JPS59159862A - Prevention of fouling of outer plate of hull - Google Patents

Abstract

PURPOSE:To protect a ship bottom stably over a long period of time from fouling and to prevent it from being blackened in polluted sea areas, by applying a specified antifouling clear varnish to the surface of the coat of an inorg. copper compd.-contg. antifouling paint applied to the ship bottom. CONSTITUTION:An antifouling clear varnish contg. a triorganotin salt of an alpha, beta-unsaturated monobasic acid (A) obtd. by condensing a tri-organotin compd. such as bis(tributyltin) oxide with (meth)acrylic acid and a copolymer compsn. (B) of an ethylenically unsaturated monomer such as acrylic acid or vinyl acetate as principal ingredients is used. Further, the varnish may contain an org. antifouling agent, a pigment, etc. The bottom of a ship is coated with an antifouling paint contg. an inorg. copper compd. such as cuprous oxide or copper rhodanide, which may contain an org. antifouling agent. The surface of the coat of said paint is then coated with said clear varnish to form a coating film having a dry thickness of 30mu or more.

Description

【発明の詳細な説明】 本発明は船体外板防汚方法にかかり、さらに詳しくは長
期にわたり安定した防汚効果を示し、しかも汚損海域に
おいて船μ（部が黒変することのない仁わだ船体外板防
汚方法に関するものである。[Detailed Description of the Invention] The present invention relates to an antifouling method for a ship's outer plate, and more specifically, it shows a stable antifouling effect over a long period of time, and furthermore, it is a method for preventing fouling of a ship's outer plate. This invention relates to an antifouling method for hull outer plating.

船ＪＪ＋’ｉに対するモ°害水中付着生物の防止には種
々の防汚塗料組成物が塗装されている。これらの防汚塗
料は、皮膜形成性の樹脂ビヒクルと、汚損生物を防除す
るための防汚剤と、これらの溶部−ないし分散用の液体
媒体（すなわち溶媒）とからなり、使用する防汚剤の水
中への溶出形式によっていくつかのタイプに大別される
。現在使用されている防汚剤どじでは、無機銅化合物系
として亜酸化銅、ロダン化鋼、水酸化銅など、有機旬化
合物系としてビス−（＋−ＩＪジブチル錫オキサイド、
トリブチル錫クロライド、トリブチル錫フルオライド、
トリブチル錫アセテート、１−リプチル絹ニコチネート
、１−リブチルタＢパーサテート、ビス−（１〜リフチ
ル翔）α、α′−ジブロムサクシネー１−１１−リフェ
ニルク８ハイドロオキサイド、１−リフェニル錫クロラ
イド、１へリフェニル錫フルオライド、トリフェニル錫
アセテ−１−、トリフェニル場ニコチネー１−、トリフ
ェニル錫ジメチルジチオ力ルバメ−１−１ｉ〜リフエニ
ル錫パーサチーｉ〜、ビス−（トリフェニル錫）α、α
′−ジブロム号クシネート、ビス−（１−リフェニル錫
）オキサイドなど、および有機含窒素イオウ化合物系と
してテトラメチルチウラムジサルファイド、テトラエチ
ルチウラムジサルファイド、ジメチルジチオカルバミン
酸亜鉛、ジングエチレンビスジチオ力ルバミン酸亜釦な
どがある。無機銅化合物と有機錫化合物の組合せは長期
の防汚性を有し、・一般に広く使用されている。Various antifouling paint compositions are applied to the ship JJ+'i to prevent harmful underwater organisms. These antifouling paints consist of a film-forming resin vehicle, an antifouling agent for controlling fouling organisms, and a liquid medium (i.e., a solvent) for dissolving or dispersing these. It is roughly divided into several types depending on the way the agent dissolves into water. Currently used antifouling agents include inorganic copper compounds such as cuprous oxide, rodanized steel, and copper hydroxide, and organic compounds such as bis-(+-IJ dibutyltin oxide,
Tributyltin chloride, Tributyltin fluoride,
Tributyltin acetate, 1-liptyl silk nicotinate, 1-ributylta B persatate, bis-(1~riftyl sho) α, α'-dibromus succine 1-11-riphenyl chloride 8 hydroxide, 1-liphenyltin chloride, to 1 Riphenyltin fluoride, triphenyltin acetate-1-, triphenyltin nicotine-1-, triphenyltin dimethyldithiorubame-1-1i ~ rifhenyltin persachii ~, bis-(triphenyltin) α, α
'-dibrome succinate, bis-(1-rephenyltin) oxide, etc., and organic nitrogen-containing sulfur compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, zinc dimethyldithiocarbamate, diethylene bisdithiorubamate substituent and so on. The combination of inorganic copper compounds and organic tin compounds has long-term antifouling properties and is widely used.

また有機錫化合物と有機含窒素イ万つ化合物との組合せ
あるいは有機錫化合物単独は長期の防汚性の点では劣る
が、塗料組成物の色を自在に設ｉ１できる利点を有し、
Ｆ　ＲＰ船、軽合金製船舶、プロペラ船等に利用されて
いる。又この種防汚塗料は銅化合物を含まぬため汚損海
域で発生する硫化水素による防汚塗料の黒変現象（硫化
鋼の生成）がなく、黒変対策用防汚塗料として使用され
ている。Furthermore, although the combination of an organic tin compound and an organic nitrogen-containing compound or the organic tin compound alone is inferior in terms of long-term stain resistance, it has the advantage that the color of the paint composition can be freely set.
It is used in FRP ships, light alloy ships, propeller ships, etc. Furthermore, since this type of antifouling paint does not contain copper compounds, there is no blackening phenomenon (formation of sulfurized steel) of the antifouling paint due to hydrogen sulfide generated in polluted sea areas, and it is used as an antifouling paint for preventing blackening.

これら防汚剤の一般的組合せによる特徴を示せば第１表
のようになる。Table 1 shows the characteristics of common combinations of these antifouling agents.

第１表 防汚剤の組合せとその塗料特徴 ＠、　、　、　、含有 特徴：　◎非常に良好 Ｏ良好 △　劣る 無機銅化合物を含む防汚塗料（Ａ、Ｃ）は防汚性におい
て有機防汚剤型の（Ｂ、Ｄ）より優れているが、汚損海
域において黒変現象が発生する。黒変現象による問題点
は１）防汚性の低下（生成した硫化銅の海水ｌ＼の溶解
度が低いため防汚性が低１ごする）２）黒変現象による
釘、の電気腐食（硫化銅は導電性て１．ウリ、黒変塗膜
と鉄（船体）が接触した場合、電位差により鉄の腐食か
促進さ牡る。Table 1 Combinations of antifouling agents and their paint characteristics @ , , , , Containing characteristics: ◎ Very good O Good △ Inferior antifouling paints containing inorganic copper compounds (A, C) have better antifouling properties than organic antifouling agents Although it is superior to types (B and D), a blackening phenomenon occurs in polluted sea areas. The problems caused by the blackening phenomenon are 1) Deterioration of stain resistance (low solubility of the produced copper sulfide in seawater, resulting in low stain resistance) 2) Electric corrosion of nails due to blackening (sulfurization) Copper is electrically conductive; 1. If the black paint film comes into contact with iron (ship hull), the potential difference will accelerate the corrosion of the iron.

但しこの電気１２食は４Ｄ　、ｉシた防食塗料を使用す
ることにより、短期間は防げる）３）黒変現象か平底部
に均一に発生しないためドック入りした１１１−美観」
二の間′題か生じる。However, this electric 12 corrosion can be prevented for a short period of time by using a 4D anti-corrosion paint.
Between the two, a problem arises.

本発明者は黒変現象解決の方法を種々検討の結果、防汚
性に優れた無機銅化合物単独おるいは有機錫化合物との
組合せ防汚塗：ｔｑ　＜第１表のＡ、Ｃ）の」−１にＩ
δろｆ４（の防汚性クリヤーワニスあるいは防汚塗３゛
１を塗：歿すれば、％）ｎｒ目工造中の舷装則間（通ツ
；（１ケ月〜６ケ月）の間、下塗の無機≦１−Ｊ化合物
含４丁：’Ａ　ＩＩダニの黒変現象が防止てざることを
見出し本発明が完成した。As a result of various studies on methods for solving the blackening phenomenon, the present inventor found that an antifouling coating using an inorganic copper compound alone or in combination with an organic tin compound, which has excellent antifouling properties: tq < A and C in Table 1 ”-1 to I
Apply antifouling clear varnish or antifouling coating 3゛1 of δ filter f4 (if it dies, %) nr during the period of shipbuilding (1 month to 6 months), The present invention was completed by discovering that the blackening phenomenon of mites was not prevented by the undercoat containing an inorganic ≦1-J compound: 'A II.

本発明の防汚１（１クリヤーフエス（以下本発明のクリ
ヤーど称す）はｒｔ　、β−不不飽和基塩基酸玉石ｆｉ
　、ｊｌ　Ｊ、ｊ、、ｊを１１１Ｇ成η１位として含む
アクリル共重合体松脂ｉｌｌ成物と溶剤（キジロール、
ドルオール、ブチルアルコール、ホワイトスピリット等
）を主要成分とし、なお必要（こ応じチクソトロピソク
性伺与剤等を配合したものである。The antifouling 1 of the present invention (1 Clear FES (hereinafter referred to as the clear of the present invention) is rt, β-unsaturated base acid cobblestone fi
, jl J, j, , an acrylic copolymer rosin ill composition containing j as the 111G η1 position and a solvent (Kijirol,
The main ingredients are doluol, butyl alcohol, white spirit, etc., and additional thixotropic agents are added as necessary.

」二重アクリル共重合体樹脂組成物は（メタ）アクリル
酸とビス１−リプチル明オギサイド、１−リフェニル匍
ハイドロオキサイドの如き三：（’Ｔ　８！ｊ　ｔＢ化
合物の縮合反応で得らｉｌ、るα、β−不飽和不飽和酸
塩基酸機翔塩と、エチレン性不飽和即累体、例えばアク
リル酸、メタアクリル酸、それらのアルキルエステル、
酎：ｍビニル、スチレン、ビニルトルエン、グリシジル
アクリレ−＋−、クリシジルメタクリレ−１−、ヒドロ
キシエチルアクリレ−１−、ヒドロキシエチルメタクリ
レート、アクリロニＩ−リル、メタタリロニ１−リル、
ビニルピリジン等の共重合体組成物である。本発明のク
リヤーを無機銅化合物を含む防、・り塗料の」二に塗装
し最グ層ｉ役として汚損海域で使用すれば水中有害生物
伺箔防止と黒変防止の効果が得られた。防汚性クリヤー
は乾燥膜Ｈて３０ミクロン以上に塗装する。乾燥膜厚を
３０ミクロン未満にすると硫化水素の透過がみられ、下
塗の無機銅化合物を含む防汚塗わが短期間に黒変し、防
汚性はともかくとし黒変防止の点で効果が期待でさない
。The double acrylic copolymer resin composition is obtained by the condensation reaction of (meth)acrylic acid and three compounds such as bis-1-lipyl hydroxide and 1-liphenyl hydroxide, α,β-unsaturated acid base acid salts, ethylenically unsaturated complexes such as acrylic acid, methacrylic acid, alkyl esters thereof,
Chu: m vinyl, styrene, vinyltoluene, glycidyl acrylate-+-, chrycidyl methacrylate-1-, hydroxyethyl acrylate-1-, hydroxyethyl methacrylate, acryloni-I-lyl, metatalyloni-1-lyl,
It is a copolymer composition of vinylpyridine and the like. When the clear of the present invention was applied to the second layer of an antifouling paint containing an inorganic copper compound and used as the final layer in polluted sea areas, it was possible to prevent the presence of harmful organisms in the water and prevent blackening. The antifouling clear should be applied to a dry film thickness of 30 microns or more. When the dry film thickness is less than 30 microns, hydrogen sulfide permeation is observed, and the antifouling coating containing an inorganic copper compound in the undercoat turns black in a short period of time, leaving aside the antifouling properties and is expected to be effective in preventing blackening. Not.

本発明のクリヤーには所望により有機防汚剤を含有せし
めることができ、また着色顔料、体質顔料等を加え着色
塗料として用いることもできる。The clear of the present invention can contain an organic antifouling agent if desired, and can also be used as a colored paint by adding coloring pigments, extender pigments, etc.

有機防汚剤としては公知のビス−（トリブチル錫）オキ
号イド、１−リプチル錫フルオライド、１−リプチル錫
ハーサテート、ビス−（トリブチル錫）α。As the organic antifouling agent, there are known bis-(tributyltin) oxide, 1-liptyltin fluoride, 1-liptyltin hersatate, and bis-(tributyltin) α.

α′−ジブロムサタシネー１−、トリフェニル錫ハイド
ロオキザイド、１へりフェニル西タロライド、Ｉ・リフ
ェニル錫フルオライド、１−リフェニル錫アセテー１−
１１−リフェニル朗パーザチー１−、ビス−（トリフェ
ニル功）α、α′−ジブロムサクシネ＝１−の一種また
は二種以上が使用でき、有機含窒素イオウ化合物系とし
ては公知のテＩ〜ラメチルチウラｌ＼モノサルファイ１
−、ジメチルジチオカルバミン酸Ｍ、ジンクエチレンビ
スジヂオカーバメ−１−、マンガニーズエチレンビスジ
チオカーバメート、テトラメチルチウラムジサルファイ
ド、テトラエチルチウラムジサルファイド、ジメチルジ
チオカルバミン酸亜鉛の一種または二種以上が使用でき
る。本発明の６徴は無機銅化合物を含む防汚塗料の上に
、アクリル共重合体樹脂組成物を主成分とするクリヤー
あるいは着色」上塗塗料を塗装し、船舶の建造中の膳装
期間中に起る黒変防止と有害生物伺着の防止をはかるこ
とにある。本発明で用いられる防汚塗料のアクリル共重
合体樹脂組成物は海水中で結合している三有機錫が加水
分解で海水に放出され、防汚剤として働くと同時に樹脂
自体が）角氷に溶解し、徐々に消耗していく。本発明の
防汚方法によりば、特装中の防汚性と黒変防止が最外層
塗膜によって得られると同時に、塗膜は消耗していくた
め、いづれ防汚性良好な無機銅化合物を含む防汚塗料が
露出されることになる。α'-dibromusatacin 1-, triphenyltin hydroxide, 1-liphenyl nitride, I-liphenyltin fluoride, 1-liphenyltin acetate 1-
One or more of the following can be used: 11-riphenylroperzachi 1-, bis-(triphenylgong) α, α'-dibromsuccine = 1-, and as organic nitrogen-containing sulfur compounds, well-known teI-ramethylthiural\ Monosulfi 1
-, dimethyldithiocarbamate M, zinc ethylene bis didiocarbamate-1-, Manganese ethylene bis dithiocarbamate, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and zinc dimethyldithiocarbamate. The six characteristics of the present invention are that a clear or colored top coat containing an acrylic copolymer resin composition as a main component is applied on top of the antifouling paint containing an inorganic copper compound, and during the preparation period during ship construction. The aim is to prevent black discoloration and the arrival of pests. In the acrylic copolymer resin composition of the antifouling paint used in the present invention, the triorganotin bound in seawater is hydrolyzed and released into the seawater, and at the same time acts as an antifouling agent, the resin itself turns into ice cubes. It dissolves and gradually wears out. According to the antifouling method of the present invention, the antifouling property and prevention of blackening during special coating can be obtained by the outermost coating film, and at the same time, as the coating film wears out, an inorganic copper compound with good antifouling properties will eventually be added. The antifouling paint contained therein will be exposed.

遊装期間中の防汚性維持と黒変防止（若干の硫化水素の
透過に由来）のため最外層の塗膜厚は乾燥膜厚で３０〜
１５０ミクロンに選定される。というのは３０ミクロン
未満ては硫化水素の透過が多くなり、下塗の無機銅化合
物防汚塗料に黒変がみられ、他方１５０ミクロンをこえ
ることは、防汚性５イ（、持、黒変防止の観点からは好
ましくとも、長期の防汚〃）果は下塗の無機銅化合物含
有防汚塗料により充分目的をＪ突成することができ、」
上塗にたよる必要性はないしまた」上塗の経済性の点か
らもりζ用的見地から上限が設定せられる。勿論所望に
より該上限をこえて上塗を適用することも自由である。In order to maintain antifouling properties and prevent blackening during the play period (due to the permeation of some hydrogen sulfide), the outermost coating film thickness should be 30~30cm (dry film thickness).
The thickness is selected to be 150 microns. This is because if the diameter is less than 30 microns, hydrogen sulfide will pass through more and the inorganic copper compound antifouling paint used as the base coat will show blackening, while if the diameter exceeds 150 microns, the antifouling property will be rated 5. Although it is preferable from the viewpoint of prevention, long-term antifouling can be achieved sufficiently by using an antifouling paint containing an inorganic copper compound as an undercoat.
There is no need to rely on a top coat, and an upper limit is set from the economic standpoint of the top coat. Of course, one is free to apply a topcoat beyond the upper limit if desired.

本発明の上塗は乾燥）摸Ｊｊ７で３０〜１００μの範囲
であることが特に好ましい。It is particularly preferred that the topcoat of the present invention has a dry coating size of 30 to 100 .mu.m.

この様に極めて容易な防汚方法によ′り汚損海域での船
舶の建造中の特装期間中に起る無機銅化合物伝用いた長
期間有効な防汚塗料の黒変現象を防ぐカイソζが見出さ
オしたことにより、従来汚損ｌ；σ域では使用できなか
った無機銅化合物を含む長期間有効な防汚塗料の使用が
可能となり、船舶塗装分野に大きな貢献をなすものであ
る。In this way, an extremely easy antifouling method is used to prevent the blackening phenomenon of long-term antifouling paints using inorganic copper compounds, which occurs during the special treatment period during the construction of ships in polluted areas. This discovery has made it possible to use a long-lasting antifouling paint containing an inorganic copper compound, which could not previously be used in the fouling l;σ region, making a major contribution to the field of ship coatings.

以下実施例により本発明を説明する。なおこれらの例に
おいて、使用したＪＪ（駒片は７０Ｘ１５０Ｘ２ｍｍの
サンドプラス１〜処理鋼板で、防汚塗料の塗装前に市販
のタールエポキシ塗、ｆ：１を１回塗りしく乾燥膜厚約
］、　Ｏ０ミクロン）、乾燥後に市販のビニルタール塗
料を２回塗り（各回乾燥膜厚約５０ミクロン）したもの
である。（以下試験片と称す）。また使用した本発明に
かかる防汚クリヤーのアクリル共重合体樹脂組成物は次
の２種である。The present invention will be explained below with reference to Examples. In these examples, the JJ used (the piece is a 70 x 150 x 2 mm Sandplus 1 to treated steel plate, and before applying the antifouling paint, apply one coat of commercially available tar epoxy, F: 1, with a dry film thickness of approximately), After drying, a commercially available vinyl tar paint was applied twice (dry film thickness of approximately 50 microns each time). (hereinafter referred to as test piece). The following two types of antifouling clear acrylic copolymer resin compositions according to the present invention were used.

（Ａ）メタクリル酸１−リプチル怨とメタクリル酸メチ
ルの（重量比７５：２５）共重合体で分子ｆｆ１２ｏ、
ｏｏｏ〜３０，０００のものの固形分５０％キジロール
溶液 （Ｂ）メタクリル酸トリブチル錫とメタクリル酸メチル
およびメタノリルミｎ−ブチル（重量比７０：２５　：
　５　）の共重合体で分子量２０，０００〜３ｏ、ｏｏ
ｏのものの固形分５０％キジロール溶液実施例Ｊ 試験片に市販の亜酸化銅を含有した塩化ゴム系防汚塗料
を２回塗装し乾燥後、供試アクリル」（重合体樹脂；；
１成物（Ａ）を乾無膜厚約３０ミクロンに塗装した。(A) A copolymer of 1-liptyl methacrylate and methyl methacrylate (weight ratio 75:25) with molecules ff12o,
ooo ~ 30,000 solid content 50% kijirol solution (B) Tributyltin methacrylate, methyl methacrylate and methanolylmin n-butyl (weight ratio 70:25:
5) copolymer with a molecular weight of 20,000 to 3o, oo
Example J of 50% solid content Kijirol solution of o.A commercially available chlorinated rubber-based antifouling paint containing cuprous oxide was applied to the test piece twice, and after drying, the sample acrylic resin (polymer resin;
1. Composition (A) was coated to a dry film thickness of about 30 microns.

実施例２ 実施例１甲の（Δ）の１ン乞燥膜厚を約５０ミクロンと
し回り二施例と同様の塗装を行った。Example 2 The same coating as in Example 2 was carried out except that the dry film thickness of (Δ) in Example 1A was set to about 50 microns.

実施例３ 試験片に市販の亜酸化ｆ４を含む三方（幾組アクリルノ
１．η【合体系防汚塗料（セルフポリシンク型）を２回
塗装し、乾燥後供試アクリル共重合体樹脂組成物（Δ）
を乾燥膜厚約５０ミクロンに塗装した。Example 3 A test piece was coated twice with a commercially available three-sided acrylic resin containing F4 suboxide (combined type antifouling paint (self-polishing type), and after drying, the composition of the test acrylic copolymer resin was Object (Δ)
was applied to a dry film thickness of approximately 50 microns.

実施例４ 試験片にｒｌｊ版の亜酸化り、４を含む三イｒ機錫アク
リル共重合体系防汚塗刺（セルフポリシンク型）を３回
塗装し、’＋’Ｖ燥後供１拭アクリル共重合体（Ａ脂組
成物（Ｂ）を軸力■膜厚約３０ミクロンに塗装した。Example 4 A test piece was coated with RLJ version of suboxide, 4-containing tri-tin acrylic copolymer antifouling coating (self-polishing type), and after drying '+'V, one wipe was applied. An acrylic copolymer (A resin composition (B)) was coated with an axial force and a film thickness of about 30 microns.

実力ｈ　１列　５ 実施例４甲の（１３）のｎＣ２力ｊｔ膜厚を約〔；０ミ
クロンどし同実施例と同もγこの塗装をイＪ゛つだ。Actual power h 1 row 5 Example 4 A (13) nC2 force jt film thickness was about 0 microns, and the same as in the same example γ This coating was also applied.

実施例Ｇ Ｊ」（駒片に市販の亜酸化銀を含む塩化ゴム系防汚塗料
を２回塗装し、乾燥後第２表の黒変防止用防汚ゆ石Ｎ（
１，１を乾燥膜厚５０ミクロンに塗装した。Example G J'' (The piece was coated with a commercially available chloride rubber antifouling paint containing silver suboxide twice, and after drying, it was coated with antifouling stone N for preventing blackening shown in Table 2.
1.1 was coated to a dry film thickness of 50 microns.

実施例７ 試験片にｉｌｊ版の亜酸化銅を含む三方機部アクリル共
重合体系防汚塗料（セルフポリシンク型）を３回塗装し
、乾燥後第２表の黒変防止用防汚塗料塗料Ｎｏ、　２を
乾燥膜厚６０ミクロンに塗装した。Example 7 A test piece was coated with ILJ version of a three-way acrylic copolymer antifouling paint (self-polysink type) containing cuprous oxide, and after drying, the antifouling paint for blackening prevention shown in Table 2 was applied. No. 2 was applied to a dry film thickness of 60 microns.

実施例８ 実施例６の黒変防止用防汚塗料Ｎｏ、　１の代りに第２
表のＮ０１３を塗装した。Example 8 Antifouling paint No. 2 for preventing blackening in Example 6 instead of No. 1
I painted N013 on the front.

実施例９ 試験片に市販の亜酸化銅を含む三方機錫アクリル共重合
体系防汚塗料（セルフポリシンク型）を３回塗装し、・
陀燥後第２表の黒変防止用防汚塗料Ｎｏ、４を乾燥膜厚
４０ミクロンに塗装した。Example 9 A commercially available tin-acrylic copolymer antifouling paint (self-polishing type) containing cuprous oxide was applied to a test piece three times.
After drying, antifouling paint No. 4 for preventing blackening in Table 2 was applied to a dry film thickness of 40 microns.

実施例１０ 実施例７の黒変防止用防汚塗料Ｎｏ、２の代りに第２表
のＮ０１５を塗装した。Example 10 Instead of antifouling paint No. 2 for preventing blackening in Example 7, No. 015 shown in Table 2 was applied.

比較例１ 試験片に市販の１コミ酸化缶を含む塩化ぢ１１系防汚塗
ネ゛４を２回塗装し、た。Comparative Example 1 A test piece was coated twice with a commercially available di-11 chloride antifouling coating 4 containing a can of oxidation.

比較例２ 試験片に市販の亜酸化銅を含む三方磯賜アクリル共重合
体系防汚塗料（セルフポリシンク型）を３（Ｑ１塗装し
た。Comparative Example 2 A test piece was coated with 3 (Q1) commercially available Mikata Isota acrylic copolymer antifouling paint (self-polishing type) containing cuprous oxide.

試１験（イｆ古生物付、？１試験）を行なった。その結
果を第２表に示す。Test 1 (with paleontology, ?1 test) was conducted. The results are shown in Table 2.

（以下余白） ］　、　ｆｉｔ、Ｆ、変テスＩ−とその結果縦、イｆ’
ｆ　３０　ｃｍ　、高さ６０　ｃｍ　（７）７　り’）
　ルｇＪ　水Ｒ’Ｊに天然ｔσ水を一杯に入Ｊし、この
中に実施例、比１１２例の試験片をつり下げ全没した。(Left below) ] , fit, F, transformation test I- and its result vertical, i f'
f 30 cm, height 60 cm (7)7 ri')
Natural tσ water was poured into water R'J, and the test pieces of Examples and Comparative Examples 112 were suspended therein and completely immersed.

この中に硫化水素／窒素（５：９５）の混合ガスを５時
間吹き込んだ。その結果を定性的にＪＡ全変度黒色にな
った程度）で判定した。A mixed gas of hydrogen sulfide/nitrogen (5:95) was blown into this for 5 hours. The results were qualitatively judged based on the extent to which the color turned black (JA total variation).

黒変稈度無−小−中一大一大人（黒変変人）実施例１〜
１０の場合、本発明の黒変防止用防汚クリヤーあるいは
男変防止用防汚塗料の塗膜を削り■りにあるｊＩ′ｌ（
酸化鋼含有塗膜の黒変度もしらべた。Black, no culm, small, medium, large, adult (black, strange) Example 1~
In the case of 10, the coating film of the antifouling clear for preventing black discoloration or the antifouling paint for preventing male discoloration of the present invention is scraped.
The degree of blackening of the coating film containing oxidized steel was also investigated.

試験結果を第３表に示しである。The test results are shown in Table 3.

比較例１，２の黒変塗膜は１１月月のテスターでＩｃｍ
はなれた点て塗膜抵抗を測定すると数Ωであり。The blackened paint films of Comparative Examples 1 and 2 were Icm on the November tester.
If you measure the resistance of the coating film at a separate point, it will be several ohms.

硫化銅の化成が明らかである。ちなみにｉ１’Ａ変前の
１１１１定では仝１かふれずほとんど無限大と思われる
。Chemical formation of copper sulfide is obvious. By the way, the 1111 constant before the i1'A change does not exceed 1 and seems to be almost infinite.

（以下余白） 第３表 ２、防汚試験（生物付ジｊ試験）とその結果防汚性の試
験は″ｙ：旅例、比較例の試験片で前３ホのｉｔ黒変性
テストを行った後、同試験片を岡１１已Ｎ玉野市後磨の
浦沖の試験用筏で海中１メー１−ルＬこ浸清し、フジッ
ボ、セルプラ等の動物およびアオサ、アオノリ等の植物
のイ」着面績％として肉眼観１４によりしらべ評価した
。ただし比較例１．２は黒変テス）・を実施し黒変した
ものと同テス１〜を行なわない正常塗膜も試験した。試
験結果を第４表に示す。(Leaving space below) Table 3 2. Antifouling test (biological test) and its results. After that, the same test piece was immersed in 1 meter of water in a test raft off the coast of Gomanoura, Tamano City, Oka 11, and was cleaned of animals such as Fujibbo and Serpura, and plants such as Ulva and Aonori. It was visually evaluated as % of surface contact by visual inspection. However, in Comparative Example 1.2, a film that turned black after being subjected to the blackening test) and a normal coating film that was not subjected to the same tests 1 to 1 were also tested. The test results are shown in Table 4.

（以下余白） 第４表 （防汚試験開始：昭和５６年４月１０日）比較例Ｑ、−
１．比校例（ン言よ比１１つ例１．比較例２の黒変テス
１〜をいていない正常塗１１す 実施例１，４は浸漬３・−６ケ月の間に、実施例２゜３
．５，６，７．Ｆｊ、９．１０は６〜９ケ月の間に最外
層の黒変防止用クリヤーあるいは防汚塗料の塗膜が消失
し、下層の防汚塗料が露出した。(Left below) Table 4 (Start of antifouling test: April 10, 1980) Comparative example Q, -
1. Examples 1 and 4 were immersed for 3 to 6 months, and Example 2.
．． 5, 6, 7. In case of Fj, 9.10, the outermost layer of blackening prevention clear or antifouling paint disappeared over a period of 6 to 9 months, and the lower layer of antifouling paint was exposed.

この様に本発明によろ尺度防止用防汚クリヤーあるいは
防ｌη塗旧ば位れた黒変防止効果を有し、その塗膜は海
水浸湾中に消失し下塗りの亜酸化銅含有長期持続性防汚
塗料が露出し、防汚効果を発揮するので極めて右意義で
ある。As described above, the present invention has an antifouling clear or antifouling coating for preventing staining, which has the effect of preventing peeling and blackening, and the coating film disappears during immersion in seawater, and the cuprous oxide content of the undercoat is long-lasting. This is extremely important because the antifouling paint is exposed and exhibits an antifouling effect.

Claims (1)

【特許請求の範囲】 （１）船体の船底部に無機銅化合物を含む防汚塗料を適
用した」二に、α、β−不飽和−塩基酸の二有機旬塩を
構成単位として含むアクリル共重合体樹脂を主成分とす
るクリヤーｄ５るいは着色上塗塗料を乾燥膜厚で少なく
とも３０μに塗装する□ことを特徴とする船体外板防汚
方法。 （２）無機銅化合物かりＦｍ化銅、ロク゛ン化銅および
水酸化銅から選ばれる行許詩求の範囲第１項記載の方法
。 （３）無畔年１化合物を含む防汚塗ｘ６゛ソにさらに右
はｊ）、ｉｊ化合物を含む特ａ′「請求の範囲５：Ｓ１
１項記載（の方法。 （・１）上塗塗料が有機防汚ｆｉｌを含有する１、〒ｉ
「請求の範囲第１項〜第３項のいづれかに記載の方法。 （５）有儀防１１テ剤が有機タリ化合物および／または
イｆ機含窒禦イオウ化合物から選ばれる１・、１許請求
の範囲第４項記載の方法。 （６）」−塗塗料がｇ・２煙）膜厚３０〜］５０μに適
用せられる特許請求の範囲第１項〜第５項のいづれかに
記載の方法。[Claims] (1) An antifouling paint containing an inorganic copper compound is applied to the bottom of the ship's hull. An antifouling method for a ship's outer panel, which comprises applying a clear D5 or colored top coat containing a polymer resin as a main component to a dry film thickness of at least 30μ. (2) The method according to item 1, wherein the inorganic copper compound is selected from copper Fmide, copper chloride, and copper hydroxide. (3) Antifouling coating containing compound No. 1 x 6 ゛ and further right is j), special a' containing ij compound "Claim 5: S1
Method of (method for) described in item 1. (・1) 1, where the top coat contains an organic antifouling film
``The method according to any one of claims 1 to 3. The method according to claim 4. (6) The method according to any one of claims 1 to 5, which is applied to a coating material having a film thickness of 30 to 50μ. .