CN107614633A - Hydrophilizing agent, hydrophilic epithelium forming method and hydrophilic epithelium - Google Patents
Hydrophilizing agent, hydrophilic epithelium forming method and hydrophilic epithelium Download PDFInfo
- Publication number
- CN107614633A CN107614633A CN201680031155.9A CN201680031155A CN107614633A CN 107614633 A CN107614633 A CN 107614633A CN 201680031155 A CN201680031155 A CN 201680031155A CN 107614633 A CN107614633 A CN 107614633A
- Authority
- CN
- China
- Prior art keywords
- hydrophilic
- epithelium
- mass
- monomer
- mentioned
- 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.)
- Pending
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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of hydrophilizing agent that can form the hydrophilic epithelium with high hydrophilic continuation and excellent drainage, the hydrophilic epithelium forming method using such hydrophilizing agent and the hydrophilic epithelium by hydrophilic epithelium forming method formation.Hydrophilizing agent for forming hydrophilic epithelium in metallic substrate surface contains hydrophilicity value and crosslinkable microparticles, as hydrophilic resin, polyalkylene ether resin containing specific (methyl) acrylic resin, polyvinyl alcohol and specified molecular weight, the composition of each composition is adjusted in specific scope.
Description
Technical field
The present invention relates to hydrophilizing agent, hydrophilic epithelium forming method and hydrophilic epithelium.
Background technology
Conventionally, there is known implement the technology of hydrophilicity-imparting treatment on the surface of metal base.For example, in the heat exchange using aluminium
In device, in order to prevent due to noise, the sputtering because of water droplet cause caused by the condensed water for being attached to fin surface the problem of, in wing
Implement hydrophilicity-imparting treatment in piece surface.
As the hydrophilizing agent used in hydrophilicity-imparting treatment, it is proposed that containing the macromolecules such as acrylic acid polymer, with
The macromolecule forms the high molecular hydrophilicity-imparting treatments such as the PEO of hydrogen bond with polymer composition (for example, referenced patent
Document 1).This is the technology for the hydrophilic continuation for improveing hydrophilic epithelium, but according to the species of the polluter of attachment not
Together, above-mentioned hydrophilic deterioration can't fully be suppressed.In addition, metal surface and hydrophilic epithelium in the state of water is attached with
Between adaptation (WET adaptations (wet adaptation)) it is also insufficient.
In addition, it is proposed that salt, N hydroxymethyl acrylamide, polyacrylic acid and PEO containing carboxymethyl cellulose
Hydrophilizing agent, and the aqueous high molecular compound containing polyoxyalkylene chain, water-base resin and N- methylol acryloyls
The hydrophilizing agent (for example, referenced patent document 2,3) of amine.These hydrophilizing agents, N- hydroxyl first is combined with as monomer
Base acrylamide, therefore the hydrophilic continuation in the case of polluter is attached to is insufficient.
In addition, it is proposed that by the monoene monomer with polyoxyalkylene chain, (methyl) acrylamide monoene monomer, N-
The N- methylols base such as NMA and the bridging property unsaturated monomer with polymerizable double bond and other monomers institute
Obtained crosslinkable microparticles are sub (for example, referenced patent document 4~6).Especially, by coordinating specific crosslinkable microparticles,
The hydrophilic continuation after being attached with pollutant can be improved and improve the hydrophilic epithelium and metal base being attached with the state of water
Adaptation (referenced patent document 7 and 8) between surface.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 6-322292 publications
Patent document 2:Japanese Unexamined Patent Publication 6-322552 publications
Patent document 3:Japanese Unexamined Patent Publication 7-102189 publications
Patent document 4:Japanese Unexamined Patent Publication 8-120003 publications
Patent document 5:Japanese Unexamined Patent Publication 2000-248225 publications
Patent document 6:Japanese Unexamined Patent Publication 2002-302644 publications
Patent document 7:Japanese Unexamined Patent Publication 2005-2151 publications
Patent document 8:Japanese Unexamined Patent Publication 2014-000534 publications
The content of the invention
Invent problem to be solved
As described above, the hydrophilizing agent described in using patent document 7 and 8, in the hydrophilic skin that metal surface is formed
Film, the excellent adhesion between hydrophilic epithelium and the metal surface being attached with the state of water, it is being attached with pollutant state
Under hydrophilic continuation it is also excellent.
However, the product formed by metal base including aluminum-made heat exchanger, it is desirable to minimize.Along with by gold
The miniaturization for the product that category base material is formed, has the situation that the distance between adjacent metal base material becomes narrow.If metal
Distance between base material becomes narrow, for example, in a heat exchanger, being easy to block because mesh occurs for water droplet.Therefore, in metal base
Surface, in addition to all the time required hydrophily, also require formed with the state of water is attached with height parent
The hydrophilic epithelium of water continuation.
In addition, if narrowing between adjacent metal base, water droplet can connect between metal base, for example, in heat exchanger
In, there is a situation where to increase flowing resistance.Therefore, in order to prevent water droplet from being connected between metal base, it is desirable to the table of metal base
Face is so that contacted water is readily flowed (drainage is high).Especially, heat exchange used in the outdoor unit in cold zone
Device, water droplet connect between fin, in the case that the water droplet freezes, dramatically increase flowing resistance.Further, in order to reduce by
Flowing resistance caused by water droplet in icing, need to close without direct with heat exchange in the case where melting frozen water droplet
The unnecessary energy of system, cost improve.
So, it is desirable to formed in metallic substrate surface with the hydrophilic epithelium for fully meeting hydrophilic continuation and drainage
Technology, but existing situation is that to form such hydrophilic epithelium highly difficult.
The present invention be in view of above-mentioned problem and complete, its object is to provide a kind of can be formed to be attached with the shape of water
Under state with higher hydrophilic continuation and excellent drainage hydrophilic epithelium hydrophilizing agent, using the hydrophiling at
The hydrophilic epithelium managed the hydrophilic epithelium forming method of agent and formed by the hydrophilic epithelium forming method.
The method for solving problem
The present inventor etc. has found, if using containing hydrophilic resin and crosslinkable microparticles, contains as hydrophilic resin
There is the polyalkylene ether (Polyalkylene of specific (methyl) acrylic resin, polyvinyl alcohol and specified molecular weight
Ether) resin, the composition of each composition is adjusted into the hydrophilizing agent to preset range, it becomes possible to solve above-mentioned problem, from
And complete the present invention.More specifically, the invention provides scheme once.
In order to solve above-mentioned problem, it is used to form the parent of hydrophilic epithelium on the surface of metal base the invention provides a kind of
Hydration process agent, contains：Containing coming from the repeat unit of acrylic monomers and/or come from the repeat unit of methacrylic acid monomer
(methyl) acrylic resin (A), polyvinyl alcohol (B), polyalkylene ether resin (C) and crosslinkable microparticles it is sub (D)；It is described
(methyl) acrylic resin (A) (1) does not have the repeat unit for coming from the monomer containing sulfo group and come from containing amide groups
Monomer repeat unit, (2) weight average molecular weight is 20000~2000000, the acid number of (3) resin solid composition for 100~
800mgKOH/g；The weight average molecular weight of the polyalkylene ether resin (C) is 5000~500000；Crosslinkable microparticles
(D) it is by the mass % of monomer (a) 30~95, the list containing polyoxyalkylene chain and polymerism double bond represented by following formula (I)s
Obtained from the mass % of body (b) 5~60 and other polymerizable monomers (c) 0~50 mass % is copolymerized,
[changing 1]
In formula, R1Represent H or methyl, R2Represent CH2Or C2H4。
In the solid composition of the hydrophilizing agent, the containing ratio of (methyl) acrylic resin (A) is 10
~30 mass %, the containing ratio of the polyvinyl alcohol (B) is 10~40 mass %, and polyalkylene ether resin (C's) contains
Rate is 15~50 mass %, and the containing ratio of the crosslinkable microparticles sub (D) is 30~65 mass %.
The present invention provides a kind of hydrophilic epithelium forming method, including：The surface of the aluminium base is set to contact chemical conversion treatment agent
Form the step of being melted into epithelium and make to contact come shape with the hydrophilizing agent by the chemical conversion epithelium obtained by the step
The step of into hydrophilic epithelium.
In addition, the present invention provides a kind of surface that the metal base is formed at by the hydrophilic epithelium forming method
Hydrophilic epithelium.
In addition, the thickness of the hydrophilic epithelium is preferably 0.3~10 μm.
Invention effect
The hydrophilic epithelium formed using the hydrophilizing agent of the present invention in metal surface, has high hydrophilic continuation
And excellent drainage.
Embodiment
Hereinafter, embodiments of the present invention are illustrated.It should be noted that the invention is not restricted to following implementation shape
Formula.
＜ metal bases ＞
According to the hydrophilizing agent of the present invention, as forming the metal base of hydrophilic epithelium on surface, such as there is aluminium base
Material.Aluminium base is the base material of aluminum.Herein, " aluminium " is the general name of metal based on aluminium and alloy, be comprising fine aluminium and
The concept of aluminium alloy.
As aluminium base, such as there is aluminum-made heat exchanger.Heat exchanger, from the viewpoint of heat exchanger effectiveness is improved, its
Surface requirements multiple fins as big as possible are configured with narrower interval, meanwhile, it is configured on these fins inserted with for carrying
The pipe of cooling matchmaker.
＜ hydrophilic finishing agents ＞
According to the hydrophilizing agent of the present invention, specific hydrophilic resin and specific crosslinking are contained with specific ratio
Property particulate.These compositions are contained by hydrophilizing agent, the hydrophilic epithelium formed is in the state of water is attached with
With higher hydrophilic continuation and excellent drainage.
[hydrophilic resin]
According to the hydrophilic resin of the present invention, it is necessary to contain：Comprising the repeat unit for coming from acrylic monomers and/or come from
(methyl) acrylic resin (A), polyvinyl alcohol (B) and the polyalkylene ether resin of the repeat unit of methacrylic acid monomer
(C)。
(methyl) acrylic resin (A) is at least containing at least one for coming from acrylic monomers and methacrylic acid monomer
Repeat unit.The repeat unit of acrylic monomers is come from, the total content of the repeat unit of methacrylic acid monomer is come from, does not have
It is specifically limited, but preferably 50~100 mass %.
(methyl) acrylic resin (A), which can also contain, to be come from the repeat unit of acrylic monomers, comes from metering system
Repeat unit beyond the repeat unit of acid monomers.For example, derivative of acrylic monomers or methacrylic acid monomer etc..
Specifically, as the monomer in monomer with 1 polymerizable unsaturated bond, such as there is methyl methacrylate
The different nonyl ester of ester, n-BMA, Isobutyl methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid, first
The alkyl acrylates such as base n-octyl, lauryl methacrylate, octadecyl methacrylate, acrylic acid first
The propylene such as the different nonyl ester of ester, n-butyl acrylate, isobutyl acrylate, 2-EHA, acrylic acid, n-octyl
The metering system of the methacrylic acid aralkyl ester such as acid alkyl ester, benzyl methacrylate, methacrylic acid butoxyethyl etc.
The alkoxyalkyl acrylates such as sour alkoxy alkyl, acrylate, butoxy ethyl.These materials can be used alone, and also may be used
It is used in combination with two or more.
In addition, (methyl) acrylic resin (A) can also contain the composition beyond above-mentioned monomer, but preferably without active
In the monomer with sulfo group repeat unit and come from the repeat unit of the monomer with amide groups.When containing these units,
In the presence of the tendency for being difficult to suppress foul smell generation.
The solid composition containing ratio of (methyl) acrylic resin (A) in the total solid composition of hydrophilizing agent is 10
~30 mass %.When the solid composition containing ratio of (methyl) acrylic resin (A) is less than 10 mass %, hydrophilic epithelium and gold
Adaptation and drainage between metal surface reduce.When the solid composition containing ratio of (methyl) acrylic resin (A) is more than 30
During quality %, hydrophilic continuation and drainage reduce.The solid composition containing ratio of (if methyl) acrylic resin (A) is above-mentioned
In the range of, then interface that almost all of (methyl) acrylic resin (A) is present between metal surface, so as to
(methyl) acrylic resin (A) is not present in the face side of hydrophilic epithelium.
The acid number of (methyl) acrylic resin (A) is 100~800mgKOH/g.(if methyl) acrylic resin (A)
Acid number less than 100mgKOH/g, then the adaptation of hydrophilic epithelium and metal surface reduces.(if methyl) acrylic resin (A)
Acid number more than 800mgKOH/g, then the sour composition in hydrophilic epithelium absorption air, so as to which resistance to stink reduces.
The weight average molecular weight of (methyl) acrylic resin (A) is 20000~2000000.(if methyl) acrylic acid series tree
The weight average molecular weight of fat (A) is less than 20000, then hydrophilic continuation reduces.The Weight-average molecular of (if methyl) acrylic resin (A)
Amount is more than 2000000, then the viscosity increase of hydrophilizing agent, operability reduce.(if methyl) acrylic resin (A)
Weight average molecular weight is small, in hydrophilic epithelium and contact with moisture, (methyl) third for the near interface being present between metal surface
Olefin(e) acid system resin (A) is moved to the face side of hydrophilic epithelium.(if methyl) acrylic resin (A) is moved to the table of hydrophilic epithelium
Surface side, then the adaptation reduction between hydrophilic epithelium and metal surface.In addition, when weight average molecular weight is too small, due to from water
Dissolution, cause the reduction of the adaptation of hydrophilic epithelium and metal surface.At the weight average molecular weight of (if methyl) acrylic resin (A)
In in above range, even if the surface attachment for being continuously in hydrophilic epithelium has the state of water, between hydrophilic epithelium and metal surface
Closing force reduce the problem of will not also occur.It is highly preferred that the scope of the weight average molecular weight of (methyl) acrylic resin (A)
For 20000~100000.It should be noted that the value of weight average molecular weight uses what is determined by gel permeation chromatography (GPC) method
Value.Specifically, it is molten as sample using the solution dissolved with the parts by weight of resin sample 0.4 relative to the mass parts of tetrahydrofuran 100
Liquid, LC-08 (A-5432) the types GPC that it is prepared by Japanese analytical industry Co., Ltd. is measured, passes through polystyrene
Convert to calculate.
Contained polyvinyl alcohol (B) is to carrying out soap by the condensate of polyvinyl acetate polyisocyanate polyaddition in hydrophilizing agent
Change to obtain.In the present invention, the degree of polymerization of polyvinyl alcohol (B) does not have special limitation, preferably less than 300~2000.
In addition, the saponification degree of polyvinyl alcohol (B) is preferably more than 95%.
The solid composition containing ratio of polyvinyl alcohol (B) in total solid composition of hydrophilizing agent is 10~40 matter
Measure %.When above-mentioned containing ratio is less than 10 mass %, the risk that hydrophilic continuation and drainage reduce be present.When above-mentioned containing ratio
During more than 40 mass %, hydrophilic epithelium is difficult to show hydrophily (initial hydrophilicity and hydrophilic continuation), and drainage also reduces.
It is preferred that above-mentioned containing ratio is 10~25 mass %.
Contained polyalkylene ether resin (C) is to assign hydrophily and lubricity to hydrophilic epithelium in hydrophilizing agent
Composition.By assigning lubricity to hydrophilic epithelium, processability when pressure processing etc. is carried out to the surface of aluminum fin-stock can be improved.
Polyalkylene ether resin (C) does not have as long as it is the material belonged in above range that it, which overlaps mean molecule quantity,
It is specifically limited.As polyalkylene ether resin (C), polyoxyethylene (PEO, polyethylene glycol), polyoxy third can be enumerated
The condensation product etc. of alkene, these materials.Furthermore it is possible to these polyalkylene ether resins are used in mixed way.As polyalkylene ether tree
Fat (C), from the viewpoint of the hydrophily for improving the hydrophilic epithelium formed, preferably using polyoxyethylene.
The weight average molecular weight of polyalkylene ether resin (C) is 5000~500000.If the weight of polyalkylene ether resin (C) is equal
Molecular weight, because polyalkylene ether resin (C) is too high to the dissolubility of water, causes the parent of hydrophilic epithelium to be formed less than 5000
Water continuation reduces.On the other hand, if the weight average molecular weight of polyalkylene ether resin (C) is more than 500000, due to polyalkylene
The viscosity of ether resin (C) increases so that coating is deteriorated.Polyalkylene ether resin (C) preferable weight-average molecular weight be 5000~
300000.Thus, the weight average molecular weight by polyalkylene ether resin (C) is smaller, polyalkylene ether resin (C) it is hydrophilic
Property increase, hydrophilic epithelium can show higher hydrophily (initial hydrophilicity and hydrophilic continuation).
The solid composition containing ratio of polyalkylene ether resin (C) in the solid composition of hydrophilizing agent is 15~50 matter
Measure %.If above-mentioned containing ratio does not show hydrophily less than 15 mass %, hydrophilic epithelium.If above-mentioned containing ratio is more than 50 matter
Measure %, then the risk that the dissolution from water of epithelium composition be present, while soil release performance also reduces.
In the present invention, the polyalkylene ether resin in the solid composition of increase hydrophilizing agent described above is improved
(C) solid composition containing ratio.Because by so, polyvinyl alcohol (B) (its improve with as forming hydrophilic epithelium
Basis aluminium surface adaptation) and polyalkylene ether resin (C) (it is present in the surface of hydrophilic epithelium) phase densely occurs
Separation, so as to hydrophilic epithelial surfaces bumps increase so that hydrophilic epithelium present compared with high-hydrophilic (initial hydrophilicity and
Hydrophilic continuation).
It should be noted that if the solid composition containing ratio of polyalkylene ether resin (C) is high, exist hydrophilic epithelium with
The tendency that the adaptation of metal surface reduces.In the present invention, by making to be present in (methyl) with the near interface of metal surface
The solid composition containing ratio of acrylic resin (A) is increased in above range, is improved between hydrophilic epithelium and metal surface
Adaptation.
[crosslinkable microparticles]
Crosslinkable microparticles in the present invention sub (D) are monomers (a) represented by following formula (I)s, have polyoxyalkylene chain
And the monomer component that is formed of the monomer (b) of polymerism double bond and other polymerizable monomers be copolymerized obtained from copolymer
The resin particle formed.Above-mentioned crosslinkable microparticles sub (D) and above-mentioned (a) methylol, the carboxyl of ethoxy and above-mentioned (b),
The functional group of hydroxyl etc. reacts, or each other condensation reaction occurs for methylol, ethoxy, or with the carboxyl of above-mentioned (c),
Hydroxyl reacts.Therefore, in the case where using above-mentioned crosslinkable microparticles sub (D) as the composition of hydrophilizing agent, energy
It is enough that firm hydrophilic epithelium not soluble in water is formed in metal surface.In addition, the hydrophily of above-mentioned crosslinkable microparticles sub (D) compared with
Height, there is more unreacted functional group, therefore in the case where being used as the composition of hydrophilizing agent, it is hydrophilic with other
Property resin reacts, and will not lose hydrophily, can greatly improve the hydrophilic continuation after being attached with pollutant.Further,
Above-mentioned crosslinkable microparticles are sub (D), due to being the less material of swelling ratio relative to water, can suppress the hydrophilic skin to be formed
Film is dissolved in water.
[changing 2]
Monomer (a) represented by above-mentioned formula (I) is N hydroxymethyl acrylamide, N- methylol methacrylamides, N- hydroxyls
Ethyl acrylamide or N- hydroxyethyl methacrylamides.Obtained when using to contain by with the monomer (a) represented by above-mentioned formula (I)
During the hydrophilizing agent of the crosslinkable microparticles that arrive sub (D), above-mentioned hydrophilic continuation and above-mentioned excellent adhesion can be formed
Hydrophilic epithelium.These may be used alone, two or more kinds can also be used.
Above-mentioned crosslinkable microparticles sub (D) are by that will contain the mass % of monomer (a) 30~95 represented by above-mentioned formula (I)
Monomer component be copolymerized what is obtained.When less than 30 mass %, hydrophilic epithelium exists hydrophilic after pollutant is attached with
The risk that continuation reduces.When more than 95 mass %, the risk for being difficult to manufacture be present.Monomer represented by above-mentioned formula (I)
(a) coordinate within the above range, therefore while being played a role as crosslinking component, also as hydrophilic epithelium formed into
Point main component and play a role.That is, in the case of coordinating only being played a role as crosslinking component, usually using few
In the use level of above range, but contained in the crosslinkable microparticles sub (D) in the present invention with the use level of above range by above-mentioned
Monomer (a) expressed by formula (I), thus, after copolymerization, also remaining has methylol, ethoxy in crosslinkable microparticles.
Therefore, in the case where forming hydrophilic epithelium using the hydrophilizing agent containing above-mentioned crosslinkable microparticles sub (D), meeting and its
His hydrophilic resin reacts to obtain firm adaptation and hydrophilic continuation.Thus, even if in the hydrophilic skin formed
Be attached with film the plastics such as palmitic acid, stearic acid, paraffin acid with lubricator, the polluter such as phthalic acid diisooctyl,
The hydrophily of hydrophilic epithelium can fully be kept.
In addition, by coordinating crosslinkable microparticles obtained by the monomer (a) represented by above-mentioned formula (I), because it is matched somebody with somebody
Resultant, which adds, to cause the degree of cross linking also to increase.Thus, the hydrophilic epithelium for suppressing to be formed dissolves because of moisture, can form adaptation
(adaptation that epithelium is exposed in the case of moisture) excellent epithelium.
The use level of monomer (a) represented by above-mentioned formula (I), it is 30~95 matter relative to the mass % of monomer component 100
Measure %.Above-mentioned lower limit is preferably 40 mass %, and the above-mentioned upper limit is preferably 80 mass %.
Above-mentioned monomer (b), as long as the monomer with polyoxyalkylene chain and polymerism double bond, is not particularly limited,
Compound preferably represented by following formula (II)s and/or following formula (III)s.Thus, the hydrophily of water stably dispersing is obtained
Excellent crosslinkable microparticles.
[changing 3]
[changing 4]
In above-mentioned formula (II), above-mentioned R3And above-mentioned R4It can be the same or different, represent H or methyl.Above-mentioned R5Represent
H, methyl, SO3H、SO3Na or SO3NH4。
In above-mentioned formula (II), n represents 6~300 integer.When less than 6, dispersion stabilization, hydrophily are insufficient, when
During more than 300, it is difficult to manufacture.Above-mentioned lower limit is preferably 30, and the above-mentioned upper limit is preferably 200.
In above-mentioned formula (III), above-mentioned R6And above-mentioned R8It can be the same or different, represent H or methyl.Above-mentioned R9Table
Show H, methyl, SO3H、SO3Na or SO3NH4.Above-mentioned R7Represent CH2Or phenyl ring (following chemical formula (IV)).
[changing 5]
In above-mentioned formula (III), m represents 6~300 integer.When less than 6, dispersion stabilization, hydrophily are insufficient,
When more than 300, it is difficult to manufacture.Above-mentioned lower limit is preferably 30, and the above-mentioned upper limit is preferably 200.
It is not particularly limited as above-mentioned monomer (b), for example, the change represented by except above-mentioned formula (II), above-mentioned formula (III)
Outside compound, such as there are methoxy poly (ethylene glycol) monomethacrylates, methoxy poly (ethylene glycol) mono acrylic ester, octyloxy to gather
Ethylene glycol-polypropylene glycol mono acrylic ester etc..These materials may be used alone, used in two or more.
Above-mentioned monomer (b), the preferably compound containing more than the mass % of polyoxyalkylene chain 50.Herein, so-called 50 matter
Amount more than % refers to that in the mass % of solid composition quality 100 of used monomer (b) the total of the part of polyoxyalkylene chain consolidates
Shape composition quality is more than 50 mass %.When less than 50 mass %, the risk that the hydrophily of hydrophilic epithelium reduces be present.It is above-mentioned
Monomer (b), preferably comprise the mass % of polyoxyalkylene chain 80~99.
The use level of above-mentioned monomer (b), it is 5~60 mass % relative to the mass % of monomer component 100.When less than 5 matter
When measuring %, the dispersiveness reduction of crosslinkable microparticles in hydrophilizing agent, in addition, the hydrophily of hydrophilic epithelium reduces.
When more than 60 mass %, the adaptation of hydrophilic epithelium is insufficient, and the hydrophilic continuation after polluter is attached with reduces.On
It is preferably 10 mass % to state lower limit, and the above-mentioned upper limit is preferably 40 mass %.
Other described polymerizable monomers (c) contain polymerism unsaturated bond in 1 molecule, as long as with by above-mentioned formula
(I) compound that monomer (a) and above-mentioned monomer (b) represented by can be copolymerized, is not particularly limited, such as have third
The vinyl monomers such as olefin(e) acid, methacrylic acid, itaconic acid, maleic acid, vinyl acetate base, acrylic acid 2- hydroxy methacrylates, acrylic acid
Hydroxy propyl ester, N- vinylacetamides, N- ethylene carboxamides, N- vinylpyrrolidones, N- vinyl imidazols, acrylonitrile, metering system
Acid esters, methyl methacrylate, styrene, the surfactant containing unsaturated double-bond, acrylamide, Methacrylamide,
N methacrylamide, N- vinyl sulfonic acids, N- propene sulfonic acids, SSS, the methyl propane sulfonic acid of 2 acrylamide 2 etc..Separately
Outside, can also be using the acrylate outside methacrylate, methyl methacrylate, methacrylate etc. generally freely
Unsaturation monomer used in base polymerization.Wherein, the hydrophilic viewpoint of crosslinkable microparticles obtained by it can improve
Set out, preferably acrylic acid, methacrylic acid.These materials, may be used alone, used in two or more.
The use level of other above-mentioned polymerizable monomers (c), it is 0~50 mass % relative to the mass % of monomer component 100.
When more than 50 mass %, the hydrophily of resulting crosslinkable microparticles (D), bridging property reduce, in addition, hydrophilic epithelium is attached
Is reduced by the hydrophilic continuation after polluter.The above-mentioned upper limit is preferably 30 mass %.
The crosslinkable microparticles of the present invention are sub (D), and preferably water-swellable rate is 1.0~1.5.Thus, hydrophilic epithelium is being formed
In the case of, the adaptation between hydrophilic epithelium and metal surface can also be suppressed by being exposed to even if hydrophilic epithelium in moisture reduce.
Less than 1.5 water-swellable rate, monomer (a), above-mentioned monomer represented by above-mentioned formula (I) can be coordinated by above-mentioned match ratio
(b) and other above-mentioned repeatability monomers (c) and reaction condition is appropriately arranged with to obtain.Above-mentioned water-swellable rate is preferably 1.0~
1.3.It should be noted that the water-swellable rate in this specification, is with particle diameter institute in particle diameter/solvent in water-swellable rate=aqueous solution
The value of calculating.In addition, particle diameter (D50) it is to be surveyed using electrophoretic light scattering luminosity PHOTAL ELS-800 (preparation of great Mound electronics commercial firm)
Surely the value obtained.
The crosslinkable microparticles of the present invention sub (D) can for example be prepared as got off, i.e. by above-mentioned N- methylols (methyl) propylene
The mass % of acid amides (A) 30~95, the above-mentioned mass % of monomer (b) 5~60 with polyoxyalkylene chain and polymerism double bond and above-mentioned
Other polymerizable monomers (c) 0~50 mass %, can be molten in used monomer under conditions of in the absence of dispersion stabilizer
Solution but the copolymer that is generated will not be in the water miscibility organic solvents of substance soluble or water miscibility organic solvent/water mixing
It is copolymerized in solvent.
Dispersant is used in the preparation of above-mentioned crosslinkable microparticles sub (D) when being copolymerized, when can also be different.As upper
State dispersant, such as can be by dispersion resins such as polyvinylpyrrolidone, polyvinyl alcohol, polycarboxylic acids, anion, cation, non-
Various surfactants of ion etc..
In the preparation of the crosslinkable microparticles sub (D) of the present invention, the list that is formed by above-mentioned (a), above-mentioned (b) and above-mentioned (c)
The copolymerization of body composition, can be in ether solvent, methoxies such as alkylidene ethylene glycol monoalkyl ethers (such as ethylene glycol monobutyl ether etc.)
Carried out in the mixed solvent equal solvent of base propyl alcohol, these materials and water.
By the copolymerization of above-mentioned (a), above-mentioned (b) and above-mentioned (c) monomer component formed, generally in radical polymerization initiator
In the presence of carry out.As above-mentioned radical polymerization initiator, it is not particularly limited, all commonly used things can be used
Matter.For example, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumyl hydroperoxide, tert-butyl group mistake
The peroxide such as caprylate, t-butyl peroxy -2 ethyl hexanoic acid ester, 2,2'- azodiisobutyronitriles, 2,2'- azos two (2,4- bis-
Methyl valeronitrile), 2,2'- azos two (4- methoxyl group -2,4- methyl pentane nitriles), dimethyl 2,2'- azobis isobutyronitriles, 4,4'-
The azo-compounds such as azo two (4- cyanopentanoic acids propionic acid), 2,2'- azo two (2- amidine propanes) dihydrochlorides, 2,2'- azos
The amidine compound such as two (N-N'- dimethyl isobutyls amidines) and 2,2'- azo two (N-N'- dimethyleneisobutylamidines), persulfuric acid
The persulfide such as potassium, ammonium persulfate series initiators or its with sodium thiosulfate, amine etc. and material.These materials can be independent
Use, two or more can also be used in combination.Its usage amount is commonly angled relative to the total amount of monomer, can be 0.2~5 mass % scope
It is interior.
Polymerization temperature during above-mentioned copolymerization, it can be changed according to species of used polymerization initiator etc., generally,
Temperature in the range of 70~140 DEG C is appropriate.When less than 70 DEG C, bridging property is insufficient, when more than 140 DEG C, it is difficult to control
Reaction.Above-mentioned lower limit is more preferably 90 DEG C, and the above-mentioned upper limit is more preferably 120 DEG C.Reaction time is usually 0.2~5 hour.If no
Foot 0.2 hour, then bridging property is insufficient, and even more than 5 hours, reaction will not also change, unfavorable for economy.By making to gather
It is more than 90 DEG C to close temperature, can carry out being crosslinked in particle.It is generally, several in polymerization in the case that polymerization temperature is less than 70 DEG C
Without cross-linking reaction in particle, generally after polymerization, temperature of the condensate generated more than 90 DEG C is heated
The operation that progress is crosslinked in particle is exercised to enter within 0.2~5 hour.
In addition, in order that obtain cross-linking reaction more F.F. in the particle of the polymeric particles in polymerisation or after polymerisation
OK, catalyst for cross-linking reaction can be added in polymerization reaction system as needed.As above-mentioned catalyst for cross-linking reaction, example
Such as, the strong acid catalysts such as DBSA, p-methyl benzenesulfonic acid, sulfomethvl ethyl acrylate etc. can be there are with poly-
The strong acid catalyst of conjunction property double bond.
The volume average particle size of crosslinkable microparticles obtained as described above is not particularly limited, from crosslinkable microparticles
Stability viewpoint sets out, generally 0.03~1 μm, preferably in the range of 0.05~0.6 μm.
Hydrophilizing agent containing above-mentioned crosslinkable microparticles and hydrophilic resin, can form hydrophilic continuation and close
The excellent hydrophilic epithelium of conjunction property.In the case that above-mentioned hydrophilizing agent is used for metal, especially aluminium or its alloy, it can be formed
The hydrophilic epithelium of hydrophilic continuation and excellent adhesion.
The content of crosslinkable microparticles sub (D) in total solid composition of hydrophilizing agent is 30~65 mass %.Work as friendship
When the content of connection property particulate (D) is less than 30 mass %, the drainage of the hydrophilic epithelium formed reduces, and soil release performance also reduces.
On the other hand, when the content of crosslinkable microparticles sub (D) is more than 65 mass %, the hydrophily of the hydrophilic epithelium formed reduces.
In the present invention, in the solid composition of hydrophilizing agent as described above, containing for crosslinkable microparticles sub (D) is improved
Amount.Thus, because the adaptation between aluminium surface polyvinyl alcohol (B) and be present in hydrophilic epithelium surface polyalkylene ether
Crosslinkable microparticles is filled with the concavo-convex recess for the hydrophilic epithelial surfaces for being densely separated and being formed between resin (C)
(D).In the concavo-convex recess of hydrophilic epithelial surfaces, crosslinkable microparticles (D) largely contained in hydrophilizing agent is inserted,
So that the surface of hydrophilic epithelial surfaces becomes flat, the drainage of hydrophilic epithelium is improved.
[other compositions]
For the purpose for the hydrophilic epithelium for forming coloring, pigment can be added in above-mentioned hydrophilizing agent.As adding
The pigment added does not have special limitation, can be applicable the commonly used coloring pigment such as inorganic pigment, organic pigment.
Above-mentioned hydrophilizing agent, according to additional function, following other compositions of necessary amount can be added.For example, surface
The hydrophilic additives such as activating agent, cataloid, titanium oxide, carbohydrate, tannic acid, imidazoles, triazines, triazole type, purine
The rust-inhibiting additives such as class, hydrazine, phenolic resin, zirconium compounds, silane coupler, melmac, epoxy resin, enclosed type
The crosslinking agents such as isocyanates, amine, phenolic resin, silica, aluminium, zirconium, antiseptic, dispersant, lubricant, deodorant, solvent
Deng.
The hydrophilic epithelium forming method ＞ of ＜
By using the hydrophilic epithelium forming method according to the present invention, it can be formed in be attached with the state of water and be in not only
Existing high hydrophilic continuation and drainage also excellent hydrophilic epithelium.Especially, it is according to the hydrophilic epithelium forming method of the present invention
Aluminium or the method for its alloy can be applied to.It should be noted that the effect above is by using at above-mentioned specific hydrophiling
Reason agent obtains, therefore can use in general method as the forming method of hydrophilic epithelium.
In the hydrophilic epithelium forming method of in general, generally, ungrease treatment is carried out to the surface of metal base first.Connect
, contact chemical conversion treatment agent further carries out following steps, connect the chemical conversion epithelium obtained by above-mentioned steps to form chemical conversion epithelium
Touch the step of hydrophilizing agent is to form hydrophilic epithelium.
Can be entered by alkaline solutions such as sodium hydroxide, sodium carbonate, sodium metasilicate, sodium phosphates as above-mentioned ungrease treatment
Capable any alkali degreasing.In addition, as above-mentioned chemical conversion treatment, the processing of phosphoric acid chromate, coating type chromic acid salt treatment, Chrome-free are enumerated
Hydrochlorate processing.Above-mentioned phosphoric acid chromate processing can be by entering in chromic anhybride with the addition of the treatment fluid of additive in phosphoric acid
OK.Above-mentioned phosphoric acid chromate processing can be carried out by being immersed in treatment fluid or by spray treatment liquid etc..As above-mentioned
Corrosion-resistant resin priming paint, enumerate the resin primer processing of acrylic acid, epoxy, polyester, phenol or polyurethane series.
The chemical conversion epithelium for handling to obtain by above-mentioned phosphoric acid chromate, chromium (Cr) amount are preferably 3~50mg/m2.Work as deficiency
3mg/m2When, then rust-preventing characteristic is insufficient, when more than 50mg/m2When, the reaction with hydrophilic epithelium, which occurs, causes hydrophily to decline.Shape
Into metals such as the aluminum or aluminum alloy for having chemical conversion epithelium, generally washed.Washing now, preferably carry out 10~30 seconds or so.
Inorganic agent used in above-mentioned coating chromic acid salt treatment, it is chromic acid salt treatment used in the coating process such as roller coat
Agent.In the case, chromium content is preferably 5~30mg/m in epithelium2。
Inorganic agent used in above-mentioned chromate-free processing is free from the inorganic agent of chromium, for example, can enumerate at zirconium class
Manage agent.Can be mixture of polyacrylic acid and zirconium fluoride etc. etc. as above-mentioned zirconium class inorganic agent.
By above-mentioned zirconium class inorganic agent to epithelium in Zr amounts be preferably 0.1~40mg/m2.When less than 0.1mg/m2
When corrosion resistance it is insufficient, if more than 40mg/m2It is then not economical enough.The processing of zirconium class is superimposed on chromium processing, then effect is more preferable.
Generally, the surface requirements hydrophily and corrosion resistance of aluminium base, it is however generally that the excellent epithelium of hydrophily is to a certain degree
Upper corrosion resistance is low.Therefore, in the hydrophilic epithelium forming method according to present embodiment, before hydrophilic epithelium is formed, in order to
Corrosion resistance epithelium is formed in substrate, after chemical conversion treatment is carried out, is preferably carried out by the prime treatment of organic resin anti-corrosion
Property surface treatment.
According to the hydrophilic epithelium forming method of the present invention, being formed by aluminum or aluminum alloy etc. for above-mentioned chemical conversion treatment is being implemented
Metal base surface on, the step of being coated above-mentioned hydrophilizing agent.As coating method, for example, have rolling method,
Stick coating method, infusion process, sputtering method, bristle rubbing method etc..After coating, it is preferable that dry 3 seconds at a temperature of 120~300 DEG C~
60 minutes, hydrophilic epithelium is obtained by sintering.When sintering temperature is less than 120 DEG C, then it can not obtain and sufficiently make film, exist
It is impregnated in the risk that epithelium after water dissolves.When more than 300 DEG C, then resin be present and decompose, damage hydrophilic epithelium
Hydrophilic risk.
The hydrophilic epithelium ＞ of ＜
The hydrophilic epithelium formed by above-mentioned hydrophilic epithelium forming method is on metal, especially aluminium and its alloy surface
The epithelium of formation, is hydrophily, is especially attached with that the hydrophilic continuation after pollutant is excellent and adaptation also excellent epithelium.
The thickness of above-mentioned hydrophilic epithelium is preferably 0.3~10 μm.When the thickness of hydrophilic epithelium is less than 0.3 μm, parent be present
The tendency that water-based and hydrophilic continuation reduces.When the thickness of hydrophilic epithelium is less than 10 μm, the tendency of drainage reduction be present.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in more detail, but the invention is not restricted to these embodiments.
＜ materials ＞
PAA-1：Polyacrylic acid (weight average molecular weight：20000, acid number 780mgKOH/g)
PVA：Polyvinyl alcohol (weight average molecular weight：20000, saponification degree：98.5)
PEO (comparative example 10)：PEO (weight average molecular weight：500000)
PEG：Polyethylene glycol (weight average molecular weight：20000)
Resin particle：Crosslinkable microparticles (preparation method subsequent descriptions)
[preparation method of crosslinkable microparticles]
The mass parts of N hydroxymethyl acrylamide 60 and the poly- second two of methoxyl group will be dissolved with the mass parts of methoxypropanol 200
Alcohol monomethacrylates (number of repeat unit is 100 Polyethylene Chain) 20 mass parts, the mass parts of acrylic acid 10, acrylamide 10
The monomer solution that mass parts obtain, and " ACVA " (Otsuka Chemical Co., Ltd is dissolved with the mass parts of methoxypropanol 50
Prepare, azo series initiators) solution of 1 mass parts, respectively from different mouths, in a nitrogen atmosphere, at 105 DEG C through 3 hours
It is added dropwise in the mass parts of methoxypropanol 150, further heating stirring is polymerize for 1 hour.In resulting dispersion liquid, hand over
The average grain diameter of connection property particulate is 350nm, and the water-swellable rate of crosslinkable microparticles is 1.15, and viscosity Ford cup No.4 is 18
Second, solid constituent concentration is 20 mass %.
The modulation ＞ of ＜ hydrophilizing agents
By the composition shown in table 1 and table 2, according to the ratio shown in table 1 and table 2 (in the solid composition of hydrophilizing agent
Amount (unit：Quality %)) mixed, modulate used in hydrophilizing agent used in embodiment and comparative example
Hydrophilizing agent.
The preparation ＞ of the breadboard of ＜ embodiments and comparative example
1000 by 150mm × 200mm × 0.13mm be the surf that aluminium is prepared by Nippon Paint Co., Ltd.
Cleaner EC370 1% solution, degreasing 5 seconds at 70 DEG C, the Alsurf 4130 prepared using Nippon Paint Co., Ltd.
10% solution carried out at 40 DEG C 5 seconds phosphoric acid chromate processing.Then, each hydrophilizing agent of above-mentioned gained is modulated
Into solid composition 5%, it is coated on by rod coater #4 on above-mentioned aluminium, being heated 20 seconds at 220 DEG C makes its drying, system
Standby each breadboard.The coating weight of hydrophilizing agent is adjusted, to cause the thickness of dried hydrophilic epithelium as 1 μm.It is resulting
Each breadboard, carry out following evaluation.
The evaluation ＞ of ＜ initial hydrophilicities
The contact angle between water droplet of evaluation test plate.Water contact angle uses automatic contact angle instrument (model：DSA20E,
It is prepared by KRUSS commercial firms) it is measured.The contact angle determined is, under room temperature environment, water droplet drip 30 seconds after breadboard with
Contact angle between water droplet.Evaluation result is shown in table 1 and table 2.It should be noted that when contact angle is less than 10 °, parent is confirmed as
It is water-based good.
The evaluation ＞ of the hydrophilic continuation of ＜
Breadboard is immersed in pure water 240 hours, its drying is made after taking-up, then, determines dry breadboard and water
The water contact angle of drop.The measure of contact angle, use automatic contact angle instrument (model：It is prepared by DSA20E, KRUSS commercial firm) surveyed
It is fixed.The contact angle determined is, under room temperature environment, water droplet drip 30 seconds after breadboard and water droplet between contact angle.Comment
Valency result is shown in table 1 and table 2.It should be noted that when contact angle is less than 10 °, it is good to confirm as hydrophily.
The evaluation ＞ of the wet adaptations of ＜
The spraying of pure water is blowed and sprayed to breadboard, epithelium is wiped with general 500g load with finger.Come and gone with 1 as 1 time,
Evaluation is until expose the number of the substrate of breadboard.Evaluation result is shown in table 1 and table 2.When until exposing the substrate of breadboard
Number is more than 8 times, then it is assumed that adaptation is good.
The evaluation ＞ of ＜ drainages
On the breadboard of horizontal arrangement, 10 μ L water droplet is loaded.Then, breadboard is placed vertically, measure water droplet moves
Move to below 8cm time, evaluate drainage.Evaluation result is shown in table 1 and table 2.When the time of measure was less than 10 seconds, then recognize
It is good for drainage.
The evaluation ＞ of ＜ soil release performance
Breadboard is immersed in pure water 24 hours, takes out, makes its drying.Then, dried breadboard is immersed in
By double (2- ethylhexyls) 3 mass of the mass parts of stearic acid 3, the mass parts of 1- octadecyl alcolols 3, the mass parts of palmitic acid 3 and phthalic acid
30 seconds in the solution that the trichloro ethylene that part is dissolved in 1188 mass parts is formed.The breadboard after spontaneously drying is taken out after being impregnated with, is blown
Spray the spraying of pure water and spontaneously dried, the water contact angle of determination test plate and water droplet.The measure of contact angle, using connecing automatically
Feeler instrument (model：It is prepared by DSA20E, KRUSS commercial firm) it is measured.The contact angle determined is, under room temperature environment, water droplet
The contact angle between breadboard and water droplet after dripping 30 seconds.Evaluation result is shown in table 1 and table 2.When water contact angle is more than B
When, it is good to confirm as hydrophily.
(evaluation criterion)
A：Water contact angle is less than 20 °
B：More than 20 ° but below 30 °
C：More than 30 ° but below 50 °
D：More than 50 °
[table 1]
[table 2]
The preparation ＞ of the breadboard of ＜ test examples
As shown in table 3, using the hydrophilizing agent of embodiment 2,4,5 or 7, the breadboard of test example is prepared.Test example
Breadboard preparation, in addition to the thickness of the dried hydrophilic epithelium formed thickness as shown in table 3, with implementation
The preparation of the breadboard of example and comparative example is carried out in the same way.To resulting each breadboard, with embodiment and comparative example
Breadboard similarly evaluated.Evaluation result is shown in table 3.
[table 3]
It was found from the comparison of embodiment 1 and comparative example 1, wet adaptation, drainage and the decontamination of the hydrophilic epithelium of embodiment 1
Property is excellent.In addition, it was found from the comparison of embodiment 2 and comparative example 2, the wet adaptation of the hydrophilic epithelium of embodiment 2, hydrophily,
Drainage and soil release performance are excellent.By these results, pass through (methyl) acrylic acid contained by hydrophilizing agent
The solid composition containing ratio for being resin (A) is 10~30 mass %, and the hydrophilic epithelium formed has excellent hydrophily, wet close
Conjunction property, drainage and soil release performance.
It was found from the comparison of embodiment 3 and comparative example 3, the hydrophily of the hydrophilic epithelium of embodiment 3, wet adaptation, draining
Property and soil release performance are excellent.In addition, it was found from the comparison of embodiment 4 and comparative example 4, the drainage of the hydrophilic epithelium of embodiment 4 and
Soil release performance is excellent.As can be known from these results, contained by the solid composition of the polyvinyl alcohol (B) contained by hydrophilizing agent
It is 10~40 mass % to have rate, and the hydrophilic epithelium formed has excellent hydrophily, wet adaptation, drainage and soil release performance.
It was found from the comparison of embodiment 5 and comparative example 5, the hydrophilic epithelium of embodiment 5 has excellent hydrophily, hydrophilic held
Continuous property and drainage.In addition, it was found from the comparison of embodiment 6 and comparative example 6, the hydrophilic epithelium of embodiment 6 has excellent parent
Water continuation, wet adaptation and soil release performance.As can be known from these results, by making hydrophilizing agent contain polyalkylene ether resin
(C) 15~50 mass %, the hydrophilic epithelium formed have excellent hydrophily, hydrophilic continuation, wet adaptation, drainage and
Soil release performance.
It was found from the comparison of embodiment 7 and comparative example 7, the hydrophilic epithelium of embodiment 7 has excellent hydrophily, wet closely sealed
Property, drainage and soil release performance.In addition, it was found from the comparison of embodiment 8 and comparative example 8, the hydrophilic epithelium of embodiment 8 has excellent
Drainage.As can be known from these results, crosslinkable microparticles son (D) 30~65 mass % is contained by hydrophilizing agent,
The hydrophilic epithelium formed has excellent hydrophily, wet adaptation, drainage and soil release performance.
It was found from the comparison of test example 1 and test example 9, the hydrophilic epithelium of test example 1 has excellent hydrophily and decontamination
Property.In addition, it was found from the comparison of test example 2 and test example 10, the hydrophilic epithelium of test example 2 have excellent hydrophilic continuation,
Wet adaptation, drainage and soil release performance.As can be known from these results, it is 0.3~10 μm by the thickness of hydrophilic epithelium, can
Improve hydrophily, hydrophilic continuation, wet adaptation, drainage and soil release performance.
Industrial applicability
According to the hydrophilizing agent of the present invention, can be formed in metal surface with the state of be attached with water compared with
High hydrophilic continuation and the hydrophilic epithelium of excellent drainage.Therefore, according to the hydrophilizing agent of the present invention, enable in particular to
Hydrophilic epithelium is formed suitable for the fin surface of the heat exchanger in air conditioner etc..
Claims (according to the 19th article of modification of treaty)
1. a kind of hydrophilizing agent, for forming hydrophilic epithelium on the surface of metal base,
With (methyl) containing the repeat unit for coming from acrylic monomers and/or the repeat unit for coming from methacrylic acid monomer
Acrylic resin (A), polyvinyl alcohol (B), polyalkylene ether resin (C) and crosslinkable microparticles are sub (D)；
(methyl) acrylic resin (A),
(1) repeat unit of the repeat unit that comes from the monomer with sulfo group and the monomer with amide groups is not contained,
(2) weight average molecular weight is 20000~2000000,
(3) acid number of resin solid composition is 100~800mgKOH/g；
The polyalkylene ether resin (C) is polyethylene glycol；
The crosslinkable microparticles sub (D) by the mass % of monomer (a) 30~95 represented by following formula (I)s, contain polyoxygenated
Alkene chain and the mass % of the monomer (b) of polymerism double bond 5~60 and other polymerizable monomers (c) 0~50 mass % are copolymerized and shape
Into,
[changing 1]
In formula, R1Represent H or methyl, R2Represent CH2Or C2H4；
In the solid composition of the hydrophilizing agent, the containing ratio of (methyl) acrylic resin (A) is 10~30
Quality %, the containing ratio of the polyvinyl alcohol (B) is 10~40 mass %, and the containing ratio of the polyalkylene ether resin (C) is
15~50 mass %, the containing ratio of the crosslinkable microparticles sub (D) is 30~65 mass %.
2. a kind of hydrophilic epithelium forming method, comprises the following steps：
The surface of the aluminium base is set to contact the step of chemical conversion treatment dosage form is into chemical conversion epithelium；
It is set to contact the hydrophilizing agent described in claim 1 to form hydrophilic skin for the chemical conversion epithelium obtained by the step
The step of film.
3. a kind of hydrophilic epithelium, by hydrophilic epithelium forming method according to claim 2 the metal base table
Face is formed.
4. hydrophilic epithelium according to claim 3, thickness is 0.3~10 μm.
Illustrate or state (according to the 19th article of modification of treaty)
The modification of claim 1
In claim 1, by " weight average molecular weight of the polyalkylene ether resin (C) is 5000~500000 " modifications
For " the polyalkylene ether resin (C) is polyethylene glycol ".That is, " polyalkylene ether resin (C) " is limited
For the correction of " polyethylene glycol ".The benefit is based on the original paragraphs 0077 of the application, paragraph 0079 and embodiment 1-11
Record carry out.
Claims (4)
1. a kind of hydrophilizing agent, for forming hydrophilic epithelium on the surface of metal base,
With (methyl) containing the repeat unit for coming from acrylic monomers and/or the repeat unit for coming from methacrylic acid monomer
Acrylic resin (A), polyvinyl alcohol (B), polyalkylene ether resin (C) and crosslinkable microparticles are sub (D)；
(methyl) acrylic resin (A),
(1) repeat unit of the repeat unit that comes from the monomer with sulfo group and the monomer with amide groups is not contained,
(2) weight average molecular weight is 20000~2000000,
(3) acid number of resin solid composition is 100~800mgKOH/g；
The weight average molecular weight of the polyalkylene ether resin (C) is 5000~500000；
The crosslinkable microparticles sub (D) by the mass % of monomer (a) 30~95 represented by following formula (I)s, contain polyoxygenated
Alkene chain and the mass % of the monomer (b) of polymerism double bond 5~60 and other polymerizable monomers (c) 0~50 mass % are copolymerized and shape
Into,
[changing 1]
In formula, R1Represent H or methyl, R2Represent CH2Or C2H4；
In the solid composition of the hydrophilizing agent, the containing ratio of (methyl) acrylic resin (A) is 10~30
Quality %, the containing ratio of the polyvinyl alcohol (B) is 10~40 mass %, and the containing ratio of the polyalkylene ether resin (C) is
15~50 mass %, the containing ratio of the crosslinkable microparticles sub (D) is 30~65 mass %.
2. a kind of hydrophilic epithelium forming method, comprises the following steps：
The surface of the aluminium base is set to contact the step of chemical conversion treatment dosage form is into chemical conversion epithelium；
It is set to contact the hydrophilizing agent described in claim 1 to form hydrophilic skin for the chemical conversion epithelium obtained by the step
The step of film.
3. a kind of hydrophilic epithelium, by hydrophilic epithelium forming method according to claim 2 the metal base table
Face is formed.
4. hydrophilic epithelium according to claim 3, thickness is 0.3~10 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-113523 | 2015-06-03 | ||
| JP2015113523A JP6654814B2 (en) | 2015-06-03 | 2015-06-03 | Hydrophilizing agent, hydrophilic film forming method and hydrophilic film |
| PCT/JP2016/066609 WO2016195081A1 (en) | 2015-06-03 | 2016-06-03 | Hydrophilization treatment agent, hydrophilic film formation method, and hydrophilic film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107614633A true CN107614633A (en) | 2018-01-19 |
Family
ID=57440479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680031155.9A Pending CN107614633A (en) | 2015-06-03 | 2016-06-03 | Hydrophilizing agent, hydrophilic epithelium forming method and hydrophilic epithelium |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6654814B2 (en) |
| KR (1) | KR20180015155A (en) |
| CN (1) | CN107614633A (en) |
| WO (1) | WO2016195081A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126346A (en) * | 2020-09-03 | 2020-12-25 | 苏州铱诺化学材料有限公司 | Aluminum fin stamping coating agent and preparation method and application thereof |
| CN113226571A (en) * | 2018-12-28 | 2021-08-06 | 日涂表面处理化工有限公司 | Hydrophilizing agent, method for forming hydrophilic coating film, and hydrophilic coating film |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660071B (en) * | 2014-06-30 | 2020-12-25 | 日涂表面处理化工有限公司 | Method for coating aluminum fin material with hydrophilic coating film, aluminum fin material, and aluminum heat exchanger |
| WO2019077746A1 (en) * | 2017-10-20 | 2019-04-25 | 東洋製罐グループホールディングス株式会社 | Organic resin coated surface-treated metal plate |
| CN112262041B (en) * | 2018-07-24 | 2023-04-21 | 株式会社Uacj | Pre-coated aluminum material |
| EP4130170A4 (en) * | 2020-03-24 | 2024-04-24 | Nitto Denko Corp | Composition for coating-film formation, and coating film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005002151A (en) * | 2003-06-09 | 2005-01-06 | Nippon Paint Co Ltd | Cross-linkable fine particle, hydrophilization treating agent, method for coating hydrophilic film and hydrophilic film |
| JP2014000534A (en) * | 2012-06-19 | 2014-01-09 | Nippon Paint Co Ltd | Hydrophilic coating film covering method of aluminum fin material, aluminum fin material and aluminum heat exchanger |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660071B (en) * | 2014-06-30 | 2020-12-25 | 日涂表面处理化工有限公司 | Method for coating aluminum fin material with hydrophilic coating film, aluminum fin material, and aluminum heat exchanger |
-
2015
- 2015-06-03 JP JP2015113523A patent/JP6654814B2/en active Active
-
2016
- 2016-06-03 CN CN201680031155.9A patent/CN107614633A/en active Pending
- 2016-06-03 KR KR1020177035699A patent/KR20180015155A/en unknown
- 2016-06-03 WO PCT/JP2016/066609 patent/WO2016195081A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005002151A (en) * | 2003-06-09 | 2005-01-06 | Nippon Paint Co Ltd | Cross-linkable fine particle, hydrophilization treating agent, method for coating hydrophilic film and hydrophilic film |
| JP2014000534A (en) * | 2012-06-19 | 2014-01-09 | Nippon Paint Co Ltd | Hydrophilic coating film covering method of aluminum fin material, aluminum fin material and aluminum heat exchanger |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113226571A (en) * | 2018-12-28 | 2021-08-06 | 日涂表面处理化工有限公司 | Hydrophilizing agent, method for forming hydrophilic coating film, and hydrophilic coating film |
| CN112126346A (en) * | 2020-09-03 | 2020-12-25 | 苏州铱诺化学材料有限公司 | Aluminum fin stamping coating agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016195081A1 (en) | 2016-12-08 |
| JP2016222879A (en) | 2016-12-28 |
| KR20180015155A (en) | 2018-02-12 |
| JP6654814B2 (en) | 2020-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107614633A (en) | Hydrophilizing agent, hydrophilic epithelium forming method and hydrophilic epithelium | |
| JP5995546B2 (en) | Method for coating hydrophilic film of aluminum fin material, aluminum fin material, and aluminum heat exchanger | |
| JP3819956B2 (en) | Composition for hydrophilic treatment and method for hydrophilic treatment | |
| CN106660071A (en) | Method for coating aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger | |
| EP0709409B1 (en) | Hydrophilic crosslinked polymer fine particles and process for production thereof | |
| JP2011148889A (en) | Hydrophilicizing treatment agent | |
| JP4464076B2 (en) | Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film | |
| KR20190137785A (en) | Method of forming hydrophilic treatment agent and hydrophilic coating | |
| JP2018023932A (en) | Hydrophilic film coating method of aluminum fin material, aluminum fin material, and heat-exchanger made of aluminum | |
| JP3488929B2 (en) | Hydrophilic crosslinked polymer fine particles and method for producing the same | |
| JP5180145B2 (en) | Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film | |
| CN113226571B (en) | Hydrophilizing agent, method for forming hydrophilic coating film, and hydrophilic coating film | |
| JP2009179811A5 (en) | ||
| JP4834194B2 (en) | Water-based paint composition | |
| JP2000248225A (en) | Composition for hydrophilic treatment, and hydrophilic treatment | |
| US5681889A (en) | Hydrophilic crosslinked polymer fine particles and process for production thereof | |
| JP7129481B2 (en) | Aqueous dispersion, method for producing the same, coating composition and coating film | |
| JP2013170211A (en) | Method of producing polymeric emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180119 |
|
| RJ01 | Rejection of invention patent application after publication |