JP6954649B2 - Antifouling coating composition, a coating material having an antifouling coating film formed by using the composition on the surface - Google Patents

Description

The present invention relates to an antifouling coating composition and a coating material having an antifouling coating film formed by using the composition on the surface.

Aquatic pollutants such as Fujitsubo, Serupura, Mussel, Fusakokemushi, Hoya, Green laver, Sea lettuce, and slime are applied to underwater structures such as ships (especially the bottom of ships), fishing nets, fishing net accessories, and other fishing equipment and power plant water pipes. Adhesion causes problems such as impairing the functions of those vessels and impairing their appearance.
Since the ban on the use of organic tin-containing copolymers that have been used in the past, triorganosilyl group-containing copolymers with low toxicity and low environmental impact have been developed and used in antifouling paints (Patent Document 1). ..
When the triorganosilyl ester copolymer is used, the coating film dissolves at a constant rate in seawater for a long period of time, but the coating film dissolution rate tends to be generally low. There is no problem if the ship is normally operated and the sailing speed is above a certain level, but under the influence of the recent global economic downturn, the berthing period of the ship is prolonged or the sailing speed is slowed down. The problem that the coating solution dissolution rate becomes too low and the antifouling effect is not sufficiently exhibited has come to occur.
Various proposals have been made to solve the above problems. For example, an antifouling coating material (Patent Documents 2 to 4) containing a highly hydrophilic triorganosilyl ester-containing copolymer using a highly hydrophilic monomer as a constituent monomer of the triorganosilyl ester-containing copolymer. , Antifouling paints and the like containing a large amount of elution aids such as rosin compounds have been proposed (Patent Documents 5 to 7).
However, the above-mentioned proposed antifouling paint cannot sufficiently improve the coating film dissolution rate, and as an adverse effect due to excessively increasing hydrophilicity, the coating film dissolves in a relatively short period of time after being immersed in seawater. There was a problem that the coating film stopped or caused deterioration of the physical properties of the coating film such as cracks.
As described above, it contains a triorganosilyl ester-containing copolymer capable of maintaining a high coating film dissolution rate for a long period of time in seawater and maintaining stable antifouling performance without causing coating film abnormalities such as cracks. There has never been an antifouling paint composition.

Japanese Unexamined Patent Publication No. 7-102193 Japanese Unexamined Patent Publication No. 2000-17203 Japanese Unexamined Patent Publication No. 2000-248029 WO2009 / 149919A1 Japanese Unexamined Patent Publication No. 10-30071 Japanese Unexamined Patent Publication No. 2003-183567 WO2015 / 156073A1

The present invention includes a triorganosilyl ester-containing copolymer capable of maintaining a high coating film dissolution rate in seawater for a long period of time and maintaining stable antifouling performance without causing coating film abnormalities such as cracks. An object of the present invention is to provide an antifouling coating composition.

（式中、Ｒ^１は、水素原子又はメチル基を示し、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ同一又は異なって、炭素数３〜６のα位が分岐したアルキル基若しくはフェニル基を示す）で表わされる（メタ）アクリル酸トリオルガノシリルエステル単量体と、
（ｂ）該（メタ）アクリル酸トリオルガノシリルエステル単量体と共重合可能なエチレン性不飽和単量体との混合物から得られるトリオルガノシリルエステル含有共重合体、及び
（Ｂ）炭素数が１〜４のアルコキシ基及びシロキサン骨格を有するシロキサン化合物（但し、シロキサン骨格中のＳｉ原子数が５〜１００）
を含有する防汚塗料組成物が提供される。According to the present invention, (A) (a) general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ each represent the same or different alkyl group or phenyl group in which the α-position having 3 to 6 carbon atoms is branched. ), And the (meth) acrylic acid triorganosilyl ester monomer.
(B) A triorganosilyl ester-containing copolymer obtained from a mixture of the (meth) acrylic acid triorganosilyl ester monomer and a copolymerizable ethylenically unsaturated monomer, and (B) the number of carbon atoms. A siloxane compound having 1 to 4 alkoxy groups and a siloxane skeleton (however, the number of Si atoms in the siloxane skeleton is 5 to 100).
An antifouling coating composition containing the above is provided.

As a result of diligent studies by the present inventor, the physical properties of the coating film (particularly crack resistance) are obtained by adding the siloxane compound (B) having a specific composition to the triorganosilyl ester-containing copolymer (A) having a specific composition. It has been found that an unexpected effect of significantly improving the coating film dissolution rate, particularly the coating film dissolution rate from the initial stage, can be obtained without impairing the above, and the present invention has been completed. The siloxane compound (B) also has an advantageous property that it does not lower the coating film hardness as compared with other coating film elution aids.

According to the present invention, there is provided an antifouling coating composition capable of forming an antifouling coating film having excellent storage stability and maintaining high antifouling performance for a long period of time.

Hereinafter, the present invention will be described in detail.

Antifouling coating composition The antifouling coating composition of the present invention contains the above-mentioned triorganosilyl ester-containing copolymer (A) and the above-mentioned siloxane compound (B).

<Copolymer (A)>
The copolymer (A) of the present invention is obtained by copolymerizing the monomer (a) and the monomer (b).
Hereinafter, a method for synthesizing the monomer (a), the monomer (b), the copolymer (A), and the like will be specifically described.

Monomer (a)
Examples of the alkyl group having a branched α-position having 3 to 6 carbon atoms include an isopropyl group, an s-butyl group, a t-butyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 1-methylpentyl group, and 1, Examples thereof include a 1-dimethylpropyl group, a 1,1-dimethylbutyl group and a texyl group.
In particular, in the present invention, ^{by selecting specific groups as R 2} , R ³ and R ⁴ , it is possible to form an antifouling coating film that is less likely to cause coating film abnormalities and has excellent water resistance. From such a viewpoint, R ^2, R ³ and R ^4, the same or different, an isopropyl group, s- butyl group, preferably a t- butyl group and phenyl group, it is an isopropyl group More preferred.
Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, and diisopropyls-butylsilyl (meth) acrylate. Diisopropyl t-butylsilyl (meth) acrylate, diisopropyltexylsilyl (meth) acrylate, diisopropylphenylsilyl (meth) acrylate, isopropyldis-butylsilyl (meth) acrylate, isopropyldiphenylsilyl (meth) acrylate, ( Examples thereof include diphenyltexylsilyl (meth) acrylate and t-butyldiphenylsilyl (meth) acrylate. In particular, triisopropylsilyl (meth) acrylic acid, tri-s-butylsilyl (meth) acrylic acid, and (meth) acrylic acid are capable of forming an antifouling coating film that is less likely to cause coating film abnormalities and has excellent water resistance. t-Butyldiphenylsilyl is preferred, and triisopropylsilyl (meth) acrylate is more preferred. These (meth) acrylic acid triorganosilyl ester monomers are used alone or in combination of two or more.

Monomer (b)
The monomer (b) is an ethylenically unsaturated monomer copolymerizable with the monomer (a), and is, for example, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, or (meth) acrylic acid. n-butyl, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl acrylate, 2-methoxy acrylate Propyl, 4-methoxybutyl acrylate, 2-ethoxyethyl (meth) acrylate, ethylene glycol monomethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic (Meta) acrylate esters such as 2-hydroxypropyl acid, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate; vinyl chloride, chloride Vinyl compounds such as vinylidene, (meth) acrylonitrile, vinyl acetate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone; aromatic compounds such as styrene, vinyltoluene, and α-methylstyrene can be mentioned. Of these, (meth) acrylic acid ester is particularly preferable, and (meth) methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) acrylic acid. 2-Ethylhexyl and 2-methoxyethyl acrylate are more preferred. The above-exemplified monomer (b) can be used alone or in combination of two or more as the monomer component of the copolymer (A).

Synthesis of Copolymer (A) The copolymer (A) can be obtained by polymerizing a mixture of the monomer (a) and the monomer (b).
The content of the monomer (a) in the mixture is preferably about 20 to 70% by mass, more preferably about 30 to 60% by weight. When the content of the monomer (a) is about 30 to 60% by weight, the coating film formed by using the obtained antifouling coating composition exhibits stable coating film solubility and is antifouling for a long period of time. Performance can be maintained.
The weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 100,000, and particularly preferably 20,000 to 70,000. When Mw is 10,000 to 100,000, the coating film is not brittle and the coating film is appropriately dissolved, so that the desired antifouling effect can be effectively exhibited. Examples of the method for measuring Mw include gel permeation chromatography (GPC).

The copolymer (A) is a copolymer of a random copolymer of a monomer (a) and a monomer (b), an alternating copolymer, a periodic copolymer, or a block copolymer. It may be. The copolymer (A) can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.

Examples of the polymerization initiator used in the polymerization reaction include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, and dimethyl-2,2'. -Azo compounds such as azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy 2-ethylhexanoate, Peroxides such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and 1,1,3,3-tetramethylbutylperoxyneodecanoate can be mentioned. These polymerization initiators can be used alone or in combination of two or more. Examples of the polymerization initiator include AIBN, tert-butylperoxy2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate or 1,1,3. , 3-Tetramethylbutylperoxyneodecanoate is preferred. The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used. At this time, a chain transfer agent such as mercaptan or α-methylstyrene dimer can also be used.

Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like. Of these, solution polymerization is particularly preferable in that the copolymer (A) can be obtained easily and accurately.

In the polymerization reaction, an organic solvent may be used if necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl. Alcohol-based solvents such as alcohol and butyl alcohol; ether-based solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned. Of these, aromatic hydrocarbon solvents are particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.

The reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually 70 to 140 ° C., preferably 80 to 120 ° C. The reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours. The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

The content of the copolymer (A) in the composition of the present invention is not particularly limited, but is usually 2 to 50% by mass, preferably 4 to 25% by mass, based on the solid content of the composition of the present invention. When the content of the copolymer (A) is 4% by mass to 25% by mass, an appropriate coating film dissolution rate and coating film physical characteristics in seawater can be obtained, and stable surface renewability can be maintained for a long period of time. The desired antifouling effect can be effectively exhibited. In addition, excellent recoating performance of the coating film can be exhibited.

<siloxane compound (B)>
The siloxane compound (B) of the present invention is a siloxane compound having an alkoxy group having 1 to 4 carbon atoms and a siloxane skeleton, and the number of Si atoms in the siloxane skeleton is 5 to 100. Specifically, the number of Si atoms of the siloxane compound (B) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85. , 90, 95, 100, and may be within the range between any two of the numerical values exemplified here. It is preferable that at least one alkoxy group having 1 to 4 carbon atoms is bonded to each Si in the siloxane skeleton.

Each Si in the siloxane skeleton has a plurality of substituents (terminal Si has 3 substituents, and other Si has 2 substituents). It is preferable that all of these plurality of substituents are alkoxy groups having 1 to 4 carbon atoms. Two of these plurality of substituents may be an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkoxy group having 1 to 4 carbon atoms. The siloxane skeleton may be linear, branched or cyclic. The siloxane compound (B) may contain one type of compound having a linear, branched chain, or cyclic siloxane skeleton, or may be a mixture containing a plurality of types.

Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy group and the like, and methoxy and ethoxy groups are preferable. Further, it is preferably an ethoxy group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl and the like, and methyl and ethyl are preferable. It is a group.

（式中、Ｒ^５は、それぞれ同一又は異なって、炭素数が１〜４のアルキル基であり、Ｒ^６は、それぞれ同一又は異なって、炭素数が１〜６のアルキル基、フェニル基、または炭素数が１〜４のアルコキシ基であり、ｎは５〜１００である）で表される。The siloxane compound (B) may contain a compound represented by the following general formula (2).
The following general formula (2):

(In the formula, R ⁵ is the same or different alkyl group having 1 to 4 carbon atoms, and R ⁶ is the same or different alkyl group having 1 to 6 carbon atoms, respectively. It is an alkoxy group having 1 to 4 carbon atoms, and n is 5 to 100).

The R ^5, include methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, and t- butyl group, preferably methyl, ethyl. More preferably, it is an ethyl group.
R ⁶ includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, phenyl group, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy. , T-Butoxy group and the like, preferably methyl, ethyl, phenyl, methoxy and ethoxy groups.

The siloxane compound (B) of the present invention may be produced, for example, by partially hydrolyzing and condensing an organosilicate, or a commercially available product may be used.
Specific examples of organosilicates include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetraisobutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, and methyl. Tripropoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, methyltriisobutoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, phenyltrin-butoxysilane, Trifunctional silanes such as phenyltriisobutoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, dimethyldin-butoxysilane, dimethyldiisobutoxysilane Examples thereof include bifunctional silanes such as silane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, diphenyldin-butoxysilane, diphenyldiisobutoxysilane, dihexyldimethoxysilane, and dihexyldiethoxysilane. .. One or a combination of two or more of these tetrafunctional, trifunctional or bifunctional silanes can be used.

Examples of commercially available products of the siloxane compound (B) include MKC silicate MS56, MKC silicate MS57, MKC silicate MS56S (all manufactured by Mitsubishi Chemical Corporation, trade names), methyl silicate 53A, ethyl silicate 40, and ethyl silicate. 48, EMS-485, SS-101 (all manufactured by Corcote Co., Ltd., product name), Silicone 40, Silicone 45 (manufactured by Tama Chemical Industry Co., Ltd., product name) KR-515, KR-500, KR -401N, KR-510 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade name), TES40WN (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and the like can be mentioned.

The method of blending the siloxane compound (B) of the present invention into the coating composition is not particularly limited, and may be blended at the time of the coating dispersion step or at the final step. Alternatively, it may be added to the paint and mixed immediately before painting.

The siloxane compound (B) of the present invention is contained in an amount of 0.2 to 5% by mass, particularly preferably 0.5 to 2% by mass, in the solid content of the composition of the present invention. When the content of the siloxane compound (B) is within the above range, the effect of promoting the dissolution rate of the coating film at the initial stage (pre-seawater immersion stage) is remarkable, and the antifouling coating film after being immersed in seawater for a certain period of time No coating film abnormality (cracks, etc.) occurs.

When the content ratio of the copolymer (A) and the siloxane compound (B) is a mass ratio (the copolymer (A) / the condensate (B)) of 1 to 75 in terms of solid content, The effect of accelerating the dissolution rate of the coating film in the initial stage (pre-immersion in seawater) is remarkably exhibited, and when the content ratio is 2.5 to 30, the effect is further exhibited.

In addition to the copolymer (A) and the siloxane compound (B), the antifouling coating composition in the present invention includes an antifouling agent (C), an elution adjuster (D), and a plasticizer (E), if necessary. ), Other resin (F) and the like can be blended. As a result, a more excellent antifouling effect can be exhibited.

<Anti-fouling agent (C)>
The antifouling agent (C) is not particularly limited as long as it is a substance having a killing or repellent action against marine polluted organisms. For example, inorganic agents and organic agents can be mentioned.
Examples of the inorganic drug include cuprous oxide, copper thiocyanate (generic name: copper rodan), cupronickel, copper powder and the like. Of these, cuprous oxide and copper rodane are particularly preferable.
Examples of the organic drug include organic copper compounds such as 2-mercaptopyridin-N-copperpyridion (generic name: copperpyrthione), 2-mercaptopyridin-N-zinc oxide (generic name: zincpyrythion), and zincethylenebisdithiocarbamate. Organic zinc compounds such as (generic name: dineb), bis (dimethyldithiocarbamic acid) zinc (generic name: dilam), bis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate) dizinc (generic name: polycarbamate); Organic boron compounds such as triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, 4-phenylpyridyl-diphenylborane, triphenylboron-n-octadecylamine, triphenyl [3- (2-ethylhexyloxy) propylamine] boron Maleimide compounds such as 2,4,6-trichloromaleimide, N- (2,6 diethylphenyl) 2,3-dichloromaleimide; Others, 4,5-dichloro-2-n-octyl-3-isothiazolone (general) Name: Sea Nine 211), 3,4-dichlorophenyl-N-N-dimethylurea (generic name: diuron), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine (generic name: irgalol) 1051), 2,4,5,6-tetrachloroisophthalonitrile (generic name: chlorotalonyl), N-dichlorofluoromethylthio-N', N'-dimethyl-N-p-tolyl sulfamide (generic name: trifluanide) ), N-dichloromethylthio-N', N'-dimethyl-N-phenylsulfamide (generic name: diclofluanide), 2- (4-thiazolyl) benzimidazole (generic name: thiabendazole), 3- (Benzo [b] thien-2-yl) -5,6-dihydro-1,4,2-oxathiazine-4-oxide (generic name: betaxazine), 2- (p-chlorophenyl) -3-cyano-4-bromo- Examples thereof include 5-trifluoromethylpyrrole (generic name: ECONEA 028). Of these, zinc pyrithione, copper pyrithione, pyridine-triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dineb, sinine 211 and irgalol 1051 are preferred, with copper pyrithione, zinc pyrithione, pyridine-triphenylborane and betoxazine being more preferred. preferable.

Antifouling agents (C) include cuprous oxide, copper rodane, zinc pyrithione, copper pyrithione, pyridine-triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dineb, cinine 211 and irgalol 1051, trifluanide, diclofluani. Copper oxide, copper pyrithione, zinc pyrithione, pyridine / triphenylborane and betoxazine are more preferable.
These antifouling agents can be used alone or in combination of two or more.
The content of the antifouling agent (C) in the composition of the present invention is not particularly limited, but is usually 0.1 to 75% by mass, preferably 1 to 60% by mass in the solid content of the composition of the present invention. be. If the content of the antifouling agent (C) is less than 0.1% by mass, a sufficient antifouling effect may not be obtained. When the content of the antifouling agent (C) exceeds 75% by mass, the coating film to be formed is fragile, and the adhesiveness to the coating film to be formed is also weak, so that the function as an antifouling coating film is sufficient. I can't do it.

<Elution adjuster (D)>
Examples of the elution adjuster (D) include rosin, rosin derivatives and metal salts thereof, monocarboxylic acids and salts thereof, alicyclic hydrocarbon resins and the like.
Examples of the rosin include tall oil rosin, gum rosin, and wood rosin. Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin. As the metal salt of rosin and the metal salt of the rosin derivative, a reaction product of the metal compound and rosin can be used, and as the metal salt of rosin, for example, gum rosin zinc (or copper) salt, wood rosin zinc (or copper) salt, etc. Tall oil rosin zinc (or copper) salt and the like can be mentioned. Examples of the metal salt of the rosin derivative include hydrogenated rosin zinc (or copper) salt, disproportionated rosin zinc (or copper) salt, maleated rosin zinc (or copper) salt, formylated rosin zinc (or copper) salt, and polymerization. Examples include rosin zinc (or copper) salts.
Examples of the monocarboxylic acid include fatty acids having about 5 to 30 carbon atoms, synthetic fatty acids, naphthenic acid and the like. Examples of the monocarboxylic acid salt include copper salt, zinc salt, magnesium salt, calcium salt and the like.
Examples of the commercially available alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Corporation) and the like.

In particular, the composition of the present invention is selected from the group consisting of rosin, rosin derivatives and metal salts thereof at least in that it can impart an appropriate elution-promoting property to the composition of the present invention as the elution adjuster (D). It is preferable to contain one kind, and it is particularly preferable to contain a copper salt or zinc salt of rosin or a rosin derivative from the viewpoint of improving crack resistance and water resistance.

The content of the elution adjuster (D) in the composition of the present invention is usually 1 to 80 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the copolymer (A). When the amount of the elution adjusting agent (D) is less than 1 part by mass, the effect of preventing the adhesion of aquatic fouling organisms, particularly the effect of preventing the adhesion of aquatic fouling organisms during the dressing period can not be expected so much. If the content of the elution adjusting agent (D) exceeds 80 parts by mass, defects such as cracks and peeling are likely to occur in the coating film, and the effect of preventing aquatic pollution and biofouling may not be sufficiently exhibited. The content of the elution adjuster (D) is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 with respect to 100 parts by mass of the copolymer (A). , 60, 65, 70, 75, 80 parts by mass, and may be within the range of any two numerical values exemplified here.

<Plasticizer (E)>
By including the plasticizer (E) in the antifouling coating composition of the present invention, the plasticity of the composition can be improved, and as a result, a tough coating film can be suitably formed.
Examples of the plasticizer (E) include phosphoric acid esthetics such as tricresyl phosphate, trioctyl phosphate and triphenyl phosphate, phthalates such as dibutyl phthalate and dioctyl phthalate, dibutyl adipate and dioctyl adipate. Adipanoic acid esters, sebacic acid esters such as dibutyl sebacate and dioctyl sebacate, epoxidized fats and oils such as epoxidized soybean oil and epoxidized flaxseed oil, alkyl vinyl ether weights such as methyl vinyl ether polymer and ethyl vinyl ether polymer. Examples thereof include polymers, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, t-nonylpentasulfide, vaseline, polybutene, tris trimellitic acid (2-ethylhexyl), liquid paraffin, chlorinated paraffin and the like. These can be used alone or in combination of two or more.
The content of the plasticizer (E) in the composition of the present invention is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A).

<Other resin (F)>
By incorporating another resin (F) in the antifouling coating composition of the present invention, it is possible to reduce costs without impairing the effects of the present invention, and a synergistic effect with the physical properties of the resin (F). Can be obtained.
Examples of the other resin (F) include (meth) acrylic resin, alkyd resin, polyester resin, rubber chloride resin, vinyl resin and the like.
The other resin (F) in the composition of the present invention can be contained within a range in which an appropriate coating film dissolution rate in seawater and the physical characteristics of the coating film are not impaired, and the content thereof is a copolymer ( A) 1 to 200 parts by mass, preferably 20 to 100 parts by mass with respect to 100 parts by mass.

<Other additives>
Further, in the antifouling coating composition of the present invention, if necessary, a pigment, a dye, an antifoaming agent, a sagging agent, a dispersant, a settling inhibitor, a dehydrating agent, an organic solvent and the like are appropriately added in seawater. It can be added within a range in which the dissolution rate of the coating film and the physical properties of the coating film are not impaired.

Method for Producing Antifouling Coating Composition The antifouling coating composition of the present invention can be obtained, for example, by mixing and dispersing a mixed solution containing the siloxysan compound (B) using a disperser, or by mixing and dispersing the siloxane compound (B). It can be produced by mixing and dispersing a mixed solution containing other than the above using a disperser, and then adding and mixing the siloxane compound (B) in the final step. Alternatively, it may be produced by adding and mixing the siloxysan compound (B) immediately before painting.
The contents of the copolymer (A), the siloxane compound (B), etc. in the mixed solution are the contents of the copolymer (A), the siloxane compound (B), etc. in the antifouling coating composition, and the contents, respectively. It may be adjusted appropriately so as to have a content ratio.
As the disperser, for example, one that can be used as a fine pulverizer can be preferably used. For example, a commercially available homomixer, sand mill, bead mill or the like can be used. Further, the mixed liquid may be mixed and dispersed by using a container provided with a stirrer to which glass beads or the like for mixing and dispersing are added.

Antifouling treatment method, antifouling coating film, and coated material In the antifouling treatment method of the present invention, an antifouling coating film is formed on the surface of the coating film to be formed using the above antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is gradually dissolved from the surface and the surface of the coating film is constantly updated, so that adhesion of aquatic polluted organisms can be prevented. Further, by overcoating the above composition after dissolving the coating film, the antifouling effect can be continuously exhibited.
Examples of the coating film-forming product include ships (particularly the bottom of ships), fishing gear, and underwater structures. Examples of fishing nets include fishing nets for aquaculture or stationary fishing nets, floats used for the fishing nets, fishing net accessories such as ropes, and the like. Examples of underwater structures include power plant water pipes, bridges, harbor facilities, and the like.
The antifouling coating film can be formed by applying the antifouling coating composition to the surface (whole or part) of the coating film to be formed.
Examples of the coating method include a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method and the like. These may be performed alone or in combination of two or more.
After application, dry. The drying temperature may be room temperature. The drying time may be appropriately set according to the thickness of the coating film and the like.
The antifouling coating film of the present invention formed by using the above antifouling coating composition exhibits an appropriate coating film dissolution rate and coating film physical characteristics in seawater, and can maintain stable surface renewal property for a long period of time. , The desired antifouling effect can be effectively exhibited. Further, it has an advantage that excellent recoating performance of the coating film can be exhibited.
The thickness of the antifouling coating film may be appropriately set according to the type of the coating film to be formed, the navigation speed of the ship, the seawater temperature, and the like. For example, when the coating film to be formed is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 500 μm, preferably 100 to 400 μm.
The antifouling coating film of the present invention has an appropriate hardness. That is, the antifouling coating film of the present invention has a hardness sufficient to prevent coating film abnormalities such as cold flow.
The coated material of the present invention has the antifouling coating film on its surface. The coated material of the present invention may have the antifouling coating film on the entire surface or a part thereof.
Since the coating film of the present invention has a coating film excellent in long-term stable surface renewal property and recoating property by improving an appropriate coating film dissolution rate and coating film physical characteristics in seawater, the above-mentioned ship ( In particular, it can be suitably used as a ship bottom), fishing equipment, underwater structures, and the like.
For example, when the antifouling coating film is formed on the bottom surface of a ship, the antifouling coating film is gradually dissolved from the surface and the coating film surface is constantly updated to prevent the adhesion of aquatic polluted organisms. can.
Moreover, the hydrolysis rate of the antifouling coating film is preferably suppressed. Therefore, the ship can maintain its antifouling performance for a long period of time, and for example, even in a stationary state such as during a mooring period or a dressing period, there is almost no adhesion or accumulation of aquatic polluted organisms, and the antifouling effect can be exhibited for a long period of time.
Further, even after a long period of time, the antifouling coating film on the surface basically does not crack or peel. Therefore, it is not necessary to perform work such as forming a coating film again after completely removing the coating film. Therefore, the antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. This makes it possible to maintain continuous antifouling performance easily and at low cost.

Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to these examples.
% In each production example, comparative production example, example and comparative example indicates mass%. The viscosity is a value measured at 25 ° C. and is a value obtained by a B-type viscometer. The weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC. The conditions for GPC are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column ・ ・ ・ TSKgel SuperHZM-M (manufactured by Tosoh Corporation) 2 Flow rate ・ ・ ・ 0.35 mL / min
Detector ・ ・ ・ RI
Column constant temperature bath temperature ・ ・ ・ 40 ℃
Eluent ・ ・ ・ THF
The heating residue is a value obtained by heating at 125 ° C. for 1 hour.
The unit of the blending amount of each component in Table 1 is g.

Production Example 1 (Production of copolymer solution A-1)
200 g of xylene was placed in a flask equipped with a thermometer, a reflux cooler, a stirrer and a dropping funnel, and while stirring at 85 ± 5 ° C. under a nitrogen atmosphere, 270 g of triisopropylsilyl methacrylate, 120 g of methyl methacrylate, and acrylic acid. A mixture of 20 g of 2-methoxyethyl, 20 g of n-butyl acrylate, 70 g of i-butyl methacrylate, and 6 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate over 2 hours. Dropped. After that, the mixture was stirred at the same temperature for 1 hour, and then 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times every hour to complete the polymerization reaction. By adding and dissolving 300 g of xylene, a triorganosilyl ester-containing copolymer solution A-1 was obtained. The viscosity of the obtained copolymer solution was 450 cps / 25 ° C., the heating residue was 49.8%, and Mw was 51,000.

Production Example 2 (Production of copolymer solution A-2)
170 g of xylene was placed in a flask equipped with a thermometer, a reflux cooler, a stirrer and a dropping funnel, and while stirring at 85 ± 5 ° C. under a nitrogen atmosphere, 300 g of triisopropylsilyl atacrylate, 130 g of methyl methacrylate, and mecrylic acid were added. A mixture of 20 g of 2-methoxyethyl, 20 g of n-butyl acrylate, 30 g of i-butyl methacrylate, and 4 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate over 2 hours. Dropped. After that, the mixture was stirred at the same temperature for 1 hour, and then 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times every hour to complete the polymerization reaction. By adding and dissolving 330 g of xylene, a triorganosilyl ester-containing copolymer solution A-2 was obtained. The viscosity of the obtained copolymer solution was 490 cps / 25 ° C., the heating residue was 50.5%, and Mw was 49,500.

Production Example 3 (Production of copolymer solution A-3)
200 g of xylene was placed in a flask equipped with a thermometer, a reflux cooler, a stirrer and a dropping funnel, and while stirring at 85 ± 5 ° C. under a nitrogen atmosphere, 270 g of triisopropylsilyl methacrylate, 160 g of methyl methacrylate, and acrylic acid. A mixed solution of 20 g of n-butyl, 50 g of n-butyl methacrylate, and 6 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added dropwise over 2 hours. After that, the mixture was stirred at the same temperature for 1 hour, and then 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times every hour to complete the polymerization reaction. By adding and dissolving 300 g of xylene, a triorganosilyl ester-containing copolymer solution A-3 was obtained. The viscosity of the obtained copolymer solution was 440 cps / 25 ° C., the heating residue was 50.3%, and Mw was 50,500.

Production Example 4 (Production of copolymer solution A-4)
350 g of xylene was placed in a flask equipped with a thermometer, a reflux cooler, a stirrer and a dropping funnel, and while stirring at 85 ± 5 ° C. under a nitrogen atmosphere, 100 g of triisopropylsilyl methacrylate, 75 g of methyl methacrylate, and acrylic acid. 2-Methoxyethyl 50 g, n-butyl acrylate 100 g, i-butyl methacrylate 100 g, 2-methoxyethyl mecrylate 75 g, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate 5 g The mixed solution of the above was added dropwise over 2 hours. After that, the mixture was stirred at the same temperature for 1 hour, and then 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times every hour to complete the polymerization reaction. By adding and dissolving 150 g of xylene, a triorganosilyl ester-containing copolymer solution A-4 was obtained. The viscosity of the obtained copolymer solution was 380 cps / 25 ° C., the heating residue was 49.5%, and Mw was 48,000.

Examples 1 to 6 and Comparative Examples 1 to 7 (manufacturing of a coating composition)
A coating composition was produced by blending the components shown in Table 1 at the ratio (mass%) shown in Table 1 and mixing and dispersing them with glass beads having a diameter of 1.5 to 2.5 mm. Details of each component in Table 1 are as follows.

Gumrosin zinc salt solution: Use the one produced in Production Example 5 Gumrosin solution: Solid content of Chinese gumrosin (WW) Approximately 60% xylene solution Copper oxide: Trade name "NC-301" (manufactured by Nissin Chemco Co., Ltd.)
Copper Pyrithione: Product name "Copper Omagin" (manufactured by Arch Chemical Co., Ltd.)
Bengala: Product name "TODA COLOR EP-13D" (manufactured by Toda Pigment Co., Ltd.)
Talc: Product name "Crown Talc 3S" (manufactured by Matsumura Sangyo Co., Ltd.)
Zinc oxide: Product name "Zinc oxide 2 types" (manufactured by Shodo Kagaku Co., Ltd.)
Titanium oxide: Product name "FR-41" (manufactured by Furukawa Co., Ltd.)
Fatty acid amide-based shaker: Product name "Disparon A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.)
Siloxane compound (B):
Product name "Ethyl silicate 40" (manufactured by Corcote Co., Ltd.)
Product name "Ethyl silicate 48" (manufactured by Corcote Co., Ltd.)
Product name "MKC Silicate MS56" (Mitsubishi Chemical Corporation)
Tetraethoxysilane: manufactured by Kishida Chemical Co., Ltd., special grade reagent Tetramethoxysilane: manufactured by Kishida Chemical Co., Ltd., special grade reagent methyl silicate 51 (tetramer): manufactured by Corcote Co., Ltd.

Production Example 5 (Production of Gamrosin Zinc Salt Solution)
In a 1 L flask equipped with a temperature system, a reflux condenser and a stirrer, 240 g of Chinese gum rosin (WW) and 240 g of xylene are placed in the flask, and zinc oxide is further formed so that all the resin acids in the gum rosin form zinc salts. 120 g was added, and the mixture was reflux-dehydrated at 70-80 ° C. for 3 hours under reduced pressure. Then, it was cooled and filtered to obtain a xylene solution (dark brown transparent liquid, solid content of about 60%) of gum rosin zinc salt. The heating residue of the obtained xylene solution was 60.6%.

Test Example 1 (Rotary test)
A rotating drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of seawater constant and an automatic pH controller for keeping the pH of seawater constant were installed.
A test plate was prepared according to the following method.
First, a rust preventive paint (epoxy vinyl A / C) is applied onto a titanium plate (75 x 150 x 0.5 mm) so that the thickness after drying is about 100 μm, and the rust preventive coating is formed by drying. bottom. Then, the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 7 were each applied onto the rust-preventive coating film so that the thickness after drying was about 300 μm. The obtained coating material was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 μm.
One of the produced test plates was fixed to the rotating drum of the rotating device of the above device so as to come into contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During that time, the temperature of the seawater was kept at 25 ° C. and the pH was maintained at 8.0 to 8.2, and the seawater was replaced every week.
The amount of dissolved coating film per month (μm / month) was measured by measuring the initial film thickness of each test plate and the residual film thickness every 3 months after the start of the test with a laser focus displacement meter, and calculating the thickness of the dissolved coating film from the difference. ) Was obtained. The measurement was carried out for 24 months, and the amount of the coating film dissolved was calculated every 6 months.
Further, after the test plate after the completion of the rotary test (24 months later) was dried, the surface of each coating film was visually observed to evaluate the state of the coating film.
The evaluation was performed by the following method.
⊚: When there is no abnormality ○: Slight hair cracks are seen △: Hair cracks are seen on the entire surface of the coating film ×: Large cracks, blister or peeling, etc.

Test Example 2 (Anti-fouling test)
The coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 7 were applied to both sides of a hard vinyl chloride plate (100 × 200 × 2 mm) so that the thickness of the dry coating film was about 200 μm. The obtained coating material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 μm. This test plate was immersed 1.5 m below the sea surface in Owase City, Mie Prefecture, and stains on the test plate due to deposits were observed 12 months and 24 months later.
The evaluation was performed by visually observing the state of the coating film surface, and judged according to the following criteria.
◎: No attachment of polluted organisms such as shellfish and algae, and almost no slime.
◯: A level at which there is no attachment of polluted organisms such as shellfish and algae, and slime is thinly attached (to the extent that the coating film surface can be seen), but it can be lightly wiped off with a brush.
Δ: There is no adhesion of polluted organisms such as shellfish and algae, but the slime is so thick that the coating film surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush.
×: Level at which polluted organisms such as shellfish and algae are attached

The results are shown in Table 1.
From Table 1, the coating film formed by using the coating composition of the present invention (Examples 1 to 6) is more in seawater than the coating film formed by using the coating composition of Comparative Examples 1 to 7. The amount of dissolution was maintained high during all periods, and the state of the dry coating film after the end of the rotary test (24 months later) was generally good without causing large cracks, and even in the antifouling test, shellfish and algae It can be seen that there is no adhesion of polluted organisms such as, and there is almost no adhesion of slime.
On the other hand, the coating films formed using the coating compositions of Comparative Examples 1 to 7 have a low dissolution amount in seawater as a whole, or the dissolution amount disappears after the latter half, resulting in the result. In some cases, cracks occur in the coating film, and in antifouling tests, it is not possible to prevent the adhesion of polluted organisms over a long period of time, and the performance of each is not balanced.

Claims (3)

(A) (a) General formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ each represent the same or different alkyl group or phenyl group in which the α-position having 3 to 6 carbon atoms is branched. ), And the (meth) acrylic acid triorganosilyl ester monomer.
(B) A triorganosilyl ester-containing copolymer obtained from a mixture of the (meth) acrylic acid triorganosilyl ester monomer and a copolymerizable ethylenically unsaturated monomer, and (B) a siloxane skeleton. Yes and, and the siloxane compound carbon number Si atoms that are bonded alkoxy groups having 1 to 4 in the siloxane skeleton (provided that the number of Si atoms in the siloxane backbone 5-100)
Antifouling paint composition containing. The antifouling coating composition according to claim 1, wherein the siloxane compound contains a compound represented by the following general formula (2).
General formula (2):

(In the formula, R ⁵ is the same or different alkyl group having 1 to 4 carbon atoms, and R ⁶ is the same or different alkyl group having 1 to 6 carbon atoms, respectively. It is an alkoxy group having 1 to 4 carbon atoms, and n is 5 to 100). A coating having an antifouling coating film formed by using the antifouling coating composition according to claim 1 or 2, on the surface thereof.