CN107151491A - A kind of aqueous rust suitable for corrosion steel surface shifts priming paint and preparation method thereof - Google Patents
A kind of aqueous rust suitable for corrosion steel surface shifts priming paint and preparation method thereof Download PDFInfo
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- CN107151491A CN107151491A CN201710318176.5A CN201710318176A CN107151491A CN 107151491 A CN107151491 A CN 107151491A CN 201710318176 A CN201710318176 A CN 201710318176A CN 107151491 A CN107151491 A CN 107151491A
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/08—Homopolymers or copolymers of vinylidene chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/12—1,2-Dichloroethene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- 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
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- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
Priming paint and preparation method thereof is shifted the invention discloses a kind of aqueous rust suitable for corrosion steel surface, applied to corrosion steel surface.The aqueous rust transfer priming paint is made up of vinylidene chloride acrylonitrile acrylate multi-copolymerization emulsion, phosphate modified polyacrylate aqueous dispersion, non-ionic wetting dispersing agent, anti-settling agent, pigment, filler, polyether silicone defoamer, coalescents, substrate wetting agents, OIT, polyurethane associative thickener and water.The aqueous rust transfer priming paint is one-component, self-drying type product, and its storage stability is high, turn rust excellent in efficiency, and the coating of formation possesses excellent vapour resistance and long-effective corrosion.
Description
Technical field
The present invention relates to one kind be applied to corrosion steel surface, possess rust conversion and anticorrosion properties aqueous priming paint and its
Preparation method.
Background technology
Steel is that modern society uses most metal materials.Loss caused by steel corrosion, not only shows material
The destruction being subject in terms of profile, color and luster, mechanical property, it is often more important that make its product, the credit rating reduction of engineering, essence
Degree, sensitivity are damaged, and are influenceed its use value or even are scrapped, the major accident of fatal crass can be more caused under individual cases.
The application of anticorrosive paint is the Main Means of current control steel corrosion.In order to obtain excellent protection effect, pass
System anticorrosive paint needs to carry out ground strict processing of rust removing before construction.Wherein, by hand, time-consuming for powertool cleaning, and
Oxide skin, iron rust are removed not thorough.Sandblasting or shot peening efficiency high, but product cost can be significantly improved, strong powder is brought
Dirt and noise, can't thoroughly handle the dead angle in complex job face, it is most important that steel construction can be caused to be thinned, its is reduced strong
Degree.Therefore, for be difficult to thoroughly derust product, engineering (such as：Heavy construction, bridge, complicated equipment, coal gas storage cabinet) with
And require to save manpower, man-hour, the protection occasion of cost, realize that application over rust is particularly important.
At present, domestic application over rust coating is based on the products such as solvent type epoxy, haloflex, chlorinated rubber.It is applied
A large amount of using aromatic hydrocarbons, alkanes, ketone and esters solvent during work, environment friendly is poor.Country is to waving after 2010
Limit row's policy of hair property organic matter (VOC) is progressively tightened up.Such as：In September, 2013, what State Council printed and distributed《Prevention and control of air pollution is taken action
Plan》Clearly the VOC emission requirement of the key industrys such as application is improved in proposition, studies and defines VOC Regulation Policy on Pollution Discharge Fee.2015 1
The moon 26, National Ministry of Finance combines with the State Tax Administration to have issued " notice on imposing the consumption tax to coating "." notice "
It is required that from 1 day 2 months 15 years, to coating of volatile organic compounds under Construction State (VOC) content higher than 420g/L in production, commission
Processing and import link impose the consumption tax, and the applicable tax rate is 4%.In face of increasingly serious Environmental Protection Situation, the water of application over rust
Propertyization upgrading is imperative.
The content of the invention
A kind of aqueous rust suitable for corrosion steel surface, which is provided, the present invention be directed to above-mentioned problem shifts priming paint
And preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of aqueous rust suitable for corrosion steel surface shifts priming paint, the priming paint by 10~50 mass parts inclined two chloroethene
Alkene-acrlylonitrile-acrylate multi-copolymerization emulsion, the phosphate modified polyacrylate aqueous dispersion of 10~50 mass parts, 0.1
The non-ionic wetting dispersing agent of~10 mass parts, the anti-settling agent of 0.1~5 mass parts, the pigment of 1~15 mass parts, 1~20 matter
The filler of amount part, the polyether silicone defoamer of 0.01~1 mass parts, the coalescents of 1~10 mass parts, 0.1~1 mass parts
Substrate wetting agents, the OIT of 0.1~1 mass parts, the polyurethane associative thickener of 0.3~3 mass parts and 1~30
The water composition of mass parts；
Wherein：Described vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion is to be prepared via a method which
Arrive：
(1) by the vinylidene chloride of 60~80 mass parts, the acrylonitrile of 5~10 mass parts, the acrylic acid of 2~5 mass parts,
The water of the esters of acrylic acid soft monomers of 10~20 mass parts, the mixed surfactant of 2~6 mass parts and 80~120 mass parts
Monomer pre-emulsion is made under agitation, the esters of acrylic acid soft monomer is that n-butyl acrylate or acrylic acid are different pungent
Ester；
(2) take 1/5 monomer pre-emulsion to add in the reactor of nitrogen protection first, be warming up to 55~65 DEG C；Secondly will
The azo diisobutyl amidine hydrochloric acid salt initiators of 0.3~1.2 mass parts are configured to 10% aqueous solution, take wherein 1/5 initiator
The aqueous solution is added in reactor, stirring polymerization 1h；It is afterwards that remaining monomer pre-emulsion and remaining initiator solution is same
When instill in reactor, 3~4h completion of dropping, and continue stirring reaction 1h；Finally, 70 DEG C are warming up to, 1h is incubated, cooled down, plus
Enter phosphate buffer regulation system pH value to 2.0~4.5, filtering, you can obtain vinylidene chloride-acrlylonitrile-acrylate
Multi-copolymerization emulsion；
Described phosphate modified polyacrylate aqueous dispersion is to be prepared via a method which to obtain：By 25~45 mass
Part senecioate-etherophosphoric acid, the acrylic acid of 2~5 mass parts, the methyl methacrylate of 25~40 mass parts, 15~35
The butyl acrylate of mass parts, the azodiisobutyronitrile of 0.2~1.0 mass parts, the mixed surfactant of 2~8 mass parts and
Monomer-initiator mixing pre-emulsion is made in the water of 90~130 mass parts under high velocity agitation；Take 1/4 the mixing pre-emulsification
Liquid is added in the reactor of nitrogen protection, is warming up to 65~70 DEG C, stirring polymerization 1h；Remaining mixing pre-emulsion is delayed afterwards
It is slow to instill in reactor, 3~4h completion of dropping, and continue stirring reaction 1h；Then, 80~90 DEG C are warming up to, 1h is incubated；It is cold
But, phosphate buffer regulation system pH value is added to 2.0~6.0, filtering, you can obtain phosphate modified polyacrylate water
Dispersion.
In some preferred technical schemes：The priming paint by 35~50 mass parts vinylidene chloride-acrylonitrile-acrylic acid
Ester multi-copolymerization emulsion, the phosphate modified polyacrylate aqueous dispersion of 15~35 mass parts, 0.4~1.5 mass parts it is non-
Ionic wetting dispersing agent, the anti-settling agent of 0.1~0.5 mass parts, the pigment of 2~7 mass parts, the filler of 5~20 mass parts,
The polyether silicone defoamer of 0.05~0.2 mass parts, the coalescents of 1~5 mass parts, the base material profit of 0.1~0.5 mass parts
Humectant, the OIT of 0.1~0.3 mass parts, the polyurethane associative thickener of 0.3~1.2 mass parts and 10~20 matter
Measure the water composition of part.
Described in technical solution of the present invention vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion preparation method
Mixed surfactant is Nonyl pheno base ether, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and cetyl front three
The mixture of base ammonium bromide, the mixed proportion of three is 1：1.5：1.
Blending surface described in the phosphate modified polyacrylate aqueous dispersion preparation method of technical solution of the present invention is lived
Property agent be Nonyl pheno base ether, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 1- allyloxys -3- (4- nonyl benzenes
Phenol) -2- propyl alcohol polyoxyethylene (10) ether monophosphate mixture, the mixed proportion of three is 1：1：2.
In technical solution of the present invention：The anti-settling agent is aerosil or the sea organically-modified lithiums of this BENTONE-LT of name
Montmorillonite auxiliary rheological agents；The pigment is iron oxide red, iron oxide black or carbon black；The filler be blanc fixe, sericite,
One or more in talcum powder；The coalescents are alcohol ester 12 or dipropylene；Described non-ionic wetting
Dispersant is the high Dispers 757W wetting dispersing agents of enlightening or the wetting dispersing agents of Bi Ke DISPERBYK 190；Described polyethers silicon
Oxygen alkane defoamer is the high defoamers of Foamex 810 of enlightening；The high substrate wetting agents of Wet KL 245 of described substrate wetting agents enlightening are finished
Gram BYK-345 substrate wetting agents or Bi Ke BYK-346 substrate wetting agents；Described polyurethane associative thickener be extra large name this
The thickeners of RHEOLATE 299.
A kind of aqueous rust suitable for corrosion steel surface shifts the preparation method of priming paint, and this method is the condition in stirring
Non-ionic wetting dispersing agent, 0.1~5 mass parts of 0.1~10 mass parts are sequentially added in the lower water to 10~50 mass parts
Anti-settling agent, the pigment of 1~15 mass parts, the polyether silicone froth breaking of the filler of 1~20 mass parts and 0.01~1 mass parts
Agent, dispersed with stirring is to uniformly without caking, obtaining slurry；Then, slurry fineness is ground to less than 40 μm using sand mill, in stirring
Vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion of 10~50 mass parts of addition, 10 in the lower slurry to after grinding
The phosphate modified polyacrylate aqueous dispersions of~50 mass parts, the coalescents of 1~10 mass parts, 0.1~1 mass parts
Substrate wetting agents, the OIT of 0.1~1 mass parts, the polyurethane associative thickener of 0.3~3 mass parts, are stirred to equal
It is even to obtain aqueous rust transfer priming paint without shrinkage cavity；
Wherein：Described vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion is to be prepared via a method which
Arrive：By the vinylidene chloride of 60~80 mass parts, the acrylonitrile of 5~10 mass parts, the acrylic acid of 2~5 mass parts, 10~20 matter
The esters of acrylic acid soft monomer, the water of the mass parts of mixed surfactant 80~120 of 2~6 mass parts of amount part are made under agitation
Into monomer pre-emulsion, the esters of acrylic acid soft monomer is n-butyl acrylate or Isooctyl acrylate monomer；Take 1/5 monomer pre-
Emulsion is added in the reactor of nitrogen protection, is warming up to 55~65 DEG C；By the azo diisobutyl amidine salt of 0.3~1.2 mass parts
Hydrochlorate initiator is configured to 10% aqueous solution, takes wherein 1/5 initiator solution to add in reactor, stirring polymerization 1h；It
Remaining monomer pre-emulsion and remaining initiator solution are instilled in reactor simultaneously afterwards, 3~4h completion of dropping, and after
Continuous stirring reaction 1h；Then, 70 DEG C are warming up to, 1h is incubated；Cooling, addition phosphate buffer regulation system pH value to 2.0~
4.5；Filtering, you can obtain vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion；
Described phosphate modified polyacrylate aqueous dispersion is to be prepared via a method which to obtain：By 25~45 mass
Part senecioate-etherophosphoric acid, the acrylic acid of 2~5 mass parts, the methyl methacrylate of 25~40 mass parts, 15~35
The butyl acrylate of mass parts, the azodiisobutyronitrile of 0.2~1.0 mass parts, the mixed surfactant of 2~8 mass parts and
Monomer-initiator mixing pre-emulsion is made in the water of 90~130 mass parts under high velocity agitation；Take 1/4 the pre- breast of above-mentioned mixing
Change liquid to add in the reactor of nitrogen protection, be warming up to 65~70 DEG C, stirring polymerization 1h；Afterwards by remaining mixing pre-emulsion
It is slowly dropped into reactor, 3~4h completion of dropping, and continues stirring reaction 1h；Then, 80~90 DEG C are warming up to, 1h is incubated；It is cold
But, phosphate buffer regulation system pH value is added to 2.0~6.0, filtering, you can obtain phosphate modified polyacrylate water
Dispersion.
The above-mentioned aqueous rust suitable for corrosion steel surface is shifted the preparation method of priming paint：It is formulated the mass parts of each component
It is as follows：
The vinylidene chloride of 35~50 mass parts-acrlylonitrile-acrylate multi-copolymerization emulsion, the phosphorus of 15~35 mass parts
Acid esters modified polyacrylate aqueous dispersion, the non-ionic wetting dispersing agent of 0.4~1.5 mass parts, 0.1~0.5 mass parts
Anti-settling agent, the pigment of 2~7 mass parts, the filler of 5~20 mass parts, the polyether silicone froth breaking of 0.05~0.2 mass parts
Agent, the coalescents of 1~5 mass parts, the substrate wetting agents of 0.1~0.5 mass parts, the isothiazoline of 0.1~0.3 mass parts
The water of ketone, the polyurethane associative thickener of 0.3~1.2 mass parts and 10~20 mass parts.
The above-mentioned aqueous rust suitable for corrosion steel surface is shifted the preparation method of priming paint：The anti-settling agent is gas phase two
Silica or the sea organically-modified hectorite auxiliary rheological agents of this BENTONE-LT of name；The pigment is iron oxide red, iron oxide black
Or carbon black；The filler is the one or more in blanc fixe, sericite, talcum powder；The coalescents are alcohol ester ten
Two or dipropylene；Described non-ionic wetting dispersing agent is the high Dispers 757W wetting dispersing agents of enlightening or Bi Ke
The wetting dispersing agents of DISPERBYK 190；Described polyether silicone defoamer is the high defoamers of Foamex 810 of enlightening；Described base
The high substrate wetting agents of Wet KL 245 of material wetting agent enlightening or the wetting of Bi Ke BYK-345 substrate wetting agents or Bi Ke BYK-346 base materials
Agent；Described polyurethane associative thickener is this thickener of RHEOLATE 299 of extra large name.
The above-mentioned aqueous rust suitable for corrosion steel surface is shifted the preparation method of priming paint：Vinylidene chloride-acrylonitrile-
Mixed surfactant described in acrylate multi-copolymerization emulsion is Nonyl pheno base ether, methylacryoyloxyethyl
The mixture of trimethyl ammonium chloride and cetyl trimethylammonium bromide, the mixed proportion of three is 1：1.5：1.
The above-mentioned aqueous rust suitable for corrosion steel surface is shifted the preparation method of priming paint：Phosphate modified polyacrylic acid
Mixed surfactant described in ester aqueous dispersion is Nonyl pheno base ether, methylacryoyloxyethyl trimethyl ammonia chloride
The mixture of ammonium and 1- allyloxys -3- (4- nonyl phenols) -2- propyl alcohol polyoxyethylene (10) ether monophosphate, the mixing ratio of three
Example is 1：1：2.
Aqueous rust transfer priming paint disclosed in this invention mainly realizes the stabilization of iron rust by infiltration, two modes of action of conversion
Change.First, film forming matter and macromolecular is helped to turn rust agent supplemented by the phosphate modified polyacrylate aqueous dispersion of design.Both tree is participated in
Fat film forming, can form stable metal salt with iron rust again, overcome inorganic phosphate, small molecule organic phosphoric acid free property strong, easy
The problems such as migration.Next, synthesis particle diameter is small, the vinylidene chloride-the third that permeability is strong, adhesive force is high, dry film vapour resistance is good
Alkene nitrile-acrylate multi-copolymerization emulsion is main film forming matter.Pass through itself and phosphate modified polyacrylate aqueous dispersion
Film forming, forms firm iron rust clad altogether, suppresses corrosion diffusion.3rd, whole resin system uses quasi- soap-free polymerization and sun
Ion emulsification system.While lifting resin shear stability, possess relatively low pH value, resin dechlorination decomposition can be prevented effectively from.
4th, unique double film forming matter blending systems cause product can flexibly be adjusted according to rusty scale thickness vinylidene chloride-acrylonitrile-
The portfolio ratio of acrylate multi-copolymerization emulsion and phosphate modified polyacrylate aqueous dispersion, the optimal turn rust of acquisition,
Protection effect.
Beneficial effects of the present invention：
Aqueous rust transfer priming paint storage stability height, turn rust excellent in efficiency, the adhesive force of the disclosure of the invention are good, the coating of formation
Possess excellent vapour resistance, resistance to salt water, humidity resistance and long-effective corrosion.
Embodiment
With reference to embodiment, the present invention will be further described, but protection scope of the present invention not limited to this：
Embodiment 1
(1) preparation of vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion：By inclined two chloroethene of 75 mass parts
Alkene, the acrylonitrile of 5 mass parts, the acrylic acid of 2.5 mass parts, the Isooctyl acrylate monomer of 15 mass parts, the blending surface of 4 mass parts
Activating agent (Nonyl pheno base ether, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and cetyl trimethylammonium bromide
Mixture, the mixed proportion of three is 1:1.5:1), monomer pre-emulsion is made in the water of 100 mass parts under agitation.Take 1/5
Above-mentioned mix monomer pre-emulsion add nitrogen protection reactor in, be warming up to 60 DEG C.By the isobutyl of azo two of 0.6 mass parts
Base amidine hydrochloric acid salt initiators are configured to 10% aqueous solution, take wherein 1/5 initiator solution to add in reactor, stirring polymerization
1h.Remaining mix monomer pre-emulsion and initiator solution are instilled in reactor simultaneously, 4h completion of dropping, and continue to stir
Mix reaction 1h.Then, 70 DEG C are warming up to, 1h is incubated.Cooling, adds phosphate buffer regulation system pH value to 2.0~4.5.
Filtering, you can obtain solid vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion containing for 49.8%.
(2) preparation of phosphate modified polyacrylate aqueous dispersion：By senecioate-etherophosphoric acid of 40 mass parts, 3
The acrylic acid of mass parts, the methyl methacrylate of 35 mass parts, the butyl acrylate of 10 mass parts, the azo of 0.4 mass parts
Mixed surfactant (Nonyl pheno base ether, the methylacryoyloxyethyl trimethyl chlorine of bis-isobutyronitrile, 3 mass parts
Change ammonium and the mixture of 1- allyloxys -3- (4- nonyl phenols) -2- propyl alcohol polyoxyethylene (10) ether monophosphate, the mixing of three
Ratio is 1:1:2), monomer-initiator mixing pre-emulsion is made in the water of 110 mass parts under high velocity agitation.Take 1/4 it is above-mentioned
Mix pre-emulsion to add in the reactor of nitrogen protection, be warming up to 70 DEG C, stirring polymerization 1h.By remaining mixing pre-emulsion
It is slowly dropped into reactor, 3.5h completion of dropping, and continues stirring reaction 1h.Then, 90 DEG C are warming up to, 1h is incubated.Cooling, plus
Enter phosphate buffer regulation system pH value to 2.0~6.0.Filtering, you can obtain it is solid containing for 43.5% it is phosphate modified poly-
Acrylate aqueous dispersion.
(3) preparation of aqueous rust transfer priming paint：The enlightening of 0.8 mass parts is sequentially added into the water of 11 mass parts under agitation
The aerosils of Degussa AEROSIL 200, the oxygen of 7 mass parts of high Dispers 757W wetting dispersing agents, 0.2 mass parts
Change iron oxide black pigment, the blanc fixe of 12 mass parts, the sericite of 5 mass parts, the high Foamex810 froth breakings of enlightening of 0.05 mass parts
Agent, dispersed with stirring is to uniformly without caking, obtaining slurry.Then, slurry fineness is ground to less than 40 μm using sand mill.In stirring
Lower vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion, the phosphoric acid of 15 mass parts that 45 mass parts are added into slurry
Ester modified polyacrylate aqueous dispersion, the dipropylene of 4.5 mass parts, the high bases of Wet KL 245 of enlightening of 0.2 mass parts
Material wetting agent, the OIT of 0.2 mass parts, the extra large name of 0.5 mass parts this thickener of RHEOLATE 299, are stirred until homogeneous
The solid aqueous rust transfer priming paint #1 containing for 54.2% can be obtained without shrinkage cavity.
Embodiment 2
(1) preparation of vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion：It is same as Example 1.
(2) preparation of phosphate modified polyacrylate aqueous dispersion：It is same as Example 1.
(3) preparation of aqueous rust transfer priming paint：The enlightening of 0.8 mass parts is sequentially added into the water of 11 mass parts under agitation
The aerosils of Degussa AEROSIL 200, the oxygen of 7 mass parts of high Dispers 757W wetting dispersing agents, 0.2 mass parts
Change iron oxide black pigment, the blanc fixe of 12 mass parts, the sericite of 5 mass parts, the high Foamex810 froth breakings of enlightening of 0.05 mass parts
Agent, dispersed with stirring is to uniformly without caking, obtaining slurry.Then, slurry fineness is ground to less than 40 μm using sand mill.In stirring
Lower vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion, the phosphoric acid of 30 mass parts that 30 mass parts are added into slurry
Ester modified polyacrylate aqueous dispersion, the dipropylene of 3.5 mass parts, the high bases of Wet KL 245 of enlightening of 0.2 mass parts
Material wetting agent, the OIT of 0.2 mass parts, the extra large name of 0.5 mass parts this thickener of RHEOLATE 299, are stirred until homogeneous
The solid aqueous rust transfer priming paint #2 containing for 53.9% can be obtained without shrinkage cavity.
The main performance index of aqueous rust transfer priming paint #1 (embodiment 1) and aqueous rust transfer priming paint #2 (embodiment 2) is such as
Under：
The key technical indexes of the aqueous rust transfer priming paint of table 1
Main performance index of the aqueous rust transfer priming paint of table 2 under different rusty scale thickness
[a]Test plate (panel) applies the aqueous rust transfer priming paint in 2 roads, per pass interval 24h, paint film gross thickness (50 ± 10) μm, and curing period is
7d；[b]Test plate (panel) applies the aqueous rust transfer priming paint in 2 roads and the single-component water-based acrylic acid top-coat in 1 road, per pass interval 24h, priming paint total thickness
Spend (50 ± 10) μm, finish paint gross thickness (25 ± 5) μm, curing period is 7d.Thickness is with the sandblasting steel plate that is applied under equal conditions
Film thickness is defined.
Water resistance, resistance to salt water, humidity resistance and the salt fog resistance of two aqueous rust transfer priming paint are contrasted it can be found that phosphorus
The relatively low priming paint #1 of acid esters modified polyacrylate aqueous dispersion ratio is more suitable for being protected under low rusty scale thickness.Improve phosphorus
After acid esters modified polyacrylate aqueous dispersion ratio (priming paint #2), priming paint turns rust ability and is obviously improved, under high rusty scale thickness
Guard time be obviously prolonged.As can be seen here, double film forming matter blending systems that the present invention is designed can be adjusted according to rusty scale thickness and led
The portfolio ratio of film forming matter and auxiliary film forming matter, obtains optimal turn rust, protection effect.
Embodiment 3
(1) preparation of vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion：By inclined two chloroethene of 60 mass parts
Alkene, the acrylonitrile of 8 mass parts, the acrylic acid of 3 mass parts, the n-butyl acrylate of 10 mass parts, the blending surface of 3 mass parts are lived
Property agent (Nonyl pheno base ether, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and cetyl trimethylammonium bromide
Mixture, the mixed proportion of three is 1:1.5:1), monomer pre-emulsion is made in the water of 100 mass parts under agitation.Take 1/5
Above-mentioned mix monomer pre-emulsion is added in the reactor of nitrogen protection, is warming up to 60 DEG C.By the azo diisobutyl of 0.4 mass parts
Amidine hydrochloric acid salt initiators are configured to 10% aqueous solution, take wherein 1/5 initiator solution to add in reactor, stirring polymerization
1h.Remaining mix monomer pre-emulsion and initiator solution are instilled in reactor simultaneously, 3.5h completion of dropping, and continued
Stirring reaction 1h.Then, 70 DEG C are warming up to, 1h is incubated.Cooling, addition phosphate buffer regulation system pH value to 2.0~
4.5.Filtering, you can obtain solid vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion containing for 45.5%.
(2) preparation of phosphate modified polyacrylate aqueous dispersion：By senecioate-etherophosphoric acid of 25 mass parts, 2
The acrylic acid of mass parts, the methyl methacrylate of 40 mass parts, the butyl acrylate of 20 mass parts, the azo of 0.5 mass parts
Mixed surfactant (Nonyl pheno base ether, the methylacryoyloxyethyl trimethyl chlorine of bis-isobutyronitrile, 5 mass parts
Change ammonium and the mixture of 1- allyloxys -3- (4- nonyl phenols) -2- propyl alcohol polyoxyethylene (10) ether monophosphate, the mixing of three
Ratio is 1:1:2), monomer-initiator mixing pre-emulsion is made in the water of 110 mass parts under high velocity agitation.Take 1/4 it is above-mentioned
Mix pre-emulsion to add in the reactor of nitrogen protection, be warming up to 70 DEG C, stirring polymerization 1h.By remaining mixing pre-emulsion
It is slowly dropped into reactor, 4h completion of dropping, and continues stirring reaction 1h.Then, 90 DEG C are warming up to, 1h is incubated.Cooling, is added
Phosphate buffer regulation system pH value is to 2.0~6.0.Filtering, you can obtain admittedly containing phosphate modified poly- third for 45.2%
Olefin(e) acid ester aqueous dispersion.
(3) preparation of aqueous rust transfer priming paint：Finishing for 0.3 mass parts is sequentially added into the water of 10 mass parts under agitation
Gram wetting dispersing agents of DISPERBYK 190, the extra large name of 0.4 mass parts this BENTONE LT montmorillonitic clay classes auxiliary rheological agents, 6.5
The ferric oxide red colorant of mass parts, the blanc fixe of 7 mass parts, the talcum powder of 6 mass parts, the enlightening height of 0.1 mass parts
The defoamers of Foamex 810, dispersed with stirring is to uniformly without caking.Then, slurry fineness is ground to less than 40 μm using sand mill.
Vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion, 35 mass parts of 35 mass parts are added into slurry under agitation
Phosphate modified polyacrylate aqueous dispersion, the alcohol ester 12 of 2.5 mass parts, the Bi Ke BYK-345 base materials of 0.1 mass parts
Wetting agent, the OIT of 0.2 mass parts, the extra large name of 0.8 mass parts this thickener of RHEOLATE 299, are stirred until homogeneous nothing
Shrinkage cavity can obtain the solid aqueous rust transfer priming paint containing for 49.8%.It is water resistance >=5d of the primer coating (50 ± 10 μm), resistance to
Salt >=3d, humidity resistance >=168h, salt fog resistance >=120h.
Embodiment 4
(1) preparation of vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion：By inclined two chloroethene of 65 mass parts
Alkene, the acrylonitrile of 6 mass parts, the acrylic acid of 3 mass parts, the n-butyl acrylate of 12 mass parts, the blending surface of 2.5 mass parts
Activating agent (Nonyl pheno base ether, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and cetyl trimethylammonium bromide
Mixture, the mixed proportion of three is 1:1.5:1), monomer pre-emulsion is made in the water of 100 mass parts under agitation.Take 1/5
Above-mentioned mix monomer pre-emulsion add nitrogen protection reactor in, be warming up to 60 DEG C.By the isobutyl of azo two of 0.3 mass parts
Base amidine hydrochloric acid salt initiators are configured to 10% aqueous solution, take wherein 1/5 initiator solution to add in reactor, stirring polymerization
1h.Remaining mix monomer pre-emulsion and initiator solution are instilled in reactor simultaneously, 3.5h completion of dropping, and continued
Stirring reaction 1h.Then, 70 DEG C are warming up to, 1h is incubated.Cooling, addition phosphate buffer regulation system pH value to 2.0~
4.5.Filtering, you can obtain solid vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion containing for 47.0%.
(2) preparation of phosphate modified polyacrylate aqueous dispersion：By senecioate-etherophosphoric acid of 30 mass parts,
The acrylic acid of 2.5 mass parts, the methyl methacrylate of 32 mass parts, the butyl acrylate of 26 mass parts, the idol of 0.7 mass parts
Mixed surfactant (Nonyl pheno base ether, the methylacryoyloxyethyl trimethyl of nitrogen bis-isobutyronitrile, 4 mass parts
The mixture of ammonium chloride and 1- allyloxys -3- (4- nonyl phenols) -2- propyl alcohol polyoxyethylene (10) ether monophosphate, three's is mixed
Composition and division in a proportion example is 1:1:2), monomer-initiator mixing pre-emulsion is made in the water of 110 mass parts under high velocity agitation.Take 1/4 it is upper
State mixing pre-emulsion to add in the reactor of nitrogen protection, be warming up to 70 DEG C, stirring polymerization 1h.By remaining mixing pre-emulsification
Liquid is slowly dropped into reactor, 4h completion of dropping, and continues stirring reaction 1h.Then, 90 DEG C are warming up to, 1h is incubated.Cooling, plus
Enter phosphate buffer regulation system pH value to 2.0~6.0.Filtering, you can obtain it is solid containing for 46.1% it is phosphate modified poly-
Acrylate aqueous dispersion.
(3) preparation of aqueous rust transfer priming paint：The Bi Ke of 1 mass parts is sequentially added into the water of 18 mass parts under agitation
The wetting dispersing agents of DISPERBYK 190, the aerosils of Degussa AEROSIL 200 of 0.4 mass parts, 3.5 mass parts
Carbon black pigment, the blanc fixe of 8 mass parts, the high defoamers of Foamex 810 of enlightening of 0.1 mass parts, dispersed with stirring to uniform nothing
Caking.Then, slurry fineness is ground to less than 40 μm using sand mill.Inclined the two of 48 mass parts are added into slurry under agitation
Chloride-acrylonitrile-acrylate multi-copolymerization emulsion, the phosphate modified polyacrylate aqueous dispersion of 20 mass parts, 1 matter
The dipropylene of amount part, the Bi Ke BYK-346 substrate wetting agents of 0.5 mass parts, the OIT of 0.2 mass parts, 1 matter
This thickener of RHEOLATE 299 of the extra large name of amount part, the solid aqueous rust turn containing for 43.0% can be obtained by being stirred until homogeneous no shrinkage cavity
Move priming paint.Water resistance >=7d of the primer coating (50 ± 10 μm), resistance to salt water >=4d, humidity resistance >=192h, salt fog resistance
≥120h。
Claims (10)
1. a kind of aqueous rust suitable for corrosion steel surface shifts priming paint, it is characterised in that：The priming paint is by 10~50 mass parts
Vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion, the phosphate modified polyacrylate water of 10~50 mass parts
Dispersion, the non-ionic wetting dispersing agent of 0.1~10 mass parts, the anti-settling agent of 0.1~5 mass parts, the face of 1~15 mass parts
Material, the polyether silicone defoamer of the filler of 1~20 mass parts, 0.01~1 mass parts, the coalescents of 1~10 mass parts,
The substrate wetting agents of 0.1~1 mass parts, the OIT of 0.1~1 mass parts, the polyurethane association type of 0.3~3 mass parts
Thickener and the water of 1~30 mass parts composition；
Wherein：Described vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion is to be prepared via a method which to obtain：
(1) by the vinylidene chloride of 60~80 mass parts, the acrylonitrile of 5~10 mass parts, the acrylic acid of 2~5 mass parts, 10~
The water of the esters of acrylic acid soft monomers of 20 mass parts, the mixed surfactant of 2~6 mass parts and 80~120 mass parts is being stirred
Monomer pre-emulsion is made under the conditions of mixing, the esters of acrylic acid soft monomer is n-butyl acrylate or Isooctyl acrylate monomer；
(2) take 1/5 monomer pre-emulsion to add in the reactor of nitrogen protection first, be warming up to 55~65 DEG C；Secondly by 0.3~
The azo diisobutyl amidine hydrochloric acid salt initiators of 1.2 mass parts are configured to 10% aqueous solution, take wherein 1/5 initiator solution
Add in reactor, stirring polymerization 1h；Remaining monomer pre-emulsion and remaining initiator solution are instilled simultaneously afterwards
In reactor, 3~4h completion of dropping, and continue stirring reaction 1h；Finally, 70 DEG C are warming up to, 1h is incubated, cooling adds phosphoric acid
Salt buffer regulation system pH value is filtered to 2.0~4.5, you can obtain vinylidene chloride-acrlylonitrile-acrylate polynary common
Poly- emulsion；
Described phosphate modified polyacrylate aqueous dispersion is to be prepared via a method which to obtain：By 25~45 mass parts
Senecioate-etherophosphoric acid, the acrylic acid of 2~5 mass parts, the methyl methacrylate of 25~40 mass parts, 15~35 mass
Part butyl acrylate, the azodiisobutyronitrile of 0.2~1.0 mass parts, the mixed surfactant of 2~8 mass parts and 90~
Monomer-initiator mixing pre-emulsion is made in the water of 130 mass parts under high velocity agitation；The 1/4 mixing pre-emulsion is taken to add
In the reactor for entering nitrogen protection, 65~70 DEG C, stirring polymerization 1h are warming up to；Remaining mixing pre-emulsion is slowly dripped afterwards
Enter in reactor, 3~4h completion of dropping, and continue stirring reaction 1h；Then, 80~90 DEG C are warming up to, 1h is incubated；Cooling, plus
Enter phosphate buffer regulation system pH value to 2.0~6.0, filtering, you can obtain phosphate modified polyacrylate moisture and dissipate
Body.
2. the aqueous rust according to claim 1 suitable for corrosion steel surface shifts priming paint, it is characterised in that：The priming paint
Changed by the phosphate of vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion of 35~50 mass parts, 15~35 mass parts
Property polyacrylate aqueous dispersion, the non-ionic wetting dispersing agent of 0.4~1.5 mass parts, 0.1~0.5 mass parts it is anti-settling
Agent, the pigment of 2~7 mass parts, the filler of 5~20 mass parts, the polyether silicone defoamer of 0.05~0.2 mass parts, 1~5
The coalescents of mass parts, the substrate wetting agents of 0.1~0.5 mass parts, the OIT of 0.1~0.3 mass parts, 0.3~
The polyurethane associative thickener of 1.2 mass parts and the water of 10~20 mass parts composition.
3. the aqueous rust according to claim 1 suitable for corrosion steel surface shifts priming paint, it is characterised in that：Inclined dichloro
Mixed surfactant described in ethylene-propylene nitrile-acrylate multi-copolymerization emulsion preparation method is polyoxyethylene nonyl phenyl second
The mixture of alkene ether, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and cetyl trimethylammonium bromide, the mixing of three
Ratio is 1：1.5：1.
4. the aqueous rust according to claim 1 suitable for corrosion steel surface shifts priming paint, it is characterised in that：Phosphate
Mixed surfactant described in modified polyacrylate aqueous dispersion preparation method is Nonyl pheno base ether, methyl
Acrylyl oxy-ethyl-trimethyl salmiac and 1- allyloxys -3- (4- nonyl phenols) -2- propyl alcohol polyoxyethylene (10) ether list phosphorus
The mixture of acid, the mixed proportion of three is 1：1：2.
5. the aqueous rust according to claim 1 suitable for corrosion steel surface shifts priming paint, it is characterised in that：It is described anti-
Heavy agent is aerosil or the sea organically-modified hectorite auxiliary rheological agents of this BENTONE-LT of name；The pigment is iron oxide
Red, iron oxide black or carbon black；The filler is the one or more in blanc fixe, sericite, talcum powder；The film forming is helped
Agent is alcohol ester 12 or dipropylene；Described non-ionic wetting dispersing agent is the high Dispers757W wetting and dispersings of enlightening
Agent or the wetting dispersing agents of Bi Ke DISPERBYK 190；Described polyether silicone defoamer is the high defoamers of Foamex 810 of enlightening；
The high substrate wetting agents of Wet KL 245 of described substrate wetting agents enlightening or Bi Ke BYK-345 substrate wetting agents or Bi Ke BYK-346
Substrate wetting agents；Described polyurethane associative thickener is this RHEOLATE299 thickener of extra large name.
6. a kind of aqueous rust suitable for corrosion steel surface shifts the preparation method of priming paint, it is characterised in that：This method be
Sequentially added under conditions of stirring into the water of 10~50 mass parts 0.1~10 mass parts non-ionic wetting dispersing agent, 0.1
The anti-settling agent of~5 mass parts, the pigment of 1~15 mass parts, the polyethers silicon of the filler of 1~20 mass parts and 0.01~1 mass parts
Oxygen alkane defoamer, dispersed with stirring is to uniformly without caking, obtaining slurry；Then, slurry fineness is ground to less than 40 μ using sand mill
M, the vinylidene chloride-acrlylonitrile-acrylate for adding 10~50 mass parts into the slurry after grinding under agitation is polynary common
Poly- emulsion, the phosphate modified polyacrylate aqueous dispersion of 10~50 mass parts, the coalescents of 1~10 mass parts, 0.1~
The substrate wetting agents of 1 mass parts, the OIT of 0.1~1 mass parts, the polyurethane association type thickening of 0.3~3 mass parts
Agent, aqueous rust transfer priming paint can be obtained by being stirred until homogeneous no shrinkage cavity；
Wherein：Described vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion is to be prepared via a method which to obtain：
By the vinylidene chloride of 60~80 mass parts, the acrylonitrile of 5~10 mass parts, the acrylic acid of 2~5 mass parts, 10~20 mass
The esters of acrylic acid soft monomer, the water of the mass parts of mixed surfactant 80~120 of 2~6 mass parts of part are made under agitation
Monomer pre-emulsion, the esters of acrylic acid soft monomer is n-butyl acrylate or Isooctyl acrylate monomer；Take 1/5 the pre- breast of monomer
Liquid is added in the reactor of nitrogen protection, is warming up to 55~65 DEG C；By the azo diisobutyl amidine hydrochloric acid of 0.3~1.2 mass parts
Salt initiators are configured to 10% aqueous solution, take wherein 1/5 initiator solution to add in reactor, stirring polymerization 1h；Afterwards
Remaining monomer pre-emulsion and remaining initiator solution are instilled in reactor simultaneously, 3~4h completion of dropping, and continued
Stirring reaction 1h；Then, 70 DEG C are warming up to, 1h is incubated；Cooling, addition phosphate buffer regulation system pH value to 2.0~
4.5；Filtering, you can obtain vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion；
Described phosphate modified polyacrylate aqueous dispersion is to be prepared via a method which to obtain：By 25~45 mass parts
Senecioate-etherophosphoric acid, the acrylic acid of 2~5 mass parts, the methyl methacrylate of 25~40 mass parts, 15~35 mass
Part butyl acrylate, the azodiisobutyronitrile of 0.2~1.0 mass parts, the mixed surfactant of 2~8 mass parts and 90~
Monomer-initiator mixing pre-emulsion is made in the water of 130 mass parts under high velocity agitation；Take 1/4 above-mentioned mixing pre-emulsion
In the reactor for adding nitrogen protection, 65~70 DEG C, stirring polymerization 1h are warming up to；It is afterwards that remaining mixing pre-emulsion is slow
Instill in reactor, 3~4h completion of dropping, and continue stirring reaction 1h；Then, 80~90 DEG C are warming up to, 1h is incubated；Cooling,
Phosphate buffer regulation system pH value is added to 2.0~6.0, filtering, you can obtain phosphate modified polyacrylate moisture
Granular media.
7. the aqueous rust according to claim 6 suitable for corrosion steel surface shifts the preparation method of priming paint, its feature
It is：The mass parts of each component are as follows in the priming paint：
The vinylidene chloride of 35~50 mass parts-acrlylonitrile-acrylate multi-copolymerization emulsion, the phosphate of 15~35 mass parts
Modified polyacrylate aqueous dispersion, the non-ionic wetting dispersing agent of 0.4~1.5 mass parts, 0.1~0.5 mass parts it is anti-
Heavy agent, the pigment of 2~7 mass parts, the filler of 5~20 mass parts, the polyether silicone defoamer of 0.05~0.2 mass parts, 1~
The coalescents of 5 mass parts, the substrate wetting agents of 0.1~0.5 mass parts, the OIT of 0.1~0.3 mass parts, 0.3~
The water of the polyurethane associative thickener of 1.2 mass parts and 10~20 mass parts.
8. the aqueous rust according to claim 6 suitable for corrosion steel surface shifts the preparation method of priming paint, its feature
It is：The anti-settling agent is aerosil or the sea organically-modified hectorite auxiliary rheological agents of this BENTONE-LT of name；It is described
Pigment is iron oxide red, iron oxide black or carbon black；The filler is one kind or several in blanc fixe, sericite, talcum powder
Kind；The coalescents are alcohol ester 12 or dipropylene；Described non-ionic wetting dispersing agent is the high Dispers of enlightening
757W wetting dispersing agents or the wetting dispersing agents of Bi Ke DISPERBYK 190；Described polyether silicone defoamer is that enlightening is high
The defoamers of Foamex 810；The high substrate wetting agents of Wet KL 245 of described substrate wetting agents enlightening or Bi Ke BYK-345 base materials profit
Humectant or Bi Ke BYK-346 substrate wetting agents；For extra large name, this RHEOLATE 299 is thickened described polyurethane associative thickener
Agent.
9. the aqueous rust according to claim 6 suitable for corrosion steel surface shifts the preparation method of priming paint, its feature
It is：Mixed surfactant described in vinylidene chloride-acrlylonitrile-acrylate multi-copolymerization emulsion is polyoxyethylene nonyl phenyl second
The mixture of alkene ether, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and cetyl trimethylammonium bromide, the mixing of three
Ratio is 1：1.5：1.
10. the aqueous rust according to claim 6 suitable for corrosion steel surface shifts the preparation method of priming paint, its feature
It is：Mixed surfactant described in phosphate modified polyacrylate aqueous dispersion is Nonyl pheno base ether, first
Base acrylyl oxy-ethyl-trimethyl salmiac and 1- allyloxys -3- (4- nonyl phenols) -2- propyl alcohol polyoxyethylene (10) ether list
The mixture of phosphoric acid, the mixed proportion of three is 1：1：2.
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| WO2019119645A1 (en) * | 2017-12-22 | 2019-06-27 | 江苏怡成屏障科技有限公司 | Eco-friendly low-carbon automatic rust conversion coating and preparation method thereof |
| CN115477874A (en) * | 2022-10-14 | 2022-12-16 | 北京汇聚和新材料有限公司 | Water-based antirust primer and preparation method thereof |
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Inventor after: Chen Zhaocong Inventor after: Zhang Weizhong Inventor before: Chen Zhaocong |
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