JPH05171064A - Antifouling coating composition - Google Patents
Antifouling coating compositionInfo
- Publication number
- JPH05171064A JPH05171064A JP3341552A JP34155291A JPH05171064A JP H05171064 A JPH05171064 A JP H05171064A JP 3341552 A JP3341552 A JP 3341552A JP 34155291 A JP34155291 A JP 34155291A JP H05171064 A JPH05171064 A JP H05171064A
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- meth
- monomer
- acrylate
- antifouling
- weight
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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）アミノ基含有ビニル単量体 ０．５〜３０重量％ （ｂ）水酸基含有単量体 ０〜３０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 ５０〜９６．８重量％ からなり、かつ単量体（ａ）と単量体（ｂ）の合計量が
全単量体中の３〜３０％であ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。That is, the present invention provides (a) an amino group-containing vinyl monomer 0.5 to 30% by weight (b) a hydroxyl group-containing monomer 0 to 30% by weight (c) an α, β-unsaturated double monomer Monomer having 2 to 4 bonds 0.2 to 10% by weight (d) Other copolymerizable monomer 50 to 96.8% by weight, and monomer (a) and monomer An antifouling coating composition comprising as a vehicle component a copolymer in which the total amount of (b) is 3 to 30% of all monomers.
【０００７】以下、本発明の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。本発明にお
ける（ａ）アミノ基含有ビニル単量体及び（ｂ）水酸基
含有単量体は、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ため塗膜に微水溶性を付与するため
の成分である。The monomer components of the vehicle copolymer used in the composition of the present invention will be described below. The (a) amino group-containing vinyl monomer and (b) hydroxyl group-containing monomer of the present invention are slightly water-soluble in the coating film because a fresh coating film is always exposed in seawater and the antifouling performance is maintained. Is a component for imparting.
【０００８】（ａ）の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。これらは
単独あるいは複数で使用される。（ａ）のアミノ基含有
単量体の使用量は共重合体中０．５〜３０重量％の範囲
である。０．５％未満では海水中での塗膜の溶出が不十
分であり、３０％を越えると溶出が促進されコントロ−
ルしにくくなるためいずれも好ましくない。Examples of the amino group-containing vinyl monomer (a) include butylaminoethyl (meth) acrylate,
Examples thereof include primary and secondary amino group-containing vinyl monomers such as (meth) acrylamide. The tertiary amino group-containing vinyl monomer may be dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate.
, Dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and the like. In addition, heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole are included. These are used alone or in plural. The amount of the amino group-containing monomer (a) used is in the range of 0.5 to 30% by weight in the copolymer. If it is less than 0.5%, the elution of the coating film in seawater is insufficient, and if it exceeds 30%, the elution is accelerated and the control is performed.
Both are not preferable because they are difficult to handle.
【０００９】（ｂ）の水酸基含有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−ト等の二量体、
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され
る。（ｂ）の水酸基含有単量体の使用量は海水中での塗
膜の溶出をコントロ−ルさせるため共重合体中３０重量
％以下の範囲で単独あるいは複数で使用される。Examples of the type of the hydroxyl group-containing monomer (b) are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 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 dimer such as hydroxypropyl (meth) acrylate,
A trimer etc. are mentioned. Furthermore, a monomer having a plurality of hydroxyl groups such as glycerol (meth) acrylate is also used. The hydroxyl group-containing monomer (b) is used alone or in a plural amount within the range of 30% by weight or less in the copolymer in order to control the elution of the coating film in seawater.
【００１０】また、単量体（ａ）と単量体（ｂ）の総量
は海水中での塗膜の溶出を長期にわたって維持するため
共重合体中３〜３０％の範囲で使用することができる。
３％未満では塗膜の溶出が不十分であり、３０％を越え
ると塗膜が溶出しすぎるためいずれも好ましくない。The total amount of the monomer (a) and the monomer (b) should be 3 to 30% in the copolymer in order to maintain the elution of the coating film in seawater for a long period of time. it can.
If it is less than 3%, the elution of the coating film is insufficient, and if it exceeds 30%, the coating film elutes too much.
【００１１】（ｃ）のα、β−不飽和二重結合を２〜４
個有する単量体の種類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、
単独あるいは複数で使用される。The α, β-unsaturated double bond of (c) is added to 2 to 4
Examples of the type of monomer having ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, divinyls such as divinylbenzene, trimethylol
Monomers having 3 to 4 α, β-unsaturated double bonds, such as propanepropane (meth) acrylate, pentaerythritoltetra (meth) acrylate, etc., and further these, ethylene oxide, propylene oxide, ε-caprolactone, adducts with organic lactones and the like, and the like,
Used alone or in combination.
【００１２】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、共重合体
中０．２〜１０重量％の範囲で使用される。０．２重量
％未満では長期にわたる防汚性能が劣り１０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 essential component for maintaining a coating film having antifouling performance for a long period of time, and is used in the range of 0.2 to 10% by weight in the copolymer. If it is less than 0.2% by weight, the antifouling property for a long period of time is inferior, and if it exceeds 10% by weight, the polymer thickens and gels easily, which is not preferable. The α, β-unsaturated double bond is 4
Use of more than one monomer is not preferable because the polymer thickens and gels easily.
【００１３】（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、ジ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 (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 (meth) acrylic acid esters such as glycidyl (meth) acrylate, carboxylic acids such as (meth) acrylic acid, and itaconic acid, maleic acid, succinic acid, and their half esters and diesters. Be done.
In addition, copolymerizable monomers such as styrene, vinyltoluene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate and vinyl propionate are also included.
【００１４】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、本発明の単量体混合物をラジカル
重合開始剤の存在下に６０〜１８０℃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 present invention is obtained by continuing the reaction in the presence of a radical polymerization initiator at a reaction temperature of 60 to 180 ° C. for 5 to 14 hours. As the polymerization method, besides solution polymerization carried out in an organic solvent, emulsion polymerization, suspension polymerization, bulk polymerization and the like can be used. Toluene, xylene, methyl isobutyl ketone, acetic acid n-
Solution polymerization using a general organic solvent such as butyl is advantageous in terms of productivity and performance.
【００１５】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.
【００１６】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.
【００１７】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 antifouling agents 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.
【００１８】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、基材にウオッシュプラ
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 base material on which a wash primer, chlorinated rubber-based, epoxy-based primer, or intermediate coating material is applied. 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.
【００１９】[0019]
【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。 実施例１〜４、比較例１〜７ 冷却機、温度計、滴下ロ−ト及び撹拌機を備えた四つ口
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１００℃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等の混合物
を３時間で等速滴下した。滴下終了１時間後タ−シャル
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。次いで、前記共重合体６０部、亜
酸化銅３０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部を添加後ボ−
ルミル中で６時間分散し防汚性塗料組成物を調整した。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. Examples 1 to 4 and Comparative Examples 1 to 7 30 parts of n-butanol and 40 parts of xylene were charged into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and stirred at 100 ° C. The temperature was raised to. Then, a mixture of the monomer, the polymerization initiator and the like shown in Table 1 was dropped at a constant rate from the dropping funnel over 3 hours. 1 hour after the end of the dropping, 1 part of tertiary butyl peroxyoctoate and 10 parts of xylene were added dropwise over 2 hours, and the mixture was further stirred for 2 hours and then xylene was added to 20 parts.
Copolymers for vehicles P-1 to 11 having the characteristic values shown in Table 1 were obtained. Then, 60 parts of the copolymer, 30 parts of cuprous oxide, 10 parts of zinc oxide, 5 parts of zinc bis (dimethyldithiocarbamate), 5 parts of colloidal silica, 15 parts of methyl isobutyl ketone, and 15 parts of xylene were added, and then added.
The antifouling coating composition was prepared by dispersing in a rumill for 6 hours.
【００２０】更に実施例−１〜４及び比較例−１〜７の
塗料をサンドブラスト処理鋼板に防錆塗料を塗布してあ
る途板に、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ヶ月浸
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。Further, the paints of Examples-1 to 4 and Comparative Examples-1 to 7 were applied on a sandblasted steel plate coated with a rust preventive paint so as to have a dry film thickness of 80 .mu.m and dried for 10 days. The test piece was immersed in Hiroshima Bay, Hiroshima Prefecture, for 24 months to evaluate the antifouling property. The results are shown in Table 2. In addition,
The numbers in the table represent the adhered area of adherent organisms in%.
【００２１】[0021]
【表１】 [Table 1]
【００２２】表１において、各記号は次の化合物を表
す。 ＊１：ＤＭＡＥＭＡ＝ジメチルアミノエチルメタクリレ
−ト ＊２：ＤＭＡＥＡＡＭ＝ジメチルアミノエチルアクリル
アミド ＊３：２−ＨＥＭＡ＝２−ヒドロキシエチルメタクリレ
−ト ＊４＝２−ＨＥＭＡ＋ε−ＣＬ：２−ヒドロキシメタク
リレ−トとε−カプロラクトンの２モル付加物 ＊５：ＰＰＧＤＭＡ＝ポリプロピレングリコ−ルメタク
リレ−ト ＊６：ＰＥＴＭＡ＝ペンタエリトリットテトラメタクリ
レ−ト ＊７：ＤＰＥＰＡ＝ジペンタエリトリットペンタアクリ
レ−ト ＊８：ｔ−ＢＰＯ＝タ−シャリブチルパ−オキシオクト
エ−ト ＊９：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: DMAEMA = dimethylaminoethyl methacrylate * 2: DMAEAAM = dimethylaminoethyl acrylamide * 3: 2-HEMA = 2-hydroxyethyl methacrylate * 4 = 2-HEMA + ε-CL: 2-hydroxy methacrylate -2 mol addition product of ε-caprolactone * 5: PPGDMA = polypropylene glycol methacrylate * 6: PETMA = pentaerythritol tetramethacrylate * 7: DPEPA = dipentaerythritol pentaacrylate * 8: t-BPO = tertiarybutylperoxyoctoate * 9: Measured by a thermal mechanical analyzer (TMA).
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【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)
全単量体中の３〜３０％である共重合体をビヒクル成分
とする防汚性塗料組成物。1. Amino group-containing vinyl monomer 0.5 to 30% by weight (b) Hydroxyl group-containing monomer 0 to 30% by weight (c) α, β-unsaturated double bond 2 to Monomer having 4 0.2 to 10% by weight (d) Other copolymerizable monomer 50 to 96.8% by weight, and comprising monomer (a) and monomer (b) An antifouling coating composition comprising as a vehicle component a copolymer having a total amount of 3 to 30% of all monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34155291A JP3194153B2 (en) | 1991-12-24 | 1991-12-24 | Antifouling paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34155291A JP3194153B2 (en) | 1991-12-24 | 1991-12-24 | Antifouling paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05171064A true JPH05171064A (en) | 1993-07-09 |
| JP3194153B2 JP3194153B2 (en) | 2001-07-30 |
Family
ID=18346955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34155291A Expired - Fee Related JP3194153B2 (en) | 1991-12-24 | 1991-12-24 | Antifouling paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3194153B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059419A (en) * | 2008-09-04 | 2010-03-18 | Rohm & Haas Co | Germicide coating |
| JP2015042716A (en) * | 2013-08-26 | 2015-03-05 | 日東化成株式会社 | Fishing net antifouling coating composition, copolymer for fishing net antifouling coating composition, fishing net having, on surface, antifouling film formed with the composition, fishing net implement and underwater structure |
-
1991
- 1991-12-24 JP JP34155291A patent/JP3194153B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059419A (en) * | 2008-09-04 | 2010-03-18 | Rohm & Haas Co | Germicide coating |
| JP2015042716A (en) * | 2013-08-26 | 2015-03-05 | 日東化成株式会社 | Fishing net antifouling coating composition, copolymer for fishing net antifouling coating composition, fishing net having, on surface, antifouling film formed with the composition, fishing net implement and underwater structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3194153B2 (en) | 2001-07-30 |
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