JPH0782511A - Antibacterial and antifouling coating material - Google Patents

Abstract

PURPOSE:To obtain an antibacterial and antifouling coating material free from pollution and excellent in antifouling activity by forming a composition containing a specified vinylphosphonium salt and a polymer made by using it as the monomer component. CONSTITUTION:This coating material contains 0.001-50wt.%, based on the whole coating material, vehicle component comprising a vinylphosphonium salt of formula I, II or III (wherein R<1>, R<2> and R<3> are each 1-20C alkyl, aryl, etc.; X<-> is an anion; A is alkylene; and Y is H, lower alkyl or aryl) and/or a polymer made by using them as the monomer component. Examples of the compounds of formulas I, II and III are tri-n-octylvinylphosphonium chloride, vinoxycarbonylmethyltri-n-butylphosphonium chloride and methacryloyloxymethyltri-n-butylphosphonium chloride respectively. A homopolymer formed from the compound and having a degree of polymerization of 10 to 200 or a copolymer of the compound with a compound having an unsaturated double bond has high safety and exhibits enhanced antibacterial and antifouling properties.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial and antifouling coating composition, and more particularly, an antibacterial and antifouling coating composition containing a vinylphosphonium salt having an antibacterial and antifouling function and / or a polymer obtained by polymerizing the salt as a monomer component in a coating composition. Regarding antifouling paint.

[0002]

2. Description of the Related Art Generally, microorganisms are attached to various industrial material products having paints and coatings and their surfaces,
When the growth conditions such as humidity, temperature and pH are satisfied, the microorganisms start to reproduce, resulting in discoloration, pollution, deterioration and deterioration.

Therefore, as a means for suppressing or killing the harmful microorganisms, various various antibacterial agents and fungicides capable of preventing the reproduction of bacteria and molds or killing them. A method for effectively preventing the above-mentioned various obstacles has been developed by using a paint mixed with an agent.

Further, as the paint itself becomes pollution-free and resource saving, emulsion paints and water-soluble paints are increasing, and prevention of decay and mold during storage and use is a serious problem.

Conventionally, as these antibacterial agents for paints, phenol type, tolidine and thiadiazine type, quaternary ammonium salt type and the like have been used. Among these,
Most of the antibacterial agents that have been put to practical use or under research are quaternary ammonium salt type.

On the other hand, it is said that there are 2000 kinds of fouling organisms attached to ship bottoms, seawater introduction pipes, undersea structures, etc., and typical ones among them are barnacles, cellulas, stime, bryozoans, oysters, squirts, aonori and It is well known that there are various kinds of obstacles, such as sea bream.

[0007] For example, in the case of the bottom of a ship, the speed of the ship decreases due to an increase in frictional resistance, which leads to an increase in the amount of fuel consumption, which hinders the normal operation and maintenance of seawater introduction pipes and subsea structures. . Conventionally, various compounds such as cuprous oxide, trialkyl-based organotin or organic lead-based compounds, or copper phosphide have been proposed as the main component of antifouling paints for the purpose of preventing the attachment of such fouling organisms. It has been put to practical use. However, since these compounds are extremely harmful in the marine environment, in recent years, the emergence of pollution-free antifouling paints has been expected.

There are some known proposals for such pollution-free antifouling paints, for example, JP-A-63-227.
No. 673 discloses a quaternary ammonium salt of carboxymethyl cellulose, JP-A No. 63-280779 discloses a tetraalkylammonium salt, and JP-B No. 2-64167 discloses a quaternary ammonium salt type cationic polymer having a cation group. Quaternary ammonium salts such as copolymers of polymers are disclosed.

Also, some phosnium salt compounds are known to be biologically active chemical substances like various nitrogen-containing compounds, and have a broad activity spectrum against bacteria, fungi and algae. . Regarding these, for example, JP-A-62-114903 and JP-A-1-93
No. 596, Japanese Patent Publication No. 2-58998, and the like. Recently, vinylbenzylphosphonium salts have been proposed as phosphonium salt-based antibacterial paints and antifouling paints. (JP-A-5-156180, JP-A-5-1)
(71067)

[0010]

However, although the quaternary ammonium salt type antibacterial agent has a broad antibacterial spectrum, the bactericidal effect of acting on microorganisms by short-time contact is insufficient and durability is also problematic. Also, the antifouling properties of compounds of this kind against marine pollutants are not so expected,
Lack of practicality.

In view of the above facts, the inventors of the present invention have conducted extensive studies and as a result, as a result, a certain kind of vinylphosphonium salt and / or a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component has antibacterial properties and protection against marine organisms. The fact that excellent performance in stain resistance is exhibited was found, and the present invention was completed.

That is, an object of the present invention is to provide a novel paint containing a phosphonium salt compound having antibacterial and antifouling properties as a paint component.

[0013]

That is, the antibacterial and antifouling paint to be provided by the present invention has the following general formula:

[0014]

[Chemical 4] and

[0015]

[Chemical 5] and

[0016]

[Chemical 6]

(Wherein R ¹ , R ² and R ³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and an alkyl group, an aryl group and The aralkyl group may be substituted with a hydroxy group or an alkoxy group, X ⁻ represents an anion, A represents an alkylene group, and Y represents a hydrogen atom, a lower alkyl group or an aryl group. Alternatively, the composition is characterized in that two or more kinds of vinylphosphonium salts and / or a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component are contained in the coating composition as an active ingredient for antibacterial and antifouling.

The present invention will be described in more detail below.
The antibacterial and antifouling paint according to the present invention is, as described above, one or two represented by the general formulas (1) and (2), (3).
A composition comprising at least one vinylphosphonium salt or / and a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component in a paint as an active ingredient having an antibacterial and antifouling effect. included.

Composition in which one or more kinds of the above vinylphosphonium salt is mixed with a paint vehicle as an antibacterial antifouling agent A paint with an antifouling polymer obtained by polymerizing one or more kinds of the above vinylphosphonium salt as a monomer component Composition mixed in vehicle or as paint vehicle component Composition in which one or more vinyl phosphonium salt and antibacterial and antifouling polymer obtained by polymerizing the vinyl phosphonium salt as monomer component are mixed in paint vehicle or as paint vehicle component object

The polymer obtained by polymerizing a vinylphosphonium salt as a monomer component in the above and above means a polymer obtained by homopolymerizing the salt or copolymerizing with a compound having an unsaturated double bond copolymerizable with the salt. Means

In the above formulas (1), (2) and (3), specific examples of R ^{1 to} R ³ in the formula are hydrogen atom; methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl and octyl. , A linear or branched alkyl group having 1 to 20 carbon atoms such as dodecyl and isopropyl; an aryl group such as phenyl, tolyl and xylyl; an aralkyl group such as benzyl and phenethyl;
The aryl group and aralkyl group may be substituted with a hydroxy group or an alkoxy group; and the like. Of these, an alkyl group, an aryl group and an aralkyl group are preferable, and an alkyl group and an aryl group are more preferable. Also, R ¹ , R ² and R ³
May be similar or different groups. Antimicrobial effect, the alkyl group, under the influence of its length, for example, methyl, ethyl, butyl, tends to antibacterial effect increases seen as octyl and longer, in particular, one in R ¹ to R ³ For example, when only one is a higher alkyl group such as octadecyl (C ₁₈ ) and the other two are lower alkyl groups such as a methyl group, the hydrophilicity is high and the cell aggressiveness is enhanced, so that the antibacterial effect is high.

Examples of the anion (X ⁻ ) include halogen ions such as fluorine, chlorine, bromine or iodine, carboxyl ions such as formic acid, acetic acid and oxalic acid, sulfate ions, phosphate ions, methyl or dimethylphosphate ions, ethyl. Alternatively, diethyl phosphate ion, antimony fluoride ion, phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion, perchlorate ion and the like can be mentioned, and of these, halogen ion is preferable.

X ^- is antimony fluoride ion,
When it is phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion, or perchlorate ion, it becomes insoluble in water,
Also, the solubility is changed by changing R ^{1 to} R ³ .

Examples of A include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group and ethylethylene group. Examples of Y include a hydrogen atom; a lower alkyl group such as a methyl group, an ethyl group and a propyl group; and an aryl group such as a phenyl group.

Next, the vinylphosphonium salts represented by the formulas (1), (2) and (3) will be more specifically described. For example, the formula (1) is represented by tri-n-octylvinylphosphonium chloride and tri-n-octyl. Allylphosphonium chloride, tri-n-octylisopropenylphosphonium chloride, tri-n-butyl-3-butenylphosphonium bromide, tri-n-butyl-4-pentenylphosphonium bromide, tri-n-butyl-5-hexynylphosphonium bromide, dimethyln -Octadecyl allylphosphonium chloride and the like.

The formula (2) is represented by, for example, binoxycarbonylmethyltri-n-butylphosphonium chloride, binoxycarbonylmethyltri-n-octylphosphonium chloride, binoxycarbonylmethyldimethyl-n-octadecylphosphonium chloride, and aryloxycarbonylmethyltri. n-octylphosphonium chloride, 2
-(Binoxycarbonyl) -ethyltri n-octylphosphonium chloride, 3- (binoxycarbonyl)-
Examples include propyltri-n-butylphosphonium bromide.

The formula (3) is represented by, for example, methyl tri-n-butylphosphonium methacrylate, methyl tri-n-octyl phosphonium chloride, methyl dimethyl n-octadecylphosphonium chloride, 2- (methacrylic acid) -ethyl tri-n-.
Octylphosphonium chloride, 3- (methacrylic acid) -propyltrin-octylphosphonium chloride, 4- (methacrylic acid) -butyltrin-butylphosphonium bromide, methyl tri-n-octylphosphonium chloride acrylate, 2- (acrylic acid) -ethyltri Examples thereof include, but are not limited to, n-octylphosphonium chloride and 3- (acrylic acid) -propyltrin-octylphosphonium chloride.

Next, as a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component, the following general formulas (4), (5) and (6) are used.

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

(Wherein R ^{1 to} R ³ , A, Y and X ⁻ are the same as defined above) or a homopolymer represented by the formula as a constituent part of the polymer is Can be mentioned.

[0033] Such (4), (5) and (6) antibacterial antifouling effect of the homopolymer of vinyl phosphonium salt represented by formula, like the vinyl phosphonium salt, R ¹ of the phosphonium salt in the formula ~R ^{When 3} is an alkyl group,
Although affected by its length, its antibacterial effect is far superior to that of the vinylphosphonium salt.

The degree of polymerization of the polymers represented by the above formulas (4), (5) and (6) is not particularly limited, but is 2 or more, and in many cases 5 or more, preferably 10 to 20.
The range of 0 is excellent in antibacterial activity and antifouling property.

Examples of the compound having an unsaturated double bond copolymerizable with the vinylphosphonium salt in the copolymers represented by the formulas (4), (5) and (6) include ethylene, propylene, butylene and butadiene. , Isobutylene, diisobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylamide, vinyl alcohol, vinyl acetic acid, acrylonitrile, vinyl sulfonate, N- Typical examples thereof include vinyl-2-pyrrolidone, maleic acid, maleic anhydride, fumaric acid, styrene, diacetone acrylamide, vinyltoluene, cinnamic acid, vinylthiophene, vinylpyridine and vinylimidazole, and these may be used alone or in combination. It may be more than one species.

The proportion of structural units of the vinylphosphonium salt in the copolymer of the compound having an unsaturated double bond and the vinylphosphonium salt is usually 1 to 99 mol%, preferably 5 to 50 mol%. desirable. The ratio of structural units of a compound having an unsaturated double bond is usually 99
˜1 mol%, preferably 95 to 50 mol%.

The above-mentioned polymer can be polymerized by heating or irradiation with active energy rays such as ultraviolet rays in the presence of a usual polymerization initiator. As a specific polymerization initiator, a radical polymerization initiator is preferable, and for example, benzoiolpoxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate,
t-butyl peroxydiisobutyrate, t-butyl peroxyisopropyl carbonate, lauroyl peroxide, azobisisobutyronitrile, azobis-
(2,4-dimethylvaleronitrile) or the like is used.
Further, in the case of irradiation with active energy rays, a photopolymerization initiator such as benzoin ether or a sensitizer is used if necessary. The amount of these initiators used is 0.001 to 5% by weight.
Is desirable. Further, the polymerized form of each structural unit in this copolymer is various and may be random, block or graft.

The degree of polymerization of the copolymer is not particularly limited, but in many cases, the antibacterial activity is excellent when it is 5 or more, preferably 40 to 200. The vinylphosphonium salt according to the present invention and the polymer obtained by polymerizing the vinylphosphonium salt as a monomer component are represented by R ^{1 to} R ³ in the general formula,
By changing A, Y and X ^- and the degree of polymerization, the antibacterial and antifouling property can be designed with the solubility depending on the use. The vinyl phosphonium salt of the formulas (1), (2) and (3) or / and the polymer obtained by polymerizing the vinyl phosphonium salt as a monomer component is a broad antibacterial spectrum effective against various bacteria, fungi, algae, viruses and the like. Indicates
It has excellent antibacterial and antifouling properties, and has extremely high chemical and thermal stability, so that its efficacy is extremely durable.

The antibacterial and antifouling coating composition of the present invention may be used in combination with other antibacterial or antifouling agent, if necessary. For example, as the antibacterial agent, an inorganic antibacterial agent such as barium metaborate, antibacterial zeolite, antibacterial apatite, or 1-[(diiodomethyl) sulfonyl] -4-methylbenzene, 3-iodo-2-probargyl butyl carbamate, N, N-dimethyl-N'-
(Fluorodimethylthio) -N'-phenylsulfanide, 2- (4-thiazolyl) benzimidazole, 2,
Organic antibacterial agents such as 3,5,6-tetrachloroisophthalonitrile, tetrachloro-4-methylsulfonylpyridine, copper 8-oxynoline, and tetradecyldimethylbenzylammonium chloride are listed, and these may be used alone or in combination of two or more. It doesn't matter even if it is used.

Other antifouling agents include, for example, triphenyltin hydroxide, triphenyltin acetate, triphenyltin chloride, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, cuprous oxide, tributyltin fluoride, tributyltin. Methacrylate copolymers, triphenyltin fluoride, triphenyltin versatic acid, quaternary ammonium salts and the like can be mentioned, and these may be used alone or in combination of two or more.

The paint vehicle containing the antibacterial and antifouling agent according to the present invention is not particularly limited, and either oily or water-based can be used depending on the purpose of use. As the paint vehicle, a commonly used paint may be used, for example, oily paint such as boil oil, paint, varnish, enamel, alkyd resin paint, cellulose derivative paint such as nitrocellulose lacquer, aminoalkyd resin paint, Vinyl paint such as vinyl chloride resin and vinyl chloride-vinyl acetate polymer resin, chlorinated polypropylene resin paint, chlorine rubber resin paint, acrylic resin paint, epoxy resin paint, polyurethane resin paint and other synthetic resin paints,
Cement-based paints, powdered and kneaded water-based paints, synthetic latex paints, emulsion paints, water-based paints such as water-soluble paints, silicon-containing resin paints, fluorine-containing resin paints, arrayed dicyclopentadiene resin paints, tributyltin-containing acrylic copolymers Further, an organic tin polymer such as an acrylic copolymer containing triphenyltin can be used.

In the antibacterial and antifouling paint of the present invention, one or more vinyl phosphonium salts represented by the formulas (1), (2) and (3) or / and the vinyl contained in the coating material. The amount of the polymer obtained by polymerizing the phosphonium salt as a monomer component varies widely depending on the application of the paint, but in many cases, it is 0.
001 to 50% by weight, preferably 0.01 to 30% by weight
The range is appropriate. This is because when the content is 0.001% by weight or less, the antibacterial action of the antibacterial and antifouling paint is not substantially obtained, and the upper limit is often limited for economic reasons, and is in a practical range. Is set.

The antibacterial and antifouling coating composition of the present invention may optionally contain a pigment and other coating auxiliary components. Examples of the pigment to be added include white pigments such as zinc white, lithobon, and titanium oxide; coloring pigments such as carbon black, benzalta, iron oxide, yellow lead, chromium oxide, phthalocyanine blue, phthalocyanine green, ultramarine blue, and toluidine red; Gypsum dihydrate, calcium carbonate, silica, bentonite, clay, talc, barium sulfate, aluminum hydroxide and other extender pigments; copper powder, aluminum and other metal powder pigments and rust preventive pigments, dispersants, wetting agents, defoamers, Foaming agent,
Surfactants such as emulsifiers; film forming aids, freeze stabilizers, organic solvents such as plasticizers; methyl cellulose, polyvinyl alcohol, hydroxymethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, guagarm, anti-aging agents,
Thickening agents such as UV inhibitors; lightweight bone agents such as foamed clay, pumice, perlite, styrofoam powder, shirasu balloon, and leucite; various additives such as water, cold water stone, silica sand, and preservatives. These additives should be appropriately selected according to the physical properties of each component in the coating composition and the purpose of use,
The amount added is not particularly limited, but is at most 80% by weight based on the total weight.

The method for preparing the antibacterial antifouling paint of the present invention is as follows:
The method is not particularly limited as long as each component is uniformly mixed, and a known method can be used. For example, a method of using a dispersing device such as a high speed mill, a ball mill, or a sand mill, sequentially adding various compounding materials, and mixing and dispersing the materials can be mentioned. The coating method includes roller coating, iron coating, spray coating, brush coating and the like, and the surface shape of the coating film and coating layer can be freely changed by selecting the coating method.

[0045]

The antibacterial and antifouling coating composition according to the present invention is a coating composition containing, as an active ingredient, a vinylphosphonium salt and / or a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component, but the detailed mechanism of its action is unknown. In Although,
Perhaps the following can be estimated.

That is, the vinyl phosphonium salt has a broad antibacterial and antifungal spectrum, regardless of whether it is a monomer or a polymer, whose specific compound which depends on the phosphonium salt has a broad antibacterial and antifungal spectrum against harmful microorganisms such as bacteria and mold.
Alternatively, it has a strong algicidal activity against fouling organisms in water and in the sea, such as shellfish and algae, and in particular, in many cases, a polymeric phosphonium salt has the above-mentioned antibacterial and antifouling function in spite of less chemical damage. It is preferable because it is excellent.

[0047]

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

Examples 1 to 10 and Comparative Example 1 (1) Preparation of Antibacterial Paint The vinylphosphonium salt of the formulas (1), (2) and (3) shown in Table 1 and / or the vinylphosphonium salt as a monomer. The following coating composition containing at least an antibacterial polymer contained as a component was kneaded with a triple roll to obtain an antibacterial coating. The polymerization degree of the polymer in the compounds shown in Table 1 is shown in Table 2.

[0049]

[Table 1]

[0050]

[Table 2]

[Antibacterial paint 1] Sample A 1.0 part Vinyl acetate emulsion paint 1000 parts (Kansai Paint Co., Ltd., Vinyl Paint 100)

[Antibacterial paint 2] Sample B 0.2 parts Vinyl acetate emulsion resin 38.6 parts Rutile titanium oxide 33.6 parts Clay 23.4 parts Calcium carbonate 23.4 parts Neugen EA-120 (Daiichi) Industrial chemicals, surfactants) 0.4 parts Soybean lecithin 1.0 parts Potassium tripolyphosphate 0.2 parts Napollo NWE (Sanyo Kasei, defoamer) 0.2 parts Dibutyl phthalate 1.8 parts Ethylene glycol 4. 2 parts Butylcellosolve 1.4 parts Water 46.6 parts

[Antibacterial paint 3] Sample C 2 parts Red achiryl emulsion paint 1000 parts (Dainippon Paint Co., Ltd., Acroze 100V)

[Antibacterial paint 4] Sample D 15 parts Yellow vinyl emulsion paint 2000 parts (Dainippon Paint Co., Ltd., Vinylose 410)

[Antibacterial paint 5] Sample E 0.3 part Styrene-acrylic acid ester copolymer 33 parts Diethylene glycol 4.5 parts Sodium hexametaphosphate 10% aqueous solution 4.5 parts Hydroxypropyl methylcellulose 2% aqueous solution 94.5 parts Rutile type titanium oxide 21.0 parts Calcium carbonate 107.4 parts Calcium silicate 6.0 parts

[Antibacterial paint 6] Sample F 0.3 parts Styrene-acrylic acid ester copolymer 33 parts Diethylene glycol 4.5 parts Sodium hexametaphosphate 10% aqueous solution 4.5 parts Hydroxypropyl methylcellulose 2% aqueous solution 94.5 parts Rutile type titanium oxide 21.0 parts Calcium carbonate 107.4 parts Calcium silicate 6.0 parts

[Antibacterial paint 7] Sample G 0.3 part Styrene-acrylic acid ester copolymer 33 parts Diethylene glycol 4.5 parts Sodium hexametaphosphate 10% aqueous solution 4.5 parts Hydroxypropyl methylcellulose 2% aqueous solution 94.5 parts Rutile type titanium oxide 21.0 parts Calcium carbonate 107.4 parts Calcium silicate 6.0 parts

[Antibacterial paint 8] Sample H 0.3 part Styrene-acrylic acid ester copolymer 33 parts Diethylene glycol 4.5 parts Sodium hexametaphosphate 10% aqueous solution 4.5 parts Hydroxypropyl methylcellulose 2% aqueous solution 94.5 parts Rutile type titanium oxide 21.0 parts Calcium carbonate 107.4 parts Calcium silicate 6.0 parts

[Antimicrobial paint 9] Sample A 0.5 part Sample B 0.5 part Vinyl acetate emulsion paint 1000 parts (Kansai Paint Co., Ltd., Vinyl Paint 100)

[Antibacterial paint 10] Sample B 0.5 part Sample C 0.5 part Vinyl acetate emulsion paint 1000 parts (Kansai Paint Co., Ltd., Vinyl Paint 100)

(2) Antibacterial activity test The above-mentioned various antibacterial paints were applied on an aluminum plate plate with a bar coater of 60 μm, and after drying 50 × 50 horizontal.
B. A test piece having a thickness of 1 mm was prepared. B) Staphylococcus aureus, a representative gram-positive bacterium
s) IFO 12732 and Escherichia col as a representative of Gram-negative bacteria
i) The test piece obtained in each example was applied to IFO 3806. The obtained antibacterial activity results are shown in Table 3.
Shown in. The evaluation of bactericidal activity was performed by the solution dilution method. Solution dilution method: Into 18 ml of physiological saline, 2 ml of 10 7 bacteria per 1 ml was ingested, a test piece (vertical 10 × horizontal 10 × thickness 1 mm) was contacted, and the number of bacteria thereafter was measured.

(B) Next, a test piece (vertical 10 × width 1)
(0 × thickness 1 mm) was added to 50 ml of preliminarily adjusted mold dilution water (Note 1), and the mixture was slowly stirred with a magnetic stirrer for 10 minutes. Next, this liquid was subjected to a culture test (Note 2) using a simple microorganism measuring device, San-Ai Bio Checker M (for fungi and yeasts inspection: manufactured by San-ai Petroleum Co., Ltd.). The evaluation results obtained are shown in Table 3. (Note 1) ± 1 g of black mold wall was diluted in 100 ml of sterile water: for fungal test (Note 2) Culture was carried out in an incubator at 27 to 30 ° C for 2 days for total bacteria and 4 days for fungi It was

[0063]

[Table 3]

(Note 3) The total number of bacteria was evaluated based on the relationship between the degree of colony formation and the number of bacteria roughly determined in advance. 0 is a case in which no colony was found. (Note 4) The degree of fungal contamination was evaluated according to the following four grades. -: No pollution +: Light pollution ++: Medium pollution +++: Severe pollution (Note 5) Coating composition except Sample A from antibacterial coating 1

Examples 11 to 20, Comparative Example 2 (3) Preparation of Antifouling Paint An antifouling paint was prepared by kneading the raw materials shown in Table 4 below.
All the numbers in Table 4 indicate parts by weight.

[0066]

[Table 4]

(4) Test An iron plate (vertical 151 mm × horizontal 100) precoated with a rust preventive paint was prepared from the paints having the respective compositions shown in Table 4 below.
mm, thickness 2 mm) was coated with a 60 μm bar coater and dried to obtain a dip test plate. Next, in Tokuyama Bay, Yamaguchi Prefecture, a comparative test of antifouling performance was conducted by immersing the product in a water depth of 1.5 m to 2 m for two years.

The results of the biofouling status are shown in Table 5. [Evaluation in Table 5] A: No or very little biological attachment. ◯: Biofouling is clearly observed, but there is no practical problem. Δ: There is considerable biofouling, which is a practical problem. X: Very much biological attachment.

[0069]

[Table 5]

[0070]

As described above, the antibacterial and antifouling coating material according to the present invention is excellent because it is prepared by adding and blending a vinylphosphonium salt or / and a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component. Since it has antibacterial and antifouling properties, and has a strong antifouling action against fouling organisms in seawater, it is a highly practical alternative to conventional antifouling paints for ship bottom paints and various undersea structure paints. Can be expected as

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuyoshi Hashimoto 9-15-1 Kameido, Koto-ku, Tokyo Nippon Chemical Industry Co., Ltd. Research & Development Division (72) Inventor Keiko Inaba 9-15 Kameido, Koto-ku, Tokyo -1 Research & Development Division, Nippon Chemical Industry Co., Ltd.

Claims (2)

[Claims] 1. The following general formula: And And (In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and an alkyl group, an aryl group and an aralkyl group are Optionally substituted with a hydroxy group or an alkoxy group, X ⁻ represents an anion, A represents an alkylene group, and Y represents a hydrogen atom, a lower alkyl group or an aryl group). An antibacterial and antifouling paint comprising the above-mentioned vinylphosphonium salt and / or a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component as an active ingredient for antibacterial and antifouling in a coating composition. 2. A vinylphosphonium salt having an antibacterial and antifouling function and / or a polymer obtained by polymerizing the vinylphosphonium salt as a monomer component is 0.00
The antibacterial and antifouling paint according to claim 1, which contains 1 to 50% by weight.