Anti-corrosive coating composition

Abstract

To provide an anti-corrosive coating composition capable of achieving both anti-corrosion performance and weather resistance.SOLUTION: An anti-corrosive coating composition comprising 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, 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 being 10 mass% or more, the silane compound comprising a silane compound (a) represented by the following formula (1): R1n-Si-R24-n (1) (where each R1 is the same or different and represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an acetoxy group; each R2 is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R2 does not have a polymerizable unsaturated group; and n is an integer of 1 to 4) and a silane compound (b) having a polymerizable unsaturated group, wherein the proportion of the structure derived from the silane compound (b) having a polymerizable unsaturated group in the silicone-modified polymer emulsion is 0.1 to 5 mass% with respect to 100 mass% of the structural unit derived from the polymerizable unsaturated monomer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an anti-rust coating composition, and more particularly to an anti-rust coating composition useful for metal members and the like. [Background technology]

[0002] Anti-rust paints are applied to steel machinery, building materials, etc. to prevent rust formation and deterioration of various structures, and the coating film formed thereby exerts a protective effect and an effect of preventing rust formation. 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.

[0003] 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.

[0004] Regarding water-based anticorrosive paints, Patent Document 1 discloses a water-based anticorrosive paint composition comprising: (I) a monomer mixture (where (a) + (b) + (c) = 100 parts by mass) comprising 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 falling under the category of (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 per 100 parts by mass of the total of the monomers (a), (b), and (c); and (II) a copolymer latex obtained by emulsion polymerization of the monomer mixture. Patent Document 2 discloses an anti-rust coating film containing a vinylidene chloride resin (1) and an acrylic resin (2), the glass transition temperature (Tg) of which is 20 to 40°C. Patent Document 3 discloses an aqueous resin dispersion containing a polymer (A) containing 0.1% by mass or more and 5.0% by mass or less of alkoxysilane group-containing polymerizable monomer units (a) and 0.2% by mass or more and 4.0% by mass or less of carboxyl group-containing polymerizable monomer units (b), and 0.05% by mass to 0.5% by mass of Na or K. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-074120 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-231587 [Patent Document 3] Japanese Patent Application Publication No. 2019-35007 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, various anti-rust paints and resins used in anti-rust paints have been disclosed in the past. However, in addition to having excellent anti-rust performance, anti-rust paints are also required to have coating films that have excellent weather resistance in order to maintain the anti-rust performance for a longer period of time.

[0007] The present invention has been made in view of the above-mentioned current situation, and has as its object to provide an anticorrosive coating composition which is capable of achieving both anticorrosive performance and weather resistance. [Means for solving the problem]

[0008] The present inventors have conducted extensive research into anti-rust coating compositions and have found that a composition containing a polymer emulsion silicone-modified in a specified ratio using a specified silane compound can achieve both anti-rust performance and weather resistance. This has led to the realization that the above-mentioned problems can be solved in an excellent manner, and has led to the completion of the present invention.

[0009] The present invention includes the following anticorrosive coating composition and the like. [1] A rust-preventive coating composition comprising 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, the proportion of the structures derived from the silane compound being 10 mass% or more relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomer, and the silane compound being a compound represented by the following formula (1): R 1 n -Si-R 2 4-n (1) (In the formula, 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.) 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. [2] The anticorrosive coating composition according to [1] above, which is used for metal members. [3] The anticorrosive coating composition according to [1] or [2] above, wherein the silicone-modified polymer emulsion has a ratio of structures derived from the silane compound (a) represented by the formula (1) above of 10 mass % or more relative to 100 mass % of structural units derived from the polymerizable unsaturated monomer. [4] The silane compound (a) is a silane compound (a) in which n is 2 in the formula (1). 2) and a silane compound (a) in which n is 3 in the above formula (1) 3 The anticorrosive coating composition according to any one of the above [1] to [3], [5] 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 R in the above formula (1). 2 is a hydrocarbon group having 3 to 20 carbon atoms. [7] In the silane compound (a), R in the formula (1) 2 The anticorrosive coating composition according to any one of the above [1] to [6], wherein the proportion of the compound which 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): [ka] (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 are the same or different and represent a hydrogen atom or a methyl group. [9] The anticorrosive coating composition according to any one of [1] to [8] above, wherein the silicone-modified polymer emulsion has a glass transition temperature of -20 to 50°C.

[10] The anticorrosive coating composition according to any one of [1] to [9] above, wherein the silicone-modified polymer emulsion is an emulsion particle having a multilayer structure.

[11] The anticorrosive coating composition according to any one of [1] to

[10] above, wherein the silicone-modified polymer emulsion is an emulsion particle having a structure of at least three layers, namely, 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.

[12] A method for producing an anticorrosive coating composition 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, the amount of the silane compound used in the silicone-modifying step being 10 mass% or more relative to 100 mass% of the polymerizable unsaturated monomer, and the silane compound is a compound represented by the following formula (1): R 1 n -Si-R 2 4-n (1) (In the formula, 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. A method for producing an anticorrosive coating composition, comprising a silane compound (a) represented by the following formula (I): and a silane compound (b) having a polymerizable unsaturated group, wherein the proportion of the silane compound (b) having a polymerizable unsaturated group is 0.1 to 5 mass% relative to 100 mass% of the polymerizable unsaturated monomer. [Effects of the Invention]

[0010] The anti-rust coating composition of the present invention has the above-mentioned constitution and can achieve both anti-rust performance and weather resistance, and therefore can be suitably used as an anti-rust coating material useful for metal members and the like. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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".

[0012] [Anti-rust paint composition] The anticorrosive coating composition of the present invention is an anticorrosive coating composition comprising 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 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, and the silane compound is a compound represented by the following formula (1): R 1 n -Si-R 2 4-n (1) (In the formula, 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.) and a silane compound (b) having a polymerizable unsaturated group, and the proportion of the structure derived from the silane compound (b) having a polymerizable unsaturated group is 0.1 to 5 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomer. The silicone-modified polymer emulsion contained in the anti-rust coating composition of the present invention has a crosslinked structure formed by silane compounds (a) and (b), and since the ratio of structures derived from silane compounds and the ratio of structures derived from silane compound (b) to 100% by mass of structural units derived from polymerizable unsaturated monomers are within the above-mentioned ranges, it exhibits excellent barrier properties against salt water, light, heat, etc., and is therefore thought to have excellent anti-rust properties and weather resistance.

[0013] The proportion of the silicone-modified polymer emulsion in the anticorrosive coating composition of the present invention is not particularly limited, but is preferably 5 to 80 mass %, more preferably 20 to 70 mass %, and even more preferably 30 to 60 mass %, relative to 100 mass % of the anticorrosive coating composition.

[0014] The anticorrosive coating composition of the present invention may contain other components in addition to the silicone-modified polymer emulsion. The proportion of the other components is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.1 to 10% by mass, relative to 100% by mass of the anticorrosive coating composition. In one aspect, the proportion of the other components is preferably 20 to 95% by mass, more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass, relative to 100% by mass of the anticorrosive coating composition.

[0015] The essential components and optional components contained in the anticorrosive coating composition of the present invention will be further described below.

[0016] <<Silicone-modified polymer emulsion>> The silicone-modified polymer emulsion contained in the anticorrosive coating composition of the present invention has 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, and the silane compound is a compound represented by the following formula (1): R 1 n -Si-R 2 4-n (1) (In the formula, 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.) and a silane compound (b) having a polymerizable unsaturated group, and the proportion of the structure derived from the silane compound (b) having a polymerizable unsaturated group is 0.1 to 5 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomer. In this specification, the polymerizable unsaturated monomer does not include the silane compound (b) having a polymerizable unsaturated group.

[0017] The silicone-modified polymer emulsion has a structural unit derived from a polymerizable unsaturated monomer, a structure derived from the silane compound (a), and a structure derived from the silane compound (b) having a polymerizable unsaturated group. The silicone-modified polymer emulsion has a structure derived from the silane compound (a), and is therefore expected to have an effect on the sliding properties of the coating film. Furthermore, in the structure derived from the silane compound (a) represented by the above formula (1), when n is 1 and / or 2, the effect of improving the flexibility of the coating film can be expected, and when n is 3 and / or 4, the effect of improving the solvent resistance and coating film hardness can be expected. In the present invention, the term "structural unit derived from a polymerizable unsaturated monomer" refers to a structural unit having the same structure as the structural unit formed by polymerization of a polymerizable unsaturated monomer. Note that the structural unit having the same structure as the structural unit formed by polymerization of a polymerizable unsaturated monomer is not limited to only the structural unit formed by actual polymerization of the polymerizable unsaturated monomer, but may also be a structural unit formed by another method as long as it has the same structure as the structural unit formed by polymerization of the polymerizable unsaturated monomer.

[0018] The silane compound (a) is a compound represented by the formula (1) above, and is —Si—R 1 It has a hydrolyzable silyl group as the aryl group. In the present invention, the term "structure derived from silane compound (a)" refers to a structure identical to the structure formed by the condensation reaction of the hydrolyzable silyl group contained in silane compound (a). Note that the structure identical to the structure formed by the condensation reaction of silane compound (a) is not limited to only the structure actually formed by the 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).

[0019] The silane compound (b) is a compound having a polymerizable unsaturated group and a silicon-containing group, and in the present invention, the "structure derived from silane compound (b)" means a structure identical to the structure formed by polymerization of the polymerizable unsaturated group of silane compound (b) and / or reaction of the silicon-containing group. Note that the structure identical to the structure formed by polymerization reaction or the like of silane compound (b) is not limited to only the structure actually formed by polymerization reaction or the like of silane compound (b), but may also be a structure formed by another method as long as it has the same structure as the structure formed by polymerization reaction or the like of silane compound (b).

[0020] In the silicone-modified polymer emulsion, the content of the silane compound-derived structure is 10% by mass or more relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer. The "content of the silane compound-derived structure" refers to the total proportion of the structure derived from silane compound (a) and the structure derived from silane compound (b). When the content of the silane compound-derived structure is 10% by mass or more, the resulting coating film has excellent weather resistance. 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, still more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass. In one aspect, an embodiment in which the content of the structure derived from the silane compound is 20 to 40 mass % is also one of the preferred embodiments of the present invention.

[0021] In the silicone-modified polymer emulsion, the proportion of the structure derived from the silane compound (b) having a polymerizable unsaturated group is 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 preferably 0.01 to 5 mass%, more preferably 0.05 to 5 mass%, and particularly preferably 0.1 to 4 mass%.

[0022] In the silicone-modified polymer emulsion, the proportion of the structure derived from 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. When the proportion of the structure derived from silane compound (a) in the silicone-modified polymer emulsion is 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 mass %, further preferably 15 to 80 mass %, even more preferably 15 to 70 mass %, and particularly preferably 20 to 65 mass %.

[0023] 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 2 However, it is preferable that the compound has a structure derived from a hydrocarbon group having 3 to 20 carbon atoms (also called a hydrophobic group-containing silane compound). This makes it possible to form a coating film with higher barrier properties. The proportion of the structure derived from the hydrophobic group-containing silane compound is not particularly limited, but is preferably 0.1 to 30 mass %, more preferably 0.5 to 28 mass %, even more preferably 1 to 25 mass %, and particularly preferably 5 to 20 mass %, relative to 100 mass % of the structure derived from the silane compound (a). The silicone-modified polymer emulsion preferably contains 0.1 to 30% by mass of hydrophobic-group-containing silane compound structures relative to 100% by mass of structural units derived from polymerizable unsaturated monomers. Having the proportion of hydrophobic-group-containing silane compound-derived structures in this range is expected to improve compatibility with acrylic polymers and film-forming properties of the coating film, leading to improved appearance of the coating film. Furthermore, having the proportion of hydrophobic-group-containing silane compound-derived structures in this range is expected to improve water resistance and water-stopping properties of the coating film, leading to improved rust prevention of the coating film. The proportion of the structure derived from the hydrophobic group-containing silane compound is more preferably 0.1 to 20 mass %, further preferably 0.2 to 15 mass %, even more preferably 0.5 to 10 mass %, and particularly preferably 1 to 10 mass %.

[0024] Although there are no particular restrictions on the weight-average molecular weight of the silicone-modified polymer emulsion, it is preferable that the weight-average molecular weight of the emulsion before the formation of the crosslinked structure is 100,000 or more, which will result in the resulting coating film having superior weather resistance and flexibility. The weight average molecular weight is more preferably 200,000 or more, further 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, the weight-average molecular weight of the resin constituting each layer (in the case of a crosslinked structure, the emulsion before the formation of the crosslinked structure) is preferably 100,000 or more. More preferably, it is 200,000 or more, even more preferably, it is 500,000 or more, and particularly preferably, it is 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 using gel permeation chromatography (Tosoh Corporation, product number: HLC-8120GPC, columns: TSKgel G-5000HXL and TSKgel GMHXL-L used in series).

[0025] The silicone-modified polymer emulsion preferably has a glass transition temperature (Tg) of -20 to 50 °C. This further improves the film-forming property. More preferably, Tg is -20 to 45 °C, still 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. <Tg Calculation Method> In this specification, the glass transition temperature of the emulsion means the temperature obtained based on the Fox's equation represented by Equation (I) using the glass transition temperature of the homopolymer of the monomer used in the monomer component constituting the emulsion: 1 / Tg = Σ(Wm / Tgm) / 100 (I) 〔In the formula, Wm represents the content ratio (mass %) of monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of monomer m〕 It means the temperature obtained based on Fox's equation.

[0026] In the present invention, unless otherwise specified, the glass transition temperature of the emulsion means the glass transition temperature obtained based on Equation (I).

[0027] The glass transition temperature of the entire resin layer constituting the emulsion particles having a plurality of resin layers means the glass transition temperature obtained from the mass fraction of each monomer in all monomer components used in the multi-stage emulsion polymerization and the glass transition temperature of the homopolymer of the corresponding monomer.

[0028] For monomers with an unknown glass transition temperature, such as special monomers and polyfunctional monomers, when the total amount of monomers with an unknown glass transition temperature in the monomer component is 10 mass % or less in mass fraction, the glass transition temperature is determined using only the monomers with a known glass transition temperature. When the total amount of monomers with an unknown glass transition temperature in the monomer component exceeds 10 mass % in mass fraction, the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermomechanical analysis (TMA), etc.

[0029] 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.

[0030] The glass transition temperatures of resins (polymers) are, 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.

[0031] 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.

[0032] 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.

[0033] 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, namely, 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 and inner layers (synthesized in the middle). When the silicone-modified polymer emulsion has a structure of three or more layers, the ratio of the inner layer to the total of the outer and intermediate layers (100% by mass) is preferably 10 to 100% by mass, more preferably 10 to 70% by mass, even more preferably 10 to 60% by mass, and particularly preferably 15 to 35% by mass.

[0034] When the silicone-modified polymer emulsion has a three-layer or more structure, the intermediate layer may contain a structure derived from a silane compound, but the proportion of this structure is preferably 5% by mass or less relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer that constitute the intermediate layer, which makes the flexibility of the silicone-modified polymer emulsion within a more suitable range. The proportion of the structure derived from the 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.

[0035] When the silicone-modified polymer emulsion has a structure of three or more layers, it is preferable that the outer layer and / or the inner layer have a structure derived from a silane compound. By using such emulsion particles, the balance between flexibility and water permeability of the coating film formed is within a suitable range. More preferably, the outer layer and the inner layer have a structure derived from a silane compound. The proportion of the silane compound-derived structure in the outer layer is preferably 2 to 80 mass %, more preferably 3 to 75 mass %, even more preferably 4 to 70 mass %, and particularly preferably 5 to 65 mass %, relative to 100 mass % of the structural units derived from the polymerizable unsaturated monomer that constitute the outer layer. The proportion of the silane compound-derived structure in the inner layer is preferably 10 to 250 mass %, more preferably 15 to 220 mass %, even more preferably 20 to 180 mass %, and particularly preferably 25 to 150 mass %, relative to 100 mass % of the structural units derived from the polymerizable unsaturated monomer that constitute the inner layer.

[0036] 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.

[0037] When the silicone-modified polymer emulsion has a multilayer structure, the Tg of the resin constituting the outermost layer is preferably from -40 to 40°C, more preferably from -35 to 35°C, and particularly preferably from -30 to 30°C.

[0038] 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 lower, more preferably −11° C. or lower, even more preferably −13° C. or lower, and particularly preferably −15° C. or lower.

[0039] When the silicone-modified polymer emulsion has a two-layer or three-layer or more 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 more layer structure, is preferably 40°C or more. By using such emulsion particles, the balance between flexibility and water permeability resistance of the coating film formed is within a suitable range. The difference is more preferably 50°C or more, even more preferably 60°C or more, and particularly preferably 70°C or more.

[0040] <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.

[0041] 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 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."

[0042] 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.

[0043] <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, and a (meth)acryloyl group. The polymerizable unsaturated monomer preferably includes a monomer having a (meth)acryloyl group.

[0044] The polymerizable unsaturated monomer is not particularly limited, and examples thereof include acyclic alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, 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.

[0045] The polymerizable unsaturated monomer preferably contains a hydrophobic monomer such as an acyclic alkyl (meth)acrylate, an alicyclic structure-containing (meth)acrylate, an aromatic monomer, etc. This allows the formation of a coating film with higher barrier properties. The total proportion of the acyclic alkyl (meth)acrylate, alicyclic structure-containing (meth)acrylate, and aromatic monomer is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to 100% by mass of the polymerizable unsaturated monomer. The proportion of the hydrophobic monomer is preferably 99% by mass or less. Among the hydrophobic monomers, acyclic alkyl (meth)acrylates and alicyclic structure-containing (meth)acrylates are preferred. In one preferred embodiment of the present invention, the ratio of the acyclic alkyl (meth)acrylate and the alicyclic structure-containing (meth)acrylate is within the above preferred range.

[0046] The silicone modified polymer emulsion has a crosslinked structure by silane compound, but may have a crosslinked structure other than the crosslinked structure by silane compound.For example, when the silicone modified polymer emulsion has a structural unit derived from a monomer having reactive group such as hydroxyl group-containing (meth)acrylate, carboxyl group-containing monomer, aromatic monomer, nitrogen atom-containing monomer, oxo group-containing monomer, etc. as a structural unit derived from polymerizable unsaturated monomer, it can form a crosslinked structure by reacting this reactive group with a crosslinking agent, etc. More preferred monomers having a reactive group are nitrogen atom-containing monomers, such as 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, more preferably 0.1 to 5% by mass, and even more preferably 0.5 to 3% by mass, relative to 100% by mass of the polymerizable unsaturated monomer.

[0047] The polymerizable monomer preferably contains an ultraviolet-absorbing monomer and / or an ultraviolet-stable monomer, which 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, 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 an ultraviolet-absorbing monomer and / or an 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, 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 monomer that forms the outermost layer.

[0048] When the silicone-modified polymer emulsion has structural units derived from UV-absorbing monomers having amino groups and / or UV-stable monomers in the outermost layer, the proportion of monomers having acid groups, 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 groups and acid groups in the outermost layer from reacting with each other, thereby preventing the stability of the emulsion particles from decreasing. The proportion of monomers having acid groups is more preferably 5% by mass or less, and even more preferably 1% by mass or less. A preferred embodiment of the present invention is one in which the outermost layer does not have structural units derived from monomers having acid groups.

[0049] 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 relative to 100% by mass of the polymerizable unsaturated monomers that form the intermediate layer, more preferably 2 to 10% by mass, and even more preferably 3 to 8% by mass.

[0050] 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, sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, n-pentyl(meth)acrylate, isopentyl(meth)acrylate, sec-pentyl(meth)acrylate, tert-pentyl(meth)acrylate, and neopentyl(meth)acrylate. , 1-methylpentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, sec-hexyl (meth)acrylate, tert-hexyl (meth)acrylate, neohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-heptyl (meth)acrylate, isoheptyl (meth)acrylate, sec-heptyl (meth)acrylate, tert-heptyl (meth)acrylate, neoheptyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate tert-octyl (meth)acrylate, isooctyl (meth)acrylate, sec-octyl (meth)acrylate, tert-octyl (meth)acrylate, neooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, sec-nonyl (meth)acrylate, tert-nonyl (meth)acrylate, neononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, sec-decyl (meth)acrylate, tert-decyl (meth)acrylate, neodecyl (meth)acrylate Acrylate, n-undecyl (meth)acrylate, isoundecyl (meth)acrylate, sec-undecyl (meth)acrylate, tert-undecyl (meth)acrylate, neoundecyl (meth)acrylate, n-dodecyl (meth)acrylate, isododecyl (meth)acrylate, sec-dodecyl (meth)acrylate, tert-dodecyl (meth)acrylate, neododecyl (meth)acrylate, n-tridecyl (meth)acrylate, isotridecyl (meth)acrylate, sec-tridecyl (meth)acrylate,tert-Tridecyl (meth)acrylate, neotridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, isotetradecyl (meth)acrylate, sec-tetradecyl (meth)acrylate, tert-tetradecyl (meth)acrylate, neotetradecyl (meth)acrylate, n-pentadecyl (meth)acrylate, isopentadecyl (meth)acrylate, sec-pentadecyl (meth)acrylate, tert-pentadecyl (meth)acrylate, neopentadecyl (meth)acrylate, n-hexadecyl (meth)acrylate, isohexadecyl (meth)acrylate, sec-hexadecyl (meth) Examples of the alkyl group include acyclic alkyl (meth)acrylates having 1 to 18 carbon atoms, such as acrylate, tert-hexadecyl (meth)acrylate, neohexadecyl (meth)acrylate, n-heptadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, sec-heptadecyl (meth)acrylate, tert-heptadecyl (meth)acrylate, neoheptadecyl (meth)acrylate, n-octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, sec-octadecyl (meth)acrylate, tert-octadecyl (meth)acrylate, and neooctadecyl (meth)acrylate. One or more of these may be used. 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. These monomers may be used alone, or two or more types may be used in combination.

[0051] The proportion of the acyclic alkyl (meth)acrylate is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, relative to 100% by mass of the polymerizable unsaturated monomer.

[0052] 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.

[0053] 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, and even more preferably 30 to 70% by mass.

[0054] 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 mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass, relative to 100% by mass of the polymerizable unsaturated monomer that constitutes the outer layer. The proportion of the alicyclic structure-containing (meth)acrylate in the inner layer is preferably 40 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 60 to 100% by mass, and particularly preferably 70 to 100% by mass, relative to 100% by mass of the polymerizable unsaturated monomer that constitutes the inner layer.

[0055] 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 mass, more preferably 25 to 75% by mass, even more preferably 28 to 70% by mass, and particularly preferably 30 to 65% by mass, relative to 100% by mass of the polymerizable unsaturated monomer that constitutes the outer layer. The proportion of the alicyclic structure-containing (meth)acrylate in the intermediate layer is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, even more preferably 18 to 40% by mass, and particularly preferably 20 to 35% by mass, relative to 100% by mass of the polymerizable unsaturated monomer that constitutes the intermediate layer. The proportion of the alicyclic structure-containing (meth)acrylate in the inner layer is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass, relative to 100% by mass of the polymerizable unsaturated monomer that constitutes the inner layer.

[0056] The hydroxyl group-containing (meth)acrylate is not particularly limited, but examples thereof 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. 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.

[0057] The carboxyl group-containing monomer is not particularly limited, but examples thereof include carboxyl group-containing aliphatic monomers such as (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and maleic anhydride, and 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.

[0058] 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 with 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. It is preferable to appropriately adjust the ratio of the aromatic monomer in the polymerizable unsaturated monomer depending on the application of the coating material of the present invention. The proportion of the aromatic monomer is not particularly limited, but is preferably 20% by mass or less relative to 100% by mass of the polymerizable unsaturated monomer. By making it 20% by mass or less, the weather resistance of the coating film is further improved. The proportion of the aromatic monomer is more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0059] The nitrogen atom-containing monomer is not particularly limited, and examples thereof include (meth)acrylamide compounds such as (meth)acrylamide, diacetone (meth)acrylamide, N-monomethyl (meth)acrylamide, N-monoethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, methylene bis (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 proportion 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.

[0060] The oxo group-containing monomer is not particularly limited, but examples thereof 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.

[0061] 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.

[0062] 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 types. The proportion 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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. Examples of suitable polymerizable piperidine compounds include (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.

[0067] <Silane compounds> The silane compound constituting the silicone-modified polymer emulsion is represented by the following formula (1): R 1 n -Si-R 2 4-n (1) (In the formula, 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. The compound includes a silane compound (a) represented by the following formula: and a silane compound (b) having a polymerizable unsaturated group. The silane compound (b) is a compound having a polymerizable unsaturated group and a silicon-containing group, and polymerizes 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. Furthermore, 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 silane compound (b) constituting a polymer chain, thereby forming a network structure.

[0068] (Silane compound (a)) The silane compound (a) is a compound represented by the above formula (1). R in the above formula (1) 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.

[0069] 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, preferred are methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups, and more preferred are methoxy and ethoxy groups.

[0070] 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.

[0071] 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 is a hydrocarbon group, it is a group that does not have a polymerizable unsaturated group. R 1 is preferably a hydrocarbon group having no polymerizable unsaturated group. Examples of the hydrocarbon group having no polymerizable unsaturated group include an alkyl group, an aryl group, and an aralkyl group.

[0072] 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, a sec -Octyl, tert-octyl, neooctyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, neononyl, n-decyl, isodecyl, sec-decyl, tert-decyl, neodecyl, n-undecyl, isoundecyl, sec-undecyl, tert-undecyl, neoundecyl, n-dodecyl, isododecyl, sec-dodecyl, tert-dodecyl, neododecyl, n-tridecyl, isotridecyl, sec-tridecyl, tert-tridecyl, 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.

[0073] 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, and a biphenylyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, and a benzhydryl group.

[0074] Above R 2 The hydrocarbon 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. The silane compound (a) may be R 2 It is preferable that the compound contains a hydrophobic group-containing silane compound in which R is a hydrocarbon group having 3 to 20 carbon atoms. 2 The hydrocarbon group preferably has 3 to 18 carbon atoms, 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 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. R in the above 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 rust prevention performance, n in formula (1) is 2, and two R 2 In one preferred embodiment of the present invention, the hydrophobic group-containing silane compound is one in which is an aryl group.

[0075] 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. 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.

[0076] In the above formula (1), n ​​is an integer of 1 to 4. n is preferably 2 or 3. By using, as the silane compound (a), a silane compound (a2) in which n in formula (1) is 2, it is expected that the coating film will have both good weather resistance and flexibility. By using, as the silane compound (a), a silane compound (a3) ​​in which n in formula (1) is 3, it is expected that the solvent resistance and hardness of the coating film will be improved. The silane compound (a) is a silane compound (a) in which n is 2 in the formula (1). 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 coating film is formed.

[0077] The silane compound (a) is 2 ) and the above silane compound (a 3 ), the silane compound (a 2 ) to the silane compound (a 3 ) 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.

[0078] The silane compound (a) in which n is 1 in the above formula (1) 1 ) may, for example, be 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, or 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-triphenoxysilane, tri-t-butylmethoxysilane, tri-t-butylethoxysilane, tri-t-butyl-n-propoxysilane, tri-t-butyl-iso-propoxysilane,Examples of such silane 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.

[0079] Silane compounds (a) in which n is 2 in the above formula (1) 2 ) may, for example, be 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 di-isopropyl-di-isopropoxysilane, di-isopropyl-di-n-butoxysilane, di-isopropyl-di-sec-butoxysilane, di-isopropyl-di-tert-butoxysilane, di-isopropyl-diphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-isopropoxysilane, 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 such 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, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, dicyclohexyldimethoxysilane, and dicyclohexyldiethoxysilane are preferred, and diphenyldimethoxysilane, diphenyldiethoxysilane, and phenylmethyldimethoxysilane are more preferred.

[0080] The silane compound (a) in which n is 3 in the above formula (1) 3 ) may, for example, be 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, Isopropyltriethoxysilane, ethyltriphenoxysilane, 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- 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 thereof include trimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyltriethoxysilane, and dicyclohexyldiethoxysilane. Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, and cyclohexyltriethoxysilane are preferred, and methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are more preferred.

[0081] (Silane compound (b)) The silane compound (b) having a polymerizable unsaturated group may be any 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. A hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to the silicon atom. The silane compound (b) is more preferably a compound represented by the following formula (2):

[0082] [ka]

[0083] (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.

[0084] 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. R 3 Specific examples and preferred forms of the alkoxy group in R 1 As stated above. R 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.

[0085] 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. R 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 alkyl groups, aryl groups, and aralkyl groups include R 2 As stated above.

[0086] The hydrocarbon 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. When the hydrocarbon group is an aryl group or an aralkyl group, it preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, even more preferably 6 to 12 carbon atoms, and particularly preferably 6 to 8 carbon atoms.

[0087] Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, and an icosenyl group. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group, and an icosynyl group.

[0088] 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.

[0089] 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.

[0090] In the above formula (2), X is a direct bond or a divalent linking group. The divalent linking group in X is not particularly limited, but may be -OR 8 -, -NHR 9 -etc. Above R 8 , R 9 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.

[0091] The alkylene 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. 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.

[0092] 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.

[0093] 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, 4-(meth)acryloyloxypropylmethyldimethoxysilane, 4-(meth)acryloyloxybutyltriethoxysilane, 4-(meth)acryloyloxybutylmethyldiethoxysilane, 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. Of these, 1-(meth)acryloyloxymethyltrimethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, and 3-(meth)acryloyloxypropyltrimethoxysilane are preferred, and 3-(meth)acryloyloxypropyltrimethoxysilane is more preferred.

[0094] <<Other ingredients>> If necessary, other components than the silicone-modified polymer emulsion may be added to the anticorrosive coating composition of the present invention, provided that the effects of the present invention are not impaired. The other components are not particularly limited, but include various fillers, various additives, other emulsions, and the like.

[0095] 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 fiber; 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.

[0096] When the anticorrosive coating composition of the present invention contains a pigment, it is preferably an anticorrosive pigment. An anticorrosive pigment is a pigment added to a coating 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, the anti-rust pigment is preferably an anti-rust pigment that does not contain lead or chromium, and examples thereof include phosphate-based metal salts, molybdate-based metal salts, borate-based metal salts, cyanamide-based metal salts, etc. These can be used alone or in combination of two or more.

[0097] 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.

[0098] Examples of the molybdate-based metal salt rust-preventive pigment include zinc molybdate, calcium molybdate, zinc calcium molybdate, magnesium molybdate, nickel molybdate, cobalt molybdate, strontium molybdate, zinc phosphomolybdate, calcium phosphomolybdate, and aluminum phosphomolybdate. Examples of the borate metal salt rust preventive pigment include barium borate, barium metaborate, calcium metaborate, and magnesium metaborate.

[0099] Examples of the anti-rust pigment of a cyanamide metal salt include zinc cyanamide and calcium cyanamide zinc. Furthermore, it is also possible to use a modified anti-rust pigment by adding zinc oxide or an oxide or hydroxide of an alkaline earth metal such as magnesium oxide or magnesium hydroxide to the above anti-rust pigment.

[0100] When the anticorrosive coating composition of the present invention contains a pigment, the content of the pigment in the anticorrosive coating composition can be set appropriately, but is preferably 0.1 to 50 mass %, more preferably 1 to 10 mass %. When the anticorrosive coating composition of the present invention contains a pigment, the content of the pigment relative to the silicone-modified polymer emulsion can be set as appropriate, but is preferably 5 to 80 mass %, more preferably 10 to 60 mass %.

[0101] The additives are not particularly limited, and examples thereof include plasticizers, anti-sagging agents, thickeners, antifoaming agents, dispersants, foaming agents, colloid stabilizers, preservatives, pH adjusters, antioxidants, colorants, crosslinking agents, hardeners, water retention agents, etc. These may be used alone or in combination of two or more.

[0102] Among the above additives, examples of thickeners include polycarboxylates, urethane association types, polyether types, cellulose ethers, polyacrylic types, and polyacrylamides. Examples of foaming agents include sodium bicarbonate, ammonium carbonate, nitroso compounds, azo compounds, and sulfonyl hydrazide compounds. Examples of crosslinking agents and curing agents include hydrazine-based crosslinking agents, polyfunctional epoxy compounds, isocyanate-based crosslinking agents, melamine resins, and oxazolin compounds.

[0103] Other emulsions include, for example, natural rubber latex, acrylic resin latex, vinyl acetate resin latex, urethane resin latex, and epoxy resin latex.

[0104] The anticorrosive coating composition of the present invention can be used by applying it to a substrate. The substrate is not particularly limited, but various metal members such as iron, plated steel, stainless steel, and aluminum are preferred. The use of the anticorrosive coating composition of the present invention on a metal member is one of the preferred embodiments of the present invention. The anticorrosive coating composition of the present invention may be applied to a substrate as a single layer, or the coating film obtained by application and drying may be topcoated with any of the commonly used water-based coating materials, such as acrylic coating materials, urethane coating materials, UV coating materials, silicone coating materials, melamine resin coating materials, epoxy coating materials, and fluororesin coating materials. The anticorrosive coating composition of the present invention has excellent anticorrosive properties and may be used as an undercoat, but also has excellent weather resistance and can be suitably used as a topcoat.

[0105] The anticorrosive coating composition of the present invention can be applied to a substrate by any conventionally known method, such as by using a spatula, a brush, an air spray, an airless spray, a mortar gun, a lysine gun, or a roll coater.

[0106] [Method for producing anti-rust coating composition] The present invention relates to a method for producing an anticorrosive coating composition containing a silicone-modified polymer emulsion, the method comprising the step of silicone-modifying a monomer component containing a polymerizable unsaturated monomer or a polymer thereof with a silane compound, wherein the amount of the silane compound used in the silicone-modifying step is 10% by mass or more relative to 100% by mass of the polymerizable unsaturated monomer, and the silane compound is a compound represented by the following formula (1): R 1 n -Si-R 2 4-n (1) (In the formula, 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.) and a silane compound (b) having a polymerizable unsaturated group, wherein the proportion of the silane compound (b) having a polymerizable unsaturated group is 0.1 to 5 mass% relative to 100 mass% of the polymerizable unsaturated monomer.

[0107] The method for producing the silicone-modified polymer emulsion is not particularly limited as long as it includes a step of silicone-modifying a monomer component containing a polymerizable unsaturated monomer or a polymer thereof with a silane compound (hereinafter also referred to as the silicone-modifying step). The polymerizable unsaturated monomer may be simultaneously reacted with the silane compound (a) and the silane compound (b), or the silane compound (a) may be reacted with a polymer obtained by polymerizing the polymerizable unsaturated monomer with the silane compound (b). Specific examples and preferred forms of the polymerizable unsaturated monomer, silane compound (a) and silane compound (b) used in the above production method are the same as those described for the silicone-modified polymer emulsion. Furthermore, the amount of silane compound used in the method for producing the silicone-modified polymer emulsion may be 10% by mass or more relative to 100% by mass of the polymerizable unsaturated monomer, but it is preferable to adjust the amounts of silane compound (a) and silane compound (b) used so that the preferred ratio of silane compound in the silicone-modified polymer emulsion is achieved. Specific examples, preferred forms and amounts of each polymerizable unsaturated monomer in the monomer component used in the above production method are the same as those described for the silicone-modified polymer emulsion.

[0108] In the silicone modification step, the reaction step of the silane compound (a) may be carried out after the polymerization step of polymerizing the monomer component containing the polymerizable unsaturated monomer and the silane compound (b), or the polymerization step and the reaction step of the silane compound (a) may be carried out simultaneously, but preferably, the polymerization reaction of the monomer component containing the polymerizable unsaturated monomer and the silane compound (b) is started, and then the reaction of the silane compound (a) is started, and the reaction of the silane compound (a) is carried out while the polymerization step is being carried out. This allows the polymerization reaction and the reaction of the silane compound (a) and the silane compound (b) to proceed in parallel. More specifically, after the initiation of the polymerization reaction of the monomer components, it is preferable to dropwise add the monomer components containing the polymerizable unsaturated monomer and the silane compound (b) and the silane compound (a) separately into a reactor using different dropping funnels to carry out the reaction.

[0109] The dropwise addition of the monomer component and the silane compound (a) in the silicone modification step is preferably carried out at a pH of 1 to 5. This allows the hydrolysis and condensation reaction of the silane compound to proceed more quickly. 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.

[0110] The polymerization of the monomer component in the silicone modification step is not particularly limited as long as it involves a polymerization reaction of a monomer component containing a polymerizable unsaturated monomer and a silane compound (b), but it is preferable to carry out the polymerization reaction by emulsion polymerization. The method for emulsion polymerizing the monomer component containing the polymerizable unsaturated monomer and the silane compound (b) is not particularly limited, and examples thereof include a method in which an emulsifier is dissolved 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 the monomer component and a polymerization initiator are added dropwise, and a method in which a monomer component that has been emulsified in advance using an emulsifier and water is added dropwise to water or an aqueous medium. The amount of the medium used in the emulsion polymerization may be appropriately determined taking into consideration the amount of nonvolatile matter contained in the resulting silicone-modified polymer emulsion.

[0111] 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.

[0112] 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. One or more of these may be used.

[0113] 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.

[0114] 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.

[0115] The amphoteric emulsifier is not particularly limited, but examples thereof include betaine ester emulsifiers, and one or more of these can be used.

[0116] The polymer emulsifier is not particularly limited, but 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.

[0117] 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.

[0118] 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 alkylpropenylphenyl ether ammonium sulfate (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, Aqualon BC-10, etc.), sulfonate salts of allyloxymethyl alkyloxy polyoxyethylene (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), sulfonate salts of allyloxymethyl nonylphenoxyethyl hydroxy polyoxyethylene (e.g., ADEKA Corporation, trade name: Adeka Reasoap SE-10, etc.), allyloxymethyl alkoxyethyl hydroxy polyoxyethylene sulfate ester salts (e.g., ADEKA Corporation, trade name: Adeka Reasoap SR-10, SR-20, SR-30, etc.), -30, etc.), bis(polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salts (for example, trade name: Antox MS-60, manufactured by Nippon Nyukazai Co., Ltd.), allyloxymethylalkoxyethylhydroxypolyoxyethylenes (for example, trade name: Adeka Reasop ER-20, manufactured by ADEKA Corporation), polyoxyethylene alkylpropenylphenyl ethers (for example, trade name: Aqualon RN-20, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), allyloxymethylnonylphenoxyethylhydroxypolyoxyethylenes (for example, trade name: Adeka Reasop NE-10, manufactured by ADEKA Corporation), polyoxyethylene styrenated propenylphenyl ether sulfate salts (for example, trade name: Aqualon AR-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene styrenated propenylphenyl ether sulfates (for example, trade name: Aqualon AN-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like. One or more of these may be used.

[0119] 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 or less.

[0120] 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 in combination of two or more.

[0121] 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.

[0122] 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.

[0123] In order to promote decomposition of the polymerization initiator, a suitable amount of a polymerization initiator decomposer, 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. Furthermore, if necessary, a suitable amount of additives, such as a chain transfer agent, 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.

[0124] In the polymerization step, a chain transfer agent may be used. This allows the molecular weight of the emulsion to be adjusted. In addition, an embodiment in which no chain transfer agent is used is also one of the preferred embodiments of the present invention. The chain transfer agent is not particularly limited, and 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, t-butanol, and the like. Examples of suitable solvents 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; 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 the chain transfer agent used is not particularly limited, but can be, for example, 0.01 to 5% by mass, preferably 0.02 to 1% by mass, and more preferably 0.05 to 0.5% by mass, relative to 100% by mass of the polymerizable monomer.

[0125] 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.

[0126] 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.

[0127] The polymerization time for emulsion polymerization of the monomer components is not particularly limited and may be set appropriately depending on the progress of the polymerization reaction, but is usually about 2 to 15 hours.

[0128] In the silicone modification step, after the dropwise addition of the monomer component and silane compound is completed, the polymerization temperature is preferably maintained at 50 to 90°C for 0.5 to 5 hours, and more preferably 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 the silane compound is preferably 1 to 5. This allows the condensation reaction of the silane compound (a) and the silane compound (b) to proceed sufficiently. The pH is more preferably 1.5 to 4.5. The pH can be adjusted using a base such as ammonia or sodium hydroxide. When producing a silicone-modified polymer emulsion having a structure of three or more layers and using a monomer having an acid group in the intermediate layer, it is preferable to adjust the pH to 6 to 7 after completion of the dropwise addition of the monomer component for the intermediate layer. This converts the acid group in the intermediate layer into a salt form, and the emulsion particles become electrically charged, thereby further improving dispersion stability.

[0129] When the emulsion particles have a multilayer structure, the polymerization reaction and the reaction of the silane compound (a) and the silane compound (b) can be repeated two or more times in the silicone modification step to prepare emulsion particles having at least two resin layers.

[0130] In the above production method, a step of crosslinking the emulsion particles may be carried out after the silicone modification step or after the polymerization reaction of the monomer components. By carrying out the crosslinking step, the resulting silicone-modified polymer emulsion will have a crosslinked structure derived from the crosslinking agent in addition to the crosslinked structure derived from the silane compound, and will have better weather resistance. The crosslinking agent used in the crosslinking step is not particularly limited, and examples thereof 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 crosslinking agents may be used alone or in combination of two or more. Among these, hydrazine-based crosslinking agents are preferred. The amount of the crosslinking agent can be appropriately set depending on the type of the crosslinking agent, etc., but is preferably 0.1 to 5% by mass, and more preferably 0.5 to 2% by mass, relative to 100% by mass of the polymerizable monomer.

[0131] Examples of the hydrazine crosslinking agent include adipic acid dihydrazide and polymers having a hydrazide group, with adipic acid dihydrazide being preferred.

[0132] 〔paint〕 The present invention also relates to a paint containing the anticorrosive paint composition of the present invention. The anti-rust coating composition of the present invention can be used as a clear coating as it is, or can be used as an enamel coating by adding an appropriate amount of a colorant such as a dye or pigment to the anti-rust coating composition of the present invention. The content of the silicone-modified polymer emulsion in the coating material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, relative to 100% by mass of the coating material.

[0133] The coating material of the present invention may further contain additives other than colorants. The additives are not particularly limited, but examples thereof include dispersants, antifoaming agents, thickeners, rheology control agents, foaming agents, plasticizers, wetting agents, antiblocking agents, antioxidants, preservatives, polymerization inhibitors, antistatic agents, ultraviolet absorbers, ultraviolet stabilizers, silane coupling agents, flame retardants, leveling agents, plasticizers, antioxidants, etc. These additives may be used alone or in combination of two or more. The amount of additive contained in the coating material varies depending on the type of additive, so it is preferable to adjust the amount appropriately depending on the type of additive. [Example]

[0134] 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."

[0135] <Solid content> The amount of nonvolatile matter in the resin emulsion was determined by weighing 1 g of the resin emulsion, drying it in a hot air dryer at 110°C for 1 hour, and calculating the nonvolatile matter content of the resulting residue using the following formula (II): [Non-volatile content in resin emulsion (mass%)] = ([mass of residue] ÷ [1 g of resin emulsion]) × 100 (II) This means the value calculated based on

[0136] [Weather resistance] Apply a sealer (SK Chemical Co., Ltd., product name: EX Sealer) with an air spray at a rate of 150 g / m 2 The coating was uniformly applied to a slate board (manufactured by Nippon Test Panel Co., Ltd.) so that the coating was as shown in the figure, and the board was dried in the air at room temperature (about 23°C) for one week to prepare a test board. Next, enamel paint was applied to the sealer surface of the test panel with an 8 mil applicator, and 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 with a gloss meter (product number: VG2000, manufactured by Nippon Denshoku Industries Co., Ltd.) Subsequently, a weathering test was conducted for 2500 hours on the test panel coated with enamel paint under the following weathering test conditions, and then the 60° specular gloss of the enamel-coated surface of the test panel was measured with the gloss meter in the same manner as above.

[0137] (Weather resistance test conditions) Testing machine: Weather resistance testing machine (manufactured by Daipla Wintes Co., Ltd., product name: Metal Weather KU-R5) Irradiation: 4 hours in air at 65°C and 50% relative humidity (irradiation intensity: 80mW / cm 2 ) Humidity: 4 hours in air at 35°C and 98% relative humidity Shower: Wet for 30 seconds before and after showering

[0138] The gloss retention of the enamel paint surface of the test board was calculated using the formula: [Gloss retention rate (%)] = [[Gloss after weather resistance test] ÷ [Gloss before weather resistance test]] × 100 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%

[0139] [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 then attaching cloth gum tape to the edge of the surface to which the release paper was attached. Next, the enamel paint obtained above was applied to the release paper surface of a test substrate so that the thickness of the coating film after drying would be 0.3 mm, and after drying in air at 23°C for one week, the formed coating film was peeled off from the test substrate and the resulting 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 specimen was held in the chuck of a tensile tester (Shimadzu Corporation, product name: Autograph AGS-100D) in air at room temperature (approximately 23°C) and a tensile test was performed under conditions of an initial gauge length of 50 mm and a tensile speed of 200 mm / min, and the formula: [Elongation rate (%)] = [(elongation at break) ÷ (50 mm)] × 100 The elongation rate of the coating film was examined based on the above, and the flexibility was evaluated based on the following evaluation criteria. (Evaluation criteria) ◎: Elongation rate is 100% or more ○: Elongation rate is 80% or more but less than 100% △: Elongation rate is 40% or more but less than 80% ×: Elongation rate is less than 40%

[0140] [Water permeability] 100 parts of enamel paint was mixed with 10 parts of deionized water, and the coating was applied to a test board (calcium silicate board, manufactured by Nippon Test Panel Co., Ltd., thickness 12 mm) at a rate of 100 g / m 2 The coating was applied with a small roller (manufactured by Trusco Nakayama Corporation) so that the coating was 15 g / cm2, and 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 kJ / cm was applied. A funnel (inner diameter: 35 mm) was placed on the coating film formed on the test plate, the contact area between the two was sealed with a silicone-based bath bond (manufactured by Konishi Co., Ltd.), and the amount of water loss after 24 hours (the difference in water surface height between the start and after 24 hours) was measured in accordance with the "Funnel Method" specified in JIS A 5422. This water permeation resistance test plate was run five times using five test plates from different lots, and the average value was taken as the amount of water loss. The water permeation resistance was evaluated based on the following evaluation criteria. (Evaluation criteria) ◎: Water loss is less than 1.0 mm ○: Water loss is 1.0 to less than 2.0 mm △: Water loss is 2.0 to less than 5.0 mm ×: Water loss is 5.0 mm or more

[0141] [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. The completed painted board was cut with a cutter knife based on JIS K 5600-7-9, 7.5 a). The rust prevention properties were evaluated under the following test conditions using a salt spray tester (manufactured by Suga Test Instruments Co., Ltd., trade name: STP-100). (Test conditions) Test chamber temperature: 35℃ Air saturator temperature: 47℃ Specimen angle: 20° Salt water concentration: 5% aqueous solution Spray volume: 1.5±0.5 ml / h at 80 cm 2 (Evaluation criteria) ◎: No rust occurs for over 200 hours in salt spray testing ○: No rust occurs for 100 hours or more but less than 200 hours in salt spray testing △: No rust occurs for 24 hours or more but less than 100 hours in salt spray testing ×: Rust appears in less than 24 hours in salt spray testing

[0142] Example 1 A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 773 parts of deionized water. 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), 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, equivalent to 6% of the total amount of all polymerizable monomer components, was added to the flask. The temperature was raised to 80°C while slowly blowing in nitrogen gas, and 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Thereafter, 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 uniformly over 120 minutes. After the dropwise addition was completed, the mixture was maintained at the same temperature for 60 minutes, and then 25% aqueous ammonia was added to adjust the pH to 7 or higher. Subsequently, a second-stage pre-emulsion consisting of 184 parts of deionized water, 100 parts of a 25% aqueous solution of ADEKA Reasoap SR-20 (manufactured by ADEKA), 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, and 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 was uniformly added dropwise over 120 minutes. After the dropwise addition was completed, the mixture 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 (water-dispersed resin composition) 1.

[0143] Example 2 Aqueous resin dispersion (water-dispersed resin composition) 2 was obtained in the same manner as in Example 1, except that the monomer components shown in Table 1 were used for polymerization.

[0144] Example 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), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA), 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 this pre-emulsion, equivalent 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 57 parts of a 3.5% aqueous solution of ammonium persulfate. Thereafter, 124 parts of methyltrimethoxysilane, 44 parts of dimethyldimethoxysilane, and 30 parts of phenyltrimethoxysilane were added to the other dropping funnel, and added dropwise uniformly over 60 minutes together with 13 parts of a 2% aqueous solution of ammonium persulfate. After the dropwise addition was completed, the mixture was maintained at the same temperature 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), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA), 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 were added dropwise uniformly over 120 minutes. After the dropwise addition was completed, the mixture was maintained at the same temperature for 60 minutes, and then 25% aqueous ammonia was added to adjust the pH to at least 7. 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), 30 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA), 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 the dropwise addition was completed, the temperature was maintained for 120 minutes to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire screen to obtain an aqueous resin dispersion (aqueous resin composition) 3.

[0145] (Examples 4 to 7, 10) Aqueous resin dispersions (water-dispersed resin compositions) 4 to 7 and 10 were obtained in the same manner as in Example 3, except that the monomer components shown in Table 1 were used for polymerization.

[0146] Example 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), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA), 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 this pre-emulsion, equivalent 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 57 parts of a 3.5% aqueous solution of ammonium persulfate. Thereafter, 124 parts of methyltrimethoxysilane, 24 parts of dimethyldimethoxysilane, and 28 parts of diphenyldimethoxysilane were added to the other dropping funnel, and added dropwise uniformly over 60 minutes together with 13 parts of a 2% aqueous solution of ammonium persulfate. After the dropwise addition was completed, the mixture was maintained at the same temperature 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), 40 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA), 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 mixture was maintained at the same temperature for 60 minutes, and then 25% aqueous ammonia was added to adjust the pH to at least 7. 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), 30 parts of a 25% aqueous solution of Adeka Reasoap SR-20 (manufactured by ADEKA), 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 organic silane 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) 8.

[0147] Example 9 Aqueous resin dispersion (water-dispersed resin composition) 9 was obtained in the same manner as in Example 8, except that the composition was changed to that shown in Table 1.

[0148] Example 11 Aqueous resin dispersion (water-dispersed resin composition) 11 was obtained in the same manner as in Example 8, except that the composition was changed to that shown in Table 1.

[0149] (Comparative Example 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 added dropwise uniformly over 90 minutes together with 25 parts of an 18% ethylene glycol monobutyl ether solution of Perbutyl D. After the dropwise addition, the mixture was maintained at the same temperature for 30 minutes, and then 45 parts of ethylene glycol monobutyl ether and 24 parts of acrylic acid were added. 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) 1 was obtained.

[0150] (Comparative Example 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), 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 this 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 Corp.) 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 (manufactured by NOF Corp.), and 40 parts of a 2.5% aqueous solution of thiourea dioxide were added dropwise uniformly over 60 minutes. After the dropwise addition was completed, the mixture was maintained at the same temperature for 40 minutes, and then 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), 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 the dropwise addition was completed, 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 filtered through a 300-mesh wire mesh to obtain a comparative aqueous resin dispersion (comparative aqueous-dispersed resin composition) 2.

[0151] (Comparative Example 3) The same operations as in Example 1 were carried out except that the monomer components shown in Table 3 were used and 1 part of OTG was used in the pre-emulsion for each of the inner and outer layers to polymerize, thereby obtaining a comparative aqueous resin dispersion (comparative aqueous-dispersed resin composition) 3.

[0152] The formulations of the polymerizable monomers and silane compounds used in the Examples and Comparative Examples are shown in Tables 1 and 2. The layer structures, Tg, and ratios of the polymerizable monomers and silane compounds in the emulsions obtained in the Examples and Comparative Examples are shown in Tables 3 and 4. The meanings of the abbreviations in Tables 1 and 2 are as follows: [Polymerizable Monomer] 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

[0153] [Silane Compound] KBM-503: γ-Methacryloyloxypropyltrimethoxysilane KBM-13: Methyltrimethoxysilane KBM-22: Dimethyldimethoxysilane KBM-103: Phenyltrimethoxysilane KBM-202SS: Diphenyldimethoxysilane KBM-3103C: Decyltrimethoxysilane ADH: Adipic acid hydrazide

[0154] [Table 1]

[0155] [Table 2]

[0156] [Table 3]

[0157] [Table 4]

[0158] <Preparation of enamel paint> 100 parts of deionized water, 15 parts of dispersant (manufactured by BYK Japan Co., Ltd., product name: DisperBYK-190), 210 parts of titanium dioxide (manufactured by Ishihara Sangyo Kaisha), 2 parts of antifoaming agent (manufactured by BYK Japan Co., Ltd., product number: BYK-024), and 2 parts of a 15% aqueous solution of thickener (manufactured by ADEKA Corporation, product name: ADEKA NOL UH-420) were mixed in a Homo Disper 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.

[0159] 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 as a film-forming aid was added, 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.

[0160] 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. The mixture was measured using a BH-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a rotation speed of 20 min -1 A thickener (ADEKA Corporation, trade name: ADEKA NOL UH-420) was added to the mixture obtained above so that the viscosity at 25°C was 4000 mPa·s, and after stirring for 30 minutes, the mixture was filtered through a 300-mesh wire mesh to obtain an enamel paint.

[0161] The enamel paint obtained above was evaluated for weather resistance, flexibility, rust prevention, and water permeability. The results are shown in Table 5.

[0162] [Table 5] < / mft>

Claims

1. A rust-preventive coating composition comprising a silicone-modified polymer emulsion, 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 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; The silane compound is represented by the following formula (1): R １ ｎ -Si-R ２ ４－ｎ (1) (In the formula, 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. The silane compound (a) is represented by the formula (I) and a silane compound (b) having a polymerizable unsaturated group, the proportion of the structure 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 the structural units derived from the polymerizable unsaturated monomer.

2. The anticorrosive coating composition according to claim 1, which is used for metal members.

3. 2. The anticorrosive coating composition according to claim 1, wherein the silicone-modified polymer emulsion contains 10 mass% or more of structures derived from the silane compound (a) represented by formula (1) relative to 100 mass% of structural units derived from the polymerizable unsaturated monomer.

4. The silane compound (a) is a silane compound (a) in which n is 2 in the formula (1). ２ ) and a silane compound (a) in which n is 3 in the formula (1). ３ 2. The anticorrosive coating composition according to claim 1, 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 anticorrosive coating composition according to claim 4, wherein the value of (a) is 0.7 to 10.

6. The silane compound (a) is represented by R ２ The anticorrosive coating composition according to claim 1, wherein the compound 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% based on 100 mass% of the silane compound (a).

8. The silane compound (b) having a polymerizable unsaturated group is represented by the following formula (2): 【Chemical 1】 (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. 2. The anticorrosive coating composition according to claim 1, wherein the silicone-modified polymer emulsion has a glass transition temperature of -20 to 50°C.

10. 2. The anticorrosive coating composition according to claim 1, wherein the silicone-modified polymer emulsion is in the form of emulsion particles having a multilayer structure.

11. 2. The anticorrosive coating composition according to claim 1, wherein the silicone-modified polymer emulsion is an emulsion particle having a structure of at least three layers, namely, 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.

12. A method for producing an anticorrosive coating composition containing a silicone-modified polymer emulsion, comprising: The production method includes a step of silicone-modifying a monomer component containing a polymerizable unsaturated monomer or a polymer thereof with a silane compound, the amount of the silane compound used in the silicone modification step is 10% by mass or more relative to 100% by mass of the polymerizable unsaturated monomer; The silane compound is represented by the following formula (1): R １ ｎ -Si-R ２ ４－ｎ (1) (In the formula, 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. The silane compound (a) is represented by the formula (I) and a silane compound (b) having a polymerizable unsaturated group, A method for producing an anticorrosive coating composition, wherein the proportion of the silane compound (b) having a polymerizable unsaturated group is 0.1 to 5 mass % relative to 100 mass % of the polymerizable unsaturated monomer.

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