JPH03128302A - Control agent for aquatic injurious organism - Google Patents

Abstract

PURPOSE:To provide the title control agent capable of preventing damages due to the attachment and propagation of injurious organisms in seawater or industrial water system, containing, as active ingredient, specific phenol derivative(s) or its combination with a water-repellent organic compound. CONSTITUTION:The objective control agent containing as active ingredient (A) at least one of phenol derivatives of the formula (R is 3-21C aliphatic saturated hydrocarbon residue; X1-X5 are each H, OH or methoxy, but except the case that all of the X1-X5 are H) [e. g. a compound where R is CH3(CH2)n, X1, X2, X4 and X5 are each H, and X3 is OH] or (B) its combination with a waterrepellent organic compound (in particular, pref. silicone oil, vaseline, petroleum wax, liquid paraffin). The present control agent is optimal for seawater or industrial water system.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an aquatic pest control agent for preventing damage caused by attachment and breeding of pests in seawater or industrial water systems. In other words, damage caused by fouling organisms on the surfaces of underwater structures such as ships, marine structures, fishing nets, buoys, and seawater conduit pipes, as well as reduced functionality due to slime adhesion and bacteria in paper manufacturing processes, industrial cooling water systems, circulating water cooling systems, etc. The purpose of the present invention is to provide an aquatic pest control agent that prevents damage such as deterioration of water quality due to the abnormal proliferation of aquatic organisms.

Conventional technology Fujibbo is used for underwater structures such as ships, offshore structures, seawater conduits for coastal plants, fishing nets, aquaculture rafts, and buoys.
Large attached animals and plants such as mussels and sea lettuce, and microorganisms such as diatoms and bacteria adhere to structures, causing corrosion of structures, increased seawater frictional resistance of ships, large numbers of fish and shellfish dying due to clogging of fishing nets, and settling and work due to increased weight. Damages such as decreased efficiency will occur. In addition, in industrial water systems such as cooling water that uses natural water such as river water and lake water, and in circulation cooling equipment that uses medium and tap water, bacteria, diatoms, orchid rings, etc.
Abnormal growth of blue-green algae causes problems such as deterioration of water quality, decreased cooling efficiency due to adhesion to vessel walls, blockage of water pipes, and decreased flow rate. In addition, slime generated in the paper pulp process used in the paper industry causes a significant deterioration in the quality of paper products.

Conventionally, methods for preventing damage caused by such harmful organisms in water include the use of chemicals such as inorganic heavy metal compounds, organic metal compounds, heavy metal salts, and inorganic 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., and these antifouling paints contain inorganic copper compounds, organic tin compounds, etc. as antifouling agents. drugs are mainly used.

In addition, in a cooling water system, agents such as organic metal agents, inorganic and organic halogen agents, and peroxides are dissolved or dispersed and added to the water system directly or in combination with a wettable powder. Control using these agents often does not show sufficient effects at low concentrations of elution and dissolution, and furthermore, effective concentrations are highly toxic and highly persistent, which is undesirable from the standpoint of environmental health and pollution.

Problems to be Solved by the Invention Therefore, there is a need for an aquatic pest control agent that has low toxicity, low persistence, and does not have a negative impact on the ecosystem or working environment. It is an object of the present invention to provide such an aquatic pest control agent.

Means for Solving the Problems The above objects are achieved by the aquatic pest control agent according to the present invention, which is characterized by containing the following phenol derivative as an active ingredient.

(In the formula, R is a linear or branched aliphatic saturated hydrocarbon residue having 3 to 21 carbon atoms; Xl to x5 are each the same or different groups selected from a hydrogen atom, a hydroxyl group and a methoxy group, but (Excluding cases where all of X1 to X5 are hydrogen atoms) is used as an active ingredient, and some or all of the conventionally used antifouling agents are replaced with the antifouling compound. or in the form of the general formula (I
) directly dissolve or suspend in an aqueous system one or a combination of two or more phenol derivatives,
It is provided as an aquatic pest control agent in the form of an aqueous solution or dispersion. Phenol (carbolic acid) has long been recognized for its bactericidal and antiseptic effects, and is widely used in the medical field as an aqueous disinfectant for hands and fingers.

However, carbolic acid has a pungent odor and is not preferred as a control agent for aquatic pests, and its efficacy is not sufficient. On the other hand, although alkyl derivatives of phenol are widely known as raw material compounds for synthetic resins, their antifouling effects have not been known at all. According to research by the present inventors, certain phenol derivatives are highly degradable in the natural world, and their persistence and accumulation are not a problem at all, and they are also effective against microorganisms such as bacteria and diatoms in the water and large sessile organisms in the sea. It was found that it has a strong control effect even at extremely low concentrations. The aquatic pest control agent according to the present invention containing such a phenol derivative as an active ingredient exhibits a sufficient control effect against aquatic pests with a very small amount of elution or dissolution into water. That is, in the present invention, carbon number 3 to 2 represented by the above formula
Phenol derivatives having one linear or branched aliphatic saturated hydrocarbon residue are used alone or in combination of two or more as an active ingredient for controlling aquatic pests. The aliphatic hydrocarbon moiety exhibits lipophilicity, and the phenol hydroxyl group exhibits hydrophilicity. Therefore, the phenol derivative used in the present invention itself has surfactant ability, is easily taken up by aquatic pests, and is easily absorbed by aquatic pests. It is believed that the bactericidal and pesticidal effects are sufficiently demonstrated. In fact, alkylphenols having hydrocarbon residues with a carbon number of 1 to 2 do not have sufficient effects, and if the number of carbon atoms becomes too large, the amount of alkylphenol used must be increased, which may result in poor economic efficiency. It has been discovered. The phenol derivative of the present invention can be made into a highly concentrated solution, for example, about 80% by weight, and can be applied by dipping fishing nets, etc., or can be blended into a paint and applied to ships and underwater structures as an antifouling paint. can. The amount of these phenol derivatives used in coating compositions or antifouling liquids for fishing nets is 0.
The amount is 5 to 80% by weight, preferably 1 to 50% by weight, and can be appropriately selected in consideration of the purpose of use, antifouling period, etc. Generally, when paints and antifouling agents are used at concentrations within the above range, a strong antifouling effect will be exhibited for more than one year.

In this case, the paint and antifouling liquid compositions that can be selected may be those conventionally used. For example, the resin vehicle may be organic solvent-based such as vinyl chloride resin, chlorinated rubber resin, or chlorinated polyethylene resin. , chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, polyamide resin, petroleum resin, silicone resin, silicone rubber resin,
Waxes, paraffins, rosin esters, rosin-based resins, and resins containing metal elements such as tin, copper, zinc tellurium, etc. in their side chains are used singly or in combination. In addition, examples of aqueous systems include acrylic emulsion resins, epoxy emulsion resins, and vinyl acetate resins. Furthermore, although it is not essential for the antifouling function, it is also possible to incorporate a known antifouling agent as an antifouling agent. In addition, commonly used plasticizers, coloring pigments, extender pigments, solvents, etc. can be contained in arbitrary proportions. In the production of MAfS paints, they can be prepared by methods known per se in the field of paint manufacturing technology.

On the other hand, when the aquatic pest control agent of the present invention is dissolved or suspended in a cooling water system, etc., one type or a combination of two or more phenol derivatives of general formula (I) is added to the water system. . The amount added to the aqueous system is 0.1 to 50 ppm as a phenol derivative, preferably 0.5 to 50 ppm.
Achieves extremely strong control effects at a low concentration of 30 PPm. The method of introducing into an aqueous system is by directly dissolving or physically suspending it in an aqueous system. Further, the input may be continuous or intermittent, and can be arbitrarily selected depending on the water system and the occurrence of pests.

Further, by combining the phenol derivative according to the present invention with a compound having aqueous properties, an extremely effective aquatic pest control agent can be provided.

That is, one or more of the above-mentioned silicone oil, vaseline, petroleum waxes, and liquid paraffins in the antifouling paint composition or antifouling agent liquid for fishing nets characterized by containing a phenol derivative. By using a water-based compound, a strong and stable antifouling effect can be achieved over a long period of time. A paint for preventing the adhesion of marine organisms, previously proposed in JP-A No. 60-258271, contains a film-forming silicone resin vehicle as an essential component and contains an effective amount of a surfactant therein.

In the present invention, a film-forming silicone resin vehicle may or may not be present. Furthermore, as mentioned above, the phenol derivative according to the present invention has surfactant ability, but it is structurally clear that it is incomparably weaker than that of commonly-called surfactants. . Therefore, the combination of a phenol derivative and an aqueous compound in the present invention is completely new.

The compound having water-promoting properties according to the present invention is one or more compounds belonging to silicone oil, petrolatum, petroleum waxes, and liquid paraffins.

Silicone oil is called polyorganosiloxane, and is an oily substance that has in its structure, such as polydimethylsiloxane where Rt and R2 are methyl groups, and methylphenyl where R, and R2 are methyl and phenyl groups. Examples include polysiloxane.

Petroleum waxes are refined crude oil whose quality is defined in JIS K2235, and specifically include paraffin wax, microcrystalline wax, petrolatum, and the like. In particular, petrolatum, which is highly purified from petrolatum, is defined by the Japanese Pharmacopoeia, and includes white petrolatum, yellow petrolatum, etc.

In addition, liquid paraffins are fractional distillation products of crude oil, and are
It is specified in K2231 and is classified according to viscosity, etc.

The ratio of the combination of the phenol derivative and the aqueous compound can be appropriately selected from 1 to 99% by weight of the amount of the aqueous compound and the phenol derivative, taking into account the purpose of use, antifouling period, etc.

When blending one or more of a phenol derivative and an aqueous compound into the antifouling paint composition or the antifouling agent liquid for fishing nets according to the present invention, the amounts of the phenol derivative and the lead aqueous compound are determined. The total amount of compounds having 0.
It can be appropriately selected from 5 to 80% by weight, preferably from 1 to 50% by weight.

Also, in this case, compositions that can be selected as other components include:
Any conventionally used one may be used, and it is the same as described above. The same applies to manufacturing.

The present invention will be explained below with reference to Examples.

(Left below) Examples 1 to 9 40% per hour in a waterway with a total length of Loom and an average cross-sectional area of 0.1 m.
The control effect was investigated in an experimental waterway introducing 0ffl of seawater. Each phenol derivative shown in Table 18
A test solution prepared by mixing 10 kg of seawater with 10 kg of seawater is dripped at the waterway entrance over a period of 8 hours every day.

The blinding effect was investigated 10 days after the start of the experiment. The effectiveness was investigated using adhesive boards (hard vinyl chloride boards, 1
The wet weight of the organisms attached to the 00x300x3.2 scale for 10 days was measured and compared with a system containing no phenol derivative as a control. The results are shown in Table 1.

Additionally, Table 1 also shows the results of Comparative Example 1 in which no phenol derivative was added.

(Leave below) The adhesion plate will be installed A: Directly below the test water drop (channel entrance) B: 10 m from the channel entrance C: 25 m from the channel entrance D = 50 m from the channel entrance E: Loom from the channel entrance (channel exit) The test plates were completely submerged in water at each location.In addition, slime and small mussels were observed in the control area, but only slime was observed in the other experimental areas.

Examples 10 to 19 and Comparative Example 2.3 Phenol derivative compounds according to the invention shown in Table 2,
The other components and the components of the comparative example were each dispersed using an SG mill using glass beads to prepare an antifouling paint and a comparative paint (not containing a phenol derivative). Antifouling tests were conducted on these antifouling paints and comparative paints. In the antifouling test, the antifouling paints and comparative paints listed in Table 2 were applied to a test steel plate of 10,100 x 300 size, which had been previously coated with a commercially available anticorrosion coating, so that the dry film thickness was 60 to 80μ.
After drying in the sun, it was placed 1m underwater in a test raft off the coast of Tamano City, Okayama Prefecture.
The soil was immersed to a depth of 100 mL to examine the degree of contamination caused by adhering soil and materials.

As Comparative Example 3, a commercially available steel plate coated with the above-mentioned anti-corrosion coating was simultaneously immersed and investigated. The results are shown in Table 3.

Table 3 Note 1: Raloflex MP-45 Vinyl chloride/vinyl isopropyl manufactured by BASF, West Germany
Ether copolymer Note 2: KE45-TS Manufactured by Shin-Etsu Chemical - Liquid type room temperature curing Silicone rubber Note 3: 5
H-510 Oil Toray Silicone ■ Methylphenyl silicone oil Note 4: Haloflex 202 IIIperial Chemical Indu
Stries PLC aqueous vinyl acrylic copolymer latex (hereinafter referred to as blank space) Examples 20 to 29 A commercially available alkylphenol compound according to the present invention shown in Table 4 and other components were dispersed and mixed using a high-speed homodisper to prepare a fishing net barrier. A staining agent was prepared.

A fishing net antifouling test was conducted using these antifouling agents for fishing nets.

In the fishing net antifouling test, each of the fishing net antifouling agents listed in Table 4 was used on a test net (60 knotless twisted 6 knots 20 cts x 30 c
After applying dyed netting by pickling and air-drying it for two days, it was immersed in the sea at a depth of 1 m in a test raft off the coast of Tamano City, Okayama Prefecture, and the degree of contamination by attached organisms was investigated.

As Comparative Example 4, an organic tin-based fishing net antifouling agent (tributyltin methacrylate copolymer) and as Comparative Example 5, a test net that had not been subjected to dyed net treatment were simultaneously immersed and investigated.

The results are shown in Table 5.

Composition of Comparative Example 4 Nitributyltin methacrylate/methyl methacrylate/
2-Ethylhexyl acrylate copolymer weight ratio: 60
/ /8) 30 parts Kijiroru 70 parts (the following is a margin) Table 5 Values are % of mesh clogging As can be seen from the above examples, the aquatic pest control agent according to the present invention has extremely good effects. it is obvious.

Claims (3)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a linear or branched aliphatic saturated hydrocarbon residue having 3 to 21 carbon atoms; X_1 to X_5 are each the same or Aquatic pests containing as an active ingredient one or more phenol derivatives represented by different groups selected from hydrogen atoms, hydroxyl groups, and methoxy groups (excluding cases in which all of X_1 to X_5 are hydrogen atoms) Pesticide (2) One or two of the phenol derivatives described in item 1.
An aquatic pest control agent characterized by containing as an active ingredient an organic compound having water repellency and a water-repellent organic compound. (3) The aquatic pest control agent according to item 2, wherein the water-repellent compound according to item 2 is one or more selected from silicone oil, petrolatum, petroleum waxes, and liquid paraffins.