Water-based coatings

Abstract

The objective is to provide a water-based paint with excellent storage stability. [Solution] A multi-component water-based paint comprising (A) liquid A containing an emulsion of alkoxysilyl group-containing synthetic resin, and (B) liquid B containing a substance that promotes hydrolysis and condensation of alkoxysilyl group, wherein the alkoxysilyl group-containing synthetic resin is a water-based paint comprising a polyorganosiloxane having a specific configuration and a graft portion having a specific configuration.

Description

[Technical Field]

[0001] This invention relates to water-based paints. [Background technology]

[0002] Various types of paints (for example, antifouling paints) have been developed. Currently, solvent-based paints are the mainstream, but in recent years, there has been a rapid shift towards water-based paints from the perspective of environmental protection and safety and health. Examples of water-based paints include the technology described in Patent Document 1. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2024-143794 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, the conventional technologies described above were insufficient from the standpoint of storage stability, and there was room for further improvement.

[0005] One embodiment of the present invention has been made in view of the above-mentioned problems, and its objective is to provide a novel water-based coating with excellent storage stability. [Means for solving the problem]

[0006] The inventors of this invention have diligently studied and conducted research to solve the aforementioned problems, and as a result, have completed this invention.

[0007] In other words, one embodiment of the present invention includes the following configuration. [1] A multi-component aqueous paint comprising: (A) a liquid A containing an alkoxysilyl group-containing synthetic resin emulsion and (B) a liquid B containing a substance that promotes hydrolysis and condensation of an alkoxysilyl group, wherein the alkoxysilyl group-containing synthetic resin includes a polyorganosiloxane and a graft portion graft-bonded to the polyorganosiloxane, and the polyorganosiloxane includes: (a) a structural unit U derived from a monomer represented by the following formula (1) 4 , , and (b) is non-crosslinked, and the graft portion includes a structural unit U derived from a monomer represented by the following formula (2) 2 An aqueous paint: R 1 m R 2 (4-m-n) SiX n ···(1) (In the formula, R 1 is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, R 2 is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are each independently an integer of 1 to 3, and the sum of m and n is 2 to 4); R 3 p R 4 (4-p-q) SiY q ···(2) (In the formula, R 3 is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, R 4 is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independently an integer of 1 to 3, and the sum of p and q is 2 to 4). [2] The aqueous paint according to [1], wherein the graft portion contains, in 100% by weight of the graft portion, 60% by weight or more of one or more structural units selected from the group consisting of a structural unit derived from a (meth)acrylate monomer having an alkyl group having 4 or more carbon atoms and a structural unit derived from a (meth)acrylate monomer having a cycloalkyl group having 4 or more carbon atoms. [3] The water-based paint according to [1] or [2], wherein the substance that promotes the hydrolysis and condensation of the (B) alkoxysilyl group comprises one or more selected from the group consisting of organometallic compounds, alkali metal compounds, acidic catalysts and basic catalysts. [4] The alkoxysilyl group-containing synthetic resin contains the constituent unit U in 100% by weight of the alkoxysilyl group-containing synthetic resin. 2 A water-based paint containing 0.5% by weight or more of the following, as described in any one of [1] to [3]. [5] A water-based paint as described in any one of [1] to [4], further comprising an antifouling agent. A method for manufacturing a coating film, comprising the step of applying a water-based paint described in any one of [6] [1] to [5] to an underwater structure. [7] A synthetic resin emulsion containing an alkoxysilyl group comprising a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane, wherein the polyorganosiloxane comprises (a) constituent units U derived from monomers represented by the following formula (1). 1 (b) is non-crosslinked, and the graft portion is composed of constituent units U derived from monomers represented by the following formula (2). 2 Water-based paints, including: R 1 m R 2 (4-m-n) SiX n ...(1) (In the formula, R 1 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 2 (where m is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are independently integers between 1 and 3, and the sum of m and n is between 2 and 4); R 3 p R 4 (4-p-q) SiY q ...(2) (In the formula, R 3 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 4(where is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independently integers between 1 and 3, and the sum of p and q is between 2 and 4). [Effects of the Invention]

[0008] According to one embodiment of the present invention, it is possible to provide a water-based paint with excellent storage stability. [Modes for carrying out the invention]

[0009] One embodiment of the present invention is described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Moreover, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic and patent documents mentioned herein are incorporated herein by reference.

[0010] In this specification, a "constituent unit derived from X monomer" contained in a polymer, copolymer, or resin may be referred to as an "X unit."

[0011] [1. Technical Concept of One Embodiment of an Embodiment] Conventional water-based paints, such as those described in Patent Document 1, are insufficient from the standpoint of storage stability and there is room for further improvement. Specifically, the inventors have independently discovered that conventional water-based paints, such as those described in Patent Document 1, have excellent film-forming properties immediately after manufacture, but may have poor film-forming properties after a long period of time (e.g., more than one week) has elapsed since manufacture, meaning they have poor storage stability.

[0012] The inventors diligently investigated the reasons why conventional water-based paints have poor storage stability. During this investigation, the inventors focused on the hydrolyzable silyl groups in the copolymers contained in the water-based paints described in Patent Document 1, and conducted further investigations. As a result, the inventors independently discovered the following novel findings, leading to the completion of the present invention: Water-based paints containing copolymers with a shell layer containing alkoxy groups of a specific number of carbon atoms exhibit excellent film-forming properties, i.e., excellent storage stability, even after a long period of time has elapsed since manufacture.

[0013] [2. Water-based paint] A water-based paint according to one embodiment of the present invention is a multi-component water-based paint comprising (A) liquid A containing an alkoxysilyl group-containing synthetic resin emulsion, and (B) liquid B containing a substance that promotes hydrolysis and condensation of alkoxysilyl groups, wherein the alkoxysilyl group-containing synthetic resin comprises a polyorganosiloxane and graft portions graft-bonded to the polyorganosiloxane, and the polyorganosiloxane comprises (a) constituent units U derived from monomers represented by the following formula (1). 1 (b) is non-crosslinked, and the graft portion is composed of constituent units U derived from monomers represented by the following formula (2). 2 Includes: R 1 m R 2 (4-m-n) SiX n ...(1) (In the formula, R 1 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 2 (where m is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are each independently integers between 1 and 3, and the sum of m and n is between 2 and 4); R 3 p R 4 (4-p-q) SiY q ...(2) (In the formula, R 3R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 4 (where is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independent integers between 1 and 3, and the sum of p and q is between 2 and 4).

[0014] In this specification, "water-based paint according to one embodiment of the present invention" may also be referred to as "this water-based paint."

[0015] Because this water-based paint has the above-described structure, it has the advantage of excellent storage stability. The storage stability of a water-based paint can be evaluated by evaluating its film-forming properties using a sample of the water-based paint that has been in use for a long period of time (e.g., one week) since its manufacture. If a water-based paint that has been in use for a long period of time (e.g., one week) since its manufacture exhibits excellent film-forming properties, it can be said that the water-based paint has excellent storage stability. Furthermore, the longer the period from manufacture during which a water-based paint with excellent film-forming properties can be provided, the better the storage stability of the water-based paint can be said to be. In this specification, the method for evaluating the "film-forming properties" of a water-based paint will be described in detail in the following examples. In addition, in a preferred embodiment of the present invention, the water-based paint can provide a coating film that is completely free of cracks or has very few cracks due to the hydrolysis and condensation of alkoxysilyl groups in the water-based paint. A coating film that is completely free of cracks or has very few cracks is considered to have excellent antifouling properties (e.g., antifouling properties against aquatic organisms). Therefore, in a preferred embodiment of the present invention, the water-based paint can provide a coating film with excellent antifouling properties (for example, antifouling properties against aquatic organisms) through hydrolysis and condensation of alkoxysilyl groups in the water-based paint.

[0016] This water-based paint comprises at least two components, A and B. This water-based paint is a multi-component water-based paint. In this specification, "multi-component" means a two-component or more paint consisting of at least two components, not a one-component paint consisting of only one component. If this water-based paint consists only of A and B, it can be said that the water-based paint is a "two-component" paint.

[0017] (2-1.A liquid) ((A) Synthetic resin emulsion containing alkoxysilyl groups) Liquid A contains (A) an alkoxysilyl group-containing synthetic resin emulsion. (A) The alkoxysilyl group-containing synthetic resin emulsion can also be described as an emulsion of (A) an alkoxysilyl group-containing synthetic resin. Liquid A can also be described as (i) containing an emulsion of an alkoxysilyl group-containing synthetic resin, (ii) containing an alkoxysilyl group-containing synthetic resin in emulsion form, or (iii) being a liquid in which the alkoxysilyl group-containing synthetic resin is dispersed. In this specification, "(A) alkoxysilyl group-containing synthetic resin emulsion" may be referred to as "(A) component".

[0018] (2-1-1. Synthetic resin containing alkoxysilyl groups) The alkoxysilyl group-containing synthetic resin in component (A) comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane.

[0019] (Polyorganosiloxane) Polyorganosiloxanes are composed of constituent units U derived from monomers represented by the following formula (1). 1 Includes: R 1 m R 2 (4-m-n) SiX n ...(1) In the formula, R 1 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 2 is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are independently integers between 1 and 3, and the sum of m and n is between 2 and 4.

[0020] R 1 Examples of ethylenically unsaturated groups in this context include vinyl groups, acryloyl groups, and methacryloyl groups.

[0021] Constituent unit U 1 R 1 If it contains two or more, in other words, if m is 2 or 3, then multiple R 1 These may be the same or they may be different.

[0022] R 2 Examples include methyl groups, ethyl groups, propyl groups, and butyl groups.

[0023] Constituent unit U 1 R 2 It does not have to include the constituent unit U. 1 R 2 If it contains two of them, in other words, if the value (difference) of "4-mn" is 2, then multiple R 2 These may be the same or they may be different.

[0024] Examples of X include methoxy groups, ethoxy groups, propoxy groups, and butoxy groups.

[0025] When the monomer represented by equation (1) contains two X, in other words, when n is 2 or 3, the multiple Xs may be the same or different.

[0026] In this specification, "monomer represented by formula (1)" is referred to as "monomer M" 1 It is sometimes referred to as "[...]."

[0027] Monomer M 1Specific examples include, for example, (a) vinylsilanes such as vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and tetramethyltetravinylcyclotetrasiloxane, and (b) β-methacryloyloxyethyldimethoxymethylsilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane, 3-(meth)acryloyloxypropylmethoxydimethylsilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyldiethoxymethylsilane, and 3-(meth)acryloyloxypropyldiethoxymethylsilane. Examples include (meth)acryloyloxyalkylsilanes such as toxyethylsilane, 3-(meth)acryloyloxypropylethoxydimethylsilane, 3-(meth)acryloyloxypropylethoxydiethylsilane, and δ-(meth)acryloyloxybutyldiethoxymethylsilane, and mercaptoalkylsilanes such as (c)3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropylmethoxydimethylsilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldiethoxymethylsilane, and 3-mercaptopropyldiethoxyethylsilane. Also, monomer M 1 Specific examples include p-vinylphenylmethyldimethoxysilane, 2-(m-vinylphenyl)ethylmethyldimethoxysilane, 1-(m-vinylphenyl)methyldimethylisopropoxysilane, 2-(p-vinylphenyl)ethylmethyldimethoxysilane, 3-(p-vinylphenoxy)propylmethyldiethoxysilane, 3-(p-vinylbenzoyloxy)propylmethyldimethoxysilane, 1-(o-vinylphenyl)-1,1,2-trimethyl-2,2-dimethoxydisilane, 1-(p-vinylphenyl)-1,1-diphenyl-3-ethyl-3,3-diethoxydisiloxane, m-vinylphenyl-[3-(triethoxysilyl)propyl]diphenylsilane, and [3-(p-isopropenylbenzoylamino)propyl]phenyldipropoxysilane. These monomers M 1One type may be used alone, or two or more types may be used in combination.

[0028] Monomer M 1 Preferably, one or more selected from the group consisting of (meth)acryloyloxyalkylsilanes such as β-methacryloyloxyethyldimethoxymethylsilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane, 3-(meth)acryloyloxypropylmethoxydimethylsilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyldiethoxymethylsilane, 3-(meth)acryloyloxypropyldiethoxyethylsilane, 3-(meth)acryloyloxypropylethoxydimethylsilane, 3-(meth)acryloyloxypropylethoxydiethylsilane, and δ-(meth)acryloyloxybutyldiethoxymethylsilane is preferred, and more preferably, one or more selected from the group consisting of 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyldimethoxymethylsilane is preferred. This configuration has the advantage of efficiently carrying out graft formation (polymerization) in the presence of polyorganosiloxane. As a result, it has the advantage of being able to obtain a synthetic resin containing alkoxysilyl groups with a high graft ratio.

[0029] Polyorganosiloxane contains, in 100% by weight, constituent unit U 1 It is preferable to contain 0.001% to 10.0% by weight of, more preferably 0.01% to 5.0% by weight of, even more preferably 0.1% to 5.0% by weight of, even more preferably 1.0% to 5.0% by weight of, and particularly preferably 1.0% to 3.0% by weight of. This configuration has the advantage of efficiently carrying out the formation (polymerization) of graft portions in the presence of polyorganosiloxane. As a result, it has the advantage of being possible to obtain an alkoxysilyl group-containing synthetic resin with a high graft rate.

[0030] <Organosiloxane System Units> Polyorganosiloxanes may further contain organosiloxane units. These organosiloxane units are not particularly limited. Examples of organosiloxane units include constituent units having at least one organic group and a silyloxy group.

[0031] Examples of organosiloxane units include (a) alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy units, diethylsilyloxy units, methylphenylsilyloxy units, diphenylsilyloxy units, and dimethylsilyloxy-diphenylsilyloxy units, and (b) alkyl or aryl monosubstituted silyloxy units such as organohydrogensilyloxy units in which part of the alkyl in the side chain is substituted with a hydrogen atom. When a polyorganosiloxane contains organosiloxane units, it may contain only one type of the above-mentioned organosiloxane units, or it may contain a combination of two or more types.

[0032] Since the resulting water-based paint can provide a coating film with excellent heat resistance, the polyorganosiloxane preferably contains 50 mol% or more of organosiloxane-based units, more preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more of organosiloxane-based units out of 100 mol% of the total constituent units contained in the polyorganosiloxane.

[0033] Since the resulting water-based paint can provide a coating film with superior heat resistance, the polyorganosiloxane preferably contains 50 mol% or more of one or more constituent units selected from the group consisting of dimethylsilyloxy units, methylphenylsilyloxy units, and dimethylsilyloxy-diphenylsilyloxy units, out of 100 mol% of the total constituent units contained in the polyorganosiloxane, more preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The raw material for dimethylsilyloxy units is more readily available and less expensive compared to other organosiloxane monomers. Therefore, from the viewpoint of availability and economics, the polyorganosiloxane more preferably contains 50 mol% or more of dimethylsilyloxy units, more preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, of the total constituent units contained in the polyorganosiloxane.

[0034] <Cross-linked structure of polyorganosiloxane> By using polyfunctional alkoxysilane compounds and / or polyfunctional monomers during the preparation of polyorganosiloxanes, a crosslinked structure can be introduced into the polyorganosiloxane. Therefore, polyfunctional alkoxysilane compounds and polyfunctional monomers can be considered crosslinking agents in polyorganosiloxanes. In one embodiment of the present invention, the polyorganosiloxane is non-crosslinked. Here, "the polyorganosiloxane is non-crosslinked" means that the total amount of polyfunctional alkoxysilane compounds and polyfunctional monomers used during the preparation of the polyorganosiloxane is 0.50% by weight or less of the monomer mixture for polyorganosiloxane formation in 100% by weight. In other words, in one embodiment of the present invention, the polyorganosiloxane is substantially non-crosslinked. The total amount of polyfunctional alkoxysilane compounds and polyfunctional monomers used in the preparation of polyorganosiloxanes is preferably 0.50% by weight or less, more preferably 0.20% by weight or less, even more preferably 0.10% by weight or less, and particularly preferably 0.01% by weight or less, based on 100% by weight of the monomer mixture for polyorganosiloxane formation. The monomer mixture for polyorganosiloxane formation used in the preparation of polyorganosiloxanes may not contain polyfunctional alkoxysilane compounds and polyfunctional monomers.

[0035] Examples of polyfunctional alkoxysilane compounds include tetramethoxysilane, tetraethoxysilane (TEOS), tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltriisopropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane.

[0036] A polyfunctional monomer can also be defined as a monomer having two or more radical polymerizable reactive groups within the same molecule. These radical polymerizable reactive groups are, for example, carbon-carbon double bonds. Examples of polyfunctional monomers do not include butadiene, but include (meth)acrylates having ethylenically unsaturated double bonds, such as allylalkyl (meth)acrylates and allyloxyalkyl (meth)acrylates. Monomers having two (meth)acrylic groups include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. Examples of polyethylene glycol di(meth)acrylates include triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol (600) di(meth)acrylate. Examples of monomers having three (meth)acrylic groups include alkoxylated trimethylolpropane tri(meth)acrylates, glycerol propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate. Examples of alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate and trimethylolpropane triethoxy tri(meth)acrylate. Furthermore, examples of monomers having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate. Also, examples of monomers having five (meth)acrylic groups include dipentaerythritol penta(meth)acrylate. And examples of monomers having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate.Other examples of polyfunctional monomers include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene.

[0037] In this specification, monomer M 1 and monomer M 2 This shall not be included in the definition of "polyfunctional monomers."

[0038] <Volume-average particle size of polyorganosiloxanes> The volume-average particle size of the polyorganosiloxane is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, more preferably 0.08 μm to 2.00 μm, even more preferably 0.10 μm to 1.00 μm, even more preferably 0.10 μm to 0.80 μm, and particularly preferably 0.10 μm to 0.50 μm. When the volume-average particle size of the polyorganosiloxane is (a) 0.03 μm or more, a polyorganosiloxane having the desired volume-average particle size can be stably obtained, and when it is 50.00 μm or less, the resulting water-based coating has the advantage of excellent film-forming properties. The volume-average particle size of the polyorganosiloxane can be measured using a dynamic light scattering particle size distribution analyzer or the like, with an aqueous latex containing polyorganosiloxane as the sample. The method for measuring the volume-average particle size of polyorganosiloxanes will be described in detail in the following examples.

[0039] In this water-based paint, the polyorganosiloxane is preferably 55% to 95% by weight, more preferably 60% to 95% by weight, even more preferably 65% ​​to 95% by weight, and particularly preferably 70% to 95% by weight in 100% by weight of the alkoxysilyl group-containing synthetic resin. When the polyorganosiloxane is (a) 55% by weight or more in 100% by weight of the alkoxysilyl group-containing synthetic resin, the water-based paint has the advantage of providing a coating film with a smaller loss tangent (tanδ) at seawater temperature, and when it is 95% by weight or less, the water-based paint has the advantage of having better film-forming properties.

[0040] In this water-based paint, of the total 100% by weight of polyorganosiloxane and graft portion, it is preferable that polyorganosiloxane accounts for 55% to 95% by weight and the graft portion accounts for 5% to 45% by weight; more preferably that polyorganosiloxane accounts for 60% to 95% by weight and the graft portion accounts for 5% to 40% by weight; even more preferably that polyorganosiloxane accounts for 65% to 95% by weight and the graft portion accounts for 5% to 35% by weight; and particularly preferably that polyorganosiloxane accounts for 70% to 95% by weight and the graft portion accounts for 5% to 30% by weight. When the polyorganosiloxane makes up 55% or more of the total 100% by weight of the polyorganosiloxane and graft portion, and the graft portion makes up 45% or less of the polyorganosiloxane, the water-based coating has the advantage of providing a coating film with a smaller loss tangent (tanδ) at seawater temperatures. When the polyorganosiloxane makes up 95% or less of the total 100% by weight of the polyorganosiloxane and graft portion, and the graft portion makes up 5% or more of the polyorganosiloxane, the water-based coating has the advantage of having superior film-forming properties.

[0041] A polyorganosiloxane may consist of only one type of polyorganosiloxane having the same composition (type and content ratio) and physical properties (such as volume-average particle size and weight-average molecular weight) of its constituent units, or it may consist of two or more types of polyorganosiloxanes with different composition and / or physical properties of their constituent units. If a polyorganosiloxane is composed of two or more types of polyorganosiloxanes with different composition and / or physical properties of their constituent units, each of those two or more polyorganosiloxanes may form a layered structure.

[0042] (Core part) The alkoxysilyl group-containing synthetic resin comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane. In the alkoxysilyl group-containing synthetic resin, the graft portion may cover at least a portion of the polyorganosiloxane or may cover the entire polyorganosiloxane. Preferably, at least a portion of the graft portion is located on the outermost side of the alkoxysilyl group-containing synthetic resin. Therefore, the polyorganosiloxane can be considered the core portion of the alkoxysilyl group-containing synthetic resin. In other words, the alkoxysilyl group-containing synthetic resin comprises a core portion containing a polyorganosiloxane and a graft portion grafted to the core portion.

[0043] The core portion may consist of only one type of polyorganosiloxane having the same composition (type and content ratio) of constituent units, or it may consist of two or more types of polyorganosiloxanes having different compositions (type and content ratio) of constituent units. In addition, the core portion may contain one or more types of other rubbers in addition to one or more types of polyorganosiloxanes.

[0044] Other types of rubber include, for example, (a) natural rubber, (b) diene rubber containing 50% by weight or more of constituent units derived from diene monomers in 100% by weight of rubber, and (c) (meth)acrylate rubber containing 50% by weight or more of constituent units derived from (meth)acrylate monomers in 100% by weight of rubber. In this specification, (meth)acrylate means acrylate and / or methacrylate.

[0045] If the core contains other rubbers in addition to polyorganosiloxane, each of the polyorganosiloxane and other rubbers may form a layered structure. If the core contains a layer of polyorganosiloxane and a layer of other rubbers, it is preferable that the polyorganosiloxane layer is located in the center (innermost) of the core.

[0046] The core portion preferably contains 55 to 100 parts by weight of polyorganosiloxane per 100 parts by weight, more preferably 60 to 100 parts by weight, more preferably more than 60 parts by weight and 100 parts by weight or less, more preferably 62 to 100 parts by weight, more preferably 65 to 100 parts by weight, more preferably 70 to 100 parts by weight, more preferably 75 to 100 parts by weight, more preferably 80 to 100 parts by weight, more preferably 85 to 100 parts by weight, even more preferably 90 to 100 parts by weight or less, and particularly preferably 95 to 100 parts by weight or less. According to this configuration, the water-based paint has the advantage of being able to provide a coating film with a smaller loss tangent (tanδ) under seawater temperature. The core portion may contain 100 parts by weight of polyorganosiloxane in 100 parts by weight of the core portion, that is, the core portion may be composed solely of polyorganosiloxane.

[0047] <Volume-average particle diameter of the core> The volume-average particle diameter of the core is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, more preferably 0.08 μm to 2.00 μm, even more preferably 0.10 μm to 1.00 μm, even more preferably 0.10 μm to 0.80 μm, and particularly preferably 0.10 μm to 0.50 μm. When the volume-average particle diameter of the core is (a) 0.03 μm or more, a core having the desired volume-average particle diameter can be stably obtained, and when it is 50.00 μm or less, the resulting water-based coating has the advantage of excellent film-forming properties. The volume-average particle diameter of the core can be measured using a dynamic light scattering particle size distribution analyzer or the like, with the aqueous latex containing the core as the sample, in the same manner as the volume-average particle diameter of polyorganosiloxane.

[0048] (graft section) The graft portion is graft-bonded to the polyorganosiloxane. It is sufficient that at least a portion of the graft portion is graft-bonded to the polyorganosiloxane; it is not necessary for the entire graft portion to be graft-bonded to the polyorganosiloxane.

[0049] The graft portion is composed of constituent units U derived from monomers represented by the following formula (2). 2 Includes: R 3 p R 4 (4-p-q) SiY q ...(2).

[0050] In the formula, R 3 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 4 is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independent integers between 1 and 3, and the sum of p and q is between 2 and 4.

[0051] R 3 Examples of ethylenically unsaturated groups in this context include vinyl groups, acryloyl groups, and methacryloyl groups.

[0052] (a) It is highly receptive to crosslinking (vinyl polymerization), (b) it is easy to handle, (c) it is inexpensive, (d) the water-based paint can provide a coating with a lower loss tangent (tanδ), and (e) blister formation when the coating obtained from the water-based paint is immersed in water is reduced or eliminated, R 3 In this compound, acryloyl or methacryloyl groups are preferred as ethylenically unsaturated groups.

[0053] Constituent unit U 2 R 3 If it contains two or more, in other words, if p is 2 or 3, then multiple R 3 These may be the same or they may be different.

[0054] R 4 Examples of [R] include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0055] Structural unit U 2 may not contain [R]. The structural unit U 4 When the structural unit U 2 contains two [R], 4 in other words, when the value (difference) of “4 - p - q” is 2, the plurality of [R] 4 may be the same or different from each other.

[0056] Examples of [Y] include an ethoxy group, a propoxy group, and a butoxy group. With this configuration, the aqueous paint has the advantage of excellent storage stability.

[0057] When the monomer represented by formula (2) contains two [Y],

[0058] in other words, when q is 2 or 3, the plurality of [Y] may be the same or different from each other.

[0058] In this specification, the “monomer represented by formula (2)” may be referred to as “monomer M 2 ”.

[0059] Monomer M 2 is not particularly limited as long as it is represented by formula (2). Since (a) it is rich in cross - linking reactivity (vinyl polymerization reactivity), (b) it is easy to handle, (c) it is inexpensive, (d) the aqueous paint can provide a coating film with a lower loss tangent (tanδ), and (e) the generation of blisters when the coating film obtained from the aqueous paint is immersed in water is further reduced or eliminated, monomer M 2(meth)acryloyloxyalkylsilanes are preferred, and one or more selected from the group consisting of 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyldiethoxymethylsilane, 3-(meth)acryloyloxypropyldiethoxyethylsilane, 3-(meth)acryloyloxypropylethoxydimethylsilane, 3-(meth)acryloyloxypropylethoxydiethylsilane, and δ-(meth)acryloyloxybutyldiethoxymethylsilane are more preferred.

[0060] The graft portion is composed of the constituent unit U in 100% by weight of the graft portion. 2It is preferable to contain 1.0% to 80.0% by weight, more preferably 1.0% to 75.0% by weight, more preferably 1.0% to 70.0% by weight, more preferably 1.0% to 65.0% by weight, more preferably 1.0% to 60.0% by weight, more preferably 1.5% to 55.0% by weight, more preferably 1.5% to 50.0% by weight, more preferably 1.5% to 45.0% by weight, more preferably 1.5% to 40.0% by weight, more preferably 2.0% to 38.0% by weight, and more preferably 2.0% to 35.0% by weight. It is more preferable to include the following: more preferably 2.0% by weight or more and 33.0% by weight or less; more preferably 2.5% by weight or more and 30.0% by weight or less; more preferably 2.5% by weight or more and 28.0% by weight or less; more preferably 2.5% by weight or more and 25.0% by weight or less; more preferably 3.0% by weight or more and 23.0% by weight or less; more preferably 3.0% by weight or more and 20.0% by weight or less; more preferably 3.5% by weight or more and 18.0% by weight or less; more preferably 3.5% by weight or more and 15.0% by weight or less; even more preferably 4.0% by weight or more and 13.0% by weight or less; and particularly preferably 4.0% by weight or more and 10.0% by weight or less. This configuration has the advantages that (a) the water-based paint can provide a coating with a lower loss tangent (tanδ), and (b) blistering when the coating obtained from the water-based paint is immersed in water is reduced or eliminated.

[0061] (A) The alkoxysilyl group-containing synthetic resin in the alkoxysilyl group-containing synthetic resin is composed of the aforementioned constituent unit U in 100% by weight of the alkoxysilyl group-containing synthetic resin. 2It is preferable to contain 0.5% by weight or more, more preferably 0.8% by weight or more, more preferably 1.0% by weight or more, more preferably 1.3% by weight or more, even more preferably 1.5% by weight or more, and particularly preferably 2.0% by weight or more. This configuration has the advantage of improving the strength of the coating film. The alkoxysilyl group-containing synthetic resin in component (A) is composed of the above-mentioned constituent unit U in 100% by weight of the alkoxysilyl group-containing synthetic resin. 2 It is preferable to contain 5.0% by weight or less, more preferably 4.0% by weight or less, more preferably 3.0% by weight or less, even more preferably 2.0% by weight or less, even more preferably 1.8% by weight or less, and particularly preferably 1.5% by weight or less. This configuration has the advantage of improving film-forming properties.

[0062] (A) The alkoxysilyl group-containing synthetic resin emulsion contains the constituent unit U in 100% by weight of the solid content of the (A) alkoxysilyl group-containing synthetic resin emulsion. 2 It is preferable to contain 0.5% by weight or more, more preferably 0.8% by weight or more, more preferably 1.0% by weight or more, more preferably 1.3% by weight or more, even more preferably 1.5% by weight or more, and particularly preferably 2.0% by weight or more. This configuration has the advantage of improving the strength of the coating film. (A) The alkoxysilyl group-containing synthetic resin emulsion contains the constituent unit U in 100% by weight of the solid content of the (A) alkoxysilyl group-containing synthetic resin emulsion. 2 It is preferable to contain 5.0% by weight or less, more preferably 4.0% by weight or less, more preferably 3.0% by weight or less, even more preferably 2.0% by weight or less, even more preferably 1.8% by weight or less, and particularly preferably 1.5% by weight or less. This configuration has the advantage of improving film-forming properties.

[0063] (A) The solid content concentration in the alkoxysilyl group-containing synthetic resin emulsion can be measured using an electronic moisture meter. The constituent unit U in the alkoxysilyl group-containing synthetic resin 2 The content of (A) the constituent unit U in an alkoxysilyl group-containing synthetic resin emulsion. 2 The content of the constituent unit U 2 It can be measured by hydrolyzing the substance and analyzing (measuring) the amount of alcohol produced during the process. If the monomer composition used during manufacturing is known, the monomer M can be measured relative to the total amount of monomers used. 2 Based on the proportion of usage, and taking into account the polymerization conversion rate, the constituent unit U in alkoxysilyl group-containing synthetic resins 2 The content of (A) the constituent unit U in an alkoxysilyl group-containing synthetic resin emulsion. 2 The content may be calculated.

[0064] The graft portion is composed of the U 2 It may also include other constituent units. Constituent unit U 2 Other constituent units are not particularly limited. The graft portion is a constituent unit U 2 In addition to the above, it is preferable to include constituent units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. With this configuration, the graft portion can perform the function of solidifying the substantially non-crosslinked polyorganosiloxane. Therefore, with this configuration, the resulting water-based paint has the advantage of excellent film-forming properties and excellent strength of the coating film.

[0065] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

[0066] Specific examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.

[0067] Specific examples of (meth)acrylate monomers include, for example, (a) alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (b) cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and butylcyclohexyl (meth)acrylate; (c) aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; and (d) 2-hydro Examples include (e) hydroxyalkyl (meth)acrylates such as xyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; (f) glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidylalkyl (meth)acrylate; (g) alkoxyalkyl (meth)acrylates; (h) allylalkyl (meth)acrylates such as allyl (meth)acrylate and allylalkyl (meth)acrylate; and polyfunctional (meth)acrylates such as monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

[0068] From the viewpoint of reactivity during graft formation, it is preferable to use one or more (meth)acrylate monomers selected from the group consisting of methyl acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.

[0069] The graft portion may consist of one or more constituent units selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers, and may contain only one type of constituent unit, or it may contain a combination of two or more constituent units.

[0070] The graft portion preferably contains, in total, 60% to 99% by weight, 62% to 98% by weight, 65% to 97% by weight, 68% to 96% by weight, and most preferably 70% to 95% by weight, of constituent units derived from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers, within 100% by weight of the graft portion. This configuration has the advantage that the resulting water-based paint has superior film-forming properties.

[0071] From the viewpoint of achieving both the film-forming properties of water-based paints and the reactivity during graft formation, the graft portion preferably contains constituent units derived from (meth)acrylate monomers, and may also be composed solely of constituent units derived from (meth)acrylate monomers.

[0072] The graft portion preferably contains 60% to 99% by weight of constituent units derived from (meth)acrylate monomers, more preferably 62% to 98% by weight, even more preferably 65% ​​to 97% by weight, particularly preferably 68% to 96% by weight, and most preferably 70% to 95% by weight. This configuration has the advantage of excellent reactivity during graft formation.

[0073] Since the storage stability of the alkoxysilyl group-containing synthetic resin emulsion is greatly improved, the graft portion preferably contains one or more structural units selected from the group consisting of structural units derived from (meth)acrylate monomers having an alkyl group having 4 or more carbon atoms and structural units derived from (meth)acrylate monomers having a cycloalkyl group having 4 or more carbon atoms, or it may consist only of one or more structural units selected from the said group.

[0074] The graft portion preferably contains 60% by weight or more of one or more constituent units selected from the group consisting of constituent units derived from (meth)acrylate monomers having an alkyl group having 4 or more carbon atoms and constituent units derived from (meth)acrylate monomers having a cycloalkyl group having 4 or more carbon atoms, in 100% by weight of the graft portion; more preferably 60% by weight or more and 99% by weight or less; more preferably 62% by weight or more and 98% by weight or less; even more preferably 65% ​​by weight or more and 97% by weight or less; particularly preferably 68% by weight or more and 96% by weight or less; and most preferably 70% by weight or more and 95% by weight or less. This configuration has the advantage of significantly improving the storage stability of the alkoxysilyl group-containing synthetic resin emulsion.

[0075] Because of its superior reactivity during graft formation, the graft portion preferably contains constituent units derived from methyl methacrylate and constituent units derived from butyl methacrylate, but it may also be composed solely of constituent units derived from methyl methacrylate and constituent units derived from butyl acrylate.

[0076] The graft portion preferably contains, in total, 60% to 99% by weight, 62% to 98% by weight, 65% to 97% by weight, 68% to 96% by weight, and most preferably 70% to 95% by weight, of constituent units derived from methyl methacrylate and butyl methacrylate in 100% by weight of the graft portion. This configuration has the advantage of superior reactivity during graft formation.

[0077] <Constituent units derived from reactive emulsifiers> The graft portion may further contain constituent units derived from a reactive emulsifier. This configuration has the advantage of reducing or eliminating scale formation during the manufacture of water-based paints.

[0078] In this specification, "reactive emulsifier" refers to an emulsifier having an ethylenically unsaturated double bond. Furthermore, "reactivity" in a reactive emulsifier refers to the ability to possess polymerizable radicals in the presence of a polymerization initiator, for example. Therefore, a "reactive emulsifier" can also be called a "polymerizable emulsifier." A "reactive emulsifier" is sometimes also referred to as a "reactive surfactant."

[0079] The type of reactive emulsifier is not particularly limited, as long as it has an ethylenically unsaturated double bond. The reactive emulsifier may be a cationic reactive emulsifier, an anionic reactive emulsifier, or a nonionic reactive emulsifier. As for the reactive emulsifier, an anionic reactive emulsifier is preferred because it is easier to control the particle size of the alkoxysilyl group-containing synthetic resin to be fine (specifically, the volume-average particle size of the alkoxysilyl group-containing synthetic resin is 30 nm or more and 200 nm or less).

[0080] The ethylenically unsaturated double bond in reactive emulsifiers originates from a group containing an ethylenically unsaturated double bond. In other words, reactive emulsifiers contain a group with an ethylenically unsaturated double bond. Specific examples of groups containing an ethylenically unsaturated double bond include oxyalkylene groups, (meth)acryloyl groups, vinyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, allyloxy groups, and styryl groups.

[0081] The reactive emulsifier preferably has an oxyalkylene group. Reactive emulsifiers having an oxyalkylene group exhibit excellent copolymerization with monomers. Examples of oxyalkylene groups include oxyethylene groups, oxypropylene groups, and oxybutylene groups, which are alkylene groups having 2 to 4 carbon atoms. Among these, the oxyethylene group is preferred as the oxyalkylene group. The oxyethylene group has higher hydrophilicity than, for example, the oxypropylene group and the oxybutylene group. Therefore, when the graft portion of the alkoxysilyl group-containing synthetic resin contains constituent units derived from a reactive emulsifier having an oxyethylene group, a dense hydration layer can be formed on the surface of the particles of the alkoxysilyl group-containing synthetic resin, and as a result, the dispersibility of the particles of the alkoxysilyl group-containing synthetic resin in an aqueous medium tends to be higher.

[0082] The average number of oxyethylene groups added per mole of reactive emulsifier is not particularly limited, but is preferably 5 moles to 40 moles, and more preferably 10 moles to 30 moles. This configuration tends to result in excellent copolymerization with monomers. Furthermore, when the average number of oxyethylene groups added is 5 moles or more, the dispersibility of alkoxysilyl group-containing synthetic resin particles in aqueous media tends to be higher.

[0083] The reactive emulsifiers described above may be used individually or in combination of two or more.

[0084] The graft portion preferably contains 0.1% to 20.0% by weight of constituent units derived from a reactive emulsifier, more preferably 0.1% to 15.0% by weight, more preferably 1.0% to 15.0% by weight, more preferably 1.0% to 10.0% by weight, even more preferably 1.0% to 8.0% by weight, even more preferably 1.0% to 5.0% by weight, and particularly preferably 1.0% to 4.0% by weight. This configuration has the advantage of further reducing or eliminating scale formation during the manufacture of water-based paints.

[0085] <Constituent units derived from chain transfer agents> The graft portion may or may not contain structural units derived from the chain transfer agent.

[0086] The chain transfer agent is not particularly limited, and known chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, and 2-ethylhexyl thioglycolate can be used.

[0087] When a chain transfer agent is used as a raw material during the preparation of the graft portion, a graft portion containing constituent units derived from the chain transfer agent can be obtained. When a chain transfer agent is used as a raw material during the preparation of the graft portion, in other words, when the graft portion contains constituent units derived from the chain transfer agent, a polymer having the same structure as the graft portion (i.e., constituent unit U) can be obtained during the preparation of the graft portion. 2 The polymer contains ( ), and polymers that are not grafted to any of the polymers (e.g., polyorganosiloxanes) (hereinafter sometimes referred to as "non-grafted polymers") may be generated. As a result, when a chain transfer agent is used as a raw material when preparing the graft portion, solution A may contain non-grafted polymers. When solution A contains non-grafted polymers, it has the advantage of excellent film-forming properties.

[0088] If the amount of chain transfer agent used in the preparation of the graft is 0.01% by weight or less per 100% by weight of the monomer mixture for graft formation, the content of constituent units derived from the chain transfer agent in the resulting graft may be 0.01% by weight or less per 100% by weight of the graft. If the content of constituent units derived from the chain transfer agent in the graft is 0.01% by weight or less per 100% by weight of the graft, then in this specification, the graft is considered to "not contain constituent units derived from the chain transfer agent." If the amount of chain transfer agent used in the preparation of the graft is 0.01% by weight or less per 100% by weight of the monomer mixture for graft formation, then no non-graft polymers will be generated at all during the preparation of the graft, or if any are generated, the amount of non-graft polymers will be extremely small. As a result, when the amount of chain transfer agent used during the preparation of the graft is 0.01% by weight or less of the monomer mixture for graft formation (100% by weight), solution A will contain no non-graft polymers, or if it does, the amount of non-graft polymers will be extremely small. When solution A contains no non-graft polymers, or if it does, the amount of non-graft polymers will be extremely small, it has the advantage of excellent water resistance.

[0089] <Cross-linking structure of the graft section> By using a polyfunctional monomer during the preparation of the graft portion, a crosslinked structure can be introduced into the graft portion. In one embodiment of the present invention, it is preferable that the graft portion is non-crosslinked. Here, "the graft portion is non-crosslinked" means that all polymers contained in the graft portion are non-crosslinked. Furthermore, "the graft portion is non-crosslinked" means that (i) the amount of polyfunctional monomer used during the preparation of the graft portion is 0.50% by weight or less of the monomer mixture for graft portion formation in 100% by weight. In other words, in one embodiment of the present invention, it is preferable that the graft portion is substantially non-crosslinked, and it is preferable that the amount of polyfunctional monomer used during the preparation of the graft portion is 0.50% by weight or less of the monomer mixture for graft portion formation in 100% by weight. The amount of polyfunctional monomer used when preparing the graft portion is preferably 0.50% by weight or less, more preferably 0.20% by weight or less, even more preferably 0.10% by weight or less, and particularly preferably 0.01% by weight or less, based on 100% by weight of the monomer mixture for graft formation.

[0090] Each graft portion may consist of only one polymer having the same composition (type and content ratio) and physical properties (such as volume-average particle size and weight-average molecular weight) of constituent units, or it may consist of two or more polymers with different composition and / or physical properties of constituent units. If the graft portion consists of two or more polymers with different composition and / or physical properties of constituent units, each of those two or more polymers may form a layered structure.

[0091] The core portion and graft portion containing the polyorganosiloxane may have a layered structure. For example, one embodiment of the present invention is one in which the core portion containing the polyorganosiloxane is the innermost layer (also referred to as the core layer), and the graft portion layer exists outside the core portion as the outermost layer (also referred to as the shell layer). A structure in which the core portion containing the polyorganosiloxane is the core layer and the graft portion is the shell layer can also be called a core-shell structure. However, as long as the graft portion is graft-bonded to the polyorganosiloxane, the alkoxysilyl group-containing synthetic resin is not limited to the above configuration.

[0092] (Volume average particle size of synthetic resin containing alkoxysilyl groups) The volume-average particle size (Mv) of the alkoxysilyl group-containing synthetic resin is preferably 0.05 μm to 60.00 μm, more preferably 0.10 μm to 20.00 μm, more preferably 0.10 μm to 8.00 μm, more preferably 0.10 μm to 6.00 μm, more preferably 0.10 μm to 4.00 μm, more preferably 0.10 μm to 2.00 μm, even more preferably 0.10 μm to 1.00 μm, and particularly preferably 0.10 μm to 0.80 μm, in order to obtain a water-based paint with the desired viscosity and high stability. This configuration has the advantage of excellent polymerization stability for the alkoxysilyl group-containing synthetic resin and excellent storage stability for the water-based paint. In this specification, unless otherwise specified, "volume-average particle size (Mv) of alkoxysilyl group-containing synthetic resin" refers to the volume-average particle size of the primary particles of the alkoxysilyl group-containing synthetic resin. The volume-average particle size of the alkoxysilyl group-containing synthetic resin can be measured using a dynamic light scattering particle size distribution analyzer or the like, with a water-based paint or emulsion containing the alkoxysilyl group-containing synthetic resin (i.e., component (A)) as a sample. The volume-average particle size of the alkoxysilyl group-containing synthetic resin will be described in detail in the following examples.

[0093] In water-based paints, the particle size distribution of the alkoxysilyl group-containing synthetic resin preferably has a full width at half maximum of 0.5 to 1 times the volume-average particle size. This configuration has the advantage of making the water-based paint low viscosity and easy to handle.

[0094] The method for producing alkoxysilyl group-containing synthetic resins will be explained in detail later in the section on "Method for producing water-based paints."

[0095] (Other optional component 1) Solution A may contain components other than component (A) (hereinafter sometimes referred to as "other optional component 1") as needed. Other optional components include colorants such as pigments and dyes, extender pigments, pigment dispersants, UV absorbers, antioxidants, heat stabilizers (gelling inhibitors), stabilizers, plasticizers, leveling agents (e.g., BYK-333 from Bic Chemie Japan), defoamers (e.g., Agitan 295 from Munzing Chemie), silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, viscosity thickeners (e.g., SN Thickener 612NC from Sunopco), viscosity modifiers, thixotropy imparters, low shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, wetting agents, dispersants, anti-sagging agents, color separation inhibitors, settling inhibitors, coating wear modifiers, surface modifiers, film-forming aids (e.g., CS-12 from JNC), antibacterial agents, antifungal agents, preservatives, antifreeze agents, tackifiers, rust inhibitors, and the like.

[0096] The aforementioned liquid A itself is also one embodiment of the present invention. That is, one embodiment of the present invention provides a water-based paint that does not contain liquid B, which will be described later, or more specifically, does not contain component (B) which will be described later.

[0097] (2-2.B liquid) ((B) Substances that promote the hydrolysis and condensation of alkoxysilyl groups) Solution B contains a substance that promotes the hydrolysis and condensation of (B) alkoxysilyl groups. "Hydrolysis and condensation" means "hydrolysis and condensation". In this specification, "(B) substance that promotes the hydrolysis and condensation of alkoxysilyl groups" may be referred to as "(B) component".

[0098] Component (B) can promote the hydrolysis and condensation of the alkoxysilyl groups contained in the alkoxysilyl group-containing synthetic resin in component (A). Therefore, this water-based paint has the advantage of excellent film formation speed due to the inclusion of component (B). Furthermore, this water-based paint also has the advantage of providing a coating film with excellent strength due to the inclusion of component (B).

[0099] Component (B) is not particularly limited, as long as it is a substance contained in component (A), and especially in the alkoxysilyl group-containing synthetic resin in component (A), that can promote the hydrolysis and condensation of alkoxysilyl groups.

[0100] (B) Examples of component include organometallic compounds, alkali metal compounds, acidic catalysts, and basic catalysts.

[0101] Examples of organometallic compounds include organotin compounds.

[0102] Organotin compounds include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl malate, dibutyltin diethyl malate, dibutyltin dibutyl malate, dibutyltin diisooctyl malate, dibutyltin ditridecyl malate, dibutyltin dibenzyl malate, dibutyltin maleate, dioctyl tin diacetate, dioctyl tin distearate, dioctyl tin dilaurate, dioctyl tin diethyl malate, dioctyl tin diisooctyl malate, etc.), dialkyltin oxides (dibutyltin oxide, dioctyl tin oxide, mixtures of dibutyltin oxide and phthalate esters, etc.), tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.), and low molecular weight silicon containing alkoxysilyl groups. Examples include reaction products with compounds (such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, and phenyltrimethoxysilane), divalent tin compounds (such as tin octoate, tin naphthenate, and tin stearate), monoalkyltin compounds (such as monobutyltin compounds (monobutyltin trisoctoate, monobutyltin triisopropoxide, etc.) and monooctyltin compounds), reaction products or mixtures of amine compounds and organotin compounds (such as reaction products or mixtures of laurylamine and tin octoate), chelate compounds (such as dibutyltin bisacetylacetonate, dioctyltin bisacetylacetonate, dibutyltin bisethylacetonate, and dioctyltin bisethylacetonate), and tin alkalis (such as dibutyltin nitride, dibutyltin diethylate, dioctyltin nitride, and dioctyltin diethylate). Other examples of organotin compounds include dibutyltin diacetylacetonate, dibutyltin dimalate, dibutyltin dioleylmalate, dibutyltin dimethoxide, dibutyltin thioglycolate, dibutyltin bisisononyl 3-mercaptopropionate, dibutyltin bisisooctylthioglycolate, dibutyltin bis-2-ethylhexylthioglycolate, dimethyltin bisdodecyl mercaptide, dibutyltin bisdodecyl mercaptide, dioctyltin bisdodecyl mercaptide, and dimethyltin bis(octylthioglycolate) salts.

[0103] Examples of basic catalysts include amine compounds, heterocyclic compounds, and phosphorus compounds. Examples of amine compounds include butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU).

[0104] The alkali metal compound is not particularly limited as long as it contains at least one alkali metal. Suitable alkali metal compounds include, for example, lithium compounds, sodium compounds, and potassium compounds. From the viewpoint of low-temperature curing properties, storage stability, and painting workability of water-based paints, lithium compounds are the most preferred among these alkali metal compounds.

[0105] Examples of alkali metal compounds include metal salts containing at least one alkali metal, and metal complexes. Among these, alkali metal salts of carboxylic acids are preferred as alkali metal compounds, and alkali metal salts of carboxylic acids containing a carboxylic acid with 6 to 24 carbon atoms are more preferred. In alkali metal salts of carboxylic acids with 6 to 24 carbon atoms, the carboxylic acid is preferably a long-chain carboxylic acid. As alkali metal compounds, alkali metal salts of long-chain carboxylic acids are particularly preferred. Here, "long-chain" in long-chain carboxylic acids means a chain with 6 or more carbon atoms.

[0106] In the alkali metal salt of the carboxylic acid, the carboxylic acid is preferably a monocarboxylic acid.

[0107] In alkali metal salts of carboxylic acids having 6 to 24 carbon atoms, the carboxylic acid having 6 to 24 carbon atoms may consist of only one type of carboxylic acid, or a combination of two or more types of carboxylic acids. From the viewpoint of ease of manufacture and improved antifouling properties of water-based paints, it is preferable that the carboxylic acid in the alkali metal salt of a carboxylic acid having 6 to 24 carbon atoms contains two or more types of carboxylic acids. When the carboxylic acid in the alkali metal salt of a carboxylic acid having 6 to 24 carbon atoms contains two or more types of carboxylic acids, the two or more types of carboxylic acids may be an isomer mixture, a mixture of multiple carboxylic acids with different numbers of carbon atoms, or a combination of an isomer mixture and a mixture of multiple carboxylic acids with different numbers of carbon atoms. In alkali metal salts of carboxylic acids having 6 to 24 carbon atoms, the hydrocarbon chain constituting the carboxylic acid may be saturated or unsaturated. In alkali metal salts of carboxylic acids having 6 to 24 carbon atoms, the hydrocarbon chain constituting the carboxylic acid may be linear, branched, or have a cyclic structure. In alkali metal salts of carboxylic acids having 6 to 24 carbon atoms, if the hydrocarbon chain constituting the carboxylic acid is branched, it is preferable that the length of the longest chain is 6 carbon atoms or more.

[0108] In the alkali metal salt of the carboxylic acid, the number of carbon atoms in the carboxylic acid is preferably 6 to 24, more preferably 8 to 22, and even more preferably 8 to 16.

[0109] In the alkali metal carboxylic acid salts mentioned above, specific examples of carboxylic acids include hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, octanoic acid, nonanoic acid, versatic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanic acid, behenic acid, erucic acid, oleic acid, linoleic acid, linolenic acid, and naphthenic acid. Among these, the carboxylic acid in the alkali metal carboxylic acid salts is preferably a long-chain carboxylic acid having a straight or branched hydrocarbon chain, more preferably a long-chain carboxylic acid having a straight or branched alkyl chain, even more preferably one or more selected from the group consisting of 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, and versatic acid, and particularly preferably one or more selected from the group consisting of 2-ethylhexanoic acid, octanoic acid, and versatic acid. Versatic acid is a mixture of monocarboxylic acids (including isomer mixtures) mainly consisting of a monocarboxylic acid with 10 carbon atoms, and alkali metal salts of versatic acid are alkali metal salts of long-chain carboxylic acids containing two or more carboxylic acids.

[0110] The alkali metal compound preferably includes (i) one or more selected from the group consisting of lithium compounds, sodium compounds, and potassium compounds, and may consist only of one or more selected from this group; (ii) it is more preferably includes one or more selected from the group consisting of lithium 2-ethylhexanoate, lithium octanoate, lithium versatate, sodium 2-ethylhexanoate, sodium octanoate, sodium versatate, potassium 2-ethylhexanoate, potassium octanoate, and potassium versatate, and may consist only of one or more selected from this group. From the viewpoint of ease of manufacture and improved antifouling properties of water-based paints, the alkali metal compound is even more preferably to include one or more selected from the group consisting of lithium versatate, sodium versatate, and potassium versatate, and may consist only of one or more selected from this group; it is particularly preferably to include lithium versatate, and may consist only of lithium versatate.

[0111] Examples of acidic catalysts include straight-chain saturated fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, and laxeric acid; and undecylenic acid, lindelic acid, tuzic acid, physetelic acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, and palmitoleic acid. Monoenonsaturated fatty acids such as petroceric acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, gadolic acid, gondouic acid, cetoleic acid, erucic acid, brassic acid, ceracoleic acid, xymenic acid, lumecitric acid; linoleic acid, 10,12-octadecadienoic acid, hiragonic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12 Polyene unsaturated fatty acids such as 16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid, sardine acid, herring acid, and docosahexaenoic acid; branched fatty acids such as iso acid, anteiso acid, tubercurostearic acid, pivalic acid, 2-ethylhexanoic acid, neodecanoic acid, and versatic acid; fatty acids with triple bonds such as tali-phosphate, stearolic acid, krepenic acid, ximenic acid, and 7-hexadecinic acid; and alicyclic carboxylic acids such as naphthenic acid, malvalumic acid, sterkric acid, hydnocarbic acid, schormuglic acid, and gol-phosphate. Examples include oxygen-containing fatty acids such as sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, jalapinolic acid, unipenic acid, ambretolic acid, allulitic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlorenic acid, lycanic acid, feronic acid, and cerebronic acid; and dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, superiic acid, azelaic acid, and sebacic acid.

[0112] (B) Component (i) preferably contains one or more selected from the group consisting of organometallic compounds, alkali metal compounds, acidic catalysts and basic catalysts, (ii) preferably contains one or more selected from the group consisting of organotin compounds, amine compounds and alkali metal compounds, and may consist only of one or more selected from the said group, (iii) dibutyltin diacetylacetonate, dibutyltin thioglycolate, dibutyltin bisisononyl 3-mercaptopropionate, dibutyltin bisisooctyl thioglycolate, dibutyltin bis-2-ethylhexyl thioglycolate, dimethyltin bisdodecyl mercaptide, dibutyltin bisdodecyl mercaptide, dioctyltin bisdodecyl mercaptide, dimethyltin bis(octylthioglycolate) salt, lithium 2-ethylhexanoate, lithium octanoate, lithium versatate, 2-ethylhexanoate (iv) It is more preferable to include one or more selected from the group consisting of sodium, sodium octanoate, sodium versatate, potassium 2-ethylhexanoate, potassium octanoate, potassium versatate, laurylamine, diethylaminopropylamine, and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU), and it may consist of only one or more selected from this group. (iv) It is even more preferable to include one or more selected from the group consisting of dibutyltin diacetylacetonate, lithium versatate, sodium versatate, potassium versatate, and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU), and it may consist of only one or more selected from this group. (v) It is particularly preferable to include dibutyltin diacetylacetonate, and it may consist of only dibutyltin diacetylacetonate. The preferred (B) components described above are readily available and have excellent catalytic activity. Furthermore, if component (B) contains or consists solely of the above-mentioned preferred compounds, it has the advantages of (i) the water-based coating being easy to manufacture and having improved stain resistance, and (ii) being less likely to be subject to restrictions on use due to legal regulations.

[0113] If component (B) is a liquid, component (B) itself may be used as solution B. In other words, solution B may consist only of component (B).

[0114] (solvent) Solution B may contain a solvent in addition to component (B). In particular, if component (B) is a solid, solution B may be a liquid in which component (B) is dissolved in the solvent, or a liquid in which component (B) is dispersed in the solvent.

[0115] The solvent is not particularly limited. Examples of solvents include water, propylene glycol, propylene glycol monomethyl ether (PGMME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-tert-butyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and tripropylene glycol n-butyl ether.

[0116] From the viewpoint of ease of manufacturing water-based paints, the solvent preferably contains (i) one or more selected from the group consisting of water, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol n-butyl ether, and tripropylene glycol n-butyl ether, and may consist only of one or more selected from the group; and (ii) preferably contains water, and may consist only of water.

[0117] (Other optional components 2) Liquid B may contain components other than component (B) as needed (hereinafter sometimes referred to as "other optional components 2"). Examples of other optional components 2 include colorants such as pigments and dyes, extender pigments, pigment dispersants, ultraviolet absorbers, antioxidants, heat stabilizers (gelling inhibitors), stabilizers, plasticizers, leveling agents, defoamers, silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, viscosity thickeners, viscosity modifiers, thixotropy imparters, low shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, wetting agents, dispersants, anti-sagging agents, color separation inhibitors, settling inhibitors, coating wear modifiers, surface modifiers, film-forming aids, antibacterial agents, antifungal agents, preservatives, antifreeze agents, tackifiers, rust inhibitors, and the like.

[0118] (2-3. Anti-fouling agent) This water-based paint may further contain an antifouling agent. The antifouling agent may be contained in either liquid A or liquid B. Because this water-based paint has a small loss tangent (tanδ) at seawater temperature, it is considered to have antifouling properties against aquatic organisms even without containing an antifouling agent. Therefore, this water-based paint can be suitably used as an antifouling paint for underwater structures without containing an antifouling agent. Since the water-based paint can provide a coating film with superior antifouling properties against aquatic organisms and / or a coating film with longer-lasting antifouling properties against aquatic organisms, it is preferable that this water-based paint further contains an antifouling agent. On the other hand, a coating film obtained from a water-based paint without an antifouling agent is less susceptible to damage than a coating film obtained from a water-based paint containing an antifouling agent. Therefore, a coating film obtained from a water-based paint without an antifouling agent has the advantage of higher durability compared to a coating film obtained from a water-based paint containing an antifouling agent.

[0119] The antifouling agent is not particularly limited, and known antifouling agents can be used. Examples of antifouling agents include inorganic compounds, organic compounds containing metals, and organic compounds that do not contain metals.

[0120] Examples of antifouling agents include metal salts such as zinc oxide, cuprous oxide, 2-pyridinethiol-1-oxide zinc salt (also known as zinc pyrithione) and copper salts, pyrithione salt compounds, p-isopropylpyridinemethyldiphenylborane, pyridinetriphenylborane, tetramethylthiuram disulfide, and carbamate compounds (e.g., zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 3-iodo-2-propylbutylcarbamate, bisdimethyldithiocarbamoylzinc ethylenebisdithio Ocarbamate and manganese-2-ethylenebisdithiocarbamate, etc.), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyldichlorophenylurea, copper rhodane, 4,5-dichloro-2-n-octyl-3(2H)isothiazolon (also known as 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one), N-(fluorodichloromethylthio)phthalimide, N,N'-dimethyl-N'-phenyl (N-fluorodichloromethylthio)sulfamide, tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, diiodomethyl paratrisulfone, phenyl(bispyridyl)bismuth dichloride, 2-(4-thiazolyl)-benzimidazole, triphenylborone pyridine salt, stearylamine-triphenylborone, laurylamine-triphenylborone, 1,1-dichloro-N-[(dimethylamino)sulfone Examples include [nyl]-1-fluoro-N-phenylmethanesulfenamide, 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfenamide, N'-(3,4-dichlorophenyl)-N,N'-dimethylurea, N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine, and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile.

[0121] (2-4. Organic Solvents) This water-based paint may contain an organic solvent. The organic solvent may be contained in either liquid A or liquid B. This water-based paint has the advantage of excellent film-forming properties without containing an organic solvent. When a water-based paint contains an organic solvent, it has the advantage of even better film-forming properties. Examples of organic solvents include hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, alcohols, etc. Examples of organic solvents for hydrocarbons include n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, cyclohexane, methylcyclohexane, cyclopentane, toluene, xylene, benzene, ethylbenzene, decalin, white spirit, naphtha, etc. Examples of organic solvents for halogenated hydrocarbons include methylene chloride, chloroform, tetrachloroethane, trichloroethylene, etc. Examples of organic solvents for ethers include dioxane, ethyl ether, diethyl ether, butyl diglycol, 2-butoxyethanol, tetrahydrofuran, tetrahydropyran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as PMAC), propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, and dipropylene glycol dimethyl ether.Examples of organic solvents for esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, methoxypropyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, n-butyl acetate, and 2-ethoxyethyl acetate. Examples of organic solvents for ketones include acetone, methyl ethyl ketone, diethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone (also known as MIBK), methyl isoamyl ketone, and diacetone alcohol. Examples of organic solvents for alcohols include methanol, ethanol, n-propanol, (iso)propanol, n-butanol, isobutanol, benzyl alcohol, ethylene glycol, and propylene glycol. Mixtures of the above-mentioned alcohols and water can also be used as organic solvents. Examples of organic solvents include dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. These organic solvents may be used individually or in combination of two or more.

[0122] From the viewpoint of environmental protection and safety and health, the lower the organic solvent content in this water-based paint, the better. The organic solvent content in this water-based paint is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, even more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less per 100 parts by weight of the water-based paint.

[0123] (2-5. Others) This water-based paint may contain, as necessary, one or more additional liquids (for example, liquid C) in addition to liquids A and B. If this water-based paint contains, as necessary, liquid C in addition to liquids A and B, liquid C may contain components other than those described above (A) and (B). Examples of components other than those described above include the other optional component 1 and other optional components 2.

[0124] [3. Method for manufacturing water-based paints] The method for manufacturing this water-based paint is not particularly limited. For example, the following manufacturing method is preferred for manufacturing the water-based paint according to one embodiment of the present invention: (A) Step A is to prepare solution A containing an alkoxysilyl group-containing synthetic resin emulsion, and (B) Step B is to prepare solution B containing a substance that promotes hydrolysis and condensation of alkoxysilyl groups. The above step A involves monomer M represented by the following formula (1). 1 A monomer mixture for polyorganosiloxane formation containing monomers is polymerized to form monomer M. 1 The constituent unit U derived from 1 Step A-1 to obtain a polyorganosiloxane containing, and in the presence of the polyorganosiloxane obtained in step A-1, monomer M represented by the following formula (2) 2 A monomer mixture for graft formation containing is polymerized to form monomer M 2 The constituent unit U derived from 2 The process includes step A-2 of forming a graft portion including, In step A-1, the total amount of polyfunctional alkoxysilane compounds and polyfunctional monomers used in 100% by weight of the polyorganosiloxane-forming monomer mixture is 0.50% by weight or less, in a method for producing a water-based paint: R 1 m R 2 (4-m-n) SiX n ...(1) (In the formula, R 1 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 2 (where m is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are each independently integers between 1 and 3, and the sum of m and n is between 2 and 4); R 3 p R 4 (4-p-q) SiY q ...(2) (In the formula, R 3 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 4(where is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independent integers between 1 and 3, and the sum of p and q is between 2 and 4).

[0125] A method for manufacturing a water-based paint according to one embodiment of the present invention has the above configuration, and therefore can provide a water-based paint with excellent storage stability.

[0126] In this specification, "a method for producing a water-based paint according to one embodiment of the present invention" may also be referred to as "this manufacturing method."

[0127] The following describes each step of this manufacturing method in detail. However, there are no particular limitations on matters other than those described below (for example, various components and their amounts), and the explanation in the above section [2. Water-based paints] may be referred to as appropriate.

[0128] (3-1.Process A) Step A is a step of preparing liquid A containing (A) alkoxysilyl group-containing synthetic resin emulsion. Step A is a step of preparing monomer M represented by formula (1) in order to prepare (A) alkoxysilyl group-containing synthetic resin emulsion. 1 A monomer mixture for polyorganosiloxane formation containing monomers is polymerized to form monomer M. 1 The constituent unit U derived from 1 Step A-1 to obtain a polyorganosiloxane containing, and in the presence of the polyorganosiloxane obtained in step A-1, monomer M represented by formula (2) 2 A monomer mixture for graft formation containing is polymerized to form monomer M 2 The constituent unit U derived from 2 Step A includes forming a graft portion including (i) constituent unit U 1 (ii) a polyorganosiloxane that is non-crosslinked and contains (ii) a graft portion that is graft-bonded to the polyorganosiloxane, and is a constituent unit U 2 An emulsion of a synthetic resin containing an alkoxysilyl group and a graft portion containing can be obtained.

[0129] (Process A-1) Process A-1 is composed of component unit U 1 This is a step in preparing a polyorganosiloxane containing [a specific compound / substance].

[0130] The organosiloxane included in the monomer mixture for polyorganosiloxane formation is not particularly limited. In step A-1, it is preferable to use a known organosiloxane so that a polyorganosiloxane having the constituent units (organosiloxane system units) described in the section (organosiloxane system units) above is obtained.

[0131] In step A-1, for example, (a) dimethyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, (b) various organosiloxane cyclic compounds with three or more membered rings such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetradecamethylcycloheptasiloxane, and dimethylcyclics (a mixture of 3 to 7 dimethylsiloxane cyclic oligomers), and (c) dimethyldichlorosilane can be used as raw material organosiloxanes. In addition, linear or branched organosiloxanes can also be used as raw material organosiloxanes.

[0132] In step A-1, a pre-polymerized polyorganosiloxane may be used as the organosiloxane. In this case, the molecular chain ends of the polyorganosiloxane may be encapsulated with hydroxyl groups, alkoxy groups, trimethylsilyl groups, dimethylvinylsilyl groups, methylphenylvinylsilyl groups, methyldiphenylsilyl groups, etc.

[0133] Because they are readily available and easy to prepare, polyorganosiloxanes are readily available and readily available, the organosiloxanes used as raw materials in step A-1 are preferably various organosiloxane-based cyclic compounds with three or more membered rings, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetradecamethylcycloheptasiloxane, and dimethylcyclics (a mixture of 3 to 7 dimethylsiloxane cyclic oligomers).

[0134] Monomer M contained in the monomer mixture for polyorganosiloxane formation 1 Since this is the same as what was explained in the section on (polyorganosiloxanes) above, we will refer to that description and omit the explanation here.

[0135] Monomer M in process A-1 1 The amount used is the constituent unit U in the resulting polyorganosiloxane. 1 It correlates with the content of monomer M in process A-1. 1 The amount used is not particularly limited, but in 100% by weight of polyorganosiloxane, the constituent unit U 1 It is preferable that the amount used is such that the content is between 0.001% by weight and 10.0% by weight. Monomer M in step A-1 1 The amount used is preferably 0.001% to 10.0% by weight, more preferably 0.01% to 5.0% by weight, even more preferably 0.1% to 5.0% by weight, even more preferably 1.0% to 5.0% by weight, and particularly preferably 1.0% to 3.0% by weight, per 100% by weight of the monomer mixture for polyorganosiloxane formation. This configuration has the advantage that (a) polymerization of the monomer mixture for graft formation can be carried out efficiently in the presence of polyorganosiloxane.

[0136] In process A-1, organosiloxane and monomer M 1The polymerization method is not particularly limited, but for example, a known emulsion polymerization method carried out in the presence of an acidic emulsifier can be used.

[0137] The acidic emulsifier is not particularly limited, but when using organosiloxane-based cyclic compounds, it is preferable to use one that can open the ring of the organosiloxane-based cyclic compound. For example, dodecylbenzenesulfonic acid is a suitable acidic emulsifier. The amount of acidic emulsifier used is not particularly limited and can be appropriately set depending on (a) the desired volume-average particle size of the polyorganosiloxane and alkoxysilyl group-containing synthetic resin, (b) the concentration of solids (monomer mixture) in the reaction solution, (c) polymerization conditions such as polymerization temperature, and (d) whether or not additives such as surfactants are used and in what amounts.

[0138] The volume-average particle size of the resulting polyorganosiloxane can be controlled by (a) the degree of pre-dispersion of the raw materials, (b) the amount of emulsifier used, (c) the polymerization temperature, and (d) the method of supplying the raw materials.

[0139] When polyorganosiloxanes are obtained by emulsion polymerization in the presence of an acidic emulsifier, the resulting aqueous latex is strongly acidic, so it is preferable to neutralize it after the polymerization reaction is complete. The basic compound used for neutralization is not particularly limited, and examples include sodium hydroxide, potassium hydroxide, ammonia, and triethylamine. The aqueous latex containing the polyorganosiloxane can be neutralized by adding these basic compounds directly or in aqueous solution to the aqueous latex.

[0140] In step A-1, it is preferable that the total amount of polyfunctional alkoxysilane compounds and polyfunctional monomers used in 100% by weight of the monomer mixture for polyorganosiloxane formation is 0.50% by weight or less. With this configuration, a non-crosslinked polyorganosiloxane is obtained.

[0141] (Process A-2) Step A-2 is a graft portion that is graft-bonded to the polyorganosiloxane, and the constituent unit U 2This is a step in forming (preparing) a graft portion containing [the specified material]. The graft portion can be formed by polymerizing monomers used for graft formation (a mixture of monomers for graft formation) in the presence of a polyorganosiloxane by known radical polymerization.

[0142] When polyorganosiloxane is obtained by emulsion polymerization in the presence of the above-mentioned acidic emulsifier (i.e., when polyorganosiloxane is obtained as aqueous latex), polymerization of the graft portion is preferably carried out by emulsion polymerization. The graft portion can be produced, for example, by the method described in International Publication No. WO2005 / 028546.

[0143] The monomer mixture for graft formation is composed of constituent unit U 2 The monomer M from which it is derived 2 Includes monomer M. 2 Since this is the same as what was explained in the section on (graft portion) above, we will refer to that description and omit the explanation here.

[0144] The type and amount of monomers contained in the monomer mixture for graft formation can determine the type and amount of constituent units of the resulting graft. Therefore, the type and amount of monomers contained in the monomer mixture for graft formation should be set appropriately so that the graft described in the (graft) section above is obtained.

[0145] Monomer M in process A-2 2 The amount used is the constituent unit U in the resulting graft. 2 It correlates with the content of monomer M in process A-2. 2 The amount used is not particularly limited, but in 100% by weight of the graft portion, the constituent unit U 2 It is preferable that the amount used is such that the content is between 1.0% by weight and 80.0% by weight. Monomer M in step A-2 2The amount used is preferably 1.0% to 80.0% by weight, more preferably 1.0% to 75.0% by weight, more preferably 1.0% to 70.0% by weight, more preferably 1.0% to 65.0% by weight, more preferably 1.0% to 60.0% by weight, more preferably 1.5% to 55.0% by weight, more preferably 1.5% to 50.0% by weight, more preferably 1.5% to 45.0% by weight, more preferably 1.5% to 40.0% by weight, and more preferably 2.0% to 38.0% by weight, in 100% by weight of the monomer mixture for graft formation. It is more preferably 2.0% by weight or more and 35.0% by weight or less, more preferably 2.0% by weight or more and 33.0% by weight or less, more preferably 2.5% by weight or more and 30.0% by weight or less, more preferably 2.5% by weight or more and 28.0% by weight or less, more preferably 2.5% by weight or more and 25.0% by weight or less, more preferably 3.0% by weight or more and 23.0% by weight or less, more preferably 3.0% by weight or more and 20.0% by weight or less, more preferably 3.5% by weight or more and 18.0% by weight or less, more preferably 3.5% by weight or more and 15.0% by weight or less, even more preferably 4.0% by weight or more and 13.0% by weight or less, and particularly preferably 4.0% by weight or more and 10.0% by weight or less. This configuration has the advantages that (a) the water-based paint can provide a coating with a lower loss tangent (tanδ), and (b) blistering when the coating obtained from the water-based paint is immersed in water is reduced or eliminated.

[0146] In step A-2, when emulsion polymerization is employed, a pyrolysis-type initiator can be used as the radical polymerization initiator. Examples of known pyrolysis-type initiators include 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate.

[0147] Redox-type initiators can also be used as radical polymerization initiators. The redox-type initiator is an initiator that combines (a) peroxides such as organic peroxides and inorganic peroxides, and (b) optionally a reducing agent such as sodium formaldehyde sulfoxylate or glucose, optionally a transition metal salt such as iron(II) sulfate, optionally a chelating agent such as disodium ethylenediaminetetraacetate, and optionally a phosphorus-containing compound such as sodium pyrophosphate. Examples of organic peroxides include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide. Examples of inorganic peroxides include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

[0148] In this manufacturing method, it is preferable that the monomer mixture for polyorganosiloxane formation constitutes 55% to 95% by weight of the total 100% by weight of the monomer mixture for polyorganosiloxane formation and the monomer mixture for graft formation. This configuration has the advantage of providing a water-based paint that can provide a coating film with excellent water repellency. In this manufacturing method, it is more preferable that the monomer mixture for polyorganosiloxane formation constitutes 55% to 95% by weight of the total 100% by weight of the monomer mixture for polyorganosiloxane formation and the monomer mixture for graft formation, more preferably 60% to 95% by weight, even more preferably 65% ​​to 95% by weight, and particularly preferably 70% to 95% by weight. This configuration has the advantage of providing a water-based paint that can provide a coating film with superior water repellency and superior film-forming properties.

[0149] Monomer M in this manufacturing method 2 The amount used is the constituent unit U in the resulting alkoxysilyl group-containing synthetic resin. 2 This correlates with the content of monomer M in this manufacturing method. 2The amount used is not particularly limited, but in 100% by weight of the alkoxysilyl group-containing synthetic resin, the constituent unit U 2 It is preferable that the amount used is such that the content of is 0.5% by weight or more. Also, monomer M in this manufacturing method 2 The amount used is, in 100% by weight of the alkoxysilyl group-containing synthetic resin, the constituent unit U 2 It is preferable that the amount used is such that the content is 5.0% by weight or less. Monomer M in this manufacturing method 2 The amount used is preferably 0.5% by weight or more, more preferably 0.8% by weight or more, more preferably 1.0% by weight or more, more preferably 1.3% by weight or more, even more preferably 1.5% by weight or more, and particularly preferably 2.0% by weight or more, based on 100% by weight of the total monomer mixture for polyorganosiloxane formation and monomer mixture for graft formation. This configuration has the advantage of improving the strength of the coating film. Monomer M in this manufacturing method 2 The amount used is preferably 5.0% by weight or less, more preferably 4.0% by weight or less, more preferably 3.0% by weight or less, even more preferably 2.0% by weight or less, even more preferably 1.8% by weight or less, and particularly preferably 1.5% by weight or less, based on 100% by weight of the total monomer mixture for polyorganosiloxane formation and monomer mixture for graft formation. This configuration has the advantage of improving film-forming properties.

[0150] Since the storage stability of the alkoxysilyl group-containing synthetic resin emulsion is greatly improved, the monomer mixture for graft formation in step A-2 preferably contains one or more selected from the group consisting of (meth)acrylate monomers having an alkyl group having 4 or more carbon atoms and (meth)acrylate monomers having a cycloalkyl group having 4 or more carbon atoms, and may also consist only of one or more constituent units selected from the said group. Since the storage stability of the alkoxysilyl group-containing synthetic resin emulsion is greatly improved, the monomer mixture for graft formation in step A-2 preferably contains 60% by weight or more of one or more selected from the group consisting of (meth)acrylate monomers having an alkyl group having 4 or more carbon atoms and (meth)acrylate monomers having a cycloalkyl group having 4 or more carbon atoms, in a quantity of 100% by weight of the monomer mixture for graft formation, more preferably 60% by weight or more and 99% by weight or less, more preferably 62% by weight or more and 98% by weight or less, even more preferably 65% ​​by weight or more and 97% by weight or less, particularly preferably 68% by weight or more and 96% by weight or less, and most preferably 70% by weight or more and 95% by weight or less.

[0151] The monomer mixture for graft formation in step A-2 preferably contains a reactive emulsifier. The reactive emulsifier is the same as that described in the section above (Constituent units derived from the reactive emulsifier), so that description is used as a reference and the explanation is omitted here. For example, the amount of reactive emulsifier used in step A-2 is preferably 0.1% by weight or more and 20.0% by weight or less, more preferably 0.1% by weight or more and 15.0% by weight or less, more preferably 1.0% by weight or more and 15.0% by weight or less, more preferably 1.0% by weight or more and 10.0% by weight or less, even more preferably 1.0% by weight or more and 8.0% by weight or less, even more preferably 1.0% by weight or more and 5.0% by weight or less, and particularly preferably 1.0% by weight or more and 4.0% by weight or less. When the amount of reactive emulsifier used in step A-2 is within the above range, there is an advantage that the generation of scale during the manufacture of water-based paint is further reduced or eliminated.

[0152] The monomer mixture for graft formation in step A-2 may or may not contain a chain transfer agent. Since the chain transfer agent is the same as that described in the section above (Constituent units derived from the chain transfer agent), that description is used here and its explanation is omitted.

[0153] In the polymerization of each monomer mixture in the manufacture of water-based paints, emulsifiers and surfactants can be used in addition to the components described above. The types and amounts of emulsifiers and surfactants used are within a known range.

[0154] In the manufacture of water-based paints, the polymerization temperature, pressure, and deoxygenation conditions for the polymerization of each monomer mixture can be those within a known range.

[0155] By carrying out step A, including step A-2, an emulsion containing an alkoxysilyl group-containing synthetic resin can be obtained. As described above, in step A-2, a non-grafted polymer may be obtained along with the grafted portion. The non-grafted polymer may form an emulsion together with the alkoxysilyl group-containing synthetic resin. In other words, if the non-grafted polymer is not removed from the emulsion in step A-2, an emulsion containing the alkoxysilyl group-containing synthetic resin and the non-grafted polymer may be obtained.

[0156] The emulsion containing the alkoxysilyl group-containing synthetic resin obtained by carrying out step A may be used as is, or diluted with water (e.g., deionized water) as needed, and used as solution A. The emulsion obtained by carrying out step A may be further to which an antifouling agent described later, an organic solvent described later, and / or the other optional component 1 described above are added to make solution A. In other words, step A may further include step A-3, in which an antifouling agent is added to the emulsion obtained in step A-2. The antifouling agent and organic solvent are described below in (2-3. Antifouling Agent) and (2-4. Organic Solvent), so refer to those descriptions and omit the explanation here. The other optional component 1 is the same as the one described above in (Other Optional Component 1), so refer to that description and omit the explanation here.

[0157] (3-2.Process B) Step B is a step of preparing solution B. Step B is not particularly limited. For example, step B may involve using a stirrer to mix the raw materials containing component (B), and optionally the solvent and other optional components 2.

[0158] [4. How to use water-based paints (method of manufacturing the paint film)] The method of using this water-based paint can also be described as a method of applying a coating film (e.g., an antifouling coating film) using a water-based paint. The method of using this water-based paint includes the step of applying the water-based paint to an underwater structure. Specifically, the method of using the water-based paint according to one embodiment of the present invention includes the step of applying the water-based paint according to one embodiment of the present invention described in section [2. Water-based paint], or the water-based paint obtained by the method of manufacturing the water-based paint according to one embodiment of the present invention described in section [3. Method of manufacturing water-based paint], to an underwater structure. The method of using the water-based paint can also be described as a method of manufacturing a coating film. Specifically, the method of manufacturing a coating film according to one embodiment of the present invention includes the step of applying the water-based paint according to one embodiment of the present invention described in section [2. Water-based paint], or the water-based paint obtained by the method of manufacturing the water-based paint according to one embodiment of the present invention described in section [3. Method of manufacturing water-based paint], to an underwater structure. This water-based paint has excellent film-forming properties. Therefore, by applying the water-based paint to an underwater structure, an antifouling coating film can be easily formed on the surface or inner surface of the underwater structure. Furthermore, in a preferred embodiment of the present invention, by implementing a method of using a water-based paint, it is possible to form a coating on the surface or interior surface of an underwater structure that is free of cracks or has very few cracks. In other words, in a preferred embodiment of the present invention, by implementing a method of using a water-based paint, it is possible to provide a coating on the surface or interior surface of an underwater structure that has excellent antifouling properties (for example, antifouling properties against aquatic organisms).

[0159] When using (applying) this water-based paint, liquid A and liquid B are mixed before use, in other words, before application. The method of mixing liquid A and liquid B is not particularly limited, and conventionally known methods can be used as appropriate. The mixture obtained by mixing liquid A and liquid B is applied to the object to be coated (e.g., an underwater structure) and dried to form a coating film on the object to be coated (e.g., an underwater structure). It is preferable that the mixture obtained by mixing liquid A and liquid B be applied to the object to be coated (e.g., an underwater structure) as soon as possible after preparation, for example, within 3 hours.

[0160] The method of applying the water-based paint in the coating process is not particularly limited, and known methods can be used. Examples of application methods include casting, dipping, spraying, brushing, rollers, dip coaters, electrostatic coating, and electrodeposition coating.

[0161] In the coating process, a coating robot may be used. Using a coating robot, the water-based coating can be extruded onto the underwater structure in a bead, monofilament, or swirl pattern. Alternatively, the water-based coating can be applied to the underwater structure using a jet spray method or a streaming method.

[0162] The water-based paint applied to the underwater structure may be dried. As described above, by applying the water-based paint to the underwater structure and optionally drying the water-based paint, it is possible to form a coating on the surface or interior surface of the underwater structure that is free of cracks or has very few cracks. As a result, by applying the water-based paint to the underwater structure and optionally drying the water-based paint, it is possible to form a coating on the surface or interior surface of the underwater structure that has antifouling properties.

[0163] A method for using a water-based paint or a method for manufacturing a coating film according to one embodiment of the present invention may have the following configuration.

[0164] A method for using a water-based paint or a method for manufacturing a paint film, including the step of applying a water-based paint to an underwater structure: Here, the water-based paint is, (A) Solution A containing an alkoxysilyl group-containing synthetic resin emulsion, (B) Solution B containing a substance that promotes the hydrolysis and condensation of alkoxysilyl groups, The alkoxysilyl group-containing synthetic resin comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane. The polyorganosiloxane is composed of (a) constituent units U derived from monomers represented by the following formula (1). 1(b) is non-crosslinked, The graft portion is composed of constituent units U derived from monomers represented by the following formula (2). 2 Includes: R 1 m R 2 (4-m-n) SiX n ...(1) (In the formula, R 1 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 2 (where m is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are each independently integers between 1 and 3, and the sum of m and n is between 2 and 4); R 3 p R 4 (4-p-q) SiY q ...(2) (In the formula, R 3 R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, 4 (where is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independent integers between 1 and 3, and the sum of p and q is between 2 and 4).

[0165] [5. Coating film] A coating film formed by the method described in section [4. Method of using water-based paint (method of manufacturing a coating film)] is also one embodiment of the present invention. That is, (a) a coating film made of the water-based paint described in section [2. Water-based paint], or (b) a coating film made of water-based paint manufactured by the manufacturing method described in section [3. Method of manufacturing water-based paint] is also one embodiment of the present invention. A coating film according to one embodiment of the present invention can also be said to include (a) the water-based paint described in section [2. Water-based paint], or (b) a water-based paint manufactured by the manufacturing method described in section [3. Method of manufacturing water-based paint].

[0166] [6.Applications] This water-based paint can be suitably used as an antifouling coating for the surface or interior surface of various underwater structures. Examples of underwater structures include ships, materials for aquaculture and fishing (e.g., ropes, fishing nets, fishing gear, floats, buoys, tetrapods, etc.), oil booms, piping such as water inlets and outlets for thermal or nuclear power plants, cooling water conduits and seawater utilization equipment, underwater tunnels, underwater bases, megafloats, port facilities, canals and waterways, various marine civil engineering works, industrial water systems, bridges, buoys, and more. [Examples]

[0167] One embodiment of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. One embodiment of the present invention can be implemented with appropriate modifications within the scope that is consistent with the spirit described above or below, and all such modifications are included within the technical scope of the present invention. In the following examples and comparative examples, "parts" and "%" mean parts by weight or weight percent.

[0168] <Evaluation Method> First, the evaluation methods for the alkoxysilyl group-containing synthetic resins and water-based paints produced by the examples and comparative examples are described below.

[0169] (Measurement of volume-average particle diameter) The volume-average particle size (Mv) of polyorganosiloxanes dispersed in aqueous latex or alkoxysilyl group-containing synthetic resins dispersed in emulsions was measured using a Nanotrac WaveII-EX150 (Microtrac Bell Co., Ltd.). Aqueous latex or emulsions diluted with deionized water were used as measurement samples. Measurements were performed by inputting the refractive index of water and the polyorganosiloxane or alkoxysilyl group-containing synthetic resin obtained in each production example, adjusting the sample concentration to a loading index of 1 to 10 with a measurement time of 120 seconds.

[0170] (Method for evaluating the film-forming properties of water-based paints) The film-forming properties of the water-based paints were evaluated by the following method: (1) Mix 100 parts by weight of liquid A and 1 part by weight of liquid B for each water-based paint; (2) After preparing the mixture (water-based paint), apply the mixture to an aluminum plate with an applicator as soon as possible (at least within 3 hours) so that the film thickness after drying would be 100 μm; (3) Leave the resulting aluminum plate to stand overnight at 25°C to create a coating of the water-based paint; (4) Visually inspect the surface condition of the resulting aluminum plate and evaluate the film-forming properties according to the following criteria. 2 (Good): No cracks, 1 (Defective): Crack present.

[0171] (Example 1) ((A) Production of synthetic resin emulsion containing alkoxysilyl groups) (Preparation of polyorganosiloxanes) 251 parts by weight of deionized water, 0.5 parts by weight of sodium dodecyl sulfate (SDS), and monomer mixture for polyorganosiloxane formation (100 parts by weight of octamethylcyclotetrasiloxane as organosiloxane, and monomer M 1A mixture consisting of 2 parts by weight of 3-acryloyloxypropyldimethoxymethylsilane was added. The resulting mixture was stirred at 10,000 rpm for 5 minutes using a homomixer to prepare an emulsion. The entire amount of the resulting emulsion was poured at once into a five-necked glass container. The glass container had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and ports for adding monomers and emulsifiers. While stirring the added raw materials, (i) an amount equivalent to 1 part by weight of the solids in a 10% aqueous solution of dodecylbenzenesulfonic acid (DSA) was added to the glass container, then (ii) the temperature inside the glass container was raised to 80°C over approximately 40 minutes, and (iii) the mixture inside the glass container was then reacted at 80°C for 6 hours. After that, the temperature inside the glass container was cooled to 25°C, and after the temperature inside the glass container reached 25°C, the reaction solution inside the glass container was left to stand for 20 hours. Subsequently, polymerization was terminated by adjusting the pH of the reaction solution to pH 6.8 using sodium hydroxide. Through these steps, an aqueous latex (R-1) containing polyorganosiloxane was obtained. The polymerization conversion rate of the monomer components was 97%. The volume-average particle size of the polyorganosiloxane contained in the obtained aqueous latex (R-1) was 280 nm.

[0172] (Preparation of the graft) Next, 275.5 parts by weight of aqueous latex polyorganosiloxane (R-1) (containing 70 parts by weight of polyorganosiloxane) was added to the glass reactor. The glass reactor was equipped with a thermometer, a stirrer, reflux condenser, nitrogen inlet, and monomer addition device. The added raw materials were stirred at 60°C while replacing the gas in the glass reactor with nitrogen. Next, 0.004 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.13 parts by weight of sodium formaldehyde sulfoxylate (SFS) were added to the glass reactor and stirred for 10 minutes. After that, a monomer mixture for graft formation (28.5 parts by weight of butyl methacrylate (BMA) and monomer M) was added. 2A mixture consisting of 1.5 parts by weight of 3-methacryloxypropyltriethoxysilane and 0.085 parts by weight of BHP was continuously added to a glass reactor over 120 minutes. Subsequently, 0.013 parts by weight of t-butyl hydroperoxide (BHP) was added to the glass reactor, and stirring of the mixture in the glass reactor was continued for another hour to complete the polymerization (production) of the alkoxysilyl group-containing synthetic resin. Through the above operations, an emulsion containing the alkoxysilyl group-containing synthetic resin, i.e., (A) alkoxysilyl group-containing synthetic resin emulsion (A-1), was obtained. The polymerization conversion rate of the monomer components was 97% or higher. The volume-average particle size of the alkoxysilyl group-containing synthetic resin contained in (A) alkoxysilyl group-containing synthetic resin emulsion (A-1) was 293 nm. The solid content of (A) alkoxysilyl group-containing synthetic resin emulsion was measured using an electronic moisture meter and was found to be 31 parts by weight. (A) In the alkoxysilyl group-containing synthetic resin emulsion (A-1), the polyorganosiloxane can be considered a core portion composed solely of polyorganosiloxane.

[0173] (Preparation of Solution A) 83 parts by weight of the obtained (A) alkoxysilyl group-containing synthetic resin emulsion (A-1) was mixed with 10 parts by weight of deionized water, 0.6 parts by weight of CS-12 (manufactured by JNC Corporation) as a film-forming aid, 0.2 parts by weight of SN Thickener 612NC (manufactured by Sunopco Corporation) as a thickening agent, 0.2 parts by weight of BYK-333 (manufactured by Bic Chemie Japan Corporation) as a leveling agent, and 0.4 parts by weight of Agitan 295 (manufactured by Munzing Chemie Corporation) as an antifoaming agent to obtain solution A.

[0174] (Preparation of Solution B) (B) One part by weight of Neostan U220 (dibutyltin diacetylacetonate, manufactured by Nitto Chemical Co., Ltd.) and one part by weight of dipropylene glycol n-butyl ether were mixed to obtain solution B.

[0175] Through the above operations, liquid A and liquid B were obtained. In other words, a water-based paint comprising liquid A and liquid B was obtained through the above operations.

[0176] (Examples 2 to 9 and Comparative Examples 1 to 2) In the preparation of the graft portion, an emulsion containing an alkoxysilyl group-containing synthetic resin, i.e., (A) alkoxysilyl group-containing synthetic resin emulsion, was obtained by the same method as in Example 1, except that the amount of aqueous latex polyorganosiloxane (R-1) used was changed to the amount indicated in the "Core portion (polyorganosiloxane) content" column of Table 1 or 2, and the monomers used for graft portion formation in the preparation of the graft portion were changed to the monomer mixture indicated in the "Monomer mixture for graft portion formation" column of Table 1 or 2. Subsequently, liquids A and B were prepared by the same method as in Example 1. By the above operations, a water-based paint comprising liquids A and B was obtained.

[0177] The film-forming properties of the obtained water-based paints were evaluated after one week or one month. For the evaluation of film-forming properties after one week, the following (A1) and (A2) were performed in order: (A1) The water-based paint was left in a 25°C environment for one week from the time of manufacture of liquid A; (A2) The film-forming properties of liquid A after one week were evaluated using the method described in the section (Evaluation Method for Film-Forming Properties of Water-Based Paints) above. The results obtained are shown in the "Film-Forming Properties of Water-Based Paints (After One Week)" column of Tables 1 and 2. For the evaluation of film-forming properties after one month, the following (B1) and (B2) were performed in order: (B1) The water-based paint was left in a 25°C environment for one month from the time of manufacture of liquid A; (B2) The film-forming properties of liquid A after one month were evaluated using the method described in the section (Evaluation Method for Film-Forming Properties of Water-Based Paints) above. The results obtained are shown in the "Film-Forming Properties of Water-Based Paints (After One Month)" column of Tables 1 and 2.

[0178] Furthermore, even just solution A from Examples 1 to 9 can be considered a water-based paint according to one embodiment of the present invention.

[0179] (Example 10) The film-forming properties of the water-based paint consisting only of liquid A in Example 3 were evaluated. The film-forming properties were evaluated by following steps (C1) to (C4) in order: (C1) The water-based paint was left in an environment of 25°C for one week after the manufacture of liquid A; (C2) The water-based paint consisting only of liquid A, after being left for one week, was applied to an aluminum plate with an applicator so that the film thickness after drying was 100 μm; (C3) The obtained aluminum plate was left to stand overnight at 25°C to create a coating film of the water-based paint consisting only of liquid A; (C4) The condition of the coated surface of the obtained aluminum plate was visually checked, and the film-forming properties of the coating film consisting only of liquid A were evaluated according to the criteria described in the section (Method for evaluating the film-forming properties of water-based paint). The film-forming properties were rated 2 (good). On the other hand, the coating film obtained from the water-based paint consisting only of liquid A crumbled when touched, resulting in low coating film strength.

[0180] [Table 1]

[0181] [Table 2] [Industrial applicability]

[0182] According to one embodiment of the present invention, a water-based paint with excellent storage stability can be provided. Therefore, the water-based paint according to one embodiment of the present invention, and the coating film made of the water-based paint, can be suitably used for ships, materials for aquaculture and fishing, oil booms, piping such as water inlets and outlets for thermal or nuclear power plants, cooling water conduits and seawater utilization equipment, various marine civil engineering works such as submarine tunnels, submarine bases, megafloats, port facilities, canals and waterways, industrial water systems, bridges, buoys and other underwater structures.

Claims

1. (A) Solution A containing an alkoxysilyl group-containing synthetic resin emulsion, (B) A multi-component water-based paint comprising liquid B containing a substance that promotes the hydrolysis and condensation of alkoxysilyl groups, The alkoxysilyl group-containing synthetic resin comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane. The polyorganosiloxane is (a) a constituent unit U derived from a monomer represented by the following formula (1) １ (b) is non-crosslinked, The graft portion is composed of constituent units U derived from monomers represented by the following formula (2). ２ Water-based paints, including: R １ ｍ R ２ （４－ｍ－ｎ） SiX ｎ ・・・(1) (wherein, R １ is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, R ２ is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are each independently an integer of 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less); R ３ ｐ R ４ （４－ｐ－ｑ） SiY ｑ ・・・(2) (In the formula, R ３ R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, ４ (where is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independently integers between 1 and 3, and the sum of p and q is between 2 and 4).

2. The water-based paint according to claim 1, wherein the graft portion contains 60% by weight or more of one or more constituent units selected from the group consisting of constituent units derived from (meth)acrylate monomers having an alkyl group having 4 or more carbon atoms and constituent units derived from (meth)acrylate monomers having a cycloalkyl group having 4 or more carbon atoms, in 100% by weight of the graft portion.

3. The water-based paint according to claim 1 or 2, wherein the substance that promotes the hydrolysis and condensation of the alkoxysilyl group (B) includes one or more selected from the group consisting of organometallic compounds, alkali metal compounds, acidic catalysts, and basic catalysts.

4. The alkoxysilyl group-containing synthetic resin contains, in 100% by weight of the alkoxysilyl group-containing synthetic resin, the constituent unit U ２ A water-based paint according to claim 1 or 2, containing 0.5% by weight or more of the following.

5. A water-based paint according to claim 1 or 2, further comprising an antifouling agent.

6. A method for manufacturing a coating film, comprising the step of applying the water-based paint described in claim 1 or 2 to an underwater structure.

7. The present invention comprises an alkoxysilyl group-containing synthetic resin emulsion containing a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane, The polyorganosiloxane is (a) a constituent unit U derived from a monomer represented by the following formula (1) １ (b) is non-crosslinked, The graft portion is composed of constituent units U derived from monomers represented by the following formula (2). ２ Water-based paints, including: R １ ｍ R ２ （４－ｍ－ｎ） SiX ｎ ・・・(1) (In the formula, R １ R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, ２ (where is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, m and n are each independently integers between 1 and 3, and the sum of m and n is between 2 and 4); R ３ ｐ R ４ （４－ｐ－ｑ） SiY ｑ ・・・(2) (In the formula, R ３ R is a monovalent organic group having an ethylenically unsaturated group and / or a mercapto group, ４ (where is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 2 to 4 carbon atoms, p and q are each independently integers between 1 and 3, and the sum of p and q is between 2 and 4).

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