JPH08119808A - Organism stick-proofing agent and antifouling coating containing the same - Google Patents

Abstract

PURPOSE: To obtain an organism stick-proofing agent having activity of preventing aquatic fouling organisms from adhering to the surfaces of ships, marine structures, bridges, etc., containing as an active-ingredient a specific low-toxic compound as a substitute for tin compounds, and to obtain an antifouling coating containing this agent. CONSTITUTION: This organism stick-proofing agent contains as an active ingredient a compound expressed by the formula [X is N or C-Y (Y is NH2 , NO2 , SO3 H, CHO or COOH); R is a 1-20C hydrocarbon or alkoxy]. As the compound of the formula, compounds of the formula in which R is a 6-12C hydrocarbon or alkoxy, or R is bound to the para site relative to X are preferable, being e.g. 4-hexylpyridine, 4-octylpyridine, 4-nonylaniline, 4-octylbenzenesulfonic acid, 2-octylbenzoic acid. When this agent is to be applied, one or more kinds of this compound of the formula may be directly used as it is, but in general is/are used as a dispersion in a suitable binder resin such as butyral resin or acrylic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biofouling preventive agent which is effective in preventing aquatic fouling organisms from adhering to the surfaces of ships, ridges and the like, and an antifouling paint using the same.

[0002]

2. Description of the Related Art Aquatic fouling organisms are large adherent organisms that attach to artificial structures in water and cause industrial and economic disadvantages. For example, barnacles, mussels, oysters, hydrozoa, mosses, ascidians, Animals such as Cerpra and plants such as Ulva grow and grow to a size that can be visually observed.

When large aquatic organisms such as barnacles, serpra, squirts, mosses, oysters, and oysters adhere to the bottom of ships, problems such as increased weight, increased water flow resistance, and reduced cruising speed occur, resulting in reduced life of ships. Cause industrial problems such as increased fuel consumption.

Methods for preventing adhesion of these aquatic organisms have been studied for a long time, and biological methods using natural enemies of organisms causing adhesion, use of structural materials that are difficult to attach (for example, use of copper alloys) , Silicone-based paint, fluorine-based paint, etc.), prevention of larva influx (for example, a method of shielding with a screen), extermination of larvae (for example, light, ultraviolet rays, color,
Environment where it is difficult to survive such as use of ultrasonic waves, temperature rise, oxygen deficiency),
Mechanical removal of attached organisms (e.g. cleaning, jet cleaning,
(Brushing, suction, etc.), chemical or biochemical methods (eg shellfish killing, repelling, use of antifouling agents, etc.) are being studied.

However, because of its wide application range, high effect, and easy treatment, a method of applying a ship bottom paint containing a shell killer, a repellent, an antifouling agent, etc. is widely adopted, It has also been studied.

However, in the paint containing these chemical agents, the drug in the coating film gradually elutes in water, or the paint containing this gradually scrapes and dissipates in water, and a new painted surface is always exposed. Because of the design, it has been pointed out that there is concern that it will have a negative impact on the marine environment. Especially 1
When it was pointed out that the tin compounds, which are the most representative antifouling agents in the 980s, contaminated fish and shellfish, various regulations were added to tin-containing ship bottom paints in European countries and the United States.
The development of alternative methods for preventing pollution by aquatic organisms has emerged as an urgent issue.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a low toxicity biofouling preventive agent which replaces a tin compound and an antifouling paint containing the biofouling preventive agent. And

[0008]

That is, the present invention provides the following general formula [I]:

Embedded image The present invention relates to a biofouling preventive agent comprising a compound represented by:

In the general formula [I], X is a nitrogen atom (N) or CY (Y is NH ₂ , SO ₃ H, CHO or COOH).
Represents). That is, the formula [I] has a pyridine ring when X is a nitrogen atom, an aniline ring when Y is NH _2, a nitrobenzene ring when NO _2, a benzenesulfonic acid ring when SO ₃ H, and a CHO ring when CHO. Represents a benzaldehyde ring and, in the case of COOH, represents a benzoic acid ring.

These rings are hydrocarbon groups having 1 to 20 carbon atoms, for example, alkyl groups which may have a branched chain such as methyl, ethyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl and stearyl, Cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cyclopeptyl, cyclooctyl and cyclododecyl, alkenyl groups such as propenyl, butenyl, hexenyl, octenyl and dodecenyl, or aryl groups such as phenyl, tolyl, xylyl and naphthyl, or the number of carbon atoms. It has 1 to 20 alkoxy groups, for example, substituents such as ethoxy, nonyloxy and oleoyl. Among these substituents, a hydrocarbon group having 6 to 12 carbon atoms and an alkoxy group having 6 to 12 carbon atoms are preferable from the viewpoints of biofouling prevention property, easy adjustment of solubility, and the like.

In the general formula [I], a compound in which these substituents are bonded to the 2-position (ortho-position) or 4-position (para-position), preferably 4-position with respect to X has the effect of preventing biofouling. large.

When the general formula [I] is an aniline ring, a nitrobenzene ring or a benzaldehyde ring, even if R is a hydrogen atom, it exerts a bioadhesive function and exhibits appropriate solubility in seawater. It can be used as an inhibitor. When R is a hydrogen atom in compounds other than the aniline ring, nitrobenzene ring or benzaldehyde ring, it is difficult to use it as a biofouling preventive agent because its solubility in seawater is too high and its durability is short.

Further, the compound represented by the general formula [I] may further have a substituent such as a halogen atom such as chlorine, fluorine or bromine.

Specific compounds represented by the general formula [I] include 2-methylpyridine, 4-ethylpyridine,
4-hexylpyridine, 4-octylpyridine, 4-nonylpyridine, 4-decylpyridine, 4-laurylpyridine, aniline, 4-ethylaniline, 4-hexylaniline, 4-octylaniline, 4-nonylaniline,
4-decylaniline, 4-dodecylaniline, 4-ethylnitrobenzene, 4-octylbenzenesulfonic acid,
4-ethylbenzenesulfonic acid, 4-hexylnitrobenzene, 4-octylbenzaldehyde, 4-nonylbenzaldehyde, 4-ethylbenzenesulfonic acid, 2-
Octylbenzoic acid, 4-hexyloxyaniline, 4-
Nonyloxypyridine, 4-hexyl-2-chloroaniline, 4-ethoxy-2-chloroaniline, 4-nonyloxyaniline, 4-decylbenzoic acid, 4-oleylaniline, 4-stearylaniline and the like can be mentioned.

Preferred among the above compounds are 4-hexylpyridine, 4-octylpyridine, 4-nonylpyridine, 4-decylpyridine, 4-laurylpyridine,
4-hexylaniline, 4-octylaniline, 4-nonylaniline, 4-decylaniline, 4-dodecylaniline, 4-octylbenzenesulfonic acid, 4-hexylnitrobenzene, 4-octylbenzaldehyde, 4-
Nonylbenzaldehyde, 2-octylbenzoic acid, 4-
Hexyloxyaniline, 4-nonyloxypyridine,
4-hexyl-2-chloroaniline, 4-nonyloxyaniline, 4-decylbenzoic acid and the like.

The compound represented by the general formula [I] is easily available as a commercial product, or can be synthesized by a known method.

When the compound used in the present invention has a carboxyl group or a sulfonic acid group, its salt may be used.

As salts, alkali metals such as Na,
Examples thereof include alkaline earth metal salts such as K, such as Ca and Mg, ammonium and other salts such as Mn, Zr (0), Al, Zn and Fe.

When it has an aniline ring or a pyridine ring, it may be used in the form of a salt such as hydrochloride.

The anti-biofouling agent of the present invention may use one or more compounds represented by the general formula [I] as they are, but generally, they are used in a suitable binder resin such as butyral resin or acrylic resin. Disperse and use. In order to disperse the resin in the resin, the compound of the general formula [I] is dissolved or dispersed in a solution prepared by dissolving the resin in a suitable solvent, and the solution is applied to the surface of the structure to be coated and dried to form a film. It can be carried out.

The effective amount of the compound represented by the general formula [I] is suitably 3 to 70% by weight, more preferably 5 to 50% by weight, based on the solid content after drying. If it is less than 3% by weight, a sufficient effect of preventing biofouling cannot be achieved. Again 7
This is because if it is more than 0% by weight, the formation of a coating film is hindered and a tough coating film cannot be obtained.

Particularly, the biofouling inhibitor of the present invention is useful as an antifouling paint for the surface of a structure, which is used by being blended in a suitable coating composition and immersed in water.

That is, the compound represented by the general formula [I] is dissolved or dispersed in a suitable solvent, and a binder resin is added if necessary, and used as an antifouling paint for underwater immersion structures such as ship bottom paints and fishing net paints. You can

The binder resin suitable for the present invention has a glass transition temperature (Tg) of 15 to 120 ° C., more preferably 2
5 to 100 ° C., number average molecular weight of 1,000 to 50,000, more preferably 5,000 to 30,000, hydroxyl value of 0 to 10
0, more preferably 0 to 80. Further, the Tg value in the above range is suitable for achieving film strength as an antifouling paint and appropriate film consumption.

When the glass transition temperature is lower than 15 ° C., the coating film becomes too soft and, for example, peeling occurs when the ship is sailing. When the temperature is higher than 120 ° C, cracks and the like occur in the coating film.

When the number average molecular weight is less than 1000, a tough coating film cannot be obtained, and when it is more than 50,000, the viscosity of the coating composition becomes high, and more solvent than necessary must be used to maintain a constant viscosity.

When the hydroxyl value is more than 100, seawater enters the membrane and elutes the compound represented by the general formula [I] more than necessary, so that the antifouling property cannot be maintained for a long time.

Examples of the binder resin which can be used in the present invention are butyral resin, acrylic resin, polyester resin, alkyd resin, vinyl resin, epoxy resin, urethane resin and urea resin.

The compound represented by the general formula [I] of the present invention is 3 to 70 in the antifouling paint, preferably per solid content of the paint.
%, More preferably 5 to 50% by weight. The binder resin is preferably 5 to 70% by weight of the total weight of the coating,
More preferably, it is blended in an amount of 15 to 60% by weight. If it is less than 3% by weight, the effect of preventing biofouling cannot be sufficiently obtained.
This is because if it is more than 0% by weight, a tough coating film cannot be obtained.

In the antifouling paint of the present invention, for example, in addition to the above-mentioned biofouling preventive compound and the binder resin, suitable diluents such as water, alcohol, alkyl glycol, cellosolve, acetic acid ester, xylene, toluene, ketone, etc.
An extender pigment such as talc, a coloring pigment, a curing agent, etc. may be added.

Further, in the present invention, known antifouling agents, agricultural chemicals and herbicides can be used as long as they do not inhibit the action of the biofouling preventing compound represented by the general formula [I].

The antifouling paint of the present invention can be applied to a structure by any method such as coating, dipping, and the like.
A spray or the like can be used. Hereinafter, the present invention will be described with reference to examples.

[0033]

[Biofouling prevention evaluation test]

Examples 1 to 30 Butyral resin (BM-2; manufactured by Sekisui Chemical Co., Ltd.) 20 g, Table 1
10 g of the compound of the general formula [I] shown in, xylene 10 g,
5 g of n-butanol was added, and this coating liquid was brush-coated on a commercially available acrylic plate (300 mm × 100 mm × 2 mm) so that the dry film thickness was about 200 μm.

COMPARATIVE EXAMPLE 1 20 g of butyral resin used in the example and bistributyltin oxide (TBTO) 7 which is an existing antifouling agent.
g, xylene 10 g, and n-butanol 5 g were added, and the dispersion solution was brush-coated on an acrylic plate to a thickness of about 200 μm.
m coating film was formed.

Comparative Example 2 In Comparative Example 1, bistributyltin oxide (TB
A coating film was formed in the same manner as in Comparative Example 1 except that 15 g of cuprous oxide and 5 g of rosin were dispersed instead of 7 g of (TO).

Comparative Example 3 20 g of the butyral resin used in Example 1 was dissolved in 15 g of methyl ethyl ketone, and the solution was treated in the same manner as in Example 1 to form a coating film.

[0037]

[Evaluation] The test plates obtained in the examples and comparative examples were immersed in a depth of about 1 m of seawater having a water temperature of about 12 to 18 ° C for 1 month.
Barnacles after 2 months, 4 months, 8 months and 12 months,
The state of attachment of animals such as cerpra and plants such as asao and aonoori was observed.

The evaluation of adhesion was carried out by expressing the area where organisms adhered in%. The biofouling-preventing compounds used and the antifouling property evaluation results are summarized in Table 1 below.

[0039]

[Table 1]

[0040]

[Antifouling paint evaluation test]

Examples 31 to 48 and Comparative Examples 4 to 5 Table 2 (Examples 31 to 39), Table 3 (Examples 40 to 48)
And each compound was disperse | distributed by the compounding shown in Table 4 (Comparative Examples 4-5), and the antifouling coating material was prepared.

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

A commercially available acrylic plate (300 mm
X 100 mm x 2 mm) with a dry film thickness of about 200 μm
Brushed so that

The test plates obtained in the Examples and Comparative Examples were immersed in seawater at a depth of about 1 m at a water temperature of about 12 to 18 ° C., and after 1 month, 2 months, 4 months, 8 months and 12 months, the barnacles, The state of attachment of animals such as cerpra and plants such as asao and aonoori was observed.

The evaluation of adhesion was performed by expressing the area where organisms adhered in%. The results are summarized in Table 5 below.

[0047]

[Table 5]

[0048]

INDUSTRIAL APPLICABILITY The present invention provides a novel anti-fouling compound which replaces a tin compound, and an antifouling paint containing the compound.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 37/10 41/04 Z C09D 5/16 PQL

Claims (4)

[Claims] 1. The following general formula: [In the formula, X is N or C—Y (Y is NH ₂ , NO ₂ , SO
₃ H, CHO or COOH) and R represents a hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms;
When Y is NH ₂ , NO ₂ or CHO, R may be a hydrogen atom. ] An anti-fouling agent comprising a compound represented by the following. 2. The biofouling inhibitor according to claim 1, wherein R is a hydrocarbon group or an alkoxy group having 6 to 12 carbon atoms. 3. The biofouling inhibitor according to claim 1 or 2, wherein R is bound to the para position with respect to X. 4. An antifouling paint containing the biofouling inhibitor according to any one of claims 1 to 3.