CN106835093A - A kind of Q types POSS modified metal surface pretreating reagent and preparation method thereof, application - Google Patents
A kind of Q types POSS modified metal surface pretreating reagent and preparation method thereof, application Download PDFInfo
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- 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
- C23C22/06—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 using aqueous acidic solutions with pH less than 6
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- 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
- C23C22/06—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 using aqueous acidic solutions with pH less than 6
- C23C22/34—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 using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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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
- C23C22/06—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 using aqueous acidic solutions with pH less than 6
- C23C22/46—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 using aqueous acidic solutions with pH less than 6 containing oxalates
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- 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
- C23C22/06—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 using aqueous acidic solutions with pH less than 6
- C23C22/48—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 using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
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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
- C23C22/78—Pretreatment of the material to be coated
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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
- 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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Abstract
The invention discloses the metal surface pretreating reagent that a kind of Q types POSS is modified, with water as solvent, using silane as main film forming agent, it is second film forming agent with fluozirconate and/or fluorine zirconic acid, and eight (aminopropyl dimethylsilyl bis) cage modle eight oligomeric silsesquioxanes (amino Q type POSS) are added as film layer sealer and healant, acid, metallic promoter agent, rare earth compound, stabilizer can also be included.Q types POSS of the present invention modified metal surface pretreating reagent is that forming silane film and fluozirconate vitrification film forming are synchronously carried out in film forming, mutually doping, form fine and close inorganic-organic hybrid film, silane can in time repair the defect in fluozirconate film forming procedure, optimization membrane structure, and multiple amino of Q types POSS can multiple sites occur conduct simultaneously and in film layer, sealing effect can be obviously improved, and realize the more preferable repairing and closing to defect in film layer.
Description
Technical field
The present invention relates to field of metal surface treatment, specifically a kind of Q types POSS modified metal surface pretreating reagent and
Its preparation method, application.
Background technology
Metal material is damaged, referred to as metal erosion by the effect of surrounding medium.During metal erosion, on the interface of metal
Metal and empty gas and water etc. there occurs chemistry or electrochemistry heterogeneous reaction, metal is transferred to oxidation (ion) state, and this can significantly drop
The mechanical properties such as intensity, plasticity, the toughness of low metal material, destroy the geometry of hardware, increase the abrasion between part,
Deteriorate the physical property such as electrical and optical, shorten the service life of equipment.
It is on the metal surface the most frequently used important method for preventing metal erosion using coating protection.The work of coating
With being metallic article is kept apart with surrounding medium, to prevent or reduce corrosion.In addition to anticorrosion, coating also has one
Fixed dicoration or feature.But, it is poor with the adhesion of metal, it is necessary to apply because paint coatings belong to organic coating
Pre-treatment is carried out before dress to metal surface, increases by one layer of transition zone, the adhesion between enhancing metal surface and organic coating.
Traditional metal surface pre-treating method mainly has chemical conversion embrane method, and typical chemical conversion embrane method has at phosphatization
Reason, chromaking Passivation Treatment etc., but these traditional process for treating surface are faced with huge environmental pressure.Because chromic acid passivation method
In the presence of serious pollution of chromium, the method has been limited and used；And parco-lubrizing has serious phosphorus pollution, while also bringing other with much money
Category pollution, falls within the technology of being eliminated.To solve the pollution problem of conventional method, emphasis of the people more and more research is put
In the technology that can substitute conventional surface handling process.
At present, new metal surface pretreatment technology mainly has titanium salt conversion film (vitrification) technology, zirconates conversion film (pottery
Change) technology, tannate conversion membrane technology, Molybdate Conversion Film, cerium-based conversion coating technology and silane conversion film etc..Titanium salt is converted
Film (vitrification) technology, tannate conversion membrane technology, Molybdate Conversion Film, cerium-based conversion coating technology are scarce because combination property has
Fall into, be only applied in some special dimensions, fail to be promoted the use of on a large scale, and zirconates conversion film (vitrification) technology and silane
Conversion film by widely studied, and is applied due to excellent performance in a big way.
Zirconates conversion film (vitrification) technology refers to, using fluozirconate as chemical composition coating active component, to be processed before metal
During, fluozirconate hydrolyzes to form zirconium dioxide film in metal surface.The advantage of this technology is that film layer is caused compared with phosphating coat
Close, required film layer is substantially reduced compared with phosphating coat, and its film-forming process flow is similar with phosphatization, therefore can be in preceding treatment production
Phosphatization is directly substituted on line.But, because the vitrification film layer still has more film forming defect, generally require addition sealer.
Silanization metal surface treatment technology overcomes the metals such as traditional phosphatization, chromaking as a kind of new technology
The shortcoming that energy consumption in process for treating surface is big, pollution is big etc. itself cannot overcome, oneself was through having obtained extensive hair in the last few years
Exhibition, the application of reality has been obtained in industrial application.Silane is the hybrid thing of a class silicon substrate, its basic molecule
Formula is：Y(CH2)nSiR2 x(OR3)3-x, wherein OR3It is hydrolyzable group, Y is organo-functional group.OR3Group promotes in hydrolysis
In the presence of agent, hydrolysis generation Si-OH groups, with metal surface-Me-OH dehydrating condensations, formed Si-O-Me keys, together
When Si-OH keys itself there is dehydrating condensation and form space three-dimensional network structure.Y(CH2)nSubstitution base and organic coating compatibility
Good, Y functional groups can occur corresponding chemical reaction with the related functional group of organic coating if necessary, realize by the molecule of silane
Bridge is acted on, and realizes the effect between inorganic metal layer and organic layer, improves adhesion of the coating in metal surface.
Begun one's study from the eighties in last century since silane is used for into metal surface pre-treatment, silane is dissolved in solvent by discovery
In, with metal surface, work well, but solvent volatilizees can cause environmental pollution in use, and cost is very high.It is most preferable
Method be that silane is dissolved in water, both reduces cost, can avoid the pollution problem of organic solvent again.But, people are in length
Phase practice, it is found that the organosilan mainly amino silane and epoxy radicals silicone hydride of water can be dissolved in, but these silane hydrolyzates
Rear stability is bad, will be typically crosslinked between a couple of days in a few hours.Additionally, pure silane pretreating reagent is when metal is processed,
First it is to be adsorbed in metal surface by hydrogen bond, certain bar is needed due to being dehydrated between Si-OH and Me-OH and Si-OH and Si-OH
Part, is difficult quickly to form the three-dimensional net structure of stabilization under the conditions of normal temperature or less than 50 DEG C, therefore pure silane inorganic agent and chromic acid
Passivation, phosphatization are compared, and film forming speed is slow, generally requires the silane film that can be stablized by the operation that is heating and curing together, and
Water flushing membrane can not be used before complete film forming, therefore phosphating process can not be directly substituted on existing phosphatization production line.Therefore, how
The fast silane finish of the aqueous silane and film forming speed stablized is that silane technology is used in the pre-treatment of metal surface
Technical bottleneck.
The content of the invention
The technical problems to be solved by the invention are directed to the deficiency of above-mentioned prior art presence and provide a kind of Q types POSS
Modified metal surface pretreating reagent and preparation method thereof, application process, can be in cold-rolled steel, hot-rolled steel, stainless steel, aluminium alloy
Deng metal surface formed one layer of three-dimensional space network shape it is inorganic/organic hybrid composite membrane, the film have extremely strong compactness and, with
The extremely strong binding ability of metal, coating.
The present invention is to solve the problems, such as that used technical scheme set forth above is：
A kind of Q types POSS modified metal surface pretreating reagent, with water as solvent, using silane as main film forming agent, with fluorine
Zirconates and/or fluorine zirconic acid are second film forming agent, and add the eight poly- silicon sesquialter oxygen of (aminopropyl dimethylsilyl bis) cage modle eight
Alkane (referred to as amino Q types POSS, or Q type POSS) is used as film layer sealer and healant.
By such scheme, can also include that acid, metal promote in above-mentioned Q types POSS modified metal surface pretreating reagent composition
Enter agent, rare earth compound and organic stabilizer.
By such scheme, the Q types POSS modified metal surface pretreating reagent, its raw material components are according to the mass fraction
Including：Silane 0.01-20 parts, fluozirconate and/or fluorine zirconic acid 0.01-20 parts, eight (aminopropyl dimethylsilyl bis) cage modles eight
It is oligomeric silsesquioxane 0.01-5 parts, sour 0-10 parts, metallic promoter agent 0-1 parts, rare earth compound 0-0.5 parts, organic stabilizer 0-5
Part, water 44-135 parts.
By such scheme, the silane is 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, N- ammonia second
Base -3- aminopropyl trimethoxysilanes, N- aminoethyl -3- aminopropyl triethoxysilanes, 3- aminopropyltriethoxy dimethoxy silicon
Alkane, 3- aminopropyltriethoxies diethoxy silane, N- aminoethyl -3- aminopropyltriethoxies dimethoxysilane, N- aminoethyl -3- ammonia third
Ylmethyl diethoxy silane, epoxypropoxy triethoxysilane, glycidoxy-propyltrimethoxy silane, the oxygen of epoxy third
Hydroxypropyl methyl dimethoxysilane, glycidoxypropyl diethoxy silane, 1,2- bis- (trimethoxy silicon substrate) ethane, 1,
One or more mixture in 2- bis- (triethoxy silicon substrate) ethane etc..
By such scheme, the fluozirconate is selected from the one kind or in ammonium fluozirconate, potassium fluorozirconate and sodium fluozirconate etc.
Plant the mixture of the above.
By such scheme, the structural formula difference of the amino Q types POSS is as follows：
Wherein, R1It is 3- aminopropyls-dimethylsilyl bis (H2NC3H6(CH3)2SiO—)。
By such scheme, the acid is hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, malic acid, citric acid, tartaric acid, lactic acid, grass
One or more mixture in acid etc..
By such scheme, the metallic promoter agent is the one kind or in manganese sulfate, manganese nitrate, copper sulphate, copper nitrate etc.
Plant the mixture of the above.
By such scheme, the rare earth compound is the one kind or in lanthanum nitrate, lanthanum chloride, cerous nitrate, cerous sulfate etc.
Plant the mixture of the above.
By such scheme, the organic stabilizer is in ethanol, methyl alcohol, glycerine, normal propyl alcohol, isopropanol, n-butanol etc.
Any one or more than one mixture.
The preparation method of above-mentioned Q types POSS modified metal surface pretreating reagent, mainly comprises the following steps：
1) after adding sour, fluozirconate and/or fluorine zirconic acid, metallic promoter agent and rare earth compound in water, stir
As component A；
2) amino Q types POSS, silane and organic stabilizer are added in water, as B component after stirring；
3) by step 2) gained B component be added to step 1) gained component A in, stir, that is, obtain Q types POSS be modified
Metal surface pretreating reagent.
By such scheme, each composition is according to the mass fraction in the component A：Water 40-95 parts, fluozirconate and/or fluorine
It is zirconic acid 0.01-20 parts, sour 0-10 parts, metallic promoter agent 0-1 parts, rare earth compound 0-0.5 parts.
By such scheme, each composition is according to the mass fraction in the B component：Water 4-40 parts, 0.01-5 parts of Q type POSS,
Silane 0.01-20 parts, organic stabilizer 0-5 parts.
Q types POSS of the present invention modified metal surface pretreating reagent can be used for steel, galvanized sheet, aluminium alloy plate etc.
Metallic surface pre-treatment.Application process is：The metal surface pretreating reagent that the Q types POSS is modified is diluted with water to and is contained admittedly
It is 0.001-1% to measure, and adjusts pH to 3.8-5.0, and carrying out pre-treatment to metal using infusion method or spray process obtains silane film
Layer.Wherein, regulation pH is generally using the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or the strong base-weak acid salt such as sodium carbonate, or NaOH
Deng alkali.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) Q types POSS of the present invention modified metal surface pretreating reagent is forming silane film and fluorine zirconic acid in film forming
Salt vitrification film forming is synchronously carried out, mutually doping, forms fine and close inorganic-organic hybridization film, and silane can in time repair fluorine zirconic acid
Defect in salt film forming procedure, optimizes membrane structure, and multiple amino of Q types POSS can multiple sites occur simultaneously and in film layer
As sealing effect can be obviously improved, and realize more preferable repairing and closing to defect in film layer.
(2) Q types POSS of the present invention modified metal surface pretreating reagent is in film forming procedure, zirconium compounds (i.e. fluorine zirconic acid
Salt and/or fluorine zirconic acid) can be conducive to accelerating forming silane film as crosslinked with silicane accelerator, make at of short duration metal surface
In the reason time, water miscible silane is adsorbed in metal surface and crosslinking film forming leaves silane without that can be dissolved in water, metal processing piece
Treatment process can be washed at once, and realize silane film can quick water scrub function；
(3) present invention utilizes the introducing of silane complex technique and Q types POSS, it is ensured that the stability of aqueous silane systems,
And aqueous silane and fluozirconate can be re-dubbed uniform solution, and very well, the single group for being capable of achieving user separates dilute making to stability
With.
(4) Q types POSS of the present invention modified metal surface pretreating reagent can obtain fine and close hydridization in metal surface
Film, the film has excellent silane film (not going up outer protective paint, the lower naked mould of abbreviation) antirust ability and is coupled energy with coating
Power.
Q types POSS of the present invention modified metal surface pretreating reagent may be substituted for conventional phosphatizing treatment technology,
It is suitable for use with the various industrial circles of metal, such as automobile, household electrical appliances application, hardware etc..
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Embodiment 1
A kind of Q types POSS modified metal surface pretreating reagent, its composition includes according to the mass fraction：54.89 parts of water, 10
Part ammonium fluozirconate, 0.02 part of eight (3- aminopropyls-dimethylsilyl bis) cage type eight oligomeric silsesquioxane ((H2NC3H6(CH3)2SiOSiO1.5)8) (molecular formula is：C40H112Si16O20N8) (CAS registration numbers：2046327-37-9), 20 parts of second of 3- aminopropyls three
TMOS, 2 parts of citric acids, 8 parts of malic acid, 0.02 part of cerous sulfate and 0.01 part of lanthanum nitrate.
The preparation method of above-mentioned Q types POSS modified metal surface pretreating reagent, mainly comprises the following steps：
1) as mass fraction, in 40 parts of water, 10 parts of ammonium fluozirconates are added under agitation, after being completely dissolved once
2 parts of citric acids, 8 parts of malic acid, 0.02 part of cerous sulfate and 0.01 part of lanthanum nitrate are added, component A is uniformly mixing to obtain；
2) in 14.89 parts of water, 20 parts of 3- aminopropyl triethoxysilanes are added under agitation, after stirring and dissolving,
0.02 part of Q type-POSS is added, as B component after stirring；
3) B component is added in component A, stirs and obtain the modified metal surface pretreating reagents of Q types POSS, i.e.,
A kind of environment-friendly type silane coating metal surfaces pretreating reagent.
Application process：The metal surface pretreating reagent that above-mentioned Q types POSS is modified and pure water 1:39 open dilute, open dilute rear apparent
Solid content is 1.0%, and the pH value for opening dilute rear solution is determined with pH meter, and 4.0 are maintained at sodium carbonate regulating solution pH；Then use
Infusion method, after the cold-reduced sheet after degreasing is soaked into 30 seconds wherein, with twice of pure water rinsing, then using the electrophoretic paint of ippon 10421
Electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
The method specified according to GB/T10125 and GB/T6461 determines cold-reduced sheet silane film (cold rolling plate surface i.e. before electrophoresis
Film layer) resistance to Neutral Salt Spray Corrosion performance, according to GB/T 1720 specify method determine cold-reduced sheet silane film adhesive force；
The method specified according to GB/T 1731 determines the pliability of cold-reduced sheet silane film；The method specified according to GB/T 1732 determines cold
Roll the impact resistance of plate silane film.The resistance to Neutral Salt Spray Corrosion of cold rolling plate electrophoresis rear electrophoresis film is tested after the same method
Energy, adhesive force and pliability.Test result is as shown in table 1.
Embodiment 2
A kind of Q types POSS modified metal surface pretreating reagent, its composition includes according to the mass fraction：98.89 parts of water,
0.01 part of fluorine zirconic acid, 0.01 part of eight (3- aminopropyls-dimethylsilyl bis) cage type eight oligomeric silsesquioxane ((H2NC3H6(CH3)2SiOSiO1.5)8) (molecular formula is：C40H112Si16O20N8) (CAS registration numbers：2046327-37-9), 0.08 part of third oxygen of epoxy third
Base trimethoxy silane, 0.9 part of N- aminoethyl -3- aminopropyl trimethoxysilanes, 0.01 part of malic acid and 0.1 part of nitric acid.
The preparation method of above-mentioned Q types POSS modified metal surface pretreating reagent, mainly comprises the following steps：
1) according to the mass fraction, in 74 parts of water, under agitation add 0.01 part of malic acid, 0.1 part of nitric acid and
0.01 part of fluorine zirconic acid, component A is obtained after being completely dissolved；
2) add 0.01 part of amino Q type POSS under agitation in 24.89 parts of water, after stirring and dissolving, add
0.08 part of glycidoxy-propyltrimethoxy silane, 0.9 part of N- aminoethyl -3- aminopropyl trimethoxysilane, after stirring
As B component；
3) B component is added in component A, is stirred, that is, obtain the modified metal surface pretreating reagents of Q types POSS.
Application process：The metal surface pretreating reagent that above-mentioned Q types POSS is modified is with pure water with volume ratio 1:1099 dilutions,
And its pH value is determined with pH meter, and it is maintained at 4.0 with NaOH regulation pH；Then infusion method is used by the cold-reduced sheet after degreasing
After soaking 3 minutes wherein, with twice of pure water rinsing, then with the electrophoretic paint electrophoresis of ippon 10421；After electrophoresis with pure water rinsing after,
Hot blast drying.
Method according to embodiment 1 determines the resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible
Property.Test result is as shown in table 1.
Embodiment 3
A kind of Q types POSS modified metal surface pretreating reagent, its composition includes according to the mass fraction：95.38 parts of water, 3
Part fluorine zirconic acid, 0.5 part of Q types-POSS, 0.1 part of N- aminoethyl -3- aminopropyl trimethoxysilanes, 1 part of tartaric acid, 0.01 part of nitre
Sour copper, 0.01 part of glycerine.
The preparation method of above-mentioned Q types POSS modified metal surface pretreating reagent, mainly comprises the following steps：
1) as mass fraction, in 91.38 parts of water, under agitation add 3 parts of fluorine zirconic acids, 1 part of tartaric acid and
0.01 part of copper nitrate, is uniformly mixing to obtain component A；
2) in 4 parts of water, 0.01 part of glycerine and 0.1 part of second of N- aminoethyl -3- aminopropyls three are added under agitation
TMOS, after stirring and dissolving, adds 0.5 part of Q type-POSS, as B component after stirring；
3) B component is added in component A, stirs and obtain the modified metal surface pretreating reagents of Q types POSS.
Application process：The metal surface pretreating reagent that above-mentioned Q types POSS is modified and pure water 1:49 open dilute, open dilute rear apparent
Solid content is 0.09%, and the pH value for opening dilute rear solution is determined with pH meter, and pH value of solution is adjusted with nitric acid, pH value of solution is maintained at 4.0,
Using spray process, after the cold-reduced sheet after degreasing is sprayed 3 minutes, with twice of pure water rinsing, using the electrophoretic paint of ippon 10421 electricity
Swimming, with after pure water rinsing after electrophoresis, hot blast drying.
Method according to embodiment 1 determines the resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible
Property.Test result is as shown in table 1.
Embodiment 4
A kind of Q types POSS modified metal surface pretreating reagent, its composition includes according to the mass fraction：89.3 parts of water, 0.2
Part fluorine zirconic acid, 5 parts of Q types-POSS, 1 part of 1,2- bis- (front three oxygen silicon base) ethane, 1 part of 2- aminoethyls trimethoxy silane, 1 part of ring
The oxygen propyl trimethoxy silicane of oxygen third, 0.5 part of hydrochloric acid, 1 part of n-butanol and 1 part of isopropanol.
The preparation method of above-mentioned Q types POSS modified metal surface pretreating reagent, mainly comprises the following steps：
1) as mass fraction, in 80 parts of water, 0.2 part of fluorine zirconic acid is added under agitation, after being completely dissolved once
0.5 part of hydrochloric acid is added, component A is uniformly mixing to obtain；
2) in 9.3 parts of water, 1 part of 1,2- bis- (front three oxygen silicon base) ethane, 1 part of 2- ammonia second are sequentially added under agitation
Base trimethoxy silane and 1 part of glycidoxy-propyltrimethoxy silane, after stirring and dissolving, add 1 part of isopropanol, 1 part just
Butanol and 5 parts of Q type-POSS, as B component after stirring；
3) B component is added in component A, stirs and obtain the modified metal surface pretreating reagents of Q types POSS.
Application process：The metal surface pretreating reagent that above-mentioned Q types POSS is modified and pure water 1:199 open dilute, open dilute rear table
It is 0.044% to see solid content, and the pH value for opening dilute rear solution is determined with pH meter, uses sodium hydrate regulator solution pH, protects pH value of solution
Hold 4.0, using infusion method, after the cold-reduced sheet after degreasing is soaked 3 minutes, with twice of pure water rinsing, using the electricity of ippon 10421
Swimming paint electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
Method according to embodiment 1 determines the resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible
Property.Test result is as shown in table 1.
Embodiment 5
A kind of Q types POSS modified metal surface pretreating reagent, its composition includes according to the mass fraction：75 parts of water, 1 part of fluorine
Sodium zirconate, 0.01 part of potassium fluorozirconate, 0.9 part of Q types-POSS, 10 parts of aminomethyl triethoxysilanes, 5 parts of (trimethoxy silicon of 1,2- bis-
Base) ethane, 3 parts of nitric acid, 0.01 part of copper nitrate, 0.02 part of lanthanum nitrate, 0.06 part of cerous sulfate, 5 parts of isopropanols.
The preparation method of above-mentioned Q types POSS modified metal surface pretreating reagent, mainly comprises the following steps：
1) as mass fraction, in 40 parts of water, 1 part of sodium fluozirconate and 0.01 part of fluorine zirconic acid are added under agitation
Potassium, once adds 3 parts of nitric acid, 0.01 part of copper nitrate, 0.02 part of lanthanum nitrate, 0.06 part of cerous sulfate after being completely dissolved, stir
Obtain component A；
2) in 35 parts of water, 5 parts of isopropanols, 10 parts of aminomethyl triethoxysilanes and 5 part 1 are added under agitation,
2- bis- (front three oxygen silicon base) ethane, after stirring and dissolving, adds 0.9 part of Q type-POSS, as B component after stirring；
3) B component is added in component A, stirs and obtain the modified metal surface pretreating reagents of Q types POSS.
Application process：The metal surface pretreating reagent that above-mentioned Q types POSS is modified and pure water 1:599 open dilute, open dilute rear table
It is 0.03% to see solid content, and the pH value for opening dilute rear solution is determined with pH meter, uses sodium hydrate regulator solution pH, keeps pH value of solution
4.0, using infusion method, after the cold-reduced sheet after degreasing is soaked 3 minutes, with twice of pure water rinsing, using the electrophoresis of ippon 10421
Paint electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
Method according to embodiment 1 determines the resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible
Property.Test result is as shown in table 1.
Embodiment 6
A kind of Q types POSS modified metal surface pretreating reagent, its composition includes according to the mass fraction：67 parts of water, 20 parts
Fluorine zirconic acid, 4 parts of Q types-POSS, 1 part of 1,2- bis- (three ethoxy silicon substrates) ethane, 1 part of 3- aminopropyltriethoxies diethoxy silane, 3 parts
98% sulfuric acid, 2 parts of citric acids, 0.5 part of copper sulphate, 0.5 part of manganese nitrate, 1 part of n-butanol.
The preparation method of above-mentioned Q types POSS modified metal surface pretreating reagent, mainly comprises the following steps：
1) as mass fraction, in 45 parts of water, add under agitation 3 part of 98% sulfuric acid, 2 parts of citric acids, 20 parts
Fluorine zirconic acid, 0.5 part of copper sulphate and 0.5 part of manganese nitrate, are uniformly mixing to obtain component A；
2) in 22 parts of water, 1 part of n-butanol and 1 part of 3- aminopropyltriethoxies diethoxy silane, 1 are added under agitation
Part 1,2- bis- (three ethoxy silicon substrates) ethane, after stirring and dissolving, adds 4 parts of Q type-POSS, as B component after stirring；
3) B component is added in component A, stirs and obtain the modified metal surface pretreating reagents of Q types POSS.
Application process：The metal surface pretreating reagent that above-mentioned Q types POSS is modified and pure water 1:639 open dilute, open dilute rear table
It is 0.05% to see solid content, and the pH value for opening dilute rear solution is determined with pH meter, uses sodium hydrate regulator solution pH, keeps pH value of solution
4.0, using infusion method, after the cold-reduced sheet after degreasing is soaked 5 minutes, with twice of pure water rinsing, using the electrophoresis of ippon 10421
Paint electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
Method according to embodiment 1 determines the resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible
Property.Test result is as shown in table 1.
Comparative example 1
A kind of metal surface pretreating reagent, its composition includes according to the mass fraction：95 parts of water, 3 parts of fluorine zirconic acids, 1 part of epoxy
Third oxygen propyl trimethoxy silicane, 1 part of citric acid.
The preparation method of above-mentioned metal surface pretreating reagent, mainly comprises the following steps：As mass fraction, in 75 parts of water
In, 3 parts of fluorine zirconic acids are added under agitation, 1 part of citric acid is stirring evenly and then adding into, it is uniformly mixing to obtain component A；At 20 parts
In water, 1 part of glycidoxy-propyltrimethoxy silane is added under agitation, as B component after stirring；By B component
It is added in component A, stirs the metal surface pretreating reagent that obtain.
Application process：By above-mentioned metal surface pretreating reagent and pure water 1:99 open dilute, open dilute rear apparent solid content and are
0.05%, the pH value for opening dilute rear solution is determined with pH meter, sodium hydroxide solution pH is used, pH value of solution is maintained at 3.8, using spray
Method, after the cold-reduced sheet after degreasing is sprayed 5 minutes, with twice of pure water rinsing, using the electrophoretic paint electrophoresis of ippon 10421, after electrophoresis
After pure water rinsing, hot blast drying.
Method according to embodiment 1 determines the resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible
Property.Test result is as shown in table 1.
Comparative example 2
A kind of metal surface pretreating reagent, its composition includes according to the mass fraction：95 parts of water, 3 parts of fluorine zirconic acids, 1 part of 3- ammonia
Propyl trimethoxy silicane, 1 part of 60% concentrated nitric acid.
The preparation method of above-mentioned metal surface pretreating reagent, mainly comprises the following steps：
As mass fraction, in 75 parts of water, 3 parts of fluorine zirconic acids are added under agitation, be stirring evenly and then adding into 1 part of nitre
Acid, is uniformly mixing to obtain component A；In 20 parts of water, 1 part of 3- aminopropyl trimethoxysilane, stirring are added under agitation
As B component after uniform；B component is added in component A, stirs the metal surface pretreating reagent that obtain.
Application process：By above-mentioned metal surface pretreating reagent and pure water 1:99 open dilute, open dilute rear apparent solid content and are
0.05%, the pH value for opening dilute rear solution is determined with pH meter, sodium hydroxide solution pH is used, pH value of solution is maintained at 3.8, using spray
Method, after the cold-reduced sheet after degreasing is sprayed 5 minutes, with twice of pure water rinsing, using the electrophoretic paint electrophoresis of ippon 10421, after electrophoresis
After pure water rinsing, hot blast drying.
Method according to embodiment 1 determines the resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible
Property.Test result is as shown in table 1.
Table 1
As it can be seen from table 1 metal surface pretreating reagent Q types POSS modified in each embodiment is formed in cold rolling plate surface
Silane film there is good adhesive force, pliability and impact resistance, with the anti-corruption in extraordinary normal temperature atmospheric environment
Erosion ability, and without addition Q type POSS compounds in comparative example, the cold-reduced sheet silane film of gained is rapid in normal temperature atmospheric environment
Get rusty；By electrophoresis after cold-reduced sheet silane film painting on surface film, in embodiment 1-6 paint film be respectively provided with extraordinary adhesive force,
Pliability, impact resistance and excellent resistance to neutral salt spray performance, combination property exceed joint auto vendor to body paint
It is required that, and the impact resistance of electrodeposited paint film does not reach requirement in comparative example, decay resistance is also very poor, and joint multiplying is not reached far
Requirement with car enterprise to body paint.
The above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, can also make some modifications and variations, these belong to of the invention
Protection domain.
Claims (10)
1. a kind of Q types POSS modified metal surface pretreating reagent, it is characterised in that it with water as solvent, using silane as it is main into
Film, is second film forming agent with fluozirconate and/or fluorine zirconic acid, and it is poly- to add eight (aminopropyl dimethylsilyl bis) cage modles eight
Silsesquioxane (Q type POSS) is used as film layer sealer and healant.
2. the metal surface pretreating reagent that a kind of Q types POSS according to claim 1 is modified, it is characterised in that its raw material
Also include acid, metallic promoter agent, rare earth compound and organic stabilizer in composition.
3. the metal surface pretreating reagent that a kind of Q types POSS is modified, it is characterised in that its raw material components are wrapped according to the mass fraction
Include：Silane 0.01-20 parts, fluozirconate and/or fluorine zirconic acid 0.01-20 parts, eight (aminopropyl dimethylsilyl bis) cage modles eight are gathered
It is silsesquioxane 0.01-5 parts, sour 0-10 parts, metallic promoter agent 0-1 parts, rare earth compound 0-0.5 parts, organic stabilizer 0-5
Part, water 44-135 parts.
4. Q types POSS according to any one in claim 1-3 modified metal surface pretreating reagent, it is characterised in that
The silane is 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, N- aminoethyl -3- aminopropyl trimethoxies
Silane, N- aminoethyl -3- aminopropyl triethoxysilanes, 3- aminopropyltriethoxies dimethoxysilane, 3- aminopropyltriethoxy diethyls
TMOS, N- aminoethyl -3- aminopropyltriethoxies dimethoxysilane, N- aminoethyl -3- aminopropyltriethoxies diethoxy silane,
Epoxypropoxy triethoxysilane, glycidoxy-propyltrimethoxy silane, glycidoxypropyl dimethoxy silicon
Alkane, glycidoxypropyl diethoxy silane, 1,2- bis- (tri-alkoxy silicon substrate) ethane are (the trimethoxy silicon of 1,2- bis-
Base) ethane, one or more the mixture in 1,2- bis- (triethoxy silicon substrate) ethane, wherein amino silicone must be had
Alkane.
5. Q types POSS piece according to any one in claim 1-3 modified metal surface pretreating reagent, its feature exists
It is amino Q type POSS in described eight (aminopropyl dimethylsilyl bis) cage modle eight oligomeric silsesquioxanes, structural formula is as follows：
Wherein, R1It is 3- aminopropyls-dimethylsilyl bis.
6. Q types POSS according to any one in claim 1-3 modified metal surface pretreating reagent, it is characterised in that
The acid for the one kind or one kind in hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, malic acid, citric acid, tartaric acid, lactic acid, oxalic acid with
On mixture；The stabilizer be in ethanol, methyl alcohol, glycerine, normal propyl alcohol, isopropanol, n-butanol etc. any one or
More than one mixture.
7. Q types POSS according to any one in claim 1-3 modified metal surface pretreating reagent, it is characterised in that
The metallic promoter agent is one or more the mixture in manganese sulfate, manganese nitrate, copper sulphate, copper nitrate；It is described dilute
Earth compounds are one or more the mixture in lanthanum nitrate, lanthanum chloride, cerous nitrate, cerous sulfate.
8. the preparation method of a kind of Q types POSS modified metal surface pretreating reagent, it is characterised in that mainly comprise the following steps：
1) after adding fluozirconate and/or fluorine zirconic acid, acid, metallic promoter agent and rare earth compound in water, stir as A
Component；
2) organic stabilizer, silane and eight (aminopropyl dimethylsilyl bis) oligomeric silsesquioxanes of cage modle eight, stirring are added in water
As B component after uniform；
3) by step 2) gained B component is added to step 1) in gained component A, stir, that is, obtain the modified gold of Q types POSS
Metal surface pretreating reagent.
9. the preparation method of Q types POSS according to claim 8 modified metal surface pretreating reagent, it is characterised in that institute
Each composition is according to the mass fraction in stating component A：Water 40-95 parts, fluozirconate and/or fluorine zirconic acid 0.01-20 parts, sour 0-10
Part, metallic promoter agent 0-1 parts, rare earth compound 0-0.5 parts；Each composition is according to the mass fraction in the B component：Water 4-40
Part, eight (aminopropyl dimethylsilyl bis) cage modles eight oligomeric silsesquioxane 0.01-5 parts, silane 0.01-20 parts, organic stabilizer
0-5 parts.
10. the application side of Q types POSS according to any one in claim 1-3 modified metal surface pretreating reagent
Method, it is characterised in that the metal surface pretreating reagent that the Q types POSS is modified is diluted with water to solid content for 0.001-1%,
And adjust in the range of pH to 3.8-5.0, pre-treatment is carried out to metal using infusion method or spray process.
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