JPH036192B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an antifouling paint composition. Conventional technology and its problems Structures and equipment that come into contact with seawater, such as ships,
Seawater contact surfaces such as marine structures, power plant cooling water pipes, fishing nets, etc. are covered with marine organisms such as sea lettuce, blue seaweed, barnacles, and mussels, causing great damage. In response to this, various countermeasures have been studied to prevent the adhesion of these marine organisms. For example, antifouling paint coating methods, ultrasonic vibration methods, chlorine injection methods, seawater electrolysis methods, copper-nitsuru alloy pasting methods, low-energy surface methods, etc. are being researched; There are currently few products in practical use due to their antifouling effects. Antifouling paints currently on the market are those in which antifouling components such as organic tin compounds such as tributyltin compounds and triphenyltin compounds, and copper compounds, which have antifouling properties, are blended into the paint. These antifouling components gradually dissolve into the seawater from the surface of the coating film, thereby physiologically preventing the adhesion of marine organisms. However, in recent years, there has been a tendency to limit or prohibit the application of this type of antifouling paint from the viewpoint of environmental pollution and hygiene. Recently, as a non-toxic antifouling paint that does not have the above-mentioned drawbacks, a paint for preventing fouling of marine organisms has been developed that contains an oligomeric room-temperature curing silicone rubber and a petroleum-based low critical surface tension substance (liquid paraffin or petrolatum). (See Special Publication No. 60-3433).
However, the antifouling performance of this paint is equal to or lower than that of conventional antifouling paints, and therefore is insufficient to exhibit excellent antifouling performance over a long period of time. Improvement is desired.
In addition, since this paint is a moisture-curing type that cures with moisture in the air, the curing speed of the coating film is slow and it needs to be cured by heating, and it also has the disadvantage of lacking film-forming properties. are doing. Means for Solving the Problems As a result of intensive research to develop an antifouling paint that does not have the above-mentioned drawbacks, the present invention has been developed using a polymer containing the following specific silicone-containing acrylic monomer as an active ingredient. It has been found that the intended purpose of the present invention can be achieved when used. The present invention was completed based on this knowledge. That is, the present invention provides (a) general formula [R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 6 carbon atoms. n is 3
Indicates an integer between ~200. ] An antifouling agent characterized by containing a homopolymer of a silicone-containing acrylic monomer represented by the formula or a copolymer with a vinyl monomer copolymerizable therewith, and (b) a water repellent. It concerns a paint composition. The silicone-containing acrylic monomer represented by the above general formula (1) used in the present invention is, for example, [In the formula, R ¹ and R ² are the same as above. ] Compounds and general formula [In the formula, n is the same as above. ] using a known dehydrochloric acid reaction (for example, JP-A-59-20360
(see Japanese Patent Publication). Also, general formula (3)
The compound can be produced, for example, according to the method disclosed in Japanese Patent Publication No. 47-44040. In the above general formula (1), the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R ² is specifically -CH ₂ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ −, −(CH ₂ ) ₄ −
,
−(CH ₂ ) ₅ −, −(CH ₂ ) ₆ −,

【formula】,

[In the formula, R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a glycidyl group which may have a hydroxyl group or a dimethylamino group as a substituent. ]

In addition to the acrylic ester represented by, styrene, acrylonitrile, vinyl acetate, etc. can be mentioned. In the above general formula (4), the monovalent organic residue containing a linear or branched perfluoroalkyl group represented by R ^f is specifically -CH( _CF3 ) ₂ , -CF (CF ₃ ) ₂ , −(CF ₂ ) _p −CF ₃ (P
is 0 or an integer from 1 to 11), −(CH ₂ ) _q − (CF ₂ ) _p −
CF ₃ (q is 0 or an integer from 1 to 10, p is the same as above) - (CF ₂ ) _p - CH (CF ₃ ) ₂ (p is the same as above), -
(CF ₂ ) _p -CF (CF ₃ ) ₂ (p is the same as above), and the like. Specifically, the acrylic esters represented by the above general formula (5) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-
-butyl methacrylate, amyl acrylate,
amyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,
2-octyl acrylate, 2-octyl methacrylate, β-hydroxyethyl acrylate,
Examples include β-hydroxyethyl methacrylate, dimethylaminotylacrylate, dithylaminomethylmethacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. The vinyl monomers mentioned above may be used alone or in combination of two or more. Among these vinyl monomers, it is preferable to use the fluorine-containing acrylic monomer of the general formula (4) above, and by using such a fluorine-containing acrylic monomer, the desired effects of the present invention can be achieved. (Especially the antifouling effect) can be further exhibited. In the present invention, the polymer used as the above component (a) can be easily produced according to the method shown below. That is, the silicone-containing acrylic monomer of the above general formula (1) or a mixture of the monomer and a vinyl monomer copolymerizable therewith is mixed with benzoyl peroxide, azobisisobutyronitrile, etc. It is produced by solution polymerization or non-aqueous dispersion polymerization in the presence of a conventional radical polymerization initiator. The amount of radical polymerization initiator used is based on the monomer to be polymerized.
The amount is usually about 0.5 to 10 parts by weight, preferably about 1 to 5 parts by weight per 100 parts by weight. When using a copolymer of the silicone-containing acrylic monomer of general formula (1) and a vinyl monomer copolymerizable with the silicone-containing acrylic monomer as component (a), these monomers are Usually the former monomer is about 5% or more,
Preferably, it is used in a proportion of about 20 to 80% by weight. In particular, when the fluorine-containing acrylic monomer of general formula (4) is used as the vinyl monomer copolymerizable with the silicone-containing acrylic monomer, the copolymer contains 5 % or more, preferably about 10 to 50% by weight. In the present invention, as the water repellent used as component (b), a wide variety of conventionally known water repellents can be used, such as liquid paraffin, petrolatum, silicone oil, paraffin, wax, vaseline, and the like. In the present invention, the blending ratio of component (a) and component (b) is not particularly limited, but usually about 5 to 200 parts by weight of the latter per 100 parts by weight of the former.
Preferably about 10 to 150 parts by weight, more preferably
The amount is preferably about 50 to 100 parts by weight. If it deviates from the above range, it is not preferable because the intended effects of the present invention will be difficult to exhibit. The composition of the present invention usually contains an organic solvent in addition to the above-mentioned components (a) and (b). Examples of the organic solvent include toluene, xylene, methyl isobutyl ketone, ethyl acetate, mineral spirits, and mixed solvents thereof. Among these, toluene and xylene are particularly preferred. There are no particular limitations on the use of the composition of the present invention, and it can be used in the same manner as conventional antifouling paints. For example, air spray painting, airless The composition of the present invention may be coated by a conventional method such as spray coating, dip coating, or brush coating. Effects of the Invention The antifouling paint composition of the present invention can exhibit excellent antifouling performance over a long period of time. Furthermore, the coating composition of the present invention is non-toxic and has excellent film-forming properties. Further, the composition of the present invention has a fast curing degree, can be cured at room temperature, and has excellent workability. Examples Production examples, examples, and comparative examples are given below to further clarify the present invention. In the following, "parts" means "parts by weight" and "%" means "% by weight." Also, the general formula used below
The silicone-containing acrylic monomers represented by (1) are shown in Table 1 below, and the fluorine-containing acrylic monomers represented by general formula (4) are shown in Table 2 below.

【table】

【table】

[Table] Production Example 1 30 parts of the compound, 50 parts of methyl methacrylate, 20 parts of butyl methacrylate, 100 parts of toluene, and 1 part of benzoyl peroxide were charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser. The mixture was heated to 80° C. while blowing nitrogen gas, and a polymerization reaction was carried out for 10 hours to obtain a transparent solution of a silicone-containing copolymer. This solution has a solid content of 50.3%, a viscosity of 400 cps (25°C), and a weight average molecular weight of the polymer of 45,000.
This solution is hereinafter referred to as "solution A." Solutions of various silicone-containing copolymers ("Solution B" to "Solution K") were obtained in the same manner as in Production Example 1 using the various monomers shown in Table 3 below. The properties of these solutions are also shown in Table 3. Further, solutions of various silicone-containing copolymers ("Solution L" to "Solution P") were obtained in the same manner as in Production Example 1 using the various monomers shown in Table 4 below. The properties of these solutions are also shown in Table 4.

【table】

【table】

[Table] Examples 1 to 33 The following 5th solution was added to the solutions A to P obtained in the above production examples.
A water repellent and a solvent were added in the formulation shown in the table and mixed using a stirrer to obtain an antifouling paint composition of the present invention. The following paints were also prepared for comparison. Comparative Example 1 100 parts of solution A obtained in the above production example Comparative Example 2 Silicone rubber [KE-45TS, manufactured by Shin-Etsu Chemical Co., Ltd.] 40 parts Petrolatum [JP-1500, manufactured by Nippon Seiro Co., Ltd.] 10 parts Toluene 50 parts Comparison Example 3 KE-45TS 40 parts Liquid paraffin #70 10 parts Toluene 50 parts Comparative example 4 KE-45TS 40 parts Silicone oil [[KF96, manufactured by Shin-Etsu Chemical]
10 parts Toluene 50 parts Comparative example 5 Organic tin/cuprous oxide combined antifouling paint [Kanaeport A/F Sp, manufactured in-house] Comparative example 6 Solution L obtained in the above production example 100 parts Comparative example 7 In the above production example Obtained solution M 100 parts

【table】

【table】

[Table] Antifouling Performance Test The coating compositions of the above Examples and Comparative Examples were applied twice to both sides of an FRP board (100 x 300 x 2 mm) with a brush so that the film thickness was 100μ, and dried. rear,
The FRP board was immersed 1.5 m below the water surface from a raft in Hiroshima Bay, Hiroshima Prefecture, and the state of adhesion of fouling organisms was observed. The results are shown in Table 6 below. The meaning of each symbol in Table 6 is as follows. ○: No adhesion ○-△: 5% or less adhesion △: 5-20% adhesion △-×: 20-50% adhesion ×: 50% or more adhesion

【table】

【table】

Claims (1)

[Claims] 1 (a) General formula [R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 6 carbon atoms. n is 3
Indicates an integer between ~200. ] A homopolymer of a silicone-containing acrylic monomer represented by or a copolymer of the monomer and a vinyl monomer copolymerizable therewith, and (b) a water repellent. Characteristic antifouling paint composition. 2 The vinyl monomer copolymerizable with the silicone-containing acrylic monomer has the general formula [In the formula, R ¹ represents a hydrogen atom or a methyl group. R ^f represents a monovalent organic residue containing a linear or branched perfluoroalkyl group. ] The composition according to claim 1, which is a fluorine-containing acrylic monomer represented by: