KR100791630B1 - Environmental friendly pollution-proof agents - Google Patents

Abstract

The present invention relates to an environmentally friendly antifouling agent, and more specifically, by confirming that the octadecane derivative has excellent antifouling performance, the production cost is lower than that of existing antifouling substances, and toxic antifouling agents such as the organic tin, copper, and mercury compounds. It relates to an environmentally friendly antifouling agent that can effectively prevent the pollution of the marine environment caused by the use of the agent.

Antifouling agent, octadecane derivative

Description

Environmental friendly pollution-proof agents

The present invention relates to an environmentally friendly antifouling agent, and more particularly, as one or two selected from 1-octadecane and 5-ethyl octadecane as an octadecane derivative, it is confirmed that the antifouling performance is superior to conventional antifouling substances. The present invention relates to an environmentally friendly antifouling agent having low production cost and effectively preventing pollution of the marine environment caused by the use of toxic antifouling agents such as organotin, copper and mercury compounds.

The antifouling agent is mixed with paints and exerts its function in order to prevent marine attachment organisms (microorganisms and animals and plants) from growing on the surface of the ship.The term "engraftment" refers to the growth and attachment of benthic organisms to artificial objects. Say.

Undersea, many sea creatures such as reef shell, shellfish, moss, diatom, oyster, pearl clam, sponge, seashell, beetle, green seaweed and sea squirrel are inhabited. Parasitic attachment to fishing nets causes damage to the deposits. In particular, when marine life is attached to the bottom of a ship, the hull surface becomes rough and needs to be repaired frequently. When the hull surface becomes 0.01 mm rough, the fuel consumption increases by 0.3 ~ 1.0%, which increases the fuel consumption burden. In the case of large ships, fuel costs account for almost 50% of the ship's operating costs, so the problem of adhesion on the bottom of the ship is not serious.

In order to solve this problem, tributyl tin (hereinafter referred to as TBT) has been used as an antifouling agent, but TBT has been found to adversely affect the marine environment. By adopting a risk resolution on organic tin under the regulation of marine antifouling systems by the MEPC, which prevents safe operation and marine pollution, the use of TBT, which was used as antifouling agent from January 1, 2003, is banned. Since 2008, regulations have been enacted that ships should be completely removed from TBT.

The non-tin antifouling agent currently being used is copper oxide or zinc as disclosed in Korean Patent Laid-Open No. 2001-0099049, and technically, the non-tin antifouling agent has an antifouling effect against green algae. Insufficient problems and anti-oxidant copper oxide anti-fouling agents are also expected to be regulated in 2008 as they can accumulate in the ocean's poor quality and adversely affect the environment.

For the purpose of preventing marine biological contamination of aquatic buildings, antifouling coating compositions in which the above antifouling agents and vinyl chloride resins or vinyl resins are mixed with rosin and plasticizers have been used, but such antifouling coating compositions are used as antifouling agents. Contaminated copper, mercury, and organotin compounds caused problems that contaminated the marine environment. In addition, U.S. Patent No. 4,191,579 and U.S. Patent No. 1,457,590 disclose self-polishing antifouling which enables hydrolysis by seawater by combining an organotin component such as tributyltin oxide in an ester form to an unsaturated monomer such as acrylic acid or methacrylic acid. Antifouling systems using coating compositions are described. In other words, the antifouling coating composition described in the patent has a new surface layer as the organic tin component is gradually hydrolyzed at the contact portion with seawater and is released, and the carboxyl group at the leaving site forms a salt so that the polymer is solubilized or swelled and released from the surface. As a protruding system, it is the most widely used antifouling system, but organic tin component, which has non-target toxicity, is continuously eluted to cause marine pollution and the ecosystem impact is very serious.

Therefore, while it is excellent in the pollution prevention effect on marine life and microorganisms, there is a demand for the development of environment-friendly antifouling agent without environmental hygiene problems.

Accordingly, the present inventors have studied to solve the above problems, as a result, one or two selected from the octadecane derivatives 1-octadecane and 5-ethyl octadecane material is known to have an excellent antifouling effect antifouling containing the same The present invention was completed by developing the agent.

Accordingly, it is an object of the present invention to provide an environmentally friendly antifouling agent that exhibits excellent antifouling effect against various marine attachment organisms without harming the marine environment and the human body.

In addition, another object of the present invention is to provide an antifouling paint that can replace organic tin, copper, mercury compounds which are marine pollutants as marine antifouling paints for fishing nets, ships, and marine structures.

The present invention is characterized by an antifouling agent containing one or two selected from 1-octadecane and 5-ethyl octadecane as an active ingredient.

In addition, the present invention is an antifouling paint comprising one or two selected from 1-octadecane and 5-ethyl octadecane as an antifouling material in an antifouling paint composed of a resin, a solvent, a pigment, other additives, and an antifouling material. Is another feature.

Hereinafter, the present invention will be described in more detail.

According to the present invention, one or two selected from the octadecane derivatives, 1-octadecane and 5-ethyl octadecane, have excellent antifouling performance, and thus, the production cost is lower than that of conventional antifouling substances. It relates to an environmentally friendly antifouling agent which can effectively prevent the pollution of the marine environment caused by the use of toxic antifouling agents such as mercury compounds.

It was confirmed that one or two selected from 1-octadecane and 5-ethyl octadecane materials according to the present invention exhibited excellent antifouling effect against thorny blue and brownish blue marine organisms without harming the marine environment and human body. It is characterized by an antifouling agent containing one or two selected from 1-octadecane and 5-ethyl octadecane as an active ingredient. An antifouling agent means one or two or more selected from 1-octadecane and 5-ethyl octadecane.

In addition, the marine antifouling paint according to the present invention contains 3 to 40% by weight of one or two selected from 1-octadecane and 5-ethyl octadecane, and is mixed uniformly with other components in the antifouling paint. In consideration of handleability, ease of manufacture, and long-term maintenance aspects of the antifouling performance, the content is more preferably 10 to 30% by weight.

As resin used for the antifouling paint for underwater use of this invention, all resin normally used for antifouling paint can be used. In particular, examples of the resin that can be used in the antifouling paint of the present invention include vinyl resins such as vinyl acetate resin and vinyl chloride resin, urethane resins, chlorinated rubber resins, phthalic acid resins, alkyd resins, epoxy resins, phenol resins, melanin resins, Natural resins, such as synthetic resins, such as an acrylic resin, a fluororesin, and a silicone resin, or rosin, can also be used, In addition to such synthetic or natural resins, various water-soluble resins or fat-soluble resins can also be used together. The amount of the resin is preferably 3 to 20% by weight based on the total coating composition, and if the amount of the resin is less than 3% by weight, there is a problem that the adhesion of the antifouling paint is poor. A problem occurs.

As a solvent used in the marine antifouling paint of the present invention, it is preferable to use 20 to 40% by weight of a hydrocarbon-based, ketone solvent and cellulsolve acetate such as xylene, methyl ethyl ketone and methyl isobutyl ketone. . If the amount of the solvent used is less than 20% by weight, a problem arises in that the viscosity becomes too high. If the amount of the solvent is used in excess of 40% by weight, problems with adhesion to the coating film and antifouling properties occur.

A mixed antifouling agent containing one or two or more selected from 1-octadecane and 5-ethyl octadecane as an antifouling agent is 3 to 40 wt% based on the total paint composition. Preference is given to using. If it is less than 3% by weight, the antifouling performance is lowered, coating problems occur, and if more than 40% by weight, the physical properties of the paint is bad, a problem that is difficult to long-term storage.

As the booster used in the marine antifouling paint of the present invention, it is preferable to use 1 to 7% by weight of one or more selected from zinc pyrithione, cappyrithione and polyhexamethyleneguanidine phosphate based on the total coating composition. If the amount of the booster is less than 1% by weight, a problem occurs that the synergistic effect on the antifouling agent is lowered, and when the amount of the booster exceeds 7% by weight, a storage stability problem of the paint occurs.

As the pigment used in the antifouling paint composition of the present invention, various pigments known in the art may be widely used, and for example, metal oxides such as titanium oxide, iron oxide, zinc oxide, and organic pigments may be used alone or in combination. have. The pigment is preferably used 20 to 50% by weight based on the total coating composition, if the amount of the pigment used is less than 20% by weight, there is a problem of discoloration, if more than 50% by weight has a disadvantage of poor weather resistance .

Marine antifouling paint composition according to the invention may comprise a variety of known additives. As the additive, a general thickener such as polyamide wax, bentonite, polyethylene wax, etc. may be exemplified, and the amount of the additive is preferably 1 to 5 wt% based on the total coating composition. If the amount of the thickener is less than 1% by weight, there is a problem of poor work during coating, and when the amount of the thickener is greater than 5% by weight, the viscosity becomes excessively high.

Marine antifouling paint of the present invention is produced by a conventional paint production method. For example, the resin is completely dissolved in xylene and some ketone solvents, then boosters and pigments are added and dispersed into a sand mill, followed by 1-octadecane (1- octadecane, 5-ethyl octadecane, mixed antifouling agent containing one or two or more selected from them, and other additives were added, stirred with a high speed dissolver, and the remaining solvent was added. The antifouling paint of the present invention is prepared by stirring.

Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

Experimental Example 1: Inhibitory activity test of spore motility of pomegranate seeds

Spore motility inhibitory activity was conducted on 1-octadecane and 5-ethyl octadecane. Each sample showed potent inhibitory activity (++++) on the motility of green spores at concentrations of 4,000, 2,000, 1,000, 500, 250, and 125 μg [Table 1].

* Remarks:

a) The inhibitory effect on each antifouling agent shows the effect on the motility inhibitory response to the motility of the control group.

b) The degree of effect on the motility inhibitory response is expressed as follows.

(Very strong reaction: ++++, 100%; strong reaction: +++, 95-75%; moderate reaction: ++, 75-50%; mild reaction: +, 50-25%; no reaction:- , 25-0%)

Test Example 2: Inhibition Effect of Spore Adhesion by Hole Shredding: ADM Test

Agar gel 2% (Bacto agar) was added to distilled water and used as a coating of spore motility inhibitors. Candidate antifouling substances were mixed on the prepared agar gel at a ratio of 100 ㎍ / mL, 10 ㎍ / mL and 1 ㎍ / mL, respectively, and then evenly spread on a slide glass (2cm * 4cm) washed with 100% methanol and distilled water for 1 hour. After drying, the dried spores were fixed vertically in a coplin jar containing spores, and then stored at room temperature for 10 hours in a condition where the spores could grow. The bioassay slide glass was washed with distilled water to remove unattached spores, and then assayed at a microscope X100 magnification. A strong inhibition result was shown in the adhesion inhibition test [Table 2].

Examples 1 to 5 and Comparative Examples 1 to 4: Preparation of antifouling paint

Dissolve the vinyl resin and rosin completely in xylene and some methyl isobutyl ketone, then add booster, zinc oxide and iron oxide, disperse twice using Sand Mill, and then dissolve 1-octane in the dispersed mixture. By adding decane and 5-ethyl octadecane and a thickener, the mixture was stirred at 3500 rpm for 60 minutes with a High Speed Dissolver, and the remaining ketone solvent was added and stirred to prepare an antifouling paint having the composition shown in Table 3 below. It was.

Test Example 3

The antifouling performance of the antifouling paints prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was measured by the following method. Using a rolled steel sheet of KSD 3501 having a width × length × 100 × 100 × 3.2 mm, three sandblasted specimens were prepared according to the KSM 5569 method and coated with tar vinyl resin. The antifouling coating paints of Examples and Comparative Examples were sprayed three times so as to have a dry thickness of 150 µm. After drying for one week at a relative humidity of 75%, 25 ℃, was deposited in a 2m depth area in the East Sea to check the antifouling state after 12 months. The contamination area within the effective area of 10,000 mm ² was rounded off in the 5% range with three arithmetic averages and is shown in Table 4 below.

As can be seen from Table 4, as the antifouling agent substance used as an antifouling paint containing one or two selected from 1-octadecane, 5-ethyl octadecane (5-ethyl octadecane) The invention was found that the antifouling performance is equivalent to or more than the control group using the conventional antifouling agent organotin compound.

As described above, one or two selected from 1-octadecane and 5-ethyl octadecane as antifouling agents according to the present invention are completely harmless to the marine environment and the human body. It exhibits excellent antifouling effect against seaweeds and barnacles such as spiny and perforated marine organisms, which are marine organisms, and replaces organic tin or mercury compounds, which are marine pollutants, and marine antifouling for fishing nets, ships, and marine structures. It is useful as an agent or antifouling paint.

Claims (9)

An environmentally friendly antifouling agent comprising octadecane derivative of 1-octadecane or 5-ethyl octadecane as an active ingredient. In antifouling paints composed of resins, solvents, pigments, other additives and antifouling substances, the antifouling substances may be octadecane derivatives of 1-octadecane or 5-ethyl octadecane. Marine antifouling paint characterized by the above-mentioned. The antifouling paint for marine use according to claim 2, wherein the resin content is 3 to 20% by weight. The antifouling paint for underwater use according to claim 2, wherein the solvent content is 20 to 40% by weight. The antifouling paint for marine use according to claim 2, wherein the pigment content is 20 to 50% by weight. The antifouling paint for marine, characterized in that 3 to 40% by weight of the antifouling material. The method of claim 2, wherein one or two or more selected from zinc pyrithione, cappyrithione, and polyhexamethyleneguanidine phosphate are added as a booster for improving antifouling performance. Antifouling paint. The antifouling paint for marine use according to claim 2, wherein the content of the other additives is 1 to 5% by weight. The antifouling paint for marine use according to claim 8, wherein the other additive is at least one thickener selected from polyamide wax, bentonite and polyethylene wax.