KR101171588B1 - Coating Composition for Forming Film on a Coating Steel Sheet and a Steel Sheet Having the Film - Google Patents
Coating Composition for Forming Film on a Coating Steel Sheet and a Steel Sheet Having the Film Download PDFInfo
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- KR101171588B1 KR101171588B1 KR1020100102436A KR20100102436A KR101171588B1 KR 101171588 B1 KR101171588 B1 KR 101171588B1 KR 1020100102436 A KR1020100102436 A KR 1020100102436A KR 20100102436 A KR20100102436 A KR 20100102436A KR 101171588 B1 KR101171588 B1 KR 101171588B1
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- coating
- film
- steel sheet
- zinc
- coating solution
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- 238000000576 coating method Methods 0.000 title claims abstract description 95
- 239000011248 coating agent Substances 0.000 title claims abstract description 92
- 239000008199 coating composition Substances 0.000 title description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011701 zinc Substances 0.000 claims abstract description 35
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 33
- 239000010959 steel Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019830 sodium polyphosphate Nutrition 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 abstract description 19
- 230000001070 adhesive effect Effects 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 229920000137 polyphosphoric acid Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- 239000010408 film Substances 0.000 description 40
- 230000001050 lubricating effect Effects 0.000 description 12
- 229910001335 Galvanized steel Inorganic materials 0.000 description 9
- 239000008397 galvanized steel Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000013521 mastic Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Abstract
본 발명은 아연 및 아연계 합금 도금강판에 코팅피막을 형성하는 코팅용액 조성물 및 이에 따라 형성된 피막을 갖는 아연 및 아연계 합금 도금강판에 관한 것으로서, 아크릴산(acrylic acid) 5~10중량%, 폴리인산나트륨(sodium polyphosphate) 1~10중량%, 폴리에틸렌글리콜(polyethylene glycol) 0.1~3중량% 및 잔부 물을 포함하는 유?무기 복합피막 형성용 코팅용액 조성물 및 상기 조성물을 사용하여 피막이 형성된 가공성, 접착제 접착성 및 화성처리성이 우수하고, 용접성이 우수한 아연 및 아연계 합금 도금 강판을 제공한다.The present invention relates to a coating solution composition for forming a coating film on zinc and zinc-based alloy plated steel sheet, and zinc and zinc-based alloy plated steel sheet having a film formed according to this, 5 to 10% by weight of acrylic acid, polyphosphoric acid A coating solution composition for forming an organic-inorganic composite film comprising 1 to 10% by weight of sodium polyphosphate, 0.1 to 3% by weight of polyethylene glycol, and the balance, and a processability and adhesive adhesion in which a film is formed using the composition. Provided are zinc and zinc-based alloy plated steel sheet excellent in castability and chemical conversion, and excellent in weldability.
Description
본 발명은 아연 및 아연계 합금 도금강판에 코팅피막을 형성하는 코팅 조성물 및 이에 따라 형성된 피막을 갖는 아연 및 아연계 합금 도금강판에 관한 것이다. 보다 상세하게는, 본 발명은 아연 및 아연계 합금 도금강판에 가공성, 접착성 및 탈막성이 우수한 코팅피막을 형성하기 위한 코팅 조성물 및 이에 따라 형성된 피막을 갖는 아연 및 아연계 합금 도금강판에 관한 것이다.The present invention relates to a coating composition for forming a coating film on zinc and zinc-based alloy plated steel sheet, and to a zinc and zinc-based alloy plated steel sheet having a film formed accordingly. More specifically, the present invention relates to a coating composition for forming a coating film excellent in workability, adhesion and film removal property on zinc and zinc-based alloy plated steel sheet, and zinc and zinc-based alloy plated steel sheet having a coating film formed accordingly. .
아연 및 아연계 합금 도금강판에는 용융아연도금강판, 전기 아연도금강판, 아연계 전기 합금도금강판 및 합금화 용융아연도금강판 등을 들 수 있다. 이중, 특히 합금화 용융아연도금강판(이하, GA 강판이라 함)은 가격이 저렴하고 내식성 및 용접성이 우수하여 자동차 내외판용으로 그 사용량이 점차 증가하고 있는 추세이나, 소지와 도금층의 밀착력이 열악하고 표면 윤활성이 부족하여, 프레스 성형시 크랙의 발생이 용이한 문제점을 동시에 가지고 있다.
Examples of zinc and zinc-based alloy plated steel sheets include hot dip galvanized steel sheets, electrogalvanized steel sheets, zinc-based electroalloy coated steel sheets, and alloyed hot dip galvanized steel sheets. Of these, in particular, alloyed hot-dip galvanized steel sheets (hereinafter referred to as GA steel sheets) are inexpensive, have excellent corrosion resistance and weldability, and are increasingly being used for automotive interior and exterior panels. Lack of lubricity, at the same time has the problem of easy generation of cracks during press molding.
따라서 프레스 성형성, 즉 가공성을 향상시키기 위하여 여러 가지 시도가 행해졌으며, 그 중에서도 표면에 윤활물질을 코팅하거나 개질하기 위한 기술개발이 다수 이루어졌다. 특히 표면에 윤활용액을 코팅하고 건조하여 피막을 형성시킴으로써 가공성을 향상시키고자 하는 기술에 대하여는 본 출원인도 여러 건의 특허를 보유하고 있다. 이러한 기술은 강판에 단순히 윤활성만 부여하면 되는 것이 아니고, 다른 품질 특성, 특히 접착성, 용접성, 내식성, 도장성 및 탈막성 등도 동시에 만족해야 하는 복잡한 기술이다. 특히 자동차 차체를 조립하는 공정에서 사용되는 매우 다양한 접착제들에 대한 접착성을 모두 만족할 것이 요구된다.
Therefore, various attempts have been made to improve press formability, that is, workability. Among them, a number of technical developments have been made for coating or modifying a surface of a lubricating substance. In particular, the present applicant also holds a number of patents for a technique for improving workability by coating a surface with a lubricating solution and drying it to form a film. This technique is not only a lubricating property to the steel sheet, but also a complex technique that must satisfy other quality characteristics, particularly adhesiveness, weldability, corrosion resistance, paintability and film-measuring property at the same time. In particular, it is required to satisfy all of the adhesion to a wide variety of adhesives used in the process of assembling an automobile body.
기존에 개시된 기술 중에서, 인산염계 윤활피막과 같은 무기계 윤활피막은 가격이 저렴하고 작업성이 우수한 장점을 가지고 있으나, 접착제와의 적합성이 매우 열악한 단점을 가지고 있다. 이와 같은 무기계 윤활피막을 코팅한 아연계 도금강판을 자동차 차체용으로 적용하는 경우에는 접착성을 확보하지 못함으로 인해 발생할 수도 있는 여러 가지 문제점을 감수해야 한다.
Among the disclosed techniques, inorganic lubricating coatings such as phosphate-based lubricating coatings have the advantages of low cost and excellent workability, but have a very poor compatibility with adhesives. When applying a zinc-based galvanized steel sheet coated with an inorganic lubricating coating film for automobile bodies, various problems that may occur due to failure to secure adhesiveness must be taken.
이와 같은 접착성 문제를 개선하기 위해 제시된 종래의 인산염계 무기 윤활피막으로서, 불용성의 축합 인산 아연이 고분자 형태로 네트워크를 갖는 피막을 형성함으로써 접착성을 확보하고 있으나, 이와 같은 피막은 화성처리 공정에 있어서 알칼리 탈지액이나 산성인 인산 아연 처리액에 용해하기가 극히 어렵다는 단점이 있어, 화성처리성이 불량하고, 그로 인해 도장 밀착성이나 도장 후 내식성이 저하된다.
As a conventional phosphate-based inorganic lubricating film proposed to improve such adhesion problems, insoluble condensed zinc phosphate forms a film having a network in the form of a polymer to secure adhesion, but such a coating is used in the chemical conversion process. There is a disadvantage in that it is extremely difficult to dissolve in an alkali degreasing solution or an acidic zinc phosphate treatment liquid, resulting in poor chemical conversion treatment, resulting in poor coating adhesion and post-coating corrosion resistance.
한편, 상기와 같은 화성처리성이 불량한 문제를 해결하기 위해, 일본 공개특허공보 제2002-226976호에는 인산염계의 무기 윤활 피막을 2층의 구조로 구성하되, 표층에는 불용성의 축합 인산 아연이 고분자화된 폴리인산 피막을 갖는 치밀한 피막을 형성하고, 하층은 가용성의 인산 아연 형태의 결정성 피막 구조를 갖는 피막을 기재하고 있다. 이러한 2층 구조를 형성함으로써 표층의 고분자 형태의 폴리인산피막에 의해 접착성을 향상시키면서 하층에 가용성 인산염을 갖는 피막을 형성함으로써 접착성과 화성처리성을 부여할 수 있다고 기재한다. 그러나, 이와 같은 2층 구조의 피막을 형성하기 위해서는 2중으로 처리를 해야 하고, 온도나 기타 다른 작업 조건들이 까다로워지는 문제가 있다. On the other hand, in order to solve the problem of poor chemical conversion as described above, Japanese Laid-Open Patent Publication No. 2002-226976 has a phosphate-based inorganic lubricating film in a two-layer structure, insoluble condensed zinc phosphate polymer A dense coating with a polyized polyphosphate coating is formed, and the lower layer describes a coating having a crystalline coating structure in the form of soluble zinc phosphate. It is described that by forming such a two-layered structure, adhesiveness and chemical conversion treatment can be imparted by forming a film having soluble phosphate in the lower layer while improving adhesiveness by a polyphosphate film in the form of a polymer in the surface layer. However, in order to form such a two-layered film, a double treatment is required, and there is a problem that temperature and other working conditions are difficult.
본 발명은 종래 기술의 문제점을 고려하여 완성된 것으로서, 아연 및 아연계 합금 도금강판에 접착제 접착력과 가공성이 우수하고, 화성처리성이 우수한 피막을 형성할 수 있는 아연 및 아연계 합금 도금강판용 코팅 용액 조성물을 제공하고자 한다.
The present invention was completed in consideration of the problems of the prior art, the coating solution for zinc and zinc-based alloy plated steel sheet capable of forming a film with excellent adhesive adhesion and workability, and excellent chemical conversion treatment to zinc and zinc-based alloy plated steel sheet It is intended to provide a composition.
나아가, 본 발명은 상기 조성물에 의해 형성된 가공성과 접착성이 우수하고, 화성처리성이 우수한 피막을 갖는 아연 및 아연계 합금 도금강판을 제공하고자 한다.Furthermore, the present invention is to provide a zinc and zinc-based alloy plated steel sheet having a coating film excellent in workability and adhesiveness formed by the composition, and excellent in chemical conversion treatment.
본 발명은 아크릴산(acrylic acid) 5~10중량%, 폴리인산나트륨(sodium polyphosphate) 1~10중량%, 폴리에틸렌글리콜(polyethylene glycol) 0.1~3중량% 및 잔부 물을 포함하는 유?무기 복합피막 형성용 코팅용액 조성물을 제공한다.The present invention is an organic-inorganic composite coating film comprising 5 to 10% by weight of acrylic acid, 1 to 10% by weight of sodium polyphosphate, 0.1 to 3% by weight of polyethylene glycol, and the balance. It provides a coating solution composition for.
상기 코팅용액은 pH가 2 내지 6인 것이 바람직하다.The coating solution preferably has a pH of 2 to 6.
나아가, 상기 코팅용액은 0.2 내지 1중량%의 레벨링제를 더욱 포함할 수 있다.
Further, the coating solution may further comprise 0.2 to 1% by weight of leveling agent.
한편, 본 발명은 상기와 같은 코팅용액 조성물을 사용하여 형성된 피막을 포함하며, 상기 피막은 건조 후의 부착량이 100-500㎎/㎡이고, 두께가 10-30㎚인 가공성, 접착제 접착성 및 화성처리성이 우수한 아연 및 아연계 합금 도금 강판을 제공한다.On the other hand, the present invention includes a coating formed using the coating solution composition as described above, the coating is 100-500mg / ㎡ adhesion amount after drying, processability, adhesive adhesion and chemical conversion treatment of 10-30nm thickness It provides a zinc and zinc-based alloy plated steel sheet with excellent properties.
본 발명에서 제시된 코팅 용액을 사용하여 피막을 형성하는 경우에는 표면처리된 건조 후 피막의 물질이 중성염이기 때문에, 탈지공정에서 알카리 용액을 산성화시키지 않으며, 다른 물성도 변화시키지 않는다.
In the case of forming the coating using the coating solution proposed in the present invention, since the material of the coating after the surface treatment is a neutral salt, the alkali solution is not acidified in the degreasing step and other physical properties are not changed.
또한, 탈막된 피막 물질은 이온화되므로, 침전되거나 슬러지화하지 않으며, 분산성 및 킬레이트성 물질이 포함되어 있어 강판 표면에 재부착하지 않아 강판 표면의 오염을 방지한다.
In addition, the film-deposited coating material is ionized, so that it does not precipitate or sludge and contains dispersible and chelating materials to prevent re-adhering to the steel sheet surface to prevent contamination of the steel sheet surface.
나아가, 중금속 물질인 Pb, Cr, Cd, As 및 기타 F 등 유해물질이 함유되어 있지 않은 친환경적인 코팅조성물이다.
Furthermore, it is an environmentally friendly coating composition that does not contain harmful substances such as Pb, Cr, Cd, As, and other heavy metals.
본 발명에서 제시된 코팅 용액으로 피막 처리한 아연 및 아연합금 도금 강판은 기존의 인산 아연계 무기 윤활 피막과 달리, 유기계 물질 및 무기계 물질이 복합체를 형성함으로써 접착제와의 화학적 친화력을 향상시키고, 가공성을 증진시키며, 화성처리성이 우수한 것은 물론, 극박의 코팅층을 구성하기 때문에 용접성도 저해하지 않는다.
Zinc and zinc alloy coated steel sheet coated with the coating solution proposed in the present invention, unlike the conventional zinc phosphate inorganic lubricating coating, by forming a composite of organic and inorganic materials to improve the chemical affinity with the adhesive, and improves the workability In addition, it is excellent in chemical conversion treatment, and does not impair weldability because it constitutes an ultra-thin coating layer.
특히 이러한 윤활 피막을 가지는 아연계 도금강판은 자동차 차체에 사용되는 각종 접착제에서 우수한 접착성을 나타내고, 예비경화(pre-cure) 상태에서도 무처리재와 동등 또는 그 이상의 접착제 적합성을 나타내므로, 특별히 자동차용으로 사용되는 GA 강판 등의 윤활 피막 처리재로 적합한 성질을 갖는다.In particular, the zinc-based galvanized steel sheet having such a lubricating coating exhibits excellent adhesiveness in various adhesives used in automobile bodies, and exhibits the same or better adhesive suitability as an untreated material even in a pre-cure state. It has properties suitable for lubricating film treatment materials such as GA steel sheet used for the purpose.
도 1은 실시예에 의해 제조된 유?무기 복합피막 형성용 코팅용액의 종류에 따라 피막이 형성된 코팅강판의 마찰계수를 측정한 결과를 무처리 강판에 대한 결과와 비교하는 그래프이다.
도 2는 실시예에 의해 제조된 유?무기 복합피막 형성용 코팅용액의 종류에 따라 피막이 형성된 코팅강판의 성형한계 하중 측정 결과를 무처리 강판에 대한 결과와 비교하는 그래프이다.
도 3은 실시예에 의해 제조된 유?무기 복합피막 형성용 코팅용액의 종류에 따라 피막이 형성된 코팅강판의 용액종류별 Mastic 접착제-EG 방청유를 사용한 경우의 전단강도 측정 결과를 무처리 강판에 대한 결과와 비교하는 그래프이다.1 is a graph comparing a result of measuring a coefficient of friction of a coated steel sheet with a coating according to the type of coating solution for forming an organic-inorganic composite coating film prepared according to an embodiment, with a result for an untreated steel sheet.
FIG. 2 is a graph comparing the result of forming limit load measurement of a coated steel sheet with a coating according to the type of coating solution for forming an organic-inorganic composite coating film prepared according to the example with the results for an untreated steel sheet.
Figure 3 is a result of measuring the shear strength of the result of the case of using the Mastic adhesive-EG rust-proof oil for each type of coating steel sheet formed with a coating according to the type of the coating solution for forming an organic-inorganic composite coating film prepared in Example It is a graph to compare.
본 발명의 유?무기 복합 피막 형성용 코팅 용액은 수용성으로서, 아크릴산, 폴리인산나트륨 및 폴리에틸렌글리콜을 최적 비율로 조정한 유?무기 복합 피막 형성용 코팅 용액이다. 이와 같은 아연계 도금강판에 적용되는 유?무기 복합 피막 형성용 코팅 용액은 필요에 따라서, pH 조절을 위한 알칼리 용액 및 화성처리 표면의 고른 피막을 위한 레벨링제를 소량 첨가할 수 있다. 본 발명의 코팅 용액에 있어서, 잔부는 물을 사용한다.
The coating solution for organic-inorganic composite film formation of the present invention is water-soluble and is a coating solution for organic-inorganic composite film formation in which acrylic acid, sodium polyphosphate and polyethylene glycol are adjusted at an optimum ratio. The coating solution for forming an organic-inorganic composite film applied to the zinc-based galvanized steel sheet may, if necessary, add a small amount of an alkali solution for adjusting pH and a leveling agent for an even coating of the chemical conversion surface. In the coating solution of the present invention, the balance uses water.
본 발명에서 제시하는 유?무기 복합피막 코팅용액으로부터 아연계 도금강판에 형성된 유?무기계 복합체로 이루어진 윤활피막은 가공성 및 접착성이 우수함은 물론, 용접성에서도 우수한 특성을 나타낸다.
The lubricating film made of the organic / inorganic composite coating formed on the zinc-based galvanized steel sheet from the organic-inorganic composite coating coating solution proposed by the present invention exhibits excellent processability and adhesion as well as excellent weldability.
종래의 오르토인산의 경우 탈수 축합이 이루어지면 주로 직쇄 상에 고분자화한 피로인산(pyrophosphoric acid), 트리폴리인산(tripolyphosphoric acid) 등의 폴리인산이 되고, 탈수 축합이 더 진행되면 삼차원적으로 가교하여 고분자화한 메타인산을 구성하는 인산염으로 결합상태가 크게 변화하는 성질을 가지게 된다. 강판에 이러한 인산염을 처리하였을 때, 피막의 인산염 결합상태와 고분자화의 진행 상태에 따라 피막의 성능은 크게 변화하고, 고분자화되는 불용성의 축합 인산아연 피막이 형성됨에 따라 가공성과 접착성 등의 특성이 다르게 나타나게 된다. 오르토인산 성분만의 처리는 접착성이 불충분하지만, 피로인산, 트리폴리인산, 메타인산의 순서로 접착성이 향상된다고 알려져 있다. 그러나 기본적으로 인산염 형태의 표면은 소량의 오르토인산이 소량의 Mn, Ni 등과 결합하기 때문에 가공성을 확보할 수는 있으나, 이런 형태의 피막은 접착성을 현저히 감소시키는 요인이 될 수밖에 없다.
In the case of conventional orthophosphoric acid, when dehydration condensation is performed, polyphosphate such as pyrophosphoric acid and tripolyphosphoric acid polymerized on a straight chain is mainly used, and when dehydration condensation is further progressed, the polymer is crosslinked three-dimensionally. Phosphate constituting the meta-phosphoric acid, which has a property of significantly changing the bonding state. When the phosphate is treated on the steel sheet, the performance of the film is greatly changed according to the phosphate bonding state and the progress of the polymerization of the film, and the characteristics of workability and adhesion are improved as the insoluble condensed zinc phosphate film is formed. It will appear different. Although treatment with only the orthophosphoric acid component is insufficient in adhesion, it is known that the adhesion is improved in the order of pyrophosphoric acid, tripolyphosphoric acid and metaphosphoric acid. Basically, however, the surface of the phosphate form can secure workability because a small amount of orthophosphoric acid binds to a small amount of Mn, Ni, etc., but this type of film is a factor that significantly reduces the adhesion.
이러한 종래의 인산염 피막에서 나타나는 접착성의 열세를 극복하기 위하여 본 발명에서는 아크릴산과 폴리에틸렌글리콜 및 폴리인산나트륨을 사용하여 접착성을 현저히 증가시킬 수 있음을 확인하고, 본 발명을 완성한 것이다.
In order to overcome the adhesive deterioration in the conventional phosphate coating, it was confirmed that the present invention can significantly increase the adhesiveness by using acrylic acid, polyethylene glycol, and sodium polyphosphate, thereby completing the present invention.
본 발명의 유?무기 복합피막 형성용 코팅용액에 있어서, 상기 아크릴산(acrylic acid)은 피막에 대하여 윤활성과 접착성을 부여하는 성분이다. 상기 아크릴산의 함량은 전체 코팅 용액의 5~10중량% 범위로 포함하는 것이 바람직하다. 아크릴산의 함량이 5중량% 미만이면 접착성과 가공성 향상을 기대할 수 없고, 10중량%를 초과하면 용액의 pH가 너무 낮아 도금층과의 반응성이 커져 표면에 얼룩을 쉽게 형성하는바, 상기 범위를 만족하는 것이 바람직하다.
In the coating solution for forming an organic-inorganic composite film of the present invention, the acrylic acid is a component that provides lubricity and adhesion to the film. The content of the acrylic acid is preferably included in the range of 5 to 10% by weight of the total coating solution. If the content of acrylic acid is less than 5% by weight can not be expected to improve the adhesion and processability, when the content of more than 10% by weight of the solution is too low pH to increase the reactivity with the plating layer to easily form a stain on the surface, satisfying the above range It is preferable.
상기 폴리에틸렌글리콜(polyethylene glycol)은 가공성 및 접착성을 향상시키는 성분이다. 이론적으로 명확한 것은 아니지만, 폴리에틸렌글리콜은 상기 아크릴산과 함께 접착제와의 수소결합력 및 화학적 친화력을 증가시켜 접착제와의 접착력을 증대시킴으로써, 본 발명에 따른 피막은 우수한 접착성을 나타내는 것으로 생각된다. 상기 폴리에틸렌 글리콜의 함량으로는 전체 코팅용액의 0.1~3중량% 포함하는 것이 바람직하다. 폴리에틸렌글리콜의 함량이 0.1중량% 미만이면 가공성 향상을 기대할 수 없고, 3중량%를 초과하면 용액에서의 거품 발생량이 많아지고, 또 침전물의 형성이 용이하게 되어, 용액 안정성을 저하시키는 문제가 있는바, 상기 범위를 만족하는 것이 바람직하다.
The polyethylene glycol is a component that improves processability and adhesion. Although not clear in theory, it is believed that polyethylene glycol, together with the acrylic acid, increases the hydrogen bonding force and chemical affinity with the adhesive, thereby increasing the adhesion with the adhesive, so that the coating according to the present invention exhibits excellent adhesion. The content of the polyethylene glycol is preferably contained 0.1 to 3% by weight of the total coating solution. If the content of polyethylene glycol is less than 0.1% by weight, workability improvement cannot be expected. If the content of polyethylene glycol is more than 3% by weight, the amount of foaming in the solution increases, and the formation of precipitates becomes easy, resulting in a decrease in solution stability. It is preferable to satisfy the said range.
나아가, 상기 폴리인산나트륨(sodium polyphosphate)은 용액의 안정을 향상시키고, 가공성에도 유리한 작용을 하는 성분으로서, 폴리인산나트륨은 전체 용액에 대하여 1~10중량% 포함한다. 폴리인산나트륨 함량이 1중량% 미만이면 용액 내에 침전물이 형성되고, 가공성도 열악하게 되며, 10중량%를 초과하면 용액의 pH를 급격하게 낮아져 반응성을 크게 하기 때문에, 얻어지는 피막의 물성을 저하시키는 문제가 있다.
In addition, the sodium polyphosphate (sodium polyphosphate) is a component that improves the stability of the solution, and also has an advantageous effect on the processability, sodium polyphosphate is contained 1 to 10% by weight based on the total solution. If the sodium polyphosphate content is less than 1% by weight, precipitates are formed in the solution, and workability is poor, and if it exceeds 10% by weight, the pH of the solution is drastically lowered to increase the reactivity, thereby lowering the physical properties of the resulting film. There is.
나아가, 본 발명의 코팅용액은 강판 표면에 균일한 피막을 형성하기 위해 평활제(Leveling제)를 첨가할 수 있다. 상기 평활제는 전체 코팅 용액에 대하여 0.2~1중량%의 함량으로 첨가할 수 있다.
Furthermore, in the coating solution of the present invention, a leveling agent may be added to form a uniform coating on the surface of the steel sheet. The leveling agent may be added in an amount of 0.2 to 1% by weight based on the total coating solution.
한편, 본 발명의 코팅용액은 pH 정도에 따라 화성처리성, 접착성 및 용액안정성이 다르게 나타나는 특성이 있다. 즉, pH가 2.0 이하로 낮은 코팅용액은 도금층과의 반응성이 커서 표면 색상이 검게 변하고, 화성처리성이 불충분해지는 현상이 나타나는 반면, pH가 6.0 이상으로 높게 되면, 화성처리성이 좋아지는 거동을 보여주며, 피막 표면 외관 상태가 양호하나, 밀착성이 저하하여 접착성 등의 특성이 열세하게 되며, 코팅 용액 자체의 안정성을 보장할 수 없게 된다. 따라서, 본 발명의 코팅 용액은 pH가 2.0~6.0의 범위를 갖는 것이 바람직하다. 이러한 특성을 고려하여 상기와 같은 pH 범위를 갖는 용액을 사용함으로써 가공성, 접착성 및 화성처리성이 우수한 피막을 형성할 수 있다.
On the other hand, the coating solution of the present invention has a characteristic that the chemical conversion treatment, adhesion and solution stability appear different depending on the pH degree. In other words, the coating solution with a low pH of 2.0 or less has a high reactivity with the plating layer, resulting in a black surface color and insufficient chemical conversion treatment. However, when the pH is higher than 6.0, the coating solution exhibits good behavior. It has good surface appearance but has good adhesion Deterioration results in inferior properties such as adhesion, and it is not possible to guarantee the stability of the coating solution itself. Therefore, it is preferable that the coating solution of this invention has a pH of 2.0-6.0. In consideration of these characteristics, by using a solution having a pH range as described above, it is possible to form a film excellent in processability, adhesion and chemical conversion treatment.
한편, 본 발명의 코팅 용액은 각 조성성분의 함량에 따라 pH가 2 이하의 낮은 상태를 유지할 수 있어, 상기한 바와 같은 문제점이 발생할 수 있다. 이의 보완을 위하여 pH를 상기와 같은 범위로 조정할 필요가 있다. 이때, pH를 높이는 방법으로 암모니아수나 수산화나트륨 등과 같은 알칼리 용액을 첨가할 수 있으며, 암모니아수를 첨가하는 것이 보다 바람직하다.
On the other hand, the coating solution of the present invention can maintain a low pH of 2 or less depending on the content of each composition, the problem as described above may occur. To compensate for this, it is necessary to adjust the pH to the above range. At this time, an alkaline solution such as ammonia water or sodium hydroxide can be added by increasing the pH, and it is more preferable to add ammonia water.
상기 용액을 강판에 코팅하는 방법으로는 침지, 분사, 도포 등, 본 기술분야에서 통상적으로 사용되는 방법을 적용할 수 있다. 코팅이 완료되면 수세없이 즉시 건조해야 하는데, 분위기 온도로 200~350℃에서 1~5초의 시간이면 건조가 가능하다.
As a method of coating the solution on a steel sheet, a method commonly used in the art, such as dipping, spraying, and coating may be applied. When the coating is completed, it should be dried immediately without washing with water, and it can be dried in a time of 1 to 5 seconds at 200-350 ° C. at ambient temperature.
상기와 같은 본 발명의 유?무기 복합피막 형성용 코팅용액으로부터 아연 및 아연합금 도금강판에 형성된 유?무기 복합 피막은 건조 후의 부착량이 100~500mg/㎡의 부착량을 가지며, 두께는 10~30㎚를 갖는 것이 바람직하다. 상기와 같은 피막 두께를 갖는 매우 얇은 피막이 아연계 도금강판 상에 형성되기 때문에 전도성에도 악영향을 끼치지 않아, 용접성에서도 매우 좋은 성능을 나타낼 수 있다.
The organic-inorganic composite coating film formed on the zinc and zinc alloy plated steel sheet from the coating solution for forming an organic-inorganic composite coating film of the present invention as described above has an adhesion amount of 100 to 500 mg /
이하, 실시예를 통하여 본 발명을 구체적으로 설명한다. 그러나, 이하의 실시예는 본 발명을 한정하려는 의도가 아니며, 본 발명의 하나의 실례를 나타내는 것이다.
Hereinafter, the present invention will be described in detail through examples. However, the following examples are not intended to limit the present invention, but rather illustrate one example of the present invention.
[실시예][Example]
본 발명의 실시예에 있어서, 코팅용액은 본 발명의 범위에 속하는 것으로서, 아래 표 1에 나타낸 바와 같은 함량을 갖는 실시예 1 내지 3의 3종류의 코팅용액을 제조하였다. 각 조성성분의 함량은 용액 1리터에 포함된 각 성분의 함량이며, 잔부는 물이다.In the embodiment of the present invention, the coating solution is to fall within the scope of the present invention, to prepare three types of coating solutions of Examples 1 to 3 having a content as shown in Table 1 below. The content of each component is the content of each component contained in 1 liter of the solution, the balance being water.
상기 실시예 1 내지 3에서 얻어진 코팅용액을 알칼리 탈지한, 두께가 0.7mm이고, 도금부착량이 45.5g/㎡인 합금화 용융아연도금강판에 바코터(bar coater) #3으로 용액을 균일하게 도포한 후, 340℃ 분위기의 열풍 건조 로에서 5초 동안 건조하여 피막을 형성시켰다. 얻어진 피막은 피막 부착량이 160㎎/㎡이고, 두께가 15㎚이었다.
Alkali degreasing of the coating solution obtained in Examples 1 to 3 was performed by uniformly applying a solution with a
얻어진 피막에 대하여 가공성, 접착성 및 용접성을 평가하여, 무처리 강판에 대한 각각의 물성과 대비하였다. 각각의 물성에 대한 실험방법은 다음과 같다.
Workability, adhesiveness, and weldability were evaluated about the obtained film, and it contrasted with the physical property with respect to an untreated steel plate. Experimental method for each property is as follows.
[가공성][Processability]
마찰계수: 피막 위에 P-DBH(범우화학 제조) 세정유를 도포하고 가압력 650kgf을 가한 상태에서 1000mm/분의 속도로 슬라이딩시켰으며, 이때 걸리는 드로우잉 하중을 가압력으로 나눔으로써 마찰계수를 구하였다.
Friction coefficient: P-DBH (manufactured by Bumwoo Chemical) was applied on the film and slid at a speed of 1000 mm / min with an applied pressure of 650 kgf. The friction coefficient was obtained by dividing the draw load by the applied pressure.
컵가공: 지름이 100mm인 시편에 세정유(P-DBH)를 도포하고 지름이 50mm인 펀치를 100mm/분의 속도로 밀어 올리면서 시편에 걸리는 최대하중(Max. drawing force)과 성형한계하중(limit drawing force)을 측정하였으며, 최대하중 측정시 BHF(blank holding force)는 1톤으로 하였다.
Cup processing: Apply the cleaning oil (P-DBH) to 100mm diameter specimen and push the 50mm diameter punch at 100mm / min to increase the maximum drawing force and forming limit load. The limit drawing force was measured, and the blank holding force (BHF) was 1 ton when the maximum load was measured.
얻어진 결과를 다음 표 2에 나타내었다.The results obtained are shown in Table 2 below.
상기 가공성 평가결과에 대한 표 2 및 도 1 및 도 2로부터 알 수 있는 바와 같이, 무처리재의 GA에 비하여 본 발명에서 제시한 3 종류의 코팅용액으로 코팅한 피막의 경우, 마찰계수가 0.04 이상 감소하여 윤활특성이 향상되었고(도 1), 최대하중도 약 1톤 이상 낮아져 성형가공시 마찰력이 크게 감소한 것을 알 수 있으며, 성형한계하중은 무처리 대비 3톤 이상 향상하는 경향을 나타내고 있는바(도 2), 전체적으로 가공성이 크게 향상되었음을 알 수 있다.
As can be seen from Table 2 and FIGS. 1 and 2 of the evaluation results of the processability, in the case of the coating film coated with the three types of coating solutions presented in the present invention as compared to the GA of the untreated material, the coefficient of friction decreased by 0.04 or more. As a result, the lubrication characteristics were improved (Fig. 1), and the maximum load was lowered by about 1 ton or more, which showed that the frictional force was greatly reduced during the molding process. 2) It can be seen that the overall workability is greatly improved.
[접착성][Adhesiveness]
접착성 평가를 위하여, 시편을 100mm x 25mm 크기로 절단하고 끝단 5mm 부분을 도유에 침지한 다음, 곧바로 꺼꾸로 세워 1일간 대기 방치하였다. 도유 침지한 시편의 25mm x 25mm 면적에 두께가 1 혹은 3mm가 되도록 다음과 같은 접착제를 도포한 다음, 2 장의 시편을 겹쳐 150℃(pre cure state), 160 ℃ 온도에서 각각 20분간 경화시킨 후, 다시 1일간 대기 방치하였다. 얻어진 시편을 인장시험기를 이용하여 50mm/분의 속도로 전단인장강도를 측정하였다. For adhesion evaluation, the specimens were cut to a size of 100 mm x 25 mm, the
상기 사용한 접착제 및 도유는 다음과 같다.The used adhesives and oils are as follows.
접착제: PV5308 (일본 자동차사 Hem Flange용 접착제)Adhesive: PV5308 (adhesive for Hem Flange from Japan Motor Company)
Mastic sealer (국내 자동차사 접착제)Mastic sealer (Domestic automotive adhesive)
도유: PM(일본자동차사 세정유) Petroleum oil: PM (Japanese automotive cleaning oil)
EG(국내 방청유) EG (domestic rust preventive oil)
PDBH(국내자동차사 세정유)
PDBH (Domestic Car Washing Oil)
측정한 전단인장강도 결과를 다음 표 3에 나타내었다. 전단인장강도는 PV5308 접착제는 40kg/cm2 이상이어야 하고, Mastic 접착제는 8kg/cm2 이상을 합격으로 판정한다.The measured shear tensile strength results are shown in Table 3 below. Shear tensile strength should be above 40kg / cm 2 for PV5308 adhesive, and above 8kg / cm 2 for Mastic adhesive.
상기 표 3 및 도 3에 나타낸 바와 같이, 무처리 GA의 EG 방청유를 사용한 경우에 전단강도가 기준치 대비 미달된 것을 제외하면, 본 발명에서 제시한 용액을 코팅한 모든 피막은 접착제 및 도유 종류에 관계없이 모두 기준치 이상의 높은 강도 값을 나타냄을 확인할 수 있다.
As shown in Table 3 and FIG. 3, except that the shear strength of the EG rust-proof oil of untreated GA was lower than the reference value, all coatings coated with the solution of the present invention were related to the type of adhesive and oiling. It can be seen that all of them show high intensity values above the reference value.
[용접성][Weldability]
용접성에 대하여는 연속 타점수와 적정 용접전류범위를 측정하였다. 실시예 1 내지 실시예 3에서 얻어진 코팅 용액을 사용하여 코팅된 0.7mm 두께의 GA강판에 대해, 전극압력 2.3KN, 팁의 지름이 6mm인 돔 형태의 전극을 사용하여 용접시간 12 사이클로 용접을 실시하였다. 용접전류 8.4KA에서부터 11.8KA까지 0.2KA씩 높이면서 용접부 파단면에 플러그 파괴가 일어나기 시작한 전류를 하한 전류로 선정하고 스패터(spatter)가 발생하기 시작하는 전류에서 0.2KA를 뺀 전류를 상한 전류로 결정하였다. 연속 타점수는 100타점마다 용접부 너겟(nugget) 크기를 측정하여 3.35mm 이하가 되는 시점을 연속타점수로 결정하였다.
For weldability, continuous RBI and proper welding current range were measured. A 0.7 mm thick GA steel sheet coated with the coating solution obtained in Examples 1 to 3 was welded with 12 cycles of welding time using a dome shaped electrode having an electrode pressure of 2.3 KN and a tip diameter of 6 mm. It was. Increasing the welding current from 8.4KA to 11.8KA in 0.2KA increments, select the lower limit current as the lower limit current and the current at which spatters begin to occur. Decided. The continuous RBI was measured as the weld nugget size every 100 RBIs, and the time when the RBI was 3.35 mm or less was determined as the continuous RBI.
실시예 1과 2의 코팅용액을 사용하여 코팅한 시편의 용접가능 전류범위는 용접부 플러그 파괴가 나타나기 시작한 하한치가 9.0KA, 상한치 11.5KA로 나타났고, 실시예 3의 코팅용액을 사용하여 코팅한 시편의 하한치는 10.1KA, 상한치는 11.8KA를 나타났으며, 연속 타점수는 실시예 1 내지 3의 코팅용액을 사용하여 코팅한 시편 모두 3000타 이상을 나타내었다. 한편, 무처리 GA의 용접가능 전류범위는 하한치 8.5KA, 상한치 11.8KA이었고 연속타점수는 3200타를 나타내었는바, 실시예 1 내지 3의 코팅용액을 사용하여 코팅한 시편은 무처리재와 유사한 용접특성을 가지고 있음을 알 수 있었다. The weldable current range of the specimens coated with the coating solutions of Examples 1 and 2 was 9.0KA and the upper limit of 11.5KA, where the weld plug breakage began to appear, and the specimens coated with the coating solution of Example 3 The lower limit of 10.1KA, the upper limit of 11.8KA appeared, and the continuous RBI was more than 3000 shots in all of the specimens coated using the coating solution of Examples 1 to 3. On the other hand, the weldable current range of untreated GA was lower limit of 8.5KA and upper limit of 11.8KA and the continuous RBI was 3200 strokes. The specimens coated using the coating solution of Examples 1 to 3 were similar to the untreated material. It can be seen that it has welding characteristics.
Claims (4)
A coating solution composition for forming an organic-inorganic composite coating film of zinc and zinc-based alloy plated steel, 5 to 10% by weight of acrylic acid, 1 to 10% by weight of sodium polyphosphate, polyethylene glycol Coating solution composition containing 0.1 to 3% by weight and the balance water.
The coating solution composition of claim 1, wherein the coating solution has a pH of 2 to 6.
The coating solution composition of claim 1, wherein the solution further comprises 0.2 to 1% by weight of a leveling agent based on the weight of the coating solution.
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