Antifouling coating composition

Abstract

The purpose of the present invention is to provide an antifouling coating film having excellent surface smoothness, and an antifouling coating composition for forming same. In addition, the purpose of the present invention is to provide a substrate having the antifouling coating film and a method for producing same.　This antifouling coating composition contains: (A) at least one curable silicone selected from (1) and (2) below; and (C) a lubricant.　(1) A polyorganosiloxane having a methyl isobutyl ketoxime group at both ends. (2) A polyorganosiloxane having a hydroxyl group at both ends, and an organosilane represented by formula (I). (In formula (I), R1 represents a substituted or unsubstituted C1-10 hydrocarbon group, X is a methyl isobutyl ketoxime group, and a is 0 or 1.)

Description

Technical Field

[0001] The present invention relates to an antifouling paint composition, an antifouling coating film using the same, and a substrate with an antifouling coating film and a method for producing the same.

Background Art

[0002] Organopolysiloxane-based antifouling coating films are widely used to prevent the attachment of aquatic organisms to ships, underwater structures, fishing materials, etc. Due to their characteristics such as low surface free energy and low elastic modulus, the antifouling coating film can prevent the attachment and settlement of macroorganisms such as barnacles and mussels, and has excellent advantages such as a lower environmental load compared to conventional hydrolyzable and water-dissociable antifouling coating films in which coating film components are released into the environment. For example, Patent Document 1 discloses an antifouling paint composition that is a curable organopolysiloxane composition.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Although the antifouling coating film formed from the antifouling paint described in Patent Document 1 is excellent in antifouling property, there is room for improvement from the viewpoint of surface smoothness. Further reduction of environmental load is also required. An object of the present invention is to provide an antifouling coating film excellent in surface smoothness and an antifouling paint composition for forming the same. Another object of the present invention is to provide a substrate with an antifouling coating film having the above antifouling coating film and a method for producing the same.

Means for Solving the Problems

[0005] In view of the above problems, the present inventors have conducted intensive research and found that the above problems can be solved by adopting a methyl isobutyl ketoxime group as a hydrolyzable group, thereby completing the present invention. The present invention relates to the following [1] to

[15] . [1] An antifouling paint composition containing at least one curable silicone (A) selected from the following (1) and (2), and a lubricant (C). (1) A polyorganosiloxane having methyl isobutyl ketoxime groups at both ends (2) A polyorganosiloxane having hydroxy groups at both ends, and an organosilane represented by the following formula (I)

[0006] [Chemical formula] (In formula (I), R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, X is a methyl isobutyl ketoxime group, and a is 0 or 1.)

[0007] [2] The antifouling paint composition according to [1], wherein the curable silicone (A) contains a polyorganosiloxane having methyl isobutyl ketoxime groups at both ends. [3] The antifouling paint composition according to [1] or [2], wherein the polyorganosiloxane has a polydimethylsiloxane structure. [4] The antifouling paint composition according to any one of [1] to [3], further containing hydrophobic silica particles (B1). [5] The antifouling paint composition according to any one of [1] to [4], further containing hydrophilic silica particles (B2). [6] The antifouling paint composition according to any one of [1] to [5], wherein the lubricant (C) is at least one selected from the group consisting of silicone oil, paraffin oil, fats and oils, an acrylic resin having a hydrophilic group, and a polyalkylene glycol. [7] The antifouling paint composition according to [6], wherein the silicone oil is at least one selected from phenyl-modified silicone oil and polyether-modified silicone oil. [8] The antifouling paint composition according to any one of [1] to [7], further containing a coloring pigment (D). [9] The antifouling paint composition according to any one of [1] to [7], wherein the content of the coloring pigment (D) in the solid content of the antifouling paint composition is 1% by mass or less.

[10] The antifouling paint composition according to [9], wherein the content of the lubricant (C) with respect to 100 parts by mass of the polyorganosiloxane is 30 parts by mass or more and 200 parts by mass or less.

[11] The antifouling paint composition according to any one of [1] to

[10] , wherein the content of the curable silicone (A) in the solid content of the antifouling paint composition is 40% by mass or more and 90% by mass or less.

[12] An antifouling paint film formed from the antifouling paint composition according to any one of [1] to

[11] .

[13] A substrate with an antifouling paint film, having a substrate and the antifouling paint film according to

[12] provided on the surface of the substrate.

[14] The substrate with an antifouling paint film according to

[13] , wherein the substrate is at least one selected from ships, underwater structures, fishing materials, and water supply and drainage pipes.

[15] A method for manufacturing a substrate with an antifouling paint film, comprising a step of applying the antifouling paint composition according to any one of [1] to

[11] to a substrate or impregnating a substrate with the antifouling paint composition according to any one of [1] to

[11] . [Effect of the Invention]

[0008] According to the present invention, there are provided an antifouling paint film excellent in surface smoothness and an antifouling paint composition for forming the same. Further, according to the present invention, there are provided a substrate with an antifouling paint film having the antifouling paint film and a method for manufacturing the same. [Embodiments for Carrying Out the Invention]

[0009] Hereinafter, the antifouling paint composition of the present invention, the antifouling paint film using the same, and the substrate with an antifouling paint film and a method for manufacturing the same will be described in detail.

[0010] [Antifouling paint composition] The antifouling paint composition of the present invention contains at least one curable silicone (A) selected from the following (1) and (2), and a lubricant (C). (1) A polyorganosiloxane having methyl isobutyl ketoxime groups at both ends (hereinafter also referred to as (A-1)). (2) A polyorganosiloxane having hydroxy groups at both ends, and an organosilane represented by the following formula (I) (hereinafter also referred to as (A-2)).

[0011] [Chemical formula] (In formula (I), R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, X is a methyl isobutyl ketoxime group, and a is 0 or 1.)

[0012] According to the antifouling paint composition of the present invention, an antifouling coating film excellent in surface smoothness can be obtained. Although the detailed reason for obtaining the above effect is unknown, in the curable silicone (A), by adopting a methyl isobutyl ketoxime group instead of the conventionally used methyl ethyl ketoxime group as the hydrolyzable group, surprisingly, the surface smoothness is considered to be improved. In addition, methyl ethyl ketoxime generated during the curing of conventional products has been pointed out to have concerns about safety by ECHA (European Chemical Agency), and there is a strong demand for providing alternatives for reducing the environmental load and exposure to painters in the painting environment. Furthermore, it is considered that excellent antifouling properties are exhibited by containing a lubricant (C) in addition to the curable silicone (A). In addition, when the antifouling paint composition is a composition that substantially does not contain a colorant, it has an effect of being excellent in transparency. Hereinafter, each component contained in the antifouling paint composition will be described.

[0013] [Curable silicone (A)] The curable silicone (A) is selected from the above (1) or (2). Each will be described in detail below. In addition, when the curable silicone (A) is in the form of (1) and is a polyorganosiloxane having methyl isobutyl ketoxime groups at both ends (hereinafter also referred to as "polyorganosiloxane (a1)"), it is designated as (A-1). When the curable silicone (A) is in the form of (2) and is a polyorganosiloxane having hydroxy groups at both ends (hereinafter also referred to as "polyorganosiloxane (a2)") and an organosilane represented by formula (I) (hereinafter also referred to as "organosilane (a3)"), it is also designated as (A-2). <(1) Polyorganosiloxane having methyl isobutyl ketoxime groups at both ends> The polyorganosiloxane having methyl isobutyl ketoxime groups at both ends (hereinafter also referred to as "polyorganosiloxane (a1)") has at least a polyorganosiloxane structure as the main chain and reactive sites having methyl isobutyl ketoxime groups, and has the reactive sites at both ends. The main chain has a polyorganosiloxane structure. Examples of the polyorganosiloxane structure include a polydimethylsiloxane structure and a polymethylphenylsiloxane structure. Among them, the polydimethylsiloxane structure is preferable. In addition, an alkylene group, a polyoxyalkylene group, etc. may be present in the main chain in a block form. In addition, as a linking site between the main chain and the reactive site, for example, an alkylene group, a polyoxyalkylene group, etc. may be present. The reactive sites react with each other of the reactive sites of the polyorganosiloxane (a1) or with an organic silicon cross-linking agent (F) described later contained in the antifouling paint composition to form a cross-linked structure, becoming a silicone cured body and forming an antifouling coating film. It may also react with a silane coupling agent (G) described later to form a part of the silicone cured body.

[0014] The reactive site preferably has a methyl isobutyl ketoxime group, and its position is preferably at both ends of the main chain. As the polyorganosiloxane having methyl isobutyl ketoxime groups at both ends, a compound represented by the following formula (II) is preferable.

[0015] [Chemical formula] (In formula (II), R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, an aryl group, an aralkyl group, or a halogenated alkyl group, n represents an integer of 10 or more and 10,000 or less, and a represents an integer of 1 or more and 3 or less.)

[0016] In formula (II), n represents an integer of 10 or more and 10,000 or less, preferably 100 or more and 1,000 or less, and it may be appropriately selected so that the kinematic viscosity and weight average molecular weight described later are in a suitable range. a represents an integer of 1 or more and 3 or less, preferably 1 or 2, and more preferably 2. R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. Note that a plurality of R 11 may be the same or different from each other, and when a plurality of R 12 exist, R 12 may be the same or different from each other. The number of carbon atoms of the alkyl group is preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less, still more preferably 1 or 2, and even more preferably 1. The number of carbon atoms of the alkenyl group is preferably 2 or more and 6 or less, more preferably 2 or more and 3 or less, and a vinyl group (-CH=CH2) is particularly preferable. The number of carbon atoms of the alkoxy group is preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2. The number of carbon atoms of the aryl group is preferably 6 or more and 8 or less, and it may have a substituent such as an alkyl group on the aromatic ring. Examples thereof include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), and a naphthyl group. The number of carbon atoms of the aralkyl group is preferably 7 or more and 9 or less. Examples thereof include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, and a diphenylmethyl group. The number of carbon atoms of the halogenated alkyl group is preferably 1 or more and 6 or less. Examples thereof include groups in which some or all of the hydrogen atoms contained in the alkyl group are replaced by halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, R 11 is preferably a methyl group, and R 12 is preferably a vinyl group.

[0017] <(2) A polyorganosiloxane having hydroxy groups at both ends and an organosilane represented by formula (I)> The polyorganosiloxane having hydroxy groups at both ends (hereinafter also referred to as "polyorganosiloxane (a2)") has at least a polyorganosiloxane structure as the main chain and reactive sites having hydroxy groups, and has the reactive sites at both ends. The main chain has a polyorganosiloxane structure. Examples of the polyorganosiloxane structure include a polydimethylsiloxane structure and a polymethylphenylsiloxane structure. Among them, a polydimethylsiloxane structure is preferable. In addition, an alkylene group, a polyoxyalkylene group, or the like may be present in the main chain in a block form. Further, as a connecting site between the main chain and the reactive site, an alkylene group, a polyoxyalkylene group, or the like may be present. The silanol group reacts with an organosilane represented by the following formula (I) (hereinafter also referred to as "organosilane (a3)") to obtain a polyorganosiloxane having methyl isobutyl ketoxime groups at both ends (polyorganosiloxane (a1)). The polyorganosiloxane (a2) reacts with the reactive sites of the polyorganosiloxane (a1) obtained by the above reaction or with an organic silicon crosslinking agent (F) described below contained in the antifouling paint composition to form a crosslinked structure, becoming a silicone cured body and forming an antifouling coating film. It may also react with a silane coupling agent (G) described below to form a part of the silicone cured body.

[0018] As the polyorganosiloxane (a2), a compound represented by the following formula (III) is preferable.

[0019] [Chemical formula] (In formula (III), p represents an integer of 10 or more and 10,000 or less, b represents an integer of 1 or more and 3 or less, and R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, an aryl group, an aralkyl group, or a halogenated alkyl group.)

[0020] In formula (III), p represents an integer of 10 or more and 10,000 or less, preferably 100 or more and 1,000 or less, and can be appropriately selected so that the viscosity and weight average molecular weight described below are in a suitable range. b represents an integer of 1 or more and 3 or less, preferably 1 or 2, and more preferably 1. R 13 and R 14Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. When there are a plurality of Rs 13 may be the same or different from each other, and when 14 there are a plurality of Rs 14 they may be the same or different from each other. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 3, still more preferably 1 or 2, and even more preferably 1. The number of carbon atoms of the alkenyl group is preferably 2 to 6, more preferably 2 to 3, and a vinyl group (-CH=CH2) is even more preferred. The number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. The number of carbon atoms of the aryl group is preferably 6 to 8, and may have a substituent such as an alkyl group on the aromatic ring. Examples include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), and a naphthyl group. The number of carbon atoms of the aralkyl group is preferably 7 to 9. Examples include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, and a diphenylmethyl group. The number of carbon atoms of the halogenated alkyl group is preferably 1 to 6. Examples include a group in which some or all of the hydrogen atoms contained in the alkyl group are replaced by halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, R 13 and R 14 are preferably methyl groups.

[0021] The organosilane (a3) is represented by the following formula (I).

[0022] [Chemical formula] (In formula (I), R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, X is a methyl isobutyl ketoxime group, and a is 0 or 1.)

[0023] In formula (I), a is 0 or 1, and from the viewpoint of the reactivity of the resulting polyorganosiloxane having methyl isobutyl ketoxime groups at both ends, it is preferably 1. R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, and is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. The number of carbon atoms of the alkenyl group is preferably 2 to 6, more preferably 2 to 3, and a vinyl group (-CH=CH2) is preferred. Among these, R 1 is preferably a vinyl group.

[0024] The polyorganosiloxane (a2) and the organosilane (a3) may be mixed with reference to the stoichiometric ratio, and it is preferable to add an excess amount of the organosilane (a3) with respect to the stoichiometric ratio. Specifically, the blending amount of the organosilane (a3) with respect to 100 parts by mass of the polyorganosiloxane (a2) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.

[0025] The weight average molecular weight (Mw) of the curable silicone (A) is preferably 500 or more, more preferably 5,000 or more, still more preferably 10,000 or more, even more preferably 15,000 or more, even more preferably 20,000 or more, from the viewpoints of improving coating workability, curability of the antifouling paint composition, and strength of the formed coating film, and is preferably 1,000,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, even more preferably 40,000 or less. In the present invention, the "weight average molecular weight (Mw)" is measured using GPC (gel permeation chromatography) and calculated by conversion with a standard polystyrene having a known molecular weight.

[0026] The viscosity of the curable silicone (A) at 25°C is preferably 20 mPa·s or more, more preferably 100 mPa·s or more, still more preferably 500 mPa·s or more, even more preferably 1,000 mPa·s or more, from the viewpoints of improving the production workability of the antifouling paint composition, coating workability, curability of the antifouling paint composition, and strength and flexibility of the formed coating film. And it is preferably 100,000 mPa·s or less, more preferably 10,000 mPa·s or less, still more preferably 7,000 mPa·s or less. The viscosity of the curable silicone (A) at 25°C is the viscosity measured by a B-type rotational viscometer (for example, model: BM, manufactured by Tokyo Keiki Co., Ltd.). When the polyorganosiloxane (a1) or polyorganosiloxane (a2) and the silica particles (B) are kneaded and then added to the antifouling paint composition as described later, the viscosity of the kneaded product is preferably 20 mPa·s or more, more preferably 100 mPa·s or more, still more preferably 500 mPa·s or more, even more preferably 1,000 mPa·s or more. And it is preferably 100,000 mPa·s or less, more preferably 10,000 mPa·s or less, still more preferably 7,000 mPa·s or less.

[0027] The content of the curable silicone (A) in the solid content of the antifouling coating composition is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, from the viewpoint of improving the strength of the formed antifouling coating film, and is preferably 90% by mass or less, more preferably 88% by mass or less. Here, the "solid content of the antifouling coating composition" is a component excluding the organic solvent (I) described later and the volatile components contained as solvents in each component, and can be regarded as an antifouling coating film. Further, the "solid content of the antifouling coating composition" may be calculated by measuring the solid content (heating residue) obtained by drying the coating composition in a hot air dryer at 125 °C for 1 hour. The "content of each component in the antifouling coating film" can be calculated from the content of each component in the component obtained by subtracting the organic solvent (I) described later, the volatile components contained as solvents in each component, and the components that are eliminated and volatilized after the curing reaction.

[0028] In the present invention, as the curable silicone (A), it is preferably a polyorganosiloxane (A-1) having methyl isobutyl ketoxime groups at both ends. When the curable silicone (A) is (A-1), it can be prepared as a one-component type coating composition, and has excellent viscosity stability and excellent handleability. On the other hand, when the curable silicone (A) is (A-2), it is necessary to use a two-component curing type coating composition. In such a coating composition, the viscosity easily changes after mixing the main agent and the curing agent, and the handleability is poor. Also, in (A-1), even if there are a plurality of methyl isobutyl ketoxime groups, when one of the methyl isobutyl ketoxime groups present at the terminal (the first methyl isobutyl ketoxime group) reacts, the reactivity of the remaining methyl isobutyl ketoxime groups is very low compared to the first methyl isobutyl ketoxime group. Therefore, a cured product with a structure close to linear is likely to be obtained. On the other hand, in the case of (A-2), since the reactivity of the methyl isobutyl ketoxime groups of the organosilane (a3) is high, it tends to form a non-uniform structure by crosslinking the organosilanes (a3) with each other. It is considered that the structure of these cured products may also affect the physical properties of the coating film. Furthermore, when the curable silicone (A) is (A-1), it has high compatibility with the lubricant (C), and as will be described later, a large amount of the lubricant (C) can be added. However, when the curable silicone (A) is (A-2), its compatibility with the lubricant (C) is low, and it is difficult to blend a large amount of the lubricant (C).

[0029] The antifouling paint composition used in the production method of the present invention preferably contains other components in addition to the curable silicone (A). Examples of other components include silica particles (B), lubricant (C), coloring pigment (D), and biocide (E), organosilicon crosslinking agent (F), silane coupling agent (G), curing catalyst (H), organic solvent (I), pigments other than silica particles (B) and coloring pigment (D), dehydrating agents other than organosilicon crosslinking agent (F), anti-sagging agents and anti-settling agents, enzymes, flame retardants, and thermal conductivity improvers. It is preferable to contain silica particles (B), lubricant (C), coloring pigment (D), and biocide (E), organosilicon crosslinking agent (F), silane coupling agent (G), curing catalyst (H), and organic solvent (I) within the range that does not inhibit the effects of the present invention.

[0030] 〔Silica particles (B)〕 The antifouling paint composition of the present invention preferably contains silica particles (B) from the viewpoints of the hardness, flexibility, and strength of the formed antifouling coating film. Examples of the silica particles (B) include hydrophobic silica particles (B1) and hydrophilic silica particles (B2). Silica particles (B) not only improve the physical properties of the formed antifouling coating film, but also improve the fluidity and thixotropy of the antifouling paint composition. The antifouling paint composition preferably contains at least one selected from the group consisting of hydrophobic silica particles (B1) and hydrophilic silica particles (B2), preferably contains at least hydrophobic silica particles (B1), and more preferably contains both hydrophobic silica particles (B1) and hydrophilic silica particles (B2).

[0031] In particular, when the curable silicone (A) is (A-1), it is preferable to use hydrophobic silica particles (B1) and hydrophilic silica particles (B2) in combination. The present inventors have found that an antifouling paint composition containing (A-2) as the curable silicone (A) has a tendency to have a reduced viscosity and it is difficult to blend hydrophilic silica particles (B2). Incidentally, hydrophobic silica particles (B1) are preferably added from the viewpoints of the hardness, flexibility, and strength of the formed antifouling coating film, and the improvement of the fluidity and thixotropy of the antifouling paint composition. Further, although the hydrophilic silica particles (B2) tend to reduce the viscosity by their addition, they have a function of improving the antifouling property of the formed antifouling coating film.

[0032] As the silica particles (B), dry-process silica and wet-process silica are preferable, and dry-process silica is more preferable.

[0033] The hydrophobic silica particles (B1) are hydrophobic-treated silica (silica whose surface has been hydrophobized), and are obtained by treating the hydroxyl groups (silanol groups) bonded to the silicon atoms on the silica surface with a hydrophobizing agent, and examples thereof include aqueous wet-process silica and hydrophobic fumed silica. Examples of the hydrophobizing agent include organodisilazane, organoalkoxysilane, organochlorosilane, cyclic organopolysilazane, linear organopolysiloxane, etc. Among these, organodisilazane, organoalkoxysilane, and organochlorosilane are preferred. More specifically, silazane compounds such as hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, 1,3 - diethyl - 1,1,3,3 - tetramethyldisilazane, 1,3 - dimethyl - 1,1,3,3 - tetraethyldisilazane, 1,3 - divinyltetramethyldisilazane, 1,3 - diallyltetramethyldisilazane, 1,3 - dibutenyltetramethyldisilazane, 1,3 - dipentenyltetramethyldisilazane, 1,3 - dihexenyltetramethyldisilazane, 1,3 - diheptenyltetramethyldisilazane, 1,3 - dioctenyltetramethyldisilazane, 1,3 - dinonenyltetramethyldisilazane, 1,3 - didecenyltetramethyldisilazane, 1,3 - divinyltetraethyldisilazane, 1,3 - dimethyltetravinyldisilazane, etc., alkoxysilane compounds such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, butenyltrimethoxysilane, etc., chlorosilane compounds such as trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dimethylvinylchlorosilane, alkyldimethylchlorosilane, etc. are included. From the viewpoints of workability and reactivity with silanol groups on the silica surface, it is preferable to use a silazane compound or a chlorosilane compound, and it is more preferable to use methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane, and 1,3 - divinyltetramethyldisilazane, and it is even more preferable to use hexamethyldisilazane, 1,3 - divinyltetramethyldisilazane, and dimethyldichlorosilane.

[0034] Examples of commercially available hydrophobic silica include "AEROSIL R974", "AEROSIL RX200", etc. manufactured by Nippon Aerosil Co., Ltd.

[0035] The hydrophilic silica particles (B2) are untreated silica (surface-untreated silica), and examples include dry-process silica (fumed silica, anhydrous silica), wet-process silica (hydrated silica), etc. Dry-process silica is preferred, and fumed silica is more preferred. Examples of commercially available hydrophilic silica include "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd.

[0036] When the antifouling paint composition of the present invention contains silica particles (B), the content of silica particles (B) in the solid content of the antifouling paint composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, from the viewpoint of improving the strength and hardness of the formed antifouling paint film, and is preferably 20% by mass or less, more preferably 10% by mass or less.

[0037] The content of silica particles (B) relative to 100 parts by mass of the curable silicone (A) is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, from the viewpoint of improving the strength and hardness of the formed antifouling paint film, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less. When hydrophobic silica particles (B1) and hydrophilic silica particles (B2) are used in combination as the silica particles (B), the ratio (B1 / B2) of the content of hydrophobic silica particles (B1) to hydrophilic silica (B2) in the antifouling paint composition is preferably 5 / 95 or more and 90 / 10 or less, more preferably 10 / 80 or more and 80 / 20 or less, still more preferably 15 / 85 or more and 70 / 30 or less, even more preferably 20 / 80 or more and 60 / 40 or less.

[0038] 〔Lubricant (C)〕 The antifouling paint composition of the present invention contains a lubricant (C) from the viewpoints of the paint application workability and antifouling property of the antifouling paint composition. The slip agent (C) can improve the adhesion inhibitory property (antifouling property) of aquatic organisms by imparting slipperiness to the formed antifouling coating film. The slip agent (C) preferably has fluidity at 25°C, and more preferably is in a liquid state. It is considered that when the slip agent has fluidity, the mobility within the antifouling coating film is high, and the effect of imparting slipperiness to the surface can be enhanced. In addition, the viscosity of the antifouling paint composition can be reduced to improve the coatability. The slip agent (C) is preferably at least one selected from oils and polymers having a hydrophilic group.

[0039] Examples of the oils include silicone oil, paraffin oil, and fats and oils, and among them, silicone oil is preferred. Examples of the paraffin oil include liquid paraffin. The fats and oils are esters of fatty acids and glycerin, and examples include animal fats and oils, vegetable fats and oils, and the like.

[0040] Examples of the polymer having a hydrophilic group include acrylic polymers having a hydrophilic group, polyalkylene glycols, etc., and acrylic polymers having a hydrophilic group are preferred. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, and their alkyl ethers.

[0041] That is, the slip agent (C) is preferably at least one selected from the group consisting of silicone oil, paraffin oil, fats and oils, acrylic polymers having a hydrophilic group, and polyalkylene glycols, more preferably at least one selected from silicone oil and acrylic polymers having a hydrophilic group, and still more preferably silicone oil. Also, from the viewpoints of the manufacturing workability of the antifouling paint composition and the antifouling property of the formed antifouling coating film, it is preferable to contain an acrylic polymer having a hydrophilic group, and more preferably to contain both silicone oil and an acrylic polymer having a hydrophilic group. The silicone oil (C1), acrylic polymer (C2) having a hydrophilic group, and paraffin oil (C3), which are suitable lubricants (C) below, will be described in detail.

[0042] <Silicone oil (C1)> Examples of the silicone oil (C1) used in the antifouling paint composition of the present invention include dimethyl silicone (polydimethylsiloxane, unmodified silicone) and modified silicone. The modified silicone is one in which some methyl groups of dimethyl silicone are substituted with organic groups other than methyl groups, and may have a reactive group at one end. Since the silicone oil has a low surface tension and its properties hardly change even in an environment such as low temperature, it easily moves to the surface of the antifouling coating film, and can efficiently improve the adhesion prevention property (antifouling property) and damage resistance of aquatic organisms. When the silicone oil (C1) has a reactive group at one end, examples of the reactive group include a silanol group, an oxime silyl group, an acyloxy silyl group, an alkoxysilyl group, an alkenyloxy silyl group, an aminosilyl group, an amidosilyl group, etc. The silanol group, oxime silyl group, acyloxy silyl group, alkoxysilyl group, and alkenyloxy silyl group are preferred, the silanol group, oxime silyl group, alkoxysilyl group, and alkenyloxy silyl group are more preferred, the silanol group, oxime silyl group, and alkenyloxy silyl group are still more preferred, the silanol group and oxime silyl group are even more preferred, and the oxime silyl group is even more preferred. As the oxime group, an oxime group having 1 to 10 carbon atoms is preferred, and a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a methyl isopropyl ketoxime group, and a methyl isobutyl ketoxime group are more preferred, and a methyl isobutyl ketoxime group is still more preferred. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferred, a methoxy group and an ethoxy group are more preferred, and a methoxy group is still more preferred. The oxime group or alkoxy group may have two or more of these groups bonded to one silicon atom, preferably two or more oxime groups or alkoxy groups bonded to one silicon atom, and more preferably two oxime groups bonded to one silicon atom.

[0043] From the viewpoint of imparting slipperiness to aquatic organisms, improving antifouling properties, and improving the coatability of the antifouling paint composition, the viscosity of the silicone oil (C1) at 25°C is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, still more preferably 40 mPa·s or more, even more preferably 60 mPa·s or more, even more preferably 80 mPa·s or more, and preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, still more preferably 4,000 mPa·s or less. In the present specification, the viscosity of the silicone oil (C1) at 25°C refers to the viscosity measured by a B-type rotational viscometer.

[0044] Also, from the viewpoint of imparting slipperiness to aquatic organisms, improving antifouling properties, and improving the coatability of the antifouling paint composition, the kinematic viscosity of the silicone oil (C1) at 25°C is preferably 10 mm 2 / s or more, more preferably 30 mm 2 / s or more, still more preferably 50 mm 2 / s or more, and preferably 5,000 mm 2 / s or less, more preferably 4,000 mm 2 / s or less, still more preferably 3,500 mm 2 / s or less.

[0045] Examples of the modified silicone include phenyl-modified silicone, polyether-modified silicone, long-chain alkyl-modified silicone, higher fatty acid ester-modified silicone, fluorinated alkyl-modified silicone, carbinol-modified silicone, carboxy-modified silicone, amino-modified silicone, epoxy-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phenol-modified silicone, and the like. Among such modified silicones, from the viewpoints of having good antifouling properties, imparting appropriate thixotropy to the antifouling paint composition, and having good coatability, as the silicone oil (C1), one or more selected from phenyl-modified silicone and polyether-modified silicone are preferred. Also, from the viewpoint of obtaining an antifouling coating film with excellent transparency, it is preferable that the lubricant (C) contains phenyl-modified silicone.

[0046] Examples of the structure of the modified silicone include side-chain modification type, both-end modification type, single-end modification type, block type, side-chain and single-end modification type, and side-chain and both-end modification type.

[0047] Examples of commercially available products of the dimethyl silicone include "KF-96-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 100 mm 2 / s), "KF-96-1,000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 1,000 mm 2 / s), etc.

[0048] From the viewpoints of antifouling properties and facilitating the formation of the antifouling coating film, the phenyl modification rate of the phenyl-modified silicone is preferably 3% or more and 50% or less, more preferably 3% or more and 20% or less, and still more preferably 4% or more and 10% or less. The phenyl modification rate is expressed as a percentage of the number of phenyl groups to the total number of phenyl groups and methyl groups bonded to silicon. From the viewpoints of the antifouling properties of the formed antifouling coating film and the coating workability of the antifouling paint composition, the kinematic viscosity at 25°C of the phenyl-modified silicone is preferably 10 mm 2 / s or more and 5,000 mm 2 / s or less, more preferably 50 mm 2 / s or more and 4,000 mm 2 / s or less, and still more preferably 80 mm 2 / s or more and 3,500 mm 2 / s or less. Examples of commercially available products of the phenyl-modified silicone include "KF-50-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25°C): 100 mm 2 / s), "KF-50-1,000 cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25 °C): 1,000 mm 2 / s), "KF-50-3,000 cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25 °C): 3,000 mm 2 / s), etc. can be mentioned. In addition, as commercially available products of one-terminal methyl ethyl ketoxime-side chain phenyl-modified silicone, "BCA-011" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25 °C): 100 mm 2 / s) can be mentioned.

[0049] When the antifouling paint composition of the present invention contains phenyl-modified silicone, the content in the solid content of the antifouling paint composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, from the viewpoints of the antifouling property of the formed antifouling paint film and the ease of forming the antifouling paint film. When the antifouling paint composition of the present invention is the clear antifouling paint composition described later and contains phenyl-modified silicone, the content of phenyl-modified silicone in the solid content of the antifouling paint composition is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, from the viewpoints of the transparency and antifouling property of the formed antifouling paint film.

[0050] Examples of the structure of the polyether-modified silicone include side chain-modified type, both-terminal modified type, one-terminal modified type, block type, side chain and one-terminal modified type, and side chain and both-terminal modified type. The side chain-modified type and both-terminal modified type are preferred. Examples of the polyether (polyalkylene glycol) constituting the polyether group (polyalkylene glycol group) of the polyether-modified silicone include polyethylene glycol, polypropylene glycol, and a copolymer of ethylene glycol and propylene glycol. A copolymer of polyethylene glycol and polypropylene glycol is preferred. From the viewpoints of the antifouling property of the formed antifouling coating film and the ease of forming the antifouling coating film, the proportion of the polyether partial structure in the structure of the polyether-modified silicone is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 50% by mass or less. When the antifouling paint composition of the present invention contains a polyether-modified silicone, the content in the solid content of the antifouling paint composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, from the viewpoints of improving the antifouling property of the formed antifouling coating film and facilitating the formation of the antifouling coating film, etc., and is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less.

[0051] When the antifouling paint composition of the present invention contains a polyether-modified silicone containing an ethyleneoxy (—OC2H4—) structural unit, from the viewpoint of imparting good antifouling property to the formed antifouling coating film, the total mass of the ethyleneoxy (—OC2H4—) partial structure is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 0.3 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the dimethylsiloxane partial structure (—(CH3)2Si—O—) of the silicone. The kinematic viscosity of the polyether-modified silicone at 25°C is preferably 10 mm 2 / s or more and 5,000 mm 2 / s or less, more preferably 50 mm 2 / s or more and 2,000 mm 2 / s or less, still more preferably 100 mm 2 / s or more and 500 mm 2 / s or less. Commercially available products of the polyether-modified silicone include “X-22-4272” (manufactured by Shin-Etsu Chemical Co., Ltd., both-end type, kinematic viscosity (25°C): 270 mm 2 / s), “KF-6020” (manufactured by Shin-Etsu Chemical Co., Ltd., side-chain type, kinematic viscosity (25°C): 180 mm 2 / s), "FZ-2203" (manufactured by Toray Dow Corning Co., Ltd., block type), "FZ-2160" (manufactured by Toray Dow Corning Co., Ltd., both ends type), "Polyflow KL-402" (manufactured by Kyoeisha Chemical Co., Ltd., kinematic viscosity (25°C): 350 mm 2 / s), etc. can be mentioned.

[0052] From the viewpoint of improving the antifouling property of the formed antifouling coating film and making it easier to form the antifouling coating film, the content of the silicone oil (C1) in the solid content of the antifouling coating composition is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less.

[0053] <Acrylic polymer (C2) having a hydrophilic group> The acrylic polymer (C2) having a hydrophilic group used in the antifouling coating composition of the present invention preferably contains a structural unit derived from a monomer having a hydrophilic group, more preferably contains a structural unit derived from a monomer having a hydrophilic group and a structural unit derived from a hydrophobic monomer, and still more preferably consists of a structural unit derived from a monomer having a hydrophilic group and a structural unit derived from a hydrophobic monomer. The content of the structural unit derived from the monomer having a hydrophilic group in the acrylic polymer (C2) having a hydrophilic group is preferably 1% by mass or more and 100% by mass or less, more preferably 3% by mass or more and 80% by mass or less, still more preferably 5% by mass or more and 70% by mass or less, and even more preferably 10% by mass or more and 60% by mass or less. Since the acrylic polymer has a hydrophilic group, the hydrophilic part of the acrylic polymer in the antifouling coating film dissolves or swells and gradually migrates to the surface of the antifouling coating film, so it is considered that the adhesion of aquatic organisms can be efficiently prevented. In addition, since it has an acrylic structure, it is considered that it undergoes gentle hydrolysis and the affinity with water changes, so that the antifouling property can be maintained for a long time. From the viewpoint of antifouling property, the hydrophilic group of the monomer having a hydrophilic group is preferably an ether group or a hydroxyl group, and more preferably an ether group.

[0054] In addition, the content of the structural unit derived from the hydrophobic monomer in the acrylic polymer (C2) having a hydrophilic group is preferably 99% by mass or less, more preferably 97% by mass or less, still more preferably 95% by mass or less, even more preferably 90% by mass or less, and preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more. By having a hydrophobic monomer, it is considered that it has a high affinity with other components of the antifouling coating film such as a silicone crosslinked body and can uniformly exhibit a sliding effect on the surface of the antifouling coating film.

[0055] From the viewpoint of antifouling property, the monomer having a hydrophilic group is preferably a monomer having a polyalkylene glycol group, a monomer having a hydroxyl group, and a monomer having an alkoxyalkyl group, and more preferably a monomer having a polyalkylene glycol group. Specifically, from the viewpoint of improving antifouling property, one or more selected from polyalkylene glycol (meth)acrylate, hydroxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloylmorpholine, and vinylpyrrolidone are preferable, one or more selected from polyalkylene glycol (meth)acrylate and hydroxyalkyl (meth)acrylate are more preferable, and polyalkylene glycol (meth)acrylate is still more preferable. Note that “(meth)acrylate” means “acrylate or methacrylate”.

[0056] Examples of the polyalkylene glycol (meth)acrylate include those in which one end of the polyalkylene glycol is bonded to (meth)acrylic acid directly through an ester bond or a linking group, and the other end is a hydroxyl group or an alkoxy group, and those having an alkoxy group are preferable. Among them, those in which one end of the polyalkylene glycol is directly ester-bonded to (meth)acrylic acid are preferable, and those in which the other end is an alkoxy group are more preferable. The terminal (meth)acrylic acid is preferably acrylic acid and methacrylic acid, more preferably acrylic acid. Examples of the terminal alkoxy group include a methoxy group, a phenoxy group, an octyloxy group, etc., preferably a methoxy group and a phenoxy group, more preferably a methoxy group.

[0057] The polyalkylene glycol constituting the polyalkylene glycol (meth)acrylate is preferably polyethylene glycol, polypropylene glycol, or a copolymer of ethylene glycol and propylene glycol, more preferably polyethylene glycol. The average number of alkylene glycol units constituting the polyalkylene glycol in the polyalkylene glycol (meth)acrylate is preferably 2 or more and 25 or less, more preferably 3 or more and 15 or less, still more preferably 5 or more and 12 or less.

[0058] Specific examples of the polyalkylene glycol (meth)acrylate include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-butylene glycol) mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, allyloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol methacrylate, octyloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, dodecyloxypolyethylene glycol mono(meth)acrylate, octadecyloxypolyethylene glycol mono(meth)acrylate, nonylphenoxypolypropylene glycol acrylate, etc., and methoxypolyethylene glycol mono(meth)acrylate is preferred.

[0059] Examples of commercially available polyalkylene glycol (meth)acrylates include NK Ester AM-90G (methoxypolyethylene glycol #400 acrylate), NK Ester AM-130G (methoxypolyethylene glycol #550 acrylate), NK Ester M-90G (methoxypolyethylene glycol #400 methacrylate), and NK Ester M-230G (methoxypolyethylene glycol #1000 methacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.; Light Acrylate MTG-A (methoxy-triethylene glycol acrylate), Light Acrylate EC-A (ethoxy-diethylene glycol acrylate), Light Acrylate EHDG-AT (2-ethylhexyl-diethylene glycol acrylate), and Light Ester 041MA (methoxypolyethylene glycol methacrylate) manufactured by Kyoeisha Chemical Co., Ltd.; Brenmer ANP-300 (nonylphenoxypolypropylene glycol acrylate), Brenmer AP-400 (polypropylene glycol monoacrylate), Brenmer 70PEP-350B (polyethylene glycol polypropylene glycol monomethacrylate), Brenmer 55PET-800 (polyethylene glycol tetramethylene glycol monomethacrylate), and Brenmer 50POEP-800B (octoxypolyethylene glycol polypropylene glycol methacrylate) manufactured by NOF Corporation; Viscote #MTG (methoxypolyethylene glycol acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

[0060] Examples of the hydroxyalkyl (meth)acrylate include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Examples of commercially available hydroxyalkyl (meth)acrylates include Light Ester HOA(N) (2-hydroxyethyl acrylate), Light Ester HO-250(N) (2-hydroxyethyl methacrylate), and Light Ester HOP(N) (2-hydroxypropyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd.

[0061] Examples of the alkoxyalkyl (meth)acrylate include methoxyethyl (meth)acrylate.

[0062] As the tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate are preferable, and tetrahydrofurfuryl acrylate is more preferable. As the 4-(meth)acryloylmorpholine, 4-acryloylmorpholine and 4-methacryloylmorpholine are preferable, and 4-acryloylmorpholine is more preferable. Examples of the vinylpyrrolidone include 1-vinyl-2-pyrrolidone (N-vinyl-2-pyrrolidone), 3-acetyl-1-vinylpyrrolidin-2-one, 3-benzoyl-1-vinylpyrrolidin-2-one, etc., and 1-vinyl-2-pyrrolidone is preferable.

[0063] Examples of the hydrophobic monomer include alkyl (meth)acrylate having a branched, linear or cyclic alkyl group with 1 to 30 carbon atoms, aryl (meth)acrylate having an aromatic group with 6 to 10 carbon atoms, and (meth)acryl group-containing silicone. Alkyl (meth)acrylate and (meth)acryl group-containing silicone are preferable, and alkyl (meth)acrylate is more preferable.

[0064] The number of carbon atoms of the alkyl group of the alkyl (meth)acrylate is preferably 1 to 30, more preferably 4 to 18, still more preferably 4 to 8, and even more preferably 4 to 6. Further, the alkyl group is branched, linear or cyclic, with branched or linear being preferable and branched being more preferable.

[0065] Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, etc. Among these, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred.

[0066] The number of carbon atoms of the aromatic group of the aryl (meth)acrylate is preferably 6 or more and 10 or less, more preferably 6 or more and 7 or less. Specific examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate, etc.

[0067] Examples of the (meth)acryl group-containing silicone include methacryl group-containing silicone and acryl group-containing silicone, and methacryl group-containing silicone is preferred. The (meth)acryl group-containing silicone is preferably one in which the (meth)acryl group is bonded to one end of the silicone main chain via a linking group, and one in which the (meth)acryl group is directly bonded to one end of the silicone main chain, and one in which the (meth)acryl group is bonded to one end of the silicone main chain via a linking group is preferred. The linking group is preferably a trimethylene group. The silicone main chain preferably consists of a linear or branched dimethyl silicone (polydimethylsiloxane), and more preferably consists of a linear dimethyl silicone. Moreover, it is more preferable that an alkyl group having 1 to 6 carbon atoms is present at the terminal on the side opposite to the (meth)acryl group, and a butyl group is preferably present. Examples of commercially available products of the (meth)acryl group-containing silicone include Silaplane TM-0701T (tris(trimethylsiloxy)silylpropyl methacrylate), Silaplane FM-0711 (methacryl group-containing dimethylpolysiloxane, number average molecular weight 1,000), and Silaplane FM-0721 (methacryl group-containing dimethylpolysiloxane, number average molecular weight 5,000) manufactured by JNC Corporation. By including the (meth)acryl group-containing silicone, the antifouling property of the formed antifouling coating film can be improved.

[0068] When the antifouling paint composition contains an acrylic polymer (C2) having a hydrophilic group having an ethyleneoxy (-OC2H4-) partial structure, from the viewpoint of imparting good antifouling property to the formed antifouling coating film, with respect to 100 parts by mass of the dimethylsiloxane partial structure (-(CH3)2Si-O-) of silicone, the total mass of the ethyleneoxy (-OC2H4-) partial structure is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 0.3 part by mass or more and 5 parts by mass or less.

[0069] The weight average molecular weight (Mw) of the acrylic polymer (C2) having a hydrophilic group is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, even more preferably 7,000 or more, and preferably 150,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, even more preferably 30,000 or less, from the viewpoints of antifouling property and the viscosity of the antifouling paint composition. When the weight average molecular weight (Mw) of the acrylic polymer (C2) having a hydrophilic group is within the above range, it is preferable in that good antifouling property can be imparted to the antifouling coating film.

[0070] When the antifouling paint composition of the present invention contains an acrylic polymer (C2) having a hydrophilic group, the content of the acrylic polymer (C2) having a hydrophilic group in the solid content of the antifouling paint composition is preferably 0.2% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, from the viewpoint of antifouling property.

[0071] <Paraffin oil (C3)> The paraffin oil (C3) is not particularly limited, and a paraffin oil having a suitable kinematic viscosity described below may be appropriately selected from known paraffin oils and used. As the paraffin oil, liquid paraffin is preferred. The kinematic viscosity of the paraffin oil (C3) at 25 ° C is preferably 10 mm 2 / s or more, more preferably 50 mm 2 / s or more, still more preferably 100 mm 2 / s or more, and preferably 5,000 mm 2 / s or less, more preferably 2,000 mm 2 / s or less, still more preferably 500 mm 2 / s or less.

[0072] The content of the paraffin oil (C3) in the solid content of the antifouling paint composition of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of improving the antifouling property of the formed antifouling paint film and facilitating the formation of the antifouling paint film.

[0073] [Colored pigment (D)] It is also preferable that the antifouling paint composition of the present invention contains a colored pigment (D). When the antifouling paint composition of the present invention contains a colored pigment (D), the film strength can be increased. The coloring pigment (D) is not particularly limited. Examples thereof include inorganic pigments such as iron oxide, titanium oxide, carbon black, zinc oxide, aluminum silicate, alumina white, and barium sulfate; and organic pigments such as naphthol red and phthalocyanine blue. From the viewpoints of the manufacturability and application workability of the antifouling paint composition, storage stability, and antifouling property of the formed antifouling paint film, it is preferably an inorganic pigment. Among them, it is preferably at least one selected from iron oxide, titanium oxide, carbon black, zinc oxide, aluminum silicate, alumina white, and barium sulfate, more preferably at least one selected from iron oxide, titanium oxide, and carbon black, and even more preferably at least one selected from iron oxide and titanium oxide. Examples of the iron oxide include red iron oxide, yellow iron oxide, and black iron oxide. As the titanium oxide, any of rutile type, anatase type, and brookite type can be used. From the viewpoints of the stability and availability of the antifouling paint film and the antifouling paint composition, it is preferable to use the rutile type.

[0074] When the antifouling paint composition of the present invention contains the coloring pigment (D), the content of the coloring pigment (D) in the solid content of the antifouling paint composition is preferably 0.01% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and still more preferably 4% by mass or more and 12% by mass or less, from the viewpoints of the antifouling property of the formed antifouling paint film, and the excellent manufacturability, application workability, and storage stability of the antifouling paint composition.

[0075] 〔Clear antifouling paint composition〕 It is also preferable that the antifouling paint composition of the present invention has a content of the coloring pigment (D) in the solid content of the antifouling paint composition of 0% by mass or more and 1% by mass or less to form a clear antifouling paint composition. In this case, the content of the coloring pigment (D) is more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and most preferably not contained. When the antifouling paint composition of the present invention is a clear antifouling paint composition, the antifouling paint composition of the present embodiment also has an effect of being excellent in transparency as compared with the case where a curable silicone having a methyl ethyl ketoxime group is used, for example.

[0076] When the antifouling paint composition of the present invention is a clear antifouling paint composition, the content of the coloring pigment (D) is 1% by mass or less, and in order to suppress a decrease in transparency, it is also preferable to reduce the amount of the biocide (E) described later used. When the antifouling paint composition is a clear antifouling paint composition, the content of the biocide base material (E) in the solid content of the antifouling paint composition is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and most preferably not contained. From the viewpoint of improving the antifouling property of the clear antifouling paint composition, the content of the lubricant (C) in the solid content of the clear antifouling paint composition is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, even more preferably 40% by mass or more, and from the viewpoints of film-forming property, strength of the antifouling paint film, etc., it is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less. Further, in the case of a clear antifouling paint composition, the content of the lubricant (C) with respect to 100 parts by mass of the polyorganosiloxane in the curable silicone (A), that is, the polyorganosiloxane (a1) having methyl isobutyl ketoxime groups at both ends in the case of (A-1) and the polyorganosiloxane (a2) having hydroxy groups at both ends in the case of (A-2), from the viewpoint of improving the antifouling property of the clear antifouling paint composition, is 30 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, and from the viewpoints of film-forming property, strength of the antifouling paint film, etc., it is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 120 parts by mass or less, even more preferably 100 parts by mass or less, and particularly preferably 90 parts by mass or less. In the case of a clear antifouling paint composition, from the viewpoint that the content of the lubricant (C) can be increased as described above, it is preferable that the curable silicone (A) is (A-1). When the curable silicone (A) is (A-1), an antifouling paint composition having a higher viscosity can be prepared compared to the case where it is (A-2). As a result, even if the content of the lubricant (C) is within the above range, an antifouling paint composition excellent in sag resistance can be obtained.

[0077] From the above, when the antifouling paint composition is a clear antifouling paint composition, it is preferable that the curable silicone (A) is (A-1) and the content of the lubricant (C) is within the above range. Thereby, an antifouling paint film excellent in smoothness, transparency, and antifouling property can be obtained. In addition, because of excellent smoothness and transparency, for example, it is suitably used for applications where transparency is required, such as antifouling paint compositions for equipment used in water or on water (solar power generation panels, observation windows of instruments and equipment, camera lenses, underwater lights, underwater sensors, etc.) and monitoring windows of submarines, as well as for antifouling properties in water. Furthermore, since the antifouling paint film obtained from the antifouling paint composition of the present invention is excellent in smoothness, when the antifouling paint film is formed, reflection is suppressed, and an antifouling paint film with better visibility can be obtained.

[0078] 〔Biological repellent (E)〕 The antifouling paint composition of the present invention preferably contains a biological repellent (E) for the purpose of enhancing the antifouling property of the formed antifouling paint film. The biological repellent (E) elutes from the antifouling paint film in water and has the effect of suppressing the adhesion of aquatic organisms to the surface of the antifouling paint film and improving the antifouling property. As the biocide (E), those having a repellent effect on aquatic organisms and a certain elution rate into water are preferred. One or more selected from copper pyrithione, zinc pyrithione, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (alias: tralopyril), and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (alias: DCOIT) are preferred. From the viewpoints of elution from the antifouling coating film and repellent effect on a wide variety of biological species, one or more selected from copper pyrithione and zinc pyrithione are more preferred. From the viewpoint of elution property, copper pyrithione is even more preferred. The biocide (E) may be used alone or in combination of two or more. When the antifouling paint composition of the present invention contains the biocide (E), the content of the biocide (E) in the solid content of the antifouling paint composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, from the viewpoints of the strength and antifouling property of the antifouling coating film and the coatability of the antifouling paint composition.

[0079] 〔Organosilicon crosslinking agent (F)〕 The antifouling paint composition of the present invention preferably contains an organosilicon crosslinking agent (F) in order to improve the curing rate, the strength of the antifouling coating film, and the adhesion to the substrate. The organosilicon crosslinking agent is not limited to those for these purposes, and may be blended, for example, for the purpose of functioning as a wetting agent for pigments. The organosilicon crosslinking agent (F) is an organosilane having three or four hydrolyzable groups on a silicon atom, and when having three hydrolyzable groups, further having one hydrocarbon group, and partial condensates thereof are also included. Note that compounds corresponding to the above organosilane (a3) are excluded. The number of the hydrolyzable groups is three or four per silicon atom. As the hydrolyzable group, an alkoxy group is preferred. As the alkoxy group, a methoxy group and an ethoxy group are preferred. As the hydrocarbon group, a hydrocarbon group having 1 to 6 carbon atoms is preferable, a methyl group, an ethyl group, or a propyl group is more preferable, and a methyl group and an ethyl group are even more preferable. Examples of the organosilicon crosslinking agent (F) include tetraethyl orthosilicate, a partial condensate of tetraethyl orthosilicate, alkyltrialkoxysilane, and oxime silane, and tetraethyl orthosilicate and a partial hydrolysis condensate of tetraethyl orthosilicate are preferable.

[0080] Examples of commercially available products of the tetraethyl orthosilicate include "Ethyl Silicate 28" manufactured by Colcoat Co., Ltd., and "Ethyl Orthosilicate" manufactured by Tama Chemical Industry Co., Ltd. Examples of commercially available products of the partial hydrolysis condensate of tetraethyl orthosilicate include "Silicate 40" manufactured by Tama Chemical Industry Co., Ltd., and "WACKER SILICATE TES 40 WN" manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Examples of commercially available products of the alkyltrialkoxysilane include "KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd. Examples of commercially available products of the oxime silane include "MTO (MOS)" (methyltris(methylethylketoxime)silane) and "VTO (VOS)" (vinyltris(methylethylketoxime)silane) manufactured by Toray Industries, Inc. The organosilicon crosslinking agent (F) may be used alone or in combination of two or more.

[0081] When the antifouling paint composition of the present invention contains the organosilicon crosslinking agent (F), the content of the organosilicon crosslinking agent (F) in the solid content of the antifouling paint composition is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 3% by mass or less. When the antifouling paint composition of the present invention contains the organosilicon crosslinking agent (F), the content of the organosilicon crosslinking agent (F) in the antifouling paint composition with respect to 100 parts by mass of the curable silicone (A) is preferably 0.1 part by mass or more and 5 parts by mass or less, and more preferably 0.5 part by mass or more and 3 parts by mass or less.

[0082] Silane coupling agent (G) The antifouling coating composition preferably contains a silane coupling agent (G) for the purpose of improving the curing rate, curability of the antifouling coating film, and adhesion to the substrate. The silane coupling agent (G) is an organoalkoxysilane having at least one alkoxy group and at least one organic reactive group bonded to a silicon atom. As the alkoxy group, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable. One to three alkoxy groups are bonded to the silicon atom, preferably two to three alkoxy groups are bonded, and more preferably three alkoxy groups are bonded. Examples of the organic reactive group include an amino group, a mercapto group, an epoxy group, an isocyanate group, a ureido group, a vinyl group, an acrylic group, a methacrylic group, and a styryl group. An amino group, a mercapto group, an epoxy group, an isocyanate group, and a ureido group are preferable, an amino group, a mercapto group, and an epoxy group are more preferable, and an amino group is even more preferable. Specific organic reactive groups containing an amino group include a 2-(aminoethyl)-3-aminopropyl group and a 3-aminopropyl group, which are preferable.

[0083] Examples of the silane coupling agent (G) include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-(2-aminoethylamino)ethylamino)propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. Among them, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane are preferable, and 3-(2-aminoethylamino)propyltrimethoxysilane is more preferable. As the silane coupling agent (G), a condensate of the above compound may be used. The silane coupling agent (G) may be used alone or in combination of two or more kinds.

[0084] When the antifouling paint composition of the present invention contains the silane coupling agent (G), the content of the silane coupling agent (G) in the solid content of the antifouling paint composition is preferably 0.05% by mass or more and 3% by mass or less, and more preferably 0.1% by mass or more and 1% by mass or less. The content of the silane coupling agent (G) in the antifouling paint composition with respect to 100 parts by mass of the curable silicone (A) is preferably 0.03 parts by mass or more and 3 parts by mass or less, and more preferably 0.1 parts by mass or more and 1 part by mass or less.

[0085] The antifouling paint composition of the present invention preferably contains an organosilicon crosslinking agent (F) and / or a silane coupling agent (G) for the purpose of improving the curability, strength, and adhesion to the substrate of the antifouling paint film.

[0086] [Curing catalyst (H)] The antifouling paint composition preferably contains a curing catalyst (H) in order to improve the curing rate and the film strength of the antifouling paint film. As the curing catalyst (H), a tin compound, a titanium compound, a fatty acid salt of an alkali metal, and an amine compound are preferable, a titanium compound and an amine compound are more preferable, and a titanium compound is still more preferable.

[0087] Examples of the tin compound include dibutyltin diacetate, dibutyltin acetoacetonate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, bis(dibutyltin laurate) oxide, dibutylbis(triethoxysiloxy)tin, bis(dibutyltin acetate) oxide, dibutyltin bis(ethyl maleate), dioctyltin bis(ethyl maleate), tin naphthenate, tin oleate, etc. Among them, dibutyltin diacetate, dibutyltin acetoacetonate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, dibutyltin dineodecanoate are preferred, and dibutyltin dilaurate is more preferred. Examples of commercially available products of the tin compound include "NEOSTANN U-100" manufactured by Nitto Kasei Co., Ltd. and "Gleck TL" manufactured by DIC Corporation.

[0088] Examples of the titanium compound include tetraisopropoxytitanium, tetra-N-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, titanium isopropoxyoctyl glycol, etc. Examples of the organometallic compound other than the tin compound and the titanium compound include zinc naphthenate, zinc stearate, zinc-2-ethyloctoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, alkoxyaluminum compound, etc. Examples of the fatty acid salt of the alkali metal include potassium acetate, potassium 2-ethylhexanoate, potassium octanoate, potassium versatate, sodium acetate, sodium 2-ethylhexanoate, sodium octanoate, sodium versatate, lithium oxalate, lithium 2-ethylhexanoate, lithium octanoate, and lithium versatate, etc. Examples of the amine compound include 1,6-hexanediamine-N,N,N,N-tetramethyl, 2,4,6-tris(dimethylaminomethyl)phenol, 1,2-dimethylimidazole, and the like. The curing catalyst (H) may be used alone or in combination of two or more.

[0089] When the antifouling paint composition of the present invention contains the curing catalyst (H), the content of the curing catalyst (H) in the solid content of the antifouling paint composition is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 3% by mass or less, and still more preferably 0.1% by mass or more and 1% by mass or less from the viewpoint of improving the curing rate. When the antifouling paint composition of the present invention contains the curing catalyst (H), the content of the curing catalyst (H) in the antifouling paint composition relative to 100 parts by mass of the curable silicone (A) is preferably 0.003 part by mass or more and 30 parts by mass or less, more preferably 0.03 part by mass or more and 5 parts by mass or less, and still more preferably 0.3 part by mass or more and 3 parts by mass or less.

[0090] 〔Organic solvent (I)〕 The antifouling paint composition of the present invention may contain an organic solvent (I) in order to keep the viscosity of the paint composition low and improve the coating workability. Examples of the organic solvent (I) include aromatic hydrocarbon-based organic solvents, aliphatic hydrocarbon-based organic solvents, alicyclic hydrocarbon-based organic solvents, ketone-based organic solvents, and ester-based organic solvents. Aromatic hydrocarbon-based organic solvents and ketone-based organic solvents are preferred, and aromatic hydrocarbon-based organic solvents are more preferred. Examples of the aromatic hydrocarbon-based organic solvent include toluene, xylene, and mesitylene. Xylene is preferred. Examples of the aliphatic hydrocarbon-based organic solvent include pentane, hexane, heptane, and octane. Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of the ketone-based organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl carbonate, etc., and acetylacetone is preferred. Examples of the ester-based organic solvent include ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, etc. The organic solvent (I) may be used alone or in combination of two or more. When the antifouling paint composition of the present invention contains the organic solvent (I), the content of the organic solvent (I) in the paint composition is preferably 3% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more from the viewpoint of improving the coating workability, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less from the viewpoint of suppressing sagging during coating or reducing the environmental load.

[0091] [Other optional components] Examples of the pigments other than the silica particles (B) and the coloring pigment (D) include mica, calcium carbonate, barium carbonate, potassium feldspar, kaolin, and glass short fibers. These inorganic fillers may be used alone or in combination of two or more. Examples of the dehydrating agent include zeolite, porous alumina, orthoesters such as alkyl orthoformate, orthoboric acid, isocyanate compounds, etc. Examples of the sag inhibitor / sedimentation inhibitor include organic clay-based waxes (stearate salts of Al, Ca, Zn, lecithin salts, alkyl sulfonates, etc.), organic waxes (polyethylene wax, oxidized polyethylene wax, amide wax, polyamide wax, hydrogenated castor oil wax, etc.), mixtures of organic clay-based waxes and organic waxes, etc. Examples of the enzyme include serine protease, cysteine protease, metalloprotease, cellulase, hemicellulase, pectinase, and glycosidase, etc. Examples of the flame retardant include antimony oxide, oxidized paraffin, etc. Examples of the thermal conductivity improver include boron nitride, aluminum oxide, and the like.

[0092] 〔Aspect of the antifouling paint composition〕 The antifouling paint composition of the present invention may be a one-component antifouling paint composition in which the above components are made into one composition, or a multi-component antifouling paint composition in which the above components are made into two or more compositions and mixed before application. However, from the viewpoint of preventing deterioration during storage, a multi-component antifouling paint composition is preferable, and from the viewpoint of painting workability, a one-component antifouling paint composition is more preferable. When it is a one-component antifouling paint composition, it is preferable that the curable silicone (A) is (A-1). Examples of the multi-component antifouling paint composition include a two-component antifouling paint composition and a multi-component antifouling paint composition of three or more components. From the viewpoint of painting workability, a two-component antifouling paint composition is preferable, and from the viewpoint of preventing deterioration during storage, a multi-component antifouling paint composition of three or more components is preferable. When the antifouling paint composition of the present invention is a multi-component antifouling paint composition, it is preferable that the polyorganosiloxane (a2), the organosilane (a3), the organosilicon crosslinking agent (F), the silane coupling agent (G), and the curing catalyst (H) are contained in different liquids, and it is more preferable that the silane coupling agent (G), the organosilane (a3), the organosilicon crosslinking agent (F), and the curing catalyst (H) are further contained in different liquids. The silica particles (B), the coloring pigment (D), and the biocide (E) are preferably contained in the same liquid as the polyorganosiloxane (a1) or the polyorganosiloxane (a2). It should be noted that the content of each component in the antifouling paint composition of the present invention is the content with respect to the total amount of all the compositions even in the case of a multi-component antifouling paint composition.

[0093] 〔Manufacturing method of the antifouling paint composition〕 The antifouling paint composition is preferably manufactured as follows. First, it is preferable to have a step of kneading polyorganosiloxane (a1) or polyorganosiloxane (a2) and silica particles (B). Further, heating may be performed during or after kneading. By kneading these in advance, the affinity between the two components can be improved, and aggregation of silica and an increase in the viscosity of the paint composition can be suppressed. When heating, the conditions are preferably 100°C or higher, more preferably 100°C or higher and 300°C or lower, and still more preferably 140°C or higher and 200°C or lower. The pressure is preferably under normal pressure or reduced pressure, and the treatment time is preferably 3 hours or more and 30 hours or less.

[0094] The antifouling paint composition is obtained by mixing and stirring the above-mentioned compounding components. When the antifouling paint composition of the present invention is a one-component antifouling paint composition, the curable silicone (A) which is an essential component, and the optional components such as silica particles (B), lubricant (C), coloring pigment (D), biocide (E), organosilicon crosslinking agent (F), silane coupling agent (G), curing catalyst (H) and organic solvent (I) are appropriately added and mixed and stirred to obtain it.

[0095] When the antifouling paint composition of the present invention is a multi-component antifouling paint composition, it is preferable that polyorganosiloxane (a2), organosilane (a3), organosilicon crosslinking agent (F), silane coupling agent (G) and curing catalyst (H) are contained in different liquids. In the case of a multi-component antifouling paint composition of three or more components, it is preferable that the silane coupling agent (G), the organosilicon crosslinking agent (F) and the curing catalyst (H) are further contained in different liquids. Further, the silica particles (B), the coloring pigment (D), and the biocide (E) are preferably contained in the same liquid as polyorganosiloxane (a1) and / or polyorganosiloxane (a2). The lubricant (C) may be contained in any liquid, and it is preferable that the liquid containing polyorganosiloxane (a1) and / or polyorganosiloxane (a2) contains silicone oil (C1), an acrylic polymer (C2) having a hydrophilic group, and paraffin oil (C3). Mixing and stirring are preferably performed at 0°C or higher and 50°C or lower.

[0096] [Antifouling coating film] The antifouling coating film of the present invention is an antifouling coating film formed from the above-described antifouling paint composition. The antifouling coating film can be formed by applying or impregnating the antifouling paint composition of this embodiment onto a substrate and then drying and curing it. Moreover, the antifouling coating film is preferably an antifouling coating film used for the purpose of preventing fouling of the substrate by aquatic organisms in water.

[0097] [Substrate with antifouling coating film and method for producing the same] The substrate with an antifouling coating film of the present invention has a substrate and an antifouling coating film provided on the surface of the substrate. The method for producing the substrate with an antifouling coating film preferably includes a step of applying the antifouling paint composition of this embodiment to the substrate (coating step) or a step of impregnating the substrate with the antifouling paint composition of this embodiment, and further preferably includes a step of drying and curing the antifouling paint composition.

[0098] [Coating step] Examples of the method for applying the antifouling paint composition of the present invention include known methods such as brush painting, roller painting, spraying, roll coater painting, flow coater painting, slit coater painting, gravure coater painting, spin coater painting, curtain roll coater painting, electrostatic painting, dip painting, silk printing, and spin coating. The thickness of the coating film formed from the antifouling paint composition of the present invention is set so that the finally formed antifouling coating film has the thickness described below. The coating film may be formed by a single coating or by two or more coatings (two or more coats). The thickness of the antifouling coating film of the present invention is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 50 μm or more, and preferably 1,000 μm or less, more preferably 500 μm or less, still more preferably 300 μm or less. When the antifouling coating film is in such a state, it becomes an antifouling coating film excellent in long-term antifouling properties.

[0099] [Drying and curing step] The antifouling paint composition of the present invention applied by the aforementioned method dries and cures, for example, under the condition of 23°C, preferably by leaving it for 0.5 days or more and 14 days or less, more preferably about 1 day or more and 10 days or less, to obtain an antifouling coating film. Note that the drying and curing of the antifouling paint composition of the present invention may be performed while heating and / or blowing air.

[0100] Here, the substrate is not particularly limited, but it is preferably a substrate that comes into contact with seawater or fresh water, and more preferably at least one selected from ships, underwater structures, fishing materials, water supply and drainage pipes, and equipment used on water and underwater. Ships and underwater structures are more preferred, and ships are particularly preferred. Specifically, ships (e.g., large steel ships such as container ships and tankers, fishing boats, FRP ships, wooden ships, yacht hulls, especially the part from the draft to the bottom of the ship, including any of these shipbuilding or repair ships), underwater structures (e.g., oil pipelines, water conduction pipes, circulating water pipes, water supply and drainage ports of factories and thermal / atomic power plants, submarine cables, seawater utilization equipment (such as seawater pumps), megafloats, coastal roads, submarine tunnels, port facilities, various underwater civil engineering structures in canals and waterways, etc.), fishing materials (e.g., ropes, fishing nets, fishing gear, floats or buoys, etc.), water supply and drainage pipes for seawater, etc. in factories and thermal / atomic power plants, equipment used on water and underwater (solar power generation panels, observation windows of instruments and equipment, camera lenses, underwater lights, underwater sensors, etc.), monitoring windows of submarines, etc. are exemplified.

[0101] The material of the substrate is not particularly limited. In particular, for ships, steel, aluminum, wood, FRP, glass, plastic, etc. can be mentioned. For equipment used on water and underwater, glass, plastic, etc. can be mentioned. In addition, the substrate may be treated with other treatment agents such as rust inhibitors, may have a coating film such as a primer formed on the surface in advance, the present composition may already be painted, or it may be an old antifouling coating film that has formed the present coating film or other antifouling coating films and has deteriorated over time, and is not particularly limited.

Examples

[0102] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0103] [Manufacture of Antifouling Paint Composition] <Kneaded Product of Curable Silicone (A) and Silica Particles (B)> The curable silicone (A) and silica particles (B) shown in Table 1 were kneaded at the ratios described in Table 1 to obtain a kneaded product.

[0104] [Table 1]

[0105] <Components of Antifouling Paint Composition> Each component used in the antifouling paint composition is shown in Table 2. The viscosity and kinematic viscosity in Table 2 are both values at 25°C.

[0106] [Table 2]

[0107] <Acrylic Polymer with Hydrophilic Group (c2-1)> Synthesis Example 1 (Synthesis of Acrylic Polymer with Hydrophilic Group (c2-1)) The reaction was carried out under normal pressure and in a nitrogen atmosphere. 42.86 parts by mass of methyl amyl ketone was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel, and heated with stirring until the methyl amyl ketone reached 100 °C. While maintaining the temperature of the reaction mixture at 100 ± 5 °C, a mixture consisting of 40.0 parts by mass of NK ester AM-90G (methoxypolyethylene glycol acrylate, average number of polyethylene glycol units 9, manufactured by Shin-Nakamura Chemical Co., Ltd.), 60.0 parts by mass of isobutyl acrylate, and 4.0 parts by mass of 2,2'-azobis(2-methylbutyronitrile) was dropped into the reaction vessel over 4 hours. Then, it was stirred for 2 hours while maintaining 100 ± 5 °C to obtain a solution of an acrylic polymer (c2-1) having a hydrophilic group. The solid content of the obtained solution was 70.3% by mass, the viscosity was 109 mPa·s, and the weight average molecular weight (Mw) of the acrylic polymer (c2-1) having a hydrophilic group was 9,100.

[0108] (Solid content of polymer solution) The solid content (%) was determined by dividing the mass of the solid content obtained by drying the polymer solution at 108 °C and 1 atm for 3 hours by the mass of the polymer solution before drying.

[0109] (Viscosity of polymer solution) The viscosity (mPa·s) of the polymer solution at a liquid temperature of 25 °C was measured using an E-type viscometer (TV-25, manufactured by Toki Sangyo Co., Ltd.).

[0110] (Average molecular weight of polymer) The weight average molecular weight (Mw) of the polymer was measured using gel permeation chromatography (GPC) under the following conditions. (GPC conditions) Apparatus: "HLC-8220GPC" (manufactured by Tosoh Corporation) Columns: "TSKgel SuperH2000" and "TSKgel SuperH4000" (each manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length)) were connected. Eluent: Tetrahydrofuran (THF) Flow rate: 0.500 mL / min Detector: RI Column thermostat temperature: 40 °C Standard substance: polystyrene Sample preparation method: THF was added to the polymer solution and filtered through a membrane filter to obtain a sample for GPC measurement.

[0111] <Antifouling paint composition> Each component was blended according to the blending amounts (parts by mass) described in Table 3, and mixed and stirred to obtain one-component antifouling paint compositions (Examples 1 to 9 and Comparative Examples 1 to 9). Also, each component was blended according to the blending amounts (parts by mass) described in Table 3, and each liquid of the main agent and the curing agent was mixed and stirred to obtain two-component antifouling paint compositions (Examples 10 to 23 and Comparative Examples 10 to 23).

[0112] [Evaluation] The following evaluations were performed on the obtained paint compositions. <Antifouling property test> An epoxy resin-based anticorrosive paint (trade name "Banno 500", manufactured by China Paint Co., Ltd.) was applied to a sandblasted steel plate (300 mm in length × 100 mm in width × 2.3 mm in thickness) using a spray coater so that the dry film thickness was 150 μm, and dried at room temperature (hereinafter, 23 °C) for 24 hours. Subsequently, an epoxy resin-based binder (trade name "CMP Bioclin SG-R", manufactured by China Paint Co., Ltd.) was applied using a spray coater so that the dry film thickness was 100 μm, and dried at room temperature for 24 hours. Next, after thoroughly mixing the antifouling paint compositions of the respective Examples and Comparative Examples on this undercoat film, it was applied using a spray coater so that the dry film thickness was 200 μm, and after 1 week at room temperature, a test plate with a coating film was prepared. The obtained test plate with an antifouling coating film was left standing and immersed in Miyajima Bay, Hiroshima Prefecture, and after 3 months, the ratio of the area where marine organisms adhered to the surface of the test plate was visually observed and evaluated according to the following criteria.

[0113] (Evaluation criteria) 5: The adhesion area of marine organisms is less than 10% of the entire test plate 4: The adhesion area of marine organisms is 10% or more and less than 30% of the entire test plate 3: The adhesion area of marine organisms is 30% or more and less than 50% of the entire test plate 2: The adhesion area of marine organisms is 50% or more and less than 80% of the entire test plate 1: The adhesion area of marine organisms is 80% or more of the entire test plate

[0114] <Measurement of smoothness> The antifouling paint compositions of the above examples and comparative examples were applied to a smooth polyvinyl chloride plate (150 mm in length × 70 mm in width × 5 mm in thickness) using a spray coater and dried at room temperature for 7 days. For the obtained polyvinyl chloride test plate with an antifouling coating film, a range of 30 mm × 30 mm was measured with a 250 μm mesh using a laser displacement meter, and 121 × 121 data points were obtained. From this data, the Rz (maximum height roughness) and RSm (average length of roughness curve elements) of the coating film were calculated.

[0115] <Evaluation of frictional resistance> On the outer surface of a polyvinyl chloride cylinder with a diameter of 310 mm, an epoxy binder (trade name "CMP Bioclin SG-R", manufactured by China Paint Co., Ltd.) was applied as a primer so that the film thickness after drying was 100 μm. On the obtained coating film, the antifouling paint compositions of the above examples and comparative examples were applied using a spray coater so that the dry film thickness was 100 μm, and dried at room temperature for 24 hours. The frictional resistance of the formed antifouling coating film was evaluated using a double-cylinder type resistance measuring device. The double-cylinder type resistance measuring device is composed of two inner and outer cylinders. An inner cylinder with an antifouling coating film formed on its outer surface as the measurement target sample is installed in the outer cylinder filled with artificial seawater, and when the outer cylinder is rotated to generate a rotating water flow, the torque stress applied to the inner cylinder is measured. The above-mentioned test cylinders with coating films of the examples and comparative examples were used as this inner cylinder, and the measured torque stress was compared with the reference torque stress obtained using an uncoated inner cylinder, and the increase rate was expressed as the torque increase rate %, which is shown in Table 3. The smaller the value of the torque increase rate %, the higher the effect of reducing the frictional resistance by the coating film. The measurement was carried out at a temperature of 23°C with the rotation speed of the outer cylinder set at 1,000 rpm.

[0116] <Measurement of Hiding Power> The hiding power was measured in accordance with JIS K 5600-4-1. That is, the antifouling paint compositions of Examples 6 to 9 and Comparative Examples 6 to 9 were applied to a hiding power test paper using a paint applicator so that the dry film thickness was 500 μm, and dried at room temperature for 7 days. The Y value (YB) of the portion painted on the black part of the hiding power test paper with the obtained antifouling coating film and the Y value (YW) of the portion painted on the white part of the test paper were measured using a spectrocolorimeter (model SD 5000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the hiding power (%) was determined by YB / YW×100. The lower the value of the hiding power, the better the transparency.

[0117]

Table 3-1

[0118]

Table 3-2

[0119]

Table 3-3

[0120] According to the examples and comparative examples, it can be seen that the antifouling coating film excellent in antifouling property and smoothness can be obtained by the antifouling paint composition of the present invention. Furthermore, in Examples 6 to 9, an antifouling coating film excellent in transparency was obtained.

Claims

1. An antifouling paint composition containing at least one curable silicone (A) selected from the following (1) and (2), and a lubricant (C). (1) A polyorganosiloxane having methyl isobutyl ketoxime groups at both ends (2) A polyorganosiloxane having hydroxy groups at both ends, and an organosilane represented by the following formula (I) 【Chemical Formula 1】 (In formula (I), R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, X is a methyl isobutyl ketoxime group, and a is 0 or 1.)

2. The antifouling paint composition according to claim 1, wherein the curable silicone (A) contains a polyorganosiloxane having methyl isobutyl ketoxime groups at both ends.

3. The antifouling paint composition according to claim 1, wherein the polyorganosiloxane has a polydimethylsiloxane structure.

4. The antifouling paint composition according to claim 1, further containing hydrophobic silica particles (B1).

5. The antifouling paint composition according to claim 1, further containing hydrophilic silica particles (B2).

6. The antifouling paint composition according to claim 1, wherein the lubricant (C) is at least one selected from the group consisting of silicone oil, paraffin oil, fats and oils, an acrylic resin having a hydrophilic group, and a polyalkylene glycol.

7. The antifouling paint composition according to claim 6, wherein the silicone oil is at least one selected from phenyl-modified silicone oil and polyether-modified silicone oil.

8. The antifouling paint composition according to claim 1, wherein the content of the coloring pigment (D) in the solid content of the antifouling paint composition is 1% by mass or less.

9. The antifouling paint composition according to claim 8, wherein the content of the lubricant (C) is 30 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyorganosiloxane.

10. The antifouling paint composition according to claim 1, wherein the content of the curable silicone (A) in the solid content of the antifouling paint composition is 40% by mass or more and 90% by mass or less.

11. An antifouling paint film formed from the antifouling paint composition according to any one of claims 1 to 10.

12. A substrate with an antifouling paint film, having a substrate and the antifouling paint film according to claim 11 provided on the surface of the substrate.

13. The substrate with an antifouling paint film according to claim 12, wherein the substrate is at least one selected from ships, underwater structures, fishing materials, and water supply and drainage pipes.

14. A method for manufacturing a substrate with an antifouling coating film, comprising the step of applying the antifouling coating composition according to any one of claims 1 to 10 to a substrate or impregnating a substrate with the antifouling coating composition according to any one of claims 1 to 10.

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