JPH073191A - Antifouling agent for coating material - Google Patents

Abstract

PURPOSE:To obtain the agent which provides antifouling effects over a very long term and is esp. effective in controlling harmful marine organisms. CONSTITUTION:The agent contains an inclusion compd. comprising an isothiazolone compd. and 5,5'-dichloro-2,2'-dihydroxydiphenylmethane. Slowly releasing the isothiazolone compd., the guest compd., into water, the agent maintains its antifouling activity over a very long term. It releases the compd. over a very longer term than an antifouling agent contg. a conventionally used inclusion compd. esp. in sea water and hence is very useful for a ship bottom coating, an antifouling agetn for a fishing net, etc., in controlling slime.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent for paints, and more particularly to an antifouling agent for paints for various underwater components such as ship bottoms and fishnets, which has a sustained release property of the active ingredient to provide an antifouling effect. The present invention relates to an antifouling agent for paint that can be maintained for a long period of time.

[0002]

2. Description of the Related Art Plants such as green algae and brown algae, animals such as barnacles, serpra, magpie squirts, squirts, mussels, oysters, and various aquatic organisms such as bacteria called slime, mold and diatoms are the bottoms of ships. If it adheres to fishnets, fishing nets, or other various underwater members, it will have a great adverse effect on the members.

Therefore, measures have been taken to prevent the adhesion of aquatic organisms by applying a paint containing an antifouling agent to these members. Conventionally, as an antifouling agent for paints, bis- (tributyltin) oxide ( Organotin compounds such as TBTO) have been used. However, TBTO is being regulated in terms of its accumulation in fish, etc.
As alternatives to 2,4,5,6-tetrachloroisophthalonitrile, zinc methyldithiocarbamate, etc. have been investigated. Also, isothiazolone compounds have been proposed.

[0004]

[Problems to be Solved by the Invention]
The antifouling effect of 4,5,6-tetrachloroisophthalonitrile and zinc methyldithiocarbamate is not sufficient,
Inferior in practicality.

The isothiazolone compounds have a good antifouling action, but they have a high solubility in water, and when they are used as antifouling agents for paints, they have the drawback that they dissolve early and the effect cannot be sustained.

As a solution to this problem, an isothiazolone-based compound is added to 1,1,6,6-tetraphenyl-
2,4-hexadiyne-1,6-diol (hereinafter "TP
It is abbreviated as "H". ) Or 1,1-di (2,4-dimethylphenyl) -2-probin-1-ol (hereinafter “DM
It is abbreviated as "P". A coating composition has been proposed in which the clathrate compound obtained by clathration with (1) is used as an antifouling agent (JP-A-62-1150).
No. 72), it cannot be said that the effect duration is sufficiently long even with this clathrate compound, and further improvement is desired.

It is an object of the present invention to solve the above-mentioned conventional problems and to provide an antifouling agent for paints, which has an extremely long antifouling effect and is particularly effective as a controlling agent for marine pests.

[0008]

The antifouling agent for paint of the present invention comprises an isothiazolone compound and 5,5'-dichloro-.
It is characterized by containing an inclusion compound with 2,2'-dihydroxydiphenylmethane.

The present invention will be described in detail below.

The isothiazolone compound used in the present invention is a compound represented by the following general formula (I).

[0011]

[Chemical 1]

In the present invention, among such isothiazolone compounds, particularly 5 represented by the following structural formula (II):
It is preferable to use -chloro-2-methyl-4-isothiazolin-3-one (hereinafter abbreviated as "CMI") because of its excellent antibacterial activity.

[0013]

[Chemical 2]

In the present invention, such an isothiazolone compound is used as a guest compound, and 5,5'-dichloro- which is a host compound represented by the following structural formula (III).
2,2'-dihydroxydiphenylmethane (hereinafter "CH
It is abbreviated as "PM". ) Is included as an inclusion compound to be an active ingredient.

[0015]

[Chemical 3]

Such an inclusion compound according to the present invention can be easily produced in a solvent or in a solventless reaction.

When a solvent is used, a solution prepared by dissolving CHPM in an ordinary water-soluble solvent such as methanol, ethanol or acetone is mixed with an isothiazolone compound such as CMI or a mixture containing impurities. To react. As a result, the clathrate compound precipitates as a solid, and the clathrate compound is filtered and separated by a conventional method to obtain the target clathrate compound.

The clathrate compound according to the present invention can be easily obtained by such a solvent reaction, but in the present invention, the inclusion compound can also be produced by a solventless reaction.

In this case, CHPM is directly added to an aqueous solution in which an isothiazolone compound such as CMI which is a guest compound is dissolved and mixed and stirred. The aqueous solution used is
It is not always necessary to include only the isothiazolone compound serving as the guest compound, and as in the case of the solvent reaction, it may include the isothiazolone compound and impurities and the like. That is, since an isothiazolone compound such as CMI reacts with CHPM with extremely high selectivity, in the production of the inclusion compound according to the present invention, an isothiazolone compound as a raw material containing impurities such as by-products is used as it is. Even when used, an inclusion compound in which only the desired isothiazolone compound is selectively included is obtained.

The reaction temperature may be any temperature in the range of 0 to 100 ° C, but is usually about 10 to 30 ° C. A reaction time of about 0.5 to 24 hours is sufficient.

After the completion of the reaction, the clathrate compound is usually obtained as a solid, and this can be separated from the aqueous layer, washed with water and dried to obtain the desired clathrate compound.

The clathrate compound according to the present invention is preferably used as an antifouling agent for paints in an amount of about 0.5 to 50% by weight based on the total weight of the paint composition. In this coating composition, other inorganics (such as cuprous oxide), organics (TBTO,
An antifouling agent may be used in combination.

As the paint vehicle of the paint composition containing the antifouling agent for paint of the present invention, a commonly used resin vehicle can be used, but a water-insoluble resin and a rosin-based vehicle are preferred. Used. Specifically, vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, petroleum resin, oil resin, Examples thereof include rosin ester-based resin, rosin-based soap, and rosin.
Further, as a vehicle having an antifouling property, α, β-unsaturated mono- or dicarboxylic acid obtained by a condensation reaction of (meth) acrylic acid and an organic tin compound such as bis (tributyltin) oxide or triphenyltin hydroxide It is also possible to use an acrylic copolymer resin composition containing the organic tin compound salt of 1 as a constituent unit.

A coating composition containing the antifouling agent for paints of the present invention is prepared by adding a predetermined amount of the antifouling agent for paints of the present invention to such a coating vehicle, and if necessary, a conventional composition. It can be easily prepared by blending a plasticizer, a coloring pigment, an organic solvent and the like used in the coating composition and mixing them according to a conventional method.

[0025]

In the antifouling agent for paints of the present invention, since the isothiazolone compound is the inclusion compound in CHPM, the isothiazolone compound, which is a guest molecule, is gradually eluted from the inclusion compound in water. The antifouling activity can be maintained for an extremely long period of time because it exhibits excellent sustained release properties.

Although the details of the reason are not clear, the antifouling agent for paints of the present invention has a markedly longer sustained release period than the conventional antifouling agents for paints using clathrate compounds, especially in seawater.
It is extremely effective in controlling slime as an antifouling agent for paints such as antifouling paints for ship bottoms and fishnets.

[0027]

EXAMPLES The present invention will be more specifically described below with reference to production examples, experimental examples, examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Production Example 1: Production of inclusion compound of CMI and CHPM: 0.2 g of CHPM and 1.5 g of a water-soluble aqueous bactericide solution containing CMI as a main component (bactericide concentration 10.4% by weight) are mixed, and the mixture is allowed to stand at room temperature. The reaction was carried out for 4 hours with stirring. The resulting semi-solid was separated from the aqueous layer and dried.

From the integrated value of the NMR spectrum of the product,
This is CHPM: CMI = 1: 0.35 (molar ratio)
It was confirmed that the inclusion compound was This clathrate compound is referred to as "CHPM-CMI clathrate compound".

Production Example 2: Production of inclusion compound of CMI and TPH TPH prepared by dissolving 0.5 g of TPH in 10 ml of methanol
4.26 g of a water-soluble fungicide containing CMI as a main component in the solution
When (CMI content 326 mg) was added and stirred, a white turbid matter was deposited. This was allowed to stand at room temperature for 3 hours and then filtered through filter paper to separate the precipitate from the solution.

As a result of NMR analysis of the precipitate, it was confirmed that the precipitate was an inclusion compound of TPH: CHI = 1: 2 (molar ratio). This clathrate compound was labeled as "TPH-CMI.
It is referred to as "inclusion compound".

Production Example 3: Production of inclusion compound of CMI and DMP DMP 0.5 g Water-soluble bactericide containing CMI as a main component 3.32 g in a DMP solution dissolved in 10 ml of methanol.
When (CMI content 283 mg) was added and stirred, a white turbid matter was deposited. When this precipitate was separated and analyzed in the same manner as in Production Example 2, the precipitate was found to be DM.
It was confirmed to be an inclusion compound with P: CMI = 2: 1 (molar ratio). This clathrate compound is referred to as "DMP-CMI clathrate compound".

Experimental Example 1 10 g of the CHPM-CMI clathrate compound was placed in a 0.8 μ membrane filter bag, immersed in 1 liter of pure water, and the active ingredient (CMI) from the clathrate compound was stirred while stirring with a stirrer. The release rate was measured over time, and the results of comparison with the case of CMI alone are shown in Table 1. From Table 1, CMI alone elutes the entire amount immediately, whereas CHPM-CM
It is clear that in the inclusion compound I, CMI gradually elutes and exhibits sustained release.

[0034]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 7 The ingredients shown in Table 2 were charged in a ball mill, and 2
Dispersion was carried out for 4 hours to prepare a coating composition.

In Table 2, * 1 to * 5 are as follows. * 1 Laroflex MP-45: Vinyl chloride-vinyl isopropyl ether copolymer manufactured by BASF, Germany * 2 Bryolite S-5B: Styrene-butadiene copolymer manufactured by Goodyear, USA * 3 VACH: Polychlorinated by UCC, USA Vinyl resin * 4 TBT acrylic copolymer solution: Produced as follows. That is, 40 parts by weight of a mixture of 65 parts by weight of tributyltin methacrylate and 35 parts by weight of methyl methacrylate was dissolved in 60 parts by weight of xylene in a reaction vessel equipped with a means capable of heating and cooling, and 0.35 parts by weight of peroxide was added thereto. Benzoyl was added. In order to control the temperature rise due to the exotherm, the temperature of the solution was gradually raised under reflux to a final temperature of 110 ° C. over 10 hours using cooling means. The final solution viscosity was 4.5 poise at 25 ° C.

* 5 ZDMC: Bis- (dimethyldithiocarbamate) zinc

[0038]

[Table 2]

An antifouling test was conducted on each of the obtained coating compositions. The antifouling test was carried out by coating each coating composition with anticorrosion coating (commercial ship bottom No. 1 paint based on coal tar / vinyl chloride resin) having a dry film thickness of 60 on a 100 × 300 mm test steel plate. Approximately 80 μm, apply twice, dry for 4 hours, dip to a depth of 1 m in the sea with a test bar, and attach the amount of animals such as barnacles, cerpra and plants such as Ulva and Aonori to the area Was examined and evaluated by visual observation.

Table 3 shows the changes in the amount of attached organisms, and Table 4 shows the changes in the amount of attached slime. Slime is a generic term for viscous membranes of various underwater bacteria and metabolites of bacteria, diatoms, and when they adhere, they will enter the spores of sea lettuce, Aonomori, or barnacle larvae and promote the propagation of contaminated organisms. Therefore, the antifouling paint must have excellent slime resistance.

[0041]

[Table 3]

[0042]

[Table 4]

As is clear from Tables 3 and 4, the antifouling agent for paint of the present invention shows remarkably good results as compared with Comparative Examples. In particular, it is extremely effective in preventing slime adhesion.

[0044]

As described in detail above, the antifouling agent for paints of the present invention exhibits a good antifouling effect against all aquatic adherent organisms and is excellent in long-term sustainability of its antifouling activity, especially in the sea. It has a very high antifouling effect against slime and is industrially extremely useful.

The isothiazolone compound, which is an active ingredient, requires caution in handling due to its skin irritation. However, the inclusion environment improves the working environment and enhances the safety.

Moreover, the clathrate compound according to the present invention has no adverse effect on the storage stability of the paint, such as viscosity increase and deterioration of the paint when it is made into a paint, and has high safety, thus improving workability and less environmental pollution. . Furthermore, since the antifouling paint using the antifouling agent for paints of the present invention is not corrosive to materials, it can be effectively used particularly without adversely affecting steel, light alloy, concrete vessels and underwater structures. You can

Claims (1)

[Claims] 1. An antifouling agent for paints, which comprises an inclusion compound of an isothiazolone compound and 5,5′-dichloro-2,2′-dihydroxydiphenylmethane.