CN104830193A - High hydrophilic coating composition and use thereof - Google Patents
High hydrophilic coating composition and use thereof Download PDFInfo
- Publication number
- CN104830193A CN104830193A CN201510046587.4A CN201510046587A CN104830193A CN 104830193 A CN104830193 A CN 104830193A CN 201510046587 A CN201510046587 A CN 201510046587A CN 104830193 A CN104830193 A CN 104830193A
- Authority
- CN
- China
- Prior art keywords
- methyl
- water
- weight
- soluble polymers
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
Abstract
High hydrophilic coating composition of the present invention contains 2-acrylamido-2-methylpropanesulfonic acid (salt), vinyl monomer having a hydroxyl group and a vinyl monomer having a carboxyl group obtained by copolymerizing Water-soluble copolymers. In addition, the heat exchanger of the present invention on the surface of the heat sink fin member made of metal having high hydrophilicity using the above-described coating composition of the hydrophilic coating film.
Description
Technical field
The present invention relates to high-hydrophilic coating composition and uses thereof.Specifically, relate to formed on the surface of various base materials etc., can to base material give wetting ability, excellent adhesion film above-mentioned high-hydrophilic coating composition and there is radiator fin for heat exchanger (fin) material of the hydrophilic film formed by this high-hydrophilic coating composition and employ its heat exchanger.
Background technology
For the radiator fin for heat exchanger material of air-conditioning etc., from the view point of thermal conductivity, processibility and lightweight, mainly employ aluminum or aluminum alloy.
If make heat exchanger work, on fin material surface, the water vapor in air is cooled and condensation, becomes dew.But for the reason of the miniaturization, raising thermo-efficiency etc. of heat exchanger, with narrow interval configuration fin material, therefore dew deposits between adjacent radiator element sometimes, makes between radiator element inaccessible thus.Its result, the dew that ability reduces, blast causes producing the heat exchanger that the increase of ventilation resistance causes such as to disperse at the problem outside air conditioning machinery.In order to prevent this problem, develop following technology: utilize high-hydrophilic coating etc. to make fin material surface hydrophilic, do not deposit at the water of fin material surface condensation, easily flow out as draining.
But due to the process between environment for use and usage period, various pollution substance is in fin material surface attachment etc., and therefore the wetting ability on surface reduces, and sometimes can not show the function set originally fully.Therefore, when utilizing high-hydrophilic coating by substrate surface hydrophilization, require give sufficient hydrophilic while, also maintain wetting ability in long-term use.
In order to tackle above-mentioned requirements, proposing utilization and at the water of condensation of fin material surface generation, the pollution substance of attachment being removed, there is the so-called high-hydrophilic coating from detergency.Such as, in patent documentation 1, disclose the high-hydrophilic coating employing alumina sol.But even if utilize the method, due to the environment used, various spot attachment, loses original function sometimes.Especially, lipid (oil droplet produced when floor wax, conditioning) insoluble in water, if be attached to film coated surface, is not easy to come off.
Patent Document 2 discloses the surface treatment agent using wetting ability organic resin particulate as principal constituent, after describing pollution substance attachment, also there is excellent wetting ability.It increases and the contact area of water for being formed concavo-convex in film coated surface, improve hydrophilic gimmick, but compared with level and smooth film, the irregular film of tool betwixt gap easily adheres to foul smell composition, the necessity be improved in the attachment of preventing pollution material.
On the other hand, the hydrophilic technology that the level and smooth film of several use remains excellent is chronically proposed.For example, Patent Document 3 discloses coating composition, it uses using the hydrophilic resin of the monomer copolymerization by having carboxyl and hydroxyl and amido and the surface treatment agent of hydrophilic resin as principal constituent with ether.In addition, owing to the hydrophilic resin with sulfonic monomer copolymerization to be had excellent initial hydrophilicity, several coating composition (patent documentation 4 ~ 6) using it as principal constituent is thus disclosed.
Prior art document
Patent documentation
Patent documentation 1: Unexamined Patent 10-168381 publication
Patent documentation 2: JP 2009-179811 publication
Patent documentation 3: JP 2005-75841 publication
Patent documentation 4: JP 2010-159379 publication
Patent documentation 5: JP 2012-72336 publication
Patent documentation 6: JP 2012-122052 publication
Summary of the invention
The problem that invention will solve
But the hydrophilic resin recorded in patent documentation 3, wetting ability is low, and it can not show sufficient wetting ability separately.In addition, there is following problems in the polyoxyethylene glycol added to improve wetting ability: easily flows out due to water of condensation, and after its stripping, wetting ability significantly reduces.
In addition, the hydrophilic coating recorded in patent documentation 4 ~ 6, owing to can give excellent wetting ability, the stain resistance from detergency that therefore make use of water of condensation generation is also excellent, but because hydrophilic persistence is not enough, the therefore performance difficulty such as long term maintenance stain resistance.
The present invention completes in view of such practical situation, its problem is to provide coating composition and have the radiator fin for heat exchanger material of the high-hydrophilic film formed by this coating composition and employ its heat exchanger, this coating composition, when the substrate surface coating of radiator fin for heat exchanger material etc., has even if formed wetting ability, this hydrophilic film of long term maintenance that the pollution substances such as grease are attached to the excellence that surface also utilizes dew to be rinsed.
For solving the means of problem
In order to solve above-mentioned problem, the present inventor thinks that display is higher compared with the hydrophilic film formed by existing coating composition wetting ability and its film also have can not because of dew etc. and the water tolerance of stripping etc. (hydrophilic persistence) becomes the hydrophilic important document of long term maintenance excellence.
The present inventor conducts in-depth research for the high-hydrophilic coating composition obtaining above-mentioned such film, found that: utilize the coating composition containing the water-soluble polymers be made up of the monomer mixture of the specific sulfonic acid monomer comprising more than specified amount can solve above-mentioned problem, complete the present invention.
Namely, first invention is high-hydrophilic coating composition, it contains water-soluble polymers (A), this water-soluble polymers (A) is based on all forming monomer, by making 2-acrylamido-2-methyl propane sulfonic acid or its salt (a1) 80 ~ 94.5 % by weight, have the ethene base system monomer (a2) 4 ~ 15 % by weight of hydroxyl, have the ethene base system monomer (a3) 0.5 ~ 8 % by weight of carboxyl and other ethene base system monomer (a4) 0 ~ 15 % by weight copolymerization and the polymkeric substance that obtains, weight-average molecular weight is 100,000 ~ 1,500,000.
Second invention is high-hydrophilic coating composition, it is characterized in that, it is the high-hydrophilic coating composition containing above-mentioned water-soluble polymers (A) and water-soluble polymers (B), the weight ratio of water-soluble polymers (A) and water-soluble polymers (B) is the ratio of (A)/(B)=30/70 ~ 95/5, above-mentioned water-soluble polymers (B) is based on all forming monomer, the polymkeric substance obtained by making to have the ethene base system monomer (b1) 50 ~ 100 % by weight of carboxyl and other ethene base system monomer (b2) 0 ~ 50 % by weight copolymerization, weight-average molecular weight is 100,000 ~ 1,500,000.
3rd invention is radiator fin for heat exchanger material, and it has the hydrophilic film formed by the high-hydrophilic coating composition described in the first or second invention on the base material be made up of aluminum or aluminum alloy.
4th invention is heat exchanger, it uses the radiator fin for heat exchanger material described in the 3rd invention.
The effect of invention
When high-hydrophilic coating composition in the present invention is coated the substrate surface of radiator fin for heat exchanger material etc., the film formed on this surface contains the hydrophilic functional group from having sulfonic 2-acrylamido-2-methyl propane sulfonic acid or its salt with height ratio, therefore shows very high wetting ability.In addition, even if the pollution substances such as grease are when its surface attachment, because the wetting ability of film is very high, water of condensation etc. is therefore easily utilized to be removed.On the other hand, film self, due to can not stripping etc. in water of condensation, has sufficient water tolerance, therefore maintains the wetting ability of giving fin material surface chronically.
Embodiment
Below to the detailed description of the invention.Further, in this specification sheets, " (methyl) vinylformic acid " means vinylformic acid and/or methacrylic acid, and " (methyl) acrylate " means acrylate and/or methacrylic ester.In addition, " (methyl) acryl " means acryl and/or methacryloyl.
< water-soluble polymers (A) >
Water-soluble polymers of the present invention (A), based on all forming monomer, by making 2-acrylamido-2-methyl propane sulfonic acid or its salt (a1) 80 ~ 94.5 % by weight, has the ethene base system monomer (a2) 4 ~ 15 % by weight of hydroxyl, has the ethene base system monomer (a3) 0.5 ~ 8 % by weight of carboxyl and other ethene base system monomer (a4) 0 ~ 15 % by weight copolymerization and obtain.
As mentioned above, water-soluble polymers (A) is using 2-acrylamido-2-methyl propane sulfonic acid or its salt (a1) as structural unit.
In order to give excellent wetting ability to the film formed at substrate surface, think that in the base resin of coating composition, import sulfonic group with high containing ratio is effective.But, usually, there is sulfonic monomer and be mostly that polymerizability is low, when the usage ratio of such monomer is high, exists and can not make the tendency that the molecular weight of the polymkeric substance obtained is high fully.Therefore, sometimes applied coating composition time coating suitability, the water tolerance of film that obtains is not enough.
But, as having sulfonic monomer, when employing 2-acrylamido-2-methyl propane sulfonic acid or its salt (a1), even if when their ratio is high in monomer mixture, the sufficiently high polymkeric substance of molecular weight also can be obtained.Therefore, the above-mentioned problem solving coating suitability such with the water tolerance of the film obtained becomes possibility.
2-acrylamido-2-methyl propane sulfonic acid in water-soluble polymers (A) or the usage quantity of its salt (a1), relative to the total amount of the monomer mixture of formation water-soluble polymers (A), it is the scope of 80 ~ 94.5 % by weight, be preferably 82 ~ 94 % by weight, be more preferably the scope of 86 ~ 93 % by weight.
The usage quantity of 2-acrylamido-2-methyl propane sulfonic acid or its salt (a1) less than 80 % by weight when, the wetting ability of the film sometimes obtained and hydrophilic persistence become not enough.On the other hand, if more than 94.5 % by weight, because the usage quantity of the monomer (a2) with hydroxyl described later and/or the vinyl monomer (a3) with carboxyl is not enough, the film of excellent water resistance therefore sometimes cannot be obtained.
As the salt of 2-acrylamido-2-methyl propane sulfonic acid, can enumerate alkali earth metal salt and the ammonium salts etc. such as an alkali metal salts such as lithium salts, sodium salt, sylvite, magnesium salts, calcium salt, what can use in these is one kind or two or more.
As (a1), preferred 2-acrylamido-2-methyl propane sulfonic acid or its sodium salt, wherein, become higher aspect from the wetting ability of the film obtained, preferably use sodium salt.
As the ethene base system monomer (a2) with hydroxyl, can enumerate such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, polyethyleneglycol (methyl) acrylate, N-methylol (methyl) acrylamide etc., what can use in these is one kind or two or more.Wherein, as the ethene base system monomer (a2) with hydroxyl, set out in the aspect of the film that the wetting ability that is easy to get calmly is high, preferably (methyl) vinylformic acid 2-hydroxy methacrylate.
The usage quantity of monomer (a2), relative to the total amount of the monomer mixture of formation water-soluble polymers (A), is the scope of 4 ~ 15 % by weight, is preferably the scope of 5 ~ 11 % by weight, is more preferably the scope of 6 ~ 9 % by weight.The usage quantity of monomer (a2) less than 4 % by weight when, because the cross-linking density of film is low, therefore its water tolerance is not enough sometimes.On the other hand, if more than 15 % by weight, excellent wetting ability and the film of water tolerance sometimes cannot be had for a long time.
By using monomer (a2) in the structural unit of water-soluble polymers (A), being coated with the film obtained while there is high-hydrophilic, also being possessed excellent water tolerance.Therefore, even if when fin material etc. such as air-conditioning, the stripping etc. of film also can not be there is because of dew etc.
Monomer (a2) has contribution in the wetting ability raising of the film obtained, simultaneously give film excellence water tolerance in also play an important role.The hydroxyl being imported water-soluble polymers (A) by monomer (a2) can form crosslinking structure with from the carboxyl with the ethene base system monomer (a3) of carboxyl described later.Therefore, when being namely used in the fin material etc. of air-conditioning, the stripping etc. of film also can not be produced because of dew etc.
As the ethene base system monomer (a3) with carboxyl, the vinyl compound containing carboxyl such as (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, (methyl) vinylformic acid 2-carboxyethyl can be enumerated such as; The unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride; The half ester compound of aforementioned unsaturated acid anhydride and alkyl alcohol; And their salt etc., what can use in these is one kind or two or more.In addition, as the kind of salt, the salt same with above-mentioned monomer (a1) can be enumerated.
In above-mentioned, as the ethene base system monomer (a3) with carboxyl, good from polymerizability, set out in the aspect easily obtaining the high film of wetting ability, preferably (methyl) vinylformic acid or their salt.
The usage quantity of monomer (a3), relative to the total amount of the monomer mixture of formation water soluble resin (A), is the scope of 0.5 ~ 8 % by weight, the preferably scope of 1 ~ 7 % by weight, the more preferably scope of 2 ~ 6 % by weight.The usage quantity of monomer (a3) less than 0.5 % by weight when, because the cross-linking density of film is low, therefore its water tolerance is not enough sometimes.On the other hand, if more than 8 % by weight, the wetting ability of film becomes not enough sometimes.
Water-soluble polymers of the present invention (A), except above-mentioned monomer (a1) ~ (a3), can use can with other the ethene base system monomer (a4) of their copolymerization.
As the concrete example of other ethene base system monomer (a4), (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) isoamyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) vinylformic acid 2-methyl pentyl ester, (methyl) n-octyl, (methyl) 2-EHA, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid dodecyl ester, (methyl) acrylic acid alkyl ester compound such as (methyl) vinylformic acid Octadecane base ester, ester ring type (methyl) acrylic compound such as (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, aromatic series (methyl) acrylic compound such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, vinylbenzene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, alpha-methyl styrene, 2, the aromatic ethenyl compounds such as 4-dimethyl styrene, 2,4-di-isopropyl vinylbenzene, 4-t-butyl styrene, t-butoxystyrene, Vinyl toluene, vinyl naphthalene, styrene sulfonic acid, alpha-methyl styrene sulfonic acid, (methyl) acrylate methyl esters, (methyl) vinylformic acid diethylamino methyl esters, (methyl) vinylformic acid 2-dimethylamino ethyl ester, (methyl) vinylformic acid 2-diethylamino ethyl ester, (methyl) vinylformic acid 2-(two-n-propyl is amino) ethyl ester, (methyl) vinylformic acid 2-dimethylamino propyl ester, (methyl) vinylformic acid 2-diethylamino propyl ester, (methyl) vinylformic acid 2-(two-n-propyl is amino) propyl ester, (methyl) vinylformic acid 3-dimethylamino propyl ester, (methyl) vinylformic acid 3-diethylamino propyl ester, (methyl) vinylformic acid 3-(two-n-propyl is amino) propyl ester etc. are containing amino vinyl compound, the vinyl compound containing amido such as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, methallyl sulfonic acid, vinyl sulfonic acid etc. are containing sulfonic vinyl compound, there is the vinyl compound that (methyl) acrylate of the alcohol of polyoxyethylene groups and/or polyoxypropylene base etc. contains polyoxyalkylenes, (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(n-propoxy-) ethyl ester, (methyl) vinylformic acid 2-(n-butoxy) ethyl ester, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) vinylformic acid 3-oxyethyl group propyl ester, (methyl) vinylformic acid 2-(n-propoxy-) propyl ester, the vinyl compound containing alkoxyl group such as (methyl) vinylformic acid 2-(n-butoxy) propyl ester, (methyl) vinylformic acid cyano methyl ester, (methyl) vinylformic acid 1-cyanaoethyl methacrylate, (methyl) 2 cyanoethyl acrylate, (methyl) vinylformic acid 1-cyanopropyl acrylate, (methyl) vinylformic acid 2-cyanopropyl acrylate, (methyl) vinylformic acid 3-cyanopropyl acrylate, (methyl) vinylformic acid 4-cyanobutyl acrylate, the own ester of (methyl) vinylformic acid 6-cyano group, the own ester of (methyl) vinylformic acid 2-ethyl-6-cyano group, (methyl) vinylformic acid 8-cyano group monooctyl ester etc. has (methyl) acrylic compound of cyano group, the vinyl cyanide based compounds such as vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, the vinyl ether compounds etc. such as vinyl methyl ether, EVE, vinyl n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether, what can use in these is one kind or two or more.
In these, because the wetting ability of the film formed auxiliarily improves, therefore preferred (methyl) acrylamide.
The usage quantity of other ethene base system monomer (a4) is the scope of 0 ~ 15 % by weight, is more preferably the scope of 0 ~ 11 % by weight, more preferably the scope of 0 ~ 7 % by weight.When using more than 15 % by weight, sometimes damage the wetting ability of film, water tolerance.
After coating composition containing aforementioned water-soluble polymers (A) is coated base material, sinter, water evaporation in coating composition, drying, the hydroxyl simultaneously from monomer (a2) improves with the interaction from the carboxyl of monomer (a3).The film formed thus is insoluble in water, and the water tolerance of film improves.More than 200 DEG C left and right temperature under when coating composition sinter, by the dehydration condensation of above-mentioned hydroxyl and carboxyl, make to be cross-linked between polymkeric substance, therefore this effect becomes more remarkable.
Like this, the crosslinking reaction when import volume impact of the carboxyl in polymkeric substance and hydroxyl sinters, it is important for being therefore set in above-mentioned scope.If the usage quantity of the monomer with hydroxyl, the monomer with carboxyl is very few, then cross-linking density reduces, and the water tolerance of the hydrophilic film of formation becomes shortage.On the other hand, if the monomer with hydroxyl, there is carboxyl the usage quantity of monomer too much, the usage quantity of above-mentioned monomer (a1) reduces relatively, therefore sometimes becomes the film of wetting ability deficiency.In addition, when also comprising water-soluble polymers described later (B), same crosslinking reaction occurs expeditiously between polymer molecule, therefore obtains more excellent water tolerance.
The weight-average molecular weight (Mw) of the water-soluble polymers (A) in the present invention be 100,000 ~ 1,500,000 scope be necessary, be preferably the scope of 200,000 ~ 1,000,000, be more preferably the scope of 300,000 ~ 800,000.Weight-average molecular weight less than 100,000 when, the water tolerance of the film sometimes obtained is not enough.On the other hand, if weight-average molecular weight is more than 1,500,000, viscosity during owing to manufacturing is high, therefore worries treatability.Weight-average molecular weight can adopt gel permeation chromatography (GPC), uses the reference materials such as polyoxyethylene glycol to measure.
There is no particular restriction for the polymerization process of water-soluble polymers (A), preferred aqueous solutions polymerization.Adopt aqueous solution polymerization, the uniform solution of water-soluble polymers (A) can be obtained.
Polymer solvent during aqueous solution polymerization can use the mixed solution of water or water and organic solvent.As preferred organic solvent when using the mixed solution of water and organic solvent, can the ketones such as alcohols, acetone such as Virahol be enumerated, be particularly preferably Virahol.
In addition, in polyreaction, known polymerization starter can be used, particularly preferably use radical polymerization initiator.
As radical polymerization initiator, such as Sodium Persulfate can be enumerated, the persulfuric acid such as Potassium Persulphate and ammonium persulphate salt, the hydroperoxide type such as t-butyl hydroperoxide, the water-soluble peroxides such as hydrogen peroxide, methylethyl ketone peroxide, the peroxidation ketones such as cyclohexanone peroxide, di-t-butyl peroxide, the oil-soluble superoxide such as dialkyl such as t-butylcumyl peroxide, 2, 2 '-azo two (2-methyl-prop amidine) dihydrochloride, 2, 2 '-azo two [N-(2-carboxy ethyl)-2-methyl-prop amidine] hydrate, 2, the azo-compounds etc. such as 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide].
The radical polymerization initiator of above-mentioned peroxidation system only can use a kind, or also two or more may be used.
In the radical polymerization initiator of above-mentioned peroxidation system, from the aspect that the control of polyreaction is easily carried out, preferred persulfuric acid salt, azo-compound.
Above-mentioned radical polymerization initiator, in middle dilutions such as such as aqueous mediums, can be supplied to reactor from the supplying opening different from above-mentioned monomer.
To the usage ratio of radical polymerization initiator, there is no particular restriction, based on the total weight of whole monomers forming water-soluble polymers (A), preferably uses with the ratio of 0.01 ~ 10 % by weight, especially 0.1 ~ 5 % by weight.By making this ratio be more than 0.01 % by weight, can percent polymerization being improved, by being less than 10 % by weight, guaranteeing the stability of the polymkeric substance obtained.
In addition, water soluble, redox system polymerization starter sometimes can be used as polymerization starter manufacture.As reducto oxydative system polymerization starter, the combination of reductive agent, iron alum, the potassium alum etc. such as oxygenant (superoxide as escribed above), sodium bisulfite, ammonium bisulfite, S-WAT, V-Brite B can be enumerated.
As the polymerization temperature in the polyreaction of water-soluble polymers (A), preferably carry out in the scope of the boiling point of 65 DEG C ~ reaction system, the more preferably scope of 70 ~ 85 DEG C.
By making polymerization temperature be more than 65 DEG C, the amount of unreacted monomer can be reduced.
In polyreaction, known chain-transfer agent can be used as required.
As chain-transfer agent, such as sodium phosphite, sodium hypophosphite, sodium bisulfite, Thiovanic acid, thiohydracrylic acid, 2-propylmercaptan, 2 mercapto ethanol, thiophenol, lauryl mercaptan, thioglycerin, mercaptosuccinic acid etc. can be enumerated.
Above-mentioned chain-transfer agent only can use a kind, or two or more may be used.
In order to the pH of the reaction solution in telo merization, regulate the pH of the water-soluble polymers (A) obtained, alkaline agent (neutralizing agent) can be used.Particularly, can enumerate the organic amines etc. such as alkaline-earth metal oxyhydroxide, ammonia, Monoethanolamine MEA BASF, diethanolamine, trolamine such as the alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, what can use in these is one kind or two or more.
In these basic cpds, the alkali metal hydroxide that the generation of preferred volatile component is few, more preferably sodium hydroxide.
< water-soluble polymers (B) >
High-hydrophilic coating composition of the present invention, except above-mentioned water-soluble polymers (A), the water-soluble polymers (B) of ethene base system monomer (b1) and other ethene base system monomer (b2) copolymerization making to have carboxyl can be comprised.Comprise water-soluble polymers (B) by high-hydrophilic coating composition, the water tolerance of the film obtained can be made higher.
As the ethene base system monomer (b1) with carboxyl, the compound same with the above-mentioned ethene base system monomer (a3) with carboxyl can be enumerated.Wherein, due to the water-soluble height of polymkeric substance, the water tolerance of the film obtained is good, therefore preferably uses (methyl) vinylformic acid and their salt.In addition, as above-mentioned salt, particular certain cancers and ammonium salt.
There is the usage quantity of the ethene base system monomer (b1) of carboxyl, based on the entire infrastructure unit of water-soluble polymers (B), be the scope of 50 ~ 100 % by weight, be preferably the scope of 60 ~ 100 % by weight, be more preferably the scope of 70 ~ 100 % by weight.If the usage quantity of monomer (b1) is more than 50 % by weight, the water-soluble of water-soluble polymers (B) becomes abundant.In addition, when using metals such as aluminium as base material, obtain the film of excellent adhesion, and can solidity to corrosion be improved.
Other ethene base system monomer (b2), as long as can with monomer (b1) copolymerization, then there is no particular restriction, as its concrete example, (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) isoamyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) vinylformic acid 2-methyl pentyl ester, (methyl) n-octyl, (methyl) 2-EHA, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid Octadecane base ester, (methyl) acrylic acid alkyl ester compound such as (methyl) isobornyl acrylate, ester ring type (methyl) acrylic compound such as (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, aromatic series (methyl) acrylic compound such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, vinylbenzene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, alpha-methyl styrene, 2, the aromatic ethenyl compounds such as 4-dimethyl styrene, 2,4-di-isopropyl vinylbenzene, 4-t-butyl styrene, t-butoxystyrene, Vinyl toluene, vinyl naphthalene, styrene sulfonic acid, alpha-methyl styrene sulfonic acid, the vinyl compound containing hydroxyl such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, polyethyleneglycol (methyl) acrylate, (methyl) acrylate methyl esters, (methyl) vinylformic acid diethylamino methyl esters, (methyl) vinylformic acid 2-dimethylamino ethyl ester, (methyl) vinylformic acid 2-diethylamino ethyl ester, (methyl) vinylformic acid 2-(two-n-propyl is amino) ethyl ester, (methyl) vinylformic acid 2-dimethylamino propyl ester, (methyl) vinylformic acid 2-diethylamino propyl ester, (methyl) vinylformic acid 2-(two-n-propyl is amino) propyl ester, (methyl) vinylformic acid 3-dimethylamino propyl ester, (methyl) vinylformic acid 3-diethylamino propyl ester, (methyl) vinylformic acid 3-(two-n-propyl is amino) propyl ester etc. are containing amino vinyl compound, the vinyl compound containing amido such as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid etc. are containing sulfonic vinyl compound, there is the vinyl compound that (methyl) acrylate of the alcohol of polyoxyethylene groups and/or polyoxypropylene base etc. contains polyoxyalkylenes, (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(n-propoxy-) ethyl ester, (methyl) vinylformic acid 2-(n-butoxy) ethyl ester, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) vinylformic acid 3-oxyethyl group propyl ester, (methyl) vinylformic acid 2-(n-propoxy-) propyl ester, the vinyl compound containing alkoxyl group such as (methyl) vinylformic acid 2-(n-butoxy) propyl ester, (methyl) vinylformic acid cyano methyl ester, (methyl) vinylformic acid 1-cyanaoethyl methacrylate, (methyl) 2 cyanoethyl acrylate, (methyl) vinylformic acid 1-cyanopropyl acrylate, (methyl) vinylformic acid 2-cyanopropyl acrylate, (methyl) vinylformic acid 3-cyanopropyl acrylate, (methyl) vinylformic acid 4-cyanobutyl acrylate, the own ester of (methyl) vinylformic acid 6-cyano group, the own ester of (methyl) vinylformic acid 2-ethyl-6-cyano group, (methyl) vinylformic acid 8-cyano group monooctyl ester etc. has (methyl) acrylic compound of cyano group, the vinyl cyanide based compounds such as vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, the vinyl ether compounds etc. such as vinyl methyl ether, EVE, vinyl n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether.
In these, polymkeric substance water-soluble become good in, preferably (methyl) acrylamide and (methyl) vinylformic acid 2-hydroxy methacrylate.
Other ethene base system monomer (b2) can be used alone any one of above-mentioned each monomer, and also two or more may be used.
The usage quantity of other ethene base system monomer (b2), based on the entire infrastructure unit of water-soluble polymers (B), is the scope of 0 ~ 50 % by weight.Preferred scope is 0 ~ 40 % by weight, and preferred scope is 0 ~ 30 % by weight.If the usage quantity of monomer (b2) is less than 50 % by weight, the usage quantity of above-mentioned monomer (b1) is more than 50 % by weight, and therefore the water-soluble of water-soluble polymers (B) becomes abundant.In addition, when using metals such as aluminium as base material, obtain the film of excellent adhesion, and can solidity to corrosion be improved.
The weight-average molecular weight (Mw) of water-soluble polymers (B) is preferably the scope of 100,000 ~ 1,500,000, is more preferably the scope of 200,000 ~ 1,000,000, more preferably the scope of 300,000 ~ 800,000.If weight-average molecular weight is more than 100,000, the film of excellent water resistance can be obtained.On the other hand, if weight-average molecular weight is less than 1,500,000, owing in the range of viscosities manufacture of practicality, therefore can process and becoming easy.
The manufacture method of water-soluble polymers (B), in the same manner as above-mentioned water-soluble polymers (A), there is no particular restriction, preferred aqueous solutions polymerization.
In addition, for polymerizing conditions such as the polymerization starter used, chain-transfer agent and polymerization temperatures, the condition same with water-soluble polymers (A) can also be adopted.
In the manufacture of water-soluble polymers (B), also same with above-mentioned water-soluble polymers (A), in order to the pH of the reaction solution in telo merization, regulate the pH of the water-soluble polymers (B) obtained, alkaline agent (neutralizing agent) can be used.Particularly, can enumerate the organic amines etc. such as alkaline-earth metal oxyhydroxide, ammonia, Monoethanolamine MEA BASF, diethanolamine, trolamine such as the alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, what can use in these is one kind or two or more.
The use level of water-soluble polymers (A) and water-soluble polymers (B), with mass ratio range, for the ratio of (A)/(B)=30/70 ~ 95/5, the preferably ratio of 40/60 ~ 90/10, the more preferably ratio of 50/50 ~ 85/15.If the use level of water soluble resin (B) is (A)/(B)=more than 95/5, the film that hydrophilic persistence is high can be obtained, if be (A)/(B)=less than 30/70, the wetting ability of film can be guaranteed.
High-hydrophilic coating composition of the present invention, as required, in addition to the foregoing, can comprise known additive.As concrete additive, tensio-active agent, antiseptic-germicide, antioxidant, dyestuff, sanitas, mould inhibitor, rust-preventive agent, deodorant, solvent etc. can be enumerated.
< radiator fin for heat exchanger material >
High-hydrophilic coating of the present invention, by coating the various substrate surfaces such as metal, plastics and inorganic materials, can implement to this substrate surface the coating process adopting high-hydrophilic coating.
Such as, when using in the radiator fin for heat exchanger material etc. of air-conditioning, form the film of high-hydrophilic on this fin material surface.
Above-mentioned fin material is made up of aluminum or aluminum alloy, such as, represents by the alloy sequence number of JIS standard, can use the aluminium such as 1100,1200,1050,3003,7072.
Further, the thickness of slab of aluminium base, preferably use about 0.06 ~ 0.3mm.If thickness of slab is more than 0.06mm, the intensity needed for base material can be guaranteed.On the other hand, if be below 0.3mm, the processibility as fin material is good.
Formed on the surface of aluminium base containing above-mentioned water-soluble polymers (A) or, the hydrophilic film of the high-hydrophilic coating composition formation of above-mentioned water-soluble polymers (A) and above-mentioned water-soluble polymers (B).High-hydrophilic coating composition of the present invention, owing to himself having very high wetting ability, therefore need not coordinate alumina sol, wetting ability organic resin particulate etc. further.The wetting ability that the film display obtained is very excellent, this wetting ability of long term maintenance.In addition, even if the pollution substances such as grease are attached to fin material surface, dew etc. is utilized to be rinsed, therefore, it is possible to play the also excellent performance of pollution substance removability.
Above-mentioned fin material, according to environment for use, purposes, can form various tunicle between aluminium base and hydrophilic film.
Such as, chemical conversion treatment is carried out to aluminium base, after imposing chemical conversion tunicle, form hydrophilic film, preferred in the tack, solidity to corrosion etc. of high hydrophilization coating composition tunicle.As above-mentioned chemical conversion treatment, known method can be used, such as Plessy's green hydrochlorate process etc. can be enumerated.
High-hydrophilic coating composition of the present invention, by being coated base material, carries out drying and sintering, thus forms the high film of wetting ability at this substrate surface.Generally carry out under sintering temperature is the temperature of about 150 ~ 300 DEG C.In addition, the adhesion amount of hydrophilic film is not particularly limited, each one side of the base materials such as aluminium, is preferably 0.05 ~ 5.0g/m
2scope.By becoming this scope, the water tolerance of hydrophilic film and long-term excellent wetting ability can be maintained.In addition, 0.3 ~ 2.0g/m is more preferably
2scope.
< heat exchanger >
Manufacture method for the radiator fin for heat exchanger material that the present invention relates to is not particularly limited, such as, by for base material (or, the base material of chemical conversion tunicle etc. is defined) on surface, use coating device etc., carry out being coated with, dry, thus can hydrophilic film be formed.Further, hydrophilic film can be coated with before shaping radiator fin for heat exchanger material wait (precoating), also can be coated with after shaping radiator fin for heat exchanger material and wait (being coated with afterwards).Purposes example below for precoating, rear coating is described.
The heat exchanger of the idle call being main composition key element with pipe, radiator element etc., the structure that radiator element is made up of aluminium, effective U-shaped bend pipe made of copper etc. is formed is main body, in recent years, due to the background of the exhaustion etc. of copper resource, the material price of copper is surging, therefore carry out further cost degradation, the raising of heat exchange performance, the pursuit etc. of recirculation, also make the entirety also comprising pipe become the full aluminum heat exchanger of aluminum in research.In any case when using such U-shaped bend pipe, the general precoat material that uses manufactures heat exchanger.On the other hand, the heat exchanger of automobile etc. become welded heat exchanger, owing to being heated to the temperature of about 600 DEG C during welding, therefore thinking and can not be coated with organic envelope before welding in advance.This is because if be heated to 600 DEG C, organic envelope burns and loses or go bad.Therefore, be generally by pipe, groups of fins are dressed up the shape of heat exchanger, carry out welding and after making the shape of heat exchanger, impregnated in hydrophilic resin liquid, be coated with after forming the such what is called of hydrophilic coating film universally, carry out the formation of hydrophilic coating film.The present invention can be applied to these all purposes.
Embodiment
Based on embodiment, the present invention is specifically described below.
The Production Example of water-soluble polymers (A)
(Production Example 1)
In 2L round-bottomed flask, add pure water 500g, be held in 80 DEG C, stir.Add the pure water-soluble Sodium Persulfate 0.01g with 5g wherein.By 2-acrylamido-2-methyl propane sulfonic acid (hereinafter referred to as " ATBS ") 288g, vinylformic acid 2-hydroxy methacrylate (hereinafter referred to as " HEA ") 25.6g, vinylformic acid 6.4g, 32% aqueous sodium hydroxide solution 181g and pure water 300g are uniformly mixed, thus the modulation monomer mixture aqueous solution, make 2,2 '-azo two (2-methyl-prop amidine) dihydrochloride 0.2g is dissolved in the initiator solution in pure water 100g, lasts 3 hours simultaneously and is supplied in flask.After supply terminates, further heated and stirred 2 hours, obtains water-soluble polymers A-1.
Gel permeation chromatography (GPC) is adopted to measure the weight-average molecular weight (Mw) of water-soluble polymers A-1.The condition determination of GPC: use GPC model 2695 (manufacture of Waters society), detect and adopt RI to carry out, post employs TSK-GEL GMPWXL 7.8*300 (Dong Caoshe manufacture).Eluat is phosphoric acid buffer agent, and calibration curve uses polyoxyethylene glycol (manufacture of Polymer Laboratories society) to be made.The result measured: the Mw of A-1 is 720,000.
(Production Example 2 ~ 16)
By monomer composition (weight ratio) shown in table 1 and table 2, be polymerized in the same manner as Production Example 1, obtain water-soluble polymers A-2 ~ A-16.Further, by regulating polymerization starter amount as required, thus regulate the weight-average molecular weight of water-soluble polymers.
(comparing Production Example 1 ~ 8)
By monomer composition (weight ratio) shown in table 3, be polymerized in the same manner as Production Example 1, obtain water-soluble polymers AC-1 ~ AC-4, AC-6 and AC-8.
Further, compare Production Example 5 and compare in Production Example 7, because the polymerizability containing sulfonic monomer is poor, be therefore polymerized and do not carry out fully, fail to obtain predetermined water-soluble polymers AC-5 and AC-7.
[table 1]
[table 2]
[table 3]
The Production Example of water-soluble polymers (B)
(Production Example 17)
In 2L round-bottomed flask, add pure water 1000g, be held in 80 DEG C, stir.Add the pure water-soluble Sodium Persulfate 0.2g with 5g wherein.By AA393g and pure water 100g is uniformly mixed, thus the modulation monomer mixture aqueous solution, makes the initiator solution be dissolved in by Sodium Persulfate 0.6g in pure water 100g, last 5 hours simultaneously and be supplied in flask.After supply terminates, further heated and stirred 2 hours, obtains water-soluble polymers B-1.
(Production Example 18)
Add 25% ammoniacal liquor by the aqueous solution of water-soluble polymers B-1 that obtains in above-mentioned Production Example 17, neutralization to pH7, thus obtains water-soluble polymers B-2.
(Production Example 19,21 ~ 24)
By the composition (weight ratio) shown in table 4, be polymerized in the same manner as Production Example 17, obtain water-soluble polymers B-3, B-5 ~ B-8.
(Production Example 20)
Add 25% ammoniacal liquor by the aqueous solution of water-soluble polymers B-3 that obtains in Production Example 19, neutralization to pH7, thus obtains water-soluble polymers B-4.
[table 4]
The details of the compound used in table 1 ~ table 4 is below shown.
ATBS:2-acrylamido-2-methyl propane sulfonic acid
HAPS:3-allyloxy-2-hydroxyl-1-propanesulfonate
AA: vinylformic acid
MAA: methacrylic acid
HEA: vinylformic acid 2-hydroxy methacrylate
HEMA: 2-hydroxyethyl methacrylate
MA: methyl acrylate
AAm: acrylamide
The formation of film
With the ratio shown in table 5 by water-soluble polymers (A) and water-soluble polymers (B) mixing, modulation high-hydrophilic coating composition.
On the other hand, adopt known manufacture method, manufacture the aluminium sheet (thickness of slab 0.10mm) be made up of the A1200 of fine aluminium system (JISH4000).With alkaline reagents (Japanese ペ イ Application ト society manufactures “ サ ー Off ク リ ー ナ ー (registered trademark) 360 "), degreasing is carried out to this aluminium sheet.And then, carry out the process of Plessy's green hydrochlorate, define chemical conversion tunicle.The adhesion amount of chemical conversion tunicle converts in Cr, is 30mg/m
2.
The high-hydrophilic coating composition of above-mentioned modulation is coated with 20mg/m at aluminium sheet
2amount (amount of water soluble resin), carry out 15 minutes dry and sintering with the throughcirculation dryers of 250 DEG C, define film, it can be used as test portion.
< performance evaluation >
For the test portion obtained, following method is adopted to carry out performance evaluation.Show the result in table 5.
Wetting ability
By at room temperature the pure water of 5 μ l being dripped to the film coated surface of each test portion, measuring contact angle, thus having carried out hydrophilic evaluation.Contact angle determination device (Ying Hongjing machine society manufactures: OCA-20 type) is used to measure contact angle.Metewand is as described below.
◎ (good especially): contact angle is less than 10 °
Zero (well): contact angle is more than 10 °, less than 30 °
△ (bad): contact angle is more than 30 °, less than 50 °
× (significantly bad): contact angle is more than 50 °
Hydrophilic persistence
After each test portion is flooded 8 hours in ion exchanged water, at 80 DEG C, drying 16 hours, using such operation as 1 circulation, has carried out 10 circulations.Then, make test portion return room temperature, the pure water of the 5 μ l that drip on surface, measures contact angle as described above.Metewand is as described below.
◎ (good especially): contact angle is less than 10 °
Zero (well): contact angle is more than 10 °, less than 30 °
△ (bad): contact angle is more than 30 °, less than 50 °
× (significantly bad): contact angle is more than 50 °
Pollution substance removability
As pollution substance, the bottom of the moisture eliminator of the capacity with 6 liters will be put into as the stearic acid 1g of preventing hydration material, the test film of the 5cm × 10cm cut out from above-mentioned each test portion that plays on the top of this reagent.Then, after moisture eliminator being heated 24 hours at 100 DEG C, after letting cool room temperature, test film is taken out, flood 1 minute in pure water, at room temperature dry.After above operation repeatedly 10 times, measure contact angle.Metewand is as described below.
◎ (good especially): contact angle is less than 20 °
Zero (well): contact angle is more than 20 °, less than 40 °
△ (bad): contact angle is more than 40 °, less than 60 °
× (significantly bad): contact angle is more than 60 °
[table 5]
The film obtained in embodiment 1 ~ 30 all shows excellent wetting ability and pollution substance removability.In addition, this wetting ability also maintains good level after the dipping repeatedly carried out in ion exchanged water and drying, and expectation can maintain above-mentioned performance chronically.
On the other hand, in the comparative example 1 of the few water-soluble polymers AC-1 of the usage quantity employing monomer (a1) as water-soluble polymers (A), result is that hydrophilic persistence and pollution substance removability are not enough.Comparative example 2 and 3 is examples of situation (comparative example 2) that the usage quantity with the ethene base system monomer (a2) of hydroxyl in water-soluble polymers (A) is fewer than the scope specified in the present invention and many situations (comparative example 3), is that hydrophilic persistence and pollution substance removability are poor equally.In addition, the hydrophilic persistence of comparative example 4 of water-soluble polymers AC-4 employed in structural unit not containing the ethene base system monomer (a3) with carboxyl is not enough.
And then, as the sulfonic acid monomer forming water-soluble polymers (A), when employing the monomer beyond 2-acrylamido-2-methyl propane sulfonic acid, because its reactivity is low, therefore must reduce usage quantity, result fails to give sufficient wetting ability (comparative example 5 and 6) to film.
Industry utilizes possibility
High-hydrophilic coating composition of the present invention, can form the high film of wetting ability, above-mentioned its wetting ability of film long term maintenance on the surface of metal, plastics and inorganic materials (glass etc.).Therefore, can be used as the coating agent of the radiator fin for heat exchanger material for these various base material, particularly air-conditionings etc.
Claims (6)
1. high-hydrophilic coating composition, it contains water-soluble polymers (A), this water-soluble polymers (A) is based on all forming monomer, by making 2-acrylamido-2-methyl propane sulfonic acid or its salt (a1) 80 ~ 94.5 % by weight, have the ethene base system monomer (a2) 4 ~ 15 % by weight of hydroxyl, have the ethene base system monomer (a3) 0.5 ~ 8 % by weight of carboxyl and other ethene base system monomer (a4) 0 ~ 15 % by weight copolymerization and the polymkeric substance that obtains, weight-average molecular weight is 100,000 ~ 1,500,000.
2. high-hydrophilic coating composition, it is characterized in that, it is the high-hydrophilic coating composition containing above-mentioned water-soluble polymers (A) and water-soluble polymers (B), the weight ratio of above-mentioned water-soluble polymers (A) and above-mentioned water-soluble polymers (B) is the ratio of (A)/(B)=30/70 ~ 95/5, above-mentioned water-soluble polymers (B) is based on all forming monomer, the polymkeric substance obtained by making to have the ethene base system monomer (b1) 50 ~ 100 % by weight of carboxyl and other ethene base system monomer (b2) 0 ~ 50 % by weight copolymerization, weight-average molecular weight is 100,000 ~ 1,500,000.
3. radiator fin for heat exchanger material, it has the hydrophilic film formed by high-hydrophilic coating composition according to claim 1 on the base material be made up of aluminum or aluminum alloy.
4. radiator fin for heat exchanger material, it has the hydrophilic film formed by high-hydrophilic coating composition according to claim 2 on the base material be made up of aluminum or aluminum alloy.
5. heat exchanger, it uses radiator fin for heat exchanger material according to claim 3.
6. heat exchanger, it uses radiator fin for heat exchanger material according to claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014020856A JP6316612B2 (en) | 2014-02-06 | 2014-02-06 | Highly hydrophilic coating composition and use thereof |
| JP2014-020856 | 2014-09-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104830193A true CN104830193A (en) | 2015-08-12 |
| CN104830193B CN104830193B (en) | 2019-02-22 |
Family
ID=53808403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510046587.4A Active CN104830193B (en) | 2014-02-06 | 2015-01-29 | High-hydrophilic coating composition and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6316612B2 (en) |
| CN (1) | CN104830193B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634389A (en) * | 2016-12-30 | 2017-05-10 | 广州慧谷化学有限公司 | Coating for preparing lubricating hydrophilic coating and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6215990B2 (en) * | 2016-03-18 | 2017-10-18 | 株式会社神戸製鋼所 | Aluminum fin material |
| US11279833B2 (en) * | 2017-03-23 | 2022-03-22 | Tokyo Ohka Kogyo Co., Ltd. | Surface treatment liquid and surface treatment method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10218909A (en) * | 1997-02-03 | 1998-08-18 | Toyo Ink Mfg Co Ltd | Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating material |
| JPH1123174A (en) * | 1997-06-30 | 1999-01-26 | Mitsubishi Alum Co Ltd | Heat exchange material |
| WO2002031010A1 (en) * | 2000-10-13 | 2002-04-18 | Kansai Paint Co., Ltd. | Resin for pigment dispersion |
| CN101591494A (en) * | 2009-07-03 | 2009-12-02 | 北京瑞博奥生物科技有限公司 | A kind of antifogging coating and special-purpose anti fogging coating composite and antifog article |
| CN102924662A (en) * | 2012-06-21 | 2013-02-13 | 江南大学 | Anti-fog type ultraviolet light curing polyacrylate copolymer preparation method |
| CN104559610A (en) * | 2013-12-20 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | Organic hydrophilic coating for air conditioner aluminum foil and preparation method of organic hydrophilic coating |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3225793B2 (en) * | 1995-06-16 | 2001-11-05 | 東洋インキ製造株式会社 | Highly hydrophilic paint |
| JPH09169946A (en) * | 1995-12-20 | 1997-06-30 | Mitsui Toatsu Chem Inc | Surface coating agent and its utilization |
| JP3403906B2 (en) * | 1996-12-06 | 2003-05-06 | 東洋インキ製造株式会社 | Manufacturing method of highly hydrophilic paint |
-
2014
- 2014-02-06 JP JP2014020856A patent/JP6316612B2/en active Active
-
2015
- 2015-01-29 CN CN201510046587.4A patent/CN104830193B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10218909A (en) * | 1997-02-03 | 1998-08-18 | Toyo Ink Mfg Co Ltd | Organic/inorganic composite particle, coating material containing the same and aluminum fin material coated with the coating material |
| JPH1123174A (en) * | 1997-06-30 | 1999-01-26 | Mitsubishi Alum Co Ltd | Heat exchange material |
| WO2002031010A1 (en) * | 2000-10-13 | 2002-04-18 | Kansai Paint Co., Ltd. | Resin for pigment dispersion |
| CN101591494A (en) * | 2009-07-03 | 2009-12-02 | 北京瑞博奥生物科技有限公司 | A kind of antifogging coating and special-purpose anti fogging coating composite and antifog article |
| CN102924662A (en) * | 2012-06-21 | 2013-02-13 | 江南大学 | Anti-fog type ultraviolet light curing polyacrylate copolymer preparation method |
| CN104559610A (en) * | 2013-12-20 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | Organic hydrophilic coating for air conditioner aluminum foil and preparation method of organic hydrophilic coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634389A (en) * | 2016-12-30 | 2017-05-10 | 广州慧谷化学有限公司 | Coating for preparing lubricating hydrophilic coating and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104830193B (en) | 2019-02-22 |
| JP2015147852A (en) | 2015-08-20 |
| JP6316612B2 (en) | 2018-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2862634B1 (en) | Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger | |
| CN100467502C (en) | Water-based emulsion for vibration damper | |
| JP6618903B2 (en) | Method for coating hydrophilic film on aluminum fin material, aluminum fin material and aluminum heat exchanger | |
| JPH01270977A (en) | Hydrophilic treatment of aluminum | |
| CN104830193A (en) | High hydrophilic coating composition and use thereof | |
| JP6654814B2 (en) | Hydrophilizing agent, hydrophilic film forming method and hydrophilic film | |
| JP2018023932A (en) | Hydrophilic film coating method of aluminum fin material, aluminum fin material, and heat-exchanger made of aluminum | |
| JPH02219876A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| CN113226571B (en) | Hydrophilizing agent, method for forming hydrophilic coating film, and hydrophilic coating film | |
| JP2507070B2 (en) | Method for hydrophilizing aluminum fin coil material | |
| JP2002012729A (en) | Water soluble resin composition | |
| JP5399607B2 (en) | Non-adhesive water-based undercoat material for leather | |
| JPH02219877A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JPH02219875A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JPH02219873A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| KR100497516B1 (en) | A hydrophilic composition of organic type using hydrophilic handling the surface aluminium and it's manufacturing method | |
| JPH0726461A (en) | Binder for nonwoven fabric | |
| JP2005075841A (en) | Coating composition for fin and fin material | |
| JP2003221555A (en) | Coating agent | |
| JPH02219874A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JPH02219879A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JP2525378B2 (en) | Resin composition for surface treatment | |
| JP2009286865A (en) | Vinylpyrrolidone copolymer and hydrophilizing agent composition using the same | |
| JPH02219878A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JP2004331693A (en) | Hydrophilic surface treating agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |