A kind of list processing agent before metal material cathode electro-coating
Technical field
The present invention relates to a kind of list processing agent before metal material cathode electro-coating, belong to industrial media technology neck
Territory.
Background technology
Metal material typically requires before carrying out application and carries out surface process to strengthen the adhesion property between metal and coating, mesh
Before, the metal surface treatment technology many employings phosphorization treatment process before application.But, this processing method is owing to having containing zinc, nickel etc.
The evil chemical composition such as heavy metal ion and phosphorus, and production produces substantial amounts of phosphatization slag, environment can be caused potentially hazardous.
Meanwhile, phosphorization treatment technology power consumption is relatively big, adjusts technique degree of dependence big in the table in front road, and this also can increase the difficulty of cost and management
Degree.
As the technology that can substitute conventional phosphatizing processing mode, it is known that have Zirconium compound or Zirconium compound combine
Organosilan processing mode.But the metal material surface chemical reaction film layer that existing non-phosphatization processing mode obtains is thin, film layer
Sparse the finest and close, thus cause metal material surface resistance low, for having relatively in car body and parts, or other industry
For the metal material of labyrinth, it is accordingly required in particular to form fine and close thick and heavy chemical composition coating layer at metal material surface, enter
And improve metal surface resistance, so that metal material is when follow-up cathode electro-coating, electrophoretic coating has high throwing power.
The exploitation of a kind of non-phosphatization list processing agent that can be effectively improved metal surface resistance value is necessary.
Summary of the invention
The technical problem to be solved is to provide a kind of list processing before metal material cathode electro-coating
Agent, this list processing agent can be greatly improved the resistance value of metal surface.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is:
A kind of list processing agent before metal material cathode electro-coating, in every L list processing agent, by the group of following quality
It is grouped into: 80~150mg water soluble oligomer siloxanes, 50mg zirconyl nitrate or fluorine zirconic acid, 100mg titanyl sulfate or fluotitanic acid,
100mg aluminum nitrate and/or zinc sulfate, 70~80mg lithium carbonate or potassium hydroxide or Ammonium bicarbonate food grade, 100~120mg Fluohydric acid. or
Nitric acid or sulphuric acid, 80~100mg surface grafting have amino and/or the oxide nano particles of hydroxyl, 100~150mg ethanol, 50
~Polyethylene Glycol, 1~5mg ferrous sulfate that 100mg molecular weight is 300~600 and water surplus;Wherein, described oxide is received
The grafting amount of rice grain surface hydroxyl is 1.4~5mmol/g, and the grafting amount of described oxide nanoparticle surface amino is 0.9
~5mmol/g, the ratio of described oxide nanoparticle surface hydroxyl and amino grafting amount is 0.3~4.1.
Further preferably, described water soluble oligomer siloxanes is trimer siloxanes, tetramer siloxanes, pentamer silica
Alkane or six aggressiveness siloxanes.
Further preferably, described oxide nano particles is nano SiO 2 particle and/or titania nanoparticles
And/or zirconium dioxide nanoparticles.
Further preferably, the particle diameter of described nano SiO 2 particle is 5~10nm;Described titania nanoparticles
Particle diameter is 6~8nm;The particle diameter of described zirconium dioxide nanoparticles is 5~6nm, and oxide nano particles is under such particle diameter
Easily dispersion, is difficult to reunite, the stability of advantageously combined objects system, and is of value to compositions and deposits film forming in metal surface.
Further preferably, described aluminum nitrate or zinc sulfate can also be substituted by the calcium salt of equivalent, manganese salt or iron salt.
Further preferably, the pH value of described list processing agent is 4~5.
Further preferably, described surface grafting has the oxide nano particles of amino and/or hydroxyl to adopt to make with the following method
For forming: the oxide nano particles that a certain amount of particle diameter is 5~10nm is placed in ethanol, isopropanol or toluene solvant;Again
The desired amount of γ-aminopropyltrimethoxysilane and/or gamma-aminopropyl-triethoxy-silane, described γ-ammonia is added in solvent
The addition of propyl trimethoxy silicane and/or gamma-aminopropyl-triethoxy-silane is the 1% of oxide nano particles addition
~1.5%;By mixed material in rotating speed be 1000~1500r/min down cuts 50~60min;By the suspension that obtains in 40~
Agitating heating 12~24h at 60 DEG C, more scrubbed, filter and dried i.e. can get the oxidation of amino and/or hydroxyl modification
Thing nano-particle.Containing of control oxide nano grain surface hydroxyl and amino is carried out by controlling the addition of silane coupler
Amount, the content ratio of oxide nanoparticle surface hydroxyl and amino just both must can make product in the range of the present invention is limited
The film layer of dense regular can be formed at metal material surface, enhancing metal material can also be played simultaneously and adhere to follow-up electrophoretic coating
The effect of power.
The method measuring oxide nanoparticle surface hydroxy radical content: to taking out equipped with modified oxide nano particles
Filter flask adds dry toluene, with dispersal oxide nano-particle;The pipeline of titration appratus is dried, and in bottle,suction
Rapidly join the methyl-magnesium-chloride being stored in constant pressure funnel, use drainage eudiometer to collect the gas V1 generated,
Until reaction is completely;Blank assay: measure the gas flow V2 generated when being added without modified oxide nano particles, as the following formula
The content of calculating oxide nanoparticle surface hydroxyl:
In formula: COHFor oxide nanoparticle surface hydroxy radical content, unit is mmol/g;P is atmospheric pressure, and unit is
Pa;V1 generates gas volume for experiment, and unit is m3;V2 is that blank assay generates gas volume, and unit is m3;M is sample matter
Amount, unit is g;T is experimental temperature, and unit is K;R is gas constant, and unit is (m3·Pa)/(K·mol)。
The method measuring oxide nanoparticle surface amino content: by a certain amount of modified oxide nano particles,
Join in 100ml dehydrated alcohol or isopropanol, ultrasonic 10min, until sample dispersion all with after, add 5~10 thymols
Blue indicator solution, with hydrochloric acid-ethanol standard solution titration, solution colour is titration end-point from the faint yellow pink that becomes, with
Shi Jinhang blank assay;Blank assay: carry out in the case of being added without modified oxide nano particles.The most according to the following formula
Computing function nano-oxide particle surface amino content:
In formula:For oxide nanoparticle surface amino content, unit is mmol/g;C is that hydrochloric acid-ethanol solution rubs
That concentration, unit is mol/L;V5 is the volume consuming hydrochloric acid-ethanol solution in EXPERIMENTALTitration, and unit is mL;V6 is blank real
Testing the volume of consumption hydrochloric acid-ethanol solution, unit is mL.
Hydrochloric acid-ethanol standard solution forming steps is as follows: 1. measure the concentrated hydrochloric acid that 9ml mass concentration is 36%, adds nothing
Water-ethanol is diluted to 1000ml, mix homogeneously and get final product;2. it is taken at 270-300 DEG C and is dried the benchmark natrium carbonicum calcinatum 0.1g to constant weight
It is placed in conical flask, after adding 50ml deionized water dissolving, adds C.I. 13020 .-bromocresol green mixed indicator 10, with above-mentioned
Hydrochloric acid-ethanol solution be titrated to solution colour by green transition be kermesinus be titration end-point, carry out blank assay simultaneously;3. empty
White test: carry out in the case of being added without sodium carbonate.It is calculated as follows the molar concentration of hydrochloric acid-ethanol solution:
In formula: the actual concentrations of c-hydrochloric acid-ethanol standard titration solution, unit is mol/L;M-benchmark natrium carbonicum calcinatum
Quality, unit is g;In V3-experiment, titration consumes hydrochloric acid-ethanol standard solution volume, and unit is mL;V4-blank experiment drips
Surely consuming hydrochloric acid-ethanol standard solution volume, unit is mL;0.0530 for (concentration is with 1.00mL Hydrochloric Standard Titration
The quality of 1mol/L) suitable benchmark natrium carbonicum calcinatum, unit is g.
Compared to prior art, technical solution of the present invention has the beneficial effect that
The advantage that list processing agent of the present invention has good stability, wettability is good, and the metal material after processing can direct water
Wash (illustrating that product of the present invention is strong at metal surface adhesive force, be difficult to come off from metal material surface);Inventive formulation uses poly-
Siloxanes substitutes monomeric silanes coupling agent, effectively enhances the stability of system, due to monomeric silanes coupling agent difficulty in system
With dispersion, easily assemble agglomerating, thus have impact on performance and the stability of system;It addition, inventive formulation uses is grafted with amino
And/or the oxide nano particles of hydroxyl, surface has the oxide nano particles of functional group and shows attachment at metal material
Power is strong, is difficult to come off from metal material surface, and follow-up electrophoresis film and the adhesive force of metal material;The present invention joins
Product can be made to get off in the calmness that metal material surface is orderly, form the film layer of dense regular, thus improve metal material table
The resistance value in face, the resistance value of the metal material surface after using the present invention non-phosphatization list processing agent to process can reach 1.5~2.5
Ohm/every square centimeter, 0.2~0.5 ohm/every square centimeter of the most existing non-phosphatization list processing agent, therefore gold
Genus material is when follow-up cathode electro-coating, and electrophoretic coating has high throwing power, and inventive formulation can also improve metal material
What surface and follow-up electrophoresis process were formed is coated with intermembranous adhesive force.
Accompanying drawing explanation
Fig. 1 is that after using list processing agent of the present invention to process, metal material shows that the chemical reaction film layer formed is partially schematic
Figure;
Fig. 2 is that after using existing non-phosphatization list processing agent to process, metal material shows that the chemical reaction film layer formed local shows
It is intended to.
Detailed description of the invention
According to following embodiment, the present invention be may be better understood.But, as it will be easily appreciated by one skilled in the art that reality
Execute the content described by example and be merely to illustrate the present invention, and should be also without limitation on basis described in detail in claims
Invention.
List processing agent treated metal material of the present invention, including ferrum and/or its alloy material, zinc and/or its alloy material
Material, aluminum and/or its alloy material and magnesium and/or its alloy material.
Water soluble oligomer siloxanes employed in list processing agent prescription of the present invention is:
Dynasylan the Hydrosil 2926 and/or Dynasylan Hydrosil 2776 of Dehussa company.
Embodiment 1
Present invention list processing agent before metal material cathode electro-coating, in every L list processing agent, by following quality
Component forms: 100mg water soluble oligomer siloxanes (Dynasylan Hydrosil 2926), 50mg zirconyl nitrate, 100mg sulfur
Acid oxygen titanium, 100mg aluminum nitrate, 70mgLi2CO3, 100mg sulphuric acid, 80mg surface grafting have the oxidate nano of amino and hydroxyl
Grain, 100mg ethanol, 50mg molecular weight are the Polyethylene Glycol of 600, (ferrous sulfate can strengthen the reaction of system to 2mg ferrous sulfate
Activity, promotes the generation of reaction and improves reaction efficiency) and water surplus;Wherein, described oxide nanoparticle surface hydroxyl
Grafting amount be 5mmol/g, the grafting amount of described oxide nanoparticle surface amino is 5mmol/g, oxide nano particles
The ratio of surface hydroxyl and amino grafting amount is 1.
The pH value of present invention list processing agent before metal material cathode electro-coating is 5.
Embodiment 2
Present invention list processing agent before metal material cathode electro-coating, in every L list processing agent, by following quality
Component forms: 80mg water soluble oligomer siloxanes (Dynasylan Hydrosil 2926), 70mg water soluble oligomer siloxanes
(Dynasylan Hydrosil 2776), 50mg fluorine zirconic acid, 100mg titanyl sulfate, 50mg aluminum nitrate, 50mg zinc sulfate, 70mg
Potassium hydroxide, 100mg nitric acid, 100mg surface grafting have amino and the oxide nano particles of hydroxyl, 120mg ethanol, 80mg to divide
Son amount is Polyethylene Glycol, 3mg ferrous sulfate and the water surplus of 600;Wherein, the connecing of described oxide nanoparticle surface hydroxyl
Branch amount is 1.4mmol/g, and the grafting amount of described oxide nanoparticle surface amino is 3.8mmol/g, oxide nano particles
The ratio of surface hydroxyl and amino grafting amount is 0.37.
The pH value of present invention list processing agent before metal material cathode electro-coating is 4.5.
Embodiment 3
Present invention list processing agent before metal material cathode electro-coating, in every L list processing agent, by following quality
Component forms: 50mg water soluble oligomer siloxanes (Dynasylan Hydrosil 2926), 100mg water soluble oligomer siloxanes
(Dynasylan Hydrosil 2776), 50mg fluorine zirconic acid, 100mg fluotitanic acid, 100mg zinc sulfate, 80mg Ammonium bicarbonate food grade,
120mg Fluohydric acid., 100mg surface grafting have amino and the oxide nano particles of hydroxyl, 150mg ethanol, the 100mg molecular weight to be
Polyethylene Glycol, 5mg ferrous sulfate and the water surplus of 600;Wherein, the grafting amount of described oxide nanoparticle surface hydroxyl is
3.7mmol/g, the grafting amount of described oxide nanoparticle surface amino is 0.9mmol/g, oxide nanoparticle surface hydroxyl
The ratio of base and amino grafting amount is 4.1.
The pH value of present invention list processing agent before metal material cathode electro-coating is 4.2.
Embodiment 4
Using commercially available Q235 cold-rolled steel sheet (species abundance in Baosteel in Shanghai production), specification is made for (170mm × 100mm × 0.8mm)
Set-iron for the present embodiment.
First metal sample is carried out the degreasing cleaning process that metal material shows;Then set-iron is placed in embodiment
Soaking 5 minutes in the list processing agent of 1, immediately process with water flushing after immersion, the resistance value on the set-iron surface after process is
1.5 ohm/every square centimeter, after flushing, set-iron is in the case of moistened surface, uses cathode electrophoresis dope HD8000 (to close
Western company manufactures) carry out ability cathode electrophoresis process, the model after electrophoretic process uses deionized water rinsing 30 seconds.After washing
After electrophoresis, model is dried 20 minutes under the conditions of 180 DEG C, takes out room temperature and dries its film thickness of detection in 20 μm ± 1 μ m
Obtaining test piece, test piece specifically detects performance and is shown in Table 1.
Embodiment 5
Using commercially available galvanized steel plain sheet, specification is the metal-like that (170mm × 100mm × 0.8mm) is used as the present embodiment
Plate.
First metal sample is carried out the degreasing cleaning process that metal material shows;Then set-iron is placed in embodiment
Soaking 2 minutes in the list processing agent of 2, immediately process with water flushing after immersion, the resistance value on the set-iron surface after process is
2.0 ohm/every square centimeter, after flushing, set-iron is in the case of moistened surface, uses cathode electrophoresis dope ECO3000
(manufacture of KCC company) carries out ability cathode electrophoresis process, and the model after electrophoretic process uses deionized water rinsing 30 seconds.After washing
Electrophoresis after model under the conditions of 180 DEG C be dried 20 minutes, take out room temperature dry detection its film thickness at 20 μm ± 1 μ m
The most i.e. obtaining test piece, test piece specifically detects performance and is shown in Table 1.
Embodiment 6
Using commercially available aluminium sheet, specification is the set-iron that (170mm × 100mm × 0.8mm) is used as the present embodiment.
First metal sample is carried out the degreasing cleaning process that metal material shows;Then set-iron is placed in embodiment
Soaking 8 minutes in the list processing agent of 3, immediately process with water flushing after immersion, the resistance value on the set-iron surface after process is
2.5 ohm/every square centimeter, after flushing, set-iron is in the case of moistened surface, uses cathode electrophoresis dope ED6C (PPG
Company manufactures) carry out ability cathode electrophoresis process, the model after electrophoretic process uses deionized water rinsing 30 seconds.By the electricity after washing
After swimming, model is dried 20 minutes under the conditions of 180 DEG C, and taking-up room temperature is dried its film thickness of detection and in 20 μm ± 1 μ m is
Obtaining test piece, test piece specifically detects performance and is shown in Table 1.
Table 1
As shown in Fig. 1~2, the precipitation that list processing agent of the present invention can be orderly in metal surface, the chemical reaction film obtained
Layer dense regular, thus cause metal material surface resistance value high, and oxide nano particles is at metal material surface adhesive force
By force, difficult drop-off, and the film layer arrangement that existing list processing agent obtains is loose, thus cause metal material surface resistance value low.
List processing agent stability of the present invention is high, wettability is good, and after process, the chemical reaction film layer of metal surface gained has
The advantage that film thickness, resistance value are high and corrosion resistance is strong, significantly improves the throwing power in follow-up electrophoretic painting, and with follow-up electricity
The adhesion of the film that swimming technique is formed is the strongest.