CN107429406B - Coated steel plate - Google Patents

Coated steel plate Download PDF

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Publication number
CN107429406B
CN107429406B CN201680019831.0A CN201680019831A CN107429406B CN 107429406 B CN107429406 B CN 107429406B CN 201680019831 A CN201680019831 A CN 201680019831A CN 107429406 B CN107429406 B CN 107429406B
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China
Prior art keywords
epithelium
steel plate
carbon black
coat
zinc phosphate
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CN107429406A (en
Inventor
河村保明
山冈育郎
东新邦彦
石塚清和
冈田克己
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Nippon Steel Corp
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Nippon Steel Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Coated steel plate provided by the invention has: matrix steel plate；The zinc coat being formed on described matrix steel plate；It is formed on the zinc coat, contains trbasic zinc phosphate crystal and adhesion amount is 0.4~2.5g/m2Zinc phosphate coat；It is formed on the zinc phosphate coat, adhesion amount is 50~2000mg/m2It and is inorganic system's epithelium or lower layer's epithelium of organo-mineral complexing epithelium；With the upper layer epithelium being formed on lower layer's epithelium, film thickness is 2.0~10.0 μm and the first carbon black containing 5~25 mass %, wherein, maximal clearance between the interface of the zinc coat and the zinc phosphate coat, the trbasic zinc phosphate crystal is 0.2 μm or less.

Description

Coated steel plate
Technical field
The present invention relates to be suitable for representated by LCD TV, organic EL TV, thin display as plasm TV AV equipment shell etc. coated steel plate.
The Japanese patent application 2015-128016 CLAIM OF PRIORITY that the application was submitted based on June 25th, 2015, and Its content is applied at this.
Background technique
When manufacturing coated steel plate (also referred to as pre-coated steel plate, PCM), coating and baking are implemented to matrix steel plate first, Film is formed on matrix steel plate.After forming film, coated steel plate is coiled into web-like, user is supplied with this state.User will Coil of strip uncoiling is processed by punching, bending, deep-draw or is combined the processing of these processes product is made.
Such coated steel plate is not because cause the deterioration of the operating environment of user side, and user side does not need to be applied Industry is pretended, so being suitable for multiple fields.
The manufacture of coated steel plate is generally carried out in a manner of two two bakings of painting.For two apply two baking modes, firstly, as pre- place It manages and chemical conversion treatment is implemented to matrix steel plate (typically comprising zinc-plated and galvanized alloy galvanized steel plain sheet).Then, it carries out The coating and baking of bottom coating (priming paint).Finally, carrying out the coating and baking of upper coating.
But it for the back side of the surface opposite side with the outside for becoming final products, also uses after the pre-treatment sometimes The coating developed for back side use, carries out coating in a manner of one baking of painting.
It is required that coated steel plate is hard in corrosion resistance (white rust of film end and/or red rust is inhibited to occur), processability, film No matter which kind of will reach high level in the multiple performances such as degree (scratch resistance), stain resistance, resistance to chemical reagents, weatherability.But In recent years, from the viewpoint of the rationalization for reducing cost, environmental protection measure and painting operation, even with wanting for coated steel plate The film in the quality assurance face of appearance design etc. is sought, also requires that film thickness (filming) is thinned.
For example, the coating for the back side of final products such as coated steel plate used in backboard to thin display For steel plate, sometimes requires that and coating thickness is limited in lower than 10 μm.The level of the coating thickness be chemical conversion treatment steel plate, The level of coating thickness required by anti-finger printing steel plate, previous coated steel plate did not require the coating thickness of the level.
If coating thickness is thinned, the organic solvent burning that occurs when can reduce to toast film and what is used burn The burden of furnace (incinerator) is burnt, and the CO thus discharged can be reduced2.Further, since being discharged when film baking organic The amount of solvent depends on coating thickness, so can improve production in the limit of power of incinerator if coating thickness is thinned Linear velocity can be such that painting operation rationalizes.
But if coating thickness is thinned, such as the brightness on coated steel plate surface is deteriorated, or makes because of film difference The tone of coated steel plate generates deviation, or is difficult to cover the scratch of matrix steel plate, is generally difficult to obtain as coated steel plate Good appearance.The invention for the purpose of improving this point is disclosed in patent document 1.In addition, being disclosed in patent document 2 to change Invention for the purpose of the kind coated steel plate corrosion resistance reduction with film filming.
In addition, the burden of the incinerator used as the organic solvent burning generated when reducing to toast film Method, to it is micro containing or be entirely free of the aqueous coating of solvent contained in coating itself and also studied, patent text Offer the invention disclosed using the backboard purposes as thin display and for the purpose of taking into account corrosion resistance in 3.
On the other hand, develop in matrix surface of steel plate formd using water system medical fluid several μm or so film a variety of tables Surface treatment steel plate (such as so-called anti-finger printing steel plate).
For example, Patent Document 4 discloses with the surface treated steel for the purpose of corrosion resistance, thermal diffusivity and electric conductivity Plate.The surface treated steel plate of patent document 4 has double-layer chemical conversion processing skin membrane, in double-layer chemical conversion processing skin membrane The chemical conversion treatment skin membrane at least upper layer contains coloring pigment.
The surface treated steel plate for the purpose of the stabilisation of appearance is disclosed in patent document 5.At the surface of patent document 5 Managing steel plate has double-layer chemical conversion processing skin membrane, and two chemical conversion treatment skin membranes all contain coloring pigment.
It is disclosed in patent document 6 with the surface treated steel plate for the purpose of anti-finger printing and corrosion resistance etc..Patent text The surface treated steel plate for offering 6 is that silica-organic resin composite film is formed on surface of steel plate.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2008-55774 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2010-115902 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2010-247396 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2009-220511 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2013-18192 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2000-263695 bulletin
Summary of the invention
Subject to be solved by the invention
Coated steel plate described in patent document 1,2 and 3 is provided to ensure appearance design and need to make (upper layer) film Film thickness at 2.0 μm or more, and at least have at least one of chemical conversion treatment epithelium and bottom film in its lower section. Therefore, described in the patent document 1,2 and 3 for coated steel plate, it is difficult to coating thickness be thinned.
Surface treated steel plate described in patent document 4 and 5 has at least 1 layer or more in surface of steel plate and contains coloring pigment Chemical conversion treatment epithelium, it is possible to the corrosion resistance of steel plate is influenced because of coloring pigment.
For the surface treated steel plate of patent document 6, the silica-organic resin formed on surface of steel plate is multiple Closing epithelium is substantially transparent epithelium.Therefore, the surface treated steel plate of patent document 6 is sometimes seriously by matrix surface of steel plate The influence of appearance (tone and scuffing).
The present invention has been made in view of the above-described circumstances, and the purpose is to provide a kind of film formed on surface of steel plate Film thickness has excellent scratch resistance and corrosion proof coated steel plate although thin.It should be noted that in the present invention, When " scratch resistance " refers to the Scratch Test as defined in implementing, assigns scuffing to coated steel plate surface, scuffing portion is difficult by visual observation To differentiate.
Means for solving the problems
The present invention in order to solve the above problems and reaches the purpose and takes following means.
(1) coated steel plate of a scheme of the invention has: matrix steel plate；Zinc coat, the Coating process is in described On matrix steel plate；Zinc phosphate coat, the zinc phosphate coat are formed on the zinc coat, containing trbasic zinc phosphate crystal, and are adhered to Amount is 0.4~2.5g/m2；Lower layer's epithelium, lower layer's epithelium are formed on the zinc phosphate coat, adhesion amount be 50~ 2000mg/m2, and be inorganic system's epithelium or organo-mineral complexing epithelium；With upper layer epithelium, which is formed in described On lower layer's epithelium, film thickness is 2.0~10.0 μm, and the first carbon black containing 5~25 mass %, wherein in the zinc coat On the interface of the zinc phosphate coat, the maximal clearance between the trbasic zinc phosphate crystal is 0.2 μm or less.
(2) coated steel plate according to above-mentioned (1), can using lower layer's epithelium contain 10~50 mass % The composition of color pigment.
(3) coated steel plate according to above-mentioned (2), can using lower layer's epithelium contain 10~30 mass % The composition of color pigment.
(4) coated steel plate according to above-mentioned (2) or (3), can use the coloring pigment for the structure of the second carbon black At.
(5) coated steel plate according to above-mentioned (4) can be more than the structure of 100nm using the partial size of second carbon black At.
(6) coated steel plate according to above-mentioned (4) or (5) can be less than using the primary particle size of first carbon black The composition of the primary particle size of second carbon black.
(7) coated steel plate according to either a program in above-mentioned (1)~(6) can contain 5 using the upper layer epithelium The resistivity of~15 mass % being selected from a temperature of 25 DEG C is 0.1 × 10-6~185 × 10-6The boride of Ω cm, carbide, The composition of the non-oxide ceramics particle of one or more of nitride and silicide.
Invention effect
According to above-mentioned each scheme, it is possible to provide the film thickness of the film formed on surface of steel plate has excellent although thin Scratch resistance and corrosion proof coated steel plate.
Detailed description of the invention
Fig. 1 is the schematic diagram for indicating the layer structure of the coated steel plate of present embodiment.
Fig. 2 is the schematic diagram for indicating the measurement method of the maximal clearance between trbasic zinc phosphate crystal.
Fig. 3 is the schematic diagram for indicating the measurement method of the maximal clearance between trbasic zinc phosphate crystal.
Fig. 4 is the grain of contained carbon black in the partial size of contained carbon black and upper layer epithelium in the lower layer's epithelium for indicate present embodiment The schematic diagram of diameter.
Specific embodiment
Hereinafter, being illustrated referring to coated steel plate 1 and its manufacturing method of the attached drawing to embodiment.
(coated steel plate 1)
Firstly, being illustrated to coated steel plate 1.
Fig. 1 is the schematic diagram for indicating the layer structure of coated steel plate 1 of present embodiment.As shown in Figure 1, coated steel plate 1 has It is standby: matrix steel plate 2；Zinc coat 3, the Coating process is on matrix steel plate 2；Zinc phosphate coat 4, the zinc phosphate coat are formed in On zinc coat 3, containing trbasic zinc phosphate, and adhesion amount is 0.4~2.5g/m2, maximal clearance be 0.2 μm or less；Lower layer's epithelium 5, Lower layer's epithelium is formed on zinc phosphate coat 4, and adhesion amount is 50~2000mg/m2, and be inorganic system's epithelium or organic nothing Machine composite film；With upper layer epithelium 6, which is formed on lower layer's epithelium 5, and film thickness is 2.0~10.0 μm, and is contained The first carbon black 7 of 5~25 mass %.
[matrix steel plate 2]
For matrix steel plate 2, there is no particular limitation, and the various steel plates with well known characteristic, chemical composition can be used. In addition, there is no particular limitation for the chemical composition of matrix steel plate 2.
[zinc coat 3]
There is no particular limitation for zinc coat 3, and generally known zinc coat 3 can be used.
The preferably every single side of the adhesion amount of zinc coat 3 is 3~100g/m2.It is lower than every single side 3g/m in the adhesion amount of zinc coat 32 In the case where, corrosion resistance is insufficient, therefore not preferably.In addition, the adhesion amount in zinc coat 3 is more than every single side 100g/m2Feelings Under condition, the processability of zinc coat 3 and the adaptation (adhesiveness) relative to matrix steel plate 2 are reduced, therefore not preferably.
The adhesion amount of preferred zinc coat 3 is every 5~70g/m of single side2。
[zinc phosphate coat 4]
The zinc phosphate coat 4 containing trbasic zinc phosphate crystal is formed on zinc coat 3.
The thickness of zinc phosphate coat 4 is preferably shorter than 1.0 μm, to further increase appearance design, the damage resistant of processing department Property.In addition, there is no particular limitation for the lower limit of thickness, such as 0.3 μm can be enumerated.
The adhesion amount of zinc phosphate coat 4 is 0.4~2.5g/m2.It is lower than 0.4g/m in the adhesion amount of zinc phosphate coat 42When, The scale (thin slice) that the crystallization of zinc phosphate coat 4 is largely generated on the surface of zinc coat 3, cannot get enough scratch resistances, because This is not preferred.On the other hand, if the adhesion amount of zinc phosphate coat 4 is more than 2.5g/m2, then the cohesiveness of zinc phosphate coat 4 drops Low, a possibility that zinc phosphate coat 4 is removed when processing, increases, and addition is led in aftermentioned upper layer epithelium 6 (coloring film) Excellent electric conductivity is seldom arrived when electric pigment, therefore not preferably.
Adaptation and electric conductivity when scratch resistance, processing, the adhesion amount of zinc phosphate coat 4 is more preferable For 0.6~2.0g/m2。
Maximal clearance between the interface of zinc coat 3 and zinc phosphate coat 4, trbasic zinc phosphate crystal is 0.2 μm or less.Pass through phosphorus Maximal clearance between sour zinc crystal is 0.2 μm hereinafter, making it possible to the high zinc coat 3 of hidden L value, and L value reduces, and can make to scratch Deng unobtrusively.On the other hand, in the case that the maximal clearance between trbasic zinc phosphate crystal is more than 0.2 μm, can not hidden zinc coat 3, It is difficult to make the reduction of L value, therefore not preferably.
Maximal clearance between trbasic zinc phosphate crystal is more preferably 0.15 μm or less.L value can be further decreased as a result,.
Fig. 2 and 3 is the schematic diagram for indicating the measurement method of the maximal clearance between trbasic zinc phosphate crystal.
As shown in Figures 2 and 3, it when measuring the maximal clearance between trbasic zinc phosphate crystal, preferably finds out using the following method.It is first First, expose its section the matrix steel plate 2 for being formed with zinc coat 3 and zinc phosphate coat 4 cutting, further the section is carried out Grinding.To the obtained section electron microscope observation, obtain disconnected near the interface of zinc coat 3 and zinc phosphate coat 4 The observation image in face.Measure the trbasic zinc phosphate present in the observation field of view in relation to zinc coat 3 Yu the interface of zinc phosphate coat 4 Maximal clearance between crystal.
The case where observation image of section near the interface of zinc coat 3 and zinc phosphate coat 4 is state shown in Fig. 2 Under, firstly, point A~H of the detection as trbasic zinc phosphate crystal and the contact of zinc coat 3.Then, line segment AB, CD, EF, GH are found out Length, using the length of the line segment with maximum length as the length of the maximal clearance between trbasic zinc phosphate crystal.Feelings shown in Fig. 2 Under condition, the length of maximal clearance of the length of line segment AB between trbasic zinc phosphate crystal.
The case where zinc coat 3 and the interface of zinc phosphate coat 4 are straight line is shown in Fig. 2, as shown in figure 3, in zinc coat 3 In the case where being not straight line with the interface of zinc phosphate coat 4, the maximal clearance between trbasic zinc phosphate crystal is found out in the following manner.It is first First, with Fig. 2 the case where in the same manner as point A '~H ' of the detection as trbasic zinc phosphate crystal and the contact of zinc coat 3.Then, line segment is found out The length of A ' B ', C ' D ', E ' F ', G ' H '.At this point, not being between finding out A ' B ' along the interface of trbasic zinc phosphate crystal and zinc coat 3, C ' Distance between D ', between E ' F ' and between G ' H ', but find out the length for being directly connected to the line segment of two o'clock.The case where with Fig. 2, is same, tool There is the length of maximal clearance of the length of the line segment of maximum length between trbasic zinc phosphate crystal.In the case of figure 3, line segment A ' The length of maximal clearance of the length of B ' between trbasic zinc phosphate crystal.
[lower layer's epithelium 5]
Lower layer's epithelium 5 is formed on zinc phosphate coat 4.Lower layer's epithelium 5 is to improve zinc phosphate coat 4 and upper layer epithelium 6 Adaptation and corrosion resistance for the purpose of and formed.
Lower layer's epithelium 5 is inorganic system's epithelium or organo-mineral complexing epithelium.It, can as the main epithelium ingredient of lower layer's epithelium 5 It enumerates: the silicon compounds such as liquid phase silica, fumed silica and silicate, zirconium compound.Lower layer's epithelium 5 is in addition to master Organic resin can also be contained other than epithelium ingredient.
From the viewpoint of environmental protection, lower layer's epithelium 5 is preferably substantially free of chromium.
The adhesion amount of lower layer's epithelium 5 is preferably 50~2000mg/m2Range.It is lower than in the adhesion amount of lower layer's epithelium 5 50mg/m2When, it cannot get sufficient corrosion resistance, therefore not preferably.If the adhesion amount of lower layer's epithelium 5 is more than 2000mg/m2, then A possibility that cohesiveness of lower layer's epithelium 5 itself reduces, and lower layer's epithelium 5 is removed when processing increases, and adds in upper layer epithelium 6 It is difficult to obtain excellent electric conductivity when adding conducting pigment, therefore not preferably.
Adaptation and electric conductivity when corrosion resistance, processing, the preferred adhesion amount of lower layer's epithelium 5 is 100~1000mg/m2。
From the viewpoint of making to scratch unobtrusively, lower layer's epithelium 5 preferably further contains coloring pigment.Lower layer's epithelium 5 with The mode of recess portion and covering zinc phosphate coat 4 into zinc phosphate coat 4 is formed, and contains coloring pigment by lower layer's epithelium 5, from And the scuffing that epithelium 6 surface in upper layer can be made to generate is more unobtrusively.
The coloring pigment contained in lower layer's epithelium 5 preferably with respect to the weight of lower layer's epithelium 5 be more than 10 mass % and 50 mass % or less.When the amount of the coloring pigment contained in lower layer's epithelium 5 is 10 mass % or less, make to scratch inconspicuous effect Fruit is insufficient, therefore not preferably.When the amount of the coloring pigment contained in lower layer's epithelium 5 is more than 50 mass %, basic medical fluid Ratio is opposite to be reduced, and cannot get sufficient corrosion resistance, therefore not preferably.
As the example of the coloring pigment contained in lower layer's epithelium 5, organic coloring pigments can be enumerated.
As the preferred example of the coloring pigment contained in lower layer's epithelium 5, carbon black (the second carbon black 8) can be enumerated. In the case where lower layer's epithelium 5 contains the second carbon black 8, as its content, the total weight preferably with respect to lower layer's epithelium 5 be more than 10 mass % and 30 mass % or less.When the amount of the second carbon black 8 contained in lower layer's epithelium 5 is 10 mass % or less, make to draw It is insufficient to hurt inconspicuous effect, therefore not preferably.The amount of the second carbon black 8 contained in lower layer's epithelium 5 is more than 30 mass % When, a possibility that differential metals contact corrosion of the second carbon black 8 and zinc coat 3, increases, it is difficult to take into account corrosion resistance, therefore unexcellent Choosing.
In the case where lower layer's epithelium 5 contains the second carbon black 8, the partial size of the second carbon black 8 is preferably greater than 100nm.Pass through The partial size of two carbon blacks 8 is more than 100nm, so that the second carbon black 8 invades reduction a possibility that in the gap of zinc phosphate coat 4. Thereby, it is possible to prevent differential metals contact corrosion, therefore preferably.
" partial size " mentioned here refers to averagely once in the case where carbon black particle individualism present in epithelium Partial size, carbon black particle cohesion and in the presence of refer to indicate cohesion when partial size average aggregate particle size, can by with Under measurement method find out.Firstly, the coated steel plate 1 for being formed with lower layer's epithelium 5 is cut off, expose its section, further The section is ground.To the obtained section electron microscope observation, the observation figure of the section of lower layer's epithelium 5 is obtained Picture.It is selected from the second carbon black 8 present in visual field of image from this several.Then, respective second carbon black 8 is measured Long side length and bond length calculate the average value of these long side lengths and the average value of bond length, then they are equalized To calculate partial size.
If adopted with the aforedescribed process, even if foring upper layer epithelium 6 on lower layer's epithelium 5, the second charcoal can be also found out Black 8 partial size.
In addition, can also find out the partial size of the first carbon black 7 using the above method.
Second carbon black 8 can also be with secondary aggregation in lower layer's epithelium 5.Therefore, not being to the surface treatment of the second carbon black 8 must It needs, the second carbon black 8 that surface treatment is not carried out also can be used.
[upper layer epithelium 6]
Upper layer epithelium 6 is formed on above-mentioned lower layer's epithelium 5, becomes the most surface layer of coated steel plate 1.Upper layer epithelium 6 contains Having the total weight relative to upper layer epithelium 6 is the carbon black (the first carbon black) 7 of 5~25 mass %.
The partial size of the first carbon black 7 in upper layer epithelium 6 is preferably smaller than the partial size of the second carbon black 8 in lower layer's epithelium 5.
Fig. 4 is first for indicating the partial size of the second carbon black 8 contained in lower layer's epithelium 5 and containing in upper layer epithelium 6 The schematic diagram of the partial size of carbon black 7.
As shown in figure 4, no matter in the case where the partial size of the second carbon black 8 is big or partial size is small, not by secondary aggregation In the gap that zinc phosphate coat 4 can be invaded.Thereby, it is possible to prevent the dissimilar metal of zinc coat 3 and the second carbon black 8 from contacting.It is another Aspect, even if in the case where the thickness of upper layer epithelium 6 is thin, it is also preferred that the partial size of the first carbon black 7 is small, so as to show black Degree.
More preferably the partial size of the partial size of the first carbon black 7 and the second carbon black 8 meets following formula (1).Pass through the first carbon black 7 The partial size of partial size and the second carbon black 8 meets following formula (1), can more reliably play above-mentioned effect.
(partial size of the first carbon black)/(partial size of the second carbon black) < 0.5 (1)
The film thickness of upper layer epithelium 6 is 2.0~10.0 μm.It, cannot in the case that on upper layer, the film thickness of epithelium 6 is lower than 2.0 μm Scratch resistance and corrosion resistance are sufficiently obtained, therefore not preferably.In the case that on upper layer, the film thickness of epithelium 6 is more than 10.0 μm, adding Electric conductivity reduces when adding conducting pigment, and economy is deteriorated, therefore not preferably.
The partial size of first carbon black 7 is preferably 50nm or less.Partial size by the first carbon black 7 is 50nm hereinafter, making upper layer The film thickness of epithelium 6 can show sufficient tone for 2.0~10.0 μm.
From scratch resistance, corrosion resistance, weldability and economy aspect, the film thickness of upper layer epithelium 6 is preferably 3.0~ 8.0μm。
Upper layer epithelium 6 can also contain the coloring pigment other than the first carbon black 7.As the coloring face other than the first carbon black 7 The specific example of material can enumerate well known organic pigment and barium sulfate and titanium dioxide etc..On upper layer, epithelium 6 contains first In the case where coloring pigment other than carbon black 7, content is preferably 25 mass % relative to the solid component quality of upper layer epithelium 6 Below.If the content of the coloring pigment other than the first carbon black 7 in upper layer epithelium 6 is more than 25 mass %, resistance to chemical reagents and Barrier property etc. reduces, therefore not preferably.
Upper layer epithelium 6 can also be 0.1 × 10 containing the resistivity at 25 DEG C-6~185 × 10-6The boronation of Ω cm Non-oxide ceramics particle in object, carbide, nitride and silicide.
Since non-oxide ceramics particle is difficult to deteriorate in water, even if in the composition for being used to form upper layer epithelium 6 In the case that object is water system constituent, it is also able to maintain higher conductive energy.Therefore, non-oxidized substance is contained by upper layer epithelium 6 Ceramic particle enables coated steel plate 1 to keep excellent electric conductivity for a long time.
Here, non-oxide ceramics are indicated oxygen-free element or the ceramics made of compound.In addition, boride Ceramics, carbide ceramics, nitride ceramics and silicide ceramics are to indicate to make with boron (B), carbon (C), nitrogen (N), silicon (Si) respectively For the non-oxide ceramics of main nonmetallic constitution element.Resistivity at their 25 DEG C is all 0.1 × 10-6~185 × 10-6Ωcm。
A small amount of non-oxide ceramics particle can have high electric conductivity.Therefore, even if it is non-oxide in upper layer epithelium 6 The content of object ceramic particle be it is a small amount of, coated steel plate 1 can also obtain suitable electric conductivity.If non-oxide in upper layer epithelium 6 The content of object ceramic particle be it is a small amount of, then corrosion resistance and forming caused by non-oxide ceramics particle are contained by upper layer epithelium 6 Property reduce will not become problem.
In addition, the resistivity of pure metal is 1.6 × 10-6Ω cm (Ag simple substance)~185 × 10-6Ω cm (Mn simple substance).It is another Aspect, the resistivity of non-oxide ceramics are 0.1 × 10-6~185 × 10-6Ωcm.It can thus be appreciated that: non-oxide ceramics have With the superior electrical conductivity of pure metal equal extent.
The content of non-oxide ceramics particle in upper layer epithelium 6 is preferably relative to the gross mass of upper layer epithelium 6 to be 0.5 ~20 mass %.If the content of non-oxide ceramics particle be lower than 0.5 mass %, even and if with others electroconductive particles It is also possible to cannot get preferred weldability, therefore not preferably.If the content of non-oxide ceramics particle is more than 20 mass %, The phenomenon that non-oxide ceramics particle stabs electrode then is easy to produce when continuous welding, it is possible to failure welding etc. occur, therefore Not preferably.
The lower limit of the content of non-oxide ceramics particle is preferably 1 mass %, and more preferably 5 mass %, the upper limit is preferably 15 mass %, more preferably 10 mass %.
As non-oxide ceramics particle, can illustrate as follows.
As boride ceramics particle, can exemplify: Group IV (Ti, Zr, Hf), group V in the periodic table of elements (V, Nb, Ta), each transition metal, Mn, Fe, Co, Ni, rare earth element or the Be of group vi (Cr, Mo, W) and the group ii other than Mg The boride ceramics particle of (Ca, Sr, Ba).
But among the boride ceramics particle of Be, the resistivity at 25 DEG C is more than 185 × 10-6Ceramics (the example of Ω cm Such as Be2B、BeB6Deng) particle is possible to that electric conductivity is low, weldability reduces, therefore not preferably.In addition, the boride ceramics of Mg (Mg3B2、MgB2Deng) particle relative to water or acid stability it is low, it is possible to weldability reduce, therefore not preferably.
As carbide ceramics particle, can exemplify: Group IV (Ti, Zr, Hf), group V in the periodic table of elements (V, Nb, Ta), the carbide ceramics particle of each transition metal of VI race (Cr, Mo, W) or Mn, Fe, Co, Ni.
But the carbide ceramics of rare earth element and group ii (such as YC2、LaC2、CeC2、PrC2、Be2C、Mg2C3、SrC2 Deng) particle easy hydrolysis under wet atmosphere, it is possible to weldability reduces, therefore not preferably.
As nitride ceramic particles, can exemplify: Group IV (Ti, Zr, Hf), group V in the periodic table of elements (V, Nb, Ta), the nitride ceramic particles of each transition metal of group vi (Cr, Mo, W) or Mn, Fe, Co, Ni.
But the nitride of rare earth element and group ii (such as LaN, Mg3N2、Ca3N2Deng) particle holds under wet atmosphere Facile hydrolysis, it is possible to which weldability reduces, therefore not preferably.
As silicide ceramics particle, can exemplify: IV race (Ti, Zr, Hf), V race in the periodic table of elements (V, Nb, Ta), the silicide particle of each transition metal or Mn, Fe, Co, Ni of VI race (Cr, Mo, W).
But the silicide of rare earth element and group ii (such as LaSi, Mg2Si、SrSi2、BaSi2Deng) particle is easy It is reacted with water under wet atmosphere and generates hydrogen, it is possible to which weldability reduces, therefore not preferably.
In addition, can be exemplified as non-oxide ceramics particle: being selected from these boride ceramicses, carbide ceramics, nitridation The particle of object ceramics and the mixture of more than two kinds in silicide ceramics mixes these ceramics simultaneously with the bond material of metal Cermet made of being toasted (cermet) particle etc..
In addition, constituting the gold of a part of cermet particle in the case where making upper layer epithelium by water system constituent The standard electrode potential of category is preferably -0.3V or more and has water-fast deterioration.This is because: constituting cermet particle In the case that the standard electrode potential of a part of metal is lower than -0.3V, if the cermet particle long-term existence is in water system group At in object, then particle surface is easy to produce rusty scale or thicker oxidation insulating layer, it is possible to lose the electric conductivity of particle.As resistance to The cermet particle of water deterioration, can enumerate: WC-12Co, WC-12Ni, TiC-20TiN-15WC-10Mo2C-5Ni etc.. The standard electrode potential of Co, Ni are respectively -0.28V, -0.25V, and all higher than -0.3V, two metals all have water-fast deterioration.
From the viewpoint of Environmental, among non-oxide ceramics, Cr system ceramics (CrB, CrB2、Cr3C2、Cr2N、 CrSi etc.) it is undesirable.From the viewpoint of the viewpoint of economy and obtaining easiness, Hf system ceramics (HfB2、HfC、HfN Deng) and heavy rare earth side more than Tb rare earth element system ceramics in major part be undesirable.
Therefore, as the non-oxide ceramics added in upper layer epithelium 6, preferably except Cr system ceramics, Hf system ceramics and ratio The particle or non-oxygen in addition to these ceramics of non-oxide ceramics other than the rare earth element system ceramics of the more heavy rare earth side Tb The particle of the mixture of more than two kinds of compound ceramics.
In addition, stablizing for non-oxide ceramics particle from the circulation of the presence or absence of industrial product and domestic and international market Property, from the perspective of price and resistivity etc., non-oxide ceramics more preferably illustrated below.
That is, non-oxide ceramics particle is more preferably: BaB6(resistivity is 77 × 10-6Ωcm)、CeB6(resistivity 30 ×10-6Ωcm)、Co2(resistivity is 33 × 10 to B-6Ω cm), CoB (resistivity be 76 × 10-6Ω cm), FeB (resistivity 80 ×10-6Ωcm)、GdB4(resistivity is 31 × 10-6Ωcm)、GdB6(resistivity is 45 × 10-6Ωcm)、LaB4(resistivity is 12×10-6Ωcm)、LaB6(resistivity is 15 × 10-6Ωcm)、Mo2(resistivity is 40 × 10 to B-6Ω cm), (resistivity is MoB 35×10-6Ωcm)、MoB2(resistivity is 45 × 10-6Ωcm)、Mo2B5(resistivity is 26 × 10-6Ωcm)、Nb3B2(resistivity It is 45 × 10-6Ω cm), NbB (resistivity be 6.5 × 10-6Ωcm)、Nb3B4(resistivity is 34 × 10-6Ωcm)、NbB2(resistance Rate is 10 × 10-6Ωcm)、NdB4(resistivity is 39 × 10-6Ωcm)、NdB6(resistivity is 20 × 10-6Ωcm)、PrB4(electricity Resistance rate is 40 × 10-6Ωcm)、PrB6(resistivity is 20 × 10-6Ωcm)、SrB6(resistivity is 77 × 10-6Ω cm), TaB (electricity Resistance rate is 100 × 10-6Ωcm)、TaB2(resistivity is 100 × 10-6Ω cm), TiB (resistivity be 40 × 10-6Ωcm)、TiB2 (resistivity is 28 × 10-6Ω cm), VB (resistivity be 35 × 10-6Ωcm)、VB2(resistivity is 150 × 10-6Ωcm)、W2B5 (resistivity is 80 × 10-6Ωcm)、YB4(resistivity is 29 × 10-6Ωcm)、YB6(resistivity is 40 × 10-6Ωcm)、YB12 (resistivity is 95 × 10-6Ωcm)、ZrB2(resistivity is 60 × 10-6Ω cm), MoC (resistivity be 97 × 10-6Ωcm)、Mo2C (resistivity is 100 × 10-6Ωcm)、Nb2(resistivity is 144 × 10 to C-6Ω cm), NbC (resistivity be 74 × 10-6Ωcm)、 Ta2(resistivity is 49 × 10 to C-6Ω cm), TaC (resistivity be 30 × 10-6Ω cm), TiC (resistivity be 180 × 10-6Ω cm)、V2(resistivity is 140 × 10 to C-6Ω cm), VC (resistivity be 150 × 10-6Ω cm), WC (resistivity be 80 × 10-6Ω cm)、W2(resistivity is 80 × 10 to C-6Ω cm), ZrC (resistivity be 70 × 10-6Ωcm)、Mo2(resistivity is 20 × 10 to N-6Ω cm)、Nb2(resistivity is 142 × 10 to N-6Ω cm), NbN (resistivity be 54 × 10-6Ω cm), ScN (resistivity be 25 × 10-6 Ωcm)、Ta2(resistivity is 135 × 10 to N-6Ω cm), TiN (resistivity be 22 × 10-6Ω cm), ZrN (resistivity be 14 × 10-6Ωcm)、CoSi2(resistivity is 18 × 10-6Ωcm)、Mo3(resistivity is 22 × 10 to Si-6Ωcm)、Mo5Si3(resistivity is 46×10-6Ωcm)、MoSi2(resistivity is 22 × 10-6Ωcm)、NbSi2(resistivity is 6.3 × 10-6Ωcm)、Ni2Si (electricity Resistance rate is 20 × 10-6Ωcm)、Ta2(resistivity is 124 × 10 to Si-6Ωcm)、TaSi2(resistivity is 8.5 × 10-6Ωcm)、 (resistivity is 63 × 10 to TiSi-6Ωcm)、TiSi2(resistivity is 123 × 10-6Ωcm)、V5Si3(resistivity is 115 × 10-6 Ωcm)、VSi2(resistivity is 9.5 × 10-6Ωcm)、W3(resistivity is 93 × 10 to Si-6Ωcm)、WSi2(resistivity be 33 × 10-6Ω cm), ZrSi (resistivity be 49 × 10-6Ωcm)、ZrSi2(resistivity is 76 × 10-6Ω cm) particle, from these grains The particle of the mixture of more than two kinds selected in son.
In them, the resistivity at particularly preferred 25 DEG C is 0.1~100 × 10-6The non-oxide ceramics particle of Ω cm. This is because: 25 DEG C of resistivity for passing through non-oxide ceramics particle is 0.1~100 × 10-6Ω cm can be further decreased The content of non-oxide ceramics particle in layer epithelium 6.By reducing containing for the non-oxide ceramics particle in upper layer epithelium 6 Amount can inhibit the formation of the turning circuit of the corrosion current of perforation upper layer epithelium 6, corrosion resistance inhibited to reduce, therefore preferably.Except this In addition, by reducing the content of the non-oxide ceramics particle in upper layer epithelium 6, upper layer skin is induced when may also suppress compression moulding The removing or scuffing of film 6 inhibit the reduction of formability, therefore preferably.
Upper layer epithelium 6 can also contain rust resisting pigment.There is no particular limitation for rust resisting pigment, but is preferably selected from tripolyphosphate Zn, Mg, Al, Ti, Zr and Ce salt, the hydrocalumite of aluminium, phosphoric acid and phosphorous acid treated phosphate cpd (as an example, have: As trbasic zinc phosphate hydrocalumite handle Dong Bang pigment company manufacture EXPERT NP-530N5), Ca ion exchange titanium dioxide Silicon and oil absorption are 100~1000ml/100g, specific surface area is 200~1000m2/ g, average grain diameter are 2~30 μm non- At least one kind of rust resisting pigment in crystalloid silica.
It is excellent among these above-mentioned rust resisting pigments from the viewpoint of improving the corrosion resistance of scuffing portion and planar portions both sides The rust resisting pigment of choosing is phosphate-based rust resisting pigment (aluminium triphosphate, hydrocalumite treated phosphate cpd etc.), dioxy SiClx system rust resisting pigment or the two combination.Particularly preferred rust resisting pigment is selected from aluminium triphosphate, hydrocalumite Treated phosphate cpd, Ca exchange silica, oil absorption are 100~1000ml/100g, specific surface area be 200~ 1000m2It is at least one kind of in/g, the amorphous silica that average grain diameter is 2~30 μm.
The oil absorption of silica can be measured according to JIS K 5101-13-2:2004.The specific surface area of silica It can be measured by BET method.Method same as the average grain diameter of electroconductive particle can be used in the average grain diameter of silica It is measured.
The content of rust resisting pigment is preferably relative to the total solid content quality of upper layer epithelium 6 to be 2.5~20 mass %.
In the case where the content of rust resisting pigment is lower than 2.5 mass %, it is possible to be unable to fully obtain corrosion resistance, therefore not It is preferred that.In the case where the content of rust resisting pigment is more than 20 mass %, it is possible to which the processability and cohesiveness of upper layer epithelium 6 drop It is low, therefore not preferably.
From corrosion resistance and processability aspect, the content of rust resisting pigment is more preferably relative to the total of upper layer epithelium 6 Solid component quality is 5~15 mass %.
Upper layer epithelium 6 can also contain other additives.It as additive, can enumerate: extender pigment, solid lubrication The well-known additives such as agent, levelling agent (leveling agent).
It as extender pigment, such as can enumerate: silica (comprising colloidal silicon dioxide), titanium dioxide, zirconium oxide Deng.The content of extender pigment is preferably relative to the total solid content quality of upper layer epithelium 6 to be 0.1~20 mass %.In constitution In the case that the content of pigment is lower than 0.1 mass %, it is possible to be unable to fully obtain the effect of addition extender pigment, therefore unexcellent Choosing.The upper limit of the content of extender pigment is not particularly limited, but if in the excessively more then upper layer epitheliums 6 of content it is other at The content divided is reduced, it is possible to can not be obtained desired effect, therefore is preferably set to substantially 20 quality % or less.
By adding solid lubricant to upper layer epithelium 6, excellent lubricity, Er Qieneng can be assigned to upper layer epithelium 6 Enough improve chalking resistance, therefore preferably.As solid lubricant, such as polyolefin-wax and paraffin and fluororesin system can be enumerated Wax.
It as polyolefin-wax and the example of paraffin, such as can enumerate: polyethylene wax, synthesis paraffin, natural paraffin wax, micro- wax And chlorinated hydrocabon etc..It as the example of fluororesin system wax, can enumerate: polyfluoroethylene resin (polyflon etc.), poly- fluorine Vinyl and polyvinylidene fluoride resin etc..
The average grain diameter of solid lubricant is preferably 0.05~25 μm.It is lower than 0.05 μm in the average grain diameter of solid lubricant In the case where, because of the surface concentration of lubricant, lubricant occupied area shared by the surface layer of upper layer epithelium 6 increases, it is possible to The adaptation of upper layer epithelium 6 and lower layer's epithelium 5 reduces, therefore not preferably.In addition, the average grain diameter in solid lubricant is lower than 0.05 μm and in the case where upper layer further progress coating (the rear coating) of upper layer epithelium 6, it is possible to upper layer epithelium 6 with pass through Afterwards coating and the adaptation of epithelium that is formed also reduces, therefore not preferably.On the other hand, super in the average grain diameter of solid lubricant In the case where crossing 25 μm, because lubricant is easy to fall off from upper layer epithelium 6, it is possible to be difficult to obtain scheduled lubricity, Er Qienai Corrosion reduces, therefore not preferably.
From obtaining excellent coating adhesion, corrosion resistance, lubricity and chalking resistance aspect, solid lubricant Average grain diameter is more preferably 1~15 μm, further preferably 3~10 μm.
The softening point of solid lubricant is preferably 100 DEG C~135 DEG C, more preferably 110~130 DEG C.If moistening solid The softening point of lubrication prescription is at 100 DEG C~135 DEG C, then lubricity, chalking resistance further increase.
The content of solid lubricant is preferably relative to the total solid content quality of upper layer epithelium 6 to be 0.1~10 mass %. In the case where the content of solid lubricant is lower than 0.1 mass %, it is possible to obtain lubricity with being unable to fully, therefore unexcellent Choosing.In the case where the content of solid lubricant is more than 10 mass %, it is possible to the adaptation of upper layer epithelium 6 and lower layer's epithelium 5 And corrosion resistance reduces, therefore not preferably.
From the adaptation of upper layer epithelium 6 and lower layer's epithelium 5, lubricity and corrosion proof aspect, solid lubricant Content be more preferably relative to upper layer epithelium 6 total solid content quality be 0.2~5 mass %, further preferably 0.5~ 2.5 mass %.
Upper layer epithelium 6 is due to containing the first carbon black 7, so all in all L value is smaller.On the other hand, matrix steel plate 2 and plating The substantially silvery white of zinc layers 3, L value are relatively large.If upper layer epithelium 6 generates scuffing, the appearance of coated steel plate 1 is being observed In the case of, it is possible to see the matrix steel plate 2 or zinc coat 3 of lower layer.In this case, the portion without scuffing of upper layer epithelium 6 It is point larger with the hue difference (difference of L value) of matrix steel plate 2 or zinc coat 3, there is a problem of that scuffing is obvious.
Coated steel plate 1 has on zinc coat 3 contains 0.4~2.5g/m to adhere to meter2Trbasic zinc phosphate phosphoric acid rolled tin Film 4.The L value of zinc phosphate coat 4 is less than matrix steel plate 2 and zinc coat 3.That is, upper layer epithelium 6 and zinc phosphate coat 4 Hue difference is less than the hue difference of upper layer epithelium 6 and matrix steel plate 2 or zinc coat 3.Therefore, by forming phosphoric acid on zinc coat 3 Rolled tin film 4, so that scratching becomes unobvious.
By forming zinc phosphate coat 4 on zinc coat 3, so that foring the recessed of several μm of grades on the surface of zinc coat 3 It is convex.It is believed that causing the diffusing reflection of light by the bumps, so that the L value of zinc phosphate coat 4 is smaller.
Moreover, when being formed with scuffing on the surface of upper layer epithelium 6, it is bad in lower layer's epithelium 5 and the adaptation of zinc coat 3 In the case where good, lower layer's epithelium 5 is easily peeled off, and scuffing is accessible to matrix steel plate 2 or zinc coat 3.
On the other hand, by zinc coat 3 formed zinc phosphate coat 4, then as mentioned above due to zinc phosphate coat 4 it is recessed It is convex, so that the adaptation of zinc coat 3 and lower layer's epithelium 5 improves.Lower layer's epithelium 5 becomes to be not easily stripped as a result, therefore scratches and be difficult to To reaching matrix steel plate 2 or zinc coat 3.
In addition, the part of upper layer epithelium 6 being shaved enters zinc phosphate coat 4 when upper layer epithelium 6 generates scuffing Bump.Since the first carbon black 7 is contained in the part of upper layer epithelium 6 being shaved, even if so scratch, but zinc phosphate coat 4 recess portion blackening scratches unobvious.
In addition, because the coloring pigments such as carbon black and the potential difference of zinc contained in coating and iron are larger, it is possible to make to apply steel loading The corrosion resistance of plate 1 reduces.It is to make the pigment in upper layer epithelium 6 by zinc phosphate coat 4 but for coated steel plate 1 (carbon black etc.) is not constituted with the mode that zinc coat 3 directly contacts.Therefore, coated steel plate 1 has good corrosion resistance.
For coated steel plate 1, upper layer epithelium 6 is formed not instead of not directly on zinc phosphate coat 4, in zinc phosphate coat Lower layer's epithelium 5 is formed between 4 and upper layer epithelium 6.As a result, with upper layer epithelium 6 is directly formed on zinc phosphate coat 4 the case where It compares, the thickness whole as coated steel plate 1 can be reduced.
[back side epithelium]
For coated steel plate 1, be formed in the back side epithelium of product back side is constructed without special restriction.
[purposes]
Coated steel plate 1 is suitable for family's electrical article shell.Coated steel plate 1 is to be formed thinly thus can due to epithelium It is manufactured inexpensively.Therefore, coated steel plate 1 is suitable for the backboard of the AV equipment such as the thin display for requiring especially to be manufactured inexpensively Deng.
(manufacturing method of coated steel plate 1)
Next, being illustrated to the manufacturing method of coated steel plate 1.
[zinc-plated process]
Firstly, forming zinc coat 3 on matrix steel plate 2 and implementing zinc-plated process to matrix steel plate 2.
There is no particular limitation for the specific method of zinc-plated process, can enumerate: plating Zn, electroplating Zn-Ni, plating Zn-Co, Galvanizing by dipping, alloyed hot-dip zinc-coated, hot dip galvanizing -55%Al-1.6%Si, hot dip galvanizing -11%Al, hot dip galvanizing -11% Al-3%Mg, hot dip galvanizing -6%Al-3%Mg, hot dip galvanizing -11%Al-3%Mg-0.2%Si etc..In addition it is also possible to steaming The coating of the methods of plating plating mentioned component.
In zinc-plated process use galvanoplastic in the case where, in the electrolyte containing Zn ion, using matrix steel plate 2 as Cathode and between electrode implement electrolysis processing.By controlling electrolyte composition, current density, electrolysis time, to control Coating adhesion amount on matrix steel plate 2 processed.
In zinc-plated process use hot dipping method in the case where, matrix steel plate 2 is impregnated in maintain it is in a molten state Zn or Zn alloy plating bath in, matrix steel plate 2 is lifted from plating bath.By adjusting the pull rate of matrix steel plate 2, by being located at The flow for cleaning gas for cleaning nozzle ejection, flow velocity above plating bath etc., to control the coating attachment on matrix steel plate 2 Amount.
After plating as described above, by using gas stove, induction heater, they are carried out and are used made of Heating furnace etc. heats the matrix steel plate 2 after foring zinc coat 3 to carry out Alloying Treatment.
About plating operation, any method in the continuous plating method of coil of strip or the plating method of cutting plate monomer can be passed through Carry out plating.
[trbasic zinc phosphate treatment process]
After zinc-plated process, by carrying out trbasic zinc phosphate treatment process, to form zinc phosphate coat 4 on zinc coat 3.Phosphorus There is no particular limitation for the specific method of sour zinc processing, can be used in response type processing, application type processing and electrolysis-type processing Any trbasic zinc phosphate processing.
Response type trbasic zinc phosphate processing in, can by the matrix steel plate 2 for foring zinc coat 3 carried out degreasing, After washing and surface adjustment processing, contacts it with response type treatment fluid and then washed, dried to be formed.At response type Reason liquid is in phosphate ion, nitrate ion and zinc ion aqueous solution as main component containing selected from iron ion, cobalt ions And it is at least one kind of in calcium ion.Response type treatment fluid can also be further containing selected from peroxide, fluoride ion, coordination At least one of fluoride ion and nitrite ion.
It, will be with phosphate ion, nitrate ion and zinc ion phosphoric acid as main component in the trbasic zinc phosphate processing of application type Zinc treatment fluid is coated in at least one side for the matrix steel plate 2 for being formed with zinc coat 3.
Coating method is arbitrary, and in addition to being coated with rolling method, can also be carried out with infusion process or spray coating method After coating, coating weight is adjusted with air knife method or roller extrusion.The surface that trbasic zinc phosphate treatment fluid is coated on to matrix steel plate 2 it Afterwards, it can be dried by using drier, hot-blast stove, high-frequency induction furnace, infrared heating heating furnace to form zinc phosphate coat 4。
Drying means when forming zinc phosphate coat 4 by application type processing is preferably with the arrival plate temperature of matrix steel plate 2 Reach 70 DEG C~400 DEG C of mode to be dried.If arrival plate temperature when dry is lower than 70 DEG C, zinc phosphate coat 4 is done Dry insufficient, zinc phosphate coat 4 is tacky, and not only coating adhesion reduces, but also the epithelium for being formed in 4 upper layer of zinc phosphate coat produces It is raw uneven, therefore not preferably.In addition, cannot get higher effect if reaching plate temperature and being more than 400 DEG C, it is not only uneconomical, and And it is easy to produce the defect of zinc phosphate coat 4, corrosion resistance is deteriorated, therefore not preferably.
From such a viewpoint, the arrival temperature of the matrix steel plate 2 when dry is more preferably 100~300 DEG C, further Preferably 120~170 DEG C.
It, can also be containing selected from nickel ion, manganese ion and magnesium other than containing zinc ion for trbasic zinc phosphate treatment fluid It is at least one kind of in ion.Wherein, in order to further increase the appearance design and scratch resistance of processing department, at trbasic zinc phosphate Liquid is managed, preferably other than containing zinc ion, also contains both magnesium ion and nickel ion.The magnesium ion of trbasic zinc phosphate treatment fluid Content is preferably 5.0~40.0g/l, more preferably 10.0~25.0g/l.The content of the nickel ion of trbasic zinc phosphate treatment fluid is preferably 0.05~2.00g/l, more preferably 0.10~1.50g/l.
In addition, the content of the phosphate ion of trbasic zinc phosphate treatment fluid is preferably 1~20g/l, more preferably 3~10g/l.Phosphoric acid The content of the Zn ion of zinc treatment fluid is preferably 0.1~10g/l, more preferably 1~5g/l.
As electrolysis-type processing, at the electrolysis-type for containing phosphate ion, nitrate ion and zinc ion as main component It manages in liquid, using matrix steel plate 2 as cathode to implementation electrolysis processing between electrode.It is formed with the matrix steel of zinc coat 3 The control of the adhesion amount of zinc phosphate coat 4 on plate 2 can carry out by adjusting electrolyte composition, current density, electrolysis time.
[5 formation process of lower layer's epithelium]
By carrying out 5 formation process of lower layer's epithelium after trbasic zinc phosphate treatment process, so that under being formed on zinc phosphate coat 4 Layer epithelium 5.In 5 formation process of lower layer's epithelium, by the way that basic medical fluid to be coated on zinc phosphate coat 4 and toast, from And form lower layer's epithelium 5.There is no particular limitation for coating and baking method, and well known method can be used.
As basic medical fluid, E300 series, PAINT plants of the Japan of the manufacture of Parkerizing Co., Ltd., Japan can be used The Surf Coat series etc. of formula commercial firm manufacture.In addition, it is contemplated that environmental pressure etc., preferably basic medical fluid is free of chromium.
In addition, can be suitable for adding coloring face in basic medical fluid in the case where lower layer's epithelium 5 contains coloring pigment Material.
[6 formation process of upper layer epithelium]
By carrying out epithelium 6 formation process in upper layer after 5 formation process of lower layer's epithelium, to be formed on lower layer's epithelium 5 Upper layer epithelium 6.In 6 formation process of upper layer epithelium, by the way that basic medical fluid to be coated on lower layer's epithelium 5 and toast, from And form upper layer epithelium 6.There is no particular limitation for coating and baking method, and well known method can be used.
When forming upper layer epithelium 6, for example, may be used at commercially available anti-finger printing steel plate surface epithelium formation in institute The well known basic medical fluid used.Anti-finger printing steel plate, which refers to, to be formed on matrix steel plate (usually clad steel sheet) with polyester It is the steel plate of the film based on resin, polyurethane series resin, acrylic resin or epoxy system resin etc..In such base It is suitable for adding carbon black to make treatment fluid in plinth medical fluid.
Embodiment
More specific description is carried out to the present invention hereinafter, enumerating embodiment.But these each embodiments are not intended to limit this hair It is bright.
[pretreatment process]
By 9 kinds of galvanized steel plain sheets below in water system alkali cleaner (the Japanese Parkerizing company containing 2.5 mass % The FC-301 of manufacture), temperature be impregnate 2 minutes in 40 DEG C of aqueous solution, to surface progress degreasing.Then, to galvanized steel plain sheet into Row washing and drying.
EG2: (plate thickness 0.8mm, coating adhesion amount are 2g/m to plated steel sheet2)
EG5: (plate thickness 0.8mm, coating adhesion amount are 5g/m to plated steel sheet2)
EG10: (plate thickness 0.8mm, coating adhesion amount are 10g/m to plated steel sheet2)
EG20: (plate thickness 0.8mm, coating adhesion amount are 20g/m to plated steel sheet2)
EG40: (plate thickness 0.8mm, coating adhesion amount are 40g/m to plated steel sheet2)
ZL: (plate thickness 0.8mm, coating adhesion amount are 10g/m to plating Zn-10 mass %Ni alloy-steel plate2)
GI: (plate thickness 0.8mm, coating adhesion amount are 60g/m to hot-dip galvanized steel sheet2)
SD: hot dip galvanizing -11 quality %Al-3 mass %Mg-0.2 mass %Si alloy-steel plate (plate thickness 0.8mm, coating Adhesion amount is 60g/m2)
GA: (plate thickness 0.8mm, 10 mass %Fe, coating adhesion amount are 45g/m to alloyed hot-dip galvanized steel plate2)
[trbasic zinc phosphate treatment process]
At normal temperature, Japan has been used to what the surface of the galvanized steel plain sheet after pretreatment process had carried out the stipulated time The spray treatment of Parkerizing corporation titanium colloid system's surface treating agent (pl-z).
Then, 60 DEG C at a temperature of, Japanese Parkerizing corporation has been used to the surface of galvanized steel plain sheet The spray treatment for trbasic zinc phosphate chemical conversion agent (PB-3312) made.It should be pointed out that zinc phosphate coat in order to make each level is attached Amount reach desired adhesion amount, have adjusted the impregnation time in trbasic zinc phosphate chemical solution according to each level,.
Later, galvanized steel plain sheet is transferred in hot-blast stove, is dried in the state that the arrival temperature on surface is 70 DEG C, Form the zinc phosphate coat for reaching regulation adhesion amount.
[formation of lower layer's epithelium]
When forming lower layer's epithelium, both basic medical fluids of p and q are prepared.
Basic medical fluid p is by silane coupling agent (3- glycidoxypropyltrimewasxysilane: 3- Glycidoxypropyltrimethoxysilane), (colloidal silicon dioxide be (manufacture of Nissan Chemical company for silicon dioxide microparticle Snowtex N)), (water dispersible polyurethane resin (the first industrial group manufacture of Zr compound (zirconium carbonate ammonium) and polyurethane resin Superflex E-2000)) made of water system coating composition.
Basic medical fluid q is by silane coupling agent (3- glycidoxypropyltrimewasxysilane), silicon dioxide microparticle (water dispersible polyester resin (spin public by Japan for (colloidal silicon dioxide (the Snowtex O of Nissan Chemical company manufacture)) and polyester resin Take charge of manufacture VYLONAL MD-1200)) made of water system coating composition.
The content of each ingredient in basic medical fluid p and q is as shown in table 1.
The ingredient (wt%) of 1 subfoundation treatment fluid of table
Silane coupling agent Silicon dioxide microparticle Zr compound Polyester resin Polyurethane resin
p 30 20 20 - 30
q 30 40 - 30 -
By adding pigment in above-mentioned basic medical fluid p, q, to make lower layer's epithelium formation treatment fluid.Water removal Other than quasi- p1, in lower layer's epithelium formation with also added C1 (carbon black dispersion liquid (Toyo Ink industrial group system in treatment fluid Make)), C2 (carbon black the MA-100 of manufacture (Mitsubishi Chemical Ind)), P (benzimidazolone (manufacture of Toyo Ink industrial group)) or Pigment more than wantonly 1 type in B (copper phthalocyanine (manufacture of Toyo Ink industrial group)).
Shown in table 2 type and content of basis medical fluid used in each lower layer's epithelium formation treatment fluid and pigment with And the partial size of carbon black when using carbon black as pigment.
Treatment fluid is used in the formation of 2 lower layer's epithelium of table
Lower layer's epithelium formation described in table 2 is coated on galvanized steel sheet surface with treatment fluid with stick rubbing method.Then, it will plate Zinc steel plate moves to hot-blast stove, is dried and air-dries in such a way that the arrival temperature of galvanized steel sheet surface reaches 70 DEG C, zinc-plated Surface of steel plate forms lower layer's epithelium.It should be pointed out that when forming lower layer's epithelium, to reach adhesion amount described in table 5~7 Mode adjust the rugosity of diluting condition and stick.
For level 120, to reach 50mg/m by Cr conversion2Mode be coated with Japanese PAINT SURF CHEMICALS The NRC300 of company's manufacture carrys out lower layer's epithelium formation treatment fluid described in substitution tables 2, is toasted with 130 DEG C, has made chromium Hydrochlorate (Cr) epithelium.
[formation of upper layer epithelium]
When forming upper layer epithelium, resin shown in table 3 and curing agent are mixed by ratio shown in table 3, made Overlying adhesive B1~B8 is made.
The composition of 3 overlying adhesive ingredient of table
It is added to carbon black, conducting pigment, rust resisting pigment, colloidal silicon dioxide and lubricant in overlying adhesive, makes Upper layer epithelium, which is formed, uses treatment fluid, and the composition of the upper layer epithelium formation treatment fluid of each level is shown in table 4.
4 upper layer epithelium of table forms the composition for using treatment fluid
Epithelium formation in upper layer shown in table 4 is coated on treatment fluid by stick spreader and is formed with the zinc-plated of lower layer's epithelium On steel plate, it is dried, is consequently formed using baking oven under the heating condition as reaching 200 DEG C of maximum temperature reached with 30 seconds Upper layer epithelium.The adhesion amount of upper layer epithelium is adjusted by the dilution of coating composition and the rugosity of stick spreader, with So that total adhesion amount of the solid component (nonvolatile component) in coating composition reaches adhesion amount shown in table 4.
In table 4, to the solid component concentration of each ingredient be denoted as the solid component (nonvolatile component) of each ingredient it is opposite In the ratio (value of quality %, single side) of the solid component (nonvolatile component) of entire coating composition.
Each compound used in table 4 is shown in detail below.
(carbon black)
C1: carbon black dispersion liquid (manufacture of Toyo Ink industrial group)
(conductive pigment)
VB: vanadium diboride particle (average grain diameter is 1~3 μm)
VC: vanadium carbide particle (average grain diameter is 1~3 μm)
VN: vanadium nitride particle (average grain diameter is 1~3 μm)
ZS: zirconium disilicide particle (average grain diameter is 1~3 μm)
ZN: zirconium nitride particle (average grain diameter is 1~3 μm)
TN: titanium nitride particle (average grain diameter is 1~3 μm)
SUS:SUS particle (average grain diameter is 3~7 μm)
Ni:Ni particle (average grain diameter is 3~7 μm) (rust resisting pigment)
PA: aluminium triphosphate (average grain diameter is 1~2 μm)
PM: magnesium phosphate (average grain diameter is 1~2 μm)
SC: calcium ion-exchanged silica (average grain diameter is 1~2 μm)
Si: (oil absorption is 100~1000ml/100g to silica, specific surface area is 200~1000m2/ g, average grain diameter Amorphous silica for 1~30 μm) (Sylomask02 of Fuji SILYSIA manufacture)
(colloidal silicon dioxide)
T: colloidal silicon dioxide (average grain diameter is 10~15nm) (the Snowtex N of Nissan Chemical company manufacture)
(lubricant)
PE: polyethylene wax (average grain diameter is 1 μm, softening point is 132 DEG C) (Mitsui Chemicals, Inc.'s system Chemipearl W700)
[performance evaluation]
Performance evaluation has been carried out to the breadboard made according to the above method by the following method and benchmark.Show in table 5~7 The manufacturing conditions of the breadboard of Examples and Comparative Examples are gone out, the breadboard of Examples and Comparative Examples are shown in table 8~10 Evaluation results.
(scratch resistance)
Cold-rolled steel sheet (0.8mm thick) is punched into the disk of 40mm φ, tilts to disk with breadboard into 45 ° of the elevation angle, The scratch of 50mm is implemented on one side the speed withed 10mm/ seconds while load for applying 0.5kg to the direction vertical with disc face.Mesh Appearance of black depending on observing the scuffing portion of scratch, is evaluated by following benchmark.
In the case where scoring is 3 or more, it is judged as that scratch resistance is excellent.
5: the appearance of black indifference in normal portion and scuffing portion.It is looked including scuffing portion outside for uniform black It sees.
4: the appearance of black indifference in scuffing portion, but seem that glossiness slightly changes.
3: can be seen that the appearance of black in scuffing portion varies slightly, but absolutely not expose substrate.
2: can be seen that the appearance of black in scuffing portion changes, there is substrate exposing.
1: can be seen that the appearance of black in scuffing portion has significant change, there is apparent substrate to expose.
(corrosion resistance)
With adhesive tape by the back side of undressed plate and edge seal, 120 hours salt spraytest (JIS-Z- have been carried out 2371:2000).Appearance after observation 120 hours, has rated corrosion resistance by corrosion condition and corroded area rate.
In the case where scoring is 3 or more, it is judged as corrosion resistance excellent.
5: white rust is lower than 2%
4: white rust is 2% more than or lower than 5%
3: white rust is 5% more than or lower than 10%
2: red rust not occurring, white rust is 10% or more
1: red rust occurs, white rust is 10% or more
(adaptation)
Implementation 0T bending (180 ° of bendings) processing, after adhesive tape removing has been carried out on the outside of to bending section, observes film to glue Attachment with side is pressed and states evaluation criteria and evaluated.
In the case where scoring is 2 or more, it is judged as excellent adhesion.
3: adhering in adhesive tape side without film
2: the removing of the painting film stripping of visible several points in adhesive tape side, steel plate side is lower than 10%
1: having painting film stripping in adhesive tape side, the removing of steel plate side is 10% or more
(electric conductivity)
Using tetra- probe assay conductivity of Loresta and measure 20 points.In 20 points for determining conductivity, according to Electric conductivity is evaluated in the number of defined resistance value point below.
In the case where following scorings are 2 or 3, it is judged as excellent electric conductivity.
3:20 point is all below defined resistance value
10~19 points in 2:20 point are below defined resistance value
0~9 point in 1:20 point is below defined resistance value
The manufacturing conditions (1/3) of 5 breadboard of table
The manufacturing conditions (2/3) of 6 breadboard of table
The manufacturing conditions (3/3) of 7 breadboard of table
The Evaluation results (1/3) of 8 breadboard of table
The Evaluation results (2/3) of 9 breadboard of table
The Evaluation results (3/3) of 10 breadboard of table
As shown in table 8~10, the breadboard of embodiment has suitable scratch resistance, corrosion resistance, adaptation and electric conductivity. On the other hand, the performance of the breadboard of comparative example is poor.
As a result, according to the present invention, it is known that: even if the epithelium that will be formed in matrix surface of steel plate is thinned, it also can get processing The generated scuffing from film coated surface is unobvious when with processing and the also relatively better surface treated steel plate such as corrosion resistance.
Industrial utilizability
According to said one embodiment, relatively thin also still have although being capable of providing the film thickness for being formed in the film of surface of steel plate There are excellent scratch resistance and corrosion proof coated steel plate.
Symbol description
1 coated steel plate
2 matrix steel plates
3 zinc coats
4 zinc phosphate coats
5 lower layer's epitheliums
6 upper layer epitheliums
7 first carbon blacks
8 second carbon blacks

Claims (12)

1. a kind of coated steel plate, which is characterized in that have:
Matrix steel plate；
Zinc coat, the Coating process is on described matrix steel plate；
Zinc phosphate coat, the zinc phosphate coat are formed on the zinc coat, and containing trbasic zinc phosphate crystal, and adhesion amount is 0.4 ~2.5g/m2；
Lower layer's epithelium, lower layer's epithelium are formed on the zinc phosphate coat, and adhesion amount is 50~2000mg/m2, and be inorganic It is epithelium or organo-mineral complexing epithelium；With
Upper layer epithelium, the upper layer epithelium are formed on lower layer's epithelium, and film thickness is 2.0~10.0 μm, and contains 5~25 matter The first carbon black of % is measured,
Wherein, the maximal clearance between the interface of the zinc coat and the zinc phosphate coat, the trbasic zinc phosphate crystal is 0.2 μm or less.
2. coated steel plate according to claim 1, which is characterized in that
Lower layer's epithelium contains the coloring pigment of 10~50 mass %.
3. coated steel plate according to claim 2, which is characterized in that
Lower layer's epithelium contains the coloring pigment of 10~30 mass %.
4. coated steel plate according to claim 2, which is characterized in that
The coloring pigment is the second carbon black.
5. coated steel plate according to claim 3, which is characterized in that
The coloring pigment is the second carbon black.
6. coated steel plate according to claim 4, which is characterized in that
The partial size of second carbon black is more than 100nm.
7. coated steel plate according to claim 5, which is characterized in that
The partial size of second carbon black is more than 100nm.
8. coated steel plate according to claim 4, which is characterized in that
The primary particle size of first carbon black is less than the primary particle size of second carbon black.
9. coated steel plate according to claim 5, which is characterized in that
The primary particle size of first carbon black is less than the primary particle size of second carbon black.
10. coated steel plate according to claim 6, which is characterized in that
The primary particle size of first carbon black is less than the primary particle size of second carbon black.
11. coated steel plate according to claim 7, which is characterized in that
The primary particle size of first carbon black is less than the primary particle size of second carbon black.
12. the coated steel plate according to according to claim 1~any one of 11, which is characterized in that
The upper layer epithelium contain 5~15 mass % selected from 25 DEG C at a temperature of resistivity be 0.1 × 10-6~185 × 10-6The non-oxide ceramics particle of one or more of boride, carbide, nitride and the silicide of Ω cm.
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TWI792619B (en) * 2020-10-20 2023-02-11 日商日本製鐵股份有限公司 Zn-based plated steel sheet
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