CN103289012B - The preparation method of oiliness aluminium-silver slurry Water-borne modification auxiliary agent and prepared water-borne coatings - Google Patents
The preparation method of oiliness aluminium-silver slurry Water-borne modification auxiliary agent and prepared water-borne coatings Download PDFInfo
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Abstract
The present invention relates to a class aqueous paint additive, be specifically related to the Water-borne modification auxiliary agent that oiliness aluminium-silver slurry directly can be applied to water-borne coatings, and use its preparation method of water-borne coatings.Described auxiliary agent is containing phosphate-based and acrylate kind phosphate ester that is hydroxyl, the content of phosphate group is 5 ~ 25wt%, the content of oh group is 1 ~ 5wt%, molecular weight control is 4000 ~ 20000, molecular weight distribution is Mw/Mn:1.1 ~ 2.0, oiliness aluminium-silver slurry adds this Water-borne modification auxiliary agent after solvent dispersion, parcel process, dispersion liquid can be formed, this dispersion liquid directly can join in water-base resin and form water-borne coatings, the method operating procedure simple and stable, product stock good stability, prevent from getting angry in aluminium-silver slurry (aluminium powder) water excellent performance, anti-high-pressure conductive, weather-proof, wet-heat resisting, acidproof, alkaline-resisting, the excellent performance of resistance to piping loop, good to the sticking power of base material, and do not fall aluminium powder for a long time.
Description
[technical field]
The present invention relates to a class aqueous paint additive, be specifically related to the Water-borne modification auxiliary agent that oiliness aluminium-silver slurry directly can be applied to water-borne coatings, and use its preparation method of water-borne coatings.
[background technology]
Aluminium-silver slurry (aluminium powder) is one of important metallic pigment, is used widely in coatings industry, plastics industry and printing-ink because it has high bright metalluster.At present, the domestic annual volume of production and marketing of aluminium-silver slurry (aluminium powder) is probably at about 20,000 tons, wherein external import and 8000 tons, goods thereof, the demand of Rail car manufacture industry to aluminium-silver slurry (aluminium powder) is 10300 tons, the demand of building materials industry aluminium-silver slurry (aluminium powder) about 2500 tons, the demand of household electrical appliance (aluminium powder) reaches 1000 tons.
Due to aluminium-silver slurry (aluminium powder) meeting and water reaction under the environment of water, 2Al+6H
2o → 2Al (OH)
3+ 3H
2produce H
2, namely so-called " getting angry " causes the problem of each side.For a long time, in coating, aluminium-silver slurry (aluminium powder) is applied in solvent-based system always.In recent years, along with further developing and the enhancing of people's environmental consciousness of coatings industry, the regulation of discharging noxious solvent in subtend atmospheric environment is increasingly strict, and the production development of low stain, nuisanceless, non-dusting coating products is paid much attention to.With water to replace organic solvent, water-borne coatings has become the inexorable trend of coating industry development.For car paint, State Bureau of Environmental Protection issued " painting dressing automobiles clean production standard " in 2006, and Eleventh Five-Year Plan requires that gross contamination emission reduces by 10%, proposed clear and definite restriction to the VOC discharge in painting dressing automobiles production process.Reach this requirement, can only water-miscible paint be passed through.American-European countries, in order to strictly limit VOC quantity discharged, has all formulated corresponding environmental regulation, impels painting dressing automobiles to the future development of high-solid level, Water-borne modification, powdered.It is reported, be coated with Water-borne modification in Europe and reach more than 38%, finish paint Water-borne modification reaches 57%.The producer of domestic application water-miscible paint also gets more and more.Aluminium-silver slurry (aluminium powder) is the source of coating flash effect, reach good decorative effect, must use aluminium-silver slurry (aluminium powder).Except car paint, ink industry, furniture industry, five metals household electric appliances, brought into use a kind of aluminium pigment being referred to as water aluminum-silver slurry (aluminium powder) that can be used for water-borne coatings in a large number.
So-called water aluminum-silver slurry (aluminium powder) is namely carry out surface modification treatment to prepare water aluminum-silver slurry (aluminium powder) at traditional oiliness aluminium-silver slurry (aluminium powder) on the market at present.Mainly contain two kinds, physical protection method and chemoproection method.
Namely physical protection method wraps up the resin of layer of transparent as protective layer on aluminium powder surface.As application number 200810031492.5, utilize in-situ polymerization at aluminium powder Surface coating polystyrene resin layer, but need know that the cohesive force of polystyrene and aluminium powder is very weak, resin is easy to come off from aluminium powder surface under high shear forces, loses the provide protection to aluminium powder.And aluminium powder particle diameter ratio is comparatively large, be that parent monomer polymerized in situ transformation efficiency and resin-coated rate all can not be too high with aluminium powder.Anti-high-pressure conductive is also poor.Application number 200810207593.3, epoxy phosphate ester resin is utilized to carry out coated, phosphoric acid ester has very strong grappling effect to aluminium powder, high adsorption capacity, solves the adhesion problem with aluminium powder, but matrix used is epoxy, the weather resistance of epoxy, all there is many problems, and molecular weight of epoxy resin is lower with the consistency of water-borne coatings base-material, stop the ability of the diffusion of water molecules more weak, increase the corrosion to aluminium-silver slurry (aluminium powder).
Chemoproection method mainly contains additive technology and coating technology two class.Also be supply of material form main on the market.Additive technology is mainly through adding organo phosphorous compounds; as the Stapa series of Eckart; AquasilBP/AN(Eckart, Siberline of Siberline are Liang great aluminium powder supplier of the world); but be micromolecular compound due to what add, be difficult to really protect the stability of aluminium powder in water.Another side effect is the performance (as time of drying, sticking power, wet fastness) (reference: PeterWissling, water-borne coatings aluminium pigment, the environment-friendly type aqueous coating of Second Committee and resin symposial, 2003) that may have influence on coating.Technique for packing also experienced by for two generations.The first-generation adopts insoluble chromium cpd (as EckartHydrolux), is also the representative preventing at present aluminium powder pitting attack performance preferably, but along with the enhancing of environmental consciousness, chromic salt, due to its carcinogenic toxicity, is eliminated gradually.The s-generation is then now more popular SiO
2coated, as application number 200610123751.8,200810030678.9,200910013247.6,200910094838.0 etc., have even at SiO
2coated basis increases organic matter modified to improve again with the consistency of paint binder, improve sticking power etc., as the aluminium powder treatment technology of Japanese Japan, the Hydrolan series of Eckart, but this type of SiO2 coating technology increases SiO on original aluminium powder basis
2coating layer reaches the effect of protection aluminium powder, although prevent from getting angry, wet-heat resisting, weather-proof and resistance to piping loop performance etc. reach very excellent over-all properties, SiO
2coating layer will certainly have influence on the original brightness of aluminium powder, sudden strain of a muscle degree and opacifying power, and also easily cause the reunion of aluminium powder in treating processes, manufacturing cost is also very expensive, marketing difficulty.
In sum, current state-of-art all respectively has relative merits, and all has a feature, before preparation coating, aluminium-silver slurry (aluminium powder) producer needs to carry out loaded down with trivial details art breading to oiliness aluminium-silver slurry (aluminium powder), could obtain the aluminium-silver slurry (aluminium powder) that can be used for water-borne coatings.And one involved in the present invention by oiliness aluminium-silver slurry (aluminium powder) after solvent dispersion, parcel auxiliary agent process, directly be used in the using method in water-borne coatings, and use such by oiliness aluminium-silver slurry (aluminium powder) after the process of parcel auxiliary agent, direct applied water-borne coatings.It is characterized in that, coating producer, by buying common oiliness aluminium-silver slurry (aluminium powder), when making coating, adds the specific auxiliary agent of the present invention, just can reach protection oiliness aluminium-silver slurry (aluminium powder), and a kind of mode directly used in water-borne coatings.The method operating procedure simple and stable, product stock good stability, prevents from getting angry in aluminium-silver slurry (aluminium powder) water excellent performance, anti-high-pressure conductive, weather-proof, wet-heat resisting, acidproof, alkaline-resisting, the excellent performance of resistance to piping loop, good to the sticking power of base material, and do not fall aluminium powder for a long time.Brightness and the film performance of oiliness aluminium-silver slurry (aluminium powder) itself is not sacrificed by the water-borne coatings prepared by these class methods, can be used for each fields such as baking vanish, self-drying paint, low-temperature lacquer, solve water aluminum-silver slurry (aluminium powder) the expensive problem that on market, water-borne coatings uses.
[summary of the invention]
The object of this invention is to provide the manufacture method that oiliness aluminium-silver slurry (aluminium powder) directly can be applied to water-borne coatings by one, aluminium-silver slurry (aluminium powder) process for treating surface and new coating auxiliary agent.The invention still further relates to the water-borne coatings using this type of preparation method.
A kind of auxiliary agent of oiliness aluminium-silver slurry, a kind of Water-borne modification auxiliary agent oiliness aluminium-silver slurry being directly used in water-borne coatings, its feature is containing phosphate-based and acrylate kind phosphate ester that is hydroxyl at described auxiliary agent, the content of phosphate group is 5 ~ 25wt%, the content of oh group is 1 ~ 5wt%, molecular weight control is 4000 ~ 20000, and molecular weight distribution is Mw/Mn:1.1 ~ 2.0.
Directly can apply to an oiliness aluminium-silver slurry dispersion liquid for water-borne coatings, oiliness aluminium-silver slurry, through solvent dispersion, is characterized in that the oiliness aluminium-silver slurry of every 10 ~ 45 weight parts also adds the above-mentioned auxiliary agent of 1 ~ 25 weight part.
The described phosphorus content that directly can apply to the oiliness aluminium-silver slurry per unit specific surface area of water-borne coatings is 0.05 ~ 1.5mg/m
2.
Described solvent is hydrophilic solvent.Be selected from butyl glycol ether, 2-Butoxyethyl acetate, butyl, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, propandiol butyl ether, propandiol butyl ether acetic ester, propylene glycol propyl ether, ethanol, ethylene glycol, isooctyl alcohol, glycol ether, ethylene glycol mono methoxy methyl ether, glycol hexyl ether, 2-Ethylhexyl Alcohol, Virahol, butanols, isopropylcarbinol, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate one or more.This acrylic phosphate auxiliary agent is through molecular designing (moleculardesign), bound phosphate groups and oh group are used for being adsorbed onto aluminium-silver slurry (aluminium powder) surface, strong by chemisorption and aluminium-silver slurry (aluminium powder) avidity, the phosphorus content of aluminium-silver slurry (aluminium powder) per unit surface-area is at 0.05 ~ 1.5mg/m
2in scope; Molecular weight control 4000 ~ 8000, molecular weight distribution mw/mn: 1.1 ~ 2.0, less molecular weight and narrow molecular weight distributions make functional groups be evenly distributed on molecular chain, improve the adsorptive power to aluminium-silver slurry (aluminium powder); The polymer side chain of particular design, improves solvated layer thickness, stop water molecules diffusion and to the anti-high-pressure conductive of burn into of aluminium-silver slurry (aluminium powder) and and the consistency of resin system; The polymeric main side chain density ratio of particular design, improves further the adsorptive power of aluminium-silver slurry (aluminium powder) and weather-proof, wet-heat resisting, acidproof, alkaline-resisting, resistance to piping loop performance, attachment to base material.
Also add Ricinate and/or neutralizing agent wherein.Wetting dispersing agent is selected from the Tego655 of goldschmidt chemical corporation, and 192,182,190,180 etc. of Tego745, Tego755, BYK company, also can not add; Neutralizing agent is selected from the one or more than one of dimethylethanolamine, AMP95, trolamine, triethylamine, also can not add, and dispersion liquid PH must be adjusted to 7.5 ~ 8.2 if add.
Can directly apply to water-borne coatings the component proportioning of oiliness aluminium-silver slurry (aluminium powder) dispersion liquid specific as follows:
Oiliness aluminium-silver slurry (aluminium powder) of the present invention is commercially available general all kinds of oiliness aluminium-silver slurrys (aluminium powder), different-grain diameter can be selected, different shapes comprises popcorn or silver dollar shape, different radius-thickness ratio one or more than one;
The present invention also comprises a kind of water-borne coatings of oiliness aluminium-silver slurry, a kind of water-borne coatings directly using oiliness aluminium-silver slurry (aluminium powder) to prepare, containing the aluminium-silver slurry dispersion liquid accounted for described in total mass 5 ~ 30% and 20 ~ 80% water-base resin.
Also comprise the deionized water of 5 ~ 30%, 5 ~ 20% solvent, the defoamer of 0.1 ~ 2%, substrate wetting agents, the auxiliary rheological agents of 0.1 ~ 3%, the neutralizing agent of 0.1 ~ 2% of 0.1 ~ 2%.PH can be adjusted to 8.1 ~ 8.5 by neutralizing agent.
Concrete formula is as follows:
Described solvent is alcohols or ether organic solvent.
Described water-base resin is selected from pure third, hydroxypropyl, benzene emulsion, acrylic acid dispersion, polyurethane dispersions, polyester dispersions, aminoresin one or more than one.Water-base resin is the main film forming substance of coating, plays crucial effect to the final performance of coating, can be selected from DIC, Baeyer, BASF, Niu Peisi, ROHM AND HAAS, Asahi Chemical Industry, Worlee, DSM, cyanogen top grade resin supply producer.
Described defoamer is selected from the one or more than one of silicon class, non-silicon base polymer defoamer, solvent oil, alkyne diol molecule defoamer.Water-borne coatings all can produce foam in manufacture and construction process, and foam also can have an impact to construction process, makes film be the various surface imperfection of dry rear generation.Tradition water-borne coatings defoamer is generally divided into three major types: mineral oil defoaming agent, polysiloxane defoamer and other defoamers.In recent years, molecular antifoaming agent was developed.This defoamer is directly grafted on carrier substance by defoaming activity material to form polymkeric substance.With the hydroxyl of humidification on this polymer molecular chain, defoaming activity species distribution is in molecule surrounding, and active substance is not easily assembled, good with coating system consistency.This kind of molecular antifoaming agent has mineral oils, as the FoamStarAIO of BASF; Siliceous class, as FoamStarA30; And non-silicon non-oil polymer class, as FoamStarMF series, the alkyne diol series etc. of Air.
Described substrate wetting agents is selected from the one or more than one of silicon class or non-silicon class.Because the surface tension of water is comparatively large, to the wetting difficulty of base material, need to add substrate wetting agents, sometimes also referred to as flow agent.Available flow agent has three classes: the restricted long-chain resin of modified polyorganosiloxane, consistency, high boiling solvent etc.
Described auxiliary rheological agents is selected from the one or more than one of mineral-type, cellulose ethers, alkali swelling type, polyurethane-type thickening material.For regulating viscosity or the rheological of water-borne coatings, some auxiliary rheological agents also can improve the thixotropy of coating, makes constructability, reduces drip and sagging.
The present invention also comprises and a kind ofly prepares the above-mentioned method that oiliness aluminium-silver slurry directly can be used in the Water-borne modification auxiliary agent of water-borne coatings, adopt free radical solution polymerization, react in described solvent, be warming up to 80 ~ 140 DEG C, drop into monomer and initiator mixed solution, reaction 2 ~ 5hr, insulation 0.5 ~ 1hr, continue to drop into monomer and initiator mixed solution, reaction 1 ~ 3hr, insulation 0.5 ~ 1hr, continue to drop into partial monosomy and initiator mixed solution, reaction 1 ~ 3hr, insulation 0.5 ~ 1hr, discharging, described monomer is acrylic monomer, vinylbenzene, esters monomer, alcohols monomer, P contained compound, vinylformic acid sodium sulfonate, the mixture of chain-transfer agent.
Above-mentioned partial monosomy may need pre-polymerization to make by oneself.Wherein acrylic monomer is acrylic monomer is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) ethyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid tetrahydrofuran ester, (methyl) glycidyl acrylate, AAEM, in (methyl) isobutyl acrylate, (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl and (methyl) acrylic acid ammonium salt, monovalent metal salt, divalent metal salt, one or more than one in organic ammonium salt.Esters monomer be selected from vinyl acetate, butoxy end-blocking polyethylene glycol allyl, methoxy group polyethylene glycol allyl, butoxy end-blocking polyoxyethylene glycol methallyl ethers, propoxy-end-blocking polyethylene glycol allyl, butoxy end-blocking polyoxyethylene glycol, 3-butene-1-ol ether or oxyethyl group end-blocking polyethylene/polypropylene glycol allyl ethers one or more.Alcohols monomer can select ethylene glycol, 1,2 propylene glycol, Isosorbide-5-Nitrae butyleneglycol, neopentyl glycol, 1,5 pentanediols, 1,6 hexylene glycols, 2-ethyl 2 butyl 1,3 propylene glycol, polytetrahydrofuran diol, Diethylene Glycol, 1,7 heptanediols, 4-methyl isophthalic acid, 8 ethohexadiols, Isosorbide-5-Nitrae cyclohexanedimethanol, Hydrogenated Bisphenol A glycol, glycerol, tetramethylolmethane, TriMethylolPropane(TMP), trimethylolethane, phosphate compound can select phosphoric acid, containing phosphorous oxides, vinyl phosphoric acid, the one or more than one in the monoesters of phosphoric acid, dibasic acid esters or three esters.In reaction process, also according to practical situation, add chain-transfer agent.Chain-transfer agent is more than one in vinyl toluene, thioglycerol, mercaptoethanol, Thiovanic acid, 2-Thiovanic acid, 3-Thiovanic acid, thiohydracrylic acid, mercaptosuccinic acid, Thiovanic acid monooctyl ester, 2-Thiovanic acid monooctyl ester or 3-mercaptoethansulfonic acid, does not also likely add.Benzoyl peroxide selected by described initiator, peroxidation 2-ethyl acid tert-pentyl ester, the peroxidation 2-ethyl acid tert-butyl ester, 1, two (t-amyl peroxy) cyclic group alkane of 1-, 1, two (t-amyl peroxy)-3 of 1-, 3, 5-trimethylammonium cyclohexane, peroxidation acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, peroxidation 3, 3, 5 trimethylammoniums tert-butyl acrylate, peroxidized t-butyl perbenzoate, 3, two (t-amyl peroxy) ethyl butyrate of 3-, , 3, two (t-butyl peroxy) ethyl butyrate of 3-, dicumyl peroxide (DCP), di t-amyl peroxide, di-t-butyl peroxide, t-amyl peroxy hydrogen, one or more of tertbutyl peroxide.
Oiliness aluminium-silver slurry is directly used in a method for water-borne coatings, it is characterized in that being made up of following steps:
I. oiliness aluminium-silver slurry is after solvent dispersion, and add above-mentioned auxiliary agent, dispersed with stirring obtains dispersion liquid;
Ii. the dispersion liquid obtained directly is added in water-borne coatings base-material, thus obtain aqueous paint with flash metal luster.
Adoptable spraying method is the one or more than one of the paint spraying modes such as aerial spraying, the spraying of electrostatic rotating cup, electrophoresis, dip-coating.Painting environments controls the basic construction window at water-borne coatings, and relative humidity 60 ~ 80% is advisable for temperature 23-26 °.Can be used for each fields such as baking vanish, self-drying paint, low-temperature lacquer, each water-borne coatings fields such as automobile, household electrical appliances, ink.
Acrylic phosphate containing phosphoric acid ester functional group, oh group of the present invention is a kind of containing bound phosphate groups 5 ~ 25wt%, the acrylic phosphate auxiliary agent of 1 ~ 5wt% oh group, be key component of the present invention, play and prevent oiliness aluminium-silver slurry (aluminium powder) from " to get angry " in water the effect of reacting.This acrylic phosphate auxiliary agent is through molecular designing (moleculardesign), bound phosphate groups and oh group are used for being adsorbed onto aluminium-silver slurry (aluminium powder) surface, strong by chemisorption and aluminium-silver slurry (aluminium powder) avidity, the phosphorus content of aluminium-silver slurry (aluminium powder) per unit surface-area is at 0.05 ~ 1.5mg/m
2in scope; Molecular weight control 4000 ~ 8000, molecular weight distribution mw/mn: 1.1 ~ 2.0, less molecular weight and narrow molecular weight distributions make functional groups be evenly distributed on molecular chain, improve the adsorptive power to aluminium-silver slurry (aluminium powder); The polymer side chain of particular design, improves solvated layer thickness, stop water molecules diffusion and to the anti-high-pressure conductive of burn into of aluminium-silver slurry (aluminium powder) and and the consistency of resin system; The polymeric main side chain density ratio of particular design, improves further the adsorptive power of aluminium-silver slurry (aluminium powder) and weather-proof, wet-heat resisting, acidproof, alkaline-resisting, resistance to piping loop performance, attachment to base material; Concrete structure and the mechanism of action is as shown in Figure 3 and Figure 4: phosphorous group plays the grappling effect on the surface to aluminium-silver slurry.Apolar chain reinforcement is to the affinity interaction on aluminium powder surface and suppress water molecules to the erosion on aluminium-silver slurry (aluminium powder) surface.Polarity segment then provides dispersion, the stablize aluminium-silver slurry effect of (aluminium powder), and strengthens the diffusion that solvated layer stops water molecules.
Beneficial effect of the present invention: 1, coating producer is by buying common oiliness aluminium-silver slurry (aluminium powder); when making coating; add the specific auxiliary agent of the present invention, just can reach protection oiliness aluminium-silver slurry (aluminium powder), and a kind of mode directly used in water-borne coatings.2, this invention operating procedure simple and stable, product stock good stability, prevents from getting angry in aluminium-silver slurry (aluminium powder) water excellent performance, anti-high-pressure conductive, weather-proof, wet-heat resisting, acidproof, alkaline-resisting, the excellent performance of resistance to piping loop, good to the sticking power of base material, and do not fall aluminium powder for a long time.3, brightness and the film performance of oiliness aluminium-silver slurry (aluminium powder) itself is not sacrificed by the water-borne coatings prepared by the present invention, can be used for each fields such as baking vanish, self-drying paint, low-temperature lacquer, solve water aluminum-silver slurry (aluminium powder) the expensive problem that on market, water-borne coatings uses.
The method operating procedure simple and stable, product stock good stability, prevents from getting angry in aluminium-silver slurry (aluminium powder) water excellent performance, anti-high-pressure conductive, weather-proof, wet-heat resisting, acidproof, alkaline-resisting, the excellent performance of resistance to piping loop, good to the sticking power of base material, and do not fall aluminium powder for a long time.
[accompanying drawing explanation]
Fig. 1 is configuration Paint Examples table;
Fig. 2 is the experimental data table of Fig. 1 embodiment table;
Fig. 3 is the structural representation of aqueous promoter of the present invention;
Fig. 4 is that water-based system-electric charge of the present invention repels each other and sterically hindered schematic diagram;
1. apolar chain A2. apolar chain B3. anchoring group 4. polar chain in figure
[embodiment]
In order to make object of the present invention, technical scheme and advantage clearly understand, the present invention being further elaborated, should be appreciated that specific embodiment described herein only in order to explain the present invention, being not intended to limit the present invention.
A-1. acrylic phosphate embodiment 1
30g butyl and the different glycol hexyl ether of 5g is dropped in reactor, be warming up to 130 DEG C, (monomer mixed solution I consists of 10g methyl acrylate for input monomer and initiator mixed solution, 20g ethyl propenoate, 5g butyl acrylate, 9g propoxy-end-blocking polyethylene glycol allyl, 15g butoxy end-blocking polyethylene glycol allyl, 3.2g makes monomer by oneself, 1g phosphoric acid), initiator I is 3.5g di-t-butyl peroxide, reaction 3hr, insulation 1hr, continue to drop into monomer and initiator mixed solution, (monomer mixed solution II consists of 2g methyl acrylate, 4g ethyl propenoate, 1g butyl acrylate, 1g propoxy-end-blocking polyethylene glycol allyl, 3g butoxy end-blocking polyethylene glycol allyl, 0.6g phosphoric acid, 1g makes monomer by oneself), initiator II is 0.8g peroxidation acetic acid tert-pentyl ester, reaction 2hr, insulation 0.5hr, continue to drop into initiator III0.2g peroxidation acetic acid tert-pentyl ester, and be cooled to 90 °, reaction 1hr, insulation 0.5hr, discharging, gained molecular weight is 4000, molecular weight distribution mw/mn: 1.8.
Self-control monomer reaction situation is as follows:
A-2. acrylic phosphate embodiment 2
Drop into 50g 1-Methoxy-2-propyl acetate in reactor, be warming up to 120 DEG C, (monomer mixed solution I consists of 20g vinylformic acid for input monomer and initiator mixed solution, 20g Hydroxyethyl acrylate, 5g glycidyl acrylate, 10g lauryl methacrylate(LMA), 2g AAEM, the ether capped polyethylene glycol allyl of 9g3-butene-1-ol, 3.2g SODIUM PHOSPHATE, MONOBASIC), initiator I is the 5g peroxidation 2-ethyl acid tert-butyl ester, reaction 4hr, insulation 2hr, and continue to drop into monomer and initiator mixed solution, (monomer mixed solution II consists of 4g vinylformic acid, 4g Hydroxyethyl acrylate, 2g glycidyl acrylate, 3g lauryl methacrylate(LMA), the ether capped polyethylene glycol allyl of 8g3-butene-1-ol, 5g SODIUM PHOSPHATE, MONOBASIC), initiator II is two (t-amyl peroxy) ethyl butyrate of 3,3-, and reaction 2hr, insulation 0.5hr, continue to drop into monomer II I2g Vanadium Pentoxide in FLAKES, initiator III0.2g peroxidation acetic acid tert-pentyl ester, reaction 2hr, insulation 1hr, discharging, gained molecular weight is 8000, molecular weight distribution mw/mn: 1.2.
A-3. acrylic phosphate embodiment 3
20g glycol ether and 20g butanols is dropped in reactor, be warming up to 130 DEG C, (monomer mixed solution I consists of 5g methacrylic acid for input monomer and initiator mixed solution, 10g vinylformic acid ammonium salt, 10g Rocryl 410, 5g THFMA, 20g vinylbenzene, 2g vinyl acetate, 15g polyoxyethylene glycol tridecyl ether phosphoric acid, 20g makes pre-polymerization monomer by oneself, 2g phosphoric acid), initiator I is 2g benzoyl peroxide, reaction 5hr, insulation 1hr, continue to drop into monomer and initiator mixed solution, (monomer mixed solution II consists of 8g vinylformic acid, 5g polyoxyethylene glycol tridecyl ether phosphoric acid, 1g phosphoric acid), initiator II is the peroxidation 2-ethyl acid tert-butyl ester, reaction 1hr, insulation 1hr, discharging, gained molecular weight is 6000, molecular weight distribution mw/mn: 1.4.
A-4. acrylic phosphate embodiment 4
40g isooctyl alcohol is dropped in reactor, be warming up to 100 DEG C, drop into monomer, monomer initiator time for adding is 3hr, monomer mixed solution I consists of 10g methyl methacrylate, 10g ethyl propenoate, 5g methacrylic acid-2-ethylhexyl, 2g lauryl methacrylate(LMA), 8g THFMA, 2g Tryfac 5573 sylvite, 4g Triphenyl phosphate, 1g vinyl phosphoric acid, 0.5g3-Thiovanic acid; Initiator time for adding is 3.5hr, is 4g di-t-butyl peroxide.After monomer and initiator dropwise, insulation 0.5hr.Continue to drop into monomer and initiator mixed solution, monomer II consists of 5g lauryl methacrylate(LMA), 2g Rocryl 410,5g vinylbenzene, 1g Vanadium Pentoxide in FLAKES, and initiator II consists of the 2.5g peroxidation 2-ethyl acid tert-butyl ester, reaction 2hr, insulation 1hr.Continue to drop into initiator III6.8g butoxy end-blocking polyoxyethylene glycol, 2g Triphenyl phosphate, 0.2g3-Thiovanic acid, reaction 0.5hr, insulation 1hr, discharging; Gained molecular weight is 19000, molecular weight distribution mw/mn: 2.0.
B-1. aluminium-silver slurry dispersion liquid embodiment 1
By 20g oiliness aluminium-silver slurry (aluminium powder), particle diameter 20 μm, silver dollar shape, after being selected from Eckart and the 20g butyl glycol ether mixing of Germany, soaking half an hour, add 6 parts of acrylated phosphate A-1 while stirring, continue to stir half an hour, add the 3gTego655(Di Gao company trade mark).
B-2. aluminium-silver slurry dispersion liquid embodiment 2
By 40g oiliness aluminium-silver slurry (aluminium powder), particle diameter 10 μm, corn flower pattern, be selected from Eckart and the 25g glycol hexyl ether of Germany, after the mixing of 15g isooctyl alcohol, soak half an hour, add 8 parts of acrylated phosphate A-2 while stirring, continue to stir half an hour, add 2gBYK190, the 1gBYK182(Bi Ke chemical company trade mark).
B-3. aluminium-silver slurry dispersion liquid embodiment 3
By 15g oiliness aluminium-silver slurry (aluminium powder), particle diameter 15 μm, silver dollar shape, after being selected from domestic race's Xinghe 30g butyl glycol ether mixing, soaking half an hour, adds 9 parts of acrylated phosphate A-3 while stirring, continue to stir half an hour.
B-4. aluminium-silver slurry dispersion liquid embodiment 4
By 10g oiliness aluminium-silver slurry (aluminium powder), particle diameter 18 μm, corn flower pattern, after being selected from domestic race's Xinghe 10g 1-Methoxy-2-propyl acetate, the mixing of 10g butyleneglycol, soaking half an hour, adds 2 parts of acrylated phosphate A-4 while stirring, continue to stir half an hour.And with the 2gAMP95(Dow Chemical trade mark) regulate aluminium-silver slurry dispersion liquid PH to 8.2.
B-5. aluminium-silver slurry dispersion liquid embodiment 5
By 20g oiliness aluminium-silver slurry (aluminium powder), particle diameter 13 μm, corn flower pattern, be selected from Japan Japan and 10g butyl glycol ether, 30g butanols mixing after, soak half an hour, add 5 parts of acrylated phosphate A-4 while stirring, continue stir half an hour.Add 2gBYK180 wetting dispersing agent while stirring, stir 10 minutes, then regulate aluminium-silver slurry dispersion liquid PH to 8.1 with 3g dimethylethanolamine.
Configure the embodiment of coating as shown in Figure 1:
Wherein:
1) Nuplex6802 is the Niu Peisi company trade mark, water-borne acrylic resin;
2) BayhydrolA145 is Beyer Co., Ltd's trade mark, water-based hydroxyl acrylic acid dispersion;
3) the ResydrolAN6481w Shi Qingte company trade mark, waterborne polyester dispersion;
4) the DaotanVTW6462 Shi Qingte company trade mark, acrylic resin modified by aqueous polyaminoester;
5) BayhydurXP2655 is Beyer Co., Ltd's resin grade, water-based polyisocyanate curing agent;
6) the Cytec303 Shi Qingte company trade mark, aminoresin;
7) FoamstarA30 is BASF AG's trade mark, defoamer;
8) the BYK011 Shi Bike chemical company trade mark, defoamer;
9) the TegoWet270 Shi Digao company trade mark, substrate wetting agents;
10) the BYK346 Shi Bike chemical company trade mark, substrate wetting agents;
11) ViscalexHV30 is BASF AG's trade mark, thickening material;
12) the BYK425 Shi Bike chemical company trade mark, thickening material;
13) water aluminum-silver slurry dispersion liquid-1 is as the contrast sample of aluminium-silver slurry dispersion liquid B-1, adopts the SiO of Eckart
2the aqueous aluminum powder handled well.By 20g aqueous aluminum powder Hydorlan series, particle diameter 20 μm, silver dollar shape, and after the mixing of 20g butyl glycol ether, soak half an hour, add the 3gTego655(Di Gao company trade mark).
14) water aluminum-silver slurry dispersion liquid-2 is as the contrast sample of aluminium-silver slurry dispersion liquid B-4, adopts the SiO of Eckart
2the aqueous aluminum powder handled well.By 20g aqueous aluminum powder Hydorlan series, particle diameter 13 μm, corn flower pattern, and 10g 1-Methoxy-2-propyl acetate, after the mixing of 10g butyleneglycol, soak half an hour, and with the 2gAMP95(Dow Chemical trade mark) regulate aluminium-silver slurry dispersion liquid PH to 8.2.
D. Performance Detection embodiment
Coating complete for above-mentioned preparation is adopted aerial spraying, and in relative humidity 60 ~ 80%, temperature 23-26 °, is sprayed on electrophoresis steel plate.Dodge dry 3-5min, 80 ° of prebake conditions 3-5min, thickness 10-20 μm, then spray supporting coating varnish 30-50 μm.C-1, C-2, C-5, C-7 are high temperature baking vanish, 140 ° of baking 30min.C-3, C-4, C-6, C-8 are low temperature baking vanish, 80 ° of baking 20min.Carry out the full Performance Detection of paint stability (hot accelerating storage), sticking power, performance of getting angry, water-fast, wet-heat resisting, acidproof, alkaline-resisting, resistance to piping loop performance, weathering resistance.Experimental result is as shown in Figure 2:
Embodiment interpretation of result,
1. the water-borne coatings Embodiment C 7 made by aqueous aluminum powder, C8 appearance effect are poor, and owing to adding SiO2 coating layer, L value, brightness obviously decline.
2. the impact of performance such as water-borne coatings Embodiment C-1, C-4, C-5 paint stability (hot accelerating storage), sticking power, performance of getting angry, water-fast, wet-heat resisting, acidproof, alkaline-resisting, resistance to piping loop performance, weathering resistance made by acrylic phosphate embodiment A-1, A-4 is better.
3. water-borne coatings Embodiment C-2 acid resistance made by acrylic phosphate embodiment A-2 is poor.
4. the water-borne coatings Embodiment C-3, the C-6 that are made by acrylic phosphate embodiment A-3 get angry performance, water-fast, paint stability is poor.
5. the water-borne coatings Embodiment C-3 made by aluminium-silver slurry dispersion liquid Embodiment B-3, B-4, C-4 do not add wetting dispersing agent, and appearance effect is general.
6. coating producer is by buying common oiliness aluminium-silver slurry (aluminium powder); when making coating, add the specific auxiliary agent of the present invention, as acrylic phosphate embodiment A-1, A-4; just can reach protection oiliness aluminium-silver slurry (aluminium powder), and a kind of mode directly used in water-borne coatings.
7. this invention, as water-borne coatings Embodiment C-1, C-4, C-5, operating procedure simple and stable, product stock good stability, prevent from getting angry in aluminium-silver slurry (aluminium powder) water excellent performance, anti-high-pressure conductive, weather-proof, wet-heat resisting, acidproof, alkaline-resisting, the excellent performance of resistance to piping loop, good to the sticking power of base material, and do not fall aluminium powder for a long time.
8. by the water-borne coatings prepared by the present invention, as water-borne coatings Embodiment C-1, C-4, C-5, do not sacrifice brightness and the film performance of oiliness aluminium-silver slurry (aluminium powder) itself, can be used for each fields such as baking vanish, self-drying paint, low-temperature lacquer, solve water aluminum-silver slurry (aluminium powder) the expensive problem that on market, water-borne coatings uses, thus further pushing ring friendly coating, Water-borne modification process.
Claims (7)
1. oiliness aluminium-silver slurry is directly used in the Water-borne modification auxiliary agent of water-borne coatings by one kind, its feature is containing phosphate-based and acrylate kind phosphate ester that is hydroxyl at described auxiliary agent, the content of bound phosphate groups is 5 ~ 25wt%, the content of oh group is 1 ~ 5wt%, molecular weight is in 4000 ~ 20000 scopes, and molecular weight distribution is Mw/Mn:1.1 ~ 2.0.
2. Water-borne modification auxiliary agent oiliness aluminium-silver slurry being directly used in water-borne coatings according to claim 1, is characterized in that oiliness aluminium-silver slurry is the one or more than one of commercially available general all kinds of specification oiliness aluminium-silver slurrys.
3. directly apply to an oiliness aluminium-silver slurry dispersion liquid for water-borne coatings, it is characterized in that common oiliness aluminium-silver slurry is through solvent dispersion, the oiliness aluminium-silver slurry of every 10 ~ 45 weight parts also adds 1 ~ 25 weight part Water-borne modification auxiliary agent according to claim 1.
4. directly apply to the oiliness aluminium-silver slurry dispersion liquid of water-borne coatings as claimed in claim 3, it is characterized in that described solvent is hydrophilic solvent.
5. directly apply to the oiliness aluminium-silver slurry dispersion liquid of water-borne coatings as claimed in claim 3, it is characterized in that also can comprising Ricinate and/or neutralizing agent.
6. the water-borne coatings directly adopting oiliness aluminium-silver slurry dispersion liquid to prepare, is characterized in that the water-base resin containing the aluminium-silver slurry dispersion liquid according to claim 3 and 20 ~ 80% accounting for total mass 5 ~ 30%, the deionized water of 5 ~ 30%, solvent, the defoamer of 0.1 ~ 2%, substrate wetting agents, the auxiliary rheological agents of 0.1 ~ 3%, the neutralizing agent of 0.1 ~ 2% of 0.1 ~ 2% of 5 ~ 20%.
7. the water-borne coatings prepared of a kind of direct employing oiliness aluminium-silver slurry dispersion liquid as claimed in claim 6, is characterized in that described solvent is alcohols or ether organic solvent.
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| CN113897103A (en) * | 2021-11-25 | 2022-01-07 | Ppg涂料(天津)有限公司 | Aqueous aluminum preparation and method for producing same |
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| CN114410162B (en) * | 2022-01-21 | 2022-08-09 | 擎天材料科技有限公司 | Water-based aluminum powder baking paint capable of being cured at low temperature and preparation method and application thereof |
| CN117683414A (en) * | 2022-09-09 | 2024-03-12 | 立邦涂料（中国）有限公司 | Aqueous color masterbatch composition containing aluminum powder pigment |
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