JPH03287507A - Fouling organism-controlling agent and anti-fouling paint composition - Google Patents

Abstract

PURPOSE:To provide the subject fouling organism-controlling agent and the subject anti-fouling paint composition containing a catechin as the active component, having a strong effect for control of fouling organisms for submarine buildings, etc., in a low concentration, capable of ready decomposition in the natural world and free from persistence and toxicity. CONSTITUTION:A fouling organism-controlling agent containing a catechin contained in various plants such as acacia, cherry and tea and readily available at a low cost, e.g. an optically active compound of formulae I-V, its dimer, trimer or polymer as the active component and capable of prevention of damage due to adhesion and progress of insect pests to a submarine or industrial water supply or water discharge system, the inner or outer walls of a land building, the wall of a bath room, etc., without a bad influence on the ecological system or on a working atmosphere because of the above-mentioned effects. In addition, if the above-mentioned controlling agent is blended in an amount of 0.5-50wt.%, preferably 1-30wt.%, an anti-fouling paint composition showing a strong anti- fouling effect over one year or more is obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to the prevention and treatment of harmful organisms on the walls of seawater or industrial supply and drainage systems, and on the interior and exterior walls of land structures, bathrooms, etc.
The present invention relates to a fouling biological control agent and a fouling prevention coating composition for the purpose of preventing damage caused by breeding. In other words, damage caused by fouling organisms on the surfaces of ships, marine construction, facilities, fishing nets, buoys, seawater conduit pipes, and other underwater structures, as well as decreased functionality due to slime adhesion in paper manufacturing processes, industrial cooling water systems, circulating main cooling systems, etc. The present invention provides a fouling organism control agent and a fouling prevention paint composition that prevent damage such as deterioration of water quality due to the proliferation of microorganisms, as well as adhering microorganisms that breed on the inside and outside walls of land structures, walls of bathrooms, etc. be.

[Prior art] Undersea structures (e.g., ships, marine structures, coastal plants), aqueous humor conduits, fishing nets, breeding rafts, buoys, etc. are covered with large attached animals and plants such as barnacles, mussels, sea squirts, and sea lettuce, as well as diatoms and bacteria. Microorganisms such as these adhere to ships, causing damage such as corrosion of structures, increased seawater frictional resistance of ships, large numbers of fish and shellfish dying due to clogging of eddy nets, sedimentation due to increased weight, and reduced work efficiency. In addition, industrial water systems such as cooling water that use natural water such as river water or lake water, and circulating cooling systems that use medium or tap water often contain bacteria,
Diatoms, blue-green algae, blue-green algae, etc. breed abnormally, resulting in deterioration of water quality, decreased cooling efficiency due to adhesion to vessel walls, and blockage of wood pipes.
This causes problems such as reduced flow rate. Furthermore, the interior and exterior walls of land structures, bathrooms, etc. are contaminated by the proliferation of various algae and microorganisms.

Conventionally, methods for preventing damage caused by such fouling organisms include using chemicals such as inorganic heavy metal compounds, organic metal compounds, heavy metal salts, organic phosphorus agents, non-411 agents, and organic halogen agents.

For example, antifouling paints have traditionally been applied to the bottom of ships, the walls of seawater inlets, fishing nets, etc. The antifouling paints contain agents such as inorganic copper compounds and organic tin compounds as antifouling agents. is mainly used.

In addition, in a cooling water system, agents such as organic metal agents, organic phosphorus agents, inorganic and organic halogen agents, and peroxides are added to the water system either directly or in the form of a solution or dispersion in combination with a hydrating agent. On the other hand, the same chemicals as above are used for the interior and exterior walls of land structures and bathrooms.

However, antifouling using these agents often does not show sufficient effects at low concentrations of elution and dissolution. Furthermore, at effective concentrations, the drug is highly toxic and persistent;
In recent years, it has become a problem, especially from the viewpoint of environmental health and pollution.

Problems to be Solved by Invention C] There is a need for a fouling organism control agent that has low toxicity and persistence, and does not have an adverse effect on the ecosystem or working environment. It is an object of the present invention to provide antifouling agents and antifouling coating compositions.

[Means and effects for solving the problems] The above object is achieved by a fouling organism control agent and a fouling prevention coating composition, which are characterized by containing catechins as an active ingredient.

That is, the catechins according to the present invention refer to the following.

H Also includes dimers or trimers of the above catechins and their polymers (catechol type tannins).

These catechins are found in many plants such as acacia, cherry blossoms, and tea, and are thought to be the parent substance of many tannins.

The catechins according to the present invention can be produced by extracting them from plants containing these catechins. That is, catechins extracted from plants containing catechins with an organic solvent such as methanol, ethanol, ethyl acetate, acetone, etc., water, or a mixture of the organic solvent and water in any proportion are used without particular limitation. I can do it.

Furthermore, when using plants containing particularly large amounts of catechins, such as acacia, cherry blossoms, and tea, as raw materials, plant powder obtained by pulverizing the leaves of these plants using a pulverizer can also be used without particular limitation.

These plants such as tea and their extracts do not contain any environmental pollutants, and unlike conventional drugs, the resulting antifouling active substances are highly degradable in nature and are not persistent.
Toxicity is not an issue at all. Furthermore, it has a strong control effect even at extremely low concentrations against microorganisms and large sessile organisms that cause fouling. Therefore, the amount of elution, dissolution or dispersion of the pesticidal agent according to the present invention into water or water droplets is extremely small to achieve sufficient effects.

When using the antifouling agent according to the present invention as an antifouling paint or an antifouling agent for fishing nets, one of the antifouling agents according to the present invention may be used as an antifouling agent for fishing nets.
0.5 species or a combination of two or more species in the paint composition
By containing up to 50% by weight, preferably 1 to 30% by weight, a strong antifouling effect can be exhibited for more than one year. In this case, the paint compositions that can be selected may be those conventionally used, such as vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, etc. as the resin vehicle. Resins, polyester resins, silicone resins, silicone rubber resins, waxes, paraffins, and rosin esters are used. Furthermore, although it is not essential for the antifouling function, it is also possible to incorporate a known antifouling agent as an auxiliary agent for antifouling activity. In addition, commonly used plasticizers, coloring pigments, extender pigments, solvents, etc. can be contained in arbitrary proportions. Further, in the production of paints, it can be adjusted by methods known per se in the field of paint manufacturing technology. The same effect can be expected on the interior and exterior walls of land structures and the walls of bathrooms.

On the other hand, when the fouling organism control agent according to the present invention is dissolved or dispersed in a cooling water system or the like and used, one type or a combination of two or more thereof is added to the water system. The amount added to the water system is 0.1 to 500 ppm as the active ingredient.
A very strong pesticidal effect can be achieved at a low concentration, preferably 1.0 to 300 ppm. As for the method of adding it to an aqueous system, it may be directly dissolved in the aqueous system, but after dispersing and dissolving it in an arbitrary hydrating agent such as an ionic surfactant, a nonionic surfactant, a water-soluble organic solvent, etc. You can also put it in. Also, the input may be continuous or intermittent. It can be arbitrarily selected depending on the water system and the occurrence of pests.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereby. That is,
Catechins can be obtained from any leaves or branches of plants that contain them, and they can be obtained easily and inexpensively.

[Example] <Manufacture of pest control agent> 500 m of 50% aqueous ethanol per 100 g of Niacassia leaves
After adding J and grinding, the mixture was heated and extracted under reflux for 3 hours.

After cooling, it was filtered, and the filtrate was concentrated under reduced pressure to obtain 7.4 g of extract.

50 g of leaves and 150 g of branches and stems of the cherry blossom tree were crushed, 500 mj of water was added thereto, and the mixture was heated and extracted under reflux for 3 hours. After cooling, filter and concentrate the furnace liquid under reduced pressure.・10.2
An extract of g was obtained.

500 mj) of 20% aqueous acetone was added to 100 g of Wataru Mihoyu bancha powder, and extraction was performed under heating and reflux for 3 hours. After volatilizing the acetone under reduced pressure, chloroform is added, and after removing chloroform-soluble materials, the aqueous layer is separated. Ethyl acetate was added to the aqueous layer for extraction, and the ethyl acetate layer was separated. The ethyl acetate layer was concentrated under reduced pressure and dried to obtain 12.0 g of crude catechins.

Tea powder (containing 15% crude catechins) was prepared in place of the above extract. Here, the term "tea powder" refers to a product obtained by pulverizing green tea using a pulverizer and collecting 50 to 500 mesh powder.

<Effect when adding a pesticidal agent to a water system> The pesticidal effect was investigated in an experimental waterway in which 300g of turbid water was introduced per hour into a waterway with a total length of 20m and a cross-sectional area of 0.1m2.

Extracts or tea powders obtained in Examples 1 to 4 above 100 to 5
A test solution prepared by dissolving or suspending 00g in Ikg of dimethyl sulfoxide and combining it with 'Ig of seawater is dripped at the waterway entrance for 8 hours every day. 20 days after the start of the exam
The effect was investigated on the second day. The effectiveness was investigated using adhesive boards (hard vinyl chloride boards, 100mm x 3) installed at 51 locations in the waterway.
The wet weight of the organisms attached to the test tube (00 mm x 3.2 am) was measured for 20 days, and a system to which no test liquid was added was used as a control for comparison. The results are shown in Table 1. The adhesion plates were installed as follows: A: Immediately below the test water drop (channel entrance) B: 5 m from the channel entrance C: 10 m from the channel entrance D: 15 m from the channel entrance E: 20 m from the channel entrance ( The test plate was completely immersed in water at each location (outlet of the waterway).

Slime and small mussels were observed in the control plot, but only slime was observed in the other experimental plots.

(Left below) <Effects of insecticides added to paints> Test example for seawater constructs of Roasted & Saramameji Prepare each in a ball mill 16
An antifouling test was conducted on the antifouling paint and the comparative paint using time dispersion. In the antifouling test, the antifouling paints and comparative paints shown in Table 2 were applied to a 50 x 15 mm test steel plate, which had been previously coated with a commercially available antifouling paint, so that the dry film thickness was 60 to 80μ. After drying in the sun, the test diameter was immersed in the sea at a depth of 1 m, and the degree of contamination by attached organisms was investigated.

Table 3 shows Comparative Example 2 in which the above-mentioned test steel plates with anti-corrosion coating were immersed and investigated at the same time.

From Table 3, it can be seen that the products of the present invention exhibit greater antifouling effects than conventional products, and can maintain this effect for a long period of time.

(Left below) Test examples and mold resistance tests for land structures that died in January (based on JIS Z 2911 ts)
Each extract or tea powder is mixed with a phthalic acid resin varnish so that the nonvolatile component ratio is 0.5% (1.5% for tea powder), and diluted with thinner as appropriate.

This sample is evenly applied to a filter paper with a diameter of 30 mm and thoroughly dried.

A test piece is placed in the center of a peptone plate medium with a petri dish diameter of 90 sam, the following mold spore suspension 1- is sprinkled over the entire surface, and cultured at about 28°C for one week.

・^spergillus niger ATCC62
75・Penicillium citrinum A
TCC9849・C1adosporiu+++he
rbarum IAM, F517・Chaetomiu
m globosum ATCC6205 A test piece prepared without adding the extract as a control and a test piece prepared using tributyltin chloride as a comparison are simultaneously tested.

After one week, mold resistance is indicated according to the following criteria.

(The following is a blank space) [Effects of the Invention] As explained above, the present invention was completed from a completely different perspective from conventional fouling biological control agents and antifouling paint compositions, and it provides strong control at low concentrations. In addition to being effective,
It is highly degradable in nature and has no problems with persistence or toxicity. Therefore, the present invention has extremely high industrial utility value.

Claims (2)

[Claims] (1) A fouling biological control agent characterized by containing catechins as an active ingredient. (2) An antifouling coating composition comprising 0.5 to 50% by weight of the antifouling agent according to claim (1).