KR100302483B1 - Water-soluble acryl-polyol resin composition, method for manufacturing the same and water-soluble paint composition containing the same - Google Patents
Water-soluble acryl-polyol resin composition, method for manufacturing the same and water-soluble paint composition containing the same Download PDFInfo
- Publication number
- KR100302483B1 KR100302483B1 KR1019990018863A KR19990018863A KR100302483B1 KR 100302483 B1 KR100302483 B1 KR 100302483B1 KR 1019990018863 A KR1019990018863 A KR 1019990018863A KR 19990018863 A KR19990018863 A KR 19990018863A KR 100302483 B1 KR100302483 B1 KR 100302483B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- double bond
- monomer
- water
- Prior art date
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- 229920005862 polyol Polymers 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000011342 resin composition Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003973 paint Substances 0.000 title abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 57
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 47
- -1 acrylic polyol Chemical class 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000008199 coating composition Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000007524 organic acids Chemical group 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 239000000049 pigment Substances 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000002576 ketones Chemical class 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000007514 bases Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 claims 1
- 241001214176 Capros Species 0.000 claims 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- AGLHVTLMKPUPKD-UHFFFAOYSA-N prop-2-enoyl butanoate Chemical compound CCCC(=O)OC(=O)C=C AGLHVTLMKPUPKD-UHFFFAOYSA-N 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 7
- 239000005456 alcohol based solvent Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 239000005453 ketone based solvent Substances 0.000 abstract description 3
- 238000005536 corrosion prevention Methods 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000012212 insulator Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000012463 white pigment Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- DXVYLFHTJZWTRF-UHFFFAOYSA-N Ethyl isobutyl ketone Chemical compound CCC(=O)CC(C)C DXVYLFHTJZWTRF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002635 aromatic organic solvent Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- TUIWMHDSXJWXOH-UHFFFAOYSA-N 2,5-dimethylhexan-3-one Chemical compound CC(C)CC(=O)C(C)C TUIWMHDSXJWXOH-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 201000004681 Psoriasis Diseases 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WRPSHEORYRRLHM-UHFFFAOYSA-N prop-2-enoyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(=O)C=C WRPSHEORYRRLHM-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000008096 xylene Substances 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Paints Or Removers (AREA)
Abstract
선박용 전선의 부식 방지용으로 도장되는 수용성 도료 조성물의 주성분인 아크릴폴리올 수지, 이의 제조방법 및 이를 포함하는 수용성 도료 조성물에 관한 것이다. 상기 수지 조성물은 비닐형 이중결합과 유기산기를 갖는 단량체, 비닐형 이중결합과 수산기를 갖는 단량체, 비닐형 이중결합을 갖는 비관능성 방향족 단량체, 비닐형 이중결합을 갖는 비관능성 지방족 단량체, 라디칼 중합을 위한 반응개시제 및 용매를 혼합하고, 이를 100∼130℃의 온도에서 교반한 후, 얻어지는 반응물에 중화제를 첨가하고, 얻어지는 반응물에 물을 첨가하는 방법에 따라 수득되며, 상기 도료 조성물은 바인더로서 상기 수용성 아크릴폴리올 수지, 안료, 알콜계 용제, 케톤계 용제 및 물을 포함한다. 얻어지는 도료 조성물은 도료의 작업성과 기본 물성면에서 우수한 것이고 특히, 선박 전선용 도료에서 가장 중요한 물성인 부착성, 탈피성 및 저장성 면에서 우수하면서도 저공해형의 환경 친화적인 조성물이다.The present invention relates to an acrylic polyol resin which is a main component of a water-soluble coating composition coated for corrosion prevention of a ship electric wire, a method for preparing the same, and a water-soluble coating composition comprising the same. The resin composition is a monomer having a vinyl double bond and an organic acid group, a monomer having a vinyl double bond and a hydroxyl group, a non-functional aromatic monomer having a vinyl double bond, a non-functional aliphatic monomer having a vinyl double bond, for radical polymerization A reaction initiator and a solvent are mixed and stirred at a temperature of 100 to 130 ° C., a neutralizing agent is added to the resulting reactant, and water is added to the resulting reactant, and the coating composition is obtained as the binder. Polyol resins, pigments, alcohol solvents, ketone solvents and water. The resulting paint composition is excellent in terms of workability and basic physical properties of the paint, and in particular, is an environmentally friendly composition of low pollution type while being excellent in adhesion, peeling and storage properties, which are the most important physical properties of paint for ship wires.
Description
본 발명은 수용성 아크릴폴리올 수지, 이의 제조방법 및 이를 포함하는 수용성 도료 조성물에 관한 것으로서, 상세하게는 선박용 전선의 부식 방지용으로 도장되는 수용성 도료 조성물의 성분인 아크릴폴리올 수지와 이의 제조방법 및 이를 포함하는 수용성 도료 조성물에 관한 것이다.The present invention relates to a water-soluble acrylic polyol resin, a method for preparing the same, and a water-soluble coating composition comprising the same, and in detail, an acrylic polyol resin and a method for preparing the same, which are components of a water-soluble coating composition coated for corrosion prevention of a ship electric wire, and the same. A water-soluble coating composition.
선박용 전선은 선박내의 쥐들에 의한 전선의 손상을 방지하기 위하여 전선 케이블의 외곽을 전선보호용 아연도편조철선으로 보호망을 입혀서 사용하고 있다. 상기 아연도 철선은 부식 방지를 위해 철선에 도료 도막을 입혀 사용하고 있으며, 이러한 용도의 도료에 대한 규격은 KSC C3326-4.11 및 5.13항에서 별도로 정하고 있다. 이러한 규격의 내용은 다음과 같다.In order to prevent damage of wires by rats in ships, ship wires are covered with wire shielding galvanized braided wire for wire protection. The galvanized iron wire is used by coating a coating film on the wire to prevent corrosion, and the specifications for the paint for this purpose are separately determined in KSC C3326-4.11 and 5.13. The contents of these standards are as follows.
KSC C3326-4.11: 페인트는 품질이 균일하고, 전선 구성 재료에 대하여 해로운 이물을 함유하지 않은 것으로 하고, 도장후 난연성을 갖고 또한 쉽게 벗겨지지않는 것으로 한다.KSC C3326-4.11: Paints are to be of uniform quality, contain no foreign substances harmful to the wire constituents, are flame retardant after coating and are not easily peeled off.
KSC C3326-5.13:KSC C3326-5.13:
5.13.1 철선 외장 위의 페인트: 강선 철선 위의 페인트는 4.11의 백색 페인트를 벗겨지지 않도록 균일하게 도포한다. 다만, 특별히 지정된 경우에 한하여 동합금 철선 외장에는 붉은색 페인트를 도포한다.5.13.1 Paint on wire sheathing: The paint on steel wire is applied evenly so that the white paint of 4.11 does not peel off. Red paint is to be applied to the copper alloy wire sheath, except where specifically specified.
5.13.2 배전반용 전선의 편조위의 페인트: 배전반용 전선의 편조위의 페인트는 4.11의 페인트를 벗겨지지 않도록 균일하게 도포한다. 페인트의 색은 원칙적으로 회색으로 한다.5.13.2 Paint on the braid of switchboard wires: The paint on the braid of switchboard wires is applied evenly so that the paint of 4.11 does not come off. The color of the paint is, in principle, gray.
이러한 용도로 사용되던 종래의 몇가지 도료에서는 요구되는 물성이 만족스러운 수준이 되지 못하였기 때문에, 요구 물성에 대한 개선이 계속적으로 요구되어 왔다. 또한, 선박전선용 아연도철선에 도장되는 도료는 도장방법의 여건상, 고형분의 함량이 매우 낮아서 20∼30% 정도밖에 안되기 때문에 도료의 배합 성분 중에서 용제가 차지하는 비율이 높을 수밖에 없다. 그런데 휘발성 용제에 대한 배출 규제가 앞으로 더욱 강화될 것이므로 환경친화적인 측면에서 저공해형 도료 형태로의 전환이 또한 필요하다.In some of the conventional paints used for this purpose, since the required physical properties did not reach satisfactory levels, improvements to the required physical properties have been continually required. In addition, the paint to be coated on the galvanized wire for ship wire has a very low solid content of only 20 to 30% due to the condition of the coating method, so that the proportion of the solvent in the coating components of the paint is high. However, as emission regulations for volatile solvents will be tightened in the future, it is also necessary to switch to a low pollution type paint in an environmentally friendly manner.
종래에 사용되던 도료는 모두가 유성이며, 이는 다음과 같이 크게 세 가지로 구분할 수 있다.The paints used in the prior art are all oil-based, which can be divided into three types as follows.
첫 번째는 비닐클로라이드/비닐아세테이트 공중합체 수지 및 셀룰로우즈아세테이트부틸레이트 수지를 단독 또는 혼합하여 도료 바인더로 사용하고, 주용제로 케톤류를 사용하는 도료 타입이다. 두 번째는 비닐부티랄/비닐알콜 공중합체 수지를 도료 바인더로 사용하고, 알콜류를 주용제로 하면서 방향성 유기 용제를 혼합하여 사용하는 도료 타입이다. 상기한 두가지 형태는 비닐계 도료이다. 세 번째로는 아크릴폴리올 수지를 도료 바인더로 사용하고 알콜류와 방향성 유기 용제를 혼합하여 사용하는 아크릴폴리올계 도료를 들 수 있다.The first is a paint type using vinyl chloride / vinylacetate copolymer resin and cellulose acetate butyrate resin alone or mixed as a coating binder and ketones as main solvents. The second is a paint type using vinyl butyral / vinyl alcohol copolymer resin as a paint binder and mixing aromatic organic solvents with alcohols as the main solvent. The two forms described above are vinyl paints. Third, an acryl polyol-based paint using an acrylic polyol resin as a coating binder and mixing alcohols and an aromatic organic solvent is used.
상기한 세 가지 종류의 유성 도료는 일반적으로 각각 다음과 같은 문제점이 있다. 비닐계 도료의 첫 번째 타입은 철선에 대한 부착성은 우수하지만 철선이 보호하고 있는 피브이시 절연체를 도료에 포함된 케톤류의 용제가 부분적으로 용해시키기 때문에, 일단 건조 도막이 형성되고 나면, 철선 그물망이 피브이시 절연체와 융착되어 떨어지지 않는 현상이 나타난다. 이는 피브이시 절연체의 재질과 도료의 주성분인 바인더의 구성물이 상용성이 있기 때문에 용제가 절연체를 용해하기만 하면 쉽게 융착되는 현상으로 나타난다. 이러한 융착 문제는 선박용 전선이 작업 현장에서 사용될 때 철선 그물망의 비탈피성이 너무 크기 때문에 전선의 이음 작업을 어렵게 하는 문제를 유발하게 된다. 이러한 문제를 해결하기 위하여, 절연체와 철선 그물망 사이에 도료에 불용성인 페트 필름을 삽입한 상태에서 도장하고 있다. 페트 필름을 삽입하는 별도의 공정 도입은 전선 생산의 지연과 비용 부담 문제를 유발하게 된다. 이에 따라, 비탈피성을 갖는 도료의 사용은 감소하고 있는 추세이다.The three types of oil-based paints generally have the following problems, respectively. The first type of vinyl paint has excellent adhesion to iron wire, but partially dissolves the fibish insulator protected by the iron wire, so that the ketones contained in the paint partially dissolve the wire. The phenomenon that does not fall fused. This is because the material of the FBish insulator and the composition of the binder, which is the main component of the paint, are compatible, so that the solvent is easily fused when the solvent dissolves the insulator. This problem of fusion causes a problem in that it is difficult to connect the wires because the stripping property of the wire mesh is too large when the ship wire is used in the work site. In order to solve such a problem, it coats in the state in which the insoluble PET film was inserted between the insulator and the wire mesh. The introduction of a separate process for inserting PET film introduces delays and cost burdens for wire production. Accordingly, the use of paints having non-peeling properties is on the trend.
비닐계 도료의 두 번째 타입은 첫 번째 타입이 갖고 있는 비탈피성 문제를 해결하기 위해 피브이시 절연체를 용해시키지 않는 알콜류를 주용제로 하고 케톤류와 같은 강용제의 사용을 배제하면서 바인더 또한 아연도 철선에 대한 부착성과 유연성이 우수하도록 설계되었다. 하지만, 건조후 단기간 내에는 이러한 우수한 성질을 유지하지만 시간이 지남에 따라 아연도 철선에 대한 부착성의 약화로 도막이 벗겨지는 문제와 도막면이 균일하지 못하다는 단점이 있다. 또한 도료 저장성에서도 취약하여 1액형으로 제조하여 보관시 분리 현상 및 작은 입자 형성이 생기는 경우가 있어 도료 분산분과 희석 용제를 분리하여 2액형으로 공급해야 한다.The second type of vinyl-based paints are mainly alcohols that do not dissolve fibish insulators and eliminate the use of strong solvents, such as ketones, to solve the non-splitting problem of the first type. Designed for excellent adhesion and flexibility. However, although the excellent properties are maintained within a short period of time after drying, there is a problem in that the coating film is peeled off due to the weakening of the adhesion to the galvanized iron wire over time and the coating surface is not uniform. In addition, it is also weak in paint storage property, so it may be separated and formed small particles when stored in one-pack form, so that the paint dispersion and diluting solvent should be separated and supplied in two-pack form.
마지막으로 아크릴폴리올계 수지 도료는 비닐계 수지 도료 보다 아연도철선에 대한 부착성과 유연성이 떨어지기 때문에 현장에서 전선을 다룰 때, 도료 도막이 부서져 가루가 되어 날리는 문제점이 있다. 아울러 비닐계 도료에 비해 건조가 느려 많은 시간을 요하기 때문에 전선의 생산성 저하를 가져온다.Finally, the acrylic polyol resin paint has a problem in that adhesion to the zinc wire is less flexible than the vinyl resin paint, so when the wire is handled in the field, the paint coating is broken and becomes powder. In addition, the drying is slow compared to the vinyl paint, which requires a lot of time, resulting in a decrease in the productivity of the wire.
이상과 같이 현재 사용되고 있는 세 가지 타입의 도료는 각각 몇가지 단점들을 갖고 있으며, 공통적으로 환경적 측면에서 불리한 유성 타입이기 때문에 본 발명자는 이러한 문제점을 해결하고 환경친화적인 저공해형 조성물을 얻기 위해 수용성 도료 조성물에 대한 연구를 거듭하여 본 연구를 완성하게 되었다.As described above, the three types of paints currently used have several disadvantages, and since they are common in terms of environmentally disadvantageous oil type, the present inventors solve the above problems and obtain an environmentally friendly low pollution type water-soluble coating composition. We have completed our research on this.
본 발명의 제1 목적은 수용성 도료 조성물에 포함되는 수용성 아크릴폴리올 수지 조성물을 제공하고자 하는 것이다.It is a first object of the present invention to provide a water-soluble acrylic polyol resin composition contained in a water-soluble coating composition.
본 발명의 제2 목적은 상기한 수용성 아크릴폴리올 수지의 제조방법을 제공하고자 하는 것이다.It is a second object of the present invention to provide a method for producing the water-soluble acrylic polyol resin.
본 발명의 제3 목적은 상기한 수용성 아크릴폴리올 수지를 포함하는 저공해형의 수용성 도료 조성물을 제공하고자 하는 것이다.It is a third object of the present invention to provide a low pollution type water-soluble coating composition containing the water-soluble acrylic polyol resin.
이와 같은 목적을 달성하기 위해, 본 발명에서는 비닐형 이중결합과 유기산기를 갖는 단량체 3∼8 중량부, 비닐형 이중결합과 수산기를 갖는 단량체 8∼20 중량부, 비닐형 이중결합을 갖는 비관능성 방향족 단량체 20∼60 중량부 및 비닐형 이중결합을 갖는 비관능성 지방족 단량체 20∼60 중량부를 라디칼 중합반응시켜 수득되는 아크릴폴리올 수지 조성물을 제공한다.In order to achieve the above object, in the present invention, 3 to 8 parts by weight of a monomer having a vinyl double bond and an organic acid group, 8 to 20 parts by weight of a monomer having a vinyl double bond and a hydroxyl group, a non-functional aromatic having a vinyl double bond Provided is an acrylic polyol resin composition obtained by radical polymerization of 20 to 60 parts by weight of a monomer and 20 to 60 parts by weight of a nonfunctional aliphatic monomer having a vinyl double bond.
특히, 상기 비닐형 이중결합과 유기산기를 갖는 단량체로는 아크릴산, 메타크릴산, 말레인산 및 이들의 무수물로 이루어진 군에서 선택된 적어도 하나의 화합물이 바람직하게 사용되며, 상기 비닐형 이중결합과 수산기를 갖는 단량체로는 2-하이드록시 에칠 아크릴레이트, 2-하이드록시 에칠 메타크릴레이트, 2-하이드록시 부칠 아크릴레이트, 하이드록시프로필 메타크릴레이트 및 카프로락톤 아크릴레이트로 이루어진 군에서 선택된 적어도 하나의 화합물이 바람직하게 사용될 수 있고, 상기 비닐형 이중결합을 갖는 비관능성 방향족 단량체로는 스티렌 및/또는 비닐톨루엔이 바람직하게 사용될 수 있으며, 상기 비닐형 이중결합을 갖는 비관능성 지방족 단량체로는 메칠메타크릴레이트, 에칠아크릴레이트, 에칠메타크릴레이트, 이소부칠아크릴레이트, 노말부칠메타크릴레이트, 노말부칠아크릴레이트 및 이소프로필메타크릴레이트로 이루어진 군에서 선택된 적어도 하나의 화합물이 바람직하게 사용될 수 있다.In particular, at least one compound selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, and anhydrides thereof is preferably used as the monomer having a vinyl double bond and an organic acid group, and the monomer having a vinyl double bond and a hydroxyl group. The furnace is preferably at least one compound selected from the group consisting of 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyrate acrylate, hydroxypropyl methacrylate and caprolactone acrylate. Styrene and / or vinyltoluene may be preferably used as the nonfunctional aromatic monomer having a vinyl double bond, and methacrylate, ethylacryl may be used as the nonfunctional aliphatic monomer having a vinyl double bond. Ethyl, Ethyl Methacrylate, Isobutyryl Acrylate , N is the Fanning methacrylate, n Fanning acrylate and isopropyl methacrylate, at least one compound selected from the group consisting of can be preferably used.
상기 라디칼 중합반응의 반응개시제로는 벤조일 퍼옥사이드, 아조이소부티로니트릴 및 t-부칠퍼옥시 2-에칠헥사노에이트로 이루어진 군에서 선택된 적어도 하나의 화합물이 바람직하게 사용될 수 있다.As the reaction initiator of the radical polymerization reaction, at least one compound selected from the group consisting of benzoyl peroxide, azoisobutyronitrile and t-butylperoxy 2-ethylhexanoate may be preferably used.
또한, 상기 아크릴폴리올 수지의 수평균분자량이 8,000∼25,000이고, 분자량분포도가 5∼10 범위이고, 유리전이온도가 25∼40℃ 범위이고, 불휘발분이 30∼45% 이며, 물의 함유량이 5∼40% 인 것이 바람직하다.The number average molecular weight of the acrylic polyol resin is 8,000 to 25,000, the molecular weight distribution is in the range of 5 to 10, the glass transition temperature is in the range of 25 to 40 ° C, the nonvolatile content is in the range of 30 to 45%, and the water content is in the range of 5 to 5. It is preferably 40%.
본 발명의 다른 목적은 비닐형 이중결합과 유기산기를 갖는 단량체 3∼8 중량부, 비닐형 이중결합과 수산기를 갖는 단량체 8∼20 중량부, 비닐형 이중결합을 갖는 비관능성 방향족 단량체 20∼60 중량부, 비닐형 이중결합을 갖는 비관능성 지방족 단량체 20∼60 중량부, 라디칼 중합을 위한 반응개시제 0.2∼0.4 중량부 및 용매를 혼합하는 단계;Another object of the present invention is 3 to 8 parts by weight of a monomer having a vinyl double bond and an organic acid group, 8 to 20 parts by weight of a monomer having a vinyl double bond and a hydroxyl group, and 20 to 60 parts by weight of a nonfunctional aromatic monomer having a vinyl double bond. A mixture of 20 to 60 parts by weight of a nonfunctional aliphatic monomer having a vinyl double bond, 0.2 to 0.4 parts by weight of a reaction initiator for radical polymerization, and a solvent;
얻어지는 혼합물을 100∼130℃의 온도에서 교반하는 단계;Stirring the resulting mixture at a temperature of 100 to 130 ° C;
얻어지는 반응물에 중화제를 첨가하는 단계; 및Adding a neutralizing agent to the resulting reactant; And
얻어지는 반응물에 물을 첨가하는 단계를 포함하는 수용성 아크릴폴리올 수지의 제조방법에 의해 달성된다.It is achieved by the method for producing a water-soluble acrylic polyol resin comprising the step of adding water to the reaction product obtained.
상기 중화제로는 암모니아, 트리에칠아민, 디에탄올아민, 트리에탄올아민, 2-아미노-2-메칠프로판올, N,N-디메칠 아미노에탄올로 이루어진 군에서 선택된 적어도 하나의 염기성 화합물이 바람직하게 사용될 수 있다.As the neutralizing agent, at least one basic compound selected from the group consisting of ammonia, triethylamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, and N, N-dimethylaminoethanol may be preferably used. have.
상기한 본 발명의 또 다른 목적은 바인더로서 비닐형 이중결합과 유기산기를 갖는 단량체 3∼8 중량부, 비닐형 이중결합과 수산기를 갖는 단량체 8∼20 중량부, 비닐형 이중결합을 갖는 비관능성 방향족 단량체 20∼60 중량부 및 비닐형 이중결합을 갖는 비관능성 지방족 단량체 20∼60 중량부를 라디칼 중합반응시켜 수득되는아크릴폴리올 수지 10∼30 중량부, 안료 10∼25 중량부, 알콜계 용제 30∼70 중량부, 케톤계 용제 2∼8 중량부 및 물 5∼50 중량부를 포함하는 수용성 도료 조성물에 의해 달성된다.Another object of the present invention described above is as a binder 3 to 8 parts by weight of a monomer having a vinyl double bond and an organic acid group, 8 to 20 parts by weight of a monomer having a vinyl double bond and a hydroxyl group, a nonfunctional aromatic having a vinyl double bond. 20 to 60 parts by weight of the monomer and 20 to 60 parts by weight of the non-functional aliphatic monomer having a vinyl double bond, 10 to 30 parts by weight of the acrylic polyol resin, 10 to 25 parts by weight of the pigment, and 30 to 70 alcohol solvents. It is achieved by the water-soluble coating composition containing a weight part, 2-8 weight part of ketone solvents, and 5-50 weight part of water.
특히, 상기 알콜계 용제로는 메칠알콜, 에칠알콜, 이소프로필알콜 및 노말 부칠알콜로 이루어진 군에서 선택된 적어도 하나의 알콜이 용이하게 사용될 수 있으며, 더욱 바람직하게는, 메칠알콜 2∼20 중량부, 이소프로필알콜 10∼50 중량부 및 노말 부칠알콜 2∼20 중량부를 혼합하여 얻어지는 알콜 용액이 사용될 수 있다.In particular, the alcohol solvent may be easily used at least one alcohol selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol and normal butyl alcohol, more preferably, 2 to 20 parts by weight of methyl alcohol, Alcohol solutions obtained by mixing 10 to 50 parts by weight of isopropyl alcohol and 2 to 20 parts by weight of normal butyl alcohol may be used.
상기 케톤계 용제로는 아세톤, 메칠에틸케톤, 에칠이소부칠케톤 및 사이클로헥사논으로 이루어진 군에서 선택된 적어도 하나의 케톤이 바람직하게 사용될 수 있으며, 더욱 바람직하게는 아세톤 2∼8 중량부, 메칠에칠케톤 2∼8 중량부 및 메칠이소부칠케톤 2∼8 중량부를 혼합하여 얻어지는 용제가 사용된다.As the ketone solvent, at least one ketone selected from the group consisting of acetone, methyl ethyl ketone, ethyl isobutyl ketone and cyclohexanone may be preferably used, and more preferably 2 to 8 parts by weight of acetone, methyl ethyl The solvent obtained by mixing 2-8 weight part of ketones and 2-8 weight part of methyl isobutyl ketones is used.
특히 상기 안료 입자의 입경이 20㎛ 이하인 것이 바람직하며 상기 수용성 도료 조성물은 바람직하게 선박용 전선의 부식방지용 도막 제조용으로 사용된다.Particularly, the particle size of the pigment particles is preferably 20 µm or less, and the water-soluble coating composition is preferably used for producing a corrosion preventing coating film of a ship electric wire.
이하, 본 발명을 더욱 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 수용성 도료 조성물에서 아크릴폴리올 수지는 알파, 베타 이중결합 즉, 비닐형 이중결합을 갖는 단량체들을 열분해 개시제에 의한 라디칼 부가중합의 용액 중합방법에 따라 합성할 수 있으며, 아크릴폴리올 수지의 제조를 위한 출발물질로서 비닐형 이중결합을 갖는 각 단량체들의 종류 및 조성비는 다음과 같다. 유기산기를 갖는 단량체 3∼8 중량부, 수산기를 갖는 단량체 8∼20 중량부, 방향족계 비관능성 단량체 20∼60 중량부 그리고 지방족계 비관능성 단량체 20∼60중량부로 이루어져 있다.In the water-soluble coating composition according to the present invention, the acrylic polyol resin may synthesize monomers having alpha, beta double bonds, that is, vinyl double bonds according to a solution polymerization method of radical addition polymerization by a pyrolysis initiator, thereby preparing an acrylic polyol resin. Type and composition ratio of each monomer having a vinyl double bond as a starting material for is as follows. It consists of 3-8 weight part of monomers which have an organic acid group, 8-20 weight part of monomers which have a hydroxyl group, 20-60 weight part of aromatic nonfunctional monomers, and 20-60 weight part of aliphatic non-functional monomers.
상기 수산기 단량체는 아크릴폴리올에 극성을 부여하여 피브이시 절연체와의 부착을 억제하는 효과와 함께 친수기로써 수용화를 원활하게 하고 도료에 적용되는 알콜계 용제와의 상용성을 높여 도료 조성물의 저장성을 향상시킨다.The hydroxyl monomers impart polarity to the acryl polyol to inhibit adhesion with fibish insulators, facilitate water solubility as a hydrophilic group, and improve compatibility with alcohol-based solvents applied to paints, thereby improving storage properties of the coating composition. .
상기 수용성 도료 조성물은 중화전의 산가가 20∼50mgKOH/g이고, 유리전이온도가 25∼40℃, 불휘발분 30∼45%, 25℃ 가드너 점도가 V∼Z2, 수평균분자량이 8,000∼25,000, 분자량분포도가 5∼10의 범위인 열경화성 아크릴폴리올 수지를 포함하는 조성물이다. 상기한 아크릴폴리올의 특성에 대해 좀 더 구체적으로 살펴 보기로 한다.The water-soluble coating composition has an acid value of 20 to 50 mgKOH / g before neutralization, a glass transition temperature of 25 to 40 ° C, a nonvolatile content of 30 to 45%, a 25 ° C Gardner viscosity of V to Z2, a number average molecular weight of 8,000 to 25,000, and a molecular weight. It is a composition containing the thermosetting acrylic polyol resin whose distribution degree is a range of 5-10. The characteristics of the acryl polyol will be described in more detail.
상기 중화전 유기산에 의한 산가 20∼50mgKOH/g 범위는 아크릴폴리올 합성시 아민류와 같은 염기로 100% 중화시 보편적인 수용화 가능 영역에 해당되도록 정하였다. 산가 범위가 20mgKOH/g 미만인 경우에는 아크릴폴리올 수지가 콜로이드 분산 또는 에멀젼 상태로 되어 수용성 상태를 벗어날 염려가 있으며, 50mgKOH/g를 초과하는 경우는 중화제가 과량 사용되기 때문에 이후 도료 도막의 건조시 아민의 휘발 속도 지연으로 인하여 건조 속도가 저하되고 도막내에 잔존하게 되는 아민으로 인하여 도막 물성이 저하될 우려가 있으므로 중화전 산가는 상기한 범위가 되도록 하는 것이 바람직하다.The acid value of 20-50 mgKOH / g by the organic acid before neutralization was set to correspond to a universally acceptable region when neutralizing 100% with a base such as amines in synthesizing acrylic polyol. If the acid value is less than 20 mgKOH / g, the acrylic polyol resin may be in the form of colloidal dispersion or emulsion and may be out of the water-soluble state. If the acid value exceeds 50 mgKOH / g, an excessive amount of neutralizing agent may be used. Due to the delayed volatilization rate, the drying rate is lowered and the coating film properties may be lowered due to the amine remaining in the coating film. Therefore, the acid value before neutralization is preferably within the above range.
아크릴폴리올 수지의 유리전이온도가 25℃ 보다 낮은 경우, 도막 건조후 도막 표면에 택기성이 있어서, 전선을 롤형태로 감아 보관할 때 전선간에 부착되는 현상을 일으킬 수 있고, 건조 속도 또한 빠르게 할 수 없다는 문제가 생긴다. 또한, 유리전이온도가 40℃ 보다 높을 때는 택기성이 감소하여 건조 속도를 빠르게 할 수는 있으나 건조 도막이 부서질 가능성이 높아져서 건선을 다룰 때 가루가 발생할 우려가 있으므로 바람직하게 상기한 온도범위가 되도록 한다.If the glass transition temperature of the acrylic polyol resin is lower than 25 ° C., the surface of the coating film may be tacky after drying, which may cause sticking between the wires when the wire is rolled and stored, and the drying speed may not be increased. There is a problem. In addition, when the glass transition temperature is higher than 40 ℃ can reduce the tackiness and speed up the drying rate, but the drying film is more likely to break, there is a possibility that powder may occur when handling psoriasis is preferably in the above temperature range .
아크릴폴리올 수지의 분자량 분포가 5 보다 적은 경우 즉, 중량평균분자량이 40,000 보다 적은 경우에는 이를 도료에 적용시 점도가 낮아 철선에 대하여 적절한 은폐 효과를 나타내기가 어려울 수 있으며, 10 보다 큰 경우 즉, 중량평균분자량이 250,000 보다 큰 경우에는 도료의 점도가 높아져 도막이 두껍게 형성되기 때문에 건조속도가 저하되고 건조도막의 가루가 발생할 가능성이 높아진다. 그러므로 분자량 분포는 상기한 범위가 되도록 하는 것이 바람직하다.When the molecular weight distribution of the acrylic polyol resin is less than 5, that is, when the weight average molecular weight is less than 40,000, it may be difficult to show a suitable hiding effect for the iron wire when the viscosity is low when applied to the paint, when larger than 10, that is, the weight If the average molecular weight is greater than 250,000, the viscosity of the paint is increased to form a thick coating film, so that the drying speed is lowered and the powder of the dry coating film is more likely to occur. Therefore, it is preferable to make molecular weight distribution into the said range.
본 발명의 도료 조성물에서는 상술한 특징을 갖는 수용성 아크릴폴리올 수지 10∼20 중량부, 안료 10∼25 중량부, 알콜계 용제 30∼70 중량부, 케톤계 용제 2∼8 중량부 및 물 5∼40 중량부를 사용하는 데, 아크릴폴리올 수지와 안료의 만약 아크릴폴리올의 양을 10 중량부 보다 적게 하면 안료 비율이 상대적으로 높아져 적정 두께의 도막 형성이 어렵고, 20 중량부 보다 많이 사용하면 아크릴폴리올 수지 성분의 비율이 높아져 건조 속도가 떨어지고 도막의 택기성이 높아지기 때문이다.In the coating composition of the present invention, 10 to 20 parts by weight of a water-soluble acrylic polyol resin having the above-mentioned characteristics, 10 to 25 parts by weight of a pigment, 30 to 70 parts by weight of an alcohol solvent, 2 to 8 parts by weight of a ketone solvent, and 5 to 40 water If the weight part is less than 10 parts by weight of the acrylic polyol and the acrylic polyol resin, the pigment ratio is relatively high, and it is difficult to form a coating film of an appropriate thickness. This is because the ratio is increased, the drying speed is lowered, and the tackiness of the coating film is increased.
본 발명에 따른 아크릴폴리올 수지 조성물의 원료로 사용한 단량체에 대한 구체적인 예를 들면, 유기산기를 갖는 단량체로는 아크릴산, 메타크릴산, 말레인산 및 이들의 무수물을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 수산기를 함유하는 단량체로는 2-하이드록시 에칠 아크릴레이트, 2-하이드록시 에칠 메타크릴레이트, 2-하이드록시 부칠 아크릴레이트, 하이드록시 프로필 메타크릴레이트 및프로락톤 아크릴레이트를 단독으로, 또는 2종 이상을 혼합하여 사용할 수 있다. 방향족계 비관능성 단량체로는 스티렌, 비닐톨루엔 등이 사용될 수 있으며, 지방족계 단량체로는 메칠메타크릴레이트, 에칠아크릴레이트, 에칠메타크릴레이트, 이소부칠아크릴레이트, 노르말부칠메타크릴레이트, 노르말 부칠아크릴레이트, 이소프로필메타크릴레이트 등 일반적인 아크릴 단량체가 포함된다.As a specific example of the monomer used as a raw material of the acrylic polyol resin composition according to the present invention, as the monomer having an organic acid group, acrylic acid, methacrylic acid, maleic acid and anhydrides thereof may be used alone or in combination of two or more thereof. . As the monomer containing a hydroxyl group, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyrate acrylate, hydroxy propyl methacrylate and prolactone acrylate alone or in combination The above can be mixed and used. Styrene, vinyltoluene, etc. may be used as the aromatic non-functional monomer, and as the aliphatic monomers, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, normal butymethacrylate, and normal butyryl Common acryl monomers, such as a rate and isopropyl methacrylate, are included.
유기산을 중화하기 위한 중화제로는 암모니아와 트리에칠아민, 디에탄올아민, 트리에톤올아민, 2-아미노-2-메칠프로판올, N,N-디메칠 아미노에탄올 등과 같은 유기 아민을 사용할 수 있다. 라디칼 용액 중합에 사용되는 벤조일 퍼옥사이드, 아조이소부티로니트릴, t-부칠퍼옥시 2-에칠헥사노에이트 등이 반응개시제로 사용될 수 있다.As a neutralizer for neutralizing the organic acid, organic amines such as ammonia and triethylamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, N, N-dimethylaminoethanol and the like can be used. Benzoyl peroxide, azoisobutyronitrile, t-butylperoxy 2-ethylhexanoate, and the like used in the radical solution polymerization may be used as the reaction initiator.
이상의 원료를 사용하여 반응 온도를 100∼130℃로 하고, 단량체 혼합물과 개시제 용액의 투입을 1.5∼2.5 시간 동안 수행하며, 개시제의 사용량을 0.2∼0.4 중량부로 하는 합성 조건으로 하였으며 용제로는 수용성 아크릴 폴리올 수지와 상용성이 있는 알콜계 용제를 주성분으로 하고 저비점 케톤류 용제의 사용량을 최소가 되도록 하였다. 알콜계 용제로는 메칠알콜, 에칠알콜, 이소프로필알콜, 노르말 부칠알콜등과 같은 일반적인 알콜을 단독으로 또는 혼합하여 사용할 수 있고, 저비점 용제로는 아세톤, 메칠에칠케톤, 메칠이소부칠케톤, 사이클로헥사논 등을 단독으로 또는 혼합하여 사용할 수 있다. 저비점 용제는 건조 속도를 단축시키는 한도 내에서 최소량으로 사용하였다.Using the above raw materials, the reaction temperature was set to 100 to 130 ° C, the monomer mixture and the initiator solution were added for 1.5 to 2.5 hours, and the amount of the initiator was set to 0.2 to 0.4 parts by weight. Alcohol-based solvents compatible with polyol resins were used as main components, and the amount of low-boiling ketone solvents was minimized. As the alcohol solvent, general alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, normal butyl alcohol and the like can be used alone or in combination.As a low boiling point solvent, acetone, methyl ethyl ketone, methyl isobuty ketone, cyclo Hexanone etc. can be used individually or in mixture. Low boiling point solvents were used in minimum amounts within the limit of shortening the drying rate.
상기한 수용성 아크릴폴리올 수지의 제조방법을 좀 더 상세히 설명하기로 한다. 먼저, 비닐형 이중결합과 유기산기를 갖는 단량체 3∼8 중량부, 비닐형 이중결합과 수산기를 갖는 단량체 8∼20 중량부, 비닐형 이중결합을 갖는 비관능성 방향족 단량체 20∼60 중량부, 비닐형 이중결합을 갖는 비관능성 지방족 단량체 20∼60 중량부, 라디칼 중합을 위한 반응개시제 0.2∼0.4 중량부 및 용매를 플라스크에 넣고 교반하여 혼합한다. 얻어지는 혼합물을 100∼130℃의 온도에서 교반한다. 얻어지는 반응물에 염기성 중화제를 첨가한다. 얻어지는 반응물에 물을 첨가하여 아크릴폴리올 수지를 수득한다.The method of preparing the water-soluble acrylic polyol resin will be described in more detail. First, 3 to 8 parts by weight of a monomer having a vinyl double bond and an organic acid group, 8 to 20 parts by weight of a monomer having a vinyl double bond and a hydroxyl group, 20 to 60 parts by weight of a nonfunctional aromatic monomer having a vinyl double bond, a vinyl type 20 to 60 parts by weight of a non-functional aliphatic monomer having a double bond, 0.2 to 0.4 parts by weight of a reaction initiator for radical polymerization, and a solvent are added to a flask and mixed with stirring. The resulting mixture is stirred at a temperature of 100 to 130 ° C. Basic neutralizing agent is added to the resulting reaction. Water is added to the resulting reaction product to obtain an acrylic polyol resin.
상기한 내용을 종합해 보면, 본 발명에서는 수평균분자량 8,000∼25,000, 분자량분포도 5∼10, 유리전이온도 25∼40℃, 불휘발분 30∼45%, 물 5∼40%를 함유하는 수용성 아크릴폴리올 수지를 바인더로하여 10∼30 중량부 사용하고, 안료를 10∼25 중량부, 알콜계 용제 30∼70 중량부, 케톤류 유기용제 2∼8 중량부, 물 5∼50 중량부를 사용하여 얻어지며, 부착성, 탈피성, 건조성이 우수한 저공해형의 선박전선용 수용성 도료 조성물을 제공한다.In summary, in the present invention, a water-soluble acrylic polyol containing a number average molecular weight of 8,000 to 25,000, a molecular weight distribution of 5 to 10, a glass transition temperature of 25 to 40 ° C, a nonvolatile content of 30 to 45% and water of 5 to 40% It is obtained using 10-30 weight part of resin as a binder, 10-25 weight part of pigments, 30-70 weight part of alcohol solvents, 2-8 weight part of ketone organic solvents, and 5-50 weight part of water, Provided is a low-pollution type water-soluble coating composition for ship cables excellent in adhesion, peeling property, and drying property.
이하, 본 발명을 구체적인 실시예를 통하여 상세히 설명하기로 하는데, 본 발명이 이로만 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through specific examples, but the present invention is not limited thereto.
<실시예 1><Example 1>
온도계, 콘덴서, 적하깔대기 및 교반기가 장착된 4구 플라스크에 노말부탄올 6g 및 부칠셀로솔브 24g을 넣고 교반하면서 115∼120℃로 승온하였다. 이후, 하기한 단량체와 개시제 혼합물을 150분 동안 균일한 속도로 적하하였다.In a four-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirrer, 6 g of normal butanol and 24 g of butyl cellosolve were added thereto, and the temperature was raised to 115 to 120 ° C. while stirring. Thereafter, the following monomer and initiator mixtures were added dropwise at a uniform rate for 150 minutes.
스티렌 22g22 g of styrene
부칠아크릴레이트 13.5gButyl acrylate 13.5g
2-에칠헥실아크릴레이트 8g8 g of 2-ethylhexyl acrylate
2-하이드록시에칠아크릴레이트 4g4 g of 2-hydroxyethyl acrylate
메칠메타크릴산 2.5gMethyl Methacrylic Acid 2.5g
아조이소부티로니트릴 0.2g0.2 g of azoisobutyronitrile
적하완료후 60분 동안 교반하였다. 여기에, 부칠셀로솔브 10g 및 t-부칠퍼옥시-2-에틸헥사노에이트 0.4g을 혼합하여 얻어지는 혼합액을 60분 동안 균일한 속도로 적하하였다. 120분 동안 반응시킨 후 냉각하여 노르말부탄올 9.4g을 투입하였다. 60∼70℃로 유지하면서 트리에틸아민 2.9g을 10분 동안 적하하였다. 10분 동안 방치한 후, 물 40g을 10분에 걸쳐 적하하였다. 이렇게 하여 25℃ 가드너 점도 V, 불휘발분 35%, 유리전이온도 32℃, 수평균분자량 11,000 및 분자량 분포도 8.2의 특성치를 갖는 수용성 아크릴폴리올 수지 용액을 수득하였다.After the dropwise addition was stirred for 60 minutes. To this, a mixed solution obtained by mixing 10 g of butyl cellosolve and 0.4 g of t-butylperoxy-2-ethylhexanoate was added dropwise at a uniform rate for 60 minutes. After reacting for 120 minutes, 9.4 g of normal butanol was added thereto. 2.9 g of triethylamine was added dropwise for 10 minutes while maintaining at 60 to 70 ° C. After standing for 10 minutes, 40 g of water was added dropwise over 10 minutes. Thus, a water-soluble acrylic polyol resin solution having a Gardner viscosity V of 25 ° C, a nonvolatile content of 35%, a glass transition temperature of 32 ° C, a number average molecular weight of 11,000 and a molecular weight distribution of 8.2 was obtained.
<실시예 2><Example 2>
온도계, 콘덴서, 적하깔대기 및 교반기가 장착된 4구 플라스크에 노말부탄올 20g 및 부칠셀로솔브 10g을 넣고 교반하면서 115∼120℃로 승온하였다. 이후, 하기한 단량체와 개시제 혼합물을 150분 동안 균일한 속도로 적하하였다.In a four-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirrer, 20 g of normal butanol and 10 g of butyl cellosolve were added thereto, and the temperature was raised to 115 to 120 ° C. while stirring. Thereafter, the following monomer and initiator mixtures were added dropwise at a uniform rate for 150 minutes.
스티렌 17g17 g of styrene
부칠아크릴레이트 24gButylacrylate 24g
2-하이드록시에칠메타크릴레이트 6g6 g of 2-hydroxyethyl methacrylate
메칠메타크릴산 3gMethyl Methacrylic Acid 3g
아조이소부티로니트릴 0.25g0.25 g of azoisobutyronitrile
적하완료후 60분 동안 교반하였다. 여기에, 노말부탄올 10g 및 t-부칠퍼옥시-2-에틸헥사노에이트 0.4g을 혼합하여 얻어지는 혼합액을 60분 동안 균일한 속도로 적하하였다. 120분 동안 반응시킨 후 냉각하여 노르말부탄올 9.4g을 투입하였다. 60∼70℃로 유지하면서 암모니아 2.4g을 10분 동안 적하하였다. 10분 동안 방치한 후, 물 50g을 10분에 걸쳐 적하하였다. 이렇게 하여 25℃ 가드너 점도 U+, 불휘발분 33%, 유리전이온도 29℃, 수평균분자량 10,000 및 분자량 분포도 7.5의 특성치를 갖는 수용성 아크릴폴리올 수지 용액을 수득하였다.After the dropwise addition was stirred for 60 minutes. To this, a mixed solution obtained by mixing 10 g of normal butanol and 0.4 g of t-butylperoxy-2-ethylhexanoate was added dropwise at a uniform rate for 60 minutes. After reacting for 120 minutes, 9.4 g of normal butanol was added thereto. 2.4 g of ammonia was dripped for 10 minutes, maintaining at 60-70 degreeC. After standing for 10 minutes, 50 g of water was added dropwise over 10 minutes. Thus, a water-soluble acrylic polyol resin solution having a characteristic value of 25 ° C. Gardner viscosity U + , a nonvolatile content of 33%, a glass transition temperature of 29 ° C., a number average molecular weight of 10,000, and a molecular weight distribution of 7.5 was obtained.
<실시예 3><Example 3>
온도계, 콘덴서, 적하깔대기 및 교반기가 장착된 4구 플라스크에 노말부탄올 30g을 넣고 교반하면서 115∼120℃로 승온하였다. 이후, 하기한 단량체와 개시제 혼합물을 150분 동안 균일한 속도로 적하하였다.In a four-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer, 30 g of normal butanol was added thereto, and the temperature was raised to 115 to 120 ° C while stirring. Thereafter, the following monomer and initiator mixtures were added dropwise at a uniform rate for 150 minutes.
스티렌 17.5g17.5 g of styrene
2-에칠헥실아크릴레이트 23g23 g of 2-ethylhexyl acrylate
2-하이드록시에칠아크릴레이트 3g3 g of 2-hydroxyethyl acrylate
2-하이드록시에칠메타크릴레이트 3g2-hydroxyethyl methacrylate 3g
아크릴산 3.5g3.5 g acrylic acid
벤조일퍼옥사이드 0.25gBenzoyl peroxide 0.25g
적하완료후 60분 동안 교반하였다. 여기에, 노말부탄올 10g 및 이소부티로니트릴 0.3g을 혼합하여 얻어지는 혼합액을 60분 동안 균일한 속도로 적하하였다. 120분 동안 반응시킨 후 냉각하여 노르말부탄올 9.4g을 투입하였다. 60∼70℃로 유지하면서 암모니아 3.3g을 10분 동안 적하하였다. 10분 동안 방치한 후, 물 30g을 10분에 걸쳐 적하하였다. 이렇게 하여 25℃ 가드너 점도 Y, 불휘발분 38%, 유리전이온도 30℃, 수평균분자량 12,200 및 분자량 분포도 9.8의 특성치를 갖는 수용성 아크릴폴리올 수지 용액을 수득하였다.After the dropwise addition was stirred for 60 minutes. Here, the liquid mixture obtained by mixing 10 g of normal butanols and 0.3 g of isobutyronitriles was dripped at the uniform speed for 60 minutes. After reacting for 120 minutes, 9.4 g of normal butanol was added thereto. 3.3 g of ammonia was dripped for 10 minutes, maintaining at 60-70 degreeC. After standing for 10 minutes, 30 g of water was added dropwise over 10 minutes. Thus, a water-soluble acrylic polyol resin solution having a characteristic value of 25 ° C Gardner viscosity Y, 38% nonvolatile content, 30 ° C glass transition temperature, number average molecular weight 12,200, and molecular weight distribution degree 9.8 was obtained.
<실시예 4><Example 4>
실시예 1에서 수득된 수용성 아크릴폴리올 수지를 하기한 분산 배합 성분과 함께 하기한 비율로 사용하여 20㎛ 이하의 균일한 안료 입도로 분산시켰다. 이후 하기한 바와 같은 배합의 용제를 첨가하여 도료 조성물을 제조하였다.The water-soluble acrylic polyol resin obtained in Example 1 was used together with the following dispersion compounding components in the following ratios to disperse to a uniform pigment particle size of 20 mu m or less. Thereafter, a solvent was added as described below to prepare a coating composition.
분산 배합Dispersion formulation
수용성 아크릴폴리올 수지 24gWater Soluble Acrylic Polyol Resin 24g
백색안료(TiO2) 15gWhite Pigment (TiO 2 ) 15g
분산제 1.2g1.2g dispersant
이소프로필알콜 10g10 g of isopropyl alcohol
용제 배합Solvent formulation
이소프로필알콜 21.8gIsopropyl alcohol 21.8g
메탄올 8gMethanol 8g
아세톤 6gAcetone 6 g
물 15g15 g of water
<실시예 5>Example 5
실시예 2에서 수득된 수용성 아크릴폴리올 수지를 하기한 분산 배합 성분과 함께 하기한 비율로 사용하여 20㎛ 이하의 균일한 안료 입도로 분산시켰다. 이후 하기한 바와 같은 배합의 용제를 첨가하여 도료 조성물을 제조하였다.The water-soluble acrylic polyol resin obtained in Example 2 was used together with the following dispersion compounding components in the following ratios to disperse it into a uniform pigment particle size of 20 mu m or less. Thereafter, a solvent was added as described below to prepare a coating composition.
분산 배합Dispersion formulation
수용성 아크릴폴리올 수지 26gWater Soluble Acrylic Polyol Resin 26g
백색안료(TiO2) 16gWhite Pigment (TiO 2 ) 16g
분산제 0.2g0.2g dispersant
이소프로필알콜 10g10 g of isopropyl alcohol
용제 배합Solvent formulation
이소프로필알콜 19.8gIsopropyl alcohol 19.8 g
메탄올 5g5 g of methanol
아세톤 3gAcetone 3g
물 20g20 g of water
<실시예 6><Example 6>
실시예 3에서 수득된 수용성 아크릴폴리올 수지를 하기한 성분과 함께 하기한 비율로 사용하여 20㎛ 이하의 균일한 안료 입도로 분산시켰다. 이후 하기한 바와 같은 배합의 용제를 첨가하여 도료 조성물을 제조하였다.The water-soluble acrylic polyol resin obtained in Example 3 was used together with the following components in the following ratios to disperse it into a uniform pigment particle size of 20 mu m or less. Thereafter, a solvent was added as described below to prepare a coating composition.
분산 배합Dispersion formulation
수용성 아크릴폴리올 수지 22gWater Soluble Acrylic Polyol Resin 22g
백색안료(TiO2) 22gWhite Pigment (TiO 2 ) 22g
분산제 0.2g0.2g dispersant
이소프로필알콜 12gIsopropyl Alcohol 12g
용제 배합Solvent formulation
이소프로필알콜 10.8gIsopropyl Alcohol 10.8g
부탄올 10g10 g of butanol
아세톤 5g5 g of acetone
물 18g18 g of water
<비교예 1>Comparative Example 1
먼저, 하기한 분산 배합을 갖는 화합물을 하기한 비율로 혼합하여 안료 입도가 20㎛ 이하인 조성물을 제조하였다. 이후 하기한 바와 같은 배합의 용제를 첨가하여 도료 조성물을 제조하였다.First, the compound which has the following dispersion formulation was mixed in the following ratio, and the composition whose pigment particle size is 20 micrometers or less was manufactured. Thereafter, a solvent was added as described below to prepare a coating composition.
분산 배합Dispersion formulation
비닐부티랄/비닐알콜 공중합체수지 10gVinyl Butyral / Vinyl Alcohol Copolymer Resin 10g
백색안료(TiO2) 15gWhite Pigment (TiO 2 ) 15g
분산제 0.3g0.3g dispersant
톨루엔 10g10 g toluene
용제 배합Solvent formulation
크실렌 10g10 g of xylene
이소프로필알콜 30gIsopropyl Alcohol 30g
메탄올 10g10 g of methanol
톨루엔 14.7gToluene 14.7g
<비교예 2>Comparative Example 2
먼저, 하기한 분산 배합을 갖는 화합물을 하기한 비율로 혼합하여 안료 입도가 20㎛ 이하인 조성물을 제조하였다. 이후 하기한 바와 같은 배합의 용제를 첨가하여 도료 조성물을 제조하였다.First, the compound which has the following dispersion formulation was mixed in the following ratio, and the composition whose pigment particle size is 20 micrometers or less was manufactured. Thereafter, a solvent was added as described below to prepare a coating composition.
분산 배합Dispersion formulation
비닐클로라이드/비닐아세테이트 7gVinyl Chloride / Vinyl Acetate 7g
백색안료(TiO2) 13gWhite Pigment (TiO 2 ) 13g
분산제 0.3g0.3g dispersant
톨루엔 10g10 g toluene
용제 배합Solvent formulation
셀룰로우즈아세테이트부틸레이트 수지 4g4 g of cellulose acetate butyrate
메칠에칠케톤 15gMethyl ethyl ketone 15g
톨루엔 30gToluene 30g
아세톤 5g5 g of acetone
메칠에칠이소부틸케톤 10gMethyl ethyl isobutyl ketone 10g
사이클로헥사논 5.7gCyclohexanone 5.7 g
상기한 실시예 3-6 및 비교예 1-2에 따라 제조한 도료 조성물의 도막 특성을 비교하여 표1에 나타내었다. 도료의 도막 평가 시험은 겉표면이 아연도편조 그물망으로 보호된 지름 1.5cm, 길이 20cm인 PVC 전선을 세로로 세워 전선을 돌려가면서 도료를 위에서부터 흘려보내는 방법으로 도장하여 120∼130℃ 건조로에서 4∼5분 동안 건조시킨 후 얻어진 도막을 평가하였다.Table 1 compares the coating properties of the coating composition prepared according to Example 3-6 and Comparative Example 1-2. The coating film evaluation test of the paint was made by vertically laying a 1.5cm diameter and 20cm long PVC wire with its outer surface protected by a galvanized braided net, and painting it by flowing the paint from above while rotating the wire. The obtained coating film was evaluated after drying for ˜5 minutes.
상기 표에서 ◎는 우수, ○는 양호, △는 보통 그리고 ×는 불량을 의미한다. 시험 항목에서 건조성과 도장 상태는 도막을 육안으로 검사하여 평가한 것이고, 부착성은 도막형성시편의 양끝을 손으로 잡고 여러번 반복하여 구부렸다 폈다를 실히한 후 평면위에 두드려서 떨어지는 도막 가루의 정도를 평가한 것이다. 탈피성은 도막형성시편의 한쪽 끝에서 아연도철선 그물망을 벗겼을 때 피브이시로부터 그물망이 잘 떨어지는 정도를 평가한 것이다. 내식성은 35℃ 5% NaCl 수용액에 3일 동안 방치한 후 녹슨 상태를 평가한 것이고, 저장성은 실온에서 7일 동안 방치한 후 분리된 정도를 평가한 것이다. 상기 표 1로부터 본 발명에 따른 수용성 도료조성물을 사용하여 제조한 도막의 특성이 월등하게 우수하다는 것을 확인할 수 있다.In the above table,? Denotes excellent, ○ denotes good,? Denotes normal and x denotes defective. The dryness and coating state in the test items were evaluated by visual inspection of the coating film, and the adhesion property was evaluated by grabbing the ends of the coating film specimens by hand and bending them repeatedly. . Peelability is an evaluation of the degree of dropping of the mesh from fibish when the galvanized wire mesh is peeled off at one end of the film-forming specimen. Corrosion resistance was evaluated for the rusty state after standing in 35 ℃ 5% aqueous NaCl solution for 3 days, storage capacity is to evaluate the degree of separation after leaving for 7 days at room temperature. It can be seen from Table 1 that the properties of the coating film prepared using the water-soluble coating composition according to the present invention are excellent.
본 발명에 따른 수용성 도료 조성물이 도료의 작업성과 기본 물성면에서 우수한 것으로 평가되었다. 특히, 선박 전선용 도료에서 가장 중요한 물성인 부착성, 탈피성 및 저장성 면에서 우수하게 나타나고 있다. 따라서, 본 발명에 따른 수용성 도료 조성물은 도료의 요구 물성을 만족시키면서 기존의 유성 도료가 가지고 있는 유해 휘발 용제량60∼80%를 30∼50% 수준으로 낮추어서, 저공해형의 환경 친화적인 특성을 갖는 제품이라고 할 수 있다.The water-soluble coating composition according to the present invention was evaluated to be excellent in workability and basic physical properties of the paint. In particular, it is excellent in terms of adhesion, peeling and storage properties, which are the most important physical properties in ship wire paints. Accordingly, the water-soluble coating composition according to the present invention has a low pollution type environmentally friendly characteristics by lowering the amount of volatile solvent 60 to 80% of the conventional oil paint to 30 to 50% while satisfying the required physical properties of the paint. It's a product.
Claims (16)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990018863A KR100302483B1 (en) | 1999-05-25 | 1999-05-25 | Water-soluble acryl-polyol resin composition, method for manufacturing the same and water-soluble paint composition containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990018863A KR100302483B1 (en) | 1999-05-25 | 1999-05-25 | Water-soluble acryl-polyol resin composition, method for manufacturing the same and water-soluble paint composition containing the same |
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| Publication Number | Publication Date |
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| KR20000074730A KR20000074730A (en) | 2000-12-15 |
| KR100302483B1 true KR100302483B1 (en) | 2001-10-18 |
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| KR100434269B1 (en) * | 2001-05-14 | 2004-06-04 | 대한비케미칼주식회사 | Coating composition including acrylic resin |
| KR100402268B1 (en) * | 2001-06-05 | 2003-10-17 | 대한비케미칼주식회사 | Paint Composition For Plastics |
| KR100724539B1 (en) * | 2004-12-24 | 2007-06-04 | (주)디피아이 홀딩스 | Paint for coating a cable used in ship |
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| KR970062000A (en) * | 1996-02-13 | 1997-09-12 | 한영재 | High Solid Acrylic Polyol Resin Composition and Manufacturing Method Thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR970062000A (en) * | 1996-02-13 | 1997-09-12 | 한영재 | High Solid Acrylic Polyol Resin Composition and Manufacturing Method Thereof |
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