COMPLETELY INORGANIC, PERMANENTLY ANTI-CORROSIVE, INNOXIOUS ANTI-FOULING PAINT

Abstract: This is a paint composed of denatured silicate as vehicle and aluminosilicate as dispersoid. Its chemical structure being made reticulated one due to silanol radical reaction, this paint forms a special, completely inorganic functional film close to organic high molecular one. This film prohibits the flow of ions of iron, thus performing anti-corrosive action and discomposing the secretion of sea adhesive organisms, amino acid calcium colloid to give innoxious anti-fouling effect. The paint is also applicable to inside and outside coating of structures and colors for pictures, which have permanent smokeless, humidity controlling, anti-bacterial, anti-static properties.

Description: Completely inorganic, permanently anti-corrosive, innoxious anti-fouling paint Present invention relates to a completely inorganic, permanently anti-corrosive, innoxious anti-fouling paint. Since it was opened up as a heat curing paint by name of DAYMETCOAT. in 1937 (Australian patent No. 1042317), the water glass system paint has been developed through chemical curing method(US patent No. 246263, 1970) and self curing method (US patent No. 4086-616, phosphoric acid method, No. 2536-871j* zinc oxide method). But, where it is used as an anti-corrosive pain the corrosion was prevented by method of increasing the concen ration of zinc without exception. After the heat curing method appeared, water glass system paint has been considered to give an anti-corrosive effect for heavy duty, special purpose steel structure, especially in des and ocean environment. But, in most cases, it is used as a primer for coating or along with organic paint. Phosphoric acid and phosphate, such as silicon polyphosph titanium phosphate and metal oxides such as calcium oxide, alu etc. are known as curing agent of water glass paint already . reported, and glass fibre, carbon fibre etc-, are proposed as i reinforcing agent. Besides, a lot of patents are suggested. Bu main defect of water glass system paint (lack of waterproofnes of bendability, of gloss etc.) have not been solved yet. There organic-inorganic complex compounds are recommended or it is replaced with alkyl silicate paint. In addition, no attempt has been made in any patent to solve anti-corrosive, anti-fouling problem by forming a special functional film of inorganic silicate. Recently, international organizations for preventing polαtion in the world have taken legal procedures to prohibit poisonous anti-fouling paint. However, still there is no effective innoxious paint appeared. The object of this invention is to provide a completely inorganic, permanently anti-corrosive, innoxious anti-fouling paint based upon the study of corrosion machanism of iron and the property of adhesively inhabitating organisms in the sea environment. Another object of this invention is to provide a paint for coating inside and outside of structures and colors for pictures which have excellent adhesiveness, waterresistance, humidity control, anti-static, anti-bacterial property and permanently unfading colors. The latter object of the invention relates directly to a noble work for inheriting and developing more the valuable cultural heritages of our ancestors (everlasting, unfading colors) displayed in the mural of tombs and pictures of many colors and designs in the historic relics of Koguryo dinasty of our country. According to the invention the paint is manufactured by various method in accordance with their uses. First method The solution of silicate I^O-SiOgof molar ratio (M ? 0/ Si0 2 ) 0,4-0,25 is mixed with ammon chloride so that molar ratio (NH 4 C1/Si0 2 ) can reach 0,2-0, where M -= K,Na, Li, Rb). Then the following reaction occurs: Na 2 0-nSi0 2 + 2 H 4 C1 + H 2 0 = 2NaCl + 2 H 3 t' 4+. τn..Sςiin0 2 _ ++ 22HH 2 -.0 The silicagel obtained by above mentioned reaction is matu for a certain period of time and washed to get gel-state denatu ammonia silicagel (xH 2 Si0,»NH 4 0H- H 2 0) which absorbed ammonia g Its molar ratio (NH 4 0H/Si0 2 ) is preferably 0,25-0,5. This mixtu is mixed with silicate solution of molar ratio (M 2 θ/Si0 2 ) 0,25- at the ratio of 1-50:100 by weight. The resulting solution is dispersed with MX solution so that MX/Si0 2 can reach 0,01-6,05 to get denatured silicate solution of high viscosity (vehicle) (where, M: K, Na, Li, Rb, Ba, Zn, Ca; X: 01, P, Br). If above-mentioned denatured silicate solution is added wi filler, dispersoid alumo silicate, metal oxides and metal powde then a paint will be obtained. (where, the alumosilicate is M(I) 2 0»M(II)0'Al 2 0 5' nSi0 2 «mH 2 0 (M(I) and M(II) are monovalent a bivalent metallic cations, n is molar m is number of mol of water). Molar ratio is preferably in the range of 0,5-20, molar ratio (Na 2 θ/CaO) is preferably in the range of 1-10, the amount of ion exchange bei 5-40 mg equivalent/100 g. The grain size of the filler is prefe ably 250-300 mesh., The vehicle is added preferably with alumo¬ silicate, one or two_kinds of metal oxides of among ZnO, Ti0 2 , Pe 2 0,, BaO, Al 2 0,, one or two kinds of metallic powders of amon Zn, Pe, Al and Cu at the proportion of 30-40, 0-20, 0-20 weight respectively. If this paint is applied, a film having a capacity of exchanging and absorbing ions is obtained. According to the molar ratio of filler and amount of its addition, the ion absorbing capacity of film changes in the ra of 90-110 mg equivalent/100 g, iron exchanging capacity being 10-30 mg equivalent/100 g. If a paint is made in this way and applied to the botto;. of a ship, inorganic film is obtained, which is prooved to have an absorbing capacity 3 times higher than natural zeolite in terms of absorption amount of cation, in particular Ca 2+ (see table 1). It was prσoved by infrared absorption spectrum analysis, X- ray difraction analysis, X-ray photoelectron analysis, differenti thermal analysis that the film has a three dimensional reticular structure capable of performing the function of ion exchange and absorption. Adhering to the bottom of a ship, the organism secretes an adhesive substance* amino acid calcium colloid, which becomes a strong high molecular adhesive on the surface of the object and firmly adheres thereto. As the surface of the film comprises very active alkali metal cations, it is able to easily exchange with other metallic cations. Therefore, the film absorbos Ca away from amino acid calcium colloid solutio* of adhesive secretion product of sea adhesive organisms, thus weakening the adhesive strength of the adhesive organisms and making them unable to inhabitate. Table 1 Comparison of ion absorbability of zeolite and inorganic film Table 2 Capacity of Ca ion absorption and exchange of fiim Absorption Absorption Exchange Exchange Equivalent of capacity capacity capacity capacity secreting liquid per 100 g per 1 cm 1 per 100 g per 1 cm of sea adhesive organism 100 mg 0,06 mg 17 mg 0,01 mg 2x10 "5 mg equiv. equiv. equiv. equiv. equiv, per 1 cm' As is seen in the table 2, the capacity of exchange per 1 CB of film is 0,01 mg equivalent and amount of calcium secreted by sea adhesive organism is 2x10 "5 mg equivalent, these figures show that calcium exchangeability of film is far higher. Therefore, not only the ilm has the capacity to absorb any amount of calcium secreted by sea adhesive organisms, including epiphytes, but also disorption-absorption process of calcium and sodium continues due to the constant reverse reaction in the sea water. Therefore, as long as ilm exists f the anti-fouling capacity against sea adhesive organisms, including epiphytes is permanent. The function of film to protect iron from corrosion is also explained by the mechanism of absorbing and fixing the ions by prohibiting the flow of iron ions due to the capacity of absorption of ion. The X-ray photoelectron analysis of film is shown in the annexed picture. It shows that the additives bond chemically to form a passivating film. Embodyment The vehicle is obtained according to the first method. Th vehicle is mixed with filler of following composition and the resulting paint is applied to specimens and bottom of a ship a cured for a week, followed by exposure test and actual test. Composition: (by weight %) Vehicle 40-60 Alumosilicate 20-30 Metal oxide 5-20 Zinc powder 5-16 The result shows that anti-fouling and anti-corrosive fun of film has still been maintained for 15 years until now since beginning of the actual test. Second method Polyethylene glycol (n=1-2000) is added to silicate solu¬ tion having molar ratio The former causes a neutralization and polysilicate elastomer (PSE) is obtained. H0-(CH 2 CH 2 0) 1| -H + Na 2 0-nSi0 2 + H 2 0 = = 2H0-(0H 2 CH 2 0)-Na + (H j SiO^'yHgO + (x-y)H 2 0 Precipitated PSE is dispersed into silicate solution so that molar ratio (PSE/Si0 2 ) can be 0,1-I 0 ,0and then aluminium salt solution is added thereto so that molar ratio(Al 2 0,/Siθ ) can be 0,01-5,0 and heated at 100 0 to get vehicle. •This vehicle is mixed with barium sulphate, calcium phospha 1-2 kinds of metal oxides such as alumina, titanium white, zinc oxide etc. at the proportion of 5:1-10 by weight, which is made paste state, thus obtaining excellent smokeless, humidity contro ling, anti-bacterial, anti-static paint needed for painting insi and outside of structures or colors for pictures. The paint thus made is applicable to fabrics, concrete plate glass, iron, slate and stone etc., excluding resin and oil colors under-coating plate. Embodyment T n e vehicle obtained according to the second method is mixed with dispersoid of following composition and applied to cement plate and cured for one week: Vehicle 40-60 % (by weight) Titanium oxide 5-10 % » " Zinc oxide 5-10 % " » Barium sulphate 10-25 % " n Table 3 Main properties of film Humidity control Anti-bacterial (Anti-static Pire-resistance property property property 5-7 g/m.h*atm assed test of 10 8 ohm No change at JIS 279 1000 β C Passed exposure test for 8 years As is seen in table 3, the paint for decoration of insid and outside of building and structure has excellent humidity control, anti-bacterial, anti-static properties and is water¬ proof and smokeless. Therefore, its serviβe time is very long and it provides a good hygenic environment. Further, it is of completely inorganic, so it has an anti-aging property, too. Actual test When organic paint was applied as a painting material fo inside and outside decoration of building, it grew moldy in a month in the mold-growing environmen (at humidity of 90 % or so, temperature of 20-30 β C) and was contaminated within a year, which caused repainting unavoidably. Though the paint has been used for inside-outside coatin and also for colors of pictures according to the invention, there has not been found any mold growing for 8 years since actual test commenced and the surface of the object has not contaminated yet even in the mold-growing environment.

Claims: Claims 1. Completely inorganic, permanently anti-rcorrosive, innoxious anti-fouling paint, characterized in that silicate solution of M 2 0« Si0 2 (M:k,Na,Li,Rb) of molar ratio (MgO/SiO^ 0,4-0,25 is mixed with ammonium chloride so that molar ratio (NH.C1/Si0 2 ) can reach 0,2-0,5 to get silicagel, which is matured for a certain period of time and washed to get a gel- state mixture, which absorbed ammonia gas, i.e. ammonia silicate (xH 2 Si0 5 *NH 4 0H«yH 2 0) of molar ratio (NH 4 0H/Si0 2 ) 0,25-0.5, which is added to silicate solution M ? 0» Si0 2 of raolar ratio (MgO/SiOg) 0,25-0,5 at the ratio of 1-50:100, resulting denatured silicate colloidal solution is again dispersed with MX (M: Li, Na, K, Ba, Ca, Al; X: P, Br, Cl) so that molar ratio(MX/Si0 2 ) can reach 0,01-0,05 to get denatured silicate solution (vehicle), which being added with alumosilicate, one or two kinds of metal oxides of among ZnO, Ti0 2 , I^O,, BaO, AlgO * , and one ortwo kinds of metal powder to provide permanently corrosive, innoxious anti- fouling function. 2. Paint according to claim 1, characterized in that ammonia silicate of molar ratio (NH.OH/SiOg) 0,25-0,5 is added to silicat solution M 2 0» Si0 2 of molar ratio (M 2 θ/Si0 2 ) 0,25-0,5 at the proportion of 1-50:100 by weight to get denatured silicate colloi solution. 3. Paint according to claim 1 or 2, characterized in that the denatured silicate colloidal solution obtained by claim 2 is added with MX (so that molar ratio (MX/Si0 2 ) can reach 0,01-0,05 to get again denaturedhigh viscosity silicate solution(vehicle). 4. Paint according to any of the claims 1 to 3, character in that its dispersoid, alumosilicate M(I) 2 0»M(II)OΑl 2 0 5 .nSi0 mH O (where M(l) or M(II) is monovalent or bivalent metallic c n is molar ratio of Si0 2 /Al 2 0,, m is number of mol of water) h molar ratio (Na ? θ/Caθ) in the range of 1-10, molar ratio (Si0 2 Al 2 o,) in the range of o, -2,0, the amount of ion exchange in £ange of 5-40 mg equivalent/100 g. 5. Paint according to any of the claims 1 to 4, character in that denatured sodium silicate solution is mixed with one two kinds of metal oxides selected of among the group of ZnO, Pe 2 °3' BaO, A1 2 0. * , alumosilicate powder and one or two kinds metal powder selected of among Zn, Pe, Al, Cu by 0-20, 30-40, 0-20 weight % respectively. 6. Paint according to any of the claims 1 to 5, character in that its chemical structure forms three dimensional one on surface of the object, thus discomposing amino acid calcium co the adhesive secretion of adhesive organisms of ship and givin anti-fouling effect. 7. Paint according to any of the claims 1 to 6, character in that it gives innoxious anti-fouling effect without using poisonous material. 8. Baint according to any of the claims 1 to 7, characteri in that it gives anti-corrosive effect by prohibiting the flow ions of iron. 9. Paint according to any of the claims 1 to 8, character in that it gives anti-corrosive, anti-fouling effect permanentl until the service time of ship ends due to the reverse process ion absorption and exchange in the sea water. • 10. Completely inorganic paint for coating inside and outs of structure and colors for pictures, characterized in that pol ethylene glycol is added to silicate solution of molar ratio (M Si0 2 ) 0,4-0,25 to get polysilicate elastomer (PSE), and that th latter is added to silicate solution so that molar ratio (PSE/S can reach 0,1-10, the resulting solution being added with alumi salt solution so that molar ratio (Al 2 0,/Si0 2 ) can reach 0,01-5 and heated at 100 β C to get denatured silicate vehicle colloida solution, which being added with one or two kinds of pigments selected of among the group of barium sulphate, calcium phospha alumina, titanium white, zinc oxide and other pigments to get mo liquid paint of paste state adequate to making functional materi for coating inside and outside of structures and colors for pict 11. Paint according to claim 10, characterized in that poly ethylene glycol (n=1-2000) is added to silicate solution of mol ratio (M O/SiO p ) 0,4-0,25 to get polysilicate elastomer (PSE). 12. Paint according to claims 10 or 11, characterized in th PSE is added to silicate solution in claim 11 so that molar rati (PSE/Si0 2 ) can reach 0,1-10, and that the resulting solution is added with aluminium salt so that molar ratio (Al p O,/SiO p ) can reach 0,01-5,0 and heated at 100 β C to get denatured silicate vehicle colloidal solution. 13. Paint accrding to any of the clamis 10 to 12, character ized in that the denatured silicate vehicle colloidal solution i added with one or two kinds of pigments selected of among the group of BaSO^, CaCΘ^, Ti0 2 , and other pigments at the ratio of 5:1-10 by weight. 14. Paint according to any of claims 10-13, characterized i that it is applicable to fabrics, concrete plate, glass, steel plate, slate and stone with the exception of resin and primer pl for oil colors.

Inventors: HYONG KIM GYU, YUN CHAE JAE, HYONG, KIM, GYU, YUN, CHAE, JAE
Applicants: HUNGSONG CORP, HUNGSONG CORPORATION
Application year: 1991
Main classification: C09D5
IPC codes: C09D1, C09D5