JPS63227673A - Antifouling coating - Google Patents
Antifouling coatingInfo
- Publication number
- JPS63227673A JPS63227673A JP6163787A JP6163787A JPS63227673A JP S63227673 A JPS63227673 A JP S63227673A JP 6163787 A JP6163787 A JP 6163787A JP 6163787 A JP6163787 A JP 6163787A JP S63227673 A JPS63227673 A JP S63227673A
- Authority
- JP
- Japan
- Prior art keywords
- ammonium salt
- quaternary ammonium
- formula
- group
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 title abstract description 9
- 239000011248 coating agent Substances 0.000 title abstract description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 27
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 claims abstract 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 239000003973 paint Substances 0.000 claims description 23
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 125000004104 aryloxy group Chemical group 0.000 claims 1
- -1 carboxymethyl quat Chemical compound 0.000 abstract description 23
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 2
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical group OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract 1
- 229960001031 glucose Drugs 0.000 abstract 1
- 239000013535 sea water Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 229940105329 carboxymethylcellulose Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 3
- WNBGYVXHFTYOBY-UHFFFAOYSA-N benzyl-dimethyl-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 WNBGYVXHFTYOBY-UHFFFAOYSA-N 0.000 description 3
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 3
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JWSQWXWJDSOPDU-UHFFFAOYSA-N (2,6-dimethyl-4-phenylheptan-4-yl)-dimethyl-[2-(2-phenoxyethoxy)ethyl]azanium Chemical compound C=1C=CC=CC=1OCCOCC[N+](C)(C)C(CC(C)C)(CC(C)C)C1=CC=CC=C1 JWSQWXWJDSOPDU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 241000196252 Ulva Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 2
- 229960003872 benzethonium Drugs 0.000 description 2
- 229960004830 cetylpyridinium Drugs 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940102728 methylbenzethonium Drugs 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 2
- DXCJSXXCGYUSIC-UHFFFAOYSA-N 1-dodecylisoquinoline Chemical class C1=CC=C2C(CCCCCCCCCCCC)=NC=CC2=C1 DXCJSXXCGYUSIC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZFCMISKWVFUWHP-UHFFFAOYSA-N 2-dodecylisoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCCCCCCCCCCC)=CC=C21 ZFCMISKWVFUWHP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000238426 Anostraca Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000202814 Cochliomyia hominivorax Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MTCUAOILFDZKCO-UHFFFAOYSA-N Decamethonium Chemical compound C[N+](C)(C)CCCCCCCCCC[N+](C)(C)C MTCUAOILFDZKCO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis 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
- 229920000297 Rayon Polymers 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- 241000196251 Ulva arasakii Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229950000405 decamethonium Drugs 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- YXUPZGKORWTXID-UHFFFAOYSA-N domiphen Chemical class CCCCCCCCCCCC[N+](C)(C)CCOC1=CC=CC=C1 YXUPZGKORWTXID-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- UGJCNRLBGKEGEH-UHFFFAOYSA-N sodium-binding benzofuran isophthalate Chemical compound COC1=CC=2C=C(C=3C(=CC(=CC=3)C(O)=O)C(O)=O)OC=2C=C1N(CCOCC1)CCOCCOCCN1C(C(=CC=1C=2)OC)=CC=1OC=2C1=CC=C(C(O)=O)C=C1C(O)=O UGJCNRLBGKEGEH-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- RQPWVAXZWDTDPH-UHFFFAOYSA-N tridodecyl(methyl)azanium Chemical group CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC RQPWVAXZWDTDPH-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
(イ)産業上の利用分野
本発明は船底、漁網、海中構築物などの生物付着防止塗
料即ち防汚塗料に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a paint for preventing biofouling on ship bottoms, fishing nets, underwater structures, etc., that is, an antifouling paint.
(ロ)従来の技術
従来より、海水にさらされる固体表面、例えば船底や魚
網などは、フジッボ、ムラサキガイ、ホヤ、アオサ、ア
オノリのような海棲生物が付着成長するものであるが、
これによりその機能が損われ大きな被害をうけている。(B) Conventional technology Traditionally, solid surfaces exposed to seawater, such as ship bottoms and fishing nets, have been home to marine organisms such as Fujitbo, mussels, sea squirts, sea lettuce, and blue seaweed.
This impairs its functionality and causes great damage.
この対策として、これら海棲生物の付着を防止する薬剤
が、防汚剤と称して使用されてきた。当初はその効果が
大きい故に有機水銀化合物が使用されたが、これは同時
に環境を汚染するものであり、使用が規制されるように
なった。その後有機錫化合物が使用されるようになった
が、このものも毒性は低いが魚類貝類等の体内に蓄積性
があり、やはり環境衛生上問題があることが判明し、同
様に規制される方向にきている。また陸上における木造
構築物から、0螺を駆除する目的で使用されているハロ
ゲン化芳香族化合物もまた地中に滲透し、地下水や海水
を汚染することが明らかになり、同様に使用禁止が検討
されている。As a countermeasure against this problem, chemicals that prevent the adhesion of these marine organisms have been used as antifouling agents. Initially, organic mercury compounds were used because they were highly effective, but they also polluted the environment, and their use came to be regulated. Later, organotin compounds began to be used, but although these compounds have low toxicity, they accumulate in the bodies of fish and shellfish, and it was found that they also pose environmental health problems, so they are likely to be regulated in the same way. I'm coming. It has also been revealed that halogenated aromatic compounds, which are used to exterminate screwworms from wooden structures on land, seep into the ground and contaminate groundwater and seawater, and banning their use is also being considered. ing.
このような現状から、環境を破壊せずに、生物の付着繁
殖を防止する防汚塗料の早急な開発が要望されている。Under these circumstances, there is an urgent need for the development of antifouling paints that prevent the attachment and propagation of living things without destroying the environment.
(ハ)発明が解決しようとする問題点
無水グルコース単位あたり 1.5〜3.0個のカルボ
キシメチル基をもつカルボキシメチルセルロースナトリ
ウム
・ハロゲン塩を共通溶媒中で混合すると、速やかに反応
してカルボキシメチルセルロース第四アンモニウム塩(
CMC第四アンモニウム塩)が得られる(特開昭61−
16901号)。このものは一般に水に水溶性であるが
、防菌、防かび等の薬理作用を有し、このものを含有す
る固体表面には、菌、かびなどが付着しにくいことが認
められている。(c) Problems to be solved by the invention When carboxymethyl cellulose sodium halide having 1.5 to 3.0 carboxymethyl groups per anhydroglucose unit is mixed in a common solvent, carboxymethyl cellulose reacts rapidly. Quaternary ammonium salt (
CMC quaternary ammonium salt) is obtained (JP-A-61-
No. 16901). Although this substance is generally water-soluble, it has pharmacological effects such as antibacterial and antifungal properties, and it is recognized that bacteria, mold, etc. are less likely to adhere to solid surfaces containing this substance.
CMC第四アンモニウム塩は、溶剤溶液を固体表面に塗
布し、溶剤を蒸発させることにより、塗膜化する。その
ようにして作製した塗膜を淡水中に浸漬したところ、淡
水中の防汚作用を有することが認められた。しかし、塗
膜′は柔かく、水膨潤性であるため、防汚塗料としては
実用上問題がある。The CMC quaternary ammonium salt is formed into a film by applying a solvent solution to a solid surface and evaporating the solvent. When the coating film thus prepared was immersed in fresh water, it was found to have an antifouling effect in fresh water. However, since the coating film is soft and water-swellable, it poses a practical problem as an antifouling paint.
防汚塗料としての大きな需要は、淡水中よりもむしろ海
水中に浸漬して使用する固体表面の塗装にある。CMC
第四アンモニウム塩は海水の場合、徐々に溶解していく
性質がある。これは、海水中の塩化ナトリウムがCMC
第四アンモニウム塩を徐々にイオン交換し、第四アンモ
ニウム・塩化物と、CMCナトリウム塩となり、いずれ
も水に溶解していくためと思われる。A great demand for antifouling coatings is for solid surface coatings that are immersed in seawater rather than freshwater. CMC
Quaternary ammonium salts have the property of gradually dissolving in seawater. This is because sodium chloride in seawater is CMC.
This seems to be because the quaternary ammonium salt is gradually ion-exchanged to become quaternary ammonium chloride and CMC sodium salt, both of which dissolve in water.
もっとも第四アンモニウム塩の溶出自体そのものは、そ
の表面からの生物排除のドライビングフォースとも考え
られるので他の海水不溶性塗料バインダーに混合し塗装
すれば、実用性のある防汚塗料が得られると考えられる
。さらに、第四アンモニウム塩が海水に溶解した状態で
の毒性を、有機錫化合物と比較したところ、通に低毒性
であることをみとめた。However, the elution of the quaternary ammonium salt itself can be thought of as a driving force for eliminating living organisms from the surface, so it is thought that a practical antifouling paint can be obtained by mixing it with other seawater-insoluble paint binders and painting. . Furthermore, when the toxicity of quaternary ammonium salts dissolved in seawater was compared with that of organic tin compounds, it was found that the toxicity was generally low.
上記の知見に基づき、有機溶媒溶解性第四アンモニウム
塩を有効成分とし、これに相溶性で有機溶媒に可溶性の
アクリルポリマーをベヒリルとし、これらを有機溶媒に
溶解して塗料を作製したところ、実用上充分な効力を有
する防汚塗料を得ることができ、本発明に到達した。Based on the above findings, we prepared a paint by dissolving an organic solvent-soluble quaternary ammonium salt as an active ingredient and an organic solvent-soluble acrylic polymer called Behiryl, which was compatible with this, and found that it could be put to practical use. Thus, an antifouling paint with sufficient efficacy can be obtained, and the present invention has been achieved.
(二)問題点を解決するための手段と作用この発明は、
下記式で表わされ有機溶媒溶解性のカルボキシメチルセ
ルロース第四アンモニウム塩
〔式中、Rは水素原子又はカルボキシメチル基の第四ア
ンモニウム塩であり、nは10〜1000である。(2) Means and effects for solving the problems This invention has the following features:
A carboxymethyl cellulose quaternary ammonium salt represented by the following formula and soluble in an organic solvent [wherein R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group, and n is 10 to 1000.
但し無水グルコース単位当りカルボキシメチル基の置換
度は1.5〜3.0であり、カルボキシメチル基の第四
アンモニウム塩は、開式:
(式中、R1−R4は、それぞれCi−2oの直鎖もし
くは分校状の飽和もしくは不飽和の脂肪族炭化水素基で
あるか、R1−R4の三つが前記炭化水素基で一つがア
ラルキル基、トリアルキルアンモニウムアルキルもしく
はアリールオキシアルキル基であるか、R1−R4の二
つが前記炭化水素基で残りの二つがアラルキルおよびジ
アルキルフェノキシ(もしくはアルキルフェノキシ)ア
ルキレンオキシアルキル基であるが、またはR1−R4
の一つもしくは二つか前記炭化水素基で残りの二つもし
くは三つが窒素原子とともに異項環を形成する)の10
〜50重量%と、前記カルボキシメチルセルロース第四
アンモニウム塩と相溶性で有機溶媒に可溶性のア多すル
酸アルキルエステルおよび/またはメタクリル酸アルキ
ルエステルを主成分とする共重合体50〜90重量%と
の有機溶媒溶液からなる防汚塗料を提供するものである
。However, the degree of substitution of the carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the quaternary ammonium salt of the carboxymethyl group has the following formula: It is a chain or branched saturated or unsaturated aliphatic hydrocarbon group, or three of R1-R4 are the above-mentioned hydrocarbon groups and one is an aralkyl group, trialkylammonium alkyl or aryloxyalkyl group, or R1- Two of R4 are the above hydrocarbon groups and the remaining two are aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or R1-R4
one or two of the above hydrocarbon groups and the remaining two or three form a heterocyclic ring with the nitrogen atom)
~50% by weight, and 50 to 90% by weight of a copolymer mainly composed of an alkyl alkyl ester and/or alkyl methacrylate that is compatible with the carboxymethyl cellulose quaternary ammonium salt and soluble in an organic solvent. The present invention provides an antifouling paint made of an organic solvent solution.
この発明に用いられるC M Cf四アンモニウム塩と
しては、前記開式における第四アンモニウム基が次のよ
うなものが挙げられる。Examples of the C M Cf tetraammonium salt used in this invention include those in which the quaternary ammonium group in the above-mentioned open formula is as follows.
(i)R”〜R4がそれぞれC1−20の直鎖もしくは
分校状の飽和もしくは不飽和の脂肪族炭化水素基のもの
。(i) R'' to R4 are each a C1-20 linear or branched saturated or unsaturated aliphatic hydrocarbon group.
ラウリルトリメチルアンモニウム、セチルトリメチルア
ンモニウム、ステアリルトリメチルアンモニウム、トリ
オクチルメチルアンモニウム、ジメチルジステアリルア
ンモニウム、ジメチルオレイルリノリルアンモニウム、
トリメチルモノベヘニルアンモニウム、メチルトリラウ
リルアンモニウム基など、
(ii)R1−R4の三つが前記炭化水素基で一つがア
ラルキル、トリアルキルアンモニウムアルキルもしくは
アリールオキシアルキル基のもの。lauryltrimethylammonium, cetyltrimethylammonium, stearyltrimethylammonium, trioctylmethylammonium, dimethyldistearylammonium, dimethyloleyllinolyl ammonium,
trimethylmonobhenylammonium, methyltrilauryl ammonium groups, etc. (ii) R1 to R4 are three of the above hydrocarbon groups and one is an aralkyl, trialkylammonium alkyl, or aryloxyalkyl group.
テトラデシルジメチルベンジルアンモニウム、(トリメ
チルアンモニウムヘキシル)トリメチルアンモニウム、
(トリメチル−アンモニウムデシル)トリメデルアンモ
ニウム〈すなわちデカメトニウム)、ラウリルフェノキ
シジメチルアンモニウムなど、
fD R”〜R4の二つが前記炭化水素基で残りの二
つがアラルキル基およびジアルキルフェノキシ(もしく
はアルキルフェノキシ)アルキレンオキシアルキル基で
あるもの。Tetradecyldimethylbenzylammonium, (trimethylammoniumhexyl)trimethylammonium,
(trimethyl-ammoniumdecyl) trimedelammonium (i.e. decamethonium), laurylphenoxydimethylammonium, etc., where two of fD R'' to R4 are the above hydrocarbon groups and the remaining two are aralkyl groups and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl What is the basis.
ジイソブチルフェノキシエトキシエチルジメチルベンジ
ルアンモニウム〔すなわちベンゼトニウム〕、(シイン
ブチルンメチルフエノキシエトキシエチルジメチルベン
ジルアンモニウム基〔すなわちメチルベンゼトニウム塩
〕など。diisobutylphenoxyethoxyethyldimethylbenzylammonium [i.e., benzethonium], (diisobutylphenoxyethoxyethyldimethylbenzylammonium group [i.e., methylbenzethonium salt]), etc.
00 R1−R4の一つもしくは二つが前記炭化水素基
で残りの二つもしくは三つが窒素原子とともに異項環を
形成するもの。00 One or two of R1 to R4 are the above hydrocarbon groups, and the remaining two or three form a heterocyclic ring together with the nitrogen atom.
ラウリルピリジニウム、セチルピリジニウム、ラウリル
イソキノリニウム、ラウリルピリジニウム、ラウリルキ
ナルシウム基など。laurylpyridinium, cetylpyridinium, laurylisoquinolinium, laurylpyridinium, laurylquinalsium group, etc.
この発明に用いられるCMCの第四アンモニウム塩とし
て好ましいものは、ラウリルトリメチルアンモニウム塩
、テトラデシルジメチルベンジルアンモニウム塩、セチ
ルトリメチルアンモニウム塩、ステアリルトリメチルア
ンモニウム塩、ラウリルピリジニウム塩、セチルピリジ
ニウム塩、ベンゼトニウム塩、メチルベンゼトニウム塩
、ラウリルフエノキシエチルジメチルアンモニウム塩、
ラウリルイソキノリニウム塩などである。Preferred quaternary ammonium salts of CMC used in this invention include lauryltrimethylammonium salt, tetradecyldimethylbenzylammonium salt, cetyltrimethylammonium salt, stearyltrimethylammonium salt, laurylpyridinium salt, cetylpyridinium salt, benzethonium salt, and methyl Benzethonium salt, laurylphenoxyethyldimethylammonium salt,
laurylisoquinolinium salts, etc.
この発明に用いられるCMC第四アンモニウム塩は、無
水グルコース単位当りのカルボキシメチル基による置換
度が1.5〜3.0のカルボキシメチルセルロース又は
その塩の溶液と、対応する第四アンモニウム化合物もし
くはその溶液とを混合して反応させ、生成したカルボキ
シメチルセルロース第四アンモニウム塩を分#f精製す
ることによって製造される。The CMC quaternary ammonium salt used in this invention consists of a solution of carboxymethylcellulose or a salt thereof having a degree of substitution by carboxymethyl groups per anhydroglucose unit of 1.5 to 3.0, and a corresponding quaternary ammonium compound or a solution thereof. It is produced by mixing and reacting the carboxymethyl cellulose quaternary ammonium salt, and purifying the resulting quaternary ammonium salt.
この発明に用いるCMC第四アンモニウム塩の原料とし
て用いるCMCは、その第四アンモニウム塩の有機溶媒
に対する溶解性からみて、DSが1.5〜3.0である
必要がある。ごのような高置換度のCMCには、例えば
特開昭58−176202号公報に記載されている多段
エーテル化法で製造されるものなどが利用できる。CM
Cは、通常ナトリウム塩、カリウム塩などのアルカリ金
属塩が用いられる。カルシウム塩などのアルカリ土類金
属塩や酸形、部分酸形も使用できるが、ナトリウム塩が
=10−
最も好ましい。The CMC used as a raw material for the CMC quaternary ammonium salt used in this invention needs to have a DS of 1.5 to 3.0 in view of the solubility of the quaternary ammonium salt in an organic solvent. As CMC having a high degree of substitution, such as CMC, those produced by the multistage etherification method described in JP-A-58-176202, for example, can be used. CM
C is usually an alkali metal salt such as sodium salt or potassium salt. Although alkaline earth metal salts such as calcium salts, acid forms, and partially acid forms can also be used, sodium salts are most preferred.
この発明に用いられるアクリル酸アルキルエステルおよ
び/またはメタクリル酸アルキルエステルを主成分とす
る共重合体とは、モノマーとして、アクリル酸および/
またはメタクリル酸の例えば炭素原子数が1〜8のアル
キルエステルを主成分として、これに少量のメタクリル
酸ヒドロキシアルキルエステル、アクリル酸ヒドロキシ
アルキルエステル、不飽和の有機酸、酢酸ビニル、塩化
ビニル、アクリルニトリル、スチレンなどを含む共重合
体を意味し、有機溶媒に可溶性でガラス転移点が一り0
℃〜30℃程度のもので、前記CMC第四アンモニウム
塩と粕溶性で、この第四アンモニウム塩とからなる有機
溶媒溶液を塗料に用いた場合、接着強度、引張り強度、
耐水性などに優れた塗膜が得られるものである。The copolymer containing acrylic acid alkyl ester and/or methacrylic acid alkyl ester as a main component used in this invention refers to acrylic acid and/or methacrylic acid alkyl ester as monomers.
Alternatively, the main component is an alkyl ester of methacrylic acid having 1 to 8 carbon atoms, with a small amount of methacrylic acid hydroxyalkyl ester, acrylic acid hydroxyalkyl ester, unsaturated organic acid, vinyl acetate, vinyl chloride, acrylonitrile. , refers to a copolymer containing styrene, etc., which is soluble in organic solvents and has a glass transition point of 0.
℃ to 30℃, and is lees-soluble with the CMC quaternary ammonium salt. When an organic solvent solution consisting of this quaternary ammonium salt is used in a paint, adhesive strength, tensile strength,
A coating film with excellent water resistance etc. can be obtained.
この発明の防汚塗料において、CMC第四アンモニウム
塩は10〜50重量%、共重合体は50〜90%の比率
で用いられる。CMC第四アンモニウム塩の含有量が上
記範囲を超えると塗膜性能が低下する傾向が増大し、逆
に含有量がこの範囲より少ないと、防汚効果が低下する
。In the antifouling paint of this invention, the CMC quaternary ammonium salt is used in a ratio of 10 to 50% by weight, and the copolymer is used in a ratio of 50 to 90%. If the content of the CMC quaternary ammonium salt exceeds the above range, there is an increased tendency for the coating film performance to deteriorate, and conversely, if the content is less than this range, the antifouling effect will decrease.
またこの発明の防汚塗料に用いられる有機溶媒は、前記
共重合体とCMC第四アンモニウム塩との共通溶媒であ
って、低級アルコールのメタノール、エタノール、プロ
パツール、イソプロパツール、ブタノール、イソブタノ
ールなど、ケトン類′のメチルエチルケトン、メチルイ
ソブチルケトンなどが挙げられる。Further, the organic solvent used in the antifouling paint of the present invention is a common solvent for the copolymer and the CMC quaternary ammonium salt, and includes lower alcohols such as methanol, ethanol, propatool, isopropanol, butanol, and isobutanol. Examples of ketones include methyl ethyl ketone and methyl isobutyl ketone.
なおこの発明の防汚塗料としては、上記有機溶媒溶液以
外に、所望により、例えば柔軟剤2着白剤などの他の成
分を含有させてもよい。The antifouling paint of the present invention may contain other components, such as a softener 2 and a whitening agent, if desired, in addition to the above-mentioned organic solvent solution.
以下に実施例により本発明を具体的に説明するが、本発
明はこれにより限定されるものではない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.
(ホ)実施例
特開昭61−16901号に記載の方法に基づいて、C
MC第四アンモニウム塩を合成した。即ち、カルボキシ
メチル基置換度2.56 、重合度約100のCMCナ
トリウムの10%水溶液に、そのカルボキシ基当間より
も10%過剰量の第四アンモニウム・ハログン塩を加え
撹拌混合した。生成する沈澱を濾別し、水洗後常温で真
空乾燥し、目的物を得た。(E) Example Based on the method described in JP-A No. 61-16901, C
MC quaternary ammonium salt was synthesized. That is, to a 10% aqueous solution of CMC sodium having a degree of carboxymethyl group substitution of 2.56 and a degree of polymerization of about 100, a quaternary ammonium halogone salt in an amount 10% in excess of the amount of the carboxylic group was added and mixed with stirring. The resulting precipitate was filtered, washed with water, and then vacuum dried at room temperature to obtain the desired product.
使用した第四アンモニウム・ハロゲン塩は次の通りであ
る。The quaternary ammonium halogen salt used is as follows.
テトラデシルジメチルベンゾアンモ
ニウム・クロライド、
セチルピリジニウム・クロライド、
ドデシルトリメチルアンモニウム・
クロライド
上記によって取得したCMC第四アンモニウム塩30g
にアクリル塗料(L R−177、三菱レイヨン:アク
リル酸アルキルエステルとメタクリル酸アルキルエステ
ルを主成分として少量のメタクリル酸ヒドロキシアルキ
ルエステルを含む共重合体樹脂40%、キシレン/イソ
プロパツール溶剤60%)175Q、イソブタノール5
601;lを加えて均一に溶解させ、それぞれ防汚塗料
溶液とした。上記塗料溶液にポリエチレン製漁網を浸漬
し、引揚げて懸吊により余剰塗料を脱落させ、2日間常
温乾燥して固型分を漁網に定着させた。Tetradecyldimethylbenzoammonium chloride, cetylpyridinium chloride, dodecyltrimethylammonium chloride 30 g of CMC quaternary ammonium salt obtained as above
Acrylic paint (L R-177, Mitsubishi Rayon: 40% copolymer resin containing acrylic acid alkyl ester and methacrylic acid alkyl ester as main components and a small amount of methacrylic acid hydroxyalkyl ester, xylene/isopropanol solvent 60%) 175Q, isobutanol 5
601; 1 was added and dissolved uniformly to prepare an antifouling paint solution. A polyethylene fishing net was immersed in the above paint solution, pulled up and suspended to remove excess paint, and dried for two days at room temperature to fix the solid content on the fishing net.
=12−
瀬戸的海岸海水中に晩秋〜初冬の2ケ月間浸漬した貝(
フジッボ、ムラサキガイ、セルプラ)、藻(アオサ、ア
オノリ)の付着状況を観察した。=12- Shellfish immersed in Seto coast seawater for 2 months from late autumn to early winter (
We observed the adhesion of algae (Ulva, Ulva, Green Nori).
第1表にその結果を示す。なお比較に用いた市販防汚塗
料は、固形分中にトリブチルスズオキサイドを2%含有
する塗料である。Table 1 shows the results. The commercially available antifouling paint used for comparison is a paint containing 2% tributyltin oxide in solid content.
(以下余白)
本願発明の実施例の塗料は、トリブチルスズオキサイド
含有の市販防汚塗料にほぼ匹敵する防汚性を有している
。(The following is a blank space) The paints of the examples of the present invention have antifouling properties that are almost comparable to commercially available antifouling paints containing tributyltin oxide.
参考例
下記方法でCMC第四アンモニウム塩の動植物に対する
毒性試験を行った。Reference Example A toxicity test of CMC quaternary ammonium salt to animals and plants was conducted in the following manner.
植物二人工高水(ハイプツト社のハイリコン)中、20
℃、24時間保持したとき7オサの死滅する薬剤濃度
動物二人工高水(ハイプツト社のハイリコン)中、20
℃、24時間保持したときブラインシュリンフの死ぬ濃
度
試験結果を第2表に示す。Plant 2 Artificial High Water (Hylicon by Hyput), 20
The drug concentration that kills 7 animals when kept for 24 hours at
Table 2 shows the test results for the concentration at which brine shrimp died when kept at ℃ for 24 hours.
(以下余白)
第 2 表
植 物 動 物 (pl)
CMCテトラデシルジメチ
ルベンジルアンモニウム 1〜21〜20〜ICセ
チルピリジニウム 1〜21〜20MCドデシルトリメ
チル
アンモニウム 2〜52〜50MCベンゼ
トニウム 2〜52〜5標 準 品
0,05〜1 0.2〜1(トリブチル錫オキシド
)
(ホ)発明の効果
本発明の塗料は漁網、船底、海上構築物などの海水中に
浸漬される固体表面の生物付着防止剤として低毒性で環
境汚染のおそれのないものである。(Left below) Table 2 Plants Animals (pl) CMC Tetradecyldimethylbenzylammonium 1-21-20-IC Cetylpyridinium 1-21-20MC Dodecyltrimethylammonium 2-52-50MC Benzethonium 2-52-5 Standard Goods
0.05-1 0.2-1 (tributyltin oxide) (e) Effects of the invention The paint of the present invention has low toxicity as a biofouling prevention agent for solid surfaces immersed in seawater, such as fishing nets, ship bottoms, and offshore structures. and there is no risk of environmental pollution.
Claims (1)
ルセルロース第四アンモニウム塩 ▲数式、化学式、表等があります▼ 〔式中、Rは水素原子又はカルボキシメチル基の第四ア
ンモニウム塩であり、nは10〜1000である。 但し無水グルコース単位当りカルボキシメチル基の置換
度は1.5〜3.0であり、カルボキシメチル基の第四
アンモニウム塩は、副式: ▲数式、化学式、表等があります▼ (式中、R^1〜R^4は、それぞれC_1_−_2_
0の直鎖もしくは分枝状の飽和もしくは不飽和の脂肪族
炭化水素基であるか、R^1〜R^4の三つが前記炭化
水素基で一つがアラルキル基、トリアルキルアンモニウ
ムアルキルもしくはアリールオキシアルキル基であるか
、R^1〜R^4の二つが前記炭化水素基で残りの二つ
がアラルキルおよびジアルキルフェノキシ(もしくはア
ルキルフェノキシ)アルキレンオキシアルキル基である
か、またはR^1〜R^4の一つもしくは二つが前記炭
化水素基で残りの二つもしくは三つが窒素原子とともに
異項環を形成する)の10〜50重量%と、前記カルボ
キシメチルセルロース第四アンモニウム塩と相溶性で有
機溶媒に可溶性のアクリル酸アルキルエステルおよび/
またはメタクリル酸アルキルエステルを主成分とする共
重合体50〜90重量%との有機溶媒溶液からなる防汚
塗料。[Claims] 1. Carboxymethylcellulose quaternary ammonium salt represented by the following formula and soluble in organic solvents ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group] It is an ammonium salt, and n is 10 to 1000. However, the degree of substitution of the carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the quaternary ammonium salt of the carboxymethyl group has the sub-formula: ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, R ^1~R^4 are respectively C_1_-_2_
0 linear or branched saturated or unsaturated aliphatic hydrocarbon groups, or three of R^1 to R^4 are the above hydrocarbon groups and one is an aralkyl group, trialkylammonium alkyl, or aryloxy is an alkyl group, two of R^1 to R^4 are the above hydrocarbon groups and the remaining two are aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or R^1 to R^4 one or two of which are the hydrocarbon groups and the remaining two or three form a heterocyclic ring with the nitrogen atom), which is compatible with the carboxymethyl cellulose quaternary ammonium salt and is compatible with the organic solvent. Soluble acrylic acid alkyl ester and/or
Alternatively, an antifouling paint consisting of an organic solvent solution of 50 to 90% by weight of a copolymer containing methacrylic acid alkyl ester as a main component.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6163787A JPS63227673A (en) | 1987-03-16 | 1987-03-16 | Antifouling coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6163787A JPS63227673A (en) | 1987-03-16 | 1987-03-16 | Antifouling coating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63227673A true JPS63227673A (en) | 1988-09-21 |
Family
ID=13176916
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6163787A Pending JPS63227673A (en) | 1987-03-16 | 1987-03-16 | Antifouling coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63227673A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004502820A (en) * | 2000-07-06 | 2004-01-29 | インターナショナル コーティングズ リミテッド | Antifouling paint |
JP2020063426A (en) * | 2018-09-06 | 2020-04-23 | 花王株式会社 | Aquatic biofouling inhibiting agent |
JP2020063427A (en) * | 2018-09-06 | 2020-04-23 | 花王株式会社 | Flow resistance reducing agent |
-
1987
- 1987-03-16 JP JP6163787A patent/JPS63227673A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004502820A (en) * | 2000-07-06 | 2004-01-29 | インターナショナル コーティングズ リミテッド | Antifouling paint |
JP4911861B2 (en) * | 2000-07-06 | 2012-04-04 | インターナショナル コーティングズ リミテッド | Antifouling paint |
JP2020063426A (en) * | 2018-09-06 | 2020-04-23 | 花王株式会社 | Aquatic biofouling inhibiting agent |
JP2020063427A (en) * | 2018-09-06 | 2020-04-23 | 花王株式会社 | Flow resistance reducing agent |
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