CN104403538A - High-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint-resistant coating used for galvanized steel sheet - Google Patents

High-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint-resistant coating used for galvanized steel sheet Download PDF

Info

Publication number
CN104403538A
CN104403538A CN201410741723.7A CN201410741723A CN104403538A CN 104403538 A CN104403538 A CN 104403538A CN 201410741723 A CN201410741723 A CN 201410741723A CN 104403538 A CN104403538 A CN 104403538A
Authority
CN
China
Prior art keywords
chromium
resistant coating
free fingerprint
solid content
total solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410741723.7A
Other languages
Chinese (zh)
Inventor
党常华
丁奋
吴文希
顾圣杰
闵茸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Coating Co Ltdtechnology Center
Original Assignee
Shanghai Coating Co Ltdtechnology Center
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Coating Co Ltdtechnology Center filed Critical Shanghai Coating Co Ltdtechnology Center
Priority to CN201410741723.7A priority Critical patent/CN104403538A/en
Publication of CN104403538A publication Critical patent/CN104403538A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C09D151/08—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • 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
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Landscapes

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

Abstract

The invention relates to a high-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint resistant coating used for a galvanized steel sheet. The water solution of the chromium-free fingerprint resistant coating consists of the following components: (A) at least two or more than two water-based resins accounting for 30-80wt% of the total solid content; (B) at least one water-based cross-linking agent accounting for 1-10wt% of the total solid content; (C) at least one organic silane coupling agent accounting for 5-40wt% of the total solid content; (D) at least one vanadium-containing compound accounting for 0.1-2wt% of the total solid content; (E) a compound of at least one element in titanium and zirconium accounting for 0.1-5wt% of the total solid content; (F) at least one organic wax compound accounting for 0.5-10wt% of the total solid content; (G) at least one organic silicon modified collosol accounting for 1-30wt% of the total solid content; (H) at least one functional hydrophobic agent accounting for 0.05-0.5wt% of the total solid content. The galvanized steel sheet on which the chromium-free fingerprint resistant coating is coated can completely meet the requirement of outdoor use.

Description

There is high anti-corrosion, high durable and the hydrophobic chromium-free fingerprint-resistant coating for steel plate galvanized of excellence
Technical field
The present invention relates to a kind of chromium-free fingerprint-resistant coating for steel plate galvanized, particularly one has high anti-corrosion, high durable and the hydrophobic chromium-free fingerprint-resistant coating for steel plate galvanized of excellence.This fingerprint-resistant coating can form the hydrophobic film of one deck at galvanized steel sheet surface, while this film can give galvanized steel sheet surface excellent corrosion resistance and weathering resistance, can form again good acid resistance, alkali resistance, resistance to black change and processibility.
Background technology
Steel plate galvanized is used widely in industries etc. such as material of construction, household electrical appliance, trolley parts, along with growing stronger day by day of these industries, also climbs up and up to the demand of the steel of resistance to fingerprint.
In order to avoid steel plate galvanized transport and use procedure in by environment in the oxidation corrosion such as oxygen and moisture, researchist's original adoption galvanized steel sheet surface apply one deck containing 3 valency chromium and 6 valency chromium dual oxide states, the film of the densification of excellent corrosion resistance, this inorganic film of resistance to fingerprint is under comparatively gentle condition, there is the rust-preventing characteristic of short-term, but solidity to corrosion is not good under long-term or severe condition, and this coating film is hard and crisp, film adds client and is easy to man-hour fracture occurs or comes off, thus greatly reduces its corrosion resisting property.
Therefore, researchist develops the treatment technology forming film-type organic hybrid films on chromate film.This treatment process is mainly divided into two-step approach and single stage method.Two-step approach refers on chromate film, then is coated with the anti-fingerprint dope that last layer is made up of organic resin and colloidal silica, and organic resin comprises polyethylene kind, acrylic acid or the like, epoxies and polyurethanes etc.Single stage method refers to and directly add organic resin in chromic salt anti-fingerprint dope, and steel plate galvanized directly forms compound coating.Above-mentioned organic-inorganic composite coating film can meet the performance requriements of client's each side, but containing sexavalent chrome in coating, it belongs to pole poisonous substance matter, there is strong carinogenicity, for the consideration of environmental protection, it is subject to more and more stricter restriction, and most of industry and exported product are forbidden.
Develop the research direction that the fingerprint-resistant coating integrating the environment-friendly type of the several functions such as anti-finger printing, solidity to corrosion, self lubricity becomes current main-stream.In recent years, chromium-free fingerprint-resistant coating technology obtains development at full speed.
Propose in Unexamined Patent 08073775 different containing 2 kinds and can interreaction silane coupling agent composition the agent of metallic surface place, can give film good solidity to corrosion.
Propose in patent EP1426466A1 and a kind of the urethane resin of cationic or non-ionic type, acrylic resin, epoxy resin, vibrin and the resin of polyamide resin and ad hoc structure and the compound of Zr, Ti, V, Mo, W and Ce are coordinated with water and formed, it can provide excellent solidity to corrosion, alkali resistance and anti-finger printing.
In patent CN200510027157, propose the film of resistance to fingerprint adding the formation of P contained compound, vanadium compound, fluoro-acid and silane in waterborne polyurethane resin, it has excellent solidity to corrosion, alkali resistance and chemical-resistant.
Japanese Unexamined Patent Publication 2006 ?272767 patent proposes a kind of film of organic resin and P contained compound, metal bridging agent, organic wax and silicon sol composition that uses and carrys out coated metal plate, and the metal sheet of gained has good solidity to corrosion, oilness, processibility and coating.
Current chromium-free fingerprint-resistant film has the performances such as good solidity to corrosion, anti-finger printing, alkali resistance, self lubricity, processibility, instead of the most chromium fingerprint-resistant coating that has, has been widely used in household electrical appliances, automobile and other industries.But for the steel plate galvanized for open air, its environment for use is more severe, and stand the test of all kinds of severe rugged environment, common chromium-free fingerprint-resistant coating cannot meet the requirement of outdoor use.Therefore film not only needs to have the performance such as anti-finger printing, self lubricity, processibility that conventional non-chrome fingerprint-resistant coating has, also should possess better corrosion resisting property and weather resistance, film is made to tolerate high/low temperature, do not crack, excellent hydrophobicity is isolated moisture better, the spot that antagonism rainprint dirt is formed.
Summary of the invention
The object of the present invention is to provide and a kind of there is high anti-corrosion, high durable and the hydrophobic chromium-free fingerprint-resistant coating for steel plate galvanized of excellence, make steel plate galvanized can meet the various severe environment of outdoor use, by long felt and research, found that and use organic resin, inorganic metal salt, silane, silicon sol and specific function auxiliary agent, the film of final formation not only has alkali resistance, anti-blackening and processibility, has more excellent solidity to corrosion, weathering resistance and hydrophobicity.
In order to obtain the film of resistance to fingerprint of above-mentioned performance, the present invention adopts following technical scheme:
There is high anti-corrosion, high durable and the hydrophobic chromium-free fingerprint-resistant coating for steel plate galvanized of excellence, it is characterized in that: this chromium-free fingerprint-resistant coating aqueous solution composition comprises:
(A) at least two or more water-base resin, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 30 ?80 % by weight;
(B) at least one water cross-linking agent, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 1 ?10 % by weight;
(C) at least one organo silane coupling agent, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 5 ?40 % by weight;
(D) at least one is containing the compound of vanadium, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 0.1 ?2 % by weight;
(E) compound of at least one element in titanium, zirconium, its account for weight percent be chromium-free fingerprint-resistant coating total solid content 0.1 ?5 % by weight;
(F) the organic wax compound of at least one, weight percent chromium-free fingerprint-resistant coating shared by it be total solid content 0.5 ?10 % by weight;
(G) the organic-silicon-modified silicon sol of at least one, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 1 ?30 % by weight;
(H) the functional hydrophobic auxiliary agent of at least one, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 0.05 ?0.5 % by weight.
Water-base resin (A) described in the present invention is emulsion-type, aqueous dispersion type or water-soluble water-base resin; Two or more being selected from waterborne polyurethane resin, water-borne acrylic resin, waterborne organic silicon modified resin carries out composite, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 30 ?8 % by weight.
Water cross-linking agent (B) described in the present invention refer to can with contained carboxyl, the amino compound that chemical reaction occurs in water-base resin (A), weight percent shared by it is the 1-10 % by weight of chromium-free fingerprint-resistant coating total solid content.
Organo silane coupling agent (C) described in the present invention is selected from one or more in the organo silane coupling agent of vinyl, allyl group, amino, epoxy group(ing), methacryloxy or cyclohexenyl used in combination, and weight percent shared by it is the 5-40 % by weight of chromium-free fingerprint-resistant coating total solid content.
Vanadium-containing compound (D) described in the present invention is selected from the fluorochemical of the oxide compound of vanadium, vanadic acid, vanadate or vanadium, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 0.1 ?2 % by weight.
The wax emulsion that organic wax compound (F) described in the present invention is wax powder or Water-borne modification; Be selected from one in paraffin, polyethylene wax, tetrafluoroethylene wax, Poly Propylene Wax, palm wax, Vinyl Acetate Copolymer wax or their modified compound or two or more used in combination, its account for weight percent be chromium-free fingerprint-resistant coating total solid content 0.5 ?10 % by weight.
Organic-silicon-modified silicon sol (G) described in the present invention carries out modification by silane coupling agent to silicon sol and obtains, described silicon sol be particle diameter be selected from 1nm ?the silica sol dispersion of 200nm, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 1 ?30 % by weight.
Functional hydrophobic auxiliary agent (H) described in the present invention is selected from one in fatty acid metal soap, paraffin, polyolefine, silicone resin or fluorocarbon polymer or two or more used in combination, weight percent shared by it be chromium-free fingerprint-resistant coating total solid content 0.05 ?0.5 % by weight.
The preparation method of the chromium-free fingerprint-resistant coating described in the present invention, component (A) is added in stainless steel or enamel glass container, component (B), component (C), component (D), component (E), component (F) and component (G) is added successively under uniform stirring, after being uniformly mixed 20-40 minute, add component (H) again, stir 10-20 minute to after evenly, filter, packaging, obtains having high anti-corrosion, high durable and excellent hydrophobic aqueous chromium-free fingerprint-resistant coating; In whole making processes, temperature should control below 35 DEG C.
The application method of the chromium-free fingerprint-resistant coating described in the present invention, coats galvanized steel sheet surface by described chromium-free fingerprint-resistant coating, makes it dry, formed 1 ?3g/m 2dry film, obtain having high anti-corrosion, high durable and excellent hydrophobicity chromium-free fingerprint-resistant film.
Above component is by by being dissolved or dispersed in water, and can obtain having high anti-corrosion, high durable and the hydrophobic chromium-free fingerprint-resistant coating of excellence, be coated on galvanized steel sheet surface, can form film after super-dry is heavily 1 ?3g/m 2the film of resistance to fingerprint protection.
Use in the present invention water-base resin (A) can be emulsion-type, aqueous dispersion type or water-soluble, be selected from and choose two or more in waterborne polyurethane resin, water-borne acrylic resin, waterborne organic silicon modified resin and carry out composite, its weight percent accounting for film is 30%-80%, if weight percent is lower than 30%, solidity to corrosion, the weathering resistance of film can decline, if weight percent is higher than 80%, after resistance to alkali cleaning, film can come off.
Water-base resin (A) preferably those and other material, as the compound of at least one element in (C) organo silane coupling agent, (D) metal salt compound, (E) titanium, zirconium, silicon and (G) organic-silicon-modified silicon sol have good consistency.
The water soluble acrylic acid fat (A2) that the present invention relates to and the solid form weight ratio of waterborne polyurethane resin (A1) composite use are 100:10 ~ 100:80, more preferably total amount is than being 100:20 ~ 100:60, if resin A1 is very few, Resin A 2 is too much, film has good weathering resistance, but processibility does not reach requirement, the easy xanthochromia of film.If resin A1 is too much, Resin A 2 is very few, and the ductility of film and snappiness improve, but the weather resistance of film declines
The waterborne organic silicon modified acroleic acid fat (A3) that the present invention relates to and the solid form weight ratio of waterborne polyurethane resin (A1) composite use are 100:10 ~ 100:70, more preferably total amount is than being 100:20 ~ 100:50, if resin A3 is very few, Resin A 1 is too much, film snappiness is better, and film temperature-change resistance and weathering resistance decline.If resin A3 is too much, Resin A 1 is very few, and film processibility declines, and film worsened wettability, weathering resistance increases.
The water cross-linking agent (B) that the present invention uses refer to can with the compound of contained carboxyl, amino groups generation chemical reaction in water-base resin (A), they can be at least one in aziridine cpd, polycarbodiimide compound, epoxy silane chemical combination compound, zinc carbonate ammonia, weight percent shared by it is the 1-10% of total solid content, and more preferably total amount is than being 2-6%.If dosage of crosslinking agent is excessive, film cross-linking density can be caused excessive, film becomes fragile thus causes processibility to decline, and greatly can reduce the stability of coating on the other hand.If dosage of crosslinking agent is very few, film can be caused not exclusively crosslinked, and the performance such as chemical-resistant, sticking power of film all can significantly decline.
Organo silane coupling agent used in the present invention (C) can be selected a kind of or two or more used in combination as required, its kind there is no particular determination, it can be vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, γ '-(methacrylic oxygen propyl group) Trimethoxy silane, (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidyl ether propyl-triethoxysilicane, γ-glycidyl ether hydroxypropyl methyl diethoxy silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl) γ-aminopropyltriethoxy dimethoxysilane, γ-nitrogen propyl-triethoxysilicane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-r-chloropropyl trimethoxyl silane, ureidopropyltriethoxysilane, the silane such as sulfydryl Trimethoxy silane.The weight percent that organo silane coupling agent used accounts for film is 5-40%, and preferred weight percent is 10-30%.If the too high levels of organo silane coupling agent, easily there is autohemagglutination in the silicone hydroxyl generated after silane hydrolyzate, thus the stability of coating is significantly declined, and causes gel.If the content of organo silane coupling agent is very few, do not have enough silicone hydroxyl metals and resin to react, the sticking power of film and metallic surface is deteriorated, and can come off after the resistance to alkali cleaning of film, the wetting ability of film improves simultaneously, and the chemical-resistant of film and solidity to corrosion all can decline.
Vanadium-containing compound used in the present invention (D), can use the fluorochemical of the oxide compound of vanadium, vanadic acid, vanadate and vanadium.The valency of vanadium can be+divalent ,+3 valencys ,+4 valencys ,+5 valencys, as sodium metavanadate, sodium pyrovanadate, sodium vanadate, ammonium meta-vanadate, vanadium tetrachloride, vanadium pentafluoride etc., the vanadium compound that the present invention uses is necessary for water miscible, its weight percent accounting for film is 0.1-2%, more preferably weight percent 0.8-1.5%.When vanadium compounds weight percent is less than 0.1%, can not show additive effect, the erosion resistance of film can decline, and when vanadium compounds weight percent is greater than 2%, the aqueous solution of too much vanadium compound can cause coating gel.
The compound (E) of at least one element containing being selected from titanium, zirconium used in the present invention, the inner complex, zirconium carbonate, acetic acid zirconium, zirconium phosphate, zirconium carbonate ammonium etc. of such as titanium phosphate, organic titanium, its weight percent accounting for film is 0.1-5%, more preferably weight percent 1-3%.When this compound weight percentage is less than 0.1%, can not show additive effect, the erosion resistance of film can and tack and weathering resistance all can decline, when this compound weight percentage is greater than 5%, coating gel can be caused, paint stability decline.
Organic wax compound (F) used in the present invention can be the wax emulsion of wax powder or Water-borne modification, it can be select a kind of or two or more used in combination from paraffin, polyethylene wax, tetrafluoroethylene wax, Poly Propylene Wax, palm wax, Vinyl Acetate Copolymer wax etc. or their modified compound, and its weight percent accounting for film is 0.5-10%.More preferably weight percent 1-8%, the fusing point of organic wax compound is preferably between 60-140 DEG C, and particle diameter is at 0.5-2.0 micron.If usage quantity very little, the oilness of film is inadequate, is unfavorable for machine-shaping.If too high, the film-forming properties of coating is deteriorated, thus cause the erosion resistance of film, solvent resistance all declines.
Organic-silicon-modified silicon sol (G) used in the present invention uses silane coupling agent to carry out modification to silicon sol, the kind that silane coupling agent uses there is no particular determination, it can be vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, γ '-(methacrylic oxygen propyl group) Trimethoxy silane, (3, 4-epoxycyclohexyl) ethyl trimethoxy silane etc., the particle diameter of silica sol dispersion is selected from 1nm-200nm, preferably at 10nm-150nm, silicon sol after silane modified, its even particulate dispersion is in film, add the compactness of film, can also and resin, there is crosslinking reaction in metallic compounds etc., the wetting ability of silicon sol is changed after silane-modified, film is made to have better hydrophobicity, effectively completely cut off entering of the materials such as moisture.Weight percent shared by it is the 1-30% of total solid content, and more preferably weight percent is 5-20%, if this compound adding proportion is too high, the anti-blackening of film can be deteriorated, film hydrophobicity is excessively strong, and coating, when applying, cissing, shrinkage cavity construction problem can occur, and causes solidity to corrosion to decline.If the adding proportion of this compound is too low, do not have additive effect, the compactness of film declines, and the hydrophobicity of film does not reach requirement yet.
(H) that the present invention relates to functional hydrophobic auxiliary agent, can be select in fatty acid metal soap, paraffin, polyolefine, silicone resin or fluorocarbon polymer a kind of or two or more used in combination, weight percent shared by it is the 0.05-0.5% of total solid content, if more preferably weight percent is that 0.1-0.4%. hydrophobic auxiliary agent usage quantity is excessive, film hydrophobicity is too strong, film is to the worsened wettability of ground, and film is discontinuous, and solidity to corrosion declines.If addition is too small, improve little to the hydrophobicity of film.
The present invention can add the aqueous promoters such as tensio-active agent, wetting agent, flow agent, defoamer, thickening material to improve the outward appearance of coating application and film, the not special requirement of above-mentioned aqueous promoter.
The constructional method that aqueous chromium-free fingerprint-resistant coating of the present invention is coated on galvanized steel sheet surface has no particular limits, have no particular limits needing the kind, size, shape etc. of steel plate galvanized to be processed, such as hot-dip galvanizing sheet steel, Al-Zn coated steel, electrogalvanizing steel plate, spendable method has spraying method, rolling method, dip coating etc., is an application.Dried coating film mode also has no particular limits, can be Hot-blast Heating, induction heating, Infrared Heating, the temperature of heating is preferably at 80 DEG C-200 DEG C, more preferably at 100 DEG C-150 DEG C, if temperature <80 DEG C is unfavorable for the solvent evaporates in system, film does not occur to be cross-linked and causes performance significantly to decline simultaneously.If temperature >200 DEG C, may produce the defect problem of a large amount of film, too high temperature also can cause film generation xanthochromia simultaneously, causes film performance significantly to decline.
The present invention is coated on dried dry film weight on steel plate galvanized and preferably controls at 1-3g/m 2if, dry film weight <1g/m 2, cannot form provide protection to galvanized steel sheet surface, the solidity to corrosion of film and weathering resistance decline.If dry film total amount >3g/m 2, greatly can increase the use cost of client.
It is a film be jointly cross-linked by organic and inorganic substance that aqueous chromium-free fingerprint-resistant coating of the present invention is coated on that galvanized steel sheet surface can be formed, acrylic resin and organosilicon modified crylic acid resin are that film provides excellent weathering resistance and temperature-change resistance, metal ion and water soluble resin reaction form insoluble resin coating and are placed on galvanized steel sheet surface formation protective layer, linking agent add the cross-linking density further increasing film, silane coupling agent is by after hydrolyzable, not only there is intermolecular polymerization, can also with the silicone hydroxyl of metallic surface, the group generation condensation reactions such as the carboxyl in silicon sol and organic resin, turn increase the shielding of film, also improve the tack of film and ground, not only filling effect is served through organic-silicon-modified silicon sol, improve the compactness of film, also improve the hydrophobicity of film, functional hydrophobic auxiliary agent add the hydrophobicity further increasing film, the surface of film is enriched in after organic wax compound adds, film is made to have better slipping and processibility.In sum, the hydrophobic film of resistance to fingerprint of this layer of organo-mineral complexing, can prevent the intrusion of moisture and oxygen etc. effectively, makes film obtain excellent solidity to corrosion and weathering resistance, also gives the excellent acid resistance of film, alkali resistance and processibility simultaneously.
The invention has the beneficial effects as follows; provide one and there is high anti-corrosion, high durable and excellent hydrophobic aqueous chromium-free fingerprint-resistant coating; steel plate galvanized coated by it can meet the requirement of outdoor use completely; its performance with also have chromium fingerprint-resistant coating suitable what use at present; chromium fingerprint-resistant coating can be substituted completely, good pushing effect can have been played to the protection of environment.
Embodiment
Exemplify examples and comparative examples of the present invention below, so that illustrate further the present invention, but therefore the present invention is not limited.
(1) test piece
1. the kind of test piece
A. pot galvanize test piece (GI): thickness of slab 0.5mm, galvanizing layer weight 40/40g/m 2.
B. aluminum-zinc alloy test piece (GL): thickness of slab 0.5mm, aluminize zinc layer weight 70/70g/m 2.
C. electro-galvanizing test piece (EG): thickness of slab 0.8mm, galvanizing layer weight 20/20g/m 2.
2. the cleaning of zinc-plated model
First adopt butanone (chemical reagent) to carry out wiping to substrate surface and eliminate greasy dirt, then carry out ultrasonic cleaning 10 minutes, dried for standby by substrate immersion alcohol (chemical reagent).
(2) preparation of matrix resin A
1. the preparation of waterborne polyurethane resin (A1)
Under the protection of dry high purity nitrogen; the molecular-weight average adding 50 parts of vacuum hydro-extractions in four-hole boiling flask be successively the polyester polyol of 1500,30 parts of diphenylmethanediisocyanates, 1.2 part 1; 4 butyleneglycols; 1.5 parts of dimethylol propionic acids, 0.5 part of TriMethylolPropane(TMP); under mechanical stirring, temperature is 75 DEG C, reacts 2 hours; then add 10 parts of ethyl acetate, then react 2 hours.When in the polymer that question response generates, isocyano-content is constant, reaction terminates.In the polymer obtained, under high shear add 100 parts of water and 1 part of dimethylaminoethanol carries out emulsification, finally add 2 parts of isophorone diamines, stir and within 10 minutes, obtain the translucent waterborne polyurethane resin of blue light.
2. the preparation of water-borne acrylic resin (A2)
200 parts of tolylene diisocyanates and 0.2 part of dibutyl tin laurate is added in the four-hole boiling flask that agitator, reflux exchanger and thermometer are housed, be preheated to 40 DEG C, slow dropping 74 parts of propyl carbinols, within about 0.5 hour, drip off, after constant temperature 40 DEG C reacts about 2.5-3 hour, more slowly drip 130 parts of Propylene glycol monoacrylates, be warming up to 70 DEG C, be incubated 2 hours, be cooled to 50 DEG C of dischargings.
60 parts of above-mentioned performed polymers and 25 parts of butyl glycol ethers are added in four-hole boiling flask, pass into nitrogen, stirring is warming up to 75 DEG C, slow dropping mix monomer (40 parts of butyl acrylates, 32 parts of methyl methacrylates), drip 0.5 part of initiator Diisopropyl azodicarboxylate, time for adding controls at 3 hours simultaneously, temperature of reaction controls at 80 DEG C, be incubated 1 hour, be cooled to 50 DEG C with bottom discharge, namely obtain water-borne acrylic resin.
3. the preparation of waterborne organic silicon acrylic resin modified (A3)
The molecular-weight average adding 167 parts in the four-hole boiling flask that agitator, reflux exchanger and thermometer are housed is the hydroxy silicon oil (120 DEG C of vacuum hydro-extraction) of 300,200 parts of tolylene diisocyanates and 0.2 part of dibutyl tin laurate, be preheated to 40 DEG C, slow dropping 74 parts of propyl carbinols, within about 0.5 hour, drip off, after constant temperature 40 DEG C reacts about 2.5-3 hour, more slowly drip 130 parts of Propylene glycol monoacrylates, be warming up to 70 DEG C, be incubated 2 hours, be cooled to 50 DEG C of dischargings.
60 parts of above-mentioned performed polymers and 25 parts of butyl glycol ethers are added in four-hole boiling flask, pass into nitrogen, stirring is warming up to 75 DEG C, slow dropping mix monomer (40 parts of butyl acrylates, 32 parts of methyl methacrylates), drip 0.5 part of initiator Diisopropyl azodicarboxylate, time for adding controls at 3 hours simultaneously, temperature of reaction controls at 80 DEG C, be incubated 1 hour, be cooled to 50 DEG C with bottom discharge, namely obtain waterborne organic silicon acrylic resin modified.
(3) preparation of organic-silicon-modified silicon sol (G)
30 parts of water and 65 parts of silicon sol (Nissan Chemical Industries are added in the four-hole boiling flask that agitator, reflux exchanger and thermometer are housed, SNOWTEX-UP), stir about 15 minutes at 40 DEG C, the ethanolic soln of slow dropping 1.37 parts of methyl three oxygen ethylsilane, time for adding controls at 1 hour, 70 DEG C are incubated 6 hours, namely obtain organic-silicon-modified silicon sol after cooling.
(4) preparation of aqueous chromium-free fingerprint-resistant coating
Carry out the preparation of aqueous chromium-free fingerprint-resistant coating by the following method, component A is added in stainless steel or enamel glass container, B component, component C, component D, component E, component F and component G is added successively under uniform stirring, after being uniformly mixed 30 minutes, then add component H, stir about 10 minutes to after evenly, in whole making processes, temperature should control below 35 DEG C, filter, packaging, obtain having high anti-corrosion, high durable and excellent hydrophobic aqueous chromium-free fingerprint-resistant coating.
In order to avoid appearance of film defect in above-mentioned making processes, the functional aids such as wetting agent, flow agent, defoamer can be added and carry out adjustment solution.The adding of these auxiliary agents, to select and addition is familiar with grasping by technician in the industry, therefore do not enumerate one by one in following concrete formula table 1.It should be noted that often adding a kind of auxiliary agent all needs to stir fully and add lower a kind of auxiliary agent again, to guarantee that each component of coating mixes.
(5) composition of fingerprint-resistant coating
The fingerprint-resistant coating composition that embodiment and comparative example use is as shown in table 1
(5) starting material explanation
The concrete title of various starting material used in embodiment 1-6 and comparative example 1-4 in the present invention, source are described as follows:
Table 2 water-base resin
Table 3 water cross-linking agent
Coding Linking agent type Trade name Vendor name
B1 Aziridine XAMA 7 Bayer
B2 Epoxy silane compounds Wetlink 78 Toshiba's organosilicon
B3 Polycarbodiimide XL-29SE Dow Chemical
B4 Zinc carbonate ammonia Zinc carbonate ammonia Chemical Reagent Co., Ltd., Sinopharm Group
Table 4 silane coupling agent
Table 5 vanadium compound
Coding Vanadium compound type Trade name Vendor name
D1 Sodium metavanadate Sodium metavanadate Chemical Reagent Co., Ltd., Sinopharm Group
D2 Ammonium meta-vanadate Ammonium meta-vanadate Chemical Reagent Co., Ltd., Sinopharm Group
D3 Vanadic acid sodium Vanadic acid sodium Chemical Reagent Co., Ltd., Sinopharm Group
D4 Vanadium tetrachloride Vanadium tetrachloride Chemical Reagent Co., Ltd., Sinopharm Group
Table 6 titanium/zirconium compounds
Coding Type of compounds Trade name Vendor name
E1 Titanium Titanium phosphate Sigma-Aldrich
E2 Zirconium Zirconium phosphate Sigma-Aldrich
E3 Zirconium Zirconium carbonate ammonium Sigma-Aldrich
E4 Zirconium Acetic acid zirconium Sigma-Aldrich
The organic wax compound of table 7
Coding Organic wax type of compounds Trade name Vendor name
F1 High density polyethylene(HDPE) Sudranol 100 Nan De emulsion chemistry company
F2 Tetrafluoroethylene Sudranol 700 Nan De emulsion chemistry company
F3 Palm wax Sudranol CAR 25 Nan De emulsion chemistry company
F4 HDPE/PTFE D-838 Germany Keim-Additec
F5 Acid amides/silicon-dioxide D-1307 Germany Keim-Additec
The organic-silicon-modified silicon sol of table 8
Coding Type of compounds Solid content
G1 Organic-silicon-modified silicon sol 20％
The functional hydrophobic auxiliary agent of table 9
Coding Type of compounds Trade name Vendor name
H1 Calcium stearate dispersion Ombrelub 533 The bright icepro chemical industry of Germany
H2 Polysiloxane SIVIN WF Tego company
H3 Water-based paraffinic wax dispersions Basophob WDS BASF
(4) film preparation of specimen and performance evaluation
In embodiment 1-6 and comparative example 1-4, the preparation method of the film of resistance to fingerprint and method of evaluating performance are described as follows:
1. the preparation of resistance to fingerprint template
Utilize masking line rod by coating blade coating in specimen surface, then put into baking oven and dry, after cooling, test properties.Often in group experiment, the type of model, the thickness of film and drying temperature are implemented according in table 1.
2. the method for testing performance of test piece
1) weathering resistance
Testing method is be placed in QUVB proofing box by the model prepared, and 8h is a loop cycle, 4h ultraviolet lighting, blackboard temperature 60 ± 3 DEG C, 4h condensation, blackboard temperature 50 ± 3 DEG C
◎: >700h product surface occurs without phenomenons such as coating foaming, efflorescence, corrosions; And surface gloss does not decline compared with original gloss
Zero: 600 ?700h product surface occur without the phenomenon such as coating foaming, efflorescence, corrosion; And surface gloss does not decline compared with original gloss;
△: 500 ?600h product surface occur without the phenomenon such as coating foaming, efflorescence, corrosion; And surface gloss does not decline compared with original gloss; ;
×: <500h product surface occurs without phenomenons such as coating foaming, efflorescence, corrosions; And surface gloss does not decline compared with original gloss; .
2) chemical resistant properties
Testing method under pressure is about 4.9N, dips methylethylketone chemical reagent wiping model 20 times back and forth with cotton balls, or with 80% ethanol chemical reagent wiping model 30 times back and forth, each distance be 50mm, visual appearance of coat changing conditions, and specifically evaluation is as follows:
◎: unchanged;
Zero: slightly wiping vestige;
△: obviously to turn white or to be coated with membrane portions show-through;
×: film is completely show-through or come off.
3) anti-blackening
Simulation test condition is boiling water Acceleration study, and experimental technique is that the sample of 150mm × 75mm is longitudinally vertically put into boiling water, takes out after 1 hour, observes the situation that its plate face produces stain, and concrete evaluation is as follows:
◎: unchanged;
Zero: stain area occupation ratio is less than 5%;
△: stain area occupation ratio is greater than 5% and is less than 10%;
×: stain area occupation ratio is greater than 10%.
4) dull and stereotyped erosion resistance
Model is carried out 120 hours salt mist experiments according to ASTM B117 standard, and then observe the situation that on model, white rust generates, concrete judgement criteria is as follows:
◎: white rust area occupation ratio is less than 5%;
Zero: white rust area occupation ratio is greater than 5% but is less than 10%;
△: white rust area occupation ratio is greater than 10% but is less than 30%;
×: white rust area occupation ratio is greater than 30%.
5) alkali resistance
Use commercially available neutral and alkali grease-removing agent first model to be sprayed 3 minutes at 50 DEG C, then this model is carried out 120 hours salt-fog tests according to ASTM B117 standard, finally observe the situation that on model, white rust generates, concrete judgement criteria is as follows:
◎: white rust area occupation ratio is less than 5%;
Zero: white rust area occupation ratio is greater than 5% but is less than 10%;
△: white rust area occupation ratio is greater than 10% but is less than 30%;
×: white rust area occupation ratio is greater than 30%.
6) humidity resistance
Testing method, for be positioned in damp heat box by model, 49 degree, humidity continuously experiment 120 hours under being the condition of 98%, then observes the corrosion situation of specimen surface, concrete evaluate as follows:
◎: non-corroding;
Zero: corrosion area occupation ratio is less than 5%;
△: corrosion area occupation ratio is less than 5% but is greater than 20%;
×: corrosion area occupation ratio is greater than 20%.
7) processibility
Testing method draws lattice experiment (100 lattice/cm for being carried out respectively by model 2), heavy ball impact experiment (ballistic work is 9J), the curved experiment of T, and then with firmly tearing after the SCOTCH-600 type transparent adhesive tape of 3M company respectively application work district, observe film coated surface with or without peeling off, concrete evaluate as follows:
Draw lattice experiment Heavy ball impact experiment The curved experiment of T
◎ Without peeling off Without peeling off 2T is without peeling off
○ Be less than 5% to peel off Sporadicly peel off 3T is without peeling off
△ Be greater than 5% to be less than 10% and to peel off Big area is peeled off 4T is without peeling off
× Be greater than 10% Peel off completely 5T is without peeling off
8) hydrophobicity
To prepare model and measure hydrophilic angle, concrete evaluation method is as follows:
◎: hydrophilic angle >100;
Zero: hydrophilic angle 90 ?100;
△: hydrophilic angle 70 ?90;
×: hydrophilic angle <70.

Claims (10)

1. there is high anti-corrosion, high durable and the hydrophobic chromium-free fingerprint-resistant coating for steel plate galvanized of excellence, it is characterized in that: this chromium-free fingerprint-resistant coating aqueous solution composition comprises:
(A) at least two or more water-base resin, weight percent shared by it is the 30-80 % by weight of chromium-free fingerprint-resistant coating total solid content;
(B) at least one water cross-linking agent, weight percent shared by it is the 1-10 % by weight of chromium-free fingerprint-resistant coating total solid content;
(C) at least one organo silane coupling agent, weight percent shared by it is the 5-40 % by weight of chromium-free fingerprint-resistant coating total solid content;
(D) at least one is containing the compound of vanadium, and weight percent shared by it is the 0.1-2 % by weight of chromium-free fingerprint-resistant coating total solid content;
(E) compound of at least one element in titanium, zirconium, it accounts for the 0.1-5 % by weight that weight percent is chromium-free fingerprint-resistant coating total solid content;
(F) the organic wax compound of at least one, weight percent chromium-free fingerprint-resistant coating shared by it is the 0.5-10 % by weight of total solid content;
(G) the organic-silicon-modified silicon sol of at least one, weight percent shared by it is the 1-30 % by weight of chromium-free fingerprint-resistant coating total solid content;
(H) the functional hydrophobic auxiliary agent of at least one, weight percent shared by it is the 0.05-0.5 % by weight of chromium-free fingerprint-resistant coating total solid content.
2. chromium-free fingerprint-resistant coating according to claim 1, is characterized in that: described water-base resin (A) is emulsion-type, aqueous dispersion type or water-soluble water-base resin; Two or more being selected from waterborne polyurethane resin, water-borne acrylic resin, waterborne organic silicon modified resin carries out composite, and weight percent shared by it is the 30-80 % by weight of chromium-free fingerprint-resistant coating total solid content.
3. chromium-free fingerprint-resistant coating according to claim 1, it is characterized in that: described water cross-linking agent (B) refer to can with contained carboxyl, the amino compound that chemical reaction occurs in water-base resin (A), weight percent shared by it is the 1-10 % by weight of chromium-free fingerprint-resistant coating total solid content.
4. chromium-free fingerprint-resistant coating according to claim 1, it is characterized in that: described organo silane coupling agent (C) is selected from one or more in the organo silane coupling agent of vinyl, allyl group, amino, epoxy group(ing), methacryloxy or cyclohexenyl used in combination, weight percent shared by it is the 5-40 % by weight of chromium-free fingerprint-resistant coating total solid content.
5. chromium-free fingerprint-resistant coating according to claim 1, it is characterized in that: described vanadium-containing compound (D) is selected from the fluorochemical of the oxide compound of vanadium, vanadic acid, vanadate or vanadium, and weight percent shared by it is the 0.1-2 % by weight of chromium-free fingerprint-resistant coating total solid content.
6. chromium-free fingerprint-resistant coating according to claim 1, is characterized in that: the wax emulsion that described organic wax compound (F) is wax powder or Water-borne modification; Be selected from one in paraffin, polyethylene wax, tetrafluoroethylene wax, Poly Propylene Wax, palm wax, Vinyl Acetate Copolymer wax or their modified compound or two or more used in combination, it accounts for the 0.5-10 % by weight that weight percent is chromium-free fingerprint-resistant coating total solid content.
7. chromium-free fingerprint-resistant coating according to claim 1, it is characterized in that: described organic-silicon-modified silicon sol (G) carries out modification by silane coupling agent to silicon sol and obtains, described silicon sol is the silica sol dispersion that particle diameter is selected from 1nm-200nm, and weight percent shared by it is the 1-30 % by weight of chromium-free fingerprint-resistant coating total solid content.
8. chromium-free fingerprint-resistant coating according to claim 1, it is characterized in that: described functional hydrophobic auxiliary agent (H) is selected from one in fatty acid metal soap, paraffin, polyolefine, silicone resin or fluorocarbon polymer or two or more used in combination, and weight percent shared by it is the 0.05-0.5 % by weight of chromium-free fingerprint-resistant coating total solid content.
9. the preparation method of the chromium-free fingerprint-resistant coating according to claim 1-8, it is characterized in that: in stainless steel or enamel glass container, add component (A), component (B), component (C), component (D), component (E), component (F) and component (G) is added successively under uniform stirring, after being uniformly mixed 20-40 minute, add component (H) again, stir 10-20 minute to after evenly, filter, packaging, obtains having high anti-corrosion, high durable and excellent hydrophobic aqueous chromium-free fingerprint-resistant coating; In whole making processes, temperature should control below 35 DEG C.
10. according to a constructional method for the chromium-free fingerprint-resistant coating described in claim 1-8, it is characterized in that, described chromium-free fingerprint-resistant coating is coated galvanized steel sheet surface, make it dry, form 1-3g/m 2dry film, obtain having high anti-corrosion, high durable and excellent hydrophobicity chromium-free fingerprint-resistant film.
CN201410741723.7A 2014-12-08 2014-12-08 High-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint-resistant coating used for galvanized steel sheet Pending CN104403538A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410741723.7A CN104403538A (en) 2014-12-08 2014-12-08 High-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint-resistant coating used for galvanized steel sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410741723.7A CN104403538A (en) 2014-12-08 2014-12-08 High-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint-resistant coating used for galvanized steel sheet

Publications (1)

Publication Number Publication Date
CN104403538A true CN104403538A (en) 2015-03-11

Family

ID=52641212

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410741723.7A Pending CN104403538A (en) 2014-12-08 2014-12-08 High-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint-resistant coating used for galvanized steel sheet

Country Status (1)

Country Link
CN (1) CN104403538A (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105400353A (en) * 2015-12-29 2016-03-16 奎克化学（中国）有限公司 Chromium-free fingerprint resistant liquid
CN105505065A (en) * 2016-01-21 2016-04-20 苏州法斯特信息科技有限公司 Fingerprint-resistant anticorrosive material and preparation method thereof
CN106318170A (en) * 2015-06-30 2017-01-11 宝山钢铁股份有限公司 Water-based environment-friendly treating agent for galvanized steel plate, manufacture method and using method thereof
CN106318169A (en) * 2015-06-30 2017-01-11 宝山钢铁股份有限公司 Organic composite coating layer galvanized steel plate with excellent bending processability
CN106703355A (en) * 2017-02-24 2017-05-24 四川金路高新材料有限公司 Production method of wall surface decoration materials capable of generating negative oxygen ions
CN108129971A (en) * 2017-12-27 2018-06-08 中山大学 A kind of anti-scraping coating of environmental protection resistance and fingerprint resistance and its application method
CN110305256A (en) * 2019-06-12 2019-10-08 武汉钢实钢福材新型产品科技有限公司 A kind of chromium-free fingerprint-resistant masking liquid and preparation method thereof
CN110387174A (en) * 2019-07-01 2019-10-29 深圳华美板材有限公司 A kind of water-based hydrophobic oleophobic Coil Coating Products and its manufacturing process
CN111040488A (en) * 2019-12-05 2020-04-21 曾令涛 UV hand feeling coating for galvanized plate of household appliance and preparation method thereof
CN111304641A (en) * 2020-02-21 2020-06-19 攀钢集团攀枝花钢铁研究院有限公司 Hot-dip aluminum-zinc plate chromium-free passivation solution and preparation method of hot-dip aluminum-zinc fingerprint-resistant plate
CN111511854A (en) * 2017-12-26 2020-08-07 Posco公司 Metal surface treatment composition having excellent sliding resistance and metal material using same
CN111849286A (en) * 2020-07-30 2020-10-30 辽宁宝瑞科技有限公司 Bacteriostatic fingerprint-resistant coating agent, and preparation method and application thereof
CN114929819A (en) * 2019-12-05 2022-08-19 Posco公司 Surface treatment composition for ternary system hot-dip galvanized alloy steel sheet for imparting excellent corrosion resistance and surface color, ternary system hot-dip galvanized alloy steel sheet surface-treated therewith, and method for manufacturing the same
CN115651435A (en) * 2022-09-07 2023-01-31 上海兴赛尔表面材料有限公司 Fingerprint-resistant liquid for aluminum-zinc-magnesium plated board and preparation method thereof
CN115679195A (en) * 2021-07-30 2023-02-03 宝山钢铁股份有限公司 Seamless steel tube for automobile driving shaft and manufacturing method thereof
CN116445065A (en) * 2023-04-14 2023-07-18 上海耀岩化学品有限公司 Chromium-free fingerprint-resistant coating liquid for galvanized steel sheet and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468461A (en) * 1992-06-03 1995-11-21 Nippon Paint Co., Ltd. Anticorrosive primer composition
CN103740255A (en) * 2013-12-27 2014-04-23 上海涂料有限公司技术中心 Aqueous colorful chromium-free anti-fingerprint coating for coating surface of metal material and construction method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468461A (en) * 1992-06-03 1995-11-21 Nippon Paint Co., Ltd. Anticorrosive primer composition
CN103740255A (en) * 2013-12-27 2014-04-23 上海涂料有限公司技术中心 Aqueous colorful chromium-free anti-fingerprint coating for coating surface of metal material and construction method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈利君等: ""甲基三乙氧基硅烷改性硅溶胶及疏水性能研究"", 《涂料工业》 *

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106318170A (en) * 2015-06-30 2017-01-11 宝山钢铁股份有限公司 Water-based environment-friendly treating agent for galvanized steel plate, manufacture method and using method thereof
CN106318169A (en) * 2015-06-30 2017-01-11 宝山钢铁股份有限公司 Organic composite coating layer galvanized steel plate with excellent bending processability
CN105400353A (en) * 2015-12-29 2016-03-16 奎克化学（中国）有限公司 Chromium-free fingerprint resistant liquid
CN105505065A (en) * 2016-01-21 2016-04-20 苏州法斯特信息科技有限公司 Fingerprint-resistant anticorrosive material and preparation method thereof
CN106703355A (en) * 2017-02-24 2017-05-24 四川金路高新材料有限公司 Production method of wall surface decoration materials capable of generating negative oxygen ions
CN106703355B (en) * 2017-02-24 2020-04-14 四川金路高新材料有限公司 Method for producing negative oxygen ion wall decoration material
CN111511854A (en) * 2017-12-26 2020-08-07 Posco公司 Metal surface treatment composition having excellent sliding resistance and metal material using same
US20210062038A1 (en) * 2017-12-26 2021-03-04 Posco Metal surface treatment composition having excellent slip resistance, and metal material to which same is applied
EP3733800A4 (en) * 2017-12-26 2021-03-10 Posco Metal surface treatment composition having excellent slip resistance, and metal material to which same is applied
CN108129971A (en) * 2017-12-27 2018-06-08 中山大学 A kind of anti-scraping coating of environmental protection resistance and fingerprint resistance and its application method
CN108129971B (en) * 2017-12-27 2020-12-15 中山大学 Environment-friendly fingerprint-resistant scratch-resistant coating of film substrate and application method thereof
CN110305256A (en) * 2019-06-12 2019-10-08 武汉钢实钢福材新型产品科技有限公司 A kind of chromium-free fingerprint-resistant masking liquid and preparation method thereof
CN110387174A (en) * 2019-07-01 2019-10-29 深圳华美板材有限公司 A kind of water-based hydrophobic oleophobic Coil Coating Products and its manufacturing process
CN111040488A (en) * 2019-12-05 2020-04-21 曾令涛 UV hand feeling coating for galvanized plate of household appliance and preparation method thereof
CN114929819A (en) * 2019-12-05 2022-08-19 Posco公司 Surface treatment composition for ternary system hot-dip galvanized alloy steel sheet for imparting excellent corrosion resistance and surface color, ternary system hot-dip galvanized alloy steel sheet surface-treated therewith, and method for manufacturing the same
CN114929819B (en) * 2019-12-05 2023-06-23 Posco公司 Surface treatment composition, ternary hot-dip galvanized alloy steel sheet surface-treated by using same, and method for producing same
CN111304641A (en) * 2020-02-21 2020-06-19 攀钢集团攀枝花钢铁研究院有限公司 Hot-dip aluminum-zinc plate chromium-free passivation solution and preparation method of hot-dip aluminum-zinc fingerprint-resistant plate
CN111849286A (en) * 2020-07-30 2020-10-30 辽宁宝瑞科技有限公司 Bacteriostatic fingerprint-resistant coating agent, and preparation method and application thereof
CN111849286B (en) * 2020-07-30 2021-11-05 辽宁宝瑞科技有限公司 Bacteriostatic fingerprint-resistant coating agent, and preparation method and application thereof
CN115679195A (en) * 2021-07-30 2023-02-03 宝山钢铁股份有限公司 Seamless steel tube for automobile driving shaft and manufacturing method thereof
CN115679195B (en) * 2021-07-30 2023-10-17 宝山钢铁股份有限公司 Seamless steel tube for automobile driving shaft and manufacturing method thereof
CN115651435A (en) * 2022-09-07 2023-01-31 上海兴赛尔表面材料有限公司 Fingerprint-resistant liquid for aluminum-zinc-magnesium plated board and preparation method thereof
CN115651435B (en) * 2022-09-07 2023-09-29 上海兴赛尔表面材料有限公司 Fingerprint-resistant liquid for aluminum-zinc-magnesium plated plate and preparation method thereof
CN116445065A (en) * 2023-04-14 2023-07-18 上海耀岩化学品有限公司 Chromium-free fingerprint-resistant coating liquid for galvanized steel sheet and preparation method thereof

Similar Documents

Publication Publication Date Title
CN104403538A (en) High-corrosion-resistance, high-weather-resistance and excellent-hydrophobicity chromium-free fingerprint-resistant coating used for galvanized steel sheet
CN103740255B (en) A kind of hydrate colour chromium-free fingerprint-resistant coating for metallizing material surface and constructional method thereof
CN101678397B (en) Method for coating a metal surface with an aqueous polymer-containing composition, use of said aqueous composition and coated substrate
TWI444504B (en) Surface-treating agent for galvanized steel plate
CN102070966B (en) Organic and inorganic mixed fingerprint-resistance coating and preparation method thereof
JP5168332B2 (en) Surface treatment liquid for galvanized steel sheet, galvanized steel sheet and method for producing the same
CN104233243B (en) Aqueous metal surface treatment agent
KR101277607B1 (en) Surface-treating agent, process for manufacturing plated steel sheet using the surface-treating agent, and plated steel sheet
JP5542706B2 (en) Clear painted stainless steel sheet and method for manufacturing the same
CN103820778A (en) Aqueous metal surface treatment agent and metal surface treatment method using same
CN102822290A (en) Surface-treating composition
TWI482880B (en) Coated steel sheet complising aluminium-zinc base alloy plating
KR20190076099A (en) Coating composition for hot dip galvanized steel sheet having excellent corrosion-resistance and blackening-resistance the surface treated hot dip galvanized steel sheet prepared by using the coating composition and method for preparing the surface treated hot dip galvanized steel sheet
CN104789954A (en) Lubricating aqueous metal surface treatment agent and metal surface treatment method using same
JP6073155B2 (en) Thin black metal sheet
JP4747625B2 (en) Surface-treated steel sheet excellent in corrosion resistance and scratch resistance and method for producing the same
JPWO2015152187A1 (en) Metal surface treatment agent for galvanized steel, coating method and coated steel
CN102002299A (en) Fingerprint-resistant paint and preparation method thereof
KR101696604B1 (en) Organic-inorganic hybrid coating composition for plated steel sheet
JP6569194B2 (en) Surface-treated hot-dip galvanized steel sheet with excellent corrosion resistance
JP2004307897A (en) Surface-treated metal having silica-zirconia film, and method of manufacturing the same
JP4611166B2 (en) Chromate-free clear-coated stainless steel sheet and method for producing the same
CN101914344B (en) Non-chrome water-based organic fingerprint-resistant coating and preparation method thereof
JP5314547B2 (en) Surface treatment agent for metal material, surface treatment method, and surface treatment metal material
JP2006281710A (en) Coated steel plate excellent in film adhesion and its manufacturing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150311