CN102690561A - Water-based antirust and antifouling paint used on wall surface and preparation method thereof - Google Patents
Water-based antirust and antifouling paint used on wall surface and preparation method thereof Download PDFInfo
- Publication number
- CN102690561A CN102690561A CN2012101945625A CN201210194562A CN102690561A CN 102690561 A CN102690561 A CN 102690561A CN 2012101945625 A CN2012101945625 A CN 2012101945625A CN 201210194562 A CN201210194562 A CN 201210194562A CN 102690561 A CN102690561 A CN 102690561A
- Authority
- CN
- China
- Prior art keywords
- water
- paint
- borne coatings
- unsaturated
- wall surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a type of water-based antirust and antifouling paint used on a wall surface. The paint contains the following components in parts by weight: 20-60 parts of film forming substance, 1-10 parts of film-forming additive, 0.5-2 parts of copolymer of unsaturated monomer which contains fluoro aliphatic groups and unsaturated silane monomer, 0-5 parts of cosolvent, 0.1-1 part of corrosion inhibitor and appropriate amount of water. The invention further designs a preparation method of the paint. The water-based paint used for preventing rust and dirt on the wall surface is environment-friendly and economic; the water-based paint and common wall surface emulsion paints have the same the construction ways. The paint disclosed by the invention can prevent rust on the wall surface, has the capability of resisting stains and can reach better beautifying and decoration effects. The paint is an excellent paint which is used on the wall surface and is antirust, antifouling, environment-friendly and economic.
Description
Technical field
The present invention relates to a kind of water-borne coatings and preparation method thereof, relate to a kind of water-borne coatings that is used for the anti-rusty stain of metope, anti-stain and preparation method thereof in particular.
Background technology
Coating is widely used in the family, in order to coating internal surfaces and outside surface.More feedback is arranged at present on the market,,, many rust stainings occur about behind metope brushing rubber-emulsion paint especially in southern humid area.The body of wall base material can roughly be divided into two kinds, and the one, putty layer, the putty powder that is used for the levelling function is of a great variety, and quality is very different; Shuanghui powder, talcum powder etc. all belong to mineral substance in its composition, wherein must be mingled with a large amount of metallic impurity, and are in the majority with iron rust impurity; The production unit of the small-sized manufacturer of part use is simultaneously safeguarded not in place; Be mingled with a large amount of iron rust impurity in the putty powder finished product that finally causes producing.The 2nd, old paint film, when old metope renovated, the iron nail on the metope was unprocessed, i.e. the brushing rubber-emulsion paint.Running into water when above base material is that the rubber-emulsion paint of dispersion medium promptly gets rusty, and rust spot is distributed on the whole paint film along with the moving of service tool, and finally causes a large amount of rust stainings to appear on the paint film, reduces greatly that it is ornamental.Especially at wet season, this phenomenon is even more serious.CN 102321413A discloses a kind of water-borne coatings that is used for the anti-rusty stain of metope, and said coating is made up of filmogen, film coalescence aid, pigment, stopping composition, solubility promoter, inhibiter, dispersion agent, skimmer, thickening material, pH regulator agent, mould inhibitor, sanitas and water.This invention also discloses the preparation method of this coating.Constructional method and common metope are identical with rubber-emulsion paint, and can prevent the generation of metope rust staining.
The antifouling property of coating also is an important factor weighing coating property, and antifouling paint is a cost-effective measure that prevents that pollutent from adhering to.Disclose a kind of coating composition like CN 1474837A, said composition can provide sufficiently high water resisting property for filming, oil-proofness and didirtresistance, and guarantee the cohesiveness high to base material.Coating composition comprises a kind of multipolymer, and this multipolymer is basic unsaturated vinegar monomer and the monomeric copolymerization product of unsaturated silane of fluorine-containing fat subsitutes family.
Summary of the invention
The object of the present invention is to provide a kind of can simultaneously antirust, antifouling wall paint; It can defend to run into metope with the water in the rubber-emulsion paint component because of the iron rust impurity of body of wall well; And the rust staining that produces; Reach good beautifying and decorating effect, sufficiently high water resisting property, oil-proofness and didirtresistance can also be provided for filming; Coating process and common metope are identical with rubber-emulsion paint.
Antirust, antifouling water-borne coatings provided by the present invention comprises the filmogen of 20-60 part, 1 ~ 10 part film coalescence aid, 0.5 ~ 2 part the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane, 0 ~ 5 part of solubility promoter, 0 ~ 1 part of pH regulator agent, 0.1 ~ 1 part of inhibiter and an amount of water by weight.
Filmogen
In order to solve the problem of rubber-emulsion paint and metope rust staining.The inventor finds; Through selecting a kind of brand-new AVANSETM technology synthetic interpolymer latex of polystyrene and acrylic ester that adopts for use; Compare with the conventional acrylic emulsion, this new technology makes polymkeric substance have more good parcel ability to pigment and stopping composition, thereby strengthens the bonding force between powder and the polymkeric substance greatly; Especially some antirust activity pigment make the whole prod system reach good preservative property and formulation stability.This emulsion adopts hydrophobic monomer, hydrophobic surfactant to synthesize, and has the self-crosslinking technology simultaneously concurrently, makes product form densification, hydrophobic coating.The excellent performance of this emulsion also shows the one side of its environmental protection, as not containing formaldehyde and APEO composition, satisfies the current even following environmental requirement.
Preferably, the glass transition temperature of said acrylic emulsions is between 10 ℃-30 ℃.Described acrylic emulsions can commercially availablely obtain; Perhaps prepare through above-mentioned technology, concrete example as, vinylbenzene and acrylate monomer, emulsifying agent, initiator etc. obtain through emulsion polymerization.
The not concrete restriction of the molecular weight of the styrene emulsion of described acrylic ester copolymer modification is as long as make glass transition temperature reach required 10 ℃-30 ℃.
The not concrete restriction of the copolymerization ratio of the styrene emulsion of described acrylic ester copolymer modification is as long as make glass transition temperature reach required 10 ℃-30 ℃.
Film coalescence aid
The not concrete restriction of film coalescence aid of the present invention can be adopted the commercially available various auxiliary agents that are applicable to acrylic coating, and this is known to those skilled in the art.
The present invention provides the preferred example of film coalescence aid; Also promptly the film coalescence aid in prescription is the mixture and 2 of pentanedioic acid two (second-methyl-prop) ester, Succinic Acid two (second-methyl-prop) ester and two (second-methyl-propyl) adipic acid ester; 2,4-trimethylammonium-1, the 3-pentanediol mono isobutyrate is composite; Tool hangs down characteristics such as smell, hydrolysis-stable, high boiling point, low toxicity, safety, acceptable biological degradation; Since better with the polymer phase capacitive, make the latex particle coalescence more complete, and sticking power, the water tolerance of therefore filming are better.And said mixture and 2,2,4-trimethylammonium-1, the weight proportion of 3-pentanediol mono isobutyrate are 1: (0.5-1.5); Can reach the object of the invention better during use.
Rubber-emulsion paint has only at a certain temperature could film coalescence, and this can form continuously and desirable minimum temperature of filming is called minimum film-forming temperature (MFT).If be lower than the construction of this temperature, then in the rubber-emulsion paint behind the moisture evaporation, latex particle can not be agglomerated into successive and film, but is discontinuous film Powdered or the cracking shape.The various performances of at this moment filming such as sticking power property is poor, with serious decline such as the cohesive force difference of pigment.The film forming of rubber-emulsion paint can be divided into moisture evaporation, emulsion particle distortion and latex molecule segment diffusion winding and be fused into continuous three steps of film; For guaranteeing that emulsion particle well is out of shape; Inclusion pigment and stopping composition form continuous, fine and close paint film better, often will add film coalescence aid.
In order to reduce MFT, reach the balance between high-performance and the low construction temperature.For guaranteeing the final high-performance of paint film, so require film coalescence aid that following characteristics are arranged: the one, should be the strong solvent of polymkeric substance, thereby can reduce the second-order transition temperature of polymkeric substance, and have good consistency, otherwise can influence paint film appearance.The 2nd, the solubleness in water is low, and being prone to is had good coalescence performance by emulsion particle absorption, and faint is water-soluble, easily by other component institute emulsifications of rubber-emulsion paint.And, in film process, can not be pulled away with moisture evaporation owing to its low water solubility.The 3rd, should have suitable evaporation rate, before film forming, be retained among the polymkeric substance, can vapor away fully after the film forming.
Can be a lot of as the organic solvent of film coalescence aid.Film coalescence aid when adopting, will be at first in water and polymer phase (organic phase) distribute, its is brought into play film forming usefulness and depends at two partition ratios in mutually, depends on the plasticising usefulness of this auxiliary agent, also depends on its evaporation rate.Film coalescence aid can be regarded the internal plasticization comonomer of polymkeric substance as, and the second-order transition temperature of film coalescence aid can be used to judge its plasticity to polymkeric substance; The contriver selects according to the rate of volatilization of various film coalescence aid, the SP of polymer emulsion, the indexs such as partition ratio of film coalescence aid; Wherein film coalescence aid is selected the mixture and 2 of pentanedioic acid two (second-methyl-prop) ester, Succinic Acid two (second-methyl-prop) ester and two (second-methyl-propyl) adipic acid ester for use; 2; 4-trimethylammonium-1, the 3-pentanediol mono isobutyrate is composite; And said mixture and 2,2,4-trimethylammonium-1, the weight proportion of 3-pentanediol mono isobutyrate are 1: (0.5-1.5); The SP that can reach well with this polymer emulsion is close, and lower rate of volatilization and low water solubility are arranged.So in prescription, select it as film coalescence aid.For guaranteeing film-forming properties preferably,, its consumption is controlled at 1-10 weight part (or 1-10%) according to the emulsion consumption.
The unsaturated ester monomer and the monomeric copolymerization product of unsaturated silane that contain the fluoro fatty group
The unsaturated ester monomer that contains fluorinated aliphatic group that is used for the copolymer of the present composition can be final coating provides water resisting property, oil-proofness and didirtresistance.For bringing into play its good water resisting property, oil-proofness and didirtresistance and do not influence the performance of the others of coating, its consumption is 0.5 ~ 2 part.The ester monomer be a kind of part that contains at least by the substituted aliphatic group of fluorine, particularly at least part by the substituted alkyl of fluorine, and the compound of the two keys of the unsaturated carbon-to-carbon of polymerizable ethylene type.More specifically, containing the compound that the unsaturated ester monomer of fluorinated aliphatic group comprises can be expressed from the next:
Wherein, Rf is a line style, side chain or cyclic, and at least partly by the substituted aliphatic group of fluorine.For example, part is preferably contained the perfluoroalkyl of 2 to 12 carbon atoms, R by the substituted alkyl of fluorine at least
1Be H or CH
3, Q is a low-grade alkylidene, as-CH
2-or-CH
2CH
2, or-SO
2NR
2-low-grade alkylidene, as-SO
2NR
2-CH
2-or-SO
2NR
2-CH
2CH
2-, R wherein
2Be hydrogen or low alkyl group, as-CH
3Or-C
2H
5
Along with the increase of carbon atom number among the Rf or fluorine replacement number, water resisting property, oil-proofness and didirtresistance also can be better.If but amount of carbon atom is too much, it is generally acknowledged that multipolymer possibly gather in main tissue.Therefore, Rf preferably contains the fluorinated aliphatic group of 3 to 7 carbon atoms, carbonatoms be 3 to 6 then better.The end group of Rf is perfluoro-CF preferably
3Group is so that obtain high waterproof, oil-proofness and didirtresistance.
In order not influence the performances such as water resisting property of multipolymer, Q can be low-grade alkylidene, preferably-and CH
2-or-CH
2CH
2-.
The unsaturated ester monomer that contains fluorinated aliphatic group generally can account for ester monomer and unsaturated silane total monomer weight at least 50% or more, preferably 70% or more.In this scope, coating can obtain high waterproof, oil-proofness and didirtresistance.
The unsaturated silane monomer segment can promote the cohesiveness of final coating and base material in the multipolymer.The unsaturated silane monomer is a kind of silane type compound, it comprise can promote and base material between the two keys of close-burning Siliciumatom and the unsaturated carbon-to-carbon of polymerizable ethylene type.More specifically, the compound that comprises of unsaturated silane monomer can be represented by following molecular formula:
Wherein, R
1Be H or CH
3, R
3Be hydrogen or low alkyl group, like methyl or ethyl, X is an alkoxyl group, halogen or RCOO-, wherein R is hydrogen or low alkyl group, like methyl or ethyl, Y be singly-bound or-CH
2-, n is 0,1 or 2 integer.When X was alkoxyl group, particular compound can be enumerated: vinyltrimethoxy silane, such as: (CH
3O)
3SiCH=CH
2, (C
2H
5O)
3SiCH=CH
2, and the allyl group trialkoxy silane, like (CH
3O)
3SiCH
2CH=CH
2When X is RCOO-, can comprise (CH
3COO)
3SiCH=CH
2
Calculate according to unsaturated ester monomer that contains fluorinated aliphatic group and unsaturated silane total monomer weight, the monomeric weight percentage of unsaturated silane is generally 1% to 50%.If the weight percentage less than 1% of silane monomer, it maybe not can show close-burning promoter action between coating and the base material.Yet if content surpasses 50%, water resisting property and oil-proofness can reduce.For performances such as cohesiveness and water resisting property between coating and the base material are balanced each other, the monomeric weight percentage of unsaturated silane preferred 1% to 30%, 1% to 10% is better, and 1.5% to 4% particularly good.
Multipolymer can be by traditional free radical polymerisation process preparation.More specifically; In the presence of radical polymerization initiator such as Diisopropyl azodicarboxylate; The unsaturated ester monomer and the unsaturated silane monomer that will contain fluorinated aliphatic group are dissolved in suitable solvent such as the hydrogen fluorohydrocarbon ether, and heating polymerization in 10 to 20 hours obtains multipolymer thus between 60 ℃ to 75 ℃.
Recommending the molecular weight of multipolymer in the compsn is 100 to 50,000, and better then is 500 to 5,000.If molecular weight is too small, then film forming properties is poor, if molecular weight is excessive, then coating composition viscosity increases, and makes final compsn be difficult to use.
Solubility promoter
The not concrete restriction of solubility promoter of the present invention can be adopted the commercially available various solubility promoters that are applicable to acrylic coating, and this is known to those skilled in the art.
In an embodiment of the present invention, the solubility promoter that is adopted is 1, the 2-Ucar 35.
In a preference, said solubility promoter is selected from Ucar 35.
With water is the water-borne coatings of dispersion medium, antifreeze being inevitable; When envrionment temperature below 0 ℃ the time; Will freeze; At this moment raw materials such as emulsion, dispersion agent, wetting agent, thickening material, pigment and stopping composition in the rubber-emulsion paint component; Because of losing this maximum of water, best stable environment, occur phenomenons such as serious back thickening, serious layering, breakdown of emulsion, gel then, thereby have influence on the quality of rubber-emulsion paint.Therefore to add solubility promoter, to reduce the freezing point of rubber-emulsion paint.Usually solubility promoter has Ucar 35, terepthaloyl moietie and glycol ethers, considers to select Ucar 35 the prescription from environmental angle.
The weight part of said solubility promoter is decided according to the requirement of rubber-emulsion paint low-temperature stability, can add the 0-5 weight part usually.More preferably, 0.1～5 weight part.
PH value regulator
PH value conditioning agent of the present invention is not specifically limited, and only otherwise goal of the invention of the present invention is produced restriction get final product, for example employing can be used for the pH conditioning agent of acrylic coating.
In an embodiment of the present invention, the pH regulator agent of being adopted is a 2-amino-2-methyl-1-propanol.Its advantage is that the coating smell is more much smaller than ammoniacal liquor after regulating, and the rubber-emulsion paint pH value is stable; This is for the system that contains active rust-stabilising pigment, and the stable of pH value is even more important, and can help to stablize the rubber-emulsion paint system.Its amount is that 0～1 weight part is good in prescription.Preferred 0.1～1 weight part.
Inhibiter
Water-borne coatings is coated in the metallic surface, and the film forming initial stage, corrosion took place easily, so must add inhibiter; The corrosion process of metal in medium is made up of two conjugated electrochemical reactions, and these two electrochemical reactions are respectively anodic reaction and cathodic reaction; Can both suppress and inhibiter can suppress in anode, the cathodic reaction one or two, just can reduce corrosion speed; So inhibiter is claimed corrosion inhibitor again.
Inhibiter generally is divided into oxidized form, deposition membranous type, metallic cation type and organic cpds class.
Oxidized form inhibiter such as chromic salt, nitrite, molybdate and tungstate etc., they itself are oxygenants or make oxygenant with the dissolved oxygen in the medium, can make the metallic surface form the close r-Fe that makes a speech
2O
3Protective membrane, the thickness of this layer protective membrane cause the metals ion process to be obstructed, thereby slow down corrosion of metal between 5 ~ 10nm.For chromic salt and nitrite, because toxicity is bigger, superseded basically in many coating at present; And, owing to itself do not have an oxidisability, when then must aerobic in the medium existing, just corrosion inhibition can be arranged for molybdate and tungstate.
The deposition membranous type, they can with the relevant ionic reaction in the medium, and the cathodic area on the metallic surface form to suppress the corrosive precipitation membrane, and is covered in cathode surface, and metal and corrosive medium are separated; Therefore can be divided into two types on negative electrode inhibition type and Mixed Inhibition type again.Negative electrode inhibition type inhibiter such as zinc sulfate, Calcium hydrogen carbonate, phosphoric acid salt etc.; Mostly Mixed Inhibition type inhibiter is organism, and this type inhibiter is interacted by the metals ion that generates in the complexing agent of the sulphur on the molecule, oxygen, nitrogen-atoms group and the corrosion process and forms precipitation membrane.
The metallic cation type mainly contains zinc powder, and its inhibition mechanism is to set up an electrochemical cell, makes iron and steel on the basis of zinc anode, become negative electrode, but zinc powder will reach 85% ~ 95% of whole solids constituent necessary electroconductibility can be provided
The organic cpds class is called the absorption membranous type again, and it has good adsorption property to the metallic surface in corrosive medium, and they are adsorbed on the metallic surface, makes medium be difficult for preventing to corrode with metallic contact.This type inhibiter, its molecule should have good consistency with the resin in the coating, loss of adhesion because excessive inhibiter can cause.
Usually select the type and the consumption of inhibiter, it suppresses corrosive nature to need integrated survey, will drop to minimum simultaneously to the influence of coating.
Preferably, select organic cpds class inhibiter in this prescription; More preferably, the inhibiter that is adopted is water-fast organic carboxyl acid salt compounds, is used for coating and can significantly improves its anti-rust property of dodging: the 0.1-1 weight part.
Said an amount of water is meant that its viscosity adjustment with the metope rust-inhibiting paint arrives required scope.In a preference, said an amount of water is meant that its viscosity adjustment with the metope rust-inhibiting paint arrives between (85-89) KU.
Antirust, antifouling water-borne coatings provided by the present invention can be chosen wantonly and contain pigment.Can adopt the commercially available various pigment that are applicable to water-borne coatings, this is known to those skilled in the art.The pigment that is fit to comprises carbon black; Titanium oxide; Modified phosphate; Iron pigment such as solid oxidation iron; Weisspiessglanz pigment; Barium pigment; Calcium pigment; Zirconium pigment; Chrome pigment; Magnesium pigment; Lead pigments; Zinc sulphide; Lithopone; Phthalocyanine blue (phthalo blue); Phthalocyanine green (phthalo green); Metallic pigment such as aluminium; Pearly pigment; Opalescence pigment; Luster pigment; With solid bead and the microspheroidal pigment of plastic pigment as containing space and vesica.
In an embodiment of the present invention, the hiding pigment that is adopted is that specific refractory power is big, resistance to chalking, chemicalstability, light stability rutile TiO preferably
2The rust-stabilising pigment that is adopted is a modified phosphate; Its mechanism of action is; Generate the shielding deposition in the positive column, the early period of origination corrosion makes steel surface produce local anode and negative electrode on the film location owing to breakage is coated with, and local anodic iron begins dissolving; Ferrous salt that is dissolved out and molysite generation hydrolysis; The proton that discharges just produces phosphoric acid and zine ion with the zn phosphate effect, and the effect of cathodic inhibitor is so just arranged, and phosphoric acid then generates the insoluble tertiary iron phosphate that shields with the metallic surface effect.Zn phosphate is a kind of colourless, nontoxic rust-stabilising pigment with good stability, and heavy metal content is extremely low, has been put in the national security standard.The particle diameter of common zn phosphate is approximately 12 ~ 20um, is the brick shape, and rustless property is not very desirable; For improving the rust-proof effect of zn phosphate, it is carried out chemistry improve processing, increase the shielding deposition, improve its rustless property greatly.
Stopping composition
Antirust, antifouling water-borne coatings provided by the present invention can be chosen wantonly and contain stopping composition.The not concrete restriction of stopping composition of the present invention can be adopted the commercially available various stopping composition that are applicable to water-borne coatings, and this is known to those skilled in the art.
In an embodiment of the present invention, the natural whiting that the stopping composition that is adopted is respectively is low-cost, physical strength is high, wear resistance is good, and can improve the dry film opacifying power, improve suspension, hydrated aluminium silicate that hardness of film is high.
As optimal technical scheme, said coating also comprises dispersion agent, skimmer, thickening material, mould inhibitor, at least one of the preservatives.
Dispersion agent
The dispersion of powder, wetting principle, the one, dispersant adsorption is in the powder particle, and the powder particle of cohesion is moistening; The 2nd, macromolecule dispersing agent is adsorbed on the powder particle surface, increases pigment and the interparticle surface charge of stopping composition, improves interparticle electrostatic repulsion, and has effectively increased interparticle sterically hinderedly, makes that the particle stabilized dispersion of powder becomes possibility in the liquid.Divide according to molecular structure, dispersion agent generally is divided into two big types: inorganic dispersant and organic dispersing agent.In the majority in the inorganic dispersant with the polyphosphoric acid salt, like Sodium hexametaphosphate 99, Potassium tripolyphosphate, sodium polyphosphate and TKPP.The mechanism of its effect is through hydrogen bond and chemisorption, plays the electrostatic repulsion stabilization.Its advantage is good to mineral dye and stopping composition dispersion effect, but with the rising of pH value and temperature, the easy hydrolysis of polyphosphoric acid salt, not good to extended storage stability.Organic dispersing agent comprises polyacrylate, PS/maleic acid salt, polyisobutene/maleic acid salt etc.Their characteristics are, produce strong absorption or anchorage effect on the powder surface, and it is sterically hindered to form to have long molecular chain, and the end of the chain has water-soluble, and what have also auxilliaryly has electrostatic repulsion, reaches stable result.
Organic dispersing agent is different because of its molecular weight, and performance can be different; Lower molecular weight type dispersion agent has the polar group that is close on one or more spaces; They are adsorbed on surface of pigments, are used for the stabilizing powder particle with spatial masking, thereby make viscosity degradation; This type dispersion agent is mainly used in mineral dye; Because of mineral dye is an ionic structure, higher surface polarity is arranged, dispersion agent is easy to absorption.And pigment dyestuff contains C, H, O group because of its surface, and no ionic activity so often use the high-molecular weight dispersion agent, has the more surface that group is adsorbed on pigment dyestuff of sticking, and it can form persistent adsorption layer on pigment dyestuff.But too Da Yi flocculation of the molecular weight of dispersion agent.So should select according to pigment and stopping composition type during the type of selection dispersion agent.
In an embodiment of the present invention, the dispersion agent that is adopted is a poly carboxylic acid sodium type dispersion agent.Reach emulsion paint system stable state based on dispersant best wetting point to pigment and inserts in prescription, confirm its optimum amount.In this prescription, select the hydrophobically modified polycarboxylate of 0～3 weight part can reach best effects.More preferably, 0.1～3 weight part.
Skimmer
Coating by produce, canned, transportation, construction all have mechanical force to forming the whole process of paint film at last; Must a large amount of air be brought in the latex system, a large amount of foams can make the production operation difficulty, and plant factor is not enough; It is insufficient to cause pigment and stopping composition to disperse, even can't produce down.It is to stay many defectives to filming that a large amount of foams brings graver results in the time of can giving construction, like shrinkage cavity, and paint film disadvantages such as pin hole, crater.An effective skimmer acts on quite important in coating system.
Foam can be regarded as a quite a large amount of insoluble gas and is dispersed in the dispersion-s in the small amount of liquid, is under the effect of mechanical force, could to form.Foam is unsettled in itself, sometimes because the effect of the thermal motion of liquid own is enough to make it to vanish.It is generally acknowledged that froth breaking mechanism can be divided into following four processes: 1, skimmer is adsorbed onto the foamy surface; 2, skimmer is penetrated into the foamy surface; 3, skimmer spreads on foam surface, and the adsorption surface promoting agent; 4, foam tension imbalance-broken bubble.
Can be known that by froth breaking mechanism skimmer is the liquid of low surface tension, generally should have following characteristic: 1, the surface tension of skimmer is less than the surface tension that needs froth breaking liquid self; 2, the solubleness in needing the liquid of froth breaking is as far as possible little; 3, good dispersiveness to be arranged.4, can not react with the liquid of want froth breaking, can not influence the force of cohesion of pigment in the coating and the stability of emulsion.5, stronger diffusive force to be arranged.6, can not influence the performance of finished product rubber-emulsion paint.7, unpleasant odor can not be arranged.
In an embodiment of the present invention, the skimmer that is adopted is the mixture of water drain silica and MO.The consumption of skimmer can add according to those skilled in the art's general knowledge, is the 0-1 weight part such as consumption, preferred 0.1-1 weight part.
Thickening material
Coating and viscosity are closely related.It has a very important characteristic is exactly thixotropy.Thixotropic being characterised in that has when static certain very weak reticulated structure to form, and forms physical crosslinking like the hydrogen bond between polymkeric substance; With the pigment particles is that bridge all shows as thickening by " crosslinked " that its polar adsorption forms between the polymkeric substance.Viscosity and shearing force then show as thixotropy, have applied viscosity degradation after the shearing force, and promptly reticulated structure is destroyed; In case the shearing force of removing, reticulated structure progressively recovers, and viscosity rises again.It is a pseudo-plasticity phenomenon relevant with time and shearing force.When coating ideal state promptly is storage, higher viscosity is arranged to stablize whole system better; During coating application, need lower viscosity to obtain to construct preferably leveling characteristics.This thixotropy needs to rely on an ideal rheology thickened systems just can reach, it well this quiet one moving viscosity of balance change, thixotropy is preferably promptly arranged.
According to its mechanism of action, can be divided into four big types of cellulose family, polyacrylic and non-ionic associative type polyurethane thickening material and inorganic thickening agents.
Cellulose thickener has methylcellulose gum, CMC 99.5 (MC), Natvosol (HEC), Vltra tears (MHPC) etc., and that wherein the most frequently used is Natvosol (HEC).The thickening mechanism of cellulose thickener cellulose thickener is that hydrophobic main chain and ambient water molecule pass through hydrogen bond association, has improved the fluid volume of polymkeric substance itself, has reduced the free active of particle space, thereby has improved the system viscosity.The advantage of this type thickening material is that thickening efficiency is high, and shortcoming is that leveling characteristics is poor.
Polyacrylate thickeners can be divided into two kinds basically: a kind of is the homopolymer of water miscible acrylate, and its thickening mechanism is, meet in the alkali and after, carboxylic acid ion is transformed into carboxylate salt.The formation of carboxylate salt causes interior molecules to be repelled, and polymkeric substance is extended, and along polymer chain, water molecules is adsorbed, and increases the viscosity of water; Another kind is the homopolymer or the copolymer emulsion thickening material of vinylformic acid, methylacrylic acid; Its thickening mechanism is the hydrophilic chain of association type thickening and water association, and hydrophobic side and powder and latex particle association; Form reticulated structure at aqueous phase, thereby increase the viscosity of system.More than these two kinds of thickening materials itself be tart, must be neutralized to pH8～9 with alkali or ammoniacal liquor and just can reach thickening effectiveness, be also referred to as propylene soda acid swelling thickening material.The relative cellulose thickener of this thickening material can be given film better leveling characteristics and gloss.
The polyurethanes thickening material belongs to the associative thickener of non-ionic type, contains hydrophilic radical and hydrophobic grouping in the molecular structure of this type thickening material respectively, makes it demonstrate the character of certain tensio-active agent.When its concentration of aqueous solution surpasses a certain certain concentration, form micella, micella and polymer particle associate and form reticulated structure, and the system viscosity is increased.Several micellas of branch subband have on the other hand reduced the transport property of water molecules, and the water viscosity is also improved.This type thickening material not only exerts an influence to the rheological of coating, and and adjacent latex particle between exist and interact.The advantage of this type thickening is that good, anti-the splashing property of leveling characteristics of filming is good, and shortcoming is that single use causes the latex layering easily.
Inorganic thickening agent is one type of water-swelling and form thixotropic gel mineral.Mainly contain wilkinite, attapulgite, pure aluminium silicate etc., wherein wilkinite is the most commonly used.The inorganic thickening agent wilkinite is a kind of layered silicate, and the suction after forms flocculent substance, has good suspension and dispersiveness, is combined into colloid with an amount of water, in water, can discharge charged corpuscle, increases the system viscosity.
Usually two or more thickening materials mix use, can compensate the defective that single thickening material uses.So in practical application, tend to adopt two kinds or above thickening material collocation use, to reach an ideal rheology state
In an embodiment of the present invention, the thickening material that is adopted is the saline and alkaline swelling type emulsion of the ROHM of water-soluble cellulose derivative, hydrophobically modified.More preferably, the two composite use
The consumption of thickening material can add according to those skilled in the art's general knowledge, is controlled at 0～3 weight part such as consumption, preferred 0.1～3 weight part.
Mould inhibitor and sanitas
The anti-algae agent of mildew-resistant of the present invention is not specifically limited with anticorrisive agent, produces to limit only otherwise to goal of the invention of the present invention to get final product.
In rubber-emulsion paint, derivatived cellulose and some auxiliary agent, the nutriment that all can become mikrobe, mould like emulsifying agent, skimmer etc. is originated.Coating is once microbial contamination, as long as growth conditions such as organism, humidity, oxygen, potential of hydrogen and temperature etc. are suitable, will ramp multiply, and the result causes coating rotten, smelly.This has just determined, in processes such as the production of water-borne coatings, storage, transportation, application, exists the serious problem that tackles mikrobe.Microbe species is various, and gram-negative bacteria is arranged usually, and especially large intestine produces oxygen Pseudomonas and Pseudomonas, and the Pseudomonas of different areas can be different.So require mould inhibitor to have broad spectrum, anti-various mikrobes, drug effect is high, for a long time active, simultaneously to human non-toxic.When the kind of the anti-algae agent of selection mildew-resistant, sanitas and consumption are higher than minimum inhibitory concentration MIC according to its active ingredient often, just can reach its effective provide protection.
In an embodiment of the present invention, the mould inhibitor that is adopted is benzoglyoxaline Urethylane, N '-(3, the 4-dichlorophenyl)-N, N-dimethyl urea or its combination.Water-soluble low, the good light stability of benzoglyoxaline Urethylane wherein, Heat stability is good, toxicity is low.And N '-(3, the 4-dichlorophenyl)-N, the N-dimethyl urea has good resistant function to algae substances.
In an embodiment of the present invention, the sanitas that is adopted is 1,2-benzisothiazole-3-1 and verivate thereof.It is release formaldehyde not, and is not halogen-containing, non-volatile, and good stability has thermally-stabilisedly, and ph stability can use in pH value scope widely, and chemicalstability is good, to had no corrosive effect on metals.
The consumption of mould inhibitor can add according to those skilled in the art's general knowledge, is 0～1 weight part such as consumption, preferred 0.1～1 weight part.
The consumption of sanitas can add according to those skilled in the art's general knowledge, is 0～1 weight part such as consumption, preferred 0.1～1 weight part.
One of the object of the invention is also to provide that a kind of metope is antirust, the preparation method of antifouling varnish, comprises the steps: by set of dispense slowly to add water-soluble thickener than earlier water, skimmer, dispersion agent being added the material-compound tank mixing respectively, stirs; Selectable then adding pigment, stopping composition grind 10-20min at a high speed; To fineness, add filmogen, stir, add other functional agents again, and regulate viscosity and pH value, filter, packing obtains metope rust-inhibiting paint finished product.
In a preference, said metope is antirust, antifouling varnish carries out according to following production technique:
Water, dispersion agent, part skimmer are added material-compound tank successively, stir, slowly add the water soluble cellulose thickening material, stir 5min; Add pigment, stopping composition then, grind 10 ~ 20min at a high speed; To fineness, add solubility promoter, film coalescence aid stirring 5min successively; Add mould inhibitor, sanitas stirring 3min then successively; Add again after filmogen, skimmer stir; Regulate viscosity and pH value with PH regulator, thickening material respectively; Regulate viscosity to (85-89) KU; Add inhibiter at last and contain the unsaturated ester monomer and the monomeric copolymerization product of unsaturated silane of fluoro fatty group, obtain promptly that metope is antirust, the antifouling varnish finished product.
The inventor is through constantly testing, studying; Make a kind of water-borne coatings that can be used for the anti-rust staining of metope, anti-stain; It can solve well that metal rust preventing lacquer constructing operation is loaded down with trivial details, not environmental protection, problem such as cost an arm and a leg; And avoided paint film because of the brushing oil-base paint too in smooth, and occur can't the brushing water-miscible paint problem; And solved rubber-emulsion paint chance iron rust and promptly got rusty, be prone to pollution problems.
This product constructing operation is very simple, and is identical with the construction of generic latex lacquer.This product also has and body of wall base material sticking power preferably, and impervious alkalescence, anti-saltouing property, water tolerance, alkaline resistance properties are excellent; Before the brushing rubber-emulsion paint, brushing earlier is this product together, can stop the generation of rust staining fully and have stain resistance, and because of all properties of its tool priming paint, can be used as one priming paint and use, and the rubber-emulsion paint of brushing twice again finish paint gets final product, construct simple and easy and save time, laborsaving.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment only is used for helping to understand the present invention, should not be regarded as concrete restriction of the present invention.
Specify like nothing, various raw materials of the present invention all can obtain through commercially available; Or prepare according to the ordinary method of this area.Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
The experimental technique of unreceipted actual conditions in the following example is measured according to national standard usually.If there is not a corresponding national standards, then carry out according to general international standard, normal condition or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is a number-average molecular weight.
Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Embodiment 1
20 parts filmogen (glass transition temperature is 29 ℃ a interpolymer latex of polystyrene and acrylic ester), 2 parts film coalescence aid, 0.5 part the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane are with (F (CF
2)
6CH
2OC (=O) C (CH
3)=CH
2(component 1) is as the unsaturated ester monomer that contains fluorinated aliphatic group, (C
2H
5O)
3SiCH=CH
2As the unsaturated silane monomer, make by preparation process provided by the invention), 1 part of solubility promoter (1, the 2-Ucar 35), 1 part of pH regulator agent (2-amino-2 methyl isophthalic acids-propyl alcohol), 0.1 part of inhibiter (aminocarboxylate) and an amount of water.
Utilize preparation method provided by the invention to prepare coating, dope viscosity is transferred to 89KU.
Embodiment 2
40 parts filmogen (glass transition temperature is 14 ℃ a interpolymer latex of polystyrene and acrylic ester), 5 parts film coalescence aid, 2 parts the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane are (with C
7F
15SO
2N (C
2H
5) C
2H
4OC (=O) C (CH
3)=CH
2As containing fluorinated aliphatic group unsaturated ester monomer, (C
2H
5O)
3SiCH=CH
2As the unsaturated silane monomer; Make by preparation process provided by the invention), 5 parts of solubility promoters (1, the 2-Ucar 35), 0.1 part of pH regulator agent (2-amino-2 methyl isophthalic acids-propyl alcohol), 1 part of inhibiter (nitrocarboxylic acid salt) and an amount of water, 0.5 dispersion agent (polycarboxylate sodium's type dispersion agent).
Utilize preparation method provided by the invention to prepare coating, dope viscosity is transferred to 85KU.
Embodiment 3
60 parts filmogen (glass transition temperature is 20 ℃ a interpolymer latex of polystyrene and acrylic ester), 10 parts film coalescence aid, 1 part the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane are (with c-C
6F
11CH
2OC (=O) C (CH
3)=CH
2As the unsaturated ester monomer that contains fluorinated aliphatic group, (C
2H
5O)
3SiCH=CH
2As the unsaturated silane monomer; Make by preparation process provided by the invention), 2 parts of solubility promoters (1, the 2-Ucar 35), 0.5 part of pH regulator agent (2-amino-2 methyl isophthalic acids-propyl alcohol), 0.5 part of inhibiter (nitrocarboxylic acid salt) and an amount of water, 0.1 dispersion agent (polycarboxylate sodium's type dispersion agent), 1 part of skimmer (mixture of water drain silica and MO).
Utilize preparation method provided by the invention to prepare coating, dope viscosity is transferred to 86KU.
Embodiment 4
30 parts filmogen (glass transition temperature is 10 ℃ a interpolymer latex of polystyrene and acrylic ester), 3 parts film coalescence aid, 1.5 parts the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane are (with C
6F
13C
2H
4OC (=O) C (CH
3)=CH
2As the unsaturated ester monomer that contains fluorinated aliphatic group, (C
2H
5O)
3SiCH=CH
2As the unsaturated silane monomer; Make by preparation process provided by the invention), 3 parts of solubility promoters (1, the 2-Ucar 35), 0.3 part of pH regulator agent (2-amino-2 methyl isophthalic acids-propyl alcohol), 0.7 part of inhibiter (nitrocarboxylic acid salt) and an amount of water, 3 parts of dispersion agents (polycarboxylate sodium's type dispersion agent), 0.1 part of skimmer (mixture of water drain silica and MO), 3 parts of thickening materials (the saline and alkaline swelling type of the ROHM of water-soluble cellulose derivative, hydrophobically modified latex composite compounding).
Utilize preparation method provided by the invention to prepare coating, dope viscosity is transferred to 88KU.
Embodiment 5
The filmogen of 20-60 part (glass transition temperature is 15 ℃ a interpolymer latex of polystyrene and acrylic ester), 1 ~ 10 part film coalescence aid, 0.5 ~ 2 part the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane are (with (CF
3)
2CF (CF
2)
2C
2H
4OC (=O) CH=CH
2As the unsaturated ester monomer that contains fluorinated aliphatic group, with (CH
3O)
3SiCH=CH
2(component 9), (C
2H
5O)
3SiCH=CH
2Or (CH
3O)
3SiCH
2CH=CH
2As the unsaturated silane monomer; Make by preparation process provided by the invention), 0 ~ 5 part of solubility promoter (1; The 2-Ucar 35), 0 ~ 1 part of pH regulator agent (2-amino-2 methyl isophthalic acids-propyl alcohol), 0.1 ~ 1 part of inhibiter (nitrocarboxylic acid salt) and an amount of water, 1.5 parts of dispersion agents (polycarboxylate sodium's type dispersion agent), 0.5 part of skimmer (mixture of water drain silica and MO), 1.5 parts of thickening materials (the saline and alkaline swelling type of the ROHM of water-soluble cellulose derivative, hydrophobically modified latex composite compounding), 0.1 part of mould inhibitor (benzoglyoxaline Urethylane, N '-(3; The 4-dichlorophenyl)-N; The N-dimethyl urea), 0.2 portion of sanitas (1,2-benzisothiazole-3-1).
Utilize preparation method provided by the invention to prepare coating, dope viscosity is transferred to 87KU.
Embodiment 6
The filmogen of 20-60 part (glass transition temperature is 25 ℃ a interpolymer latex of polystyrene and acrylic ester), 1 ~ 10 part film coalescence aid, 0.5 ~ 2 part the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane are (with H (CF
2)
4CH
2OC (=O) CH=CH
2As the unsaturated ester monomer that contains fluorinated aliphatic group, (C
2H
5O)
3SiCH=CH
2As the unsaturated silane monomer; Make by preparation process provided by the invention), 0 ~ 5 part of solubility promoter (1; The 2-Ucar 35), 0 ~ 1 part of pH regulator agent (2-amino-2 methyl isophthalic acids-propyl alcohol), 0.1 ~ 1 part of inhibiter (nitrocarboxylic acid salt) and an amount of water, 2 parts of dispersion agents (polycarboxylate sodium's type dispersion agent), 0.3 part of skimmer (mixture of water drain silica and MO), 0.3 part of thickening material (the saline and alkaline swelling type of the ROHM of water-soluble cellulose derivative, hydrophobically modified latex composite compounding), 1 part of mould inhibitor (benzoglyoxaline Urethylane, N '-(3; The 4-dichlorophenyl)-N; The N-dimethyl urea), 1 portion of sanitas (1,2-benzisothiazole-3-1), 15 parts of pigment (rutile TiO
2And modified phosphate), 20 parts of stopping composition (natural whiting and hydrated aluminium silicate).
Utilize preparation method provided by the invention to prepare coating, dope viscosity is transferred to 85KU.
Comparative Examples
The coating that the prescription preparation in accordance with the present invention that is provided by the embodiment among the CN 102321413A 1 and 2 makes.
Performance evaluation:
Specimen preparation: 76 * 16mm sheet glass of a precleaning is immersed in the coating solution of the present invention and Comparative Examples preparation (room temperature), follow quick pull-up, dry sample.
Salt water resistance, salt-fog resistant test: with reference to the metal anti-corrosion paint standard test.
Antifouling property is estimated: the reagent that is used to test the coating resistance to crocking comprises blue food dye, red ink, red wine, tea and coffee solution and a kind of special hydrophobicity test compounds " K and N ".These contamination reagent are applied to film go up and polluted 1 hour.Remove excessive contamination reagent then and with the thorough cleaning of will filming of household cleaners and toilet paper.The antifouling property that visually rank is filmed, and compare with suitable control and to be divided into 5 ranks, wherein the 5=resistance to crocking is good, and the 1=resistance to crocking is poor.Common antipollution grade is at least 3 and shows that coating has the good resistance contaminative.
Evaluation result such as following table:
It is thus clear that coating provided by the present invention has good antirust, stain resistance.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a water-borne coatings that is used for the anti-rusty stain of metope, anti-stain comprises the filmogen of 20-60 part, 1 ~ 10 part film coalescence aid, 0.5 ~ 2 part the unsaturated ester monomer that contains the fluoro fatty group and the monomeric copolymerization product of unsaturated silane, 0 ~ 5 part of solubility promoter, 0 ~ 1 part of pH regulator agent, 0.1 ~ 1 part of inhibiter and an amount of water by weight.
2. water-borne coatings according to claim 1, said coating also comprises dispersion agent, skimmer, thickening material, mould inhibitor, at least one of the preservatives.
3. water-borne coatings according to claim 1, described filmogen are selected from the acrylic emulsions of glass transition temperature between 10 ℃-30 ℃.
4. water-borne coatings according to claim 1; Described film coalescence aid is the mixture and 2 of pentanedioic acid two (second-methyl-prop) ester, Succinic Acid two (second-methyl-prop) ester and two (second-methyl-propyl) adipic acid ester; 2,4-trimethylammonium-1, the 3-pentanediol mono isobutyrate is composite; And said mixture and 2,2,4-trimethylammonium-1, the weight proportion of 3-pentanediol mono isobutyrate are 1: (0.5-1.5).
5. water-borne coatings according to claim 1, described unsaturated silane monomer is selected from vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide and vinyl-uncle-butoxy silane;
Preferably, calculate by basic unsaturated ester monomer and the unsaturated silane total monomer weight of fluorine-containing fat subsitutes family, the monomeric content of said unsaturated silane is 1-50 weight %.
6. water-borne coatings according to claim 1, described solubility promoter are 1, the 2-Ucar 35.
7. water-borne coatings according to claim 1, described pH regulator agent is a 2-amino-2-methyl-1-propanol.
8. water-borne coatings according to claim 1, described inhibiter are water-fast organic carboxyl acid salt compounds.
9. water-borne coatings according to claim 1, described dispersion agent are polycarboxylate sodium's type dispersion agent;
Preferably, described skimmer is the mixture of water drain silica and MO;
Preferably, described thickening material is the saline and alkaline swelling type latex composite compounding of ROHM of water-soluble cellulose derivative and hydrophobically modified;
Preferably, described mould inhibitor is benzoglyoxaline Urethylane, N '-(3, the 4-dichlorophenyl)-N, N-dimethyl urea or its combination;
Preferably, described sanitas is 1,2-benzisothiazole-3-1 and verivate thereof.
10. water-borne coatings preparation method according to the anti-rusty stain of each described metope of claim 1 ~ 9, anti-stain; It is characterized in that; Than earlier water, skimmer, dispersion agent being added the material-compound tank mixing respectively, slowly add water-soluble thickener by set of dispense, stir; Selectable then adding pigment, stopping composition grind 10-20min at a high speed; To fineness, add filmogen, stir, add other functional agents again, and regulate viscosity and pH value, filter, packing obtains metope rust-inhibiting paint finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101945625A CN102690561A (en) | 2012-06-13 | 2012-06-13 | Water-based antirust and antifouling paint used on wall surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101945625A CN102690561A (en) | 2012-06-13 | 2012-06-13 | Water-based antirust and antifouling paint used on wall surface and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102690561A true CN102690561A (en) | 2012-09-26 |
Family
ID=46856307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101945625A Pending CN102690561A (en) | 2012-06-13 | 2012-06-13 | Water-based antirust and antifouling paint used on wall surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102690561A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571294A (en) * | 2013-11-25 | 2014-02-12 | 漳州鑫展旺化工有限公司 | Pollution-free environment-friendly corrugated paint and preparation method thereof |
| CN112322119A (en) * | 2020-11-23 | 2021-02-05 | 安徽嘉年华漆业有限公司 | Novel environment-friendly wall antifouling paint and production process thereof |
-
2012
- 2012-06-13 CN CN2012101945625A patent/CN102690561A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571294A (en) * | 2013-11-25 | 2014-02-12 | 漳州鑫展旺化工有限公司 | Pollution-free environment-friendly corrugated paint and preparation method thereof |
| CN103571294B (en) * | 2013-11-25 | 2016-04-13 | 漳州鑫展旺化工有限公司 | Pollution-free environmental protection wrinkle varnish and preparation method thereof |
| CN112322119A (en) * | 2020-11-23 | 2021-02-05 | 安徽嘉年华漆业有限公司 | Novel environment-friendly wall antifouling paint and production process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102321413A (en) | A kind of water-borne coatings that is used for the anti-rusty stain of metope and preparation method thereof | |
| CN101215438B (en) | Anti-soiling aging-resisting stainless steel paint and preparation method thereof | |
| CN104098972B (en) | Water-based antirust and antiseptic paint for metal and preparation method thereof | |
| CN101649153B (en) | Organic silicon modified acrylic ester aqueous wood lacquer latex and synthesizing method thereof | |
| CN103849267B (en) | A kind of water-based paint compositions and preparation method thereof | |
| CN106243852A (en) | High-performance water-based light non-corrosive metal (NCM) protective paint and preparation method thereof | |
| CN102993906A (en) | Waterborne epoxy antirust paint and preparation method | |
| CN106243966A (en) | A kind of composite multifunction double-component aqueous woodenware white finish paint and preparation method thereof | |
| CN102702899B (en) | Water-based modified pure acrylic acid anticorrosive paint | |
| CN101528812A (en) | Optimized alkanolamines for latex paints | |
| CN109207034A (en) | A kind of aqueous rusty anti-corrosion primer and preparation method thereof | |
| CN110003750A (en) | Water-based paint compositions and its coating of formation | |
| CN108047839A (en) | A kind of aqueous inorganic environmental protection coating material and preparation method thereof | |
| CN103360874A (en) | Waterborne exterior-wall paint and its preparation method | |
| CN104725969B (en) | Water-based anti-corrosion floating type aluminium powder paint and preparation method thereof | |
| CN102250519A (en) | Latex paint for plastic base material painting and preparation method thereof | |
| CN106752498A (en) | A kind of multifunctional aqueous paint and preparation method thereof | |
| CN107118626A (en) | A kind of water-based exterior wall paint for exempting from priming paint | |
| CN107267003A (en) | Vehicle bridge coating of waterborne organic silicon modified acroleic acid bottom surface unification and preparation method thereof | |
| CN102220058A (en) | Bi-component aqueous epoxy latex paint capable of substituting for ceramic tile | |
| CN102690561A (en) | Water-based antirust and antifouling paint used on wall surface and preparation method thereof | |
| CN110003744A (en) | Scratch resistance imitates the art coatings and its manufacturing method of nap effect | |
| CN107903725A (en) | Non-through constitution sense finish and its preparation method and application | |
| CN104559591A (en) | Environment-friendly water-based paint for aluminum profile production and preparation method thereof | |
| CN1626586A (en) | Water born paint in use for plastic painting dressing and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120926 |