JP2006001879A - Antifoulant for underwater member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a safe antifoulant for underwater members having excellent antifouling effects on aquatic damaging organisms including coelenterate and shellfishes, Polychaeta living in pipes and algae sticking on culturing or stationary fishnets, and the like, having high storage stability with low-polluting tendency, and slight in environmental burden as well. <P>SOLUTION: The antifoulant for underwater members that enables the surfaces of the underwater members to be imparted with antifoulingness by applying it to the surfaces of the members used by immersing underwater comprises a phenolic oligomer obtained by reaction between a phenolic compound and an alkenyl aromatic hydrocarbon in the presence of an acid catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention prevents contamination of shells, tubules, algae, and other organisms that adhere to the surface of the member by immersing it in water and applying it to the surface of the member to be used. It is related with the antifouling property imparting agent for underwater members which can be carried out and has little environmental load.

  Fishing nets for aquaculture or stationary are kept in the sea or fresh water for a long time. Aquatic organisms such as adhere. The fish nets and the like to which these aquatic organisms are attached will increase in weight and will sink into the sea, causing the fish to escape. Therefore, a great deal of labor is required to remove these deposits, and the economic loss due to this is immeasurable.

  So far, various studies and proposals have been made as countermeasures against attached organisms, and a series of organotin compounds have been used for many years. However, organic tin compounds have environmental hormone action, and their use is prohibited in Japan because they are highly likely to destroy the environment. For these reasons, the emergence of antifouling properties for underwater members such as low-pollution fishing net antifouling agents and antifouling paints is desired.

Under such circumstances, for example, an underwater antifouling paint containing a benzothiazole compound as an active ingredient (see Patent Document 1), various fishing net antifouling combinations of tetraalkylthiuram disulfide compounds and other compounds. Agent, antifouling paint composition and fishing net antifouling agent solution (see Patent Document 2, Patent Document 3 and Patent Document 4), antibacterial agent containing pyrithione metal salt as active ingredient, and underwater antifouling paint (Patent Document 5, Patent Document) 6), an anti-fouling agent for marine structures containing a 3-isothiazolone compound as an active ingredient (see Patent Document 7), and an antifouling paint containing a maleimide compound as an active ingredient (Patent Document 8, Patent Document 9, Patent Document 10, Patent) Document 11, Patent Document 12, and Patent Document 13) have been proposed.
However, when the antifouling agent or the like is applied to the surface of the underwater member for several months, the surface of the underwater member is covered with various kinds of dirt, and aquatic organisms start to adhere abruptly. In addition, heavy metals and the like similar to tin compounds are often used for these antifouling agents, and there is a concern about the environmental impact due to long-term continuous use.
Japanese Patent Publication No.51-10849 JP 60-38306 A JP-A 63-284275 Japanese Examined Patent Publication No. 1-1606 Japanese Patent Publication No.54-14610 JP 54-15939 A Japanese Patent Publication No. 61-50984 Japanese Patent Publication No. 1-20665 Japanese Patent Publication No. 2-2424 JP-A-53-9320 JP-A-5-201804 JP-A-6-100405 JP-A-6-100408

  Therefore, the present inventors applied an antifouling property imparting agent to the surface of an underwater member used by being immersed in water, and the antifouling property imparting agent was washed with seawater or fresh water and gradually dissolved in water. The antifouling imparting agent that keeps a new surface on the surface of the underwater member to which the antifouling imparting agent is always applied and prevents the dirt from adhering to the surface of the underwater member, and at the same time dissolves in the water. It has been found that all the above-mentioned problems can be solved by reducing the burden on the environment without containing toxic or environmental hormonal substances, and the present invention has been completed.

  Therefore, the object of the present invention is to apply it to the surface of a member to be used by immersing it in water, so that it can be used as a coelenterate such as hydroworm and oberia, shellfish, tubules, seaweeds, bryozoans and soft bodies. The object is to provide an antifouling agent that prevents the attachment of aquatic organisms such as animals and the like, and at the same time, does not worry about secondary contamination and has a low environmental burden.

  That is, the present invention is an antifouling imparting agent for underwater members that can impart antifouling properties to the surface of the member by being applied to the surface of the member used by being immersed in water, An antifouling agent for underwater members, comprising a phenol-based oligomer obtained by reacting alkenyl aromatic hydrocarbon with alkenyl aromatic hydrocarbon in the presence of an acid catalyst.

The antifouling property imparting agent for underwater members of the present invention contains a phenolic oligomer obtained by reacting phenols with an alkenyl aromatic hydrocarbon in the presence of an acid catalyst. Such a phenolic oligomer is preferably composed mainly of a compound represented by the following general formula (1) from the viewpoints of solubility in water, safety, and no fear as an environmental hormone. There should be.
(Ar ₁ -R _1- ) _m Ar ₂ -OH (1)
(In the formula, Ar ₁ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, R ₁ represents an aliphatic hydrocarbon group having 2 to 5 carbon atoms, m represents a number of 1 to 4, Ar ₂ Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms.)

  The phenolic oligomer in the present invention may be an oligomer having a number average molecular weight of 300 to 1200, a hydroxyl group equivalent of 100 to 500, and a softening point of 120 ° C. or lower. Phenols include monovalent phenols such as phenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol, 3,5-xylenol, p-tert-butylphenol, resorcinol, bisphenol A, etc. 2 Valent phenols and the like can be mentioned, but phenol or lower alkylphenol is preferred, and phenol is more preferred. These phenols may be used alone or in combination of two or more. Crude phenol obtained in the phenol production process, a mixture of phenol and lower alkylphenol, distillation residual oil and the like are also preferred phenols. For example, there are a crude tar acid obtained by hydrolyzing a tar acid obtained by extracting tar oil with an alkaline extraction aqueous solution, and a crude phenol mainly composed of phenol obtained by distillation thereof.

  Examples of the alkenyl aromatic hydrocarbon include styrene, α-methyl styrene, divinyl styrene, and vinyl compounds whose basic structure is naphthalene or biphenyl. Styrene and divinyl benzene are preferable. Further, these alkenyl aromatic hydrocarbons may be used alone or in combination of two or more.

  The ratio of phenols to alkenyl aromatic hydrocarbons should be 1 part by weight or more and less than 4 parts by weight, preferably 2 to 3 parts by weight, with respect to 1 part by weight of phenols. However, the optimum ratio varies slightly depending on the type of phenol. If the proportion of alkenyl aromatic hydrocarbon is too large, the solubility in water tends to decrease. For example, the effect of improving the solubility in water when phenols are mixed in the same proportion increases in the order of p-tert-butylphenol, p-cresol, and phenol.

  The acid catalyst used in the reaction of phenols with alkenyl aromatic hydrocarbons includes hydrochloric acid, sulfuric acid, sulfonic acids, phosphoric acids, protonic acids such as chloric acids, aluminum chloride, boron trifluoride and their complexes, etc. Solid acids such as Lewis acids, zeolites and activated clays can be used. In terms of reactivity, boron trifluoride ether complex is preferred.

  This reaction can be carried out without a solvent or diluted with a solvent. When using a solvent, it must be a solvent that can dissolve the reaction mixture. For example, one or more organic solvents such as toluene, xylene, methyl ethyl ketone (MEK), and methyl isobutyl ketone should be used in combination. Can do. Toluene or xylene is preferable in terms of reactivity and economy.

  About the temperature which performs this reaction, 60-140 degreeC is preferable, and an unreacted component will remain at 60 degrees C or less, a side reaction will occur at 140 degrees C or more, and the performance of a modifier will fall. In view of reaction activity, the reaction temperature is particularly preferably 80 to 85 ° C.

  Moreover, it is possible to adjust the physical property of the oligomer obtained by changing reaction conditions. For example, by adjusting the reaction temperature, it is possible to increase the average molecular weight or increase the softening point, and it is possible to change the hydroxyl equivalent by changing the proportion of phenols and alkenyl aromatic hydrocarbons. It is. The number average molecular weight is 200 to 1200, preferably 300 to 1000, hydroxyl group equivalent 50 to 500, preferably 150 to 400, softening point 120 ° C. or lower, preferably room temperature liquid or 50 ° C. or lower.

The antifouling agent for underwater members of the present invention may be used after being diluted with a solvent or may be used without a solvent. When diluted with a solvent, it is preferably used after being dissolved in a less toxic solvent such as methylcyclohexane or ethylcyclohexane. When a solvent is used, it is desirable to use after immersing the underwater member in water after the solvent has been applied to the surface of the underwater member. As a solvent to be used, an ester solvent or an ether solvent having a high dissolving power can be used as a matter of course. Can be used for purposes.
On the other hand, when using the antifouling agent for underwater members in the present invention without using a solvent, it is preferable to heat for the purpose of reducing the viscosity of the oligomer.

  Further, the antifouling agent for underwater members in the present invention may be used alone as the antifouling agent by the above-mentioned phenolic oligomer, or may be used in combination with other known antifouling agents.

The antifouling agent for underwater members in the present invention includes fish nets for aquaculture or stationary and fishing equipment such as buoys that support them, and those used by immersing them in water such as marine structures and bridges. Applying to the surface of underwater parts that are used by immersing a part of the bottom of the ship underwater, etc., thereby preventing the adhesion of water fouling organisms such as shellfish, tubules and algae, and coelenterate Excellent antifouling property can be imparted. That is, the antifouling property imparting agent applied to the surface of the underwater member as described above is washed with seawater or fresh water and gradually dissolves in the water. Always keep a new face. Therefore, it prevents dirt from adhering to the surface of the underwater member, and hydrozoa such as hydroworms and oberias, and aquatic organisms such as shellfish, tubules, seaweeds, bryozoans and molluscs It can prevent adhering to the surface of a member.
Moreover, since the antifouling property-imparting agent in the present invention does not contain a toxic or environmental hormonal substance or the like, even if it is dissolved in water, there is no concern about secondary contamination to the environment, and the burden on the environment is small. Furthermore, the antifouling property-imparting agent in the present invention is excellent in storage stability.

  Next, the present invention will be described with reference to examples. In addition, this invention is not limited at all by these examples.

[Synthesis of oligomers]
100 parts of phenol, 150 parts of toluene, 3 parts of boron trifluoride, and 200 parts of styrene were placed in a flask and reacted at 80 ° C. for 2 hours. After completion of the reaction, water was added to quench the catalyst. Thereafter, a condenser was attached to the flask, and distillation was started at normal pressure. After distillation of toluene, unreacted phenol was recovered, and 299 parts of oligomer remained in the flask.

[Preparation of antifouling agent]
Example 1
50 parts of the oligomer synthesized above and 50 parts of methylcyclohexane were mixed and dissolved to obtain an antifouling agent.

[Efficacy confirmation test as antifouling agent for fishing nets]
The antifouling property imparting agent prepared above was dip-coated on a polyethylene knotless net (6 nodes, 400 denier / 60) and dried. In this way, a fishnet coated with an antifouling agent is fixed to a 40 cm x 60 cm steel frame, and from May 2003 to 6 months, it will be 0.5 m in the NS area port of Tobata-ku, Kitakyushu City. I kept inundation and investigated the pollution situation to the net.
Further, as a comparative example, 50 parts of polybutene and 50 parts of methylcyclohexane and 5 parts of zinc pyrithione (Pr. G, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and dispersed. / 60) was dip-coated and dried, and the state of soiling on the net was examined in the same manner as in Example 1 (Comparative Example 1).
The results are shown in Table 1. The numbers in the table represent the adhesion area (%) of marine organisms.

[Solution test in water]
The antifouling property imparting agent according to Example 1 prepared above was dip-coated on a cotton fabric of 5 cm × 5 cm, dried, then placed in a beaker filled with distilled water with a stirrer, and stirred for 10 hours. After taking out more, it was dried and the dissolution rate was calculated by comparison with the initial weight.
The respective reduction rates were as follows.
(Example 1) 0.1%
(Comparative Example 1) 0.0%

[Safety test]
About the antifouling property imparting agent according to Example 1 above, two types of oligomers A and B (A is obtained by adding 1 or 2 styrene to phenol, B is obtained by adding phenol to the phenol). AMES test of 2 to 3 styrene added). All the results were negative.

[Environmental hormone test]
The estrogen activity test was performed on the above two kinds of oligomers A and B by a screen test using a genetically modified yeast. The test was based on the yeast screen test developed by Sumpter et al. (Routledge, EJ and Sumpter JP (1996) Estrogenic Activity of Surfactants and Some of Their Degradation Products Assessed Using a Recombinant Yeast Screen. Environmental Toxicology and Chemistry 15, 241- 248). Oligomer A and B were respectively 0.049, 0.098, 0.20, 0.39, 0.78, 1.56, 3.13, 6.25, 12.5, 25, 50 and 100 mg / l ( Recombinant yeast (Saccharomyces cerevisiae) was added to each aqueous solution as an aqueous solution having a concentration of n = 4) and kept at a temperature of 25 ± 1 ° C. for about 3 days. The response of the screen test with genetically modified yeast was confirmed using 17β-estradiol and bisphenol A as positive control substances for estrogen-like substances. As a result, oligomer A was 1 / 90,000 activity compared to 17β-estradiol, oligomer B was 1 / 95,000 activity compared to 17β-estradiol, and in the above estrogen activity test, the two types of oligomers A and B were Both were negative at a concentration of 12.5 mg / l or less. The influence of bisphenol A is 1 / 18,500 activity of 17β-estradiol.

Claims (3)

  An antifouling agent for underwater members that can impart antifouling properties to the surface of the member by immersing it in water and applying it to the surface of the member. An antifouling agent for underwater members, comprising a phenolic oligomer obtained by reacting hydrogen with an acid catalyst. The antifouling agent for underwater members according to claim 1, wherein the phenol oligomer is represented by the following general formula (1).
(Ar ₁ -R _1- ) _m Ar ₂ -OH (1)
(In the formula, Ar ₁ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, R ₁ represents an aliphatic hydrocarbon group having 2 to 5 carbon atoms, m represents a number of 1 to 4, Ar ₂ Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms)   The antifouling agent for underwater parts according to claim 1 or 2, wherein the underwater parts are fishing gear.