JPS5935938B2 - Method for extending antifouling effect using water-permeable resin composition - Google Patents

Method for extending antifouling effect using water-permeable resin composition

Info

Publication number
JPS5935938B2
JPS5935938B2 JP51030521A JP3052176A JPS5935938B2 JP S5935938 B2 JPS5935938 B2 JP S5935938B2 JP 51030521 A JP51030521 A JP 51030521A JP 3052176 A JP3052176 A JP 3052176A JP S5935938 B2 JPS5935938 B2 JP S5935938B2
Authority
JP
Japan
Prior art keywords
antifouling
resin composition
coating
water
film
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.)
Expired
Application number
JP51030521A
Other languages
Japanese (ja)
Other versions
JPS52112633A (en
Inventor
守男 吉田
郁夫 安里
亨 仙波
潔 村瀬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toa Paint Co Ltd
Original Assignee
Toa Paint Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toa Paint Co Ltd filed Critical Toa Paint Co Ltd
Priority to JP51030521A priority Critical patent/JPS5935938B2/en
Priority to NO770913A priority patent/NO153972C/en
Priority to DE2711458A priority patent/DE2711458C2/en
Priority to GB11363/77A priority patent/GB1551513A/en
Priority to NL7702975A priority patent/NL7702975A/en
Publication of JPS52112633A publication Critical patent/JPS52112633A/en
Publication of JPS5935938B2 publication Critical patent/JPS5935938B2/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Description

【発明の詳細な説明】 本発明は水中防汚塗膜の防汚効果を延長する方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for extending the antifouling effectiveness of underwater antifouling coatings.

更に詳しくは水中防汚塗膜上に塗装して、その防汚効果
期間の延長を可能にするような機能を有する樹脂組成物
を用いた防汚効果の延長方法に関するものである。More specifically, the present invention relates to a method for extending the antifouling effect using a resin composition that is coated on an underwater antifouling coating and has a function of extending the duration of the antifouling effect.

水中防汚塗膜の防汚効果を長期間保持することは、船舶
や装置の経済的運行や質源の有効活用に寄与するところ
が非常に大きいので、そのような塗料や方法の開発は常
にのぞまれているところである。Maintaining the antifouling effect of underwater antifouling coatings for a long period of time greatly contributes to the economical operation of ships and equipment and the effective use of quality resources, so the development of such coatings and methods is a constant endeavor. It is a place that is desired.

本発明はこのような防汚効果を延長させることが可能な
樹脂組成物を用いる方法である。水棲動植物の付着を防
止する防汚塗料は、大きく分けて二つの種類があり、そ
の一つは耐水性の合成樹脂皮膜中に防汚剤を分散させた
もので、例えば塩化ビニル樹脂系防汚塗料がある。他の
一つはロジンを主なバインダーとして水中でロジンの溶
出に伴つて防汚剤を溶出させるタイプのもので、従来の
油性防汚塗料の多くはこのタイプのものである。しかし
ながらこの後者の場合、防汚塗膜中からの頭ノジの溶出
は、防汚塗膜自体の消耗劣化を意味し、事実この種の防
汚塗膜は水中に数か月間浸漬されると大きな消耗を示し
てやせ、かつ塗膜の強靭性が失なわれて来る。本発明者
等はこのような問題を改善すべく研究した結果、従来の
防汚塗膜を、耐水性を有しかつ透水性を有する皮膜で被
覆することによつて、防汚塗膜の過度の劣化を防止する
と同時に、防汚塗膜に強靭性を与える方法を発明したの
である。The present invention is a method using a resin composition that can extend such an antifouling effect. Antifouling paints that prevent aquatic animals and plants from adhering can be roughly divided into two types. One is a water-resistant synthetic resin film with an antifouling agent dispersed in it. There's paint. The other type is one in which rosin is the main binder and the antifouling agent is eluted as the rosin is eluted in water, and most conventional oil-based antifouling paints are of this type. However, in this latter case, the elution of the head nozzles from the antifouling film means the wear and tear of the antifouling film itself, and in fact, this kind of antifouling film becomes large when immersed in water for several months. The paint shows signs of wear and tear, and the toughness of the paint film is lost. As a result of research to improve these problems, the inventors of the present invention discovered that by covering the conventional antifouling coating with a film that is both water resistant and permeable, the overexposure of the antifouling coating was solved. He invented a method to prevent the deterioration of the stain-resistant coating while at the same time imparting toughness to the antifouling coating.

従来より着色塗膜上にクリヤー薄膜を塗布して強靭性を
増す方法はあるが、水中防汚塗膜の場合にその上に通常
のクリヤー薄膜を塗布すれば、塗膜の強靭性は増大でき
ても水分の透過性がなければ防汚効果は得られず、また
従来の水透過性のある膜は耐水性が劣つているためこの
ような目的に・（ま適さなかつたわけである。従つてこ
のような目的のためには耐水性が良好でかつ適度の透水
性を有する皮膜を形成するような樹脂組成物を得る必要
があり、皮膜の耐水性は水中で長期間皮膜を維持するた
めには不可欠であり、耐水性に乏しければ皮膜の早期劣
化をもたらす。Conventionally, there is a method to increase toughness by applying a thin clear film on top of a colored paint film, but in the case of an underwater antifouling film, the toughness of the paint film cannot be increased by applying a regular clear thin film on top of it. However, if there is no water permeability, an antifouling effect cannot be obtained, and conventional water permeable membranes have poor water resistance, making them unsuitable for this purpose. For this purpose, it is necessary to obtain a resin composition that forms a film with good water resistance and appropriate water permeability. is essential, and poor water resistance will lead to early deterioration of the film.

また適度の透水性は本発明の方法に従つて防汚塗膜上に
被覆された場合に、防汚塗膜中の防汚剤の溶出が本皮膜
の透水性によつてコントロールされるため是非とも必要
である。本発明者等はそのような考え方に基づいてこの
目的に適した新しい樹脂組成物を開発した。In addition, appropriate water permeability is essential because when coated on an antifouling coating according to the method of the present invention, the elution of the antifouling agent in the antifouling coating is controlled by the water permeability of the coating. Both are necessary. Based on this idea, the present inventors have developed a new resin composition suitable for this purpose.

即ち本発明による樹脂組成物は、親水性単量体の重合体
を幹ポリマーとしてこれに３種のアクリル単量体をグラ
フト共重合させたものである。親水性単量体の重合体を
利用して樹脂組成物皮膜に透水性を付与するには、本発
明のグラフト重合樹脂とする方法の外に、親水性単量体
の重合体とアクリル樹脂等との混合樹脂とする方法と、
２−ヒドロキシエチルアクリレートのような親水性単量
体の重合体をそのまま利用する方法とがあるが、単に混
合しただけでは耐水性が極端におちるばかりでなく、透
湿率においても第１図、第２図に示すようにグラフト樹
脂より低く、また親水性単量体の重合体をそのまま利用
する方法では耐水性が十分でなく、この点を補うために
は架橋させるなどの操作が必要である。That is, the resin composition according to the present invention is obtained by graft copolymerizing three types of acrylic monomers to a polymer of hydrophilic monomers as a backbone polymer. In order to impart water permeability to a resin composition film using a polymer of a hydrophilic monomer, in addition to the method of making a graft polymer resin of the present invention, a polymer of a hydrophilic monomer and an acrylic resin, etc. A method of making a mixed resin with
There is a method of using a polymer of hydrophilic monomers such as 2-hydroxyethyl acrylate as is, but simply mixing them together not only results in extremely low water resistance, but also in terms of moisture permeability (Figure 1). As shown in Figure 2, the water resistance is lower than that of the graft resin, and methods that use hydrophilic monomer polymers as they are do not have sufficient water resistance, so operations such as crosslinking are required to compensate for this point. .

これらの点に鑑みてグラフト樹脂とすることにより耐水
性を低下させず透湿率を高くできるのが本発明で使用す
る樹脂組成物の特徴である。この樹脂組成物中の親水性
単量体の重合体はポリプロピレングリコールおよびポリ
ビニルピロリドンよりなる群から選ばれた１種であり、
３種のアクリル単量体は、メタクリル酸メチル、メタク
リル酸２−ヒドロキシエチルおよびアクリル酸の炭素数
２〜４個のアルキルエステル（たとえばアクリル酸エチ
ル、アクリル酸ブチル）である。In view of these points, a characteristic of the resin composition used in the present invention is that by using a graft resin, the moisture permeability can be increased without reducing water resistance. The hydrophilic monomer polymer in this resin composition is one selected from the group consisting of polypropylene glycol and polyvinylpyrrolidone,
The three acrylic monomers are methyl methacrylate, 2-hydroxyethyl methacrylate, and a C2-4 alkyl ester of acrylic acid (eg, ethyl acrylate, butyl acrylate).

これらは親水性単量体の重合体５〜２０部（重量部、以
下同様）に対し、メタクリル酸メチル３７〜６４部、メ
タクリル酸２−ヒドロキシエチル４〜５部およびアクリ
ル酸のアルキルエステル２〜４６部用いられる。ただし
、重合体および３種のアクリル単量体の合計は１００部
である。また要すれば、酢酸ビニル、スチレン、ビニル
エーテル類およびアリルアルコール類のようなビニルお
よびアリル構造を有する非アクリル系単量体をさらに共
重合してもよい。これらのほかにさらに不飽和二重結合
のような反応性の基を導入することにより、架橋重合体
とすることも可能である。These are 37 to 64 parts of methyl methacrylate, 4 to 5 parts of 2-hydroxyethyl methacrylate, and 2 to 2 to 20 parts of alkyl ester of acrylic acid to 5 to 20 parts (by weight, the same applies hereinafter) of the hydrophilic monomer polymer. 46 copies are used. However, the total amount of the polymer and three types of acrylic monomers is 100 parts. If necessary, non-acrylic monomers having vinyl and allyl structures such as vinyl acetate, styrene, vinyl ethers and allyl alcohols may be further copolymerized. In addition to these, a crosslinked polymer can also be obtained by further introducing a reactive group such as an unsaturated double bond.

樹脂組成物中の親水性重合体、アクリル系、非アクリル
系重合体の組成範囲は適宜きめることができるが、得ら
れる樹脂組成物から形成される皮膜の特性として、４５
〜 ４８０ｇ・ ０．１ｍｗＬ／ゴ・２４ｈ− Ｃ！Ｒ
ＬＨｇの透湿率を有するものが最も適当である。Although the composition range of the hydrophilic polymer, acrylic polymer, and non-acrylic polymer in the resin composition can be determined as appropriate, the characteristics of the film formed from the resulting resin composition are as follows:
~ 480g・0.1mwL/Go・24h-C! R
A material having a moisture permeability of LHg is most suitable.

透湿率が’この値よりも小さい場合は防汚剤の溶出が十
分に行なわれず、またこの範囲より大きい場合は耐水性
が低下して来るので適当でない。If the moisture permeability is smaller than this value, the antifouling agent will not be eluted sufficiently, and if it is larger than this range, the water resistance will decrease, which is not appropriate.

更に好ましくは５％程度以上の吸水性を有するものであ
る。本樹脂組成物は顔料その他の添加剤を配合しても使
用でき、その場合でも上記範囲の透湿率をもつならばも
ちろん有効である。More preferably, it has a water absorption of about 5% or more. This resin composition can be used even if it contains pigments and other additives, and even in that case, it is of course effective as long as it has a moisture permeability within the above range.

このようにして得られた樹脂組成物は通常無色透明ない
し僅かに白濁した樹脂液となる。The resin composition thus obtained usually becomes a colorless and transparent to slightly cloudy resin liquid.

防汚塗膜上には本樹脂液を固形分１０〜２０ｑ６に希釈
して塗布するが、希釈溶剤としてはイソプロピルアルコ
ール、ブタノール等のアルコール系溶剤を主体とすれば
、これにトルオール、メチルイソブチルケトン、酢酸エ
チル等の他の溶剤を一部混合して使用しても差支えなく
、下塗となる防汚塗膜の性質によつて選択することがで
きる。This resin liquid is diluted to a solid content of 10 to 20q6 and applied onto the antifouling coating.The diluent is mainly an alcoholic solvent such as isopropyl alcohol or butanol, and toluol or methyl isobutyl ketone is used as the diluting solvent. There is no problem even if a part of other solvents such as ethyl acetate and the like are mixed and used, and the selection can be made depending on the properties of the antifouling coating film to be used as the undercoat.

防汚塗膜上に塗布する方法は、はけ塗り、スプレー塗り
、ローラー塗り等の通常の方法でよく、また本樹脂組成
物を塗布した皮膜の上には更に他の防錆塗料や防汚塗料
を塗布することも可能である。本発明による樹脂組成物
を既存の防汚塗膜上に被覆した場合は、皮膜は強靭で耐
水性があるので防汚塗膜を補強しその劣化を抑制すると
同時に外界の水はこの被覆層を通過して常に防汚塗膜面
まで達し、防汚塗膜中の防汚剤を溶出させるので防汚効
果は低下せずかつ防汚剤の一時的急激な溶出をおさえて
防汚性能を長期間にわたつて保持することができる。各
種の防汚塗料、すなわち塩化ゴムー亜酸化銅系、塩化ビ
ニルー亜酸化銅系、油性−亜酸化銅系、塩化ゴムー有機
すず系等の防汚塗膜上に本発明の方法による被覆を施し
たものと、比較対照の塗装を施した試験片について、和
歌山県下の海中に１２箇月にわたつて浸漬試験を行つた
結果では、本発明の方法による試験片は防汚性の持続が
みられ、かつ塗膜の消耗も少なく、本発明の塗膜自体何
ら異常が見られず、本発明の方法の優れた効果を示した
。The antifouling coating may be applied by any conventional method such as brushing, spraying, or roller coating, and the coating coated with this resin composition may be coated with other anticorrosive paints or antifouling coatings. It is also possible to apply paint. When the resin composition of the present invention is coated on an existing antifouling coating, the coating is tough and water resistant, reinforcing the antifouling coating and suppressing its deterioration, and at the same time, water from the outside world can penetrate this coating layer. It passes through and always reaches the antifouling coating surface and elutes the antifouling agent in the antifouling coating, so the antifouling effect does not decrease and the antifouling performance is extended by suppressing the temporary rapid elution of the antifouling agent. Can be retained for a period of time. The coating according to the method of the present invention was applied to various antifouling paints, such as those based on chlorinated rubber and cuprous oxide, vinyl chloride and cuprous oxide, oil-based cuprous oxide, and rubber chloride and organic tin. The results of a 12-month immersion test in the sea in Wakayama Prefecture on coated test pieces and a comparative control showed that the test pieces obtained by the method of the present invention maintained their antifouling properties, and There was little wear on the coating film, and no abnormalities were observed in the coating film itself, demonstrating the excellent effects of the method of the present invention.

以上述べたように本発明の樹脂組成物を防汚塗膜上に被
覆することによつて、防汚塗膜の強化と防汚効果の延長
をすることができる。As described above, by coating an antifouling coating film with the resin composition of the present invention, the antifouling coating film can be strengthened and the antifouling effect can be extended.

次にこれを実施例によつて具体的に説明する。Next, this will be specifically explained using examples.

実施例以下各例とも同様に樹脂組成物を合成しにれを既
存の防汚塗膜上の被覆し、海中浸漬試験を行一た。In each of the examples below, a resin composition was synthesized in the same manner, and the resin composition was coated on an existing antifouling coating, and an underwater immersion test was conducted.

樹脂組成物例１、下記配合（いずれも重量、以下同じ）
で樹脂組成物を合成した。ポリプロピレングリコールと
トルエンを５００而四ツロフラスコ中に仕込み、９０±
５℃まで温度をあげ、窒素気流中で残りのモノマー溶液
を ：第１表 樹脂組成物例３〜７※１．５時間かけて
滴下し、６時間そのままの温度で重合させた。Resin composition example 1, the following formulation (all weights, same below)
A resin composition was synthesized. Pour polypropylene glycol and toluene into a 500ml flask, and add 90±
The temperature was raised to 5° C., and the remaining monomer solution was added dropwise in a nitrogen stream over a period of 1.5 hours, followed by polymerization at the same temperature for 6 hours.

得られた樹脂液より皮膜を形成させ、その透湿率と吸水
率を測定した。結果は他の樹脂組成物例および比較例と
共に第２表に示す。上記成分で樹脂組成物例１と全く同
様にして合成した。樹脂組成物例３ないし例７は第１表
の組成で、また比較例は下記配合で同様に合成した。A film was formed from the obtained resin liquid, and its moisture permeability and water absorption rate were measured. The results are shown in Table 2 along with other resin composition examples and comparative examples. It was synthesized in exactly the same manner as Resin Composition Example 1 using the above components. Resin composition examples 3 to 7 had the compositions shown in Table 1, and comparative examples were synthesized in the same manner using the following formulations.

こうして得られた樹脂組成物を、下記の防汚塗料を塗布
した試験板上に、約１２μの膜厚になるようにスプレー
塗装して試験片とし、透湿率の小さい比較例および本被
覆を施さない被覆無しの例と同時に、和歌山県下１ｍの
海中に浸漬し、生物付着と塗膜の消耗の状態を調べた。The resin composition thus obtained was spray-coated onto a test plate coated with the following antifouling paint to a film thickness of approximately 12μ to obtain a test piece. At the same time as the uncoated example, it was immersed in the sea 1 meter below Wakayama Prefecture to examine the state of biofouling and wear and tear of the coating.

使用した防汚塗料は次の樹脂および防汚剤系である。The antifouling paint used was the following resin and antifouling agent system.

塩化ゴム一亜酸化銅系（ＳＲ船底塗料２号）塩化ビニル
亜酸化銅系（船底用ビナール２号）油性亜酸一化銅系（
東亜船底塗料２号）塩化ゴム一有機すず系（ＳＲ船底塗
料２号０Ｇ）浸漬試験の結果は、生物の付着状況および
塗膜の消耗の程度によつて、次のように段階的に示す。Chloride rubber cuprous oxide type (SR ship bottom paint No. 2) Vinyl chloride cuprous oxide type (ship bottom vinyl No. 2) Oil-based cuprous oxide type (
Toa Ship Bottom Paint No. 2) Chlorinated rubber-organotin system (SR Ship Bottom Paint No. 2 0G) The results of the immersion test are shown in stages as follows, depending on the state of attachment of organisms and the degree of wear of the paint film.

生物付着については、海藻類、有殼類、無殼類の生物付
着を総合して、次の６段階に示す。 ※０：ほとんど
付着していない１゜わずかに付着している ２：かなり付着している ３：広く付着している ４ 全面に付着している 全面に密に厚く付着している 膜性の評価は塗膜の消耗を次の３段階で示す。Regarding biofouling, biofouling of seaweed, shellfish, and shellless species is summarized into the following six levels. *0: Hardly adhered 1° Slightly adhered 2: Considerably adhered 3: Widely adhered 4 Adhered to the entire surface Densely and thickly adhered to the entire surface Film quality evaluation indicates the wear of the coating film in the following three stages.

◎：ほとんど消耗していない△：かなり消耗している ×：著しく消耗している ：生物付着のため判定困難 浸漬期間３か月、６か月、９か月、１２か月について調
査し、各防汚塗料の塗装系について、それぞれ第３表、
第４表、第５表、および第６表に示した。◎: Hardly worn out △: Considerably worn out Regarding the coating system of antifouling paint, Table 3 and
It is shown in Table 4, Table 5, and Table 6.

第３表から明らかなように、本発明の樹脂組成物を被覆
した例１〜例７と、透湿率の小さい比較例および被覆を
施していない場合をくらべると、本発明の方法にくらべ
て、比較例は防汚効果が一段と劣り、被覆していないも
・のは膜の消耗が早く、本発明の方法の優れていること
がわかる。As is clear from Table 3, when comparing Examples 1 to 7 in which the resin composition of the present invention was coated with a comparative example with a low moisture permeability and a case in which no coating was applied, the method of the present invention showed that It can be seen that the antifouling effect of the comparative example was much worse, and the membrane was worn out quickly in the uncoated case, indicating that the method of the present invention is superior.

第４〜第６表でもほぼ同様の結果がみられる。Almost similar results are seen in Tables 4 to 6.

【図面の簡単な説明】[Brief explanation of drawings]

第１図および第２図は、親水性単量体の重合体をグラフ
ト重合体とした場合と混合物とした場合の透湿率の比較
を示す。FIG. 1 and FIG. 2 show a comparison of the moisture permeability of a graft polymer and a mixture of hydrophilic monomers.

Claims (1)

【特許請求の範囲】[Claims] １ ポリプロピレングリコールおよびポリビニルピロリ
ドンよりなる群から選ばれた１種の親水性単量体の重合
体５〜２０重量部の存在下において、メタクリル酸メチ
ル、メタクリル酸２−ヒドロキシエチルおよびアクリル
酸の炭素数２〜４個のアルキルエステルをメタクリル酸
メチル３７〜６４重量部、メタクリル酸２−ヒドロキシ
エチル４〜５重量部および前記アクリル酸のアルキルエ
ステル２〜４６重量部（ただし前記重合体と３種の単量
体の合計は１００重量部である）で共重合することによ
つて得られる透水性樹脂組成物を水中防汚塗膜上に被覆
することを特徴とする防汚効果延長方法。1 In the presence of 5 to 20 parts by weight of a polymer of one kind of hydrophilic monomer selected from the group consisting of polypropylene glycol and polyvinylpyrrolidone, the number of carbon atoms of methyl methacrylate, 2-hydroxyethyl methacrylate and acrylic acid 2 to 4 alkyl esters of 37 to 64 parts by weight of methyl methacrylate, 4 to 5 parts by weight of 2-hydroxyethyl methacrylate, and 2 to 46 parts by weight of the alkyl ester of acrylic acid (however, if the above polymer and the three monomers are 1. A method for extending an antifouling effect, which comprises coating an underwater antifouling coating with a water permeable resin composition obtained by copolymerizing a total of 100 parts by weight.
JP51030521A 1976-03-18 1976-03-18 Method for extending antifouling effect using water-permeable resin composition Expired JPS5935938B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP51030521A JPS5935938B2 (en) 1976-03-18 1976-03-18 Method for extending antifouling effect using water-permeable resin composition
NO770913A NO153972C (en) 1976-03-18 1977-03-15 PROCEDURE FOR AA EXTEND THE LIFE AGE FOR AN MOVIE OF ANTIGROMALING.
DE2711458A DE2711458C2 (en) 1976-03-18 1977-03-16 Method of extending the shelf life of a protective antifouling paint film
GB11363/77A GB1551513A (en) 1976-03-18 1977-03-17 Process for extending the life or an antifouling paint film
NL7702975A NL7702975A (en) 1976-03-18 1977-03-18 PROCEDURE FOR EXTENDING THE LIFE OF ANTI-FROSTING FLAKES EXPOSED TO SEA WATER.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP51030521A JPS5935938B2 (en) 1976-03-18 1976-03-18 Method for extending antifouling effect using water-permeable resin composition

Publications (2)

Publication Number Publication Date
JPS52112633A JPS52112633A (en) 1977-09-21
JPS5935938B2 true JPS5935938B2 (en) 1984-08-31

Family

ID=12306105

Family Applications (1)

Application Number Title Priority Date Filing Date
JP51030521A Expired JPS5935938B2 (en) 1976-03-18 1976-03-18 Method for extending antifouling effect using water-permeable resin composition

Country Status (5)

Country Link
JP (1) JPS5935938B2 (en)
DE (1) DE2711458C2 (en)
GB (1) GB1551513A (en)
NL (1) NL7702975A (en)
NO (1) NO153972C (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2052520A (en) * 1979-06-25 1981-01-28 Trimetal Paint Co Belgium Nv Coating compositions and coatings comprising polymer-transition metal chelates
NO152012C (en) * 1983-04-06 1985-07-17 Rasmussen Oeystein PROCEDURE FOR THE PROTECTION OF EXISTING METALLIC SURFACES, SPECIFICALLY STEEL SURFACES, AGAINST CORROSION
DE4409903A1 (en) * 1994-03-23 1995-09-28 Basf Ag Graft polymers containing N-vinyl units, process for their preparation and their use
DE19651243A1 (en) * 1996-12-10 1998-06-18 Basf Ag Amphiphilic graft polymers based on graft bases containing N-vinylcarboxamide units, process for their preparation and their use
JP4484336B2 (en) * 2000-08-04 2010-06-16 伯東株式会社 Pitch control agent and pitch control method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS517034A (en) * 1974-07-08 1976-01-21 Toa Paint Co Ltd SUICHUBOOTORYO

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1409048A (en) * 1971-10-20 1975-10-08 Int Paint Co Marine top coat composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS517034A (en) * 1974-07-08 1976-01-21 Toa Paint Co Ltd SUICHUBOOTORYO

Also Published As

Publication number Publication date
NL7702975A (en) 1977-09-20
NO770913L (en) 1977-09-20
NO153972C (en) 1986-06-25
DE2711458C2 (en) 1986-09-11
JPS52112633A (en) 1977-09-21
DE2711458A1 (en) 1977-09-22
GB1551513A (en) 1979-08-30
NO153972B (en) 1986-03-17

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