JPH0551030B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifouling paint composition, and more particularly to a nontoxic antifouling paint composition for preventing the adhesion of marine organisms to submerged parts of ships and offshore structures. Conventionally, submerged parts of ships and offshore structures have been painted with paints containing cuprous oxide and organic tin compounds, which have been highly effective in preventing marine organisms from adhering to them. There is a problem of environmental pollution caused by compounds, and there is a demand for the development of non-toxic antifouling paints that do not contain organic metals such as copper and tin compounds. The adhesion of marine organisms such as barnacles, sea breams, sea squirts, and algae to paint films decreases as the surface energy of the paint film decreases, and as the paint film contains fewer polar components, non-toxic forms using paraffin are used. Antifouling paints have been developed, and although their antifouling effects are recognized in the short term,
It has the disadvantage that it cannot exhibit a sufficient antifouling effect over a long period of time. Therefore, the present inventors conducted extensive research in order to develop a non-toxic antifouling paint that does not contain metal compounds or organic metals that cause environmental pollution and maintains its antifouling effect over a long period of time. As a result, we discovered that a paint that reduces the surface energy of the paint film and forms a paint film that is gradually polished by the force of ocean currents has antifouling properties over a long period of time.
The present invention was accomplished by developing specific binder components that meet this purpose. In addition,
Polishing the surface of a coating film in the present invention refers to a phenomenon in which the surface of the coating film gradually peels off over a long period of time. Therefore, according to the present invention, (A) a vinyl copolymer containing 5 to 80% by weight of a (meth)acrylooxyalkyltrialkoxysilane compound and/or a vinyltrialkoxysilane compound as an essential component; ) Provided is an antifouling paint composition characterized by containing a saturated long-chain alcohol represented by the following general formula C _o H _2o+1 OH (wherein n represents an integer from 12 to 60). . According to the antifouling paint composition of the present invention, the coating film formed therefrom has low surface energy, and the surface of the coating film is easily polished by ocean currents, so it has excellent long-term antifouling properties, and it also has excellent long-term antifouling properties. can also be easily removed. Hereinafter, the main components constituting the antifouling paint composition of the present invention will be specifically explained. The (meth)acryloxyalkyltrialkoxysilane compound, which is a constituent component of the vinyl polymer (A) in the antifouling paint composition of the present invention, has the following general formula: (In the formula, R ₁ represents a hydrogen atom or a methyl group,
(R ₂ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 to 5) can be advantageously used, and specific examples include (meth)acryloxymethyltrimethoxysilane, ( (meth)acryloxyethyltrimethoxysilane, (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropyltriethoxysilane, (meth)acryloxyethyltriethoxysilane, (meth)acryloxypropyltributoxysilane, etc. can be mentioned. Among these compounds, when R ₂ in the above formula (1) becomes an alkyl group having 3 or more carbon atoms, the reactivity between alkoxy and the hydroxyl group of the long-chain alcohol compound (B) _decreases . It is a methyl group or an ethyl group. In addition, when m in the formula (1) is 0, the stability of the compound is poor, and when m is 6 or more, the reactivity of the alkoxy group decreases, so it is usually an integer of 1 to 5, preferably 1 to 3. is an integer. Next, the vinyltrialkoxysilane compound is a compound represented by the following general formula CH ₂ =CH-Si(-OR ₂ ) ₃ ...() (in the formula, R ₂ represents the above-mentioned meaning), for example, vinyl Examples include trimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, and vinyltributoxysilane. R ₂ in the above formula () is as in the case of the compound of the above formula (),
Preferably it is a methyl group or an ethyl group. Vinyl polymer (A) used in the present invention
is 5 to 80% by weight of the above-mentioned (meth)acrylooxyalkyltrialkoxysilane compound and/or vinyltrialkoxysilane compound, preferably
It contains 20 to 50% by weight as an essential component, and is produced by adding a polymerizable unsaturated vinyl monomer thereto and copolymerizing it by a conventionally known method. Examples of the above-mentioned polymerizable unsaturated vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, (meth)hexyl acrylate, (meth)
Acrylics such as (meth)acrylic acid alkyl esters such as 2-ethylhexyl acrylate, octyl (meth)acrylate, and lauryl (meth)acrylate; glycidyl (meth)acrylate; (meth)acrylic acid; allyl (meth)acrylate; Examples of unsaturated monomers and unsaturated monomers other than those mentioned above include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, acrolein, methacrolein, butadiene, isoprene, and the like. However, monomers containing hydroxyl groups as polymerizable unsaturated vinyl monomers cannot be used because they will react with the alkoxy groups of (meth)acryloxyalkyltrialkoxysilane compounds and vinyltrialkoxysilane compounds. . The vinyl polymer (A) used in the present invention has a number average molecular weight of about 3,000 to about 100,000, preferably about 5,000 to about
50000 and the glass transition temperature is -
A temperature range of 10°C to 100°C, preferably 0 to 30°C is suitable because a good coating film can be formed at room temperature. The saturated long chain alcohol (B) used in the present invention is
It is an alcohol represented by the following general formula C _o H _2o+1 OH (in the formula, n represents an integer from 12 to 60), such as lauryl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol, merisyl alcohol, etc. Examples include alcohol (C30H ₆₁ OH), tetracontanol (C ₄₀ H ₈₁ OH), pentacontanol (C ₅₀ H ₁₀₁ OH), pentacontanol (C ₆₀ H ₁₂₁ OH), and the like. Among these alcohols, those having n of 12 to 30 are preferred. The antifouling paint composition of the present invention is a combination of the above-mentioned vinyl polymer (A) and saturated long-chain alcohol (B), and the ratio of the (B) component to the (A) component is from 1 to 150 PHR, preferably from 5 to 50 PHR.
If the blending ratio of component (B) is less than 5 PHR, the effect of lowering the surface energy of the coating film will be small, while if it exceeds 150 PHR, the stability of the mixture will deteriorate. According to the antifouling paint composition of the present invention, the physical properties of the coating film are excellent due to the curing reaction of the component (A) itself based on the alkoxy groups in the component (A), and due to the reaction between the component (A) and the component (B). A reduction in the surface energy of the coating film after film formation based on the saturated long-chain alcohol component and abrasiveness of the coating film based on the saturated long-chain alcohol component are obtained.
As a result, a non-toxic and excellent antifouling coating can be formed. The antifouling paint composition of the present invention can also contain small amounts of coloring pigments, anticorrosive pigments, anti-sagging agents, plasticizers, etc. as necessary, and further maintains the surface energy of the paint film at a constant level. Paraffin, petrolactam, etc. may also be added for this purpose. The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited only to the Examples. Note that the numerical values in Examples and Comparative Examples indicate parts by weight unless otherwise specified. Production Example Production Example of Vinyl Copolymer 1 95g of n-butyl methacrylate and 5g of KBM503 (Methacryloxypropyltrimethoxysilane manufactured by Shin-Etsu Silicon Co., Ltd.) were dissolved in 67g of xylene, and 2.0g of benzoyl peroxide was added thereto and the mixture was heated for 90~
The mixture was maintained at 100°C for 6 hours to obtain a pale yellow viscous liquid. Production example of vinyl copolymer 2 40 g of t-butyl methacrylate, 40 g of 1-butyl methacrylate, SH6030 (methacryloxypropyltrimethoxysilane manufactured by Toray Silicone) 20
g was dissolved in 25 g of xylene, 0.4 g of azobisisobutyronitrile was added, and the temperature was maintained at 90 to 100°C for 3 hours with stirring. Then, 42 g of xylene was added and the mixture was heated to 90 to 100°C.
The reaction was completed by maintaining the temperature at 100°C for 3 hours. Production example of vinyl copolymer 3 Vinyl acetate 30g, vinyl chloride 20g and V4917
(Vinyltrimethoxysilane manufactured by Chitsuso Co., Ltd.) 50g
was dissolved in a mixed solution of 33 g of xylene and 34 g of butyl acetate, and 1.0 g of benzoyl peroxide was added to the solution at 90°C.
The reaction was completed by maintaining the temperature at ~100°C for 6 hours. Production example of vinyl copolymer 4 30 g of styrene, 40 g of t-butyl methacrylate
Dissolve 30 g of KBE1003 (vinyltriethoxysilane manufactured by Shin-Etsu Silicon Co., Ltd.) in 67 g of xylene, add 0.7 g of azobisisobutyronitrile, and stir.
The reaction was completed by maintaining the temperature at 90°C to 100°C for 6 hours. All of the above vinyl copolymers were pale yellow liquids and formed good coating films after solvent evaporation. Example 1 70.0 parts of the vinyl copolymer solution obtained in Production Example 1 (solid content 60%), 4.2 parts of stearyl alcohol, 0.5 parts of Erosil #200 (manufactured by Degussa, Germany) and 25.3 parts of xylene were mixed with a paint conditioner. The antifouling paint composition of the present invention was obtained by mixing and dispersing. Examples 2 to 8 Antifouling paint compositions were prepared in the same manner as in Example 1 using the blending ratios shown in Table-1. In the examples, both stearyl alcohol and mericyl alcohol were solid at room temperature, so they were melted by heating before use. Comparative Examples 1 to 3 Antifouling paint compositions were prepared in the same manner as in Example 1 with the following formulations. The coating film performance test results are shown in Table 2 below. Comparative example 1 Vinyl chloride resin 10.0 Rosin 10.0 Tricresyl phosphate 4.0 Triphenyltin fluoride 10.0 Talc 5.0 Valve handle 5.0 Xylol 28.0 Methyl isobutyl ketone 28.0 Total 100.0 Comparative example 2 Chlorinated rubber resin 5.0 Rosin 15.0 Tricresyl phosphate 4.0 Cuprous oxide 30.0 Talc 5.0 Baryta 3.0 Valve handle 4.0 Xylol 34.0 Total 100.0 Comparative example 3 Vinyl chloride resin 5.5 Rosin 5.5 Tricresyl phosphate 2.0 Cuprous oxide 30.0 Triphenyltin hydroxide 10.0 Barium sulfate 4.0 Talc 11.0 Pengara 10. 0 Xylol 11.0 Methyl isobutyl ketone 11.0 Total 100.0 Antifouling performance test results For the paints obtained in Examples 1 to 8 and Comparative Examples 1 to 3 above, zinc epoxy shop primer (dry film thickness 15μ) and epoxy paint were applied to a sandblasted steel plate with a size of 100 x 300 x 2 mm. Anti-rust paint (same as
200μ) was coated in advance to give a dry film thickness of 50μ, which was used as a test coated board and dried for 7 days. When applying the antifouling paint, it was heated to the extent that the required fluidity was obtained. Table-2
These test plates were immersed in Toba Bay, Mie Prefecture for 18 months, and the antifouling properties (numbers indicate adhesion percentage) were evaluated. Comparative Examples 4-5 Antifouling paint compositions were prepared in the same manner as in Example 1 with the following formulations, coated plates were prepared in the same manner, and subjected to antifouling performance tests in the same manner. The results are shown in Table-3. Comparative Example 4 Vinyl copolymer solution of Production Example 1 (solid content 60%)
70.0 Propanol 4.2 Erosil #200 0.5 xylene 25.3 total 100.0 Comparative example 5 Vinyl copolymer solution of Production Example 2 (solid content 60%)
70.0 n-butanol 12.6 Erosil #200 0.5 xylene 16.9 total 100.0

[Table] From Table 3 above, it can be seen that when component (B) is propanol with carbon number n = 3 and n-butanol with carbon number n = 4, and saturated long-chain alcohol is not mixed, the antifouling performance will be significantly reduced. I understand.

【table】

【table】

[Table] As is clear from the test results, the antifouling agent according to the present invention exhibited antifouling performance comparable to that of conventional paints containing antifouling agents such as organic tinnous oxide.

Claims (1)

[Scope of Claims] 1 (A) A vinyl copolymer containing 5 to 80% by weight of a (meth)acrylooxyalkyltrialkoxysilane compound and/or a vinyltrialkoxysilane compound as an essential component, and (B) the following: An antifouling paint composition characterized by containing a saturated long-chain alcohol represented by the general formula C _o H _2o+1 OH (wherein n represents an integer of 12 to 60).