CN1887449A - Surface treating agent with excellent alkali resistance and solvent resistance and for zinc coated steel plate - Google Patents
Surface treating agent with excellent alkali resistance and solvent resistance and for zinc coated steel plate Download PDFInfo
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- CN1887449A CN1887449A CNA2005100271574A CN200510027157A CN1887449A CN 1887449 A CN1887449 A CN 1887449A CN A2005100271574 A CNA2005100271574 A CN A2005100271574A CN 200510027157 A CN200510027157 A CN 200510027157A CN 1887449 A CN1887449 A CN 1887449A
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- galvanized steel
- alkali resistance
- solvent resistance
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention relates to surface treating agent for zinc coated steel plate, and is especially one kind of surface treating agent with excellent alkali resistance and solvent resistance for zinc coated steel plate. The surface treating agent is water solution, which consists of fluoric acid with 4 or more fluorine atoms and at least one of Ti, Zr and Si atome in 0.1-5.0 wt%; phsosphorus containing compounding 0.01-0.5 wt%; one or more organic silicon coupling agent with amino group containing at least one active hydrogen atom 10-20 wt%, one or more organic silane coupling agent with at least one epoxy group 25-50 wt%; at least one kind of cationic or non-ionic water soluble polyurethane resin 30-60 wt% and vanadium compound 0.1-1.0 wt%. It is used in forming protecting film with excellent performance on the surface of zinc coated steel plate.
Description
Technical field
The present invention relates to a kind of surface conditioning agent that is used for galvanized steel plain sheet; this surface conditioning agent can form diaphragm at galvanized steel sheet surface; when this diaphragm is given galvanized steel sheet surface excellent alkali resistance and solvent resistance, can form performances such as good corrosion resistance, anti-finger printing, painting adhesion again.
Background technology
Galvanized steel plain sheet is widely used in every field such as automobile, building materials, household electrical appliances.But these metal materials are corroded in atmospheric environment easily owing to contain compositions such as zinc and aluminium, form white rust.This phenomenon not only influences the outward appearance of galvanized steel plain sheet, also painting adhesion is had a negative impact.In order to improve corrosion resistance and painting adhesion, usually galvanizing surface is carried out Passivation Treatment, use more inorganic agent to contain chromic acid, dichromic acid or their salts substances mostly at present.
In recent years along with the improving constantly of environmental requirement, 6 contained in the inactivating treatment liquid that metal material surface is handled valency chromium are because of causing direct negative effect to human body, and Passivation Treatment is kept someone at a respectful distance by people.In addition, as containing 6 valency chromium, must take specially treated in the waste water of discharge according to the relevant laws regulation.This also becomes one of assignable cause of overall cost rising.Also have, can't carry out recyclingly through the metal material after the Passivation Treatment when scrapping owing to contain chromium, this is its very big shortcoming and has caused social problem.After particularly country such as European Union had issued the regulation of forbidding poisonous and harmful substances such as 6 valency chromium, the passivation treating agent that contains 6 valency chromium was just progressively replaced by chromium-free passivating treatment agent.In the metal material surface process field, relevant departments are are all researching and developing chromium-free deactivation and the inorganic agent of anti-fingerprint that does not contain harmful substances such as 6 valency chromium both at home and abroad, and have proposed various methods.
For example, the application of tannic acid in surface conditioning agent that includes the polyhydric phenols carboxylic acid is widely known by the people.With after containing the tannin aqueous acid metal material being handled; the diaphragm that tannic acid and metal material reaction back generate can form screen effect to the intrusion of corrosive deposit; reduce the chance that corrosive deposit contacts with metal material surface, improved decay resistance thus.But, owing to, the corrosion resistance of diaphragm is also had higher requirement in recent years to the high-quality requirement of product; therefore; if use tannic acid or while also with the diaphragm that other inorganic constituents obtained separately, its corrosion resistance is still unsatisfactory, can't carry out industrial applications.In order further to improve decay resistance; open in the clear 53-121034 communique the spy; disclose and utilized the aqueous solution that contains water-dispersible silica, alkyd resins, trialkoxy silane compound to be coated on the metal surface, dry back forms the processing method of diaphragm.Open in the clear 54-56037 communique the spy, also disclose and used the water-soluble resin that is constituted by hydroxyl dipyrryl ketone compound derivatives, giving the surface treatment method that the metal material corrosion resistance is a purpose, and use the aqueous solution of hydroxy styrenes compound or the method that aqueous dispersion polymers is given the metal material corrosion resistance.But its corrosion resistance of diaphragm that above-mentioned any method obtains is not as the passivation protection film.In order to address this problem, the spy opens the metal conditioner composition that the suggestion use is made of the metal ion more than the divalent, acid, organosilan coupling agent and water-soluble polymer in the flat 11-106945 communique.But, in fact the problems referred to above point is still failed to obtain to solve effectively.With the surface treated steel plate that above chromium-free treatment agent is produced, when household electrical appliances such as making computer part, a lot of producers will coat punching oil in the contour machining procedure section, use alkaline degreasing agent that punching oil is removed then, even use solvent to carry out degreasing sometimes.At this moment, variable color can take place even problem such as come off in the diaphragm of surface of steel plate.Therefore, market in urgent need is through after above-mentioned degreasing process, the contour machining procedure, and diaphragm can not damage, and can give the Chrome-free surface conditioning agent and the corresponding processing method of decay resistance simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance, satisfy household electrical appliances user's high-quality and environmental requirement, the technical issues that need to address are: the galvanized steel plain sheet that only applies this inorganic agent of one deck also will have good anti-corrosion, anti-finger printing and painting adhesion when having excellent alkali resistance, solvent resistance.Satisfy user's highly basic degreasing, solvent clean and high performance requirement such as anti-corrosion.
In order to solve the problem that conventional art exists; through after the arduous research; found that contain surface conditioning agent that fluoracid, phosphorus-containing compound, organosilan coupling agent, the specific one-tenth such as water soluble polyurethane resin of special metal is grouped into the surface of metal material handled by use after; the diaphragm that forms had both had excellent alkali resistance, solvent resistance, also had good corrosion resistance, anti-finger printing and painting adhesion simultaneously.
Technical scheme of the present invention is: have the surface conditioning agent that is used for galvanized steel plain sheet of excellent alkali resistance and solvent resistance, its aqueous solution contains following component:
A) fluoracid contains the fluorine atom more than 4 at least in the fluoracid, contain selected at least more than one element from the groups of elements that titanium, zirconium and silicon are formed in addition, and the percentage by weight of the shared total solid content of fluoracid is 0.1～5.0%;
B) phosphorus-containing compound, shared percentage by weight is calculated as 0.01～0.5% of total solid content with phosphorus;
C) one or more contain the organosilan coupling agent of the amido functional group of at least one reactive hydrogen, and shared percentage by weight is 10～20% of total solid content;
D) one or more contain the organosilan coupling agent of at least one epoxy functionality, and shared percentage by weight is 25～50% of total solid content;
E) water soluble polyurethane resin of at least a cationic or nonionic, shared percentage by weight is 30～60% of total solid content;
F) vfanadium compound, shared percentage by weight are 0.1～1.0% of total solid content.
Above component is by dissolving or be scattered in the water, and as feature, forms the chromium-free fingerprint-resistant surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance.Surface treatment method of the present invention is: will be adjusted to 2.0～6.5 according to the surface conditioning agent pH value of solution value that proportioning obtains, and then this aqueous surface treatment fluid will be coated in galvanized steel sheet surface, dry back forms 0.3～3.0g/m
2Diaphragm.
Surface conditioning agent of the present invention, its aqueous solution contain the fluoracid that includes special metal, phosphorus-containing compound, 2 kinds water soluble polyurethane resin and the vfanadium compound by the organosilan coupling agent that compound constituted that includes specific reactivity functional group more than a kind, cationic or nonionic.
(a) in the surface treatment composition of the present invention refers to the fluorine atom that contains at least more than 4, contains the fluoracid of selected at least more than one element from the groups of elements that titanium, zirconium and silicon are formed in addition.There is no particular limitation to their use level, but wish that pH value with this fluoracid adjustment surface treatment composition is in 2.0～6.5 scopes.In addition, (a) in total solid content shared percentage by weight be preferably 0.1～5.0%.(a) if percentage by weight is lower than 0.1%, and pH can't adjust in the above-mentioned scope, causes that film forming is poor, and corrosion resistance reduces; If percentage by weight exceeds 5%, may cause surface treatment composition and contain the bad stability of the aqueous solution of said composition.
(b) in the surface treatment composition of the present invention is phosphorus-containing compound, can be orthophosphoric acid form or polyphosphoric acid form.The orthophosphoric acid form can be H
3PO
4Or ammonium phosphate, the polyphosphoric acid form can be pyrophosphoric acid, triphosphoric acid, three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid or its ammonium salt.In addition, (b) in total solid content shared percentage by weight calculate with phosphorus and be preferably 0.01～0.5%.During percentage by weight less than 0.01%, additive effect is poor, and corrosion resistance descends; Percentage by weight surpasses at 0.5% o'clock, may cause the reduction of alkali resistance, painting adhesion.
The organosilan coupling agent (c) that uses among the present invention contains the amino that contains reactive hydrogen as reactive functional groups at least in each molecule.There is no particular limitation for structure, and for example: N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl) 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane etc. similarly constituent can use.In addition, (c) in total solid content shared percentage by weight be preferably 10～20%.Discontented 10% o'clock of percentage by weight, alkali resistance, solvent resistance, anti-blackening reduce; Percentage by weight surpasses at 20% o'clock, may cause corrosion resistance to descend.
The organosilan coupling agent (d) that uses among the present invention contains an epoxy radicals as reactive functional groups at least in each molecule, textural nothing limits especially.For example: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane etc. similarly constituent can use.In addition, (d) in total solid content shared percentage by weight be preferably 25～50%.Discontented 25% o'clock of percentage by weight, alkali resistance, solvent resistance, anti-blackening reduce; Percentage by weight surpasses at 50% o'clock, may cause corrosion resistance to descend.
The water soluble polyurethane resin that uses among the present invention (e) can be cationic, also can be nonionic; Can select wherein a kind of, also can select multiple mixing wherein.In the cation type resin, except containing cationic functional groups such as amino, imino group, secondary amino group and uncle's amino, also can contain nonionic functional groups such as polyethylene oxide chain, hydroxyl; In the non-ionic resin, a kind of nonionic functional group be can contain, other nonionic functional groups and/or cationic functional group also can be contained.First-selection contains the polyurethane resin of said structure; From resin, select the kind of water-soluble type or water-dispersion type again.
That is to say that above-mentioned cationic functional group and/or nonionic functional group can be used as hydrophilic group makes resin be dissolvable in water water, or disperse to form emulsion form by the oneself; Perhaps use cationic and/or nonionic surface active agent make resin be dissolvable in water water, or force to be scattered in and form water-soluble resin in the water.
For the diaphragm of giving water soluble polyurethane resin (e) formation has good alkali resistance, need to select cationic or non-ionic resin.In addition, preferably and other materials, good intermiscibility as fluoracid (a), phosphorus-containing compound (b), organosilan coupling agent (c) and (d) is arranged.
As polyurethane resin, be to form by polymerization between polyalcohols such as polyester polyalcohols, polyether polyols, Merlon polyalcohols and aliphatic isocyanates and/or the aromatic isocyanate compound, the part of its employed polyalcohols can be to contain N, the polyalcohols that TMSDMA N dimethylamine base dihydroxy methylpropane etc. are amino also can be to contain the polyalcohols that is similar to the such polyethylene oxide chain of polyethylene glycol.
It is 30～60% that these water soluble polyurethane resins (e) preferably account for hundred parts of ratios of total solid content weight.If percentage by weight is lower than 30%, corrosion resistance and solvent resistance can descend.If percentage by weight surpasses 60%, then alkali resistance can reduce.
The vfanadium compound that uses among the present invention (f), the chemical valence of vanadium can be+divalent ,+3 valencys ,+4 valencys ,+5 valencys, its indefinite of originating is such as being sulfate, fluoride, oxide, metal etc.Particularly, in the sulfate chemical valence of vanadium can be+divalent ,+3 valencys etc., in the fluoride price of vanadium can be+3 valencys ,+4 valencys ,+5 valencys etc., in the oxide price of vanadium can be+divalent ,+3 valencys ,+4 valencys ,+5 valencys etc.These compounds can be anhydrous compounds, also can be hydrates.Vanadium-containing compound shared percentage by weight in total solid content is preferably 0.1～1.0%.If percentage by weight is lower than 0.1%, just can not manifest additive effect, corrosion resistance can not get improving; If percentage by weight surpasses 1.0%, vanadium-containing compound and the bad stability that contains the aqueous solution of this vanadium-containing compound.
The pH that contains the aqueous surface treatment fluid of surface treatment composition of the present invention preferably is adjusted in 2.0～6.5 the scope.When improving aqueous surface treatment fluid pH value, can select for use pH such as ammoniacal liquor, hydroxide to adjust agent; When reducing the pH value, preferably use used among the present invention (a) and/or (b).PH easily causes the film forming of diaphragm bad less than the hyperergy of and substrate surface at 2.0 o'clock, and the alkali resistance of the diaphragm that obtains, solvent resistance, corrosion resistance, anti-finger printing, anti-blackening and painting adhesion etc. are not very desirable.If pH is greater than 6.5, organosilan coupling agent (d), water-soluble resin itself precipitate from the aqueous surface treatment fluid easily separates out, and causes the aqueous surface treatment fluid to get and shortens service life.
The present invention makes the aqueous surface treatment fluid be attached to the surface of galvanized steel plain sheet, and dried dry film weight preferably is controlled at 0.3～3.0g/m
2Less than 0.3g/m
2The time, galvanized steel sheet surface is difficult to protected film and thoroughly covers, and performance such as alkali resistance, corrosion resistance, anti-finger printing, anti-blackening and painting adhesion is undesirable.If surpass 3.0g/m
2The time, the surface treatment cost of unit are is higher, and painting adhesion also may descend.The aqueous surface treatment fluid is attached to not special qualification the on the method for surface of steel plate, such as adopting methods such as dipping, spray and roller coat to handle.Also have no particular limits to treatment temperature with on the processing time.The drying of the aqueous surface treatment fluid that galvanized steel sheet surface is adhered to is preferably under the heated condition carries out.Heating-up temperature preferably is controlled at 60～200 ℃.Later technology also can adopt the water-cooled cooling as required.
In the surface treatment composition of the present invention, also can be used filler and lubricant.As filler can be: the colloidal sol of zirconium, the colloidal sol of aluminium oxide, Ludox etc.; Lubricant can be: Tissuemat E, polypropylene wax etc.Above-mentioned filler and lubricant etc. can be used in surface treatment composition of the present invention in advance.
The object that inorganic agent of the present invention is handled is that the kind, size, shape of galvanized steel plain sheet etc. has no particular limits, and all is suitable for such as hot-dip galvanizing sheet steel, galvanizing aluminium alloy steel plate, plated steel sheet, electroplated zinc nickel alloy steel plate.
Inorganic agent of the present invention is coated on the galvanized steel sheet surface, has significantly improved the performances such as alkali resistance, solvent resistance, corrosion resistance and painting adhesion of galvanized steel plain sheet by following effect.At first, galvanized steel sheet surface is with after inorganic agent of the present invention contacts, and the fluoracid in the inorganic agent on the zinc coat surface etching takes place.Make the pH of reaction interface rise thus, the metal ion of stripping and water-soluble resin reaction form the resin protection film of slightly solubility and are attached to reaction interface.In addition, the special metal element that fluoracid is contained, promptly titanium, zirconium and silicon ion and phosphoric acid react, and have played the effect of antirust agent behind the formation phosphate.The phosphate that the resin protection film of slightly solubility and reaction form has been brought into play the corrosion resistant effect of raising galvanized steel plain sheet together.But; iff so; tack between zinc coat and the diaphragm is also poor; therefore be used the organosilan coupling agent of amino and epoxy radicals; after adding water decomposition; the dehydration polymerization taking place between the functional group in each organosilan coupling agent (OR yl), formed the very tough and tensile diaphragm with screen effect, has improved alkali resistance and solvent resistance thus.If have only a kind of organosilan coupling agent, just be difficult to form this tough and tensile diaphragm with screen effect, the performance performance can be very not desirable yet.Functional group in these coupling agents can also form the hydrogen-oxygen key with the zinc coat surface; in addition; reactive functional groups that the organosilan coupling agent is all and the water-soluble resin in the agent composition and in the organic coating of chromium-free fingerprint-resistant diaphragm surface spraying contained ester group, hydroxyl react, improved zinc coat and chromium-free fingerprint-resistant diaphragm and the tack between the organic coating of diaphragm surface spraying thus.Also have, vanadium ion, makes an addition in the inorganic agent of the present invention and can further improve decay resistance for known to everybody as the ion with rust-preventing characteristic.
Beneficial effect of the present invention:
1) do not contain poisonous and harmful substances such as Cr VI in the galvanized steel sheet surface treating agent of the present invention, belong to environmentally friendly machine;
2) galvanized steel sheet surface treating agent of the present invention can adopt one-step method that galvanized steel sheet surface is handled, and has simplified treatment process;
3) galvanized steel plain sheet that is coated with surface conditioning agent of the present invention also has performances such as good anti-corrosion, anti-finger printing and painting adhesion when having excellent alkali resistance, solvent resistance.
The specific embodiment
Embodiment: the embodiment of the invention 1～9, comparative example 1～6 performance is as follows:
Following examples have been used electrogalvanizing, galvanizing and galvanizing aluminium alloy steel plate, but scope of the present invention is not limited by these specific embodiments.Below employed galvanized steel plain sheet, its surperficial cleaning method, surface conditioning agent and Performance Detection in embodiment and the comparative example are described.
1, test piece
(a) product of market sale, thickness of slab 0.6mm, two-sided plated steel sheet (EG), coating adhesion amount 20g/m
2
(b) product of market sale, thickness of slab 0.6mm, hot-dip galvanizing sheet steel (GI), coating adhesion amount 40g/m
2
(c) product of market sale, thickness of slab 0.6mm, galvanizing aluminium alloy steel plate (GF), coating adhesion amount 40g/m
2
2, the cleaning method of galvanized steel plain sheet
The aqueous solution (concentration is 20g/L) with the degreasing agent of moderate alkalescence (login trade mark: FC-4336, Nihon Parkerizing Co., Ltd. produces) cleans galvanized steel sheet surface.Treatment temperature: 60 ℃; Processing time: 20 seconds; Processing mode: spray.With the running water washing, remove the remaining alkaline components in surface then.
3, surface conditioning agent is formed
The employed surface conditioning agent of embodiment and comparative example is formed as shown in table 1.
Table 1 surface conditioning agent is formed
| Numbering | Fluoracid (a) | Phosphorus-containing compound (b) | Organosilan coupling agent (c) | Organosilan coupling agent (d) | Water soluble polyurethane resin (e) | Vanadium-containing compound (F) | |||||
| Kind | Proportional quantity (accounting for solid content %) | Kind | Proportional quantity (accounting for solid content %) with phosphorus calculating | Kind 1) | Proportional quantity (accounting for solid content %) | Kind 2) | Proportional quantity (accounting for solid content %) | Kind 3) | Proportional quantity (accounting for solid content %) | Proportional quantity (accounting for solid content %) | |
| The scope of application | - | 0.1-5.0％ | - | 0.01-0.5％ | - | 10-20％ | - | 25-50％ | - | 30-60％ | 0.1-1.0％ |
| Embodiment 1 | Fluotitanic acid | 0.7 | Ammonium phosphate | 0.3 | c1 | 20 | d1 | 38.8 | e1 | 40 | 0.2 |
| Embodiment 2 | Fluosilicic acid | 1 | Phosphoric acid | 0.2 | c1 | 13 | d1 | 38 | e1 | 47.5 | 0.3 |
| Embodiment 3 | The fluorine zirconic acid | 0.2 | Ammonium pyrophosphate | 0.2 | c1 | 10 | d1 | 40 | e2 | 49.2 | 0.4 |
| Embodiment 4 | Fluotitanic acid | 4.2 | Ammonium phosphate | 0.3 | c2 | 15 | d2 | 40 | e2 | 40 | 0.5 |
| Embodiment 5 | Fluotitanic acid | 1.72 | Phosphoric acid | 0.08 | c2 | 10 | d2 | 45.5 | e3 | 42 | 0.7 |
| Embodiment 6 | Fluotitanic acid | 0.95 | Four metaphosphoric acids | 0.05 | c2 | 20 | d1 | 43.3 | e3 | 35 | 0.7 |
| Embodiment 7 | The fluorine zirconic acid | 0.95 | Three ammonium metaphosphates | 0.05 | c1 | 16 | d1 | 37.6 | e3 | 45 | 0.4 |
| Embodiment 8 | The fluorine zirconic acid | 1.22 | Hexamethylphosphoric acid triamide | 0.08 | c1 | 20 | d1 | 36.3 | e3 | 42 | 0.4 |
| Embodiment 9 | Fluosilicic acid | 0.92 | Ammonium phosphate | 0.08 | c1 | 16 | d1 | 37.6 | e1 | 45 | 0.4 |
| Comparative example 1 | - | - | Ammonium phosphate | 0.5 | c1 | 20 | d1 | 48 | e1 | 31 | 0.5 |
| Comparative example 2 | The fluorine zirconic acid | 0.5 | - | - | c1 | 20 | d1 | 45 | e1 | 34 | 0.5 |
| Comparative example 3 | Fluotitanic acid | 0.95 | Phosphoric acid | 0.05 | - | - | d1 | 49 | e2 | 49 | 1 |
| Comparative example 4 | The fluorine zirconic acid | 0.95 | Phosphoric acid | 0.05 | c1 | 20 | d1 | 45 | e2 | 34 | - |
| Comparative example 5 | The fluorine zirconic acid | 1 | Ammonium phosphate | 1 | c1 | 20 | d1 | 40 | e4 | 37 | 1 |
| Comparative example 6 | Contain chromium resin medicament 4) | ||||||||||
Annotate 1) the c1:3-aminopropyl trimethoxysilane
The c2:3-aminopropyl triethoxysilane
Annotate 2) the d1:3-glycidoxypropyltrime,hoxysilane
D2:3-glycidoxy propyl group methyl dimethoxysilane
Annotate 3) el: cation type polyurethane resin: condensation polymer, the N of polyether polyols and HDI (hexamethylene diisocyanate), TMSDMA N dimethylamine base dihydroxymethyl propylene additives
E2: cation type polyurethane resin: condensation polymer, the N of polyether polyols and MDI (methyl diphenylene diisocyanate), N-dimethylethanolamine additives
E3: nonionic polyurethane resin: the condensation polymer of polyether polyols and MDI (methyl diphenylene diisocyanate)
E4: anionic polyurethane resin: the condensation polymer notes 4 of polyether polyols and MDI (methyl diphenylene diisocyanate)) contain chromium resin medicament: TOP-5241 (Nihon Parkerizing Co., Ltd.'s production)
4, the coating of galvanized steel plain sheet is handled
At the clean above-mentioned surface conditioning agent of galvanized steel sheet surface coating one deck of cleaning by degreasing, the diaphragm amount of coating and steel plate heating-up temperature (PMT) see Table 2.
The coating of table 2 galvanized steel plain sheet is handled
| The steel plate kind | Diaphragm amount (g/m 2) | PMT(℃) | |
| Embodiment 1 | EG | 0.9 | 120 |
| Embodiment 2 | GI | 0.8 | 80 |
| Embodiment 3 | EG | 0.4 | 120 |
| Embodiment 4 | GI | 0.3 | 60 |
| Embodiment 5 | EG | 0.8 | 140 |
| Embodiment 6 | GI | 2.0 | 100 |
| Embodiment 7 | GI | 0.8 | 80 |
| Embodiment 8 | GF | 0.6 | 80 |
| Embodiment 9 | EG | 0.8 | 140 |
| Comparative example 1 | EG | 0.9 | 80 |
| Comparative example 2 | EG | 2.4 | 180 |
| Comparative example 3 | GI | 0.6 | 80 |
| Comparative example 4 | GI | 0.6 | 80 |
| Comparative example 5 | EG | 0.8 | 120 |
| Comparative example 6 | GI | 0.7 | 80 |
5, performance test
Galvanized steel plain sheet through above-mentioned coating is handled carries out Performance Detection by following test method.
5.1 alkali resistance
5.1.1 alkali resistance 1.
1% NaOH about 10 μ L are altogether dripped on surface-treated galvanized steel plain sheet model surface, place 30 seconds, and the variation of appearance is confirmed in water flushing back range estimation.
◎: the drippage position does not have any vestige
Zero: slight trace is only arranged
△: slight trace is arranged
*: the dissolving of sharp trace or diaphragm is arranged
5.1.2 alkali resistance 2.
The 2% concentration inorganic agent that uses alkaline defatting agent FC-4370H (Nihon Parkerizing Co., Ltd.'s productions) is to surface-treated 10 seconds of galvanized steel plain sheet model surface spraying, then with the nail surface of steel plate of swiping, by the variation of range estimation affirmation appearance.Validation criteria is as follows:
◎: the wiping position does not have any vestige
Zero: only there is slight trace at the wiping position
△: there is slight trace at the wiping position
*: there are sharp trace or diaphragm dissolving in the wiping position
5.2 solvent resistance
Solvent is selected: ethanol, butanone, dimethylbenzene.After soaking into gauze, in the firmly wiping 50 times back and forth of surface-treated galvanized steel sheet surface, the variation of appearance is confirmed in range estimation.Validation criteria is as follows:
◎: the wiping position does not have any vestige
Zero: only there is slight trace at the wiping position
△: there is slight trace at the wiping position
*: there are sharp trace or diaphragm dissolving in the wiping position
5.3 corrosion resistance
SST tests (JIS Z 2371), and white rust generation area is measured in range estimation.The white rust area reaches termination in 5% o'clock, confirms the SST time.
5.4 painting adhesion
After the galvanized steel plain sheet of coated processing carried out application according to following condition, carry out the painting adhesion test.
＜application condition〉alkyd be coating (big Japanese coating, trade name: delicon#700), the coating of coating rod, baking condition: 140 ℃ * 20 minutes.Coating thickness: 25 μ m.
5.4.1 tack
1, draw 100 little lattice with cutter in film coated surface, size is that 1mm is square, and the degree of depth should reach the surface of substrate steel sheet.Cellotape paper is peeled off, and confirms the residual lattice number of filming.
2, draw 100 little lattice with cutter in film coated surface, size is that 1mm is square, and the degree of depth should reach the surface of substrate steel sheet.Draw lattice position cupping 5mm, protrude the position and peel off, confirm the residual lattice number of filming with cellotape paper.
5.4.2 secondary tack
Application was pulled in the pure water that impregnated in boiling after 2 hours, used and the same method of tack is confirmed.
5.5 anti-finger printing
Finger is pressed and is pressed on the model surface, and the boldness of fingerprint is confirmed in range estimation.Evaluation method is as follows:
◎: do not have the fingerprint vestige fully.
Zero: extremely slight fingerprint trace.
△: slight fingerprint trace.
*: obvious fingerprint trace is arranged.
5.6 anti-blackening
The confirming performance of model: superimposed face-to-face, as 1 pair, superpose 5～10 pairs with this altogether, after tying up with the vinyl wrapping paper, four angles are screwed with screw, use torque wrench to be forced into 0.67kgf.cm then.Putting into temperature and be 70 ℃, relative humidity is that 80% climatic chamber took out after 240 hours, and the black change situation of overlapping part is judged in range estimation.
Criterion is as follows:
◎: do not have black the change
Zero: only slight burnt hair
△: obvious burnt hair
*: obviously turn black
The result of above-mentioned every Performance Detection is as shown in table 3:
Table 3 performance test results
| Number | Alkali resistance 1. | Alkali resistance 2. | Solvent resistance | Corrosion resistance | Painting adhesion 1) | Anti-finger printing | Anti-blackening | |||
| A tack | The secondary tack | |||||||||
| Draw lattice | Draw the lattice cupping | Draw lattice | Draw the lattice cupping | |||||||
| Embodiment 1 | ◎ | ◎ | ◎ | 120hr | 100 | 98 | 100 | 99 | ◎ | ◎ |
| Embodiment 2 | ○ | ○ | ○ | 144hr | 100 | 98 | 100 | 98 | ◎ | ◎ |
| Embodiment 3 | ◎ | ○ | ◎ | 96hr | 100 | 98 | 100 | 100 | ○ | ◎ |
| Embodiment 4 | ○ | ○ | ○ | 120hr | 100 | 100 | 100 | 100 | ○ | ◎ |
| Embodiment 5 | ◎ | ◎ | ◎ | 144hr | 100 | 100 | 100 | 100 | ◎ | ◎ |
| Embodiment 6 | ○ | ○ | ◎ | 192hr | 100 | 100 | 100 | 100 | ◎ | ◎ |
| Embodiment 7 | ○ | ○ | ○ | 144hr | 98 | 96 | 96 | 98 | ◎ | ◎ |
| Embodiment 8 | ○ | ○ | ○ | 120hr | 100 | 100 | 100 | 100 | ○ | ○ |
| Embodiment 9 | ◎ | ○ | ◎ | 144hr | 100 | 100 | 100 | 100 | ◎ | ◎ |
| Comparative example 1 | ○ | ○ | ○ | 48hr | 98 | 70 | 100 | 60 | ◎ | ◎ |
| Comparative example 2 | ◎ | ○ | ◎ | 24hr | 98 | 98 | 96 | 96 | ◎ | ○ |
| Comparative example 3 | × | × | × | 24hr | 98 | 94 | 96 | 94 | ○ | △ |
| Comparative example 4 | ○ | △ | △ | 48hr | 98 | 95 | 98 | 96 | ◎ | ◎ |
| Comparative example 5 2) | × | × | × | 12hr | 10 | 5 | 10 | 5 | × | ○ |
| Comparative example 6 | ○ | △ | △ | 240hr | 100 | 100 | 100 | 100 | ◎ | △ |
Notes 1) residual lattice number after the cross cut test
Annotate 2) comparative example 5 is in the affirmation process, because inorganic agent generation gel phenomenon causes film forming bad.
The performance test results of table 3 does not contain fluoracid (a) or phosphorus-containing compound (b), corrosion-resistant obviously as can be seen in comparative example 1 and the comparative example 2; Do not contain organosilan coupling agent (c) in the comparative example 3, alkali resistance, solvent resistance, corrosion resistance and anti-blackening are all poor; Do not contain vanadium-containing compound (f) in the comparative example 4, corrosion resistance and solvent resistance are relatively poor; In addition, using the anion outside the scope of the invention is the comparative example 5 of resin, and its inorganic agent poor stability has gelatin phenomenon to produce, and film forming is poor.Compare with these examples, embodiment 1～9 after handling with the chromium-free fingerprint-resistant inorganic agent that contains component of the present invention has demonstrated good alkali resistance, solvent resistance, corrosion resistance, painting adhesion, anti-finger printing and anti-blackening, compares and has identical even better alkali resistance and solvent resistance with the employed chromium resin medicament that contains in the comparative example 6.
Claims (9)
1, have the surface conditioning agent that is used for galvanized steel plain sheet of excellent alkali resistance and solvent resistance, its aqueous solution contains following component:
A) fluoracid contains the fluorine atom more than 4 at least in the fluoracid, contain selected at least more than one element from the groups of elements that titanium, zirconium and silicon are formed in addition, and the percentage by weight of the shared total solid content of fluoracid is 0.1～5.0%;
B) phosphorus-containing compound, shared percentage by weight is calculated as 0.01～0.5% of total solid content with phosphorus;
C) one or more contain the organosilan coupling agent of the amido functional group of at least one reactive hydrogen, and shared percentage by weight is 10～20% of total solid content;
D) one or more contain the organosilan coupling agent of at least one epoxy functionality, and shared percentage by weight is 25～50% of total solid content;
E) water soluble polyurethane resin of at least a cationic or nonionic, shared percentage by weight is 30～60% of total solid content;
F) vfanadium compound, shared percentage by weight are 0.1～1.0% of total solid content.
2, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 1 is characterized in that: described phosphorus-containing compound is orthophosphoric acid form or polyphosphoric acid form.
3, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 2, it is characterized in that: described orthophosphoric acid form is H
3PO
4Or ammonium phosphate.
4, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 2 is characterized in that: described polyphosphoric acid form is pyrophosphoric acid, triphosphoric acid, three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid or its ammonium salt.
5, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 1 is characterized in that: the described organosilan coupling agent that contains the amido functional group of at least one reactive hydrogen is selected from N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl) 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane.
6, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 1 is characterized in that: the described organosilan coupling agent that contains at least one epoxy functionality is selected from 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane.
7, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 1, it is characterized in that: described polyurethane resin is to be formed by polymerization between the polyalcohols that is selected from polyester polyalcohols, polyether polyols, Merlon polyalcohols and aliphatic isocyanates and/or the aromatic isocyanate compound, the part of polyalcohols is to contain N, the polyalcohols that TMSDMA N dimethylamine base dihydroxy methylpropane etc. are amino or the polyalcohols of polyethylene oxide chain.
8, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 1, it is characterized in that: described vfanadium compound is selected from sulfate, fluoride, oxide or the metal that contains vanadium.
9, the surface conditioning agent that is used for galvanized steel plain sheet with excellent alkali resistance and solvent resistance according to claim 1 is characterized in that: described surface conditioning agent pH value of water solution 2.0～6.5.
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