KR100979950B1 - Eco-Friendly Chrome Free Film Composition for Galvanized Steel Sheet - Google Patents
Eco-Friendly Chrome Free Film Composition for Galvanized Steel Sheet Download PDFInfo
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- KR100979950B1 KR100979950B1 KR1020080102289A KR20080102289A KR100979950B1 KR 100979950 B1 KR100979950 B1 KR 100979950B1 KR 1020080102289 A KR1020080102289 A KR 1020080102289A KR 20080102289 A KR20080102289 A KR 20080102289A KR 100979950 B1 KR100979950 B1 KR 100979950B1
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- South Korea
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- steel sheet
- galvanized steel
- chromium
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 28
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title description 3
- -1 titanium ions Chemical class 0.000 claims abstract description 22
- 239000008199 coating composition Substances 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 150000002823 nitrates Chemical class 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 abstract description 34
- 238000005260 corrosion Methods 0.000 abstract description 34
- 229910000831 Steel Inorganic materials 0.000 abstract description 9
- 239000010959 steel Substances 0.000 abstract description 9
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004071 soot Substances 0.000 abstract description 5
- 238000003466 welding Methods 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 208000022133 pulmonary valve agenesis Diseases 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- VGNJJNFWWIDONZ-UHFFFAOYSA-N acetyl acetate;titanium Chemical compound [Ti].CC(=O)OC(C)=O VGNJJNFWWIDONZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- ABXXWVKOBZHNNF-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)chromium Chemical compound [Cr+3].[Cr+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O ABXXWVKOBZHNNF-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
본 발명은 아연도 강판용 친환경 크롬프리 피막 조성물에 있어서, 증류수 1L에 대하여, 티탄이온 2~5g/L, 인산이온 20~40g/L, 칼슘이온 5~10g/L, 질산이온 5~10g/L, 규소 이온 5~10g/L, 폴리비닐알코올 5~10g/L로 이루어진 것을 특징으로 하는 아연도 강판용 친환경 크롬프리 피막 조성물에 관한 것으로, 전기 및 용융아연도 강판의 피막 후처리용액으로 기존의 설비에 모두 적용이 가능하고, 크롬프리이면서 6가 크롬 크로메이트와 동등 혹은 그 이상으로 내식성이 우수하고, 용접시 그을음이 발생하지 않으며, 특히 내식성 및 미려한 표면외관 및 내지문성이 우수한 친환경적 조성물인 것이 장점이다. The present invention is an environmentally friendly chromium-free coating composition for galvanized steel sheet, with respect to 1 L of distilled water, 2 to 5 g / L titanium ions, 20 to 40 g / L phosphate ions, 5 to 10 g / L calcium ions, and 5 to 10 g / L nitrates The present invention relates to an environment-friendly chrome-free coating composition for galvanized steel sheet, comprising 5 to 10 g / L of silicon ions and 5 to 10 g / L of polyvinyl alcohol, and existing equipment as an after-treatment solution for electric and molten zinc steel sheets. It is applicable to all of them, and it is chromium-free and has superior corrosion resistance to hexavalent chromium chromate, and it does not generate soot during welding, and it is especially an eco-friendly composition with excellent corrosion resistance and beautiful surface appearance and rubbing resistance. .
아연도 강판용, 친환경, 크롬프리, 피막 조성물, 증류수, 폴리비닐알코올 For galvanized steel, eco-friendly, chromium-free, coating composition, distilled water, polyvinyl alcohol
Description
본 발명은 전기 및 용융아연도 강판의 피막 조성물로 기존의 설비에 모두 적용이 가능하고, 크롬프리이면서 6가 크롬 크로메이트와 동등 혹은 그 이상으로 내식성이 우수하고, 용접시 그을음이 발생하지 않으며, 특히 내식성 및 미려한 표면외관 및 내지문성이 우수한 친환경적 조성물인 것을 특징으로 하는 아연도 강판용 친환경 크롬프리 피막 조성물에 관한 것이다.The present invention can be applied to all existing equipment as a coating composition of the electrical and molten zinc steel sheet, is chromium-free and excellent corrosion resistance equivalent to or greater than hexavalent chromium chromate, soot does not occur during welding, in particular The present invention relates to an environmentally friendly chromium-free coating composition for galvanized steel sheet, which is characterized by being an environmentally friendly composition having excellent corrosion resistance and beautiful surface appearance and fingerprint resistance.
일반적으로 종래에는 아연도 강판에 내식성을 향상시키기 위해 아연도금강판에 크로메이트 처리하는 피막처리방법이 널리 이용되어왔으나 크로메이트 용액 내의 6가 크롬이온의 맹독성으로 인한 환경문제의 대두에 따른 각종 규제로 인해 사용이 불가능한 상태에 이르렀으며 현재까지 개발된 크롬프리제품의 여러 문제로 인해 동등한 내식성을 가지는 것과 동시에 6가 크로메이트의 특성을 가진 대체 물질이 대두되고 있다.In general, the coating method of chromate treatment of galvanized steel sheet has been widely used in order to improve the corrosion resistance of galvanized steel sheet, but it is used due to various regulations due to the environmental problems caused by the high toxicity of hexavalent chromium ion in chromate solution. This impossible condition has been reached, and several problems with chromium-free products developed to date have led to alternative materials having hexavalent chromate properties as well as equivalent corrosion resistance.
상기와 같은 6가 크로메이트를 대체하기 위한 기술로는 국내 공개특허 특2003-0021774호와 국내 등록특허 제10-0793561호 등에 개시되었으며 주로 이러한 특허들은 몰리브덴용액을 기본베이스로 하여 몰리브덴 포스페이트 피막이 형성되도록 한 기술에 관한 특허들이다. As a technology for replacing the hexavalent chromate as disclosed in Korean Patent Laid-Open No. 2003-0021774 and Korean Patent No. 10-0793561, etc., and these patents are mainly used to form a molybdenum phosphate film based on a molybdenum solution as a base. Patents on technology.
그리고 아연도 강판의 피막형성 방법에 대하여서는 국내 공개특허 특1999-53140호, 특 1999-53132호 및 특 2000-38944호등에 침지에 의한 방법과 반응시간단축 및 내지문성, 윤활성을 확보하기 위한 수지를 동시에 도포하도록 하여 사용되고 있으니 이러한 방법도 기술적인 한계를 가진으로 파악되고되고.In addition, the film formation method of galvanized steel sheet is a method by dipping in Korean Patent Laid-Open Publication Nos. 1999-53140, 1999-53132, and 2000-38944, and a resin for shortening the reaction time, fingerprint resistance, and lubricity. These methods are also being identified as having technical limitations as they are being used to apply simultaneously.
아연도 강판의 피막 도포 방법은 크게 롤코팅 방법과 스프레이방식을 사용하여 도포를 시행하는 방법을 기존철강업체 에서 취하고 있고 도막 두께 또한 0.1~1㎛로 되어져 있어 이에 맞는 용액을 찾기가 힘든 상황이다. As for the coating method of galvanized steel sheet, the roll coating method and the spray method are applied by existing steel companies, and the film thickness is 0.1 ~ 1㎛, so it is difficult to find a suitable solution.
아연도 강판의 특성상 피막이 도포된 후에 용접 시 그을음이 발생되어지면 안되며, 절단시 피막이 벗겨지지 않도록 철강강판과의 점착력이 우수해야한다. 이러 것과 동시에 도장시 도장제와의 밀착성이 우수하여야하는 여러가지 성능의 만족을 가져야 하는 특성을 지니고 있으니 현재의 기술은 모든 면에서 6가 크롬 크로메이트에 만족을 시키지 못하고 있는 것이 현실이다.Due to the characteristics of galvanized steel sheet, soot should not be generated during welding after coating is applied, and adhesiveness with steel sheet should be excellent so that the coating does not come off during cutting. At the same time, it has the characteristics of having various performances that should be excellent in adhesion with the coating agent when painting, and the present technology does not satisfy the hexavalent chromium chromate in all respects.
현재 사용되고 있는 크롬프리 제품의 경우 용접성, 내식성, 도포량 등에 여러 문제점을 가지고 있으며 기존의 6가 크롬 크로메이트에 비하여 상당히 고가로 사용되고 있다. 이런단점을 가진 크롬프리는 사용후에도 많은 클레임의 원인이 되기도 한다 따라서 6가크롬과 동일하지만 동등 혹은 이상의 내식성과 내흑변성, 고광택의 성질을 가진 크롬프리 제품의 개발 필요성이 절실히 요구되고 있다.Currently used chromium-free products have various problems such as weldability, corrosion resistance, coating amount, etc., and are used at a considerably higher price than conventional hexavalent chromium chromate. Chromium-free, which has these disadvantages, is also a cause of many claims after use. Therefore, there is an urgent need for the development of chromium-free products having the same or better corrosion resistance, blackening resistance, and high gloss properties.
따라서 본 발명은 상기와 같은 종래의 문제점을 해결하고자 제안된 것으로 인체에 무해하며 친환경의 성격을 크롬프리이면서 6가 크롬 크로메이트 동등 혹은 그 이상의 내식성이 우수하고, 용접시 그을음이 발생하지 않으며, 기존의 3가 크롬 크로메이트의 불안정한 저장 안정성의 개선과 함께 기존의 설비인 롤 코팅공정과 스프레이 코팅공정에 모두 적용 가능하도록 크롬 프리 컨버젼 타입의 크로메이트 피막을 형성시킬 수 있도록 한 것을 특징으로 하는 아연도 강판용 친환경 크롬프리 후처리용액 조성물을 제공하는 것을 그 과제로 한다.Therefore, the present invention is proposed to solve the conventional problems as described above is harmless to the human body and is excellent in corrosion resistance of chromium-free and hexavalent chromium chromate equivalent or more of the environmentally friendly nature, soot does not occur during welding, conventional Eco-friendly chromium for galvanized steel sheet characterized by the formation of chromium-free conversion type chromate coatings to improve the unstable storage stability of trivalent chromium chromate and to be applicable to both existing roll coating processes and spray coating processes. It is the subject to provide a pre-treatment solution composition.
상기의 과제를 해결하기 위한 본 발명은 아연도 강판용 친환경 크롬프리 피막 조성물에 있어서, The present invention for solving the above problems in the environmentally friendly chromium-free coating composition for galvanized steel sheet,
증류수 1L에 대하여, 티탄이온 2~5g/L, 인산이온 20~40g/L, 칼슘이온 5~10g/L, 질산이온 5~10g/L, 규소 이온 5~10g/L, 폴리비닐알코올 5~10g/L로 이루어진 것을 특징으로 하는 아연도 강판용 친환경 크롬프리 피막 조성물을 과제 해결 수단으로 한다.Titanium ions 2 to 5 g / L, phosphate ions 20 to 40 g / L, calcium ions 5 to 10 g / L, nitrates 5 to 10 g / L, silicon ions 5 to 10 g / L and polyvinyl alcohol 5 to 1 L of distilled water An environmentally friendly chromium-free coating composition for galvanized steel sheet characterized by consisting of 10 g / L as a means for solving the problem.
상기의 과제 해결 수단에 의한 본 발명은 전기 및 용융아연도 강판의 피막 후처리용액으로 기존의 설비에 모두 적용이 가능하고, 크롬프리이면서 6가 크롬 크로메이트 동등 혹은 그 이상의 내식성이 우수하고, 용접시 그을음이 발생하지 않으며, 특히 내식성 및 미려한 표면외관 및 내지문성이 우수한 친환경적 조성물인 것이 장점이다. The present invention by the above problem solving means can be applied to both existing facilities as a film after-treatment solution of electrical and molten zinc steel sheet, and is excellent in corrosion resistance of chromium-free and hexavalent chromium chromate equivalent or higher, and when welding Soot does not occur, and in particular, it is an advantage of being an environmentally friendly composition excellent in corrosion resistance and beautiful surface appearance and fingerprint resistance.
상기의 효과를 달성하기 위한 본 발명은 아연도 강판용 친환경 크롬프리 피막 조성물에 있어서, In the present invention for achieving the above effects in an environmentally friendly chromium-free coating composition for galvanized steel sheet,
증류수 1L에 대하여, 티탄이온 2~5g/L, 인산이온 20~40g/L, 칼슘이온 5~10g/L, 질산이온 5~10g/L, 규소 이온 5~10g/L, 폴리비닐알코올 5~10g/L로 이루어진 것을 특징으로 하는 아연도 강판용 친환경 크롬프리 피막 조성물에 관한 것이다. Titanium ions 2 to 5 g / L, phosphate ions 20 to 40 g / L, calcium ions 5 to 10 g / L, nitrates 5 to 10 g / L, silicon ions 5 to 10 g / L and polyvinyl alcohol 5 to 1 L of distilled water It relates to an environment-friendly chrome-free coating composition for galvanized steel sheet, characterized in that consisting of 10g / L.
본 발명에 따른 아연도 강판용 친환경 크롬프리 피막 조성물은 아연도 강판에 범용으로 사용되고, 동시에 스프레이코팅 공정과 롤 코팅공정에 동시에 적용이 가능한 것이 특징이다. Eco-friendly chromium-free coating composition for galvanized steel sheet according to the present invention is characterized in that it can be used in general for galvanized steel sheet, and can be applied simultaneously to the spray coating process and roll coating process.
즉, 상온에서 롤 코팅공정 혹은 스프레이 코팅공정을 통하여 피막을 형성하고 80~100의 온도에서 수초동안 건조하여 모든 아연도금 강판에 피막을 형성시킨다. That is, the film is formed through a roll coating process or a spray coating process at room temperature, and dried for several seconds at a temperature of 80 to 100 to form a film on all galvanized steel sheets.
이하 본 발명에 따른 구성성분을 각 성분별로 상세히 설명하면 아래의 내용과 같다.Hereinafter, the components according to the present invention will be described in detail for each component.
먼저 티탄이온의 경우 일반적으로 여러 가지 용도로 사용되어지나 특히 이용액에서는 내식성을 가지는 산화물 형성의 가장 중요한 부분을 차지하게 된다. 특히 티탄이온이 2 g/L 미만일 경우에는 내식성이 약하게 되며 동시에 피막형성이 제대로 이루어지지 않아 부식 억제력이 상당히 하락 되는 것을 볼 수 있다. 반면 5g/L를 초과할 경우에는 산도의 상승으로 인해 아연도금층이 급속히 부식되어지며, 부식촉진에 의한 내흑변성이 심각하게 이루어짐으로 적정량의 티탄이온을 사용하는 것이 바람직하다.First of all, titanium ions are generally used for various purposes, but especially in the use solution, they occupy the most important part of oxide formation having corrosion resistance. In particular, when the titanium ion is less than 2 g / L, the corrosion resistance is weak and at the same time the film formation is not properly made it can be seen that the corrosion inhibitory ability is significantly reduced. On the other hand, when it exceeds 5g / L, the galvanized layer is rapidly corroded due to the increase in acidity, it is preferable to use an appropriate amount of titanium ions due to the severe blackening due to the acceleration of corrosion.
본 발명에서 사용가능한 티탄이온이 함유된 화합물은 티탄불화산, 티타네이트, 티타늄아세틸 아세테이트 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다. The compound containing titanium ions usable in the present invention is preferably selected from one or more of titanium fluoric acid, titanate and titanium acetyl acetate.
그리고 인산이온의 경우 코팅층의 광택을 확보하는 것으로 활용되어지며 알칼리토금속인 칼슘이온과의 칼슘포스페이트 형성으로 피막에서의 포스페이트 부식억제력을 가지게 되는데 인산이온이 20g/L 미만일 경우에는 광택의 효과를 얻을수 없으며, 40g/L를 초과할 경우에는 규소 이온과의 반응에 의해서 백색의 침전이 발 생되어지고 동시에 표면의 에칭에 영향을 미쳐 아연도 강판의 스팡글(spangle)이 크게 나타나는 문제가 발생하였다. 또한 용액의 저장안정성에서 침전의 발생으로 인해 칼륨포스페이트가 침전되는 것으로 파악되었다.In the case of phosphate ions, it is used to secure the gloss of the coating layer, and it has phosphate corrosion inhibiting ability in the film by forming calcium phosphate with alkaline earth metal calcium ion. When phosphate ion is less than 20g / L, the gloss effect cannot be obtained. In the case of more than 40g / L, white precipitates are generated by the reaction with silicon ions and at the same time, the surface etching is affected, resulting in a large spangle of the galvanized steel sheet. It was also found that potassium phosphate precipitates due to the occurrence of precipitation in the storage stability of the solution.
본 발명에서 사용가능한 인산이온이 함유된 화합물은 인산수용액을 사용하는 것이 바람직하다.For the compound containing phosphate ions usable in the present invention, it is preferable to use an aqueous solution of phosphate.
그리고 칼슘이온의 경우에는 양이온의 역할을 하며, 전자의 이동중 부동태의 상태를 만들어주기 위해서 충분한 양이온이 필요한데 타 알칼리 금속 혹은 알칼리 토금속에 비하여 칼슘이온은 보다 큰 전자를 제공해주며 동시에 분자의 격자속에 염분의 성분들이 침투하지 못하도록 막아주는 역할을 제공한다. 이러한 역할을 하는 칼슘이온이 5g/L 미만일 경우에는 염수중의 나트륨이 침투하여 부식저항성을 낮추거나 혹은 양이온의 부족으로 인한 염소이온이 공격할 우려가 있고, 10g/L를 초과할 경우에는 반응시 다른 성분과의 과다한 반응으로 인해서 피막 형성이 제대로 이루어지지 못하도록 할 우려가 있다. In the case of calcium ions, it functions as a cation, and sufficient cations are needed to make the state of passivation during the movement of electrons. Compared with other alkali metals or alkaline earth metals, calcium ions provide larger electrons and at the same time, It serves to prevent ingredients from penetrating. If calcium ions that play such a role are less than 5 g / L, sodium in brine penetrates to reduce corrosion resistance, or chlorine ions may attack due to lack of cation. Due to excessive reaction with the components, there is a fear that the film formation is not properly made.
본 발명에서 사용가능한 칼슘이온이 함유된 화합물은 질산칼슘, 탄산칼슘, 탄산수소칼슘 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.The compound containing calcium ions usable in the present invention is preferably used by selecting one or more of calcium nitrate, calcium carbonate and calcium hydrogen carbonate.
그리고 질산이온의 경우에는 여러 가지 효과를 예상할 수 있으나 가장 큰 효 과는 티탄이온 화합물에 결합되어 있는 음이온과 더불어 아연표면을 에칭하여 주는 것이 가장 큰 효과이다. 즉 질산이온이 되면서 표면을 에칭해 주는 것과 동시에 표면에 질산아연 층을 발생시킴으로 아연도금 층의 부동태를 가속화 시켜 내식성을 높이는 효과를 가져 올 수 있다. 이러한 질산이온의 경우에는 과량이 들어갈 경우 과다한 에칭으로 인한 아연도금 층의 부식이 일어나며 적게 들어가면 에칭을 하지 못하게 된다. 또 1.0g/L이상 투입될 경우에는 표면의 흑변이 발생하는 것으로 파악되었다.In the case of nitrate ion, various effects can be expected, but the biggest effect is to etch the zinc surface together with the anion bound to the titanium ion compound. In other words, as the nitrate ion is etched and the zinc nitrate layer is generated on the surface, the passivation of the galvanized layer can be accelerated to increase the corrosion resistance. In the case of such nitrate ions, corrosion of the galvanized layer due to excessive etching occurs when excessive amounts are entered, and when less, nitrate ions cannot be etched. In addition, when more than 1.0g / L is added to the black side of the surface was found to occur.
본 발명에서 사용가능한 질산이온이 함유된 화합물은 질산수용액을 사용하는 것이 바람직하다.For the compound containing nitrate ions usable in the present invention, it is preferable to use an aqueous solution of nitrate.
규소 이온의 경우 소량의 유기층 및 각종 금속산화물 층 피막을 형성하기 위하여 사용된 것으로 실리콘 커플링제와 동일한 의미로 사용되었으며, 규소 이온이 5g/L 미만일 경우 폴리비닐알코올과 산화물 층이 완전히 결합되지 않아 피막이 물에 녹아내리거나 혹은 표면에 도포성이 하락되어지는 결과를 낳았으며 이로 인해 부분적인 부식이 촉진되는 현상을 발견할 수 있었으며, 10g/L를 초과할 경우 미 반응물로 존재하여 폴리비닐알코올과 층 분리 현상을 일으켜 저장 안정성에 문제를 나타내는 것으로 파악되었다.In the case of silicon ions, it is used to form a small amount of organic layer and various metal oxide layer coatings. It is used in the same sense as the silicon coupling agent. When silicon ions are less than 5 g / L, the polyvinyl alcohol and the oxide layer are not completely bonded to form a coating. This resulted in dissolution in water or poor applicability to the surface. This resulted in the partial corrosion promotion. If it exceeds 10g / L, it is an unreacted material and thus polyvinyl alcohol and layer It was found to cause segregation and show a problem in storage stability.
본 발명에서 사용가능한 규소 이온은 비닐 트리클로로 실란, 비닐 트리 메톡 시 실란, 트리오르소에톡시 실란, N-페놀-3-아미노프로필 트리 메톡시 실란, 3-우레이도 알킬 트리에톡시 실란으로 이루어진 군에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다. Silicon ions usable in the present invention consist of vinyl trichloro silane, vinyl trimethoxy silane, triorthoethoxy silane, N-phenol-3-aminopropyl trimethoxy silane, 3-ureido alkyl triethoxy silane It is preferable to select and use 1 type or more from a group.
일반적으로 크롬프리 크로메이트의 경우 에폭시, 혹은 우레탄 등을 수지를 많이 사용되게 되나 이러한 수지의 경우 따로 용매를 사용되어야 하며 동시에 강한 피막형성으로 인해 전체적으로 도포량이 증가되는 현상을 나타내게 되며 유연성, 용접시 그을음 발생, 절단시 깨어짐의 문제를 야기함으로 소량의 폴리비닐알코올을 이용하여 물에 녹여 사용하며 이러한 문제를 해결하였고 녹은 후 상온으로 냉각시킬지라도 고형화 되거나 분산이 되지 않는 점을 미연에 차단하였다. 특히 이런 수지는 과량이 들어갈 경우 자기들의 엉김현상으로 사용이 되지 못할 정도로 점도가 높아지는 현상이 발생하였고 기존의 문제들을 해결되지 않았으며 소량이 들어갈 경우 도포성이 하락되어 부분적인 부식이 발생하는 것으로 파악되었다. 폴리비닐알코올 경우는 80℃ 수준의 건조로도 충분히 피막이 형성될 수 있는 특징에 의해서 일반적으로 6가 크롬 크로메이트에도 널리 사용되어지기도 한다. In general, chromium-free chromate uses epoxy or urethane resins a lot, but in the case of these resins, solvents must be used separately, and at the same time, the overall coating amount is increased due to strong film formation. In order to solve this problem, a small amount of polyvinyl alcohol is used to dissolve it in water. This problem has been solved, and even after cooling to room temperature, it solidifies or does not disperse. In particular, such resins have a phenomenon that the viscosity becomes so high that they cannot be used due to their entanglement when excessive amounts are entered, and existing problems have not been solved. It became. In the case of polyvinyl alcohol, due to the characteristic that the film can be sufficiently formed even at 80 ° C. drying, it is generally used widely in hexavalent chromium chromate.
상기와 같이 조성된 크롬프리 크로메이트 피막 처리 용액은 상온에서도 동등한 도포성과 밀착성을 가지고 있으나 피막형성을 위해서 열풍건조방식 혹은 기타 건조 방식에서 80℃ 이상에서 수초간 건조를 하여 피막을 형성한다. 기존의 아연도강판의 크로메이트 처리에 있어서도 동일한 건조조건으로 피막을 형성하였으며, 이 피막용액의 특징은 기존의 설비의 변경없이 액의 점도 조절을 통해서 모든 강판 코팅방법에 모두 적용이 가능하다는 특징을 가지고 있다. The chromium-free chromate coating treatment solution prepared as described above has equivalent coating properties and adhesion even at room temperature, but is dried for several seconds at 80 ° C. or higher in a hot air drying method or other drying method to form a film. In the chromate treatment of the existing galvanized steel sheet, the film was formed under the same drying conditions, and the coating solution was characterized by being applicable to all steel plate coating methods by adjusting the viscosity of the liquid without changing the existing equipment. have.
이하 본 발명을 실시예에 의거하여 상세히 설명하겠는 바, 본 발명이 아래의 실시예에 의해서만 반드시 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not necessarily limited to the following Examples.
(실시예)(Example)
아래 [표 1]의 내용과 같이 구성성분을 증류수 1/L에 첨가하여 티탄산화물이 함유되어 있는 아연도 강판용 친환경 크롬프리 피막 조성물을 제조한 다음 아연도 강판에 상기에서 제조한 조성물을 스프레이 코팅하여 15~25㎛ 두께의 피막을 성성시킨다. 이때 80℃에서 2~3초간 건조시키면 피막이 형성되어진다. 이와같은 방법에 의해 아연도 강판의 표면에 형성시킨 피막의 내식성, 내흑변성, 표면 광택 등을 평가하여 아래 [표 1] 나타내었다.As shown in Table 1 below, components were added to 1 / L of distilled water to prepare an eco-friendly chromium free film composition for galvanized steel sheet containing titanium oxide, and then spray-coated the composition prepared above on galvanized steel sheet. A film having a thickness of 15 to 25 μm is formed. At this time, the film is formed by drying for 2 to 3 seconds at 80 ℃. Corrosion resistance, blackening resistance, surface glossiness, and the like of the coating film formed on the surface of the galvanized steel sheet by this method were evaluated and shown in Table 1 below.
이온titanium
ion
이온silicon
ion
이온Phosphoric Acid
ion
이온
nitric acid
ion
이온calcium
ion
Comparative example
Example
Comparative example
주 1) ◎(매우좋음), ○(좋음), △(보통), ×(나쁨) Note 1) ◎ (very good), ○ (good), △ (normal), × (bad)
TEST 방법 : 침지 3초후 롤러 이용 도포, 건조조건 80℃에서 5~15초 TEST Method: After 3 seconds of immersion, use roller and apply 5 ~ 15 seconds at 80 ℃
상기 [표 1]에서 내식성 시험은 ASTM B-117 규격으로 144시간 동안 백청 5% 발생을 기준으로 하여 평가하였다. In Table 1, the corrosion resistance test was evaluated based on 5% occurrence of white rust for 144 hours in ASTM B-117 standard.
내식성 평가에 있어서는 실시예 1 내지 8과 비교예 9 내지 16의 경우에는 좋거나 또는 매우 좋은 것으로 평가된 반면에 비교예 1 내지 8의 경우에는 내식성이 보통으로 평가되었다. In evaluation of corrosion resistance, it was evaluated as good or very good in Examples 1 to 8 and Comparative Examples 9 to 16, whereas in Comparative Examples 1 to 8, corrosion resistance was evaluated as normal.
본 명세서에 첨부된 사진을 중심으로 실시예에서 평가한 내식성 평가에 대해 설명하면, 도 1a 및 도 2a의 시료들을 에릭션기기로 5mm 가공하여 도 1b 및 도 2b의 시료와 같이 제작한 다음 내식성 시험을 144시간 동안 실시하여 비교하여 시험을 진행하였다. 본 발명에 따른 실시예 1은 도 1b에 나타난 바와 같이 내식성이 우수한 것으로 평가되었지만, 비교예 1은 도 2b에 나타난 바와 같이 백청이 10% 정도 발생하여 내식성이 보통 수준인 것으로 평가되었다. Referring to the evaluation of the corrosion resistance evaluated in the embodiment based on the photographs attached to the present specification, the samples of FIGS. 1A and 2A are processed by 5 mm using an elimination device and manufactured as shown in the samples of FIGS. 1B and 2B and then subjected to the corrosion resistance test. The test was carried out by comparing for 144 hours. Example 1 according to the present invention was evaluated as being excellent in corrosion resistance as shown in Figure 1b, Comparative Example 1 was evaluated as having a normal level of corrosion resistance by generating about 10% white rust as shown in Figure 2b.
그리고 내흑변성 시험은 내흑변성 시험은 수지피복한 환경친화형 강판을 대상으로 65℃, 85% 분위기에서 144시간 후에 백색도를 시험전의 백색도와 비교하여 평가하였으며 차이가 10이하이면 내흑변성이 우수한 강판으로 평가하였다. The black denaturation test was conducted on the environmentally-friendly steel sheet coated with resin and evaluated for whiteness after 144 hours at 65 ° C and 85% atmosphere, compared to the whiteness before the test. Evaluated.
상기 내흑변성 평가에 있어서도 실시예 1 내지 8과 비교예 9 내지 16의 경우에는 최소 보통이상이거나 또는 매우 좋은 것으로 평가된 반면에 비교예 1 내지 8의 경우에는 일부가 나쁜 것으로 평가되었다. Also in the blackening resistance evaluation, in the case of Examples 1 to 8 and Comparative Examples 9 to 16 were evaluated to be at least normal or very good, whereas in Comparative Examples 1 to 8, some were evaluated as bad.
또한 광택 평가에 있어서는 실시예 1 내지 8의 경우에는 좋거나 또는 매우 좋은 것으로 평가된 반면에 비교예 1 내지 8는 일부 시료가 나쁘게 평가되었으며, 비교예 9 내지 16의 경우에는 거의 대부분 나쁘게 평가되었다. In addition, in the evaluation of gloss, in the case of Examples 1 to 8, it was evaluated as good or very good, while in Comparative Examples 1 to 8, some samples were badly evaluated, and in the case of Comparative Examples 9 to 16, almost all of them were badly evaluated.
상기 [표 1]에 나타난 바와 같이 피막 조성물이 본 발명의 범위를 만족하는 실시예 1 내지 8의 내식성, 표면광택, 내흑변성 등의 피막이 우수하게 나타났다. 인산이온과 질산이온, 칼슘이온의 경우의 변화에 따라 용액 자체의 피막이 형성이 불량함으로 인해서 그 범위를 고정하였으며 피막의 주된 영향을 미치는 티탄이온, 규소이온, PVA를 기준으로 특성을 기술하였다.As shown in Table 1, the coating composition exhibited excellent coatings such as corrosion resistance, surface gloss, and blackening resistance of Examples 1 to 8 in which the coating composition satisfies the scope of the present invention. The range was fixed due to the poor formation of the solution itself according to the change of phosphate ion, nitrate ion and calcium ion, and the characteristics were described based on titanium ion, silicon ion, and PVA, which have the main effect of the film.
이상에서 설명한 바와 같이 아연도금강판을 하지 강판으로 사용하였으며 도금도착량은 용도에 따라 변화 가능하고 위의 티탄, 규소, PVA를 함유하는 피막처리용액을 처리하였으며 이외에 내지문성, 도장성, 용접성등이 우수한 것으로 측정되었다. 또한 피막 처리위에 통상의 유기수지를 도포한 수지 피복강판을 제조할수도 있다.As described above, the galvanized steel sheet was used as the base steel sheet, and the coating amount could be changed according to the use, and the above-described coating solution containing titanium, silicon, and PVA was treated. It was determined to be excellent. It is also possible to produce a resin coated steel sheet coated with a conventional organic resin on the coating treatment.
상술한 바와 같이, 본 발명의 바람직한 실시 예를 참조하여 설명하였지만 해당 기술분야의 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated.
도 1 a 및 도 1b는 본 발명에 따른 실시예에서 내식성 시험을 실시하기 위한 시료인 평판을 촬영하여 나타낸 사진, 1a and 1b are photographs showing the plate as a sample for performing a corrosion resistance test in an embodiment according to the present invention,
도 2a 및 도 2b는 비교예에 따른 내식성 시험을 실시하기 위한 시료인 평판을 내식성 시험한 결과 내식성이 보통으로 평가된 시료인 평판을 촬영하여 나타낸 사진에 관한 것이다.2A and 2B relate to a photograph taken by photographing a plate which is a sample whose corrosion resistance is evaluated as a result of the corrosion resistance test of a sample for performing a corrosion resistance test according to a comparative example.
Claims (2)
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| KR100256361B1 (en) | 1995-12-30 | 2000-05-15 | 이구택 | Molyphosphate solution showing excellent whiteness and corrosion resistance when forming film and film forming method using same |
| KR100536884B1 (en) | 2002-08-14 | 2005-12-16 | 김시연 | Zinc-calcium based coloring composition, preparation thereof and parkerizing process using the same |
| KR100643353B1 (en) | 2004-12-27 | 2006-11-10 | 주식회사 포스코 | Metal surface treatment agent excellent in corrosion resistance, alkali resistance and fingerprint resistance, and steel sheet treated using the same |
| KR100728468B1 (en) | 2005-12-30 | 2007-06-13 | 동부제강주식회사 | Chrome-free inorganic composition with high heat resistance and a method of manufacturing a coated steel sheet coated with the same |
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|---|---|---|---|---|
| KR100256361B1 (en) | 1995-12-30 | 2000-05-15 | 이구택 | Molyphosphate solution showing excellent whiteness and corrosion resistance when forming film and film forming method using same |
| KR100536884B1 (en) | 2002-08-14 | 2005-12-16 | 김시연 | Zinc-calcium based coloring composition, preparation thereof and parkerizing process using the same |
| KR100643353B1 (en) | 2004-12-27 | 2006-11-10 | 주식회사 포스코 | Metal surface treatment agent excellent in corrosion resistance, alkali resistance and fingerprint resistance, and steel sheet treated using the same |
| KR100728468B1 (en) | 2005-12-30 | 2007-06-13 | 동부제강주식회사 | Chrome-free inorganic composition with high heat resistance and a method of manufacturing a coated steel sheet coated with the same |
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