CN102070927B - Water-based surface treatment agent for color coating pretreatment of galvanized plates - Google Patents
Water-based surface treatment agent for color coating pretreatment of galvanized plates Download PDFInfo
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- CN102070927B CN102070927B CN 201110030304 CN201110030304A CN102070927B CN 102070927 B CN102070927 B CN 102070927B CN 201110030304 CN201110030304 CN 201110030304 CN 201110030304 A CN201110030304 A CN 201110030304A CN 102070927 B CN102070927 B CN 102070927B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000009500 colour coating Methods 0.000 title claims abstract description 22
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008393 encapsulating agent Substances 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910003978 SiClx Inorganic materials 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
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- 229920002635 polyurethane Polymers 0.000 claims description 2
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- 239000011591 potassium Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract 2
- 238000002161 passivation Methods 0.000 description 15
- 238000002203 pretreatment Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
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- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
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- 150000001875 compounds Chemical class 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
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- 206010037844 rash Diseases 0.000 description 3
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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Landscapes
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a water-based surface treatment agent for the color coating pretreatment of galvanized plates, and belongs to the technical field of the surface treatment of color-coated galvanized plates. The water-based surface treatment agent comprises the following components in percentage by mass: 20 to 60 percent of water-based resin, 1 to 5 percent of organosilane, 0.5 to 2.5 percent of inorganic corrosion inhibitor, 0.5 to 3 percent of sealant, 1 to 3 percent of accelerating agent and the balance of deionized water. In the water-based surface treatment agent, the inorganic corrosion inhibitor, nano particles, the organosilane and the water-based resin are combined organically to form a composite passivating film, so the bonding force of the passivating film and a galvanizedlayer is improved, and the coating performance of the galvanized plate subjected to the surface treatment is improved. Nano-silicon dioxide serving as the sealant can be distributed in the passivating film uniformly after being modified to improve the compactness of a film layer, so the decay resistance of the film layer is improved. The water-based surface treatment agent does not contain chromium with any valence state, and is environmentally-friendly, the pretreatment process is simple, and the requirement of a color coating process can be met.
Description
Technical field:
The invention belongs to the technical field of surface of color coating galvanized sheet, relate in particular to a kind of water-based surface treatment agent for color coating pretreatment of galvanized plates that improves galvanized sheet solidity to corrosion and coating.
Technical background:
Colour coated plate is the ultimate product of world today iron and steel enterprise sheet material deep processing, has lightweight, characteristics and the good Corrosion Protection such as attractive in appearance, is widely used in the industries such as building, light industry, household electrical appliances.Because organic coating has the ability that steel are isolated from the outside, so can prolong the work-ing life of steel.But the organic coating of making to have coating and application techniques now, often there is small pin hole, extraneous moisture, steam, oxygen and various ion all can permeate by pin hole, when the interface that infiltrates into base steel and coating, and when forming local element, then make coated steel produce the underfilm corrosion reaction, thereby make apparent loss of gloss, variable color, efflorescence, checking, cracking, bubbling and the rust staining etc. of occurring of coating.Colour coated plate substrate commonly used is galvanized sheet, for improving the solidity to corrosion of colour coated plate, must carry out pre-treatment to galvanized sheet before application.That uses traditionally contains the sexavalent chrome passivating solution, owing to have very large toxicity, do not met the requirement of environmental protection theory, so the research of environment-friendly type galvanized sheet color coating pre-treatment use tensio-active agent is subject to extensive concern.
For the research of chromium-free passivation liquid, the domestic report that pertinent literature was arranged from the nineties in last century.Document " application of molybdate in Surface Treatment Industry " ([J]. electroplate and covering with paint 1994,13 (3): 54-57) disclose and utilized Sodium orthomolybdate for main filmogen galvanized sheet to be carried out passivation, improved to a certain extent the solidity to corrosion of galvanized sheet.Document " zinc coating rare earth Passivation Treatment and the dissolving in sodium chloride solution thereof " ([J]. electroplate and covering with paint 1994,18 (4): 1-5) report is with earth solution Ce (NO
3)
3, La (NO
3)
3And Pr (NO
3)
3The surface that is coated in galvanized sheet has formed one deck passivating coating.Chinese patent CN 101117710A discloses a kind of Zinc coating plate molybdate inactivating method, and the method soaks decorations by acidity and passivation has realized Passivation Treatment to steel plate galvanized.These passivation treating agents form one deck unit molecule passive film on the galvanized sheet surface, although fine with the sticking power of zinc layer, because inorganic passive film compactness is bad, passive film is very thin, so erosion resistance is relatively poor.
The scientific research personnel turns to sight the research of organism passive film in recent years.Chinese patent CN 101137766A discloses a kind of surface of steel plate prescription for the treatment of liquid, this prescription is by containing amino silane coupling agent, containing amino water-based phenolic compound, form with zirconium-containing compound and fluorochemicals, fully Chrome-free and demonstrate high erosion resistance and good stability.United States Patent (USP) (US Pat., 4341558,1997) a kind of Chrome-free alloy surface treatment agent is disclosed, this treatment agent is comprised of phytic acid, silica gel and titanium or zirconium compounds, metallic substance after the processing can not wash with water, directly in 120 ℃ of dryings, is coated with at last Synolac melamine lacquer, find that through salt mist experiment this organic coating sticking power and metallic substance corrosion stability are much better than conventional chromating.
The organic resin passivation is another large class research direction, utilizes the barrier property of resin film forming, stops Among Corrosive Factors, such as steam, oxygen etc., with the steel plate substrate contact, introduces simultaneously inorganic inhibitor and improves its corrosion resisting property.Document " research of Nano silica sol/vinylformic acid composite anti-corrosive film " ([J]. material protection; 2005; 38 (1): 17-19) report: o'clock form afterwards stable dispersion system in pH=7～8 with acrylic resin and silicon sol are compound; dip-coating forms fine and close crosslinking net film at galvanized sheet, and erosion resistance still can not surpass 72h.Document " research of the composite passivated technique of galvanized sheet " ([J]. chemistry and biotechnology, 2010,27 (1): 75-78) report: benzene emulsion and phytic acid, organosilane, the compound rear formation passivating solution of composite salt, the passive film erosion resistance that forms after the passivation is better, the area of white rust＜5% appears after 72h NSS processes, but dip-coating 60s in passivating solution, passivation time is longer, is unfavorable for demand of industrial production.Chinese patent CN101250699A discloses organic resin chromium-free passivation liquid of a kind of galvanized sheet and preparation method thereof.This patent is aided with inorganic inhibitor and encapsulant take organosilicon crylic acid latex as main membrane-forming agent, and by the introducing of resin barrier layer and silicon compound, the solidity to corrosion of raising passivation layer can't affect the coating processing after the passivation.
Summary of the invention:
The purpose of this patent is to overcome in the existing color coating preconditioning technique uses the problem that contains the chromium treatment solution, and a kind of environmental protection is provided, and pretreatment technology is simple, has the water-based surface treatment agent for color coating pretreatment of galvanized plates of excellent coating performance.
Water-based surface treatment agent for color coating pretreatment of galvanized plates component provided by the present invention and mass percent are as follows:
Constituent mass per-cent (%)
Water-base resin 20～60
Organosilane 1～5
Inorganic inhibitor 0.5～2.5
Encapsulant 0.5～3
Promotor 1～3
The deionized water surplus
Described water-base resin is that solids content is 28～30%, the pH value is 7.0～9.0 aqueous polyurethane.
Described organosilane is γ-glycidyl ether oxygen propyl trimethoxy silicane.
Described inorganic inhibitor is a kind of or two kinds of compositions in Sodium orthomolybdate, ammonium molybdate, the potassium molybdate.
Described encapsulant is the organically-modified nano-silica SiClx.
Described promotor is the hydrogen peroxide of 30% content.
Water-based surface treatment agent for color coating pretreatment of galvanized plates provided by the present invention prepares by the following method:
It is in 3～4 the deionized water that described encapsulant is dispersed in the pH value, under agitation drips described organosilane, then stirs 4h under 20～30 ℃ of conditions; To be dissolved in the deionized water without described machine inhibiter and promotor; With two kinds of aqueous solution, add while stirring described water-base resin, stir at normal temperatures at last 1～2h and get final product.
Estimating the erosion resistance with gained galvanized sheet of the present invention, mainly is to realize by neutral salt spray test.Other performances of pretreatment fluid and passive film are also estimated by test such as stability, water tolerance, film adhesive etc.Evaluation result can obtain by following experiment content.
(1) stability of passivating solution
Passivating solution is placed under the room temperature condition airtight preservation two months, the state of observation passivating solution.Evaluation method is as follows:
Zero: stable
◎: a small amount of floss
●: unstable
(2) neutral salt spray test
Galvanized sheet sample through the present invention processed adopts continuously spraying with reference to GB/T 10125-1997, takes out in the different time periods, and gently brush specimen surface with banister brush, use flushing with clean water after taking out, observe the area that " white rust " occur, calculate the area of " white rust " with cross-hatching.Evaluation method is as follows:
Zero: 72h the white rust area occurs less than 5%
White rust area 5%～15% appears in ◎: 72h
●: 72h the white rust area occurs greater than 15%
(3) coating adhesion
With reference to the cross cut test of GB/T 9286-1998 paint film, utilize cutter to draw lattice at three different positionss of film coated surface, about 1 square millimeter of size, the degree of depth reach zinc layer surface, use the 3M tape stripping, then rating.
Zero: more than the one-level
◎: more than the secondary
●: below the secondary
(4) water resistance of passive film
The water tolerance test of this patent adopts 100 ℃ boiling water to drop on the passive film surface, observes its appearance change behind its natural air drying.Evaluation method is as follows:
Zero: without any variation
◎: not obvious efflorescence, breakage or defective
●: obviously efflorescence, breakage or defective
(5) anti-finger printing test
The anti-finger printing test of this patent is to utilize finger to press to be pressed on the galvanized sheet surface passivated membrane, and the readability of fingerprint is confirmed in range estimation.Evaluation method is as follows:
Zero: fully without the fingerprint vestige
◎: slight fingerprint trace
●: obvious fingerprint trace
Effect of the present invention and benefit are organically in conjunction with forming composite passivation film with inorganic inhibitor, nanoparticle, organosilane and water-base resin.Because the introducing of organosilane can not only improve the bonding force of passive film and zinc coating, and can improve the coating performance after the galvanized sheet surface treatment.Nano silicon as encapsulant can be evenly distributed in after modification in the passive film, improves the compactness of rete, thereby improves its corrosion resistance nature.The present invention does not contain the chromium of any valence state, is a kind of environment-friendly type water-based surface treatment agent for color coating pretreatment of galvanized plates.Pretreatment technology of the present invention is simple, can satisfy the demand of colour-coating technology.
Embodiment:
Electrochemical deoiling is carried out with degreasing fluid in the galvanized sheet surface, the tap water flushing, rinsed with deionized water is treated pre-treatment behind the hot blast drying.
The pretreatment fluid temperature: room temperature, passivation time: 10s, the passivation mode: dip-coating, spraying, roller coat all can, drying temperature: 80～100 ℃ of oven dry.
Embodiment 1: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 20
Organosilane 1.5
Inorganic inhibitor 1.5
Encapsulant 0.5
Promotor 1
The deionized water surplus
Embodiment 2: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 25
Organosilane 2
Inorganic inhibitor 1
Encapsulant 0.5
Promotor 1.5
The deionized water surplus
Embodiment 3: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 35
Organosilane 3
Inorganic inhibitor 2
Encapsulant 1.5
Promotor 1.5
The deionized water surplus
Embodiment 4: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 50
Organosilane 2
Inorganic inhibitor 2.5
Encapsulant 0.5
Promotor 3
The deionized water surplus
Embodiment 5: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 60
Organosilane 1
Inorganic inhibitor 2.5
Encapsulant 2
Promotor 1
The deionized water surplus
Embodiment 6: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 35
Organosilane 5
Inorganic inhibitor 2.5
Encapsulant 2.5
Promotor 3
The deionized water surplus
Embodiment 7: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 45
Organosilane 3
Inorganic inhibitor 2
Encapsulant 3
Promotor 2.5
The deionized water surplus
Embodiment 8: prepare color coating pre-treatment use surface treatment agent of the present invention according to the following component of listing and weight part:
Constituent mass per-cent (%)
Water-base resin 25
Organosilane 2
Inorganic inhibitor 2.5
Encapsulant 3
Promotor 3
The deionized water surplus
The properties detected result of embodiment sees Table 1.
Table 1 performance test results
| Stability | Erosion resistance | Water tolerance | Sticking power | Anti-finger printing | |
| Implement 1 | ○ | ◎ | ◎ | ◎ | ◎ |
| Implement 2 | ○ | ◎ | ◎ | ○ | ◎ |
| Implement 3 | ○ | ○ | ○ | ○ | ○ |
| Implement 4 | ◎ | ◎ | ○ | ○ | ○ |
| Implement 5 | ● | ◎ | ○ | ○ | ◎ |
| Implement 6 | ○ | ○ | ○ | ○ | ○ |
| Implement 7 | ○ | ○ | ○ | ○ | ○ |
| Implement 8 | ○ | ◎ | ○ | ○ | ○ |
Claims (1)
1. water-based surface treatment agent for color coating pretreatment of galvanized plates is characterized in that the component of this aqueous surface-treating agent and mass percent are as follows:
Constituent mass per-cent (%)
Water-base resin 20～60
Organosilane 1～5
Inorganic inhibitor 0.5～2.5
Encapsulant 0.5～3
Promotor 1～3
The deionized water surplus
Described water-base resin is that solids content is 28～30%, the pH value is 7.0～9.0 aqueous polyurethane;
Described organosilane is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Described inorganic inhibitor is a kind of or two kinds of compositions in Sodium orthomolybdate, ammonium molybdate, the potassium molybdate;
Described encapsulant is the organically-modified nano-silica SiClx;
Described promotor is the hydrogen peroxide of 30% content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110030304 CN102070927B (en) | 2011-01-22 | 2011-01-22 | Water-based surface treatment agent for color coating pretreatment of galvanized plates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110030304 CN102070927B (en) | 2011-01-22 | 2011-01-22 | Water-based surface treatment agent for color coating pretreatment of galvanized plates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102070927A CN102070927A (en) | 2011-05-25 |
| CN102070927B true CN102070927B (en) | 2013-05-29 |
Family
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Family Applications (1)
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| CN 201110030304 Expired - Fee Related CN102070927B (en) | 2011-01-22 | 2011-01-22 | Water-based surface treatment agent for color coating pretreatment of galvanized plates |
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| CN114874691B (en) * | 2022-06-20 | 2023-04-07 | 马鞍山钢铁股份有限公司 | Pre-priming integrated agent for color-coated sheet, preparation method of pre-priming-integrated agent, color-coated sheet and production method of color-coated sheet |
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