JPH06340511A - Antifouling agent against marine organism - Google Patents

Abstract

PURPOSE:To obtain an antifouling agent against marine organism functioning as an antifouling active ingredient for an antifouling coating compound, an antifouling agent for fishing nets, etc., or an elution adjustor of an antifouling active ingredient. CONSTITUTION:This antifouling agent for marine organism contains a metal salt of an organic acid having 80-3,000ppm water solubility, preferably 7-13C saturated aliphatic monocarboxylic acid having 250-400 acid value (e.g. octylic acid, octanoic acid or undecanoic acid). A metal belonging to the group Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, VIa, VIb, VIIa or VIII is preferable as the metal of the metal salt and, for example, Cu, Zn, Ni, Mn, etc., may be cited as the metal. Since the antifouling agent is hydrolyzed in a wide pH range, a metal ion is eluted in a contaminated sea area at pH4-7 and further organic acids formed in the surface of the metal salt are dissolved in sea water, thus the agent shows excellent antifouling properties for a long period of time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marine antifouling agent which functions as an antifouling active ingredient such as an antifouling paint or a fishing net antifouling agent, or an elution control agent for an antifouling active ingredient.

[0002]

2. Description of the Related Art On the bottom of a ship, long-term oils and fats, vinyl chloride resins, chlorinated rubber resins, etc. are used as vehicles, and rosin is used as an elution control agent for antifouling active ingredients. Organic and inorganic antifouling active ingredients (for example: What was made into a paint together with copper oxide) was used as an antifouling paint, but it was difficult to adjust the elution of the antifouling active ingredient, so there was a problem in long-term antifouling properties. Therefore, as a result of the demand for better antifouling properties, an antifouling paint using a trialkyltin polymer compound as a vehicle was developed, and the paint can maintain the antifouling property by elution amount of the antifouling active ingredient. The antifouling property is excellent because it can be suppressed to the lowest level and a certain amount can be eluted over a long period of time. Moreover, this vehicle hydrolyzes in a slightly alkaline atmosphere in seawater,
It is known that the coating film becomes smooth and the seawater friction resistance of the ship is reduced to contribute to the reduction of fuel consumption. However, the workability is poor due to strong irritation when painting the bottom of the ship and antifouling treatment of fishing nets. Further, when the treated product is immersed in seawater, it has been found that marine pollution due to the eluted organic tin has a problem such as an adverse effect on the human body due to accumulation in seafood, and its use is regulated worldwide. As a result, it replaces the antifouling paint using the trialkyltin polymer compound as the vehicle.
A self-polishing antifouling paint having a long-term antifouling property is desired, and is disclosed in Japanese Patent Publication No. 1-450501 and JP-A-63-128084.
Are known. However, all of them are intended to provide a hydrolyzable coating vehicle having a metal bond at the end of the resin, and the antifouling property of the resin itself is not practical. Therefore, when the resin is used for antifouling paints, other antifouling active ingredients must be used.

Further, recently, an anti-adhesion agent for marine organisms has been proposed in which a metal salt of copper naphthenate, copper stearate or the like is dissolved or dispersed in an ethylene vinyl acetate copolymer, a chlorinated rubber resin, a synthetic rubber or the like (special feature: Kaihei 1-149702). However, in this case, the active ingredient is hydrolyzed to elute copper ions, and the organic acid formed on the surface has a poor solubility in seawater, so that there is a drawback that the elution of copper ions as an antifouling active ingredient is hindered. This tendency is remarkable when a ship anchors in a polluted sea area where the pH is 4 to 7 where organisms are most likely to adhere.

[0004]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide an antifouling agent which does not contain an organic tin compound, does not cause environmental pollution, and in which the active ingredient is eluted even in a weakly acidic polluted sea area having a pH of 4 to 7, and which has a long term antifouling property. To do.

[0005]

As a result of intensive studies to solve the above-mentioned drawbacks, the present invention shows that the solubility in water is 80 to 3
It was found that the metal salt of organic acid of 000 ppm is hydrolyzed in the entire pH range of seawater to elute metal ions, and the organic acid itself which is hydrolyzed and formed on the surface is dissolved regardless of the pH of seawater. Further, in the case of an antifouling paint using a vehicle such as fats and oils, vinyl chloride resin, chlorinated rubber resin, etc., by dissolving and mixing the required amount of the metal salt of the present invention in the resin, or dispersing in the resin, They have found that it is possible to make an antifouling paint that exhibits excellent antifouling properties without using the cuprous oxide or rosin that was always used, and it has been completed. That is, the present invention is a marine organism antifouling agent containing a metal salt of an organic acid having a solubility in water of 80 to 3000 ppm.

The antifouling agent of the present invention is characterized in that it is hydrolyzed in all pH sea areas, and metal ions are eluted and the organic acid remaining on the surface is also dissolved in water. Therefore, when it is used for an antifouling paint, it is hydrolyzed by the weak alkalinity of seawater to elute the metal ions and also dissolve the formed organic acid, so that the state in which the active ingredient is always eluted is maintained. In addition, even in sea areas with a pH of 7 or less, metal ions are eluted and the generated organic acid is also dissolved in water, so active ingredients are eluted even in contaminated areas such as harbors where organisms are most likely to attach and where organisms are most likely to attach. And exhibits an antifouling effect. Further, as described above, the conventional ordinary antifouling paint is a binder (vehicle) resin,
The antifouling agent of the present invention consists of an antifouling active ingredient, an elution control agent, etc., but since the antifouling active ingredient and the elution control agent have the same performance as described above, in particular, another antifouling active ingredient and It is not necessary to use an elution regulator, but, of course, these may be further added and used.

The organic acid used in the present invention is not limited as long as the organic acid alone has a solubility in water of 80 to 3000 ppm, but it has 7 to 13 carbon atoms and an acid value of 2 in particular.
50-400 saturated aliphatic monocarboxylic acids are preferred,
Examples thereof include isooctanoic acid, isononanoic acid, isodecanoic acid, isoundecanoic acid, isotridecanoic acid, octylic acid, versatic acid, n-heptanoic acid and n-nonanoic acid. When the solubility in water exceeds 3000 ppm, the hydrophilicity of the organic acid itself is so strong that it dissolves in water too quickly, making it difficult to control the elution of the entire active ingredient and shortening the antifouling period. On the other hand, if the solubility in water is less than 80 ppm, the organic acid produced is slow to dissolve even if the metal ions are hydrolyzed and the metal ions are eluted, so the elution concentration of the antifouling active ingredient is low and the antifouling property is low. become worse. The solubility of the organic acid in water of the present invention means the concentration of the organic acid in the saturated aqueous solution of the organic acid.

The metal of the metal salt used in the present invention is not particularly limited, but in particular, the periodic table Ib, IIa, IIb, IIIa,
Group IIIb, IVa, IVb, Va, VIa, VIb, VIIa and VIII are preferred, for example Cu, Zn, Ni, M
n and the like. In the present invention, when the antifouling agent of the present invention is used for the purpose of adjusting the elution property of the antifouling active ingredient, there is no limitation on the type of metal, and metal salts can be used alone or in combination. . At this time, an elution control agent such as rosin, which has been conventionally used, is not particularly required, but can be used in combination as necessary. At this time, the amount of antifouling active ingredient such as cuprous oxide can be reduced. Furthermore, metal salts of organic acids other than those of the present invention can be used in combination for the purpose of adjusting dissolution. When the antifouling agent of the present invention is used as an antifouling active ingredient, salts of Cu, Zn, Ni and the like are desirable, but not limited to these, other metal salts alone or in combination with several kinds of metal salts. You can At this time, if necessary, an organic antifouling active ingredient that has been conventionally used and an inorganic antifouling active ingredient such as cuprous oxide can be used in combination. The method for producing a metal salt of an organic acid of the present invention is not particularly limited, and a metathesis method of reacting an alkali salt of an organic acid with an aqueous solution of a metal salt, a melting method of reacting a metal oxide with an organic acid, a metal powder and an organic acid Although a direct method of directly reacting is possible, it is desirable to select it based on the reactivity depending on the kind of metal salt and the reactivity of organic acid.

When using the antifouling agent of the present invention, an oily varnish, a chlorinated rubber resin varnish, a vinyl chloride resin varnish,
It can be used by dissolving it in a vehicle such as an acrylic resin varnish in a necessary amount or by dispersing it with other antifouling active ingredients, pigments and the like. Further, when the compatibility with the resin varnish is poor, it is not necessary to dissolve the resin varnish, and it is possible to use it by dispersing it in the resin varnish by increasing impurities to reduce the solvent solubility. Antifouling paints using the antifouling agent of the present invention are oils and fats, chlorinated rubber resin varnishes, vinyl chloride resin varnishes,
Along with vehicles such as acrylic resin varnish, extender pigment,
A color pigment, various solvents, and various additives are blended, and these are prepared by uniformly mixing and dispersing with a dispersing machine such as a ball mill or a sand mill according to a conventional method for producing a coating material.

[0010]

【Example】

Test Example 1 Based on the formulation (parts by weight) shown in Table 1, a ball mill was used to mix and disperse the coating material for 5 hours by a usual method to prepare a coating material, which was air sprayed onto a vinyl chloride plate of 8 cm × 20 cm. The coating was applied so that the dry film thickness was 100 μm. The obtained test piece was placed in Toba Bay, Mie Prefecture from October 1991
It was immersed until April 993, and during that period, the state of attachment of organisms was observed regularly. The results are shown in Table 2, and the antifouling paints of Examples 1 to 5 showed good antifouling properties for a long time.

[0011]

[Table 1]

(Note 1) Sample organic acid metal salt Metal content (% weight) Solubility of organic acid (PPM) Copper octylate: Cu 18% 1360 Copper octanoic acid: Cu 18% 1430 Copper undecanoic acid: Cu 14% 170 Octylic acid Tin: Sn 28% 1360 Zinc octylate: Zn 22% 1360 Copper rosinate: Cu 8.5% 70 Copper naphthenate: Cu 10% 50 Copper stearate: Cu 10% 25 Copper heptanoic acid: Cu 19% 3580 (Note 2) Test organic acid The amount of the metal salt used was adjusted so that the metal content in the coating film was constant.

[0013]

[Table 2]

(Note 1) Evaluation criteria (adhesion area%) ◎: 0 to 5% ○: 6 to 20% △: 21 to 40% ×: 41 to 70% XX: 71 to 100%

Test Example 2 The same test piece as in Test Example 1 was prepared and the elution of copper ions was examined under the following conditions. The results are shown in Table 3, and the elution of copper ions from the antifouling paints of Examples 1 to 5 was stable for a long period of time. (Measurement conditions) The same as in Test Example 1, immersed, pulled up at regular intervals, briefly rinsed the surface with artificial seawater, and immersed in a glass container containing 2 liters of artificial seawater at 20 ° C. for 24 hours at 20 ° C. for copper ions in the artificial seawater. Was measured by the atomic absorption method.

[0016]

[Table 3]

(Note) Copper ion elution amount: μg / cm ² / day

Test Example 3 Based on the formulation (parts by weight) of the coating composition shown in Table 4, a ball mill was used to mix and disperse the coating composition for 5 hours by a conventional method to prepare a coating composition, which was then air-coated on a vinyl chloride plate of 8 cm × 20 cm. It was applied by spraying so that the dry film thickness was 100 μm.
The obtained test piece was immersed in Toba Bay, Mie Prefecture from October 1991 to April 1993, and during that period, the adhered state of organisms was observed regularly. The results are shown in Table 5, and the antifouling paints of Examples 6 to 11 had the same results as the conventional commercially available organotin antifouling paints.

[0019]

[Table 4]

(Note 1) Evaluation Criteria (Adhesion Area%) Same as Test Example 1 (Note 2) (*) Commercial Antifouling Paint Using Organotin

[0021]

[Table 5]

(Note 1) Evaluation Criteria (Adhesion Area%) Same as Test Example 1

[0023]

Since the antifouling agent of the present invention is hydrolyzed in all pH sea areas, metal ions are eluted even in contaminated sea areas having a low pH of 4 to 7, and the organic acid formed on the surface is also dissolved in sea water. Therefore, when used in an antifouling paint, it can be used alone or in combination with a conventional antifouling active ingredient such as cuprous oxide, or can be substituted for rosin. Therefore, it is possible to produce an antifouling paint having a long-term antifouling property by combining with an appropriate resin and an antifouling active ingredient.

Claims (3)

[Claims] 1. A marine biological antifouling agent containing a metal salt of an organic acid having a solubility in water of 80 to 3000 ppm. 2. The marine antifouling agent according to claim 1, wherein the organic acid is a saturated aliphatic monocarboxylic acid having 7 to 10 carbon atoms. 3. The metal of the organic acid metal salt is a periodic table Ib or II.
a, IIb, IIIa, IIIb, IVa, IVb, Va, VIa, VIb
The antifouling agent for marine organisms according to claim 1 or 2, which belongs to Group VIIa or VIII.