CN105670480B - Zn-ni alloy deposits and zinc coat nano modification sealer and its preparation, application method - Google Patents
Zn-ni alloy deposits and zinc coat nano modification sealer and its preparation, application method Download PDFInfo
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- CN105670480B CN105670480B CN201610196448.4A CN201610196448A CN105670480B CN 105670480 B CN105670480 B CN 105670480B CN 201610196448 A CN201610196448 A CN 201610196448A CN 105670480 B CN105670480 B CN 105670480B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses zn-ni alloy deposits and zinc coat nano modification sealer and its preparation, application method, sealer includes following components：Soluble polyurethane, soluble silane polymer, nanometer polytetrafluoroethylcomposite lotion, nano silicon dioxide sol, wetting agent, accelerating agent, deionized water；Wetting agent compounds for one or both of polyether-modified alkyl copolymer or 2 ethylhexylsulfate sodium salts, and the accelerating agent compounds for one or both of ethylene glycol or 1,3 propane diols；The self lubricity of the sealer of present invention nanometer polytetrafluoroethylcomposite increase confining bed, with the hardness of nano silicon dioxide increase confining bed, hence it is evident that improve the greasy property and wear-resisting property of admiro and zinc coating.
Description
Technical field
The present invention relates to field of electroplating, the composition and application and preparation skill of admiro and zinc coating sealer are particularly related to
Art.
Background technology
Have been obtained for being widely applied as coating for protection against corrosion with admiro and zinc coating, in order to improve the corrosion resistant of coating
Corrosion energy, often also needs to after coating Passivation Treatment carry out Seal treatment, could meet the technical requirements of manufacturing industry high-end product.
The traditional sealer of admiro and zinc coating mainly has two kinds, and a kind of is with as polyvinyl alcohol crosslinked sodium metasilicate is a kind of
Colloid is the sealer of film forming matter, and another kind is the sealer using paraffin wax emulsions and water-soluble resin as film forming matter.Poly- second
The close membrane brittleness that this kind of material of enol crosslinking sodium metasilicate is formed is big and lubricity is low, and film layer is easily damaged；Paraffin wax emulsions and water
Closing film hardness that soluble resin is formed is low, wears no resistance, and in transport and is easy to be scratched in and scratches.
Authorization Notice No. is " 101514457 B of CN " Chinese invention patent《Multi-purpose metal surface protectant and its system
Preparation Method》Disclose a kind of metal or coating sealer, the sealer by organic inhibitor, film forming matter, surfactant and
Organic solvent forms.This product cost is higher, and organic solvent volatilization pollution working environment in use, receives its application
Limitation.
Authorization Notice No. is the Chinese invention patent of " 103147104 B of CN "《Corrosion-resistant coating sealer》Disclose one
Coating sealer is planted, contains following material in the sealer：Allantoin, dimethyl silicone polymer, Polyquaternium-10, third
Olefin(e) acid polymer, methyl propylhomoserin proline, methylisothiazolinone, surplus are water.This sealer is gathered using soluble silane
Compound and water soluble organic substance resin make film forming matter, are the methods for researching and developing coating sealer prevalence at this stage.With it is traditional
Admiro and zinc coating sealer are similar, and the confining bed that this sealer is formed is lacked there is also lubricity and wearability are low
Fall into.
Application publication number is " the Chinese invention patent application file of CN104059498 A "《Water-based coating sealer and its
Preparation method and purposes and hot-dip metal plated material》In disclose a kind of water-based coating sealer, sealer includes following component：
Water, silane coupling agent, water-soluble silicate, accelerating agent, cilicon oxide filler, water-soluble film-forming resin (including water-soluble polyester into
Film resin, water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, soluble polyurethane film-forming resin, water-soluble silicon third
At least one of film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin), when preparation, mixes successively
Close uniform.The technical solution application silane coupling agent, the silane coupling agent hydrolysis generation silane polymer in process for preparation, due to
The polymer is not sufficiently stable in the capping reagent, can further aggregate into net structure, increases the viscosity of sealer, sealing performance
Decline；In addition, cilicon oxide filler can be nano-silica powder and/or nano silicon dioxide sol, aoxidized in cilicon oxide filler
The particle diameter of silicon can be 5~90nm, more preferably 5~30nm, and during the too small especially less than 10nm of the particle diameter of Ludox, it is to film forming
The resistance slided between material molecule reduces, and is unfavorable for improving the hardness and strength of film layer.
Nanometer technology is to be subject to national governments to pay attention to extensively, the cutting edge technology that input huge fund organizational strength is competitively studied.Receive
Rice corpuscles is due to special natures such as skin effect, small-size effect, quantum size effect, macroscopic quantum effects, on surface
Have been obtained for being widely applied in many fields such as processing, nanometer technology has the performance for improving material huge
Potentiality.
The content of the invention
The present invention proposes a kind of zn-ni alloy deposits and zinc coat nano modification sealer, by adding in the capping reagent
Nanometer polytetrafluoroethylcomposite and nanometer silicon dioxide material, nano particle is uniformly filled in three dimensional network during close membrane is formed
Surface and its inside in shape film layer, can be effectively increased the hardness and self lubricity of film layer, solve current admiro and
The problem of zinc coating confining bed greasy property and low wear-resisting property.
The technical proposal of the invention is realized in this way：Zn-ni alloy deposits and zinc coat nano modification sealer, by matter
Measure percentages, including following each component：
Preferably, the film forming matter includes soluble polyurethane and soluble silane polymer, soluble polyurethane account for
The mass fraction of film forming matter is 80%, and soluble silane polymer accounts for the mass fraction 20% of film forming matter.
The soluble silane polymer trade name is PU 113, this Dutch tal fibre Products, are silane coupled
Agent, by the silane polymer of hydrolysis generation, has higher stability under certain process conditions.
Preferably, the lubricant uses nanometer polytetrafluoroethylcomposite lotion, and wherein resin content is 50%, particle diameter for 20~
90nm, lotion pH >=7.5.
Preferably, the coalescents use nano silicon dioxide sol, and dioxide-containing silica is 25%~30%, pH=
8~10, appearance is micro- blue-tinted transparent to milky white liquid；The particle size range of Ludox is 10~120nm, when size is small to be micro-
Blue-tinted transparent liquid, has intermediate color when size is big close to milky, centre.
Preferably, the particle size range of Ludox is 20~50nm；
More preferably, the particle size range of Ludox can be 30~40nm；In favor of improving the hardness and strength of closing film layer.Silicon
When the particle diameter of colloidal sol is too small, it reduces the resistance that is slided between film forming matter molecule, is unfavorable for improving the hardness of film layer and strong
Degree；When Ludox particle diameter is excessive, dispersion degree of the Ludox in film layer declines, and is also unfavorable for improving the hardness and strength of film layer.
Preferably, the wetting agent for polyether-modified alkyl copolymer or one kind in 2- ethylhexylsulfate sodium salts or
Compounding, can reduce the surface tension of confining liquid, penetrating power of the increase confining liquid into coating hole, while can also improve envelope
The flow leveling of film is closed, makes close membrane smooth.
Preferably, the accelerating agent is ethylene glycol or one kind or compounding in 1,3-PD, by increasing capacitance it is possible to increase confining bed
Speed is formed, and increases the smoothness of film layer.
The sealer is prepared by following methods：
(1) following components is measured by mass percentage：
Soluble polyurethane presses 35%~45%；
Soluble silane polymer presses 5%~15%；
Nanometer polytetrafluoroethylcomposite lotion presses 1.5%~2.5%；
Nano silicon dioxide sol presses 1.5%~2.5%；
Wetting agent presses 0.4%~0.6%；
Accelerating agent presses 1.5%~2.5%；
Deionized water presses 31.9~55.1%；
(2) said components are mixed, stirred evenly.
The sealer uses as follows：
(1) sealer deionized water is diluted 8~12 times in enclosed slot；
(2) 10~30s in confining liquid made from step (1) will be immersed after admiro or the passivation of zinc plating piece, washing, goes out groove
Drip-dry afterwards；
(3) blow the confining liquid of plating piece excess surface off with pressure-air, then toast 30 under 70~100oC hot environments
~90min.
The zn-ni alloy deposits of the present invention and having the beneficial effect that for zinc coat nano modification sealer：
(1) make film forming matter using soluble polyurethane and soluble silane polymer, there is good closing to make to coating
With the combination power between close membrane and coating is higher；
(2) the directly high soluble silane polymer of stability in use makees film forming matter, eliminates existing method and uses silicon
The destabilizing factor that alkane coupling agent hydrolysis generation silane polymer is brought；
(3) alcohol groups in silane polymer can generate stable compound with metallic zinc and nickel, and protection is played to coating
Effect, after close membrane scratches, these alcohol groups can also the new close membrane of spontaneous crosslinking generation；
(4) make filler using nanometer polytetrafluoroethylcomposite and nano silicon dioxide sol, have to coat of metal hole hypertonic
Permeability, sealing of hole ability is strong, is permeable to coat of metal pore interior depths；
(5) lubricity of confining bed is added using the appropriate nanometer polytetrafluoroethylcomposite of particle size and nano silicon dioxide
Energy and wear-resisting property, while the compactness and corrosion resistance of confining bed are also contributed to, extend the service life of plating piece.
Embodiment
To more fully understand the present invention, make further specific elaboration, but can not manage to the present invention by following embodiments
Solve as limitation of the invention, for those skilled in the art according to some nonessential improvement that foregoing invention content is made
With adjustment, it is also considered as being within the scope of the present invention.
Matched by following embodiment, prepare sealer：
The component and proportioning of the nano modification sealer of the present invention of table 1
In table unless otherwise specified, film forming matter includes soluble polyurethane and soluble silane polymer, wherein water-soluble
Property polyurethane account for film forming matter mass fraction be 75%~85%, soluble silane polymer accounts for the mass fraction of film forming matter
For 15%~25%.
Lubricant uses nanometer polytetrafluoroethylcomposite lotion, and wherein resin content is 50%, and particle diameter is 20~90nm, lotion pH
≥7.5；
Coalescents use nano silicon dioxide sol, and dioxide-containing silica is 25%~30%, pH=8~10, appearance
Milky white liquid is clear to for micro- indigo plant.The particle size range of Ludox is 10~120nm.Preferable particle size range is 20~50nm,
More preferably particle size range is 30~40nm；
After measuring each component by the mass percent of the various embodiments described above, sealer is prepared by following methods：By water solubility
Polyurethane is pressed, soluble silane polymer, nanometer polytetrafluoroethylcomposite lotion, nano silicon dioxide sol, wetting agent, accelerating agent,
Deionized water mixes, and stirs evenly, and after sealer is made, keeps spare.Certainly between the sealant components of the present invention
Ratio collocation not limited to this table, only makees example.
In the case of steel and iron parts plating alkaline zinc-nickel alloy, 11.3 μm of thickness of coating, carries out trivalent chromium true qualities passivation, uses
The blocking agent of the present invention, places 24h agings, by GB/T 10125-1997《Artificial atmosphere corrosion test salt spray test》Into
Row neutral salt spray test 240h, coating surface are generated without white corrosion thing, meet industry requirement.
Sealer uses as follows：The sealer of present invention deionized water is diluted into 8~10 times of preparation confining liquids,
It should be noted that：Deionized water dosage used herein does not include deionized water used in sealer preparation process；Zinc-nickel
Alloy plating piece is passivated and immerses 10~30s in above-mentioned confining liquid after washing, and goes out drip-dry after groove, then blow plating piece table off with pressure-air
The unnecessary confining liquid in face, then toasts 60min in 90~100oC.
In the case that steel and iron parts use non-cyanide alkali zinc-plated, 10.6 μm of thickness of coating, carries out trivalent chromium blueness passivation, uses
The blocking agent of the present invention, places 24h agings, by GB/T 10125-1997《Artificial atmosphere corrosion test salt spray test》Into
Row neutral salt spray test 96h, coating surface are generated without white corrosion thing, meet industry requirement.
Sealer uses as follows：The sealer deionized water of the present invention is diluted 10~12 times to be configured to close
Liquid, it should be noted that：Deionized water dosage used herein does not include deionized water used in sealer preparation process；Plating
Zinc part be passivated and washing after immerse 10~30s in above-mentioned confining liquid, go out drip-dry after groove, then with pressure-air to blow plating piece surface off more
Remaining confining liquid, then toasts 60min in 70~80oC.
With reference to the countries concerned's standard, the basic skill of zn-ni alloy deposits and zinc coat nano modification sealer to the present invention
Art performance indicator is measured, and test result is as shown in table 2.
The technical performance index of the nano modification sealer of the present invention of table 2
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention god.
Claims (7)
1. zn-ni alloy deposits and zinc coat nano modification sealer, it is characterised in that by mass percentage, including it is following
Component：
The film forming matter includes soluble polyurethane and soluble silane polymer；
The mass fraction that soluble polyurethane accounts for film forming matter is 75%~85%；
Soluble silane polymer accounts for the mass fraction 15~25% of film forming matter；
The soluble silane polymer trade name is PU 113；
The lubricant uses nanometer polytetrafluoroethylcomposite lotion, and wherein resin content is 50%, and particle diameter is 20~90nm, lotion pH
≥7.5；
The coalescents use nano silicon dioxide sol, and appearance contains for micro- blue-tinted transparent to milky white liquid, silica
Measure as 25%~30%, average grain diameter is 10~120nm, pH=8~10.
2. zn-ni alloy deposits as claimed in claim 1 and zinc coat nano modification sealer, it is characterised in that：The nanometer
Silica average grain diameter is 20~50nm in silicon dioxide gel.
3. zn-ni alloy deposits as claimed in claim 1 and zinc coat nano modification sealer, it is characterised in that：The nanometer
Silica average grain diameter is 30~40nm in silicon dioxide gel.
4. zn-ni alloy deposits as claimed in claim 1 and zinc coat nano modification sealer, it is characterised in that：The moistening
Agent compounds for one or both of polyether-modified alkyl copolymer or 2- ethylhexylsulfate sodium salts.
5. zn-ni alloy deposits as claimed in claim 1 and zinc coat nano modification sealer, it is characterised in that：The promotion
Agent compounds for one or both of ethylene glycol or 1,3- propane diols.
6. the application method of zn-ni alloy deposits as claimed in claim 1 and zinc coat nano modification sealer, its feature exist
In：
(1) sealer deionized water is diluted 8~12 times in enclosed slot；
(2) 10~30s in confining liquid made from step (1) will be immersed after admiro or the passivation of zinc plating piece, washing, is dripped after going out groove
It is dry；
(3) blow the confining liquid of plating piece excess surface off with pressure-air, then under 70~100 DEG C of hot environments baking 30~
90min。
7. the preparation method of zn-ni alloy deposits and zinc coat nano modification sealer, it is characterised in that：
(1) each material is measured by following mass percents：
Soluble polyurethane presses 35%~45%；
Soluble silane polymer presses 5%~15%；
Nanometer polytetrafluoroethylcomposite lotion presses 1.5%~2.5%；
Nano silicon dioxide sol presses 1.5%~2.5%；
Wetting agent presses 0.4%~0.6%；
Accelerating agent presses 1.5%~2.5%；
Deionized water presses 31.9~55.1%；
(2) each material mixing for measuring (1) together, stirs evenly, you can obtain the product to be produced.
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| CN106435688A (en) * | 2016-09-30 | 2017-02-22 | 湖北奥美伦科技有限公司 | Novel aluminum anodic oxidation close ash removing agent and preparation method and application process thereof |
| CN107460482A (en) * | 2017-08-09 | 2017-12-12 | 广州超邦化工有限公司 | A kind of environment-friendly type coating structure suitable for Aero-Space parts |
| CN107829082A (en) * | 2017-11-07 | 2018-03-23 | 北京安邦之星科技有限公司 | Environment-friendly galvanizing layer film agent, preparation method and the rust-preventing film comprising the film agent |
| CN107951461B (en) * | 2017-12-25 | 2021-08-06 | 青岛市妇女儿童医院 | Vaginal dilation blade for vaginal speculum used in obstetrics and gynecology department |
| CN108893766B (en) * | 2018-05-23 | 2019-08-30 | 深圳市赛邦新材料有限公司 | Improve the one-component medium temperature hole sealing agent and method for sealing of aluminium alloy salt spray resistance |
| CN109554734A (en) * | 2018-12-29 | 2019-04-02 | 南通申海工业科技有限公司 | Vehicle door bonnet lock abnormal sound solves technique |
| CN110157313B (en) * | 2019-05-14 | 2021-12-10 | 东莞市瑞欧表面处理科技有限公司 | Metal surface high-hardness scratch-resistant fingerprint-resistant sealant |
| CN110184594A (en) * | 2019-05-29 | 2019-08-30 | 宁波亚大金属表面处理有限公司 | A kind of barrel plating technique of trivalent Huang zinc |
| CN110256922A (en) * | 2019-06-27 | 2019-09-20 | 安徽鼎旺环保材料科技有限公司 | Latex sealer and preparation method thereof |
| CN111962053B (en) * | 2020-08-12 | 2023-01-10 | 广东东明新材科技有限公司 | Sealant for inhibiting white spots of AZ91D magnesium alloy and using method thereof |
| CN113402689A (en) * | 2021-06-23 | 2021-09-17 | 科文特亚环保电镀技术（江苏）有限公司 | Sealing agent for corrosion-resistant electroplated nickel layer |
| CN114481261B (en) * | 2022-01-19 | 2023-11-07 | 江门市瑞期精细化学工程有限公司 | Copper-tin alloy surface treatment liquid and preparation method and application thereof |
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| CN1786288A (en) * | 2005-11-09 | 2006-06-14 | 万向钱潮股份有限公司 | Galvanization technology |
| WO2008066319A1 (en) * | 2006-11-28 | 2008-06-05 | Woo-Jae Lee | Inorganic pigments composition having high hardness |
| CN101225280B (en) * | 2007-12-26 | 2010-12-08 | 傅晓平 | Dual-component silicane polymeric metal heavy-duty aqueous industrial coating |
| CN104059501B (en) * | 2013-05-03 | 2016-06-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Antirust sealer and its production and use and hot-dip metal plated material |
| CN103397327B (en) * | 2013-07-22 | 2015-12-02 | 江苏博业涂装工程有限公司 | For watersoluble closed dose of the micro-coating of zinc-base and preparation method thereof |
| CN103923560B (en) * | 2014-04-30 | 2016-04-06 | 武汉迪赛新材料有限公司 | A kind of water-based plate close agent and preparation method thereof |
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