CN103289012A - Preparation method of water-borne coating additive for oily aluminum paste and water-borne coating prepared from water-borne coating auxiliary - Google Patents
Preparation method of water-borne coating additive for oily aluminum paste and water-borne coating prepared from water-borne coating auxiliary Download PDFInfo
- Publication number
- CN103289012A CN103289012A CN2013102535641A CN201310253564A CN103289012A CN 103289012 A CN103289012 A CN 103289012A CN 2013102535641 A CN2013102535641 A CN 2013102535641A CN 201310253564 A CN201310253564 A CN 201310253564A CN 103289012 A CN103289012 A CN 103289012A
- Authority
- CN
- China
- Prior art keywords
- water
- silver slurry
- aluminium
- borne
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to a water-borne coating additive, more specifically to the water-borne coating additive by the application of which oily aluminum paste may be directly used in a water-bone coating, and a preparation method of the water-born coating. The water-borne coating additive is an acrylate phosphate containing phosphate and hydroxyl. The content of phosphate is 5 to 25% by weight, and the content of hydroxyl is 1 to 5% by weight. Molecular weight is controlled at a range from 4000 to 20000, and molecular weight distribution Mw/Mn is 1.1 to 2.0. The oily aluminum paste is dispersed by a solvent, and then the water-borne coating additive is added. A dispersion liquid can be formed by wrapping treatment, and the dispersion liquid can be directly added into a water-borne resin to produce the water-borne coating. Operation processes of the method are simple, storage stability of the product is excellent. Gas generation of the aluminum paste (aluminum powder) in water can be prevented effectively. Resistances to high pressure conductivity, weather, heat and humidity, acid, alkali and pipeline circulation are excellent, and adhesive force to base materials is strong. No aluminum powder will drop in a long term.
Description
[technical field]
The present invention relates to a class aqueous paint additive, be specifically related to the oiliness aluminium-silver slurry directly to be applied to the Water-borne modification auxiliary agent of water-borne coatings, and the preparation method who uses its 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 volume of production and marketing in aluminium-silver slurry (aluminium powder) domestic every year is probably about 20,000 tons, wherein external import and goods thereof are 8000 tons, the vehicle production is 10300 tons to the demand of aluminium-silver slurry (aluminium powder), about 2500 tons of the demands of building materials industry aluminium-silver slurry (aluminium powder), the demand of household electrical appliance (aluminium powder) reaches 1000 tons.
Because aluminium-silver slurry (aluminium powder) is 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, aspect coating, aluminium-silver slurry (aluminium powder) is applied in the 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 is strict day by day in the subtend atmospheric environment, lowly pollutes, production exploitation nuisanceless, non-dusting coating products obtains paying much attention to.Use water to replace organic solvent, water-borne coatings has become the inexorable trend of coating industry development.Be example with the car paint, State Bureau of Environmental Protection was issued " painting dressing automobiles cleaner production standard " in 2006, and Eleventh Five-Year Plan requires gross contamination emission to reduce by 10%, and discharging proposes clear and definite restriction to the VOC in the painting dressing automobiles production process.Reach this requirement, can only pass through water-miscible paint.American-European countries has all formulated corresponding environmental regulation for strictness restriction VOC quantity discharged, impels painting dressing automobiles to develop to the direction of high-solid level, Water-borne modification, powdered.It is reported that be coated with Water-borne modification in the Europe and reached more than 38%, the finish paint Water-borne modification has reached 57%.The producer of domestic applying waterborne lacquer is also more and more.Aluminium-silver slurry (aluminium powder) is the source of coating flash effect, reach good decoration effect, must use aluminium-silver slurry (aluminium powder).Except automobile coating, printing ink industry, furniture industry, five metals household electric appliances have brought into use a kind of energy to be used for the aluminium pigment that is referred to as water aluminum-silver slurry (aluminium powder) of water-borne coatings in a large number.
So-called water aluminum-silver slurry (aluminium powder) namely is to carry out surface modification treatment at traditional oiliness aluminium-silver slurry (aluminium powder) to prepare water aluminum-silver slurry (aluminium powder) on the market at present.Mainly contain two kinds, physical protection method and chemoproection method.
The physical protection method is namely wrapped up the resin of layer of transparent as protective layer on the aluminium powder surface.As application number 200810031492.5, utilize in-situ polymerization to coat the polystyrene resin layer on the aluminium powder surface, but need know that the cohesive force of polystyrene and aluminium powder is very weak, resin is easy to come off from the aluminium powder surface under high shear forces, loses the provide protection to aluminium powder.And the aluminium powder particle diameter ratio is bigger, is that parent in-situ polymerization monomer conversion and resin-coated rate can be too not high with the aluminium powder.Anti-high pressure electroconductibility is also relatively poor.Application number 200810207593.3, utilize the epoxy phosphate ester resin to coat, phosphoric acid ester has very strong grappling effect to aluminium powder, and high adsorption capacity has solved the adhesion problem with aluminium powder, but matrix used is epoxy, the weather resistance of epoxy all have many problems with the consistency of water-borne coatings base-material, and molecular weight of epoxy resin is lower, stop water molecules diffusion ability a little less than, increase the corrosion to aluminium-silver slurry (aluminium powder).
The chemoproection method mainly contains additive technology and coating technology two classes.It also is on the market main supply of material form.Additive technology is mainly by adding organo phosphorous compounds; Stapa series as Eckart; the AquasilBP/AN(Eckart of Siberline, Siberline are the world two big aluminium powder suppliers); but because interpolation is micromolecular compound, 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) that may have influence on coating (reference: PeterWissling, water-borne coatings aluminium pigment, second environment-friendly type aqueous coating and resin symposial, 2003).Technique for packing also experienced for two generations.The first-generation adopts insoluble chromium cpd (as Eckart Hydrolux), also is the representative that prevents at present aluminium powder pitting attack performance preferably, but along with the enhancing of environmental consciousness, chromic salt since its carcinogenic toxicity be eliminated gradually.The s-generation then is present more popular SiO
2Coat, as application number 200610123751.8,200810030678.9,200910013247.6,200910094838.0 etc., have in addition at SiO
2Coating increases organism again and modifies to improve with the consistency of paint binder, improves sticking power etc. on the basis, as the aluminium powder treatment technology of Japanese Japan, and the Hydrolan series of Eckart, but this type of SiO2 coating technology is to increase SiO on original aluminium powder basis
2Coating layer reaches the effect of protection aluminium powder, though prevent from getting angry, moisture-proof heat, the weather-proof and cycle performance of anti-pipeline the etc. reach very excellent comprehensive performance, SiO
2Coating layer will certainly have influence on original brightness, sudden strain of a muscle degree and the opacifying power of aluminium powder, also causes the reunion of aluminium powder in the treating processes easily, and manufacturing cost is also very expensive, the marketing difficulty.
In sum, present state-of-art all respectively has relative merits, and all has characteristics, before preparation coating, aluminium-silver slurry (aluminium powder) producer need carry out loaded down with trivial details art breading to oiliness aluminium-silver slurry (aluminium powder), just can make the aluminium-silver slurry (aluminium powder) that can be used for water-borne coatings.And involved in the present invention a kind of oiliness aluminium-silver slurry (aluminium powder) is handled through solvent dispersion, parcel auxiliary agent after, directly be used in the using method in the water-borne coatings, and use such with oiliness aluminium-silver slurry (aluminium powder) after the parcel auxiliary agent is handled, direct applied water-borne coatings.It is characterized in that coating producer when making coating, adds the specific auxiliary agent of the present invention by buying common oiliness aluminium-silver slurry (aluminium powder), just can reach protection oiliness aluminium-silver slurry (aluminium powder), and a kind of mode of directly using in water-borne coatings.This method operating procedure simple and stable, the product stock good stability prevents the excellent performance of getting angry in aluminium-silver slurry (aluminium powder) water, anti-high pressure conduction, weather-proof, moisture-proof is warm, acidproof, alkaline-resisting, the cycle performance of anti-pipeline excellence, sticking power to base material is good, and does not fall aluminium powder for a long time.Do not sacrifice brightness and the film performance of oiliness aluminium-silver slurry (aluminium powder) itself by the prepared water-borne coatings of these class methods, can be used for each field such as baking vanish, self-drying paint, low-temperature lacquer, solved the expensive problem of water aluminum-silver slurry (aluminium powder) that water-borne coatings uses on the market.
[summary of the invention]
The purpose of this invention is to provide a kind of manufacture method that oiliness aluminium-silver slurry (aluminium powder) directly can be applied to water-borne coatings, aluminium-silver slurry (aluminium powder) process for treating surface and new coating auxiliary agent.The invention still further relates to the water-borne coatings that uses this type of preparation method.
A kind of auxiliary agent of oiliness aluminium-silver slurry, a kind of Water-borne modification auxiliary agent that the oiliness aluminium-silver slurry directly is used in water-borne coatings, its feature is to contain phosphate-based and acrylate kind phosphate ester 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.
A kind of oiliness aluminium-silver slurry dispersion liquid that can directly apply to water-borne coatings, the oiliness aluminium-silver slurry is characterized in that through solvent dispersion the oiliness aluminium-silver slurry of per 10～45 weight parts also adds the above-mentioned auxiliary agent of 1～25 weight part.
The described phosphorus content that can directly 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 one or more of butyl glycol ether, 2-Butoxyethyl acetate, Diethylene Glycol butyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, propylene glycol butyl ether, propylene glycol monobutyl ether acetate, propylene glycol propyl ether, ethanol, ethylene glycol, isooctyl alcohol, glycol ether, glycol monomethyl methoxymethyl ether, glycol hexyl ether, 2-Ethylhexyl Alcohol, Virahol, butanols, isopropylcarbinol, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate.This acrylic acid or the like phosphoric acid ester 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 the scope; Molecular weight control is 4000～8000, molecular weight distribution mw/mn: 1.1～2.0, and less molecular weight and narrow molecular weight distributions are evenly distributed on the molecular chain functional groups, 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 electroconductibility of the 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, further improve to the adsorptive power of aluminium-silver slurry (aluminium powder) and weather-proof, moisture-proof is warm, acidproof, alkaline-resisting, the cycle performance of anti-pipeline the, adhering to base material.
Also add Ricinate and/or neutralizing agent therein.Wetting dispersing agent is selected from the Tego655 of goldschmidt chemical corporation, Tego745, and Tego755,192,182,190,180 etc. of BYK company also can not add; Neutralizing agent is selected from a kind of of dimethylethanolamine, AMP95, trolamine, triethylamine or more than one, also can not add, if add and dispersion liquid PH must be adjusted to 7.5～8.2.
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 of the present invention (aluminium powder) is commercially available general all kinds of oiliness aluminium-silver slurrys (aluminium powder), can select different-grain diameter, different shapes to comprise a kind of of popcorn or silver dollar shape, different radius-thickness ratios or more than one;
The present invention also comprises a kind of water-borne coatings of oiliness aluminium-silver slurry, and the water-borne coatings of a kind of direct use oiliness aluminium-silver slurry (aluminium powder) preparation contains the described aluminium-silver slurry dispersion liquid that accounts for total mass 5～30% and 20～80% water-base resin.
Also comprise 5～30% deionized water, 5～20% solvent, 0.1～2% defoamer, 0.1～2% base material wetting agent, 0.1～3% auxiliary rheological agents, 0.1～2% neutralizing agent.Neutralizing agent can be adjusted to 8.1～8.5 with PH.
Concrete prescription is as follows:
Described solvent is alcohols or ether organic solvent.
That described water-base resin is selected from is pure third, hydroxypropyl, benzene emulsion, acrylic acid dispersion, polyurethane dispersions, polyester dispersions, aminoresin a kind of or more than one.Water-base resin is the main film forming substance of coating, and the final performance of coating is played crucial effect, 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 a kind of of silicon class, non-silicon base polymer defoamer, solvent oil, alkyne diol molecule defoamer or more than one.Water-borne coatings all can produce foam in manufacturing and construction process, foam also can exert an influence to construction process, and making films is that dry back produces various surface imperfection.Tradition water-based paint antifoaming agent generally is divided into three major types: mineral oil defoaming agent, polysiloxane defoamer and other defoamers.In recent years, developed the molecular level defoamer.This defoamer is the froth breaking active substance directly to be grafted on form polymkeric substance on the carrier substance.The hydroxyl that has humidification on this polymer molecular chain, the froth breaking active substance is distributed in around the molecule, and active substance is difficult for assembling, and is good with the coating system consistency.This quasi-molecule grade defoamer has mineral oils, as the FoamStarAIO of BASF; Siliceous class is as FoamStarA30; And the non-oil polymer class of non-silicon, as FoamStarMF series, the alkyne diol series of Air etc.
Described base material wetting agent is selected from a kind of of silicon class or non-silicon class or more than one.Because the surface tension of water is bigger, to the wetting difficulty of base material, need to add the base material wetting agent, be also referred to as flow agent sometimes.Available flow agent has three classes: modified polyorganosiloxane, the restricted long-chain resin of consistency, high boiling solvent etc.
Described auxiliary rheological agents is selected from a kind of of mineral-type, cellulose ethers, alkali swelling type, polyurethane-type thickening material or more than one.Be used for regulating viscosity or the rheological of water-borne coatings, some auxiliary rheological agents also can improve the thixotropy of coating, makes to be convenient to construction, reduces drip and sagging.
The present invention also comprises a kind of above-mentioned method that the oiliness aluminium-silver slurry directly can be used in the Water-borne modification auxiliary agent of water-borne coatings for preparing, adopt free radical solution polymerization, in described solvent, react, be warming up to 80～140 ℃, drop into monomer and initiator mixed solution, reaction 2～5hr, insulation 0.5～1hr continues 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 are acrylic monomer, vinylbenzene, esters monomer, the alcohols monomer, P contained compound, the vinylformic acid sodium sulfonate, the mixture of chain-transfer agent.
Above-mentioned partial monosomy may need the pre-polymerization self-control.Wherein acrylic monomer is that 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) vinylformic acid hydroxy butyl ester and (methyl) acrylic acid ammonium salt, monovalent metal salt, divalent metal salt, a kind of in the organic ammonium salt or more than one.Esters monomer is selected from one or more in vinyl acetate, butoxy end-blocking polyoxyethylene glycol allyl ethers, methoxyl group end-blocking polyoxyethylene glycol allyl ethers, butoxy end-blocking polyoxyethylene glycol methallyl ethers, propoxy-end-blocking polyoxyethylene glycol allyl ethers, butoxy end-blocking polyoxyethylene glycol, 3-butene-1-alcohol ether or the oxyethyl group end-blocking polyethylene/polypropylene glycol allyl ethers.The alcohols monomer can be selected ethylene glycol, 1,2 propylene glycol, 1,4 butyleneglycol, neopentyl glycol, 1,5 pentanediol, 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, 1,4 cyclohexanedimethanol, the Hydrogenated Bisphenol A glycol, glycerol, tetramethylolmethane, TriMethylolPropane(TMP), trimethylolethane, phosphate compound can be selected phosphoric acid, contains phosphorous oxides, vinyl phosphoric acid, a kind of in the monoesters of phosphoric acid, dibasic acid esters or three esters or more than one.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 the 3-sulfydryl ethyl sulfonic acid, also might not add.Described initiator is selected benzoyl peroxide, peroxidation 2-ethyl acid tert-pentyl ester, the peroxidation 2-ethyl acid tert-butyl ester, 1, two (tert-pentyl peroxide) the cyclic group alkane of 1-, 1, two (the tert-pentyl peroxides)-3 of 1-, 3,5-trimethylammonium cyclohexane, peroxidation acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, peroxidation 3,3,5 trimethylammoniums are tert-butyl acrylate, peroxidized t-butyl perbenzoate, 3, two (tert-pentyl peroxide) ethyl butyrates of 3-, two (t-butyl peroxy) ethyl butyrates of 3,3-, dicumyl peroxide (DCP), peroxidation two tert-pentyls, di-t-butyl peroxide, t-amyl peroxy hydrogen, one or more of tertbutyl peroxide.
A kind of oiliness aluminium-silver slurry is directly used in the method for water-borne coatings, it is characterized in that being made up of following steps:
I. the oiliness aluminium-silver slurry adds above-mentioned auxiliary agent behind solvent dispersion, and dispersed with stirring obtains dispersion liquid;
Ii. the dispersion liquid that obtains is directly added in the water-borne coatings base-material, thereby obtain aqueous paint with flash metal luster.
Adoptable spraying method is a kind of of paint spraying modes such as aerial spraying, the spraying of electrostatic rotating cup, electrophoresis, dip-coating or more than one.The control of spraying environment is at the basic construction window of water-borne coatings, and relative humidity 60～80% is advisable for temperature 23-26 °.Can be used for each field such as baking vanish, self-drying paint, low-temperature lacquer, each water-borne coatings fields such as automobile, household electrical appliances, printing ink.
The acrylic acid or the like phosphoric acid ester that contains phosphoric acid ester functional group, oh group of the present invention is a kind of bound phosphate groups 5～25wt% that contains, the acrylic acid or the like phosphoric acid ester auxiliary agent of 1～5wt% oh group, be key component of the present invention, play the effect that prevents that oiliness aluminium-silver slurry (aluminium powder) from " getting angry " and reacting in water.This acrylic acid or the like phosphoric acid ester 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 the scope; Molecular weight control is 4000～8000, molecular weight distribution mw/mn: 1.1～2.0, and less molecular weight and narrow molecular weight distributions are evenly distributed on the molecular chain functional groups, 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 electroconductibility of the 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, further improve to the adsorptive power of aluminium-silver slurry (aluminium powder) and weather-proof, moisture-proof is warm, acidproof, alkaline-resisting, the cycle performance of anti-pipeline the, adhering 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 to the surface of aluminium-silver slurry.Apolar chain is strengthened the affinity interaction on aluminium powder surface and is suppressed water molecules to the erosion on aluminium-silver slurry (aluminium powder) surface.The 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 of directly in water-borne coatings, using.2, this invention operating procedure simple and stable, the product stock good stability prevents the excellent performance of getting angry in aluminium-silver slurry (aluminium powder) water, anti-high pressure conduction, weather-proof, moisture-proof is warm, acidproof, alkaline-resisting, the cycle performance of anti-pipeline excellence, sticking power to base material is good, and does not fall aluminium powder for a long time.3, do not sacrifice brightness and the film performance of oiliness aluminium-silver slurry (aluminium powder) itself by the prepared water-borne coatings of the present invention, can be used for each field such as baking vanish, self-drying paint, low-temperature lacquer, solved the expensive problem of water aluminum-silver slurry (aluminium powder) that water-borne coatings uses on the market.
This method operating procedure simple and stable, the product stock good stability prevents the excellent performance of getting angry in aluminium-silver slurry (aluminium powder) water, anti-high pressure electroconductibility, weather-proof, moisture-proof is warm, acidproof, alkaline-resisting, the cycle performance of anti-pipeline excellence, sticking power to base material is good, and does not fall aluminium powder for a long time.
[description of drawings]
Fig. 1 is configuration coating embodiment 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 repels each other and sterically hindered synoptic diagram for water-based system-electric charge of the present invention;
1. apolar chain A2. apolar chain B3. anchoring groups, 4. polar chain among the figure
[embodiment]
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is further elaborated, should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
A-1. acrylic acid or the like phosphoric acid ester embodiment 1
Drop into 30g Diethylene Glycol butyl ether and the different glycol hexyl ether of 5g in the reactor, be warming up to 130 ℃, (monomer mixed solution I consists of the 10g methyl acrylate to drop into monomer and initiator mixed solution, the 20g ethyl propenoate, the 5g butyl acrylate, 9g propoxy-end-blocking polyoxyethylene glycol allyl ethers, 15g butoxy end-blocking polyoxyethylene glycol allyl ethers, 3.2g self-control monomer, 1g phosphoric acid), initiator I is the 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 the 2g methyl acrylate, the 4g ethyl propenoate, the 1g butyl acrylate, 1g propoxy-end-blocking polyoxyethylene glycol allyl ethers, 3g butoxy end-blocking polyoxyethylene glycol allyl ethers, 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 continues to drop into initiator III0.2g peroxidation acetic acid tert-pentyl ester, and be cooled to 90 °, reaction 1hr, insulation 0.5hr, discharging; The gained molecular weight is 4000, molecular weight distribution mw/mn: 1.8.
Self-control monomer reaction situation is as follows:
A-2. acrylic acid or the like phosphoric acid ester embodiment 2
Drop into the 50g 1-Methoxy-2-propyl acetate in the reactor, be warming up to 120 ℃, (monomer mixed solution I consists of 20g vinylformic acid to drop into monomer and initiator mixed solution, the 20g Hydroxyethyl acrylate, the 5g glycidyl acrylate, the 10g lauryl methacrylate(LMA), the 2g AAEM, 9g3-butene-1-pure ether capped polyoxyethylene glycol allyl ethers, 3.2g SODIUM PHOSPHATE, MONOBASIC), initiator I is the 5g peroxidation 2-ethyl acid tert-butyl ester, reaction 4hr, insulation 2hr, continue to drop into monomer and initiator mixed solution, (monomer mixed solution II consists of 4g vinylformic acid, the 4g Hydroxyethyl acrylate, the 2g glycidyl acrylate, the 3g lauryl methacrylate(LMA), 8g3-butene-1-pure ether capped polyoxyethylene glycol allyl ethers, the 5g SODIUM PHOSPHATE, MONOBASIC), initiator II is 3, two (tert-pentyl peroxide) ethyl butyrates of 3-, 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; The gained molecular weight is 8000, molecular weight distribution mw/mn: 1.2.
A-3. acrylic acid or the like phosphoric acid ester embodiment 3
Drop into 20g glycol ether and 20g butanols in the reactor, be warming up to 130 ℃, (monomer mixed solution I consists of the 5g methacrylic acid to drop into monomer and initiator mixed solution, 10g vinylformic acid ammonium salt, the 10g Rocryl 410,5g methacrylic acid tetrahydrofuran ester, 20g vinylbenzene, the 2g vinyl acetate, 15g polyoxyethylene glycol tridecyl ether phosphoric acid, 20g self-control pre-polymerization monomer, 2g phosphoric acid), initiator I is the 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; The gained molecular weight is 6000, molecular weight distribution mw/mn: 1.4.
A-4. acrylic acid or the like phosphoric acid ester embodiment 4
Drop into the 40g isooctyl alcohol in the reactor, be warming up to 100 ℃, drop into monomer, the monomer initiator dropping time is 3hr, monomer mixed solution I consists of 10g methyl methacrylate, 10g ethyl propenoate, 5g methacrylic acid-2-ethylhexyl, 2g lauryl methacrylate(LMA), 8g methacrylic acid tetrahydrofuran ester, 2g Tryfac 5573 sylvite, 4g Triphenyl phosphate, 1g vinyl phosphoric acid, 0.5g3-Thiovanic acid; The initiator dropping time is 3.5hr, is the 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, and 5g vinylbenzene, 1g Vanadium Pentoxide in FLAKES, initiator II consist 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; The gained molecular weight is 19000, molecular weight distribution mw/mn: 2.0.
B-1. aluminium-silver slurry dispersion liquid embodiment 1
With 20g oiliness aluminium-silver slurry (aluminium powder), particle diameter 20 μ m, silver dollar shape, after being selected from the Eckart and the mixing of 20g butyl glycol ether of Germany, soak half an hour, add 6 parts of vinylformic acid phosphoric acid ester 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
With 40g oiliness aluminium-silver slurry (aluminium powder), particle diameter 10 μ m, the popcorn type, be selected from Eckart and the 25g glycol hexyl ether of Germany, after the 15g isooctyl alcohol mixes, soak half an hour, add 8 parts of vinylformic acid phosphoric acid ester 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
With 15g oiliness aluminium-silver slurry (aluminium powder), particle diameter 15 μ m, silver dollar shape after being selected from homemade family Xinghe 30g butyl glycol ether and mixing, is soaked half an hour, adds 9 parts of vinylformic acid phosphoric acid ester A-3 while stirring, continues to stir half an hour.
B-4. aluminium-silver slurry dispersion liquid embodiment 4
With 10g oiliness aluminium-silver slurry (aluminium powder), particle diameter 18 μ m, the popcorn type after being selected from homemade family's Xinghe 10g 1-Methoxy-2-propyl acetate, 10g butyleneglycol and mixing, soaks half an hour, adds 2 parts of vinylformic acid phosphoric acid ester A-4 while stirring, continues 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
With 20g oiliness aluminium-silver slurry (aluminium powder), particle diameter 13 μ m, the popcorn type after being selected from Japan of Japan and 10g butyl glycol ether, 30g butanols and mixing, soaks half an hour, adds 5 parts of vinylformic acid phosphoric acid ester A-4 while stirring, continues to stir half an hour.Add the 2gBYK180 wetting dispersing agent while stirring, stirred 10 minutes, regulate aluminium-silver slurry dispersion liquid PH to 8.1 with the 3g dimethylethanolamine again.
Dispose 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, the water-based hydroxyl acrylic acid dispersion;
3) Resydrol AN6481w is the special company of the cyanogen trade mark, the waterborne polyester dispersion;
4) Daotan VTW6462 is the special company of the cyanogen trade mark, acrylic resin modified by aqueous polyaminoester;
5) BayhydurXP2655 is Beyer Co., Ltd's resin trade mark, the water-based polyisocyanate curing agent;
6) Cytec303 is the special company of the cyanogen trade mark, aminoresin;
7) Foamstar A30 is BASF AG's trade mark, defoamer;
8) BYK011 is the Bi Ke chemical company trade mark, defoamer;
9) Tego Wet270 is the Di Gao company trade mark, the base material wetting agent;
10) BYK346 is the Bi Ke chemical company trade mark, the base material wetting agent;
11) Viscalex HV30 is BASF AG's trade mark, thickening material;
12) BYK425 is the Bi Ke chemical company trade mark, thickening material;
13) water aluminum-silver slurry dispersion liquid-1 adopts the SiO of Eckart as the contrast sample of aluminium-silver slurry dispersion liquid B-1
2The water-based aluminium powder of having handled well.With 20g water-based aluminium powder Hydorlan series, particle diameter 20 μ m after silver dollar shape and 20g butyl glycol ether mix, soak half an hour, add the 3gTego655(Di Gao company trade mark).
14) water aluminum-silver slurry dispersion liquid-2 adopts the SiO of Eckart as the contrast sample of aluminium-silver slurry dispersion liquid B-4
2The water-based aluminium powder of having handled well.With 20g water-based aluminium powder Hydorlan series, particle diameter 13 μ m after popcorn type and 10g 1-Methoxy-2-propyl acetate, 10g butyleneglycol mix, soak half an hour, and with the 2gAMP95(Dow Chemical trade mark) adjusting aluminium-silver slurry dispersion liquid PH to 8.2.
D. Performance Detection embodiment
The coating that above-mentioned preparation is finished adopts aerial spraying, in relative humidity 60～80%, temperature 23-26 °, is sprayed on the electrophoresis steel plate.Dodge and do 3-5min, 80 ° of prebake conditions 3-5min, thickness 10-20 μ m sprays supporting coating varnish 30-50 μ m again.C-1, C-2, C-5, C-7 are the high temperature baking vanish, 140 ° of baking 30min.C-3, C-4, C-6, C-8 are the low temperature baking vanish, 80 ° of baking 20min.Carry out paint stability (heat accelerate store), sticking power, the performance of getting angry, water-fast, moisture-proof is warm, the full Performance Detection of acidproof, alkaline-resisting, the cycle performance of anti-pipeline the, weathering resistance.Experimental result is as shown in Figure 2:
The embodiment interpretation of result,
1. relatively poor by water-borne coatings Embodiment C 7, the C8 appearance effect of the making of water-based aluminium powder, owing to increased the SiO2 coating layer, L value, brightness obviously descend.
The water-borne coatings Embodiment C-1 of being made by acrylic acid or the like phosphoric acid ester embodiment A-1, A-4, C-4, C-5 paint stability (heat is accelerated to store), sticking power, the performance of getting angry, water-fast, the impacts of performance such as moisture-proof is warm, acidproof, alkaline-resisting, the cycle performance of anti-pipeline the, weathering resistance are better.
3. relatively poor by water-borne coatings Embodiment C-2 acid resistance of acrylic acid or the like phosphoric acid ester embodiment A-2 making.
Water-borne coatings Embodiment C-3, the C-6 that is made by acrylic acid or the like phosphoric acid ester embodiment A-3 get angry performance, water-fast, paint stability is relatively poor.
5. water-borne coatings Embodiment C-3, the C-4 that is made by aluminium-silver slurry dispersion liquid Embodiment B-3, B-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 acid or the like phosphoric acid ester embodiment A-1, A-4; just can reach protection oiliness aluminium-silver slurry (aluminium powder), and a kind of mode of directly in water-borne coatings, using.
7. should invent, as water-borne coatings Embodiment C-1, C-4, C-5, the operating procedure simple and stable, the product stock good stability, prevent the excellent performance of getting angry in aluminium-silver slurry (aluminium powder) water, anti-high pressure conduction, weather-proof, moisture-proof is warm, acidproof, alkaline-resisting, the cycle performance of anti-pipeline excellence, and is good to the sticking power of base material, and do not fall aluminium powder for a long time.
8. by the prepared water-borne coatings of 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 field such as baking vanish, self-drying paint, low-temperature lacquer, solve the expensive problem of water aluminum-silver slurry (aluminium powder) that water-borne coatings uses on the market, thereby further promoted environmental protection coating material, Water-borne modification process.
Claims (10)
1. Water-borne modification auxiliary agent that the oiliness aluminium-silver slurry directly is used in water-borne coatings, its feature is to contain phosphate-based and acrylate kind phosphate ester hydroxyl at described auxiliary agent, the content of phosphate group 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. according to claim 1 the oiliness aluminium-silver slurry directly is used in the Water-borne modification auxiliary agent of water-borne coatings, it is characterized in that the oiliness aluminium-silver slurry is a kind of of commercially available general all kinds of specification oiliness aluminium-silver slurrys or more than one.
3. the oiliness aluminium-silver slurry dispersion liquid that can directly apply to water-borne coatings is characterized in that, common oiliness aluminium-silver slurry is through solvent dispersion, and the oiliness aluminium-silver slurry of per 10～45 weight parts also adds the described Water-borne modification auxiliary agent of 1～25 weight part claim 1.
4. the oiliness aluminium-silver slurry dispersion liquid that can directly apply to water-borne coatings as claimed in claim 3 is characterized in that described solvent is hydrophilic solvent.
5. the oiliness aluminium-silver slurry dispersion liquid that can directly apply to water-borne coatings as claimed in claim 3 is characterized in that also can comprising Ricinate and/or neutralizing agent.
6. water-borne coatings that directly adopts the preparation of oiliness aluminium-silver slurry dispersion liquid is characterized in that containing the water-base resin of the described aluminium-silver slurry dispersion liquid of the claim 3 that accounts for total mass 5～30% and 20～80%.
7. the water-borne coatings of a kind of direct employing oiliness aluminium-silver slurry dispersion liquid preparation as claimed in claim 6 is characterized in that also comprising 5～30% deionized water, 5～20% solvent, 0.1～2% defoamer, 0.1～2% base material wetting agent, 0.1～3% auxiliary rheological agents, 0.1～2% neutralizing agent.
8. the water-borne coatings of a kind of direct employing oiliness aluminium-silver slurry dispersion liquid preparation as claimed in claim 7 is characterized in that described solvent is alcohols or ether organic solvent.
9. method for preparing the described auxiliary agent of claim 1, it is characterized in that adopting free radical solution polymerization, in described solvent, react, be warming up to 80～140 ℃, 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, phosphoric acid, phosphoric acid ester, P contained compound, the vinylformic acid sodium sulfonate, the mixture of chain-transfer agent, described monomer is acrylic monomer, vinylbenzene, esters monomer, the alcohols monomer, P contained compound, the vinylformic acid sodium sulfonate, the mixture of chain-transfer agent, initiator are that tradition is used for a kind of of the synthetic peroxide initiator of acrylic resin or more than one.
10. an oiliness aluminium-silver slurry is directly used in the method for water-borne coatings, it is characterized in that being made up of following steps: i. oiliness aluminium-silver slurry adds the described auxiliary agent of claim 1 behind solvent dispersion, dispersed with stirring obtains dispersion liquid;
Ii. the dispersion liquid that obtains is directly added in the water-borne coatings base-material, thereby obtain aqueous paint with flash metal luster.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310253564.1A CN103289012B (en) | 2013-06-24 | 2013-06-24 | The preparation method of oiliness aluminium-silver slurry Water-borne modification auxiliary agent and prepared water-borne coatings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310253564.1A CN103289012B (en) | 2013-06-24 | 2013-06-24 | The preparation method of oiliness aluminium-silver slurry Water-borne modification auxiliary agent and prepared water-borne coatings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103289012A true CN103289012A (en) | 2013-09-11 |
| CN103289012B CN103289012B (en) | 2016-01-20 |
Family
ID=49090585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310253564.1A Expired - Fee Related CN103289012B (en) | 2013-06-24 | 2013-06-24 | The preparation method of oiliness aluminium-silver slurry Water-borne modification auxiliary agent and prepared water-borne coatings |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103289012B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403462A (en) * | 2014-12-29 | 2015-03-11 | 湖南湘江关西涂料有限公司 | Solvent-type thermosetting quick-drying primary-colored paint for automobile and preparation method of solvent-type thermosetting quick-drying primary-colored paint |
| CN104789103A (en) * | 2015-04-30 | 2015-07-22 | 常州浩阳水性新材料有限公司 | Water-based photocuring paint for 3C electronic industry and preparation method thereof |
| CN104926985A (en) * | 2015-06-01 | 2015-09-23 | 南通拜森化工有限公司 | Phosphate-acrylic resin for silver paint and preparation method thereof |
| CN105273503A (en) * | 2015-02-16 | 2016-01-27 | 上海荟百精细化工有限公司 | Aqueous aluminum paste for aqueous silver printing ink and preparation method therefor |
| CN106085064A (en) * | 2016-06-07 | 2016-11-09 | 蚌埠市禹会区贵宾装饰材料商行 | A kind of fire resistant water-based flash coating material of photo frame |
| CN106554706A (en) * | 2016-11-29 | 2017-04-05 | 天津市瑞宝绿色纳米涂料有限公司 | A kind of waterborne epoxy modified acrylic resin aluminium paint of use oiliness aluminum paste |
| CN108976891A (en) * | 2018-08-09 | 2018-12-11 | 阜阳市诗雅涤新材料科技有限公司 | A kind of hard monomer cladding aluminium silver powder and its production method and application |
| CN109836951A (en) * | 2019-01-17 | 2019-06-04 | 浙江省海洋开发研究院 | A kind of cupric is linearly from polishing marine antifouling coating |
| CN110028861A (en) * | 2019-04-10 | 2019-07-19 | 河北晨阳工贸集团有限公司 | Aqueous industrial aluminium paint, preparation method and its flatulence detection device |
| CN111057430A (en) * | 2020-01-02 | 2020-04-24 | 廊坊立邦涂料有限公司 | Universal composition with good covering property and preparation method and application thereof |
| CN113402952A (en) * | 2021-06-08 | 2021-09-17 | 清远市实创涂料科技有限公司 | Two-component water-based epoxy silver powder paint and preparation method and application thereof |
| CN113785021A (en) * | 2019-04-12 | 2021-12-10 | Viavi科技有限公司 | Method for preparing special effect pigments using emulsions |
| 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 |
| CN114292542A (en) * | 2021-12-23 | 2022-04-08 | 广东邦荣新材料有限公司 | Water-based electrosilvering coating and preparation method thereof |
| CN114410162A (en) * | 2022-01-21 | 2022-04-29 | 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 |
| WO2024051315A1 (en) * | 2022-09-09 | 2024-03-14 | 立邦涂料（中国）有限公司 | Aqueous color masterbatch composition containing aluminum powder pigment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0156089A1 (en) * | 1984-03-12 | 1985-10-02 | Etablissements LE SIMPLEX (société à responsabilité limitée) | Method for making and assembling members rotating between side plates, and the products obtained, especially for use in the tending and winding of the chain in speed changes for bicycles and similar vehicles |
| CN1986665A (en) * | 2005-12-22 | 2007-06-27 | 关西油漆株式会社 | Aqueous coating composition |
| CN101412781A (en) * | 2008-12-01 | 2009-04-22 | 中国海洋石油总公司 | Hydroxy acrylic ester emulsion containing phosphoester group |
| CN101760071A (en) * | 2008-12-23 | 2010-06-30 | 上海涂料有限公司技术中心 | Method for using solvent type resin aluminum pigment in water paint |
| CN103102460A (en) * | 2011-11-14 | 2013-05-15 | 大日精化工业株式会社 | Phosphoric group-containing block copolymer, pigment dispersant, and pigment-based colorant composition |
-
2013
- 2013-06-24 CN CN201310253564.1A patent/CN103289012B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0156089A1 (en) * | 1984-03-12 | 1985-10-02 | Etablissements LE SIMPLEX (société à responsabilité limitée) | Method for making and assembling members rotating between side plates, and the products obtained, especially for use in the tending and winding of the chain in speed changes for bicycles and similar vehicles |
| CN1986665A (en) * | 2005-12-22 | 2007-06-27 | 关西油漆株式会社 | Aqueous coating composition |
| CN101412781A (en) * | 2008-12-01 | 2009-04-22 | 中国海洋石油总公司 | Hydroxy acrylic ester emulsion containing phosphoester group |
| CN101760071A (en) * | 2008-12-23 | 2010-06-30 | 上海涂料有限公司技术中心 | Method for using solvent type resin aluminum pigment in water paint |
| CN103102460A (en) * | 2011-11-14 | 2013-05-15 | 大日精化工业株式会社 | Phosphoric group-containing block copolymer, pigment dispersant, and pigment-based colorant composition |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403462A (en) * | 2014-12-29 | 2015-03-11 | 湖南湘江关西涂料有限公司 | Solvent-type thermosetting quick-drying primary-colored paint for automobile and preparation method of solvent-type thermosetting quick-drying primary-colored paint |
| CN104403462B (en) * | 2014-12-29 | 2017-08-04 | 湖南湘江关西涂料有限公司 | A kind of automobile solvent type heat-curing quick-drying primary colours paint and preparation method thereof |
| CN105273503B (en) * | 2015-02-16 | 2018-05-22 | 上海荟百精细化工有限公司 | A kind of aqueous silver ink water aluminum-silver slurry of printing and preparation method thereof |
| CN105273503A (en) * | 2015-02-16 | 2016-01-27 | 上海荟百精细化工有限公司 | Aqueous aluminum paste for aqueous silver printing ink and preparation method therefor |
| CN104789103A (en) * | 2015-04-30 | 2015-07-22 | 常州浩阳水性新材料有限公司 | Water-based photocuring paint for 3C electronic industry and preparation method thereof |
| CN104789103B (en) * | 2015-04-30 | 2016-11-16 | 常州浩阳水性新材料有限公司 | A kind of 3C used in electronic industry waterborne radiation curable coating and preparation method thereof |
| CN104926985A (en) * | 2015-06-01 | 2015-09-23 | 南通拜森化工有限公司 | Phosphate-acrylic resin for silver paint and preparation method thereof |
| CN106085064A (en) * | 2016-06-07 | 2016-11-09 | 蚌埠市禹会区贵宾装饰材料商行 | A kind of fire resistant water-based flash coating material of photo frame |
| CN106554706A (en) * | 2016-11-29 | 2017-04-05 | 天津市瑞宝绿色纳米涂料有限公司 | A kind of waterborne epoxy modified acrylic resin aluminium paint of use oiliness aluminum paste |
| CN106554706B (en) * | 2016-11-29 | 2019-07-16 | 天津市瑞宝绿色纳米涂料有限公司 | A kind of waterborne epoxy modified acrylic resin aluminium paint using oiliness aluminum paste |
| CN108976891A (en) * | 2018-08-09 | 2018-12-11 | 阜阳市诗雅涤新材料科技有限公司 | A kind of hard monomer cladding aluminium silver powder and its production method and application |
| CN109836951A (en) * | 2019-01-17 | 2019-06-04 | 浙江省海洋开发研究院 | A kind of cupric is linearly from polishing marine antifouling coating |
| CN109836951B (en) * | 2019-01-17 | 2021-01-05 | 浙江省海洋开发研究院 | Copper-containing linear self-polishing marine antifouling paint |
| CN110028861A (en) * | 2019-04-10 | 2019-07-19 | 河北晨阳工贸集团有限公司 | Aqueous industrial aluminium paint, preparation method and its flatulence detection device |
| CN113785021A (en) * | 2019-04-12 | 2021-12-10 | Viavi科技有限公司 | Method for preparing special effect pigments using emulsions |
| US11655374B2 (en) | 2019-04-12 | 2023-05-23 | Viavi Solutions Inc. | Method for manufacturing a special effect pigment using an emulsion |
| CN111057430A (en) * | 2020-01-02 | 2020-04-24 | 廊坊立邦涂料有限公司 | Universal composition with good covering property and preparation method and application thereof |
| CN113402952A (en) * | 2021-06-08 | 2021-09-17 | 清远市实创涂料科技有限公司 | Two-component water-based epoxy silver powder paint and preparation method and application thereof |
| 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 |
| WO2023093806A1 (en) * | 2021-11-25 | 2023-06-01 | Ppg Coatings (Tianjin) Co., Ltd. | Waterborne aluminum formulation and method of preparing the same |
| CN114292542A (en) * | 2021-12-23 | 2022-04-08 | 广东邦荣新材料有限公司 | Water-based electrosilvering coating and preparation method thereof |
| CN114410162A (en) * | 2022-01-21 | 2022-04-29 | 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 |
| 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 |
| WO2024051315A1 (en) * | 2022-09-09 | 2024-03-14 | 立邦涂料（中国）有限公司 | Aqueous color masterbatch composition containing aluminum powder pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103289012B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103289012B (en) | The preparation method of oiliness aluminium-silver slurry Water-borne modification auxiliary agent and prepared water-borne coatings | |
| CN101885943B (en) | Nano-glass heat insulation paint and preparation method thereof | |
| CN101649153B (en) | Organic silicon modified acrylic ester aqueous wood lacquer latex and synthesizing method thereof | |
| CN102432743B (en) | Polymer emulsion for waterborne metal anticorrosive coating and preparation method of polymer emulsion | |
| CN107964317A (en) | Water soluble acrylic acid amino-stoving varnish and preparation method thereof | |
| CN103409026B (en) | A kind of environment-friendly water-based anti-flaming dope | |
| CN102108252B (en) | Waterborne vacuum film-coated finish paint | |
| CN102134434A (en) | High-performance water-based white sealing primer | |
| CN101775245A (en) | Multifunctional putty and preparation method thereof | |
| CN110054976B (en) | Aqueous hydroxy acrylic acid dispersoid modified by multi-heterocyclic acrylate monomer and preparation method thereof | |
| CN103012714A (en) | High-flexibility aqueous acrylic acid polyurethane elastic resin and coating thereof | |
| CN102432766A (en) | Hydroxyl-containing water-based acrylic ester polymer and preparation method thereof | |
| CN106632893A (en) | Acrylic acid finish emulsion and preparation method thereof | |
| CN107286777A (en) | A kind of conductive anti-corrosive primer coating of water nano polyaniline epoxy acrylic resin | |
| CN109517516A (en) | A kind of cerium bentonite modified watersoluble polyurethane paint and preparation method thereof | |
| CN103540217A (en) | Aziridine crosslinked acrylate resin two-component water-based automobile coating and preparation method thereof | |
| CN105111360A (en) | Preparation method of multiple-crosslinked water-based acrylic resin | |
| CN101270254B (en) | Watersoluble modified acrylic acid bi-component plastic rubber paint and preparation method thereof | |
| CN110105856A (en) | The preparation method and applications of water based acrylic resin and 3C coating | |
| CN106009960B (en) | A kind of preparation method of water-acid resistance damping paint | |
| CN101747827B (en) | Environment-friendly alkyd coating | |
| CN102492100B (en) | Water-dispersed fluorine-containing hydroxyl acrylic-epoxy ester heterozygous body resin and coating thereof | |
| CN102559104B (en) | Waterborne gravure printing aluminum-coated compound glue and preparation method thereof | |
| CN107383943B (en) | Water aluminum-silver slurry and preparation method thereof with clad | |
| CN102086347A (en) | Edge banding agent for consolidated floor, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20160624 |