JP2009235373A - Clear type antifouling paint composition containing stability improved triphenylboron compound, for fishing net - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clear type antifouling paint composition for a fishing net, the antifouling paint composition containing both a triphenylboron compound and tetraethylthiuramsulphide, in which the decomposition of the triphenylboron compound is controlled by a means for generating no precipitation, and the antifouling activity of the composition remaining even in a long term storage. <P>SOLUTION: The clear type antifouling paint composition for a fishing net comprises (A) a paint film forming resin; (B) as antifouling agents, (b1) a triphenylboron-amine complex (for example, triphenyl [3-(2-ethylhexyloxy) propylamine] boron and/or triphenyl (n-octadecyl) amineboron), and (b2) tetraethylthiuramsulphide; and (C) an isothiazole compound (for example, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-on) as a decomposition controlling agent for (b1) the triphenylboron-amine complex. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a clear type antifouling coating composition containing a triphenylboron compound (triphenylboron / amine complex) and tetraethylthiuram disulfide and suitable for fishing nets. More specifically, the present invention relates to a clear antifouling paint composition for fishing nets containing the above-mentioned components having improved stability (degradation of triphenylboron compound during storage is suppressed).

  Conventionally, boron compounds such as triphenylboron and diphenylmethylboron have been widely used as antifouling agents in antifouling coating compositions for fishing nets. These boron compounds are easily dissolved in organic solvents such as xylene, toluene, etc., and do not require agitation before net dyeing work and can be easily carried out. It is characterized by being used for manufacturing products.

  Among boron compounds, the antifouling effect is best with the diisopropylmethylboron 4-isopropylpyridine complex, but this compound has low solubility in xylene, so the antifouling coating composition is a clear type. In such a case, it is impossible to add an amount sufficient to exhibit the antifouling property. For this reason, triphenyl [3- (2-ethylhexyloxy) propylamine] boron and triphenyl (n-octadecyl) amineboron, which have high solubility in organic solvents such as xylene, are the most clear antifouling coating compositions. Widely used.

  In addition, the above two types of triphenylboron compounds alone are insufficient in antifouling properties in highly polluted sea areas, so other antifouling agents are often used together, and tetraethylthiuram disulfide is widely used as an antifouling agent for that purpose. Have been used. Tetraethylthiuram disulfide also has high solubility in organic solvents, is highly safe among alkylthiuram disulfides, has a good anti-fouling effect on aquatic organisms, and has a synergistic antifouling effect when used in combination with boron compounds. It has the property of increasing.

  Thus, clear type antifouling paint compositions for fishing nets using a triphenylboron compound and tetraethylthiuram disulfide in combination are widely used. However, as will be described in detail later, when such an antifouling coating composition is used after storage for a while, the antifouling activity of the resulting antifouling coating film tends to be reduced, and the original antifouling performance is fully exhibited. Had the problem of not being.

So far, for example, the following has been proposed as an antifouling paint composition containing an antifouling agent such as triphenylboron.
Japanese Patent Application Laid-Open No. 08-295608 (Patent Document 1) discloses an organic solvent-dissolved fishing net antifouling agent which contains a triphenylboron alkylamine complex compound and may further contain a tetraalkylthiuram disulfide. ing.

  JP-A-11-199414 (Patent Document 2) contains a triphenylboron rosinamine salt or a triphenylboron alkylamine salt, a predetermined polyether silicone, a resin and an organic solvent, and further contains tetraethylthiuram disulfide, 4, Fishing net antifouling agents that may contain organic antifouling agents such as 5-dichloro-2-n-octyl-4-isothiazolin-3-one are disclosed.

  Japanese Patent Application Laid-Open No. 11-322863 (Patent Document 3) discloses a marine antifouling agent containing a triphenylboron / alkoxy group-containing amine complex compound (such as triphenylborane / 3- (2-ethylhexyloxy) propylamine complex). It is also described that the antifouling property is remarkably enhanced when a tetraalkylthiuram disulfide is further added thereto. Further, isothiazolone antifouling agents and the like are exemplified as an antifouling component that can be appropriately used in combination with this composition.

  In JP-A-10-182322 (Patent Document 4), triphenylborane or an alkali metal hydroxide adduct thereof and a higher aliphatic amine are reacted in advance, and the reaction product is blended in an antifouling paint. It is described to improve the performance. Further, examples of the antifouling component that can be appropriately used in the composition include tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the like.

  In JP-A-10-182323 (Patent Document 5), triphenylborane or an alkali metal hydroxide adduct thereof and a specific higher aliphatic secondary or tertiary amine or a salt thereof are used as antifouling active ingredients. Marine antifouling agents contained (for fishing net antifouling agents and antifouling paints) are disclosed, and this antifouling agent exhibits a so-called synergistic antifouling effect and continues its antifouling effect It is described that it can be made. Further, examples of the antifouling component that can be appropriately used in the composition include tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the like.

  However, in any of the inventions described in Patent Documents 1 to 5, when a boron compound (such as triphenylboron) and a tetraalkylthiuram disulfide are used in combination, the decomposition of the boron compound progresses during storage, resulting in antifouling activity. It is not recognized that the original antifouling performance will not be fully exhibited due to the decrease, and no means for solving this problem is specifically presented.

Japanese Patent Application Laid-Open No. 10-072202 (Patent Document 6) discloses a seawater in which an antifouling active ingredient comprising pyridine-triphenylborane and a higher aliphatic mono- or polyamine having an amino group is dissolved in an organic solvent. A raw adherent antifouling composition (for fishing net antifouling agents, antifouling paints) is disclosed. And this antifouling composition is stable and does not produce a precipitate (triphenylboron precipitate), and the solubility of pyridine-triphenylborane in an organic solvent is improved, so it is used as an antifouling agent for fishing nets. In this case, it is described that the mesh can be uniformly dyed in the dyeing tank. Examples of known antifouling components that can be used in combination with this composition include tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the like. Further, the higher aliphatic mono- or polyamines (diamine, triamine, etc.) having the amino group are represented by the formula R ^1- [N (R ² ) (CH ₂ ) _a ] _b -NH ₂ [wherein R ¹ is β- A saturated or unsaturated aliphatic hydrocarbon group having 8 to 28 carbon atoms which may be substituted with a hydroxy group (which may have an alkoxy group), R ² is a hydrogen atom or — (CH ₂ ) _{a = 1 -6} NH _2, a is an integer from 1 to 6, b is 0 to 4 integer. It is a compound represented by this.

Japanese Patent Application Laid-Open No. 10-167914 (Patent Document 7) discloses marine-adherent organism antifouling containing pyridine-triphenylborane and a higher aliphatic secondary or tertiary amine or a salt thereof as an antifouling active ingredient. A composition is disclosed. It is described that when this antifouling composition is applied to a fishing net, a ship bottom or the like, a so-called synergistic antifouling effect is exhibited and the antifouling effect can be maintained. Examples of known antifouling components that can be used in combination with this composition include tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the like. The higher aliphatic secondary or tertiary amine is represented by the formula N (R ¹ ) (R ² ) (R ³ ), wherein R ¹ , R ² and R ³ are substituted with one hydroxyl group or alkoxy group. Or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 28 carbon atoms, wherein one of R ^{1 to} R ³ may be a hydrogen atom. Specifically, di-n-coconut alkylamine, dimethyl beef tallow alkylamine, di-n-octylamine, dimethylhexadecylamine and the like are used.

  However, in these inventions, an amine compound is used in combination to dissolve pyridine-triphenylborane, which is not soluble in general-purpose organic solvents such as xylene and toluene, in these solvents (Patent Document 6), or pyridine-triphenyl. In order to further synergistically improve the antifouling property by borane, an amine compound is used in combination, and the above-mentioned problems in the case of using a boron compound (such as triphenylboron) and a tetraalkylthiuram disulfide together There is no specific disclosure of means for solving this.

Further, JP-A-2004-244395 (Patent Document 8) discloses a composition containing (4-isopropylpyridinio) methyldiphenylboron (IPMB) and a primary alkylamine having 8 to 18 carbon atoms (in water An antifouling composition) is disclosed. IPBM usually has low stability when dissolved in a solvent or in a mixed system such as paint. However, the above composition is excellent in stability and maintains its effect even when stored for a long period of time. It is described that it is possible to prevent the attachment of organisms over a long period of time when used as a paint. Examples of known antifouling components that can be used in combination with this composition include tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the like.

  Examples of the primary alkylamine include n-octylamine, 2-ethylhexylamine, n-dodecylamine, n-octadecylamine, and the like. These amines are usually 0.5 mol per 1 mol of IPMB. It is added at a ratio of ˜2 mol, and if this ratio is less than 0.5 mol, the antifouling effect after long-term storage is lowered, and if it exceeds 2 mol, further improvement in stability and antifouling property cannot be expected. Is described.

  However, the invention described in Patent Document 8 aims to increase the solubility of the diphenylboron compound in an organic solvent in order to eliminate the need for stirring before net dyeing, particularly considering the use as an antifouling agent for fishing nets. And an antifouling composition having a stable property with no precipitation over a long period of time by adding an amine compound. Again, when a triphenylboron compound and a tetraalkylthiuram disulfide as described above are used in combination, There is no specific disclosure about the problem and the means for solving it.

  In JP 2000-143417 A (Patent Document 9), an underwater antifouling paint containing a compound having a triphenylboron skeleton (fishnet antifouling agent, ship bottom antifouling paint, etc.) has a -CONH-structure in the molecule. And at least one compound selected from compounds having a heterocycle having 3 or more nitrogen atoms in the molecule (for example, tolyltriazole, 3- (N-salicyloyl) amino-1,2,4-triazole , 1,2,3-benzotriazole) is disclosed. In such an underwater antifouling paint, cuprous oxide or rhodan copper is further blended, and even when the triphenylboron compound comes into contact with these, the triphenylboron skeleton is almost decomposed by the action of the predetermined compound. In addition, it is described that an underwater antifouling paint can exhibit an excellent antifouling effect even after long-term storage. Examples of known antifouling components that can be used in combination with this composition include tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the like.

  However, the invention described in Patent Document 9 is intended to stabilize the triphenylboron compound in the coating composition in which the copper compound is used in combination. There is no specific disclosure about the problems when alkylthiuram disulfides are used in combination and the means for solving them.

In short, the invention described in any of the above-mentioned patent documents also has a problem that the antifouling performance is impaired due to decomposition of the triphenylboron compound during storage in the antifouling coating composition using both the triphenylboron compound and the tetraalkylthiuram disulfide. It is not intended to solve the problem, and by adding an isothiazole compound to the antifouling coating composition, the above problem can be solved without causing precipitation that impedes the netting of fishing nets. However, a specific technical idea that an antifouling coating film excellent in long-term antifouling properties can be formed is not disclosed.
Japanese Patent Laid-Open No. 08-295608 JP 11-199414 A Japanese Patent Laid-Open No. 11-322863 Japanese Patent Laid-Open No. 10-182322 Japanese Patent Laid-Open No. 10-182323 JP-A-10-072202 Japanese Patent Laid-Open No. 10-167914 JP 2004-244395 A JP 2000-143417 A

  When the triphenylboron compound and tetraethylthiuram disulfide are used in combination as an antifouling agent for the clear antifouling paint composition, the present inventors have reduced the antifouling activity of the coating film formed from this antifouling paint. I noticed the above-mentioned problem that the antifouling performance tends to be insufficient.

  Furthermore, the present inventors have noticed a problem that a triphenylboron compound is decomposed during storage in an antifouling paint composition using a triphenylboron compound and tetraethylthiuram disulfide in combination.

Furthermore, the present inventors have noticed a problem that heterocyclic amines that suppress the decomposition of the triphenylboron compound cause precipitation.
Under such circumstances, the present invention is an antifouling coating composition containing a triphenylboron compound and tetraethylthiuram disulfide, wherein the decomposition of the triphenylboron compound is suppressed by a means that does not produce a precipitate, and a long-term An object of the present invention is to provide a clear antifouling paint composition suitable for fishing nets, which has improved antifouling activity stability during storage.

  As a result of intensive research, the present inventors have further decomposed the triphenylboron / amine complex by adding an isothiazole compound to the antifouling coating composition containing the triphenylboron / amine complex and tetraethylthiuram disulfide. As a result, the inventors have found that it is possible to satisfy the requirement of clearness and to satisfy the improvement of antifouling property because precipitation is not caused and precipitation does not occur, and the present invention has been completed.

  That is, the clear antifouling coating composition for fishing nets of the present invention comprises (A) a film-forming resin, (B) (b1) triphenylboron / amine complex as an antifouling agent, and (b2) tetraethylthiuram disulfide. And (C) an isothiazole compound as a decomposition inhibitor of the triphenylboron / amine complex (b1).

This antifouling coating composition preferably contains the isothiazole compound (C) in a proportion of 0.01 to 10 mol with respect to 1 mol of the triphenylboron / amine complex (b1). Also,
The triphenylboron / amine complex (b1) is preferably triphenyl [3- (2-ethylhexyloxy) propylamine] boron and / or triphenyl (n-octadecyl) amineboron, and the isothiazole compound (C) is 4 , 5-dichloro-2-n-octyl-4-isothiazolin-3-one.

  In addition to the components (A), (b1), (b2) and (C), the clear antifouling paint composition for fishing nets of the present invention further comprises (b2) a triphenylboron / amine complex (b1 ) And tetraethylthiuram disulfide (b2), (D) oxyalkylene group-containing chain organopolysiloxane, and (E) polybutenes, paraffins, petroleum jelly, or dialkyl sulfide compounds It is also preferable to contain one or more components selected from the group consisting of the above plastic resins.

For example, as the organic antifouling agent (b3), N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino S triazine, chloro Methyl-n-octyl disulfide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, N, N′-dimethyl-N′-tolyl- (N-fluorodichloromethylthio) sulfamide, 2 , 3-dichloro-N- (2 ′, 6′-diethylphenyl) maleimide and at least one selected from the group consisting of 2,3-dichloro-N- (2′-ethyl-6′-methylphenyl) maleimide Preferably contains seeds;
The oxyalkylene group-containing chain organopolysiloxane (D) is represented by the following formula [Ia] and has a hydrophilic / lipophilic balance (HLB: 5% by weight of oxyethylene in the oxyalkylene group-containing chain organopolysiloxane). The ratio of 0.5 to 200 parts by weight of the oxyalkylene group-containing chain organopolysiloxane having a divided value of 2 to 12 with respect to 100 parts by weight of the film-forming resin (A) (solid content converted value) Is preferably contained in;

（式［Iａ］中、Ｘ¹、Ｘ²、Ｘ³はそれぞれ独立にポリエーテル基：-Ｒ-Ａ-(Ｒ³Ｏ)_n-Ｒ⁴
［Ｒは炭素数１〜５のアルキレン基、Ａは単結合または酸素原子、Ｒ³は炭素数１〜５の
アルキレン基、Ｒ⁴は炭素数１〜５のアルキル基または水素を示し、ｎは繰返し単位数を
示す。］または炭素数１〜５のアルキル基を示し、これらＸ¹、Ｘ²、Ｘ³のうちの少なく
とも１個は当該ポリエーテル基であり、Ｒ²は炭素数１〜３のアルキル基を示し、ｒおよ
びｍはそれぞれ繰返し単位総数を示し、繰返し単位［−Ｓｉ(Ｒ²)₂Ｏ−］および［−Ｓｉ(Ｒ²)(Ｘ¹)Ｏ−］の結合順序は任意である。)

(In the formula [Ia], X ¹ , X ² and X ³ are each independently a polyether group: —R—A— (R ³ O) _n —R ⁴
[R represents an alkylene group having 1 to 5 carbon atoms, A represents a single bond or an oxygen atom, R ³ represents an alkylene group having 1 to 5 carbon atoms, R ⁴ represents an alkyl group having 1 to 5 carbon atoms or hydrogen, and n represents Indicates the number of repeating units. Or an alkyl group having 1 to 5 carbon atoms, at least one of these X ¹ , X ² and X ³ is the polyether group, R ² represents an alkyl group having 1 to 3 carbon atoms, Each of r and m represents the total number of repeating units, and the bonding order of the repeating units [—Si (R ² ) ₂ O—] and [—Si (R ² ) (X ¹ ) O—] is arbitrary. )

  As the component (E), one or more plastic resins of polybutenes, paraffins, petrolatums, or dialkyl sulfide compounds represented by the formula [IV] are used as a film-forming resin (A) (solid content) (Converted value) It is preferable to contain in the ratio of 5-100 weight part with respect to 100 weight part.

R ^3d- (S) _n -R ^3e [IV]
(In the formula [IV], a plurality of R ^3d and R ^3e may be the same or different from each other, and each represents a linear or branched alkyl group having 1 to 20 carbon atoms, and n is 1 to 20) Indicates an integer.)
Moreover, it is preferable that the solvent component used for the clear antifouling paint composition for fishing nets of the present invention contains 1% by weight or more of an alcohol solvent and / or an ester solvent.

  A fishing net is immersed in the clear antifouling paint composition for a fishing net of the present invention, and the antifouling coating composition is impregnated inside the fishing net and adhered thereto. A fishing net that demonstrates its fouling performance is obtained.

  In the present invention, the isothiazole compound blended in the antifouling coating composition functions as a decomposition inhibitor when the triphenylboron / amine complex and tetraethylthiuram disulfide are combined, so that the triphenylboron / amine complex is stabilized and stored. Decrease in antifouling activity can be suppressed. In addition, at this time, no unfavorable precipitation or the like occurs for the clear type antifouling coating composition for fishing nets, and the netting workability of fishing nets is excellent. In particular, the effect of the isothiazole compound as a decomposition inhibitor is characterized in that it is exhibited even when the amount is significantly lower than the general amount when used as an antifouling agent. According to the present invention, a clear antifouling paint composition that is extremely useful for fishing nets can be formed, which can form a coating film that permanently exhibits excellent antifouling performance against a wide range of aquatic organisms even after storage. become able to.

  In the present invention, those listed as the respective components of the antifouling coating composition may be used alone or in combination of two or more unless otherwise specified. In addition, in the definition of the blending amount based on parts by weight, unless otherwise specified, components such as the film-forming resin (A) that are generally dissolved and dispersed in a solvent have a solid content (non-volatile content). ) Weight is used. In addition to the components described below, other components can be added to the antifouling coating composition of the present invention as necessary within a range not inhibiting the effects of the present invention.

− Antifouling paint composition components −
(A) Film-forming resin As the film-forming resin (A) in the present invention, a film-forming property blended in a known antifouling paint composition, particularly a clear antifouling paint composition for fishing nets. Resin can be used. For example, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, phenol resin, synthetic rubber, silicone rubber, silicone resin, petroleum resin, rosin ester resin, rosin soap, rosin, etc. These film-forming resins may be used alone or in combination of two or more. Among these, acrylic resins are particularly preferable from the viewpoints of flexibility and antifouling properties when applied to fishing nets.

  The blending amount of the coating film-forming resin (A) in the antifouling coating composition of the present invention may be the same as that of a known antifouling coating composition, for example, 20 to 70% by weight based on the entire solid content. Or it is preferable to set it as 5 to 30 weight% with respect to the whole antifouling coating material composition containing a solvent.

(B) Antifouling agent (b1) Triphenylboron / amine complex The triphenylboron / amine complex (b1) in the present invention is a known antifouling coating composition, particularly a clear antifouling coating composition for fishing nets. The compounded triphenylboron / amine complex can be used.

However, from the viewpoint of making the antifouling coating composition of the present invention a clear type, a compound that precipitates without dissolving in the organic solvent blended in the composition, such as triphenylboron insoluble in xylene, toluene, etc. The use of pyridine and the like should be avoided. As long as these conditions are satisfied, the amine that forms a complex in the triphenylboron compound may be any of an aliphatic amine, an alicyclic amine, an aromatic amine, a heterocyclic amine, etc., and a primary amine, Either a secondary amine or a tertiary amine may be used. For example, the following amine represented by the following formula [II] can be mentioned:

Propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine, 3- (2-ethylhexyl) propylamine, 3- (2-ethylhexyloxy) propyl Primary amines such as amines, anilines, toluidines;
Secondary amines such as dibutylamine, dihexylamine, dioctylamine, didecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, diphenylamine;
Tertiary amines such as tripropylamine, trihexylamine, trioctylamine, tridecylamine, tridodecylamine, tritridecylamine, tritetradecylamine, trihexadecylamine, trioctadecylamine, triphenylamine;
3-ethoxypropylamine, 3-butoxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3-lauryloxypropylamine, 3-stearyloxypropylamine, 4- (2-ethylhexyloxy) butylamine, 4-lauryl Alkoxy group-containing amines such as oxybutylamine, 8-ethoxyoctylamine, 8- (2-ethylhexyloxy) octylamine, 2-ethylhexyloxyphenylamine and lauryloxyphenylamine.

式［II］中、ｔは０、１、または２であり、Ｒは、直鎖状または分岐状の炭素数３〜３０のアルキル基か、または式−Ｒ¹−Ｏ−Ｒ²（Ｒ¹は炭素数１〜８の直鎖状もしくは分枝
状のアルキレン基またはフェニレン基を表し、Ｒ²は炭素数１〜１８の直鎖状または分枝
状のアルキル基を表す。）で表されるアルコキシ基である。

In the formula [II], t is 0, 1 or 2, and R is a linear or branched alkyl group having 3 to 30 carbon atoms, or a formula —R ¹ —O—R ² (R ¹ Represents a linear or branched alkylene group having 1 to 8 carbon atoms or a phenylene group, and R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms. An alkoxy group;

  Of these, a complex of triphenylboron and a primary amine is preferable because of its relatively high stability. In particular, the triphenylboron / amine complex (b1) of the present invention is triphenyl [3- (2-ethylhexyloxy) propylamine] boron in terms of antifouling properties, stability, and solubility in xylene and toluene. And triphenyl (n-octadecyl) amine boron are preferred.

  The blending amount of the triphenylboron / amine complex (b1) into the antifouling coating composition of the present invention is determined in consideration of the antifouling property of the coating, the physical properties of the coating, and the like. It is preferable to mix | blend in the ratio of 5-150 weight part with respect to 100 weight part, and it is more preferable to mix | blend in the ratio of 20-80 weight part.

(B2) Tetraethylthiuram disulfide Tetraethylthiuram disulfide (b2) blended in the antifouling coating composition of the present invention is a compound represented by the following formula [III] known as an antifouling agent.

  The amount of tetraethylthiuram disulfide (b2) to be added to the antifouling coating composition of the present invention is determined by considering the antifouling properties of the coating and the influence on the decomposition of the triphenylboron / amine complex (b1). It is preferable to mix | blend in the ratio of 30-400 weight part with respect to 100 weight part of amine complexes (b1), and it is more preferable to mix | blend in the ratio of 0.5-10 mol.

(B3) Other antifouling agent The antifouling coating composition of the present invention includes a triphenylboron / amine complex blended in a known antifouling coating composition, particularly a clear antifouling coating composition for fishing nets. An organic antifouling agent (b3) soluble in an organic solvent other than (b1) and tetraethylthiuram disulfide (b2) may be further blended.

  Examples of the organic antifouling agent (b3) include N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino S triazine, Chloromethyl-n-octyl disulfide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, N, N′-dimethyl-N′-tolyl- (N-fluorodichloromethylthio) sulfamide, 2,3-dichloro-N- (2 ′, 6′-diethylphenyl) maleimide, 2,3-dichloro-N- (2′-ethyl-6′-methylphenyl) maleimide and the like are soluble in the solvent and It is preferable because of its excellent antifouling effect. In addition, although the compounding quantity of an organic antifouling agent (b3) should just be the same grade as about a well-known antifouling coating composition, it is 5-100 weight with respect to 100 weight part of film forming resin (A), for example. It is preferable to mix | blend in the ratio of a part.

(C) Isothiazole compound The isothiazole compound (C) to be blended in the antifouling coating composition of the present invention has an action of suppressing the decomposition of the triphenylboron / amine complex (b1) and stabilizing it for a long period of time. Although not particularly limited, a compound having an antifouling action is more desirable.

  Examples of such isothiazole compounds include 4,5 dichloro-2-n-octyl-4isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 2-methyl-4-isothiazoline. -3-one, 2-phenyl-1,2-benzisothiazol-3-one, 4-isothiazolin-3-one, 3-chloroisothiazole, 2-phenylisothiazol-3-one, 1,2-benz And isothiazoline-3-one, 2-phenyl-4-isothiazolin-3-one, and the like.

  Among these, 4,5dichloro-2-n-octyl-4isothiazolin-3-one is particularly preferable from the viewpoints of both the effect as a stabilizer and the effect of improving the antifouling property of the antifouling coating composition. This compound is commercially available, for example, from Rohm and Haas as trade name “Sine Nine 211”.

The blending amount of the isothiazole compound (C) in the antifouling coating composition of the present invention is determined by considering the effect of suppressing the decomposition of the triphenylboron / amine complex (b1) and the antifouling property. (B1) It is preferable to mix | blend in the ratio of 0.01-10 mol with respect to 1 mol, and it is more preferable to mix | blend in the ratio of 0.04-5 mol. The effect as a decomposition inhibitor of the isothiazole compound (C) is sufficient even if the amount is as small as 0.5 mol or less, further 0.1 mol or less with respect to 1 mol of the triphenylboron / amine complex (b1). To be demonstrated.

(D) Oxyalkylene group-containing chain organopolysiloxane In the present invention, the oxyalkylene group-containing chain organopolysiloxane (D) (also referred to as polyether (modified) silicone) is a known antifouling paint composition, particularly Although what is mix | blended with the clear type | mold antifouling paint composition for fishing nets can be used, for example, what is shown by following formula [Ia] is suitable.

式［Ｉa］中、Ｘ¹、Ｘ²、Ｘ³はそれぞれ独立にポリエーテル基：-Ｒ-Ａ-(Ｒ³Ｏ)_n-Ｒ⁴
［Ｒは炭素数１〜５のアルキレン基、Ａは単結合または酸素原子、Ｒ³は炭素数１〜５の
アルキレン基、Ｒ⁴は炭素数１〜５のアルキル基または水素を示し、ｎは繰返し単位数を
示す。］または炭素数１〜５のアルキル基を表し、これらＸ¹、Ｘ²、Ｘ³のうちの少なく
とも１個は当該ポリエーテル基である。上記ｎは１〜３０の整数である。上記ポリエーテル基としては、防汚塗料組成物の防汚性や、ポリエーテルシリコーン（Ｄ）と塗膜形成樹脂（Ａ）との相溶性などを考慮すると、末端がメトキシ基のポリエーテル基、特に-Ｃ₃Ｈ₆-Ｏ-(Ｃ₂Ｈ₄Ｏ)_n-ＣＨ₃、-Ｃ₂Ｈ₄-Ｏ-(Ｃ₃Ｈ₆Ｏ)_n-ＣＨ₃が好ましい。

In the formula [Ia], X ¹ , X ² and X ³ are each independently a polyether group: —RA— (R ³ O) _n —R ⁴
[R represents an alkylene group having 1 to 5 carbon atoms, A represents a single bond or an oxygen atom, R ³ represents an alkylene group having 1 to 5 carbon atoms, R ⁴ represents an alkyl group having 1 to 5 carbon atoms or hydrogen, and n represents Indicates the number of repeating units. Or an alkyl group having 1 to 5 carbon atoms, and at least one of these X ¹ , X ² and X ³ is the polyether group. N is an integer of 1-30. As the polyether group, considering the antifouling property of the antifouling coating composition and the compatibility between the polyether silicone (D) and the coating film forming resin (A), a polyether group having a methoxy group at the end, In particular, —C ₃ H ₆ —O— (C ₂ H ₄ O) _n —CH ₃ and —C ₂ H ₄ —O— (C ₃ H ₆ O) _n —CH ₃ are preferable.

R ² represents an alkyl group having 1 to 3 carbon atoms. A plurality of R ² may be the same as or different from each other, but all are preferably methyl groups (so-called polyether-modified polydimethylsiloxane).

r and m each represent the total number of repeating units, r is an integer of 1 to 7000, and m is an integer of 1 to 50. The bonding order of the repeating units [—Si (R ¹ ) ₂ O—] and [—Si (R ¹ ) (X ¹ ) O—] is arbitrary. The molecular weight of such polyether silicone is usually 1,000 to 50,000, preferably about 3,000 to 10,000.

  The hydrophilic / lipophilic balance of the oxyalkylene group-containing chain organopolysiloxane (D) represented by the formula [Ia] (HLB: 5% by weight of oxyethylene in the oxyalkylene group-containing chain organopolysiloxane is 5%). 2 to 12 is preferable, and 2 to 7 is more preferable. When the HLB is small, the dissolution rate of the antifouling agent tends to be low and the antifouling effect tends to be low. On the other hand, when the HLB is large, the elution rate is high and the antifouling effect tends to be difficult to maintain for a long period of time.

  The blending amount of the oxyalkylene group-containing chain organopolysiloxane (D) into the antifouling coating composition of the present invention can be adjusted in consideration of the antifouling property of the resulting coating film. It is preferable to mix | blend in the ratio of 0.5-200 weight part with respect to 100 weight part of conductive resin (A).

(E) Plastic Resin As the plastic resin (E) in the present invention, a polybutene resin, paraffins, petrolatums, etc. blended in a known antifouling paint composition, particularly a clear antifouling paint composition for fishing nets, Polysulfide resins can also be used.

In terms of antifouling properties, the polybutene resin has a kinematic viscosity at 40 ° C. (measured with an Ostwald viscometer conforming to JIS K6726) of 5 to 400 C · S · t, and a number average molecular weight of 280 to 1000. Are preferred. Such polybutene resins are commercially available from Nippon Petrochemical Co., Ltd. under trade names such as “Polybutene LV-7”, “Polybutene LV-10”, “Polybutene LV-50”, and “Polybutene LV-100”. ing.

Examples of paraffins include n-paraffin, chlorinated paraffin, and liquid paraffin (a liquid hydrocarbon mainly composed of alkyl naphthenes).
Examples of petrolatum include white petrolatum and yellow petrolatum.

The polysulfide resin refers to a dialkyl sulfide compound represented by the following formula [IV].
R ^3d- (S) _n -R ^3e [IV]
In the formula [IV], a plurality of R ^3d and R ^3e each represents a linear or branched alkyl group having 1 to 20 carbon atoms, and may be the same or different from each other. n is an integer of 1-20.

  Examples of such polysulfide resins include diethyl pentasulfide, di-tert-butyl disulfide, di-tert-butyl tetrasulfide, di-tert-pentyl tetrasulfide, dioctyl polysulfide, di-tert-octyl pentasulfide, di- Examples thereof include tert-nonyl pentasulfide, di-tert-dodecyl pentasulfide, and dinonadecyl tetrasulfide.

  The blending amount of the plastic resin (E) in the antifouling coating composition of the present invention can be adjusted in consideration of the antifouling property of the resulting coating film, but the coating film forming resin (A) is 100 weights. It is preferable to mix | blend in the ratio of 0.5-50 weight part with respect to a part.

(F) Solvent As the solvent (F) in the present invention, it is blended in a known antifouling paint composition, particularly a clear antifouling paint composition for fishing nets, and dissolves various components such as the antifouling agent (B). It is possible to use organic solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, alcohols, ethers and the like.

  Examples of the aromatic hydrocarbon include xylene, toluene, trimethylbenzene, methylethylbenzene, and propylbenzene. Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, and methyl ethyl isobutyl ketone. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the alcohol solvent include ethanol, isopropyl alcohol, n-butanol, and isobutanol. Among these solvents, xylene is preferable from the viewpoints of dissolving power, flash point, evaporation rate, and odor. In the case where the triphenylboron / amine complex is triphenyl (n-octadecyl) amineboron, it is more preferable to contain 1% by weight or more of an alcohol solvent and / or an ester solvent in the paint. The compounding quantity of these solvents (F) should just be the same grade as well-known antifouling paint composition.

− Method for producing antifouling paint composition −
The antifouling coating composition of the present invention can be produced by mixing and stirring a predetermined amount of each component using a general apparatus and method.

− Use of antifouling paint composition −
The clear antifouling paint composition of the present invention is suitable for use in netting of fishing nets. Since this antifouling coating composition is composed entirely of solvent-soluble components, it has excellent uniform processing (fishing net can be uniformly dyed) and workability, and has an appropriate antifouling agent elution rate after coating and curing. In addition, it can continuously exhibit excellent antifouling performance for a wide range of fishing net deposits.

  The antifouling coating composition of the present invention is satisfactorily impregnated and attached if the fishing net is of a general material such as polyethylene, nylon, hemp, metal, polyester. The antifouling coating composition of the present invention can also be applied (for repair) to the surface of a fishing net that has already been subjected to antifouling treatment or the like and on which a coating film has been formed.

  The fishing net may be dyed according to a conventional method. For example, the fishing net is dipped in an antifouling coating composition, and the composition is infiltrated and impregnated in or between the fibers of the fishing net, and then the fishing net is pulled up and dried. Just do it. The antifouling coating composition may be sprayed on the front and back surfaces of the fishing net that has been spread or hung by an electrostatic coating method, an air gun, an airless coating method, or the like. Thus, the increase in weight of the fishing net after net dyeing and drying is usually about 80 to 200 g per kg of the fishing net.

  Such fishing nets that have been subjected to an antifouling treatment using the antifouling paint composition of the present invention and have an antifouling coating formed on the surface are widely used, such as Aosa, Barnacles, Aonori, Cellpra, Oyster, Fusakomushi, Hydrozoa It exhibits excellent antifouling properties such as being able to continuously prevent the attachment of aquatic organisms for a long period of time.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, the embodiment of this invention is not limited at all by these Examples.
[Preparation of antifouling paint composition]
(1) Examples A-1 to A-11
According to the composition (unit: parts by weight) listed in Table 1, the film-forming resin (A): acrylic resin “ACP-450” / antifouling agent (b1): triphenyl [3- (2-ethylhexyloxy) Propylamine] boron and triphenyl (n-octadecyl) amineboron / antifouling agent (b2): tetraethylthiuram disulfide / isothiazole compound (C): 4,5-dichloro-2-n-octyl-4-isothiazoline-3- ON, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-phenyl-1,2-benzisothiazol-3-one, 2-phenylisothiazole- 3-one / oxyalkylene group-containing chain organopolysiloxane (D): silicone oil “KF6016” / plastic resin (E): poly Ten “LV50” and polysulfide “DAF-1” / solvent (F): Antifouling paint compositions of Examples A-1 to A-11 were prepared using components such as ethyl acetate, n-butanol, and xylene. .

The details of the products used as the above components are as follows:
(A) “ACP-450”: Akira Otake Chemical Co., Ltd., xylene solution of acrylic resin (solid content 50%).
(B) “KF6016”: a polyether-modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.
(C) “Polybutene LV50”: polybutene resin manufactured by Nippon Petrochemical Industries, Ltd.
(D) “DAF-1”: manufactured by Dainippon Ink & Chemicals, Inc., polysulfide resin.

Moreover, the structural formula of the compound mix | blended as said isothiazole compound (C) is shown below.

(2) Comparative Examples B-1 to B-10
According to the blending composition (unit: parts by weight) listed in Table 2, the isothiazole compound (C) is not blended, or another amine is blended instead, and the rest is the same as in the above Example, Comparative Example B Antifouling paint compositions of -1 to B-10 were prepared.

[Performance evaluation]
For each of the antifouling paint compositions prepared in Examples and Comparative Examples, prepared in a sealed container and stored for 4 months in a constant temperature room at 23 ° C. and for one month stored in a constant temperature room at 50 ° C. Then, an evaluation test of three items was performed according to the following method.

(1) Amount of benzene generated As a means for verifying the decomposition of the triphenylboron compound, the benzene concentration in the antifouling coating composition was measured by “headspace-GC / MS”. A composition solution diluted with a solvent such as dimethylformamide was used as a sample, sampled so as not to exceed 0.015 g in a 40 mL vial, and sealed. Details of the analysis conditions are as follows:
-Headspace (made by HT3 Teledyne-Tekmar)
Valve oven temperature 160 ℃
Transfer line temperature 160 ℃
Sample oven temperature 50 ℃
Sample pressure 9PSIG
Sample pressurization time 2min
Pressure equilibration time 0.2min
Loop filling pressure 5PSIG
Loop filling time 2min
Injection time 1min
・ GC (GC6890N made by Agilent)
Column DB-5MS (length 30m inner diameter 0.25mm film thickness 0.25μm
(J & W Scientific)
Oven temperature 40 ℃ (1min) −10 ℃ / min−200 ℃
Carrier gas helium
Injection method Splitter (GCI5010 made by GL Sciences) injection
Column flow rate 1.5mL / min
Split ratio 2: 1
・ MS (JMS-K9 made by JEOL)
Measurement mode Selected ion detection method
Monitor ion 52/77/78/79
Ionization current 200uA
Ionization energy 70eV
Detector voltage -1000Volt
Ion source temperature 200 ° C
Interface temperature 200 ° C.

(2) Clearness The presence or absence of antifouling agent precipitation in the antifouling paint composition was examined and evaluated according to the following criteria:
Good: No precipitation has occurred. Bad: Precipitation has occurred.

(3) Standing antifouling property The antifouling coating composition was dip-coated on a polyethylene knotless net (7th, 400 denier / 50) and air-dried. The net on which the coating film was formed was immersed and held about 2 m below the sea surface off Sukumo City, Kochi Prefecture for five months from May 11 to October 12, 2007, and the state of attachment of marine organisms was investigated. Static antifouling property was evaluated according to the following 10-point criteria;
10: No marine organisms attached 5: Some marine organisms attached, 50% of the weight or area of the deposits 0: Submarine organisms attached to the entire surface of the net, the same level as the blank (no coating) 9 to 6 and 4 to 1 indicate intermediate stages (with an equal interval) when 10 and 5, 5 and 0 are used as references, respectively.

  The results of the evaluation test are as shown in Table 1 (Examples) and Table 2 (Comparative Examples). The antifouling paint compositions of the examples (invention) are generally comparative examples (B-1 to 3) in which no isothiazole compound is blended after storage at 23 ° C. for 4 months and after storage at 50 ° C. for 1 month. It can be seen that the amount of benzene generated is suppressed as compared with the above, and the triphenylboron compound is stabilized. For example, by comparison of A-1, A-7, A-11 and B-1, about 0.04 mol of isothiazole compound (C) is blended with 1 mol of triphenylboron / amine complex (b1). It is shown that the decomposition of the triphenylboron / amine complex (b1) is sufficiently suppressed as much as 0.5 mol or 1 mol. In addition, these antifouling coating compositions are maintained in the clearing property, and it can be seen that they exhibit excellent static antifouling performance even when stored for one month at a high temperature of 50 ° C. On the other hand, the antifouling coating composition of the comparative example has an unstable triphenylboron compound and the amount of benzene generated is not suppressed, or the clearness is impaired even if the triphenylboron compound is stabilized. Or And the static stain resistance of such an antifouling coating composition is generally poor, and it can be seen that the static stain resistance is significantly deteriorated particularly when stored at a high temperature of 50 ° C. for one month. .

Claims (11)

  In addition to (A) a film-forming resin, (B) (b1) triphenylboron / amine complex and (b2) tetraethylthiuram disulfide as antifouling agents, decomposition of the triphenylboron / amine complex (b1) A clear antifouling paint composition for fishing nets, comprising (C) an isothiazole compound as an inhibitor.   The clear antifouling paint composition for fishing nets according to claim 1, wherein the isothiazole compound (C) is contained in an amount of 0.01 to 10 mol with respect to 1 mol of the triphenylboron / amine complex (b1).   The fishing net according to claim 1 or 2, wherein the triphenylboron / amine complex (b1) is triphenyl [3- (2-ethylhexyloxy) propylamine] boron and / or triphenyl (n-octadecyl) amineboron. Clear type antifouling paint composition.   The clear antifouling paint composition for fishnets according to any one of claims 1 to 3, wherein the isothiazole compound (C) is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. .   In addition to the above components (A), (b1), (b2) and (C), (b3) an organic antifouling agent other than triphenylboron / amine complex (b1) and tetraethylthiuram disulfide (b2); One or more components selected from the group consisting of D) oxyalkylene group-containing chain organopolysiloxane, and (E) one or more plastic resins of polybutenes, paraffins, petrolatums, or dialkyl sulfide compounds. The clear antifouling paint composition for fishing nets according to claim 1, comprising:   As the organic antifouling agent (b3), N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino S triazine, chloromethyl- n-octyl disulfide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, N, N′-dimethyl-N′-tolyl- (N-fluorodichloromethylthio) sulfamide, 2,3 At least one selected from the group consisting of -dichloro-N- (2 ', 6'-diethylphenyl) maleimide and 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide The clear antifouling paint composition for fishing nets according to claim 5, which is contained. The oxyalkylene group-containing chain organopolysiloxane (D) is represented by the following formula [Ia] and has a hydrophilic / lipophilic balance (HLB: 5% by weight of oxyethylene in the oxyalkylene group-containing chain organopolysiloxane). The oxyalkylene group-containing chain organopolysiloxane having a value obtained by dividing by 2 to 12 is 0.5 to 200 parts by weight with respect to 100 parts by weight of the film-forming resin (A) (solid content converted value). The clear antifouling paint composition for fishing nets according to claim 5, which is contained in a proportion.

(In the formula [Ia], X ¹ , X ² and X ³ are each independently a polyether group: —R—A— (R ³ O) _n —R ⁴
[R represents an alkylene group having 1 to 5 carbon atoms, A represents a single bond or an oxygen atom, R ³ represents an alkylene group having 1 to 5 carbon atoms, R ⁴ represents an alkyl group having 1 to 5 carbon atoms or hydrogen, and n represents Indicates the number of repeating units. Or an alkyl group having 1 to 5 carbon atoms, at least one of these X ¹ , X ² and X ³ is the polyether group, R ² represents an alkyl group having 1 to 3 carbon atoms, Each of r and m represents the total number of repeating units, and the bonding order of the repeating units [—Si (R ² ) ₂ O—] and [—Si (R ² ) (X ¹ ) O—] is arbitrary. ) As the component (E), one or more plastic resins of polybutenes, paraffins, petrolatums, or dialkyl sulfide compounds represented by the formula (VI) are used as a film-forming resin (A) (solid content) The clear type antifouling paint composition for fishing nets according to claim 5, which is contained at a ratio of 5 to 100 parts by weight per 100 parts by weight.
R ^3d- (S) _n -R ^3e (VI)
(In the formula (VI), a plurality of R ^3d and R ^3e may be the same as or different from each other, and each represents a linear or branched alkyl group having 1 to 20 carbon atoms, and n is 1 to 20) Indicates an integer.)   The clear antifouling paint composition for fishing nets according to any one of claims 1 to 8, comprising 1% by weight or more of an alcohol solvent and / or an ester solvent as a solvent component.   An antifouling treatment for a fishing net, wherein the fishing net is immersed in the clear antifouling paint composition for fishing nets according to any one of claims 1 to 9, impregnated into the fishing net and adhered thereto. Method.   A fishing net subjected to an antifouling treatment using the clear antifouling paint composition for a fishing net according to any one of claims 1 to 9.