JP3154301B2 - Antifouling paints against marine fouling organisms. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint for marine fouling organisms , and more particularly to a vinylbenzylphosphonium salt or / and a polymer containing at least the salt as a monomer component as an active ingredient. Subsea pollution
The present invention relates to an antifouling paint for organisms .

[0002]

2. Description of the Related Art It is said that there are 2,000 kinds of fouling organisms adhering to ship bottoms, seawater introduction pipes, underwater structures, etc. Among them, barnacles, selbra, stime,
There are beetles, oysters, sea squirts, Aonori and Aosa,
It is well known that these cause various obstacles.

[0003] For example, in the case of a ship bottom, a decrease in ship speed due to an increase in frictional resistance, and hence an increase in fuel consumption, impede normal operation and maintenance of seawater introduction pipes and underwater structures. .

Conventionally, as a main agent of an antifouling paint for the purpose of preventing such fouling organisms from adhering, typically, various compounds such as cuprous oxide, trialkyl organotin or organolead compounds, or copper phosphide have been proposed. And has been put to practical use. However, since these compounds are extremely harmful in the marine environment, the emergence of pollution-free antifouling paints has recently been demanded.

Some proposals regarding such pollution-free antifouling paints are also known, for example, see JP-A-63-227.
No. 673, quaternary ammonium salt of carboxymethylcellulose, JP-A-63-280779, a tetraalkylammonium salt, and JP-B-2-64167, a radical polymer having a quaternary ammonium salt type cationic group. Quaternary ammonium salts such as monomeric copolymers are disclosed.

[0006]

However, the above quaternary ammonium salt bactericides are not yet sufficient in preventing marine fouling organisms from adhering for a long time. Means for Solving the Problems In view of the above facts, the inventors of the present invention have conducted intensive studies and have found that an antifouling paint containing, as an active ingredient, a vinylbenzylphosphonium salt or / and a polymer containing at least the vinylbenzylphosphonium salt as a monomer component can be used in seawater. The present inventors have found that they exhibit an excellent antifouling effect on the fouling organisms therein, and have completed the present invention.

[0007]

That is, the present invention provides an antifouling paint (hereinafter, referred to as an antifouling paint for marine fouling organisms).
Abbreviated as antifouling paint) is represented by the following general formula (1)

[0008]

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(Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group; The aryl group and the aralkyl group may be substituted with a hydroxy group or an alkoxy group.
X ^- represents an anion. )) And / or a polymer containing at least the vinylbenzylphosphonium salt as a monomer component (hereinafter referred to as “vinylbenzylphosphonium compound”) as an active ingredient. It is.

Hereinafter, the present invention will be described in more detail.
As described above, the antifouling paint according to the present invention is a composition containing a vinylbenzylphosphonium compound as an effective component of the antifouling action in the paint, and includes the following three embodiments.

A mixture of the above-mentioned vinylbenzylphosphonium salt and a paint vehicle A mixture of a polymer containing at least the vinylbenzylphosphonium salt as a monomer component and a paint vehicle The above-mentioned vinylbenzylphosphonium salt and at least the vinylbenzylphosphonium salt are contained as a monomer component Needless to say, in the above mixture, for example, an organic or inorganic compound described below can be used in combination in the above mixture, if necessary.

In the vinylbenzylphosphonium compound according to the present invention, the vinylbenzylphosphonium salt is represented by the following general formula (1):

[0013]

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In the formula, specific examples of R _{1 to} R ₃ include:
Hydrogen atom; hydroxy group; linear or branched alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl, octyl, dodecyl, isopropyl; phenyl, tolyl, xylyl, etc. An aralkyl group such as benzyl and phenyl; the alkyl group, the aryl group and the aralkyl group may be substituted with a hydroxy group or an alkoxy group. Among them, preferred are an alkyl group, an aryl group and an aralkyl group, and more preferred are an alkyl group and an aryl group. Also,
R ₁ , R ₂ and R ₃ may be the same or different groups.

Further, the anion (X ^-) include, for example fluorine, chlorine, bromine or a halogen such as iodine ions,
Carboxyl ion such as formic acid, acetic acid, oxalic acid, sulfate ion, phosphate ion, methyl or dimethyl phosphate ion, ethyl or diethyl phosphate ion, antimony fluoride ion, phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion , Perchlorate ion and the like, and among them, a halogen ion is preferable.

X ^- is an antimony fluoride ion,
When it is phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion, perchlorate ion, it becomes water-insoluble,
The solubility can be changed by changing R _{1 to} R ₃ . Therefore, by changing R _{1 to} R ₃ and X ⁻ in the general formula (1), the vinylbenzylphosphonium compound contained in the paint can design an antifouling agent with a solubility according to the use. When R _{1 to} R ₃ of the phosphonium salt are alkyl groups, the antifouling effect is affected by the length thereof. For example, as the length increases with methyl, ethyl, butyl, and octyl, the antifouling effect increases.

Next, the vinylbenzylphosphonium salt represented by the general formula (1) will be described more specifically. For example, triethyl-3-vinylbenzylphosphonium chloride, triethyl-4-vinylbenzylphosphonium chloride, tributyl-3-vinyl Benzylphosphonium chloride and tributyl-4-vinylbenzylphosphonium chloride, triphenyl-3-vinylbenzylphosphonium chloride and triphenyl-4-vinylbenzylphosphonium chloride, trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4-vinylbenzylphosphonium chloride , Triethyl-3
-Vinylbenzylphosphonium bromide and triethyl-4-vinylbenzylphosphonium bromide, triethyl-3-vinylbenzylphosphonium tetrafluoroborate and triethyl-4-vinylbenzylphosphonium tetrafluoroborate, but are not limited thereto. is not.

Next, as the polymer containing the vinylbenzylphosphonium salt represented by the general formula (1) as a monomer in the structural unit of the polymer, the following general formula (2)

[0019]

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(Wherein, R _{1 to} R ₃ , X ⁻ are the same as described above; n is an integer of 2 or more), and a vinylbenzylphosphonium salt represented by the above general formula (1) And / or a copolymer of the above-mentioned vinylbenzylphosphonium salt and a compound having an unsaturated double bond copolymerizable with the salt.

The antifouling effect of the homopolymer of the vinylbenzylphosphonium salt represented by the general formula (2) is the same as that of the vinylbenzylphosphonium salt in the case where R _{1 to} R ₃ of the phosphonium salt in the formula are alkyl groups. Although it is affected by its length, its antifouling effect is several orders of magnitude better than the vinylbenzylphosphonium salt.

The degree of polymerization of the polymer represented by the general formula (2) is not particularly limited, but is 2 or more, and in many cases, 5 or more, preferably 10 to 200.

Next, as the compound having an unsaturated double bond copolymerizable with the vinylbenzylphosphonium salt represented by the general formula (1), for example, ethylene, propylene, butylene, isobutylene, diisobutylene, vinyl chloride, chloride Vinylidene, vinyl bromide, (meth) acrylic acid, alkyl (meth) acrylate, (meth) acrylamide, vinyl alcohol, vinyl acetic acid, acrylonitrile, vinyl sulfonate, N-vinyl-2-pyrrolidone, maleic acid, fumaral Acid, styrene, vinyltoluene, cinnamic acid, vinylthiophene, vinylpyridine or vinylimidazole.
Species or two or more species may be used.

The ratio of the structural unit of the vinylbenzylphosphonium salt in the copolymer of the compound having an unsaturated double bond and the vinylbenzylphosphonium salt is usually 1 to 99 mol%, preferably 5 to 50 mol. % Is desirable. The ratio of the structural unit of the compound having an unsaturated double bond is usually 99 to 1 mol%, preferably 95 to 50 mol%.

The polymerization form of each structural unit in the copolymer is various, and may be any of random, block and graft.

The degree of polymerization of the copolymer is not particularly limited, but in most cases, a degree of 5 or more, preferably 40 to 200, is excellent in antifouling properties.

In the paint containing the antifouling agent according to the present invention, the paint vehicle refers to a liquid paint component excluding a vinylbenzylphosphonium compound having an antifouling action, a pigment, and the like. It is composed of oils such as varnish, resin, desiccant, plasticizer, solvent diluent, etc., and is used according to the purpose of use without any change, especially without any change from the conventional coating vehicle it can.

As the resin, for example, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, chloride rubber resin, chlorinated polyethylene, chlorinated polypropylene, acrylic resin, styrene-butadiene copolymer resin, epoxy resin,
Examples include silicon-containing resins, fluorine-containing resins, arrayed dicyclopentadiene resins, and organic tin polymers such as tributyltin-containing acrylic copolymers and triphenyltin-containing acrylic copolymers.

In the present invention, the amount of the vinylbenzylphosphonium compound contained in the antifouling paint varies depending on the use of the paint, but in most cases is in the range of 0.001 to 50% by weight based on the total weight of the antifouling paint. It is in. Preferably, 0.01 to 20% by weight is appropriate. Content is 0.
When the amount is less than 001% by weight, the coating composition cannot substantially achieve the antifouling action, and the upper limit is often limited for economic reasons and set as a practical range.

The antifouling paint of the present invention may be used in combination with another antifouling agent, if necessary, for example, triphenyltin hydroxide, triphenyltin acetate, triphenyltin chloride, tetramethylthiuramdi. Examples include sulfide, zinc dimethyldithiocarbamate, cuprous oxide, tributyltin fluoride, tributyltin methacrylate copolymer, triphenyltin fluoride, triphenyltin versatic acid, and quaternary ammonium salts. It can be used in combination with more than one species.

Further, if necessary, for example, clay, talc, calcium carbonate, silica, aluminum hydroxide,
Inorganic fillers such as glass powder, organic or inorganic colorants such as titanium oxide, carbon black and phthalocyanine pigments, plasticizers such as phthalate esters and phosphate esters, antioxidants, ultraviolet absorbers, and light Various additives such as stabilizers and preservatives can be used in combination as needed.

The method for preparing the antifouling paint of the present invention is not particularly limited as long as each component is uniformly mixed, and a known method can be used. For example, it is achieved by using a dispersing device such as a high speed mill, a ball mill, and a sand mill, and sequentially adding and mixing and dispersing various compounding materials.

The antifouling paint of the present invention thus prepared is
As it is or after adjusting the viscosity with a solvent, usually by airless spray coating, sometimes roller coating,
Used with a dry film thickness of about 30 to 300 µm on ship bottoms and offshore structures by brush painting, two-head gun painting, etc.

[0034]

The antifouling paint according to the present invention is a paint containing a vinylbenzylphosphonium compound as an effective component of the antifouling action. Although the detailed mechanism of the action is unknown, it is probably the following. Can be estimated.

That is, vinylbenzylphosphonium compounds, whether monomeric or polymeric, rely on phosphonium salts for their particular compounds to have strong biocidal activity against polluting organisms in water and in the sea, such as shellfish, as well as algae. Have.

[0036]

The present invention will be further described below with reference to examples.

Examples 1 to 6 and Comparative Example 1 (1) Synthesis of antifouling agent of vinylbenzylphosphonium compound (i) In a 100 ml flask sufficiently purged with nitrogen,
9.85 parts by weight of chloromethylstyrene and 10.88 parts by weight of trioctylphosphine were added, and then 20 parts by volume of n-hexane was added. The liquid temperature in the flask was set to 25 ° C., and the reaction was carried out for 24 hours to obtain a product of white crystals. The crystals were filtered and sufficiently washed with n-hexane. The obtained product was dried under reduced pressure and room temperature to obtain 8.84 parts by weight of a mixture of trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4-vinylbenzylphosphonium chloride (referred to as sample A).

(Ii) 2.00 parts by weight of a mixture of trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4-vinylbenzylphosphonium chloride is dissolved in 20 parts by volume of water, and 2,2-azobis- (2-
After adding 0.0367 parts by weight of (aminodipropane) hydrochloride, the tube was degassed and sealed. This was left to polymerize at 60 ° C. for 6 hours, then poured into a large excess of tetrahydrofuran, and the precipitated precipitate was collected by filtration. 0.97 parts by weight of a mixture of polytrioctyl-3-vinylbenzylphosphonium chloride and polytrioctyl-4-vinylbenzylphosphonium chloride (hereinafter referred to as sample B) was obtained. The weight average molecular weight of the polymer was 76,200.

(Iii) 1.5 parts by weight of a mixture of trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4-vinylbenzylphosphonium chloride and 0.47 parts by weight of N-vinyl-2-pyrrolidone in 10 parts by weight of dimethylformamide. After dissolving, 0.0176 parts by weight of azobisisobutyronitrile was added and the tube was degassed and sealed. This was left to polymerize at 60 ° C. for 6 hours, then poured into a large excess of tetrahydrofuran, and the resulting precipitate was collected by filtration to give polytrioctyl-3-vinylbenzylphosphonium chloride and polytrioctyl-4.
1.40 parts by weight of -vinylbenzylphosphonium chloride: N-vinyl-2-pyrrolidone copolymer (referred to as sample C) was obtained. The weight average molecular weight of the copolymer is 17,4.
00.

(Iv) A mixture of tributyl-3- (vinylbenzyl) phosphonium chloride and tributyl-4- (vinylbenzyl) phosphonium chloride 1.50
A weight part and 0.31 part by weight of acrylamide were dissolved in 10 parts by weight of dimethylformamide, and 0.0181 part by weight of azobisisobutyronitrile was added, followed by degassing and sealing. This was left to polymerize at 60 ° C. for 6 hours, then poured into a large excess of acetone, and the resulting precipitate was collected by filtration to give poly (tributyl-3- (vinylbenzyl) phosphonium chloride and tributyl-4-methyl-4-butyl). 1.11 parts by weight of (vinylbenzyl) phosphonium chloride: acrylamide) copolymer (referred to as sample D) was obtained. The weight average molecular weight of the copolymer was 10,500.

(2) Preparation of antifouling paint Each of the raw materials shown in Table 1 below was kneaded to prepare an antifouling paint.

(3) Test An iron plate (length: 151 mm × width: 100 mm) previously coated with a paint of each composition shown in Table 1 below was coated with a rust preventive paint.
mm, thickness 2 mm) with a 60 μm bar coater, and dried to obtain an immersion test plate. Next, in Tokuyama Bay, Yamaguchi Prefecture, they were immersed in a water depth of 1.5 m to 2 m for two years, and a comparative test of antifouling performance was performed.

Table 2 shows the results of the biofouling. [Evaluation in Table 2] A: No or very little biofouling. ：: Biofouling is clearly observed, but there is no practical problem. Δ: There is considerable biofouling and there is a problem in practical use. X: Very much biofouling.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

As described above, the antifouling paint according to the present invention has a strong antifouling action against fouling organisms in seawater.
It can be expected as a highly practical alternative to conventional antifouling paints.

Continuation of the front page (56) References JP-A-5-156180 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 5/14 C09D 143/02 CA (STN) REGISTRY ( STN)

Claims (4)

(57) [Claims] 1. The following general formula (1): (Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group; aralkyl group optionally substituted by a hydroxy group or an alkoxy group .X ^-. effective polymers containing at least vinylbenzyl phosphonium salt and / or the vinylbenzyl phosphonium salt represented by showing the anion) as a monomer component component An antifouling paint for marine fouling organisms , characterized in that it is contained as an antifouling organism . 2. A vinylbenzylphosphonium salt and / or a polymer containing at least the vinylbenzylphosphonium salt as a monomer component is added in an amount of 0.000.00% by weight.
The marine fouling organism according to claim 1, which contains 1 to 50% by weight.
Antifouling paint for. 3. Use by applying to ship bottoms or underwater structures.
Antifouling against marine fouling organisms according to claim 1 or 2.
paint. 4. The method according to claim 1, wherein the polluted organism is a ship bottom, a seawater introduction pipe or
The sea according to claim 1, which is a fouling organism attached to the undersea structure.
Antifouling paint for fouling organisms inside.