JP6887783B2 - Antifouling paint compositions, antifouling coatings and their uses - Google Patents

Description

The present invention relates to an antifouling paint composition, and more specifically, is used for preventing contamination due to adhesion of aquatic organisms to the surface of fishing gear (eg, rope, fishing net, float, buoy), ship, underwater structure, etc. Antifouling paint composition, etc.

Conventionally, aquatic organisms have been used in underwater structures such as water supply and drainage ports of nuclear power plants, sludge diffusion prevention membranes for various marine civil engineering works, ships, fishing gear (eg ropes, fishing nets, floats, buoys), etc. When the material adheres and grows, for example, the surface roughness of the base material increases, which leads to a decrease in the speed of the ship and an increase in fuel consumption, and the anticorrosion coating film applied to the surface of the base material is damaged, resulting in an underwater structure. There is a risk of damage such as deterioration of the strength and function of the object and significant shortening of the life. Furthermore, if aquatic organisms adhere to and propagate in the water supply and drainage pipes of seawater such as thermal power plants and nuclear power plants, the circulation of cooling water supply and drainage may be hindered.

In addition, since fishing nets such as aquaculture nets and fixed nets are installed in the sea for a long period of time, various aquatic organisms such as coelenterates such as hydrozoa, seaweeds such as green laver and green laver, bivalves, fujitsubo, and white squirrel , Serpra, coelenterates, mollusks, etc. adhere in large quantities. Fishing nets need to be replaced frequently because they become heavier due to the attachment of aquatic organisms, making them less manageable and more vulnerable to damage. Furthermore, the attachment of aquatic organisms may cause clogging of fishing nets, obstructing the flow of seawater, and causing damage such as death of farmed fish.

Furthermore, if aquatic organisms adhere to and propagate in the water supply and drainage pipes of seawater such as thermal power plants and nuclear power plants, the circulation of cooling water supply and drainage may be hindered.
In response to such problems, it is common practice to apply an antifouling paint (antifouling paint composition) containing an antifouling agent to a base material to prevent the adhesion of aquatic organisms.

For example, Patent Document 1 discloses an antifouling coating composition containing a hydrolyzable copolymer and medetomidine as an antifouling agent, and further, an antifouling coating formed from the antifouling coating composition. It is described that the membrane has excellent long-term antifouling properties.

Further, Patent Document 2 discloses an antifouling coating composition containing a polysiloxane block-containing metal salt copolymer, silicone oil, and an antifouling agent, and is further formed from this antifouling coating composition. The antifouling coating material has excellent long-term antifouling properties, specifically, it is excellent in a test in which an antifouling coating composition is applied onto a plate and the test plate obtained by drying is immersed in the sea. It is described that long-term antifouling property was exhibited.

International Publication No. 2011/118526 Japanese Unexamined Patent Publication No. 2006-77095

However, although the antifouling coating composition disclosed in Patent Document 1 or 2 exhibits excellent long-term antifouling property as described above, when impregnated and applied to a fishing net, the long-term antifouling property is further improved. It turned out that there was room. Furthermore, it was found that there is room for improvement in terms of storage stability.

In view of these problems, the present invention is an antifouling coating composition used for preventing contamination of a base material by aquatic organisms, which is excellent in storage stability and is a basis for ships and underwater structures. An antifouling paint composition capable of exhibiting excellent antifouling properties for a long period of time even when impregnated and applied not only to a material but also to a fishing net, and an antifouling coating composition formed from the antifouling coating composition. An object of the present invention is to provide a coating film or the like.

As a result of repeated studies, the present inventors have found that antifouling paints containing polyether-modified silicone oil, medetomidin, and coating resin have excellent storage stability, and fishing gear (eg, ropes, floats, buoys), ships, etc. The present invention has been completed by finding that a coating film having excellent long-term antifouling property can be formed not only on a base material such as an underwater structure but also on a fishing net by impregnation and coating. The gist of the present invention is as follows.

[1]
An antifouling coating composition containing a polyether-modified silicone oil (A), an antifouling agent (B), and a coating film-forming resin (C).
The polyether-modified silicone oil (A) has a general formula [I]:

〔式［Ｉ］中、Ｒ¹はそれぞれ独立に炭素数１〜３のアルキル基を示し、
Ｘ¹、Ｘ²およびＸ³はそれぞれ独立に炭素数１〜５のアルキル基、フェニル基またはポリエーテル基を示し、
Ｘ⁴は炭素数１〜１８のアルキル基またはフェニル基を示し、
ｍは１以上の整数を示し、
ｎは０以上の整数を示し、
ｐは０以上の整数を示し、
前記ポリエーテル基は下式［Ｉａ］：
−Ｒ²−Ａ−（Ｒ³Ｏ）_q（Ｒ⁴Ｏ）_r−Ｒ⁵ ・・・［Ｉａ］
（式［Ｉａ］中、Ａは単結合または酸素原子を示し、
Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に炭素数１〜５の２価の炭化水素基を示し、
Ｒ⁵は炭素数１〜５のアルキル基または水素原子を示し、
ｑは１〜３０の整数を示し、
ｒは０〜３０の整数を示し、
左端の線はケイ素原子への結合を示す。）
で表される。〕で表され、１分子中に少なくとも１つの前記ポリエーテル基を有し、
前記防汚剤（Ｂ）としてメデトミジン（Ｂ１）を含有する
防汚塗料組成物。

[In the formula [I], R ¹ independently represents an alkyl group having 1 to 3 carbon atoms.
X ¹ , X ² and X ³ independently represent an alkyl group, a phenyl group or a polyether group having 1 to 5 carbon atoms, respectively.
X ⁴ represents an alkyl or phenyl group having 1 to 18 carbon atoms.
m indicates an integer of 1 or more,
n indicates an integer greater than or equal to 0,
p indicates an integer greater than or equal to 0,
The polyether group has the following formula [Ia]:
−R ² −A− (R ³ O) _q (R ⁴ O) _r −R ⁵・ ・ ・ [Ia]
(In formula [Ia], A represents a single bond or an oxygen atom,
R ² , R ³ and R ⁴ each independently represent a divalent hydrocarbon group having 1 to 5 carbon atoms.
R ⁵ represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms.
q indicates an integer from 1 to 30
r represents an integer from 0 to 30
The leftmost line shows the bond to the silicon atom. )
It is represented by. ], Which has at least one of the above-mentioned polyether groups in one molecule.
An antifouling coating composition containing medetomidine (B1) as the antifouling agent (B).

[2]
The antifouling coating composition according to the above [1], wherein the content of the medetomidine (B1) is 0.01 to 1,000 parts by mass with respect to 100 parts by mass of the polyether-modified silicone oil (A).

[3]
The coating film-forming resin (C) is a (meth) acrylic acid metal salt copolymer, a polyester metal salt copolymer, a silyl ester-containing copolymer, a polysiloxane block-containing metal salt copolymer, and a sulfur-containing organopolysiloxane. Block vinyl copolymer, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, rubber chloride resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy The antifouling coating composition according to the above [1] or [2], which is one or more selected from the group consisting of resins, phenolic resins, synthetic rubbers, petroleum resins, rosin ester resins, rosin soaps, and rosins. ..

[4]
The antifouling coating composition according to any one of the above [1] to [3], which further contains an antifouling agent (B2) other than medetomidine as the antifouling agent (B).

[5]
Antifouling agents (B2) other than medetomidin include cuprous oxide, rodane copper, copper powder, bisdimethyldithiocarbamoyl disulfide bisdithiocarbamate, disulfide dithiocarbamate, disulfide bisdithiocarbamate, N, N-dimethyl-N. '-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, Tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, copper pyrithione, zincpyrythione, 2,3-dichloro-N- (2', 6'-diethylphenyl) maleimide, 2 , 3-Dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, Triphenylboran amine complex, diphenylmethylboran 4-isopropylviridine, chloromethyl-n-octyl disulfide, N', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, and N', N The antifouling coating composition according to the above [4], which is one or more selected from the group consisting of'-dimethyl-N-tolyl- (N-fluorodichloromethylthio) sulfamide.

[6]
The antifouling coating composition according to the above [4] or [5], which contains the antifouling agent (B2) in a proportion of 600 parts by mass or less with respect to 1 part by mass of the medetomidine (B1).

[7]
The antifouling coating composition according to any one of the above [1] to [6], further containing at least one plastic resin (D) selected from the group consisting of polyolefins, polysulfides, paraffins, and petrolatums. Stuff.

[8]
The antifouling coating composition according to any one of the above [1] to [7], wherein the HLB of the polyether-modified silicone oil (A) is 0.5 to 10.

[9]
Further, any one of the above [1] to [8] containing one or more metal oxides (E) selected from the group consisting of CuO, ZnO, TiO ₂ , Al ₂ O ₃ , SiO _{2, and MgO.} The antifouling paint composition according to the description.

[10]
The antifouling paint composition according to any one of the above [1] to [9], which is used for painting fishing gear.

[11]
An antifouling coating film formed from the antifouling coating composition according to any one of [1] to [10].

[12]
A base material with an antifouling coating film having a base material and the antifouling coating film according to the above [11] provided on the surface of the base material.

[13]
The base material with an antifouling coating film according to the above [12], wherein the base material is a fishing gear, a ship, or an underwater structure.

[14]
A fishing net dyed with the antifouling paint composition according to any one of [1] to [10].

[15]
An antifouling method for a base material, wherein the base material is coated with or impregnated with the antifouling coating composition according to any one of [1] to [10] and then cured.

[16]
The step of applying or impregnating the surface of the base material with the antifouling coating composition according to any one of [1] to [10], and the step of applying or impregnating the base material by the step. A method for producing a base material with an antifouling coating film, which comprises a step of curing the antifouling coating composition.

The antifouling coating composition of the present invention is excellent in film forming property. Further, since the antifouling coating composition of the present invention is excellent in storage stability, it can be stored for a long period of time. Further, the antifouling coating composition of the present invention provides long-term antifouling property even when impregnated / applied to fishing nets as well as base materials such as fishing gear (eg, ropes, buoys, buoys), ships, and underwater structures. Can be demonstrated. Further, when the antifouling coating composition of the present invention is used for a fishing net, for example, it exerts an antifouling effect on a wide range of organisms such as coelenterates, algae, bivalves and mollusks, and particularly barnacles. Demonstrates a long-term antifouling effect on species and coelenterates.

Hereinafter, the antifouling coating composition, the antifouling coating film, and their uses according to the present invention will be specifically described.
In addition, "(meth) acrylic ((meth) acryl)" is a general term for acrylic (acryl) and methacryl (methacryl).

[Anti-fouling paint composition]
The antifouling coating composition of the present invention contains a polyether-modified silicone oil (A), an antifouling agent (B), and a coating film-forming resin (C), and further contains an arbitrary component depending on the purpose. You may.

(A) Polyether-modified silicone oil:
The polyether-modified silicone oil (A) is a compound represented by the following general formula [I].

式［Ｉ］において、複数個あるＲ¹はそれぞれ独立に炭素数１〜３のアルキル基を示す。炭素数１〜３のアルキル基としては、メチル基、エチル基およびプロピル基が挙げられる。

In the formula [I], an alkyl group having 1 to 3 carbon atoms in each plurality is R ¹ is independently. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group and a propyl group.

X ¹ , X ² and X ³ independently represent an alkyl group, a phenyl group or a polyether group having 1 to 5 carbon atoms, respectively. If X ¹ is present a plurality (i.e., if p is an integer of 2 or more), they may being the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.
X ⁴ represents an alkyl group or a phenyl group having 1 to 18 carbon atoms, if X ⁴ is present a plurality (i.e., when n is an integer of 2 or more), be different even they are identical to each other Good. Examples of the alkyl group having 1 to 18 carbon atoms include those exemplified as an alkyl group having 1 to 5 carbon atoms, a hexyl group, an octyl group, a 2-ethylhexyl group, a lauryl group and a stearyl group.

m indicates an integer of 1 or more, n indicates an integer of 0 or more, and p indicates an integer of 0 or more. Further, in the formula [I],

で示される３種類の繰返し単位が並ぶ順序は、特に限定されず、ランダム、交互または連続のいずれでであってもよい。

The order in which the three types of repeating units indicated by are arranged is not particularly limited, and may be random, alternating, or continuous.

The polyether group is of the formula [Ia] :.
−R ² −A− (R ³ O) _q − (R ⁴ O) _r −R ⁵・ ・ ・ [Ia]
It is represented by.

In formula [Ia], A represents a single bond or an oxygen atom. The leftmost line shows the bond to the adjacent silicon atom.
R ² , R ³ and R ⁴ independently represent a divalent hydrocarbon group having 1 to 5 carbon atoms, preferably a divalent saturated hydrocarbon group, and more preferably an alkylene group having 2 to 5 carbon atoms. The alkylene group may be linear or branched, preferably linear. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a propylene group and a tetramethylene group, and an ethylene group and a trimethylene group are preferable.

R ² is preferably an ethylene group or a trimethylene group, R ³ is preferably an ethylene group, and R ⁴ is preferably a trimethylene group.
R ⁵ represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms, and is preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.

q indicates an integer of 1 to 30 (number of repeating units), and r indicates an integer of 0 to 30 (number of repeating units).
Antifouling properties, or by considering the compatibility with the polyether-modified silicone oil (A) and later to film-forming resin (C), examples of the polyether group, preferably, -C ₃ H ₆ -O- (C ₂ H ₄ O) _q -C ₂ H ₅ , -C ₂ H ₄ -O- (C ₃ H ₆ O) _q -CH ₃ , -C ₃ H ₆ -O- (C ₂ H ₄ O) _{q -CH 3, -C 2 H 4 -O-} (C 3 H 6 O) q -CH 3, -C 3 H 6 - (C 2 H 4 O) q -CH 3, -C 2 H 4 - (C _{3 H 6 O) q -CH 3} , -C 3 H 6 - (C 2 H 4 O) q -H, -C 2 H 4 - (C 3 H 6 O) q -H, -C 3 H 6 - O- (C ₃ H ₆ O) _q -CH ₃ , -CH ₂ -O- (C ₂ H ₄ O) _q -CH ₃ , -CH ₂ -O- (C ₂ H ₄ O) _q -H,- C ₂ H ₄ -O- (C ₂ H ₄ O) _q -CH ₃ , -C ₂ H ₄ -O- (C ₂ H ₄ O) _q -H, -CH ₂ -O- (C ₃ H ₆ O) ) _Q -CH ₃ , -CH ₂ -O- (C ₃ H ₆ O) _q -H, -CH ₂ -O- (C ₄ H ₈ O) _q -CH ₃ , -CH ₂ -O- (C ₄₎ H ₈ O) _q -H, -C ₃ H ₆ -O- (C ₃ H ₆ O) _q -H, -C ₄ H ₈ -O- (C ₄ H ₈ O) _q -H, -C ₃ H ₆ -O- (C ₂ H ₄ O) _q- (C ₃ H ₆ O) _r -CH ₃ , -C ₃ H ₆ -O- (C ₂ H ₄ O) _q- (C ₃ H ₆ O) _r -H, -C ₃ H ₆ -O- (C ₃ H ₆ O) _q- (C ₂ H ₄ O) _r -CH ₃ , and -C ₃ H ₆ -O- (C ₃ H ₆ O) _q- (C ₂ H ₄ O) _r -H can be mentioned. In these chemical formulas, C ₂ H ₄ is (CH ₂ ) ₂ (ethylene group) and C ₃ H ₆ is (CH ₂ ) ₃ (trimethylene group) or CH (CH ₃ ) CH ₂ (propylene group). , Preferably (CH ₂ ) ₃ .

As the polyether group,-(CH ₂ ) ₃ -O- (C ₂ H ₄ O) _q -CH ₃ and -C ₂ H ₄ -O-((CH ₂ ) ₃ O) _{q -CH 3} are particularly suitable. preferable.
The polyether-modified silicone oil (A) has at least one of the polyether groups in one molecule.

The polyether-modified silicone oil (A) includes
(A): In the formula [I], X ¹ is a polyether group represented by the formula [Ia], X ² and X ³ are an alkyl group such as a methyl group or a phenyl group, and p is 1. Side-chain type polyether-modified silicone oil, which is an integer above
(B): In the formula [I], X ¹ is an alkyl group such as a methyl group or a phenyl group, and X ² and X ³ are a polyether group represented by the formula [Ia]. Ether-modified silicone oil,
(C): In the formula [I], one of X ^1, X ² and X ³ is a polyether group represented by the formula [Ia], and one of X ² and X ³ is an alkyl such as a methyl group. Polyether-modified silicone oil, which is a group or a phenyl group and p is an integer of 1 or more.
(D): In the formula [I], ^{a polyether-modified silicone oil in which X 1} , X ² and X ³ are the polyether groups represented by the formula [Ia] and p is an integer of 1 or more.
(E): In the formula [I], one of X ² and X ³ is a polyether group represented by the formula [Ia], ^{and one} of X 1 and X ² and X ³ is an alkyl such as a methyl group. Examples thereof include polyether-modified silicone oil having a group or a phenyl group. Among these, the side chain type polyether-modified silicone oil (a) and the double-ended type polyether-modified silicone oil (b) are preferable from the viewpoint of antifouling property and the like.

The number average molecular weight of the polyether-modified silicone oil (A) is usually about 1,000 to 50,000, preferably about 3,000 to 10,000.
The polyether-modified silicone oil (A) can be used alone or in combination of two or more.

The hydrophilic lipophilic balance (HLB) of the polyether-modified silicone oil (A) is
It is indicated by the value (amount of ethylene oxide / 5) obtained by dividing the amount (mass%) of ethylene oxide contained in the polyether group by 5, preferably 0.5 to 10 and particularly preferably 1 to 7. When the HLB is in the range of 0.5 to 10, the elution amount of the antifouling agent is appropriately maintained, so that the antifouling property tends to be good.

Such a polyether-modified silicone oil (A) can be produced by a conventionally known method, and if it is a commercially available product, it is "KF-6016 (HLB = 4.5)" or "KF-945 (HLB = 4)". .0) ”,“ X-22-6515 (HLB = 5.7) ”,“ X-22-6191 (HLB = 2.0) (all manufactured by Shin-Etsu Chemical Co., Ltd.), “TSF4446” (Toshiba) Silicone Co., Ltd., HLB = 4.8), "ST-114PA (HLB = 5.6)", "FZ-2120 (HLB = 6.0)" (all manufactured by Toray Dow Corning Co., Ltd., etc. Can be mentioned.

The content of the polyether-modified silicone oil (A) in the antifouling coating composition of the present invention is preferably 0.5 to 40% by mass, more preferably 0.5% by mass, assuming that the solid content of the antifouling coating composition is 100% by mass. It is 2 to 35% by mass. In the present invention, the "solid content" is the amount when the solvent, which is an optional component, is removed from the antifouling coating composition or each component. For example, the amount of the residue when the antifouling coating composition or each component is left at 105 ° C. for 3 hours to volatilize the solvent can be defined as the “solid content”.

When the content of the polyether-modified silicone oil (A) is in this range, the antifouling coating film obtained from the antifouling coating composition of the present invention and the fishing net dyed with the antifouling coating composition of the present invention are used. Is excellent in antifouling property and film forming property.

(B) Antifouling agent:
The antifouling coating composition of the present invention contains at least medetomidine (B1) as an antifouling agent (B).

<Medetomidine (B1)>
Medetomidine is (±) -4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole.

The content of medetomidine (B1) in the antifouling coating composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0.05 to, assuming that the solid content of the antifouling coating composition is 100% by mass. It is 45% by mass. When the content of medetomidin (B1) is in this range, the antifouling coating film obtained from the antifouling coating composition of the present invention and the fishing net dyed with the antifouling coating composition of the present invention are barnacles. It also has excellent antifouling properties for coelenterates (hydra, etc.).

The content of medetomidine (B1) is preferably 0.01 to 1,000 parts by mass, more preferably 0.1 to 500 parts by mass, based on 100 parts by mass of the polyether-modified silicone oil (A). It is more preferably 1 to 200 parts by mass.

<Antifouling agent other than medetomidine (B2)>
The antifouling coating composition of the present invention exhibits excellent antifouling property by containing medetomidine (B1) as the antifouling agent (B), but in order to further improve the antifouling property, if necessary. , An antifouling agent (B2) other than medetomidine (hereinafter, also referred to as “another antifouling agent (B2)”) may be contained.

Other antifouling agents (B2) include, for example, cuprous oxide, rodane copper, copper powder, bisdimethyldithiocarbamoylzincethylenebisdithiocarbamate, zincdimethyldithiocarbamate, zincethylenebisdithiocarbamate, N, N-dimethyl-N. '-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, Tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, copper pyrithione, zincpyrythione, 2,3-dichloro-N- (2', 6'-diethylphenyl) maleimide, 2 , 3-Dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, Triphenylboran amine complex (triphenylboran pyridine complex, triphenylboran n-octadecylamine, triphenylboran 3- (2-ethylhexyloxy) propylamine, etc.), diphenylmethylboran 4-isopropylviridine, chloro Methyl-n-octyldisulfide, N', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, and N', N'-dimethyl-N-tolyl- (N-fluorodichloromethylthio) sulfamide Can be mentioned.

The other antifouling agent (B2) may be used alone or in combination of two or more.
The content of the other antifouling agent (B2) in the antifouling coating composition of the present invention is not particularly limited as long as it does not adversely affect the physical properties of the coating film such as crack resistance, but the antifouling coating composition When the solid content is 100% by mass, it is preferably 1 to 80% by mass, and more preferably 5 to 60% by mass. The content of the other antifouling agent (B2) is preferably 600 parts by mass or less, more preferably 1 to 400 parts by mass, and further preferably 2 with respect to 1 part by mass of medetomidine (B1). ~ 200 parts by mass.

(C) Coating film forming resin:
As the coating film-forming resin (C), a coating film-forming resin blended in a conventional ship bottom paint, an antifouling agent for fishing nets, or the like can be used.

By being hydrolyzed in seawater (eg, in the case of (meth) acrylic acid metal salt-based copolymers) or by dissolving (eg, in the case of rosin), a new coating surface appears (eg, in the case of rosin). In addition to resins that can release antifouling agents contained in the coating film to exert an antifouling effect as well as self-renewal properties of the coating film, water-insoluble and non-hydrolyzable resins (eg, vinyl chloride) System resin) can also be used.

Examples of the coating film-forming resin (C) include (meth) acrylic acid metal salt copolymer, polyester metal salt copolymer, silyl ester-containing copolymer, polysiloxane block-containing metal salt copolymer, and sulfur-containing organopoly. Siloxane block vinyl copolymer, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, rubber chloride resin, acrylic resin (the (meth) acrylic acid metal salt copolymer , The silyl ester-containing copolymer, the polysiloxane block-containing metal salt copolymer, and the sulfur-containing organopolysiloxane block vinyl copolymer are excluded), a styrene-butadiene resin, and a polyester resin (the polyester metal). Salt copolymers are excluded.), Epoxy resins, phenolic resins, synthetic rubbers, petroleum resins, rosin ester resins, rosin soaps, rosins and the like can be used.

Examples of the (meth) acrylic acid metal salt copolymer, polyester metal salt copolymer, or silyl ester-containing copolymer include hydrolysis as described in Patent Document 1 (International Publication No. 2011/118526). Degradable copolymers can be mentioned, specifically, degradable copolymers.
Acrylic resin (or polyester resin), general formula [II]:
COO-MO-COR ⁶ ... [II]
[In formula [II], M represents Zn or Cu, and R ⁶ represents a monovalent organic group. ]
(Meta) acrylic acid metal salt copolymer (or polyester metal salt copolymer) having a side chain terminal group represented by
General formula [III]:
CH ₂ = C (R ⁷ ) -COO-MO-CO-C (R ⁷ ) = CH ₂ ... [III]
[In formula [III], M represents Zn or Cu, and R ⁷ independently represents a hydrogen atom or a methyl group. ]
A (meth) acrylic acid metal salt copolymer containing a structural unit derived from a monomer represented by the above and a structural unit derived from another unsaturated monomer copolymerizable with the monomer. , And the general formula [IV]:
CH (R ⁸ ) = C (R ⁹ ) -COO-SiR ¹⁰ R ¹¹ R ¹² ... [IV]
[In formula [IV], R ⁹ represents a hydrogen atom or a methyl group,
R ¹⁰ , R ¹¹ and R ¹² each represent a monovalent organic group having 1 to 20 carbon atoms which may independently have a heteroatom.
R ⁸ is a hydrogen atom or R ^13- O-CO (where R ¹³ is a monovalent organic group having 1 to 20 carbon atoms which may independently have a hetero atom or a silyl represented by Si R ¹⁴ R ^{15 R 16} Indicates a group, and R ¹⁴ , R ¹⁵ and R ¹⁶ each indicate a monovalent organic group having 1 to 20 carbon atoms which may independently have a heteroatom.)
Is shown. ]
Examples thereof include a silyl ester-containing copolymer containing a structural unit derived from the monomer represented by the above and a structural unit derived from another unsaturated monomer copolymerizable with the monomer.

^{The monovalent organic group R 6} in the general formula [II] includes a saturated or unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or the like. Aromatic hydrocarbon groups having 6 to 18 carbon atoms, or substituents thereof are preferred, with saturated or unsaturated aliphatic hydrocarbon groups having 10 to 20 carbon atoms or saturated or unsaturated alicyclic hydrocarbons having 3 to 20 carbon atoms. Hydrogen groups, or substituents thereof, are more preferred.

Other unsaturated monomers that can be copolymerized with the monomer represented by the general formula [III] or the general formula [IV] include, for example,
(Meta) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid lauryl ester, (meth) acrylic acid tridecyl ester , (Meta) acrylic acid stearyl ester, (meth) acrylic acid allyl ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid isobornyl ester, (meth) acrylic acid methoxyester , (Meta) acrylic acid ethoxyester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid (Meta) acrylic acid esters such as hydroxybutyl ester;
Monocarboxylic acids such as (meth) acrylic acid;
Dicarboxylic acids such as itaconic acid, maleic acid, succinic acid or their half-esters (monoesters) or diesters;
Examples include styrenes such as styrene and α-methylstyrene; and vinyl esters such as vinyl acetate and vinyl propionate, which may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the (meth) acrylic acid metal salt copolymer and the polyester metal salt copolymer measured by the GPC method under the conditions of Examples described later or equivalent conditions is the antifouling paint. Considering the viscosity of the composition, storage stability, or the elution rate of the antifouling coating or the like (antifouling coating and antifouling coating composition impregnated in the fishing net), it is usually 1,000 to 200,000, preferably 1,000 to 200,000. Is 1,000 to 100,000.

The number average molecular weight (Mn) of the silyl ester-containing copolymer measured under the conditions described in Examples described later or equivalent conditions is the viscosity, storage stability, or antifouling coating film of the antifouling coating composition. In consideration of the dissolution rate of the above, it is usually 1,000 to 200,000, preferably 1,000 to 100,000.

Examples of the polysiloxane block-containing metal salt copolymer include resins as described in Patent Document 2 (Japanese Unexamined Patent Publication No. 2006-77095), and specifically, the following (A1) to (A3). At least one polysiloxane block-containing metal salt copolymer selected from the group consisting of the above can be used.
(A1): A structural unit (a11) derived from a polysiloxane block-containing polymerizable unsaturated monomer, and
The following formula (a12):
CH ₂ = C (R ¹⁷ ) -COO-MO-CO-R ¹⁸ ... (a12)
(In the formula (a12), M represents a divalent metal atom, R ¹⁷ represents a hydrogen atom or a methyl group, and R ¹⁸ represents a monovalent organic group having no radical reactivity.)
The structural unit (a12) derived from the polymerizable unsaturated carboxylic acid metal salt represented by
A polysiloxane block-containing metal salt copolymer having a polymerizable unsaturated carboxylic acid or a structural unit (a13) derived from an ester thereof,
(A2): A structural unit (a21) derived from a polysiloxane block-containing polymerizable unsaturated monomer, a structural unit (a22) derived from a divalent metal di (meth) acrylate, and a polymerizable unsaturated carboxylic acid. A polysiloxane block-containing metal salt copolymer having a structural unit (a23) derived from an acid or an ester thereof,
(A3): The polysiloxane block (a31) and the acrylic resin block (a32) are expressed by the following formula (a33):
[-MO-CO- (G-CO-O-) _r- (CH ₂ ) _p- ] ... (a33)
(In the formula, M represents a divalent metal atom, G represents a divalent hydrocarbon group, r represents 0 or 1, p represents an integer of 0 to 5, and the leftmost line is an acrylic resin block. The bond with the group represented by COO of (a32) is shown, and the rightmost line shows the bond with the polysiloxane block (a31).)
A polysiloxane block-containing metal salt copolymer bonded by the metal-containing bond (a33) represented by.

Examples of the polysiloxane block include a monovalent group represented by the following formula (a0).

（式（ａ０）において、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜５のアルキル基またはフェニル基を示し、
ｍは５〜７，０００の整数を示し、
ｎは０〜５０の整数を示し、
左端の線は、隣接する原子との結合を示す。）

(In the formula (a0), R ¹ and R ² independently represent an alkyl group or a phenyl group having 1 to 5 carbon atoms, respectively.
m represents an integer of 5 to 7,000,
n represents an integer from 0 to 50
The leftmost line shows the bond with the adjacent atom. )

Examples of the polysiloxane block-containing polymerizable unsaturated monomer for deriving the structural units (a11) and (a21) include the following formula:
CH ₂ = CR-COO- (CH ₂ ) _p- [PS]
(In the formula, R represents a hydrogen atom or a methyl group, p represents an integer of 0 to 5, and − [PS] represents a polysiloxane block represented by the formula (a0).)
The ones represented by are mentioned.

As the [-O-CO-R ¹⁸ ] portion in the above formula (a12), for example,
Saturated aliphatic carboxylic acid residues that may be linear or branched, propionic acid residues (C ₂ H ₅ COO-), valerate residues (CH ₃ (CH ₂ ) ₃ COO-), Palmitic acid residue (CH ₃ (CH ₂ ) ₁₄ COO-), myristic acid residue (CH ₃ (CH ₂ ) ₁₂ COO-), lauric acid residue (CH ₃ (CH ₂ ) ₁₀ COO-), stearic acid Residues (C ₁₇ H ₃₅ COO-), Versatic acid residues ((C ₃ H ₇ ) ₃ C-COO-), etc .;
_{Naphthenic acid residue (C 5} H ₉ (CH ₂ ) _n COO-), which is a saturated alicyclic carboxylic acid residue;
_{Benzoic acid residue (C 6} H ₅ COO-), which is an aromatic ring-type carboxylic acid residue;
Included are resin acid residues contained in rosin.

Among these, those having a total carbon number of about 3 to 20 in the carboxylic acid residue [-O-CO-R ¹⁸ ] portion are preferable, and are contained in, for example, versatic acid residue, naphthenic acid residue, and rosin. The residue of the resin acid is desirable in terms of physical properties such as film-forming property and crack resistance of the antifouling coating film according to the present invention, and elution property.

Examples of the divalent metal contained in the polysiloxane block-containing metal salt copolymers (A1) to (A3) include Zn, Cu and Mg.
As derived from the polymerizable unsaturated carboxylic acid or its ester that induces the structural units (a13) and (a23), it is the same as the monomer represented by the general formula [III] or the general formula [IV]. Unsaturated monomers similar to other unsaturated monomers that can be polymerized can be used.

Examples of the polysiloxane block (a31) include a polysiloxane block represented by the formula (a0). The acrylic resin block (a32) is a portion from which R of at least one of the side chains represented by COOR (R is a hydrogen atom or an organic group) of the acrylic resin is removed from the acrylic resin.

The number average molecular weight (Mn) of the polysiloxane block-containing metal salt copolymer measured by liquid chromatography under the conditions of Examples described later or equivalent conditions is the viscosity of the copolymer solution and the copolymer. From the viewpoint of preventing gelation or antifouling property of an antifouling coating film or the like, it is usually 1,000 to 50,000, preferably 1,000 to 10,000, and more preferably 2,000 to 5,000. is there.

The sulfur-containing organopolysiloxane block vinyl copolymer includes a vinyl polymer block having a structural unit derived from a radically polymerizable vinyl-based monomer and a general formula [V] :.

（式［Ｖ］中、複数個あるＲ¹⁹は、それぞれ独立にフッ素原子を有してもよい炭素数が１〜２０の１価の炭化水素基を示し、Ｒ²⁰、Ｒ²¹およびＲ²²は、それぞれ独立に、前記Ｒ¹⁹または炭素数が１〜２０の２価の硫黄含有有機基を示し、ｓは正の数を、ｔは０以上の数を示す。Ｒ²²が複数個存在する場合（すなわち、ｔが２以上の整数の場合）、これらは互いに同一であっても異なっていてもよい。）
で表され、かつ少なくとも１つの前記硫黄含有有機基を有する硫黄含有オルガノポリシロキサンブロックとを有する共重合体などが挙げられる。この共重合体は、前記ビニル系モノマー（たとえば、ヘテロ原子を含んでいてもよい（メタ）アクリル酸エステル）と、前記硫黄含有オルガノポリシロキサンブロックにおいて前記硫黄含有有機基をメルカプト基（ＳＨ基）に置き換えた化合物とを、ラジカル重合開始剤等のラジカル発生源の存在下で反応させることにより、製造することができる。

(In the formula [V], a plurality of R ^19s represent monovalent hydrocarbon groups having 1 to 20 carbon atoms, each of which may independently have a fluorine atom, and R ²⁰ , R ²¹ and R ²² are. , Independently each of the above R ¹⁹ or a divalent sulfur-containing organic group having 1 to 20 carbon atoms, where s indicates a positive number and t indicates a number of 0 or more. When a ^{plurality of R 22} are present. (That is, if t is an integer greater than or equal to 2), they may be the same or different from each other.)
Examples thereof include a copolymer represented by and having a sulfur-containing organopolysiloxane block having at least one sulfur-containing organic group. In this copolymer, the vinyl-based monomer (for example, a (meth) acrylic acid ester which may contain a hetero atom) and the sulfur-containing organic group in the sulfur-containing organopolysiloxane block are mercapto groups (SH groups). It can be produced by reacting the compound replaced with the above compound in the presence of a radical generation source such as a radical polymerization initiator.

Examples of the acrylic resin include homopolymers or copolymers of (meth) acrylic acid-based esters, homopolymers of (meth) acrylic acid esters, and copolymerization of at least two or more (meth) acrylic acid esters. Examples thereof include coalescence, (meth) acrylic acid ester / styrene copolymer, and the like. As the (meth) acrylic acid-based ester, an unsaturated monomer similar to other unsaturated monomers that can be copolymerized with the monomer represented by the general formula [III] or the general formula [IV] can be used. Can be used. The weight average molecular weight (Mw) of the acrylic resin based on polystyrene, which is measured by the GPC method in the conditions described later in Examples or equivalent conditions, is preferably 1,000 to 300,000, and is coated. From the viewpoint of performance and physical properties of the coating film, it is more preferably 20,000 to 200,000.

The viscosity of a 50% solution of xylene of the coating film-forming resin (C) (measured by an E-type viscometer, "VISCONIC EMD" manufactured by Tokimec Co., Ltd.) is preferably 10 to 20,000 mPa · s at 25 ° C. Further, a resin having a Tg (glass transition point) of -20 to 30 ° C. can usually be used.

Among these, the coating film-forming resin (C) includes both a (meth) acrylic acid metal salt copolymer and a polysiloxane block-containing metal salt from the viewpoint of film-forming property and antifouling property when applied to a fishing net. Polymers and acrylic resins are preferred.

The content of the coating film-forming resin (C) in the antifouling coating composition of the present invention is preferably 10 to 99.49% by mass, more preferably 20%, assuming that the solid content of the antifouling coating composition is 100% by mass. ~ 97.95% by mass. When the content of the coating film-forming resin (C) is in this range, the antifouling coating film formed from the antifouling coating composition of the present invention is excellent in film-forming property and adhesion to a substrate.

(D) Plastic resin:
The antifouling coating composition of the present invention may contain a plastic resin (D) (however, the coating film forming resin (C) is excluded). Examples of the plastic resin (D) include polyolefins, polysulfides, liquid paraffins, waxes, and petrolatum. By adding the plastic resin (D), the antifouling property of the antifouling coating film and the like is improved, and the elution of the antifouling agent (B) from the antifouling coating film and the like is adjusted to have a long-term antifouling effect. Can be demonstrated.

Examples of the polyolefin include polyethylene, an ethylene / α-olefin copolymer, polypropylene, and polybutene. Polybutene is preferable, and polybutene having a number average molecular weight of 280 to 1,500 is particularly preferable from the viewpoint of antifouling property. As such polybutene, if it is a commercially available product, for example, LV-5, LV-10, LV-25, LV-50, LV-100, HV-35, HV-50, HV-100, and HV-300. (Both are trade names, JX Energy Co., Ltd.).

The polysulfide has the following formula [VI]:
R- (S) _u- R ... [VI]
It is a dialkyl polysulfide represented by.

In the formula [VI], each of the two Rs independently represents an alkyl group having 1 to 20 carbon atoms.
u is an integer of 2 or more, and is preferably an integer of 2 to 10 from the viewpoint of antifouling property of the antifouling coating film and the like.

Examples of the polysulfide include diethylpentasulfide, di-tert-butyldisulfide, di-tert-butyltetrasulfide, di-tert-pentyltetrasulfide, dioctylpolysulfide, di-tert-octylpentasulfide, and di-tert-nonylpenta. Included are sulfides, di-tert-dodecylpentasulfides, and dinonadesyltetrasulfides.

The liquid paraffin is a liquid hydrocarbon oil mainly composed of alkylnaphthenes, which is obtained by distilling crude oil to remove gasoline, kerosene, light oil, etc., taking a fraction from spindle oil to engine oil, and refining it. Yes, preferably, it conforms to the provisions of JIS K9003.

Examples of the wax include petroleum-based wax, polyethylene-based wax, and polypropylene-based wax.
Examples of the petroleum-based wax include paraffin wax, microcrystalline wax, and petrolatum wax, and paraffin wax is particularly preferable.

Examples of the petrolatum include white petrolatum and yellow petrolatum.
Among such plastic resins (D), polybutene and polysulfide are preferable from the viewpoint of improving the antifouling effect.

These can be used alone or in combination of two or more.
The content of the plastic resin (D) in the antifouling coating composition of the present invention is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, assuming that the solid content of the antifouling coating composition is 100% by mass. Is. When the content of the plastic resin (D) is in this range, the antifouling coating film formed from the composition of the present invention and the fishing net dyed with the composition of the present invention are excellent in flexibility.

(E) Metal oxide:
The antifouling coating composition of the present invention may contain a metal oxide (E) (excluding cuprous oxide as the other antifouling agent (B2)) in order to improve the strength of the coating film. .. Examples of the metal oxide include one or more metal oxides selected from the group consisting of CuO (copper oxide (II) oxide), ZnO, TiO ₂ , Al ₂ O ₃ , SiO _{2, and MgO.}

The content of the metal oxide (E) in the antifouling coating composition of the present invention is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, assuming that the solid content of the antifouling coating composition is 100% by mass. %.

Other ingredients:
In addition to the above-mentioned components, the antifouling coating composition of the present invention contains various components used in general coating compositions such as coloring pigments, extender pigments, dehydrating agents, stiffeners, organic acids, and solvents. It may be included. These may be used alone or in combination of two or more.
Examples of the rocking agent (anti-sedimentation agent / anti-sagging agent) include polyethylene oxide wax, fatty acid amide wax, and Benton.

solvent:
As the solvent, an aliphatic hydrocarbon solvent and fragrance that can easily disperse various components such as an antifouling agent, which are blended in a conventional antifouling coating composition, particularly an antifouling coating composition for fishing nets, can be easily dispersed. Group hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, or ether solvents can be used.

Examples of the aliphatic hydrocarbon solvent include tarpen.
Examples of the aromatic hydrocarbon solvent include xylene, toluene, ethylbenzene, trimethylbenzene, methylethylbenzene, and propylbenzene.

Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, and methyl ethyl isobutyl ketone.
Examples of the ester solvent include ethyl acetate and butyl acetate.

Examples of the alcohol solvent include ethanol, isopropyl alcohol, n-butanol, and isobutanol.
Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PMAC).

These can be used alone or in combination of two or more.
Among these solvents, xylene, ethylbenzene, butyl acetate, and propylene glycol monomethyl ether are preferable from the viewpoint of dissolving power, flash point, and evaporation rate.
The blending amount of the solvent in the antifouling coating composition of the present invention is usually 10 to 90% by mass, preferably 20 to 80% by mass, assuming that the amount of the antifouling coating composition is 100% by mass.

[Manufacturing method of antifouling paint composition]
The antifouling coating composition of the present invention can be produced, for example, by mixing and stirring a predetermined amount of each of the above components using a general device and method for producing a coating composition.

[Use of antifouling paint composition]
The antifouling coating composition of the present invention prevents the spread of sludge in various marine civil engineering works such as thermal power, underwater structures such as water supply and drainage ports of nuclear power plants, bay roads, submarine tunnels, harbor facilities, canals, and waterways. It can also be used to prevent stains on the surface of various base materials that come into contact with seawater or fresh water such as membranes, ships (eg, bottom of ships), fishing gear (eg, ropes, fishing nets, floats, buoys). Specifically, the antifouling coating composition of the present invention is applied to the surface of a base material once or multiple times according to a conventional method, impregnated, and then dried to cure, thereby excellent in antifouling property. The antifouling agent component can be released slowly over a long period of time, and even if it is applied thickly, an antifouling coating film having appropriate flexibility and excellent crack resistance is formed. The antifouling coating film of the present invention that can be formed in this way comprises the solid content of the antifouling coating composition of the present invention. A base material having an antifouling coating film on the surface is also referred to as a "base material with an antifouling coating film".

Further, the antifouling coating composition of the present invention is preferably used for painting fishing gear, particularly for net dyeing of fishing nets. Examples of the material of the fishing net include polyethylene, nylon, hemp, metal, polyester and the like, and in the case of such a material, the antifouling paint composition is satisfactorily impregnated and adhered. Net dyeing of fishing nets can be performed using a general method. For example, the fishing net is immersed in the antifouling paint composition and impregnated with the antifouling paint composition in or between the fibers of the fishing net. After that, the fishing net can be pulled up and dried to cure the antifouling paint composition. Further, the antifouling paint composition may be sprayed on the front and back surfaces of the fishing net spread or spread and hung by a method of electrostatic coating, or by a method of air gun, airless coating or the like. As described above, the weight increase of the fishing net by net dyeing is usually about 80 to 300 g per 1 kg of the fishing net. A fishing net dyed with the composition of the present invention has the solid content of the antifouling coating composition of the present invention in or between the fibers, and further has the antifouling coating film of the present invention on the surface thereof. You may be doing it.

The antifouling coating film or the base material with the antifouling coating film formed from the composition of the present invention, and the fishing nets dyed with the compositions of the present invention and the present invention include sea lettuce, hydra, green laver, celpra, oyster, and fusakokemushi. , Hydra and other aquatic organisms (especially Fujitsubo and Hydra) can be prevented from adhering continuously for a long period of time and have excellent antifouling properties.

Further, the antifouling method for the base material of the present invention is to apply or impregnate the base material with the antifouling coating composition of the present invention and then cure the base material. Adhesion of aquatic organisms (particularly Fujitsubo and Hydra) such as sea lettuce, Fujitsubo, green laver, Serpra, oyster, Bugula neritina, and hydra can be continuously prevented for a long period of time.

Hereinafter, the present invention will be described in more detail based on Examples, but the embodiments of the present invention are not limited to these Examples.
[Measuring method]
<Weight average molecular weight (Mw) of coating film forming resin>
The weight average molecular weight (Mw) of the coating film-forming resin was measured by the GPC (gel permeation chromatography) method under the following conditions.
Equipment: "HLC-8120GPC" (manufactured by Tosoh Corporation)
Column: "TSKgel SuperH2000" and "TSKgel SuperH4000" are connected (both manufactured by Tosoh Corporation, 6 mm (inner diameter) x 15 cm (length))
Eluent: tetrahydrofuran (THF)
Flow velocity: 0.500 ml / min
Detector: RI
Column constant temperature bath temperature: 40 ° C
Standard substance: Polystyrene Sample preparation method: The polymer solution prepared in each production example was dehydrated by adding a small amount of calcium chloride, and then filtered through a membrane filter to obtain a filter product as a GPC measurement sample.

<Number average molecular weight (Mn) of coating film forming resin>
The number average molecular weight (Mn) of the coating film-forming resin was measured by liquid chromatography under the following conditions.
Equipment: "Waters 2695"
Column: "TSKgel SuperH2000" and "TSKgel SuperH4000" are connected (both manufactured by Tosoh Corporation, 6 mm (inner diameter) x 15 cm (length))
Eluent: tetrahydrofuran (THF)
Flow velocity: 0.6 ml / min
Detector: "Shodex RI-104"
Column constant temperature bath temperature: 40 ° C

<Viscosity of coating film forming resin solution>
The viscosity of the coating film-forming resin solution was measured at 25 ° C. with an E-type viscometer (“VISCONIC EMD” manufactured by Tokimec Co., Ltd.).

[Manufacturing Example 1] (Manufacturing of acrylic resin)
67 parts by mass of xylene was placed in a four-necked flask equipped with a stirrer, a reflux condenser, and a dropping funnel, and the temperature was maintained at 90 ° C. with stirring. Here, a mixed solution of 42 parts by mass of isobutyl methacrylate (IBMA), 27 parts by mass of butyl acrylate (BA), 18 parts by mass of methyl methacrylate (MMA) and 0.09 parts by mass of t-butylperoxy-2-ethylhexanoate is added. It was added dropwise over 2 hours. To this, t-butylperoxy-2-ethylhexanoate was added twice every hour by 0.045 parts by mass while continuing stirring 2 hours after the completion of the dropping, and t-butylperoxy- was further continued while stirring. 0.045 parts by mass of 2-ethylhexanoate was added twice every 30 minutes. Then, the temperature was raised to 105 ° C., and after stirring for 30 minutes, 20 parts by weight of xylene was added to obtain an acrylic resin solution (varnish A1). The appearance of the obtained varnish A1 is transparent, the NV (heat residue after drying in a hot air dryer at 105 ° C. for 3 hours) is 50.3%, and the viscosity at 25 ° C. is 9,200 mPa · s. The weight average molecular weight (Mw) of the contained resin was 151,200.

[Production Example 2] (Production of (meth) acrylic acid metal salt copolymer)
(Preparation of solution (A2-1) containing metal-containing monomer)
85.4 parts by mass of propylene glycol monomethyl ether (PGM) and 40.7 parts by mass of zinc oxide were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and the temperature was raised to 75 ° C. with stirring. did. Subsequently, a mixture consisting of 43.1 parts by mass of methacrylic acid (MAA), 36.1 parts by mass of acrylic acid (AA), and 5 parts by mass of water was added dropwise from the dropping funnel at a constant velocity over 3 hours. The reaction solution, which was in a milky white state, became transparent after the completion of dropping. After further stirring for 2 hours, 36 parts by mass of propylene glycol monomethyl ether was added to obtain a solution (A2-1) containing a metal-containing monomer. The NV of the metal-containing monomer solution (A2-1) was 44.8%.

(Production of (meth) acrylic acid metal salt copolymer)
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts by mass of propylene glycol monomethyl ether (PGM) and 57 parts by mass of xylene, and the temperature was raised to 100 ° C. with stirring. Subsequently, 52 parts by mass of the metal-containing monomer solution (A2-1), 1 part by mass of methyl methacrylate (MMA), 66.2 parts by mass of ethyl acrylate (EA), and 2-methoxyethyl acrylate (2-MEA) 5 .4 parts by mass, azobisisobutyronitrile (AIBN) (manufactured by Nippon Hydrazin Industry Co., Ltd.) 2.5 parts by mass, azobismethylbutyronitrile (AMBN) (manufactured by Nippon Hydrazin Industry Co., Ltd.) 7 parts by mass A transparent mixture consisting of 1 part by mass of the chain transfer agent "Nofmer MSD" (manufactured by Nippon Oil & Fats Co., Ltd.) and 10 parts by mass of xylene was added dropwise from the dropping funnel at a constant velocity over 6 hours. After completion of the dropping, 0.5 parts by mass of t-butyl peroctate (TBPO) and 7 parts by mass of xylene were added dropwise over 30 minutes, and after further stirring for 1 hour and 30 minutes, 4.4 parts by mass of xylene was added. A reaction mixture (varnish A2) containing a (meth) acrylic acid metal salt copolymer having no insoluble matter and being pale yellow and transparent was obtained. The NV (heat residue after drying in a hot air dryer at 105 ° C. for 3 hours) of the reaction mixture (varnish A2) was 45.6%, the viscosity at 25 ° C. was 1,650 mPa · s, and the resin contained in the varnish A2. The weight average molecular weight (Mw) of was 5,200.

[Production Example 3] (Production of Polysiloxane Block-Containing Metal Salt Copolymer)
In a four-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel, 20 parts by mass of propylene glycol monomethyl ether and 82 parts by mass of xylene were charged, the temperature was raised to 90 ° C., and the temperature was maintained. Next, in this flask, 7 parts by mass of zinc dimethacrylate, 7 parts by mass of zinc diacrylate, 6 parts by mass of methyl methacrylate, 45 parts by mass of ethyl acrylate, 0.5 parts by mass of pure water, 16 parts by mass of propylene glycol monomethyl ether, and methacryloxy. A mixed solution of 35 parts by mass of propylpolydimethylsiloxane (trade name "Silaplane FM-0711", manufactured by JNC Co., Ltd., having a number average molecular weight of about 1,000) and 3 parts by mass of azobisisobutyronitrile as a polymerization catalyst. Was added dropwise over 2 hours, and after the addition, the temperature (90 ° C.) was maintained for about 4 hours, and the methacryloxypropyl polydimethylsiloxane component calculated based on the charged amount was 35% by mass, and zinc di ( A reaction mixture containing a polysiloxane block-containing metal salt copolymer having a metal Zn content of 4.2% by mass and a component derived from methyl methacrylate and ethyl acrylate of 51% by mass in the meta) acrylate. (However, the mass of the copolymer is 100% by mass.) Was obtained. The NV of varnish A3 (heat residue after drying in a hot air dryer at 105 ° C for 3 hours) is 45.2%, the viscosity at 25 ° C is 12,000 mPa · s, and the number average molecular weight of the resin contained in varnish A3 (Mn). ) Was 2,380, and the solid acid value was 71 mgKOH / g.

[Manufacturing of antifouling paint composition]
[Examples 1 to 40, Comparative Examples 1 to 15]
An antifouling coating composition is obtained by uniformly mixing the varnish A1, varnish A2 or varnish A3 obtained in Production Examples 1 to 3 with other components at the ratios shown in Tables 2 to 5 using a paint shaker. Manufactured. Each antifouling coating composition was evaluated by the method described later. The results are shown in Tables 2-5.
Details of the raw materials used in the examples and comparative examples are as follows.

[Performance evaluation]
(1) Static antifouling property (fishing net)
A fishing net (polyethylene knotless net (7 nodes, 400 denier / 50 lines, length 15 cm x width 15 cm)) was immersed in each of the antifouling paint compositions prepared in Examples and Comparative Examples for about 1 to 3 minutes. After taking it out, it was air-dried indoors for 7 days to obtain a fishing net with a coating film.
This coated fishing net was fixed to a stainless steel frame of 80 cm × 40 cm and immersed in about 2 m below the sea surface in Hiroshima Bay, Hiroshima Prefecture. Every two months from the start of immersion, the area (attachment area) (%) of the part of the fishing net to which aquatic organisms are attached is measured (the total area of the fishing net is 100%), and it is static based on the following evaluation criteria. The antifouling property (fishing net) was evaluated.
<Evaluation criteria>
A: Adhesion area is 0%
B: Adhesion area is greater than 0% and less than 10% C: Adhesion area is 10% or more and less than 30% D: Adhesion area is 30% or more and less than 50% E: Adhesion area is 50% or more and less than 90% F: Adhesion area is 90% or more

(2) Static antifouling property (panel)
Epoxy-based rust preventive paint (epoxy AC paint, trade name "Banno 500", manufactured by China Paint Co., Ltd.) is applied to a sandblasted steel plate (length 300 mm x width 100 mm x thickness 3.2 mm) with a dry film thickness of 150 μm. After that, an epoxy-based binder paint (trade name "Banno 500N", manufactured by China Paint Co., Ltd.) was applied so that the dry film thickness was 100 μm. Subsequently, the antifouling coating composition produced in Examples and Comparative Examples was applied once so that the dry film thickness was 100 μm, and dried at room temperature for 7 days to prepare a test plate with an antifouling coating film. did. The three coating intervals were set to 1 day / 1 coat.

The prepared test plate was soaked in Hiroshima Bay, Hiroshima Prefecture for 10 months, and every 2 months during that period, the area (adhesion area) (%) (prevention) of the part where marine organisms other than slime on the coating film surface adhered. The total area of the dirty coating film is 100%.) Was measured. Then, the static antifouling property (panel) was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Adhesion area is 0%
B: Adhesion area is greater than 0% and less than 10% C: Adhesion area is 10% or more and less than 30% D: Adhesion area is 30% or more and less than 50% E: Adhesion area is 50% or more and less than 90% F: Adhesion area is 90% or more

(3) Barnacle resistance The barnacle resistance evaluation is based on the adhesion area of the fishing net or test plate 10 months after the start of immersion in the sea with the static antifouling property (1) or the static antifouling property (2). The ratio of the area of the barnacles attached to the barnacles (barnacles attached area) was measured, and the barnacle resistance was evaluated based on the following evaluation criteria.
<Evaluation criteria>
A: Barnacle adhesion area is 0%
B: Barnacle adhesion area is greater than 0% and less than 10% C: Barnacle adhesion area is 10% or more and less than 30% D: Barnacle adhesion area is 30% or more and less than 50% E: Barnacle adhesion area is 50% or more and less than 90% F : Barnacle adhesion area is 90% or more

(4) Coelenterate (Hydra) In the evaluation of coelenterate (Hydra), a fishing net with a coating film prepared by the same method as the static antifouling property (1) was placed in a 80 cm x 40 cm stainless steel frame. It was fixed and immersed in about 2 m below the sea level in Sagami Bay, Kanagawa Prefecture. The ratio of the area where the hydra was attached (hydra adhesion area) to the adhesion area 4 months after the start of immersion was measured, and the hydra resistance was evaluated based on the following evaluation criteria.
<Evaluation criteria>
A: Hydra adhesion area is 0%
B: Hydra adhesion area is greater than 0% and less than 10% C: Hydra adhesion area is 10% or more and less than 30% D: Hydra adhesion area is 30% or more and less than 50% E: Hydra adhesion area is 50% or more and less than 90% F : Hydra adhesion area is 90% or more

(5) Film-forming property Each of the antifouling coating compositions prepared in Examples and Comparative Examples was applied onto a glass plate using an applicator so that the dry film thickness was 100 μm, and dried and applied indoors for 2 weeks. A film was formed. The coating film was touched with a fingertip and evaluated based on the following criteria.
<Evaluation criteria>
◎ ・ ・ ・ Slightly scratched on the coating film ○ ・ ・ ・ Slightly scratched on the coating film surface □ ・ ・ ・ Clearly scratched on the coating film surface △ ・ ・ ・ Easily applied to the coating film Cracks occur × ・ ・ ・ The coating film is easily destroyed

(6) Storage stability Each of the antifouling paint compositions prepared in Examples and Comparative Examples was placed in a sealed container and stored in an incubator at 40 ° C. for 2 months, and the state of the paint after storage was prepared. And the viscosity was confirmed, compared with the state before storage, and evaluated based on the following evaluation criteria.
<Evaluation criteria>
5 ... No change 4 ... Slight increase in viscosity is observed 3 ... Slight increase in viscosity and fine grains are observed 2 ... Significant increase in viscosity and minute grains are observed 1 ...・ Significant increase in viscosity and grains are observed.

Claims (15)

An antifouling coating composition containing a polyether-modified silicone oil (A), an antifouling agent (B), and a coating film-forming resin (C).
The polyether-modified silicone oil (A) has a general formula [I]:

[In the formula [I], R ¹ independently represents an alkyl group having 1 to 3 carbon atoms.
X ¹ , X ² and X ³ independently represent an alkyl group, a phenyl group or a polyether group having 1 to 5 carbon atoms, respectively.
X ⁴ represents an alkyl or phenyl group having 1 to 18 carbon atoms.
m indicates an integer of 1 or more,
n indicates an integer greater than or equal to 0,
p indicates an integer greater than or equal to 0,
The polyether group has the following formula [Ia]:
−R ² −A− (R ³ O) _q (R ⁴ O) _r −R ⁵・ ・ ・ [Ia]
(In formula [Ia], A represents a single bond or an oxygen atom,
R ² , R ³ and R ⁴ each independently represent a divalent hydrocarbon group having 1 to 5 carbon atoms.
R ⁵ represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms.
q indicates an integer from 1 to 30
r represents an integer from 0 to 30
The leftmost line shows the bond to the silicon atom. ). ], Which has at least one of the above-mentioned polyether groups in one molecule.
Medetomidine (B1) is contained as the antifouling agent (B) ,
The antifouling coating composition contains 1 to 200 parts by mass of the medetomidine (B1) with respect to 100 parts by mass of the polyether-modified silicone oil (A). The coating film-forming resin (C) is a (meth) acrylic acid metal salt copolymer, a polyester metal salt copolymer, a silyl ester-containing copolymer, a polysiloxane block-containing metal salt copolymer, and a sulfur-containing organopolysiloxane. Block vinyl copolymer, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, rubber chloride resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy The antifouling coating composition according to claim 1, which is one or more selected from the group consisting of resins, phenolic resins, synthetic rubbers, petroleum resins, rosin ester resins, rosin soaps, and rosins. The antifouling coating composition according to claim 1 or 2 , further containing an antifouling agent (B2) other than medetomidine as the antifouling agent (B). Antifouling agents (B2) other than medetomidin include cuprous oxide, rodane copper, copper powder, bisdimethyldithiocarbamoyl disulfide bisdithiocarbamate, disulfide dithiocarbamate, disulfide bisdithiocarbamate, N, N-dimethyl-N. '-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, Tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, copper pyrithione, zincpyrythione, 2,3-dichloro-N- (2', 6'-diethylphenyl) maleimide, 2 , 3-Dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, Triphenylboran amine complex, diphenylmethylboran 4-isopropylviridine, chloromethyl-n-octyl disulfide, N', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, and N', N The antifouling coating composition according to claim 3 , which is one or more selected from the group consisting of'-dimethyl-N-tolyl- (N-fluorodichloromethylthio) sulfamide. The antifouling coating composition according to claim 3 or 4 , wherein the antifouling agent (B2) is contained in a proportion of 600 parts by mass or less with respect to 1 part by mass of the medetomidine (B1). The invention according to any one of claims 1 to 5 , further comprising at least one plastic resin (D) selected from the group consisting of polyolefins, polysulfides, paraffins, and petrolatums. Antifouling paint composition. The antifouling coating composition according to any one of claims 1 to 6 , wherein the HLB of the polyether-modified silicone oil (A) is 0.5 to 10. Further, according to any one of claims 1 to 7 , which further comprises one or more metal oxides (E) selected from the group consisting of CuO, ZnO, TiO ₂ , Al ₂ O ₃ , SiO _{2, and MgO.} Antifouling paint composition. The antifouling paint composition according to any one of claims 1 to 8 , which is used for painting fishing gear. An antifouling coating film formed from the antifouling coating composition according to any one of claims 1 to 9. A base material with an antifouling coating film having a base material and the antifouling coating film according to claim 10 provided on the surface of the base material. The base material with an antifouling coating film according to claim 11 , wherein the base material is a fishing gear, a ship, or an underwater structure. A fishing net dyed with the antifouling paint composition according to any one of claims 1 to 9. An antifouling method for a base material, wherein the base material is coated with or impregnated with the antifouling coating composition according to any one of claims 1 to 9, and then cured. A step of applying or impregnating the surface of the base material with the antifouling coating composition according to any one of claims 1 to 9 , and the step of preventing the base material from being coated or impregnated by the step. A method for producing a base material with an antifouling coating film, which comprises a step of curing the stain coating composition.