MATTE CLEAR ANTI-FOULING ANTI-CORROSION SURFACE COATING AND USES THEREOF, AND MATTE CLEAR ANTI-FOULING ANTI-CORROSION SURFACE LAYER AND MATTE CLEAR ANTI-FOULING ANTI-CORROSION METAL

Abstract

A matte clear anti-fouling anti-corrosion surface coating and uses thereof, and a matte clear anti-fouling anti-corrosion surface layer and a matte clear anti-fouling anti-corrosion metal, wherein the matte clear anti-fouling anti-corrosion surface coating comprises: a fluorine-modified polysilazane and a solvent, wherein the content of the fluorine-modified polysilazane is approximately 5-80% by weight based on the total weight of the matte clear anti-fouling anti-corrosion surface coating. Accordingly, the coating can be applied to a corrosion-prone metal sheet or a corrosion-prone metal plate with a protective priming coat (a coated object). The coating is stain repellent, hydrophobic, anti-graffiti, corrosion resistant, clear, matte clear, resistant to temperature changes, resistant to impact, and tough among other characteristics, and is capable of not changing the original color or gloss of the coated object; the coating can be cured at room temperature for direct uses outdoors, and/or can be heated and cured for uses in factories. Additionally, the coating can also be applied directly on a surface of a metal that is not susceptible to rusting, wherein the coating can be applied directly after the addition of a matting agent, or without the addition of a matting agent and the coating can still be matte clear as described above.

Claims

1. A matte clear anti-fouling anti-corrosion surface coating, comprising: a fluorine-modified polysilazane and a solvent, wherein the content of the fluorine-modified polysilazane is approximately 5%˜80% by weight based on the total weight of the matte clear anti-fouling anti-corrosion surface coating.

2. The matte clear anti-fouling anti-corrosion surface coating of claim 1, wherein the fluorine-modified polysilazane comprises a copolymer derived from a fluoride, a siloxane and a silazane.

3. The matte clear anti-fouling anti-corrosion surface coating of claim 2, wherein by weight percentage, the fluoride accounts for approximately 10%˜30%, the siloxane accounts for approximately 20%˜30%, and the silazane accounts for approximately 40%˜70%.

4. The matte clear anti-fouling anti-corrosion surface coating of claim 2, wherein the fluorine-modified polysilazane comprises but is not limited to: poly(perfluorodecyl methylsiloxane), poly(nonafluorohexyl siloxane), poly(methyl trifluoropropyl siloxane), polydimethylsiloxane, hexafluoropropylene oxide, perfluoropolyether sulfonic acid, trifluoromethyl trifluorovinyl ether, poly(tetrafluoroethylene-co-trifluoromethyl trifluorovinyl ether), perfluoro(propylvinyl ether), perfluoro(sulfonylvinyl ether), hexafluoroisobutylene, pentafluoroethyl trifluorovinyl ether, perfluoro-3,5-dioxahexyl vinyl ether or hexafluoropropylene oxide trimer vinyl ether.

5. The matte clear anti-fouling anti-corrosion surface coating of claim 2, wherein the siloxane comprises but is not limited to polydimethylsiloxane (PDMS), methyl siloxane resin, cyclopentasiloxane, phenyl trimethicone, amodimethicone or cyclomethicone.

6. The matte clear anti-fouling anti-corrosion surface coating of claim 1, wherein the surface coating is used as a top coating to be applied on a metal sheet which is coated with a protective coating for metals.

7. The matte clear anti-fouling anti-corrosion surface coating of claim 6, wherein the protective coating for metals comprises but is not limited to: a fluoropolymer coating, a silicone modified polyester (SMP) coating, a silicone modified PVDF (SMPF) coating or a polyester (PE) coating.

8. The matte clear anti-fouling anti-corrosion surface coating of claim 6, wherein the metal sheet comprises but is not limited to an iron sheet, a steel sheet, a galvanized steel sheet, a nickel-plated iron sheet, a magnesium-aluminum-zinc alloy sheet or an aluminium alloy sheet.

9. The matte clear anti-fouling anti-corrosion surface coating of claim 1, wherein the surface coating is used to be applied directly to a metal sheet as a top coating.

10. The matte clear anti-fouling anti-corrosion surface coating of claim 9, wherein the metal sheet comprises but is not limited to a titanium sheet or a titanium alloy sheet.

11. A matte clear anti-fouling anti-corrosion surface layer, comprising the matte clear anti-fouling anti-corrosion surface coating of claim 1 being applied and then hardened into a layer by moisture at room temperature or by heat curing.

12. A matte clear anti-fouling anti-corrosion metal, comprising binding the matte clear anti-fouling anti-corrosion surface coating of claim 1 to a corrosion-resistant metal surface, or a corrosion-prone metal surface with a protective coating for metals.

13. The matte clear anti-fouling anti-corrosion metal of claim 12, wherein the corrosion-resistant metal comprises but is not limited to a titanium or a titanium alloy.

14. The matte clear anti-fouling anti-corrosion metal of claim 12, wherein the corrosion-prone metal comprises but is not limited to an iron, a steel, a galvanized steel, a nickel-plated iron, a magnesium-aluminum-zinc alloy or an aluminium alloy.

15. The matte clear anti-fouling anti-corrosion metal of claim 12, wherein the protective coating for metals comprises but is not limited to: a fluoropolymer coating, a silicone modified polyester (SMP) coating, a silicone modified PVDF (SMPF) coating or a polyester (PE) coating.

Description

DESCRIPTION OF THE EMBODIMENTS

Comparative Example 1

[0024] Gamet Primer W (Toa Resin Co. Ltd.) and Gamet #1000 (Toa Resin Co. Ltd.) were applied on a galvanized steel sheet (Yieh Phui Z27) as a priming coat and a top coat (or finishing coat), respectively, wherein the dry film thickness of the priming coat (or bottom coat) and the top coat was 5 μm and 20 μm, respectively, and a finished sheet was obtained after heating at 240° C. for 10 min each. After being fastened on a wooden board with screws, the finished sheet was subjected to tests for determination of the water contact angle, the sliding angle and the salt spray resistance. According to the test results, the water contact angle was 85±5 degrees, the sliding angle was 55±5 degrees, and the salt spray resistance test resulted in rusting around the screws.

Comparative Example 2

[0025] A Yieh Phui 2C energy-efficient coated steel pre-painted with a silicon modified polyester coating was used a plank. The dry film thickness of the priming coat and heating conditions were the same as in Comparative Example 1. After being fastened on a wooden board with screws, the finished sheet was subjected to tests for determination of the water contact angle, the sliding angle and the salt spray resistance. According to the test results, the water contact angle was 75±5 degrees, the sliding angle was 50±5 degrees, and the salt spray resistance test resulted in rusting around the screws.

Example 1

[0026] The matte clear anti-fouling anti-corrosion surface coating of the present invention (model: HyperDurays CP series) was applied on the finished sheet of Comparative Example 1 and then cured by moisture at room temperature. The finished product was obtained after 1-hour surface drying and 4-hour hardening. After being fastened on a wooden board with screws, the finished sheet of Example 1 was subjected to tests for determination of the water contact angle, the sliding angle and the salt spray resistance. According to the test results, the water contact angle was 107±5 degrees, the sliding angle was 15±5 degrees, and the salt spray resistance test resulted in no rusting.

Example 2

[0027] The matte clear anti-fouling anti-corrosion surface coating of the present invention (model: HyperDurays CP series) was applied on the finished sheet of Comparative Example 2 and then cured by moisture at room temperature. The finished product was obtained after 1-hour surface drying and 4-hour hardening. After being fastened on a wooden board with screws, the finished sheet of Example 2 was subjected to tests for determination of the water contact angle, the sliding angle and the salt spray resistance. According to the test results, the water contact angle was 107±5 degrees, the sliding angle was 15±5 degrees, and the salt spray resistance test resulted in no rusting.

[0028] In other words, both Examples 1 and 2 of the present invention have higher hydrophobicity (water contact angle and sliding angle) as well as higher salt spray resistance.

[0029] Hence, the matte clear anti-fouling anti-corrosion surface coating disclosed in the present invention is suitable as a top coating to be applied on a metal sheet which is coated with a protective coating for metals. The protective coating for metals may be a PVDF fluoropolymer coating, a silicone modified PVDF (SMPF) coating, a silicone modified polyester (SMP) coating, or a polyester (PE) coating. The metal sheet may be an iron sheet, an aluminum sheet, a steel sheet, a galvanized steel sheet, a nickel-plated iron sheet or any kind of a metal sheet which is suitable for steel panel walls.

Comparative Example 3

[0030] An easy-to-clean resin (Merck 1500RC) in combination with a propylene glycol methyl ether acetate (PMA) solvent, the weight percentage thereof being 10% and 90%, respectively, was used as an easy-to-clean coating to be applied on a surface of a titanium sheet (TC4, Heqiang Titanium Industry). The dry film thickness was 1 μm after the completion of hardening by moisture at room temperature, 1-hour surface drying and 4-hour hardening. Tests were conducted for determination of the water contact angle, the sliding angle, the ultraviolet accelerating aging (QUV weathering resistance), gloss and bending (0T “T” Bend). According to the test results, the water contact angle was 100±5 degrees, the sliding angle was 55±5 degrees, the gloss value at 60° was 640, and the coat fractured in a 0T bend. The contact angles before and after QUV weathering were: 200 hours, less than 100 degrees; 400 hours, less than 90 degrees; and 2000 hours, less than 80 degrees.

[0031] According to the analysis of the results of Comparative Example 3, the previously uncoated titanium sheet had gloss at 60° of 800, which changed to 640 after coating, and hence the metal sheet was still reflective and could cause light pollution to building facades. Although the contact angle increased after coating, leading to an effect of easy cleaning, the weather resistance was poor; and additionally, the coat is prone to fracturing when the bending angle of the titanium panel is too large during actual outdoor applications.

Comparative Example 4

[0032] An easy-to-clean resin (Merck 1800RC) was mixed with a propylene glycol methyl ether acetate (PMA) solvent, the weight percentage thereof being approximately 10% and approximately 90%, respectively, and a matting agent (Fuji SylysiaSY-350) of 0.03% by weight percentage was added, giving an easy-to-clean coating to be applied on a surface of a titanium sheet (TC4, Heqiang Titanium Industry). The dry film thickness was 1 μm after the completion of hardening by moisture at room temperature, 1-hour surface drying and 4-hour hardening. Tests were conducted for determination of the water contact angle, the sliding angle, the gloss and bending (0T “T” Bend). According to the test results, the water contact angle was 100±5 degrees, the sliding angle was 55±5 degrees, the gloss value at 60° was 318, and the coat fractured in a 0T bend.

[0033] According to the analysis of the results of Comparative Example 4. the previously uncoated titanium sheet had a gloss at 60° of 800, which changed to 318 after coating. Although the titanium sheet was not reflective, the original metallic luster of the titanium plate was not exhibited because of the opaque white matting agent. Moreover, the coat is prone to fracturing when the bending angle of the titanium sheet is too large during actual outdoor applications. Additionally, the addition of the matting agent might even destroy the metal structure because of thermal expansion and contraction thereof.

Example 3

[0034] The matte clear anti-fouling anti-corrosion surface coating of the present invention (model: HyperDurays CP series) was applied on a surface of a titanium sheet (TC4, Heqiang Titanium Industry). The dry film thickness was 1 μm after the completion of hardening by moisture at room temperature, 1-hour surface drying and 4-hour hardening. Tests were conducted for determination of the water contact angle, the sliding angle, the gloss and bending (0T “T” Bend). According to the test results, the water contact angle was 107±5 degrees, the sliding angle was 15±5 degrees, the gloss value at 60° was 540, and the coating was intact with no fracture in a 0T bend. The contact angles before and after QUV weathering were: 200 hours, less than 112 degrees; 400 hours, less than 110 degrees; and 2000 hours, less than 108 degrees.

[0035] According to the analysis of the results of Example 3, the previously uncoated titanium sheet had gloss at 60° of 800, which changed to 540 after coating, thereby causing no light pollution to building facades any more but retaining a matte metallic luster. Meanwhile, the coated metal had an effect of easy cleaning and is weather resistant. Moreover, the titanium sheet can be bended to a large enough angle during actual outdoor applications and the coat is not susceptible to fracturing.

[0036] Hence, the matte clear anti-fouling anti-corrosion surface coating disclosed in the present invention is suitable for applications as a top coating to be applied directly on a metal sheet. Here, the metal is a titanium alloy. It is worth mentioning that the matte effect of the matte clear anti-fouling anti-corrosion surface coating does not require an addition of another material like a matting agent.

[0037] In order to verify the technical effects of the above examples, organizations including the SGS Material and Engineering Laboratory, the Taiwan Paint Industry Association and the Industrial Technology Research Institute of Taiwan were further commissioned to verify the present invention, and the tests included: gloss, dry film hardness, adhesion, impact resistance, abrasion resistance, chemical resistance, dry film thickness, humidity resistance, water contact angle, cyclic corrosion test, weather resistance and salt spray test among others.

[0038] Table 1 shows the test apparatus. Table 2 shows the test conditions. Table 3 shows the test results.

TABLE-US-00001 TABLE 1 Test Apparatus Name Brand Model Micro-TRI-Gloss BYK 4446 Gloss Meter Pencil MITSU-BISHI uni N/A Impact Tester BYK 5512 Humidity Tester J.T.M. Technology JTM-1274 Cyclic Corrosion Tester Q-LAB Q-Fog/CRH1100HSC Coating Thickness Gauge QuaNix 8500 Basic C Q-SUN Xe-3 Xenon Arc Q-LAB Q-SUNXe-3-HBS Test Chamber Spectrophotometer MINOLTA CM-3600d Contact Angle Meter ASTP VCA Optima XE Salt Spray Tester ERICHSEN 606/400I

TABLE-US-00002 TABLE 2 Test Conditions Cyclic Corrosion Test Test solution 0.05% NaCl + 0.35% (NH.sub.4).sub.2SO.sub.4 Conditions of each cycle One-hour fog + one-hour dry-off Chamber temperature during 24 ± 3 the fog condition (° C.) Chamber temperature during  35 ± 1.5 the dry-off condition (° C.) Spray volume (ml/hr/80 cm.sup.2) 1.0-2.0 pH value of collected salt fog 5.0-5.4 Specimen placement angle 15-30 Weather Resistance Lamp Xenon-arc lamp Filter Daylight Irradiance 0.35 W/m.sup.2/nm @340 nm Conditions of each cycle 102-minute irradiation (@ Black Panel Temperature 63° C.) + 18- minute irradiation and water spray Salt Spray Test Salt solution 5 wt. % NaCl solution pH value of the salt solution 6.5-7.2 Spray chamber temperature 35 ± 2 (° C.) Spray volume (ml/hr/80 cm.sup.2) 1.0-2.0

TABLE-US-00003 TABLE 3 Test Results Test Test method Test result Gloss (60°) ASTM D523-14 (2018) 47 Dry film hardness (scratch) ASTM D3363-05 (2011) 4H Adhesion AAMA 2605-17a, a. Dry film ASTM D3359-17 5B b. Wet film 5B c. Boiling water 5B Impact resistance (deformation AAMA 2605-17a, ASTM No removal of coating from of 3 ± 0.3 mm, 5/8″, 134 in-lb) D2794-93 (2019) the substrate Abrasion resistance (L/mil.) ASTM D968-17 A 28 Chemical resistance AAMA 2605-17a, a. Muriatic acid resistance ASTM D2244-16 No blistering and no visual (15 mins) change in appearance when examined by the unaided eye. b. Mortar resistance (38° C., No loss of coating adhesion or 100% RH, 24 h) visual change in appearance when examined by the unaided eye. c. Detergent resistance No loss of coating adhesion or (3%, 72 h) visual change in appearance when examined by the unaided eye. No removal of coating under the tape; 100% adhesion. d. Nitric acid resistance No visual change in appearance (30 mins) when examined by the unaided eye and ΔE equaled to 1.15. e. Window cleaner resistance No loss of coating adhesion or (24 h) visual change in appearance when examined by the unaided eye. No removal of coating under the tape; 100% adhesion. Dry film thickness (μm) ASTM-D7091-13 16.2 Humidity resistance (100° F., AAMA 2605-17a No abnormalities in visual 100% RH, 4000 h) appearance Water contact angle (degrees) ASTM D7334-08 (2013) 111.1 ± 1.2 Cyclic Corrosion Test (2000 h) AAMA 2605-17a, G85-11, a. Appearance ASTM D7334-08 (2013) No abnormalities in visual appearance b. Water contact angle (degrees) 105.3 ± 0.6 Weather Resistance ASTM G155-13, ASTM D523- a. Appearance 14 (2018), ASTM D4214-07 No abnormalities in visual (2015), ASTM D7334-08 appearance b. Gloss retention (%) (2013) 76.6 c. Chalking No chalking d. Water contact angle (degrees) 103.8 ± 1.3 Salt Spray Test (4000 h) ASTM B117-18, ASTM No rusting in visual D7334-08 (2013) appearance

[0039] In summary, the matte clear anti-fouling anti-graffiti anti-corrosion surface coating of the present examples comprising fluorine-modified polysilazane can be applied directly on a corrosion-prone metal sheet with a protective priming coat; the surface coating is stain repellent, hydrophobic, anti-graffiti, corrosion resistant, clear, matte clear, resistant to temperature changes, resistant to impact, and tough among other characteristics. The surface coating is also capable of not changing the original color or gloss of the coated object. The coating can be cured at room temperature for direct uses outdoors, and/or can be heated and cured for uses in a factory. Additionally, the matte clear anti-fouling anti-graffiti anti-corrosion surface coating of the examples herein can also be applied directly to a surface of a metal that is not susceptible to rusting. The surface coating herein can be applied directly after the addition of a matting agent, or without the addition of a matting agent and the coating is still matte clear as described above.