JPH0253874A - Method for antifouling coating - Google Patents
Method for antifouling coatingInfo
- Publication number
- JPH0253874A JPH0253874A JP20547488A JP20547488A JPH0253874A JP H0253874 A JPH0253874 A JP H0253874A JP 20547488 A JP20547488 A JP 20547488A JP 20547488 A JP20547488 A JP 20547488A JP H0253874 A JPH0253874 A JP H0253874A
- Authority
- JP
- Japan
- Prior art keywords
- antifouling
- coating layer
- antifouling coating
- microcapsules
- resin
- 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.)
- Pending
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 64
- 238000000576 coating method Methods 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 title abstract description 18
- 238000000034 method Methods 0.000 title description 8
- 239000002519 antifouling agent Substances 0.000 claims abstract description 31
- 239000003094 microcapsule Substances 0.000 claims abstract description 31
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 239000010410 layer Substances 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 abstract description 21
- 229920005989 resin Polymers 0.000 abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- PWBHRVGYSMBMIO-UHFFFAOYSA-M tributylstannanylium;acetate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(C)=O PWBHRVGYSMBMIO-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 3
- 238000005498 polishing Methods 0.000 abstract 2
- 230000001413 cellular effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 15
- 239000002775 capsule Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- -1 organic nitrogen sulfur compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical class [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- BDIWFCKBPZPBQT-UHFFFAOYSA-N tributyl(tributylstannylsulfanyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)S[Sn](CCCC)(CCCC)CCCC BDIWFCKBPZPBQT-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical class CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- HZFSIJCQPSIJHB-UHFFFAOYSA-L zinc;n-methylcarbamodithioate Chemical compound [Zn+2].CNC([S-])=S.CNC([S-])=S HZFSIJCQPSIJHB-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、船底或いは取水管、海水タンク等において、
生物付着による効率の低下を防止するための防汚被覆方
法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to ship bottoms, water intake pipes, seawater tanks, etc.
This invention relates to an antifouling coating method for preventing a decrease in efficiency due to biofouling.
船底や取水管等に、動物性或いは植物性の水中汚染生物
、とりわけ海水汚染生物が付着、繁殖することは、船舶
の航行速度の減少や燃費の増大、また取水管の液送効率
の減少や取水管のつまりによる事故等の大きな被害をも
たらすことは周知である。そのため各種の防汚成分を含
有した防汚塗料が広く用いられている。The adhesion and proliferation of animal or plant-based aquatic contaminants, especially seawater contaminants, on the bottom of ships, intake pipes, etc. can reduce the vessel's sailing speed, increase fuel consumption, and reduce the liquid transport efficiency of intake pipes. It is well known that clogged water intake pipes can cause major damage such as accidents. Therefore, antifouling paints containing various antifouling components are widely used.
防汚塗料有効成分としては、亜酸化銅、有機錫化合物、
有機窒素化合物、有機硫黄化合物、有機塩素化合物やそ
の他多くの化合物がある。これらは、その毒性により生
物を殺傷し、あるいは生物を忌避させることにより、生
物の付着を防止する。Antifouling paint active ingredients include cuprous oxide, organic tin compounds,
These include organic nitrogen compounds, organic sulfur compounds, organic chlorine compounds, and many other compounds. These prevent the attachment of living organisms by killing or repelling living organisms due to their toxicity.
この防汚能力は、水中で塗膜から防汚有効成分が水中に
溶出されて、その効力が発揮される。したがって、塗料
の寿命は防汚有効成分の溶出速度をいかに有効に調整す
るかにかかっており、これまで種々の溶出速度調整方法
が検討されているが、防汚効果の持続時間を延長させる
適確な方法はまだ確立されていない。This antifouling ability is exerted when the antifouling active ingredient is eluted from the coating film into water. Therefore, the lifespan of a paint depends on how effectively the elution rate of the antifouling active ingredient is adjusted, and various elution rate adjustment methods have been studied so far, but there are some methods that can extend the duration of the antifouling effect. A precise method has not yet been established.
防汚塗料は、従来防汚剤を水溶性又は水不溶性樹脂に分
散、溶解して含有させたものが使われて来たが、近年防
汚剤を有機又は無機のマイクロカプセルに内包させたも
のが試みはしめられた。前者は初期防汚性能は確保でき
るが溶出速度が速く、長期的に性能が維持できない。一
方、後者は長期にわたり防汚性能が維持できるが初期の
防汚性能が不充分であった。すなわち、後者のものでは
、初期段階でマイクロカプセルから塗膜表面に防汚剤が
拡散するのに時間を要するため、生物繁殖の激しい場所
においては、この初期段階に生物が付着することがあり
、この付着した生物の大部分は防汚剤の拡散と共に殺傷
されるが、場合によっては付着した生物の上に次々と生
物が付着していく虞れがあった。Antifouling paints have traditionally contained antifouling agents dispersed or dissolved in water-soluble or water-insoluble resins, but in recent years, antifouling paints have been developed in which antifouling agents are encapsulated in organic or inorganic microcapsules. But the attempt was stopped. The former can ensure initial antifouling performance, but the elution rate is fast and the performance cannot be maintained over a long period of time. On the other hand, although the latter can maintain its antifouling performance over a long period of time, its initial antifouling performance was insufficient. In other words, in the latter case, it takes time for the antifouling agent to diffuse from the microcapsules to the coating surface at the initial stage, so in areas where biological growth is intense, organisms may attach at this early stage. Most of these attached organisms are killed as the antifouling agent spreads, but in some cases, there is a possibility that other organisms may adhere to the attached organisms one after another.
そこで本発明の目的は、長期にわたり生物の付着を防止
する防汚被覆方法を提供することにある。Therefore, an object of the present invention is to provide an antifouling coating method that prevents attachment of living things over a long period of time.
上記課題の解決のため、本発明者は、防汚剤を内包する
マイクロカプセル型防汚被覆層と防汚剤を含む樹脂型防
汚被覆層を積層することで、上記課題が解決されること
を見い出し、本発明に至った。従って本発明は、基材に
対しで、防汚剤を内包する無機多孔質マイクロカプセル
を含む防汚被覆層を下層に設け、その上に加水分解によ
り樹脂と防汚有効性成分を溶出する自己研掃型防汚被覆
層又は水溶性樹脂に防汚剤を混入した溶解マｌ−ＩＪノ
クス型防汚被覆層を上層に設けることを特徴とする防汚
被覆方法を提供する。In order to solve the above problem, the present inventor has proposed that the above problem can be solved by laminating a microcapsule type antifouling coating layer containing an antifouling agent and a resin type antifouling coating layer containing an antifouling agent. We have discovered this, and have arrived at the present invention. Therefore, the present invention provides a base material with an antifouling coating layer containing inorganic porous microcapsules containing an antifouling agent as a lower layer, and a self-containing coating layer on which a resin and an effective antifouling component are eluted by hydrolysis. Provided is an antifouling coating method characterized by providing an abrasive type antifouling coating layer or a dissolved Mal-IJ Nox type antifouling coating layer in which an antifouling agent is mixed in a water-soluble resin as an upper layer.
本発明は、下層の防汚被覆層に無機多孔質マイクロカプ
セルを用いているので、有機樹脂をカプセル壁とした防
汚被覆のように、壁膜の厚薄による問題が生じない。つ
まり壁膜が厚いと防汚剤の溶出が過度に抑制され、防汚
性能が低下し、壁膜が薄いと、強度が弱くなりカプセル
破壊による徐放性が消失するという問題が生しない。そ
こで、防汚剤を内包した無機多孔質マイクロカプセルを
下層に用いると、防汚剤の溶出が安定に制御され、長期
間防汚効果が持続する。一方上層の防汚被覆層に自己研
掃型又は溶解マトリックス型を使用すると、初期防汚性
能が発揮される。In the present invention, since inorganic porous microcapsules are used in the lower antifouling coating layer, problems due to the thickness of the wall film do not occur, unlike antifouling coatings with capsule walls made of organic resin. In other words, if the wall film is thick, the elution of the antifouling agent will be excessively suppressed and the antifouling performance will be lowered, and if the wall film is thin, the strength will be weakened and the sustained release property will not be lost due to capsule destruction. Therefore, when inorganic porous microcapsules containing an antifouling agent are used as the lower layer, the elution of the antifouling agent is stably controlled and the antifouling effect is maintained for a long period of time. On the other hand, when a self-cleaning type or a dissolving matrix type is used for the upper antifouling coating layer, initial antifouling performance is exhibited.
このようにして、積層型の防汚被覆層により、生物の付
着を長期間安定に防くことができる。In this way, the laminated antifouling coating layer can stably prevent attachment of living organisms for a long period of time.
以下本発明をさらに詳説する。 The present invention will be explained in more detail below.
本発明において、マイクロカプセル中に内包させる防汚
剤の例として、トリブチル錫アセテート、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
サルファイド等のトリブチル錫化合物、トリフェニル錫
クロライド、トリフェニル錫フルオライド等のトリフェ
ニル錫化合物、テトラメチルチラウムジサルファイドや
ジンクメチルジチオカルバメート等の有機窒素硫黄化合
物、塩化キノン化合物、ジニトロ化合物、フェノール系
化合物、イミダシリン化合物、有機含塩素化合物、亜鉛
化銅を始めとする銅化合物等が挙げられる。これらは、
有機錫化合物のように、毒性により生物を殺傷するタイ
プと、シリル第４アミン化合物のように毒性は低いが生
物を忌避させるタイプのものがあるが、いずれもマイク
ロカプセルに内包することにより、防汚性能の長寿命化
が可能である。In the present invention, examples of antifouling agents to be encapsulated in microcapsules include tributyltin compounds such as tributyltin acetate, tributyltin chloride, tributyltin fluoride, and tributyltin sulfide; Phenyltin compounds, organic nitrogen sulfur compounds such as tetramethylthiraum disulfide and zinc methyldithiocarbamate, quinone chloride compounds, dinitro compounds, phenolic compounds, imidacillin compounds, organic chlorine-containing compounds, copper compounds such as zincated copper etc. these are,
There are types such as organotin compounds that kill living things due to their toxicity, and types such as silyl quaternary amine compounds that have low toxicity but repel living things, but both can be prevented by encapsulating them in microcapsules. It is possible to extend the life of soiling performance.
カプセル壁の材質としては、水不溶性の無機多孔質物質
がよく、具体的には、二酸化硅素やアルカリ土金属の珪
酸塩等が挙げられる。水溶性の無機物質では、カプセル
壁が溶けてしまい拡散障壁としての機能を失うため好ま
しくない。The material for the capsule wall is preferably a water-insoluble inorganic porous substance, and specific examples include silicon dioxide and alkaline earth metal silicates. Water-soluble inorganic substances are undesirable because the capsule wall dissolves and loses its function as a diffusion barrier.
マイクロカプセル内に防汚剤を内包させるには、種々の
方法がある。たとえば防汚剤を核としてその表面で界面
重合を行う方法、多孔質中空マイクロカプセルを真空引
きした後、防汚剤の溶液を注入し、加熱あるいは真空引
き等で溶媒を蒸発させる方法等がある。例えば水や有溶
液に不溶な防汚剤を使用する時はこれを芯物質としてＷ
２Ｏ型のエマルジョンを調整し界面重合（沈殿）法によ
りマイクロカプセル化することができる。また水溶性や
油溶性の防汚剤を使用する時は、予め中空マイクロカプ
セルを作製して、これ含浸ないしは真空吸引させること
によりカプセル化できる。中空マイクロカプセルは芯物
質を用いずに上記と同様の方法でカプセル壁を作り、適
当な時に反応を中止させ、洗浄、蒸発（カプセル内の溶
剤）させることにより多孔質中空カプセルを得ることが
できる。There are various methods for encapsulating an antifouling agent in microcapsules. For example, there is a method in which interfacial polymerization is carried out on the surface using an antifouling agent as a core, or a method in which a porous hollow microcapsule is evacuated, an antifouling agent solution is injected, and the solvent is evaporated by heating or vacuuming. . For example, when using an antifouling agent that is insoluble in water or other solutions, use W as the core material.
A 2O type emulsion can be prepared and microencapsulated by an interfacial polymerization (precipitation) method. Further, when using a water-soluble or oil-soluble antifouling agent, hollow microcapsules are prepared in advance and encapsulation can be carried out by impregnating them or vacuum suction. Hollow microcapsules can be obtained by creating capsule walls in the same manner as above without using a core material, stopping the reaction at an appropriate time, washing, and evaporating (solvent inside the capsule) to obtain porous hollow capsules. .
マイクロカプセルの大きさは、種々の大きさが使用され
るが０．５〜１５０μｍが好ましく、更には０．５〜２
５μｍが好ましい。０．５μｍ以下ではカプセル中の防
汚剤の含有量が少なく防汚性能が低下する。１５０μｍ
以上では塗料中でのマイクロカプセルの分散性が低下す
る。特に０．５〜２５μｍの大きさのマイクロカプセル
を用いると安定な性能が得られる。Various sizes of microcapsules are used, but preferably 0.5 to 150 μm, more preferably 0.5 to 2 μm.
5 μm is preferred. If the diameter is less than 0.5 μm, the content of the antifouling agent in the capsule is small and the antifouling performance decreases. 150μm
Above this, the dispersibility of the microcapsules in the paint decreases. In particular, stable performance can be obtained by using microcapsules with a size of 0.5 to 25 μm.
カプセルの細孔径は２０Å以上が好ましく、２０人未満
では、防汚剤の溶出が抑制され、防汚性能が低下する。The pore diameter of the capsule is preferably 20 Å or more; if it is less than 20, the elution of the antifouling agent will be suppressed and the antifouling performance will deteriorate.
下層の防汚被覆中の防汚剤内包カプセルの量は１０〜８
Ｑｗｔ％が好ましく、１０呵％未満では防汚性能が十分
でなく、８０ｗｔ％を超えると造膜性が悪くなる。The amount of antifouling agent-containing capsules in the lower antifouling coating is 10 to 8.
Qwt% is preferred; if it is less than 10wt%, the antifouling performance will not be sufficient, and if it exceeds 80wt%, the film forming property will be poor.
上記防汚剤を内包するマイクロカプセルは、マＩ・ワッ
クス樹脂中に分散される。このマトリックス樹脂として
は、水不溶性樹脂が好ましい。もし、水溶性樹脂である
と、この樹脂が早期に溶出してしまい、長寿命化を望め
ないためである。この水不溶性樹脂としては、エポキシ
樹脂、クールエポキシ、ウレタン、塩化ゴム、ポリエス
テル、アクリル樹脂、フェノール樹脂、シリコーン系樹
脂、等水不溶性の樹脂であればいずれを用いてもよい。The microcapsules containing the antifouling agent are dispersed in the MAI wax resin. As this matrix resin, a water-insoluble resin is preferable. This is because if the resin is water-soluble, the resin will be eluted early, making it impossible to expect a longer life. As this water-insoluble resin, any water-insoluble resin such as epoxy resin, cool epoxy, urethane, chlorinated rubber, polyester, acrylic resin, phenol resin, silicone resin, etc. may be used.
塗料中の防汚剤内包マイクロカプセルの量は、３〜８０
重量％が好ましく、３重量％未満では防汚性能が発揮で
きず、８０重量％を超えると、樹脂が不足するので造膜
が困難になり、マイクロカプセルが脱落したり、塗膜が
剥離することがある。The amount of antifouling agent-containing microcapsules in the paint is 3 to 80
Weight% is preferable; if it is less than 3% by weight, antifouling performance cannot be achieved, and if it exceeds 80% by weight, there will be a shortage of resin, making it difficult to form a film, causing microcapsules to fall off or the coating to peel off. There is.
一方、上層に用いられる樹脂は、水溶性又は加水分解性
の樹脂が好ましい。なぜなら不溶解マトリックス型や拡
散型のような水不溶性樹脂を用いた防汚被覆を施すと、
水不溶性樹脂が被覆表面に残り、下層のマイクロカプセ
ルから拡散してくる防汚剤の障壁となるとともに、不溶
解マトリックス型の時は上層被覆の防汚剤が溶出した後
、表面状態が粗くなるため好ましくない。さらにこの上
層被覆層の厚さは５μｍ〜１００μｍが好ましい。On the other hand, the resin used in the upper layer is preferably a water-soluble or hydrolyzable resin. This is because when applying an antifouling coating using water-insoluble resin such as an insoluble matrix type or a diffusion type,
The water-insoluble resin remains on the coating surface and acts as a barrier to the antifouling agent that diffuses from the microcapsules in the lower layer, and in the case of an insoluble matrix type, the surface becomes rough after the antifouling agent in the upper coating is eluted. Therefore, it is undesirable. Further, the thickness of this upper coating layer is preferably 5 μm to 100 μm.
５μｍ未満では初期防汚性能が充分に得られない。If it is less than 5 μm, sufficient initial antifouling performance cannot be obtained.
また防汚性能の持続のためにはマイクロカプセルらであ
る。さらに本発明の下層の防汚被覆には、塗膜の色、外
観等を調節するための体質顔料、塗料の安定性、塗装の
作業性を改良するためのチキソ剤、マイクロカプセル、
体質顔料等の塗料中での沈降、凝集を防止するための分
散剤等を使用してもよく、さらにカプセル化されてない
防汚剤を含有させてもよい。Microcapsules are also used to maintain antifouling performance. Furthermore, the lower antifouling coating of the present invention includes extender pigments for adjusting the color and appearance of the paint film, thixotropic agents for improving paint stability and painting workability, microcapsules, etc.
A dispersant or the like may be used to prevent sedimentation or aggregation of extender pigments or the like in the paint, and an unencapsulated antifouling agent may also be included.
本発明の積層型の防汚被覆は、−船釣には第１図のよう
に、金属、プラスチック、木材等を材質とする板や管等
の基材１上に直接或いは防食塗料２で前処理された後、
マイクロカプセル３ａを有するマイクロカプセル型防汚
被覆３を下層に、自己研掃型又は溶解型防汚被覆層４を
上層に設けて塗装される。The laminated antifouling coating of the present invention is applied directly to a base material 1 such as a plate or pipe made of metal, plastic, wood, etc., or coated with anticorrosive paint 2, as shown in FIG. After being processed,
A microcapsule type antifouling coating 3 having microcapsules 3a is provided as a lower layer, and a self-cleaning type or dissolving type antifouling coating layer 4 is provided as an upper layer.
次に実施例および比較例を示し本発明の効果を明らかに
する。Next, Examples and Comparative Examples will be shown to clarify the effects of the present invention.
第１表に示すＡ−Ｅの５種類の防汚塗料を準備した。マ
イクロカプセルは、シリカ製で粒子径０．５〜２５μｍ
（平均６．５μｍ）、細孔範囲２０〜１５０人ものを
使用した。なおりデセル中に含まれる防汚剤の量はトリ
ブチル錫フルオライド（ＴＢＴＦ）で２５重量％、シリ
ル第４アミン化合物で５０重量％である。これを予め防
錆塗装した３ ００ Ｘ ３００ 龍の鋼板の両面に乾
燥膜厚が第２表の条件になるように塗装して試験鋼板を
得た。Five types of antifouling paints A to E shown in Table 1 were prepared. Microcapsules are made of silica and have a particle size of 0.5 to 25 μm.
(average 6.5 μm) and pores ranging from 20 to 150 were used. The amount of antifouling agent contained in Decel is 25% by weight of tributyltin fluoride (TBTF) and 50% by weight of a silyl quaternary amine compound. This was coated on both sides of a 300 x 300 dragon steel plate, which had been previously coated with anti-rust coating, so that the dry film thickness would meet the conditions shown in Table 2 to obtain a test steel plate.
この試験板を三重県鳥羽湾の界面下１ｍの位置に浸漬し
、６ケ月毎に２年間生物付着状況を観察した。なお浸漬
は１２月及び６月に開始するという２つの条件で行なっ
た。結果を第２表に示す。This test plate was immersed 1 m below the interface in Toba Bay, Mie Prefecture, and the state of biofouling was observed every 6 months for 2 years. The immersion was carried out under two conditions: starting in December and June. The results are shown in Table 2.
マイクロカプセル型防汚皮膜に従来の自己研掃型塗料あ
るいは溶解マトリックス型塗料をトップコートした実施
例１〜６においては、いずれも優秀な防汚性能を示した
。実施例５と比較例１の比較からこのトップコートは１
０μｍ以上必要なことがわかる。また比較例２のように
トップコートに不溶解マトリックス型のトップコートを
用いると、トップコートの水不溶性樹脂が表面に残るた
め、防汚性能の低下を招き、また表面粗度も大きくなる
ことから好ましくない。In Examples 1 to 6, in which the microcapsule type antifouling coating was top-coated with a conventional self-cleaning paint or a dissolving matrix type paint, all exhibited excellent antifouling performance. From the comparison between Example 5 and Comparative Example 1, this top coat was 1
It can be seen that 0 μm or more is required. Furthermore, if an insoluble matrix type top coat is used as in Comparative Example 2, the water-insoluble resin of the top coat remains on the surface, resulting in a decrease in antifouling performance and an increase in surface roughness. Undesirable.
比較例３，４はそれぞれ従来の防汚被覆の場合であるが
、比較例３では樹脂が加水分解により溶出していくため
長期の防汚性能が得られない。また比較例４では、冬季
のように比較的生物繁殖の速度が遅い時期に浸漬が開始
されると、防汚剤がカプセル内から表面へ拡散するまで
に付着する生物の量が少ないため良好な防汚性能が発揮
できるが、夏季に浸漬を開始すると、防汚剤が拡散する
までの初期に速やかに生物付着が発生ずるため好ましく
ない。Comparative Examples 3 and 4 are cases of conventional antifouling coatings, but in Comparative Example 3, long-term antifouling performance cannot be obtained because the resin is eluted by hydrolysis. In addition, in Comparative Example 4, if immersion is started in the winter when the rate of biological reproduction is relatively slow, the amount of organisms that adhere to the antifouling agent before it diffuses from the inside of the capsule to the surface is small, so it is favorable. Although antifouling performance can be exhibited, starting immersion in summer is not preferable because biofouling will quickly occur in the early stages until the antifouling agent has diffused.
以上のように、本発明によれば、マイクロカプセル型防
汚被覆の上に従来型防汚被覆層を設けることにより、初
期から長期間十分な防汚性能を発揮する被覆が得られる
。As described above, according to the present invention, by providing a conventional antifouling coating layer on a microcapsule type antifouling coating, a coating that exhibits sufficient antifouling performance for a long period of time from the initial stage can be obtained.
第１図は防汚被覆態様例の層構成断面図である。
１・・・基材、２・・・防食塗料、３・・・マイクロカ
プセル型防汚被覆、３ａ・・・マイクロカプセル、４・
・・防汚被覆層。FIG. 1 is a sectional view of the layer structure of an example of an embodiment of the antifouling coating. DESCRIPTION OF SYMBOLS 1... Base material, 2... Anticorrosion paint, 3... Microcapsule type antifouling coating, 3a... Microcapsule, 4.
...Antifouling coating layer.
Claims (1)
クロカプセルを含む防汚被覆層を下層に設け、その上に
自己研掃型防汚被覆層又は溶解マトリックス型防汚被覆
層を上層に設けることを特徴とする防汚被覆方法。(1) An antifouling coating layer containing inorganic porous microcapsules containing an antifouling agent is provided as a lower layer on the base material, and a self-cleaning antifouling coating layer or a dissolving matrix type antifouling coating layer is provided on the lower layer. An antifouling coating method characterized by providing an upper layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20547488A JPH0253874A (en) | 1988-08-18 | 1988-08-18 | Method for antifouling coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20547488A JPH0253874A (en) | 1988-08-18 | 1988-08-18 | Method for antifouling coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0253874A true JPH0253874A (en) | 1990-02-22 |
Family
ID=16507458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20547488A Pending JPH0253874A (en) | 1988-08-18 | 1988-08-18 | Method for antifouling coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0253874A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114947A (en) * | 2000-10-06 | 2002-04-16 | Takeda Chem Ind Ltd | Coating composition and method for preparing coating composition |
| CN104755564A (en) * | 2012-11-06 | 2015-07-01 | 罗门哈斯公司 | Antifouling paint system |
| WO2018221642A1 (en) * | 2017-06-01 | 2018-12-06 | 中国塗料株式会社 | Multilayer antifouling coating, multilayer antifouling coating-equipped substrate and method for producing same, coating material kit for forming multilayer antifouling coating, top-layer antifouling coating material composition, and antifouling method |
| WO2018221641A1 (en) * | 2017-06-01 | 2018-12-06 | 中国塗料株式会社 | Multilayer antifouling coating, multilayer antifouling coating-equipped substrate and method for producing same, coating material kit for forming multilayer antifouling coating, top-layer antifouling coating material composition, and antifouling method |
-
1988
- 1988-08-18 JP JP20547488A patent/JPH0253874A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114947A (en) * | 2000-10-06 | 2002-04-16 | Takeda Chem Ind Ltd | Coating composition and method for preparing coating composition |
| CN104755564A (en) * | 2012-11-06 | 2015-07-01 | 罗门哈斯公司 | Antifouling paint system |
| JP2016502574A (en) * | 2012-11-06 | 2016-01-28 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Antifouling paint system |
| JP2018204017A (en) * | 2012-11-06 | 2018-12-27 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Antifouling coating system |
| WO2018221642A1 (en) * | 2017-06-01 | 2018-12-06 | 中国塗料株式会社 | Multilayer antifouling coating, multilayer antifouling coating-equipped substrate and method for producing same, coating material kit for forming multilayer antifouling coating, top-layer antifouling coating material composition, and antifouling method |
| WO2018221641A1 (en) * | 2017-06-01 | 2018-12-06 | 中国塗料株式会社 | Multilayer antifouling coating, multilayer antifouling coating-equipped substrate and method for producing same, coating material kit for forming multilayer antifouling coating, top-layer antifouling coating material composition, and antifouling method |
| JPWO2018221641A1 (en) * | 2017-06-01 | 2020-05-21 | 中国塗料株式会社 | Laminated antifouling coating film, substrate with laminated antifouling coating film and manufacturing method thereof, coating kit for forming laminated antifouling coating film, upper layer antifouling coating composition, and antifouling method |
| JPWO2018221642A1 (en) * | 2017-06-01 | 2020-05-21 | 中国塗料株式会社 | Laminated antifouling coating film, substrate with laminated antifouling coating film and manufacturing method thereof, coating kit for forming laminated antifouling coating film, upper layer antifouling coating composition, and antifouling method |
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