KR100925617B1 - Preparing method of painted steel sheet of galvannealed iron with excellent anti-blister property - Google Patents
Preparing method of painted steel sheet of galvannealed iron with excellent anti-blister property Download PDFInfo
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- KR100925617B1 KR100925617B1 KR1020020084720A KR20020084720A KR100925617B1 KR 100925617 B1 KR100925617 B1 KR 100925617B1 KR 1020020084720 A KR1020020084720 A KR 1020020084720A KR 20020084720 A KR20020084720 A KR 20020084720A KR 100925617 B1 KR100925617 B1 KR 100925617B1
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- degreasing
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 27
- 239000010959 steel Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 6
- 229910052742 iron Inorganic materials 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims abstract description 70
- 239000011248 coating agent Substances 0.000 claims abstract description 66
- 238000005238 degreasing Methods 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 10
- 239000008397 galvanized steel Substances 0.000 claims abstract description 10
- 230000001680 brushing effect Effects 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 abstract description 5
- 239000003973 paint Substances 0.000 description 25
- 230000007547 defect Effects 0.000 description 19
- 229910019142 PO4 Inorganic materials 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 18
- 239000010452 phosphate Substances 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 230000003449 preventive effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C19/00—Apparatus specially adapted for applying particulate materials to surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
- B24B29/005—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents using brushes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
본 발명은 내블리스터성이 우수한 GA(합금화 용융아연도금강판) 분체도장강판 제조방법에 관한 것으로,The present invention relates to a method for producing GA (alloyed hot dip galvanized steel) powder coated steel sheet having excellent blister resistance,
분체도장 하지로 사용되는 GA재 분체도장강판 제조방법에 있어서, In the GA material powder coated steel sheet manufacturing method used as a powder coating base,
도유량이 0.2~1.7g/㎡인 GA재를 농도 3~5중량%인 알칼리 탈지용액에 탈지온도 40~60℃ 및 탈지시간 90~120초의 탈지조건하에서 전처리한 다음, 분체도장 처리하는 것을 특징으로 하는 내블리스터성이 우수한 GA 분체도장강판 제조방법이 제공된다.The GA material having 0.2 ~ 1.7g / m2 of oil content is pretreated to alkaline degreasing solution having a concentration of 3 ~ 5% by weight under degreasing conditions of 40 ~ 60 ℃ and degreasing time of 90 ~ 120 seconds, followed by powder coating. Provided is a method for producing GA powder coated steel sheet having excellent blister resistance.
본 발명에 따라, GA 분체도장재의 도장후 도장층의 일부분이 부풀어 오르는 도장 블리스터를 방지할 수 있는 내블리스터성이 우수한 GA 분체도장강판 제조할 수 있다.According to the present invention, it is possible to produce a GA powder coating steel sheet excellent in blister resistance that can prevent a portion of the coating layer after the coating of the GA powder coating material to swell.
합금화 용융아연도금강판, 분체도장강판, 내블리스터성, 탈지Alloyed hot dip galvanized steel sheet, powder coated steel sheet, blister resistance, degreasing
Description
도 1은 도장 블리스터 결함부 단면조직/이물분석 및 인산염처리재 표면 및 이물분석 결과, 1 is a cross-sectional structure / foreign material analysis and phosphate treatment surface and foreign material analysis results of the paint blister defect,
1) 도장 블리스터 결함부 단면조직(SEM) 1) Paint blister defect section (SEM)
2) 도장 블리스터 결함부 이물성분분석(EDS)2) Foreign substance analysis (EDS) on defective parts of painted blisters
3) 인산염처리재 표면조직(SEM)3) Phosphate treatment surface texture (SEM)
4) 표면 이물성분분석(EDS)4) Surface Foreign Material Analysis (EDS)
를 나타낸 것이며, Which represents
도 2는 도유량에 따른 GA 분체도장강판의 블리스터 발생수 변화를 나타낸 것이며, 그리고 Figure 2 shows the change in the number of blister generation of GA powder coated steel sheet according to the oil flow rate, and
도 3은 전처리 조건 및 브러싱 유무에 따른 GA 분체도장강판의 블리스터 발생수 변화를 나타낸 것이다.Figure 3 shows the change in the number of blister generation of GA powder coated steel sheet according to the pre-treatment conditions and the presence or absence of brushing.
본 발명은 내블리스터(anti-blister)성이 우수한 합금화 용융아연도금 분체도장강판 제조 방법에 관한 것이다. 보다 상세하게는 도장강판의 하지로 사용되는 합금화 용융아연도금강판의 도유량, 탈지조건 및 전처리 조건 조정으로 합금화 용융아연도금 분체도장재의 도장후 도장층의 일부분이 부풀어 오르는 도장 블리스터를 방지하는 내블리스터성이 우수한 합금화 용융아연도금 분체도장강판 제조 방법에 관한 것이다.
The present invention relates to a method for producing an alloyed hot dip galvanized powder coated steel sheet excellent in anti-blister resistance. More specifically, to prevent the coating blister from swelling a part of the coating layer after coating the alloyed hot-dip galvanized powder coating material by adjusting the coating amount, degreasing condition and pretreatment condition of the alloyed hot-dip galvanized steel sheet used as the base of the coated steel sheet. The present invention relates to a method for producing an alloyed hot dip galvanized powder coated steel sheet having excellent blister property.
합금화 용융아연도금강판(Galvannealed Iron, 이하 'GA'라칭함)은 용융아연도금강판 및 전기아연도금강판 대비 점(spot)용접성, 나내식성 및 도장후 내식성이 우수하여 건자재용, 가전용 및 자동차용으로 그 수요가 증대하고 있다. 또한 분체도장은 용제형 도료와 달리 불필요한 성분을 일체 포함하지 않는 100% 고형분의 분체도료를 사용하기 때문에 용제에 의한 화재위험이나 대기오염 및 도장실의 배수 등의 공해문제 없으며, 도장형성시 주름이나 흐름현상이 없기 때문에 도장작업에 용이하다. 이러한 장점 때문에 GA재를 도장하지로 하는 GA 분체도장재가 가구 및 가전 외판용 등으로 많이 사용되고 있다. Alloy galvannealed iron (hereinafter referred to as 'GA') has excellent spot weldability, corrosion resistance and corrosion resistance after painting compared to hot-dip galvanized steel and galvanized steel. The demand is increasing. In addition, powder coating uses 100% solid powder, which does not contain any unnecessary ingredients, unlike solvent-based paints. Therefore, there is no risk of fire hazard, air pollution, or drainage of coating room. Since there is no flow phenomenon, it is easy to paint. Because of these advantages, GA powder coating material, which does not paint GA materials, is used for furniture and home appliances.
특히 가구 및 가전용으로 사용되는 분체도장재는 주로 외판용으로 사용되기 때문에 도장결함이 없는 우수한 표면외관이 요구되므로 이제까지는 표면외관이 우수한 전기도금강판이 주로 사용되어 왔다. 그러나 최근 GA재를 비롯한 용융아연도금강판의 품질향상과 전기아연도금강판에 비해 제조 비용이 싸기 때문에 점차적으로 전기아연도금강판에서 GA재로 전환되고 있는 추세이다. 그러나 도장강판의 하지로 사용되는 GA재는 도금표면에 요철이 많고, 고압하 조질압연에 따른 표면손상 등으로 분체도장시 각종 결함이 발생하고 있다. 특히 GA재를 도장하지로 사용하는 GA 분체도장의 경우, 도장시 도장층의 일부분이 부풀어 오르는 도장 블리스터가 발생하여 표면외관을 저해하는 문제가 빈번하게 발생하고 있다.In particular, since powder coating materials used for furniture and home appliances are mainly used for exterior plates, excellent surface appearance without coating defects is required, and thus, electroplating steel sheets having excellent surface appearance have been mainly used. Recently, however, the quality of hot-dip galvanized steel sheets, including GA materials, and manufacturing costs are cheaper than those of galvanized steel sheets. However, the GA material used as the base of the coated steel sheet has a lot of irregularities on the plating surface, and various defects are generated during powder coating due to surface damage due to temper rolling under high pressure. In particular, in the case of GA powder coating using the GA material as the unsubstrate, a problem occurs that frequently inhibits the surface appearance due to the occurrence of a coating blister in which a part of the coating layer swells during coating.
지금까지 이러한 도장 블리스터를 방지하기 위한 공지기술로는 1) 공보2002-0026160호, 특개 평10-53729호 및 특개 평8-113652호와 같이 분체도료 제조시 주제 수지, 경화제 및 각종 첨가제를 용제 중에 용해하거나 분산시킨 원료용액의 용제를 제거하는 공정에서 원료용액을 고온으로 가열하면 주제와 경화반응으로 겔화 현상이 발생하고, 유분이 잔존할 우려가 있다. 이렇게 제조된 분체도료는 핀홀, 기포, 블리스터 등의 도장결함을 유발할 수 있다. 따라서 분체도장 블리스터를 방지하기 의한 방법으로는 대부분이 다양한 분체도료 제조 방법에 집중되어 있다. 또한 2) 특개 평8-28779호, 특개 평9-241859호 및 특개 평 11-217682호와 같이 도장하지인 아연도금강판이나 및 아연도금계 합금도금강판의 후처리인 크로메이트 피막이 도장전처리인 알칼리 탈지공정에서 제거되지 않고, 일정량이상 유지되게 하기 위하여 크롬조성을 조정하여 크롬 6가의 용출을 방지하고, 후공정인 인산염처리성 향상 및 인산염 피막과 도료와의 밀착성을 향상시켜 도장 블리스터 결함을 방지하는 방법이 제시되고 있다.Until now, known techniques for preventing such coating blisters include 1) solvents for main resins, hardeners and various additives in the manufacture of powder coatings, such as publication 2002-0026160, Japanese Patent Application Laid-Open No. 10-53729 and Japanese Patent Application Laid-Open No. 8-113652. If the raw material solution is heated to a high temperature in the step of removing the solvent of the raw material solution dissolved or dispersed in the solvent, gelation may occur due to the main component and the curing reaction, and oil may remain. The powder coating prepared in this way may cause paint defects such as pinholes, bubbles, and blisters. Therefore, most of the methods for preventing powder coating blisters are concentrated on various powder coating methods. 2) Alkaline degreasing as a pretreatment of the chromate coating, which is a post-treatment of galvanized steel sheets and galvanized alloy plated steel sheets not coated as in Japanese Patent Laid-Open Nos. 8-28779, 9-241859 and 11-217682. To prevent bleeding of chromium hexavalent by adjusting chromium composition so as not to be removed in the process and to maintain a certain amount, and to improve the phosphate treatment property and the adhesion between the phosphate film and the paint, which is a post-process, to prevent the defect of the paint blister. Is being presented.
그러나 종례의 방법 1)과 같이 분체도료의 겔화 및 유분 잔존이 원인인 경우에는 블리스터 결함부에 공공이나 핀홀이 존재하여야 하나, 본 발명자가 분체도장 블리스터를 분석한 결과, 도장 블리스터는 결함부에 공공이나 핀홀 현상을 관찰할 수 없었다. 또한 도 1과 같이 결함의 정점에 탄소와 산소로 구성된 이물질이 존재하고, 그 상부에 도장이 되게 되어 블리스터가 발생하였다. However, as in the case of the method 1), in the case of the cause of gelation and oil residue of the powder coating, a void or pinhole should be present in the blister defect. However, as a result of the present inventors analyzing the powder coating blister, the coated blister has a defect portion. No public or pinhole phenomena were observed. In addition, as shown in FIG. 1, foreign substances composed of carbon and oxygen are present at the apex of the defect, and the upper surface of the defect is coated to produce a blister.
또한 후처리 크로메이트 용액의 조성 개선에 의한 인산염 처리성 및 도료 밀착성 향상으로 도장 블리스터를 방지하는 방법 2)은 도장후 일정기간 경과후 도장밀착성 저하에 의해서 발생되는 블리스터를 방지하는 방법이며, 일반 도장용 하지로 사용되는 도금강판은 크로메이트 처리를 실시하지 않고, 방청유 처리를 실시하게 되며, 자공정에서 탈지, 인산염 처리, 도장을 실시하게 되므로 일반적으로 분체도장시 발생하는 도장 블리스터 방지에는 바람직하지 않다. In addition, the method of preventing the paint blister by improving the phosphate treatment property and paint adhesion by improving the composition of the post-treatment chromate solution 2) is a method of preventing blister caused by the decrease in the paint adhesion after a certain period of time after coating. The plated steel sheet used as the base for painting is subjected to rust prevention oil treatment without chromate treatment and degreasing, phosphate treatment, and painting in the self process, which is generally not preferable for preventing coating blisters generated during powder coating. not.
이에 따라 본 발명은 도장공정시 발생되는 블리스터를 방지하기 위하여, 도장하지인 GA재의 도유량, 도장 탈지조건 조정 및 브러싱 처리로 도장 블리스터 원인이 되는 잔류 탄소 및 산소로 구성된 이물질 제거로 GA 분체도장재의 도장후 도장층의 일부분이 부풀어 오르는 도장 블리스터를 방지할 수 있는 내블리스터성이 우수한 GA 분체도장강판 제조 방법을 제공하는 것이다.Accordingly, in order to prevent blisters generated during the painting process, the present invention provides GA powder by removing foreign substances composed of residual carbon and oxygen, which are the cause of the blistering of the coating, by adjusting the oiling amount of the GA material which is not the coating, the coating degreasing condition, and the brushing treatment. It is to provide a method for producing a GA powder coating steel sheet excellent in blister resistance that can prevent the coating blister swelling a portion of the coating layer after the coating of the coating material.
본 발명의 일견지에 의하면,According to one aspect of the invention,
분체도장 하지로 사용되는 GA(합금화 용융아연도금강판)재 분체도장강판 제조방법에 있어서, In the GA (alloyed hot dip galvanized steel) material powder coating steel sheet manufacturing method used as a powder coating base,
도유량이 0.2~1.7g/㎡인 GA재를 농도 3~5중량%인 알칼리 탈지용액에 탈지온도 40~60℃ 및 탈지시간 90~120초의 탈지조건하에서 전처리한 다음, 분체도장 처리 하는 것을 특징으로 하는 내블리스터성이 우수한 GA 분체도장강판 제조방법이 제공된다.
The GA material having 0.2 ~ 1.7g / m2 of oil coating is pre-treated in an alkaline degreasing solution with a concentration of 3 ~ 5% by weight under degreasing conditions of 40 ~ 60 ℃ and degreasing time of 90 ~ 120 seconds, followed by powder coating. Provided is a method for producing GA powder coated steel sheet having excellent blister resistance.
이하 본 발명에 대하여 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명자는 도장 블리스터 발생 원인을 규명하기 위하여 도장하지인 GA재, 도장전처리 조건, 도료, 도장라인 등에 대해서 체계적으로 연구한 결과, 도 1과 같이 도장 블리스터 결함의 정점에 탄소와 산소로 구성된 이물질이 존재하며, 이물질은 분체도장 처리의 전공정인 인산염 처리 후에도 관찰됨을 발견하였다. 일반적으로 분체도장 공정은 예비탈지→탈지-탕세 및 수세→표면조정→인산염처리→수세→건조→분체도장→소부처리로 구성되어 있으므로, 이 이물질은 인산염처리 이전 공정인 탈지조건과 도장하지인 GA제조 조건에서 발생되는 것으로 판단된다.The present inventors systematically researched the GA material, pre-painting conditions, paint, coating line, etc., which are not coated to find the cause of paint blister generation, and as a result, carbon and oxygen are formed at the apex of the paint blister defect as shown in FIG. It was found that foreign substances existed and were observed after phosphate treatment, which is a preliminary process of powder coating process. In general, the powder coating process consists of preliminary degreasing → degreasing-hot washing and washing → surface adjustment → phosphate treatment → washing → drying → powder coating → baking treatment. It is judged to occur in manufacturing conditions.
또한 알칼리 탈지온도 및 시간을 변화시켜 탈지한 표 1에 의하면, 탈지온도 및 탈지시간이 증가할수록 인산염처리후 이물질 검출이 없고, 도장시 도장 블리스터 결함의 발생 정도도 감소하는 것을 알 수 있다. 또한 도유량에 따른 도장 블리스터 결함수를 나타낸 도 2에 의하면 동일한 탈지조건에서도 도유량이 감소할수록 도장 블리스터 결함수가 감소함을 알 수 있다. 이는 도장 블리스터가 도장하지인 GA재의 탈지불량이 발생의 원인인 것을 알 수 있다.In addition, according to Table 1 degreased by changing the alkali degreasing temperature and time, it can be seen that as degreasing temperature and degreasing time increases, there is no foreign matter detection after phosphate treatment, and the degree of occurrence of coating blister defects during coating decreases. In addition, according to FIG. 2, which shows the number of defects of the paint blister according to the oiling amount, it can be seen that the number of the paint blister defects decreases as the oiling amount decreases even under the same degreasing condition. It can be seen that this is the cause of the degreasing of the GA material that the paint blister is not coated.
즉 도유량 및 탈지조건 변화에 따른 도장 블리스터 발생 정도를 측정한 결과에 의하면, 도유량이 작을수록 도장 블리스터 발생이 비례적으로 감소하나, GA 제 조후 분체도장 까지는 일정한 시간이 요구되므로 방청처리를 하지 않을 수 없으며, 탈지조건도 강화할수록 도장 블리스터 발생이 감소하나, 탈지시간 증가에 따른 생산성 저하 등의 문제가 발생하게 된다. 특히 도장하지인 GA재 경우, 표면형상 및 표면조도 확보를 위해 고압하의 조질압연을 실시하기 때문에 조질압연으로 활성화된 표면과 방청유가 반응하여 고착성의 스컴(scum)이 형성되거나 회수되어 재사용되는 방청유 및 조질압연유의 표면부착으로 탈지능이 저하하게 된다. That is, according to the result of measuring the degree of coating blister occurrence according to the change of oiling amount and degreasing condition, the smaller the oiling amount is, the proportion of paint blister decreases proportionally.However, a certain time is required until the powder coating after GA production. Inevitably, as the degreasing conditions are strengthened, the occurrence of paint blisters decreases, but problems such as productivity decrease due to increased degreasing time occur. In particular, in the case of GA material which is not coated, rust preventive oil which is formed by high pressure rough rolling under high pressure to secure surface shape and surface roughness, reacts with rust preventive oil, and forms or recovers and reuses scum. Degreasing ability decreases by surface adhesion of crude rolling oil.
따라서 표 1과 같이 GA재의 도유량이 0.2g/㎡이하일 경우에는 도장전에 백청이 발생하기 때문에 바람직하지 않다. 또한 GA재의 도유량이 1.7g/㎡이상일 경우에는 완전 탈지를 위하여 탈지조건을 강화해야 하는 문제가 발생하게 된다. 따라서 본 발명에서는 GA재의 도유량을 0.2~1.7g/㎡으로 한정한다.Therefore, as shown in Table 1, when the oiling amount of the GA material is 0.2g /
또한 알칼리 탈지온도는 탈지용액이 저온탈지용액이므로 40~60℃로 한정하고, 탈지시간은 90~120초로 한정한다. 탈지온도가 40℃이하인 경우에는 탈지가 일어나기 위한 비누화 반응이 일어나지 않아 바람직하지 않고, 또한 저온탈지제이기 때문에 60℃이상에서는 탈지능 향상이 없기 때문에 고온으로 유지하는 것은 욕관리 및 경제적으로도 바람직하지 않다. In addition, the alkali degreasing temperature is limited to 40-60 ° C., and the degreasing time is limited to 90-120 seconds since the degreasing solution is a low temperature degreasing solution. If the degreasing temperature is 40 ° C. or lower, it is not preferable because a saponification reaction for degreasing does not occur, and since it is a low temperature degreasing agent, the degreasing ability is not improved at 60 ° C. or higher. .
알칼리 탈지시간은 90초 이하일 경우에는 탈지능 부족으로 탈지 및 인산염 처리후에도 이물질이 존재하여 도장 블리스터를 유발하게 되며, 탈지시간이 증가할수록 탈지능이 증가하게 되어 도장 블리스터 발생이 감소하나 생산성 저하를 초래하므로 최대 120초로 한정한다. If the alkali degreasing time is less than 90 seconds, foreign substances exist even after degreasing and phosphate treatment due to lack of degreasing, which causes paint blisters, and as degreasing time increases, degreasing ability increases, which reduces paint blistering, but decreases productivity. Limit to 120 seconds.
도장하지인 GA재의 고압하 조질압연 실시와 방청유 회수 재사용에 의한 고착성 의 스컴을 탈지과정에서 제거하기 위해서는 상대적으로 방청유량을 한정할 수 밖에 없다. 따라서 본 발명자는 GA재의 탈지능을 향상시키기 위한 방안을 연구한 결과, 도 2와 같이 탈지전 공정에서 GA재 표면을 0.05~0.1g/㎡정도 브러싱 처리하는 경우 상기 목적을 달성할 수 있음을 발견하였다. 탈지처리전 GA표면을 브러싱하게 됨에 따라 고착성의 스컴과 방청유를 기계적으로 제거가 가능하므로 결과적으로 기계적인 탈지공정을 추가한 것과 같은 효과를 나타내었다. 본 발명에서 브러싱량이 0.05g/㎡ 이하일 경우에는 스컴 및 방청유 제거에 효과가 없고, 0.1g/㎡이상에서는 브러싱 효과가 일정하고, 국부적으로 GA도금층 손실로 인한 내식성 저하 및 브라싱 처리 부하가 증가하기 때문에 바람직하지 않다. 상기와 같이 탈지 전공정으로 브러싱 처리시 도유량을 0.2~2.9g/㎡까지 증가가 가능하며, 탈지시간은 탈지온도 40~60℃에서 탈지온도를 60초 까지 낮추는 것이 가능하므로 GA 방청유 도포량 및 탈지조건을 완화시키는 효과가 있다. In order to remove the sticking scum from degreasing process under high pressure rough rolling of GA material under coating and de-using antirust oil, the rust prevention flow has to be limited. Therefore, the present inventors have studied a method for improving the degreasing ability of the GA material, and found that the above object can be achieved when the surface of the GA material is brushed about 0.05 to 0.1 g /
여기서 브러싱은 SiC로 구성된 브러싱 롤을 사용하였으나 이에 한정하지 않고 일반적으로 도금층 표면을 브러싱할 수 있는 샌드페이퍼(sand paper), 폴리싱 천(polishing cloth) 등의 연마장치 어느 것으로도 가능하다.
The brushing used here is a brushing roll made of SiC, but is not limited thereto, and may be any polishing device such as sand paper or polishing cloth which can generally brush the surface of the plating layer.
이하 본 발명의 실시예를 통하여 보다 상세히 설명한다.
Hereinafter will be described in more detail through embodiments of the present invention.
실시예Example
단면 도금부착량이 50g/㎡이고, 합금화도(도금층의 철농도)가 11~12%이며, 두께가 0.7~0.8㎜인 GA재를 70x150㎜로 절단하여 분체도장 하지로 사용하였다. 이 시험편을 300톤 이상으로 조질압연 한 후 도유량이 0~4.5g/㎡ 되도록 정전기스프레이도유장치로 도유처리를 실시하였다. 이렇게 도유처리된 GA재를 농도가 3%인 수산화암모늄계 저온탈지제로 탈지온도 및 탈지시간이 표 1과 같은 탈지조건에서 탈지한 후 화성처리시 피막생성의 핵역할을 하는 표면조정처리를 행하고, 내식성 향상 및 도장밀착성 향상을 목적으로 인산염 처리를 실시한 다음, 폴리에스테르-에폭시계 분체도료를 정전기스프레이도장장치로 두께가 약 60㎛ 되도록 분체도장을 실시하고, 180℃에서 600초 동안 소부처리를 실시하였다.The cross-sectional plating deposition amount was 50 g /
또한 GA 방청유 도포량 및 탈지조건 완화시키기 위하여 표 2와 같이 도유처리된 GA재 표면을 탈지 전공정으로 SiC로 구성된 브러싱롤로 GA재 표면을 0.05~0.1 g/㎡ 로 브러싱 처리하고, 상기와 동일한 방법으로 탈지처리 및 분체도장 처리를 실시하였다.In addition, in order to alleviate the amount of GA rust preventive oil and degreasing conditions, as shown in Table 2, the surface of the GA-treated oil is brushed with 0.05C to 0.1 g / m2 with a brushing roll composed of SiC as a degreasing step. Degreasing and powder coating were carried out.
이렇게 처리한 시료의 분체도장 블리스터 발생 정도, 인산염 처리재의 이물질 검출 유무를 각각 평가하여 표 1과 표 2에 나타내었다. 표 1는 GA표면을 브러싱 처리하지 않은 경우이고, 표 2은 GA 표면을 브러싱 처리한 경우의 도장 블리스터를 평가한 것이다. 여기서 GA 분체도장 블리스터는 육안으로 관찰하였으며, 조건당 평가 시편수는 5개이고, 도장 블리스터 발생 정도는 발생수가 평균 5개 이하일 경우에 우수한 것으로 평가하였다. 또한 도유량 및 탈지조건에 따른 탈지성을 평가하기 위하여 인산염 처리까지 실시한 GA 인산염처리재의 표면을 SEM으로 관찰하여 이물의 존재 여부를 판단하였으며, 이물의 성분은 EDS 점분석으로 실시하였다. Thus, the degree of powder coating blister generation and the presence or absence of foreign matter detection in the phosphate treatment material were evaluated in Table 1 and Table 2, respectively. Table 1 shows the case where the GA surface is not brushed, and Table 2 evaluates the coated blisters when the GA surface is brushed. Here, GA powder coating blisters were visually observed, and the number of evaluation specimens per condition was five, and the degree of coating blister generation was evaluated to be excellent when the number of occurrences was five or less on average. In addition, in order to evaluate the degreasing property according to the oiling amount and the degreasing condition, the surface of the GA phosphate treated material, which was subjected to the phosphate treatment, was observed by SEM to determine the presence of foreign substances, and the foreign substances were analyzed by EDS point analysis.
하기 도 1에 도장 블리스터 결함부 단면조직/이물분석 및 인산염처리재 표면 및 이물분석 결과를 나타내었으며, 여기서 1) 도장 블리스터 결함부 단면조직(SEM), 2) 도장 블리스터 결함부 이물성분분석(EDS), 3) 인산염처리재 표면조직(SEM), 그리고 4) 표면 이물성분분석(EDS)을 나타낸다.1 shows the result of cross-sectional structure / foreign material analysis of the paint blister defect part and the surface and foreign material analysis of the phosphate treatment material, where 1) the coating blister defect part cross-sectional structure (SEM), and 2) foreign material component of the paint blister defect part Analysis (EDS), 3) phosphate treatment surface texture (SEM), and 4) surface foreign substance analysis (EDS).
또한 도 2에 도유량에 따른 GA 분체도장강판의 블리스터 발생수 변화를 그래프로 나타내었으며 그리고 도 3에 전처리 조건 및 브러싱 유무에 따른 GA 분체도장강판의 블리스터 발생수 변화를 그래프로 나타내었다. In addition, Fig. 2 shows the change in the number of blister generation of the GA powder coated steel sheet according to the oil flow rate, and in Fig. 3 shows the change in the number of blister generation of the GA powder coated steel sheet with or without brushing.
이 결과에 의하면 본 발명에서 제시한 도유량 및 탈지조건으로 조업한 경우(No. 14, 15, 18~20, 22~25)에는 인산염처리시 이물질이 관찰되지 않았으며, 또한 도장 블리스터 결함이 평균 5개 이하로 내블리스터성이 우수한 GA 분체도장강판 제조가 가능하였다. According to this result, when operating with the oiling amount and degreasing condition suggested in the present invention (No. 14, 15, 18-20, 22-25), no foreign matter was observed during phosphate treatment, and paint blister defects were observed. It was possible to manufacture GA powder coated steel sheet excellent in blister resistance to an average of five or less.
이에 반해서 도유량이나 알칼리 탈지온도 및 시간이 본 발명의 범위를 벗어날 경우(No. 1, 2~5, 8~10, 12, 13, 17)에는 탈지부족에 의한 이물질 검출로 도장 블리스터가 발생함으로 바람직하지 못하였다. 또한 도유처리를 하지 않은 경우(No. 6, 11, 16, 21, 26)에는 모든 조건에서 도장 블리스터가 발생하지 않았으나, GA재 제조후 도장처리까지의 시간이 경과하기 때문에 아연산화물인 백청 발생으로 바람직하지 않았다.On the other hand, when the oiling amount, alkali degreasing temperature and time are out of the scope of the present invention (No. 1, 2 to 5, 8 to 10, 12, 13, 17), coating blister occurs due to the detection of foreign substances due to degreasing. It was not desirable. In addition, when the oil treatment was not carried out (No. 6, 11, 16, 21, 26), the paint blister did not occur under all conditions, but the white rust, which is zinc oxide, occurred because the time elapsed after the GA material was manufactured. Not preferred.
또한 GA표면을 브러싱 처리한 경우인 표 2에 의하면, 본 발명에서 제시한 도유량 및 탈지조건으로 조업한 경우(No. 5, 12, 13, 19~21)에는 인산염처리시 이물질이 관찰되지 않았으며, 또한 도장 블리스터 결함이 평균 5개 이하로 내블리스터성이 우수한 GA 분체도장 강판 제조가 가능하였다. 이에 반해서 도유량이나 알칼리 탈지온도 및 시간이 본 발명의 범위를 벗어날 경우(No. 1, 2~4, 10~11, 22)에는 탈지부족에 의한 이물질 검출로 도장 블리스터가 발생함으로 바람직하지 못하였다.
In addition, according to Table 2, which is a case where the GA surface is brushed, foreign matters were not observed during phosphate treatment in the case of operating with the oiling amount and degreasing condition suggested in the present invention (No. 5, 12, 13, 19 to 21). In addition, it is possible to manufacture GA powder coated steel sheet having excellent blister resistance with an average of 5 or less painted blister defects. On the other hand, if the oiling amount or alkali degreasing temperature and time is out of the scope of the present invention (No. 1, 2-4, 10-11, 22), it is not preferable because the coating blister occurs due to the detection of foreign substances due to degreasing. It was.
본 발명에 따라, 도장하지인 GA재의 도유량, 도장 탈지조건 조정 및 브러싱 처리로 도장 블리스터 원인이 되는 잔류 탄소 및 산소로 구성된 이물질 제거로 GA 분체도장재의 도장후 도장층의 일부분이 부풀어 오르는 도장 블리스터를 방지할 수 있는 내블리스터성이 우수한 GA 분체도장강판 제조할 수 있다.According to the present invention, after the coating of the GA powder coating material, the part of the coating layer swells after the coating of the GA powder coating material by removing the foreign matter composed of residual carbon and oxygen which causes the coating blister cause by adjusting the oiling amount, coating degreasing condition and brushing treatment of the GA material which is not coated. GA powder coated steel sheet excellent in blister resistance that can prevent blister can be produced.
또한 표면엄격재인 가전용 외판용에 GA재 사용이 가능하기 때문에 GA재의 용도확대와 전기도금강판의 대체에 따른 제조비용 감소의 부대효과를 얻을 수 있다.In addition, since GA materials can be used for exterior panels for home appliances that are surface stiffening materials, it is possible to obtain side effects of expanding the use of GA materials and reducing manufacturing costs by replacing electroplating steel sheets.
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| JPH10121265A (en) | 1996-10-18 | 1998-05-12 | Nippon Steel Corp | Galvannealed steel sheet having excellent lubricity, degreasability and weldability |
| JP2001271153A (en) | 2000-03-27 | 2001-10-02 | Sumitomo Metal Ind Ltd | Galvannealed steel sheet and its manufacturing method |
| KR20020041099A (en) * | 2000-11-27 | 2002-06-01 | 윤대근 | Environment affinitive color clear coated steel sheet |
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| JPH10121265A (en) | 1996-10-18 | 1998-05-12 | Nippon Steel Corp | Galvannealed steel sheet having excellent lubricity, degreasability and weldability |
| JP2001271153A (en) | 2000-03-27 | 2001-10-02 | Sumitomo Metal Ind Ltd | Galvannealed steel sheet and its manufacturing method |
| KR20020041099A (en) * | 2000-11-27 | 2002-06-01 | 윤대근 | Environment affinitive color clear coated steel sheet |
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| KR20210147253A (en) * | 2020-05-28 | 2021-12-07 | 현대제철 주식회사 | Galva-annealed steel sheet and the method for manufacturing the same |
| KR102352192B1 (en) * | 2020-05-28 | 2022-01-17 | 현대제철 주식회사 | Galva-annealed steel sheet and the method for manufacturing the same |
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