TW200417584A - Anti-fouling coating compositions - Google Patents

Abstract

The invention pertains to a coating composition comprising a polymer, a solvent, and a curing agent, characterized in that the polymer is obtained by polymerizing the following monomers: (a) an acrylate monomer; (b) a tertiary carboxylic ester; and (c) a monomer selected from the group consisting of an acrylate fluoride monomer, a silicone monomer, and the mixture thereof. The coating composition of the invention can be coated on a substrate to impart an anti-fouling effect to the coated surface.

Description

200417584 发明 、. Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings are simple. The present invention relates to a coating composition that includes a polymer and an agent. And hardener. Using the coating composition of the present invention to coat the substrate can achieve anti-fouling effect on the surface of the substrate to be covered. #Previous technology In the past, the coating requirements for protective layers of substrates generally required only appearance. Beautiful and colorful, but the pollution resistance of the coating is not strictly required. However, in our daily life, there are many sources of pollution, such as airborne dust, oily smoke, good conductors of charged materials and The industrial Ziyu Temple often pollutes the surface of the substrate and impairs its appearance. Thin paint is a multi-phase and multi-composition substance, which usually contains solvents, resins, pigments: additives, and traditional paints. Its resin content is not only The reason is that acrylic acid is not known, phenolic resins, phenolic resins, amine resins, epoxy resins, etc., the structure of the resin itself is not good, the surface hardness is low and The reason for the large temple is that the pollution resistance of the pollution source is obviously insufficient. Therefore, 'coating companies are looking for coatings with anti-fouling properties to meet consumer needs.'-The discovery of organic messy polymer coatings for the coatings industry In fact, it is a revolutionary progress. Organic fluorinated polymers have a special chemical structure, so they exhibit a certain degree of anti-fouling performance. Japanese Patent Laid-Open No. 6_345823, proposes-a kind of good weather resistance after long-term external exposure And water-repellent gas-containing #polymer resin> The copolymerization (2) (2) 200417584 is prepared by copolymerizing a monomer containing acryl acrylic acid, a fluoroene monomer and a perfluorovinyl monomer. The resin was bridge-hardened with a non-yellowing isocyanate hardener at room temperature to obtain a coating film. After the coating film was exposed to the outdoors for six months, the gloss retention and water repellency on the surface of the coating film could maintain the original performance. Japanese Unexamined Patent Publication No. 7-26204 proposes a fluorine-containing polyurethane polymer, which is composed of a polyhydric alcohol containing an unsaturated group (molecular weight 300-3000) and perfluoroacrylic acid Or perfluoroethylene Made of alkenyl monomer. This resin and isohydroic acid are cured under the main M to obtain a coating film. After being exposed to an accelerated weathering test machine for 2000 hours, the gloss retention rate is more than 88%, which is more than that of Japan. The gloss retention rate of the fluorofluorene-ethylfluorene ether polymer coating film of the Nishin subsidiary is 70%. The organic fluoropolymer coating film proposed in the bulletin is a coating with excellent weather resistance, corrosion resistance and chemical resistance. Although the prior art can solve the pollution of some pollution sources to the coating, the anti-fouling resistance to other pollution sources still needs to be strengthened. In addition, some technologies are implanted into the resin with side-chain long-chain fluorine and pay -0Η It is based on providing reactivity, but due to the difference in monomer polarity, it is easy to cause phase separation of the resin, which can easily lead to cracking of the coating film, thereby reducing the antifouling property of the coating film. SUMMARY OF THE INVENTION The inventors of this case have conducted extensive research and found that the resin side length The chain fluorine segment or the silicone segment can reduce the surface tension of the resulting coating and improve the stain resistance of the coating. In addition, the present invention utilizes a tertiary carbonate to further provide compatibility, so that a fluorine-containing coating film having excellent compatibility can be obtained, which can effectively solve the problems of long-term ash coating film degradation and degradation of stain resistance. Therefore, the present invention provides a coating composition comprising a polymer, a solvent, and a solvent.

(3) agent and hardener, the polymer is polymerized from the following monomers: (1) acrylic monomers; (2) tertiary carboxylic acid esters; and (3) selected from fluorinated acrylic monomers, Monomers of groups consisting of siloxane monomers and mixtures thereof. Solvents which can be used in the coating composition of the present invention are well known to those skilled in the art, and may be, for example, benzene, ester or ketone or a mixture thereof. Non-limiting examples of benzene-based solvents include benzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, or styrene or a mixture thereof. Non-limiting examples of ester solvents include, for example, ethyl acetate, butyl acetate, diethyl carbonate, ethyl formate, methyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, or monomethyl ether Propylene glycol esters or mixtures thereof. Non-limiting examples of the ketone-based solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone or a mixture thereof. The solvent content in the coating composition of the present invention is 20-70% by weight, preferably 30-60% by weight based on the total composition weight. The hardener that can be used in the coating composition of the present invention is not particularly limited and is well known to those skilled in the art, and may be, for example, one or more polyisocyanates or alkylated melamine-formaldehyde resins. When used in the present invention, the polyisocyanate may be blocked or unblocked, and the polyisocyanate that may be used in the present invention is an aliphatic polyisocyanate or an aromatic polyisocyanate or a mixture thereof. Non-limiting examples of aliphatic polyisocyanates include dimer, trimer or adduct of cyclohexane diisocyanate, dimer of trimethylcyclohexane diisocyanate, tri 200417584

(4) Polymer or its adduct, dimer of cyclohexane bis <methyl isocyanate>, trimer or its adduct or dimer of isophorone diisocyanate , Trimer or its adduct. Non-limiting examples of aromatic polyisocyanates include dimers, trimers, or adducts of toluene diisocyanate, dimers, trimers, or adducts of xylene diisocyanate Or dimer, dimer, or adduct of diphenylmethane diisocyanate. The alkylated melamine-formaldehyde resin that can be used in the present invention may be a methylated, ethylated, propylated, or butylated melamine-formaldehyde resin, and non-limiting examples thereof include hexa (methyl formaldehyde) melamine resin, six <Ethyl formaldehyde> melamine resin, tetra <methyl formaldehyde> diamine melamine resin, tetra <methyl formaldehyde> di <butyl formaldehyde> melamine resin, or tetra <methyl formaldehyde> di <propyl formaldehyde> melamine tree , Or a mixture thereof. The content of the hardener in the coating composition of the present invention is 5 to 40% by weight based on the total composition weight. The acrylic monomer used to form a polymer in the present invention may be, for example, propionic acid, methacrylic acid, methyl acrylate, methyl 2-methylpropionate, butyl acrylate, butyl methacrylate, acrylic acid, etc. -2-Hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 2-ethylhexylpropionate or mixtures thereof. The acrylic monomer is used in an amount of 20 to 80% by weight, preferably 30 to 70% by weight based on the total amount of monomers. The present invention is used to form a tertiary carboxylic acid ester of a polymer, which may be composed of, for example, free saturated tertiary decanoate ethyl acetate, saturated tertiary nonanoate vinyl ester, and saturated tertiary decanoate glycidyl ester. Group. The amount of the tertiary carboxylic acid ester is 5-50% by weight, preferably 5-30% by weight based on the total monomer amount. 200417584

(5) The fluorinated acrylic monomer used to form a polymer according to the present invention has the following general formula:

RfCH2CH20 (0) CC (R) = CH2 where Rf is a linear or branched perfluorinated alkyl group CnF2n + 1, where n = an integer from 2 to 20, and R is H, CH3, C2H5 or C3H7 . Preferred fluorinated acrylic monomers are fluorinated alkyl methacrylates or mixtures thereof, and more preferred are fluorinated alkyl methacrylates or mixtures thereof where n = 6 to 14. According to the present invention, the amount of φ of the fluorinated acrylic monomer is 1 to 40% by weight, preferably 1 to 20% by weight based on the total amount of the monomer. Monomer, with the following general formula:

Me O-ii—

Me 0—and a R8 n Me, where R7 and R8 are each H, Me, CH2 = CH, NH2, NH2-C3H6, OH-C2H4OC3H6, CH = CCH3-COOH, CH = CH-COOH or cACHCH2 (x3H6, where n = 1u 250. When used in the present invention, the amount of the siloxane monomer is 1-40% by weight, preferably 1-20% by weight based on the total monomer amount. Composition of the coating of the present invention The additives may further include pigments and / or additives well known to those skilled in the art. The additives that can be used in the composition of the present invention include dispersants, wetting agents, defoamers, accelerators, leveling agents, light stabilizers, Ultraviolet absorbent, anti-settling agent or mixture thereof. The coating composition of the present invention can be prepared by any method known to those skilled in the art. For example, the present invention is first used for polymerization to prepare -10-200417584.

(6) The various monomers of the polymer are mixed with a suitable solvent and an appropriate starter as required, and polymerization is performed under appropriate temperature and reaction time conditions, and then a hardener and additives are added to obtain The coating of the present invention. The coating composition of the present invention can be applied to any suitable substrate surface, such as metal, alloy, computer case, wood, plastic, leather, or stone, etc., and the surface of the substrate can have antifouling effect. Embodiments The following examples will further illustrate the present invention, but are not intended to limit the scope of the present invention. Anyone familiar with the technical field of the present invention can achieve modifications and changes obtained without departing from the spirit of the present invention. It belongs to the scope of the present invention. In the examples, the abbreviations used are defined as follows: AA: propionic acid MAA: methacrylic acid MMA: methyl methacrylate

IBMA · Isobornyl Methacrylate @ Purpose (Isobornyl Methacrylate) BA: Butyl acrylate BAc: Butyl acetate n-BMA: N-butyl methyl methacrylate 2-HPMA: 2-hydroxypropyl methacrylate FAMA: 2- (perfluoroalkyl) ethyl acrylate and its mixture AS: Silylone methyl methacrylate GETCA · Neodecanoic acid glycidyl ester ) PMA: Propylene glycol monomethyl ester -11-200417584

acetate) TBPB: Third butyl perbenzoate Examples 1-7 Resin compositions were prepared by taking different proportions of monomers and solvents, the preparation conditions are shown in Table 1 below: Table 1 Example No. 1 2 3 4 5 6 7 Type and amount of monomer (g) AA 13.4 10.5 10.5 10.5 13.4 10.5 10.5 MAA 0.6 0.6 0.6 0.6 0.6 0.6 0.6 MMA 39.6 21.8 14.5 43.6 23.8 39.6 39.6 IBMA-21.8 29.0---BA 17.1-39.6 14.9 14.9 n-BMA-10.5 10.5 10.5---HPMA 13.2 31.5 31.5 31.5 6.6 28.6 28.6 FAMA 7.0 3.6 Bu 3.6 3.0 7.0 7.0-AS _ 7.0 7.0 7.0---GETCA 46.6 18.6 18.6 18.6 46.6 36.3 23.3 Solvent (xylene) (g) ^ 88 111 105 111 88 88 88 Addition (g) PMA 17.6 17.6 17.6 17.6 17.6 17.6 17.6 TBPB 0.5 3.0 3.0 3.6 0.5 0.5 0.5 Reaction temperature ΓΟ 130 ° C 130 ° C 130 ° C 130 V 130 ° C 130 ° C 130 ° C Time 8 hours 8 hours 8 hours 8 hours 8 hours 8 hours 8 hours Solid content (% by weight) 56.9 49.1 49.8 51.5 55.6 56.4 54

Antifouling test of coating composition The resin composition of Table 1 was formulated into a coating according to the ratio shown in the table below to conduct an antifouling test. The results obtained are shown in Table 2. -12-200417584 Coating Formulation Composition 10 Grams — Hardener (cymel 303a) or N-3390 ") 1.4 g / 2.1 g bac 5-7 g __ ifylbenzenesulfonic acid 0.01 g &gt; Cytec Technology Co., Ltd. Sold by Cytec. B) Substrate sold by Bayer · Tinplate maturation: high temperature cymel 303: 150 ° C X 30 minutes low temperature N-3390: 60 ° C X 30 minutes and room temperature for 3 days Table 2 · Stain resistance test data, _ Synthesis example Pollution source ~ High temperature curing Low temperature curing __ 1 5 6 7 2 3 4 7 Lipstick (Shiseido) Staining time 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours noodles Surface cleanliness after paper wiping 1 2 1 5 2 2 2 5 Black singular pen staining time 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes Surface cleanliness after paper wiping 1 2 2 5 2 2 2 5 Coffee staining time 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes Surface cleanliness after tissue wiping 1 1 1 4 1 1 1 4 China Oil Company No. 30 oil staining time 3 hours 3 hours 3 hours 3 hours 3 Hours 3 hours 3 hours 3 hours Rear surface cleanliness 1 2 1 4 2 2 2 4 Gold paint pen staining time 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes 60 minutes Surface cleanliness after wiping the paper 2 2 2 5 2 2 2 5 black Crayon stain time 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours Surface cleanliness after wiping the tissue 1 2 1 5 2 2 1 5 5% Carbon black stain time 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours After wiping the paper 4¾ The surface cleanliness 1 2 2 5 2 2 2 5 Note ·· The surface cleanliness indicates: 1-good 2 -may 3 -still acceptable 4 -poor 5 -very poor from Table 2 As a result, it was found that the use of a polymer containing a fluorinated acrylic monomer or a silane monomer enables the coating composition to have good antifouling properties.

Claims (1)

200417584. Application patent scope 1. A coating composition comprising (1) a polymer; (2) benzenes, esters, ketones or a mixed solvent thereof; (3) a hardener, which is characterized by the polymerization The system is polymerized from the following monomers: (1) acrylic monomers; (2) tertiary carboxylic acid esters; and (3) selected from fluorinated acrylic monomers, siloxane monomers, and mixtures thereof The monomers that make up the group. 2. The composition according to item 1 of the scope of the patent application, wherein the benzene solvent is selected from the group consisting of benzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, styrene, and mixtures thereof. 3. The composition according to item 1 of the scope of patent application, wherein the ester solvent is selected from the group consisting of ethyl acetate, butyl acetate, diethyl carbonate, ethyl formate, methyl acetate, ethoxyethyl acetate, and acetic acid. A group of ethoxypropyl esters and monomethyl ether propylene glycol esters and mixtures thereof. 4. The composition according to item 1 of the scope of patent application, wherein the ketone solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. 5. The composition according to item 1 of the scope of patent application, wherein the hardener is selected from one or more kinds of polyisocyanate and alkylated melamine · formaldehyde resin. 6. The composition according to item 5 of the application, wherein the polyisocyanate is an aliphatic polyisocyanate or an aromatic polyisocyanate. 7. The composition according to item 5 of the patent application, wherein the polyisocyanate is Blocked. 200417584 8. The composition according to item 5 of the patent application, wherein the polyisocyanate is unblocked. 9. The composition according to item 5 of the scope of patent application, wherein the alkylation is nailing, ethylating, propylating, or butylating. 10. The composition according to item 5 of the scope of patent application, wherein the alkylated melamine-formaldehyde resin is hexa (methylformaldehyde) melamine resin, hexa (ethyl formaldehyde) melamine resin, tetra (methylformaldehyde) diamine melamine Resin, tetrakis (methylformaldehyde) bis (butylformaldehyde) melamine resin or tetrakis (methylformaldehyde) bis (propylformaldehyde) melamine resin or mixtures thereof. 11. The composition according to item 1 of the scope of the patent application, wherein the acrylic monomers are acrylic acid, methacrylic acid, methyl acrylate, 2-methyl methacrylate, butyl acrylate, butyl methacrylate, and propionic acid -2-hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 2-ethylhexyl acrylate or mixtures thereof. 12. The composition according to item 1 of the scope of the patent application, wherein the tertiary carboxylic acid ester is selected from the group consisting of saturated tertiary decanoate vinyl ester, saturated tertiary nonanoate ethyl carboxylate, and saturated tertiary decanoate epoxy propylene Groups of esters. 13. The composition according to item 1 of the scope of patent application, wherein the fluorinated acrylic single system has the following general formula: RfCH2CH2〇 (〇) CC (R) = CH2 where Rf is a linear or branched perfluorinated Alkyl: CnF2n + 1, where n = an integer from 2 to 20, and R is H, CH3, C2H5 or C3H7. 14. The composition according to item 13 of the scope of patent application, in which the fluorinated acrylic is 200417584 The monomer is a fluorinated alkyl methacrylate or a mixture thereof. 15. The composition according to item 1 of the scope of the patent application, in which the siloxane single system has the following general formula: Me R-έί- Me Me Ο-έί- Me Me Ο-έί-R8 I n Me Among them, R7 and R8 is H, Me, CH2 = CH, NH2, NH2-C3H6, OH-C2H4OC3H6, CH = CCH3-C00H, CH = CH-C00H or Gi ^ CHC ^ OCaHe and n = 10 to 250. 16. The composition according to item 1 of the scope of patent application, wherein the content of the solvent is 20 to 70% by weight based on the total composition weight. 17. The composition according to item 16 of the scope of patent application, wherein the content of the solvent is 30 to 60% by weight based on the total composition weight. 18. The composition according to item 1 of the scope of patent application, wherein the content of the hardener is 5 to 40% by weight based on the total composition weight. 19. The composition according to item 1 of the scope of patent application, wherein the amount of acrylic monomers is 20 to 80% by weight based on the total amount of monomers. 20. The composition according to item 19 of the scope of patent application, wherein the amount of acrylic monomer is 30 to 70% by weight based on the total amount of monomer. 21. The composition according to item 1 of the scope of patent application, wherein the amount of tertiary carboxylic acid ester is 5 to 50 weight based on the total monomer amount. / 〇. 22. The composition according to item 21 of the scope of patent application, wherein the amount of the tertiary carboxylic acid ester is 5 to 30% by weight based on the total monomer amount. 200417584 23. The composition according to item 1 of the patent application scope, wherein the amount of the fluorinated acrylic monomer is 1 to 40% by weight based on the total amount of the monomer. 24. The composition according to item 23 of the scope of the patent application, wherein the amount of the fluorinated acrylic monomer is 1-20% by weight based on the total monomer amount. 25. The composition according to item 1 of the scope of the patent application, wherein the amount of the siloxane monomer is 1 to 40% by weight based on the total amount of the monomer. 26. The composition according to item 25 of the scope of the patent application, wherein the amount of the siloxane monomer is 1-20% by weight based on the total amount of the monomer. 27. The composition according to item 13 of the scope of patent application, wherein the amount of the vinyl monomer is 5-40% by weight based on the total amount of the monomer. 28. The composition according to item 27 of the scope of patent application, wherein the amount of the vinyl monomer is 5-25% by weight based on the total amount of the monomer. 29. The composition according to item 1 of the scope of patent application, further comprising a pigment. 30. The composition according to item 1 of the patent application scope, further comprising an additive selected from a dispersant, a wetting agent, an antifoaming agent, an accelerator, a leveling agent, a light stabilizer, an ultraviolet absorbent, an anti-settling agent, or a mixture thereof. 31. A method for coating the surface of a substrate, comprising coating a coating composition as described in item 1 of the patent application on the surface of the substrate. 32. The method according to item 31 of the patent application, wherein the substrate comprises metal, alloy, computer case, wood, plastic, leather or stone. 200417584 Lu, (1), the designated representative countries in this case are: · · plaque (2), the component representative symbols of this representative map are briefly explained: 柒, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: