CN104776750A - Metal plate coated by resin and heat exchanger fin material comprising same - Google Patents
Metal plate coated by resin and heat exchanger fin material comprising same Download PDFInfo
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- CN104776750A CN104776750A CN201410806757.XA CN201410806757A CN104776750A CN 104776750 A CN104776750 A CN 104776750A CN 201410806757 A CN201410806757 A CN 201410806757A CN 104776750 A CN104776750 A CN 104776750A
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Abstract
The invention provides a metal plate coated by resin, and the metal plate can maintain excellent hydrophilicity for a long time. The metal plate coated by resin is characterized in that a resin coating coats the surface of the metal plate to form the metal plate coated by resin, the resin coating is obtained by a composition for forming the resin coating, and the composition comprises (A) a grafted polymer obtained by graft polymerization of vinyl pyrrolidone onto polyvinyl alcohol, (B) an anionic polymer employing at least one of sulfonic acid (sulphonate) and carboxylic acid (carboxylate) as the polymerization component, and (C) a cross-linking agent of at least one of the above grafted polymer and the anionic polymer.
Description
Technical field
The present invention relates to the resin-coated metal sheet of the resin-coated layer being formed with hydrophily excellence on the surface of metallic plate.In addition, the present invention relates to the heat exchanger fin material continuing the surface texture that dew etc. easily soaks chronically.
Background technology
In the heat exchanger of air conditioner, from the aspect that thermal conductivity, processability, corrosion resistance etc. are excellent, widely use aluminium, in order to effectively carry out heat exchange, in addition, in order to suppress compact by space, the structure that aluminum fin material is set with narrow spacing parallel arranging is become.Therefore, when the running of air conditioner, if the temperature of wing sheet surface reaches below the dew point of air, be then attached to the dew condensation of wing sheet surface, sometimes make the fin that adjoins inaccessible to each other.Now, when the hydrophily on aluminum fin material surface is low, owing to becoming greatly with the contact angle of water, so accompanying dew becomes hemispherical, the blocked state of fin is worsened further.Consequently, the known heat exchange function that causes is hindered all the time, or makes dew disperse to problems such as air conditioner are outer because of blast.
In order to improve above-mentioned condensation water problem, develop by carrying out hydrophilicity-imparting treatment to the surface of aluminium sheet self, thus when being processed into fin material and using, dew can not rest on fin surface and easily be removed the technology of discharge.Such as Patent Document 1 discloses synthetic silica and water paint and technology.
But, if use synthetic silica, because obtained film is hardening, so there is the problem that the wearing and tearing of instrument, mould etc. are violent when the formed machining of fin material.In addition, also have that the cement of silica uniqueness is smelly or dust is smelly, infer that resulting from the foul smell dispersed of absorption material on silica or silicon dioxide microparticle causes the problem of sense of discomfort to human body.Therefore, such as Patent Document 2 discloses use alumina sol to replace the high-hydrophilic coating of silica.With regard to this technology, although alleviate and still observe foul smell compared with during application silica, and if use for a long time, foul smell increases gradually, so from suppressing the aspect of foul smell also insufficient.
On the other hand, Patent Document 3 discloses to suppress the dew being attached to wing sheet surface to be detained for a long time and bring out hydration reaction, corrosion reaction, using the technology using the salt of carboxymethyl cellulose and N hydroxymethyl acrylamide as the surface conditioning agent of principal component.In addition, Patent Document 4 discloses to give corrosion resistance and hydrophily to fin material, it is effective for using using polyvinyl alcohol and PVP as the surface conditioning agent of principal component.In the technology of patent document 3,4, owing to not using silica etc., so the problem that the wearing and tearing of foul smell, mould can not be caused such.
But, if the hydrophilic resin epithelium of organic system contacts with water for a long time, then due to epithelium stripping at leisure, thus exist hydrophily through time the problem that reduces.Therefore, be difficult to the hydrophily maintaining wing sheet surface chronically, there is room for improvement.
In addition, Patent Document 5 discloses and use the polymer obtained by glycerol polymerization vinyl pyrrolidone on polyvinyl alcohol and the composition formed as the blocked isocyanates of crosslinking agent as metal conditioner, by said composition being applied to the surface of metal material, good hydrophily can be obtained.
Even if the metallic plate recorded in above-mentioned patent document 5 is repeatedly flooding with dry (following repeatedly, also referred to as repeatedly flooding) when, also the stripping of epithelium can be suppressed, substantially do not have the contact angle relative to water of metallic plate (following yet, be called water contact angle) change, for this water contact angle value, the present application persons have carried out supplementary test, result is known, from initial stage, substantially exceed 40 ° and remain high, in any case so can not say satisfied with the water-wet behavior needed for heat exchanger fin material, room for improvement is still very large.
Prior art document
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 55-164264 publication
Patent document 2: Japanese Unexamined Patent Publication 10-168381 publication
Patent document 3: Japanese Unexamined Patent Publication 2-258874 publication
Patent document 4: Japanese Unexamined Patent Publication 5-302042 publication
Patent document 5: Japanese Unexamined Patent Publication 2009-108111 publication
Summary of the invention
Invent problem to be solved
In the present invention, also contemplate obviousization due to global warming, the surging problem of resource etc., cause the requirement of the performance improvements such as the high efficiency of air conditioner, miniaturization improving, its problem is to provide the heat exchanger fin material that can maintain excellent hydrophilic resin-coated metal sheet chronically and use it.
For solving the scheme of problem
The present invention is the resin-coated metal sheet of the surface-coated resin-coated layer at metallic plate, it is characterized in that, above-mentioned resin-coated layer is formed by resin-coated layer and obtains with composition, described resin-coated layer formation composition comprises: glycerol polymerization vinyl pyrrolidone on polyvinyl alcohol and the graft polymers (A) obtained, comprise the anionic polymer (B) of at least one in sulfonic acid (salt) and carboxylic acid (salt) as polymeric composition, and the crosslinking agent (C) of at least one in above-mentioned graft polymers and above-mentioned anionic polymer.
Above-mentioned resin combination preferably comprises more than a kind in the group being selected from and being made up of polyvinyl alcohol, PVP, carboxymethyl cellulose salt, methylcellulose, hydroxypropyl cellulose, alginate, polyethylene glycol, polyacrylamide and their modifier further.
Above-mentioned metallic plate is preferably aluminium sheet or aluminium alloy plate.
In addition, in the present invention, the heat exchanger fin material be made up of above-mentioned resin-coated metal sheet is also comprised.
Invention effect
Resin-coated metal sheet of the present invention can maintain the hydrophily on surface chronically.In addition, by using the heat exchanger fin material that is made up of resin-coated metal sheet of the present invention, the unfavorable conditions such as the fin material obturation to each other caused because of dew can be reduced, the heat exchanger that effectively can carry out heat exchange can be provided.
Detailed description of the invention
Resin-coated metal sheet of the present invention is that the resin-coated layer formation composition that the surface of metallic plate is prescribed is coated to.
[metallic plate]
The metal plate used in resin-coated metal sheet of the present invention is as listed aluminium sheet, aluminium alloy plate, steel plate, steel plating plate, copper coin, titanium plate etc.In them, preferred aluminium sheet or aluminium alloy plate, from the aspect of thermal conductivity and excellent in workability, use 1000 aluminium being specified in JIS H4000, preferred alloy is numbered the aluminium of 1200.Thickness of slab is preferably about 0.08 ~ 0.3mm.
[resin-coated layer formation composition]
The graft polymers (A) that resin-coated layer formation composition (hereinafter referred to as resin combination) is included in glycerol polymerization vinyl pyrrolidone on polyvinyl alcohol and obtains, comprise the crosslinking agent (C) of at least one in sulfonic acid (salt) and carboxylic acid (salt) as at least one in the anionic polymer (B) of polymeric composition and above-mentioned graft polymers and above-mentioned anionic polymer.
The water soluble polymer that glycerol polymerization vinyl pyrrolidone (NVP) on polyvinyl alcohol and the graft polymers (hereinafter referred to as graft polymers (A)) obtained are nonionic.
Above-mentioned graft polymers (A) if manufacture be suitable for known technology, on the books in such as patent document 5 (Japanese Unexamined Patent Publication 2009-108111 publication).
Polyvinyl alcohol preferred degree of polymerization for the manufacture of above-mentioned graft polymers (A) is 100 ~ 4000, is more preferably 100 ~ 3000.If the degree of polymerization is lower than 100, then likely the intensity of resin-coated layer becomes insufficient, if more than 4000, then becomes high viscosity, and likely operability reduces.
The saponification degree of polyvinyl alcohol is preferably 70 ~ 100mol%.If saponification degree is lower than 70mol%, then the weakened of likely resin-coated layer.
The K value of graft polymers is preferably 12 ~ 150.So-called K value is the constant of the expression degree of polymerization proposed by the change scholar Fikentscher of Germany, if K value is lower than 12, then the weakened of resin-coated layer, if more than 150, then becomes high viscosity, and likely operability reduces.
Amount for the manufacture of the vinyl pyrrolidone of above-mentioned graft polymers (A) is preferably 5 ~ 900 quality % relative to polyvinyl alcohol.If lower than 5 quality %, then can not get sufficient hydrophily, if more than 900 quality %, then likely the intensity of resin-coated layer reduces.
Such as can by polymer reactor as the graft polymers of main chain and above-mentioned graft polymers (A) using polyvinyl alcohol, in poly-vinyl alcohol solution, coordinate vinyl pyrrolidone, use the manufacture method of known radical polymerization initiator glycerol polymerization vinyl pyrrolidone on polyvinyl alcohol chain and obtain.
As polymerization initiator, the hydrogen peroxide, organic peroxide, azo series initiators etc. that are generally used for radical polymerization can be used.As the example of organic peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide etc. can be listed.As azo-compound, can 2 be listed, 2 '-azobis isobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile) etc.As long as reaction method and reaction condition are selected according to the example of general radical polymerization.
Comprise the water soluble polymer that at least one in sulfonic acid (salt) and carboxylic acid (salt) is anionic property as the anionic polymer (B) (hereinafter also referred to as anionic polymer (B)) of polymeric composition.In addition, so-called sulfonic acid (salt) is sulfonic acid or its salt, and so-called carboxylic acid (salt) is carboxylic acid or its salt.
As sulfonic acid (salt), include, for example out the 3-allyloxy-2-hydroxyl-1-propane sulfonic acid or its salt etc. recorded in allyl sulphonic acid or its salt, methylpropenyl sulfonic acid or its salt, vinyl sulfonic acid or its salt, 2-acrylamide-2-methyl propane sulfonic or its salt, Japanese Unexamined Patent Publication 2012-122052 publication.
As carboxylic acid (salt), include, for example out (methyl) acrylic acid or its alkali metal salt, itaconic acid or its alkali metal salt etc.
Above-mentioned anionic polymer (B) can be by the a kind of polymer formed be selected from sulfonic acid (salt) or carboxylic acid (salt), also can be selected from the copolymer of more than two kinds in sulfonic acid (salt) and carboxylic acid (salt), can also be their modifier.Above-mentioned anionic polymer (B) is preferably the copolymer of sulfonic acid (salt) and (methyl) acrylic acid (salt).
Above-mentioned graft polymers (A) is counted (A) with quality ratio with the preferred compounding ratio of above-mentioned anionic polymer (B): (B)=10: 90 ~ 90: 10.Due to above-mentioned graft polymers (A) compared with above-mentioned anionic polymer (B) too much and become outside above-mentioned scope time, although because the increase amplitude of repeatedly flooding caused water contact angle is little, likely the water contact angle at initial stage becomes large.In addition, due to above-mentioned anionic polymer (B) compared with above-mentioned graft polymers (A) too much and become outside above-mentioned scope time, although the water contact angle at initial stage is little, likely cause water contact angle to increase because repeatedly flooding.
Crosslinking agent as at least one in above-mentioned graft polymers and above-mentioned anionic polymer is (following, be called crosslinking agent (C)), as long as the compound that the hydroxyl of the polyvinyl alcohol part in above-mentioned graft polymers (A) can be carried out each other being cross-linked, the compound that the carboxyl of the carboxylic moiety in above-mentioned anionic polymer (B) can be carried out being cross-linked, the compound of association body (ion complexation body) that maybe can form above-mentioned anionic polymer (B).By using above-mentioned crosslinking agent (C) to be cross-linked, the resistance to water of resin-coated metal sheet can be improved.
As the crosslinking agent that the hydroxyl of the polyvinyl alcohol part in above-mentioned graft polymers (A) can be carried out each other being cross-linked, the boric acid based compounds such as glycidyl ether compound, isocyanate compound, melamine compound, aldehyde compound, butane tetracarboxylic acid dianhydride, the amines with multiple functional group, boric acid borax can be listed, there is the metal alkoxide etc. of the one kind or two or more metallic element be selected from Ti, Zr, Al.As the crosslinking agent that the carboxyl of the carboxylic moiety in above-mentioned anionic polymer (B) can be carried out being cross-linked, glycidyl ether compound, isocyanate compound can be listed, there is the amines, oxazoline compound, carbodiimide compound etc. of multiple functional group.And then, as the crosslinking agent of polyion complexing body can be formed with above-mentioned anionic polymer (B), can the polycationic compounds such as chitosan compound be listed.As the preferred crosslinking agent (C) that can embody lower water contact angle, be preferably suitable for glycidyl ether compound Huo oxazoline compound etc.
The preferred compounding ratio of above-mentioned crosslinking agent (C) is 5 ~ 50 mass parts relative to above-mentioned graft polymers (A) and total 100 mass parts of above-mentioned anionic polymer (B), is more preferably 10 ~ 40 mass parts.If lower than 5 mass parts, then can not get sufficient resistance to water, the likely resin-coated layer more stripping when flooding, if more than 50 mass parts, then hydrophily reduces sometimes.
Possess by comprising above-mentioned (A) ~ (C) though the resin-coated layer resin-coated metal sheet that forms the resin-coated layer obtained with composition after repeatedly flooding, also can maintain low water contact angle, in addition, even when being submerged chronically, the stripping of resin-coated layer also can be suppressed.As its reason, even if although infer the slightly high but stripping that is resin-coated layer after repeatedly flooding of the water contact angle at initial stage also less and the cross-linking agent of the above-mentioned graft polymers (A) of excellent in te pins of durability is effective with the water contact angle for the initial stage of reduction, but due to cause stripping of resin-coated layer etc. because repeatedly flooding and easily produce through time deterioration the cross-linking agent of above-mentioned anionic polymer (B) mutually wrapped around one another, form the form close to IPN (Interpenetrating Polymer Network: interpenetrating polymer network) structure.
In addition, above-mentioned resin combination preferably comprises more than a kind in the group (hereinafter referred to as (D)) being selected from and being made up of polyvinyl alcohol, PVP, carboxymethyl cellulose salt, methylcellulose, hydroxypropyl cellulose, alginate, polyethylene glycol, polyacrylamide and their modifier further.
By comprising more than a kind that is selected from above-mentioned (D) in above-mentioned resin combination further, thus in the resin-coated metal sheet being coated with this resin combination, water contact angle can not excessively increase and hydrophily excessively reduces, and in addition, easily forms the epithelium of homogeneous when application.And then, above-mentioned (D) is compared with above-mentioned graft polymers (A), the unit price of raw material is cheap, so when use comprises the resin-coated layer formation composition of above-mentioned (A) ~ (D), compared with the resin-coated layer formation composition only comprising above-mentioned (A) ~ (C) with use, coating cost can be reduced.The addition of above-mentioned (D) is preferably set to below 50 mass parts relative to above-mentioned graft polymers (A) and total quality 100 mass parts of above-mentioned anionic polymer (B).If more than 50 mass parts, then when being submerged chronically, likely resin-coated layer stripping, corrosion resistance reduce.
In addition, in resin-coated metal sheet of the present invention, can also arrange between resin-coated layer and metallic plate and improve corrosion proof anti-corrosion skin membrane.When resin-coated metal sheet of the present invention is used as heat exchanger fin material, by the formation of anti-corrosion skin membrane, because the corrosion resistance of fin material improves further, so the durability of heat exchanger can be improved.In addition, by making anti-corrosion skin membrane become hydrophobicity, can suppress to produce foul smell because being coated with underfilm corrosion in water permeation to resin-coated layer.In anti-corrosion skin membrane, known coating resin can be used, polyester based resin, polyolefin-based resins, epoxy system resin, carbamate system resin, acrylic resin etc. can be used.These resins also can be cross-linked by crosslinking agent.Such as, when polyester based resin, can be cross-linked with melamine series crosslinking agent that can be crosslinked with hydroxyl.
And then, in order to further improve corrosion resistance, the inorganic oxide process such as the process of chromium phosphate hydrochlorate, the process of application type zirconium can also be implemented to metallic plate, utilizing the known chemical conversion treatment such as the process of organic-inorganic composite compound.If these process are before the anti-corrosion skin membrane of formation or do not have stacked anti-corrosion skin membrane, then carried out before the resin combination containing above-mentioned (A) ~ (D) being layed onto on metallic plate.
As long as the solvent of each component dissolves that the solvent used in resin combination of the present invention can make resin combination of the present invention contain or dispersion, be then not particularly limited, preferably mainly use water.
In addition, in resin combination of the present invention, in the scope not hindering performance of the present invention, in order to improve coating or operability, Physical properties of coating film etc., also can be used together various coating additive, such as, also the cosolvent such as alcohols, glycol ethers or surfactant, surface conditioner, crosslinking agent, defoamer, levelling agent, rheology control agent, antiseptic, other mould inhibitors etc. can be used arbitrarily.
[resin-coated layer]
Resin combination is 0.1 ~ 10g/m at the preferred every metallic plate one side of the adhesion amount (amount of coating) of metal sheet surface
2.If adhesion amount is lower than 0.1g/m
2, then not only likely do not embody sufficient hydrophily, and likely moistening corrosion resistance worsens.Moistening corrosion resistance is evaluated by evaluation method described later.In addition, if adhesion amount is more than 10g/m
2, then because resin-coated layer becomes heat insulation layer, so likely heat transfer property reduces, and then also high cost is become economically.The preferred every metallic plate one side of adhesion amount of resin combination is 0.2 ~ 3.0g/m
2, preferably every metallic plate one side is 0.3 ~ 2.0g/m further
2.
[manufacture method of resin-coated metal sheet]
The manufacture method of resin-coated metal sheet of the present invention is not particularly limited, and such as, by the metallic plate application roller coat machine etc. to web-like, heats, can form resin-coated layer thus after resin combination being applied to the surface of metallic plate.In addition, also on the metallic plate being formed with above-mentioned anti-corrosion skin membrane, resin-coated layer can similarly be formed.
[heat exchanger fin material]
Resin-coated metal sheet of the present invention can use as heat exchanger fin material.The heat exchanger fin material water contact angle be made up of resin-coated metal sheet of the present invention is little, even if contact with water for a long time, also can suppress the increase of water contact angle.Therefore, in the heat exchanger using the heat exchanger fin material be made up of resin-coated metal sheet of the present invention to manufacture, dew is present in wing sheet surface with the state of little water contact angle.Afterwards, by being removed under gravity current, even if so use chronically, also not easily cause the reduction of the increase of flowing resistance or the heat exchange property with it.
Embodiment
By the following examples the present invention is described in detail further, but following embodiment does not limit the present invention, change without departing from the spirit and scope of the invention and implement all to comprise in the present invention.
Below, " % " expression " quality % ", " part " expression " mass parts ".
[manufacture method for examination material]
By known manufacture method, manufacture the aluminium sheet (thickness of slab is 0.10mm) formed by the A1200 of fine aluminium system (JIS H4000).This aluminium sheet alkaline reagent (Nippon Paint Co., Ltd. system " Surfcleaner (registration mark) 360 ") is carried out degreasing, carries out the process of chromium phosphate hydrochlorate.The adhesion amount of chemical conversion treatment epithelium converts by Cr and is set to 30mg/m
2.
[manufacture method of aluminum fin material]
Resin combination is prepared with the mass ratio shown in table 1 and table 2, on the aluminium sheet utilizing bar coater to be applied to after the process of above-mentioned chromium phosphate hydrochlorate according to the mode reaching the adhesion amount shown in table 3 6% aqueous solution of this resin combination, use hot-air drying stove to carry out heat drying at highest threshold temperature 220 DEG C, manufacture aluminum fin material.Highest threshold temperature is confirmed by heat sealing adhesive tape.Table 1 and each composition shown in table 2 obtain following material to use, or are manufactured by the manufacture method of following record.
A1: polyvinyl alcohol-Polyvinylpyrrolidone graft copolymer: according to Japanese Unexamined Patent Publication 2009-108111 publication: PVA/PVP mass ratio=50/50:PVA degree of polymerization 1700: fully saponified type
The salt of B1:3-allyloxy-2-hydroxyl-1-propane sulfonic acid (HAPS) and acrylic acid copolymer: according to Japanese Unexamined Patent Publication 2012-122052 publication: Mw=182000:HAPS ratio 25%
B2: acrylic acid-sulfonic acid copolymer: Aron (registration mark) A-6012: Toagosei Co., Ltd's system
B3: the acrylic resin 1 containing sulfonic acid functional group: manufacture method describes later
B4: the acrylic resin 2 containing sulfonic acid functional group: manufacture method describes later
C1: polyfunctional glycidyl ether: Denacol (registration mark) EX-614B:Nagase ChemtexCorporation system
C2: blocked isocyanates: Elastron (registration mark) H-38: Di-ichi Kogyo Seiyaku Co., Ltd.'s system
C3: melmac: Nikalac (registration mark) M-035:Sanwa Chemical Co., Ltd. system
C4: butane tetracarboxylic acid dianhydride: Wako Pure Chemical Industries, Ltd.'s reagent
C5: oxazoline compound: Epocros (registration mark) WS-500: Nippon Shokubai Co., Ltd's system
C6: chitosan compound: Daichitosan (registration mark) W-10: industrial society system of refining day greatly
D1: polyvinyl alcohol: NL-05R (fully saponified type): Japanese synthetic chemical industry society system
D2: PVP: Polyvinylpyrrolidone K90: Nippon Shokubai Co., Ltd's system
D3: sodium carboxymethylcellulose: Cellogen (registration mark) PR: Di-ichi Kogyo Seiyaku Co., Ltd.'s system
D4: hydroxypropyl cellulose: HPC-LEP: Shin-Etsu Chemial Co., Ltd's system
D5: sodium alginate: Duck Algin NSPL:Kikkoman Biochemifa Company system
D6: polyethylene glycol: PEG20000: Sanyo Chemical Industries, Ltd.'s system
D7: polyacrylamide: EFH-06:SENKA corporation system
E1: sodium metasilicate: No. 4 sodium metasilicate: Fuji Chemical KK's system
E2: the aqueous solution of Sodium Polyacrylate: Jurimer (registration mark) AC-10HN: Nihon Junyaku Co., Ltd.'s system
(manufacture method containing the acrylic resin 1 of sulfonic acid functional group)
Possessing thermometer, mixer, and in the reactor of partial reflux formula cooler, add methyl methacrylate (MMA) 110.6 parts, 2-acrylamide-2-methyl propane sulfonic (AMPS) 10.4 parts, methacryloxy polyoxypropylene sodium sulfovinate (ELEMINOL (registration mark) RS-3000: Sanyo Chemical Industries, Ltd.'s system) 2.2 parts, and pure water 200 parts, limit is stirred, backflow, react while add 1 part of azobis isobutyronitrile (AIBN) at 120 DEG C, obtain the acrylic resin 1 (Mn:30 containing sulfonic acid functional group, 000, sulfonic acid functional group measures: 0.4mmol/g).
(manufacture method containing the acrylic resin 2 of sulfonic acid functional group)
In the manufacture method of the acrylic resin 1 containing sulfonic acid functional group, except the addition of azobis isobutyronitrile (AIBN) is set to except 0.3 part, operate in the same manner as the acrylic resin 1 containing sulfonic acid functional group, obtain acrylic resin 2 (Mn:86,000, sulfonic acid functional group's amount: 0.4mmol/g) containing sulfonic acid functional group.
Table 1
Table 2
[method of evaluating performance]
Carry out performance evaluation by following method, obtained evaluation result is shown in Table 3.
< hydrophily evaluates >
If the operation of aluminum fin material to be flooded in ion exchange water after 8 hours dry 16 hours at 80 DEG C is 1 circulation, maximumly repeats enforcement 12 and to circulate such wetting-drying test.By carried out 0 circulation (before flooding), 3 circulations, 6 circulations, 9 circulations, 12 circulations the aluminum fin material of above-mentioned wetting-drying tests return to room temperature, the pure water of about 0.5 μ l is dripped on surface, use contact angle determination device (consonance interface science Co., Ltd. system: CA-05 type), measure the contact angle relative to water of fin material, evaluate hydrophily thus.Metewand is as described below.
◎ (good especially): water contact angle is lower than 20 °
Zero (well): water contact angle is more than 20 ° and lower than 30 °
△ (generally good): water contact angle is more than 30 ° and lower than 40 °
× (bad): water contact angle is more than 40 °
< resin-coated layer residual rate >
The test film of 80 × 62.5mm is cut out from resin-coated metal sheet, before flooding, (drying regime) uses precision balance quality measurement, the quality of only metallic plate will be deducted by measured quality and the value obtained as the quality (hereinafter referred to as resin-coated amount) of resin-coated layer.In addition, after above-mentioned wetting-drying test being carried out 3 circulations, carry out 12 circulations after measure the resin-coated amount of drying regime similarly.In addition, only the quality of metallic plate is heated to 580 DEG C of front and back obtains carrying out measuring with precision balance after resin-coated layer thermal decomposition removing by 12 times being flooded this test film after quality determination.
Resin-coated layer residual rate (hereinafter referred to as residual rate) is obtained by said determination result and following formula.
Residual rate (%)=[(the resin-coated amount in the resin-coated metal sheet after flooding for 3 times or 12 times) ÷ (the resin-coated amount in the resin-coated metal sheet before flooding)] × 100
◎ (good especially): residual rate is more than 80%
Zero (well): residual rate is more than 60% and lower than 80%
△ (generally good): residual rate is more than 40% and lower than 60%
× (bad): residual rate is lower than 40%
The moistening corrosion resistance > of <
In tank with cover, add ion exchange water, remain on 40 DEG C.On its water surface, hang aluminum fin material according to the mode directly do not contacted with water, expose the situation after 200 hours by visual valuation by under the state of water bath containment.Metewand is as described below.
Zero (well): do not see change on resin-coated layer and aluminium.Or slight variable color is had on resin-coated layer.
△ (generally good): see variable color in the part of resin-coated layer or whole.
× (bad): the remarkable variable color, chalking etc. that produce the resin-coated layer of burn into of aluminium.
< foul smell >
By breathing out lightly to application face, and the method for smelling the smell getting resin-coated layer is evaluated.Metewand is as described below.
Zero (well): do not feel foul smell
△ (centre): feel slight foul smell
× (bad): feel obvious foul smell
Table 3
Utilizability in industry
Resin-coated metal sheet of the present invention can maintain the hydrophily on surface chronically.In addition, the heat exchanger fin material be made up of resin-coated metal sheet of the present invention is useful for middle heat exchangers used such as air conditioners.Use the heat exchanger of the heat exchanger fin material be made up of resin-coated metal sheet of the present invention owing to not easily causing the reduction of the increase of flowing resistance or the heat exchange property with it, institute thinks high-quality.
Claims (4)
1. a resin-coated metal sheet, is characterized in that, it is the resin-coated metal sheet of the surface-coated resin-coated layer at metallic plate,
Described resin-coated layer is formed by resin-coated layer and obtains with composition, and described resin-coated layer formation composition comprises: (A) glycerol polymerization vinyl pyrrolidone and the graft polymers obtained, (B) on polyvinyl alcohol comprises the crosslinking agent of at least one in sulfonic acid (salt) and carboxylic acid (salt) as at least one in the anionic polymer of polymeric composition and (C) described graft polymers and described anionic polymer.
2. resin-coated metal sheet according to claim 1, wherein, described resin-coated layer formation composition comprises more than a kind in the group being selected from and being made up of polyvinyl alcohol, PVP, carboxymethyl cellulose salt, methylcellulose, hydroxypropyl cellulose, alginate, polyethylene glycol, polyacrylamide and their modifier further.
3. resin-coated metal sheet according to claim 1 and 2, wherein, described metallic plate is aluminium sheet or aluminium alloy plate.
4. a heat exchanger fin material, it is made up of resin-coated metal sheet according to claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014-002400 | 2014-01-09 | ||
| JP2014002400A JP6250405B2 (en) | 2014-01-09 | 2014-01-09 | Resin-coated metal plate and fin material for heat exchanger comprising the same |
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| CN104776750A true CN104776750A (en) | 2015-07-15 |
| CN104776750B CN104776750B (en) | 2017-04-12 |
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| CN112048115A (en) * | 2019-06-06 | 2020-12-08 | 国家能源投资集团有限责任公司 | Composite material of metal and polyolefin, preparation method and container thereof |
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| JP6857996B2 (en) * | 2016-10-25 | 2021-04-14 | 日本パーカライジング株式会社 | Surface treatment agent, film and surface treatment method |
| JP6732644B2 (en) | 2016-12-02 | 2020-07-29 | 日本ペイント・サーフケミカルズ株式会社 | Heat exchanger and method for hydrophilizing heat exchanger |
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| CN101381540A (en) * | 2007-09-04 | 2009-03-11 | 株式会社神户制钢所 | Resin coating metal plate with excellent roller formability |
| JP5006758B2 (en) * | 2007-10-26 | 2012-08-22 | 第一工業製薬株式会社 | Metal surface treatment agent |
| WO2013191149A1 (en) * | 2012-06-19 | 2013-12-27 | 日本ペイント株式会社 | Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316434A (en) * | 1996-06-03 | 1997-12-09 | Nippon Parkerizing Co Ltd | Aqueous treating agent for converting metal material into hydrophilic metal material and treatment therefor |
| JPH1036757A (en) * | 1996-07-23 | 1998-02-10 | Dai Ichi Kogyo Seiyaku Co Ltd | Hydrophilic surface treatment agent for heat exchanger fin |
| EP2380938B8 (en) * | 2009-01-21 | 2013-09-25 | Nihon Parkerizing Co., Ltd. | Hydrophilizing agent for aluminum-containing metal material, hydrophilizing method, and hydrophilized aluminum-containing metal material |
-
2014
- 2014-01-09 JP JP2014002400A patent/JP6250405B2/en not_active Expired - Fee Related
- 2014-12-22 CN CN201410806757.XA patent/CN104776750B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381540A (en) * | 2007-09-04 | 2009-03-11 | 株式会社神户制钢所 | Resin coating metal plate with excellent roller formability |
| JP5006758B2 (en) * | 2007-10-26 | 2012-08-22 | 第一工業製薬株式会社 | Metal surface treatment agent |
| WO2013191149A1 (en) * | 2012-06-19 | 2013-12-27 | 日本ペイント株式会社 | Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048115A (en) * | 2019-06-06 | 2020-12-08 | 国家能源投资集团有限责任公司 | Composite material of metal and polyolefin, preparation method and container thereof |
| CN112048115B (en) * | 2019-06-06 | 2023-09-26 | 神华(北京)新材料科技有限公司 | Composite material of metal and polyolefin, preparation method and container thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015131389A (en) | 2015-07-23 |
| JP6250405B2 (en) | 2017-12-20 |
| CN104776750B (en) | 2017-04-12 |
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