JP2001294810A - Underwater antifouling paint composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an underwater antifouling paint composition excellent in safety to human bodies and aquatic animals and plants, having high persistence in antifouling effects and capable of preventing adhesion of aquatic lives to the surfaces of the waterlines of ships, undersea parts of offshore constructs, aqueducts, channels in contact with sea water in electric power plants, fishing nets, etc. SOLUTION: This underwater antifouling paint composition comprises a quaternary ammonium salt-containing organosiloxane containing at least one unit expressed by a structure of formula (1) (wherein R1 expresses H or a substituted or unsubstituted 1-10C monovalent organic group; R2 expresses a monovalent organic group containing at least one quaternary ammonium salt; R3 expresses a group expressed by R1 or R2; p expresses a positive number in the range of 5<=p<=500) and a binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ship
The present invention relates to an underwater antifouling paint composition for preventing underwater animals and plants from adhering to underwater structures and fishing nets.

[0002]

2. Description of the Related Art
Quaternary ammonium salt-containing silanes represented by 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride are used as treatment agents for imparting antibacterial properties to various fibers or fillers for molded articles.
This silane is characterized by its low toxicity, little irritation to the skin, and excellent washing resistance to natural fibers such as cotton, but to synthetic fibers such as nylon and polyester. There was a disadvantage that the washing resistance was insufficient. Further, since the quaternary ammonium salt-containing silane is a solid, it must be supplied as an alcohol solution of methanol or the like, which raises the cost of the transportation surface, and the volatilization of methanol during coating leads to environmental problems. There was a risk of contamination and a danger of ignition, and there was also a problem in safety.

[0003] In order to make up for these drawbacks, several quaternary ammonium salt-containing compounds have been proposed. That is, in JP-A-6-101174, a polysiloxane having a quaternary ammonium salt in a side chain is further disclosed in JP-A-6-29.
No. 8775 proposes a compound having a quaternary ammonium base at both ends. However, all of these polysiloxane intermediates have complicated production processes and are expensive, and have poor adhesion to various fibers because the groups bonded to silicon atoms are quaternary ammonium bases and alkyl groups. There was a disadvantage.

Further, as antifouling paints for hulls and fishing nets, 4
Although the use of trimethoxysilane containing a quaternary ammonium salt is disclosed in JP-A-6-179603, problems such as environmental pollution, lack of safety, and economic problems due to handling with a methanol solution still remain. Was. An organopolysiloxane-based underwater antifouling agent containing a quaternary ammonium salt and a polyether group is disclosed in
No. 3,306,687, the production method of this organopolysiloxane is complicated and the synthesis route is long,
Economic advantages are small.

An object of the present invention is to provide a product which solves the above-mentioned problems of the conventional underwater antifouling agent. That is, it does not contain toxic substances such as organotin and cuprous oxide, and therefore, is excellent in safety to human body and aquatic animals and plants, is environmentally friendly, and has excellent adhesion and persistence to the object to be treated, and therefore, antifouling. The effect is highly durable.Especially when applied to seawater, such as the draft of ships, the lower part of the sea surface of marine structures, the water pipes and conduits of power plants, and the surface of fish nets, it prevents the adhesion of underwater organisms. It is an object of the present invention to provide an underwater antifouling paint composition which is effective for water.

[0006]

That is, the present invention provides a liquid crystal display device comprising at least one unit represented by the following general formula (1):
An underwater antifouling coating composition comprising a quaternary ammonium salt-containing organopolysiloxane and a binder resin.

Embedded image (Wherein R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms, R ² is a monovalent organic group containing at least one quaternary ammonium salt, and R ³ is R ¹ Alternatively, a group represented by OR ¹ and p represents a positive number of 5 ≦ p ≦ 500.) According to a second aspect of the present invention, the terminal of the quaternary ammonium salt-containing organopolysiloxane is represented by the following general formula (2): The underwater antifouling paint composition according to claim 1, which is represented by a structure.

Embedded image (Here, R ¹ , R ² , R ³ , and p are the same as described above.) In the third invention of the present invention, R ² is represented by the general formula (3): —CH ₂ CH ₂ CH ₂ N ⁺ R ⁴ R ⁵ R ⁶ Cl ⁻ (3) (where R ⁴ and R ⁵ represent the same or different monovalent hydrocarbon groups having 1 to 3 carbon atoms, and R ⁶ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms) a monovalent water antifouling paint composition according to claim 1 or 2, wherein an organic group represented, the fourth invention R ² is the compounds of general formula _{(4) -CH 2 CH 2 CH} 2 N + _{(CH 3) 2 C n H} 2n + 1 Cl - (4) (n represents a positive number of 12 to 24) a monovalent water antifouling coating composition according to claim 3, wherein an organic group represented by is there.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, R ¹ of the quaternary ammonium salt-containing organopolysiloxane containing at least one unit represented by the structure of the general formula (1) is a hydrogen atom or a substituted or unsubstituted monovalent organic compound having 1 to 10 carbon atoms. Alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group; alkenyl group such as vinyl, allyl, propenyl, butenyl and hexenyl; Aralkyl groups such as benzyl, phenylethyl and phenylpropyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; or some or all of the hydrogen atoms bonded to these carbon atoms are substituted with halogen atoms Chloromethyl group, trifluoropropyl group, chlorophenyl group, etc. Halogenated alkyl group,
Examples include a halogenated aryl group such as a halogenated phenyl group. Further, as the organic group for R ¹ , a part of the hydrogen atoms bonded to these carbon atoms may be substituted with a nitrogen atom-containing monovalent organic group such as an amino group or an alkylamino group. Among them, particularly, 90 of R ¹
Preferably, at least mol% is a methyl group, a phenyl group, or a trifluoropropyl group. Industrially, it is more preferred that 90 mol% or more is a methyl group.

In the present invention, the organic group R ² of the organopolysiloxane containing a quaternary ammonium salt containing at least one unit represented by the structure of the general formula (1) is a monovalent organic compound containing at least one quaternary ammonium salt. And a group represented by the following general formula (3) is exemplified as preferred. —CH ₂ CH ₂ CH ₂ N ⁺ R ⁴ R ⁵ R ⁶ Cl ⁻ (3) Among the groups represented by the general formula (3), particularly preferred are groups represented by the following two formulas. is there. _{H -CH 2 CH 2 CH 2 N} + (CH 3) 2 C 18 H 37 Cl - -CH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 (C 6 H 5) Cl - Furthermore, R ² is The group represented by the general formula (4) is also preferable.

In the present invention, R ³ of the quaternary ammonium salt-containing organopolysiloxane containing at least one unit represented by the structure represented by the general formula (1) is a group represented by R ¹ or —OR ^1. Examples include a hydrogen atom, a hydroxy group, a methoxy group, an ethoxy group, a propoxy and the like, with a methoxy group being most preferred.

In the general formula (1) or (2), p is 5 ≦
It represents a positive number of p ≦ 500, but if it exceeds 500, the content of the quaternary ammonium salt is reduced and the antifouling property is reduced. Therefore, p needs to be a positive number of 5 ≦ p ≦ 500. And preferably 10 ≦ p ≦ 200.

In the present invention, the terminal group of the quaternary ammonium salt-containing organopolysiloxane containing at least one unit represented by the general formula (1) is arbitrary, and may be a dialkylhydroxysilyl group, a trialkylsilyl group, an alkyldialkoxysilyl. Groups, dialkylalkoxy groups and the like are exemplified, and from the viewpoint of stability, dialkylhydroxysilyl groups, trialkylsilyl groups, and alkyldialkoxysilyl groups are preferred. Further, a terminal group represented by the structure of the general formula (2) is also exemplified.

Specific examples of the quaternary ammonium salt-containing organopolysiloxane containing at least one unit represented by the general formula (1) in the present invention include the following (a) to (m)
Is exemplified.

Embedded image

[0013]

Embedded image ^{_{However, A 1: CH 2 CH 2}} CH 2 N + (CH 3) 2 C 18 H 37 Cl - A 2: CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2

The method for producing the organopolysiloxane containing a quaternary ammonium salt, which is the main component of the underwater antifouling coating composition of the present invention, comprises (A) α, ω- represented by the following general formula (5).
It can be obtained by subjecting dihydroxydimethylsiloxane and (B) to a dealcoholation reaction with a quaternary ammonium salt-containing trialkoxysilane or a quaternary ammonium salt-containing dialkoxysilane represented by the following general formula (6). This manufacturing method has already been filed as a prior application by the present inventors (Japanese Patent Application No. 11-313778).
issue).

Embedded image (Where R ¹ and p are the same as above)

Embedded image (Where R ¹ , R ² and R ³ are the same as above)

The trialkoxysilane or dialkoxysilane containing the quaternary ammonium salt is also industrially produced in large quantities as an alcohol solution.
An organopolysiloxane containing a quaternary ammonium salt can also be obtained at a lower cost than that obtained by a conventional synthesis method. Furthermore, since alcohol is distilled off under reduced pressure during the manufacturing process, the final product does not contain alcohol, and is excellent in safety.

The quaternary ammonium salt-containing organopolysiloxane is exemplified in Japanese Patent Publication No. 49-11760, but is used as a foam stabilizer. Does not contain the alkoxy group necessary to impart adhesion,
The synthesis method is completely different since it does not utilize a dealcoholation reaction.

As described above, the inventors of the present invention filed a patent application for a method for producing a quaternary ammonium salt-containing organopolysiloxane by a method of subjecting α, ω-dihydroxydimethylpolysiloxane and a quaternary ammonium salt-containing trialkoxysilane to a dealcoholation reaction. did. Since this quaternary ammonium salt-containing organopolysiloxane has both a polysiloxane skeleton and an alkoxy group, it imparts excellent adhesion and persistence to various objects to be treated to an underwater antifouling paint containing this compound. I do. In addition, α, ω-
Dihydroxydimethylpolysiloxane is inexpensive, and the other raw material, quaternary ammonium salt-containing trialkoxysilane or dialkoxysilane, is industrially mass-produced as an alcohol solution.
Organopolysiloxanes containing quaternary ammonium salts are also less expensive than those produced by conventional synthetic methods. Furthermore, since alcohol is distilled off under reduced pressure during the manufacturing process, the final product does not contain alcohol, and is excellent in safety. By using aminosilanes such as aminopropylaminotrialkoxysilane and N-aminoethyl-3-aminopropyltrialkoxysilane [hereinafter referred to as the component (C)], amino groups and quaternary ammonium salts are contained. An organopolysiloxane containing both groups is obtained, and the use of this compound has the advantage that antibacterial properties can be imparted.

In the general formula (5) of the component (A), p is 5
It is a positive number of ≦ p ≦ 500. If p is less than 5, the silanol is unstable, so that a condensation reaction occurs simultaneously with the reaction with the component (B) represented by the general formula (6), and as a result, a cyclic compound is by-produced. Further, when p exceeds 500, the content of the quaternary ammonium salt decreases, and therefore, the antifouling property decreases. Therefore, p needs to be a positive number of 5 ≦ p ≦ 500, and preferably 10 ≦ p ≦ 500. p ≦ 200.
R ¹ is the same as described above, and it is particularly preferable that 90 mol% or more is a methyl group, a phenyl group, or a trifluoropropyl group. Formulas (n) to (n) of specific examples of the α, ω-dihydroxydimethylpolysiloxane represented by the general formula (5)
(P) is exemplified below.

[0019]

Embedded image

In the formula of the general formula (6) of the component (B), R ² , R
³ is the same as that in the general formula (1), and as R ² , those represented by the general formula (3) have excellent reactivity with the component (A), high antifouling property, and easy synthesis. Among them, a quaternary ammonium salt-containing organic group represented by the following formula is most preferable. -CH ₂ CH ₂ CH
_{^{2 N + (CH 3) 2}} C 18 C 37 Cl -

In the formula (6), R ³ is most preferably a methoxy group in which a dealcoholization reaction easily proceeds. Specific examples of the preferable quaternary ammonium salt-containing silane of the component (B) represented by the general formula (6) include those represented by the following formula. (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ C ₁₈ H ₃₇ C
_{^{l - (CH 3 O) 2}} (CH 3) SiCH 2 CH 2 CH 2 N + (CH 3) 2 C
_{^{18 H 37 Cl - (CH 3}} O) 3 SiCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 (C 6
_{^{H 5) Cl - (CH 3}} O) 2 (CH 3) SiCH 2 CH 2 CH 2 N + (CH 3) 2 C
_{H 2 (C 6 H 5)} Cl -

In addition to the silane represented by the general formula (6), it is optional to use an aminosilane as the component (C) as shown below. As the aminosilane, those shown below can be used. Is exemplified. (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NH ₂ (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NH ₂ (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHC
H ₂ CH ₂ NH ₂

[0023]

Embedded image

The reaction conditions of the components (A) and (B) are as follows:
Although it depends on the reactivity of the silanol of the component (A) and the reactivity of the alkoxy group of the component (B), the reaction is generally preferably performed at a reaction temperature of 50 to 180 ° C. for 3 to 20 hours. By this reaction, a quaternary ammonium salt-containing organopolysiloxane represented by the general formula (1) or (2) can be easily obtained. Since the quaternary ammonium salt in the component (B) is usually in the form of an alcohol solution such as methanol, it is necessary to react in an alcohol solution or to remove the alcohol before the reaction. In order to promote the reaction efficiently, it is preferable to carry out the reaction while removing the alcohol from the system. In addition to the components (A) and (B), it is also possible to use the above-mentioned aminosilanes in combination, thereby promoting the dealcoholation reaction. A solvent is not particularly required in this reaction, but when the viscosity of the component (A) is high or the viscosity of the product is high, the reaction may be performed using a solvent such as toluene or xylene. When the molar ratio (A) / (B) of the reaction conditions of the component (A) and the component (B) is greater than 2.0, a large amount of polysiloxane containing no quaternary ammonium salt remains. It is not preferable because
If this is less than 0.5, quaternary ammonium silane will remain. Therefore, preferably 0.5 ≦ (A) /
(B) ≦ 2.0. If the quaternary ammonium salt content of the obtained quaternary ammonium salt-containing organopolysiloxane is less than 0.05% by weight, a sufficient antifouling effect cannot be obtained, so that it is preferably 0.05% by weight or more. .

Usually, the modification or crosslinking of the organopolysiloxane is carried out by reacting the amino group-containing organopolysiloxane with an organic compound containing an organic acid, an epoxy group or the like. The quaternary ammonium salt-containing organopolysiloxane obtained by the reaction of the components is also modified with an organic acid and an epoxy group-containing organic compound when the aforementioned aminosilane is used in addition to the components (A) and (B). Or cross-linking is optional. Particularly, a crosslinkable polymer is preferable for imparting durability to the coating film, and these organic compounds are also useful as the binder resin of the present invention. Examples of the organic acid include formic acid, acetic acid, acetic anhydride, and propanoic acid.

The binder resin usable in the underwater antifouling coating composition of the present invention includes silicone resin, acrylic resin, styrene resin, epoxy resin, alkyd resin, polybutene resin, butadiene resin, polyamide resin, urethane resin, fluorine resin, A resin selected from a polyester resin, a phenol resin, and the like, or a resin obtained by combining two or more of these resins may be used. The blending amount of the binder resin is not particularly limited as long as the quaternary ammonium salt-containing organopolysiloxane can be fixed, but the blending ratio of binder resin / quaternary ammonium salt-containing organopolysiloxane is 20/80 to 95% by weight. / 5 is preferred.
In particular, it is more preferable to mix in the range of 40/60 to 90/10. When the amount of the binder resin is less than 20% by weight, the fixing ability becomes weak. When the amount of the binder resin exceeds 95% by weight, the content of the quaternary ammonium salt-containing organopolysiloxane of the present invention becomes low and the antifouling property tends to be poor.

The underwater antifouling coating composition of the present invention using an organopolysiloxane can be handled in a solvent-free state. Further, toluene, xylene, n-hexane, n-heptane, methyl ethyl ketone, methyl isobutyl ketone, acetic acid It can also be treated as a solution dissolved in an organic solvent such as ethyl, butyl acetate, or mineral turbene, or as an emulsion emulsified using a nonionic, anionic, cationic, or amphoteric surfactant.

There are no particular restrictions on the use of these surfactants. Examples of nonionic surfactants include ethoxylated higher alcohols, ethoxylated alkylphenols, polyhydric alcohol fatty acid esters, ethoxylated polyhydric alcohol fatty acid esters, and the like. Ethoxylated fatty acids, ethoxylated fatty acid amides, sorbitol, sorbitan fatty acid esters,
Examples thereof include ethoxylated sorbitan fatty acid esters and sucrose fatty acid esters, and their HLB is preferably in the range of 5 to 20, and particularly preferably in the range of 10 to 16. Examples of anionic surfactants include higher alcohol sulfates, alkylphenyl ether sulfates, alkylbenzene sulfonates, higher alcohol phosphates, ethoxylated higher alcohol sulfates, and ethoxylated alkylphenyl ether sulfates. Ester salts, ethoxylated higher alcohol phosphates, and the like.Examples of the cationic surfactant include alkyl trimethyl ammonium chloride, alkyl amine hydrochloride, coconut amine acetate, alkyl amine acetate, alkyl benzene dimethyl ammonium chloride, and the like. No. Examples of the amphoteric surfactant include N-acylamidopropyl-N, N-
Examples include dimethylammoniobetaines, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxypropylammoniobetaines, and the like. Further, the use amount thereof is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the organopolysiloxane and the binder resin of the present invention. In the emulsification, the amount of water used may be such that the solid concentration is 10 to 80% by weight, preferably 20 to 60% by weight.

The above emulsion can be obtained by a conventionally known method. The quaternary ammonium salt-containing organopolysiloxane of the present invention is mixed with a surfactant, and the resulting mixture is mixed with a homomixer, a homogenizer, a colloid mill, a line mixer, a universal mixer (trade name), an ultra mixer (trade name), and a planetary mixer. It may be emulsified by an emulsifier such as (trade name), Combimix (trade name), or a three-roll mixer. Industrially, it is preferable to mix the quaternary ammonium salt-containing organopolysiloxane of the present invention with an organic solvent solution or emulsified dispersion of the binder resin.

The water-based antifouling coating composition of the present invention may further contain other additives as long as its properties are not impaired, such as a coloring pigment, a moisture-resistant pigment, a coloring dye, an antistatic agent, an antioxidant and an antioxidant. Preservatives, rust preventives, thickeners, plasticizers, anti-sagging agents, physiologically active substances and the like can be added. The type and amount are not particularly limited.

When the underwater antifouling coating composition of the present invention is applied to various objects to be treated using the underwater antifouling coating composition of the present invention, the underwater antifouling coating composition of the present invention is adjusted to a predetermined concentration, and immersion, spraying, roll coating, etc. Is applied to the object to be treated. The object to which the underwater antifouling paint composition of the present invention is applied is an outer flank and an outer hull of a ship; a pier portion immersed under the sea surface of a bridge; an offshore structure such as an offshore oil drilling plant, an offshore tank, a buoy; It is a part that comes into contact with seawater, such as a water pipe and a water channel, a fish culture prop, a fish net, and a fixed net. In addition, as the material of the object, concrete, natural stone, iron, metal such as aluminum, synthetic resin such as FRP can be applied without any particular limitation, and raw materials for fish nets are natural fibers such as cotton and hemp, polyvinyl chloride, and polyvinyl chloride. The present invention can be applied to synthetic fibers such as polyethylene, nylon, polypropylene, polyester, and polyacrylonitrile.

The treatment amount of the underwater antifouling coating composition of the present invention for various objects to be treated is not particularly limited, but in consideration of the durability and economic efficiency of the antifouling effect, the coating thickness is 5 to 100 g / m ² . Alternatively, for a fish net or the like, it is effective and economical to set the dry weight to 3 to 30% by weight.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The viscosities in the examples are all values at 25 ° C.

<Structural Analysis by ²⁹ Si-NMR> 1.65 g of sample, 1.50 g of toluene, benzene-d
⁶ 0.20 g, tris- (2,4-pentanedionate) chromium as a relaxation reagent was uniformly dissolved,
Fill a 0 mm sample tube and use Lambda30
Using 0WB (JEOL), the peak of ²⁹ Si-NMR was observed by integrating 600 to 3,000 times.

<Synthesis Example 1> An α, ω-dihydroxydimethylpolyamine represented by the following average structural formula (7) as a component (A) was placed in a 1,000 ml glass flask equipped with a mechanical stirring blade, a cooling tube, and a thermometer. Siloxane 308.
3g (0.100mol)

Embedded image And 261.1 g (0.3%) of a 38% by weight solids solution of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as a component (B) in methanol.
200 ml) and reacted at 70 ° C. under reflux of methanol for 2 hours. Next, an ester adapter was attached, and methanol was distilled off under a stream of nitrogen. afterwards,
The liquid temperature was set to 120 ° C., and the mixture was stirred for 4 hours under nitrogen. After completion of the reaction, a highly viscous colorless and transparent oily substance was obtained. This is designated as (A-1). For the product obtained, ²⁹ Si
The result of Table 1 was obtained by performing structural analysis by -NMR.

[0036]

[Table 1]

From the analysis results and the reaction route, 95% of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride was reacted with the polysiloxane, and (A-1) was represented by the following average structural formula (8) Was found to contain 60% of the structure represented by the formula and 35% of the structure represented by the average structural formula (9). Table 3 shows the measurement results of the volatile content and rotational viscosity of (A-1).

Embedded image

Embedded image A ¹ : CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ C ₁₈ H ₃₇ Cl ⁻

<Synthesis Example 2> (A) was placed in a 500 ml glass flask equipped with an ester adapter, a cooling tube, and a thermometer.
308.3 g (0.0%) of α, ω-dihydroxydimethylpolysiloxane represented by the average structural formula (7) as a component
50 mol) and N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane 1 as the component (C)
0.3 g (0.050 mol) was charged and 2
Allowed to react for hours. Distillation of methanol by demethanol reaction was observed in the ester adapter. After cooling,
32.7 g (0.025 mol) of a 38% solids methanol solution of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as the component (B)
l) and charged at 70 ° C. under reflux of methanol.
The reaction was allowed to proceed for an hour, and then methanol was distilled off under a stream of nitrogen. Thereafter, the liquid temperature was set to 120 ° C., and the mixture was stirred for 2 hours under a stream of nitrogen. After the completion of the reaction, a viscous colorless and transparent oily substance was obtained. This is designated as (A-2). When the obtained product was subjected to structural analysis by ²⁹ Si-NMR, it was found that (A-2) had the following structural formula (10). Table 3 shows the measurement results of the volatile content and rotational viscosity of (A-2).

Embedded image A ¹ : CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ C ₁₈ H ₃₇ Cl ^- A ² : CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂

<Synthesis Example 3> α, ω represented by the average structural formula (7) as the component (A) was placed in a 500 ml glass flask equipped with an ester adapter, a cooling tube, and a thermometer.
308.3 g of dihydroxydimethylpolysiloxane
(0.050 mol) and N-β- as component (C)
5.56 g (0.050 mol) of (aminoethyl) γ-aminopropylmethyltrimethoxysilane was charged, and 1
The reaction was performed at 20 ° C. for 2 hours. Distillation of methanol by demethanol reaction was observed in the ester adapter. After cooling, 3- (trimethoxysilyl) as the component (B)
130.6 g of a 38% solids methanol solution of propyldimethyloctadecyl ammonium chloride (0.1%
(00 mol), and methanol was distilled off under a stream of nitrogen. Thereafter, the liquid temperature was set to 120 ° C., and the mixture was stirred for 2 hours under a stream of nitrogen. After the completion of the reaction, a viscous colorless and transparent oily substance was obtained. This is designated as (A-3). When the obtained product was subjected to structural analysis by ²⁹ Si-NMR, it was found that the product had an average structure shown in Table 2 below.

[0040]

[Table 2]

From the results of the analysis and the reaction route, it was found that 85% of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride had reacted with the polysiloxane, and (A-3) showed the above average structural formula (9) )) And 25% of the structure represented by the average structural formula (10). Table 3 shows the measurement results of the volatile content and rotational viscosity of (A-3).

[0042]

[Table 3]

<Examples 1, 2, 3, Comparative Example>
3, quaternary ammonium salt-containing organopolysiloxane (A-1) obtained in Synthesis Examples 1 to 3 in 100 parts by weight of a commercially available xylene-based acrylic black paint (non-volatile content 50%, acrylic resin solid content 40%), After adding (A-2) and (A-3) each in an amount of 20 parts by weight and mixing, the stainless steel plate was added with 20 g / m2.
² and dried at 120 ° C. for 30 minutes to prepare a test piece. As a comparative example, a test piece using an organopolysiloxane containing no quaternary ammonium salt was produced. These test pieces were subjected to a suspension test at a depth of 1.5 m for 6 months off the coast of Mie Prefecture. The state of adhesion of shellfish and seaweeds such as barnacles was observed, and the results are shown in Table 4.

[0044]

[Table 4]

[0045]

The underwater antifouling paint composition of the present invention is different from conventional underwater antifouling paints in that it does not contain toxic substances such as organotin and cuprous oxide. The anti-fouling effect has high sustainability. In particular, the draft section of ships, the lower part of the sea surface of marine structures,
When applied to the surface of a water channel, a fish net or the like, it is effective in preventing the adhesion of underwater organisms.

Claims (4)

[Claims] 1. A unit represented by the following general formula (1):
Containing at least one quaternary ammonium salt
Characterized by consisting of polysiloxane and binder resin
Underwater antifouling paint composition. Embedded image(Where R¹Is a hydrogen atom or a substituted or unsubstituted carbon
A monovalent organic group having a prime number of 1 to 10, R^TwoIs a quaternary ammonium salt
A monovalent organic group containing at least one^ThreeIs R ¹Also
Is OR¹And p is a positive number satisfying 5 ≦ p ≦ 500
You. ) 2. The underwater antifouling coating composition according to claim 1, wherein the terminal of the quaternary ammonium salt-containing organopolysiloxane is represented by the following general formula (2). Embedded image (Wherein R ¹ , R ² , R ³ , and p are the same as in the general formula (1)) 3. R^TwoHas the following general formula (3) -CH_TwoCH_TwoCH_TwoN⁺R^FourR^FiveR⁶Cl^- (3) (where R^Four, R^FiveAre the same or different and have 1 to 1 carbon atoms
A monovalent hydrocarbon group of 3, R ⁶Is a monovalent carbon having 1 to 30 carbon atoms
A monovalent organic group represented by the formula:
Or the underwater antifouling paint composition according to claim 2. 4. R ² is represented by the following general formula (4): —CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ C _n H _{2n + 1} Cl ⁻ (4) (n is a positive number of 12 to 24) The underwater antifouling paint composition according to claim 3, which is a monovalent organic group represented by the following formula: