KR20240001585A - Hard coating composition and Method of manufacturing thereof - Google Patents
Hard coating composition and Method of manufacturing thereof Download PDFInfo
- Publication number
- KR20240001585A KR20240001585A KR1020220078414A KR20220078414A KR20240001585A KR 20240001585 A KR20240001585 A KR 20240001585A KR 1020220078414 A KR1020220078414 A KR 1020220078414A KR 20220078414 A KR20220078414 A KR 20220078414A KR 20240001585 A KR20240001585 A KR 20240001585A
- Authority
- KR
- South Korea
- Prior art keywords
- hard coating
- coating composition
- silver nanoparticles
- silver
- weight
- Prior art date
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000002270 dispersing agent Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 150000002576 ketones Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims description 41
- 239000004332 silver Substances 0.000 claims description 40
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 37
- -1 Ag+ ions Chemical class 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 28
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 241000588724 Escherichia coli Species 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 241000295644 Staphylococcaceae Species 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 40
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 24
- 239000010410 layer Substances 0.000 description 16
- 239000002243 precursor Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 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 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001449 anionic compounds Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001412 inorganic anion Inorganic materials 0.000 description 3
- 150000002891 organic anions Chemical class 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Chemical class 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Chemical class 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229940087596 sodium phenolsulfonate Drugs 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- BLXAGSNYHSQSRC-UHFFFAOYSA-M sodium;2-hydroxybenzenesulfonate Chemical compound [Na+].OC1=CC=CC=C1S([O-])(=O)=O BLXAGSNYHSQSRC-UHFFFAOYSA-M 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910017745 AgNP Inorganic materials 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 1
- 238000012261 overproduction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229940054334 silver cation Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
Abstract
본 발명에 따른 항균성 하드코팅 조성물은, 상기 항균성 하드 조성물 중량의 0.02 내지 0.2 중량%로 포함되고, 표면에 고분자로 형성된 캡핑층이 구비된 은 나노입자(silver nanoparticles); 바인더 수지; 상기 바인더 수지를 경화시키는 경화제; 상기 바인더 수지를 용해시키고, 케톤류 용매를 포함하는 유기용매; 및 상기 은 나노입자를 분산시키는 염기성 분산제; 를 포함하는 것을 특징으로 한다. The antibacterial hard coating composition according to the present invention includes silver nanoparticles, which are contained in an amount of 0.02 to 0.2% by weight of the antibacterial hard composition and have a capping layer formed of a polymer on the surface; binder resin; A curing agent that hardens the binder resin; An organic solvent that dissolves the binder resin and includes a ketone solvent; and a basic dispersant for dispersing the silver nanoparticles; It is characterized by including.
Description
본 발명은 하드 코팅 조성물에 관한 것으로, 보다 상세하게는 항균성이 뛰어난 하드코팅 조성물 및 그 제조방법에 관한 것이다.The present invention relates to a hard coating composition, and more specifically, to a hard coating composition with excellent antibacterial properties and a method for producing the same.
하드코팅은 건축용 자재, 자동차 외장 부품, 가구 및 디스플레이 패널 등의 각종 플라스틱 제품이 속하는 분야에서 이들의 표면을 보호하기 위해 광범위하게 적용되는 기술이다.Hard coating is a technology widely applied to protect the surfaces of various plastic products such as building materials, automobile exterior parts, furniture, and display panels.
최근에는 표면 보호나 스크래치 방지와 더불어, 사람의 손길이 많이 닿는 각종 가전제품, 태블릿 또는 스마트폰이 사용자의 손을 통해 세균이 전파되어 상해를 입히는 것을 방지하기 위하여 항균성을 갖는 하드코팅 조성물에 대한 필요성이 증가하고 있다.Recently, in addition to surface protection and scratch prevention, there is a need for a hard coating composition with antibacterial properties to prevent bacteria from being spread through the user's hands and causing injury to various home appliances, tablets, or smartphones that are frequently touched by people. This is increasing.
한편, 은 나노입자(silver nanoparticles;AgNP)는 항균력과 살균력을 갖고 있음이 알려져 있어, 최근 도료, 전자소자, 촉매, 생체재료 등의 다양한 분야에 응용되고 있으며, 인체와 접촉하는 다양한 제품에 포함하여 사용하는 방법들이 개발되고 있다.Meanwhile, silver nanoparticles (AgNP) are known to have antibacterial and sterilizing properties, and have recently been applied in various fields such as paints, electronic devices, catalysts, and biomaterials, and are included in various products that come in contact with the human body. Methods for use are being developed.
본 발명은 항균력과 살균력을 갖는 은 나노입자를 포함하면서, 은 나노입자가 하드코팅 조성물 내에서의 뭉침이 일어나지 않아 분산성이 뛰어나고 항균성이 우수한 하드코팅 조성물을 제공하는 것을 목적으로 한다.The purpose of the present invention is to provide a hard coating composition that contains silver nanoparticles having antibacterial and sterilizing properties and has excellent dispersibility and antibacterial properties because the silver nanoparticles do not agglomerate within the hard coating composition.
본 발명의 일 측면에 따른 항균성 하드코팅 조성물로서, An antibacterial hard coating composition according to one aspect of the present invention,
상기 항균성 하드 조성물 중량의 0.02 내지 0.2 중량%로 포함되고, 표면에 고분자로 형성된 캡핑층이 구비된 은 나노입자(silver nanoparticles);Silver nanoparticles included in an amount of 0.02 to 0.2% by weight of the antibacterial hard composition and having a capping layer formed of a polymer on the surface;
바인더 수지;binder resin;
상기 바인더 수지를 경화시키는 경화제;A curing agent that hardens the binder resin;
상기 바인더 수지를 용해시키고, 케톤류 용매를 포함하는 유기용매; 및An organic solvent that dissolves the binder resin and includes a ketone solvent; and
상기 은 나노입자를 분산시키는 염기성 분산제;를 포함하는 것을 특징으로 한다. It is characterized in that it contains a basic dispersant that disperses the silver nanoparticles.
이 때, 상기 하드코팅 조성물은 경화된 이후의 포도상구균과 대장균에 대한 항균 성능이 99.9% 이상인 것이 바람직하다. At this time, the hard coating composition preferably has an antibacterial performance against staphylococci and E. coli of 99.9% or more after curing.
또한, 상기 염기성 분산제가 수산화나트륨, 다이에탄올아민, 트리에탄올아민, 포스핀리간드 치환 물질로 이루어진 군에서 선택되는 1종 이상인 것이 바람직하다. In addition, it is preferable that the basic dispersant is at least one selected from the group consisting of sodium hydroxide, diethanolamine, triethanolamine, and phosphine ligand-substituted substances.
또한, 상기 염기성 분산제는 상기 은 나노입자 100 중량부에 대해서 5 내지 20 중량부로 포함되는 것이 바람직하다. In addition, the basic dispersant is preferably included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the silver nanoparticles.
또한, 상기 은 나노입자의 평균 입경은 5 내지 50 nm 인 것이 바람직하다. Additionally, the average particle diameter of the silver nanoparticles is preferably 5 to 50 nm.
또한, 상기 은 나노입자는 구형인 것이 바람직하다. Additionally, the silver nanoparticles are preferably spherical.
또한, 상기 캡핑제의 분자량은 10,000 내지 360,000인 것이 바람직하다. Additionally, the molecular weight of the capping agent is preferably 10,000 to 360,000.
또한, 상기 캡핑층은 0.5 nm 내지 10 nm인 것이 바람직하다. Additionally, the capping layer is preferably 0.5 nm to 10 nm.
또한, 상기 케톤류 용매는 메틸 에틸 케톤인 것이 바람직하다. Additionally, the ketone solvent is preferably methyl ethyl ketone.
본 발명의 다른 측면은, Another aspect of the present invention is,
환원용매에 의해 환원된 Ag+ 이온 표면에 고분자로 형성된 캡핑층이 구비된 은 나노입자를 합성하는 은 나노입자 제조단계;A silver nanoparticle manufacturing step of synthesizing silver nanoparticles having a capping layer formed of a polymer on the surface of Ag+ ions reduced by a reducing solvent;
상기 은 나노입자를 메틸에틸케톤과 혼합하는 분산액 제조단계;A dispersion preparation step of mixing the silver nanoparticles with methyl ethyl ketone;
상기 분산액을 바인더 수지 및 염기성 분산제와 혼합하여 은 나노입자가 하드 코팅 조성물 중량의 0.02 내지 0.2 중량%로 포함되도록 하드 코팅액을 제조하는 하드 코팅액 제조단계;를 포함하는 것을 특징으로 한다. A hard coating solution preparation step of mixing the dispersion with a binder resin and a basic dispersant to prepare a hard coating solution such that silver nanoparticles are included in 0.02 to 0.2% by weight of the hard coating composition.
본 발명에 따른 하드코팅 조성물은 코팅을 통하여 엘리베이터, 손잡이, 책상 등 다용도로 사용 가능하며, 주로 투명한 디스플레이에 적용 가능한 코팅 재료로서, 은 나노입자를 포함하여 항균력과 살균력이 뛰어난 것이 특징이다. The hard coating composition according to the present invention can be used for various purposes such as elevators, handles, and desks through coating. It is a coating material mainly applicable to transparent displays, and is characterized by excellent antibacterial and sterilizing properties as it contains silver nanoparticles.
또한 은 나노입자가 뭉치지 않고 잘 분산될 수 있도록 염기성 분산제를 포함하여, 하드코팅 조성물이 플라스틱 기재에 적용되어 코팅된 후에도 은 나노입자가 뭉치지 않고 단위 면적당 높은 표면적을 유지할 수 있어 오염방지 능력이 우수한 효과를 갖는다.In addition, it contains a basic dispersant so that the silver nanoparticles can be well dispersed without agglomerating. Even after the hard coating composition is applied to the plastic substrate and coated, the silver nanoparticles do not agglomerate and maintain a high surface area per unit area, resulting in excellent anti-fouling ability. has
도 1은 하드코팅액에 적용된 은 나노입자가 하드코팅액의 주 용매인 메틸 에틸 케톤(MEK)과 결합을 이루지 못하여 은 나노입자 간의 거리가 짧아지고 뭉치는 현상을 나타낸 모식도이다.
도 2는 하드코팅액에 적용된 은 나노입자가 산성 분위기의 하드 코팅액에서 잘 분산되지 않고 뭉치는 현상을 설명하기 위한 모식도이다.
도 3은 본 발명에 따른 하드코팅액에 적용된 은 나노입자가 염기성 분위기의 하드 코팅액에서 뭉치지 않고 잘 분산되는 현상을 설명하기 위한 모식도이다.
도 4는 본 발명의 일 측면인 하드코팅 조성물의 제조방법을 나타낸 개략도이다.Figure 1 is a schematic diagram showing the phenomenon in which silver nanoparticles applied to a hard coating solution fail to combine with methyl ethyl ketone (MEK), the main solvent of the hard coating solution, and the distance between silver nanoparticles shortens and agglomerates.
Figure 2 is a schematic diagram to explain the phenomenon in which silver nanoparticles applied to a hard coating solution do not disperse well and agglomerate in a hard coating solution in an acidic atmosphere.
Figure 3 is a schematic diagram to explain the phenomenon in which silver nanoparticles applied to the hard coating solution according to the present invention are well dispersed without agglomerating in the hard coating solution in a basic atmosphere.
Figure 4 is a schematic diagram showing a method of manufacturing a hard coating composition, which is an aspect of the present invention.
이하에 본 발명을 상세하게 설명하기에 앞서, 본 명세서에 사용된 용어는 특정의 실시예를 기술하기 위한 것일 뿐 첨부하는 특허청구의 범위에 의해서만 한정되는 것은 아님을 이해하여야 한다. 본 명세서에 사용되는 모든 기술용어 및 과학용어는 다른 언급이 없는 한 기술적으로 통상의 기술을 가진 자에게 일반적으로 이해되는 것과 동일한 의미를 가진다. Before describing the present invention in detail below, it should be understood that the terms used in this specification are only for describing specific embodiments and are not limited only by the scope of the appended claims. All technical and scientific terms used in this specification have the same meaning as generally understood by those skilled in the art unless otherwise specified.
또한, 이하 본 명세서 및 청구 범위에 사용된 용어나 단어를 해석함에 있어서는, 발명자가 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 반드시 통상적이거나 사전적인 의미로만 한정해서 해석할 것이 아니며, 본 명세서에서 기재하는 바에 따라 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석하여야 한다.In addition, in interpreting the terms and words used in the specification and claims hereinafter, conventional interpretation must be used based on the principle that the inventor can appropriately define the concept of the term in order to explain his or her invention in the best way. It should not be interpreted limited to the dictionary meaning, but should be interpreted as meaning and concept consistent with the technical idea of the present invention as described in this specification.
본 명세서 및 청구범위의 전반에 걸쳐, 다른 언급이 없는 한 포함(comprise, comprises, comprising)이라는 용어는 언급된 물건, 단계 또는 일군의 물건, 및 단계를 포함하는 것을 의미하고, 임의의 어떤 다른 물건, 단계 또는 일군의 물건 또는 일군의 단계를 배제하는 의미로 사용된 것은 아니다.Throughout this specification and claims, unless otherwise stated, the terms comprise, comprises, and comprise mean to include the mentioned article, step, or group of articles, and steps, and any other article. , it is not used in the sense of excluding a step, a group of objects, or a group of steps.
한편, 본 발명의 여러가지 실시예들은 명확한 반대의 지적이 없는 한 그 외의 어떤 다른 실시예들과 결합될 수 있다. 특히 바람직하거나 유리하다고 지시하는 어떤 특징도 바람직하거나 유리하다고 지시한 그 외의 어떤 특징 및 특징들과 결합될 수 있다. 이하, 첨부된 도면을 참조하여 본 발명의 실시예 및 이에 따른 효과를 설명하기로 한다.Meanwhile, various embodiments of the present invention may be combined with any other embodiments unless clearly indicated to the contrary. Any feature indicated as being particularly preferred or advantageous may be combined with any other feature or feature indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the attached drawings.
<본 발명의 제1측면><First aspect of the present invention>
본 발명의 제1측면에 따르면, 은 나노입자를 포함한 하드코팅 조성물이 제공된다. 하드코팅 조성물은 은 나노입자와 염기성 분산제, 바인더 수지 및 유기용매를 포함한다. According to a first aspect of the present invention, a hard coating composition containing silver nanoparticles is provided. The hard coating composition includes silver nanoparticles, a basic dispersant, a binder resin, and an organic solvent.
은 나노입자는 하드코팅 조성물의 오염방지 능력을 향상시키는 역할을 하는 재료로서, 특히 캡핑제로 코팅된 은 입자를 사용하며, 정전기적 반발력과 함께 입체장애에 의해 은 입자 간의 뭉침으로 입자 크기가 증가하는 것을 방지하고, 분산 안전성을 증가시키는 역할을 한다.Silver nanoparticles are a material that plays a role in improving the anti-contamination ability of the hard coating composition. In particular, silver particles coated with a capping agent are used. The particle size increases due to agglomeration between silver particles due to steric hindrance along with electrostatic repulsion. It serves to prevent dispersion and increase dispersion safety.
본 발명의 은 나노입자는 Ag+ 이온 표면에 캡핑제를 결합시켜, 캡핑층을 갖는 것을 특징으로 한다. The silver nanoparticles of the present invention are characterized by having a capping layer by binding a capping agent to the surface of Ag+ ions.
캡핑제는 은 나노입자의 표면이 결정화 될 수 있도록 은 나노구조체의 표면에 부착되는 고분자 물질을 말한다.A capping agent refers to a polymer material that is attached to the surface of a silver nanostructure so that the surface of the silver nanoparticle can be crystallized.
캡핑제는 폴리비닐피롤리돈(Polyvinylpyrrolidone, PVP), 폴리비닐알코올(Polyvinylalcohol, PVA), 폴리아크릴아마이드(Polyacrylamide, PAM) 또는 폴리아크릴산(Polyacrylicacid, PAA) 등의 표면부착 고분자가 사용될 수 있으며, 바람직하게는 PVP을 사용하는 것이 좋다.The capping agent may be a surface-adhering polymer such as polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA), polyacrylamide (PAM), or polyacrylicacid (PAA), and is preferred. It is better to use PVP.
이때, 캡핑제의 분자량은 10,000 내지 360,000 인 것이 바람직하다. 캡핑제의 분자량이 10,000 미만인 경우 형성되는 고분자 막이 너무 얇아 은 나노입자 간에 서로 뭉치는 것을 효과적으로 막을 수 없다는 문제점이 있을 수 있고, 캡핑제의 분자량이 360,000 초과인 경우 고분자 사슬의 길이가 길기 때문에 입체 장애로 인하여 은 전구체 표면에 붙기 어렵고 은 나노입자를 잘 형성할 수 없는 문제가 있다. At this time, the molecular weight of the capping agent is preferably 10,000 to 360,000. If the molecular weight of the capping agent is less than 10,000, there may be a problem in that the polymer film formed is too thin to effectively prevent silver nanoparticles from agglomerating together. If the molecular weight of the capping agent is greater than 360,000, steric hindrance may occur due to the long polymer chain. Due to this, there is a problem in that it is difficult to attach to the surface of the silver precursor and silver nanoparticles cannot be formed well.
이때, 은 나노입자는 5 nm 내지 50 nm, 바람직하게는 20 내지 40 nm의 평균 입경을 갖는 입자가 사용된다. 은 나노입자의 평균 입경이 상기 범위 미만이면, 은 나노입자를 합성 후, 정제하는 단계에서 손실률이 크다는 문제점이 있으며, 상기 범위를 초과하는 경우 같은 고형분 함량에 비해 단위 면적당 노출되는 은 나노입자의 표면적이 작아져 항균 성능을 잘 나타내지 못하는 문제점이 있었다.At this time, silver nanoparticles are used having an average particle diameter of 5 nm to 50 nm, preferably 20 to 40 nm. If the average particle diameter of the silver nanoparticles is less than the above range, there is a problem that the loss rate is large during the purification step after synthesizing the silver nanoparticles, and if it exceeds the above range, the surface area of the silver nanoparticles exposed per unit area compared to the same solid content There was a problem in that it was small and did not show good antibacterial performance.
또한, 캡핑제는 은 전구체 100 중량부에 대하여 1000 내지 10,000 중량부 혼합되고, 바람직하게는 3,000 내지 5,000 중량부로 혼합되는 것이 좋다. In addition, the capping agent is mixed in an amount of 1,000 to 10,000 parts by weight, preferably 3,000 to 5,000 parts by weight, based on 100 parts by weight of the silver precursor.
또한, 은 나노입자의 PVP로 형성된 캡핑층은 0.5 nm 내지 10 nm의 두께를 갖으며, 바람직하게는 1 nm 내지 6 nm의 두께를 갖는 것이 바람직하다.Additionally, the capping layer formed of PVP of silver nanoparticles has a thickness of 0.5 nm to 10 nm, and preferably has a thickness of 1 nm to 6 nm.
은 나노입자는 하드코팅 조성물 중량의 0.02 내지 0.2 중량%로 포함되는 것이 좋다. 보다 바람직하게 0.09 내지 0.12wt%로 포함되는 것이 바람직하다. 은 나노입자의 함유량이 상기 범위 미만인 경우에는 단위 면적당 노출되는 은 나노입자의 표면적이 작아져 항균 성능을 잘 나타내지 못하는 문제점이 있을 수 있고, 상기 범위 초과인 경우에는 전체 조성물의 점도가 상승하여 작업성이 떨어지고, 코팅 후 기재와의 접착력이 떨어지는 문제점이 있을 수 있다.Silver nanoparticles are preferably included in an amount of 0.02 to 0.2% by weight of the hard coating composition. More preferably, it is contained in 0.09 to 0.12 wt%. If the content of silver nanoparticles is less than the above range, the surface area of the silver nanoparticles exposed per unit area becomes small and there may be a problem of poor antibacterial performance, and if it exceeds the above range, the viscosity of the entire composition increases, reducing workability. There may be a problem in that the adhesive strength with the substrate decreases after coating.
한편 캡핑층을 갖는 은 나노입자를 제조하는 방법으로는 대표적으로 용액합성법인 폴리올(Polyol) 합성법이 이용될 수 있다. Meanwhile, as a method of manufacturing silver nanoparticles with a capping layer, a typical solution synthesis method, polyol synthesis method, can be used.
폴리올(Polyol)이란 분자 중에 2개 이상의 수산기(Hydroxy group, -OH)를 함유하는 알코올류를 말하며, 폴리올 합성법은 이러한 폴리올, 즉 다가 알코올을 용매이자 환원제로 이용하여 은 나노구조체를 합성하는 방법이다. Polyol refers to alcohols containing two or more hydroxy groups (-OH) in the molecule. Polyol synthesis is a method of synthesizing silver nanostructures using polyols, i.e. polyhydric alcohols, as a solvent and reducing agent. .
일반적으로 미리 가열한 폴리올에 성장 제어와 보호막의 역할을 하는 고분자 물질을 은 이온과 함께 넣어 환원 반응이 일어나게 유도할 수 있다.In general, a reduction reaction can be induced by adding a polymer material that acts as a growth control and protective film to preheated polyol along with silver ions.
이때, 고분자 물질은 은 나노구조체의 표면에 붙는 캡핑제(capping agent)로서 작용하여, 용액 내의 산화 환원 반응과 함께 입자 표면을 둘러싸 캡핑층(capping layer)을 형성하고 합성된 은 나노입자가 오랜 시간 안정하게 유지되도록 해준다.At this time, the polymer material acts as a capping agent attached to the surface of the silver nanostructure, forming a capping layer surrounding the surface of the particle along with the redox reaction in the solution, and the synthesized silver nanoparticles remain for a long time. It keeps it stable.
은 나노입자 합성에 많이 사용하는 고분자 물질로는 폴리비닐피롤리돈(Polyvinylpyrrolidone, PVP)이 있으며, PVP는 은 이온을 은 나노입자로 환원시키는 환원제와 합성된 은 나노입자를 안정적으로 분산되도록 하는 안정제 역할을 동시에 수행할 수 있다.Polyvinylpyrrolidone (PVP) is a polymer material commonly used in the synthesis of silver nanoparticles. PVP is a reducing agent that reduces silver ions to silver nanoparticles and a stabilizer that ensures stable dispersion of the synthesized silver nanoparticles. Can perform roles simultaneously.
예컨대, 은 나노입자는 질산은(silver nitrate;AgNO3)을 용해한 에틸렌 글리콜(Ethylene Glycol;EG)용액과 폴리비닐피롤리돈(Polyvinylpyrrolidone, PVP)을 용해한 EG 용액을 혼합 및 가열하여 제조할 수 있다.For example, silver nanoparticles can be produced by mixing and heating an ethylene glycol (EG) solution in which silver nitrate (AgNO3) is dissolved and an EG solution in which polyvinylpyrrolidone (PVP) is dissolved.
염기성 분산제는 폴리올 합성법으로 제조된 은 나노입자가 캡핑층을 가지고 있으므로 하드코팅 조성물에 적용되어 항균 특성을 나타내기 위해서는 하드코팅 조성물에 뭉치지 않고 잘 분산시키기 위해 포함된다. 수산화나트륨, 다이에탄올아민, 트리에탄올아민, 포스핀 리간드가 치환되어 있는 물질 등이 염기성 분산제로 사용할 수 있으며, 유기용매 100 중량부에 대하여 0.005 내지 0.05 중량부, 바람직하게는 0.01 내지 0.03중량부 포함되는 것이 바람직하다.Since silver nanoparticles manufactured by polyol synthesis have a capping layer, the basic dispersant is included to disperse well without agglomerating in the hard coating composition in order to exhibit antibacterial properties when applied to the hard coating composition. Sodium hydroxide, diethanolamine, triethanolamine, substances with substituted phosphine ligands, etc. can be used as basic dispersants, and are contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent. It is desirable.
은 나노입자의 분산성은 적용되는 용매에 따라 다르게 나타나는데, 예를 들어, 도 1에서 나타나는 것과 같이 PVP 코팅층을 갖는 은 나노입자가 물이나 에탄올에 분산되는 경우, PVP 분자 내 산소 원자와 에탄올 또는 물 분자의 수소 원자 사이에 생기는 정전기적 인력으로 인하여 분산성이 나타날 수 있다.The dispersibility of silver nanoparticles varies depending on the applied solvent. For example, when silver nanoparticles with a PVP coating layer are dispersed in water or ethanol as shown in Figure 1, the oxygen atoms in the PVP molecule and the ethanol or water molecules Dispersibility may occur due to the electrostatic attraction between hydrogen atoms.
그러나, 은 나노입자의 캡핑층을 형성하는 PVP가 물과 에탄올과는 달리, 본 발명의 실시예에서와 같이 하드코팅액의 주 용매인 메틸 에틸 케톤 (Methyl Ethyl Ketone, MEK) 분자와 정전기적 인력을 형성할 수 없어 잘 분산되지 않고 뭉치며, 이로 인하여 은 나노입자의 입자 사이즈가 커질 수 있기 때문에 은 나노입자가 뭉쳐서 항균 성능을 구현 못할 수 있다. However, unlike water and ethanol, PVP, which forms the capping layer of silver nanoparticles, has electrostatic attraction with molecules of methyl ethyl ketone (MEK), the main solvent of the hard coating solution, as in the embodiment of the present invention. Since it cannot be formed, it does not disperse well and clumps together. As a result, the particle size of the silver nanoparticles may increase, so the silver nanoparticles may aggregate and not achieve antibacterial performance.
또한, 일반적인 하드코팅액은 pH가 낮은 산성을 띄고 있어, 도 2에서 나타나는 것과 같이 은 나노입자 주변의 전자가 수소 양이온(H+)과의 결합을 유도하여 은 나노입자가 뭉치는 현상이 발생하고, 이렇게 제조된 하드코팅액을 코팅하여 항균 평가시 단위 면적당 노출되는 은 나노입자의 표면적이 작아져 항균 성능을 잘 나타내지 못할 수 있다. In addition, typical hard coating solutions are acidic with a low pH, and as shown in Figure 2, electrons around the silver nanoparticles induce bonding with hydrogen cations (H+), causing the silver nanoparticles to agglomerate. When evaluating antibacterial properties by coating the prepared hard coating solution, the surface area of the silver nanoparticles exposed per unit area becomes small, which may result in poor antibacterial performance.
이에 전술한 염기성 분산제를 첨가하여 은 나노입자의 분산성을 향상시킬 수 있다. 도 3은 하드코팅액에 적용된 은 나노입자가 염기성 분위기의 하드 코팅액에서 뭉치지 않고 잘 분산되는 현상을 설명하기 위한 모식도이다.Accordingly, the dispersibility of silver nanoparticles can be improved by adding the above-described basic dispersant. Figure 3 is a schematic diagram to explain the phenomenon in which silver nanoparticles applied to a hard coating solution are well dispersed without agglomerating in a hard coating solution in a basic atmosphere.
바인더 수지는 아크릴계, 우레탄계 또는 실리콘계 수지 (또는 단량체)를 포함할 수 있다. The binder resin may include an acrylic-based, urethane-based, or silicone-based resin (or monomer).
바인더 수지는 구체적으로 폴리(메틸) 아크릴산 및 이의 염, 폴리(메틸) 아크릴 레이트, 부틸 에스테르, 폴리 아크릴 아미드, 폴리 아크릴로 니트릴, 폴리 우레탄, 폴리에스터, 멜라민, 비닐아세테이트, 폴리에틸렌, 폴리프로필렌, 폴리비닐알콜, 폴리에틸렌글리콜, 에폭시, 실록산, 폴리다이메틸실록세인, 또는 이들의 공중합체를 포함 할 수 있다. Binder resins specifically include poly(methyl) acrylic acid and its salts, poly(methyl) acrylate, butyl ester, polyacrylamide, polyacrylonitrile, polyurethane, polyester, melamine, vinyl acetate, polyethylene, polypropylene, and polyester. It may include vinyl alcohol, polyethylene glycol, epoxy, siloxane, polydimethylsiloxane, or copolymers thereof.
바인더 수지는 유기용매 100 중량부에 대하여 50 내지 100 중량부, 바람직하게는 60 내지 80중량부 포함되는 것이 바람직하다.The binder resin is preferably contained in an amount of 50 to 100 parts by weight, preferably 60 to 80 parts by weight, based on 100 parts by weight of the organic solvent.
또한, 하드코팅 조성물은 상기 바인더 수지를 경화시키기 위한 물질로서 경화제를 더 포함할 수 있다. 경화제의 소재는 제한되지 않으나, 구체적으로 디에틸렌트리아민, 트리에틸렌테트라민등의 지방족 아민류, 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐술폰, 아조메틸페놀등의 방향족 아민류, 페놀노볼락수지, 오르토크레졸노볼락수지, 나프톨노볼락수지, 페놀아랄킬수지등의 다가 히드록시화합물, 및 이들의 변성물, 무수 프탈산, 무수 말레산, 무수 헥사히드로프탈산, 무수 피로멜리트산등의 산무수물계경화제, 디시안디아미드, 이미다졸, BF3-아민착체 및 구아니딘유도체 등을 사용할 수 있고, 상기 언급한 경화제 중에서 1종 또는 2종 이상을 혼합하여 사용하는 것이 바람직하다.Additionally, the hard coating composition may further include a curing agent as a material for curing the binder resin. The material of the hardener is not limited, but specifically, aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and azomethylphenol, and phenol. Polyhydric hydroxy compounds such as novolak resin, orthocresol novolak resin, naphthol novolak resin, and phenol aralkyl resin, and their modified products, such as phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride. Acid anhydride-based curing agents, dicyandiamide, imidazole, BF3-amine complexes, guanidine derivatives, etc. can be used, and it is preferable to use one or a mixture of two or more of the above-mentioned curing agents.
경화제는 유기용매 100 중량부에 대하여 5 내지 10 중량부, 바람직하게는 5 내지 8중량부 포함되는 것이 바람직하다.The curing agent is preferably contained in an amount of 5 to 10 parts by weight, preferably 5 to 8 parts by weight, based on 100 parts by weight of the organic solvent.
유기용매는 상기 바인더 수지 등을 용해시켜 하드코팅 조성물의 흐름성을 조절하는 역할을 한다.The organic solvent serves to control the flowability of the hard coating composition by dissolving the binder resin.
구체적으로, 유기용매는 메탄올 또는 이소프로판올과 같은 알코올류, 아세톤, 메틸에틸케톤, 메틸부틸케톤 또는 메틸이소부틸케톤과 같은 케톤류, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸에테르, 디메틸에테르, 또는 프로필렌글리콜에테르과 같은 에테르류 등이 사용될 수 있으며, 하드코팅 필름의 밀착성 향상을 위하여 메틸에틸케톤을 사용하는 것이 가장 바람직하다. 한편 본원발명에서 유기용매는 Ag나노입자 제조시 Ag나노입자 분산액에 포함되는 유기용매를 포함한다. Specifically, the organic solvent is alcohol such as methanol or isopropanol, ketone such as acetone, methyl ethyl ketone, methyl butyl ketone or methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ethers such as diethyl ether, dimethyl ether, or propylene glycol ether may be used, and it is most preferable to use methyl ethyl ketone to improve the adhesion of the hard coating film. Meanwhile, in the present invention, the organic solvent includes an organic solvent included in the Ag nanoparticle dispersion when producing Ag nanoparticles.
첨가제는 비염기성 분산제, 가소제, 침강방지제, 소포제, 증점제, 피막방지제 등이 사용될 수 있다. 비염기성 분산제는 블록 공중합체, 나프탈렌술폰산나트륨, 알킬나프탈렌술폰산나트륨, 페놀술폰산나트륨, 알킬 디페닐 에테르, 폴리옥시에틸렌 알킬에테르, 비이온계 계면활성제, 폴리아크릴산나트륨, 올레핀-말레인산나트륨, 축합인산염, 카르복시메틸셀룰로스, 아민유도체 등이 사용될 수 있으며, 하드코팅 조성물들의 분산성 향상을 위하여 블록 공중합체 계열의 분산제를 사용할 수 있다. Additives may include non-basic dispersants, plasticizers, anti-settling agents, anti-foaming agents, thickeners, and anti-filming agents. Non-basic dispersants include block copolymers, sodium naphthalenesulfonate, sodium alkylnaphthalenesulfonate, sodium phenolsulfonate, alkyl diphenyl ether, polyoxyethylene alkyl ether, nonionic surfactant, sodium polyacrylate, sodium olefin-maleate, condensed phosphate, Carboxymethylcellulose, amine derivatives, etc. can be used, and block copolymer-based dispersants can be used to improve the dispersibility of hard coating compositions.
비염기성 분산제는 유기용매 100중량부에 대하여 0.005 내지 0.05 중량부, 바람직하게는 0.01 내지 0.03중량부 포함되는 것이 바람직하다.The non-basic dispersant is preferably contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent.
한편, 본 발명의 하드코팅 조성물은 경화된 이후의 포도상구균과 대장균에 대한 항균 성능이 99.9% 이상인 특징을 갖는다.Meanwhile, the hard coating composition of the present invention has an antibacterial performance of 99.9% or more against staphylococci and Escherichia coli after curing.
<본 발명의 제2측면><Second aspect of the present invention>
본 발명의 제2측면에 따르면, 하드코팅 조성물의 제조방법이 제공된다.According to a second aspect of the present invention, a method for producing a hard coating composition is provided.
도 4은 본 발명의 일 측면인 하드코팅 조성물의 제조방법을 나타낸 개략도이다.Figure 4 is a schematic diagram showing a method of manufacturing a hard coating composition, which is an aspect of the present invention.
하드코팅 조성물의 제조방법은, 은 나노입자 제조단계, 은 나노입자 분산액 제조단계, 및 하드 코팅액 제조단계를 포함한다.The manufacturing method of the hard coating composition includes a silver nanoparticle preparation step, a silver nanoparticle dispersion preparation step, and a hard coating solution preparation step.
은 나노입자 제조단계는 캡핑제 용액을 제조하는 제1용액 제조공정, 은 전구체 용액을 제조하는 제2용액 제조공정, 제1용액과 제2용액을 혼합하여 은 나노입자를 합성하는 합성공정, 및 은 나노입자를 정제하는 정제공정을 포함한다.The silver nanoparticle manufacturing step includes a first solution manufacturing process for preparing a capping agent solution, a second solution manufacturing process for preparing a silver precursor solution, a synthesis process for synthesizing silver nanoparticles by mixing the first solution and the second solution, and It includes a purification process to purify silver nanoparticles.
제1용액 제조공정는 캡핑제를 환원성 용매에 용해 및 가열하여 캡핑제 용액을 제조하는 단계이다.The first solution preparation process is a step of preparing a capping agent solution by dissolving and heating the capping agent in a reducing solvent.
캡핑제는 은 나노입자의 표면이 결정화 될 수 있도록 은 나노구조체의 표면에 부착되는 고분자 물질을 말한다.A capping agent refers to a polymer material that is attached to the surface of a silver nanostructure so that the surface of the silver nanoparticle can be crystallized.
캡핑제는 폴리비닐피롤리돈(Polyvinylpyrrolidone, PVP), 폴리비닐알코올(Polyvinylalcohol, PVA), 폴리아크릴아마이드(Polyacrylamide, PAM) 또는 폴리아크릴산(Polyacrylicacid, PAA) 등의 표면부착 고분자가 사용될 수 있으며, 바람직하게는 PVP을 사용하는 것이 좋다.The capping agent may be a surface-adhering polymer such as polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA), polyacrylamide (PAM), or polyacrylicacid (PAA), and is preferred. It is better to use PVP.
이때, 캡핑제의 분자량은 10,000 내지 360,000 인 것이 바람직하다. 캡핑제의 분자량이 10,000 미만인 경우 형성되는 고분자 막이 너무 얇아 은 나노입자 간에 서로 뭉치는 것을 효과적으로 막을 수 없다는 문제점이 있을 수 있고, 캡핑제의 분자량이 360,000 초과인 경우 고분자 사슬의 길이가 길기 때문에 입체 장애로 인하여 은 전구체 표면에 붙기 어렵고 은 나노입자를 잘 형성할 수 없는 문제가 있다. At this time, the molecular weight of the capping agent is preferably 10,000 to 360,000. If the molecular weight of the capping agent is less than 10,000, there may be a problem in that the polymer film formed is too thin to effectively prevent silver nanoparticles from agglomerating, and if the molecular weight of the capping agent is greater than 360,000, steric hindrance may occur due to the long polymer chain. Due to this, there is a problem that it is difficult to attach to the surface of the silver precursor and silver nanoparticles cannot be formed well.
환원성 용매는 은 전구체와 캡핑제가 용해되는 극성 용매로서 분자 내에 히드록시기를 적어도 2개 이상 가지는, 예를 들어, 다이올, 폴리올 또는 글리콜 등의 용매가 사용될 수 있다. The reducing solvent is a polar solvent in which the silver precursor and the capping agent are dissolved, and a solvent having at least two hydroxy groups in the molecule, such as diol, polyol, or glycol, may be used.
구체적으로, 환원성 용매는 에틸렌글리콜(ethylene glycol; EG), 프로필렌글리콜(propylene glycol; PG), 또는 글리세롤(glycerol)을 포함하며, 더욱 구체적으로는 에틸렌글리콜, 폴리에틸렌글리콜, 1, 2-프로필렌글리콜, 1, 3-프로필렌글리콜, 글리세린, 글리세롤 및 다이에틸 글리콜 중에서 적어도 하나를 포함할 수 있고, 바람직하게는 에틸렌글리콜, 폴리에틸렌글리콜 또는 프로필렌글리콜 중의 1종 이상을 사용하는 것이 좋으며, 더 바람직하게는 에틸렌글리콜을 포함하는 것이 좋다.Specifically, the reducing solvent includes ethylene glycol (EG), propylene glycol (PG), or glycerol, and more specifically, ethylene glycol, polyethylene glycol, 1, 2-propylene glycol, It may contain at least one of 1, 3-propylene glycol, glycerin, glycerol and diethyl glycol, preferably at least one of ethylene glycol, polyethylene glycol or propylene glycol, more preferably ethylene glycol. It is good to include .
이때, 환원성 용매는 캡핑제 중량의 0.5배 내지 5배를 사용하여 혼합하는 것이 바람직하다. At this time, it is preferable to mix the reducing solvent in an amount of 0.5 to 5 times the weight of the capping agent.
또한, 캡핑제와 환원성 용매가 혼합하여 형성된 캡핑제 용액은 가열하여 130℃ 내지 170 ℃로 유지하는 것이 바람직하다.In addition, it is desirable to heat the capping agent solution formed by mixing the capping agent and the reducing solvent and maintain it at 130°C to 170°C.
일 실시예에 따르면, 반응기에 환원성 용매와 캡핑제를 투입하여 임펠러를 이용하여 교반하며 혼합하고, 가열하여 반응기 내부 온도가 140도 내지 170 ℃가 되도록하여 제1용액을 제조한다.According to one embodiment, the first solution is prepared by adding a reducing solvent and a capping agent to the reactor, mixing and stirring using an impeller, and heating the reactor so that the internal temperature of the reactor is 140 to 170 degrees Celsius.
제2용액 제조단계는 은 전구체를 환원성 용매에 용해하여 은 전구체 용액을 제조하는 단계이다. The second solution preparation step is a step of preparing a silver precursor solution by dissolving the silver precursor in a reducing solvent.
은 전구체는 은 양이온(Ag+) 및 유기 또는 무기 음이온으로 이루어진 화합물로서, 유기 또는 무기 음이온은 [NO3]-, [ClO4]-, [BF4]-, [PF6]-, [CH3COO]-, [CF3SO3]-, [SO4]2-, [CH3COCH=COCH3]- 등의 유기 또는 무기 음이온을 포함한다.The silver precursor is a compound consisting of a silver cation (Ag+) and an organic or inorganic anion. The organic or inorganic anion is [NO 3 ] - , [ClO 4 ] - , [BF 4 ] - , [PF 6 ] - , [CH 3 COO] - , [CF 3 SO 3 ] - , [SO 4 ] 2- , [CH 3 COCH=COCH 3 ] - and other organic or inorganic anions.
은 전구체는 구체적으로 AgBF4, AgCF3SO3, AgClO4, AgNO3, Ag(CH3COO), AgPF6 또는 Ag(CF3COO)로부터 선택되는 어느 하나, 또는 이들의 혼합물일 수 있다.The silver precursor may be specifically selected from AgBF 4 , AgCF 3 SO 3 , AgClO 4 , AgNO 3 , Ag(CH 3 COO), AgPF 6 or Ag(CF 3 COO), or a mixture thereof.
제2용액 제조단계에 사용하는 환원성 용매는 전술한 제1용액 제조단계에서 나열한 환원성 용매를 사용할 수 있으며, 제1용액 제조단계에서 사용한 환원성 용매 중의 1종 이상을 포함하는 것이 바람직하다. 이때, 환원성 용매는 환원제로서 역할을 하며 은 전구체를 환원시켜 은 이온을 형성시킨다.The reducing solvent used in the second solution preparation step may be any of the reducing solvents listed in the above-mentioned first solution preparation step, and preferably includes one or more of the reducing solvents used in the first solution preparation step. At this time, the reducing solvent acts as a reducing agent and reduces the silver precursor to form silver ions.
이때, 환원성 용매는 은 전구체 중량의 1배 내지 20배를 사용하여 혼합하는 것이 바람직하다.At this time, it is preferable to mix the reducing solvent using 1 to 20 times the weight of the silver precursor.
또한, 은 전구체와 환원성 용매가 혼합하여 형성된 은 전구체 용액은 10℃ 내지 30℃의 온도에서 3시간 이상 교반하여 유지하는 것이 바람직하다.In addition, it is preferable that the silver precursor solution formed by mixing the silver precursor and the reducing solvent is stirred and maintained at a temperature of 10°C to 30°C for 3 hours or more.
합성단계는 제1용액 제조단계와 제2용액 제조단계에서 제조된 캡핑제 용액 및 은 전구체 용액을 혼합하여 혼합용액을 형성하고, 은 나노입자를 합성하는 단계이다.The synthesis step is a step of mixing the capping agent solution and the silver precursor solution prepared in the first solution preparation step and the second solution preparation step to form a mixed solution and synthesize silver nanoparticles.
여기서, 혼합용액에서 환원용매에 의해 환원된 Ag+ 이온 표면에 캡핑제(capping agent)가 둘러싸고 결합하여 막 또는 캡핑층(capping layer)을 형성한다.Here, a capping agent surrounds and binds to the surface of Ag+ ions reduced by a reducing solvent in the mixed solution to form a film or capping layer.
이때, 형성된 은 나노입자는 5 ㎚ 내지 50 ㎚ 의 입경을 갖고, 캡핑층은 1 nm 내지 6 nm 의 두께를 갖는 것이 바람직하다. 이 때, 캡핑층의 두께는 용매 및 폴리머를 제거하여 은 나노입자가 완전한 구형이라고 가정하에 Ag입자의 부피 및 질량을 계산한 뒤, 이에 따른 폴리머의 질량, 부피를 계산할 수 있다. 즉, PVP가 Ag에 구형의 형태로 캡핑한다는 가정하에 캡핑하고 있는 부분의 직경을 역산하여 예상으로 산출한다. At this time, the formed silver nanoparticles preferably have a particle diameter of 5 nm to 50 nm, and the capping layer preferably has a thickness of 1 nm to 6 nm. At this time, the thickness of the capping layer can be determined by removing the solvent and polymer, calculating the volume and mass of the Ag particles under the assumption that the silver nanoparticles are perfectly spherical, and then calculating the mass and volume of the polymer accordingly. In other words, assuming that PVP caps Ag in a spherical shape, the diameter of the capping portion is calculated backwards and calculated as expected.
합성단계에서 은 전구체는 전체 혼합용액에 대하여 0.01 mol/l 내지 1.0 mol/l 의 농도로 혼합될 수 있고, 중량 대비 5 g/kg 내지 100 g/kg 의 농도로 혼합될 수 있다. 이때, 농도가 0.01 mol/l 또는 5 g/kg 미만인 경우 나노입자의 생성량이 급격히 감소하며 1.0 mol/l 초과 또는 100 g/kg 인 경우 과잉생산으로 인해 나노입자들이 응집되는 문제점이 있다. 더욱 바람직하게는 0.05 mol/l 내지 0.5 mol/l 또는 10 g/kg 내지 30 g/kg로 혼합되는 것이 좋다.In the synthesis step, the silver precursor may be mixed at a concentration of 0.01 mol/l to 1.0 mol/l with respect to the entire mixed solution, and may be mixed at a concentration of 5 g/kg to 100 g/kg by weight. At this time, if the concentration is less than 0.01 mol/l or 5 g/kg, the amount of nanoparticles produced decreases rapidly, and if the concentration is more than 1.0 mol/l or 100 g/kg, there is a problem of nanoparticles agglomerating due to overproduction. More preferably, it is mixed at 0.05 mol/l to 0.5 mol/l or 10 g/kg to 30 g/kg.
또한, 캡핑제는 은 전구체 100 중량부에 대하여 1000 내지 10,000 중량부 혼합되고, 바람직하게는 3,000 내지 5,000 중량부로 혼합되는 것이 좋다. 캡핑제가 상기 범위 미만인 경우 생성된 나노입자의 직경이 증가하는 문제가 발생하며, 상기 범위 초과의 경우 캡핑층의 두께가 증가하여 항균성을 나타내기 어려운 문제점이 발생된다.In addition, the capping agent is mixed in an amount of 1,000 to 10,000 parts by weight, preferably 3,000 to 5,000 parts by weight, based on 100 parts by weight of the silver precursor. If the capping agent is less than the above range, a problem occurs in which the diameter of the generated nanoparticles increases, and if it exceeds the above range, the thickness of the capping layer increases, making it difficult to exhibit antibacterial properties.
정제단계는 반응이 끝난 나노입자를 상온으로 냉각하고 아세톤, 에탄올 등을 이용해 세척 및 정제하여 합성된 은 나노입자를 수득하는 단계이다. The purification step is a step in which the reacted nanoparticles are cooled to room temperature, washed and purified using acetone, ethanol, etc. to obtain synthesized silver nanoparticles.
이때, 정제단계에서 은 나노입자는 용매 및 미반응 폴리머가 제거되고, 수득된 은 나노입자의 부피 및 질량을 계산한 뒤, 이에 따른 폴리머의 질량 및 부피를 계산한다. 또한, 은 나노입자가 완전한 구형으로 형성되고, PVP가 은 입자에 구형의 형태로 캡핑된다는 가정하에 은 입자를 캡핑하고 있는 부분의 직경을 역산하여 캡핑층의 두께를 산출할 수 있다. At this time, in the purification step, the solvent and unreacted polymer are removed from the silver nanoparticles, the volume and mass of the obtained silver nanoparticles are calculated, and then the mass and volume of the polymer are calculated accordingly. Additionally, under the assumption that the silver nanoparticles are formed in a perfect spherical shape and that the PVP caps the silver particles in a spherical shape, the thickness of the capping layer can be calculated by recalculating the diameter of the part capping the silver particles.
은 나노입자 분산액 제조단계는 은 나노입자 제조단계에서 수득된 은 나노입자를 분산 용매와 혼합하여 분산액을 제조하는 단계이다.The silver nanoparticle dispersion preparation step is a step of preparing a dispersion by mixing the silver nanoparticles obtained in the silver nanoparticle preparation step with a dispersion solvent.
분산 용매는 증류수, 에탄올, 이소프로판올 등의 용매를 사용할 수 있고, 다음 단계인 하드코팅액 제조단계에서 사용하는 용매와 같은 용매를 사용하는 것이 바람직하다.The dispersion solvent can be a solvent such as distilled water, ethanol, or isopropanol, and it is preferable to use the same solvent as the solvent used in the next step, the hard coating solution preparation step.
이때, 은 나노입자 분산액은 전체 100 중량부에 대하여 은 나노입자가 5 내지 25 중량부 포함되도록 하는 것이 바람직하고, 12 내지 16 중량부 포함되도록 하는 것이 더 바람직하다.At this time, the silver nanoparticle dispersion preferably contains 5 to 25 parts by weight of silver nanoparticles, and more preferably 12 to 16 parts by weight, based on a total of 100 parts by weight.
하드 코팅액 제조단계는 바인더 수지, 은 나노입자 분산액, 염기성 분산제를 혼합하여 하드코팅 조성물을 제조하는 단계이다.The hard coating solution preparation step is a step of preparing a hard coating composition by mixing a binder resin, a silver nanoparticle dispersion, and a basic dispersant.
구체적으로 은 나노입자 분산액에 바인더 수지를 혼합한 후, 염기성 분산제를 투입한 후, 쉐이커를 통하여 분산시켜 하드코팅 조성물을 제조한다.Specifically, a hard coating composition is prepared by mixing a binder resin with a silver nanoparticle dispersion, adding a basic dispersant, and dispersing through a shaker.
이때, 바인더 수지는 아크릴계, 우레탄계 또는 실리콘계 수지 (또는 단량체)를 포함할 수 있다. At this time, the binder resin may include acrylic, urethane, or silicone resin (or monomer).
상기 바인더의 수지는 폴리(메틸) 아크릴산 및 이의 염, 폴리(메틸) 아크릴 레이트, 부틸 에스테르, 폴리 아크릴 아미드, 폴리 아크릴로 니트릴, 폴리 우레탄, 폴리에스터, 멜라민, 비닐아세테이트, 폴리에틸렌, 폴리프로필렌, 폴리비닐알콜, 폴리에틸렌글리콜, 에폭시, 실록산, 폴리다이메틸실록세인, 또는 이들의 공중합체를 포함 할 수 있다. The binder resin includes poly(methyl) acrylic acid and its salts, poly(methyl) acrylate, butyl ester, polyacrylamide, polyacrylonitrile, polyurethane, polyester, melamine, vinyl acetate, polyethylene, polypropylene, and polyester. It may include vinyl alcohol, polyethylene glycol, epoxy, siloxane, polydimethylsiloxane, or copolymers thereof.
또한, 하드코팅 조성물은 상기 바인더 수지를 경화시키기 위한 물질로서 경화제를 더 포함할 수 있다. 경화제의 소재는 제한되지 않으나, 구체적으로 디에틸렌트리아민, 트리에틸렌테트라민등의 지방족 아민류, 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐술폰, 아조메틸페놀등의 방향족 아민류, 페놀노볼락수지, 오르토크레졸노볼락수지, 나프톨노볼락수지, 페놀아랄킬수지등의 다가 히드록시화합물, 및 이들의 변성물, 무수 프탈산, 무수 말레산, 무수 헥사히드로프탈산, 무수 피로멜리트산등의 산무수물계경화제, 디시안디아미드, 이미다졸, BF3-아민착체 및 구아니딘유도체 등을 사용할 수 있고, 상기 언급한 경화제 중에서 1종 또는 2종 이상을 혼합하여 사용하는 것이 바람직하다. Additionally, the hard coating composition may further include a curing agent as a material for curing the binder resin. The material of the hardener is not limited, but specifically, aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and azomethylphenol, and phenol. Polyhydric hydroxy compounds such as novolak resin, orthocresol novolak resin, naphthol novolak resin, and phenol aralkyl resin, and their modified products, such as phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride. Acid anhydride-based curing agents, dicyandiamide, imidazole, BF3-amine complexes, guanidine derivatives, etc. can be used, and it is preferable to use one or a mixture of two or more of the above-mentioned curing agents.
경화제는 유기용매 100 중량부에 대하여 5 내지 10 중량부, 바람직하게는 5 내지 8중량부 포함되는 것이 바람직하다.The curing agent is preferably contained in an amount of 5 to 10 parts by weight, preferably 5 to 8 parts by weight, based on 100 parts by weight of the organic solvent.
유기용매는 상기 바인더 수지 등을 용해시켜 하드코팅 조성물의 흐름성을 조절하는 역할을 한다.The organic solvent serves to control the flowability of the hard coating composition by dissolving the binder resin.
구체적으로, 유기용매는 메탄올, 에탄올 및 이소프로판올과 같은 알코올류, 아세톤, 메틸에틸케톤, 메틸부틸케톤 및 메틸이소부틸케톤과 같은 케톤류, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸에테르, 디메틸에테르, 프로필렌글리콜에테르과 같은 에테르류 등이 사용될 수 있으며, 하드코팅 필름의 밀착성 향상을 위하여 메틸에틸케톤을 사용하는 것이 가장 바람직하다.Specifically, the organic solvent includes alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl. Ethers such as ether, diethyl ether, dimethyl ether, and propylene glycol ether can be used, and it is most preferable to use methyl ethyl ketone to improve the adhesion of the hard coating film.
염기성 분산제는 하드코팅 조성물의 유기용매에 PVP로 코팅된 은 나노입자가 잘 분산되도록 첨가하는 물질로서, 수산화나트륨, 다이에탄올아민, 트리에탄올아민, 포스핀 리간드가 치환되어 있는 물질의 적어도 1종 이상을 사용할 수 있다.The basic dispersant is a substance added to ensure that the PVP-coated silver nanoparticles are well dispersed in the organic solvent of the hard coating composition, and is composed of at least one type of sodium hydroxide, diethanolamine, triethanolamine, or a substance substituted with a phosphine ligand. You can use it.
염기성 분산제는 유기용매 100 중량부에 대하여 0.005 내지 0.05 중량부, 바람직하게는 0.01 내지 0.03중량부 포함되는 것이 바람직하다.The basic dispersant is preferably contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent.
첨가제는 은 나노입자 및 하드코팅 조성물의 전체적인 분산성을 조절하는 역할을 한다.The additive serves to control the overall dispersibility of the silver nanoparticles and hard coating composition.
구체적으로 첨가제는 비염기성 분산제, 가소제, 침강방지제, 소포제, 증점제, 피막방지제 등이 사용될 수 있으며, 하드코팅 조성물들의 분산성 향상을 위하여 비염기성 분산제를 사용하였다. 비염기성 분산제는 블록 공중합체, 나프탈렌술폰산나트륨, 알킬나프탈렌술폰산나트륨, 페놀술폰산나트륨, 알킬 디페닐 에테르, 폴리옥시에틸렌 알킬에테르, 비이온계 계면활성제, 폴리아크릴산나트륨, 올레핀-말레인산나트륨, 축합인산염, 카르복시메틸셀룰로스, 아민유도체 등이 사용될 수 있으며, 하드코팅 조성물들의 분산성 향상을 위하여 블록 공중합체 계열의 분산제를 사용하였다.Specifically, additives may include non-basic dispersants, plasticizers, anti-settling agents, anti-foaming agents, thickeners, anti-filming agents, etc., and non-basic dispersants were used to improve the dispersibility of hard coating compositions. Non-basic dispersants include block copolymers, sodium naphthalenesulfonate, sodium alkylnaphthalenesulfonate, sodium phenolsulfonate, alkyl diphenyl ether, polyoxyethylene alkyl ether, nonionic surfactant, sodium polyacrylate, sodium olefin-maleate, condensed phosphate, Carboxymethylcellulose, amine derivatives, etc. can be used, and a block copolymer-based dispersant is used to improve the dispersibility of hard coating compositions.
비염기성 분산제는 유기용매 100중량부에 대하여 0.005 내지 0.05 중량부, 바람직하게는 0.01 내지 0.03중량부 포함되는 것이 바람직하다. 또한 비염기성 분산제를 포함할 때 염기성분산제와 비염기성분산제는 1 : 0.8 내지 1: 1의 비율로 사용하는 것이 바람직하다.The non-basic dispersant is preferably contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent. In addition, when a non-basic dispersant is included, it is preferable to use the basic dispersant and the non-basic dispersant in a ratio of 1:0.8 to 1:1.
본 발명의 하드 코팅액 제조단계에 따라 제조된 하드코팅 조성물은 25℃에서 pH가 2 내지 6 바람직하게는 2.5 내지 5.5 인 것을 특징으로 하고, pH가 2 미만인 경우 은 나노입자가 하드코팅 조성물에 잘 분산되지 못하고 은 나노입자 간에 거리가 짧아져 뭉치며, 이로 인하여 은 나노입자의 입자 사이즈가 커지는 문제점이 있다.The hard coating composition prepared according to the hard coating solution preparation step of the present invention is characterized by a pH of 2 to 6, preferably 2.5 to 5.5 at 25°C, and when the pH is less than 2, silver nanoparticles are well dispersed in the hard coating composition. There is a problem in that the distance between silver nanoparticles is shortened and they clump together, which causes the particle size of the silver nanoparticles to increase.
실시예 및 비교예Examples and Comparative Examples
하드코팅 조성물 제조Hard coating composition manufacturing
<실시예 1 ><Example 1>
폴리에틸렌 글리콜(분자량 약 400g/mol) 700 g, 에틸렌 글리콜 500 g을 이중자켓반응기에 투입한 후 잘 교반하고, PVP(Polyvinylpyrrolidone, 분자량 약 10,000g/mol) 30 g을 반응기에 투입한 후 잘 교반하고, 써큘레이터를 이용하여 반응기 내부 온도가 150℃로 안정화될 때까지 열을 가해주면서 제1용액을 제조하였다.700 g of polyethylene glycol (molecular weight about 400 g/mol) and 500 g of ethylene glycol were added to the double jacket reactor and stirred well. Then, 30 g of PVP (Polyvinylpyrrolidone, molecular weight about 10,000 g/mol) was added to the reactor and stirred well. The first solution was prepared by applying heat using a circulator until the temperature inside the reactor was stabilized at 150°C.
다른 반응기에 용매 Ethylene glycol 50 g를 준비한 후, Silver nitrate 15 g을 넣고 3시간 이상 교반하여 용해시켜 제2용액을 제조하였다.After preparing 50 g of solvent ethylene glycol in another reactor, 15 g of silver nitrate was added and stirred for more than 3 hours to dissolve, thereby preparing a second solution.
상기 제 2용액을 제 1용액에 투입하여 혼합용액을 제조하고, 5분간 교반하여 Ag입자 표면에 PVP가 코팅된 은 나노입자를 합성하였다. The second solution was added to the first solution to prepare a mixed solution, and stirred for 5 minutes to synthesize silver nanoparticles coated with PVP on the surface of the Ag particles.
이후 혼합용액을 상온으로 냉각하고, 은 나노입자를 수득하기 위하여 정제하였다. 정제공정은 은 나노입자에 혼합용액 부피의 3배 이상에 해당하는 아세톤을 첨가한 후 원심분리를 이용하여 침전시킨 후 미반응 고분자 및 합성잔여물이 포함된 상등액을 제거한 뒤 침전물인 정제된 PVP가 코팅된 은 나노입자를 얻었다. Afterwards, the mixed solution was cooled to room temperature and purified to obtain silver nanoparticles. The purification process involves adding acetone equivalent to more than 3 times the volume of the mixed solution to the silver nanoparticles, precipitating them using centrifugation, removing the supernatant containing unreacted polymers and synthetic residues, and then purifying PVP as a precipitate. Coated silver nanoparticles were obtained.
이때, 정제과정은 3회 실시하여 목표하는 고분자의 함량에 맞출 수 있었으며, 평균입경 35 nm을 갖고, 고분자로 형성된 캡핑층의 평균 두께가 5 nm 인 은 나노입자 7.0 g을 수득하였다.At this time, the purification process was performed three times to match the target polymer content, and 7.0 g of silver nanoparticles with an average particle diameter of 35 nm and an average thickness of the polymer capping layer of 5 nm were obtained.
추가적으로 은 나노입자의 함량을 측정한 뒤, 에탄올을 사용하여 15% 분산액을 제조하여, 하드코팅 조성물 내 은 나노입자 분산액을 준비하였다.Additionally, after measuring the content of silver nanoparticles, a 15% dispersion was prepared using ethanol to prepare a dispersion of silver nanoparticles in the hard coating composition.
이후 수득된 15% 은 나노입자 분산액 1.0 g, 염기성 분산제인 다이에탄올아민 0.015g, 폴리(메틸) 아크릴산 56 g, 경화제 5.6 g을 메틸에틸케톤 87 g에 혼합하여 하드코팅액을 제조하였다.Afterwards, 1.0 g of the obtained 15% silver nanoparticle dispersion, 0.015 g of diethanolamine as a basic dispersant, 56 g of poly(methyl) acrylic acid, and 5.6 g of hardener were mixed with 87 g of methyl ethyl ketone to prepare a hard coating solution.
<실시예 2 내지 4> <Examples 2 to 4>
아래 표 1과 표 2의 제조성분 및 배합비로 실시예 1과 같은 제조방법을 사용하여 실시예 2 내지 4의 하드코팅 조성물을 제조하였다.The hard coating compositions of Examples 2 to 4 were prepared using the same manufacturing method as Example 1 using the ingredients and mixing ratios shown in Tables 1 and 2 below.
<비교예 1 내지 2> <Comparative Examples 1 to 2>
아래 표 1과 표 2의 제조성분 및 배합비로 실시예 1과 같은 제조방법을 사용하여 비교예 1 내지 2의 하드코팅 조성물을 제조하였다. The hard coating compositions of Comparative Examples 1 and 2 were prepared using the same manufacturing method as in Example 1 using the ingredients and mixing ratios shown in Tables 1 and 2 below.
4Comparative example
4
바인더 수지
binder resin
분산제basic
dispersant
<실시예 5 내지 8 , 비교예 3 내지 4><Examples 5 to 8, Comparative Examples 3 to 4>
PET 기판에 실시예 5 내지 실시예 8, 비교예 3 내지 비교예 4의 항균특성이 부여된 코팅제를 도포한 뒤, 100℃ 로 가열 후 경화하였다. 하드코팅 필름을 제조하였다. The coating agents imparted with antibacterial properties of Examples 5 to 8 and Comparative Examples 3 to 4 were applied to the PET substrate, heated to 100°C, and then cured. A hard coating film was prepared.
실험예Experiment example
<실험예 1: 항균성 테스트><Experimental Example 1: Antibacterial Test>
실시예 5 내지 실시예 8, 비교예 3 내지 비교예 4의 필름에 대해서 항균성을 평가하기 위하여, '필름밀착법 JIS Z 2801'으로 평가하였다. 전술한 필름들을 5㎝x5㎝의 시편으로 만들고, 항균성능을 평가하고자 하는 필름 위에 액상 세균 일정량을 접종한 뒤, 멸균필름(4㎝x4㎝)을 밀착시킨 후, 온도 35℃정도 습도 90%이상의 항온항습기에 24시간 방치 후, 균의 사멸정도를 측정한다. 실험군과 대조군의 세균 활성도를 비교하여 항균 성능을 평가하여 표 3에 정리하였다. In order to evaluate the antibacterial properties of the films of Examples 5 to 8 and Comparative Examples 3 to 4, they were evaluated using the 'Film Adhesion Method JIS Z 2801'. Make the above-mentioned films into specimens of 5cm x 5cm, inoculate a certain amount of liquid bacteria on the film whose antibacterial performance is to be evaluated, attach a sterilization film (4cm x 4cm), and then place it in the film at a temperature of about 35°C and a humidity of 90% or more. After leaving in a constant temperature and humidity chamber for 24 hours, the degree of death of bacteria is measured. Antibacterial performance was evaluated by comparing the bacterial activity of the experimental and control groups and is summarized in Table 3.
전술한 각 실시예에서 예시된 특징, 구조, 효과 등은 실시예들이 속하는 분야의 통상의 지식을 가지는 자에 의하여 다른 실시예들에 대해서도 조합 또는 변형되어 실시 가능하다. 따라서 이러한 조합과 변형에 관계된 내용들은 본 발명의 범위에 포함되는 것으로 해석되어야 할 것이다.The features, structures, effects, etc. illustrated in each of the above-described embodiments can be combined or modified and implemented in other embodiments by a person with ordinary knowledge in the field to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.
Claims (10)
상기 항균성 하드 조성물 중량의 0.02 내지 0.2 중량%로 포함되고, 표면에 고분자로 형성된 캡핑층이 구비된 은 나노입자(silver nanoparticles);
바인더 수지;
상기 바인더 수지를 경화시키는 경화제;
상기 바인더 수지를 용해시키고, 케톤류 용매를 포함하는 유기용매; 및
상기 은 나노입자를 분산시키는 염기성 분산제;
를 포함하는 하드코팅 조성물.An antibacterial hard coating composition,
Silver nanoparticles included in an amount of 0.02 to 0.2% by weight of the antibacterial hard composition and having a capping layer formed of a polymer on the surface;
binder resin;
A curing agent that hardens the binder resin;
An organic solvent that dissolves the binder resin and includes a ketone solvent; and
A basic dispersant that disperses the silver nanoparticles;
A hard coating composition comprising.
상기 하드코팅 조성물은 경화된 이후의 포도상구균과 대장균에 대한 항균 성능이 99.9% 이상인 하드코팅 조성물.According to clause 1,
The hard coating composition is a hard coating composition that has an antibacterial performance against staphylococci and E. coli of 99.9% or more after curing.
상기 염기성 분산제가 수산화나트륨, 다이에탄올아민, 트리에탄올아민, 포스핀리간드 치환 물질로 이루어진 군에서 선택되는 1종 이상인 하드코팅 조성물.According to clause 2,
A hard coating composition wherein the basic dispersant is at least one selected from the group consisting of sodium hydroxide, diethanolamine, triethanolamine, and phosphine ligand-substituted materials.
상기 염기성 분산제는 상기 은 나노입자 100 중량부에 대해서 5 내지 20 중량부로 포함되는 하드코팅 조성물.According to clause 3,
The basic dispersant is a hard coating composition included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the silver nanoparticles.
상기 은 나노입자의 평균 입경은 5 내지 50 nm 인 하드코팅 조성물.According to clause 4,
A hard coating composition wherein the average particle diameter of the silver nanoparticles is 5 to 50 nm.
상기 은 나노입자는 구형인 하드코팅 조성물. According to clause 4,
A hard coating composition in which the silver nanoparticles are spherical.
상기 캡핑제의 분자량은 10,000 내지 360,000인 하드코팅 조성물. According to clause 1,
A hard coating composition wherein the capping agent has a molecular weight of 10,000 to 360,000.
상기 캡핑층은 0.5 nm 내지 10 nm인 하드코팅 조성물. According to clause 1,
A hard coating composition wherein the capping layer has a thickness of 0.5 nm to 10 nm.
상기 케톤류 용매는 메틸에틸케톤인 하드코팅 조성물. According to clause 1,
A hard coating composition in which the ketone solvent is methyl ethyl ketone.
상기 은 나노입자를 메틸에틸케톤과 혼합하는 분산액 제조단계;
상기 분산액을 바인더 수지 및 염기성 분산제와 혼합하여 은 나노입자가 하드 코팅 조성물 중량의 0.02 내지 0.2 중량%로 포함되도록 하드 코팅액을 제조하는 하드 코팅액 제조단계;를 포함하는 하드코팅 조성물의 제조방법.
A silver nanoparticle manufacturing step of synthesizing silver nanoparticles having a capping layer formed of a polymer on the surface of Ag+ ions reduced by a reducing solvent;
A dispersion preparation step of mixing the silver nanoparticles with methyl ethyl ketone;
A hard coating solution preparation step of mixing the dispersion with a binder resin and a basic dispersant to prepare a hard coating solution so that silver nanoparticles are included in an amount of 0.02 to 0.2% by weight of the hard coating composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020220078414A KR20240001585A (en) | 2022-06-27 | 2022-06-27 | Hard coating composition and Method of manufacturing thereof |
| PCT/KR2023/008793 WO2024005466A1 (en) | 2022-06-27 | 2023-06-23 | Hard coating composition and method for producing same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020220078414A KR20240001585A (en) | 2022-06-27 | 2022-06-27 | Hard coating composition and Method of manufacturing thereof |
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| KR1020220078414A KR20240001585A (en) | 2022-06-27 | 2022-06-27 | Hard coating composition and Method of manufacturing thereof |
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| KR102332025B1 (en) | 2021-06-24 | 2021-12-01 | (주)쉐어켐 | Preparation method of optical film comprising anti-microbial composition and anti-microbial nanoparticle |
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| EP2752470A1 (en) * | 2006-08-07 | 2014-07-09 | Inktec Co., Ltd. | Process for preparation of silver nanoparticles, and the compositions of silver ink containing the same |
| BRPI0921629A2 (en) * | 2008-10-31 | 2016-01-05 | Dsm Ip Assets Bv | antifouling coating composition comprising nanoparticles |
| DE102009059276A1 (en) * | 2009-12-22 | 2011-06-30 | Rent-a-Scientist GmbH, 93059 | Formulation with metal nanoparticles |
| JP2017071562A (en) * | 2015-10-05 | 2017-04-13 | 住友ベークライト株式会社 | Antibacterial composition |
| KR20200001927A (en) * | 2018-06-28 | 2020-01-07 | 덕영산업주식회사 | PAINT ADDED NANO-Ag-PARTICLES AND MANUFACTURING METHODTHEREOF |
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| KR102332025B1 (en) | 2021-06-24 | 2021-12-01 | (주)쉐어켐 | Preparation method of optical film comprising anti-microbial composition and anti-microbial nanoparticle |
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