JPH05112740A - Antifouling coating composition - Google Patents
Antifouling coating compositionInfo
- Publication number
- JPH05112740A JPH05112740A JP27565991A JP27565991A JPH05112740A JP H05112740 A JPH05112740 A JP H05112740A JP 27565991 A JP27565991 A JP 27565991A JP 27565991 A JP27565991 A JP 27565991A JP H05112740 A JPH05112740 A JP H05112740A
- Authority
- JP
- Japan
- Prior art keywords
- tannin
- antifouling
- tannic acid
- compsn
- coating
- 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.)
- Withdrawn
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、船底あるいは取水管、
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材に関する。BACKGROUND OF THE INVENTION The present invention relates to a ship bottom or an intake pipe,
The present invention relates to an antifouling coating material for preventing a decrease in efficiency due to biological attachment in a seawater tank or the like.
【０００２】[0002]
【従来の技術】船底や取水管等に、動物性あるいは植物
性の水中汚染生物、とりわけ海水汚染生物が付着、繁殖
してそれらの機能の低下を招くことは周知である。例え
ば、船舶では航行速度の減少や燃費の増大をもたらし、
また取水管では液走効率の減少、あるいは取水管のつま
りによる事故等の大きな被害をもたらすこともある。そ
のため各種の防汚有効成分を含有した防汚被覆材が広く
用いられている。防汚有効成分としては、有機錫、水
銀、砒素、亜酸化銅など多くの物質が知られているが、
これらはその毒性により、生物を殺傷しあるいは忌避さ
せることにより生物の付着を防止するものである。2. Description of the Related Art It is well known that animal or plant underwater contaminated organisms, especially seawater contaminated organisms, adhere to and propagate on ship bottoms, intake pipes, etc., leading to deterioration of their functions. For example, in a ship, it causes a decrease in navigation speed and an increase in fuel consumption.
In addition, the intake pipe may reduce liquid running efficiency or cause serious damage such as an accident due to clogging of the intake pipe. Therefore, antifouling coating materials containing various antifouling active ingredients are widely used. Although many substances such as organic tin, mercury, arsenic, and cuprous oxide are known as antifouling active ingredients,
Due to their toxicity, these prevent the attachment of organisms by killing or repelling them.
【０００３】従来、海洋は無限に広いものと考えて、こ
れら毒物が溶出しても拡散することにより海洋汚染の問
題はないと考えられてきた。ところが、近年、これら毒
物が生体内に濃縮することにより、著しく海洋汚染を進
行させていることが判明した。特に発電所等に認められ
るように海水を取水して冷却水として使用した後排水す
るようなシステムにおいては、配管が固定されるため配
管内を毒性の防汚材で被覆すると排水口付近での汚染度
が非常に高まることになる。このため現在では、海水取
水管において、毒性物質を含んだ防汚被覆は規制されて
いる。また、性能および価格の点で船底塗料等に広く使
用されてきた有機スズ化合物について、海洋汚染が問題
化し、これに代わる有効な防汚剤の開発が望まれてい
る。It has been conventionally considered that the ocean is infinitely wide, and even if these poisons are dissolved, they diffuse and do not pose a problem of ocean pollution. However, in recent years, it has been found that the concentration of these toxic substances in the living body causes remarkable marine pollution. In particular, in systems where seawater is taken in, used as cooling water, and then drained, as recognized in power plants, etc., the pipes are fixed, so covering the pipes with a toxic antifouling material may cause The degree of pollution will be greatly increased. Therefore, at present, antifouling coatings containing toxic substances are regulated in seawater intake pipes. Further, with respect to organotin compounds that have been widely used in ship bottom paints and the like in terms of performance and price, marine pollution has become a problem, and development of effective antifouling agents to replace them has been desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、毒性
物質を使用することなく、安全無公害型の防汚被覆材料
を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a safe and pollution-free antifouling coating material without using toxic substances.
【０００５】[0005]
【課題を解決するための手段】本発明者らは毒性は持た
ないが生物忌避作用を有する物質について種々検討の結
果、植物類より抽出されるタンニンまたはタンニン酸が
顕著な生物忌避作用を有することを見いだした。そして
さらに、タンニンまたはタンニン酸を被覆材中に含有さ
せると優れた防汚性能を発揮させることができるという
知見に基づき、本発明に至ったものである。本発明は、
防汚成分としてタンニンまたはタンニン酸を被覆材の全
固形分中0.5 重量％以上含むことを特徴とする防汚被覆
材を要旨とする。Means for Solving the Problems The present inventors have conducted various studies on substances which are non-toxic but have biological repellency, and as a result, tannin or tannic acid extracted from plants has a remarkable biological repellency. I found it. Further, the present invention has been completed based on the finding that excellent antifouling performance can be exhibited by containing tannin or tannic acid in the coating material. The present invention is
A gist of an antifouling coating material is characterized by containing tannin or tannic acid as an antifouling component in an amount of 0.5% by weight or more based on the total solid content of the coating material.
【０００６】本発明において防汚成分として用いるタン
ニンは、植物界に広く存在する複数のフェノール性水酸
基を有する芳香族化合物であって、分子量は、少ないも
ので400 〜500 、多いものでは数千〜数万に達する。タ
ンニンは加水分解により糖(主としてＤ−グルコース)
とフェノールカルボン酸に分解される加水分解型タンニ
ンと、加水分解を受けない縮合型タンニン (フラバン３
オールが主構成単位となるものが多い) に大別される。
本発明で使用されるタンニンは、特に限定されず、いず
れのタイプのタンニンでも使用できる。またその混合物
であってもよい。The tannin used as an antifouling component in the present invention is an aromatic compound having a plurality of phenolic hydroxyl groups widely existing in the plant kingdom, and has a low molecular weight of 400 to 500, and a large number of thousands. Reach tens of thousands. Tannin is a sugar (mainly D-glucose) by hydrolysis.
And hydrolyzable tannin that is decomposed into phenolcarboxylic acid and condensed tannin that does not undergo hydrolysis (flavan 3
All are the main constituent units in many cases).
The tannin used in the present invention is not particularly limited, and any type of tannin can be used. It may also be a mixture thereof.
【０００７】タンニンは通常植物より抽出したものを使
用するが、植物より抽出されるタンニンは単体化合物で
はなく複数のタンニンの混合物であり、通常前記加水分
解型タンニンと縮合型タンニンの両者を含むものであ
る。例えば、阿仙薬 (ガンビール) 、ケブラコ、スマッ
ク、五倍子、ワットル、ディビディビ、ベロネ、没食
子、カシ、ミロバラン等を細断したものに水を加え煮沸
して煎じた後、濾過して冷却固化することによって抽出
されたタンニンが使用できるが、その抽出材料や抽出方
法は制約されない。また、ゲンノショウコや柿渋等市販
のタンニン高含有生薬を利用してもよい。The tannin is usually extracted from a plant, but the tannin extracted from the plant is not a single compound but a mixture of a plurality of tannins, and usually contains both the hydrolyzable tannin and the condensed tannin. .. For example, shredded Asenyaku (Gambir), Quebraco, Smack, Quintuplet, Wattle, Dividibi, Verone, Gallicum, Oak, Myrobalan, etc., add water to simmer and boil, then filter and solidify by cooling. Although the tannin extracted by can be used, the extraction material and the extraction method are not limited. Alternatively, a commercially available crude drug with a high tannin content, such as ginger ginger and persimmon astringent, may be used.
【０００８】タンニン酸(m−ガロイル没食子酸) はタン
ニンの加水分解により得られる化合物であり、市販のも
のを利用できる。このようにタンニンまたはタンニン酸
は容易にしかも安価に入手することができ、しかも天然
物由来のため毒性もない。タンニンまたはタンニン酸が
優れた防汚性能を示す理由については、明らかではない
が、生理活性の強いフェノール性水酸基 (−OH) を多数
有することが一因と考えられる。Tannic acid (m-galloyl gallic acid) is a compound obtained by hydrolysis of tannin, and a commercially available product can be used. As described above, tannin or tannic acid can be easily obtained at low cost, and since they are derived from natural products, they are not toxic. The reason why tannin or tannic acid exhibits excellent antifouling performance is not clear, but it is considered to be due to the fact that it has a large number of phenolic hydroxyl groups (—OH) having strong physiological activity.
【０００９】ここで、被覆材の全固形分中のタンニンま
たはタンニン酸の含有量を0.5 重量％以上とするのは0.
5 重量％未満では、十分な防汚性能を発揮できないから
であり、好ましい含有量は３重量％以上である。含有量
の上限については、特に制限を受けるものではないが、
塗料として被覆する場合、含有量が80重量％を越えると
造膜性が不良となるため80重量％以下が好ましく、60重
量％以下にするのがさらに好ましい。The content of tannin or tannic acid in the total solid content of the coating material is 0.5% by weight or more.
This is because if it is less than 5% by weight, sufficient antifouling performance cannot be exhibited, and the preferable content is 3% by weight or more. The upper limit of the content is not particularly limited,
In the case of coating as a paint, if the content exceeds 80% by weight, the film forming property becomes poor, so 80% by weight or less is preferable, and 60% by weight or less is more preferable.
【００１０】被覆材中のバインダー樹脂としては、通常
有機樹脂を使用するが、その種類は何ら制限されること
なくいずれの樹脂も使用できる。例えば、塩化ゴム樹
脂、エポキシ樹脂、シリコン樹脂、ウレタン樹脂、フェ
ノール樹脂、ポリエステル樹脂等汎用の樹脂を用いるこ
とができる。この被覆材中には、タルク、マイカ、シリ
カ、炭酸カルシウム、硫酸バリウム等の体質顔料や二酸
化チタン、ベンガラ、フタロシアニンブルー、カーボン
ブラック等の着色顔料を含むことができる。また、分散
化剤、酸化安定剤、チキソ剤等を含むこともできる。さ
らには、ロジンやポリビニールアルコール樹脂等の水溶
性樹脂を添加してもよい。水溶性樹脂の添加は、バイン
ダー樹脂が水中に徐々に溶出することにより活性の高い
タンニンを常に表面に露出させておくという効果をも
つ。As the binder resin in the coating material, an organic resin is usually used, but the kind thereof is not limited at all and any resin can be used. For example, general-purpose resins such as chlorinated rubber resin, epoxy resin, silicon resin, urethane resin, phenol resin, polyester resin can be used. This coating material may contain extender pigments such as talc, mica, silica, calcium carbonate and barium sulfate, and coloring pigments such as titanium dioxide, red iron oxide, phthalocyanine blue and carbon black. Further, a dispersant, an oxidation stabilizer, a thixotropic agent and the like can be included. Further, a water-soluble resin such as rosin or polyvinyl alcohol resin may be added. The addition of the water-soluble resin has the effect that the binder resin is gradually eluted into water so that highly active tannin is always exposed on the surface.
【００１１】また、タンニンおよびタンニン酸以外の毒
性のない生物忌避剤や低毒性の防汚剤を複合添加して
も、特に問題はないが、有機錫等の毒性の強い物質の併
用は、本発明の目的には合わない。本発明の被覆材は、
船底塗料や取水管、海水タンク等の被覆材として有用で
ある。その際、被覆材単独で用いることもできるし、ま
た基材が鋼材の場合は防食被覆に重ねて被覆しても良
い。防食被覆上に被覆する場合は、バインダー樹脂を、
防食被覆樹脂との密着性の優れたものにする必要があ
り、同一樹脂系を用いるのが好ましい。There is no particular problem if a nontoxic biorepellent other than tannin and tannic acid and a low toxicity antifouling agent are added in combination, but the combination of highly toxic substances such as organic tin is not recommended. It does not meet the purpose of the invention. The coating material of the present invention is
It is useful as a coating material for ship bottom paint, intake pipes, seawater tanks, etc. At that time, the coating material may be used alone, or when the base material is a steel material, it may be coated on the anticorrosion coating. When coating on anticorrosion coating, binder resin,
It is necessary to have excellent adhesion to the anticorrosion coating resin, and it is preferable to use the same resin system.
【００１２】[0012]
【実施例】以下、実施例を用いて説明する。EXAMPLES Examples will be described below.
【００１３】まず、表１に示す配合組成の塗料を調製し
た。これに各種防汚剤を所定量添加して表２ (実施例１
〜11、比較例１〜５) に示す組成の塗料を作製した。塗
料は、必要に応じてMEK 、トルエン等の溶剤を添加して
粘度 (常温) を2000〜5000cps の範囲になるように調整
した。なお、防汚剤として添加したタンニンは各種植物
より煮沸して煎じることにより抽出したものを使用し、
その純度は80％以上のものを使用した。また、タンニン
酸は市販のタンニン酸をそのまま使用した。First, a paint having the composition shown in Table 1 was prepared. A predetermined amount of various antifouling agents was added to this, and the results are shown in Table 2 (Example 1).
-11 and Comparative Examples 1-5) were prepared. The paint was adjusted to have a viscosity (normal temperature) in the range of 2000 to 5000 cps by adding a solvent such as MEK and toluene as needed. The tannin added as an antifouling agent uses those extracted by boiling and decocting from various plants,
Its purity was 80% or more. As the tannic acid, commercially available tannic acid was used as it was.
【００１４】一方、300 ×300 ×3.2 mm厚の熱延鋼板を
準備し脱脂後、サンドブラストを全面に行い、表面をSa
21/2以上になるよう調整した。On the other hand, a hot rolled steel sheet having a thickness of 300 × 300 × 3.2 mm is prepared and degreased, and then sandblasting is performed on the entire surface, and the surface is sacrificed.
Adjusted to 21/2 or more.
【００１５】このブラスト鋼板に前記試作塗料をエアレ
ススプレー塗装した。被覆厚は、乾燥膜厚で300 ±50μ
m になるように調整した。被覆は両面に行い端面は刷毛
塗りにより被覆した。こうして得たサンプルを、鳥羽湾
の海岸から20ｍ離れた位置に停留した筏に取り付けて実
海水浸漬試験を実施した。サンプルの上方部を吊り下げ
ることにより垂直方向に浸漬し、サンプル上端が海面下
10cmの位置となるように調整した。このサンプルの防汚
性能 (生物付着状況) を６ヶ月後、１年後、２年後に目
視観察した。The blast steel plate was airless spray coated with the trial paint. Coating thickness is 300 ± 50μ in dry film thickness
Adjusted to be m. The coating was performed on both sides, and the end faces were coated with a brush. The sample thus obtained was attached to a raft stopped at a position 20 m away from the coast of Toba Bay to carry out an actual seawater immersion test. Dip vertically in the upper part of the sample so that the upper end of the sample is below sea level.
The position was adjusted to 10 cm. The antifouling performance (biological adhesion state) of this sample was visually observed after 6 months, 1 year and 2 years.
【００１６】またこれとは別にこのサンプルを500 ×50
0 ×400 の水槽に浸漬し、ヒメダカを20匹放流し、10日
後の生存率で毒性を評価した。防汚性能および毒性試験
の結果を表２に示す。実施例１〜11に認められるように
タンニンを0.5 重量％以上添加することにより、無毒性
にもかかわらず、優れた防汚性能を付与することが可能
となる。Separately from this, this sample is 500 × 50
After immersing it in a 0 × 400 water tank, 20 medaka were released, and the toxicity was evaluated by the survival rate after 10 days. Table 2 shows the results of the antifouling performance and the toxicity test. As can be seen from Examples 1 to 11, by adding tannin in an amount of 0.5% by weight or more, it is possible to impart excellent antifouling performance in spite of nontoxicity.
【００１７】一方、比較例１〜３に認められるように有
機錫系化合物は優れた防汚性能を示すが、毒性が強く、
水質汚染の点で問題となる。また、タンニンの添加量が
0.5重量％未満の比較例４や無添加の比較例５において
は、生物付着が著しく、防汚被覆材としては不適当であ
ることがわかる。On the other hand, as can be seen in Comparative Examples 1 to 3, organotin compounds show excellent antifouling performance, but have strong toxicity.
It becomes a problem in terms of water pollution. Also, the amount of tannin added
In Comparative Example 4 containing less than 0.5% by weight and Comparative Example 5 with no addition, it is understood that biofouling is remarkable and it is unsuitable as an antifouling coating material.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【発明の効果】以上説明したように、タンニンを0.5 重
量％以上含む防汚被覆材は優れた防汚性能を有し、かつ
無毒性であるため、水質汚染を引き起こすことのない安
全な防汚被覆として、海水取水管や船底等の防汚被覆に
利用することができる。As described above, since the antifouling coating material containing 0.5% by weight or more of tannin has excellent antifouling performance and is nontoxic, it is a safe antifouling agent that does not cause water pollution. As a coating, it can be used as an antifouling coating for seawater intake pipes and ship bottoms.
Claims (1)
酸を被覆材の全固形分中0.5 重量％以上含むことを特徴
とする防汚被覆材。1. An antifouling coating material comprising tannin or tannic acid as an antifouling component in an amount of 0.5% by weight or more based on the total solid content of the coating material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27565991A JPH05112740A (en) | 1991-10-23 | 1991-10-23 | Antifouling coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27565991A JPH05112740A (en) | 1991-10-23 | 1991-10-23 | Antifouling coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05112740A true JPH05112740A (en) | 1993-05-07 |
Family
ID=17558553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27565991A Withdrawn JPH05112740A (en) | 1991-10-23 | 1991-10-23 | Antifouling coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05112740A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001139316A (en) * | 1999-11-09 | 2001-05-22 | Forestry & Forest Products Research Inst Forestry Agency | Liquid carbide and method for manufacturing the same |
| WO2014116812A3 (en) * | 2013-01-24 | 2014-09-18 | Northwestern University | Phenolic coatings and methods of making and using same |
-
1991
- 1991-10-23 JP JP27565991A patent/JPH05112740A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001139316A (en) * | 1999-11-09 | 2001-05-22 | Forestry & Forest Products Research Inst Forestry Agency | Liquid carbide and method for manufacturing the same |
| WO2014116812A3 (en) * | 2013-01-24 | 2014-09-18 | Northwestern University | Phenolic coatings and methods of making and using same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990107 |