Resin composition for paint

Abstract

To provide a resin composition for paint which exhibits excellent long-term resistance to contamination.SOLUTION: A resin composition for paint containing a silicone-modified polymer emulsion and a hydrophilic polymer, wherein the silicone-modified polymer emulsion has a structural unit derived from a polymerizable unsaturated monomer and a structure derived from a silane compound, and a proportion of the structure derived from the silane compound is 10 mass% or more relative 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 a resin composition for paint, and more particularly to a resin composition for paint that can be suitably used as a paint (exterior paint) for painting the exterior walls of buildings and the like. [Background technology]

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

[0003] To improve the stain resistance of paints for the exterior walls of buildings, etc., a technique has been developed in which a water-soluble polymer is blended to hydrophilize the coating surface, allowing rainwater to blend with the coating surface and wash away dirt (oil) more easily. For example, Patent Document 1 discloses an aqueous resin composition for paints that contains emulsion particles having at least two resin layers and a water-soluble polymer, wherein the outer layer of the emulsion particles is composed of a polymer obtained by polymerizing a monomer component containing 0.1 to 10% by mass of a carbonyl group-containing monomer, and the water-soluble polymer is obtained by polymerizing a monomer component containing 1 to 30% by mass of a carbonyl group-containing monomer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-188368 Summary of the Invention [Problem to be solved by the invention]

[0005] As mentioned above, various techniques have been developed to improve antifouling properties, but conventional resin compositions for paints have room for improvement in long-term stain resistance.

[0006] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a resin composition for paints which has excellent long-term stain resistance. [Means for solving the problem]

[0007] The present inventors have conducted extensive research into paint resin compositions and have found that by combining a hydrophilic polymer with a silicone-modified polymer emulsion in a specified ratio, a paint resin composition containing these has excellent long-term stain resistance. This led to the realization that the above-mentioned problems could be solved brilliantly, and has led to the present invention.

[0008] The present invention includes the following resin compositions for paints, etc. [1] A resin composition for paint comprising a silicone-modified polymer emulsion and a hydrophilic polymer, 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. [2] The resin composition for paint according to [1] above, wherein the hydrophilic polymer has a solubility in water of 50 g / 100 g or more at 25°C. [3] The hydrophilic polymer has a solubility parameter of 11 (cal / cm) of the homopolymer calculated by the following method. 3 ) 1 / 2 The resin composition for coating according to the above [1] or [2], wherein the proportion of the structural units derived from the above monomers is 70 to 100% by mass relative to 100% by mass of all structural units. <Calculation method of solubility parameter> Solubility parameter (δ) of homopolymer (cal / cm 3 ) 1 / 2is calculated by the following calculation method based on the vaporization energy (Δei) and molar volume (Δvi) of the structural units that form the polymer. δ=(△ei / △vi) 1 / 2 [4] The coating resin composition according to any one of [1] to [3] above, wherein the content of the hydrophilic polymer is 1.0 to 15 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomer in the silicone-modified polymer emulsion. [5] The coating resin composition according to any one of [1] to [4] above, wherein the silicone-modified polymer emulsion has structural units derived from monomers having a branched alkyl group in a proportion of 5 to 75 mass % relative to 100 mass % of all structural units derived from polymerizable unsaturated monomers. [6] The resin composition for coating according to any one of the above [1] to [5], wherein the silicone-modified polymer emulsion has a glass transition temperature of -20 to 50°C. [7] The resin composition for coating according to any one of the above [1] to [6], wherein the silicone-modified polymer emulsion is emulsion particles having a multilayer structure. [8] The coating resin composition according to any one of [1] to [7] above, wherein the silicone-modified polymer emulsion is an emulsion particle having at least a three-layer structure of an outer layer, an intermediate layer, and an inner layer, and the proportion of the inner layer relative to the total of the outer layer and the intermediate layer (100% by mass) is 10 to 100% by mass. [9] The coating resin composition according to any one of [1] to [8] above, wherein the silicone-modified polymer emulsion has structural units derived from an ultraviolet-absorbing monomer and / or an ultraviolet-stable monomer.

[10] The resin composition for coating according to any one of the above [1] to [9], further comprising a crosslinking agent. [Effects of the Invention]

[0009] The resin composition for coating of the present invention has the above-mentioned constitution and is excellent in long-term stain resistance, and therefore can be suitably used as a coating material for painting the exterior walls of buildings. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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".

[0011] [Resin composition for paint] The paint resin composition of the present invention is a paint resin composition comprising a silicone-modified polymer emulsion (hereinafter simply referred to as emulsion) and a hydrophilic polymer, 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. The silicone-modified polymer emulsion has a structure in which at least one structural unit derived from a polymerizable unsaturated monomer is directly or indirectly bonded to at least one structure derived from a silane compound. By having the silane compound-derived structures in the above ratio, the network structure of the silane compound-derived structures exhibits barrier properties, and it is thought that by suppressing the elution of the hydrophilic polymer over time, the silicone-modified polymer emulsion can exhibit long-term contamination resistance.

[0012] The proportion of the silicone-modified polymer emulsion in the coating resin composition of the present invention is not particularly limited, but is preferably 5 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, relative to 100% by mass of the coating resin composition.

[0013] The proportion of the hydrophilic polymer in the coating resin composition of the present invention is not particularly limited, but is preferably 1.0 to 15% by mass relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer in the silicone-modified polymer emulsion. This further improves stain resistance. It is more preferably 2.0 to 12% by mass, even more preferably 2.5 to 10% by mass, and particularly preferably 3.0 to 10% by mass. From the viewpoint of long-term stain resistance, an embodiment in which the proportion of the hydrophilic polymer is 2.0 to 8% by mass or 2.5 to 5% by mass is also one of the preferred embodiments of the present invention.

[0014] The paint resin composition of the present invention may contain other components in addition to the silicone-modified polymer emulsion and hydrophilic polymer. 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 paint resin composition. In one embodiment, when the other components include a solvent, 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 paint resin composition.

[0015] The coating resin composition of the present invention may contain a crosslinking agent, and although there are no particular limitations on the proportion thereof, it is preferably 0 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 2 to 10% by mass, relative to 100% by mass, which is the total mass of the silicone-modified polymer emulsion and the hydrophilic polymer.

[0016] The essential components and optional components contained in the resin composition for coating of the present invention will be further described below.

[0017] <<Silicone-modified polymer emulsion>> The silicone-modified polymer emulsion contained in the coating resin composition of the present invention has structural units derived from polymerizable unsaturated monomers and structures derived from silane compounds, and the proportion of structures derived from silane compounds relative to 100% by mass of structural units derived from polymerizable unsaturated monomers is 10% by mass or more. 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. The silane compound may have a silicon-containing group and may further have a reactive group other than the silicon-containing group, such as a polymerizable unsaturated group. In the present invention, the term "structure derived from a silane compound" refers to a structure identical to the structure formed by reaction of the silicon-containing group of the silane compound and / or, if the silane compound has a reactive group other than the silicon-containing group, by reaction of the reactive group. In the silicone-modified polymer emulsion, the proportion of the structure derived from the silane compound is preferably 10 to 120% by mass, more preferably 15 to 110% by mass, even more preferably 18 to 100% by mass, still more preferably 20 to 95% by mass, even more preferably 25 to 90% by mass, and particularly preferably 28 to 85% by mass, relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer. In one aspect, an embodiment in which the content of the structure derived from the silane compound is 20 to 50 mass % is also one of the preferred embodiments of the present invention. In this specification, the polymerizable unsaturated monomer does not include the silane compound (b) having a polymerizable unsaturated group, which will be described later, and the silane compound having a polymerizable unsaturated group is classified as a silane compound in this specification.

[0018] The silicone-modified polymer emulsion contains a silane 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. Preferably, the silane compound (a) has a structure derived from the silane compound (a) represented by the following formula: In the silicone-modified polymer emulsion, the proportion of the structure derived from the silane compound (a) is not particularly limited, but is preferably 8 to 90% by mass, more preferably 10 to 85% by mass, even more preferably 15 to 80% by mass, even more preferably 15 to 70% by mass, and particularly preferably 20 to 65% by mass, relative to 100% by mass of the structural units derived from the polymerizable unsaturated monomer.

[0019] 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. In the silicone-modified polymer emulsion, 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 %, and even more preferably 1 to 25 mass %, relative to 100 mass % of the structure derived from the silane compound (a). In the silicone-modified polymer emulsion, the proportion of the hydrophobic group-containing silane compound structure is preferably 0.1 to 30 mass %, more preferably 0.2 to 15 mass %, even more preferably 0.5 to 10 mass %, and particularly preferably 1 to 10 mass %, relative to 100 mass % of the structural units derived from the polymerizable unsaturated monomer.

[0020] The silicone-modified polymer emulsion preferably contains, as the silane compound, a structure derived from a silane compound (b) having a polymerizable unsaturated group. In the silicone-modified polymer emulsion, the proportion of the structure derived from the silane compound (b) having a polymerizable unsaturated group is preferably 0.1 to 5 mass% relative to 100 mass% of the structural units derived from the polymerizable unsaturated monomer. This ensures that the flexibility of the resulting coating film is within a suitable range. The proportion of the structure derived from the silane compound (b) is more preferably 0.01 to 5 mass%, even more preferably 0.05 to 5 mass%, and particularly preferably 0.1 to 4 mass%.

[0021] The silicone-modified polymer emulsion preferably contains structural units derived from a monomer having a branched alkyl group as the polymerizable unsaturated monomer, which is thought to result in improved barrier properties due to the entanglement of the branched alkyl groups, thereby further improving water blister resistance. In the silicone-modified polymer emulsion, the proportion of structural units derived from monomers having a branched alkyl group is not particularly limited, but is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, even more preferably 15 to 65% by mass, and particularly preferably 20 to 60% by mass, relative to 100% by mass of structural units derived from polymerizable unsaturated monomers.

[0022] 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 above silicone-modified polymer emulsion has a multilayer structure, it is preferable that the weight average molecular weight of the resin constituting each layer (in the case of having a crosslinked structure, the emulsion before forming the crosslinked structure) is 100,000 or more. More preferably, it is 200,000 or more, still more preferably 500,000 or more, and particularly preferably 1,000,000 or more. The above weight average molecular weight is preferably 10,000,000 or less. The above weight average molecular weight can be measured using gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120GPC, columns: TSKgel G-5000HXL and TSKgel GMHXL-L used in series].

[0023] The above silicone-modified polymer emulsion preferably has a glass transition temperature (Tg) of -20 to 50 °C. Thereby, the film-forming property is further improved, and cracks in the coating film can be sufficiently suppressed. 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 of formula (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 (% by 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 the Fox's equation represented by.

[0024] In the present invention, unless otherwise specified, the glass transition temperature of the emulsion means the glass transition temperature obtained based on formula (I).

[0025] The glass transition temperature of the entire resin layers constituting emulsion particles having a plurality of resin layers means the glass transition temperature calculated from the mass fraction of each monomer in all the monomer components used in the multistage emulsion polymerization and the glass transition temperature of the homopolymer of the corresponding monomer.

[0026] For monomers with unknown glass transition temperatures, such as special monomers and polyfunctional monomers, if the total amount of monomers with unknown glass transition temperatures in the monomer composition is 10% by mass or less, the glass transition temperature can be determined using only monomers with known glass transition temperatures. If the total amount of monomers with unknown glass transition temperatures in the monomer composition exceeds 10% by mass, the glass transition temperature of the polymer can be determined by differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermomechanical analysis (TMA), etc.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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 150% by mass, more preferably 3 to 100% by mass, even more preferably 4 to 80% by mass, and particularly preferably 5 to 70% by mass, relative to 100% by 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.

[0034] 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.

[0035] 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.

[0036] 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 0°C or lower, even more preferably -10°C or lower, still more preferably -11°C or lower, still more preferably -13°C or lower, and particularly preferably -15°C or lower.

[0037] 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.

[0038] <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.

[0039] The minimum film-forming temperature of the silicone-modified polymer emulsion refers to the boundary temperature between the film-forming area and the non-film-forming area when the emulsion is applied in a band shape to a flat plate having an appropriate temperature gradient, and is defined as "the minimum temperature at which a crack-free, uniform coating film is formed."

[0040] 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.

[0041] <Silane compounds> The silane compound constituting the silicone-modified polymer emulsion may be any compound having a silicon-containing group, but is preferably a compound having a hydrolyzable silyl group. When the silane compound is a compound having a hydrolyzable silyl group, the silane compounds react with each other and / or with reactive groups in the structural units derived from the polymerizable monomer to form a network structure, thereby further improving the barrier properties of the coating film.

[0042] The silane compound has 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. It is preferable that the silane compound (a) is represented by the following formula (I): and / or a silane compound (b) having a polymerizable unsaturated group.

[0043] The silane compound more preferably contains the silane compound (a) and the silane compound (b). 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 polymer chain, thereby forming a denser network structure.

[0044] (Silane compound (a)) The silane compound (a) is a compound represented by the above formula (1), and is —Si—R 1 It has a hydrolyzable silyl group as the aryl group. 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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 barrier properties of the coating film, it is preferable that 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.

[0051] 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.

[0052] In the above formula (1), n ​​is an integer of 1 to 4. n is preferably 2 or 3. 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] (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):

[0058] [ka]

[0059] (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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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 x’ -, -NHR x’’ -etc. Above R x’ , R x’’ is preferably an alkylene group having 1 to 20 carbon atoms. The alkylene group is not particularly limited, but examples thereof include a methylene group, a methylmethylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a neopentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] <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.

[0071] The polymerizable unsaturated monomer is not particularly limited, and examples thereof include acyclic alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, carbonyl group-containing monomers, hydroxyl group-containing (meth)acrylates, carboxyl group-containing monomers, aromatic monomers, nitrogen atom-containing monomers, oxo group-containing monomers, halogen atom-containing monomers, epoxy group-containing monomers, ultraviolet absorbing monomers, and ultraviolet stable monomers. These monomers may be used alone or in combination of two or more.

[0072] 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 total proportion of the acyclic alkyl (meth)acrylates and alicyclic structure-containing (meth)acrylates is within the above preferred range.

[0073] The silicone-modified polymer emulsion has a crosslinked structure by silane compound, but may also 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 the monomer having reactive group such as carbonyl group-containing monomer, hydroxyl group-containing (meth)acrylate, unsaturated carboxylic acid monomer, aromatic monomer, nitrogen atom-containing monomer, oxo group-containing monomer as the structural unit derived from polymerizable unsaturated monomer, it can form a crosslinked structure by reacting this reactive group with a crosslinking agent or the like. More preferred monomers having a reactive group include carbonyl group-containing monomers and nitrogen atom-containing monomers. 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 1 to 9% by mass, and even more preferably 2 to 8% by mass, relative to 100% by mass of the polymerizable unsaturated monomer.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] Examples of the acyclic alkyl(meth)acrylate include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, 2-butyl(meth)acrylate, tert-butyl(meth)acrylate, n-pentyl(meth)acrylate, isopentyl(meth)acrylate (isoamyl(meth)acrylate), 2-pentyl(meth)acrylate, tert-pentyl(meth)acrylate, 3-methyl(meth)acrylate, ... 2-butyl (meth)acrylate, 3-pentyl (meth)acrylate, neopentyl (meth)acrylate, 1-methylpentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, 2-hexyl (meth)acrylate, tert-hexyl (meth)acrylate, 3,3-dimethyl-2-butyl (meth)acrylate, 3-methyl-2-pentyl (meth)acrylate, neohexyl (meth)acrylate, 4-methyl-2-pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate acrylate, n-heptyl (meth)acrylate, isoheptyl (meth)acrylate, 2-heptyl (meth)acrylate, tert-heptyl (meth)acrylate, 2,4-dimethyl-3-pentyl (meth)acrylate, neoheptyl (meth)acrylate, 2-methyl-3-hexyl (meth)acrylate, 3-heptyl (meth)acrylate, 4-heptyl (meth)acrylate, 5-methyl-2-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate , tert-octyl (meth)acrylate, neooctyl (meth)acrylate, 2,2-dimethyl-3-hexyl (meth)acrylate, 2,5-dimethyl-3-hexyl (meth)acrylate, 3-octyl (meth)acrylate, 4-octyl (meth)acrylate, 5-methyl-2-heptyl (meth)acrylate, 5-methyl-3-heptyl (meth)acrylate, 6-methyl-2-heptyl (meth)acrylate, 6-methyl-3-heptyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate,2-nonyl(meth)acrylate, tert-nonyl(meth)acrylate, neononyl(meth)acrylate, n-decyl(meth)acrylate, isodecyl(meth)acrylate, 2-decyl(meth)acrylate, tert-decyl(meth)acrylate, neodecyl(meth)acrylate, n-undecyl(meth)acrylate, isoundecyl(meth)acrylate, 2-undecyl(meth)acrylate, tert-undecyl(meth)acrylate, neoundecyl(meth)acrylate, n-dodecyl(meth)acrylate tert-Dodecyl (meth)acrylate, Isododecyl (meth)acrylate, 2-Dodecyl (meth)acrylate, tert-Dodecyl (meth)acrylate, Neododecyl (meth)acrylate, n-Tridecyl (meth)acrylate, Isotridecyl (meth)acrylate, 2-Tridecyl (meth)acrylate, tert-Tridecyl (meth)acrylate, Neotridecyl (meth)acrylate, n-Tetradecyl (meth)acrylate, Isotetradecyl (meth)acrylate, 2-Tetradecyl (meth)acrylate, tert- Tetradecyl (meth)acrylate, neotetradecyl (meth)acrylate, n-pentadecyl (meth)acrylate, isopentadecyl (meth)acrylate, 2-pentadecyl (meth)acrylate, tert-pentadecyl (meth)acrylate, neopentadecyl (meth)acrylate, n-hexadecyl (meth)acrylate, isohexadecyl (meth)acrylate, 2-hexadecyl (meth)acrylate, tert-hexadecyl (meth)acrylate, neohexadecyl (meth)acrylate, n-hexadecyl Examples of the alkyl group include acyclic alkyl (meth)acrylates having 1 to 18 carbon atoms, such as n-octadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, 2-heptadecyl (meth)acrylate, tert-heptadecyl (meth)acrylate, neoheptadecyl (meth)acrylate, n-octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, 2-octadecyl (meth)acrylate, tert-octadecyl (meth)acrylate, and neooctadecyl (meth)acrylate. These may be used alone or in combination of two or more. These monomers may be used alone or in combination.Two or more types may be used in combination. From the viewpoint of forming a coating film that is comprehensively superior in weather resistance, low-temperature film-forming properties, extensibility, water resistance, frost resistance, and stain resistance, acyclic alkyl (meth)acrylates in which the alkyl group has 1 to 8 carbon atoms are preferred. Furthermore, from the viewpoint of improving water blister resistance and adjusting Tg, among cyclic alkyl(meth)acrylates, branched alkyl(meth)acrylates having a branched alkyl group are more preferred.

[0078] The silicone-modified polymer emulsion preferably contains structural units derived from monomers having branched alkyl groups, which are believed to further improve barrier properties by causing the branched alkyl groups to become entangled with each other, thereby further improving water blister resistance. Examples of the monomer having a branched alkyl group include the above-mentioned branched alkyl (meth)acrylates. The branched alkyl (meth)acrylate is preferably a compound represented by the following formula (3): [ka] (In the formula, R 8 represents a hydrogen atom or a methyl group. 9 and R 10 represents an alkyl group, and R 9 and R 10 The total number of carbon atoms in the alkyl group of R is 2 to 20, and 9 Number of carbon atoms ≦ R 10 The number of carbon atoms satisfies the following formula: Above R 9 and R 10 The alkyl group in the formula (1) is not particularly limited, and specific examples thereof include R 2 This is the same as described above for (an alkyl group as a specific example of a hydrocarbon group). R 9 and R 10 More specific examples of the alkyl group represented by the formula (I) include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, and an n-dodecyl group; and branched alkyl groups such as an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 2,3-dimethyl-2-butyl group, a 3-methylheptyl group, and a 2-ethylhexyl group. R 9 and R 10 The alkyl group preferably has 3 to 20 carbon atoms in total, more preferably 3 to 15 carbon atoms, and even more preferably 5 to 14 carbon atoms. R 9 The alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms. R 10 The alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms.

[0079] Specific examples of the branched alkyl (meth)acrylate include isopropyl (meth)acrylate, 2-butyl (meth)acrylate, 2-pentyl (meth)acrylate, 3-methyl-2-butyl (meth)acrylate, 3-pentyl (meth)acrylate, 2-hexyl (meth)acrylate, 3,3-dimethyl-2-butyl (meth)acrylate, 3-methyl-2-pentyl (meth)acrylate, 4-methyl-2-pentyl (meth)acrylate, 2,4-dimethyl-3-pentyl (meth)acrylate, 2-heptyl (meth)acrylate, 2-methyl-3-hexyl (meth)acrylate, 3-heptyl (meth)acrylate, 4-heptyl (meth)acrylate, 5-methyl-2-hexyl (meth)acrylate, and 2-octyl (meth)acrylate. acrylate, 2,2-dimethyl-3-hexyl (meth)acrylate, 2,5-dimethyl-3-hexyl (meth)acrylate, 3-octyl (meth)acrylate, 4-octyl (meth)acrylate, 5-methyl-2-heptyl (meth)acrylate, 5-methyl-3-heptyl (meth)acrylate, 6-methyl-2-heptyl (meth)acrylate, 6-methyl-3-heptyl (meth)acrylate, more preferably isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, even more preferably isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and most preferably 2-octyl (meth)acrylate.

[0080] 2-octyl (meth)acrylate can be synthesized from biomass materials, which is preferable from the viewpoint of reducing environmental impact. Specifically, it can be obtained by, for example, cracking ricinoleic acid derived from castor oil collected and extracted from castor bean seeds, followed by distillation of a mixture containing sebacic acid as a by-product, to obtain 2-octanol, which is then esterified with (meth)acrylic acid. The (meth)acrylic acid used in the present invention may be bio-derived or petroleum-derived.

[0081] 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 35 to 60% by mass, relative to 100% by mass of the polymerizable unsaturated monomer.

[0082] The proportion of the branched alkyl (meth)acrylate is not particularly limited, but is preferably 5 to 75% by mass relative to 100% by mass of the polymerizable unsaturated monomer, more preferably 10 to 70% by mass, even more preferably 20 to 65% by mass, still more preferably 25 to 60% by mass, and particularly preferably 30 to 55% by mass.

[0083] The polymerizable unsaturated monomer may contain a linear alkyl (meth)acrylate among acyclic alkyl (meth)acrylates, and the proportion thereof is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, relative to 100% by mass of the polymerizable unsaturated monomer.

[0084] 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. Among these, cyclohexyl (meth)acrylate is preferred. Since the alicyclic structure-containing (meth)acrylate is highly hydrophobic, its use can sufficiently reduce the water absorption rate of the coating film and more sufficiently suppress the elution of the hydrophilic polymer.

[0085] The proportion of the alicyclic structure-containing (meth)acrylate is not particularly limited, but is preferably 20 to 80% by mass relative to 100% by mass of the polymerizable unsaturated monomer. A proportion of 20% by mass or more further improves the weather resistance of the coating film. Furthermore, a proportion of 80% by mass or less further improves the low-temperature film-forming properties and extensibility of the coating film. The proportion of the alicyclic structure-containing (meth)acrylate is more preferably 25 to 75% by mass, even more preferably 30 to 70% by mass, even more preferably 35 to 65% by mass, and particularly preferably 40 to 60% by mass.

[0086] When the silicone-modified polymer emulsion has a two-layer structure, the proportion of the alicyclic structure-containing (meth)acrylate in the outer layer is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and particularly preferably 20 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.

[0087] 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.

[0088] Examples of the carbonyl group-containing monomer include (meth)acryloyl, humylstyrene, vinyl ethyl ketone, (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, diacetone (meth)acrylamide, 2-hydroxypropyl (meth)acrylate acetylacetate, butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate, 2-(acetoacetoxy)ethyl methacrylate, etc. The carbonyl group in the carbonyl group-containing monomer can react with a crosslinking agent such as a hydrazine-based crosslinking agent, which will be described later. Among these, diacetone (meth)acrylate, diacetone (meth)acrylamide, etc. are preferred, and diacetone (meth)acrylamide is more preferred.

[0089] 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. Of these, 2-hydroxyethyl (meth)acrylate is preferred. The proportion 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.

[0090] The unsaturated carboxylic acid monomer is not particularly limited, but examples thereof include unsaturated monocarboxylic acid monomers such as (meth)acrylic acid, crotonic acid, etc., and salts thereof; and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., and salts and acid anhydrides thereof. Of these, (meth)acrylic acid is preferred. These monomers may be used alone or in combination of two or more. The ratio of the carboxyl group-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0091] By using a monomer having a polar group, such as a hydroxyl group-containing (meth)acrylate or an unsaturated carboxylic acid monomer, as the polymerizable unsaturated monomer, charge repulsion occurs in the emulsion, further improving the mechanical stability, thereby more sufficiently suppressing the aggregation of the emulsion.

[0092] 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. A proportion of 20% by mass or less further improves the weather resistance of the coating film. The proportion of the aromatic monomer is more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 1% by mass or less, and most preferably 0% by mass.

[0093] The nitrogen atom-containing monomer is not particularly limited, but examples thereof include (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, diacetone(meth)acrylamide, and other (meth)acrylamide compounds; nitrogen atom-containing (meth)acrylate compounds; dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate; N-vinylpyrrolidone; and (meth)acrylonitrile. These nitrogen atom-containing monomers may be used alone or in combination of two or more. The ratio of the nitrogen atom-containing monomer in the polymerizable unsaturated monomer is preferably adjusted appropriately depending on the application of the coating material of the present invention.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] <<Hydrophilic polymer>> The hydrophilic polymer contained in the resin composition for coating of the present invention may be any polymer as long as it exhibits hydrophilicity, but it is preferable that the solubility in water at 25°C is 50 g / 100 g or more. The solubility in water at 25°C is more preferably 55 g / 100 g or more, and even more preferably 60 g / 100 g or more.

[0102] The hydrophilic polymer has a homopolymer solubility parameter of 11 (cal / cm) calculated by the following method. 3 ) 1 / 2 The proportion of structural units derived from the above monomers (hereinafter also referred to as hydrophilic monomers) is preferably 70 to 100% by mass relative to 100% by mass of all structural units, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass. <Calculation method of solubility parameter> Solubility parameter (δ) of homopolymer (cal / cm 3 ) 1 / 2 is calculated from the evaporation energy (Δei) and molar volume (Δvi) of the structural units forming the polymer using the following formula based on Fedors' estimation method (RF Fedors, Polym. Eng. Sci., 14(2), 147-154 (1974)). δ=(△ei / △vi) 1 / 2

[0103] The solubility parameter of the homopolymer calculated by the above method is more preferably 11.5 or more, and even more preferably 12 or more.

[0104] The hydrophilic polymer preferably has structural units derived from a carbonyl group-containing monomer, which allows a crosslinked structure to be formed between the hydrophilic polymer and the silicone-modified polymer emulsion using a crosslinking agent such as a hydrazine-based crosslinking agent described below.

[0105] The hydrophilic polymer may have structural units derived from monomers other than the hydrophilic monomers. The other monomer is not particularly limited, but may be, for example, a polymerizable monomer in the silicone-modified polymer emulsion described above that does not fall under the category of a hydrophilic monomer. A preferred example of the other monomer is an acyclic alkyl (meth)acrylate.

[0106] The proportion of structural units derived from other monomers in the hydrophilic polymer is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass, relative to 100% by mass of all structural units.

[0107] The hydrophilic polymer preferably has structural units derived from an N-vinyl lactam monomer, which will be described later, and the proportion thereof is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, relative to 100% by mass of all structural units.

[0108] The hydrophilic polymer may have structural units derived from the carbonyl group-containing monomer described below, and the proportion thereof is not particularly limited, but is preferably 0 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass, relative to 100% by mass of all structural units.

[0109] The weight average molecular weight of the hydrophilic polymer is not particularly limited, but is preferably 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, even more preferably 5,000 to 500,000, still more preferably 7,000 to 300,000, and particularly preferably 10,000 to 100,000. The weight average molecular weight can be measured by gel permeation chromatography.

[0110] The hydrophilic polymer may be any polymer obtained by polymerizing a monomer component containing the hydrophilic monomer, and may be any of a homopolymer, a random copolymer, a block copolymer, and a graft copolymer. Of these, a random copolymer is preferred.

[0111] The hydrophilic monomer is not particularly limited, but examples thereof include N-vinyl lactam monomers, unsaturated carboxylic acid monomers, carbonyl group-containing monomers, hydroxyl group-containing monomers, unsaturated polyalkylene glycol monomers, alkylene oxides, etc. Among these, N-vinyl lactam monomers are preferred.

[0112] The N-vinyl lactam monomer is not particularly limited as long as it is a monomer having a cyclic N-vinyl lactam structure, and specific examples thereof include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, 1-(2-propenyl)-2-pyrrolidone, etc. Among these, N-vinylpyrrolidone is preferred.

[0113] Specific and preferred examples of the unsaturated carboxylic acid monomer, the carbonyl group-containing monomer, and the hydroxyl group-containing monomer are as described above.

[0114] The unsaturated polyalkylene glycol monomer may be any monomer having a (poly)oxyalkylene group, and examples thereof include polyalkylene glycol (meth)acrylates such as polyethylene glycol (meth)acrylate; and compounds in which alkylene oxide is added to unsaturated alcohols having 2 to 8 carbon atoms, such as vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, 2-methyl-2-buten-1-ol, and 3-allyloxy-1,2-propanediol. The average number of moles of alkylene oxide added in the unsaturated polyalkylene glycol monomer is preferably 1-10.

[0115] Examples of the alkylene oxide include alkylene oxides having 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. More preferred are alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide, still more preferred are ethylene oxide and propylene oxide, and particularly preferred is ethylene oxide. In a preferred embodiment of the present invention, the hydrophilic polymer is a polyalkylene glycol obtained by addition polymerization of the alkylene oxide.

[0116] The number average molecular weight of the polyalkylene glycol is not particularly limited, but is preferably 1,000 or more and less than 1,000,000, and more preferably 10,000 to 500,000. The number average molecular weight can be measured by gel permeation chromatography.

[0117] <<Other ingredients>> If necessary, other components than the silicone-modified polymer emulsion and hydrophilic polymer may be added to the resin composition for coating of the present invention, as long as the effects of the present invention are not impaired. The other components are not particularly limited, and examples thereof include various additives such as crosslinking agents, curing agents, film-forming aids, fillers, thickeners, antifoaming agents, pigments, dispersants, pH buffers, chelating agents, dyes, UV absorbers, UV stabilizers, leveling agents, wetting agents, plasticizers, stabilizers, antioxidants, delustering agents, antifreezing agents, colloidal silica, other emulsions, solvents, and the like. The embodiment in which the resin composition for paint contains a crosslinking agent is one of the preferred embodiments of the present invention.

[0118] Examples of the crosslinking agent and curing agent include hydrazine-based crosslinking agents, melamine-based crosslinking agents, oxazoline-based crosslinking agents, acrylamide-based crosslinking agents, polyamide-based crosslinking agents, epoxy-based crosslinking agents, isocyanate-based crosslinking agents, aziridine-based crosslinking agents, titanate-based crosslinking agents, urea-based crosslinking agents, alkyl alcohol-based urea-based crosslinking agents, carbodiimide compounds, zirconium compounds, zinc compounds, titanium compounds, aluminum compounds, and other polyvalent metal compounds. These may be used alone or in combination of two or more. A hydrazine-based crosslinking agent is preferred.

[0119] Examples of the thickener include urethane association types, polycarboxylates, polyether types, cellulose ethers, polyacrylic types, polyacrylamides, etc. These may be used alone or in combination of two or more.

[0120] Examples of the film-forming aid include glycol ethers, esters, etc. These may be used alone or in combination of two or more.

[0121] 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.

[0122] Examples of the thickener include polycarboxylates, urethane association types, polyether types, cellulose ethers, polyacrylic types, and polyacrylamides. Examples of the antifoaming agent include silicon-based antifoaming agents. Examples of the dispersant include dispersants having a polypropylene glycol group or a polyethylene glycol group.

[0123] Examples of the pigment include inorganic pigments (e.g., inorganic color pigments such as titanium oxide, iron oxide, aluminum, and pearl pigments), organic pigments (e.g., organic color pigments such as quinacridone, anthraquinone, perylene, diketopyrrolopyrrole, benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, threne, dioxazine, and carbon black), and extender pigments (e.g., calcium carbonate, barium sulfate, kaolin, mica, and talc).

[0124] Examples of other emulsions include natural rubber latex, acrylic resin latex, vinyl acetate resin latex, urethane resin latex, epoxy resin latex, etc. These can be used alone or in combination of two or more.

[0125] 〔paint〕 The present invention also relates to a paint containing the resin composition for paint of the present invention. The paint resin composition of the present invention can be used as a clear paint as is, or can be used as an enamel paint by adding an appropriate amount of a colorant such as a dye or pigment to the paint resin composition of the present invention. The 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.

[0126] The coating material of the present invention may further contain the above-mentioned additives other than the colorant. The amount of additive contained in the paint varies depending on the type of additive, and therefore it is preferable to adjust it appropriately depending on the type of additive. The resin composition for paint or paint of the present invention can be used by applying it to substrates made of various materials (for example, metal, glass, porcelain, concrete, siding board, resin, etc.). It may also be used for surface finishing of the above-mentioned substrates. The resin composition for paint or paint of the present invention is preferably used for architectural paint, and because it has excellent long-term stain resistance, it can be suitably used as a top coat or top coat material (for example, a top coat or top coat material for building materials such as interior materials and exterior materials).

[0127] Examples of building materials include inorganic building materials such as flexible boards, calcium silicate boards, gypsum slag perlite boards, wood-chip cement boards, precast concrete boards, ALC boards, and gypsum boards; ceramic building materials such as roofing tiles and exterior wall materials; and metal building materials such as Galvalume Steel Sheets (registered trademark). Ceramic building materials can be obtained, for example, by adding an inorganic filler, a fibrous material, and the like to a hydraulic adhesive material that serves as the raw material for the inorganic hardened body, molding the resulting mixture, and curing and hardening the resulting molded body.

[0128] The resin composition for coating or the coating 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.

[0129] The resin composition for coating or the coating 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. The amount of the resin composition for coating or coating of the present invention to be applied cannot be determined in general because it varies depending on the type of coating material and substrate, but is preferably 10 to 300 g / m 2 It is preferable that the degree of

[0130] [Method for producing a resin composition for paint] There are no particular restrictions on the method for producing the coating resin composition of the present invention, and it can be produced by mixing a silicone-modified polymer emulsion with a hydrophilic polymer. There are no particular restrictions on the mixing ratio of the silicone-modified polymer emulsion and the hydrophilic polymer, and it can be determined based on the preferred ratio of the silicone-modified polymer emulsion and the hydrophilic polymer in the above-mentioned resin composition for coating.

[0131] <Method for producing silicone-modified polymer emulsion> 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). For example, the polymerizable unsaturated monomer and the silane compound may be reacted simultaneously, or the silane compound may be reacted with a polymer of a polymerizable unsaturated monomer. Furthermore, when the silane compound contains the above-mentioned silane compound (a) and silane compound (b), for example, the polymerizable unsaturated monomer, the silane compound (a), and the silane compound (b) may be reacted simultaneously, or the silane compound (a) may be reacted with a polymer obtained by polymerizing the polymerizable unsaturated monomer and the silane compound (b). Specific examples and preferred forms of the polymerizable unsaturated monomers and silane compounds in the monomer components used in the above production method are the same as those described for the silicone-modified polymer emulsion. The amounts of these used can be determined based on the above-mentioned preferred proportions of the structural units derived from each monomer and the structure derived from the silane compound in the silicone-modified polymer emulsion.

[0132] In the silicone modification step, when silane compounds (a) and (b) are used, the reaction step of silane compound (a) may be carried out after the polymerization step of polymerizing the monomer component containing polymerizable unsaturated monomer and silane compound (b), or the polymerization step and the reaction step of silane compound (a) may be carried out simultaneously.However, preferably, the polymerization reaction of the monomer component containing polymerizable unsaturated monomer and silane compound (b) is started, and then the reaction of silane compound (a) is started, and the reaction of silane compound (a) is carried out while the polymerization step is being carried out.This allows the polymerization reaction and the reaction of silane compound (a) and 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.

[0133] 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 or 8 to 11. 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.

[0134] When the silane compound (b) is used in the silicone modification step, the polymerization of the monomer component is preferably carried out by polymerizing a monomer component containing a polymerizable unsaturated monomer and the silane compound (b). The polymerization reaction is preferably carried out 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] The amphoteric emulsifier is not particularly limited, but examples thereof include betaine ester emulsifiers, and one or more of these can be used.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] In the polymerization step, a chain transfer agent may be used. This allows the molecular weight of the emulsion to be adjusted. In addition, in the present invention, 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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 or 8 to 11. This allows the condensation reaction of the silane compound to proceed sufficiently. The pH is more preferably 1.5 to 4.5 or 8 to 10. 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.

[0153] When the emulsion particles have a multilayer structure, the polymerization reaction and the reaction with the silane compound can be repeated two or more times in the silicone modification step to prepare emulsion particles having at least two resin layers.

[0154] In the above production method, a step of crosslinking the emulsion particles may be carried out after the silicone modification step, after the polymerization reaction of the monomer components, or after mixing the silicone modified polymer emulsion with the hydrophilic polymer. The crosslinking step is preferably carried out after the mixing step. This allows the resulting silicone-modified polymer emulsion to have a crosslinked structure derived from the crosslinking agent in addition to the crosslinked structure derived from the silane compound, making it possible to more sufficiently suppress elution of the hydrophilic polymer from the coating film. The crosslinking agent used in the crosslinking step is not particularly limited, and the above-mentioned crosslinking agents can be used, among which 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.

[0155] Examples of the hydrazine crosslinking agent include adipic acid dihydrazide and polymers having a hydrazide group, with adipic acid dihydrazide being preferred.

[0156] <Method of manufacturing hydrophilic polymer> The method for producing the hydrophilic polymer is not particularly limited, and the polymer can be produced by polymerizing the monomer components, specific and preferred examples of which are as described above. The content of each monomer component relative to 100% by mass of all the monomer components can be determined based on the proportion of each structural unit relative to 100% by mass of all the structural units described above.

[0157] The polymerization method of the above-mentioned monomer components is not particularly limited, and the polymerizable composition can be prepared by a polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a precipitation polymerization method, etc. Among these polymerization methods, a solution polymerization method using water as a solvent is preferred, and a solution polymerization method using water as a solvent is more preferred. When the monomer is an alkylene oxide, the polyalkylene glycol can be produced by addition polymerization of the alkylene oxide in the presence of a catalyst by a commonly used method. Commercially available polyalkylene glycols can also be used.

[0158] When the polymerization is carried out by the solution polymerization method, a solvent is used. Examples of the solvent include water, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane, ester compounds such as ethyl acetate, ketone compounds such as acetone and methyl ethyl ketone, and cyclic ether compounds such as tetrahydrofuran and dioxane. Among these, aqueous solution polymerization is preferred.

[0159] In the production of the hydrophilic polymer, a chain transfer agent can be used to adjust the molecular weight of the resulting polymer. As the chain transfer agent, those described in the production of the silicone-modified polymer emulsion can be used.

[0160] In the production of the hydrophilic polymer, it is preferable to use a polymerization initiator. As the polymerization initiator, those described in the production of the silicone-modified polymer emulsion can be used. Among them, azo compounds are preferred, and 2,2-azobis(2-methylpropionamidine) is more preferred. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.01 to 10% by mass relative to 100% by mass of the monomer component.

[0161] The polymerization temperature for the polymerization reaction of the above monomer components is not particularly limited, but is preferably 0 to 100°C, and more preferably 50 to 80°C. The pressure during the polymerization reaction may be normal pressure, reduced pressure, or increased pressure. The atmosphere during the polymerization reaction is preferably an inert gas such as nitrogen gas, argon gas, or carbon dioxide gas. [Example]

[0162] 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."

[0163] <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

[0164] <mft> The minimum film-forming temperature of a resin emulsion means the boundary temperature between the film-forming area and the non-film-forming area when the resin emulsion is applied in a strip shape to a flat plate having an appropriate temperature gradient, and is defined as "the minimum temperature at which a crack-free, uniform coating film is formed."

[0165] The minimum film-forming temperature of a resin emulsion can be measured, for example, in accordance with JIS K6828-2 (2003). More specifically, using an MFT tester (manufactured by Tester Sangyo Co., Ltd., product number: TP-801 LT), a coating film of the resin emulsion having a 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.

[0166] <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.

[0167] 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.

[0168] 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.

[0169] [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.

[0170] (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

[0171] 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%

[0172] [water 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 24 hours to prepare a test board. Next, enamel paint was applied to the sealer side of the test panel using a 6-mil applicator and allowed to dry in the air at room temperature (approximately 23°C) for two hours. After that, another enamel paint was applied using a 6-mil applicator so that it overlapped the paint film, and allowed to dry at room temperature for 24 hours, forming a two-layer paint film. The test panel was then immersed in deionized water adjusted to room temperature for 24 hours. After that, a 5mm x 5mm cut was made in the paint film with a utility knife, and the behavior of the cut area when peeled off with the utility knife was visually observed. Water resistance was evaluated based on the following evaluation criteria. (Evaluation criteria) ◎: Both layers of the coating have peeled off ○: Most of the coating has peeled off. △: Only one layer of the coating peels off ×: The coating film decomposes

[0173] [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 elongation 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%

[0174] [Stain resistance] Glass beads with a diameter of 1 mm were added to deionized water at a ratio of 5 parts per 95 parts of deionized water, and 5 parts of carbon black (manufactured by Mitsubishi Chemical Corporation) was added to the deionized water while stirring the deionized water with a Homo Disper at a rotation speed of 500 min-1. The deionized water was then further stirred at a rotation speed of 2500 min-1 for 30 minutes to obtain a dispersion. The dispersion obtained above was filtered through a 300-mesh wire screen to obtain a carbon black dispersion.

[0175] Next, the enamel paint obtained above was applied to a white acrylic plate (manufactured by Nippon Test Panel Co., Ltd.) using a 6 mil applicator and allowed to dry in air at room temperature (approximately 23°C) for 24 hours. After drying, the initial L value (L0) of the enamel paint-coated surface of the test plate was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: Spectroscopic Color Difference Meter SE-2000).

[0176] The carbon black dispersion obtained above was then applied to the enamel-coated surface of the test plate using a 20 mil applicator and allowed to dry for 24 hours at room temperature (approximately 23°C). After drying, the carbon black adhering to the enamel-coated surface of the test plate was washed away using running water and a brush (with 40 mm bristles), and the L value (L1) of the carbon black dispersion-coated surface was measured using the color difference meter.

[0177] Next, the change in L value (△L) is calculated using the formula: △L=L1-L0 The stain resistance was evaluated based on the following evaluation criteria.

[0178] (Evaluation criteria) ◎: △L is less than 20 ○: △L is 20 or more and less than 40 △:△L is 40 or more and less than 60 ×: △L is 60 or more

[0179] [Stain resistance after 6 months] Enamel paint was applied twice to an aluminum plate (manufactured by Nippon Test Panel Co., Ltd., length: 400 mm, width: 100 mm, thickness: 1 mm) using a 6-mil applicator and allowed to dry at 23°C for one week. The test plate was then bent lengthwise in half (200 mm) to create a 30-degree incline facing south. The initial L value (L0) of the inclined portion of the test plate was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number: ZE-6000). An outdoor exposure test was conducted in accordance with JIS Z2381 (General Rules for Atmospheric Exposure Testing Methods) under the following conditions. After six months, the test plate was removed and the L value (L1) of the inclined portion of the test plate was measured using the same color difference meter. -Test conditions- (30 degrees south facing, direct exposure (exposure location: Suita City, Osaka Prefecture / on the premises of Nippon Shokubai Co., Ltd.)).

[0180] Next, calculate the change in L value using the formula: ΔL=(L1)-(L0) The stain resistance for 6 months was evaluated based on the following evaluation criteria. (Evaluation criteria) ◎: ΔL is less than 5 ○: ΔL is 5 or more and less than 10 △: ΔL is 10 or more and less than 15 ×: ΔL is 15 or more

[0181] (Manufacturing Example A1) A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 938 parts of deionized water. A pre-emulsion for dropping, consisting of 238 parts of deionized water, 100 parts of a 25% aqueous solution of ADEKA Reasoap SR-20 (manufactured by ADEKA), 380 parts of cyclohexyl methacrylate, 50 parts of 2-octyl acrylate, 35 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 5 parts of methacrylic acid, 10 parts of diacetone acrylamide, and 5 parts of γ-methacryloyloxypropyltrimethoxysilane, was prepared in the dropping funnel. 54 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, 30 parts of methyltrimethoxysilane, 75 parts of dimethyldimethoxysilane, and 10 parts of decyltrimethoxysilane were added to the other dropping funnel, and the pre-emulsion and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise 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 8. Subsequently, a second-stage pre-emulsion consisting of 158 parts of deionized water, 100 parts of a 25% aqueous solution of ADEKA Reasoap SR-20 (manufactured by ADEKA), 90 parts of 2-ethylhexyl acrylate, 20 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 50 parts of butyl acrylate, 205 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 15 parts of diacetone acrylamide, 10 parts of 1,2,2,6,6-pentamethylpiperidine-4-methacrylate, and 10 parts of γ-methacryloyloxypropyltrimethoxysilane, 120 parts of methyltrimethoxysilane, 130 parts of dimethyldimethoxysilane, 10 parts of phenyltrimethoxysilane, and 25 parts of a 2% aqueous solution of ammonium persulfate was uniformly added dropwise over 120 minutes. After the dropwise addition was completed, the temperature was maintained for 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 Resin Emulsion A1.

[0182] (Manufacturing example A2) A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 713 parts of deionized water. A pre-emulsion for dropping, consisting of 238 parts of deionized water, 50 parts of a 25% aqueous solution of ADEKA Reasoap SR-20 (manufactured by ADEKA), 10 parts of methyl methacrylate, 130 parts of cyclohexyl methacrylate, 5 parts of 2-octyl acrylate, 5 parts of isoamyl acrylate, and 2 parts of γ-methacryloyloxypropyltrimethoxysilane, was prepared in the dropping funnel. 54 parts of 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. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Thereafter, 120 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane, and 30 parts of diphenyldimethoxysilane were added to the other dropping funnel, and the mixture was uniformly added dropwise over 120 minutes together with the above pre-emulsion and 25 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 203 parts of deionized water, 110 parts of a 25% aqueous solution of ADEKA Reasoap SR-20 (manufactured by ADEKA), 150 parts of 2-ethylhexyl acrylate, 190 parts of cyclohexyl methacrylate, 50 parts of 2-octyl acrylate, 125 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 5 parts of methacrylic acid, and 10 parts of diacetone acrylamide, and 25 parts of a 2% aqueous solution of ammonium persulfate were added dropwise uniformly over 120 minutes. After the dropwise addition was completed, the mixture was maintained at the same temperature for 60 minutes, and then 25% aqueous ammonia was added to adjust the pH to 8 or higher. Subsequently, a third-stage pre-emulsion consisting of 120 parts of deionized water, 40 parts of a 25% aqueous solution of ADEKA Reasoap SR-20 (manufactured by ADEKA), 180 parts of cyclohexyl methacrylate, 25 parts of isoamyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 15 parts of diacetone acrylamide, 10 parts of 1,2,2,6,6-pentamethylpiperidine-4-(meth)acrylate, 5 parts of γ-methacryloyloxypropyltrimethoxysilane, and 60 parts of 2-octyl acrylate, 80 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane, 20 parts of diphenyldimethoxysilane, and 25 parts of a 2% aqueous solution of ammonium persulfate 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 mesh to obtain a resin emulsion A2.

[0183] (Manufacturing examples A3 to A7) Resin emulsions A3 to A7 were obtained in the same manner as in Production Example A1, except that the monomer components shown in Tables 1-1 and 1-2 were used for polymerization.

[0184] (Manufacturing example A8) A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 788 parts of deionized water. The dropping funnel was charged with 500 parts of deionized water, 160 parts of a 25% aqueous solution of ADEKA Reasoap SR-20 (manufactured by ADEKA), 180 parts of 2-ethylhexyl acrylate, 15 parts of methyl methacrylate, 445 parts of cyclohexyl methacrylate, 75 parts of 2-octyl acrylate, 110 parts of isoamyl acrylate, 75 parts of butyl acrylate, 20 parts of 2-hydroxyethyl acrylate, 20 parts of acrylic acid, 10 parts of methacrylic acid, and diacetone. A pre-emulsion for dropping was prepared, consisting of 30 parts of tetramethyl acrylamide, 20 parts of 1,2,2,6,6-pentamethylpiperidine-4-(meth)acrylate, and 10 parts of γ-methacryloyloxypropyltrimethoxysilane. 95 parts of this, equivalent to 6% of the total amount of all polymerizable monomer components, was added to a flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 57 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Subsequently, 70 parts of methyltrimethoxysilane, 100 parts of dimethyldimethoxysilane, 10 parts of phenyltrimethoxysilane, and 10 parts of decyltrimethoxysilane were added to the other dropping funnel, and the pre-emulsion and 50 parts of a 2% aqueous solution of ammonium persulfate were added dropwise over 240 minutes. After 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 mesh to obtain Resin Emulsion A8.

[0185] (Manufacturing example B1) A reaction vessel equipped with a condenser, nitrogen gas inlet, and thermometer was charged with 71 parts of deionized water, 200 parts of N-vinylpyrrolidone, 10 parts of methyl methacrylate, 10 parts of acrylic acid, and 30 parts of diacetone acrylamide. Nitrogen gas was then introduced into the reaction vessel to create a nitrogen gas atmosphere. Polymerization was initiated by adding 2 parts of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries) to the reaction vessel while stirring at room temperature. After the internal temperature rose due to the heat of reaction, stirring was continued at 80°C for 2 hours. Next, 1 part of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel, and the mixture was further stirred at 80° C. for 1 hour to obtain a polymer solution B1 containing a water-soluble polymer.

[0186] (Manufacturing examples B2~B3, B5~B8) Hydrophilic polymers B2 to B3 and B5 to B8 were obtained in the same manner as in Production Example B1, except that the monomer components shown in Tables 1-1 and 1-2 were used for polymerization.

[0187] Example 1 The resin emulsion obtained in Production Example A1 and the hydrophilic polymer obtained in Production Example B1 were mixed so that the mass ratio of the non-volatile content of the resin emulsion to the non-volatile content of the water-soluble polymer (resin emulsion / hydrophilic polymer) was 97 / 3, thereby preparing aqueous resin composition 1.

[0188] Example 2 The resin emulsion obtained in Production Example A2 and the hydrophilic polymer obtained in Production Example B2 were mixed so that the mass ratio of the non-volatile content of the resin emulsion to the non-volatile content of the water-soluble polymer (resin emulsion / hydrophilic polymer) was 97 / 3. 100 parts of the aqueous resin composition obtained above and 10 parts of a 5% aqueous solution of adipic acid dihydrazide were added to a flask to prepare aqueous resin composition 2.

[0189] (Examples 3, 5 to 8) Aqueous resin dispersions (water-dispersed resin compositions) 3 and 5 to 8 were obtained in the same manner as in Example 1, except that the compositions were changed to those shown in Tables 1-1 and 1-2.

[0190] Example 4 The resin emulsion obtained in Production Example A4 and PEG-20000 (manufactured by ADEKA) were mixed so that the mass ratio of the non-volatile content of the resin emulsion to the non-volatile content of the water-soluble polymer (resin emulsion / hydrophilic polymer) was 97 / 3. 100 parts of the aqueous resin composition obtained above and 10 parts of a 5% aqueous solution of adipic acid dihydrazide were added to a flask to prepare aqueous resin composition 2.

[0191] (Comparative manufacturing example C1) Resin emulsion C1 was obtained in the same manner as in Production Example A1, except that the monomer components shown in Table 2 were used for polymerization.

[0192] (Comparative production examples C3 and C4) Resin emulsions C3 and C4 were obtained in the same manner as in Production Example A2, except that the monomer components shown in Table 2 were used for polymerization.

[0193] (Comparative Manufacturing Examples D3 and D4) Comparative hydrophilic polymers D3 and D4 were obtained in the same manner as in Production Example B1, except that the monomer components shown in Table 2 were used for polymerization.

[0194] (Comparative Example 1) A comparative aqueous resin composition 1 was obtained by adding 100 parts of the resin emulsion obtained in Comparative Production Example C1 and 10 parts of a 5% aqueous solution of adipic acid dihydrazide to a flask.

[0195] (Comparative Examples 2 and 3) Comparative aqueous resin dispersions (comparative water-dispersed resin compositions) 2 and 3 were obtained in the same manner as in Example 1, except that the compositions were changed to those shown in Table 2. The formulations of the polymerizable monomers and silane compounds used in the Examples and Comparative Examples are shown in Tables 1-1, 1-2, and 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 1-1, 1-2, and 2 are as follows:

[0196] [Polymerizable Monomer] CHMA: Cyclohexyl methacrylate IBOA: Isobornyl acrylate MMA: Methyl methacrylate 2EHA: 2-Ethylhexyl acrylate BA: n-butyl acrylate 2OA: 2-octyl acrylate IAA: Isoamyl acrylate HEMA: 2-hydroxymethyl methacrylate AA: Acrylic acid ·MAA: methacrylic acid DAAM: Diacetone acrylamide HALS1: 1,2,2,6,6-pentamethylpiperidine-4-methacrylate NVP: N-vinylpyrrolidone

[0197] [Silane Compound] KBM-503: γ-Methacryloyloxypropyltrimethoxysilane KBM-13: Methyltrimethoxysilane KBM-22: Dimethyldimethoxysilane KBM-103: Phenyltrimethoxysilane KBM-202SS: Diphenyldimethoxysilane KBM-3103C: Decyltrimethoxysilane

[0198] [Table 1-1]

[0199] [Table 1-2]

[0200] [Table 2]

[0201] [Table 3]

[0202] [Table 4]

[0203] The enamel paints obtained using the aqueous resin compositions obtained in the above Examples and Comparative Examples were evaluated for weather resistance, water resistance, flexibility, stain resistance, and stain resistance after 6 months. The results are shown in Table 5.

[0204] [Table 5] < / mft> < / mft>

Claims

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

2. 2. The resin composition for paint according to claim 1, wherein the hydrophilic polymer has a solubility in water of 50 g / 100 g or more at 25°C.

3. The hydrophilic polymer has a solubility parameter of 11 (cal / cm) of the homopolymer calculated by the following method. ３ ) １／２ 3. The resin composition for paint according to claim 1, wherein the proportion of the structural units derived from the above monomers is 70 to 100% by mass relative to 100% by mass of all structural units. <Method for calculating solubility parameter> Solubility parameter of homopolymer (δ) (cal / cm ３ ) １／２ is calculated by the following calculation method based on the vaporization energy (Δei) and molar volume (Δvi) of the structural units forming the polymer. δ=(△e / △ｽ) １／２

4. 3. The coating resin composition according to claim 1, wherein the content of the hydrophilic polymer is 1.0 to 15% by mass relative to 100% by mass of structural units derived from polymerizable unsaturated monomers in the silicone-modified polymer emulsion.

5. 3. The coating resin composition according to claim 1, wherein the silicone-modified polymer emulsion contains structural units derived from monomers having a branched alkyl group in a proportion of 5 to 75% by mass, relative to 100% by mass of all structural units derived from polymerizable unsaturated monomers.

6. 3. The coating resin composition according to claim 1, wherein the silicone-modified polymer emulsion has a glass transition temperature of -20 to 50°C.

7. 3. The paint resin composition according to claim 1, wherein the silicone-modified polymer emulsion is in the form of emulsion particles having a multilayer structure.

8. 3. The paint resin composition according to claim 1, wherein the silicone-modified polymer emulsion is an emulsion particle having at least a three-layer structure of an outer layer, an intermediate layer, and an inner layer, and the proportion of the inner layer relative to the total of the outer layer and the intermediate layer (100% by mass) is 10 to 100% by mass.

9. 3. The coating resin composition according to claim 1, wherein the silicone-modified polymer emulsion has structural units derived from an ultraviolet-absorbing monomer and / or an ultraviolet-stable monomer.

10. The resin composition for paint according to claim 1 or 2, further comprising a crosslinking agent.

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