MARINE SESSILE ORGANISM-REPELLING COMPOSITION

Abstract

A compound represented by the formula below:

##STR00001##

wherein R is selected from the group consisting of benzyl, C.sub.3-11 alkyl, C.sub.3-11 alkenyl, C.sub.2-9 branched alkenyl, C.sub.3-9 branched alkyl, and CH.sub.2OAc.

Claims

1. A compound represented by the formula: ##STR00032## wherein R is selected from the group consisting of benzyl, C.sub.3-11 alkyl, C.sub.3-11 alkenyl, C.sub.2-9 branched alkenyl, C.sub.3-9 branched alkyl, and CH.sub.2OAc.

2. The compound according to claim 1, represented by the formula: ##STR00033##

3. A compound, represented by the formula: ##STR00034## wherein R is selected from the group consisting of C.sub.1-6 alkyl, C.sub.2-6 alkenyl, halogen, C(O)OCC.sub.1-6 alkyl, nitro, and OC.sub.1-6 alkyl.

4. The compound according to claim 3, represented by the formula: ##STR00035##

5. A marine sessile organisms-repelling composition comprising the compound according to claim 1, and a film-forming agent.

6. The marine sessile organisms-repelling composition according to claim 5, wherein the compound is represented by the formula: ##STR00036## ##STR00037##

7. The marine sessile organisms-repelling composition according to claim 6, wherein the marine sessile organisms is Hydrozoa.

8. The marine sessile organisms-repelling composition according to claim 5, further comprising a polyether-modified polydimethylsiloxane having a hydrophile-lipophile balance (HLB) of 2 to 12.

9. A marine sessile organisms-repelling composition comprising the compound according to claim 3, and a film-forming agent.

10. The marine sessile organisms-repelling composition according to claim 9, wherein the compound is represented by the formula: ##STR00038## ##STR00039##

11. The marine sessile organisms-repelling composition according to claim 10, wherein the marine sessile organisms is Hydrozoa.

12. The marine sessile organisms-repelling composition according to claim 9, further comprising a polyether-modified polydimethylsiloxane having a hydrophile-lipophile balance (HLB) of 2 to 12.

Description

EXAMPLE 1

[0020] Preparation of Each Compound

[0021] [AF-149]

[0022] Each compound was synthesized according to a method as described in the literature: Synthesis, 2011, No. 20, pp 3225-3234.

[0023] [AF-153]

[0024] 4-Aminophenol (25 g) was suspended in ethyl formate (250 mL), to which p-toluenesulfonic acid monohydrate (4.36 g) was then added, and the mixture was heated to reflux for 24 hours, followed by distilling off the solvent under reduced pressure to provide an N-(4-hydroxyphenyl)formamide mixture (A) (32 g). 18 g of (A) was dissolved in DMF (250 mL), to which potassium carbonate (36 g) and 2-bromoethyl acetate (33 g) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=1/1) to provide 2-(4-formamidophenoxy) ethyl acetate (14 g). 2-(4-Formamidophenoxy) ethyl acetate (14 g) was dissolved in methylene chloride (100 mL), to which triethylamine (100 mL) was then added, followed by adding phenyl dichlorophosphate (16 g) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=10/1) to provide 2-(4-isocyanophenoxy) ethyl acetate [AF-153] (9.2 g).

[0025] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.29 (2H, d, J=8.1 Hz), 6.85 (2H, d, J=8.1 Hz), 4.46-4.40 (4H, m), 2.04 (3H, s)

[0026] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 170.1, 162.7 (br), 159.3, 127.5, 119.4 (t, J=12.4 Hz), 114.9, 66.7, 64.0

[0027] [AF-154]

[0028] (A) (18 g) was dissolved in DMF (250 mL), to which potassium carbonate (36 g) and 1-bromohexane (32.5 g) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=3/1) to provide N-(4-(hexyloxy)phenyl)formamide (21.5 g). N-(4-(Hexyloxy)phenyl)formamide (15 g) was dissolved in methylene chloride (100 mL), to which triethylamine (100 mL) was then added, followed by adding phenyl dichlorophosphate (17 g) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-(hexyloxy)-4-isocyanobenzene [AF-154] (10 g).

[0029] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.29 (2H, d, J=8.1 Hz), 6.85 (2H, d, J=8.1 Hz), 3.95 (2H, t, J=6.6 Hz), 1.78 (2H, quint, J=6.6 Hz), 1.50-1.33 (6H, m), 0.89 (3H, t, J=6.6 Hz)

[0030] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.4, 159.4, 127.6, 119.1 (t, J=12.4 Hz), 114.9, 68.3, 31.7, 29.2, 25.6, 22.7, 14.1

[0031] [AF-155]

[0032] (A) (15 g) was dissolved in DMF (200 mL), to which potassium carbonate (30 g) and 1-bromo-3-methylbutane (25 g) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=3/1) to provide N-(4-(isopentyloxy)phenyl)formamide (19 g). N-(4-(Isopentyloxy)phenyl)formamide (15 g) was dissolved in methylene chloride (100 mL), to which trimethylamine (100 mL) was then added, followed by adding phenyl dichlorophosphate (18 g) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-(isopentyloxy)benzene [AF-155] (11.2 g).

[0033] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.29 (2H, d, J=8.1 Hz), 6.85 (2H, d, J=8.1 Hz), 3.98 (211, t, J=6.6 Hz), 1.82 (1H, septet, J=6.6 Hz), 1.68 (1H, q, J=6.6 Hz), 0.96 (6H, d, J=6.6 Hz)

[0034] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.5, 159.4, 127.5, 119.1 (t, J=12.4 Hz), 114.9, 66.7, 37.6, 24.9, 22.4

[0035] [AF-158]

[0036] (A) (12 g) was dissolved in DMF (180 mL), to which potassium carbonate (24 g) and citronellyl chloride (18 g) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=3/1) to provide N-(4((3,7-dimethyl-6-octen-1-yl) oxy) phenylformamide (14.5 g). N-(4((3,7-Dimethyl-6-octen-1-yl) oxy) phenylformamide (14 g) was dissolved in methylene chloride (100 mL), to which triethylamine (100 mL) was then added, followed by adding phenyl dichlorophosphate (12.8 g) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-((3,7-dimethyl-6-octen-1-yl)oxy)-4-isocyanobenzene [AF-158] (10

[0037] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.29 (2H, d, J=8.1 Hz), 6.85 (2H, d, J=8.1 Hz), 5.21-5.19 (1H, m), 3.97 (2H, t, J=6.6 Hz), 1.96-1.92 (2H, m), 1.82 (3H, s), 1.70 (3H, s), 1.66-1.36 (5H, m), 0.95 (3H, d, J=6.6 Hz)

[0038] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.5, 159.4, 131.3, 127.5, 124.7, 119.1 (t, J=12.4 Hz), 114.9, 66.2, 38.1, 37.4, 30.8, 24.6, 24.4, 21.1, 18.5

[0039] [AF-159]

[0040] (A) (20 g) was dissolved in DMF (230 mL), to which potassium carbonate (40 g) and 1-bromo-3-methyl-2-butene (34 g) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=3/1) to provide N-(4-((3-methyl-2-buten-1yl)oxy)phenyl)formamide (13.3 g). N-(4((3-Methyl-2-buten-1-yl)oxy)phenyl)formamide (13 g) was dissolved in methylene chloride (100 mL), to which triethylamine (100 mL) was then added, followed by adding phenyl dichlorophosphate (16.4 g) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.

[0041] The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-((3-methyl-2-buten-1-yl)oxy)benzene [AF-159] (10 g).

[0042] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.16 (2H, d, J=8.1 Hz), 6.78 (2H, d, J=8.1 Hz), 5.41-5.37 (1H, m), 4.70-4.66 (2H, m), 1.82 (3H, s), 1.70 (3H, s)

[0043] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.5, 159.4, 138.4, 127.9, 119.8 (t, J=12.4 Hz), 119.6, 114.6, 65.7, 24.6, 18.6

[0044] [AF-169]

[0045] (A) (16 g) was dissolved in DMF (250 mL), to which potassium carbonate (35 g) and (2-bromoethyl)benzene (25 g) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=3/1) to provide N-(4-phenetoxyphenyl)formamide (20 g). N(4-(Hexyloxy)phenyl)formamide (13.8 g) was dissolved in methylene chloride (100 mL), to which triethylamine (100 mL) was then added, followed by adding phenyl dichlorophosphate (14.4 g) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-phenetoxybenzene [AF-169] (11 g).

[0046] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.35-7.23 (7H, m), 6.85 (2H, d, J=8.1 Hz), 4.17 (2H, t, J=6.6 Hz), 3.10 (2H, t, J=6.6 Hz)

[0047] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.7, 158.9, 158.3, 129.5, 127.7, 121.2, 119.6 (t, J=12.4 Hz), 115.2, 114.6, 66.8, 66.1

[0048] [AF-170]

[0049] (A) (15 g) was dissolved in DMF (200 mL), to which potassium carbonate (30 g) and 1-bromoctane (24.8 g) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=3/1) to provide N-(4-(octyloxy)phenyl)formamide (20 g). N-(4(Hexyloxy)phenyl)formamide (15 g) was dissolved in methylene chloride (100 mL), to which triethylamine (100 mL) was then added, followed by adding phenyl dichlorophosphate (16.5 g) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-(octyloxy) benzene [AF-170] (10.8 g).

[0050] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.29 (2H, d, J=8.1 Hz), 6.85 (2H, d, J=8.1 Hz), 3.95 (2H, t, J=6.6 Hz), 1.78 (1H, quint, J=6.6 Hz), 1.50-1.30 (10H, m), 0.89 (3H, t, J=6.6 Hz)

[0051] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.4, 159.4, 127.6, 119.1 (t, J=12.4 Hz), 114.9, 68.3, 31.7, 29.2, 29.1, 29.0, 25.8, 22.5, 14.0

[0052] AF-173

[0053] (A) (26.9 g) was dissolved in DMF (250 mL), to which potassium carbonate (52 g) and 1-bromononane (25 mL) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=1/1) to provide N-(4-(nonyloxy)phenyl)formamide (26.1 g). N-(4(Hexyloxy)phenyl)formamide (26.1 g) was dissolved in tetrahydrofuran (250 mL), to which triethylamine (42 mL) was then added, followed by adding phenyl dichlorophosphate (20 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-(nonyloxy) benzene [AF-173] (15.7 g).

[0054] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.28 (2H, d, J=8.1 Hz), 6.84 (2H, d, J=8.1 Hz), 3.94 (2H, t, J=6.6 Hz), 1.77 (2H, quint, J=6.6 Hz), 1.47-1.15 (12H, m), 0.87 (3H, t, J=6.6 Hz)

[0055] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.9, 159.5, 127.7, 119.3 (t, J=12.4 Hz), 114.8, 68.5, 31.9, 29.6, 29.4, 29.3, 29.1, 26.0, 22.7, 14.2

[0056] AF-174

[0057] (A) (21.2 g) was dissolved in DMF (250 mL), to which potassium carbonate (43 g) and 1-bromoundecane (21 mL) were then added, followed by stirring the mixture at 60 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=1/1) to provide N-(4-(undecyloxy)phenyl)formamide (18.3 g). N-(4-(Undecyloxy)phenyl)formamide (18.3 g) was dissolved in tetrahydrofuran (250 mL), to which triethylamine (25 mL) was then added, followed by adding phenyl dichlorophosphate (12 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-(undecyloxy)benzene [AF-174] (12.4 g).

[0058] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.30 (2H, d, J=8.1 Hz), 6.84 (2H, d, J=8.1 Hz), 3.94 (2H, t, J=6.6 Hz), 1.77 (2H, quint, J=6.6 Hz), 1.48-1.18 (16H, m), 0.87 (3H, t, J=6.6 Hz)

[0059] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.9, 159.6, 127.7, 119.3 (t, J=12.4 Hz), 115.1, 68.5, 32.0, 29.72, 29.70, 29.65, 29.5, 29.4, 29.2, 26.2, 22.8, 14.2

[0060] AF-175

[0061] (A) (11.2 g) was dissolved in DMF (250 mL), to which potassium carbonate (16.7 g) and 11-bromo-1-undecene (20.7 g) were then added, followed by stirring the mixture at 80 C. for 18 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=1/1) to provide N-(4-(10-undecenyloxy)phenyl)formamide (11.9 g). N-(4-(10-Undecenyloxy)phenyl)formamide (11.9 g) was dissolved in tetrahydrofuran (100 mL), to which triethylamine (18 mL) was then added, followed by adding phenyl dichlorophosphate (8.3 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-(10-undecenyloxy)benzene [AF-175] (7.5 g).

[0062] 1H-NMR (600 MHz, CDCl3, TMS) : 7.30 (2H, d, J=8.1 Hz), 6.85 (2H, d, J=8.1 Hz), 5.85-5.78 (1H, m), 5.01-4.98 (1H, m), 4.94-4.92 (1H, m), 3.95 (2H, t, J=6.6 Hz), 2.04 (2H, q, J=7.3 Hz), 1.77 (2H, quint, J=6.6 Hz), 1.48-1.18 (16H, m), 0.87 (3H, t, J=6.6 Hz)

[0063] 13C-NMR (150.8 MHz, CDCl3, TMS) : 162.6, 159.5, 139.2, 127.7, 119.3 (t, J=12.4 Hz), 115.1, 114.2, 68.5, 33.8, 29.5, 29.4, 29.2, 29.1, 29.0, 26.0

[0064] AF-176

[0065] Aminophenol (25 g) was suspended in ethyl formate (350 mL), to which p-toluene sulfonic acid monohydrate (4.35 g) was then added, and the mixture was heated to reflux for 24 hours, followed by distilling off the solvent under reduced pressure to provide an N(2-hydroxyphenyl)formamide mixture (B) (46.2 g). (B) (46.2 g) was dissolved in DMF (250 mL), to which potassium carbonate (48 g) and 1-bromoctane (58 mL) were then added, followed by stirring the mixture at 80 C. for 22 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by recrystallization (hexane/ethyl acetate) to provide N-(2-(octyloxy)phenyl)formamide (34.7 g). N-(2-(Hexyloxy)phenyl)formamide (17.9 g) was dissolved in tetrahydrofuran (100 mL), to which triethylamine (30 mL) was then added, followed by adding phenyl dichlorophosphate (14 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-2-(octyloxy)benzene [AF-176] (11.4 g).

[0066] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.33-7.28 (2H, m), 6.93-6.87 (2H, m), 4.04 (2H, t, J=6.6 Hz), 1.80-1.82 (2H, m), 1.49 (1H, quint, J=6.6 Hz), 0.39-1.23 (8H, m), 0.88 (3H, t, J=6.6 Hz)

[0067] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 167.2, 154.7, 130.4, 127.7, 120.3 (t, J=12.4 Hz), 116.5, 112.8, 69.1, 31.9, 29.4, 29.3, 29.1, 26.0, 22.7, 14.2

[0068] AF-177

[0069] 3-Aminophenol (25 g) was suspended in ethyl formate (250 mL), to which p-toluene sulfonic acid monohydrate (4.37 g) was then added, and the mixture was heated to reflux for 24 hours, followed by distilling off the solvent under reduced pressure to provide an N(3-hydroxyphenyl)formamide mixture (C) (38.8 g). (C) (38.8 g) was dissolved in DMF (300 mL), to which potassium carbonate (50 g) and 1-bromoctane (73 mL) were then added, followed by stirring the mixture at 80 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by recrystallization (hexane/ethyl acetate) to provide N-(3(octyloxy)phenyl)formamide 23.6 g). N-(3-(Hexyloxy)phenyl)formamide (17.9 g) was dissolved in tetrahydrofuran (150 mL), to which triethylamine (40 mL) was then added, followed by adding phenyl dichlorophosphate (18 mL) under cooling in an ice bath and stirring the mixture for 3 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-3-(octyloxy) benzene [AF-176] (13.2 g).

[0070] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.28-7.23 (1H, m), 6.94-6.90 (2H, m), 6.87-6.86 (1H, m), 3.93 (2H, t, J=6.6 Hz), 1.79-1.74 (2H, m), 1.43 (1H, quint, J=6.6 Hz), 1.36-1.23 (8H, m), 0.88 (3H, t, J=6.6 Hz)

[0071] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 164.1, 159.7, 130.2, 127.4, 118.4 (t, J=12.4 Hz), 116.1, 112.4, 68.5, 31.9, 29.4, 29.3, 29.1, 26.1, 22.8, 14.2

[0072] AF-178

[0073] (A) (11.2 g) was dissolved in DMF (100 mL), to which potassium carbonate (22.6 g), -chloro-p-xylene (12.9 mL), and tetrabutylammonium iodide (530 mg) were then added, followed by stirring the mixture at 80 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=1/1) to provide N-(4-((4-methylbenzyl)oxy)phenyl)formamide (10.7 g). N(4-((4-Methylbenzyl)oxy) phenyl)formamide (13.7 g) was dissolved in tetrahydrofuran (200 mL), to which triethylamine (24 mL) was then added, followed by adding phenyl dichlorophosphate (10 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-((4methylbenzyl)oxy)benzene [AF-178] (9.8 g).

[0074] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.31-7.27 (4H, m), 7.20 (2H, d, J=8.2 Hz), 6.92 (2H, d, J=8.9 Hz), 5.02 (2H, s), 2.36 (3H, s)

[0075] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.5, 158.9, 138.1, 132.8, 129.3, 127.7, 127.5, 119.5 (t, J=12.4 Hz), 115.3, 70.2, 21.2

[0076] AF-179

[0077] (A) (13.7 g) was dissolved in DMF (100 mL), to which potassium carbonate (27.6 g), 4-chlorostyrene (16.9 mL), and tetrabutylammonium iodide (370 mg) were then added, followed by stirring the mixture at 80 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by recrystallization (hexane/ethyl acetate) to provide N-(4-((4vinylbenzyl)oxy) phenyl)formamide (18.3 g). N-(4-((4Vinylbenzyl)oxy)phenyl)formamide (18.3 g) was dissolved in tetrahydrofuran (200 mL), to which triethylamine (30 mL) was then added, followed by adding phenyl dichlorophosphate (14 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-isocyano-4-((4vinylbenzyl)oxy)benzene [AF-179] (13.1 g).

[0078] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.43 (2H, d, J=8.2 Hz), 7.36 (2H, d, J=8.2 Hz), 7.30 (2H, d, J=8.9 Hz), 6.93 (2H, d, J=8.9 Hz), 6.72 (1H, dd, J=17.9, 11.0 Hz), 5.77 (1H, d, J=17.9 Hz), 5.27 (1H, d, J=17.9, 11.0 Hz), 5.06 (2H, s)

[0079] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.6, 158.9, 137.6, 136.2, 135.4, 127.6, 127.6, 126.5, 119.7 (t, J=12.4 Hz), 115.5, 114.4, 70.1

[0080] AF-180

[0081] (A) (16.3 g) was dissolved in DMF (100 mL), to which potassium carbonate (33.8 g), 4-chlorobenzyl chloride (16.9 mL), and tetrabutylammonium iodide (450 mg) were then added, followed by stirring the mixture at 80 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by recrystallization (hexane/ethyl acetate) to provide N-(4-((4chlorobenzyl)oxy)phenyl)formamide (27.0 g). N-(4-((4Chlorobenzyl)oxy)phenyl)formamide (14.0 g) was dissolved in tetrahydrofuran (200 mL), to which triethylamine (22.4 mL) was then added, followed by adding phenyl dichlorophosphate (10.4 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-chloro-4-((4isocyanophenoxy)methyl)benzene [AF-180] (12 g).

[0082] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.36 (2H, d, J=8.9 Hz), 7.34 (2H, d, J=8.9 Hz), 7.30 (2H, d, J=8.9 Hz), 6.92 (21-1, d, J=8.9 Hz), 5.03 (2H, s)

[0083] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.7, 158.7, 134.4, 134.1, 128.9, 128.7, 127.8, 119.8 (t, J=12.4 Hz), 115.4, 69.5

[0084] AF-181

[0085] (A) (11.0 g) was dissolved in DMF (100 mL), to which potassium carbonate (22.1 g), 4-bromobenzyl bromide (24.0 g), and tetrabutylammonium iodide (300 mg) were then added, followed by stirring the mixture at 80 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by recrystallization (hexane/ethyl acetate) to provide N-(4-((4bromobenzyl)oxy)phenyl)formamide (15.9 g). N-(4-((4Bromobenzyl)oxy) phenyl)formamide (5.14 g) was dissolved in tetrahydrofuran (200 mL), to which triethylamine (7.0 mL) was then added, followed by adding phenyl dichlorophosphate (3.3 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide 1-bromo-4-((4isocyanophenoxy)methyl)benzene [AF-181] (3.0 g).

[0086] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.52 (2H, d, J=8.9 Hz), 7.31 (2H, d, J=8.9 Hz), 7.28 (2H, d, J=8.9 Hz), 6.91 (2H, d, J=8.9 Hz), 5.02 (2H, s)

[0087] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.7, 158.6, 135.0, 131.8, 129.0, 127.8, 122.2, 119.9 (t, J=12.4 Hz), 115.4, 69.5

[0088] A-182

[0089] (A) (13.8 g) was dissolved in acetonitrile (200 mL), to which potassium carbonate (27.6 g), methyl (4-chloromethyl)benzoate (22.3 g), and tetrabutylammonium iodide (395 mg) were then added, followed by stirring the mixture at 80 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by recrystallization (hexane/ethyl acetate) to provide methyl 4-(4formamidophenoxy)methyl)benzoate (27.4 g). Methyl 4-(4formamidophenoxy) methyl) benzoate (6.9 g) was dissolved in dichloromethane (200 mL), to which triethylamine (10.0 mL) was then added, followed by adding phosphorus oxychloride (3.0 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (hexane/ethyl acetate=20/1) to provide methyl 4-((4isocyanophenoxy)methyl)benzoate [AF-182] (3.5 g).

[0090] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 8.06 (2H, d, J=8.2 Hz), 7.48 (2H, d, J=8.2 Hz), 7.31 (2H, d, J=8.9 Hz), 6.93 (2H, d, J=8.9 Hz), 5.14 (2H, s), 3.93 (3H, s)

[0091] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 166.6, 162.9, 158.6, 141.1, 130.0, 129.9, 127.8, 126.9, 120.0 (t, J=12.4 Hz), 115.4, 69.6, 52.2

[0092] AF-183

[0093] (A) (2.75 g) was dissolved in acetonitrile (30 mL), to which potassium carbonate (5.52 g), 4-methoxybenzyl chloride (3.25 mL), and tetrabutylammonium iodide (73.8 mg) were then added, followed by stirring the mixture at 80 C. for 48 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure to provide N-(4-((4methoxybenzyl)oxy)phenyl)formamide (6.9 g). N-(4-((4Methoxybenzyl)oxy)phenyl)formamide (6.9 g) was dissolved in dichloromethane (200 mL), to which triethylamine (10.0 mL) was then added, followed by adding phosphorus oxychloride (3.0 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (methylene chloride 100%) to provide 1-isocyano-4-((4methoxybenzyl)oxy)benzene [AF-183] (600 mg).

[0094] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 7.33 (2H, d, J=8.9 Hz), 7.30 (2H, d, J=8.9 Hz), 6.92 (2H, d, J=8.9 Hz), 6.91 (2H, d, J=8.9 Hz), 4.99 (2H, s), 3.82 (3H, s)

[0095] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 162.5, 159.6, 159.0, 129.2, 127.9, 127.7, 119.6 (t, J=12.4 Hz), 115.4, 114.1, 70.1, 55.3

[0096] AF-184

[0097] (A) (13.7 g) was dissolved in acetonitrile (200 mL), to which potassium carbonate (27.9 g), 4-nitrobenzyl bromide (21.7 g), and tetrabutylammonium iodide (405 mg) were then added, followed by stirring the mixture at 80 C. for 24 hours. After adding water to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline and then dried using anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by recrystallization (hexane/ethyl acetate) to provide N-(4-((4nitrobenzyl)oxy)phenyl)formamide (22.6 g). N-(4-((4Nitrobenzyl)oxy)phenyl)formamide (22.6 g) was dissolved in tetrahydrofuran (200 mL), to which triethylamine (34.7 mL) was then added, followed by adding phenyl dichlorophosphate (16.1 mL) under cooling in an ice bath and stirring the mixture for 2 hours while returning to room temperature. Water was added to the reaction solution under cooling in an ice bath, which was then extracted with ethyl acetate. The organic layer was washed with 3M hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution, and saturated saline and then dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography (methylene chloride 100%) to provide 1-isocyano-4-((4nitrobenzyl)oxy)benzene [AF-184] (2.9 g).

[0098] .sup.1H-NMR (600 MHz, CDCl.sub.3, TMS) : 8.26 (2H, d, J=8.9 Hz), 7.59 (2H, d, J=8.9 Hz), 7.34 (2H, d, J=8.9 Hz), 6.94 (2H, d, J=8.9 Hz), 5.18 (2H, s)

[0099] .sup.13C-NMR (150.8 MHz, CDCl.sub.3, TMS) : 163.1, 158.2, 147.7, 143.3, 128.0, 127.6, 123.9, 120.3 (t, J=12.4 Hz), 115.4, 68.9

[0100] AF-024

[0101] AF-024 was synthesized according to the method of the patent literature (Japanese Patent Laid-Open No. 2002-370907).

[0102] AF-035

[0103] AF-035 was synthesized according to the method of the patent literature (Japanese Patent Laid-Open No. 2002-370907).

[0104] AF-034

[0105] AF-034 was synthesized according to the method of the patent literature (Japanese Patent Laid-Open No. 2002-370907).

[0106] AF-048

[0107] AF-048 was synthesized according to the method of a literature (BIOFOULING, 2004, Vol. 20, No. 2, pp 93-100).

EXAMPLE 2

[0108]

TABLE-US-00001 TABLE 1 Compound Number Structural Formula CAS Number 024 [00008] 356533-74-9 149 [00009] 1245736-13-3 153 [00010] None 154 [00011] 178864-63-6 155 [00012] None 158 [00013] None 159 [00014] None 169 [00015] None 170 [00016] 178864-64-7 173 [00017] None 174 [00018] None 175 [00019] None 176 [00020] None 177 [00021] None 178 [00022] None 179 [00023] None 180 [00024] None 181 [00025] None 182 [00026] None 183 [00027] None 184 [00028] None 035 [00029] 479075-78-0 034 [00030] 341534-99-4 048 [00031] 479075-67-7

[0109] Among the above compounds, AF-024, AF-034, AF-035, and AF-048 are reported to have concentrations corresponding to the 50% adhesion inhibition rate to Barnacle (EC.sub.50) of 0.054, 0.0084, 0.03, and 0.019 g/ml, respectively. The EC.sub.50s of the remaining compounds are still not known. AF-034, AF-035, and AF-048 were used as comparative examples for describing effects in actual ocean tests since they had lower EC.sub.50 values than that of AF-024. As clear from the following Examples, AF-024 exhibited an especially excellent repelling effect compared to AF-034, AF-035, and AF-048.

[0110] Test with Fishing Net

[0111] The compositions shown in the following tables were each dipapplied to a polyethylene knotless net (6 knots, 400 deniers, 60 strings) and air-dried, which was then fixed to a 35 cm45 cm iron frame and dipped and held at 3 m below the level of sea in a raft in the inner section of Ochiishi Bay in Nemuro City, Hokkaido from Apr. 14, 2015 to Dec. 15, 2015.

TABLE-US-00002 TABLE 2 Example 1 2 3 4 5 6 7 8 9 10 11 AF-024 5 AF-178 5 AF-179 5 AF-180 5 AF-181 5 AF-182 5 AF-183 5 AF-184 5 AF-153 5 AF-154 5 AF-155 5 AF-158 AF-159 AF-169 AF-170 AF-173 AF-174 AF-175 AF-176 AF-177 AF-149 AF-034 AF-035 AF-048 Silicone Oil 3 3 3 3 3 3 3 3 3 3 3 KF-6020 1 Acrylic Resin 30 30 30 30 30 30 30 30 30 30 30 (60% Xylene) 2 Polybutene OH 3 5 5 5 5 5 5 5 5 5 5 5 Xylene 57 57 57 57 57 57 57 57 57 57 57 Total (Parts by Weight) 100 100 100 100 100 100 100 100 100 100 100 Example Comparative Example 12 13 14 15 16 17 18 19 20 21 1 2 3 4 AF-024 AF-178 AF-179 AF-180 AF-181 AF-182 AF-183 AF-184 AF-153 AF-154 AF-155 AF-158 5 AF-159 5 AF-169 5 AF-170 5 AF-173 5 AF-174 5 AF-175 5 AF-176 5 AF-177 5 AF-149 5 AF-034 5 AF-035 5 AF-048 5 Silicone Oil 3 3 3 3 3 3 3 3 3 3 3 3 3 3 KF-6020 1 Acrylic Resin 30 30 30 30 30 30 30 30 30 30 30 30 30 30 (60% Xylene) 2 Polybutene OH 3 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Xylene 57 57 57 57 57 57 57 57 57 57 57 57 57 62 Total (Parts by Weight) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Notes 1 Silicone Oil KF-6020 (Trade Name): Polyether-modified Polydimethylsiloxane (HBL = 4), manufactured by Shin-Etsu Chemical Co., Ltd. 2 Acrylic Resin: Isobutylmethacrylate-Butylacrylate Copolymer, Tg = 20 C. 3 Polybutene 0H (Trade Name): manufactured by Idemitsu Kosan Co., Ltd.

[0112] Test Result

TABLE-US-00003 TABLE 3 Adhesion Situations of Organisms Hydrozoa Shellfish Algae Example 1 S S A Example 2 S A A Example 3 S A A Example 4 S B A Example 5 S A A Example 6 S A A Example 7 S A B Example 8 S A B Example 9 A A A Example 10 A B A Example 11 A A B Example 12 A A A Example 13 A A B Example 14 A B A Example 15 S A A Example 16 A B A Example 17 A B A Example 18 A A B Example 19 S A A Example 20 S A A Example 21 A B A Comparative Example 1 E D D Comparative Example 2 E C D Comparative Example 3 E C D Comparative Example 4 E D D Notes S: No Adhesion A: Minimal Adhesion B: Slight Adhesion C: Slightly More Adhesion D: Considerably More Adhesion E: Extremely More Adhesion

[0113] The compositions shown in the following tables were each applied to a 10 cm 30 cm test plate before drying and dipped and held at 1.5 m below the level of sea in a raft in the inner section of Kigatsu Bay in Hirado City, Nagasaki Prefecture from Mar. 24, 2015 to Apr. 26, 2016.

TABLE-US-00004 TABLE 4 Example 1 2 3 4 5 6 7 8 9 10 11 AF-024 10 AF-178 10 AF-179 10 AF-180 10 AF-181 10 AF-182 10 AF-183 10 AF-184 10 AF-153 10 AF-154 10 AF-155 10 AF-158 AF-159 AF-169 AF-170 AF-173 AF-174 AF-175 AF-176 AF-177 AF-149 AF-034 AF-035 AF-048 Silicone Oil 7 7 7 7 7 7 7 7 7 7 7 KF-6020 1 Acrylic Resin 58 58 58 58 58 58 58 58 58 58 58 (60% Xylene) 2 Polybutene OH 3 10 10 10 10 10 10 10 10 10 10 10 Xylene 15 15 15 15 15 15 15 15 15 15 15 Total (Parts by Weight) 100 100 100 100 100 100 100 100 100 100 100 Example Comparative Example 12 13 14 15 16 17 18 19 20 21 1 2 3 4 AF-024 AF-178 AF-179 AF-180 AF-181 AF-182 AF-183 AF-184 AF-153 AF-154 AF-155 AF-158 10 AF-159 10 AF-169 10 AF-170 10 AF-173 10 AF-174 10 AF-175 10 AF-176 10 AF-177 10 AF-149 10 AF-034 10 AF-035 10 AF-048 10 Silicone Oil 7 7 7 7 7 7 7 7 7 7 7 7 7 7 KF-6020 1 Acrylic Resin 58 58 58 58 58 58 58 58 58 58 58 58 58 58 (60% Xylene) 2 Polybutene OH 3 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Xylene 15 15 15 15 15 15 15 15 15 15 15 15 15 25 Total (Parts by Weight) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Notes 1 Silicone Oil KF-6020 (Trade Name): Polyether-modified Polydimethylsiloxane (HBL = 4), manufactured by Shin-Etsu Chemical Co., Ltd. 2 Acrylic Resin: Isobutylmethacrylate, Tg = 48 C 3 Polybutene 0H (Trade Name): manufactured by Idemitsu Kosan Co., Ltd.

[0114] Test Result

TABLE-US-00005 TABLE 5 Adhesion Situations of Organisms Hydrozoa Shellfish Algae Example 1 S S A Example 2 S A B Example 3 S B B Example 4 S B B Example 5 S B B Example 6 S B A Example 7 S A B Example 8 S B B Example 9 A B B Example 10 A B B Example 11 S A B Example 12 A B B Example 13 S B B Example 14 S B A Example 15 S A A Example 16 A B B Example 17 A B B Example 18 A B B Example 19 S A A Example 20 S A A Example 21 A B B Comparative Example 1 E D C Comparative Example 2 E D D Comparative Example 3 E C D Comparative Example 4 E D D Notes S: No Adhesion A: Minimal Adhesion B: Slight Adhesion C: Slightly More Adhesion D: Considerably More Adhesion E: Extremely More Adhesion

[0115] Test with Fishing Net

[0116] The compositions shown in the following tables were each dipapplied to a polyethylene knotless net (6 knots, 400 deniers, 60 strings) and air-dried, which was then fixed to a 35 cm45 cm iron frame and dipped and held at 3 m below the level of sea in a raft in a fishing port in front of Minami Kayabe Fishery Association, Usujiri-cho, Hakodate City, Hokkaido from May 28, 2015 to Sep. 8, 2015.

TABLE-US-00006 TABLE 6 Example Comparative Example 1 2 1 2 3 4 Non-treatment AF-024 5 5 5 AF-170 5 5 5 Silicone Oil 3 3 KF-6020 1 Silicone Oil 3 3 KF-354L 2 Silicone Oil 3 3 KF-96 3 Acrylic Resin 30 30 30 30 30 30 (60% Xylene) 4 Polybutene OH 5 5 5 5 5 5 5 Xylene 57 57 57 57 57 57 Total (Parts by Weight) 100 100 100 100 100 100 Notes 1 Silicone Oil KF-6020 (Trade Name): Polyether-modified Polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., HBL = 4 2 Silicone Oil KF-354L (Trade Name): Polyether-modified Polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., HBL = 16 3 Silicone Oil KF-96 (Trade Name): Dimethylsilicone Oil, manufactured by Shin-Etsu Chemical Co., Ltd., HBL = 0 4 Acrylic Resin: Isobutylmethacrylate-Butylacrylate Copolymer, Tg = 20 C. 5 Polybutene 0H (Trade Name): manufactured by Idemitsu Kosan Co., Ltd.

[0117] Test Result

TABLE-US-00007 TABLE 7 Adhesion Situations of Organisms Hydrozoa Shellfish Algae Example 1 S S A Example 2 S A A Comparative Example 1 B A B Comparative Example 2 B B B Comparative Example 3 B B B Comparative Example 4 B B B Non-treatment E E E Notes S: No Adhesion A: Minimal Adhesion B: Slight Adhesion C: Slightly More Adhesion D: Considerably More Adhesion E: Extremely More Adhesion

INDUSTRIAL APPLICABILITY

[0118] The present invention can be used for repelling marine sessile organisms.