CN104776750B - 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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- CN104776750B CN104776750B CN201410806757.XA CN201410806757A CN104776750B CN 104776750 B CN104776750 B CN 104776750B CN 201410806757 A CN201410806757 A CN 201410806757A CN 104776750 B CN104776750 B CN 104776750B
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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 be formed with the resin-coated metal sheet of the excellent resin-coated layer of hydrophilic on the surface of metallic plate.
Additionally, the present invention relates to can chronically continue the heat exchanger fin material of the surface texture that dew etc. is easily wetted.
Background technology
In the heat exchanger of air conditioner, from the aspect that heat conductivity, processability, corrosion resistance etc. are excellent, aluminum is widely used
Material, in order to effectively be exchanged heat, additionally, in order to suppress in space compact, becoming and arranging aluminum with narrow spacing parallel arranging
The structure of fin material.Therefore, it is attached if the temperature of wing sheet surface is reached below the dew point of air in the operating of air conditioner
The dew condensation in wing sheet surface, makes adjacent fin inaccessible to each other sometimes.Now, on aluminum fin material surface
In the case that hydrophilic is low, because the contact angle with water becomes big, so accompanying dew becomes hemispherical, closing for fin is made
Plug-like state further deteriorates.As a result, all the time known cause heat exchange function hindered, or dew is made because of blast
The problems such as dispersing to outside air conditioner.
In order to improve the problem of above-mentioned dew, develop carries out hydrophilicity-imparting treatment by the surface to aluminium sheet itself,
So as to when being processed into fin material and using, dew will not rest on fin surface and be easily removed the technology of discharge.Example
Such as Patent Document 1 discloses the technology by synthetic silica and water paint.
However, because resulting film is hardened if using synthetic silica, so there is the shaping in fin material
Plus the violent problem of abrasion of man-hour instrument, mould etc..Additionally, also having that the unique cement of silicon dioxide is smelly or dust is smelly, pushing away
Survey gives people body and causes asking for sense of discomfort due to the foul smell for dispersing of the material or silicon dioxide microparticle that adsorb on silica
Topic.Thus, for example Patent Document 2 discloses using alumina sol to replace the high-hydrophilic coating of silicon dioxide.Just
It is for the technology, although mitigate but still observe foul smell compared with when using silicon dioxide and smelly using if if long-time
Gas gradually increases, thus from suppress foul smell in terms of for it is also insufficient.
On the other hand, Patent Document 3 discloses to suppress the dew long-time for being attached to wing sheet surface to be detained
And hydration reaction, corrosion reaction are induced, use using the salt and N hydroxymethyl acrylamide of carboxymethyl cellulose as main constituent
The technology of surface conditioning agent.Additionally, Patent Document 4 discloses to give corrosion resistance and hydrophilic to fin material, using with
Polyvinyl alcohol and polyvinyl pyrrolidone are effective as the surface conditioning agent of main constituent.In the technology of patent documentation 3,4
In, due to not using silicon dioxide etc., so problem as the abrasion of foul smell, mould will not be caused.
But, if the hydrophilic resin epithelium long-time of organic system is contacted with water, due to epithelium dissolution at leisure, so
Reduce when there is hydrophilic Jing.Accordingly, it is difficult to chronically maintain the hydrophilic of wing sheet surface, there is the remaining of improvement
Ground.
Additionally, Patent Document 5 discloses being used by the glycerol polymerization second on polyvinyl alcohol as metal conditioner
The compositionss that polymer obtained from vinyl pyrrolidone and the blocked isocyanates as cross-linking agent are constituted, by by the group
Compound is applied to the surface of metal material, can obtain good hydrophilic.
Even if the metallic plate described in above-mentioned patent documentation 5 floods and is dried (hereinafter also referred to as anti-being repeated a number of times
Flood again) in the case of, it is also possible to suppress the dissolution of epithelium, also there is no the contact angle relative to water of metallic plate substantially (below,
Referred to as water contact angle) change, for the water contact angle value, the present application person have carried out supplementary test, have as a result known, from
Initial stage rises and substantially exceeds 40 ° and remain high, so can not say satisfaction as heat exchanger fin material institute anyway
The water-wet behavior for needing, room for improvement is still very big.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Application 55-164264 publication
Patent documentation 2：Japanese Unexamined Patent Publication 10-168381 publication
Patent documentation 3：Japanese Unexamined Patent Publication 2-258874 publication
Patent documentation 4：Japanese Unexamined Patent Publication 5-302042 publication
Patent documentation 5：Japanese Unexamined Patent Publication 2009-108111 publications
The content of the invention
Invent problem to be solved
In the present invention, it is also contemplated that due to obviousization of global warming, the surging problem of resource etc., cause the efficient of air conditioner
The requirement of the performance improvements such as rate, miniaturization is improved, and its problem is to provide the hydrophilic tree that can chronically remain excellent
Fat coated metal plate and using its heat exchanger fin material.
For solving the scheme of problem
The present invention is the resin-coated metal sheet of the surface coated with resin coating in metallic plate, it is characterised in that
Above-mentioned resin-coated layer is formed by resin-coated layer and obtained with compositionss, and the resin-coated layer formation is included with compositionss：
Graft polymers (A) obtained from glycerol polymerization vinyl pyrrolidone on polyvinyl alcohol, comprising sulfonic acid (salt) and carboxylic acid (salt)
At least one of as polymeric composition anionic polymer (B) and above-mentioned graft polymers and above-mentioned anionic property
The cross-linking agent (C) of at least one of polymer.
Above-mentioned resin combination is preferably further comprising fine selected from polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl
The plain salt of dimension, methylcellulose, hydroxypropyl cellulose, alginate, Polyethylene Glycol, polyacrylamide and their modifier group
Into group in more than a kind.
Above-mentioned metallic plate is preferably aluminium sheet or aluminium alloy plate.
Additionally, in the present invention, also comprising the heat exchanger being made up of above-mentioned resin-coated metal sheet fin material.
Invention effect
The resin-coated metal sheet of the present invention can chronically maintain the hydrophilic on surface.Additionally, by using by this
The heat exchanger fin material that bright resin-coated metal sheet is constituted, can be reduced because of dew institute caused fin material to each other
Inaccessible a problem that, using the teaching of the invention it is possible to provide the heat exchanger that can be effectively exchanged heat.
Specific embodiment
The resin-coated metal sheet of the present invention is the resin-coated layer formation compositionss quilt that the surface of metallic plate is prescribed
Cover.
[metallic plate]
Metal plate used in the resin-coated metal sheet of the present invention can such as include aluminium sheet, aluminium alloy plate, steel plate, plating
Steel plate, copper coin, titanium plate etc..In them, preferred aluminium sheet or aluminium alloy plate, from heat conductivity and excellent in workability aspect, make
With 1000 aluminum for being specified in JIS H4000, preferred alloy numbering is 1200 aluminum.It is left that thickness of slab is preferably 0.08～0.3mm
It is right.
[resin-coated layer formation compositionss]
Resin-coated layer formation compositionss (hereinafter referred to as resin combination) are included in glycerol polymerization second on polyvinyl alcohol
Graft polymers obtained from vinyl pyrrolidone (A), comprising at least one of sulfonic acid (salt) and carboxylic acid (salt) as be polymerized
The anionic polymer (B) of composition and at least one of above-mentioned graft polymers and above-mentioned anionic polymer
Cross-linking agent (C).
It is grafted obtained from glycerol polymerization vinyl pyrrolidone (NVP) on polyvinyl alcohol poly-
Compound (hereinafter referred to as graft polymers (A)) is the water soluble polymer of nonionic.
Above-mentioned graft polymers (A) if manufacture be suitable for known technology, in such as patent documentation 5 (Japan spy
Open 2009-108111 publications) in it is on the books.
Polyvinyl alcohol preferred degree of polymerization for manufacturing above-mentioned graft polymers (A) is 100～4000, more preferably 100
～3000.If the degree of polymerization is less than 100, it is likely that the intensity of resin-coated layer becomes insufficient, if more than 4000, becoming high
Viscosity, it is possible to which operability is reduced.
The saponification degree of polyvinyl alcohol is preferably 70～100mol%.If saponification degree is less than 70mol%, it is likely that resin quilt
The weakened of coating.
The K values of graft polymers are preferably 12～150.So-called K values are to change what scholar Fikentscher was proposed by Germany
The constant of the degree of polymerization is represented, if K values are less than 12, the weakened of resin-coated layer, if more than 150, becoming high viscosity, has
Possible operation is reduced.
For manufacture above-mentioned graft polymers (A) vinyl pyrrolidone amount preferably with respect to polyvinyl alcohol be 5～
900 mass %.If being less than 5 mass %, cannot get sufficient hydrophilic, if more than 900 mass %, it is likely that resin-coated
The intensity decreases of layer.
It is that above-mentioned graft polymers (A) for example can be by anti-in polymerization using polyvinyl alcohol as the graft polymers of main chain
In answering device, vinyl pyrrolidone is coordinated in poly-vinyl alcohol solution, using known radical polymerization initiator in polyethylene
The manufacture method of glycerol polymerization vinyl pyrrolidone on alcohol chain and obtain.
As polymerization initiator, it is possible to use be generally used for hydrogen peroxide, organic peroxide, the azo of radical polymerization
Series initiators etc..As the example of organic peroxide, can include tert-butyl hydroperoxide, di-tert-butyl peroxide,
Benzoyl peroxide etc..As azo-compound, 2 can be included, 2 '-azobis isobutyronitrile, 2, double (the 2- methyl of 2 '-azo
Butyronitrile), 2,2 '-azo double (2,4- methyl pentane nitrile), 2,2 '-azo double (4- methoxyl group -2,4- methyl pentane nitriles) etc..Reaction
As long as method and reaction condition are selected according to the example of general radical polymerization.
Comprising at least one of sulfonic acid (salt) and carboxylic acid (salt) as polymeric composition anionic polymer (B) (with
Under, also referred to as anionic polymer (B)) for the water soluble polymer of anionic property.In addition, so-called sulfonic acid (salt) be sulfonic acid or
Its salt, so-called carboxylic acid (salt) is carboxylic acid or its salt.
As sulfonic acid (salt), for example, can include allyl sulphonic acid or its salt, methylpropenyl sulfonic acid or its salt, vinyl
3- described in sulfonic acid or its salt, 2- acrylamide-2-methyl propane sulfonics or its salt, Japanese Unexamined Patent Publication 2012-122052 publications
Allyloxy -2- hydroxyl -1- propane sulfonic acid or its salt etc..
As carboxylic acid (salt), for example, can include (methyl) acrylic acid or its alkali metal salt, itaconic acid or its alkali metal salt
Deng.
Above-mentioned anionic polymer (B) can be by a kind of polymerization for constituting in sulfonic acid (salt) or carboxylic acid (salt)
Thing, or the copolymer of more than two kinds in sulfonic acid (salt) and carboxylic acid (salt), can also be their modifier.On
State the copolymer that anionic polymer (B) is preferably sulfonic acid (salt) and (methyl) acrylic acid (salt).
The preferred compounding ratio of above-mentioned graft polymers (A) and above-mentioned anionic polymer (B) is in terms of quality ratio
For (A): (B)=10: 90～90: 10.Due to above-mentioned graft polymers (A) it is excessive compared with above-mentioned anionic polymer (B)
And when becoming outside above range, although because flood repeatedly caused by water contact angle increase amplitude it is little, it is likely that initial stage
Water contact angle becomes big.Further, since above-mentioned anionic polymer (B) excessively becomes compared with above-mentioned graft polymers (A)
When outside above range, although the water contact angle at initial stage is little, it is likely that causing water contact angle to increase because flooding repeatedly.
As at least one of above-mentioned graft polymers and above-mentioned anionic polymer cross-linking agent (hereinafter referred to as
Cross-linking agent (C)), as long as the hydroxyl of the polyvinyl alcohol part in above-mentioned graft polymers (A) can be each other crosslinked
Compound, the compound that the carboxyl of the carboxylic moiety in above-mentioned anionic polymer (B) can be crosslinked or being capable of shape
Into the compound of the association body (ion complexation body) of above-mentioned anionic polymer (B).By using above-mentioned cross-linking agent (C)
It is crosslinked, it is possible to increase the resistance to water of resin-coated metal sheet.
As the crosslinking that can be each other crosslinked the hydroxyl of the polyvinyl alcohol part in above-mentioned graft polymers (A)
Agent, can include glycidyl ether compound, isocyanate compound, melamine compound, aldehyde compound, BTCA
The boric acid based compounds such as dianhydride, the amines with multiple functional groups, boric acid borax, with 1 in Ti, Zr, Al
Metal alkoxide of kind or metallic element of more than two kinds etc..As can be by the carboxylic moiety in above-mentioned anionic polymer (B)
The cross-linking agent that is crosslinked of carboxyl, glycidyl ether compound, isocyanate compound can be included, with multiple functional groups
Amines, oxazoline compounds, carbodiimide compound etc..Further, as can be with above-mentioned anionic polymer (B)
The cross-linking agent of polyion complexation body is formed, the polycationic compounds such as chitosan compound can be included.As can embody more
The preferred cross-linking agent (C) of low water contact angle, preferably applicable glycidyl ether compound Huo oxazoline compounds etc..
The preferred compounding ratio of above-mentioned cross-linking agent (C) is poly- with above-mentioned anionic property relative to above-mentioned graft polymers (A)
Total 100 mass parts of compound (B) are 5～50 mass parts, more preferably 10～40 mass parts.If being less than 5 mass parts, obtain not
To sufficient resistance to water, it is possible to the resin-coated layer more dissolution when flooding, if more than 50 mass parts, hydrophilic sometimes
Reduce.
Possesses the resin that the resin-coated layer obtained with compositionss is formed by the resin-coated layer comprising above-mentioned (A)～(C)
Even if coated metal plate is also able to maintain that low water contact angle after flooding repeatedly, even additionally, the feelings being chronically submerged
Under condition, it is also possible to suppress the dissolution of resin-coated layer.As its reason, thus it is speculated that although the water contact angle at initial stage it is slightly higher even in
After flooding repeatedly the dissolution of resin-coated layer also less and the cross-linking agent of the above-mentioned graft polymers (A) of excellent in te pins of durability with for drop
The water contact angle at low initial stage is effective, but bad when easily producing Jing due to causing dissolution of resin-coated layer etc. because flooding repeatedly
The cross-linking agent of the above-mentioned anionic polymer (B) changed is mutually wrapped around one another, forms close IPN (Interpenetrating
Polymer Network：Interpenetrating polymer network) structure form.
Additionally, above-mentioned resin combination is preferably further comprising selected from polyvinyl alcohol, polyvinyl pyrrolidone, carboxylic first
Base cellulosate, methylcellulose, hydroxypropyl cellulose, alginate, Polyethylene Glycol, polyacrylamide and theirs is modified
More than a kind in the group (hereinafter referred to as (D)) of thing composition.
By further including more than a kind in above-mentioned (D) in above-mentioned resin combination, so as to be coated with this
In the resin-coated metal sheet of resin combination, water contact angle will not excessively increase and hydrophilic is excessively reduced, additionally, in application
Shi Rongyi forms the epithelium of homogenizing.Further, above-mentioned (D) compared with above-mentioned graft polymers (A), the unit price of raw material is cheap, so
During using the resin-coated layer formation compositionss comprising above-mentioned (A)～(D), with the use only resin comprising above-mentioned (A)～(C)
Coating formation is compared with compositionss, can reduce coating cost.The addition of above-mentioned (D) is preferably with respect to above-mentioned glycerol polymerization
Thing (A) is set to below 50 mass parts with the mass parts of total quality 100 of above-mentioned anionic polymer (B).If more than 50 mass
Part, then in the case where being chronically submerged, it is possible to which resin-coated layer dissolution, corrosion resistance are reduced.
Additionally, in the resin-coated metal sheet of the present invention, can be carried with arranging between resin-coated layer and metallic plate
The anti-corrosion skin membrane of high corrosion-resistant.Using the present invention resin-coated metal sheet as heat exchanger fin material use when, by resistance to
The formation of erosion skin membrane, because the corrosion resistance of fin material is further improved, it is possible to improving the durability of heat exchanger.Additionally,
Become hydrophobicity by making anti-corrosion skin membrane, water penetration can be suppressed into resin-coated layer and because apply underfilm corrosion produce it is smelly
Gas.In anti-corrosion skin membrane, it is possible to use known coating resin, it is possible to use polyester based resin, polyolefin-based resins,
Epoxy system resin, carbamate system resin, acrylic resin etc..These resins can also be crosslinked by cross-linking agent.Example
Such as, in the case of polyester based resin, can be crosslinked with the melamine series cross-linking agent that can be crosslinked with hydroxyl.
Further, in order to further improve corrosion resistance, the process of phosphoric acid chromate, application type zirconium can also be implemented to metallic plate
Process etc. inorganic oxide process, using the known chemical conversion treatment such as process of organic-inorganic composite compound.At these
If reason is before anti-corrosion skin membrane is formed or is not laminated anti-corrosion skin membrane, then will be containing the resin group of above-mentioned (A)～(D)
Compound is carried out before being layed onto on metallic plate.
As long as the solvent used in the resin combination of the present invention can be such that the resin combination of the present invention contains
Each composition dissolving or scattered solvent, then be not particularly limited, preferably mainly use water.
Additionally, in the resin combination of the present invention, in the range of the performance of the without prejudice to present invention, in order to improve coating
Or operability, Physical properties of coating film etc., it is also possible to and various coating additives are used, for example, it is also possible to arbitrarily use alcohols, glycol ethers
Deng cosolvent or surfactant, surface conditioner, cross-linking agent, deaeration agent, levelling agent, rheology control agent, antibacterial, other prevent
Mould dose etc..
[resin-coated layer]
Resin combination is 0.1～10g/m preferably per metallic plate one side in the adhesion amount (amount of coating) of metal sheet surface2。
If adhesion amount is less than 0.1g/m2, then it is not only the possibility to not embody sufficient hydrophilic, and be possible to moisten corrosion resistance evil
Change.Moistening corrosion resistance is evaluated by evaluation methodology described later.If additionally, adhesion amount is more than 10g/m2, then due to resin quilt
Coating becomes heat insulation layer, it is possible to heat transfer property is reduced, and then economically also becomes high cost.Resin combination it is attached
The amount of wearing is 0.2～3.0g/m preferably per metallic plate one side2, it is 0.3～2.0g/m further preferably per metallic plate one side2。
[manufacture method of resin-coated metal sheet]
The manufacture method of the resin-coated metal sheet of the present invention is not particularly limited, for example should by the metallic plate to web-like
With roll coater device etc., resin combination is applied to behind the surface of metallic plate carries out heat treated, it is possible thereby to form resin
Coating.In addition it is also possible to be formed with the metallic plate of above-mentioned anti-corrosion skin membrane, resin-coated layer is identically formed.
[heat exchanger fin material]
The resin-coated metal sheet of the present invention can be used as heat exchanger fin material.By the resin-coated gold of the present invention
The heat exchanger that category plate is constituted is little with fin material water contact angle, even if long-time is contacted with water, it is also possible to suppress the increasing of water contact angle
Greatly.Therefore, in the heat exchanger for being manufactured with fin material using the heat exchanger that constitutes of resin-coated metal sheet by the present invention, dew
Wing sheet surface is present in the state of little water contact angle.Afterwards, by being removed under gravity stream, even if so chronically
Use, be not easy to cause the increase of flowing resistance or the reduction with its heat exchange property.
Embodiment
The present invention is further described in detail by the following examples, but following embodiments are not intended to limit the present invention,
Change enforcement without departing from the spirit and scope of the invention to be integrally incorporated in the present invention.
Hereinafter, " % " expression " quality % ", " part " expression " mass parts ".
[manufacture method of material to be tested]
By known manufacture method, the aluminium sheet (thickness of slab formed by the A1200 (JIS H4000) of fine aluminium system is manufactured
For 0.10mm).By aluminium sheet alkaline reagent (Nippon Paint Co., Ltd.s system " Surfcleaner (registered trade mark)
360 ") defat is carried out, carries out phosphoric acid chromate process.The adhesion amount of chemical conversion treatment epithelium is set to 30mg/m by Cr conversions2。
[manufacture method of aluminum fin material]
Resin combination is prepared with the mass ratio shown in table 1 and table 2, by 6% aqueous solution of the resin combination according to
The mode for reaching the adhesion amount shown in table 3 is applied on the aluminium sheet after above-mentioned phosphoric acid chromate is processed using bar coater, is used
Hot-air drying stove is thermally dried at 220 DEG C of highest threshold temperature, manufactures aluminum fin material.Highest threshold temperature is by heat
Sealed adhesive tape is confirmed.Each composition shown in table 1 and table 2 obtains following material to use, or by the system of following record
Make method to manufacture.
A1：Polyvinyl alcohol-Polyvinylpyrrolidone graft copolymer：According to Japanese Unexamined Patent Publication 2009-108111 publications：
PVA/PVP mass ratio=50/50：The PVA degree of polymerization 1700：Fully saponified type
B1：The salt of 3- allyloxys -2- hydroxyls -1- propane sulfonic acid (HAPS) and acrylic acid copolymer：According to Japanese Unexamined Patent Publication
2012-122052 publications：Mw=182000：HAPS ratios 25%
B2：Acrylic acid-sulfonic acid copolymer：Aron (registered trade mark) A-6012：Toagosei Co., Ltd's system
B3：Acrylic resin 1 containing sulfonic acid functional group：Manufacture method is described below
B4：Acrylic resin 2 containing sulfonic acid functional group：Manufacture method is described below
C1：Polyfunctional glycidyl ether：Denacol (registered trade mark) EX-614B：Nagase Chemtex
Corporation systems
C2：Blocked isocyanates：Elastron (registered trade mark) H-38：Di-ichi Kogyo Seiyaku Co., Ltd.'s system
C3：Melmac：Nikalac (registered trade mark) M-035：Sanwa Chemical Co., Ltd.s system
C4：Butane tetracarboxylic acid dianhydride：Wako Pure Chemical Industries, Ltd.'s reagent
C5：Oxazoline compound：Epocros (registered trade mark) WS-500：Nippon Shokubai Co., Ltd's system
C6：Chitosan compound：Daichitosan (registered trade mark) W-10：Big industrial society's system of refining day
D1：Polyvinyl alcohol：NL-05R (fully saponified type)：Japanese synthetic chemical industry society system
D2：Polyvinyl pyrrolidone：Polyvinylpyrrolidone K90：Nippon Shokubai Co., Ltd's system
D3：Sodium carboxymethyl cellulose：Cellogen (registered trade 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 systems
D6：Polyethylene Glycol：PEG20000：Sanyo Chemical Industries, Ltd.'s system
D7：Polyacrylamide：EFH-06：SENKA corporation systems
E1：Sodium silicate：No. 4 sodium silicate：Fuji Chemical KK's system
E2：The aqueous solution of sodium polyacrylate：Jurimer (registered trade mark) AC-10HN：Nihon Junyaku Co., Ltd.'s system
(manufacture method of the acrylic resin 1 containing sulfonic acid functional group)
In the reactor for possessing thermometer, blender and partial reflux formula cooler, add methyl methacrylate
(MMA) 110.6 parts, 10.4 parts of 2- acrylamide-2-methyl propane sulfonics (AMPS), methacryloxy polyoxypropylene sulfuric ester
Sodium (ELEMINOL (registered trade mark) RS-3000：Sanyo Chemical Industries, Ltd.'s system) 2.2 parts and 200 parts of pure water, side stirring,
Backflow, while add 1 part of azobis isobutyronitrile (AIBN) at 120 DEG C being reacted, obtains the acrylic acid seriess containing sulfonic acid functional group
(the Mn of resin 1：30,000th, sulfonic acid functional group's amount：0.4mmol/g).
(manufacture method of the acrylic resin 2 containing sulfonic acid functional group)
In the manufacture method of the acrylic resin 1 containing sulfonic acid functional group, except by azobis isobutyronitrile (AIBN)
Addition is set to 0.3 part in addition, operates in the same manner as the acrylic resin 1 containing sulfonic acid functional group, obtains containing sulfonic acid functional group
(the Mn of acrylic resin 2：86,000th, sulfonic acid functional group's amount：0.4mmol/g).
Table 1
Table 2
[method of evaluating performance]
Performance evaluation is carried out by following methods, resulting evaluation result is shown in Table 3.
<Hydrophilic is evaluated>
If dry 16 hours operation at 80 DEG C is 1 after aluminum fin material is impregnated 8 hours in ion exchange water
Circulation, maximum repeats the such wetting-drying test of 12 circulations of enforcement.To carry out 0 circulation (before flooding), 3 circulation, 6
Individual circulation, 9 circulations, the aluminum fin materials of above-mentioned wetting-drying tests of 12 circulations recover to room temperature, and on surface, Deca is about
The pure water of 0.5 μ l, using contact angle determination device (consonance interface science Co. Ltd. system：CA-05 types), determine the relative of fin material
In the contact angle of water, hydrophilic is thus evaluated.Metewand is as described below.
◎ (especially good)：Water contact angle is less than 20 °
Zero (good)：Water contact angle is 20 ° less than 30 °
△ (general good)：Water contact angle is 30 ° less 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, (drying regime) is surveyed with precision balance before flooding
Determine quality, be worth obtained from the only quality of metallic plate is deducted by the quality for being determined as resin-coated layer quality (below,
Referred to as resin-coated amount).Additionally, above-mentioned wetting-drying test being carried out after 3 circulations, carrying out similarly being surveyed after 12 circulations
Determine the resin-coated amount of drying regime.In addition, only the quality of metallic plate is by the test of 12 times being flooded after quality determination
Piece is heated to 580 DEG C and will be measured with precision balance after the thermal decomposition removing of resin-coated layer in front and back and obtained.
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 resin-coated metal sheet after flooding for 3 times or 12 times) ÷ is (before flooding
Resin-coated metal sheet in resin-coated amount)] × 100
◎ (especially good)：Residual rate is more than 80%
Zero (good)：Residual rate is 60% less than 80%
△ (general good)：Residual rate is 40% less than 60%
× (bad)：Residual rate is less than 40%
<Moistening corrosion resistance>
Ion exchange water is added in tank with cover, 40 DEG C are maintained at.On its water surface, according to not with water directly contact
Mode hang aluminum fin material, evaluate by visual observation in the state of by water bath containment expose 200 hours after situation.Evaluate
Benchmark is as described below.
Zero (good)：Change is not seen on resin-coated layer and aluminum.Or have slight discoloration on resin-coated layer.
△ (general good)：Discoloration is seen in a part for resin-coated layer or whole face.
× (bad)：Produce notable discoloration, chalking of the resin-coated layer of burn into of aluminum etc..
<Foul smell>
By lightly breathing out to application face, and the method for the abnormal smells from the patient for taking resin-coated layer is smelt being evaluated.Evaluate base
It is accurate as described below.
Zero (good)：Foul smell is not felt
△ (centre)：Feel slight foul smell
× (bad)：Feel obvious foul smell
Table 3
Industrial applicability
The resin-coated metal sheet of the present invention can chronically maintain the hydrophilic on surface.Additionally, by the resin of the present invention
The heat exchanger fin material that coated metal plate is constituted is useful for the heat exchanger used in air conditioner etc..Using by the present invention
The heat exchanger of heat exchanger fin material that constitutes of resin-coated metal sheet cause the increase of flowing resistance or adjoint due to being difficult
The reduction of its heat exchange property, so being high-quality.
Claims (4)
1. a kind of resin-coated metal sheet, it is characterised in that it is the tree of the surface coated with resin coating in metallic plate
Fat coated metal plate,
The resin-coated layer is formed by resin-coated layer and obtained with compositionss, the resin-coated layer formation compositionss bag
Contain：(A) on polyvinyl alcohol graft polymers obtained from glycerol polymerization vinyl pyrrolidone, (B) comprising sulfonic acid (salt) and
At least one of carboxylic acid (salt) is used as the anionic polymer and (C) described graft polymers of polymeric composition and described
The cross-linking agent of at least one of anionic polymer.
2. resin-coated metal sheet according to claim 1, wherein, the resin-coated layer formation is further with compositionss
Comprising selected from polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose salt, methylcellulose, hydroxypropyl cellulose, sea
More than a kind in the group of alginate, Polyethylene Glycol, polyacrylamide and their modifier composition.
3. resin-coated metal sheet according to claim 1 and 2, wherein, the metallic plate is aluminium sheet or aluminium alloy plate.
4. a kind of heat exchanger fin material, it is made up of the resin-coated metal sheet described in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104776750A CN104776750A (en) | 2015-07-15 |
| CN104776750B true CN104776750B (en) | 2017-04-12 |
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| CN201410806757.XA Expired - Fee Related CN104776750B (en) | 2014-01-09 | 2014-12-22 | Metal plate coated by resin and heat exchanger fin material comprising same |
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| CN (1) | CN104776750B (en) |
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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 |
| 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 |
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 |
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| 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 |
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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 |
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| Publication number | Publication date |
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| JP2015131389A (en) | 2015-07-23 |
| JP6250405B2 (en) | 2017-12-20 |
| CN104776750A (en) | 2015-07-15 |
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