Water-based coatings

Abstract

The objective of this invention is to provide a waterborne coating with excellent storage stability. This waterborne coating is a multi-component waterborne coating comprising a liquid A and a liquid B, wherein liquid A comprises (A) an emulsion of a synthetic resin containing alkoxysilyl groups, and liquid B comprises (B) a substance that promotes the hydrolysis / condensation of alkoxysilyl groups. The synthetic resin containing alkoxysilyl groups comprises a polyorganosiloxane having a specific structure and a graft portion having a specific composition.

Description

Technical Field

[0001] This invention relates to water-based coatings. Background Technology

[0002] Various coatings have been developed as paints (e.g., antifouling coatings). Currently, solvent-based coatings are the mainstream, but in recent years, from the perspective of environmental protection and safety, the shift to water-based coatings is progressing rapidly. As a water-based coating, the technology described in Patent Document 1 can be cited as an example.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2024-143794 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, from the perspective of storage stability, as mentioned above, the existing technology has shortcomings and room for further improvement.

[0008] In view of the above problems, one embodiment of the present invention aims to provide a novel waterborne coating with excellent storage stability.

[0009] Problem Solving Methods

[0010] In order to solve the above problems, the inventors conducted in-depth research and completed the present invention.

[0011] That is, one embodiment of the waterborne coating of the present invention is a multi-liquid waterborne coating comprising liquid A and liquid B, wherein liquid A comprises (A) an emulsion of a synthetic resin containing alkoxysilyl groups, and liquid B comprises (B) a substance that promotes the hydrolysis / condensation of alkoxysilyl groups, wherein the synthetic resin containing alkoxysilyl groups comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane, wherein the polyorganosiloxane (a) comprises a structural unit U from a monomer represented by the following formula (1). 1 Furthermore, (b) the grafted portion is non-crosslinked, comprising structural units U derived from the monomer represented by the following formula (2). 2 ,

[0012] R 1 m R 2 (4-m-n) SiX n ···(1)

[0013] (where R is in the formula) 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2X is an alkyl group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less.

[0014] R 3 p R 4 (4-p-q) SiY q ··· (2)

[0015] (where R is in the formula) 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an independent integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0016] Another embodiment of the waterborne coating of the present invention comprises an emulsion of a synthetic resin containing alkoxysilyl groups, the emulsion of the synthetic resin containing alkoxysilyl groups comprising a polyorganosiloxane and graft portions grafted to the polyorganosiloxane, wherein the polyorganosiloxane (a) comprises a structural unit U derived from a monomer represented by the following formula (1). 1 Furthermore, (b) the grafted portion is non-crosslinked, comprising structural units U derived from the monomer represented by the following formula (2). 2 ,

[0017] R 1 m R 2 (4-m-n) SiX n ···(1)

[0018] (where R is in the formula) 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 X is an alkyl group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less.

[0019] R 3 p R 4 (4-p-q) SiY q ···(2)

[0020] (where R is in the formula) 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an independent integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0021] The effects of the invention

[0022] According to one embodiment of the present invention, it is possible to achieve the effect of providing water-based coatings with excellent storage stability. Detailed Implementation

[0023] The following describes one embodiment of the present invention, but the invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope shown in the claims. Furthermore, embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included within the technical scope of the present invention. Moreover, new technical features can be formed by combining the technical means disclosed in each embodiment. It should be noted that all academic and patent documents described in this specification are incorporated herein by reference.

[0024] In this specification, the "structural unit derived from monomer X" contained in a polymer, copolymer or resin is sometimes referred to as "unit X".

[0025] [1. Technical concept of one embodiment of the present invention]

[0026] From the perspective of storage stability, existing water-based coatings as described in Patent Document 1 have shortcomings and room for further improvement. Specifically, the inventors have independently discovered the following insight: although existing water-based coatings as described in Patent Document 1 have excellent film-forming properties immediately after manufacturing, they exhibit poor film-forming properties after a long period (e.g., more than one week), i.e., poor storage stability.

[0027] The inventors conducted in-depth research into the reasons for the poor storage stability of existing water-based coatings. During this research, the inventors focused on the hydrolyzable silane groups of the copolymers contained in the water-based coatings described in Patent Document 1, and conducted further in-depth studies. As a result, the inventors independently discovered the following new insights, thereby completing this invention.

[0028] As long as the water-based coating contains a copolymer with a shell of alkoxy groups containing a specific number of carbon atoms, it will have excellent film-forming properties, i.e., excellent storage stability, even after a long period of time since its manufacture.

[0029] [2. Water-based coatings]

[0030] One embodiment of the present invention is a multi-component waterborne coating comprising liquid A and liquid B, wherein liquid A comprises (A) an emulsion of a synthetic resin containing alkoxysilyl groups, and liquid B comprises (B) a substance that promotes the hydrolysis / condensation of alkoxysilyl groups. The synthetic resin containing alkoxysilyl groups comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane. The polyorganosiloxane (a) comprises a structural unit U derived from a monomer represented by the following formula (1). 1 Furthermore, (b) the grafted portion is non-crosslinked, comprising structural units U derived from the monomer represented by the following formula (2). 2 ,

[0031] R 1 m R 2 (4-m-n) SiX n ···(1)

[0032] (where R is in the formula) 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 X is an alkyl group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less.

[0033] R 3 p R 4 (4-p-q) SiY q ···(2)

[0034] (where R is in the formula) 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an independent integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0035] In this specification, the term "aqueous coating of one embodiment of the present invention" is sometimes referred to as "the present water-based coating".

[0036] This waterborne coating, due to its aforementioned composition, possesses the advantage of excellent storage stability. The storage stability of the waterborne coating can be evaluated by assessing its film-forming properties using a sample of the waterborne coating after a long period (e.g., one week) since manufacturing. If the waterborne coating exhibits excellent film-forming properties after a long period (e.g., one week) since manufacturing, its storage stability is considered excellent. Furthermore, it is considered that a waterborne coating with excellent film-forming properties can be provided, and the longer the period since manufacturing, the better the storage stability of the waterborne coating. In this specification, the method for evaluating the "film-forming properties" of the waterborne coating is described in detail in the following examples. Additionally, in a preferred embodiment of the invention, the waterborne coating can provide a film completely free of cracks or with very few cracks even if present, through the hydrolysis and condensation of alkoxysilyl groups in the waterborne coating. A film completely free of cracks or with very few cracks is considered to have excellent antifouling properties (e.g., antifouling against aquatic organisms). Therefore, in a preferred embodiment of the present invention, the waterborne coating can provide a film with excellent antifouling properties (e.g., antifouling against aquatic organisms) through the hydrolysis and condensation of alkoxysilyl groups in the waterborne coating.

[0037] This water-based coating contains at least liquid A and liquid B. This water-based coating is a multi-liquid type. In this specification, "multi-liquid type" does not mean a single-liquid type formed by only one liquid, but rather a two-liquid type formed by at least two liquids. If this water-based coating consists only of liquid A and liquid B, it can be considered a "two-liquid type".

[0038] (2-1. Solution A)

[0039] ((A) Emulsion of synthetic resin containing alkoxysilane)

[0040] Liquid A comprises an emulsion of (A) an alkoxysilyl-containing synthetic resin. The emulsion of (A) an alkoxysilyl-containing synthetic resin may also be referred to as an emulsion of (A) an alkoxysilyl-containing synthetic resin. Liquid A may be considered as (i) an emulsion of an alkoxysilyl-containing synthetic resin, (ii) an emulsion containing an alkoxysilyl-containing synthetic resin, or (iii) a liquid in which an alkoxysilyl-containing synthetic resin is dispersed. In this specification, "(A) an emulsion of an alkoxysilyl-containing synthetic resin" is sometimes referred to as "(A) component".

[0041] (2-1-1. Synthetic resins containing alkoxysilyl groups)

[0042] (A) The alkoxysilyl-containing synthetic resin in the composition comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane.

[0043] (Polyorganosiloxane)

[0044] Polyorganosiloxanes contain structural units U derived from monomers represented by the following formula (1). 1 ,

[0045] R 1 m R 2 (4-m-n) SiX n ···(1)

[0046] In the formula, R 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 X is an alkyl group with 1 or more carbon atoms and 4 or less, X is an alkoxy group with 1 or more carbon atoms and 4 or less, m and n are each an integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less.

[0047] As R 1 Examples of olefinic unsaturated groups in olefins include vinyl, acryloyl, and methacryloyl groups.

[0048] In structural unit U 1 Contains 2 or more R 1 In other words, when m is 2 or 3, multiple R 1彼此 They can be the same or different.

[0049] As R 2 Examples include methyl, ethyl, propyl, and butyl.

[0050] Structural unit U 1 It is also possible to omit R. 2 In structural unit U 1 Contains 2 Rs 2 In other words, when the value (difference) of "4-mn" is 2, multiple R 2 They can be the same or different.

[0051] Examples of X include methoxy, ethoxy, propoxy, and butoxy.

[0052] In the case where the single entity represented by equation (1) contains 2 X, in other words, when n is 2 or 3, the multiple X can be the same as each other or different.

[0053] In this specification, the "monomer represented by formula (1)" is sometimes referred to as "monomer M". 1 ".

[0054] As a monomer M 1Specific examples include: (a) vinyl methyl dimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, tetramethyl tetravinylcyclotetrasiloxane, and other vinyl silanes; (b) β-methacryloyloxyethyl dimethoxymethylsilane, 3-(meth)acryloyloxypropyl trimethoxysilane, 3-(meth)acryloyloxypropyl dimethoxymethylsilane, 3-(meth)acryloyloxypropyl methoxydimethylsilane, 3-(meth)acryloyloxypropyl triethoxysilane, 3-( Methacryloyloxypropyldiethoxyethylsilane, 3-(methacryloyloxypropylethoxydimethylsilane, 3-(methacryloyloxypropylethoxydiethylsilane, δ-(methacryloyloxybutyldiethoxymethylsilane) and other (meth)acryloyloxyalkylsilanes, and (c)3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropylmethoxydimethylsilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyldiethoxyethylsilane and other mercaptoalkylsilanes, etc. Additionally, as a 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, etc. These monomers M 1 One type can be used alone, or two or more types can be used in combination.

[0055] As a monomer M 1Preferably, it is selected from one or more of the following (meth)acryloyloxyalkyl silanes: β-methacryloyloxyethyl dimethoxymethylsilane, 3-(meth)acryloyloxypropyl trimethoxysilane, 3-(meth)acryloyloxypropyl dimethoxymethylsilane, 3-(meth)acryloyloxypropyl methoxydimethylsilane, 3-(meth)acryloyloxypropyl triethoxysilane, 3-(meth)acryloyloxypropyl diethoxymethylsilane, 3-(meth)acryloyloxypropyl diethoxyethylsilane, 3-(meth)acryloyloxypropyl ethoxydimethylsilane, 3-(meth)acryloyloxypropyl ethoxydiethylsilane, and δ-(meth)acryloyloxybutyl diethoxymethylsilane. More preferably, it is selected from one or more of the following meth)acryloyloxyalkyl silanes: 3-(meth)acryloyloxypropyl trimethoxysilane and 3-(meth)acryloyloxypropyl dimethoxymethylsilane. This configuration offers the advantage of efficiently performing graft formation (polymerization) in the presence of polyorganosiloxanes. Consequently, it provides the advantage of obtaining synthetic resins containing alkoxysilanes with high grafting rates.

[0056] In 100% by weight of the polyorganosiloxane, the polyorganosiloxane preferably contains 0.001% by weight and less than 10.0% by weight of the structural unit U. 1 More preferably, it contains 0.01% by weight or more and 5.0% by weight or less; even more preferably, it contains 0.1% by weight or more and 5.0% by weight or less; even more preferably, it contains 1.0% by weight or more and 5.0% by weight or less; and particularly preferably, it contains 1.0% by weight or more and 3.0% by weight or less. According to this composition, it has the advantage of being able to efficiently carry out the formation (polymerization) of the grafted portion in the presence of the polyorganosiloxane. As a result, it has the advantage of being able to obtain a synthetic resin containing alkoxysilane with a high grafting rate.

[0057] <Organosiloxane units>

[0058] Polyorganosiloxanes may further comprise organosiloxane units. There are no particular limitations on the organosiloxane units. Examples of organosiloxane units include structural units having at least one organic group and a silanoxy group.

[0059] Examples of organosiloxane units include: (a) alkyl or aryl 2-substituted siloxane units such as dimethylsiloxane unit, diethylsiloxane unit, methylphenylsiloxane unit, diphenylsiloxane unit, and dimethylsiloxane-diphenylsiloxane unit; and (b) alkyl or aryl 1-substituted siloxane units such as organohydrosiloxane units in which a portion of the alkyl group of the side chain is substituted with a hydrogen atom. When a polyorganosiloxane contains organosiloxane units, the polyorganosiloxane may contain only one of the aforementioned organosiloxane units, or it may contain two or more in combination.

[0060] From the perspective that the obtained water-based coating can provide a coating film with excellent heat resistance, of all 100 mol% of the structural units contained in the polyorganosiloxane, the polyorganosiloxane preferably contains more than 50 mol% of organosiloxane units, more preferably more than 60 mol%, more preferably more than 70 mol%, even more preferably more than 80 mol%, even more preferably more than 90 mol%, and particularly preferably more than 95 mol%.

[0061] From the perspective that the resulting water-based coating can provide a film with superior heat resistance, of all 100 mol% of the structural units contained in the polyorganosiloxane, the polyorganosiloxane preferably contains at least 50 mol% of one or more structural units selected from dimethylsiloxy units, methylphenylsiloxy units, and dimethylsiloxy-diphenylsiloxy units; more preferably, at least 60 mol%; even more preferably, at least 70 mol%; further preferably, at least 80 mol%; even more preferably, at least 90 mol%; and particularly preferably, at least 95 mol%. The raw materials for dimethylsiloxy units are easier to obtain and less expensive than other organosiloxane monomers. Therefore, from the viewpoint of availability and economy, of all 100 mol% of the structural units contained in the polyorganosiloxane, the polyorganosiloxane more preferably contains 50 mol% or more of dimethylsiloxy 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.

[0062] <Crosslinked Structure of Polyorganosiloxanes>

[0063] By using multifunctional alkoxysilane compounds and / or multifunctional monomers in the preparation of polyorganosiloxanes, a crosslinking structure can be introduced into the polyorganosiloxanes. Therefore, the multifunctional alkoxysilane compounds and multifunctional monomers can also be considered as crosslinking agents in the polyorganosiloxanes. In one embodiment of the present invention, the polyorganosiloxane is non-crosslinked. Here, "non-crosslinked polyorganosiloxane" means that the total amount of the multifunctional alkoxysilane compounds and multifunctional monomers used in the preparation of the polyorganosiloxane is 0.50% by weight or less in 100% by weight of the monomer mixture for forming the polyorganosiloxane. In other words, in one embodiment of the present invention, the polyorganosiloxane is substantially non-crosslinked. The total amount of the multifunctional alkoxysilane compounds and multifunctional monomers used in the preparation of the polyorganosiloxane is preferably 0.50% by weight or less, more preferably 0.20% by weight or less, further preferably 0.10% by weight or less, and particularly preferably 0.01% by weight or less in 100% by weight of the monomer mixture for forming the polyorganosiloxane. The monomer mixture used in the preparation of polyorganosiloxanes may also not contain polyfunctional alkoxysilane compounds and polyfunctional monomers.

[0064] Examples of polyfunctional alkoxysilane compounds include tetramethoxysilane, tetraethoxysilane (TEOS), tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltriisopropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane.

[0065] A polyfunctional monomer can also be considered as a monomer having two or more free radical polymerizable reactive groups within the same molecule. These free radical polymerizable reactive groups are, for example, carbon-carbon double bonds. Examples of polyfunctional monomers include allyl alkyl methacrylates and allyloxyalkyl methacrylates, which do not contain butadiene and are olefinically unsaturated double bonds. Examples of monomers having two methacrylate groups include ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, cyclohexanediol dimethacrylate, and polyethylene glycol dimethacrylates. Examples of polyethylene glycol dimethacrylates include triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol (600) dimethacrylate. In addition, examples of monomers having three (meth)acrylate groups include alkoxylated trimethylolpropane tri(meth)acrylates, glyceryl tri(meth)acrylate propoxylate, pentaerythritol tri(meth)acrylate, and tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate. Examples of alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate and trimethylolpropane triethoxylate. Furthermore, examples of monomers having four (meth)acrylate groups include pentaerythritol tetra(meth)acrylate and bis(trimethylolpropane tetra(meth)acrylate. Furthermore, examples of monomers having five (meth)acrylate groups include dipentaerythritol penta(meth)acrylate. Furthermore, examples of monomers having six (meth)acrylate groups include bis(trimethylolpropane hexa(meth)acrylate. In addition, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene are also examples of multifunctional monomers.

[0066] It should be noted that in this specification, monomer M 1 and monomer M 2 It is not included in "multifunctional monomers".

[0067] <Volume average particle size of polyorganosiloxanes>

[0068] The volume average particle size of the polyorganosiloxane is preferably 0.03 μm or more and 50.00 μm or less, more preferably 0.05 μm or more and 10.00 μm or less, more preferably 0.08 μm or more and 2.00 μm or less, further preferably 0.10 μm or more and 1.00 μm or less, even more preferably 0.10 μm or more and 0.80 μm or less, and particularly preferably 0.10 μm or more and 0.50 μm or less. When the volume average particle size of the polyorganosiloxane is (a) 0.03 μm or more, a polyorganosiloxane with a desired volume average particle size can be stably obtained. When it is (b) 50.00 μm or less, the resulting waterborne coating has the advantage of excellent film-forming properties. The volume average particle size of the polyorganosiloxane can be measured using an aqueous latex containing the polyorganosiloxane as a sample and a dynamic light scattering particle size distribution measuring device, etc. The method for determining the volume average particle size of polyorganosiloxanes is described in detail in the following examples.

[0069] In this waterborne coating, of the 100% by weight of the alkoxysilyl-containing synthetic resin, the polyorganosiloxane is preferably 55% by weight or more and 95% by weight or less, more preferably 60% by weight or more and 95% by weight or less, further preferably 65% ​​by weight or more and 95% by weight or less, and particularly preferably 70% by weight or more and 95% by weight or less. When the polyorganosiloxane content in the 100% by weight of the alkoxysilyl-containing synthetic resin is (a) 55% by weight or more, the waterborne coating has the advantage of providing a coating film with a smaller dielectric loss tangent (tanδ) at seawater temperatures; and when it is (b) 95% by weight or less, the waterborne coating has the advantage of superior film-forming properties.

[0070] In this waterborne coating, of the total 100% by weight of polysiloxane and grafted portion, it is preferable that the polysiloxane is 55% by weight or more and 95% by weight or less, and the grafted portion is 5% by weight or more and 45% by weight or less; more preferably, the polysiloxane is 60% by weight or more and 95% by weight, and the grafted portion is 5% by weight or more and 40% by weight or less; even more preferably, the polysiloxane is 65% by weight or more and 95% by weight, and the grafted portion is 5% by weight or more and 35% by weight or less; particularly preferably, the polysiloxane is 70% by weight or more and 95% by weight, and the grafted portion is 5% by weight or more and 30% by weight or less. When the total 100% by weight of polysiloxane and grafted portion contains 55% by weight or more and the grafted portion is 45% by weight or less, the waterborne coating has the advantage of providing a coating film with a smaller dielectric loss tangent (tanδ) at seawater temperatures. In a total of 100% by weight of polyorganosiloxane and grafted portion, waterborne coatings have the advantage of superior film-forming properties when the polyorganosiloxane is 95% or less and the grafted portion is 5% or more.

[0071] Polyorganosiloxanes can be composed of only one type of polyorganosiloxane with the same composition (type and content ratio) and physical properties (volume average particle size and weight average molecular weight, etc.) of structural units, or they can be composed of two or more polyorganosiloxanes with different compositions and / or physical properties of structural units. When a polyorganosiloxane is composed of two or more polyorganosiloxanes with different compositions and / or physical properties of structural units, the two or more polyorganosiloxanes can each form a layered structure.

[0072] (Core)

[0073] Alkoxysilyl-containing synthetic resins comprise a polyorganosiloxane and graft portions grafted to the polyorganosiloxane. In the alkoxysilyl-containing synthetic resin, the graft portions may cover at least a portion of the polyorganosiloxane, or may cover the entire polyorganosiloxane. Preferably, at least a portion of the graft portions is located on the outermost side of the alkoxysilyl-containing synthetic resin. Therefore, the polyorganosiloxane can also be considered as the core of the alkoxysilyl-containing synthetic resin. In other words, the alkoxysilyl-containing synthetic resin comprises a core containing a polyorganosiloxane and graft portions grafted to the core.

[0074] The core may consist of only one type of polysiloxane with the same composition (type and content ratio) of structural units, or it may consist of two or more types of polysiloxanes with different composition (type and content ratio) of structural units. In addition, the core may contain one or more other types of rubber besides one or two or more types of polysiloxanes.

[0075] Other types of rubber include, for example: (a) natural rubber, (b) diene rubber containing 50% or more of structural units derived from diene monomers in 100% by weight of the rubber, and (c) (meth)acrylate rubber containing 50% or more of structural units derived from (meth)acrylate monomers in 100% by weight of the rubber. In this specification, (meth)acrylate refers to acrylates and / or methacrylates.

[0076] When the core contains other rubbers besides polysiloxane, the polysiloxane and other rubbers can each form a layered structure. When the core contains both a layer of polysiloxane and a layer of other rubbers, it is preferable that the polysiloxane layer is located at the very center (inner side) of the core.

[0077] Of the 100 parts by weight of the core, the core preferably contains 55 parts by weight or more and 100 parts by weight of polyorganosiloxane, more preferably 60 parts by weight or more and 100 parts by weight, more preferably more than 60 parts by weight and 100 parts by weight, more preferably 62 parts by weight or more and 100 parts by weight, more preferably 65 parts by weight or more and 100 parts by weight, more preferably 70 parts by weight or more and 100 parts by weight, more preferably 75 parts by weight or more and 100 parts by weight, more preferably 80 parts by weight or more and 100 parts by weight, more preferably 85 parts by weight or more and 100 parts by weight, further preferably 90 parts by weight or more and 100 parts by weight, and particularly preferably 95 parts by weight or more and 100 parts by weight. According to this composition, the waterborne coating has the advantage of providing a coating film with a smaller dielectric loss tangent (tanδ) at seawater temperatures. Of the 100 parts by weight of the core, the core may contain 100 parts by weight of polyorganosiloxane, that is, the core may be composed solely of polyorganosiloxane.

[0078] <Volume average particle size of the core>

[0079] The volume average particle size of the core is preferably 0.03 μm or more and 50.00 μm or less, more preferably 0.05 μm or more and 10.00 μm or less, more preferably 0.08 μm or more and 2.00 μm or less, further preferably 0.10 μm or more and 1.00 μm or less, even more preferably 0.10 μm or more and 0.80 μm or less, and particularly preferably 0.10 μm or more and 0.50 μm or less. When the volume average particle size of the core is (a) 0.03 μm or more, a core with the desired volume average particle size can be stably obtained. When it is (b) 50.00 μm or less, the resulting waterborne coating has the advantage of excellent film-forming properties. The volume average particle size of the core can be measured using a waterborne latex containing the core as a sample, and using a dynamic light scattering particle size distribution measuring device, etc., by the same method as for the volume average particle size of polyorganosiloxanes.

[0080] (Grafting point)

[0081] The grafted portion is grafted and bonded to the polyorganosiloxane. At least a portion of the grafted portion needs to be grafted and bonded to the polyorganosiloxane; it is not necessary for the entire grafted portion to be grafted and bonded to the polyorganosiloxane.

[0082] The graft portion comprises structural units U derived from the monomer represented by the following formula (2). 2 ,

[0083] R 3 p R 4 (4-p-q) SiY q···(2).

[0084] In the formula, R 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0085] As R 3 Examples of olefinic unsaturated groups in olefins include vinyl, acryloyl, and methacryloyl groups.

[0086] Considering (a) high crosslinking reactivity (vinyl polymerization reactivity), (b) ease of processing, (c) low cost, (d) waterborne coatings can provide coatings with lower dielectric loss tangent (tanδ), and (e) further reduction or elimination of bubbling when the coating obtained by waterborne coatings is immersed in water, as R 3 The olefinic unsaturated group in the olefin is preferably acryloyl or methacryloyl.

[0087] In structural unit U 2 Contains 2 or more R 3 In other words, when p is 2 or 3, multiple R 3 They can be the same or different.

[0088] As R 4 Examples include methyl, ethyl, propyl, and butyl.

[0089] Structural unit U 2 It is also possible to omit R. 4 In structural unit U 2 Contains 2 Rs 4 In other words, when the value (difference) of "4-pq" is 2, multiple R 4 They can be the same or different.

[0090] Examples of Y include ethoxy, propoxy, and butoxy. This composition gives the waterborne coating the advantage of excellent storage stability.

[0091] In the case where the monomer represented by equation (2) contains 2 Y, in other words, when q is 2 or 3, the multiple Y can be the same or different from each other.

[0092] In this specification, the monomer represented by formula (2) is sometimes referred to as "monomer M". 2 ".

[0093] As a monomer M 2There are no particular limitations as long as it is expressed by equation (2). Considering (a) high crosslinking reactivity (vinyl polymerization reactivity), (b) easy processing, (c) low cost, (d) waterborne coatings can provide coatings with lower dielectric loss tangent (tanδ), and (e) further reduction or disappearance of bubbling when the coating obtained by waterborne coatings is immersed in water, monomer M 2 Preferably, it is a (meth)acryloyloxyalkylsilane, more preferably selected from one or more of 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyldiethoxymethylsilane, 3-(meth)acryloyloxypropyldiethoxyethylsilane, 3-(meth)acryloyloxypropylethoxydimethylsilane, 3-(meth)acryloyloxypropylethoxydiethylsilane and δ-(meth)acryloyloxybutyldiethoxymethylsilane.

[0094] In the graft portion, which comprises 100% by weight, the graft portion preferably includes 1.0% by weight or more and 80.0% by weight or less of structural unit U. 2 More preferably, it contains 1.0% by weight or more and 75.0% by weight or less; more preferably, it contains 1.0% by weight or more and 70.0% by weight or less; more preferably, it contains 1.0% by weight or more and 65.0% by weight or less; more preferably, it contains 1.0% by weight or more and 60.0% by weight or less; more preferably, it contains 1.5% by weight or more and 55.0% by weight or less; more preferably, it contains 1.5% by weight or more and 50.0% by weight or less; more preferably, it contains 1.5% by weight or more and 45.0% by weight or less; more preferably, it contains 1.5% by weight or more and 40.0% by weight or less; more preferably, it contains 2.0% by weight or more and 38.0% by weight or less; more preferably, it contains 2.0% by weight or more and 35.0% by weight or less; more preferably, it contains 2.0% by weight or more and 33.0% by weight or less; more preferably, it contains 2.5% by weight or more and... The composition contains 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, 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. According to this composition, it has the advantages that (a) the water-based coating can provide a coating film with a lower dielectric loss tangent (tanδ) and (b) the bubbling generated when the coating film obtained by the water-based coating is immersed in water is further reduced or eliminated.

[0095] In 100% by weight of the alkoxysilyl-containing synthetic resin, the alkoxysilyl-containing synthetic resin in component (A) preferably contains 0.5% by weight or more of the above-mentioned structural unit U. 2 More preferably, it contains 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. According to this composition, it has the advantage of improved coating strength. In 100% by weight of this alkoxysilyl-containing synthetic resin, the alkoxysilyl-containing synthetic resin in component (A) preferably contains 5.0% by weight or less of the aforementioned structural unit U. 2 More preferably, it contains 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. According to this composition, it has the advantage of improved film-forming properties.

[0096] In 100% by weight of the solids component of the emulsion of (A) alkoxysilyl-containing synthetic resin, the emulsion of (A) alkoxysilyl-containing synthetic resin contains 0.5% by weight or more of the above-described structural unit U. 2 More preferably, it contains 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. According to this composition, it has the advantage of improved coating strength. In 100% by weight of the solids content of the (A) alkoxysilyl-containing synthetic resin emulsion, the (A) alkoxysilyl-containing synthetic resin emulsion preferably contains 5.0% by weight or less of the aforementioned structural unit U. 2 More preferably, it contains 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. According to this composition, it has the advantage of improved film-forming properties.

[0097] (A) The concentration of solids in emulsions of alkoxysilyl-containing synthetic resins can be determined using an electronic moisture meter. The structural unit U in alkoxysilyl-containing synthetic resins... 2 The content of, or (A) the structural unit U in the emulsion of synthetic resin containing alkoxysilyl groups. 2 The content can be adjusted by making the structural unit U 2 Hydrolysis is performed, and the amount of alcohol produced is analyzed (determined). Given that the composition of the monomers used in manufacturing is known, the determination is based on monomer M. 2The ratio of the amount of [specific component] to the total amount of monomers was used to calculate the structural unit U in the alkoxysilyl-containing synthetic resin, taking into account the polymerization conversion rate. 2 The content of, or (A) the structural unit U in the emulsion of synthetic resin containing alkoxysilyl groups. 2 The content of.

[0098] The grafting portion may include structural unit U. 2 Other structural units besides structural unit U. 2 Other structural units are not particularly limited. The grafting portion preferably comprises, for example, structural units derived from one or more monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers. According to this configuration, the grafting portion can perform the function of solidifying substantially non-crosslinked polyorganosiloxanes. Therefore, according to this configuration, the resulting waterborne coating has the advantages of excellent film-forming properties and excellent coating film strength.

[0099] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

[0100] Specific examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.

[0101] Specific examples of (meth)acrylate monomers include: (a) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and behenyl methacrylate; (b) cyclohexyl methacrylates such as butyl methacrylate and cyclohexyl methacrylate; (c) aromatic ring-containing (meth)acrylates such as phenoxyethyl methacrylate and benzyl methacrylate; (d) (e) Hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, and other hydroxyalkyl methacrylates; (f) Alkoxyalkyl methacrylates; (g) Allyl methacrylate, allyl alkyl methacrylate, and other allyl methacrylates; (h) Polyfunctional methacrylates such as monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

[0102] From the viewpoint of reactivity during the formation of the graft, the (meth)acrylate monomer is preferably selected from one or more of methyl acrylate, ethyl methacrylate and butyl methacrylate.

[0103] The graft portion may contain only one structural unit as a structural unit from one or more monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers, or it may contain a combination of two or more structural units.

[0104] Of the 100% by weight of the grafted portion, the grafted portion preferably comprises a total of 60% by weight and 99% by weight or less structural units from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers; more preferably, 62% by weight and 98% by weight or less; even more preferably, 65% by weight and 97% by weight or less; particularly preferably, 68% by weight and 96% by weight or less; and most preferably, 70% by weight and 95% by weight or less. According to this composition, the resulting waterborne coating has the advantage of superior film-forming properties.

[0105] From the viewpoint of balancing the film-forming properties of water-based coatings and the reactivity during the formation of grafted portions, the grafted portions preferably contain structural units derived from (meth)acrylate monomers, and more preferably consist only of structural units derived from (meth)acrylate monomers.

[0106] Of the 100% by weight of the grafted portion, the grafted portion preferably contains 60% by weight or more and 99% by less structural units derived from (meth)acrylate monomers, more preferably 62% by weight or more and 98% by less, even more preferably 65% ​​by weight or more and 97% by less, particularly preferably 68% by weight or more and 96% by less, and most preferably 70% by weight or more and 95% by less. According to this configuration, it has the advantage of excellent reactivity when forming the grafted portion.

[0107] From the perspective of significantly improving the storage stability of emulsions of synthetic resins containing alkoxysilyl groups, the graft portion preferably includes one or more structural units selected from the following, or may be composed of only one or more structural units selected from the following: structural units from (meth)acrylate monomers having alkyl groups having 4 or more carbon atoms, and structural units from (meth)acrylate monomers having cycloalkyl groups having 4 or more carbon atoms.

[0108] Regarding the grafted portion, of 100% by weight, it preferably contains at least 60% by weight of structural units selected from structural units derived from (meth)acrylate monomers having alkyl groups having 4 or more carbon atoms and structural units derived from (meth)acrylate monomers having cycloalkyl groups having 4 or more carbon atoms; more preferably, it contains at least 60% by weight and 99% by weight; more preferably, it contains at least 62% by weight and 98% by weight; even more preferably, it contains at least 65% by weight and 97% by weight; particularly preferably, it contains at least 68% by weight and 96% by weight; and most preferably, it contains at least 70% by weight and 95% by weight. According to this configuration, the emulsion of the synthetic resin containing alkoxysilyl groups has the advantage of significantly improved storage stability.

[0109] From the perspective of better reactivity when forming the graft, the graft preferably includes structural units from methyl methacrylate and structural units from butyl methacrylate, and more preferably consists only of structural units from methyl methacrylate and structural units from butyl acrylate.

[0110] Regarding the graft portion, in 100% by weight, it preferably contains 60% by weight or more and 99% by weight of structural units derived from methyl methacrylate and butyl methacrylate, more preferably 62% by weight or more and 98% by weight, even more preferably 65% ​​by weight or more and 97% by weight, particularly preferably 68% by weight or more and 96% by weight, and most preferably 70% by weight or more and 95% by weight or less. According to this configuration, it has the advantage of superior reactivity when forming the graft portion.

[0111] <Structural units derived from reactive emulsifiers>

[0112] The grafted portion may further include structural units derived from reactive emulsifiers. This configuration offers the advantage of reduced or eliminated scaling during the manufacture of water-based coatings.

[0113] In this specification, "reactive emulsifier" refers to an emulsifier containing olefinic unsaturated double bonds. Furthermore, "reactivity" in reactive emulsifier refers to the property of possessing polymerizable free radicals, such as those found in the presence of a polymerization initiator. Therefore, "reactive emulsifier" can also be considered a "polymerizable emulsifier." Sometimes, "reactive emulsifier" is also referred to as a "reactive surfactant."

[0114] As a reactive emulsifier, there is no particular limitation on its type as long as it has an olefinic unsaturated double bond. The reactive emulsifier can be cationic, anionic, or nonionic. For example, from the perspective of easily controlling the particle size of alkoxysilyl-containing synthetic resins to a fine particle size (specifically, controlling the volume average particle size of alkoxysilyl-containing synthetic resins to 30 nm or more and 200 nm or less), anionic reactive emulsifiers are preferred.

[0115] The olefinic unsaturated double bonds in reactive emulsifiers originate from groups possessing olefinic unsaturated double bonds. In other words, reactive emulsifiers possess groups possessing olefinic unsaturated double bonds. Specific examples of groups possessing olefinic unsaturated double bonds include oxoalkylene, (meth)acryloyl, vinyl, allyl, isopropenyl, 1-propenyl, allyloxy, styryl, etc.

[0116] Reactive emulsifiers preferably have oxoalkylene groups. Reactive emulsifiers with oxoalkylene groups exhibit excellent copolymerization properties with monomers. Examples of oxoalkylene groups include oxoethylene, oxopropylene, and oxobutylene, which have alkylene groups with 2 or more but less than 4 carbon atoms. Among these, oxoethylene is preferred. Oxoethylene, for example, has higher hydrophilicity than oxopropylene and oxobutylene. Therefore, when the graft portion of an alkoxysilyl-containing synthetic resin contains structural units from a reactive emulsifier with oxoethylene, a high-density hydrated layer is easily formed on the surface of the alkoxysilyl-containing synthetic resin particles. As a result, the dispersibility of the alkoxysilyl-containing synthetic resin particles in an aqueous medium tends to be further improved.

[0117] There is no particular limitation on the average number of moles of oxyethylidene added per mole of reactive emulsifier, but it is preferably 5 moles or more and 40 moles or less, more preferably 10 moles or more and 30 moles or less. With this configuration, there is a tendency for excellent copolymerization with the monomer. Furthermore, if the average number of moles of oxyethylidene added is 5 moles or more, there is a tendency for further improvement in the dispersibility of alkoxysilyl-containing synthetic resin particles in aqueous media.

[0118] The above-mentioned reactive emulsifiers can be used alone or in combination of two or more.

[0119] In the 100% by weight of the grafted portion, the grafted portion preferably contains 0.1% by weight or more and 20.0% by weight or less structural units from the reactive emulsifier, 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. According to this configuration, it has the advantage of further reducing or eliminating the generation of scale during the manufacture of water-based coatings.

[0120] <Structural units from chain transfer agents>

[0121] The graft may or may not contain structural units from the chain transfer agent.

[0122] There are no particular limitations on the chain transfer agent used; known chain transfer agents such as tert-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, and 2-ethylhexyl thioglycolate can be used.

[0123] When a chain transfer agent is used as a raw material in the preparation of the graft, a graft containing structural units from the chain transfer agent can be obtained. In other words, when a chain transfer agent is used as a raw material in the preparation of the graft, and the graft contains structural units from the chain transfer agent, the preparation of the graft will produce a graft with the same structure as the graft (i.e., containing structural units U). 2 And polymers that are not grafted with any polymer (e.g., polyorganosiloxanes) (hereinafter, sometimes referred to as "ungrafted polymers"). As a result, when a chain transfer agent is used as a raw material in the preparation of the grafted portion, solution A can contain ungrafted polymers. When solution A contains ungrafted polymers, it has the advantage of excellent film-forming properties.

[0124] When the amount of chain transfer agent used in preparing the grafted portion is 0.01% by weight or less in 100% by weight of the monomer mixture for grafting, the content of structural units from the chain transfer agent in the resulting grafted portion can be 0.01% by weight or less in 100% by weight of the grafted portion. When the content of structural units from the chain transfer agent in the grafted portion is 0.01% by weight or less in 100% by weight of the grafted portion, it is considered in this specification that "the grafted portion does not contain structural units from the chain transfer agent." When the amount of chain transfer agent used in preparing the grafted portion is 0.01% by weight or less in 100% by weight of the monomer mixture for grafting, no non-grafted polymer is generated during the preparation of the grafted portion, or even if there is non-grafted polymer, its amount is extremely small. As a result, when the amount of chain transfer agent used in preparing the graft is less than 0.01% by weight in 100% by weight of the monomer mixture for graft formation, solution A contains no non-grafted polymer, or if it does contain non-grafted polymer, its content is extremely low. When solution A contains no non-grafted polymer, or if it does contain non-grafted polymer, its content is extremely low, it exhibits excellent water resistance.

[0125] <Cross-linking structure of the graft>

[0126] By using a multifunctional monomer in the preparation of the graft portion, a cross-linked structure can be introduced into the graft portion. In one embodiment of the present invention, it is preferable that the graft portion is non-cross-linked. Here, "non-cross-linked graft portion" means that all polymers contained in the graft portion are non-cross-linked. In addition, "non-cross-linked graft portion" means that (i) the amount of the multifunctional monomer used in the preparation of the graft portion is 0.50% by weight or less in 100% by weight of the monomer mixture for forming the graft portion. In other words, in one embodiment of the present invention, it is preferable that the graft portion is substantially non-cross-linked, and the amount of the multifunctional monomer used in the preparation of the graft portion is preferably 0.50% by weight or less in 100% by weight of the monomer mixture for forming the graft portion. The amount of the multifunctional monomer used in the preparation of the graft portion is preferably 0.50% by weight or less, more preferably 0.20% by weight or less, further preferably 0.10% by weight or less, and particularly preferably 0.01% by weight or less in 100% by weight of the monomer mixture for forming the graft portion.

[0127] The grafted portion may be composed of only one type of polymer with the same composition (type and content ratio) and physical properties (volume average particle size and weight average molecular weight, etc.) of structural units, or it may be composed of two or more polymers with different compositions and / or physical properties of structural units. When the grafted portion is composed of two or more polymers with different compositions and / or physical properties of structural units, the two or more polymers may each form a layered structure.

[0128] The core and grafted portion containing polyorganosiloxane can have a layered structure. For example, one embodiment of the invention is a core containing polyorganosiloxane as the innermost layer (also called the core layer) and a layer of grafted portion outside the core as the outermost layer (also called the shell layer). Alternatively, the structure with the core containing polyorganosiloxane as the core layer and the grafted portion as the shell layer can be considered a core-shell structure. However, the grafted portion only needs to be grafted and bonded to the polyorganosiloxane, and the synthetic resin containing alkoxysilane is not limited to the above configuration.

[0129] (Volume average particle size of synthetic resins containing alkoxysilyl groups)

[0130] From the perspective of obtaining a waterborne coating with desired viscosity and high stability, the volume average particle size (Mv) of the alkoxysilyl-containing synthetic resin is preferably 0.05 μm or more and 60.00 μm or less, more preferably 0.10 μm or more and 20.00 μm or less, more preferably 0.10 μm or more and 8.00 μm or less, more preferably 0.10 μm or more and 6.00 μm or less, more preferably 0.10 μm or more and 4.00 μm or less, more preferably 0.10 μm or more and 2.00 μm or less, further preferably 0.10 μm or more and 1.00 μm or less, and particularly preferably 0.10 μm or more and 0.80 μm or less. According to this configuration, it has the advantages of excellent polymerization stability of the alkoxysilyl-containing synthetic resin and excellent storage stability of the waterborne coating. It should be noted that, unless otherwise specified, in this specification, "volume average particle size (Mv) of the alkoxysilyl-containing synthetic resin" refers to the volume average particle size of the primary particles of the alkoxysilyl-containing synthetic resin. The volume average particle size of the alkoxysilyl-containing synthetic resin can be measured using a dynamic light scattering particle size distribution measuring device, etc., with water-based coatings or emulsions containing the alkoxysilyl-containing synthetic resin (i.e., component (A)) as samples. The volume average particle size of the alkoxysilyl-containing synthetic resin is described in detail in the following examples.

[0131] The preferred waterborne coating has a particle size distribution of alkoxysilyl-containing synthetic resins with a half-width of 0.5 to 1 times the volume average particle size. Based on this composition, the waterborne coating has the advantages of low viscosity and ease of handling.

[0132] The method for manufacturing synthetic resins containing alkoxysilyl groups will be described in detail in the section on [Manufacturing Method of Waterborne Coatings] described later.

[0133] (Other arbitrary components 1)

[0134] As needed, liquid A may also contain components other than component (A) (hereinafter sometimes referred to as "other arbitrary components 1"). Examples of other arbitrary components 1 include colorants such as pigments and dyes, extender pigments, pigment dispersants, ultraviolet absorbers, antioxidants, heat stabilizers (anti-gelling agents), stabilizers, plasticizers, leveling agents (e.g., BYK-333 manufactured by BYK Japan Co., Ltd.), defoamers (e.g., Agitan295 manufactured by MUNZING CHEMIE Co., Ltd.), silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, and tackifiers (e.g., SN manufactured by Sannopco Co., Ltd.). Thickener 612NC), viscosity modifiers, thixotropic agents, low-shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, wetting agents, dispersants, anti-sagging agents, anti-color separation agents, anti-settling agents, film consumption modifiers, surface modifiers, film-forming aids (e.g., CS-12 manufactured by JNC), antibacterial agents, mildew inhibitors, preservatives, antifreeze agents, tackifiers, rust inhibitors, etc.

[0135] The aforementioned liquid A is itself an embodiment of the present invention. That is, an embodiment of the present invention provides an aqueous coating that does not contain liquid B described later, or more specifically, component (B) described later.

[0136] (2-2. Solution B)

[0137] ((B) Substances that promote the hydrolysis / condensation of alkoxysilyl groups)

[0138] Solution B contains (B) a substance that promotes the hydrolysis / condensation of alkoxysilyl groups. "Hydrolysis / condensation" refers to both hydrolysis and condensation. In this specification, "(B) the substance that promotes the hydrolysis / condensation of alkoxysilyl groups" is sometimes referred to as "(B) component".

[0139] Component (B) promotes the hydrolysis and condensation of alkoxysilyl groups contained in the synthetic resin containing alkoxysilyl groups in component (A). Therefore, this waterborne coating, by containing component (B), has the advantage of excellent film-forming speed. In addition, this waterborne coating, by containing component (B), also has the advantage of providing a coating film with excellent strength.

[0140] As component (B), any substance that can promote the hydrolysis and condensation of alkoxysilanes contained in component (A), especially in synthetic resins containing alkoxysilanes in component (A), is acceptable, without any particular limitation.

[0141] As components (B), examples include organometallic compounds, alkali metal compounds, acidic catalysts, and basic catalysts.

[0142] Examples of organometallic compounds include organotin compounds.

[0143] Examples of organotin compounds include dialkyltin carboxylic acid salts (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctanoate, dibutyltin dimethylmaleate, diethyltin dibutyltin dibutyltin, dibutyltin dibutylmaleate, diisooctyltin maleate, dibutyltin didecyl maleate, dibenzyltin dibutyltin dibutyltin, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, diethyltin dioctyltin dioctyltin, diisooctyltin dioctylmaleate, etc.), dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, mixtures of dibutyltin oxide and phthalates, etc.), tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) and... Reactants containing alkoxysilyl low-molecular-weight silicon compounds (tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, etc.), divalent tin compounds (tin octoate, tin naphthenate, tin stearate, etc.), monoalkyltin compounds (monobutyltin compounds (monobutyltrioctanoate, monobutyltriisopropoxytin, etc.), monooctyltin compounds, etc.), reactants or mixtures of amine compounds and organotin compounds (reactants or mixtures of laurylamine and tin octoate, etc.), chelates (diacetylacetonate dibutyltin, diacetylacetonate dioctyltin, diethylacetoneate dibutyltin, diethylacetoneate dioctyltin, etc.), and tin alkoxides (dibutyldiethanoltin, dibutyldiethanoltin, dioctyldiethanoltin, dioctyldiethanoltin, etc.). In addition, examples of organotin compounds include diacetylacetonate dibutyltin, dibutyltin dimaleate, dioleoyl dibutyltin maleate, dibutyldimethoxytin, dibutyltin mercaptoacetate, dibutyltin diisononyl3-mercaptopropionate, dibutyltin diisooctylmercaptoacetate, dibutyltin diisooctylmercaptoacetate, dibutyltin diisooctylmercaptoacetate, dibutyltin diisooctyldioctyltin, di(octylthioglycolate)dimethyltin salt, etc.

[0144] 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, phenylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazolium, and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU).

[0145] There are no particular limitations on the alkali metal compound as long as it contains at least one alkali metal. Suitable examples of alkali metal compounds include lithium compounds, sodium compounds, and potassium compounds. From the viewpoint of low-temperature curing properties, storage stability, and coating operability of water-based coatings, lithium compounds are the most preferred among these alkali metal compounds.

[0146] 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, and alkali metal salts of carboxylic acids containing 6 or more but less than 24 carbon atoms are more preferred. In alkali metal salts of carboxylic acids containing 6 or more but less than 24 carbon atoms, the aforementioned carboxylic acid is preferably a long-chain carboxylic acid. Long-chain alkali metal salts of carboxylic acids are particularly preferred as alkali metal compounds. Here, "long chain" in long-chain carboxylic acids refers to a chain with 6 or more carbon atoms.

[0147] Among the above-mentioned alkali metal salts of carboxylic acids, the carboxylic acid is preferably a monocarboxylic acid.

[0148] In alkali metal salts of carboxylic acids with 6 or more but less than 24 carbon atoms, the carboxylic acid may consist of only one type of carboxylic acid or a combination of two or more carboxylic acids. From the viewpoint of improving the ease of manufacture and antifouling properties of water-based coatings, it is preferable that the carboxylic acid in the alkali metal salt of carboxylic acids with 6 or more but less than 24 carbon atoms contains two or more carboxylic acids. When the carboxylic acid in the alkali metal salt of carboxylic acids with 6 or more but less than 24 carbon atoms contains two or more carboxylic acids, these two or more carboxylic acids may be a mixture of isomers, a mixture of multiple carboxylic acids with different numbers of carbon atoms, or a combination of a mixture of isomers and a mixture of multiple carboxylic acids with different numbers of carbon atoms. In alkali metal salts of carboxylic acids with 6 or more but less than 24 carbon atoms, the hydrocarbon chain constituting the carboxylic acid may be saturated or unsaturated. In alkali metal salts of carboxylic acids with 6 or more but less than 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 with 6 or more but less than 24 carbon atoms, when the hydrocarbon chain constituting the carboxylic acid is branched, the longest chain preferably has 6 or more carbon atoms.

[0149] In the above-mentioned alkali metal salts of carboxylic acids, the number of carbon atoms in the carboxylic acid is preferably 6 or more and 24 or less, more preferably 8 or more and 22 or less, and even more preferably 8 or more and 16 or less.

[0150] Specific examples of carboxylic acid alkali metal salts 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, eicosanoic acid, behenic acid, erucic acid, oleic acid, linoleic acid, linolenic acid, and cycloalkanoic acid. Among these carboxylic acids, long-chain carboxylic acids having straight or branched hydrocarbon chains are preferred, long-chain carboxylic acids having straight or branched alkyl chains are more preferred, and one or more selected from 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, and versatic acid are even more preferred. Particularly preferred are one or more selected from 2-ethylhexanoic acid, octanoic acid, and versatic acid. Tertiary carbonic acid refers to a mixture of monocarboxylic acids (including mixtures of isomers) with a monocarboxylic acid having 10 carbon atoms as the main component. The alkali metal salt of tertiary carbonic acid is an alkali metal salt of a long-chain carboxylic acid containing two or more carboxylic acids.

[0151] The alkali metal compound (i) preferably comprises one or more compounds selected from lithium compounds, sodium compounds, and potassium compounds, or may consist of only one or more compounds selected from these compounds; (ii) more preferably comprises one or more compounds selected from lithium 2-ethylhexanoate, lithium octanoate, lithium tertiary carbonate, sodium 2-ethylhexanoate, sodium octanoate, sodium tertiary carbonate, potassium 2-ethylhexanoate, potassium octanoate, and potassium tertiary carbonate, or may consist of only one or more compounds selected from these compounds. From the viewpoint of improving the ease of manufacture and antifouling properties of waterborne coatings, the alkali metal compound further preferably comprises one or more compounds selected from lithium tertiary carbonate, sodium tertiary carbonate, and potassium tertiary carbonate, or may consist of only one or more compounds selected from these compounds, and particularly preferably comprises lithium tertiary carbonate, or may consist of only lithium tertiary carbonate.

[0152] Examples of acidic catalysts include: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, tetracosanoic acid, hexacosanoic acid, nonadecanoic acid, triacontanoic acid, tridodecanoic acid, and other straight-chain saturated fatty acids; undecenoic acid, dodecenoic acid, tsuzuic acid, physeteric acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, phellandrenic acid, oleic acid, transoleic acid, cis-11-octadecanoic acid, 11-octadecanoic acid, cis-9-eicosenoic acid, cis-11-eicosenoic acid, and setoleic acid. Monounsaturated fatty acids such as erucic acid, trans-13-docosahexaenoic acid, squalane, simulinic acid, and cis-21-trianediol; linoleic acid, 10,12-octadecadienoic acid, hiragoic acid, α-tungsten acid, β-tungsten acid, punicic acid, linolenic acid, 8,11,14-eicosatetrienoic acid, 7,10,13-docosahexaenoic acid, 4,8,11,14-hexadecanetraenoic acid, morotic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosahexaenoic acid, 4,8,12,15,18-eicosapentaenoic acid, clupanodonic acid, etc. Polyene unsaturated fatty acids such as docosahexaenoic acid (DHA), nisinicacid, and docosahexaenoic acid; branched fatty acids such as iso-acid, anteiso-acid, nodular stearic acid, neopentanoic acid, 2-ethylhexanoic acid, neodecanoic acid, and tert-carbonic acid; fatty acids with triple bonds such as tariricacid, stearyleneic acid, crepenynic acid, simendynic acid, and 7-hexadecanoic acid; alicyclic carboxylic acids such as cycloalkanoic acid, malvaic acid, styraciferic acid, crocinoleic acid, and cyclopentenetridecenoic acid; and juniperic acids such as hinoki acid, 2-hydroxytetradecanoic acid, ipurolic acid, 2-hydroxyhexadecanoic acid, 11-hydroxyhexadecanoic acid, and 16-hydroxyhexadecanoic acid. Oxygenated fatty acids such as succinic acid, lauric acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlolenic acid, licanicacid, 22-hydroxydocosahexadecanoic acid, and cerebroside; and dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, and sebacic acid.

[0153] (B) Component (i) preferably includes one or more selected from organometallic compounds, alkali metal compounds, acidic catalysts, and basic catalysts; (ii) preferably includes one or more selected from organotin compounds, amine compounds, and alkali metal compounds, or may consist of only one or more selected from these; (iii) more preferably includes diacetylacetonate dibutyltin, thioglycolic acid dibutyltin, diisooctylthioglycolic acid dibutyltin, diisooctylthioglycolic acid dibutyltin, diisooctylthioglycolic acid dibutyltin, didodecylthiodimethyltin, didodecylthiodibutyltin, didodecylthiodioctyltin, di(octylthioglycolate) dimethyltin salt, and 2-ethylhexanoic acid. The catalyst may consist of one or more of lithium, lithium octanoate, lithium tertiary carbonate, sodium 2-ethylhexanoate, sodium octanoate, sodium tertiary carbonate, potassium 2-ethylhexanoate, potassium octanoate, potassium tertiary carbonate, laurylamine, diethylaminopropylamine, and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU), or may consist of only one or more of these. (iv) More preferably, the catalyst may contain one or more of diacetylacetonate dibutyltin, lithium tertiary carbonate, sodium tertiary carbonate, potassium tertiary carbonate, and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU), or may consist of only one or more of these. (v) Particularly preferably, the catalyst may contain diacetylacetonate dibutyltin, or may consist of only diacetylacetonate dibutyltin. The preferred component (B) described above is readily available and exhibits excellent catalyst activity. In addition, when component (B) contains the aforementioned preferred compound, or is composed solely of the compound, it has the advantages of (i) excellent ease of manufacture and improved antifouling properties of water-based coatings, and (ii) a low likelihood of being subject to use restrictions based on laws and regulations.

[0154] When component (B) is a liquid, component (B) itself can be used as liquid B. In other words, liquid B can consist solely of component (B).

[0155] (solvent)

[0156] In addition to component (B), liquid B may further contain a solvent. In particular, when component (B) is a solid, liquid B may be a liquid obtained by dissolving component (B) in a solvent, or a liquid obtained by dispersing component (B) in a solvent.

[0157] There are no particular limitations on the solvent. 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 monoisobutyl 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, etc.

[0158] From the viewpoint of ease of manufacture of water-based coatings, the solvent (i) preferably contains one or more selected from 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 be composed of only one or more selected from these, (ii) more preferably contains water, and may also be composed of only water.

[0159] (2 other arbitrary components)

[0160] Depending on the requirements, liquid B may contain components other than component (B) (hereinafter sometimes referred to as "other arbitrary components 2"). Examples of other arbitrary components 2 include colorants such as pigments and dyes, extender pigments, pigment dispersants, ultraviolet absorbers, antioxidants, heat stabilizers (anti-gelling agents), stabilizers, plasticizers, leveling agents, defoamers, silane coupling agents, antistatic agents, flame retardants, lubricants, tackifiers, thickeners, viscosity modifiers, thixotropic agents, low-shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, wetting agents, dispersants, anti-sagging agents, anti-color separation agents, anti-settling agents, coating consumption modifiers, surface modifiers, film-forming aids, antibacterial agents, mildew inhibitors, preservatives, antifreeze agents, thickeners, rust inhibitors, etc.

[0161] (2-3. Antifouling agent)

[0162] This waterborne coating may further include an antifouling agent. The antifouling agent may be included in either solution A or solution B. It is believed that this waterborne coating, due to its small dielectric loss tangent (tanδ) at seawater temperatures, possesses antifouling properties against aquatic organisms even without containing an antifouling agent. Therefore, this waterborne coating, without containing an antifouling agent, can be suitably used as an antifouling coating for underwater structures. Since waterborne coatings 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, this waterborne coating preferably further includes an antifouling agent. On the other hand, a coating film obtained from a waterborne coating without an antifouling agent is less susceptible to damage compared to a coating film obtained from a waterborne coating containing an antifouling agent. Therefore, a coating film obtained from a waterborne coating without an antifouling agent has the advantage of higher durability compared to a coating film obtained from a waterborne coating containing an antifouling agent.

[0163] There are no particular limitations on the antifouling agent used; any known antifouling agent can be used. Examples of antifouling agents include: inorganic compounds, organic compounds containing metals, and organic compounds that do not contain metals.

[0164] Examples of antifouling agents include: zinc oxide, cuprous oxide, zinc 2-pyridinethiol-1-oxohydrin (also known as zinc pyridinethione) and copper salts, pyridinethione salt compounds, p-isopropylpyridinemethyldiphenylborane, pyridinetriphenylborane, tetramethylthiuram disulfide, and carbamate compounds (e.g., zinc dimethyldithiocarbamate, zinc ethylidene didithiocarbamate, 3-iodo-2-propylbutylcarbamate, dimethyldithiocarbamate). Acyl zinc ethylidene bis(dithiocarbamate) and manganese ethylidene bis(dithiocarbamate), etc.), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachlorophthalonitrile, N,N-dimethyldichlorophenylurea, cuprous thiocyanate, 4,5-dichloro-2-n-octyl-3(2H)isothiazolidinone (also known as 4,5-dichloro-2-n-octyl-4-isothiazolidin-3-one), N-(fluorodichloromethylthio)phthalamide Imide, N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfonamide, tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4-(methanesulfonyl)pyridine, diiodomethyl-p-tolyl sulfone, phenyl(bipyridyl)bismuth dichloride, 2-(4-thiazolyl)benzimidazole, triphenylborone pyridine salt, stearylamine-triphenylborone, laurylamine-triphenylborone, 1,1-dichloro-N-[(dimethyl... [(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfonamide, 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfonamide, N'-(3,4-dichlorophenyl)-N,N'-dimethylurea, N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-nitrile, etc.

[0165] (2-4. Organic solvents)

[0166] This water-based coating may contain organic solvents. These organic solvents may be contained in either liquid A or liquid B. This water-based coating does not contain organic solvents and has excellent film-forming properties. When the water-based coating contains organic solvents, it has even better film-forming properties. Examples of organic solvents include: hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, and alcohols. Examples of hydrocarbon organic solvents include n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, cyclohexane, methylcyclohexane, cyclopentane, toluene, xylene, benzene, ethylbenzene, naphthane, petroleum solvent oil, and naphtha. Examples of halogenated hydrocarbon organic solvents include dichloromethane, chloroform, tetrachloroethane, and trichloroethane. Examples of ether organic solvents include dichloromethane, chloroform, tetrachloroethane, and trichloroethane. Alkane, ethyl ether, diethyl ether, butyl diethylene glycol, 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 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, dipropylene glycol dimethyl ether, etc. Examples of organic solvents that can be used as 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 that can be used as 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 that can be used as 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 can be used individually or in combination of two or more.

[0167] From an environmental protection and safety perspective, the lower the content of organic solvents in this water-based coating, the better. The content of organic solvents in this water-based coating is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, further 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 coating.

[0168] (2-5. Others)

[0169] In addition to liquid A and liquid B, this water-based coating may further contain one or more liquids (e.g., liquid C, etc.) as needed. When this water-based coating further contains liquid C in addition to liquid A and liquid B as needed, liquid C may contain components other than those described in (A) and (B). Examples of components other than those described in (A) and (B) include any other component 1 and any other component 2, etc.

[0170] [3. Manufacturing method of water-based coatings]

[0171] The manufacturing method of this water-based coating is not particularly limited. As one embodiment of the present invention, a suitable manufacturing method for the water-based coating may be the following, comprising:

[0172] Step A in preparing emulsion A containing (A) an alkoxysilyl-containing synthetic resin; and

[0173] Step B, which prepares solution B containing (B) a substance that promotes the hydrolysis / condensation of alkoxysilyl groups.

[0174] The above process A has the following characteristics: process A-1, which makes the monomer M containing the following formula (1) 1 Polymerization of organosiloxanes using a monomer mixture yields a product containing monomer M. 1 Structural unit U 1 The polyorganosiloxane; and step A-2, in the presence of the polyorganosiloxane obtained in step A-1, to make the monomer M containing the following formula (2) 2 The grafted portion is formed by polymerization of a monomer mixture to form a graft containing monomer M. 2 Structural unit U 2 The grafting part,

[0175] In step A-1 above, the total amount of the polyfunctional alkoxysilane compound and the polyfunctional monomer in the 100% by weight mixture of monomers for forming the polyorganosiloxane is 0.50% by weight or less.

[0176] R 1 m R 2 (4-m-n) SiX n ···(1)

[0177] (where R is in the formula) 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 X is an alkyl group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less.

[0178] R 3 p R 4 (4-p-q) SiY q ···(2)

[0179] (where R is in the formula) 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an independent integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0180] The method for manufacturing a water-based coating according to one embodiment of the present invention, having the above-described structure, is able to provide a water-based coating with excellent storage stability.

[0181] In this specification, "a method for manufacturing a water-based coating according to an embodiment of the present invention" is sometimes referred to as "this manufacturing method".

[0182] The following describes each step of the manufacturing method in detail. Except as otherwise provided below, there are no particular limitations on matters (e.g., various components and their amounts), and the description in section [2. Waterborne Coatings] above is used as appropriate.

[0183] (3-1. Process A)

[0184] Step A is the step of preparing emulsion A containing an alkoxysilyl-containing synthetic resin (A). To prepare the emulsion of the alkoxysilyl-containing synthetic resin (A), step A includes: step A-1, which involves preparing a monomer M containing the monomer represented by formula (1) above. 1 Polymerization of organosiloxanes using a monomer mixture yields a product containing monomer M. 1 Structural unit U 1 The polyorganosiloxane; and step A-2, in the presence of the polyorganosiloxane obtained in step A-1, making the monomer M represented by the above formula (2) contain... 2 The grafted portion is formed by polymerization of a monomer mixture to form a graft containing monomer M. 2 Structural unit U 2 The grafting portion. Through process A, an emulsion of a synthetic resin containing alkoxysilyl groups can be obtained, the emulsion of the synthetic resin containing alkoxysilyl groups comprising (i) a structural unit U. 1 Furthermore, the non-crosslinked polyorganosiloxane, and (ii) are grafted onto the polyorganosiloxane and contain the structural unit U. 2 The grafting part.

[0185] (Process A-1)

[0186] Step A-1 is the preparation of a structure containing unit U. 1 The process of producing polyorganosiloxanes.

[0187] The organosiloxane contained in the monomer mixture for forming polyorganosiloxanes is not particularly limited. In step A-1, it is preferable to use a known organosiloxane, for example, in a manner that yields a polyorganosiloxane having the structural unit (organosiloxane unit) described in the above item (organosiloxane unit).

[0188] In process A-1, organosiloxanes such as (a) dimethyldimethoxysilane, dimethyldiethoxysilane, and other dimethyldialkoxysilanes; (b) hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetradecylcycloheptasiloxane, dimethylcyclic compounds (mixtures of dimethylsiloxane cyclic oligomers with 3 or more but less than 7 polymers); and (c) dimethyldichlorosilane can be used as raw materials. Furthermore, linear or branched organosiloxanes can also be used as raw materials.

[0189] In step A-1, a pre-polymerized polyorganosiloxane can be used as the organosiloxane. In this case, the molecular chain ends of the polyorganosiloxane can be capped with hydroxyl, alkoxy, trimethylsilyl, dimethylvinylsilyl, methylphenylvinylsilyl, methyldiphenylsilyl, etc.

[0190] From the perspective of easy availability and easy preparation of polyorganosiloxanes, the organosiloxanes used as raw materials in step A-1 are preferably various organosiloxane cyclic compounds with three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetradecylcycloheptasiloxane, and dimethyl cyclic compounds (a mixture of dimethylsiloxane cyclic oligomers with more than three members and less than seven members).

[0191] Monomer M contained in the monomer mixture for forming polyorganosiloxanes 1 The monomer M described in the above (polyorganosiloxane) section 1 Since the records are identical, the explanation is omitted here.

[0192] Monomer M in process A-1 1 The amount used and the structural unit U in the obtained polyorganosiloxane 1 The content is related to the monomer M in process A-1. 1 The amount used is not particularly limited, but in 100% by weight of polyorganosiloxane, the preferred structural unit is U. 1 The content is 0.001% by weight or more and 10.0% by weight or less. Monomer M in process A-1 1The amount used, for example, in 100% by weight of the monomer mixture for forming polyorganosiloxane, is preferably 0.001% by weight or more and 10.0% by weight or less, more preferably 0.01% by weight or more and 5.0% by weight or less, further preferably 0.1% by weight or more and 5.0% 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 3.0% by weight or less. According to this configuration, it has the advantage of (a) being able to efficiently carry out the polymerization of the monomer mixture for grafting in the presence of polyorganosiloxane.

[0193] In process A-1, as organosiloxane and monomer M 1 The polymerization method is not particularly limited; for example, well-known emulsion polymerization carried out in the presence of an acidic emulsifier can be cited.

[0194] There are no particular limitations on the acidic emulsifier used, but when using organosiloxane cyclic compounds, it is preferable to use an agent that can cause the organosiloxane cyclic compounds to undergo ring-opening. Examples of suitable acidic emulsifiers include dodecylbenzenesulfonic acid. The amount of acidic emulsifier used is not particularly limited, and can be appropriately set based on (a) the desired volume average particle size of the polyorganosiloxane and the alkoxysilyl-containing synthetic resin, (b) the concentration of the solid components (monomer mixture) in the reaction solution, (c) polymerization conditions such as polymerization temperature, and (d) whether and how much of an additive such as a surfactant is used.

[0195] The volume average particle size of the obtained polyorganosiloxane can be controlled by (a) the degree of pre-dispersion of the raw materials, (b) the amount of emulsifier, (c) the polymerization temperature, and (d) the method of supplying the raw materials.

[0196] When polyorganosiloxanes are obtained through emulsion polymerization in the presence of an acidic emulsifier, the resulting aqueous latex is strongly acidic. Therefore, neutralization is preferably performed after the polymerization reaction is complete. The alkaline compound used for neutralization is not particularly limited, but examples include sodium hydroxide, potassium hydroxide, ammonia, and triethylamine. The aqueous latex can be neutralized by adding these alkaline compounds directly or in aqueous solution to the polyorganosiloxane-containing aqueous latex.

[0197] In step A-1, the total amount of the polyfunctional alkoxysilane compound and the polyfunctional monomer in the 100% by weight mixture for forming the polyorganosiloxane is preferably 0.50% by weight or less. Based on this configuration, a non-crosslinked polyorganosiloxane can be obtained.

[0198] (Process A-2)

[0199] Step A-2 is the formation (preparation) of a graft bond with a polyorganosiloxane containing the structural unit U.2 The grafting process. The grafted portion can be formed by polymerizing the monomers used to form the grafted portion (a mixture of monomers for grafting) in the presence of a polyorganosiloxane using known free radical polymerization.

[0200] In cases where polyorganosiloxanes are obtained through emulsion polymerization in the presence of the aforementioned acidic emulsifier (i.e., polyorganosiloxanes are obtained in the form of aqueous latex), the polymerization of the grafted portion is preferably carried out by emulsion polymerization. The grafted portion can be manufactured, for example, according to the method described in International Publication No. WO2005 / 028546.

[0201] The monomer mixture for grafting contains structural unit U. 2 The source of monomer M 2 Regarding monomer M 2 The monomer M described in the above (grafting part) section. 2 Since the records are identical, this account is cited, and further explanation is omitted here.

[0202] The type and amount of structural units of the grafted portion can be determined based on the type and amount of monomers contained in the monomer mixture for grafting. Therefore, the type and amount of monomers contained in the monomer mixture for grafting can be appropriately set in a manner that allows the grafted portion described in the above-mentioned (grafted portion) item to be obtained.

[0203] Monomer M in process A-2 2 The amount used and the structural unit U in the obtained grafting part 2 The content is related to the monomer M in process A-2. 2 There is no particular limitation on the amount used, but structural unit U is preferred in 100% by weight of the grafting portion. 2 The content is 1.0% by weight or more and 80.0% by weight or less. Monomer M in process A-2 2The amount used, for example, in 100% by weight of the monomer mixture for grafting, is preferably 1.0% by weight or more and 80.0% by weight or less, more preferably 1.0% by weight or more and 75.0% by weight or less, more preferably 1.0% by weight or more and 70.0% by weight or less, more preferably 1.0% by weight or more and 65.0% by weight or less, more preferably 1.0% by weight or more and 60.0% by weight or less, more preferably 1.5% by weight or more and 55.0% by weight or less, more preferably 1.5% by weight or more and 50.0% by weight or less, more preferably 1.5% by weight or more and 45.0% by weight or less, more preferably 1.5% by weight or more and 40.0% by weight or less, more preferably 2.0% by weight or more and 38.0% by weight or less, more preferably... Preferably, the concentration is 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; further 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. According to this configuration, it has the advantages that (a) the water-based coating can provide a coating film with a lower dielectric loss tangent (tanδ), and (b) the bubbling generated when the coating film obtained by the water-based coating is immersed in water is further reduced or eliminated.

[0204] In step A-2, when emulsion polymerization is used, a thermally decomposable initiator can be used as the free radical polymerization initiator. Examples of such thermally decomposable initiators include 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate, which are well-known initiators.

[0205] Redox initiators can also be used as free radical polymerization initiators. Examples of redox initiators include combinations of peroxides such as (a) organic and inorganic peroxides, (b) reducing agents such as sodium formaldehyde sulfoxylate and glucose as needed, transition metal salts such as ferric sulfate (II) as needed, chelating agents such as disodium ethylenediaminetetraacetate as needed, and phosphorus-containing compounds such as sodium pyrophosphate as needed. Examples of organic peroxides include tert-butyl peroxyisopropyl carbonate, terpene hydrogen peroxide, cumene hydroperoxide, dicumene peroxide, tert-butyl hydrogen peroxide, di-tert-butyl peroxide, and tert-hexyl peroxide. Examples of inorganic peroxides include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

[0206] In this manufacturing method, of the total 100% by weight of the polyorganosiloxane-forming monomer mixture and the grafting monomer mixture, the polyorganosiloxane-forming monomer mixture is preferably 55% by weight or more and 95% by weight or less. According to this configuration, it has the advantage of providing a waterborne coating capable of producing a film with excellent water repellency. In this manufacturing method, of the total 100% by weight of the polyorganosiloxane-forming monomer mixture and the grafting monomer mixture, the polyorganosiloxane-forming monomer mixture is more preferably 55% by weight or more and 95% by weight or less, more preferably 60% by weight or more and 95% by weight or less, further preferably 65% ​​by weight or more and 95% by weight or less, and particularly preferably 70% by weight or more and 95% by weight or less. According to this configuration, it has the advantage of providing a waterborne coating capable of forming a film with even better water repellency and better film-forming properties.

[0207] The monomer M in this manufacturing method 2 The amount of [the substance] used and the structural unit U in the resulting alkoxysilyl-containing synthetic resin 2 The content is related to the monomer M in this manufacturing method. 2 The amount used is not particularly limited, but in 100% by weight of synthetic resins containing alkoxysilyl groups, the preferred structural unit is U. 2 The content is 0.5% by weight or more. Additionally, the monomer M in this manufacturing method... 2 The preferred amount of [specific component] in 100% by weight of alkoxysilyl-containing synthetic resins is structural unit U. 2 The content is such that it is used in an amount of 5.0% by weight or less. The monomer M in this manufacturing method... 2 The amount of monomer 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, further preferably 1.5% by weight or more, and particularly preferably 2.0% by weight or more, in a total of 100% by weight of the mixture of monomers for forming polyorganosiloxane and the mixture of monomers for forming grafting. According to this configuration, it has the advantage of improved coating strength. The monomer M in this manufacturing method... 2 The amount of [the monomer 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, in a total of 100% by weight of the monomer mixture for forming polyorganosiloxane and the monomer mixture for forming graft portion. According to this configuration, it has the advantage of improved film-forming properties.

[0208] From the perspective of significantly improving the storage stability of emulsions of synthetic resins containing alkoxysilyl groups, the monomer mixture for grafting in step A-2 preferably contains one or more of (meth)acrylate monomers selected from alkyl groups having 4 or more carbon atoms and (meth)acrylate monomers with cycloalkyl groups having 4 or more carbon atoms, or it may consist of only one or more structural units selected from these. From the perspective of significantly improving the storage stability of emulsions of synthetic resins containing alkoxysilyl groups, the grafting monomer mixture in step A-2 preferably contains at least 60% by weight of one or more selected from (meth)acrylate monomers having alkyl groups having 4 or more carbon atoms and (meth)acrylate monomers having cycloalkyl groups having 4 or more carbon atoms, more preferably 60% by weight and 99% by weight or less, more preferably 62% by weight and 98% by weight or less, further preferably 65% ​​by weight and 97% by weight or less, particularly preferably 68% by weight and 96% by weight or less, and most preferably 70% by weight and 95% by weight or less.

[0209] The monomer mixture for grafting formation in step A-2 preferably includes a reactive emulsifier. Regarding the reactive emulsifier, it is the same as the reactive emulsifier described in the above-mentioned item (from the structural unit of the reactive emulsifier), therefore, that description is cited and 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 in 100% by weight of the monomer mixture for grafting formation, 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, further 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-mentioned range, it has the advantage of further reducing or eliminating the generation of scale when manufacturing water-based coatings.

[0210] The monomer mixture for grafting in step A-2 may or may not contain a chain transfer agent. Regarding the chain transfer agent, it is the same as the chain transfer agent described in the section on (structural units from chain transfer agents) above, therefore, that description is cited and omitted here.

[0211] In the polymerization of the monomer mixtures during the manufacture of water-based coatings, in addition to the components mentioned above, emulsifiers and surfactants may be further used. The types and amounts of the emulsifiers and surfactants mentioned above are within the known range.

[0212] In the manufacture of waterborne coatings, the polymerization temperature, pressure, and deoxidation conditions of the monomer mixture can be within a known range.

[0213] By implementing step A, which includes step A-2, an emulsion containing an alkoxysilyl-containing synthetic resin can be obtained. As described above, in step A-2, a non-grafted polymer can be obtained simultaneously with the grafted portion. The non-grafted polymer can form an emulsion together with the alkoxysilyl-containing synthetic resin. In other words, without removing the non-grafted polymer from the emulsion in step A-2, an emulsion containing both an alkoxysilyl-containing synthetic resin and a non-grafted polymer can be obtained.

[0214] The emulsion containing the alkoxysilyl-containing synthetic resin obtained through step A can be used directly as solution A, or diluted with water (e.g., deionized water) as needed. Solution A can be prepared by further adding the antifouling agent (described later), the organic solvent (described later), and / or any other component 1 mentioned above to the emulsion obtained through step A. In other words, step A can 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 explained below in (2-3. Antifouling Agent) and (2-4. Organic Solvent), and therefore, their description is omitted here. The other component 1 is the same as the other component 1 described above in (Other Component 1), and therefore, their description is omitted here.

[0215] (3-2. Process B)

[0216] Step B is the step of preparing liquid B. There are no particular limitations on step B. For example, step B can be a method of mixing component (B) and any raw materials containing the solvent and any other component 2 mentioned above using a mixer.

[0217] [4. Application Methods of Water-Based Coatings (Coating Film Manufacturing Methods)]

[0218] This method of using water-based coating can also be considered a construction method that uses a water-based coating film (e.g., an antifouling coating film). This method of using water-based coating includes the step of applying the water-based coating to an underwater structure. Specifically, one embodiment of the water-based coating method of the present invention includes the step of applying the water-based coating of one embodiment of the present invention described in [2. Water-based Coating] above, or the water-based coating obtained by the water-based coating manufacturing method of one embodiment of the present invention described in [3. Water-based Coating Manufacturing Method] above, to an underwater structure. This method of using water-based coating can also be considered a method of manufacturing a coating film. Specifically, one embodiment of the coating film manufacturing method of the present invention includes the step of applying the water-based coating of one embodiment of the present invention described in [2. Water-based Coating] above, or the water-based coating obtained by the water-based coating manufacturing method of one embodiment of the present invention described in [3. Water-based Coating Manufacturing Method] above, to an underwater structure. This water-based coating has excellent film-forming properties. Therefore, by applying the water-based coating 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 the method of applying the water-based coating, a coating film with no cracks or very few cracks can be formed on the surface or inner surface of a structure in water. That is, in a preferred embodiment of the present invention, by implementing the method of applying the water-based coating, a coating film with excellent antifouling properties (e.g., antifouling properties against aquatic organisms) can be provided on the surface or inner surface of a structure in water.

[0219] When using (applying) this water-based coating, mix liquid A and liquid B before use, in other words, before application. There are no particular limitations on the method of mixing liquid A and liquid B; any existing known method may be used. Apply the mixture obtained by mixing liquid A and liquid B to the substrate (e.g., an underwater structure) and allow it to dry, thereby forming a coating film on the substrate (e.g., the underwater structure). Preferably, the mixture obtained by mixing liquid A and liquid B is applied to the substrate (e.g., the underwater structure) as early as possible after preparation, for example, within 3 hours.

[0220] There are no particular limitations on the application method of water-based coatings in the coating process, and known methods can be used. For example, coating methods can include casting, dipping, spraying, brushing, roller coating, dip coating, electrostatic coating, electrodeposition coating, etc.

[0221] In the coating process, coating robots can be used. Coating robots can also be used to press water-based coatings onto underwater structures in bead, monofilament, or swirl patterns. Alternatively, water-based coatings can be applied to underwater structures using spraying or streaming methods.

[0222] Water-based coatings applied to underwater structures can be dried. As described above, by applying a water-based coating to an underwater structure and allowing it to dry arbitrarily, a coating film can be formed on the surface or inner surface of the underwater structure that is completely free of cracks or has very few cracks. As a result, by applying a water-based coating to an underwater structure and allowing it to dry arbitrarily, an antifouling coating film can be formed on the surface or inner surface of the underwater structure.

[0223] One embodiment of the present invention provides a method for using water-based coatings or a method for manufacturing coating films, which may be configured as described below.

[0224] The method for applying water-based coatings or the method for manufacturing coating films, the method including:

[0225] The process of applying water-based coatings to structures in water.

[0226] Here, the above-mentioned water-based coating contains:

[0227] Emulsion A comprising (A) an emulsion of a synthetic resin containing alkoxysilyl groups, and

[0228] Solution B contains (B) a substance that promotes the hydrolysis / condensation of alkoxysilyl groups.

[0229] The aforementioned alkoxysilyl-containing synthetic resin comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane.

[0230] The aforementioned polyorganosiloxane (a) comprises a structural unit U derived from a monomer represented by the following formula (1). 1 And (b) is not cross-linked.

[0231] The graft portion described above includes structural unit U from the monomer represented by the following formula (2). 2 ,

[0232] R 1 m R 2 (4-m-n) SiX n ···(1)

[0233] In the formula, R 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2It is an alkyl group with 1 or more and 4 or less carbon atoms, X is an alkoxy group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less;

[0234] R 3 p R 4 (4-p-q) SiY q ···(2)

[0235] In the formula, R 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0236] [5. Coating]

[0237] The coating film formed by the method described in item [4. Method of using water-based coating (method of manufacturing coating film)] above is also an embodiment of the present invention. That is, (a) a coating film formed by the present water-based coating described in item [2. Water-based coating] above, or (b) a coating film formed by the water-based coating manufactured by the present manufacturing method described in item [3. Method of manufacturing water-based coating] above, is also an embodiment of the present invention. It can also be considered that the coating film of an embodiment of the present invention (a) includes the present water-based coating described in item [2. Water-based coating] above, or (b) includes the water-based coating manufactured by the present manufacturing method described in item [3. Method of manufacturing water-based coating] above.

[0238] [6. Applications]

[0239] This water-based coating can be suitable as an antifouling coating for the surface or interior surfaces of various underwater structures. Examples of underwater structures include ships, aquaculture and fishing equipment (e.g., ropes, fishing nets, fishing gear, floats, buoys, TetraPOT, etc.), oil booms, water supply and drainage outlets of thermal or nuclear power plants, cooling water pipes and piping for seawater utilization machinery, submarine tunnels, seabed bases, artificial floating islands, harbor facilities, canals and waterways, various marine civil engineering projects, industrial water-based facilities, bridges, and buoys.

[0240] One embodiment of the present invention may include the following configuration.

[0241] [1] A waterborne coating comprising a multi-component waterborne coating having a liquid A and a liquid B, wherein the liquid A comprises (A) an emulsion of a synthetic resin containing an alkoxysilyl group, and the liquid B comprises (B) a substance that promotes the hydrolysis / condensation of the alkoxysilyl group, wherein the synthetic resin containing the alkoxysilyl group comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane, wherein the polyorganosiloxane (a) comprises a structural unit U from a monomer represented by the following formula (1). 1 Furthermore, (b) the grafted portion is non-crosslinked, comprising structural units U derived from the monomer represented by the following formula (2). 2 ,

[0242] R 1 m R 2 (4-m-n) SiX n ···(1)

[0243] In the formula, R 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 X is an alkyl group with 1 or more and 4 or less carbon atoms, m and n are each an independent integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less.

[0244] R 3 p R 4 (4-p-q) SiY q ···(2)

[0245] In the formula, R 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0246] [2] According to the water-based coating described in [1], wherein,

[0247] Of the 100% by weight of the graft portion described above, the graft portion comprises 60% by weight or more of one or more structural units selected from the following:

[0248] Structural units derived from (meth)acrylate monomers having alkyl groups having 4 or more carbon atoms, and

[0249] Structural units derived from cycloalkyl (meth)acrylate monomers having 4 or more carbon atoms.

[0250] [3] According to the water-based coating described in [1] or [2], wherein,

[0251] The substances in (B) that promote the hydrolysis / condensation of alkoxysilyl groups include one or more selected from organometallic compounds, alkali metal compounds, acidic catalysts, and basic catalysts.

[0252] [4] The water-based coating according to any one of [1] to [3], wherein,

[0253] In 100% by weight of the above-mentioned alkoxysilyl-containing synthetic resin, the alkoxysilyl-containing synthetic resin contains 0.5% by weight or more of the above-mentioned structural unit U. 2 .

[0254] [5] The water-based coating according to any one of [1] to [4] further comprises an antifouling agent.

[0255] [6] A method for manufacturing a coating film, the method comprising:

[0256] The process of applying the water-based coating described in any one of [1] to [5] to a structure in water.

[0257] [7] An aqueous coating comprising an emulsion of a synthetic resin containing an alkoxysilyl group, the emulsion of the synthetic resin containing the alkoxysilyl group comprising a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane, wherein the polyorganosiloxane (a) comprises a structural unit U from a monomer represented by the following formula (1). 1 Furthermore, (b) the grafted portion is non-crosslinked, comprising structural units U derived from the monomer represented by the following formula (2). 2 ,

[0258] R 1 m R 2 (4-m-n) SiX n ···(1)

[0259] In the formula, R 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 It is an alkyl group with 1 or more and 4 or less carbon atoms, X is an alkoxy group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 1 or more and 3 or less, and the sum of m and n is 2 or more and 4 or less;

[0260] R 3 p R 4 (4-p-q) SiY q ···(2)

[0261] In the formula, R 3 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

[0262] Example

[0263] The following describes one embodiment of the present invention in more detail through examples and comparative examples, but the present invention is not limited to these examples. An embodiment of the present invention may be implemented with appropriate modifications within the scope of the above or subsequent descriptions, all of which are included within the technical scope of the present invention. It should be noted that in the following examples and comparative examples, "parts" and "%" refer to parts by weight or percentage by weight.

[0264] <Evaluation Methods>

[0265] First, the evaluation method for the alkoxysilyl-containing synthetic resins and waterborne coatings manufactured through the examples and comparative examples will be described below.

[0266] (Determination of volume average particle size)

[0267] The volume average particle size (Mv) of polyorganosiloxanes dispersed in aqueous latex or alkoxysilyl-containing synthetic resins dispersed in emulsions was determined using a Nanotrac WaveII-EX150 (manufactured by Microtrac BEL Co., Ltd.). Materials obtained by diluting the aqueous latex or emulsion with deionized water were used as test samples. The determination was performed by adjusting the sample concentration to a range where the loading index was between 1 and 10, using water and the refractive index of the polyorganosiloxanes or alkoxysilyl-containing synthetic resins obtained in each manufacturing example, measuring for 120 seconds.

[0268] (Evaluation method for film-forming properties of water-based coatings)

[0269] The film-forming properties of water-based coatings were evaluated using the following methods: (1) For each water-based coating, 100 parts by weight of liquid A and 1 part by weight of liquid B were mixed; (2) After adjusting the mixture (water-based coating), the mixture was applied to an aluminum plate as early as possible (at least within 3 hours) so that the dried film thickness reached 100 μm; (3) The aluminum plate was left to stand at 25°C overnight to form a coating film of the water-based coating; (4) The coating surface condition of the aluminum plate was confirmed by visual inspection, and the film-forming properties were evaluated according to the following criteria.

[0270] 2 (Good): No cracks.

[0271] 1 (Defective): Cracks are present.

[0272] (Example 1)

[0273] ((A) Manufacturing of emulsions of synthetic resins containing alkoxysilyl groups)

[0274] (Preparation of polyorganosiloxanes)

[0275] 251 parts by weight of deionized water, 0.5 parts by weight of sodium dodecyl sulfate (SDS), and a mixture of monomers for forming polyorganosiloxanes (composed of 100 parts by weight of octamethylcyclotetrasiloxane as the organosiloxane and M as the monomer) 1 A mixture of 2 parts by weight of 3-acryloyloxypropyl dimethoxymethylsilane was mixed. The resulting mixture was stirred at 10,000 rpm for 5 minutes using a homogenizer to prepare an emulsion. The total volume of the resulting emulsion was then added to a five-necked glass container. This glass container was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and inlets 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. The temperature inside the glass container was then cooled to 25°C, and the reaction solution was left to stand for 20 hours after reaching 25°C. The polymerization was then terminated by adjusting the pH of the reaction solution to pH 6.8 using sodium hydroxide. Through the above operations, an aqueous latex (R-1) containing polyorganosiloxane was obtained. The polymerization conversion rate of the monomer component was 97%. The volume average particle size of the polyorganosiloxane contained in the obtained aqueous latex (R-1) was 280 nm.

[0276] (Preparation of the graft)

[0277] Next, 275.5 parts by weight of aqueous latex (R-1) containing polysiloxane (70 parts by weight of polysiloxane) was added to a glass reactor. This glass reactor was equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The added raw materials were stirred at 60°C while the gas inside the glass reactor was purged with nitrogen. Next, 0.004 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by weight of ferrous sulfate 7-hydrate, and 0.13 parts by weight of sodium formaldehyde sulfoxylate (SFS) were added to the glass reactor and stirred for 10 minutes. Then, a monomer mixture for grafting (consisting of 28.5 parts by weight of butyl methacrylate (BMA) and monomer M) was continuously added to the glass reactor over 120 minutes. 2 A mixture of 1.5 parts by weight of 3-methacryloyloxypropyltriethoxysilane and 0.085 parts by weight of BHP was prepared. Then, 0.013 parts by weight of tert-butyl hydroperoxide (BHP) was added to a glass reactor, and the mixture was stirred for another hour to complete the polymerization (manufacturing) of the alkoxysilyl-containing synthetic resin. Through the above operations, an emulsion containing the alkoxysilyl-containing synthetic resin, namely (A) alkoxysilyl-containing synthetic resin emulsion (A-1), was obtained. The polymerization conversion rate of the monomer components was over 97%. The volume average particle size of the alkoxysilyl-containing synthetic resin contained in the (A) alkoxysilyl-containing synthetic resin emulsion (A-1) was 293 nm. The solid content in the (A) alkoxysilyl-containing synthetic resin emulsion was determined using an electronic moisture meter, and the result was 31 parts by weight. In the emulsion (A-1) of the synthetic resin containing alkoxysilane (A), the polyorganosiloxane can be considered as the core composed solely of polyorganosiloxane.

[0278] (Manufacturing of Liquid A)

[0279] 83 parts by weight of the obtained (A) alkoxysilyl-containing synthetic resin emulsion (A-1), 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 Sannopco Corporation) as a tackifier, 0.2 parts by weight of BYK-333 (manufactured by BYK Japan Corporation) as a leveling agent, and 0.4 parts by weight of Agitan295 (manufactured by MUNZING CHEMIE Corporation) as a defoamer were mixed to obtain liquid A.

[0280] (Manufacturing of Liquid B)

[0281] One part by weight of Neostann U220 (diacetylacetonate dibutyltin, manufactured by Nitto Chemical Co., Ltd.), which is component (B), was mixed with one part by weight of dipropylene glycol n-butyl ether to obtain solution B.

[0282] Through the above operations, liquid A and liquid B were obtained. That is, through the above operations, a water-based coating containing liquid A and liquid B was obtained.

[0283] (Examples 2-9 and Comparative Examples 1-2)

[0284] In the preparation of the grafted portion, the amount of the aqueous latex (R-1) containing polyorganosiloxane was changed to the amount recorded in the "Core (Polyorganosiloxane) Content" column of Table 1 or 2, and the grafting monomer used in the preparation of the grafted portion was changed to a mixture of monomers recorded in the "Mixture of Grafting Monomers" column of Table 1 or 2. Otherwise, an emulsion containing an alkoxysilyl-containing synthetic resin, namely (A) an emulsion containing an alkoxysilyl-containing synthetic resin, was obtained by the same method as in Example 1. Next, liquid A and liquid B were manufactured by the same method as in Example 1. Through the above operations, an aqueous coating having liquid A and liquid B was obtained.

[0285] The film-forming properties of the obtained water-based coatings were evaluated after one week or one month. As for the evaluation method for film-forming properties after one week, the following procedures were performed sequentially: (A1) The water-based coating was placed in an environment at 25°C for one week from the time of manufacture of A; (A2) Using A solution after one week of placement, the film-forming properties were evaluated using the method described in the section on (Evaluation Method for Film-forming Properties of Water-based Coatings) above. The results are shown in the "Film-forming Properties of Water-based Coatings (After 1 Week)" column of Tables 1 and 2. As for the evaluation method for film-forming properties after one month, the following procedures were performed sequentially: (B1) The water-based coating was placed in an environment at 25°C for one month from the time of manufacture of A solution; (B2) Using A solution after one month of placement, the film-forming properties were evaluated using the method described in the section on (Evaluation Method for Film-forming Properties of Water-based Coatings) above. The results are shown in the "Film-forming Properties of Water-based Coatings (After 1 Month)" column of Tables 1 and 2.

[0286] It should be noted that only liquid A in Examples 1-9 can be considered as an embodiment of the water-based coating of the present invention.

[0287] (Example 10)

[0288] The film-forming properties of the water-based coating formed solely from liquid A in Example 3 were evaluated. As a method for evaluating film-forming properties, the following procedures (C1) to (C4) were performed sequentially: (C1) The water-based coating was placed in an environment at 25°C for one week from the time liquid A was manufactured; (C2) The water-based coating formed solely from liquid A was applied to an aluminum plate after one week of placement using a coating applicator to achieve a dried film thickness of 100 μm; (C3) The resulting aluminum plate was placed at 25°C overnight to create a coating film of the water-based coating formed solely from liquid A; (C4) The surface condition of the obtained aluminum plate was confirmed by visual inspection, and the film-forming properties of the coating film formed solely from liquid A were evaluated according to the criteria described in the above-mentioned (Method for Evaluating the Film-Forming Properties of Water-Based Coatings). The film-forming property was 2 (good). On the other hand, the coating film obtained by the water-based coating formed solely from liquid A deformed upon touch, resulting in low coating strength.

[0289]

[0290]

[0291] Industrial applicability

[0292] According to one embodiment of the present invention, a water-based coating with excellent storage stability can be provided. Therefore, the water-based coating of one embodiment of the present invention, and the coating film formed by the water-based coating, can be suitably used in various marine civil engineering projects, industrial water-based facilities, bridges, and floating structures such as ships, materials for aquaculture and fishing, oil booms, water supply and drainage outlets of thermal or nuclear power plants, cooling water pipes and seawater utilization machinery, submarine tunnels, submarine bases, artificial floating islands, harbor facilities, canals and waterways, etc.

Claims

1. A water-based coating, comprising a multi-component water-based coating having a liquid A and a liquid B, wherein liquid A comprises (A) an emulsion of a synthetic resin containing alkoxysilyl groups, and liquid B comprises (B) a substance that promotes the hydrolysis / condensation of alkoxysilyl groups. The alkoxysilyl-containing synthetic resin comprises a polyorganosiloxane and a graft portion grafted to the polyorganosiloxane. The polyorganosiloxane (a) comprises a structural unit U derived from a monomer represented by the following formula (1). 1 And (b) is not cross-linked. The graft portion comprises structural units U from the monomer represented by the following formula (2). 2 , R 1 m R 2 (4-m-n) SiX n ···(1) In the formula, R 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 It is an alkyl group with 1 or more and 4 or less carbon atoms, X is an alkoxy group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 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 olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

2. The water-based coating according to claim 1, wherein, Of the 100% by weight of the graft portion, the graft portion comprises 60% by weight or more of one or more structural units selected from the following: Structural units derived from (meth)acrylate monomers having alkyl groups having 4 or more carbon atoms, and Structural units derived from cycloalkyl (meth)acrylate monomers having 4 or more carbon atoms.

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

4. The water-based coating according to claim 1 or 2, wherein, In 100% by weight of the alkoxysilyl-containing synthetic resin, the alkoxysilyl-containing synthetic resin contains 0.5% by weight or more of the structural unit U. 2 .

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

6. A method for manufacturing a coating film, the method comprising: The process of applying the water-based coating according to any one of claims 1 to 5 to an underwater structure.

7. A water-based coating comprising an emulsion of a synthetic resin containing an alkoxysilyl group, said emulsion containing an alkoxysilyl group comprising a polyorganosiloxane and graft portions grafted to said polyorganosiloxane. The polyorganosiloxane (a) comprises a structural unit U derived from a monomer represented by the following formula (1). 1 And (b) is not cross-linked. The graft portion comprises structural units U from the monomer represented by the following formula (2). 2 , R 1 m R 2 (4-m-n) SiX n ···(1) In the formula, R 1 R is a monovalent organic group having an olefinic unsaturated group and / or a mercapto group. 2 It is an alkyl group with 1 or more and 4 or less carbon atoms, X is an alkoxy group with 1 or more and 4 or less carbon atoms, m and n are each an integer with 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 olefinic unsaturated group and / or a mercapto group. 4 It is an alkyl group with 1 or more carbon atoms and 4 or less, Y is an alkoxy group with 2 or more carbon atoms and 4 or less, p and q are each an integer with 1 or more and 3 or less, and the sum of p and q is 2 or more and 4 or less.

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