CN103132117A - Film-forming method - Google Patents
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- CN103132117A CN103132117A CN2012104975069A CN201210497506A CN103132117A CN 103132117 A CN103132117 A CN 103132117A CN 2012104975069 A CN2012104975069 A CN 2012104975069A CN 201210497506 A CN201210497506 A CN 201210497506A CN 103132117 A CN103132117 A CN 103132117A
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- oxide film
- film
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- electrodeposition coating
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Abstract
An object of the invention is to provide a film-forming method. The method comprises the steps of forming anionic electrodeposition coating film with a dry film thickness of 1 [mu]m to 5 [mu]m on an anodic oxide film with a thickness of 2 [mu]m to 5 [mu]m, wherein the anodic oxide film has holes with average hole diameter of 30 nm to 300 nm; and providing coating articles with excellent impact resistance and water resistance obtained by the film-forming method. The film-forming method provided by the invention comprises the steps of immersing aluminum or an aluminum alloy in a phosphoric acid aqueous solution or an oxalic acid aqueous solution (A); anodizing the surface of the aluminum or an aluminum alloy to form the anodic oxide film with the thickness of 2 [mu]m to 5 [mu]m; wherein the oxide film has holes with average hole diameter of 30 nm to 300 nm; and electro-depositing an anionic electrodeposition coating (B) to form the electrodeposition film on the surface of the anodic oxide film, wherein the dry thickness of the electrodeposition coating film is 1 [mu]m to 5 [mu]m metering from the surface of the anodic oxide film; and the depth of the electrodeposition coating film in the anodic oxide film is larger than 1 [mu]m.
Description
Technical field
The present invention relates to film formation method, it is included in and forms desciccator diaphragm thickness on the anode oxide film that thickness is 2 μ m to 5 μ m is the negatively charged ion electrodeposition coating of 1 μ m to 5 μ m, and described anode oxide film has the hole that mean pore size is 30nm to 300nm; And relate to the coated article with excellent impact resistance and water tolerance that obtains by described film formation method.
Background technology
The anodic oxidation of the aspect excellences such as lightweight and intensity, erosion resistance (alumite is processed) aluminum has been used for various building materials, for example aluminium windowframe, gold utensil, balcony base material, roof Material, window shutter, door, sliding gate, door pocket and solaria thereon in moulding and after galvanic deposit acrylic resin/melamine cured anionic electrodeposition electrodeposition coating compositions is filmed with formation.
In the conventional aluminium windowframe manufacture method that comprises " anodic oxidation and electrodeposition-coating " step, for example, be (referring to the Fig. 3 about coating structure) when forming the desciccator diaphragm thickness of 7 μ m on the anode oxide film of 9 μ m when making electrodeposition coating at thickness, for anodic oxidation, the electric power that every square metre of building materials use is 1.32kWh/m
2, and be 0.15kWh/m for electrodeposition-coating
2
Recently, the requirement of energy-conservation in order to satisfy (power save, saving of fuel) has required anode oxide film (2 μ m to 5 μ m) and negatively charged ion electrodeposition coating (desciccator diaphragm thickness: 1 μ m to 5 μ m) all attenuation (referring to the Fig. 4 about coating structure).Existed making anode oxide film and the equal attenuation of negatively charged ion electrodeposition coating, keeping simultaneously the demand of coating performance.
It is that the desciccator diaphragm thickness that forms on the anode oxide film of approximately 9 μ m is the specific negatively charged ion electrodeposition coating of 1 μ m to 7 μ m that patent documentation (PTL) 1 discloses at thickness.Yet when on the anode oxide film that at very thin thickness is 2 μ m to 5 μ m, formation desciccator diaphragm thickness was the negatively charged ion electrodeposition coating of 1 μ m to 5 μ m, shock resistance and water tolerance significantly reduced.
The prior art document
Patent documentation
1: the 2007-9059 Japanese unexamined patent of PTL is open
Summary of the invention
Technical problem
The object of the invention is to find film formation method, it can be that to form desciccator diaphragm thickness on the anode oxide film of 2 μ m to 5 μ m be the negatively charged ion electrodeposition coating with excellent coating performance of 1 μ m to 5 μ m at thickness, and the coated article with excellent shock resistance, water tolerance and the electrodeposition coating formability in the anodic oxidation fenestra is provided.
The solution of problem scheme
The inventor conducts extensive research, and find by comprising that following film formation method can realize this purpose, described method comprises aluminum is immersed specific aqueous solution (A) to form thickness as the anode oxide film of 2 μ m to 5 μ m on the aluminum surface, described anode oxide film has the hole that mean pore size is 30nm to 300nm, then make negatively charged ion electrocoating paint (B) galvanic deposit on anode oxide film to form desciccator diaphragm thickness as 1 μ m to 5 μ m and the degree of depth in the described anodic oxidation fenestra electrodeposition coating more than or equal to 1 μ m.
More specifically, the invention provides down and list:
1. be used to form the method for film, it comprises aluminum or aluminum alloy is immersed in phosphate aqueous solution or oxalic acid aqueous solution (A), and make the surperficial anodic oxidation of described aluminum or aluminum alloy and form the anode oxide film that thickness is 2 μ m to 5 μ m, described anode oxide film has the hole that mean pore size is 30nm to 300nm, then make negatively charged ion electrocoating paint (B) galvanic deposit form electrodeposition coating on the surface of described anode oxide film, the dry film thickness of described electrodeposition coating is 1 μ m to 5 μ m from the meter of the surface of described anode oxide film, and the degree of depth of described electrodeposition coating in the hole of described anode oxide film is more than or equal to 1 μ m, wherein, it is the emulsion of 30nm to 100nm that described negatively charged ion electrocoating paint (B) comprises by making the resin Composition that comprises carboxylic resin (b1) and blocked isocyanate (b2) be dispersed in water the median size that obtains, and the mean pore size that the median size of described emulsion deducts described hole is equal to or less than 20nm.
2. as 1 a described method, wherein said carboxylic resin (b1) is to comprise carboxylic unsaturated monomer, polyether-modified vinylformic acid unsaturated monomer and the free-radical polymerized acrylic resin that obtains of monomer mixture (b) of the polymerisable unsaturated monomer of another kind of free radical by making.
3. as 1 or 2 a described method, wherein said anionic electrodeposition electrodeposition coating compositions (B) comprises the compound by following general formula (1) expression:
Wherein R is the alkyl that contains 7 to 9 carbon atoms, and n is 10 to 16 integer.
4. the described method of any one as in 1 to 3, wherein said anode oxide film is by immersing aluminum or aluminum alloy phosphate aqueous solution or oxalic acid aqueous solution (A) and with 0.5A/dm
2To 3.0A/dm
2Current density apply electric current and form.
5. the article that apply, it obtains by the described method of any one in item 1 to 4.
Advantageous effects of the present invention
The article of the coating that obtains by film formation method of the present invention have excellent shock resistance and water tolerance.Such excellent properties may be realized due to underlying cause: be the hole of 30nm to 300nm because the anode oxide film that uses in the present invention has mean pore size, so the anionic electrodeposition electrodeposition coating compositions can easily be penetrated in the hole and form the degree of depth more than or equal to the electrodeposition coating of 1 μ m in the hole; Therefore, having excellent shock resistance and the electrodeposition coating of water tolerance can obtain due to the grappling effect of filming.
The accompanying drawing summary
Fig. 1 is for by immersing aluminium the electron photomicrograph (* 5,000) of " anode oxide film " that the described aluminium of aqueous sulfuric acid and anodic oxidation surface obtains.
Fig. 2 is for by immersing aluminium the electron photomicrograph (* 5,000) of " anode oxide film " that the described aluminium of phosphate aqueous solution and anodic oxidation surface obtains.
Fig. 3 has described the graph model of the conventional film that forms by " anodic oxidation and electrodeposition-coating ".
Fig. 4 has described the graph model of the film of the present invention that forms by " anodic oxidation and electrodeposition-coating ".
Embodiment is described
the invention provides film formation method, it comprises aluminum or aluminum alloy is immersed in phosphate aqueous solution or oxalic acid aqueous solution (A) to form desciccator diaphragm thickness as the anode oxide film of 2 μ m to 5 μ m, described anode oxide film has the hole that mean pore size is 30nm to 300nm, then make negatively charged ion electrocoating paint (B) galvanic deposit on the surface of described anode oxide film to form electrodeposition coating, the desciccator diaphragm thickness of described electrodeposition coating is 1 μ m to 5 μ m from the meter of the surface of described anode oxide film, and the degree of depth of described electrodeposition coating in the hole of described anode oxide film is more than or equal to 1 μ m, it is the emulsion of 30nm to 100nm that wherein said electrocoating paint (B) comprises by making the resin Composition that comprises carboxylic resin (b1) and blocked isocyanate (b2) be dispersed in water the median size that obtains, and the mean pore size that the median size of described emulsion deducts described hole is equal to or less than 20nm.
According to film formation method of the present invention, at first aluminum or aluminum alloy is carried out degreasing, etching and neutralization, then immerse in phosphate aqueous solution or oxalic acid aqueous solution (A).Make the surface " anodic oxidation " of aluminum or aluminum alloy to form anode oxide film.
Then, after randomly using hot water injection's film, " negatively charged ion electrocoating paint (B) " is used for carrying out the negatively charged ion electrodeposition-coating.Subsequently, (do not rinse) in the situation that wash with water or washing (flushings) with water afterwards, heating and dry with formation negatively charged ion electrodeposition coating, until desciccator diaphragm thickness is 1 μ m to 5 μ m, 2 μ m to 4 μ m more preferably.Term used herein " desciccator diaphragm thickness " refers to the thickness of the electrodeposition coating that forms on the atresia plane surface of anode oxide film.
These steps can form the degree of depth filming more than or equal to the negatively charged ion electrocoating paint of 1 μ m in the hole of anode oxide film.Due to the grappling effect of filming, can obtain to have excellent shock resistance and the coated article of water tolerance.Detailed hereafter the present invention.
Anodic oxidation
Carry out anodic oxidation by aluminum or aluminum alloy being immersed phosphate aqueous solution or oxalic acid aqueous solution (A) and subsequently aluminum or aluminum alloy being applied direct current as anode.The bath temperature of phosphate aqueous solution or oxalic acid aqueous solution (A) is preferably 10 ° of C to 50 ° of C, and 18 ° of C to 40 ° of C more preferably.Preferably with 0.5A/dm
2To 3.0A/dm
2, more preferably 0.7A/dm
2To 2.3A/dm
2Current density apply electric current.Electric current preferably applies 10 seconds to 60 minutes, more preferably 20 seconds to 20 minutes.
Anode oxidation process can form thickness to be 1 μ m to 5 μ m, preferred 2 μ m to 4 μ m and to have mean pore size (annotate 1) and be the anode oxide film in the hole of 30nm to 300nm, preferred 50nm to 250nm.If need, electric current can repeatedly apply for several times.In the present invention, the mean pore size in hole refers to the mean value (annotating 1) of major diameter (or maximum diameter) of the opening in the hole that forms by anode oxidation process.The degree of depth in hole is usually less than 3 μ m, and at least the degree of depth in some hole more than or equal to 1 μ m.
The mean pore size in (annotating 1) hole: can be by using scanning electron microscope (* 5,000) major diameter of metering orifice on the electron photomicrograph of taking (being maximum diameter during close to circle when shape), calculate the mean value in 20 holes (n=20), and this value is defined as mean pore size (nm), thereby determines the mean pore size in hole.
The example of aluminium alloy comprises the alloy of aluminium and at least a metal, for example: non-heat treated alloy, for example 3000 series A l-Mn alloys, 4000 series A l-Si alloys and 5000 series A l-Mg alloys; And heat treated alloy, for example 2000 series A l-Cu-Mg alloys, 6000 series A l-Mg-Si alloys and 7000 series A l-Zn-Mg alloys.
Anodised reaction mechanism of the present invention is as follows.When aluminum or aluminum alloy being immersed in " phosphate aqueous solution " bath and applying electric current, form " Al according to reaction formula as follows
2O
3" film.
The liberation degree of phosphoric acid is pK
a1=2.15, pK
a2=7.2 and pK
a3=12.4; " Al
2O
3" generation be considered to minute slowly to carry out as the next stage:
2Al+3H
3PO
4+3H
2O→Al
2O
3+2H
3PO
4+9H
++PO
4 3-+6e
-
2Al+2H
2PO
4 -+3H
2O→Al
2O
3+H
3PO
4+7H
++PO
4 3-+6e
-
2Al+HPO
4 2-+3H
2O→Al
2O
3+7H
++PO
4 3-+6e
-
Perhaps, when aluminum or aluminum alloy being immersed in " oxalic acid aqueous solution " bath and applying electric current, form " Al according to following formula
2O
3" film.The liberation degree of oxalic acid is pK
a1=1.27 and pK
a2=4.27.Be similar to the situation of use " phosphate aqueous solution ", " Al
2O
3" generation be considered to minute slowly to carry out as the next stage:
2Al+2H
2C
2O
4+3H
2O→Al
2O
3+2HC
2O
4 -+8H
++8e
-
2Al+2HC
2O
4 -+3H
2O→Al
2O
3+2C
2O
4 -+8H
++8e
-
Consequent " Al
2O
3" be believed to be helpful in the water tolerance of improving the negatively charged ion electrodeposition coating.Compare with the situation of using conventional electrolyte sulfuric acid, use " phosphate aqueous solution " or " oxalic acid aqueous solution " can be easy to due to underlying cause as ionogen mean pore size is adjusted to above-mentioned scope.The conventional sulfuric acid that uses has high liberation degree (acid ionization constant pK
a1=1.99), therefore can form rapidly Al
2O
3Preformed " Al
2O
3" be tending towards causing electric current unstable, and become and be difficult to form the anode oxide film with wide aperture and good smooth finish.
Yet, because carrying out multistep, phosphoric acid and oxalic acid dissociates, so compare with the situation of using sulfuric acid, form more lentamente Al
2O
3, relatively can not electric current occur unstable, and can form the anode oxide film with wide aperture and good smooth finish.In addition, can form anode oxide film in the depths in the hole.The concentration of phosphate aqueous solution or oxalic acid aqueous solution (A) is preferably 1 quality % to 40 quality %, 20 quality % to 35 quality % more preferably, thereby be easy to control current density and current duration, and form that to have hole and the thickness that mean pore size is 30nm to 300nm be the anode oxide film of 2 μ m to 5 μ m.This makes it possible to form the negatively charged ion electrodeposition coating with excellent adhesion, and it is preferred thus.
Negatively charged ion electrocoating paint (B)
The negatively charged ion electrocoating paint (B) that uses in the present invention comprises median size and is the emulsion of 30nm to 100nm, it obtains by the resin Composition that comprises carboxylic resin (b1) and blocked isocyanate (b2) is dispersed in water, and satisfies following equation:
[mean pore size in the median size-hole of emulsion]≤20nm.
Especially, for forming the degree of depth in the anodic oxidation fenestra more than or equal to for the electrodeposition coating of 1 μ m, it is preferred satisfying following equation.
[mean pore size in the median size-hole of emulsion]≤0nm.
The example of carboxylic resin (b1) comprises acrylic resin, vibrin, polyether resin, polycarbonate resin, urethane resin etc.In view of weathering resistance and smooth finish, acrylic resin is particularly preferred.
Can be used for acrylic resin of the present invention by using polymerization starter, make the monomer mixture that comprises carboxylic unsaturated monomer and the polymerisable unsaturated monomer of another kind of free radical free-radical polymerized and obtain in solvent.
Preferably, acrylic resin (b) is by using polymerization starter, make the monomer mixture that comprises carboxylic unsaturated monomer, polyether-modified vinylformic acid unsaturated monomer and the polymerisable unsaturated monomer of another kind of free radical free-radical polymerized and obtain in solvent.
The example of carboxylic unsaturated monomer like this comprises the monomer such as vinylformic acid, methacrylic acid, β-crotonic acid, methylene-succinic acid, toxilic acid and fumaric acid.
the example of the polymerisable unsaturated monomer of another kind of free radical comprises the polymerisable unsaturated monomer of free radical of hydroxyl, for example (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester and (methyl) vinylformic acid hydroxyl butyl ester, and PLACCEL FM1, PLACCEL FM2, PLACCEL FM3, PLACCEL FA1, PLACCEL FA2 and PLACCEL FA3 (trade(brand)name, produced the hydroxyl of caprolactone modification (methyl) acrylate by Daicel company), the unsaturated monomer that contains alkoxysilyl, for example γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl-triethoxysilicane and vinyltrimethoxy silane, alkyl or cycloalkyl (methyl) acrylate monomer, wherein alkyl or cycloalkyl partly comprises 1 to 18 carbon atom, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) dodecyl acrylate, (methyl) 2-EHA and (methyl) cyclohexyl acrylate, aromatic vinyl monomer, for example vinylbenzene, and (methyl) acrylamide monomer, (methyl) acrylic acid amides ((meth) acrylic acid amide) for example, N-methylol (methyl) acrylamide, N, N-dihydroxymethyl (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-ethoxyl methyl (methyl) acrylamide, N-isopropoxy methyl (methyl) acrylamide, N-n-butoxy methyl (methyl) acrylamide, the positive hexyloxy methyl of N-(methyl) acrylamide, N, N-dimethoxy-methyl (methyl) acrylamide, N, N-two-n-butoxy methyl (methyl) acrylamide and N-methoxymethyl-N-methylol (methyl) acrylamide.
The polyether-modified vinylformic acid unsaturated monomer of can be as required and adding is expressed from the next: CH
2=CRCOO (R ' O)
n(wherein R is hydrogen atom or methyl to-X, and R ' is-C
2H
4-or-C
3H
6-, X is hydrogen atom or methyl, n is 2 to 100, preferred 5 to 60, even more preferably 10 to 30 integer).
The example of polyether-modified vinylformic acid unsaturated monomer comprises polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, poly glycol monomethyl ether list (methyl) acrylate etc.
In the present invention, the initial monomers of carboxylic resin (b1) is preferably, for example, comprise carboxylic unsaturated monomer, wherein alkyl or cycloalkyl partly comprises the monomer mixture of the polymerisable unsaturated monomer of free radical of alkyl or cycloalkyl ester monomer, aromatic vinyl monomer and the hydroxyl of 1 to 18 carbon atom; Comprise the unsaturated monomer that contains alkoxysilyl, carboxylic unsaturated monomer, wherein alkyl or cycloalkyl partly comprises the monomer mixture of the polymerisable unsaturated monomer of free radical of alkyl or cycloalkyl ester monomer, aromatic vinyl monomer and the hydroxyl of 1 to 18 carbon atom; Comprise carboxylic unsaturated monomer, wherein alkyl or cycloalkyl partly comprises the polymerisable unsaturated monomer of free radical of alkyl or cycloalkyl ester monomer, aromatic vinyl monomer, hydroxyl of 1 to 18 carbon atom and the monomer mixture of polyether-modified vinylformic acid unsaturated monomer; Comprise the unsaturated monomer that contains alkoxysilyl, carboxylic unsaturated monomer, wherein alkyl or cycloalkyl partly comprises the polymerisable unsaturated monomer of free radical of alkyl or cycloalkyl ester monomer, aromatic vinyl monomer, hydroxyl of 1 to 18 carbon atom and the monomer mixture of polyether-modified vinylformic acid unsaturated monomer.
In radical polymerization, total amount based on monomer, polymeric solution preferably comprises the carboxylic polymerizable unsaturated monomer of 1 quality % to 20 quality %, preferred 4 quality % to 10 quality %, the polyether-modified vinylformic acid unsaturated monomer of 0 quality % to 30 quality %, preferred 10 quality % to 25 quality %, and the polymerisable unsaturated monomer of another kind of free radical of 50 quality % to 99 quality %, preferred 65 quality % to 86 quality %.
In acrylic resin, to comprise carboxylic unsaturated monomer, polyether-modified vinylformic acid unsaturated monomer and the monomer mixture acrylic resin that radical polymerization obtains in solvent (b) of the polymerisable unsaturated monomer of another kind of free radical be preferred by making to use polymerization starter, because the median size of emulsion can easily be adjusted to 30nm to 100nm.
The example of solvent comprises alcoholic solvent, for example n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol and isopropylcarbinol; Ether solvents, for example ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 2-methyl cellosolve, cellosolvo, 2-isopropoxide ethanol, butoxy ethanol, Diethylene Glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol and dipropylene glycol monomethyl ether.
The example of solvent also comprises aromatic solvent, for example dimethylbenzene and toluene; Ketone solvent, for example acetone, methyl ethyl ketone, 2 pentanone, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK), isophorone and pimelinketone; And ester solvent, for example methyl acetate, ethyl acetate, pentyl acetate, acetic acid 3-methoxyl group butyl ester, acetic acid 2-ethylhexyl, jasmal, hexalin acetate, propionic acid methyl and ethyl propionate.
The example that is used for the radical polymerization initiator of radical polymerization comprises superoxide, for example benzoyl peroxide, di-tert-butyl hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, t-butyl per(oxy)benzoate, lauryl peroxide, acetyl peroxide and the peroxidation 2 ethyl hexanoic acid tert-butyl ester; And azo-compound, α for example, α '-Diisopropyl azodicarboxylate, azo two (methyl pentane nitrile) (azobis (dimethylvaleronitrile)) and azo two (hexanaphthene formonitrile HCN) (azobis (cyclohexanecarbonitrile)).
The carboxylic resin (b1) that uses in the present invention have be preferably 5,000 to 150,000,20,000 to 100,000 weight-average molecular weight more preferably; Be preferably 20mg KOH/g to 150mg KOH/g, the acid number of 40mg KOH/g to 100mg KOH/g more preferably; And preferred 0mg KOH/g to 200mg KOH/g, the hydroxyl value of 15mg KOH/g to 150mgKOH/g more preferably.
" number-average molecular weight " used herein refers to the molecular weight based on polystyrene standard, according to JIS K 0124-83 method, and the value of the chromatogram calculation of measuring from gel permeation chromatography.For gel permeation chromatography, use " HLC8120GPC " (being produced by Tosoh company).Under following condition, use four kinds of posts, i.e. " TSK GEL G-4000HXL ", " TSK GEL G-3000HXL ", " TSK GEL G-2500HXL " and " TSK GEL G-2000HXL " (trade(brand)name; Produced by Tosoh company) measure: moving phase: tetrahydrofuran (THF), measure temperature: 40 ° of C, flow velocity: 1ml/min, and detector: RI.
Except carboxylic resin (b1), the negatively charged ion electrocoating paint (B) that uses in the present invention comprises block polyisocyanate compound (b2).Block polyisocyanate compound (b2) obtains by the isocyanate groups that uses the encapsulant blocked polyisocyanate compound.
The example of polyisocyanate compounds comprises aromatic series, aliphatics or alicyclic polymeric isocyanate compound, for example toluylene group diisocyanate, eylylene diisocyanate, phenylene diisocyanate (phenylene diisocyanate), two (isocyanic ester ylmethyl) hexanaphthene (bis (isocyanatemethyl) cyclohexane), tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate and isophorone diisocyanate; And the compound that contains terminal isocyanate by compound reaction that excessive such isocyanate compound and lower molecular weight contain active hydrogen is obtained, the described compound that contains active hydrogen is ethylene glycol, propylene glycol, TriMethylolPropane(TMP), hexanetriol or Viscotrol C for example.
On the other hand, add encapsulant with the isocyanate group of blocked polyisocyanate compound, and encapsulant preferably has following character: at room temperature stable by adding the block polyisocyanate compound that such encapsulant forms, yet, when the storing temperature that is heated to film (usually approximately 100 ° of C to about 200 ° of C), encapsulant produces free isocyanate group from Xie Yizai.
The example that satisfies the encapsulant of this demand comprises lactam compound, for example ε-caprolactam and butyrolactam; Oxime compound, for example methyl ethyl ketone oxime and cyclohexanone-oxime; Phenolic compound, for example phenol, p-tert-butyl phenol and cresols; Fatty Alcohol(C12-C14 and C12-C18), for example propyl carbinol and 2-Ethylhexyl Alcohol; Aromatic series alkyl alcohol, for example phenyl methanol and methyl phenyl carbinol; And ethyl alcohol compound, for example ethylene glycol monobutyl ether.
The example that is purchased product of block polyisocyanate compound (b2) comprises " BarnockD-750 ", " Barnock-800 ", " Barnock DN-950 ", " Barnock DN-970 " and " Barnock DN-15-455 " (trade(brand)name; By Dainippon Ink ﹠amp; Chemicals, Inc. produces), " Desmodule L ", " Desmodule N ", " Desmodule HL ", " DesmoduleIL " and " Desmodule N3390 " (trade(brand)name; Produced by Bayer AG); " TakenateD-102 ", " Takenate D-202 ", " Takenate D-110N " and " Takenate D-123N " (trade(brand)name; By Takeda Chemical Industries, Ltd. produces); " Coronate L ", " Coronate HL ", " Coronate EH " and " Coronate 203 " (trade(brand)name; By NipponPolyurethane Industry Co., Ltd. produces); And " Duranate 24A-90CX " (trade(brand)name; By Asahi Chemical Industry Co., Ltd. produces).
in view of water tolerance, adhesivity and smooth finish, carboxylic resin (b1) in negatively charged ion electrocoating paint (B) and the ratio of block polyisocyanate compound (b2) are preferably as follows: based on solid, total amount with respect to carboxylic resin (b1) and the block polyisocyanate compound (b2) of every 100 mass parts, the amount of carboxylic resin (b1) is 50 mass parts to 75 mass parts, and be preferably 50 mass parts to 65 mass parts, and the amount of block polyisocyanate compound (b2) is 25 mass parts to 50 mass parts, and be preferably 35 mass parts to 50 mass parts.
The emulsion of using in negatively charged ion electrocoating paint (B) can prepare in the following manner.With carboxylic resin (b1) and block polyisocyanate compound.After randomly adding curing catalysts, tensio-active agent etc., with respect to the carboxyl of carboxylic resin (b1), add basic cpd with the amount of 0.1 equivalent to 1.5 equivalent, preferred 0.2 equivalent to 1.2 equivalent.The gained mixture is mixed and disperses, and drip deionized water to realize solids content as 10 quality % to 60 quality %, preferred 10 quality % to 40 quality % to it.To 8.0, obtain thus median size is the emulsion of 30nm to 100nm, preferred 50nm to 90nm to the use neutralizing agent with pH regulator to 7.0.In order to be easy to that median size is adjusted to above-mentioned scope, the use of the adjustment of the amount of basic cpd and acrylic resin (b), tensio-active agent etc. is effective.
In view of deeper form electrodeposition coating in the hole, the emulsion with the median size in above-mentioned scope is preferred.Above-mentioned median size can be measured by the dynamic light scattering that uses " COULTER N5 " (trade(brand)name, by Beckman Coulter, Inc. produces) for example.
Add curing catalysts to strengthen low-temperature curable.In view of with the adhesivity of the excellence of filming of the superior compatibility of carboxylic resin (b1) and acquisition, curing catalysts is preferably the liquid tin compound, for example two lauric acid dioctyl tins, dibenzoic acid dioctyl tin and dibenzoic acid dibutyl tin.
Other examples of curing catalysts include but not limited to bismuth organic compound, for example bismuth lactate and Bismuth Octoate; Titanate compound, for example tetrabutyl titanate, titanium isopropylate and triethanolamine titanate; Metal carboxylate, for example lead octoate 36, lead naphthenate, nickel naphthenate, naphthenic acid lithium and cobalt naphthenate; Metal acetylacetonate title complex (metal acetylacetonato complexes), for example aluminium acetyl acetone complex and vanadium acetyl acetone complex; And U-200 and U-600 (trade(brand)name; By Nitto Kasei Co., Ltd. produces, organo-tin compound).
The example of basic cpd comprises uncle monoamine, for example ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol and 3-aminopropanol; Secondary monoamine, for example diethylamine, diethanolamine, two n-propyl alcohol amine or diisopropanolamine (DIPA), N-Mono Methyl Ethanol Amine and N-ehtylethanolamine; Uncle's monoamine, for example dimethylethanolamine, Trimethylamine 99, triethylamine, tri-isopropyl amine, methyldiethanolamine and dimethylaminoethanol; Polyamines, for example Diethylenetriamine, hydroxyethyl amino ethyl amine, ethylamino ethylamine and methylamino propyl group amine.According to neutralization equivalent, the amount of the basic cpd that use is preferably 0.1 to 1.2 equivalent.
Tensio-active agent can be nonionogenic tenside, anion surfactant, cats product and amphoterics arbitrarily.The example of nonionogenic tenside comprises polyethylene oxide alkyl ethers, polyoxyethylene allylic alkylation allyl ethers, polyethylene oxide derivatives (such as polyoxyethylene toluylene phenyl ether and polyoxyethylene tribenzyl phenyl ether), sorbitan aliphatic ester, polyoxyethylene sorbitan aliphatic ester, glycerol fatty acid ester, polyoxyethylene fatty acid esters, polyoxyethylene alkylamine, alkyl alkylolamide etc.
The example of anion surfactant comprises soap, alkylsulfonate, alkylbenzene sulfonate and alkylphosphonic.The example of cats product comprises alkylamine salt and quaternary ammonium salt.The example of amphoterics comprises alkyl betaine.
In order to realize emulsion particle diameter in specified range, it is effective that the nonionogenic tenside of general formula (1) is added in negatively charged ion electrocoating paint (B).Preferably use nonionogenic tenside, wherein represent repeating unit-(CH
2CH
2The n of O)-quantity is 10 to 16, more preferably 12 to 15, and be particularly preferably 14 or 15.
Formula (1)
Wherein R is C
7-9Alkyl, and n is 10 to 16 integer.
In the present invention, with negatively charged ion electrocoating paint (B) galvanic deposit on the surface of the anode oxide film that obtains by above-mentioned anode oxidation method.More specifically, after the anodised aluminum or aluminum alloy of at least a portion is dipped into the electropaining bath, applying electric current as the aluminum or aluminum alloy of anode and between to electrode.More specifically, for example, usually carry out in the following manner the negatively charged ion electrodeposition-coating.Preparation by deionized water etc. be diluted to solids content be 5% to 40% mass ratio and be adjusted to pH be 5.5 to 12.0 and preferred pH be that the electropaining of 7 to 10 electrodeposition coating composition is bathed, and bath temperature is adjusted to 15 ° of C to 35 ° of C, then, under the load voltage of 50V to 400V, preferred 80V to 350V, use aluminum or aluminum alloy as anode, apply electric current.
After electrodeposition-coating, can make water wash fully (flushing) surface, thereby remove the excessive lip-deep anionic electrodeposition electrodeposition coating compositions that remains in anodised aluminum or aluminum alloy, perhaps not washing (not rinsing) with water can be for enough, as mentioned above.
Afterwards, can carry out heat drying.By using the dryer such as electrothermal air dryer or gas hot air dries machine to heat to toast and dry electrodeposition coating.The heat drying temperature is generally 100 ° of C to 180 ° of C, is preferably 120 ° of C to 160 ° of C; And the heat drying time is generally 20 minutes to 50 minutes, is preferably 25 minutes to 40 minutes.By baking and dry filming of obtaining to solidify.
The present invention also provides the coated article that obtains by above-mentioned film formation method.Coated article is not subjected to special restriction, and comprises for example building materials, such as aluminium windowframe, gold utensil, balcony base material, roof Material, window shutter, door, sliding gate, door pocket, solaria etc.; And their parts.
Embodiment
Reference example and Comparative Examples are described the present invention in more detail.The invention is not restricted to the following example, as long as it does not exceed its purport.Hereinafter, part and per-cent are mass ratio.
The preparation example of carboxylic resin (b1)
The preparation example of 1: the No. 1 acrylic resin soln of preparation example (having gloss)
70 parts of Virahols are added reaction vessel.In 3 hours, contain the mixture of 10 parts of vinylbenzene, 40 parts of methyl methacrylates, 15 parts of n-butyl acrylates, 18 parts of ethyl propenoates, 10 parts of vinylformic acid 2-hydroxy methacrylates, 7 parts of vinylformic acid and 2 parts of two methyl pentane nitriles of azo to its dropping, simultaneously temperature is remained on 80 ° of C.Subsequently, add the two methyl pentane nitriles of 1 part of azo to it, and mixture is kept 1 hour to react under 80 ° of C, prepare thus No. 1 acrylic resin soln with 70% solids content.For the resin solid content of No. 1 acrylic resin soln, weight-average molecular weight is approximately 2 * 10
4, acid number is 55mg KOH/g, and hydroxyl value is 48mg KOH/g.
The preparation example of 2: the No. 2 acrylic resin solns of preparation example (not having gloss)
70 parts of Virahols are added reaction vessel.In 3 hours, contain the mixture of 10 parts of vinylbenzene, 45 parts of methyl methacrylates, 15 parts of n-butyl acrylates, 10 parts of ethyl propenoates, 12 parts of vinylformic acid 2-hydroxy methacrylates, 5 parts of vinylformic acid, 3 parts of γ-methacryloxypropyl trimethoxy silane and 1 part of two methyl pentane nitrile of azo to its dropping, simultaneously temperature is remained on 80C.Subsequently, add the two methyl pentane nitriles of 1 part of azo to it, and mixture is kept 1 hour to react under 80 ° of C, prepare thus No. 2 acrylic resin soln with 70% solids content.For the resin solid content of No. 2 acrylic resin soln, weight-average molecular weight is approximately 5 * 10
4, acid number is 39mg KOH/g, and hydroxyl value is 58mg KOH/g.
The preparation example of 3: the No. 3 acrylic resin solns of preparation example (having gloss)
70 parts of Virahols are added reaction vessel.In 3 hours, contain the mixture of 10 parts of vinylbenzene, 40 parts of methyl methacrylates, 10 parts of n-butyl acrylates, 13 parts of ethyl propenoates, 10 parts of RMH1053 monomers (annotating 2), 10 parts of vinylformic acid 2-hydroxy methacrylates, 7 parts of vinylformic acid and 2 parts of two methyl pentane nitriles of azo to its dropping, simultaneously temperature is remained on 80 ° of C.Subsequently, add the two methyl pentane nitriles of 1 part of azo to it, and mixture is kept 1 hour to react under 80 ° of C, prepare thus No. 3 acrylic resin soln with 70% solids content.For the resin solid content of No. 3 acrylic resin soln, weight-average molecular weight is approximately 2 * 10
4, acid number is 55mg KOH/g, and hydroxyl value is 48mg KOH/g.
(annotating 2) RMH1053 monomer: Nippon Nyukazai Co., Ltd., trade(brand)name, polyethylene glycol monoacrylate; Molecule content, approximately 700
The preparation example of 4: the No. 4 acrylic resin solns of preparation example (not having gloss)
70 parts of Virahols are added reaction vessel.In 3 hours, contain the mixture of 10 parts of vinylbenzene, 45 parts of methyl methacrylates, 10 parts of n-butyl acrylates, 5 parts of ethyl propenoates, 10 parts of RMH1053 monomers, 12 parts of vinylformic acid 2-hydroxy methacrylates, 5 parts of vinylformic acid, 3 parts of γ-methacryloxypropyl trimethoxy silane and 1 part of two methyl pentane nitrile of azo to its dropping, simultaneously temperature is remained on 80C.Subsequently, add the two methyl pentane nitriles of 1 part of azo to it, and mixture is kept 1 hour to react under 80 ° of C, prepare thus No. 4 acrylic resin soln with 70% solids content.For the resin solid content of No. 4 acrylic resin soln, weight-average molecular weight is approximately 5 * 10
4, acid number is 39mg KOH/g, and hydroxyl value is 58mg KOH/g.
The preparation of 5: the No. 1 solidifying agent of preparation example
222 parts of isophorone diisocyanates and 174 parts of methyl ethyl ketone oxime are added reaction vessel, and temperature is risen to 70 ° of C.Take a sample in time to determine no longer can observe the absorption from unreacted isocyanate groups.Use ethylene glycol monobutyl ether to regulate resin solid content.Therefore, the acquisition resin solid content is 80% No. 1 solidifying agent.
The preparation of 6: the No. 2 solidifying agent of preparation example
168 parts of hexamethylene diisocyanates and 174 parts of methyl ethyl ketone oxime are added reaction vessel, and temperature is risen to 70 ° of C.Take a sample in time to determine no longer can observe the absorption from unreacted isocyanate groups.Use ethylene glycol monobutyl ether to regulate resin solid content.Therefore, the acquisition resin solid content is 80% No. 2 solidifying agent.
The preparation of 7: the No. 1 emulsions of preparation example
No. 1 solidifying agent of No. 1 acrylic resin soln of 80 part 70% (solids content) that will obtain in preparation example 1,20 part 80% (solids content), triethylamine and the deionized water of 1.9 parts (0.4 neutralization equivalents) add and disperse.Then, use deionized water to regulate solids content to obtain 40% No. 1 emulsion.No. 1 emulsion has the median size (annotating 5) of 80nm.
Preparation example 8 is to the preparation of 17: the 2 to No. 11 emulsions
Except using at the formula shown in table 1, obtain emulsion the 2nd to No. 11 in the mode identical with preparation example 7.
(annotating 3) surfactant A: polyoxyethylene glycol octyl phenyl ether (Polyoxy ethylene glycoloctylphenyl ether), n=14 in general formula (1)
(annotating 4) surfactant B: polyoxyethylene glycol octyl phenyl ether, n=15 in general formula (1)
(annotating 5) median size: particles diameter measuring device, Beckman Coulter, Inc., N5 MD.
The preparation of 18: the No. 1 negatively charged ion electrocoating paints of preparation example
It is 10% No. 1 negatively charged ion electrocoating paint that 250 parts (solids contents: 100 parts, 40%) No. 1 emulsion and 750 parts of deionized waters are added to obtain solids content.
Preparation example 19 is to the preparation of 28: the 2 to No. 11 negatively charged ion electrocoating paints
Except using at the formula shown in table 2, obtain the negatively charged ion electrocoating paint the 2nd to No. 11 in the mode identical with preparation example 18.
Table 2
Numeral solids content in formula.
The preparation of test panel
The preparation of 29: the No. 1 test panels of preparation example
By (150mm * 70mm * 0.5mm) immerses 10% sulfuric acid (25 ° of C, 5 minutes) makes its degreasing, then immerses 8% sodium hydroxide (50 ° of C, 4 minutes) to carry out etching with aluminium #6000.Afterwards, wash, then with 15% sulfuric acid neutralization (room temperature, 2 minutes).
Be 20 ° of C with the Temperature Setting of phosphate aqueous solution (30 quality %), the aluminium #6000 that will process in aqueous solution immerses as anode, and with 1.0A/dm
2Constant current density apply electric current 600 seconds to carry out anodic oxidation.Afterwards, carry out hot wash (70 ° of C, 4 minutes), and prepare test panel No. 1.Observation to cross section electron photomicrograph and surface electronic Photomicrograph shows that the anodic oxidation film thickness is 3 μ m, and mean pore size is 60nm.
Preparation example 30 is to the preparation of 40: the 2 to No. 12 test panels
Except using the content shown in table 3 and 4, obtain test panel the 2nd to No. 12 in the mode identical with preparation example 29.
Table 3
Table 4 (table 3 is continuous)
1: the No. 1 multilayer film of embodiment
Under following coated conditions, carry out electrodeposition-coating on above-mentioned " No. 1 test panel ": by regulating the time length of electric current, No. 1 negatively charged ion electrocoating paint has the desciccator diaphragm thickness (solids content of described electrocoating paint: 10% of 3 μ m, the pH:8.5 of electrodeposition bath, bath temperature: 23 ° of C, and voltage: 100V).Afterwards, water washs, and then at room temperature solidifies 3 minutes.Then, use the hot air dries machine, carried out heat drying 20 minutes under 150 ° of C, obtain thus multilayer film No. 1.
Embodiment 2 to 17 and comparative example 1 are to 14: the 2 to No. 31 multilayer films
Obtain multilayer film the 2nd to No. 31 in the mode identical with embodiment 1, except using table 5 to the process shown in 8 and film thickness.Table 5 is to 8 film properties that illustrate according to following test condition acquisition.
(annotating 6) shock resistance:
Each plate is placed in the chamber of steady temperature, constant humidity, temperature is that 20 ° of C ± 1 and humidity are 75 ± 2%, continues 24 hours.According to JIS K 5600-5-3 (1999), the basic point that has separately predetermined size is connected with the DuPont impact test instrument with shock point, and upwards places the coated surface of test panel between basic point and shock point.Next, make weight (500g) drop on (1/2 inch) on shock point, and measure due to impact at film (front surface) the upper height of drop (cm) that breaks or peel off.According to following standard evaluation shock resistance.
A: break under the height of drop more than or equal to 50cm or peel off.
B: break or peel off under more than or equal to 40cm and the height of drop less than 50cm.
C: break or peel off under more than or equal to 30cm and the height of drop less than 40cm.
D: break under the height of drop less than 30cm or peel off.
(annotating 7) water tolerance:
The test panel that will have multilayer film immerses in the water of 40 ° of C, continues 10 days.Afterwards, according to JIS K5600-5-6 (1999) (lattice adhesive tape method (adhering to test (crosscut test) method), with the about interval of 1mm, use pocket knife to produce 11 vertical parallel otch and 11 horizontal parallel otch of the substrate of the coated surface that arrives coated board, thereby form lattice.Cellophane tape is adhered to the surface of coated board, and peel off moment.Afterwards, the coated surface that has lattice according to following standard evaluation.
A: at all do not observe peeling off of filming.
B: some cuttves of filming damage arm of angle light spalling.
C: in 100 grids, observe 1 to 20 grid and peel off.
D: in 100 grids, observe more than or equal to 21 grids and peel off.
The plasticity of the electrodeposition coating in (annotating 8) hole:
Cutting has the test panel of multilayer film, and gathers electron photomicrograph.Measure the maximum value (degree of depth) of wherein observing electrodeposition coating in the hole of anode oxide film.
A: form the electrodeposition coating that the degree of depth is not less than 1.9 μ m in the hole of anode oxide film.
B: form in the hole of anode oxide film that the degree of depth is not less than 1.5 μ m and less than the electrodeposition coating of 1.9 μ m.
C: form in the hole of anode oxide film that the degree of depth is not less than 1.0 μ m and less than the electrodeposition coating of 1.5 μ m.
D: form in the hole of anode oxide film that the degree of depth is not less than 0.5 μ m and less than the electrodeposition coating of 1.0 μ m.
E: form the degree of depth less than the electrodeposition coating of 0.5 μ m in the hole of anode oxide film.
(annotating 9) 60 ° of specular glosss:
According to JIS K5600-4-7 (1999), based on 60 ° of specular glosss, measure the reflectivity of 60 ° of input angles and 60 ° of light acceptance angles.
The mirror surface luster of supposing reference surface is 100, and the glossiness of multilayer film is expressed as the per-cent form.
Industrial applicibility
Coated product with excellent impact resistance and water tolerance can be provided.
Claims (5)
1. be used to form the method for film, it comprises aluminum or aluminum alloy is immersed in phosphate aqueous solution or oxalic acid aqueous solution (A), make the surperficial anodic oxidation of described aluminum or aluminum alloy and form the anode oxide film that thickness is 2 μ m to 5 μ m, described anode oxide film has the hole that mean pore size is 30nm to 300nm, then make negatively charged ion electrocoating paint (B) galvanic deposit form electrodeposition coating on the surface of described anode oxide film, the dry film thickness of described electrodeposition coating is 1 μ m to 5 μ m from the meter of the surface of described anode oxide film, and the degree of depth of described electrodeposition coating in the hole of described anode oxide film is more than or equal to 1 μ m, wherein, it is the emulsion of 30nm to 100nm that described negatively charged ion electrocoating paint (B) comprises by making the resin Composition that comprises carboxylic resin (b1) and blocked isocyanate (b2) be dispersed in water the median size that obtains, and the mean pore size that the median size of described emulsion deducts described hole is equal to or less than 20nm.
2. the method for claim 1, wherein said carboxylic resin (b 1) are to comprise carboxylic unsaturated monomer, polyether-modified vinylformic acid unsaturated monomer and the free-radical polymerized acrylic resin that obtains of monomer mixture (b) of the polymerisable unsaturated monomer of another kind of free radical by making.
3. method as claimed in claim 1 or 2, wherein said negatively charged ion electrocoating paint (B) comprise the compound by following general formula (1) expression:
Wherein, R is the alkyl that contains 7 to 9 carbon atoms, and n is 10 to 16 integer.
4. the method for claim 1, wherein said anode oxide film is by immersing aluminum or aluminum alloy phosphate aqueous solution or oxalic acid aqueous solution (A) and with 0.5A/dm
2To 3.0A/dm
2Current density apply electric current and form.
5. the article that apply, it obtains by the described method of arbitrary claim in claim 1 to 4.
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| JP4794923B2 (en) * | 2005-06-30 | 2011-10-19 | 関西ペイント株式会社 | Anionic electrodeposition paint and coating film forming method |
| JP5485593B2 (en) * | 2008-11-14 | 2014-05-07 | 関西ペイント株式会社 | Method for forming coating film of colored anionic electrodeposition paint |
| JP2010138873A (en) * | 2008-12-15 | 2010-06-24 | Nissan Motor Co Ltd | Multi-cylinder internal combustion engine of variable compression ratio mechanism |
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| JPS5952719B2 (en) * | 1979-10-23 | 1984-12-21 | ホクセイアルミニウム株式会社 | Method for forming a corrosion-resistant anodic oxide film with a thick electrodeposition coating |
| JPH07258888A (en) * | 1994-03-24 | 1995-10-09 | Nikko Kinzoku Kk | Method for sealing pinhole on gold-plated material |
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| JP6016593B2 (en) | 2016-10-26 |
| CN103132117B (en) | 2015-12-09 |
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