JPH0513192B2 - - 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 other 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. Therefore, the present inventors conducted intensive research to develop a non-toxic antifouling paint that does not contain metal compounds or organic metals that cause environmental pollution. They found that the lower the surface energy of the paint film, and the fewer polar components there are in the paint film, the more easily water droplets fall on the paint film surface, the less likely it is for organisms to attach to the surface, and the weaker the adhesion force, which meets this objective. The invention was accomplished by developing specific binder components. Therefore, according to the present invention, (A) 1 to 50% by weight of a (meth)acrylooxyalkyltrialkoxysilane compound and/or a vinyltrialkoxysilane compound and 0 to 50% by weight of a (meth)acrylate compound containing a perfluoroalkyl group; A vinyl copolymer containing % by weight as an essential monomer component and (B) the following general formula (wherein, R represents an alkyl group or aryl group having 1 to 4 carbon atoms, a represents an integer of 1 to 6, and b represents a numerical value of 3 to 200) Provided is an antifouling paint composition characterized by containing the following. According to the antifouling coating composition of the present invention, the coating film formed therefrom has low surface energy, and water droplets easily fall on the coating surface, so it has excellent antifouling properties.
Furthermore, even if living organisms adhere to the surface, they can 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 4 carbon atoms, and 1 represents an integer of 1 to 5) can be advantageously used, and specific examples thereof include (meth)acryloxymethyltrimethoxysilane, ( (meth)acryloxyethyltrimethoxysilane, (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropyltriethoxysilane, (meth)acryloxyethyltriethoxysilane, (meth)acryloxypropyltriptoxysilane, etc. can be mentioned. Among these compounds, the formula ()
When R ₂ in is an alkyl group having 3 or more carbon atoms, the reactivity between alkoxy and the hydroxyl group of the hydroxyl group-containing silicon compound (B) decreases, so more preferably
R ₂ is a methyl group or an ethyl group. In addition, when l in the above formula () is 0, the stability of the compound is poor, while when it 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 ... () (wherein R ₂ represents the above-mentioned meaning), for example. Examples include vinyltrimethoxysilane, 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. In addition, as a perfluoroalkyl group-containing (meth)acrylate compound, the following general formula (In the formula, R ₁ represents the above meaning, m is 1 to 5
n is an integer of 1 to 21) are preferably used, for example, 2-perfluorobutylethyl methacrylate. 2-Perfluorobutylethyl acrylate 2-Perfluorooctylethyl acrylate CH ₂ = CH-COO-CH ₂ CH ₂ -C ₈ F ₁₇ 2-Perfluorooctylethyl methacrylate 2-perfluorooctyl methacrylate 2-Perfluorononylethyl methacrylate 2-Perfluoroisononylethyl methacrylate 2-Perfluoroisononylethyl acrylate 2-Perfluorodecylethyl methacrylate Examples include. Among the compounds represented by the above formula (), compounds with m value of 0 are unstable and easily hydrolyzed, while compounds with m value of 6 or more have little effect on lowering the surface tension of the coating film, so m is preferably 1. ~5 compounds. In addition, values of n in the range of 1 to 21 can be used, but even if n is 10 or more, there is no difference in the effect of lowering the surface tension of the coating film, and in terms of price, n is 1 to 9.
Compounds within the range of are preferred. Vinyl polymer (A) used in the present invention
is 1 to 50% by weight, preferably 5 to 30% by weight of the above-mentioned (meth)acrylooxyalkyltrialkoxysilane compound and/or vinyltrialkoxysilane compound and 0 to 50% by weight of the (meth)acrylate compound containing a perfluoroalkyl group. It is produced by adding a polymerizable unsaturated vinyl monomer as necessary to a mixture consisting of 5% to 30% by weight, 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, pryl (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. Hydroxyl group-containing silicon compound used in the present invention
(B) is the following general formula (In the formula, R represents an alkyl group or aryl group having 1 to 4 carbon atoms, a represents an integer of 1 to 6, and b
(represents a numerical value from 3 to 200) is a compound having primary hydroxyl groups at both ends, for example: etc. can be mentioned. In the hydroxyl group-containing silicon compound (B), if R in the general formula is an alkyl group having 5 or more carbon atoms, the stability of the compound is poor, and more preferably R is an alkyl group having 1 to 2 carbon atoms. Further, a compound having an integer of 7 or more has poor reactivity with the vinyl polymer (A), and the value of a is more preferably an integer of 1 to 3. Furthermore, the value of b, which represents the number of repetitions of siloxane bonds, is in the range of 3 to 200, preferably 20 to 100; if it is less than 3, the effect of lowering the surface tension and friction of the coating film is poor; on the other hand, if it exceeds 200, and the stability of the compound decreases. The antifouling paint composition of the present invention is a combination of the above-mentioned vinyl polymer (A) and hydroxyl group-containing silicone compound (B), and the ratio of the (B) component to the (A) component is 0.5~140PHR, preferably 5~50PHR
It is. If the blending ratio of component (B) is less than 0.5 PHR, the surface energy effect of the coating film and the sliding effect of water droplets will be small, while if it exceeds 140 PHR, the stability of the mixture will be poor. The antifouling paint composition of the present invention aims to improve the physical properties of the coating film through the curing reaction of component (A) itself based on the alkoxy group in component (A) and the curing reaction between component (A) and component (B). Moreover, the surface energy of the coating film is reduced by the optionally introduced perfluoroalkyl group. On the other hand, component (B) has primary hydroxyl groups at both ends, which act as a crosslinker with the alkoxy group of component (A), and the crosslinking reaction only needs to proceed during film formation. If necessary, components (A) and (B) may be hot-blended and crosslinked in advance without any particular impediment to the effects of the present invention. The surface energy of the coating film formed from the resin component obtained by the crosslinking reaction of component (A) and component (B) is somewhat higher than that of the coating film containing only component (A). It facilitates the falling of water droplets and achieves the antifouling properties and the reduction in the adhesion of living things, which are the objectives of the present invention. In addition to components (A) and (B), the composition of the present invention may also contain coloring pigments, anticorrosion pigments, plasticizers, anti-sagging agents, and the like. The present invention will be explained below with reference to Examples, but the present invention is not limited only to the Examples. Note that the numbers in Examples and Comparative Examples indicate parts by weight unless otherwise specified. Production Example Production Example of a Vinyl Copolymer Containing Trialkoxysilane 1 60g of MMA (methyl methacrylate), 20g of n-butyl methacrylate and 20g of methacryloxypropyltrimethoxysilane were dissolved in 67g of xylene, and 1.0g of benzoyl peroxide was added. ,
The reaction was completed by maintaining the temperature at 90 to 100°C for 6 hours while stirring. Example 1 80 parts of the vinyl copolymer solution obtained in Production Example 1 (solid content 60%), 4.8 parts of silicon compound, Erosil #200
(manufactured by Degussa AG, West Germany) and 14.7 parts of xylene were mixed and dispersed using a paint conditioner to obtain the antifouling paint composition of the present invention. The coating film performance test results are shown in Table 2 below. 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. The coating film performance test results are shown in Table 2 below. Comparative Examples 1 to 4 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 (parts) Rosin 10.0 Tricresyl phosphate 4.0 Triphenyltin fluoride 10.0 Talc 5.0 Bengara 5.0 Xylol 28.0 Methyl isobutyl ketone 28.0 Total 100.0 (parts) Comparative example 2 Chlorinated rubber resin 5.0 (parts) Rosin 15.0 Tricresyl phosphate 4.0 Cuprous oxide 30.0 Talc 5.0 (parts) Palita 3.0 Bengara 4.0 Xylol 34.0 Total 100.0 (parts) Production example of vinyl copolymer containing trialkoxysilane 2 Styrene 40g, t-butyl methacrylate 30
g, perfluoropropylethyl methacrylate
Dissolve 20g of acryloxypropyltriethoxysilane and 10g of acryloxypropyltriethoxysilane in a mixed solvent of 33g of xylene and 34g of butyl acetate, and dissolve 0.7g of azobisisobutyronitrile.
g was added thereto, and the temperature was maintained at 100 to 110°C for 6 hours while stirring to complete the reaction. Production example of vinyl copolymer containing trialkoxysilane 3 30 g of vinyl acetate, 20 g of vinyl chloride, 10 g of vinyltrimethoxysilane and 40 g of perfluorooctylethyl methacrylate were dissolved in a mixed solvent of 20 g of xylene and 47 g of butyl acetate, and dissolved in a mixed solvent of 20 g of xylene and 47 g of butyl acetate. 0.5 g of oxide was added and kept at 90-100°C for 6 hours with stirring to complete the reaction. Production example of vinyl copolymer containing trialkoxysilane 4 10 g of t-butyl methacrylate, 20 g of 1-butyl methacrylate, 30 g of vinyltriethoxysilane
g and perfluoromethylethyl acrylate 40
g to a mixed solvent of 20 g of xylene and 47 g of butyl acetate, add 0.5 g of azobisisobutyronitrile,
The reaction was completed by maintaining the temperature at 90 to 100°C for 7 hours while stirring. The above copolymers are all pale yellow liquids,
A good coating film was formed after the solvent evaporated. Comparative example 3 Vinyl chloride resin 5.5 (parts) Rosin 5.5 Tricresyl phosphate 2.0 Cuprous oxide 30.0 Triphenyltin hydroxide 10.0 Barium sulfate 4.0 Talc 11.0 (parts) Red iron 10.0 Xylol 11.0 Methyl isobutyl ketone 11.0 Total 100.0 (parts) Comparison Example 4 Room temperature curing silicone resin 50 (parts) Xylol 50 total 100 (parts) Paint film performance test Sandplast of size 100 x 300 x 2 mm for the paints obtained in Examples 1 to 8 and Comparative Examples 1 to 3 above Zinc epoxy shop primer (dry film thickness 15 μm) and epoxy anti-corrosion paint (dry film thickness 15μ) were applied to treated steel sheets.
A dry film thickness of 50μ is applied to the plate coated with 200μ) in advance.
A test board was prepared by painting it so that it looked like this, and it was dried for 7 days and used for testing. (1) Water droplet sliding test A 0.03ml water droplet was placed on the paint film, and one end was gradually lifted to indicate the angle of the paint plate at which the water droplet began to slide. (2) Critical surface tension measurement results The critical surface tension of the coated surface was measured by measuring the contact angle between water and paraffin droplets. (3) Antifouling test results Test plates were immersed in Toba Bay, Mie Prefecture for 12 months, and the state of adhesion of organisms was investigated. Values are % adhesion.

【table】

【table】

[Table] As is clear from Table 2, the antifouling paint according to the present invention exhibited performance comparable to that of conventional paints using cuprous oxide and organic tin.

Claims (1)

[Scope of Claims] 1 (A) 1 to 50% by weight of a (meth)acrylooxyalkyltrialkoxysilane compound and/or a vinyltrialkoxysilane compound and 0 to 50% by weight of a perfluoroalkyl group-containing (meth)acrylate compound A vinyl copolymer containing as an essential monomer component and (B) the following general formula (wherein, R represents an alkyl group or aryl group having 1 to 4 carbon atoms, a represents an integer of 1 to 6, and b represents a numerical value of 3 to 200) An antifouling paint composition characterized by containing.