JP4144049B2 - Antifouling agent for fishing nets - Google Patents
Antifouling agent for fishing nets Download PDFInfo
- Publication number
- JP4144049B2 JP4144049B2 JP26960297A JP26960297A JP4144049B2 JP 4144049 B2 JP4144049 B2 JP 4144049B2 JP 26960297 A JP26960297 A JP 26960297A JP 26960297 A JP26960297 A JP 26960297A JP 4144049 B2 JP4144049 B2 JP 4144049B2
- Authority
- JP
- Japan
- Prior art keywords
- antifouling
- fishing nets
- antifouling agent
- component
- group
- 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 - Fee Related
Links
- 239000002519 antifouling agent Substances 0.000 title claims description 53
- 230000003373 anti-fouling effect Effects 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 22
- 230000009477 glass transition Effects 0.000 claims description 13
- -1 isothiazolone compound Chemical class 0.000 claims description 13
- 239000004310 lactic acid Substances 0.000 claims description 12
- 235000014655 lactic acid Nutrition 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 229920000747 poly(lactic acid) Polymers 0.000 description 13
- 239000004626 polylactic acid Substances 0.000 description 13
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 239000013535 sea water Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000009360 aquaculture Methods 0.000 description 5
- 244000144974 aquaculture Species 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000238586 Cirripedia Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XASSXGVLGXNHLF-UHFFFAOYSA-N 4,5-dibromo-2-[(4-chlorophenyl)methyl]-1,2-thiazol-3-one Chemical compound C1=CC(Cl)=CC=C1CN1C(=O)C(Br)=C(Br)S1 XASSXGVLGXNHLF-UHFFFAOYSA-N 0.000 description 1
- GTYVCFZGYDUDAF-UHFFFAOYSA-N 4,5-dichloro-2-(4-chlorophenyl)-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1=CC=C(Cl)C=C1 GTYVCFZGYDUDAF-UHFFFAOYSA-N 0.000 description 1
- GYXRKHGSQNXWRZ-UHFFFAOYSA-N 4,5-dichloro-2-[(4-chlorophenyl)methyl]-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1CC1=CC=C(Cl)C=C1 GYXRKHGSQNXWRZ-UHFFFAOYSA-N 0.000 description 1
- JSPDPUAKFJOUDW-UHFFFAOYSA-N 4,5-dichloro-2-hexyl-1,2-thiazol-3-one Chemical compound CCCCCCN1SC(Cl)=C(Cl)C1=O JSPDPUAKFJOUDW-UHFFFAOYSA-N 0.000 description 1
- SJKDXDDFKGSTDN-UHFFFAOYSA-N 5-chloro-2-decyl-1,2-thiazol-3-one Chemical compound CCCCCCCCCCN1SC(Cl)=CC1=O SJKDXDDFKGSTDN-UHFFFAOYSA-N 0.000 description 1
- QWWNALHRDHGNMO-UHFFFAOYSA-N 5-chloro-4-methyl-2-octyl-1,2-thiazol-3-one Chemical compound CCCCCCCCN1SC(Cl)=C(C)C1=O QWWNALHRDHGNMO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000700670 Bryozoa Species 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 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 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、養殖網や定置網等の漁網およびこれらに使用されるロープ等の漁網付属具に水生生物が付着するのを防止し、しかもその効果が長時間においても持続される漁網用防汚剤に関するものである。
【０００２】
【従来の技術】
養殖網や定置網等の漁網およびこれらに使用されるロープ等の漁網付属具は、海中に長時間浸漬されるため、海藻類、フジツボ、軟体動物等の水生生物が付着することにより、これらの保守に多大な費用と労力が要されているのが現状である。これら水生生物の付着を防止するために、従来から有機錫系の防汚剤が広く使用されてきた。しかし、有機錫系の防汚剤は毒性があり、また蓄積性も高いので、食用の養殖生物に使用される場合の人体への影響、および防汚剤を直接取り扱う作業者への影響が危惧される。
【０００３】
一方、非錫系防汚剤として、亜酸化銅を有効成分とする漁網用防汚剤が使用されるようになってきた。しかし、亜酸化銅は海水中に溶出して銅イオンまたは銅化合物として残留するため、環境に好ましくない影響を及ぼす可能性が大きい。従って、これらの漁網用防汚剤の使用は困難な状況になってきている。
【０００４】
上記のような理由から重金属を含まない低公害性漁網用防汚剤の出現が望まれている。特開昭６０−３８３０６号公報、特開平１−２５４６０３号公報には、比較的毒性の低い有機化合物を使用した防汚剤、またこれらの化合物とアクリル系共重合体を併用する防汚剤が提案されている。しかし、これらの防汚剤は塗膜に柔軟性を付与したり、防汚成分を徐放させるための種々の添加物が配合されている。また、防汚成分および樹脂が均一に溶剤に溶解している場合、塗布後の乾燥工程で防汚成分が結晶化しながら析出する。そのため、塗膜中の防汚成分の濃度分布にバラツキが生じて長時間安定して防汚成分を溶出させることが困難となる。
【０００５】
【発明が解決しようとする課題】
本発明は、上記の問題を解決しようとするものであり、その目的は、環境への安全性が高く、得られる塗膜の柔軟性が良好であり、防汚性能およびその持続性の点においても優れた漁網用防汚剤を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討した結果、特定の有機防汚成分と、特定のガラス転移温度を有するポリエステル樹脂を併用することにより、得られる塗膜の柔軟性が良好で、かつ防汚成分の徐放性が得られて防汚性能が持続し、さらには環境汚染等の問題が生じない、漁網用防汚剤が得られることを見いだし、本発明を完成するに至った。
【０００７】
即ち、本発明は以下の通りである。
(1) 有機防汚成分と樹脂成分を含有する漁網用防汚剤であって、有機防汚成分が下記一般式（Ｉ）で示されるイソチアゾロン化合物の少なくとも１種を含んでなり、かつ樹脂成分が−２０〜５０℃のガラス転移温度を有するポリエステル樹脂を含んでなることを特徴とする漁網用防汚剤。
【０００８】
【化２】
（式中、ＸおよびＹは、同一または相異なって水素原子、ハロゲン原子または低級アルキル基を示し、Ｚは炭素数１〜１５のアルキル基、置換されていてもよいアリール基または置換されていてもよいアラルキル基を示す。）
(2) イソチアゾロン化合物が、４，５−ジクロロ−２−ｎ−オクチル−３−イソチアゾロンであることを特徴とする上記(1) に記載の漁網用防汚剤。
(3) ポリエステル樹脂が、ポリ乳酸、乳酸のコポリマー、あるいはこれらを主成分としたブレンド物であることを特徴とする上記(1) または(2) に記載の漁網用防汚剤。
(4) ポリエステル樹脂が、乳酸とカプロラクトンの共重合体であることを特徴とする上記(1) 〜(3) のいずれかに記載の漁網用防汚剤。
(5) 樹脂成分が１０重量％以上、有機防汚成分が１重量％以上配合され、有機溶媒で希釈された溶液または分散液であることを特徴とする上記(1) 〜(4) のいずれかに記載の漁網用防汚剤。
【００１０】
【発明の実施の形態】
以下に、本発明を詳細に説明する。本発明の漁網用防汚剤は、有機防汚成分と樹脂成分を主成分とするものである。有機防汚成分は、下記一般式（Ｉ）で示されるイソチアゾロン化合物を少なくとも１種含んでなる。
【００１１】
【化３】
（式中、ＸおよびＹは、同一または相異なって水素原子、ハロゲン原子または低級アルキル基を示し、Ｚは炭素数１〜１５のアルキル基、置換されていてもよいアリール基または置換されていてもよいアラルキル基を示す。）
【００１３】
上記一般式（Ｉ）において、Ｘ、Ｙにおけるハロゲン原子とは、フッ素原子、塩素原子、臭素原子、ヨウ素原子を表し、低級アルキル基とは、炭素数１〜６の直鎖状または分岐鎖状のアルキル基を示し、例えば、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。中でも、メチル基が好ましい。
【００１４】
Ｚにおける炭素数１〜１５のアルキル基とは、直鎖状、分岐鎖状のいずれでもよく、例えば、メチル基、エチル基、プロピル基、ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−デシル基等が挙げられる。中でも、ｎ−オクチル基が好ましい。
【００１５】
Ｚにおける「置換されていてもよいアリール基」のアリール基としては、例えば、フェニル基、トリル基、ナフチル基等が挙げられる。置換基としては、ハロゲン原子、メチル基等が挙げられる。
【００１６】
Ｚにおける「置換されていてもよいアラルキル基」のアラルキル基としては、例えば、ベンジル基、フェネチル基等が挙げられ、中でも、ベンジル基が好ましい。置換基としては、ハロゲン原子、メチル基等が挙げられる。
【００１７】
上記一般式（Ｉ）で表されるイソチアゾロン化合物の具体例としては、例えば、４，５−ジクロロ−２−ｎ−オクチル−３−イソチアゾロン、５−クロロ−２−ｎ−デシル−３−イソチアゾロン、４，５−ジクロロ−２−（４−クロロベンジル）−３−イソチアゾロン、４，５−ジクロロ−２−（４−クロロフェニル）−３−イソチアゾロン、４，５−ジクロロ−２−ｎ−ヘキシル−３−イソチアゾロン、４，５−ジブロモ−２−（４−クロロベンジル）−３−イソチアゾロン、４−メチル−５−クロロ−２−ｎ−オクチル−３−イソチアゾロン等が挙げられるが、特にこれらに限定されるものではない。これらの中では、防汚性能が特に優れている点から、４，５−ジクロロ−２−ｎ−オクチル−３−イソチアゾロンが特に好ましい。また、これらのイソチアゾロン化合物は単独で使用してもよいし、また複数を組み合わせて使用してもよい。
【００１８】
本発明の漁網用防汚剤のもう１つの成分である樹脂成分は、ガラス転移温度が−２０〜５０℃、好ましくは−１５〜４０℃のポリエステル樹脂を含む。ポリエステル樹脂のガラス転移温度が５０℃を超える場合、当該防汚剤から得られる塗膜の柔軟性が乏しくなって、海水への浸漬中に塗膜の剥離が生じ、防汚性能を持続させることが困難になる。逆にガラス転移温度が−２０℃未満の場合、防汚剤塗布後の漁網にブロッキングが生じ、作業性が著しく悪くなる。本発明においては、ポリエステル樹脂のガラス転移温度はＤＳＣを用いて測定される。
【００１９】
上記ガラス転移温度が−２０〜５０℃のポリエステル樹脂としては、一般的によく知られている脂肪族ポリエステル、脂肪族ポリエステルアミド、それらのブレンド体あるいは共重合体等が挙げられる。具体的には、ポリ乳酸または乳酸のコポリマー、ポリエチレンサクシネート、グリコール酸のコポリマーあるいはこれらを主成分としたブレンド物が挙げられる。
【００２０】
ポリ乳酸は、生体適合性、生分解性（生物化学的に加水分解を受けやすい性質）を有する高分子として医療用途にも既に使用されているので、ポリ乳酸、乳酸のコポリマー、またはこれらを主成分としたブレンド物を含有する防汚剤を使用しても環境問題はないと思われる。また、ポリ乳酸、乳酸のコポリマー、上記ブレンド物は、乳酸の光学異性比率の調節、共重合成分およびブレンドされる他の樹脂の種類や量により、ガラス転移温度、加水分解性を制御することが可能である。
【００２１】
上記ポリ乳酸は、通常用いられる方法で合成される。即ち、乳酸の環状二量体であるラクチドを原料とする開環重合、または乳酸水溶液を原料とする脱水縮重合で合成される。必要に応じて、通常用いられる触媒を使用することもできるし、溶融状態あるいは適当な溶剤中での合成も可能である。また、合成の際に第２成分を存在せしめることにより、乳酸のコポリマーを得ることが可能であるし、溶融あるいは溶液状態において別途合成された高分子とのブレンド体を製造することもできる。
【００２２】
乳酸と共重合する成分として、多塩基酸および多価アルコール等が挙げられる。多塩基酸としては、シュウ酸、コハク酸、アジピン酸等の脂肪族カルボン酸；グリコール酸、カプロラクトン、リンゴ酸等のオキシ酸等が例示される。多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、ブタンジオール等のグリコール等が例示される。これらの中でも、加水分解性および反応性の点でカプロラクトンが好ましい。また、ポリ乳酸や乳酸のコポリマーにブレンドされ得る高分子としては、ポリカプロラクトン、ポリエチレングリコール等が挙げられる。
【００２３】
このような樹脂成分を漁網用防汚剤に配合することにより、当該防汚剤から得られる塗膜に柔軟性が付与され、海水への浸漬中での当該塗膜の剥離を防止することができる。また、樹脂成分として生分解性に優れるポリ乳酸等を使用すると、海水中での塗膜表面からのポリ乳酸等の加水分解により、防汚成分を徐放させて防汚性能を持続させることができる。この防汚成分の徐放性の調整は、ポリ乳酸等の加水分解性を調整することにより行うことができる。さらに、例え水生生物が漁網に付着したとしても、ポリ乳酸等の加水分解と共に脱落させることができる。加えて、ポリ乳酸等は、その生分解性に起因して、海水中での塗膜表面からの加水分解や、塗膜の漁網から剥離が生じても環境を汚染することがない。
【００２４】
本発明の漁網用防汚剤の形態は特に限定されるものではないが、有機溶剤により希釈された溶液もしくは分散液のように製剤化されたものが好ましい。この場合の有機溶剤としては特に限定されるものではないが、例えば、トルエン、キシレン、トリメチルベンゼン等の芳香族炭化水素系溶剤、エタノール、イソプロパノール等のアルコール系溶剤、その他に、ケトン系、エーテル系、アミド系、エステル系溶剤等が挙げられる。また、これらの有機溶剤は１種単独でもよいし２種以上組み合わせて用いてもよい。
【００２５】
本発明の漁網用防汚剤が、上記のような有機溶剤による溶液もしくは分散液の場合の樹脂成分の配合割合は、好ましくは１０重量％以上、より好ましくは１０〜５０重量％、特に好ましくは２０〜４０重量％である。樹脂成分が１０重量％未満であると、必要量の防汚成分を漁網に塗付することが困難となるおそれがある。なお、樹脂成分の配合割合の上限は特に限定されないが、一般には５０重量％を超えると、防汚剤塗付量の増加による漁網の重量増が大きく、作業性が悪くなるおそれがある。
【００２６】
本発明の漁網用防汚剤が、上記のような有機溶剤による溶液もしくは分散液の場合の防汚成分の配合割合は、好ましくは１重量％以上、より好ましくは１〜３０重量％、特に好ましくは５〜２５重量％である。有機防汚成分の配合割合が１重量％未満であると、必要量の防汚成分を塗付するために防汚剤として多量に塗付することになり、コスト、作業性が悪くなるおそれがある。なお、有機防汚成分の配合割合の上限は特に限定されないが、一般には３０重量％を超えると塗膜と漁網との接着性が悪くなったり、水中への浸漬初期に防汚成分が大量に溶出する等の、特性が悪化するおそれがある。
【００２７】
製剤化の方法は、特に限定されないが、例えば、防汚成分と樹脂成分をそれぞれ別の溶剤に溶解または分散させた後、これらを混合してもよいし、または防汚成分と樹脂成分を同じ溶剤に逐次または同時に添加して溶解または分散させてもよい。
【００２８】
本発明の漁網用防汚剤は、有機防汚成分としての上記一般式（Ｉ）で示したイソチアゾロン化合物に加えて、他の防汚剤を併用することもできるが、その場合においては有機系のものであり、しかも安全性が確認されている防汚剤を併用することが好ましい。
【００２９】
本発明の漁網用防汚剤は、上述のように、特に添加剤を配合しなくとも防汚剤としての性能を発揮するが、得られる塗膜の撥水性の向上または防汚成分の溶出調整剤として、シリコーンオイルや流動パラフィン、あるいは椰子油、亜麻仁油、桐油等の植物油を配合することも可能である。
【００３０】
本発明において、漁網とは養殖用、定置用等の漁網およびこれらに使用されるロープ、浮き子等の漁網付属具をいう。また本発明の漁網用防汚剤が適用される漁網の種類は特に制限されるものではなく、例えばポリエチレン、ポリエステル等の種々の素材からなるものが挙げられる。
【００３１】
本発明の漁網用防汚剤は、上記一般式（Ｉ）で示したイソチアゾロン化合物とガラス転移温度が−２０〜５０℃のポリエステル樹脂を主成分とするため、得られる塗膜に柔軟性が付与され、海水での塗膜の剥離を防止することができ、また、樹脂成分として生分解性に優れるポリ乳酸等を使用すると防汚成分を徐放させて防汚性能を持続させることができる。さらには、高い安全性および環境汚染も少ないという利点を有する。また、防汚性能においても、養殖海域においてよく見られるフジツボ、ホヤ、コケムシ等に対して強い防汚効果を示す。加えて、重金属系防汚剤と比較して比重が非常に小さく、漁網用防汚剤として製剤化した場合、沈降を起こすことなく、作業性も非常に良好である。
【００３２】
【実施例】
以下、本発明を実施例によりさらに具体的に説明するが、これらにより本発明が限定されるものではない。なお、実施例における評価試験は以下の方法により行った。
【００３３】
１．樹脂の溶液粘度（ηsp/c)
樹脂０．１２５ｇをクロロホルム２５ｍｌに溶解して、ウベローデ粘度管を用いて２５℃で測定した。
２．樹脂のガラス転移温度
試料約１０ｍｇを調製後、ＤＳＣ−５０（島津製作所製）を用いて、窒素気流下において、昇温速度１０℃／分の条件で測定した。
【００３４】
＜樹脂の製造＞
窒素導入管、攪拌機、温度計を備えた５００ｍｌセパラブルフラスコに再沈殿により精製したＤＬ−ラクチド２００ｇ、カプロラクトン６７ｇ、触媒としてオクチル酸スズ０．０８ｇ、重合開始剤としてラウリルアルコール０．７３ｇを加えて、窒素気流下、１９０℃で６時間攪拌することにより重合体を得た。引き続き減圧下で１時間攪拌を続けて未反応の原料を除去した。得られた樹脂Ａの溶液粘度は０．８０ｄｌ／ｇ、ガラス転移温度は２３℃であった。以下、表１に示すように原料の仕込み比を変えて、上記と同様の方法により、異なったガラス転移温度を有する樹脂Ｂ〜樹脂Ｆを得た。
【００３５】
【表１】
実施例１〜６および比較例１〜３
上記で得られた樹脂Ａ〜樹脂Ｆに、有機防汚剤として４，５−ジクロロ−２−ｎ−オクチル−３−イソチアゾロン（ロームアンドハース社製シーナイン）を用い、表２に示すような割合で配合して漁網用防汚剤を調製した。各漁網用防汚剤について、漁網に浸漬塗装後、風乾して、４０ｃｍ×６０ｃｍの銅枠に固定した。これらの漁網を高知県須崎市の海洋中、水深１ｍに静置浸漬し、経時的に付着生物種と付着面積の割合（浸漬した漁網の面積を１００％とした時、生物がどの程度の面積に付着したか）を目視により観察した。その結果を表３に示す。
【００３７】
【表２】
【表３】
表３より、実施例１〜６で得られた漁網用防汚剤においては、４ヵ月経過後であっても、水生生物の付着を防止することができた。しかし、比較例１で得られた漁網用防汚剤においては、塗布乾燥後、ブロッキングが生じて供試不可能であった。比較例２〜３で得られた漁網用防汚剤においては、４ヵ月経過後では、水生生物の付着を抑制することがあまりできなかった。
【００４０】
【発明の効果】
以上の説明で明らかなように、本発明の漁網用防汚剤は、各水生生物に対する防汚性に優れ、得られる塗膜に柔軟性が付与されて海水での塗膜の剥離を防止することができ、防汚成分を徐放させて防汚性能を持続させることができ、さらには、高い安全性および環境汚染も少ないという利点を有する。加えて、重金属系防汚剤と比較して製剤化した場合、沈降を起こすことなく、作業性も非常に良好である。[0001]
BACKGROUND OF THE INVENTION
The present invention is an antifouling agent for fishing nets which prevents aquatic organisms from adhering to fishing nets such as aquaculture nets and stationary nets, and fishing net accessories such as ropes used therefor, and whose effects are sustained even for a long time. It is about.
[0002]
[Prior art]
Since fishing nets such as aquaculture nets and stationary nets and fishing net accessories such as ropes used in these are immersed in the sea for a long time, maintenance of these can be done by attaching aquatic organisms such as seaweeds, barnacles, mollusks, etc. The current situation is that a great deal of cost and labor are required. In order to prevent adhesion of these aquatic organisms, organotin antifouling agents have been widely used. However, since organotin antifouling agents are toxic and highly accumulative, there are concerns about the effects on the human body when used in edible aquaculture organisms, and on the workers who handle the antifouling agents directly. It is.
[0003]
On the other hand, antifouling agents for fishing nets containing cuprous oxide as an active ingredient have been used as non-tin antifouling agents. However, since cuprous oxide elutes in seawater and remains as copper ions or a copper compound, there is a great possibility that it has an unfavorable effect on the environment. Therefore, the use of these antifouling agents for fishing nets has become difficult.
[0004]
For the reasons described above, the advent of antifouling agents for low pollution fishing nets that do not contain heavy metals is desired. JP-A-60-38306 and JP-A-1-254603 disclose antifouling agents using organic compounds having relatively low toxicity, and antifouling agents using these compounds in combination with acrylic copolymers. Proposed. However, these antifouling agents are blended with various additives for imparting flexibility to the coating film and for releasing the antifouling components gradually. Further, when the antifouling component and the resin are uniformly dissolved in the solvent, the antifouling component is precipitated while crystallizing in the drying step after application. Therefore, the concentration distribution of the antifouling component in the coating film varies, and it becomes difficult to elute the antifouling component stably for a long time.
[0005]
[Problems to be solved by the invention]
The present invention is intended to solve the above-mentioned problems, and its purpose is high in safety to the environment, good flexibility of the resulting coating film, and in terms of antifouling performance and its sustainability. Is to provide an excellent antifouling agent for fishing nets.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a specific organic antifouling component and a polyester resin having a specific glass transition temperature, so that the obtained coating film has good flexibility. In addition, the present inventors have found that an antifouling agent for fishing nets can be obtained that provides sustained release properties of the antifouling components, maintains the antifouling performance, and does not cause problems such as environmental pollution, thereby completing the present invention. It was.
[0007]
That is, the present invention is as follows.
(1) A fishing net antifouling agent comprising an organic antifouling component and a resin component, wherein the organic antifouling component comprises at least one isothiazolone compound represented by the following general formula (I), and the resin component An antifouling agent for fishing nets comprising a polyester resin having a glass transition temperature of -20 to 50 ° C.
[0008]
[Chemical 2]
Wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom or a lower alkyl group, and Z is an alkyl group having 1 to 15 carbon atoms, an optionally substituted aryl group or a substituted one. Represents a good aralkyl group.)
(2) The antifouling agent for fishing nets according to (1) above, wherein the isothiazolone compound is 4,5-dichloro-2-n-octyl-3-isothiazolone.
(3) The antifouling agent for fishing nets according to the above (1) or (2), wherein the polyester resin is polylactic acid, a copolymer of lactic acid, or a blended product thereof.
(4) The antifouling agent for fishing nets according to any one of the above (1) to (3), wherein the polyester resin is a copolymer of lactic acid and caprolactone.
(5) Any of the above (1) to (4), wherein the resin component is a solution or dispersion containing 10% by weight or more of the organic antifouling component and 1% by weight or more of the organic antifouling component and diluted with an organic solvent. Antifouling agent for fishnets according to crab.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. The antifouling agent for fishing nets of the present invention comprises an organic antifouling component and a resin component as main components. The organic antifouling component comprises at least one isothiazolone compound represented by the following general formula (I).
[0011]
[Chemical 3]
Wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom or a lower alkyl group, and Z is an alkyl group having 1 to 15 carbon atoms, an optionally substituted aryl group or a substituted one. Represents a good aralkyl group.)
[0013]
In the general formula (I), the halogen atom in X and Y represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and the lower alkyl group is a linear or branched chain having 1 to 6 carbon atoms. And examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, a methyl group is preferable.
[0014]
The alkyl group having 1 to 15 carbon atoms in Z may be linear or branched. For example, methyl group, ethyl group, propyl group, butyl group, n-hexyl group, n-octyl group, n -A decyl group etc. are mentioned. Of these, an n-octyl group is preferable.
[0015]
Examples of the aryl group of the “optionally substituted aryl group” in Z include a phenyl group, a tolyl group, and a naphthyl group. Examples of the substituent include a halogen atom and a methyl group.
[0016]
Examples of the aralkyl group of the “optionally substituted aralkyl group” in Z include a benzyl group and a phenethyl group, and among them, a benzyl group is preferable. Examples of the substituent include a halogen atom and a methyl group.
[0017]
Specific examples of the isothiazolone compound represented by the general formula (I) include, for example, 4,5-dichloro-2-n-octyl-3-isothiazolone, 5-chloro-2-n-decyl-3-isothiazolone, 4,5-dichloro-2- (4-chlorobenzyl) -3-isothiazolone, 4,5-dichloro-2- (4-chlorophenyl) -3-isothiazolone, 4,5-dichloro-2-n-hexyl-3 -Isothiazolone, 4,5-dibromo-2- (4-chlorobenzyl) -3-isothiazolone, 4-methyl-5-chloro-2-n-octyl-3-isothiazolone, and the like. It is not something. Among these, 4,5-dichloro-2-n-octyl-3-isothiazolone is particularly preferable because of its particularly excellent antifouling performance. These isothiazolone compounds may be used alone or in combination of two or more.
[0018]
The resin component which is another component of the antifouling agent for fishing nets of the present invention contains a polyester resin having a glass transition temperature of -20 to 50 ° C, preferably -15 to 40 ° C. When the glass transition temperature of the polyester resin exceeds 50 ° C., the coating film obtained from the antifouling agent becomes less flexible, and the coating film peels off during immersion in seawater, thereby maintaining the antifouling performance. Becomes difficult. Conversely, when the glass transition temperature is less than −20 ° C., blocking occurs in the fishing net after application of the antifouling agent, and workability is significantly deteriorated. In the present invention, the glass transition temperature of the polyester resin is measured using DSC.
[0019]
Examples of the polyester resin having a glass transition temperature of -20 to 50 ° C. include generally known aliphatic polyesters, aliphatic polyester amides, blends or copolymers thereof. Specific examples include polylactic acid or a copolymer of lactic acid, polyethylene succinate, a copolymer of glycolic acid, or a blend based on these.
[0020]
Polylactic acid has already been used in medical applications as a polymer having biocompatibility and biodegradability (a property that is susceptible to biochemical hydrolysis). Therefore, polylactic acid, a copolymer of lactic acid, or these are mainly used. There seems to be no environmental problem even if an antifouling agent containing a blended product as an ingredient is used. Polylactic acid, lactic acid copolymer, and blends can control the glass transition temperature and hydrolyzability by adjusting the optical isomer ratio of lactic acid and the type and amount of copolymer components and other resins blended. Is possible.
[0021]
The polylactic acid is synthesized by a commonly used method. That is, it is synthesized by ring-opening polymerization using lactide, which is a cyclic dimer of lactic acid, or dehydration condensation polymerization using lactic acid aqueous solution as a raw material. If necessary, a commonly used catalyst can be used, and synthesis in a molten state or an appropriate solvent is also possible. In addition, a lactic acid copolymer can be obtained by making the second component present during the synthesis, and a blend with a polymer separately synthesized in a molten or solution state can also be produced.
[0022]
Examples of components copolymerized with lactic acid include polybasic acids and polyhydric alcohols. Examples of the polybasic acid include aliphatic carboxylic acids such as oxalic acid, succinic acid, and adipic acid; oxyacids such as glycolic acid, caprolactone, and malic acid. Examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, and butanediol. Among these, caprolactone is preferable in terms of hydrolyzability and reactivity. Examples of the polymer that can be blended with polylactic acid or a copolymer of lactic acid include polycaprolactone and polyethylene glycol.
[0023]
By blending such a resin component into the antifouling agent for fishing nets, flexibility is imparted to the coating film obtained from the antifouling agent, and peeling of the coating film during immersion in seawater can be prevented. it can. In addition, when polylactic acid with excellent biodegradability is used as the resin component, the antifouling component can be sustainedly released by hydrolysis of the polylactic acid from the coating surface in seawater to maintain the antifouling performance. it can. The sustained release property of the antifouling component can be adjusted by adjusting the hydrolyzability of polylactic acid or the like. Furthermore, even if aquatic organisms adhere to the fishing net, they can be removed with hydrolysis of polylactic acid or the like. In addition, polylactic acid or the like does not contaminate the environment even if hydrolysis from the coating film surface in seawater or peeling from the fishing net of the coating film occurs due to its biodegradability.
[0024]
The form of the antifouling agent for fishing nets of the present invention is not particularly limited, but is preferably formulated as a solution or dispersion diluted with an organic solvent. The organic solvent in this case is not particularly limited, but for example, aromatic hydrocarbon solvents such as toluene, xylene and trimethylbenzene, alcohol solvents such as ethanol and isopropanol, in addition to ketones and ethers. Amide-based and ester-based solvents. These organic solvents may be used alone or in combination of two or more.
[0025]
The mixing ratio of the resin component when the antifouling agent for fishing nets of the present invention is a solution or dispersion with an organic solvent as described above is preferably 10% by weight or more, more preferably 10 to 50% by weight, particularly preferably. 20 to 40% by weight. If the resin component is less than 10% by weight, it may be difficult to apply a necessary amount of the antifouling component to the fishing net. In addition, although the upper limit of the compounding ratio of the resin component is not particularly limited, in general, when it exceeds 50% by weight, the weight of the fishing net is greatly increased due to an increase in the amount of the antifouling agent applied, and workability may be deteriorated.
[0026]
The mixing ratio of the antifouling component when the antifouling agent for fishing nets of the present invention is a solution or dispersion with an organic solvent as described above is preferably 1% by weight or more, more preferably 1 to 30% by weight, particularly preferably. Is 5 to 25% by weight. If the blending ratio of the organic antifouling component is less than 1% by weight, a large amount of antifouling component will be applied to apply the necessary amount of antifouling component, which may reduce the cost and workability. is there. In addition, the upper limit of the blending ratio of the organic antifouling component is not particularly limited, but generally, when it exceeds 30% by weight, the adhesion between the coating film and the fishing net is deteriorated, or a large amount of the antifouling component is in the initial stage of immersion in water. The characteristics such as elution may be deteriorated.
[0027]
The formulation method is not particularly limited. For example, the antifouling component and the resin component may be dissolved or dispersed in different solvents and then mixed, or the antifouling component and the resin component may be the same. It may be added to the solvent sequentially or simultaneously to dissolve or disperse.
[0028]
The antifouling agent for fishing nets of the present invention may be used in combination with other antifouling agents in addition to the isothiazolone compound represented by the above general formula (I) as an organic antifouling component. In addition, it is preferable to use an antifouling agent that is safe and has been confirmed to be safe.
[0029]
As described above, the antifouling agent for fishing nets of the present invention exhibits the performance as an antifouling agent without any particular additives, but improves the water repellency of the resulting coating film or adjusts the dissolution of antifouling components. As an agent, it is also possible to mix vegetable oils such as silicone oil, liquid paraffin, coconut oil, linseed oil and tung oil.
[0030]
In the present invention, the fishing net refers to fishing nets for aquaculture, stationary, etc. and fishing net accessories such as ropes and floats used for these. The type of fishing net to which the antifouling agent for fishing nets of the present invention is applied is not particularly limited, and examples thereof include those made of various materials such as polyethylene and polyester.
[0031]
Since the antifouling agent for fishing nets of the present invention is composed mainly of the isothiazolone compound represented by the above general formula (I) and a polyester resin having a glass transition temperature of -20 to 50 ° C., flexibility is imparted to the resulting coating film. In addition, peeling of the coating film in seawater can be prevented, and when polylactic acid or the like having excellent biodegradability is used as the resin component, the antifouling component can be gradually released to maintain the antifouling performance. Furthermore, it has the advantage of high safety and less environmental pollution. Moreover, also in antifouling performance, it shows a strong antifouling effect against barnacles, sea squirts, bryozoans and the like often found in aquaculture areas. In addition, the specific gravity is very small compared to heavy metal antifouling agents, and when formulated as an antifouling agent for fishing nets, the workability is very good without causing sedimentation.
[0032]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition, the evaluation test in an Example was done with the following method.
[0033]
1. Resin solution viscosity (ηsp / c)
0.125 g of resin was dissolved in 25 ml of chloroform and measured at 25 ° C. using an Ubbelohde viscosity tube.
2. About 10 mg of a glass transition temperature sample of the resin was prepared and then measured using DSC-50 (manufactured by Shimadzu Corporation) under a nitrogen stream at a temperature increase rate of 10 ° C./min.
[0034]
<Manufacture of resin>
To a 500 ml separable flask equipped with a nitrogen inlet tube, a stirrer and a thermometer, add 200 g of DL-lactide purified by reprecipitation, 67 g of caprolactone, 0.08 g of tin octylate as a catalyst, and 0.73 g of lauryl alcohol as a polymerization initiator. The polymer was obtained by stirring at 190 ° C. for 6 hours under a nitrogen stream. Subsequently, stirring was continued for 1 hour under reduced pressure to remove unreacted raw materials. The solution viscosity of the obtained resin A was 0.80 dl / g, and the glass transition temperature was 23 ° C. Hereinafter, as shown in Table 1, resin B to resin F having different glass transition temperatures were obtained by the same method as above while changing the raw material charge ratio.
[0035]
[Table 1]
Examples 1-6 and Comparative Examples 1-3
The ratio as shown in Table 2 using 4,5-dichloro-2-n-octyl-3-isothiazolone (Rohm and Haas Co., Ltd. Sea Nine) as the organic antifouling agent for the resins A to F obtained above. The antifouling agent for fishing nets was prepared by blending with the above. About each anti-fouling agent for fishing nets, it was air-dried after dip-coating on the fishing nets and fixed to a 40 cm × 60 cm copper frame. These fishing nets are immersed in the sea of Susaki City, Kochi Prefecture, at a depth of 1 m, and the ratio of the attached species and the attached area over time (how much area the organism has when the area of the immersed fishing net is 100%) It was observed visually. The results are shown in Table 3.
[0037]
[Table 2]
[Table 3]
From Table 3, in the antifouling agent for fishing nets obtained in Examples 1 to 6, it was possible to prevent the attachment of aquatic organisms even after 4 months. However, the antifouling agent for fishing nets obtained in Comparative Example 1 was not able to be tested because of blocking after coating and drying. In the antifouling agent for fishing nets obtained in Comparative Examples 2 to 3, the adhesion of aquatic organisms could not be much suppressed after 4 months.
[0040]
【The invention's effect】
As is apparent from the above description, the antifouling agent for fishing nets of the present invention has excellent antifouling properties against aquatic organisms, and the resulting coating film is given flexibility to prevent peeling of the coating film in seawater. The antifouling component can be gradually released to maintain the antifouling performance, and further, it has the advantages of high safety and less environmental pollution. In addition, when formulated as a heavy metal antifouling agent, the workability is very good without causing sedimentation.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26960297A JP4144049B2 (en) | 1997-10-02 | 1997-10-02 | Antifouling agent for fishing nets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26960297A JP4144049B2 (en) | 1997-10-02 | 1997-10-02 | Antifouling agent for fishing nets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11106302A JPH11106302A (en) | 1999-04-20 |
| JP4144049B2 true JP4144049B2 (en) | 2008-09-03 |
Family
ID=17474657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26960297A Expired - Fee Related JP4144049B2 (en) | 1997-10-02 | 1997-10-02 | Antifouling agent for fishing nets |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4144049B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6676954B2 (en) * | 2000-04-06 | 2004-01-13 | Rohm And Haas Company | Controlled release compositions |
-
1997
- 1997-10-02 JP JP26960297A patent/JP4144049B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11106302A (en) | 1999-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5705212B2 (en) | Antifouling paint composition and use thereof | |
| KR102155024B1 (en) | Antifouling coating composition, antifouling coating film formed using said composition, and coated article having antifouling coating film on surface | |
| KR101670428B1 (en) | Antifouling coating composition, and fishing net, fishing net gear, and underwater structure coated with antifouling coating composition | |
| JP3914437B2 (en) | Antifouling paint, antifouling coating film, submerged structure and antifouling method | |
| TW200923037A (en) | Antifouling paint composition, antifouling paint film, base material with paint film, antifouling base material, method for forming paint film on surface of base material and method for antifouling base material | |
| JP2001139816A (en) | Curable composition, coating composition, paint, antifouling paint, cured product thereof, and antifouling method for substrate | |
| JPH0320370A (en) | Stainproofing paint | |
| JP2009173914A (en) | Water-based antifouling paint composition, production method thereof, coating film thereof, substrate coated with the coating film, and antifouling method | |
| JPH10168350A (en) | Antifouling paint composition | |
| JP4610763B2 (en) | Paint composition | |
| CN102892844A (en) | Antifouling coating composition, method for producing antifouling coating film, and antifouling coating film | |
| JP4902037B2 (en) | Antifouling agent composition, antifouling treatment substrate, and antifouling treatment method for substrate | |
| JP4144049B2 (en) | Antifouling agent for fishing nets | |
| JP3342815B2 (en) | Antifouling paint composition | |
| JP2003277680A (en) | Aqueous pollution-preventing resin composition | |
| JPS6357676A (en) | antifouling paint | |
| JP4056308B2 (en) | Underwater antifouling composition, antifouling coating film, fish net, etc. and antifouling method | |
| JP3733197B2 (en) | Antifouling paint composition, paint film formed from this antifouling paint composition, antifouling method using the antifouling paint composition, hull, underwater / water structure or fishery material coated with the paint film | |
| JP4144051B2 (en) | Antifouling agent for fishing nets | |
| JP4144050B2 (en) | Antifouling agent for fishing nets | |
| JPH0693214A (en) | Antifouling coating for fishing net | |
| JPH0582865B2 (en) | ||
| JP3362485B2 (en) | Fishing net implement antifouling agent | |
| JPH04142373A (en) | Antifouling coating material | |
| JP3910228B2 (en) | Underwater antifouling agent composition, and fishing net and underwater structure antifouling treatment method using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040902 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080311 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080428 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080527 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080609 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110627 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120627 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130627 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130627 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |