CN1498928A - Coloured anion electroplating paint and coloured aluminum - Google Patents
Coloured anion electroplating paint and coloured aluminum Download PDFInfo
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- CN1498928A CN1498928A CNA2003101148582A CN200310114858A CN1498928A CN 1498928 A CN1498928 A CN 1498928A CN A2003101148582 A CNA2003101148582 A CN A2003101148582A CN 200310114858 A CN200310114858 A CN 200310114858A CN 1498928 A CN1498928 A CN 1498928A
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Abstract
The color anionic electrodeposition coating material comprises an anionic resin, a crosslinking agent, and a color pigment, and the color pigment is a particulate color pigment (A), and simultaneously the compounding amount of the pigment (A) is in the range of 0.1 to 20 pts.wt. based on 100 pts.wt. sum of the anionic resin (B) and the crosslinking agent (C), and the colored aluminum material is obtained by subjecting the electrodeposition coating material to electrodeposition coating.
Description
Technical field
The present invention relates to painted anion electroplating paint and painted aluminium.
Background technology
In the past, aluminium was owing to belonged to light-duty and intensity is high and erosion resistance etc. is good, was applied to usually in the material of construction such as framework.As aluminium, usually for additional weathering resistance and weather resistance, use covering on the aluminium on the aluminium base of anodic oxidation film, cover the material of anionic electrodeposition plated coating film.
In recent years, along with the bigger variation of social environment, the human consumer has been not only for protecting materials to the requirement of coating, and is also additional attractive in appearance to material, the appearance effect of the additional perception that exceeds impression in the past, feeling of high class etc.Thereby, require to increase appearance effect attractive in appearance, additional too for aluminium.
For these requirements, the painted aluminium of a kind of application is for example disclosed, the color harmony colorama face of the anodic oxidation film that overlapping anodic oxidation aluminium base has is electroplated the tone of filming, thereby can obtain special colour, this moment is as tinting material, uses Chromatic color pigment (opening the 2001-73191 communique with reference to the spy) such as Achromatic color pigment such as white pigments, mineral black or blue pigments, veridian, yellow ultramarine, red pigment.
In addition, known have electroplating coating, the tinting pigment that will not contain tinting pigment, the painted delustring electroplating coating that contains hydrophobic solvent to mix, and can adjust the painted delustring electroplating paint composition (opening the 2000-34428 communique with reference to the spy) of the top and following foxy of the anodic oxidation aluminium base that is coated.
In addition; also known mixing contains acrylic resin and the aldehydes with ethanoyl; and the electroplating coating that does not contain tinting pigment; with the electroplating coating that contains tinting pigment; compoundization of tone that the color harmony of anodic oxidation aluminium base is filmed can obtain special colour (opening the 2000-80311 communique with reference to the spy).
And then, the known delustring electroplating coating that will contain the ethene copolymer of carboxyl and hydroxyl, the ethene copolymer that contains carboxyl and alkoxysilyl group, aminoresin, contain organic or inorganic pigment, be coated on the plating that obtains on the anodic oxidation aluminium base and film, present the tone (opening flat 11-286632 communique) of the metal sense of low gloss with reference to the spy.
Like this, the aluminium base that has carried out having anodic oxidation film is as coated article, and application cooperates the anion electroplating paint of painted pigment such as mineral dye and pigment dyestuff, obtains the research of various tones, based on this, has proposed additional new appearance effect.
But, in the anion electroplating paint that in above-mentioned prior art, uses, each tone of filming must use dispersion resin or dispersing auxiliary, pass through a few hours and carry out dispersion treatment, make pigment dispersion paste, and then use this pigment dispersion paste to make anion electroplating paint, there is the problem that needs a lot of times and operation of making.
In addition, in anion electroplating paint in the past, because employed pigment dispersion paste, the storage stability of coating is insufficient, and in the anion electroplating paint running since additional mechanical such as the circulation of pump or strainer filtration when participating in dispersing of pigments stability insufficient.
That is, use the anion electroplating paint of pigment dispersion paste in the past, pigment precipitates easily when storage coating, and in case generation precipitates, then pigment cake layer is difficult to redispersion.Therefore, general painted anion electroplating paint in order to prevent the pigment precipitation, needs continuously stirring, also needs to stir coating even do not carry out the day off of painting operation, needs significant cost during running.
And then, on the anodic oxidation aluminium base, after in a single day the tone during the painted anion electroplating paint of application is determined, be difficult to replace color.On the other hand, according to customer requirement, also need to carry out the produced in small quantities of the painted aluminium of various tones.
Therefore, need a kind of painted anion electroplating paint and painted aluminium, the saving energy the when storage stability of coating and running is good, adjusts tone easily, can add new appearance effect on the anodic oxidation aluminium base.
Summary of the invention
The object of the present invention is to provide a kind of painted anion electroplating paint and painted aluminium, the saving energy the when storage stability of coating and running is good, adjusts tone easily, can add new appearance effect on the anodic oxidation aluminium base.
The present inventor has carried out multiple research in order to solve above-mentioned problem, it found that, as tinting pigment, cooperate the painted anion electroplating paint that need not form with the particulate state tinting pigment of pigment dispersion paste state use, the saving energy when storage stability of coating and running is good, adjust tone easily, on the anodic oxidation aluminium base, can add new appearance effect.Based on above-mentioned new discovery, and then the result who carries out various researchs, the present invention finished.
The invention provides following painted anion electroplating paint and painted aluminium.
1. painted anion electroplating paint, contain anionic resin, linking agent and tinting pigment, it is characterized in that, described tinting pigment is particulate state tinting pigment (A), and the cooperation ratio of this pigment (A), solids component total amount 100 weight parts of relative anionic resin (B) and linking agent (C) are in the scope of 0.1～20 weight part.
2. according to above-mentioned 1 described painted anion electroplating paint, particulate state tinting pigment (A) obtains by covering Powdered tinting pigment (a) with nonionic surface active agent (b) and/or covering resin (c).
3. according to above-mentioned 1 or 2 described painted anion electroplating paints, the median size of particulate state tinting pigment (A) is in the scope of 50～500 μ m.
4. according to each described painted anion electroplating paint of above-mentioned 1～3, the volume density of particulate state tinting pigment (A) is at 0.2～0.6g/cm
3Scope in.
5. according to each described painted anion electroplating paint of above-mentioned 1～4, the slope of repose of particulate state tinting pigment (A) is in 20～45 ° scope.
6. according to each described painted anion electroplating paint of above-mentioned 1～5, the form of particulate state tinting pigment (A) is the hollow body structures of median size in 50～300 mu m ranges.
7. painted aluminium, by with each described painted anion electroplating paint of above-mentioned 1～6, electro dipping with the painting object washing or do not wash, carries out sintering and obtains on the aluminium base of anodic oxidation treatment.
Painted anion electroplating paint
Colored plating coating of the present invention contains anionic resin, linking agent and tinting pigment, it is characterized in that, as this tinting pigment, specified quantitative uses particulate state tinting pigment (A).
Particulate state tinting pigment (A) for example, obtains by covering Powdered tinting pigment (a) with nonionic surface active agent (b) and/or covering resin (c).
As Powdered tinting pigment (a), can use any of organic coloring pigment and inorganic coloring pigment.
As Powdered organic coloring pigment, can exemplify monoazo pigment, disazo pigment, anthraquinone pigment, anthrapyrimidones pigment, quinacridone pigments, quinophthalone pigment, diketopyrrolo-pyrrole ketone pigment, dioxazines pigment, yellow anthrone pigment, indanthrene pigment, isoindoline pigment, isoindolinone pigment, iso-violanthrone pigment, perylene quinone pigments, perylene pigment, phthalocyanine pigment, pyranthrone pigments, tritane pigment, thioindigo color, and the metal complex pigment of these pigment etc.
In addition, as Powdered inorganic coloring pigment, can exemplify carbon black, titanium white, ferric oxide etc.
As nonionic surface active agent (b), can exemplify Voranol EP 2001 class, polyoxyethylene alkyl amine class, polyoxyethylene allyl ethers, polyoxyethylene alkyl phenyl ether class, polyoxyethylene and encircle polyoxyethylene deriv classes such as phenyl ethers more; Fatty acid esters such as lipid acid span, polyoxyethylene fatty acid span, polyoxyethylene fatty acid ester class; The mixture of alcoxylates, particularly propoxylated glycerine, ethoxylate, propoxylated glycerine and ethoxylates such as fatty alcohol, aromatic alcohols, fatty amine; The reaction product of three kinds of materials such as quadrol, propylene oxide and ethylene oxide etc.
As the commercially available prod of nonionic surface active agent (b), can exemplify " ノ イ ゲ Application EA-150 " (the first industrial pharmacy (strain) is made, trade(brand)name, polyoxyethylene nonylplenyl ether).
As covering resin (c), can the exemplified by acrylic resin, synthetic resins such as Resins, epoxy, vibrin, urethane resin; The resin of natural foundations such as toxilic acid modified rosin, fumaric acid modified rosin.
As above-mentioned particulate state tinting pigment (A), Powdered relatively tinting pigment (a) 100 weight parts preferably use nonionic surface active agent (b) and/or covering resin (c) with the ratio about 5～60 weight parts.In addition, the usage ratio of this tensio-active agent (b) and this resin (c), both total amounts relatively are about preferred 60～100 weight % of this tensio-active agent (b), about preferred 0～40 weight % of this resin (c).
The particulate state tinting pigment (A) of Shi Yonging in the present invention, in the scope of its median size about 50～500 μ m, but consider the scope about preferred especially 50～300 μ m from the storage stability of the dispersiveness coating, coating, the processing outward appearance equal angles that gained is filmed.At this moment, median size is, as the particle size measurement device, and the value of using " MICROTRAC HRA model9320-X100 " (trade(brand)name, day machine dress (strain) is made) to measure.
In addition, particulate state tinting pigment (A) considers that from stability, water dispersible, the painted spreadability equal angles of pigment (A) itself its volume density is preferably at 0.2～0.6g/cm
3About scope in.And then, consider the scope that its slope of repose is preferred about 20～45 ° from equal angular.
In addition, tone as this pigment (A), by one or more selection, combination and the usage ratio during combination etc. from powder dress tinting pigment (a), tones such as red, blue, green, yellow, black, white can be adjusted into, and then the two or more complicated tone of combination from these tones can be adjusted into.
In addition, as particulate state tinting pigment (A), comprise that also its median size is the form of the hollow body structures of 50～300 μ m left and right sides scopes.This hollow body structures for example is spherical ampuliform.The particulate state tinting pigment (A) of spherical ampuliform is made of spheric shell and cavity usually, and the thickness of shell is for counting about μ m～tens of μ m.
Manufacture method as particulate state tinting pigment (A), there is no particular limitation, it is described that for example the spy opens flat 5-184901 communique, in the waterborne suspension of pigment, under high degree of agitation, with not with the air of suspension reaction, nitrogen, gases such as carbonic acid gas, plus-pressure and disperseing not in fact with the rill form, then pass through the mechanical separation of spraying drying or liquid, or the shaping of wettability pigment cake and lasting dry, make the pigment suspension that obtains be transformed into the manufacture method of the easily disperse granules of pigments of granules of pigments, can adopt above-mentioned pigment (a), under the existence condition of nonionic surface active agent (b) and/or covering resin (c), be transformed into the method for particulate state tinting pigment.
In addition, it is described that for example the spy opens flat 10-7924 communique, with resin with the acid number more than the 200mgKOH/g and/or nonionic surface active agent, cover the pigment dyestuff that suspends in the aqueous solvent, and mechanical disintegration and the method for the concoction that makes paints can adopt the method for above-mentioned pigment (a) as the particulate state tinting pigment.
As the concrete example of particulate state tinting pigment (A), for example can use " Xfast
TMBlueED 6879 ", " Xfast
TMGreen ED 6880 ", " Xfast
TMYellow ED 6983 ", " Xfast
TMRed ED 7179 " (more than, BASF AG makes, trade(brand)name) etc.These pigment can use a kind ofly, or mix two or more uses with arbitrary proportion.
Particulate state tinting pigment (A), in the emulsion that contains anionic resin and linking agent, can be not as pigment dispersion paste, and directly add, mix.In addition, this pigment (A) adds in water, utilizes water-dispersions easily such as common stirrer or manual stirring, so the aqueous dispersions that obtains directly can be added in the above-mentioned emulsion.And then, in the anion electroplating paint of modulated anion electroplating paint or application circuit is bathed,, can carry out the adjustment or the revisal of tone by adding the particulate state tinting pigment (A) of water-dispersion afterwards.
With particulate state tinting pigment (A), in the anion electroplating paint that does not contain tinting pigment, when directly interpolation, mixing, or when in water, adding, by for example diameter be agitating vane about 3～5cm with 300～1, stir about 000rpm, or manually stir, can disperse easily.Disperseing required time is about 10 seconds～10 minutes, preferred about 30 seconds～5 minutes, be more preferably 1 minute～and about 3 minutes, the scope of temperature about 5～80 ℃, preferred about 15～30 ℃ scope can be disperseed easily and in the short period of time.
In addition, when using above-mentioned particulate state tinting pigment (A) separately, can not get under the situation of target tone the pigment paste that can also constitute with other tinting pigments and dispersion resin etc.This pigment paste, can by with this pigment (A) in addition tinting pigment and as required with pigment extender, with suitable dispersion with resin simultaneously, utilize ball mill or sand mill etc. to disperse as the dispersion means, modulate.As this pigment (A) tinting pigment in addition, can exemplify titanium oxide, carbon black, red iron oxide pigment etc.In addition, as pigment extender, can exemplify kaolin, mica, barium oxide, lime carbonate, silicon-dioxide etc.
As anionic resin (B), so long as can use any as the anion-type water-thinned resin of anion electroplating paint with matrix resin.
As anionic resin (B), for example, can use one or more combination of resins such as the ethene copolymer that contains hydroxyl and carboxyl, vibrin, Synolac, fluoro-resin, silicone resin.Wherein, consider the preferred ethene copolymer that contains hydroxyl and carboxyl that uses from the angle of weathering resistance.
As the ethene copolymer that contains hydroxyl and carboxyl, preferred material can exemplify vinyl-type monomer, ethylene type unsaturated carboxylic acid that contains hydroxyl and the ethene copolymer that obtains with other unsaturated monomer free radicals copolymerization reactions as required.
In above-mentioned monomer component, as the vinyl-type monomer that contains hydroxyl, can exemplify (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, (methyl) vinylformic acid (gathering) ethylene glycol ester, (methyl) vinylformic acid (gathering) propylene glycol monoester, hydroxy butyl vinyl ether, (methyl) vinyl carbinol etc.; And these contain the vinyl-type monomer of hydroxyl and the reaction product of lactone compound etc.
As above-mentioned lactone compound, can exemplify beta-propiolactone, dimethyl propylene lactone, butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-decalactone, γ-dodecalactone, 6-caprolactone, δ-caprolactone etc.
Commercially available prod as the reaction product of vinyl-type monomer that contains hydroxyl and lactone compound, can exemplify " プ ラ Network セ Le FM1 ", " プ ラ Network セ Le FM2 ", " プ ラ Network セ Le FM3 ", " プ ラ Network セ Le FA1 ", " プ ラ Network セ Le FA2 ", " プ ラ Network セ Le FA3 " (more than, ダ イ セ Le chemical company makes, trade(brand)name all belongs to caprolactone modification (methyl) vinylformic acid hydroxyl ester class) etc.
As the ethylene type unsaturated carboxylic acid, can exemplify (methyl) vinylformic acid, toxilic acid, " プ ラ Network セ Le FM1A ", " プ ラ Network セ Le FM4A ", " プ ラ Network セ Le FM10A " (more than, ダ イ セ Le chemical company makes, trade(brand)name all belongs to caprolactone modification carboxylic (methyl) Acrylic Acid Monomer) etc.
As other unsaturated monomers, can exemplify (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) dodecyl acrylate, (methyl) cyclohexyl acrylate, etc. (methyl) acrylic acid C
1～C
18The alkyl or cycloalkyl ester; Aromatic vinyl type monomers such as vinylbenzene; (methyl) third rare acid amides and derivatives thereof such as (methyl) acrylic amine, N-butoxy (methyl) third rare acid amides, N-methylol (methyl) third rare acid amides; (methyl) third rare nitrile; The vinyl-type monomer of alkoxysilyls such as γ-(methyl) acryloxy propyl trimethoxy silicane, vinyltrimethoxy silane etc.
These monomeric cooperation ratios, the monomer of hydroxyl, the base number that preferably fits in multipolymer is approximately the scope of 30～300mgKOH/g.As the cooperation ratio, the solids component total amount of the total monomer amount of above-mentioned relatively monomer class, the monomer that contains hydroxyl is approximately 3～40 weight %, and preferably approximately is the scope of 5～30 weight %.
The ethylene type unsaturated carboxylic acid, the acid number that preferably fits in multipolymer is approximately the scope of 10～200mgKOH/g.As the cooperation ratio, the total monomer amount of above-mentioned relatively monomer class, the ethylene type unsaturated carboxylic acid is approximately 3～30 weight %, and preferably approximately is the scope of 4～20 weight %.
As other unsaturated monomers, preferred (methyl) the acrylic acid C that uses
1～C
18Alkyl or cycloalkyl ester and aromatic vinyl type monomer.The use level of other unsaturated monomers, the total monomer amount of above-mentioned relatively monomer class is approximately 37～95 weight %, and preferably approximately is the scope of 60～91 weight %.
By making these monomers produce free radicals copolymerization reaction, can prepare water-based anionic resin (B).As making it produce the method for free radicals copolymerization reaction, can use known solution copolymerization method, block copolymerization, emulsification copolymerization, suspension copolymerization etc.In these methods, the preferred solution copolymerization process.
As linking agent (C), so long as can use any as the linking agent of anion electroplating paint with matrix resin.
As linking agent (C), part or all of methylol that for example can use terpolycyantoamino-formaldehyde resin is by one or more the material of monohydroxy-alcohol modification such as methyl alcohol, ethanol, propyl alcohol, butanols, octanol, 2-Ethylhexyl Alcohol.In addition, the material of the monokaryon element of the preferred triazine ring of terpolycyantoamino-formaldehyde resin～many (about 2～5) nucleic accounts for more than the 50 weight %.In addition, in terpolycyantoamino-formaldehyde resin, can contain other functional groups such as imino-, methylol.As terpolycyantoamino-formaldehyde resin, utilize C
3Above monohydroxy-alcohol is C particularly
4～C
18Preferred every triazine ring 1 nuclear of the ether of monohydroxy-alcohol modification average about more than 2.0, especially preferably contain 2.0～5.0.
In addition,, can become the piece polymeric polyisocyanate, use separately or also use with above-mentioned terpolycyantoamino-formaldehyde resin as linking agent (C).As becoming the piece polymeric polyisocyanate, for example, can use aliphatics or alicyclic polymeric isocyanate compounds such as isophorone diisocyanate, cyclohexyl diisocyanate, become the material of blocking.For example, can use lactone such as 6-caprolactone; Alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol; One-tenth piece agent such as oximes such as methyl ethyl ketoxime, methyl isobutyl ketoxime and carrying out.
The cooperation ratio of particulate state tinting pigment (A) in the painted anion electroplating paint of the present invention, solids component total amount 100 weight parts of relative anionic resin (B) and linking agent (C), particulate state tinting pigment (A) is about 0.1～20 weight part, about preferred 0.5～10 weight part, be more preferably about 1～5 weight part.The use level of this pigment (A), if less than 0.1 weight part, then the adjustment of tone is insufficient.On the other hand, if surpass 20 weight parts, cost height not only, and can lose processibility.
The cooperation ratio of anionic resin (B) and linking agent (C), solids component total amount 100 weight parts of relative two compositions, anionic resin (B) is about 40～80 weight parts, scope about preferred 50～80 weight parts, linking agent (C) is about 15～60 weight parts, the scope about preferred 20～50 weight parts.
If the cooperation ratio of anionic resin (B) is less than 40 weight parts, processibility can reduce, and on the other hand, if surpass 85 weight parts, then has the tendency that hardening reduces.Linking agent (C) is during less than 15 weight parts, and hardening descends, and when surpassing 60 weight parts, has the tendency that paint stability reduces.
Painted anion electroplating paint of the present invention, usually in stirred vessel, pack into anionic resin (B) and linking agent (C), utilize on one side basic cpd to neutralize anionic property group that this resin (B) has, carry out under the stirring condition on one side, in the water-based emulsion that adds deionized water and obtain, composite grain shape tinting pigment (A), and then as required, add tensio-active agent, surface conditioner, pH adjustment agent, deionized water etc., stir, mix and obtain easily.The solid component concentration of this electroplating coating, common scope about 5～20 weight %, pH is the scope about 7.0～10.0 usually, can be with these plating baths as electro dipping.
As the basic cpd that in above-mentioned neutralization, uses, can exemplify one-level monoamines such as ethamine, propylamine, butylamine, aniline, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol; Secondary monoamines such as diethanolamine, two n-propyl alcohol amine, diisopropanolamine (DIPA), N-Mono Methyl Ethanol Amine, N-ehtylethanolamine; Three grades of monoamines such as dimethylethanolamine, Trimethylamine 99, triethylamine, tri-isopropanolamine, methyldiethanolamine, Deanol etc., these can use one or more.
Painted aluminium
Painted aluminium of the present invention, by with painted anion electroplating paint of the present invention, electro dipping with the painting object washing or do not wash, carries out sintering and obtains to the aluminium base of anodic oxidation treatment.
The anodic oxidation aluminium base that uses as coated object is with the anodic oxidation film electrolytic coloring of anodised aluminum or do not carry out electrolytic coloring.
As the method for electrolytic coloring, can adopt the method for known dye technology in the past.For example, carry out after the anodic oxidation, in containing the electrolytic solution of metal-salt, carry out 2 electrolysis and make oxide film painted, or add metal-salt in the electrolytic solution when anodic oxidation, in anodic oxidation treatment, make oxide film painted.
As above-mentioned metal-salt, can exemplify nickel salt, mantoquita, cobalt salt, lead salt, manganese salt, golden salt, silver salt, molybdenum salt, selenium salt etc.Form as salt comprises inorganic acid salts such as vitriol, organic acid salts such as acetate, oxysalt.
By having on the anodic oxidation aluminium surface of above-mentioned anodic oxidation film, anion electroplating application painted anion electroplating paint of the present invention can form and film.
Utilize the formation of filming of anion electroplating application, the painted anion electroplating paint of the invention described above of in plating tank, packing into usually, as plating bath, in this is bathed, after this aluminium base of dipping, carry out electro dipping, make the cured film thickness behind the sintering reach about 5～30 μ m usually, do not wash (not washing), or wash (flushing), then after the setting at room temperature, undertaken by sintering.Sintering condition is typically about 150～220 ℃, about 15～50 minutes.
The painted aluminium that obtains, the painted anionic electrodeposition plated coating film that on base material, forms, can when being colored, have the transparency, diffusion, the anodic oxidation film surface reflection below of this light of filming of transmission, or form complicated overlapping with absorbed optics, present special colour, can add the new appearance effect that did not in the past have.
Embodiment
Below, utilize Production Example, embodiment and comparative example, be described more specifically the present invention.But the present invention is unqualified in these examples.In each example, " part " reaches " % " and represents that respectively " weight part " reaches " weight % ".
Production Example 1 contains the manufacturing of the acrylic resin of hydroxyl and carboxyl
In reaction vessel, Virahol 70g and keep 80 ℃ packs into, wherein through the mixture of 3 hours drip styrene 10g, methyl methacrylate 31g, n-butyl acrylate 10g, ethyl propenoate 30g, 2-hydroxyl acrylic ethyl ester 12g, vinylformic acid 7g and azo two methyl pentane nitrile 2g, then add azo two methyl pentane nitrile 1g, kept 1 hour and reacted at 80 ℃ times, make the acrylic resin that contains hydroxyl and carboxyl.This acrylic resin, weight-average molecular weight is about 25,000, and acid number is 55mgKOH/g, and base number is 58mgKOH/g.
The manufacturing of emulsion of Production Example 2 anion electroplating paints
In the acrylic resin that in Production Example 1, obtains 70 parts (solids component), the carboxyl of relative this resin, blending dispersion 0.4 normal triethylamine, then therein, (Sanwa Chemical Co., Ltd makes blending dispersion " ニ カ ラ Star Network MX600 ", trade(brand)name, butyl alcohol etherified melamine-formaldehyde resin) 30 parts, the limit is stirred the limit and is slowly dripped deionized water afterwards, and then adds triethylamine, make pH reach 7.5, make the anion electroplating paint emulsion of solids component 8%.
The manufacturing of Production Example 3 pigment dispersion paste No.1 (comparative example usefulness, blue system)
Add 5.45 parts of (3 parts of solids components), phthalocyanine blue (trade(brand)names " CYANINE BLUE AD-2 " of carboxylic acid additive type acrylic acid or the like pigment dispersing resin, the manufacturing of Japan イ Application キ company) 3 part, add 0.5 part of triethylamine, 3.05 parts of deionized waters, obtain the pigment dispersion paste No.1 of solids component 50%.
The manufacturing of Production Example 4 pigment dispersion paste No.2 (comparative example usefulness, green system)
Add carboxylic acid additive type acrylic acid or the like pigment dispersing resin 5.45 parts of (3 parts of solids components), phthalocyanine green (trade(brand)names " CYANINE GREEN 5301 ", the big Japan company that refines makes) 3 parts, add 0.5 part of triethylamine, 3.05 parts of deionized waters, obtain the pigment dispersion paste No.2 of solids component 50%.
The manufacturing of Production Example 5 pigment dispersion paste No.3 (comparative example usefulness, yellow system)
Add 5.45 parts of (3 parts of solids components), monoazo yellow (trade(brand)names " FAST YELLOW 10GS " of carboxylic acid additive type acrylic acid or the like pigment dispersing resin, the manufacturing of adret pigment company) 3 part, add 0.5 part of triethylamine, 3.05 parts of deionized waters, obtain the pigment dispersion paste No.3 of solids component 50%.
The one-tenth of the pigment dispersion paste No.1～No.3 that obtains in Production Example 3～5 is grouped into as shown in table 1.In table 1, become component to represent with " part ".In addition, the resin in () is represented solids component.
Table 1
| 50% pigment dispersion paste | ??No.1 | ??No.2 | ??No.3 | |
| Color | Blue | Green | Yellow | |
| Carboxylic acid additive type acrylic acid or the like dispersion resin | ??5.45 ??(3) | ??5.45 ??(3) | ??5.45 ??(3) | |
| Tinting pigment | Phthalocyanine blue | ??3 | ||
| Phthalocyanine green | ??3 | |||
| Monoazo yellow | ??3 | |||
| Triethylamine | ??0.5 | ??0.5 | ??0.5 | |
| Deionized water | ??3.05 | ??3.05 | ??3.05 | |
| Total amount | ??12 ??(6.0) | ??12 ??(6.0) | ??12 ??(6.0) | |
The manufacturing of embodiment 1 painted anion electroplating paint No.1
The anion electroplating paint of the solids component 8% that obtains in Production Example 2 is with in the emulsion 1,250 part (100 parts of solids components), and cooperating indigo plant is particulate state tinting pigment (trade(brand)name, " Xfast
TMBlue ED 6879 ", BASF AG makes, median size is 200 μ m, volume density is 0.5g/cm
3, the slope of repose is 38 °) and 1 part, and then add triethylamine, and make pH reach 8, and add deionized water, obtain the painted anion electroplating paint No.1 of solids component 8%.
The manufacturing of embodiment 2 painted anion electroplating paint No.2
The anion electroplating paint of the solids component 8% that obtains in Production Example 2 is with in the emulsion 1,250 part (100 parts of solids components), and cooperating green is particulate state tinting pigment (trade(brand)name, " Xfast
TMGreen ED 6880 ", BASF AG makes, median size is 250 μ m, volume density is 0.46g/cm
3, the slope of repose is 37 °) and 1 part, and then add triethylamine, and make pH reach 8, and add deionized water, obtain the painted anion electroplating paint No.2 of solids component 8%.
The manufacturing of embodiment 3 painted anion electroplating paint No.3
The anion electroplating paint of the solids component 8% that obtains in Production Example 2 is with in the emulsion 1,250 part (100 parts of solids components), and cooperating Huang is particulate state tinting pigment (trade(brand)name, " Xfast
TMYellow ED 6983 ", BASF AG makes, median size is 250 μ m, volume density is 0.35g/cm
3, the slope of repose is 35 °) and 1 part, and then add triethylamine, and make pH reach 8, and add deionized water, obtain the painted anion electroplating paint No.3 of solids component 8%.
Embodiment 4～6
Except the use level of particulate state tinting pigment is set at 3 parts, carry out 1～3 identical operations with embodiment, obtain painted anion electroplating paint No.4～6 of solids component 8%.
The manufacturing of comparative example 1 painted anion electroplating paint No.7
The anion electroplating paint of the solids component 8% that in Production Example 2, obtains emulsion 1, in 250 parts (100 parts of solids components), the pigment dispersion paste No.1 that in Production Example 3, obtains that cooperates 8 parts (4 parts of solids components), and then interpolation triethylamine, make pH reach 8, and the interpolation deionized water, obtain the painted anion electroplating paint No.7 of solids component 8%.
Comparative example 2～3
By with comparative example 1 identical operations, and the cooperation content of pressing table 2 obtains the painted anion electroplating paint No.8 and the No.9 of the solids component 8% of comparative example 2～3.
The one-tenth of each the painted anion electroplating paint that obtains in embodiment 1～6 and comparative example 1～3 is grouped into as shown in table 2.In table 2, become component to represent with " part ".In addition, the resin in () is represented solids component.
Table 2
| Embodiment | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 |
| Painted anion electroplating paint | ??No.1 | ??No.2 | ??No.3 | ??No.4 | ??No.5 | ??No.6 |
| The emulsion that Production Example 2 obtains | ??1250 ??(100) | ??1250 ??(100) | ??1250 ??(100) | ??1250 ??(100) | ??1250 ??(100) | ??1250 ??(100) |
| Indigo plant is the particulate state tinting pigment | ??1 | ??3 | ||||
| Green is the particulate state tinting pigment | ??1 | ??3 | ||||
| Huang is the particulate state tinting pigment | ??1 | ??3 | ||||
| Triethylamine | Be adjusted into pH=8 | |||||
| Deionized water | The solids component adjustment amount | |||||
| Total amount | ??1263 ??(101) | ??1263 ??(101) | ??1263 ??(101) | ??1288 ??(103) | ??1288 ??(103) | ??1288 ??(103) |
Table 2 (continuing)
| Comparative example | ??1 | ??2 | ??3 | |
| Painted anion electroplating paint | ??No.7 | ??No.8 | ??No.9 | |
| The emulsion that Production Example 2 obtains | ??1250 ??(100) | ??1250 ??(100) | ??1250 ??(100) | |
| 50% pigment dispersion paste | Kind | ??No.1 | ??No.2 | ??No.3 |
| Amount | ??4 ??(2) | ??4 ??(2) | ??4 ??(2) | |
| Triethylamine | Be adjusted into pH=8 | |||
| Deionized water | The solids component adjustment amount | |||
| Total amount | ??1275 ??(102) | ??1275 ??(102) | ??1275 ??(102) | |
Then, detect storage stability, total transmissivity light and the scattering of light transmission of the painted anion electroplating paint that in embodiment 1～6 and comparative example 1～3, obtains by the following method.
Storage stability: coating 3L packed into open wide jar, under 20 ℃, left standstill 1 day, utilize stirrer (trade(brand)name " TK ホ モ デ イ ス パ one ", society of aboveground makings institute makes) afterwards, with rotation number 700rpm stirring 1 hour.Afterwards, utilize 400 order filtering nets to measure the filtration residue amount of coating, and then confirm the state of jar base paint.The evaluation of storage stability by visual inspection, is undertaken by following standard.
Zero: filtration residue is less than 10mg/L, and a jar end do not have the pigment precipitation, storage stability is good.
△: filtration residue is below the above 20mg/L of 10mg/L, and there is the small amounts of pigment precipitation at a jar end, and storage stability is bad slightly.
*: filtration residue is more than the 20mg/L, and there is a certain amount of pigment precipitation at a jar end, and storage stability is bad.
Total transmissivity light and scattering of light transmission: on sheet glass, use the material feeder coating composition, make the cured film thickness behind the sintering reach 10 μ m,, make test and film 180 ℃ of following sintering 30 minutes.Only the transmitted light of sheet glass is as benchmark, utilizes " ヘ イ ズ メ one one COH-300A " (Japanese electric look Industrial Co., Ltd make trade(brand)name) to measure this directional light transmissivity (P) of filming and scattered light transmissivity (D).P+D is set at total transmissivity light (%).In addition, scattering of light transmission (H) (%) is tried to achieve by following calculating formula.
Scattering of light transmission (H)=[(D/ (P+D)] * 100
Test-results is as shown in table 3.
Table 3
| Embodiment | Comparative example | ||||||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??1 | ??2 | ??3 | |
| Electroplating coating | ??No. ??1 | ??No. ??2 | ??No. ??3 | ??No. ??4 | ??No. ??5 | ??No. ??6 | ??No. ??7 | ??No. ??8 | ??No. ??9 |
| Storage stability | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??△ | ??× | ??△ |
| Total transmissivity light | ??99 | ??99 | ??99 | ??96 | ??95 | ??93 | ??94 | ??91 | ??93 |
| The scattering of light transmission | ??1 | ??1.5 | ??1.5 | ??2 | ??3 | ??5 | ??8 | ??8 | ??6 |
Embodiment 7～12 and comparative example 4～6
Painted anion electroplating paint No.1～9 that will obtain in embodiment 1～6 and comparative example 1～3 are respectively as plating bath.As coated article, to implement 2 electrolysis treatment (degreasing-corrode-neutralize-be anodizing to processing-sealing of hole) obtains, oxide film thickness be about 10 μ m the anodic oxidation aluminium base (silver color (non-coloring), size is 150 * 70 * 0.5mm), is impregnated in the plating bath, carry out electro dipping, make the cured film thickness behind the sintering reach 10 μ m, after the washing, 180 ℃ of following sintering 30 minutes, form to electroplate and film, obtain painted aluminium.
Electroplate each painted aluminium of filming for forming, carry out the test of tone, gloss, colourimetric number and the smoothness of filming.Test method is as follows.
Tone:, detect and electroplate the tone of filming by visual inspection.
Gloss: according to the 60 degree mirror surface lusters of JIS K-5400 7.6 (1990), the gloss intensity of filming is by measuring input angle and be subjected to firing angle to be respectively 60 reflectivity when spending, per-cent (%) expression that is set at 100 o'clock with the reference plane glossiness of mirror surface luster.
Colourimetric number: according to the L of JIS Z8729
*a
*The b color specification system utilizes angle spectrophotometer " Minolta CR-300 " (Minolta company makes, trade(brand)name) to measure.L
*Be brightness index, a
*And b
*Be the color index.
The smoothness of filming (1):, determine that film coated surface has or not tangerine peel phenomenon, concavo-convex etc., and estimate according to following standard by visual inspection.
◎: do not have tangerine peel phenomenon, concavo-convex etc., smoothness is good;
Zero: do not have tangerine peel phenomenon, concavo-convex etc. substantially, smoothness is roughly good;
△: tangerine peel phenomenon, concavo-convex etc. is arranged, and smoothness is bad slightly;
*: the tangerine peel phenomenon, concavo-convex etc. significantly, smoothness is bad.
The smoothness of filming (2): after above-mentioned storage stability test, filter and the electroplating coating that obtains with 400 order filtering nets, on coated article same as described above, carry out after the electro dipping as above-mentioned, the same with the smoothness of filming (1), estimate the smoothness of filming.
Above-mentioned test-results is as shown in table 4.
Table 4
| Embodiment | 7 | 8 | 9 | 10 | 11 | 12 | |
| Electroplating coating | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 | |
| Tone | The indigo plant that transparent feel is arranged | The green of transparent feel arranged | The Huang that transparent feel is arranged | Dense a little indigo plant | Dense a little is green | Dense a little Huang | |
| Gloss | 105 | 108 | 105 | 100 | 103 | 93 | |
| Colourimetric number | ??L * | 70.82 | 81.97 | 86.46 | 61.36 | 72.46 | 81.06 |
| ??a * | -20.66 | -26.77 | -12.56 | -26.21 | -55.21 | -11.15 | |
| ??b * | -26.64 | -2.42 | +47.11 | -41.54 | +0.18 | +75.12 | |
| The smoothness of filming (1) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | |
| The smoothness of filming (2) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | |
Table 4 (continuing)
| Comparative example | 4 | 5 | 6 | |
| Electroplating coating | No.7 | No.8 | No.9 | |
| Tone | Blue | Green | Yellow | |
| Gloss | 97 | 93 | 95 | |
| Colourimetric number | L * | 72.25 | 84.39 | 86.95 |
| a * | -21.04 | -30.22 | -12.98 | |
| b * | -28.34 | -2.15 | +51.08 | |
| The smoothness of filming (1) | ??○ | △ | ○ | |
| The smoothness of filming (2) | ??△ | × | △ | |
According to painted anionic electroplating coating of the present invention, particularly, by using particulate state tinting pigment (A) as tinting pigment, the storage stability that can reach coating is good, in the stirring of coating, can save energy running, adjust tone easily, on painted aluminium base, additional attractive in appearance, can add the unusual effect of the appearance effect of the perception that exceeds impression in the past, feeling of high class etc.Specifically, can obtain following effect.
1. in the past, the electroplating coating pigment dispersion paste usually was not put in application circuit or the warehouse there to be the state that stirs, because this moment, pigment produced precipitation, needed mechanical stirring and recovered, and form during redispersion and condense or piece and damage processibility.
Relatively therewith, painted anion electroplating paint of the present invention, employed particulate state tinting pigment (A), can directly use so need not make pigment dispersion paste because dispersed good, therefore can not produce the problems referred to above.That is, coating of the present invention has following effect: even directly use this pigment (A), also can seldom produce precipitation in coating; By simple agitation redispersion easily; And be difficult to during redispersion produce and condense or piece, so can not damage processibility; Because use granular pigment, the dust generation is few, and be very easy to handle; Loss is few etc.
2. painted anion electroplating paint of the present invention there is no need in order to prevent that pigment produces precipitation and continuously stirring beyond the operating time, can accomplish that when day off or non-application the discontinuous running that stirs or the part of recycle pump stop, and can significantly save the energy.
3. in coating of the present invention because with particulate state tinting pigment (A), after add in the bath of painted anion electroplating paint, so adjust tone easily, can carry out easily various tones painted aluminium on a small quantity from producing.
4. by will adding the of the present invention painted anion electroplating paint of particulate state tinting pigment (A), electro dipping for example can obtain the indigo plant of transparent feel, the tone of green, Huang Dengxin to the anodic oxidation treatment film of aluminium base.Can obtain such tone with transparent feel, be because add filming of particulate state tinting pigment, compare with filming of common interpolation pigment dispersion paste, and total transmissivity light quantity height, and the scattering of light transmission is low.
Claims (7)
1. a painted anion electroplating paint contains anionic resin, linking agent and tinting pigment, it is characterized in that,
Described tinting pigment is particulate state tinting pigment (A), and the cooperation ratio of this pigment (A), and solids component total amount 100 weight parts of relative anionic resin (B) and linking agent (C) are in the scope of 0.1～20 weight part.
2. painted anion electroplating paint according to claim 1, particulate state tinting pigment (A) obtains by covering Powdered tinting pigment (a) with nonionic surface active agent (b) and/or covering resin (c).
3. painted anion electroplating paint according to claim 1 and 2, the median size of particulate state tinting pigment (A) is in the scope of 50～500 μ m.
4. according to each described painted anion electroplating paint of claim 1～3, the volume density of particulate state tinting pigment (A) is at 0.2～0.6g/cm
3Scope in.
5. according to each described painted anion electroplating paint of claim 1～4, the slope of repose of particulate state tinting pigment (A) is in 20～45 ° scope.
6. according to each described painted anion electroplating paint of claim 1～5, the form of particulate state tinting pigment (A) is the hollow body structures of median size in 50～300 mu m ranges.
7. painted aluminium, by aforesaid right is required each described painted anion electroplating paint of 1～6, electro dipping with the painting object washing or do not wash, carries out sintering and obtains on the aluminium base of anodic oxidation treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002325709A JP4374485B2 (en) | 2002-11-08 | 2002-11-08 | Colored anion electrodeposition paint and colored aluminum material |
| JP325709/2002 | 2002-11-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1498928A true CN1498928A (en) | 2004-05-26 |
| CN100393823C CN100393823C (en) | 2008-06-11 |
Family
ID=32804848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101148582A Expired - Fee Related CN100393823C (en) | 2002-11-08 | 2003-11-07 | Coloured anion electroplating paint and coloured aluminum |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4374485B2 (en) |
| CN (1) | CN100393823C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4748720B2 (en) * | 2006-03-13 | 2011-08-17 | 日本軽金属株式会社 | Multi-layer coating formation method |
| CN101675127A (en) * | 2007-04-02 | 2010-03-17 | 因艾克斯塞尔商标专利公司 | Method for preparing paints and inks using a resin coated pigment |
| 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 |
| JP5417607B2 (en) * | 2009-03-23 | 2014-02-19 | 株式会社Ｌｉｘｉｌ | Aluminum building materials or processed products |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859637A (en) * | 1987-12-17 | 1989-08-22 | Ferro Corporation | Lead-free U.V. absorbing glass |
| US5646213A (en) * | 1996-06-28 | 1997-07-08 | Arco Chemical Technology, L.P. | High-solids and powder coatings from hydroxy-functional acrylic resins |
| US6204319B1 (en) * | 1998-10-30 | 2001-03-20 | E.I. Du Pont De Nemours And Company | Aqueous coating compositions |
-
2002
- 2002-11-08 JP JP2002325709A patent/JP4374485B2/en not_active Expired - Lifetime
-
2003
- 2003-11-07 CN CNB2003101148582A patent/CN100393823C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN100393823C (en) | 2008-06-11 |
| JP4374485B2 (en) | 2009-12-02 |
| JP2004161785A (en) | 2004-06-10 |
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