CN101353548A - Organic composite film for galvanized steel sheet surface - Google Patents
Organic composite film for galvanized steel sheet surface Download PDFInfo
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- CN101353548A CN101353548A CNA2007100442098A CN200710044209A CN101353548A CN 101353548 A CN101353548 A CN 101353548A CN A2007100442098 A CNA2007100442098 A CN A2007100442098A CN 200710044209 A CN200710044209 A CN 200710044209A CN 101353548 A CN101353548 A CN 101353548A
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- steel sheet
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- organic composite
- titanium
- sheet surface
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Abstract
The invention discloses a galvanized steel sheet surface organic composite coating which is mainly characterized by comprising the following chemical elements by weight percentage: Ti: 0.1 to 1.0 percent, P: 0.05 to 0.5 percent, Si: 5 to 15 percent, polyurethane resin, with the glass transition temperature of 50 to 100 DEG C: 30 to 50 percent, and the rest is water. The thickness of the organic composite coating is 0.3 to 3Mum. The invention can be used for galvanized steel sheet surface and lead the galvanized steel sheet surface to have excellent corrosion resistance and paint adhesion on the coating when avoiding environmental pollution.
Description
Technical field
The invention belongs to field of metallurgy, particularly the organic composite film for galvanized steel sheet surface in the field of metallurgy.
Background technology
Metallic substance such as steel plate galvanized and aluminium sheet is at automobile, and fields such as building materials and household electric appliances are widely used.But,, therefore can cause the metallic substance visual appearance to descend, even can bring negative impact last paint coating tack owing to after zinc that these metallic substance adopted and aluminium is corroded, promptly generate the corrosion product that is called as white rust in atmosphere.In order to improve painting adhesion and solidity to corrosion, generally all can use and mainly contain chromic acid at metal material surface, the treatment solution of dichromic acid or other salts is handled.
Yet, the 6 valency chromium of handling in the employed chromate treating liquid because of metal material surface have direct harm to human body, and, must prevent that the regulation of method from handling especially according to the water quality dirt when containing the discharge of wastewater of 6 valency chromium, in addition, the metallic substance that chromate treating is crossed can't utilize after going out of use owing to contain chromium again, along with the raising of environmental consciousness in the last few years, these reasons all are that the use of chromate treating liquid has brought obstacle.
On the other hand, as the surface treatment method beyond the chromate treating, adopt and contain the surface treatment agent of (containing multivalence phenol carboxylic acid) Weibull to handle.Use the tannin aqueous acid that metallic substance is handled, the reaction formation protection epithelium by Weibull and metallic substance can stop the intrusion of corrosive deposit, has improved solidity to corrosion and painting adhesion.Yet in recent years, along with the high quality of product, skin required the high anti-corrosion of film self and went up the paint coating tack, therefore, use Weibull separately or and inorganic and with the epithelium of gained, its solidity to corrosion is also insufficient, also impossible at present practicability.So, as the treatment process that can improve these performances, the spy opens to have issued on the clear 53-121034 communique will contain water-dispersible silica and Synolac, and the aqueous solution of trialkoxy silane compound is coated on the metallic surface, and dry back forms the method for lining epithelium.
Use the formed water soluble resin of carboxyl dipyrryl ketone compound inductor in addition, to reach the surface treatment method of giving metallic substance solidity to corrosion purpose, and use the aqueous solution and the water dispersible doubling body of carboxyl styrene ene compound to give metallic substance corrosion proof method, issued that the spy opens clear 57-44751 communique and the spy opens flat 1-177380 communique etc.
Yet above-mentioned which kind of method all can't the substitute chromium hydrochlorate, forms the epithelium with high anti-corrosion and painting adhesion.We open the spy and propose to use the steel plate galvanized of handling with the treatment agent of the metal ion more than the divalent and acid, organosilane coupler and water-soluble coincidence thing composition on the flat 11-106945 communique as this way to solve the problem.Yet in the reality, the problems referred to above are still unresolved.Simultaneously, when steel plate is used for household appliances, carry out powder body coating or solvent application many times all can for the steel plate that has formed these epitheliums, if the tack of these powder body coatings or solvent application is very poor, may cause to film during use and peel off, and then cause value of the product to descend.Simultaneously, if the incomplete words of the solidity to corrosion of steel plate self can be corroded under filming, can cause to film equally and peel off.Under such situation, must carry out the replacing of product or repairing etc., make burden economically become big.Therefore, need badly implemented the surface-treated steel plate galvanized to have excellent solidity to corrosion and with powder body coating, solvent painting adhesion.
Summary of the invention
The purpose of this invention is to provide a kind of organic composite film for galvanized steel sheet surface, have excellent corrosion resistance by improving the chemical ingredients of this epithelium, producing, on be coated with painting adhesion, and even yellowing resistance, the organic composite film for galvanized steel sheet surface of solvent resistance.
The present invention realizes that the technical scheme of above-mentioned purpose is: a kind of organic composite film for galvanized steel sheet surface, the chemical element that comprises following weight percent proportioning: Ti:0.1～1.0%, P:0.05～0.5%, Si:5～15%, the glass tansition temperature is at 50～100 ℃ urethane resin: 30～50%, and all the other are water.
In technical solution of the present invention, the general employing of raw material contained titanium, phosphorus, the titanium compound of element silicon, phosphorus compound and silicon compound; And the glass tansition temperature is at 50～100 ℃ urethane resin.Titanium compound of the present invention has no particular limits, for example titanium fluoride and salt thereof; titanium boride, titanium sulfate, titanium nitride; titanium phosphates etc. also have the acidylate titanium, titanium oxyoxalate; metatitanic acid ethylene glycol; tetraisopropoxy titanium, 1,3-propane dihydroxy basic weight titanium (ethyl acetoacetic acid salt); two (acryl hydroxyl) isopropoxy isostearoyl hydroxyl titaniums (IV), isopropoxy three-n-octyl group hydroxyl titanium (IV) etc.Titanium compound can play the metal stiffening agent effect of urethane resin etc., can improve the solidity to corrosion of organic composite film etc.The scope that the combined amount of titanium wishes to occupy 0.1～1.0% in the machine epithelium is good.Below 0.1%, the effect of stiffening agent reduces, and the performance of organic composite film is had any problem on improving; If surpass 1.0%, effect reaction surplus then because epithelium is really up to the mark, might make processibility and on be coated with painting adhesion and descend.
Phosphorus compound is that ortho-phosphoric acid, Tripyrophosphoric acid also have a kind of of organic phospho acid compound at least.Tripyrophosphoric acid can use tetra-sodium, triphosphoric acid, three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid or its alkaline metal salt and ammonium salt.Also have the organic phospho acid compound can use the amino-cyclopropane phosphonic acids, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid, ethylene diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acids, or its alkaline metal salt.Perhaps also can use above-mentioned ortho-phosphoric acid, Tripyrophosphoric acid also has a kind of of organic phospho acid compound and any other kind combination.Phosphorus compound can play the rust-preventive agent effect to steel plate galvanized, can improve the solidity to corrosion of organic composite film.The scope that the combined amount of phosphorus wishes to occupy 0.05～0.5% in the machine composite film is good.Below 0.05%, then the effect as rust-preventive agent descends the solidity to corrosion imperfection of organic composite film.Surpass 0.5%, then Guo Sheng phosphorus compound will dissolve, and be coated with painting adhesion on might reducing.
Silicon compound can be selected potassium silicate for use, water glass, and the silicate and the silicon monoxide of lithium silicate etc., the oxide compound of silicon-dioxide etc.Can also use with these silicate and oxide compound product as the raw material gained.Silicomethane for example, silicoethane, silane compound and sily oxide such as Trisilicopropane, silicone compounds such as trisiloxanes.Silicon compound plays the effect of linking agent and tackiness agent to organic composite film, can improve the solidity to corrosion of organic composite film, on be coated with painting adhesion, performances such as anti-blackening.Si should be 5～15% in organic composite film.If be lower than 5%, then the effect of tackiness agent descends, each performance imperfection of organic composite film.If, surpass 15%, then the hardness of epithelium is too high, may cause processibility and on be coated with painting adhesion and descend.
As long as it is that the glass tansition temperature is in 50～100 ℃ the scope that urethane resin is selected for use.Urethane resin is by repeatedly containing urethane bonded compound in the bone, contain the polyisocyanate compound (O=C=N-R-N=C=O) of 2 above isocyanate group and contain 2 above water acidic groups many alkylol cpds (HO-R '-OH), polyamines (H
2N-R " NH
2), (NH of moisture etc. active water element
2,-NH ,-CONH-な ど) reaction such as compound gained (R, R ', R ": aliphatics, aromatic series etc.).The glass tansition temperature of this resin, according to the kind and the combined amount of many alcohol, and urethane changes in conjunction with concentration.Urethane resin of the present invention is wished the scope of 50～100 ℃ of glass tansition temperatures.If it is too soft to be lower than 50 ℃ then epithelium hardness, might reduce with on the tack of filming.If surpass 100 ℃, the organic composite film that then particularly adds the Ministry of worker produces fracture, may cause and on tack deterioration between the application.
In addition, when the oxygen in the atmosphere and water saw through organic composite film, urethane resin can be controlled transmitance effectively, postpones galvanized corrosion with this, improves solidity to corrosion effectively, anti-blackening.The weight percent of urethane resin in organic composite film joined account for 30～50%.Be lower than all imperfections of 30% solidity to corrosion, anti-blackening, if be higher than 50%, other compositions then of the present invention: titanium compound, phosphorus compound, therefore the content of silicon compound can reduce, and each performance may deterioration.
Preferably, described organic composite film for galvanized steel sheet surface, wherein: Ti:0.4～0.8%, P:0.1～0.3%, Si:8～12%, urethane resin: 35～45%.
Preferably, described organic composite film for galvanized steel sheet surface, its thickness are 0.3～3 μ m.
The thickness of epithelium should be good in the scope of 0.3～3 μ m.Be lower than 0.3 μ m, then galvanized steel sheet surface can not fully be covered, and can expose galvanizing surface, can't embody solidity to corrosion and painting adhesion; If surpass 3.0 μ m, then the epithelium opposing increases, when making household appliances, and can, surface resistivity high cause ground connection property deterioration poor owing to weldability.
On steel plate galvanized of the present invention, form and contain titanium compound, phosphorus compound, the method for the epithelium of silicon compound and urethane resin is not particularly limited, pickling process for example, spraying process and rolling method etc. can both be suitable for.Also have, about treatment temp, the treatment time, also there is no particular limitation.And wish the oven dry of the processing of the aqueous surface on galvanized steel sheet surface liquid layer is carried out under heating.Heating temperature is good at 60～200 ℃.According to circumstances need also can carry out water-cooled thereafter.
The kind of steel plate galvanized of the present invention, specification, shapes etc. are not particularly limited, hot-dip galvanizing sheet steel for example, hot-dip aluminizing zincium steel plate, electrogalvanizing steel plate, electro-galvanizing nickel steel plate can be selected for use.
The present invention compared with prior art has good yellowing resistance, solvent resistance, simultaneously, and its erosion resistance, last paint coating tack all improves a lot.
Embodiment
Embodiment
1. the experiment material that supplies
Steel plate galvanized
(A) city dealer product, thickness of slab 0.6mm hot-dip galvanizing sheet steel (GI) target adhesion amount 40g/m
2/ face
(B) city dealer product, thickness of slab 0.6mm hot-dip aluminizing zincium steel plate (G F) target adhesion amount 40g/m
2/ face
2. (the login trade mark: Off ア イ Application Network リ one Na 1 of alkali cleaner during adopt on the surface of the above-mentioned steel plate galvanized of purging method of metal sheet, Japan's rapids essence of handkerchief card (strain) system) aqueous solution (drug concentration: the 20g/ litre), treatment temp: 60 ℃, treatment time: spraying is handled under 20 seconds the condition, and the rubbish and the oil of surface attachment is removed.Secondly wash the remaining alkali branch in surface with tap water, the surface of confession experiment material is cleaned.
3. aqueous surface is handled and is formed liquid
It is as shown in table 1 that the used aqueous surface of present embodiment and comparative example is handled composition liquid.
Table 1
Annotate 1)
U1: nonionic urethane resin: 50 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and HDI (HDI)
U2: anionic property urethane resin: 60 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and MDI ('-diphenylmethane diisocyanate)
U3: nonionic urethane resin: 90 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and HDI
U4: cationic urethane resin: 70 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and MDI
U5: nonionic urethane resin: the polycondensate of 20 ℃ of glass tansition temperatures, polyester polyalcohols and MDI
Annotate 2) resin chromium processing: TOP-5241 (the rapids essence of Japanese handkerchief card (strain) product)
4. the treatment process of surface treatment steel plate galvanized
Shown the formed organic composite film amount of embodiment and comparative example in the table 2.
Table 2
5. evaluation experimental method
The performance of the surface treatment steel plate galvanized of the foregoing description and comparative example gained adopts following method to estimate.
5.1 solidity to corrosion
By salt mist experiment (JIS Z 2371), the anti-white rust of visual judgement arrives 5% time spent with the white rust area and estimates.
5.2 coating adhesion
Experiment is carried out the application of following condition with the surface treatment steel plate galvanized and is filmed and adhere to experiment.＜application condition〉alkyd is coating (big Japanese coating (strain) trade name デ リ コ Application #700) application: scraper method, baking condition: formed filming of 25 μ m in 140 ℃ * 20 minutes
5.2.1 tack
1. cross is drawn lattice experiments and is drawn on filming after 100 length and width are the grid of 1mm, peels off with scotch tape, estimates by the remaining number of filming.
2. cross is drawn the experiment of lattice Eriksson and draw the grid that 100 length and width are 1mm on being filmed, and behind Eriksson experiment instrument release 5mm, peels off with scotch tape at lug boss, by the remaining number evaluation of coating.
5.2.2 secondary tack
Coated plate floods after 2 hours in the ebullient pure water, carries out and an identical evaluation of tack.
5.3 anti-finger printing
On brassboard, press...with one's finger, the vestige state of fingerprint is passed through visual valuation.In addition, evaluation result is as follows:
◎: the vestige that does not stay fingerprint fully.
Zero: the vestige that only stays some fingerprints.
△: the vestige of slight residual fingerprint.
*: the vestige that obviously leaves fingerprint.
5.4 anti-blackening
Brassboard is cut into plural piece, downcut on same brassboard in twos relatively for a pair of, 5～10 pairs are overlapping, behind plastic wrapping paper bale packing, screw down on 4 angles, clamp with the loading of torque spanner with 0.67Kgf.cm.Then, at 70 ℃, put 240 hours in the moistening case of 80% relative humidity after, take out, the black change situation of coincidence part is carried out visual judgement.In addition, determinating reference is as follows:
◎: not black the change.
Zero: the extremely slight ash that becomes.
△: obviously ashing.
*: obvious melanism.
5.5 solvent resistance
Experiment is used with solvent, ethanol, and butanone, dimethylbenzene, after each absorbed with cotton balls, the visual observation surface changed and evaluation wiping 50 times is exerted oneself in experiment with the surface treatment galvanized steel sheet surface after.In addition, judgement criteria is as follows:
◎: the part of wiping does not have vestige fully.
Zero: the wiping part only has some vestiges.
△: wiping partly has slight vestige.
*: the obviously albefaction of wiping part, epithelium dissolving.
Above-mentioned experimental evaluation result is as shown in table 3.Notes 1) the residual number of lattice drawn in 100 expression crosses
Table 3
By the result of table 3 can be clear and definite find out: the solidity to corrosion of the comparative example 1,2 of titanium-containing compound and phosphorus compound is not poor outside scope of the present invention; The solidity to corrosion of the comparative example 3 of silicon-containing compound and solvent resistance are all not poor; Do not contain the comparative example 4 of urethane resin solidity to corrosion, on be coated with painting adhesion, anti-finger printing and poor solvent resistance; Use extraneous urethane resin of the present invention comparative example 5 on to be coated with painting adhesion poor.With these relatively, 1～9 of embodiments of the invention demonstrated good solidity to corrosion, on be coated with painting adhesion, anti-finger printing, anti-blackening and solvent resistance, handle with the resin chromium of comparative example 6 and have equal above performance.
Claims (9)
1. organic composite film for galvanized steel sheet surface, it is characterized in that comprising the chemical element of following weight percent proportioning: Ti:0.1～1.0%, P:0.05～0.5%, Si:5～15%, the glass tansition temperature is at 50～100 ℃ urethane resin: 30～50%, and all the other are water.
2. organic composite film for galvanized steel sheet surface as claimed in claim 1, its feature also is: Ti:0.4～0.8%, P:0.1～0.3%, Si:8～12%, glass tansition temperature are at 50～100 ℃ urethane resin: 35～45%.
3. organic composite film for galvanized steel sheet surface as claimed in claim 1 is characterized in that its thickness is 0.3～3 μ m.
4. organic composite film for galvanized steel sheet surface as claimed in claim 1; it is characterized in that the Ti element can by following compound one or more combination and obtain: titanium fluoride and salt thereof, titanium boride, titanium sulfate, titanium nitride, titanium phosphate, acidylate titanium, titanium oxyoxalate, metatitanic acid ethylene glycol, tetraisopropoxy titanium, 1,3-propane dihydroxy basic weight titanium, two isopropoxy isostearoyl hydroxyl titanium, isopropoxy three-n-octyl group hydroxyl titanium.
5. organic composite film for galvanized steel sheet surface as claimed in claim 1, it is characterized in that the P element can by following compound one or more combination and obtain: phosphoric acid, ammonium phosphate, tetra-sodium, trimerization hexa metaphosphoric acid or its alkaline metal salt and ammonium salt, three metaphosphoric acids, four metaphosphoric acids, amino-cyclopropane phosphonic acids, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid, ethylene diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acids or its alkaline metal salt.
6. organic composite film for galvanized steel sheet surface as claimed in claim 1, it is characterized in that the Si element can by following compound one or more combination and obtain: the oxide compound of silicate, silicon, with the oxide compound of silicate and silicon product as the raw material gained.
7. organic composite film for galvanized steel sheet surface as claimed in claim 6, the oxide compound that it is characterized in that described silicate and silicon as the product of raw material gained is: silane compound and silicone compounds.
8. organic composite film for galvanized steel sheet surface as claimed in claim 7, it is characterized in that described silane compound be silicomethane, silicoethane, Trisilicopropane; Described silicone compounds is sily oxide, trisiloxanes.
9. organic composite film for galvanized steel sheet surface as claimed in claim 1 is characterized in that urethane resin is following a kind of:
(1) nonionic urethane resin: 50 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and HDI two isocyanic acids;
(2) anionic property urethane resin: 60 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and MDI;
(3) nonionic urethane resin: 90 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and HDI;
(4) cationic urethane resin: 70 ℃ of glass tansition temperatures, the polycondensate of polyester polyalcohols and MDI.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100442098A CN101353548A (en) | 2007-07-26 | 2007-07-26 | Organic composite film for galvanized steel sheet surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100442098A CN101353548A (en) | 2007-07-26 | 2007-07-26 | Organic composite film for galvanized steel sheet surface |
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| CN101353548A true CN101353548A (en) | 2009-01-28 |
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| CNA2007100442098A Pending CN101353548A (en) | 2007-07-26 | 2007-07-26 | Organic composite film for galvanized steel sheet surface |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924235A (en) * | 2014-04-22 | 2014-07-16 | 刘建忠 | Passivation process of hot dip galvanized steel plate |
| CN108291312A (en) * | 2015-12-28 | 2018-07-17 | 新日铁住金株式会社 | Hot-dip galvanized steel sheet and its manufacturing method |
| CN111560607A (en) * | 2020-06-24 | 2020-08-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Surface treatment liquid for hot-dip galvanized aluminum magnesium steel plate and preparation method of hot-dip galvanized aluminum magnesium chromium-free passivated plate |
-
2007
- 2007-07-26 CN CNA2007100442098A patent/CN101353548A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924235A (en) * | 2014-04-22 | 2014-07-16 | 刘建忠 | Passivation process of hot dip galvanized steel plate |
| CN103924235B (en) * | 2014-04-22 | 2016-04-13 | 刘建忠 | The passivation technology of hot galvanized steel pipe |
| CN108291312A (en) * | 2015-12-28 | 2018-07-17 | 新日铁住金株式会社 | Hot-dip galvanized steel sheet and its manufacturing method |
| CN108291312B (en) * | 2015-12-28 | 2020-05-26 | 日本制铁株式会社 | Hot-dip galvanized steel sheet and method for producing same |
| CN111560607A (en) * | 2020-06-24 | 2020-08-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Surface treatment liquid for hot-dip galvanized aluminum magnesium steel plate and preparation method of hot-dip galvanized aluminum magnesium chromium-free passivated plate |
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Open date: 20090128 |