CN106835093B - A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application - Google Patents

A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application Download PDF

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CN106835093B
CN106835093B CN201710104044.2A CN201710104044A CN106835093B CN 106835093 B CN106835093 B CN 106835093B CN 201710104044 A CN201710104044 A CN 201710104044A CN 106835093 B CN106835093 B CN 106835093B
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metal surface
silane
acid
pretreating reagent
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CN106835093A (en
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黄驰
刘张洋
文宇佳
方振天
李安然
吕思雨
高子茹
王光明
廖俊
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Wuhan University WHU
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/46Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/48Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2222/00Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20Use of solutions containing silanes

Abstract

The invention discloses a kind of modified metal surface pretreating reagents of Q type POSS, it takes water as a solvent, using silane as main film forming agent, with fluozirconate and/or fluorine zirconic acid for second of film forming agent, and add eight (aminopropyl dimethylsilyl bis) cage modles, eight oligomeric silsesquioxane (amino Q type POSS) and be used as film layer sealer and healant, it can also include acid, metallic promoter agent, rare earth compound, stabilizer.Q type POSS of the present invention modified metal surface pretreating reagent, which is that forming silane film is synchronous with fluozirconate vitrification film forming in film forming, to carry out, mutually doping, form fine and close inorganic-organic hybridization film, silane can repair the defects of fluozirconate film forming procedure in time, optimize membrane structure, and multiple amino of Q type POSS can conduct occurs for multiple sites simultaneously and in film layer, sealing effect can be obviously improved, and realize more preferable repairing and closing to defect in film layer.

Description

A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application
Technical field
The present invention relates to field of metal surface treatment, specifically a kind of Q type POSS modified metal surface pretreating reagent and Preparation method, application.
Background technique
Metal material by surrounding medium effect and damage, referred to as metal erosion.When metal erosion, on the interface of metal Chemistry or electrochemistry heterogeneous reaction has occurred in metal and empty gas and water etc., so that metal is transferred to oxidation (ion) state, this can significantly be dropped The mechanical properties such as intensity, plasticity, the toughness of low metal material destroy the geometry of metal component, increase the abrasion between part, Deteriorate the physical properties such as electrical and optical, shortens the service life of equipment.
The protection of application coating is the most common important method for preventing metal erosion on the metal surface.The work of coating With being to keep apart metal product with surrounding medium, to prevent or reduce corrosion.Other than anticorrosion, there are also one for coating Fixed dicoration or functionality.It is poor with the binding force of metal but since paint coatings belong to organic coating, it needs applying Pre-treatment is carried out to metal surface before dress, increases by one layer of transition zone, enhances the binding force between 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 of chromic acid passivation method There are serious pollution of chromium, this method has limited use;And parco-lubrizing is polluted there are serious phosphorus, while also bringing an other huge sum of moneys Belong to pollution, also belongs to the technology of being eliminated.For the pollution problem for solving conventional method, people more and more put the emphasis of research In the technology that can substitute conventional surface treatment process.
Currently, novel 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 conversion Film (vitrification) technology, tannate conversion membrane technology, Molybdate Conversion Film, cerium-based conversion coating technology are scarce since comprehensive performance has It falls into, is only applied in certain special dimensions, fails to promote the use of on a large scale, and zirconates conversion film (vitrification) technology and silane Conversion film is studied extensively due to haveing excellent performance, and obtains larger range application.
Zirconates conversion film (vitrification) technology refers to using fluozirconate as chemical composition coating active component, handles before metal In the process, 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 process is similar with phosphatization, therefore can be produced in preceding processing Phosphatization is directly substituted on line.But since 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 novel technology Energy consumption is high in process for treating surface, pollutes the shortcomings that of itself can not overcoming such as big, oneself had been obtained extensive hair in recent years Exhibition, has obtained actual application in industrial application.Silane is the hybrid object of a kind of silicon substrate, basic molecule Formula are as follows: Y (CH2)nSiR2 x(OR3)3-x, wherein OR3It is hydrolyzable group, Y is organo-functional group.OR3Group promotes in hydrolysis Under the action of agent, hydrolysis generate Si-OH group, with metal surface-Me-OH dehydrating condensation, formed Si-O-Me key, together When Si-OH key itself occur dehydrating condensation formed space three-dimensional network structure.Y(CH2)nSubstituent group and organic coating compatibility Good, corresponding chemical reaction can occur with the related functional group of organic coating for Y functional group when necessary, realize the molecule by silane Bridge effect, realizes the effect between inorganic metal layer and organic layer, improves coating in the binding force of metal surface.
Since beginning one's study silane being used for metal surface pre-treatment the eighties in last century, silane is dissolved in solvent by discovery In, it with metal surface, works well, but solvent volatilizees in use will cause environmental pollution, and cost is very high.It is most ideal Method be silane is molten in water, not only reduce cost, but also can be to avoid the pollution problem of organic solvent.But, people are in length Phase practice, it is found that the organosilan that can be dissolved in water is mainly amino silane and epoxy radicals silicone hydride, but these silane hydrolyzates Rear stability is bad, will generally be crosslinked in a few hours between a couple of days.In addition, pure silane pretreating reagent is when handling metal, It is to be adsorbed by hydrogen bond in metal surface first, since dehydration needs certain item between Si-OH and Me-OH and Si-OH and Si-OH Part is difficult quickly to form stable three-dimensional net structure under room temperature or 50 DEG C of the following conditions, therefore pure silane inorganic agent and chromic acid Passivation, phosphatization are compared, and film forming speed is slow, generally require that stable silane film can be obtained by the process that is heating and curing together, and It cannot be rinsed with water film before complete film forming, therefore cannot directly substitute phosphating process on existing phosphatization production line.Therefore, how Obtaining stable aqueous silane and the fast silane finish of film forming speed is that silane technology is used in the pre-treatment of metal surface Technical bottleneck.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of Q type POSS in view of the deficiency of the prior art Modified metal surface pretreating reagent and preparation method thereof, application method, can be in cold-rolled steel, hot-rolled steel, stainless steel, aluminium alloy Equal metal surfaces 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 be solve the problems, such as it is set forth above used by technical solution are as follows:
A kind of metal surface pretreating reagent that Q type POSS is modified, takes water as a solvent, using silane as main film forming agent, with fluorine Zirconates and/or fluorine zirconic acid are second of film forming agent, and add the poly- silicon sesquialter oxygen of eight (aminopropyl dimethylsilyl bis) cage modle eight Alkane (referred to as amino Q type POSS or Q type POSS) is used as film layer sealer and healant.
It according to the above scheme, can also include acid, metal rush in above-mentioned Q type POSS modified metal surface pretreating reagent composition Into agent, rare earth compound and organic stabilizer.
According to the above scheme, the Q type POSS modified metal surface pretreating reagent, its raw material components are according to the mass fraction It include: 0.01-20 parts of silane, fluozirconate and/or 0.01-20 parts of fluorine zirconic acid, eight (aminopropyl dimethylsilyl bis) cage modles eight It is 0.01-5 parts of oligomeric silsesquioxane, 0-10 parts sour, 0-1 parts of metallic promoter agent, 0-0.5 parts of rare earth compound, organic stabilizer 0-5 Part, 44-135 parts of water.
According to the above scheme, the silane is 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, N- ammonia second Base -3- aminopropyl trimethoxysilane, N- aminoethyl -3- aminopropyl triethoxysilane, 3- aminopropyltriethoxy dimethoxy silicon Alkane, 3- aminopropyltriethoxy diethoxy silane, N- aminoethyl -3- aminopropyltriethoxy dimethoxysilane, N- aminoethyl -3- ammonia third Ylmethyl diethoxy silane, epoxypropoxy triethoxysilane, glycidoxy-propyltrimethoxy silane, the third oxygen of epoxy Hydroxypropyl methyl dimethoxysilane, glycidoxypropyl diethoxy silane, 1,2- bis- (trimethoxy silicon substrate) ethane, 1, One of 2- bis- (triethoxy silicon substrate) ethane etc. or more than one mixture.
According to the above scheme, the fluozirconate is selected from one of ammonium fluozirconate, potassium fluorozirconate and sodium fluozirconate etc. or one Kind or more mixture.
According to the above scheme, the structural formula difference of the amino Q type POSS is as follows:
Wherein, R1For 3- aminopropyl-dimethylsilyl bis (H2NC3H6(CH3)2SiO—)。
According to the above scheme, the acid is hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, malic acid, citric acid, tartaric acid, lactic acid, grass One of acid etc. or more than one mixture.
According to the above scheme, the metallic promoter agent is one of manganese sulfate, manganese nitrate, copper sulphate, copper nitrate etc. or one Kind or more mixture.
According to the above scheme, the rare earth compound is one of lanthanum nitrate, lanthanum chloride, cerous nitrate, cerous sulfate etc. or one Kind or more mixture.
According to the above scheme, the organic stabilizer is in ethyl alcohol, methanol, glycerine, normal propyl alcohol, isopropanol, n-butanol etc. Any one or more than one mixture.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) it after sour, fluozirconate and/or fluorine zirconic acid, metallic promoter agent and rare earth compound being added in water, stirs evenly As component A;
2) amino Q type POSS, silane and organic stabilizer are added in water, is used as B component after mixing evenly;
3) B component obtained by step 2) is added in component A obtained by step 1), is stirred evenly to get modified to Q type POSS Metal surface pretreating reagent.
According to the above scheme, it is respectively formed in the component A according to the mass fraction are as follows: 40-95 parts of water, fluozirconate and/or fluorine It is 0.01-20 parts of zirconic acid, 0-10 parts sour, 0-1 parts of metallic promoter agent, 0-0.5 parts of rare earth compound.
According to the above scheme, it is respectively formed in the B component according to the mass fraction are as follows: 4-40 parts of water, 0.01-5 parts of Q type POSS, 0.01-20 parts of silane, 0-5 parts of organic stabilizer.
Q type 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 method is: the modified metal surface pretreating reagent of the Q type POSS being diluted with water to and is contained admittedly Amount is 0.001-1%, and adjusts pH to 3.8-5.0, carries out pre-treatment to metal using infusion method or spray process and obtains silane film Layer.Wherein, it adjusts pH and generallys use the strong base-weak acid salts such as the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid or sodium carbonate or sodium hydroxide Equal alkali.
Compared with prior art, the beneficial effects of the present invention are:
(1) Q type 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 synchronous to be carried out, and is mutually adulterated, is formed fine and close inorganic-organic hybridization film, silane can repair fluorine zirconic acid in time The defects of salt film forming procedure optimizes membrane structure, and multiple amino of Q type 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 type 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) it can be used as crosslinked with silicane promotor, be conducive to accelerate forming silane film, make at of short duration metal surface It manages in the time, water-soluble silane adsorbs and be crosslinked film forming without that can be dissolved in water in metal surface, and metal processing piece leaves silane 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 type POSS, ensure that the stability of aqueous silane systems, And aqueous silane and fluozirconate can be re-dubbed uniform solution, and stability is very well, it can be achieved that the single group of user separates dilute make With.
(4) Q type POSS of the present invention modified metal surface pretreating reagent can obtain fine and close hydridization in metal surface Film, the film have excellent silane film (i.e. no upper outer protective paint, the lower naked mould of abbreviation) antirust ability and are coupled energy with coating Power.
Q type POSS of the present invention modified metal surface pretreating reagent may be substituted for conventional phosphatizing processing technique, Suitable for using various industrial circles of metal, such as automobile, household electrical appliances coating, hardware etc..
Specific embodiment
For a better understanding of the present invention, below 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 metal surface pretreating reagent that Q type POSS is modified, composition includes: 54.89 parts of water, 10 according to the mass fraction Part ammonium fluozirconate, 0.02 part of eight eight oligomeric silsesquioxane ((H of (3- aminopropyl-dimethylsilyl bis) cage type2NC3H6(CH3)2SiOSiO1.5)8) (molecular formula are as follows: C40H112Si16O20N8) (CAS registration number: 2046327-37-9), 20 parts of three second of 3- aminopropyl Oxysilane, 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 type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 40 parts of water, 10 parts of ammonium fluozirconates are added under agitation, it is primary after being completely dissolved 2 parts of citric acids, 8 parts of malic acid, 0.02 part of cerous sulfate and 0.01 part of lanthanum nitrate is added, is uniformly mixing to obtain component A;
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, is used as B component after mixing evenly;
3) B component is added in component A, stirs evenly and obtain the modified metal surface pretreating reagent of Q type POSS, i.e., A kind of environment-friendly type silane coating metal surfaces pretreating reagent.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent is opened with pure water 1:39 it is dilute, open it is dilute after apparently Solid content is 1.0%, and the pH value of dilute rear solution is opened with pH meter measurement, is maintained at 4.0 with sodium carbonate regulating solution pH;Then it uses Infusion method after the cold-reduced sheet after degreasing is impregnated 30 seconds wherein, with twice of pure water rinsing, then uses 10421 electrophoretic paint of ippon Electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
According to measurement cold-reduced sheet silane film (the cold rolling plate surface i.e. before electrophoresis of method as defined in GB/T10125 and GB/T6461 Film layer) resistance to Neutral Salt Spray Corrosion performance, according to method as defined in GB/T 1720 measurement cold-reduced sheet silane film adhesive force; According to the flexibility of the measurement cold-reduced sheet silane film of method as defined in GB/T 1731;It is measured according to method as defined in GB/T 1732 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 flexibility.Test result is as shown in table 1.
Embodiment 2
A kind of Q type POSS modified metal surface pretreating reagent, composition include: according to the mass fraction 98.89 parts of water, 0.01 part of fluorine zirconic acid, 0.01 part of eight eight oligomeric silsesquioxane ((H of (3- aminopropyl-dimethylsilyl bis) cage type2NC3H6(CH3)2SiOSiO1.5)8) (molecular formula are as follows: C40H112Si16O20N8) (CAS registration number: 2046327-37-9), 0.08 part of third oxygen of epoxy third Base trimethoxy silane, 0.9 part of N- aminoethyl -3- aminopropyl trimethoxysilane, 0.01 part of malic acid and 0.1 part of nitric acid.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) according to the mass fraction, in 74 parts of water, under agitation be added 0.01 part of malic acid, 0.1 part of nitric acid and 0.01 part of fluorine zirconic acid, obtains component A after being completely dissolved;
2) it is added 0.01 part of amino Q type POSS under agitation in 24.89 parts of water, after stirring and dissolving, adds 0.08 part of glycidoxy-propyltrimethoxy silane, 0.9 part of N- aminoethyl -3- aminopropyl trimethoxysilane, after mixing evenly As B component;
3) B component is added in component A, is stirred evenly to get the metal surface pretreating reagent modified to Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent and pure water are diluted with volume ratio 1:1099, And its pH value is measured with pH meter, and adjust pH with sodium hydroxide and be maintained at 4.0;Then use infusion method by the cold-reduced sheet after degreasing After impregnating 3 minutes wherein, with twice of pure water rinsing, then with 10421 electrophoretic paint electrophoresis of ippon;With after pure water rinsing after electrophoresis, Hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1 Property.Test result is as shown in table 1.
Embodiment 3
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 95.38 parts of water, 3 according to the mass fraction Part fluorine zirconic acid, 0.5 part of Q type-POSS, 0.1 part of N- aminoethyl -3- aminopropyl trimethoxysilane, 1 part of tartaric acid, 0.01 part of nitre Sour copper, 0.01 part of glycerine.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 91.38 parts of water, under agitation be added 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 three second of N- aminoethyl -3- aminopropyl are added under agitation Oxysilane after stirring and dissolving, adds 0.5 part of Q type-POSS, is used as B component after mixing evenly;
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent is opened with pure water 1:49 it is dilute, open it is dilute after apparently Solid content is 0.09%, and the pH value of dilute rear solution is opened with pH meter measurement, pH value of solution is adjusted with nitric acid, pH value of solution is made to be 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 ippon 10421 electrophoretic paint electricity Swimming, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1 Property.Test result is as shown in table 1.
Embodiment 4
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 89.3 parts of water, 0.2 according to the mass fraction Part fluorine zirconic acid, 5 parts of Q type-POSS, 1 part of 1,2- bis- (front three oxygen silicon base) ethane, 1 part of 2- aminoethyl trimethoxy silane, 1 part of ring The third oxygen propyl trimethoxy silicane of oxygen, 0.5 part of hydrochloric acid, 1 part of n-butanol and 1 part of isopropanol.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 80 parts of water, 0.2 part of fluorine zirconic acid is added under agitation, it is primary after being completely dissolved 0.5 part of hydrochloric acid is added, is uniformly mixing to obtain component A;
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 are used as B component after mixing evenly;
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent being opened with pure water 1:199 dilute, opens dilute table afterwards Seeing solid content is 0.044%, protects pH value of solution with sodium hydrate regulator solution pH with the pH value that dilute rear solution is opened in pH meter measurement It holds 4.0, using infusion method, after the cold-reduced sheet after degreasing is impregnated 3 minutes, with twice of pure water rinsing, using 10421 electricity of ippon Swimming paint electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1 Property.Test result is as shown in table 1.
Embodiment 5
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 75 parts of water, 1 part of fluorine according to the mass fraction Sodium zirconate, 0.01 part of potassium fluorozirconate, 0.9 part of Q type-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 type POSS modified metal surface pretreating reagent, mainly includes 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, it is primary after being completely dissolved that 3 parts of nitric acid, 0.01 part of copper nitrate, 0.02 part of lanthanum nitrate, 0.06 part of cerous sulfate are added, it stirs evenly 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, is used as B component after mixing evenly;
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent being opened with pure water 1:599 dilute, opens dilute table afterwards Seeing solid content is 0.03%, keeps pH value of solution with sodium hydrate regulator solution pH with the pH value that dilute rear solution is opened in pH meter measurement 4.0, using infusion method, after the cold-reduced sheet after degreasing is impregnated 3 minutes, with twice of pure water rinsing, using 10421 electrophoresis of ippon Electrophoresis is painted, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1 Property.Test result is as shown in table 1.
Embodiment 6
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 67 parts of water, 20 parts according to the mass fraction Fluorine zirconic acid, 4 parts of Q type-POSS, 1 part of 1,2- bis- (three ethoxy silicon substrates) ethane, 1 part of 3- aminopropyltriethoxy 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 type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 45 parts of water, 3 part of 98% sulfuric acid, 2 parts of citric acids, 20 parts are added under agitation 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- aminopropyltriethoxy 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, is used as B component after mixing evenly;
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent being opened with pure water 1:639 dilute, opens dilute table afterwards Seeing solid content is 0.05%, keeps pH value of solution with sodium hydrate regulator solution pH with the pH value that dilute rear solution is opened in pH meter measurement 4.0, using infusion method, the cold-reduced sheet after degreasing is impregnated after five minutes, with twice of pure water rinsing, using 10421 electrophoresis of ippon Electrophoresis is painted, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1 Property.Test result is as shown in table 1.
Comparative example 1
A kind of metal surface pretreating reagent, composition includes: 95 parts of water, 3 parts of fluorine zirconic acids, 1 part of epoxy according to the mass fraction Third oxygen propyl trimethoxy silicane, 1 part of citric acid.
The preparation method of above-mentioned metal surface pretreating reagent mainly includes the following steps: as mass fraction, in 75 parts of water In, 3 parts of fluorine zirconic acids are added under agitation, is stirring evenly and then adding into 1 part of citric acid, is uniformly mixing to obtain component A;At 20 parts In water, 1 part of glycidoxy-propyltrimethoxy silane is added under agitation, is used as B component after mixing evenly;By B component It is added in component A, stirs evenly and obtain metal surface pretreating reagent.
Application method: above-mentioned metal surface pretreating reagent is opened with pure water 1:99 it is dilute, open it is dilute after apparent solid content be 0.05%, so that pH value of solution is maintained at 3.8 with sodium hydroxide solution pH with the pH value that dilute rear solution is opened in pH meter measurement, using spray Method, after five minutes by the cold-reduced sheet spray after degreasing, with twice of pure water rinsing, using 10421 electrophoretic paint electrophoresis of ippon, after electrophoresis After pure water rinsing, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1 Property.Test result is as shown in table 1.
Comparative example 2
A kind of metal surface pretreating reagent, composition includes: 95 parts of water, 3 parts of fluorine zirconic acids, 1 part of 3- ammonia according to the mass fraction Propyl trimethoxy silicane, 1 part of 60% concentrated nitric acid.
The preparation method of above-mentioned metal surface pretreating reagent, mainly includes the following steps:
As mass fraction, in 75 parts of water, 3 parts of fluorine zirconic acids is added under agitation, are 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 B component is used as after uniformly;B component is added in component A, stirs evenly and obtains metal surface pretreating reagent.
Application method: above-mentioned metal surface pretreating reagent is opened with pure water 1:99 it is dilute, open it is dilute after apparent solid content be 0.05%, so that pH value of solution is maintained at 3.8 with sodium hydroxide solution pH with the pH value that dilute rear solution is opened in pH meter measurement, using spray Method, after five minutes by the cold-reduced sheet spray after degreasing, with twice of pure water rinsing, using 10421 electrophoretic paint electrophoresis of ippon, after electrophoresis After pure water rinsing, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1 Property.Test result is as shown in table 1.
Table 1
As it can be seen from table 1 metal surface pretreating reagent Q type POSS modified in each embodiment is formed in cold rolling plate surface Silane film there is good adhesive force, flexibility and impact resistance, with the anti-corruption in extraordinary room temperature atmospheric environment Erosion ability, and without addition Q type POSS compound in comparative example, resulting cold-reduced sheet silane film is rapid in room temperature atmospheric environment It gets rusty;Through electrophoresis after cold-reduced sheet silane film painting on surface film, in embodiment 1-6 paint film all have extraordinary adhesive force, Flexibility, impact resistance and excellent resistance to neutral salt spray performance, comprehensive performance are more than 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, corrosion resistance is also very poor, and joint multiply far is not achieved Requirement with vehicle enterprise to body paint.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention Protection scope.

Claims (7)

1. a kind of Q type POSS modified metal surface pretreating reagent, it is characterised in that the raw material of the metal surface pretreating reagent Component includes: 0.01-20 parts of silane according to the mass fraction, fluozirconate and/or 0.01-20 parts of fluorine zirconic acid, eight (aminopropyl diformazans Base siloxy) 0.01-5 parts of eight oligomeric silsesquioxane of cage modle, it is 0-10 parts sour, 0-1 parts of metallic promoter agent, rare earth compound 0-0.5 Part, 0-5 parts of organic stabilizer, 44-135 parts of water.
2. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the silane is 3- Aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, N- aminoethyl -3- aminopropyl trimethoxysilane, N- ammonia second Base -3- aminopropyl triethoxysilane, 3- aminopropyltriethoxy dimethoxysilane, 3- aminopropyltriethoxy diethoxy silane, N- Aminoethyl -3- aminopropyltriethoxy dimethoxysilane, N- aminoethyl -3- aminopropyltriethoxy diethoxy silane, the third oxygen of epoxy third Ethyl triethoxy silicane alkane, glycidoxy-propyltrimethoxy silane, glycidoxypropyl dimethoxysilane, the third oxygen of epoxy One of hydroxypropyl methyl diethoxy silane, 1,2- bis- (tri-alkoxy silicon substrate) ethane or more than one mixture;Work as institute When to state silane be more than one mixture, wherein must have amino silane.
3. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the eight (ammonia third Base dimethylsilyl bis) cage modle eight oligomeric silsesquioxane be amino Q type POSS, structural formula is as follows:
Wherein, R1For 3- aminopropyl-dimethylsilyl bis.
4. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the acid is hydrogen fluorine One of acid, hydrochloric acid, sulfuric acid, nitric acid, malic acid, citric acid, tartaric acid, lactic acid, oxalic acid or more than one mixture;Institute State organic stabilizer be ethyl alcohol, it is methanol, glycerine, normal propyl alcohol, isopropanol, any one or more than one mixed in n-butanol Close object.
5. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the metal promoted Agent is one of manganese sulfate, manganese nitrate, copper sulphate, copper nitrate or more than one mixture;The rare earth compound is nitre One of sour lanthanum, lanthanum chloride, cerous nitrate, cerous sulfate or more than one mixture.
6. a kind of preparation method of Q type POSS modified metal surface pretreating reagent, it is characterised in that mainly include the following steps:
1) it after fluozirconate and/or fluorine zirconic acid, acid, metallic promoter agent and rare earth compound being added in water, stirs evenly as A Component;
2) add eight oligomeric silsesquioxane of organic stabilizer, silane and eight (aminopropyl dimethylsilyl bis) cage modles, stirring in water B component is used as after uniformly;
3) B component obtained by step 2) is added in component A obtained by step 1), is stirred evenly to get the gold modified to Q type POSS Metal surface pretreating reagent;
It is respectively formed in the component A according to the mass fraction are as follows: 40-95 parts of water, fluozirconate and/or 0.01-20 parts of fluorine zirconic acid, acid 0-10 parts, 0-1 parts of metallic promoter agent, 0-0.5 parts of rare earth compound;It is respectively formed in the B component according to the mass fraction are as follows: water 4- 40 parts, eight 0.01-5 parts of eight oligomeric silsesquioxanes of (aminopropyl dimethylsilyl bis) cage modles, 0.01-20 parts of silane, organic stabilizers 0-5 parts of agent.
7. the application method of Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that will It is 0.001-1% that the Q type POSS modified metal surface pretreating reagent, which is diluted with water to solid content, and adjusts pH to 3.8- In the range of 5.0, pre-treatment is carried out to metal using infusion method or spray process.
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