CN113444386A

CN113444386A - Antifouling coating composition

Info

Publication number: CN113444386A
Application number: CN202110317876.9A
Authority: CN
Inventors: 原田祥太郎; 筏井淳内; 名部玲乃; 今井庆彦
Original assignee: Chugoku Marine Paints Ltd
Current assignee: Chugoku Marine Paints Ltd
Priority date: 2020-03-26
Filing date: 2021-03-25
Publication date: 2021-09-28
Also published as: KR20210120866A; JP2021155727A

Abstract

The invention provides a forming energyAn antifouling coating composition which can realize an antifouling coating film having both long-term antifouling properties and crack resistance of the coating film in seawater and fresh water. An antifouling paint composition comprising a silicone ester polymer (A) and a copolymer (B) having a structural unit (B-1) derived from styrene and a structural unit (B-2) derived from a polymerizable monomer (B2) represented by the formula (B2). Formula (b 2): CH (CH)₂＝CH－COO－(R^b1－O)_n－R^b2In the formula (b2), R^b1Is an alkanediyl group having 1 to 5 carbon atoms, R^b2Is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 3.]。

Description

Antifouling coating composition

Technical Field

The present invention relates to an antifouling coating composition, an antifouling coating film, a substrate with an antifouling coating film, and a method for producing a substrate with an antifouling coating film.

Background

A wide variety of aquatic organisms are likely to adhere to the surface of a substrate (such as a ship, an underwater structure, a fishing net, and a seawater supply and drainage pipe in a factory) exposed to water (such as an ocean, a river, and a lake or the like) in a natural environment for a long time. If aquatic organisms adhere to the surface of the substrate, the appearance is impaired or various problems occur. For example, when the base material is a ship, the resistance due to water flow is increased, which may result in a decrease in ship speed or an increase in fuel consumption. When the substrate is an underwater structure, the anticorrosive coating applied to the surface of the substrate may be damaged, which may result in a reduction in strength and function and a significant reduction in life. When the substrate is a fishing net such as a net for farming or a fixing net, the net may be clogged with aquatic organisms, which causes a serious problem such as death of the farmed organisms and the captured organisms due to oxygen deficiency. When aquatic organisms adhere to and propagate in seawater supply and drainage pipes in factories, thermal power stations, nuclear power stations, and the like, the aquatic organisms may cause clogging of the supply and drainage pipes and a reduction in flow velocity.

In order to prevent the adhesion of aquatic organisms causing such a problem, an operation of applying an antifouling paint to the surface of a substrate to form an antifouling coating film is generally performed. Among these antifouling paints, hydrolysis type antifouling paints are widely used because of their advantages such as excellent antifouling performance, and an antifouling paint containing a silicone ester polymer has been developed as one of them.

Patent document 1 describes an antifouling paint composition obtained by blending a copolymer containing a structural unit derived from styrene and a structural unit derived from glycidyl (meth) acrylate with an antifouling paint containing a silicone ester polymer.

Patent document 2 describes an antifouling coating composition in which an organosilyl copolymer and a (meth) acrylate polymer that is incompatible with the copolymer and has phase-separating properties are mixed to form a self-polishing antifouling coating film.

Patent document 3 discloses an antifouling paint composition containing a polymeric plasticizer comprising an ethylenically unsaturated carboxylic acid ester polymer having a glass transition temperature of-20 ℃ or lower and a number average molecular weight of 500 to 20000 and a triorganosilyl (meth) acrylate copolymer.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2014/175246

Patent document 2: japanese Kokai publication No. 2006-503115

Patent document 3: international publication No. 2008/105122

Disclosure of Invention

Problems to be solved by the invention

The coating film containing the silicone ester polymer dissolves in seawater at a constant rate for a certain period of time from the initial stage of immersion, but over a long period of time, the water resistance of the coating film decreases, and cracks and peeling occur due to hydrolysis inside the coating film. In order to solve this problem, when an acrylic copolymer is blended with a silicone ester polymer, the crack resistance of the coating film is improved, but the stain resistance is often reduced. In patent documents 1 to 3, these problems have been studied, but there is still room for further improvement in terms of both antifouling property over a long period of time (long-term antifouling property) and water resistance of a coating film (crack resistance).

The present invention addresses the problem of providing an antifouling coating composition capable of forming an antifouling coating film that can achieve both long-term antifouling properties and crack resistance of the coating film in seawater and fresh water.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the following antifouling paint composition can solve the above problems. That is, the present invention relates to the following [1] to [15 ].

[1] An antifouling coating composition comprising:

a silicone ester polymer (A) and a copolymer (B) having a structural unit (B-1) derived from styrene and a structural unit (B-2) derived from a polymerizable monomer (B2) represented by the formula (B2).

Formula (b 2): CH (CH)₂＝CH－COO－(R^b1－O)_n－R^b2

[ formula (b2) wherein R^b1Is an alkanediyl group having 1 to 5 carbon atoms, R^b2Is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 3.]

[2] The antifouling paint composition as claimed in the above [1], wherein the proportion of the structural unit (B-1) in the copolymer (B) is 30 to 80% by mass.

[3] The antifouling paint composition as claimed in the above [1], wherein the proportion of the structural unit (B-2) in the copolymer (B) is 15 to 45% by mass.

[4] The antifouling paint composition as claimed in the above [1], wherein the proportion of the structural unit (B-1) in the copolymer (B) is 30 to 80% by mass, and the proportion of the structural unit (B-2) is 15 to 45% by mass.

[5] The antifouling paint composition as claimed in any one of the above [1] to [4], wherein the polymerizable monomer (b2) represented by the formula (b2) is an alkoxyalkyl acrylate.

[6] The antifouling paint composition as described in the above [5], wherein the polymerizable monomer (b2) represented by the formula (b2) is 2-methoxyethyl acrylate.

[7] The antifouling paint composition as claimed in any one of the above [1] to [6], wherein the silicone-based polymer (A) has a structural unit derived from triisopropylsilyl methacrylate.

[8] The antifouling paint composition as claimed in any one of the above [1] to [7], wherein the mass ratio (A: B) of the silicone ester polymer (A) to the copolymer (B) is 90:10 to 30: 70.

[9] The antifouling paint composition as claimed in any one of the above [1] to [8], further comprising a monocarboxylic acid compound (C).

[10] The antifouling paint composition as claimed in any one of the above [1] to [9], further comprising copper and/or a copper compound (D).

[11] The antifouling paint composition as claimed in any one of the above [1] to [10], further comprising an organic antifouling agent (E).

[12] An antifouling coating film formed from the antifouling paint composition according to any one of the above [1] to [11 ].

[13] A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film according to [12] above provided on the surface of the substrate.

[14] The substrate with an antifouling coating film according to item [13], wherein the substrate is at least 1 selected from the group consisting of ships, underwater structures, fishery materials and water supply and drainage pipes.

[15] A method for producing a substrate with an antifouling coating film, comprising the step of applying or impregnating the substrate with the antifouling paint composition according to any one of the above [1] to [11 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an antifouling coating composition capable of forming an antifouling coating film that achieves both long-term antifouling properties and crack resistance of the coating film in seawater and fresh water can be provided.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail.

Each component described in the present specification can be used in 1 kind or 2 or more kinds.

"Polymer" is used in a sense to include homopolymers and copolymers.

"(meth) acrylate" is a word that includes both acrylates and methacrylates. The same applies to examples of (meth) acrylic acid and the like.

"structural Unit from XX" means that XX is represented as A¹A²C＝CA³A⁴(C ═ C is a polymerizable carbon-carbon double bond, A¹～A⁴An atom or a group bonded to a carbon atom, respectively), for example, a structural unit represented by the following formula.

[ antifouling paint composition]

The antifouling paint composition of the present embodiment (hereinafter also referred to as "composition (I)") contains a silicone ester polymer (A) and a copolymer (B) having a structural unit (B-1) derived from styrene and a structural unit (B-2) derived from a polymerizable monomer (B2) represented by formula (B2) described later.

< Silicone ester Polymer (A) >

The silicone ester polymer (a) (hereinafter also referred to as "polymer (a)") is a polymer having a structural unit derived from a silicone ester monomer. The polymer (a) preferably has a structural unit (a-1) derived from a polymerizable monomer (a1) represented by the formula (a 1).

The respective symbols in the formula (a1) will be described below.

R¹Is a hydrogen atom or a methyl group, preferably a methyl group.

R²～R⁶Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom. Examples of the organic group include a linear or branched alkyl group, a cycloalkyl group, and an aryl group, which may have a heteroatom such as an oxygen atom interposed between a carbon atom and a carbon source, and from the viewpoint of easily obtaining an excellent antifouling coating film having a proper hydrolysis property and a good balance between long-term antifouling property and water resistance (crack resistance), at least 1 selected from a linear or branched alkyl group having 1 to 8 carbon atoms and a phenyl group is preferable, and a branched alkyl group is more preferable.

Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group, and an isopropyl group is preferable.

n is 0 or an integer of 1 or more, preferably 0. The upper limit value of n may be 50, for example.

X is a hydrogen atom or R⁷The group represented by — O — C (═ O) -, is preferably a hydrogen atom. R⁷A hydrogen atom, a 1-valent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R⁸R⁹R¹⁰Si-silyl group. R⁸、R⁹And R¹⁰Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom. The organic group having a valence of 1 to 20 carbon atoms, which may have a hetero atom, includes the above-mentioned specific examples.

The polymerizable monomer (a1) is preferably a trialkylsilyl (meth) acrylate, an alkyldiarylsilyl (meth) acrylate, or an aryldialkylsilyl (meth) acrylate, and more preferably a trialkylsilyl (meth) acrylate. Examples of the trialkylsilyl (meth) acrylate include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tripropylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tributylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-sec-butylsilyl (meth) acrylate, tri-2-ethylhexylsilyl (meth) acrylate, and butyldiisopropylsilyl (meth) acrylate. Further, as the polymerizable monomer (a1), a polymerizable monomer having n of 2 or more in the above formula (a1), such as 1- (meth) acryloyloxynetamethyltetrasiloxane, can be cited. Among these, from the viewpoint of easily obtaining an excellent antifouling coating film having a good balance between long-term antifouling property and water resistance (crack resistance) and having an appropriate hydrolysis property, a trialkylsilyl (meth) acrylate having a branched alkyl group is preferable, triisopropylsilyl (meth) acrylate is more preferable, and (triisopropylsilyl) methacrylate is particularly preferable.

The number of the structural units (a-1) may be 1 or 2 or more.

The polymer (a) may further have a structural unit (a-2) derived from another ethylenically unsaturated monomer (hereinafter also referred to as "monomer (a 2)").

Examples of the monomer (a2) include:

(meth) acrylic acid;

(meth) acrylates, specifically, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (3,5, 5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, and stearyl (meth) acrylate; alicyclic group-containing (meth) acrylates such as cyclohexyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; alkoxyalkyl (meth) acrylates or aryloxyalkyl (meth) acrylates such as methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like; glycol-based (meth) acrylates such as ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, and methoxy-dipropylene glycol (meth) acrylate;

vinyl monomers, specifically, vinyl acetate, isobutyl vinyl ether, styrene, vinyl toluene, (meth) acrylonitrile, vinyl propionate, and vinyl benzoate;

the (meth) acrylate containing a metal ester group includes, specifically, zinc (meth) acrylate, zinc di (meth) acrylate, copper (meth) acrylate, and copper di (meth) acrylate.

The number of the structural units (a-2) may be 1, or 2 or more.

The proportion of the structural unit (a-1) in the polymer (a) is preferably 35% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less.

The proportion of the structural unit (a-2) in the polymer (a) is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, preferably 65% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less.

When the ratio of each structural unit is within the above range, the antifouling coating film formed from the composition (I) tends to have appropriate hydrolyzability and to have excellent antifouling properties over a long period of time. The ratio of each structural unit can be determined by NMR (nuclear magnetic resonance spectroscopy), Pyro-GC/MS (thermal decomposition gas chromatography mass spectrometry), or the like

The weight average molecular weight (Mw) of the polymer (a) is preferably 3,000 or more, more preferably 10,000 or more, preferably 70,000 or less, more preferably 50,000 or less, from the viewpoint of improving the crack resistance of the antifouling coating film formed from the composition (I). Mw can be determined by Gel Permeation Chromatography (GPC) measurement under the conditions employed in the examples described below or by an equivalent method.

The polymer (A) may be used in 1 kind or 2 or more kinds.

< copolymer (B) >

The copolymer (B) has a structural unit (B-1) derived from styrene and a structural unit (B-2) derived from a polymerizable monomer (B2) represented by the formula (B2).

Formula (b 2): CH (CH)₂＝CH－COO－(R^b1－O)_n－R^b2

In the formula (b2), R^b1Is an alkanediyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, R^b2Is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n is an integer of 1 to 3, preferably 1.

Examples of the alkanediyl group include a methanediyl group, an ethane-1, 2-diyl group, a propane-1, 3-diyl group, a propane-1, 2-diyl group and a butane-1, 4-diyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.

Examples of the polymerizable monomer (b2) include:

alkoxyalkyl acrylates such as methoxymethyl acrylate, 2-methoxyethyl acrylate, ethoxymethyl acrylate, 2-ethoxyethyl acrylate, 4-methoxybutyl acrylate, methoxypropyl acrylate, ethoxypropyl acrylate, propoxyethyl acrylate, 2-butoxyethyl acrylate, and isobutoxyethyl acrylate;

glycol-based acrylates such as ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, and methoxy-dipropylene glycol acrylate.

Among these, alkoxyalkyl acrylates are preferred, and 2-methoxyethyl acrylate (MEA) is particularly preferred.

The number of the structural units (b-2) may be 1, or 2 or more.

The structural unit (b-1) has a hydrophobic functional group, i.e., a phenyl group, and contributes to the improvement of the water resistance (crack resistance) of the antifouling coating film formed from the composition (I), and also contributes to the improvement of the hardness, impact resistance and polishing properties (Japanese polishing). The reason for the improvement in polishing performance (polishing performance) is not clear, and it is presumed that the constituent unit (b-1) improves the hardness of the formed antifouling coating film and exhibits physical polishing performance (polishing performance) against external forces such as frictional resistance in water.

The structural unit (b-2) contributes to the improvement of the hydrophilicity of the antifouling coating film.

The copolymer (B) usually does not have a structural unit derived from a silicone ester monomer.

When an acrylic copolymer having no hydrolyzable group is blended with a silicone ester polymer, the crack resistance of the coating film is generally improved, but the stain resistance tends to be lowered. This is considered to be caused by the fact that the side chain of the silicone ester polymer undergoes a hydrolysis reaction in water to elute a water-soluble polymer, and as a result, an acrylic copolymer having no hydrolyzable group is present in the coating film to suppress the hydrolysis reaction and the like. Therefore, it is considered that when a copolymer of styrene and a hydrophilic monomer is used as the acrylic copolymer, the antifouling coating film has a good balance between hydrophobicity and hydrophilicity, and can achieve both long-term antifouling property and crack resistance, but according to the study of the inventors of the present invention, it is found that such an effect is not necessarily exhibited depending on the type of the hydrophilic monomer.

As a result of further studies, the inventors of the present invention have found that by blending styrene and the polymerizable monomer (b2) described above, particularly a copolymer with MEA, with a silicone ester polymer, the balance between the hydrophobicity and hydrophilicity of the antifouling coating film becomes particularly good, and both long-term antifouling property and crack resistance can be achieved.

The proportion of the structural unit (B-1) in the copolymer (B) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less. When the proportion of the structural unit (b-1) is not less than the lower limit, the antifouling coating film preferably has high water resistance (crack resistance). When the proportion of the structural unit (b-1) is not more than the above upper limit, the antifouling coating film is excellent in antifouling property because the hydrophobicity does not become excessively high and hydrolysis of the polymer (a) is not inhibited.

The proportion of the structural unit (B-2) in the copolymer (B) is preferably 15% by mass or more, more preferably 20% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less. When the proportion of the structural unit (b-2) is not less than the lower limit, the antifouling property of the antifouling coating film is high, which is preferable. When the proportion of the structural unit (b-2) is not more than the above upper limit, the hydrophilicity of the antifouling coating film is not excessively high, and the antifouling agent is not excessively eluted in water, and therefore, the antifouling property is high not only for a short period (e.g., 12 months) but also for a long period (e.g., 36 months), which is preferable.

In recent years, the durability of the antifouling coating film is sometimes as long as, for example, 90 months. By using the copolymer (B) having the structural unit (B-1) and the structural unit (B-2), both long-term antifouling property and crack resistance of the antifouling coating film can be achieved. In particular, by setting the proportions of the structural unit (b-1) and the structural unit (b-2) to the above ranges, the reduction in the crack resistance of the antifouling coating film can be compensated for by the hydrophobicity of the structural unit (b-1) in the region where the proportion of the structural unit (b-2) is high, and therefore, long-term antifouling property and crack resistance can be achieved at the same time.

In one embodiment of the copolymer (B), when the proportion of the structural unit (B-2) is 15 to 45% by mass, the antifouling property is further improved as compared with when the proportion of the structural unit (B-2) is less than 15% by mass, and the long-term antifouling property is further improved as compared with when the proportion of the structural unit (B-2) exceeds 45% by mass. In one embodiment of the copolymer (B), when the proportion of the structural unit (B-1) is 30 to 80% by mass, the crack resistance is further improved as compared with when the proportion of the structural unit (B-1) is less than 30% by mass, and the stain resistance is further improved as compared with when the proportion of the structural unit (B-1) exceeds 80% by mass.

The ratio of each structural unit can be determined by the same method as that for the polymer (a).

The copolymer (B) may further have a structural unit (B-3) derived from another ethylenically unsaturated monomer (hereinafter also referred to as "monomer (B3)").

Examples of the monomer (b3) include:

(meth) acrylic acid;

(meth) acrylic acid esters (excluding the polymerizable monomer (b2)), specifically, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (3,5, 5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, and stearyl (meth) acrylate; alicyclic group-containing (meth) acrylates such as cyclohexyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; alkoxyalkyl methacrylates such as methoxymethyl methacrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, 4-methoxybutyl methacrylate, methoxypropyl methacrylate, ethoxypropyl methacrylate, propoxyethyl methacrylate, 2-butoxyethyl methacrylate, isobutoxyethyl methacrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, or aryloxyalkyl (meth) acrylate; glycol methacrylates such as ethoxy-diethylene glycol methacrylate, methoxy-triethylene glycol methacrylate, and methoxy-dipropylene glycol methacrylate; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate;

polyfunctional (meth) acrylates, specifically tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate;

specific examples of the vinyl monomer include vinyl acetate, isobutyl vinyl ether, vinyl toluene, (meth) acrylonitrile, vinyl propionate, and vinyl benzoate.

Among these, the (meth) acrylates are preferable, the alkyl (meth) acrylates are more preferable, and the methyl (meth) acrylate is further preferable.

The number of the structural units (b-3) may be 1 or 2 or more.

The proportion of the structural unit (B-3) in the copolymer (B) is preferably 55% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less, from the viewpoint of not inhibiting the above-described effects obtained by the structural unit (B-1) and the structural unit (B-2).

The weight average molecular weight (Mw) of the copolymer (B) is preferably 3,000 or more, more preferably 5,000 or more, further preferably 7,000 or more, preferably 35,000 or less, more preferably 30,000 or less, further preferably 25,000 or less, from the viewpoint of improving the crack resistance of the antifouling coating film formed from the composition (I). Mw can be determined by Gel Permeation Chromatography (GPC) measurement under the conditions employed in the examples described below or by an equivalent method.

The copolymer (B) may be used in 1 or 2 or more species.

The content ratio of the polymer (a) to the copolymer (B) in the composition (I) is preferably as follows. That is, the mass ratio (A: B) of the polymer (A) to the copolymer (B) is preferably 90:10 to 30:70, more preferably 80:20 to 40:60, and still more preferably 75:25 to 45: 55. In such an embodiment, the long-term antifouling property and crack resistance of the antifouling coating film are further improved, which is preferable.

The total content of the polymer (a) and the copolymer (B) is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, based on 100% by mass of the total solid content of the composition (I). When the total content is within this range, an antifouling coating film having excellent crack resistance can be easily obtained.

The content of the solid content in the composition (I) is preferably 50% by mass or more, more preferably 65% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of forming a composition having excellent coating workability.

In the present specification, the solid content and the content of the composition (I) are the residual heating component (nonvolatile component) and the content thereof obtained by the following method or an equivalent method. The composition (I) was weighed out into a metal test dish having a predetermined mass, developed on the bottom surface, placed in a constant temperature bath maintained at a temperature of 105 to 110 ℃ and heated for 3 hours, taken out, cooled at room temperature (example: 23 ℃), and then weighed again to determine the remaining amount in the metal test dish. The content (mass%) of the solid content was calculated by the following formula.

Content of solid matter (% by mass) is the remaining amount (g) in a metal test dish x 100/measured mass (g) of composition (I)

The same applies to the solid content and the content of each component.

< method for producing Polymer >

The method for producing the polymer (a) and the copolymer (B) is not particularly limited, and examples thereof include solution polymerization, suspension polymerization, and pressure polymerization, and solution polymerization using a general organic solvent under normal pressure is preferable from the viewpoint of high versatility. The solution polymerization may be carried out by the following method.

A reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube and a heating/cooling jacket was charged with a solvent, and heated and stirred at a temperature of about 60 to 200 ℃ under a nitrogen gas flow. The polymer (a) or the copolymer (B) can be obtained by dropping a mixture of the monomers, the polymerization initiator, and if necessary, the solvent, the chain transfer agent, and the like from the dropping device while maintaining the same temperature so as to be a ratio preferably to the structural unit, and performing a polymerization reaction.

The polymerization initiator is not particularly limited, and various radical polymerization initiators can be used. Specific examples thereof include 2,2 '-azobis (isobutyronitrile), 2' -azobis (2-methylbutyronitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), 4' -azobis-4-cyanovaleric acid, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, t-butyl peroctoate, t-butyl peroxybenzoate, potassium persulfate, and sodium persulfate. Further, these radical polymerization initiators may be added to the reaction system only at the start of the reaction, or may be added to the reaction system in both directions at the start of the reaction and during the reaction.

The amount of the polymerization initiator used in the production of the polymer (a) or the copolymer (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total of the monomers (reaction raw materials).

Examples of the solvent that can be used for producing the polymer (a) or the copolymer (B) include an organic solvent and water. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, ethylbenzene, mesitylene, and coal tar; alcohol solvents such as ethanol, propanol, isopropanol, butanol, and isobutanol; ether solvents such as propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate.

The chain transfer agent is not particularly limited, and examples thereof include α -methylstyrene dimer, thioglycolic acid, diterpenes, terpineol, and γ -terpinene; mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, and the like; secondary alcohols such as isopropyl alcohol and glycerin.

When a chain transfer agent is used in the production of the silicone ester polymer (a), the amount thereof to be used is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total of the monomers (reaction raw materials).

< other ingredients >

The composition (I) may further contain 1 or more of a monocarboxylic acid compound (C), copper and/or a copper compound (D), an organic antifouling agent (E), a coloring agent, an extender pigment, a thixotropic agent, a dehydrating agent, a plasticizer, a resin other than the polymer (A) and the copolymer (B), and a solvent as other components.

Each of the components described below can be used in 1 type or 2 or more types.

< monocarboxylic acid compound (C) >)

The composition (I) preferably contains the monocarboxylic acid compound (C) from the viewpoint of not only improving the antifouling property but also adjusting the consumption rate of the coating film.

Examples of the monocarboxylic acid compound (C) include aliphatic or alicyclic monocarboxylic acids, monocarboxylic acid derivatives thereof, and metal salts thereof. Examples of the monocarboxylic acid derivative include an ester and an amide of a monocarboxylic acid. Examples of the metal salt include zinc salt, copper salt, aluminum salt, magnesium salt, calcium salt, and barium salt. Specific examples of monocarboxylic acids include rosins, naphthenic acids, cycloolefin carboxylic acids, bicycloalkene carboxylic acids, trimethylisobutylene cyclohexene carboxylic acids, isononanoic acid, neodecanoic acid (Versatic acid), stearic acid, hydroxystearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, pimaric acid, abietic acid, and neoabietic acid. Examples of the rosin include rosins such as rubber rosin, wet rosin, tall oil rosin, and the like; rosin derivatives such as hydrogenated rosin, non-homogenized rosin, and rosin metal salt, and pine tar. As the monocarboxylic acid compound (C), rosin derivatives, naphthenic acid, neodecanoic acid, trimethylisobutylene cyclohexene carboxylic acid, and metal salts thereof are preferable.

The mass ratio of the monocarboxylic acid compound (C) in the composition (I) (total mass of the polymer (a) and the copolymer (B): mass of the monocarboxylic acid compound (C)) is preferably 95:5 to 40:60, more preferably 90:10 to 50: 50.

< copper and/or copper compound (D) >)

The composition (I) preferably contains copper and/or a copper compound (D) as the antifouling agent, from the viewpoint of further improving the antifouling property against the aquatic organisms such as animals. Copper is, for example, copper powder. Examples of the copper compound include cuprous oxide, copper thiocyanate, and copper-nickel alloy, and cuprous oxide and copper thiocyanate are preferable. Further, copper pyrithione is not a copper compound and is therefore classified as the following organic antifouling agent (E).

The content of copper and/or copper compound (D) is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on 100% by mass of the total solid content of composition (I).

Organic antifouling agent (E) >, and its preparation method

The composition (I) preferably contains an organic antifouling agent (E) as the antifouling agent. The organic antifouling agent (E) is a component for further improving the antifouling property of the antifouling coating film.

As the organic antifouling agent (E), for example, pyrithione metals such as copper pyrithione and zinc pyrithione, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, pyridine triphenylborane, 4-isopropylpyridine diphenylmethyl borane, N-dimethyl-N' - (3, 4-dichlorophenyl) urea, N- (2,4, 6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1, 3, 5-triazine, metomidine ((+/-) -4- [ 1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole), 2,4,5, 6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamate ethylzinc ethylenedithiocarbamate, bis (dimethyldithiocarbamate), sodium dithiocarbamoylamine, sodium dithioamine, sodium dimethyldithiocarbamate, sodium dithioamine, sodium hydrogen sulfite, sodium, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium carbonate, sodium carbonate, chloromethyl-N-octyl disulfide, N '-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, N' -dimethyl-N-tolyl- (N-fluorodichloromethylthio) sulfamide, tetraalkyl thiram disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2, 3-dichloro-N- (2',6' -diethylphenyl) maleimide, 2, 3-dichloro-N- (2 '-ethyl-6' -methylphenyl) maleimide and the like. Among these, preferred are pyrithione metals such as copper pyrithione and zinc pyrithione, medetomidine, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bisdimethyldithiocarbamate, ethylzinc dithiocarbamate, more preferred are copper pyrithione, medetomidine, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, and even more preferred are copper pyrithione and medetomidine.

The content of the organic antifouling agent (E) is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, based on 100% by mass of the total solid content of the composition (I).

＜＜Coloring agent >

As the colorant, various conventionally known organic and inorganic pigments and dyes can be used. Examples of the organic pigment include naphthol red and phthalocyanine blue. Examples of the inorganic pigment include carbon black, red iron oxide, barite powder, titanium white (titanium oxide), and yellow iron oxide. When the composition (I) contains a colorant, it is preferable in terms of being able to arbitrarily adjust the hue of the antifouling coating film obtained from the composition.

The content of the colorant is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, based on 100% by mass of the total solid content of the composition (I).

Extender pigment

Examples of the extender pigment include zinc oxide, talc, silica, mica, clay, potash feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium sulfate, and zinc sulfide. Among these, zinc oxide, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, and potash feldspar are preferable.

The composition (I) preferably contains an extender pigment in view of improving the coating film properties such as crack resistance of the obtained antifouling coating film.

The content of the extender pigment is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the total solid content of the composition (I).

Thixotropic agent

Thixotropic agents are ingredients that contribute to the sag and sedimentation resistance of the coating.

Examples of the thixotropic agent (anti-sagging agent, anti-settling agent) include organobentonite, salts of Al, Ca or Zn selected from amine salts, stearate salts, lecithin salts and alkylsulfonate salts; a wax selected from the group consisting of polyethylene wax, oxidized polyethylene wax, amide wax, hydrogenated castor bean oil wax, and polyamide wax; synthesizing the micro-powder silicon dioxide.

The thixotropic agent is used for improving the precipitation resistance of copper and/or a copper compound (D), an organic antifouling agent (E), a coloring agent, an extender pigment, a dehydrating agent and other solid materials during storage of the antifouling paint composition and for improving the painting workability during painting.

The content of the thixotropic agent is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on 100% by mass of the total solid content of the composition (I).

(dewatering agent)

Examples of the dehydrating agent include inorganic dehydrating agents and organic dehydrating agents, and examples of the inorganic dehydrating agents include synthetic zeolite, anhydrite and hemihydrate gypsum, and examples of the organic dehydrating agents include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane, and alkyl orthoformates such as polyalkoxysilanes, methyl orthoformate and ethyl orthoformate, which are condensates thereof. The dehydrating agent is used for preventing gelation and the like caused by decomposition of the hydrolyzable resin due to water generated at the time of production and/or storage of the antifouling coating composition.

The content of the dehydrating agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the total solid content of the composition (I).

(plasticizer)

Examples of the plasticizer include n-alkanes, chlorinated paraffins, petroleum resins, ketone resins, tricresyl phosphate, polyvinyl ethyl ether, and dialkyl phthalates, and among these, chlorinated paraffins, petroleum resins, and ketone resins are preferable. When the composition (I) contains a plasticizer, it is preferable from the viewpoint of further improving the crack resistance and water resistance of the antifouling coating film obtained from the composition.

The chlorinated paraffin may have any of a linear or branched molecular structure, and may be liquid or solid (powder) at room temperature.

The average carbon number of the chlorinated paraffin is preferably 8 to 30, more preferably 10 to 26 in 1 molecule. The antifouling paint composition containing the chlorinated paraffin can form an antifouling coating film with less cracks and peeling. The average carbon number is preferably 8 or more because the effect of suppressing the occurrence of cracks is high, and the average carbon number is preferably 30 or less because the antifouling property is not suppressed.

The chlorinated paraffin preferably has a viscosity (unit POISE, measurement temperature 25 ℃) of 1 or more, more preferably 1.2 or more, and a specific gravity (25 ℃) of 1.05 to 1.80g/cm³More preferably 1.10 to 1.70g/cm³。

Examples of the petroleum resin include C5-based, C9-based, styrene-based, dicyclopentadiene-based petroleum resins, and hydrogenated products thereof.

The content of the plasticizer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the total solid content of the composition (I).

Resins other than the polymer (A) and the copolymer (B)

The composition (I) may contain resins other than the polymer (A) and the copolymer (B). Examples of the resins include water-insoluble or water-insoluble resins such as polyester resins, unsaturated polyester resins, fluorine resins, polybutene resins, polyurethane resins, epoxy resins, polyamide resins, vinyl resins (vinyl chloride copolymers, ethylene-vinyl acetate copolymers, etc.), chlorinated olefin resins, styrene-butadiene copolymer resins, alkyd resins, coumarone resins, terpene phenol resins, organic silicone rubbers, and chlorinated rubbers.

The content of the resin is, for example, 0.01 to 100 parts by mass based on 100 parts by mass of the total of the polymer (A) and the copolymer (B).

Solvent

The composition (I) may contain a solvent such as water or an organic solvent as needed for improving the dispersibility of each component or adjusting the viscosity of the composition. The solvent may be a solvent used in the preparation of the polymer (a) or the copolymer (B), or may be a solvent separately added in the preparation of the antifouling paint composition by mixing the polymer (a) and the copolymer (B) with other components as required. As the solvent, an organic solvent is preferable. The organic solvent may be the organic solvent described in the item < method for producing a polymer >.

When the composition (I) contains a solvent, the content thereof is determined to be a preferable amount according to a desired viscosity according to a coating form of the coating composition. The content of the solvent in the composition (I) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When the content of the solvent is too large, problems such as a reduction in sagging prevention property may occur.

< method for producing antifouling paint composition >

The composition (I) can be produced by a known method as appropriate, except for using the polymer (a) and the copolymer (B). For example, the polymer (a), the copolymer (B), and the other components described above as necessary may be added to a stirring vessel at once or in any order, and the components may be mixed by a known stirring and mixing method and dispersed or dissolved in a solvent to produce the copolymer.

Examples of the stirring and mixing method include a method using a paint stirrer, a high-speed homogenizer, a sand mill, a basket mill, a ball mill, a three-roll mixer, a Ross mixer (ロスミキサ A), a planetary mixer, and a Utility agitation machine

[ use of antifouling paint composition]

The antifouling coating film (hereinafter also referred to as "antifouling coating film (J)") of the present embodiment is formed from the composition (I). The substrate with an antifouling coating film (hereinafter also referred to as "antifouling substrate (K)") according to the present embodiment has a substrate and an antifouling coating film (J) provided on the surface of the substrate.

The method for producing the antifouling substrate (K) comprises a step of coating or impregnating the substrate (target object, coated object) with the composition (I), and a step of drying a coated body or impregnated body obtained by coating or impregnating the substrate when the composition (I) contains a solvent.

For the coating, for example, a known method such as air spraying, airless spraying, brushing, and roller can be used.

The composition (I) coated or impregnated by the above method can be dried by leaving it at-5 to 30 ℃ for preferably about 1 to 10 days, more preferably about 1 to 7 days, to obtain an antifouling coating film (J). In addition, the drying of the composition (I) may be carried out while blowing air under heating.

Alternatively, the stain-repellent substrate (K) can be produced by forming the stain-repellent coating film (J) obtained from the composition (I) on the surface of another substrate, peeling the stain-repellent coating film (J) from the other substrate, and attaching the same to the substrate to be stain-repellent. In this case, the stain-proofing coating film (J) may be attached to the substrate via an adhesive.

The substrate may have a primer treatment on its surface, or may have a layer formed of various resin-based coatings such as an epoxy resin-based coating, a vinyl resin-based coating, an acrylic resin-based coating, and a urethane resin-based coating on its surface. The surface of the substrate on which the antifouling coating film (J) is provided is the surface after the primer treatment or the surface of the layer formed of the above-mentioned coating material.

The base material is not particularly limited, and the composition (I) is preferably used for long-term antifouling of the base material in a wide industrial field such as ships, fisheries, and underwater structures. Thus, as the base material, for example, examples of the material include hull plates of ships (e.g., large steel ships such as container ships and tankers, fishing boats, FRP (fiber reinforced plastic) ships, wooden ships, yachts, and the like, and also any of these new ships or renovation ships), underwater structures (e.g., various underwater civil engineering structures in petroleum pipelines, water pipes, circulating pipes, water supply and drainage ports of plants, thermal power stations, and nuclear power stations, submarine cables, equipment using seawater (e.g., sea water pumps), ultra-large floating ocean buildings, bay coastal roads, submarine tunnels, harbor facilities, canals, and waterways), fishery materials (e.g., ropes, fishing nets, fishing gears, floats, buoys), water supply and drainage pipes of seawater in plants, thermal power stations, and nuclear power stations, and the like, underwater wear, underwater glasses, oxygen bottles, swim wear, and torpedoes. Among these, ships, underwater structures, fishery materials, and water supply and drainage pipes are preferable, and ships and underwater structures are more preferable, and ships are particularly preferable.

In the case of producing the antifouling substrate (K), when the substrate is a fishing net or a steel plate, the composition (I) may be applied directly to the surface of the substrate, and when the substrate is a fishing net, the composition (I) may be impregnated into the surface of the substrate. Further, like a steel sheet having a deteriorated antifouling coating film, the antifouling coating film (J) can be formed on the surface of the antifouling coating film (J) or the substrate on which the antifouling coating film has been formed before, for the purpose of repair.

The thickness of the antifouling coating film (J) is not particularly limited, and is, for example, about 30 to 1000 μm. When the antifouling coating film (J) is formed by applying the composition (I) to a substrate, the antifouling coating film (J) is preferably applied 1 to 300 μm, more preferably 30 to 200 μm, in a thickness of 1 to a plurality of times.

The ship having the antifouling coating film (J) can prevent adhesion of aquatic organisms, and thus can prevent a reduction in ship speed and an increase in fuel consumption caused thereby. The underwater structure having the antifouling coating film (J) can prevent the adhesion of aquatic organisms for a long period of time, thereby maintaining the function of the underwater structure for a long period of time. The fishing net having the antifouling coating film (J) can prevent the adhesion of aquatic organisms, thereby preventing the clogging of the net. In addition, the water supply and drainage pipe having the antifouling coating film (J) on the inner surface can prevent the adhesion and propagation of aquatic organisms, thereby preventing the clogging of the water supply and drainage pipe and the reduction of the flow rate.

Examples

The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, "part" means "part by mass".

[ measurement conditions]

The polymer was subjected to Gel Permeation Chromatography (GPC) measurement, and the content of the heating residue component was measured with respect to the copolymer solution. The measurement conditions are as follows.

< GPC measurement Condition >

The device comprises the following steps: "HLC-8320 GPC" (manufactured by Tosoh corporation)

Column: "TSKgel guard column SuperMP (HZ) -M + TSKgel SuperMultiporeHZ-M + TSKgel SuperMultiporeHZ-M" (all made by Tosoh Co., Ltd.)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.35ml/min

A detector: RI (Ri)

Column thermostat temperature: 40 deg.C

Standard curve: standard office styrene and styrene monomer

The sample preparation method comprises the following steps: THF was added to the copolymer solution obtained in each production example to dilute the copolymer solution, and the resulting solution was filtered through a membrane filter, and the obtained filtrate was used as a GPC measurement sample.

< measurement Condition for content of heating residue component >

The copolymer solution was weighed in a metal test dish having a predetermined mass, developed on the bottom surface, placed in a constant temperature bath maintained at a temperature of 105 to 110 ℃ and heated for 3 hours, taken out, cooled to room temperature, and then weighed again to determine the remaining amount in the metal test dish. The content (mass%) of the solid content was calculated by the following equation.

The solid content (% by mass) is equivalent to the mass (g) of the copolymer solution measured by subtracting 100/g from the residual amount (g) in the metal test dish

[ production example of Polymer]

Production example 1]Production of solution of Silicone ester Polymer (A)

A reaction vessel equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet tube and a dropping device was charged with 43 parts of xylene and 10 parts of triisopropylsilyl methacrylate, and heated and stirred under a nitrogen atmosphere so that the liquid temperature became 80 ℃. A mixture of monomers (50 parts of triisopropylsilyl methacrylate, 25 parts of 2-methoxyethyl methacrylate, 10 parts of methyl methacrylate, and 5 parts of butyl acrylate) and a polymerization initiator (1.35 parts of 2,2' -azobis (isobutyronitrile)) was added dropwise from a dropping device while maintaining the same temperature for 2 hours in a reaction vessel. Then, the mixture was heated and stirred at the same temperature for 1 hour, and at a liquid temperature of 88 ℃ for 1 hour, and then the liquid temperature was increased to 95 ℃. The same temperature was maintained and 0.1 part of 2,2' -azobis (isobutyronitrile) was added dropwise every 30 minutes for a total of 4 times, after which the liquid temperature was increased to 105 ℃. After stirring and heating at the same temperature for 30 minutes, 23.7 parts of xylene were added to the reaction vessel to obtain a solution of the silicone ester copolymer (A-1) (copolymer solution (A-1)). The weight-average molecular weight of the silicone ester copolymer (A-1) was 28,649. The content of the residual components after heating of the solution was 60.0 mass%.

Production example 2]Production of solution of copolymer (B)

A reaction vessel equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet tube and a dropping device was charged with 66.7 parts of xylene, and heated and stirred under a nitrogen atmosphere so that the liquid temperature became 110 ℃. A mixture of monomers (70 parts of styrene, 30 parts of 2-methoxyethyl acrylate) and a polymerization initiator (4 parts of 2,2' -azobis (isobutyronitrile), 1 part of t-butylperoxybenzoyl) was added dropwise from a dropping device while maintaining the same temperature for 3 hours in a reaction vessel, and the mixture was heated and stirred at the same temperature for 1 hour, at 120 ℃ for 1 hour, and at 130 ℃ for 1 hour to obtain a solution of the copolymer (B-1) (copolymer solution (B-1)).

The solution of the copolymer (B) (copolymer solutions (B-2) to (B-14)) and the solution of the comparative copolymer (cB) (copolymer solutions (cB-1) to (cB-7)) were obtained by changing the monomers as shown in table 1 and adjusting the liquid temperature and the amount of the polymerization initiator as appropriate.

The property values are shown in Table 1. The numerical value of the monomer represents the amount (parts by mass) to be blended.

The content of the heating residue in the solution was about 60% by mass.

St: styrene (meth) acrylic acid ester

MMA: methacrylic acid methyl ester

BA: acrylic acid n-butyl ester

MEA: 2-Methoxyethyl acrylate

And (4) MEMA: 2-Methoxyethyl methacrylate

HEA: 2-Hydroxyethyl acrylate

HPA: 2-hydroxypropyl acrylate

GMA: glycidyl methacrylate

PhOEtA: 2-Phenoxyethyl acrylate

[ TABLE 1]

[ preparation of antifouling paint composition]

[ example 1]

An antifouling paint composition was prepared by the following procedure.

To a plastic container were added 11.3 parts of xylene, 1 part of an aromatic hydrocarbon mixture (Solvesso 150), 4 parts of rubber rosin (chinese rubber rosin WW), 0.5 part of alkoxysilane (Ethyl silicate 28), 12 parts of a silicone ester copolymer solution (a-1), and 8 parts of a copolymer solution (B-1), and the components were mixed until uniformly dispersed or dissolved using a paint shaker. Thereafter, 7 parts of talc (FC-1), 7 parts of zinc oxide (Zinc oxide No. 3), 9.5 parts of barium sulfate (precipitated barium sulfate 100), 35 parts of cuprous oxide (NORDOX), 0.7 parts of red iron dioxide (TODA COLOR NM-50), 1 part of titanium oxide (TIPAQUE R-930), 1 part of Copper pyrithione (Copper Omadine Powder), 1 part of polyethylene oxide (DISPARLON 4200-20X) and 150 parts of glass beads were added to a polyethylene container, and these components were dispersed by stirring with a paint stirrer for 1 hour. After the dispersion, 1 part of fatty acid amide (DISPARLON A630-20X) was further added, and after stirring for 20 minutes using a paint shaker, glass beads were removed from the mixture by means of a filter screen (mesh: 80 mesh), to obtain an antifouling paint composition.

[ examples 2 to 20 ]]

An antifouling paint composition was prepared in the same manner as in example 1, except that the kinds and loading of the components were changed as shown in table 2.

[ comparative examples 1 to 7]

Antifouling paint compositions were prepared in the same manner as in example 1, except that the kinds and loading of the components were changed as shown in table 3.

In tables 2 and 3, (A), (B) and (cB) are the amounts of the copolymer solutions.

[ evaluation of physical Properties of antifouling paint composition]

The physical properties of the coating films formed by using the antifouling paint compositions obtained in examples and comparative examples were evaluated as follows. The results obtained are shown in tables 2 and 3.

< static antifouling test >

An epoxy anticorrosive paint (trade name "Bannoh 500", manufactured by Chinese paint Corp.) was applied to a sandblasted steel sheet (300 mm. times.100 mm. times.2.3 mm) by air spraying so that the thickness of the paint film was 150 μm, and the resultant was dried at 23 ℃ for 1 week to form a cured coating film. Subsequently, a vinyl adhesive coating (trade name "SILVAX SQ-K", manufactured by Chinese paint Ltd.) was applied to the cured coating film by air spray coating so that the dry film thickness became 40 μm, and the cured coating film was dried at 23 ℃ for 24 hours.

Next, each of the antifouling paint compositions prepared in examples and comparative examples was applied to the surface of the dried coating film formed from the vinyl binder paint in a dry film thickness of 200 μm, and then dried at 23 ℃ for 7 days to form an antifouling coating film, thereby producing a static antifouling test panel.

The static antifouling test plate thus produced was suspended and immersed on a water surface of 400mm or less in the inner sea of a rice-laboratory, a water area of twenty-day city, guangdao, japan, and was set in a static state, and the area of a portion to which aquatic organisms were attached (hereinafter also referred to as "attached area") (%) on the antifouling coating film was measured when the total area of the antifouling coating film in the seawater-free area of the test plate was 100% after 6 months, 12 months, 24 months, and 36 months from the start of immersion, and static antifouling property was evaluated based on the following evaluation criteria.

(evaluation criteria)

5: the attachment area is less than 5%.

4: the adhesion area is 5% or more but less than 20%.

3: the adhesion area is 20% or more but less than 50%.

2: the attachment area is 50% or more and less than 70%.

1: the attachment area is 70% or more.

< test for cracking resistance (Water resistance) of coating film >

An epoxy anticorrosive paint (trade name "Bannoh 500", manufactured by Chinese paint Corp.) was applied to a sandblasted steel sheet (150 mm. times.70 mm. times.1.6 mm) by air spraying so that the thickness of the paint film was 150 μm, and the resultant was dried at 23 ℃ for 1 week to form a cured coating film. Subsequently, a vinyl adhesive coating (trade name "SILVAX SQ-K", manufactured by Chinese paint Ltd.) was applied to the cured coating film by air spray coating so that the dry film thickness became 40 μm, and the cured coating film was dried at 23 ℃ for 24 hours.

Then, each of the antifouling paint compositions prepared in examples and comparative examples was applied to the surface of the dried coating film formed from the vinyl binder paint so that the thickness of the coating film was 300 μm, and then dried at 23 ℃ for 7 days to form an antifouling coating film, thereby preparing a test plate.

The test plate was immersed in artificial seawater at 50 ℃ and the appearance of the coating film was examined every 1 month, followed by 6 months. In addition, the artificial seawater was replaced with fresh artificial seawater every 1 week. The crack resistance of the coating film was evaluated based on the following evaluation criteria (i.e., the ratio of the area of cracks to the total area of the surface of the coating film).

(evaluation criteria)

5: there was no abnormal condition at all.

4: cracking was observed to occur at less than 10% of the total area of the surface of the coating film.

3: it was confirmed that cracks were generated in 10% or more and less than 30% of the total area of the coating film surface.

2: it was confirmed that cracks were generated in 30% or more and less than 50% of the total area of the coating film surface.

1: it was confirmed that cracks occurred in 50% or more of the total area of the coating film surface.

[ TABLE 2]

[ TABLE 3]

The details of the components used in the examples and comparative examples are as follows.

[ TABLE 4]

When a copolymer having HEA cells or HPA cells is used instead of MEA cells, the antifouling property and crack resistance are exhibited in a short period of time, but the antifouling property and crack resistance are low over a long period of time. This is presumably due to the fact that HEA and HPA are too hydrophilic compared to MEA.

When a copolymer having GMA units instead of MEA units is used, there is a tendency that long-term antifouling properties are low. This is presumably because GMA units are less hydrophilic than MEA units, and the hydrolysis reaction of the silicone ester polymer becomes insufficient.

When a copolymer having a MEMA unit in place of an MEA unit is used, the antifouling property is low. This is presumably because the MEMA unit has higher hydrophobicity than the MEA unit, and the hydrolysis reaction of the silicone ester polymer is suppressed.

When a copolymer having MMA units or BA units is used in place of St units, the antifouling property and crack resistance are low.

In comparison with the above comparative examples, when a copolymer having St units and MEA units is used, the long-term antifouling property and crack resistance are excellent. The reason is not clear, and it is presumed that the balance between the hydrophobicity and the hydrophilicity of the antifouling coating film is particularly good by blending a copolymer of St and MEA with the silicone ester polymer.

Claims

1. An antifouling paint composition characterized by comprising:

a silicone-based polymer (A), and

a copolymer (B) comprising a structural unit (B-1) derived from styrene and a structural unit (B-2) derived from a polymerizable monomer (B2) represented by the formula (B2),

formula (b 2): CH (CH)₂＝CH－COO－(R^b1－O)_n－R^b2

In the formula (b2), R^b1Is an alkanediyl group having 1 to 5 carbon atoms, R^b2Is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 3.

2. The antifouling paint composition according to claim 1, wherein:

in the copolymer (B), the proportion of the structural unit (B-1) is 30 to 80% by mass.

3. The antifouling paint composition according to claim 1, wherein:

in the copolymer (B), the proportion of the structural unit (B-2) is 15 to 45% by mass.

4. The antifouling paint composition according to claim 1, wherein:

in the copolymer (B), the proportion of the structural unit (B-1) is 30 to 80% by mass, and the proportion of the structural unit (B-2) is 15 to 45% by mass.

5. The antifouling paint composition according to claim 1, wherein:

the polymerizable monomer (b2) represented by the formula (b2) is an alkoxyalkyl acrylate.

6. The antifouling paint composition according to claim 5, wherein:

the polymerizable monomer (b2) represented by the formula (b2) is 2-methoxyethyl acrylate.

7. The antifouling paint composition according to claim 1, wherein:

the silicone-based polymer (A) has a structural unit derived from triisopropylsilyl methacrylate.

8. The antifouling paint composition according to claim 1, wherein:

the mass ratio (A: B) of the silicone ester polymer (A) to the copolymer (B) is 90:10 to 30: 70.

9. The antifouling paint composition according to claim 1, wherein:

further comprises a monocarboxylic acid compound (C).

10. The antifouling paint composition according to claim 1, wherein:

further contains copper and/or a copper compound (D).

11. The antifouling paint composition according to claim 1, wherein:

further contains an organic antifouling agent (E).

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

13. A substrate with an antifouling coating film, comprising:

a substrate, and

the antifouling coating film according to claim 12 provided on the surface of the substrate.

14. The substrate with an antifouling coating film according to claim 13, wherein:

the base material is at least 1 selected from the group consisting of ships, underwater structures, fishery materials and water supply and drainage pipes.

15. A method for producing a substrate with an antifouling coating film, comprising:

the method comprises a step of coating or impregnating a substrate with the antifouling paint composition according to any one of claims 1 to 11.