CN104830193B - High-hydrophilic coating composition and application thereof - Google Patents
High-hydrophilic coating composition and application thereof Download PDFInfo
- Publication number
- CN104830193B CN104830193B CN201510046587.4A CN201510046587A CN104830193B CN 104830193 B CN104830193 B CN 104830193B CN 201510046587 A CN201510046587 A CN 201510046587A CN 104830193 B CN104830193 B CN 104830193B
- Authority
- CN
- China
- Prior art keywords
- methyl
- water
- weight
- soluble polymer
- acrylic acid
- 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.)
- Active
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]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Combustion & Propulsion (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
High-hydrophilic coating composition of the invention contain make 2- acrylamido -2- methyl propane sulfonic acid (salt), the vinyl monomer with hydroxyl and the vinyl monomer with carboxyl copolymerization obtained from water solubility copolymer.In addition, radiator fin for heat exchanger of the invention has the hydrophilic film formed using above-mentioned high-hydrophilic coating composition on the surface of metal cooling fin component.
Description
Technical field
The present invention relates to high-hydrophilic coating compositions and application thereof.Specifically, being related on the surface of various substrates etc.
Formed, substrate can be given hydrophily, excellent adhesion film above-mentioned high-hydrophilic coating composition and have by
Radiator fin for heat exchanger (fin) material for the hydrophilic film that the high-hydrophilic coating composition is formed and the heat for having used it
Exchanger.
Background technique
For the radiator fin for heat exchanger material of air-conditioning etc., from the viewpoint of thermal conductivity, processability and lightweight, mainly
Aluminum or aluminum alloy is used.
If heat exchanger is made to work, on fin material surface, the water vapour in air is cooled and condenses, and becomes knot
Dew.But for the reason of the miniaturization of heat exchanger, the raising thermal efficiency etc., fin material is configured with narrow interval,
Therefore dew deposits between adjacent cooling fin sometimes, thus makes to occlude between cooling fin.As a result, generating the increasing of ventilation resistance
The problems such as ability of heat exchanger caused by adding reduces, dew caused by wind pressure disperses to outside air conditioner.This is asked in order to prevent
Topic, develops following technologies: making fin material surface hydrophilic using high-hydrophilic coating etc., cold on fin material surface
Solidifying water does not deposit, and is easy as draining outflow.
But due to the process during use environment and use, various pollutants matter is adhered on fin material surface etc.,
Therefore the hydrophily on surface reduces, and cannot fully show the function of setting originally sometimes.It therefore, will using high-hydrophilic coating
In the case where substrate surface hydrophiling, it is desirable that it is adequately hydrophilic simultaneously in imparting, it also maintains in long-term use hydrophilic
Property.
In order to cope with above-mentioned requirements, propose the pollutant of attachment using the condensed water generated on fin material surface
Matter removes, with the so-called high-hydrophilic coating from detergency.For example, disclosing in patent document 1 and having used alumina sol
High-hydrophilic coating.But even if, due to the environment used, various spot attachments, lose original sometimes using this method
Function.Particularly, insoluble grease type (oil droplet generated when floor wax, conditioning) in water, if being attached to film coated surface
It is then not easy to fall off.
The surface treating agent using hydrophily organic resin particle as principal component is disclosed in patent document 2, describes dirt
Also there is excellent hydrophily after contaminating substance attachment.It is to be formed concave-convex in film coated surface and increase the contact area with water, is mentioned
The gimmick of high-hydrophilic, but compared with smooth film, have indent and convex film gap stink odor easy to attach therebetween, anti-
Only the aspect of polluter attachment has improved necessity.
On the other hand, it proposes and several chronically maintains excellent hydrophilic technology with smooth film.For example, patent
Coating composition is disclosed in document 3, it is hydrophilic made of using will have the copolymerization of the monomer of carboxyl and hydroxyl and acylamino-
Property resin and surface treating agent of the hydrophilic resin as principal component with ether.Further, since will have sulfonic list
Hydrophilic resin made of body copolymerization has excellent initial hydrophilicity, thus discloses several coating using it as principal component
Composition (patent document 4~6).
Existing technical literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 10-168381 bulletin
Patent document 2: special open 2009-179811 bulletin
Patent document 3: special open 2005-75841 bulletin
Patent document 4: special open 2010-159379 bulletin
Patent document 5: special open 2012-72336 bulletin
Patent document 6: special open 2012-122052 bulletin
Summary of the invention
Subject to be solved by the invention
But the hydrophilic resin recorded in patent document 3, hydrophily is low, cannot individually show sufficient hydrophily.
In addition, there are following problems for the polyethylene glycol added to improve hydrophily: being easily flowed out due to condensed water, after dissolution
Hydrophily is greatly lowered.
In addition, the hydrophilic coating recorded in patent document 4~6 is utilized due to that can assign excellent hydrophily
The stain resistance from detergency that condensed water generates is also excellent, but since hydrophilic duration is insufficient, maintains resistant for a long time
The performances such as metachromia are difficult.
The present invention in view of such actual situation completes, and project is to provide coating composition and have by the painting
The radiator fin for heat exchanger material for the high-hydrophilic film that feed composition is formed and the heat exchanger for having used it, the coating group
Object is closed in the case where the coating of the substrate surface of radiator fin for heat exchanger material etc., even if being formed has the polluters such as grease
It is attached to excellent hydrophily that surface also utilizes dew to be rinsed, maintains the hydrophilic film for a long time.
Means for solving the problems
In order to solve the above problems, inventors believe that compared with the hydrophilic film formed by existing coating composition
Show higher hydrophily and water resistance (hydrophilic duration) that its film also has will not dissolve out etc. because of dew etc. at
To maintain excellent hydrophilic important document for a long time.
The present inventor has made intensive studies for obtaining the high-hydrophilic coating composition of above-mentioned such film, as a result
It was found that: it utilizes containing the water-soluble polymer made of the monomer mixture comprising specific sulfonic acid monomer more than specified amount
Coating composition is able to solve the above subject, completes the present invention.
That is, first invention is high-hydrophilic coating composition, contain water-soluble polymer (A), the water-soluble polymer
It (A) is based on all composition monomers, by making 2- acrylamido -2- methyl propane sulfonic acid or its 80~94.5 weight of salt (a1)
Measure %, 4~15 weight % of vinyl monomer (a2) with hydroxyl, 0.5~8 weight of vinyl monomer (a3) with carboxyl
Measure polymer obtained from % and others vinyl monomer (a4) 0~15 weight % copolymerization, weight average molecular weight for 100,000~
1500000.
Second invention is high-hydrophilic coating composition, which is characterized in that is containing above-mentioned water-soluble polymer (A) and water
The weight ratio of the high-hydrophilic coating composition of soluble polymer (B), water-soluble polymer (A) and water-soluble polymer (B) is
(A)/(B)=30/70~95/5 ratio, above-mentioned water-soluble polymer (B) are based on all composition monomers, by making with carboxylic
50~100 weight % of vinyl monomer (b1) and others vinyl monomer (b2) 0~50 weight % of base are copolymerized and obtain
The polymer arrived, weight average molecular weight are 100,000~1,500,000.
Third invention is radiator fin for heat exchanger material, is had on the substrate made of aluminum or aluminum alloy by first
Or second hydrophilic film that is formed of high-hydrophilic coating composition described in invention.
4th invention is heat exchanger, and it uses radiator fin for heat exchanger materials described in third invention.
The effect of invention
High-hydrophilic coating composition in the present invention is coated on to the substrate surface of radiator fin for heat exchanger material etc.
In the case where, contained with height ratio from sulfonic 2- acrylamido -2- methyl-prop in the film that the surface is formed
The hydrophilic functional group of sulfonic acid or its salt, therefore show very high hydrophily.In addition, even if the polluters such as grease are in its table
In the case that face is adhered to, since the hydrophily of film is very high, condensed water easy to use etc. is removed.On the other hand,
Film itself has sufficient water resistance, therefore chronically maintain to assign fin material due to that will not dissolve out in condensed water etc.
Expect the hydrophily on surface.
Specific embodiment
Below to the detailed description of the invention.Further more, in this specification, " (methyl) acrylic acid " mean acrylic acid and/or
Methacrylic acid, " (methyl) acrylate " mean acrylate and/or methacrylate.In addition, " (methyl) acryloyl
Base " means acryloyl group and/or methylacryloyl.
<water-soluble polymer (A)>
Water-soluble polymer (A) of the invention is based on all constituting monomer, by making 2- acrylamido -2- methyl-prop sulphur
Acid or 80~94.5 weight % of its salt (a1), 4~15 weight % of vinyl monomer (a2) with hydroxyl, the second with carboxyl
Alkenyl system monomer (a3) 0.5~8 weight % and others vinyl monomer (a4) 0~15 weight % copolymerization obtains.
As described above, water-soluble polymer (A) is using 2- acrylamido -2- methyl propane sulfonic acid or its salt (a1) as structure
Unit.
In order to assign excellent hydrophily to the film formed in substrate surface, it is believed that in the basic tree of coating composition
It is effective for importing sulfonic group in rouge with high containing ratio.But generally, having sulfonic monomer is mostly that polymerism is low,
In the case that the use ratio of such monomer is high, there is the molecular weight of the polymer that cannot make fully high tendency.
Therefore, sometimes be coated with coating composition when coating adaptability, the water resistance of obtained film deficiency.
But as with sulfonic monomer, having used 2- acrylamido -2- methyl propane sulfonic acid or its salt (a1)
In the case of, even if can also obtain the sufficiently high polymer of molecular weight in the case that their ratio is high in monomer mixture.Cause
This, solves the above subject as coating adaptability and the water resistance of obtained film and is possibly realized.
The usage amount of 2- acrylamido -2- methyl propane sulfonic acid or its salt (a1) in water-soluble polymer (A), relative to
The total amount of the monomer mixture of water-soluble polymer (A) is constituted, is the range of 80~94.5 weight %, preferably 82~94 weights
Measure %, the more preferably range of 86~93 weight %.
In the case that the usage amount of 2- acrylamido -2- methyl propane sulfonic acid or its salt (a1) is less than 80 weight %, sometimes
The hydrophily of obtained film and hydrophilic duration become insufficient.On the other hand, if it exceeds 94.5 weight %, due to aftermentioned
The usage amount of monomer (a2) with hydroxyl and/or the vinyl monomer (a3) with carboxyl is insufficient, therefore is unable to get sometimes
The film of excellent water resistance.
As the salt of 2- acrylamido -2- methyl propane sulfonic acid, the alkali metal salts such as lithium salts, sodium salt, sylvite, magnesium can be enumerated
The alkali earth metal salts such as salt, calcium salt and ammonium salt etc. are able to use one kind or two or more in these.
As (a1), preferably 2- acrylamido -2- methyl propane sulfonic acid or its sodium salt, wherein from the parent of obtained film
It is aqueous to become higher aspect and set out, it is preferable to use sodium salt.
As the vinyl monomer (a2) with hydroxyl, it can be mentioned, for example (methyl) acrylic acid 2- hydroxy methacrylates, (first
Base) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, polyethyleneglycol (methyl) acrylate, N- methylol
(methyl) acrylamide etc. is able to use one kind or two or more in these.Wherein, as the vinyl monomer with hydroxyl
(a2), from being easy to get the high film aspect of hydrophily, preferably (methyl) acrylic acid 2- hydroxy methacrylate.
The usage amount of monomer (a2) is 4~15 relative to the total amount for the monomer mixture for constituting water-soluble polymer (A)
The range of weight %, the preferably range of 5~11 weight %, the more preferably range of 6~9 weight %.The use of monomer (a2)
In the case that amount is less than 4 weight %, since the crosslink density of film is low, its water resistance is insufficient sometimes.On the other hand, if
More than 15 weight %, it is unable to get film for a long time with excellent hydrophily and water resistance sometimes.
By using monomer (a2) in the structural unit of water-soluble polymer (A), the film being coated with is having
Have and also has excellent water resistance while high-hydrophilic.Therefore, even if the situation such as the fin material for air-conditioning
Under, the dissolution etc. of film will not occur because of dew etc..
Monomer (a2) contributes in terms of the hydrophily raising of obtained film, while assigning film excellent water resistance
Aspect also play an important role.By monomer (a2) import water-soluble polymer (A) hydroxyl can with from aftermentioned
The vinyl monomer (a3) with carboxyl carboxyl formed cross-linked structure.Therefore, that is, it is used in the fin material of air-conditioning
Deng in the case where, the dissolution etc. of film will not be generated because of dew etc..
As the vinyl monomer (a3) with carboxyl, it can be mentioned, for example (methyl) acrylic acid, itaconic acid, maleic acid,
The vinyl compounds containing carboxyl such as fumaric acid, crotonic acid, (methyl) acrylic acid 2- carboxyethyl；Maleic anhydride, clothing health
The unsaturated acid anhydrides such as acid anhydrides, citraconic anhydride；The half ester compound of aforementioned unsaturated acid anhydride and alkylol；And their salt etc.,
It is able to use one kind or two or more in these.In addition, the type as salt, can enumerate the same salt with above-mentioned monomer (a1).
Among the above, good from polymerism as the vinyl monomer (a3) with carboxyl, it is easy to get the high painting of hydrophily
It sets out in terms of film, preferably (methyl) acrylic acid or their salt.
The usage amount of monomer (a3) is 0.5~8 weight relative to the total amount for the monomer mixture for constituting water-soluble resin (A)
Measure the range of %, the preferably range of 1~7 weight %, the range of more preferable 2~6 weight %.The usage amount of monomer (a3) less than
In the case where 0.5 weight %, since the crosslink density of film is low, its water resistance is insufficient sometimes.On the other hand, if it exceeds
8 weight %, the hydrophily of film becomes insufficient sometimes.
Water-soluble polymer (A) of the invention, other than above-mentioned monomer (a1)~(a3), being able to use can be total with them
Poly- other vinyl monomers (a4).
As the concrete example of other vinyl monomers (a4), (methyl) methyl acrylate, (methyl) propylene can be enumerated
Acetoacetic ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid
Isobutyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid
Isopentyl ester, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid 2- methyl pentyl ester, (methyl) n-octyl, (methyl) third
Olefin(e) acid 2- ethylhexyl, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) acrylic acid n-dodecane base ester, (methyl) acrylic acid positive 18
Arrcostab etc. (methyl) acrylic acid alkyl ester compound；The rouge such as (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate
Ring type (methyl) acrylate compounds；(methyl) phenyl acrylate, (methyl) benzyl acrylate etc. aromatic series (methyl) propylene
Ester compound；Styrene, 2-methyl styrene, 3- methyl styrene, 4- methyl styrene, α-methylstyrene, 2,4- bis-
Methyl styrene, 2,4- diisopropyl styrene, 4- t-butyl styrene, t-butoxystyrene, vinyltoluene, vinyl
The aromatic ethenyl compounds such as naphthalene, styrene sulfonic acid, α-methylstyrene sulfonic acid；(methyl) acrylate first
Ester, (methyl) acrylic acid diethylamino methyl esters, (methyl) acrylic acid 2- dimethylamino ethyl ester, (methyl) acrylic acid 2- diethyl
Base amino ethyl ester, (methyl) acrylic acid 2- (two-n-propyl aminos) ethyl ester, (methyl) acrylic acid 2- dimethylamino propyl ester, (first
Base) acrylic acid 2- diethylamino propyl ester, (methyl) acrylic acid 2- (two-n-propyl aminos) propyl ester, (methyl) acrylic acid 3- bis-
Methylamino propyl ester, (methyl) acrylic acid 3- diethylamino propyl ester, (methyl) acrylic acid 3- (two-n-propyl aminos) propyl ester etc.
Vinyl compound containing amino；(methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- dimethylamino
The vinyl compounds containing acylamino- such as propyl (methyl) acrylamide；Methallyl sulfonic acid, vinyl sulfonic acid etc. contain
Sulfonic vinyl compound；(methyl) acrylate of alcohol with polyoxyethylene groups and/or polyoxypropylene base etc. contains
The vinyl compound of polyoxyalkylenes；(methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester,
(methyl) acrylic acid 2- (n-propoxy) ethyl ester, (methyl) acrylic acid 2- (n-butoxy) ethyl ester, (methyl) acrylic acid 3- first
Oxygroup propyl ester, (methyl) acrylic acid 3- ethyoxyl propyl ester, (methyl) acrylic acid 2- (n-propoxy) propyl ester, (methyl) acrylic acid
The vinyl compounds containing alkoxy such as 2- (n-butoxy) propyl ester；(methyl) acrylic acid cyano methyl ester, (methyl) acrylic acid
1- cyanaoethyl methacrylate, (methyl) 2 cyanoethyl acrylate, (methyl) acrylic acid 1- cyanopropyl acrylate, (methyl) acrylic acid 2- cyano third
Ester, (methyl) acrylic acid 3- cyanopropyl acrylate, (methyl) acrylic acid 4- cyanobutyl acrylate, the own ester of (methyl) acrylic acid 6- cyano, (first
Base) (methyl) acroleic acid esterification with cyano such as the own ester of acrylic acid 2- ethyl -6- cyano, (methyl) acrylic acid 8- cyano monooctyl ester
Close object；The vinyl cyanides based compound such as acrylonitrile, methacrylonitrile, ethyl acrylonitrile；Vinyl methyl ether, vinyl ethyl
Vinyl ether compounds such as ether, vinyl n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether etc., are able to use these
In it is one kind or two or more.
In these, since the hydrophily of the film of formation auxiliarily improves, preferred (methyl) acrylamide.
The usage amount of other vinyl monomers (a4) is the range of 0~15 weight %, more preferably 0~11 weight
Measure the range of %, the further preferably range of 0~7 weight %.In the case where more than 15 weight % uses, film is damaged sometimes
Hydrophily, water resistance.
After coating composition containing aforementioned water-soluble polymer (A) is coated on substrate, it is sintered, coating composition
In water evaporation, drying, be simultaneously from the hydroxyl of monomer (a2) and the interaction of the carboxyl from monomer (a3) improve.Thus
The film of formation is insoluble in water, and the water resistance of film improves.200 DEG C or more Zuo You at a temperature of coating composition burnt
In the case where knot, by the dehydration condensation of above-mentioned hydroxyl and carboxyl, make to be crosslinked between polymer, therefore the effect becomes more
It is significant.
In this way, the import volume of carboxyl and hydroxyl in polymer influences cross-linking reaction when being sintered, therefore it is set in above-mentioned
Range be important.If the usage amount of the monomer with hydroxyl, the monomer with carboxyl is very few, crosslink density is reduced,
The water resistance of the hydrophilic film of formation becomes to lack.On the other hand, if monomer with hydroxyl, the monomer with carboxyl
Usage amount is excessive, and the usage amount of above-mentioned monomer (a1) is opposite to be reduced, therefore becomes the insufficient film of hydrophily sometimes.In addition, also
In the case where comprising aftermentioned water-soluble polymer (B), same cross-linking reaction expeditiously occurs between polymer molecule, because
This obtains superior water resistance.
The range that the weight average molecular weight (Mw) of water-soluble polymer (A) in the present invention is 100,000~1,500,000 is necessary,
Preferably 200,000~1,000,000 range, more preferably 300,000~800,000 range.In the case that weight average molecular weight is less than 100,000,
Sometimes the water resistance of the film obtained is insufficient.On the other hand, the viscosity if weight average molecular weight is more than 1,500,000, when due to manufacture
Height, therefore worry treatability.Weight average molecular weight can use gel permeation chromatography (GPC), use the standard substances such as polyethylene glycol
Measurement.
There is no particular restriction for the polymerization of water-soluble polymer (A), preferred aqueous solutions polymerization.It is poly- using aqueous solution
It closes, the uniform solution of water-soluble polymer (A) can be obtained.
Polymer solvent when aqueous solution polymerization is able to use the mixed liquor of water or water and organic solvent.As use water and
Preferred organic solvent when the mixed liquor of organic solvent can enumerate the ketones such as the alcohols such as isopropanol, acetone, particularly preferably different
Propyl alcohol.
In addition, being able to use well known polymerization initiator in polymerization reaction, particularly preferably being caused using free radical polymerization
Agent.
As radical polymerization initiator, it can be mentioned, for example the persulfates such as sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate
The water-soluble peroxides such as the hydroperoxide types such as class, t-butyl hydroperoxide, hydrogen peroxide, methyl ethyl ketone peroxide, peroxidating
The oil-soluble mistakes such as the dialkyls such as the peroxidating such as cyclohexanone ketone, di-t-butyl peroxide, t-butylcumyl peroxide
Oxide, 2,2 '-azo two (2- methyl-prop amidine) dihydrochlorides, 2,2 '-azos two [N- (2- carboxy ethyl) -2- methyl-prop amidine]
Azo-compounds such as hydrate, 2,2 '-azos two [2- methyl-N- (2- hydroxyethyl) propionamide] etc..
The radical polymerization initiator of above-mentioned peroxide system can only use a kind, or also two or more may be used.
In the radical polymerization initiator of above-mentioned peroxide system, go out in terms of the control of polymerization reaction is easy to perform
Hair, preferably persulfuric acid salt, azo-compound.
Above-mentioned radical polymerization initiator can dilute in such as aqueous medium etc., from the confession different from above-mentioned monomer
Reactor is given to confession.
To the use ratio of radical polymerization initiator, there is no particular restriction, based on constituting the complete of water-soluble polymer (A)
Total weight of portion's monomer, preferably with 0.01~10 weight %, particularly 0.1~5 weight % ratio use.By making the ratio
Example be 0.01 weight % or more, can be improved aggregate rate, by making its 10 weight % or less, it is ensured that obtained polymer it is steady
It is qualitative.
In addition, water soluble, redox system polymerization initiator can be used to manufacture as polymerization initiator sometimes.As oxidation
Reduction is polymerization initiator, can enumerate oxidant (peroxide as escribed above), sodium hydrogensulfite, ammonium bisulfite, sulfurous
The combination of the reducing agents such as sour sodium, sodium dithionite, iron alum, potassium alum etc..
As the polymerization temperature in the polymerization reaction of water-soluble polymer (A), preferably in the boiling point of 65 DEG C~reaction system
Range carries out, more preferable 70~85 DEG C of range.
By making 65 DEG C of polymerization temperature or more, the amount of unreacted monomer can be reduced.
In polymerization reaction, well known chain-transferring agent can be used as needed.
As chain-transferring agent, it can be mentioned, for example sodium phosphite, sodium hypophosphite, sodium hydrogensulfite, thioacetic acid, sulfydryls third
Acid, 2- propanethiol, 2 mercapto ethanol, benzenethiol, lauryl mercaptan, thioglycerol, thiomalic acid etc..
Above-mentioned chain-transferring agent can only use a kind, or two or more may be used.
For the pH of the reaction solution in telo merization, alkali is can be used in the pH of the water-soluble polymer (A) adjusted
Agent (neutralizer).Specifically, the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide etc. can be enumerated
Organic amines such as alkaline-earth metal hydroxide, ammonia, monoethanolamine, diethanol amine, triethanolamine etc., are able to use in these
It is one kind or two or more.
In these alkali compounds, the few alkali metal hydroxide of the generation of preferably volatile ingredient, more preferable sodium hydroxide.
<water-soluble polymer (B)>
High-hydrophilic coating composition of the invention may include making with carboxylic other than above-mentioned water-soluble polymer (A)
Water-soluble polymer (B) made of the vinyl monomer (b1) of base and other vinyl monomers (b2) are copolymerized.Pass through height
Hydrophilic coating compositions include water-soluble polymer (B), and the water resistance of the film enabled to is higher.
As the vinyl monomer (b1) with carboxyl, can enumerate and the above-mentioned vinyl monomer with carboxyl
(a3) same compound.Wherein, due to the high water solubility of polymer, the water resistance of obtained film is good, therefore preferably makes
With the salt of (methyl) acrylic acid and they.In addition, as above-mentioned salt, particular certain cancers and ammonium salt.
The usage amount of vinyl monomer (b1) with carboxyl is based on the entire infrastructure unit of water-soluble polymer (B),
For the range of 50~100 weight %, the preferably range of 60~100 weight %, the more preferably range of 70~100 weight %.
If the usage amount of monomer (b1) is 50 weight % or more, the water solubility of water-soluble polymer (B) becomes abundant.In addition, with aluminium
In the case that equal metals are as substrate, the film of excellent adhesion is obtained, and can be improved corrosion resistance.
Other vinyl monomers (b2), as long as can be copolymerized with monomer (b1), there is no particular restriction, specific as it
Example, it is different can to enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid
Propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) acrylic acid uncle
Butyl ester, (methyl) acrylic acid n-pentyl ester, (methyl) isoamyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid 2-
Methyl pentyl ester, (methyl) n-octyl, (methyl) 2-EHA, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl)
(methyl) propylene such as acrylic acid n-dodecane base ester, (methyl) acrylic acid n-octadecane base ester, (methyl) isobornyl acrylate
Acid alkyl ester compound；(methyl) cyclohexyl acrylate, (methyl) phenyl acrylate etc. ester ring types (methyl) acrylate chemical combination
Object；(methyl) phenyl acrylate, (methyl) benzyl acrylate etc. aromatic series (methyl) acrylate compounds；Styrene, 2- first
Base styrene, 3- methyl styrene, 4- methyl styrene, α-methylstyrene, 2,4- dimethyl styrene, 2,4- diisopropyl
Styrene, 4- t-butyl styrene, t-butoxystyrene, vinyltoluene, vinyl naphthalene, styrene sulfonic acid, Alpha-Methyl benzene
The aromatic ethenyl compounds such as vinyl sulfonic acid；(methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester,
The vinyl compounds containing hydroxyl such as (methyl) acrylic acid 4- hydroxybutyl, polyethyleneglycol (methyl) acrylate；(first
Base) acrylate methyl esters, (methyl) acrylic acid diethylamino methyl esters, (methyl) acrylic acid 2- dimethylaminoethyl
Ester, (methyl) acrylic acid 2- diethylamino ethyl ester, (methyl) acrylic acid 2- (two-n-propyl aminos) ethyl ester, (methyl) propylene
Sour 2- dimethylamino propyl ester, (methyl) acrylic acid 2- diethylamino propyl ester, (methyl) acrylic acid 2- (two-n-propyl aminos)
Propyl ester, (methyl) acrylic acid 3- dimethylamino propyl ester, (methyl) acrylic acid 3- diethylamino propyl ester, (methyl) acrylic acid 3-
The vinyl compounds containing amino such as (two-n-propyl aminos) propyl ester；(methyl) acrylamide, N, N- dimethyl (methyl) third
Acrylamide, N, the vinyl compound containing acylamino- such as N- dimethylaminopropyl (methyl) acrylamide；2- acrylamide
Base -2- methyl propane sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid etc. contain sulfonic vinyl compound；With polyoxy
The vinyl compounds containing polyoxyalkylenes such as (methyl) acrylate of the alcohol of vinyl and/or polyoxypropylene base；(first
Base) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- (n-propoxy) ethyl ester,
(methyl) acrylic acid 2- (n-butoxy) ethyl ester, (methyl) acrylic acid 3- methoxyl group propyl ester, (methyl) acrylic acid 3- ethoxy-c
Ester, (methyl) acrylic acid 2- (n-propoxy) propyl ester, (methyl) acrylic acid 2- (n-butoxy) propyl ester etc. contain alkoxy
Vinyl compound；(methyl) acrylic acid cyano methyl ester, (methyl) acrylic acid 1- cyanaoethyl methacrylate, (methyl) acrylic acid 2- cyano second
Ester, (methyl) acrylic acid 1- cyanopropyl acrylate, (methyl) acrylic acid 2- cyanopropyl acrylate, (methyl) acrylic acid 3- cyanopropyl acrylate, (first
Base) acrylic acid 4- cyanobutyl acrylate, the own ester of (methyl) acrylic acid 6- cyano, the own ester of (methyl) acrylic acid 2- ethyl -6- cyano, (first
Base) (methyl) acrylate compounds with cyano such as acrylic acid 8- cyano monooctyl ester；Acrylonitrile, methacrylonitrile, ethyl third
The vinyl cyanides based compound such as alkene nitrile；Vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl phenyl ether,
Vinyl ether compounds such as vinyl cyclohexyl ether etc..
In these, become good aspect in the water solubility of polymer, preferably (methyl) acrylamide and (methyl) propylene
Sour 2- hydroxy methacrylate.
Other vinyl monomers (b2) can be used alone any of above-mentioned each monomer, can also be by two or more simultaneously
With.
The usage amount of other vinyl monomers (b2) is based on the entire infrastructure unit of water-soluble polymer (B), is 0
The range of~50 weight %.Preferred range is 0~40 weight %, and preferred range is 0~30 weight %.If monomer
(b2) usage amount is 50 weight % hereinafter, the usage amount of above-mentioned monomer (b1) is 50 weight % or more, therefore water-soluble polymeric
The water solubility of object (B) becomes abundant.In addition, the film of excellent adhesion is obtained in the case where using metals such as aluminium as substrate, and
And it can be improved corrosion resistance.
The weight average molecular weight (Mw) of water-soluble polymer (B) is preferably 100,000~1,500,000 range, more preferably 200,000~
1000000 range, further preferably 300,000~800,000 range.If weight average molecular weight is 100,000 or more, can be obtained water-fast
The excellent film of property.On the other hand, if weight average molecular weight is 1,500,000 hereinafter, due to that can manufacture in practical range of viscosities,
Therefore processing becomes easy.
The manufacturing method of water-soluble polymer (B), in the same manner as above-mentioned water-soluble polymer (A), there is no particular restriction,
Preferred aqueous solutions polymerization.
In addition, for polymerizing conditions such as the polymerization initiators, chain-transferring agent and polymerization temperature that use, also can using with
The same condition of water-soluble polymer (A).
In the manufacture of water-soluble polymer (B), also equally with above-mentioned water-soluble polymer (A), for telo merization
In reaction solution pH, the pH of the water-soluble polymer adjusted (B), can be used alkaline agent (neutralizer).Specifically, it can enumerate
The alkaline-earth metals such as the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide hydroxide, ammonia, one
Organic amines such as ethanol amine, diethanol amine, triethanolamine etc. are able to use one kind or two or more in these.
The use level of water-soluble polymer (A) and water-soluble polymer (B) is (A)/(B)=30/70 with weight ratio meter
~95/5 ratio, preferably 40/60~90/10 ratio, more preferable 50/50~85/15 ratio.If water-soluble resin
(B) use level is (A)/(B)=95/5 or more, the high film of hydrophilic duration can be obtained, if it is (A)/(B)=30/
70 or less, it can be ensured that the hydrophily of film.
High-hydrophilic coating composition of the invention may include as needed well known additive in addition to the foregoing.
As specific additive, can enumerate surfactant, antibacterial agent, antioxidant, dyestuff, preservative, mould inhibitor, antirust agent,
Deodorant, solvent etc..
<radiator fin for heat exchanger material>
High-hydrophilic coating of the invention can by being coated on the various substrate surfaces such as metal, plastics and inorganic material
Coating process using high-hydrophilic coating is implemented to the substrate surface.
For example, used in radiator fin for heat exchanger material of air-conditioning etc., on the fin material surface
Form the film of high-hydrophilic.
Above-mentioned fin material is made of aluminum or aluminum alloy, for example, being indicated with the alloy serial number of JIS standard, can be used
1100, the aluminium such as 1200,1050,3003,7072.
Further more, the plate thickness of aluminium base is, it is preferable to use 0.06~0.3mm or so.If plate thickness is 0.06mm or more, can be true
Intensity needed for protecting substrate.On the other hand, if it is 0.3mm hereinafter, the processability as fin material is good.
Formed containing above-mentioned water-soluble polymer (A) or above-mentioned water-soluble polymer (A) on the surface of aluminium base and
The hydrophilic film that the high-hydrophilic coating composition of above-mentioned water-soluble polymer (B) is formed.High-hydrophilic of the invention applies
Feed composition need not further cooperate alumina sol, hydrophily organic since its own is with very high hydrophily
Resin particle etc..Obtained film shows very excellent hydrophily, maintains the hydrophily for a long time.In addition, even if the dirts such as grease
Dye substance is attached to fin material surface, is rinsed using dew etc., therefore can play polluter removability
Excellent performance.
Above-mentioned fin material can form various quilts according to use environment, purposes between aluminium base and hydrophilic film
Film.
For example, carrying out chemical conversion treatment to aluminium base, hydrophilic film is formed after imposing chemical conversion envelope, in high parent
The adhesion of aquation coating composition envelope, corrosion resistance etc. are preferably.As above-mentioned chemical conversion treatment, it is able to use previous
Well known method, it can be mentioned, for example phosphoric acid chromate processing etc..
High-hydrophilic coating composition of the invention is dried and is sintered, thus at this by being coated on substrate
Substrate surface forms the high film of hydrophily.Generally carried out at a temperature of sintering temperature is 150~300 DEG C or so.In addition, right
The adhesion amount of hydrophilic film is not particularly limited, each single side of the substrates such as aluminium, preferably 0.05~5.0g/m2Range.
By becoming the range, it is able to maintain that the water resistance and long-term excellent hydrophily of hydrophilic film.In addition, more preferably 0.3
~2.0g/m2Range.
<heat exchanger>
The manufacturing method of radiator fin for heat exchanger material of the present invention is not particularly limited, for example, passing through
For substrate (alternatively, foring the substrate of chemical conversion envelope etc. on surface), using coating device etc., be coated,
It is dry, so as to form hydrophilic film.Further more, hydrophilic film can apply before forming radiator fin for heat exchanger material
Cloth etc. (pre-coating) can also be coated with etc. (rear coating) after forming radiator fin for heat exchanger material.Below for pre-coating, after
The purposes example of coating is illustrated.
With pipe, the heat exchanger for the idle call etc. that cooling fin is main constituent element, cooling fin is made of aluminium, effective copper
The structure of compositions such as U-shaped bend pipe based on, in recent years, due to the background of the exhaustion of copper resource etc., the material price of copper is high
Rise, therefore carry out further cost effective, heat exchange performance raising, the pursuit of recycling property etc., also make in research
Become the full aluminum heat exchanger of aluminum comprising the entirety including pipe.Anyway, in the case where using such U-shaped bend pipe,
Generally heat exchanger is manufactured using precoat material.On the other hand, heat exchanger of automobile etc. becomes welded heat and hands over
Parallel operation, due to being heated to 600 DEG C or so of temperature when welding, therefore, it is considered that organic envelope cannot be coated with before welding in advance.This
It is because if being heated to 600 DEG C, organic envelope, which is burnt, to be lost or go bad.Therefore, generally by will manage, cooling fin is assembled into heat
The shape of exchanger is impregnated in hydrophilic resin liquid, is universally formed hydrophilic after being welded and the shape of heat exchanger being made
Property envelope as it is so-called after coating, carry out the formation of hydrophilic coating film.The present invention can be applied to these all purposes.
Embodiment
The present invention is specifically described below based on embodiment.
The Production Example of water-soluble polymer (A)
(Production Example 1)
Pure water 500g is added in 2L round-bottomed flask, is held in 80 DEG C, stirring.The pure water dissolution for using 5g is added thereto
Sodium peroxydisulfate 0.01g.By by 2- acrylamido -2- methyl propane sulfonic acid (hereinafter referred to as " ATBS ") 288g, acrylic acid 2- hydroxyl
Base ethyl ester (hereinafter referred to as " HEA ") 25.6g, acrylic acid 6.4g, 32% sodium hydrate aqueous solution 181g and pure water 300g stirring are mixed
Close, to modulate monomer mixture aqueous solution, be made 2,2 '-azo two (2- methyl-prop amidine) dihydrochloride 0.2g are dissolved in it is pure
Initiator solution made of in water 100g, while lasting 3 hours and being supplied in flask.After supply, further heating stirring 2
Hour, obtain water-soluble polymer A-1.
Using the weight average molecular weight (Mw) of gel permeation chromatography (GPC) measurement water-soluble polymer A-1.The measurement strip of GPC
Part: using GPC model 2695 (manufacture of Waters society), and detection is carried out using RI, and column has used TSK-GEL GMPWXL 7.8*
300 (manufactures of Tosoh society).Eluat is phosphoric acid buffer agent, and calibration curve uses polyethylene glycol (Polymer Laboratories
Society's manufacture) it is made.The result of measurement: the Mw of A-1 is 720,000.
(Production Example 2~16)
It by monomer composition shown in Tables 1 and 2 (weight ratio), is carried out similarly and polymerize with Production Example 1, obtained water-soluble
Property polymer A-2~A-16.Further more, by adjusting polymerization initiator amount as needed, to adjust the weight of water-soluble polymer
Average molecular weight.
(comparison manufacturing example 1~8)
By monomer composition shown in table 3 (weight ratio), it is carried out similarly and polymerize with Production Example 1, obtained water-soluble poly
Close object AC-1~AC-4, AC-6 and AC-8.
Further more, since the polymerism containing sulfonic monomer is poor, gathering in comparison manufacturing example 5 and comparison manufacturing example 7
Conjunction is not sufficiently carried out, and fails to obtain scheduled water-soluble polymer AC-5 and AC-7.
[table 1]
[table 2]
[table 3]
The Production Example of water-soluble polymer (B)
(Production Example 17)
Pure water 1000g is added in 2L round-bottomed flask, is held in 80 DEG C, stirring.It is added and is dissolved with the pure water of 5g thereto
Sodium peroxydisulfate 0.2g.By the way that AA393g and pure water 100g are stirred, to modulate monomer mixture aqueous solution, be made by
Sodium peroxydisulfate 0.6g is dissolved in initiator solution made of in pure water 100g, while lasting 5 hours and being supplied in flask.Supply knot
Shu Hou, further heating stirring 2 hours, has obtained water-soluble polymer B-1.
(Production Example 18)
25% ammonium hydroxide is added in aqueous solution by the water-soluble polymer B-1 obtained in above-mentioned Production Example 17, is neutralized
To pH7, to obtain water-soluble polymer B-2.
(Production Example 19,21~24)
(weight ratio) is formed by shown in table 4, is carried out similarly and polymerize with Production Example 17, obtained water-soluble polymer
B-3, B-5~B-8.
(Production Example 20)
By adding 25% ammonium hydroxide in the aqueous solution of water-soluble polymer B-3 obtained in Production Example 19, neutralization is arrived
PH7, to obtain water-soluble polymer B-4.
[table 4]
The details of compound used in 1~table of table 4 described below.
ATBS:2- acrylamido -2- methyl propane sulfonic acid
HAPS:3- allyloxy -2- hydroxyl -1- propanesulfonate
AA: acrylic acid
MAA: methacrylic acid
HEA: acrylic acid 2- hydroxy methacrylate
HEMA: 2-hydroxyethyl methacrylate
MA: methyl acrylate
AAm: acrylamide
The formation of film
Water-soluble polymer (A) and water-soluble polymer (B) are mixed with ratio shown in table 5, modulate high-hydrophilic
Coating composition.
On the other hand, using known manufacturing method, the aluminium made of the A1200 (JISH4000) of fine aluminium system is manufactured
Plate (plate thickness 0.10mm).It is right with alkaline reagent (Japanese ペ イ Application ト society manufactures " サ ー Off ク リ ー ナ ー (registered trademark) 360 ")
The aluminium sheet carries out degreasing.In turn, the processing of phosphoric acid chromate is carried out, chemical conversion envelope is formd.The attachment of chemical conversion envelope
Amount is 30mg/m in terms of Cr conversion2。
The high-hydrophilic coating composition of above-mentioned modulation is coated with 20mg/m in aluminium sheet2Amount (amount of water-soluble resin),
Drying in 15 minutes and sintering are carried out with 250 DEG C of throughcirculation dryers, film is formd, as sample.
<performance evaluation>
For obtained sample, performance evaluation has been carried out using following methods.It shows the result in table 5.
Hydrophily
By the way that the pure water of 5 μ l to be dripped to the film coated surface of each sample at room temperature, contact angle is measured, to carry out hydrophilic
The evaluation of property.Use contact angle determination device (Ying Hongjing machine society manufactures: OCA-20 type) measurement contact angle.The following institute of evaluation criteria
It states.
◎ (especially good): contact angle is less than 10 °
Zero (good): contact angle is 10 ° or more, less than 30 °
△ (bad): contact angle is 30 ° or more, less than 50 °
× (significant bad): contact angle is 50 ° or more
Hydrophilic duration
After each sample is impregnated 8 hours in ion exchange water, dry 16 hours at 80 DEG C, using such process as
1 circulation has carried out 10 circulations.Then, so that sample is returned to room temperature, drip the pure water of 5 μ l on surface, survey as described above
Determine contact angle.Evaluation criteria is as described below.
◎ (especially good): contact angle is less than 10 °
Zero (good): contact angle is 10 ° or more, less than 30 °
△ (bad): contact angle is 30 ° or more, less than 50 °
× (significant bad): contact angle is 50 ° or more
Polluter removability
As polluter, the stearic acid 1g as preventing hydration substance is put into the bottom of the drier with 6 liters of capacity
Portion plays the test film of the 5cm × 10cm cut out from above-mentioned each sample on the top of the reagent.Then, it will be done at 100 DEG C
After dry device heats 24 hours, after letting cool room temperature, test film is taken out, impregnates 1 minute, is dried at room temperature in pure water.It will
Above operation after 10 times, measures contact angle repeatedly.Evaluation criteria is as described below.
◎ (especially good): contact angle is less than 20 °
Zero (good): contact angle is 20 ° or more, less than 40 °
△ (bad): contact angle is 40 ° or more, less than 60 °
× (significant bad): contact angle is 60 ° or more
[table 5]
Film obtained in Examples 1 to 30 shows excellent hydrophily and polluter removability.In addition, this is hydrophilic
Property the dipping that has been repeated in ion exchange water and it is dry after also maintain good level, expectation can be maintained chronically
Above-mentioned performance.
On the other hand, in the water-soluble polymer AC-1 for having used the usage amount of monomer (a1) few as water-soluble polymer
(A) in comparative example 1, the result is that hydrophilic duration and polluter removability are insufficient.Comparative example 2 and 3 is water-soluble polymer
(A) usage amount of the vinyl monomer (a2) with hydroxyl in the situation (comparative example fewer than range specified in the present invention
It 2) is equally that hydrophilic duration and polluter removability are poor with the example of more situations (comparative example 3).In addition, using finishing
The hydrophilic duration of the comparative example 4 of water-soluble polymer AC-4 without the vinyl monomer (a3) with carboxyl in structure unit
It is insufficient.
In turn, as the sulfonic acid monomer for constituting water-soluble polymer (A), 2- acrylamido -2- methyl-prop sulphur has been used
In the case where monomer other than acid, since its reactivity is low, it is therefore necessary to reduce usage amount, as a result fail to assign film abundant
Hydrophily (comparative example 5 and 6).
Utilization possibility in industry
High-hydrophilic coating composition of the invention, can be in the surface shape of metal, plastics and inorganic material (glass etc.)
At the high film of hydrophily, above-mentioned film maintains its hydrophily for a long time.Therefore, can be used as these various substrates, particularly
The smears of the radiator fin for heat exchanger material of air-conditioning etc..
Claims (3)
1. high-hydrophilic coating composition is applied containing the high-hydrophilic of water-soluble polymer (A) and water-soluble polymer (B)
Feed composition,
Above-mentioned water-soluble polymer (A) be based on all constitute monomers, by make 2- acrylamido -2- methyl propane sulfonic acid or its
80~94.5 weight % of salt (a1), 4~15 weight % of vinyl monomer (a2), the ethylene base system with carboxyl with hydroxyl
Polymer obtained from 0.5~8 weight % of monomer (a3) and others vinyl monomer (a4) 0~15 weight % copolymerization, weight
Average molecular weight is 100,000~1,500,000,
Above-mentioned water-soluble polymer (B) is to pass through the vinyl monomer (b1) 50 for making to have carboxyl based on monomer is all constituted
Polymer obtained from~100 weight % and others vinyl monomer (b2) 0~50 weight % copolymerization, weight average molecular weight are
100000~1,500,000,
The weight ratio of above-mentioned water-soluble polymer (A) and above-mentioned water-soluble polymer (B) is (A)/(B's)=30/70~95/5
Ratio.
2. radiator fin for heat exchanger material has on the substrate made of aluminum or aluminum alloy by described in claim 1
The hydrophilic film that high-hydrophilic coating composition is formed.
3. heat exchanger, it uses radiator fin for heat exchanger materials as claimed in claim 2.
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 CN104830193A (en) | 2015-08-12 |
| CN104830193B true 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) |
Families Citing this family (3)
| 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 |
| CN106634389B (en) * | 2016-12-30 | 2019-12-27 | 广州慧谷化学有限公司 | Coating for preparing lubricating hydrophilic coating and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104830193A (en) | 2015-08-12 |
| JP2015147852A (en) | 2015-08-20 |
| JP6316612B2 (en) | 2018-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104884177B (en) | Hydrophilic coating film method, aluminum fin material and the aluminum-made heat exchanger of aluminum fin material | |
| JP6618903B2 (en) | Method for coating hydrophilic film on aluminum fin material, aluminum fin material and aluminum heat exchanger | |
| CN104830193B (en) | High-hydrophilic coating composition and application thereof | |
| JP6654814B2 (en) | Hydrophilizing agent, hydrophilic film forming method and hydrophilic film | |
| JP4464076B2 (en) | Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film | |
| JP2018023932A (en) | Hydrophilic film coating method of aluminum fin material, aluminum fin material, and heat-exchanger made of aluminum | |
| 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 | |
| JPH02107678A (en) | Coating composition for heat-exchanger fin | |
| JP3843024B2 (en) | Coating agent | |
| JP2525378B2 (en) | Resin composition for surface treatment | |
| JP2005075841A (en) | Coating composition for fin and fin material | |
| JP2936259B1 (en) | Surface treatment agent for heat exchanger fin, surface treatment method and surface treatment coating | |
| WO2016170698A1 (en) | Water-based surface-treating agent, process for producing coating film, and surface-treated material | |
| JPH02219879A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JPH0570711A (en) | Hydrophilizer for aluminumcontaining metallic material | |
| JPH02218765A (en) | Hydrophilic coating agent, aluminum or aluminum alloy plate for fin and heat-exchanger | |
| JPH02219878A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JPH02219874A (en) | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger | |
| JP2022139286A (en) | Hydrophilizing agent composition for metal | |
| JPH06172777A (en) | Aluminum-containing metallic material having hydrophilic film and lubricating film | |
| JP2009286865A (en) | Vinylpyrrolidone copolymer and hydrophilizing agent composition using the same | |
| JPH0389974A (en) | Method for forming hydrophilic film |
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 |