Antifouling paint composition and product coated therewith

An antifouling paint composition which comprises (a) a non-hydrolyzable polymer having a film-forming property and a Young's modulus of from 0.01 to 10 MPa at 25° C. in its unvulcanized state, (b) a solid antifouling substance and (c) a dispersing medium or a solvent. The composition can be readily applied to a substrate and the resulting coated film on the substrate has an excellent antifouling property for a long period. An antifouling painted product is obtained by coating the antifouling paint composition on a substrate.

EXAMPLES In the following, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Examples 1-6 and Examples 9-14 are embodiments of the present invention, and Examples 7-8 and Examples 15-17 are comparative examples. &lsqb;Preparation Example 1&rsqb; A fluorine-containing rubber composition was obtained by mixing 100 parts of a fluorine-containing rubber composed of polymerizing units of tetrafluoroethylene/propylene (molar ratio: 55/45) and having a Young's modulus of 3.15 MPa at 25° C. in its unvulcanized state and 10 parts of MT carbon (N 990, manufactured by CANCARB company). 100 parts of the fluorine-containing rubber composition was homogeneously dispersed into 400 parts of butyl acetate to obtain a base paint 1. &lsqb;Preparation Example 2&rsqb; 100 parts of a fluorine-containing rubber composed of polymerizing units of vinylidene fluoride/tetrafluoroethylene/propylene (molar ratio: 3/55/42) and having a Young's modulus of 1.42 MPa at 25° C., 10 parts of MT carbon (N 990, manufactured by CANCARB Company) and 3 parts of magnesium oxide (Kyowamag 150, manufactured by Kyowa Chemical Industries Company Limited), 6 parts of calcium hydroxide (Calvit, manufactured by Ohmi Chemical Company), 1 part of bisphenol AF and 0.5 parts of tetrabutylammonium hydroxide) were homogeneously mixed by using two-roll mill to obtain a fluorine-containing rubber composition. 100 Parts of the resulting fluorine-containing rubber composition was homogeneously dispersed into 400 parts of ethyl acetate to obtain a base paint 2. &lsqb;Preparation Example 3&rsqb; 100 parts of a fluorine-containing rubber composed of polymerizing units of vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene (molar ratio: 60/22/18) and having a Young's modulus of 0.86 MPa at 25° C. was homogeneously dispersed into 400 parts of methyl ethyl ketone to obtain a base paint 3. &lsqb;Preparation Example 4&rsqb; 100 parts of a fluorine-containing rubber composed of polymerizing units of vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene (molar ratio: 60/22/18) and having a Young's modulus of 0.31 MPa at 25° C., 30 parts of N 990, 3 parts of Kyowamag 150, 6 parts of Calvit, 2 parts of bisphenol AF, 0.5 parts of triphenylbenzyl phosphonium chloride and 1 part of 3-aminopropyltriethoxysilane were homogeneously mixed to obtain a fluorine-containing rubber composition. 100 parts of the resulting fluorine-containing rubber composition was homogeneously dispersed into 400 parts of methyl ethyl ketone to obtain a base paint 4. &lsqb;Preparation Example 5&rsqb; A natural rubber composition was obtained by mixing 100 parts of a natural rubber having a Young's modulus of 0.25 MPa at 25° C. and 30 parts of HAF carbon (Asahi &num;70, manufactured by Asahi Carbon Company). 100 Parts of the natural rubber composition was homogeneously dispersed into 400 parts of gasoline to obtain a base paint 5. &lsqb;Preparation Example 6&rsqb; 100 parts of a nitrile rubber (NBR) having a Young's modulus of 0.92 MPa at 25° C., 100 parts of mistron vaper talc, 3 parts of zinc oxide No. 1, 1 part of stearic acid, 5 parts of octylated diphenyl amine (NOCRAC AD-F, manufactured by Ouchishinko Chemical Industrial Co., Ltd.), 2.5 parts of tetramethyl thiuram disulfide (NOCCELER TT, manufactured by Ouchishinko Chemical Industrial Co., Ltd.), 2 parts of tetrabutyl thiuram disulfide (NOCCELER TBTS, manufactured by Ouchishinko Chemical Industrial Co., Ltd.) and 0.4 parts of sulfur were mixed to obtain a NBR composition. 100 parts of the resulting NBR composition was homogeneously dispersed into 700 parts of cyclohexanone to obtain a base paint 6. &lsqb;Preparation Example 7&rsqb; 100 parts of a fluorine-containing rubber composed of polymerizing units of vinylidene fluoride/tetrafluoroethylene/propylene (molar ratio: 35/40/25) and having a Young's modulus of 0.002 MPa at 25° C., 10 parts of N 990, 3 parts of Kyowamag 150, 6 parts of Calvit, 1 part of bisphenol AF and 0.5 parts of tetrabutyl ammonium hydroxide were homogeneously mixed by using two-roll mill to obtain a fluorine-containing rubber composition. 100 parts of the resulting fluorine-containing rubber composition was homogeneously dispersed into 400 parts of ethyl acetate to obtain a base paint 7. &lsqb;Preparation Example 8&rsqb; 100 parts of a fluorine-containing rubber composed of polymerizing units of vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene (molar 15 ratio: 50/40/10) and having a Young's modulus of 57 MPa at 25° C. was homogeneously dispersed into 400 parts of methyl ethyl ketone to obtain a base paint 8. &lsqb;Examples 1-6&rsqb; and &lsqb;Examples 7-8 (Comparative Examples)&rsqb; Paint 1-Paint 8 were obtained by adding various solid antifouling substances to the base paints with stirring at room temperature in the ratio shown in Table 1. The solid antifouling substances were copper(I) oxide (average particle diameter: 2.5 &mgr;m, specific surface area: 4500 m 2 /g, manufactured by Kanto Chemical Company), zinc pyrithione (average particle diameter: 7.5 &mgr;m, specific surface area: 2000 m 2 /g, ZINC OMADINE, manufactured by Arch Chemical Company) and copper pyrithione (average particle diameter: 5.0 &mgr;m, specific surface area: 2500 m 2 /g, COPPER OMADINE, manufactured by Arch Chemical Company). 1 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Paint 1 Paint 2 Paint 3 Paint 4 Paint 5 Paint 6 Paint 7 Paint 8 Base Paint 1 60 Base Paint 2 60 Base Paint 3 60 Base Paint 4 60 Base Paint 5 60 Base Paint 6 60 Base Paint 7 60 Base Paint 8 60 Copper (I) 10 10 30 30 50 50 10 30 oxide Zinc 3 3 5 5 5 5 3 5 pyrithione Copper 5 5 5 3 5 5 5 3 pyrithione &lsqb;Example 9&rsqb; The paint 1 was coated uniformly with a brush on the plate made of stainless steal (SUS 304) having a size of 30 cm×30 cm and dried at room temperature for 24 hours to obtain a test piece having a coated film (thickness: 30 &mgr;m) comprising a fluorine-containing rubber. The test piece was fixed to the side wall of a raft floating on the sea of an inner bay at Ichihara city in Chiba prefecture, so that the upper &frac15; part of the test piece was always come out from sea level regardless of high and low tides. The immersion-exposure test was carried out in the above way. The adhesion of organisms to the test piece and the change of the surface state of the test piece by the adhered organisms with a passage of time were evaluated with the eyes. The raft was moored at a jetty so that it was not influenced by water flow in comparison with a sailing ship, etc. Consequently, the conditions employed in this immersion-exposure test were severe from the viewpoint of adhesion of organisms. &lsqb;EXAMPLE 10&rsqb; The paint 2 was coated uniformly with a brush on the plate made of glass fiber-reinforced polyvinyl chloride (manufactured by Asahi Glass Engineering Company) having a size of 30 cm×30 cm and dried at 200° C. for 30 minutes to obtain a test piece having a coated film (thickness: 30 &mgr;m) comprising a fluorine-containing rubber. The immersion-exposure test of the test piece was carried out in the same manner as in Example 9. &lsqb;Example 11&rsqb; The immersion-exposure test was carried out using the sample obtained in the same manner as in Example 9 except that Paint 3 and a titanium plate were used instead of Paint 1 and a stainless steal plate, respectively. &lsqb;Example 12&rsqb; The immersion-exposure test was carried out using the sample in the same manner as in Example 10 except that Paint 4 and a polyvinyl chloride plate were used instead of Paint 2 and a FRV-R plate, respectively. &lsqb;EXAMPLE 13&rsqb; The immersion-exposure test was carried out using the sample in the same manner as in Example 9 except that Paint 5 was used instead of Paint 1. &lsqb;Example 14&rsqb; The immersion-exposure test of was carried out using the sample in the same manner as in Example 10 except that Paint 6 was used instead of Paint 2. &lsqb;Example 15 (Comparative Example)&rsqb; The immersion-exposure test was carried out using the sample in the same manner as in Example 1 except that Paint 9 was used instead of Paint 2. &lsqb;Example 16 (Comparative Example)&rsqb; The immersion-exposure test was carried out using the sample in the same manner as in Example 9 except that Paint 10 was used instead of Paint 3. &lsqb;Example 17 (Comparative Example)&rsqb; The immersion-exposure test was carried out using the sample in the same manner as in Example 9 except that YEAL Paint NO. 1 (manufactured by NIPPON PAINT CO., LTD.) was used instead of Paint 3. The results of the immersion-exposure tests of Examples 9-17 are shown in Table 2. &compfn;no adhesion of organisms was observed. &Dgr;: a small amount of adhesion of sea weeds were observed. X: adhesion of acorn shells and sea weeds were observed. XX: a large quantity of adhesion of organisms was observed. 2 TABLE 2 Days of immersion-exposure (day) Substrate Paint 65 300 700 Ex. 9 Stainless Paint 1 $ $ $ Steal Ex. 10 FRV-R Paint 2 &compfn; &compfn; &compfn; Ex. 11 Titanium Paint 3 &compfn; &compfn; &compfn; Ex. 12 PVC Paint 4 &compfn; &compfn; &compfn; Ex. 13 Stainless Paint 5 &compfn; &compfn; &Dgr; Steal Ex. 14 FRV Paint 6 &compfn; &compfn; &Dgr; Ex. 15 FRV Paint 7 X XX XX Ex. 16 Titanium Paint 8 X XX XX Ex. 17 Stainless YEAL Paint X X XX Steal No. 1 (Partially) 
 INDUSTRIAL APPLICABILITY According to the present invention, a new antifouling paint composition was provided. The composition can be readily applied to the surface of a substrate and the resulting film on the substrate has an excellent antifouling property for a long period. An antifouling painted product is also provided by coating the antifouling paint composition on a substrate. The entire disclosure of Japanese Patent Application No. 2000-21871 filed on Jan. 26, 2000 including specification, claims and summary are incorporated herein by reference in its entirety.