CN103333535A - Nano-coating liquid, coating formed from the nano-coating liquid, use of the nano-coating liquid on base material and coating method - Google Patents
Nano-coating liquid, coating formed from the nano-coating liquid, use of the nano-coating liquid on base material and coating method Download PDFInfo
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Abstract
The invention provides a nano-coating liquid for being coated on surfaces of base materials such as stainless steel, glass, ceramic and a painting plate. The nano-coating liquid comprises silica nano-particles, a metal salt, an acid, an aqueous solvent and/or a surfactant. Compared with the existing like products, the nano-coating liquid can be coated easily and has better environmental friendliness. A nano-coating formed from the nano-coating liquid on the surface of a base material such as stainless steel has good fingerprint and food stain cleanability, and good salt spray and acid corrosion resistance.
Description
Technical field
The present invention relates to the nano coating liquid field, more specifically, relate to a kind of nano coating liquid that is mainly used in stainless steel, glass, pottery, the substrate surfaces such as plate that spray paint.
Background technology
Stainless steel is used widely in fields such as building decoration (as elevator, curtain wall etc.), kitchen and bath facilities (as rinse bath, fireplace, smoke exhaust ventilator, the kitchen range top etc.), household electrical appliance (as refrigerator, microwave oven, dishwasher etc.), industrial production, communications and transportation.According to statistics, in China, building decoration, kitchen and bath facilities and household appliance technical field, stainless usage quantity have accounted for 60% (about 1,000,000,000 square metres) of its ultimate production.For being applied to the stainless steel in these fields, fingerprint easy to clean and food stains, and the corrosion of salt spray resistance, acid and/or food sauce is very important performance.And have certain thickness coating in the stainless steel surface coating, can satisfy more aforesaid demands at least in part.
Current, several solvent based polymer coating fluid products of these Application Areass have appearred on the Chinese market being used for, for example from the NT5300 in Taiwan, from the Alpha337 of Singapore, etc.The dried thickness of the formed coating of these coating fluids is generally 2-3 μ m.
Early-stage Study finds that nano coating that acidified nano particle coating fluid forms all presents good performance easy to clean comprising on the various base materials such as stainless steel.Yet this coating is for salt fog, acid and still not ideal enough such as the erosion resistance of food sauces such as soy sauce, hot sauce, tomato-sauce.
Therefore, be desirable to provide a kind of novel environment-protection nano coating fluid product, the property easy to clean of fingerprint and food stains better, more tolerated the corrosion of salt fog, acid by its Clear coating that forms.In addition, wish that the Clear coating that is formed at base material by this coating fluid has thinner thickness, makes that the appearance of base material is unaffected basically.
Summary of the invention
The present invention aims to provide a kind of nano coating liquid for stainless steel, glass, pottery, the substrate surfaces such as plate that spray paint.Compare with existing several like products on the market, more environmental protection of nano coating liquid of the present invention, be easier to coating, have good property easy to clean by its coating that forms for fingerprint, food stains etc., and can tolerate the corrosion of salt fog, acid and food sauce etc. preferably.
In one embodiment, a kind of nano coating liquid is provided, described nano coating liquid comprises the nano SiO 2 particle of 1-10 weight %, 0.4-2.0 the metal-salt of weight %, the pH value that its content is enough to guarantee described nano coating liquid is less than 4 acid, and the aqueous solvent that total content is added to 100 weight %.
In one embodiment, described nano coating liquid also comprises the tensio-active agent of 0.05-1.0 weight %.
In one embodiment, the median size of described nano SiO 2 particle is between the 2nm to 75nm, preferably is between the 2nm to 30nm, more preferably is between the 2nm to 10nm.
In one embodiment, described nano SiO 2 particle comprises the nano SiO 2 particle of single median size.
In one embodiment, described nano SiO 2 particle comprises the nano SiO 2 particle of two or more median size.
In one embodiment, described metal-salt comprises the divalent metal-salt, 3 valency metal-salts, 4 valency metal-salts and their mixture.
In one embodiment, described divalent metal-salt comprises nitrate, vitriol, preferably includes strontium nitrate, zinc sulfate, sal epsom, copper sulfate.
In one embodiment, described 3 valency metal-salts comprise nitrate, muriate, vitriol, preferably include aluminum nitrate, aluminum chloride, potassium aluminium sulfate, cerous nitrate, iron(ic) chloride.
In one embodiment, described 4 valency metal-salts comprise nitrate, preferably include zirconium nitrate.
In one embodiment, the mixture of described metal-salt comprises the mixture of aluminum nitrate and cerous nitrate.
In one embodiment, described acid is mineral acid, comprises phosphoric acid, hydrochloric acid and nitric acid.
In one embodiment, described aqueous solvent comprises water, water and the mixture of alcohol and the mixture of water and alcohol ether.
In one embodiment, described tensio-active agent comprises nonionogenic tenside, anion surfactant, zwitterionics and their mixture.
In one embodiment, described ionic surfactant pack is drawn together polyoxyethylene-type nonionogenic tenside, polyol-based non-ionic surfactant, alkylol amide type nonionogenic tenside, fluorine carbon type nonionogenic tenside, organosilicon type and modified organic silicon type nonionogenic tenside and their mixture.
In one embodiment, described anion surfactant comprises carboxylic acid type anion surfactant, sulfonate type anion surfactant, sulfuric acid type anion surfactant, phosphate ester salt type anion surfactant and their mixture.
In one embodiment, described zwitterionics comprises amino acid type surfactant, betaine type amphoteric surfactant and their mixture.
In one embodiment, provide the above-mentioned application of nano coating liquid in base material.This base material can comprise stainless steel, glass, pottery, plate sprays paint.This plate that sprays paint comprises the sheet material with polyester, urethane or Resins, epoxy coating.
In one embodiment, provide the nano coating corrosion-resistant and easy to clean that is formed at substrate surface by above-mentioned nano coating liquid.This base material can comprise stainless steel, glass, pottery, plate sprays paint.This plate that sprays paint comprises the sheet material with polyester, urethane or Resins, epoxy coating.
In one embodiment, also provide the method that above-mentioned nano coating liquid is coated on substrate surface, this method comprises and adopts dip-coating coating, roller coat coating, brushes in the coating any this nano coating liquid is coated on substrate surface.This base material can comprise stainless steel, glass, pottery, plate sprays paint.This plate that sprays paint comprises the sheet material with polyester, urethane or Resins, epoxy coating.
Embodiment
Nano coating liquid for stainless steel, glass, pottery, the substrate surfaces such as plate that spray paint according to the present invention comprises nano SiO 2 particle, metal-salt, acid and aqueous solvent.Alternatively, this nano coating liquid also comprises tensio-active agent.
In the present invention, have no particular limits for employed nano SiO 2 particle.In concrete example, used median size to be between the 2nm to 75nm, preferably be between the 2nm to 30nm, more preferably be in the nano SiO 2 particle between the 2nm to 10nm.Yet those of ordinary skills will understand, except more than the nano SiO 2 particle that illustrates, also can use the nano SiO 2 particle of other median sizes.In addition, in the present invention, the nano SiO 2 particle with single median size can be used, also the nano SiO 2 particle of being formed by the nano SiO 2 particle of two or more median size can be used.
In addition, the contriver finds, adds metal-salt in the coating fluid that with nano SiO 2 particle and acid is major ingredient, will promote the formed corrosion resistance of coating of this coating fluid significantly.In the present invention, employed metal-salt can be the divalent metal-salt, 3 valency metal-salts, 4 valency metal-salts and their mixture.Wherein, described divalent metal-salt can be nitrate, vitriol, preferably includes strontium nitrate, zinc sulfate, sal epsom, copper sulfate.Described 3 valency metal-salts can be nitrate, muriate, vitriol, preferably include aluminum nitrate, aluminum chloride, potassium aluminium sulfate, cerous nitrate, iron(ic) chloride.Described 4 valency metal-salts can be nitrate, preferably include zirconium nitrate.Described metal salt mixture can be the mixture of aluminum nitrate and cerous nitrate.One skilled in the art will appreciate that above metal-salt only is used for the purpose of example, but not be used for restriction the present invention.In fact, also can use other divalent, 3 valencys, 4 valency metal-salts and their mixture.
In the present invention, employed acid is mineral acid.Concrete, spendable mineral acid comprises phosphoric acid, hydrochloric acid and nitric acid.Content to this mineral acid has no particular limits, as long as it can make the pH value of this nano coating liquid less than 4.One skilled in the art will appreciate that, except acid listed above, can also use other mineral acid.
In the present invention, employed aqueous solvent can be water, water and the mixture of alcohol and the mixture of water and alcohol ether.Yet those skilled in the art will understand equally, also can use the aqueous solvent of the other types except aqueous solvent listed above.
In the present invention, tensio-active agent not necessarily, have only when coating fluid when the substrate surface wetting and spreading is problematic, can solve this problem by selecting the method for adding tensio-active agent for use.Certainly, also can pass through methods such as other known method such as surface corona processing, Cement Composite Treated by Plasma, surface hydrophilic processing, solve coating fluid in the problem of substrate surface wetting and spreading.Operable tensio-active agent can be nonionogenic tenside, anion surfactant, zwitterionics and their mixture.This nonionogenic tenside can be polyoxyethylene-type nonionogenic tenside, polyol-based non-ionic surfactant, alkylol amide type nonionogenic tenside, fluorine carbon type nonionogenic tenside, organosilicon type and modified organic silicon type nonionogenic tenside and their mixture.This anion surfactant can be carboxylic acid type anion surfactant, sulfonate type anion surfactant, sulfuric acid type anion surfactant, phosphate ester salt type anion surfactant and their mixture.This zwitterionics can be amino acid type surfactant, betaine type amphoteric surfactant and their mixture.Equally, those skilled in the art also will understand, can use divided by on list tensio-active agent outside the tensio-active agent that comes.
Embodiment
Below with reference to embodiment the present invention is described, but these embodiment do not limit the scope of the invention.
The raw material of Cai Yonging is as shown in table 1 below in an embodiment.
Embodiment 1
With 36.67 gram Nalco 2326 (15 weight % colloid silica aqueous liquid dispersions, median size 5nm, pH=9, Nalco Company USA) joins in 250 milliliters of vials, adds 132.67 gram deionized waters under magnetic stirrer stirs, drip 0.88 gram strong phosphoric acid (＞85 weight %) then and regulate pH to 2-3, stir adding 25.78 grams 3.2 weight % aluminum nitrate aqueous solutions after 10 minutes, continue to stir 10 minutes, add 4.00 gram Triton again
TM10 weight %BG-10 (DOW Chemical, 70 weight % solution) finally obtain the clarification coating fluid of 2.75 weight % silicon-dioxide solid contents.
Embodiment 2-34
Prepare the coating fluid of embodiment 2-34 with the preparation method identical with embodiment 1, but used metal-salt, nano SiO 2 particle, acid, aqueous solvent may be different.Specifying information sees Table 2.
Comparing embodiment 1
Prepare the coating fluid of comparing embodiment with the preparation method identical with embodiment 1, but this coating fluid metal-containing salt not.Specifying information sees Table 2.
The preparation of stainless steel print:
Coating embodiment 1:
200 grams are poured by the coating fluid of embodiment 1 preparation in the stainless steel tank of 400ml into (15cm * 15cm * 2cm) uses automatic dip coater (SKVDX2S-500) dip-coating stainless steel substrates (5cm * 10cm * 1mm) at room temperature then.Before the stainless steel substrates coating, carry out cleaning surfaces with ethyl acetate, with pressurized air it is dried up afterwards.The dip-coating condition is: immerse speed 100mm/min, Immersion time 1min, pull rate 100mm/min; In baking oven, heat-treat afterwards, baking oven is warmed up to 200 ℃ from 80 ℃, then 200 ℃ of insulations 10 minutes down.See table 3 for details.
Coating embodiment 2-51:
Use the coating process identical with being coated with embodiment 1, but kind is different with dip-coating condition and heat-treat condition.See table 3 for details.It needs to be noted that those skilled in the art expect that easily although with dip-coating method base material is coated with in this manual, roller coat coating, brushing coating also can be adopted.And, the stainless steel that employed base material is listed, glass, the plate that sprays paint, can also comprise pottery in following table.The plate that sprays paint here comprises with the sheet material of polyester, urethane or Resins, epoxy coating (metal sheet, plank, etc.).
Coating comparative example 1:
Use the coating process identical with being coated with embodiment 1, but used coating fluid is the coating fluid of comparative example 1 preparation.See table 3 for details.
According to following testing method, surface hydrophilicity, weather resistance, property easy to clean, preservative property, the high temperature resistant/high wet performance of the nano coating of the present invention for preparing among the embodiment are estimated.
1. surface hydrophilic property testing
The surface hydrophilicity of nano coating characterizes by contact angle, and testing tool is the automatic contact angle tester of Kruss DSA100.The water droplet of 5 μ l is dropped on the test panel of coating nano coating during test, when the shape for the treatment of water droplet does not change, test its contact angle.Three different zones of each sample test, and get its mean value.The value of contact angle is more little, and more hydrophilic surface is described.Test result sees Table 4.
2. wet-milling test
The weather resistance of coating tests to characterize by wet-milling, and testing tool is Sheen Wet Abrasion Scrub Tester REF 903.Test condition is: 1 kilogram of load-carrying, friction materials are that 3M thinks noble and unsullied board rag, and friction media is water.1000 circulations of every friction (circulation refers to back and forth once), whether the range estimation coating fluid peels off, if having, stops test, and the cycle number of record test.If no, then continue test, reach 5000 up to the test loop number, stop test, and record test loop number is 5000.The results are shown in Table 4.
3. performance test easy to clean
The performance test 3.1 deoil
Drip the natural grain mixed oil on the stainless steel plate of coating nano coating, the surface coverage upper glass plates, room temperature was placed 18 hours, washed with water afterwards or dried cloth wiping, saw whether the surface has greasy dirt residual.If no, then be designated as " by "; If have, then be designated as " not passing through ".Test result sees Table 4.
3.2 remove the fingerprint performance test
The grease of face secretion is coated on the stainless steel plate, the surface coverage upper glass plates, room temperature was placed 18 hours, washed with water afterwards or dried cloth wiping, saw whether the surface has greasy dirt residual.If no, then be designated as " by "; If have, then be designated as " not passing through ".Test result sees Table 4.
4. antiseptic property test:
4.1 acid resistance test:
The stainless steel plate of coating nano coating is immersed in the 10 weight % aqueous acetic acids, and room temperature was placed 5 hours.Take out afterwards and clean up with clear water, dry up with pressurized air.Whether the range estimation coating peels off.If peel off, then be designated as " not passing through ", if do not peel off, then be designated as " by ".Test result sees Table 4.
4.2 it is high temperature resistant/the high humidity performance test
The stainless steel plate of coating nano coating was immersed in the boiling water 2 hours, take out afterwards and water cleans up, and dry up with pressurized air.Afterwards with the delta E value of X-Rite 8400 color difference meter testing coatings before and after test.Delta E value is more little, illustrates that the aberration variation before and after this coating test is more little, and the performance of coating withstand high temperatures/high humidity is more good.Test result sees Table 4.
4.3 salt-fog test:
Draw " * " with blade at the stainless steel plate of coating, be put into then that (Q-Fog SF-1600L, Q-Lab, the U.S.) carries out SaltSprayTest in the salt fog cabinet.The SaltSprayTest condition is carried out according to ASTM B117.Took out every 250 hours, clean up the surface with clear water, dry up with pressurized air, whether visual observations edge " * " notching edge has the corrosion above 2mm afterwards, and whether other dispensing area has rust staining, or whether coating peels off.If wherein have any situation to take place, then stop to test and recording total test duration; If no, then proceed test till test reaches 1000 hours total time, and to record total test duration be 1000 hours.Test result sees Table 5.
4.4 the sauce of anti-food test:
With a soy sauce, a tomato-sauce and a hot sauce drop in respectively on the stainless steel plate of coating nano coating, the surface coverage upper glass plates, and room temperature was placed 18 hours, and water cleans up afterwards, and dries up with pressurized air.Whether the range estimation coating peels off.If peel off, then be designated as " not passing through ", if do not peel off, then be designated as " by ".Test result sees Table 6.
The salt spray resistance test result of table 5 coating embodiment
| Coating embodiment numbering | The salt spray resistance test (hour) |
| Coating embodiment 2 | 500 |
| Coating embodiment 4 | 1000 |
| Coating embodiment 7 | 750 |
| Coating embodiment 14 | 500 |
| Coating embodiment 18 | 750 |
| Coating embodiment 19 | 750 |
| Coating embodiment 20 | 750 |
| Coating embodiment 22 | 1000 |
| Coating embodiment 23 | 1000 |
| Coating embodiment 24 | 1000 |
| Coating embodiment 25 | 1000 |
| Coating embodiment 26 | 500 |
| Coating embodiment 27 | 500 |
| Coating embodiment 28 | 500 |
| Coating embodiment 29 | 750 |
| Coating embodiment 30 | 500 |
| Coating embodiment 31 | 1000 |
| Coating embodiment 32 | 1000 |
| Coating embodiment 33 | 1000 |
| Coating embodiment 34 | 1000 |
| Coating embodiment 35 | 500 |
| Coating embodiment 36 | 500 |
| Coating embodiment 37 | 500 |
| Coating embodiment 38 | 500 |
| Coating embodiment 39 | 500 |
| Coating embodiment 43 | 500 |
| Coating embodiment 46 | 500 |
| Coating embodiment 47 | 1000 |
| Coating embodiment 48 | 1000 |
| Coating comparative example 1 | 200 |
The sauce of the anti-food The performance test results of table 6 coating embodiment
| Coating embodiment numbering | Anti-soy sauce test | Anti-hot sauce test | Anti-tomato-sauce test |
| Coating embodiment 1 | By | Do not pass through | Do not pass through |
| Coating embodiment 2 | By | By | By |
| Coating embodiment 3 | By | By | Do not pass through |
| Coating embodiment 4 | By | Do not pass through | Do not pass through |
| Coating embodiment 5 | By | Do not pass through | Do not pass through |
| Coating embodiment 6 | By | By | By |
| Coating embodiment 8 | By | By | By |
| Coating embodiment 9 | By | By | By |
| Coating embodiment 10 | By | By | By |
| Coating embodiment 11 | By | By | By |
| Coating embodiment 12 | By | By | By |
| Coating embodiment 13 | By | By | By |
| Coating embodiment 14 | By | By | Do not pass through |
| Coating embodiment 15 | By | Do not pass through | Do not pass through |
| Coating embodiment 16 | By | Do not pass through | Do not pass through |
| Coating embodiment 17 | By | Do not pass through | Do not pass through |
| Coating embodiment 40 | By | By | ? |
| Coating embodiment 41 | By | Do not pass through | Do not pass through |
| Coating embodiment 42 | By | Do not pass through | Do not pass through |
| Coating embodiment 44 | By | ? | ? |
| Coating embodiment 45 | By | ? | ? |
| Coating embodiment 47 | By | Do not pass through | Do not pass through |
| Coating embodiment 48 | By | Do not pass through | Do not pass through |
| Coating embodiment 49 | By | ? | ? |
| Coating embodiment 50 | By | ? | ? |
| Coating embodiment 51 | By | ? | ? |
| Coating comparative example 1 | Do not pass through | Do not pass through | Do not pass through |
By the test result of above-described embodiment as can be known, if forming the nano oxidized silicon coating that metal-salt of the present invention strengthens such as substrate surfaces such as stainless steel, glass, pottery, the plates that sprays paint, then these base materials will have good performance easy to clean.That is to say that lip-deep oil stain, fingerprint and the food stains etc. of these base materials can be removed rapidly.And, because the nano oxidized silicon coating that this metal-salt strengthens can tolerate salt fog, acid, hot and humid etc. corrosion well, thereby provide permanently effective protection for the surface of these base materials.
Claims (25)
1. nano coating liquid, described nano coating liquid comprises the nano SiO 2 particle of 1-10 weight %, 0.4-2.0 the pH value that the metal-salt of weight %, its content are enough to guarantee described nano coating liquid is less than 4 acid, and the aqueous solvent that total content is added to 100 weight %.
2. nano coating liquid according to claim 1, wherein said nano coating liquid also comprises the tensio-active agent of 0.05-1.0 weight %.
3. nano coating liquid according to claim 1, the median size of wherein said nano SiO 2 particle is between the 2nm to 75nm, preferably is between the 2nm to 30nm, more preferably is between the 2nm to 10nm.
4. nano coating liquid according to claim 3, wherein said nano SiO 2 particle comprises the nano SiO 2 particle of single median size.
5. nano coating liquid according to claim 3, wherein said nano SiO 2 particle comprises the nano SiO 2 particle of two or more median size.
6. nano coating liquid according to claim 1, wherein said metal-salt comprises the divalent metal-salt, 3 valency metal-salts, 4 valency metal-salts and their mixture.
7. nano coating liquid according to claim 6, wherein said divalent metal-salt comprises nitrate, vitriol, preferably includes strontium nitrate, zinc sulfate, sal epsom, copper sulfate.
8. nano coating liquid according to claim 6, wherein said 3 valency metal-salts comprise nitrate, muriate, vitriol, preferably include aluminum nitrate, aluminum chloride, potassium aluminium sulfate, cerous nitrate, iron(ic) chloride.
9. nano coating liquid according to claim 6, wherein said 4 valency metal-salts comprise nitrate, preferably include zirconium nitrate.
10. nano coating liquid according to claim 6, the mixture of wherein said metal-salt comprises the mixture of aluminum nitrate and cerous nitrate.
11. nano coating liquid according to claim 1, wherein said acid is mineral acid, comprises phosphoric acid, hydrochloric acid and nitric acid.
12. nano coating liquid according to claim 1, wherein said aqueous solvent comprise water, water and the mixture of alcohol and the mixture of water and alcohol ether.
13. nano coating liquid according to claim 2, wherein said tensio-active agent comprise nonionogenic tenside, anion surfactant, zwitterionics and their mixture.
14. nano coating liquid according to claim 13, wherein said ionic surfactant pack are drawn together polyoxyethylene-type nonionogenic tenside, polyol-based non-ionic surfactant, alkylol amide type nonionogenic tenside, fluorine carbon type nonionogenic tenside, organosilicon type and modified organic silicon type nonionogenic tenside and their mixture.
15. nano coating liquid according to claim 13, wherein said anion surfactant comprise carboxylic acid type anion surfactant, sulfonate type anion surfactant, sulfuric acid type anion surfactant, phosphate ester salt type anion surfactant and their mixture.
16. nano coating liquid according to claim 13, wherein said zwitterionics comprise amino acid type surfactant, betaine type amphoteric surfactant and their mixture.
17. according to each described nano coating liquid application in base material in the claim 1 to 16.
18. application according to claim 17, wherein said base material comprise stainless steel, glass, pottery, plate sprays paint.
19. application according to claim 18, the wherein said plate that sprays paint comprise the sheet material with polyester, urethane or Resins, epoxy coating.
20. by the nano coating corrosion-resistant and easy to clean that forms at substrate surface according to each described nano coating liquid in the claim 1 to 16.
21. nano coating as claimed in claim 20, wherein said base material comprise stainless steel, glass, pottery, plate sprays paint.
22. nano coating as claimed in claim 21, the wherein said plate that sprays paint comprise the sheet material with polyester, urethane or Resins, epoxy coating.
23. one kind will be coated on the method for substrate surface according to each described nano coating liquid in the claim 1 to 16, this method comprises and adopts dip-coating coating, roller coat coating, brushes in the coating any described nano coating liquid is coated on substrate surface.
24. method as claimed in claim 23, wherein said base material comprise stainless steel, glass, pottery, plate sprays paint.
25. method as claimed in claim 24, the wherein said plate that sprays paint comprise the sheet material with polyester, urethane or Resins, epoxy coating.
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| CN109663727A (en) * | 2018-12-14 | 2019-04-23 | 上海大学 | Metal surface coating method |
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