JPH01266180A - Antifouling agent for aquatic organism - Google Patents

Abstract

PURPOSE:To provide the title agent which is safe and exhibits a high antifouling effect in a low dosage, which comprises a particular naphthoquinone derivative as an active ingredient. CONSTITUTION:This antifouling agent for aquatic organisms comprises a naphthoquinone derivative of the formula as an active ingredient. In the formula R<1>, R<2>, R<3> and R<4> are each H, an alkyl, or a halogen atom except for the case where R<3> and R<4> are both H and R<1> and R<2> are both alkyl, or one of R<1> and R<2> is alkyl and the other is H. Examples of the naphthoquinone derivative of the formula include 2,6-dichloro-5,8,4a,8a-tetrahydro-1,4-naphthoquinone and 2-methyl-3,7-dichloro-5,8,4a,8a-tetrahydro-1,4-naphthoquinone. The naphtoquinone of the formula is incorporated in a paint forming agent to prepare an antifouling paint, and the paint may be applied to the bottom of a ship, an underwater structure, the wall of an inlet channel for cooling water, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an aquatic biological antifouling agent containing a naphthoquinone derivative as an active ingredient.

(Prior art) Undersea equipment such as the bottom of a ship, fishing nets, and buoys, dam accessory equipment, underwater structures such as bridge piers, and thermal power plants 1
Parts that are in constant contact with water, such as the cooling water intake channels of heat exchangers in the petrochemical industry, are exposed to fujibo, oysters, mussels, hydrobugs, serpura, bryozoans, sea squirts, bulrushes, and sea lettuce.

Shellfish and algae, such as blue laver and seaweed, propagate, and these attached organisms cause undesirable conditions such as increased fluid resistance, decreased thermal conductivity, etc., and reduced equipment functionality.

Conventionally, various antifouling agents have been used to prevent the adhesion and propagation of such seawater and freshwater harmful organisms. Cuprous oxide, organic tin compounds, and the like have been known as active ingredients of such antifouling agents (see Japanese Patent Publication No. 34-15526) and are still widely used. These active ingredients are contained in the paint in an amount of 10 to 50% and are eluted in seawater to prevent attachment of harmful organisms.

(Problems to be solved by the invention) Recently, however, heavy metals and harmful elements have caused social problems such as contamination of environments such as rivers and seawater, and even harm to the human body through fish. The use of organic tin compounds and the like in antifouling agents is now being advised.

(Means for solving the problem) Until now, the present inventors have developed a non-metallic organic compound other than organotin compounds that is safe and has a high antifouling effect at a low dose. As a result of intensive research to develop naphthoquinone derivatives, it was surprisingly found that aquatic animal substances,
The present invention was completed based on the discovery that it has an excellent repellent effect against plant substances.

That is, the present invention relates to the general formula (where R1, R2, R3 and R4 represent a hydrogen atom, an alkyl group or a halogen atom. However, R3 and R
4 are both hydrogen atoms, and R1 and R2 are both alkyl groups or one is an alkyl group and the other is a hydrogen atom, except when R1 and R2 are both alkyl groups or one is an alkyl group and the other is a hydrogen atom. This is an aquatic biological antifouling agent characterized by containing a naphthoquinone derivative shown in ) as an active ingredient.

Specific examples of the naphthoquinone derivative represented by the general formula (I), which is an active ingredient of the present invention, include the following compounds. In addition, compound no.

are referenced in the following description.

Compound NO,1; 2,6-dichloro-5,8,4a,8
a -Tetrahydro-1,4-naphthoquinone compound NO,2i2,7-dichloro-5,8,4a,8
a -Tetrahydro-1,4-naphthoquinone compound NO,3; 2,3.6-1-dichloro5+8.4
a+88-Tetrahydro-1,4-naphthoquinone compound NO,4; 2-methyl-3,7-dichloro-5,8,
4a, 8a-tetrahydro-1,4-naphthoquinone compound NO,5; 2. 7.4a -) dichloro-5,
8,8a-trihydro-1,4-naphthoquinone compound NO,6; 6-chloro-5,8,4a, 8a
-Tetrahydro-1,4-naphthoquinone compound No. 7; 2. 6.8a -Trichloro-5,8,4a.

-Trihydro-1,4-naphthoquinone compound NO, 8; 2. 7.8a -trichloro-5
, 8, 4a.

-trihydro-1,4-naphthoquinone etc. and its tautomer 1,4-dihydroxy-
Examples include 5,8-dihydronaphthalene derivatives.

Naphtoki represented by the general formula (1) of the present invention (in the formula R
A p-benzoquinone derivative represented by 1, R4 has the same meaning as above, and 2-halobutadiene represented by the general formula % (wherein, X represents a halogen atom) in a solvent. Alternatively, it can be synthesized by reacting without a solvent according to a conventional method. Examples of the solvent used at this time include aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, ether solvents such as ether, tetrahydrofuran, and dioxane, and mixed solvents thereof.The reaction temperature ranges from room temperature to 150°C. The reaction proceeds smoothly.

The naphthoquinone derivative represented by formula (1) of the present invention is useful as an aquatic biological antifouling agent.

In addition, the aquatic biological antifouling agent of the present invention containing the naphthoquinone derivative represented by the general formula (1) as an active ingredient may be one or two of naphthoquinone derivatives and 1,4-dihydroxynaphthalene derivatives, which are tautomers thereof. Mixtures of more than one species are prepared and used in the form of paints, solvents, emulsions, etc. For example, when used as a paint, the naphthoquinone derivative represented by the general formula (1) can be mixed with a paint forming agent to prepare an antifouling paint, and this can be applied to the bottom of a ship, underwater structures, and walls of cooling water intake channels. can. Examples of the coating film forming agent used in this case include Aburesu 9, Synthetic Resin, and Artificial Rubber. Pigments and extender pigments can be added to the antifouling paint as desired.

In this case, the amount of the compound of the present invention is 1 to 20% based on the total weight of the paint.
%, preferably 2 to 10%. For the purpose of preventing the adhesion and propagation of aquatic organisms in the cooling water intake channel, the naphthoquinone derivative shown in the above-mentioned - Shipman may be added into the intake channel in the form of a solution or emulsion. but,
In order to maintain the antifouling effect for a long period of time, it is preferable to apply it in the form of a paint.

(Effect of the invention) According to the aquatic biological antifouling agent containing the naphthoquinone derivative of the present invention as an active ingredient, it is possible to safely maintain high antifouling effects for a long period of time with a low content without using an organic tin compound. can.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Test Examples 1 to 5 (Algae Growth Inhibition Test) Using the algae collected from the sea as the test algae, 5 g of it was atomized in a mortar, diluted with 11n+1 seawater, and filtered using gauze. When filtered seawater was observed under a microscope, large numbers of Aonori spores were seen moving. 19 ml of seawater containing the spores was transferred to a Petri dish with a diameter of 5 cm and used as a sample.

50 mg of the compound of the present invention was made into a 1 g emulsion with an emulsion containing cyclohexanone and Tween-80 (trade name, manufactured by Atlas Powder Co., Ltd.) in a ratio of 10:1, diluted with seawater to a predetermined concentration, and 1 ml of the emulsion was prepared as described above. was added to a petri dish containing seawater containing nori spores. The petri dish was left standing in a constant temperature room at 20°C, and after 1 hour, the contents II were transferred to a slide glass, and the presence or absence of spore movement was examined under a microscope.

The test was repeated three times to determine the growth-inhibiting concentration of A. aonori. The results are shown in Table 1.

In addition, rAJ of compound No. in the table is 2.6-dichloro-1
,4-dihydroxy-5,8-dihydronaphthalene (tautomer of compound No. 1), and rBJ is 2,7-dichloro-1,4-dihydroxy-5,8-dihydronaphthalene (tautomer of compound No. 1). represents the gender body).

Table 1 Formulation Example 1 (Preparation of ?'8 liquid) Using the naphthoquinone derivative shown in Saito (1) above, the mixture was blended in the following proportions and sufficiently ground and mixed in a bot mill to prepare a solution. .

-Seaman (1) compound 10% by weight Rosin ww 13% by weight Tocopaflax A40 1
Weight% xylene 76% by weight *Toyoparafukusu 840; Chlorinated paraffin, Toyo Soda■
Preparation Example 2 manufactured by Seiko Co., Ltd. Using the naphthoquinone derivative shown in Shipin (1) above, an antifouling paint was prepared by blending the naphthoquinone derivative in the following proportions and thoroughly mixing in a ball mill.

Compound of general formula (1) 5% by weight 10% by weight
20% by weight Zinc white 20% by weight CR-1012% by weight Plasticizer 2% by weight Xylene 31% by weight *CR-10; Chlorinated rubber resin (manufactured by Asahi Denka ■) Patent applicant Wasaku Central Research Institute

Claims (1)

[Claims] 1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (In the formula, R^1, R^2, R^3 and R^4 represent a hydrogen atom, an alkyl group or a halogen atom. However, R^
3 and R^4 are both hydrogen atoms, and R^1 and R
Except when ^2 are both alkyl groups or one is an alkyl group and the other is a hydrogen atom. ) An aquatic biological antifouling agent characterized by containing a naphthoquinone derivative represented by the following as an active ingredient.