KR101258363B1 - Black-colored resin composition for excellent adhesion with uv coating layer and its coated steel sheet - Google Patents
Black-colored resin composition for excellent adhesion with uv coating layer and its coated steel sheet Download PDFInfo
- Publication number
- KR101258363B1 KR101258363B1 KR1020110109369A KR20110109369A KR101258363B1 KR 101258363 B1 KR101258363 B1 KR 101258363B1 KR 1020110109369 A KR1020110109369 A KR 1020110109369A KR 20110109369 A KR20110109369 A KR 20110109369A KR 101258363 B1 KR101258363 B1 KR 101258363B1
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- South Korea
- Prior art keywords
- resin composition
- black
- black resin
- parts
- weight
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 50
- 239000010959 steel Substances 0.000 title claims abstract description 50
- 239000011247 coating layer Substances 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000000049 pigment Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 11
- 239000006224 matting agent Substances 0.000 claims abstract description 10
- 239000012860 organic pigment Substances 0.000 claims abstract description 10
- 239000004645 polyester resin Substances 0.000 claims abstract description 9
- 229920001225 polyester resin Polymers 0.000 claims abstract description 9
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 3
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- -1 methylethyl Chemical group 0.000 claims description 10
- 239000013638 trimer Substances 0.000 claims description 10
- 239000002318 adhesion promoter Substances 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910017813 Cu—Cr Inorganic materials 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 50
- 239000011248 coating agent Substances 0.000 description 43
- 238000001723 curing Methods 0.000 description 21
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HUVAAOZUPLEYBH-UHFFFAOYSA-N 3,4,5-trimethyl-1h-pyrazole Chemical compound CC1=NNC(C)=C1C HUVAAOZUPLEYBH-UHFFFAOYSA-N 0.000 description 1
- XEIVCDDCSGGZSG-UHFFFAOYSA-N 7-[3-[(3-formylphenoxy)methyl]-1,5-dimethylpyrazol-4-yl]-3-(3-naphthalen-1-yloxypropyl)-1H-indole-2-carboxylic acid Chemical compound Cc1c(c(COc2cccc(C=O)c2)nn1C)-c1cccc2c(CCCOc3cccc4ccccc34)c([nH]c12)C(O)=O XEIVCDDCSGGZSG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920003274 CYMEL® 303 LF Polymers 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004924 electrostatic deposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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Abstract
Description
본 발명은 UV 도막층과 밀착성이 우수한 흑색 수지 조성물 및 이를 이용한 강판에 관한 것이다.
The present invention relates to a black resin composition excellent in adhesion with the UV coating layer and a steel sheet using the same.
최근 기술적 발전과 더불어 보다 좋은 제품에 대한 소비자의 요구가 높아짐에 따라 표면 외관이 미려하고 선영성이 우수한 제품의 선호도가 높아지고 있다.With recent technological developments, consumers' demand for better products has increased, so that the appearance of products with excellent surface appearance and good spirituality is increasing.
특히, 표면 보호, 부식 방지, 재료의 미려함을 주기 위하여 각종 철강 재료들은 코팅 도막을 형성하여 그러한 목적을 달성하게 된다. 일반적으로, 상기 목적을 달성하기 위해서 도장 강판과 라미네이트 강판 등이 주로 사용되어 오고 있다. In particular, in order to provide surface protection, corrosion protection, and material beauty, various steel materials form a coating film to achieve such an object. In general, in order to achieve the above object, a coated steel sheet and a laminated steel sheet have been mainly used.
그러나, 이들 두 가지 제품 모두 용제형의 열 경화방식으로 코팅 시 용제의 증발에 필요한 고온 건조 설비가 필요하다. However, both of these products are solvent-type thermal curing methods that require high temperature drying equipment for evaporation of the solvent during coating.
자외선(UV) 코팅 방식은 단시간에 작업이 가능하여 생산성이 뛰어나고, 용제를 사용하지 않아 환경 오염 문제를 줄일 수 있으며, 다른 기타 도장방식, 예를 들어 용제 휘발형 도장방법, 열경화타입 도장방법, 정전 및 전착 도장방법, 분체 도장방법에 비해 가열과정이 필요 없어 에너지 소모가 아주 적은 에너지 세이브 건조방식이다.Ultraviolet (UV) coating method is able to work in a short time, so it is very productive, and it does not use solvents to reduce the environmental pollution problem, and other coating methods, for example, solvent volatile coating method, thermosetting type coating method, It is an energy save drying method with very low energy consumption because no heating process is required compared to electrostatic and electrodeposition coating methods and powder coating methods.
그러나, 이러한 자외선 건조방식을 이용하여 강판의 고부가가치를 부여하기 위해 다양한 코팅강판에 추가로 도장을 하였으나, 기존 사용되고 있는 흑색수지 강판[특허문헌 1]은 흑색수지 코팅자체가 최종공정으로 제품화에 맞춰져 있어 추가로 도장이 되는 UV 도막층과 부착성이 낮아 도막이 탈락하고, 표면결함이 많아 UV 도막층 추가도장용으로 적합하지 않았다. However, in order to give a high value of the steel sheet by using the UV drying method, the coating was additionally applied to various coated steel sheets, but the black resin steel sheet [Patent Document 1], which is currently used, is adapted to commercialization of the black resin coating itself. In addition, the UV coating layer and the adhesion to the coating is low, the coating film is falling off, there are a lot of surface defects were not suitable for the additional coating of the UV coating layer.
따라서, UV 도막층과의 부착성을 개선한 흑색 수지 조성물이 절실히 요구된다.
Therefore, the black resin composition which improved the adhesiveness with a UV coating film layer is urgently needed.
본 발명의 목적은 UV 도막층과 밀착성이 우수한 흑색 수지 조성물 및 이를 이용한 강판을 제공하는데 있다.
An object of the present invention is to provide a black resin composition excellent in adhesion with the UV coating layer and a steel sheet using the same.
상기 과제를 해결하기 위한 수단으로서, 본 발명은As means for solving the above problems,
주제 수지와 우레탄계 경화제의 혼합 수지; Mixed resins of the main resin and the urethane curing agent;
흑색 유기안료 및 흑색 무기 안료를 안료를 1 : 0.7 내지 3의 중량비로 혼합한 흑색안료; A black pigment obtained by mixing a black organic pigment and a black inorganic pigment in a weight ratio of 1: 0.7 to 3;
평균 입경이 3 내지 7 ㎛인 소광제; Quencher with an average particle diameter of 3 to 7 μm;
레벨링제; 및 Leveling agents; And
용매menstruum
를 포함하는 흑색 수지 조성물을 제공한다.
It provides a black resin composition comprising a.
또한, 상기 과제를 해결하기 위한 다른 수단으로서, 본 발명은 상기 흑색 수지 조성물의 경화물을 함유하는 코팅층을 포함하는 강판을 제공한다.
Moreover, as another means for solving the said subject, this invention provides the steel plate containing the coating layer containing the hardened | cured material of the said black resin composition.
본 발명에 따른 흑색 수지 조성물은 아연도금강판에 코팅하고 추가로 자외선(UV) 경화 도막층이 코팅 처리 시 도막간 밀착력이 우수하고, 기존의 흑색 PCM 강판에 사용되는 흑색 수지 조성물에 비해 수지 두께가 얇으면서도 우수한 UV 도막과의 밀착성 및 표면 외관을 나타내며, 내식성, 가공성 및 내용제성이 우수한 가전제품 외장 판넬용 강판을 제공한다.
The black resin composition according to the present invention is coated on a galvanized steel sheet and additionally, the ultraviolet (UV) cured coating layer has excellent adhesion between coatings when the coating is applied, and the resin thickness is higher than that of the black resin composition used for the existing black PCM steel sheet. The present invention provides a steel sheet for home appliance exterior panels that exhibits thinness and excellent adhesion to a UV coating film and surface appearance, and which is excellent in corrosion resistance, processability and solvent resistance.
도 1은 본 발명에 따른 자외선(UV) 경화 코팅 흑색수지 강판의 측 단면도이다.1 is a side cross-sectional view of an ultraviolet (UV) cured coated black resin steel sheet according to the present invention.
본 발명은 주제 수지와 우레탄계 경화제의 혼합 수지; 흑색 유기안료 및 흑색 무기 안료를 1 : 0.7 내지 3의 중량비로 혼합한 흑색안료; 평균 입경이 3 내지 7 ㎛인 소광제; 레벨링제; 및 용매를 포함하는 흑색 수지 조성물에 관한 것이다.
The present invention is a mixed resin of the main resin and the urethane-based curing agent; A black pigment obtained by mixing a black organic pigment and a black inorganic pigment in a weight ratio of 1: 0.7 to 3; Quencher with an average particle diameter of 3 to 7 μm; Leveling agents; And a black resin composition comprising a solvent.
이하, 본 발명을 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 흑색 수지 조성물에서 주제 수지로는 일반 PCM(precoated metal) 산업에서 많이 사용하고 있는 종류의 수지들을 모두 사용할 수 있으나, 바람직하게는 폴리에스테르계 수지, 불소계 수지, 염화비닐 수지(PVC), 에폭시계 수지 및 아크릴계 수지로 이루어진 군으로부터 선택된 하나 이상의 주제 수지를 사용한다. 보다 바람직하게는 우수한 연신성 및 가공성을 나타내도록 고분자량의 폴리에스테르 수지를 사용한다. 분자구조 또한 지방족으로 이루어진 폴리에스테르 수지가 저점도 및 고연신성을 나타내는 것으로 바람직한 것이다. 상기 폴리에스테르 수지로는 수평균 분자량이 5,000 내지 20,000, 바람직하게는 5,500 내지 15,000, 보다 바람직하게는 6,000 내지 12,000인 것이 바람직하다. 수평균 분자량이 5,000 미만이면 가공성이 저하되는 문제가 있으며, 수평균 분자량이 20,000을 초과하면 내약품성 및 광택저하의 문제가 있다. 또한, 수지는 수평균 분자량이 클수록 분자들의 유연성이 증가하여 심가공 시 수지 연신이 쉬우므로 내도막크랙성 측면에서 유리하다. As the main resin in the black resin composition according to the present invention, all kinds of resins widely used in the general PCM (precoated metal) industry can be used. Preferably, the polyester resin, the fluorine resin, and the vinyl chloride resin (PVC) are used. And at least one main resin selected from the group consisting of epoxy resins and acrylic resins. More preferably, a high molecular weight polyester resin is used to exhibit excellent stretchability and processability. The molecular structure is also preferred that polyester resins composed of aliphatic exhibit low viscosity and high stretchability. The polyester resin preferably has a number average molecular weight of 5,000 to 20,000, preferably 5,500 to 15,000, and more preferably 6,000 to 12,000. If the number average molecular weight is less than 5,000, there is a problem that workability is lowered, and if the number average molecular weight exceeds 20,000, there is a problem of chemical resistance and gloss decrease. In addition, the resin is advantageous in terms of coating film crack resistance because the greater the number average molecular weight, the flexibility of the molecules is increased and the resin is easily stretched during deep processing.
상기 주제수지와 함께 사용되는 경화제로는 기존 멜라민계 경화제 대신 우레탄계 경화제를 사용함으로써 기존 흑색 수지 대비 UV층과의 밀착력이 향상된다. 상기 우레탄계 경화제로는 MEKO-HDI((methylethyl ketoxime blocked hexamethylene diisocyanate) 트라이머(trimer), MEKO-IPDI(methylethyl keoxime blocked isophorone diisocyanate) 트라이머 및 DMP-HDI(3,5-Dimethyl Pyrazole blocked hexamethylene diisocyanate) 트라이머, DMP-IPDI(3,5-Dimethyl Pyrazole blocked isophorone diisocyanate) 트라이머로 이루어진 군에서 선택된 하나 이상이 바람직하나, 이에 한정되지 않으며, 구체적으로 Bayer사의 Desmodur BL3175, Desmodur BL4265, Desmodur PL350 및 Bexenden사의 Trixene BI7984, Trixene BI7982, Trixene BI7951 등이 사용될 수 있다. 상기 우레탄계 경화제는 단독으로 혹은 2종 이상이 함께 사용될 수 있다.As the curing agent used in conjunction with the main resin, by using a urethane-based curing agent instead of the existing melamine-based curing agent, adhesion to the UV layer compared to the existing black resin is improved. The urethane-based curing agents include MEKO-HDI (methylethyl ketoxime blocked hexamethylene diisocyanate) trimer, MEKO-IPDI (methylethyl keoxime blocked isophorone diisocyanate) trimer, and DMP-HDI (3,5-dimethyl methyl pyrazole blocked hexamethylene diisocyanate) trimer. Mercury, one or more selected from the group consisting of DMP-IPDI (3,5-Dimethyl Pyrazole blocked isophorone diisocyanate) trimers, but is not limited thereto, specifically, Bayer's Desmodur BL3175, Desmodur BL4265, Desmodur PL350 and Bexenden's Trixene BI7984 , Trixene BI7982, Trixene BI7951, etc. The urethane-based curing agent may be used alone or in combination of two or more.
본 발명에 따른 흑색 수지 조성물에서, 수지는 주제 수지와 우레탄계 경화제를 혼합한 혼합 수지를 사용하는 것이 특징이다. 특히, 상기 수지는 주제 수지와 우레탄계 경화제를 10 : 2 내지 7의 중량비, 바람직하게는 10 : 3 내지 5 중량비로 배합된 수지이며, 전체 흑색 수지 조성물 100 중량부에 대하여 혼합수지 20 내지 60 중량부를 사용한다. 상기 주제수지와 우레탄계 경화제의 배합비가 10 : 2 내지 7 중량비를 벗어나면, 치밀한 피막이 형성되지 않아 도막의 물성이 저하된다. 또한, 상기 혼합 수지의 함량이 20 중량부 미만이면, 내식성, 가공성의 향상효과가 부족하며, 60 중량부를 초과하면 수지의 함량이 너무 높아 점도가 높아지고, 표면 전도성이 저하되고 또한, 점도가 높아져 도막의 물성이 저하되므로 바람직하지 않다.In the black resin composition according to the present invention, the resin is characterized by using a mixed resin obtained by mixing a main resin and a urethane curing agent. In particular, the resin is a resin in which the main resin and the urethane-based curing agent are blended in a weight ratio of 10: 2 to 7, preferably 10: 3 to 5 by weight, and 20 to 60 parts by weight of the mixed resin with respect to 100 parts by weight of the total black resin composition. use. When the blending ratio of the main resin and the urethane curing agent is out of the 10: 2 to 7 weight ratio, a dense film is not formed and the physical properties of the coating film are lowered. In addition, when the content of the mixed resin is less than 20 parts by weight, the effect of improving the corrosion resistance and workability is insufficient, and when the content of the mixed resin exceeds 60 parts by weight, the content of the resin is too high, the viscosity is high, the surface conductivity is lowered, and the viscosity is high, the coating film It is not preferable because the physical properties of.
본 발명에 따른 흑색 수지 조성물에 첨가되는 흑색 안료는 기존 유기 안료 대신 무기 안료를 혼합 사용함으로써 기존 흑색 수지 대비 표면 결함이 저감되어 고품질 확보가 가능하다. 본 발명의 흑색 수지 조성물은. 바람직하게 유기 흑색 안료와 무기 흑색 안료를 1: 0.7 내지 3의 중량비로 혼합하여 사용한다. 상기 범위를 벗어나면 색상구현 어려움 및 용액 유동특성 저하 대한 문제가 있다. 또한, 상기 흑색 안료는 전체 흑색 수지 조성물 100 중량부에 대하여 8 내지 25 중량부를 사용하는 것이 바람직하며, 8 중량부 미만으로 사용할 경우에는 고형분 저하로 인한 작업성 확보의 어려움이 있고, 25 중량부를 초과 사용하면 용액의 가격상승 문제가 있다.In the black pigment added to the black resin composition according to the present invention, by using an inorganic pigment instead of the existing organic pigment, surface defects are reduced compared to the existing black resin, thereby ensuring high quality. The black resin composition of this invention is. Preferably, the organic black pigment and the inorganic black pigment are mixed and used in a weight ratio of 1: 0.7 to 3. Outside the above range, there is a problem in color implementation difficulty and solution flow characteristics deterioration. In addition, the black pigment is preferably used 8 to 25 parts by weight with respect to 100 parts by weight of the total black resin composition, when using less than 8 parts by weight, there is a difficulty in securing workability due to a decrease in solid content, exceeding 25 parts by weight If used, there is a problem of a price increase of the solution.
상기 유기 흑색 안료로는 나노 카본블랙을 사용할 수 있으며, 특히 평균 입경이 10∼30 nm범위의 에보닉스사(독일)의 네록스(Nerox) 시리즈, 프린텍스 시리즈(Printex) TM, 하이블랙 시리즈(Highblack) TM 등을 사용하는 것이 바람직하다.Nano carbon black may be used as the organic black pigment, and in particular, an average particle diameter of 10 to 30 nm range of Nerox series, Printex TM, and High black series of Ebonics Inc. (Germany) Highblack) TM or the like is preferable.
상기 무기 흑색 안료로는 Cu-Cr계, 산화철계, (Fe,Mn)2O3계 등을 사용할 수 있으며, 특히 평균 입경이 1~2 ㎛ 범위의 바이엘사 Black 318 시리즈, Shepherd사의 Black 430시리즈 등을 사용하는 것이 바람직하다.As the inorganic black pigment, Cu-Cr-based, iron oxide-based, (Fe, Mn) 2 O 3 -based, and the like may be used, and in particular, Bayer's Black 318 series and Shepherd's Black 430 series having an average particle diameter of 1 to 2 μm It is preferable to use etc.
본 발명에 따른 흑색 수지 조성물에 첨가되는 소광제는 고형분 상승 및 도막의 경도(Hardness)를 부여하는 필러 역할을 하며, 구체적으로 실리카, 산화마그네슘, 지르코니아, 알루미나, 피엠엠에이 및 티타니아로 이루어진 군에서 선택된 1종 이상일 수 있다. 특히, 본 발명에서는 평균 입경이 3 내지 7 ㎛인 것을 사용하는 것은 도막 위로 돌출되어 외관불량 야기하는 것을 방지하는 이유에서 바람직하다. 또한, 상기 소광제는 전체 흑색 수지 조성물 100 중량부에 대하여 1 내지 10 중량부로 배합될 수 있다. 소광제가 1 중량부 미만으로 사용될 경우에는 도막의 경도 및 작업성 저하 문제가 있으며, 10 중량부를 초과 사용하면 용액의 가격 상승 및 흑색감이 크게 저하되는 문제가 있어 바람직하지 못하다.The matting agent added to the black resin composition according to the present invention serves as a filler to impart a solid content increase and a hardness of the coating film, and specifically, in the group consisting of silica, magnesium oxide, zirconia, alumina, PMA, and titania. It may be one or more selected. Particularly, in the present invention, the use of an average particle diameter of 3 to 7 µm is preferable for the reason of preventing protruding onto the coating and causing poor appearance. In addition, the quencher may be blended in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total black resin composition. When the matting agent is used in less than 1 part by weight, there is a problem of deterioration in hardness and workability of the coating film, and when used in excess of 10 parts by weight, there is a problem that the price of the solution and the blackness is greatly reduced, which is not preferable.
본 발명에 따른 흑색 수지 조성물에서 레벨링제로는 기존 실리콘 화합물 대신 아크릴계 화합물을 사용하여 표면 장력을 통한 접착력을 향상시킨다. 상기 레벨링제는 전체 흑색 수지 조성물 100 중량부에 대하여 0.5 내지 5 중량부를 사용하는 것이 바람직하다. 만일 레벨링제가 0.5 중량부 미만 사용되면 기포과다로 인한 외관불량 발생 문제가 있고, 5 중량부 초과 사용되면 도막 표면장력을 낮춰 UV층과의 접착력에 문제가 발생될 수 있다.In the black resin composition according to the present invention, as a leveling agent, an acrylic compound is used instead of a conventional silicone compound to improve adhesion through surface tension. The leveling agent is preferably used 0.5 to 5 parts by weight based on 100 parts by weight of the total black resin composition. If the leveling agent is used less than 0.5 parts by weight, there is a problem of appearance defects due to excessive bubbles, and when the leveling agent is used more than 5 parts by weight, the coating film surface tension is lowered, which may cause a problem in adhesion to the UV layer.
본 발명에 따른 흑색 수지 조성물에서 용매로 솔벤트 나프타, 셀로솔브 아세테이트, 부틸 셀로솔브, PMA(propylene glycol methyl ether acetate), DBE(Dibasic ester), 사이클로헥사논(Cyclohexanone) 등을 사용할 수 있다. 상기 용매는 1종 혹은 2종 이상의 혼합물로 사용될 수 있다. 특히, 용매의 함량에 따라 흑색수지 조성물의 점도가 조절되며, 용매의 양은 특히, 한정하는 것은 아니며, 이 기술분야에서 통상적으로 사용되는 기술에 따라 그 함량도 적절히 조절할 수 있다. 용매의 함량은 이로서 한정되는 것은 아니나, 예를 들어, 딘 컵(DIN, 53211)에서 배출되는데 50~100초가 소요되는 정도의 점도가 되는 양으로 조절될 수 있도록 하는 것이 바람직하다. 보다 바람직하게는 전체 흑색 수지 조성물 100 중량부에 대하여 30 내지 70 중량부를 사용하는 것이 바람직하다. 상기 용매를 30 중량부 미만 사용할 경우에는 점도 상승으로 인한 작업성 저하 문제가 있으며, 70 중량부를 초과하면 고형분이 낮아져 작업성이 저하되는 문제가 있다.In the black resin composition according to the present invention, solvents such as solvent naphtha, cellosolve acetate, butyl cellosolve, propylene glycol methyl ether acetate (PMA), dibasic ester ( DBE ), cyclohexanone, and the like may be used. The solvent may be used in one kind or in a mixture of two or more kinds. In particular, the viscosity of the black resin composition is adjusted according to the content of the solvent, and the amount of the solvent is not particularly limited, and its content may also be appropriately adjusted according to techniques commonly used in the art. The content of the solvent is not limited thereto, but, for example, it is preferable to adjust the amount to a viscosity such that it takes 50 to 100 seconds to be discharged from the Dean cup (DIN, 53211). More preferably, it is preferable to use 30-70 weight part with respect to 100 weight part of all black resin compositions. When the solvent is used less than 30 parts by weight, there is a problem of workability deterioration due to the increase in viscosity, and if it exceeds 70 parts by weight, there is a problem that the workability is lowered because the solid content is lowered.
본 발명에 따른 흑색 수지 조성물은 상기 주제 수지, 우레탄계 경화제, 흑색안료, 레벨링제, 소광제 및 용매뿐만 아니라 흑색수지 조성물을 사용하여 처리된 강판 위 추가 도장을 위해 필요한 물성을 더욱 개선하기 위해, 필요에 따라, 경화 촉매, 안료 응집 방지제 및 부착증진제 등의 첨가제를 최소 1종 이상 포함하도록 배합될 수 있다. 상기 첨가제는 전체 흑색 수지 조성물 100 중량부에 대하여 0.1 내지 7 중량부를 사용할 수 있다. 상기 경화 촉매로는 DNNDSA, DNNSA, DDBSA, pTSA 등을, 상기 안료 응집 방지제로는 BYK Chemie사의 DISPERBYK-170, DISPERBYK-174, DISPERBYK-180, DISPERBYK-110 등을, 부착증진제는 인산염계 화합물, 실란계 화합물 등을 사용할 수 있다.
The black resin composition according to the present invention is necessary to further improve the physical properties necessary for further coating on the steel sheet treated using the black resin composition as well as the main resin, urethane-based curing agent, black pigment, leveling agent, quencher and solvent. According to the present invention, it may be formulated to include at least one additive such as a curing catalyst, a pigment aggregation inhibitor and an adhesion promoter. The additive may be used 0.1 to 7 parts by weight based on 100 parts by weight of the total black resin composition. The curing catalyst is DNNDSA, DNNSA, DDBSA, pTSA and the like, the pigment agglomeration inhibitors BYK Chemie's DISPERBYK-170, DISPERBYK-174, DISPERBYK-180, DISPERBYK-110 and the like, the adhesion promoter is a phosphate compound, silane System compounds and the like can be used.
본 발명에 따른 흑색 수지 조성물은 주제수지에 우레탄계 경화제를 도입하여 기존의 흑색 수지 대비 UV 도막층과의 밀착성을 향상시켰으며, 흑색 무기안료를 유기안료와 함께 사용하여 유동성을 확보하고, 레벨링제로 아크릴계 화합물을 사용하여 표면장력 조절을 통한 접착력을 향상시킴으로써 가전기기 판넬용으로 사용하기 위한 가공성, 도막밀착성, 광택성 및 선영성이 우수한 자외선 코팅 강판을 형성할 수 있다.
The black resin composition according to the present invention improves adhesion to the UV coating layer by introducing a urethane-based curing agent to the main resin, and secures fluidity by using a black inorganic pigment with an organic pigment, acrylic as a leveling agent By using the compound to improve the adhesion through the surface tension control can be formed UV coating steel sheet excellent in workability, coating film adhesion, glossiness and screenability for use in home appliance panel.
본 발명은 또한, 상기 흑색 수지 조성물의 경화물을 함유하는 코팅층을 포함하는 강판에 관한 것이다.The present invention also relates to a steel sheet comprising a coating layer containing the cured product of the black resin composition.
상기 강판은 자동차 재료, 가전제품, 건축재료 등의 용도로 이용되는 금속, 특정적으로 철판 등의 금속을 의미하는 것으로서, 이러한 목적으로 당업계에서 통상적으로 사용되는 강판이라면 어떠한 것이라도 무방하지만, 바람직하게는 냉연강판; 아연도금 강판, 아연니켈 도금강판, 아연철 도금강판, 아연티탄 도금강판, 아연마그네슘 도금강판, 아연망간 도금강판, 아연알루미늄 도금강판 등의 아연계 전기도금 강판; 용융도금강판; 알루미늄 도금강판; 또한 이들 도금층에 이종금속 또는 불순물로서, 예를 들면, 코발트, 몰리브덴, 텅스텐, 니켈, 티탄, 알루미늄, 망간, 철, 마그네슘, 주석, 동 등을 함유한 도금 강판; 또한 이들 도금층에 실리카, 알루미나 등의 무기물을 분산시킨 도금강판; 또는 실리콘, 동, 마그네슘, 철, 망간, 티탄, 아연 등을 첨가한 알루미늄 합금판; 또는 인산염이 도포된 아연도금강판; 또는 열연강판을 사용할 수 있고, 필요에 따라 상기 도금 중에 2종류 이상을 순차적으로 처리한 다층 도금판을 사용할 수 있다.The steel sheet means a metal used for the purpose of automobile materials, home appliances, building materials, and the like, specifically, a metal such as an iron plate, and may be any steel sheet commonly used in the art for this purpose. Cold rolled steel sheet; Galvanized electroplated steel sheets such as galvanized steel sheets, zinc-nickel-plated steel sheets, zinc-iron-plated steel sheets, zinc-titanium-coated steel sheets, zinc-magnesium coated steel sheets, zinc manganese-coated steel sheets and zinc- Hot - dip galvanized steel; Aluminum-plated steel sheet; A plating steel sheet containing a different metal or an impurity such as cobalt, molybdenum, tungsten, nickel, titanium, aluminum, manganese, iron, magnesium, tin or copper in these plating layers; A coated steel sheet in which inorganic substances such as silica and alumina are dispersed in these plating layers; Or an aluminum alloy plate to which silicon, copper, magnesium, iron, manganese, titanium, zinc or the like is added; Or zinc phosphate coated with phosphate; Or a hot-rolled steel sheet may be used, and if necessary, a multi-layered plated sheet obtained by sequentially treating two or more kinds of the above-mentioned platings may be used.
상기 흑색 수지 조성물을 강판에 처리하는 방법을 구체적으로 설명하면 다음과 같다.The method of treating the black resin composition to the steel sheet in detail is as follows.
먼저, 강판에 상기 본 발명에 일반적인 크롬프리 조성물을 건조도막 두께가 0.5 내지 2 ㎛이 되도록 도포한 후, 흑색 수지 조성물을 건조 도막 두께가 5 내지 20 ㎛가 되도록 도포한다. 흑색 수지 조성물이 건조 도막 두께가 5 ㎛ 미만이 되도록 도포되면 도막의 은폐력과 가공성 및 내용제성이 나쁘고, 20 ㎛을 초과하면 제조원가가 높고, 생산성이 낮아져 바람직하지 않다. First, after coating the chromium-free composition common to the present invention on the steel sheet so that the dry coating thickness is 0.5 to 2 ㎛, the black resin composition is applied so that the dry coating thickness is 5 to 20 ㎛. When a black resin composition is apply | coated so that a dry coating film thickness may be less than 5 micrometers, the hiding power, workability, and solvent resistance of a coating film are bad, and when it exceeds 20 micrometers, manufacturing cost will be high and productivity will become low, and it is unpreferable.
상기 본 발명의 흑색 수지 조성물은 강판의 일면 또는 양면에 도포하며, 도포는 이로써 한정되는 것은 아니며, 어떠한 통상적인 방법으로 행할 수 있으며, 예를 들어, 바-코터, 롤 코터 혹은 커튼 코터 방법이 사용될 수 있다.
The black resin composition of the present invention is applied to one or both sides of the steel sheet, and the coating is not limited thereto, and may be performed by any conventional method, for example, a bar coater, a roll coater or a curtain coater method may be used. Can be.
강판에 흑색 수지 조성물을 도포한 후, 건조하여 본 발명의 흑색수지 코팅층이 된다. 건조는 이로써 한정하는 것은 아니지만, 열풍 가열방식, 적외선 가열방식 혹은 유도 가열방식으로 행할 수 있다. 이렇게 건조된 흑색수지 조성물 위에 대한민국 공개 특허 제2011-0043234 호의 자외선 경화 도막층을 코팅하여 UV 흑색 고광택 강판을 얻었다.After apply | coating the black resin composition to a steel plate, it dries and becomes the black resin coating layer of this invention. Although drying is not limited to this, it can carry out by a hot air heating system, an infrared heating system, or an induction heating system. The UV cured coating layer of Korea Patent Publication No. 2011-0043234 was coated on the dried black resin composition to obtain a UV black high gloss steel sheet.
상기 열풍가열 방식인 경우 160 내지 340 ℃ 분위기 온도에서 흑색수지 코팅은 10~50초 동안 건조를 행할 수 있다. 상기 유도가열 방식인 경우, 주파수 범위 5~50MHz, 전력 3~15KW으로 흑색 수지 코팅을 5~20초 동안 건조를 행할 수 있다.In the case of the hot air heating method, the black resin coating may be dried for 10 to 50 seconds at 160 to 340 ° C. atmosphere temperature. In the case of the induction heating method, the black resin coating may be dried for 5 to 20 seconds in a frequency range of 5 to 50 MHz and a power of 3 to 15 KW.
상기 흑색 수지 조성물의 코팅 후, 건조 온도는 PMT(Peak metal temperature) 온도로 흑색수지 210 내지 250 ℃의 온도에서 건조하는 것이 바람직하다. After coating of the black resin composition, the drying temperature is preferably dried at a temperature of 210 to 250 ℃ black resin at a PMT (Peak metal temperature) temperature.
상기 본 발명에 의한 흑색수지 조성물 및 처리방법으로 처리된 강판은 전, 후면 모두 또는 일면에 흑색수지 상도 도막층, 구체적으로는 건조도막 두께 5 내지 20 ㎛, 바람직하게는 8 내지 12㎛ 의 본 발명에 의한 흑색수지 조성물로 된 피막이 형성된 것으로, 상기 피막은 크롬이 함유되어 있지 않으며, 전면의 우수한 표면 외관과 흑색의 미려한 색상, 특히, UV도막층과의 도막밀착성 및 가공성이 우수한 것이 특징이다. The steel sheet treated with the black resin composition and the treatment method according to the present invention may be a black resin top coat layer, particularly a dry film thickness of 5 to 20 μm, preferably 8 to 12 μm, on all or one surface of the front and rear surfaces. The film is formed of a black resin composition according to the present invention, and the film does not contain chromium, and is characterized by excellent surface appearance on the front and beautiful black color, in particular, film adhesion and workability with the UV coating layer.
도 1에 본 발명에 의한 흑색 수지 조성물을 이용해 코팅한 UV 흑색수지 강판의 측단면도를 나타내었다. 본 발명은 이로서 한정하는 것은 아니지만, 도 1에 도시한 바와 같이 본 발명에 의한 강판은 강판 위에 아연도금층이 형성되고 아연도금층 위에 크롬프리 처리와 그 위에 흑색 수지 조성물로 된 수지층이 형성되었으며, 최종적으로 자외선 경화 도막이 도장된 것이다. 1 is a side cross-sectional view of a UV black resin steel sheet coated with the black resin composition according to the present invention. Although the present invention is not limited thereto, as shown in FIG. 1, the steel sheet according to the present invention has a galvanized layer formed on the steel sheet, a chromium free treatment formed on the galvanized layer, and a resin layer formed of a black resin composition formed thereon. The ultraviolet cured coating film is coated.
또한, 본 발명에 의한 피막이 형성된 강판은 기존 PCM 강판에 비해 우수한 도막밀착력과 표면품질을 나타낸다.
In addition, the coated steel sheet according to the present invention exhibits excellent film adhesion and surface quality compared to conventional PCM steel sheet.
이하, 본 발명을 실시예에 의해 더욱 상세히 설명한다. 단, 하기의 실시예는 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 의해 제한되는 것은 아니다.
Hereinafter, the present invention will be described in more detail by way of examples. It should be noted, however, that the following examples are illustrative of the invention and are not intended to limit the scope of the invention.
실시예Example 1 ~ 10 및 1 to 10 and 비교예Comparative example 1 ~ 8 1 to 8
편면 도금량 20g/m2 로 양면에 아연도금된 전기아연 도금강판을 사용하였다. An electrogalvanized steel sheet galvanized on both sides with a single plating amount of 20 g / m 2 was used.
흑색 수지 조성물은 100 중량부에 대하여 혼합 수지, 흑색 안료, 소광제, 레벨링제, 용매 기타 첨가제를 하기 표 1 또는 표 2의 함량으로 혼합하고, 지르코니아 볼이 들어있는 고속교반기로 3000 rpm의 속도로 30분간 교반하여 흑색 수지 조성물을 제조하였다. 상기 우레탄계 경화제로는 Blocked Isocyanate를 사용하였는데 이소시아네이트는 HDI(1,6-hexamethylene Diisocyanate) trimer를 블록체로 MEK Oxime을 사용하였다. 흑색 수지 조성물은 용매로 신나(PMA/DBE=1/1)를 사용하여 딘 컵(DIN 53211)에서 배출시 약 50~100초의 시간이 소요되는 점도가 되도록 배합하였다.The black resin composition is mixed with 100 parts by weight of a mixed resin, a black pigment, a matting agent, a leveling agent, a solvent, and other additives in the amounts shown in Table 1 or Table 2 below, using a high speed stirrer containing zirconia balls at a speed of 3000 rpm. It stirred for 30 minutes and manufactured the black resin composition. Blocked Isocyanate was used as the urethane-based curing agent, and isocyanate used MEK Oxime as a block body using an HDI (1,6-hexamethylene Diisocyanate) trimer. The black resin composition was blended using a thinner (PMA / DBE = 1/1) as a solvent to have a viscosity of about 50 to 100 seconds when discharged from the Dean cup (DIN 53211).
그 후, 상기 제조된 실시예 1 내지 10 및 비교예 1 내지 8의 흑색 수지 조성물을 상기 강판의 일면에 건조 도막 두께가 10 um가 되도록 롤-코팅하고, PMT 241 ℃로 열풍 건조시켜 조성물로 처리된 흑색 수지 코팅강판 시편을 제조하였다.
Thereafter, the black resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were roll-coated to one surface of the steel sheet so as to have a dry coating thickness of 10 um, and hot-air dried at PMT 241 ° C. to treat the composition. A black resin coated steel specimen was prepared.
제조된 코팅강판 위에 자외선 경화형 코팅도막을 도장하고 밀착력 및 표면외관을 관찰하였다.
An ultraviolet curable coating film was coated on the prepared coated steel sheet, and adhesion and surface appearance were observed.
비교예Comparative example 9 ~ 11 9-11
A,B,C 사의 가전기기용 판넬로 사용되는 전기아연도금 강판에 흑색 PCM 도장 처리된 강판을 사용하였다. A black PCM-coated steel sheet was used as an electrogalvanized steel sheet used as A, B, C panel for home appliances.
* A사 : 세일철강, BKN-P824, B사 : 동부제철, A9A061E* Company A: Sail Steel, BKN-P824, Company B: Dongbu Steel, A9A061E
C사 : 포스코 강판, HT312E Company C: POSCO Steel Sheet, HT312E
(1:2)Organic 2 ) Inorganic 3 )
(1: 2)
(1:1)Organic 2 ) Inorganic 3 )
(1: 1)
1) 분자량 6000 내지 12000의 고가공용 폴리에스테르 수지와 우레탄계 경화제 MEKO-HDI 트라이머(Desmodur BL3175, Bayer)를 10:4 중량비로 혼합한 수지1) A resin obtained by mixing a highly processed polyester resin having a molecular weight of 6000 to 12000 and a urethane curing agent MEKO-HDI trimer (Desmodur BL3175, Bayer) in a 10: 4 weight ratio.
2) 유기안료: 나노 카본 블랙(Mitsubishi CARBON BLACK MA-100, Mitsubishi Chemical Corporation)2) Organic Pigments: Nano Carbon Black (Mitsubishi CARBON BLACK MA-100, Mitsubishi Chemical Corporation)
3) 무기안료: (Fe,Mn)2O3계열(Black 444, Shepherd)3) Inorganic Pigments: (Fe, Mn) 2 O 3 series (Black 444, Shepherd)
4) 레벨링제: (LA-45, FTC KOREA)4) Leveling agent: (LA-45, FTC KOREA)
5) 안료응집방지제: 습윤분산제(DISPERBYK-180, BYK chemie사)5) Pigment agglomeration inhibitor: Wetting Dispersant (DISPERBYK-180, BYK chemie)
6) 부착증진제: 인산염계(LUBRIZOL 2063, LUBRIZOL)6) Adhesion Promoter: Phosphate (LUBRIZOL 2063, LUBRIZOL)
7) PMA(Propylene glycol methylether acetate), DBE(Dibasic ester) 7) Propylene glycol methylether acetate (PMA), Dibasic ester (DBE)
(1:2)Organic 3 ) -Inorganic 4 )
(1: 2)
(2:1)Organic 3 ) -Inorganic 4 )
(2: 1)
1) 분자량 6000 내지 12000의 고가공용 폴리에스테르 수지와 우레탄계 경화제 MEKO-HDI 트라이머(Desmodur BL3175, Bayer)를 10:4 중량비로 혼합한 수지1) A resin obtained by mixing a highly processed polyester resin having a molecular weight of 6000 to 12000 and a urethane curing agent MEKO-HDI trimer (Desmodur BL3175, Bayer) in a 10: 4 weight ratio.
2) 분자량 6000 내지 12000의 고가공용 폴리에스테르 수지와 멜라민계 경화제(CYMEL 303 LF, CYTEC)를 10:4 중량비로 혼합한 수지2) A resin obtained by mixing a high processing polyester resin having a molecular weight of 6000 to 12000 and a melamine curing agent (CYMEL 303 LF, CYTEC) in a 10: 4 weight ratio.
3) 유기안료: 나노 카본 블랙(Mitsubishi CARBON BLACK MA-100, Mitsubishi Chemical Corporation)3) Organic Pigments: Nano Carbon Black (Mitsubishi CARBON BLACK MA-100, Mitsubishi Chemical Corporation)
4) 무기안료: (Fe,Mn)2O3계열(Black 444, Shepherd)4) Inorganic Pigments: (Fe, Mn) 2 O 3 series (Black 444, Shepherd)
5) 레벨링제: 아크릴계 화합물(LA-45, FTC KOREA)5) Leveling agent: Acrylic compound (LA-45, FTC KOREA)
6) 레벨링제: 실리콘계 화합물(BYK-320, BYK-Chemie)6) Leveling agent: Silicone compound (BYK-320, BYK-Chemie)
7) 안료응집방지제: 습윤분산제(DISPERBYK-180, BYK chemie사)7) Pigment agglomeration inhibitor: Wetting Dispersant (DISPERBYK-180, BYK chemie)
8) 부착증진제: 인산염계(LUBRIZOL 2063, LUBRIZOL)8) Adhesion Promoter: Phosphate (LUBRIZOL 2063, LUBRIZOL)
9) PMA(Propylene glycol methyl ether acetate), DBE(Dibasic ester)
9) Propylene glycol methyl ether acetate (PMA), Dibasic ester (DBE)
시험예Test Example : 물성 평가 Physical property evaluation
하기 조건으로 상기 실시예 1 ~ 10 및 비교예 1 ~ 11의 강판의 성능을 평가하여 그 결과를 하기 표 3에 나타내었다.The performance of the steel sheets of Examples 1 to 10 and Comparative Examples 1 to 11 was evaluated under the following conditions, and the results are shown in Table 3 below.
1) 벤딩 가공성 1) bending workability
상기 흑색수지 코팅강판 표면을 180°구부린 다음, 바이스에 넣어서 평면이 될 때까지 조였다(0, 1, 2T-Bending 실시). 구부러진 도막에 스카치테이프를 부착시킨 후 도막을 박리시켰을 때 테이프에 박리된 상태를 평가하였다. The surface of the black resin coated steel sheet was bent 180 ° and then placed in a vise and tightened until it became flat (0, 1, 2T-Bending). A scotch tape was attached to the curved coating film, and when the coating film was peeled off, the state of peeling off the tape was evaluated.
[평가기준] [Evaluation standard]
우수: 0T, 1T, 2T 모두 박리 없음Excellent: No peeling off at 0T, 1T, or 2T
양호: 0T, 1T에서만 박리됨Good: Peel only at 0T, 1T
불량: 0T, 1T, 2T 모두 박리됨.Poor: 0T, 1T, 2T are all peeled off.
2) 도막 밀착성 2) Coating film adhesion
1 mm 간격으로 바둑판 형태의 눈금을 100개 만든 다음 Erichsen 가공 7 mm 후 스카치 테이프로 도막을 박리시켰을 때 테이프에 박리되어 나오는 도막의 개수로 도막의 밀착성을 평가하였다. 100 sheets of checkerboard-shaped scales were made at 1 mm intervals, and when the coating film was peeled off with Scotch tape after 7 mm of Erichsen processing, the adhesion of the coating film was evaluated by the number of coating films peeling off the tape.
[평가기준] [Evaluation standard]
우수: 박리 없음, Excellent: no peeling off,
양호: 박리율 3% 미만, Good: less than 3% of peel rate,
불량: 박리율 5% 이상.
Poor: Peeling rate 5% or more.
3) 표면 외관 3) surface appearance
UV층이 코팅된 도막의 외관이 이물질 및 미도장 부위가 없이 양호한지 평가하였다.It was evaluated whether the appearance of the coating film coated with the UV layer was good without foreign matter and unpainted sites.
[평가기준][Evaluation standard]
우수: 이상 없음, Excellent: no abnormalities,
양호: 티가 약간 있음, Good: some tee,
불량: 티가 다수 있음.
Poor: Multiple tees.
4) 내용제성 4) solvent resistance
흑색 수지 코팅 강판을 50x100 mm 크기로 시편을 만든 후 메틸에틸케톤(MEK)를 적신 가제로 1 Kgf의 힘으로 문지를 때 도막이 박리될 때까지의 횟수로 판정하였다. The black resin coated steel sheet was made into a size of 50 × 100 mm, and then rubbed with a force of 1 Kgf with a gauze soaked with methyl ethyl ketone (MEK) to determine the number of times until the coating film was peeled off.
[평가기준] [Evaluation standard]
우수: 50회 이상,Excellent: over 50 times,
양호: 20 내지 50회, Good: 20-50 times,
불량: 20회 이하
Bad: 20 or less
5) 광택성 ( 선영성 ): 60°기준5) gloss (distinctness of image): 60 ° based
광택측정설비(sheen사, Tri-Glossmaster)를 이용하여 측정하였다Measurement was carried out using a gloss measuring equipment (Sheen, Tri-Glossmaster)
[평가기준] [Evaluation standard]
우수: 반사율 91% 이상, Excellent: 91% or more reflectance
양호: 반사율 80% 내지 90%, Good: reflectance of 80% to 90%,
불량: 반사율 80% 이하Poor: 80% or less reflectivity
비교예 1, 2는 평균 입경이 10 ㎛인 소광제를 사용한 경우로, 실시예에 비해 표면 외관이 불량하였다.Comparative Examples 1 and 2 used a matting agent having an average particle diameter of 10 µm, and had a poor surface appearance compared to the examples.
비교예 3, 4는 무기 안료가 유기 안료에 비해 적게 포함된 경우로, 실시예에 비해 표면 외관이 불량하였다.In Comparative Examples 3 and 4, less inorganic pigments were included than organic pigments, and the surface appearance was poor compared to the Examples.
비교예 5, 6은 무기 안료를 사용하지 않고, 평균 입경이 10 ㎛인 소광제를 사용하고, 레벨링제로 실리콘을 사용한 경우로 실시예에 비해 벤딩가공성, 도막 밀착성, 표면 외관 모두 불량하였다.In Comparative Examples 5 and 6, a matting agent having an average particle diameter of 10 µm was used without using an inorganic pigment, and silicon was used as a leveling agent. The bending processability, coating film adhesion, and surface appearance were poor in comparison with Examples.
비교예 7, 8은 멜라민계 경화제를 사용한 경우로 실시예에 비해 도막 밀착성이 불량하였다.In Comparative Examples 7, 8, the melamine curing agent was used, and the coating film adhesion was poor compared to the Example.
Claims (16)
흑색 유기안료 및 흑색 무기 안료를 1 : 0.7 내지 3의 중량비로 혼합한 흑색안료;
평균 입경이 3 내지 7 ㎛인 소광제;
레벨링제;
및 용매를 포함하는 것을 특징으로 하는 흑색 수지 조성물.
Mixed resins of the main resin and the urethane curing agent;
A black pigment obtained by mixing a black organic pigment and a black inorganic pigment in a weight ratio of 1: 0.7 to 3;
Quencher with an average particle diameter of 3 to 7 μm;
Leveling agents;
And a black resin composition comprising a solvent.
상기 혼합 수지는 주제 수지와 우레탄계 경화제를 10 : 2 내지 7의 중량비로 혼합한 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The mixed resin is a black resin composition, characterized in that the main resin and the urethane-based curing agent is mixed in a weight ratio of 10: 2 to 7.
상기 주제 수지는 폴리에스테르 수지, 불소계 수지, 염화비닐 수지(PVC), 에폭시계 수지 및 아크릴계 수지로 이루어진 군에서 선택된 하나 이상인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The main resin is at least one selected from the group consisting of polyester resins, fluorine resins, vinyl chloride resins (PVC), epoxy resins and acrylic resins.
상기 우레탄계 경화제는 MEKO-HDI((methylethyl keoxime blocked hexamethylene diisocyanate) 트라이머(trimer), MEKO-IPDI(methylethyl keoxime blocked isophorone diisocyanate) 트라이머 및 DMP-HDI(3,5-Dimethyl Pyrazole blocked hexamethylene diisocyanate) 트라이머, DMP-IPDI(3,5-Dimethyl Pyrazole blocked isophorone diisocyanate) 트라이머로 이루어진 군에서 선택된 하나 이상인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The urethane-based curing agent is a MEKO-HDI (methylethyl keoxime blocked hexamethylene diisocyanate) trimer, MEKO-IPDI (methylethyl keoxime blocked isophorone diisocyanate) trimer and DMP-HDI (3,5-Dimethyl Pyrazole blocked hexamethylene diisocyanate) trimer , DMP-IPDI (3,5-Dimethyl Pyrazole blocked isophorone diisocyanate) black resin composition, characterized in that at least one selected from the group consisting of.
상기 혼합 수지는 전체 흑색 수지 조성물 100 중량부에 대하여 20 내지 60 중량부인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The black resin composition, wherein the mixed resin is 20 to 60 parts by weight based on 100 parts by weight of the total black resin composition.
상기 흑색 안료는 전체 흑색 수지 조성물 100 중량부에 대하여 8 내지 25 중량부인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The black pigment is a black resin composition, characterized in that 8 to 25 parts by weight based on 100 parts by weight of the total black resin composition.
상기 흑색 유기 안료는 카본블랙인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The black organic pigment is a black resin composition, characterized in that carbon black.
상기 흑색 무기 안료는 Cu-Cr계, 산화철계 및 (Fe,Mn)2O3계로 이루어진 군에서 선택된 하나 이상인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The black inorganic pigment is black resin composition, characterized in that at least one selected from the group consisting of Cu-Cr-based, iron oxide-based and (Fe, Mn) 2 O 3 system.
상기 소광제는 실리카, 산화마그네슘, 지르코니아, 알루미나, 폴리메틸메타크릴레이트(PMMA) 및 티타니아로 이루어진 군에서 선택된 하나 이상인 인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The matting agent is black resin composition, characterized in that at least one selected from the group consisting of silica, magnesium oxide, zirconia, alumina, polymethyl methacrylate (PMMA) and titania.
상기 소광제는 전체 흑색 수지 조성물 100 중량부에 대하여 1 ~ 10 중량부인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The matting agent is 1 to 10 parts by weight based on 100 parts by weight of the total black resin composition, the black resin composition.
상기 레벨링제는 아크릴계 화합물인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The leveling agent is a black resin composition, characterized in that the acrylic compound.
상기 레벨링제는 전체 흑색수지 조성물 100 중량부에 대하여 0.5 내지 5 중량부인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The leveling agent is a black resin composition, characterized in that 0.5 to 5 parts by weight based on 100 parts by weight of the total black resin composition.
상기 용매는 전체 흑색수지 조성물 100 중량부에 대하여 30 내지 70 중량부인 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The solvent is a black resin composition, characterized in that 30 to 70 parts by weight based on 100 parts by weight of the total black resin composition.
경화촉매, 부착증진제 및 안료 응집 방지제로 이루어진 군에서 선택된 1종 이상의 첨가제를 추가로 포함하는 것을 특징으로 하는 흑색 수지 조성물.
The method of claim 1,
The black resin composition further comprises at least one additive selected from the group consisting of a curing catalyst, an adhesion promoter and a pigment aggregation inhibitor.
상기 첨가제는 전체 흑색수지 조성물 100 중량부에 대하여 0.1 내지 7 중량부인 것을 특징으로 하는 흑색 수지 조성물.
15. The method of claim 14,
The additive is a black resin composition, characterized in that 0.1 to 7 parts by weight based on 100 parts by weight of the total black resin composition.
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| EP3578613A3 (en) * | 2018-05-17 | 2020-04-08 | Canon Kabushiki Kaisha | Article including film, optical apparatus, coating material, and method for producing article |
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| KR20100066197A (en) * | 2008-12-09 | 2010-06-17 | 제일모직주식회사 | Black photosensitive resin composition, and black matrix and column spacer using the same |
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| KR20050098606A (en) * | 2004-04-08 | 2005-10-12 | 삼성물산 주식회사 | Composite for black-colored concrete |
| KR20090020843A (en) * | 2007-08-24 | 2009-02-27 | 주식회사 포스코 | Zinc coated steel sheet having excellent heat-dissipating black resin coating layer |
| KR20100043365A (en) * | 2008-10-20 | 2010-04-29 | 현대모비스 주식회사 | Black paint for radiator grill of automobile |
| KR20100066197A (en) * | 2008-12-09 | 2010-06-17 | 제일모직주식회사 | Black photosensitive resin composition, and black matrix and column spacer using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3578613A3 (en) * | 2018-05-17 | 2020-04-08 | Canon Kabushiki Kaisha | Article including film, optical apparatus, coating material, and method for producing article |
| US11815656B2 (en) | 2018-05-17 | 2023-11-14 | Canon Kabushiki Kaisha | Article including film, optical apparatus, coating material, and method for producing article |
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