CN102648090A - Chromate-free precoated steel sheet having excellent end-surface rust corrosion resistance - Google Patents
Chromate-free precoated steel sheet having excellent end-surface rust corrosion resistance Download PDFInfo
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- CN102648090A CN102648090A CN2010800554905A CN201080055490A CN102648090A CN 102648090 A CN102648090 A CN 102648090A CN 2010800554905 A CN2010800554905 A CN 2010800554905A CN 201080055490 A CN201080055490 A CN 201080055490A CN 102648090 A CN102648090 A CN 102648090A
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- C—CHEMISTRY; METALLURGY
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
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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
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Abstract
Provided is a novel type of chromate-free precoated steel sheet having excellent end-surface rust corrosion resistance, which can be used without concern for the generation of appearance-harming rust, even in an outdoor environment where the chromate-free precoated steel sheet is exposed to rainwater and the like. The chromate-free precoated steel sheet having excellent end-surface rust corrosion resistance has a chromate-free chemical conversion treatment layer on both surfaces of a zinc-plated steel sheet and one or more coating films formed on the chromate-free chemical conversion treatment layers. At least the outermost coating film from among the coating films on the rear surface of the precoated steel sheet includes tungstate or silicate which has high end-surface retentivity.
Description
Technical field
The present invention relates to the excellent chromium-less pre-coated steel plate of anti-red rust corrosivity of end face.More particularly; The present invention relates to by the environment of water-wet, particularly be exposed to the chromium-less pre-coated steel plate that uses in the fields that use under the room external environment of rainwater etc., electric product, building etc., is the excellent chromium-less pre-coated steel plate of anti-red rust corrosivity of end face.
Background technology
Pre-coated steel plate (also being called as " PCM ") is to form the steel plate of filming and dispatching from the factory of the person of needs for this goods requirement in advance; Owing to can omit by the needs person and carry out application and relative operation; And also need not be used for such apparatus operating, therefore it utilizes constantly expansion in various fields.In the pre-coated steel plate in the early stage,, use the chromate of the antirust processing of having implemented the employing chromate to handle steel plate as the base steel sheet of implementing application.Thereafter; Because the chromic toxicity problem of handling the possibility of epithelium stripping from chromate is arranged; Replace chromate to handle pre-coated steel plate, use the chromium-less pre-coated steel plate of the base steel sheet of having implemented the antirust processing of Chrome-free to receive publicity, thereby it utilizes increase especially in recent years.In chromium-less pre-coated steel plate in the past, the rust resisting pigment that is contained in filming (usually, calcium exchange silica (also being called as calcium silicates sometimes as being commonly called as), aluminium triphosphate etc.) is born rust inhibition.
Along with the main flow of pre-coated steel plate is handled pre-coated steel plate from silicate and shifted to the chromium-less pre-coated steel plate, the pre-coated steel plate that uses down at the room external environment that is exposed to rainwater etc. appears at end face the problem attractive in appearance etc. that produces red rust, damages the goods that utilized pre-coated steel plate in one's mind quickly.This problem is handled in the pre-coated steel plate at chromate and is not taken place, and as distinctive problem in the chromium-less pre-coated steel plate, requires its solution.
About the corrosive raising of the anti-red rust of the end face of chromium-less pre-coated steel plate, more known prior aries.
For example; Known following chromium-less pre-coated steel plate: through on having the clad steel sheet that contains Zn coating, form outermost film contain satisfied: the pH when (A) being dissolved in ion exchange water with the concentration of 0.1 quality % is 7 ~ 12; Electrical conductivity when (B) being dissolved in ion exchange water with the concentration of 0.1 quality % is more than the 500 μ S/cm; And the non-chromium compounds (being sodium phosphate trimer as an example) that (C) the such condition of thermal decomposition do not take place before 200 ℃ are as rust resisting pigment, can not use the chromate rust resisting pigment and prevent the generation (patent documentation 1) of the end face red rust that the influence because of the low water of electrical conductivity causes.
In addition; Known following chromium-less pre-coated steel plate: through on having the clad steel sheet that contains Zn coating, form outermost film contain satisfied: the electrical conductivity of water when (A) being dissolved in ion exchange water (electrical conductivity: below the 4 μ S/cm) with the concentration of 0.1 quality % is more than the 500 μ S/cm; And (B) up to 200 ℃ of non-chromium compounds (being alkali metal phosphate, chloride, alkaline-earth metal hypochlorite as an example) that the such condition of thermal decomposition does not take place before, the red rust that can suppress end face produces (patent documentation 2).
In addition; The chromium-less precoated metal sheet of known following end face corrosion resistance excellent: the primary coat on the non-chromium base treatment epithelium of metallic plate film and/or on film and contain porous matter inorganic particles (as an example for porous silica particulate) and the antirust particulate of slow release that compoundization of metal compound system rust resisting pigment (being Mg or Ca compound as an example) forms, stipulated the time from the dissolution rate (patent documentation 3) of the metal ion of the rust resisting pigment stripping of filming of the grid of stroke having carved 100 1mm * 1mm to 40 ℃ carbonate pH titer dipping.
In addition; Also known following chromium-less precoated metal sheet: contain filming of alkaline earth metal compound particle, zinc compound particle and phosphate particle through having; And when being defined in the pure water that impregnated in normal temperature from the stripping quantity mol ratio of alkaline-earth metal, zinc and the phosphorus composition of the stripping of filming, the red rust that can suppress end face produces (patent documentation 4).
The prior art document
Patent documentation 1: TOHKEMY 2008-229518 communique
Patent documentation 2: TOHKEMY 2009-045923 communique
Patent documentation 3: TOHKEMY 2009-078450 communique
Patent documentation 4: TOHKEMY 2008-189965 communique
Summary of the invention
The objective of the invention is to enlarge for the utilization of the chromium-less pre-coated steel plate of the stripping that promotes not have harmful chromium; A kind of novel excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of end face is provided; Even this steel plate is being exposed under the room external environment of rainwater etc., the generation institute that also can not be compromised red rust attractive in appearance uses agonisingly.
The excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of end face of the present invention; Be to be that the two sides of clad steel sheet has chromium-less chemical conversion processing layer and the chromium-less pre-coated steel plate of filming more than the one deck that forms on this chemical conversion processing layer at zinc; It is characterized in that the outermost layer among the filming of the back side at least of this pre-coated steel plate is filmed and contained high tungstates of end face anelasticity or silicate.So-called " the end face anelasticity is high " of using in this manual is meant that end face anelasticity evaluation test through following explanation is judged as zero or the character of △.
Typical chromium-less pre-coated steel plate of the present invention has primer coating film layer and last coating film layer on the chromium-less chemical conversion processing layer of each face, the last coating film layer at the back side contains tungstates.
Except the last coating film layer at the back side, the primer coating film layer at the back side also can contain high tungstates of end face anelasticity or silicate.
The example of preferred tungstates is sodium tungstate, artificial schellite, ammonium tungstate, tungstate lithium, magnesium tungstate, preferred especially sodium tungstate and magnesium tungstate.Also can be also with two or more tungstates.
Preferably: the content of the tungstates in filming is 6 ~ 50 weight %.
The example of preferred silicate is sodium metasilicate, potassium silicate, lithium metasilicate, preferred especially sodium metasilicate and potassium silicate.Also can be also with two or more silicate.
Preferably: the content of the silicate in filming is 5 ~ 50 weight %.
As the pre-coated steel plate (PCM) of goods, general to be provided with the form supply person of needs who films at single face with the desired performance of the person of needs of its processing and manufacturing end article.In the present invention, regard the face of filming that is provided with the performance that the person of needs requires " surface " of pre-coated steel plate as, the face of the opposition side of this face is called " back side "." surface " is positioned at the outside in the end article that the person of needs makes, relative therewith by the face that human eye is felt, and " back side " is not felt by human eye in end article, so filming of the back side do not require the performance of the surperficial desired degree of filming.From like this, " surface " of pre-coated steel plate and the difference at " back side " are open-and-shut from its outward appearance, relatively both, " back side " is inferior from the viewpoint of aesthetic feeling particularly, can easily distinguish thus.
According to the present invention; At least high tungstates or the silicate of end face anelasticity that the outermost layer among the filming of the back side of chromium-less pre-coated steel plate is filmed and contained; Help the corrosive embodiment of the anti-red rust of end face, produce being exposed to the red rust that suppresses end face under the room external environment of rainwater etc. effectively.Thus, can enlarge the utilization of the chromium-less pre-coated steel plate of the stripping that do not have harmful chromium and make major contribution.
The specific embodiment
At this, explain that at first the inventor accomplishes fact of the invention of the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of the application's novel end face.
Handling in the pre-coated steel plate with widely used chromate before the chromium-less pre-coated steel plate is compared; Talk about the end face corrosion resistance; Be meant near the characteristic of the expansion of filming (blister) that prevents end face; Therefore, even in order to expand from end face part in such salt damage region, the region in coastline, using also can prevent to film, with how preventing that zinc is from the zinc coating stripping of the pre-coated steel plate target as exploitation.Its reason is; Handle the epoch of pre-coated steel plate at chromate; Because the corrosion resistance of the excellence of chromate; Therefore under the simple moist environment degree of wetting grade, do not produce red rust basically, not have to note the corrosion resistance under simple moist environment, but concern results from the expansion of filming of dissolving of zinc at end face by rainwater.Thereby, when chromate is handled the exploitation of new product of pre-coated steel plate, pay attention in vitro salt spraytest (SST).In the electrolyte environment of salt spraytest, because the sacrifice corrosion protection result of the zinc coat of pre-coated steel plate even produce white rust, also never produces red rust till zinc is consumed.
But when the utilization of handling the chromium-less pre-coated steel plate of pre-coated steel plate difference than chromate in the corrosion resistance level enlarged, the problem of the red rust that under non-electrolyte atmosphere, produces at end face with the short time was significantly changed quickly.For example, the red rust of air-conditioner outdoor unit produces becomes big problem.What particularly the generation of red rust was regarded as serious problem is, the top board that drawing and forming goes out and fitting portion side plate, ejection part (knock-out) (forming grooving on the steel plate and the structure division about 1mm of staggering) wait, accumulate water easily and the lasting wetting part of steel plate end face long-time (according to circumstances being a few days) because of capillarity.In addition, the center that mainly produces the region of red rust is not salt damage region but the intermountain portion of coastwise grade.This is because end face continues the wetting corrosion cell that do not form thus in not containing electrolytical water, therefore when becoming the environment of high humility (particularly plum rains period etc.), zinc is not sacrificed dissolving, and the cause of corrosion takes place in the iron-based body end face that exposes.
In chromate is handled pre-coated steel plate, be not easy to produce such red rust and be since chromate composition (strontium chromate) near end face (chromate handle epithelium) stripping to water, form the cause of protective layer at iron-based body end face.Relative therewith; The rust resisting pigment that is contained in the filming of common chromium-less pre-coated steel plate (calcium exchange silica, aluminium triphosphate etc.); Water-soluble low; Even stripping antirust ability in the water is also poor than the chromate composition, therefore, the sacrifice corrosion protection of zinc do not prevent that red rust from producing is inadequate under bringing into play the moist environment of function effectively.
In view of above-mentioned viewpoint, the inventor has considered to suppress effect in order to obtain sufficient end face red rust full terms (1) ~ (3) below needing to satisfy when exploitation novel chromium-less pre-coated steel plate of the present invention.
(1) at the pre-coated steel plate end face during for a long time by water-wet, fully composition stripping from film of amount.
(2) composition of stripping produces effectively suppressing red rust or red rust and white rust.
(3) near the composition of stripping lasting delay end face.
Under regard to these conditions and at length explain.
About condition (1)
The generation of the red rust of pre-coated steel plate end face is a phenomenon: when the high humidity in plum rains period etc.; Continue under the wetting environment at the end face water few by electrolyte content; Can not embody the sacrifice corrosion protection result of zinc, the iron stripping is in water, and therefore red rust produces from end face between utmost point short-term.Produce in order to suppress this red rust, effectively make and contain antirust effective composition in filming, in end face active ingredient stripping from film during by water-wet, the red rust that is suppressed at end face produces.If the material that contains in filming is water-soluble insufficient, have antirust ability even then suppose this material, can not stripping in water, therefore can not get the effect that red rust suppresses.Thereby the material that contains in filming must have water-soluble fully.
By the way, the rust resisting pigment of employed calcium exchange silica (trade name シ one Le デ Star Network ス) of existing chromium-less pre-coated steel plate and aluminium triphosphate etc. is not have sufficient water miscible examples of substances.
About condition (2)
From the composition of stripping to the water of filming, must be the material that can suppress the generation of red rust or red rust and white rust.Even have the material that red rust suppresses ability, its rust-proof mechanism also is various, and according to its rust-proof mechanism, the material with red rust inhibition ability can be classified as follows.
(i) stripping becomes electrolyte in the water electrical conductivity is risen, thereby embodies the sacrifice corrosion protection result of zinc, suppresses the material of the generation of red rust thus.
(ii) form passivation attitude etc., suppress the material (material that plays a role as the dissolution inhibitor of iron) of the stripping of iron itself in iron surface absorption.
The material that (iii) except above-mentioned effect (ii), also plays a role as the dissolution inhibitor of zinc.
If water miscible salt, ionization becomes electrolyte when then being dissolved in water, therefore thinks as long as its characteristic that does not have (ii) above-mentioned or material (iii) then is classified as the material of above-mentioned (i).But the prerequisite of the mechanism that the red rust of the material of above-mentioned (i) suppresses is to make the zinc corrosion, therefore can not avoid the generation of white rust and the generation of expansion (blister) of filming down.Sacrifice corrosion protection result if the corrosion of zinc advances and disappear, the generation of red rust as a result begins.
On the other hand, above-mentioned material (ii), owing to the sacrifice corrosion protection result that does not rely on zinc prevents the stripping of iron itself, so the dissolving of zinc is suppressed the level into the self-dissolving in water, and the generation of white rust, blister tails off.Above-mentioned material (iii), because the self-dissolving of zinc also suppresses, so the generation of the generation of white rust, blister becomes still less.From above viewpoint, in the present invention,, be not to use the material of above-mentioned (i) as the inhibition effective substances that the red rust to chromium-less pre-coated steel plate end face produces, use material (ii) above-mentioned or (iii).
Can roughly adopt following method to judge whether specific material is a certain of above-mentioned (i) ~ (iii).
For the material of subjects, carry out 2 following tests.
(test 1) flooded cold-rolled steel sheet (500 hours) in the solution that in distilled water 40ml, has dissolved subjects material 100mg.
(test 2) be the common chromium-less pre-coated steel plate (being easy to generate the steel plate of the tendency of red rust at end face) (500 hours) of dipping in the identical aqueous solution, and this steel plate is formed with and contains calcium exchange silica and/or aluminium triphosphate filming as rust resisting pigment.
500 hours dip time in these tests; It is the actual service conditions of imagination pre-coated steel plate; Producing even continuous impregnating also can suppress the red rust of end face in 500 hours, is for concerning the red rust that suppresses end face produces effective substances, setting for essential important document.
For each steel plate investigation red rust that takes out from the aqueous solution, the generation situation of white rust, judge a certain among the material that whether is classified as above-mentioned (i) ~ (iii) through following benchmark.
Be classified as the material of (i)
Produce red rust in test in 1, in test 2, do not produce red rust and produce a large amount of white rusts.
Be classified as material (ii)
Do not produce red rust in test in 1, in test 2, do not produce red rust and produce micro-white rust.
Be classified as material (iii)
In test 1, do not produce red rust, red rust, white rust do not produce in test 2.
About condition (3)
Even substances satisfies the important document (that is, even from filming stripping fully to water, playing a role as the dissolution inhibitor of iron) of above-mentioned condition (1) and (2), this material is washed away at once, does not also play a role as inhibitor.Thereby, in order to ensure the anti-red rust corrosivity of end face, as the material demand of inhibitor composition in " delay " constantly near end face or its.
In this said " delay ", comprise the various meanings.For example; (a) the inhibitor composition forms absorption or passivation epithelium, and the lining end face is (b) because of the physical factor of viscosity and surface tension etc.; Inhibitor solution continues to be detained existence at end face; (c) (because the flow velocity of the part that contact with the surface of solids among surface of solids flowing fluid is 0), so the high mobile liquid film boundary layer region of inhibitor concentration is present on the end face, or the like any all be equivalent in this said " delay ".And by " delay " that any phenomenon causes, when being in the state of the inhibitor effect that can bring into play substances, this material all shows as has " end face anelasticity ".
Method below adopting for the evaluation of the end face anelasticity of specific material is carried out.
1) material 10mg is dissolved among the distilled water 40ml, formation is contained after calcium exchange silica and/or aluminium triphosphate are cut to 50 * 50mm as the common chromium-less pre-coated steel plate (being easy to generate the steel plate of the tendency of red rust at end face) of filming of rust resisting pigment (inhibitor) it was flooded 72 hours in this aqueous solution.
2) with taking out (not producing red rust) the aqueous solution of pre-coated steel plate (50 * 50mm) from above-mentioned 1), after washing gently with distilled water, impregnated in apace in the distilled water, placed 350 hours and 500 hours in this moment.
Above-mentioned 2) in, as the evaluation of end face anelasticity, with 350 hours situation be with interior generation red rust *, flood that not produce red rust but flooded situation about producing in 500 hours in 350 hours be △, flooding the situation that did not also produce red rust in 500 hours fully is zero.Placing the situation do not produce red rust in 350 hours (△ or zero situation), this material is judged as " the end face anelasticity is high ".72 hours inhibitor aqueous solution dip time of the pre-coated steel plate above-mentioned 1) is to set as the model condition of remarkableization of difference of the end face anelasticity that is used to make material.This be with in fact in the roughly consistent condition of conditional outcome of top board fitting portion of a large amount of air-conditioner outdoor units that produce red rust in period of plum rains.Above-mentioned 2) 350 hours and 500 hours dip time in are to set to have the identical reason of dip time that above-mentioned red rust suppresses in the test of type of material of ability with judgement.
Based on above prerequisite, whether it plays a role as the dissolution inhibitor of iron the inventor for the investigation of various materials, has found some materials likely.On this basis, for these materials, tested its end face anelasticity.The part of evaluation result is summarized in table 1.
The red rust of the various substances of table 1 suppresses ability and end face anelasticity
As its result; Though the high end face anelasticity of which embodiment through above-mentioned " delay " mechanism it be unclear that; But found out in the tungstates crowd; The tungstates of sodium tungstate, artificial schellite, ammonium tungstate, tungstate lithium and magnesium tungstate representative works as the dissolution inhibitor of iron, is to give the anti-red rust of end face corrosive useful material to the chromium-less pre-coated steel plate.
Can know in the tungstates crowd preferred especially sodium tungstate and magnesium tungstate.Confirmed also that from table 1 the anti-red rust corrosivity of end face that these tungstates show is equal with the antirust composition strontium chromate of chromate processing pre-coated steel plate.In addition, though be tungstates, barium tungstate is judged as zero in the evaluation of test 1 and test 2, but in the test of end face anelasticity, be judged as *.Also in the evaluation of test 1 and test 2, be judged as zero as the known sodium molybdate of antirust material in the past, in the test of end face anelasticity, be judged as *.
Tungstates through sodium tungstate etc. obtains mechanism that the end face red rust suppresses effect as above-mentioned and insufficient clear and definite; But infer that its mechanism is the passivation attitude that forms fine and close ferriferous oxide through the iron surface at the pre-coated steel plate end face, play a role as the dissolution inhibitor of iron.In the above-mentioned test 2 of the type of judging material, can confirm the generation of some white rusts, it is low to think that thus tungstates suppresses the effect of stripping of zinc of coating.But think; On the contrary; Tungstates does not suppress the stripping (self-dissolving) of zinc, and the stripping that therefore moderately produces zinc can obtain sacrificing corrosion protection result; Forming end face protection epithelium down as doing the wet actual exposed environment of condition repeatedly (the actual environment for use of the end article of the pre-coated steel plate that comprises processed), producing and advantageously play a role through suppressing red rust.In addition, through with the rust resisting pigment and the usefulness of the employed calcium of existing chromium-less pre-coated steel plate exchange silica (trade name シ one デ Star Network ス), aluminium triphosphate etc., also can improve the anti-red rust corrosivity of end face synergistically.
Found out that in the silicate crowd silicate of sodium metasilicate, potassium silicate, lithium metasilicate representative also works as the dissolution inhibitor of zinc, is to give the anti-red rust of end face corrosive useful material to the chromium-less pre-coated steel plate when being the dissolution inhibitor of iron.Wherein, can know preferred especially sodium metasilicate and potassium silicate.Confirmed also that from table 1 the anti-red rust corrosivity of end face that silicate of the present invention shows is equal with the antirust composition strontium chromate of chromate processing pre-coated steel plate.In addition, though be silicate, calcium silicates is not estimated rust-proof effect in test 1 with testing all to be judged as in 2.Think that its reason is that calcium silicates is an indissoluble salt.In addition, magnesium silicate is judged as zero in the evaluation of test 1 and test 2, but in the test of end face anelasticity, be judged as *.
Silicate through sodium metasilicate etc. can obtain mechanism that the end face red rust suppresses effect as above-mentioned and insufficient clear and definite, but thinks iron surface and the zinc surface that it is trapped in the pre-coated steel plate end face, plays a role as the dissolution inhibitor of two metals.Above-mentioned end face anelasticity estimate 2) with 3) if test in dip time above 500 hours then can confirm to begin to produce the form of red rust; Even think thus silicate be adsorbed in its strength of end face also a little less than, the possibility of the delay that is caused by the existence in liquid film boundary layer is high.
The phosphate-based material of known sodium phosphate, magnesium monohydrogen phosphate etc. has the characteristic to iron surface absorption, can expect " the end face anelasticity is high " thus, but their results in above-mentioned end face anelasticity test be *.This example has shown to the high material of ironing surface adsorption capacity may not we can say that the end face anelasticity is high.
In the present invention, give the corrosive end face anelasticity of the anti-red rust of end face high tungstates or silicate, preferably be present in the filming of rear side of pre-coated steel plate the chromium-less pre-coated steel plate.Under filming of rear side was a plurality of situation, tungstates that the end face anelasticity is high or silicate may reside in all filming, and perhaps also can exist only in the filming an of part.That is to say, tungstates that the end face anelasticity is high or silicate, in order to embody the anti-red rust corrosivity of end face effectively, this tungstates or silicate preferably are present in outermost at least the filming.Because tungstates that the end face anelasticity is high or silicate are in order to embody the anti-red rust corrosivity of end face; Need be dissolved in the water of wetting pre-coated steel plate, outermost the filming of exposing at the back side of pre-coated steel plate can be provided as this required area (by the area of water-wet).Filming beyond the outermost layer just exposed at end face part, and it exposes area seldom, therefore thinks to only depend on filming beyond the outermost layer, is not enough to guarantee the tungstates that the end face anelasticity of effective dose is high or the stripping of silicate.Also can contain high tungstates of end face anelasticity or silicate in the filming of face side, but under this situation, should sneak into this tungstates or silicate in the scope of not damaging the desired important document from the person of needs of filming of face side.
The tungstates that the end face anelasticity is high can be sneaked in the outermost layer at the pre-coated steel plate back side is filmed about 6 ~ 50 weight %, and the silicate that the end face anelasticity is high can be sneaked in the outermost layer at the pre-coated steel plate back side is filmed about 5 ~ 50 weight %.If lack than this scope; Then be not enough to embody the anti-red rust corrosivity of end face; If more than 50 weight %, then tungstates or the silicate stripping exceedingly that this end face anelasticity is high when being exposed to moist environment of filming after the film forming, the generation of filming is sometimes expanded and/or is peeled off.Tungstates or silicate concentration that end face anelasticity during back side outermost layer is filmed is high, more preferably 7 ~ 40 weight %, most preferably be 10 ~ 30 weight %.
Filming beyond filming to the outermost layer at the pre-coated steel plate back side sneaked under the situation of high tungstates of end face anelasticity or silicate; From carrying out the viewpoint of the stripping to water easily, the approaching amount of the upper limit among the concentration range during preferred employing is filmed with above-mentioned outermost layer.
Tungstates that the end face anelasticity of using in the present invention is high or silicate are powder at normal temperatures, consider the thickness of filming sneak into, and preferably in coating, disperse to become 5 ~ 20 μ m, more preferably become about 5 ~ 10 μ m and use up to maximum particle diameter.
Tungstates that the end face anelasticity is high or silicate powder can adopt arbitrary method to be blended in the coating of the usefulness of filming of target.For example; Can join the coating (comprising neccessary composition and solvent beyond high tungstates of end face anelasticity or the silicate) of the preparation of having accomplished application; The mixture that perhaps also can more than one the composition with coating mixed in advance and form mixes with other compositions of coating and to modulate coating.
Filming of chromium-less pre-coated steel plate of the present invention given the high tungstates of end face anelasticity that the anti-red rust corrosivity of end face needs or the silicate except interpolation, and the coating that can adopt the manufacturing of common chromium-less pre-coated steel plate to adopt forms.As an example, film in the top layer that can form the primer coating film that is made up of polyester based resin, melmac, isocyanates, calcium exchange silica, aluminium triphosphate, titanium oxide, silica, other additive etc. on the surface, is made up of polyester based resin, melmac, isocyanates, calcium exchange silica, aluminium triphosphate, titanium oxide, silica, various coloring pigment, wax, other additive etc.Film in the top layer that can form the primer coating film that is made up of polyester based resin, melmac, isocyanates, calcium exchange silica, aluminium triphosphate, titanium oxide, silica, other additive etc. overleaf, be made up of polyester based resin, melmac, isocyanates, calcium exchange silica, aluminium triphosphate, titanium oxide, silica, various coloring pigment, wax, other additive etc.During the outermost at the back side was filmed at least among these were filmed, comprise high tungstates of end face anelasticity or silicate according to the present invention.
As the steel plate that becomes these substrates of filming, can use zinc is clad steel sheet.As zinc is clad steel sheet; Can use steel plate arbitrarily such as the steel plate of for example hot-dip galvanized steel sheet, plated steel sheet, plating Al-zinc, the steel plate of plating Al-Mg-Si-zinc; But under the situation of the steel plate that uses plating Al-Mg-Si-zinc, the raising of anti-red rust property is remarkable especially.
At zinc is the surface of clad steel sheet, is used to be coated with above-mentioned filming with the pretreatment layer of coating, and common chromium-less chemical conversion processing layer can be set.As an example, the chemical treatment layer can use the epithelium of any two or more and resin that contains silica, silane coupling agent, tannin or tannic acid, zirconium compounds, titanium compound.The chemical conversion processing layer can through chemical conversion treatment solution is carried out dip coated, roll coater application, the application of ring roller (ringer roll), hairbrush coating, spraying waits and forms.
Chromium-less pre-coated steel plate of the present invention; Except in the formation that the outermost at the back side is at least filmed, using the coating that has added high tungstates of end face anelasticity or silicate; Can adopt common manufacturing equipment, the manufacturing approach of chromium-less pre-coated steel plate to make, not be elaborated at this for these.
Embodiment
Further specify the present invention through embodiment.Certainly the present invention is not limited at the embodiment shown in this.
A. sample raw sheet
Raw sheet GI, SD below using process sample.
(1) GI: (0.6mm thickness, coating adhesion amount are 80g/m to hot-dip galvanized steel sheet
2Single face)
(2) SD: (0.6mm thickness, coating adhesion amount are 80g/m to the steel plate of plating 11%Al-3%Mg-0.2%Si-zinc
2Single face)
B. the chemical conversion of raw sheet is handled
Through silane coupling agent, tannic acid, silica and mylar mixed stocker inorganic agent, raw sheet has been carried out the chromate-free chemical conversion handled (100mg/m
2).
C. the application of sample
Use has cooperated the coating of the shown rust resisting pigment composition of table 2 to following coating resin, in advance each face of the raw sheet handled of chemical conversion implement priming paint (primer) application and finish paint (top coat) application.
(1) the primer base resin at the surface and the back side
Polyester/melamine+isocyanates is also with curing type (Japanese Off ア イ Application コ one テ Application グ ス corporate system FLC687 coating resin)
(2) surperficial finish paint coating resin
Macromolecule polyester/melamine cured type (Japanese Off ア イ Application コ one テ Application グ ス corporate system FLC7000 coating resin)
(3) back side finish paint coating resin
Polyester/melamine cured type (Japanese Off ア イ Application コ one テ Application グ ス corporate system FLC100HQ coating resin)
The rust resisting pigment composition that cooperates in the coating of table 2 is following.
A: calcium exchange silica
B: aluminium triphosphate
C: sodium tungstate
D: artificial schellite
E: ammonium tungstate
F: tungstate lithium
G: sodium phosphotungstate (comparison)
H: sodium acid carbonate (comparison)
I: potassium chloride (comparison)
J: magnesium tungstate
K: barium tungstate (comparison)
L: sodium molybdate (comparison)
Table 2
In table 2, then the numerical value in the bracket of the mark of rust resisting pigment is represented the weight concentration percentage (for example, " A (20) " expression coating contain the pigment A of 20 weight %s) of rust resisting pigment with respect to the total solid composition of coating.Table 2 only is illustrated in the rust resisting pigment composition that cooperates in the coating, does not represent the coloring pigment composition.
Sample to processing carries out following performance test.
1. area, rural area exposure test
The purpose of area, rural area exposure test is the patience of directly estimating about at the red rust that ground produces between short-term under the moist environment of non-electrolyte.
The workpiece and the unprocessed flat board of shape that has reproduced the top board fitting portion of air-conditioner outdoor unit with processing sample uses as test block.
After just having got into plum rains, each test block is arranged on area, rural area (monarch Jinshi City, Chiba county is landlocked), visualization after 1 month.
The red rust evaluation of top board fitting portion, with the average evaluation that does not produce red rust fully be ◎, red rust generation for the average evaluation of trace (red rust is lower than 1%) is zero, the average evaluation of red rust generation few (red rust is 1 ~ 5%) is △, red rust generation many (red rust surpasses 5%) average evaluation be *.
The blister of dull and stereotyped surface plane portion (bubbles; Blister) estimate, with the average evaluation that does not produce blister fully be that the average evaluation of ◎, trace (in ASTM D 714 for more than the 8F level) is zero, the average evaluation of few ~ many (being lower than the 8F level) is *.
2. salt damage area exposure test
The purpose of salt damage area exposure test is to estimate the corrosion resistance that is based on long-term this existing viewpoint of patience under the electrolyte environment.
The workpiece and the unprocessed flat board of shape that has reproduced the top board fitting portion of air-conditioner outdoor unit with processing sample uses as test block.
Each test block is arranged on salt damage area (coastal strip in Okinawa), visualization after 2 years.
The red rust evaluation of top board fitting portion, with the average evaluation that does not produce red rust fully be ◎, red rust generation for the average evaluation of trace (red rust is lower than 1%) is zero, the average evaluation of red rust generation few (red rust is 1 ~ 5%) is △, red rust generation many (red rust surpasses 5%) average evaluation be *.
The end face on dull and stereotyped surface expands and estimates, the average evaluation that will be that the average evaluation below the 2mm is zero from the maximum of the expansion of end face, surpasses 2mm for *.
3. laboratory test
The purpose of laboratory test (distilled water immersion test, 40 ℃ HCT test, 2 hours immersion tests of boiled water) is the patience of estimating simply about at the red rust that ground produces between short-term under the moist environment of non-electrolyte.But about the present invention, the exposure test result in the area, rural area well is primary meaning, and laboratory test is tested as a reference.
Material from film stripping the aqueous solution near end face, be detained the time that exists, extremely long in the distilled water immersion test, short on the contrary in 40 ℃ HCT test.Think that the actual environment condition is in the condition of the centre of these laboratory tests.Thereby, can think and bring the good result under actual environment can obtaining good result under the condition of these laboratory tests.
In the distilled water immersion test, the sample of 50 * 50mm flooded 500 hours in distilled water 40ml after, estimate the red rust of end face.With the average evaluation that does not produce red rust fully be the average evaluation that the average evaluation of ◎, trace (red rust is lower than 1%) is zero, the average evaluation of few (red rust is 1 ~ 10%) is △, many (red rust surpasses 10%) be *.
In 40 ℃ HCT test,, estimate the red rust of the end face after 240 hours with sample vertically suspension setting lengthways in the high wet sump of constant temperature (40 ℃, 98%RH) of 50 * 100mm.With the average evaluation that does not produce red rust fully be the average evaluation that the average evaluation of ◎, trace (red rust is lower than 5%) is zero, the average evaluation of few (red rust is 5 ~ 10%) is △, many (red rust surpasses 10%) be *.
In 2 hours immersion tests of boiled water, flat board was flooded 2 hours the blister of evaluation table facial plane portion and back side plane portion in boiled water.With the average evaluation that does not produce blister fully be that the average evaluation of ◎, trace (in ASTM D 714 for more than the 8F level) is zero, the average evaluation of few ~ many (being lower than the 8F level) is *.
The result of above-mentioned each test is shown in table 3.
Table 3
In addition, with the rust resisting pigment composition replace to below shown in the rust resisting pigment composition, likewise carry out above-mentioned each the test.The composition that table 4 expression cooperates, table 5 expression result of the test.
The rust resisting pigment composition that cooperates in the coating of table 4 is following.
A: calcium exchange silica
B: aluminium triphosphate
C: sodium metasilicate
D: magnesium silicate (comparison)
E: potassium silicate
F: calcium silicates (comparison)
G: sodium acid carbonate (comparison)
H: potassium chloride (comparison)
I: lithium metasilicate
Table 4
Table 5
Claims (9)
1. the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of an end face; Be to be that the two sides of clad steel sheet has chromium-less chemical conversion processing layer and the chromium-less pre-coated steel plate of filming more than the one deck that forms on this chemical conversion processing layer at zinc; It is characterized in that the outermost layer among the filming of the back side at least of this pre-coated steel plate is filmed and contained high tungstates of end face anelasticity or silicate.
2. the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of end face according to claim 1; On the chromium-less chemical conversion processing layer of each face, have primer coating film layer and last coating film layer, the last coating film layer at the back side contains high tungstates of end face anelasticity or silicate.
3. the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of end face according to claim 2, the primer coating film layer at the back side also contains high tungstates of end face anelasticity or silicate.
4. according to the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of each described end face of claim 1 ~ 3, the high tungstates of said end face anelasticity is sodium tungstate, artificial schellite, ammonium tungstate, tungstate lithium, magnesium tungstate or their mixture.
5. according to the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of each described end face of claim 1 ~ 3, the high silicate of said end face anelasticity is sodium metasilicate, potassium silicate, lithium metasilicate or their mixture.
6. the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of end face according to claim 4, the high tungstates of said end face anelasticity is sodium tungstate and magnesium tungstate.
7. the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of end face according to claim 5, the high silicate of said end face anelasticity is sodium metasilicate and potassium silicate.
8. according to the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of each described end face of claim 1 ~ 5, the content of the tungstates that the said end face anelasticity in filming is high is 6 ~ 50 weight %.
9. according to the excellent chromium-less pre-coated steel plate of the anti-red rust corrosivity of each described end face of claim 1 ~ 5, the content of the silicate that the said end face anelasticity in filming is high is 5 ~ 50 weight %.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP277770/2009 | 2009-12-07 | ||
| JP2009277787 | 2009-12-07 | ||
| JP2009277770 | 2009-12-07 | ||
| JP277787/2009 | 2009-12-07 | ||
| PCT/JP2010/072315 WO2011071175A1 (en) | 2009-12-07 | 2010-12-07 | Chromate-free precoated steel sheet having excellent end-surface rust corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102648090A true CN102648090A (en) | 2012-08-22 |
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ID=44145717
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800554905A Pending CN102648090A (en) | 2009-12-07 | 2010-12-07 | Chromate-free precoated steel sheet having excellent end-surface rust corrosion resistance |
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| Country | Link |
|---|---|
| JP (1) | JP4927233B2 (en) |
| KR (1) | KR101357881B1 (en) |
| CN (1) | CN102648090A (en) |
| MY (1) | MY156857A (en) |
| TW (1) | TWI431158B (en) |
| WO (1) | WO2011071175A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110520290A (en) * | 2017-04-05 | 2019-11-29 | 日本制铁株式会社 | The marresistance of film and the pre-coated steel plate that resistance to hygroscopicity is good and the resistance to red rust corrosivity in end face is excellent |
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| JP2001247980A (en) * | 2000-03-03 | 2001-09-14 | Nippon Steel Corp | Hexavalent chromium-free precoated steel sheet excellent in corrosion resistance |
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| JP2004169145A (en) * | 2002-11-21 | 2004-06-17 | Nisshin Steel Co Ltd | Precoated steel sheet for wiper and wiper |
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2010
- 2010-12-06 TW TW099142345A patent/TWI431158B/en active
- 2010-12-07 JP JP2011522340A patent/JP4927233B2/en active Active
- 2010-12-07 CN CN2010800554905A patent/CN102648090A/en active Pending
- 2010-12-07 MY MYPI2012700301A patent/MY156857A/en unknown
- 2010-12-07 WO PCT/JP2010/072315 patent/WO2011071175A1/en active Application Filing
- 2010-12-07 KR KR1020127014117A patent/KR101357881B1/en active IP Right Grant
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| JPH07132574A (en) * | 1993-11-09 | 1995-05-23 | Nippon Parkerizing Co Ltd | Method for coating metal surface |
| JP2001247980A (en) * | 2000-03-03 | 2001-09-14 | Nippon Steel Corp | Hexavalent chromium-free precoated steel sheet excellent in corrosion resistance |
| CN1914358A (en) * | 2003-12-09 | 2007-02-14 | 关西涂料株式会社 | Electroplating solution composition for organic polymer-zinc alloy composite plating and plated metal material using such composition |
| CN101235498A (en) * | 2008-02-28 | 2008-08-06 | 武汉钢铁(集团)公司 | Chromium-free inactivating liquid used for galvanized steel sheet surface |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20120088797A (en) | 2012-08-08 |
| TWI431158B (en) | 2014-03-21 |
| MY156857A (en) | 2016-04-15 |
| JP4927233B2 (en) | 2012-05-09 |
| JPWO2011071175A1 (en) | 2013-04-22 |
| WO2011071175A1 (en) | 2011-06-16 |
| TW201129716A (en) | 2011-09-01 |
| KR101357881B1 (en) | 2014-02-03 |
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