cyclic alkyl (meth)acrylates.

[0087] The silicone-modified polymer emulsion preferably has a structural unit derived from a monomer having a branched alkyl group. This is thought to further improve the barrier properties by causing the branched alkyl groups to intertwine with each other, thereby further improving the water blister resistance. Examples of the monomer having a branched alkyl group include the branched alkyl (meth)acrylates described above. The branched alkyl (meth)acrylate is preferably a monomer represented by the following formula (3): (In the formula, R ８ represents a hydrogen atom or a methyl group. ９ and R １０ represents an alkyl group, and R ９ and R １０ The total number of carbon atoms in the alkyl groups of R is 2 to 20, and ９ The number of carbon atoms in ≦R １０ The number of carbon atoms satisfies the above formula (1). ９ and R １０ The alkyl group in is not particularly limited, and specific examples include R ２ The same as described above for (an alkyl group as a specific example of a hydrocarbon group). ９ and R １０ More specific examples of the alkyl group represented by R include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl groups; and branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 2,3-dimethyl-2-butyl, 3-methylheptyl, and 2-ethylhexyl. ９ and R １０The total number of carbon atoms in the alkyl groups of R is preferably 3 to 20, more preferably 3 to 15, and even more preferably 5 to 14. ９ The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2. １０ The alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms.

[0088] Specific examples of the branched alkyl (meth)acrylate include isopropyl (meth)acrylate, 2-butyl (meth)acrylate, 2-pentyl (meth)acrylate, 3-methyl-2-butyl (meth)acrylate, 3-pentyl (meth)acrylate, 2-hexyl (meth)acrylate, 3,3-dimethyl-2-butyl (meth)acrylate, 3-methyl-2-pentyl (meth)acrylate, 4-methyl-2-pentyl (meth)acrylate, 2,4-dimethyl-3-pentyl (meth)acrylate, 2-heptyl (meth)acrylate, 2-methyl-3-hexyl (meth)acrylate, 3-heptyl (meth)acrylate, 4-heptyl (meth)acrylate, 5-methyl-2-hexyl (meth)acrylate, and 2-octyl (meth)acrylate. acrylate, 2,2-dimethyl-3-hexyl(meth)acrylate, 2,5-dimethyl-3-hexyl(meth)acrylate, 3-octyl(meth)acrylate, 4-octyl(meth)acrylate, 5-methyl-2-heptyl(meth)acrylate, 5-methyl-3-heptyl(meth)acrylate, 6-methyl-2-heptyl(meth)acrylate, 6-methyl-3-heptyl(meth)acrylate, more preferably isoamyl(meth)acrylate, 2-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, even more preferably isoamyl(meth)acrylate, 2-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and most preferably 2-octyl(meth)acrylate.

[0089] 2-octyl (meth)acrylate can be synthesized using biomass materials as raw materials, which is preferable from the perspective of reducing environmental impact. Specifically, it can be obtained by, for example, cracking ricinoleic acid derived from castor oil collected and extracted from castor bean seeds, followed by distillation of a mixture containing the by-product sebacic acid to obtain 2-octanol, and then esterifying this with (meth)acrylic acid. The (meth)acrylic acid used in this application may be derived from either biomass or petroleum.

[0090] The proportion of the acyclic alkyl (meth)acrylate is not particularly limited, but is preferably 10 to 90% by mass relative to 100% by mass of the polymerizable unsaturated monomer. It is more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 35 to 60% by mass. In one embodiment, the proportion of the acyclic alkyl (meth)acrylate relative to 100% by mass of the polymerizable unsaturated monomer is also preferably 40 to 60% by mass.

[0091] The proportion of the branched alkyl (meth)acrylate is not particularly limited, but is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 65% by mass, still more preferably 25 to 60% by mass, and particularly preferably 30 to 55% by mass, relative to 100% by mass of the polymerizable unsaturated monomer.

[0092] The polymerizable unsaturated monomer may contain a linear alkyl (meth)acrylate among acyclic alkyl (meth)acrylates, and the proportion thereof is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, relative to 100% by mass of the polymerizable unsaturated monomer.

[0093] Examples of the alicyclic structure-containing (meth)acrylate include alicyclic structure-containing (meth)acrylates having an alicyclic structure with 3 to 12 carbon atoms, such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, and isobornyl (meth)acrylate. These alicyclic structure-containing (meth)acrylates may be used alone or in combination of two or more. Of these, cyclohexyl (meth)acrylate is preferred. Because alicyclic structure-containing (meth)acrylates are highly hydrophobic, their use can sufficiently reduce the water absorption of the coating film and more sufficiently suppress leaching of the hydrophilic polymer.

[0094] The proportion of the alicyclic structure-containing (meth)acrylate is not particularly limited, but is preferably 20 to 80% by mass relative to 100% by mass of the polymerizable unsaturated monomer. A proportion of 20% by mass or more further improves the weather resistance of the coating film. Furthermore, a proportion of 80% by mass or less further improves the low-temperature film-forming properties and extensibility of the coating film. The proportion of the alicyclic structure-containing (meth)acrylate is more preferably 25 to 75% by mass, even more preferably 30 to 70% by mass, even more preferably 35 to 65% by mass, and particularly preferably 40 to 60% by mass.

[0095] When the silicone-modified polymer emulsion has a two-layer structure, the proportion of the alicyclic structure-containing (meth)acrylate in the outer layer is preferably 10 to 80% by weight, based on 100% by weight of the polymerizable unsaturated monomer constituting the outer layer. It is more preferably 15 to 70% by weight, and particularly preferably 20 to 60% by weight. In one embodiment, when the silicone-modified polymer emulsion has a two-layer structure, the proportion of the alicyclic structure-containing (meth)acrylate in the outer layer is preferably 20 to 80% by weight, based on 100% by weight of the polymerizable unsaturated monomer constituting the outer layer. It is more preferably 25 to 70% by weight, and particularly preferably 30 to 60% by weight. The proportion of the alicyclic structure-containing (meth)acrylate in the inner layer is preferably 40 to 100% by weight, based on 100% by weight of the polymerizable unsaturated monomer constituting the inner layer. It is more preferably 50 to 100% by weight, even more preferably 60 to 100% by weight, and particularly preferably 70 to 100% by weight.

[0096] When the silicone-modified polymer emulsion has a structure of three or more layers, the proportion of the alicyclic structure-containing (meth)acrylate in the outer layer is preferably 20 to 80% by weight, based on 100% by weight of the polymerizable unsaturated monomer constituting the outer layer. It is more preferably 25 to 75% by weight, even more preferably 28 to 70% by weight, and particularly preferably 30 to 65% by weight. The proportion of the alicyclic structure-containing (meth)acrylate in the intermediate layer is preferably 10 to 50% by weight, based on 100% by weight of the polymerizable unsaturated monomer constituting the intermediate layer. It is more preferably 15 to 45% by weight, even more preferably 18 to 40% by weight, and particularly preferably 20 to 35% by weight. The proportion of the alicyclic structure-containing (meth)acrylate in the inner layer is preferably 50 to 100% by weight, based on 100% by weight of the polymerizable unsaturated monomer constituting the inner layer. It is more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass.

[0097] Examples of the carbonyl group-containing monomer include (meth)acryloyl, humylstyrol, vinyl ethyl ketone, (meth)acryloxyalkyl propenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, diacetone (meth)acrylamide, 2-hydroxypropyl (meth)acrylate acetylacetate, butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate, and 2-(acetoacetoxy)ethyl methacrylate. The carbonyl group in the carbonyl group-containing monomer can react with a crosslinking agent, such as a hydrazine-based crosslinking agent, as described below. Among these, diacetone (meth)acrylate, diacetone (meth)acrylamide, and the like are preferred, and diacetone (meth)acrylamide is more preferred.

[0098] The hydroxyl group-containing (meth)acrylate is not particularly limited, but examples include hydroxyl group-containing (meth)acrylates in which the hydroxyalkyl group has 1 to 18 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Of these, 2-hydroxyethyl (meth)acrylate is preferred. The ratio of the hydroxyl group-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0099] The unsaturated carboxylic acid monomer is not particularly limited, but examples thereof include unsaturated monocarboxylic acid monomers such as (meth)acrylic acid, crotonic acid, etc., and salts thereof; and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., and salts and acid anhydrides thereof. Among these, (meth)acrylic acid is preferred. These monomers may be used alone or in combination of two or more. The ratio of the carboxyl group-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0100] By using a monomer having a polar group, such as a hydroxyl group-containing (meth)acrylate or an unsaturated carboxylic acid monomer, as the polymerizable unsaturated monomer, charge repulsion and the like occurs in the emulsion, further improving the mechanical stability, thereby more sufficiently suppressing the aggregation of the emulsion.

[0101] The aromatic monomer is not particularly limited, but examples include styrene-based monomers such as styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, and vinyltoluene, and aralkyl (meth)acrylates, but the present invention is not limited to these examples. Examples of aralkyl (meth)acrylates include aralkyl (meth)acrylates having an aralkyl group containing 7 to 18 carbon atoms, such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate. These aromatic monomers may be used alone or in combination of two or more. The proportion of aromatic monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention. The proportion of aromatic monomer is not particularly limited, but is preferably 20% by mass or less relative to 100% by mass of polymerizable unsaturated monomer. A proportion of 20% by mass or less further improves the weather resistance of the coating film. The proportion of aromatic monomers is more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 1% by mass or less, and most preferably 0% by mass.

[0102] The nitrogen atom-containing monomer is not particularly limited, but examples thereof include (meth)acrylamide compounds such as (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-n-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, and diacetone(meth)acrylamide; nitrogen atom-containing (meth)acrylate compounds such as dimethylaminoethyl(meth)acrylate and diethylaminoethyl(meth)acrylate; N-vinylpyrrolidone; and (meth)acrylonitrile. These nitrogen atom-containing monomers may be used alone or in combination of two or more. The ratio of the nitrogen atom-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0103] The oxo group-containing monomer is not particularly limited, but examples include (di)ethylene glycol (methoxy) (meth)acrylates such as ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth)acrylate, diethylene glycol (meth)acrylate, and diethylene glycol methoxy (meth)acrylate, and 2-(acetoacetoxy)ethyl (meth)acrylate. These monomers may be used alone or in combination of two or more. The proportion of the oxo group-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0104] The halogen atom-containing monomer is not particularly limited, but examples thereof include halogen atom-containing alkyl (meth)acrylates in which the haloalkyl group has 2 to 6 carbon atoms, such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and octafluoropentyl (meth)acrylate. These monomers may be used alone or in combination of two or more. The halogen atom is preferably a fluorine atom. The proportion of the halogen atom-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0105] The epoxy group-containing monomer is not particularly limited, but examples thereof include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, and these monomers may be used alone or in combination of two or more. The ratio of the epoxy group-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0106] The ultraviolet absorbing monomer is not particularly limited, but examples thereof include benzotriazole-based ultraviolet absorbing monomers and benzophenone-based ultraviolet absorbing monomers. These monomers may be used alone or in combination of two or more.

[0107] The benzotriazole-based ultraviolet absorbing monomer is not particularly limited, but examples thereof include 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-( 2-[2'-hydroxy-5'-(meth)acryloyloxypropylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'- Hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl-3'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]- Examples of such benzotriazole-based ultraviolet absorbing monomers include 5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-tert-butyl-2H-benzotriazole, and 2-[2'-hydroxy-5'-(β-(meth)acryloyloxyethoxy)-3'-tert-butylphenyl]-4-tert-butyl-2H-benzotriazole. These benzotriazole-based ultraviolet absorbing monomers may be used alone or in combination of two or more.

[0108] The benzophenone-based ultraviolet absorbing monomer is not particularly limited, but examples thereof include 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-[2-hydroxy-3-(meth)acryloyloxy]propoxybenzophenone, 2-hydroxy-4-[2-(meth)acryloyloxy]ethoxybenzophenone, 2-hydroxy-4-[3-(meth)acryloyloxy-2-hydroxypropoxy]benzophenone, and 2-hydroxy-3-tert-butyl-4-[2-(meth)acryloyloxy]butoxybenzophenone. These benzophenone-based ultraviolet absorbing monomers may be used alone or in combination of two or more.

[0109] The ultraviolet stable monomer is not particularly limited, and examples thereof include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, and 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine. and (meth)acryloyloxy group-containing piperidines such as 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine and 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine; and crotonoyl group-containing piperidines such as 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine. These ultraviolet-stable monomers may be used alone or in combination of two or more.

[0110] <<Hydrophilic Polymer>> The hydrophilic polymer contained in the resin composition for paint of the present invention may be any polymer as long as it exhibits hydrophilicity, but preferably has a solubility in water of 50 g / 100 g or more at 25° C. The solubility in water at 25° C. is more preferably 55 g / 100 g or more, and even more preferably 60 g / 100 g or more.

[0111] The hydrophilic polymer has a homopolymer solubility parameter of 11 (cal / cm) calculated by the following method. ３ ) １／２ The proportion of structural units derived from a monomer having a molecular weight of 100 or more (hereinafter also referred to as a hydrophilic monomer) is preferably 70 to 100% by mass relative to 100% by mass of all structural units. The proportion is more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass. <Method of calculating solubility parameter> The solubility parameter (δ) (cal / cm) of the homopolymer is calculated as follows: ３ ) １／２ is calculated from the evaporation energy (Δei) and molar volume (Δvi) of the structural units forming the polymer using the following formula based on Fedors' estimation method (R.F. Fedors, Polym. Eng. Sci., 14(2), 147-154 (1974)): δ=(Δei / Δvi) １／２

[0112] The solubility parameter of the homopolymer calculated by the above method is more preferably 11.5 or more, and even more preferably 12 or more.

[0113] The hydrophilic polymer preferably has structural units derived from a carbonyl group-containing monomer, which allows a crosslinked structure to be formed between the hydrophilic polymer and the silicone-modified polymer emulsion using a crosslinking agent such as a hydrazine-based crosslinking agent described below.

[0114] The hydrophilic polymer may have a structural unit derived from a monomer other than the hydrophilic monomer. The other monomer is not particularly limited, but may be, for example, a polymerizable monomer in the silicone-modified polymer emulsion that does not fall under the category of a hydrophilic monomer. The other monomer is preferably an acyclic alkyl (meth)acrylate.

[0115] The proportion of structural units derived from other monomers in the hydrophilic polymer is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass, relative to 100% by mass of all structural units.

[0116] The hydrophilic polymer preferably contains structural units derived from an N-vinyl lactam monomer, which will be described later, and the proportion thereof is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, relative to 100% by mass of all structural units.

[0117] The hydrophilic polymer may have a structural unit derived from a carbonyl group-containing monomer, which will be described later, and the proportion thereof is not particularly limited, but is preferably 0 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass, relative to 100% by mass of all structural units.

[0118] The weight-average molecular weight of the hydrophilic polymer is not particularly limited, but is preferably 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, even more preferably 5,000 to 500,000, still more preferably 7,000 to 300,000, and particularly preferably 10,000 to 100,000. The weight-average molecular weight can be measured using gel permeation chromatography.

[0119] The hydrophilic polymer may be any polymer obtained by polymerizing a monomer component containing the hydrophilic monomer, and may be any of a homopolymer, a random copolymer, a block copolymer, and a graft copolymer. Of these, a random copolymer is preferred.

[0120] The hydrophilic monomer is not particularly limited, but examples thereof include N-vinyl lactam monomers, unsaturated carboxylic acid monomers, carbonyl group-containing monomers, hydroxyl group-containing monomers, unsaturated polyalkylene glycol monomers, alkylene oxides, etc. Among these, N-vinyl lactam monomers are preferred.

[0121] The N-vinyl lactam monomer is not particularly limited as long as it is a monomer having a cyclic N-vinyl lactam structure, and specific examples thereof include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, 1-(2-propenyl)-2-pyrrolidone, etc. Among these, N-vinylpyrrolidone is preferred.

[0122] Specific and preferred examples of the unsaturated carboxylic acid monomer, the carbonyl group-containing monomer, and the hydroxyl group-containing monomer are as described above.

[0123] The unsaturated polyalkylene glycol monomer may be any monomer having a (poly)oxyalkylene group, and examples thereof include polyalkylene glycol (meth)acrylates such as polyethylene glycol (meth)acrylate; and compounds in which alkylene oxide is added to unsaturated alcohols having 2 to 8 carbon atoms, such as vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, 2-methyl-2-buten-1-ol, and 3-allyloxy-1,2-propanediol. The average number of moles of alkylene oxide added in the unsaturated polyalkylene glycol monomer is preferably 1 to 10.

[0124] Examples of the alkylene oxide include alkylene oxides having 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. More preferred are alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being even more preferred, and ethylene oxide being particularly preferred. A preferred embodiment of the present invention is one in which the hydrophilic polymer is a polyalkylene glycol obtained by addition polymerization of the alkylene oxide.

[0125] The number average molecular weight of the polyalkylene glycol is not particularly limited, but is preferably at least 1,000 and less than 1,000,000, and more preferably 10,000 to 500,000. The number average molecular weight can be measured using gel permeation chromatography.

[0126] <<Other Components>> Other components other than the silicone-modified polymer emulsion and hydrophilic polymer can be added to the coating resin composition of the present invention as needed, as long as they do not impair the effects of the present invention. These other components are not particularly limited, and include various additives such as crosslinkers, curing agents, film-forming aids, fillers, thickeners, defoamers, pigments, dispersants, pH buffers, chelating agents, dyes, UV absorbers, UV stabilizers, leveling agents, wetting agents, plasticizers, stabilizers, antioxidants, matting agents, antifreezing agents, colloidal silica, rheology control agents, foaming agents, antiblocking agents, antioxidants, preservatives, polymerization inhibitors, antistatic agents, silane coupling agents, and flame retardants, as well as other emulsions and solvents. A preferred embodiment of the present invention is one in which the coating resin composition contains a crosslinker.

[0127] Examples of the crosslinking agent and curing agent include hydrazine-based crosslinking agents, melamine-based crosslinking agents, oxazoline-based crosslinking agents, acrylamide-based crosslinking agents, polyamide-based crosslinking agents, epoxy-based crosslinking agents, isocyanate-based crosslinking agents, aziridine-based crosslinking agents, titanate-based crosslinking agents, urea-based crosslinking agents, alkyl alcohol-modified urea-based crosslinking agents, carbodiimide compounds, zirconium compounds, zinc compounds, titanium compounds, and polyvalent metal compounds such as aluminum compounds. These may be used alone or in combination of two or more. Preferred are hydrazine-based crosslinking agents.

[0128] Examples of the thickener include urethane association types, polycarboxylates, polyether types, cellulose ethers, polyacrylic types, polyacrylamides, etc. These may be used alone or in combination of two or more.

[0129] Examples of the film-forming aid include glycol ethers, esters, etc. These may be used alone or in combination of two or more.

[0130] Examples of the filler include inorganic fillers (pigments) such as calcium carbonate, kaolin clay, talc, diatomaceous earth, silica, mica, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, sepiolite, alumina, titanium oxide, barium sulfate, talc, and red iron oxide, glass materials such as glass beads, foamed glass beads, hollow volcanic glass, and glass fibers, and organic fillers such as resin powder, rubber powder, carbon black, and cellulose powder. These may be used alone or in combination of two or more.

[0131] Examples of the thickener include polycarboxylates, urethane association types, polyether types, cellulose ethers, polyacrylic types, and polyacrylamides. Examples of the defoaming agent include silicon-based defoaming agents. Examples of the dispersing agent include dispersing agents having a polypropylene glycol group or a polyethylene glycol group.

[0132] Examples of the pigment include inorganic pigments (e.g., inorganic color pigments such as titanium oxide, iron oxide, aluminum, and pearl pigments), organic pigments (e.g., organic color pigments such as quinacridone, anthraquinone, perylene, diketopyrrolopyrrole, benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, threne, dioxazine, and carbon black), and extender pigments (e.g., calcium carbonate, barium sulfate, kaolin, mica, and talc).

[0133] As described below, the resin composition for paint of the present invention is also an anti-rust paint composition. When the anti-rust paint composition contains a pigment, it is preferably an anti-rust pigment. An anti-rust pigment is a pigment added to paint for the purpose of providing some resistance to metal corrosion factors and protecting the metal from corrosion. From the viewpoint of safety and environmental considerations, anti-rust pigments that do not contain lead or chromium are preferred, and examples of anti-rust pigments that are preferred include phosphate-based metal salts, molybdate-based metal salts, borate-based metal salts, and cyanamide-based metal salts. These can be used alone or in combination of two or more.

[0134] Examples of phosphate metal salt rust preventive pigments include metal orthophosphates such as zinc orthophosphate, calcium orthophosphate, aluminum orthophosphate, and magnesium orthophosphate; metal pyrophosphates such as aluminum pyrophosphate, calcium pyrophosphate, tin pyrophosphate, iron pyrophosphate, titanium pyrophosphate, magnesium pyrophosphate, and manganese pyrophosphate; metal tripolyphosphates such as iron tripolyphosphate and aluminum tripolyphosphate; metal metaphosphates such as aluminum metaphosphate, calcium metaphosphate, iron metaphosphate, and tin metaphosphate; and metal phosphate layer compounds such as layered titanium phosphate, layered zirconium phosphate, and layered tin phosphate.

[0135] Examples of anti-rust pigments of molybdate-based metal salts include zinc molybdate, calcium molybdate, zinc calcium molybdate, magnesium molybdate, nickel molybdate, cobalt molybdate, strontium molybdate, zinc phosphomolybdate, calcium phosphomolybdate, aluminum phosphomolybdate, etc. Examples of anti-rust pigments of borate-based metal salts include barium borate, barium metaborate, calcium metaborate, magnesium metaborate, etc.

[0136] Examples of anti-rust pigments of cyanamide-based metal salts include zinc cyanamide, zinc calcium cyanamide, etc. In addition, anti-rust pigments modified by adding zinc oxide or an oxide or hydroxide of an alkaline earth metal such as magnesium oxide or magnesium hydroxide to the above-mentioned anti-rust pigments can also be used.

[0137] When the anticorrosive coating composition contains a pigment, the content of the pigment in the anticorrosive coating composition can be appropriately set but is preferably 0.1 to 50% by mass, more preferably 1 to 10% by mass. When the anticorrosive coating composition contains a pigment, the content of the pigment in the silicone-modified polymer emulsion can be appropriately set but is preferably 5 to 80% by mass, more preferably 10 to 60% by mass.

[0138] Examples of other emulsions include natural rubber latex, acrylic resin latex, vinyl acetate resin latex, urethane resin latex, and epoxy resin latex. These may be used alone or in combination of two or more.

[0139] The paint resin composition of the present invention also has excellent rust-preventing properties, making it suitable for use in rust prevention applications. The present invention also relates to an anti-rust paint composition containing the above-mentioned silicone-modified polymer emulsion. One preferred embodiment of the present invention is an anti-rust paint composition containing the silicone-modified polymer emulsion, wherein the silicone-modified polymer emulsion has structural units derived from polymerizable unsaturated monomers and structures derived from silane compounds, and the proportion of the silane compound-derived structures relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomers is 10 mass% or more, the silane compounds include silane compound (a) represented by formula (1) above and silane compound (b) having a polymerizable unsaturated group, and the proportion of the structure derived from silane compound (b) having a polymerizable unsaturated group in the silicone-modified polymer emulsion is 0.1 to 5 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomers.

[0140] [Paint] The present invention also relates to a paint containing the paint resin composition or anticorrosive paint composition of the present invention. The paint resin composition of the present invention can be used as a clear paint as is, or can be used as an enamel paint by adding an appropriate amount of a colorant such as a dye or pigment to the paint resin composition of the present invention. The present invention also relates to a method for producing a paint, which includes a step of mixing the paint resin composition with components other than the silicone-modified polymer emulsion. The present invention also relates to a method for using the paint resin composition containing the silicone-modified polymer emulsion as a paint. The content of the silicone-modified polymer emulsion in the paint is not particularly limited, but is preferably 10 to 90% by mass, based on 100% by mass of the paint. It is more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0141] The coating material of the present invention may further contain additives other than the colorant, as described above. The amount of additive contained in the coating material varies depending on the type of additive, and is preferably adjusted appropriately depending on the type of additive. The resin composition for coating or coating material of the present invention can be used, for example, by applying it to substrates formed from various materials (e.g., metal, glass, porcelain, concrete, siding board, resin, etc.). It may also be used for surface finishing of the above substrates. The resin composition for coating or coating material of the present invention is preferably used as an architectural coating material, and because of its excellent long-term stain resistance, it can be suitably used as a top coat or top coat material (e.g., a top coat or top coat material for building materials such as interior and exterior materials).

[0142] Examples of building materials include inorganic building materials such as flexible boards, calcium silicate boards, gypsum slag perlite boards, wood-chip cement boards, precast concrete boards, ALC boards, and gypsum boards; ceramic building materials such as roofing tiles and exterior wall materials; and metal building materials such as Galvalume Steel Sheets (registered trademark). Ceramic building materials can be obtained, for example, by adding an inorganic filler, a fibrous material, and the like to a hydraulic adhesive material that serves as the raw material for the inorganic hardened body, molding the resulting mixture, and curing and hardening the resulting molded body.

[0143] When the resin composition for paint of the present invention is a rust-preventive paint composition, the substrate is preferably a metal member such as iron, plated steel sheet, stainless steel, aluminum, etc. The use of the above-mentioned rust-preventive paint composition on a metal member is one of the preferred embodiments of the present invention.

[0144] The resin composition for paint, the anticorrosive paint composition, or the paint of the present invention may be applied to a substrate in a single layer, or a commonly used water-based paint may be freely selected and applied as a topcoat on the coating film obtained by applying and drying the composition. Examples of such water-based paints include acrylic paints, urethane paints, UV paints, silicone paints, melamine resin paints, epoxy paints, and fluororesin paints. The anticorrosive paint composition has excellent anticorrosion properties and may therefore be used as an undercoat, but it also has excellent weather resistance and can therefore be suitably used as a topcoat.

[0145] The coating resin composition or coating material of the present invention can be applied to a substrate by any conventional method. For example, it can be applied to a substrate using a spatula, brush, air spray, airless spray, mortar gun, lysine gun, roll coater, etc. The amount of coating resin composition or coating material of the present invention to be applied varies depending on the type of coating material and substrate, and cannot be determined in general, but is generally in the range of 10 to 300 g / m. 2 It is preferable that the degree of

[0146] [Method for producing a paint resin composition] The method for producing the paint resin composition of the present invention is not particularly limited, and the paint resin composition can be produced by mixing a silicone-modified polymer emulsion with, as needed, components other than the silicone-modified polymer emulsion, such as a hydrophilic polymer. The mixing ratio of the silicone-modified polymer emulsion to components other than the silicone-modified polymer emulsion, such as a hydrophilic polymer, is not particularly limited, and can be determined based on the preferred ratio of the silicone-modified polymer emulsion and components other than the silicone-modified polymer emulsion, such as a hydrophilic polymer, in the paint resin composition described above.

[0147] <Method for producing silicone-modified polymer emulsion> The method for producing the silicone-modified polymer emulsion is not particularly limited, as long as it comprises the step of silicone-modifying the monomer component containing polymerizable unsaturated monomer or its polymer with silane compound (hereinafter also referred to as silicone-modifying step).For example, polymerizable unsaturated monomer and silane compound can be reacted simultaneously, or polymer of polymerizable unsaturated monomer can be reacted with silane compound.In addition, when the silane compound comprises the above-mentioned silane compound (a) and silane compound (b), for example, polymerizable unsaturated monomer, silane compound (a) and silane compound (b) can be reacted simultaneously, or polymer obtained by polymerizing polymerizable unsaturated monomer and silane compound (b) can be reacted with silane compound (a).The specific examples and preferred forms of each polymerizable unsaturated monomer and silane compound in the monomer component used in the above-mentioned production method are as described for silicone-modified polymer emulsion. The amounts of these used can be determined based on the above-mentioned preferred proportions of the structural units derived from each monomer and the structure derived from the silane compound in the silicone-modified polymer emulsion.

[0148] In the silicone modification step, when using silane compounds (a) and (b), the reaction step of silane compound (a) can be carried out after the polymerization step of carrying out the polymerization reaction of the monomer component comprising polymerizable unsaturated monomer and silane compound (b), or the reaction step of silane compound (a) can be carried out simultaneously.However, preferably, the polymerization reaction of the monomer component comprising polymerizable unsaturated monomer and silane compound (b) is started, and then the reaction of silane compound (a) is started, and the reaction of silane compound (a) is carried out while carrying out the polymerization step.Therefore, the polymerization reaction and the reaction of silane compound (a) and silane compound (b) can proceed in parallel.More specifically, after the polymerization reaction of monomer component starts, it is preferred to dropwisely add the monomer component comprising polymerizable unsaturated monomer and silane compound (b) and silane compound (a) into a reactor separately using different dropping funnels to carry out the reaction.

[0149] The dropwise addition of the monomer component and silane compound (a) in the silicone modification step is preferably carried out at a pH of 1 to 5 or 8 to 11. This allows the hydrolysis and condensation reaction of the silane compound to proceed more rapidly. The pH can be adjusted using an acidic monomer such as (meth)acrylic acid, or an acid such as sulfuric acid, dodecylbenzenesulfonic acid, or hydrochloric acid.

[0150] When using a silane compound (b) in the silicone modification step, the polymerization of the monomer component is preferably carried out by polymerizing a monomer component containing a polymerizable unsaturated monomer and a silane compound (b).The polymerization reaction is preferably carried out by emulsion polymerization.The method of emulsion polymerizing a monomer component containing a polymerizable unsaturated monomer and a silane compound (b) is not particularly limited, but for example, a method of dissolving an emulsifier in a medium such as an aqueous medium containing water and a water-soluble organic solvent such as water or a lower alcohol such as methanol, and then dropping the monomer component and a polymerization initiator, or a method of dropping the monomer component that has been emulsified in advance using an emulsifier and water into water or an aqueous medium, etc.The amount of the medium used in emulsion polymerization can be appropriately determined taking into account the amount of nonvolatile matter contained in the resulting silicone modified polymer emulsion.

[0151] Examples of the emulsifier include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, and polymeric emulsifiers. These emulsifiers may be used alone or in combination of two or more.

[0152] The anionic emulsifier is not particularly limited, and examples thereof include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkylaryl sulfonate salts such as ammonium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate; polyoxyalkylene alkenyl ether sulfate salts such as ammonium polyoxyalkylene alkenyl ether sulfate (for example, manufactured by Kao Corporation, trade name: Ramtel PD-104); polyoxyethylene alkyl sulfate salts; polyoxyethylene alkylaryl sulfate salts; dialkyl sulfosuccinates; arylsulfonic acid-formalin condensates; and fatty acid salts such as ammonium laurate and sodium stearylate, and these may be used alone or in combination.

[0153] The nonionic emulsifier is not particularly limited, but examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, and condensates of ethylene oxide and aliphatic amines, and one or more of these can be used.

[0154] The cationic emulsifier is not particularly limited, but examples thereof include alkyl ammonium salts such as dodecyl ammonium chloride, and one or more of these can be used.

[0155] The amphoteric emulsifier is not particularly limited, but examples thereof include betaine ester emulsifiers, and one or more of these may be used.

[0156] The polymer emulsifier is not particularly limited, and examples thereof include poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; and polymers containing one or more of the monomers constituting these polymers as copolymerization components, and one or more of these may be used.

[0157] As the emulsifier, from the viewpoint of improving the mechanical stability of emulsion particles, an emulsifier having a reactive group, i.e., a so-called reactive emulsifier, is preferred, and from the viewpoint of environmental protection, a non-nonylphenyl type emulsifier is preferred.

[0158] The reactive emulsifier is not particularly limited, and examples thereof include propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts (e.g., Sanyo Chemical Industries, Ltd., trade name: Eleminol RS-30, etc.), polyoxyethylene alkylpropenyl phenyl ether ammonium sulfate (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, Aqualon BC-10, etc.), allyl methyl ... sulfonate salts of hydroxymethyl alkyloxy polyoxyethylene (e.g., Aqualon KH-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), sulfonate salts of allyloxymethyl nonylphenoxyethyl hydroxy polyoxyethylene (e.g., Adeka Reasop SE-10, manufactured by ADEKA Corporation), allyloxymethyl alkoxyethyl hydroxy polyoxyethylene sulfate ester salts (e.g., Adeka Reasop SR-10, SR-20, SR-30, SR-40, SR-50, SR-60, SR-70, SR-80, SR-90, SR-10, SR-11, SR-12, SR-13, SR-14, SR-15, SR-16, SR-17, SR-18, SR-19, SR-20, SR-21, SR-22, SR-23, SR-24, SR-25, SR-26, SR-27, SR-28, SR-29, SR-29, SR-29, SR-29, SR-30, SR-31, SR-32, SR-33, SR-34, SR-35, SR-36, SR-37, SR-38, SR-39, SR-40, SR-41, SR-42, SR-43, SR-44, SR-45, SR-46, SR-47, SR-48, SR-49, SR-49, SR-49, SR-49, SR-49, SR-49, SR-49, SR-49, SR-41, SR-42, SR-43, SR-44, SR-45, SR-46, -30, etc.), bis(polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salts [for example, trade name: Antox MS-60, manufactured by Nippon Nyukazai Co., Ltd., etc.], allyloxymethyl alkoxyethyl hydroxypolyoxyethylene [for example, trade name: Adeka Reasop ER-20, manufactured by ADEKA Corporation, etc.], polyoxyethylene alkylpropenylphenyl ether [for example, trade name: Aqualon RN-20, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene [for example, trade name: Adeka Reasop NE-10, etc.], polyoxyethylene styrenated propenylphenyl ether sulfate salts [for example, trade name: Aqualon AR-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., etc.], polyoxyethylene styrenated propenylphenyl ether sulfate [for example, trade name: Aqualon AN-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., etc.], and these may be used alone or in combination.

[0159] The amount of the emulsifier is not particularly limited, but is preferably 0.5 to 10% by mass relative to 100% by mass of the polymerizable monomer. If it is 0.5% by mass or more, the homopolymerization stability can be further improved, and if it is 10% by mass or less, the water penetration resistance of the coating film can be further improved. It is more preferably 1 to 7% by mass, and even more preferably 1 to 5% by mass.

[0160] The polymerization initiator is not particularly limited, but examples thereof include azo compounds such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as potassium persulfate and ammonium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. These polymerization initiators may be used alone, or two or more types may be used in combination.

[0161] The amount of the polymerization initiator is not particularly limited, but is preferably 0.01 to 1% by mass relative to 100% by mass of the polymerizable monomer. If it is 0.01% by mass or more, the polymerization rate can be increased and the amount of remaining unreacted monomer can be more sufficiently reduced, and if it is 1% by mass or less, the water penetration resistance of the coating film can be further improved. A more preferred amount is 0.03 to 0.5% by mass.

[0162] The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch addition, divided addition, continuous dropwise addition, etc. In order to hasten the completion of the polymerization reaction, a portion of the polymerization initiator may be added to the flask before or after the completion of the addition of the monomer components to the reaction system.

[0163] In order to promote decomposition of the polymerization initiator, a suitable amount of a decomposer for the polymerization initiator, such as a reducing agent such as sodium hydrogen sulfite or a transition metal salt such as ferrous sulfate, may be added to the reaction system. If necessary, a suitable amount of additives, such as a chain transfer agent (e.g., a compound having a thiol group such as tert-dodecyl mercaptan), a pH buffer, a chelating agent, or a film-forming aid, may be added to the reaction system in the flask.

[0164] A chain transfer agent may be used in the polymerization step. This allows the molecular weight of the emulsion to be adjusted. A preferred embodiment of the present invention also includes an embodiment in which no chain transfer agent is used. The chain transfer agent is not particularly limited, but examples thereof include mercaptans such as methyl mercaptan, t-butyl mercaptan, decyl mercaptan, benzyl mercaptan, lauryl mercaptan, stearyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid and its esters, 2-ethylhexyl thioglycol, and octyl thioglycolate; methanol, ethanol, propanol, n-butanol, isopropanol, and t-butanol; Examples of suitable chain transfer agents include alcohols such as ethanol, hexanol, benzyl alcohol, and allyl alcohol; halogenated hydrocarbons such as chloroethane, fluoroethane, and trichloroethylene; carbonyls such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, acetaldehyde, propionaldehyde, n-butylaldehyde, furfural, and benzaldehyde; and methyl-4-cyclohexene-1,2-dicarboxylic anhydride, α-methylstyrene, and α-methylstyrene dimer. Among these, mercaptans are preferred, and octyl thioglycolate is more preferred. The amount of chain transfer agent used is not particularly limited, but can be, for example, 0.01 to 5% by mass relative to 100% by mass of the polymerizable monomer. It is preferably 0.02 to 1% by mass, and more preferably 0.05 to 0.5% by mass.

[0165] The atmosphere in which the monomer components are emulsion-polymerized is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, an inert gas such as nitrogen gas is preferred.

[0166] The polymerization temperature when emulsion polymerizing the monomer components is not particularly limited, but is usually preferably 50 to 100° C., more preferably 60 to 95° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

[0167] The polymerization time for emulsion polymerization of the monomer components is not particularly limited and may be appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 15 hours.

[0168] In the silicone modification step, after the dropwise addition of the monomer component and silane compound is complete, the polymerization temperature is preferably maintained at 50 to 90°C for 0.5 to 5 hours. More preferably, the polymerization temperature is maintained at 70 to 90°C for 0.5 to 4 hours. The pH when maintaining the polymerization temperature after the dropwise addition of the monomer component and silane compound is preferably 1 to 5 or 8 to 11. This allows the condensation reaction of the silane compound to proceed sufficiently. The pH is more preferably 1.5 to 4.5 or 8 to 10. A base such as ammonia or sodium hydroxide can be used to adjust the pH. When producing a silicone-modified polymer emulsion having a three- or more-layer structure and using a monomer having an acid group in the intermediate layer, the pH is preferably adjusted to 6 to 7 after the dropwise addition of the monomer component for the intermediate layer is complete. This converts the acid group in the intermediate layer into a salt form, causing the emulsion particles to become electrically charged, thereby further improving dispersion stability.

[0169] When the emulsion particles have a multilayer structure, the polymerization reaction and the reaction with the silane compound can be repeated two or more times in the silicone modification step to prepare emulsion particles having at least two resin layers.

[0170] In the above-mentioned production method, a step of crosslinking the emulsion particles may be carried out after the silicone modification step, after the polymerization reaction of the monomer components, or after mixing the silicone-modified polymer emulsion with the hydrophilic polymer. The crosslinking step is preferably carried out after the mixing step. This results in the resulting silicone-modified polymer emulsion having a crosslinked structure derived from the crosslinking agent in addition to a crosslinked structure derived from the silane compound, thereby more sufficiently suppressing leaching of the hydrophilic polymer in the coating film. The crosslinking agent used in the crosslinking step is not particularly limited, and the above-mentioned crosslinking agents can be used. Among these, hydrazine-based crosslinking agents are preferred. The amount of the crosslinking agent can be appropriately set depending on the type of crosslinking agent, etc., but is preferably 0.1 to 5% by mass relative to 100% by mass of the polymerizable monomer. It is more preferably 0.5 to 2% by mass.

[0171] Examples of the hydrazine crosslinking agent include adipic acid dihydrazide and polymers having a hydrazide group, with adipic acid dihydrazide being preferred.

[0172] <Method for producing hydrophilic polymer> The method for producing the hydrophilic polymer is not particularly limited, and the hydrophilic polymer can be produced by polymerizing a monomer component. Specific and preferred examples of the monomer component are as described above. The content of each monomer component relative to 100% by mass of all the monomer components can be determined based on the proportion of each structural unit relative to 100% by mass of all the structural units described above.

[0173] The polymerization method of the monomer component is not particularly limited, and the polyalkylene glycol can be prepared by a polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, or precipitation polymerization. Among these polymerization methods, solution polymerization is preferred, and solution polymerization using water as a solvent is more preferred. When the monomer is an alkylene oxide, polyalkylene glycol can be produced by addition polymerization of the alkylene oxide in the presence of a catalyst using a commonly used method. Commercially available polyalkylene glycols can also be used.

[0174] When polymerization is carried out by the solution polymerization method, a solvent is used. Examples of the solvent include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; and cyclic ether compounds such as tetrahydrofuran and dioxane. Among these, polymerization by aqueous solution polymerization is preferred.

[0175] In the production of the hydrophilic polymer, a chain transfer agent can be used to adjust the molecular weight of the resulting polymer. As the chain transfer agent, those described in the production of the silicone-modified polymer emulsion can be used.

[0176] In the production of the hydrophilic polymer, it is preferable to use a polymerization initiator. As the polymerization initiator, those mentioned in the production of the silicone-modified polymer emulsion can be used. Among them, azo compounds are preferred, and 2,2-azobis(2-methylpropionamidine) is more preferred. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.01 to 10% by mass relative to 100% by mass of the monomer component.

[0177] The polymerization temperature for the polymerization reaction of the monomer components is not particularly limited, but is preferably 0 to 100°C, and more preferably 50 to 80°C. The pressure during the polymerization reaction may be normal pressure, reduced pressure, or increased pressure. The atmosphere during the polymerization reaction is preferably an inert gas such as nitrogen gas, argon gas, or carbon dioxide gas.

[0178] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by mass."

[0179] <Solid Content> The nonvolatile content in the resin emulsion means a value calculated by weighing 1 g of the resin emulsion, drying the resulting residue in a hot air dryer at 110°C for 1 hour, and calculating the nonvolatile content based on the following formula (II): [Nonvolatile content in resin emulsion (mass %)] = ([mass of residue] ÷ (1 g of resin emulsion]) × 100 (II).

[0180] <MFT> The minimum film-forming temperature of a resin emulsion means the boundary temperature between the film-forming area and the non-film-forming area when the resin emulsion is applied in a strip shape to a flat plate having an appropriate temperature gradient, and is defined as "the minimum temperature at which a crack-free, uniform coating film is formed."

[0181] The minimum film-forming temperature of a resin emulsion can be measured, for example, in accordance with JIS K6828-2 (2003). More specifically, using an MFT tester (manufactured by Tester Sangyo Co., Ltd., product number: TP-801 LT), a coating film of the resin emulsion having a thickness of 250 μm after drying is formed with an applicator on a grooveless stainless steel plate, and the minimum temperature (°C) at which a crack-free, uniform coating film is formed is measured. The presence or absence of cracks in the coating film can be determined visually in accordance with JIS K6828-2. Note that if the minimum film-forming temperature of the coating film is 0°C or lower, the minimum film-forming temperature of the coating film is considered to be 0°C.

[0182] <Preparation of Enamel Paint> 100 parts of deionized water, 15 parts of a dispersant (manufactured by BYK Japan K.K., trade name: DisperBYK-190), 210 parts of titanium oxide (manufactured by Ishihara Sangyo Kaisha, Ltd.), 2 parts of a defoaming agent (manufactured by BYK Japan K.K., product number: BYK-024), and 2 parts of a 15% aqueous solution of a thickener (manufactured by ADEKA Corporation, trade name: ADEKA NOL UH-420) were mixed in a homodisper at a rotation speed of 300 min. －１ After dispersing for 60 minutes, the mixture was filtered through a 300 mesh wire netting to obtain a white paste.

[0183] To 100 parts of the water-dispersed resin composition obtained in each Example or Comparative Example, 10 parts of 2,2,4-trimethyl-1,3-pentanediol isobutyrate was added as a film-forming aid, and the mixture was mixed in a homodisper at a rotation speed of 1500 min －１The mixture was stirred at RT for 30 minutes to obtain a dispersion.

[0184] To the dispersion obtained above, 80 parts of the white paste obtained above and 0.6 parts of an antifoaming agent (manufactured by BYK Japan Co., Ltd., product number: BYK-024) were added to obtain a mixture. －１ A thickener (manufactured by ADEKA Corporation, trade name: ADEKA NOL UH-420) was added to the mixture obtained above so that the viscosity at 25°C would be 4000 mPa s, and the mixture was stirred for 30 minutes, and then filtered through a 300-mesh wire netting to obtain an enamel paint.

[0185] [Weather resistance] A sealer (SK Chemical Co., Ltd., product name: EX Sealer) was applied with an air spray at a rate of 150 g / m ２ Test panels were prepared by uniformly applying the paint to a slate board (manufactured by Nippon Test Panel Co., Ltd.) so that the paint was uniformly applied to the sealer side of the test panel, and then drying in the air at room temperature (approximately 23°C) for one week. Next, an enamel paint was applied to the sealer side of the test panel using an 8-mil applicator. After drying in the air at room temperature (approximately 23°C) for one week, the 60° specular gloss of the enamel-coated surface of the test panel was measured using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG2000). Subsequently, a weathering test was conducted for 2500 hours on the test panel coated with the enamel paint under the following weathering test conditions, and the 60° specular gloss of the enamel-coated surface of the test panel was then measured using the gloss meter in the same manner as above.

[0186] (Test conditions for weather resistance test) Testing machine: Weather resistance tester (manufactured by Daipla Wintes Co., Ltd., product name: Metal Weather KU-R5) Irradiation: Irradiated for 4 hours in air at a temperature of 65°C and a relative humidity of 50% (irradiation intensity: 80 mW / cm ２ ) Wetting: 4 hours in air at a temperature of 35°C and a relative humidity of 98%. Shower: 30 seconds before and after wetting.

[0187] The gloss retention of the enamel paint-coated surface of the test plate was calculated based on the formula: [Gloss retention (%)] = [[Gloss after weather resistance test] ÷ [Gloss before weather resistance test]] × 100, and the weather resistance was evaluated based on the following evaluation criteria: (Evaluation criteria) ◎: Gloss retention is 90% or more ○: Gloss retention is 80% or more but less than 90% △: Gloss retention is 60% or more but less than 80% ×: Gloss retention is less than 60%

[0188] [Water resistance] A sealer (SK Chemical Co., Ltd., product name: EX Sealer) was applied with an air spray at an amount of 150 g / m ２ A test panel was prepared by uniformly applying the coating to a slate board (manufactured by Nippon Test Panel Co., Ltd.) so that the coating would be uniform, and then drying in the air at room temperature (approximately 23°C) for 24 hours. Next, enamel paint was applied to the sealer side of the test panel using a 6-mil applicator. After drying in the air at room temperature (approximately 23°C) for 2 hours, another enamel paint was applied using a 6-mil applicator so as to overlap the coating film, and then drying at room temperature for 24 hours to form a two-layer coating film. Subsequently, the test panel was immersed in deionized water adjusted to room temperature for 24 hours. Thereafter, a 5 mm x 5 mm cut was made in the coating film with a cutter knife, and the behavior when peeled off with the cutter knife was visually observed, and water resistance was evaluated based on the following evaluation criteria: (Evaluation criteria) ⊚: All of the coating film peeled off in both layers; ○: Most of the coating film peeled off in both layers; Δ: Only one coating film peeled off; ×: The coating decomposed.

[0189] [Flexibility] A test substrate was prepared by attaching release paper to one surface of a square glass plate with a side length of 5 cm, and attaching cloth gum tape to the edge of the surface where the release paper was attached. Next, the enamel paint obtained above was applied to the release paper surface of the test substrate so that the thickness of the coating film after drying was 0.3 mm, and after drying in air at 23 ° C. for 1 week, the formed coating film was peeled off from the test substrate, and the obtained coating film was cut into a dumbbell shape as specified in JIS K 6909 (2014) to prepare a test specimen. The short side of the test piece was held in the chuck of a tensile tester (Shimadzu Corporation, trade name: Autograph AGS-100D) in air at room temperature (approximately 23°C), and a tensile test was carried out under conditions of an initial gauge length of 50 mm and a tensile speed of 200 mm / min. The elongation of the coating film was determined based on the formula: [Elongation (%)] = [(elongation at break) ÷ (50 mm)] x 100, and flexibility was evaluated based on the following evaluation criteria: (Evaluation criteria) ◎: Elongation rate 100% or more ○: Elongation rate 80% or more but less than 100% △: Elongation rate 40% or more but less than 80% ×: Elongation rate less than 40%

[0190] [Stain Resistance] Glass beads having a diameter of 1 mm were added to deionized water at a ratio of 5 parts per 95 parts of deionized water, and 5 parts of carbon black (manufactured by Mitsubishi Chemical Corporation) was added to the deionized water while stirring the deionized water with a Homo Disper at a rotation speed of 500 min-1. The deionized water was then further stirred at a rotation speed of 2500 min-1 for 30 minutes to obtain a dispersion. The obtained dispersion was filtered through a 300-mesh wire screen to obtain a carbon black dispersion.

[0191] Next, the enamel paint obtained above was applied to a white acrylic plate (manufactured by Nippon Test Panel Co., Ltd.) using a 6 mil applicator and dried in air at room temperature (approximately 23°C) for 24 hours. After drying, the initial L value (L0) of the enamel paint-coated surface of the test plate was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: Spectroscopic Color Difference Meter SE-2000).

[0192] Subsequently, the carbon black dispersion obtained above was applied to the enamel-coated surface of the test plate using a 20 mil applicator and dried for 24 hours at room temperature (approximately 23° C.). After drying, the carbon black adhering to the enamel-coated surface of the test plate was washed away using running water and a brush (pig bristles with a bristle length of 40 mm), and the L value (L1) of the carbon black dispersion-coated surface was measured using the color difference meter.

[0193] Next, the change in L value (ΔL) was calculated based on the formula: ΔL=L1−L0, and the stain resistance was evaluated based on the following evaluation criteria.

[0194] (Evaluation criteria) ⊚: ΔL is less than 20 ◯: ΔL is 20 or more and less than 40 △: ΔL is 40 or more and less than 60 ×: ΔL is 60 or more

[0195] [Stain Resistance After 6 Months] Enamel paint was applied twice to an aluminum plate (manufactured by Nippon Test Panel Co., Ltd., length: 400 mm, width: 100 mm, thickness: 1 mm) using a 6-mil applicator and allowed to dry at 23°C for one week. Subsequently, the test plate was bent lengthwise in half (200 mm) so as to create a 30-degree incline facing south. The initial L value (L0) of the inclined portion of the test plate was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000), and an outdoor exposure test was performed in accordance with JIS Z2381 (General Rules for Atmospheric Exposure Test Methods) under the following conditions. After six months, the test plate was removed, and the L value (L1) of the inclined portion of the test plate was measured using the color difference meter. - Test Conditions - (South facing 30 degrees, direct exposure (exposure location: Suita City, Osaka Prefecture / within the premises of Nippon Shokubai Co., Ltd.)).

[0196] Next, the change in L value was calculated based on the formula: ΔL=(L1)-(L0), and the stain resistance was evaluated for 6 months based on the following evaluation criteria: (Evaluation criteria) ⊚: ΔL is less than 5 ◯: ΔL is 5 or more but less than 10 △: ΔL is 10 or more but less than 15 ×: ΔL is 15 or more

[0197] [Water permeability resistance] 10 parts of deionized water was added to 100 parts of enamel paint, and the mixture was applied to a test board (calcium silicate board, manufactured by Nippon Test Panel Co., Ltd., thickness 12 mm) in an amount of 100 g / m ２The coating was applied with a small roller (manufactured by Trusco Nakayama Corporation) so that the coating was 15 g / cm. The coating was then dried in a dryer at 100°C for 10 minutes to form a coating film. ２ The test was carried out under conditions where a roller pressure of 1000 psi was applied. A funnel (inner diameter: 35 mm) was placed on the coating film formed on the test plate, and the contact area between the two was sealed with a silicone-based bath bond (manufactured by Konishi Co., Ltd.). The water loss after 24 hours (the difference in water level height between the start and 24 hours) was measured in accordance with the "Funnel Method" specified in JIS A 5422. This water permeation resistance test plate was tested five times using five test plates from different lots, and the average value was taken as the water loss. The water permeation resistance was evaluated based on the following evaluation criteria. (Evaluation criteria) ◎: Water loss less than 1.0 mm ○: Water loss 1.0 to less than 2.0 mm △: Water loss 2.0 to less than 5.0 mm ×: Water loss 5.0 mm or more

[0198] [Rust Prevention] Enamel paint was applied to a black steel plate (manufactured by TP Giken Co., Ltd., product name: Black Steel Plate (SS400)) using a 4 mil applicator, dried at room temperature for 20 minutes, then dried at 100°C for 30 minutes, and further dried at room temperature for 7 days to form a coating film. The completed coated plate was cut with a cutter knife in accordance with 7.5 a) of JIS K 5600-7-9. Rust prevention was evaluated under the following test conditions using a salt spray tester (manufactured by Suga Test Instruments Co., Ltd., product name: STP-100). (Test Conditions) Test Tank Temperature: 35°C Air Saturator Temperature: 47°C Test Piece Angle: 20° Salt Water Concentration: 5% Aqueous Solution Spray Amount: 1.5±0.5 ml / h at 80 cm ２ (Evaluation criteria) ◎: No rust occurs for 200 hours or more in the salt spray test ○: No rust occurs for 100 hours or more but less than 200 hours in the salt spray test △: No rust occurs for 24 hours or more but less than 100 hours in the salt spray test ×: Rust occurs in less than 24 hours in the salt spray test

[0199] (Production Example A1) A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 938 parts of deionized water. A pre-emulsion for dropping consisting of 238 parts of deionized water, 100 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 380 parts of cyclohexyl methacrylate, 50 parts of 2-octyl acrylate, 35 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 5 parts of methacrylic acid, 10 parts of diacetone acrylamide, and 5 parts of γ-methacryloyloxypropyltrimethoxysilane was prepared and added to the dropping funnel. 54 parts of the pre-emulsion, corresponding to 6% of the total amount of all polymerizable monomer components, was added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Then, 30 parts of methyltrimethoxysilane, 75 parts of dimethyldimethoxysilane, and 10 parts of decyltrimethoxysilane were added to the other dropping funnel, and the pre-emulsion and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise over 120 minutes. After the addition was completed, the temperature was maintained for 60 minutes, and 25% aqueous ammonia was added to adjust the pH to 8 or higher. Subsequently, 158 parts of deionized water, 100 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 90 parts of 2-ethylhexyl acrylate, 20 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 50 parts of n-butyl acrylate, 205 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 15 parts of diacetone acrylamide, 10 parts of 1,2,2,6,6-pentamethylpiperidine-4-methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane, 120 parts of a second-stage pre-emulsion, 130 parts of dimethyldimethoxysilane, 10 parts of phenyltrimethoxysilane, and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 120 minutes. After completion of the dropwise addition, the temperature was maintained at the same temperature for 120 minutes to complete the polymerization. The resulting reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain a resin emulsion A1.

[0200] (Production Example A2) A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 713 parts of deionized water. A pre-emulsion for dropping, consisting of 238 parts of deionized water, 50 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 10 parts of methyl methacrylate, 130 parts of cyclohexyl methacrylate, 5 parts of 2-octyl acrylate, 5 parts of isoamyl acrylate, and 2 parts of γ-methacryloyloxypropyltrimethoxysilane, was prepared in the dropping funnel. 54 parts of the pre-emulsion, corresponding to 6% of the total amount of all polymerizable monomer components, was added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Then, 120 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane, and 30 parts of diphenyldimethoxysilane were added to the other dropping funnel, and the pre-emulsion and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 120 minutes. After the dropwise addition was completed, the temperature was maintained for 60 minutes, and then a second pre-emulsion consisting of 203 parts of deionized water, 110 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 150 parts of 2-ethylhexyl acrylate, 190 parts of cyclohexyl methacrylate, 50 parts of 2-octyl acrylate, 125 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 5 parts of methacrylic acid, and 10 parts of diacetone acrylamide, and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 120 minutes. After the dropwise addition was completed, the temperature was maintained for 60 minutes, and then 25% aqueous ammonia was added to adjust the pH to 8 or higher.Subsequently, 120 parts of deionized water, 40 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 180 parts of cyclohexyl methacrylate, 25 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 15 parts of diacetone acrylamide, 10 parts of 1,2,2,6,6-pentamethylpiperidine-4-methacrylate, 5 parts of γ-methacryloyloxypropyltrimethoxysilane, 60 parts of 2-octyl acrylate, 80 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane, 20 parts of diphenyldimethoxysilane, and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 120 minutes. After completion of the dropwise addition, the mixture was maintained at the same temperature for 120 minutes to terminate the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain Resin Emulsion A2.

[0201] (Production Examples A3 to A7) Resin emulsions A3 to A7 were obtained in the same manner as in Production Example A1, except that the monomer components shown in Tables 1-1 and 1-2 were used for polymerization.

[0202] (Production Example A8) A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 788 parts of deionized water. The dropping funnel was charged with 500 parts of deionized water, 160 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 180 parts of 2-ethylhexyl acrylate, 15 parts of methyl methacrylate, 445 parts of cyclohexyl methacrylate, 75 parts of 2-octyl acrylate, 110 parts of isoamyl acrylate, 75 parts of n-butyl acrylate, 20 parts of 2-hydroxyethyl acrylate, 20 parts of acrylic acid, 10 parts of methacrylic acid, A pre-emulsion for dropping was prepared, consisting of 30 parts of diacetone acrylamide, 20 parts of 1,2,2,6,6-pentamethylpiperidine-4-methacrylate, and 10 parts of γ-methacryloyloxypropyltrimethoxysilane. 95 parts of this, corresponding to 6% of the total amount of all polymerizable monomer components, was added to a flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Subsequently, 70 parts of methyltrimethoxysilane, 100 parts of dimethyldimethoxysilane, 10 parts of phenyltrimethoxysilane, and 10 parts of decyltrimethoxysilane were added to the other dropping funnel, and the pre-emulsion and 50 parts of a 2% aqueous solution of ammonium persulfate were added dropwise over 240 minutes. After completion of the dropwise addition, the same temperature was maintained for 120 minutes, and the polymerization was terminated. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire net to obtain Resin Emulsion A8.

[0203] (Production Example A9) Resin emulsion A9 was obtained in the same manner as in Production Example A2, except that the monomer components shown in Table 1-3 were used for polymerization.

[0204] (Production Example A10) Resin emulsion A10 was obtained in the same manner as in Production Example A1, except that the monomer components shown in Table 1-3 were used for polymerization.

[0205] (Production Example B1) 71 parts of deionized water, 200 parts of N-vinylpyrrolidone, 10 parts of methyl methacrylate, 10 parts of acrylic acid, and 30 parts of diacetone acrylamide were added to a reaction vessel equipped with a condenser, a nitrogen gas inlet tube, and a thermometer, and nitrogen gas was introduced into the reaction vessel to create a nitrogen gas atmosphere. Polymerization was initiated by adding 2 parts of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to the reaction vessel while stirring at room temperature. After the internal temperature rose due to the heat of reaction, stirring was continued at 80°C for 2 hours. Next, 1 part of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel, and the mixture was further stirred at 80°C for 1 hour to obtain a polymer solution B1 containing a water-soluble polymer.

[0206] (Production Examples B2 to B3, B5 to B8) Hydrophilic polymers B2 to B3 and B5 to B8 were obtained in the same manner as in Production Example B1, except that the monomer components shown in Tables 1-1 and 1-2 were used for polymerization.

[0207] (Production Example B9) Hydrophilic polymer B9 was obtained in the same manner as in Production Example B1, except that the monomer components shown in Table 1-3 were used for polymerization.

[0208] Example 1-1 The resin emulsion obtained in Production Example A1 and the hydrophilic polymer obtained in Production Example B1 were mixed so that the mass ratio of the non-volatile content of the resin emulsion to the non-volatile content of the water-soluble polymer (resin emulsion / hydrophilic polymer) was 97 / 3, thereby preparing an aqueous resin composition 1-1.

[0209] (Example 1-2) The resin emulsion obtained in Production Example A2 and the hydrophilic polymer obtained in Production Example B2 were mixed so that the mass ratio of the non-volatile content of the resin emulsion to the non-volatile content of the water-soluble polymer (resin emulsion / hydrophilic polymer) was 97 / 3. 100 parts of the aqueous resin composition obtained above and 10 parts of a 5% aqueous solution of adipic acid dihydrazide were added to a flask to prepare aqueous resin composition 1-2.

[0210] Examples 1-3, 1-5 to 1-9 Aqueous resin dispersions (water-dispersed resin compositions) 1-3, 1-5 to 1-9 were obtained in the same manner as in Example 1-1, except that the compositions were changed as shown in Tables 1-1, 1-2 and 1-3.

[0211] (Example 1-4) The resin emulsion obtained in Production Example A4 and PEG-20000 (manufactured by ADEKA Corporation) (hydrophilic polymer B4) were mixed so that the mass ratio of the non-volatile content of the resin emulsion to the non-volatile content of the water-soluble polymer (resin emulsion / hydrophilic polymer) was 97 / 3. 100 parts of the aqueous resin composition obtained above and 10 parts of a 5% aqueous solution of adipic acid dihydrazide were added to a flask to prepare aqueous resin composition 1-4.

[0212] Example 1-10 100 parts of the resin emulsion obtained in Production Example A10 and 10 parts of a 5% aqueous solution of adipic acid dihydrazide were added to a flask to obtain an aqueous resin composition 1-10.

[0213] Comparative Production Example C1 Resin emulsion C1 was obtained in the same manner as in Production Example A2, except that the monomer components shown in Table 1-3 were used for polymerization.

[0214] Comparative Production Example D1 Comparative hydrophilic polymer D1 was obtained in the same manner as in Production Example B1, except that the monomer components shown in Table 1-3 were used for polymerization.

[0215] (Comparative Example 1-1) A comparative aqueous resin dispersion (comparative water-dispersed resin composition) 1-1 was obtained in the same manner as in Example 1-1, except that the composition was changed to that shown in Table 1-3. The formulations of the polymerizable monomers and silane compounds used in the examples and comparative examples are shown in Tables 1-1, 1-2, and 1-3. The layer structures, Tg, ratios of polymerizable monomers and silane compounds, etc. in the emulsions obtained in the examples and comparative examples are also shown in Tables 1-4 and 1-5. The meanings of the abbreviations in Tables 1-1, 1-2, and 1-3 are as follows:

[0216] [Polymerizable monomers] CHMA: cyclohexyl methacrylate IBOA: isobornyl acrylate MMA: methyl methacrylate 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate 2OA: 2-octyl acrylate IAA: isoamyl acrylate HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid MAA: methacrylic acid DAAM: diacetone acrylamide HALS1: 1,2,2,6,6-pentamethylpiperidine-4-methacrylate NVP: N-vinylpyrrolidone

[0217] [Silane compounds] KBM-503: γ-methacryloyloxypropyltrimethoxysilane KBM-13: methyltrimethoxysilane KBM-22: dimethyldimethoxysilane KBM-103: phenyltrimethoxysilane KBM-202SS: diphenyldimethoxysilane KBM-3103C: decyltrimethoxysilane

[0218]

[0219]

[0220]

[0221]

[0222]

[0223] The enamel paints obtained using the aqueous resin compositions obtained in the above Examples and Comparative Examples were evaluated for weather resistance, water resistance, flexibility, stain resistance, and stain resistance after 6 months. The results are shown in Tables 1-6.

[0224]

[0225] Example 2-1 773 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser. A pre-emulsion for dropping, consisting of 156 parts of deionized water, 100 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 30 parts of 2-ethylhexyl acrylate, 50 parts of methyl methacrylate, 350 parts of cyclohexyl methacrylate, 55 parts of n-butyl acrylate, 10 parts of acrylic acid, 5 parts of methacrylic acid, and 5 parts of γ-methacryloyloxypropyltrimethoxysilane, was prepared in the dropping funnel. 95 parts of the pre-emulsion, corresponding to 6% of the total amount of all polymerizable monomer components, was added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Then, 40 parts of methyltrimethoxysilane, 25 parts of dimethyldimethoxysilane, and 10 parts of decyltrimethoxysilane were added to the other dropping funnel, and the pre-emulsion and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise over 120 minutes. After the addition was completed, the temperature was maintained for 60 minutes, and 25% aqueous ammonia was added to adjust the pH to 7 or higher. Subsequently, 184 parts of deionized water, 100 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 250 parts of 2-ethylhexyl acrylate, 20 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 25 parts of n-butyl acrylate, 5 parts of 1,2,2,6,6-pentamethylpiperidine-4-methacrylate, a second-stage pre-emulsion consisting of 10 parts of γ-methacryloyloxypropyltrimethoxysilane, 155 parts of methyltrimethoxysilane, 45 parts of dimethyldimethoxysilane, 10 parts of decyltrimethoxysilane, and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 120 minutes. After completion of the dropwise addition, the mixture was maintained at the same temperature for 120 minutes to terminate the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire net to obtain an aqueous resin dispersion (water-dispersed resin composition) 2-1.

[0226] Example 2-2 Aqueous resin dispersion (water-dispersed resin composition) 2-2 was obtained in the same manner as in Example 2-1, except that the monomer components shown in Table 2-1 were used for polymerization.

[0227] Example 2-3 A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 775 parts of deionized water. A pre-emulsion for dropping, consisting of 96 parts of deionized water, 51 parts of a 20% aqueous solution of Ramtel PD-104 (manufactured by Kao Corporation), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA Corporation), 5 parts of methyl methacrylate, 140 parts of cyclohexyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, and 2 parts of γ-methacryloyloxypropyltrimethoxysilane, was prepared in the dropping funnel. 95 parts of the pre-emulsion, corresponding to 6% of the total amount of all polymerizable monomer components, was added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Subsequently, 124 parts of methyltrimethoxysilane, 44 parts of dimethyldimethoxysilane, and 30 parts of phenyltrimethoxysilane were added to the other dropping funnel, and this was uniformly added dropwise over 60 minutes together with 13 parts of a 2% aqueous solution of ammonium persulfate. After completion of the dropping, the temperature was maintained for 60 minutes, and then a second-stage pre-emulsion consisting of 147 parts of deionized water, 50 parts of a 20% aqueous solution of Ramtel PD-104 (manufactured by Kao Corporation), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA Corporation), 140 parts of 2-octyl acrylate, 155 parts of cyclohexyl methacrylate, 235 parts of n-butyl acrylate, 10 parts of acrylic acid, 5 parts of methacrylic acid, and 5 parts of 2-hydroxyethyl methacrylate, and 25 parts of a 2% aqueous solution of ammonium persulfate was uniformly added dropwise over 120 minutes. After the dropwise addition was completed, the temperature was maintained for 60 minutes, and then 25% aqueous ammonia was added to adjust the pH to 7 or higher.Subsequently, a third-stage pre-emulsion consisting of 111 parts of deionized water, 38 parts of a 20% aqueous solution of Ramtel PD-104 (manufactured by Kao Corporation), 30 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA Corporation), 10 parts of 2-ethylhexyl acrylate, 139 parts of cyclohexyl methacrylate, 131 parts of n-butyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of 1,2,2,6,6-pentamethylpiperidine-4-methacrylate, and 3 parts of γ-methacryloyloxypropyltrimethoxysilane, an organosilane compound mixture consisting of 97 parts of methyltrimethoxysilane, 70 parts of dimethyldimethoxysilane, and 30 parts of phenyltrimethoxysilane, and 13 parts of a 2% aqueous solution of ammonium persulfate were uniformly added dropwise over 60 minutes. After completion of the dropwise addition, the temperature was maintained at the same temperature for 120 minutes to complete the polymerization. The resulting reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion (aqueous dispersed resin composition) 2-3.

[0228] Examples 2-4 to 2-7, 2-10 Aqueous resin dispersions (water-dispersed resin compositions) 2-4 to 2-7, and 2-10 were obtained in the same manner as in Example 2-3, except that the monomer components shown in Table 2-1 were used for polymerization.

[0229] Example 2-8 A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 575 parts of deionized water. A pre-emulsion for dropping, consisting of 96 parts of deionized water, 51 parts of a 20% aqueous solution of Ramtel PD-104 (manufactured by Kao Corporation), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA Corporation), 5 parts of methyl methacrylate, 140 parts of cyclohexyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, and 2 parts of γ-methacryloyloxypropyltrimethoxysilane, was prepared in the dropping funnel. 95 parts of the pre-emulsion, corresponding to 6% of the total amount of all polymerizable monomer components, was added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Then, 124 parts of methyltrimethoxysilane, 24 parts of dimethyldimethoxysilane, and 28 parts of diphenyldimethoxysilane were added to the other dropping funnel, and 13 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 60 minutes. After completion of the dropping, the temperature was maintained for 60 minutes, and then a second pre-emulsion consisting of 147 parts of deionized water, 50 parts of a 20% aqueous solution of Ramtel PD-104 (manufactured by Kao Corporation), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA Corporation), 240 parts of 2-octyl acrylate, 119 parts of cyclohexyl methacrylate, 20 parts of isobornyl acrylate, 141 parts of isoamyl acrylate, 10 parts of acrylic acid, 5 parts of methacrylic acid, 5 parts of 2-hydroxyethyl methacrylate, and 10 parts of diacetone acrylamide, and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 120 minutes. After the dropwise addition was completed, the temperature was maintained for 60 minutes, and then 25% aqueous ammonia was added to adjust the pH to 7 or higher.Subsequently, a third-stage pre-emulsion consisting of 111 parts of deionized water, 38 parts of a 20% aqueous solution of Ramtel PD-104 (manufactured by Kao Corporation), 30 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA Corporation), 151 parts of cyclohexyl methacrylate, 106 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 20 parts of 1,2,2,6,6-pentamethylpiperidine-4-methacrylate, 3 parts of γ-methacryloyloxypropyltrimethoxysilane, and 13 parts of diacetone acrylamide, an organosilane compound mixture consisting of 77 parts of methyltrimethoxysilane, 15 parts of dimethyldimethoxysilane, and 17 parts of diphenyldimethoxysilane, and 13 parts of a 2% aqueous solution of ammonium persulfate were uniformly added dropwise over 60 minutes. After the dropwise addition was completed, the mixture was maintained at the same temperature for 120 minutes, then cooled to 30°C, and 200 parts of a 5% aqueous solution of adipic acid dihydrazide was added to terminate the polymerization. The resulting reaction liquid was cooled to room temperature and filtered through a 300-mesh wire screen to obtain an aqueous resin dispersion (water-dispersed resin composition) 2-8.

[0230] Example 2-9 Aqueous resin dispersion (water-dispersed resin composition) 2-9 was obtained in the same manner as in Example 2-8, except that the composition was changed to that shown in Table 2-1.

[0231] Example 2-11 Aqueous resin dispersion (water-dispersed resin composition) 2-11 was obtained in the same manner as in Example 2-8, except that the composition was changed to that shown in Table 2-1.

[0232] Example 2-12 An aqueous resin dispersion (water-dispersed resin composition) 2-12 was obtained in the same manner as in Example 2-1, except that the composition was changed to that shown in Table 2-2 and 1 part of n-octyl thioglycolate (OTG) was used in each of the pre-emulsions for the inner layer and the outer layer for polymerization.

[0233] Comparative Example 2-1 A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 190 parts of ethylene glycol monobutyl ether, 200 parts of highly conjugated dehydrated castor oil fatty acid, 100 parts of dehydrated castor oil, 80 parts of Epotohto YD-128 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), 320 parts of Epotohto YD-014 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), 2 parts of acrylic acid, and 2 parts of triethylamine. The mixture was heated and stirred at 140°C for 210 minutes. Next, 50 parts of n-butyl methacrylate, 180 parts of styrene, 24 parts of acrylic acid, and 20 parts of cyclohexyl methacrylate were added to the dropping funnel, and the mixture was uniformly added dropwise over 90 minutes together with 25 parts of an 18% ethylene glycol monobutyl ether solution of Perbutyl D. After the dropwise addition was completed, the mixture was maintained at the same temperature for 30 minutes, followed by the addition of 45 parts of ethylene glycol monobutyl ether and 24 parts of acrylic acid. After the addition, the mixture was heated and stirred at the same temperature for 150 minutes. The reaction temperature was lowered to 100°C, and 72 parts of triethylamine was added over 30 minutes. Next, 1,410 parts of deionized water was added, and the mixture was allowed to cool. After the resulting reaction solution was cooled to room temperature, a comparative aqueous resin dispersion (comparative aqueous-dispersed resin composition) 2-1 was obtained.

[0234] Comparative Example 2-2 A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 505 parts of deionized water. A pre-emulsion for dropping, consisting of 119 parts of deionized water, 80 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 140 parts of 2-ethylhexyl acrylate, 160 parts of styrene, 30 parts of methyl methacrylate, 60 parts of cyclohexyl methacrylate, 9 parts of acrylic acid, and 1 part of n-octyl thioglycolate (OTG), was prepared in the dropping funnel. 95 parts of the pre-emulsion, corresponding to 6% of the total amount of all polymerizable monomer components, was added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. Polymerization was initiated by adding 10 parts of a 5% aqueous solution of PERBUTYL H (manufactured by NOF Corporation) and 20 parts of a 2.5% aqueous solution of thiourea dioxide. The above pre-emulsion, 30 parts of a 5% aqueous solution of Perbutyl H (NOF Corp.), and 40 parts of a 2.5% aqueous solution of thiourea dioxide were added dropwise uniformly over 60 minutes. After the addition was completed, the temperature was maintained at the same level for 40 minutes, and 25% aqueous ammonia was added to adjust the pH to 7 or higher. Subsequently, a second-stage pre-emulsion consisting of 237 parts of deionized water, 32 parts of a 25% aqueous solution of ADEKA REASOAP SR-20 (manufactured by ADEKA Corporation), 205 parts of 2-ethylhexyl acrylate, 50 parts of methyl methacrylate, 80 parts of cyclohexyl methacrylate, 220 parts of styrene, 20 parts of glycidyl methacrylate, 14 parts of acrylic acid, 10 parts of 2-hydroxyethyl methacrylate, and 1 part of n-octyl thioglycolate (OTG), as well as 60 parts of a 5% aqueous solution of Perbutyl H (manufactured by NOF Corp.) and 80 parts of a 2.5% aqueous solution of thiourea dioxide, were uniformly added dropwise over 120 minutes. After completion of the dropwise addition, the mixture was maintained at the same temperature for 60 minutes to terminate the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire netting to obtain a comparative aqueous resin dispersion (comparative aqueous-dispersed resin composition) 2-2.

[0235] The formulations of polymerizable monomers and silane compounds used in the Examples and Comparative Examples are shown in Tables 2-1 and 2-2. Furthermore, the layer structures, Tg, and ratios of polymerizable monomers and silane compounds in the emulsions obtained in the Examples and Comparative Examples are shown in Tables 2-3 and 2-4. The meanings of the abbreviations in Tables 2-1 and 2-2 are as follows: [Polymerizable monomers] CHMA: cyclohexyl methacrylate St: styrene IBOA: isobornyl acrylate MMA: methyl methacrylate 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate 2OA: 2-octyl acrylate GMA: glycidyl methacrylate BMA: n-butyl methacrylate IAA: isoamyl acrylate HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid MAA: methacrylic acid DAAM: diacetone acrylamide HALS1: 1,2,2,6,6-pentamethylpiperidine-4-methacrylate

[0236] [Silane compounds] KBM-503: γ-methacryloyloxypropyltrimethoxysilane KBM-13: methyltrimethoxysilane KBM-22: dimethyldimethoxysilane KBM-103: phenyltrimethoxysilane KBM-202SS: diphenyldimethoxysilane KBM-3103C: decyltrimethoxysilane ADH: adipic acid hydrazide

[0237]

[0238]

[0239]

[0240]

[0241] <Preparation of Enamel Paint> 100 parts of deionized water, 15 parts of a dispersant (manufactured by BYK Japan K.K., trade name: DisperBYK-190), 210 parts of titanium oxide (manufactured by Ishihara Sangyo Kaisha, Ltd.), 2 parts of a defoaming agent (manufactured by BYK Japan K.K., product number: BYK-024), and 2 parts of a 15% aqueous solution of a thickener (manufactured by ADEKA Corporation, trade name: ADEKA NOL UH-420) were mixed in a homodisper at a rotation speed of 300 min.－１ After dispersing for 60 minutes, the mixture was filtered through a 300 mesh wire netting to obtain a white paste.

[0242] To 100 parts of the water-dispersed resin composition obtained in each Example or Comparative Example, 10 parts of 2,2,4-trimethyl-1,3-pentanediol isobutyrate was added as a film-forming aid, and the mixture was mixed in a homodisper at a rotation speed of 1500 min －１ The mixture was stirred at RT for 30 minutes to obtain a dispersion.

[0243] To the dispersion obtained above, 80 parts of the white paste obtained above and 0.6 parts of an antifoaming agent (manufactured by BYK Japan Co., Ltd., product number: BYK-024) were added to obtain a mixture. －１ A thickener (manufactured by ADEKA Corporation, trade name: ADEKA NOL UH-420) was added to the mixture obtained above so that the viscosity at 25°C would be 4000 mPa s, and the mixture was stirred for 30 minutes, and then filtered through a 300-mesh wire netting to obtain an enamel paint.

[0244] The enamel paint obtained above was evaluated for weather resistance, flexibility, rust prevention, and water permeability. The results are shown in Table 2-5.

[0245]

Claims

1. A resin composition for paint containing a silicone-modified polymer emulsion, wherein the silicone-modified polymer emulsion has structural units derived from a polymerizable unsaturated monomer and structures derived from a silane compound, and the proportion of structures derived from the silane compound relative to 100% by mass of structural units derived from the polymerizable unsaturated monomer is 10% by mass or more.

2. The silane compound is represented by the following formula (1): R １ ｎ -Si-R ２ ４－ｎ (1) (wherein, R １ are the same or different and represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ２ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ does not have a polymerizable unsaturated group. n is an integer of 1 to 4. The coating resin composition according to claim 1, comprising a silane compound (a) represented by the formula (I) and a silane compound (b) having a polymerizable unsaturated group, wherein the proportion of structures derived from the silane compound (b) having a polymerizable unsaturated group in the silicone-modified polymer emulsion is 0.1 to 5 mass% relative to 100 mass% of structural units derived from the polymerizable unsaturated monomer.

3. A resin composition for paint according to claim 2, wherein the silicone-modified polymer emulsion has a ratio of structures derived from the silane compound (a) represented by formula (1) of 10 mass % or more relative to 100 mass % of structural units derived from polymerizable unsaturated monomers.

4. The silane compound (a) is a silane compound (a) represented by the formula (1) in which n is 2. ２ ) and a silane compound (a) in which n is 3 in the formula (1). ３ 4. The resin composition for paint according to claim 2 or 3, comprising:

5. The silane compound (a ２ ) to the silane compound (a ３ ) mass ratio (silane compound (a ３ ) / silane compound (a ２ 5. The resin composition for paint according to claim 4, wherein the value of (a) is 0.7 to 10.

6. The silane compound (a) is R in the formula (1). ２ The resin composition for paint according to any one of claims 2 to 5, comprising a compound in which is a hydrocarbon group having 3 to 20 carbon atoms.

7. In the silane compound (a), R in the formula (1) ２ is a hydrocarbon group having 3 to 20 carbon atoms is 0.1 to 30 mass% relative to 100 mass% of the silane compound (a).

8. The silane compound (b) having a polymerizable unsaturated group is represented by the following formula (2): (In the formula, R ３ are the same or different and represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group. ４ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X represents a direct bond or a divalent linking group. m is an integer of 1 to 3. R ５ , R ６ and R ７ and (b) are the same or different and represent a hydrogen atom or a methyl group.

9. The paint resin composition according to claim 1, wherein the paint resin composition contains a hydrophilic polymer.

10. The resin composition for paint according to claim 9, wherein the hydrophilic polymer has a solubility in water of 50 g / 100 g or more at 25°C.

11. The hydrophilic polymer has a homopolymer solubility parameter of 11 (cal / cm), calculated by the following method: ３ ) １／２ The resin composition for paint according to claim 9 or 10, wherein the proportion of structural units derived from the above monomers is 70 to 100% by mass relative to 100% by mass of all structural units. <Method for calculating solubility parameter> The solubility parameter (δ) (cal / cm) of the homopolymer is ３ ) １／２ is calculated by the following calculation method based on the evaporation energy (Δei) and molar volume (Δvi) of the structural units forming the polymer: δ=(Δei / Δvi) １／２ 12. A paint resin composition according to any one of claims 9 to 11, wherein the content of the hydrophilic polymer is 1.0 to 15 mass% relative to 100 mass% of structural units derived from polymerizable unsaturated monomers in the silicone-modified polymer emulsion.

13. A paint resin composition according to any one of claims 1 to 12, wherein the silicone-modified polymer emulsion has structural units derived from monomers having branched alkyl groups in a proportion of 5 to 75% by mass relative to 100% by mass of all structural units derived from polymerizable unsaturated monomers.

14. A resin composition for paint according to any one of claims 1 to 13, wherein the silicone-modified polymer emulsion has a glass transition temperature of -20 to 50°C.

15. A resin composition for paint according to any one of claims 1 to 14, wherein the silicone-modified polymer emulsion is an emulsion particle having a multilayer structure.

16. A paint resin composition according to any one of claims 1 to 15, wherein the silicone-modified polymer emulsion is an emulsion particle having at least a three-layer structure consisting of an outer layer, an intermediate layer, and an inner layer, and the proportion of the inner layer relative to the total of the outer layer and the intermediate layer (100% by mass) is 10 to 100% by mass.

17. A paint resin composition according to any one of claims 1 to 16, wherein the silicone-modified polymer emulsion has structural units derived from ultraviolet-absorbing monomers and / or ultraviolet-stable monomers.

18. The resin composition for paint according to any one of claims 1 to 17, further comprising a crosslinking agent.

19. The paint resin composition according to any one of claims 1 to 18, which is used for rust prevention purposes.

20. A resin composition for coating according to any one of claims 1 to 19, which is used for metal parts.

21. A method for producing a resin composition for paint containing a silicone-modified polymer emulsion, the method comprising a step of silicone-modifying a monomer component containing a polymerizable unsaturated monomer or a polymer thereof with a silane compound, wherein the amount of silane compound used in the silicone-modifying step is 10% by mass or more relative to 100% by mass of the polymerizable unsaturated monomer.

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