TWI248459B - 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

1248459 (1) Rose, invention description 〇 (description of the invention should be stated: the technical field, prior art, content, implementation and simple description of the invention) FIELD OF THE INVENTION The present invention relates to a coating composition comprising a polymer , falling agent and hardener. Application of the coating composition of the present invention to a substrate allows the surface of the coated substrate to have an antifouling effect. Prior Art In the past, the coating requirements of a general substrate for a protective layer were often only required to be beautiful and colorful, but the stain resistance of the coating was not strictly required. However, in our daily life, there are many sources of pollution, such as dust floating in the gas, oily smoke, poorly charged electricity and industrial acid rain, which often cause pollution on the surface of the substrate, which impairs its appearance and protection. performance. The coating is a multi-phase and multi-component material, usually containing solvents, resins, pigments and additives. Generally, the traditional coatings are composed of an acrylic acid (acrylic) resin, an alkyd resin, a phenolic resin, an amine resin. Epoxy resin, etc. However, due to the poor structure of the resin itself, low surface hardness and high surface energy, the anti-fouling property of the pollution source is obviously insufficient. As a result, coatings companies are looking for coatings with anti-fouling properties to meet consumer demand. The recent discovery of organic fluorinated polymer coatings is a revolutionary advancement for the coatings industry. Organic fluorinated polymers exhibit a certain degree of stain resistance due to their special morphogenesis and σ structure.曰本特开平平6-345823, a fluorocopolymer resin with good weatherability and water repellency after long-term outdoor violent sputum 'S /, and 1248459

(7) The system consists of a thin matrix acrylic acid monomer, a fluoroolefin monomer and a perfluorovinyl monomer copolymer disk j, a "σ, 'm resin and then a non-yellowing isocyanate hardener at room temperature to harden the wood bridge' After obtaining a coating film, the coating film can maintain the original performance on the surface of the coating film after 6 months of outdoor exposure. Japanese Patent Laid-Open No. Hei 7/26204 proposes a fluorine-containing polyurethane forge urethane. The polymer is a ruthenium-containing 70 Å perfluoroacrylic acid or perfluorovinyl group containing an unsaturated group (molecular weight 300 to 3000). Single system. The resin and isohydrogen acid § 曰 under the main temperature bridging to obtain a coating film, the coating film after exposure to accelerated weathering 4 inspection machine for 2000 hours, the gloss retention rate is (4)% α, The gloss retention of the fluoroolefin-ethyl oxime ether polymer coating film was as high as 70%. The organic fluoropolymer coating film proposed in the publication is a coating which is excellent in weather resistance, time history and chemical resistance. g The foregoing prior art can solve the pollution of the coating by some pollution sources, but the anti-fouling property of other cold dye sources still needs to be strengthened. In addition, some technologies are based on the side-chain long-chain fluorine implanted in the resin, and the -OH group is added to provide reactivity, and (4) the difference in monomer polarity, which tends to cause phase separation of the resin, which easily leads to cracking of the coating film, thereby lowering the coating film. Stain resistance. Inventive Internal Crossing The inventors of the present invention have found through extensive research that the use of a resin-side long-chain fluorine segment or a ketamine segment can reduce the surface tension of the resulting coating and improve the cold resistance of the coating. In addition, the present invention further utilizes the third-grade carbonic acid vinegar to further provide compatibility, so that a fine-grained film with excellent eye-catching properties can be obtained, and the right-handed soil film can be used to solve the long-term coating film degradation and the anti-fouling property. problem. Therefore, the present invention provides a coating composition, which comprises a polymer, dissolved 1248459

(3) a agent and a hardener which are polymerized from the following monomers: (1) an acrylic monomer; (2) a tertiary carboxylic acid ester; and (3) a fluorinated acrylic monomer, A monomer of the group consisting of a siloxane monomer and a mixture thereof. Solvents which can be used in the coating compositions of the present invention are well known to those skilled in the art and may be, for example, benzenes, vinegars or ketones or mixtures thereof. Non-limiting examples of the benzene solvent 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 ester or a mixture thereof. Non-limiting examples of the ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone or a mixture thereof. The solvent content of the coating composition of the present invention is from 20 to 70% by weight, preferably from 30 to 60% by weight, based on the total composition. The hardener which 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 usable in the present invention is an aliphatic polyisocyanate or an aromatic polyisocyanate or a mixture thereof. Non-limiting examples of aliphatic polyisocyanates include dimers, trimers or adducts thereof of cyclohexane diisocyanate, dimers of trimethylcyclohexane diisocyanate, three 1248459 (4) Dimerization of a spheroid or its adduct, a dimer of cyclohexane bis <methyl isocyanate>, a trimer or an adduct thereof or isophorone diisocyanate Body, trimer or its adduct. Non-limiting examples of aromatic polyisocyanates include dimers of toluene diisocyanate, trimers or adducts thereof, dimers of xylene diisocyanate, trimers or adducts thereof Or a dimer, a trimer or an adduct of diphenylmethane diisocyanate. The alkylated melamine-formaldehyde resin useful in the present invention may be a methylated, ethylated, propylated or butylated melamine-formaldehyde resin, non-limiting examples of which include hexa-methylformaldehyde melamine resin, six <Ethylformaldehyde>melamine resin, tetramethylammonium diamine melamine resin, tetramethylammonium hydride, melamine resin, or tetramethylammonium hydride melamine tree , or a mixture thereof. The hardener content of the coating composition of the present invention is from 5 to 40% by weight based on the total composition. The acrylic monomer for forming a polymer of the present invention may be, for example, acrylic acid, methacrylic acid, methyl acrylate, methyl 2-methylpropionate, butyl acrylate, butyl methacrylate or propionic acid. 2-hydroxyethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 2-hexyl hexyl acrylate or a mixture 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 the monomers. The present invention is used to form a tertiary carboxylic acid ester of a polymer, which may be, for example, a group consisting of a saturated tri-n-carboxylic acid vinyl ester, a saturated tertiary fluorinated vinyl carboxylate, and a saturated tertiary glycerol carboxylate. group. The tertiary carboxylic acid ester is used in an amount of 5 to 50% by weight, preferably 5 to 30% by weight based on the total amount of the monomers. J248459

(5) The fluorinated acrylic monomer of the present invention for forming a polymer has the following formula:

RfCH2CH20(0)CC(R) = CH2 wherein R/ 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 . The preferred fluorinated acrylic monomer is a fluorinated alkyl methacrylate or a mixture thereof, and more preferably a fluorinated alkyl methacrylate wherein n = 6 to 14 or a mixture thereof. According to the present invention, the fluorinated acrylic monomer is used in an amount of from 1 to 40% by weight, preferably from 1 to 20 by weight, based on the total amount of the monomers. The oxirane monomer used in the invention to form a polymer has the following formula:

Me R-ii — I Me

Me O-ii—

Me

Me 〇-έπ n Me R8 where R7 and R8 are each H, Me, CH2 = CH, NH2, NH2-C3H6 〇H-C2H4OC3H6, CH = CCH3-COOH, CH = CH-COOH or

A CH2—CHCH2OC3H6, where...(7) to 25〇. When used in the present invention, the amount of the siloxane monomer is from 1 to 40% by weight, preferably from 1 to 20% by weight, based on the total monomers. The coating composition of the present invention may further comprise pigments and/or additives well known to those skilled in the art, and additives useful in the compositions of the present invention include dispersants, wetting agents, defoamers, accelerators, leveling agents, Light stabilizer, UV absorber, anti-settling agent or a mixture thereof. The coating compositions of the present invention can be prepared by any of the means well known to those skilled in the art. For example, the invention is first used for polymerization to make -10 - 1248459 (6)

The various monomers of the polymer are mixed with a suitable solvent and an appropriate initiator as needed, and polymerized at a suitable temperature and reaction time, and then a hardener and an additive are added to prepare the coating of the present invention. . The coating composition of the present invention can be applied to the surface of any suitable substrate, such as a metal, an alloy, a computer case, a wood, a plastic, a leather or a stone, to impart a stain-repellent effect to the surface of the substrate. Implementation

The invention is further described in the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be made without departing from the spirit of the invention are intended to be included in the invention. The scope. In the examples, the abbreviations used are defined as follows: AA: propylene glycol acid MAA: methacrylic acid MMA: methyl methacrylate

IBMA · Isobornyl Methacrylate BA : butyl acrylate BAc : butyl acetate n-BMA : n-butyl methacrylate 2-HPMA : 2-hydroxypropyl methacrylate FAMA : acrylic acid 2-(Perfluoroalkyl)ethyl ester and mixtures thereof AS: Silicone methyl methacrylate GETCA: Neodecanoic acid glycidyl ester PMA: Propylene glycol acetate Propylene glycol monomethyl ester -11 - 1248459

Acetate) TBPB: Tert-Butyl Perbenzoate Example 1 _ 7 A resin composition was prepared by taking different proportions of monomers and solvents. The preparation conditions are as follows: 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 • Abuse • 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 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 amount (g) PMA 17,6 17.6 17.6 17.6 17.6 17.6 17.6 Starting agent (g) TBPB 0.5 3.0 3.0 3.6 0.5 0.5 0.5 Reaction temperature (°C) 130°C 130°C 130°C 130° C 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

Anti-fouling test of the composition of the stimuli The resin composition of Table 1 was formulated into a coating according to the ratio shown in the table below for the anti-fouling test. The results obtained are shown in Table 2. -12 - 1248459

(δ) Coating formula nir ---- Wang / π team knife --- 10 grams each i^JLicymel 303a) or N-3390b)) 1.4 g / 2.1 g Bac a 5-7 g benzenesulfonic acid ^ 0.01 g _) It is sold by Cytec Technology Co., Ltd. (Cytec). Bayer sells substrates: tinplate ripening · high temperature cymel 303 : 15 ° ° C X30 minutes

Red (Shiseido) smudged dark paper wiped after cleaning surface Jane black singular pen smudge dark paper wiped surface clean room low temperature N-3390: 60 ° C X30 minutes and room temperature 3 days Table 2: anti-fouling property test Data Coffee Stained Time Paper Wipe Surface Cleanliness - CNPC No. 30 Oil Stained Dark Paper Wipe Surface Cleanliness Golden Paint Pen Stained Time Paper Wipe Surface Cleansing Black Crayon Stained Time Paper Wipe Surface Cleanliness; f 5% Thai black station stained surface paper after wiping surface cleanliness

Note: Surface cleanliness indicates: 1-good 2 · can be 3 - still 4 - poor 5 - very poor From the results of Table 2, it can be known that the use of polymers containing fluorinated acrylic monomers or calcined monomers can make coatings The composition has good antifouling properties. -13 -

Claims (1)

1248459 Pickup, Patent Application No. 1 A coating composition comprising (1) a polymer; (2) a benzene, a S-type, a ketone or a mixed solvent thereof; (3) a hardener characterized by the polymerization The system is polymerized from the following monomers: (1) an acrylic monomer; (2) a tertiary carboxylic acid ester; and (3) selected from a fluorinated acrylic monomer, a siloxane monomer, and a mixture thereof. The monomers that make up the group. 2. The composition according to claim 1, wherein the benzene solvent is selected from the group consisting of benzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, and styrene, and mixtures thereof. 3. The composition according to claim 1, 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 consisting of ethoxypropyl propyl ester and monomethyl ether propylene glycol ester and mixtures thereof. 4. The composition according to claim 1, wherein the ketone solvent is selected from the group consisting of acetone, methyl ethyl ketone and methyl isobutyl ketone and mixtures thereof. 5. The composition of claim 1, wherein the hardener is selected from the group consisting of one or more polyisocyanates and alkylated melamine-formaldehyde resins. 6. The composition according to claim 5, 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. 1248459 8. The composition according to item 5 of the patent application, wherein the polyisocyanate is Unblocked. 9. The composition of claim 5, wherein the alkylation is nailed, ethylated, propylated or butylated. 10. The composition according to claim 5, wherein the alkylated melamine-formaldehyde resin is hexa(methylformaldehyde) melamine resin, hexa(ethylformaldehyde) melamine resin, tetrakis(methylformaldehyde)diamine melamine Resin, tetrakis(methylformaldehyde) bis(butylformaldehyde) melamine resin or tetrakis(methylformaldehyde) bis(propylformaldehyde) melamine resin or a mixture thereof. 11. The composition according to claim 1 of the patent application, wherein the pro-glycolic acid monomer is propyl benzoic acid, methacrylic acid, methyl acrylate, methyl 2-methyl acrylate, butyl propyl acrylate, butyl methacrylate Ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 2-hexyl hexyl acrylate or a mixture thereof. 12. The composition according to claim 1, wherein the tertiary carboxylic acid ester is selected from the group consisting of saturated tertiary carboxylic acid vinyl ester, saturated tertiary carboxylic acid vinyl ester and saturated tertiary dimethyl carboxylic acid butyl acrylate. The group formed. 13. The composition according to claim 1, wherein the fluorinated acrylic single system has the formula: RfCH2CH20(0)CC(R) = CH2 wherein Rf is a linear or branched perfluorinated alkane Base: 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 patent application, wherein the fluorinated acrylic 1248459 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, wherein the monooxane single system has the following formula: Wherein R7 and R8 are each H, Me, CH2 = CH, NH2, NH2-C3H6, OH-C2H4OC3H6, CH2CCH3-COOH, CH=CH-COOH or CH^CHCH2OC3H6 and wherein n=10 to 250. 16. The composition according to item 1 of the patent application, wherein the content of the solvent is from 20 to 70% by weight based on the total composition. 17. The composition according to item 16 of the patent application, wherein the content of the solvent is from 3 to 60% by weight based on the total composition. 18. The composition according to item 1 of the patent application, wherein the content of the hardener is 5% to 40% by weight based on the total composition. 19. The composition according to claim 1, wherein the amount of the acrylic monomer is from 20 to 80% by weight based on the total monomer. 20. The composition according to claim 19, wherein the amount of the acrylic monomer, based on the total monomer amount, is from 30 to 70% by weight. 21. The composition according to claim 1, wherein the tertiary carboxylic acid ester is used in an amount of from 5 to 50% by weight based on the total monomer. 22. The composition according to item 21 of the patent application, wherein the amount of the tertiary carboxylic acid ester is 5 to 30% by weight based on the total monomer amount. 1248459 23. The composition according to claim 1, wherein the fluorinated acrylic monomer is used in an amount of from 1 to 40% by weight based on the total monomer. 24. The composition according to claim 23, wherein the fluorinated acrylic monomer is used in an amount of from 1 to 20% by weight based on the total monomer. 25. The composition according to claim 1, wherein the amount of the siloxane monomer is from 1 to 40% by weight based on the total monomer. 26. The composition according to claim 25, wherein the amount of the siloxane monomer is from 1 to 20% by weight based on the total monomer. 27. The composition according to item 13 of the patent application, wherein the amount of the vinyl monomer is from 5 to 40% by weight based on the total monomer. 28. The composition according to claim 27, wherein the amount of the ethylenic monomer is from 5 to 25% by weight based on the total monomer. 29. The composition according to item 1 of the scope of the patent application additionally comprises a pigment. 30. The composition according to item 1 of the patent application, further comprising an additive selected from the group consisting of a dispersant, a wetting agent, an antifoaming agent, an accelerator, a leveling agent, a photostabilizer, an ultraviolet absorber, an anti-settling agent, or a mixture thereof. 31. A method of coating a surface of a substrate comprising applying a coating composition as disclosed in claim 1 to a surface of a substrate. 32. The method of claim 31, wherein the substrate comprises a metal, an alloy, a computer case, wood, plastic, leather or stone.