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CN109666928A - A kind of protective coating of fastener and preparation method thereof and its application - Google Patents

A kind of protective coating of fastener and preparation method thereof and its application Download PDF

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Publication number
CN109666928A
CN109666928A CN201811585078.9A CN201811585078A CN109666928A CN 109666928 A CN109666928 A CN 109666928A CN 201811585078 A CN201811585078 A CN 201811585078A CN 109666928 A CN109666928 A CN 109666928A
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CN
China
Prior art keywords
protective coating
silane
coating
thickness
sodium
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
CN201811585078.9A
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Chinese (zh)
Inventor
智强
李庆鹏
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.)
Beijing Sai Zhi Technology Co Ltd
Dongguan University of Technology
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Beijing Sai Zhi Technology Co Ltd
Dongguan University of Technology
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Application filed by Beijing Sai Zhi Technology Co Ltd, Dongguan University of Technology filed Critical Beijing Sai Zhi Technology Co Ltd
Priority to CN201811585078.9A priority Critical patent/CN109666928A/en
Publication of CN109666928A publication Critical patent/CN109666928A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0881—Titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

本发明提供了一种紧固件的防护涂层及其制备方法和其应用。本发明提供的防护涂层，采用硅烷转化膜做为紧固件的表面处理层，再采用有机涂层对转化膜进行封闭，是一种具有耐蚀性能好、涂层薄、且与基体结合强度高、耐磨性能好的复合涂层。本发明采用硅烷转化膜/有机涂层双层防护的表面处理技术，解决了紧固件在应用上的限制，且在保证涂层薄(8～15μm)，与基体结合强度高的情况下，较大程度的提高涂层的耐中性盐雾腐蚀性能和改善了涂层的耐磨性能，且防护涂层的制备工艺简单，方便。The present invention provides a protective coating for fasteners and a preparation method and application thereof. The protective coating provided by the invention adopts the silane conversion film as the surface treatment layer of the fastener, and then uses the organic coating to seal the conversion film. Composite coating with high strength and good wear resistance. The invention adopts the surface treatment technology of double-layer protection of silane conversion film/organic coating, which solves the limitation on the application of fasteners. The neutral salt spray corrosion resistance of the coating is greatly improved and the wear resistance of the coating is improved, and the preparation process of the protective coating is simple and convenient.

Description

A kind of protective coating of fastener and preparation method thereof and its application
Technical field
The invention belongs to the surface protection technique fields of fastener, and in particular to a kind of protective coating and its system of fastener Preparation Method and its application.
Background technique
Marine environment is one of corrosiveness the most harsh environment in nature, and most metals material is all intolerant to sea Water, sea atmosphere corrosion.Many be chronically exposed to the threaded fastener in marine environment corrosion it is very serious, corrosion cause to fasten Part is difficult to dismantle, and bonding strength decline, or even the problems such as forfeiture occur, and causes to fastener normal service and maintenance very big Difficulty, and there are dimensional problems for fastener, can not coat thicker coating and be protected.
By factors such as analysis fastener material, design feature, use conditions, in conjunction with marine environment feature, screw thread Fastener is primarily present a variety of corrosion types such as crevice corrosion, galvanic corrosion, stress corrosion and fretting corrosion, corrosion influence factors It is extremely complex.Single sufacing not can effectively solve corrosion present in fastener and asked due to itself intrinsic limitation Topic [theory and Beijing technology [M] of Xu Binshi, Zhu Shaohua Surface Engineering: National Defense Industry Press, 2009:333.].Currently, Threaded fastener is more commonly used in engineering anti-corrosion applies, coating has galvanizing by dipping, Electroless Plating Ni-P alloy layer, vacuum zincizing, Zinc-chromium coating etc..Wherein, galvanizing by dipping antiseptic property is general, and coating is thicker, be easy to cause bolts and nuts assembly difficulty；Vacuum Zinc coat has certain corrosion resistance, and with substrate combinating strength height, wearability is good, but salt spray corrosion resistance≤300h； Zinc-chromium coating excellent anti-corrosion performance, salt spray test time >=1000h, coating layer thickness≤10 μm do not influence the assembly of fastener, But hardness is low, wearability is slightly worse, and [threaded fastener is compound anti-under Bian Feilong, Huang Yanbin, Shi little Jun, Song Gaowei marine environment Rotten technology [J] plating and covering with paint, 2010,29 (12): 64-66.].
Summary of the invention
The present invention aiming at the shortcomings in the prior art, mainly for some surfaces such as current plating, chemical plating, composite coatings Means of defence is unable to satisfy application of the fastener in more adverse circumstances, provides a kind of good, coating with corrosion resisting property Preparation method thin and with substrate combinating strength is high, wear-resisting property is good composite coating and the composite coating.The present invention mentions The preparation method of confession solves fastener and exists including using silane conversion film/organic coating Double-protection process for treating surface Using upper limitation, and in the case where guaranteeing coating thin (5~15 μm) with substrate combinating strength height, largely improve The resistance to Neutral Salt Spray Corrosion performance of coating and the wear-resisting property for improving coating.
It is an object of the present invention to provide a kind of protective coating, the protective coating includes silane conversion film and organic painting Layer；
Wherein the raw material for preparing of silane conversion film includes: silane coupling agent, cosolvent, corrosion inhibiter, surfactant and pH Regulator；
The raw material for preparing of organic coating includes: resin, filler, auxiliary agent and solvent；
It will be soaked in the solution for preparing raw material including the silane conversion film i.e. silane conversion fluid, take out to shielding Silane conversion film is obtained after solidification；The organic coating is coated on silane conversion film again and obtains protective coating.
At least one of specifically, the protective coating further includes following 1) -21) described:
1) in the silane conversion fluid of every 1L, the content of each component includes:
4~40g/L of silane coupling agent；
4~50g/L of cosolvent；
1~15g/L of corrosion inhibiter；
0.1~15g/L of surfactant；
0.1~5g/L of pH adjusting agent；
2) the silane conversion fluid further includes water；
Specifically, the water is deionized water；
3) organic coating prepares the mass percentage of raw material and includes:
Resin 5%~65%；
Filler 4%~30%；
Auxiliary agent 0.1%~5%；
Remaining is solvent, and the sum of each component mass percentage is 100%；
4) silane coupling agent includes KH540, KH550, KH560, KH561, KH570, KH571, KH580 and/or KH590；
5) cosolvent includes ethylene glycol ether acetate, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether and/or third Glycol methyl ether acetate；
6) corrosion inhibiter includes calgon, sodium molybdate, salicylic acid, benzotriazole, 8-hydroxyquinoline, pyridine, benzene first Acid and/or citric acid；
7) surfactant includes cationic surfactant, anionic surfactant and/or non-ionic surface active Agent；
8) pH adjusting agent includes ammonium hydroxide and/or acetic acid；
9) resin includes epoxy resin, acrylic resin, fluorocarbon resin and/or polyurethane resin；
10) filler includes aluminium powder, titanium valve, molybdenum disulfide, polytetrafluoroethylene (PTFE), polyethylene wax, zinc powder, silica, oxidation Aluminium, zinc oxide, ferrotitanium powder, iron oxide red and/or copper powder；
11) auxiliary agent includes dispersing agent, levelling agent and/or defoaming agent；
12) solvent includes dimethylbenzene, gylcol ether, propylene glycol, propylene glycol ethers, methanol, ethyl alcohol, ethylene glycol esters And/or propylene glycol esters；
13) soaking time includes 1min~5min；
14) curing time includes 10min~60min；
15) solidification temperature includes 30 DEG C~200 DEG C；
It 16) further include carrying out oil removing and/or derusting to shielding to described before the immersion；
17) thickness of silane conversion film includes 0.5~10 μm；
18) thickness of organic coating includes 3~10 μm；
19) thickness of protective coating includes 5~15 μm；
It 20) further include solidifying again after the coating organic coating；
21) described to shielding includes fastener.
At least one of again specifically, any protective coating further includes following 1) -17) described:
1) cationic surfactant include dodecyl trimethyl ammonium bromide, octadecyltrimethylammonium chloride, and/or Hexadecyltrimethylammonium chloride；
2) anionic surfactant includes neopelex, fatty alcohol acyl sulfate sodium and/or ethoxylation rouge Fatty acid methyl esters sodium sulfonate；
3) nonionic surfactant includes that alkyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, octyl phenol are poly- Ethylene oxide ether, NP-4 and/or aliphatic acid polyethenoxy ether；
4) oil removing includes carrying out oil removing using degreasing fluid, and the degreasing fluid includes: sodium hydroxide, sodium carbonate, phosphoric acid Trisodium, sodium metasilicate and OP-10 emulsifier；
5) derusting includes being derusted using rust removing solution, and the rust removing solution includes hydrochloric acid and nitric acid；
6) soaking time includes 2min~3min；
7) curing time includes 30min~40min；
8) solidification temperature includes 100 DEG C~170 DEG C；
9) thickness of silane conversion film includes 2~5 μm；
10) thickness of organic coating includes 5~10 μm；
11) thickness of protective coating includes 7~15 μm；
12) curing time cured again includes 30min~60min；
13) solidification temperature cured again includes 200 DEG C~240 DEG C；
14) in the silane conversion fluid of every 1L, the content of each component includes:
Silane coupling agent 25g/L~31g/L；
Cosolvent 15g/L~35g/L；
Corrosion inhibiter 1g/L~3g/L；
Surfactant 1g/L~2g/L；
PH adjusting agent 0.1g/L~0.3g/L；
15) organic coating prepares the mass percentage of raw material and includes:
Resin 20%~30%；
Filler 12%~16%；
Auxiliary agent 0.5%~0.6%；
Remaining is solvent, and the sum of each component mass percentage is 100%.
16) fastener includes the fastener of iron and steel material quality；
17) fastener includes fastener used in marine environment.
At least one of also specifically, any protective coating further includes following 1) -11) described:
It 1) include: 3~15g/L of sodium hydroxide in the degreasing fluid of every 1L；20~80g/L of sodium carbonate；Tertiary sodium phosphate 50~ 100g/L；5~15g/L of sodium metasilicate；0.2~3g/L of OP-10 emulsifier；Remaining is water；
It specifically includes: 5~10g/L of sodium hydroxide；20~65g/L of sodium carbonate；50~85g/L of tertiary sodium phosphate；Sodium metasilicate 5~ 10g/L；0.2~3g/L of OP-10 emulsifier；Remaining is water；
It specifically includes again: 10,5 and/or 8g/L of sodium hydroxide；20,50 and/or 65g/L of sodium carbonate；Tertiary sodium phosphate 50,60, 80 and/or 85g/L；5,7,10 and/or 9g/L of sodium metasilicate；0.2,3,0.7 and/or 0.5g/L of OP-10 emulsifier；Remaining is water；
2) (please verify) in the rust removing solution of every 1L includes: 2~10g/L of hydrochloric acid；10~20g/L of nitric acid；Remaining is water；
It specifically includes: 5~10g/L of hydrochloric acid；10~15g/L of nitric acid；
It specifically includes again: 5,10,8 and/or 9g/L of hydrochloric acid；15,10 and/or 12g/L of nitric acid；
3) soaking time includes 2min and/or 3min；
4) curing time includes 40min and/or 30min；
5) solidification temperature includes 100 DEG C, 110 DEG C, 120 DEG C, 150 DEG C and/or 170 DEG C；
6) thickness of silane conversion film includes 2~4 μm, 1~3 μm and/or 3~5 μm；
7) thickness of organic coating includes 5~8 μm, 6~10 μm, 7~10 μm, 5~7 μm and/or 6~8 μm；
8) thickness of protective coating include 8~15 μm, 10~15 μm, 7~12 μm, 7~13 μm, 7~11 μm and/or 9~ 13μm；
9) cured solidification temperature includes 200 DEG C, 220 DEG C, 230 DEG C and/or 240 DEG C again；
10) in the silane conversion fluid of every 1L, the content of each component includes:
Silane coupling agent 25g/L, 31g/L, 30g/L and/or 27g/L；
Cosolvent 25g/L, 35g/L and/or 15g/L；
Corrosion inhibiter 3g/L and/or 1g/L；
Surfactant 1g/L and/or 2g/L；
PH adjusting agent 0.1g/L, 0.2g/L and/or 0.3g/L；
11) organic coating prepares the mass percentage of raw material and includes:
Resin 30%, 25%, 23%, 28% and/or 20%；
Filler 13%, 12%, 14% and/or 16%；
Auxiliary agent 0.6% and/or 0.5%；
Remaining is solvent, and the sum of each component mass percentage is 100%.
It is a further object to provide a kind of preparation methods of protective coating, which comprises will be wait protect Product are soaked in the solution for preparing raw material including silane conversion film i.e. silane conversion fluid, obtain silane conversion film after taking out solidification； Organic coating is coated on silane conversion film again obtains protective coating；
Wherein the raw material for preparing of silane conversion film includes: silane coupling agent, cosolvent, corrosion inhibiter, surfactant and pH Regulator；
The raw material for preparing of organic coating includes: resin, filler, auxiliary agent and solvent.
At least one of specifically, the method also includes following 1) -21) described:
1) in the silane conversion fluid of every 1L, the content of each component includes:
4~40g/L of silane coupling agent；
4~50g/L of cosolvent；
1~15g/L of corrosion inhibiter；
0.1~15g/L of surfactant；
0.1~5g/L of pH adjusting agent；
2) the silane conversion fluid further includes water；
Specifically, the water is deionized water；
3) organic coating prepares the mass percentage of raw material and includes:
Resin 5%~65%；
Filler 4%~30%；
Auxiliary agent 0.1%~5%；
Remaining is solvent, and the sum of each component mass percentage is 100%；
4) silane coupling agent includes KH540, KH550, KH560, KH561, KH570, KH571, KH580 and/or KH590；
5) cosolvent includes ethylene glycol ether acetate, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether and/or third Glycol methyl ether acetate；
6) corrosion inhibiter includes calgon, sodium molybdate, salicylic acid, benzotriazole, 8-hydroxyquinoline, pyridine, benzene first Acid and/or citric acid；
7) surfactant includes cationic surfactant, anionic surfactant and/or non-ionic surface active Agent；
8) pH adjusting agent includes ammonium hydroxide and/or acetic acid；
9) resin includes epoxy resin, acrylic resin, fluorocarbon resin and/or polyurethane resin；
10) filler includes aluminium powder, titanium valve, molybdenum disulfide, polytetrafluoroethylene (PTFE), polyethylene wax, zinc powder, silica, oxidation Aluminium, zinc oxide, ferrotitanium powder, iron oxide red and/or copper powder；
11) auxiliary agent includes dispersing agent, levelling agent and/or defoaming agent；
12) solvent includes dimethylbenzene, gylcol ether, propylene glycol, propylene glycol ethers, methanol, ethyl alcohol, ethylene glycol esters And/or propylene glycol esters；
13) soaking time includes 1min~5min；
14) curing time includes 10min~60min；
15) solidification temperature includes 30 DEG C~200 DEG C；
It 16) further include carrying out oil removing and/or derusting to shielding to described before the immersion；
17) thickness of silane conversion film includes 0.5~10 μm；
18) thickness of organic coating includes 3~10 μm；
19) thickness of protective coating includes 5~15 μm；
It 20) further include solidifying again after the coating organic coating；
21) described to shielding includes fastener.
At least one of again specifically, any protective coating further includes following 1) -17) described:
1) cationic surfactant include dodecyl trimethyl ammonium bromide, octadecyltrimethylammonium chloride, and/or Hexadecyltrimethylammonium chloride；
2) anionic surfactant includes neopelex, fatty alcohol acyl sulfate sodium and/or ethoxylation rouge Fatty acid methyl esters sodium sulfonate；
3) nonionic surfactant includes that alkyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, octyl phenol are poly- Ethylene oxide ether, NP-4 and/or aliphatic acid polyethenoxy ether；
4) oil removing includes carrying out oil removing using degreasing fluid, and the degreasing fluid includes: sodium hydroxide, sodium carbonate, phosphoric acid Trisodium, sodium metasilicate and OP-10 emulsifier；
5) derusting includes being derusted using rust removing solution, and the rust removing solution includes hydrochloric acid and nitric acid；
6) soaking time includes 2min~3min；
7) curing time includes 30min~40min；
8) solidification temperature includes 100 DEG C~170 DEG C；
9) thickness of silane conversion film includes 2~5 μm；
10) thickness of organic coating includes 5~10 μm；
11) thickness of protective coating includes 7~15 μm；
12) curing time cured again includes 30min~60min；
13) solidification temperature cured again includes 200 DEG C~240 DEG C；
14) in the silane conversion fluid of every 1L, the content of each component includes:
Silane coupling agent 25g/L~31g/L；
Cosolvent 15g/L~35g/L；
Corrosion inhibiter 1g/L~3g/L；
Surfactant 1g/L~2g/L；
PH adjusting agent 0.1g/L~0.3g/L；
15) organic coating prepares the mass percentage of raw material and includes:
Resin 20%~30%；
Filler 12%~16%；
Auxiliary agent 0.5%~0.6%；
Remaining is solvent, and the sum of each component mass percentage is 100%.
16) fastener includes the fastener of iron and steel material quality；
17) fastener includes fastener used in marine environment.
At least one of also specifically, any protective coating further includes following 1) -11) described:
It 1) include: 3~15g/L of sodium hydroxide in the degreasing fluid of every 1L；20~80g/L of sodium carbonate；Tertiary sodium phosphate 50~ 100g/L；5~15g/L of sodium metasilicate；0.2~3g/L of OP-10 emulsifier；Remaining is water；
It specifically includes: 5~10g/L of sodium hydroxide；20~65g/L of sodium carbonate；50~85g/L of tertiary sodium phosphate；Sodium metasilicate 5~ 10g/L；0.2~3g/L of OP-10 emulsifier；Remaining is water；
It specifically includes again: 10,5 and/or 8g/L of sodium hydroxide；20,50 and/or 65g/L of sodium carbonate；Tertiary sodium phosphate 50,60, 80 and/or 85g/L；5,7,10 and/or 9g/L of sodium metasilicate；0.2,3,0.7 and/or 0.5g/L of OP-10 emulsifier；Remaining is water；
It 2) include: 2~10g/L of hydrochloric acid in the rust removing solution of every 1L；10~20g/L of nitric acid；Remaining is water；
It specifically includes: 5~10g/L of hydrochloric acid；10~15g/L of nitric acid；
It specifically includes again: 5,10,8 and/or 9g/L of hydrochloric acid；15,10 and/or 12g/L of nitric acid；
3) soaking time includes 2min and/or 3min；
4) curing time includes 40min and/or 30min；
5) solidification temperature includes 100 DEG C, 110 DEG C, 120 DEG C, 150 DEG C and/or 170 DEG C；
6) thickness of silane conversion film includes 2~4 μm, 1~3 μm and/or 3~5 μm；
7) thickness of organic coating includes 5~8 μm, 6~10 μm, 7~10 μm, 5~7 μm and/or 6~8 μm；
8) thickness of protective coating include 8~15 μm, 10~15 μm, 7~12 μm, 7~13 μm, 7~11 μm and/or 9~ 13μm；
9) cured solidification temperature includes 200 DEG C, 220 DEG C, 230 DEG C and/or 240 DEG C again；
10) in the silane conversion fluid of every 1L, the content of each component includes:
Silane coupling agent 25g/L, 31g/L, 30g/L and/or 27g/L；
Cosolvent 25g/L, 35g/L and/or 15g/L；
Corrosion inhibiter 3g/L and/or 1g/L；
Surfactant 1g/L and/or 2g/L；
PH adjusting agent 0.1g/L, 0.2g/L and/or 0.3g/L；
11) organic coating prepares the mass percentage of raw material and includes:
Resin 30%, 25%, 23%, 28% and/or 20%；
Filler 13%, 12%, 14% and/or 16%；
Auxiliary agent 0.6% and/or 0.5%；
Remaining is solvent, and the sum of each component mass percentage is 100%.
It is also another object of the present invention to provide the protective coatings that any the method for the present invention is directly prepared.
It is of the invention a further object is the present invention any protective coating is provided, any the method for the invention is answered With.
Specifically, the application includes
1) protection of fastener；
2) product of the preparation for fastener protection.
The fastener includes fastener used in marine environment；And/or the fastener includes the tight of iron and steel material quality Firmware.
Any silane coupling agent of the present invention includes gamma-amino propyl trimethoxy silicane, gamma-aminopropyl-triethoxy Silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidoxypropyltrietandysilane andysilane, γ-(methyl Acryloyl-oxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) hydroxypropyl methyl dimethoxysilane, γ-three second of mercapto propyl One of oxysilane, γ-mercaptopropyl trimethoxysilane are a variety of.
The advantages of the present invention are:
1, the present invention using silane conversion film as fastener surface-treated layer, the layer not only with metal fastenings matrix It is combined, and can largely improve the binding force between coating and matrix as middle layer, film layer treatment process is simple, side Just.
2, conversion film is closed using organic coating, Double-protection effect, efficiently solve corrosion resistance coating can it is poor, The disadvantages of wear-resisting property is poor.
3, coated bodies of the present invention are rationally perfect, and composite coating plays excellent performance in the case where relatively thin.
In short, total coating thickness of the present invention at 5~15 μm, in the binding force for guaranteeing coating and matrix, changes compound painting Layer current potential makes coating have preferable corrosion resistance, and the resistance to neutral salt spray time is not corroded or even resistance to neutrality in 720h or more The salt fog time can reach 1500h and not corrode.
Specific embodiment
Made in following embodiments, experimental method is conventional method unless otherwise specified.
Material as used in the following examples etc., is commercially available unless otherwise specified.
Following embodiments and its illustrate for explanation and understanding the present invention, do not constitute to improper limit of the invention It is fixed.
Embodiment 1
Firstly, preparing sample, the fastener of iron and steel material quality is subjected to oil removing in alkaline degreasing liquid, later with a large amount of water It is cleaned, is then derusted in acidic derusting liquid, massive laundering is dry.
Degreasing fluid is mixed by sodium hydroxide, sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifier, each component Content is as follows:
Sodium hydroxide 10g/L；Sodium carbonate 20g/L；Tertiary sodium phosphate 50g/L；Sodium metasilicate 5g/L；OP-10 emulsifier 0.2g/L； Remaining is water (total amount 1L).
Rust removing solution is mixed by hydrochloric acid, nitric acid, and the content of each component is as follows:
Hydrochloric acid 5g/L；Nitric acid 15g/L；Remaining is water (total amount 1L).
Then, fastener is immersed in 2min in hydrolyzed silane solution, hydrolyzed silane solution composition is as follows:
KH560 20g/L；KH570 5g/L；Ethylene glycol ether acetate 15g/L；Sodium molybdate 3g/L；Surfactant OP- 10 1g/L；Acetic acid 0.1g/L；Remaining is water (total amount 1L).
It takes out, solidifies 40min at 120 DEG C, 2~4 μm of thicknesses of layers.
There is the fastener of silane film to coat one layer of organic coating, by weight percentage, the present embodiment organic painting on surface Material is uniformly mixed by following component:
Epoxy resin 25；Aluminium powder 10；Molybdenum disulfide 2；Dispersing agent (German Bi Ke chemical company BYK-163) 0.2；Levelling agent (German Bi Ke chemical company BYK-306) 0.3；Defoaming agent (German Bi Ke chemical company BYK-141) 0.1；Remaining is ethylene glycol Butyl ether (the sum of all components are 100%).
Then, solidify 30-60min at 200 DEG C, take out, coating preparation finishes, coating with a thickness of 5~8 μm, coating Overall thickness is at 7~12 μm.
The composite coating protection system coating binding force prepared with the method is good, and wearability is excellent, the 800h of resistance to neutral salt spray It does not corrode.
Embodiment 2:
Firstly, preparing sample, the fastener of iron and steel material quality is subjected to oil removing in alkaline degreasing liquid, later with a large amount of water It is cleaned, is then derusted in acidic derusting liquid, massive laundering is dry.
Degreasing fluid is mixed by sodium hydroxide, sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifier, each component Content is as follows:
Sodium hydroxide 10g/L；Sodium carbonate 20g/L；Tertiary sodium phosphate 50g/L；Sodium metasilicate 5g/L；OP-10 emulsifier 0.2g/L； Remaining is water (total amount 1L).
Rust removing solution is mixed by hydrochloric acid, nitric acid, and the content of each component is as follows:
Hydrochloric acid 5g/L；Nitric acid 15g/L；Remaining is water (total amount 1L).
Then, fastener is immersed in 3min in hydrolyzed silane solution, hydrolyzed silane solution composition is as follows:
KH560 21g/L；KH540 10g/L；Propylene glycol methyl ether acetate 25g/L；Citric acid 1g/L；Surfactant NP-9 1g/L；Acetic acid 0.1g/L；Remaining is water (total amount 1L).
It takes out, solidifies 30min at 100 DEG C, 1~3 μm of thicknesses of layers.
There is the fastener of silane film to coat one layer of organic coating, by weight percentage, the present embodiment organic painting on surface Material is uniformly mixed by following component:
Acrylic resin 30；Aluminium powder 12；Polytetrafluoroethylene (PTFE) 1；Dispersing agent (German Bi Ke chemical company BYK-110) 0.3；Stream Flat agent (German Bi Ke chemical company BYK-331) 0.2；Defoaming agent (German Bi Ke chemical company BYK-141) 0.1；Remaining is second Glycol butyl ether (the sum of all components are 100%).
Then, solidify 30-60min at 230 DEG C, take out, coating preparation finishes, coating with a thickness of 6~10 μm, coating Overall thickness is at 7~13 μm.
The composite coating protection system coating binding force prepared with the method is good, and wearability is excellent, the 720h of resistance to neutral salt spray It does not corrode.
Embodiment 3:
Firstly, preparing sample, the fastener of iron and steel material quality is subjected to oil removing in alkaline degreasing liquid, later with a large amount of water It is cleaned, is then derusted in acidic derusting liquid, massive laundering is dry.
Degreasing fluid is mixed by sodium hydroxide, sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifier, each component Content is as follows:
Sodium hydroxide 10g/L；Sodium carbonate 50g/L；Tertiary sodium phosphate 60g/L；Sodium metasilicate 7g/L；OP-10 emulsifier 3g/L；Its Yu Weishui (total amount 1L).
Rust removing solution is mixed by hydrochloric acid, nitric acid, and the content of each component is as follows:
Hydrochloric acid 10g/L；Nitric acid 10g/L；Remaining is water (total amount 1L).
Then, fastener is immersed in 2min in hydrolyzed silane solution, hydrolyzed silane solution composition is as follows:
KH560 25g/L；KH561 5g/L；Propylene glycol methyl ether acetate 35g/L；Sodium molybdate 1g/L；Surfactant NP- 9 1g/L；Face activating agent NP-4 1g/L；Acetic acid 0.2g/L；Remaining is water (total amount 1L).
It takes out, solidifies 40min at 170 DEG C, 3~5 μm of thicknesses of layers.
There is the fastener of silane film to coat one layer of organic coating, by weight percentage, the present embodiment organic painting on surface Material is uniformly mixed by following component:
Fluorocarbon resin 23；Aluminium powder 11；Titanium valve 3；Dispersing agent (German Bi Ke chemical company BYK-161) 0.3；Levelling agent (moral Guo Bike chemical company BYK-331) 0.2；Defoaming agent (German Bi Ke chemical company BYK-141) 0.1；Remaining is propandiol butyl ether (the sum of all components are 100%).
Then, solidify 30-60min at 240 DEG C, take out, coating preparation finishes, coating with a thickness of 7~10 μm, coating Overall thickness is at 10~15 μm.
The composite coating protection system coating binding force prepared with the method is good, and wearability is excellent, the 1300h of resistance to neutral salt spray It does not corrode.
Embodiment 4:
Firstly, preparing sample, the fastener of iron and steel material quality is subjected to oil removing in alkaline degreasing liquid, later with a large amount of water It is cleaned, is then derusted in acidic derusting liquid, massive laundering is dry.
Degreasing fluid is mixed by sodium hydroxide, sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifier, each component Content is as follows:
Sodium hydroxide 5g/L；Sodium carbonate 65g/L；Tertiary sodium phosphate 80g/L；Sodium metasilicate 10g/L；OP-10 emulsifier 0.7g/L； Remaining is water (total amount 1L).
Rust removing solution is mixed by hydrochloric acid, nitric acid, and the content of each component is as follows:
Hydrochloric acid 8g/L；Nitric acid 12g/L；Remaining is water (total amount 1L).
Then, fastener is immersed in 2min in hydrolyzed silane solution, hydrolyzed silane solution composition is as follows:
KH570 25g/L；KH540 5g/L；Propylene glycol monomethyl ether 25g/L；Sodium molybdate 1g/L；Surfactant NP-9 1g/ L；Acetic acid 0.3g/L；Remaining is water (total amount 1L).
It takes out, solidifies 40min at 110 DEG C, 2~4 μm of thicknesses of layers.
There is the fastener of silane film to coat one layer of organic coating, by weight percentage, the present embodiment organic painting on surface Material is uniformly mixed by following component:
Epoxy resin 28；Aluminium powder 15；Polytetrafluoroethylene (PTFE) 1；Dispersing agent (German Bi Ke chemical company BYK-161) 0.3；Levelling Agent (German Bi Ke chemical company BYK-331) 0.2；Defoaming agent (German Bi Ke chemical company BYK-141) 0.1；Remaining is the third two Alcohol methyl ether (the sum of all components are 100%).
Then, solidify 30-60min at 220 DEG C, take out, coating preparation finishes, coating with a thickness of 5~7 μm, coating Overall thickness is at 7~11 μm.
The composite coating protection system coating binding force prepared with the method is good, and wearability is excellent, the 800h of resistance to neutral salt spray It does not corrode.
Embodiment 5:
Firstly, preparing sample, the fastener of iron and steel material quality is subjected to oil removing in alkaline degreasing liquid, later with a large amount of water It is cleaned, is then derusted in acidic derusting liquid, massive laundering is dry.
Degreasing fluid is mixed by sodium hydroxide, sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifier, each component Content is as follows:
Sodium hydroxide 8g/L；Sodium carbonate 65g/L；Tertiary sodium phosphate 85g/L；Sodium metasilicate 9g/L；OP-10 emulsifier 0.5g/L； Remaining is water (total amount 1L).
Rust removing solution is mixed by hydrochloric acid, nitric acid, and the content of each component is as follows:
Hydrochloric acid 9g/L；Nitric acid 15g/L；Remaining is water (total amount 1L).
Then, fastener is immersed in 2min in hydrolyzed silane solution, hydrolyzed silane solution composition is as follows:
KH561 22g/L；KH570 5g/L；Ethylene glycol monobutyl ether 25g/L；Sodium molybdate 1g/L；Surfactant NP-9 1g/L；Acetic acid 0.2g/L；Remaining is water (total amount 1L).
It takes out, solidifies 40min at 150 DEG C, 3~5 μm of thicknesses of layers.
There is the fastener of silane film to coat one layer of organic coating, by weight percentage, the present embodiment organic painting on surface Material is uniformly mixed by following component:
Epoxy resin 20；Aluminium powder 13；Polytetrafluoroethylene (PTFE) 1；Dispersing agent (German Bi Ke chemical company BYK-161) 0.2；Levelling Agent (German Bi Ke chemical company BYK-331) 0.1；Defoaming agent (German Bi Ke chemical company BYK-141) 0.2；Remaining is second two Alcohol butyl ether (the sum of all components are 100%).
Then, solidify 30-60min at 200 DEG C, take out, coating preparation finishes, coating with a thickness of 6~8 μm, coating Overall thickness is at 9~13 μm.
The composite coating protection system coating binding force prepared with the method is good, and wearability is excellent, the 900h of resistance to neutral salt spray It does not corrode.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations Art scheme should all be fallen within the scope and spirit of the invention.

Claims (10)

1.一种防护涂层，其特征在于，所述防护涂层包括硅烷转化膜和有机涂层；1. A protective coating, characterized in that the protective coating comprises a silane conversion film and an organic coating; 其中硅烷转化膜的制备原料包括：硅烷偶联剂、助溶剂、缓蚀剂、表面活性剂和pH调节剂；The raw materials for the preparation of the silane conversion film include: silane coupling agent, cosolvent, corrosion inhibitor, surfactant and pH adjuster; 有机涂层的制备原料包括：树脂、填料、助剂和溶剂；The raw materials for the preparation of organic coatings include: resins, fillers, additives and solvents; 将待防护品浸泡于包括所述硅烷转化膜的制备原料的溶液即硅烷转化液中，取出固化后得硅烷转化膜；再在硅烷转化膜上涂覆所述有机涂层得防护涂层。The product to be protected is immersed in a solution containing the raw materials for preparing the silane conversion film, that is, a silane conversion solution, taken out and cured to obtain a silane conversion film; and then the organic coating is applied on the silane conversion film to obtain a protective coating. 2.根据权利要求1所述的防护涂层，其特征在于，所述防护涂层还包括下述1)-21)所述中的至少一种：2. The protective coating according to claim 1, wherein the protective coating further comprises at least one of the following 1)-21): 1)每1L的硅烷转化液中，各组分的含量包括：1) In every 1L of silane conversion solution, the content of each component includes: 硅烷偶联剂4～40g/L；Silane coupling agent 4～40g/L; 助溶剂4～50g/L；Cosolvent 4～50g/L; 缓蚀剂1～15g/L；Corrosion inhibitor 1～15g/L; 表面活性剂0.1～15g/L；Surfactant 0.1～15g/L; pH调节剂0.1～5g/L；pH adjuster 0.1～5g/L; 2)所述硅烷转化液还包括水；2) the silane conversion liquid also includes water; 具体的，所述水为去离子水；Specifically, the water is deionized water; 3)有机涂层制备原料的质量百分含量包括：3) The mass percentage of raw materials for organic coating preparation includes: 树脂5％～65％；Resin 5%～65%; 填料4％～30％；Filler 4%～30%; 助剂0.1％～5％；Auxiliary 0.1%～5%; 其余为溶剂，各组分质量百分含量之和为100％；The rest are solvents, and the sum of the mass percentages of each component is 100%; 4)硅烷偶联剂包括KH540、KH550、KH560、KH561、KH570、KH571、KH580和/或KH590；4) Silane coupling agents include KH540, KH550, KH560, KH561, KH570, KH571, KH580 and/or KH590; 5)助溶剂包括乙二醇乙醚醋酸酯、乙二醇乙醚、乙二醇丁醚、丙二醇甲醚和/或丙二醇甲醚醋酸酯；5) cosolvents include ethylene glycol ethyl ether acetate, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether and/or propylene glycol methyl ether acetate; 6)缓蚀剂包括六偏磷酸钠、钼酸钠、水杨酸、苯并三氮唑、8-羟基喹啉、吡啶、苯甲酸和/或柠檬酸；6) Corrosion inhibitors include sodium hexametaphosphate, sodium molybdate, salicylic acid, benzotriazole, 8-hydroxyquinoline, pyridine, benzoic acid and/or citric acid; 7)表面活性剂包括阳离子表面活性剂、阴离子表面活性剂和/或非离子表面活性剂；7) Surfactants include cationic surfactants, anionic surfactants and/or nonionic surfactants; 8)pH调节剂包括氨水和/或醋酸；8) pH regulators include ammonia and/or acetic acid; 9)树脂包括环氧树脂、丙烯酸树脂、氟碳树脂和/或聚氨酯树脂；9) Resins include epoxy resin, acrylic resin, fluorocarbon resin and/or polyurethane resin; 10)填料包括铝粉、钛粉、二硫化钼、聚四氟乙烯、聚乙烯蜡、锌粉、二氧化硅、氧化铝、氧化锌、铁钛粉、氧化铁红和/或铜粉；10) Fillers include aluminum powder, titanium powder, molybdenum disulfide, polytetrafluoroethylene, polyethylene wax, zinc powder, silica, alumina, zinc oxide, iron titanium powder, red iron oxide and/or copper powder; 11)所述助剂包括分散剂、流平剂和/或消泡剂；11) The auxiliary agent includes a dispersing agent, a leveling agent and/or a defoaming agent; 12)溶剂包括二甲苯、乙二醇醚类、丙二醇、丙二醇醚类、甲醇、乙醇、乙二醇酯类和/或丙二醇酯类；12) Solvents include xylene, glycol ethers, propylene glycol, propylene glycol ethers, methanol, ethanol, ethylene glycol esters and/or propylene glycol esters; 13)浸泡时间包括1min～5min；13) The soaking time includes 1min～5min; 14)固化时间包括10min～60min；14) Curing time includes 10min～60min; 15)固化温度包括30℃～200℃；15) Curing temperature includes 30℃～200℃; 16)所述浸泡前还包括对所述待防护品进行除油和/或除锈；16) Before the soaking, it also includes degreasing and/or rust removal on the object to be protected; 17)硅烷转化膜的厚度包括0.5～10μm；17) The thickness of the silane conversion film includes 0.5 to 10 μm; 18)有机涂层的厚度包括3～10μm；18) The thickness of the organic coating includes 3 to 10 μm; 19)防护涂层的厚度包括5～15μm；19) The thickness of the protective coating includes 5 to 15 μm; 20)所述涂覆所述有机涂层后，还包括再次固化；20) after the organic coating is applied, further curing is included; 21)所述待防护品包括紧固件。21) The item to be protected includes a fastener. 3.根据权利要求2所述的防护涂层，其特征在于，所述任一防护涂层还包括下述1)-17)所述中的至少一种：3. The protective coating according to claim 2, wherein any protective coating further comprises at least one of the following 1)-17): 1)阳离子表面活性剂包括十二烷基三甲基溴化铵、十八烷基三甲基氯化铵、和/或十六烷基三甲基氯化铵；1) cationic surfactants include dodecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, and/or cetyltrimethylammonium chloride; 2)阴离子表面活性剂包括十二烷基苯磺酸钠、脂肪醇酰硫酸钠和/或乙氧基化脂肪酸甲酯磺酸钠；2) anionic surfactants include sodium dodecylbenzenesulfonate, sodium fatty alcohol acyl sulfate and/or sodium ethoxylated fatty acid methyl ester sulfonate; 3)非离子表面活性剂包括烷基酚聚氧乙烯醚、壬基酚聚氧乙烯醚、辛烷基苯酚聚氧乙烯醚、NP-4和/或脂肪酸聚氧乙烯醚；3) Nonionic surfactants include alkylphenol ethoxylates, nonylphenol ethoxylates, octylphenol ethoxylates, NP-4 and/or fatty acid ethoxylates; 4)所述除油包括使用除油液进行除油，所述除油液包括：氢氧化钠、碳酸钠、磷酸三钠、硅酸钠和OP-10乳化剂；4) The degreasing comprises using degreasing liquid to remove oil, and the degreasing liquid includes: sodium hydroxide, sodium carbonate, trisodium phosphate, sodium silicate and OP-10 emulsifier; 5)所述除锈包括使用除锈液进行除锈，所述除锈液包括盐酸和硝酸；5) described rust removal comprises using rust removal liquid to carry out rust removal, and described rust removal liquid comprises hydrochloric acid and nitric acid; 6)浸泡时间包括2min～3min；6) The soaking time includes 2min～3min; 7)固化时间包括30min～40min；7) The curing time includes 30min～40min; 8)固化温度包括100℃～170℃；8) Curing temperature includes 100℃～170℃; 9)硅烷转化膜的厚度包括2～5μm；9) The thickness of the silane conversion film includes 2 to 5 μm; 10)有机涂层的厚度包括5～10μm；10) The thickness of the organic coating includes 5 to 10 μm; 11)防护涂层的厚度包括7～15μm；11) The thickness of the protective coating includes 7 to 15 μm; 12)所述再次固化的固化时间包括30min～60min；12) The curing time of the re-curing includes 30min～60min; 13)所述再次固化的固化温度包括200℃～240℃；13) The curing temperature of the re-curing includes 200°C to 240°C; 14)每1L的硅烷转化液中，各组分的含量包括：14) In every 1L of silane conversion solution, the content of each component includes: 硅烷偶联剂25g/L～31g/L；Silane coupling agent 25g/L～31g/L; 助溶剂15g/L～35g/L；Cosolvent 15g/L～35g/L; 缓蚀剂1g/L～3g/L；Corrosion inhibitor 1g/L～3g/L; 表面活性剂1g/L～2g/L；Surfactant 1g/L～2g/L; pH调节剂0.1g/L～0.3g/L；pH adjuster 0.1g/L～0.3g/L; 15)有机涂层制备原料的质量百分含量包括：15) The mass percentage of organic coating preparation raw materials includes: 树脂20％～30％；Resin 20%～30%; 填料12％～16％；Filler 12%～16%; 助剂0.5％～0.6％；Auxiliary 0.5%～0.6%; 其余为溶剂，各组分质量百分含量之和为100％。The rest are solvents, and the sum of the mass percentages of each component is 100%. 16)所述紧固件包括钢铁材质的紧固件；16) The fasteners include fasteners made of steel; 17)所述紧固件包括海洋环境中使用的紧固件。17) The fasteners include those used in marine environments. 4.根据权利要求3述的防护涂层，其特征在于，所述任一防护涂层还包括下述1)-11)所述中的至少一种：4. The protective coating according to claim 3, wherein any protective coating further comprises at least one of the following 1)-11): 1)每1L的除油液中包括：氢氧化钠3～15g/L；碳酸钠20～80g/L；磷酸三钠50～100g/L；硅酸钠5～15g/L；OP-10乳化剂0.2～3g/L；其余为水；1) Each 1L of degreasing solution includes: sodium hydroxide 3-15g/L; sodium carbonate 20-80g/L; trisodium phosphate 50-100g/L; sodium silicate 5-15g/L; OP-10 emulsification agent 0.2～3g/L; the rest is water; 2)每1L的除锈液中(请核实)包括：盐酸2～10g/L；硝酸10～20g/L；其余为水；2) Each 1L of rust removal solution (please verify) includes: hydrochloric acid 2～10g/L; nitric acid 10～20g/L; the rest is water; 3)浸泡时间包括2min和/或3min；3) The soaking time includes 2min and/or 3min; 4)固化时间包括40min和/或30min；4) Curing time includes 40min and/or 30min; 5)固化温度包括100℃、110℃、120℃、150℃和/或170℃；5) Curing temperature includes 100°C, 110°C, 120°C, 150°C and/or 170°C; 6)硅烷转化膜的厚度包括2～4μm、1～3μm和/或3～5μm；6) The thickness of the silane conversion film includes 2-4 μm, 1-3 μm and/or 3-5 μm; 7)有机涂层的厚度包括5～8μm、6～10μm、7～10μm、5～7μm和/或6～8μm；7) The thickness of the organic coating includes 5-8 μm, 6-10 μm, 7-10 μm, 5-7 μm and/or 6-8 μm; 8)防护涂层的厚度包括8～15μm、10～15μm、7～12μm、7～13μm、7～11μm和/或9～13μm；8) The thickness of the protective coating includes 8-15 μm, 10-15 μm, 7-12 μm, 7-13 μm, 7-11 μm and/or 9-13 μm; 9)再次固化的固化温度包括200℃、220℃、230℃和/或240℃；9) The curing temperature for re-curing includes 200°C, 220°C, 230°C and/or 240°C; 10)每1L的硅烷转化液中，各组分的含量包括：10) In every 1L of silane conversion solution, the content of each component includes: 硅烷偶联剂25g/L、31g/L、30g/L和/或27g/L；Silane coupling agent 25g/L, 31g/L, 30g/L and/or 27g/L; 助溶剂25g/L、35g/L和/或15g/L；Cosolvent 25g/L, 35g/L and/or 15g/L; 缓蚀剂3g/L和/或1g/L；Corrosion inhibitor 3g/L and/or 1g/L; 表面活性剂1g/L和/或2g/L；Surfactant 1g/L and/or 2g/L; pH调节剂0.1g/L、0.2g/L和/或0.3g/L；pH adjuster 0.1g/L, 0.2g/L and/or 0.3g/L; 11)有机涂层制备原料的质量百分含量包括：11) The mass percentage of raw materials for organic coating preparation includes: 树脂30％、25％、23％、28％和/或20％；Resin 30%, 25%, 23%, 28% and/or 20%; 填料13％、12％、14％和/或16％；Filler 13%, 12%, 14% and/or 16%; 助剂0.6％和/或0.5％；Auxiliary 0.6% and/or 0.5%; 其余为溶剂，各组分质量百分含量之和为100％。The rest are solvents, and the sum of the mass percentages of each component is 100%. 5.一种防护涂层的制备方法，其特征在于，所述方法包括：将待防护品浸泡于包括硅烷转化膜的制备原料的溶液即硅烷转化液中，取出固化后得硅烷转化膜；再在硅烷转化膜上涂覆有机涂层得防护涂层；5. A method for preparing a protective coating, characterized in that the method comprises: soaking a product to be protected in a solution comprising a silane conversion film preparation raw material, namely a silane conversion liquid, taking out and curing to obtain a silane conversion film; Coating an organic coating on the silane conversion film to obtain a protective coating; 其中硅烷转化膜的制备原料包括：硅烷偶联剂、助溶剂、缓蚀剂、表面活性剂和pH调节剂；The raw materials for the preparation of the silane conversion film include: silane coupling agent, cosolvent, corrosion inhibitor, surfactant and pH adjuster; 有机涂层的制备原料包括：树脂、填料、助剂和溶剂。The raw materials for the preparation of organic coatings include: resins, fillers, additives and solvents. 6.根据权利要求5所述的方法，其特征在于，所述方法还包括下述1)-21)所述中的至少一种：6. The method according to claim 5, wherein the method further comprises at least one of the following 1)-21): 1)每1L的硅烷转化液中，各组分的含量包括：1) In every 1L of silane conversion solution, the content of each component includes: 硅烷偶联剂4～40g/L；Silane coupling agent 4～40g/L; 助溶剂4～50g/L；Cosolvent 4～50g/L; 缓蚀剂1～15g/L；Corrosion inhibitor 1～15g/L; 表面活性剂0.1～15g/L；Surfactant 0.1～15g/L; pH调节剂0.1～5g/L；pH adjuster 0.1～5g/L; 2)所述硅烷转化液还包括水；2) the silane conversion liquid also includes water; 具体的，所述水为去离子水；Specifically, the water is deionized water; 3)有机涂层制备原料的质量百分含量包括：3) The mass percentage of raw materials for organic coating preparation includes: 树脂5％～65％；Resin 5%～65%; 填料4％～30％；Filler 4%～30%; 助剂0.1％～5％；Auxiliary 0.1%～5%; 其余为溶剂，各组分质量百分含量之和为100％；The rest are solvents, and the sum of the mass percentages of each component is 100%; 4)硅烷偶联剂包括KH540、KH550、KH560、KH561、KH570、KH571、KH580和/或KH590；4) Silane coupling agents include KH540, KH550, KH560, KH561, KH570, KH571, KH580 and/or KH590; 5)助溶剂包括乙二醇乙醚醋酸酯、乙二醇乙醚、乙二醇丁醚、丙二醇甲醚和/或丙二醇甲醚醋酸酯；5) cosolvents include ethylene glycol ethyl ether acetate, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether and/or propylene glycol methyl ether acetate; 6)缓蚀剂包括六偏磷酸钠、钼酸钠、水杨酸、苯并三氮唑、8-羟基喹啉、吡啶、苯甲酸和/或柠檬酸；6) Corrosion inhibitors include sodium hexametaphosphate, sodium molybdate, salicylic acid, benzotriazole, 8-hydroxyquinoline, pyridine, benzoic acid and/or citric acid; 7)表面活性剂包括阳离子表面活性剂、阴离子表面活性剂和/或非离子表面活性剂；7) Surfactants include cationic surfactants, anionic surfactants and/or nonionic surfactants; 8)pH调节剂包括氨水和/或醋酸；8) pH regulators include ammonia and/or acetic acid; 9)树脂包括环氧树脂、丙烯酸树脂、氟碳树脂和/或聚氨酯树脂；9) Resins include epoxy resin, acrylic resin, fluorocarbon resin and/or polyurethane resin; 10)填料包括铝粉、钛粉、二硫化钼、聚四氟乙烯、聚乙烯蜡、锌粉、二氧化硅、氧化铝、氧化锌、铁钛粉、氧化铁红和/或铜粉；10) Fillers include aluminum powder, titanium powder, molybdenum disulfide, polytetrafluoroethylene, polyethylene wax, zinc powder, silica, alumina, zinc oxide, iron titanium powder, red iron oxide and/or copper powder; 11)所述助剂包括分散剂、流平剂和/或消泡剂；11) The auxiliary agent includes a dispersing agent, a leveling agent and/or a defoaming agent; 12)溶剂包括二甲苯、乙二醇醚类、丙二醇、丙二醇醚类、甲醇、乙醇、乙二醇酯类和/或丙二醇酯类；12) Solvents include xylene, glycol ethers, propylene glycol, propylene glycol ethers, methanol, ethanol, ethylene glycol esters and/or propylene glycol esters; 13)浸泡时间包括1min～5min；13) The soaking time includes 1min～5min; 14)固化时间包括10min～60min；14) Curing time includes 10min～60min; 15)固化温度包括30℃～200℃；15) Curing temperature includes 30℃～200℃; 16)所述浸泡前还包括对所述待防护品进行除油和/或除锈；16) Before the soaking, it also includes degreasing and/or rust removal on the object to be protected; 17)硅烷转化膜的厚度包括0.5～10μm；17) The thickness of the silane conversion film includes 0.5 to 10 μm; 18)有机涂层的厚度包括3～10μm；18) The thickness of the organic coating includes 3 to 10 μm; 19)防护涂层的厚度包括5～15μm；19) The thickness of the protective coating includes 5 to 15 μm; 20)所述涂覆所述有机涂层后，还包括再次固化；20) after the organic coating is applied, further curing is included; 21)所述待防护品包括紧固件。21) The item to be protected includes a fastener. 7.根据权利要求6所述的防护涂层，其特征在于，所述任一防护涂层还包括下述1)-17)所述中的至少一种：7. The protective coating according to claim 6, wherein said any protective coating further comprises at least one of the following 1)-17): 1)阳离子表面活性剂包括十二烷基三甲基溴化铵、十八烷基三甲基氯化铵、和/或十六烷基三甲基氯化铵；1) cationic surfactants include dodecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, and/or cetyltrimethylammonium chloride; 2)阴离子表面活性剂包括十二烷基苯磺酸钠、脂肪醇酰硫酸钠和/或乙氧基化脂肪酸甲酯磺酸钠；2) anionic surfactants include sodium dodecylbenzenesulfonate, sodium fatty alcohol acyl sulfate and/or sodium ethoxylated fatty acid methyl ester sulfonate; 3)非离子表面活性剂包括烷基酚聚氧乙烯醚、壬基酚聚氧乙烯醚、辛烷基苯酚聚氧乙烯醚、NP-4和/或脂肪酸聚氧乙烯醚；3) Nonionic surfactants include alkylphenol ethoxylates, nonylphenol ethoxylates, octylphenol ethoxylates, NP-4 and/or fatty acid ethoxylates; 4)所述除油包括使用除油液进行除油，所述除油液包括：氢氧化钠、碳酸钠、磷酸三钠、硅酸钠和OP-10乳化剂；4) The degreasing includes using degreasing liquid to remove oil, and the degreasing liquid includes: sodium hydroxide, sodium carbonate, trisodium phosphate, sodium silicate and OP-10 emulsifier; 5)所述除锈包括使用除锈液进行除锈，所述除锈液包括盐酸和硝酸；5) described rust removal comprises using rust removal liquid to carry out rust removal, and described rust removal liquid comprises hydrochloric acid and nitric acid; 6)浸泡时间包括2min～3min；6) The soaking time includes 2min～3min; 7)固化时间包括30min～40min；7) The curing time includes 30min～40min; 8)固化温度包括100℃～170℃；8) Curing temperature includes 100℃～170℃; 9)硅烷转化膜的厚度包括2～5μm；9) The thickness of the silane conversion film includes 2 to 5 μm; 10)有机涂层的厚度包括5～10μm；10) The thickness of the organic coating includes 5 to 10 μm; 11)防护涂层的厚度包括7～15μm；11) The thickness of the protective coating includes 7 to 15 μm; 12)所述再次固化的固化时间包括30min～60min；12) The curing time of the re-curing includes 30min～60min; 13)所述再次固化的固化温度包括200℃～240℃；13) The curing temperature of the re-curing includes 200°C to 240°C; 14)每1L的硅烷转化液中，各组分的含量包括：14) In every 1L of silane conversion solution, the content of each component includes: 硅烷偶联剂25g/L～31g/L；Silane coupling agent 25g/L～31g/L; 助溶剂15g/L～35g/L；Cosolvent 15g/L～35g/L; 缓蚀剂1g/L～3g/L；Corrosion inhibitor 1g/L～3g/L; 表面活性剂1g/L～2g/L；Surfactant 1g/L～2g/L; pH调节剂0.1g/L～0.3g/L；pH adjuster 0.1g/L～0.3g/L; 15)有机涂层制备原料的质量百分含量包括：15) The mass percentage of organic coating preparation raw materials includes: 树脂20％～30％；Resin 20%～30%; 填料12％～16％；Filler 12%～16%; 助剂0.5％～0.6％；Auxiliary 0.5%～0.6%; 其余为溶剂，各组分质量百分含量之和为100％。The rest are solvents, and the sum of the mass percentages of each component is 100%. 16)所述紧固件包括钢铁材质的紧固件；16) The fasteners include fasteners made of steel; 17)所述紧固件包括海洋环境中使用的紧固件。17) The fasteners include those used in marine environments. 8.根据权利要求7述的防护涂层，其特征在于，所述任一防护涂层还包括下述1)-11)所述中的至少一种：8. The protective coating according to claim 7, wherein said any protective coating further comprises at least one of the following 1)-11): 1)每1L的除油液中包括：氢氧化钠3～15g/L；碳酸钠20～80g/L；磷酸三钠50～100g/L；硅酸钠5～15g/L；OP-10乳化剂0.2～3g/L；其余为水；1) Each 1L of degreasing solution includes: sodium hydroxide 3-15g/L; sodium carbonate 20-80g/L; trisodium phosphate 50-100g/L; sodium silicate 5-15g/L; OP-10 emulsification agent 0.2～3g/L; the rest is water; 2)每1L的除锈液中包括：盐酸2～10g/L；硝酸10～20g/L；其余为水；2) Each 1L of rust removal solution includes: hydrochloric acid 2～10g/L; nitric acid 10～20g/L; the rest is water; 3)浸泡时间包括2min和/或3min；3) The soaking time includes 2min and/or 3min; 4)固化时间包括40min和/或30min；4) Curing time includes 40min and/or 30min; 5)固化温度包括100℃、110℃、120℃、150℃和/或170℃；5) Curing temperature includes 100°C, 110°C, 120°C, 150°C and/or 170°C; 6)硅烷转化膜的厚度包括2～4μm、1～3μm和/或3～5μm；6) The thickness of the silane conversion film includes 2-4 μm, 1-3 μm and/or 3-5 μm; 7)有机涂层的厚度包括5～8μm、6～10μm、7～10μm、5～7μm和/或6～8μm；7) The thickness of the organic coating includes 5-8 μm, 6-10 μm, 7-10 μm, 5-7 μm and/or 6-8 μm; 8)防护涂层的厚度包括8～15μm、10～15μm、7～12μm、7～13μm、7～11μm和/或9～13μm；8) The thickness of the protective coating includes 8-15 μm, 10-15 μm, 7-12 μm, 7-13 μm, 7-11 μm and/or 9-13 μm; 9)再次固化的固化温度包括200℃、220℃、230℃和/或240℃；9) The curing temperature for re-curing includes 200°C, 220°C, 230°C and/or 240°C; 10)每1L的硅烷转化液中，各组分的含量包括：10) In every 1L of silane conversion solution, the content of each component includes: 硅烷偶联剂25g/L、31g/L、30g/L和/或27g/L；Silane coupling agent 25g/L, 31g/L, 30g/L and/or 27g/L; 助溶剂25g/L、35g/L和/或15g/L；Cosolvent 25g/L, 35g/L and/or 15g/L; 缓蚀剂3g/L和/或1g/L；Corrosion inhibitor 3g/L and/or 1g/L; 表面活性剂1g/L和/或2g/L；Surfactant 1g/L and/or 2g/L; pH调节剂0.1g/L、0.2g/L和/或0.3g/L；pH adjuster 0.1g/L, 0.2g/L and/or 0.3g/L; 11)有机涂层制备原料的质量百分含量包括：11) The mass percentage of raw materials for organic coating preparation includes: 树脂30％、25％、23％、28％和/或20％；Resin 30%, 25%, 23%, 28% and/or 20%; 填料13％、12％、14％和/或16％；Filler 13%, 12%, 14% and/or 16%; 助剂0.6％和/或0.5％；Auxiliary 0.6% and/or 0.5%; 其余为溶剂，各组分质量百分含量之和为100％。The rest are solvents, and the sum of the mass percentages of each component is 100%. 9.权利要求5、6、7和/或8任一所述方法直接制备得到的防护涂层。9. The protective coating directly prepared by the method of any one of claims 5, 6, 7 and/or 8. 10.权利要求1、2、3和/或4任一所述防护涂层、权利要求5、6、7和/或8任一所述方法、权利要求9所述防护涂层的应用。10. Use of the protective coating of any one of claims 1, 2, 3 and/or 4, the method of any of claims 5, 6, 7 and/or 8, and the protective coating of claim 9. 具体的，所述应用包括Specifically, the application includes 1)紧固件的防护；1) Protection of fasteners; 2)制备用于紧固件防护的产品。2) Preparation of products for fastener protection. 所述紧固件包括海洋环境中使用的紧固件；和/或所述紧固件包括钢铁材质的紧固件。The fasteners include fasteners used in marine environments; and/or the fasteners include steel fasteners.
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Application publication date: 20190423