CN1176169C - Nm-class hydrophilic coating material for aluminium foil and its preparing process - Google Patents
Nm-class hydrophilic coating material for aluminium foil and its preparing process Download PDFInfo
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- CN1176169C CN1176169C CNB01134055XA CN01134055A CN1176169C CN 1176169 C CN1176169 C CN 1176169C CN B01134055X A CNB01134055X A CN B01134055XA CN 01134055 A CN01134055 A CN 01134055A CN 1176169 C CN1176169 C CN 1176169C
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Abstract
The present invention relates to a nanometer hydrophilic coating material for aluminum foils, which is mainly used for aluminum sheets for heat exchange and has the excellent performance of corrosion resistance, the self-lubrication property and the excellent hydrophilicity, and a preparation method thereof. The coating material is composed of a hydrophilic polymer A and hydrophilic nanometer polymer particles B, wherein the hydrophilic polymer A comprises polyether, and the hydrophilic nanometer polymer particles B comprises 5 to 50 wt% of macromolecular surface active agent, 20 to 90 wt% of acrylamide, 10 to 80 wt% of acrylic acid and 1 to 30 wt% of crosslinkable unsaturated monomer; the mass ratio of the hydrophilic polymer A to the hydrophilic nanometer polymer particles B is 1: (9 to 9:1). The nanometer hydrophilic coating material for aluminum foils is obtained by the following steps: according to the weight proportion, adding a water-soluble polymer A and methanol into a proportioning kettle for dissolution at normal temperature; adding deionized water, spirit blue and a sterilizing mildew inhibitor into the kettle for uniform mixing; adding the hydrophilic nanometer polymer particles B and uniformly stirring to obtain the nanometer hydrophilic coating material for aluminum foils.
Description
One, technical field
The present invention relates to a kind of application aluminium foil and prepare nm-class hydrophilic coating material for aluminium foil of hydrophilic aluminium foil and preparation method thereof.More particularly, what the present invention relates to is that a kind of aluminium heat exchanger fin that makes has excellent hydrophilicity (initial contact angle＜5 ° continue hydrophilic angle＜10 °), and has excellent Corrosion Protection, do not have smell, have the nm-class hydrophilic coating material for aluminium foil of self-lubricating ability.
Two, background technology
In recent years, conditioner developed rapidly, and the producer that produces conditioner extensively adopts the aluminium foil fin of small pieces distance, complicated sheet type to obtain good heat exchange effect in heat exchanger, and reaches the purpose of conditioner miniaturization.When the heat exchanger of conditioner is worked, the water of condensation that air produces can form the globule on the fin of heat exchanger, when spacing of fin during less than 2mm, the condensation globule can couple together with the globule on the adjacent fins and form the water bridge, and at present along with the miniaturization development of conditioner, it is more and more little that the spacing between fin requires, even require to reach the spacing of 1.2mm, therefore, water bridge phenomenon is very serious.The generation of water bridge phenomenon causes windage increase, air quantity to descend, thereby influences the thermal property of system, and refrigerating capacity is lowered.In addition, although aluminium and aluminium alloy thereof have good erosion resistance, but the water of condensation on the long-term aluminium surface of being detained absorbs airborne oxygen and sulphur, nitrogen etc., form corrosion cell on the aluminium surface, the generation of meeting accelerated corrosion causes the efflorescence of aluminium foil surface, can cause the pollution of environment after blowing out, particularly in the coastland, this phenomenon is just more serious.
In order to prevent the generation of above-mentioned phenomenon, improve and improve the performance of conditioner, just must carry out hydrophilic and rotproofing to the fin of heat exchanger, also promptly adopt to have hydrophilic rot-resistant aluminium foil and prepare heat exchanger.
The technology of this aspect roughly can be divided into three classes at present: (1) polymkeric substance-nano inorganic material complex class; (2) polymer nano-particle-polymkeric substance complex class; (3) simple polymkeric substance or polymkeric substance and inorganic hydrophilic material complex class.
The preparation method of first kind class hydrophilic coating material for aluminium foil is as follows: at first by 0.1～10 (wt) SiO
2The water-sol and 100 (wt) ethene siloxane reactions obtains composite organic-inorganic material, contains the vinyl monomer polymerization with water miscible then, and last and solidifying agent and the vibrin that contains carboxyl, hydroxyl be compound to obtain final product.The disadvantage of this kind product is that the ethene siloxanes that adopts is expensive especially, and the organic and inorganic composite particles that obtains is bigger, and the hydrophilic angle of the hydrophilic aluminium foil that obtains only reaches 20 °; The preparation method of the second class class hydrophilic coating material for aluminium foil is as follows: with the vinylformic acid polyoxyethylene ether-ester, vinylformic acid, acrylamide and crosslinkable unsaturated monomer carry out polymerization in the propylene glycol monomethyl ether solvent, utilize the surfactivity effect of vinylformic acid polyoxyethylene ether-ester to stablize the gained particle, obtain final product with polyethers is compound then, it is crosslinked to form hydrogen bond during film forming between vinylformic acid and polyethers, polyethers also plays lubricant simultaneously, its shortcoming is that the propionic acid polyoxyethylene ether-ester is somewhat expensive, the particle that obtains simultaneously reaches hundreds of nanometers, be not easy to be deep in the hole of aluminium foil, thereby and aluminium foil between bonding force strong inadequately, need to handle with chromic salt in advance, this in environmental requirement than not allowing higher today; The preparation method of the 3rd class class hydrophilic coating material for aluminium foil is as follows: directly with polyethers and hydrophilic polymer, as: poly-glutamic acid, polyvinylpyrrolidone, water-soluble epoxy resin and aqueous alkide resin etc. are compound to obtain final product, and the problem of this kind method maximum is to be difficult to reduce effectively continue hydrophilic angle.According to the literature, the hydrophilic aluminium foil that the product that this kind method obtains obtains after applying continues hydrophilic angle about 30 degree, is difficult to satisfy the super miniaturization requirement of conditioner.
Three, technology contents
(1) goal of the invention
The purpose of this invention is to provide that a kind of hydrophilic angle is little, pollution-free, cost is low, free from extraneous odour, strong adhesion and have nm-class hydrophilic coating material for aluminium foil of antiseptic property and preparation method thereof.
(2) technical scheme
Coating material of the present invention is by hydrophilic polymer A, hydrophilic nano polymer particle B and other typical additives combine, wherein hydrophilic polymer A comprises polyethers, hydrophilic nano polymer particle B comprises molecules surfactant 5-50% (wt), acrylamide 20-90% (wt), vinylformic acid 10-80% (wt), crosslinkable unsaturated monomer 1-30% (wt), the percentage composition sum of each component is 100% among the nanometer polymer particle B, the mass ratio of hydrophilic polymer A and hydrophilic nano polymer particle B is 1: 9～9: 1, polyethers is Soxylat A 25-7 or polyethenoxy ether or polyoxy butylene ether or its block polymer or for by esterification, the modified polyether that condensation and crosslinking reaction obtain, hydrophilic polymer A also comprises polyvinylpyrrolidone and other hydrophilic polymer, the composition by weight of hydrophilic polymer A is a polyethers 69～99%, polyvinyl alcohol 0.1～30%, polyvinylpyrrolidone 0.1～30%, other hydrophilic polymer 0.1～30%, other hydrophilic polymer comprises carboxymethyl cellulose, water-soluble epoxy resin, polyvinyl alcohol, molecules surfactant is a polymer-type efficient petroleum crude oil emulsion splitter, the crosslinkable unsaturated monomer is a hydroxy methyl methacrylate, or hydroxyethyl methylacrylate or glytidyl methacrylate or divinylbenzene and butadiene type contain the monomer of two two keys or two other functional groups of key, also comprise other monomer 0.1～40% (wt) among the hydrophilic nano polymer particle B, be vinyl acetate or vinylbenzene or methyl methacrylate or methyl acrylate or ethyl propenoate class monomer, calculate by weight water-soluble polymers A and methyl alcohol joined in the batching still and add deionized water behind the normal-temperature dissolution, spirit blue, biocide mildewcide, even back adding hydrophilic nano polymer particle B is mixed, promptly obtain nm-class hydrophilic coating material for aluminium foil after restir is even, the preparation method of water-soluble polymers A is for joining 50 parts of ethylene glycol and potassium hydroxide in the reactor, with nitrogen replacement and vacuumizing, warming while stirring to 125 then ± 10 ℃ feed oxyethane again, keep still internal pressure 0.25Mpa, keep temperature in the reaction pressure still after 1 hour the still internal pressure reduce to 0.1Mpa and be evacuated to 0.08Mpa and keep 0.5h, obtaining polyethers is waterborne polymeric A, the preparation method of hydrophilic polymer particles B is: (1) is with vinylformic acid, acrylamide, glytidyl methacrylate, molecules surfactant, ethylene glycol monomethyl ether joins carries out emulsification in the emulsion tank, obtain emulsified monomer; (2) Ammonium Persulfate 98.5 initiator and deionized water are joined in the dissolving vessel, stirring at normal temperature makes initiator fully dissolve the aqueous solution that obtains initiator; (3) emulsified monomer, molecules surfactant, initiator solution, ethylene glycol monomethyl ether are joined be warming up to 80 ℃ in the polymeric kettle and carry out polymerization, finally obtain the hydrophilic nano polymer particle.
(3) technique effect
The present invention has that hydrophilic angle is little, pollution-free, cost is low, free from extraneous odour, strong adhesion and antiseptic property is arranged.Concrete testing method is:
1. the wetting ability of hydrophilic layer adopts water droplet to represent at the contact angle of coatingsurface, and the JC2000A type interfacial tension contact angle measurement of marine numeral company limited production in morning is tested in the employing.
2. under room temperature environment, it is 15kg/m that sample is fixed in discharge
2In the flowing water of h, take out behind the dipping 8h and place 80 ℃ baking oven then, dry 16h more than is 1 flowing water cycle, repeats 4 times, and the hydrophilic angle that measures at last is and continues hydrophilic angle.
3. antiseptic property adopts salt mist experiment to determine that it is definite to experimentize by GB5944-86.
4. the sticking power experimental technique is as follows: with the monolithic cutter on the coating of sample is to mark 11 anyhow at interval with 1mm, make 100 little lattice, firmly press earlier adhesive tape in drawing the lattice position then, then firmly pull back, make adhesive tape from the hydrophilic layer surfacial spalling, the range estimation hydrophilic layer has or not and comes off, each little lattice hydrophilic layer keep less than 70% be considered as come off.
5. the odor detection of hydrophilic layer directly adopts the sense of smell check.
1, The performance test results:
A initial contact angle＜5 °;
B continues contact angle＜10 °;
C water scholar; Complete, no condensation of moisture film and demixing phenomenon;
D erosion resistance: corrosion class 〉=6 grade;
E adhesion property: expulsion rate≤5%;
G coating smell: free from extraneous odour
Four, embodiment
Water-soluble polymers A: comprising polyethers 70～100% (wt); Polyvinyl alcohol 0～30% (wt); Polyvinylpyrrolidone 0～30% (wt); Other hydrophilic polymer 0～30% (wt).Hydrophilic nano polymer particle B: its component comprises: (1) molecules surfactant 5～50% (wt); (2) acrylamide 20～90% (wt); (3) vinylformic acid 10～80% (wt); (4) crosslinkable unsaturated monomer 1～30 (wt); (5) other monomer 0～40% (wt) beyond the above-mentioned monomer;
(a) polyethers in the water-soluble polymers can be Soxylat A 25-7, polyethenoxy ether, polyoxy butylene ether or its segmented copolymer, can also be the modified polyether that obtains by esterification, condensation and crosslinking reaction; The molecular weight of polyvinyl alcohol and polyvinylpyrrolidone is in 500～50000 scope: other hydrophilic polymer comprises carboxymethyl cellulose and water-soluble epoxy resin;
(b) molecules surfactant adopts is the polymer-type efficient petroleum crude oil emulsion splitter that provides among we the patent CN01113543.3 that applied for;
(c) Acrylic Acid Monomer is meant the monomer of vinylformic acid and methacrylic or the monomer of acrylamide and n-methylolacrylamide class;
(d) crosslinkable unsaturated monomer comprises: hydroxy methyl methacrylate, hydroxyethyl methylacrylate, glytidyl methacrylate, divinylbenzene and butadiene type contain the monomer of two two keys or two other functional groups of key;
(e) other monomer is meant vinyl acetate, vinylbenzene, methyl methacrylate, methyl acrylate and ethyl propenoate class monomer;
What (f) preparation of hydrophilic nano polymer particle was adopted is emulsion polymerization, initiator is ammonium persulphate, the water miscible initiator of Potassium Persulphate class, its add-on is 0.1～5% (wt), and solvent is the solvent of water, methyl alcohol, ethanol, propylene glycol butyl ether class, design solid content 10～50%;
(g) mass ratio of A and B (by solid content) is 1: 9～9: 1;
(h) if necessary, the component of nm-class hydrophilic coating material for aluminium foil can also comprise linking agent, sterilant, mould resistant and pigment, its add-on 0～30%.
The present invention will further be described in detail by following example.
The preparation of hydrophilic polymer A
Ethylene glycol 50 parts (wt) and potassium hydroxide 4.2 parts (wt) join in the reactor, with nitrogen replacement and vacuumizing 3 times, warming while stirring to 125 then ± 10 ℃, feed 1320 parts in oxyethane (wt) then, keep below the still internal pressure 0.25Mpa, after oxyethane feeds in raw material and finishes, continue to keep this thermotonus 1h and reduce to 0.1Mpa to the still internal pressure, vacuumize 0.085Mpa then, and keep 0.5h, its product is that required polyethers is water-soluble polymers A.
The preparation of hydrophilic nano polymer particle B
(1) 6 parts of (wt) vinylformic acid, 12 parts of (wt) acryloyl ammoniums, 4 parts of (wt) glytidyl methacrylate, 4 parts of (wt) macromole surface washing agents, 40 parts of (wt) ethylene glycol monomethyl ether are joined and carry out emulsification among the emulsion tank B, obtain emulsified monomer;
(2) 0.5 part of (wt) ammonium persulfate initiator and 10 parts of (wt) deionized waters are joined in the dissolving vessel, stirring at normal temperature makes initiator fully dissolve the aqueous solution that obtains initiator;
(3) 6 parts of (wt) emulsified monomers, 4 parts of (wt) molecules surfactants, 4 parts of (wt) initiator solutions, 50 parts of (wt) ethylene glycol monomethyl ether are joined in the polymeric kettle, be warming up to 80 ℃ and carry out polymerization.Replenish 1 part of (wt) initiator solution every 1.5h, emulsified monomer added in 12 hours, and after being added dropwise to complete, insulation reaction 6h obtains final hydrophilic nano polymer particle again.
The nano-hydrophilic aluminium foil covers the preparation of material slowly
35 parts of (wt) methyl alcohol of 30 parts of (wt) hydrophilic polymers are joined in the batching still behind the normal-temperature dissolution, add 360 parts of (wt) deionized waters, add 20 parts of 5 parts of (wt) spirit blues and biocide mildewcides (wt) again, mix the back and add 30 parts of (wt) hydrophilic nano polymer particles, promptly obtain the final nano-hydrophilic paper tinsel coating material product of solid content 10% after restir is even.
The coating method of nm-class hydrophilic coating material for aluminium foil is as follows: at first with trieline, gasoline kind solvent aluminium foil is washed degreasing, use acid and/or alkali degreasing then, it is dry down at 100 ℃ to clean the back with flowing water, adopt dipping or roller coating class methods to carry out application then, keep 5s～5min can obtain final hydrophilic aluminium foil down at 100～250 ℃.
Claims (8)
1, a kind of nm-class hydrophilic coating material for aluminium foil, it is characterized in that this coating material is by hydrophilic polymer A, hydrophilic nano polymer particle B and other typical additives combine, wherein hydrophilic polymer A comprises polyethers, hydrophilic nano polymer particle B comprises molecules surfactant 5-50% (wt), acrylamide 20-90% (wt), vinylformic acid 10-70% (wt), crosslinkable unsaturated monomer 1-30% (wt), the percentage composition sum of each component is 100% among the nanometer polymer particle B, and the mass ratio of hydrophilic polymer A and hydrophilic nano polymer particle B is 1: 9～9: 1; Polyethers is Soxylat A 25-7 or polyethenoxy ether or polyoxy butylene ether or its block polymer or the modified polyether for obtaining by esterification, condensation and crosslinking reaction; The crosslinkable unsaturated monomer is the monomer that hydroxy methyl methacrylate or hydroxyethyl methylacrylate or glytidyl methacrylate or divinylbenzene and butadiene type contain two two keys or two other functional groups of key.
2, nm-class hydrophilic coating material for aluminium foil according to claim 1, it is characterized in that hydrophilic polymer A also comprises polyvinylpyrrolidone and other hydrophilic polymer, the composition by weight of hydrophilic polymer A is polyethers 69～99%, polyvinyl alcohol 0.1～30%, polyvinylpyrrolidone 0.1～30%, other hydrophilic polymer 0.1～30%.
3, nm-class hydrophilic coating material for aluminium foil according to claim 2 is characterized in that other hydrophilic polymer comprises carboxymethyl cellulose, water-soluble epoxy resin, polyvinyl alcohol.
4, nano-hydrophilic coating material for aluminium foil according to claim 1 is characterized in that molecules surfactant is a polymer-type efficient petroleum crude oil emulsion splitter.
5, nm-class hydrophilic coating material for aluminium foil according to claim 1, it is characterized in that also comprising among the hydrophilic nano polymer particle B other monomer 0.1～40% (wt), be vinyl acetate or vinylbenzene or methyl methacrylate or methyl acrylate or ethyl propenoate class monomer.
6, a kind of preparation method of nm-class hydrophilic coating material for aluminium foil as claimed in claim 1, it is characterized in that calculating by weight water-soluble polymers A and methyl alcohol joined in the batching still and add deionized water, spirit blue, biocide mildewcide behind the normal-temperature dissolution, be mixed and spare back adding hydrophilic nano polymer particle B, promptly obtain nm-class hydrophilic coating material for aluminium foil after restir is even.
7, the preparation method of nm-class hydrophilic coating material for aluminium foil according to claim 6, the preparation method who it is characterized in that water-soluble polymers A is for joining 50 parts of ethylene glycol and potassium hydroxide in the reactor, with nitrogen replacement and vacuumizing, warming while stirring to 125 then ± 10 ℃ feed oxyethane again, keep still internal pressure 0.25Mpa, keep temperature in the reaction pressure still after 1 hour the still internal pressure reduce to 0.1Mpa and be evacuated to 0.08Mpa and keep 0.5h, obtaining polyethers is waterborne polymeric A.
8, the preparation method of nm-class hydrophilic coating material for aluminium foil according to claim 6 is characterized in that the preparation method of hydrophilic polymer particles B is:
(1) with vinylformic acid, acrylamide, glytidyl methacrylate, molecules surfactant, ethylene glycol monomethyl ether joins carries out emulsification in the emulsion tank, obtain emulsified monomer;
(2) Ammonium Persulfate 98.5 initiator and deionized water are joined in the dissolving vessel, stirring at normal temperature makes initiator fully dissolve the aqueous solution that obtains initiator;
(3) emulsified monomer, molecules surfactant, initiator solution, ethylene glycol monomethyl ether are joined be warming up to 80 ℃ in the polymeric kettle and carry out polymerization, finally obtain the hydrophilic nano polymer particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01134055XA CN1176169C (en) | 2001-10-18 | 2001-10-18 | Nm-class hydrophilic coating material for aluminium foil and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01134055XA CN1176169C (en) | 2001-10-18 | 2001-10-18 | Nm-class hydrophilic coating material for aluminium foil and its preparing process |
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| CN1176169C true CN1176169C (en) | 2004-11-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4464076B2 (en) * | 2003-06-09 | 2010-05-19 | 日本ペイント株式会社 | Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film |
| CN100999640B (en) * | 2006-12-19 | 2010-06-23 | 乳源瑶族自治县阳之光亲水箔有限公司 | Non-solvent type aluminum foil coating for air conditioner |
| JP5995546B2 (en) * | 2012-06-19 | 2016-09-21 | 日本ペイント・サーフケミカルズ株式会社 | Method for coating hydrophilic film of aluminum fin material, aluminum fin material, and aluminum heat exchanger |
| CN102876200B (en) * | 2012-11-05 | 2015-06-10 | 江苏科技大学 | Hydrophilic aluminum foil coating and method for preparing and curing same |
| CN105273144A (en) * | 2014-06-18 | 2016-01-27 | 上海丰野表面处理剂有限公司 | Pollution-resistant hydrophilic aluminium foil coating and preparation method and application method thereof |
| CN109439094A (en) * | 2018-09-12 | 2019-03-08 | 安徽康瑞高科新材料技术工程有限公司 | A kind of method that hydrocolloid particle prepares pollution resistance hydrophilic coating |
| CN111410898A (en) * | 2020-04-21 | 2020-07-14 | 哈尔滨鑫科纳米科技发展有限公司 | Rare metal heat-dissipation anticorrosive paint for L ED heat-dissipation fins and preparation method thereof |
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