CN108192403A - A kind of solvent type zinc-aluminum paint - Google Patents

A kind of solvent type zinc-aluminum paint Download PDF

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Publication number
CN108192403A
CN108192403A CN201810064748.6A CN201810064748A CN108192403A CN 108192403 A CN108192403 A CN 108192403A CN 201810064748 A CN201810064748 A CN 201810064748A CN 108192403 A CN108192403 A CN 108192403A
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zinc
solvent
aluminum paint
coupling agent
type zinc
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CN108192403B (en
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张志恒
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Winstar Chemicals Shanghai Co Ltd
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Winstar Chemicals Shanghai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to protecting metallic surface fields, and in particular to a kind of solvent type zinc-aluminum paint.A kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4：1~5：1 mixing composition；By weight, the component A includes：75~90 parts of zinc aluminium alloy powders, 15~18 parts of organic solvents, 3~12 parts of fillers, 0.2~0.7 part of coupling agent, 0.3~0.9 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2With the mixture of isocyanate-terminated super branched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 5~9：1.

Description

A kind of solvent type zinc-aluminum paint
Technical field
The present invention relates to metal protection fields, and in particular to a kind of solvent type zinc-aluminum paint.
Background technology
Metal erosion is widely present in nature, this not only results in the waste of resource, is even caused the accident, is given sometimes The people's lives and property safety belt carrys out immeasurable loss.From world wide, all material is every year because of corrosion loss About 1% weight corrodes the economic loss brought accounts for about national economy total amount 4%, and this loss is in the torrid zone and marine environment In it is even more serious, at present China's only marine corrosion bring loss just be more than GDP 3%, anti-corrosion road is shouldered heavy responsibilities.Ocean The industries such as engineering, shipbuilding and green marine wind energy are grown rapidly, industrial antisepsis coating and field of coating enter at a high speed into Long gold period, market scale have been only second to building coating in various coating varieties and have occupied second.In recent years, China is in infrastructure construction, cities and towns My Perspective On The Co-building and new countryside construction, the Olympic Games, the Asian Games, Shanghai World's Fair and the whole world Shanghai etc. is settled in maximum Disneyland, suffers from huge coating demand, under new international situation and national policy, Fast development for coating industry and industrial antisepsis coating provides new opportunity, greatly develops new anti-corrosion coating, has wide Prospect and realistic meaning.
Based on this background, the present invention provides a kind of solvent type zinc-aluminum paints with excellent properties, it is not only relatively low Temperature and humidity under also can rapid draing, and coating adhesion is good, and flexibility is good, excellent corrosion resistance, even if applying Also there is excellent corrosion resistance in the case of covering compared with shallow layer.
The solvent type zinc-aluminum paint of the present invention can apply to every field, including：Emerging ocean engineering：Offshore Units, sea Bank and bay structure, offshore oil platform；Modern Traffic is transported；Energy industry：Water conservancy project equipment, petroleum refinement equipment, oil Bunkerage, power transmission and transforming equipment, nuclear power, steam-electric power plant, wind energy generating plant；Large size industrial enterprise；Urban operating mechanism etc..
Invention content
The first aspect of the invention provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4： 1~5：1 mixing composition；By weight, the component A includes：75~90 parts of zinc aluminium alloy powders, 15~18 parts it is organic molten Agent, 3~12 parts of fillers, 0.2~0.7 part of coupling agent, 0.3~0.9 portion of anti-settling agent；The component B is teos hydrolysis Liquid；The anti-settling auxiliary agent is MoS2With the mixture of isocyanate-terminated super branched polyurethane, the MoS2And isocyanic acid The mass ratio of ester terminated super branched polyurethane is 5~9：1.
As a kind of preferred technical solution of the present invention, the organic solvent is selected from ethyl alcohol, n-butanol, isopropanol, uncle Butanol, butanone, cyclohexanone, butyl acetate, ethylene glycol ether acetate, butyl glycol ether, butanediol methyl ether, methyl-isobutyl Ketone, isobutyl acetate, ethyl acetate, octyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl hexyl ketone, 120#Solvent Oil, 200#Solvent naphtha, D30#Solvent naphtha, D40#Solvent naphtha, D60#Solvent naphtha, D65#Solvent naphtha, D80#Solvent naphtha, D90#Solvent Oil, D100#Solvent naphtha, D110#Solvent naphtha, D130#Solvent naphtha, D160#Solvent naphtha any one or more of.
As a kind of preferred technical solution of the present invention, the filler be selected from modified graphene, ferrotitanium powder, hydrotalcite, Bentonite, wollastonite in powder, zinc oxide, La2O3、Ce2O3、CeO2、Ce9O16、Ce7O12、Ce6O11、 Ce10O8、Ce11O20、Pr6O11、 PrO1.65、PrO1.714、PrO1.800、Nd2O3、Tb2O3、Tb4O5、 Tb4O7、Ho2O3、Sm2O3、Tm2O3、Yb2O3、Y2O3、MnO2、 WO3、WO2.90、WO2.72、 WO2、MoO3Any one or more of.
As a kind of preferred technical solution of the present invention, the filler is modified graphene, talcum powder, zinc oxide, water The mixture of talcum, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2~0.5：1~3：3~4：0.3 ~0.7.
As a kind of preferred technical solution of the present invention, the modified graphene is furane resins modified graphene.
As a kind of preferred technical solution of the present invention, the coupling agent be selected from silane coupling agent, titanate coupling agent, Zirconium ester coupling agent, aluminate coupling agent any one or more of.
As a kind of preferred technical solution of the present invention, the coupling agent be selected from gamma-aminopropyl-triethoxy-silane, N- phenylaminomethyls triethoxysilane, (3- trimethoxy silicon propyl) diethyl ethylenediamine, anilinomethyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidoxypropyltrietandysilane andysilane, β-(3,4- epoxide rings Hexyl) ethyl trimethoxy silane, 3- (isobutene acyl-oxygen) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, γ-mercapto hydroxypropyl methyl dimethoxysilane, double-(γ-triethoxysilylpropyl)-tetrasulfide, 3- (isobutene acyl-oxygen) propyl Trimethoxy silane, vinyl three (2- methoxy ethoxies) silane, vinyltrimethoxysilane, three (dioctyl of isopropyl Pyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, (two is pungent for two oleic acid acyloxy of isopropyl Base phosphoric acid acyloxy) titanate esters, three iso stearate isopropyl titanates, Di(dioctylpyrophosphato) ethylene titanate, four In isopropyl two (dioctyl phosphito acyloxy) titanate esters, four n-propyl zirconates, distearyl acyl-oxygen isopropyl Aluminate It is any one or more.
As a kind of preferred technical solution of the present invention, other auxiliary agents, institute are further included in the solvent type zinc-aluminum paint The auxiliary agent stated is selected from any one of pigment, wetting dispersing agent, toughener, thickener, leveling auxiliary agent, kollag or more Kind.
The second aspect of the invention provides the preparation method of the solvent type zinc-aluminum paint, which is characterized in that extremely Include the following steps less：
A. according to parts by weight, zinc aluminium alloy powder, organic solvent, filler, coupling agent, anti-settling agent, stirring are added in a reservoir 0.5~1h obtains component A after dispersion mixing is uniform；
B. component A and component B that step a is obtained proportionally are mixed, stirs 0.5~1h, obtained described molten Dosage form zinc-aluminum paint.
The third aspect of the present invention provides application of the solvent type zinc-aluminum paint in protecting metallic surface field.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Solvent type zinc-aluminum paint in the present invention has very excellent performance, also can at relatively low temperature and humidity Rapid draing, and coating adhesion is good, and flexibility is good, excellent corrosion resistance.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Object, step, method, product or device are not necessarily limited to those elements, but can include not expressly listed other elements or Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element do not pointed out, step or component.If in claim, this Phrase will make claim be closed, it be made not include the material in addition to the material of those descriptions, but relative normal Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body, It is only limited to the element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range All ranges that any pairing of lower limit or preferred value is formed, regardless of whether the range separately discloses.For example, when open During range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end Value and all integers and score in the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " arbitrary It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents specific the present invention is not limited to this Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, it is approximate Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with It combines and/or exchanges, these ranges include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before element of the present invention or component and "one" quantitative requirement to element or component (i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
The first aspect of the invention provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4： 1~5：1 mixing composition；By weight, the component A includes：75~90 parts of zinc aluminium alloy powders, 15~18 parts it is organic molten Agent, 3~12 parts of fillers, 0.2~0.7 part of coupling agent, 0.3~0.9 portion of anti-settling agent；The component B is teos hydrolysis Liquid.
Zinc aluminium alloy powder
The current potential of zinc is far defeated by carbon steel, after coating is accidentally damaged or by long-term use, water, oxygen, chloride permeability to painting When layer is with the interfaces of steel, zinc in coating then as sacrificial anode, can considerably long in the period of in steel is protected not generate corruption Erosion.And zinc and water, oxygen, chlorion and carbon dioxide reaction and the corrosion products such as difficulty soluble salt, such as 2ZnCO can be generated3·Zn (OH)2And Zn5(OH)8Cl2, their volume is more than the volume of consumed metallic zinc, is conducive to block coating hole in itself Gap makes coating surface more fine and close.In addition in corrosion process, the surface of aluminium easily generates fine and close aluminum oxide film, Neng Gouji The big redox reaction for inhibiting cathode, the reduction of cathodic partial current results in the reduction of anodic partial current, so as to inhibit zinc Dissolving and the formation of " white rust ".When flake zinc aluminium powder is transferred coating film forming in coating, metal scale is put down with substrate surface Row, multilayer arrangement, is covered mutually, forms barrier layer by layer, so as to extend the surface that corrosive medium reaches matrix carbon steel, is significantly reduced The corrosion factors such as water, oxygen in the permeability of coating, preferably shielding environment.In the solvent type zinc-aluminum paint of the present invention, zinc Al alloy powder assigns coating " electrochemical protection " and " machinery barrier " double effects, has superior metal protection performance.
Using zinc-aluminium powder mixture in traditional chromium-free zinc aluminum coating, but the density variation of Zn and Al is very big, easily causes Weight is segregated, therefore zinc powder and aluminium powder dispersion are uneven in high alumina powder content masking liquid, inevitably be there is local aluminium powder and is enriched with Phenomenon leads to part significantly poor zinc, and when corrosive medium reaches matrix, Pin Xin areas cannot provide effective anode loss protection, This can cause the Aluminum Coating premature failure of high alumina powder content.And using zinc aluminium alloy powder can to avoid use zinc, aluminium powder occur Zinc powder and aluminium powder disperse non-uniform situation, and zinc aluminium alloy powder have concurrently zinc powder cathodic protection ability and aluminium powder height it is resistance to Corrosion energy.
As a kind of preferred technical solution of the present invention, the zinc aluminium alloy powder is flakey, and grain size is 500~800 Mesh, the content of aluminium is 10wt%~30wt% in the zinc aluminium alloy powder.
The zinc aluminium alloy powder of the present invention is purchased from Scott Chemical Co., Ltd..
As a kind of preferred technical solution of the present invention, the organic solvent appointing in alcohol, ether, ketone, ester, alkane It is one or more.
The alcohol is specifiable ethyl alcohol, n-butanol, isopropanol, tert-butyl alcohol etc.；
The ether is specifiable butyl glycol ether, butanediol methyl ether etc.；
The ketone is specifiable butanone, cyclohexanone, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, methyl iso-butyl ketone (MIBK), first Base hexyl ketone etc.；
The ester is specifiable butyl acetate, ethylene glycol ether acetate, isobutyl acetate, ethyl acetate, acetic acid Monooctyl ester etc.；
The alkane includes branched paraffin, branched paraffin and cycloalkane etc., and alkane of the present invention contains 6~18 A carbon atom.
The alkane can be commercially available environment-friendlysolvent solvent oil, specifiable to have 120#Solvent naphtha, 200#Solvent naphtha, D30#It is molten Agent oil, D40#Solvent naphtha, D60#Solvent naphtha, D65#Solvent naphtha, D80#Solvent naphtha, D90#Solvent naphtha, D100#Solvent naphtha, D110#It is molten Agent oil, D130#Solvent naphtha, D160#Solvent naphtha etc..
As a kind of preferred technical solution of the present invention, the organic solvent is selected from ethyl alcohol, n-butanol, isopropanol, uncle Butanol, butanone, cyclohexanone, butyl acetate, ethylene glycol ether acetate, butyl glycol ether, butanediol methyl ether, methyl-isobutyl Ketone, isobutyl acetate, ethyl acetate, octyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl hexyl ketone, 120#Solvent Oil, 200#Solvent naphtha, D30#Solvent naphtha, D40#Solvent naphtha, D60#Solvent naphtha, D65#Solvent naphtha, D80#Solvent naphtha, D90#Solvent Oil, D100#Solvent naphtha, D110#Solvent naphtha, D130#Solvent naphtha, D160#Solvent naphtha any one or more of.
The electro-chemical activity that filler mainly enhances zinc powder in cathodic protection, reduction coating by improving coated conductive delays Corrosion rate changes coating shield protective effect to improve the whole corrosion resisting property of coating.The addition of filler can also reduce zinc-aluminium The addition of powder reduces the production cost of coating.
Filler of the present invention is limited there is no other, specifiable to have：Modified graphene, ferrotitanium powder, talcum powder, Wollastonite in powder, zinc oxide, barium sulfate, zirconium silicide, zirconium carbide, Zirconium oxide fibre, alumina silicate fibre, potassium titanate crystal whisker, aluminium borate Whisker, mullite crystal whisker, silicon carbide whisker, bentonite, high titanium ash, mica powder, kaolin, calcium carbonate, silica flour, feldspar powder, Molochite, zeolite, molecular sieve, hydrotalcite, blanc fixe, montmorillonite, aerosil and rare-earth oxide etc..
The rare-earth oxide is limited there is no other, can be La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, The oxide of the metals such as Dy, Ho, Er, Tm, Yb, Lu.
The rare-earth oxide is specifiable La2O3、Ce2O3、CeO2、Ce9O16、Ce7O12、 Ce6O11、 Ce10O8、Ce11O20、Pr6O11、PrO1.65、PrO1.714、PrO1.800、Nd2O3、Tb2O3、 Tb4O5、Tb4O7、Ho2O3、Sm2O3、 Tm2O3、Yb2O3、Y2O3、MnO2、WO3、WO2.90、 WO2.72、WO2、MoO3Deng.
As a kind of preferred technical solution of the present invention, the filler be selected from modified graphene, ferrotitanium powder, talcum powder, Wollastonite in powder, zinc oxide, barium sulfate, zirconium silicide, zirconium carbide, Zirconium oxide fibre, alumina silicate fibre, potassium titanate crystal whisker, aluminium borate Whisker, mullite crystal whisker, silicon carbide whisker, bentonite, high titanium ash, mica powder, kaolin, calcium carbonate, silica flour, feldspar powder, Molochite, zeolite, molecular sieve, hydrotalcite, blanc fixe, montmorillonite, aerosil, La2O3、Ce2O3、CeO2、 Ce9O16、Ce7O12、Ce6O11、 Ce10O8、Ce11O20、Pr6O11、PrO1.65、PrO1.714、PrO1.800、Nd2O3、Tb2O3、Tb4O5、 Tb4O7、Ho2O3、Sm2O3、Tm2O3、Yb2O3、Y2O3、MnO2、WO3、WO2.90、WO2.72、 WO2、MoO3Any one or more of.
As a kind of preferred technical solution of the present invention, the filler be selected from modified graphene, ferrotitanium powder, hydrotalcite, Bentonite, wollastonite in powder, zinc oxide, La2O3、Ce2O3、CeO2、Ce9O16、Ce7O12、Ce6O11、 Ce10O8、Ce11O20、Pr6O11、 PrO1.65、PrO1.714、PrO1.800、Nd2O3、Tb2O3、Tb4O5、 Tb4O7、Ho2O3、Sm2O3、Tm2O3、Yb2O3、Y2O3、MnO2、 WO3、WO2.90、WO2.72、 WO2、MoO3Any one or more of.
As a kind of preferred technical solution of the present invention, the filler is modified graphene, talcum powder, zinc oxide, water The mixture of talcum, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2~0.5：1~3：3~4：0.3 ~0.7.
As a kind of preferred technical solution of the present invention, the filler is modified graphene, talcum powder, zinc oxide, water The mixture of talcum, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.3：2： 3：0.5.
As a kind of preferred technical solution of the present invention, the modified graphene is furane resins modified graphene.
As a kind of preferred technical solution of the present invention, the preparation method of the modified graphene, including at least following Step：
A. graphite powder is taken to add in dissolved with K2S2O8And P2O580 DEG C of 18mol/L sulfuric acid solution in, graphite powder, K2S2O8、 P2O5Mass ratio with sulfuric acid is 2：1：1：5, stirring, cooled to room temperature is diluted with deionized water, is filtered, in being washed to Property, product dries in air；Above-mentioned product is added in the 18mol/L sulfuric acid of ice bath, be gradually added during stirring KMnO4, graphite powder, sulfuric acid and KMnO4Mass ratio be 1： 36：3, reaction temperature is controlled within 15 DEG C；Then by mixture It is transferred in 35 DEG C of water-baths, is gradually added deionized water, the quality of deionized water is 45 times of graphite powder quality, is stirred to react 2h；Then the hydrogen peroxide for adding in deionized water and 30wt% terminates reaction, the hydrogen peroxide of graphite powder, deionized water and 30wt% Mass ratio is 1：140：3, with the salt acid elution of 3.7wt% removing metal ion after filtering, centrifuge, 50 DEG C of dry 12h are obtained Obtain product a；
B. product a is taken to be dissolved in furfuryl alcohol, the mass ratio of product a and furfuryl alcohol is 1：75,3~8h of ultrasound；Then acetic acid is added in, The acetic acid and the mass ratio of furfuryl alcohol are 0.4：1, stir 0.5~1.5h；Add in the matter of furil, the furil and furfuryl alcohol Amount is than being 1：0.8, react 4h at 100~110 DEG C；Stop heating, allow mixture natural cooling, add in ethylenediamine adjust pH to 7, vacuum dehydration makes the water content of product be down to 2% hereinafter, be cooled to 30 DEG C, obtains the modified graphene.
Graphite powder, CAS：7782-42-5, purchased from Sinopharm Chemical Reagent Co., Ltd..
Furfuryl alcohol, CAS：98-00-0, purchased from Sinopharm Chemical Reagent Co., Ltd..
Furil, CAS：492-94-4, purchased from AlfaAesar (Alfa Aesar).
Talcum powder
Talcum powder is a kind of aqueous magnesium silicate mineral, is formed as 3MgO4SiO2·H2O.In the crystalline substance of superfine talcum powder During lattice is made, oxygen-octahedron is connected to layer structure, between layers with faint hydrogen bond is attracting and easily parallel off, while it Also there is higher draw ratio.At present, superfine talcum powder has been widely used in the industries such as coating, papermaking, plastics and cosmetics.
Talcum powder can assign the excellent brush of coating, levelability, gloss retention, and the coating containing talcum powder has preferable Impact resistance and flexibility, and hardness is higher, while talcum powder can also effectively improve the corrosion resistance of coating.The sheet knot of talcum powder Structure can both be effectively improved the levelability of coating, fill the gap between zinc aluminium alloy powder, reduce holiday, improve coating Shielding, and can effectively extend the diffusion path of corrosive medium, so as to improve the corrosion resistance of coating.Meanwhile talcum powder is because of it It can assign coating higher impact resistance and fracture toughness with higher draw ratio.
The talcum powder of the present invention is the superfine talcum powder of 1250 mesh, purchased from Shanghai Yuan Jiang Chemical Co., Ltd.s.
Zinc oxide
Zinc oxide grain size is small, large specific surface area, there is stronger adhesive force and covering power, and zinc oxide is added in coating can be big Big the effect of improving coating；And it is small to aoxidize zinc weight proportion, is not easy to form precipitation in use or in final products；In addition zinc oxide Also there are certain shielding ultraviolet rays, anti-aging effect can be played in coating.There are some researches prove add suitable oxygen The corrosion resistance coating of zinc-aluminum paint acquisition can be improved by changing zinc.Zinc oxide improves the corrosion proof mechanism of action：On the one hand, there is p The zinc of type semiconductor property and as n-type semiconductor zinc oxide contact after will be likely formed a kind of p-n junction, it allow electron stream Cross, and can control corrosion rate electrochemical reaction well, provide better cathodic protection for matrix；On the other hand, zinc oxide is micro- Grain can fill the hole of coating, improve shielding properties.
The zinc oxide of the present invention is purchased from Shanghai Yuan Jiang Chemical Co., Ltd.s, model coating pigment grade.
Hydrotalcite
Hydrotalcite is a kind of layered inorganic material with broad prospect of application, and ideal chemical composition is Mg6Al2 (OH)16CO3·4H2O, CAS：11097-59-9, structure are similar to shepardite Mg (OH)2.Hydrotalcite system hexagonal crystal system, by Mg2+、 Al3+、OH-The unit laminate of composition carries positive charge, therefore there are tradable anion CO for interlayer3 2-With balancing charge, make knot It is brilliant whole in electroneutral；It, can be at a proper temperature since binding force is small simultaneously there is also the hydrone of certain amount between laminate The structure removed without destroying hydrotalcite.Cationic difference and interlayer anion is differently formed variety classes on laminate Hydrotalcite.Structures shape as hydrotalcite it mainly there is alkalinity, interlayer anion exchangeability and thermal stability.
The hydrotalcite of the present invention is purchased from Kang Gaote plastics Science and Technology Ltd. of Jingjiang City, model FM300.
Coupling agent
The coating matter obtained using solvent type zinc-aluminum paint is crisp, and flexibility is poor, to improve its workability, generally requires Coupling agent is added in, the addition of coupling agent can enhance the flexibility of film forming agent ethyl orthosilicate alkyl side chain, can obtain more Complete coating, and then enhance the corrosion resisting property of Aluminum Coating.Coupling agent also known as accelerating agent is cohered, be a kind of existing in the molecule Group physically or chemically can be played with inorganic material, and have the chemical combination that can play group physically or chemically with polymer Object.Since it can work simultaneously with inorganic matter and polymer, therefore can be in inorganic material and the interface of high molecular synthetic material On set up " molecular bridge ", them is made closely to combine, achievees the purpose that enhancing, so referred to as coupling agent.
Coupling agent of the present invention is limited there is no other, it is specifiable have silane coupling agent, titanate coupling agent, Zirconium ester coupling agent, aluminate coupling agent, rare-earth salts coupling agent etc..
It is specifiable to have amino silicane coupling agent, epoxy silane coupling, hydrosulphonyl silane idol as silane coupling agent Join agent, vinyl silicane coupling agent etc..
It is specifiable to have gamma-aminopropyl-triethoxy-silane, three ethoxy of N- phenylaminomethyls as amino silicane coupling agent Base silane, (3- trimethoxy silicon propyl) diethyl ethylenediamine, anilinomethyl trimethoxy silane etc..
It is specifiable to have γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-contracting as epoxy silane coupling Water glycerine ether oxygen propyl triethoxysilane, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- (isobutene acyl-oxygen) Propyl trimethoxy silicane etc..
It is specifiable to have γ-mercaptopropyl trimethoxysilane, γ-mercapto hydroxypropyl methyl diformazan as mercaptosilane coupling agents Oxysilane, double-(γ-triethoxysilylpropyl)-tetrasulfide etc..
It is specifiable to have 3- (isobutene acyl-oxygen) propyl trimethoxy silicane, vinyl as vinyl silicane coupling agent Three (2- methoxy ethoxies) silane, vinyltrimethoxysilanes etc..
The titanate coupling agent is limited there is no other, specifiable to have (the dioctylphyrophosphoric acid acyl of isopropyl three Oxygroup) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyl Oxygroup) titanate esters, three iso stearate isopropyl titanates, Di(dioctylpyrophosphato) ethylene titanate, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters etc..
The zirconium ester coupling agent refers to four n-propyl zirconates, CAS：23519-77-9.
The aluminate coupling agent is limited there is no other, specifiable to have SG-AI821 (distearyl acyl-oxygen isopropyls Base Aluminate), DL-411, DL-411AF, DL-411D, DL-411DF, anti-settling Aluminate ASA etc..
The rare-earth salts coupling agent includes the chemical salt of the metallic element in addition to chromium in III B-, VII B races.
The chemical salt of metallic element in III B-, the VII B races in addition to chromium is limited there is no other, specifiable to have The chemical salt of the metals such as Sc, Ti, V, Mn, Y, Zr, Nb, Mo, Tc, Lu, Hf, Ta, W, Re, La, Ce, Pr.
As a kind of preferred technical solution of the present invention, the coupling agent be selected from silane coupling agent, titanate coupling agent, Zirconium ester coupling agent, aluminate coupling agent, rare-earth salts coupling agent any one or more of.
As a kind of preferred technical solution of the present invention, the coupling agent be selected from silane coupling agent, titanate coupling agent, Zirconium ester coupling agent, aluminate coupling agent any one or more of.
As a kind of preferred technical solution of the present invention, the coupling agent be selected from gamma-aminopropyl-triethoxy-silane, N- phenylaminomethyls triethoxysilane, (3- trimethoxy silicon propyl) diethyl ethylenediamine, anilinomethyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidoxypropyltrietandysilane andysilane, β-(3,4- epoxide rings Hexyl) ethyl trimethoxy silane, 3- (isobutene acyl-oxygen) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, γ-mercapto hydroxypropyl methyl dimethoxysilane, double-(γ-triethoxysilylpropyl)-tetrasulfide, 3- (isobutene acyl-oxygen) propyl Trimethoxy silane, vinyl three (2- methoxy ethoxies) silane, vinyltrimethoxysilane, three (dioctyl of isopropyl Pyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, (two is pungent for two oleic acid acyloxy of isopropyl Base phosphoric acid acyloxy) titanate esters, three iso stearate isopropyl titanates, Di(dioctylpyrophosphato) ethylene titanate, four In isopropyl two (dioctyl phosphito acyloxy) titanate esters, four n-propyl zirconates, distearyl acyl-oxygen isopropyl Aluminate It is any one or more.
As a kind of preferred technical solution of the present invention, the coupling agent is selected from gamma-aminopropyl-triethoxy-silane, N- In phenylaminomethyl triethoxysilane, (3- trimethoxy silicon propyl) diethyl ethylenediamine, anilinomethyl trimethoxy silane It is any one or more.
Anti-settling auxiliary agent
Solvent type zinc-aluminum paint settles when constructing in order to prevent, improves its storage characteristics, needs to add in dust-proof auxiliary agent.This The anti-settling auxiliary agent of invention is specifiable to be had：Organobentonite, isocyanate-terminated super branched polyurethane, organic clay, gas phase two Silica and MoS2, graphite powder, talcum powder.
As a kind of preferred technical solution of the present invention, the anti-settling auxiliary agent is MoS2With isocyanate-terminated over-expense Change the mixture of polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 5~9：1.
MoS2
MoS2, molybdenum disulfide, English name molybdenum disulfide, CAS：1317-33-5, molybdenite it is main Ingredient.Black solid powder, there is metallic luster.Chemical formula MoS2,1185 DEG C of fusing point, density 4.80g/cm3 (14 DEG C), Mohs is hard Degree 1.0~1.5.Molybdenum disulfide is important kollag, especially suitable under high temperature and pressure.It also has diamagnetism, can use Make linear photoconductor conductor and show the semiconductor of p-type or N-type conductivity energy, there is rectification and transducing.Molybdenum disulfide is also It can be used as the catalyst of complicated dehydrogenation of hydrocarbons.It is also known as " advanced solid oil king ".
Molybdenum disulfide be by natural molybdenum concntrate powder change molecular structure after chemical purification and made of solid powder.This product The black slightly band silver gray of color, has metallic luster, that touches has a soapy feeling, not soluble in water.Product has good dispersion, inadherent excellent Point can be added in various greases, form inadherent colloidal state absolutely, can increase the lubricity and extreme pressure property of grease.Also it fits For high temperature, high pressure, the machine work state of high rotating speed high load capacity, extend equipment life.Molybdenum disulfide is used for friction material master Antifriction when to want function be low temperature, when high temperature, which increases, rubs, and loss on ignition is small, volatile in friction material.The pH value of molybdenum disulfide for 7~ 8, show slightly alkalinity.It is covered in the surface of friction material, can protect other materials, prevents them from being aoxidized, especially makes other Material is not easily to fall off, attaches power enhancing.
As a kind of preferred technical solution of the present invention, the preparation side of the isocyanate-terminated super branched polyurethane Method includes at least following steps：
A. isophorone diisocyanate and glycerine are dissolved separately in dimethyl sulfoxide solvent, obtain isophorone two Isocyanate solution and glycerite；
B. at 80 DEG C, under nitrogen protection atmosphere, isophorone diisocyanate solution is added to glycerite by side stirring In, wherein the molar ratio of isocyanate group and hydroxyl is 2：1；After the completion of isophorone diisocyanate solution adds in, reaction system Insulation reaction 12h；Then protective agent caprolactam, the reaction was continued at 100 DEG C 10h are added in into reaction system；
C. after reaction, after being evaporated under reduced pressure out solvent, obtained material is dissolved through tetrahydrofuran, in methyl alcohol sedimentation and After filtering, by it in 100 DEG C of vacuum drying 15h, isocyanate-terminated super branched polyurethane is obtained.
As a kind of preferred technical solution of the present invention, the preparation method of the teos hydrolysis liquid includes at least Following steps：
Distilled water is added in the mixed solution of n-butanol, propylene glycol monomethyl ether, ethyl acetate, wherein distilled water, just Butanol, propylene glycol monomethyl ether, ethyl acetate mass ratio be 1：0.37：0.1：0.32,15~30min of stirring make its mixing equal It is even；The mass ratio of addition ethyl orthosilicate, the ethyl orthosilicate and distilled water is 1：0.8, it is warming up to 40~60 under stirring ℃；The mixed acid solution of hydrochloric acid, acetic acid is added dropwise thereto, 40~60min drops finish, the mass fraction of hydrochloric acid in mixed acid solution It is 0.5%, the mass fraction of acetic acid is 0.5%, and the mass ratio of hydrochloric acid and ethyl orthosilicate is 0.1~0.2：1；At 60~70 DEG C 2h is stirred to react, filtering and discharging is to obtain the teos hydrolysis liquid.
Ethyl orthosilicate, CAS：78-10-4, ethyl orthosilicate of the invention are purchased from the limited public affairs of Chinese medicines group chemical reagent The ethyl orthosilicate -28 of department.
As a kind of preferred technical solution of the present invention, other auxiliary agents, institute are further included in the solvent type zinc-aluminum paint The auxiliary agent stated is selected from any one of pigment, wetting dispersing agent, toughener, thickener, leveling auxiliary agent, kollag or more Kind.
As a kind of preferred technical solution of the present invention, the pigment be selected from iron oxide red, iron oxide yellow, phthalocyanine blue, Any one of titanium dioxide, chrome yellow, ultramarine, chrome oxide green.
As a kind of preferred technical solution of the present invention, the wetting dispersing agent includes the high score of the affinity groups containing pigment Son amount block copolymer solution, low molecular weight unsaturation polycarboxylic acid polymers' addition polymerization silicone copolymers solution one kind or Its mixture.
Toughener can further improve the flexible power and adhesive force of coating, and improve the shock resistance of coating, this hair The bright toughener includes but not limited to polyvinyl butyral.The polyvinyl butyral of the present invention is wide purchased from Tianjin Icy mountain peak new material Co., Ltd, specification 8s.
As a kind of preferred technical solution of the present invention, the thickener is cellulose ethers thickener.
The kollag is specifiable MoS2, graphite powder, talcum powder, ptfe emulsion etc..
The second aspect of the invention provides the preparation method of the solvent type zinc-aluminum paint, which is characterized in that extremely Include the following steps less：
A. according to parts by weight, zinc aluminium alloy powder, organic solvent, filler, coupling agent, anti-settling agent, stirring are added in a reservoir 0.5~1h obtains component A after dispersion mixing is uniform；
B. component A and component B that step a is obtained proportionally are mixed, stirs 0.5~1h, obtained described molten Dosage form zinc-aluminum paint.
The third aspect of the present invention provides application of the solvent type zinc-aluminum paint in protecting metallic surface field.
Metal of the present invention is limited there is no other, specifiable to have steel, iron, alloy, sintering metal and spy Different surface treatment etc..
After the solvent type zinc-aluminum paint of the present invention is coated in metal surface, nature placement 12h, which may be selected, makes its curing；Also may be used To make its curing by baking, the metal of the solvent type zinc-aluminum paint is coated with respectively at 90~120 DEG C, 220~250 DEG C At a temperature of carry out preliminary drying 10min and curing 25min, then natural cooling makes masking liquid form a film on piece.The purpose of preliminary drying is to make painting Solvent volatilization in liquid, the volatilization point for setting the solvent arrived according to used in formulation for coating material of temperature is reference；If baking Temperature is too low, and the evaporation rate of the solvent in masking liquid is slow, may result in the sagging and uneven thickness of masking liquid, influences outside coating It sees；If baking temperature is excessively high, the evaporation rate of solvent in coating can be made too fast and gap occur, influence coating performance.
The solvent type zinc-aluminum paint of the present invention can be applied to the every field of daily life, specifiable to have：Automobile, motor The more high-grade parts product such as the parts of vehicle, daily household electrical appliance, electronic product, Communication Equipment, subway, tunnel The hardware of the metalworks such as track, screw, bolt, highway baffle, viaduct, bridge etc., ultra-high-tension power transmission line Steel tower, the cross-arm of electric pole, iron brace clamp, elbow, bolt, steel cap, the fuel tank on transformer, fastener etc., screw, nut, pad The surfacecti proteon of the hardware tools such as circle.
In addition to this, solvent type zinc-aluminum paint of the invention apply also for municipal works, mechanical motor, railroad wharf, Shipbuilding shiprepair, building decoration, space flight and aviation, ocean engineering, geological drilling, petrochemical industry, agricultural science and technology, bioengineering, medical treatment The industries such as instrument.
The present invention uses MoS2With isocyanate-terminated super branched polyurethane as anti-settling agent, enhance the stabilization of coating Property, and can be sufficiently mixed each component, avoid phenomena such as coating aggregation is agglomerating, dispersion is uneven.It is main in dissaving polymer It is branched moiety, branch point is relatively more, and molecule has the spheroidal cramped construction of class, and the hydrodynamics radius of gyration is small, strand It tangles few, so the increase of relative molecular mass is smaller to viscosity influence.Add in isocyanate-terminated super branched polyurethane Solvent type zinc-aluminum paint solid content is high, viscosity is low, is suitble to brush and spray, and hyperbranched macromolecular has superior resistance to purple Outer performance extends the service life of coating.In organic solvent, isocyanate-terminated super branched polyurethane can well divide It dissipates, the corrosion product that terminal isocyanate base can not completely not remove with substrate surface reacts, and generates hard solidify coating And displace water.Isocyanate-terminated super branched polyurethane can also be crosslinked with butyl silicate and coupling agent, be formed Fine and close cross-linked network enhances the corrosion resistance of coating.Isocyanate-terminated super branched polyurethane includes many branches, The impact resistance and flexibility of coating can be effectively improved, and also can further extend the road that corrosive medium reaches substrate surface Diameter enhances Corrosion Protection.
The filler of the present invention employs a variety of compounded mixs compounding, the advantages of making full use of various different fillers, improves and applies The corrosion resisting property of the rheology of material, bin stability and coating, and also help and reduce cost.The furane resins of the present invention Modified graphene can effectively enhance the toughness of coating, and during component A and component B is mixed, and furane resins are modified stone Black alkene, isocyanate-terminated super branched polyurethane, coupling agent can be sent out with ethyl orthosilicate into crosslinking, participate in solidification process, The compactness of coating is further improved, enhances the mechanical barriering effect of coating.Moreover, isocyanate-terminated hyperbranched poly Urethane, furane resins modified graphene and other fillers, coupling agent can accelerate the curing of ethyl orthosilicate, various ingredients Compounding enables the solvent type zinc-aluminum paint of the invention rapid curing under conditions of low temperature and low humidity degree, expands the painting of solvent type zinc-aluminium The use scope of material.Furane resins modified graphene and other fillers have good electronic conduction ability, reduce coating Conductivity, improve the cathodic protection ability of coating.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
It is if raw materials used to be all commercially available in addition, without other explanations.
Embodiment 1：
Embodiment 1 provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4：1 mixing composition； By weight, the component A includes：75 parts of zinc aluminium alloy powders, 15 parts of organic solvents, 3 parts of fillers, 0.2 part of coupling agent, 0.3 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2It is sealed with isocyanate group Hold the mixture of super branched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 5：1.
The zinc aluminium alloy powder is flakey, and grain size is 500~800 mesh, the content of aluminium in the zinc aluminium alloy powder For 10wt%；The organic solvent is n-butanol；The filler is modified graphene, talcum powder, zinc oxide, hydrotalcite Mixture, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2：3：1：3：0.3；The coupling agent is Gamma-aminopropyl-triethoxy-silane.
The preparation method of the isocyanate-terminated super branched polyurethane includes at least following steps：
A. isophorone diisocyanate and glycerine are dissolved separately in dimethyl sulfoxide solvent, obtain isophorone two Isocyanate solution and glycerite；
B. at 80 DEG C, under nitrogen protection atmosphere, isophorone diisocyanate solution is added to glycerite by side stirring In, wherein the molar ratio of isocyanate group and hydroxyl is 2：1；After the completion of isophorone diisocyanate solution adds in, reaction system Insulation reaction 12h；Then protective agent caprolactam, the reaction was continued at 100 DEG C 10h are added in into reaction system；
C. after reaction, after being evaporated under reduced pressure out solvent, obtained material is dissolved through tetrahydrofuran, in methyl alcohol sedimentation and After filtering, by it in 100 DEG C of vacuum drying 15h, isocyanate-terminated super branched polyurethane is obtained.
Isophorone diisocyanate, CAS：4098-71-9 is purchased from Shanghai Mike's woods biochemical technology Co., Ltd.
The preparation method of the teos hydrolysis liquid, including at least following steps：
Distilled water is added in the mixed solution of n-butanol, propylene glycol monomethyl ether, ethyl acetate, wherein distilled water, just Butanol, propylene glycol monomethyl ether, ethyl acetate mass ratio be 1：0.37：0.1：0.32, stirring 25min is uniformly mixed it；Add Enter ethyl orthosilicate, the mass ratio of the ethyl orthosilicate and distilled water is 1：0.8,50 DEG C are warming up under stirring；Thereto The mixed acid solution of hydrochloric acid, acetic acid is added dropwise, 55min drops finish, and the mass fraction of hydrochloric acid is 0.5% in mixed acid solution, acetic acid Mass fraction is 0.5%, and the mass ratio of hydrochloric acid and ethyl orthosilicate is 0.16：1；2h is stirred to react at 65 DEG C, filtering and discharging is Obtain the teos hydrolysis liquid.
Ethyl orthosilicate, CAS：78-10-4, ethyl orthosilicate of the invention are purchased from the limited public affairs of Chinese medicines group chemical reagent The ethyl orthosilicate -28 of department.
The preparation method of the solvent type zinc-aluminum paint, including at least following steps：
A. according to parts by weight, zinc aluminium alloy powder, organic solvent, filler, coupling agent, anti-settling agent, stirring are added in a reservoir 1h obtains component A after dispersion mixing is uniform；
B. component A and component B that step a is obtained proportionally are mixed, stirs 0.5h, obtain the solvent type Zinc-aluminum paint.
Embodiment 2：
Embodiment 2 provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 5：1 mixing composition； By weight, the component A includes：90 parts of zinc aluminium alloy powders, 18 parts of organic solvents, 12 parts of fillers, 0.7 part of coupling agent, 0.9 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2It is sealed with isocyanate group Hold the mixture of super branched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 5：1.
The zinc aluminium alloy powder is flakey, and grain size is 500~800 mesh, the content of aluminium in the zinc aluminium alloy powder For 30wt%.The organic solvent is n-butanol；The filler is modified graphene, talcum powder, zinc oxide, hydrotalcite Mixture, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2：3：1：3：0.3；The coupling agent is Gamma-aminopropyl-triethoxy-silane.
The preparation method is the same as that of Example 1 for the isocyanate-terminated super branched polyurethane.
The preparation method is the same as that of Example 1 for the teos hydrolysis liquid.
The preparation method is the same as that of Example 1 for the solvent type zinc-aluminum paint.
Embodiment 3：
Embodiment 3 provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4.8：1 mixing group Into；By weight, the component A includes：86 parts of zinc aluminium alloy powders, 16 parts of organic solvents, 8 parts of fillers, 0.6 part of coupling Agent, 0.5 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2And isocyanate group The mixture of terminated hyperbranched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 5：1.
The zinc aluminium alloy powder is flakey, and grain size is 500~800 mesh, the content of aluminium in the zinc aluminium alloy powder For 30wt%.The organic solvent is n-butanol；The filler is modified graphene, talcum powder, zinc oxide, hydrotalcite Mixture, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2：3：1：3：0.3；The coupling agent is Gamma-aminopropyl-triethoxy-silane.
The preparation method is the same as that of Example 1 for the isocyanate-terminated super branched polyurethane.
The preparation method is the same as that of Example 1 for the teos hydrolysis liquid.
The preparation method is the same as that of Example 1 for the solvent type zinc-aluminum paint.
Embodiment 4：
Embodiment 4 provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4.8：1 mixing group Into；By weight, the component A includes：86 parts of zinc aluminium alloy powders, 16 parts of organic solvents, 8 parts of fillers, 0.6 part of coupling Agent, 0.5 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2And isocyanate group The mixture of terminated hyperbranched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 9：1.
The zinc aluminium alloy powder is flakey, and grain size is 500~800 mesh, the content of aluminium in the zinc aluminium alloy powder For 30wt%.The organic solvent is ethylene glycol ether acetate；The filler is modified graphene, talcum powder, oxidation The mixture of zinc, hydrotalcite, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2：3：1：3：0.3；It is described Coupling agent be gamma-aminopropyl-triethoxy-silane.
The preparation method is the same as that of Example 1 for the isocyanate-terminated super branched polyurethane.
The preparation method is the same as that of Example 1 for the teos hydrolysis liquid.
The preparation method is the same as that of Example 1 for the solvent type zinc-aluminum paint.
Embodiment 5：
Embodiment 5 provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4.8：1 mixing group Into；By weight, the component A includes：86 parts of zinc aluminium alloy powders, 16 parts of organic solvents, 8 parts of fillers, 0.6 part of coupling Agent, 0.5 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2And isocyanate group The mixture of terminated hyperbranched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 8：1.
The zinc aluminium alloy powder is flakey, and grain size is 500~800 mesh, the content of aluminium in the zinc aluminium alloy powder For 30wt%.The organic solvent is ethylene glycol ether acetate；The filler is modified graphene, talcum powder, oxidation The mixture of zinc, hydrotalcite, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2：3：1：3：0.3；It is described Coupling agent be gamma-aminopropyl-triethoxy-silane.
The preparation method is the same as that of Example 1 for the isocyanate-terminated super branched polyurethane.
The preparation method is the same as that of Example 1 for the teos hydrolysis liquid.
The preparation method is the same as that of Example 1 for the solvent type zinc-aluminum paint.
Embodiment 6：
Embodiment 6 provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4.8：1 mixing group Into；By weight, the component A includes：86 parts of zinc aluminium alloy powders, 16 parts of organic solvents, 8 parts of fillers, 0.6 part of coupling Agent, 0.5 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2And isocyanate group The mixture of terminated hyperbranched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 8：1.
The zinc aluminium alloy powder is flakey, and grain size is 500~800 mesh, the content of aluminium in the zinc aluminium alloy powder For 30wt%.The organic solvent is ethylene glycol ether acetate；The filler is modified graphene, talcum powder, oxidation The mixture of zinc, hydrotalcite, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.5：3：4：0.7；Described Coupling agent is gamma-aminopropyl-triethoxy-silane.
The preparation method is the same as that of Example 1 for the isocyanate-terminated super branched polyurethane.
The preparation method is the same as that of Example 1 for the teos hydrolysis liquid.
The preparation method is the same as that of Example 1 for the solvent type zinc-aluminum paint.
The modified graphene is furane resins modified graphene.
The preparation method of the modified graphene, including at least following steps：
A. graphite powder is taken to add in dissolved with K2S2O8And P2O580 DEG C of 18mol/L sulfuric acid solution in, graphite powder, K2S2O8、 P2O5Mass ratio with sulfuric acid is 2：1：1：5, cooled to room temperature is stirred, is diluted with deionized water, filters, is washed to neutrality, Product dries in air；Above-mentioned product is added in the 18mol/L sulfuric acid of ice bath, be gradually added during stirring KMnO4, graphite powder, sulfuric acid and KMnO4Mass ratio be 1： 36：3, reaction temperature is controlled within 15 DEG C；Then by mixture It is transferred in 35 DEG C of water-baths, is gradually added deionized water, the quality of deionized water is 45 times of graphite powder quality, is stirred to react 2h；Then the hydrogen peroxide for adding in deionized water and 30wt% terminates reaction, the hydrogen peroxide of graphite powder, deionized water and 30wt% Mass ratio is 1：140：3, with the salt acid elution of 3.7wt% removing metal ion after filtering, centrifuge, 50 DEG C of dry 12h are obtained Obtain product a；
B. product a is taken to be dissolved in furfuryl alcohol, the mass ratio of product a and furfuryl alcohol is 1：75, ultrasonic 6h；Then acetic acid is added in, institute The acetic acid and the mass ratio of furfuryl alcohol stated are 0.4：1, stir 1.2h；Furil is added in, the mass ratio of the furil and furfuryl alcohol is 1：0.45, react 4h at 106 DEG C；Stop heating, allow mixture natural cooling, add in ethylenediamine and adjust pH to 7, vacuum dehydration The water content of product is made to be down to 2% hereinafter, be cooled to 30 DEG C, obtains the modified graphene.
Embodiment 7：
Embodiment 7 provides a kind of solvent type zinc-aluminum paint, by component A and component B according to mass ratio 4.8：1 mixing group Into；By weight, the component A includes：86 parts of zinc aluminium alloy powders, 16 parts of organic solvents, 8 parts of fillers, 0.6 part of coupling Agent, 0.5 portion of anti-settling agent；The component B is teos hydrolysis liquid；The anti-settling auxiliary agent is MoS2And isocyanate group The mixture of terminated hyperbranched polyurethane, the MoS2Mass ratio with isocyanate-terminated super branched polyurethane is 8：1.
The zinc aluminium alloy powder is flakey, and grain size is 500~800 mesh, the content of aluminium in the zinc aluminium alloy powder For 30wt%.The organic solvent is ethylene glycol ether acetate；The filler is modified graphene, talcum powder, oxidation The mixture of zinc, hydrotalcite, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.3：4：2：3：0.5；It is described Coupling agent be gamma-aminopropyl-triethoxy-silane.
The preparation method is the same as that of Example 1 for the isocyanate-terminated super branched polyurethane.
The preparation method is the same as that of Example 1 for the teos hydrolysis liquid.
The preparation method is the same as that of Example 1 for the solvent type zinc-aluminum paint.
The modified graphene is furane resins modified graphene.
The preparation method of the modified graphene is the same as embodiment 6.
Embodiment 8：
The specific embodiment of embodiment 8 is with embodiment 7, and the difference lies in the solvent type zinc-aluminum paint also Include the toughener of 0.6 parts by weight, the toughener is polyvinyl butyral.The polyvinyl butyral of the present invention is purchased from The wide icy mountain peak new material Co., Ltd in Tianjin, specification 8s.
Comparative example 1：
The specific embodiment of comparative example 1 is with embodiment 8, and the difference lies in the anti-settling auxiliary agent is MoS2。
Comparative example 2：
The specific embodiment of comparative example 2 is with embodiment 8, and the difference lies in the anti-settling auxiliary agent is isocyanates The terminated hyperbranched polyurethane of base.
Comparative example 3：
The specific embodiment of comparative example 3 is with embodiment 8, and the difference lies in the anti-settling auxiliary agent is MoS2With it is different The mixture of the terminated hyperbranched polyurethane of cyanic acid ester group, the MoS2With the quality of isocyanate-terminated super branched polyurethane Than being 3：1.
Comparative example 4：
For the specific embodiment of comparative example 4 with embodiment 8, the difference lies in will be described isocyanate-terminated super Branched polyurethanes such as are changed at mole of the isophorone diisocyanate of quality and the mixture of glycerine, isocyanate group and hydroxyl Than being 2：1.
Comparative example 5：
For the specific embodiment of comparative example 5 with embodiment 8, the difference lies in do not include modified stone in the filler Black alkene.
Comparative example 6：
For the specific embodiment of comparative example 6 with embodiment 8, the difference lies in be changed to the modified graphene Graphene, i.e., the preparation method of described modified graphene do not include step b.
Comparative example 7：
For the specific embodiment of comparative example 7 with embodiment 8, the difference lies in be changed to the modified graphene Graphite powder, furfuryl alcohol, furil mixture, the graphite powder, furfuryl alcohol, furil mass ratio synthesized with modified graphene Metering is than identical used in journey.
Performance evaluation：
Experiment sample used is tinplate, and size is 40mm × 40mm × 3mm.By coating be coated in specimen surface it Before pre-treatment is carried out to sample to remove the grease of specimen surface, floating rust and oxide.This experiment uses non-phosphor degreaser first Oil removing cleaning solution (manufacture of Shanghai Yao Yan Chemical Companies) removes the grease of specimen surface, is then removed and tried using shot-peening method The floating rust and oxide on sample surface.
This experiment carries out aerial spraying, air pressure using PE2090 types air compressor and PQ-2 type spray guns： 0.6MPa；Distance of the spray gun rifle mouth away from sample is 30cm or so.
Hardening time
The sample sprayed is put into damp heat box and is cured, damp heat box parameter：15 DEG C, relative humidity 40%.According to state Family's standard《GBT201728-1979 paint films/putty membrane drying time measuring method》Record using Examples 1 to 8 and comparative example 1~ The surface drying time for the coating that solvent type zinc-aluminum paint described in 7 obtains and do solid work the time.
To applying after being completely dried with the coating of the solvent type zinc-aluminum paint acquisition described in Examples 1 to 8 and comparative example 1~7 The performance of layer carries out following test.It can make its natural drying by the way that sample to be placed to more than 12h naturally；Baking can also be passed through Sample is made to cure drying, the metal for being coated with the solvent type zinc-aluminum paint carries out at a temperature of 120 DEG C, 260 DEG C respectively Preliminary drying 10min and curing 25min, then natural cooling, obtain dry coating.
Adhesive force
Coating adhesion test is carried out according to GB/T9286-1998 standards, is handed over cutting tool is vertical in length and breadth on sample Fork 5 parallel cuts of cutting, spacing 6mm with transparent glue coating cut-off part, uniformly tear adhesive tape off, check that cutting applies Damage layer situation, 0~5 grade of result of the test, 0 grade excellent, and for general service, preceding three-level is qualified.
0 grade：Cut edge is completely smooth, none lattice comes off；
1 grade：There is a little thin slice to detach in cutting infall coating, the impacted area in Hua Ge areas is not more than 5%；
2 grades：The area of notching edge or infall coating shedding is more than 5%, but no more than 15%；
3 grades：There is part to peel off along notching edge or whole sheet peels off or partial grid is peeled off by full wafer, the area of peeling More than 15%, but it is less than 35%；
4 grades：Notching edge sheet peels off or some grids partly or entirely peel off, and area is more than the 35% of Hua Ge areas, But it is less than 65%；
5 grades：There is sheet of coating shedding at the edge of scribing line and intersection, and the gross area that comes off is more than 65%.
Flexibility
Flexibility refer to colored paint, varnish coat at the standard conditions around cylinder curvature when cracking resistance or remove from ground Performance is one of the leading indicator for weighing coating property, selection to coating variety, using there is very restricted publication of international news and commentary entitled value.This experiment According to national standard《GB/T1731-93 film flexibility measuring methods》Test.Test method：With defined pole, through 90 ° around Song, the diameter of pole have 6 kinds of 1mm, 2mm, 3mm, 4mm, 5mm, 10mm etc., and the diameter of bending is smaller, then the elongation of film (flexibility) is bigger.The flexibility for generally requiring coating is 1~3mm.When measuring flexibility, can be whether there is with 4 times of amplification sem observations Phenomena such as crackle, reticulate pattern and peeling, such as without abnormal for qualification.The diameter of pole that record uses when qualified.
Corrosion resistance
Neutral salt spray test method is a kind of most wide artificial acceleration simulation salt mist environmental test method of current application range, it Suitable for examining metal and its alloy, metal cladding, organic coating layer, anode oxide film and the corrosion resistance of conversion film. Neutral salt spray test carries out in HS-101B type salt spraytest casees.
Concrete operations are according to international standard ISO3768-1976《Coat of metal-neutral salt spray test (NSS experiments)》In Regulation carry out, using NaCl aqueous solutions, a concentration of 5 ± 0.5wt%, pH value be 6.5~7.2, test temperature be 35 ± 2 DEG C, Humidity is more than 95%, and nozzle exit pressure is 0.7~1kgfcm-2, amount of fog is 1~2mL/ (80cm2·h).After the test, Sample is taken out, to reduce coming off for corrosion product, sample before cleaning, is placed on Indoor Natural and dries 0.5~1h, then with originally Water gently cleans, and to remove the remaining salt fog solution of specimen surface, then dried up immediately with hair-dryer, observes coating corrosion pattern.
Since time and experiment condition limit, the present invention is first carried out at scribing line coating sample in neutral salt spray test Reason, places into salt fog cabinet accelerated corrosion, the corrosion condition of sample is as corrosion proof evaluation criterion after 60 days.According to it is identical when The extent of corrosion difference of interior sample examines the corrosion resistance of coating fine or not.Complete non-corroding, no blistering divide for full marks 10, completely Corrosion is 0 point, other corrosion situations are chosen as 1~9 point successively.
1 performance characterization of table is tested
As can be seen from Table 1, the solvent type zinc-aluminum paint in the present invention has very excellent performance, in relatively low temperature And under humidity also can rapid draing, and coating adhesion is good, and flexibility is good, excellent corrosion resistance.
Aforementioned example is merely illustrative, for explaining some features of the method for the invention.Appended right will It asks and is intended to the range as wide as possible that requirement is contemplated that, and embodiments as presented herein is only according to all possible implementation The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that appended claim is not illustrated this hair The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims It encloses, the variation in these ranges should be also construed in the conceived case by appended claim covering.

Claims (10)

1. a kind of solvent type zinc-aluminum paint, which is characterized in that by component A and component B according to mass ratio 4：1~5：1 mixing composition； By weight, the component A includes：75~90 parts of zinc aluminium alloy powders, 15~18 parts of organic solvents, 3~12 parts of fillers, 0.2~0.7 part of coupling agent, 0.3~0.9 portion of anti-settling agent；The component B is teos hydrolysis liquid；It is described anti-settling to help Agent is MoS2With the mixture of isocyanate-terminated super branched polyurethane, the MoS2With it is isocyanate-terminated hyperbranched The mass ratio of polyurethane is 5~9：1.
2. solvent type zinc-aluminum paint as described in claim 1, which is characterized in that the organic solvent is selected from ethyl alcohol, positive fourth Alcohol, isopropanol, the tert-butyl alcohol, butanone, cyclohexanone, butyl acetate, ethylene glycol ether acetate, butyl glycol ether, butanediol methyl ether, Methyl iso-butyl ketone (MIBK), isobutyl acetate, ethyl acetate, octyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl hexyl ketone, 120#Solvent naphtha, 200#Solvent naphtha, D30#Solvent naphtha, D40#Solvent naphtha, D60#Solvent naphtha, D65#Solvent naphtha, D80#Solvent naphtha, D90#Solvent naphtha, D100#Solvent naphtha, D110#Solvent naphtha, D130#Solvent naphtha, D160#Solvent naphtha any one or more of.
3. solvent type zinc-aluminum paint as described in claim 1, which is characterized in that the filler is selected from modified graphene, iron Titanium valve, hydrotalcite, bentonite, wollastonite in powder, zinc oxide, La2O3、Ce2O3、CeO2、Ce9O16、Ce7O12、Ce6O11、Ce10O8、 Ce11O20、Pr6O11、PrO1.65、PrO1.714、PrO1.800、Nd2O3、Tb2O3、Tb4O5、Tb4O7、Ho2O3、Sm2O3、Tm2O3、Yb2O3、 Y2O3、MnO2、WO3、WO2.90、WO2.72、WO2、MoO3Any one or more of.
4. solvent type zinc-aluminum paint as claimed in claim 3, which is characterized in that the filler is modified graphene, talcum Powder, zinc oxide, hydrotalcite mixture, modified graphene, talcum powder, zinc oxide, hydrotalcite mass ratio be 0.2~0.5：1 ~3：3~4：0.3~0.7.
5. solvent type zinc-aluminum paint as claimed in claim 4, which is characterized in that the modified graphene changes for furane resins Property graphene.
6. solvent type zinc-aluminum paint as described in claim 1, which is characterized in that the coupling agent be selected from silane coupling agent, Titanate coupling agent, zirconium ester coupling agent, aluminate coupling agent any one or more of.
7. solvent type zinc-aluminum paint as claimed in claim 6, which is characterized in that the coupling agent is selected from γ-aminopropyl three Ethoxysilane, N- phenylaminomethyls triethoxysilane, (3- trimethoxy silicon propyl) diethyl ethylenediamine, anilinomethyl three Methoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidoxypropyltrietandysilane andysilane, β- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- (isobutene acyl-oxygen) propyl trimethoxy silicane, γ-mercapto propyl front three Oxysilane, γ-mercapto hydroxypropyl methyl dimethoxysilane, double-(γ-triethoxysilylpropyl)-tetrasulfide, 3- (isobutenes Acyl-oxygen) propyl trimethoxy silicane, vinyl three (2- methoxy ethoxies) silane, vinyltrimethoxysilane, isopropyl Three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, two oleic acid acyl of isopropyl Oxygroup (dioctyl phosphoric acid acyloxy) titanate esters, three iso stearate isopropyl titanates, bis- (two octyloxy pyrophosphoric acid ester groups) ethylenes Titanate esters, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters, four n-propyl zirconates, distearyl acyl-oxygen isopropyl aluminium Acid esters any one or more of.
8. solvent type zinc-aluminum paint as described in claim 1, which is characterized in that further included in the solvent type zinc-aluminum paint Other auxiliary agents, the auxiliary agent is in pigment, wetting dispersing agent, toughener, thickener, leveling auxiliary agent, kollag It is any one or more.
9. such as the preparation method of claim 1~8 any one of them solvent type zinc-aluminum paint, which is characterized in that include at least Following steps：
A. zinc aluminium alloy powder, organic solvent, filler, coupling agent, anti-settling agent are added according to parts by weight, in a reservoir, stirring 0.5~ 1h obtains component A after dispersion mixing is uniform；
B. component A and component B that step a is obtained proportionally are mixed, stirs 0.5~1h, obtain the solvent type Zinc-aluminum paint.
10. such as application of the claim 1~8 any one of them solvent type zinc-aluminum paint in protecting metallic surface field.
CN201810064748.6A 2018-01-23 2018-01-23 Solvent type zinc-aluminum coating Active CN108192403B (en)

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CN110294954A (en) * 2019-07-01 2019-10-01 洛阳市科创绿色建材研究院 A kind of preparation method of the inorganic fire-retarded packing material for PVC coating
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CN113493351A (en) * 2021-07-07 2021-10-12 邦得(浙江)新材料科技有限公司 Preparation method of metal coating on ceramic surface
CN115433483A (en) * 2022-10-14 2022-12-06 新乡学院 High-hardness chromium-free Dacromet coating, anticorrosive coating and preparation method of anticorrosive coating
CN117165156A (en) * 2023-08-29 2023-12-05 湖北彩龙涂料科技有限公司 Quick-drying alkyd paint and preparation method thereof
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CN109135575A (en) * 2018-07-03 2019-01-04 九江中船消防设备有限公司 A kind of coating and preparation method thereof for ships anticorrosion anti-pollution
CN110294954A (en) * 2019-07-01 2019-10-01 洛阳市科创绿色建材研究院 A kind of preparation method of the inorganic fire-retarded packing material for PVC coating
CN111073507B (en) * 2019-10-12 2022-03-25 广东省测试分析研究所（中国广州分析测试中心） Water-based chromium-free zinc-aluminum anticorrosive paint and preparation method thereof
CN111073507A (en) * 2019-10-12 2020-04-28 广东省测试分析研究所（中国广州分析测试中心） Water-based chromium-free zinc-aluminum anticorrosive paint and preparation method thereof
CN110776825A (en) * 2019-11-07 2020-02-11 山东蓝桥工程材料有限公司 Antirust salt-spray-resistant graphene zinc-aluminum coating for metal surface, and preparation method and application thereof
CN112323623A (en) * 2020-09-15 2021-02-05 江苏固迈新材料技术有限公司 Steel bridge deck pavement structure and pavement process thereof
CN112426046A (en) * 2020-10-29 2021-03-02 苏州加益不锈钢制品有限公司 Heat conduction new material non-stick pan with annular concave-convex texture at bottom
CN113493351A (en) * 2021-07-07 2021-10-12 邦得(浙江)新材料科技有限公司 Preparation method of metal coating on ceramic surface
CN113493351B (en) * 2021-07-07 2023-07-11 邦得(浙江)新材料科技有限公司 Preparation method of ceramic surface metal coating
NL2033262B1 (en) * 2022-10-10 2024-04-26 Gmd Metal Coating B V Method for coating a metal substrate
CN115433483A (en) * 2022-10-14 2022-12-06 新乡学院 High-hardness chromium-free Dacromet coating, anticorrosive coating and preparation method of anticorrosive coating
CN117165156A (en) * 2023-08-29 2023-12-05 湖北彩龙涂料科技有限公司 Quick-drying alkyd paint and preparation method thereof
CN117165156B (en) * 2023-08-29 2024-03-12 湖北彩龙涂料科技有限公司 Quick-drying alkyd paint and preparation method thereof

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