JPH1161002A5

JPH1161002A5 -

Info

Publication number: JPH1161002A5
Application number: JP1997231445A
Authority: JP
Filing date: 1997-08-27
Publication date: 2004-12-16
Anticipated expiration: 2017-08-27

Description

【００１２】
【発明の概要】
本発明に係る非錫系防汚塗料組成物は、(a)非錫系塗膜形成樹脂成分と、(b)エチレン・酢酸ビニル共重合体の塩素化物または該共重合体の部分加水分解物の塩素化物と、(c)防汚剤とを含有することを特徴としている。
［但し、（ａ）（メタ）アクリル酸金属塩系共重合体、（ｉｉ）下記式［ I ］で表されるトリフェニルボロン・アミン錯体またはピリジントリフェニルボロン、及び（ｉｉｉ）無機脱水剤としての無水石膏を含有する防汚塗料組成物、及び
（ａ）（メタ）アクリル酸金属塩系共重合体、（ｉｉ）下記式［ I ］で表されるトリフ
ェニルボロン・アミン錯体またはピリジントリフェニルボロン、及び（ｉｖ）金属ピリチオンおよび４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オンからなる群から選択される何れか 1 種以上の有機防汚剤を含有する防汚塗料組成物を除く。
【化２】
｛式［ I ］中、Ｒ ¹ は、炭素数３〜３０のアルキル基を示す。｝。］。 [0012]
Summary of the Invention
The tin-free antifouling coating composition according to the present invention is characterized by containing (a) a tin-free film-forming resin component, (b) a chlorinated ethylene-vinyl acetate copolymer or a chlorinated partial hydrolyzate of said copolymer, and (c) an antifouling agent.
[However, the present invention provides an antifouling coating composition containing (a) a (meth)acrylic acid metal salt copolymer, (ii) a triphenylboron-amine complex represented by the following formula [ I ] or pyridinetriphenylboron, and (iii) anhydrous gypsum as an inorganic dehydrating agent, and
(a) a (meth)acrylic acid metal salt copolymer, (ii) a trifluoromethyl-2-(2-methyl-2-propanol) represented by the following formula [ I ]:
and (iv) any one or more organic antifouling agents selected from the group consisting of metal pyrithione and 4,5-dichloro-2-n-octyl-4-isothiazolin-3- one .
[Chemical 2]
{ In formula [ I ], ^R1 represents an alkyl group having 3 to 30 carbon atoms.}.

【００１４】
本発明の非錫系防汚塗料組成物には、防汚剤として、Ｎ，Ｎ−ジメチルジクロロフェニル尿素、２，４，６−トリクロロフェニルマレイミド、２-メチルチオ-４-ｔ-ブチルアミノ-６-シクロプロピルアミノＳトリアジン、４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オン、２，４，５，６−テトラクロロイソフタロニトリル、２-ピリジンチオール-１-オキシド亜鉛塩、２-ピリジンチオール-１-オキシド銅塩のうちの何れか１種以上と、亜酸化銅とが組み合わせて含有されているか、あるいは上記防汚剤として、ピリジン−トリフェニルボラン、２-ピリジンチオール-１-オキシド亜鉛塩のうちの何れか１種以上と、ロダン銅とが組み合わせて含有されていることが好ましい。[0014]
The tin-free antifouling coating composition of the present invention preferably contains, as an antifouling agent, a combination of cuprous oxide and one or more of N,N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2 -methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine, 4,5-dichloro-2-n-octyl-isothiazolin-3-one , 2,4,5,6-tetrachloroisophthalonitrile, 2-pyridinethiol-1-oxide zinc salt, and 2-pyridinethiol-1-oxide copper salt, or a combination of pyridine-triphenylborane and 2-pyridinethiol-1-oxide zinc salt and copper rhodanide as the antifouling agent.

【００５４】
、テトラメチルチウラムジサルファイド、カーバメート系の毒物（例：ジンクジメチルジチオカーバメート、マンガン-２-エチレンビスジチオカーバメート）、２，４，５，６−テトラクロロイソフタロニトリル、Ｎ，Ｎ−ジメチルジクロロフェニル尿素、４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オン、２，４，６−トリクロロフェニルマレイミド、ピリジン−トリフェニルボラン（商品名「ＰＫボロン」）、２、２-メチルチオ-４-ｔ-ブチルアミノ-６-シクロプロピルアミノＳトリアジン（商品名「イルガロール１０５１」）等を挙げることができる。[0054]
, tetramethylthiuram disulfide, carbamate-based poisons (e.g., zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyldichlorophenylurea, 4,5-dichloro-2-n-octyl-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, pyridine-triphenylborane (trade name "PK Boron"), 2,2-methylthio-4-t-butylamino-6-cyclopropylamino S-triazine (trade name "Irgarol 1051"), etc.

【００５６】
特に、これらの防汚剤の中でも好ましく用いられる亜酸化銅は、それ以外の防汚剤と組み合わせて用いることが好ましく、このように亜酸化銅と併用することが好ましい防汚剤としては、Ｎ，Ｎ−ジメチルジクロロフェニル尿素（商品名「ＤＣＭＵ」）、２，４，６−トリクロロフェニルマレイミド（商品名「ＩＴ３５４」）、２-メチルチオ-４-ｔ-ブチルアミノ-６-シクロプロピルアミノＳトリアジン（商品名「イルガロール１０５１」）、４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オン（商品名「ケーソン９３０」）、２，４，５，６−テトラクロロイソフタロニトリル（商品名「Ｎ-９６」）、
２-ピリジンチオール-１-オキシド亜鉛塩（商品名「ジンクピリチオン、ＺＰＴ」）、２-ピリジンチオール-１-オキシド銅塩（ＣｕＰＴ）等が挙げられる。[0056]
In particular, cuprous oxide, which is preferably used among these antifouling agents, is preferably used in combination with other antifouling agents. Examples of antifouling agents that are preferably used in combination with cuprous oxide include N,N-dimethyldichlorophenylurea (trade name "DCMU"), 2,4,6-trichlorophenylmaleimide (trade name "IT354"), 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine (trade name "Irgarol 1051"), 4,5-dichloro-2-n-octyl-isothiazolin-3-one (trade name "Cason 930"), 2,4,5,6-tetrachloroisophthalonitrile (trade name "N-96"),
Examples include 2-pyridinethiol-1-oxide zinc salt (trade name "zinc pyrithione, ZPT") and 2-pyridinethiol-1-oxide copper salt (CuPT).

【００７９】
【実施例Ａ１】
下記表２に示す防汚塗料組成物を常法に従って以下のようにして調製した。すなわち、塩素化エチレン酢酸ビニル共重合樹脂［日本製紙社製：商品名「スーパークロンＢ」、塩素化率約２６．５％、分子量約２５万、固形分（加熱残分）２０％］７．５重量部、ロジンＷＷ（固形分１００％）１０重量部、塩化ビニル・ビニルイソブチルエーテル共重合体［ＢＡＳＦ社製：ラロフレックスＭＰ-１５、固形分１００％］５重量部、酸化亜鉛５重量部、フタロシアニンブルー２．５重量部、チタン白５重量部、亜酸化銅４０重量部、２，４，５，６-テトラクロロイソフタロニトリル［サンノプコ社製：商品名「ノプコサイドＮ-９６」、固形分１００％］３重量部、４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オン［ロームアンドハース社製：商品名「ケーソン９３０」、固形分３０％］３．５重量部、酸化ポリエチレンワックス［楠本化成社製：商品名「ディスパロン４２００-２０」、固形分２０％］３重量部、ポリアマイドワックス［楠本化成社製：ディスパロンＡ６３０-２０Ｘ、固形分２０％］３重量部、エポキシ樹脂［大竹化学社製：Ｅ−０２８−９０Ｘ、分子量約３８０、固形分９０％］３重量部、キシレン７．２重量部、トルエン２重量部、メチルイソブチルケトン（MIBK）３重量部を、ペイントコンディショナーを用いて混練分散を行い防汚塗料組成物を得た。[0079]
Example A1
The antifouling coating compositions shown in Table 2 below were prepared according to a conventional method as follows: 7.5 parts by weight of chlorinated ethylene vinyl acetate copolymer resin [manufactured by Nippon Paper Industries Co., Ltd.: trade name "Superchlor B", chlorination rate approximately 26.5%, molecular weight approximately 250,000, solid content (heating residue) 20%], 10 parts by weight of rosin WW (solid content 100%), 5 parts by weight of vinyl chloride/vinyl isobutyl ether copolymer [manufactured by BASF: Laloflex MP-15, solid content 100%], 5 parts by weight of zinc oxide, 2.5 parts by weight of phthalocyanine blue, 5 parts by weight of titanium white, 40 parts by weight of cuprous oxide, 3 parts by weight of 2,4,5,6-tetrachloroisophthalonitrile [manufactured by San Nopco Ltd.: trade name "Nopcoside N-96", solid content 100%], An antifouling coating composition was obtained by kneading and dispersing 3.5 parts by weight of 4,5-dichloro-2-n-octyl-isothiazolin-3-one (manufactured by Rohm and Haas Company: trade name "Caisson 930", solids content 30%), 3 parts by weight of oxidized polyethylene wax (manufactured by Kusumoto Chemicals Co., Ltd.: trade name "Disparlon 4200-20", solids content 20%), 3 parts by weight of polyamide wax (manufactured by Kusumoto Chemicals Co., Ltd.: Disparlon A630-20X, solids content 20%), 3 parts by weight of epoxy resin (manufactured by Ohtake Chemicals Co., Ltd.: E-028-90X, molecular weight approximately 380, solids content 90%), 7.2 parts by weight of xylene, 2 parts by weight of toluene, and 3 parts by weight of methyl isobutyl ketone (MIBK) using a paint conditioner.

【０１０２】
(11)４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オン：ケーソン９３０、固形分３０％、ロームアンドハース社製、防汚剤。
(12)ピリジントリフェニルボラン：ＰＫボロン、北興化学社製、防汚剤。[0102]
(11) 4,5-dichloro-2-n-octyl-isothiazolin-3-one : Caison 930, 30% solids, manufactured by Rohm and Haas, antifouling agent.
(12) Pyridinetriphenylborane: PK Boron, manufactured by Hokko Chemical Co., Ltd., antifouling agent.

【０１０６】
【表２】
[0106]
[Table 2]

【０１０７】
【表３】
[0107]
[Table 3]

【０１１０】
【表４】
[0110]
[Table 4]

【０１１１】
【表５】
[0111]
[Table 5]

Claims

A non-tin-based antifouling coating composition comprising (a) a non-tin-based film-forming resin component, (b) a chlorinated ethylene-vinyl acetate copolymer or a chlorinated partial hydrolyzate of said copolymer, and (c) an antifouling agent (however, excluding antifouling coating compositions containing (a) a (meth)acrylic acid metal salt-based copolymer, (ii) a triphenylboron-amine complex represented by the following formula [ I ] or pyridinetriphenylboron, and (iii) anhydrous gypsum as an inorganic dehydrating agent, and antifouling coating compositions containing (a) a (meth)acrylic acid metal salt-based copolymer, (ii) a triphenylboron-amine complex represented by the following formula [ I ] or pyridinetriphenylboron, and (iv) any one or more organic antifouling agents selected from the group consisting of metal pyrithione and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one ) :
{ In formula [ I ], ^R1 represents an alkyl group having 3 to 30 carbon atoms.}.

2. The non-tin-based antifouling coating composition according to claim 1, wherein the non-tin-based film-forming resin component (a) is any one of (i) a combination of a vinyl chloride copolymer resin and a water-soluble resin, (ii) a combination of an acrylic resin and a water-soluble resin, (iii) an acrylic zinc polymer, and (iv) a silyl acrylate resin.

3. The tin-free antifouling coating composition according to claim 2, wherein the water-soluble resin is rosin.

4. The tin-free antifouling coating composition according to claim 1, wherein the antifouling agent comprises one or more of N,N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2 -methylthio-4-t- butylamino-6-cyclopropylamino-S-triazine, 4,5-dichloro-2-n-octyl-isothiazolin-3-one, 2,4,5,6-tetrachloroisophthalonitrile, 2-pyridinethiol-1-oxide zinc salt, and 2-pyridinethiol-1-oxide copper salt, and cuprous oxide.

4. A tin-free antifouling coating composition according to claim 1, characterized in that the antifouling agent contains at least one of pyridine-triphenylborane and 2-pyridinethiol-1-oxide zinc salt, and copper rhodanide.

An antifouling coating film formed from the tin-free antifouling coating composition according to any one of claims 1 to 5.

6. A method for antifouling a ship's outer panel, comprising applying a tin-free antifouling paint composition according to any one of claims 1 to 5 to a surface of the ship's outer panel that comes into contact with seawater, to form an antifouling coating film.

A ship, characterized in that the surface of a ship's outer plate that comes into contact with seawater is coated with an antifouling coating film obtained by applying and curing the tin-free antifouling coating composition according to any one of claims 1 to 5.