CN1159368A - Metal plate coated with color resin and making method - Google Patents
Metal plate coated with color resin and making method Download PDFInfo
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- CN1159368A CN1159368A CN96122712A CN96122712A CN1159368A CN 1159368 A CN1159368 A CN 1159368A CN 96122712 A CN96122712 A CN 96122712A CN 96122712 A CN96122712 A CN 96122712A CN 1159368 A CN1159368 A CN 1159368A
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- metallic plate
- coating
- resin
- color resin
- pigment
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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
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
-
- 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
- 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
-
- 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
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a metal plate spread with colorized resin, which has low cost and simple equipment manufacture, excellent stable surface gloss, hue of original metal before reflective coating resin is spread, excellent anti-corrosion and chrome-resistant solubility. The utility model also provides the method of manufacturing the metal plate. A metal plate is formed with a layer of resin coating containing pigments, wherein G1 meets the following formula (1), the gloss of the 60 degrees mirror surface of the metal plate before forming colorized resin coating is prescribed to be G0, the gloss of the 60 degrees mirror surface of the metal plate after forming colorized resin coating is prescribed to be G1. G0> G1 >=0.5G0 (1).
Description
The present invention relates to a kind of metallic plate that scribbles color resin, can be used for the inside and outside member of automobile and household electrical appliance and the outside sheet material of steel systeming equipment etc., or be used for construction material; More particularly, it is bright and at the metallic plate that scribbles color resin that has good articulation aspect the gloss of reflective metals ground to the present invention relates to a kind of color and luster, with and manufacture method.
Usually, the metallic plate that is coated with zinc one class is widely used in automobile, household electrical appliance, construction material etc.Because these anti-corrosive properties of metallic plate self that are coated with zinc one class are not enough and bad with the adhesiveness of coating, thereby with the upper surface of chromate or phosphate treated coating.For reaching performance demands such as required higher anti-corrosive properties, chemical resistance, usually resin film layer can be located on these treated top layers.Because used metallic plate need carry out the excellence design from product outward appearance and desirable tone aspect attractive in appearance, therefore the resin molding as the outermost layer coating should be undertaken painted by the required tone of user.
Generally include for the resin molding method of colouring and add coloring pigment in coating, such as organic pigment or inorganic pigment, well-known organic pigment is painted higher and the inorganic pigment covering power is higher.In order to hide the tone of metallic plate, general, usually only contain inorganic pigment in the coating or also be combined with organic pigment, and, then need 10g/m in order to hide the tone of ground fully
2Thick films.
In addition, in order to give resin molding such as higher anti-corrosive properties and than the performance of high chemical resistance one class, suitable is the baking hardening type organic solvent coating that can make dense film.Therefore this class coating can be used to scribble the metallic plate of resin, yet disadvantageously, because the volatilization of organic solvent makes the coating weight of filming be difficult to stablize, or this baking hardening needs large-scale drying equipment, the organic solvent that maybe need settle partial exhaust gas equipment to volatilize with recovery.Therefore, be difficult in the metallic plate that this class of high-speed production on the production line of producing plated metal sheet scribbles resin.Have the very high coating weight and the problem of equipment investment because requiring films, so the metallic sheet of gained is very expensive.
In order to address these problems, adopted a kind of steel plate that scribbles color resin that can in the production procedure of producing plated metal sheet, make in mode cheaply.For example, Japan Patent discloses and discloses a kind of color steel sheet of making in order to the below method among the flat 5-16292: on the surface of the steel plate that is coated with zinc one class material the chromate coat is set, forms one deck L more thereon
*The color resin layer of value≤60, thickness≤5 μ m.Yet the tone of this class color steel sheet depends on the tone of ground metallic plate and the color harmony thickness of resin molding as everyone knows; If the thickness of color resin film is little, even the potential L of color resin coating
*Value≤60, still less to the tinting strength, tinting power and the covering power that are coated with steel plate.Therefore be difficult to produce stable tone.Here, " L
*Value ＂ is a kind of designator, and expression is by JIS Z 8730 defined " brightness "; The darkness increase is L then
*Value is (-) value, and the whiteness increase is L then
*Value is (+) value.More particularly, when color resin layer is black tone, L
*Value≤60; When its tone is white, L
*Value finally can be 60 or higher.Therefore, L
*Value is not that representative hides the designated symbol (opposite, this value can be represented the glossiness of ground metallic plate) add to the ground metallic plate, and like this, the gained color steel sheet is aspect quality stability and L
*Value is relevant.
Scheme as an alternative, Japan Patent discloses flat 5-31450 and discloses a kind of colour, through applying and surface treated steel plate, the part of its processing has good ground covering power and good welding performance, this steel plate is made by following method: the steel plate that makes the surface be coated with zinc one class material is handled through perchromate again, 30-100 part colouring agent (comprise coloring pigment and account for the titanium white of coloring pigment total amount 0.30-0.95) and 20-40 part cataloid as the film reinforcing material is dispensed in 100 parts of resins, then, form the thick coating of 1-3 μ m thereon with the water-soluble type or the above-mentioned steel plate of water-dispersion type resin-coating of gained.
Yet, in order to improve the ground covering power of treated part, the concentration limits that Japan Patent discloses among the flat 5-31450 pigment is decided to be up to 30 parts or higher, but disadvantageously, increase owing to add the concentration of the pigment of resin molding, resin molding is reduced the adhesion of ground metallic plate.It is additionally noted that,, can make anti-corrosive properties reduction as the key property of resin-coating metallic plate in case add pigment with higher concentration.
Increase along with chromatic metallic plate application in recent years, the outward appearance that all do not hidden of the tone of a kind of metallic luster that keeps and utilize ground of demand, ground more and more, for example be used for being difficult on the product appearance part of seeing, such as the chassis plate of refrigerator base plate, washing machine base plate and backboard, FDD part, case and be used for those and need the metallic luster part from design viewpoint.Because from design aspect, be bad if those parts that are difficult to see keep the outward appearance of ground metallic plates, what need is that color and luster is bright and kept the coloring metal plate of metallic luster, says nothing of the part that needs metallic luster.
Because this class has the usually preferred golden coloring of the metallic plate of metallic luster and good design, therefore carries out chromate traditionally and handles.Handle by chromate, the yellow film that mainly contains the hydrate of chromium and oxide is gone up golden and with the gloss of ground metallic plate.Yet as mentioned above, it is unstable that the tone of this class chromate film becomes easily along with the carrying out of reduction process.The method that formation has special glossy film is called ＂ unichro ＂, and is well-known, and it is different from common chromate and handles.This method comprises in a kind of glossiness zinc-plating material immersion sulfuric acid solution or the salpeter solution, and this material immersed added in the solution of chromic acid and oxidant, produce a kind of surface treated metallic plate thus with higher gloss degree, but owing to taken place to produce chromic variation, this ＂ unichro ＂ method also is difficult to obtain stable tone.
Disadvantageously, if the metallic plate of handling through chromate is exposed in the wet environment often in practical application, just has the small additions of chromium ion and from chromate film, be dissolved out.In the chromium ion, hexavalent chromium is dangerous to the people, and therefore this dissolving (to environmental emission) is subjected to legal restraint.
Therefore develop a kind of through special chemical surface-treated metallic plate, it has performances such as good anti-corrosive properties, anti-finger printing, lubricity, this metallic plate is made by following method: handle the ground metallic plate with chromate, then on this metallic plate, apply the organic resin transparent membrane of about 1 μ m, suppressed the dissolving of chromium ion thus.Thisly be characterised in that through special chemical surface-treated metallic plate resin molding is transparent; Can see the tone of the ground that chromate was handled by resin molding; The outward appearance of metallic plate is golden.Yet disadvantageously,, increased the weight of Cr coating in the chromate processing procedure,, can not stop the dissolving of chromium even metallic plate has passed through the processing of organic resin coating in order to improve tone stability and anti-corrosive properties.
In order to solve variety of issue of the prior art, the purpose of this invention is to provide a kind of metallic plate that scribbles color resin, this metallic plate can be made by simple equipment, low-cost mode, and stably has an excellent lustrous surface, reflect the tone of coated with resins rete metallic plate before, but also have good anti-corrosive properties and prevent the performance that Cr dissolves; The method of making this metallic plate also is provided.
The present invention relates to a kind of metallic plate that scribbles color resin, scribble a kind of resin molding that contains coloring pigment on the described metallic plate, wherein G
1Satisfy formula given below (1), 60 ° of bright lusters of metallic plate are defined as G with applying before
0, 60 ° of bright lusters of metallic plate are defined as G after the coating color resin film
1
G
0＞G
1≥0.5G
0????(1)
In order to satisfy above-mentioned requirements, the coating weight of importantly color resin being filmed is 0.2-3.0g/m after regulating and being converted into the dry weight of filming
2, in addition, also the content of coloring pigment should be adjusted to the 1-30% of dry coating film weight.Particularly in order to make golden metallic plate, should satisfy following formula (2) with " b " value as " a " value of the psychrometric chroma coordinates of Hunter color difference equation through applying.
-4≤a≤6 and 2≤b≤25 (2)
According to a preferred embodiment of the invention, as the metallic plate before the coated with resins film, its gloss of metallic plate through resin-coating of gained has had significant improvement with galvanized steel plain sheet.Specifically, particularly found as long as the orientation of six side Zn crystal satisfies following formula (3) in the zinc coat
2.0 the orientation coefficient (3) of the orientation coefficient of≤(002) face/(103) face and/or as long as in the arbitrary face on observed zinc coat surface, oriented growth its surface area of face that length is no more than the Zn monocrystalline of 5 μ m and is no more than 70% of viewed this arbitrary face total surface area, just can make the metallic plate that scribbles color resin with excellent metallic luster.
In order to make the metallic plate that scribbles color resin, also comprised among the present invention with containing the water-dispersion type of coloring pigment or the method that the manufacturing of water-soluble type coating scribbles the metallic plate of color resin.
It is a kind of metallic plates that scribble color resin with excellent metallic luster that the present invention has the aspect of characteristics most.According to the present invention, the glossiness G of the metallic plate that color resin applied
1Should be color resin film form before the glossiness G of metallic plate (hereinafter claiming " original metal plate " sometimes)
01/2 or higher, i.e. G
1Be not less than 0.5G
0In other words, G
1Should satisfy following formula (1).Wherein, G of the present invention
0And G
1Be by JIS Z 8741 defined 60 ° of mirror surface lusters, by Nippon Denshoku, the gloss meter that Co.L+d. makes records.
G
0＞G
1≥≥0.5G
0????(1)
If G in the following formula
1＜0.5G
0, there is notable difference in appearance through the metallic plate and the original metal plate of resin-coating, this just means the color harmony gloss that does not reflect original metallic plate, or has not given play to good gloss.Therefore among the present invention above-mentioned requirements is defined as basic demand.After color resin was filmed and formed, the light reflex took place in the interface between original metal plate and resin coating film.Therefore G can not take place in fact
1〉=G
0Situation.On the contrary, if G
1〉=G
0(if not G
0＞G
1), apply color resin and just bring into play less than any effect.
For instance, if also contain metal dust (Al powder, Zn powder etc.) in containing the cold coating of coloring pigment (hereinafter only abbreviating " coating " sometimes as), these metal dusts in the resin coating film will reverberation, thereby G finally occurred
0≤ G
1Situation.Because these metal dusts are gray nearly all, thereby be unfavorable for producing other beautiful tone, and, because the metal dust with larger specific gravity is disadvantageous with regard to it with regard to the dispersiveness in the coating, can cause outward appearance inhomogeneous or cause coating performance to descend such as anti-corrosive properties.In addition, consider that cost improves this shortcoming, does not advise using metal dust yet.
In order to satisfy the above-mentioned formula (1) among the present invention, it is 0.2-3.0g/m that suggestion makes the coating weight of resin coating film on the original metal plate
2(being converted into the dry weight of filming).If coating weight is lower than 0.2g/m
2, resin coating film has only extremely weak coloring effect on the original metal plate.Because the solid content in the coating can be very low, thereby be difficult to be formed uniformly a coating film on original metal plate surface, in addition, such as anti-corrosive properties and operability one class very important performance can not be satisfactory concerning the metallic plate that scribbles resin.
If the coating weight of filming is very big, will improves a lot to the covering power of original metal plate, thereby satisfy above-mentioned formula (1).If the coating weight of filming is higher than 3.0g/m
2, filming just needs drying for a long time, causes continuous production efficiency to reduce, and increases the consumption that contains pigmental resin coating, and its result has just improved expense.In addition owing to film in the pressure operation process and peel off easily, thereby anti-corrosive properties can reduce, and the film that peels off can accumulate on the mould, are unfavorable for compression molding.Preferably, under the prerequisite that does not produce these shortcomings, the coating weight higher limit of resin coating film of the present invention is 3.0g/m
2Or it is lower.Consider that from practical application the coating weight of preferred resin coating film is at 0.3-2g/m
2Scope in.
The coating weight part of filming except adjusting, the concentration of regulating pigment in the coating also are for satisfying the method for the preferred employing of formula (1) institute.Among the present invention, the concentration of coloring pigment should be adjusted to the 1-30% that accounts for the dry weight of all filming (coating solid content) in the coating.If the concentration of coloring pigment less than 1% weight portion, has just reduced the coloring effect to filming, be unfavorable for purpose of the present invention.On the contrary, pigment concentration is higher, and coloring effect just increases.Because resin coating film is tending towards variation to the adhesion of original metal plate, Gu and the suggestion higher limit is 30% weight portion.If pigment is too much in the coating, will reduce as the anti-corrosive properties of resin coating film key property, the tone of filming after causing unfriendly corroding changes.The concentration range of pigment is the 5-20% of dry weight (coating solid content) of filming in the preferred coating.
For the metallic plate that scribbles color resin of the present invention, preferably use a kind of coating that contains particulate colored pigment, described pigment favorable dispersibility in coating.Can mix the tone of various resin-coating metallic plate in conjunction with various pigment.
It is as follows to be used for the following versicolor pigment type of giving an example:
Red; Organic pigment such as insoluble azo colour (naphthols pigment or N-anilide pigment) or solubility AZOpigments, and inorganic pigment such as iron oxide red, cadmium red and red lead;
Yellow: organic pigment such as insoluble even oxygen pigment (tea phenol pigment or N-anilide pigment).Solubility AZOpigments and quinacridone pigment, inorganic pigment such as chrome yellow, cadmium yellow, nickel titanium yellow and strontium chromate;
Green: organic phthalocyanine color;
Blue: organic phthalocyanine color, barba hispanica, ultramarine, cobalt blue and emerald green;
Black: organic pigment such as nigrosine and carbon black, inorganic pigment such as iron oxide black;
White: inorganic pigment such as titanium oxide, calcium carbonate, zinc oxide, barium sulfate, lithopone and white lead.
Homochromy pigment or not homochromy pigment that two or more chemical constitutions in the above-mentioned coloring pigment are different mix by proper proportion, just can go up required color such as grey, brown, purple, orange and golden.
The average grain diameter of coloring pigment is preferably 0.05-1.0 μ m.If particle diameter less than 0.05 μ m, a little less than the coloring effect of film, sees it is disadvantageous from good design aspect.On the contrary, if particle diameter is greater than 1.0 μ m, along with the increase of pigment concentration, the ratio that is exposed to the big granules of pigments of coating surface will raise, just may cause the prepared metallic plate pigment in sliding process that scribbles color resin to come off, and may influence the change of tone.In addition, the particle diameter of pigment is big more, and its dispersiveness in coating is just poor more, just is not easy to produce evenly painted filming.The particle diameter of this class pigment is more preferably in the scope of 0.1-0.7 μ m.
As constituting the basic resin that color resin is filmed in the coating, available is polyvinyl resin, polyurethane resin, mylar, epoxy resin, acrylic resin etc., does not limit especially.Preferably by in basic resin, introducing functional group to improve the adhesiveness of basic resin to coloring pigment.In addition, because organic solvent type coating can produce adventurous working environment, and therefore need the reclaimer of solvent flashing, so water-dispersed paint or the water-soluble type resin solution that contains coloring pigment used in suggestion.
In order to prepare this coating, can suitably in coating, add various additives to improve adhesiveness and anti-corrosive properties, gap material, retarder thinner, sealant, levelling agent, defoamer, bleeding agent, coalescents, thickener, lubricant, finely powdered silica, cataloid and silane coupler are striden in these additives such as part, its amount ranges can not make the metallic plate that scribbles color resin of the present invention, and great changes will take place aspect outward appearance and tone, can further improve the coating performance of filming thus.
As mentioned above, the invention provides the metallic plate that scribbles color resin of the original metallic plate gloss of reflection; In addition, the present invention has successfully developed a kind of metallic plate that scribbles color resin that has the chromate film tone, and this point is that the user especially needs.More particularly, if make the psychrometric chroma coordinates value " a " of JIS Z 8730 defined Hunter color difference equations and " b " satisfy following formula (2), the metallic plate through resin-coating of the present invention just can have the gold that is similar to chromate film.
-4≤a≤6 and 2≤b≤2 5 (2)
Wherein, " a " value of numerical value form and the representative of " b " value demonstrate the chromatic value of the tone of JIS approval, and wherein " a " value is the green that (-) interval scale strengthens, the redness that " a " value strengthens for (+) interval scale; The blueness that " b " value strengthens for (-) interval scale, b " yellow that strengthens for (+) interval scale of value.For " a " value and " b " value are in the above-mentioned scope, only adding yellow uitramarine in coating just can be satisfactory, but also is preferably in conjunction with two or more yellow or red pigment, because the adjusting of colourity is easy to accomplish.
As the metallic plate that applies any resin molding original metal plate before, the wide range of Available Material comprises AlAl alloy sheets, CuCu alloy sheets and TiTi alloy sheets in the present invention; The various above-mentioned metallic plates that are coated with ZnZn alloy or AlAl alloy, plating Cu, plate Ni, plating Cr etc.; And, also have various alloy-steel plates such as low carbon steel plate or corrosion resistant plate in addition with the chemical treatment metallic plate that phosphate or chromate are handled.
In the above-mentioned material, galvanized steel plain sheet has excellent appearance and lustrous surface, thereby this plate is preferred for making the metallic plate that scribbles color resin that can reflect the color harmony gloss of original metallic plate of the present invention.Reason is if the good luster of original metal plate, and the gloss that then applies behind the color resin also should be excellent.Found that the crystal orientation in the zinc coat is influential to lustrous surface, thereby most preferably with having the galvanized steel plain sheet of following performance as original metal plate of the present invention.
The galvanized steel plain sheet of selecting to have six side's zinc crystal in the zinc coat and satisfying following formula (3) is as preferred original metal plate.
2.0 the orientation coefficient (3) of the orientation coefficient of≤(002) face/(103) face
Known Zn crystal is present in the close-packed hexagonal crystal structure.In addition, most of Zn crystal all are oriented in (002) face and (103) face, but crystal mainly is oriented in the part of (103) face in the coating, and the density of its specular light line is lower than the density of incident ray, and the surface gloss of gained is also poor in the part of (002) face than crystal orientation.Therefore, the steel plate with the Zn coating that satisfies above-mentioned condition (being that crystal mainly is oriented in (002) face) is preferably used as the metallic plate that scribbles color resin of the present invention.
Each orientation coefficient numeric representation in the following formula compares by the orientation intensity with the orientation intensity of each minute surface (002 and 103 faces) and non-anisotropic powder sample and to calculate.More particularly, measure the diffracted intensity I (hkl) of (hkl) face in 2 θ=30-85 ° scope by X-ray diffraction, calculate the relative intensity IF (hkl) of I (hkl) to whole peak value diffracted intensity ∑ I (hkl), be I (hkl)/∑ I (hkl), and with the relative intensity IFR (hkl) of the relative intensity that calculates, just recorded the orientation coefficient of (hkl) face divided by Powder samples (can obtain) by the ASTM method.The orientation coefficient of independent measurement (002) face and (103) face, respectively being worth in the introduction-type (3) gained then, the gained intensity that calculates thus is 2.0 or higher, and it is relatively low to prepare a kind of (103) face glossiness numerical value, thereby the good zinc coat of overall shine degree.Unspecial qualification higher limit, but see that from the operability aspect suggestion is defined as 15.If higher limit is higher than 15, in operating process, cause peeling phenomenon easily.Japan Patent discloses the above-mentioned phenomenon of describing galvanized steel plain sheet among the flat 7-2939 in detail.
The present invention preferably uses following galvanized steel plain sheet: wherein the oriented growth surface area of face of the Zn monocrystalline of length 〉=5 μ m account for viewed arbitrary face in the steel plate zinc coat total surface area 70% or still less.
Here, " oriented growth the face of Zn monocrystalline " is meant following situation: the Zn monocrystalline that is plated on the coating surface is by the assigned direction growth (oriented growth form) that is in line, rather than arbitrarily growth.Because tiny raised or sunken before zinc-plated on the steel plate or because other influence, exist inhomogeneous crystal situation, if yet it is excessive the face of Zn monocrystalline along simple interest, even if only there is the situation of the slight inhomogeneous crystal of this class on the surface, also can tell tone difference significantly.When using this original metal plate, its definition performance of metallic plate through resin-coating of gained can descend.
Find that based on these above-mentioned this condition is confirmed as preferred necessary condition: the surface area of face that oriented growth the Zn monocrystalline of length 〉=5 μ m account for the viewed gross area 70% or still less.If the Zn monocrystalline is very little, even Zn monocrystalline oriented growth, the definition performance that has applied the metallic plate of resin can obviously not reduce yet.The length that is included in the Zn monocrystalline in the demand scope should 〉=5 μ m.Because it is functional to satisfy the original metal plate uniform hue and the definition of above-mentioned requirements, if therefore be used for the present invention, this original metal plate just can provide the metallic plate that scribbles color resin of outward appearance grace.
Now then narrate the manufacture method of the metallic plate that scribbles color resin among the present invention.This metallic plate through resin-coating can be made by the following method: a kind of coating (being preferably a kind of water-dispersed paint) that contains above-mentioned resinous principle and above-mentioned coloring pigment is coated on the surface of original metal plate dry then this coating with known method.Do not limit painting method is special, for example comprise a kind of method: the surface of cleaning long size metal tape with following steps, then also preliminary treatment (for example handling with phosphate or chromate) is carried out on this surface as needs, apply coating with methods such as roll coating process, spraying process, curtain coating methods, and make the gained metal tape pass hot-air drying stove to make it dry.Generally consider uniformity, producing cost and the coating efficiency of coating thickness, it is preferred adopting roll coating process from practical significance.According to different purposes, the original metal plate can form color resin and film on a face or two faces.In order to prevent because the tone variations that the change of coloring pigment causes, the baking temperature of filming preferably should be lower than add the heat resisting temperature of coloring pigment.
In order to improve adhesiveness and antiseptic property to resin coating film, the metallic plate that pending resin coating film is handled before applying through the preliminary treatment of phosphate or chromate aptly.For carrying out the material that chromate is handled, the aspect that the chromium dissolving in use takes place from prepared metallic plate through resin-coating considers, the weight of the Cr coating of handling through chromate should be suppressed at and be lower than 35mg/m
2In this scope, instead can suppress chromium through the metallic plate of resin-coating among the present invention and from the bottom that chromate was handled, be dissolved out.
In addition, be arranged on the top coat of carrying out as required often showing on the material that chromate handles, its water-fast adhesiveness is tending towards reducing along with chromic dissolving in wet environment, but in the metallic plate of resin-coating, suppressed this dissolving owing to of the present invention, so the water-fast adhesiveness of top coat does not reduce fully.
The present invention will elaborate in an embodiment, but the present invention is not limited to these embodiment.Under the prerequisite that does not depart from the spirit of the present invention described in the context, also comprise the changes and improvements in the technology of the present invention scope.Embodiment 1
The basic resin of filming as formation with water-dispersion type polyvinyl resin emulsion, and with organic pigment shown in 10% (weight) solid content adding table 1 and inorganic pigment (average grain diameter is 0.2-0.5 μ m) with different tones, just made the water-dispersed paint that contains coloring pigment, i.e. ＂ A-＂ F ＂.Here, coating " G " and " H " have used the organic pigment mixture.As a comparison case, prepared a kind of only the formation and do not added the coating " I " of any pigment by polyethylene emulsion.
Table 1
*C.I. value: the chemical composition of pigment of representing a kind of numeric representation of usefulness 5 figure places.
| Coating | Coloring pigment | Note | |||
| Color | C.I. be worth | Concentration in coating (is converted into solid content; Wt%) | Particle diameter μ m | ||
| ?A | Red | ??20730 | ????10 | ??0.5 | Embodiment |
| ?B | Yellow | ??21108 | ????10 | ??0.5 | |
| ?C | Blue | ??74160 | ????10 | ??0.3 | |
| ?D | Green | ??74260 | ????10 | ??0.2 | |
| ?E | Black | ??77260 | ????10 | ??0.3 | |
| ?F | In vain | ??77891 | ????10 | ??0.3 | |
| ?G | Purple | ??74160 | ?????2 | ??0.3 | |
| ??20730 | ?????8 | ||||
| ?H | Ash | ??77260 | ?????2 | ??0.3 | Comparative Examples |
| ??77891 | ?????8 | ||||
| ?I | Colourless | ???— | ?????0 | ||
The cold-rolled steel sheet of using the Al deoxidation then carries out zinc-plated as the ground steel plate according to the following steps.
(1) alkali cleaning oil removing
Use 60 ℃ 3% the sodium orthosilicate aqueous solution.
(2) electrolytic degreasing → washing
At 60 ℃, 20A/dm
2Condition under use 3% the sodium orthosilicate aqueous solution.Wash then.
(3) pickling → washing
Use 5% aqueous sulfuric acid, washing then in 60 ℃.
(4) zinc-plated → washing
Before washing, zinc-plated under the following conditions.The composition of galvanizing solution:
ZnSO
4·7H
2O???????????300～400g/l
Na
2SO
4????????????????50～100g/l
H
2SO
4The temperature of 25～35g/l galvanizing solution: the flow velocity of 50～70 ℃ of galvanizing solutions: 0.8～2.4m/sec current density: 30～150A/dm
2Zinc coating weight: 20g/m
2
In following embodiment 3 and 4, under zinc-plated condition, in bathing, pickling added an amount of quaternary ammonium salt, thereby the ratio (hereinafter being called " oriented growth rate ") that makes oriented growth arbitrary face total surface area in the surface area of face of the above Zn monocrystalline of length 5 μ m and the observed galvanized steel plain sheet coating is 70% or still less, thus in the coating in (002) face the orientation coefficient of six side Zn crystal can reach the twice of six side Zn crystal orientation coefficients in (103) face or many times.Zinc-plated condition can be improved in scope mentioned above.
The galvanized steel plain sheet of gained is carried out chromate handle that (the Cr coating weight is 20mg/m
2), the original steel plate that this steel plate is used as coated with resins then.In addition, the bright luster of original steel plate (is measured by the following method, hereinafter is called " G before the coating
0") be 60.The oriented growth rate is 0.51.Can cross coating roller and on this steel plate, apply the various coating solutions " A " shown in the table 1 to " I ", steel plate is moved in the hot-air drying stove, make the coating drying with given thickness.The steel plate of the various resin-coating of usefulness of gained is again through following performance evaluation test.The results are shown in table 2 and 3.(1) glossiness
Use Nippon Denshoku, the gloss meter that Co.Lrd. produces is pressed the method for JIS Z8741 regulation and is measured 60 ° of mirror surface lusters (G60).60 ° of mirror surface lusters of original steel plate are decided to be G
0, and the bright luster after the coated with resins is decided to be G
1, calculate expression and apply the chatoyant numerical value G in front and back
1/ G
0(2) outward appearance
By judging with observing to examine whether steel plate reflects the tone of original steel plate after resin is enameled in coating.Evaluation criterion is as follows: the reflectivity to the original steel plate tone is estimated the ◎ excellence: the tone of reflection original steel plate, * bad: the tone that does not reflect original steel plate.(3) tone (colourity)
The colorimeter measurement of producing with Nippon Denshoku Co.L+d press psychrometric chroma coordinates value " a " and " b " in the Hunter color difference equation that JIS Z 8730 defines, through the chrominance C of the metallic plate of resin-coating
1=(a
2+ b
2)
1/2Calculated.Similarly measure the chrominance C of original metal plate
0, the difference △ C=C of calculating colourity
1-C
0Thereby, by following standard evaluation colourity.Chromaticity evaluation method ◎ excellence: colourity difference 〉=8, zero are good: colourity difference 〉=2, but＜8, * bad: colourity difference＜2.(4) anti-corrosive properties (anti-white rust)
Carry out spray testing by JIS Z 2371 usefulness 5% (weight) salt solution, to measure anti-corrosive properties through the metallic plate of resin-coating.Measurement has the pure zinc coating of resin coating film bottom the required time of 1% white rust to occur, and presses following standard evaluation: the ◎ excellence; It is good white rust required time 〉=240 hour zero to occur: occur white rust required time 〉=120 hour and＜△ was poor slightly in 240 hours: occur white rust required time 〉=48 hour and＜120 hours * bad: white rust required time＜48 hour appear
Table 2
| Numbering | Coating type | Coating weight (the g/m that films 2) | Gloss changes G 1/G 0 | Outward appearance | Colourity | Anti-corrosive properties | Note |
| ?1 ?2 ?3 ?4 | ??A ??A ??A ??A | ????0.3 ????0.8 ????1.5 ????2.7 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| ?5 ?6 | ??A ??A | ????0.1 ????3.2 | ????1.0 ????0.4 | × × | × ◎ | × ◎ | Comparative Examples |
| ?7 ?8 ?9 10 | ??B ??B ??B ??B | ????0.4 ????0.8 ????1.5 ????2.8 | ????0.9 ????0.8 ????0.7 ????0.3 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| 11 12 | ??B ??B | ????0.1 ????3.1 | ????1.0 ????0.4 | × × | × ◎ | × ◎ | Comparative Examples |
| 13 14 15 16 | ??C ??C ??C ??C | ????0.4 ????0.8 ????1.5 ????2.8 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| 17 18 | ??C ??C | ????0.1 ????3.1 | ????1.0 ????0.4 | × × | × ◎ | × ◎ | Comparative Examples |
| 19 20 21 22 | ??D ??D ??D ??D | ????0.4 ????0.8 ????1.5 ????2.8 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| 23 24 | ??D ??D | ????0.1 ????3.2 | ????1.0 ????0.3 | × × | × ◎ | × ◎ | Comparative Examples |
| 25 26 27 28 | ??E ??E ??E ??E | ????0.3 ????0.6 ????1.4 ????2.7 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | ○ ○ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| 29 30 | ??E ??E | ????0.1 ????3.1 | ????1.0 ????0.4 | × × | × ◎ | × ◎ | Comparative Examples |
Table 3
| Numbering | Coating type | Coating weight (the g/m that films 2) | Gloss changes G 1/G 0 | Outward appearance | Colourity | Anti-corrosive properties | Note |
| ?31 ?32 ?33 ?34 | ????F ????F ????F ????F | ????0.4 ????0.8 ????1.5 ????2.8 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | ○ ○ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| ?35 ?36 | ????F ????F | ????0.1 ????3.1 | ????1.0 ????0.4 | × × | × ◎ | × ◎ | Comparative Examples |
| ?37 ?38 ?39 ?40 | ????G ????G ????G ????G | ????0.4 ????0.8 ????1.5 ????2.8 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| ?41 ?42 | ????G ????G | ????0.1 ????3.1 | ????1.0 ????0.4 | × × | × ◎ | × ◎ | Comparative Examples |
| ?43 ?44 ?45 ?46 | ????H ????H ????H ????H | ????0.4 ????0.8 ????1.5 ????2.8 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | ○ ○ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| ?47 ?48 | ????H ????H | ????0.1 ????3.1 | ????1.0 ????0.4 | × × | × ◎ | × ◎ | Comparative Examples |
| ?49 ?50 ?51 ?52 | ????I ????I ????I ????I | ????0.3 ????0.8 ????1.5 ????2.7 | ????0.9 ????0.8 ????0.7 ????0.5 | ◎ ◎ ◎ ◎ | × × × × | ○ ◎ ◎ ◎ | Comparative Examples |
All embodiment satisfy the formula (1) of the present invention's regulation: G
0＞G
1〉=0.5G
0, promptly satisfy 1＞G
1/ G
0〉=0.5 embodiment has excellent outward appearance (tone to the original metal plate has good reflecting properties), colourity and anti-corrosive properties.This may be owing to the coating weight that is in the coloring pigment concentration in the preferable range and films.
On the other hand, not the Comparative Examples in prescribed limit of the present invention (gloss changes G
1/ G
0＜0.5) also have excellent colourity and anti-corrosive properties, but its appearance poor, glossiness is lower, does not reflect the tone of original metallic plate.This is because the coating weight of filming is too high.
If the coating weight of filming is low excessively, just almost do not observe gloss and change, use G
1/ G
0=1.0 expressions.In addition, observe bad colourity.Therefore think that applying color resin does not play a role.Anti-corrosive properties are also very poor, therefore show that this low excessively coating weight is not suitable among the present invention.In addition, the example of a coating " I " that has used not contain coloring pigment has kept the gloss of original metal plate, but much less its colourity is inevitable very poor.Embodiment 2
Prepare the listed coating that contains pigment " J " of table 4 to " L " with the method among the embodiment 1.Make the steel plate that scribbles color resin with the method among the embodiment 1 with these coating, to carry out following benchmark test.
Table 4
*C.I. value: the chemical composition of pigment of representing a kind of numeric representation of usefulness 5 figure places.(5) tone
| Coating | Coloring pigment | Note | |||
| Color | C.I. be worth | Concentration in coating (is converted into solid content; Wt%) | Particle diameter μ m | ||
| ?J | Yellow | 21108 | ????10 | ????0.5 | Embodiment |
| ?K | Orange | 21108 | ????8.5 | ????0.5 | |
| 20730 | ????1.5 | ||||
| ?L | Orange | 21108 | ????7.5 | ????0.5 | |
| 20730 | ????2.5 | ||||
The method of pressing among the embodiment 1-(2) is measured psychrometric chroma coordinates value " a " and " b ".(6) outward appearance (with the tone contrast after the chromate processing)
Whether the metallic plate that scribbles color resin is had the tone identical with chromate processing back is estimated.Evaluation criterion is as follows:
Compare evaluation ◎ excellence with the tone after chromate is handled: the tone after handling with chromate is identical, * bad: different with the tone after chromate is handled.(7) anti-Cr dissolubility
50 anti-Cr dissolubilities that are of a size of the steel plate that scribbles color resin of 70mm * 70mm have below been measured.Method of testing: (1) uses the fluorescent x-ray analysis analytic sample back side and the positive thickness of going up the Cr coating, the average Cr coating weight (mg/m on the back side of working sample and the front
2).(2) sample being immersed pH value is in 11 80 ℃ the NaOH aqueous solution, then with sonicated 2 minutes.(3) the gained sample is immersed in the pure water of 80 ℃ of 500ml, then use sonicated 2 minutes.This process repeats twice.(4) to the dissolving that obtains by above-mentioned steps (2) and (3) add 10ml hydrochloric acid in the solution of Cr (solution in the 500mlNaOH aqueous solution and 1000ml water), then heating and volume finally is concentrated into 100ml.(5) with methyl iso-butyl ketone (MIBK) sexavalence Cr is extracted concentrated extract, the Cr (mg/m of the per unit test chart area dissolving of usefulness Atomic Absorption Spectrometry sample from the solution that heats and concentrate
2).(6) the Cr meltage in the usefulness above-mentioned steps (5) has just recorded Cr dissolution rate (%) divided by the average Cr coating weight in the above-mentioned steps (1).
By the anti-Cr dissolubility of following standard evaluation: anti-Cr dissolubility ◎ excellence: Cr dissolution rate＜0.01%, zero is good: Cr dissolution rate 〉=0.01% also＜0.1%, * bad: Cr dissolution rate 〉=0.1%.
Table 5
| Numbering | Coating type | Coating weight (the g/m that films 2) | Tone | Outward appearance | Anti-Cr dissolubility | Note | |
| The a value | The b value | ||||||
| ??53 ??54 ??55 ??56 | ??J ??J ??J ??J | ????0.4 ????0.8 ????1.5 ????2.8 | ??-2.5 ??-2.8 ??-3.2 ??-3.9 | ??5.0 ??11.2 ??18.3 ??24.4 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | Embodiment |
| ??57 ??58 ??59 | ??J ??J ??J | ????0.1 ????3.1 ????0.5 | ??-2.4 ??-4.0 ??-5.0 | ??3.2 ??16.2 ??10.1 | × × × | × ◎ ◎ | Comparative Examples |
| ??60 ??61 ??62 ??63 | ??K ??K ??K ??K | ????0.4 ????0.8 ????1.5 ????2.8 | ??-2.6 ??-2.9 ??-3.3 ??-3.8 | ??4.1 ??10.7 ??17.5 ??23.6 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | |
| ??64 ??65 ??66 | ??K ??K ??K | ????0.1 ????3.1 ????0.5 | ??-2.4 ??-4.0 ??-5.2 | ??2.5 ??15.0 ??10.3 | × × × | × ◎ ◎ | |
| ??67 ??68 ??69 ??70 | ??L ??L ??L ??L | ????0.4 ????0.8 ????1.5 ????2.8 | ??-2.9 ??-3.0 ??-3.1 ??-3.5 | ??3.6 ??9.5 ??15.4 ??23.6 | ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ | |
| ??71 ??72 ??73 | ??L ??L ??L | ????0.1 ????3.1 ????0.5 | ??-2.4 ??-4.0 ??-5.2 | ??2.3 ??15.4 ??8.4 | × × × | × ◎ ◎ | |
Embodiments of the invention have " a " value and " b " value in the prescribed limit of the present invention, so all embodiment have and the identical tone in chromate processing back.In addition, this shows that also these embodiment have excellent anti-Cr dissolubility.On the contrary, Comparative Examples does not form the outward appearance that any chromate is handled, and anti-in other words Cr is poorly soluble.Embodiment 3
In order to make galvanized steel plain sheet, bathe an amount of quaternary ammonium salt of adding to pickling, and in above-mentioned scope, suitably change zinc-plated condition to improve the oriented growth rate by the method for embodiment 1.Use the coating " A " shown in the table 1 and " F " that the galvanized steel plain sheet of gained is carried out resin-coating.Estimate gloss variation, oriented growth rate and the definition performance of every kind of sample (No. 74 to 79, sample), and be listed in the table 6 together.Press following standard evaluation definition performance: ◎ definition excellent performance, zero definition is functional, and * definition performance is bad.
Table 6
| Numbering | Coating type | Coating weight (the g/m that films 2) | The oriented growth rate | Gloss changes G 1/G 0 | Definition performance after the coated with resins | Note |
| ?74 ?75 | ??A ??A | ??0.6 ??0.6 | ????0.51 ????0.65 | ????0.8 ????0.8 | ◎ ○ | Embodiment |
| ?76 | ??A | ??0.6 | ????0.73 | ????0.8 | × | Comparative Examples |
| ?77 ?78 | ??F ??F | ??0.6 ??0.6 | ????0.50 ????0.64 | ????0.7 ????0.7 | ◎ ○ | Embodiment |
| ?79 | ??F | ??0.6 | ????0.72 | ????0.7 | × | Comparative Examples |
Adopted galvanized steel plain sheet among the embodiment 74,75,77 and 78 with the oriented growth rate in the preferable range of the present invention.Therefore, can make the steel plate through resin-coating of definition excellent performance.On the other hand, the definition performance in the Comparative Examples is bad.Embodiment 4
In order to make galvanized steel plain sheet, in pickling is bathed, add an amount of quaternary ammonium salt, and in above-mentioned scope, suitably change zinc-plated condition, to improve in the zinc coating orientation with respect to six side Zn crystal in (002) face of (103) face by the method for embodiment 1.Then carry out resin-coating with the coating among the embodiment 3.Zinc-plated orientation coefficient, the gloss of having estimated every kind of sample change and outward appearance (to the reflectivity of original metal plate tone), and list in the table 7 together.
Table 7
| Numbering | Coating type | Coating weight (the g/m that films 2) | Ratio (002) face/(103) face of zinc-plated orientation coefficient | Gloss changes G 1/G 0 | Outward appearance | Note |
| ??80 ??81 ??82 | ??A ??A ??A | ??0.7 ??0.7 ??0.7 | ????2.2 ????5.0 ????12.0 | ????0.7 ????0.8 ????0.9 | ◎ ◎ ◎ | Embodiment |
| ??83 ??84 | ??A ??A | ??0.7 ??0.7 | ????1.5 ????1.0 | ????0.4 ????0.4 | × × | Comparative Examples |
| ??85 ??86 ??87 | ??F ??F ??F | ??0.8 ??0.8 ??0.8 | ????2.4 ????5.7 ????13.2 | ????0.6 ????0.7 ????0.8 | ○ ◎ ◎ | Embodiment |
| ??88 ??89 | ??F ??F | ??0.8 ??0.8 | ????1.6 ????1.0 | ????0.4 ????0.4 | × × | Comparative Examples |
In a preferred embodiment, the orientation of Zn crystal is two in (103) face or many times in (002) face, has made the metallic plate through resin-coating of outward appearance than Comparative Examples excellence.
Because the present invention is made of the mode of above-mentioned explanation, therefore the present invention can provide a kind of metallic plate that scribbles color resin, it can be with low-cost and simple device fabrication, has stable excellent lustrous surface, can reflect the tone of the preceding original metal plate of coated with resins film, and have excellent antiseptic property and good anti-chromium dissolubility; The method of making this metallic plate also is provided.
Claims (7)
1. one kind is formed with the metallic plate that scribbles color resin that one deck contains the resin coating film of coloring pigment, wherein G on metallic plate
1Satisfy with following formula (1), precondition is that 60 mirror surface lusters of metallic plate were defined as G before the formation color resin was filmed
0, 60 ° of mirror surface lusters of metallic plate are defined as G after the formation resin coating film
1
G
0＞G
1≥0.5G
0????(1)
2. the metallic plate that scribbles color resin of claim 1, wherein the color resin coating weight of filming is counted 0.2-3.0g/m with the dry weight of filming
2, coloring pigment accounts for the 1-30% of the dry weight of filming.
3. claim 1 or 2 the metallic plate that scribbles color resin have golden tone, and wherein ＂ a ＂ value and the ＂ b ＂ value as the psychrometric chroma coordinates of Hunter color difference equation satisfies following formula (2).
-4≤a≤6 and 2≤b≤25 (2)
4. each the metallic plate that scribbles color resin among the claim 1-3, the metallic plate before wherein coated with resins is filmed is a galvanized steel plain sheet.
5. the metallic plate that scribbles color resin of claim 4, the orientation of six side Zn crystal in the zinc coating of galvanized steel plain sheet satisfies following formula (3).
6. claim 4 or 5 the metallic plate that scribbles color resin, wherein in the arbitrary face of the zinc coating of observed fat galvanized steel sheet surface, the surface area that oriented growth the face of length 〉=5 μ m Zn monocrystalline account for observed arbitrary face total surface area 70% or still less.
7. make the method for each the metallic plate that scribbles color resin among the claim 1-6, use water-dispersion type or water-soluble type to contain the coating of coloring pigment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP220899/95 | 1995-08-29 | ||
| JP220899/1995 | 1995-08-29 | ||
| JP22089995 | 1995-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1159368A true CN1159368A (en) | 1997-09-17 |
| CN1124907C CN1124907C (en) | 2003-10-22 |
Family
ID=16758282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96122712A Expired - Lifetime CN1124907C (en) | 1995-08-29 | 1996-08-29 | Metal plate coated with color resin and making method |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100213541B1 (en) |
| CN (1) | CN1124907C (en) |
| TW (1) | TW380059B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844427A (en) * | 2009-03-27 | 2010-09-29 | 株式会社神户制钢所 | Resin-coated zinc plated steel plate |
| CN103287018A (en) * | 2012-03-01 | 2013-09-11 | 株式会社神户制钢所 | Colored resin-coated metal sheet |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050341A (en) * | 1989-12-12 | 1991-04-03 | 马立 | Briquet stove oven for baking amino-finish |
| CN1028896C (en) * | 1992-07-30 | 1995-06-14 | 宣定智 | Galvanized steel pipe with coating at internal and external of it and processing method thereof |
-
1996
- 1996-08-07 TW TW085109576A patent/TW380059B/en not_active IP Right Cessation
- 1996-08-16 KR KR1019960033832A patent/KR100213541B1/en not_active IP Right Cessation
- 1996-08-29 CN CN96122712A patent/CN1124907C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844427A (en) * | 2009-03-27 | 2010-09-29 | 株式会社神户制钢所 | Resin-coated zinc plated steel plate |
| CN101844427B (en) * | 2009-03-27 | 2013-08-07 | 株式会社神户制钢所 | Resin-coated zinc plated steel plate |
| CN103287018A (en) * | 2012-03-01 | 2013-09-11 | 株式会社神户制钢所 | Colored resin-coated metal sheet |
| CN103287018B (en) * | 2012-03-01 | 2016-04-06 | 株式会社神户制钢所 | Pigmentary resin coated metal plate |
Also Published As
| Publication number | Publication date |
|---|---|
| TW380059B (en) | 2000-01-21 |
| KR970011015A (en) | 1997-03-27 |
| KR100213541B1 (en) | 1999-08-02 |
| CN1124907C (en) | 2003-10-22 |
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