CN104073100B - A kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet - Google Patents
A kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet Download PDFInfo
- Publication number
- CN104073100B CN104073100B CN201310108818.0A CN201310108818A CN104073100B CN 104073100 B CN104073100 B CN 104073100B CN 201310108818 A CN201310108818 A CN 201310108818A CN 104073100 B CN104073100 B CN 104073100B
- Authority
- CN
- China
- Prior art keywords
- galvanized steel
- plain sheet
- steel plain
- weight
- epithelium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and use this surface conditioning agent to carry out the environment-friendly type surface process galvanized steel plain sheet that surface process obtains.The surface of the galvanized steel plain sheet of the present invention without chromium and is dried without high temperature, surface can be formed under conditions of cold drying and process epithelium, manufacture process environmental protection and consume energy low, by using containing specific aqueous resin and phosphide, specific organo-silicon compound, titanium compound, vanadium compounds, the constituent (i.e. surface conditioning agent) of oxidic polyethylene granule is coated on galvanized steel sheet surface, again through the cold drying of 50 75 DEG C, the galvanized steel plain sheet that the surface obtained processes has the alkali resistance of excellence simultaneously, solvent resistance, corrosion resistance, the excellent properties such as anti-finger printing and application adherence.
Description
Technical field
The invention belongs to field of metal material surface treatment, relate to a kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent
And use this surface conditioning agent to carry out the environment-friendly type surface process galvanized steel plain sheet that surface process obtains, the surface of described galvanized steel plain sheet
Without chromium and dry without high temperature, manufacture process environmental protection and consume energy low, and the galvanized steel plain sheet that this surface processes has excellent simultaneously
The excellent properties such as different alkali resistance, solvent resistance, corrosion resistance, anti-finger printing and application adherence.
Background technology
The metal material of metal foil containing zinc and aluminium sheet etc. is widely used in automobile, building materials and household electric appliances.But, make
Zinc and aluminum with above metal material can be corroded or occur white rust in an atmosphere, thus have influence on the outward appearance of metal material, more
The harmful effect that coating performance is low can be caused.
Expedite the emergence of metal surface and used to improve corrosion resistance and painting adhesion containing chromic acid, dichromic acid or its esters be
Main treatment fluid, namely our usually said chromium processes.
But, along with improving constantly of environmental consciousness in recent years, due to the chromium treatment fluid used when metal material surface processes
In 6 valency chromium harmful, chromium process gradually be eliminated.It addition, the draining containing 6 valency chromium must be deferred to water quality dirt and be prevented method
Regulation, need particularly process, this becomes the reason that totle drilling cost is too high.Furthermore, implemented the metal material that chromium processes
As containing chromium industrial waste can not the huge shortcoming of regeneration, become social problem.
On the other hand, as chromium process beyond surface treatment method be also widely known by the people containing multivalence polycarboxylic acids phenol
The process of the surface conditioning agent of tannic acid.By using tannin aqueous acid that metal material is processed, tannic acid and gold
Genus material reacts and forms protection epithelium, and the intrusion to corrosive deposit forms obstacle raising corrosion resistance.
But along with the high-quality of product in recent years, the high corrosion-resistant of epithelium itself is proposed requirement, therefore tannin
Acid or with inorganic and insufficient with obtained epithelium corrosion resistance, present situation is impossible practical.
Thus as improve corrosion proof processing method Japanese Patent Laid-Open No. Sho 53-121034 publication disclose containing
Water-dispersible silane, alkyd resin, the aqueous solution of compound recipe trialkoxy silane are coated on metal surface and are dried, and cover epithelium
Forming method is disclosed.
Additionally, by using the hydroxy compounds pyrone derivative of water-soluble resin composition to give metal material corrosion resistance
The surface treatment method of purpose and the aqueous solution of use hydroxy compounds or aqueous dispersion polymers give metal material corrosion resistance
Method also disclosed in Japanese Patent Laid-Open No. Sho 57-44751 publication and Unexamined Patent 1-177380 publication.
But, above any method all cannot replace the high corrosion-resistant that chromium epithelium is had.Ask as solving this
The method of topic, Japanese Patent Laid-Open 11-106945 publication proposes metal ion and acid, the silane coupling agent of more than divalent
And the motion of the surface conditioning agent of water-soluble polymer composition.But the technical problem point above-mentioned as realistic problem not yet can
Enough solutions.
It addition, form the surface treated steel plate of such epithelium, during especially for electrical home appliances such as computer parts, coating punching
Carry out processing and forming after force feed, wash punching oil off with degreasing agent subsequently.Degreasing agent is used mostly strong basicity or solvent.In this process
Light plate surface there will be the problems such as epithelium variable color stripping.In order in alkali degreasing and processing and forming operation etc. later epithelium not
Damaged also gives the performances such as higher corrosion resistance, when manufacturing surface treated steel plate, needs to carry out more than 90 DEG C, and even 150
Baking more than DEG C, production cost and CO2The problem of output need to solve.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the invention provides a kind of galvanized steel plain sheet low temperature resistance to
Fingerprint surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet, and this surface processes galvanized steel sheet surface and do not contains chromium, and can be low
Temperature forms surface under conditions of being dried and processes epithelium.
To achieve these goals, the present invention adopts the following technical scheme that:
Technical problem present in prior art is conducted in-depth research by the present invention, by using containing specific water
It is resin and phosphide, specific organo-silicon compound, titanium compound, vanadium compounds, constituent (the i.e. table of oxidic polyethylene granule
Face inorganic agent) it is coated on galvanized steel sheet surface, then the cold drying through 50～75 DEG C, find that it has the alkaline-resisting of excellence simultaneously
Property, solvent resistance, corrosion resistance, anti-finger printing and application adherence.
Present invention firstly provides a kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent.
A kind of galvanized steel plain sheet low temperature anti-finger printing surface conditioning agent, its aqueous solution contains following component:
(A) (a1) the minimum polyurethane resin making the cationic that film temperature is 50～100 DEG C of scopes, shared weight percent
Ratio is the 10～20% of total solid content；
(a2) the minimum acrylic resin making the nonionic that film temperature is 30～50 DEG C of scopes, shared percentage by weight is
The 20%～40% of total solid content；
(B) phosphide, shared percentage by weight is the 1～5% of total solid content；
(C) organo-silane coupling agents containing amino, in each molecule of the organo-silane coupling agents that should contain amino extremely
Contain the amino containing reactive hydrogen as reactive functional groups less, shared percentage by weight be total solid content 5～
10%；
(D) organo-silane coupling agents containing epoxy radicals, should contain each molecule of the organo-silane coupling agents of epoxy radicals
In at least contain an epoxy radicals as reactive functional groups, shared percentage by weight is the 15～25% of total solid content；
(E) titanium compound, shared percentage by weight is the 1～5% of total solid content；
(F) vfanadium compound, shared percentage by weight is the 1～5% of total solid content；
(G) oxidic polyethylene granule, shared percentage by weight is the 5～10% of total solid content；
Total solid content in described galvanized steel plain sheet anti-finger printing surface conditioning agent accounts for the 10-of surface conditioning agent weight
20%；Water accounts for the 80-90% of surface conditioning agent weight.
The total solid content of the present invention refers in galvanized steel plain sheet low temperature anti-finger printing surface conditioning agent component in addition to water
Gross weight.
The polyurethane resin of the cationic that the present invention is above-mentioned and the acrylic resin of nonionic are all without membrane producing promoter.
A kind of galvanized steel plain sheet low temperature anti-finger printing surface conditioning agent of the present invention processes the method for galvanized steel plain sheet, for using
Above-mentioned galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent covers at least one surface of galvanized steel plain sheet, at 50～75 DEG C
At a temperature of be dried remove moisture removal, it is thus achieved that surface process epithelium (i.e. dry film) be 0.5～2.0g/m2Surface process anti-finger printing
Galvanized steel plain sheet.
Another object of the present invention is to provide the anti-finger printing galvanized steel plain sheet that a kind of surface processes.
The anti-finger printing galvanized steel plain sheet that a kind of surface processes, its at least one face is coated with surface reason epithelium, described
Surface processes epithelium and contains following component:
(A) (a1) the minimum polyurethane resin making the cationic that film temperature is 50～100 DEG C of scopes, shared weight percent
Than processing the 10～20% of epithelium for surface；
(a2) the minimum acrylic resin making the nonionic that film temperature is 30～50 DEG C of scopes, shared percentage by weight is
Surface processes the 20%～40% of epithelium；
(B) phosphide, shared percentage by weight is that surface processes the 1～5% of epithelium；
(C) organo-silane coupling agents containing amino, in each molecule of the organo-silane coupling agents that should contain amino extremely
Containing the amino containing reactive hydrogen as reactive functional groups less, shared percentage by weight is that surface processes the 5 of epithelium
～10%；
(D) organo-silane coupling agents containing epoxy radicals, should contain each molecule of the organo-silane coupling agents of epoxy radicals
In at least contain an epoxy radicals as reactive functional groups, shared percentage by weight be surface process epithelium 15～
25%；
(E) titanium compound, shared percentage by weight is that surface processes the 1～5% of epithelium；
(F) vfanadium compound, shared percentage by weight is that surface processes the 1～5% of epithelium；
(G) oxidic polyethylene granule, shared percentage by weight is that surface processes the 5～10% of epithelium.
The anti-finger printing galvanized steel plain sheet that above-mentioned surface processes is the environmental protection that Chrome-free skin membrane (i.e. surface process epithelium) covers
Type surface processes galvanized steel plain sheet.Minimum film temperature 50～the scope of 100 DEG C made of its cationic polyurethane resin, and before having
State the minimum film temperature of making of nonionic acrylic resin within the scope of 30～50 DEG C.
The anti-finger printing galvanized steel plain sheet that the surface of the present invention processes, uses above-mentioned galvanized steel plain sheet low temperature resistance and fingerprint resistance surface
Inorganic agent covers at least one surface of galvanized steel plain sheet, is dried and removes moisture removal, it is thus achieved that surface at a temperature of 50～75 DEG C
Reason epithelium (i.e. dry film) is 0.5～2.0g/m2Surface process anti-finger printing galvanized steel plain sheet.
The galvanized steel plain sheet that the environment-friendly type surface of the present invention processes is by specific aqueous resin, specific phosphide, specific
Organo-silicon compound, titanium compound, vanadium compounds, oxidic polyethylene granule composition epithelium be formed at galvanized steel sheet surface through low
Temperature processes and forms.
Further, the polyurethane resin (a1) of the cationic that the present invention is above-mentioned, containing primaquine in molecular configuration
The cation type polyurethane resin of at least one cationic functional group of base, secondary amine, tertiary amino and season amino etc., above-mentioned sun
Ionic polyurethanes resin is the material of water solublity or water dispersible.
The polyurethane resin of the most above-mentioned cationic cationic functional group by hydrophilic group, dissolves in aqueous medium
Water or self-dispersing emulsifying resins or use cationic surfactant can water-solubleization, or become by water Forced Dispersion
For aqueous resin or water-base resin.The epithelium formed due to the polyurethane resin (a1) of cationic has been assigned the alkaline-resisting of excellence
Property, it is therefore desirable to there is cationic；It addition, the polyurethane resin of this cationic is also required to the phosphide (B) with other, has
The fluoric acid (E) of machine silane coupling agent (C) and (D) and metal has the good compatibility.
Preferably, described cationic polyurethane resin (a1), is by polyester polyalcohols, polyether polyols, Merlon polyalcohols
Being formed Deng polymerization between polyalcohols and aliphatic isocyanates and/or aromatic isocyanate compound, it is poly-that it is used
A part for alcohol can be containing N, the polyalcohols of the amino such as N dimethylamine base dihydroxy methylpropane, it is also possible to be containing polycyclic oxygen second
The polyalcohols of alkane chain.
Above-mentioned cationic polyurethane resin resin (a1) processes on surface in epithelium and controls as containing 10～20% weight
Percentage ratio.During containing percentage by weight less than 10%, its solvent resistance, topcoating coating are low.When proportion is more than 20%, it is low
Hardening during temperature is insufficient, and it is bad that result may result in corrosion resistance, solvent resistance, alkali resistance.More preferably 12～
20%.
Further, the present invention above-mentioned nonionic acrylic resin (a2), is at least selected from a kind of nonionic functional group
Acrylic resin, containing polyoxyethylene chain, hydroxy, the 1st amide groups, the 2nd amide groups, the 3rd amide in molecular configuration
The nonionic acrylic resin of at least one nonionic functional group of base etc. selects water solublity or moisture from this resinoid
Dissipate the material of property.
The most above-mentioned cationic polyurethane resin passes through the nonionic functional group water soluble as hydrophilic group, or
It is self-dispersing emulsifying resins or uses the nonionic surfactant can water-solubleization or become water system tree by water Forced Dispersion
Fat.
Preferably, above-mentioned nonionic acrylic resin (a2), for example with Polyethylene Glycol methacrylic acid and 2-methyl
One or more non-ionic hydrophilic base monomers in 2-(Acryloyloxy)ethanol etc., with acrylate monomer and methacrylate list
One or both in body, and with additional polymerization unsaturated monomer copolymerization co-polypropylene acid resin；Wherein institute
State non-ionic hydrophilic base monomer and contain the hydrophilic group such as polyoxyethylene chain and hydroxy；Described additional polymerization unsaturated monomer selects
One or more in styrene, acrylonitrile and vinyl acetate etc..
Above-mentioned nonionic acrylic resin (a2) process on surface the amount in epithelium control weight ratio 20～
40%.If discontented 20%, the nonionic resinous principle in epithelium is very few, and its corrosion resistance and topcoating coating performance are low.As
Fruit is more than 40%, and the nonionic resinous principle in epithelium is too much, then may result in its corrosion resistance and alkali resistance is bad.
Aforesaid cations resin (a1) minimum film formation temperature of the present invention is between 50～100 DEG C, if conditions permit is
Can control well between 60～80 DEG C.If discontented 50 DEG C of minimum film formation temperature is likely to result in solvent resistance and molding processibility
Bad.If it exceeds cationic resin can cause corrosion resistance and drug resistance not because not being sufficiently hardened during 100 DEG C of cold drying
Good.
The present invention aforementioned nonionic resin (a2) minimum film formation temperature is between 30～50 DEG C, if conditions permit is best
Can control between 35～45 DEG C.If discontented 30 DEG C of minimum film formation temperature is likely to result in solvent resistance and molding processibility not
Good.If it exceeds nonionic resin can cause corrosion resistance and drug resistance bad because not being sufficiently hardened during 50 DEG C of cold drying.
The resin (A) of the above-mentioned use of the present invention has cationic polyurethane resin (a1) and nonionic acrylic resin
(a2) feature, due to cationic polyurethane resin (a1) relatively nonionic acrylic resin (a2) film forming design temperature
Height, during cold drying, nonionic acrylic resin is first in galvanized steel sheet surface film forming, and the polyurethane resin of cationic becomes
In the surface denseization after-hardening of epithelium before film, the distinctive processability of polyurethane resin and solvent resistance and topcoating coating are given play to
Energy.It addition, the low nonionic acrylic resin (a2) of film-forming temperature is sufficiently hardened in the critical part near steel plate and epithelium, convex
Show corrosion resistance and drug resistance.It is monolayer constructions will that the surface of the present invention processes epithelium, uses the polyurethane of different film-forming temperature
Resin and acrylic resin, it is ionic, the difference of cationic, nonionic is allowed in epithelium occur to be separated formed respectively
From Concentraton gradient, and give full play to respective performance characteristics, obtain the function of multilamellar epithelium with the structure of monolayer epithelium.
Further, (B) phosphide during the surface of the present invention processes epithelium is orthophosphoric acid as zinc-plated antirust agent
Compound and polyphosphoric acids compound.Described polyphosphoric acids is selected from pyrophosphoric acid, triphosphoric acid, three Metaphosphoric acids, four Metaphosphoric acids, hexa metaphosphoric acid
Or its ammonium salt.It addition, the percentage by weight in surface processes epithelium of phosphide (B) controls 1～5%.Weight percent
Ratio is not enough to embody additive effect during less than 1%, its corrosion resistance is low；May result in resistance to when percentage by weight is more than 5%
The performances such as alkalescence, coating bad.
Further, above-mentioned the used organo-silane coupling agents (C) of the present invention, at least contains a work in each molecule
For the amino containing reactive hydrogen of reactive functional groups, molecular configuration is not limited.Such as it is selected from N-(2-amino second
Base) 3-aminopropyltriethoxy dimethoxysilane, N-(amino-ethyl) 3-TSL 8330,3-aminopropyl three ethoxy
One or more in base silane, 3-aminopropyl trimethoxysilane and aminopropyltriethoxywerene werene etc..It addition, this is organic
The silane coupling agent (C) percentage by weight in surface processes epithelium controls 5～10%.When percentage by weight is less than 5%, its
Alkali resistance, solvent resistance, anti-blackening are low；When percentage by weight is more than 10%, it is bad that it may result in corrosion resistance.Enter one
Step is preferably 7～10%.
Further, above-mentioned the used organo-silane coupling agents (D) of the present invention, at least contains a work in each molecule
For the epoxy radicals of reactive functional groups, molecular configuration is not particularly limited.Such as be selected from 3-propyl trimethoxy silicane,
3-hydroxypropyl methyl dimethoxysilane, 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane and 3-glycidoxypropyl group first
One or more in base diethoxy silane etc..It addition, the weight that this organo-silane coupling agents (D) is in surface processes epithelium
Percentage ratio controls 15～25%.When weight ratio is less than 15%, its alkali resistance, solvent resistance, anti-blackening are low；Weight ratio surpasses
Corrosion resistance is may result in bad after 25% time.More preferably 18～25%.
Further, the titanium compound (E) of the above-mentioned use of the present invention does not has specific restriction for titanium-containing compound, it is therefore desirable to
Enough use the titanium compound at least containing more than 4 fluorine atoms in 1 molecule.This titanium compound (E) can be by the oxygen of galvanizing surface
Change epithelium to remove, improve the adherence of epithelium.This titanium compound (E) percentage by weight in surface processes epithelium wishes to control
1～5%.Addition is not less than finding effect when 1%, epithelium adherence, corrosion resistance are low；If it exceeds when 5%, add
Harden and saturated on the contrary the quality of galvanized steel plain sheet is had undesirable effect.
Further, the valence mumber of the vanadium ion of the vfanadium compound (F) of the above-mentioned use of the present invention can be divalent, trivalent, 4 valencys and
Any one of 5 valencys form, does not limit to its supply source fixed, for example, sulfate of vanadium, fluoride salt, oxide or metal
Deng.For concrete example, the sulfate of described vanadium has: sulphuric acid vitriol (II), sulphuric acid vitriol (III) etc.；The fluoride salt of vanadium has: vanadium fluoride
(III), vanadium fluoride (IV), vanadium fluoride (V) etc.；The saline oxide of vanadium has: vanadium oxide (II), vanadium oxide (III), vanadium oxide (IV)),
Vanadium oxide (V) etc..The material containing vanadium of these vanadium both can be anhydride can also be hydrate.It addition, vfanadium compound is at table
The percentage by weight that face processes in epithelium wishes to control 1～5%.When addition is less than 1%, do not find effect, it is impossible to carry
High corrosion-resistant；When adding weight ratio more than 5%, the quality of galvanized steel plain sheet is had undesirable effect by additive effect supersaturation on the contrary.
Further, the oxidic polyethylene granule (G) of the above-mentioned use of the present invention is for be divided by ethylene polymerization process and polyethylene heat
Solve the oxidized acquisition of Tissuemat E that thing obtains, containing the group such as carboxyl, hydroxy in its structure；Its molecular weight general is 1000
～10000.Above-mentioned oxidic polyethylene granule weight ratio in epithelium wishes to control 5～10%.If discontented 5%, could not
Obtain sufficient processability；If it exceeds 10% is likely to result in corrosion resistance, solvent resistance, even application adherence not
Good.Optimal weight percentage ranges controls between 5～8%.
The feature of the galvanized steel plain sheet that the surface of the present invention processes is one layer of water system epithelium of covering on the surface of galvanized steel plain sheet,
In the range of 50～75 DEG C, it is dried moisture removal, thus obtaining one layer of weight is 0.5～2.0g/m2Epithelium.
Above-mentioned baking temperature can not reach 50 DEG C and then be dried insufficient, and the galvanized steel plain sheet that surface processes can not reach simultaneously
State required many combination properties；If baking temperature is more than 75 DEG C, although ensure that epithelium is functional, but can increase
Production cost and CO2Output, power consumption is big.
It addition, the surface of the present invention processes the dried Weight control of epithelium 0.5～2.0g/m2.Dried epithelium weight
The discontented 0.5g/m of amount2Time be not easy to the biofilm of galvanized steel sheet surface, alkali resistance, corrosion resistance, anti-finger printing, anti-blackening and application
Adherence is the most insufficient；If dried epithelium weight is more than 2.0g/m2Time unit are surface processing cost can increase, be coated with
Dress adherence the most also can reduce.
How water system constituent (i.e. galvanized steel plain sheet low temperature anti-finger printing surface conditioning agent) for the present invention is attached to
There is no particular limitation for the method for galvanized steel sheet surface, such as: infusion process, spray process and roll coating process etc. are the most applicable.
There is no particular limitation, such as to the kind of object galvanized steel plain sheet, size, shape etc. for the present invention: hot-dip galvanizing sheet steel,
Plated steel sheet, electrogalvanizing nickel steel plate etc. all can use.
The present invention uses above-mentioned surface conditioning agent, under conditions of cold drying, galvanized steel plain sheet is carried out surface process, its table
The mutual synergism of component in the inorganic agent of face, it is thus achieved that the galvanized steel plain sheet that processes of surface there is the alkali resistance, resistance to of excellence simultaneously
Solvent borne, corrosion resistance, application adherence, anti-finger printing, anti-blackening and processability.
First, after metal surface material contact surface inorganic agent component, the phosphide (B) in surface conditioning agent component is to plating
The change of zinc table erodes, and the zinc of dissolution and phosphide react and form insoluble chemical compound in metal surface.During it addition, be dried
The silanol dehydrating condensation that silane coupling agent (C) and (D) hydrolyzable generate forms continuous epithelium.Through containing of above-mentioned generation
Insoluble chemical compound, coupling agent epithelium play isolation effect and improve corrosion resistance and the anti-blackening of metal material.On the other hand,
Silane coupling agent (C) and (D) hydrolyzable generate silanol and metal surface reacts and forms the combination of Si-O-M, with
Time silane coupling agent (C) and (D) reactive functional groups (reactive hydrogen contains amino and glycidyl) that has and organic resin
Functional group's (such as ester group and carboxyl) reaction, improve metal material and surface of the present invention and process the adherence of epithelium.Above
Reaction is to carry out under than relatively low state of temperature, in order to obtain anti-finger printing and processability, allows in surface conditioning agent component
Containing resin (A), when using membrane producing promoter can also under the conditions of cold drying film forming, but membrane producing promoter remains in epithelium
In, all performances can be had undesirable effect, thus it is common to use need heating-up temperature during membrane producing promoter more than 100 DEG C.This
Bright not using membrane producing promoter to prevent the appearance of this kind of situation, the surface of the present invention processes resin that galvanized steel plain sheet uses
Low make film temperature acrylic resin design temperature 30 DEG C or even 50 DEG C；Polyurethane resin design temperature 50 DEG C or even 100 DEG C.
It addition, the phosphide of the present invention (B) promotes the gelation of nonionic acrylic resin when dry, thus carry
High hardening at subcritical temerature.Speculate that the galvanized steel plain sheet that the surface of the present invention processes can be when cold drying simultaneously according to above effect
There is alkali resistance, solvent resistance, corrosion resistance, film adherence, anti-finger printing, anti-blackening and the processability of excellence.
Detailed description of the invention
Below by specific embodiment, the present invention is described further.
Following embodiment 1-11 and comparative example 1-7 illustrate the zinc-plating material of use and method for cleaning surface thereof and water
Property surface treatment liquid and process galvanized steel plain sheet method.
1. test portion
Containing the gold-plated steel plate of zinc
1) market products, thickness of slab 0.6mm two sides plated steel sheet (EG) adhesion amount 20g/m2；
2) market products, thickness of slab 0.6mm hot-dip galvanizing sheet steel (GI) adhesion amount 40g/m2；
3) market products, thickness of slab 0.6mm hot-dip aluminizing zincium steel plate (GF) adhesion amount 40g/m2。
2. the cleaning method of metallic plate
Alkali cleaner in the surface use of above-mentioned galvanized steel plain sheet (is logged in trade mark: FC-4336, Japan's rapids essence of handkerchief card (strain)
System) aqueous solution (drug concentration: 20g/L) carry out surface cleaning, treatment temperature: 60 DEG C, process the time: 20 seconds, condition for spray
Pouring processes, and removes dirt and the oils and fats of its surface attachment.The alkali liquor of surface remaining is rinsed out the most again, to test portion with tap water
Surface be cleaned.
3. surface processes epithelium composition
The composition that the surface that embodiment 1-11 and comparative example 1-7 are used processes epithelium is as shown in table 1.
4. surface processes the processing method of galvanized steel plain sheet
The galvanized steel plain sheet that the surface of the present invention processes, uses surface in table 1 to process surface conditioning agent corresponding to epithelium to phase
Answer galvanized steel plain sheet to cover, and be dried in a low temperature of 50～75 DEG C and remove moisture removal, it is thus achieved that it is resistance to that surface shown in table 2 processes
Fingerprint galvanized steel plain sheet.Table 2 is the content of the surface process galvanized steel plain sheet of embodiment 1-11 and comparative example 1-7 use.
Table 2
| Material | Epithelium amount (g/m2) | PMT(℃) | |
| Embodiment 1 | GI | 0.8 | 60 |
| Embodiment 2 | GI | 0.8 | 60 |
| Embodiment 3 | GI | 1.0 | 60 |
| Embodiment 4 | GF | 0.5 | 75 |
| Embodiment 5 | GF | 0.5 | 75 |
| Embodiment 6 | GF | 0.8 | 75 |
| Embodiment 7 | EG | 0.8 | 60 |
| Embodiment 8 | EG | 1.2 | 60 |
| Embodiment 9 | EG | 1.2 | 50 |
| Embodiment 10 | EG | 1.3 | 50 |
| Embodiment 11 | EG | 1.0 | 60 |
| Comparative example 1 | EG | 0.8 | 60 |
| Comparative example 2 | EG | 1.2 | 60 |
| Comparative example 3 | EG | 1.0 | 75 |
| Comparative example 4 | GI | 0.8 | 75 |
| Comparative example 5 | GI | 0.8 | 75 |
| Comparative example 6 | GI | 1.0 | 50 |
| Comparative example 7 | GF | 0.5 | 50 |
5. evaluation test method
The surface that above-described embodiment and comparative example obtain processes the performance of galvanized steel plain sheet and is evaluated by the following method.
5.1 alkali resistance
5.1.1 alkali resistance is 1.
The surface that provided process the surface of galvanized steel plain sheet drip 1% caustic soda aqueous solution 10 μ L, place 30 seconds after,
The change of perusal appearance is rinsed with water.Evaluation criterion is as follows:
◎: part of dripping is entirely without vestige；
Zero: and trickle vestige；
△: slight vestige；
×: having obvious albefaction vestige, epithelium dissolves.
5.1.2 alkali resistance is 2.
The surface processing galvanized steel plain sheet on the surface provided uses alkaline defatting agent CL-364S (Japan handkerchief Ka Lai refines)
2% join tank liquor 120 seconds spray, washing after with colour difference meter △ E, outward appearance is evaluated.Evaluation criterion is as follows:
◎: △ E≤1；
Zero: 1 ＜ △ E≤3；
△: 3 ＜ △ E≤5；
×: △ E ＞ 5.
5.2 solvent resistance
Reagent uses ethanol and 80% ethanol and the mixed solution of 20% water, methyl ethyl ketone, dimethylbenzene, uses gauze respectively
Processing the surface of galvanized steel plain sheet after dipping on surface firmly the most back and forth after friction 50 times, surface cosmetic variation is evaluated in visualization.Comment
Price card is accurate as follows:
◎: wiping part is entirely without vestige；
Zero: wiping part has few vestige；
△: wiping part has slight vestige；
×: having obvious albefaction vestige, epithelium dissolves.
5.3 corrosion resistance
By salt spraytest (JIS Z 2371), visually measure resistance to white rust, white rust area is reached the time of 5%
It is evaluated.
5.4 film adherences
Process the surface of galvanized steel plain sheet on the surface provided, implement application by following condition, carry out application adherence examination
Test.
<application condition>alkyd resin coating (big Nippon Paint Co., Ltd., trade name Derikon, #700) application: coating rod method,
Baking condition: the film that 140 DEG C × 20 point 25 μm is formed.
1. exert oneself after (until base material) hundred lattice draw lattice with NT cutter at film surface of steel plate, then shell with mightiness belt
From, film remaining number is evaluated.
2. after first hundred lattice draw lattice again with the convex tester of cup do 5mm cup convex after with mightiness belt, protuberance is peeled off, right
Coating remaining number is evaluated.
5.5 anti-finger printing
Press...with one's finger bread board, is evaluated the vestige state of fingerprint.Evaluation criterion is as follows:
◎: entirely without fingerprint；
Zero: have few fingerprint trace；
△: have slight fingerprint trace；
×: there is obvious fingerprint trace.
5.6 anti-blackening
Cutting the bread board of plural number, each bread board face-to-face 5～10, to overlap, is screwed after packing with plastics package paper
Behind 4 angles, then apply the loading of 0.67Kgf.cm with torque spanner, be placed on 70 DEG C, in the moistening case of the relative humidity of 80%
Take out after 240 hours, the black change situation stacking position is judged.Evaluation criterion is as follows:
◎: without black change
Zero: the most slight Lycoperdon polymorphum Vitt；
△: the most graying；
×: substantially blackening.
5.7 processability
The evaluation of processability implements Draw Bead test.
The bread board that embodiment and comparative example provide is cut into the test film of 30mm × 300mm size, and Draw Bead tests
Condition is: pressurization loading 1000Kgf, Bead tip radius 5.0mm, draw speed 260mm/ divide.The surface shape of sample after test
State is judged by following standard.
<Draw Bead test evaluation standard>
◎: epithelium is entirely without damage；
Zero: denier epithelium melanism；
△: it can be seen that significantly blackstreak；
×: fracture.
Above-mentioned evaluation result is shown in Table 3.
Table 3 evaluation test result
Note: 1) hundred lattice remaining numbers.
Can be evident that by the result of table 3, at the outer nonionic acrylic resin (a2) of the scope of the present invention or
Can not be sufficiently hardened without resin when cationic polyurethane resin (a1) comparative example 1,2 low temperature, alkali resistance is poor.It addition, do not contain
Organic silicon compound (C) and (D) comparative example 3, the alkali resistance of comparative example 7, corrosion resistance and poor in processability.Not titanium-containing compound (E),
Vanadium (F) comparative example 4,6 alkali resistance, solvent resistance and anti-blackening are poor.It addition, the poly(ethylene oxide) particle (G) without the present invention
Comparative example 5 poor in processability.Process galvanized steel plain sheet embodiment 1-11 according to the surface comparing the present invention above and show good
Alkali resistance, solvent resistance, corrosion resistance, film adherence, anti-finger printing, anti-blackening and processability.
As it has been described above, it is that one can reduce carrying capacity of environment, suppression chromium and CO that the surface of the present invention processes galvanized steel plain sheet2Row
The surface treated steel plate put.To the social problem such as environmental conservation and cyclicity, extremely effectively and practicality effect is very big.
Claims (14)
1. a galvanized steel plain sheet anti-finger printing surface conditioning agent, its aqueous solution contains following component:
(A) (a1) the minimum polyurethane resin making the cationic that film temperature is 50～100 DEG C of scopes, shared percentage by weight is
The 10～20% of total solid content；
(a2) the minimum acrylic resin making the nonionic that film temperature is 30～50 DEG C of scopes, shared percentage by weight is total solid
The 20%～40% of content；
(B) phosphide, shared percentage by weight is the 1～5% of total solid content；
(C) organo-silane coupling agents containing amino, at least should contain containing in each molecule of the organo-silane coupling agents of amino
Having the amino containing reactive hydrogen as reactive functional groups, shared percentage by weight is the 5～10% of total solid content；
(D) organo-silane coupling agents containing epoxy radicals, in each molecule of the organo-silane coupling agents that should contain epoxy radicals extremely
Containing an epoxy radicals as reactive functional groups less, shared percentage by weight is the 15～25% of total solid content；
(E) titanium compound, shared percentage by weight is the 1～5% of total solid content；
(F) vfanadium compound, shared percentage by weight is the 1～5% of total solid content；
(G) oxidic polyethylene granule, shared percentage by weight is the 5～10% of total solid content；
Total solid content in described galvanized steel plain sheet anti-finger printing surface conditioning agent accounts for the 10-20% of surface conditioning agent weight；Water
Account for the 80-90% of surface conditioning agent weight.
2. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 1, it is characterised in that described cationic
The acrylic resin of polyurethane resin and nonionic is all without membrane producing promoter.
3. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 1, it is characterised in that described cationic
Polyurethane resin (a1) in the molecular configuration containing at least one sun in primary amino radical, secondary amine, tertiary amino and season amino from
The cation type polyurethane resin of Zi Xing functional group.
4. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 3, it is characterised in that described cationic is gathered
Urethane resin (a1) is by polyester polyalcohols, polyether polyols or Merlon polyalcohols and aliphatic isocyanates and/or fragrance
Between race's isocyanate compound, polymerization is formed, and a part for its polyalcohols used is containing N, N dimethylamine base dihydroxymethyl
The polyalcohols of propane or the polyalcohols containing polyethylene oxide chain.
5. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 1, it is characterised in that described nonionic third
Olefin(e) acid resin (a2) contains polyoxyethylene chain, hydroxy, the 1st amide groups, the 2nd amide groups, the 3rd amide groups in molecular configuration
In the nonionic acrylic resin of at least one nonionic functional group.
6. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 5, it is characterised in that described nonionic third
Olefin(e) acid resin (a2) is to use one or more nonionics in Polyethylene Glycol methacrylic acid and 2-hydroxyethyl methylacrylate
Type hydrophilic group monomer, and one or both in acrylate monomer and methacrylate monomer, and with additional polymerization
The co-polypropylene acid resin of unsaturated monomer copolymerization；Described additional polymerization unsaturated monomer is selected from styrene, acrylonitrile
With one or more in vinyl acetate.
7. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 1, it is characterised in that described phosphide (B)
It is orthophosphoric acid compound and polyphosphoric acids compound as zinc-plated antirust agent.
8. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 7, it is characterised in that described polyphosphoric acids
Compound is selected from pyrophosphoric acid, triphosphoric acid, three Metaphosphoric acids, four Metaphosphoric acids, hexa metaphosphoric acid or its ammonium salt.
9. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 1, it is characterised in that
The described organo-silane coupling agents (C) containing amino is selected from N-(2-amino-ethyl) 3-aminopropyltriethoxy dimethoxy
Silane, N-(amino-ethyl) 3-TSL 8330,3-aminopropyl triethoxysilane, 3-aminopropyl front three
One or more in TMOS and aminopropyltriethoxywerene werene；
The described organo-silane coupling agents (D) containing epoxy radicals selected from 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane and
One or more in 3-glycidoxypropyl diethoxy silane.
10. galvanized steel plain sheet anti-finger printing surface conditioning agent as claimed in claim 1, it is characterised in that
Described titanium compound (E) uses the titanium compound at least containing more than 4 fluorine atoms in 1 molecule；
The valence state of the valence mumber of the vanadium ion of described vfanadium compound (F) is any one of divalent, trivalent, 4 valencys and 5 valencys valence state；Choosing
From the sulfate of vanadium, fluoride salt or oxide.
11. galvanized steel plain sheet anti-finger printing surface conditioning agents as claimed in claim 1, it is characterised in that the poly-second of described oxidation
Alkene granule (G) is the oxidized acquisition of Tissuemat E obtained by ethylene polymerization process and polyethylene pyrolysate, this oxidic polyethylene
Granule contains carboxyl and hydroxy；Its molecular weight is between 1000～10000.
12. 1 kinds of methods processing galvanized steel plain sheet, for using the arbitrary described galvanized steel plain sheet anti-finger printing of claim 1-11
Surface conditioning agent covers at least one surface of galvanized steel plain sheet, is dried and removes moisture removal, it is thus achieved that table at a temperature of 50～75 DEG C
It is 0.5～2.0g/m that face processes epithelium2Surface process anti-finger printing galvanized steel plain sheet.
The anti-finger printing galvanized steel plain sheet that 13. 1 kinds of surfaces process, its at least one face is coated with surface reason epithelium, described table
Face processes epithelium and contains following component:
(A) (a1) the minimum polyurethane resin making the cationic that film temperature is 50～100 DEG C of scopes, shared percentage by weight is
Surface processes the 10～20% of epithelium；
(a2) the minimum acrylic resin making the nonionic that film temperature is 30～50 DEG C of scopes, shared percentage by weight is surface
Process the 20%～40% of epithelium；
(B) phosphide, shared percentage by weight is that surface processes the 1～5% of epithelium；
(C) organo-silane coupling agents containing amino, at least should contain containing in each molecule of the organo-silane coupling agents of amino
Have the amino containing reactive hydrogen as reactive functional groups, shared percentage by weight be surface process epithelium 5～
10%；
(D) organo-silane coupling agents containing epoxy radicals, in each molecule of the organo-silane coupling agents that should contain epoxy radicals extremely
Containing an epoxy radicals as reactive functional groups less, shared percentage by weight is that surface processes the 15～25% of epithelium；
(E) titanium compound, shared percentage by weight is that surface processes the 1～5% of epithelium；
(F) vfanadium compound, shared percentage by weight is that surface processes the 1～5% of epithelium；
(G) oxidic polyethylene granule, shared percentage by weight is that surface processes the 5～10% of epithelium.
The anti-finger printing galvanized steel plain sheet that 14. surfaces as claimed in claim 13 process, it is characterised in that described surface processes skin
The weight of film is 0.5～2.0g/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310108818.0A CN104073100B (en) | 2013-03-29 | 2013-03-29 | A kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310108818.0A CN104073100B (en) | 2013-03-29 | 2013-03-29 | A kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104073100A CN104073100A (en) | 2014-10-01 |
| CN104073100B true CN104073100B (en) | 2016-12-07 |
Family
ID=51594718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310108818.0A Active CN104073100B (en) | 2013-03-29 | 2013-03-29 | A kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104073100B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105463436B (en) * | 2015-07-27 | 2018-03-09 | 宝山钢铁股份有限公司 | A kind of manufacture method for the environmentally friendly surface conditioning agent of galvanized steel plain sheet, galvanized steel plain sheet and galvanized steel plain sheet |
| CN109943837A (en) * | 2019-05-08 | 2019-06-28 | 兴化市华成镀锌管件有限公司 | A kind of surface treating agent for galvanized steel plain sheet |
| CN109943841A (en) * | 2019-05-08 | 2019-06-28 | 兴化市华成镀锌管件有限公司 | A kind of galvanized steel plain sheet resistance and fingerprint resistance inorganic agent and preparation method thereof |
| CN110205008A (en) * | 2019-05-24 | 2019-09-06 | 上海丰野表面处理剂有限公司 | A kind of chromium-free fingerprint-resistant inorganic agent |
| CN111849286B (en) * | 2020-07-30 | 2021-11-05 | 辽宁宝瑞科技有限公司 | Bacteriostatic fingerprint-resistant coating agent, and preparation method and application thereof |
| CN113817391A (en) * | 2020-09-07 | 2021-12-21 | 帕珂表面处理技术(上海)有限公司 | Surface treatment agent for stainless steel material |
| CN112280453A (en) * | 2020-10-29 | 2021-01-29 | 蓝帆新材料技术(广州)有限公司 | Fingerprint-resistant surface treating agent for galvanized steel sheet and preparation method thereof |
| CN112280452B (en) * | 2020-10-29 | 2021-11-02 | 蓝帆新材料技术(广州)有限公司 | Chromium-free fingerprint-resistant coating composition for galvanized steel sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787527A (en) * | 2009-01-22 | 2010-07-28 | 宝山钢铁股份有限公司 | Galvanized steel plate with excellent machining property and alkali and solvent resistance and surface treating agent |
| CN102378827A (en) * | 2009-03-31 | 2012-03-14 | 杰富意钢铁株式会社 | Surface-treating agent, process for manufacturing plated steel sheet using the surface-treating agent, and plated steel sheet |
| CN102632656A (en) * | 2012-04-26 | 2012-08-15 | 宝山钢铁股份有限公司 | Galvanized steel sheet excellent in processability and corrosion resistance as well as surface treating agent for same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY181000A (en) * | 2010-09-29 | 2020-12-15 | Jfe Steel Corp | Method for manufacturing zinc or zinc alloy coated steel sheet and zinc or zinc alloy coated steel sheet manufactured by the method |
-
2013
- 2013-03-29 CN CN201310108818.0A patent/CN104073100B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787527A (en) * | 2009-01-22 | 2010-07-28 | 宝山钢铁股份有限公司 | Galvanized steel plate with excellent machining property and alkali and solvent resistance and surface treating agent |
| CN102378827A (en) * | 2009-03-31 | 2012-03-14 | 杰富意钢铁株式会社 | Surface-treating agent, process for manufacturing plated steel sheet using the surface-treating agent, and plated steel sheet |
| CN102632656A (en) * | 2012-04-26 | 2012-08-15 | 宝山钢铁股份有限公司 | Galvanized steel sheet excellent in processability and corrosion resistance as well as surface treating agent for same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104073100A (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104073100B (en) | A kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet | |
| TWI555881B (en) | A water-based metal surface treatment agent and a metal surface treatment method using the same | |
| CN100391623C (en) | Surface treating agent with excellent alkali resistance and solvent resistance and for zinc coated steel plate | |
| CN105255338B (en) | Galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali and aqueous surface-treating agent | |
| AU2006260006B2 (en) | Chrome-free composition of low temperature curing for treating a metal surface and a metal sheet using the same | |
| CN100584908C (en) | Environment-friendly type galvanizing metal surface treating agent | |
| CN100391625C (en) | Zinc coated steel plate with excellent alkali resistance and solvent resistance | |
| CN102746778B (en) | Galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, surface treatment agent and treatment method | |
| CN103124808B (en) | Hot-dip galvanized steel sheet and manufacturing method therefor | |
| CN101787527B (en) | Galvanized steel plate with excellent machining property and alkali and solvent resistance and surface treating agent | |
| CN100510177C (en) | Composition and method for surface treatment of metal materials | |
| TWI534216B (en) | Water - based metal surface treatment agent | |
| CN105463436B (en) | A kind of manufacture method for the environmentally friendly surface conditioning agent of galvanized steel plain sheet, galvanized steel plain sheet and galvanized steel plain sheet | |
| CN102877054A (en) | Metal surface treatment agent and metal material obtained through processing with same | |
| JP2006213958A (en) | Composition for surface treatment of metallic material, and treatment method | |
| AU2016363456A1 (en) | Chromium-free surface-treated tinplate, production method and surface treating agent therefor | |
| JP2005120469A (en) | Composition for treating surface of metallic material, and surface treatment method | |
| KR20130051997A (en) | Surface treatment fluid for zinc-plated steel sheet, zinc-plated steel sheet, and manufacturing method for same | |
| CN109321908A (en) | A kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application method | |
| AU2012254470B2 (en) | Chemical conversion treatment agent for surface treatment of metal substrate, and surface treatment method of metal substrate using same | |
| CN103726043A (en) | Water-based metal surface treatment agent, metal surface processing envelope and metal material with same | |
| CN101792903A (en) | Non-chrome alkali-resistant and solvent-resistant galvanized steel sheet surface treatment liquid and preparation method thereof | |
| JP2007002330A (en) | Surface treatment agent for zinc or zinc alloy galvanized steel sheet, and surface treated zinc or zinc alloy galvanized steel sheet | |
| CN102632656A (en) | Galvanized steel sheet excellent in processability and corrosion resistance as well as surface treating agent for same | |
| KR100643353B1 (en) | Composition For Treating Metal Surface With Excellent Corrosion Resistance, Anti-Alkalinity And Anti-Finger Property And Treated Steel Sheet Therewith |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |