KR20140084643A - Composite resin coating steel sheet - Google Patents
Composite resin coating steel sheet Download PDFInfo
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- KR20140084643A KR20140084643A KR1020120154315A KR20120154315A KR20140084643A KR 20140084643 A KR20140084643 A KR 20140084643A KR 1020120154315 A KR1020120154315 A KR 1020120154315A KR 20120154315 A KR20120154315 A KR 20120154315A KR 20140084643 A KR20140084643 A KR 20140084643A
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- South Korea
- Prior art keywords
- steel sheet
- resin
- weight
- conductive additive
- composite resin
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 60
- 239000010959 steel Substances 0.000 title claims abstract description 60
- 239000000805 composite resin Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims description 49
- 239000011248 coating agent Substances 0.000 title claims description 46
- 239000002482 conductive additive Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 26
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 25
- 239000011247 coating layer Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- -1 silicate compound Chemical class 0.000 claims description 14
- 150000003609 titanium compounds Chemical class 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 8
- 239000008397 galvanized steel Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 6
- 150000003673 urethanes Chemical class 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001722 carbon compounds Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 2
- SRLPPRVVQNACSW-UHFFFAOYSA-L 2-hydroxypropanoate;titanium(2+) Chemical compound [Ti+2].CC(O)C([O-])=O.CC(O)C([O-])=O SRLPPRVVQNACSW-UHFFFAOYSA-L 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000010960 cold rolled steel Substances 0.000 claims description 2
- 239000008119 colloidal silica Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 32
- 230000007797 corrosion Effects 0.000 abstract description 32
- 239000000446 fuel Substances 0.000 abstract description 22
- 238000003466 welding Methods 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000002952 polymeric resin Substances 0.000 description 9
- 229920003002 synthetic resin Polymers 0.000 description 9
- 239000002828 fuel tank Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000004640 Melamine resin Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- NXKOSHBFVWYVIH-UHFFFAOYSA-N 2-n-(butoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCOCNC1=NC(N)=NC(N)=N1 NXKOSHBFVWYVIH-UHFFFAOYSA-N 0.000 description 1
- AOSPVUKRNAQARI-UHFFFAOYSA-N 2-n-(trimethoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COC(OC)(OC)NC1=NC(N)=NC(N)=N1 AOSPVUKRNAQARI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 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
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005493 welding type Methods 0.000 description 1
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Classifications
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- 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
-
- 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
-
- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Laminated Bodies (AREA)
Abstract
Description
본 발명은 내연료성 및 용접성이 우수한 복합수지 코팅 강판에 관한 것이다.
The present invention relates to a composite resin-coated steel sheet excellent in fuel resistance and weldability.
자동차 연료탱크는 스폿(Spot)용접, 심(seam)용접, 브레이징(Brazing) 및 프로젝션(Projection) 용접 등 다양한 종류의 용접에 의해 만들어진다. 따라서 연료탱크용 강판은 용접특성이 우수해야 하고, 동시에 연료에 대한 내구성이 우수해야 한다. 특히 최근에는 화석연료의 사용량을 줄이기 위해 다양한 종류의 바이오 연료를 기존 가솔린이나 디젤연료에 혼합하여 사용함에 따라 연료탱크는 더욱 심한 부식환경에 도출되어 있다.Automobile fuel tanks are made by various types of welding such as spot welding, seam welding, brazing and projection welding. Therefore, the steel plate for the fuel tank should have excellent welding characteristics and at the same time have excellent durability against fuel. In recent years, in order to reduce the use of fossil fuels, various types of biofuels are mixed with existing gasoline or diesel fuels.
자동차용 연료탱크용으로 주로 사용되고 있는 고분자 수지를 주성분으로 하는 수지계아연도금 코팅 강판은 내연료성과 내부식성은 우수한 반면, 코팅면이 절연특성을 가지므로 용접 특성이 나쁘다. 이와 같은 단점 때문에 고분자 수지 조성물에 금속입자를 혼합하여 전도성을 향상하여 용접성을 향상하는 기술들이 개시되었다. 그러나 이러한 기술은 도막 두께가 증가하여 제조비용이 높을 뿐만 아니라 작업성이 나쁘고 가공 시 가루가 발생하여 추가적인 불량이 발생하는 단점이 있다. 또한, 고가의 Sn-Zn 합금 용융도금 강판을 적용하는 기술이 상용화되어 있으나 고가일 뿐만 아니라, 내연료성과 내부식성이 나쁜 단점이 있다. Resin-based galvanized steel sheets mainly composed of polymer resins mainly used for fuel tanks for automobiles are excellent in fuel resistance and corrosion resistance, but have poor welding characteristics because the coated surface has insulation characteristics. Techniques have been disclosed for improving the weldability by improving the conductivity by mixing the metal particles with the polymer resin composition due to such disadvantages. However, such a technique has a disadvantage that not only the manufacturing cost is increased due to an increase in the thickness of the coating film, but also the workability is poor and the powder is generated during the processing, resulting in additional defects. In addition, although a technique of applying an expensive Sn-Zn alloy-plated steel sheet is commercialized, it is not only expensive, but also has a disadvantage in that it has poor resistance to fuel and corrosion.
최근 바이오 연료와 같은 다종연료의 사용량이 증가함에 따라 연료탱크의 사용 환경이 점점 더 나빠지고 있으므로 더 우수한 내연료성을 갖는 연료탱크용 강판의 개발이 필요하다.Recently, the usage environment of the fuel tank is getting worse as the amount of various kinds of fuel such as biofuel is increased, so it is necessary to develop a steel sheet for a fuel tank having better fuel resistance.
특허문헌 1과 같이, 마이크론 사이즈의 금속 분말이 고분자 수지와 단순 혼합된 경우에는 방치하면 비중이 큰 금속이 가라앉게 되므로 고분자 매트릭스 외부에 금속 분말이 결합되어 있어, 건조도막 형성 시 내용제성과 내식성이 나쁘고, 가공 시에도 가루가 발생하는 단점이 있다,
When a micron-sized metal powder is simply mixed with a polymer resin as in Patent Document 1, a metal having a large specific gravity is submerged when it is left to stand, so that the metal powder is bonded to the outside of the polymer matrix. There is a disadvantage that dust is generated even at the time of processing,
이에, 본 발명자들은 고분자 매트릭스 내 전도성 첨가제를 함입시킨 코팅층을 포함하는 복합수지 코팅 강판을 제조함으로써 본 발명을 완성하게 되었다. Accordingly, the present inventors have completed the present invention by producing a composite resin-coated steel sheet including a coating layer containing a conductive additive in a polymer matrix.
따라서, 본 발명은 아연 도금 강판 상에 고분자 매트릭스 내부에 전도성 첨가제가 함입된 수지 코팅층이 형성된 복합수지 코팅강판 및 이의 제조방법을 제공하는데 그 목적이 있다.
Accordingly, it is an object of the present invention to provide a composite resin-coated steel sheet on which a resin coating layer containing a conductive additive is formed in a polymer matrix on a galvanized steel sheet and a method for manufacturing the same.
상기 과제를 해결하기 위한 수단으로서, 본 발명은 As means for solving the above problems,
강판 상에 고분자 매트릭스 내부에 전도성 첨가제가 함입된 수지 코팅층이 형성된 복합수지 코팅강판을 제공한다.
A composite resin coated steel sheet on which a resin coating layer containing a conductive additive is formed in a polymer matrix is provided on a steel sheet.
상기 과제를 해결하기 위한 다른 수단으로서, 본 발명은, According to another aspect of the present invention,
강판 상에 고분자 매트릭스 내부에 전도성 첨가제가 함입된 수지 코팅층을 형성하는 단계를 포함하는 복합수지 코팅강판의 제조방법을 제공한다.
And a step of forming a resin coating layer in which a conductive additive is embedded in the polymer matrix on the steel sheet.
본 발명에서 고분자 매트릭스에 전도성 첨가제가 함입된 복합수지 코팅으로 제조한 연료탱크용 강판은 표면 전기전도성이 우수하여 용접성이 우수하고, 다양한 다종연료의 사용 시에도 내부식성이 우수하며, 내연료성이 우수하다.
In the present invention, a steel sheet for a fuel tank manufactured by a composite resin coating containing a conductive additive in a polymer matrix is excellent in weldability because of excellent surface electrical conductivity, excellent in corrosion resistance even when using various kinds of fuels, great.
도 1은 본 발명에 따른 복합수지 코팅강판의 단면모식도이다.
도 2는 본 발명의 일 실시예에 따른 복합수지 코팅강판의 단면모식도이다.
도 3은 내연료성 평가를 위한 장치를 나타낸 것이다.1 is a schematic cross-sectional view of a composite resin-coated steel sheet according to the present invention.
2 is a schematic cross-sectional view of a composite resin-coated steel sheet according to an embodiment of the present invention.
Fig. 3 shows an apparatus for evaluating fuel resistance.
본 발명은 강판 상에 고분자 매트릭스 내부에 전도성 첨가제가 함입된 수지 코팅층이 형성된 복합수지 코팅강판에 관한 것이다.The present invention relates to a composite resin-coated steel sheet on which a resin coating layer containing a conductive additive is formed in a polymer matrix on a steel sheet.
상기 강판은 연료탱크용 강판이면 모두 가능하며, 아연 도금 강판이 보다 바람직하다.The steel sheet may be any steel sheet for a fuel tank, and a galvanized steel sheet is more preferable.
상기 아연 도금 강판은 냉연강판에 아연 단독, 아연을 포함하는 2종 또는 3종 합금 도금 강판, 용융 도금 강판, 건식 도금 강판을 모두 포함할 수 있다.The zinc-plated steel sheet may include zinc alone, zinc-plated two or three alloy-plated steel sheets, hot-dip galvanized steel sheets, and dry galvanized steel sheets.
상기 2종 합금의 경우에는 Zn-X(X=Fe, Co, Ni, Mg), 상기 3종 합금의 경우에는 Zn-A-B(A=Al, B=Si,Mg)가 바람직하다. Zn-X (X = Fe, Co, Ni, Mg) is preferable for the two kinds of alloys and Zn-A-B (A = Al, B = Si, Mg) is preferable for the three kinds of alloys.
특히, 상기 아연도금 강판으로는 냉연강판에 5 내지 60 g/m2의 도금 부착량으로 아연 또는 아연합금, 용융아연 또는 합금 용융아연이 도금된 것이 보다 바람직하다.In particular, as the zinc-plated steel sheet, it is more preferable that the cold-rolled steel sheet is plated with zinc or zinc alloy, molten zinc or molten zinc with an amount of plating of 5 to 60 g / m 2 .
본 발명에서 수지 코팅층은 우레탄 수지, 멜라민 경화제, 실리케이트 화합물, 티타늄 화합물, 인산에스테르 및 전도성 첨가제를 포함하는 강판 코팅 용액을 경화시켜 형성된 것이 바람직하다In the present invention, the resin coating layer is preferably formed by curing a steel plate coating solution containing a urethane resin, a melamine curing agent, a silicate compound, a titanium compound, a phosphoric acid ester and a conductive additive
본 발명의 복합 수지 코팅 용액에 사용되는 주제 수지는 내부식성과 내연료성이 우수한 우레탄 수지와 경화제로 멜라민 수지를 사용하며, 우레탄 수지로는 수분산된 페녹시 변성 우레탄 수지가 보다 바람직하다. 우레탄 수지가 내연료성과 내식성에서 우수한 특징을 나타내는 이유는 페녹시 변성 우레탄 수지가 다른 고분자 수지와는 달리 유리 전이 온도(Glass Transition Temperature, Tg)가 높기 때문이다. Tg 가 높으면 사용 환경의 온도가 높아져도 고분자의 분자운동이 일어나지 않으므로 외부의 부식인자(수분, 휘발유 등)에 대하여 영향을 받지 않는 장점이 있다. 즉, Tg가 높으면 부식인자가 소지강판에 도달하지 못하도록 차폐 효가가 우수하다고 할 수 있다. The main resin used in the composite resin coating solution of the present invention is a urethane resin having excellent corrosion resistance and fuel resistance and a melamine resin as a curing agent, and as the urethane resin, a phenoxy-modified urethane resin which is water-dispersed is more preferable. The reason why urethane resin shows excellent characteristics in fuel resistance and corrosion resistance is that the phenoxy-modified urethane resin has a high glass transition temperature (Tg) unlike other polymer resins. If the Tg is high, the molecular motion of the polymer does not occur even when the temperature of the environment of use is increased, which is advantageous in that it is not affected by external corrosive factors (moisture, gasoline, etc.). That is, when the Tg is high, the shielding effect is excellent so that the corrosion factor can not reach the steel sheet.
상기 우레탄 수지는 수평균 분자량이 25,000 내지 70,000이 바람직하고, 35,000 내지 60,000이 보다 바람직하다. 우레탄 수지의 수평균 분자량이 25,000 미만이면 내연료성이 나빠지고, 70,000을 초과하면 조성물의 저장안정성 및 작업성이 나빠지는 문제가 있어 바람직하지 않다. The number average molecular weight of the urethane resin is preferably 25,000 to 70,000, more preferably 35,000 to 60,000. When the number average molecular weight of the urethane resin is less than 25,000, the fuel resistance is deteriorated. When the number average molecular weight is more than 70,000, the storage stability and workability of the composition deteriorate.
우레탄 수지 100 중량부에 대하여 멜라민 수지는 3 내지 40 중량부를 사용하는 것이 바람직하다. 3 중량부 미만으로 사용하면 건조도막의 경화반응이 완벽하게 않아 도막의 물성이 나쁘며, 40 중량부를 초과 사용하면 과량의 경화제에 의해 부반응이 일어나 도막의 가공물성이 나빠지기 때문에 바람직하지 않다. 이때, 경화제는 반응성이 우수한 것을 선정하는 것이 좋으며, 이로서 한정하는 것으로 아니지만, 멜라민, 부톡시메틸 멜라민, 헥사메톡시메틸 멜라민 및 트리메톡시메틸 멜라민 등이 사용될 수 있다. 상기 멜라민계 경화제는 단독으로 혹은 2종 이상의 혼합물로 사용될 수 있다. The melamine resin is preferably used in an amount of 3 to 40 parts by weight based on 100 parts by weight of the urethane resin. When the amount is less than 3 parts by weight, the curing reaction of the dry film is not perfect and the physical properties of the coating film are poor. When the amount of the curing agent is more than 40 parts by weight, side reactions occur due to excessive curing agent. At this time, it is preferable to select a curing agent having excellent reactivity, and it is not limited thereto, but melamine, butoxymethylmelamine, hexamethoxymethylmelamine, trimethoxymethylmelamine and the like can be used. The melamine-based curing agent may be used alone or as a mixture of two or more thereof.
상기 복합 수지 코팅 용액에는 건조도막의 내부식성을 향상시키기 위하여 실리케이트 화합물을 첨가한다. 상기 실리케이트 화합물의 예로는 이로서 한정하는 것은 아니지만, 리튬 폴리실리케이트, 소듐 폴리실리케이트, 포타슘 폴리실리케이트 및 콜로이달 실리카로 구성되는 군으로부터 단독 혹은 2종 이상의 혼합물로 사용될 수 있다. 우레탄 수지 100 중량부에 대하여 실리케이트 화합물은 5 내지 60 중량부를 사용하는 것이 바람직하다. 만약 실리케이트 함량이 5 중량부 미만이면 함량이 너무 적어서 내부식성 효과가 미흡하고, 60 중량부를 초과하면 내부식성은 향상되나 도막이 거칠어져서 좋지 않다. A silicate compound is added to the composite resin coating solution in order to improve the corrosion resistance of the dried coating film. Examples of the silicate compound include, but are not limited to, lithium poly silicate, sodium polysilicate, potassium polysilicate, and colloidal silica, or a mixture of two or more thereof. The silicate compound is preferably used in an amount of 5 to 60 parts by weight based on 100 parts by weight of the urethane resin. If the amount of the silicate is less than 5 parts by weight, the content is too small and the corrosion resistance effect is insufficient. When the amount exceeds 60 parts by weight, the corrosion resistance is improved but the coating film becomes rough.
상기 복합 수지 코팅 용액에는, 또한 건조도막의 내부식성을 향상시키기 위하여 티타늄 화합물을 첨가한다. 상기 티타늄 화합물은 작은 함량을 투입하여도 가공부에 대한 내부식성이 향상되는 장점이 있다. 본 발명에 사용되는 티타늄 화합물로는 Dupont 사에서 제조하는 티타늄 카보네이트, 이소프로필디트리에탄올아미노 티타네이트, 락틱산 티타늄킬레이트 및 티타늄 아세틸아세토네이트로 이루어진 군으로부터 선택하여 사용할 수 있다. 이들 티타늄 화합물은 1종 또는 2종 이상의 혼합물로 사용될 수 있다. 우레탄 수지 100 중량부에 대하여 티타늄 화합물 함량은 3 내지 20 중량부를 사용하는 것이 바람직하다. 만약 티타늄 화합물 함량이 3 중량부 미만이면 함량이 너무 적어 내부식성 효과가 미흡하고, 20 중량부 초과하면 내부식성은 향상되나 제조원가가 지나치게 상승하여 바람직하지 않다.A titanium compound is added to the composite resin coating solution to improve the corrosion resistance of the dried coating film. The titanium compound is advantageous in that corrosion resistance to the processed portion is improved even when a small amount of titanium compound is added. The titanium compound used in the present invention may be selected from the group consisting of titanium carbonate, isopropyl ditriethanol aminotitanate, titanium lactate lactate, and titanium acetylacetonate manufactured by Dupont. These titanium compounds may be used alone or in combination of two or more. The content of the titanium compound is preferably 3 to 20 parts by weight based on 100 parts by weight of the urethane resin. If the content of the titanium compound is less than 3 parts by weight, the corrosion resistance is insufficient and if it exceeds 20 parts by weight, the corrosion resistance is improved but the manufacturing cost is undesirably increased.
또한, 상기 복합 수지 코팅 용액에는 소지강판과의 밀착성을 향상시키기 위하여 인산 에스테르를 첨가한다. 인산 에스테르에 의한 도막밀착력은 계면에서 인산에스테르 작용기와 고분자 수지 및 도금층과의 다중결합에 의해 향상된다. 즉, 금속과 비금속과의 가교 역할을 함으로써 도막의 밀착력이 향상하고 이에 따라 가공성 및 내연료성이 향상된다. 우레탄 수지 100 중량부에 대하여 인산에스테르는 1 내지 20 중량부를 사용하는 것이 바람직하다. 만일 인산에스테르를 1 중량부 미만 사용하게 되면 함량이 너무 적어 효과가 미흡하고, 20 중량부를 초과 사용하면 조성물의 저장 안정성이 저해되어 바람직하지 않다.In addition, phosphoric acid ester is added to the composite resin coating solution in order to improve the adhesion with the base steel sheet. The adhesion of the film to the film by the phosphate ester is improved by the multiple bonds of the phosphate ester functional group with the polymer resin and the plating layer at the interface. In other words, the adhesion between the metal and the nonmetal improves the adhesion of the coating, thereby improving the workability and fuel resistance. The phosphate ester is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the urethane resin. If less than 1 part by weight of phosphoric acid ester is used, the effect is insufficient because the content is too small, and if it exceeds 20 parts by weight, the storage stability of the composition is impaired.
다음으로, 상기 복합 수지 코팅 용액에는 용접성 향상을 위하여 전도성 첨가체를 첨가한다. 전도성 첨가제가 고분자 수지와 단순 혼합된 경우에는 건조도막 형성 시 내용제성과 내식성이 나쁘고, 가공 시에도 가루가 발생하는 단점이 있다. 이를 개선하기 위해 전도성 첨가제를 고분자 수지 매트릭스에 함입하여 용액제조 시 안정성이 우수하고 건조도막이 형성될 때 내부식성과 용접성이 동시에 좋아지는 장점이 있다.Next, a conductive additive is added to the composite resin coating solution to improve the weldability. When the conductive additive is simply mixed with the polymer resin, there is a disadvantage that the solvent resistance and corrosion resistance are poor when the dry film is formed, and the powder is also produced at the time of processing. In order to solve this problem, the conductive additive is incorporated into the polymer resin matrix to provide excellent stability in solution preparation, and corrosion resistance and weldability are improved at the same time when a dry film is formed.
우레탄 수지 100 중량부에 대하여 첨가되는 전도성 첨가제 함량은 1 내지 20 중량부가 바람직하다. 만일 전도성 첨가제 함량이 1 중량부 미만이면 함량이 너무 적어 건조도막의 표면 전기전도성이 미흡하고, 20 중량부를 초과하면 건조도막의 물성이 나빠져 내연료성이 나빠지는 단점이 있다. 상기 전도성 첨가제로는 전기전도성이 우수한 나노크기의 그라파이트, 탄소나노튜브 또는 그래핀 등의 탄소화합물과 나노 크기의 금속 입자가 사용될 수 있다. 나노 금속의 종류로는 Ni, Zn, Al, Cu, Ag, W, Mo, Co, Pd, Au 등의 전이금속이 사용된다. 상기 나노 금속은 평균 입경이 0.5 내지 400 nm가 바람직하며, 1 내지 350 nm가 보다 바람직하며, 10 내지 300 nm가 더욱 바람직하다. 입경이 400 nm를 초과하면 비중이 커서 고분자 매트릭스에 혼입되지 않아 방치 시 침전되어 저장성이 문제될 수 있기 때문이다.The content of the conductive additive added to 100 parts by weight of the urethane resin is preferably 1 to 20 parts by weight. If the content of the conductive additive is less than 1 part by weight, the surface electrical conductivity of the dry coating film is insufficient, and if it exceeds 20 parts by weight, the physical properties of the dry coating film deteriorate and the fuel property is deteriorated. As the conductive additive, carbon compounds such as nano-sized graphite, carbon nanotubes, or graphene having excellent electrical conductivity and nano-sized metal particles may be used. As the nano metal, transition metals such as Ni, Zn, Al, Cu, Ag, W, Mo, Co, Pd and Au are used. The nanometer metal preferably has an average particle diameter of 0.5 to 400 nm, more preferably 1 to 350 nm, further preferably 10 to 300 nm. If the particle diameter is more than 400 nm, the specific gravity is too large to be incorporated into the polymer matrix, which may precipitate when left standing, resulting in poor storage stability.
상기 복합 수지 코팅 용액에 사용될 수 있는 용제로는 물, 메탄올, 에탄올, 이소프로판올 등을 사용할 수 있으며, 이의 함량은 우레탄 수지 100 중량부에 대하여 50 내지 500 중량부가 바람직하다. Water, methanol, ethanol, isopropanol and the like may be used as the solvent for the composite resin coating solution, and the content thereof is preferably 50 to 500 parts by weight based on 100 parts by weight of the urethane resin.
또한, 본 발명은 강팡 상에 고분자 매트릭스 내부에 전도성 첨가제가 함입된 수지 코팅층을 형성하는 단계를 포함하는 복합수지 코팅강판의 제조방법에 관한 것이다.The present invention also relates to a method of manufacturing a composite resin-coated steel sheet, which comprises the step of forming a resin coating layer in which a conductive additive is embedded in a polymer matrix.
보다 구체적으로는, 본 발명은 우레탄 수지와 전도성 첨가제를 고속 혼합하고 초음파 처리하고, 멜라민 경화제, 실리케이트 화합물, 티타늄 화합물 및 인산에스테르를 혼합하여 복합수지 코팅 용액을 제조하는 단계; 및 강판 상에 상기 복합수지 코팅 용액을 코팅하여 수지 코팅층을 형성하는 단계를 복합수지 코팅 강판의 제조방법을 포함한다.More specifically, the present invention relates to a method for preparing a composite resin coating solution, which comprises mixing a urethane resin and a conductive additive at a high speed, subjecting the mixture to ultrasonic treatment, mixing a melamine curing agent, a silicate compound, a titanium compound and a phosphate ester to prepare a composite resin coating solution; And coating the composite resin coating solution on the steel sheet to form a resin coating layer.
특히, 본 발명에 따른 복합수지 코팅 용액은 기존 마이크로 사이즈의 금속 분말과 고분자 수지를 단순 혼합시켜 제조되는 것과 달리, 전도성 첨가제와 우레탄 수지를 비드(Bead)를 이용하여 고속 혼합하고 초음파 처리 과정을 거침으로써 고분자 매트릭스 내부에 전도성 첨가제가 함입된 수지 코팅층을 형성할 수 있다. Particularly, the composite resin coating solution according to the present invention is prepared by simple mixing of a conventional micro-sized metal powder and a polymer resin, the conductive additive and the urethane resin are mixed at a high speed using a bead, A resin coating layer in which a conductive additive is embedded in the polymer matrix can be formed.
상기 우레탄 수지는 수평균 분자량이 25,000 내지 70,000인 것이 바람직하며, 상기 전도성 첨가제로 나노 사이즈의 나노 금속이 바람직하다. 상기 "고속 혼합"이라 함은 500 내지 10000 rpm의 속도로 5시간 내지 24시간 동안 20 내지 30 ℃의 온도 조건 하에서 교반하는 것을 의미한다. 상기 초음파 처리는 1 KA 내지 10 KA 세기의 조건에서 24 내지 72시간 처리하는 것을 의미한다. 추가적으로, 초음파 처리 후 24 내지 72시간 방치하여 입자가 큰 침전물을 제거하는 단계를 거칠 수 있다.The urethane resin preferably has a number average molecular weight of 25,000 to 70,000, and the conductive additive is preferably a nano-sized nano metal. The term "high-speed mixing" means stirring under a temperature condition of 20 to 30 DEG C for 5 to 24 hours at a speed of 500 to 10,000 rpm. The ultrasonic treatment means treatment for 24 to 72 hours under the condition of 1 KA to 10 KA strength. In addition, it may be left to stand for 24 to 72 hours after the ultrasonic treatment to remove large sediment.
상기 전도성 첨가제와 고분자 수지를 포함하는 조성에, 멜라민 경화제, 실리케이트 화합물, 티타늄 화합물 및 인산에스테르를 혼합하여 복합수지 코팅 용액을 제조한다.The composition containing the conductive additive and the polymer resin is mixed with a melamine curing agent, a silicate compound, a titanium compound and a phosphate ester to prepare a composite resin coating solution.
상기와 같은 조성으로 이루어진 복합수지 코팅 용액을 강판에 롤 코팅 혹은 스프레이 코팅방법으로 코팅한 다음 열풍 또는 유도가열로 오븐에서 소부경화하여 복합코팅 도막을 형성한다.The composite resin coating solution having the above composition is coated on a steel sheet by a roll coating or a spray coating method, followed by baking in an oven by hot air or induction heating to form a composite coating film.
상기 복합수지 코팅층의 코팅량은 0.2 내지 2.5 g/m2이 바람직하며, 부착량이 0.2 g/m2 미만에서는 원하는 내식성과 내연료성 확보가 어렵게 되고, 2.5 g/m2 초과하면 절연성이 커져 용접성이 나빠지게 되므로 바람직하지 않다. 코팅도막의 소부 건조 온도는 강판온도(PMT, Peak Metal Temperature) 기준으로 160 내지 250 ℃의 온도범위가 바람직한데 온도가 160℃ 미만에서는 경화반응이 미흡하여 내부식성과 내연료성 확보가 곤란하다. 반대로 250 ℃를 초과할 경우에는 멜라민 경화제의 가교반응이 너무 증가하여 도막이 딱딱해져 가공성이 나빠지는 단점이 있다. 상기 코팅층의 두께는 0.3 내지 2 ㎛인 것이 좋다. 코팅층 두께가 0.3 ㎛ 미만이면 도막 두께가 얇아 충분한 내부식성과 내연료성을 확보하기 어렵고, 2 ㎛ 초과하면 내부식성과 내연료성은 향상되나 절연성이 커져 용접성이 저하되는 단점이 있다. 복합수지 조성물을 강판에 도포하는 방법으로는 롤코팅, 스프레이 코팅, 침적법 등 여러 가지 방법이 있으나 롤코팅 방법이 가장 바람직하다.
The coating amount of the composite resin coating layer is preferably 0.2 to 2.5 g / m 2. When the adhesion amount is less than 0.2 g / m 2 , the desired corrosion resistance and fuel resistance are difficult to be secured. When the coating amount exceeds 2.5 g / m 2, Which is undesirable. The baking temperature of the coating film is preferably 160 to 250 ° C. on the basis of the steel plate temperature (PMT). When the temperature is lower than 160 ° C., the curing reaction is insufficient and it is difficult to secure corrosion resistance and fuel resistance. On the other hand, when the temperature is higher than 250 ° C, the crosslinking reaction of the melamine curing agent is excessively increased, resulting in a hard coating film, resulting in poor processability. The thickness of the coating layer is preferably 0.3 to 2 占 퐉. If the thickness of the coating layer is less than 0.3 탆, it is difficult to ensure sufficient corrosion resistance and fuel resistance, and when it exceeds 2 탆, the corrosion resistance and fuel resistance are improved but the insulating property is increased and the weldability is deteriorated. As a method of applying the composite resin composition to a steel sheet, there are various methods such as roll coating, spray coating, and deposition, but a roll coating method is most preferred.
이하, 본 발명에 따르는 실시예 통하여 본 발명을 보다 상세히 설명하나, 본 발명의 범위가 하기 제시된 실시예에 의해 제한되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention, but the scope of the present invention is not limited by the following Examples.
실시예Example 1 ~ 20: 복합수지 강판 제조 1 to 20: Manufacture of composite resin steel sheet
주제 수지로 수평균 분자량이 50,000인 페녹시 변성 우레탄 수지 및 입경이 200 nm인 Cu 분말을 5000 rpm의 속도로 24시간 동안 상온에서 비드를 이용하여 고속 교반하고, 5 KA 세기의 초음파로 48시간 동안 처리하였다. 또한, 48시간 동안 방치한 후 입자가 큰 침전물을 제거하였다. 상기 혼합물에 경화제로 멜라민 수지, 입경이 20 nm인 소듐 실리케이트, 티타네이트, 인산 에스테르 및 순수를 첨가하여 고형분이 10 내지 35 중량%가 되도록 복합수지 코팅을 제조하였다.Phenoxy-modified urethane resin having a number average molecular weight of 50,000 and Cu powder having a particle diameter of 200 nm were stirred at a high speed of 5000 rpm for 24 hours at a room temperature using beads and ultrasonicated for 48 hours Respectively. Further, after allowing to stand for 48 hours, a large sediment was removed. A melamine resin as a curing agent, sodium silicate having a particle diameter of 20 nm, titanate, phosphoric ester and pure water were added to the mixture to prepare a composite resin coating such that the solid content was 10 to 35% by weight.
도금량이 30g/m2인 아연도금 강판 상에 상기 복합수지 코팅 용액을 롤 코팅 방법으로 코팅하고, 강판 온도가 190 ℃되게 소부 건조한 다음, 냉각하여 건조도막의 중량이 0.3 내지 2 g/m2인 복합수지 코팅 강판을 제조하였다. The composite resin coating solution was coated on a galvanized steel sheet having a plating amount of 30 g / m 2 by a roll coating method, and the steel sheet was baked to a temperature of 190 ° C., followed by cooling to obtain a dry film having a weight of 0.3 to 2 g / m 2 A composite resin coated steel sheet was produced.
비교예Comparative Example 1 ~ 4: 마이크론 사이즈의 금속 분말을 사용하여 단순 혼합한 경우 1 to 4: In case of simple mixing using a metal powder of micron size
주제 수지로 수평균 분자량이 50,000인 페녹시 변성 우레탄 수지, 입경이 1 마이크론 크기의 Cu 분말, 경화제로 멜라민 수지, 입경이 20 nm인 소듐 실리케이트, 티타네이트, 인산 에스테르 및 순수를 첨가하여 고형분이 10 내지 35 중량%가 되도록 복합수지 코팅 용액을 제조하였다.A phenoxy-modified urethane resin having a number average molecular weight of 50,000 as a main resin, a Cu powder having a particle size of 1 micron, a melamine resin as a hardening agent, sodium silicate having a particle diameter of 20 nm, titanate, phosphoric acid ester and pure water to give a solid content of 10 By weight to 35% by weight.
도금량이 30g/m2인 아연도금 강판 상에 상기 복합수지 코팅 용액을 롤 코팅 방법으로 코팅하고, 강판 온도가 190 ℃되게 소부 건조한 다음, 냉각하여 건조도막의 중량이 0.3 내지 2 g/m2인 복합수지 코팅 강판을 제조하였다. The composite resin coating solution was coated on a galvanized steel sheet having a plating amount of 30 g / m 2 by a roll coating method, and the steel sheet was baked to a temperature of 190 ° C., followed by cooling to obtain a dry film having a weight of 0.3 to 2 g / m 2 A composite resin coated steel sheet was produced.
[표 1] [Table 1]
실시예 1 내지 20은 나노 금속 분말이 주제 수지와 혼합 후 방치하면 침전이 일어나지 않아 용액 안정성이 우수하며, 가공 시 가루가 발생하는 문제가 없어 프로세스 작업성도 우수하다. 반면에, 비교예 1 내지 4는 마이크론 금속 입자가 주제 수지와 단순 혼합 후 방치하면 침전이 일어나 용액 안정성이 우수하지 못하며, 가공 시 가루가 발생하여 프로세스 작업성 역시 좋지 않다. Examples 1 to 20 are excellent in solution stability because no precipitation occurs when the nano-metal powder is mixed with the main resin and left standing, there is no problem of generating powder during processing, and the process workability is also excellent. On the other hand, in Comparative Examples 1 to 4, when the micron metal particles were left to stand after mixing with the main resin, precipitation occurred and the solution stability was not excellent.
실험예Experimental Example
품질평가로는 도막 밀착성, 내식성, 표면 전기전도성, 내연료성 및 용접성 등 연료탱크 강판에 필요한 물성을 평가하였다.
The evaluation of the properties required for the steel plate of the fuel tank, such as coating adhesion, corrosion resistance, surface electric conductivity, fuel resistance and weldability.
강판의 건조도막의 밀착성 평가는 강판을 비등수에 넣고 끓인 후 내비등수성과 컵가공 후 가공부 도막 박리성 평가를 하였다. The evaluation of the adhesion of the dried coating film to the steel sheet was carried out by evaluating the water resistance of the steel sheet after boiling in a boiling water and the peelability of the coating film after the cup processing.
내비등수 도막 밀착성은 비등수에 30분 동안 끓인 다음 5분간 자연 방치시켜 건조한 후, 스카치 테이프를 강판에 붙인 후 박리하여 평가하였다. 그 평가 기준은 다음과 같다. The coating adhesion of the coating film was evaluated by boiling for 30 minutes in boiling water, drying after allowing to stand for 5 minutes, sticking a scotch tape to the steel sheet, peeling off. The evaluation criteria are as follows.
◎ : 박리된 면적이 0~5% ⊚: The peeled area is 0 to 5%
○ : 박리된 면적이 5~20%○: The peeled area is 5 to 20%
△ : 박리된 면적이 20~50% B: The peeled area was 20 to 50%
× : 박리된 면적이 50% 이상X: Peeled area is 50% or more
컵가공 후의 도막 밀착성은 강판을 95mmφ 크기로 펀칭하고, 가공다이의 곡률반경이 4가 되도록 하여 높이 25mm로 컵가공한 다음 가공 벽면을 스카치 테이프로 강판에 붙인 후 박리하여 평가하였다. 그 평가 기준은 다음과 같다.The coated film adhesion after cup processing was evaluated by punching the steel sheet to a size of 95 mmφ, cupping it to a height of 25 mm so that the radius of curvature of the processing die was 4, and then peeling the coated wall surface with a scotch tape. The evaluation criteria are as follows.
◎ : 박리된 면적이 0~5% ⊚: The peeled area is 0 to 5%
○ : 박리된 면적이 5~20%○: The peeled area is 5 to 20%
△ : 박리된 면적이 20~50% B: The peeled area was 20 to 50%
× : 박리된 면적이 50% 이상
X: Peeled area is 50% or more
내식성은 염수농도 5%, 35℃에서 1kg/cm2의 분무압 조건에서 복합코팅한 강판이 1,000시간이 지난 후 표면에 발생한 적녹의 발생면적으로 평가하였다. 그 평가 기준은 다음과 같다.Corrosion resistance was evaluated by the area of the green rust generated on the surface after 1,000 hours of the coated steel sheet at 5% salinity concentration and spray pressure of 1 kg / cm 2 at 35 ° C. The evaluation criteria are as follows.
◎ : 부식 면적이 0% ◎: Corrosion area is 0%
○ : 부식 면적이 5% 이하○: Corrosion area less than 5%
△ : 부식 면적이 5~30% ?: Corrosion area is 5 to 30%
× : 부식 면적이 30% 이상
X: Corrosion area of 30% or more
표면 전기전도성은 LORESTA EP (미씨비씨㈜) 기기를 이용하여 저항값을 측정하여 평가하였다. 그 평가 기준은 다음과 같다.The surface electrical conductivity was evaluated by measuring the resistance value using a LORESTA EP (Misc. The evaluation criteria are as follows.
◎ : 저항 10mW 이하 ◎: Resistance 10 mW or less
○ : 10mW 이상 100mW 이하 ○: 10 mW or more and 100 mW or less
△ : 100mW 이상 1000mW 이하 ?: 100 mW or more and 1000 mW or less
× : 1000mW 이상
×: 1000 mW or more
내연료성은 에탄올과 바이오디젤의 고온 내연료성으로 평가하였다. 평가시편은 상기와 같이 컵 가공 후 도 3과 같이 컵에 연료를 넣고 오링과 유리판을 이용하여 덮어 고정하여 평가하였다. The fuel resistance was evaluated by the high temperature resistance of ethanol and biodiesel. After the cup was processed as described above, the evaluation specimen was evaluated by putting the fuel into the cup and fixing it by using an o-ring and a glass plate as shown in Fig.
에탄올 연료성은 85% 에탄올 (5% 순수) + 15% 무연휘발류 + 20ppm 개미산을 60 ℃에서 3개월 방치한 다음 강판의 부식상태를 평가하였다. Ethanol fuelability was evaluated by evaluating the corrosion of the steel sheet after leaving ethanol at 85% ethanol (5% pure) + 15% unburned gasoline + 20 ppm formic acid at 60 ℃ for 3 months.
바이오 디젤의 경우에는 80% 경유(10% 순수 포함) + 20% 바이오 디젤을 90 ℃에서 3개월 방치 후 강판의 부식상태를 평가하였다. 그 평가 기준은 다음과 같다. In the case of biodiesel, corrosion of the steel sheet was evaluated after 80% diesel (including 10% pure water) + 20% biodiesel was left at 90 ° C for 3 months. The evaluation criteria are as follows.
◎ : 부식 면적이 0% ◎: Corrosion area is 0%
○ : 부식 면적이 5% 이하○: Corrosion area less than 5%
△ : 부식 면적이 5~30% ?: Corrosion area is 5 to 30%
× : 부식 면적이 30% 이상
X: Corrosion area of 30% or more
용접성은 공압식 AC 스폿 용접기를 이용하여 가압력 250kg, 용접시간 15Cycle 통전전류는 7.5kA에서 스패이트(Spatter)가 없으며 일정한 강도를 유지하는 것으로 평가하였다. 평가 기준은 용접이 가능한 점 용접타점 수로 평가하였다. Weldability was evaluated by using a pneumatic AC spot welding machine to maintain a constant strength without spatter at a pressing force of 250 kg and a welding time of 15 cycles and an electrification current of 7.5 kA. The evaluation criteria were evaluated by the number of spot welded spot points that can be welded.
◎ : 1200 타점 이상 ◎: Over 1200 RB points
○ : 900 이상 1200 이하○: 900 or more and 1200 or less
△ : 600 이상 900 이하 ?: 600 or more and 900 or less
× : 500 이하×: not more than 500
[표 2] [Table 2]
하기 표 3은 강판 소재만을 변경시킨 것 외에는 실시예 1과 동일한 방법으로 복합수지 코팅 강판을 제조하였고, 물성을 평가한 결과를 나타낸 것이다. The following Table 3 shows the result of evaluating the physical properties of the composite resin-coated steel sheet prepared in the same manner as in Example 1 except that only the steel sheet material was changed.
[표 3][Table 3]
다양한 소재별 강판의 품질평가Quality evaluation of various steel sheets
Claims (19)
A composite resin coated steel sheet on which a resin coating layer containing a conductive additive is formed on a steel sheet in a polymer matrix.
상기 수지 코팅층은 우레탄 수지, 멜라민 경화제, 실리케이트 화합물, 티타늄 화합물, 인산에스테르 및 전도성 첨가제를 포함하는 강판 코팅 용액을 경화시켜 형성된 복합수지 코팅 강판.
The method according to claim 1,
Wherein the resin coating layer is formed by curing a steel plate coating solution comprising a urethane resin, a melamine curing agent, a silicate compound, a titanium compound, a phosphoric acid ester, and a conductive additive.
상기 수지 코팅층은 우레탄 수지 100 중량부, 멜라민 경화제 3 내지 40 중량부, 실리케이트 화합물 5 내지 60 중량부, 티타늄 화합물 3 내지 20 중량부, 인산에스테르 1 내지 20 중량부, 전도성 첨가제 1 내지 20 중량부를 포함하는 강판 코팅 용액을 경화시켜 형성된 복합수지 코팅 강판.
3. The method of claim 2,
The resin coating layer contains 100 parts by weight of a urethane resin, 3 to 40 parts by weight of a melamine curing agent, 5 to 60 parts by weight of a silicate compound, 3 to 20 parts by weight of a titanium compound, 1 to 20 parts by weight of a phosphoric ester, and 1 to 20 parts by weight of a conductive additive Coated steel plate formed by curing a steel plate coating solution.
상기 우레탄 수지는 수평균 분자량이 25,000 내지 70,000인 복합수지 코팅 강판.
3. The method of claim 2,
Wherein the urethane resin has a number average molecular weight of 25,000 to 70,000.
상기 우레탄 수지는 페녹시 변성 우레탄 수지인 복합수지 코팅 강판.
3. The method of claim 2,
Wherein the urethane resin is a phenoxy-modified urethane resin.
상기 실리케이트 화합물은 리튬 폴리실리케이트, 소디움 폴리실리케이트, 포타슘 폴리실리케이트 및 콜로이달 실리카로 구성되는 군으로부터 1종 이상인 복합수지 코팅 강판.
3. The method of claim 2,
Wherein the silicate compound is at least one member selected from the group consisting of lithium polysilicate, sodium polysilicate, potassium polysilicate, and colloidal silica.
상기 티타늄 화합물은 티타늄 카보네이트, 이소프로필디트리에탄올아미노 티타네이트, 락틱산 티타늄킬레이트 및 티타늄 아세틸아세토네이트로 구성되는 군으로부터 1종 이상인 복합수지 코팅 강판.
3. The method of claim 2,
Wherein the titanium compound is at least one member selected from the group consisting of titanium carbonate, isopropyl ditriethanol aminotitanate, titanium lactate lactate, and titanium acetylacetonate.
상기 전도성 첨가제는 나노 금속 또는 탄소 화합물인 복합수지 코팅 강판.
3. The method of claim 2,
Wherein the conductive additive is a nano metal or a carbon compound.
상기 탄소 화합물은 그라파이트, 탄소나노튜브 또는 그래핀인 복합수지 코팅 강판.
8. The method of claim 7,
Wherein the carbon compound is graphite, carbon nanotube or graphene.
상기 금속은 Ni, Zn, Al, Cu, Ag, W, Mo, Co, Pd 및 Au 로 이루어진 군으로부터 선택된 1종 이상인 복합수지 코팅 강판.
9. The method of claim 8,
Wherein the metal is at least one selected from the group consisting of Ni, Zn, Al, Cu, Ag, W, Mo, Co, Pd and Au.
상기 나노 금속은 평균 입경이 0.1 내지 400 nm인 복합수지 코팅 강판.
9. The method of claim 8,
Wherein the nano metal has an average particle diameter of 0.1 to 400 nm.
상기 강판 코팅 용액의 코팅량은 0.1 내지 2.5 g/m2인 복합수지 코팅 강판.
3. The method of claim 2,
The coating amount of the steel plate coating solution is 0.1 to 2.5 g / m 2 .
상기 코팅층의 두께는 0.3 내지 2μm 인 복합수지 코팅 강판.
The method according to claim 1,
Wherein the coating layer has a thickness of 0.3 to 2 占 퐉.
상기 강판은 아연 도금 강판인 복합수지 코팅 강판.
The method according to claim 1,
Wherein the steel sheet is a galvanized steel sheet.
상기 아연 도금 강판은 냉연강판에 아연 또는 아연합금, 용융아연 또는 합금 용융아연이 도금된 복합수지 코팅 강판.
15. The method of claim 14,
The zinc-plated steel sheet is a composite resin-coated steel sheet in which a cold-rolled steel sheet is plated with zinc or a zinc alloy, hot-dip zinc or alloy hot-dip zinc.
And forming a resin coating layer in which a conductive additive is embedded in the polymer matrix on the steel sheet.
수평균 분자량이 25,000 내지 70,000인 우레탄 수지와 전도성 첨가제를 고속 혼합하고 초음파 처리하고, 멜라민 경화제, 실리케이트 화합물, 티타늄 화합물 및 인산에스테르를 혼합하여 복합수지 코팅 용액을 제조하는 단계 및
강판 상에 상기 복합수지 코팅 용액을 코팅하여 수지 코팅층을 형성하는 단계를 복합수지 코팅 강판의 제조방법.
17. The method of claim 16,
Mixing a urethane resin having a number average molecular weight of 25,000 to 70,000 with a conductive additive at a high speed and subjecting the mixture to ultrasonic treatment to prepare a composite resin coating solution by mixing a melamine curing agent, a silicate compound, a titanium compound and a phosphoric acid ester;
A method for manufacturing a composite resin-coated steel sheet, comprising the steps of: coating a steel sheet with the composite resin coating solution to form a resin coating layer.
상기 고속 혼합은 500 내지 10000 rpm의 속도로 5시간 내지 24시간 동안 20 내지 30 ℃의 온도 조건 하에서 교반하는 복합수지 코팅 강판의 제조방법.
18. The method of claim 17,
Wherein the high-speed mixing is performed at a temperature of from 20 to 30 占 폚 for from 5 hours to 24 hours at a speed of from 500 to 10000 rpm.
상기 초음파는 1 KA 내지 10 KA 세기의 조건에서 24 내지 72시간 처리하는 복합수지 코팅 강판의 제조방법.18. The method of claim 17,
Wherein the ultrasonic waves are treated for 24 to 72 hours under the condition of 1 KA to 10 KA.
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| WO2020067802A1 (en) * | 2018-09-28 | 2020-04-02 | 주식회사 포스코 | Composite resin composition for fuel tank steel sheet, composite resin coating steel sheet using same and producing method thereof |
| KR20230099057A (en) | 2021-12-27 | 2023-07-04 | 정대승 | Automatic removal of residual thread wound on bobbin that minimizes the wear of the cutting blade for cutting residual thread |
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| CN101945566A (en) * | 2007-03-23 | 2011-01-12 | 株式会社神户制钢所 | Conductive resin coating metal panel |
| JP2008246974A (en) * | 2007-03-30 | 2008-10-16 | Kobe Steel Ltd | Laminated resin coated metal plate excellent in electromagnetic wave absorbency |
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| KR20200036667A (en) * | 2018-09-28 | 2020-04-07 | 주식회사 포스코 | Composite resin composition for steel sheet of fuel tank, coated steel sheet using the same and method for manufacturing the coated steel sheet |
| CN112867767A (en) * | 2018-09-28 | 2021-05-28 | Posco公司 | Composite resin composition for fuel tank steel plate, composite resin-coated steel plate using same, and method for producing same |
| KR20230099057A (en) | 2021-12-27 | 2023-07-04 | 정대승 | Automatic removal of residual thread wound on bobbin that minimizes the wear of the cutting blade for cutting residual thread |
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