CN1530462A - Metal surface processing agent and steel plates with aluminum plated sub-lead alloys processed thereby - Google Patents
Metal surface processing agent and steel plates with aluminum plated sub-lead alloys processed thereby Download PDFInfo
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- CN1530462A CN1530462A CNA031195342A CN03119534A CN1530462A CN 1530462 A CN1530462 A CN 1530462A CN A031195342 A CNA031195342 A CN A031195342A CN 03119534 A CN03119534 A CN 03119534A CN 1530462 A CN1530462 A CN 1530462A
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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)
- Chemical Treatment Of Metals (AREA)
Abstract
A surface treating agent for metallic material contains the water resin (urane resin or acrylic resin) with carboxy and acid-amine, the compound of metals chosen from Al, Mg, Ca, Zn, Ni, Co, Fe, Zr, Ti, V, W, Mn and Ce, and the surface treating agent (silicic acid, silicate, colloidal SiO2, or organic silane) containing silicon compound, but not Cr. A steel plate which is treated by said surface treating agent and plated by aluminium-plumbo alloy is also disclosed.
Description
Technical field
The sub-lead series alloy steel plate of aluminizing that the present invention relates to no applications such as making building materials or household electrical appliances has alkali resistance, calendering constancy, solidity to corrosion and does not contain the metal conditioner of chromium, and utilizes this treatment agent to do the surface-treated sub-lead series alloy steel plate of aluminizing.
Background technology
The inferior lead alloy of aluminizing is a steel plate, 55% the inferior lead alloy steel plate of aluminizing particularly since its solidity to corrosion is good the eaves building materials through being usually used in buildings or outer wall building materials, agricultural with the building material mades such as pillar of moist closet; Building goods such as Auxiliary Track (guard rail), soundproof wall, waterways; Therefore no application purposes such as family's electrical article, industry machine, must make the surperficial nondiscoloration of electroplating steel plate, keep beautiful appearance for a long time; In addition, when using as building materials, because electroplating steel plate is to utilize the machine-shaping of running roller institute, therefore plating must have the performance that is not piled up in running roller, that is the calendering constancy; And it is also extremely important through the outward appearance after the calendering typing, it is good to reach no epithelium damage and solidity to corrosion, moreover, as the building materials purposes time, be exposed under the alkali corrosion environment owing to contacting sometimes, then must make its electroplating steel plate surface nondiscoloration this moment and keep its outward appearance for a long time with concrete.
In response to the prior art that aforementioned requirement and expectation worked out, propose to adopt the resin-coated technology that contains chromium mostly, its object lesson then is No. 2097278 inventions of patent, the invention of No. 2097278, this patent is to be purpose to improve calendering constancy and solidity to corrosion, cooperate 6 valency chromium of specified proportion with specific water-soluble or water-dispersed resin, and pH is adjusted into the treatment process that 3～10 treatment solution is coated the sub-lead series alloy steel plate surface of aluminizing; Adopt the sub-lead series alloy steel plate of aluminizing of this processing, its solidity to corrosion though it is good particularly to add Ministry of worker's solidity to corrosion, by the chromium of epithelium stripping, particularly adds man-hour by grade a large amount of chromium of institute's stripping of epithelium pars affecta, not goodly on environmental health probably problem can take place; Therefore as can be known, prior art can't obtain satisfying good alkali resistance, calendering constancy and solidity to corrosion, and has the sub-lead series alloy steel plate of aluminizing of the surface-treated layer that does not contain chromium.
Summary of the invention
The problem points of the present invention for being hidden in the above-mentioned prior art of solution, purpose is to provide a kind of good alkali resistance, calendering constancy, solidity to corrosion of can giving on the metal to be treated material, and the metallic substance that does not contain chromium surface treatment medicament, and a kind of all good, and the surface treatment that does not the contain chromium sub-lead series alloy steel plate of aluminizing with this surface treatment agent lining back alkali resistance, calendering constancy, solidity to corrosion.The result that the problem that this case inventor deposits at aforesaid prior art deepens continuously and examines, find by forming lining as main component with specific resin, finish the present invention so can solve foregoing problems, that is, the present invention be serve as reasons the formed metal finishing medicament that does not contain chromium of following formation, and through not containing the sub-lead series alloy steel plate of aluminizing that chromium surface is handled.That is the present invention is the metallic substance surface treatment agent that does not contain chromium, it is characterized in that containing following (A) composition, (B) composition and (C) composition:
(A) have carboxyl and acid amide bonded aqueous resin;
(B) select metallic compound more than a kind or 2 kinds in the metallic compound by aluminium Al, magnesium Mg, calcium Ca, zinc Zn, nickel, cobalt Co, iron Fe, zirconium Zr, titanium Ti, vanadium V, tungsten W, manganese Mn and cerium Ce;
(C) silicon compound;
(A) composition herein is urethane resin or acrylic resin; (B) composition is a zirconium Zr compound; (C) composition is then being good by selecting the metallic substance surface treatment agent that does not contain chromium in silicic acid, silicate, colloidal silicon-dioxide, the organosilane couplant; In addition, (C) composition is preferable with the organosilane couplant again.Above-mentioned metallic substance surface treatment agent, with the solid shape that has carboxyl and acid amide bonded aqueous resin in (A) composition divide with (B) composition in the zirconium compounds zirconium mass ratio (resin/zirconium) with in 1～300 scope for good; In addition, the weight ratio (resin/silicon) that (A) has the silicon in the organosilane couplant in the solid shape branch quality of carboxyl and acid amide bonded aqueous resin and (C) composition in the composition with in 10～800 scopes for good.
Moreover, the present invention will contain the metallic compound selected in the metallic compound by aluminium Al, magnesium Mg, calcium Ca, zinc Zn, nickel, cobalt Co, iron Fe, zirconium Zr, titanium Ti, vanadium V, tungsten W, manganese Mn and cerium Ce with carboxyl and acid amide bonded aqueous resin, (B) composition of (A) composition more than a kind or 2 kinds, and (C) coating of the silicon compound of composition, and its single face epithelium adhesion amount is at least 0.2～5.0g/m
2, and alkali resistance, calendering constancy, solidity to corrosion are all good, do not contain the sub-lead series alloy steel plate of aluminizing after the surface treatment of chromium again.(A) composition herein is urethane resin or acrylic resin; (B) composition is a zirconium Zr compound; (C) composition is then so that the person is good more than a kind or 2 kinds by selecting in silicic acid, silicate, colloidal silicon-dioxide, the organosilane couplant; In addition, (C) silicon compound of composition is preferable with the organosilane couplant.
Above-mentioned in not containing the sub-lead series alloy steel plate of aluminizing that chromium surface handles, with the solid shape that has carboxyl and acid amide bonded aqueous resin in (A) composition divide with (B) composition in the zirconium compounds with the mass ratio (resin/zirconium) of zirconium with in 1～300 scope for good; In addition, the solid shape that (A) has carboxyl and acid amide bonded aqueous resin in the composition divide with (C) composition in the organosilane couplant silicon mass ratio (resin/silicon) with in 50～800 scopes for good.
As described above, metallic substance of the present invention can be by using at metallic substance with surface treatment agent, particularly contain in the surface treatment of aluminium sub-lead series alloy plating steel plate, can give good solidity to corrosion and alkali resistance, because its calendering constancy is good, the utility value on industry is very big, in addition again, because it does not contain chromium, therefore the advantage that does not produce the environmental health problem is arranged.
Embodiment
Below do one with regard to formation of the present invention and describe in detail.
As the electroplating steel plate that contains the substrate of aluminium plating sub-lead series alloy steel plate among the present invention, its content of electroplating aluminium in the epithelium is 5～75% the sub-lead series alloy steel plate of aluminizing, for example representative with the 55% sub-lead series alloy steel plate of aluminizing, in general, the silicon Si in the plating epithelium of this sub-lead series alloy steel plate of aluminizing mostly is more than 0.5% of aluminium Al content; In addition, with the 55% sub-lead series alloy steel plate of aluminizing, the aluminize sub-lead series alloy steel plate (in the following description represent 55% aluminize sub-lead series alloy steel plate) of general expression aluminium content about 50～60%, it electroplates the silicon Si that contains usually in the epithelium about 1～3%, as described below, though characteristic of the present invention improve effect can be in electroplating epithelium aluminium content be that 5～75% the sub-lead series alloy steel plate of aluminizing fully obtains, wherein then improve effect to obtain significant especially characteristic in above-mentioned 55% the sub-lead series alloy steel plate of aluminizing.Be specially adapted among the present invention the to aluminize metallic substance surface treatment agent of sub-lead series alloy steel plate is used the metallic compound of (B) composition and (C) the silicon compound gained of composition in the resin of (A) composition; For example, in container, add entry,, utilize screw mixer etc. to mix, can be modulated into the metallic substance surface treatment agent again according to the metallic compound of the resin of (A) composition, (B) composition, and (C) the order input of the silicon compound of composition.
Aqueous resin in (A) used herein composition is to have carboxyl and acid amide bonded resin as main component, this resin can form epithelium on metal material surface, and the carboxyl in the resin is except bringing into play the stability of latex as the hydrophilic composition of resin, still can be by the existence raising of carboxyl and the adherence between metallic substance, moreover metallic compound that cooperates and silicon compound generation crosslinking reaction, can obtain solidity to corrosion, tunicle that alkali resistance is good; Carboxylic acid content in the aqueous resin used herein is good with 0.15～3.5mg equivalent/g, in addition, acid amide combination-CONH-in the resin with respect to alkali get tautomerism structure-C (OH) N-and produce the acid effect, in addition since acid amide in conjunction with acid-respons after can generate destabilization salt, in alkali, can bring into play the effect of neutralization bases, therefore containing acid amide bonded resin all has patience for acid and alkali, and has good alkali resistance and solidity to corrosion; Acid amide content in the aqueous resin used herein is good with 0.05～3.5mg equivalent/g.This has carboxyl and acid amide bonded resin the carboxyl of importing and acid amide bonded acrylic resin, vibrin, urethane resin etc. is arranged, these resins use under water systems such as water soluble state or water based emulsion state, that is aqueous resin, and, if consider anti-water decomposition, the wearability of adding of epithelium itself, be good then, wherein with urethane resin, though the synthetic method of relevant this resin is not particularly limited, can use the method for industrial normal use to synthesize.
The metallic compound that cooperates (B) composition of aforementioned (A) composition aqueous resin is to select in the metallic compound by aluminium Al, magnesium Mg, calcium Ca, zinc Zn, nickel, cobalt Co, iron Fe, zirconium Zr, titanium Ti, vanadium V, tungsten W, manganese Mn and cerium Ce more than a kind or 2 kinds to good; Can use phosphoric acid salt, acetate, nitrate, vitriol, carbonate, ammonium carbonate salts, muriate, fluorochemical, Neutral ammonium fluoride thing, coordination fluorochemical etc. as this metallic compound.Particularly when using the metallic compound of zirconium compounds conduct (B) composition, solid shape with carboxyl and acid amide bonded (A) composition aqueous resin divide with zirconium compounds in zirconium mass ratio (resin/zirconium Zr) with in 1～300 the scope for good, being preferably 1～200, is good with 10～150 scope more; If have that the solid shape of carboxyl and acid amide bonded (A) composition aqueous resin is divided and zirconium compounds in the mass ratio (resin/zirconium Zr) of zirconium less than 1 o'clock, zirconium compounds can cause corrosion protection result to reach capacity and be uneconomical, on the other hand, if have that the solid shape of carboxyl and acid amide bonded (A) composition aqueous resin is divided and zirconium compounds in the mass ratio (resin/zirconium Zr) of zirconium above 300 o'clock, then lacking the corrosion protection result that is caused by zirconium compounds is for not good, and this situation is also same when using other metallic compound.
Cooperate the silicon compound of (C) composition of aforementioned (A) composition aqueous resin to be not particularly limited, but it is good should using by the silicon compound of selecting in silicic acid, silicate, silica colloidal, the organosilane couplant more than a kind or 2 kinds, particularly should use organosilane couplants such as ethene Trimethoxy silane, γ-Bing Jisanjiayangjiguiwan.Particularly when using the silicon compound of organosilane couplant conduct (C) composition, solid shape with carboxyl and acid amide bonded aqueous resin (A) divide with the organosilane couplant in silicon Si mass ratio (resin/silicon Si) with in 10～800 the scope for good, be preferably 50～600, be more preferred from 100～400 scope; Mass ratio (resin/silicon Si) as if silicon Si in solid shape branch with carboxyl and acid amide bonded aqueous resin (A) and the organosilane couplant is discontented with at 10 o'clock, the corrosion protection result that is caused by the organosilane couplant reaches capacity and is uneconomical, on the other hand, if have that the solid shape of carboxyl and acid amide bonded resin is divided and the organosilane couplant in the mass ratio (resin/silicon Si) of silicon Si above 800 o'clock, then lacking the corrosion protection result that is caused by the organosilane couplant is for relatively poor, and this situation is also same when using other silicon compound.And, also can add molybdenumdisulphide, graphite, fluorine resin, polyene among the present invention in surface-treating agent for metallic material is that wax etc. is as lubricant, in addition, can give the epithelium color by adding tinting pigment, moreover, in the scope that does not undermine original performance, also can add defoamer and equal in this treatment solution.
Use the surface treatment method person of surface-treating agent for metallic material of the present invention as the sub-lead series alloy steel plate of aluminizing, be not particularly limited, for example just having begun arbitrary method such as available roller coat is coated with, re-use electric stove, hotblast stove, induce process furnace etc., arriving 60～200 ℃ of plate temperatures, make it dry form resin involucra be good with interior 60 seconds time of drying.
The metallic substance of the present invention that forms in the sub-lead series alloy steel plate surface of aluminizing is not particularly limited with dried resin involucra amount with the epithelium amount of surface treatment agent, but with 0.5～5g/m
2Scope in be good; Aluminium content is aluminium-Zn based alloy electroplating steel plate of 5～75% in the plating epithelium, and it electroplates epithelium itself more crisp shortcoming really up to the mark, can peel off to prevent to electroplate by covering one deck resin for improving this point, if the resin involucra amount is less than 0.5g/m
2The time, this plating peel off prevent effect cross low thereby bad, on the other hand, if surpass 5g/m
2In time, then electroplates to peel off and prevents that effect from reaching capacity is for uneconomical.
Below utilize embodiment and comparative example to do one the present invention to specify.
(making of brassboard)
(1) for the examination material
5% aluminium sub-lead series alloy plating steel plate (GE)
55% aluminium sub-lead series alloy plating steel plate (GL)
(2) skimming treatment
With silicate is after the Finecleaner4336 (Japanese Ba Kalai closely estimate (share) system) of alkaline defatting agent carries out skimming treatment (concentration 20g/L, spraying in 60 ℃, 20 seconds), to utilize tap water to clean.
(3) resin is synthetic
(3-1) have a fling at urethane resin
The diatomic alcohol compounds 100 minutes, 2 that two ends is had the vibrin 100 minutes of several molecular-weight average 1000 of carboxyl, several molecular-weight average 1000 that two ends have the hydrogen base, 2-dimethylol propionic acid 15 minutes, dicyclohexyl methane diisocyanate 100 minutes, N-methyl-2-mouth compared mouthful each alkane ketone 100 minutes, one prepolymer that reacts the back gained is scattered in the deionized water, and obtaining the carboxylic acid equivalent is that 0.75mg equivalent/g, acid amide equivalent are the urethane resin that studies of 0.5mg equivalent/g.
(3-2) have a fling at acrylic resin
With vinylformic acid 10 minutes and isophorone diisocyanate 5 minutes in organic solvent after the reaction, added vinylbenzene 25 minutes, methacrylic acid methyl 10 minutes, methacrylic acid butyl 20 minutes and vinylformic acid 2-ethylhexyl 30 minutes, drip to make its polymerization in the aqueous solution that contains interfacial agent, obtaining the carboxylic acid equivalent is that 1.0mg equivalent/g, acid amide equivalent are the acrylic resin that studies of 0.3mg equivalent/g.
(4) inflation method of surface treatment agent
At room temperature, in distilled water, drop into the silicon compound shown in resin as shown in table 1, the metallic compound shown in the table 2, the table 3 in order, utilize screw mixer to mix, be modulated into the surface treatment agent of table 4.
Table 1
| No. | The resin detail | The acid amide combination | Carboxyl |
| A1 A2 A3 | Have a fling at urethane resin and have a fling at the acrylic resin styrene acrylic resin | Having does not have | Have |
Table 2
| No. | Metallic compound |
| B1 B2 B3 B4 B5 | Zirconium carbonate ammonium zirconium Neutral ammonium fluoride titanium second vinegar acetone dentate ammonium vanadate cobaltous carbonate |
Table 3
| No. | Silicon compound |
| C1 C2 C3 C4 | Ethene Trimethoxy silane γ-Bing Jisanjiayangjiguiwan colloid silica potassium silicate |
Table 4
| ????No. | The cooperation ratio (weight fraction) of treatment agent | Resin/metal | Resin/silicon | ||
| Resin | Metallic compound | Silicon compound | |||
| ????D1 ????D2 ????D3 ????D4 ????D5 ????D6 ????D7 ????D8 ????D9 ????D10 ????D11 ????D12 ????D13 ????D14 ????D15 | ????A1 ????A1 ????A1 ????A1 ????A1 ????A1 ????A1 ????A2 ????A2 ????A1 ????A1 ????A1 ????A1 ????A3 ????A3 | B1 B2 B3 B4 B5 B1 B1 B1 B2 B2 B2 B1 does not have B1 B2 | C1 C1 C2 C2 C2 C3 C4 C1 C2 C1 C1 does not have C2 C1 C2 | ????50 ????100 ????150 ????200 ????100 ????150 ????150 ????100 ????50 ????400 ????50 ????100 ????- ????50 ????150 | ????500 ????300 ????200 ????700 ????100 ????300 ????200 ????300 ????400 ????500 ????1000 ????- ????200 ????500 ????300 |
(5) making method of surface treated steel plate
Above-mentioned adjusted surface treatment agent is coated for examination material surface with roller coating machine, dry under 240 ℃ envrionment temperature, wherein, epithelium amount (g/m
2) adjustment be to see through appropriateness to adjust the solid shape branch concentration of surface treatment agent and carry out.
Epithelium performance evaluation:
(1) planar portions solidity to corrosion
Utilize JIS-Z-2371 to implement brine spray experiment 240 hours, observe its white rust situation occurred, below the note benchmark is estimated.
＜metewand 〉
◎: do not produce white rust
Zero: white rust produces 10% of the discontented gross area of area occupation ratio
△: what white rust produced that area occupation ratio accounts for gross area is discontented with 30% 10% or more
*: white rust produces area occupation ratio and accounts for more than 30% of gross area
(2) alkali resistance
Brassboard be impregnated in 1% aqueous sodium hydroxide solution 5 hours, observe the epithelium state before and after the dipping, below the note benchmark is estimated.
＜metewand 〉
◎: outward appearance does not change
Zero: 10% of the discontented gross area of variable color area
△: the variable color area accounts for more than 10% discontented 30% of gross area
*: the variable color area accounts for more than 30% of gross area
Table 5
| No. | Treatment agent | Thickness (g/m2) | Material | The planar portions solidity to corrosion | Alkali resistance |
| 1 2 3 4 5 6 7 8 9 10 11 12 | D1 D2 D3 D4 D5 D6 D7 D8 D9 D1 D2 D3 | 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 0.5 2.0 2.0 | GL GL GL GL GL GL GL GL GL GL GF GF | ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ ○ ◎ ◎ | ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ ○ ◎ ◎ |
Table 6
| Comparative example No. | Treatment agent | Thickness (g/m2) | Material | The planar portions solidity to corrosion | Alkali resistance |
| 1 2 3 4 5 6 7 | D10 D11 D12 D13 D14 D15 D1 | 2.0 2.0 2.0 2.0 2.0 2.0 0.2 | GL GL GL GL GL GF GL | △ △ △ △ × × △ | × × × △ × × × |
With the experimental result of embodiment among the present invention and comparative example shown in table 5 and table 6.In the embodiment 1～12 that uses surface treated steel plate of the present invention, both are all good for solidity to corrosion, alkali resistance, on the other hand, use in the comparative example 1～7 of the present invention's surface treated steel plate in addition, and solidity to corrosion, alkali resistance are all inferior.
Claims (10)
1. metallic substance surface treatment agent is characterised in that and contains following (A) composition, (B) composition and (C) composition:
(A) have carboxyl and acid amide bonded aqueous resin;
(B) select metallic compound more than a kind or 2 kinds in the metallic compound by aluminium Al, magnesium Mg, calcium Ca, zinc Zn, nickel, cobalt Co, iron Fe, zirconium Zr, titanium Ti, vanadium V, tungsten W, manganese Mn and cerium Ce;
(C) silicon compound.
2. metallic substance surface treatment agent as claimed in claim 1 is characterized in that (A) composition is urethane resin or acrylic resin; (B) composition is a zirconium Zr compound; (C) composition is then with by selecting more than a kind or 2 kinds in silicic acid, silicate, colloidal silicon-dioxide, the organosilane couplant.
3. metallic substance surface treatment agent as claimed in claim 1 or 2 is characterized in that (C) composition is the organosilane couplant.
4. as each the described metallic substance surface treatment agent in the claim 1 to 3, the solid shape that it is characterized in that having in (A) composition carboxyl and acid amide bonded aqueous resin divide with (B) composition in the zirconium compounds with the mass ratio of zirconium in 1～300 scope.
5. as claim 3 or 4 described metallic substance surface treatment agents, it is characterized in that the weight ratio that (A) has the silicon in the organosilane couplant in the solid shape branch quality of carboxyl and acid amide bonded aqueous resin and (C) composition in the composition is in 10～800 scope.
6. surface treatment aluminium sub-lead series alloy plating steel plate that uses surface-treating agent for metallic material as claimed in claim 1 to handle, be characterised in that by (A) to have the coating of selecting the metallic compound more than a kind or 2 kinds and (C) containing silicon compound in carboxyl and acid amide bonded aqueous resin, (B) metallic compound, and single face epithelium adhesion amount is at least 0.2～5.0g/m by aluminium Al, magnesium Mg, calcium Ca, zinc Zn, nickel, cobalt Co, iron Fe, zirconium Zr, titanium Ti, vanadium V, tungsten W, manganese Mn and cerium Ce
2
7. surface treatment aluminium sub-lead series alloy plating steel plate as claimed in claim 6 is characterized in that (A) composition is urethane resin or acrylic resin; (B) composition is a zirconium Zr compound; (C) composition is then with by selecting more than a kind or 2 kinds in silicic acid, silicate, colloidal silicon-dioxide, the organosilane couplant.
8. as claim 6 or 7 described surface treatment aluminium sub-lead series alloy plating steel plates, the silicon compound that it is characterized in that (C) composition is the organosilane couplant.
9. as each described surface treatment aluminium sub-lead series alloy plating steel plate of claim 6 to 8, the solid shape that it is characterized in that having in (A) composition carboxyl and acid amide bonded aqueous resin divide with (B) composition in the zirconium compounds with the mass ratio of zirconium in 1～300 scope.
10. surface treatment aluminium sub-lead series alloy plating steel plate as claimed in claim 8 or 9, it is characterized in that the weight ratio that (A) has the silicon in the organosilane couplant in the solid shape branch quality of carboxyl and acid amide bonded aqueous resin and (C) composition in the composition is in 50～800 scope.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031195342A CN100494495C (en) | 2003-03-10 | 2003-03-10 | A treatment agent for the surface of metal materials, and an aluminum-zinc-based alloy-plated steel sheet treated with the treatment agent |
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|---|---|---|---|
| CNB031195342A CN100494495C (en) | 2003-03-10 | 2003-03-10 | A treatment agent for the surface of metal materials, and an aluminum-zinc-based alloy-plated steel sheet treated with the treatment agent |
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| CN1530462A true CN1530462A (en) | 2004-09-22 |
| CN100494495C CN100494495C (en) | 2009-06-03 |
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