CN108085664A - Environment-friendly type macromolecule modified silane vitrification liquid and preparation method thereof - Google Patents
Environment-friendly type macromolecule modified silane vitrification liquid and preparation method thereof Download PDFInfo
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- CN108085664A CN108085664A CN201711452474.XA CN201711452474A CN108085664A CN 108085664 A CN108085664 A CN 108085664A CN 201711452474 A CN201711452474 A CN 201711452474A CN 108085664 A CN108085664 A CN 108085664A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C22/68—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 solutions with pH between 6 and 8
-
- 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
Abstract
The present invention relates to a kind of environment-friendly type macromolecule modified silane vitrification liquid, using water as solvent, contain vitrified agent in raw material；The vitrified agent includes silane, fluozirconate and/or fluorine zirconic acid, colloidal silicon dioxide and the resin compound at least containing MQ silicones and polyurethane resin.The epithelium that the vitrification liquid obtains meet basic adhesive force and it is flexible simultaneously, there is excellent anti-corrosion capability.The vitrification liquid can be used for Coating Pretreatment, and can be with overpickling.
Description
Technical field
The invention belongs to field of metal surface treatment, and in particular to a kind of macromolecule modified silane vitrification liquid and its preparation side
Method.
Background technology
Metal material is damaged by the effect of surrounding medium, is known as metal erosion.During metal erosion, on the interface of metal
Chemistry or electrochemistry heterogeneous reaction has occurred in metal and empty gas and water etc., metal is made to be 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, shorten the service life of equipment.
It is the most common important method for preventing metal erosion to apply epithelium protection on the metal surface.Traditional is main
Metal surface pre-treating method mainly have a chemical conversion embrane method, typical chemical conversion embrane method has phosphorating treatment, chromaking passivation
Processing etc., but these traditional process for treating surface are faced with huge environmental pressure.Because there are serious for chromic acid passivation method
Pollution of chromium, this method have limited use；And parco-lubrizing is polluted there are serious phosphorus, while other heavy metal pollutions are also brought,
Belong to the technology of being eliminated.To solve the pollution problem of conventional method, people more and more can having focused on for research
Substitute the technical of conventional surface treatment process.
At present, new metal surface pretreatment technology mainly has vitrification technology（Titanium salt/zirconates conversion film, silane conversion
Film）, tannate conversion membrane technology, Molybdate Conversion Film, cerium-based conversion coating technology etc..Titanium salt conversion film vitrification technology, tannin
Hydrochlorate converts membrane technology, Molybdate Conversion Film, cerium-based conversion coating technology since comprehensive performance is defective, only in some special dimensions
It is applied, fails to promote the use of on a large scale, and zirconates conversion film and silane conversion film vitrification technology be due to haveing excellent performance, by
To widely studied, and applied in a big way.
Zirconates conversion film vitrification technology refers to, using fluozirconate as chemical composition coating active component, handle before metal
Cheng Zhong, fluozirconate hydrolyze to form silica coating in metal surface.The advantage of this technology is that film layer is fine and close compared with phosphating coat,
Required film layer is substantially reduced compared with phosphating coat, and its film-forming process flow is similar with phosphatization, therefore can be in Pretreatment Line
It is upper directly to substitute phosphatization.But since the vitrification film layer still has more film forming defect, addition sealer is generally required, such as
NaNO2Deng progress after-treatment, that is, increase process, also increase pollution.Silanization metal surface treatment technology is as a kind of new
Technology, overcoming that the energy consumption in the metal surface treatment technologies such as traditional phosphatization, chromaking is big, pollution is big etc. itself can not overcome
The shortcomings that, oneself had obtained actual application through having obtained extensive development in industrial application in recent years.Silane is a kind of
The hybrid object of silicon substrate, basic molecular formula are：Y(CH2)nSiR2x(OR3)3-x, wherein OR3It is hydrolyzable base
Group, Y is organo-functional group.Although silanization improves epithelium corrosion resistance and processability, but the film forming speed when being coated with to metal
Slowly the dhering strength that, forms a film is low.
In view of the problem of above-mentioned zirconates conversion film and silanization form a film, it is therefore desirable to explore environment-friendly high-efficiency have both it is simple for process
Metal surface treatment process.
The content of the invention
From the above mentioned, in a first aspect, the Section 1 technical solution of the present invention provides a kind of environment-friendly type macromolecule modified silicon
Alkane vitrification liquid, using water as solvent,
Contain vitrified agent in raw material；
The vitrified agent includes silane, fluozirconate and/or fluorine zirconic acid, colloidal silicon dioxide and at least contains MQ silicon trees
The resin compound of fat and polyurethane resin.
Preferably, the raw material components of the vitrification liquid are contained according to the mass fraction on the basis of 100 mass fraction of gross mass
Have：0.01-10 parts of 0.05-35 parts of silane, fluozirconate and/or fluorine zirconic acid, 0.5-10 parts of colloidal silicon dioxide at least contain MQ
5-15 parts of the resin compound of silicones and polyurethane resin, 0.1-5 parts of lubricant, remaining is water.
Preferably, the silane is selected from 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, 2- aminoethyls three
Methoxy silane, 2- aminoethyls triethoxysilane, ammonia first propyl trimethoxy silicane, aminomethyl triethoxysilane, N- ammonia
Ethyl -3- aminopropyl trimethoxysilanes, N- aminoethyl -3- aminopropyl triethoxysilanes, 3- aminopropyltriethoxy dimethoxys
Silane, 3- aminopropyltriethoxies diethoxy silane, N- aminoethyl -3- aminopropyltriethoxies dimethoxysilane, N- aminoethyl -3- ammonia
Hydroxypropyl methyl diethoxy silane, epoxypropoxy triethoxysilane, glycidoxy-propyltrimethoxy silane, epoxy third
Oxygen propyl group methyl dimethoxysilane, glycidoxypropyl diethoxy silane, 1,2- bis- (trimethoxy silicon substrate) second
Any one in alkane, 1,2- bis- (triethoxy silicon substrate) ethane or more than one mixture.
Preferably, the fluozirconate is any one in ammonium fluozirconate, potassium fluorozirconate and sodium fluozirconate or one
Kind or more mixture.
Preferably, it is 50nm containing the colloidal silicon dioxide that grain size is below 20nm and grain size in the colloidal silicon dioxide
Above colloidal silicon dioxide.
Preferably, the siloxy units of the MQ silicones are selected from (R3SiO1/2) a M units represented and with (SiO4/
2) Q unit that b is represented, a and b represent more than 0 integer；And the value that MQ silicones is molecular weight 50~700,000, a/b is
0.6~1.0 solid vinyl ylmethyl MQ silicones or the methyl MQ silicones containing silicone hydroxyl.
Preferably, the polyurethane resin is superbrnaching end-hydroxy polyurethane.
Preferably, the lubricant is at least one kind of in polyethylene wax, polypropylene wax or Brazil wax.
Preferably, the mass ratio of the MQ silicones in the resin compound and polyurethane resin is 0.5-2.5.
Second aspect, Section 2 technical solution of the invention are a kind of environment-friendly type macromolecule modified silane vitrification liquid of preparing
Method adds fluozirconate and/or fluorine zirconic acid, colloidal silicon dioxide in water, stir 5-10 minutes, obtains the first solution；
Silane and the resin compound at least containing MQ silicones and polyurethane resin are added in water, stirs 0.5-2h, obtain second
Solution；First solution and the second solution are uniformly mixed, obtain environment-friendly type macromolecule modified silane vitrification liquid.
Vitrification liquid of the present invention can substitute conventional phosphatizing treatment technology, be led suitable for the various industry for using metal
Domain, such as automobile, household electrical appliances application, hardware etc..
Vitrification liquid of the present invention can be also used for Coating Pretreatment.Coating Pretreatment eliminates coated article table before referring to application
Various greasy dirts on face（Such as lubricating oil, emulsion, grease, sweat stain）And dust, the cleaning process for making coated surface cleaning are to apply
Fill the essential process of pre-treating technology；Clean coated surface（Whether）Which kind of chemical treatment carried out（Or conversion film process）
Or machining processes（Such as Shot Blasting）, according to the ground and surface state of coated article, coating process requirement is selected.
Vitrification liquid of the present invention can be also used for overpickling.
Below with reference to specific embodiment and embodiment to the technique effect of the design of the present invention, concrete structure and generation
It is described further, to be fully understood from the purpose of the present invention, feature and effect.
Description of the drawings Fig. 1 is MQ resin structure formulas
Specific embodiment
Some details are elaborated in being described below, to understand various embodiments of the present invention.Association area
Ordinarily skilled artisan will understand that they can put into practice other embodiments of the present invention without one or more described herein
Details.Therefore, applicant is not intended to is limited to this details by the scope of the appended claims in any way.It is although right
The description of various processes with reference to the step and order in disclosure below, but it is not considered that these steps and step it is suitable
Sequence be practice the present invention all embodiments necessary to.
Vitrification liquid of the present invention is a kind of macromolecule modified silane vitrification liquid of non-phosphate environment-friendly type Treatment of Metal Surface,
Using water as solvent, contain vitrified agent in raw material；The vitrified agent includes silane, fluozirconate and/or fluorine zirconic acid, colloid dioxy
SiClx and the resin compound at least containing MQ silicones and polyurethane resin.
As preferred technical solution, the vitrification liquid raw material components are on the basis of 100 mass fraction of gross mass, by quality
Number meter contains：0.01-10 parts of 0.05-35 parts of silane, fluozirconate and/or fluorine zirconic acid, 0.5-10 parts of colloidal silicon dioxide, until
Few 5-15 parts of resin compound containing MQ silicones and polyurethane resin, 0.1-5 parts of lubricant, remaining is water.
As preferred technical solution, the vitrification liquid raw material components are on the basis of 100 mass fraction of gross mass, by quality
Number meter contains：0.1-5 parts of 5-25 parts of silane, fluozirconate and/or fluorine zirconic acid, 1-8 parts of colloidal silicon dioxide at least contain MQ
5-15 parts of the resin compound of silicones and polyurethane resin, 0.1-5 parts of lubricant, remaining is water.
Silane：Contain silane in vitrified agent of the present invention, the silane is selected from 3- aminopropyl trimethoxysilanes, 3-
Aminopropyl triethoxysilane, 2- aminoethyls trimethoxy silane, 2- aminoethyls triethoxysilane, ammonia first propyl trimethoxy
Silane, aminomethyl triethoxysilane, N- aminoethyl -3- aminopropyl trimethoxysilanes, three ethoxy of N- aminoethyl -3- aminopropyls
Base silane, 3- aminopropyltriethoxies dimethoxysilane, 3- aminopropyltriethoxies diethoxy silane, N- aminoethyl -3- aminopropyl first
Base dimethoxysilane, N- aminoethyl -3- aminopropyltriethoxies diethoxy silane, epoxypropoxy triethoxysilane, ring
The third oxygen propyl trimethoxy silicane of oxygen, glycidoxypropyl dimethoxysilane, glycidoxypropyl diethoxy
It is one or more kinds of mixed in silane, 1,2- bis- (trimethoxy silicon substrate) ethane, 1,2- bis- (triethoxy silicon substrate) ethane
Close object.And then preferably comprise the silane of amino.
Fluozirconate：The fluozirconate is one kind or one in ammonium fluozirconate, potassium fluorozirconate and sodium fluozirconate etc.
Kind or more mixture.
Colloidal silicon dioxide：The species of colloidal silicon dioxide is not particularly limited, such as can be grain size 4-200nm or so
Graininess SiO2, and then sodium, potassium, ammonia etc. can be contained and be used as stabilizer.As the preferred embodiment of colloidal silicon dioxide, Ke Yiju
Go out the scheme containing average grain diameter different 2 kinds or colloidal silicon dioxide of more than two kinds.If the program, then the table that obtains
The various characteristics of surface treatment metal material are more excellent.It should be noted that in the assay method of average grain diameter, using laser diffraction/
The measured value of scattering formula particle size distribution device.
It should be noted that during colloidal silicon dioxide containing two or more grain size, it is preferable to use the glue that grain size is below 20nm
Body silica and the colloidal silicon dioxide that grain size is more than 50nm.
Wherein, the 2nd colloid dioxy for the use of the 1st colloidal silicon dioxide that grain size is below 20nm being more than 50nm with grain size
During SiClx, mass ratio (quality of the colloidal silicon dioxide of the quality of the 1st colloidal silicon dioxide/the 2nd) is preferably 4.1-5.0, into
And it is preferred that 4.1-4.5, is more easy to carry out merging the stable epithelium of formation with other raw material components at this time.
Contain at least two kinds of trees in MQ silicones, polyurethane resin and acrylic resin in vitrification liquid of the present invention
Compound.The more preferably combination of MQ silicones and polyurethane resin.
MQ silicones：MQ silicones is one kind of organic siliconresin, is by single functionality siloxane unit
(R3SiO1/2) a, abbreviation M units with tetra functional siloxane polycondensation chain link (SiO4/2) b, claim the structure that Q unit is formed to compare
Special organic siliconresin.Primary structure is the M chain links and Q in [R3SiO1/2] a [SiO4/2] b, MQ silicones molecular structure
The ratio between chain link amount determines its property and application range, and wherein R can be the groups such as hydroxyl, alkyl, phenyl, alkenyl.
It is generally acknowledged that MQ resins are the close orbicule of double-deck three-dimensional structure, core part links for silicon oxygen bond, and appearance is double
The close orbicule of layer structure, the caged SiO that the degree of polymerization is 15~50 and degree is higher2, a part for spherical shell is smaller by density
R3SiO0.5Layer is surrounded.MQ resin structure formulas are illustrated in fig. 1 shown below：
Scheme is preferably carried out as one, the molecular weight of MQ silicones of the present invention is 50~700,000, the MQ silicones
Siloxy units be selected from (R3SiO1/2) a represent M units and with (SiO4/2) Q unit that b is represented, the R independently is
The alkyl group or alkenyl group of hydroxyl, 1~6 carbon, a and b represent more than 0 integer.And then the ratio of preferably a/b is
0.6~1.0 solid vinyl ylmethyl MQ silicones or the methyl MQ silicones containing silicone hydroxyl.
Scheme is preferably carried out as one, MQ silicones of the present invention is the methyl MQ silicones containing silicone hydroxyl, and
Hydroxy radical content is 1%~10wt%, and the ratio of a/b is 0.7~0.9.
Polyurethane resin：The species of polyurethane resin is not particularly limited, as long as it can by known manufacturing method
Obtained polyurethane resin then can be used.Polyurethane resin may be used alone, or two or more kinds may be used in combination.Example
Such as, the dispersion by obtaining as follows can be used：Using polyalcohol, polyisocyanates or with 2 or more hydroxyl or
Compound of amino and the carboxyl of 1 or more etc. is commonly used in the compound of the manufacture of polyurethane resin, according to known
Method polymerize, scattered by being added to the water together with the alkali compounds such as obtained urethane polymer and ammonia, polyamines.
As particularly preferred, the polyurethane resin is superbrnaching end-hydroxy polyurethane.Hyper-branched polymer is unique with it
Molecular structure, it is soluble, containing substantial amounts of end group, strand not easy entanglement.It can be by using the very high end of purity
Hydroxyl small molecule polyol low molecular polylol is initiator, is surpassed using diisocyanate and dialkanol amine as Material synthesis terminal hydroxy group
Branched polyurethanes.
Specifically, the superbrnaching end-hydroxy polyurethane synthesizes by the following method：
（1）3~4 grams of terminal hydroxy group small molecule polyols is taken to be dissolved in 20 grams of aprotic organic solvents, it is more to obtain terminal hydroxy group small molecule
First alcoholic solution；
The terminal hydroxy group small molecule polyol includes trimethylolpropane, 1,4- butanediols, 1,6-HD, pentaerythrite or sweet
Oil；The aprotic organic solvent is N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
（2）10~30 grams of diisocyanate are taken, are warming up to 70~90 DEG C, terminal hydroxy group small molecule polyol solution is added in, adds
Enter the catalyst of 0~0.3% mass fraction, when reaction 4~6 is small, obtain prepolymer a1；
The diisocyanate is isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methyl hydride diisocyanate
(HMDI), toluene diisocyanate（TDI）, hexamethylene diisocyanate (HDI), Methylcyclohexyl diisocyanate
(HTDI) or 4,4 '-methyl diphenylene diisocyanate (MDI)；The catalyst is sub- for dibutyl tin laurate or octanoic acid
Tin.
（3）20~45 grams of hyper-branched prepolymers a1 and 15~25 grams of dialkanol amines are cooled to 0~15 DEG C, it is anti-after blending
Answer 4~6 it is small when, product with precipitating reagent separating-purifying vacuum drying just obtain superbrnaching end-hydroxy polyurethane；
The precipitating reagent is acetone, ether, water or isopropanol.
Scheme is preferably carried out as one, and the mass ratio of MQ silicones and polyurethane resin in resin compound is
0.5-2.5, and then preferred 1-2 are most preferably 1：1.
Metal material is surface-treated by using environment-friendly type macromolecule modified silane vitrification liquid of the present invention, can be obtained
Excellent effect is obtained, by inference, the Q structures in the MQ silicones contain a large amount of reactive hydroxyl end group groups, energy and metal watch
Face contacts and hydrogen bond action absorption occurs in metal surface, and the different types of R group in M structure has can be with vitrified agent
Middle other components carry out crosslinked action to build metal surface three-dimensional network shape epithelium, and some R groups have good hydrophobicity,
It can stop directly etching of the aqueous caustic product to metal.And the superbrnaching end-hydroxy polyurethane in preferred embodiment and MQ trees
Fat all has special macromolecular structure, can cooperate with the stabilization for promoting epithelium structure, improve the anti-corrosion long-term effect used.
Lubricant：The species of lubricant is not particularly limited in vitrification liquid of the present invention, it is contemplated that the surface-treated metal of gained
The superior aspect of various characteristics of material, is preferably selected from least one kind of in polyethylene wax, polypropylene wax, Brazil wax.
In vitrification liquid of the present invention, in addition to above-mentioned each neccessary composition and water.Alcohol, ketone, molten fibre can be also added as needed on
The water-soluble secondary solvent of agent system, surfactant, antifoaming agent, levelling agent, fungi-proofing mould inhibitor, colorant etc..It is possible thereby to it carries
Drying property, coating appearance, workability, storage characteristics, the design of high disposal agent.It it should be noted, however, that should be by them with lossless
The degree of gained quality of the invention adds, is environment friendly and pollution-free, can be added according to addition custom commonly used in the art.
Another aspect of the invention provides a kind of method for preparing environment-friendly type macromolecule modified silane vitrification liquid, including
Following steps add fluozirconate and/or fluorine zirconic acid, colloidal silicon dioxide in water, stir 5-10 minutes, and it is molten to obtain first
Liquid；Silane and the resin compound at least containing MQ silicones and polyurethane resin are added in water, stir 0.5-2h, acquisition the
Two solution；First solution and the second solution are uniformly mixed, obtain environment-friendly type macromolecule modified silane vitrification liquid.
The pH of vitrification liquid of the present invention is not particularly limited, be preferably 6-8, adjust pH can be used hydrochloric acid, sulfuric acid or ammonium hydroxide,
The alkali such as sodium hydroxide.Vitrification liquid of the present invention can be used for the metallic surfaces pre-treatments such as steel, galvanized sheet, aluminium alloy plate.Specifically,
Vitrification liquid can be diluted with water as needed, dilution ratio 1：100-10000.
It, as needed, can be real to metal material in order to remove the oil on metal material surface, spot before coating
Apply pretreatment.Metal material scribbles antirust oil for antirust mostly.Moreover, even if do not using the situation of antirust oil oiling
Under, also there are the oil adhered in operation, spot etc..By implementing to pre-process, it will be cleaned on metal material surface, make metal material
Surface is easily equably soaked by vitrification liquid.It should be noted that no oil, spot etc., material surface is by metal material surface
In the case that inorganic agent equably soaks, do not need especially to pre-process stroke.It should be noted that the method for pretreatment is without special
It limits, the method that hot water wash, solvent washing, alkali degreasing washing etc. can be enumerated.Infusion method or spray process can be used afterwards to gold
Belong to the surface treatment for carrying out vitrification liquid.
Embodiment
Embodiment and comparative example are exemplified below, the present invention is further illustrated, but the present invention is not limited to these realities
Apply example.
Further more, in following, as silane, fluozirconate and/or fluorine zirconic acid, colloidal silicon dioxide, MQ silicones and poly- ammonia
Ester resin is not as having specified otherwise, using commercial product.
[silane]
A：3- aminopropyl triethoxysilanes
[fluozirconate and/or fluorine zirconic acid]
B1：Sodium fluozirconate
B2：Fluorine zirconic acid
[colloidal silicon dioxide]
C1:Grain size is the colloidal silicon dioxide of below 20nm
C2：The 2nd colloidal silicon dioxide that the 1st colloidal silicon dioxide that grain size is below 20nm is more than 50nm with grain size, matter
It is 4.5 to measure than (quality of the colloidal silicon dioxide of the quality of the 1st colloidal silicon dioxide/the 2nd)：1
[resin compound]
D1:Methyl MQ silicones containing silicone hydroxyl, a/b=0.9, hydroxyl 1.1wt%
D2：Polyurethane resin（Commercially available Superflex650）
D3：Superbrnaching end-hydroxy polyurethane resin：
（1）3 grams of pentaerythrites is taken to be dissolved in 20 grams of n,N-dimethylacetamide, obtain terminal hydroxy group small molecule polyol solution；
（2）10 grams of isophorone diisocyanate are taken, are warming up to 75 DEG C, add in pentaerythrite, two bays of 0.15% mass fraction
Sour dibutyl tin when reaction 4.5 is small, obtains prepolymer；
（3）30 grams of prepolymers and 20 grams of dialkanol amines are mixed, are cooled to 5 DEG C, when reaction 5 is small after blending, product acetone point
Superbrnaching end-hydroxy polyurethane D3 is obtained from purification vacuum drying.
[lubricant]
Polyethylene wax（Commercially available three wells W700）
Embodiment 1：
By mass parts number scale, 0.7 part of sodium fluozirconate, 0.1 part of fluorine zirconic acid, 2.5 parts of colloidal silicon dioxide C1 are added in 60 parts of water,
Stirring 5 minutes obtains the first solution；21 parts of silane A, 8 parts of MQ silicones D1 and 4 parts of polyurethane resins are added in 40 parts of water
D2,0.5 part of lubricant polyethylene wax stir 1h, obtain the second solution；First solution and the second solution are uniformly mixed,
Obtain environment-friendly type macromolecule modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Embodiment 2：
By mass parts number scale, 0.7 part of sodium fluozirconate, 0.1 part of fluorine zirconic acid, 2.5 parts of colloidal silicon dioxide C2 are added in 60 parts of water,
Stirring 10 minutes obtains the first solution；20 parts of silane A, 8 parts of MQ silicones D1 and 4 parts of polyurethane resins are added in 40 parts of water
D2,0.5 part of lubricant polyethylene wax stir 1h, obtain the second solution；First solution and the second solution are uniformly mixed,
Obtain environment-friendly type macromolecule modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Embodiment 3：
By mass parts number scale, 0.6 part of sodium fluozirconate, 0.2 part of fluorine zirconic acid, 2.5 parts of colloidal silicon dioxide C2 are added in 60 parts of water,
Stirring 10 minutes obtains the first solution；21 parts of silane A, 8 parts of MQ silicones D1 and 4 parts of polyurethane resins are added in 40 parts of water
D3,0.5 part of lubricant polyethylene wax stir 1.2h, obtain the second solution；First solution and the second solution are stirred
It is even, obtain environment-friendly type macromolecule modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Embodiment 4：
By mass parts number scale, 0.6 part of sodium fluozirconate, 0.2 part of fluorine zirconic acid, 2.5 parts of colloidal silicon dioxide C2 are added in 60 parts of water,
Stirring 10 minutes obtains the first solution；21 parts of silane A, 8 parts of MQ silicones D1 and 4 parts of polyurethane resins are added in 40 parts of water
D3,0.5 part of lubricant polyethylene wax stir 1.2h, obtain the second solution；First solution and the second solution are stirred
It is even, obtain environment-friendly type macromolecule modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Embodiment 5：
By mass parts number scale, 0.6 part of sodium fluozirconate, 0.2 part of fluorine zirconic acid, 2.5 parts of colloidal silicon dioxide C2 are added in 60 parts of water,
Stirring 10 minutes obtains the first solution；21 parts of silane A, 4 parts of MQ silicones D1 and 8 parts of polyurethane resins are added in 40 parts of water
D3,0.5 part of lubricant polyethylene wax stir 1 h, obtain the second solution；First solution and the second solution are uniformly mixed,
Obtain environment-friendly type macromolecule modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Embodiment 6：
By mass parts number scale, 0.6 part of sodium fluozirconate, 0.2 part of fluorine zirconic acid, 4.3 parts of colloidal silicon dioxide C2 are added in 60 parts of water,
Stirring 10 minutes obtains the first solution；21 parts of silane A, 3.5 parts of MQ silicones D1 and 3.5 parts of polyurethane are added in 40 parts of water
Resin D3,0.5 part of lubricant polyethylene wax stir 0.5h, obtain the second solution；First solution and the second solution are stirred
Uniformly, environment-friendly type macromolecule modified silane vitrification liquid is obtained.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Embodiment 7：
By mass parts number scale, 0.6 part of sodium fluozirconate, 0.2 part of fluorine zirconic acid, 4.3 parts of colloidal silicon dioxide C2 are added in 60 parts of water,
Stirring 10 minutes obtains the first solution；21 parts of silane A, 2.5 parts of MQ silicones D1,1 part of polyurethane resin are added in 40 parts of water
D2,3.5 parts of polyurethane resin D3,0.5 part of lubricant polyethylene wax stir 1.2h, obtain the second solution；By the first solution and
Two solution are uniformly mixed, and obtain environment-friendly type macromolecule modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Comparative example 1：
By mass parts number scale, 0.7 part of sodium fluozirconate, 0.1 part of fluorine zirconic acid are added in 60 parts of water, is stirred 5 minutes, it is molten to obtain first
Liquid；21 parts of silane A, 8 parts of polyurethane resin D2,0.5 part of lubricant polyethylene wax are added in 40 parts of water, stirs 1h, obtains the
Two solution；First solution and the second solution are uniformly mixed, obtain environment-friendly type macromolecule modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Comparative example 2：
By mass parts number scale, 0.6 part of sodium fluozirconate, 0.2 part of fluorine zirconic acid, 3 parts of colloidal silicon dioxide C1 are added in 60 parts of water, are stirred
It mixes 10 minutes, obtains the first solution；21 parts of silane A, 8 parts of polyurethane resin D2,0.5 part of poly- second of lubricant are added in 40 parts of water
Alkene wax stirs 1.2h, obtains the second solution；First solution and the second solution are uniformly mixed, obtain environment-friendly type macromolecule
Modified silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
Comparative example 3：
By mass parts number scale, 0.6 part of sodium fluozirconate, 0.2 part of fluorine zirconic acid, 3 parts of colloidal silicon dioxide C1 are added in 60 parts of water, are stirred
It mixes 10 minutes, obtains the first solution；21 parts of silane A, 8 parts of polyurethane resin D1,0.5 part of poly- second of lubricant are added in 40 parts of water
Alkene wax stirs 1h, obtains the second solution；First solution and the second solution are uniformly mixed, environment-friendly type macromolecule is obtained and changes
Property silane vitrification liquid.
Application process：By above-mentioned vitrification liquid and pure water 1：600 dilutions, it is 6.5 to adjust solution ph, will using infusion method
The pretreated cold-reduced sheet of degreasing impregnates 5 minutes in above-mentioned solution, then with twice of pure water rinsing, hot blast drying.
[test method]
The resistance to Neutral Salt Spray Corrosion performance of cold-reduced sheet vitrification film is measured according to method as defined in GB/T10125 and GB/T6461, is pressed
The adhesive force of cold-reduced sheet silane film is measured according to method as defined in GB/T 1720；Cold rolling is measured according to method as defined in GB/T 1731
The flexibility of plate silane film.Test result is as shown in table 1.
Table 1
| Adhesive force | Flexibility/mm | 25 DEG C, there is the rust staining time in 85 humidity | Neutral salt spray/h | |
| Embodiment 1 | 0 | 1 | ＞ is for 24 hours | 0.2 |
| Embodiment 2 | 0 | 1 | ＞ is for 24 hours | 0.3 |
| Embodiment 3 | 0 | 1 | ＞ 36h | 0.6 |
| Embodiment 4 | 0 | 1 | ＞ 48h | 0.8 |
| Embodiment 5 | 0 | 1 | ＞ is for 24 hours | 0.3 |
| Embodiment 6 | 0 | 1 | ＞ 48h | 0.8 |
| Embodiment 7 | 0 | 1 | ＞ 30h | 0.4 |
| Comparative example 1 | 1 | 2 | ＜ 20min | 0 |
| Comparative example 2 | 1 | 1 | ＜ 1h | 0 |
| Comparative example 3 | 0 | 1 | ＜ 1h | 0 |
As it can be seen from table 1 vitrification liquid of the present invention has been used containing silane, fluozirconate and/or fluorine zirconic acid, colloidal silica
The vitrified agent of silicon and resin compound at least containing MQ silicones and polyurethane resin, the epithelium of acquisition meet it is basic
Adhesive force and it is flexible simultaneously, have excellent anti-corrosion capability.
Although describing the present invention with regard to special embodiment and application, based on this teaching, common skill in the art
Art personnel can implement additional embodiment in the case of without departing from the purport of the present invention or not past the scope of the present invention,
And carry out additional modification.It is therefore to be understood that attached drawing and description provide to help to understand herein as example
The present invention, and should not be taken to be limiting its scope.
Claims (10)
1. a kind of environment-friendly type macromolecule modified silane vitrification liquid, which is characterized in that it contains vitrification using water as solvent in raw material
Agent；
The vitrified agent includes silane, fluozirconate and/or fluorine zirconic acid, colloidal silicon dioxide and at least contains MQ silicon trees
The resin compound of fat and polyurethane resin.
2. environment-friendly type macromolecule modified silane vitrification liquid according to claim 1, which is characterized in that its raw material components is with total
On the basis of 100 mass fraction of quality, contain according to the mass fraction：0.05-35 parts of silane, fluozirconate and/or fluorine zirconic acid 0.01-
10 parts, 0.5-10 parts of colloidal silicon dioxide, 5-15 parts of the resin compound at least containing MQ silicones and polyurethane resin, lubrication
0.1-5 parts of agent, remaining is water.
3. environment-friendly type macromolecule modified silane vitrification liquid according to claim 1, which is characterized in that the silane be selected from
3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, 2- aminoethyls trimethoxy silane, three ethoxy of 2- aminoethyls
Base silane, ammonia first propyl trimethoxy silicane, aminomethyl triethoxysilane, N- aminoethyl -3- aminopropyl trimethoxysilanes,
N- aminoethyl -3- aminopropyl triethoxysilanes, 3- aminopropyltriethoxies dimethoxysilane, 3- aminopropyltriethoxy diethoxy silicon
Alkane, N- aminoethyl -3- aminopropyltriethoxies dimethoxysilane, N- aminoethyl -3- aminopropyltriethoxies diethoxy silane, epoxy third
Oxygen propyl group triethoxysilane, glycidoxy-propyltrimethoxy silane, glycidoxypropyl dimethoxysilane, epoxy
In third oxygen propyl group methyldiethoxysilane, 1,2- bis- (trimethoxy silicon substrate) ethane, 1,2- bis- (triethoxy silicon substrate) ethane
Any one or more than one mixture.
4. environment-friendly type macromolecule modified silane vitrification liquid according to claim 1, which is characterized in that the fluozirconate is
Any one in ammonium fluozirconate, potassium fluorozirconate and sodium fluozirconate or more than one mixture.
5. environment-friendly type macromolecule modified silane vitrification liquid according to claim 1, which is characterized in that the colloidal silica
The colloidal silicon dioxide for being more than 50nm with grain size containing the colloidal silicon dioxide that grain size is below 20nm in silicon.
6. environment-friendly type macromolecule modified silane vitrification liquid according to claim 1, which is characterized in that the MQ silicones
Siloxy units are selected from (R3SiO1/2) a represent M units and with (SiO4/2) b represent Q unit, a and b are represented more than
0 integer；And the solid vinyl ylmethyl MQ silicones that the value that MQ silicones is molecular weight 50~700,000, a/b is 0.6~1.0
Or the methyl MQ silicones containing silicone hydroxyl.
7. environment-friendly type macromolecule modified silane vitrification liquid according to claim 1, which is characterized in that the polyurethane resin
For superbrnaching end-hydroxy polyurethane.
8. environment-friendly type macromolecule modified silane vitrification liquid according to claim 2, which is characterized in that the lubricant is selected from
It is at least one kind of in polyethylene wax, polypropylene wax or Brazil wax.
9. environment-friendly type macromolecule modified silane vitrification liquid according to claim 1, which is characterized in that the resin compound
In MQ silicones and polyurethane resin mass ratio be 0.5-2.5.
A kind of 10. method for preparing environment-friendly type macromolecule modified silane vitrification liquid described in claim 1, which is characterized in that
Fluozirconate and/or fluorine zirconic acid, colloidal silicon dioxide are added in water, is stirred 5-10 minutes, obtains the first solution；It adds in water
Silane and the resin compound at least containing MQ silicones and polyurethane resin stir 0.5-2h, obtain the second solution；By first
Solution and the second solution are uniformly mixed, and obtain environment-friendly type macromolecule modified silane vitrification liquid.
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