JPH05186715A - Antifouling coating composition - Google Patents
Antifouling coating compositionInfo
- Publication number
- JPH05186715A JPH05186715A JP34155791A JP34155791A JPH05186715A JP H05186715 A JPH05186715 A JP H05186715A JP 34155791 A JP34155791 A JP 34155791A JP 34155791 A JP34155791 A JP 34155791A JP H05186715 A JPH05186715 A JP H05186715A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- antifouling
- monomer
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、防汚機能を長期間発揮
する塗膜を形成することのできる新規な防汚性塗料組成
物に関する。FIELD OF THE INVENTION The present invention relates to a novel antifouling coating composition capable of forming a coating film exhibiting an antifouling function for a long time.
【０００２】[0002]
【従来の技術】従来、船舶や海洋構造物の没水部にはフ
ジツボ、フナクイムシ、藻類等海中生物の付着による腐
食防止や船舶の航行速度の低下防止を目的に、また養殖
用の網には海中生物の付着による魚介類の致死防止等を
目的にロジン系物質や有機錫を含有する防汚塗料が塗装
されている。2. Description of the Related Art Conventionally, for the purpose of preventing corrosion due to adhesion of marine organisms such as barnacles, beetles, algae, etc. in the submerged part of ships and marine structures and preventing the decrease in the navigation speed of ships, and for nets for aquaculture An antifouling paint containing a rosin-based substance or organic tin is applied for the purpose of preventing the death of fish and shellfish due to the adhesion of marine organisms.
【０００３】しかしながら、前者のロジン系物質を含有
する塗料は、塗膜に含まれるロジン及び防汚剤成分が溶
出することによって防汚効果を発揮するものであるが、
該塗膜は長期間の海水浸漬において不溶性成分が多くな
ると共に塗面が凸凹状となり海中生物の付着を防止する
効果が劣ってくる。また、後者の有機錫を含有する防汚
塗料は、毒性が強いことから魚介類に対し悪影響を及ぼ
す欠点がある。However, the former paint containing a rosin-based substance exhibits an antifouling effect by elution of the rosin and the antifouling agent component contained in the coating film.
The coating film has a large amount of insoluble components after long-term immersion in seawater, and the coating surface becomes uneven, so that the effect of preventing adhesion of marine organisms becomes poor. Further, the latter antifouling paint containing organotin has a drawback that it has a bad effect on fish and shellfish due to its strong toxicity.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、毒性が少な
くかつ長期にわたり防汚機能を発揮する防汚性組成物、
すなわち、毒性の低い防汚剤を用いても従来の毒性の高
い有機錫系防汚塗料と同等以上の長期にわたる防汚性能
を発揮する防汚性組成物を提供することを目的とする。The present invention provides an antifouling composition having low toxicity and exhibiting an antifouling function for a long period of time,
That is, it is an object of the present invention to provide an antifouling composition that exhibits a long-term antifouling performance equivalent to or higher than that of a conventional highly toxic organic tin antifouling paint even if a low toxic antifouling agent is used.
【０００５】[0005]
【課題を解決するための手段】本発明者は、毒性が少な
くかつ長期にわたり防汚機能を発揮する防汚性組成物を
得るべく鋭意研究を重ねた結果、特定の共重合体をビヒ
クル成分とすることによって、達成できることを知見し
本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to obtain an antifouling composition having a low toxicity and exhibiting an antifouling function for a long period of time, and as a result, a specific copolymer was identified as a vehicle component. By doing so, they have found that they can be achieved and completed the present invention.
【０００６】すなわち、本発明は、 （Ａ）次式の一般式That is, the present invention provides (A) the following general formula
【化２】 （式中Ｒ1はＨ又はＣＨ3、ｍは１又は２、Ｒｆはフッ素
原子を３〜２５個有するフロロアルキル基又はパ−フロ
ロアルキル基含有の置換基である。） で表されるフッ素系（メタ）アクリレ−ト
３〜５０重量％ （Ｂ）アミノ基又は水酸基含有ビニル単量体
３〜３０重量％ （Ｃ）α、β−不飽和二重結合を２〜４個有する単量体
０．２〜１０重量％ （Ｄ）共重合可能な他の単量体
２０〜９３．８重量％ からなる共重合体をビヒクル成分とする防汚性塗料組成
物である。[Chemical 2] (In the formula, R 1 is H or CH 3 , m is 1 or 2, and Rf is a fluoroalkyl group having 3 to 25 fluorine atoms or a perfluoroalkyl group-containing substituent.) (Meth) acrylate
3 to 50 wt% (B) Amino group- or hydroxyl group-containing vinyl monomer
3 to 30% by weight (C) Monomer having 2 to 4 α, β-unsaturated double bonds 0.2 to 10% by weight (D) Other copolymerizable monomer
It is an antifouling coating composition containing a copolymer of 20 to 93.8% by weight as a vehicle component.
【０００７】以下、本発明の防汚性塗料組成物で使用す
るビヒクル用共重合体の単量体成分について説明する。
（Ａ）の一般式化１で表されるフッ素系（メタ）アクリ
レ−トは、表面自由エネルギ−制御により、生物が付着
しにくい塗膜表面を形成するために用いる成分であり、
例えば以下に列記するような化合物である。The monomer components of the vehicle copolymer used in the antifouling coating composition of the present invention will be described below.
The fluorine-based (meth) acrylate represented by the general formula 1 of (A) is a component used for forming a coating film surface on which organisms are unlikely to adhere, by controlling the surface free energy,
For example, compounds listed below.
【０００８】ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ3 ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ3 ＣＨ2＝ＣＨＣＯＯＣＨ2Ｃ2Ｈ5 ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2Ｃ2Ｆ5 ＣＨ2＝ＣＨＣＯＯＣＨ（ＣＨ3）Ｃ2Ｆ5 ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ（ＣＨ3）Ｃ2Ｆ5 ＣＨ2＝ＣＨＣＯＯＣＨ（ＣＦ3）2 ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ（ＣＦ3） ＣＨ2＝ＣＨＣＯＯＣＨ（ＣＨ3）Ｃ3Ｆ7 [0008] CH 2 = CHCOOCH 2 CF 3 CH 2 = C (CH 3) COOCH 2 CF 3 CH 2 = CHCOOCH 2 C 2 H 5 CH 2 = C (CH 3) COOCH 2 C 2 F 5 CH 2 = CHCOOCH ( CH 3) C 2 F 5 CH 2 = C (CH 3) COOCH (CH 3) C 2 F 5 CH 2 = CHCOOCH (CF 3) 2 CH 2 = C (CH 3) COOCH (CF 3) CH 2 = CHCOOCH (CH 3 ) C 3 F 7
【０００９】 ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ（ＣＨ3）Ｃ3Ｆ7 ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）4Ｈ ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）4Ｈ ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）2（ＣＦ2）4Ｆ ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）2（ＣＦ2）4Ｆ ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）2Ｃ8Ｆ17 ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）2Ｃ8Ｆ17 ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）2Ｃ12Ｆ25 ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）2Ｃ12Ｆ25 [0009] CH 2 = C (CH 3) COOCH (CH 3) C 3 F 7 CH 2 = CHCOOCH 2 (CF 2) 4 H CH 2 = C (CH 3) COOCH 2 (CF 2) 4 H CH 2 = CHCOO (CH 2) 2 (CF 2) 4 F CH 2 = C (CH 3) COO (CH 2) 2 (CF 2) 4 F CH 2 = CHCOO (CH 2) 2 C 8 F 17 CH 2 = C ( CH 3) COO (CH 2) 2 C 8 F 17 CH 2 = CHCOO (CH 2) 2 C 12 F 25 CH 2 = C (CH 3) COO (CH 2) 2 C 12 F 25
【００１０】これらは単独あるいは複数組み合わせて使
用される。汎用の溶剤に対する溶解性の点からフッ素原
子の数は２５以下にする必要があり、また該フッ素系
（メタ）アクリレ−トの使用量は共重合体中３〜５０重
量％の範囲である。３％未満では表面自由エネルギ−の
低下が十分でないため生物が付着し易くなり、５０％を
越えると汎用溶剤に対する溶解性、付着性、発泡等の作
業等の作業性が低下すると共に、コストも高くなり、い
ずれも好ましくない。These are used alone or in combination. The number of fluorine atoms must be 25 or less from the viewpoint of solubility in a general-purpose solvent, and the amount of the fluorine-based (meth) acrylate used is in the range of 3 to 50% by weight in the copolymer. If it is less than 3%, the surface free energy is not sufficiently reduced, so that organisms are likely to adhere to it. If it exceeds 50%, solubility in general-purpose solvents, adhesiveness, workability such as foaming work, and the like, and cost are also reduced. It becomes high and neither is preferable.
【００１１】（Ｂ）のアミノ基又は水酸基含有ビニル単
量体は海水中に於いて常に新鮮な塗膜が露出し、防汚性
能を維持することを目的とした塗膜に微水溶性を付与す
るための成分である。The amino group- or hydroxyl group-containing vinyl monomer (B) imparts slightly water-soluble property to the coating film for the purpose of maintaining the antifouling performance by always exposing a fresh coating film in seawater. It is an ingredient for doing.
【００１２】アミノ基含有ビニル単量体の例としては、
ブチルアミノエチル（メタ）アクリレ−ト、（メタ）ア
クリルアミド等の第一級及び第二級アミノ基含有ビニル
単量体等が挙げられる。また、第三級アミノ基含有ビニ
ル単量体としてはジメチルアミノエチル（メタ）アクリ
レ−ト、ジエチルアミノエチル（メタ）アクリレ−ト、
ジメチルアミノプロピル（メタ）アクリレ−ト、ジメチ
ルアミノブチル（メタ）アクリレ−ト、ジブチルアミノ
エチル（メタ）アクリレ−ト、ジメチルアミノエチル
（メタ）アクリルアミド、ジメチルアミノプロピル（メ
タ）アクリルアミド等が挙げられる。その他ビニルピロ
リドン、ビニルピリジン、ビニルカルバゾ−ルの如き複
素環族系塩基性単量体等が含まれる。Examples of amino group-containing vinyl monomers include:
Examples include primary and secondary amino group-containing vinyl monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide. Further, as the tertiary amino group-containing vinyl monomer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Examples thereof include dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide. In addition, heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole are included.
【００１３】水酸機含有ビニル単量体の種類としては２
−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロ
キシプロピル（メタ）アクリレ−ト、３−ヒドロキシプ
ロピル（メタ）アクリレ−ト、２−ヒドロキシブチル
（メタ）アクリレ−ト、４−ヒドロキシブチル（メタ）
アクリレ−ト、２−ヒドロキシエチル（メタ）アクリレ
−トとエチレンオキサイド、プロピレンオキサイド、γ
−ブチロラクトン、ε−カプロラクトン等との付加物、
また２−ヒドロキシエチル（メタ）アクリレ−ト、２−
ヒドロキシプロピル（メタ）アクリレ−ト等の二重体、
三量体等が挙げられる。更にはグリセロ−ル（メタ）ア
クリレ−トの如く水酸基を複数有する単量体も使用でき
る。There are two types of vinyl monomers containing hydroxyl units.
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate and ethylene oxide, propylene oxide, γ
-Addition products with butyrolactone, ε-caprolactone, etc.,
2-hydroxyethyl (meth) acrylate, 2-
A double body such as hydroxypropyl (meth) acrylate,
A trimer etc. are mentioned. Furthermore, a monomer having a plurality of hydroxyl groups such as glycerol (meth) acrylate can be used.
【００１４】該アミノ基又は水酸基含有ビニル単量体
は、単独あるいは複数組み合わせて使用することがで
き、その使用量は共重合体中３〜３０重量％の範囲であ
る。３％未満では塗膜の溶出効果が不十分であり、３０
重量％を越えると塗膜が溶出し易くなり長期にわたる防
汚性が維持できなくなるためいずれも好ましくない。The amino group- or hydroxyl group-containing vinyl monomer may be used alone or in combination of two or more, and the amount thereof used is in the range of 3 to 30% by weight in the copolymer. If it is less than 3%, the elution effect of the coating film is insufficient,
If the content is more than 10% by weight, the coating film is likely to be eluted and the stainproof property cannot be maintained for a long period of time.
【００１５】（Ｃ）のα、β−不飽和結合を２〜４個有
する単量体としては、エチレングリコ−ルジ（メタ）ア
クリレ−ト、プロピレングリコ−ルジ（メタ）アクリレ
−ト、ブチレングリコ−ルジ（メタ）アクリレ−ト、ネ
オペンチルグリコ−ルジ（メタ）アクリレ−ト、ジビニ
ルベンゼン等のジビニル類、トリメチロ−ルプロパント
リ（メタ）アクリレ−ト、ペンタエリトリットテトラ
（メタ）アクリレ−ト等の如きα、β−不飽和二重結合
を３〜４個有する単量体、更にはこれらとエチレンオキ
サイド、プロピレンオキサイド、ε−カプロラクトン、
有機ラクトン類等との付加物等が挙げられ、これらは単
独あるいは複数で使用される。Examples of the monomer (C) having 2 to 4 α, β-unsaturated bonds include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and butylene glycol. Such as divinyls such as rudi (meth) acrylate, neopentylglycol di (meth) acrylate, divinylbenzene, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. Such a monomer having 3 to 4 α, β-unsaturated double bonds, and further these and ethylene oxide, propylene oxide, ε-caprolactone,
Examples thereof include adducts with organic lactones and the like, and these are used alone or in plural.
【００１６】この成分は、長期にわたり防汚性能を有す
る塗膜を維持するための不可欠な成分であり、その使用
量は共重合体中０．２〜１０重量％の範囲である。０．
２重量％未満では長期にわたる防汚性能が劣り２０重量
％を越えるとポリマ−が増粘したりゲル化し易くなるた
めいずれも好ましくない。なお、α、β−不飽和二重結
合が４個を越える単量体を使用するとポリマ−が増粘し
たりゲル化し易くなるため好ましくない。This component is an indispensable component for maintaining a coating film having antifouling performance for a long period of time, and its amount used is in the range of 0.2 to 10% by weight in the copolymer. 0.
If it is less than 2% by weight, the antifouling performance for a long period of time is inferior, and if it exceeds 20% by weight, the viscosity of the polymer increases and gelation easily occurs, which is not preferable. It is not preferable to use a monomer having more than 4 α, β-unsaturated double bonds because the polymer thickens and gels easily.
【００１７】（Ｄ）の共重合可能な他の単量体はメチル
（メタ）アクリレ−ト、エチル（メタ）アクリレ−トｎ
−プロピル（メタ）アクリレ−ト、ｉ−プロピル（メ
タ）アクリレ−ト、ｎ−ブチル（メタ）アクリレ−ト、
ｉ−ブチル（メタ）アクリレ−ト、ｔ−ブチル（メタ）
アクリレ−ト、２−エチルヘキシル（メタ）アクリレ−
ト、ラウリル（メタ）アクリレ−ト、ステアリル（メ
タ）アクリレ−ト、ベンジル（メタ）アクリレ−ト、フ
ェニル（メタ）アクリレ−ト、イソボルニル（メタ）ア
クリレ−ト、シクロヘキシル（メタ）アクリレ−ト、グ
リシジル（メタ）アクリレ−トの如き（メタ）アクリル
酸エステル類を始め、（メタ）アクリル酸などのカルボ
ン酸類、またイタコン酸、マレイン酸、コハク酸更には
これらのハ−フエステル、シエステル等が挙げられる。
その他スチレン、ビニルトルエン、α−メチルスチレ
ン、（メタ）アクリロニトリル、酢酸ビニル、プロピオ
ン酸ビニル等の共重合可能な単量体も含まれる。Other copolymerizable monomers of (D) are methyl (meth) acrylate and ethyl (meth) acrylate n.
-Propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,
i-Butyl (meth) acrylate, t-butyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate
, Lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, Examples include carboxylic acids such as (meth) acrylic acid, including (meth) acrylic acid esters such as glycidyl (meth) acrylate, and itaconic acid, maleic acid, succinic acid, and half-esters and cis esters thereof. Be done.
In addition, copolymerizable monomers such as styrene, vinyltoluene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate and vinyl propionate are also included.
【００１８】本発明の防汚性塗料組成物のビヒクル成分
として使用する共重合体は、公知の方法にしたがって製
造される。すなわち、本発明の上記（Ａ）〜（Ｄ）の単
量体混合物をラジカル重合開始剤の存在下に６０〜１８
０℃の反応温度に於いて５〜１４時間反応を続けること
により得られる。重合方法としても有機溶剤中で行う溶
液重合のほか乳化重合、懸濁重合、塊状重合等の方法に
より得られるが、トルエン、キシレン、メチルイソブチ
ルケトン、酢酸ｎ−ブチル等の様な一般の有機溶剤を用
いる溶液重合が生産性、性能の点で有利である。The copolymer used as the vehicle component of the antifouling coating composition of the present invention is produced by a known method. That is, the monomer mixture of the above (A) to (D) of the present invention is added in the presence of a radical polymerization initiator in an amount of 60 to 18
It is obtained by continuing the reaction at a reaction temperature of 0 ° C. for 5 to 14 hours. As the polymerization method, solution polymerization carried out in an organic solvent as well as emulsion polymerization, suspension polymerization, bulk polymerization and the like can be used. Common organic solvents such as toluene, xylene, methyl isobutyl ketone, n-butyl acetate and the like can be used. Solution polymerization using is advantageous in terms of productivity and performance.
【００１９】本発明で使用する共重合体は数平均分子量
５０００〜１０００００の範囲のものである。５０００
未満では長期の防汚性能が劣り、１０００００を越える
と防汚剤が溶出しにくくなると共に塗装作業しにくくな
りいずれも好ましくない。また、本発明で使用する共重
合体のガラス転移温度は−２０〜５０℃の範囲のもので
ある。−２０℃未満では塗膜に粘着性を生じ５０℃を越
えると塗膜がもろくなるためいずれも好ましくない。The copolymer used in the present invention has a number average molecular weight of 5,000 to 100,000. 5000
If it is less than 100, the long-term antifouling performance is poor, and if it exceeds 100,000, the antifouling agent is difficult to elute and the coating work becomes difficult, which is not preferable. The glass transition temperature of the copolymer used in the present invention is in the range of -20 to 50 ° C. If it is lower than -20 ° C, the coating film becomes tacky, and if it exceeds 50 ° C, the coating film becomes brittle, which is not preferable.
【００２０】本発明の共重合体は、長期にわたり塗膜に
微水溶性を付与する特徴を有する。この共重合体に、要
求性能に応じて従来公知の防汚剤を配合して防汚性塗料
組成物を調製し、これで塗膜を形成すると、防汚剤が均
一にかつ徐々に海水中に溶出し、その結果長期にわたり
優れた防汚性が発揮される。The copolymer of the present invention is characterized by imparting slightly water solubility to the coating film for a long period of time. This copolymer is mixed with a conventionally known antifouling agent according to the required performance to prepare an antifouling coating composition, and when a coating film is formed with this, the antifouling agent is uniformly and gradually in seawater. The result is excellent antifouling properties over a long period of time.
【００２１】防汚剤としては、例えば亜酸化銅、チオシ
アン銅、銅粉末等の銅系防汚剤を始め、鉛、亜鉛、ニッ
ケル等その他の金属化合物、ジフェニルアミン等のアミ
ン誘導体、ニトリル化合物、ベンゾチアゾ−ル系化合
物、マレイミド系化合物、ピリジン系化合物等を単独あ
るいは複数で使用する。その他防汚剤ではないが、塗膜
の表面に潤滑性を付与し生物の付着を防止する目的でジ
メチルポリシロキサン、シリコ−ンオイル等のシリコン
化合物やフッ化炭素等の含フッ素化合物等も使用するこ
とができる。更に本発明の防汚性塗料組成物は、前記し
た防汚剤以外にも体質顔料、着色顔料、可塑剤、各種塗
料用添加剤、その他の樹脂等を必要に応じて配合するこ
とができる。Examples of the antifouling agent include copper-based antifouling agents such as cuprous oxide, thiocyanic copper and copper powder, other metal compounds such as lead, zinc and nickel, amine derivatives such as diphenylamine, nitrile compounds and benzothiazo. -A compound, a maleimide compound, a pyridine compound or the like is used alone or in combination. Although it is not an antifouling agent, silicon compounds such as dimethylpolysiloxane and silicone oil, and fluorine-containing compounds such as fluorocarbon are also used for the purpose of imparting lubricity to the surface of the coating film and preventing the adhesion of organisms. be able to. Furthermore, the antifouling coating composition of the present invention may contain, in addition to the above-mentioned antifouling agent, an extender pigment, a coloring pigment, a plasticizer, various paint additives, and other resins, if necessary.
【００２２】本発明の組成物を用いて塗膜を形成する方
法は、前記した防汚性塗料組成物を船舶、各種漁網、港
湾施設、オイルフェンス、橋梁、海底基地等の水中構造
物等の基材表面に直接もしくは、基材にウォッシュプラ
イマ−、塩化ゴム系、エポキシ系等のプライマ−、中塗
り塗料類等を塗布した塗膜の上に刷毛塗り、吹き付け塗
り、ロ−ラ−塗り、浸漬塗り等の手段で塗布する。塗布
量は一般的には乾燥膜厚として５０〜４００μｍの範囲
である。塗膜の乾燥は一般的には室温で行われるが、加
熱乾燥しても差し支えない。The method of forming a coating film using the composition of the present invention is the above-mentioned antifouling coating composition applied to underwater structures such as ships, various fishing nets, harbor facilities, oil fences, bridges and submarine bases. Brush coating, spray coating, roller coating, directly on the surface of the base material or on the coating film on which the base material is coated with wash primer, chlorinated rubber type, epoxy type primer, etc. It is applied by means such as dip coating. The coating amount is generally in the range of 50 to 400 μm as a dry film thickness. The coating film is generally dried at room temperature, but may be dried by heating.
【００２３】[0023]
【実施例】本発明を実施例及び比較例により説明する。
なお、部及び％は夫々重量部及び重量％を表す。 （ビヒクル用共重合体の製造例）冷却器、温度計、滴下
ロ−ト及び撹拌器を備えた四つ口フラスコにｎ−ブタノ
−ル３０部及びキシレン４０部を仕込み撹拌しながら１
００℃に昇温した。次いで、滴下ロ−トより表１に示す
単量体及び重合開始剤の混合物を３時間で等速滴下し
た。滴下終了１時間後タ−シャリブチルパ−オキシオク
トエ−ト１部とキシレン１０部を２時間で滴下し、更に
２時間撹拌した後キシレンを２０部添加し表１に示す特
性値を有するビヒクル用共重合体Ｐ−１〜１１を得た。EXAMPLES The present invention will be described with reference to Examples and Comparative Examples.
In addition, part and% represent a weight part and weight%, respectively. (Production Example of Copolymer for Vehicle) 30 parts of n-butanol and 40 parts of xylene were charged into a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer while stirring 1
The temperature was raised to 00 ° C. Then, the mixture of the monomer and the polymerization initiator shown in Table 1 was added dropwise at a constant rate over 3 hours from the dropping funnel. 1 hour after the end of the dropping, 1 part of tert-butylperoxyoctoate and 10 parts of xylene were added dropwise over 2 hours, and after stirring for 2 hours, 20 parts of xylene was added and a copolymer for vehicles having the characteristic values shown in Table 1 was added. P-1 to 11 were obtained.
【００２４】次いで、前記共重合体６０部、亜鉛化銅３
０部、亜鉛化１０部、ビス（ジメチルジチオカルバミン
酸）亜鉛５部、コロイド状シリカ５部、メチルイソブチ
ルケトン１５部、キシレン１５部を混合後ボ−ルミル中
で６時間分散し実施例１〜５及び比較例１〜７の防汚性
塗料組成物を調整した。Then, 60 parts of the above-mentioned copolymer, copper zincate 3
0 parts, 10 parts of zincation, 5 parts of zinc bis (dimethyldithiocarbamate), 5 parts of colloidal silica, 15 parts of methyl isobutyl ketone, and 15 parts of xylene were mixed and dispersed in a ball mill for 6 hours. And the antifouling coating material compositions of Comparative Examples 1 to 7 were prepared.
【００２５】更に実施例１〜５及び比較例１〜７の塗料
をサンドブラスト処理綱板に防錆塗料を塗布したある塗
板に、乾燥膜厚８０μになる様塗装し、１０日間乾燥し
たものを試験板として広島県広島湾内で２４ケ月浸漬し
て防汚性を評価した。結果を表２に示した。なお、表内
の数字は付着生物の付着面積を％で表した。表２の結果
から分かるごとく、本発明のビヒクル用共重合体を用い
た防汚性塗料組成物は、単独でも長期にわたり優れた防
汚効果を発揮するが、本発明以外の重合体にブレンドし
た場合も防汚性能を格段に向上させることができる。Furthermore, the paints of Examples 1 to 5 and Comparative Examples 1 to 7 were applied on a sandblasted steel plate coated with an anticorrosive paint so as to have a dry film thickness of 80 μ, and dried for 10 days. The plate was immersed in Hiroshima Bay in Hiroshima Prefecture for 24 months and evaluated for antifouling property. The results are shown in Table 2. The numbers in the table represent the adhered area of adherent organisms in%. As can be seen from the results in Table 2, the antifouling coating composition using the vehicle copolymer of the present invention exhibits excellent antifouling effect alone for a long period of time, but was blended with a polymer other than the present invention. Also in this case, the antifouling performance can be remarkably improved.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表１において、各記号は次ぎの化合物を表
す。 ＊ １：３ＦＡ＝ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ3 ＊ ２：８ＦＭ＝ＣＨ2（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）
4Ｈ ＊ ３：１７ＦＭ＝ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（Ｃ
Ｈ2）2Ｃ8Ｆ17 ＊ ４：２１ＦＭ＝ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（Ｃ
Ｈ2）2Ｃ10Ｆ21 ＊ ５：ＤＭＡＥＭＡ＝ジメチルアミノエチルメタクリ
レ−ト ＊ ６：ＤＭＡＥＡＡＭ＝ジメチルアミノエチルアクリ
ルアミド ＊ ７：２−ＨＥＭＡ＝２−ヒドロキシエチルメタクリ
レ−ト ＊ ８：ＰＰＧＤＭＡ＝ポリプロピレングリコ−ルジメ
タクリレ−ト ＊ ９：ＰＥＴＭＡ＝ペンタエリトリットテトラメタク
リレ−ト ＊１０：ＤＰＥＰＡ＝ジペンタエリトリットペンタアク
リレ−ト ＊１１：ｔ−ＢＰＯ＝タ−シャリブチルパ−オキシオク
トエ−ト ＊１２：サ−マルメカニカルアナライザ−（ＴＭＡ）に
より実測した。In Table 1, each symbol represents the following compound. * 1: 3FA = CH 2 = CHCOOCH 2 CF 3 * 2: 8FM = CH 2 (CH 3) COOCH 2 (CF 2)
4 H * 3: 17FM = CH 2 = C (CH 3) COO (C
H 2) 2 C 8 F 17 * 4: 21FM = CH 2 = C (CH 3) COO (C
H 2) 2 C 10 F 21 * 5: DMAEMA = dimethylaminoethyl methacrylate - DOO * 6: DMAEAAM = dimethylaminoethyl acrylamide * 7: 2-HEMA = 2- hydroxyethyl methacrylate - DOO * 8: PPGDMA = Polypropylene Glycol dimethacrylate * 9: PETMA = pentaerythritol tetramethacrylate * 10: DPEPA = dipentaerythritol pentaacrylate * 11: t-BPO = tertiary butyl butyl oxyoctate * 12: sa -Measurement was performed using a Malmechanical Analyzer- (TMA).
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【発明の効果】本発明の防汚塗料用組成物は、長期にわ
たり微水溶性の維持できる共重合体をビヒクル成分とし
たので、毒性の低い防汚剤を用いても従来の毒性の高い
有機錫系防汚塗料と同等以上の長期にわたる防汚性能を
発揮し、したがって海洋汚染防止の点からも極めて有用
である。The antifouling coating composition of the present invention uses a copolymer that can maintain slightly water-soluble property for a long period of time as a vehicle component. It exhibits a long-term antifouling performance equivalent to or better than that of a tin-based antifouling paint, and is extremely useful from the viewpoint of preventing marine pollution.
Claims (1)
原子を３〜２５個有するフロロアルキル基又はパ−フロ
ロアルキル基含有の置換基である。） で表されるフッ素系（メタ）アクリレ−ト
３〜５０重量％ （Ｂ）アミノ基又は水酸基含有ビニル単量体
３〜３０重量％ （Ｃ）α、β−不飽和二重結合を２〜４個有する単量体
０．２〜１０重量％ （Ｄ）共重合可能な他の単量体
２０〜９３．８重量％ からなる共重合体をビヒクル成分とする防汚性塗料組成
物。1. (A) The following general formula: (In the formula, R 1 is H or CH 3 , m is 1 or 2, and Rf is a fluoroalkyl group having 3 to 25 fluorine atoms or a perfluoroalkyl group-containing substituent.) (Meth) acrylate
3 to 50 wt% (B) Amino group- or hydroxyl group-containing vinyl monomer
3 to 30% by weight (C) Monomer having 2 to 4 α, β-unsaturated double bonds 0.2 to 10% by weight (D) Other copolymerizable monomer
An antifouling coating composition comprising a vehicle component of 20 to 93.8% by weight of a copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03341557A JP3104039B2 (en) | 1991-12-24 | 1991-12-24 | Antifouling paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03341557A JP3104039B2 (en) | 1991-12-24 | 1991-12-24 | Antifouling paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05186715A true JPH05186715A (en) | 1993-07-27 |
| JP3104039B2 JP3104039B2 (en) | 2000-10-30 |
Family
ID=18346995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03341557A Expired - Fee Related JP3104039B2 (en) | 1991-12-24 | 1991-12-24 | Antifouling paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3104039B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009256471A (en) * | 2008-04-17 | 2009-11-05 | Mitsubishi Rayon Co Ltd | Coating composition and copolymer |
| CN102190759A (en) * | 2011-03-22 | 2011-09-21 | 温州大学 | Polyester modified fluoro acrylic resin, and preparation method and coating thereof |
| CN106632886A (en) * | 2016-11-14 | 2017-05-10 | 清华大学 | Polymer as well as preparation method and application thereof |
| CN110734519A (en) * | 2019-11-13 | 2020-01-31 | 中国科学院兰州化学物理研究所 | low-surface-energy water-based self-polishing emulsion, preparation method thereof and low-surface-energy water-based self-polishing anti-drag antifouling paint |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2467168B (en) | 2009-01-26 | 2011-03-16 | Air Bearings Ltd | Gas bearing and method of manufacturing the same |
-
1991
- 1991-12-24 JP JP03341557A patent/JP3104039B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009256471A (en) * | 2008-04-17 | 2009-11-05 | Mitsubishi Rayon Co Ltd | Coating composition and copolymer |
| CN102190759A (en) * | 2011-03-22 | 2011-09-21 | 温州大学 | Polyester modified fluoro acrylic resin, and preparation method and coating thereof |
| CN106632886A (en) * | 2016-11-14 | 2017-05-10 | 清华大学 | Polymer as well as preparation method and application thereof |
| CN110734519A (en) * | 2019-11-13 | 2020-01-31 | 中国科学院兰州化学物理研究所 | low-surface-energy water-based self-polishing emulsion, preparation method thereof and low-surface-energy water-based self-polishing anti-drag antifouling paint |
| CN110734519B (en) * | 2019-11-13 | 2020-08-14 | 中国科学院兰州化学物理研究所 | Low-surface-energy aqueous self-polishing emulsion, preparation method thereof and low-surface-energy aqueous self-polishing anti-drag antifouling paint |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3104039B2 (en) | 2000-10-30 |
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