JPH0812513A - Aquatic antifouling agent - Google Patents
Aquatic antifouling agentInfo
- Publication number
- JPH0812513A JPH0812513A JP15073894A JP15073894A JPH0812513A JP H0812513 A JPH0812513 A JP H0812513A JP 15073894 A JP15073894 A JP 15073894A JP 15073894 A JP15073894 A JP 15073894A JP H0812513 A JPH0812513 A JP H0812513A
- Authority
- JP
- Japan
- Prior art keywords
- cuprous oxide
- antifouling agent
- fine powder
- coating
- antifouling
- 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
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、主として船舶、水中構
造物等の防汚塗料に配合されて使用される水中防汚剤に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater antifouling agent which is mainly used by being mixed with an antifouling paint for ships, underwater structures and the like.
【０００２】[0002]
【従来の技術】船舶、港湾施設、橋脚等の水中構造物の
塗覆装表面には、フジツボ、アオノリ等の海中生物が付
着堆積するため、防食塗膜の損傷をきたす一方、船舶に
あっては航行する際の摩擦抵抗が大きくなり燃料消費の
増大につながる。2. Description of the Related Art Marine organisms such as barnacles and sea lions adhere to and deposit on the coated surface of underwater structures such as ships, harbor facilities, and bridge piers, causing damage to the anticorrosive coating while Causes increased frictional resistance when navigating, leading to increased fuel consumption.
【０００３】このための対策として、従来、錫を主体と
した防汚塗料が用いられてきた。ところが、この防汚塗
料の防汚成分である有機錫化合物又は加錫共重合体は、
防汚性には優れているものの、海洋汚染、毒性問題（魚
類への蓄積性等）から全面的に使用規制されることとな
った。このようなことから、非錫系の防汚成分として、
魚類への蓄積性がなく、しかも以前から使用実績のある
亜酸化銅が再び用いられることとなった。As a countermeasure for this, conventionally, an antifouling paint mainly containing tin has been used. However, the organic tin compound or tin-containing copolymer, which is the antifouling component of this antifouling paint,
Although it has excellent antifouling properties, its use has been completely regulated due to marine pollution and toxicity issues (accumulation in fish, etc.). From this, as a non-tin antifouling component,
Cuprous oxide, which has no accumulation in fish and has a long history of use, has been reused.
【０００４】[0004]
【発明が解決しようとする課題】上記亜酸化銅を用いた
防汚塗料においては、銅イオンの溶出を促進するために
アビエチン酸等の溶出促進物質を添加しているが、その
溶出量は初期に多く経時的に減少する傾向にあり、長期
間、安定した防汚作用を達成することができなかった
（例えば、中尾学著「船舶の塗料と塗装」７０〜７１
頁、昭和６３年１２月２０日発行、株式会社船舶技術協
会）。In the antifouling paint using cuprous oxide, an elution promoting substance such as abietic acid is added to promote the elution of copper ions, but the elution amount is initially However, the stable antifouling effect could not be achieved for a long period of time (for example, Manabu Nakao, "Paints and coatings for ships" 70-71).
Page, published December 20, 1988, Ship Technology Association of Japan).
【０００５】また、亜酸化銅と塗膜形成ビヒクルとの結
合力（接着力）が弱いことから（図３参照）、防汚塗膜
の加水分解中に膜面に海流、波力等が加わると、亜酸化
銅が流亡消失してしまうことがあった。Further, since the binding force (adhesion) between cuprous oxide and the vehicle for forming a coating film is weak (see FIG. 3), ocean current, wave force, etc. are applied to the film surface during hydrolysis of the antifouling coating film. Then, the cuprous oxide was sometimes washed away.
【０００６】本発明はこのような問題点に鑑みてなされ
たもので、長期間、高くかつ安定した銅イオン溶出性能
を有するとともに、防汚塗料に配合した場合には、塗膜
形成ビヒクルとの結合力が高められるようにした水中防
汚剤を提供することを目的とする。The present invention has been made in view of the above problems, and has a high and stable copper ion elution performance for a long period of time, and when it is mixed with an antifouling paint, it forms a coating film-forming vehicle. It is an object of the present invention to provide an underwater antifouling agent having an improved binding force.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、本発明の水中防汚剤は、亜酸化銅の微粉末を、末端
にカルボキシル基を有するメタアクリレート又はアクリ
レートによってコーティングした。In order to achieve the above object, the underwater antifouling agent of the present invention is obtained by coating fine powder of cuprous oxide with a methacrylate or acrylate having a carboxyl group at the terminal.
【０００８】亜酸化銅からの銅イオンの溶出速度は、や
や酸性に近い中性近傍からアルカリ性になるにしたがっ
て小さくなる傾向があるので、本発明はこれに対応すべ
く亜酸化銅微粉末を上記物質でコーティングし、そのコ
ーティング膜が海水又は淡水により微溶する際に酸性域
とならしめ、銅イオンの溶出を促進することとした。Since the elution rate of copper ions from cuprous oxide tends to decrease as the pH changes from near neutral to alkaline to alkaline, the present invention responds to this by using fine cuprous oxide powder as described above. The substance was coated, and when the coating film was slightly dissolved in seawater or fresh water, it was made to be in an acidic region to promote the elution of copper ions.
【０００９】また、上記コーティング膜によって亜酸化
銅と塗膜形成ビヒクルとの相溶性を高め、両者の結合力
を高めようとするものである。即ち、図３に示す従来の
未処理亜酸化銅の場合には、亜酸化銅微粉末１と塗膜形
成ビヒクル５の高分子鎖４とがからみ合わないため、両
者の結合力は弱いが、図２に示す本発明のコーティング
亜酸化銅の場合には、コーティング膜２から伸びる高分
子鎖３と、塗膜形成ビヒクル５の高分子鎖４とがからみ
合うため、両者の結合力が高められるのである。Further, the coating film is intended to enhance the compatibility between cuprous oxide and the vehicle for forming a coating film, thereby enhancing the binding force between the two. That is, in the case of the conventional untreated cuprous oxide shown in FIG. 3, since the cuprous oxide fine powder 1 and the polymer chain 4 of the coating film forming vehicle 5 do not entangle with each other, the bonding force between them is weak, In the case of the coated cuprous oxide of the present invention shown in FIG. 2, since the polymer chains 3 extending from the coating film 2 and the polymer chains 4 of the coating film forming vehicle 5 are entangled with each other, the binding force between them is enhanced. Of.
【００１０】本発明におけるコーティング材料として
は、分子中にカルボキシル基を有する重合性のモノマー
又はオリゴマーであればよいが、塗膜形成ビヒクルとの
相溶性が良好であるモノマーとして、分子末端にカルボ
キシル基を有するメタアクリレート又はアクリレートが
適している。The coating material in the present invention may be a polymerizable monomer or oligomer having a carboxyl group in the molecule, but as a monomer having good compatibility with the coating film forming vehicle, a carboxyl group at the molecular end is used. Methacrylates or acrylates with are suitable.
【００１１】特には、亜酸化銅微粉末に対し３．５〜２
０重量％の割合からなるメタクリロイルオキシエチルハ
イドロゲンフタレート、あるいは、亜酸化銅微粉末に対
し１．０〜２０重量％の割合からなるメタクリロイルオ
キシエチルハイドロゲンサクシネートとするのがよい。
なお、メタクリロイルオキシエチルハイドロゲンフタレ
ートでコーティングした防汚剤を以下、水中防汚剤
（イ）、メタクリロイルオキシエチルハイドロゲンサク
シネートでコーティングした防汚剤を以下、水中防汚剤
（ロ）という。Particularly, it is 3.5 to 2 with respect to the cuprous oxide fine powder.
It is preferable to use methacryloyloxyethyl hydrogen phthalate in a proportion of 0% by weight or methacryloyloxyethyl hydrogen succinate in a proportion of 1.0 to 20% by weight with respect to cuprous oxide fine powder.
The antifouling agent coated with methacryloyloxyethyl hydrogen phthalate is hereinafter referred to as an underwater antifouling agent (a), and the antifouling agent coated with methacryloyloxyethyl hydrogen succinate is hereinafter referred to as an underwater antifouling agent (b).
【００１２】水中防汚剤（イ）及び（ロ）において、メ
タクリロイルオキシエチルハイドロゲンフタレート及び
メタクリロイルオキシエチルハイドロゲンサクシネート
が、それぞれ３．５重量％未満及び１．０重量％未満の
場合には、十分な銅イオンの溶出効果が得られず、また
それぞれ２０重量％を越える場合には、製剤が微粉末状
になり難くなるという製造上の難点がある。In the underwater antifouling agents (a) and (b), when methacryloyloxyethyl hydrogen phthalate and methacryloyloxyethyl hydrogen succinate are less than 3.5% by weight and less than 1.0% by weight, respectively, it is sufficient. However, if the amount of each copper ion exceeds 20% by weight, there is a problem in production that the formulation is difficult to form into a fine powder.
【００１３】本発明に係る亜酸化銅コーティング組成物
の製法としては、公知の重合法を応用することができ
る。例えば、Ａ相にモノマー，Ｂ相に触媒を溶媒液とし
ておき、Ａ相とＢ相の混合溶液にただちに亜酸化銅粉末
を加え、その粒子表面を均一な重合被膜に形成する。As a method for producing the cuprous oxide coating composition according to the present invention, a known polymerization method can be applied. For example, a monomer liquid is used as the A phase and a catalyst is used as the B phase, and cuprous oxide powder is immediately added to the mixed solution of the A phase and the B phase to form a uniform polymerized film on the particle surface.
【００１４】[0014]
（実施例１）反応器にＡ相のβ−メタクリロイルオキシ
エチルハイドロゲンフタレート（ＨＯＯＣ Ｃ6 Ｈ4
ＣＨ2 ＣＨ2 ＯＣＯＣ（ＣＨ3 ）＝ＣＨ2 ）２部及
びＢ相のメタノール５部とベンゾイルパーオキサイド
０．０２部を加え、この混合溶液を攪拌しながら亜酸化
銅粉末２０部を混入し、６０℃で１時間、及び１００℃
で１時間加熱したのち乾燥粉砕して水中防汚剤（イ）を
製造した。(Example 1) Phase A β-methacryloyloxyethyl hydrogen phthalate (HOOC C 6 H 4 ) was placed in a reactor.
2 parts of CH 2 CH 2 OCOC (CH 3 ) = CH 2 ) and 5 parts of B-phase methanol and 0.02 part of benzoyl peroxide are added, and 20 parts of cuprous oxide powder are mixed while stirring the mixed solution, 1 hour at 60 ℃, and 100 ℃
After heating for 1 hour, it was dried and pulverized to produce an underwater antifouling agent (a).
【００１５】（実施例２）反応器にＡ相のβ−メタクリ
ロイルオキシエチルハイドロゲンサクシネート（ＨＯＯ
Ｃ ＣＨ2 ＣＨ2 ＣＯＯ ＣＨ2 ＣＨ2 ＯＣＯ
ＣＣ （ＣＨ3 ）＝ＣＨ2 ） ２部及びＢ相のメタノー
ル５部とベンゾイルパーオキサイド０．０４部を加え、
この混合溶解を攪拌しながら亜酸化銅粉末２０部を混入
し、６０℃で１時間，及び１００℃で１時間加熱したの
ち乾燥粉砕して水中防汚剤（ロ）を製造した。Example 2 Phase A of β-methacryloyloxyethyl hydrogen succinate (HOO) was placed in a reactor.
C CH 2 CH 2 COO CH 2 CH 2 OCO
CC (CH 3 ) = CH 2 ) 2 parts and phase B methanol 5 parts and benzoyl peroxide 0.04 parts are added,
This mixed solution was mixed with 20 parts of cuprous oxide powder while stirring, heated at 60 ° C. for 1 hour and at 100 ° C. for 1 hour, and then dried and pulverized to produce an underwater antifouling agent (b).
【００１６】（銅イオン溶出量の測定）水中防汚剤
（イ）、（ロ）の銅イオン溶出効果を測定評価するた
め、コーティング処理液濃度の異なる各防汚剤の５ｇを
秤量して３％ ＮａＣｌ水溶液５０ml中に浸漬し、室温
（２５℃前後）で２週間静置したのち水溶液中に溶出し
た銅イオンを、日立製作所製原子吸光分析装置１８０−
３０型を使用して測定した。(Measurement of Copper Ion Elution Amount) In order to measure and evaluate the copper ion elution effect of the antifouling agents (a) and (b) in water, 5 g of each antifouling agent having a different concentration of the coating solution was weighed and 3 % NaCl aqueous solution 50 ml, and allowed to stand at room temperature (around 25 ° C.) for 2 weeks, then the copper ions eluted in the aqueous solution were used for atomic absorption spectrophotometer 180-
It was measured using a Model 30.
【００１７】その結果を表１及び図１のグラフに示す。The results are shown in Table 1 and the graph of FIG.
【００１８】[0018]
【表１】 [Table 1]
【００１９】この結果から明らかなように、銅イオン溶
出量は、未処理亜酸化銅では０．０４mg/l (ppm)である
のに対し、本発明の水中防汚剤（イ）、（ロ）において
は、代表的なコーティング処理液濃度１０重量％の場
合、それぞれ５２０、５４０mg/l (ppm)であり、ブラン
クに比較していずれも約１３，０００倍の溶出度であっ
た。As is clear from these results, the amount of copper ions eluted is 0.04 mg / l (ppm) for untreated cuprous oxide, whereas the underwater antifouling agent (a), (ro ), When the concentration of the representative coating treatment liquid was 10% by weight, it was 520 and 540 mg / l (ppm), respectively, and the elution degree was about 13,000 times that of the blank.
【００２０】次に、銅イオン溶出後の水溶液のＰＨをガ
ラス電極を用いて測定したところ、ＰＨ４〜５の酸性を
示した。Next, when the pH of the aqueous solution after elution of copper ions was measured using a glass electrode, it showed an acidity of PH 4-5.
【００２１】[0021]
【発明の効果】以上のように本発明の水中防汚剤は、そ
の優れた銅イオン溶出性能によって、長期間、高くかつ
安定した防汚効果を発揮することができる。INDUSTRIAL APPLICABILITY As described above, the underwater antifouling agent of the present invention can exhibit a high and stable antifouling effect for a long period of time due to its excellent copper ion elution performance.
【００２２】また、水和型又は加水分解型等の防汚塗料
に配合された場合には、その塗膜形成ビヒクルとの結合
力が強いので、海流、波力等による流亡消失を防止する
ことができる。Further, when it is blended with a hydration type or hydrolysis type antifouling paint, it has a strong binding force with the coating film forming vehicle, so it is necessary to prevent runoff disappearance due to ocean currents, wave forces, etc. You can
【図１】本発明の水中防汚剤の銅イオン溶出効果を示す
グラフである。FIG. 1 is a graph showing a copper ion elution effect of an underwater antifouling agent of the present invention.
【図２】本発明の水中防汚剤の、塗膜形成ビヒクル中に
おける状態を示す拡大断面図である。FIG. 2 is an enlarged cross-sectional view showing a state of the underwater antifouling agent of the present invention in a coating film forming vehicle.
【図３】未処理亜酸化銅の、塗膜形成ビヒクル中におけ
る状態を示す拡大断面図である。FIG. 3 is an enlarged sectional view showing a state of untreated cuprous oxide in a vehicle for forming a coating film.
１ 亜酸化銅微粉末 ２ コーティング膜 ３ コーティング膜からの高分子鎖 ４ 塗膜形成ビヒクルの高分子鎖 ５ 塗膜形成ビヒクル 1 Fine cuprous oxide powder 2 Coating film 3 Polymer chain from coating film 4 Polymer chain of coating film forming vehicle 5 Coating film forming vehicle
Claims (3)
ル基を有するメタアクリレート又はアクリレートによっ
てコーティングしたことを特徴とする水中防汚剤。1. An underwater antifouling agent, characterized in that a fine powder of cuprous oxide is coated with a methacrylate or acrylate having a carboxyl group at the terminal.
３．５〜２０重量％の割合からなるメタクリロイルオキ
シエチルハイドロゲンフタレートであることを特徴とす
る請求項１記載の水中防汚剤。2. The underwater antifouling agent according to claim 1, wherein the coating film is methacryloyloxyethyl hydrogen phthalate in an amount of 3.5 to 20% by weight based on the cuprous oxide fine powder.
１．０〜２０重量％の割合からなるメタクリロイルオキ
シエチルハイドロゲンサクシネートであることを特徴と
する請求項１記載の水中防汚剤。3. The underwater antifouling agent according to claim 1, wherein the coating film is methacryloyloxyethyl hydrogen succinate in an amount of 1.0 to 20% by weight based on the cuprous oxide fine powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15073894A JPH0812513A (en) | 1994-07-01 | 1994-07-01 | Aquatic antifouling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15073894A JPH0812513A (en) | 1994-07-01 | 1994-07-01 | Aquatic antifouling agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0812513A true JPH0812513A (en) | 1996-01-16 |
Family
ID=15503341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15073894A Pending JPH0812513A (en) | 1994-07-01 | 1994-07-01 | Aquatic antifouling agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812513A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016140307A (en) * | 2015-02-02 | 2016-08-08 | 株式会社シマブンコーポレーション | Mosquito larva suppression tool |
| WO2018110332A1 (en) * | 2016-12-15 | 2018-06-21 | 東洋製罐グループホールディングス株式会社 | Dispersion having antiviral properties |
-
1994
- 1994-07-01 JP JP15073894A patent/JPH0812513A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016140307A (en) * | 2015-02-02 | 2016-08-08 | 株式会社シマブンコーポレーション | Mosquito larva suppression tool |
| WO2018110332A1 (en) * | 2016-12-15 | 2018-06-21 | 東洋製罐グループホールディングス株式会社 | Dispersion having antiviral properties |
| JP2018095607A (en) * | 2016-12-15 | 2018-06-21 | 東洋製罐グループホールディングス株式会社 | Dispersion liquid having antiviral properties |
| US11647744B2 (en) | 2016-12-15 | 2023-05-16 | Toyo Seikan Group Holdings, Ltd. | Dispersion solution having antiviral property |
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