JP2000143672A - Underwater antifouling coating containing triphenyl(alkylenediamine)boron - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject coating capable of exhibiting an excellent antifouling activity, even when used together with coprous oxide or copper rhodanide, by adding a specific triphenyl(alkylenediamine)boron. SOLUTION: This underwater antifouling agent contains a compound of the formula [Ph is phenyl; (m) is 1-6; (n) is 0 or 1]. The coating may further contain cuprous oxide or copper rhodanide. The compound of the formula preferably includes bistriphenyl(propylenediamine)boron and bistriphenyl(pentylenediamine). The compound of the formula can be synthesized, for example, by reacting triphenylboron with an alkylenediamine in an organic solvent. The underwater antifouling coating capable of expressing a sufficient antifouling effect can be provided only by adding the compound of the formula as an antifouling active ingredient. When further mixed with the cuprous oxide or the copper rhodanide, the expansion of the kinds of aquatic organisms to be antifouling treatment targets and the extension of an effect-retaining time can be expected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is applied to underwater structures such as ships, aquaculture nets, stationary nets, offshore oilfield bases, buoys, power plant waterway facilities, bridges, etc., and adheres to the surface of the underwater portion of these structures. The present invention relates to an underwater antifouling paint containing triphenyl (alkylenediamine) boron as an active ingredient, which is effective for preventing the attachment of aquatic organisms that grow. Further, the present invention relates to an underwater antifouling paint containing cuprous oxide or rhodan copper and exhibiting a long-term storage stability and a continuous antifouling effect during use.

[0002]

2. Description of the Related Art Aquatic organisms such as barnacles, sea squirts, serpula, purple mussels, mussels, bryozoans, blue seaweeds and blue seaweeds adhere to the surface of underwater structures and grow and cause various damages. For example, when aquatic organisms attach to and grow on the hull of a ship, the speed of the ship decreases and fuel efficiency increases. In addition, when aquatic organisms adhere to underwater structures such as underwater or a port facility fixed to the surface of water, the individual functions of these devices are not sufficiently exhibited. Furthermore, it is also known that when these aquatic organisms adhere to fishing nets such as aquaculture nets and fixed nets, the meshes can kill fish. Attachment of aquatic organisms causes a great economic loss, and therefore, at present, efforts are being made to maintain these contaminated objects with great effort and cost. In particular, applying an underwater antifouling paint containing an active ingredient having an effect of inhibiting the growth and adhesion of aquatic organisms to an underwater structure is known as an effective measure, and various underwater antifouling paints have been researched and developed. Has been put to practical use.

Conventionally, it has been known that it is particularly effective to use cuprous oxide or copper rhodan in combination with an organotin compound as an underwater antifouling paint, and it has been widely used. Tin compounds are generally highly toxic, and careless handling of products containing them may cause harm to the user, and may also have a negative impact on the environment. It is. By the way, an organic boron compound is used as an active ingredient for preventing adhesion of aquatic organisms used in an underwater antifouling paint.
For example, U.S. Pat. No. 3,11,679 discloses, as antifouling compounds, an addition compound of triphenylboron and a substituted or unsubstituted pyridine or an addition compound of triphenylboron and an aliphatic monoamine in JP-A-8-295608 or JP-A-8-295608. In Japanese Unexamined Patent Publication No. Hei 8-295609, a solution of a fish net antifouling agent or an organic solvent containing a triphenylborane-alkylamine complex compound is disclosed in International Application WO 97/2725.
Japanese Patent Application Laid-Open No. 4 (1999) -264 discloses an underwater antifouling paint containing a triphenylborane-rosinamine addition compound. Although these triphenylboron derivatives are useful compounds, the triphenylboron skeleton is decomposed when used in combination with cuprous oxide or rhodan copper, and the point that the antifouling performance is impaired becomes an obstacle. It could not be used for underwater antifouling paints that are desired to be used in combination with rodan copper.

Further, bistriphenyl (ethylenediamine) boron and bistriphenyl (hexamethylenediamine) boron used in the underwater antifouling paint of the present invention are described in US Pat. No. 3,062,708 as foliar plant inhibitors. Also, bistriphenyl (butylene diamine)
Boron is described as a pesticide in U.S. Pat. No. 5,075,292. However, the above document does not disclose that bistriphenyl (alkylenediamine) boron is used as an active ingredient in an underwater antifouling paint for the purpose of preventing aquatic organisms from adhering, or that it can be used in combination with cuprous oxide or rodan copper. Not. Note that bistriphenyl (propylenediamine) boron and bistriphenyl (pentadiamine) boron are compounds that are not known without being described in the literature.

[0005]

Under such circumstances, an underwater antifouling paint which can maintain an excellent antifouling effect for a long period of time even when used in combination with cuprous oxide or copper rhodan which is widely used in underwater antifouling paints. Active ingredients were sought.

[0006]

The present inventors have made intensive studies to develop an underwater antifouling paint which solves the above-mentioned problems, and as a result, the formula (1)

Embedded image (Where Ph is a phenyl group, m is an integer of 1 to 6, n is 0)
Or 1 is indicated. It has been found that the triphenyl (alkylenediamine) boron represented by the formula (1) has excellent antifouling activity even when used in combination with cuprous oxide or copper rhodan.

That is, the present invention provides the following equation (1).

Embedded image (In the formula, Ph represents a phenyl group, m represents an integer of 1 to 6, and n represents 0 or 1.) An underwater antifouling paint containing triphenyl (alkylenediamine) boron represented by the following formula:
(2) In the formula (1), n is 1; the underwater antifouling paint according to the above (1); (3) In the formula (1), n is 0; (4) The underwater antifouling paint according to the above (1), wherein m is 2 in the formula (1).
(5) In the formula (1), m is 2 and n is 1. The underwater antifouling paint according to the above (1), wherein in the formula (1),
The underwater antifouling paint according to the above (1), wherein m is 2 and n is 0, (7) any one of the above (1) to (6) further comprising cuprous oxide or copper rhodan. And an underwater antifouling paint according to (8), and formula (8)

Embedded image (In the formula, Ph represents a phenyl group, and p represents an integer of 3 or 5.) Bistriphenyl (propylenediamine) boron or bistriphenyl (pentylenediamine) boron represented by the following formula:

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Triphenyl (alkylenediamine) boron represented by the formula (1) used in the paint of the present invention can be produced by the following method. That is, the following reaction formula

Embedded image (Where Ph is a phenyl group, m is an integer of 1 to 6, n is 0)
Or 1 is indicated. ), 1 or 2 mol of triphenylboron is reacted with 1 mol of alkylenediamine in an organic solvent to produce triphenyl (alkylenediamine) boron represented by the formula (1). be able to.

In the above reaction formula, for example, when m is 2, n
The production method when is 0 or 1 will be described in more detail. First, triphenylboron and ethylenediamine are dissolved in an organic solvent such as ethers such as diethyl ether and tetrahydrofuran and aromatic hydrocarbons such as benzene, toluene and xylene in a molar ratio of 1: 1 or 2: 1. . The obtained solution is stirred at 0 to 60 ° C. for 30 minutes to 2 days in an atmosphere of an inert gas such as nitrogen while excluding air to obtain the desired mono- or bistriphenyl (ethylenediamine) boron. Next, the solvent is distilled off from the reaction solution and concentrated, and then the crystals are separated by filtration, washed with a small amount of a solvent and dried to obtain mono- or bistriphenyl (ethylenediamine) boron as a high-purity product. If necessary, it can be further purified by recrystallization with a solvent such as toluene.
Even when m is 1 or 3 to 6, the corresponding mono- or bistriphenyl (alkylenediamine) boron can be produced by using the corresponding alkylenediamine by the method according to the above.

In the underwater antifouling paint of the present invention, triphenyl (alkylenediamine) boron represented by the formula (1), which is used as an antifouling active ingredient, is blended with a coating composition to be made antifouling by ordinary means. It can be manufactured by the following. As a means for blending such an active ingredient compound, the active ingredient compound is dissolved in an organic solvent that dissolves the active ingredient compound,
Alternatively, when there is no suitable organic solvent, the active ingredient compound is mechanically and uniformly pulverized and mixed by a mixing and pulverizer, for example, an atomizer or the like, in a powder state. An organic solvent for coating, a surfactant, a coating resin, a plasticizer, a pigment, and other necessary coating auxiliary components are added to the solution of the active ingredient compound or the powder of the active ingredient compound thus obtained. However, by uniformly mixing, it is possible to formulate an antifouling paint. The paint resin that can be used in the underwater antifouling paint of the present invention is a film-forming resin for forming a coating film on the surface of the substrate, and is a resin commonly used in conventional underwater antifouling paints. Similar ones can be used. For example, as the resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, styrene-butadiene copolymer, chloride rubber resin, chlorinated polypropylene resin, petroleum resin, alkyd Resin, acrylic resin, phenol resin, synthetic rubber, epoxy resin, silicone rubber, silicone resin, Teflon resin, and the like. Formula (1) in the underwater antifouling paint of the present invention
The amount of triphenyl (alkylenediamine) boron is 0.1 to 350 parts by weight, preferably about 1 to 150 parts by weight, per 100 parts by weight of the coating resin. Further, the above-mentioned plasticizer is used for the paint resin 1.
It is desirable to add 20 parts by weight or less per 100 parts by weight.

The underwater antifouling paint of the present invention may contain, if necessary, a coloring pigment or coloring agent, for example, titanium white, red iron oxide,
Carbon, cyan blue, cyanine green, or the like, or an extender such as talc, barita, or zinc white can be blended. The type of the organic solvent to be used is not particularly limited as long as it can dissolve or disperse the above-mentioned coating resin and other components to be blended. Examples of such an organic solvent include alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, etc.), and aromatic hydrocarbons (toluene, xylene, ethylbenzene, Chlorobenzene, cumene, etc.), ethers (ethyl ether, ethylene oxide, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone,
Methyl isobutyl ketone, etc.), esters (ethyl acetate, ethylene glycol acetate, amyl acetate, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.), glycol ethers (ethylene glycol monomethyl) Ethers, ethylene glycol monoethyl ether, etc.), amines (ethylamine,
Dimethylamine, triethylamine, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), petroleum fractions (paraffins, kerosene, gas oil, etc.).

In the underwater antifouling paint of the present invention, a sufficient antifouling effect can be exhibited only by adding triphenyl (alkylenediamine) boron of the formula (1) as an antifouling active ingredient. By adding rodan copper, it is possible to increase the types of aquatic organisms to be antifouling and extend the effect duration. The mixing ratio of the cuprous oxide or the copper rodan in the paint is usually 1 to 30% by weight, preferably 2 to 2% by weight.
It is about 0% by weight. In addition, antifouling and antifungal agents generally known in the art, such as zinc dimethyldithiocarbamate and 2-methylthio-4-t-butylamino-
6-cyclopropylamino-s-triazine, 2,4
5,6-tetrachloroisophthalonitrile, zinc ethylenebisdithiocarbamate, 4,5-dichloro-2-
n-octyl-3 (2H) isothiazoline, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt , 2-pyridinethiol-1-oxide copper salt, tetramethylthiuram disulfide, tetraethylthiuram disulfide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,6
One or two of trichlorophenylmaleimide, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatolylsulfone, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, 2-methyl-4-isothiazolin-3-one and the like You may mix together the above.

[0013]

The present invention will be described more specifically with reference to the following examples, synthesis examples and test examples, but the present invention is not limited to these examples. Parts used in the examples are on a weight basis. Synthesis Example 1 Synthesis of bistriphenyl (ethylenediamine) boron Dry nitrogen gas was injected into a glove box, and the following operation was performed in a glove box from which oxygen and moisture were expelled. 2.42 g (10 mmol) of triphenylboron was dissolved in 50 ml of a mixed solvent of tetrahydrofuran and benzene, and the triphenylboron solution was placed in a 100-ml separating funnel. In a 200 ml four-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet, 0.30 g (5 mmol) of ethylenediamine and 50 ml of the above mixed solvent of tetrahydrofuran-benzene were stirred and dissolved. Nitrogen gas was flowed from the nitrogen inlet to replace the inside of the flask with nitrogen gas. The triphenylboron solution was added dropwise at room temperature over 10 minutes from the separating funnel with stirring, and the mixture was stirred and reacted at the same temperature for 5 hours. After completion of the reaction, the organic solvent was distilled off under reduced pressure to obtain a white solid. The white solid was recrystallized from a toluene solvent, filtered and dried to obtain 2.58 g (95% yield) of bistriphenyl (ethylenediamine) boron. The obtained compound was analyzed by infrared spectrum (IR), and the result was [FIG. 1].
It was shown to.

Synthesis Example 2 Synthesis of bistriphenyl (propylenediamine) boron A white solid obtained by the same operation as in Synthesis Example 1 except that 0.37 g (5 mmol) of propylenediamine was used instead of 0.30 g (5 mmol) of ethylenediamine. I got The white solid was operated in the same manner as in Synthesis Example 1 to obtain 2.62 g of bistriphenyl (propylenediamine) boron (yield: 94).
%)was gotten. The obtained compound was subjected to infrared spectroscopy (I
R) and the results are shown in FIG.

Synthesis Example 3 Synthesis of bistriphenyl (pentylenediamine) boron The same operation as in Synthesis Example 1 was carried out except that 0.51 g (5 mmol) of pentadiamine was used instead of 0.30 g (5 mmol) of ethylenediamine. To give a white solid. This white solid was operated in the same manner as in Synthesis Example 1 to obtain 2.79 g of bistriphenyl (pentadiamine) boron (yield: 9).
5%). The obtained compound was analyzed by infrared spectrum (IR), and the results are shown in FIG.

Synthesis Example 4 Synthesis of triphenyl (ethylenediamine) boron Dry nitrogen gas was injected into a glove box, and the following operation was performed in a glove box from which oxygen and moisture were expelled. 1.21 g (5 mmol) of triphenylboron
It was dissolved in 0 ml of a mixed solvent of tetrahydrofuran and benzene, and the triphenylboron solution was put into a 100-ml separating funnel. In a 200 ml four-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet, 0.30 g (5 mmol) of ethylenediamine and 50 ml of the above-mentioned mixed solvent of tetrahydrofuran-benzene were stirred and dissolved. Nitrogen gas was flowed from the nitrogen inlet to replace the inside of the flask with nitrogen gas. The triphenylboron solution was added dropwise at room temperature over 10 minutes from the separating funnel with stirring, and the mixture was stirred and reacted at the same temperature for 5 hours. After completion of the reaction, the organic solvent was distilled off under reduced pressure to obtain a white solid. The white solid was recrystallized from a toluene solvent, filtered and dried, and triphenyl (ethylenediamine) boron 1.44 was obtained.
g (yield 95%) was obtained. mp 157.8-159.8 ° C .; Elemental analysis: as C ₂₀ H ₂₃ BN ₂ Calculated: C 79.48, H 7.67, N 9.27 Found: C 79.68, H 7.78, N 9.08 IR (KBr) cm ^-1 : 3382, 3322, 323
8; NMR (CDCl ₃ ): δ 1.00 (2H), δ 2.6
4 (4H), δ4.66 (2H), δ7.07 to 7.5
0 (15H). MS (EI, Pos.): M / e (strength) 242 (5
8), 164 (100), 61 (6)

Next, the bistriphenyl (alkylenediamine) boron of the present invention is a triphenylboron derivative,
Compared to the same type of alkylenediamine derivative, to show that it is more stable to cuprous oxide and copper rhodan,
A stability test was performed. Stability Test 1 Stability tests were performed on the following compounds A to H by the following method. A: Triphenyl (pyridine) boron (U.S. Pat.
It was synthesized according to the description in JP-A-1679. B) Triphenyl (octylamine) boron (JP-A-8
The compound was synthesized according to the description in US Pat. C: bistriphenyl (ethylenediamine) boron (compound of formula (1) where m = 2, n = 1, synthesized according to Synthesis Example 1) D: bistriphenyl (propylenediamine) boron (m = of formula (1)) 3, compound of n = 1, synthesized according to Synthesis Example 2. E: bistriphenyl (pentylenediamine) boron (compound of formula (1) where m = 5, n = 1, synthesized according to Synthesis Example 3) F: bistriphenyl (octylenediamine) boron (compound of formula (1) where m = 6, n = 1, synthesized according to Synthesis Example 1) G: bistriphenyl (dodecylenediamine) boron (formula (1) 1) Compound of m = 12, n = 1, synthesized according to Synthesis Example 1. H: Triphenyl (ethylenediamine) boron (Compound of Formula (1) where m = 2, n = 0, Synthesis Example 4) It was synthesized according to.)

One part by weight of each of the test compounds of A to H, 6 parts by weight of cuprous oxide, and 30 parts by weight of xylene are mixed, and the mixture is mixed with about 2 parts by weight.
After heating for 0 minute, the temperature was raised from 25 ° C. to 80 ° C., kept at 80 ° C., taken out a little after 2 hours, 4 hours, and 8 hours, and quantitatively analyzed the test compound by high performance liquid chromatography (HPLC). The residual ratio of the test compound was calculated. The measurement conditions of HPLC were ODS column, the eluent was methanol / tetra-n-butylammonium phosphite pH 7.5, and the detector was ultraviolet (UV) 220 n
m. Stability test 2 Stability test 1 using rodan copper instead of cuprous oxide
Was carried out in the same manner as described above. The test results are shown in [Table 1] and [Table 2].

[0019]

[Table 1]

[0020]

[Table 2]

According to the results of the stability test, triphenyl (alkylenediamine) boron of formula (1) wherein m is 2 to 6, preferably 2 to 5, and more preferably m is 2 Is present, triphenyl (pyridine) boron, triphenyl (octylamine) boron, or triphenyl (dodecalenediamine) having an alkylene group having 12 carbon atoms
It turns out that it is extremely stable as compared with boron.

Example 1 10 parts of bistriphenyl (ethylenediamine) boron,
30 parts of vinyl resin varnish, chlorinated isoprene rubber 10
Parts, zinc white 10 parts, red bengara 5 parts, colloidal silica 3
Parts, 10 parts of talc, 15 parts of xylene, 5 parts of methyl isobutyl ketone, and 100 parts of n-butyl alcohol in total of 100 parts were dispersed by tumbling and mixing in a ball mill for 5 hours to obtain a homogeneous underwater antifouling paint. Obtained.

Examples 2 to 3 The coating materials of Examples 2 to 3 were prepared in the same manner as in Example 1 by mixing the components according to the coating composition shown in Table 3. Example 4 A homogeneous underwater antifouling paint was obtained in the same manner as in Example 1, except that 10 parts of bistriphenyl (ethylenediamine) boron was replaced with 10 parts of triphenyl (ethylenediamine) boron. Examples 5 and 6 By the same preparation method as in Example 4, the coating components shown in [Table 3] were mixed to prepare antifouling underwater coatings of Examples 5 and 6. Comparative Examples 1 to 6 Underwater antifouling paints of Comparative Examples 1 to 6 were prepared by the same preparation method as in Example 1 except that the antifouling active ingredients were changed to those shown in [Table 3].

[0024]

[Table 3]

Efficacy Test of Examples 1 to 6 and Comparative Examples 1 to 6 An ordinary rust preventive paint was previously applied to a sandplast-treated steel sheet, and the dried coating film was applied to Examples 1 to 6 for comparison. A paint (100 mm × 30 mm) was obtained by applying the paints of Examples 1 to 6 twice with a brush and having a dry paint film thickness of about 100 μm.
0 mm). This test plate was immersed for 24 months in the sea at a depth of 1.5 m in Sukumo Bay, Sukumo City, Kochi Prefecture,
At 6 months, 12 months, 18 months, and 24 months after the immersion, the state of adhesion of the aquatic organisms was observed, and the antifouling effect was determined according to the evaluation criteria for the degree of aquatic organisms shown below. The results are shown in [Table 4]. No adhesion ◎ Adhesion area: less than 10% ○ Adhesion area: less than 10 to 20% △ Adhesion area: 20 to less than 30% × Adhesion area: 30% or more XX

[0026]

[Table 4]

As is clear from Table 4, Examples 1 to
The test plate coated with an underwater antifouling paint containing bistriphenyl (ethylenediamine) boron or triphenyl (ethylenediamine) boron had an adhesion area of less than 10% even after 24 months of immersion, showing a good effect. On the other hand, the test plates coated with the paints of Comparative Examples 1 to 6 show a decrease in the antifouling effect already at 6 months after immersion, and furthermore cannot be used together with cuprous oxide or copper rhodan.

[0028]

The underwater antifouling paint containing triphenyl (alkylenediamine) boron of the formula (1) of the present invention has excellent underwater antifouling effect and is a component generally used in underwater antifouling paint. It is stable for a long time even when used in combination with copper oxide or rodan copper, and exhibits an excellent antifouling effect.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum (IR chart) of bistriphenyl (ethylenediamine) boron obtained in Synthesis Example 1.

FIG. 2 is an infrared absorption spectrum (IR) of bistriphenyl (propylenediamine) boron obtained in Synthesis Example 2.
chart).

FIG. 3 is an infrared absorption spectrum (IR) of bistriphenyl (pentylenediamine) boron obtained in Synthesis Example 3.
chart).

Continuing from the front page (72) Inventor Masanori Yoshimaru 955 Komatsuri, Yoshitomi-cho, Chikugami-gun, Fukuoka Yoshitomi Fine Chemical Co., Ltd.F-term (reference) 4H011 AD01 BA01 BB16 BC19 DA23 4H048 AA01 AA03 AB99 VA30 VA75 VB10 4J038 EA011 HA216 JC18 JC37 NA05 PB05

Claims (8)

[Claims] (1) Formula (1) (In the formula, Ph represents a phenyl group, m represents an integer of 1 to 6, and n represents 0 or 1.) An underwater antifouling paint containing triphenyl (alkylenediamine) boron represented by the following formula: 2. In the formula (1), n is 1.
Underwater antifouling paint as described. 3. In the formula (1), n is 0.
Underwater antifouling paint as described. 4. In the formula (1), m is 2.
Underwater antifouling paint as described. 5. The underwater antifouling paint according to claim 1, wherein m is 2 and n is 1 in the formula (1). 6. The underwater antifouling paint according to claim 1, wherein m is 2 and n is 0 in the formula (1). 7. The underwater antifouling paint according to claim 1, further comprising cuprous oxide or copper rhodan. 8. The formula (2) (In the formula, Ph represents a phenyl group, and p represents an integer of 3 or 5.) Bistriphenyl (propylenediamine) boron or bistriphenyl (pentylenediamine) boron represented by the following formula: