JP3883715B2 - Underwater antifouling agent - Google Patents
Underwater antifouling agent Download PDFInfo
- Publication number
- JP3883715B2 JP3883715B2 JP30297498A JP30297498A JP3883715B2 JP 3883715 B2 JP3883715 B2 JP 3883715B2 JP 30297498 A JP30297498 A JP 30297498A JP 30297498 A JP30297498 A JP 30297498A JP 3883715 B2 JP3883715 B2 JP 3883715B2
- Authority
- JP
- Japan
- Prior art keywords
- triphenylborane
- group
- antifouling agent
- carbon atoms
- containing amine
- 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 - Lifetime
Links
- 239000002519 antifouling agent Substances 0.000 title claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 73
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 57
- 150000001412 amines Chemical class 0.000 claims description 32
- 229920001083 polybutene Polymers 0.000 claims description 31
- 125000003545 alkoxy group Chemical group 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 229920002545 silicone oil Polymers 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- DVFGEIYOLIFSRX-UHFFFAOYSA-N 3-(2-ethylhexoxy)propan-1-amine Chemical compound CCCCC(CC)COCCCN DVFGEIYOLIFSRX-UHFFFAOYSA-N 0.000 claims description 14
- 235000019271 petrolatum Nutrition 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 150000002019 disulfides Chemical class 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- URJWRNMPAAIGMO-UHFFFAOYSA-N 3-(2-ethylhexoxy)propan-1-amine;triphenylborane Chemical compound CCCCC(CC)COCCCN.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 URJWRNMPAAIGMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 2
- -1 (substituted) pyridine Chemical class 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 28
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 230000003373 anti-fouling effect Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 150000004763 sulfides Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical class CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
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- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 3
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- LPUBRQWGZPPVBS-UHFFFAOYSA-N 3-butoxypropan-1-amine Chemical compound CCCCOCCCN LPUBRQWGZPPVBS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 241000700670 Bryozoa Species 0.000 description 2
- DXVYLFHTJZWTRF-UHFFFAOYSA-N Ethyl isobutyl ketone Chemical compound CCC(=O)CC(C)C DXVYLFHTJZWTRF-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000025 natural resin Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
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- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- WBYWKMUGWXSFIH-UHFFFAOYSA-N 1-(decyltetrasulfanyl)decane Chemical compound CCCCCCCCCCSSSSCCCCCCCCCC WBYWKMUGWXSFIH-UHFFFAOYSA-N 0.000 description 1
- DWXUFQGAQNIMSO-UHFFFAOYSA-N 1-(dodecyltetrasulfanyl)dodecane Chemical compound CCCCCCCCCCCCSSSSCCCCCCCCCCCC DWXUFQGAQNIMSO-UHFFFAOYSA-N 0.000 description 1
- MHHDOGIKXLEAOX-UHFFFAOYSA-N 1-(nonadecyltetrasulfanyl)nonadecane Chemical compound CCCCCCCCCCCCCCCCCCCSSSSCCCCCCCCCCCCCCCCCCC MHHDOGIKXLEAOX-UHFFFAOYSA-N 0.000 description 1
- HEGKYDWLIATKCZ-UHFFFAOYSA-N 1-(nonylpentasulfanyl)nonane Chemical compound CCCCCCCCCSSSSSCCCCCCCCC HEGKYDWLIATKCZ-UHFFFAOYSA-N 0.000 description 1
- SYPMTHVZNBWTIK-UHFFFAOYSA-N 1-(nonyltetrasulfanyl)nonane Chemical compound CCCCCCCCCSSSSCCCCCCCCC SYPMTHVZNBWTIK-UHFFFAOYSA-N 0.000 description 1
- PBCMRNUMIAQRBZ-UHFFFAOYSA-N 1-(octadecyltetrasulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSSSCCCCCCCCCCCCCCCCCC PBCMRNUMIAQRBZ-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、養殖用または定置用の漁網およびこれらに使用される浮き子、ロープなどの漁網付属具、船底、海水取水路及び海中構築物などに水棲汚損生物が付着するのを長期にわたって防止するための海中防汚剤に関する。
【０００２】
【従来の技術】
漁網および漁網付属具、船底、海水取水路および海中構築物などは、海中で長期保持されるため、海藻類、フジツボ、セルプラ、コケムシ、軟体動物類などの水棲汚損生物の付着が激しく、それらの保守に多大の労力と費用をかけている。
【０００３】
これらの水棲汚損生物の付着を防止するために、従来は有機錫重合体が広く使用されてきたが、有機錫化合物は環境に対する配慮などから使用できなくなった。
【０００４】
そこで、有機錫重合体に替わる防汚薬剤として種々の研究、提案がなされ、現在亜酸化銅、ロダン銅などの銅化合物、エチレンビスジチオカルバミン酸の亜鉛塩やマンガン塩などのチオカーバメイト化合物、テトラエチルチウラムジスルフィド、テトラクロロイソフタロニトリル、ジメチルフェニルジクロロマレイミドなどの有機化合物を有効成分とし、これを油性系または合成樹脂系ビヒクルに配合した防汚剤が使用されているが、塗膜物性、防汚性の面で満足しうる化合物は、未だ見出されていないのが現状である。
【０００５】
また、防汚剤の有効成分として、トリフェニルボランと（置換）ピリジン誘導体との錯体化合物が提案されている（米国特許第３２１１６７９号明細書、特開平７−１３３２０７号公報）。しかし、これら化合物は、溶剤に不溶の為、分散型防汚剤となり、作業効率が非常に悪くなるという欠点がある上に、防汚性能および物性面でも満足できるものになっていない。さらに、トリフェニルボラン・脂肪族アミン錯体化合物（米国特許第３２１１６７９号明細書、特開平８−２９５６０８号公報、特開平８−２９５６０９号公報）、トリフェニルボラン・ヒドロキシル基含有アミン錯体化合物（特開平９−７８００７号公報）、トリフェニルボラン・高級脂肪族ポリアミン錯体化合物（特開平１０−１８２３２２号公報）、トリフェニルボラン・高級脂肪族第二または第三アミン錯体化合物（特開平１０−１８２３２３号公報）も提案されており、これらの化合物は溶剤に溶解するため作業効率の点では改善されるが、ある程度の効果を出すためには薬剤量を多くする必要があり、価格および防汚性能の点で充分に満足できるものになっていない。
【０００６】
【発明が解決しようとする課題】
本発明は、前記の点に鑑みて、魚網および漁網付属具、船底、海水取水路、海中構築物などに対する塗布作業性が良好で、かつ長期間すぐれた防汚効果を維持することのできる海中防汚剤を提供することを課題とする。
【０００７】
【課題を解決するための手段】
本発明者らは、前記の観点から、鋭意検討を進めた結果、一般式（Ｉ）で示されるトリフェニルボラン・アルコキシ基含有アミン錯体化合物が、フジツボ、ムラサキイガイ、カキ、セルプラなどの貝類、および、カサネカンザシ、ヒトエカンザシ、ヤッコカンザシ、ウズマキゴカイなどの管棲多毛類、ヒドロ虫などの腔腸動物、あるいはその他の生物の付着に対してすぐれた防汚効果を示し、さらに、キシレンなどの有機溶剤に可溶であるため、特に網染めにおいて極めて作業性のよい、実用的な製剤が可能であることを見出し、さらに前述のトリフェニルボラン・アルコキシ基含有アミン錯体化合物に、シリコーンオイル、ポリブテン類、パラフィン類、ワセリン類、ジアルキルスルフィド化合物よりなる群から選ばれた少なくとも１種を併用するか、および／または、一般式（III）で表されるテトラアルキルチウラムジスルフィドを併用すると飛躍的に防汚性能が向上し、通常使用される薬剤量の半量以下であっても、長期間にわたってフジツボ、セルプラ、ホヤ、コケムシなどの大型生物や藻類などに対する防汚効果が持続することを見出し、本発明を完成するに至った。
【０００８】
すなわち、請求項１に係る発明は、一般式（Ｉ）：
【０００９】
【化５】
（式中、Ｒ1は炭素数１〜８の直鎖もしくは分枝状のアルキレン基、またはフェニレン基を、Ｒ2は炭素数１〜１８の直鎖または分枝状のアルキル基を示す）で表わされるトリフェニルボラン・アルコキシ基含有アミン錯体化合物の１種または２種以上を有効成分として含有することを特徴とする海中防汚剤に関する。
【００１１】
さらに請求項２に係る発明は、（Ａ）請求項１記載のトリフェニルボラン・アルコキシ基含有アミン錯体化合物の１種または２種以上と、（Ｂ）シリコーンオイル、ポリブテン類、パラフィン類、ワセリン類、および一般式（II）：
Ｒ3−（Ｓ）n −Ｒ3 （II）
（式中、Ｒ3は炭素数１〜２０の直鎖または分枝状のアルキル基を、ｎは１〜２０の整数を示す）で表されるジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上とを含有することを特徴とする海中防汚剤に関する。
【００１２】
さらに請求項３に係る発明は、（Ａ）請求項１記載のトリフェニルボラン・アルコキシ基含有アミン錯体化合物の１種または２種以上と、（Ｃ）一般式（III）：
【００１３】
【化６】
（式中、Ｒ4は炭素数１〜８の直鎖または分枝状のアルキル基を示す）で表されるテトラアルキルチウラムジスルフィド化合物の１種または２種以上とを含有することを特徴とする海中防汚剤に関する。
【００１５】
さらに請求項４に係る発明は、（Ａ）請求項１記載のトリフェニルボラン・アルコキシ基含有アミン錯体化合物の１種または２種以上と、（Ｂ）シリコーンオイル、ポリブテン類、パラフィン類、ワセリン類、および一般式（II）：
Ｒ3−（Ｓ）n −Ｒ3 （II）
（式中、Ｒ3は炭素数１〜２０の直鎖または分枝状のアルキル基を、ｎは１〜２０の整数を示す）で表されるジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上と、（Ｃ）一般式（III）：
【００１６】
【化７】
（式中、Ｒ4は炭素数１〜８の直鎖または分枝状のアルキル基を示す）で表されるテトラアルキルチウラムジスルフィド化合物の１種または２種以上とを含有することを特徴とする海中防汚剤に関する。
【００１８】
さらに請求項５に係る発明は、一般式（Ｉ）で表されるトリフェニルボラン・アルコキシ基含有アミン錯体化合物がトリフェニルボラン・３−（２−エチルヘキシルオキシ）プロピルアミン錯体化合物である請求項１〜４のいずれかに記載の海中防汚剤に関する。
【００１９】
さらに請求項６に係る発明は、一般式（Ｉ）：
【００２０】
【化８】
（式中、Ｒ1は炭素数１〜８の直鎖もしくは分枝状のアルキレン基、またはフェニレン基を、Ｒ2は炭素数１〜１８の直鎖または分枝状のアルキル基を示す）で表わされるトリフェニルボラン・アルコキシ基含有アミン錯体化合物に関する。
【００２２】
さらに請求項７に係る発明は、トリフェニルボラン・アルコキシ基含有アミン錯体化合物がトリフェニルボラン・３−（２−エチルヘキシルオキシ）プロピルアミン錯体化合物である請求項６記載の化合物に関する。
【００２３】
【発明の実施の形態】
本発明において、必須の有効成分として使用する化合物は、一般式（Ｉ）で表されるトリフェニルボラン・アルコキシ基含有アミン錯体化合物である。
【００２４】
一般式（Ｉ）において、Ｒ1で示される炭素数１〜８の直鎖または分枝状アルキレン基としては、たとえばメチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、２−メチルトリメチレン基、１，１−ジメチルエチレン基、１，２−ジメチルエチレン基、１−エチルエチレン基、ペンタメチレン基、ヘキサメチレン基、１−ブチルエチレン基、オクタメチレン基、２−エチルヘキサメチレン基などがあげられ、Ｒ2で示される炭素数１〜１８の直鎖または分枝状アルキル基としては、たとえば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、２−エチルヘキシル、ノニル、デシル、ウンデシル、ラウリル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、ステアリルなどがあげられる。
【００２５】
前記一般式（Ｉ）で表されるトリフェニルボラン・アルコキシ基含有アミン錯体化合物の具体例としては、たとえばトリフェニルボラン・３−エトキシプロピルアミン、トリフェニルボラン・３−ブトキシプロピルアミン、トリフェニルボラン・３−（２−エチルへキシルオキシ）プロピルアミン、トリフェニルボラン・３−ラウリルオキシプロピルアミン、トリフェニルボラン・３−ステアリルオキシプロピルアミン、トリフェニルボラン・４−（２−エチルヘキシルオキシ）ブチルアミン、トリフェニルボラン・４−ラウリルオキシブチルアミン、トリフェニルボラン・８−エトキシオクチルアミン、トリフェニルボラン・８−（２−エチルヘキシルオキシ）オクチルアミン、トリフェニルボラン・２−エチルヘキシルオキシフェニルアミン、トリフェニルボラン・ラウリルオキシフェニルアミンなどがあげられる。
【００２６】
これらトリフェニルボラン・アルコキシ基含有アミン錯体化合物は、単独で用いてもよく、２種以上を組みあわせて用いてもよい。
【００２７】
前記一般式（Ｉ）で表されるトリフェニルボラン・アルコキシ基含有アミン錯体化合物は、トリフェニルボランとアルコキシ基含有アミンとを、好ましくは不活性雰囲気下で、両者を溶解し得る有機溶剤中で常温下または加熱下に反応させることによって得ることができる。有機溶剤としては、たとえばテトラヒドロフラン、ベンゼン、トルエン、キシレン、ミネラルスピリット、ヘキサン、ヘプタン、オクタン、メチルエチルケトン、エチルイソブチルケトン、ジブチルエーテル、メタノール、エタノール、プロパノールなどが使用できる。トリフェニルボランとアルコキシ基含有アミンの使用割合は等モル比ないしその近傍のモル比が好ましい。反応混合物の処理は溶剤の留去、結晶化など常法によって行なうことができ、必要により再結晶などにより精製してもよい。
【００２８】
本発明においては、有効成分として（Ａ）前記トリフェニルボラン・アルコキシ基含有アミン錯体化合物を単独で用いてもよいが、（Ｂ）シリコーンオイル、ポリブテン類、パラフィン類、ワセリン類および一般式（II）で表されるジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上を併用するか、および／または、（Ｃ）一般式（III）で表されるテトラアルキルチウラムジスルフィド化合物を併用することにより、防汚効果が飛躍的に向上する。
【００２９】
本発明に用いられるシリコーンオイルとしては、たとえばポリジメチルシロキサン、ポリメチルフェニルシロキサン、メチルフェニルシロキサン−ジメチルシロキサン共重合体、ポリエーテル変性ポリジメチルシロキサン、ポリエーテル変性ポリアルキル（メチル）シロキサン、ポリエステル変性ポリジメチルシロキサン、フロロシリコーンオイル、アミノ変性シリコーンオイル、その他各種官能基による変性シリコーンオイルなどがあげられるが、これらに限られるものではない。これらのシリコーンオイルのうちでとくに好ましいものは、親水性親油性バランス（ＨＬＢ）が２〜１２の範囲にある、ポリジメチルシロキサン、メチルフェニルシロキサン−ジメチルシロキサン共重合体、ポリエーテル変性ポリジメチルシロキサンである。これらのシリコーンオイルは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また本発明に用いるシリコーンオイルは、海中防汚剤の塗工性能、塗膜物性の点から、粘度が１〜１万ポイズ、なかんづく５０〜５００ポイズの範囲のものが好ましい。
【００３０】
本発明に用いられるポリブテン類としては、たとえば、日本石油化学（株）製のポリブテンＬＶ−７、ポリブテンＬＶ−１０、ポリブテンＬＶ−２５、ポリブテンＬＶ−５０、ポリブテンＬＶ−１００、ポリブテンＨＶ−３５、ポリブテンＨＶ−１００、ポリブテンＨＶ−３００、ポリブテンＨＶ−１９００、出光石油化学（株）製のポリブテン０Ｈ、ポリブテン５Ｈ、ポリブテン１０Ｈ、ポリブテン３００Ｈ、ポリブテン２０００Ｈ、ポリブテン０Ｒ、ポリブテン１５Ｒ、ポリブテン３５Ｒ、ポリブテン１００Ｒ、ポリブテン３５０Ｒ、日本油脂（株）製のポリビスＯＳＨ、三井化学（株）製のルーカントＨＣ−２０、ルーカントＨＣ−１５０、ルーカントＨＣ−６００、ルーカントＨＣ−２０００などがあげられる。
【００３１】
本発明に用いられるパラフィン類としては、たとえば、ｎ−パラフィン（日本石油化学（株）製など）、固形パラフィン（日本精蝋（株）製など）、流動パラフィン（松村石油（株）製のスモイルＰ−１００、スモイルＰ−１５０など）、塩素化パラフィン（東ソー（株）製のＡ−４０、Ａ−５０、Ａ−７０、Ａ−１４５、Ａ−１５０、Ａ−２６５、Ａ−２７０など）などがあげられる。
【００３２】
本発明に用いられるワセリン類としては、たとえば、白色ワセリン、黄色ワセリン（安藤パラケミー（株）製など）があげられる。
【００３３】
本発明に用いられる一般式（II）で表されるジアルキルスルフィド化合物には、ｎが１であるジアルキルモノスルフィド化合物と、ｎが２〜２０の整数であるジアルキルポリスルフィド化合物が含まれる。一般式（II）において、Ｒ3で示される炭素数１〜２０の直鎖または分枝状のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、オクチル、ノニル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシルなどがあげられる。海中防汚剤の塗工性能、塗膜物性の点から、とくに炭素数４〜１９のアルキル基が好ましい。一般式（II）において、ｎは１〜２０の整数であるが、海中防汚剤の塗工性能、塗膜物性の点からｎが１〜１０、なかんづく４〜１０であるのが好ましい。これらジアルキルスルフィド化合物は単独で用いてもよく、あるいは２種以上を組み合わせて用いてもよい。海中防汚剤の塗工性能、塗膜物性の点から好ましいジアルキルスルフィド化合物としては、ジ−ｔｅｒｔ−ブチルデカスルフィド、ジペンチルテトラスルフィド、ジペンチルペンタスルフィド、ジペンチルデカスルフィド、ジオクチルテトラスルフィド、ジオクチルペンタスルフィド、ジノニルテトラスルフィド、ジノニルペンタスルフィド、ジ−ｔｅｒｔ−ノニルテトラスルフィド、ジ−ｔｅｒｔ−ノニルペンタスルフィド、ジデシルテトラスルフィド、ジドデシルテトラスルフィド、ジオクタデシルテトラスルフィド、ジノナデシルテトラスルフィドなどがあげられるが、これに限定されるものではない。
【００３４】
本発明においては、（Ｂ）成分として、前記シリコーンオイルと、前記ポリブテン類、パラフィン類、ワセリン類およびジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上とを併用するのが好ましい。
【００３５】
本発明に用いられるテトラアルキルチウラムジスルフィド化合物は一般式（III）で表わされるものである。一般式（III）において、Ｒ4で示される炭素数１〜８のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、２−エチルヘキシルなどがあげられる。一般式（III）で表されるテトラアルキルチウラムジスルフィド化合物の具体例としては、たとえばテトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラプロピルチウラムジスルフィド、テトライソプロピルチウラムジスルフィド、テトラブチルチウラムジスルフィド、テトラ−ｓｅｃ−ブチルチウラムジスルフィド、テトライソブチルチウラムジスルフィド、テトラ−ｔｅｒｔ−ブチルチウラムジスルフィド、テトラペンチルチウラムジスルフィド、テトラヘキシルチウラムジスルフィド、テトラヘプチルチウラムジスルフィド、テトラオクチルチウラムジスルフィド、テトラ（２−エチルヘキシル）チウラムジスルフィドなどがあげられるが、これらに限定されるものではない。これらのテトラアルキルジスルフィド化合物のうち、好ましいものはテトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィドである。テトラアルキルチウラムジスルフィド化合物は単独で用いてもよく、あるいは２種以上を組み合わせて用いてもよい。
【００３６】
本発明においては、テトラアルキルチウラルジスルフィド化合物を前記のシリコーンオイル、ポリブテン類、パラフィン類、ワセリン類および一般式（II）で表されるジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上と併用するのが好ましい。
【００３７】
本発明の海中防汚剤には、ビヒクルとして合成樹脂および／または天然樹脂が用いられる。合成樹脂系ビヒクルとしては、塩化ビニル／酢酸ビニル共重合体、塩化ビニル／アルキルビニルエーテル共重合体、塩化ビニル樹脂などのビニル樹脂系、アルキッド樹脂系、アクリル樹脂系、ウレタン樹脂系、ポリエステル樹脂系、合成ゴム系、塩素化ポリエチレンなどがあげられる。また、天然樹脂としては、ウッドロジン、ガムロジン、変性ロジンなどがあげられる。ビヒクルに用いられる樹脂としては、特にアクリル樹脂が好ましい。
【００３８】
また、本発明の海中防汚剤には、通常溶剤が含まれる。溶剤としては、特に限定されるものではなく種々の溶剤が使用でき、たとえばベンゼン、トルエン、キシレン、トリメチルベンゼンなどの芳香族系炭化水素溶剤、エタノール、イソプロパノール、ｎ−ブタノールなどのアルコール系溶剤、アセトン、ジエチルケトン、メチルイソブチルケトンなどのケトン系溶剤などがあげられる。これらの溶剤は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。
【００３９】
本発明の海中防汚剤において、有効成分として、トリフェニルボラン・アルコキシ基含有アミン錯体化合物を単独で使用するばあい、その使用量は、特に制限されるものではないが、防汚剤中の不揮発分量に対して、通常０．１〜８０重量％であり、好ましくは、１〜５０重量％である。トリフェニルボラン・アルコキシ基含有アミン錯体化合物の使用量が前記範囲未満では防汚性が充分でなく、一方前記範囲を超えると塗工性能、塗膜物性が劣化する傾向がある。
【００４０】
さらに、本発明の海中防汚剤において、（Ａ）トリフェニルボラン・アルコキシ基含有アミン錯体化合物に、（Ｂ）シリコーンオイル、ポリブテン類、パラフィン類、ワセリン類およびジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上を併用するばあい、これらの配合比は特に制限されるものではないが、（Ａ）成分／（Ｂ）成分の重量比は通常１／９９〜９９／１の範囲であり、好ましくは１０／９０〜９０／１０の範囲である。また、防汚剤中の不揮発分量に対する（Ａ）成分と（Ｂ）成分の合計配合量は特に制限されるものではないが、通常０．１〜８０重量％であり、好ましくは１〜５０重量％の範囲である。合計配合量が前記範囲未満では防汚性が充分でなく、一方前記範囲を超えると海中防汚剤としての塗工性能、塗膜物性が劣化する傾向がある。
【００４１】
さらに、本発明の海中防汚剤において、（Ａ）トリフェニルボラン・アルコキシ基含有アミン錯体化合物に、（Ｃ）テトラアルキルチウラムジスルフィド化合物を併用するばあい、これらの配合比は特に制限されるものではないが、（Ａ）成分／（Ｃ）成分の重量比は通常１／９９〜９９／１の範囲であり、好ましくは１０／９０〜９０／１０の範囲である。また、防汚剤中の不揮発分量に対する（Ａ）成分と（Ｃ）成分の合計配合量は特に制限されるものではないが、通常０．１〜８０重量％であり、好ましくは１〜５０重量％の範囲である。合計配合量が前記範囲未満では防汚性が充分でなく、一方前記範囲を超えると海中防汚剤としての塗工性能、塗膜物性が劣化する傾向にある。
【００４２】
さらに、本発明では、（Ａ）トリフェニルボラン・アルコキシ基含有アミン錯体化合物と、（Ｃ）テトラアルキルチウラムジスルフィド化合物を前記の割合で配合したものに、（Ｂ）前記シリコーンオイル、ポリブテン類、パラフィン類、ワセリン類およびジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上を併用することができる。その場合、これら成分の配合比はとくに制限されるものではないが、（Ａ）成分と（Ｃ）成分の混合物（混合比は１／９９〜９９／１、好ましくは１０／９０〜９０／１０である）／（Ｂ）成分の重量比は通常１／９９〜９９／１の範囲であり、好ましくは１０／９０〜９０／１０の範囲である。また、防汚剤中の不揮発分量に対する（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計配合量は特に制限されるものではないが、通常０．１〜８０重量％であり、好ましくは１〜５０重量％の範囲である。合計配合量が前記範囲未満では防汚性が充分でなく、一方前記範囲を超えると海中防汚剤としての塗工性能、塗膜物性が劣化する傾向にある。
【００４３】
本発明の海中防汚剤には、他の防汚剤を添加してもよい。これらの防汚剤としては、たとえばジチオカーバート系防汚剤、カーバメート系防汚剤、マレイミド系防汚剤、イソチアゾロン系防汚剤、テトラクロロイソフタロニトリルなどが挙げられる。また、本発明の海中防汚剤には、フタル酸エステル、アジピン酸エステル、トリクレジルフォスフェートなどの可塑剤も加えることができる。さらに、本発明の海中防汚剤には、顔料、その他の添加剤、たとえばポリアマイド燐酸系、ポリアマイド系、不飽和ポリカルボン酸系などの分散剤、消泡剤、タレ止め剤、界面活性剤などを添加することができる。本発明の海中防汚剤においては、他の防汚剤、可塑剤、顔料、その他の添加剤は、本発明の目的を損なわない範囲で任意の配合割合で含有させることができる。
【００４４】
本発明の海中防汚剤は、前記した成分を混合し、必要に応じて各種添加剤を配合し、混合することにより製造することができる。各成分の混合方法および各種添加剤の添加方法は、特に制限されるものではなく、種々の方法により行うことができ、混合順序および添加順序も種々の方法で行うことができる。
【００４５】
本発明は、本発明の海中防汚剤を、漁網具等に塗布することにより、水棲汚損生物の付着を防止し、優れた防汚性を発揮させる漁網具等の防汚方法も提供することができる。海中防汚剤の漁網具等への塗布方法は、たとえば浸漬塗装、吹きつけ塗装などの種々の塗装方法を適用することができるが、浸漬塗装が好ましい。付着量は、漁網の場合漁網重量の１〜２０重量％の範囲が好ましい。
【００４６】
【実施例】
つぎにトリフェニルボラン・アルコキシ基含有アミン錯体化合物の製造例、実施例および試験例をあげて本発明を説明する。各例中の％および部はそれぞれ重量％および重量部を示す。
【００４７】
製造例１ トリフェニルボラン・３−（２−エチルヘキシルオキシ）プロピルアミン錯体化合物の製造
冷却器、攪拌機を取り付けた３００ｍｌ四ツ口フラスコにトリフェニルボラン
（試薬特級、Ａｌｄｒｉｃｈ社製）２４．２ｇ（０．１００ｍｏｌ）、３−（２−エチルヘキシルオキシ）プロピルアミン（試薬特級、東京化成工業（株）製）１８．７ｇ（０．１００ｍｏｌ）、脱水テトラヒドロフラン（ＴＨＦ）１００ｍｌを仕込み、Ｎ2気流下、室温で４時間反応させた後、ＴＨＦを減圧下留去した。残留物をメタノールから再結晶することにより、融点６６．５〜６７．５℃の白色粉末４０．３ｇ（収率９４％）を得た。この化合物はＦＴＩＲ、ＮＭＲおよびつぎの元素分析の結果により、トリフェニルボラン・３−（２−エチルヘキシルオキシ）プロピルアミン錯体化合物であることを確認した。図１にこの化合物のＦＴＩＲスペクトルを、図２にＮＭＲスペクトルを示す。ＦＴＩＲは、（株）島津製作所製 ＦＴＩＲ−８１００Ｍを使用し、ＫＢｒ錠剤法で測定した。ＮＭＲは日本電子（株）製 ＪＮＭ−ＰＭＸ６０を使用し、テトラメチルシランを内部基準としてＣＤＣｌ3中で測定した。
【００４８】
製造例２ トリフェニルボラン・３−エトキシプロピルアミン錯体化合物の製造
製造例１で、３−（２−エチルヘキシルオキシ）プロピルアミンの替わりに、３−エトキシプロピルアミン（広栄化学工業（株）製）１０．３ｇ（０．１００ｍｏｌ）を用い、製造例１と同様にして、融点１７５〜１７６℃の白色粉末３０．０ｇ（収率８７％）を得た。この化合物はＦＴＩＲ、ＮＭＲおよびつぎの元素分析の結果により、トリフェニルボラン・３−エトキシプロピルアミン錯体化合物であることを確認した。
【００５０】
製造例３ トリフェニルボラン・３−ブトキシプロピルアミン錯体化合物の製造
製造例１で、３−（２−エチルヘキシルオキシ）プロピルアミンの替わりに、３−ブトキシプロピルアミン（広栄化学工業（株）製）１３．１ｇ（０．１００ｍｏｌ）を用い、製造例１と同様にして、融点１０６〜１０７℃の白色粉末３４．０ｇ（収率９１％）を得た。この化合物はＦＴＩＲ、ＮＭＲおよびつぎの元素分析の結果により、トリフェニルボラン・３−ブトキシプロピルアミン錯体化合物であることを確認した。
【００５２】
製造例４ トリフェニルボラン−３−ラウリルオキシプロピルアミン錯体化合物の製造
製造例１で、３−（２−エチルヘキシルオキシ）プロピルアミンの替わりに、３−ラウリルオキシプロピルアミン（広栄化学工業（株）製）２４．３ｇ（０．１００ｍｏｌ）を用い、製造例１と同様にして、融点７３．５〜７４．０℃の白色粉末４３．３ｇ（収率８９％）を得た。この化合物はＦＴＩＲ、ＮＭＲおよびつぎの元素分析の結果により、トリフェニルボラン・３−ラウリルオキシプロピルアミン錯体化合物であることを確認した。
【００５４】
比較製造例１ トリフェニルボラン・ピリジン錯体化合物の製造
（米国特許第３２１１６７９号明細書および特開平７−１３３２０７号公報記載の化合物）
製造例１で３−（２−エチルヘキシルオキシ）プロピルアミンの替わりに、ピリジン（試薬特級、キシダ化学（株）製）７．９ｇ（０．１００ｍｏｌ）を用い、製造例１と同様にして、白色粉末のトリフェニルボラン・ピリジン錯体化合物２７．６ｇ（収率８６％）を得た。
【００５６】
比較製造例２ トリフェニルボラン・オクタデシルアミン錯体化合物の製造
（米国特許第３２１１６７９号明細書、特開平８−２９５６０８号公報および特開平８−２９５６０９号公報記載の化合物）
製造例１で３−（２−エチルヘキシルオキシ）プロピルアミンの替わりに、オクタデシルアミン（試薬特級、東京化成工業（株）製）２７．０ｇ（０．１００ｍｏｌ）を用い、製造例１と同様にして、白色粉末のトリフェニルボラン・オクタデシルアミン錯体化合物４３．０ｇ（収率８４％）を得た。
【００５７】
比較製造例３ トリフェニルボラン・エタノールアミン錯体化合物の製造
（特開平９−７８００７号公報記載の化合物）
製造例１で３−（２−エチルヘキシルオキシ）プロピルアミンの替わりに、エタノールアミン（試薬特級、東京化成工業（株）製）６．１ｇ（０．１００ｍｏｌ）を用い、製造例１と同様にして、白色粉末のトリフェニルボラン・エタノールアミン錯体化合物２６．１ｇ（収率８６％）を得た。
【００５８】
実施例１〜１７および比較例１〜５
製造例１〜４および比較製造例１〜３で得られた化合物を用い、表１、２に記載の配合成分を添加して、実施例１〜１７および比較例１〜５の海中防汚剤を得た。
【００５９】
【表１】
【表２】
試験例（防汚性試験）
実施例１〜１７および比較例１〜５で得られた海中防汚剤を、ポリエチレン製の漁網（４００デニール、４０本、８節）に浸漬塗装し、乾燥した。このように防汚剤を塗布した漁網を４０ｃｍ×６０ｃｍの鉄棒の枠に固定し、三重県尾鷲湾にて海中筏から水深約１ｍに垂下浸漬し、その防汚性能を６カ月にわたって定期的に観測した。結果を表３に示す。表中の数字は海棲生物の付着面積（％）を表す。
【００６２】
【表３】
【発明の効果】
表３の結果から明らかな様に、一般式（Ｉ）で表されるトリフェニルボラン・アルコキシ基含有アミン錯体化合物を用いた本発明の海中防汚剤は水棲汚損生物の付着を効果的に防止することができる。また、トリフェニルボラン・アルコキシ基含有アミン錯体化合物と、シリコーンオイル、ポリブテン類、パラフィン類、ワセリン類、ジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上と、および／または、テトラアルキルチウラムジスルフィドとを併用した本発明の海中防汚剤は、長期にわたって水棲汚損生物の付着を防止できる。
【図面の簡単な説明】
【図１】本発明の製造例１におけるトリフェニルボラン・３−（２−エチルヘキシルオキシ）プロピルアミン錯体化合物のＦＴＩＲスペクトルである。
【図２】本発明の製造例１におけるトリフェニルボラン・３−（２−エチルヘキシルオキシ）プロピルアミン錯体化合物のＮＭＲスペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention is intended to prevent aquatic fouling organisms from sticking to aquaculture or stationary fishing nets and fishing net accessories such as floats and ropes, ship bottoms, seawater intakes and underwater structures for a long period of time. Of marine antifouling agent.
[0002]
[Prior art]
Since fishing nets and fishing net accessories, ship bottoms, seawater intakes and underwater structures are maintained for a long time in the sea, the attachment of aquatic fouling organisms such as seaweeds, barnacles, cell plastics, bryozoans and molluscs is severe and their maintenance It takes a lot of effort and cost.
[0003]
Conventionally, organotin polymers have been widely used in order to prevent the adhesion of these varicella-fouling organisms. However, organotin compounds cannot be used because of environmental considerations.
[0004]
Therefore, various researches and proposals have been made as antifouling agents in place of organotin polymers. Currently, copper compounds such as cuprous oxide and rhodan copper, thiocarbamate compounds such as zinc and manganese salts of ethylenebisdithiocarbamate, and tetraethylthiuram. Antifouling agents containing organic compounds such as disulfide, tetrachloroisophthalonitrile, and dimethylphenyldichloromaleimide as active ingredients and blended with oil-based or synthetic resin-based vehicles are used. At present, no compound that is satisfactory in terms of the above has been found.
[0005]
As an active ingredient of the antifouling agent, a complex compound of triphenylborane and a (substituted) pyridine derivative has been proposed (US Pat. No. 3,321,679, JP-A-7-133207). However, these compounds are insoluble in a solvent, so that they become a dispersion-type antifouling agent, resulting in a very poor working efficiency and are not satisfactory in terms of antifouling performance and physical properties. Further, triphenylborane / aliphatic amine complex compounds (US Pat. No. 3,321,679, JP-A-8-295608, JP-A-8-295609), triphenylborane / hydroxyl group-containing amine complex compounds (JP 9-78007), triphenylborane / higher aliphatic polyamine complex compound (JP-A-10-182322), triphenylborane / higher aliphatic secondary or tertiary amine complex compound (JP-A-10-182323). ) Have been proposed, and these compounds are dissolved in a solvent, so that the work efficiency is improved. However, in order to achieve a certain level of effect, the amount of the chemical must be increased, and the cost and antifouling performance must be increased. It is not satisfactory enough.
[0006]
[Problems to be solved by the invention]
In view of the above points, the present invention has excellent coating workability for fish nets and fishing net accessories, ship bottoms, seawater intakes, underwater structures, etc., and can maintain an excellent antifouling effect for a long period of time. It is an object to provide a soiling agent.
[0007]
[Means for Solving the Problems]
As a result of intensive studies from the above viewpoint, the present inventors have found that triphenylborane / alkoxy group-containing amine complex compounds represented by the general formula (I) are shellfish such as barnacles, mussels, oysters, and cell plastics, and It exhibits excellent antifouling effect against the adhesion of tuberculid polychaetes such as Kasane Kanzashi, Human Ekanzashi, Yakko Kanzashi, Uzumakigokai, and hydrozoa, and other organisms, and organic solvents such as xylene. It is found that a practical preparation with extremely good workability can be obtained particularly in net dyeing, and further, the triphenylborane-alkoxy group-containing amine complex compound described above can be added to silicone oil, polybutenes, At least one selected from the group consisting of paraffins, petrolatums and dialkyl sulfide compounds; When used, and / or when used together with the tetraalkylthiuram disulfide represented by the general formula (III), the antifouling performance is dramatically improved. Over time, the present inventors have found that the antifouling effect on large organisms such as barnacles, cell plastics, sea squirts, bryozoans, and algae persists, thereby completing the present invention.
[0008]
That is, the invention according to
[0009]
[Chemical formula 5]
(Wherein R1Represents a linear or branched alkylene group having 1 to 8 carbon atoms, or a phenylene group, R2Is a linear or branched alkyl group having 1 to 18 carbon atoms), and contains one or more triphenylborane / alkoxy group-containing amine complex compounds represented by It relates to an underwater antifouling agent.
[0011]
Further, the invention according to
RThree-(S) n -RThree (II)
(Wherein RThreeIs a linear or branched alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 20, and contains one or more selected from the group consisting of dialkyl sulfide compounds The present invention relates to an underwater antifouling agent.
[0012]
Further, the invention according to
[0013]
[Chemical 6]
(Wherein RFourIs a linear or branched alkyl group having 1 to 8 carbon atoms), and relates to a marine antifouling agent characterized by containing one or more tetraalkylthiuram disulfide compounds.
[0015]
Further, the invention according to
RThree-(S) n -RThree (II)
(Wherein RThreeIs a linear or branched alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 20, and one or more selected from the group consisting of dialkyl sulfide compounds represented by: C) General formula (III):
[0016]
[Chemical 7]
(Wherein RFourIs a linear or branched alkyl group having 1 to 8 carbon atoms), and relates to a marine antifouling agent characterized by containing one or more tetraalkylthiuram disulfide compounds.
[0018]
Further, in the invention according to
[0019]
Further, the invention according to
[0020]
[Chemical 8]
(Wherein R1Represents a linear or branched alkylene group having 1 to 8 carbon atoms, or a phenylene group, R2Represents a straight-chain or branched alkyl group having 1 to 18 carbon atoms) and a triphenylborane / alkoxy group-containing amine complex compound.
[0022]
The invention according to
[0023]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the compound used as an essential active ingredient is a triphenylborane / alkoxy group-containing amine complex compound represented by the general formula (I).
[0024]
In general formula (I), R1Examples of the straight-chain or branched alkylene group having 1 to 8 carbon atoms represented by: methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene Group, 1,2-dimethylethylene group, 1-ethylethylene group, pentamethylene group, hexamethylene group, 1-butylethylene group, octamethylene group, 2-ethylhexamethylene group, etc.2Examples of the linear or branched alkyl group having 1 to 18 carbon atoms represented by: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, Examples include 2-ethylhexyl, nonyl, decyl, undecyl, lauryl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl and the like.
[0025]
Specific examples of the triphenylborane / alkoxy group-containing amine complex compound represented by the general formula (I) include triphenylborane-3ethoxypropylamine, triphenylborane-3-butoxypropylamine, and triphenylborane. 3- (2-ethylhexyloxy) propylamine, triphenylborane, 3-lauryloxypropylamine, triphenylborane, 3-stearyloxypropylamine, triphenylborane, 4- (2-ethylhexyloxy) butylamine, tri Phenylborane, 4-lauryloxybutylamine, triphenylborane, 8-ethoxyoctylamine, triphenylborane, 8- (2-ethylhexyloxy) octylamine, triphenylborane, 2-ethylhexyloxyphenylamine Emissions, such as triphenyl borane lauryl oxyphenyl amines.
[0026]
These triphenylborane / alkoxy group-containing amine complex compounds may be used alone or in combination of two or more.
[0027]
The triphenylborane / alkoxy group-containing amine complex compound represented by the general formula (I) is an organic solvent capable of dissolving triphenylborane and an alkoxy group-containing amine, preferably in an inert atmosphere. It can be obtained by reacting at room temperature or under heating. As the organic solvent, for example, tetrahydrofuran, benzene, toluene, xylene, mineral spirit, hexane, heptane, octane, methyl ethyl ketone, ethyl isobutyl ketone, dibutyl ether, methanol, ethanol, propanol and the like can be used. The use ratio of triphenylborane and alkoxy group-containing amine is preferably an equimolar ratio or a molar ratio in the vicinity thereof. The reaction mixture can be treated by conventional methods such as evaporation of the solvent and crystallization, and may be purified by recrystallization, if necessary.
[0028]
In the present invention, (A) the triphenylborane / alkoxy group-containing amine complex compound may be used alone as an active ingredient, but (B) silicone oil, polybutenes, paraffins, petrolatums and the general formula (II) ) Or a combination of two or more selected from the group consisting of dialkyl sulfide compounds represented by formula (III) and / or (C) a tetraalkylthiuram disulfide compound represented by formula (III) As a result, the antifouling effect is dramatically improved.
[0029]
Examples of the silicone oil used in the present invention include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, polyether-modified polyalkyl (methyl) siloxane, and polyester-modified poly. Examples include, but are not limited to, dimethylsiloxane, fluorosilicone oil, amino-modified silicone oil, and other modified silicone oils with various functional groups. Particularly preferred among these silicone oils are polydimethylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, and polyether-modified polydimethylsiloxane having a hydrophilic / lipophilic balance (HLB) in the range of 2-12. is there. These silicone oils may be used alone or in combination of two or more. In addition, the silicone oil used in the present invention preferably has a viscosity in the range of 1 to 10,000 poise, especially 50 to 500 poise, from the viewpoint of coating performance of the antifouling agent in the sea and physical properties of the coating film.
[0030]
Examples of the polybutenes used in the present invention include polybutene LV-7, polybutene LV-10, polybutene LV-25, polybutene LV-50, polybutene LV-100, polybutene HV-35 manufactured by Nippon Petrochemical Co., Ltd. Polybutene HV-100, Polybutene HV-300, Polybutene HV-1900, Polybutene 0H, Polybutene 5H, Polybutene 10H, Polybutene 300H, Polybutene 2000H, Polybutene 0R, Polybutene 15R, Polybutene 35R, Polybutene 100R, manufactured by Idemitsu Petrochemical Co., Ltd. Examples include Polybutene 350R, Polybis OSH manufactured by NOF Corporation, Lucant HC-20, Lucant HC-150, Lucant HC-600, Lucant HC-2000 manufactured by Mitsui Chemicals.
[0031]
Examples of the paraffins used in the present invention include n-paraffin (manufactured by Nippon Petrochemical Co., Ltd.), solid paraffin (manufactured by Nippon Seiwa Co., Ltd.), liquid paraffin (Sumoil made by Matsumura Oil Co., Ltd.). P-100, sumoyl P-150, etc.), chlorinated paraffin (A-40, A-50, A-70, A-145, A-150, A-265, A-270, etc., manufactured by Tosoh Corporation) Etc.
[0032]
Examples of petrolatums used in the present invention include white petrolatum and yellow petrolatum (manufactured by Ando Parachemy Co., Ltd.).
[0033]
The dialkyl sulfide compound represented by the general formula (II) used in the present invention includes a dialkyl monosulfide compound in which n is 1 and a dialkyl polysulfide compound in which n is an integer of 2 to 20. In the general formula (II), RThreeExamples of the straight chain or branched alkyl group having 1 to 20 carbon atoms represented by: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl And octadecyl. An alkyl group having 4 to 19 carbon atoms is particularly preferable from the viewpoint of the coating performance of the marine antifouling agent and the physical properties of the coating film. In the general formula (II), n is an integer of 1 to 20, and n is preferably 1 to 10, especially 4 to 10 from the viewpoint of coating performance and coating film physical properties of the marine antifouling agent. These dialkyl sulfide compounds may be used alone or in combination of two or more. Preferred dialkyl sulfide compounds from the viewpoint of coating performance of marine antifouling agents and coating film properties include di-tert-butyl decasulfide, dipentyl tetrasulfide, dipentyl pentasulfide, dipentyl decasulfide, dioctyl tetrasulfide, dioctyl pentasulfide, Examples include dinonyl tetrasulfide, dinonyl pentasulfide, di-tert-nonyl tetrasulfide, di-tert-nonyl pentasulfide, didecyl tetrasulfide, didodecyl tetrasulfide, dioctadecyl tetrasulfide, and dinonadecyl tetrasulfide. However, the present invention is not limited to this.
[0034]
In the present invention, as the component (B), it is preferable to use the silicone oil in combination with one or more selected from the group consisting of the polybutenes, paraffins, petrolatums and dialkyl sulfide compounds.
[0035]
The tetraalkyl thiuram disulfide compound used in the present invention is represented by the general formula (III). In general formula (III), RFourExamples of the alkyl group having 1 to 8 carbon atoms represented by: include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl and the like. Specific examples of the tetraalkylthiuram disulfide compound represented by the general formula (III) include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetra-sec-butyl. Thiuram disulfide, tetraisobutyl thiuram disulfide, tetra-tert-butyl thiuram disulfide, tetrapentyl thiuram disulfide, tetrahexyl thiuram disulfide, tetraheptyl thiuram disulfide, tetraoctyl thiuram disulfide, tetra (2-ethylhexyl) thiuram disulfide, etc. It is not limited to these. Of these tetraalkyl disulfide compounds, preferred are tetraethyl thiuram disulfide and tetrabutyl thiuram disulfide. Tetraalkyl thiuram disulfide compounds may be used alone or in combination of two or more.
[0036]
In the present invention, the tetraalkylthioural disulfide compound is one or more selected from the group consisting of the aforementioned silicone oil, polybutenes, paraffins, petrolatums and dialkylsulfide compounds represented by the general formula (II). It is preferable to use together.
[0037]
In the marine antifouling agent of the present invention, a synthetic resin and / or a natural resin is used as a vehicle. Synthetic resin-based vehicles include vinyl chloride / vinyl acetate copolymer, vinyl chloride / alkyl vinyl ether copolymer, vinyl resin such as vinyl chloride resin, alkyd resin, acrylic resin, urethane resin, polyester resin, Synthetic rubber type, chlorinated polyethylene and the like can be mentioned. Examples of natural resins include wood rosin, gum rosin, and modified rosin. As the resin used for the vehicle, an acrylic resin is particularly preferable.
[0038]
Moreover, the marine antifouling agent of the present invention usually contains a solvent. The solvent is not particularly limited, and various solvents can be used. For example, aromatic hydrocarbon solvents such as benzene, toluene, xylene and trimethylbenzene, alcohol solvents such as ethanol, isopropanol and n-butanol, acetone And ketone solvents such as diethyl ketone and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more.
[0039]
In the marine antifouling agent of the present invention, when a triphenylborane / alkoxy group-containing amine complex compound is used alone as an active ingredient, the amount used is not particularly limited. It is 0.1 to 80 weight% normally with respect to a non-volatile content, Preferably, it is 1 to 50 weight%. If the amount of the triphenylborane / alkoxy group-containing amine complex compound is less than the above range, the antifouling property is not sufficient, while if it exceeds the above range, the coating performance and the physical properties of the coating film tend to deteriorate.
[0040]
Further, in the marine antifouling agent of the present invention, (A) the triphenylborane / alkoxy group-containing amine complex compound is selected from the group consisting of (B) silicone oil, polybutenes, paraffins, petrolatums and dialkyl sulfide compounds. When using 1 type or 2 types or more together, these compounding ratios are not particularly limited, but the weight ratio of component (A) / component (B) is usually in the range of 1/99 to 99/1. Yes, preferably in the range of 10/90 to 90/10. The total blending amount of the component (A) and the component (B) with respect to the nonvolatile content in the antifouling agent is not particularly limited, but is usually 0.1 to 80% by weight, preferably 1 to 50% by weight. % Range. If the total blending amount is less than the above range, the antifouling property is not sufficient, while if it exceeds the above range, the coating performance as a marine antifouling agent and the physical properties of the coating film tend to deteriorate.
[0041]
Further, in the marine antifouling agent of the present invention, when (A) a triphenylborane / alkoxy group-containing amine complex compound is used in combination with (C) a tetraalkylthiuram disulfide compound, the mixing ratio thereof is particularly limited. However, the weight ratio of component (A) / component (C) is usually in the range of 1/99 to 99/1, preferably in the range of 10/90 to 90/10. The total blending amount of the component (A) and the component (C) with respect to the nonvolatile content in the antifouling agent is not particularly limited, but is usually 0.1 to 80% by weight, preferably 1 to 50% by weight. % Range. If the total blending amount is less than the above range, the antifouling property is not sufficient. On the other hand, if it exceeds the above range, the coating performance as a marine antifouling agent and the physical properties of the coating film tend to deteriorate.
[0042]
Further, in the present invention, (B) the silicone oil, polybutenes, paraffin are blended with (A) a triphenylborane / alkoxy group-containing amine complex compound and (C) a tetraalkylthiuram disulfide compound in the above proportions. 1 type, or 2 or more types selected from the group consisting of catechins, petrolatums and dialkyl sulfide compounds can be used in combination. In that case, the compounding ratio of these components is not particularly limited, but a mixture of component (A) and component (C) (mixing ratio is 1/99 to 99/1, preferably 10/90 to 90/10. The weight ratio of the component (B) is usually in the range of 1/99 to 99/1, preferably in the range of 10/90 to 90/10. Further, the total blending amount of the component (A), the component (B) and the component (C) with respect to the nonvolatile content in the antifouling agent is not particularly limited, but is usually 0.1 to 80% by weight, preferably Is in the range of 1-50% by weight. If the total blending amount is less than the above range, the antifouling property is not sufficient. On the other hand, if it exceeds the above range, the coating performance as a marine antifouling agent and the physical properties of the coating film tend to deteriorate.
[0043]
You may add another antifouling agent to the underwater antifouling agent of this invention. Examples of these antifouling agents include dithiocarbate antifouling agents, carbamate antifouling agents, maleimide antifouling agents, isothiazolone antifouling agents, and tetrachloroisophthalonitrile. In addition, a plasticizer such as phthalic acid ester, adipic acid ester or tricresyl phosphate can be added to the marine antifouling agent of the present invention. Further, the marine antifouling agent of the present invention includes pigments and other additives, for example, dispersants such as polyamide phosphates, polyamides and unsaturated polycarboxylic acids, antifoaming agents, anti-sagging agents, surfactants, etc. Can be added. In the marine antifouling agent of the present invention, other antifouling agents, plasticizers, pigments, and other additives can be contained in any blending ratio as long as the object of the present invention is not impaired.
[0044]
The underwater antifouling agent of the present invention can be produced by mixing the aforementioned components, blending various additives as necessary, and mixing them. The mixing method of each component and the adding method of various additives are not particularly limited, and can be performed by various methods. The mixing order and the adding order can also be performed by various methods.
[0045]
The present invention also provides an antifouling method for fishing nets and the like that prevents the adhesion of water fouling organisms and exhibits excellent antifouling properties by applying the underwater antifouling agent of the present invention to fishing nets and the like. Can do. Various coating methods such as dip coating and spray coating can be applied as the method for applying the marine antifouling agent to the fishing net equipment, but dip coating is preferred. In the case of a fishing net, the adhesion amount is preferably in the range of 1 to 20% by weight of the fishing net.
[0046]
【Example】
Next, the present invention will be described with reference to production examples, examples and test examples of triphenylborane / alkoxy group-containing amine complex compounds. In each example, “%” and “part” represent “% by weight” and “part by weight”, respectively.
[0047]
Production Example 1Preparation of triphenylborane • 3- (2-ethylhexyloxy) propylamine complex compound
Triphenylborane in a 300 ml four-necked flask equipped with a condenser and a stirrer
(Reagent special grade, manufactured by Aldrich) 24.2 g (0.100 mol), 3- (2-ethylhexyloxy) propylamine (reagent special grade, manufactured by Tokyo Chemical Industry Co., Ltd.) 18.7 g (0.100 mol), dehydrated tetrahydrofuran (THF) 100ml is charged, N2After reacting for 4 hours at room temperature under an air stream, THF was distilled off under reduced pressure. The residue was recrystallized from methanol to obtain 40.3 g (yield 94%) of white powder having a melting point of 66.5 to 67.5 ° C. This compound was confirmed to be a triphenylborane.3- (2-ethylhexyloxy) propylamine complex compound from the results of FTIR, NMR and the following elemental analysis. FIG. 1 shows the FTIR spectrum of this compound, and FIG. 2 shows the NMR spectrum. FTIR was measured by KBr tablet method using FTIR-8100M manufactured by Shimadzu Corporation. NMR uses JNM-PMX60 manufactured by JEOL Ltd., and CDCl with tetramethylsilane as an internal standard.ThreeMeasured in.
[0048]
Production Example 2Production of triphenylborane and 3-ethoxypropylamine complex compound
In Production Example 1, instead of 3- (2-ethylhexyloxy) propylamine, 10.3 g (0.100 mol) of 3-ethoxypropylamine (manufactured by Guangei Chemical Industry Co., Ltd.) was used, and the same procedure as in Production Example 1 was performed. As a result, 30.0 g (yield 87%) of white powder having a melting point of 175 to 176 ° C. was obtained. This compound was confirmed to be a triphenylborane · 3-ethoxypropylamine complex compound from the results of FTIR, NMR and the following elemental analysis.
[0050]
Production Example 3Preparation of triphenylborane 3-butoxypropylamine complex compound
In Production Example 1, instead of 3- (2-ethylhexyloxy) propylamine, 13.1 g (0.100 mol) of 3-butoxypropylamine (manufactured by Guangei Chemical Industry Co., Ltd.) was used, and the same as in Production Example 1. As a result, 34.0 g (yield 91%) of white powder having a melting point of 106 to 107 ° C. was obtained. This compound was confirmed to be a triphenylborane · 3-butoxypropylamine complex compound from the results of FTIR, NMR and the following elemental analysis.
[0052]
Production Example 4Production of triphenylborane-3-lauryloxypropylamine complex compound
In Production Example 1, instead of 3- (2-ethylhexyloxy) propylamine, 24.3 g (0.100 mol) of 3-lauryloxypropylamine (manufactured by Koei Chemical Industry Co., Ltd.) was used, and the same as in Production Example 1. Thus, 43.3 g (yield 89%) of white powder having a melting point of 73.5 to 74.0 ° C. was obtained. This compound was confirmed to be a triphenylborane.3-lauryloxypropylamine complex compound from the results of FTIR, NMR and the following elemental analysis.
[0054]
Comparative production example 1Production of triphenylborane / pyridine complex compounds
(Compounds described in US Pat. No. 3,111,679 and JP-A-7-133207)
Instead of 3- (2-ethylhexyloxy) propylamine in Production Example 1, 7.9 g (0.100 mol) of pyridine (special grade reagent, manufactured by Kishida Chemical Co., Ltd.) was used, As a result, 27.6 g (yield 86%) of triphenylborane / pyridine complex compound was obtained.
[0056]
Comparative production example 2Production of triphenylborane octadecylamine complex compound
(Compounds described in U.S. Pat. No. 3,211,679, JP-A-8-295608 and JP-A-8-295609)
Instead of 3- (2-ethylhexyloxy) propylamine in Production Example 1, 27.0 g (0.100 mol) of octadecylamine (special grade reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used in the same manner as in Production Example 1. Thus, 43.0 g (yield 84%) of triphenylborane / octadecylamine complex compound as a white powder was obtained.
[0057]
Comparative production example 3Production of triphenylborane / ethanolamine complex compound
(Compound described in JP-A-9-78007)
In place of 3- (2-ethylhexyloxy) propylamine in Production Example 1, 6.1 g (0.100 mol) of ethanolamine (special grade reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used in the same manner as in Production Example 1. As a result, 26.1 g (yield 86%) of triphenylborane / ethanolamine complex compound as white powder was obtained.
[0058]
Examples 1-17 and Comparative Examples 1-5
Using the compounds obtained in Production Examples 1 to 4 and Comparative Production Examples 1 to 3, the ingredients listed in Tables 1 and 2 were added, and the marine antifouling agents of Examples 1 to 17 and Comparative Examples 1 to 5 Got.
[0059]
[Table 1]
[Table 2]
Test example (antifouling test)
The marine antifouling agents obtained in Examples 1 to 17 and Comparative Examples 1 to 5 were dip-coated on a polyethylene fishing net (400 denier, 40, 8 sections) and dried. The fishing net coated with the antifouling agent is fixed to a 40cm x 60cm iron rod frame and immersed in the water at about 1m from the underwater ridge in Owase Bay, Mie Prefecture. Observed. The results are shown in Table 3. The numbers in the table represent the marine organism attachment area (%).
[0062]
[Table 3]
【The invention's effect】
As is apparent from the results in Table 3, the marine antifouling agent of the present invention using the triphenylborane / alkoxy group-containing amine complex compound represented by the general formula (I) effectively prevents adhesion of waterpox fouling organisms. can do. Also, triphenylborane / alkoxy group-containing amine complex compound and one or more selected from the group consisting of silicone oil, polybutenes, paraffins, petrolatums, dialkyl sulfide compounds, and / or tetraalkylthiuram The underwater antifouling agent of the present invention used in combination with disulfide can prevent the attachment of water fouling organisms over a long period of time.
[Brief description of the drawings]
FIG. 1 is an FTIR spectrum of a triphenylborane • 3- (2-ethylhexyloxy) propylamine complex compound in Production Example 1 of the present invention.
FIG. 2 is an NMR spectrum of a triphenylborane • 3- (2-ethylhexyloxy) propylamine complex compound in Production Example 1 of the present invention.
Claims (7)
Ｒ3−（Ｓ）n −Ｒ3 （II）
（式中、Ｒ3は炭素数１〜２０の直鎖または分枝状のアルキル基を、ｎは１〜２０の整数を示す）で表されるジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上とを含有することを特徴とする海中防汚剤。(A) One or more of the triphenylborane / alkoxy group-containing amine complex compounds according to claim 1, (B) silicone oil, polybutenes, paraffins, petrolatums, and general formula (II):
R 3- (S) n -R 3 (II)
(Wherein R 3 represents a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20), or one selected from the group consisting of dialkyl sulfide compounds Underwater antifouling agent characterized by containing 2 or more types.
Ｒ3−（Ｓ）n −Ｒ3 （II）
（式中、Ｒ3は炭素数１〜２０の直鎖または分枝状のアルキル基を、ｎは１〜２０の整数を示す）で表されるジアルキルスルフィド化合物よりなる群から選ばれる１種または２種以上と、（Ｃ）一般式（III）：
R 3- (S) n -R 3 (II)
(Wherein R 3 represents a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20), or one selected from the group consisting of dialkyl sulfide compounds Two or more, and (C) general formula (III):
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30297498A JP3883715B2 (en) | 1998-03-19 | 1998-10-23 | Underwater antifouling agent |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7083398 | 1998-03-19 | ||
| JP10-70833 | 1998-03-19 | ||
| JP30297498A JP3883715B2 (en) | 1998-03-19 | 1998-10-23 | Underwater antifouling agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11322763A JPH11322763A (en) | 1999-11-24 |
| JP3883715B2 true JP3883715B2 (en) | 2007-02-21 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30297498A Expired - Lifetime JP3883715B2 (en) | 1998-03-19 | 1998-10-23 | Underwater antifouling agent |
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| JP (1) | JP3883715B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001348532A (en) * | 2000-06-08 | 2001-12-18 | Nippon Paint Marine Kk | Antifouling paint |
| JP4064100B2 (en) * | 2001-12-13 | 2008-03-19 | 日東化成株式会社 | Anti-fouling composition for fishing nets, fishing nets coated with the anti-fouling composition for fishing nets, and anti-fouling method for fishing nets using the anti-fouling composition for fishing nets |
| JP2006045171A (en) * | 2004-08-09 | 2006-02-16 | Api Corporation | Minamata fouling bioadhesive composition |
| JP2007246482A (en) * | 2006-03-17 | 2007-09-27 | Chugoku Marine Paints Ltd | Antifouling composition, and film and fishing net formed from the composition |
| EP2006336A1 (en) | 2007-06-21 | 2008-12-24 | SigmaKalon B.V. | Antifouling coating, resin composition and methods of production thereof |
| WO2009001829A1 (en) * | 2007-06-26 | 2008-12-31 | Chugoku Marine Paints, Ltd. | Triphenylboron compound-containing antifouling coating composition having improved stability, antifouling agent set used therefor, and method for suppressing/controlling decomposition of triphenylboron compound |
| JP2009127010A (en) * | 2007-11-27 | 2009-06-11 | Nitto Kasei Co Ltd | Antifouling coating material composition, antifouling coating film formed by using the same, method for forming the coating film, and fishing net having the coating film on its surface |
| EP2199349A1 (en) | 2008-12-19 | 2010-06-23 | Ppg B.V. | Resin composition, antifouling coating comprising barnacle antifoulant and processes of production thereof |
| JP5561462B2 (en) * | 2009-09-17 | 2014-07-30 | 日東化成株式会社 | Fishing net antifouling paint composition, antifouling coating film formed using the composition, method for forming the coating film, and fishing net, fishing net tool or underwater structure having the coating film on the surface |
| JP2011102251A (en) * | 2009-11-10 | 2011-05-26 | Hitachi Chem Co Ltd | Method for manufacturing triarylborane complex |
| JP6186199B2 (en) * | 2013-07-30 | 2017-08-23 | 日東化成株式会社 | A fishing net antifouling paint composition, a fishing net having an antifouling coating film formed using the composition, a fishing net tool, or an underwater structure. |
| KR102404839B1 (en) | 2016-08-25 | 2022-06-07 | 비엘 테크놀러지스 인크. | Reduce contamination of hydrocarbon oils |
-
1998
- 1998-10-23 JP JP30297498A patent/JP3883715B2/en not_active Expired - Lifetime
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| JPH11322763A (en) | 1999-11-24 |
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