CN109651917A - A kind of polystyrene microsphere modified acroleic acid aqueous industrial coating - Google Patents
A kind of polystyrene microsphere modified acroleic acid aqueous industrial coating Download PDFInfo
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- CN109651917A CN109651917A CN201811523197.1A CN201811523197A CN109651917A CN 109651917 A CN109651917 A CN 109651917A CN 201811523197 A CN201811523197 A CN 201811523197A CN 109651917 A CN109651917 A CN 109651917A
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- polystyrene
- modified acroleic
- polystyrene microsphere
- acroleic acid
- nano
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
Abstract
The present invention relates to a kind of polystyrene microsphere modified acroleic acid aqueous industrial coatings, are made of polystyrene microsphere modified acroleic acid water-base resin, cosolvent, ground modifying agent, nano-functional material, pigments and fillers, auxiliary agent and water；Wherein, the nano-functional material is Nano-meter SiO_22, nano-ZnO, nano-TiO2, nanometer Al2O3, nano SnO2, nm-class boron nitride, potassium titanate crystal whisker, carbon nanotube or graphene；The polystyrene microsphere modified acroleic acid water-base resin, as function monomer, is then synthesized by ATRP Raolical polymerizable by allyl polystyrene microsphere；Polystyrene microsphere modified acroleic acid aqueous industrial coating produced by the present invention has excellent adhesive force, water resistance, corrosion resistance, wearability, humidity resistance, salt fog resistance, resistance to ag(e)ing, anti-flash rusting, resistance to rust and corrosion and crack resistance.
Description
Technical field
The present invention relates to a kind of acrylic resin modified water paint more particularly to a kind of polystyrene microspheres modified third
Olefin(e) acid aqueous industrial coating belongs to aqueous functional coatings technical field.
Background technique
Coating is that daily production takes good care of infrastructure indispensable material, is widely used in building, all kinds of hardware
The fields such as part, the decoration of industrial product and machinery, vehicle, ship, aircraft, instrument.Acrylic resin paint has raw material valence
The advantages that lattice are cheap, good to pigment wettability, and there is good application property, play important angle always in paint field
Color.But contains a large amount of organic solvents in traditional acrylic resin paint, human body and ecological environment are caused to seriously affect.
With the enhancing of people's environmental protection consciousness, the production and application of environment-friendly aqueous coating have been general trend of events institutes
Become.Compared with solvent based coating, or seldom volatile organic matter (VOC) is not contained in water paint.It is with safety collar
It protects, is at low cost, the multiple advantage such as flexible of constructing.Water-based acrylic resin coating, takes water as a solvent, and is widely used in each
Field.
That there are anticorrosion time limits is short for water-borne acrylic coatings at present, and easy flash rusting after coating, acidproof weatherability is poor, hardness and stabilization
The problems such as property is poor.Acrylate paint belongs to organic substance simultaneously, and it is inflammable to meet fire after film forming, produces thick smoke and a large amount of nuisances
The generation of matter affects its application range, thus it is carried out anti-flammability modification be very important.
Summary of the invention
Current functional polystyrene microsphere refer to microsphere surface contain functional group for example carboxyl, amino, aldehyde radical, ketone group,
Ester group, sulfonic group, chloromethyl, halogen, acid chloride group, sulfuryl chlorio etc., to give microballoon more new functions.
The present invention uses polystyrene microsphere modified acroleic acid water-base resin, which is by being modified containing allyl
Polystyrene microsphere, then by ATRP Raolical polymerizable, draws as function monomer on acrylic resin molecular structure
Enter polystyrene microsphere structural unit, hardness, drawing crack, temperature tolerance, wearability, water resistance and the corrosion resistant of coating can be effectively improved
Corrosion.
The present invention provides a kind of polystyrene microsphere modified acroleic acid aqueous industrial coating.
In order to solve the problems, such as that techniques as described above, the present invention take following technical scheme: the present invention relates to a kind of polyphenyl
The microsphere modified acrylic acid aqueous industrial coating of ethylene, by weight percentage, component are as follows: polystyrene microsphere modified acroleic acid
Water-base resin 35.0~75.0%, cosolvent 1.0~8.0%, substrate wetting agents 0.2~2.0%, nano-functional material 0~
15.0%, pigments and fillers 0~35.0%, auxiliary agent 0.5~10.0%, deionized water to 100%.
Wherein, the polystyrene microsphere modified acroleic acid water-base resin is synthesized using ATRP technology, in application
It is recorded in patent of invention " a kind of polystyrene microsphere modified acroleic acid water-base resin and preparation method thereof "；Its preparation step is such as
Under:
Initiator is dissolved in deionized water, 5%~10% initiator solution is configured to；By formulation weight ratio, according to
It is secondary to be added to allyl polystyrene microsphere, catalyst, soft monomer, hard monomer, emulsifier, ligand, remaining deionized water
In reactor, leads to nitrogen and replace 0.5~1h, then 15~30min of high-speed stirred is warming up to 60~110 DEG C to after emulsifying uniformly,
Initiator solution is added dropwise, is added dropwise in 0.5~1h, keeps the reaction was continued 6~12h under constant temperature, obtains the polyphenyl second
The microsphere modified acrylic acid aqueous resin of alkene；
According to parts by weight, each material composition are as follows: 6.0~15.0 parts of allyl polystyrene microsphere, soft monomer 20.0~
40.0 parts, 5.0~12.0 parts of hard monomer, 0.2~2.5 part of emulsifier, 0.5~1.5 part of ligand, 0.6~2.0 part of catalyst, draw
Send out 0.4~1.5 part of agent, 50.0~80.0 parts of deionized water.
The allyl polystyrene microsphere is allyl amine polystyrene crosslinked microsphere, amide allyl base polystyrene
Crosslinked microsphere or sulfonamide allyl base polystyrene crosslinked microsphere.
The allyl amine polystyrene crosslinked microsphere, passes through chloromethyl by polystyrene-divinylbenzene crosslinked microsphere
Change reaction, then react and be made with allyl amine, in a kind of patent " polystyrene crosslinked microsphere allyl of polymerizable reaction of application
It is had been described in base amine and preparation method thereof ".
The amide allyl base polystyrene crosslinked microsphere, it is molten in inertia by carboxylated polystyrene crosslinked microsphere
After being sufficiently swollen in agent, is reacted with thionyl chloride generate acyl chlorides ball in the presence of a catalyst, then reacted and be made with allyl amine,
It is had been described in the patent " a kind of amide allyl base polystyrene crosslinked microsphere and preparation method thereof " of application.
The sulfonamide allyl base polystyrene crosslinked microsphere, passes through chlorine by polystyrene-divinylbenzene crosslinked microsphere
The direct chlorosulfonation of sulfonic acid prepares sulfonic acid chloride, then reacts and be made with allyl amine, in a kind of patent " sulfonamide allyl of application
It is had been described in polystyrene crosslinked microsphere and preparation method thereof ".
The soft monomer is methyl acrylate, ethyl acrylate, n-propyl, n-butyl acrylate, acrylic acid
Isobutyl ester, tert-butyl acrylate, Isooctyl acrylate monomer, n-BMA, Isobutyl methacrylate, methacrylic acid
At least one of the tert-butyl ester, lauryl acrylate, lauryl methacrylate, isooctyl methacrylate.
The hard monomer is styrene, methyl methacrylate, ethyl methacrylate, isobornyl methacrylate
At least one of.
The emulsifier is lauryl sodium sulfate, neopelex, potassium oleate, enuatrol, succinate
Sodium sulfonate, stearine, glyceryl oleate, ethoxylated dodecyl alcohol, lauric acid polyoxyethylene ester, double detergent alkylates
At least one of base ether sodium disulfonate, sodium laurate, OP-10, phenethyl phenol polyethenoxy ether, tween.
The ligand is N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N ', N "-pentamethyl methyl acrylate base two
Vinyl triamine, N, N, N ', N ', N ", N "-hexamethyl n-butyl acrylate base triethylene tetraamine, 2,2 '-bipyridyls, N, N,
N ', N ', N "-pentamethyldivinyltriamine, N, N, N ', N ', N ", in N "-hexamethyl methyl acrylate base triethylene tetraamine
At least one.
The catalyst is at least one of cuprous bromide, stannous chloride, copper bromide.
The initiator is 4- [2- (the bromo- 2- methylpropionyloxy of 2-) ethyoxyl] -4- oxo -2- sulfonic group butyric acid two
Sodium, 4- [10- (the bromo- 2- methylpropionyloxy of 2-) decyloxy] -4- oxo -2- sulfonic group butyric acid disodium, 4- [6- (the bromo- 2- first of 2-
Base propionyloxy) hexyloxy] -4- oxo -2- sulfonic group butyric acid disodium, 4- [10- (the bromo- 2- methylpropionyloxy of 2-) pungent oxygen
Base] -4- oxo -2- sulfonic group butyric acid disodium, 2- chlorine propionamide, 2- bromine propionamide, 2- iodo methyl acrylate, 2- chloro third
Nitrile, 2- bromopropene acetoacetic ester, 2- bromopropene acid methyl esters, propylene bromide acetoacetic ester, 1- bromoacetonitrile, 2- methyl -2- bromo propylene
Acetoacetic ester, 2- isobutyl ethyl bromide, 2- bromopropene acetoacetic ester, N, at least one of N- diethyl -2- bromo acrylamide.
The cosolvent is at least one of alcohols solvent, alcohol ethers solvent.
The substrate wetting agents are fatty alcohol polyoxyethylene ether, silicone-polyether copolymer, organo-fluorine polymer, acetylenic glycols
At least one of copolyether, silane coupling agent.
The auxiliary agent include at least dispersing agent, wetting agent, defoaming agent, levelling agent, hand feeling agent, delustering agent, anti-settling rheological agent,
At least two or more in anti-flash rusting agent, pH adjusting agent.
The nano-functional material is Nano-meter SiO_22, nano-ZnO, nano-TiO2, nanometer Al2O3, nano SnO2, nano silicon nitride
At least one of boron, potassium titanate crystal whisker, carbon nanotube, graphene.
The pigments and fillers be trbasic zinc phosphate, zinc molybdate, iron oxide red, aluminium triphosphate, titanium-iron powder, ferrophosphorus powder, graphite powder, partially
One or more of barium borate, talcum powder, Cab-O-sil, mica powder, kaolin, bentonite, borax, flake asbestos, aqueous color paste
Combination.
A kind of polystyrene microsphere modified acroleic acid aqueous industrial coating produced by the present invention, have excellent adhesive force,
Water resistance, corrosion resistance, wearability, humidity resistance, salt fog resistance, resistance to ag(e)ing, anti-flash rusting, resistance to rust and corrosion and cracking resistance
Property.
Specific embodiment
The present invention is with the following Examples described further polystyrene microsphere modified acroleic acid aqueous industrial coating.
It is understood that specific embodiment described herein is used only for explaining related invention, rather than the restriction to the invention.
Embodiment 1
A kind of polystyrene microsphere modified acroleic acid aqueous industrial coating, by weight, consisting of: polystyrene is micro-
65.0 parts of ball modified acroleic acid water-base resin, 3.0 parts of propylene glycol, 2.5 parts of dipropylene, 0.5 part of dispersing agent, siloxanes are poly-
0.3 part of ether copolymer, Nano-meter SiO_223.0 parts, 0.3 part of silane levelling agent, 0.2 part of defoaming agent, thickening 0.5 part of anti-settling agent, pH tune
Save 0.2 part of agent, 24.5 parts of deionized water；
Wherein, the polystyrene microsphere modified acroleic acid water-base resin is a kind of patent of invention " polystyrene microsphere
Embodiment 4 in modified acroleic acid water-base resin and preparation method thereof ".
Embodiment 2
A kind of acids radiation shielding coating of polystyrene microsphere modified propylene, by weight, consisting of: polystyrene
35.0 parts of microsphere modified acrylic acid aqueous resin, 3.0 parts of dipropylene glycol methyl ether, 1.5 parts of dispersing agent, 12.0 parts of potassium titanate crystal whisker,
3.0 parts of nm-class boron nitride, 18.0 parts of mica powder, 12.0 parts of talcum powder, 0.1 part of silane levelling agent, disappears at 1.0 parts of silane coupling agent
0.2 part of infusion, 0.5 part of anti-settling agent, 0.1 part of pH adjusting agent, 13.6 parts of deionized water；
Wherein, the polystyrene microsphere modified acroleic acid water-base resin is that " a kind of polystyrene microsphere changes patent of invention
Embodiment 5 in acrylic acid aqueous resin of property and preparation method thereof ".
Embodiment 3
A kind of polystyrene microsphere modified acroleic acid aqueous rust-proof coatings, by weight, consisting of: polystyrene is micro-
40.0 parts of ball modified acroleic acid water-base resin, 3.0 parts of propylene glycol monobutyl ether, 6.0 parts of barium sulfate, 12.0 parts of talcum powder, trbasic zinc phosphate
12.0 parts, 6.0 parts of titanium dioxide, 4.0 parts of barium metaborate, 0.3 part of levelling agent, 1.5 parts of dispersing agent, 0.2 part of wetting agent, defoaming agent
0.2 part, 1.0 parts of anti-flash rusting agent, 0.5 part of anti-settling agent, 0.1 part of pH adjusting agent, 13.2 parts of deionized water；
Wherein, the polystyrene microsphere modified acroleic acid water-base resin is that " a kind of polystyrene microsphere changes patent of invention
Embodiment 6 in acrylic acid aqueous resin of property and preparation method thereof ".
Embodiment 4
A kind of acids engineering coating of polystyrene microsphere modified propylene, by weight, consisting of: polystyrene is micro-
0.5 part, 30% nanometer 60.0 parts of ball modified acroleic acid water-base resin, 3.0 parts of dipropylene, dispersing agent Al2O3Dispersion
3.0 parts, 10.0 parts of 70% titanium dioxide slurry, 0.2 part of substrate wetting agents, 0.1 part of pH adjusting agent, 8.0 parts of yellow mill base, anti-flash rusting agent
1.0 parts, 0.2 part of defoaming agent, 0.3 part of anti-settling agent, 0.2 part of levelling agent, 13.5 parts of deionized water；
Wherein, the polystyrene microsphere modified acroleic acid water-base resin is that " a kind of polystyrene microsphere changes patent of invention
Embodiment 4 in acrylic acid aqueous resin of property and preparation method thereof ".
The embodiment of the present invention is detected according to relevant criterion, the performance indicator of detection is as shown in table 1.
Table 1: polystyrene microsphere modified acroleic acid aqueous industrial coating performance technologies index
Although the present invention has described it in detail and cited embodiments, but for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (10)
1. a kind of polystyrene microsphere modified acroleic acid aqueous industrial coating, it is characterised in that: the polystyrene microsphere changes
The acrylic acid aqueous industrial coating of property, by weight percentage, component are as follows: polystyrene microsphere modified acroleic acid water-base resin
35.0~75.0%, cosolvent 1.0~8.0%, substrate wetting agents 0.2~2.0%, nano-functional material 0~15.0%, face are filled out
Expect 0~35.0%, auxiliary agent 0.5~10.0%, deionized water to 100%；
Wherein, the polystyrene microsphere modified acroleic acid water-base resin is synthesized using ATRP technology, and preparation step is as follows:
First initiator is dissolved in deionized water, is configured to 5%~10% initiator solution；It is successively that allyl base polystyrene is micro-
Ball, catalyst, soft monomer, hard monomer, emulsifier, ligand, remaining deionized water are added in reactor, lead to N2Displacement 0.5
~1h, then 15~30min of high-speed stirred is warming up to 60~110 DEG C to after emulsifying uniformly, initiator solution is added dropwise, 0.5
It is added dropwise in~1h, keeps the reaction was continued 6~12h under constant temperature, obtain the polystyrene microsphere modified acroleic acid water-base resin；
According to parts by weight, each material composition are as follows:
The allyl polystyrene microsphere is allyl amine polystyrene crosslinked microsphere, the crosslinking of amide allyl base polystyrene
Microballoon or sulfonamide allyl base polystyrene crosslinked microsphere；
The allyl amine polystyrene crosslinked microsphere, it is anti-by chloromethylation by polystyrene-divinylbenzene crosslinked microsphere
It answers, then reacts and be made with allyl amine；
The amide allyl base polystyrene crosslinked microsphere, by carboxylated polystyrene crosslinked microsphere in atent solvent
Sufficiently after swelling, is reacted with thionyl chloride generate acyl chlorides ball in the presence of a catalyst, then reacted and be made with allyl amine；
The sulfonamide allyl base polystyrene crosslinked microsphere, passes through chlorosulfonic acid by polystyrene-divinylbenzene crosslinked microsphere
Direct chlorosulfonation prepares sulfonic acid chloride, then reacts and be made with allyl amine.
2. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Nano-functional material is Nano-meter SiO_22, nano-ZnO, nano-TiO2, nanometer Al2O3, nano SnO2, nm-class boron nitride, potassium titanate it is brilliant
At least one of palpus, carbon nanotube, graphene.
3. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described to help
Solvent is at least one of alcohols solvent, alcohol ethers solvent.
4. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Substrate wetting agents be fatty alcohol polyoxyethylene ether, silicone-polyether copolymer, organo-fluorine polymer, acetylenic glycols copolyether,
At least one of silane coupling agent.
5. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Pigments and fillers are trbasic zinc phosphate, zinc molybdate, iron oxide red, aluminium triphosphate, titanium-iron powder, ferrophosphorus powder, graphite powder, barium metaborate, talcum
The combination of one or more of powder, Cab-O-sil, mica powder, kaolin, bentonite, borax, flake asbestos, aqueous color paste.
6. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Auxiliary agent includes at least dispersing agent, wetting agent, defoaming agent, levelling agent, hand feeling agent, delustering agent, anti-settling rheological agent, anti-flash rusting agent, pH
At least two or more in regulator.
7. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Soft monomer is methyl acrylate, ethyl acrylate, n-propyl, n-butyl acrylate, isobutyl acrylate, acrylic acid uncle
Butyl ester, Isooctyl acrylate monomer, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, the acrylic acid moon
At least one of osmanthus ester, lauryl methacrylate, isooctyl methacrylate；The hard monomer is styrene, methyl
At least one of methyl acrylate, ethyl methacrylate, isobornyl methacrylate.
8. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Ligand is N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N ', N "-pentamethyl methyl acrylate base diethylene triamine, N, N,
N ', N ', N ", N "-hexamethyl n-butyl acrylate base triethylene tetraamine, 2,2 '-bipyridyls, N, N, N ', N ', N "-pentamethyl
Diethylene triamine, N, N, N ', N ', N ", at least one of N "-hexamethyl methyl acrylate base triethylene tetraamine；It is described
Catalyst be at least one of cuprous bromide, stannous chloride, copper bromide.
9. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Initiator is 4- [2- (the bromo- 2- methylpropionyloxy of 2-) ethyoxyl] -4- oxo -2- sulfonic group butyric acid disodium, 4- [10- (2-
Bromo- 2- methylpropionyloxy) decyloxy] -4- oxo -2- sulfonic group butyric acid disodium, 4- [6- (the bromo- 2- methylpropionyloxy of 2-)
Hexyloxy] -4- oxo -2- sulfonic group butyric acid disodium, 4- [10- (the bromo- 2- methylpropionyloxy of 2-) octyloxy] -4- oxo -2-
Sulfonic group butyric acid disodium, 2- chlorine propionamide, 2- bromine propionamide, 2- iodo methyl acrylate, 2- chloro propionitrile, 2- bromopropene acid second
Ester, 2- bromopropene acid methyl esters, propylene bromide acetoacetic ester, 1- bromoacetonitrile, 2- methyl -2- bromoacrylic acid ethyl ester, 2- bromo are different
Ethyl butyrate, 2- bromopropene acetoacetic ester, N, at least one of N- diethyl -2- bromo acrylamide.
10. polystyrene microsphere modified acroleic acid aqueous industrial coating according to claim 1, it is characterised in that: described
Emulsifier be lauryl sodium sulfate, neopelex, potassium oleate, enuatrol or Disodium sulfosuccinate, glycerol
Stearate, glyceryl oleate, ethoxylated dodecyl alcohol, lauric acid polyoxyethylene ester, double dodecylphenyl ether disulfonic acid
At least one of sodium, sodium laurate, OP-10, phenethyl phenol polyethenoxy ether, tween.
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| CN201811523197.1A CN109651917B (en) | 2018-12-12 | 2018-12-12 | Polystyrene microsphere modified acrylic acid water-based industrial coating |
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Cited By (1)
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| CN112029359A (en) * | 2020-09-17 | 2020-12-04 | 扬州大学 | Filling type water-based acrylic resin composite coating and application thereof as anticorrosive coating on surface of metal material |
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| CN112029359A (en) * | 2020-09-17 | 2020-12-04 | 扬州大学 | Filling type water-based acrylic resin composite coating and application thereof as anticorrosive coating on surface of metal material |
| CN112029359B (en) * | 2020-09-17 | 2021-11-30 | 扬州大学 | Filling type water-based acrylic resin composite coating and application thereof as anticorrosive coating on surface of metal material |
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| CN109651917B (en) | 2020-11-17 |
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Denomination of invention: A Polystyrene Microspheres Modified Acrylic Waterborne Industrial Coating Effective date of registration: 20230607 Granted publication date: 20201117 Pledgee: Agricultural Bank of China Limited Shaoguan Wujiang Sub branch Pledgor: SHAOGUAN UNION CHEMICAL Co.,Ltd.|UNION (FOSHAN) CHEMICAL Co.,Ltd. Registration number: Y2023980043074 |
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