JPH0733741A - Liposoluble vitamin c-nicotinamide complex and antifouling agent - Google Patents

Abstract

PURPOSE:To obtain an antifouling agent containing the complex of a liposoluble vitamin C with nicotinamide and exhibiting the antifouling effect and its persistency which have not been achieved by conventional methods. CONSTITUTION:An antifouling agent containing the complex of nicotinamide with a liposoluble vitamin C of the formula (R1 is 1-30C alkyl or alkenyl), e.g. L-ascorbic acid 6-acetate-nicotinic acid amide. The complex is obtained by dissolving the liposoluble vitamin C of the formula and the nicotinamide in amounts of the same moles, respectively, in an alcoholic solvent, stirring the solution at room component, and subsequently filtering out the produced deposits. The antifouling agent can especially advantageously be used for protecting sea water-contacting articles such as fishing nets, marine structures, sea water-conducting pipes, the bottoms of steel ships, wooden ships and reinforced plastic ships, etc., and can furthermore also be applied to the protection of articles liable to receive damages due to fouling organisms because of being utilized in river water, lake water or other waters over long periods.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a complex of fat-soluble vitamin C and nicotinic acid amide and its use as an antifouling agent. This antifouling agent is used to prevent the adhesion of marine organisms such as ships and undersea structures.

[0002]

2. Description of the Related Art Conventionally, organotin compounds have been used as antifouling agents for ships and undersea structures for preventing the adhesion of marine organisms. However, organotin compounds are difficult to use due to toxicity problems. At present, cuprous oxide is used as an antifouling agent as an alternative, but it cannot be said that it has the effect and sustainability of an organotin compound, and cuprous oxide is also a compound containing heavy metals. Therefore, compounds with higher safety and higher efficacy are required. The fact that nicotinic acid amide, which is a highly safe compound, has excellent performance as an antifouling agent for preventing the attachment of marine organisms is disclosed in JP-A-57-53291 and is a known fact. is there. However, nicotinamide
It has a high water solubility, and has a drawback in that, for example, even when it is blended in an antifouling paint, it quickly flows into seawater and the effect cannot be maintained. On the other hand, it is known that nicotinic acid amide and vitamin C form a complex (US Pat. No. 2,433,688). However, the fact that fat-soluble vitamin C and nicotinic acid amide form a complex and an antifouling agent containing the same have not been known at all.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a complex of nicotinic acid amide and vitamin C and a sustained release antifouling agent.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a complex of fat-soluble vitamin C and nicotinic acid amide is formed, and that the coplex releases nicotinic acid amide slowly. As a result, they have completed the present invention. That is, the present invention provides a compound represented by the general formula (1)

[0005]

[Chemical 2] (In the formula, R ₁ represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms.) A complex of fat-soluble vitamin C and nicotinic acid amide, and an antifouling agent containing the same It is provided.

Fat-soluble vitamin C is vitamin C and carbon number 1
To 30 fatty acids having an alkyl group or an alkenyl group can be easily produced by ester synthesis using a commonly used acid catalyst or alkali catalyst. The alkyl group and the alkenyl group have 1 to 30 carbon atoms, and the sustained release property of nicotinamide can be controlled by the number of carbon atoms. Preferably, it has 6 to 25 carbon atoms. Carbon number 5
In the following, the water-solubility is increased and the water easily flows out into seawater, and the antifouling effect tends to be less durable. Carbon number 27
Above, the antifouling effect tends to decrease. The complex of fat-soluble vitamin C and nicotinic acid amide is obtained by dissolving equimolar amounts of fat-soluble vitamin and nicotinic acid amide in an alcohol-based organic solvent, and stirring at room temperature to filter out a precipitate that precipitates. To be It has been confirmed by NMR analysis and elemental analysis that the complex of the present invention is a complex in which a fat-soluble vitamin and nicotinic acid amide are bonded at a ratio of 1: 1. A complex of these fat-soluble vitamins and nicotinic acid amide can be blended with an oil-based or synthetic resin-based vehicle to give the antifouling agent of the present invention. Examples of oil-based or synthetic resin-based vehicles include linseed oil, boiled oil such as hemp oil,
Examples thereof include vinyl-based, alkyd-based, acrylic-based, urethane-based, tar-epoxy-based, epoxy-based, chlorinated rubber-based, synthetic rubber-based, chlorinated polyethylene, and other synthetic resins. Although the antifouling agent of the present invention is used alone as an antifouling active ingredient, it can be used as a main component in combination with other known antifouling effective substances. Further, the antifouling agent of the present invention can be produced by optionally adding other additives such as pigments, dyes, plasticizers and other additives depending on the purpose of implementation, and further adding them to hydrocarbons, hydrogen halides and ketones. It is manufactured by diluting or dissolving it with an organic solvent such as ester. Examples of the method for treating the substrate material which is damaged by the contaminating organism with the antifouling agent of the present invention include, for example, coating, dipping and spraying methods. The amount of the antifouling active ingredient in the antifouling agent of the present invention is selected according to the purpose of antifouling, but it is 1 to 80 in the total solid content.
It may be contained in an amount of, preferably 10% by weight or more. The antifouling agent of the present invention is particularly advantageously used for the protection of objects in contact with seawater such as steel vessels, wooden vessels, ship bottoms of reinforced plastic vessels, fishnets, undersea structures, and seawater introduction pipes.
It can be applied to the protection of objects that are vulnerable to polluted organisms due to the long-term use of river water, lake water and other water.

[0007]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 (L-ascorbic acid 6-acetate-nicotinic acid amide) 1.22 g (0.01 mol) of nicotinic acid amide was dissolved in 50 ml of methanol, and 2.18 g of L-ascorbic acid 6-acetate (0. 01 mol) of 50
A ml methanol solution was added at room temperature. The obtained white precipitate was collected by suction filtration and washed with a small amount of a methanol solution to obtain 2.34 g (yield 68.8%) of a white solid.
When the structure was confirmed by NMR analysis and elemental analysis,
It was confirmed that the fat-soluble vitamin and nicotinic acid amide formed a 1: 1 complex. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0 ppm (1 H, m) 2.3 ppm (3 H, s) Elemental analysis (C14 H16 N2 O8) Calculated value C; 49.41% H; 4.71% N;
8.24% Found C; 49.75% H; 4.73% N;
8.29%

Example 2 (L-ascorbic acid 6-caprylate-nicotinic acid amide) Using 2.74 g of L-ascorbic acid 6-caprylate, 2.9 g of a white solid (yield 7 was obtained in the same manner as in Example 1).
3%) was obtained. When the structure was confirmed by NMR analysis and elemental analysis, fat-soluble vitamin and nicotinic acid amide
It was confirmed that a complex of 1 was formed. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (6H, s)
0.9 ppm (3H, m) Elemental analysis (C18H24N2O8) Calculated value C; 54.55% H; 6.06% N;
7.07% found C; 54.34% H; 6.08% N;
7.05%

Example 3 (L-ascorbic acid 6-heptanate-nicotinic acid amide) Using 2.88 g of L-ascorbic acid 6-heptanate, 3.4 g of white solid was obtained in the same manner as in Example 1 (yield 8
3%) was obtained. When the structure was confirmed by NMR analysis and elemental analysis, fat-soluble vitamin and nicotinic acid amide
It was confirmed that a complex of 1 was formed. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (8H, s)
0.9 ppm (3H, m) Elemental analysis (C19H26N2O8) Calculated value C; 55.61% H; 6.34% N;
6.83% Found C; 55.66% H; 6.35% N;
6.95%

Example 4 (L-ascorbic acid 6-palmitate-nicotinic acid amide) Using 4.14 g of L-ascorbic acid 6-palmitate, 4.9 g of a white solid (yield 9 was obtained in the same manner as in Example 1).
1%) was obtained. When the structure was confirmed by NMR analysis and elemental analysis, fat-soluble vitamin and nicotinic acid amide
It was confirmed that a complex of 1 was formed. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (26H, s)
0.9 ppm (3H, m) Elemental analysis (C28H44N2O8) Calculated value C; 62.69% H; 8.21% N;
5.22% found C; 62.66% H; 8.22% N;
5.23%

Example 5 (L-ascorbic acid 6-stearate-nicotinic acid amide) Using 4.22 g of L-ascorbic acid 6-stearate, 5.1 g of a white solid (yield 9 was obtained in the same manner as in Example 1).
0%). When the structure was confirmed by NMR analysis and elemental analysis, fat-soluble vitamin and nicotinic acid amide
It was confirmed that a complex of 1 was formed. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (30H, s)
0.9 ppm (3H, m) Elemental analysis (C30H48N2O8) Calculated value C; 63.83% H; 8.51% N;
4.96% Found C; 64.00% H; 8.62% N;
4.98%

Example 6 (L-ascorbic acid 6-tricosanate-nicotinic acid amide) Using 5.12 g of L-ascorbic acid 6-tricosanate, 5.4 g of a white solid (yield 85%) was obtained in the same manner as in Example 1. Got When the structure was confirmed by NMR analysis and elemental analysis, it was confirmed that the fat-soluble vitamin and nicotinic acid amide formed a 1: 1 complex. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (40H, s)
0.9ppm (3H, m) Elemental analysis (C35H58N2O8) Calculated value C; 66.25% H; 9.15% N;
4.42% found C; 65.98% H; 9.18% N;
4.40%

Example 7 (L-ascorbic acid 6-hexacosanoate-nicotinic acid amide) 5.8 g of a white solid (yield 86%) was obtained in the same manner as in Example 1 using 5.54 g of L-ascorbic acid 6-hexacosanoate. Got When the structure was confirmed by NMR analysis and elemental analysis, it was confirmed that the fat-soluble vitamin and nicotinic acid amide formed a 1: 1 complex. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (46H, s)
0.9 ppm (3H, m) Elemental analysis (C38H64N2O8) Calculated value C; 67.46% H; 9.47% N;
4.14% Found C; 67.16% H; 9.48% N;
4.12%

Example 8 (L-ascorbic acid 6-octacosanoate-nicotinic acid amide) 6.4 g of white solid (yield 91%) was obtained by the same method as in Example 1 using 5.82 g of L-ascorbic acid 6-octacosanoate. Got When the structure was confirmed by NMR analysis and elemental analysis, it was confirmed that the fat-soluble vitamin and nicotinic acid amide formed a 1: 1 complex. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (50H, s)
0.9 ppm (3H, m) Elemental analysis (C40H68N2O8) Calculated value C; 68.18% H; 9.66% N;
3.98% Found C; 67.98% H; 9.59% N;
3.97%

Example 9 (L-ascorbic acid 6-triacontanate-nicotinic acid amide) L-ascorbic acid 6-triacontanate 6.10 g
In the same manner as in Example 1 except that 6.9 g of a white solid was obtained.
(Yield 94%) was obtained. When the structure was confirmed by NMR analysis and elemental analysis, it was confirmed that the fat-soluble vitamin and nicotinic acid amide formed a 1: 1 complex. NMR analysis (d6-DMSO) chemical shift 8.0-7.6 ppm (4H, m) 5.3
ppm (1H, d) 4.6ppm (1H, s) 4.1ppm (2H, d)
4.0ppm (1H, m) 2.3ppm (2H, t) 1.2ppm (54H, s)
0.9 ppm (3H, m) Elemental analysis (C42H72N2O8) Calculated value C; 68.85% H; 9.84% N;
3.83% found C; 68.58% H; 9.78% N;
3.82%

Example 10 and Comparative Example 1 (Antifouling agent performance test) 1 part of the complexes shown in Table 1 [Table 1] was kneaded into 9 parts of the coating resin to make it uniform. This resin was applied on a plastic plate so as to draw a circle having a radius of 5 cm. This was dipped in a place 1 m below the sea level, and the state of adhesion of marine organisms and the state of slime formation were observed for 3 months. Table 1 shows the evaluation results.
The results are shown in [Table 1]. The same antifouling agent performance test as in Example 10 was conducted using nicotinic acid amide instead of the complex of fat-soluble vitamin C and nicotinic acid amide. The results are shown in Table 1 [Table 1].

[0017]

[Table 1] Table-1 Antifouling agent performance test ──────────────────────────────────── 1 month 2 months 3 months Carbon number Adhesion Slime Adhesion Slime Adhesion Slime ────────────────────────────────────── L- Ascorbic acid -1-+ + +++ ++ 6-acetate L-ascorbic acid -5 ---- + + 6-caprylate L-ascorbic acid-6 ------- 6-heptanate L-ascorbic acid-15 − − − − − − 6-Permitate L-Ascorbic acid-17 − − − − − − − 6-Stearate L-Ascorbic acid-22 − − − − − − − 6-Trichosanate L-Ascorbic acid-25 − − − − − − − 6-Hexacosanoate L-Ascorbic acid − 27 − − + + + + 6-o Tacosanoate L-Ascorbic acid-29 --- +++++ 6-Triacontanate Comparative Example 1 ++++++++++++++ ─────────────────────── ───────────── −: None +: Slightly adhered ++: Significantly adhered

Example 11 and Comparative Example 2 (Solubility Test) 0.1 g of the complexes shown in Table 2 [Table 2] was suspended in 10 g of seawater and stirred for 5 hours, and the concentration of nicotinic acid amide was measured. The concentration was measured by measuring the absorbance at 260 nm with a spectrophotometer. The results are shown in Table 2 [Table 2]. Using nicotinamide instead of the complex of fat-soluble vitamin C and nicotinamide,
The same solubility test as in Example 11 was performed. The results are shown in Table-2.
The results are shown in [Table 2].

[0019]

[Table 2]

[0020]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an antifouling agent having a high effect and a long-lasting effect, which has not been achieved by the prior art. That is, while nicotinic acid amide (Comparative Example 1) had no effect in the antifouling agent performance test, the complexes showed excellent effect. In addition, as shown by the solubility test, it is thought that it exhibits higher durability due to its lower solubility in seawater.

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Claims (2)

[Claims] 1. General formula (1) [Chemical formula 1] (In the formula, R ₁ represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms.) A complex of fat-soluble vitamin C and nicotinic acid amide. 2. A complex of a fat-soluble vitamin C represented by the general formula (1) [Chemical formula 1] (in the formula, R ₁ represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms) and nicotinic acid amide. An antifouling agent containing: