阅读说明：本技术 防污涂料组合物 (Antifouling coating composition ) 是由 岩田雄树 于 2021-03-25 设计创作，主要内容包括：本发明提供能够形成耐裂纹性、对劣化涂膜的附着性和动态防污性优异的防污涂膜且含有硅酯系聚合物和美托咪定的防污涂料组合物。该防污涂料组合物含有：具有来自式(a1)所示的聚合性单体(a1)的结构单元(a－1)的硅酯系聚合物(A)、具有来自(甲基)丙烯酸缩水甘油酯的结构单元(b－1)的丙烯酸系聚合物(B)、美托咪定(C)和特定量的氧化亚铜(D),R～(1)－CH＝C(CH-3)－COO－(SiR～(2)R～(3)O)-n－SiR～(4)R～(5)R～(6)…(a1)式(a1)中,R～(2)～R～(6)分别独立为可以具有杂原子的碳原子数1～20的1价有机基团。n为0或1以上的整数。R～(1)为氢原子或R～(7)－O－C(＝O)－所示的基团,R～(7)为氢原子等。(The invention provides an antifouling coating composition which can form an antifouling coating film with excellent crack resistance, adhesion to a deteriorated coating film and dynamic antifouling property and contains a silicone ester polymer and medetomidine. The antifouling paint composition comprises: a silicone ester polymer (A) having a structural unit (a-1) derived from a polymerizable monomer (a1) represented by the formula (a1), an acrylic polymer (B) having a structural unit (B-1) derived from glycidyl (meth) acrylate, medetomidine (C), and a specific amount of cuprous oxide (D), R 1 －CH＝C(CH 3 )－COO－(SiR 2 R 3 O) n －SiR 4 R 5 R 6 … (a1) formula (a1) wherein R is 2 ～R 6 Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom. n is 0 or an integer of 1 or more. R 1 Is a hydrogen atom or R 7 -O-C (═ O) -, group, R 7 Hydrogen atom, etc.)

1. An antifouling paint composition characterized by comprising:

a silicone ester polymer (A) having a structural unit (a-1) derived from a polymerizable monomer (a1) represented by the formula (a1),

An acrylic polymer (B) having a structural unit (B-1) derived from glycidyl (meth) acrylate,

Medetomidine (C), and

(ii) cuprous oxide (D),

the content of the cuprous oxide (D) is more than 0 mass% and 55 mass% or less in the solid content of the antifouling paint composition,

R¹－CH＝C(CH₃)－COO－(SiR²R³O)_n－SiR⁴R⁵R⁶…(a1)

in the formula (a1), R²～R⁶Each independently represents a 1-valent organic group having 1 to 20 carbon atoms and may have a hetero atom, n is an integer of 0 or 1 or more, R¹Is a hydrogen atom or R⁷-O-C (═ O) -, group, R⁷A hydrogen atom, a 1-valent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R⁸R⁹R¹⁰Silyl radicals represented by Si-, R⁸、R⁹And R¹⁰Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom.

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

further comprises a monocarboxylic acid compound (E).

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

the monocarboxylic acid compound (E) is a rosin (E1).

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

the mass ratio of the rosin (E1) to the sum of the silicone ester polymer (A) and the acrylic polymer (B), i.e., the sum of the mass of the polymer (A) and the mass of the polymer (B)/the mass of the rosin (E1) is 0.7 to 4.

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

and talc, wherein the content of talc is 2 to 17% by mass in the solid content of the antifouling paint composition.

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

which is used for repairing a deteriorated coating film of an antifouling coating film.

7. An antifouling coating film characterized by:

an antifouling paint composition according to any one of claims 1 to 6.

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

a base material, and

the antifouling coating film according to claim 7 provided on the surface of the substrate.

9. The substrate with an antifouling coating film according to claim 8, 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.

10. 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 6.

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 deteriorated or various problems occur. For example, when the base material is a ship, resistance due to water flow is increased, and thus the ship speed may be reduced or fuel consumption may be increased. When the substrate is an underwater structure, the anticorrosive coating film 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 lifetime. When the substrate is a fishing net such as a net for farming or a fixing net, the net is clogged with aquatic organisms, and there may be a serious problem such as death due to oxygen deficiency of the farmed organisms and the captured organisms. When aquatic organisms adhere to and propagate in seawater supply and drainage pipes in factories, thermal power plants, nuclear power plants, and the like, they may cause clogging of the supply and drainage pipes and a decrease 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 development of an antifouling paint containing a silicone ester polymer has been advanced as one of them.

Patent document 1 describes an antifouling coating composition containing a silicone ester copolymer containing triisopropylsilyl methacrylate and a hydrophilic (meth) acrylate comonomer, and medetomidine.

Patent document 2 describes an antifouling paint composition in which a copolymer containing a structural unit derived from styrene and a structural unit derived from glycidyl (meth) acrylate is blended with an antifouling paint containing a silicone ester polymer.

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication No. 2019-535868

Patent document 2: international publication No. 2014/175246

Disclosure of Invention

Technical problem to be solved by the invention

Patent document 1 discloses that the antifouling coating composition can form a coating film having crack resistance and excellent antifouling properties, particularly excellent barnacle adhesion-inhibiting properties. However, in the examples of this document, the barnacle resistance was evaluated as the antifouling performance by the static immersion test, but the dynamic antifouling performance was not clear. Further, according to the study of the present inventors, it has been found that an antifouling coating film formed from an antifouling coating composition containing medetomidine is difficult to form an antifouling coating film having excellent crack resistance, adhesion to a conventional antifouling coating film deteriorated by immersion in seawater or the like (hereinafter, also simply referred to as a deteriorated coating film), and dynamic antifouling property. Further, it is clear that the antifouling coating composition still has room for improvement from the viewpoint of long-term storage stability.

The present invention addresses the problem of providing an antifouling coating composition containing a silicone ester polymer and medetomidine, which is capable of forming an antifouling coating film having excellent crack resistance, adhesion to a deteriorated coating film, and dynamic antifouling properties.

Technical solution for solving technical problem

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an antifouling paint composition as described below can solve the above-mentioned problems. That is, the present invention relates to the following [1] to [10 ].

[1] An antifouling coating composition comprising: a silicone ester polymer (A) having a structural unit (a-1) derived from a polymerizable monomer (a1) represented by the formula (a1), an acrylic polymer (B) having a structural unit (B-1) derived from glycidyl (meth) acrylate, medetomidine (C), and cuprous oxide (D), wherein the content of cuprous oxide (D) is more than 0 mass% and 55 mass% or less in the solid content of the antifouling paint composition.

R¹－CH＝C(CH₃)－COO－(SiR²R³O)_n－SiR⁴R⁵R⁶…(a1)

[ in the formula (a1), R²～R⁶Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom. n is 0 or an integer of 1 or more. R¹Is a hydrogen atom or R⁷－O－C(＝O) -a group represented by R⁷A hydrogen atom, a 1-valent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R⁸R⁹R¹⁰Silyl radicals represented by Si-, R⁸、R⁹And R¹⁰Each independently represents a 1-valent organic group having 1 to 20 carbon atoms which may have a heteroatom.]

[2] The antifouling paint composition as claimed in the above [1], further comprising a monocarboxylic acid compound (E).

[3] The antifouling paint composition as claimed in the above [2], wherein the monocarboxylic acid compound (E) is a rosin (E1).

[4] The antifouling paint composition as claimed in [3], wherein the mass ratio of the rosin (E1) to the total of the silicone ester polymer (A) and the acrylic polymer (B) (total mass of the polymer (A) and the polymer (B)/mass of the rosin (E1)) is 0.7 to 4.

[5] The antifouling paint composition as claimed in any one of the above [1] to [4], further comprising talc, wherein the talc is contained in an amount of 2 to 17 mass% in the solid content of the antifouling paint composition.

[6] The antifouling paint composition as claimed in any one of the above [1] to [5], which is used for repairing a deteriorated coating film of an antifouling coating film.

[7] An antifouling coating film formed from the antifouling paint composition according to any one of the above [1] to [6 ].

[8] A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film according to [7] provided on the surface of the substrate.

[9] The substrate with an antifouling coating film according to the above [8], wherein the substrate is at least 1 selected from the group consisting of ships, underwater structures, fishery materials and water supply and drainage pipes.

[10] 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 [6 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an antifouling coating composition containing a silicone ester polymer and medetomidine can be provided, which can form an antifouling coating film having excellent crack resistance, adhesion to a deteriorated coating film, and dynamic antifouling properties.

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 generic term for both acrylates and methacrylates. The same applies to the use examples of (meth) acrylic acid and the like.

"structural unit from XX" means that if 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 (hereinafter also referred to as "composition (I)") according to the present embodiment contains a silicone ester polymer (a), an acrylic polymer (B), medetomidine (C), and cuprous oxide (D), which are described below.

< Silicone ester Polymer (A) >

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

R¹－CH＝C(CH₃)－COO－(SiR²R³O)_n－SiR⁴R⁵R⁶…(a1)

Each symbol in the formula (a1) will be described below.

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, each of which may have a heteroatom such as an oxygen atom between the bonds of carbon atoms, and from the viewpoint of easily obtaining an excellent antifouling coating film having a good balance between crack resistance and long-term dynamic antifouling property due to appropriate hydrolyzability, 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.

R¹Is 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 trialkylsilyl methacrylate, alkyldiarylsilyl methacrylate, or aryldialkylsilyl methacrylate, and more preferably trialkylsilyl methacrylate. Examples of the trialkylsilyl methacrylate include trimethylsilyl methacrylate, triethylsilyl methacrylate, tripropylsilyl methacrylate, triisopropylsilyl methacrylate, tributylsilyl methacrylate, triisobutylsilyl methacrylate, tri-sec-butylsilyl methacrylate, tri-2-ethylhexylsilyl methacrylate, and butyldiisopropylsilyl methacrylate. Further, as the polymerizable monomer (a1), a polymerizable monomer having n of 2 or more in the above formula (a1) such as 1-methacryloxynonamethyltetrasiloxane may be mentioned. Among these, trialkylsilyl methacrylate having a branched alkyl group is preferable, and triisopropylsilyl methacrylate is more preferable, from the viewpoint of easily obtaining an antifouling coating film having excellent balance between crack resistance and long-term dynamic antifouling properties with appropriate hydrolysis properties.

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 a polymerizable monomer (a11) represented by the formula (a 11).

R¹－CH＝CH－COO－(SiR²R³O)_n－SiR⁴R⁵R⁶…(a11)

In the formula (a11), R¹～R⁶And n is the same as the same notation in the formula (a 1).

Examples of the polymerizable monomer (a11) include trialkylsilyl acrylate, alkyldiarylsilyl acrylate, and aryldialkylsilyl acrylate. Examples of the trialkylsilyl acrylate include trimethylsilyl acrylate, triethylsilyl acrylate, tripropylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, triisobutylsilyl acrylate, tri-sec-butylsilyl acrylate, tri-2-ethylhexylsilyl acrylate, and butyldiisopropylsilyl acrylate. Further, as the polymerizable monomer (a11), a polymerizable monomer having n of 2 or more in the above formula (a11) such as 1-acryloyloxy nonamethyltetrasiloxane may be mentioned.

From the viewpoint of crack resistance (water resistance) of the antifouling coating film, it is preferable to use the polymerizable monomer (a1) represented by the formula (a1) instead of the polymerizable monomer (a11) represented by the formula (a 11).

Examples of the monomer (a2) include:

(meth) acrylic acid;

(meth) acrylic acid esters (excluding the polymerizable monomers (a1) and (a11)) including, 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, stearyl (meth) acrylate, and the like;

alicyclic-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;

examples of the (meth) acrylate containing a metal ester group include zinc (meth) acrylate, zinc di (meth) acrylate, copper (meth) acrylate, and copper di (meth) acrylate.

Among the monomers (a2), alkyl (meth) acrylates, alicyclic group-containing (meth) acrylates, alkoxyalkyl (meth) acrylates, and glycol-based (meth) acrylates are preferable, and alkyl (meth) acrylates and alkoxyalkyl (meth) acrylates are more preferable.

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) has appropriate hydrolyzability, and tends 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 cracking 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.

< acrylic Polymer (B) >

The hydrolysis-type coating film containing the silicone ester polymer (a) and the medetomidine (C) dissolves in water at a constant rate for a certain period of time from the initial stage of immersion, but the water resistance of the coating film is lowered by hydrolysis of the inside of the coating film, and cracks or peeling may occur. In view of this problem, when the following specific acrylic polymer (B) is blended with the silicone ester polymer (A), the dynamic stain resistance of the coating film can be maintained and the crack resistance can be improved.

The acrylic polymer (B) (hereinafter also referred to as "polymer (B)") has a structural unit (B-1) derived from glycidyl (meth) acrylate. The structural unit (b-1) contributes to improvement of dynamic antifouling property and adhesion to a deteriorated coating film of an antifouling coating film formed from the composition (I).

The structural unit (b-1) may be 1 or 2.

The proportion of the structural unit (B-1) in the acrylic polymer (B) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 15% by mass or less. When the proportion of the structural unit (b-1) is not less than the lower limit, the antifouling coating film is preferably high in dynamic antifouling property and adhesion to a deteriorated coating film, and sufficient dispersibility of the pigment can be obtained when the antifouling paint composition contains the pigment described later. When the proportion of the structural unit (b-1) is not more than the above upper limit, the antifouling property is high, which is preferable. Further, when the proportion of the structural unit (b-1) is in a particularly preferable range, the storage stability of the composition tends to be further excellent.

The acrylic polymer (B) preferably further has a structural unit (B-2) derived from an aromatic vinyl compound.

The structural unit (b-2) has a hydrophobic functional group, i.e., a phenyl group, and contributes to the improvement of the 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 of the coating film. The reason for the improvement of the polishing properties is not clear, but it is presumed that the structural unit (b-2) improves the coating hardness of the formed antifouling coating film and can exhibit physical polishing properties against an external force such as frictional resistance in water.

Examples of the aromatic vinyl compound include styrene compounds such as styrene, methylstyrene, 2, 4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, and monochlorostyrene, and among these, styrene is preferable.

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

The proportion of the structural unit (B-2) in the acrylic polymer (B) is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less. When the proportion of the structural unit (b-2) is not less than the lower limit, the antifouling coating film is preferably high in crack resistance and impact resistance. When the proportion of the structural unit (b-2) is not more than the above upper limit, the antifouling coating film has excellent antifouling properties because the hydrophobicity is not excessively high and hydrolysis of the polymer (a) is not inhibited.

The acrylic polymer (B) further has 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;

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, stearyl (meth) acrylate, and the like;

alicyclic-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;

an epoxy group-containing (meth) acrylate other than 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 tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate;

vinyl monomers (excluding aromatic vinyl compounds) include, specifically, vinyl acetate, isobutyl vinyl ether, vinyl toluene, (meth) acrylonitrile, vinyl propionate, and vinyl benzoate.

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

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

The viscosity and glass transition temperature of the acrylic polymer (B), the hardness of the antifouling coating film, and the like can be adjusted by changing the type or amount of the structural unit (B-3).

The proportion of the structural unit (B-3) in the acrylic polymer (B) is preferably 89% by mass or less, more preferably 82% by mass or less, and still more preferably 75% by mass or less.

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

The weight average molecular weight (Mw) of the acrylic polymer (B) is preferably 2,000 or more, more preferably 5,000 or more, preferably 50,000 or less, more preferably 30,000 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 acrylic polymer (B) may be used in 1 kind or 2 or more kinds.

The content of the acrylic polymer (B) in the composition (I) is preferably 5 parts by mass or more per 100 parts by mass of the silicone ester polymer (a), more preferably 15 parts by mass or more, further preferably 20 parts by mass or more, and preferably 200 parts by mass or less, from the viewpoint of further improving the crack resistance of the antifouling coating film and the adhesion to a deteriorated coating film, and more preferably 130 parts by mass or less, and further preferably 110 parts by mass or less, from the viewpoint of further improving the dynamic antifouling property of the antifouling coating film.

The total content of the silicone ester polymer (a) and the acrylic polymer (B) is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, relative to 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 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less.

In the present specification, the solid content and the content of the composition (I) are a heating residue (nonvolatile content) and a content thereof obtained by the following method or an equivalent method. Composition (I) was measured in a test dish of known mass made of metal and spread evenly on the bottom. Heating the mixture in a hot air drier at 105-110 deg.C for 3 hr to remove volatile components. After taking out and cooling to room temperature (example: 23 ℃), the mass of the obtained nonvolatile components (heating residue) was weighed again, and the content of the solid components (heating residue) was calculated by the following formula.

The content (%) of the solid component (heating residual component) is the mass (g) of the heating residual component (g) × 100/measured amount of the composition (I)

The solid content and the content of each component were obtained in the same manner.

< method for producing Polymer >

The method for producing the polymer (a) and the polymer (B) is not particularly limited, and examples thereof include solution polymerization, suspension polymerization, and pressure polymerization, and solution polymerization using a common 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 polymer (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 temperature at the above temperature in a preferable ratio to the above-mentioned structural unit to perform 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 both 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 polymer (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 polymer (B) include an organic solvent and water. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, mesitylene, and kerosine naphtha; 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, terpinolene, and γ -terpinolene; 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).

< medetomidine (C) >

Medetomidine (C) is a compound represented by the following formula (C1) (+/-) -4- [ 1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole, has optical isomers, and may be a mixture of only one of them or in any ratio.

In the composition (I), an adduct of an imidazole salt, a metal, or the like may be used as a part or all of medetomidine. In this case, as a raw material for preparing the composition (I), an adduct of an imidazolium salt, a metal or the like may be used, or an adduct of an imidazolium salt, a metal or the like may be formed in the composition (I) or the antifouling coating film formed from the composition (I).

Conventional antifouling paint compositions containing no acrylic polymer have insufficient adhesion to a deteriorated coating film such as a rosin-containing zinc acrylate resin antifouling coating film, and are difficult to be directly applied. In response to this problem, the composition (I) can greatly improve the above adhesion to a deteriorated coating film while maintaining dynamic antifouling properties. Further, if a deteriorated coating film is directly coated with an antifouling paint composition for repair, the surface roughness of the formed antifouling coating film tends to be high due to the surface roughness of the deteriorated coating film, and thus aquatic organisms tend to physically attach thereto. Since the composition (I) contains medetomidine (C), an antifouling coating film having excellent antifouling properties can be formed even when the composition is directly applied to the deteriorated coating film as described above. That is, the composition (I) can be said to be suitable for repair coating and repair of a deteriorated coating film. Here, the deteriorated coating film is a coating film (coating film after use) which is actually immersed in seawater or fresh water for a certain period of time (for example, 30 weeks or more, preferably 50 weeks or more).

Examples of the antifouling coating film (deteriorated coating film) to be repaired include a zinc acrylate resin-based antifouling coating film and a silyl resin-based antifouling coating film, and particularly, an antifouling coating film containing rosin is preferable, and a zinc acrylate resin-based antifouling coating film containing rosin is more preferable because the problem of adhesion can be solved more favorably.

The rosin-containing antifouling coating film is an antifouling coating film containing rosin in an amount of usually 0.5 to 40 mass%, and is preferably 1 to 30 mass%, more preferably 1.5 to 15 mass%, from the viewpoint of further achieving the effects of the present invention. The antifouling coating film is formed from an antifouling paint composition containing rosin in an amount of usually 0.5 to 40% by mass, preferably 1 to 30% by mass, and more preferably 1.5 to 15% by mass, based on 100% by mass of the solid content of the composition. Specific examples of the rosin include rosins (E1) described later.

The content of medetomidine (C) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 2% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.15% by mass or less, of the solid content 100% by mass of composition (I). The content of medetomidine (C) in composition (I) is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, further preferably 0.5 part by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, further preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of the total of silicone ester polymer (a) and acrylic polymer (B). When the content of medetomidine (C) is in this range, the stain-resistant coating film formed from composition (I) exhibits more excellent stain resistance. Further, by setting the content of medetomidine (C) within a particularly preferable range, composition (I) exhibits more excellent storage stability.

< cuprous oxide (D) >

The antifouling paint composition containing the silicone ester polymer (a) and medetomidine (C) can improve dynamic antifouling properties against mucus and aquatic organisms of plant species such as algae represented by ulva (sea lettuce) by containing cuprous oxide (D).

The content of the cuprous oxide (D) is more than 0% by mass and 55% by mass or less, preferably 10 to 53% by mass, and more preferably 20 to 52% by mass in the solid content of the antifouling paint composition. When the content of copper (D) oxide is not less than the lower limit, the dynamic antifouling property of the formed antifouling coating film is improved, and when the content is not more than the upper limit, the composition (I) has excellent long-term storage stability and the dynamic antifouling property of the formed antifouling coating film is improved.

The mechanism of action for the above-mentioned effects is not clear, and it is presumed that, for example, in the antifouling paint composition containing the silicone ester polymer (a), the medetomidine (C), and the cuprous oxide (D) in an amount exceeding a specific amount, the silicone ester polymer (a) is significantly increased in molecular weight and the paint composition is increased in viscosity due to the interaction of these components, and it is presumed that the antifouling paint composition (I) of the present invention is suppressed in viscosity and improved in long-term storage stability because the amount of the cuprous oxide (D) is not more than a specific amount. Further, the mechanism of action is not clear, and it is presumed that the interaction between the silicone ester polymer (a) and the polymer (B) and the antifouling paint composition (I) containing a specific amount or less of cuprous oxide (D) increases the consumption rate of the coating film to a suitable extent, and improves the dynamic antifouling property against aquatic organisms of plant species.

The cuprous oxide (D) preferably has an average particle size of about 1 to 30 μm, and more preferably contains 2 to 10 μm in terms of improving the antifouling property and water resistance of the antifouling coating film formed.

As the cuprous oxide (D), cuprous oxide surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, or the like is preferable from the viewpoint of long-term stability during storage of the composition (I).

As such cuprous oxide (D), commercially available products can be used, and examples thereof include NC-301 (average particle diameter: 2 to 4 μm) manufactured by NC TECH Co., Ltd, NC-803 (average particle diameter: 6 to 10 μm), Red Copp97N Premium manufactured by AMERICAN CHEMET Co., Ltd, pure Copp, LoLoLoLoTint 97, and the like

< monocarboxylic acid Compound (E) >)

The composition (I) preferably contains the monocarboxylic acid compound (E) from the viewpoint that the antifouling property is not only improved but also the consumption rate of the coating film can be adjusted.

Examples of the monocarboxylic acid compound (E) 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 (E1), naphthenic acids, cycloalkenyl carboxylic acids, bicycloalkenyl carboxylic acids, trimethylisobutenylcyclohexene carboxylic acids, isononanoic acids, neodecanoic acids, tertiary carboxylic acids (Versatic acid), stearic acid, hydroxystearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, pimaric acid, abietic acid, and neoabietic acid. Among these, rosins (E1) are preferred in that a coating film having excellent crack resistance and long-term antifouling properties can be easily obtained.

Examples of the rosin (E1) include rosins such as gum rosin, wood rosin, and tall oil rosin; hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salts, pine tar.

The monocarboxylic acid compound (E) may be used in 1 or 2 or more species.

The mass ratio of the monocarboxylic acid compound (E) to the total of the silicone ester polymer (a) and the acrylic polymer (B) (total mass of the polymer (a) and the polymer (B)/mass of the monocarboxylic acid compound (E)) in the composition (I) is preferably 0.5 or more, more preferably 0.7 or more, preferably 5 or less, more preferably 4 or less.

In particular, the mass ratio of the rosin (E1) to the total of the silicone ester polymer (a) and the acrylic polymer (B) (total mass of the polymer (a) and the polymer (B)/mass of the rosin (E1)) in the composition (I) is preferably 0.7 to 4, more preferably 0.7 to 3.5, and still more preferably 0.7 to 3. In one embodiment, the mass ratio is more than 1.5 and 3.5 or less. In such an embodiment, the antifouling coating film formed from the composition (I) tends to have more excellent adhesion to a deteriorated coating film such as an antifouling coating film containing rosin, dynamic antifouling property, and crack resistance.

That is, when the mass ratio is 4 or less, the adhesion to the deteriorated coating film and the dynamic stain resistance tend to be more excellent than when it exceeds 4, and when the mass ratio is 0.7 or more, the adhesion to the deteriorated coating film and the crack resistance tend to be more excellent than when it is less than 0.7. Therefore, the composition (I) satisfying the conditions of the mass ratio can be directly applied to the deteriorated coating film without using a binder or the like, and is particularly suitable for repair coating or repair application of the deteriorated coating film.

< other ingredients >

The composition (I) may further contain, as other components of the above components, at least 1 kind of component selected from the group consisting of copper and/or copper compounds, organic antifouling agents other than medetomidine (C), coloring agents, extender pigments, thixotropic agents, dehydrating agents, plasticizers, resins other than the polymers (a) and (B), and solvents.

The components described below may be used in 1 type or 2 or more types, respectively.

Copper and/or copper compounds

The composition (I) preferably contains copper and/or a copper compound as an antifouling agent from the viewpoint of further improving the antifouling property against aquatic organisms of animal species. Copper is, for example, copper powder. Examples of the copper compound include copper thiocyanate and a copper-nickel alloy, and copper thiocyanate is preferable. Copper (D) oxide is not classified into the copper compound, and copper pyrithione is not a copper compound but is classified into the following organic antifouling agents.

The content of copper and/or a copper compound is preferably 0.1 to 45% by mass, more preferably 1 to 35% by mass, based on 100% by mass of the total solid content of the composition (I).

Organic antifouling agent

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

Examples of the organic antifouling agent include metals pyrithione 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-isopropyl pyridine 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, 2,4,5, 6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamyl zinc ethylene dithiocarbamate, chloromethyl-N-octyl disulfide, N' -dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfonamide, and the like, N ', N' -dimethyl-N-tolyl- (N-fluorodichloromethylthio) sulfonamide, thiuram tetraalkyldisulfide, 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, metal pyrithione 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, and bisdimethyldithiocarbamylzinc ethylene dithiocarbamate are preferable, and copper pyrithione and 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one are more preferable.

The content of the organic antifouling agent other than medetomidine (C) is preferably 0.05 to 20 mass%, more preferably 0.1 to 10 mass%, relative to 100 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. The composition (I) contains a colorant, and is preferably used in that the hue of an antifouling coating film obtained from the composition can be arbitrarily adjusted.

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, more preferably talc, from the viewpoint 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).

The content of talc is preferably 2 to 17% by mass based on 100% by mass of the total solid content of the composition (I) from the viewpoint of further improving the coating film properties such as crack resistance.

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 salts selected from organobentonite, amine salts of Al, Ca or Zn, stearate salts, lecithin salts, and alkylsulfonate salts; a wax selected from the group consisting of polyethylene wax, oxidized polyethylene wax, amide wax, hydrogenated castor oil wax, and polyamide wax; synthesizing the micro-powder silicon dioxide.

The thixotropic agent is used for improving the precipitation prevention of solid materials such as copper and/or copper compounds, organic antifouling agents, colorants, extender pigments, dehydrating agents, etc. during storage of the antifouling paint composition and the coating workability during coating.

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).

A dehydrating 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 or the like due to decomposition of the hydrolyzable resin, which is caused by water generated during 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).

(plasticizers)

Examples of the plasticizer include normal paraffin, chlorinated paraffin, petroleum resin, ketone resin, tricresyl phosphate, polyvinyl ethyl ether, and dialkyl phthalate, and among these, chlorinated paraffin, petroleum resin, and ketone resin are preferable. The composition (I) preferably contains a plasticizer, and is more preferably used in view of further improving the crack resistance and water resistance of the antifouling coating film obtained from the composition.

The chlorinated paraffin may have any molecular structure of straight chain and branched chain, 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. Further, the average carbon number of 8 or more is preferable because the effect of suppressing the occurrence of cracks is high, while the average carbon number of 30 or less does not suppress the antifouling property.

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-series, C9-series, styrene-series, dicyclopentadiene-series 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 Polymer (B)

The composition (I) may contain resins other than the above-mentioned polymer (A) and polymer (B). Examples of the resins include water-insoluble or water-sparingly-soluble 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.), styrene-butadiene copolymer resins, alkyd resins, coumarone resins, terpene phenol resins, silicone rubbers, and chlorinated rubbers.

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

Solvents

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 polymer (B), or a solvent separately added in the preparation of the antifouling paint composition by mixing the polymer (A) and the polymer (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 in accordance with a desired viscosity corresponding 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, using the polymer (a), the polymer (B), the medetomidine (C), and a specific amount of cuprous oxide (D). For example, the polymer (a), the polymer (B), the medetomidine (C), and a specific amount of cuprous oxide (D), and if necessary, the monocarboxylic acid compound (E) and/or the other components described above may be added to a stirring vessel at once or in any order, and the respective components may be mixed by a known stirring and mixing method, and dispersed or dissolved in a solvent to produce the medetomidine.

Examples of the stirring and mixing method include a method using a paint shaker, a high-speed disperser, a sand mill, a basket mill, a ball mill, a three-roll mill, a Ross mixer (Ross mixer), a planetary mixer, and a pinkish universal mixer.

[ 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 14 days, more preferably about 1 to 7 days, and still more preferably about 1 to 5 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 antifouling substrate (K) can be produced by forming the antifouling coating film (J) from the composition (I) on the surface of a temporary substrate, peeling the antifouling coating film (J) from the temporary substrate, and attaching the coating film to the substrate to be antifouling. In this case, the antifouling coating film (J) may be attached to the base material through the adhesive layer.

The surface of the substrate may be subjected to an undercoating treatment, or the substrate may have on the surface thereof 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. The substrate may be an antifouling substrate having an antifouling coating film, and for example, may be an antifouling substrate having a deteriorated coating film such as a rosin-containing zinc acrylate resin-based antifouling coating film. The surface of the substrate provided with the antifouling coating film (J) in this case means a surface after plasma treatment, a surface of a layer formed of the above-mentioned coating material, and a surface of the antifouling coating film.

The base material is not particularly limited, and the composition (I) is preferably used for long-term antifouling and the like of the base material in a wide industrial field such as ships, fisheries, underwater structures and the like. Therefore, examples of the base 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, including new ships and repair ships), underwater structures (e.g., oil pipelines, water pipelines, circulating pipes, plant and fire power, water supply and drainage ports of nuclear power plants, submarine cables, machines using seawater (e.g., sea water pumps), ultra-large floating marine structures, bay coastal roads, submarine tunnels, harbor facilities, and various underwater civil engineering and construction equipment in canals and waterways), fishing materials (e.g., ropes, fishing nets, fishing gears, floats, buoys), water supply and drainage pipes of seawater in plants and fire power plants, nuclear power plants, and the like, diving suits, underwater glasses, oxygen bottles, swimming suits, fishes, and the like. Among these, ships, underwater structures, fishery materials, and water supply and drainage pipes are preferable, 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, or when the substrate is a fishing net, the composition (I) may be impregnated into the surface of the substrate, or when the substrate is a steel plate, a primer material such as a rust inhibitor or a primer may be applied in advance to the surface of the substrate to form a primer layer, and then the composition (I) may be applied to the surface of the primer layer. Further, the antifouling coating film (J) can be formed on the surface of the substrate on which the antifouling coating film (J) or the conventional antifouling coating film (e.g., a deteriorated coating film comprising a rosin-based zinc acrylate-based antifouling coating film) is formed for the purpose of repairing, as in a steel sheet having a deteriorated antifouling coating film (e.g., a deteriorated coating film comprising a rosin-based zinc acrylate-based antifouling coating film).

The thickness of the antifouling coating film (J) is not particularly limited, and is, for example, about 30 to 1000 μm. In addition, when the composition (I) is applied to a substrate to form an antifouling coating film (J), a method of applying the antifouling coating film (J) in 1-pass coating, preferably 10 to 300 μm, more preferably 30 to 200 μm, in 1-pass to a plurality of passes (when the composition (I) contains a solvent, the thickness of the coating film after removal of the solvent).

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, and can maintain 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 blockage of the water supply and drainage pipe and the reduction of the flow rate.

Examples

The present invention will be further specifically described below based on examples and comparative examples, but the present invention is not limited to the following examples at all. 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 residual component was measured by heating the polymer 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)

Temperature of chromatographic column thermostatic bath: 40 deg.C

Standard curve: standard polystyrene and styrene monomer

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

< measurement Condition for content of solid component (heating residual component) >

A polymer solution was measured in a metal test dish of a known mass, spread evenly on the bottom, and heated in a hot air dryer at a temperature of 105 to 110 ℃ for 3 hours to remove volatile components. After taking out and cooling to room temperature (example: 23 ℃), the mass of the obtained nonvolatile components (heating residue) was weighed, and the solid content was calculated by the following formula.

The content (%) of the solid component (heating residual component) is the mass (g) of the heating residual component (g) × 100/amount of the polymer solution measured

[ production example of Polymer]

Production example 1]Production of a solution of the 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 ℃. While maintaining this temperature, a mixture of monomers (50 parts of triisopropylsilyl methacrylate, 25 parts of 2-methoxyethyl methacrylate, 10 parts of methyl methacrylate, and 5 parts of n-butyl acrylate) and a polymerization initiator (1.35 parts of 2,2' -azobis (isobutyronitrile)) was added dropwise from the dropping device into the reaction vessel over 2 hours. 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 ℃. After maintaining the temperature and adding 0.1 part of 2,2' -azobis (isobutyronitrile) dropwise in total 4 times every 30 minutes, the liquid temperature was increased to 105 ℃. After stirring at this temperature for 30 minutes, 23.7 parts of xylene was added to the reaction vessel to obtain a solution of the silicone ester polymer (A-1).

A solution of the silicone ester polymer (A-2) and a solution of the comparative silicone ester polymer (cA-1) were obtained in the same manner as described above, except that the monomers were changed as described in Table 1.

Production example 2]Production of solution of acrylic Polymer (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 ℃. Under these conditions, a mixture of monomers (50 parts of styrene, 15 parts of methyl methacrylate, 25 parts of n-butyl acrylate, 10 parts of glycidyl methacrylate) and a polymerization initiator (1.5 parts of 2,2' -azobis (isobutyronitrile), 1 part of t-butyl peroxybenzoate) was added dropwise from the dropping device into the reaction vessel over 3 hours, while maintaining the same temperature, and the mixture was heated and stirred at 120 ℃ for 1 hour, and after heating and stirring at 130 ℃ for 1 hour, 7.16 parts of xylene was added to the reaction vessel, thereby obtaining a solution of the acrylic polymer (B-1).

Solutions of acrylic polymers (B-2) to (B-4) and solutions of comparative acrylic polymers (cB-1) to (cB-2) were obtained in the same manner as described above except that the monomers were changed as shown in Table 2.

The weight average molecular weights of these silicone ester polymer and acrylic polymer, and the solid content (residual heat) contents of these solutions are shown in tables 1 and 2. The numerical values of the monomers indicate the amounts (parts by mass) to be blended

[ Table 1]

[ Table 2]

[ preparation of antifouling paint composition]

[ example 1]

An antifouling paint composition was prepared by the following procedure.

To a polyethylene container, 0.1 part of medetomidine (Selektope (registered trademark)) and 0.9 part of methoxypropanol (PGM) were added, and mixed using a paint shaker until the medetomidine was uniformly dissolved. To the resulting solution were added 14.0 parts of xylene and 6.5 parts of gum rosin (chinese gum rosin WW), and mixed again using a paint shaker until the rosin was uniformly dissolved. Thereafter, 12.0 parts of a solution of the silicone-based polymer (A-1) and 5.0 parts of a solution of the acrylic polymer (B-1) were added to the obtained solution, and the mixture was stirred until uniform mixing, followed by further addition of 10 parts of zinc oxide (Zinc oxide No. 3), 37 parts of cuprous oxide (NC-301), 2.0 parts of titanium oxide (TIPAQUE R-930), 1.5 parts of iron oxide Red (TODA COLOR NM-50), 6.0 parts of talc (FC-1), 1.0 part of Copper pyrithione (Copper oxide Powder), 2.0 parts of polyethylene oxide wax (DISLON 4200-20X) and 0.5 part of tetraethoxysilane (Ethyl silicate 28), further addition of 200 parts of glass beads, and stirring with a paint shaker for 1 hour to disperse the mixture. To the obtained dispersion, 1.5 parts of amide wax (DISPARLON A630-20X) was added, and after stirring for 20 minutes using a paint shaker, glass beads were removed from the mixture with an 80-mesh filter screen to obtain an antifouling paint composition.

Examples 2 to 19 and 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.

[ 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 obtained results are shown in table 3.

< crack resistance >

An epoxy anticorrosive paint (trade name "Bannoh 500", manufactured by China coatings Co., Ltd., hereinafter referred to as "epoxy 1") was applied to a sandblasted steel sheet having a length of 300mm, a width of 100mm and a thickness of 2.3mm by air spraying so as to have a dry film thickness of 150 μm, and dried at 23 ℃ for 1 week to form a cured coating film. Then, an epoxy-based pressure-sensitive adhesive coating (trade name "Bannoh 500N", manufactured by China coatings Co., Ltd., hereinafter referred to as "epoxy 2") was applied by air spray to the cured coating film of epoxy 1 so that the dry film thickness became 100 μm, and the film was dried at 23 ℃ for 24 hours.

Then, each of the compositions prepared in examples and comparative examples was applied to the surface of the cured coating film of epoxy-2 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 crack resistance test plate.

The crack resistance test plate thus produced was immersed in natural seawater heated to 50 ℃ for 6 months to confirm the presence or absence of cracks (area basis).

Evaluation criteria (evaluation based on the ratio of the area of cracks to the total area of the coating film surface).

Above 4 is qualified. )

5: no cracks were confirmed.

4: cracks were confirmed in the portion below 2%.

3: cracks were observed in the portion of 2% or more and less than 30%.

2: cracks were observed in the portion of 30% or more and less than 80%.

1: cracks were observed in 80% or more of the portions.

< adhesion to deteriorated coating film >

The sandblasted steel sheet having a length of 300mm, a width of 100mm and a thickness of 3.2mm was coated with epoxy 1 having a dry film thickness of 150 μm and epoxy 2 having a dry film thickness of 100 μm in the same procedure as in the cracking resistance test. A zinc acrylate-based antifouling paint 1 containing rosin (the rosin content was 6% by mass based on 100% by mass of the solid content of the antifouling paint) was applied to the surface of a cured coating film made of epoxy 2 in a dry film thickness of 200 μm, and dried at 23 ℃ for 7 days. The panels were immersed in seawater for 1 year with a test raft. The plate was lifted up at 80kgf/cm²The water washing is carried out under the pressure of (1). After drying, the antifouling paint composition prepared in examples or comparative examples was applied to the surface of the deteriorated coating film 1 formed from the zinc acrylate-based antifouling paint 1 in a dry film thickness of 200 μm, and dried at 23 ℃ for 7 days to form an antifouling coating film, thereby producing an adhesion test panel 1 to the deteriorated coating film 1. The plate was immersed in natural seawater at 23 ℃ for 10 months, and then dried at 23 ℃ for 1 day. Then, basically, a 25-piece checkerboard peel test (cross cut method) of 4 mm. times.4 mm was carried out in accordance with JIS K5600-5-6 (1999), and the adhesion was evaluated in terms of the area of the remaining coating film to the area to be tested.

Evaluation criteria (pass 4 or more)

5: the stripping area is less than 5 percent

4: the peeling area is more than 5% and less than 10%

3: the peeling area is more than 10% and less than 40%

2: the peeling area is more than 40% and less than 70%

1: the peeling area is more than 70% and less than 100%

As the deteriorated coating film, a test panel was produced in the same manner as in the zinc acrylate-based antifouling paint 1, using a zinc acrylate-based antifouling paint 2 containing no rosin, a silyl-based antifouling paint 3 containing rosin (the rosin content was 7% by mass relative to 100% by mass of the solid content of the antifouling paint 3), and a silyl-based antifouling paint 4 containing rosin (the rosin content was 2% by mass relative to 100% by mass of the solid content of the antifouling paint 4), instead of the zinc acrylate-based antifouling paint 1. After these test rafts for test panels were immersed in seawater for 1 year, they were washed with water in the same manner as described above, and the antifouling paint compositions prepared in examples and comparative examples were applied to the surfaces of the deteriorated coating film 2 formed of the zinc acrylate-based antifouling paint 2, the deteriorated coating film 3 formed of the silyl group-based antifouling paint 3, and the deteriorated coating film 4 formed of the silyl group-based antifouling paint 4 to a dry film thickness of 200 μm, and dried at 23 ℃ for 7 days to form antifouling coating films, thereby producing test panels 2 to 4 having adhesion to the deteriorated coating films 2 to 4. Then, these plates were immersed in artificial seawater at 40 ℃ for 6 months, and the adhesion was evaluated in the same manner as described above.

< dynamic antifouling Property >

A dynamic antifouling test panel was produced in the same manner as the crack resistance test panel using a sandblasted steel sheet having a length of 150mm, a width of 70mm and a thickness of 1.6 mm. The test plate thus obtained was immersed in sea water in the sea area of wu city, guangdao, japan, and a water flow was generated using a rotating rotor so as to be about 15 knots per hour, the water flow was allowed to wash the antifouling coating surface of the test plate for 12 months, and the ratio of the area to which aquatic organisms were attached to the antifouling coating surface of the test plate was evaluated by visual observation.

Evaluation criteria (pass 4 or more)

5: no deposit was confirmed.

4: adhesion of mucus was confirmed in the portion below 10%.

3: mucus attachment was confirmed in the portion of 10% or more and less than 60%.

2: mucus attachment was confirmed in the portion of 60% or more and less than 90%.

1: mucus attachment was confirmed in 90% or more of the portions.

[ Table 3]

[ Table 3 shows the results ]

[ evaluation of storage stability of antifouling paint composition]

The storage stability of the antifouling paint compositions obtained in examples and comparative examples was evaluated as follows. The obtained results are shown in table 4.

< storage stability >

A part of each of the antifouling paint compositions of examples and comparative examples prepared by the above-mentioned method was measured for initial viscosity 1 day after the preparation and then stored at 50 ℃ for 2 months. The viscosity of each composition after storage was measured, and the rate of increase in viscosity was calculated from the following formula. If the viscosity increase rate is less than 20%, the product is qualified.

Further, an antifouling paint composition having a viscosity increase rate of 20% or more has problems that the workability of painting is remarkably reduced, the amount of an organic solvent used for dilution is increased, and the environmental load is increased.

Viscosity increase rate (viscosity after storage-initial viscosity)/initial viscosity × 100

[ Table 4]

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

[ Table 5]