CN104846359B - Composite treating agent for pretreatment of metal surface and its preparation method and application - Google Patents
Composite treating agent for pretreatment of metal surface and its preparation method and application Download PDFInfo
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- CN104846359B CN104846359B CN201410054012.2A CN201410054012A CN104846359B CN 104846359 B CN104846359 B CN 104846359B CN 201410054012 A CN201410054012 A CN 201410054012A CN 104846359 B CN104846359 B CN 104846359B
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Abstract
The invention discloses a kind of composite treating agent for pretreatment of metal surface and its preparation method and application, the composite treating agent is prepared by following raw materials：Film forming agent A：0.1 8g, film forming agent B：4 30g, coalescents：1 10g, antirust agent：1 4g, metal ion chelation agent：1 4g, amine buffering agent：1 4g, surfactant：0.05 2g, solubilizer to 1000mL, it is 35 to adjust pH.Composite treating agent of the present invention can be formed and metal binding coating good, corrosion resistance is strong.The preparation method is simple to operation, and environmental protection, cost is cheap, does not produce the contaminated ions such as phosphate, nickel, manganese, chromium, no precipitation waste residue in preparation process.
Description
Technical field
The present invention relates to pretreatment of metal surface field, more particularly to a kind of compound place for pretreatment of metal surface
Manage agent and its preparation method and application.
Background technology
Report display, the hardware and material that the whole world is scrapped due to corrosion every year are approximately equivalent to metal year according to statistics
The 1/3 of yield, the wherein metal material of total output 1/10 because corrosion and can not recycling, this not only cause metal money
The huge waste in source, returns daily production and health of people brings serious threat；The whole world is every year caused by metal erosion
About 7,000,000,000,000 dollars of direct economic loss, it is that the natural calamities such as earthquake, floods, typhoon cause damage 6 times of summation, as
Because equipment corrosion damage caused by suspending operation or slashing production, product quality decline, pollution environment, health hazard and caused by secondary damage
Lose, can not even more estimate.China is in the energy, traffic, building, machinery, chemical industry, infrastructure, water conservancy and military installations etc. at present
Typical industry and enterprise, because corrosion loss caused by metal material and surrounding environment generation chemistry or electrochemical reaction is every
In about 500,000,000,000 yuans of year, account for 6% or so of China's gross national product.And anticorrosive coating is to prevent metal erosion
One of the most frequently used method.
Therefore, must be surface-treated before coated metal, the Coating Pretreatment of metal material is generally divided into phosphatization at present
With two kinds of processing modes of passivation.Phosphorus/Passivation Treatment refers to that carrying out processing to metal surface using phosphorus/passivator forms its surface
One layer of phosphorus/passivating film, film forming is relatively strong, corrosion resistance and adhesive force are all preferable, but produces a large amount of phosphoric acids in use
The waste water and waste residue of salt, bichromate, high energy consumption and pollution environment.Some without phosphorus processing start to apply in recent years in addition, and it is given birth to
Into film layer just correspond to the effect of antirust coat, although can have certain protective action to metal, this diaphragm and priming paint
Adhesion and adhesive force are all very poor, are easy to come off over time.
The content of the invention
Based on this, it is an object of the invention to provide a kind of composite treating agent for pretreatment of metal surface.
The concrete technical scheme for solving above-mentioned technical problem is as follows：
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A：0.1-8g,
Film forming agent B：4-30g,
Coalescents：1-10g,
Antirust agent：1-4g,
Metal ion chelation agent：1-4g,
Amine buffering agent：1-4g,
Surfactant：0.05-2g,
Solubilizer to 1000mL, pH 3-5,
The film forming agent A is at least one in fluoboric acid, fluorine zirconic acid, fluotitanic acid, fluosilicic acid, potassium fluorozirconate or sodium fluozirconate
Kind,
The film forming agent B is gamma-aminopropyl-triethoxy-silane (γ-APS) or γ-(oxygen of 2,3- epoxies third) propyl group front three
At least one of TMOS (γ-GPS).
In wherein some embodiments, the composite treating agent is prepared by the raw material of following weight：
Film forming agent A：5-8g,
Film forming agent B：15-20g,
Coalescents：3-5g,
Antirust agent：1-2g,
Metal ion chelation agent：1-4g,
Amine buffering agent：1-4g,
Surfactant：0.1-1g,
Solubilizer is to 1000mL.
In wherein some embodiments, the composite treating agent is prepared by the raw material of following weight：
Film forming agent A：5-6g,
Film forming agent B：15-18g,
Coalescents：3-5g,
Antirust agent：1-2g,
Metal ion chelation agent：1-2g,
Amine buffering agent：1-2g,
Surfactant：0.1-1g,
Solubilizer is to 1000mL.
In wherein some embodiments, the film forming agent A be fluoboric acid, fluorine zirconic acid, fluotitanic acid or fluosilicic acid at least
It is a kind of.
In wherein some embodiments, gamma-aminopropyl-triethoxy-silane (γ-APS) and γ in the film forming agent B-(2,
The oxygen of 3- epoxies third) propyl trimethoxy silicane (γ-GPS) mass ratio be 1:1.2-2.
In wherein some embodiments, the coalescents are sodium fluoride.
In wherein some embodiments, the antirust agent is boric acid or Boratex.
In wherein some embodiments, the metal ion chelation agent is tartaric acid or oxalic acid.
In wherein some embodiments, the amine buffering agent is triethanolamine or diethanol amine.
In wherein some embodiments, the surfactant is lauryl sodium sulfate or octyl phenol polyoxyethylene
Ether -10（OP-10）.
In wherein some embodiments, the solvent is at least one in deionized water, ethanol, isopropanol or n-butanol
Kind.
It is another object of the present invention to provide a kind of system of the above-mentioned composite treating agent for pretreatment of metal surface
Preparation Method, comprise the following steps：
（1）Film forming agent A is dissolved in appropriate solvent, it is 4-5 to adjust pH with acetic acid, adds film forming agent B, obtains solution A；
（2）Coalescents, antirust agent, metal ion chelation agent, amine buffering agent and surfactant are dissolved in right amount respectively
Solvent in, obtain solution B；
（3）By step（2）Obtained solution B adds step（1）In obtained solution A, it is settled to solvent
1000mL, it is 3-5 to adjust pH with acetic acid, you can.
It is another object of the present invention to provide a kind of application of above-mentioned composite treating agent in pretreatment of metal surface,
Pending metal is soaked in composite treating agent after 30-360s, water rinses, compressed air drying, and in 110-130 DEG C of baking
Dry 50-70min, you can；
Or spray composite treating agent in pending metal surface, after spraying 30-360s, water rinses, compressed air drying,
And dry 50-70min in 110-130 DEG C, you can.
The principle of the present invention is as follows：
Film forming agent A be it is a kind of with fluosilicic acid, fluorine zirconic acid, fluoboric acid, fluotitanic acid, potassium fluorozirconate or sodium fluozirconate at least
Nanometer technology based on a kind of, it can be in the fluosilicic acid in one layer of nano coating of the metal surface of cleaning formation, inorganic agent, fluorine
Zirconic acid, fluoboric acid, fluotitanic acid, potassium fluorozirconate or sodium fluozirconate etc. can react to form combination product with the oxide of metal surface,
After drying, the product deposits the nano ceramics chemical composition coating to form compact texture in metal surface, can significantly improve metal
The decay resistance of coating；Film forming agent B is forming silane film technology, and this molecular formula of silylation is Y-Si- (OR) 3, and wherein OR is can
The group of hydrolysis, hydrolysis produce silanol, and chemical bonds are carried out with metal surface hydroxyl.Metal works after silane treatment,
Interface forms the very strong Si-O-Me covalent bonds (wherein Me=metal) of adhesion, and Si-O-Me bond energys are very strong, than Si-O-Si bond energy
It is also strong, while Y group is organo-functional group, can be attached with organic coating, therefore have with follow-up organic coating good
Good adhesive force；Coalescents are used to stablize fluorine ion, are advantageous to the formation of combination product；Antirust agent is to increase film layer
Decay resistance；Metal ion chelation agent is in order that free metal ion is chelated in composite treating agent, and formation molecular weight is more
Big compound, is easy to film forming；Amine buffering agent is the acid-base value for stablizing composite treating agent；Surfactant is made using its wetting
With reducing the interfacial tension of composite treating agent and metal surface, make composite treating agent be easier to contact with metal surface, be advantageous to
The formation of coating.Silicon/titanium/zirconium/boron fluorochemical film forming agent the A and epoxy radicals silicone hydride film forming agent B of proper proportion, can improve
The shortcomings that single silane film and basal body binding force are bad, and film layer consistency is little, passes through the silicon in film forming agent A, zirconium, boron, titanium etc.
The addition of element, improve the consistency of film forming agent B coatings, reduce the crackle in film layer, improve the corrosion resisting property of coating；Match somebody with somebody simultaneously
Suitable suitable coalescents, antirust agent, metal ion chelation agent, amine buffering agent and surfactant so that obtained compound place
Reason agent has excellent performance.
A kind of composite treating agent for pretreatment of metal surface of the present invention and its preparation method and application have with
Lower advantage and beneficial effect：
（1）Composite treating agent of the present invention by the fluorochemical of film forming agent A silicon/titanium/zirconium/boron and film forming agent B (γ-
APS) and/or (γ-GPS) is compound, and by adjust the fluorochemical of film forming agent A silicon/titanium/zirconium/boron and film forming agent B (γ-
APS) and/or (γ-GPS) ratio, and its with coalescents, antirust agent, metal ion chelation agent, amine buffering agent and surface live
Property agent ratio, obtained composite treating agent can be formed with it is metal binding it is good, corrosion resistance is strong, without cavity, split it is sunken,
The coating of dense uniform.
（2）The preparation method of composite treating agent of the present invention is simple to operation, environmental protection, and phosphoric acid is not produced in preparation process
The contaminated ions such as salt, nickel, manganese, chromium, no precipitation waste residue.
（3）In the application of pretreatment of metal surface, the preprocess method is suitable for composite treating agent of the present invention
The pretreatment of the materials such as galvanized steel plain sheet, aluminium and aluminium alloy, film forming procedure can produce in same tank liquor, eliminate metal surface and answer
Miscellaneous pretreatment process, production technology is simplified, and cost is cheap.
Embodiment
Below with reference to specific embodiment, the present invention will be further described.
Embodiment 1
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- fluorine zirconic acid：5g,
Film forming agent B --- gamma-aminopropyl-triethoxy-silane (γ-APS)：5g,
γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane (γ-GPS)：10g
Coalescents --- sodium fluoride：5g,
Antirust agent --- boric acid：1g,
Metal ion chelation agent --- tartaric acid：2g,
Amine buffering agent --- triethanolamine：1g,
Surfactant --- OP-10：0.1g,
Solubilizer --- deionized water is to 1000mL, pH 3-5.
The preparation method of above-mentioned composite treating agent, comprises the following steps：
(1) 5g gamma-aminopropyl-triethoxy-silanes (γ-APS) are weighed, and are added into 500ml deionized waters, are stirred
1~2h, make its hydrolysis, and it is 4~5 to adjust solution pH value with acetic acid, adds 10g γ-(2,3- the third oxygen of epoxy) propyl group front three
TMOS (γ-GPS), adds 5g fluorine zirconic acids under stirring, continues stirring 2~3h of hydrolysis, is configured to solution A；
(2) 5g sodium fluorides, 1g boric acid, 2g tartaric acid, 1g triethanolamines, 0.1gOP-10 are weighed, and is added into respectively
In 300ml deionized waters, solution B is configured to；
(3) solution B made from step (2) is added in solution A made from step (1), adds deionized water to 1L, and
It is 3~5 with acetic acid regulation pH value.
Embodiment 2
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- potassium fluorozirconate：6g,
Film forming agent B --- gamma-aminopropyl-triethoxy-silane (γ-APS)：5g,
γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane (γ-GPS)：10g
Coalescents --- sodium fluoride：1g,
Antirust agent --- Boratex：2g,
Metal ion chelation agent --- tartaric acid：2g,
Amine buffering agent --- diethanol amine：2g,
Surfactant --- lauryl sodium sulfate：0.1g,
Solubilizer deionized water is to 1000mL, pH 3-5.
The method of above-mentioned metal material surface composite treating agent, comprises the following steps：
(1) 5g gamma-aminopropyl-triethoxy-silanes (γ-APS) are weighed, and are added into 500ml deionized waters, are stirred
1~2h, make its hydrolysis, and be 4~5 with acetic acid regulation solution ph, add 10g γ-(2,3- the third oxygen of epoxy) propyl group front three
TMOS (γ-GPS), adds 6g potassium fluorozirconates under stirring, continues stirring 2~3h of hydrolysis, is configured to solution A；
(2) 1g sodium fluorides, 2g Boratexes, 2g tartaric acid, 2g diethanol amine, 0.1g lauryl sodium sulfate are weighed, and is divided
It is not added into 300ml deionized waters, is configured to solution B；
(3) solution B made from step (2) is added in solution A made from step (1), adds deionized water to 1L, and
It is 3~5 with acetic acid regulation pH value.
Embodiment 3
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- fluosilicic acid：6g,
Film forming agent B --- gamma-aminopropyl-triethoxy-silane (γ-APS)：7.5g
γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane (γ-GPS)：10g
Coalescents --- sodium fluoride：5g,
Antirust agent --- Boratex：2g,
Metal ion chelation agent --- tartaric acid：2g,
Amine buffering agent --- diethanol amine：2g,
Surfactant --- lauryl sodium sulfate：0.1g,
Solubilizer --- deionized water：Ethanol=3:2（v/v）To 1000mL, pH 3-5.
The method of above-mentioned metal material surface composite treating agent, comprises the following steps：
(1) 7.5g gamma-aminopropyl-triethoxy-silanes (γ-APS) are weighed, and is added into 500ml in the mixed solvents and (goes
The volume ratio of ionized water and ethanol is 3:2) 1~2h, is stirred, makes its hydrolysis, and is 4~5 with acetic acid regulation solution ph, then is added
Enter 10g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (γ-GPS), 6g fluosilicic acid is added under stirring, after
2~3h of continuous stirring hydrolysis, is configured to solution A；
(2) 5g sodium fluorides, 2g Boratexes, 2g tartaric acid, 2g diethanol amine, 0.1g lauryl sodium sulfate are weighed, and is divided
Not being added into 300ml in the mixed solvents, (deionized water and the volume ratio of ethanol are 3:2), it is configured to solution B；
(3) solution B made from step (2) is added in solution A made from step (1), adds mixed solvent to 1L, and
It is 3~5 with acetic acid regulation pH value.
Embodiment 4
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- sodium fluozirconate：4g,
Film forming agent B --- gamma-aminopropyl-triethoxy-silane：10g,
Coalescents --- sodium fluoride：1g,
Antirust agent --- boric acid：1g,
Metal ion chelation agent --- oxalic acid：1g,
Amine buffering agent --- triethanolamine：1g,
Surfactant --- lauryl sodium sulfate：0.5g,
Solubilizer deionized water：Isopropanol=4:1（v/v）To 1000mL, pH 3-5,
The preparation method of above-mentioned composite treating agent, comprises the following steps：
(1) 10g gamma-aminopropyl-triethoxy-silanes (γ-APS) are weighed, and are added into 500ml in the mixed solvents, are stirred
1~2h is mixed, makes its hydrolysis, and is 4~5 with acetic acid regulation solution ph, 4g sodium fluozirconates are added under stirring, are continued
Stirring 2~3h of hydrolysis, is configured to solution A；
(2) 1g sodium fluorides, 1g boric acid, 1g oxalic acid, 1g triethanolamines, 0.5g lauryl sodium sulfate are weighed, and respectively will
It adds 300ml in the mixed solvents, is configured to solution B；
(3) solution B made from step (2) is added in solution A made from step (1), adds mixed solvent to 1L, and
It is 3~5 with acetic acid regulation pH value.
Embodiment 5
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- fluotitanic acid：8g,
Film forming agent B --- γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane：20g,
Coalescents --- sodium fluoride：3g,
Antirust agent --- boric acid：2g,
Metal ion chelation agent --- oxalic acid：4g,
Amine buffering agent --- triethanolamine：3g,
Surfactant --- lauryl sodium sulfate：1g,
Solubilizer deionized water：Ethanol：N-butanol=4:0.5:0.5（v/v）To 1000mL, pH 3-5,
The preparation method of above-mentioned composite treating agent, comprises the following steps：
(1) 20g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane is weighed, and is added into 500ml mixed solvents
In, 1~2h is stirred, makes its hydrolysis, and it is 4~5 to adjust solution pH value with acetic acid, and 8g fluotitanic acids are added under stirring,
Continue stirring 2~3h of hydrolysis, be configured to solution A；
(2) 3g sodium fluorides, 2g boric acid, 4g oxalic acid, 3g triethanolamines, 1g lauryl sodium sulfate are weighed, and respectively by it
300ml in the mixed solvents are added, are configured to solution B；
(3) solution B made from step (2) is added in solution A made from step (1), adds mixed solvent to 1L, and
It is 3~5 with acetic acid regulation pH value, you can.
Embodiment 6
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- fluoboric acid：8g,
Film forming agent B --- γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane：20g,
Coalescents --- sodium fluoride：3g,
Antirust agent --- boric acid：2g,
Metal ion chelation agent --- oxalic acid：4g,
Amine buffering agent --- triethanolamine：3g,
Surfactant --- lauryl sodium sulfate：1g,
Solubilizer deionized water：Ethanol：N-butanol=4:0.5:0.5（v/v）To 1000mL, pH 3-5,
The preparation method of above-mentioned composite treating agent, comprises the following steps：
(1) 20g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane is weighed, and is added into 500ml mixed solvents
In, 1~2h is stirred, makes its hydrolysis, and be 4~5 with acetic acid regulation solution ph, 8g fluoboric acid is added under stirring,
Continue stirring 2~3h of hydrolysis, be configured to solution A；
(2) 3g sodium fluorides, 2g boric acid, 4g oxalic acid, 3g triethanolamines, 1g lauryl sodium sulfate are weighed, and respectively by it
300ml in the mixed solvents are added, are configured to solution B；
(3) solution B made from step (2) is added in solution A made from step (1), adds mixed solvent to 1L, and
It is 3~5 with acetic acid regulation pH value, you can.
Embodiment 7
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- fluosilicic acid：0.1g,
Film forming agent B --- γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane：4g,
Coalescents --- sodium fluoride：1g,
Antirust agent --- boric acid：1g,
Metal ion chelation agent --- oxalic acid：1g,
Amine buffering agent --- triethanolamine：1g,
Surfactant --- lauryl sodium sulfate：0.05g,
Solubilizer deionized water：Ethanol：Isopropanol=4:0.5:0.5（v/v）To 1000mL, pH 3-5,
The preparation method of above-mentioned composite treating agent, comprises the following steps：
(1) 4g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane is weighed, and is added into 500ml in the mixed solvents,
1~2h is stirred, makes its hydrolysis, and is 4~5 with acetic acid regulation solution ph, 0.1g fluosilicic acid is added under stirring, after
2~3h of continuous stirring hydrolysis, is configured to solution A；
(2) 1g sodium fluorides, 1g boric acid, 1g oxalic acid, 1g triethanolamines, 0.05g lauryl sodium sulfate are weighed, and respectively will
It adds 300ml in the mixed solvents, is configured to solution B；
(3) solution B made from step (2) is added in solution A made from step (1), adds mixed solvent to 1L, and
It is 3~5 with acetic acid regulation pH value, you can.
Embodiment 8
A kind of composite treating agent for pretreatment of metal surface, the composite treating agent are prepared by the raw material of following weight
Form：
Film forming agent A --- fluotitanic acid：8g,
Film forming agent B --- γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane：20g,
Gamma-aminopropyl-triethoxy-silane (γ-APS)：10g,
Coalescents --- sodium fluoride：10g,
Antirust agent --- boric acid：4g,
Metal ion chelation agent --- oxalic acid：4g,
Amine buffering agent --- triethanolamine：4g,
Surfactant --- lauryl sodium sulfate：2g,
Solubilizer deionized water：Ethanol：Isopropanol=4:0.5:0.5（v/v）To 1000mL, pH 3-5,
The preparation method of above-mentioned composite treating agent, comprises the following steps：
(1) 10g gamma-aminopropyl-triethoxy-silanes are weighed, and are added into 500ml in the mixed solvents, stir 1~2h,
Make its hydrolysis, and be 4~5 with acetic acid regulation solution ph, add 20g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane, 8g fluotitanic acids are added under stirring, continue stirring 2~3h of hydrolysis, be configured to solution A；
(2) 10g sodium fluorides, 4g boric acid, 4g oxalic acid, 4g triethanolamines, 2g lauryl sodium sulfate are weighed, and respectively by it
300ml in the mixed solvents are added, are configured to solution B；
(3) solution B made from step (2) is added in solution A made from step (1), adds mixed solvent to 1L, and
It is 3~5 with acetic acid regulation pH value, you can.
Embodiment 9 evaluates the corrosion resistance of composite treating agent described in embodiment 1-8
First, experiment purpose
The corrosion resistance of composite treating agent described in embodiment 1-8 is evaluated by comparative analysis.
2nd, experimental method
This experiment is divided into experimental group and control group, and experimental group is embodiment 1-8, and control group is comparative example 1 and comparative example 2；
Wherein,
Comparative example 1：899ml deionized waters are taken, side stirring just adds normal temperature color ink fast bonderizing liquor 111ml（Purchased from Sichuan
Zi Gong Bo Sheng sufacings Co., Ltd produces）, sample is handled at 35 DEG C.
Comparative example 2：According to the literature, silane coupler gamma-aminopropyl-triethoxy-silane (γ-APS) is added and distilled
In water and absolute ethyl alcohol, V（Absolute ethyl alcohol）：V（Distilled water）：V（Silane）=65：35：5.With magnetic stirring apparatus to molten at 30 DEG C
Liquid is stirred, and glacial acetic acid adjustment solution PH most 6~8 is slowly added dropwise, after hydrolyzing certain time, handles sample.
Tinplate is first used into 240#, 360#, 600#, 800#, 1200#, 1500# liquid honing respectively, then spend from
Sub- water cleaning, surface grease is removed with alkaline defatting agent, then is cleaned up with deionized water, is dried up with compressed air, is immersed real
A 1-8 is applied, 300s is handled in the surface compound treatment agent obtained by comparative example 1-2, spends Ion Cleaning surface, compressed air is blown
It is dry, and 60min is dried in 120 DEG C of drying boxes, that is, obtain one layer of ceramics-silane complex film.
Corrosion resistance test is evaluated with copper sulphate point dropping liquid.Copper sulphate point dropping liquid is dripped in specimen surface with dropper,
Reacted after drop corrosion film layer with metallic matrix.
3rd, experimental result
As a result referring to table 1：
The cupric sulphate dropping test result of table 1
As can be seen from Table 1：Compared with comparative example 1 and comparative example 2, handled through the composite treating agent obtained by embodiment 1-8
The tinplate sample crossed, its decay resistance are obviously improved.This works in coordination mainly due to film forming agent A's and film forming agent B,
Consistency, the uniformity of obtained coating are significantly improved, reduces the crack defect of coating.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (5)
- A kind of 1. without phosphorus Chrome-free composite treating agent for pretreatment of metal surface, it is characterised in that the composite treating agent by The raw material of following weight is prepared：Film forming agent A：5-8g,Film forming agent B：15-20g,Coalescents：3-5g,Antirust agent：1-2g,Metal ion chelation agent：1-4g,Amine buffering agent：1-4g,Surfactant：0.1-1g,For solubilizer to 1000mL, tune pH is 3-5,The film forming agent A is fluosilicic acid or fluoboric acid,The film forming agent B is the mixed of gamma-aminopropyl-triethoxy-silane and γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane Compound, or be γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane；The metal ion chelation agent is tartaric acid or oxalic acid；The antirust agent is boric acid or Boratex；The amine buffering agent is triethanolamine or diethanol amine；The solvent is the mixed liquor of deionized water and ethanol or is the mixed liquor of deionized water, ethanol and n-butanol.
- 2. a kind of without phosphorus Chrome-free composite treating agent for pretreatment of metal surface according to claim 1, its feature exist In the coalescents are sodium fluoride.
- 3. a kind of without phosphorus Chrome-free composite treating agent for pretreatment of metal surface according to claim 1, its feature exist In the surfactant is lauryl sodium sulfate or octyl phenol APEO -10.
- A kind of 4. preparation of without phosphorus Chrome-free composite treating agent for pretreatment of metal surface described in claim any one of 1-3 Method, it is characterised in that comprise the following steps：(1) film forming agent A is dissolved in appropriate solvent, it is 4-5 to adjust pH with acetic acid, adds film forming agent B, obtains solution A；(2) coalescents, antirust agent, metal ion chelation agent, amine buffering agent and surfactant are dissolved in appropriate step respectively (1) in the solvent described in, solution B is obtained；(3) solution B obtained by step (2) is added in the solution A obtained by step (1), with step (1) the solvent constant volume To 1000mL, acetic acid adjustment pH to 3-5, you can.
- 5. application of the without phosphorus Chrome-free composite treating agent in pretreatment of metal surface described in claim any one of 1-3, it is special Sign is, then pending metal liquid honing is cleaned with deionized water, and surface oil is removed with alkaline defatting agent Fat, then cleaned up with deionized water, dried up, be soaked in composite treating agent after 30-360s with compressed air, water rinses, pressure Contracting air blow drying, and dry 50-70min in 110-130 DEG C, you can；Or spray composite treating agent in pending metal surface, after spraying 30-360s, water rinses, compressed air drying, and in 110-130 DEG C of drying 50-70min, you can.
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| CN105349984A (en) * | 2015-11-25 | 2016-02-24 | 安徽红桥金属制造有限公司 | Anti-corrosion treatment agent for metal material surface |
| CN105803440B (en) * | 2016-03-17 | 2018-07-20 | 湖南工程学院 | A kind of carbon steel, galvanized sheet, aluminium are the same as rooved face pretreating agent, preparation method and metal surface pretreatment |
| CN106752225A (en) * | 2016-12-28 | 2017-05-31 | 河南恒润昌环保科技有限公司 | A kind of acid washing silane finish and preparation method thereof |
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| CN114075663B (en) * | 2020-08-21 | 2023-09-12 | 宝山钢铁股份有限公司 | Water-based treating agent for carbon steel surface, well corrosion-resistant carbon steel and preparation method thereof |
| CN114790545B (en) * | 2022-05-07 | 2023-11-21 | 安徽未来表面技术有限公司 | Corrosion-resistant and color-change-resistant color-coated chromium-free coating liquid for galvanized sheet |
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