KR20060017992A - Environmental-friendly anti pollution agent from mustard leaf - Google Patents

Abstract

The present invention relates to an environmentally friendly antifouling agent containing a substance extracted from mustard leaf, which is a natural substance, and contains allyl isothiocyanate, which is harmless to the environment by the present invention, and is protected against a wide range of target organisms. Since it has a potency and is extracted from natural products, it is possible to obtain an inexpensive antifouling agent, thereby effectively preventing the pollution of the marine environment caused by the use of toxic antifouling agents such as TBT.

Mustard leaf, allyl isothiocyanate, antifouling agent, eco-friendly

Description

Environment-friendly anti pollution agent from mustard leaf             

1 is a profile of ¹³ C NMR spectrum of allyl isothiocyanate,

Figure 2 is a profile of the ¹ H NMR spectrum of allyl isothiocyanate.

The present invention relates to an environmentally friendly antifouling agent, and more particularly, to an environmentally friendly antifouling agent containing a material extracted from mustard leaf (Mustard) which is a natural substance.

Antifouling material refers to a material mixed with paint to prevent marine adherents (microorganisms and plants) from growing on the surface of the ship. The engraftment refers to the growth and attachment of benthic organisms to artificial objects. When benthic organisms adhere to the surface of a ship, economic losses occur due to the increase of frictional force, slowing the ship, promoting corrosion, and increasing fuel use.

If the bottom of the ship is exposed to seawater for 6 months, the amount of attached organisms is about 150kg / m ² In large ships, it has been reported that the friction force increases by 0.3-1.0% for every 0.01mm roughness due to the attachment of the living organisms to the hull surface, and the speed decreases by 50% due to the increase of the friction force. Done.

To solve this problem, tributyl tin (hereinafter referred to as "TBT") has been used as an antifouling agent, but TBT has been found to have an adverse effect on the marine environment. The use of TBT, which has been used as an antifouling agent since January 1, 2003, has been adopted by the Marine Environment Protection Committee (MEPC), which is responsible for the safe operation of IMO) and the prevention of marine pollution, by adopting a risk resolution on organic tin under the regulation of marine antifouling systems. It has been banned entirely, and from 2008 onwards, regulations have been enacted that ships should be completely removed from TBT.

Non-tin antifouling agents currently being used are copper oxide or zinc as disclosed in Korean Patent Laid-Open No. 2001-0099049, and technically, non-tin antifouling paints have insufficient antifouling effect against green seaweed. It is also expected that the use of nitrous oxide antifouling agent will be banned between 2006 and 2008 because it will accumulate in the ocean and adversely affect the environment. Therefore, it is urgent to develop an antifouling agent which is excellent in antifouling effects and environmentally friendly. It is true.

The present invention has been made to solve the above problems, and an object thereof is to provide an antifouling agent that is harmless to the environment. Another object of the present invention is to provide an antifouling agent having an antifouling effect against a wide range of target organisms. Another object of the present invention is to provide an antifouling agent having a low production cost.

The antifouling agent of the present invention contains allyl isothiocyanate, which is a substance separated from a mustard leaf, which is a natural substance.

Hereinafter, the present invention will be described in detail.

The present inventors tested the antifouling ability against various kinds of seaweeds and land plants to develop antifouling agents that are harmless to the environment. Seaweeds were classified into species that dwelled in intertidal zones in the east and south coasts of Korea, and species collected by submerging, crushed and crushed with a crusher. Powder samples were stored in glass bottles and used when necessary. Terrestrial plants were extracted from the terrestrial plants inhabiting the whole country through literature information, which could be classified as secondary metabolites with antifouling ability, and then classified and crushed with a crusher.

The anti-adhesion effect of the extract on adherent seaweeds was carried out using spores of thorny seaweed and perforated brown seaweed, which are typical sticky seaweeds, and the mustard leaf extract of various seaweeds and terrestrial plants showed excellent antifouling properties.

The inventors have found out that allyl isothiocyanate is an antifouling substance from mustard leaf extract having excellent antifouling properties through various experiments.

Embodiments of the present invention are as follows.

(Example 1)

Sampling and Extraction

The mustard leaves (Vaccinium corymbosum) used in this experiment were collected from Pyeongchang, Gangwon-do to remove this material, washed and dried. In order to increase the extraction yield was pulverized using a grinder to make a powder was used as an experimental material. The collected land plants were shaded and ground to make powder of 1 kg of lemon each. 1 kg of sample powder was added to 10 l of methanol, stored for 24 h, extracted, and only the supernatant was collected and combined three times. After evaporating methanol at 1/10 using a vacuum condenser at 37 ° C, the mixture was removed and filtered through a 0.22 μm filter. It was used for the experiment while storing at -20 ℃.

(Example 2)

Fraction

Silica gel (70-230 mesh) was filled under hexane, and a glass tube column (10 cm ㅧ 90 cm, PTEE end plate attached) was selected according to the amount of the sample, and the amount of silica gel was 50-60 times the amount of the sample. The main developing solvents were [hexane, hexane: ethyl acetate = 95: 5, hexane: ethyl acetate = 90: 10, hexane: ethyl acetate = 85: 15, hexane: ethyl acetate = 80: 20, hexane: ethyl acetate = 70 : 30, Hexane: ethyl acetate = 60: 40, Hexane: ethyl acetate = 50: 50, ethyl acetate, ethyl acetate: methanol = 95: 5, ethyl acetate: methanol = 90: 10, ethyl acetate: methanol = 80: 20] were sequentially collected at a flow rate of 5 ml min-1 (Table 1), and the experiment was conducted on the mustard leaf extract under the same conditions. Thin layer chromatography was carried out under developing solvent conditions and fractionated into six fractions (I-VI).

(Example 3)

* Inhibitory effect of spore motility of hole crab

The anti-adhesion effect of the sample was tested on Ulva pertusa , one of the typical adherent seaweeds. The forked leeks were collected from Gyeongpodae near Gangneung and transported to the laboratory to sort only the forked leeks. After sorting, the ultrasonic treatment was repeated three times for 1 minute to remove adherents, and then washed clean with sterile seawater. After immersion in 1% betadine and 2% trition X-100 mixed solution for 1 minute, the solution was semi-dried after simple sterilization. Semi-dried green seaweed was put in sterile seawater and spore release was induced in an incubator at 80 μmol m ^-2 s ^-1 and 20 ℃

10 μl of dimethyl sulfoxide (DMSO) was added to the prepared tube, and spores released from seawater were added to dilute concentrations of 500, 1000, 1500, 2000, and 4000 μl of spore motility inhibitory effect under microscope (Olympus CK2) at X100 magnification. Assay. If the motility inhibitory effect exceeds 95%, it is '++++'. If the spore motility inhibitory effect is 95% -75%, it is '++++', and if it is 75% -50%, '++' In case of 50% -20%, '+' was indicated, and in case of no motility inhibitory effect, '-' was indicated. Before inoculation at each dilution concentration, the movement state of the spores in seawater was checked and used in comparison with the control group.

Test results for the fraction fraction (I-VI) fractionated by Example 2 showed a strong activity in the III fraction, as shown in Table 2 below.

(Example 4)

* Nuclear Magnetic Resonance

As a result of analysis by hydrogen-nuclear magnetic resonance and carbon-nuclear magnetic resonance for fractional sphere III (FIGS. 1-4), fractional sphere III was found to be allyl isothiocyanate, and the structure thereof is represented by Chemical Formula 1 below.

(Example 5)

* Manufacture of panels

Paints used for panel painting to test antifouling properties include self-polishing copolymers (SPC; self-polishing copolymer, installed in July 2003) and CDP (Controlled Depletion Polymer, 2004 2004). Month) type was used. The self-wearing model consists of Laroflex MP15, Copper Acryl Resin and Sillica, and CDP consists of VAGH and Wood Rosin, and common components include Bentone SD-2, Tricresyl Phosphate, Disperbyk-163, MIBK and Xylene (Table 3). - 4). These paints were mixed with the new antifouling material identified in Example 4 and coated on a panel of PVC material (50 mm X 50 mm X 5 mm). Each anti-fouling material was added with low concentration (0.1 g · mL ⁻¹ ) and high concentration (0.3 g · mL ⁻¹ ), respectively, and stirred using a meat grinder (MOTOR MILL, Hwa sung industrial Co.). Mix for 20 minutes with a disperser.

 * Composition of self-wear paint ingredient Composition ratio (%) Laroflex MP15 8.37 Bentone SD-2 1.13 Tricresyl Phosphate 5.2 Disperbyk-163 4.3 Copper Acryl Resin 14.48 MIBK 33.9 Xylene 23.3 Sillica 9.95

* Composition of CDP type paint ingredient Composition ratio (%) VAGH 35 Bentone SD-2 1.5-1.8 Tricresyl Phosphate 8-9 Disperbyk-163 7 Wood rosin 17.5 MIBK 18 Xylene 12

(Example 6)

* Panel test of new antifouling agent (image analysis)

After installation of the new antifouling agent-coated panels, the images were analyzed using a digital camera at intervals of 30 days for 30, 60, 90, 120, and 150 days. The coloration rate of the panel coated with antifouling agent containing allyl isothiocyanate was 30, 60, 90 days image analysis at low concentration (10%) and the control (commercial antifouling agent using TBT as antifouling material). (Painted panels), anti-adhesion effect, and 120, 150 days image analysis showed 14 to 18% more adherent organisms than control, 30, 60, 90, 120 days image at high concentration (30%) As a result of the analysis, it showed the same anti-adhesion effect as the control group, and 150 days of image analysis showed a 5% increase in adherent organisms than the control group.

* Antifouling test result  Antifouling substances Day (%) 30 60 90 120 150 Low Concentration (10%) Allyl isothiocyanate 0 0 0 2 6 High Concentration (30%) Allyl isothiocyanate 0 0 0 0 5  Commercially available antifouling paint Waterways 0 0 0 0 0 Epifanes 0 0 0 0 0 Interspeed 0 0 0 0 0 Cruiser 0 0 0 0 0

The present invention is harmless to the environment, has antifouling ability against a wide range of target organisms, and since it is extracted from natural products, it is possible to obtain an inexpensive antifouling agent, thereby effectively preventing the pollution of the marine environment caused by the use of toxic antifouling agents such as TBT. can do.

Claims (1)

Eco-friendly antifouling agent derived from mustard leaf containing allyl isothiocyanate.

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